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2. Synthesis and properties of processible copolymer microparticles from chloroanilines and anilineElectronic supplementary information (ESI) available: Table S1: Solubility and solution color of o-chloroaniline (OC)/AN and m-chloroaniline (MC)/AN copolymer base microparticles with an oxidant [(NH4)2S2O8]/monomer molar ratio of 1/2 in 1 M HCl. Table S2: The membrane formability of the OC/AN and MC/AN copolymer base microparticles in NMP by solution casting methods on glass and the characteristics of the membranes formed. Fig. S1: Wide-angle X-ray diffractograms of the virgin HCl salt and emeraldine base of OC homopolymer microparticles. Fig. S2: Actual air-separation performance through the blend membranes of the MC/AN (30/70) copolymer and 90 wt% ethylcellulose (EC) with operational temperature. See http://www.rsc.org/suppdata/jm/b4/b412587h/

Author

LiPresent address: Institute of Materials Chemistry, Xin-Gui, Engineering, School of Materials Science, Tongji, Huang, Mei-Rong, Lu, Ya-Qing, and Zhu, Mei-Fang

Abstract

Two series of functional copolymer microparticles were simply synthesized viaan oxidative polymerization of o-and m-chloroanilines OC and MC and aniline AN in HCl aqueous medium, for a detailed comparison between OCAN and MCAN copolymers. The polymerization characteristics, structures, and properties of the copolymers were systematically studied by gel permeation chromatographic, IR and UV-visible spectroscopic, wide-angle X-ray diffractive, and thermogravimetric techniques. The results showed that a small amount of AN can efficiently activate the oxidative polymerization of MC monomer although MC monomer can not homopolymerize oxidatively. A non-linear variation of the polymerization effect, molecular weight, and properties of the copolymers with the comonomer ratio suggests that the OCAN and MCAN polymers formed are genuine copolymers rather than a mixture of the corresponding homopolymers. The resultant copolymers show a remarkably enhanced solubility, a colorful solvatochromism and an improved processibility in comparison with polyaniline. The OCAN copolymers demonstrate a faster polymerization rate, narrower molecular weight distribution, and higher conductivity, but have a lower polymerization yield, molecular weight, thermostability, and air-separation capability than the MCAN copolymers.

Published
2005
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9. Flowered graphene: Growth, charge and thermal transport

Author

Cresti, Alessandro, Carrete, Jesús, Okuno, Hanako, Tao, Wang, Madsen, Georg K.H., Mingo, Natalio, Pochet, Pascal, Institut de Microélectronique, Electromagnétisme et Photonique - Laboratoire d'Hyperfréquences et Caractérisation (IMEP-LAHC), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Institute of Materials Chemistry, Vienna University of Technology (TU Wien), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Interdisciplinary Centre for Advanced Materials Simulation (ICAMS), Ruhr-Universität Bochum [Bochum], Laboratoire d'Innovation pour les Technologies des Energies Nouvelles et les nanomatériaux (LITEN), Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Modélisation et Exploration des Matériaux (MEM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), European Project: 645776,H2020,H2020-NMP-2014-two-stage,ALMA(2015), Cresti, Alessandro, ALL-SCALE PREDICTIVE DESIGN OF HEAT MANAGEMENT MATERIAL STRUCTURES WITH APPLICATIONS IN POWER ELECTRONICS - ALMA - - H20202015-06-01 - 2018-05-31 - 645776 - VALID, and Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
[SPI.NANO] Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, [PHYS.COND] Physics [physics]/Condensed Matter [cond-mat]
Abstract

International audience; Flower defects are the smallest dislocation loops observable in graphene. In this contribution [1], we illustrate their structural and transport properties investigated by means of high-resolution transmission electron microscopy and multiscale simulation tools based on density functional theory, Green’s functionsand Boltzmann transport equation. On the basis of our experimental images, we propose that flower defects are the grains left overby a bulge-type mechanism during the dynamic recrystallization of CVD graphene [2]. In order to explore their properties and the potential applications, we simulate electron and phonon transport in large graphene samples with different densities of flowers. At large densities, an energy-filtering effect is observed, with an almost unaffected hole transport and a significantly suppressed electron transport. This asymmetry originates from the flower-broken sublattice symmetry. For the same flower densities, heat transport is strongly decreased as a consequence of the dominant elastic scattering induced by the defects. Interestingly, even for low flower concentrations, the contribution of flexural phonons, which is significant in pristine graphene, is largely suppressed.[1] A. Cresti et al., Carbon161, 256 (2020)[2] A. Tyurnina et al., Carbon 102, 499 (2016)

Published
2020

10. Formation of Interstellar Complex Polycyclic Aromatic Hydrocarbons: Insights from Molecular Dynamics Simulations of Dehydrogenated Benzene

Author

Michel Devel, Meriem Hanine, Sylvain Picaud, Zhao Wang, Shiru Lu, Zhisen Meng, Peng Xie, Guangxi University [Nanning], Univers, Transport, Interfaces, Nanostructures, Atmosphère et environnement, Molécules (UMR 6213) (UTINAM), Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Franche-Comté Électronique Mécanique, Thermique et Optique - Sciences et Technologies (UMR 6174) (FEMTO-ST), Université de Technologie de Belfort-Montbeliard (UTBM)-Ecole Nationale Supérieure de Mécanique et des Microtechniques (ENSMM)-Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-Centre National de la Recherche Scientifique (CNRS), Institute of Materials Chemistry, Technical University of Vienna [Vienna] (TU WIEN), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC), and Vienna University of Technology (TU Wien)

Subjects
Fullerene, Astrochemistry, 010504 meteorology & atmospheric sciences, [SDU.ASTR.EP]Sciences of the Universe [physics]/Astrophysics [astro-ph]/Earth and Planetary Astrophysics [astro-ph.EP], chemistry.chemical_element, FOS: Physical sciences, 01 natural sciences, Chemical reaction, Interstellar medium, 0103 physical sciences, Reactivity (chemistry), Dehydrogenation, Molecule formation, Physics::Chemical Physics, 010303 astronomy & astrophysics, Astrophysics::Galaxy Astrophysics, Solar and Stellar Astrophysics (astro-ph.SR), 0105 earth and related environmental sciences, Cosmic dust, Physics, Interstellar molecules (849), [PHYS.PHYS.PHYS-ATM-PH]Physics [physics]/Physics [physics]/Atomic and Molecular Clusters [physics.atm-clus], Astronomy and Astrophysics, Interstellar molecules, Astrophysics - Astrophysics of Galaxies, Polycyclic aromatic hydrocarbons (1280), Polycyclic aromatic hydrocarbons, Astrophysics - Solar and Stellar Astrophysics, chemistry, Space and Planetary Science, Chemical physics, Astrophysics of Galaxies (astro-ph.GA), Astrochemistry (75), [PHYS.ASTR]Physics [physics]/Astrophysics [astro-ph], Carbon, Interstellar medium (847), Molecule formation (2076)
Abstract

Small organic molecules are thought to provide building blocks for the formation of complex interstellar polycyclic aromatic hydrocarbons (PAHs). However, the underlying chemical mechanisms remain unclear, particularly concerning the role of interstellar dust. Using molecular dynamics, we simulate the chemical reaction between dehydrogenated benzene molecules in the gas phase or on the surface of an onion-like carbon nanoparticle (NP). The reaction leads to the formation of PAHs of complex structures. The size of the formed molecules is found to roughly increase with increasing temperature up to 800 K, and to be correlated with the level of dehydrogenation. Morphology analysis features the formation of large rings that contain up to 32 carbon atom at high temperature. Density functional theory (DFT) calculations are performed to search the fundamental energetic reaction pathways. The DFT results quantitatively confirm the correlation between the reactivity and the dehydrogenation level, and the formation of stable C-8 rings. Moreover, the nanostructures formed on the NP surface point to a possible layer-by-layer formation mechanism for interstellar fullerene and carbon onions., Comment: 9 figures

Published
2020

11. Growth, charge and thermal transport of flowered graphene

Author

Georg K. H. Madsen, Pascal Pochet, Tao Wang, Hanako Okuno, Alessandro Cresti, Natalio Mingo, Jesús Carrete, Institut de Microélectronique, Electromagnétisme et Photonique - Laboratoire d'Hyperfréquences et Caractérisation (IMEP-LAHC), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Institute of Materials Chemistry, Vienna University of Technology (TU Wien), Laboratoire d'Etude des Matériaux par Microscopie Avancée (LEMMA ), Modélisation et Exploration des Matériaux (MEM), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Ruhr-Universität Bochum [Bochum], Laboratoire d'Innovation pour les Technologies des Energies Nouvelles et les nanomatériaux (LITEN), Institut National de L'Energie Solaire (INES), Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratory of Atomistic Simulation (LSIM), European Project: 645776,H2020,H2020-NMP-2014-two-stage,ALMA(2015), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut National Polytechnique de Grenoble (INPG)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Université Grenoble Alpes (UGA), Technical University of Vienna [Vienna] (TU WIEN), Laboratoire d'Etude des Matériaux par Microscopie Avancée (LEMMA), Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
Materials science, Phonon, FOS: Physical sciences, 02 engineering and technology, Electron, 010402 general chemistry, 01 natural sciences, law.invention, law, Mesoscale and Nanoscale Physics (cond-mat.mes-hall), General Materials Science, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], ComputingMilieux_MISCELLANEOUS, Elastic scattering, Condensed Matter - Materials Science, Condensed Matter - Mesoscale and Nanoscale Physics, Graphene, Recrystallization (metallurgy), Materials Science (cond-mat.mtrl-sci), General Chemistry, 021001 nanoscience & nanotechnology, Multiscale modeling, Electron transport chain, 0104 chemical sciences, Chemical physics, Dynamic recrystallization, 0210 nano-technology
Abstract

We report on the structural and transport properties of the smallest dislocation loop in graphene, known as a flower defect. First, by means of advanced experimental imaging techniques, we deduce how flower defects are formed during recrystallization of chemical vapor deposited graphene. We propose that the flower defects arise from a bulge type mechanism in which the flower domains are the grains left over by dynamic recrystallisation. Next, in order to evaluate the use of such defects as possible building blocks for all-graphene electronics, we combine multiscale modeling tools to investigate the structure and the electron and phonon transport properties of large monolayer graphene samples with a random distribution of flower defects. For large enough flower densities, we find that electron transport is strongly suppressed while, surprisingly, hole transport remains almost unaffected. These results suggest possible applications of flowered graphene for electron energy filtering. For the same defect densities, phonon transport is reduced by orders of magnitude as elastic scattering by defects becomes dominant. Heat transport by flexural phonons, key in graphene, is largely suppressed even for very low concentrations., Comment: 12 pages, 7 figures

Published
2020

15. Assessment of Artificial and Natural Transport Mechanisms of Ice Nucleating Particles in an Alpine Ski Resort in Obergurgl, Austria

Author

Baloh, Philipp, Els, Nora, Dávid, Róbert, Larose, Catherine, Whitmore, Karin, Sattler, Birgit, Grothe, Hinrich, Institute of Materials Chemistry, Vienna University of Technology (TU Wien), Cognition Behaviour Technology (CobTek), Université Côte d'Azur (UCA)-Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Centre Hospitalier Universitaire de Nice (CHU Nice)-Institut Claude Pompidou [Nice] (ICP - Nice), Ampère, Département Bioingénierie (BioIng), Ampère (AMPERE), École Centrale de Lyon (ECL), Université de Lyon-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-École Centrale de Lyon (ECL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), and Universitaere Service-Einrichtung fuer Transmissionselektronenmikroskopie (USTEM)

Subjects
ice nucleating particles, artificial snow, biological ice nucleation, alpine, particle transport, [SDV]Life Sciences [q-bio], lcsh:QR1-502, Microbiology, lcsh:Microbiology, [SPI]Engineering Sciences [physics], ice nucleating particles, artificial snow, biological ice nucleation, alpine, particle transport, human activities, Original Research
Abstract

International audience; Artificial snow production is a crucial part of modern skiing resorts in Austria and globally, and will develop even more so with changing precipitation patterns and a warming climate trend. Producing artificial snow requires major investments in energy, water, infrastructure and manpower for skiing resorts. In addition to appropriate meteorological conditions, the efficiency of artificial snow production depends on heterogeneous ice-nucleation, which can occur at temperatures as high as −2°C when induced by specific bacterial ice nucleating particles (INPs). We aimed to investigate the presence, source and ice nucleating properties of these particles in the water cycle of an alpine ski resort in Obergurgl, Tyrol, Austria. We sampled artificial snow, river water, water pumped from a storage pond and compared it to samples collected from fresh natural snow and aged piste snow from the area. Particles from each sampled system were characterized in order to determine their transport mechanisms at a ski resort. We applied a physical droplet freezing assay [DRoplet Ice Nuclei Counter Zurich (DRINCZ)] to heated and unheated samples to characterize the biological and non-biological component of IN-activity. Bacterial abundance and community structure of the samples was obtained using quantitative PCR and Illumina Mi-Seq Amplicon Sequencing, and their chemical properties were determined by liquid ion-chromatography, energy dispersive X-ray spectroscopy (EDX) and scanning electron microscopy (SEM). The results show the flow of biological and inorganic material from the river to the slopes, an uptake of new microorganisms through the air and the piping, and possible proliferation or introduction of ice nucleation active biological particles in aged piste snow. Natural snow, as the first stage in this system, had the lowest amount of ice nucleation active particles and the least amount of biological and mineral particles in general, yet shares some microbial characteristics with fresh artificial snow.

Published
2019

16. Synthesis of fluorescent polycarbonates with highly twisted N , N -bis(dialkylamino)anthracene AIE luminogens in the main chain

Author

Amir Sharidan Sairi, Kohei Kuwahara, Kazunobu Igawa, Gen-ichi Konishi, Tomoyoshi Suenobu, Shinji Ando, Satoshi Suzuki, Keiji Morokuma, Shunsuke Sasaki, Masatoshi Tokita, Tokyo Institute of Technology [Tokyo] (TITECH), Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Fukui Institute for Fundamental Chemistry, Kyoto University, Institute for Materials Chemistry and Engineering, Kyushu University [Fukuoka], Department of Material and Life Science, Graduate School of Engineering, Osaka University, Osaka University [Osaka], PRESTO [JST, and Japan Science and Technology Agency

Subjects
Anthracene, Bisphenol A, Scanning electron microscope, General Chemical Engineering, Solid-state, Quantum yield, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Fluorescence, 0104 chemical sciences, chemistry.chemical_compound, Differential scanning calorimetry, Monomer, chemistry, Polymer chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

A synthetic route to embed aggregation-induced-emission-(AIE)-active luminophores in polycarbonates (PCs) in various ratios is reported. The AIE-active monomer is based on the structure of 9,10-bis(piperidyl)anthracene. The obtained PCs display good film-forming properties, similar to those observed in poly(bisphenol A carbonate) (Ba-PC). The fluorescence quantum yield (Φ) of the PC with 5 mol% AIE-active monomer was 0.04 in solution and 0.53 in solid state. Moreover, this PC is also miscible with commercially available Ba-PC at any blending ratio. A combined analysis by scanning electron microscopy and differential scanning calorimetry did not indicate any clear phase separation. These results thus suggest that even engineering plastics like polycarbonates can be functionalized with AIE luminogens without adverse effects on their physical properties.

Published
2019

17. An investigation of the structural properties of Li and Na fast ion conductors using high-throughput bond-valence calculations and machine learning

Author

Marine Reynaud, Natalio Mingo, Juan Rodríguez-Carvajal, Javier Carrasco, Gwenaëlle Rousse, Jesús Carrete, Montse Casas-Cabanas, Nebil A. Katcho, Institute of Materials Chemistry, Vienna University of Technology (TU Wien), CIC EnergiGUNE (SPAIN), Université Pierre et Marie Curie - Paris 6 (UPMC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Innovation pour les Technologies des Energies Nouvelles et les nanomatériaux (LITEN), Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Institut Laue-Langevin (ILL), and CICEnergigune

Subjects
Valence (chemistry), Materials science, Coordination number, Ionic bonding, 02 engineering and technology, Crystal structure, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, General Biochemistry, Genetics and Molecular Biology, Chemical space, 0104 chemical sciences, Chemical physics, Volume fraction, Fast ion conductor, 0210 nano-technology, Electrical conductor
Abstract

Progress in energy-related technologies demands new and improved materials with high ionic conductivities. Na- and Li-based compounds have high priority in this regard owing to their importance for batteries. This work presents a high-throughput exploration of the chemical space for such compounds. The results suggest that there are significantly fewer Na-based conductors with low migration energies as compared to Li-based ones. This is traced to the fact that, in contrast to Li, the low diffusion barriers hinge on unusual values of some structural properties. Crystal structures are characterized through descriptors derived from bond-valence theory, graph percolation and geometric analysis. A machine-learning analysis reveals that the ion migration energy is mainly determined by the global bottleneck for ion migration, by the coordination number of the cation and by the volume fraction of the mobile species. This workflow has been implemented in the open-source Crystallographic Fortran Modules Library (CrysFML) and the program BondStr. A ranking of Li- and Na-based ionic compounds with low migration energies is provided.

Published
2019

18. Efficient and accurate calculation of band gaps of halide perovskites with the Tran-Blaha modified Becke-Johnson potential

Author

Mikael Kepenekian, Xavier Rocquefelte, Fabien Tran, Gaëlle Bouder, Boubacar Traore, Claudine Katan, William Lafargue-Dit-Hauret, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Institute of Materials Chemistry, Vienna University of Technology (TU Wien), 2017-A0010907682, Grand Équipement National De Calcul Intensif, 687008, Horizon 2020, F41, Austrian Science Fund, ANR-15-CE05-0018,TRANSHYPERO,Vers une compréhension des propriétés de transport électronique des cellules solaires basées sur les pérovskites hybrides(2015), European Project: 687008,H2020,H2020-FETOPEN-2014-2015-RIA,GOTSolar(2016), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), and Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)

Subjects
Materials science, hybrid organic-inorganic, Band gap, band structure, perovskites, Halide, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Electronic structure, Large range, electronic structure, 021001 nanoscience & nanotechnology, DFT, 01 natural sciences, 7. Clean energy, Computational physics, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Pseudopotential, 0103 physical sciences, Density functional theory, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], Hop (telecommunications), 010306 general physics, 0210 nano-technology, Electronic band structure
Abstract

This work was granted access to the HPC resources of [TGCC/CINES/IDRIS] under allocation 2017-A0010907682 made by GENCI.; International audience; We report on a reoptimization of the Tran-Blaha modified Becke-Johnson (TB-mBJ) potential dedicated to the prediction of the band gaps of 3-dimensional (3D) and layered hybrid organic-inorganic perovskites (HOP) within pseudopotential-based density functional theory methods. These materials hold promise for future photovoltaic and optoelectronic applications. We begin by determining a set of parameters for 3D HOP optimized over a large range of materials. Then we consider the case of layered HOP. We design an empirical relationship that facilitates the prediction of band gaps of layered HOP with arbitrary interlayer molecular spacers with a computational cost considerably lower than more advanced methods like hybrid or GW. Our study also shows that substituting interlayer molecular chains of layered HOP with Cs atoms is an appealing and cost-effective route to band gap calculations. Finally, we discuss on the pitfalls and limitations of TB-mBJ for HOP, notably its tendency to overestimate the effective masses due to the narrowing of the band dispersions. We expect our results to extend the use of TB-mBJ for other low-dimensional materials.

Published
2019

19. Synthesis, Structures and Conformational Studies of 1,2-Dimethyl[2.10]metacyclophan-1-enes

Author

Shofiur Rahman, Thamina Akther, Taisuke Matsumoto, Carl Redshaw, Pierre Thuéry, Junji Tanaka, Paris E. Georghiou, Takehiko Yamato, Monarul Islam, Department of Applied Chemistry, Saga University [Japon], Memorial University of Newfoundland = Université Memorial de Terre-Neuve [St. John's, Canada] (MUN), Institute of Materials Chemistry and Engineering (Japan), Kyushu University, Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Hull [United Kingdom], and Memorial University of Newfoundland [St. John's]

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Stereochemistry, Hydrogen bond, Substituent, General Chemistry, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Coupling reaction, 0104 chemical sciences, Acylation, chemistry.chemical_compound, chemistry, Intramolecular force, [CHIM.CRIS]Chemical Sciences/Cristallography, Boron tribromide, Hexamethylenetetramine, Demethylation
Abstract

International audience; A series of 1,2‐dimethyl[2.10]metacyclophan‐1‐enes (MCP‐1‐enes) containing different substituent groups has been synthesized to illustrate their conformational behavior. 4,22‐dimethoxy‐1,2‐dimethyl[2.10]MCP‐1‐ene 3 was synthesized by a Grignard coupling reaction, Friedel‐Crafts acylation reactions and McMurry coupling reaction from 1,10‐dibromodecane. The formation of 4,22‐dihydroxy‐1,2‐dimethyl[2.10]MCP‐1‐ene 4 was carried out by demethylation of compound 3 with boron tribromide at room temperature. The syn type conformation of 4 was characterized by X‐ray diffraction and was found to form both intramolecular and intermolecular hydrogen bonds between the two hydroxyl groups. From this reaction an interesting compound [10]tetrahydrobenzofuranophane 5 was afforded on prolonging the reaction time. 5,21‐diformyl‐4,22‐dihydroxy‐1,2‐dimethyl[2.10]MCP‐1‐ene 6 has been prepared from 4,22‐dihydroxy‐1,2‐dimethyl[2.10]MCP‐1‐ene 4 by using the Duff method in the presence of hexamethylenetetramine. Structural analysis by 1H NMR spectroscopy and X‐ray diffraction confirmed that both the solution and the crystalline state of compound 6 adopts an anti‐conformation which forms an intramolecular hydrogen bond between the formyl group and the hydroxyl group, which is an interesting finding for long carbon chain MCP compounds.

Published
2016

20. Aerogels from Cellulose Phosphates of Low Degree of Substitution: A TBAF·H2O/DMSO Based Approach

Author

Christian Bruno Schimper, Thomas Rosenau, Hubert Hettegger, Martin Wendland, Marie-Alexandra Neouze, Paul Pachschwoell, Falk Liebner, Jean-Marie Nedelec, University of Natural Resources and Life Sciences (BOKU), Vienna University of Technology, Institute of Materials Chemistry, Getreidemarkt 9/165, A-1060 Vienna, Institut de Chimie de Clermont-Ferrand (ICCF), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne (UCA)-Institut national polytechnique Clermont Auvergne (INP Clermont Auvergne), Université Clermont Auvergne (UCA)-Université Clermont Auvergne (UCA), University Aveiro, Department of Chemistry and CICECO Aveiro Institute of Materials, Campus Universitário de Santiago, 3810-193 Aveiro, and Universität für Bodenkultur Wien = University of Natural Resources and Life [Vienne, Autriche] (BOKU)

Subjects
cellulose phosphate aerogel, Pharmaceutical Science, 02 engineering and technology, engineering.material, 010402 general chemistry, 01 natural sciences, Article, Phosphates, Analytical Chemistry, lcsh:QD241-441, chemistry.chemical_compound, tetrabutylammonium fluoride, Biopolymers, lcsh:Organic chemistry, supercritical carbon dioxide, Cellulose phosphate, interconnected porosity, Drug Discovery, [CHIM]Chemical Sciences, Dimethyl Sulfoxide, Physical and Theoretical Chemistry, Cellulose, Porosity, Dissolution, Supercritical carbon dioxide, Organic Chemistry, cellulose phosphate, Water, TBAF/DMSO, 021001 nanoscience & nanotechnology, Nanostructures, 0104 chemical sciences, Quaternary Ammonium Compounds, Solvent, Chemical engineering, chemistry, Chemistry (miscellaneous), Cellulosic ethanol, Solvents, engineering, Molecular Medicine, Biopolymer, 0210 nano-technology, Gels
Abstract

Biopolymer aerogels of appropriate open-porous morphology, nanotopology, surface chemistry, and mechanical properties can be promising cell scaffolding materials. Here, we report a facile approach towards the preparation of cellulose phosphate aerogels from two types of cellulosic source materials. Since high degrees of phosphorylation would afford water-soluble products inappropriate for cell scaffolding, products of low DSP (ca. 0.2) were prepared by a heterogeneous approach. Aiming at both i) full preservation of chemical integrity of cellulose during dissolution and ii) utilization of specific phase separation mechanisms upon coagulation of cellulose, TBAF&middot, H2O/DMSO was employed as a non-derivatizing solvent. Sequential dissolution of cellulose phosphates, casting, coagulation, solvent exchange, and scCO2 drying afforded lightweight, nano-porous aerogels. Compared to their non-derivatized counterparts, cellulose phosphate aerogels are less sensitive towards shrinking during solvent exchange. This is presumably due to electrostatic repulsion and translates into faster scCO2 drying. The low DSP values have no negative impact on pore size distribution, specific surface (SBET &le, 310 m2 g&minus, 1), porosity (&Pi, 95.5&ndash, 97 vol.%), or stiffness (E&rho, &le, 211 MPa cm3 g&minus, 1). Considering the sterilization capabilities of scCO2, existing templating opportunities to afford dual-porous scaffolds and the good hemocompatibility of phosphorylated cellulose, TBAF&middot, H2O/DMSO can be regarded a promising solvent system for the manufacture of cell scaffolding materials.

Published
2020

21. Emulsion and Foam Templating-Promising Routes to Tailor-Made Porous Polymers

Author

Cosima Stubenrauch, Wiebke Drenckhan, Alexander Bismarck, Angelika Menner, Institut für Physikalische Chemie [Stuttgart], Universität Stuttgart [Stuttgart], Institute of Materials Chemistry and Research, University of Vienna, Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), and Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Materials science, Dispersity, Nanotechnology, 02 engineering and technology, General Chemistry, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Bridge (interpersonal), Catalysis, 0104 chemical sciences, Template, chemistry, Emulsion, 0210 nano-technology, Porosity
Abstract

International audience; Emulsions, foams, and foamed emulsions have been used successfully as templates for the synthesis of macroporous polymers. Based on this knowledge this Minireview presents strategies to use, optimise, and upscale these templating methods to synthesise tailor‐made porous polymers. The uniqueness of such polymers lies in the ability to tailor their structures and, therefore, their properties. However, systematic studies on structure–property relations are lacking mainly because the templating scientific community is “split into two”: the polydisperse and monodisperse camps. Thus, it is time to build a bridge between the camps, that is, to synthesise porous polymers with very different structures from the same precursors to determine the relationship between the structure and the properties.

Published
2018

22. Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane

Author

Taisuke Matsumoto, Carl Redshaw, Takehiko Yamato, Junji Tanaka, Thamina Akther, Md. Monarul Islam, Pierre Thuéry, Saga University [Japon], Chemical Research Division (Bengladesh), Bangladesh Council of Scientific and Industrial Research (BCSIR), Institute of Materials Chemistry and Engineering (Japan), Kyushu University, Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Hull [United Kingdom], Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Metacyclophane, chirality, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Coupling reaction, chemistry.chemical_compound, Drug Discovery, Pyridine, McMurry reaction, Diels–Alder reaction, Dimethyl acetylenedicarboxylate, 010405 organic chemistry, Chemistry, Bromination, Organic Chemistry, Aromatization, [CHIM.MATE]Chemical Sciences/Material chemistry, 0104 chemical sciences, 3. Good health, Enantiomer, Chirality (chemistry)
Abstract

International audience; The reductive coupling reaction of 1,4-bis(3-acetyl-5-tert-butyl-2-methoxyphenyl)butane 3 was carried out using TiCl4-Zn in pyridine followed by a McMurry coupling reaction to afford the compounds anti and syn 1,2-dimethyl[2.4]MCP-1-ene 4. Bromination of 4 with BTMA-Br$_3$ in dry CH$_2$Cl$_2$ afforded the interesting compound 1,2-bis-(bromomethyl)-5,15-di-tert-butyl-8,18-dimethoxy[2.4]MCP-1-ene 6 and consecutive debromination with Zn and AcOH in CH2$_C$l$_2$ solution afforded the stable solid 5,15-di-tert-butyl-8,18-dimethoxy-1,2-dimethylene[2.4]MCP 7 in 89% yield. Compound 7 was conveniently employed in a Diels–Alder reaction with dimethyl acetylenedicarboxylate (DMAD) to provide 2-(3′,6′-dihydrobenzo)-5,15-di-tert-butyl-8,18-dimethoxy[2.4]MCP-4′,5′-dimethylcarboxylate 8 in good yield. Diels–Alder adduct 8 was converted into a novel and inherently chiral areno-bridged compound [2.4]MCP 9 by aromatization. The chirality of the two conformers was characterized by circular dichroism (CD) spectra of the separated enantiomer which are perfect mirror images of each other.

Published
2017

23. Investigation of the Optical and Excitonic Properties of the Visible Light-Driven Photocatalytic BiVO4 Material

Author

Peter Blaha, Robert Laskowski, Tilak Das, Stéphane Jobic, Xavier Rocquefelte, Luc Lajaunie, Karlheinz Schwarz, Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institute of High Performance Computing (IHPC), Institute of Materials Chemistry, Vienna University of Technology (TU Wien), Austrian Science Foundation FWF [SFB F41], European Union [312483 ESTEEM2, 696656], European Project: 312483,EC:FP7:INFRA,FP7-INFRASTRUCTURES-2012-1,ESTEEM 2(2012), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Anatase, Materials science, business.industry, General Chemical Engineering, 02 engineering and technology, General Chemistry, Electron, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Crystal, Optics, Rutile, Materials Chemistry, Photocatalysis, Optoelectronics, Density functional theory, 0210 nano-technology, business, Spectroscopy, Visible spectrum
Abstract

International audience; An investigation of the optical and excitonic properties of photocatalytic compounds based on both experimental and theoretical approaches is proposed. More specifically, this paper reports, for the first time, the local-field, optical anisotropy, and excitonic effects in BiVO4, an active photocatalytic material in the visible range. The analyses are based on electron energy-loss spectroscopy measurements, ground-state density functional theory calculations, including crystal local-field effects, and many-body corrections using the Bethe-Salpeter equation. These results are supported by a comparison with two materials, namely, TiO2 anatase and rutile, which are well-known to differ in their photocatalytic properties, those being important and negligible, respectively. The analogies found for these two categories of compounds allow the proposal of criteria that appear to be essential for producing an optimal photocatalytic material.

Published
2017

24. Synthesis and structure of 1,2-dimethylene[2.10]metacyclophane and its conversion to chiral [10]benzenometacyclophanes

Author

Akhter, Thamina, Islam, Md Monarul, Matsumoto, Taisuke, Tanaka, Junji, Thuéry, Pierre, Redshaw, Carl, Department of Applied Chemistry, Saga University [Japon], Institute of Materials Chemistry and Engineering, Kyushu University, Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
[CHIM.MATE]Chemical Sciences/Material chemistry
Abstract

International audience; Bromination of 5,21-di-tert-butyl-8,24-dimethoxy-1,2-dimethyl[2.10]metacyclophan-1-ene (MCP-1-ene) 1 with benzyltrimethylammonium tribromide exclusively afforded 1,2-bis(bromomethyl)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-1-ene 2. Debromination of 2 with Zn and AcOH in CH2Cl2 solution at room temperature for 24 h produced the identical dimethylene[2.10]MCP 7 in 92% yield, which is a stable solid compound. Subsequently, compound 7 was reacted with dimethyl acetylenedicarboxylate (DMAD) to provide 1,2-(3',6'-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-4',5'-dimethylcarboxylate 8 in good yield. Diels-Alder adduct 8 was converted to a novel and inherently chiral areno-bridged dimethoxy[2.10]MCP-4',5'-dimethylcarboxylate 9 by aromatization with dichlorodicyano-p-benzoquinone (DDQ), possessing C1 symmetry. Also a new type of N-phenyl-maleimide substituted 1,2-(3',6'-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy [2.10]MCP-4',5'-N-phenylmaleimide 10 was synthesised from 7 via treatment with N-phenylmaleimide in toluene at 110°C followed by aromatization with DDQ. Single crystal X-ray analysis of 9 revealed the adoption of a syn-isomer.

Published
2017
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25. Ethanol–water co-condensation into hydrophobic mesoporous thin films: example of a photonic ethanol vapor sensor in humid environment

Author

Marco Faustini, Andrea Cattoni, David Grosso, Mickael Boudot, Institute for Materials Chemistry and Engineering, Kyushu University [Fukuoka], Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Collège de France (CdF)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de photonique et de nanostructures (LPN), Centre National de la Recherche Scientifique (CNRS), Centre de Nanosciences et de Nanotechnologies [Marcoussis] (C2N), Université Paris-Sud - Paris 11 (UP11)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut des Matériaux, de Microélectronique et des Nanosciences de Provence (IM2NP), Aix Marseille Université (AMU)-Université de Toulon (UTLN)-Centre National de la Recherche Scientifique (CNRS), Matériaux Hybrides et Nanomatériaux (LCMCP-MHN), Collège de France (CdF)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Vapor pressure, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biomaterials, Adsorption, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Materials Chemistry, Organic chemistry, Relative humidity, Thin film, optical sensor, Capillary condensation, Humidity, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Mesoporous silica, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, sol gel nanoimprinting, Chemical engineering, ethanol sensing, Ceramics and Composites, 0210 nano-technology, Mesoporous material, Hydro-alcoholic capillary co-condensation
Abstract

International audience; In this work, we report a new generation of sol gel photonic vapor sensor based on water repellent methyl functionalized mesoporous silica thin films for the detection of alcohol vapors. Relative humidity, generally accountable for sensor performance deterioration, was demonstrated as a key parameter to detect and enhance sensor sensitivity concerning ethanol. The ethanol-assisted water vapors capillary condensation into hydrophobic mesopores was observed and investigated as an innovative sensing mechanism. We showed that water condensation was triggered by the surfactant-like behavior of alcohol molecules whose alkyl moieties preferentially interact with the hydrophobic walls and reversibly switch the surface energy from hydrophobic to hydrophilic. Influence of the ethanol and water pressure conditions for which the capillary condensation occurs were studied by in situ-ellipsometry. This study revealed a synergic mechanism of co-adsorption where the minimum ethanol concentration allowing water capillary adsorption decreases when humidity increases. Nanopatterned diffraction gratings films, fabricated via a nanoimprinting process, were demonstrated to be efficient transductor to transform the capillary induced nanoscale variations of refractive index of the porous materials into optical signals easily measurable by conventional camera. Sensing results exhibited an ethanol vapor pressure threshold limit of detection of P/P0 EtOH = 0.07 at 100% relative humidity and typical response and regeneration times are below one minute.

Published
2017

26. Reproducibility in density functional theory calculations of solids

Author

Patrik Thunström, Ulrike Nitzsche, Georg Kresse, Stefan Goedecker, Stewart J. Clark, Claudia Draxl, José A. Flores-Livas, Martin Schlipf, Xavier Gonze, P. J. Hasnip, Klaus Koepernik, Marc Torrent, Matthias Scheffler, F. Jollet, Alexandre Tkatchenko, Martijn Marsman, Jonathan R. Yates, Volker Blum, Paolo Giannozzi, Gustav Bihlmayer, D. R. Hamann, Oscar Grånäs, Torbjörn Björkman, Nicola Marzari, Matteo Giantomassi, Keith Refson, Yaroslav Kvashnin, Natalie Holzwarth, Michiel van Setten, Guo-Xu Zhang, Taisuke Ozaki, Stefano de Gironcoli, Ivano E. Castelli, Stefaan Cottenier, Chris J. Pickard, J. K. Dewhurst, David Vanderbilt, Manuel Richter, Thierry Deutsch, Veronique Van Speybroeck, Gian-Marco Rignanese, Ward Poelmans, Kurt Lejaeghere, Sangeeta Sharma, Damien Caliste, Lorenzo Paulatto, Igor Di Marco, Francesca Tavazza, Emine Kucukbenli, Peter Blaha, Francois Gygi, Stefan Blügel, Andrea Dal Corso, Dominik B. Jochym, Lars Nordström, Karlheinz Schwarz, Luigi Genovese, Santanu Saha, Diana Iusan, Matt Probert, John M. Wills, Andris Gulans, Daniel M. Jones, E. K. U. Gross, Inka L. M. Locht, Sven Lubeck, Marcin Dulak, Kevin F. Garrity, Olle Eriksson, Center for molecular modeling, Universiteit Gent = Ghent University (UGENT), Institute of Materials Chemistry, Vienna University of Technology (TU Wien), Laboratory of Atomistic Simulation (LSIM ), Modélisation et Exploration des Matériaux (MEM), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Department of Physics [Durham], Durham University, Department of Physics and Astronomy [Uppsala], Uppsala University, Max-Planck-Institut für Mikrostrukturphysik (MPI-HALLE), Max-Planck-Gesellschaft, University of Udine Italy, University of Basel (Unibas), Institut de la matière condensée et des nanosciences / Institute of Condensed Matter and Nanosciences (IMCN), Université Catholique de Louvain = Catholic University of Louvain (UCL), University of Oxford, Ecole Polytechnique Fédérale de Lausanne (EPFL), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de recherche pour le développement [IRD] : UR206-Centre National de la Recherche Scientifique (CNRS), Department of Materials Science and Metallurgy [Cambridge University] (DMSM), University of Cambridge [UK] (CAM), STFC Rutherford Appleton Laboratory (RAL), Science and Technology Facilities Council (STFC), DAM Île-de-France (DAM/DIF), Direction des Applications Militaires (DAM), European Project: 329386,EC:FP7:PEOPLE,FP7-PEOPLE-2012-IEF,EXMAMA(2013), European Project: 676580,H2020,H2020-EINFRA-2015-1,NoMaD(2015), Universiteit Gent = Ghent University [Belgium] (UGENT), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), University of Oxford [Oxford], Pickard, Christopher [0000-0002-9684-5432], and Apollo - University of Cambridge Repository

Subjects
REGULAR APPROXIMATIONS, DFT, first principles, delta test, Materialkemi, 02 engineering and technology, generalized-gradient approximation, augmented-wave method, regular approximations, pseudopotentials, silicon, state, 1st-principles, crystals, science, energy, 01 natural sciences, 1st-Principles, ENERGY, Materials Chemistry, Statistical physics, Pseudopotentials, validation, [PHYS]Physics [physics], Physics, Multidisciplinary, 0104 Statistics, SCIENCE, Condensed Matter Physics, 021001 nanoscience & nanotechnology, STATE, Generalized-Gradient Approximation, Density functional theory, 0210 nano-technology, Den kondenserade materiens fysik, Theory of Condensed Matter, Augmented-Wave Method, 010402 general chemistry, AUGMENTED-WAVE METHOD, Settore FIS/03 - Fisica della Materia, Theoretical physics, Generalized gradient, Clinical Research, SILICON, Basis set, GENERALIZED-GRADIENT APPROXIMATION, Reproducibility, ta114, 1ST-PRINCIPLES, PSEUDOPOTENTIALS, 0104 chemical sciences, CRYSTALS, Formalism (philosophy of mathematics), Physics and Astronomy, numerical simulation, Pairwise comparison
Abstract

NTRODUCTION The reproducibility of results is one of the underlying principles of science. An observation can only be accepted by the scientific community when it can be confirmed by independent studies. However, reproducibility does not come easily. Recent works have painfully exposed cases where previous conclusions were not upheld. The scrutiny of the scientific community has also turned to research involving computer programs, finding that reproducibility depends more strongly on implementation than commonly thought. These problems are especially relevant for property predictions of crystals and molecules, which hinge on precise computer implementations of the governing equation of quantum physics. RATIONALE This work focuses on density functional theory (DFT), a particularly popular quantum method for both academic and industrial applications. More than 15,000 DFT papers are published each year, and DFT is now increasingly used in an automated fashion to build large databases or apply multiscale techniques with limited human supervision. Therefore, the reproducibility of DFT results underlies the scientific credibility of a substantial fraction of current work in the natural and engineering sciences. A plethora of DFT computer codes are available, many of them differing considerably in their details of implementation, and each yielding a certain “precision” relative to other codes. How is one to decide for more than a few simple cases which code predicts the correct result, and which does not? We devised a procedure to assess the precision of DFT methods and used this to demonstrate reproducibility among many of the most widely used DFT codes. The essential part of this assessment is a pairwise comparison of a wide range of methods with respect to their predictions of the equations of state of the elemental crystals. This effort required the combined expertise of a large group of code developers and expert users. RESULTS We calculated equation-of-state data for four classes of DFT implementations, totaling 40 methods. Most codes agree very well, with pairwise differences that are comparable to those between different high-precision experiments. Even in the case of pseudization approaches, which largely depend on the atomic potentials used, a similar precision can be obtained as when using the full potential. The remaining deviations are due to subtle effects, such as specific numerical implementations or the treatment of relativistic terms. CONCLUSION Our work demonstrates that the precision of DFT implementations can be determined, even in the absence of one absolute reference code. Although this was not the case 5 to 10 years ago, most of the commonly used codes and methods are now found to predict essentially identical results. The established precision of DFT codes not only ensures the reproducibility of DFT predictions but also puts several past and future developments on a firmer footing. Any newly developed methodology can now be tested against the benchmark to verify whether it reaches the same level of precision. New DFT applications can be shown to have used a sufficiently precise method. Moreover, high-precision DFT calculations are essential for developing improvements to DFT methodology, such as new density functionals, which may further increase the predictive power of the simulations.

Published
2016

27. Unique Difference in Transition Temperature of Two Similar Fluorinated Side Chain Polymers Forming Hexatic Smectic Phase: Poly{2-(perfluorooctyl)ethyl acrylate} and Poly{2- (perfluorooctyl)ethyl vinyl ether}

Author

Ahmed Meskini, Kevin L. White, Atsushi Takahara, Mustapha Raihane, Takamichi Shinohara, Ryohei Ishige, Bruno Ameduri, Kyushu University [Fukuoka], Institute for Materials Chemistry and Engineering, Kyushu Univesity, Kyushu University [Fukuoka]-Kyushu University [Fukuoka], Laboratoire de Chimie Bioorganique et Macromoléculaire - Faculté des Sciences et Techniques (LCBM), Université Cadi Ayyad [Marrakech] (UCA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and collaboration apres sejours (BA) en 2012 et 2013

Subjects
Materials science, Polymers and Plastics, fluoropolymer, 02 engineering and technology, thermal behavior, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, liquid-crystalline structure, chemistry.chemical_compound, Phase (matter), Polymer chemistry, Materials Chemistry, medicine, Side chain, Fourier transform infrared spectroscopy, chemistry.chemical_classification, Acrylate, comb-shaped polymers, Organic Chemistry, Polymer, Vinyl ether, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Functional group, hexatic smectic structures poly(fluoro acrylate ), Ethyl acrylate, surface properties, 0210 nano-technology, isotropization temperature, medicine.drug
Abstract

collaboration; International audience; The surface properties of comb-shaped polymers with perfluorooctyl ethyl side-chains are strongly related to the ordered structure of the side-chains at the surface. In this work, the thermal behavior, liquid- crystalline structure, and functional group orientation ofcomb-shaped polymers containing perfluorooctyl side-chains with poly(acrylate) (PFA-C8) 21 and poly(vinyl ether) (PFAVE8) backbones are discussed based on DSC, synchrotron-source X-ray diffraction, and FTIR measurements. Despite the similar tilted hexatic smectic structures and packing entropies, the isotropization temperature, Ti, of the PFA-C8 is significantly higher than the PFAVE8. Detailed characterization of the conformation, alignment, and organization of the perfluorooctyl side-chains indicate that the difference in Ti is related to the configuration of side-chains and interactions between the carbonyl groups along the acrylate backbone. The present findings show that the type of the linkage between the polymerbackbone and fluorinated side-chain mesogens affects the conformation and plays an important role in determining thermal behavior.

Published
2014

28. Nanoparticle assemblies from molecular mediator

Author

Néouze, Marie-Alexandra, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institute of Materials Chemistry, Vienna University of Technology (TU Wien), Pignataro, Bruno, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.MATE]Chemical Sciences/Material chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2014

29. A community effort to assess and improve drug sensitivity prediction algorithms

Author

Costello, James C, Heiser, Laura M, Georgii, Elisabeth, Gönen, Mehmet, Menden, Michael P, Wang, Nicholas J, Bansal, Mukesh, Ammad-ud-din, Muhammad, Hintsanen, Petteri, Khan, Suleiman A, Mpindi, John-Patrick, Kallioniemi, Olli, Honkela, Antti, Aittokallio, Tero, Wennerberg, Krister, Abbuehl, Jean-Paul, Allen, Jeffrey, Altman, Russ B, Balcome, Shawn, Battle, Alexis, Bender, Andreas, Berger, Bonnie, Bernard, Jonathan, Bhattacharjee, Madhuchhanda, Bhuvaneshwar, Krithika, Bieberich, Andrew A, Boehm, Fred, Califano, Andrea, Chan, Christina, Chen, Beibei, Chen, Ting-Huei, Choi, Jaejoon, Coelho, Luis Pedro, Cokelaer, Thomas, Collins, James C, Creighton, Chad J, Cui, Jike, Dampier, Will, Davisson, V Jo, De Baets, Bernard, Deshpande, Raamesh, DiCamillo, Barbara, Dundar, Murat, Duren, Zhana, Ertel, Adam, Fan, Haoyang, Fang, Hongbin, Gallahan, Dan, Gauba, Robinder, Gottlieb, Assaf, Grau, Michael, Gray, Joe W, Gusev, Yuriy, Ha, Min Jin, Han, Leng, Harris, Michael, Henderson, Nicholas, Hejase, Hussein A, Homicsko, Krisztian, Hou, Jack P, Hwang, Woochang, IJzerman, Adriaan P, Karacali, Bilge, Kaski, Samuel, Keles, Sunduz, Kendziorski, Christina, Kim, Junho, Kim, Min, Kim, Youngchul, Knowles, David A, Koller, Daphne, Lee, Junehawk, Lee, Jae K, Lenselink, Eelke B, Li, Biao, Li, Bin, Li, Jun, Liang, Han, Ma, Jian, Madhavan, Subha, Mooney, Sean, Myers, Chad L, Newton, Michael A, Overington, John P, Pal, Ranadip, Peng, Jian, Pestell, Richard, Prill, Robert J, Qiu, Peng, Rajwa, Bartek, Sadanandam, Anguraj, Saez-Rodriguez, Julio, Sambo, Francesco, Shin, Hyunjin, Singer, Dinah, Song, Jiuzhou, Song, Lei, Sridhar, Arvind, Stock, Michiel, Stolovitzky, Gustavo, Sun, Wei, Ta, Tram, Tadesse, Mahlet, Tan, Ming, Tang, Hao, Theodorescu, Dan, Toffolo, Gianna Maria, Tozeren, Aydin, Trepicchio, William, Varoquaux, Nelle, Vert, Jean-Philippe, Waegeman, Willem, Walter, Thomas, Wan, Qian, Wang, Difei, Wang, Wen, Wang, Yong, Wang, Zhishi, Wegner, Joerg K, Wu, Tongtong, Xia, Tian, Xiao, Guanghua, Xie, Yang, Xu, Yanxun, Yang, Jichen, Yuan, Yuan, Zhang, Shihua, Zhang, Xiang-Sun, Zhao, Junfei, Zuo, Chandler, van Vlijmen, Herman W T, van Westen, Gerard J P, Collins, James J, National Centre for Plasma Science and Technology (NCPST), Dublin City University [Dublin] ( DCU ), Institut Lumière Matière [Villeurbanne] ( ILM ), Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Mécanique des Contacts et des Structures [Villeurbanne] ( LaMCoS ), Institut National des Sciences Appliquées de Lyon ( INSA Lyon ), Université de Lyon-Institut National des Sciences Appliquées ( INSA ) -Université de Lyon-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Helsinki Institute for Information Technology, University of Westminster [London] ( UOW ), Stanford Center for BioMedical Informatics Research ( BMIR ), Stanford University [Stanford], DSTO, Equipe NEMESIS - Centre de Recherches de l'Institut du Cerveau et de la Moelle épinière ( NEMESIS-CRICM ), Centre de Recherche de l'Institut du Cerveau et de la Moelle épinière ( CRICM ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Institut National de la Santé et de la Recherche Médicale ( INSERM ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Institut National de la Santé et de la Recherche Médicale ( INSERM ) -Centre National de la Recherche Scientifique ( CNRS ), Institute for Molecular Bioscience, and ARC Centre of Excellence in Bioinformatics, The University of Queensland, Brisbane, QLD 4072, Nanjing University of Information Science & Technology, Department of Physics [Stockholm], Stockholm University, Chercheur indépendant, Instituto de Engenharia de Sistemas e Computadores ( INESC ), European Bioinformatics Institute [Hinxton] ( EMBL-EBI ), European Molecular Biology Laboratory [Hinxton], Department of Agronomy, Tianjin Agricultural University ( TJAU ), Medicine Faculty, Erciyes University, Faculty of anima Medicine l, Northeast Agricultural University [Harbin], Oxford e-Research Centre [Oxford], University of Oxford [Oxford], Department of Computer Science [Alabama], University of Alabama [Tuscaloosa] ( UA ), Roberval, Université de Technologie de Compiègne ( UTC ), Institut de Mathématiques de Jussieu ( IMJ ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Université Paris Diderot - Paris 7 ( UPD7 ) -Centre National de la Recherche Scientifique ( CNRS ), Centre for Inflammation Research, University of Edinburgh-Queen's Medical Research Institute, Division of Medicinal Chemistry, Universiteit Leiden [Leiden], University of Pittsburgh [Pittsburg], University of Pittsburgh, Department of Chemistry and Nano Science, EWHA Womans University ( EWHA ), Institute of Materials Chemistry, Technical University of Vienna [Vienna] ( TU WIEN ), Leiden Academic Center for Drug Research, Peking Univ, Coll Urban & Environm Sci, Lab Earth Surface Proc, Beijing 100871, Peoples R China, Queensland Research Lab, National ICT Australia [Sydney] ( NICTA ), Institut des Systèmes Intelligents et de Robotique ( ISIR ), Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Centre National de la Recherche Scientifique ( CNRS ), Centre for Plant Integrative Biology [Nothingham] ( CPIB ), University of Nottingham, UK ( UON ), Department of Electrical and Computer Engineering, University of Utah, SUN Yatsen University, Sidney Kimmel Cancer Center, Jefferson (Philadelphia University + Thomas Jefferson University), Molecular Carcinogenesis [Sutton], Institute of cancer research, Centre d'études et de recherches appliquées à la gestion (Grenoble), Centre d'études et de recherches appliquées à la gestion ( CERAG ), Centre National de la Recherche Scientifique ( CNRS ) -Université Pierre Mendès France - Grenoble 2 ( UPMF ) -Université Grenoble Alpes ( UGA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Pierre Mendès France - Grenoble 2 ( UPMF ) -Université Grenoble Alpes ( UGA ), China Meteorological Administration, Equipe de Recherche Interdisciplinaire sur le Tourisme ( IUKB ), Institut Universitaire Kurt Bösch, University of Leeds, Dipartimento di Chimica, Università degli Studi di Roma 'La Sapienza' [Rome], Centre d'élaboration de matériaux et d'études structurales ( CEMES ), Institut National des Sciences Appliquées - Toulouse ( INSA Toulouse ), Institut National des Sciences Appliquées ( INSA ) -Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Toulouse III - Paul Sabatier ( UPS ), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, Cancer et génôme: Bioinformatique, biostatistiques et épidémiologie d'un système complexe, MINES ParisTech - École nationale supérieure des mines de Paris-Institut National de la Santé et de la Recherche Médicale ( INSERM ) -INSTITUT CURIE, Centre de Bioinformatique ( CBIO ), MINES ParisTech - École nationale supérieure des mines de Paris-PSL Research University ( PSL ), Computer Graphics Group, Department of Computer Science [Hong Kong], City University of Hong Kong [Hong Kong] ( CUHK ) -City University of Hong Kong [Hong Kong] ( CUHK ), Ingénierie Moléculaire et Physiopathologie Articulaire ( IMoPA ), Université de Lorraine ( UL ) -Centre National de la Recherche Scientifique ( CNRS ), Department of Computing [London], Biomedical Image Analysis Group [London] ( BioMedIA ), Imperial College London-Imperial College London, State Key Laboratory of Virology, Wuhan University [China], MoNOS, Huygens Laboratory, Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000, China ( IMP ), University of Science and Technology Beijing [Beijing] ( USTB ), Laboratoire de Chimie Physique - Matière et Rayonnement ( LCPMR ), Dalian University of Technology, Chalmers University of Technology [Göteborg], Advanced Photon Source [ANL] ( APS ), Argonne National Laboratory [Lemont] ( ANL ) -University of Chicago-US Department of Energy, Beth Israel Deaconess Medical Center, Harvard Medical School [Boston] ( HMS ), Dublin City University [Dublin] (DCU), Helsinki Institute for Information Technology (HIIT), Helsingin yliopisto = Helsingfors universitet = University of Helsinki-Aalto University, University of Westminster [London] (UOW), Stanford Center for BioMedical Informatics Research (BMIR), Stanford University, Equipe NEMESIS - Centre de Recherches de l'Institut du Cerveau et de la Moelle épinière (NEMESIS-CRICM), Centre de Recherche de l'Institut du Cerveau et de la Moelle épinière (CRICM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Institute for Molecular Bioscience, University of Queensland [Brisbane], Nanjing University of Information Science and Technology (NUIST), Instituto de Engenharia de Sistemas e Computadores (INESC), European Bioinformatics Institute [Hinxton] (EMBL-EBI), EMBL Heidelberg, Tianjin Agricultural University (TJAU), University of Oxford, University of Alabama [Tuscaloosa] (UA), Roberval (Roberval), Université de Technologie de Compiègne (UTC), University of Edinburgh-Queen's Medical Researche Institute, University of Edinburgh, Universiteit Leiden, University of Pittsburgh (PITT), Pennsylvania Commonwealth System of Higher Education (PCSHE), EWHA Womans University (EWHA), Vienna University of Technology (TU Wien), National ICT Australia [Sydney] (NICTA), Centre for Plant Integrative Biology [Nothingham] (CPIB), University of Nottingham, UK (UON), Innovation Center for Biomedical Informatics, Georgetown University Medical Center, Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome] (UNIROMA), Cancer et génome: Bioinformatique, biostatistiques et épidémiologie d'un système complexe, Mines Paris - PSL (École nationale supérieure des mines de Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut Curie [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM), Centre de Bioinformatique (CBIO), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Computer Graphics Group [Hong Kong], City University of Hong Kong [Hong Kong] (CUHK)-City University of Hong Kong [Hong Kong] (CUHK), Biomedical Image Analysis Group [London] (BioMedIA), Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000, China (IMP), University of Science and Technology Beijing [Beijing] (USTB), Advanced Photon Source [ANL] (APS), Argonne National Laboratory [Lemont] (ANL)-University of Chicago-US Department of Energy, Harvard Medical School [Boston] (HMS), Aalto University-University of Helsinki, Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome], MINES ParisTech - École nationale supérieure des mines de Paris, TR11527, Karaçalı, Bilge, and Izmir Institute of Technology. Electronics and Communication Engineering

Subjects
Epigenomics, Proteomics, Biological pathways, Inference, computer.software_genre, Genomic information, Applied Microbiology and Biotechnology, 0302 clinical medicine, Neoplasms, Computational models, Profiling (information science), ta518, [ SDV.BIBS ] Life Sciences [q-bio]/Quantitative Methods [q-bio.QM], ta515, ComputingMilieux_MISCELLANEOUS, 0303 health sciences, Computational model, ta213, Genomics, [SDV.BIBS]Life Sciences [q-bio]/Quantitative Methods [q-bio.QM], 3. Good health, Gene Expression Regulation, Neoplastic, 030220 oncology & carcinogenesis, Molecular Medicine, Algorithms, Biotechnology, Data integration, Bayesian probability, Biomedical Engineering, Antineoplastic Agents, Bioengineering, Biology, Machine learning, Article, 03 medical and health sciences, Humans, 030304 developmental biology, ta113, ta112, Proteomic Profiling, business.industry, Gene Expression Profiling, Precision medicine, Drug Resistance, Neoplasm, ta5141, Gene expression, Artificial intelligence, business, computer, Forecasting
Abstract

Predicting the best treatment strategy from genomic information is a core goal of precision medicine. Here we focus on predicting drug response based on a cohort of genomic, epigenomic and proteomic profiling data sets measured in human breast cancer cell lines. Through a collaborative effort between the National Cancer Institute (NCI) and the Dialogue on Reverse Engineering Assessment and Methods (DREAM) project, we analyzed a total of 44 drug sensitivity prediction algorithms. The top-performing approaches modeled nonlinear relationships and incorporated biological pathway information. We found that gene expression microarrays consistently provided the best predictive power of the individual profiling data sets; however, performance was increased by including multiple, independent data sets. We discuss the innovations underlying the top-performing methodology, Bayesian multitask MKL, and we provide detailed descriptions of all methods. This study establishes benchmarks for drug sensitivity prediction and identifies approaches that can be leveraged for the development of new methods., MaGNeT grant 5U54CA121852-08; National Institutes of Health, National Cancer Institute (U54 CA 112970); Stand Up To Cancer-American Association for Cancer Research Dream Team Translational Cancer Research (SU2C-AACR-DT0409); Prospect Creek Foundation; Howard Hughes Medical Institute (HHMI); Academy of Finland (Finnish Center of Excellence in Computational Inference Research COIN) (251170--140057)

Published
2014

30. The Intermetallic Compound ZnPd and Its Role in Methanol Steam Reforming

Author

Marc Armbrüster, Matthias Friedrich, S.T. Matam, Emilie Gaudry, Karin Föttinger, Hem Raj Sharma, Malte Behrens, Max-Planck-Institut für Chemische Physik fester Stoffe (CPfS), Max-Planck-Gesellschaft, Department of Inorganic Chemistry [Berlin], Fritz-Haber-Institut der Max-Planck-Gesellschaft (FHI), Max Planck Society-Max Planck Society, Institute of Materials Chemistry, Vienna University of Technology (TU Wien), Institut Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Empa, Swiss Federal Laboratories for Materials Science and Technology [Thun] (EMPA), Department of Physics, and University of Liverpool

Subjects
Quantum chemical, Hydrogen, Chemistry, Process Chemistry and Technology, Inorganic chemistry, Intermetallic, Chemie, chemistry.chemical_element, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, Steam reforming, chemistry.chemical_compound, Chemical engineering, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Experimental work, Methanol, 0210 nano-technology, Hydrogen production
Abstract

International audience; The rich literature about the intermetallic compound ZnPd as well as several ZnPd near-surface intermetallic phases is reviewed. ZnPd is frequently observed in different catalytic reactions triggering this review in order to collect the knowledge about the compound. The review addresses the chemical and physical properties of the compound and relates these comprehensively to the catalytic properties of ZnPd in methanol steam reforming--an interesting reaction to release hydrogen for a future hydrogen-based energy infrastructure from water/methanol mixtures. The broad scope of the review covers experimental work as well as quantum chemical calculations on a variety of Pd-Zn materials, aiming at covering all relevant literature to derive a sound state-of-the-art picture of the understanding gained so far.

Published
2013

31. Room-temperature spin-spiral multiferroicity in high-pressure cupric oxide

Author

Karlheinz Schwarz, Peter Blaha, Xavier Rocquefelte, Jeroen van den Brink, Sanjeev Kumar, Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Institute of Materials Chemistry, Vienna University of Technology (TU Wien), Indian Institute of Science Education and Research Thiruvananthapuram (IISER TVM), Institute of Theoretical Solid State Physics, Leibniz-Institut für Festkörper- und Werkstoffforschung Dresden (IFW Dresden), Leibniz Association-Leibniz Association, Institut für Theoretische Physik [Dresden], and Technische Universität Dresden = Dresden University of Technology (TU Dresden)

Subjects
Multidisciplinary, Materials science, Condensed matter physics, Monte Carlo method, Oxide, General Physics and Astronomy, 02 engineering and technology, General Chemistry, Atmospheric temperature range, 021001 nanoscience & nanotechnology, Polarization (waves), 01 natural sciences, 7. Clean energy, Ferroelectricity, General Biochemistry, Genetics and Molecular Biology, Article, chemistry.chemical_compound, chemistry, High pressure, 0103 physical sciences, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Multiferroics, Density functional theory, 010306 general physics, 0210 nano-technology
Abstract

International audience; Multiferroic materials, in which ferroelectric and magnetic ordering coexist, are of fundamental interest for the development of multi-state memory devices that allow for electrical writing and non-destructive magnetic readout operation. The great challenge is to create multiferroic materials that operate at room temperature and have a large ferroelectric polarization P. Cupric oxide, CuO, is promising because it exhibits a significant polarization, that is, P~0.1 μC cm−2, for a spin-spiral multiferroic. Unfortunately, CuO is only ferroelectric in a temperature range of 20 K, from 210 to 230 K. Here, by using a combination of density functional theory and Monte Carlo calculations, we establish that pressure-driven phase competition induces a giant stabilization of the multiferroic phase of CuO, which at 20-40 GPa becomes stable in a domain larger than 300 K, from 0 to T>300 K. Thus, under high pressure, CuO is predicted to be a room-temperature multiferroic with large polarization.

Published
2013

32. Structural analysis and surface wettability of a novel alternated vinylidene cyanide with fluorinated vinyl ether copolymer

Author

Mustapha Raihane, Hiroki Yamaguchi, Bruno Ameduri, Takamichi Shinohara, Ahmed Meskini, Ryohei Ishige, Atsushi Takahara, Kyushu University [Fukuoka], Institute for Materials Chemistry and Engineering, Laboratoire de Chimie Bioorganique et Macromoléculaire - Faculté des Sciences et Techniques (LCBM), Université Cadi Ayyad [Marrakech] (UCA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and partenariat international informel

Subjects
Materials science, Polymers and Plastics, Ether, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Contact angle, chemistry.chemical_compound, Differential scanning calorimetry, Polymer chemistry, Materials Chemistry, Side chain, Copolymer, medicine, hydrophobic, alternated copolymer, perfluorooctyl, thin-film WAXD, Vinyl ether, 021001 nanoscience & nanotechnology, 0104 chemical sciences, surface reorganization, [CHIM.POLY]Chemical Sciences/Polymers, Chemical engineering, chemistry, Ethyl acrylate, Wetting, fluoropolymers, 0210 nano-technology, medicine.drug
Abstract

The structure, thermal properties and surface wettability of a novel alternating poly(VCN-alt-FAVE8) copolymer based on vinylidene cyanide (VCN) and perfluorooctyl ethyl vinyl ether (FAVE8) were investigated via both temperature-variable wide-angle X-ray powder diffraction (WAXD) and thin-film WAXD using a small angle incidence synchrotron radiation source, differential scanning calorimetry and contact angle measurements, respectively. The results of the WAXD and thin-film WAXD indicated that the alternating copolymer possessed a smectic liquid-crystalline phase at ambient temperature with a couple of fluoroalkyl side chains forming a bilayer with a 3.24 nm spacing and that the fluoroalkyl side chains in a thin-film on a Si wafer align perpendicularly to the surface. The isotropization temperature of the alternating copolymer was 150 °C, which was higher than the 29.5 °C for the poly(FAVE8) homopolymer. The spin-coated poly(VCN-alt-FAVE8) copolymer thin-film yielded high static contact angles for both water and oil similar to those for poly(perfluorooctyl ethyl acrylate), which is known as a superhydrophobic polymer. Dynamic contact angle and X-ray photoelectron spectroscopy measurements in both the dry and hydrated states suggested that the polar cyano and ether groups are enriched at the surface in the wet state, and this reorganization of the surface polar groups caused a large hysteresis of the contact angle. High ordered structure, thermal property and surface wettability of a novel alternated copolymer of vinylidene cyanide and perfluorooctyl ethyl vinyl ether were investigated with wide-angle X-ray diffraction, differential scanning calorimetry, X-ray photoelectron spectroscopy and contact angle measurement. The alternated copolymer showed a smectic liquid crystalline structure and extremely high isotropization temperature of 150 °C, compared with 29.5 °C for the perfluorooctyl ethyl vinyl ether homopolymer. The alternated copolymer also showed large contact angle hysteresis, indicating that surface reorganization of the polar cyano and ether groups occur.

Published
2013

33. Structure evolution of layered double hydroxides activated by ultrasound induced reconstruction

Author

R.J. Chimentão, Didier Tichit, Karin Föttinger, F. Gispert-Guirado, Mayra G. Álvarez, Noelia Barrabés, Francesc Medina, Evgeny Kleymenov, Enginyeria Química, Universitat Rovira i Virgili., EMaS-Centro de Investigación en Ingeniería de Materiales y micro/nano Sistemas, Departament d'Enginyeria Quimica, Universitat Rovira i Virgili, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institute of Materials Chemistry, Vienna University of Technology (TU Wien), Servei de Recursos Científics i Tècnics, Paul Scherrer Institute (PSI), Spanish Government's Ministry of Science and Innovation (project CTQ2006-08196 and CTQ2008-03043-E, ACENET), and CSIC-MICINN financial support to the Experiment 25-01-775 at the Splinebeamline at the ESRF

Subjects
education.field_of_study, Materials science, Sonication, Thermal decomposition, Population, Inorganic chemistry, Layered double hydroxides, Geology, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, engineering.material, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, XANES, 0104 chemical sciences, Crystallinity, Geochemistry and Petrology, Phase (matter), engineering, Crystallite, 0210 nano-technology, education
Abstract

International audience; Reconstruction of mixed oxides resulting from the thermal decomposition at 723 K of ZnAl and ZnMgAl layered double hydroxides (LDHs) has been studied performing mechanical stirring or ultrasonic treatments for different periods of time in aqueous media. Thesematerialswere fully characterized by several physico-chemicalmethods including powder X-Ray diffraction and Rietveld refinements, XANES and XASF spectroscopies. The results show that the crystallinity increases in the LDH samples after the reconstruction. The crystallite sizes of the reconstructed LDHs increase in comparison to the as-prepared LDHs and this effect is improved upon ultrasound treatments. Moreover, reconstructed samples did not completely recover the original structure and ZnO phase was formed at the expense of an amorphous phase present in the as-prepared LDH. The application of ultrasound favors the formation of ZnO. Incorporation ofMg as ternary cation to obtain Mg/Zn/Al LDH decreases the crystallinity and leads to more disordered materials. The Mg/Zn/Al LDHs present lower amount of amorphous phase than ZnAl LDHs which also decreases in the reconstructed samples. But, in contrast to the behavior observed for Zn/Al, ultrasonication alters the crystallinity and increase of the amount of amorphous phasewhen sonication timeincreases. The basicity (number, strength and nature of sites) increases after reconstruction of themixed oxides into the LDH structures as well as with the sonication time; while the opposite trend was observed for the acid sites. Moreover the basicity is greatly enhanced upon introduction ofMg in the LDH. The changes in the population of acid-base sites affect the behavior of the catalysts in the carbonylation of glycerol.

Published
2013

34. Pt-Cu bimetallic catalysts obtained from layered double hydroxides by an anion-exchange route

Author

Jordi Llorca, Gunter Rupprechter, Karin Föttinger, Noelia Barrabés, Didier Tichit, A. Frare, Atsushi Urakawa, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institute of Materials Chemistry, Vienna University of Technology (TU Wien), Institute of Chemical Research of Catalonia (ICIQ), Institut de Tecniques Energetiques, Universitat Politècnica de Catalunya [Barcelona] (UPC), and ICREA Academia program and MICINN project CTQ2009-12520

Subjects
Inorganic chemistry, chemistry.chemical_element, Hydrotalcite, 02 engineering and technology, engineering.material, 010402 general chemistry, 01 natural sciences, law.invention, Catalysis, chemistry.chemical_compound, Geochemistry and Petrology, law, Bimetallic catalyst, Calcination, Nitrate removal, Citrate colloids, Anionic-exchange, Bimetallic strip, Ion exchange, Layered double hydroxides, Geology, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Copper, 0104 chemical sciences, chemistry, engineering, Hydroxide, 0210 nano-technology
Abstract

Article history:Received 16 February 2012Received in revised form 13 July 2012Accepted 17 July 2012Available online 13 October 2012Keywords:Anionic-exchangeHydrotalciteNitrate removalBimetallic catalystCitrate colloids Bimetallic Pt-Cu catalyst precursors have been prepared from NO 3− ‐Mg/Al layered double hydroxide (LDH)by anionic exchange with negatively charged copper hydroxy citrate colloids ([Cu(C 6 O 7 H 3 ) x (OH)] yy(3x −1) )and [PtCl 6 ] 2− species. Successive exchanges by varying the addition order of the two anionic species allowedremoving NO 3− almost completely and obtaining Cu/Pt molar ratios of 50.2 and 6.8 when Cu-containing col-loids were introduced first (CuPt) or second (PtCu), respectively. After calcination and reduction treatments,the resulting materials were characterized by TPR and XPS analyses. Pt and Cu particles were homogeneouslydispersed with the particle size of 2–7 nm and the portion of Cu present as Pt-Cu alloy was 48.9% (CuPt) and69.8% (PtCu), showing remarkably enhanced alloy formation by the PtCu exchange order.Using thisPtCu ma-terial, total conversion in nitrate hydrogenation reaction was achieved with higher selectivity toward nitro-gen than those reported with bimetallic Pd-Cu catalysts prepared from LDH precursors by impregnation andco-precipitation routes.© 2012 Elsevier B.V. All rights reserved.

Published
2012

35. One-electron oxidized copper(II) salophen complexes: phenoxyl versus diiminobenzene radical species

Author

Fumito Tani, Benoit Baptiste, Hervé Vezin, Olivier Jarjayes, Fabrice Thomas, Christian Philouze, Kazuaki Tsukidate, Amélie Kochem, Yuichi Shimazaki, Maylis Orio, Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE), Département de Chimie Moléculaire (DCM), Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), College of Science, Ibaraki University Bunkyo, Institute for Materials Chemistry and Engineering, Kyushu University [Fukuoka], Département de Chimie Moléculaire - Chimie Inorganique Redox (DCM - CIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Kyushu University

Subjects
Free Radicals, Radical, chemistry.chemical_element, Electrons, Electron, salophen, 010402 general chemistry, Photochemistry, Crystallography, X-Ray, 01 natural sciences, Catalysis, Polymer chemistry, Organometallic Compounds, Redox active, Molecular Structure, 010405 organic chemistry, Organic Chemistry, Benzene, General Chemistry, radicals, Copper, Salicylates, 3. Good health, 0104 chemical sciences, X-ray diffraction, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, X-ray crystallography, density functional calculations, Quantum Theory, Imines, Oxidation-Reduction
Abstract

Where is the radical? The π-system of the diiminobenzene bridge adds a putative oxidation site to prophenoxyl copper(II) salophen complexes. It is shown that the bridge is effectively redox active and that the radical site (phenoxyl vs. diiminobenzene bridge) in the above cations is tuned by selective methoxy substitution (see figure).

Published
2011

36. Short-range magnetic order and temperature-dependent properties of cupric oxide

Author

Antoine Villesuzanne, Karlheinz Schwarz, Stéphane Jobic, Fabien Tran, Peter Blaha, Xavier Rocquefelte, Myung-Hwan Whangbo, Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Department of Chemistry (NCSU), North Carolina State University [Raleigh] (NC State), University of North Carolina System (UNC)-University of North Carolina System (UNC), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Université de Bordeaux (UB), Institute of Materials Chemistry, Vienna University of Technology (TU Wien), and Department of Chemistry, North Carolina Raleigh

Subjects
Work (thermodynamics), Materials science, Band gap, Oxide, Condensed matter, Inorganic compounds, FOS: Physical sciences, 02 engineering and technology, Electronic structure, 01 natural sciences, DFT, chemistry.chemical_compound, Condensed Matter - Strongly Correlated Electrons, Condensed Matter::Superconductivity, 0103 physical sciences, General Materials Science, 010306 general physics, Spin (physics), Electrical, Range (particle radiation), Condensed Matter - Materials Science, Condensed matter physics, Strongly Correlated Electrons (cond-mat.str-el), Materials Science (cond-mat.mtrl-sci), Oxides, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, magnetic and optical, chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, Condensed Matter::Strongly Correlated Electrons, 0210 nano-technology, Nuclear quadrupole resonance
Abstract

The temperature dependence of the optical and magnetic properties of CuO were examined by means of hybrid density functional theory calculations. Our work shows that the spin exchange interactions in CuO are neither fully one-dimensional nor fully three-dimensional. The large temperature dependence of the optical band gap and the 63Cu nuclear quadrupole resonance frequency of CuO originate from the combined effect of a strong coupling between the spin order and the electronic structure and the progressive appearance of short-range order with temperature., Comment: 22 pages, 4 figure, 2 tables, letters submitted in Europhysics Letters

Published
2011

37. Light emission spectroscopy of self-assembled arrays of silver nano-crystals with the STM

Author

Hans-Joachim Freund, Caroline Salzemann, Arnaud Brioude, Marie-Paule Pileni, Hadj-Mohamed Benia, Günther Rupprechter, Niklas Nilius, De la Molécule aux Nanos-objets : Réactivité, Interactions et Spectroscopies (MONARIS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institute of Materials Chemistry, Vienna University of Technology (TU Wien), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des Matériaux Mésoscopiques et Nanométriques (LMMN), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chemistry, General Physics and Astronomy, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 021001 nanoscience & nanotechnology, Polarization (waves), 01 natural sciences, Molecular physics, Spectral line, [SPI.MAT]Engineering Sciences [physics]/Materials, Dipole, Delocalized electron, 0103 physical sciences, Quasiparticle, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Light emission, Physical and Theoretical Chemistry, Atomic physics, [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, 010306 general physics, 0210 nano-technology, Spectroscopy, Plasmon, ComputingMilieux_MISCELLANEOUS
Abstract

The optical properties of ordered and disordered assemblies of Ag nano-crystals on HOPG have been characterized by photon emission spectroscopy with the STM. The spectra reveal two emission maxima, which are attributed to plasmon modes oscillating parallel and perpendicular to the substrate plane. The interpretation of the emission mechanism is supported by polarization measurements and model calculations. The effect of long-range order in the particle layer on the optical properties is discussed. � 2005 Elsevier B.V. All rights reserved. In analogy to the formation of bulk crystals from single atoms, well-ordered two- and three-dimensional (2D, 3D) super-lattices can be aggregated from nano-particles with small size distribution [1–4]. The properties of these supra-crystals dramatically deviate from those of the isolated objects. Static and dynamic electromagnetic dipoles in the individual particles couple in the ensemble and stimulate the formation of new delocalized modes. Such collective excitations dominate the optical [5–7], magnetic [8] and vibronic properties of the supra-crystals [9]. The development of collective modes depends on the nature and efficiency of the coupling mechanism, the lattice constant and the long-range order in the network. Control over these parameters allows certain adjustment of the ensemble properties, opening the way to tailor novel materials with potential applications in optical and storage devices. Intensive investigations of 2D self-organizations were initiated by the first development of reliable soft-chemi

Published
2005

38. Rapid and ultrasensitive detection of thiram and carbaryl pesticide residues in fruit juices using SERS coupled with the chemometrics technique.

Author

Adhikari S, Joshi R, Joshi R, Kim M, Jang Y, Tufa LT, Gicha BB, Lee J, Lee D, and Cho BK

Subjects
Chemometrics, Metal Nanoparticles chemistry, Limit of Detection, Fruit chemistry, Pesticide Residues analysis, Spectrum Analysis, Raman methods, Carbaryl analysis, Fruit and Vegetable Juices analysis, Thiram analysis, Food Contamination analysis, Gold chemistry
Abstract

A gold nanogap substrate was used to measure the thiram and carbaryl residues in various fruit juices using surface-enhanced Raman scattering (SERS). The gold nanogap substrates can detect carbaryl and thiram with limits of detection of 0.13 ppb (0.13 μgkg -1 ) and 0.22 ppb (0.22 μgkg -1 ). Raw SERS data were first preprocessed to reduce noise and undesirable effects and, were later used for model creation, implementing classification, and regression analysis techniques. The partial least-squares regression models achieved the highest prediction correlation coefficient (R 2 ) of 0.99 and the lowest root mean square of prediction value below 0.62 ppb for both pesticide-infected juice samples. Furthermore, to differentiate between juice samples contaminated by both pesticides and control (pesticide-free), logistic-regression classification models were produced and achieved the highest classification accuracies of 100% and 99% for contaminated juice containing thiram and 100% accurate results for contaminated juice containing carbaryl. This indicates that the gold nanogap surface has significant potential for achieving high sensitivity in detecting trace contaminants in food samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Published
2024
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39. Ligand engineering enhances (photo) electrocatalytic activity and stability of zeolitic imidazolate frameworks via in-situ surface reconstruction.

Author

Huang Z, Wang Z, Rabl H, Naghdi S, Zhou Q, Schwarz S, Apaydin DH, Yu Y, and Eder D

Abstract

The current limitations in utilizing metal-organic frameworks for (photo)electrochemical applications stem from their diminished electrochemical stability. In our study, we illustrate a method to bolster the activity and stability of (photo)electrocatalytically active metal-organic frameworks through ligand engineering. We synthesize four distinct mixed-ligand versions of zeolitic imidazolate framework-67, and conduct a comprehensive investigation into the structural evolution and self-reconstruction during electrocatalytic oxygen evolution reactions. In contrast to the conventional single-ligand ZIF, where the framework undergoes a complete transformation into CoOOH via a stepwise oxidation, the ligand-engineered zeolitic imidazolate frameworks manage to preserve the fundamental framework structure by in-situ forming a protective cobalt (oxy)hydroxide layer on the surface. This surface reconstruction facilitates both conductivity and catalytic activity by one order of magnitude and considerably enhances the (photo)electrochemical stability. This work highlights the vital role of ligand engineering for designing advanced and stable metal-organic frameworks for photo- and electrocatalysis., (© 2024. The Author(s).)

Published
2024
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40. Regulating the Hydrophilicity of Hyper-Cross-Linked Polymers via Thermal Oxidation for Atmospheric Water Harvesting.

Author

Schweng P, Präg L, and Woodward RT

Abstract

We explore the thermal oxidation of hyper-cross-linked polymers to enhance their hydrophilicity and efficacy in atmospheric water harvesting. Comprehensive chemical and physical characterizations are used to confirm the successful incorporation of polar oxygen moieties and the preservation of porosity upon thermal treatment. Newly introduced oxygen-based functional groups significantly improve water sorption properties, increasing total water uptake capacities by up to 400% and shifting water uptake onsets to significantly lower relative humidity. We also investigate the regeneration of oxidized hyper-cross-linked polymers after water sorption to probe their potential for multiple water harvesting cycles and reuse. Our findings outline a simple and cost-effective postsynthetic modification route for optimizing porous organic polymers for more sustainable and efficient atmospheric water harvesting.

Published
2024
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41. A Sulfonated Covalent Organic Framework for Atmospheric Water Harvesting.

Author

Schweng P, Li C, Guggenberger P, Kleitz F, and Woodward RT

Abstract

We report a sulfonated covalent organic framework (COF) capable of atmospheric water harvesting in arid conditions. The isothermal water uptake profile of the framework was studied, and the network displayed steep water sorption at low relative humidity (RH) in temperatures of up to 45 °C, reaching a water uptake of 0.12 g g -1 at 10 % RH and even 0.08 g g -1 at just 5 % RH, representing some of the most extreme conditions on the planet. We found that the inclusion of sulfonate moieties shifted uptake in the water isotherm profiles to lower RH compared to non-sulfonated equivalents, demonstrating well the benefits of including these hydrophilic sites for water uptake in hot, arid locations. Repeated uptake and desorption cycles were performed on the material without significant detriment to its adsorption performance, demonstrating the potential of the sulfonated COF for real-world implementation., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Published
2024
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42. Poly(lactide) Upcycling Approach through Transesterification for Stereolithography 3D Printing.

Author

Figalla S, Jašek V, Fučík J, Menčík P, and Přikryl R

Subjects
Esterification, Stereolithography, Polymerization, Viscosity, Rheology, Printing, Three-Dimensional, Polyesters chemistry
Abstract

The legislature determines the recycled and waste contents in fabrication processes to ensure more sustainable production. PLA's mechanical recycling and reuse are limited due to the performance decrease caused by thermal or hydrolytic instability. Our concept introduces an upcycling route involving PLA depolymerization using propylene glycol as a reactant, followed by the methacrylation, assuring the liquid systems' curability provided by radical polymerization. PLA-containing curable systems were studied from a rheological and thermomechanical viewpoint. The viscosity levels varied from 33 to 3911 mPa·s at 30 °C, giving a wide capability potential. The best system reached 2240 MPa storage modulus, 164.1 °C glass-transition temperature, and 145.6 °C heat-resistant index, competitive values to commercial systems. The printability was verified for all of the systems. Eventually, our concept led to SLA resin production containing PLA waste content up to 51 wt %.

Published
2024
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43. Hydrothermal synthesis of ZnZrO x catalysts for CO 2 hydrogenation to methanol: the effect of pH on structure and activity.

Author

Rakngam I, Alves GAS, Osakoo N, Wittayakun J, Konegger T, and Föttinger K

Abstract

With the growing necessity of achieving carbon neutrality in the industrial sector, the catalytic hydrogenation of carbon dioxide into methanol has been widely considered one of the key strategies for the utilization of captured CO 2 . For this reason, the development of alternative catalysts such as ZnZrO x has attracted considerable interest, given its superior stability and versatility in comparison to the conventional Cu-based materials. In this work, ZnZrO x has been produced by a hydrothermal synthesis method at varied synthesis pH between 7 and 10 and a positive association between pH and catalytic CO 2 conversion is observed. At 2.0 MPa and 250 °C, ZnZrO x produced at pH 10 shows a methanol selectivity of 95% at a CO 2 conversion of 3.4%. According to characterization, basic pH conditions enable the formation of abundant t-ZrO 2 and the subsequent incorporation of Zn 2+ into this phase, although the content of surface Zn does not increase between pH 8 and 10. Nevertheless, synthesis pH values can be correlated with surface oxygen content and CO 2 adsorption capacity, which could be important contributors to the higher catalytic activity observed as a result of higher synthesis pH values. However, upon synthesis at pH 10, an inferior selectivity to methanol is observed above 250 °C, as a possible result of the excessive formation of ZnO. Interestingly, this secondary phase can be prevented and the selectivity can be slightly improved by utilizing NH 4 OH instead of NaOH in the hydrothermal method., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Published
2024
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44. How reduction temperature influences the structure of perovskite-oxide catalysts during the dry reforming of methane.

Author

Schrenk F, Lindenthal L, Drexler H, Berger T, Rameshan R, Ruh T, Föttinger K, and Rameshan C

Abstract

Dry reforming of methane is a promising reaction to convert CO 2 and combat climate change. However, the reaction is still not feasible in large-scale industrial applications. The thermodynamic need for high temperatures and the potential of carbon deposition leads to high requirements for potential catalyst materials. As shown in previous publications, the Ni-doped perovskite-oxide Nd 0.6 Ca 0.4 Fe 0.97 Ni 0.03 O 3 is a potential candidate as it can exsolve highly active Ni nanoparticles on its surface. This study focused on controlling the particle size by varying the reduction temperature. We found the optimal temperature that allows the Ni nanoparticles to exsolve while not yet enabling the formation of deactivating CaCO 3 . Furthermore, the exsolution process and the behaviour of the phases during the dry reforming of methane were investigated using in situ XRD measurements at the DESY beamline P02.1 at PETRA III in Hamburg. They revealed that the formed deactivated phases would, at high temperatures, form a brownmillerite phase, thus hinting at a potential self-healing mechanism of these materials., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Published
2024
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45. A Stable Perovskite Sensitized Photonic Crystal P-N Junction with Enhanced Photoelectrochemical Hydrogen Production.

Author

Nwaji N, Kang H, Bayissa Gicha B, Osial M, Vapaavuori J, Lee J, and Giersig M

Abstract

The slow photon effect in inverse opal photonic crystals represents a promising approach to manipulate the interactions between light and matter through the design of material structures. This study introduces a novel ordered inverse opal photonic crystal (IOPC) sensitized with perovskite quantum dots (PQDs), demonstrating its efficacy for efficient visible-light-driven H 2 generation via water splitting. The rational structural design contributes to enhanced light harvesting. The sensitization of the IOPC with PQDs improves optical response performance and enhances photocatalytic H 2 generation under visible light irradiation compared to the IOPC alone. The designed photoanode exhibits a photocurrent density of 3.42 mA cm -2 at 1.23 V vs RHE. This work advances the rational design of visible light-responsive photocatalytic heterostructure materials based on wide band gap metal oxides for photoelectrochemical applications., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Published
2024
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46. Digging Its Own Site: Linear Coordination Stabilizes a Pt 1 /Fe 2 O 3 Single-Atom Catalyst.

Author

Rafsanjani-Abbasi A, Buchner F, Lewis FJ, Puntscher L, Kraushofer F, Sombut P, Eder M, Pavelec J, Rheinfrank E, Franceschi G, Birschitzky V, Riva M, Franchini C, Schmid M, Diebold U, Meier M, Madsen GKH, and Parkinson GS

Abstract

Determining the local coordination of the active site is a prerequisite for the reliable modeling of single-atom catalysts (SACs). Obtaining such information is difficult on powder-based systems and much emphasis is placed on density functional theory computations based on idealized low-index surfaces of the support. In this work, we investigate how Pt atoms bind to the (11̅02) facet of α-Fe 2 O 3 ; a common support material in SACs. Using a combination of scanning tunneling microscopy, X-ray photoelectron spectroscopy, and an extensive computational evolutionary search, we find that Pt atoms significantly reconfigure the support lattice to facilitate a pseudolinear coordination to surface oxygen atoms. Despite breaking three surface Fe-O bonds, this geometry is favored by 0.84 eV over the best configuration involving an unperturbed support. We suggest that the linear O-Pt-O configuration is common in reactive Pt-based SAC systems because it balances thermal stability with the ability to adsorb reactants from the gas phase. Moreover, we conclude that extensive structural searches are necessary to determine realistic active site geometries in single-atom catalysis.

Published
2024
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47. Crystal structures, bonding and electronic structures of α- and β-Ir 2 B 3- x compounds.

Author

Sologub O, Salamakha LP, Stöger B, Mori T, Barisic N, Rogl PF, Michor H, and Bauer E

Abstract

The binary boron-rich compounds α-Ir 2 B 3- x and β-Ir 2 B 3- x , formerly denoted as α- and β-Ir 4 B 5 , were synthesized via both arc melting followed by annealing at 800 °C (900 °C) and high-temperature thermal treatment of mixtures of the elements. X-ray structure analysis of α-Ir 2 B 3- x was performed on a single crystal (space group C 2/ m , a = 10.5515(11) Å, b = 2.8842(3) Å, c = 6.0965(7) Å, β = 91.121(9)°). The orthorhombic structure of β-Ir 2 B 3- x was confirmed by X-ray powder diffraction (space group Pnma ; a = 10.7519(3) Å, b = 2.83193(7) Å, c = 6.0293(1) Å). The α-Ir 2 B 3- x structure exhibits ordered arrangements of iridium atoms. The structure is composed of corrugated layers of boron hexagons (interlinked via external B-B bonds) alternating with two corrugated layers of iridium along the c -direction; an additional boron atom (Oc. 0.46(7)) is located between iridium layers in Ir 6 trigonal prisms. The boron partial structure in β-Ir 2 B 3- x is composed of ribbons made up of slightly corrugated quadrilateral units running along the b -direction in the channels formed by 8 iridium atoms each. DFT calculations revealed a number of bands crossing the Fermi level, predicting metallic behaviors of the two compounds. β-Ir 2 B 3- x is characterized by a pseudogap around the Fermi level and a smaller eDOS of 0.6405 states per eV per f.u. at the Fermi level, as compared to the α-Ir 2 B 3- x value of 1.405 states per eV per f.u. The calculated electron localization functions revealed strong covalent bonds between boron atoms in the core part of the B 6 hexagons, metallic B-B bonds within the quadrilateral boron partial structure and mixed covalent and metallic interactions between iridium and boron atoms. Structural relationships of α-Ir 2 B 3- x and β-Ir 2 B 3- x with ReB 2 -type structures as well as the common structural features with layered binary borides with CrB-type related structures have been discussed.

Published
2024
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48. Chemically recycled commercial polyurethane (PUR) foam using 2-hydroxypropyl ricinoleate as a glycolysis reactant for flexibility-enhanced automotive applications.

Author

Jašek V, Montag P, Menčík P, Přikryl R, Kalendová A, and Figalla S

Abstract

The automotive industry uses polyurethane (PUR) foam core in the vehicle headliner composite. The sector demands recycling suggestions to reduce its scrap and decrease the expenses. This work investigated the PUR depolymerization using synthesized 2-hydroxypropyl ricinoleate (2-HPR) from castor oil and incorporated the liquid recyclate (REC) into the original PUR foam. The synthesis of 2-HPR yielded 97.5%, and the following PUR depolymerization ( via glycolysis) reached 87.2% yield. The synthesized products were verified by GPC, FTIR, ESI-MS, and 1 H NMR cross-analysis. The laboratory experiments (565 mL) included rheological, structural, and reactivity investigations. Added 30% REC content decreased the apparent viscosity to 109 mPa s from standard 274 mPa s. The reactivity of the 30% REC system increased by 51.2% based on the cream time due to the high REC amine value. The block foam density of systems with 15% REC and above decreased by 14.8%. A system with 20% REC content was the most prospective for up-scale. The industrially significant up-scale (125 L) was performed successfully, and the tensile and flexural test specimens were sampled from the up-scaled foam. The tensile characteristic (tensile strength 107 ± 8 kPa and elongation 9.2 ± 0.7%) and flexural characteristic (flexural strength 156 ± 12 kPa and flexural strain at deformation limit 23.4 ± 0.6%) confirmed that the REC incorporation in the standard PUR foam improves the applicable significant mechanical properties and assures the manufacture improve., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

Published
2024
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49. Exploring inhomogeneous surfaces: Ti-rich SrTiO 3 (110) reconstructions via active learning.

Author

Wanzenböck R, Heid E, Riva M, Franceschi G, Imre AM, Carrete J, Diebold U, and Madsen GKH

Abstract

The investigation of inhomogeneous surfaces, where various local structures coexist, is crucial for understanding interfaces of technological interest, yet it presents significant challenges. Here, we study the atomic configurations of the (2 × m ) Ti-rich surfaces at (110)-oriented SrTiO 3 by bringing together scanning tunneling microscopy and transferable neural-network force fields combined with evolutionary exploration. We leverage an active learning methodology to iteratively extend the training data as needed for different configurations. Training on only small well-known reconstructions, we are able to extrapolate to the complicated and diverse overlayers encountered in different regions of the inhomogeneous SrTiO 3 (110)-(2 × m ) surface. Our machine-learning-backed approach generates several new candidate structures, in good agreement with experiment and verified using density functional theory. The approach could be extended to other complex metal oxides featuring large coexisting surface reconstructions., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Published
2024
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50. Bimetallic CuPd nanoparticles supported on ZnO or graphene for CO 2 and CO conversion to methane and methanol.

Author

Maqbool Q, Dobrezberger K, Stropp J, Huber M, Kontrus KL, Aspalter A, Neuhauser J, Schachinger T, Löffler S, and Rupprechter G

Abstract

Carbon dioxide (CO 2 ) and carbon monoxide (CO) hydrogenation to methane (CH 4 ) or methanol (MeOH) is a promising pathway to reduce CO 2 emissions and to mitigate dependence on rapidly depleting fossil fuels. Along these lines, a series of catalysts comprising copper (Cu) or palladium (Pd) nanoparticles (NPs) supported on zinc oxide (ZnO) as well as bimetallic CuPd NPs supported on ZnO or graphene were synthesized via various methodologies. The prepared catalysts underwent comprehensive characterization via high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX) mapping, electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), hydrogen temperature-programmed reduction and desorption (H 2 -TPR and H 2 -TPD), and deuterium temperature-programmed desorption (D 2 O-TPD). In the CO 2 hydrogenation process carried out at 20 bar and elevated temperatures (300 to 500 °C), Cu, Pd, and CuPd NPs (<5 wt% loading) supported on ZnO or graphene predominantly yielded CH 4 as the primary product, with CO generated as a byproduct via the reverse water gas shift (RWGS) reaction. For CO hydrogenation between 400 and 500 °C, the CO conversion was at least 40% higher than the CO 2 conversion, with CH 4 and CO 2 identified as the main products, the latter from water gas shift. Employing 90 wt% Cu on ZnO led to an enhanced CO conversion of 14%, with the MeOH yield reaching 10% and the CO 2 yield reaching 4.3% at 230 °C. Overall, the results demonstrate that lower Cu/Pd loading (<5 wt%) supported on ZnO/graphene favored CH 4 production, while higher Cu content (90 wt%) promoted MeOH production, for both CO 2 and CO hydrogenation at high pressure., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Published
2024
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