101 results on '"Matthew J. Rosseinsky"'
Search Results
2. Extended Condensed Ultraphosphate Frameworks with Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical Stability
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Marco Zanella, Luke M. Daniels, Frédéric Blanc, Matthew S. Dyer, Alex R. Neale, Craig M. Robertson, Yun Dang, Laurence J. Hardwick, Laurence J Kershaw Cook, Guopeng Han, Matthew J. Rosseinsky, Michael Knapp, Anna-Lena Hansen, Benjamin B. Duff, John B. Claridge, Ruiyong Chen, and Andrij Vasylenko
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chemistry.chemical_element ,Ionic bonding ,General Chemistry ,Electrolyte ,Electrochemistry ,Biochemistry ,Catalysis ,Article ,Dielectric spectroscopy ,Colloid and Surface Chemistry ,chemistry ,ddc:540 ,Fast ion conductor ,Physical chemistry ,Ionic conductivity ,Lithium ,Chemical stability - Abstract
Journal of the American Chemical Society 143(43), 18216 - 18232 (2021). doi:10.1021/jacs.1c07874, Extended anionic frameworks based on condensation of polyhedral main group non-metal anions offer a wide range of structure types. Despite the widespread chemistry and earth abundance of phosphates and silicates, there are no reports of extended ultraphosphate anions with lithium. We describe the lithium ultraphosphates Li$_3$P$_5$O$_{14}$ and Li$_4$P$_6$O$_{17}$ based on extended layers and chains of phosphate, respectively. Li$_3$P$_5$O$_{14}$ presents a complex structure containing infinite ultraphosphate layers with 12-membered rings that are stacked alternately with lithium polyhedral layers. Two distinct vacant tetrahedral sites were identified at the end of two distinct finite Li$_6$O_{16}$^{26���}$ chains. Li$_4$P$_6$O$_{17}$ features a new type of loop-branched chain defined by six PO43��� tetrahedra. The ionic conductivities and electrochemical properties of Li$_3$P$_5$O$_{14}$ were examined by impedance spectroscopy combined with DC polarization, NMR spectroscopy, and galvanostatic plating/stripping measurements. The structure of Li$_3$P$_5$O$_{14}$ enables three-dimensional lithium migration that affords the highest ionic conductivity (8.5(5) �� 10$^{���7}$ S cm$^{���1}$ at room temperature for bulk), comparable to that of commercialized LiPON glass thin film electrolytes, and lowest activation energy (0.43(7) eV) among all reported ternary Li���P���O phases. Both new lithium ultraphosphates are predicted to have high thermodynamic stability against oxidation, especially Li$_3$P$_5$O$_{14}$ which is predicted to be stable to 4.8 V, significantly higher than that of LiPON and other solid electrolytes. The condensed phosphate units defining these ultraphosphate structures offer a new route to optimize the interplay of conductivity and electrochemical stability required, for example, in cathode coatings for lithium ion batteries., Published by American Chemical Society, Washington, DC
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- 2021
3. High-throughput discovery of Hf promotion on the stabilisation of hcp Co and Fischer-Tropsch activity
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Elliot J. Carrington, Marco Zanella, Robert P. Tooze, Troy D. Manning, Alexandros P. Katsoulidis, Alexios Grigoropoulos, John B. Claridge, Rebecca Vismara, Hendrik Van Rensburg, Luis Alvarado Rupflin, and Matthew J. Rosseinsky
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Chemical engineering ,Chemistry ,Bulk samples ,Active phase ,Support materials ,Fischer–Tropsch process ,Particle size ,Physical and Theoretical Chemistry ,Selectivity ,Catalysis ,Syngas - Abstract
A proxy-based high-throughput experimental approach was used to explore the stability and activity of Co-based Fischer-Tropsch Synthesis catalysts with different promoters on a variety of supports. The protocol is based on XRD estimation of the active phase polymorph, particle size and ratio of crystalline phases of Co to support. Sequential sample libraries enabled exploration of four Co loadings with five different promoters on six support materials. Catalysts stable to aging in syngas, i.e. displaying minimal change of particle size or active phase concentration, were evaluated under industrial conditions. This procedure identified SiC as a support that confers catalyst stability and that a combination of Ru and Hf promotes the stabilisation of hcp Co. Unsupported bulk samples of Co with appropriate amounts of Ru and Hf revealed that the formation of hcp Co is independent of the support. The hcp Co-containing catalyst afforded the highest catalytic activity and C5+ selectivity amongst the samples tested in this study, confirming the effectiveness of the proxy-based high-throughput method.
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- 2021
4. Machine‐Learning Prediction of Metal–Organic Framework Guest Accessibility from Linker and Metal Chemistry
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Rémi Pétuya, Samantha Durdy, Dmytro Antypov, Michael W. Gaultois, Neil G. Berry, George R. Darling, Alexandros P. Katsoulidis, Matthew S. Dyer, and Matthew J. Rosseinsky
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General Medicine ,General Chemistry ,Catalysis - Abstract
The choice of metal and linker together define the structure and therefore the guest accessibility of a metal-organic framework (MOF), but the large number of possible metal-linker combinations makes the selection of components for synthesis challenging. We predict the guest accessibility of a MOF with 80.5 % certainty based solely on the identity of these two components as chosen by the experimentalist, by decomposing reported experimental three-dimensional MOF structures in the Cambridge Structural Database into metal and linker and then learning the connection between the components' chemistry and the MOF porosity. Pore dimensions of the guest-accessible space are classified into four ranges with three sequential models. Both the dataset and the predictive models are available to download and offer simple guidance in prioritization of the choice of the components for exploratory MOF synthesis for separation and catalysis based on guest accessibility considerations.
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- 2022
5. Modular Design via Multiple Anion Chemistry of the High Mobility van der Waals Semiconductor Bi4O4SeCl2
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Tianqi Zhao, Rasmita Raval, Furio Corà, Matthew S. Dyer, Craig M. Robertson, Ben Slater, Vin Dhanak, Marco Zanella, Matthew J. Rosseinsky, Jonathan Alaria, Leanne A. H. Jones, John B. Claridge, Troy D. Manning, Fiona McBride, Quinn Gibson, and Philip A. E. Murgatroyd
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Bridging (networking) ,business.industry ,Superlattice ,Configuration entropy ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Catalysis ,0104 chemical sciences ,Ion ,symbols.namesake ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,Semiconductor ,chemistry ,Chemical physics ,Selenide ,symbols ,van der Waals force ,business ,Curse of dimensionality - Abstract
Making new van der Waals materials with electronic or magnetic functionality is a chemical design challenge for the development of two-dimensional nanoelectronic and energy conversion devices. We present the synthesis and properties of the van der Waals material Bi4O4SeCl2, which is a 1:1 superlattice of the structural units present in the van der Waals insulator BiOCl and the three-dimensionally connected semiconductor Bi2O2Se. The presence of three anions gives the new structure both the bridging selenide anion sites that connect pairs of Bi2O2 layers in Bi2O2Se and the terminal chloride sites that produce the van der Waals gap in BiOCl. This retains the electronic properties of Bi2O2Se, while reducing the dimensionality of the bonding network connecting the Bi2O2Se units to allow exfoliation of Bi4O4SeCl2 to 1.4 nm height. The superlattice structure is stabilised by the configurational entropy of anion disorder across the terminal and bridging sites. The reduction in connective dimensionality with retention of electronic functionality stems from the expanded anion compositional diversity.
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- 2019
6. Highly absorbing lead-free semiconductor Cu2AgBiI6 for photovoltaic applications from the quaternary CuI-AgI-BiI3 phase space
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Bernard Wenger, Matthew J. Rosseinsky, Laura M. Herz, Giulia Longo, Henry J. Snaith, Matthew S. Dyer, Leonardo R. V. Buizza, John B. Claridge, Troy D. Manning, Harry C. Sansom, Mojtaba Abdi-Jalebi, Adam D. Wright, Suhas Mahesh, Michael J. Pitcher, Marco Zanella, and Richard H. Friend
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Photoluminescence ,Chemistry ,business.industry ,F100 ,General Chemistry ,Quaternary compound ,C700 ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Article ,C900 ,Catalysis ,0104 chemical sciences ,symbols.namesake ,Colloid and Surface Chemistry ,Semiconductor ,Photovoltaics ,Chemical physics ,Stokes shift ,symbols ,Direct and indirect band gaps ,Thin film ,Absorption (electromagnetic radiation) ,business - Abstract
Since the emergence of lead halide perovskites for photovoltaic research, there has been mounting effort in the search for alternative compounds with improved or complementary physical, chemical, or optoelectronic properties. Here, we report the discovery of Cu2AgBiI6: a stable, inorganic, lead-free wide-band-gap semiconductor, well suited for use in lead-free tandem photovoltaics. We measure a very high absorption coefficient of 1.0 × 105 cm–1 near the absorption onset, several times that of CH3NH3PbI3. Solution-processed Cu2AgBiI6 thin films show a direct band gap of 2.06(1) eV, an exciton binding energy of 25 meV, a substantial charge-carrier mobility (1.7 cm2 V–1 s–1), a long photoluminescence lifetime (33 ns), and a relatively small Stokes shift between absorption and emission. Crucially, we solve the structure of the first quaternary compound in the phase space among CuI, AgI and BiI3. The structure includes both tetrahedral and octahedral species which are open to compositional tuning and chemical substitution to further enhance properties. Since the proposed double-perovskite Cs2AgBiI6 thin films have not been synthesized to date, Cu2AgBiI6 is a valuable example of a stable Ag+/Bi3+ octahedral motif in a close-packed iodide sublattice that is accessed via the enhanced chemical diversity of the quaternary phase space.
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- 2021
7. Discovery of a Low Thermal Conductivity Oxide Guided by Probe Structure Prediction and Machine Learning
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Christopher Collins, Michael Moran, Matthew S. Dyer, George R. Darling, Olivier Perez, Charlene Delacotte, Gyorgyi Glodan, Quinn Gibson, Richard Feetham, Michael J. Pitcher, Denis Pelloquin, Marco Zanella, Jonathan Alaria, Luke M. Daniels, Matthew J. Rosseinsky, John B. Claridge, Michael W. Gaultois, Troy D. Manning, Claire A. Murray, University of Liverpool, DIAMOND Light source, University of Manchester [Manchester], Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry University of Liverpool, Univ Liverpool, Dept Chem, Crown St, Liverpool L69 7ZD, Merseyside, England, Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC), and University of Liverpool - Department of Chemistry
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Materials science ,Oxide ,Structure (category theory) ,02 engineering and technology ,[CHIM.INOR]Chemical Sciences/Inorganic chemistry ,Machine learning ,computer.software_genre ,010402 general chemistry ,Heat capacity ,01 natural sciences ,Catalysis ,symbols.namesake ,chemistry.chemical_compound ,Thermal conductivity ,README ,[CHIM.CRIS]Chemical Sciences/Cristallography ,[CHIM]Chemical Sciences ,Aperiodic structure ,ComputingMilieux_MISCELLANEOUS ,Research Articles ,titanium oxides ,Titanium ,010405 organic chemistry ,business.industry ,Experimental data ,Oxides ,General Chemistry ,General Medicine ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,chemistry ,Aperiodic graph ,symbols ,Transition‐Metal Oxides | Very Important Paper ,Artificial intelligence ,Metastable compounds ,Raman spectroscopy ,business ,0210 nano-technology ,computer ,Research Article - Abstract
We report the aperiodic titanate Ba10Y6Ti4O27 with a room‐temperature thermal conductivity that equals the lowest reported for an oxide. The structure is characterised by discontinuous occupancy modulation of each of the sites and can be considered as a quasicrystal. The resulting localisation of lattice vibrations suppresses phonon transport of heat. This new lead material for low‐thermal‐conductivity oxides is metastable and located within a quaternary phase field that has been previously explored. Its isolation thus requires a precisely defined synthetic protocol. The necessary narrowing of the search space for experimental investigation was achieved by evaluation of titanate crystal chemistry, prediction of unexplored structural motifs that would favour synthetically accessible new compositions, and assessment of their properties with machine‐learning models., Ba10Y6Ti4O27 has a complex aperiodic structure with the lowest thermal conductivity of any first‐transition‐series oxide. It is metastable, which makes it challenging to identify. Experimental exploration was focused sufficiently by structure prediction and property‐targeted machine learning to enable the isolation of this material (see picture), whose structural motifs provide new insight into the control of heat transport.
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- 2021
8. Selective conversion of 5-hydroxymethylfurfural to diketone derivatives over Beta zeolite-supported Pd catalysts in water
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Alexios Grigoropoulos, Marco Zanella, Frédéric Blanc, Alexandros P. Katsoulidis, Rubén Ramos, Matthew J. Rosseinsky, John B. Claridge, Troy D. Manning, and Ben L. Griffiths
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Diketone ,010405 organic chemistry ,010402 general chemistry ,01 natural sciences ,Catalysis ,0104 chemical sciences ,chemistry.chemical_compound ,Hydrolysis ,Transition metal ,chemistry ,Furan ,Physical and Theoretical Chemistry ,Selectivity ,Bifunctional ,Zeolite ,Nuclear chemistry - Abstract
Conversion of 5-hydroxymethylfurfural (HMF) in water to the linear diketone derivatives 1-hydroxyhexane-2,5-dione (HHD) and 2,5-hexanedione (HXD) was investigated over a series of Beta zeolite-supported transition metal catalysts (Co, Ni, Cu, Ru, Pd). Their catalytic performance was tested in a batch stirred reactor (T = 110 °C, PH2 = 20 bar) with Pd showing the highest activity and selectivity to HHD and HXD. The effects of Pd particle size, zeolite Si/Al ratio and reaction conditions (T = 80–155 °C, PH2 = 5–60 bar) were also investigated. The incorporation of Pd into Beta zeolite by the deposition-coprecipitation method produced the most efficient catalyst, affording complete HMF conversion (T = 110 °C, PH2 = 60 bar) predominantly to HHD (68% selectivity) and HXD (8% selectivity). The combination of a bifunctional acid/redox solid catalyst and water enhances the hydrolytic ring-opening and subsequent hydrogenation of the furan ring. Catalytic activity can be partially restored by a simple regeneration treatment. This work establishes a catalytic route to produce valuable diketone derivatives from renewable furanic platform sources in water.
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- 2019
9. Stabilization of O–O Bonds by d0 Cations in Li4+xNi1–xWO6 (0 ≤ x ≤ 0.25) Rock Salt Oxides as the Origin of Large Voltage Hysteresis
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John B. Claridge, Sarah J. Day, Arnaud J. Perez, Chiu C. Tang, Michael J. Pitcher, Filipe Braga, Laurence J. Hardwick, Marco Zanella, William J. Thomas, Christopher Collins, Jose A. Coca-Clemente, Johnson Timothy Allan, Matthew S. Dyer, Zoe N. Taylor, Nicholas E. Drewett, Vinod R. Dhanak, and Matthew J. Rosseinsky
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chemistry.chemical_classification ,Inorganic chemistry ,Oxide ,chemistry.chemical_element ,Salt (chemistry) ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Redox ,Catalysis ,Cathode ,0104 chemical sciences ,Ion ,law.invention ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,Transition metal ,chemistry ,law ,Single bond ,Lithium - Abstract
Multinary lithium oxides with the rock salt structure are of technological importance as cathode materials in rechargeable lithium ion batteries. Current state-of-the-art cathodes such as LiNi1/3Mn1/3Co1/3O2 rely on redox cycling of earth-abundant transition-metal cations to provide charge capacity. Recently, the possibility of using the oxide anion as a redox center in Li-rich rock salt oxides has been established as a new paradigm in the design of cathode materials with enhanced capacities (>200 mAh/g). To increase the lithium content and access electrons from oxygen-derived states, these materials typically require transition metals in high oxidation states, which can be easily achieved using d0 cations. However, Li-rich rock salt oxides with high valent d0 cations such as Nb5+ and Mo6+ show strikingly high voltage hysteresis between charge and discharge, the origin of which is uninvestigated. In this work, we study a series of Li-rich compounds, Li4+ xNi1- xWO6 (0 ≤ x ≤ 0.25) adopting two new and distinct cation-ordered variants of the rock salt structure. The Li4.15Ni0.85WO6 (x = 0.15) phase has a large reversible capacity of 200 mAh/g, without accessing the Ni3+/Ni4+ redox couple, implying that more than two-thirds of the capacity is due to anionic redox, with good cyclability. The presence of the 5d0 W6+ cation affords extensive (>2 V) voltage hysteresis associated with the anionic redox. We present experimental evidence for the formation of strongly stabilized localized O-O single bonds that explain the energy penalty required to reduce the material upon discharge. The high valent d0 cation associates localized anion-anion bonding with the anion redox capacity.
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- 2019
10. One site, two cations, three environments: s2 and s0 electronic configurations generate Pb-free relaxor behaviour in a perovskite oxide
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Marco Zanella, William J. Thomas, Jonathan Alaria, Luke M. Daniels, Jacinthe Gamon, Thomas A. Whittle, Philippa M. Shepley, Matthew J. Rosseinsky, Anton Goetzee-Barral, Quinn Gibson, T. Wesley Surta, Matthew A. Wright, Yang Li, John B. Claridge, Andrew J. Bell, Hongjun Niu, Department of Chemistry University of Liverpool, University of Liverpool, School of Physics and Astronomy [Leeds], University of Leeds, School of Chemical and Process Engineering, Department of Physics - University of Liverpool, and We thank the EPSRC (EP/R011753 and EP/R010293) for funding this research. J.G. and Q.D.G. acknowledge support through EP/N004884. We thank the STFC for access to Polaris (Xpress proposal 1890309) and Dr. Ron Smith for collecting the data and performing absorption corrections. We thank Argonne National Laboratory for access to the 11BM beamline (Rapid Access proposal 65125) and to Dr. Saul Lapidus and Dr. Lynn Ribaud for collecting the data
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010302 applied physics ,Phase boundary ,Oxide ,02 engineering and technology ,General Chemistry ,[CHIM.MATE]Chemical Sciences/Material chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Biochemistry ,Piezoelectricity ,Ferroelectricity ,Catalysis ,Article ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,chemistry ,Chemical physics ,Local symmetry ,0103 physical sciences ,Electron configuration ,0210 nano-technology ,Solid solution ,Perovskite (structure) - Abstract
The piezoelectric devices widespread in society use noncentrosymmetric Pb-based oxides because of their outstanding functional properties. The highest figures of merit reported are for perovskites based on the parent Pb(Mg1/3Nb2/3)O3 (PMN), which is a relaxor: a centrosymmetric material with local symmetry breaking that enables functional properties, which resemble those of a noncentrosymmetric material. We present the Pb-free relaxor (K1/2Bi1/2)(Mg1/3Nb2/3)O3 (KBMN), where the thermal and (di)electric behavior emerges from the discrete structural roles of the s0 K+ and s2 Bi3+ cations occupying the same A site in the perovskite structure, as revealed by diffraction methods. This opens a distinctive route to Pb-free piezoelectrics based on relaxor parents, which we demonstrate in a solid solution of KBMN with the Pb-free ferroelectric (K1/2Bi1/2)TiO3, where the structure and function evolve together, revealing a morphotropic phase boundary, as seen in PMN-derived systems. The detailed multiple-length-scale understanding of the functional behavior of KBMN suggests that precise chemical manipulation of the more diverse local displacements in the Pb-free relaxor will enhance performance.
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- 2021
11. Amino Acid Residues Determine the Response of Flexible Metal–Organic Frameworks to Guests
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Matthew J. Rosseinsky, Neil G. Berry, George F. S. Whitehead, Elliot J. Carrington, Chiu C. Tang, Rebecca K. Hylton, Yong Yan, Alexandros P. Katsoulidis, Rémi Pétuya, Matthew S. Dyer, George R. Darling, Dmytro Antypov, and Ajay Verma
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Chemistry ,fungi ,macromolecular substances ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Combinatorial chemistry ,Article ,Catalysis ,0104 chemical sciences ,Colloid and Surface Chemistry ,Chemical stimuli ,Metal-organic framework ,Amino acid residue - Abstract
Flexible metal-organic frameworks (MOFs) undergo structural transformations in response to physical and chemical stimuli. This is hard to control because of feedback between guest uptake and host structure change. We report a family of flexible MOFs based on derivatized amino acid linkers. Their porosity consists of a one-dimensional channel connected to three peripheral pockets. This network structure amplifies small local changes in linker conformation, which are strongly coupled to the guest packing in and the shape of the peripheral pockets, to afford large changes in the global pore geometry that can, for example, segment the pore into four isolated components. The synergy among pore volume, guest packing, and linker conformation that characterizes this family of structures can be determined by the amino acid side chain, because it is repositioned by linker torsion. The resulting control optimizes noncovalent interactions to differentiate the uptake and structure response of host-guest pairs with similar chemistries.
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- 2020
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12. Encapsulation of Crabtree's Catalyst in Sulfonated MIL‐101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment
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Alexios Grigoropoulos, Alasdair I. McKay, Alexandros P. Katsoulidis, Robert P. Davies, Anthony Haynes, Lee Brammer, Jianliang Xiao, Andrew S. Weller, and Matthew J. Rosseinsky
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SINGLE-SITE CATALYSTS ,Chemistry, Multidisciplinary ,OXIDATION ,010402 general chemistry ,01 natural sciences ,Metal–Organic Frameworks ,allylic alcohols ,Catalysis ,Gas phase ,chemistry.chemical_compound ,METAL-ORGANIC FRAMEWORK ,PRIMARY ALLYLIC ALCOHOLS ,Crabtree's catalyst ,PINCER COMPLEX ,metal-organic frameworks ,ISOMERIZATION ,Science & Technology ,010405 organic chemistry ,Chemistry ,Communication ,Organic Chemistry ,OLEFIN HYDROGENATION ,PORE ENVIRONMENT ,General Medicine ,General Chemistry ,HETEROCYCLIC CARBENE LIGANDS ,Communications ,0104 chemical sciences ,HOMOGENEOUS CATALYSTS ,Chemical engineering ,Homogeneous ,Physical Sciences ,encapsulation ,Metal-organic framework ,hydrogenation ,03 Chemical Sciences ,Selectivity ,Isomerization - Abstract
Crabtree's catalyst was encapsulated inside the pores of the sulfonated MIL‐101(Cr) metal–organic framework (MOF) by cation exchange. This hybrid catalyst is active for the heterogeneous hydrogenation of non‐functionalized alkenes either in solution or in the gas phase. Moreover, encapsulation inside a well‐defined hydrophilic microenvironment enhances catalyst stability and selectivity to hydrogenation over isomerization for substrates bearing ligating functionalities. Accordingly, the encapsulated catalyst significantly outperforms its homogeneous counterpart in the hydrogenation of olefinic alcohols in terms of overall conversion and selectivity, with the chemical microenvironment of the MOF host favouring one out of two competing reaction pathways.
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- 2018
13. Bi4O4Cu1.7Se2.7Cl0.3: Intergrowth of BiOCuSe and Bi2O2Se Stabilized by the Addition of a Third Anion
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Matthew S. Dyer, George F. S. Whitehead, Quinn Gibson, John B. Claridge, Michael J. Pitcher, Holly J. Edwards, Matthew J. Rosseinsky, Troy D. Manning, Vin Dhanak, Marco Zanella, Jonathan Alaria, and Karl Dawson
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Chemistry ,Stacking ,Formal charge ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Biochemistry ,Catalysis ,0104 chemical sciences ,Ion ,Crystal ,Crystallography ,Colloid and Surface Chemistry ,Thermal conductivity ,Phase (matter) ,0210 nano-technology ,Layer (electronics) ,Stoichiometry - Abstract
Layered two-anion compounds are of interest for their diverse electronic properties. The modular nature of their layered structures offers opportunities for the construction of complex stackings used to introduce or tune functionality, but the accessible layer combinations are limited by the crystal chemistries of the available anions. We present a layered three-anion material, Bi4O4Cu1.7Se2.7Cl0.3, which adopts a new structure type composed of alternately stacked BiOCuSe and Bi2O2Se-like units. This structure is accessed by inclusion of three chemically distinct anions, which are accommodated by aliovalently substituted Bi2O2Se0.7Cl0.3 blocks coupled to Cu-deficient Bi2O2Cu1.7Se2 blocks, producing a formal charge modulation along the stacking direction. The hypothetical parent phase Bi4O4Cu2Se3 is unstable with respect to its charge-neutral stoichiometric building blocks. The complex layer stacking confers excellent thermal properties upon Bi4O4Cu1.7Se2.7Cl0.3: a room tem-perature thermal conductivity (κ) of 0.4(1) W/mK was measured on a pellet with preferred crystallite orientation along the stacking axis, with perpendicular measurement indicating it is also highly anisotropic. This κ value lies in the ultra-low regime and is smaller than that of both BiOCuSe and Bi2O2Se. Bi4O4Cu1.7Se2.7Cl0.3 behaves like a charge-balanced semiconductor with a narrow band gap. The chemical diversity offered by the additional anion allows the integration of two common structural units in a single phase by the simultaneous and coupled creation of charge-balancing defects in each of the units.
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- 2017
14. Peptide Metal–Organic Frameworks for Enantioselective Separation of Chiral Drugs
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Yolanda Moliner-Martínez, Dmytro Antypov, Pilar Campíns-Falcó, Matthew J. Rosseinsky, Carlos Martí-Gastaldo, A. Argente-García, Daniel Roca-Sanjuán, and José Navarro-Sánchez
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Stereoisomerism ,Tripeptide ,Molecular Dynamics Simulation ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Catalysis ,Methamphetamine ,Colloid and Surface Chemistry ,Organic chemistry ,Molecule ,Metal-Organic Frameworks ,Ephedrine ,Molecular Structure ,010405 organic chemistry ,Chemistry ,Diastereomer ,Enantioselective synthesis ,Química ,General Chemistry ,Combinatorial chemistry ,0104 chemical sciences ,13. Climate action ,Racemic mixture ,Metal-organic framework ,Pèptids ,Enantiomer ,Peptides ,Monte Carlo Method ,Copper - Abstract
We report the ability of a chiral Cu(II) 3D MOF based on the tripeptide Gly-L-His-Gly (GHG) for the enantioselective separation of metamphetamine and ephedrine. Monte Carlo simulations suggest that chiral recognition is linked to preferential binding of one of the enantiomers as result of either stronger or additional H-bonds with the framework that lead to energetically more stable diastereomeric adducts. Solid phase extraction (SPE) of a racemic mixture by using Cu(GHG) as extractive phase permits isolating more than 50% of the (+)-ephedrine enantiomer as target compound in only four minutes. To the best of our knowledge, this represents the first example of a MOF capable of separating chiral polar drugs.
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- 2017
15. Selective conversion of 5-hydroxymethylfurfural to cyclopentanone derivatives over Cu–Al2O3 and Co–Al2O3 catalysts in water
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Rubén Ramos, Matthew J. Rosseinsky, Noémie Perret, Troy D. Manning, Alexios Grigoropoulos, John B. Claridge, Marco Zanella, and Alexandros P. Katsoulidis
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Reaction mechanism ,010405 organic chemistry ,Inorganic chemistry ,Diol ,Sorption ,010402 general chemistry ,Cyclopentanone ,01 natural sciences ,Pollution ,0104 chemical sciences ,Catalysis ,Metal ,chemistry.chemical_compound ,chemistry ,Transition metal ,visual_art ,visual_art.visual_art_medium ,Environmental Chemistry ,Mesoporous material - Abstract
The production of cyclopentanone derivatives from 5-hydroxymethylfurfural (HMF) using non-noble metal based catalysts is reported for the first time. Five different mixed oxides containing Ni, Cu, Co, Zn and Mg phases on an Al-rich amorphous support were prepared and characterised (XRD, ICP, SEM, TEM, H2-TPR, NH3/CO2-TPD and N2 sorption). The synthesised materials resulted in well-dispersed high metal loadings in a mesoporous network, exhibiting acid/base properties. The catalytic performance was tested in a batch stirred reactor under H2 pressure (20–50 bar) in the range T = 140–180 °C. The Cu–Al2O3 and the Co–Al2O3 catalysts showed a highly selective production of 3-hydroxymethylcyclopentanone (HCPN, 86%) and 3-hydroxymethylcyclopentanol (HCPL, 94%), respectively. A plausible reaction mechanism is proposed, clarifying the role of the reduced metal phases and the acid/basic sites on the main conversion pathways. Both Cu–Al2O3 and Co–Al2O3 catalysts showed a loss of activity after the first run, which can be reversed by a regeneration treatment. The results establish an efficient catalytic route for the production of the diol HCPL (reported for the first time) and the ketone HCPN from bio-derived HMF over 3d transition metals based catalysts in an environmental friendly medium such as water.
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- 2017
16. In Vitro Determination of the Immunogenic Impact of Nanomaterials on Primary Peripheral Blood Mononuclear Cells
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Matthew J. Rosseinsky, Patricia Murray, Neill J. Liptrott, Christopher David, Andrew Owen, and Michael Barrow
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0301 basic medicine ,Metal Nanoparticles ,02 engineering and technology ,Ferric Compounds ,lcsh:Chemistry ,Interleukin-1alpha ,Mononuclear Phagocyte System ,lcsh:QH301-705.5 ,nanomaterials ,Spectroscopy ,chemistry.chemical_classification ,Chemistry ,Caspase 1 ,General Medicine ,Silicon Dioxide ,021001 nanoscience & nanotechnology ,Interleukin-10 ,Computer Science Applications ,nanotoxicology ,0210 nano-technology ,Oxidation-Reduction ,Cell Survival ,Context (language use) ,Peripheral blood mononuclear cell ,Article ,Catalysis ,Inorganic Chemistry ,03 medical and health sciences ,inflammasome ,In vivo ,Humans ,Physical and Theoretical Chemistry ,Molecular Biology ,Reactive oxygen species ,Tumor Necrosis Factor-alpha ,Organic Chemistry ,In vitro ,Nanostructures ,immunotoxicology ,030104 developmental biology ,Gene Expression Regulation ,lcsh:Biology (General) ,lcsh:QD1-999 ,Nanotoxicology ,Cell culture ,Leukocytes, Mononuclear ,Biophysics ,Polystyrenes ,nanoparticles ,Reactive Oxygen Species ,Ex vivo - Abstract
Investigation of the potential for nanomaterials to generate immunogenic effects is a key aspect of a robust preclinical evaluation. In combination with physicochemical characterization, such assessments also provide context for how material attributes influence biological outcomes. Furthermore, appropriate models for these assessments allow accurate in vitro to in vivo extrapolation, which is vital for the mechanistic understanding of nanomaterial action. Here we have assessed the immunogenic impact of a small panel of commercially available and in-house prepared nanomaterials on primary human peripheral blood mononuclear cells (PBMCs). A diethylaminoethyl-dextran (DEAE-dex) functionalized superparamagnetic iron oxide nanoparticle (SPION) generated detectable quantities of tumor necrosis factor &alpha, (TNF&alpha, ), interleukin-1&beta, (IL-1&beta, ), and IL-10, the only tested material to do so. The human leukemia monocytic cell line THP-1 was used to assess the potential for the nanomaterial panel to affect cellular oxidation-reduction (REDOX) via measurement of reactive oxygen species and reduced glutathione. Negatively charged sulfonate-functionalized polystyrene nanoparticles demonstrated a size-related trend for the inhibition of caspase-1, which was not observed for amine-functionalized polystyrene of similar sizes. Silica nanoparticles (310 nm) resulted in a 93% increase in proliferation compared to the untreated control (p <, 0.01). No other nanomaterial treatments resulted in significant change from that of unstimulated PBMCs. Responses to the nanomaterials in the assays described demonstrate the utility of primary cells as ex vivo models for nanomaterial biological impact.
- Published
- 2020
17. Sponge‐Like Behaviour in Isoreticular Cu(Gly‐His‐X) Peptide‐Based Porous Materials
- Author
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John E. Warren, Jayne A. Armstrong, Matthew J. Rosseinsky, Michael E. Briggs, K. Mark Thomas, and Carlos Martí-Gastaldo
- Subjects
postsynthetic modifications ,Peptide ,Tripeptide ,Catalysis ,metal–organic frameworks ,Adsorption ,Metalloproteins ,Polymer chemistry ,Urea ,Molecule ,Porosity ,water adsorption ,chemistry.chemical_classification ,Molecular Structure ,nanoporous materials ,Organic Chemistry ,Sorption ,General Chemistry ,Full Papers ,chemistry ,Chemical engineering ,peptides ,Metal-organic framework ,Porous medium ,Oligopeptides ,Copper - Abstract
We report two isoreticular 3D peptide-based porous frameworks formed by coordination of the tripeptides Gly-L-His-Gly and Gly-L-His-L-Lys to Cu(II) which display sponge-like behaviour. These porous materials undergo structural collapse upon evacuation that can be reversed by exposure to water vapour, which permits recovery of the original open channel structure. This is further confirmed by sorption studies that reveal that both solids exhibit selective sorption of H2 O while CO2 adsorption does not result in recovery of the original structures. We also show how the pendant aliphatic amine chains, present in the framework from the introduction of the lysine amino acid in the peptidic backbone, can be post-synthetically modified to produce urea-functionalised networks by following methodologies typically used for metal-organic frameworks built from more rigid "classical" linkers.
- Published
- 2015
18. Room Temperature Magnetically Ordered Polar Corundum GaFeO3 Displaying Magnetoelectric Coupling
- Author
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Hongjun Niu, Michael J. Pitcher, Dmitry Batuk, Sanliang Ling, Matthew J. Rosseinsky, Pranab K. Mandal, Claire A. Murray, Sarah J. Day, Artem M. Abakumov, Marco Zanella, Craig L. Bull, Ronald I. Smith, Furio Corà, Plamen Stamenov, John B. Claridge, Karl Dawson, Alex J. Corkett, and Ben Slater
- Subjects
Neutron diffraction ,Configuration entropy ,Point reflection ,Mineralogy ,Corundum ,02 engineering and technology ,engineering.material ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Catalysis ,Condensed Matter::Materials Science ,Colloid and Surface Chemistry ,Multiferroics ,Isostructural ,Chemistry ,Physics ,General Chemistry ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Electron diffraction ,Chemical physics ,engineering ,Polar ,0210 nano-technology - Abstract
The polar corundum structure type offers a route to new room temperature multiferroic materials, as the partial LiNbO3-type cation ordering that breaks inversion symmetry may be combined with long-range magnetic ordering of high spin d5 cations above room temperature in the AFeO3 system. We report the synthesis of a polar corundum GaFeO3 by a high-pressure, high-temperature route and demonstrate that its polarity arises from partial LiNbO3-type cation ordering by complementary use of neutron, X-ray, and electron diffraction methods. In situ neutron diffraction shows that the polar corundum forms directly from AlFeO3-type GaFeO3 under the synthesis conditions. The A3+/Fe3+ cations are shown to be more ordered in polar corundum GaFeO3 than in isostructural ScFeO3. This is explained by DFT calculations which indicate that the extent of ordering is dependent on the configurational entropy available to each system at the very different synthesis temperatures required to form their corundum structures. Polar corundum GaFeO3 exhibits weak ferromagnetism at room temperature that arises from its Fe2O3-like magnetic ordering, which persists to a temperature of 408 K. We demonstrate that the polarity and magnetization are coupled in this system with a measured linear magnetoelectric coupling coefficient of 0.057 ps/m. Such coupling is a prerequisite for potential applications of polar corundum materials in multiferroic/magnetoelectric devices.
- Published
- 2017
19. Catalysis in MOFs: general discussion
- Author
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Mohamed Eddaoudi, Zhijie Chen, Lauren N. McHugh, Matthew R. Ryder, Monique A. van der Veen, Valeska P. Ting, Frederik Haase, Wenbin Lin, Susumu Kitagawa, Marco Ranocchiari, Connie C. Lu, Karena W. Chapman, Jeffrey R. Long, Nathaniel L. Rosi, Duncan J. Woods, Ross S. Forgan, Jeffrey Paulo H. Perez, Mircea Dincă, Francesco Carraro, Dirk Volkmer, Aron Walsh, Omar K. Farha, Jet-Sing M. Lee, Omar M. Yaghi, Matthew J. Rosseinsky, Karen Leus, Shengqian Ma, Jing Li, Carlo Lamberti, Timothy L. Easun, Laura Gagliardi, Pascal Van Der Voort, David Harris, Gareth O. Lloyd, and Jane Knichal
- Subjects
Chemistry ,Organic chemistry ,Metal-organic framework ,Nanotechnology ,Homogeneous catalysis ,02 engineering and technology ,Physical and Theoretical Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,0210 nano-technology ,01 natural sciences ,0104 chemical sciences ,Catalysis - Published
- 2017
20. Acid loaded porphyrin-based metal–organic framework for ammonia uptake
- Author
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Alexandra Fateeva, Corinne A. Stone, Oliver T. Wilcox, Alexandros P. Katsoulidis, Matthew J. Rosseinsky, and Martin W. Smith
- Subjects
Sorbent ,Formic acid ,Inorganic chemistry ,Metals and Alloys ,Nanotechnology ,General Chemistry ,Acid load ,Porphyrin ,humanities ,Catalysis ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,chemistry.chemical_compound ,Ammonia ,chemistry ,Materials Chemistry ,Ceramics and Composites ,Metal-organic framework - Abstract
A porphyrin-based metal-organic framework is shown to be structurally stable towards acid loading using either hydrochloric or formic acid. The capacity of this material as an ammonia sorbent was analysed using micro-breakthrough experiments in both dry and humid ammonia flows. The acid loaded material exhibited excellent uptake in comparison with the parent MOF.
- Published
- 2015
21. Preparation of Fischer–Tropsch Supported Cobalt Catalysts Using a New Gas Anti-Solvent Process
- Author
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Garry B. Combes, Raimon P. Marin, Jonathan K. Bartley, Thomas E. Davies, Peter B. Williams, Simon A. Kondrat, John B. Claridge, Paul John Smith, James R. Gallagher, Stuart Hamilton Taylor, Graham J. Hutchings, Dan I. Enache, Paul Boldrin, and Matthew J. Rosseinsky
- Subjects
inorganic chemicals ,Materials science ,Coprecipitation ,Precipitation (chemistry) ,organic chemicals ,Inorganic chemistry ,chemistry.chemical_element ,Fischer–Tropsch process ,General Chemistry ,Catalysis ,Ruthenium ,law.invention ,Cobalt extraction techniques ,chemistry ,law ,heterocyclic compounds ,Calcination ,Cobalt ,Nuclear chemistry - Abstract
Cobalt and ruthenium-promoted cobalt Fischer–Tropsch catalysts supported on titania have been prepared for the first time by gas anti-solvent precipitation. The use of dense CO2 as an anti-solvent enables the precipitation of cobalt acetate and ruthenium acetylacetonate onto preformed titania. The gas anti-solvent process produces catalysts with the desired 20 wt % cobalt content as precursors, which on calcination give highly dispersed Co3O4. The addition of ruthenium to the gas anti-solvent prepared cobalt catalysts has been investigated by two methods (a) coprecipitation with cobalt acetate and (b) wet impregnation onto a precalcined cobalt titania catalyst, and these resulted in catalysts with distinctly different properties. These catalysts were compared with a standard ruthenium-promoted cobalt catalyst prepared by wet impregnation and were found to be substantially more active for the Fischer–Tropsch reaction.
- Published
- 2013
22. Desolvation of a novel microporous hydrogen-bonded framework: Characterization by in situ single-crystal and powder X-ray diffraction
- Author
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Matthew J. Rosseinsky, Paul D. Beer, Dusan Hesek, and Cameron J. Kepert
- Subjects
Materials science ,Hydrogen ,Hydrogen bond ,chemistry.chemical_element ,General Chemistry ,Microporous material ,Crystal engineering ,Catalysis ,Crystallography ,chemistry.chemical_compound ,chemistry ,X-ray crystallography ,Molecule ,Single crystal ,Tetrathiafulvalene - Abstract
Despite significant structural rearrangement upon desolvation of a three-dimensional molecular framework of hexaaquacobalt cations and redox- active functionalized tetrathiafulvalene anions (see the picture; the area filled with water molecules is shown in gray), monocrystallinity and microporosity are retained. X-ray analyses show that a unique combination of hydrogen bonds and π ·· π interactions within the framework gives this material a structural flexibility not seen in zeolites or their analogues.
- Published
- 2016
23. Sodium hydride as a powerful reducing agent for topotactic oxide deintercalation: Synthesis and characterization of the nickel(I) oxide LaNiO2
- Author
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Matthew J. Rosseinsky, Michael A. Hayward, Jeremy Sloan, and Mark Green
- Subjects
Inorganic chemistry ,Oxide ,chemistry.chemical_element ,General Chemistry ,Biochemistry ,Catalysis ,Sodium hydride ,chemistry.chemical_compound ,Nickel ,Colloid and Surface Chemistry ,chemistry ,Lamellar structure ,Cuprate ,Isostructural ,Stoichiometry ,Perovskite (structure) - Abstract
The capability of sodium hydride as a reducing agent in oxide deintercalation reactions is explored. The Ni(III) perovskite LaNiO3 can be reduced topotactically to LaNiO2, isostructural with the 'infinite layer' cuprates, using solid sodium hydride in a sealed evacuated tube at 190 ≤ T/°C ≤ 210, and a similar infinite-layer phase is prepared by reduction of NdNiO3. Structural characterization indicates the coexistence of incompletely reduced regions, with five-coordinate Ni centers due to the introduction of oxide anions between the NiO23- sheets, giving samples with a refined stoichiometry of LaNiO(2.025(3)). Neutron powder diffraction and magnetization measurements indicate that the lamellar Ni(I) phase does not show the long-range antiferromagnetic ordering characteristic of isoelectronic Cu(II) oxides. This may be due either to the influence of the interlamellar oxide defect regions or to the reduced covalent mixing of Ni 3d and O 2p levels.
- Published
- 2016
24. A first transition series pseudotetrahedral oxynitride anion: synthesis and characterization of Ba(2)VO(3)N
- Author
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Simon J. Clarke, Matthieu Puyet, Jasper Holman, Charles W. Michie, Matthew J. Rosseinsky, and Paul R. Chalker
- Subjects
Oxide ,Vanadium ,chemistry.chemical_element ,Disproportionation ,General Chemistry ,Crystal structure ,Biochemistry ,Catalysis ,Crystallography ,symbols.namesake ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,chemistry ,Phase (matter) ,X-ray crystallography ,symbols ,Molecule ,Raman spectroscopy - Abstract
Ammonolysis of reactive oxide precursors affords the vanadium(V) phase Ba(2)VO(3)N that is shown by X-ray and neutron powder diffraction and Raman spectroscopy to contain pseudotetrahedral VO(3)N(4-) anions. This is the first example of such species for the first transition series metals.
- Published
- 2016
25. Catalytic Response and Stability of Nickel/Alumina for the Hydrogenation of 5-Hydroxymethylfurfural in Water
- Author
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Marco Zanella, John B. Claridge, Troy D. Manning, Matthew J. Rosseinsky, Alexios Grigoropoulos, and Noémie Perret
- Subjects
General Chemical Engineering ,Inorganic chemistry ,chemistry.chemical_element ,engineering.material ,010402 general chemistry ,Furfural ,Cyclopentanone ,01 natural sciences ,Catalysis ,law.invention ,chemistry.chemical_compound ,Microscopy, Electron, Transmission ,X-Ray Diffraction ,law ,Nickel ,Environmental Chemistry ,General Materials Science ,Calcination ,Hydroxymethyl ,Furaldehyde ,010405 organic chemistry ,Layered double hydroxides ,Water ,0104 chemical sciences ,General Energy ,chemistry ,engineering ,Microscopy, Electron, Scanning ,Mixed oxide ,Hydrogenation ,Aluminum - Abstract
The catalytic response of Ni on Al2O3 obtained from Ni-Al layered double hydroxides was studied for the liquid-phase hydrogenation of hydroxymethyl furfural to tetrahydrofuran-2,5-diyldimethanol (THFDM) in water. The successive calcination and reduction of the precursors caused the removal of interlayer hydroxyl and carbonate groups and the reduction of Ni(2+) to Ni(0). Four reduced mixed oxide catalysts were obtained, consisting of different amount of Ni metal contents (47-68 wt%) on an Al-rich amorphous component. The catalytic activity was linked to Ni content whereas selectivity was mainly affected by reaction temperature. THFDM was formed in a stepwise manner at low temperature (353 K) whereas 3-hydroxymethyl cyclopentanone was generated at higher temperature. Coke formation caused deactivation; however, the catalytic activity can be regenerated using heat treatment. The results establish Ni on Al2O3 as a promising catalyst for the production of THFDM in water.
- Published
- 2016
26. Encapsulation of an organometallic cationic catalyst by direct exchange into an anionic MOF
- Author
-
Alexandros P. Katsoulidis, Robert P. Davies, Noémie Perret, George F. S. Whitehead, Anthony Haynes, Jianliang Xiao, F. Mark Chadwick, Lee Brammer, Andrew S. Weller, Matthew J. Rosseinsky, and Alexios Grigoropoulos
- Subjects
Chemistry, Multidisciplinary ,Inorganic chemistry ,AROMATIC-ALDEHYDES ,ETHYL DIAZOACETATE ,010402 general chemistry ,Heterogeneous catalysis ,01 natural sciences ,CYCLOPROPANATION REACTIONS ,Catalysis ,chemistry.chemical_compound ,Ethyl diazoacetate ,METAL-ORGANIC FRAMEWORK ,Polymer chemistry ,Science & Technology ,010405 organic chemistry ,Cationic polymerization ,IRON LEWIS-ACID ,General Chemistry ,WATER OXIDATION ,0104 chemical sciences ,Solvent ,Chemistry ,HOMOGENEOUS CATALYSTS ,chemistry ,DIELS-ALDER REACTIONS ,Physical Sciences ,OXIDATION CATALYSTS ,Metal-organic framework ,Hybrid material ,Stoichiometry ,BUILDING-BLOCKS - Abstract
Metal–Organic Frameworks (MOFs) are porous crystalline materials that have emerged as promising hosts\ud for the heterogenization of homogeneous organometallic catalysts, forming hybrid materials which\ud combine the benefits of both classes of catalysts. Herein, we report the encapsulation of the\ud organometallic cationic Lewis acidic catalyst [CpFe(CO)2(L)]+ ([Fp–L]+, Cp ¼ h5\ud -C5H5, L ¼ weakly bound\ud solvent) inside the pores of the anionic [Et4N]3[In3(BTC)4] MOF (H3BTC ¼ benzenetricarboxylic acid) via\ud a direct one-step cation exchange process. To conclusively validate this methodology, initially [Cp2Co]+\ud was used as an inert spatial probe to (i) test the stability of the selected host; (ii) monitor the\ud stoichiometry of the cation exchange process and (iii) assess pore dimensions, spatial location of the\ud cationic species and guest-accessible space by single crystal X-ray crystallography. Subsequently,\ud the quasi-isosteric [Fp–L]+ was encapsulated inside the pores via partial cation exchange to form\ud [(Fp–L)0.6(Et4N)2.4][In3(BTC)4]. The latter was rigorously characterized and benchmarked as\ud a heterogeneous catalyst in a simple Diels–Alder reaction, thus verifying the integrity and reactivity of\ud the encapsulated molecular catalyst. These results provide a platform for the development of\ud heterogeneous catalysts with chemically and spatially well-defined catalytic sites by direct exchange\ud of cationic catalysts into anionic MOFs.
- Published
- 2016
27. The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site
- Author
-
Paul J. Smith, Christopher John Evans, Stuart Hamilton Taylor, Graham J. Hutchings, Gemma Louise Brett, Jonathan K. Bartley, Troy D. Manning, Peter J. Miedziak, Matthew J. Rosseinsky, Simon A. Kondrat, and Robert Armstrong
- Subjects
Tartronic acid ,Materials science ,Supercritical carbon dioxide ,Inorganic chemistry ,Oxide ,chemistry.chemical_element ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Catalysis ,chemistry.chemical_compound ,Chemistry ,Catalytic oxidation ,chemistry ,Dehydration reaction ,Lanthanum ,QD ,Physical and Theoretical Chemistry ,0210 nano-technology ,Perovskite (structure) - Abstract
Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology.
- Published
- 2016
28. Artificial Construction of the Layered Ruddlesden–Popper Manganite La2Sr2Mn3O10 by Reflection High Energy Electron Diffraction Monitored Pulsed Laser Deposition
- Author
-
George R. Darling, Haiyan Tan, Jo Verbeeck, Robert G. Palgrave, Maria Batuk, Matthew J. Rosseinsky, Matthew S. Dyer, Pavel Borisov, John B. Claridge, Joke Hadermann, S. R. C. McMitchell, and He Tian
- Subjects
Spin glass ,Chemistry ,Analytical chemistry ,Nanotechnology ,02 engineering and technology ,General Chemistry ,021001 nanoscience & nanotechnology ,Manganite ,01 natural sciences ,Biochemistry ,Article ,Catalysis ,Pulsed laser deposition ,Condensed Matter::Materials Science ,Magnetic anisotropy ,Colloid and Surface Chemistry ,Lattice constant ,Ferromagnetism ,Electron diffraction ,0103 physical sciences ,Antiferromagnetism ,010306 general physics ,0210 nano-technology - Abstract
Pulsed laser deposition has been used to artificially construct the n = 3 Ruddlesden Popper structure La2Sr2Mn3O10 in epitaxial thin film form by sequentially layering La1-xSrxMnO3 and SrO unit cells aided by in situ reflection high energy electron diffraction monitoring. The interval deposition technique was used to promote two-dimensional SrO growth. X-ray diffraction and cross-sectional transmission electron microscopy indicated that the trilayer structure had been formed. A site ordering was found to differ from that expected thermodynamically, with the smaller Sr2+ predominantly on the R site due to kinetic trapping of the deposited cation sequence. A dependence of the out-of-plane lattice parameter on growth pressure was interpreted as changing the oxygen content of the films. Magnetic and transport measurements on fully oxygenated films indicated a frustrated magnetic ground state characterized as a spin glass-like magnetic phase with the glass temperature T-g approximate to 34 K. The magnetic frustration has a clear in-plane (ab) magnetic anisotropy, which is maintained up to temperatures of 150 K. Density functional theory calculations suggest competing antiferromagnetic and ferromagnetic long-range orders, which are proposed as the origin of the low-temperature glassy state.
- Published
- 2012
29. Chemical Bonding and Atomic Structure in Y2O3:ZrO2-SrTiO3 Layered Heterostructures
- Author
-
Matthew S. Dyer, George R. Darling, Matthew J. Rosseinsky, and John B. Claridge
- Subjects
Range (particle radiation) ,Chemistry ,Nanotechnology ,Heterojunction ,General Medicine ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Metal ,Condensed Matter::Materials Science ,Chemical bond ,Chemical physics ,visual_art ,0103 physical sciences ,visual_art.visual_art_medium ,Deposition (phase transition) ,010306 general physics ,Fermi gas ,0210 nano-technology ,Bulk crystal - Abstract
Deposition of nanosized layers of two different metal oxides upon one another produces layered heterostructures with a wide range of new physical properties.1 For example, a conducting two-dimensional electron gas was discovered at the interface between the two insulators LaAlO3 and SrTiO3.2 The atomic arrangements within heterostructures of complex functional oxides determine the resulting properties and are not necessarily straightforward to construct based on the bulk crystal structures of the independent components.
- Published
- 2012
30. A Polar Corundum Oxide Displaying Weak Ferromagnetism at Room Temperature
- Author
-
Michael F. Thomas, Zhongling Xu, Matthew J. Rosseinsky, Furio Corà, Florian Schiffmann, Gustaaf Van Tendeloo, Hongjun Niu, Xinming Wan, Robert G. Palgrave, Artem M. Abakumov, John E. Warren, Ben Slater, Umut Adem, Man-Rong Li, S. R. C. McMitchell, Markys G. Cain, Chris I. Thomas, Duong V. Giap, Timothy L. Burnett, and John B. Claridge
- Subjects
Oxide ,Mineralogy ,Corundum ,02 engineering and technology ,engineering.material ,010402 general chemistry ,Ferric Compounds ,01 natural sciences ,Biochemistry ,Article ,Catalysis ,Condensed Matter::Materials Science ,chemistry.chemical_compound ,Magnetization ,Colloid and Surface Chemistry ,Aluminum Oxide ,Antiferromagnetism ,Multiferroics ,Condensed matter physics ,Magnetic Phenomena ,Temperature ,Membranes, Artificial ,Oxides ,General Chemistry ,021001 nanoscience & nanotechnology ,Ferroelectricity ,0104 chemical sciences ,Chemistry ,chemistry ,Ferromagnetism ,engineering ,0210 nano-technology ,Ground state ,Scandium - Abstract
Combining long-range magnetic order with polarity in the same structure is a prerequisite for the design of (magnetoelectric) multiferroic materials. There are now several demonstrated strategies to achieve this goal, but retaining magnetic order above room temperature remains a difficult target. Iron oxides in the +3 oxidation state have high magnetic ordering temperatures due to the size of the coupled moments. Here we prepare and characterize ScFeO3 (SFO), which under pressure and in strain-stabilized thin films adopts a polar variant of the corundum structure, one of the archetypal binary oxide structures. Polar corundum ScFeO3 has a weak ferromagnetic ground state below 356 K-this is in contrast to the purely antiferromagnetic ground state adopted by the well-studied ferroelectric BiFeO3.
- Published
- 2012
31. The effect of heat treatment on phase formation of copper manganese oxide: Influence on catalytic activity for ambient temperature carbon monoxide oxidation
- Author
-
Matthew J. Rosseinsky, Jonathan K. Bartley, Thomas E. Davies, Paul Boldrin, Stuart Hamilton Taylor, Graham J. Hutchings, Simon A. Kondrat, Albert Frederick Carley, and Zhongling Zu
- Subjects
Copper oxide ,Inorganic chemistry ,Spinel ,chemistry.chemical_element ,Manganese ,engineering.material ,Copper ,Catalysis ,Supercritical fluid ,chemistry.chemical_compound ,Hopcalite ,chemistry ,engineering ,Physical and Theoretical Chemistry ,Carbon monoxide - Abstract
The auto-reduction of copper and manganese acetates has been investigated using in situ X-ray diffraction and thermogravimetric analysis, with the intention of manipulating the phenomena to tailor specific phase formation for synthesising catalysts. Subsequently catalysts prepared in this controlled manner were evaluated for ambient temperature CO oxidation. The decomposition of mixed copper and manganese acetate systems was controlled to form MnO x-supported Cu or CuMnOx spinel structures, depending on the oxygen concentration and flow conditions during the heat treatment. Catalyst precursors were prepared by physical grinding and by a supercritical CO 2 anti-solvent precipitation process. The use of supercritical anti-solvent precipitation allows for the formation of well-mixed metal acetates that decompose to form active spinel CO-oxidation catalysts or small copper nano-particles supported on MnOx, depending on the oxygen content of the heat treatment atmosphere. The ability to tune oxidation state and phase composition of catalysts is a key preparation parameter for controlling the activity and provides insight into the active sites for CO oxidation. © 2011 Elsevier Inc. All rights reserved.
- Published
- 2011
32. The effect of platinum on the performance of WO3 nanocrystal photocatalysts for the oxidation of Methyl Orange and iso-propanol
- Author
-
Humphrey H. P. Yiu, James R. Darwent, Upendra A. Joshi, and Matthew J. Rosseinsky
- Subjects
Materials science ,Renewable Energy, Sustainability and the Environment ,General Chemical Engineering ,Organic Chemistry ,chemistry.chemical_element ,Photochemistry ,Pollution ,Nanocrystalline material ,law.invention ,Catalysis ,Inorganic Chemistry ,chemistry.chemical_compound ,Fuel Technology ,chemistry ,Nanocrystal ,law ,Photocatalysis ,Methyl orange ,Platinum ,Waste Management and Disposal ,Clark electrode ,Biotechnology ,Visible spectrum - Abstract
BACKGROUND: This research investigated the effect of platinum (Pt) on the reactivity of tungsten oxide (WO3) for the visible light photocatalytic oxidation of dyes. RESULTS: Nanocrystalline tungsten oxide (WO3) photocatalysts were synthesised by a sol-gel process and employed for the photocatalytic degradation of Methyl Orange under visible light. For comparison commercial bulk WO3 materials were also studied for the same reaction. These materials were fully characterised using X-ray diffraction (XRD), UV-visible diffuse reflection spectroscopy and transmission electron microscopy (TEM). The photocatalytic oxidation of iso-propanol was used as a model reaction to follow the concomitant reduction of molecular oxygen. No reactions occured in the absence of platinum, which is an essential co-catalyst for the multi-electron reduction of oxygen. The platinised WO3 catalysts were stable for multiple oxidation–reduction cycles. The results from the catalytic activity measurements showed that platinised nanocrystalline WO3 is a superior oxidation photocatalyst when compared with bulk WO3. Methyl Orange was completely decolourised in 4 h. CONCLUSIONS: The enhanced performance of nanocrystalline Pt-WO3 is attributed to improved charge separation in the nanosized photocatalyst. Platinum is an essential co-catalyst to reduce oxygen. This photocatalyst could be applied to the treatment of organic pollutants in wastewater, with the advantage of using visible light compared with the widely studied TiO2, which requires UV light. Copyright © 2011 Society of Chemical Industry
- Published
- 2011
33. Visible Light Photo-oxidation of Model Pollutants Using CaCu3Ti4O12: An Experimental and Theoretical Study of Optical Properties, Electronic Structure, and Selectivity
- Author
-
Matthew S. Dyer, Christopher P. Ireland, Robert G. Palgrave, James R. Darwent, Matthew J. Rosseinsky, John B. Claridge, and Joanna H. Clark
- Subjects
Electronic correlation ,Chemistry ,Nanotechnology ,02 engineering and technology ,General Chemistry ,Electronic structure ,Electron ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Photochemistry ,01 natural sciences ,Biochemistry ,Catalysis ,Article ,0104 chemical sciences ,Colloid and Surface Chemistry ,13. Climate action ,Photocatalysis ,Charge carrier ,Reactivity (chemistry) ,QD ,0210 nano-technology ,Absorption (electromagnetic radiation) ,Visible spectrum - Abstract
Charge transfer between metal ions occupying distinct crystallographic sublattices in an ordered material is a strategy to confer visible light absorption on complex oxides to generate potentially catalytically active electron and hole charge carriers. CaCu3Ti4O12 has distinct octahedral Ti4+ and square planar Cu2+ sites and is thus a candidate material for this approach. The sol−gel synthesis of high surface area CaCu3Ti4O12 and investigation of its optical absorption and photocatalytic reactivity with model pollutants are reported. Two gaps of 2.21 and 1.39 eV are observed in the visible region. These absorptions are explained by LSDA+U electronic structure calculations, including electron correlation on the Cu sites, as arising from transitions from a Cu-hybridized O 2p-derived valence band to localized empty states on Cu (attributed to the isolation of CuO4 units within the structure of CaCu3Ti4O12) and to a Ti-based conduction band. The resulting charge carriers produce selective visible light photodegradation of 4-chlorophenol (monitored by mass spectrometry) by Pt-loaded CaCu3Ti4O12 which is attributed to the chemical nature of the photogenerated charge carriers and has a quantum yield comparable with commercial visible light photocatalysts.
- Published
- 2010
34. A Guest-Responsive Fluorescent 3D Microporous Metal−Organic Framework Derived from a Long-Lifetime Pyrene Core
- Author
-
John Bacsa, James T. A. Jones, Matthew J. Rosseinsky, Darren Bradshaw, Romain Heck, Kyriakos C. Stylianou, Samantha Y. Chong, and Yaroslav Z. Khimyak
- Subjects
Ligand ,General Chemistry ,Microporous material ,Photochemistry ,Biochemistry ,Fluorescence ,Catalysis ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,chemistry ,Organic chemistry ,Pyrene ,Molecule ,Metal-organic framework ,Thermal stability ,Carboxylate - Abstract
The carboxylate ligand 1,3,6,8-tetrakis(p-benzoic acid)pyrene (TBAPy)-based on the strongly fluorescent long-lifetime pyrene core-affords a permanently microporous fluorescent metal-organic framework, [In(2)(OH)(2)(TBAPy)].(guests) (1), displaying 54% total accessible volume and excellent thermal stability. Fluorescence studies reveal that both 1 and TBAPy display strong emission bands at 471 and 529 nm, respectively, upon excitation at 390 nm, with framework coordination of the TBAPy ligands significantly increasing the emission lifetime from 0.089 to 0.110 ms. Upon desolvation, the emission band for the framework is shifted to lower energy: however, upon re-exposure to DMF the as-made material is regenerated with reversible fluorescence behavior. Together with the lifetime, the emission intensity is strongly enhanced by spatial separation of the optically active ligand molecules within the MOF structure and is found to be dependent on the amount and chemical nature of the guest species in the pores. The quantum yield of the material is found to be 6.7% and, coupled with the fluorescence lifetime on the millisecond time scale, begins to approach the values observed for Eu(III)-cryptate-derived commercial sensors.
- Published
- 2010
35. Interstitial Oxide Ion Order and Conductivity in La1.64Ca0.36Ga3O7.32 Melilite
- Author
-
John B. Claridge, Hongjun Niu, Xiaojun Kuang, Chris I. Thomas, Samantha Y. Chong, Zhongling Xu, Matthew J. Rosseinsky, and Man-Rong Li
- Subjects
Oxide ,chemistry.chemical_element ,Nanotechnology ,defect structures ,02 engineering and technology ,Electrolyte ,Conductivity ,engineering.material ,010402 general chemistry ,01 natural sciences ,7. Clean energy ,Oxygen ,Catalysis ,Ion ,chemistry.chemical_compound ,calcium lanthanum gallate melilite interstitial oxide ion order cond ,QD ,Electrical conductor ,oxido ligands ,Chemistry ,Melilite ,General Medicine ,General Chemistry ,021001 nanoscience & nanotechnology ,Communications ,0104 chemical sciences ,Chemical engineering ,solid-state structures ,engineering ,Charge carrier ,ion conductivity ,0210 nano-technology - Abstract
Solid oxide fuel cells (SOFCs) are a major candidate technology for clean energy conversion because of their high efficiency and fuel flexibility.1 The development of intermediate-temperature (500–750 °C) SOFCs requires electrolytes with high oxide ion conductivity (exceeding 10−2 S cm−1 assuming an electrolyte thickness of 15 μm1). This conductivity, in turn, necessitates enhanced understanding of the mechanisms of oxide ion charge carrier creation and mobility at an atomic level. The charge carriers are most commonly oxygen vacancies in fluorites2, 3 and perovskites.3, 4 There are fewer examples of interstitial-oxygen-based conductors such as the apatites5, 6 and La2Mo2O9-based materials,7–9 so information on how these excess anion defects are accommodated and the factors controlling their mobility is important.
- Published
- 2010
36. New Nanocrystalline Cu/MnOxCatalysts Prepared from Supercritical Antisolvent Precipitation
- Author
-
Zi-Rong Tang, Mathieu Allix, John B. Claridge, Zhongling Xu, Mandy J. Crudace, Calum Dickinson, Matthew J. Rosseinsky, Christopher David Jones, Jonathan K. Bartley, Thomas E. Davies, Stuart Hamilton Taylor, Graham J. Hutchings, Albert Frederick Carley, and James K. W. Aldridge
- Subjects
Materials science ,Precipitation (chemistry) ,Organic Chemistry ,Inorganic chemistry ,Spinel ,engineering.material ,Catalysis ,Supercritical fluid ,Nanocrystalline material ,law.invention ,Inorganic Chemistry ,Hopcalite ,chemistry.chemical_compound ,chemistry ,Chemical engineering ,law ,engineering ,Calcination ,Crystallite ,Physical and Theoretical Chemistry - Abstract
Supercritical CO2 is used as an antisolvent to precipitate out nanostructured homogeneous mixtures of Cu2+ and Mn3+ with crystallites of 10–20 nm in diameter. Following calcination, this material forms a crystalline tetragonal spinel, CuMn2O4, with a branched chainlike structure with a length of 160–200nm and diameters of approximately 40nm. This new material is more than twice as active per unit surface area as the conventionally prepared hopcalite catalysts for the oxidation of carbon monoxide. This is the first time that homogeneous mixed oxides have been formed using this method.
- Published
- 2009
37. Frustration of Magnetic and Ferroelectric Long-Range Order in Bi2Mn4/3Ni2/3O6
- Author
-
Mathieu Allix, Stephen J. Blundell, Denis Pelloquin, Craig A. Bridges, Matthew Suchomel, Olivier Perez, Natalia Bellido, Hongjun Niu, Matthew J. Rosseinsky, Peter J. Baker, Francis L. Pratt, John B. Claridge, Dominique Grebille, Charles Simon, Helen Hughes, Tom Lancaster, Xiaojun Kuang, and P. Shiv Halasyamani
- Subjects
Condensed matter physics ,Chemistry ,media_common.quotation_subject ,Frustration ,General Chemistry ,Biochemistry ,Ferroelectricity ,Catalysis ,Colloid and Surface Chemistry ,Transition metal ,Lattice (order) ,Polar ,Magnetocapacitance ,Antiferroelectricity ,Condensed Matter::Strongly Correlated Electrons ,Ground state ,media_common - Abstract
The slight incommensurate modulation of the structure of Bi(2)Mn(4/3)Ni(2/3)O(6) is sufficient to suppress the electrical polarization which arises in commensurate treatments of the structure, due to antiferroelectric coupling of local polar units of over 900 A(3). The incommensurate structure is produced by the competition between ferroelectric Bi lone pair-driven A site displacement, chemical order of Mn and Ni on the B site, and both charge and orbital order at these transition metals. The interplay between the frustrated polar Bi displacements and the frustrated spin order at the B site, induced by positional disorder, produces magnetodielectric coupling between the incommensurately modulated lattice and the spin-glass-like ground state with an unusual relationship between the magnetocapacitance and the applied field.
- Published
- 2009
38. Structure and Phase Behavior of the Expanded‐Metal Compound 7 Li(ND 3 ) 4
- Author
-
Amelia J. Fowkes, Matthew J. Rosseinsky, Richard M. Ibberson, Peter P. Edwards, and William I. F. David
- Subjects
Neutron powder diffraction ,Materials science ,Structure (category theory) ,chemistry.chemical_element ,General Chemistry ,Cubic crystal system ,Catalysis ,Metal ,chemistry ,Phase (matter) ,visual_art ,visual_art.visual_art_medium ,Physical chemistry ,Lithium ,Expanded metal ,Electronic properties - Abstract
Metal lite: High-resolution neutron powder diffraction data reveals that the body-centered cubic crystal structure of lithium(0)tetraamine transforms to a simple cubic structure below 22 K. The detailed structure determinations will allow new insights into the coupled structural and electronic properties of the lightest metal.
- Published
- 2009
39. Production of titania nanoparticles by a green process route
- Author
-
Sean Alexander Axon, Gary A. Leeke, Calum Dickinson, Graham J. Hutchings, Tiejun Lu, Matthew J. Rosseinsky, and Stuart Blackburn
- Subjects
chemistry.chemical_compound ,Materials science ,Aqueous solution ,Supercritical carbon dioxide ,chemistry ,Precipitation (chemistry) ,General Chemical Engineering ,Inorganic chemistry ,Nanoparticle ,Particle ,Methanol ,Particle size ,Catalysis - Abstract
The manufacture of heterogeneous catalysts and catalyst supports produces substantial amounts of nitrate containing aqueous effluent. The use of nitrate free precursors and an environmentally friendly process would change the manufacture so that the entire process of catalyst synthesis and use can be considered green. In this work the precipitation of titania acetylacetonate nanoparticles for use as catalytic supports using a supercritical carbon dioxide anti-solvent process was investigated over a range of conditions. The effects of 1) pressure, 2) temperature, 3) solution flowrate, 4) solution concentration of TiO(acac) 2 in methanol, 5) nozzle diameter and 6) CO 2 /methanol flow ratio on the mean particle size and morphology were studied. Particle sizes between 27 and 78 nm were obtained and were generally string and branch-like with an amorphous nature. Pressure and temperature had little effect on the mean particle size. A decrease in the velocity of the solution flow rate led to an increase in mean particle size and to particles that exhibited greater interconnectivity. It was also observed that an increase in concentration of TiO(acac) 2 in methanol led to an increase in mean particle size. The process shows promise for the production of catalysts by an environmentally acceptable route.
- Published
- 2009
40. Control of Porosity Geometry in Amino Acid Derived Nanoporous Materials
- Author
-
John E. Warren, Jean-Noël Rebilly, John Bacsa, Benjamin O. Carter, Ramanathan Vaidhyanathan, Jorge Perez Barrio, Matthew J. Rosseinsky, Abbie Trewin, Hyunsoo Park, Darren Bradshaw, Alexey Y. Ganin, and Andrew I. Cooper
- Subjects
Models, Molecular ,Surface Properties ,Stereochemistry ,Ligands ,Phase Transition ,Catalysis ,2,2'-Dipyridyl ,Nickel ,Organometallic Compounds ,Porosity ,chemistry.chemical_classification ,Aspartic Acid ,Molecular Structure ,Ligand ,Nanoporous ,Organic Chemistry ,General Chemistry ,Nanostructures ,Amino acid ,Crystallography ,chemistry ,Sublimation (phase transition) ,Metal-organic framework ,Porous medium ,Linker ,Powder Diffraction - Abstract
Substitution of the pillaring ligand in the homochiral open-framework [Ni(2)(L-asp)(2)(bipy)] by extended bipy-type ligands leads to a family of layer-structured, homochiral metal-organic frameworks. The 1D channel topology can be modified by the nature of the organic linker, with shape, cross-section and the chemical functionality tuneable. In addition, the volume of these channels can be increased by up to 36 % compared to the parent [Ni(2)(L-asp)(2)(bipy)]. The linker 1,4-dipyridylbenzene (3rbp) gives access to a new layered homochiral framework [Ni(2)(L-asp)(2)(3rbp)] with channels of a different shape. In specific cases, non-porous analogues with the linker also present as a guest can be activated to give porous materials after sublimation. Their CO(2) uptake shows an increase of up to 30 % with respect to the parent [Ni(2)(L-asp)(2)(bipy)] framework.
- Published
- 2008
41. Stable amorphous georgeite as a precursor to a high-activity catalyst
- Author
-
Simon A. Kondrat, Li Lu, Elisabetta Maria Fiordaliso, James H. Carter, Jakob Birkedal Wagner, Christopher J. Kiely, Stuart Hamilton Taylor, Graham J. Hutchings, Matthew J. Rosseinsky, Paul J. Smith, David J. Morgan, Gordon J. Kelly, Peter P. Wells, Philip A. Chater, Colin William Park, Jonathan K. Bartley, Thomas E. Davies, and Michael S. Spencer
- Subjects
Multidisciplinary ,Chemistry ,Catalyst support ,Inorganic chemistry ,Industrial catalysts ,02 engineering and technology ,Aurichalcite ,engineering.material ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Rosasite ,Supercritical fluid ,0104 chemical sciences ,Catalysis ,chemistry.chemical_compound ,engineering ,QD ,0210 nano-technology ,Sodium carbonate ,Low sodium - Abstract
Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable—and hence little known and largely ignored1—georgeite. The first three of these minerals are widely used as catalyst precursors2, 3, 4 for the industrially important methanol-synthesis and low-temperature water–gas shift (LTS) reactions5, 6, 7, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase2, 3, 8, 9, 10 is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite11; with few exceptions12 it uses sodium carbonate as the carbonate source, but this also introduces sodium ions—a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts.
- Published
- 2015
42. A Family of Nanoporous Materials Based on an Amino Acid Backbone
- Author
-
Jean-Noël Rebilly, Neil G. Berry, Jamie A. Gould, Jorge Perez Barrio, Darren Bradshaw, Matthew J. Rosseinsky, and Ramanathan Vaidhyanathan
- Subjects
Models, Molecular ,chemistry.chemical_classification ,Aspartic Acid ,Nanoporous ,Hydrogen bond ,Hydrogen Bonding ,General Medicine ,General Chemistry ,Catalysis ,Amino acid ,Glycols ,Pentanols ,chemistry ,Pentanes ,Aspartic acid ,Polymer chemistry ,Nanotechnology ,Indicators and Reagents ,Metal-organic framework ,Amino Acids ,Chirality (chemistry) ,Porosity - Published
- 2006
43. Ba8CoNb6O24: A d0 Dielectric Oxide Host Containing Ordered d7 Cation Layers 1.88 nm Apart
- Author
-
David M. Iddles, Tim Price, Phillip M. Mallinson, John B. Claridge, Richard M. Ibberson, Matthew J. Rosseinsky, and Mathieu Allix
- Subjects
Crystallography ,chemistry.chemical_compound ,chemistry ,X-ray crystallography ,Oxide ,Mineralogy ,General Medicine ,General Chemistry ,Dielectric ,Host (network) ,Catalysis - Published
- 2005
44. Adsorption of Gases and Vapors on Nanoporous Ni2(4,4‘-Bipyridine)3(NO3)4 Metal−Organic Framework Materials Templated with Methanol and Ethanol: Structural Effects in Adsorption Kinetics
- Author
-
K.M. Thomas, Edmund J. Cussen, Ashleigh J. Fletcher, Matthew J. Rosseinsky, and D Bradshaw
- Subjects
Nanoporous ,Kinetics ,Inorganic chemistry ,Sorption ,General Chemistry ,Biochemistry ,Catalysis ,4,4'-Bipyridine ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,Adsorption ,chemistry ,Mass transfer ,Metal-organic framework ,Methanol - Abstract
Desolvation of Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2CH(3)OH and Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2C(2)H(5)OH give flexible metal-organic porous structures M and E, respectively, which have the same stoichiometry, but subtly different structures. This study combines measurements of the thermodynamics and kinetics of carbon dioxide, methanol, and ethanol sorption on adsorbents M and E over a range of temperatures with adsorbent structural characterization at different adsorbate (guest) loadings. The adsorption kinetics for methanol and ethanol adsorption on porous structure E obey a linear driving force (LDF) mass transfer model for adsorption at low surface coverage. The corresponding adsorption kinetics for porous structure M follow a double exponential (DE) model, which is consistent with two different barriers for diffusion through the windows and along the pores in the structure. The former is a high-energy barrier due to the opening of the windows in the structure, required to allow adsorption to occur, while the latter is a lower-energy barrier for diffusion in the pore cavities. X-ray diffraction studies at various methanol and ethanol loadings showed that the host porous structures E and M underwent different scissoring motions, leading to an increase in unit cell volume with the space group remaining unchanged during adsorption. The results are discussed in terms of reversible adsorbate/adsorbent (host/guest) structural changes and the adsorption mechanism involving hydrogen-bonding interactions with specific surface sites for methanol and ethanol adsorption in relation to pore size and extent of filling. This paper contains the first evidence for individual kinetic barriers to diffusion through windows and pore cavities in flexible porous coordination polymer frameworks.
- Published
- 2004
45. Permanent Microporosity and Enantioselective Sorption in a Chiral Open Framework
- Author
-
Darren Bradshaw, Matthew J. Rosseinsky, Edmund J. Cussen, Timothy J. Prior, and John B. Claridge
- Subjects
chemistry.chemical_classification ,Chemistry ,Stereochemistry ,Enantioselective synthesis ,Sorption ,General Chemistry ,Microporous material ,Biochemistry ,Open framework ,Catalysis ,Colloid and Surface Chemistry ,Chemical engineering ,Molecule ,Non-covalent interactions ,Porosity ,Porous medium - Abstract
A homochiral microporous material is presented. The phase has 47% permanently porous void volume and is shown to have >1 nm diameter pores with three-dimensional channels using probe molecule sorption. Enantioselective guest sorption is strongly dependent on guest size. The homochiral microporous phase was identified by reactive selection from a first-generation chiral but nonporous framework. Chiral permanent porosity is established by directional noncovalent interactions between framework-forming and nonframework forming components of the stable second-generation material, which become stronger upon loss of the guests from the pore system.
- Published
- 2004
46. Flexible Sorption and Transformation Behavior in a Microporous Metal-Organic Framework
- Author
-
John B. Claridge, Matthew J. Rosseinsky, Cameron J. Kepert, and Edmund J. Cussen
- Subjects
Diffraction ,Chemistry ,Stereochemistry ,Sorption ,General Chemistry ,Crystal structure ,Microporous material ,Biochemistry ,Catalysis ,Colloid and Surface Chemistry ,Chemical engineering ,Covalent bond ,Molecule ,Metal-organic framework ,Porosity - Abstract
Crystals of the metal-organic framework material Ni(2)(4,4'-bipyridine)(3)(NO(3))(4) (A) have been grown by reaction of Ni(NO(3))(2).6H(2)O and 4,4'-bipyridine in methanol solution. Single-crystal X-ray diffraction experiments show that the ladder structure of the framework is maintained after desolvation of the material, resulting in the production of a porous solid stable to 215(4) degrees C. Powder X-ray diffraction has been employed to confirm the bulk purity and temperature stability of this material. The crystal structure indicates that the pore window has an area of 12.3 A(2). However, sorption experiments show these windows will admit toluene, which has a minimum cross-sectional area of 26.6 A(2), with no significant change in the structure. Monte Carlo docking calculations show that toluene can be accommodated within the large pores of the structure. Exposure of the related microporous material Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2C(2)H(5)OH (B) to methanol vapor causes a guest-driven solid-state transformation to A which is observed using powder X-ray diffraction. This structural rearrangement proceeds directly from crystalline B to crystalline A and is complete in less than 1 day. Mechanisms for the transformation are proposed which require breaking of at least one in six of the covalent bonds that confer rigidity on the framework.
- Published
- 2002
47. Close-Packed C703- Phases − Synthesis, Structure, and Electronic Properties
- Author
-
Sandra M. Moussa, Mark S. Denning, Matthew J. Rosseinsky, Katsumi Tanigaki, Ian D. Watts, and Pierrick Durand
- Subjects
Superconductivity ,Fullerene ,Fermi level ,General Chemistry ,Biochemistry ,Catalysis ,Higher fullerenes ,law.invention ,chemistry.chemical_compound ,symbols.namesake ,Crystallography ,Colloid and Surface Chemistry ,Buckminsterfullerene ,Nuclear magnetic resonance ,chemistry ,Octahedron ,law ,Phase (matter) ,Physics::Atomic and Molecular Clusters ,symbols ,Physics::Chemical Physics ,Electron paramagnetic resonance - Abstract
The high symmetry and resulting electronic degeneracy of the C(60)(3)(-) anion is viewed as the key molecular feature in the high superconducting transition temperatures of fulleride and oxidized fullerene systems. The experimental evaluation of this hypothesis requires the synthesis of face-centered cubic (fcc) trivalent fulleride anion salts derived from higher fullerenes such as C(70), which have thus far proved elusive with only stable A(1)C(70), A(4)C(70), and A(6)C(70) phases known. In this paper, we report the synthesis of fcc A(3)C(70) phases stabilized by size-matching the tetrahedral site with the sodium cation. The structures are strongly dependent on the cooling protocol due to the existence of metastable partially or completely orientationally disordered phases. EPR data indicate that the phases are metallic but not superconducting. The densities of states at the Fermi level appear too low to give superconductivity at above 5 K, consistent with recent observations that four electrons per C(70) anion are required for superconductivity. Size-matching on both the octahedral and tetrahedral sites is required for A(3)C(70) stability - K(2)CsC(70) is only stable at elevated temperature and Na(2)C(70) is unstable, the composition corresponding to C(70) and a sodium-rich trigonal phase.
- Published
- 2002
48. Magnetism and Structural Chemistry of the n = 1 Ruddlesden−Popper Phases La4LiMnO8 and La3SrLiMnO8
- Author
-
Jeremy Sloan, Jonathan C. Burley, Clare P. Grey, Daniel J. Gallon, Peter D. Battle, and Matthew J. Rosseinsky
- Subjects
Magnetic moment ,Chemistry ,Magnetism ,Neutron diffraction ,General Chemistry ,Nuclear magnetic resonance spectroscopy ,Crystal structure ,Paracrystalline ,Biochemistry ,Magnetic susceptibility ,Catalysis ,Crystallography ,Colloid and Surface Chemistry ,Crystallite - Abstract
Polycrystalline samples of La4LiMnO8 and La3SrLiMnO8 have been studied by a combination of X-ray diffraction (XRD), neutron diffraction (ND), 6Li MAS NMR, electron microscopy (EM), and magnetometry. Room-temperature XRD and ND measurements suggest that both compounds have the K2NiF4 structure, with a disordered arrangement of Li and Mn over the six-coordinate sites. However, MAS NMR and EM demonstrate the presence of local 1:1 Li:Mn order on these sites, and EM shows that although cation order is well-developed in each xy sheet of corner-sharing octahedra, the sheets are stacked randomly along z. The structures are best described as paracrystalline, and many of the concepts of conventional crystallography are inapplicable. Magnetometry and low-temperature ND experiments show that, despite their paracrystallinity, the two compounds are ordered antiferromagnetically with susceptibility maxima at 26 and 18 K, respectively, and with ordered magnetic moments of 3.61(6) and 2.3(1) muB per Mn cation at 2 K. Anisotropic peak broadening reveals a 2D character in the magnetic behavior of both compounds, and La3SrLiMnO8 is well-modeled as a quadratic layer S = 3/2 Heisenberg antiferromagnet.
- Published
- 2002
49. Room temperature oxidation of methyl orange and methanol over Pt–HCa2Nb3O10and Pt–WO3catalysts without light
- Author
-
Upendra A. Joshi, Zhongling Xu, Matthew J. Rosseinsky, James R. Darwent, John B. Claridge, and Emiliana Dvininov
- Subjects
business.industry ,Chemistry ,Inorganic chemistry ,Temperature ,Metals and Alloys ,General Chemistry ,Photochemistry ,Catalysis ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,chemistry.chemical_compound ,Semiconductor ,Semiconductors ,Oxidizing agent ,Materials Chemistry ,Ceramics and Composites ,Methyl orange ,Methanol ,business ,Azo Compounds ,Oxidation-Reduction ,Platinum - Abstract
The layered semiconductor Pt-HCa(2)Nb(3)O(10) can catalyze room temperature air oxidation of methyl orange. It is also more effective than Pt-WO(3) in catalyzing reaction of methanol with air. Pt-HCa(2)Nb(3)O(10) could find wide application as a mild oxidizing catalyst.
- Published
- 2011
50. Proxy-based accelerated discovery of Fischer–Tropsch catalysts
- Author
-
Gary Bevan Combes, John B. Claridge, Peter Ellis, Dan I. Enache, Matthew J. Rosseinsky, Paul Boldrin, James R. Gallagher, Gordon J. Kelly, and David James
- Subjects
Reaction conditions ,Stability test ,Chemical engineering ,Chemistry ,Chemisorption ,High surface area ,Fischer–Tropsch process ,Nanotechnology ,General Chemistry ,Selectivity ,Catalysis - Abstract
© The Royal Society of Chemistry 2015.Development of heterogeneous catalysts for complex reactions such as Fischer-Tropsch synthesis of fuels is hampered by difficult reaction conditions, slow characterisation techniques such as chemisorption and temperature-programmed reduction and the need for long term stability. High-throughput (HT) methods may help, but their use has until now focused on bespoke micro-reactors for direct measurements of activity and selectivity. These are specific to individual reactions and do not provide more fundamental information on the materials. Here we report using simpler HT characterisation techniques (XRD and TGA) along with ageing under Fischer-Tropsch reaction conditions to provide information analogous to metal surface area, degree of reduction and thousands of hours of stability testing time for hundreds of samples per month. The use of this method allowed the identification of a series of highly stable, high surface area catalysts promoted by Mg and Ru. In an advance over traditional multichannel HT reactors, the chemical and structural information we obtain on the materials allows us to identify the structural effects of the promoters and their effects on the modes of deactivation observed.
- Published
- 2014
Catalog
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