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High surface area mixed oxide 8.7% NiO-CeO2 nanoparticles (122 m2/g; 6–7 nm) were prepared using a reversed microemulsion method, and were tested for dry methane reforming (DRM). The catalytic activity of these nanoparticles remains stable under the severe conditions of DRM (700 °C), and they show better carbon resistance than conventional NiO-CeO2 catalysts prepared without control of the size. The activity and selectivity of nanoparticles and reference catalyst are similar, but nanoparticles reduce by 63% the accumulation of carbon during the DRM tests, which is a key feature for this reaction. XPS and H2-TPR suggest that the improved carbon resistance of the nanoparticles is the better interaction and cooperation between NiO and CeO2 mixed phases. In nanoparticles, the participation of cerium cations in the redox processes taking place during DRM stabilize cationic species of nickel. On the contrary, the catalyst prepared without control of the size suffered segregation of Ni during DRM reaction, and segregated Ni explains the higher catalytic formation of carbon. Project supported by the Generalitat Valenciana (Project PROMETEO/2018/076; ACA GRISOLIAP/2017/185; EBG APOSTD/2019/030), MINECO (CTQ2015-67597-C2-2-R), MICINN (PID2019-105960RB-C22) and European Union FEDER funds.

Low-valent group 15 compounds stabilized by pincer ligands have gained particular interest, given their direct access to fine-tune their reactivity by the coordination pattern. Recently, bismuth has been employed in a variety of catalytic transformations by taking advantage of the (+1/+3) redox couple. In this work, we present a detailed quantum–chemical study on the electronic structure of bismuth pincer complexes from two different families, namely, bis(ketimine)phenyl (NCN) and triamide bismuthinidene (NNN). The use of the so-called effective oxidation state analysis allows the unambiguous assignation of the bismuth oxidation state. In contrast to previous studies, our calculations suggest a Bi(+1) assignation for NCN pincer ligands, while Bi(+3) character is found for NNN pincer complexes. Notably, regardless of its oxidation state, the central bismuth atom disposes of up to two lone pairs for coordinating Lewis acids, as indicated by very high first and second proton affinity values. Besides, the Bi–NNN systems can also accommodate two Lewis base ligands, indicating also ambiphilic behavior. The effective fragment orbital analysis of Bi and the ligand allows monitoring of the intricate electron flow of these processes, revealing the noninnocent nature of the NNN ligand, in contrast with the NCN one. By the dissection of the electron density into effective fragment orbitals, we are able to quantify and rationalize the Lewis base/acid character., Effective oxidation state analysis sheds light on the electronic structure of chemical systems. The oxidation state of bismuthinidene pincer complexes can be assigned as Bi(+1) or Bi(+3) depending on the nature of the ligands. Despite this assignation, the reactivity pattern as Lewis base or acid is similar. The occupation of the effective fragment orbitals gives a straightforward method to quantify the reactivity.

Two micro-mesoporous carbons (MMCs): a disordered mesoporous carbon (DMC) and an ordered mesoporous carbon (OMC), synthesized by an easy, low-cost, and green method are proposed as efficient hydrocarbon sieves for the separation of C6 isomers: n-hexane (nHEX), 2-methylpenthane (2 MP) and 2,2-dimethylbutane (22DMB). Their textural characterization reveals a highly interconnected pore network within the DMC, while a reverse hierarchy of ordered mesopores only accessible through narrow micropores is found in the OMC. The pore texture strongly affects their adsorption performance by kinetic and molecular sieving effects; the narrow constrictions in the OMC allow adsorption of nHEX and partially 2 MP but not 22DMB, whereas the highly connected pore network of DMC allows adsorption of the three isomers. Multi-component adsorption isotherms calculated from the single-component experimental results by ideal adsorbed solution theory (IAST) demonstrates that the OMC material has a remarkably high selectivity for the adsorption of nHEX and nHEX + 2 MP from binary and ternary mixtures, respectively. To the best of the authors’ knowledge, such behavior has never been reported so far for carbon materials. Hence, this study shows that tannin-derived MMCs have great potential to be used as an eco-friendly and low-cost alternative for the selective separation of di-branched C6 isomers. Jimena Castro-Gutiérrez gratefully acknowledges CONACYT-SENER for the scholarship awarded (601021/438978) to support her PhD studies, resulting in the work presented herein. This study was partly funded by the French PIA project "Lorraine Université d’Excellence”, reference ANR-15-IDEX-04-LUE, and TALiSMAN project, funded by FEDER (2019-000214). Joaquín Silvestre-Albero would like to acknowledge the financial support from MINECO (PID2019-108453GB-C21) and H2020 (MSCA-RISE-2016/NanoMed Project).

MAX phases are layered ternary carbides or nitrides that are attractive for catalysis applications due to their unusual set of properties. They show high thermal stability like ceramics, but they are also tough, ductile, and good conductors of heat and electricity like metals. Here, we study the potential of the Ti3AlC2 MAX phase as a support for molybdenum oxide for the reverse water–gas shift (RWGS) reaction, comparing this new catalyst to more traditional materials. The catalyst showed higher turnover frequency values than MoO3/TiO2 and MoO3/Al2O3 catalysts, due to the outstanding electronic properties of the Ti3AlC2 support. We observed a charge transfer effect from the electronically rich Ti3AlC2 MAX phase to the catalyst surface, which in turn enhances the reducibility of MoO3 species during reaction. The redox properties of the MoO3/Ti3AlC2 catalyst improve its RWGS intrinsic activity compared to TiO2- and Al2O3-based catalysts. We thank the Netherlands Organisation for Scientific Research (NWO) for the grant “Developing novel catalytic materials for converting CO2, methane and ethane to high-value chemicals in a hybrid plasma-catalytic reactor” (China.15.119). We also acknowledge financial support by MINECO (Spain) through projects MAT2017-86992-R and MAT2016-80285-P. Z.S. was supported by the project LTAUSA19034, from the Ministry of Education Youth and Sports (MEYS). M.H. and M.T. gratefully acknowledge NWO under LIFT, Launchpad for Innovative Future Technology, PreCiOuS, 731.015.407. We also thank the staff of the Swiss Light Source (SLS) synchrotron (SuperXAS beamline and proposal number 20190956), Maarten Nachtegaal and Adam Clark, for support during synchrotron measurements.

In this study, we assessed the effect of the incorporation of multi-walled carbon nanotubes (MWCNT) on a TiO2 support containing different active metals to obtain Metal/TiO2-MWCNT photocatalytic systems. The materials prepared in this work were characterized by ICP-OES, TEM, EDX, XRD, PL, UV–vis, and nitrogen physisorption techniques. Among those investigated metals, Cu was shown to be the most promising for the present application. The assessment of the photocatalytic performance of Cu/TiO2-MWCNT with various Cu contents revealed that the catalytic activity depends on the Cu loading and the photocatalyst with 1 wt.% of Cu displayed the best performance among investigated. The incorporation of MWCNT in the support enhanced the photocatalytic activity towards the production of H2 under visible and UV–vis light irradiation at room temperature. The authors thank Ministerio de Ciencia Innovación y Universidades and FEDER (Project RTI2018-095291-B-I00) and the Generalitat Valenciana (PROMETEOII/2018/076) for financial support. JFC thanks MINECO for a researcher formation grant (BES-2016-078079). MNG gratefully acknowledges Generalitat Valenciana and Plan GenT (CDEIGENT/2018/027) for the postdoctoral grant. The present work was partially supported by Grants-in-Aid for Scientific Research (Nos. 26220911, 19H00838) from the Japan Society for the Promotion of Science (JSPS) and MEXT. KM, YK, and HY thank MEXT program “Elements Strategy Initiative to Form Core Research Center.

[EN] beta-Galactosidase (beta-Gal) is a widely used enzyme as a reporter gene in the field of molecular biology which hydrolyzes the beta-galactosides into monosaccharides. beta-Gal is an essential enzyme in humans and its deficiency or its overexpression results in several rare diseases. Cellular senescence is probably one of the most relevant physiological disorders that involve beta-Gal enzyme. In this review, we assess the progress made to date in the design of molecular-based probes for the detection of beta-Gal both in vitro and in vivo. Most of the reported molecular probes for the detection of beta-Gal consist of a galactopyranoside residue attached to a signalling unit through glycosidic bonds. The beta-Gal-induced hydrolysis of the glycosidic bonds released the signalling unit with remarkable changes in color and/or emission. Additional examples based on other approaches are also described. The wide applicability of these probes for the rapid and in situ detection of de-regulation beta-Gal-related diseases has boosted the research in this fertile field, R.M laboratory members received the financial support from the Spanish Government (project RTI2018-100910-B-C41) and the Generalitat Valenciana (project PROMETEO 2018/024). B.L-T. received support from the Spanish Ministry of Economy for their PhD grants (FPU15/02707). J. F.-B received fellowship (CD19/00038)

This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (NanoMOFdeli), ERC-2016-COG 726380, Innovate UK (104384) and EPSRC IAA (IAA/RG85685). N.R. acknowledges the support of the Cambridge International Scholarship and the TrinityHenry Barlow Scholarship (Honorary). O.K.F. and R.Q.S. acknowledge funding from the U.S. Department of Energy (DE-FG02-08ER15967). R.S.F. and D.B. acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (SCoTMOF), ERC-2015-StG 677289. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA-0003525. The authors gratefully acknowledge funding from the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office, through the Hydrogen Storage Materials Advanced Research Consortium (HyMARC). This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. J.D.E. acknowledges the support of the Alexander von Humboldt Foundation and the Center for Information Services and High Performance Computing (ZIH) at TU Dresden. S.K.G. and S.M. acknowledge SERB (Project No. CRG/2019/000906), India for financial support. K.K. and R.K. acknowledge Active Co. Research Grant for funding. S.K. acknowledges funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (COSMOS), ERC-2017-StG 756489. N.L. and J.G.M acknowledge funding from the European Commission through the H2020-MSCA-RISE-2019 program (ZEOBIOCHEM -872102) and the Spanish MICINN and AEI/FEDER (RTI2018-099504-B-C21). N.L. thanks the University of Alicante for funding (UATALENTO17-05). ICN2 is supported by the Severo Ochoa program from the Spanish MINECO (Grant No. SEV-2017-0706) S.M.J.R. and A.L. wish to thank the Fund for Scientific Research Flanders (FWO), under grant nos. 12T3519N and 11D2220N. L.S. was supported by the EPSRC Cambridge NanoDTC EP/L015978/1. C.T.Y. and T.S.N. acknowledges funds from the National Research Foundation of Korea, NRF-2017M3A7B4042140 and NRF-2017M3A7B4042235. P.F. and H. Y. acknowledge US Department of Energy, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under Award No. DE-SC0010596 (P.F.). R.O. would like to acknowledge funding support during his Ph.D. study from Indonesian Endowment Fund for Education-LPDP with the contract No. 202002220216006. Daniel Siderius: Official contribution of the National Institute of Standards and Technology (NIST), not subject to copyright in the United States of America. Daniel Siderius: Certain commercially available items may be identified in this paper. This identification does not imply recommendation by NIST, nor does it imply that it is the best available for the purposes described. B.V.L, S.T.E and A.M.P acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Program (Grant agreement no. 639233, COFLeaf)., Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer–Emmett–Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of microand mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This roundrobin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called “BET surface identification” (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible., European Research Council (ERC) ERC-2016-COG 726380 ERC-2015-StG 677289 ERC-2017-StG 756489 639233, UK Research & Innovation (UKRI) Innovate UK 104384 UK Research & Innovation (UKRI), Engineering & Physical Sciences Research Council (EPSRC) IAA/RG85685, Cambridge International Scholarship TrinityHenry Barlow Scholarship, United States Department of Energy (DOE) DE-FG02-08ER15967, National Nuclear Security Administration DE-NA-0003525, United States Department of Energy (DOE), Alexander von Humboldt Foundation, Center for Information Services and High Performance Computing (ZIH) at TU Dresden, Department of Science & Technology (India), Science Engineering Research Board (SERB), India CRG/2019/000906, Active Co. Research Grant, European Commission through the H2020-MSCA-RISE-2019 program ZEOBIOCHEM -872102, Spanish MICINN and AEI/FEDER RTI2018-099504-B-C21, University of Alicante UATALENTO17-05, Spanish Government SEV-2017-0706 FWO 12T3519N 11D2220N, UK Research & Innovation (UKRI), Engineering & Physical Sciences Research Council (EPSRC) EP/L015978/1, National Research Foundation of Korea NRF-2017M3A7B4042140 NRF-2017M3A7B4042235, United States Department of Energy (DOE) DE-SC0010596, Indonesian Endowment Fund for Education-LPDP 202002220216006

The individual and simultaneous removal of NOx by Storage and Reduction with H2 (H2‐NSR) and combustion of soot have been studied for La and CuLa catalysts. The NOx storage capacity of pure lanthanum oxide is improved either by copper addition or by using a colloidal crystal hard template for the synthesis of a macroporous structure. Although the NOx storage capacity of the CuLa macroporous material is around ten times lower regarding conventional PtBa catalysts, the kinetics of the H2‐NSR cycles are fast enough to allow high NOx removal (until 90 % removal). Lanthanum oxide catalyst prepared with uncontrolled structure has no activity for soot combustion, but the activity increases for a macroporous counterpart prepared using the colloidal crystal template because the macroporous structure improves the soot‐catalyst contact and allows the nitrogen‐oxygen surface groups yielded upon NOx chemisorption to oxidize soot. The soot combustion activity of lanthanum catalysts is also enhanced upon copper loading, because copper improves the NO2‐assisted soot combustion mechanism and favors the chemisorption of NOx, enhancing soot oxidation by nitrogen‐oxygen surface species. Finally, it is demonstrated that the simultaneous removal of NOx by H2‐NSR and soot combustion can be carried out with a CuLa catalyst at 450 °C. The simultaneous removal does not affect the combustion of soot and only has a small effect in NOx removal. Spanish Ministry of Economy and Competitiveness (Project CTQ2015-67597-C2-2-R), Spanish Ministry of Science and Innovation (PID2019-105960RB-C22), Generalitat Valenciana (Project PROMETEO/2018/076 and APOSTD/2019/030) and European Union (FEDER funding).

In the process of synthesis of a new drug, as important as the drug itself is the formulation used, because the same compound can present a very different efficacy depending on how it is administered. In this work, we demonstrate how the antitumor capacity of a new octahedral organo-ruthenium complex, [Ru(ppy-CHO)(phen)(2)][PF(6)] is affected by its encapsulation in different types of mesoporous silica nanoparticles. The interactions between the Ru complex and the silica matrix and how these interactions are affected at two different pHs (7.4 and 5.4, mimicking physiological and endolysosomal acidic conditions, respectively) have been studied. The encapsulation has also been shown to affect the induction of apoptosis and necrosis and progression of the cell cycle compared to the free drug. The encapsulation of the Ru complex in nanoparticles functionalized with amino groups produced very high anticancer activity in cancer cells in vitro, especially against U87 glioblastoma cells, favoring cellular internalization and significantly increasing the anticancer capacity of the initial non-encapsulated Ru complex.

We have investigated the gas-phase (P = 1 atm; T = 373 K) hydrogenation of (tertiary alkynol) 2-methyl-3-butyn-2-ol (MBY) and (secondary) 3-butyn-2-ol (BY) over a series of carbon (C), non-reducible (Al2O3 and MgO), and reducible (CeO2 and ZnO) supported monometallic [Pd (0.6–1.2% wt) and Zn (1% wt)] and bimetallic Pd–Zn (Pd:Zn mol ratio = 95:5, 70:30, and 30:70) catalysts synthesized by deposition–precipitation and colloidal deposition. The catalysts have been characterized by H2 chemisorption, hydrogen temperature-programmed desorption (H2-TPD), specific surface area (SSA), X-ray photoelectron spectroscopy (XPS), and transmission (TEM) and scanning transmission electron microscopy (STEM) analyses. Reaction over these catalysts generated the target alkenol [2-methyl-3-buten-2-ol (MBE) and 3-buten-2-ol (BE)] through partial hydrogenation and alkanol [2-methyl-butan-2-ol (MBA) and 2-butanol (BA)]/ketone [2-butanone (BONE)] as a result of full hydrogenation and double-bond migration. The catalysts exhibit a similar Pd nanoparticle size (2.7 ± 0.3 nm) but a modified electronic character (based on XPS). Hydrogenation activity is linked to surface hydrogen (from H2 chemisorption and H2-TPD). An increase in H2:alkynol (from 1 → 10) results in enhanced alkynol consumption with a greater rate in the transformation of MBY (vs BY); H2:alkynol had negligible effect on product distribution. Reaction selectivity is insensitive to the Pd site electron density with a similar response (SMBE = 65 ± 9% and SBE = 70 ± 8%) over Pdδ− (on Al2O3 and MgO) and Pdδ+ (on C and CeO2). A Pd/ZnO catalyst delivered enhanced alkenol selectivity (SMBE = 90% and SBE = 96%) attributed to PdZn alloy phase formation (proved by XRD and XPS) but low activity, ascribed to metal encapsulation. A two-fold increase in the consumption rate was recorded for Pd–Zn/Al2O3 (30:70) versus Pd/ZnO with a similar alloy content (32 ± 4% from XPS), ascribed to a contribution due to spillover hydrogen (from H2-TPD) where high alkenol selectivity was maintained. This research was funded by the Engineering and Physical Sciences Research Council (EPRSC; grant number EP/L016419/1; Ph.D. studentship to A.G.-F., CRITICAT program), the Spanish Ministerio de Ciencia Innovación y Universidades, Generalitat Valenciana and FEDER (RTI2018-095291-B-I00, MAT2017-87579-R MINECO/FEDER and PROMETEO/2018/076).

Hypothesis The treatment of bone fractures still represents a challenging clinical issue when complications due to impaired bone remodelling (i.e. osteoporosis) or infections occur. These clinical needs still require a radical improvement of the existing therapeutic approach through the design of advanced biomaterials combining the ability to promote bone regeneration with anti-fouling/anti-adhesive properties able to minimise unspecific biomolecules adsorption and bacterial adhesion. Strontium-containing mesoporous bioactive glasses (Sr-MBG), able to exert a pro-osteogenic effect by releasing Sr2+ ions, have been successfully functionalised to provide mixed-charge surface groups with low-fouling abilities. Experiments Sr-MBG have been post-synthesis modified by co-grafting hydrolysable short chain silanes containing amino (aminopropylsilanetriol) and carboxylate (carboxyethylsilanetriol) moieties to achieve a zwitterionic zero-charge surface and then characterised in terms of textural-structural properties, bioactivity, cytotoxicity, pro-osteogenic and low-fouling capabilities. Findings After zwitterionization the in vitro bioactivity is maintained, as well as the ability to release Sr2+ ions capable to induce a mineralization process. Irrespective of their size, Sr-MBG particles did not exhibit any cytotoxicity in pre-osteoblastic MC3T3-E1 up to the concentration of 75 ug/mL. Finally, the zwitterionic Sr-MBGs show a significant reduction of serum protein adhesion with respect to pristine ones. These results open promising future expectations in the design of nanosystems combining pro-osteogenic and anti-adhesive properties., Comment: 26 pages, 8 figures

Intracrystalline mesoporosity can be conveniently introduced in zeolites using cationic surfactants in a mild basic solution –a process known as surfactant-templating. However, this technique is limited to small-headed and single-chain surfactants because they need to diffuse through the narrow micropores of the zeolite, which limits the potential of this approach. Herein, we show that the mesoporosity generated in zeolites with small-headed and single-chain surfactants, such as CTAB, provides enough accessibility to allow the use of bulky surfactants that otherwise cannot enter the structure of the zeolite. Moreover, in this contribution, a USY zeolite has been successively treated with cationic surfactants of different chain lengths (C12 to C22) proving that the mesopores introduced in the zeolite can be efficiently widened and narrowed by consecutive treatments with surfactants of the suitable size. Finally, the use of consecutive surfactant-templating opens up the possibility of using surfactants of different packing parameters to produce new hierarchical architectures in zeolites. The authors thank the synchrotron ALBA (2018022824) and Spanish MINECO-AEI/FEDER (CTQ2015-74494-JIN and RTI2018-099504-B-C21). E. Serrano and N. Linares acknowledges the University of Alicante (refs UATALENTO 16-03 and 17-05, respectively).

Synthesis of SiC-based composites using microwave(MW)-assisted reactive infiltration is a promising way to obtain these materials at lower costs due to a reduction in processing time and energy consumption. Hot spots are likely to form during this process due to the different dielectric properties of the various phases and the exothermic nature of the reaction between Si and C. To study these effects Cf/SiC composites were subjected to high-temperature treatments (1800, 2000, 2200 °C) to simulate hot spots within the material. Microstructural changes were evaluated after the thermal treatments and thermo-mechanical properties were measured and correlated to the microstructural changes. Our results indicate that evaporation of silicon is the primary damaging mechanism, causing a decrease in the bending strength of the composite due to formation of porosity and a volume increase. These effects are countered by the densification of carbon phases that improve the intrinsic thermal properties of the material. Financial support from the Ministerio de Economia y Competitividad of Spain (MAT2017-86992-R), the PhD grant Vali+d grantted by the Generalitat Valenciana (Spain), and the European Union’s Seventh Framework Programme (FP7/2007-2013) under the HELM project, grant agreement no. 280464 are gratefully acknowledged.

A mild alkaline treatment with the assistance of surfactants has proved to be an effective way to introduce uniform mesopores into zeolites, yielding hierarchical materials with superior catalytic performance. Accelerating this process may open new opportunities in the scale-up of this new class of materials. In this study, we present an ultrafast surfactant-templating (UST) approach achieved within only a few minutes for the fast production of mesoporous ultra-stable Y (USY) zeolites by combining several favorable factors including high treating temperature, reactors featuring fast heating, and optimized reagent composition. Temperatures in the range of 150–220 °C yielded high quality materials, while too high temperatures (260–280 °C) produced inferior samples. The use of a flow reactor allowed for completing the UST in just one minute, which evidences the remarkable structural flexibility of zeolites that can reorganize in such a short time to accommodate a large amount of intracrystalline mesoporosity, without compromising their integrity or main properties. C. P. is grateful to the Chinese Scholarship Council and the Ministry of Education, Culture, Sports, Science and Technology, Japan for a MonbuKagakusho Scholarship. N. L. acknowledges funding from the University of Alicante, through the “Programa de captación y retención de talento” (ref. UATALENTO17-05). C. A Trujillo acknowledges the Universidad Nacional de Colombia and Ecopetrol for the support of the Laboratorio de Catálisis Heterogénea. Z. L. acknowledges the Japan Society for the Promotion of Science (JSPS) for financial support (a Grant-in-Aid for Young Scientists: 18K14049).

Biolubricants may be obtained from vegetable oils using appropriate chemical modifications, to improve their physicochemical properties for lubrication applications. In this study, the esterification of a free fatty acid (FFA) with long chain alcohols was performed using sulfonated mesoporous silica as catalyst. Fresh and functionalized MCM-41 samples were prepared to evaluate the effect of the sulfonic surface group on the esterification reaction. MCM-41 was functionalized via post-synthesis modification using 3-mercaptopropyltrimethoxysilane (MPTS) as silylating agent. The synthesized catalysts were characterized using several techniques. After the functionalization, a decrease in the apparent surface area and pore diameter were observed. The MCM-41/SO3H sample was applied in the esterification reaction of oleic acid (as a FFA model) using two different long-chain alcohols (octanol and 2-ethylhexanol). The catalytic results reveal that sulfonated catalyst showed excellent conversions (~ 100% mol when using octanol and > 93% mol using 2-ethylhexanol) and selectivities to esters (ca. 90%). The authors wish to acknowledge the financial support provided by FUNCAP (Fundação Cearense de Apoio ao Desenvolvimento Científico e Tecnológico) and CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico). This study was financed in part by the CAPES (Coordenação de Aperfeiçoamento de Pessoal de Nível Superior)—Brazil, Finance Code 001. Also, financial support from GV (PROMETEOII/2014/004), MINECO (MAT2016-80285-p) and H2020 (MSCA-RISE-2016/NanoMed Project) is gratefully acknowledged.

Micelle formation inside faujasite (FAU) zeolite, a critical step in the introduction of mesoporosity in zeolites by surfactant templating, has been confirmed by both 13C NMR and Raman spectroscopy. Here we provide unambiguous evidence of the incorporation of surfactant molecules inside zeolites during the first step of the surfactant-templating process followed by their self-assembly into micelles after hydrothermal treatment. The homogeneous presence of these micelles throughout zeolite crystals has been directly observed by Raman microspectroscopy, confirming the uniform incorporation of mesoporosity in zeolites by surfactant templating. We thank the European Commission for funding through the H2020-MSCA-RISE-2019 program (ref. ZEOBIOCHEM - 872102) and the Spanish MINECO and AEI/FEDER, UE through the project ref RTI2018-099504-B-C21. N.L. acknowledges the University of Alicante support (UATALENTO17-05). M.J.M.-C. thanks the Generalitat Valenciana for a Ph.D. fellowship (GRISOLIAP/2020/165). M.B.J.R. acknowledges financial support from the FWO for the investment in microscopy (AKUL/15/15 - G0H0816N and G0H6316N - ZW15_09) and financial support from the KU Leuven Research Fund (C14/19/079).

The preferential CO oxidation (so-called CO-PROX) is the selective CO oxidation amid H2-rich atmospheres, a process where ceria-based materials are consolidated catalysts. This article aims to disentangle the potential CO–H2 synergism under CO-PROX conditions on the low-index ceria surfaces (111), (110) and (100). Polycrystalline ceria, nanorods and ceria nanocubes were prepared to assess the physicochemical features of the targeted surfaces. Diffuse reflectance infrared Fourier-transformed spectroscopy (DRIFTS) shows that ceria surfaces are strongly carbonated even at room temperature by the effect of CO, with their depletion related to the CO oxidation onset. Conversely, formate species formed upon OH + CO interaction appear at temperatures around 60 °C and remain adsorbed regardless the reaction degree, indicating that these species do not take part in the CO oxidation. Density functional theory calculations (DFT) reveal that ceria facets exhibit high OH coverages all along the CO-PROX reaction, whilst CO is only chemisorbed on the (110) termination. A CO oxidation mechanism that explains the early formation of carbonates on ceria and the effect of the OH coverage in the overall catalytic cycle is proposed. In short, hydroxyl groups induce surface defects on ceria that increase the COx–catalyst interaction, revealed by the CO adsorption energies and the stabilization of intermediates and readsorbed products. In addition, high OH coverages are shown to facilitate the hydrogen transfer to form less stable HCOx products, which, in the case of the (110) and (100), is key to prevent surface poisoning. Altogether, this work sheds light on the yet unclear CO–H2 interactions on ceria surfaces during CO-PROX reaction, providing valuable insights to guide the design of more efficient reactors and catalysts for this process. The research was funded by the EU Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No 713567 and SFI Research Centre award 12/RC/2278_P2. The authors thank the financial support of the Spanish Ministry of Science and Innovation, PID2019-105960RB-C22, Generalitat Valenciana, PROMETEO/2018/076), and the EU (FEDER funding). The computational results of this research have been achieved using the DECI resource Salomon based in Czech Republic at the IT4Innovations National Supercomputing Center with support from the PRACE aisbl and the DJEI/DES/SFI/HEA Irish Centre for High-End Computing (ICHEC).

The conversion of CO2 towards added valuable products is considered as a potential alternative to achieve the increase of the petrochemical industry while reducing the CO2 emissions. In the present work, the effect of Ru loading on CeO2 supports has been studied for the CO2 methanation reaction, and catalysts with different Ru loading in the 1–5 wt. % range have been prepared, characterized, and tested. The optimum Ru loading has been found to be 2.5 wt. %. Ruthenium cations are reduced at the lowest temperature for this optimum loading according to H2-TPR experiments (even at room temperature), and the highest proportion of ruthenium cations with strong interaction with ceria is achieved, as deduced from XPS. XRD characterization suggests partial insertion of ruthenium cations into the ceria lattice. In situ DRIFTS experiments evidenced that the balance between formation upon CO2 chemisorption and further hydrogenation of surface carbon intermediates is optimum for 2.5 wt. % Ru/CeO2. For low metal contents, the CO2 chemisorption is limited and no relevant, while as the metal content is increased, the hydrogenation of carbon species is less favourable. The 2.5 wt.% Ru/CeO2 catalyst comprises a balance between surface-carbon groups formation and further hydrogenation. Generalitat Valenciana (PROMETEO/2018/0765); MICINN (PID2019-105960RB-C22); Junta de Andalucía (Project P18-RTJ-2974); European Union's Horizon 2020 research and innovation program (Marie Skłodowska-Curie grant agreement No 713567); Science Foundation Ireland Research Centre (award 12/RC/2278_P2).

The catalytic reduction of nitrites over Pt-In catalysts supported on activated carbon has been studied in a semi-batch reactor, at room temperature and atmospheric pressure, and using hydrogen as the reducing agent. The influence of the indium content on the activity and selectivity was evaluated. Monometallic Pt catalysts are very active for nitrite reduction, but the addition of up to 1 wt% of indium significantly increases the nitrogen selectivity from 0 to 96%. The decrease in the accessible noble metal surface area reduces the amount of hydrogen available at the catalyst surface, this favoring the combination of nitrogen-containing intermediate molecules to promote the formation of N2 instead of being deeply hydrogenated into NH4+. Several activated carbon-supported Pt-In catalysts, activated under different calcination and reduction temperatures, have been also evaluated in nitrite reduction. The catalyst calcined and reduced at 400°C showed the best performance considering both the activity and the selectivity to nitrogen. This enhanced selectivity is ascribed to the formation of Pt-In alloy. The electronic properties of Pt change upon alloy formation, as it is demonstrated by XPS. This work was financially supported by Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM, funded by natiunal funds through FCT/MCTES (PIDDAC). Financial support from Ministerio de Ciencia e Innovación (Spain, Project PID 2019-108453GB-C21 and PID 2020-116998RB-I00) is gratefully acknowledged.

Small amounts—0.04 wt.%—graphene oxide derivatives with different surface chemistry (graphene oxide—GO-, amine-functionalized GO—A-GO-, reduced GO—r-GO) were added during prepolymer formation in the synthesis of waterborne poly(urethane urea) dispersions (PUDs). Covalent interactions between the surface groups on the graphene oxide derivatives and the end NCO groups of the prepolymer were created, these interactions differently altered the degree of micro-phase separation of the PUDs and their structure–properties relationships. The amine functional groups on the A-GO surface reacted preferentially with the prepolymer, producing new urea hard domains and higher percentage of soft segments than in the PUD without GO derivative. All GO derivatives were well dispersed into the PU matrix. The PUD without GO derivative showed the most noticeable shear thinning and the addition of the GO derivative reduced the extent of shear thinning differently depending on its functional chemistry. The free urethane groups were dominant in all PUs and the addition of the GO derivative increased the percentage of the associated by hydrogen bond urethane groups. As a consequence, the addition of GO derivative caused a lower degree of micro-phase separation. All PUs containing GO derivatives exhibited an additional thermal decomposition at 190–206 °C which was ascribed to the GO derivative-poly(urethane urea) interactions, the lowest temperature corresponded to PU+A-GO. The PUs exhibited two structural relaxations, their temperatures decreased by adding the GO derivative, and the values of the maximum of tan delta in PU+r-GO and PU+A-GO were significantly higher than in the rest. The addition of the GO derivative increased the elongation-at-break, imparted some toughening, and increased the adhesion of the PUD. The highest T-peel strength values corresponded to the joints made with PUD+GO and PUD+r-GO, and a rupture of the substrate was obtained.

This article discloses a rare and outstanding type of Mn-rich black-blue patina found on mural painting and granite ashlars located in the church of Sta. Marinha, north of Portugal, and conjectures the phenomenon associated to the appearance of such patinas in different surface materials. This Mn-patina reported on mural painting and their origin is probably assigned to manganese leaching from building materials (i.e., granite and phyllites). Stained mural painting and granite examined by XPS and SEM have showed patinas enriched with manganese (IV) oxide, potentially catalysed by a microbiota, like fungi, observed in SEM micrographs. The pigments used to depict mural painting and groundwater were also analysed by micro-Raman and ICP-MS, respectively, indicating that they are unlikely manganese sources. Unstained building materials, such as granite ashlars, historic joints, mortars and phyllite rocks, were also analysed by ICP-MS showing that historic joints and mortars present significant concentrations of manganese, possibly associated to their absorbing feature. The main materials with potential to impart manganese to Mn-rich patinas are granite ashlars and phyllites. The aim of this investigation is to reveal and ascertain the hypothetical sources and the phenomenon responsible for the Mn-rich black-blue patina appearance, both on mural painting and granite ashlars. We would like to thanks the financial support of the project BIO4MURAL—Biotechnology innovative solutions for the removal of pigmentation and preventive conservation of cultural and historically relevant mural painting was funded by FEDER through project reference POCI-01-0145-FEDER-029157—Operational Competitiveness and Internationalization Program and by National Funds from FCT—Foundation for Science and Technology (PTDC/HAR-ARQ/29157/2017); Alexandra Marco PhD research was supported by Foundation for Science and Technology (FCT) through POCH—Operational Human Capital Program, co-participated by the Social European Fund (FSE) and MCTES National Fund (SFRH/BD/125596/2016); Dr. David M. Freire-Lista is supported by FCT through Stimulus of Scientific Employment, Individual Support 2017. CEECIND/03568/2017. HERCULES Laboratory—Évora University and E-RHIS.pt infra-structure for the access to the platforms PT-MOLAB and PT-FIXLAB; and scientific collaboration through the Strategic Projects CITAR (UID/EAT/0622/2016), CBQF (UID/Multi/50016/2013) and GEOBIOTEC (UID/GEO/04035/2020).

Carbon dioxide (CO2) is both a primary contributor to global warming and a major industrial impurity. Traditional approaches to carbon capture involve corrosive and energy-intensive processes such as liquid amine absorption. Although adsorptive separation has long been a promising alternative to traditional processes, up to this point there has been a lack of appropriate adsorbents capable of capturing CO2 whilst maintaining low regeneration energies. In the context of CO2 capture, metal–organic frameworks (MOFs) have gained much attention in the past two decades as potential materials. Their tuneable nature allows for precise control over the pore size and chemistry, which allows for the tailoring of their properties for the selective adsorption of CO2. While many candidate materials exist, the amount of research into material shaping for use in industrial processes has been limited. Traditional shaping strategies such as pelletisation involve the use of binders and/or mechanical processes, which can have a detrimental impact on the adsorption properties of the resulting materials or can result in low-density structures with low volumetric adsorption capacities. Herein, we demonstrate the use of a series of monolithic MOFs (monoUiO-66, monoUiO-66-NH2 & monoHKUST-1) for use in gas separation processes., The use of metal–organic frameworks (MOFs) in industry has been limited due to a lack of shaping technologies. Monolithic MOFs (monoMOFs) offer a viable alternative to traditional shaping offering high density materials for adsorption processes.

Using macro-perforations in a generic porous media may not only make the resonance frequency of a rigidly backed sound absorber lower but also its sound absorption amplitude increase. Given the rise of 3D-printing in the field of acoustic materials over the last years, it turns out of great interest to explore the possibilities of this technology on the fabrication of these absorbers. Unlike conventional fabrication processes, additive manufacturing lets design the material at the microscopic scale, thus allowing choosing the appropriate geometrical dimensions of both the macro-perforations and the micro-pores that let enhance its sound absorption. In this work, a preliminary insight into the use of additive manufacturing technology for the fabrication of macro-perforated porous media for sound absorption is reported. For this purpose, several specimens having different pore sizes and porosities in the microporous medium were produced and tested in an impedance tube. Experimental results showed an improved absorption performance for those samples having macro-perforations. Additionally, predictions through the double porosity theory together with the JCA approach using macroscopic parameters obtained by an inverse characterization procedure were compared to the absorption measurements showing a good agreement. This research suggests that the use of additive manufacturing technology may provide an excellent workbench for the optimal design of such absorbers. This work was developed in the framework of the COST Action CA15125 - DENORMS: “Designs for Noise Reducing Materials and Structures”. J. M. M-J. and L. P. M. acknowledge partial financial support from the Spanish Agencia Estatal de Investigación (AEI) and European Union (FEDER funds) through grant MAT2016-77742-C2-2-P.

For decades, carbons have been the support of choice in acetylene hydrochlorination, a key industrial process for polyvinyl chloride manufacture. However, no unequivocal design criteria could be established to date, due to the complex interplay between the carbon host and the metal nanostructure. Herein, we disentangle the roles of carbon in determining activity and stability of platinum-, ruthenium-, and gold-based hydrochlorination catalysts and derive descriptors for optimal host design, by systematically varying the porous properties and surface functionalization of carbon, while preserving the active metal sites. The acetylene adsorption capacity is identified as central activity descriptor, while the density of acidic oxygen sites determines the coking tendency and thus catalyst stability. With this understanding, a platinum single-atom catalyst is developed with stable catalytic performance under two-fold accelerated deactivation conditions compared to the state-of-the-art system, marking a step ahead towards sustainable PVC production., Nature Communications, 12 (1), ISSN:2041-1723

Ceria-based catalysts, with Cu in substitution of noble metals, were studied in a vertical microreactor system under isothermal conditions, where NOx was previously stored, followed by the reduction step conducted under H2. The possible remaining ad-NOx species after the reduction stage, were investigated by Temperature Programmed Desorption in He. In situ DRIFTS was used as a complementary technique for the analysis of the surface species formation/transformation on the catalysts’ surface. Catalysts containing both Ba and Cu were found to be selective in the NOx reduction, producing N2 and minor amounts of NH3 during the reduction step, as well as NO. The different ceria-based formulations (containing copper and/or barium) were prepared and tested at two different temperatures in the NOx reduction (NSR) processes. Their catalytic activities were analyzed in terms of their compositions and have been useful in the elucidation of the possible origin and relevant pathways for NOx reduction product formation, which seems to involve the oxygen vacancies of the ceria-based materials (whose generation seems to be promoted by copper) during the rich step. The scope of this work involves an interdisciplinary study of the impact that catalysts’ formulations (noble metal-free) have on their LNT performance under simulated conditions, thus covering aspects of Materials Science and Chemical Engineering in a highly applied context, related to the development of control strategies for hybrid powertrains and/or the reduction of the impact of cold-start emissions. This research was funded by the financial support from the Generalitat Valenciana (PROMETEO/2018/076 project) and the Spanish Ministry of Science and Innovation (PID2019-105542RB-I00 project) and the UE-FEDER funding. J.C.M.-M. also acknowledges Spanish Ministry of Science and Innovation for the financial support through an FPU grant (FPU17/00603).

Made available in DSpace on 2021-06-25T10:32:26Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-06-14 A series of new manganese(ii) complexes were prepared with three bidentate Schiff-base ligands derived by condensation of salicylaldehyde and different cycloalkylamines (cycloalkyl = cyclopentyl, cyclohexyl, and cycloheptyl): [Mn(CyPen-Salicyl)2] (1), [Mn(CyHex-Salicyl)2] (2), and [Mn(CyHep-Salicyl)2] (3). The complexes 1-3 were characterized by FTIR, UV-vis and EPR spectroscopy, elemental analysis, cyclic voltammetry, and computational methods. The manganese(ii) complexes (1-3) were used as controlling agents for the polymerization of vinyl acetate (VAc) initiated by AIBN according to an organometallic-mediated radical polymerization (OMRP) mechanism. The VAc polymerization mediated by the Mn complexes suggests that the control level can be slightly tuned through substitution of the cycloalkyl group on the Schiff-base ligand. Kinetics studies and computational investigations support an RT mechanism and a tailorable Mn complex reactivity mainly altered by steric factors of the Schiff-base ligands. The calculated thermodynamic parameters agree with the mediating ability of these complexes, since the degree of polymerization control decreases with increasing steric hindrance of the Schiff-base ligands, as well as with increasing ΔG values for the formation of dormant species. Faculdade de Ciências e Tecnologia UNESP-Univ. Estadual Paulista Instituto de Química Universidade Federal de Uberlândia, P.O. Box 593 CEITEC-Central European Institute of Technology Brno University of Technology, Purkyňova 123 Instituto de Física de São Carlos Usp Universidade de São Paulo Faculdade de Ciências e Tecnologia UNESP-Univ. Estadual Paulista

To evaluate the structural and spectroscopic steering factors of noble metal promotion in the catalytic reduction of NO by CO, a series of La(Cu0.7Mn0.3)0.98M0.02O3−δ (M = Pd, Pt, Ru, Rh) perovskite catalysts is investigated. The materials are synthesized by a sol-gel method and characterized by X-ray powder diffraction (XRD), electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). All metal-promoted perovskites exhibit a comparatively higher activity for catalytic reduction of NO by CO with respect to pure La(Cu0.7Mn0.3)O3−δ . Among all catalysts tested, the La(Cu0.7Mn0.3)0.98Pd0.02O3−δ perovskite shows the highest catalytic activity, which is tentatively related to a combined synergistic effect of improved oxygen vacancy activity and noble metals. Additionally, the redox chemistry of the catalysts in different reducing (H2) and oxidizing (NO, O2) atmospheres is tested. An enhanced kinetic reducibility, especially with Pd, was observed. All the H2-reduced catalysts are capable of reducing NO. At low and intermediate temperatures, the formation of N2O is observed, but at higher temperatures NO is exclusively converted to N2. The introduction of noble metals leads to new adsorption sites for NO. As XPS suggests a tendency for depletion of noble metals in the surface-near regions, while the catalytic activity in NO reduction at the same time appears much improved, directed noble metal promotion with modest amounts especially in surface-near regions during synthesis appears as an encouraging method to economize the use of the latter. This work was performed within the framework of the funding programme IMPULSE Iran Austria, financed by funds of the OeAD fonds and of the Ministry of Science, Research and Technology of the Islamic Republic of Iran. We also thank the SFB F45-N16 special research program for financial support. This work was performed within the framework of the research platform ‘‘Materials and Nanoscience” and the special PhD program ‘‘Reactivity and Catalysis”, both at the University of Innsbruck.

P-postmodified polyaniline was obtained by reacting phosphorus trichloride (PCl3) and chlorodiphenylphosphine (PPh2Cl) and polyaniline (PANI), under mild conditions. The reaction was found to be very selective, as only the imine groups were involved in the P-functionalization, and efficient as well, affording a P-loading of 3 at.% and 5 at.% for PPh2Cl and PCl3, respectively. All the polymers were characterized by different techniques and the results were endorsed by theoretical calculations. Experimental and Density Functional Theory results proved that the reaction occurs through the imine groups and the phosphorus atoms, generating NP bonds. The electrochemical properties of the NP modified materials were evaluated and the catalytic activity towards oxygen reduction reaction was measured. It was found that a high concentration of phenyl groups from PPh2Cl (about 3 at.%) affected negatively the activity of the catalyst since they prevented the access of the oxygen molecules to the catalytic active sites. However, a lower amount of PPh2 groups (1 at.%) or the use of PCl3 avoided this hindrance and resulted in an improved catalytic activity with respect to pristine PANI. The authors thank MINECO, MICIUNIN, FIS2015-64222-C2-2-P and FEDER (RTI2018-095291-B-I00 and MAT2016-76595-R) for the financial support.

[EN] The construction of communication models at the micro¿/nanoscale involving abiotic nanodevices and living organisms has the potential to open a wide range of applications in biomedical and communication technologies. However, this area remains almost unexplored. Herein, we report, as a proof of concept, a stimuli¿responsive interactive paradigm of communication between yeasts (as a model microorganism) and enzyme¿controlled Janus Au¿mesoporous silica nanoparticles. In the presence of the stimulus, the information flows from the microorganism to the nanodevice, and then returns from the nanodevice to the microorganism as a feedback., B.dL. is grateful to the Spanish Government for her FPU PhD fellowship. The authors wish to thank the Spanish Government (projects RTI2018-100910-B-C41 (MCUI/AEI/FEDER, UE) and CTQ2017-87954-P), the Generalitat Valenciana (project PROMETEO2018/024), the Comunidad de Madrid (Project IND2017/BMD-7642) and CIBER-BBN (NANOCOM project) for support.

We present a process for the synthesis of binder-free carbon monoliths, which were prepared from carbon microspheres at room temperature. The microspheres were obtained through hydrothermal treatment of sucrose, and monoliths with a bulk density around 1 g cm−3 were prepared from them by a simple pressurization process. Subsequently, the monoliths were activated with CO2 in order to increase their porosity. The activation preserved the monolithic shape and yielded maximum BET surface areas close to 4000 m2 g-1. High pressure gas adsorption isotherms reveal that the activated carbon monoliths are interesting candidates for gas storage applications. High excess adsorption amounts are measured for hydrogen (1.2 wt. %) and methane (453 mg g−1) at room temperature and pressures up to 20 MPa. Taking into account the measured densities of the monoliths, a maximum volumetric excess adsorption amount of CH4 of 230 cm3cm−3 is reached. The authors thank Generalitat Valenciana/Feder (PROMETEO/2018/076) and University of Alicante (VIGROB-136) for financial support.

[EN] A new delivery microdevice, based on hydrophobic oleic acid¿capped mesoporous silica particles and able to payload release in the presence of surfactants, has been developed. The oleic acid functionalization confers to the system a high hydrophobic character, which avoids cargo release unless surfactant molecules are present. The performance of this oleic¿acid capped microdevice in the presence of different surfactants is presented and its zero¿release operation in the absence of surfactants is demonstrated., The authors want to thank the Spanish Government (projects MAT2015-64139-C4-1-R, AGL2015-70235-C2-1-R and AGL2015-70235-C2-2-R (MINECO/FEDER)) and RTI2018-100910-B-C41, RTI2018-101599-B-C22 and RTI2018-101599-B-C21 (MCUI/AEI/FEDER, UE)) and Generalitat Valenciana (project PROMETEO/2018/024) for support. E.P.-R. thanks the Generalitat Valenciana for her predoctoral fellowship. A.B. wants to acknowledge the Spanish Government for the financial support Juan de la Cierva Incorporación IJCI-2014-21534. The authors also thank the Electron Microscopy Service at the UPV for support.

A series of α-alumina-supported cobalt spinel catalysts of various expositions of the (100), (111), and (110) planes was synthesized and tested in the preferential oxidation of CO (CO-PROX) reaction. Successful control of the polyhedral shape of the nanospinel active phase was achieved via glycerol and/or Zn addition to the impregnation solution. This allowed for the application of such catalysts for resolving the shape–reactivity relationships in a more controlled fashion in comparison to previous studies, where various catalysts of an entirely unlike origin were used. The catalysts were thoroughly characterized by means of X-ray fluorescence, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, scanning transmission electron microscopy, and temperature-programmed reduction techniques. The CO-PROX catalytic performance of the obtained catalysts was examined in the temperature-programmed surface reaction mode. A strong impact of the spinel nanograin morphology on the activity was observed, with the (100) termination found as the most active among all of the exposed low-index (111) and (110) planes. Furthermore, a linear correlation between the abundance of the surface Co3+ cations and the yield of carbon monoxide oxidation reveals their vital relevance as the catalytically CO-PROX active sites. The results are discussed in terms of a thermodynamic diagram of the surface oxygen, water, and oxygen vacancy stabilities on the Co3O4 most abundant planes, providing the rational background for the superior behavior of the (100) termination in the CO-PROX reaction. The obtained results speak in favor of the involvement of the suprafacial oxygen species in the CO oxidation process. The authors would like to acknowledge the funding awarded by the Polish National Science Center (decision number 2017/27/B/ST4/01155) and the financial support from Generalitat Valenciana (Project PROMETEOII/2014/010), Spanish Ministry of Economy and Competitiveness (Project CTQ2015-67597-C2-2-R), and Spanish Ministry of Education, Culture and Sports (grant FPU14/01178). The research was partially carried out with the equipment purchased as a result of the financial support of the European Regional Development Fund in the framework of the Polish Innovation Economy Operational Program (contract no. POIG.02.01.00-12-023/08).

Knowledge of the carbon active sites for Oxygen Reduction Reaction (ORR) remains confusing and controversial and thus the detailed mechanism is still not clarified. Considering the nature of the carbon-oxygen interaction in active sites during the gasification reaction, it could be inferred that the sites for this reaction are the same as those participating in the ORR. Herein, the relationship between carbon-oxygen gasification properties and ORR activities was elucidated. Carbon materials including different structures and porosities were selected and extensively characterized in terms of structural and electrochemical properties. Regarding gasification properties, active surface area (ASA) and reactivity for carbon-oxygen reaction were determined. A good linear correlation is found between ORR activity and carbon-oxygen gasification reactivity. Interestingly, similar correlation is found between ORR activity or gasification reactivity and ASA, although two different slopes are observed for the analyzed samples, being higher for the carbon nanotubes (CNT) based samples. The results suggest that the active sites participating in the gasification reaction can be catalytic sites for ORR although the specific catalytic activity is determined by the carbon structure. Thus, active sites in CNT show higher activities toward ORR and carbon gasification reactivities than others. The authors gratefully acknowledge the financial support by MINECO (CTQ2015-66080-R MINECO/FEDER) and HEIWA NAKAJIMA FOUNDATION.

The purpose of this work was the assembly of multicomponent nano-bioconjugates based on mesoporous silica nanoparticles (MSNs), proteins (bovine serum albumin, BSA, or lysozyme, LYZ), and gold nanoparticles (GNPs). These nano-bioconjugates may find applications in nanomedicine as theranostic devices. Indeed, MSNs can act as drug carriers, proteins stabilize MSNs within the bloodstream, or may have therapeutic or targeting functions. Finally, GNPs can either be used as contrast agents for imaging or for photothermal therapy. Here, amino-functionalized MSNs (MSN–NH2) were synthesized and characterized through various techniques (small angle X-rays scattering TEM, N2 adsorption/desorption isotherms, and thermogravimetric analysis (TGA)). BSA or lysozyme were then grafted on the external surface of MSN–NH2 to obtain MSN–BSA and MSN–LYZ bioconjugates, respectively. Protein immobilization on MSNs surface was confirmed by Fourier transform infrared spectroscopy, ζ-potential measurements, and TGA, which also allowed the estimation of protein loading. The MSN–protein samples were then dispersed in a GNP solution to obtain MSN–protein–GNPs nano-bioconjugates. Transmission electron microscopy (TEM) analysis showed the occurrence of GNPs on the MSN–protein surface, whereas almost no GNPs occurred in the protein-free control samples. Fluorescence and Raman spectroscopies suggested that proteins–GNP interactions involve tryptophan residues.

Immersion calorimetry into liquids of different dimensions is a powerful tool to learn about the pore size and shape in nanoporous solids. In general, in the absence of specific interactions with the solid surface, the accessibility of the liquid probe molecule to the inner porosity and the associated enthalpy value decreases with an increase in its kinetic diameter (bulkier molecules have lower accessibility and packing density). Although this is true for the majority of solids (e.g., activated carbons and zeolites), this study anticipates that this is not straightforward in the specific case of metal–organic frameworks (MOFs). The evaluation of different hydrocarbons and their derivatives reveals the presence of reverse selectivity for C6 isomers (2,2-dimethylbutane > 2-methylpentane > n-hexane) in UiO-66 and HKUST-1, whereas size exclusion effects take place in ZIF-8. The immersion calorimetric findings have been compared with vapor adsorption isotherms and computational studies. Monte Carlo simulations suggest that the reverse selectivity in UiO-66 is attributed to the strong confinement of the dibranched hydrocarbons in the small tetragonal cages, whereas the presence of strong interactions with the open metal sites accounts for the preferential adsorption in HKUST-1. These results open the gate toward the application of immersion calorimetry for the prescreening of MOFs to identify in an easy, fast and reliable way interesting characteristics and/or properties such as separation ability, reversed hierarchy, pore-window size, presence of unsaturated metal sites, molecular accessibility, and so on. Authors would like to acknowledge financial support from MINECO (MAT2016-80285-p), Generalitat Valenciana (PROMETEOII/2014/004) and H2020 (MSCA-RISE-2016/NanoMed Project). P.Z.M. is grateful for start-up funds from the University of Sheffield.

An improved honeycomb-like monolith with asymmetrical channels, where the channels section decrease along the monolith, was fabricated using a template prepared by 3D printing. A reference honeycomb monolith was also prepared in the same way but with conventional straight channels. Cu/Ceria active phase was loaded on these supports, and SEM-EDX, Raman spectroscopy and XRD showed that the supported active phase is similar on both monoliths. The supported catalysts were tested for CO oxidation in excess oxygen and for preferential CO oxidation in H2-rich mixtures (CO-PROX), and the catalyst with the improved support achieved higher conversions in both reactions. The supported catalyst with asymmetrical channels has two benefits with regard to the counterpart catalyst with conventional symmetrical channels: improves the reaction rate with regard to the conventional one because fits better to the equation rate, and favors the turbulent regime of gases with regard to the laminar flow that prevails in symmetrical channels. This work was supported by the Spanish Ministry of Economy and Competitiveness (Projects MAT2014-61992-EXP and CTQ2015-67597-C2-2-R), Spanish Ministry of Education, Culture and Sports (grant FPU14/01178), Generalitat Valenciana (Project PROMETEO/2018/076) and EU (FEDER funding).

[EN] A nanodevice based on mesoporous silica nanoparticles with rhodamine B in the pore framework, functionalized with carboxylates on the outer surface and capped with the cationic polymyxin B peptide, was used to selectively detect endotoxin in aqueous solutions with a limit of detection in the picomolar range., The authors thank the Spanish Government (MAT2015 64139-C4-1-R) and the Generalitat Valenciana (PROMETEO2018/024) for their support. I.O. thanks to Erasmus Mundus Programme, Action 2, Lot 1, Syria, for his predoctoral fellowship. S.S. is grateful to Spanish Ministerio de Economia y Competitividad for his Juan de la Cierva contract (FJCI-2015-27201).

In this work, bimetallic Cu–Ni catalysts have been studied in the water-gas shift (WGS) reaction, and they have shown different levels of synergy and anti-synergy in terms of catalytic activity and selectivity to the desired products. Cu–Ni interactions alter the physicochemical properties of the prepared materials (i.e. surface chemistry, redox behaviour, etc.) and as a result, the catalytic trends are influenced by the catalysts' composition. Our study reveals that Cu enhances Ni selectivity to CO2 and H2 by preventing CO/CO2 methanation, while Ni does not help to improve Cu catalytic performance by any means. Indeed, the monometallic Cu formulation has shown the best results in this study, yielding high levels of reactants conversion and excellent long-term stability. Interestingly, for medium-high temperatures, the bimetallic 1Cu–1Ni outperforms the stability levels reached with the monometallic formulation and becomes an interesting choice even when start-up/shutdowns operations are considered during the catalytic experiments. Financial support for this work was provided by the EPSRC grants EP/J020184/2 and EP/R512904/1 as well as the Royal Society Research Grant RSGR1180353. The Spanish team acknowledges Ministerio de Economía, Industria y Competitividad of Spain (Project MAT2013-45008-P). L. Pastor-Perez acknowledges Generalitat Valenciana for her postdoctoral grant (APOSTD/2017). Sasol is kindly acknowledged for providing the support.

[EN] Microalgae play a fundamental role in aquatic primary production and the food chain. They are a recognized source of fatty acids and fatty acid-based lipids of potential interest in the preparation of functional health products, biofuels and renewable chemicals. The exploitation of this bioresource requires a fine monitoring of each production stage. The aim of this work is the microalgae degradation follow up after the concentration stage at the end of the production process by voltammetric electronic tongue, impedance spectroscopy and H-1 NMR spectroscopy. Microalgae samples were allowed to progress along time (from 1 to 23 days). At scheduled selected times, voltammetry, impedance spectroscopy and H-1 NMR measurements were performed. Multivariate analysis was carried out on these data by PLSR. A model calculated in a training set was then applied to a set of validation to predict the time of evolution. For the three techniques good results in prediction for the validation set were obtained (R-2/RMSEP of 0.961/1.51, 0.956/1.67 and 0.969/1.25 respectively for impedance, voltammetry and NMR spectroscopy). The three techniques were sensitive to the evolution of the microalgae samples. The detection of metabolical changes in the H-1 NMR spectra is also included. This proof of concept could be the basis for future development of rapid and robust strategies for quality control on microalgae production plants., Authors gratefully acknowledge the financial support of MAT2015-64139-C4-1-R and MAT2015-64139-C4-3-R (MINECO/FEDER, UE) and PROMETEOII/2014/047 projects. BUGGYPOWER, S.L. is acknowledged for the financial support and for providing the samples. U26 Nanbiosis is acknowledged by the NMR measurements.

Nanotechnology, which has already revolutionised many technological areas, is expected to transform life sciences. In this sense, nanomedicine could address some of the most important limitations of conventional medicine. In general, nanomedicine includes three major objectives: (1) trap and protect a great amount of therapeutic agents; (2) carry them to the specific site of disease avoiding any leakage; and (3) release on-demand high local concentrations of therapeutic agents. This feature article will make special emphasis on mesoporous silica nanoparticles that release their therapeutic cargo in response to ultrasound.

A hierarchical USY zeolite has been produced using the surfactant-templating method and used as a catalyst for the production of two important active pharmaceutical ingredients. The presence of intracrystalline mesoporosity in the zeolite results in a significant increase in both the activity (up to 30 fold increase in TOF) and reusability for Friedel–Crafts alkylation and aldol condensation steps. N. L. wishes to thank the Generalitat Valenciana for financial support under the project BEST/2018/039 and the University of Alicante, through the “Programa de captación y retención de talento” (UATALENTO17-05).

Synthesizing high-activity metal/heteroatom-co-doped carbon (M/H–C) electrocatalysts for the oxygen reduction reaction (ORR) is critical for the commercialization of fuel cells, but remains challenging because of the difficulty in making highly dispersed (M/H–C) electrocatalysts. Herein, a commercial ion-exchange resin, Amberlyst 15, is used as a support, and Co/2-methylimidazole is anchored on the ion-exchange site of the support to obtain Co/N/Amb as the precursor of the M/H–C electrocatalyst. After the precursor is pyrolyzed and converted into Co/N/C materials, it is activated with CO2, and the obtained material (act-Co/N/C) exhibits remarkable ORR activity with a high onset potential of 0.943 V (vs. the reversible hydrogen electrode) and an excellent kinetic current density comparable to commercial 5 wt% Pt/C in an alkaline medium. The favorable activity is mainly attributed to the ultra-dispersed CoNx and high porosity of act-Co/N/C. Our synthetic strategy could be applied to the preparation of other well-dispersed M/H–C materials. This work opens a new direction in the synthetic strategy of carbon materials. Financial support from MINECO (CTQ2015-66080-R) and HEIWA NAKAJIMA FOUNDATION is acknowledged.

A series of BaFe1−xCuxO3 catalysts (x = 0, 0.1, 0.3 and 0.4) have been synthetized, characterized and used for soot oxidation in gasoline direct injection (GDI) exhaust conditions. The characterization of the catalysts (by BET, ICP-OES, XRD, XPS, H2-TPR and O2-TPD) reveals that copper is incorporated into the perovskite lattice leading to: (i) the distortion of the original hexagonal perovskite structure for the lowest copper content catalyst (BFC1) and the modification of the structure, from hexagonal to cubic, for the catalysts with higher copper content (BFC3 and BFC4), (ii) the generation of a BaOx–CuOx oxide as minority segregated phase for BFC4 catalyst, (iii) the increase in the amount of oxygen surface vacancies for BFC3 and BFC4 catalysts, and (iv) the decrease in the total amount of O2 released during O2-TPD experiments. All the BaFe1−xCuxO3 perovskites are active for soot oxidation under the highest demanding GDI exhaust conditions (regular stoichiometric GDI operation, i.e., 0% O2). The catalyst with the highest copper content (BFC4) shows the highest soot conversion, related to its largest amount of β-oxygen evolved, and, to the presence of a high amount of copper species (as BaOx–CuOx oxide) on its surface. The authors thank Generalitat Valenciana (PROMETEO/2018/076), Spanish Government (MINECO Project CTQ2015-64801-R) and UE (FEDER Founding) for the financial support. V. Torregrosa-Rivero thanks the Generalitat Valenciana for her Ph.D. Grant (ACIF 2017/221).

PrOx nanoparticles (10nm; 81m2/g) were synthesized and analysed as soot combustion catalyst in comparation with other reference materials including CeO2 nanoparticles and PrOx and CeO2 catalysts with three dimensionally ordered (3DOM) and without controlled structure. PrOx nanoparticles reached the highest activity; T50 decreases from 603 °C (uncatalysed combustion) to 494 °C. This high activity can be attributed to the high surface area/low crystal size, which enhances the soot catalyst contact, and to the improved reducibility. PrOx nanoparticles kept high activity (T50 = 520 °C) after aging at 800 °C, being significantly more active than aged PrOx catalysts with 3DOM and uncontrolled structure and also significantly more active than all aged CeO2 catalysis which suffer almost total deactivation upon aging. In all cases, PrOx catalysts are more active than CeO2 counterpart materials with the same structure and thermal history, and this applies to nanoparticles, 3DOM and uncontrolled structures. The authors thank the financial support of the Spanish Ministry of Economy and Competitiveness (Project CTQ2015-67597-C2-2-R), Ministry of Science, Innovation and Universities (Project PID2019-105960RB-C22), Generalitat Valenciana (Project PROMETEO/2018/076 and grant APOSTD/2019/030), Junta de Andalucía (Project P18-RTJ-2974), University of Alicante (Project GRE18-01A) and the UE (FEDER funding).

The antiferromagnetic behavior of Fe3+ oxides of composition RE1.2Ba1.2Ca0.6Fe3O8, RE2.2Ba3.2Ca2.6Fe8O21, and REBa2Ca2Fe5O13 (RE = Gd, Tb) is highly influenced by the type of oxygen polyhedron around the Fe3+ cations and their ordering, which is coupled with the layered RE/Ba/Ca arrangement within the perovskite-related structure. Determination of the magnetic structures reveals different magnetic moments associated with Fe3+ spins in the different oxygen polyhedra (octahedron, tetrahedron, and square pyramid). The structural aspects impact on the strength of the Fe-O-Fe superexchange interactions and, therefore, on the Néel temperature (TN) of the compounds. The oxides present an interesting transition from three-dimensional (3D) to two-dimensional (2D) magnetic behavior above TN. The 2D magnetic interactions are stronger within the FeO6 octahedra layers than in the FeO4 tetrahedra layers., The antiferromagnetic behavior of Fe3+ oxides is highly influenced by the type of oxygen polyhedron around the Fe3+ cations and their ordering, which is coupled with the layered RE/Ba/Ca arrangement, within the perovskite-related structure in this striking (RE, Ba, Ca)3m+5nFe3m+5nO8m+13n (m, n) homologous series.

The preparation of MOFs including a metal with an easily exchangeable oxidation state, while maintaining the same crystal structure and stability, is of paramount importance for myriad applications. In this work, a new synthesis method is reported that can be used to prepare Ce/Zr‐MOFs (UiO‐66 structure) having only Ce(III), a mixed‐valence Ce(IV)/Ce(III), or only Ce(IV) cations, as desired. The materials are characterized using a large number of techniques, including X‐ray absorption and X‐ray photoelectron spectroscopies. Authors acknowledge financial support by MINECO (Spain) through projects, MAT2017-86992-R and MAT2016-80285-P. EVRF acknowledges MINECO for his Ramón y Cajal fellow RYC-2012-11427. The authors also would like to thank Diamond Light Source (I20-Scanning beamline) for the beamtime given at the proposal SP19114.

[EN] For the preparation of methyl ketones, cross Ketonic Decarboxylation, i.e., the formation of a ketone from two different carboxylic acids, and the reketonization, i.e., the transformation of a carboxylic acid into a ketone employing a ketone as alkyl transfer agent, may be interesting alternatives to classical pathways involving metalorganic reagents. The fine chemical 2-undecanone was chosen as model compound and ketonic decarboxylation and reketonization evaluated by Green Chemistry matrices, namely the carbon atom efficiency and the e-factor. The efactor of the reaction of decanoic acid with acetic acid was less than five and, therewith, in the acceptable range for bulk chemicals, when valorizing acetone (e.g., as a solvent) and considering a 90% solvent recycling. The reketonization of decanoic acid with acetone provided a different main product, namely 10-nonadecanone, with a detrimental effect on atom efficiency. By means of labeling experiments it was shown that ketonic decarboxylation is significantly faster than the reketonization reaction. The transformation of acetic acid into acetone was studied by in-situ and operando IR spectroscopy. Thereby it was found that the surface was covered by acetic acid. The lack of adsorption of acetone is a clear drawback for the reketonization of carboxylic acids. To improve the reaction outcome, and therewith, its sustainability a possibility has to be found to stabilize the ketone molecules on the surface in the presence of carboxylic acids., Financial support from the Spanish Government is acknowledged (Ministry of Science, Innovation and Universities, RTC-2017-6087-5 and PGC2018-097277-B-I00). MR is grateful to the Generalitat Valenciana for a BEST-2015 fellowship and to Dilyana Mladenova, Arturo Valero Jim ' enez and Claudia Fern ' andez de la Pena for their contributions to the experimental work of the catalytic reactions.

Ru catalysts (1 wt.%) supported on commercial and biomass-derived activated carbons (AC) have been prepared, thoroughly characterized, and used in the hydrogenation of levulinic acid to produce gamma-valerolactone (GVL). This is an important platform compound that plays a key role in the production of liquid fuels and that can also be used, for example, as a food flavoring agent, antifreeze, and solvent. The study focuses on the influence of the carbon support characteristics, such as porous texture and acidity, on the properties and performance (LA conversion and selectivity to GVL) of the catalysts. Catalytic activity tests have been carried out at 170 °C and also in noticeably milder conditions (70 °C) to implement a less energy-demanding process. All the catalysts show high LA conversion and GVL yield at 170 °C, while at 70 °C, important differences between them, related to the support properties, have been found. The catalysts prepared with more acidic supports show better catalytic properties: very good catalytic performance (98% LA conversion and 77% selectivity to GVL) has been obtained in mild temperature conditions. This research was funded by the Spanish Ministry of Science, Innovation and Universities (RTI2018-095291-B-I00), Generalitat Valenciana (PROMETEO/2018/076), European ComissionFEDER, and the University of Alicante (VIGROB-136).

Conventional methods to prepare hierarchical zeolites depend upon the use of organic structure‐directing agents and often require multiple synthesis steps with limited product yield and Brønsted acid concentration. Here, it is shown that the use of MEL‐ or MFI‐type zeolites as crystalline seeds induces the spontaneous formation of self‐pillared pentasil zeolites, thus avoiding the use of any organic or branching template for the crystallization of these hierarchical structures. The mechanism of formation is evaluated by time‐resolved electron microscopy to provide evidence for the heterogeneous nucleation and growth of sequentially branched nanosheets from amorphous precursors. The resulting hierarchical zeolites have large external surface area and high percentages of external acid sites, which markedly improves their catalytic performance in the Friedel–Crafts alkylation and methanol to hydrocarbons reactions. These findings highlight a facile, commercially viable synthesis method to reduce mass‐transport limitations and improve the performance of zeolite catalysts. J.D.R. acknowledges support primarily from the U.S. Department of Energy Office of Basic Energy Sciences (Award DE-SC0014468). J.D.R. acknowledges additional funding from the Welch Foundation (Award E-1794). N.L and J.G.M thank the European Commission for funding through the H2020-MSCARISE-2019 program (Ref. ZEOBIOCHEM – 872102) and the Spanish MINECO and AEI/FEDER, UE through the project ref. RTI2018-099504-B-C21. N.L. also acknowledges the University of Alicante support (UATALENTO17-05).

Cryptomelane is an abundant mineral manganese oxide with unique physicochemical features. This work investigates the real capabilities of cryptomelane as an oxidation catalyst. In particular, the preferential CO oxidation (CO-PROX), has been studied as a simple reaction model. When doped with copper, the cryptomelane-based material has revealed a great potential, displaying a comparable activity to the high-performance CuO/CeO2. Despite stability concerns that compromise the primary catalyst reusability, CuO/cryptomelane is particularly robust in the presence of CO2 and H2O, typical components of realistic CO-PROX streams. The CO-PROX reaction mechanism has been assessed by means of isotopic oxygen pulse experiments. Altogether, CuO/CeO2 shows a greater oxygen lability, which facilitates lattice oxygen enrolment in the CO-PROX mechanism. In the case of CuO/cryptomelane, in spite of its lower oxygen mobility, the intrinsic structural water co-assists as active oxygen species involved in CO-PROX. Thus, the presence of moisture in the reaction stream turns out to be beneficial for the stability of the cryptomelane structure, besides aiding into the active oxygen restitution in the catalyst. Overall, this study proves that CuO/cryptomelane is a promising competitor to CuO/CeO2 in CO-PROX technology, whose implementation can bring the CO-PROX technology and H2 purification processes a more sustainable nature. The authors thank the financial support of the Spanish Ministry of Economy and Competitiveness (Project CTQ2015-67597-C2-2-R and grant FJCI-2015-23769), the Spanish Ministry of Science and Innovation (PID2019-105960RB-C22), Spanish Ministry of Education (FPU14/01178), Generalitat Valenciana (Project PROMETEO/2018/076), and the EU (FEDER funding).