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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.

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.

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.

The hydrogenation of nitroarenes to produce the corresponding amines using dihydrogen as reducing agent has an important industrial role, since it allows to obtain important added-value products. This reaction needs the help of a catalyst to proceed. Many catalysts have been already tested and studied. Most of them are based on noble metals supported on metal oxides. These catalysts perform well, but they are expensive and thus, alternative systems are needed. In this context, cobalt-based catalysts have emerged as adequate alternatives, despite cobalt nanoparticles per se are not very active for this reaction. A way to improve the catalytic activity of cobalt nanoparticles is by supporting them on a support with functional groups that are able to change their intrinsic properties and to enhance their catalytic properties. In this sense, N-containing carbons are promising candidates to be used as support, since nitrogen functionalities may modify the catalytic properties of cobalt. In this work, cobalt nanoparticles supported on N-doped activated carbons have been prepared and studied as catalysts for the hydrogenation of 1-chloro-4-nitrobencene to the corresponding chloro-aniline. It is demonstrated that the catalytic activity is enhanced by the presence of nitrogen species in the support. When the temperature of the catalyst activation treatment (reduction under flowing hydrogen) is increased, the catalytic activity increases drastically in the presence of nitrogen functionalities on the support. The catalysts have been characterised by transmission electron microscopy (TEM), temperature-programmed reduction (TPR), X-ray diffraction, X-ray photoelectron spectroscopi (XPS) and N2 adsorption at 77 K. It has been found that the enhanced catalytic activity was due to two different factors, namely the interaction of the cobalt particles with the nitrogen functional groups (forming Co4N), and the development of mesopores in the support during the activation process that increases the accessibility of reactants to the active sites. Authors acknowledge financial support by MINECO (Spain) through the projects MAT2017-86992-R and MAT2016-80285-P and the European Union for the project “eForFuel”, grant agreement 763911. J. C. S. R. would like to thank the Spanish Ministry of Science and Innovation for financial support through the Ramón y Cajal Program, Grant: RYC-2015-19230 J. C. S. R. would also like to thank Junta de Andalucía for financial support through the projects PY18-RE-0012 and IE18_0047_FUNDACIÓN LOYOLA.

MXenes are a new family of two-dimensional carbides and/or nitrides. Their 2D surfaces are typically terminated by O, OH and/or F atoms. Here we show that Ti3C2T x —the most studied compound of the MXene family—is a good acid catalyst, thanks to the surface acid functionalities. We demonstrate this by applying Ti3C2T x in the epoxide ring-opening reaction of styrene oxide (SO) and its isomerization in the liquid phase. Modifying the MXene surface changes the catalytic activity and selectivity. By oxidizing the surface, we succeeded in controlling the type and number of acid sites and thereby improving the yield of the mono-alkylated product to >80%. Characterisation studies show that a thin oxide layer, which forms directly on the Ti3C2T x surface, is essential for catalysing the SO ring-opening. We hypothesize that two kinds of acid sites are responsible for this catalysis: In the MXene, strong acid sites (both Lewis and Brønsted) catalyse both the ring-opening and the isomerization reactions, while in the Mxene–TiO2 composite weaker acid sites catalyse only the ring-opening reaction, increasing the selectivity to the mono-alkylated product.

In-situ hydrodeoxygenation of guaiacol over Ni-based nitrogen-doped activated carbon supported catalysts is presented in this paper as an economically viable route for bio-resources upgrading. The overriding concept of this paper is to use water as hydrogen donor for the HDO reaction suppressing the input of external high-pressure hydrogen. The effect of nitrogen sources, including polyporrole (PPy), polyaniline (PANI) and melamine (Mel) on the structural, electronic and ultimately of catalytic features of the design materials have been addressed. Nitrogen-doped samples, are more active than the undoped counterparts in the “H2-free” HDO process. For instance, the conversion of guaiacol increased by 8% for Ni/PANI-AC compared to that of Ni/AC catalysts. The superior performance of Ni/NC can be attributed to the acid-base properties and modified electronic properties which favours the C-O cleavage and water activation as well as enhances dispersion of Ni particles on the catalysts’ surface

The carbothermal synthesis of monometallic and bimetallic molybdenum carbide and copper, supported on high surface area graphite (H), has been studied by in situ XRD, XPS, D2-TPD, TEM/STEM, TG-mass spectrometry, and N2 adsorption. The catalysts were prepared using H2 at 600 °C or 700 °C and tested in the hydrogenation of CO2 to methanol. Molybdenum carbide and oxycarbide phases were obtained, as well as hydride species, at 600 °C on both monometallic MoxC/H and bimetallic CuMoxC/H in a similar proportion. Upon increasing the temperature up to 700 °C, the formation of metallic Mo is favourable. Although this is observed on supported MoxC and CuMoxC, the bimetallic sample is less affected by the formation of the hydride, and molybdenum carbide is also observed upon treatment at 700 °C. With regards to the catalytic performance, supported monometallic copper was not active, but copper increased the activity and selectivity of the molybdenum carbide. The yield of methanol per catalyst's weight increases upon increasing the copper loading, indicating that a cooperation reaction takes place between the smallest Cu particles in contact with the molybdenum phase. The catalysts synthesized at 700 °C are less active and less selective to methanol favouring the reverse water gas shift under the studied conditions. Interestingly, the catalysts are stable under the reaction conditions, and the detected phases by XRD of the spent catalysts suggest that the hydride species favoured transformations involving MoOxCyHz ↔ β-Mo2C. A. B. Dongil acknowledges financial support from the Fundación General CSIC (Programa ComFuturo and iLink project No 20211 from CSIC (Spain)). Financial support from the Spanish Agencia Estatal de Investigación (AEI) and EU (FEDER) (projects MAT2016-80285-P, CTQ2017-89443-C3-1-R and CTQ2017-89443-C3-3-R) is also acknowledged.

MXenes, first discovered in 2011, are two-dimensional transition metal carbides or nitrides. Because of their interesting electrical and optical properties, they are studied for applications in batteries, supercapacitors and electrocatalysis. However, MXenes are rarely used in heterogeneous catalysis and, to our knowledge, there are no reports on the use of oxidized MXenes in catalysis. Here we used Ti3C2Tx-derived materials as supports for platinum nanoparticles and studied their effectiveness for the hydrolysis of ammonia borane, which is a promising hydrogen carrier. Hydrogen can be released from ammonia borane through catalytic hydrolysis. Most heterogeneous catalysts reported for this purpose contain a noble metal supported on a metal oxide support. The interaction between the metal and the support is important in determining the catalytic performance. Our results show that the electronic environment of platinum can be modified by oxidising the surface of MXene, thus providing a new way of developing active catalysts. Oxidising agents such as water and ozone can be used for this purpose. This electronic modification enhances the catalytic activity of platinum for ammonia borane hydrolysis, which is relevant for other reactions related to energy production/storage. T K S was supported by NWO TOP-PUNT grant 718.015.004. Z S was supported by project LTAUSA19034 from Ministry of Education Youth and Sports (MEYS). E V R F and A S E would like to thanks financial support by MINECO (Spain) through the projects MAT2017-86992-R and MAT2016-80285-P.

A mechanism for the reduction of aqueous nitrate with metal-free polypyrrole (PPy) is proposed. The activity and selectivity of the polymer has been compared to those of metal catalysts supported on polypyrrole, activated carbon or titania (TiO2). The role of formic acid (FA) and hydrogen (H2) as reductants, and carbon dioxide (CO2) as buffer of the aqueous nitrate solution is discussed and compared to the performance of PPy by itself. The ion-exchange and the redox properties of PPy are strongly affected by the oxidation state of the nitrogen moieties in the polymeric chain. This is determined by the oxidant/dopant used in the polymer synthesis (FeCl3 or K2S2O8). The degree of oxidation of PPy can also be modified by a plasma treatment of the polymer, which determines the ability of PPy to carry out the reduction of nitrate by the electrons provided by the polymeric chain and also affects the selectivity of the nitrate reduction. Financial support from Generalitat Valenciana, Spain (PROMETEOII/2014/004) and Ministry of Economy and Competitiveness (MAT2016-80285-P) is gratefully acknowledged.

CO2 utilisation is becoming an appealing topic in catalysis science due to the urgent need to deal with greenhouse gases (GHG) emissions. Herein, the dry reforming of methane (DRM) represents a viable route to convert CO2 and CH4 (two of the major GHG) into syngas, a highly valuable intermediate in chemical synthesis. Nickel-based catalysts are economically viable materials for this reaction, however they show inevitable signs of deactivation. In this work stabilisation of Ni in a pyrochlore-perovskite structure is reported as a viable method to prevent fast deactivation. Substitution of Zirconium by Ni at various loadings in the lanthanum zirconate pyrochlore La2Zr2O7 is investigated in terms of reactant conversions under various reaction conditions (temperature and space velocity). XRD analysis of the calcined and reduced catalysts showed the formation of crystalline phases corresponding to the pyrochlore structure La2Zr2-xNixO7-δ and an additional La2NiZrO6 perovskite phase at high Ni loadings. Carbon formation is limited using this formulation strategy and, as a consequence, our best catalyst shows excellent activity for DRM at temperatures as low as 600 °C and displays great stability over 350 h of continuous operation. Exsolution of Ni from the oxide structure, leading to small and well dispersed Ni clusters, could explain the enhanced performance. Financial support for this work was provided by the Department of Chemical and Process Engineering of the University of Surrey and the EPSRC grants EP/J020184/2 and EP/R512904/1 as well as the Royal Society Research Grant RSGR1180353. Authors would also like to acknowledge the Ministerio de Economía, Industria y Competitividad of Spain (Project MAT2013-45008-P).

Herein, we have studied an alternative route for preparing CuOx/CeO2 catalysts using metal organic frameworks (MOFs) as precursors. Usually, CuOx/CeO2 materials are prepared by wet impregnation of ceria support. In this study, we have impregnated a Cu-MOF with a ceria precursor and then pyrolized the impregnated MOF using different conditions and procedures. The prepared catalysts have been characterized by using a wide range of techniques such as XRD, XPS, Raman, and TPR. We have found that the pyrolysis method determines the dispersion of the oxidized copper species on the ceria surface what, in turn, controls the catalytic activity and selectivity of the catalysts in the reverse water-gas shift (RWGS) reaction. We have compared the behavior of the MOF-derived catalysts against an optimized catalyst prepared by a conventional method (wet impregnation), finding that the MOF-derived catalyst shows better catalytic performance. Financial support from Generalitat Valenciana (project PROMETEOII/2014/004) and MINECO (Project MAT2013-45008-P) is gratefully acknowledged. EVRF also thanks MINECO for his Ramon y Cajal fellow RYC-2012-11427 and the following project MAT2016-81732-ERC.

We report a facile and general approach for preparing ultrafine ruthenium nanocatalysts by using a plasma-assisted synthesis at

Three different conducting polymers, polythiophene (PT), polypirrol (PPY) and polyaniline (PANI) have been synthesized via oxidative chemical polymerization in aqueous media, in such a way that the synthesis protocol did not involve any toxic solvents. They have been tested in the abatement of nitrates from an aqueous solution without the need of any metal catalyst. The N-containing polymers (PANI and PPy) were able to remove nitrates to a level that accomplishes the European legislation requirements; however, the nature of each polymer greatly influenced the process mechanism. Whereas ion exchange between Cl- and SO42- counter-ions in the polymer and NO3- from water is the main responsible for the effective nitrate removal in PANI, as assessed by FTIR and XPS analyses, the nitrate removal mechanism on PPy is based in an electron transfer from the polymer to nitrate through N sites located in the pyrrolic ring. On the other hand, PT was not able to exchange nitrate unless it was synthesized with FeCl3 as oxidant/dopant and an anionic surfactant (sodium dodecyl sulfate -SDS-) is used. In that case, the electrostatic attraction between sulfate (OSO3-) groups from the surfactant and Fe3+ ions from FeCl3 produced the anchoring of Cl- to the oxidized PT growing chain, this favoring ion exchange with nitrate in the aqueous solution, followed by a redox process. Financial support from Generalitat Valenciana, Spain (PROMETEOII/2014/004) is gratefully acknowledged.

MAX (Mn+1AXn) phases are layered carbides or nitrides with a high thermal and mechanical bulk stability. Recently, it was shown that their surface structure can be modified to form a thin non‐stoichiometric oxide layer, which can catalyze the oxidative dehydrogenation of butane. Here, the use of a Ti2AlC MAX phase as a support for cobalt oxide was explored for the dry reforming of butane with CO2, comparing this new catalyst to more traditional materials. The catalyst was active and selective to synthesis gas. Although the surface structure changed during the reaction, the activity remained stable. Under the same conditions, a titania‐supported cobalt oxide catalyst gave low activity and stability due to the agglomeration of cobalt oxide particles. The Co3O4/Al2O3 catalyst was active, but the acidic surface led to a faster deactivation. The less acidic surface of the Ti2AlC was better at inhibiting coke formation. Thanks to their thermal stability and acid‐base properties, MAX phases are promising supports for CO2 conversion reactions., Take it to the MAX: The reaction of carbon dioxide with butane to give syn‐gas is a valid method for converting CO2 into something useful and is catalyzed efficiently by cobalt oxide supported on a MAX phase.

Bio-hydrogenated diesel (BHD), derived from vegetable oil via hydrotreating technology, is a promising alternative transportation fuel to replace nonsustainable petroleum diesel. In this work, a novel Pt-based catalyst supported on N-doped activated carbon prepared from polypyrrole as the nitrogen source (Pt/N-AC) was developed and applied in the palm oil deoxygenation process to produce BHD in a fixed bed reactor system. High conversion rates of triglycerides (conversion of TG > 90%) and high deoxygenation percentage (DeCOx% = 76% and HDO% = 7%) were obtained for the palm oil deoxygenation over Pt/N-AC catalyst at optimised reaction conditions: T = 300 °C, 30 bar of H2, and LHSV = 1.5 h−1. In addition to the excellent performance, the Pt/N-AC catalyst is highly stable in the deoxygenation reaction, as confirmed by the XRD and TEM analyses of the spent sample. The incorporation of N atoms in the carbon structure alters the electronic density of the catalyst, favouring the interaction with electrophilic groups such as carbonyls, and thus boosting the DeCOx route over the HDO pathway. Overall, this work showcases a promising route to produce added value bio-fuels from bio-compounds using advanced N-doped catalysts. This research was funded by the Department of Chemical and Process Engineering of the University of Surrey and the EPSRC grants EP/J020184/2 and EP/R512904/1 as well as the Royal Society Research Grant RSGR1180353. Authors would also like to acknowledge the Ministerio de Economía, Industrial Competitividad of Spain (Project MAT2016-80285-P) and the Chinese Scholarship Council (CSC). L.P.-P. also thanks Comunitat Valenciana for her postdoctoral fellow APOSTD2017. K.P. is grateful for the support of the Hellenic Foundation for Research and Innovation (HFRI) and the General Secretariat for Research and Technology (GSRT), under the HFRI PhD Fellowship grant (GA. No. 359). The APC was funded by University of Surrey.

This work showcases an innovative route for biocompound upgrading via hydrodeoxygenation (HDO) reactions, eliminating the need for external high-pressure hydrogen supply. We propose the use of water as reaction media and the utilization of multifunctional catalysts that are able to conduct multiple steps such as water activation and HDO. In this study, we validate our hypothesis in a high-pressure batch reactor process using guaiacol as a model compound and multicomponent Ni-based catalysts. In particular, a comparison between ceria-supported and carbon/ceria-supported samples is established, the carbon-based materials being the suitable choice for this reaction. The physicochemical study by X-ray photoelectron spectroscopy, transmission electron microscopy, X-ray diffraction, and temperature-programmed reduction reveals the greater dispersion of Ni clusters and the strong metal-support interaction in the carbon/ceria-based samples accounting for the enhanced performance. In addition, the characterization of the spent samples points out the resistance of our catalysts toward sintering and coking. Overall, the novel catalytic approach proposed in this paper opens new research possibilities to achieve low-cost bio-oil upgrading processes. Financial support for this work was provided by the Department of Chemical and Process Engineering of the University of Surrey and the EPSRC grants EP/J020184/2 and EP/R512904/1 as well as the Royal Society Research grant RSGR1180353. Authors would also like to acknowledge the Ministerio de Economía, Industrial Competitividad of Spain (project MAT2016-80285-P) and the Chinese Scholarship Council (CSC). L.P.-P. also thanks Comunitat Valenciana for her postdoctoral fellow APOSTD2017.

Microporous activated carbons were prepared from date pits using thermal activation with CO2 or steam. The adsorbents were characterized by N2 and CO2 adsorption at 77 K and 273K, respectively. The H2 adsorption was measured at 298K and 100 bar using a volumetric equipment. To increase the hydrogen storage, activated carbons are doped by metals. The results show that the H 2 adsorption capacity is influenced by the size and volume of micropores in the activated carbon adsorbent. A relationship between hydrogen adsorption capacity calculated using Langmuir isotherm and the volume of narrow micropores deduced from the CO2 adsorption isotherm at 273 K was found. A correlation was also found between both micropore volumes and the amount of hydrogen adsorbed at 298 K and 100 bar. Additionally, vanadium doping of activated carbons could positively influence hydrogen adsorption.

We studied the catalytic hydrogenation of CO2 to methane using nickel-niobia composite catalysts. Catalysts containing 10–70 wt% Ni were synthesized by wet impregnation and tested for CO2 hydrogenation in a flow reactor. 40 wt% was found to be the optimum Ni loading, which resulted in CO2 conversion of 81% at 325 °C. We also calcined the Nb2O5 support at different temperatures to study the influence of calcination temperature on the catalytic performance. 40 wt% Ni loaded on Nb2O5, which was calcined at 700 °C gave higher methanation activity (91% conversion of CO2). Time on stream study for 50 h showed a stable activity and selectivity; thus confirming the scope for practical application. E.S.G. and N.R.S acknowledge the financial support from NOW CAPITA project (732.013.002). ASE acknowledges the financial support from the MINECO projects MAT-2013-45008-P and MAT2016-81732-ERC. EVRF gratefully acknowledge support from MINECO for his Ramón y Cajal grant (RyC-2012-11427) and University of Alicante for the project GRE-13-31. Generalitat Valenciana is also acknowledged for financial support (PROMETEOII/ 2014/004).

Offsetting the impact of human activities on the biogeochemical cycle of mercury has become necessary for a sustainable planet. Herein, we report the development of a water-stable and eco-friendly metal–organic framework, which has the formula {Cu4II[(S,S)-methox]2}·5H2O (1), where methox is bis[(S)-methionine]oxalyl diamide. Its features include narrow functional channels decorated with thioalkyl chains, which are able to capture HgCl2 from aqueous media in an efficient, selective, and rapid manner. The conscious design effort in terms of size, shape, and reactivity of the channels results in extremely efficient immobilization of HgCl2 guest species in a very stable conformation, similar to that of the enzyme mercury reductase. Thus, 1 enables the highly efficient removal of toxic HgCl2 from aqueous media and reduces the [Hg2+] concentration from the dangerous level of 10 ppm to acceptable limits of below 2 ppb in drinking water. The unusual combination of a low-cost straightforward synthetic procedure and high stability under environmental conditions, together with its ability to efficiently and rapidly remove poisonous mercury ions, places 1 among the most attractive adsorbents reported to date for the purification of contaminated water. This work was supported by the MINECO (Spain) (Project CTQ2016-75671-P and Excellence Unit “Maria de Maeztu” MDM-2015-0538), the Generalitat Valenciana (Spain) (Project PROMETEOII/2014/070), and the Ministero dell'Istruzione, dell'Università e della Ricerca (Italy). M. M. and X. Q. thank the MINECO and the China Scholarship Council for grants. Thanks are also extended to the Ramón y Cajal program (E. P and E. V. R.-F.).

Commercial carbon nanotubes have been oxidized with HNO3, H2O2 and air and they have been tested on the cyclization of citronellal. The materials have been characterized by N2 adsorption/desorption isotherms, transmission electron microscopy, X-ray diffraction, temperature programmed desorption, potentiometry titration and X-ray photoelectron spectroscopy. The HNO3-treated samples displayed the largest concentration of carboxylic acids which increased by increasing the oxidation time and by a previous ball-milling treatment. The carboxylic acid groups were found to be the active groups on the reaction and the activity increased by increasing its content. The selectivity to isopulegols was higher (98%) over the most active samples (activity 0.20–0.68 mmol/g min), which has been explained by their smaller pore size caused by the oxidation treatment. The stability of the most active CNT sample was also proved by recycling the catalyst in 3 cycles. Financial support for the present study was received from CON-ICYT Chile, project 3130483 (Postdoctoral), Generalitat Valenciana, Spain (PROMETEOII/2014/004) is also gratefully acknowledged.

The low temperature water-gas shift (WGS) reaction has been studied over two commercial multiwall carbon nanotubes-supported nickel catalysts promoted by ceria. For comparison purposes, activated carbon-supported catalysts have also been studied. The catalytic performance and the characterization by N2 adsorption analysis, powder X-ray diffraction (XRD), temperature-programmed reduction with H2 (TPR-H2), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analysis showed that the surface chemistry has an important effect on the dispersion of ceria. As a result, ceria was successfully dispersed over the carbon nanotubes (CNTs) with less graphitic character, and the catalyst afforded better activity in WGS than the catalyst prepared over massive ceria. Moreover, a 20 wt.% CeO2 loading over this support was more active than the analogous catalyst with a 40 wt.% loading. The ceria nanoparticles were smaller when the support was previously oxidized, however this resulted in a decrease of the activity. Financial support from CONICYT (Chile, Postdoc FONDECYT 3130483), Ministerio de Economía y Competitividad (Spain, MAT2010-21147 and MAT2013-45008-P) and Generalitat Valenciana (Spain, PROMETEOII/2014/004) is gratefully acknowledged.

Pd nanoparticles have been synthesized over carbon nanotubes (CNT) and graphite oxide (GO) by reduction with ethylene glycol and by conventional impregnation method. The catalysts were tested on the chemoselective hydrogenation of p-chloronitrobenzene and the effect of the synthesis method and surface chemistry on their catalytic performance was evaluated. The catalysts were characterized by N2 adsorption/desorption isotherms at 77 K, TEM, powder X-ray diffraction, thermogravimetry, infrared and X-ray photoelectron spectroscopy and ICP-OES. It was observed that the synthesis of Pd nanoparticles employing ethylene glycol resulted in metallic palladium particles of smaller size compared to those prepared by the impregnation method and similar for both supports. The presence of oxygen groups on the support surface favored the activity and diminished the selectivity. It seems that ethylene glycol reacted with the surface groups of GO, this favoring the selectivity. The activity was higher over the CNT-based catalysts and both catalysts prepared by reduction in ethylene glycol were quite stable upon recycling. Financial support for the present study was received from CON-ICYT Chile, project 3130483 (Postdoctoral), Generalitat Valenciana, Spain (PROMETEOII/2014/004) is also gratefully acknowledged.

A comparative study of three different ceria synthesis procedures (template- and MW- assisted hydrothermal synthesis and urea homogeneous precipitation) is reported in this paper. The obtained materials were employed as supports for Pt nanoparticles, and the Pt/CeO2 catalysts were evaluated in the WGS reaction under model and realistic conditions. The influence of the support, e.g., its morphology and electronic properties, has been studied in detail by means of XRD, H2-TPR, XPS, UV–Vis spectroscopy and toluene hydrogenation (for metal dispersion assessment). The catalytic performance of the samples is directly correlated with the modification of the electronic properties, as a result of the preparation method used. The conventional homogeneous precipitation method with urea resulted to be the best option, leading to enhanced ceria reducibility and adequate Pt dispersion, which in turns resulted in a very efficient WGS catalyst. Financial support from Generalitat Valenciana (project PROMETEOII/2014/004) and MINECO (projects MAT2013-45008-P and MAT2017-86992-R) are gratefully acknowledged. EVRF also thanks MINECO for his Ramon y Cajal fellow RYC-2012-11427 and the MAT2016-81732-ERC project. LPP also thanks Generalitat Valenciana for her postdoctoral fellow APOSTD2017.

Materials able to produce the reduction of nitrate from water without the need of a metal catalyst and with avoiding the use of gaseous hydrogen have been developed by combining the synergistic properties of titania and two conducting polymers. Polymerization of aniline and pyrrol on titanium dioxide in the presence of two different oxidants/dopants (iron trichloride or potassium persulfate) has been evaluated. The resulting hybrid materials have good thermal stability imparted by the titania counterpart, and a considerable conductivity provided by the conducting polymers. The capability of the hybrid materials of reducing aqueous nitrate has been assessed and compared to the catalytic hydrogenation of nitrate using a platinum catalyst supported on these hybrid synthesized materials. The mechanism of nitrate abatement implies adsorption of nitrate on the polymer by ion exchange with the dopant anion, followed by the reduction of nitrate. The electron transfer from titania to the conducting polymer in the hybrid material favors the reductive ability of the polymer, in such a way that nitrate is selectively reduced with a very low production of undesirable side products. The obtained results show that the activity and selectivity of the catalytic reduction of nitrate with dihydrogen in the presence of a platinum catalyst supported on the hybrid materials are considerably lower than those of the metal-free nanocomposites. Financial support from Generalitat Valenciana, Spain (PROMETEOII/2014/004) and Ministry of Economy and Competitivity (MAT2016-80285-P) is gratefully acknowledged. E.S. acknowledges the Spanish MINECO and AEI/FEDER (ref CTQ2015-74494-JIN) and the University of Alicante (ref UATALENTO16-03).

The RWGS reaction represents a direct approach for gas-phase CO2 upgrading. This work showcases the efficiency of Fe/CeO2-Al2O3 catalysts for this process, and the effect of selected transition metal promoters such as Cu, Ni and Mo. Our results demonstrated that both Ni and Cu remarkably improved the performance of the monometallic Fe-catalyst. The competition Reverse Water-Gas Shift (RWGS) reaction/CO2 methanation reaction was evident particularly for the Ni-catalyst, which displayed high selectivity to methane in the low-temperature range. Among the studied catalysts the Cu promoted sample represented the best choice, exhibiting the best activity/selectivity balance. In addition, the Cu-doped catalyst was very stable for long-term runs – an essential requisite for its implementation in flue gas upgrading units. This material can effectively catalyse the RWGS reaction at medium-low temperatures, providing the possibility to couple the RWGS reactor with a syngas conversion reaction. Such an integrated unit opens the horizons for a direct CO2 to fuels/chemicals approach. Financial support for this work was provided by the Department of Chemical and Process Engineering of the University of Surrey and the EPSRC grants EP/J020184/2 and EP/R512904/1 as well as the Royal Society Research Grant RSGR1180353. Authors would also like to acknowledge the Ministerio de Economía, Industrial Competitividad of Spain (Project MAT2016-80285-P). LPP also thanks Generalitat Valenciana for her postdoctoral fellow APOSTD2017.

Platinum nanoparticles have been synthesized on polyaniline (PANI) and polypyrrole (PPy) as supports using H2PtCl6 as metal precursor and a reducing treatment with cold Ar plasma. The catalytic activity of the polymer-supported catalysts in the reduction of aqueous nitrate with H2 at room temperature was evaluated. These systems are able to considerably decrease the concentration of nitrate in water in only 5 min. The mechanism of the nitrate abatement process is determined by the nature of the conducting polymer. The nitrogen functionalities in polyaniline are external to the ring system, and favor nitrate retention at the platinum complex either by the formation of an adduct or by nitrate participating as a ligand. In contrast, polypyrrole possesses aromatic nitrogen atoms with a considerably more important steric hindrance. In this case, ion exchange between the counter ions in the doped polymer (SO42−) and nitrate from water is produced, followed by reduction of nitrate by hydrogen chemisorbed on the platinum nanoparticles. Financial support from Generalitat Valenciana, Spain (PROMETEOII/2014/004) is gratefully acknowledged.

In the context of Carbon Capture and Utilisation (CCU), the catalytic reduction of CO2 to CO via reverse water-gas shift (RWGS) reaction is a desirable route for CO2 valorisation. Herein, we have developed highly effective Ni-based catalysts for this reaction. Our study reveals that CeO2-Al2O3 is an excellent support for this process helping to achieve high degrees of CO2 conversions. Interestingly, FeOx and CrOx, which are well-known active components for the forward shift reaction, have opposite effects when used as promoters in the RWGS reaction. The use of iron remarkably boosts the activity, selectivity and stability of the Ni-based catalysts, while adding chromium results detrimental to the overall catalytic performance. In fact, the iron-doped material was tested under extreme conditions (in terms of space velocity) displaying fairly good activity/stability results. This indicates that this sort of catalysts could be potentially used to design compact RWGS reactors for flexible CO2 utilisation units. Financial support for this work was provided by the Department of Chemical and Process Engineering at the University of Surrey and the EPSRC projects EP/J020184/2 and EP/R512904/1 as well as the Royal Society Research Grant RSGR1180353. The Spanish team acknowledges Ministerio de Economia, Industria y Competitividad of Spain (Project MAT2013-45008-P). LPP also thanks Comunitat Valenciana for her postdoctoral fellow (APOSTD2017).

A detailed study on the preparation of bimetallic PtSn/C catalysts using surfacecontrolled synthesis methods, and on their catalytic performance in the glycerol steam reforming reaction has been carried out. In order to obtain these well-defined bimetallic phases, techniques derived from Surface Organometallic Chemistry of Metals (SOMC/M) were used. The preparation process involved the reaction between an organometallic compound ((C4H9)4Sn) and a supported transition metal (Pt) in a H2 atmosphere. Catalysts with Sn/Pt atomic ratios of 0.2, 0.3, 0.5, and 0.7 were obtained, and characterized using several techniques: ICP, H2 chemisorption, TEM and XPS. These systems were tested in the glycerol steam reforming varying the reaction conditions (glycerol concentration and reaction temperature). The best performance was observed for the catalysts with the lowest tin contents (PtSn0.2/C and PtSn0.3/C). It was observed that the presence of tin increased the catalysts’ stability when working under more severe reaction conditions., Centro de Investigación y Desarrollo en Ciencias Aplicadas

The low temperature water–gas shift (WGS) reaction has been studied over Ni–CeO2/Graphene and Ni/Graphene. The catalysts were prepared with 5 wt.% Ni and 20 wt.% CeO2 loadings, by deposition-precipitation employing sodium hydroxide and urea as precipitating agents. The materials were characterized by TEM, powder X-ray diffraction, Raman spectroscopy, H2-temperature-programmed reduction and X-ray photoelectron spectroscopy (XPS). The characterization and the reaction results indicated that the interaction between the active species and the support is higher than with activated carbon, and this hinders the reducibility of ceria and thus the catalytic performance. On the other hand, the presence of residual sodium in samples prepared by precipitation with NaOH facilitated the reduction of ceria. The catalytic activity was highly improved in the presence of sodium, what can be explained on the basis of an associative reaction mechanism which is favored over Ni-O-Na entities. Authors thank to CONICYT (Chile, Postdoc FONDECYT 3130483) and Ministerio de Economía y Competitividad (Spain, MAT2010-21147 and MAT2013-45008-P) for financial support.

Copper-based catalysts supported on niobium-doped ceria have been prepared and tested in the preferential oxidation of CO in excess of H2 (PROX) and in total oxidation of toluene. Supports and catalysts have been characterized by several techniques: N2 adsorption, ICP-OES, XRF, XRD, Raman Spectroscopy, SEM, TEM, H2-TPR and XPS, and their catalytic performance has been measured in PROX, with an ideal gas mixture (CO, O2 and H2) with or without CO2 and H2O, and in total oxidation of toluene. The effects of the copper loading and the amount of niobium in the supports have been evaluated. Remarkably, the addition of niobia to the catalysts may improve the catalytic performance in total oxidation of toluene. It allows us to prepare cheaper catalysts (niobia it is far cheaper than ceria) with improved catalytic performance. The authors gratefully acknowledge the financial support from MINECO (Spain, Project MAT2010-21147)8/346) and Generalitat Valenciana (PROMETEOII/2014/004). EVRF thanks the MINECO for his Ramón y Cajal Fellow RYC-2012-11427. EOJ thanks the CNPq –Brazil for her grant.

In this work, the WGS performance of a conventional Ni/CeO2 bulk catalyst is compared to that of a carbon-supported Ni-CeO2 catalyst. The carbon-supported sample resulted to be much more active than the bulk one. The higher activity of the Ni-CeO2/C catalyst is associated to its oxygen storage capacity, a parameter that strongly influences the WGS behavior. The stability of the carbon-supported catalyst under realistic operation conditions is also a subject of this paper. In summary, our study represents an approach towards a new generation of Ni-ceria based catalyst for the pure hydrogen production via WGS. The dispersion of ceria nanoparticles on an activated carbon support drives to improved catalytic skills with a considerable reduction of the amount of ceria in the catalyst formulation., We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI)., Financial support of Ministerio de Ciencia e Innovacion of Spain (Project MAT2010-21147) is gratefully acknowledged. L.P.P. acknowledges her grant BES-2011-0406508. The Spanish Ministerio de Economía y Competitividad (MINECO) is also acknowledged for the funding linked to the projects ENE2012-374301-C03-01 and ENE2013-47880-C3-2-R.

Catalysts consisting in platinum supported on cerium oxide highly dispersed on activated carbon, with a Pt loading of 1 wt.% and ceria loadings of 5, 10 and 20 wt.% have been prepared by impregnation method and characterized by several techniques (N2 adsorption at 77 K, ICP, XRD, H2-TPR and XPS). Their catalytic behavior has been evaluated in the total oxidation of ethanol and toluene after reduction at 473 K. The obtained results show that the prepared catalysts have better performances than platinum supported on bulk CeO2. The best catalytic performance was obtained for 10 wt.% ceria loading, likely due to an optimum synergistic interaction between highly dispersed cerium oxide and platinum particles. Pt-10Ce/C achieves total conversion of ethanol and toluene to CO2 at 433 K and 453 K, respectively, and shows no deactivation during a test for 100 h. Under humid conditions (relative humidity, RH, of 40 and 80%), the activity was only slightly influenced due to the hydrophobic character of the activated carbon support, which prevents the adsorption of water. Financial support from Generalitat Valenciana (Spain, PROMETEO/2009/002-FEDER and PROMETEOII/2014/004) is gratefully acknowledged.

We analyzed the adsorption of CO2 in a Cu-BTC metal-organic framework (MOF) impregnated with ionic liquids (ILs) experimentally and by molecular simulation using the Monte Carlo method. The ILs [bmim][PF6] and [bmim][Tf2N] were impregnated in concentrations of 1, 5 and 10 wt%. Monte Carlo computations showed maximum impregnation load of approximately 30 wt% and improved CO2 adsorption up to 2 bar for all the concentrations tested. Experimentally, the impregnated material was carefully characterized and CO2 isotherms were measured. High concentrations of IL solution (10 wt%) had a pronounced detrimental effect on the textural properties of Cu-BTC, whereas for low concentration (5 wt%), no improvement in CO2 adsorption was observed. Based on the experimental and simulated data, the suitability of Cu-BTC as a target MOF for IL impregnation was examined. This work was supported by the Brazilian research agencies, CNPq and CAPES. E.O. Jardim thanks the CNPq (Brazil) for her grant.

The effect of Ar plasma treatment on the catalytic performance of Pt/CeO2 has been studied. The catalyst was activated using different procedures separately or in combination: calcination, reduction under pure H2 and cold Ar plasma treatment. The resulting materials were characterized by X-ray photoelectron spectroscopy, X-ray adsorption near edge structure and temperature-programmed reduction with H2. The resulting materials were tested in the water-gas shift reaction (WGS). It has been found that the combination of calcination, plasma and hydrogen treatments leads to a very active catalyst for WGS. Furthermore, the catalyst structure–performance relationship has been assessed. The plasma treatment generated electron-enriched Pt particles which show a very strong interaction with the ceria support. This favoured CO chemisorption and increased the reducibility of the support, which takes part in the WGS the reaction by favouring water splitting. Financial support from Generalitat Valenciana (project PROMETEOII/2014/004) and MINECO (Project MAT2013-45008-P) is gratefully acknowledged. EVRF also thanks MINECO for his Ramon y Cajal fellow RYC-2012-11427 and the following project MAT2016-81732-ERC.

In this work, we have prepared two series of layered double hydroxides (LDHs) based on three different divalent cations (Zn2+, Ni2+ and Mg2+), that were ion-exchanged by a trivalent cation (Al3+). The charge was balanced with interlayer anions, either silicate or carbonate. Thus, we have synthetized six different samples and we have studied their physicochemical properties by a wide range of techniques, in order to elucidate their properties. Finally, we have used the prepared materials as catalysts in the transesterification of ethylene carbonate with methanol to produce dimethyl carbonate and ethylene glycol. We have found that materials containing Ni as divalent cation present better catalytic activity due to their basic properties, whereas catalysts containing silicate as interlayer anion yield better selectivity, since they have a lower amount of acid sites. The authors acknowledge financial support from the MINECO projects MAT-2013-45008-P, MAT2016-81732-ERC. EVRF gratefully acknowledge support from MINECO for his Ramón y Cajal grant (RyC-2012-11427) and University of Alicante for the project GRE-13-31. Generalitat Valenciana is acknowledges for support (PROMETEOII/2014/004). JGL Fellowship for National Master Studies 2014 of the National Council of Science and Technology (CONACYT), Mexico.

[EN] Heterogeneous single-site catalysts consist of isolated, well-defined, active sites that are spatially separated in a given solid and, ideally, structurally identical. In this review, the potential of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) as platforms for the development of heterogeneous single-site catalysts is reviewed thoroughly. In the first part of this article, synthetic strategies and progress in the implementation of such sites in these two classes of materials are discussed. Because these solids are excellent playgrounds to allow a better understanding of catalytic functions, we highlight the most important recent advances in the modelling and spectroscopic characterization of single-site catalysts based on these materials. Finally, we discuss the potential of MOFs as materials in which several single-site catalytic functions can be combined within one framework along with their potential as powerful enzyme-mimicking materials. The review is wrapped up with our personal vision on future research directions., S. M. J. Rogge, J. Hajek, and V. Van Speybroeck acknowledge the Fund for Scientific Research - Flanders (FWO), the Research Board of Ghent University (BOF) and BELSPO in the frame of IAP/7/05 for financial support. V. Van Speybroeck acknowledges funding from the European Union's Horizon 2020 research and innovation programme (consolidator ERC grant agreement no. 647755 - DYNPOR (2015-2020)). This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement no. 641887 (project acronym: DEFNET). W. Dewitte and C. Caratelli are acknowledged for technical support with the figures. J. Gascon acknowledges funding from the European Union's 2020 research and innovation programme (ERC grant agreement no. 335746 - CrystEng-MOF-MMM) and from the Dutch Organization for Scientific Research (NWO, VIDI grant agreement 723.012.107 - MetMOFCat).

The low temperature water–gas shift (WGS) reaction has been studied over carbon-supported nickel catalysts promoted by ceria. To this end, cerium oxide has been dispersed (at different loadings: 10, 20, 30 and 40 wt.%) on the activated carbon surface with the aim of obtaining small ceria particles and a highly available surface area. Furthermore, carbon- and ceria-supported nickel catalysts have also been studied as references. A combination of N2 adsorption analysis, powder X-ray diffraction, temperature-programmed reduction with H2, X-ray photoelectron spectroscopy and TEM analysis were used to characterize the Ni–CeO2 interactions and the CeO2 dispersion over the activated carbon support. Catalysts were tested in the low temperature WGS reaction with two different feed gas mixtures: the idealized one (with only CO and H2O) and a slightly harder one (with CO, CO2, H2, and H2O). The obtained results show that there is a clear effect of the ceria loading on the catalytic activity. In both cases, catalysts with 20 and 10 wt.% CeO2 were the most active materials at low temperature. On the other hand, Ni/C shows a lower activity, this assessing the determinant role of ceria in this reaction. Methane, a product of side reactions, was observed in very low amounts, when CO2 and H2 were included in the WGS feed. Nevertheless, our data indicate that the methanation process is mainly due to CO2, and no CO consumption via methanation takes place at the relevant WGS temperatures. Finally, a stability test was carried out, obtaining CO conversions greater than 40% after 150 h of reaction. Financial support of Ministerio de Ciencia e Innovación of Spain (Project MAT2010-21147) is gratefully acknowledged. L.P.P. acknowledges her grant BES-2011-0406508.

Platinum nanoparticles supported on titania efficiently catalyzed the diboration of alkynes and alkenes under solvent- and ligand-free conditions in air. The cis-1,2-diborylalkenes and 1,2-diborylalkanes were obtained in moderate to excellent yields following, in most cases, a simple filtration workup protocol. The versatility of the cis-1,2-diboronvinyl compounds was demonstrated in a series of organic transformations, including the Suzuki–Miyaura cross coupling and the boron–halogen exchange. This work was generously supported by the Spanish Ministerio de Economía y Competitividad (MINECO; CTQ2007-65218 and CTQ2011-24151), the Generalitat Valenciana (GV; PROMETEO/2009/002 and PROMETEO/2009/039), and FEDER.

Steam reforming of glycerol to produce syngas or H2-enriched streams is a promising route that has caught the attention of many researchers around the world. This reaction is typically carried out over metal-based catalysts supported on stable materials. Herein we report a study on the effect of Sn on the catalytic properties of Pt/C in the aforementioned reaction. A series of Pt-Sn/C catalysts with different Pt:Sn ratios were prepared and characterized using ICP, H2-TPR, TEM and XPS techniques, and they were tested in the glycerol steam reforming reaction at 623 K and atmospheric pressure. The best performance was observed for the catalysts with low tin contents. It was found that Sn promoted oxidation reactions and inhibited methanation. Furthermore, the presence of Sn improved the stability of the catalysts when operating at harsher conditions of temperature and glycerol concentration. A promoter effect of Sn hindering platinum sintering and the formation of coke precursors is proposed as the origin of the observed behaviour. This work has been supported by Ministerio de Economía y Competitividad (Spain, Project MAT2010-21147). L.P.P. acknowledges her grant BES-2011-0406508.

Cu-ZnO based catalysts are the benchmark materials for the low-temperature WGS reaction. However, they present a crucial drawback which limits their application in portable devices: they only work under very low space velocities. In this study, we have developed a series of multicomponent Cu-ZnO catalysts able to work at relatively high space velocities with outstanding activity and stability. Different reference supports have been utilised with CeO2-Al2O3 being the most promising system. Overall, this work describes a strategy to design advanced Cu-based catalysts that can overcome the residence time restrictions in the WGS reaction. Financial support for this work was provided by the Department of Chemical and Process Engineering at the University of Surrey. The Spanish team acknowledges Ministerio de Economía, Industria y Competitividad of Spain (Project MAT2013-45008-P).

In this work, the low-temperature hydrogen production via glycerol steam reforming over activated carbon-supported Ni and Ni-Sn catalysts promoted by ceria was studied. A combination of N2 adsorption, powder X-ray diffraction, temperature-programmed reduction with H2, X-ray photoelectron spectroscopy and TEM analysis were used to characterise the Ni-Sn-CeO2 interactions and the CeO2 dispersion over the activated carbon support. The catalytic activity results show that the presence of ceria enhances the water-gas shift reaction, thus promoting the selectivity towards hydrogen. The inclusion of Sn stresses the influence of ceria in the displayed performance. Moreover, the formation of a Ni-Sn alloy seems to be an efficient way to mitigate Ni sintering and therefore to improve the overall catalyst’s stability. This work has been supported by Ministerio de Economía y Competitividad (Spain, project MAT2013-45008-P). L. P-P. acknowledges her grant BES-2011-0406508.

Ni nanoparticles have been selectively loaded inside or outside commercial carbon nanotubes by the wet impregnation method, and their catalytic performance on the conversion of guaiacol in batch reactor at 5 MPa and 573 K has been studied. Different characterization techniques were used to investigate the effect of confinement in nanotubes. The catalysts showed different selectivity to cyclohexene compared to cyclohexane was enhanced when the nanoparticles were loaded inside. This result was attributed to the different adsorption mode of the molecule inside the nanotubes. Financial support for the present study was received from CONICYT Chile, projects FONDECYT Nº1140528 and 3130483 (Postdoctoral), PFB-27, FONDEQUIP EQM 120096 Grants. Financial support from Generalitat Valenciana, Spain (PROMETEOII/2014/004) is also gratefully acknowledged.

The effect of the textural properties of a series of commercial carbon molecular sieves (CMS), prepared from different polymeric precursors, on their ability for CO2 adsorption at different temperatures has been studied. The adsorbents have been characterized by N2 and CO2 adsorption at 77 and 273 K, respectively, together with measurements of immersion calorimetry into liquids of different molecular dimensions. The studied CMSs cover a wide range of porosity, from purely microporous carbons to samples containing wide micropores as well as a certain proportion of mesoporosity. Studies of CO2 adsorption, at atmospheric pressure (1 bar) and three different temperatures (273, 298 and 323 K), have shown that a high CO2 adsorption capacity requires the presence of a well-developed microporosity, as well as a high volume of narrow micropores. On the other hand, narrow micropores seem to be the key factor leading to a maximum capacity of CO2 adsorption, even at temperatures close to that of anthropogenic emissions of CO2.

Ni-based catalysts supported on Zn-modified alumina were investigated in the ethanol steam reforming reaction. A commercial γ-alumina was impregnated with different amounts of zinc nitrate (0, 2, 5, 10, 15, 20 wt.% on Zn basis), calcined, and then impregnated with nickel nitrate aqueous solutions. The samples were characterized by a number of techniques: N(2) adsorption at 77 K, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray fluorescence (XRF), and temperature-programmed reduction (TPR). Their catalytic behavior in the ethanol steam reforming reaction was studied at 873 K, with a H(2)O/ethanol ratio of 5:1. Two effects of the presence of Zn were detected. On the one hand, zinc modifies the surface structure and the surface chemistry of the catalysts by formation of zinc aluminates, and on the other hand, zinc oxide can be reduced to metallic zinc under reaction conditions, thus modifying the catalytic properties of the active phase. The presence of Zn increases the ethanol conversion to gaseous compounds as compared with the catalyst supported on the Zn-free commercial alumina. The addition of a small amount of Pt (1 wt.%) causes a beneficial effect in the reaction. When Ni catalysts were used without a previous reduction treatment, ethylene was formed in high amounts; however, the Pt-Ni catalysts need no reduction pre-treatment to achieve high H(2) yields (close to 70%) and showed a high stability versus time on stream because of the control of the production of ethylene, a coke precursor.

Titania-supported platinum (mainly as Pt(II)) has been found to effectively catalyze the hydrosilylation of 1,3-diynes at 70 °C with low catalyst loading (0.25 mol %) under solvent-free conditions. Monohydrosilylation was achieved for diaryl-substituted diynes, whereas dialkyl-substituted diynes were transformed into the corresponding dihydrosilylated products in good yields. In every case, the process was proven to be highly stereoselective, with syn addition of the silicon–hydrogen bond, and regioselective, with the silicon moiety exclusively bonded to the most internal carbon atom of the 1,3-diyne (β-E product), as confirmed by X-ray crystallography. This work was generously supported by the Spanish Ministerio de Ciencia e Innovación (MICINN; CTQ2007-65218, CTQ2011-24151, and Consolider Ingenio 2010-CSD2007-00006), the Generalitat Valenciana (GV; PROMETEO/2009/002 and PROMETEO/2009/039), and FEDER. Y.M. thanks the ISO of the Universidad de Alicante for a grant. R.B. acknowledges the Universidad de Alicante, CAM, and Union Fenosa for his grant (UF2007-X9159987F).

The effect of the support (activated carbon or titanium dioxide) on the catalytic activity and selectivity to nitrogen of Pt-Sn catalysts in nitrate reduction was studied. The effects of the preparation conditions and the Pt:Sn atomic ratio were also evaluated. It was observed that the support plays an important role in nitrate reduction and that different preparation conditions lead to different catalytic activities and selectivities. Generally, the catalysts supported on activated carbon were less active but more selective to nitrogen than those supported on titanium dioxide. The monometallic Pt catalyst is active for nitrate reduction only when supported on titanium dioxide, which is explained by the involvement of the support in the reaction mechanism. The catalysts were characterized by different techniques, and significant changes on metal chemical states were observed for the different preparation conditions used. Only metallic Pt and oxidized Sn were observed at low calcination and reduction temperatures, but some metallic Sn was also present when high temperatures were used, being also possible the formation of Pt-Sn alloys.

Preferential oxidation of CO in excess hydrogen (PROX) was studied over Pt catalysts supported on multi-wall carbon nanotubes in the temperature range between room temperature and the temperature of the water–gas shift unit (∼473 K). Experimental results show that the Pt/CNT catalyst exhibit a superior performance in terms of catalytic activity and selectivity towards CO 2 formation compared to a Pt/AC catalyst prepared under similar conditions. Apparently, preferential CO oxidation in excess hydrogen over Pt nanoparticles supported on carbon materials is a particle size dependent reaction, i.e. larger particles exhibit higher activity and selectivity. In any case, the incorporation of oxygen functionalities to the carbon support becomes detrimental for the CO oxidation reaction independently of the carbon support used. Finally, CeO 2 addition to the Pt/CNT catalyst further improves both catalytic activity and selectivity at low temperatures (CO conversion rate of 46% at 313 K), the catalytic performance being superior to that exhibited by a traditional PROX catalyst such as Pt/CeO 2 .