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Three samples that correspond to the evolution of optimal catalytic systems for the oxidative dehydrogenation of ethane have been synthesized and compared in terms of catalytic behavior and adsorption properties: (i) vanadium oxide supported on alumina, (ii) Sn-promoted NiO, and (iii) multicomponent MoVTeNbO with the M1 structure. The main difference in catalytic performance lies in the extent of the overoxidation of the ethylene formed, following the order VOx/Al2O3 > NiSnOx > MoVTeNb-M1. Accordingly, the selectivity to ethylene at medium and high ethane conversion follows the order MoVTeNb-M1 > NiSnOx > VOx/Al2O3. These results are confirmed by the relative reaction rates observed for the oxidation of ethane and the oxidation of ethylene. Microcalorimetry studies indicate that the heat of adsorption of both ethane and ethylene is the highest in the most selective MoVTeNb-M1 sample. Thus, the low olefin decomposition in the MoVTeNb-M1 catalyst is not due to weaker adsorption of ethylene but to the reduced ability of its active sites to activate ethylene. The same conclusion regarding the MoVTeNb-M1 catalyst can be drawn by FT-IR of adsorbed ethylene. On the other hand, NiSnOx active sites present a high overoxidation ability, as demonstrated by the notorious formation of oxygenated species, precursors of COx. However, the ethylene decomposition is rather mild because of the existence of many free Lewis sites not involved in the overoxidation reaction. In contrast, in the case of the VOx/Al2O3 catalyst, almost all active sites are involved in the oxidation path, so that the olefins decompose readily., The authors acknowledge the Spanish Ministry of Science, Innovation and Universities (MCIU) for their funding (RTl2018-099668-B-C21, MAT2017-84118-C2-1-R and MAT2017-87500-P) and FEDER. The authors from ITQ also thank Programa Severo Ochoa (SEV-2016-0683). A.A. acknowledges the Severo Ochoa Excellence Program for his grant (BES-2017-080329).

9 figures, 2 tables., In the present work, a simple soft chemistry method was employed to prepare cobalt mixed oxide (Co3O4) materials, which have shown remarkably high activity in the heterogeneously catalyzed total oxidation of low reactive VOCs such as the light alkanes propane, ethane, and methane. The optimal heat-treatment temperature of the catalysts was shown to depend on the reactivity of the alkane studied. The catalytic activity of the Co3O4 catalysts was found to be as high as that of the most effective catalysts based on noble metals. The physicochemical properties, from either the bulk (using XRD, TPR, TPD-O2, and TEM) or the surface (using XPS), of the catalysts were investigated to correlate the properties with the catalytic performance in the total oxidation of VOCs. The presence of S1 low-coordinated oxygen species at the near surface of the Co3O4-based catalysts appeared to be linked with the higher reducibility of the catalysts and, consequently, with the higher catalytic activity, not only per mass of catalyst but also per surface area (enhanced areal rate). The co-presence of propane and methane in the feed at low reaction temperatures did not negatively affect the propane reactivity. However, the co-presence of propane and methane in the feed at higher reaction temperatures negatively affected the methane reactivity., This research was funded by MINECO-Spain, grant number PRE2018-085211. This work was also funded by the MAT2017-84118-C2-1-R MCIN/AEI/10.13039/501100011033/ project and FEDER Una manera de hacer Europa. Comunidad de Madrid, grant number 2017-T1/IND-6025, within the program “Atracción y Retención de Talento Investigador” of the V PRICIT.

1 scheme, 2 tables, 7 figures.-- Supplementary material available., In the present article, gamma-valerolactone has been obtained from levulinic acid with a yield exceeding 25% using very mild conditions without feeding hydrogen (30 degrees C, atmospheric pressure, water as the hydrogen source). The overall reaction conducted is a two-step process: first, a redox reaction involving the oxidation of metallic Zn to ZnO for in situ hydrogen production through the water splitting reaction and, second, a catalytic reaction involving Ni-supported catalysts for the production of gamma-valerolactone from levulinic acid. Ni active sites have been supported on sepiolite, an abundant and cheap material. The nickel particle size has been demonstrated to be a parameter of paramount importance determining the catalytic activity, since the best catalytic performance is obtained with the smallest Ni nanoparticles. This combination of Zn and Ni supported on sepiolite shows a good catalytic stability after three catalytic runs., Authors from UCM thank MINECO (MAT2017-84118-C2-2-R project) and UCM CAI center of EM. Authors from UV thank MINECO (MAT2017-84118-C2-1-R project) and FEDER for funding. A. G. thanks MINECO for the pre-doctoral grant.

[EN] A Nb-containing siliceous porous clay heterostructure (PCH) with Nb contents from 0 to 30 wt %) was prepared from a bentonite and used as support in the preparation of supported NiO catalysts with NiO loading from 15 to 80 wt %. Supports and NiO-containing catalysts were characterised by several physicochemical techniques and tested in the oxidative dehydrogenation (ODH) of ethane. The characterisation studies on Nb-containing supports showed the presence of well-anchored Nb(5+)species without the formation of Nb(2)O(5)crystals. High dispersion of nickel oxide with low crystallinity was observed for the Nb-containing PCH supports. In addition, when NiO is supported on these Nb-containing porous clays, it is more effective in the ODH of ethane (ethylene selectivity of ca. 90 %) than NiO supported on the corresponding Nb-free siliceous PCH or on Nb2O5(ethylene selectivities of ca. 30 and 60 %, respectively). Factors such as the NiO-Nb(5+)interaction, the NiO particle size and the properties of surface Ni(n+)species were shown to determine the catalytic performance., The authors would like to acknowledge the Ministerio de Ciencia, Innovacion y Universidades of Spain (CRTl2018-099668-B-C21, RTl2018-099668-B-C22 and MAT2017-84118-C2-1-R projects). Authors from ITQ also thank Project SEV-2016-0683 for supporting this research. D.D. thanks MINECO and Severo Ochoa Excellence Program for his fellowship (SVP-2014-068669).

[EN] Porous Clays Heterostructures (PCH) from natural pillared clays (bentonite with a high proportion of montmorillonite) have been used as supports of iron oxide for two reactions of environmental interest: i) the elimination of toluene (a representative compound of one of the most toxic subsets of volatile organic compounds, aromatics) by total oxidation and ii) the selective oxidation of H2S to elemental sulfur. For both reactions these catalysts have resulted to be remarkably more efficient than similar catalysts prepared using conventional silica as a support. Thus, in the total oxidation of toluene it has been observed that the catalytic activity obtained using siliceous PCH is two orders of magnitude higher than that with conventional silica. The catalytic activity has shown to be dependant of the capacity of the support for dispersing iron oxide in a way that the higher the dispersion of iron oxide on the surface of the support, the higher is the activity. In the case of the selective oxidation of H2S to S both higher catalytic activity and higher selectivity to S have been observed using siliceous porous clays heterostructures than using conventional silica. Highly dispersed FeOx species have been shown as highly selective towards elemental sulfur whereas more aggregated FeOx species favour the formation of sulphur oxides decreasing the selectivity to S. Analyses of the surface by XPS have shown the predominance of sulfate species in the catalysts presenting low selectivity to elemental sulfur., The authors would like to acknowledge the DGICYT in Spain (CTQ2015-68951-C3-1-R, CTQ2015-68951-C3-3-R, CTQ2012-37925-C03-2, CTQ2012-37925-C03-3 and CTQ2012-37984-C02-01) and FEDER for financial support. We also thank the University of Valencia for funding (UV-INV-AE-16-484416) and SCSIE-UV for assistance.

[EN] Porous clay heterostructures (PCH) have shown to be highly efficient supports for nickel oxide in the oxidative dehydrogenation of ethane. Thus NiO supported on silica with a PCH structure shows productivity towards ethylene three times higher than if NiO is supported on a conventional silica. This enhanced productivity is due to the increase in the catalytic activity and especially to the drastic increase in the selectivity to ethylene. Additionally, PCH silica partially modified with titanium in the columns (PCH-Ti) have also been synthesized and used as supports for NiO. An enhanced activity and selectivity to ethylene was found over NiO supported over PCH-Ti compared to the corresponding catalysts supported over the Ti-free PCH. The enhanced catalytic performance has been related to the high dispersion of nickel oxide particles on the support, which leads to a lower reducibility of the nickel oxide, hindering the oxidation of ethane into carbon oxides. More interestingly, the particle morphology plays an important role on the catalyst selectivity since a higher distortion of the NiO crystal lattice parameter meant an enhanced selectivity to ethylene., The authors would like to acknowledge the DGICYT in Spain (CTQ2012-37925-C03-1, CTQ2012-37925-C03-2 and CTQ2012-37925-C03-3) and the FEDER for financial support. We also thank the University of Valencia and SCSIE-UV for assistance.

Differently prepared vanadium promoted Pt/alumina catalysts have been prepared, characterized and tested for propane total oxidation. V-promoted Pt/Al2O3 catalysts have shown remarkably higher catalytic activity than V-free Pt/Al2O3 catalyst. Among V-promoted Pt catalysts that prepared by coimpregnation gave the highest alkane conversions in the whole range of reaction temperatures studied. Factors such as Pt particle size or the oxidation state of platinum do not seem to be the responsible for the enhanced performance. Modification of the redox properties of the catalyst (i.e. high reducibility of vanadium species) likely provoked by the close contact between platinum particles and vanadium species and the partial introduction of vanadium in the platinum particles can be related to the improved reactivity of the PtV catalysts.

Iron oxides (FeOx) are non-toxic, non-expensive and environmentally friendly compounds, which makes them good candidates for many industrial applications, among them catalysis. In the present article five catalysts based on FeOx were synthesized by mild routes: hydrothermal in subcritical and supercritical conditions (Fe-HT, Few200, Few450) and solvothermal (Fe-ST1 and Fe-ST2). The catalytic activity of these catalysts was studied for the total oxidation of toluene using very demanding conditions with high space velocities and including water and CO2 in the feed. The samples were characterized by X-ray diffraction (XRD), scanning and high-resolution transmission electron microscopy (SEM and HRTEM), X-ray photoelectron spectroscopy (XPS) and nitrogen adsorption-desorption isotherms. It was observed that the most active catalyst was a cavity-containing porous sample prepared by a solvothermal method with a relatively high surface area (55 m2 g−1) and constituted by flower-like aggregates with open cavities at the catalyst surface. This catalyst displayed superior performance (100% of toluene conversion at 325 °C using highly demanding conditions) and this performance can be maintained for several catalytic cycles. Interestingly, the porous iron oxides present not only a higher catalytic activity than the non-porous but also a higher specific activity per surface area. The high activity of this catalyst has been related to the possible synergistic effect of compositional, structural and microstructural features emphasizing the role of the surface area, the crystalline phase present, and the properties of the surface., Authors from UV thank the University of Valencia (UV-INV-AE16-484416 project) and MINECO (MAT2017-84118-C2-1-R project) for funding. Authors from UCM thank Santander-UCM institution (PR41/17-20951 project) and MINECO (MAT2017-84118-C2-2-R project) for funding.

[EN] The robustness of one selected Ni-W-O catalyst has been studied in the oxidative dehydrogenation of ethane. This catalyst initially deactivates for the first 10 h online decreasing 15% of its catalytic activity compared to its initial stable catalytic activity. However from 10 to 60 h online the catalytic activity keeps almost stable. On the other hand, it has been shown that the Ni-W-O catalyst cannot tolerate an oxygen-free atmosphere (C-2 and He) as nickel oxide is transformed into metallic nickel. Methane and hydrogen as well as abundant coke were formed on the surface of the catalyst in these O-free conditions. However a re-calcination in air leads to the removal of coke, the catalytic performance in the oxidative dehydrogenation of ethane being almost completely restored., Financial support from DGICYT in Spain (Projects CTQ2012-37925-C03-01 and CTQ2012-37925-C03-03) is gratefully acknowledged. The authors also want to thank the SCSIE, University of Valencia, for providing HRTEM facilities.

Different nickel catalysts have been tested for the transformation of levulinic acid into &gamma, valerolactone using an easy hydrothermal method, taking advantage of the properties of the high temperature water. A metallic nickel catalyst derived from NiO synthesized by a nanocasting procedure can achieve a productivity to &gamma, valerolactone, which is two orders of magnitude higher than that obtained by a commercial nickel catalyst. This nanocasted metallic nickel catalyst has shown bifunctionality as it is capable of activating water as the source for hydrogen and undertaking the further hydrogenation step. In contrast with metallic nickel, nickel oxide has shown to be incapable of transforming levulinic acid into &gamma, valerolactone.

Cobalt oxide and manganese oxide catalysts have been prepared through aqueous synthesis using a wet combustion procedure. These materials have been tested as catalysts for the total oxidation of propane. It has been observed a different catalytic behaviour between cobalt and manganese oxides although for both oxides a very high catalytic activity has been obtained. Cobalt oxides prepared by the wet combustion procedure are less reactive than a simple cobalt oxide prepared without the addition of organic acids. However, in the case of manganese oxide the use of organic acids highly increases the catalytic activity. The different catalytic behaviour has been related to the variation of the surface characteristics and also to the crystalline phases formed. The activity of Co catalysts has been observed to be mainly determined by the surface area as the specific activity of all cobalt oxide catalysts is comparable. This fact has been related to the similar bulk and surface redox catalyst characteristics. In the case of manganese oxide the specific reaction rate is remarkably higher in those catalysts prepared by wet combustion and this has been linked to the presence of a reduced phase and surface. The most active manganese oxide catalysts are those that present the best redox properties and the highest oxygen mobility.

Several CeO2 and CuO-CeO2 catalysts were prepared using different methods, i.e., a homogeneous precipitation with urea, a nanocasting route using CMK-3 carbon as a hard template and a sol–gel process using Poly(methyl methacrylate) (PMMA) polymer as a soft template, and tested in the total oxidation of propane. The catalysts were characterized by a number of physicochemical techniques (XRD, N2 adsorption, TPR, XPS, Raman spectroscopy) showing distinct characteristics. For each series, Cu-Ce-O catalysts with low Cu-loadings (5 wt % CuO) showed the highest activity, higher than those samples either without copper or with high Cu-loading (13 wt % CuO). The incorporation of copper leads to an increase of the concentration of bulk defects but if the Cu-loading is too high the surface area drastically falls. The highest activity in the total oxidation of propane was achieved by Cu-containing ceria catalysts synthesized using a polymer as a template, as this method yields high surface area materials. The surface area and the number of bulk/sub-surface defects of the ceria seem to be the main properties determining the catalytic activity., The authors would like to acknowledge the DGICYT in Spain CTQ2012-37925-C03-2, CTQ2015-68951-C3-1-R, CTQ2015-68951-C3-3-R. Authors from ITQ also thank Project SEV-2012-0267 for financial support. B.S, R.S and A.M.D also thank UV-INV-AE16-484416.

Several Mn2O3 catalysts have been synthesized using different preparation methods and tested for the total oxidation of naphthalene, a model polycyclic aromatic compound. The catalysts have been characterized by several physico-chemical techniques such as XRD, TPR, XPS, EDX and TEM. The surface area of the catalyst seems to be of paramount importance, since the mass normalized activity of catalysts increases as the surface area of the Mn2O3 catalysts increases. Consequently, a high surface area ordered mesoporous Mn2O3 catalyst, obtained through a nanocasting route using mesoporous KIT-6 silica as a hard template, was the most efficient catalyst for the deep oxidation of naphthalene. In addition, this catalyst also exerts the highest surface area normalized catalytic activity, which can be related to the highest reducibility and mobility of its lattice oxygen. It was also observed that the Mn2O3 crystalline phase presents a higher intrinsic activity than MnO2.

Gold deposited on a cobalt containing siliceous mesoporous structure, UVM-7, presents a good catalytic performance in the total oxidation of propane and toluene. The presence of both gold and cobalt is necessary as bimetallic Au/Co-UVM-7 catalysts are remarkably more active than monometallic Au/UVM-7 or Co-UVM-7 catalysts. The improved activity of the bimetallic AuCo-samples if compared to gold free cobalt catalysts can be explained on the basis of the enhanced reducibility of some cobalt species in the presence of gold, which facilitates the redox cycle. This high reducibility of cobalt species in the bimetallic samples is probably due to the formation of Co 3 O 4 domains at the gold–CoO interface perimeter, which are absent in the gold free cobalt containing UVM-7 catalysts. More interestingly, these catalysts have shown a high stability during the oxidation of propane and toluene, showing stable activity for at least 50 h and 3 catalytic cycles. In fact, these catalysts have hardly modified their physicochemical properties after the catalytic runs. This stability has been explained on the basis of the architecture of the siliceous UVM-7 support. A deep characterization of all samples was carried out, before and after reaction, by means of N 2 adsorption, Transmission Electron Microscopy, chemical analyses, X-ray diffraction, temperature programmed reduction and X-ray photoelectron spectroscopy, what allowed us to explain the observed stability.

Gold supported on nickel cerium oxide catalysts (Ni–Ce–O) have been studied for the total oxidation of propane, as a model for hydrocarbon volatile organic compound emission control. High surface area Ni–Ce–O catalysts were synthesized using a very simple evaporation method, where cerium and nickel salts were evaporated in the presence of a mixture of methanol and oxalic acid. Gold catalysts were prepared following a deposition–precipitation method. A very efficient catalyst for the oxidation of propane, in terms of both activity and selectivity, was obtained. This high activity has been related to the high surface area of the catalyst (and therefore to the presence of more active sites available), a high reducibility of Ni-sites and a low strength of the Ni–O bond. Additionally, all the gold catalysts tested are highly selective towards CO2 (close to 100%), in contrast to gold-free catalysts.

Mixed Ni–W–O catalysts (with a W/(Ni + W) atomic ratio of 0.3) supported on γ-Al2O3 or on mesoporous alumina have been prepared, characterized and tested in the oxidation of ethane. For comparison unsupported and supported NiO as well as bulk Ni–W–O mixed oxides catalysts have also been studied. Supported Ni–W–O materials show interesting catalytic performances in the oxidative dehydrogenation of ethane. They show similar catalytic activities than the corresponding unsupported Ni–W–O catalysts. However, the selectivity to ethylene over supported catalysts was higher than that achieved over unsupported samples (the selectivity to ethylene followed the trend: mesoporous-supported > γ-Al2O3-supported > unsupported Ni–W–O). In addition, it has also been observed that Ni–W–O catalysts are more efficient than the corresponding W-free NiO catalysts. The discussion of the catalytic results will be undertaken on the basis of the modification of active sites of NiO when incorporating WO3 and/or metal oxide supports.

Mo–V–X (X = Nb, Sb and/or Te) mixed oxides have been prepared by hydrothermal synthesis and heat-treated in N2 at 450 °C or 600 °C for 2 h. The calcination temperature and the presence or absence of Nb determines the nature of crystalline phases in the catalyst. Nb-containing catalysts heat-treated at 450 °C are mostly amorphous solids, while Nb-free catalysts heat-treated at 450 °C and samples treated at 600 °C clearly contain crystalline phases. TPR-H2 experiments show higher H2-consumption on catalysts with amorphous phases. Catalytic results in the oxidative dehydrogenation of ethane indicate that the selective production of the olefin is strongly related to the development of the orthorhombic Te2M20O57 or (SbO)2M20O56 (M = Mo, V, Nb) phase (the so-called M1 phase), which is mainly formed at 600 °C. This active and selective crystalline phase is characterized to show moderate reducibility and active centers enough for the selective oxidative activation of ethane with the minimum quantity possible of active centers for ethylene activation. In this sense, the best yield to ethylene has been achieved on a Mo–V–Te–Nb mixed oxide.

Supported and unsupported nanocrystalline cobalt oxides have been shown to be extremely efficient catalysts for the total oxidation of propane. Total conversion with a high stability has been achieved at reaction temperatures as low as 250 °C. In the present work, a comparison between the catalytic performance of bulk and alumina-supported nanocrystalline cobalt oxide catalysts has been made. The influence of crystallite size, nature of the support (alpha, gamma and mesoporous alumina) and cobalt loading, has been probed. Unsupported cobalt oxide catalysts were more active than any supported cobalt oxide catalysts. The catalytic activity was mainly dependent on the crystallite size, decreasing with an increase in the crystallite size. Whilst the TOF of supported catalysts increases with both a decrease in the surface area of the support and an increase of the cobalt content. Only those catalysts with a cobalt content of 50 wt% achieve a catalytic activity per cobalt atom similar to that of unsupported Co3O4 prepared under similar conditions. High surface area alumina was shown to be a less efficient support especially at low Co-loadings due to the dispersion of cobalt on the surface leading to the formation of inactive Co–O–Al species. The low surface area support (α-Al2O3) presents a low capacity to isolate the cobalt oxide species resulting in a lower concentration of inactive Co–O–Al species and, therefore, the highest activity among supported catalysts. In conclusion, two parameters seem to determine the catalytic activity of nanocrystalline cobalt oxide: these are the presence of inactive Co–Al bonds (prevalent in supported catalysts) and also the size of the active Co3O4 particles.

[EN] Bulk Ni-Sn-O catalysts have been synthesized, tested in the oxidative dehydrogenation of ethane and characterized by several physicochemical techniques. The catalysts have been prepared by evaporation of the corresponding salts using several additives in the synthesis gel, i.e. ammonium hydroxide, nitric acid, glyoxylic acid or oxalic acid, in the synthesis gel. The catalysts were finally calcined at 500 degrees C in air. Important changes in the catalytic behaviour have been observed depending on the additive. In fact, an important improvement in the catalytic performance is observed especially when some additives, such as glyoxylic or oxalic acid, are used. Thus the productivity to ethylene multiplies by 6 compared to the reference Ni-Sn-O catalyst if appropriate templates are used, and this is the result of an improvement in both the catalytic activity and the selectivity to ethylene. This improved performance has been explained in terms of the decrease of the crystallite size (and the increase in the surface area of catalyst) as well as the modification of the lattice parameter of nickel oxide., The authors would like to acknowledge the DGICYT in Spain (CTQ2015-68951-C3-1-R and CTQ2012-37925-C03-2) for financial support. We also thank the University of Valencia and SCSIE-UV for assistance

9 figures, 3 tables.-- Supplemantary information available, The total oxidation of two representative VOCs, propane and toluene, has been studied using mesoporous α-FeO catalysts. Different preparation methods have been followed leading to mesoporous materials with different characteristics. Whilst a mesoporous catalyst formed by aggregation of nanocrystals has been produced by soft chemistry using oxalic acid as precipitating agent, a mesoporous material with crystalline walls have been prepared by a nanocasting route using a hard template. These catalysts have been characterized by several physicochemical techniques: XRD, N adsorption, TPR, XPS, TEM, HR-TEM, SAED and EDX. Among the different α-FeO catalysts synthesized differences not only in the surface area and morphology have been observed but also in the lattice parameter, in the concentration of oxygen defects for VOCs adsorption and in the reducibility. In the case of the toluene oxidation it has been observed that the catalytic activity is highest for the catalysts prepared by a nanocasting route, which presents a very high surface area of 208 m g. Conversely, for propane oxidation the most active catalyst resulted to be the mesoporous nanocrystalline catalyst formed by aggregation. In this case, a direct relationship between reducibility and catalytic activity normalized per surface area has been observed. The differences between toluene and propane oxidation can be tentatively ascribed to different reaction mechanisms to be accounted for., The authors would like to acknowledge the DGICYT in Spain (CTQ2012-37925-C03-1, CTQ2012-37925-C03-2, CTQ2012-37925-C03-3 and CTQ2012-37984-C02-01) and FEDER for financial support.

Te-free and Te-containing Mo–V–Nb mixed oxide catalysts were diluted with several metal oxides (SiO 2 , γ -Al 2 O 3 , α -Al 2 O 3 , Nb 2 O 5 , or ZrO 2 ), characterized, and tested in the oxidation of ethane and propane. Bulk and diluted Mo–V–Nb–Te catalysts exhibited high selectivity to ethylene (up to 96%) at ethane conversions 10 % , whereas the corresponding Te-free catalysts exhibited lower selectivity to ethylene. The selectivity to ethylene decreased with the ethane conversion, with this effect depending strongly on the diluter and the catalyst composition. For propane oxidation, the presence of diluter exerted a negative effect on catalytic performance (decreasing the formation of acrylic acid), and α -Al 2 O 3 can be considered only a relatively efficient diluter. The higher or lower interaction between diluter and active-phase precursors, promoting or hindering an unfavorable formation of the active and selective crystalline phase [i.e., Te 2 M 20 O 57 (M = Mo, V, and Nb)], determines the catalytic performance of these materials.

Vanadium and/or molybdenum oxides supported on mesoporous alumina have been prepared by a “wet” impregnation method, characterized (by using several physico-chemical techniques TPR, DR-UV–vis, Raman spectroscopies) and tested in the oxidative dehydrogenation (ODH) of ethane. For comparison Mo–V-mixed oxides supported on γ-Al2O3 have also been studied. The characterization results indicate that the main vanadium species in both Mo-free and Mo-containing V-based samples present low aggregation and coordination, whereas molybdenum is present as monomeric or polymeric tetrahedral molybdenum species. Interestingly, no apparent interaction between molybdenum and vanadia takes place. The catalytic results show that V-containing catalysts are ca. four times more active than pure Mo-catalyst, whereas Mo–V-containing catalysts resulted to be the most selective ones in the ODH of ethane to ethylene, indicating that a synergetic effect between Mo and V takes place. In all cases, catalysts supported on mesoporous alumina were more active and selective in the ODH of ethane than the corresponding catalysts supported on γ-Al2O3.

MoVTe-Nb oxide catalysts have been prepared by a hydrothermal method and tested in the selective oxidation of propane to acrylic acid and in the oxidative dehydrogenation of ethane to ethylene. The influence of the concentration of oxalate anions in the hydrothermal gel has been studied for two series of catalysts, Nb-free and Nb-containing, respectively. Results show that the development of an active and selective active orthorhombic phase (Te2M20O57, M = Mo, V, Nb) requires an oxalate/Mo molar ratio of 0.4–0.6 in the synthesis gel in both types of samples. The presence of Nb favours a higher catalytic activity in both ethane and propane oxidation, and a better production of acrylic acid.

Mo–V–Sb–O mixed metal oxides were prepared, characterized and tested for the oxidative dehydrogenation of ethane (ODH). These catalysts are active and selective in the oxidative dehydrogenation of ethane to ethylene, although their catalytic performance depends strongly on the calcination temperature. The best catalytic results were obtained on samples heat-treated at 600 °C in N 2 (with selectivities to ethylene higher than 80% at ethane conversions about 65%). Moreover, a loss in the catalyst activity is initially observed on these catalysts as a consequence of modifications in the nature of the crystalline phases. Changes on the oxidation state of antimony ions on the surface of the used catalyst have also been observed, with the appearance of Sb 5+ on the surface of used catalysts. The good catalytic performance of these catalysts is related to the presence of (SbO) 2 M 20 O 56 crystalline phase in a similar way to that proposed for selective Mo–V–Te–Nb–O mixed metal oxide catalysts.

MoVTeNbO catalysts, prepared by hydrothermal synthesis, are active and highly selective in the ODH of ethane, especially those with a MoVTeNb molar ratio of 1–0.15–0.16–0.17 and heat-treated at 600–650 °C. On the best catalyst, selectivities higher than 80% at ethane conversion levels higher than 80% have been obtained operating at relatively low reaction temperatures (340–400 °C). Thus, yields of ethylene of ca. 75% have been obtained, which exceeds the best yield reported in the literature. Te 2 M 20 O 57 ( M =Mo, V, Nb) and (V,Nb)-substituted θ -Mo 5 O 14 , in addition to small amounts of the Te 0.33 M O 3.33 ( M =Mo, V, Nb) phase, can be proposed in the most selective catalysts from XRD, SAED, and HREM results. However, the catalytic performance in ethane oxidation can mainly be related to the presence of the multifunctional Te 2 M 20 O 57 orthorhombic phase in cooperation with the Mo 5 O 14 -type phase. The nature of active and selective sites is discussed.

Ethylene has selectively been obtained during the oxidative dehydrogenation of ethane on a Mo–V–Te–Nb–O mixed oxide catalyst. The catalyst was prepared hydrothermally and heat-treated at 600 °C for 2 h in a N2-stream. For comparison, undoped and Te-doped Mo–V–Nb–O catalysts and Mo–V–Te–O and Mo–Te–Nb–O mixed oxides have also been prepared. The catalytic performance of the Mo–V–Nb–Te–O mixed oxide catalyst cannot be explained by the incorporation of Te on the surface of a Mo–V–Nb–O mixed oxide but by the presence of an orthorhombic Te2M20O57 (M=Mo, V, Nb) crystalline phase. The role of tellurium in these catalysts is also discussed.

Mo–V–Nb–O mixed metal oxides, obtained by heat-treatment in N 2 at 425 °C, have been studied as catalysts in the oxidative dehydrogenation of ethane. They present higher catalytic activity, while maintaining the same selectivity to ethylene, than the corresponding metal oxides calcined under air. Both amorphous and crystalline phases are present on active and selective catalysts. The implications of the presence of these phases as well as their physicochemical characteristics on the nature of active and selective sites are discussed.

7 figures.-- © 2015. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/, H2 and propylene can be obtained from propane and oxygen in defect using appropriate catalysts. Meanwhile propylene is formed from propane via oxidative or non-oxidative dehydrogenation, molecular hydrogen can be obtained from several reactions such as propane dehydrogenation, coke formation and water gas shift. It has been observed that a gold catalyst hardly activates propane and no H2 was detected, whereas using vanadium oxide a relatively high concentration of propylene and H2 was obtained. Interestingly, the simultaneous use of vanadium oxide and gold has meant a higher hydrogen production, higher in a 40% than that of the catalyst containing only vanadium oxide. This performance has been related to the capacity of gold to activate CO in the water gas shift reaction., The authors would like to acknowledge the DGICYT in Spain (CTQ2012-37925-C03-1, CTQ2012-37925-C03-2 and CTQ2012-37984-C02-01) for financial support. We also thank the University of Valencia and SCSIE-UV for assistance. J.M. López would also like to thank Spanish MICINN and CSIC for funding his Ramon y Cajal contract (RYC-2009-04483).

1 figures, 3 tables.-- © 2014. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/, The industrial implementation of hydrogen peroxide as a green oxidant requires the development of efficient catalytic systems for its direct synthesis from molecular oxygen and hydrogen. Bimetallic Au-Pd nanoparticles supported on acid pre-treated ordered CMK-3 carbon catalysts show high H2O2 productivities and high H2 selectivities (>99%). Encapsulation of the nanoparticles within the pore network lead to stable small size (∼2 nm) particles. This paper reveals that the acid pre-treatment, does not only improve the metal dispersion of metals but most importantly, it promotes their gold enrichment, dramatically decreasing the parallel H2O2 decomposition, which is key for the economic feasibility of the process., The authors would like to thank MINECO and FEDER (project CTQ2012-37984-C02-01 and CTQ2012-37925-C03-02 Spain) and EPSRC (grant number EP/K016334/1, UK) for funding. B.P. acknowledges the Spanish Ministry of Education for her scholarship (FPU grant AP2009-3544).

Well-organised V-containing MCM-41 and -48 (0.3‐1 wt.% of V content) have been synthesised by one-pot synthesis or by grafting using VOSO4 or VOCl3 as V sources, respectively. The samples before and after the calcination step have been characterised by several physicochemical techniques (Ar and N2 adsorption, XRD, diffuse reflectance-UV‐VIS (DR-UV‐VIS) spectroscopy, temperature-programmed reduction). It was found that V species in the as-prepared catalysts were mainly as vanadyl ions (VO 2C ), while highly dispersed V 5C species with tetrahedral coordination were observed in the calcined materials. The catalytic behaviour of the calcined materials for the gas phase oxidation of propane has been studied using low propane/oxygen ratios in the 500‐550C temperature range. Also, the catalytic results of V-containing mesoporous materials have been compared to those obtained on SiO2-supported vanadia catalysts with similar vanadia contents. In all cases, propylene, CO and CO2 were the main reaction products although partial oxygenated products (selectivities lower than 10%) were also observed. V-containing MCMs materials show a selectivity to propylene higher than SiO2-supported vanadia catalysts. These results can be explained by taking into account the higher surface area of MCMs materials which allows a better dispersion of V species on the mesoporous supports. © 2001 Elsevier Science B.V. All rights reserved.

Unsupported and SiO 2 -supported VMgO mixed oxides catalysts have been prepared, characterized and tested in the oxidation of propane, n -butane and propylene. Mg-vanadates are observed by XRD, IR and Raman spectroscopy in both pure and supported VMgO catalysts, although the effective Mg/V ratio, in the VMgO phases formed, depends on the silica content. Since SiO 2 reacts partially with MgO during the calcination step, forming Mg 2 SiO 4 , the effective Mg/V ratio depends on the silica content. In this sense, pyro -Mg 2 V 2 O 7 is mainly formed on supported catalysts with Mg/V atomic ratios lower than 4, while ortho -Mg 3 V 2 O 8 is observed on supported catalysts with Mg/V atomic ratios higher than 4. For this reason, it can be concluded that the Mg/V atomic ratio of crystalline VMgO phases observed on supported catalysts is lower than those observed on unsupported ones. The catalytic tests for the oxidation of propane and n -butane indicate that the catalytic behavior of supported catalysts depends on both the SiO 2 content and the Mg/V atomic ratio, although a different behavior during the oxidation of n -butane or propane is observed: the most selective catalysts for the oxydehydrogenation (OXDH) of propane were those with ortho -Mg 3 V 2 O 8 / pyro -Mg 2 V 2 O 7 /MgO or ortho -Mg 3 V 2 O 8 /MgO mixed phases while the most selective catalysts for the OXDH of n -butane are formed by ortho -Mg 3 V 2 O 8 /MgO mixed phases. On the other hand, V-containing compounds with VO double bonds are required in order to obtain selective catalysts for the oxidation of propylene to acrolein. In the selective oxidation of propylene, acrolein is not formed on catalysts in which ortho -Mg 3 V 2 O 8 /MgO mixed phases are mainly detected. However, acrolein was obtained on catalysts in which VO double bonds are present.

The oxidative dehydrogenation (OXDH) of n-butane and 1-butene on undoped and K-doped alumina-supported vanadia catalysts has been studied. The low selectivity to OXDH products on alumina-supported vanadia catalysts is a consequence of the isomerization of olefins (low temperatures) and the formation of carbon oxides (high temperatures) on acid sites. The presence of potassium results in a decrease of the number of acid sites and a higher selectivity to OXDH products from both n-butane and 1-butene. Infrared spectroscopy data of 1-butene adsorbed on the catalysts suggest the presence of different adsorbed species: (i) O-containing species on the undoped catalyst, or (ii) adsorbed butadiene on K-doped catalyst. A reaction network including parallel and consecutive reactions is proposed.

A detailed study on the influence of the addition of molybdenum ions on the catalytic behaviour of a selective vanadium–magnesium mixed oxide catalyst in the oxidation of n-butane has been performed. The catalysts have been prepared by impregnation of a calcined V–Mg–O mixed oxides (23.8 wt% of V2O5) with an aqueous solution of ammonium heptamolybdate, and then calcined, and further characterised by several physico-chemical techniques, i.e. SBET, XRD, FTIR, FT-Raman, XPS, H2-TPR. MgMoO4, in addition to Mg3V2O8 and MgO, have been detected in all the Mo-doped samples. The incorporation of molybdenum modifies not only the number of V5+-species on the catalyst surface and the reducibility of selective sites but also the catalytic performance of V–Mg–O catalysts. The incorporation of MoO3 favours a selectivity and a yield to oxydehydrogenation products (especially butadiene) higher than undoped sample. In this way, the best catalyst was obtained with a Mo-loading of 17.3 wt% of MoO3 and a bulk Mo/V atomic ratio of 0.6. From the comparison between the catalytic properties and the catalyst characterisation of undoped and Mo-doped V–Mg–O catalysts, the nature of selective sites in the oxidative dehydrogenation of n-butane is also discussed.

Isobaric vapor−liquid equilibria have been obtained for the systems tetrachloroethylene + 1-pentanol, tetrachloroethylene + 3-methyl-1-butanol, and tetrachloroethylene + 2-methyl-1-butanol, using a...

Isobaric vapor–liquid equilibria (VLE) have been obtained for the systems trichloroethylene+1-pentanol, trichloroethylene+2-methyl-1-butanol and trichloroethylene+3-methyl-1-butanol at 100 kPa using a dynamic still. The experimental error in temperature is ±0.1 K, in pressure ±0.1 kPa, and in the liquid and vapor mole fraction ±0.001. The three systems satisfy the point-to-point thermodynamic consistency test. All the systems show positive deviations from ideality. The data have been correlated with the Margules, van Laar, Wilson, NRTL and UNIQUAC equations.

Isobaric vapor–liquid equilibria have been obtained for the systems 3-methyl-1-butanol+chlorobenzene, 3-methyl-2-butanol+chlorobenzene and 2-methyl-2-butanol+chlorobenzene at 100 kPa, using a dynamic still. The experimental error in temperature is ±0.1 K, in pressure ±0.1 kPa, and in the liquid and vapor mole fraction ±0.001. The three systems satisfy the point-to-point thermodynamic consistency test. All the systems show positive deviations from ideality. The data have been correlated with the Margules, Van Laar, Wilson, NRTL and UNIQUAC equations.

Isobaric vapor-liquid equilibria were obtained for the systems 1-propanol + chlorobenzene and 1-butanol + chlorobenzene at 200 and 300 kPa using a dynamic still. The mole fraction of the alcohol in the azeotropic point increases with pressure and for the 1-propanol + chlorobenzene system at 300 kPa, the azeotrope has disappeared. The two systems satisfy the point-to-point thermodynamic consistency test. Both systems show a positive deviation from ideality. The data were well correlated with the Margules, van Laar, Wilson. NRTL and UNIQUAC equations.

Vanadium–magnesium oxide (VMgO) catalysts have been prepared, characterized and tested in the ODH of n-butane. The catalysts were prepared by two variations of the wet-impregnation method using aqueous ammonium metavanadate or organically-based methanolic vanadyl acetylacetonate solutions. The catalyst surface area depends on the vanadium content and the preparation method. Catalyst characterization (i.e. XRD, 51V NMR, FTIR, LRS) results indicate the presence of poor crystalline Mg-orthovanadate (Mg3V2O8), while the presence of other Mg-vanadates is not clear. Oxygen isotopic-exchange experiments on VMgO catalysts indicate an R2 process: [ 18 O 2 +2 16 O 2− (s) → ( 18 O 18 O 16 O 16 O) 4− (s) →2 18 O 2− (s) + 16 O 2(g) ] at temperatures higher than 1023 K, while an R0-type [18O2(g)+16O2(g)→216O18O(g)] is observed at 823 K, as a consequence of a small activity for homophase isotopic. Both the catalytic activity and the selectivity to oxydehydrogenation products depend on the vanadium content but is independent on the catalyst preparation method. This behavior is observed in the ODH of n-butane with both O2 and N2O. However, while conversion of n-butane was higher when using O2 as oxidant, the selectivity to C4-olefins was higher with N2O as oxidant. Pulse experiments show that prereduced surfaces are not effective in producing olefins while selective catalysts are achieved with preoxidized surface. A mechanism for the oxidative dehydrogenation of n-butane is proposed.

Isobaric vapor−liquid equilibria were obtained for 1-butanol + chlorobenzene and for 2-butanol + chlorobenzene systems at 20 and 100 kPa using a dynamic still. The experimental error in temperature was ±0.1 K, in pressure ±0.01 kPa and ±0.1 kPa for the experiments carried out at 20 and 100 kPa, respectively, and in liquid and vapor composition ±0.001. The two systems satisfy the point-to-point thermodynamic consistency test. Both systems show a positive deviation from ideality. The data were correlated with the Wilson equation.

Vapor−liquid equilibria for trichloroethylene + 1-butanol, and + 2-butanol are reported at 20 and 100 kPa. The two systems satisfy the point-to-point thermodynamic consistency test. Both systems show a positive deviation from ideality.

Isobaric vapor−liquid equilibria were obtained for tetrachloroethylene + 1-propanol and +2-propanol systems at 20 and 100 kPa using a dynamic still. The experimental error in temperature was ±0.1 K, in pressure ±0.01 kPa and ±0.1 kPa for the experiments carried out at 20 and 100 kPa, respectively, and in liquid and vapor composition 0.001. The two systems satisfy the point-to-point thermodynamic consistency test. Both systems show a positive deviation from ideality. The data were well correlated with the Wilson equation.

Vanadium oxide supported on calcined hydrotalcite has been investigated for the oxidehydrogenation of n-butane in the 500–550°C temperature interval. Hydrotalcite (Mg/Al atomic ratio of 2.77), consisting of a single phase only, has been employed as a support precursor. The vanadium catalysts (0–50, referred as wt.-% V 2 O 5 ) were prepared by impregnation of calcined hydrotalcite (450°C) with ammonium metavanadate (in an aqueous solution) or vanadyl acetylacetonate (in a methanolic solution), and then calcined at 600°C for 4 h. During the impregnation step, the support is transformed into hydrotalcite if aqueous solutions are used. However, it is not modified if methanolic solutions are used. After calcination, diffuse X-ray diffraction patterns of MgO, in addition of a broad peak at 2θ=35° which intensity increases with the vanadium loading, were observed. Magnesium vanadates, i.e. ortho- and pyro-magnesium vanadates, were observed by FT-IR, FT-Raman and DR UV-vis. Similar activities for n-butane conversion are observed on all the catalysts studied, although the specific activity increases with the vanadium loading. However, independently of the catalysts preparation procedure, the selectivity to each oxydehydrogenation products (1-, cis -2-, trans -2-butenes and butadiene) initially increases with the vanadium loading, showing a maximum on catalysts with 30 wt.-% V 2 O 5 . The nature of active and selective sites is also discussed.

The catalytic properties of undoped and K-doped (K/V atomic ratio of 0.5) Al2O3-supported vanadia catalysts (∼4.5 wt% of V2O5) for the oxidation ofn-butane and ethane were studied. Isolated tetrahedral V5+ species are mainly observed in both undoped and K-doped samples. The incorporation of potassium decreases both the reducibility of surface vanadium species and the number of surface acid sites. Potassium-free vanadium catalysts show a high selectivity during the oxidative dehydrogenation (ODH) of ethane but a low selectivity during the ODH ofn-butane. However, the presence of potassium on the vanadium catalysts strongly influences their catalytic properties, increasing the selectivity to C4-olefins fromn-butane and decreasing the selectivity to ethene from ethane. The role of the acid-base characteristics of catalysts on selectivity to ODH reactions is proposed.

Ni-W-O mixed oxides were prepared through the evaporation of aqueous solutions of nickel nitrate and ammonium tungstate and calcined in air at 500 degrees C for 2 h. The catalysts were characterized by several techniques (N(2) adsorption, X-ray diffraction, temperature-programmed reduction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy of adsorbed CO, and (18)O/(16)O isotope exchange) and tested in the oxidative dehydrogenation of ethane. The catalytic activity and catalyst reducibility decrease when the W content increases. Thus, nickel sites seem to be the active centers for ethane activation in these catalysts. However, the selectivity to ethylene strongly changes depending on the Ni/W ratio. In W-rich catalysts, in which NiWO(4) and WO(3) are mainly observed, a strong influence of ethane conversion on the selectivity to ethylene is observed. However, in Ni-rich catalysts, in which NiO crystallites and WO(x) nanoparticles are mainly observed, ethane conversion hardly influences the selectivity to ethylene. It has been demonstrated that the nature of the Ni sites and the characteristics and number of the acid sites determine the catalytic behavior of these catalysts. The presence of Lewis acid sites with high acid strength in W-rich catalysts facilitates the decomposition of ethylene during ethane oxidation. (C) 2011 Elsevier Inc. All rights reserved., Financial support from DGICYT in Spain (Project CTQ-2009-14495) and Generalitat Valenciana (ACOMP/2010/091) is gratefully acknowledged.

Ordered Co3O4 with high surface area (until 173 m2/g) has been successfully obtained through a nanocasting route using mesoporous KIT-6 silica as a hard template and tested in the deep oxidation of a series of representative volatile organic compounds (VOCs): propane as a model of short chain alkane and toluene as a model of monoaromatic hydrocarbon. It has been demonstrated that the catalytic activity for VOC deep oxidation is very elevated and its catalytic stability at moderate temperatures very good. However, the role of the ordered structure in the catalytic performance does not seem to be beneficial. The enhanced catalytic activity has been explained in terms of both the high surface area and the presence of oxygen vacancies. In the present work we show for the first time the catalytic behaviour of a nanocasted cobalt oxide for the elimination of different VOCs., Authors wish to thank the Ministry of Science and Innovation (Spain) and to the Generalitat Valenciana through projects CTQ2009-14495, CTQ2006-02386 and GVPRE2008/352 for funding. S.A. wishes to thank the “Ministerio de Educacion y Ciencia” and the “Fondo Social Europeo” for its financial support.

[EN] The catalytic properties of MoVTeNbO catalysts during the selective oxidation of short chain alkanes and olefins (C-2-C-4) have been comparatively studied The main reaction products have been ethylene from ethane acrylic acid from propane maim anhydride from n-butane and methacrolein from isobutane FTIR studies of the adsorption of the main reaction products i e olefins and aldehydes over MoVTeNbO catalyst has been carried out Accordingly the reaction pathway is explained on the basis of the characteristics of the alkane fed the stability and reactivity of both the intermediates and the reaction products and the nature of the catalytic sites involved in each reaction (C) 2010 Elsevier B V All rights reserved, This work was supported by DGICYT in Spain (CTQ2006-09358/BQU). J.M.L.N., P.C. and F.I. also thank to the European Union for FP6 Integrated Project TOPCOMBI (Project No. NMP2-CT2005-515792).

During the catalytic combustion of naphthalene, compounds other than CO 2 are often obtained. These products, as polymerized polycyclic aromatic hydrocarbons, oxygenated aromatic compounds and benzene derivate compounds, are usually more toxic than naphthalene. At the present work it is shown a nanocrystalline cerium oxide prepared by a combustion method employing a proper ethylene glycol concentration that exhibits very high activity in the decomposition of naphthalene in the presence of air and, most importantly, a selectivity value towards CO 2 of 100% for any range of conversions and/or temperatures used. In addition, it has been demonstrated that the amount of ethylene glycol employed in the synthesis of the catalyst is determinant to achieve the optimal catalytic performance. The catalytic results have been explained in terms of the amount of cerium oxide defects.

Summary The physicochemical properties of potassium-, bismuth-, phosphorous- and molybdenum-doped (Me/V atomic ratios of 0 to 1) V 2 O 5 /γ-Al 2 O 3 catalysts and their catalytic behavior in the oxidative dehydrogenation of propane have been compared. The incorporation of metal oxides modifies the catalytic behavior of alumina-supported vanadia catalysts by changing both their redox and their acid-base properties. In this way, the addition of potassium leads to the best increase in the selectivity to propylene. This performance can be related to the modification of the acid character of the surface of the catalysts. The possible role of both redox and acid-base properties of catalysts on the selectivity to propylene during the oxidation of propane is also discussed.