0000000000011330
AUTHOR
Benjamín Solsona
The catalytic performance of mesoporous cerium oxides prepared through a nanocasting route for the total oxidation of naphthalene
Cerium oxides have been prepared by nanocasting of a mesoporous siliceous KIT-6. Through this synthesis method a partially ordered mesoporous structure, as demonstrated by several characterization techniques (N2 adsorption, XRD and HRTEM) has been obtained. Accordingly, very high surface areas have been achieved (up to 163 m2/g), despite using high calcination temperatures (550 °C). We have demonstrated that the aging temperature of the siliceous template is of outstanding importance, as this parameter is directly responsible for both the pore size and the surface area of the catalysts. In addition, whilst a low preparation temperature (40 °C) makes the further removal of the silica templat…
Total oxidation of VOCs on mesoporous iron oxide catalysts: Soft chemistry route versus hard template method
9 figures, 3 tables.-- Supplemantary information available
Mo-W-containing tetragonal tungsten bronzes through isomorphic substitution of molybdenum by tungsten
Mixed metal oxides based in Mo(W)–Nb–V–Te with tetragonal tungsten bronze (TTB) structure have been synthesized by a hydrothermal method from aqueous solutions of the corresponding Keggin-type heteropolyacids and further heat-treatment in N2 at 700 ◦ C. The materials have been characterized by several physico-chemical techniques, i.e. XRD, Raman, FTIR, SEM-EDS, and TEM. This procedure allows controlling the chemical species to be distributed in the different interstices of the TTB skeleton, which is a key factor to regulate the catalytic properties of the final solid. In this sense, the isomorphic replacement of Mo by W results in lattice parameter and crystal morphology variation, although…
Influence of annealing atmosphere on photoelectrochemical response of TiO2 nanotubes anodized under controlled hydrodynamic conditions
[EN] The influence of three annealing atmospheres (air, nitrogen and argon) and the use of controlled hydrodynamic conditions (from 0 to 5000 rpm) on morphological, structural, chemical and photoelectrochemical properties of TiO2 nanotubes have been evaluated. For this purpose, different characterization techniques have been used: Field Emission Scanning Electron Microscopy, Raman Confocal Laser Spectroscopy, X-Ray Diffraction, X-Ray Photoelectron Spectroscopy, Incident Photon-to-electron Conversion Efficiency measurements, ultraviolet-visible absorption spectra, Mott-Schottky analysis and photoelectrochemical water splitting tests. According to the results, it can be concluded that both hy…
Promoting Deoxygenation of Bio-Oil by Metal-Loaded Hierarchical ZSM-5 Zeolites
3 Figuras.- 5 tablas.-1 Esquema.- This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Sustainable Chemistry & Engineering, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acssuschemeng.5b01606 ”
Insights into the catalytic production of hydrogen from propane in the presence of oxygen: Cooperative presence of vanadium and gold catalysts
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/
Evolution of the optimal catalytic systems for the oxidative dehydrogenation of ethane: The role of adsorption in the catalytic performance
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…
The key role of nanocasting in gold-based Fe2 O3 nanocasted catalysts for oxygen activation at the metal-support interface
5 Tablas.- 10 Figuras.- This is the peer reviewed version of the following article: The key role of nanocasting in gold‐based Fe2O3 nanocasted catalysts for oxygen activation at the metal‐support interface, ChemCatChem 11: 1915-1927 (2019), which has been published in final form at http://dx.doi.org/10.1002/cctc.201900210. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
Redox and Catalytic Properties of Promoted NiO Catalysts for the Oxidative Dehydrogenation of Ethane
[EN] NiO and metal-promoted NiO catalysts (M-NiO, with a M/(M+Ni) atomic ratio of 0.08, with M = Nb, Sn, or La) have been prepared, tested in the oxidative dehydrogenation (ODH) of ethane, and characterized by means of XRD, TPR, HRTEM, Raman, XPS, and in situ XAS (using H-2/He, air or C2H6/He mixtures). The selectivity to ethylene during the ODH of ethane decreases according to the following trend: Nb NiO Sn NiO > La NiO > NiO, whereas the catalyst reducibility (determined by both TPR and XAS using H-2/He mixtures) shows the opposite trend. However, different reducibility and catalytic behavior in the absence of oxygen (ethane/He mixtures) have been observed, especially when comparing Nb- a…
Selective propane oxidation over MoVSbO catalysts. On the preparation, characterization and catalytic behavior of M1 phase
Nb-free (SbO)(2)M(20)O(56) catalysts (M = Mo, V) presenting pure M1 phase have been prepared by a post-synthesis treatment with hydrogen peroxide of a heat-treated MoVSbO mixed metal oxide catalyst previously prepared by hydrothermal method. The characterization of catalysts and their results for propane oxidation suggest that the optimization in the preparation of the M1 phase depends strongly on the washing procedure. The optimal removing of Sb species formed during post-synthesis treatment can explain the improvement in the catalytic activity; while the better selectivity to acrylic acid of the catalysts obtained by post-synthesis treatment can be explained by the elimination of M2 phase…
Size-activity relationship of iridium particles supported on silica for the total oxidation of volatile organic compounds (VOCs)
12 Figures, 2 Tables.-- Datos suplementarios disponibles en línea en la página web del editor.-- © 2019. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
Low temperature conversion of levulinic acid into γ-valerolactone using Zn to generate hydrogen from water and nickel catalysts supported on sepiolite
1 scheme, 2 tables, 7 figures.-- Supplementary material available.
Relationship between bulk phase, near surface and outermost atomic layer of VPO catalysts and their catalytic performance in the oxidative dehydrogenation of ethane
Abstract A set of vanadium phosphorous oxide (VPO) catalysts, mainly consisting of (VO) 2 P 2 O 7 , VO(PO 3 ) 2 or VOPO 4 ·2H 2 O bulk crystalline phases, has been investigated for the oxidative dehydrogenation (ODH) of ethane to ethylene, a key potential reaction for a sustainable industrial and socioeconomic development. The catalytic performance on these VPO catalysts has been explained on the basis of the main crystalline phases and the corresponding surface features found by XPS and LEISS at 400 °C, i.e. within the temperature range used for ODH reaction. The catalysts based on (VO) 2 P 2 O 7 phase presented the highest catalytic activity and productivity to ethylene. Nevertheless, the…
Deep oxidation of volatile organic compounds using ordered cobalt oxides prepared by a nanocasting route
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 …
Promoting the activity and selectivity of high surface area Ni–Ce–O mixed oxides by gold deposition for VOC catalytic combustion
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 ava…
The effect of gold addition on the catalytic performance of copper manganese oxide catalysts for the total oxidation of propane
Mixed copper manganese oxide catalysts (Hopcalite) have been studied for the total oxidation of propane, as a model for hydrocarbon volatile organic compound emission control. Catalysts were prepared using coprecipitation with and without gold. Calcination temperature influenced the catalyst activity and those prepared at 300 °C were the most active. Characterization showed that the catalysts had a nanowire-type morphology, and for those containing gold it was present as metallic particles occluded within the nanowires. The incorporation of gold into the catalyst enhanced the activity for propane conversion, but the presence of gold did not noticeably enhance the light-off activity. Althou…
Oxygen defects: The key parameter controlling the activity and selectivity of mesoporous copper-doped ceria for the total oxidation of naphthalene
Mesoporous CeO2 modified by the addition of copper has shown high efficiency for the total oxidation of naphthalene. High activity and 100% selectivity to carbon dioxide throughout the whole range of temperatures studied were achieved for copper loadings of 3.6% and lower. The catalytic behaviour has been related to the concentration of surface oxygen defects. A clear correlation between the concentration of surface oxygen defects (determined by XPS and DRIFTS) and the catalytic performance has been identified. Catalytic activity increased as copper was incorporated into the ceria up to 3.6%. In this range of copper content the copper was incorporated into the cubic fluorite lattice of CeO2…
Selective oxidation of C3–C4 olefins over Mo-containing catalysts with tetragonal tungsten bronze structure
Abstract Mo–V–Nb–P–O-based catalysts with a tetragonal tungsten bronze-type (TTB) structure have been prepared hydrothemally from a H 3 PMo 12 O 40 Keggin-type heteropolyacid. These catalysts have been tested in the oxidation of C 3 –C 4 olefins (propene, isobutene and 1-butene). Although the catalytic performance depends on the nature of the olefin fed the TTB-type catalysts prepared in the presence of elements of the V and VI groups such as Te, Sb and Bi have shown a high selectivity to partial oxidation products, especially that with Te. However, in the absence of these elements the TTB-catalysts present a high catalytic activity to deep oxidation. The selectivity to partial oxidation pr…
Oxidative dehydrogenation of ethane over NiO–CeO2 mixed oxides catalysts
[EN] In this paper we present the synthesis, characterization and catalytic behaviour in the oxidative dehydrogenation of ethane of NiO-CeO2 mixed oxides. The addition of cerium oxide to NiO strongly modifies its catalytic performance, although the changes in the catalytic behaviour depend on the catalyst composition. The incorporation of low amounts of cerium oxide to NiO multiplies the productivity to ethylene in the oxidative dehydrogenation of ethane by a factor of ca. 7, which is the result of an increase in both catalytic activity and selectivity to ethylene. The enhanced activity has been related to the remarkable increase of the surface area of catalyst and the low crystal sizes of …
Au deposited on CeO2 prepared by a nanocasting route: A high activity catalyst for CO oxidation
Abstract A set of catalysts comprised of gold on different CeO 2 supports has been prepared by a nanocasting route and characterized by several physicochemical techniques. These catalysts have been tested for CO oxidation and show outstanding catalytic activity. Higher calcination temperatures of the hard template, producing a poorly ordered silica template, have led to a higher amount of oxygen vacancies on the surface of CeO 2 . The presence of surface oxygen defects in the support combined with the deposition of Au nanoparticles ( ca. 3 nm) homogeneously dispersed on the CeO 2 support may explain the excellent behaviour for low temperature CO oxidation. Surprisingly, it has been observed…
Enhanced NiO Dispersion on a High Surface Area Pillared Heterostructure Covered by Niobium Leads to Optimal Behaviour in the Oxidative Dehydrogenation of Ethane
[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-containi…
Niobium phosphates as new highly selective catalysts for the oxidative dehydrogenation of ethane
Several niobium phosphate phases have been prepared, fully characterized and tested as catalysts for the selective oxidation of ethane to ethylene. Three distinct niobium phosphate catalysts were prepared, and each was comprised predominantly of a different bulk phase, namely Nb(2)P(4)O(15), NbOPO(4) and Nb(1.91)P(2.82)O(12). All of the niobium phosphate catalysts showed high selectivity towards ethylene, but the best catalyst was Nb(1.91)P(2.82)O(12), which was produced from the reduction of niobium oxide phosphate (NbOPO(4)) by hydrogen. It was particularly selective for ethylene, giving ca. 95% selectivity at 5% conversion, decreasing to ca. 90% at 15% conversion, and only produced low l…
The influence of cerium to urea preparation ratio of nanocrystalline ceria catalysts for the total oxidation of naphthalene
The influence of cerium salt/urea ratio on the activity of nanocrystalline ceria catalysts prepared by homogeneous precipitation with urea for the complete oxidation of naphthalene has been evaluated. Ceria catalysts were prepared from five different cerium salt/urea ratios (2:1, 1:1, 1:2, 1:3 and 1:4). Catalyst characterization (by BET, XRD and TPR) only revealed subtle differences in the characteristics of these catalysts with cerium salt to urea ratio. However, Raman and scanning electron microscopy (SEM) results indicated differences in the oxygen defect concentration (FWHM of Raman band) and morphology of the catalysts with variation of the preparation ratio. Catalysts prepared with 2:…
Understanding the role of Ti-rich domains in the stabilization of gold nanoparticles on mesoporous silica-based catalysts
3 Tablae, 14 Figures.-- Supplementary material.-- © 2018. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
Highly dispersed encapsulated AuPd nanoparticles on ordered mesoporous carbons for the direct synthesis of H2O2 from molecular oxygen and hydrogen
AuPd nanoparticles (<3 nm) have been encapsulated on the pores of a nanostructured CMK-3 carbon prepared by a nanocasting procedure. This material has been shown to be an excellent catalyst for the direct synthesis of hydrogen peroxide from molecular hydrogen and oxygen.
The nickel-support interaction as determining factor of the selectivity to ethylene in the oxidative dehydrogenation of ethane over nickel oxide/alumina catalysts
[EN] Nickel oxides supported on gamma-alumina (Ni-loading from 5 to 30 wt% NiO) have been synthesized and tested in the oxidative dehydrogenation (ODH) of ethane in order to determine the importance of the NiO-support interaction. The best performance was achieved by the catalyst with 15 wt% NiO; higher NiO-loadings lead to the formation of unselective bulk-like NiO and lower Ni-loadings present high proportion of free alumina surface sites. The presence of oxalic acid and/or niobium in the synthesis gel resulted in the formation of NiO particles with similar size, but higher crystallinity and reducibility than the standard 15 wt% NiO catalyst. The obtained results have revealed that, in ad…
Total oxidation of naphthalene using bulk manganese oxide catalysts
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 add…
High activity mesoporous copper doped cerium oxide catalysts for the total oxidation of polyaromatic hydrocarbon pollutants
The doping of mesoporous ceria with copper significantly enhances activity for naphthalene total oxidation, the enhanced performance is controlled by the increased concentration of surface oxygen defects.
Supported iridium catalysts for the total oxidation of short chain alkanes and their mixtures: Influence of the support
13 figures, 3 tables.-- Supplementary information available.-- © 2020. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
SiO2-supported vanadium magnesium mixed oxides as selective catalysts for the oxydehydrogenation of short chain alkanes
Abstract 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 …
Reaction products and pathways in the selective oxidation of C-2-C-4 alkanes on MoVTeNb mixed oxide catalysts
[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 …
The prevalence of surface oxygen vacancies over the mobility of bulk oxygen in nanostructured ceria for the total toluene oxidation
12 figures, 2 tables
Support effects on NiO-based catalysts for the oxidative dehydrogenation (ODH) of ethane
[EN] We report on the effect of NiO-support interactions on the chemical nature of Ni species in a series of supported NiO catalysts for the ODH of ethane. SiO2, TiO2-anatase, a high surface area TiO2 and a porous clay hetero-structure (PCH) with TiO2 and SiO2 pillars were used as supports, which led to a selectivity to ethylene in the range 30-90% over supported NiO catalysts. The catalysts were characterized by means of XRD, N-2-Adsorption, H-2-TPR, XPS and in situ (under H-2 reductive atmosphere) and ex situ XAS spectroscopy. The catalytic performance of supported materials is discussed in terms of their reducibility and specific reduction kinetics, but also taking into account the speci…
Gamma-valerolactone from levulinic acid and its esters: Substrate and reaction media determine the optimal catalyst
13 figures, 7 tables.-- © 2021. This manuscript version is made available under the CC-BY-NC-ND 4.0 license https://creativecommons.org/licenses/by-nc-nd/4.0
Deep oxidation of pollutants using gold deposited on a high surface area cobalt oxide prepared by a nanocasting route.
Gold deposited on a cobalt oxide with high surface area (138 m2 g−1), obtained through a nanocasting route using a siliceous KIT-6 mesoporous material as a hard template, has demonstrated high activity for the total oxidation of propane and toluene, and ambient temperature CO oxidation. The addition of gold promotes the activity when compared to a gold-free Co3O4 catalyst prepared using the same nanocasting technique. The enhanced catalytic activity when gold is present has been explained for the deep oxidation of propane and toluene in terms of the improved reducibility of cobalt oxide when gold is added, rather than to the intrinsic activity of metallic gold particles. The improved behavi…
The promoter effect of Nb species on the catalytic performance of Ir-based catalysts for VOCs total oxidation
12 figures, 2 tables.-- Supporting information available.
Selective oxidation of propane and ethane on diluted Mo–V–Nb–Te mixed-oxide catalysts
Abstract 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 forma…
TAP reactor study of the deep oxidation of propane using cobalt oxide and gold-containing cobalt oxide catalysts
Abstract A transient reactor study of the oxidation of propane to CO 2 on gold-free and gold-doped CoO x catalysts has been carried out. It has been demonstrated that the presence of gold markedly promotes the catalytic reactivity of cobalt oxide in the total oxidation of propane. Both catalysts oxidised propane directly to CO 2 via a Mars–Van Krevelen mechanism, and this was confirmed using isotopically labelled oxygen experiments. The increased activity of the gold catalyst is related to the faster reoxidation of the cobalt oxide when gold is present in the catalyst, since the reaction step in which the catalyst is reduced, due to propane oxidation, is similar for both catalysts. The fast…
Eco-friendly cavity-containing iron oxides prepared by mild routes as very efficient catalysts for the total oxidation of VOCs
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…
Selective oxidation of propane over alkali-doped Mo-V-Sb-O catalysts
[EN] Alkali metal-doped MoVSbO catalysts have been prepared by impregnation of a MoVSbO-mixed oxide (prepared previously by a hydrothermal synthesis) and finally activated at 500 or 600 degrees C in N-2. The catalysts have been characterized and tested for the selective oxidation of propane and propylene. Alkali-doped catalysts improved in general the catalytic performance of MoVSbO, resulting more selective to acrylic acid and less selective to acetic acid than the corresponding alkali-free MoVSbO catalysts. However, the specific behaviour strongly depends on both the alkali metal added and/or the final activation temperature. At isoconversion conditions, catalysts activated at 600 degrees…
Total oxidation of propane using nanocrystalline cobalt oxide and supported cobalt oxide catalysts
Abstract 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…
Influence of gel composition in the synthesis of MoVTeNb catalysts over their catalytic performance in partial propane and propylene oxidation
[EN] MoVTeNb mixed oxides catalysts have been prepared by a slurry method with different molar compositions (Mo/Te ratio from 2 to 6 and Nb/(V + Nb) ratio from 0 to 0.7) in the synthesis gel leading to different crystalline phases distribution and catalytic behaviour in the partial oxidation of both propane and propylene to acrylic acid. Chemical analysis indicates that the composition of samples before and after the heat-treatment changes, especially the Te-content, since a significant amount of Te is lost during the heat-treatment step when the amount of oxalate (from niobium oxalate) increases in the synthesis gel. Thus, the nature of the crystalline phases and the catalytic performance …
Easy Method for the Transformation of Levulinic Acid into Gamma-Valerolactone Using a Nickel Catalyst Derived from Nanocasted Nickel Oxide
Different nickel catalysts have been tested for the transformation of levulinic acid into &gamma
The significance of the order of impregnation on the activity of vanadia promoted palladium-alumina catalysts for propane total oxidation
The increased activity of alumina-supported palladium catalysts promoted with vanadium oxide has been investigated. Three different vanadium promoted Pd/Al2O3 catalysts with the same composition but synthesized employing sequential and co-impregnation were tested for the total oxidation of propane. The order of impregnation was critical to produce high activity catalysts. Vanadium and palladium co-impregnation on the Al2O3 support led to the most active catalyst, whereas the step-wise impregnated catalysts show a catalytic performance similar to or slightly better than unpromoted palladium catalysts. The high activity of the co-impregnated catalysts is related to the particle size and oxida…
Porous clays heterostructures as supports of iron oxide for environmental catalysis
[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 o…
Stable anchoring of dispersed gold nanoparticles on hierarchic porous silica-based materials
The nanometric organization of MOx (M = Co, Zn, Ni) domains partially embedded inside the mesoporous silica walls but accessible to the pore voids, which is achieved through a simple one-pot surfactant-assisted procedure, define optimal anchors for the nucleation and growth of gold nanoparticles, which in turn favours an exceptional thermal stability for the final Au-supported materials. As silica support we have selected a UVM-7 silica having a highly accessible architecture defined by two hierarchic pore systems. The combination of nanometric pore length, tortuous mesopores and MOx inorganic anchors favours the stability of the final Au/CoOx-UVM-7 nanocomposites.
Structural characterization of Niobium Phosphate Catalysts used for the Oxidative Dehydrogenation of Ethane to Ethylene
Extended abstract of a paper presented at Microscopy and Microanalysis 2011 in Nashville, Tennessee, USA, August 7–August 11, 2011.
Selective oxidative dehydrogenation of ethane over SnO2-promoted NiO catalysts
[EN] Ni-Sn-O mixed oxides catalysts have been investigated for the oxidative dehydrogenation of ethane. The catalysts were prepared through the evaporation of aqueous solutions of nickel nitrate and tin oxalate and finally calcined in air at 500 degrees C for 2 h. These materials have been characterized by several techniques (N-2-adsorption, X-ray diffraction, High-Resolution Electron Microscopy, temperature programmed reduction, X-Ray Photoelectron Spectroscopy, Fourier Transformed Infrared Spectroscopy of adsorbed CO and O-18/O-16 isotope exchange). The addition of just a tiny amount of tin highly increases the selectivity to ethylene (from ca. 40% to 80-90%). Thus, high selectivity to et…
Shape-dependency activity of nanostructured CeO2 in the total oxidation of polycyclic aromatic hydrocarbons
11 figures, 2 tables.-- © 2012. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
High-Temperature Stable Gold Nanoparticle Catalysts for Application under Severe Conditions: The Role of TiO2 Nanodomains in Structure and Activity
Metal nanoparticles with precisely controlled size are highly attractive for heterogeneous catalysis. However, their poor thermal stability remains a major concern in their application at realistic operating conditions. This paper demonstrates the possibility of synthesizing gold nanoparticles with exceptional thermal stability. This has been achieved by using a simple conventional deposition–precipitation technique. The material employed as catalyst consists of gold supported on a TiO2-impregnated SiO2 bimodal mesoporous support. The resulting material shows gold nanoparticles with a narrow size distribution around 3.0 nm, homogeneously dispersed over the TiO2/SiO2 material. Most interesti…
Glycerol selective oxidation to lactic acid over AuPt nanoparticles; Enhancing reaction selectivity and understanding by support modification
2 Schemes, 3 Tables, 5 Figures.
Highly Active Co3O4-Based Catalysts for Total Oxidation of Light C1–C3 Alkanes Prepared by a Simple Soft Chemistry Method: Effect of the Heat-Treatment Temperature and Mixture of Alkanes
9 figures, 2 tables.
Green synthesis of cavity-containing manganese oxides with superior catalytic performance in toluene oxidation
10 Figuras.- 2 Tablas.- Datos suplementarios disponibles en línea en la página web del editor.-- © 2019. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
Synergy between tungsten and palladium supported on titania for the catalytic total oxidation of propane
Titania-supported palladium catalysts modified by tungsten have been tested for the total oxidation of propane. The addition of tungsten significantly enhanced the catalytic activity. Highly active catalysts were prepared containing a low loading of 0.5 wt.% palladium, and activity increased as the tungsten loading was increased up to 6 wt.%. Catalysts were characterised using a variety of techniques, including powder X-ray diffraction, laser Raman spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction and aberration-corrected scanning transmission electron microscopy. Highly dispersed palladium nanoparticles were present on the catalyst with and without the additi…
Mixed oxide Ti Si O prepared by non-hydrolytic Xerogel method as a diluter of nickel oxide for the oxidative dehydrogenation of ethane
Abstract Mixed Ti Si O materials prepared by non-hydrolytic xerogel method have been employed as diluters for nickel oxide and used in the catalytic oxidative dehydrogenation of ethane. These catalysts have been characterized by several physicochemical techniques such as N2 adsorption, XRD, TPR, TEM, HR-TEM, and XPS. Supported nickel oxide catalysts have been reported to be efficient but only if the nature and the amount of support are controlled. In the present article it is shown that highly loaded (80 wt% NiO) nickel catalysts are more efficient when diluted on mixed Ti Si O materials with appropriate Ti/Si ratios than on pure TiO2 and SiO2 diluters. The catalytic results have been expla…
The different catalytic behaviour in the propane total oxidation of cobalt and manganese oxides prepared by a wet combustion procedure
Abstract 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 …
Low temperature total oxidation of toluene by bimetallic Au–Ir catalysts
9 Figuras.- 3 Tablas.- Información suplementaria disponible en la página web del editor
Mo-containing tetragonal tungsten bronzes. The influence of tellurium on catalytic behaviour in selective oxidation of propene
Abstract Te-free and Te-containing multicomponent Mo-based catalysts presenting tetragonal tungsten bronze (TTB) structure have been prepared, characterized and tested for the selective oxidation of propene. The catalysts were prepared hydrothermally and heat treated at 700 °C. The structural characterization performed by means of XRD, FTIR, SAED and HRTEM confirms the incorporation of tellurium to the TTB structural framework and shows that its presence does not modify in essence the crystalline structure. However, the incorporation of Te strongly modifies the catalytic performance, and the highest yield to acrolein has been achieved on catalysts with Te/Mo atomic ratios in bulk of 0.03. T…
Ferric sludge derived from the process of water purification as an efficient catalyst and/or support for the removal of volatile organic compounds
Ferric chloride solutions are used as coagulants or flocculants in water treatment operations for human consumption. This treatment produces large amounts of clay-type solids formed mainly of montmorillonite with iron oxides and humic substances. This ferric sludge can be used as an efficient catalyst for the removal of volatile organic compounds (VOCs) by total oxidation. This waste isolated in the purification process has been activated by calcinations in air, characterized by several physicochemical techniques and employed as a catalyst for the removal by total oxidation of representative VOCs: toluene, propane and mixtures of toluene/propane with or without water. This ferric sludge has…
Implementación del método del caso en la asignatura de Ingeniería de Procesos y Productos II del grado en Ingeniería Química
[EN] In this work, the case method has been used in the subject Process and Product Engineering II, which belongs to the fourth course of the Chemical Engineering Degree of the Universitat de València. Different cases have been proposed in the classroom practices in order to students acquire the competences of the subject and improve the results of the exam. A rubric was designed to evaluate the cases which was accessible to the students. The cases were proposed in the exam, in particular, cases related to four lessons which are usually complicated to students and the results obtained for these cases were compared with the results obtained in the questions (presented in a theoretical way) o…
(Ag)Pd-Fe3O4 Nanocomposites as Novel Catalysts for Methane Partial Oxidation at Low Temperature
Nanostructured composite materials based on noble mono-(Pd) or bi-metallic (Ag/Pd) particles supported on mixed iron oxides (II/III) with bulk magnetite structure (Fe3O4) have been developed in order to assess their potential for heterogeneous catalysis applications in methane partial oxidation. Advancing the direct transformation of methane into value-added chemicals is consensually accepted as the key to ensuring sustainable development in the forthcoming future. On the one hand, nanosized Fe3O4 particles with spherical morphology were synthesized by an aqueous-based reflux method employing different Fe (II)/Fe (III) molar ratios (2 or 4) and reflux temperatures (80, 95 or 110 °
Influence of the preparation method on the activity of ceria zirconia mixed oxides for naphthalene total oxidation
Cerium/zirconium mixed oxides, with different Ce/Zr ratios, have been synthesised by a co-precipitation method using two different precipitating agents (sodium carbonate and urea) and tested for the total oxidation of naphthalene. Catalysts were characterized by N2 adsorption, XRD, Raman, TPR, XPS and DRIFTS. Ceria prepared by carbonate precipitation had low activity and this is likely to be related to the high concentration of residual surface carbonate that covers catalytic sites and inhibits reaction. For carbonate precipitation, increasing the Zr content to 1% resulted in a significant increase of activity, which is related to the decrease of surface carbonate. Increasing the Zr content…
Total oxidation of naphthalene with high selectivity using a ceria catalyst prepared by a combustion method employing ethylene glycol.
Abstract 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 …
In-situ synthesis of hydrogen peroxide in tandem with selective oxidation reactions: A mini-review
7 Figuras, 6 Tablas
Enhanced H2O2 production over Au-rich bimetallic Au-Pd nanoparticles on ordered mesoporous carbons
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/
Influence of preparation conditions of nano-crystalline ceria catalysts on the total oxidation of naphthalene, a model polycyclic aromatic hydrocarbon
Abstract Nano-crystalline ceria catalysts prepared by homogeneous precipitation with urea were tested for the total oxidation of naphthalene, a model polycyclic aromatic hydrocarbon (PAH). Systematic variation of preparation conditions, including calcination temperature, calcination time and aging time, resulted in differences in surface area, reducibility, morphology and crystallite size of the CeO 2 catalyst and hence differences in catalytic performance. A combination of high surface area, small crystallite size and high oxygen defect concentration was found to favor the efficiency of the ceria catalysts for the total oxidation of naphthalene. Optimum preparation conditions for this stud…
Insights into the production of upgraded biofuels using Mg-loaded mesoporous ZSM-5 zeolites
9 figures, 6 tables.-- Supplementary information available.-- https://authorservices.wiley.com/author-resources/Journal-Authors/licensing/self-archiving.html
Oxidative dehydrogenation of ethane: A study over the structure and robustness of Ni–W–O catalysts
[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 cata…
"Partial oxidation of methane and methanol on FeOx-, MoOx- and FeMoOx -SiO2 catalysts prepared by sol-gel method: a comparative study"
[EN] FeOx-, MoOx and FeMoOx-SiO2 materials prepared by a sol-gel procedure have been evaluated as catalysts for the partial oxidation of methane and methanol. The effect of decreasing the pH of the synthesis gel on the chemical nature of FeOx and MoOx species has been investigated. Characterization results show that low pH improves the dispersion of metal oxide species present in SiO2 matrix. For FeOx/SiO2 materials, the presence of dispersed FeOx species (rather than bulk Fe2O3) improves the selectivity to formaldehyde in the partial oxidation of methane and methanol. For FeMoOx/SiOx catalysts, dispersed species favor the selectivity to formaldehyde only for methane oxidation. In contrast,…
Oxidative dehydrogenation of ethane on diluted or promoted nickel oxide catalysts: Influence of the promoter/diluter
Ti- and Nb- containing NiO catalysts have been synthesized by two different preparation methods: i) by precipitation (Me-Ni-O oxides, Me = Nb or Ti), in order to prepare promoted NiO catalysts; and ii) by wet impregnation on TiO or NbO supports, in order to prepare diluted/supported NiO catalysts. The catalysts have been also characterized and tested in the oxidative dehydrogenation of ethane. The catalytic performance of Ti- and Nb-promoted catalysts strongly depends on the composition, although in both cases the optimal one is found at similar Ti or Nb loadings (ca. 90 wt% NiO), showing similar ethylene selectivity in the ODH of ethane (ca. 90% at 10–20% ethane conversion). However, in th…
Tungsten-titanium mixed oxide bronzes: Synthesis, characterization and catalytic behavior in methanol transformation
[EN] Tungsten oxide bronze-based materials show extremely adaptive structural and compositional features that make them suitable for functional properties modulation. Herein we report the preparation of a series of Ti-containing tungsten oxide catalysts presenting a hexagonal tungsten bronze-type structure. The insertion of Ti4+ within the structure (likely in the octahedral framework of the hexagonal tungsten bronze) leads to an increase in the number of strong acid sites, and the disappearance of W5+ surface species found in the undoped tungsten oxide. With the aim of studying the acid-redox properties of the titled catalysts, the catalytic transformation of methanol has been carried out …
Assessing the Electrochemical Performance of Different Nanostructured CeO2 Samples as Anodes for Lithium-Ion Batteries
In this work, six samples of CeO2 are successfully prepared by diverse synthesis routes leading to different microstructures regarding both morphology and particle size. The structural and microstructural characteristics presented by the samples and their influence on the electrochemical response of the prepared anodes are analyzed. In particular, the Ce-CMK3 sample, synthesized from a mesoporous carbon obtained through a CMK3 silica template, displays an enhanced electrochemical response. Thus, capacity values of ~220 mA h g−1 are obtained at a current rate of 0.155 A g−1 after 50 cycles and an excellent cyclability at intermediate current densities. On the other hand, it is observed that …
Total oxidation of VOCs on Au nanoparticles anchored on Co doped mesoporous UVM-7 silica
Abstract 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 g…
Nickel oxide supported on porous clay heterostructures as selective catalysts for the oxidative dehydrogenation of ethane
[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 corresp…
Gas phase heterogeneous partial oxidation reactions
Abstract Mixed metal oxides are used as catalysts in the gas phase partial oxidation of hydrocarbons. This paper will present the principles of catalyst choice for selective oxidation reactions as well as the structural features of metal oxide catalysts. The nature of active sites in selective oxidation reactions will also be briefly discussed. We will pay special attention to several representative reactions: (1) ODH of short chain alkanes (from C1 to C4), (2) propene partial oxidation/ammoxidation on bismuth molybdate based catalysts, (3) n-butane direct oxidation to maleic anhydride on VPO type catalysts, and (4) propane direct oxidation/ammoxidation on mixed MoVTe(Sb)Nb–O catalysts. Fin…
Deep oxidation of propane using palladium–titania catalysts modified by niobium
Abstract Pd/TiO 2 catalysts modified by niobium have been prepared and tested for the complete oxidation of propane. The catalysts have been characterised by BET, XRD, laser Raman spectroscopy, XPS, DRS and TPR. The incorporation of niobium into Pd/TiO 2 catalysts resulted in a marked increase in the catalytic activity compared to the Nb-free Pd/TiO 2 catalysts, and the activity increased as the niobium and/or palladium loading increased. The addition of Nb significantly modified the nature of the palladium and niobium species. There was a marked increase in the oxygen mobility after niobium addition. This could not only promote the presence of palladium species in a totally oxidized state …
Molybdenum–vanadium supported on mesoporous alumina catalysts for the oxidative dehydrogenation of ethane
Abstract 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 …
Total oxidation of propane in vanadia-promoted platinum-alumina catalysts: Influence of the order of impregnation
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 vanadiu…
NiO diluted in high surface area TiO2 as efficient catalysts for the oxidative dehydrogenation of ethane
[EN] Catalysts consisting of NiO diluted in high surface area TiO2 can be as efficient in the oxidative dehydrogenation of ethane as the most selective NiO-promoted catalysts reported previously in the literature. By selecting the titania matrix and the NiO loading, yields to ethylene over 40% have been obtained. In the present article, three different titanium oxides (TiO2) have been employed as supports or diluters of nickel oxide and have been tested in the oxidative dehydrogenation of ethane to ethylene. All TiO2 used present anatase as the main crystalline phase and different surface areas of 11,55 and 85 m(2) g(-1). It has been observed that by selecting an appropriate nickel loading …