Behavior of Molybdenum–Vanadium Mixed Oxides in Selective Oxidation and Disproportionation of Toluene

This study deals with the behavior of molybdenum–vanadium (Mo/V) mixed oxides catalysts in both disproportionation and selective oxidation of toluene. Samples containing different Mo/V ratios were prepared by a modified method using tetradecyltrimethylammonium bromide and acetic acid. The catalysts were characterized using several techniques: nitrogen adsorption–desorption isotherms, X-Ray diffraction (XRD), ammonia temperature-programmed desorption (TPD-NH3), temperature-programmed reduction by hydrogen (H2-TPR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, Fourier-transform infrared-spectroscopy (FTIR) and ultraviolet-visible spectroscopies (UV–VIS). The XRD results evidenced the presence of orthorhombic α-MoO3 and V2O5 phases, as well as monoclinic β-MoO3 and V2MoO8 phases, their abundance depending on the Mo to V ratio, while the TPD-NH3 emphasized that, the total amount of the acid sites diminished with the increase of the Mo loading. The TPR investigations indicated that the samples with higher Mo/V ratio possess a higher reducibility. The main findings of this study led to the conclusion that the presence of strong acid sites afforded a high conversion in toluene disproportionation (Mo/V = 1), while a higher reducibility is a prerequisite to accomplishing high conversion in toluene oxidation (Mo/V = 2). The catalyst with Mo/V = 1 acquires the best yield to xylenes from the toluene disproportionation reaction, while the catalyst with Mo/V = 0.33 presents the highest yield to benzaldehyde.

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Influence of Sulfur-Containing Sodium Salt Poisoned V2O5–WO3/TiO2 Catalysts on SO2–SO3 Conversion and NO Removal

Catalysts ◽

10.3390/catal8110541 ◽

2018 ◽

Vol 8 (11) ◽

pp. 541 ◽

Cited By ~ 3

Author(s):

Haiping Xiao ◽

Chaozong Dou ◽

Hao Shi ◽

Jinlin Ge ◽

Li Cai

Keyword(s):

Photoelectron Spectroscopy ◽

No Reduction ◽

Catalytic Performance ◽

Acid Sites ◽

Impregnation Method ◽

So2 Oxidation ◽

Sodium Salts ◽

X Ray ◽

Temperature Programmed ◽

Physical Features

A series of poisoned catalysts with various forms and contents of sodium salts (Na2SO4 and Na2S2O7) were prepared using the wet impregnation method. The influence of sodium salts poisoned catalysts on SO2 oxidation and NO reduction was investigated. The chemical and physical features of the catalysts were characterized via NH3-temperature programmed desorption (NH3-TPD), H2-temperature programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), and Fourier Transform Infrared Spectroscopy (FT-IR). The results showed that sodium salts poisoned catalysts led to a decrease in the denitration efficiency. The 3.6% Na2SO4 poisoned catalyst was the most severely deactivated with denitration efficiency of only 50.97% at 350 °C. The introduction of SO42− and S2O72− created new Brønsted acid sites, which facilitated the adsorption of NH3 and NO reduction. The sodium salts poisoned catalysts significantly increased the conversion of SO2–SO3. 3.6%Na2S2O7 poisoned catalyst had the strongest effect on SO2 oxidation and the catalyst achieved a maximum SO2–SO3-conversion of 1.44% at 410 °C. Characterization results showed sodium salts poisoned catalysts consumed the active ingredient and lowered the V4+/V5+ ratio, which suppressed catalytic performance. However, they increased the content of chemically adsorbed oxygen and the strength of V5+=O bonds, which promoted SO2 oxidation.

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Bulk Versus Surface Modification of Alumina with Mn and Ce Based Oxides for CH4 Catalytic Combustion

Materials ◽

10.3390/ma12111771 ◽

2019 ◽

Vol 12 (11) ◽

pp. 1771 ◽

Cited By ~ 2

Author(s):

Stefan Neatu ◽

Mihaela M. Trandafir ◽

Adelina Stănoiu ◽

Ovidiu G. Florea ◽

Cristian E. Simion ◽

...

Keyword(s):

Photoelectron Spectroscopy ◽

Catalytic Combustion ◽

Mixed Oxides ◽

Sol Gel ◽

Nitrogen Adsorption ◽

X Ray Diffraction ◽

X Ray ◽

Temperature Programmed ◽

Catalytic Combustion Of Methane ◽

Adsorption Desorption

This study presents the synthesis and characterization of lanthanum-modified alumina supported cerium–manganese mixed oxides, which were prepared by three different methods (coprecipitation, impregnation and citrate-based sol-gel method) followed by calcination at 500 °C. The physicochemical properties of the synthesized materials were investigated by various characterization techniques, namely: nitrogen adsorption-desorption isotherms, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and H2–temperature programmed reduction (TPR). This experimental study demonstrated that the role of the catalytic surface is much more important than the bulk one. Indeed, the incipient impregnation of CeO2–MnOx catalyst, supported on an optimized amount of 4 wt.% La2O3–Al2O3, provided the best results of the catalytic combustion of methane on our catalytic micro-convertors. This is mainly due to: (i) the highest pore size dimensions according to the Brunauer-Emmett-Teller (BET) investigations, (ii) the highest amount of Mn4+ or/and Ce4+ on the surface as revealed by XPS, (iii) the presence of a mixed phase (Ce2MnO6) as shown by X-ray diffraction; and (iv) a higher reducibility of Mn4+ or/and Ce4+ species as displayed by H2–TPR and therefore more reactive oxygen species.

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Synthesis of Zirconia Doped Molybdenum Oxide as Efficient Catalysts for Ultrasound Assisted Synthesis of Substituted Pyrazoles

Asian Journal of Chemistry ◽

10.14233/ajchem.2021.23260 ◽

2021 ◽

Vol 33 (9) ◽

pp. 2007-2014

Author(s):

Amal A. Muftah ◽

Shobha A. Waghmode ◽

Sharda R. Gadale

Keyword(s):

Photoelectron Spectroscopy ◽

Mixed Oxides ◽

Sol Gel ◽

Temperature Stability ◽

Acid Sites ◽

High Yield ◽

Ultra Sound ◽

Electron Microscopes ◽

Temperature Programmed ◽

Substituted Pyrazoles

To explore green methodology for the synthesis of mixed oxide, its catalytic activity and temperature stability of series of ZrO2/MoO3 and ZrO2 were prepared by sol-gel method and characterized by XRD, FT-IR, X-ray photoelectron spectroscopy (XPS), temperature programmed Desorption (TPD), Raman spectroscopy and transmission electron microscopes (TEM). These mixed oxides were showed high stability with nanocrystalline nature. Due to highly acidic nature of the catalysts, ultra sound assisted synthesis of substituted pyrazoles was carried out successfully with high yield. The reaction was carried out in solvent free medium, which showed green approach and energy saving reaction. Condensation of dibenzoyl methane and hydrazine to form substituted pyrazoles with 97.7% yield. The acid strength and acid amount of synthesized catalysts were determined by temperature programmed desoprtion (TPD), incorporation of zirconia into the molybdenum, network has changed its surface acid properties due to the Zr2+ and Mo6+ ions. After addition of ZrO2 on MoO3, it showed weak and strong acid sites.

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Palladium-doped hierarchical ZSM-5 for catalytic selective oxidation of allylic and benzylic alcohols

Royal Society Open Science ◽

10.1098/rsos.211086 ◽

2021 ◽

Vol 8 (10) ◽

Author(s):

Shengzhe Ding ◽

Muhammad Ganesh ◽

Yilai Jiao ◽

Xiaoxia Ou ◽

Mark A. Isaacs ◽

...

Keyword(s):

Selective Oxidation ◽

Active Site ◽

Photoelectron Spectroscopy ◽

Active Sites ◽

Hierarchical Zeolites ◽

X Ray ◽

Transmission Electron ◽

Scanning Transmission ◽

Temperature Programmed ◽

Alcohol Conversion

Hierarchical zeolites have the potential to provide a breakthrough in transport limitation, which hinders pristine microporous zeolites and thus may broaden their range of applications. We have explored the use of Pd-doped hierarchical ZSM-5 zeolites for aerobic selective oxidation (selox) of cinnamyl alcohol and benzyl alcohol to their corresponding aldehydes. Hierarchical ZSM-5 with differing acidity (H-form and Na-form) were employed and compared with two microporous ZSM-5 equivalents. Characterization of the four catalysts by X-ray diffraction, nitrogen porosimetry, NH 3 temperature-programmed desorption, CO chemisorption, high-resolution scanning transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy allowed investigation of their porosity, acidity, as well as Pd active sites. The incorporation of complementary mesoporosity, within the hierarchical zeolites, enhances both active site dispersion and PdO active site generation. Likewise, alcohol conversion was also improved with the presence of secondary mesoporosity, while strong Brønsted acidity, present solely within the H-form systems, negatively impacted overall selectivity through undesirable self-etherification. Therefore, tuning support porosity and acidity alongside active site dispersion is paramount for optimal aldehyde production.

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Zn-Al Mixed Oxides Decorated with Potassium as Catalysts for HT-WGS: Preparation and Properties

Catalysts ◽

10.3390/catal10091094 ◽

2020 ◽

Vol 10 (9) ◽

pp. 1094 ◽

Cited By ~ 1

Author(s):

Katarzyna Antoniak-Jurak ◽

Paweł Kowalik ◽

Kamila Michalska ◽

Wiesław Próchniak ◽

Robert Bicki

Keyword(s):

Photoelectron Spectroscopy ◽

Mixed Oxides ◽

Catalyst Activity ◽

Molar Ratio ◽

X Ray ◽

Molar Ratios ◽

Mixed Oxide Catalysts ◽

Wgs Reaction ◽

Temperature Programmed ◽

Co Precipitation

A set of ex-ZnAl-LDHs catalysts with a molar ratio of Zn/Al in the range of 0.3–1.0 was prepared using co-precipitation and thermal treatment. The samples were characterized using various methods, including X-ray fluorescence spectroscopy (XRF), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy FT-IR, N2 adsorption, Temperature-programmed desorption of CO2 (TPD-CO2) as well as Scanning electron microscopy (SEM-EDS). Catalyst activity and long-term stability measurements were carried out in a high-temperature water–gas shift (HT-WGS) reaction. Mixed oxide catalysts with various Zn/Al molar ratios decorated with potassium showed high activity in the HT-WGS reaction within the temperature range of 330–400 °C. The highest activity was found for the Zn/Al molar ratio of 0.5 corresponding to spinel stoichiometry. However, the catalyst with a stoichiometric spinel molar ratio of Zn/Al (ZnAl_0.5_K) revealed a higher tendency for surface migration and/or vaporization of potassium during overheating at 450 °C. The correlation of the activity results and TPD-CO2 data show that medium basic sites enhance the progress of the HT-WGS reaction.

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Cellulose Conversion to 5 Hydroxymethyl Furfural (5-HMF) Using Al-Incorporated SBA-15 as Highly Efficient Catalyst

Journal of Chemistry ◽

10.1155/2019/5785621 ◽

2019 ◽

Vol 2019 ◽

pp. 1-8 ◽

Cited By ~ 1

Author(s):

Son Tung Pham ◽

Manh B. Nguyen ◽

Giang H. Le ◽

Trang T. T. Pham ◽

Trang T. T. Quan ◽

...

Keyword(s):

Hydrothermal Process ◽

Strong Acid ◽

Acid Sites ◽

Efficient Catalyst ◽

Cellulose Conversion ◽

X Ray ◽

Hydroxymethyl Furfural ◽

Temperature Programmed ◽

Strong Acid Sites ◽

Adsorption Desorption

Al-incorporated SBA-15 samples (xAl/SBA-15) were successfully prepared by “atomic implantation” method. The samples were characterized by X-ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), N2 adsorption-desorption isotherms (BET), and temperature-programmed desorption (NH3-TPD). In this catalyst, metal oxide species were highly dispersed on the SBA-15 surface and existed as isolated atoms. It was shown that the Al incorporation lead to the formation of medium and strong acid sites. The catalytic activity and selectivity were tested in a mild hydrothermal process for degradation of cotton cellulose to 5-hydroxymethyl furfural (5-HMF). A cellulose conversion of 68.5% and 5-HMF selectivity of 62.1% after 2 h of reaction at 170°C were achieved. The very high 5-HMF yield (42.57%) obtained in this paper is much higher than that was reported in the literature.

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Effect of the Ni/Al Ratio on the Performance of NiAl2O4 Spinel-Based Catalysts for Supercritical Methylcyclohexane Catalytic Cracking

Catalysts ◽

10.3390/catal11030323 ◽

2021 ◽

Vol 11 (3) ◽

pp. 323

Author(s):

Kyoung Ho Song ◽

Soon Kwan Jeong ◽

Byung Hun Jeong ◽

Kwan-Young Lee ◽

Hak Joo Kim

Keyword(s):

Spinel Structure ◽

Coke Formation ◽

Strong Acid ◽

Acid Sites ◽

The Other ◽

X Ray ◽

Temperature Programmed Oxidation ◽

Temperature Programmed ◽

Co Precipitation ◽

Strong Acid Sites

Supercritical methylcyclohexane cracking of NiAl2O4 spinel-based catalysts with varying Ni/Al deficiencies was investigated. Thus, catalysts with Ni content of 10–50 wt.% were prepared by typical co-precipitation methods. The calcined, reduced, and spent catalysts were characterized by X-ray diffraction, O2 temperature-programmed oxidation, NH3 temperature-programmed desorption, N2 physisorption, O2 chemisorption, scanning and transmission electron microscopy, and X-ray fluorescence. The performance and physicochemical properties of the reference stoichiometric Ni3Al7 catalyst differed significantly from those of the other catalysts. Indeed, the Ni-deficient Ni1Al9 catalyst led to the formation of large Ni particles (diameter: 20 nm) and abundant strong acid sites, without spinel structure formation, owing to the excess Al. These acted with sufficient environment and structure to form the coke precursor nickel carbide, resulting in a pressure drop within 17 min. On the other hand, the additional NiO linked to the NiAl2O4 spinel structure of the Al-deficient Ni5Al5 catalyst formed small crystals (10 nm), owing to the excess Ni, and displayed improved Ni dispersion. Thus, dehydrogenation proceeded effectively, thereby improving the resistance to coke formation. This catalytic behavior further demonstrated the remarkable activity and stability of this catalyst under mild conditions (450 °C and 4 Mpa).

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Synthesis, Characterization and Kinetic Behavior of Supported Cobalt Catalysts for Oxidative after-Treatment of Methane Lean Mixtures

Materials ◽

10.3390/ma12193174 ◽

2019 ◽

Vol 12 (19) ◽

pp. 3174 ◽

Cited By ~ 1

Author(s):

Andoni Choya ◽

Beatriz de Rivas ◽

Jose Ignacio Gutiérrez-Ortiz ◽

Juan Ramón González-Velasco ◽

Rubén López-Fonseca

Keyword(s):

Photoelectron Spectroscopy ◽

Mixed Oxides ◽

Cobalt Content ◽

Cobalt Catalysts ◽

X Ray Diffraction ◽

X Ray ◽

Good Thermal Stability ◽

Supported Cobalt Catalysts ◽

Temperature Programmed ◽

Cobalt Species

The present work addresses the influence of the support on the catalytic behavior of Co3O4-based catalysts in the combustion of lean methane present in the exhaust gases from natural gas vehicular engines. Three different supports were selected, namely γ-alumina, magnesia and ceria and the corresponding catalysts were loaded with a nominal cobalt content of 30 wt. %. The samples were characterized by N2 physisorption, wavelength dispersive X-ray fluorescence (WDXRF), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction with hydrogen and methane. The performance was negatively influenced by a strong cobalt-support interaction, which in turn reduced the amount of active cobalt species as Co3O4. Hence, when alumina or magnesia supports were employed, the formation of CoAl2O4 or Co–Mg mixed oxides, respectively, with a low reducibility was evident, while ceria showed a lower affinity for deposited cobalt and this remained essentially as Co3O4. Furthermore, the observed partial insertion of Ce into the Co3O4 lattice played a beneficial role in promoting the oxygen mobility at low temperatures and consequently the catalytic activity. This catalyst also exhibited a good thermal stability while the presence of water vapor in the feedstream induced a partial inhibition, which was found to be completely reversible.

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The Effect of Noble Metal (M: Ir, Pt, Pd) on M/Ce2O3-γ-Al2O3 Catalysts for Hydrogen Production via the Steam Reforming of Glycerol

Catalysts ◽

10.3390/catal10070790 ◽

2020 ◽

Vol 10 (7) ◽

pp. 790

Author(s):

Nikolaos D. Charisiou ◽

Georgios I. Siakavelas ◽

Kyriakos N. Papageridis ◽

Davide Motta ◽

Nikolaos Dimitratos ◽

...

Keyword(s):

Steam Reforming ◽

Photoelectron Spectroscopy ◽

Acid Sites ◽

Unsaturated Hydrocarbon ◽

Effect Of Temperature ◽

Incipient Wetness Impregnation ◽

X Ray ◽

Gaseous Products ◽

Metal Support Interaction ◽

Temperature Programmed

A promising route for the energetic valorisation of the main by-product of the biodiesel industry is the steam reforming of glycerol, as it can theoretically produce seven moles of H2 for every mole of C3H8O3. In the work presented herein, CeO2–Al2O3 was used as supporting material for Ir, Pd and Pt catalysts, which were prepared using the incipient wetness impregnation technique and characterized by employing N2 adsorption–desorption, X-Ray Diffraction (XRD), Temperature Programmed Reduction (TPR), Temperature Programmed Desorption (TPD), X-ray Photoelectron Spectroscopy (XPS) and Transmission Electron Microscopy (TEM). The catalytic experiments aimed at identifying the effect of temperature on the total conversion of glycerol, on the conversion of glycerol to gaseous products, the selectivity towards the gaseous products (H2, CO2, CO, CH4) and the determination of the H2/CO and CO/CO2 molar ratios. The main liquid effluents produced during the reaction were quantified. The results revealed that the Pt/CeAl catalyst was more selective towards H2, which can be related to its increased number of Brønsted acid sites, which improved the hydrogenolysis and dehydrogenation–dehydration of condensable intermediates. The time-on-stream experiments, undertaken at low Water Glycerol Feed Ratios (WGFR), showed gradual deactivation for all catalysts. This is likely due to the dehydration reaction, which leads to the formation of unsaturated hydrocarbon species and eventually to carbon deposition. The weak metal–support interaction shown for the Ir/CeAl catalyst also led to pronounced sintering of the metallic particles.

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Comparision on the Low-Temperature NH3-SCR Performance of γ-Fe2O3 Catalysts Prepared by Two Different Methods

Catalysts ◽

10.3390/catal9121018 ◽

2019 ◽

Vol 9 (12) ◽

pp. 1018

Author(s):

Naveed Husnain ◽

Enlu Wang ◽

Shagufta Fareed ◽

Muhammad Tuoqeer Anwar

Keyword(s):

Photoelectron Spectroscopy ◽

Catalytic Reduction ◽

Acid Sites ◽

High Concentration ◽

X Ray ◽

Nh3 Scr ◽

Transmission Electron ◽

Temperature Programmed ◽

Diffuse Reflectance Infrared

Maghemite (γ-Fe2O3) catalysts were prepared by two different methods, and their activities and selectivities for selective catalytic reduction of NO with NH3 were investigated. The methods of X-ray powder diffraction (XRD), Brunauer–Emmett–Teller (BET), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR), ammonia temperature-programmed desorption (NH3-TPD), transmission electron microscopy (TEM), Energy-dispersive X-ray spectroscopy (EDS), and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) were used to characterize the catalysts. The resulted demonstrated that the γ-Fe2O3 nanoparticles prepared by the facile method (γ-Fe2O3–FM) not only exhibited better NH3-SCR activity and selectivity than the catalyst prepared by the coprecipitation method but also showed improved SO2 tolerance. This superior NH3-SCR performance was credited to the existence of the larger surface area, better pore structure, a high concentration of lattice oxygen and surface-adsorbed oxygen, good reducibility, a lot of acid sites, lower activation energy, adsorption of the reactants, and the existence of unstable nitrates on the surface of the γ-Fe2O3–FM.

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