Density Functional Study of the CO Oxidation on a Doped Rutile TiO2(110): Effect of Ionic Au in Catalysis

We used density functional theory to examine whether doping oxides makes them better oxidation catalysts. We studied in detail titania doped with Au and used CO oxidation as a test of the oxidizing power of the system. We show that doping with Au, Ag, Cu, Pt, Pd, Ni reduces dramatically the bond of surface oxygen to titania or ceria, making them better oxidation catalysts. These calculations suggest that it is worthwhile to explore doped oxides as oxidation catalysts.     

Effects of the structure of ceria on the activity of gold/ceria catalysts for the oxidation of carbon monoxide and benzene

Using precipitated cerium hydroxide dried at 100 °C as the support, highly dispersed ceria-supported gold catalyst was prepared. Compared with similarly prepared catalysts supported on low-surface area ceria, gold on the high-surface area support showed more resistance to sintering and was more active toward the oxidation of CO and benzene. The oxidation of benzene was very dependent on the structure of ceria. Temperature-programmed reduction showed that the reducibility of surface oxygen was higher for high-surface area ceria. It is proposed that the creation of surface oxygen vacancies by ceria surface reduction promoted oxygen adsorption. Active oxygen formed by dissociation of the adsorbed oxygen is the active species for benzene oxidation, and the dissociation is promoted by gold nanoparticles. When present together in the reactant mixture, benzene inhibited the oxidation of CO, but CO enhanced the oxidation of benzene. Moisture had a promoting effect on both CO and benzene oxidation.     

Transition metal/fluorite-type oxides as active catalysts for reduction of sulfur dioxide to elemental sulfur by carbon monoxide

Reduction of SO₂ by CO to elemental sulfur on fluorite oxide and transition metal/fluorite oxide composite catalysts is discussed within the redox framework. The oxygen vacancies on the fluorite oxide are active catalyst sites and their creation is a key step to initiate the redox reaction. Transition metal/fluorite oxide composites demonstrate a strong synergism for the reaction. A reduction kinetics study of the copper/ceria system as a model composite catalyst has found that surface oxygen is highly active but its activity is inhibited by SO₂ adsorption. The TPR profile of the copper/ceria catalyst shows a significantly lower reduction peak than the individual components.     

Water–Gas Shift Reaction Over Aluminum Promoted Cu/CeO2 Nanocatalysts Characterized by XRD, BET, TPR and Cyclic Voltammetry (CV)

A series of aluminum promoted Cu/CeO₂ nanocatalysts with aluminum content in the range of 0–5wt.% were prepared by co-precipitation method and examined with respect to their catalytic performance for the water–gas shift (WGS) reaction. The catalysts were characterized by XRD, BET, H₂-TPR and cyclic voltammetry (CV) techniques. The results indicate that catalytic activity increases with the aluminum content at first, but then decreases with the further increase of aluminum content. Hereinto, Cu/CeO₂ catalyst doped with 1 wt.% of aluminum shows the highest catalytic activity (CO conversion reaches 84.4% at 200 °C) and thermal stability for WGS reaction. Correlation to the results from above characterization, it is found that the variation of catalytic activity is in very agreement with that of the surface area, the area of peak γ (i.e., the reduction of surface copper oxide (crystalline forms) interacted with surface oxygen vacancies on ceria), and the area of peak C₂ and in cyclic voltammetry process), respectively. Enough evidence was found for the fact that the metallic copper (Cu⁰) interacted with surface oxygen vacancies on ceria is the active site for WGS reaction over Cu/CeO₂ catalysts.     

Ceria‐based nanomaterials as catalysts for CO oxidation and soot combustion: Effect of Zr‐Pr doping and structural properties on the catalytic activity

In this work, we investigated a set of ceria‐based catalysts prepared by the hydrothermal and solution combustion synthesis. For the first time to our knowledge, we synthesized nanocubes of ceria doped with zirconium and praseodymium. The catalysts were tested for the CO and soot oxidation reactions. These materials exhibited different surface reducibility, as measured by H₂‐TPR, CO‐TPR and Soot‐TPR, despite their comparable chemical compositions. As a whole, Soot‐TPR appears a suitable characterization technique for the soot oxidation catalysts, whereas CO‐TPR technique allows to better discriminate among the CO oxidation activities. Praseodymium contributes positively toward the soot oxidation. On the other hand, it has an adverse effect on the CO oxidation over the same catalysts, as compared to pure ceria. The incorporation of zirconium into the ceria lattice does not have a direct beneficial effect on the soot oxidation activity, although it increases the catalyst performances for CO oxidation. © 2016 American Institute of Chemical Engineers AIChE J, 63: 216–225, 2017     

Catalysis by doped oxides: CO oxidation by AuxCe1−xO2

Density functional theory calculations for the CeO₂(111) surface doped with Au, Ag, and Cu show that the bond between the oxygen atoms and the oxide is weakened by presence of the dopant. In CO oxidation, doping of CeO₂ with Au allows the oxide to react readily with CO and make carbonates. These decompose to release CO₂ and form an oxygen vacancy on the surface. The vacancy adsorbs oxygen from the gas and weakens its bond, so that it reacts with CO to form a carbonate, which decomposes to release CO₂ and heal the oxygen vacancy. To be a good oxidation catalyst, a doped oxide must achieve a balance between two conflicting requirements: It must make surface oxygen reactive but not so much that it will hinder the healing of the oxygen vacancies created by the oxidation reaction.     

Comparison of the activity of Au/CeO2 and Au/Fe2O3 catalysts for the CO oxidation and the water-gas shift reactions

We compare the activity and relevant gold species of nanostructured gold–cerium oxide and gold–iron oxide catalysts for the CO oxidation by dioxygen and water. Well dispersed gold nanoparticles in reduced form provide the active sites for the CO oxidation reaction on both oxide supports. On the other hand, oxidized gold species, strongly bound on the support catalyze the water-gas shift reaction. Gold species weakly bound to ceria (doped with lanthana) or iron oxide can be removed by sodium cyanide at pH ≥12. Both parent and leached catalysts were investigated. The activity of the leached gold–iron oxide catalyst in CO oxidation is approximately two orders of magnitude lower than that of the parent material. However, after exposure to H₂ up to 400 °C gold diffuses out and is in reduced form on the surface, a process accompanied by a dramatic enhancement of the CO oxidation activity. Similar results were found with the gold–ceria catalysts. On the other hand, pre-reduction of the calcined leached catalyst samples did not promote their water-gas shift activity. UV–Vis, XANES and XPS were used to probe the oxidation state of the catalysts after various treatments.     

Gadolinia Doped Ceria Thin Films Prepared by Aerosol Assisted Chemical Vapor Deposition and Applications in Intermediate‐Temperature Solid Oxide Fuel Cells

Furthermore, deposition at such low temperatures is promising for processing of thin film assemblies. The preparation of bi‐layer electrolytes of yttria stabilized zirconia and gadolinia doped ceria thin films by aerosol assisted chemical vapor deposition is demonstrated. Gadolinia doped ceria films as thin as 150 nm are applied as barrier layers between yttria stabilized zirconia electrolyte and La_0.6Sr_0.4CoO_3–δ cathode in anode supported solid oxide fuel cells. High power densities above 850 mW cm^–2 at 650 °C are only obtained with these barrier layers, indicating that the GDC thin films effectively inhibit the formation of unwanted interface reactions.     

Selective oxidation of soot over Cu doped ceria/ceria–zirconia catalysts

Copper doped ceria and ceria–zirconia mixed oxides were prepared using the citric acid sol–gel method. The temperature-programmed oxidation (TPO) results showed that the Cu modification helped to improve the activity and selectivity of ceria and ceria–zirconia for soot catalytic oxidation. The CO-TPR results showed that Cu–Ce had a better reducibility than pure ceria at low temperatures. After ageing at 800 °C for 20 h in flow air, CuO–CeO₂ showed the maximum soot oxidation rate at 378 and 519 °C under tight and loose contact conditions, respectively, achieving a nearly 100% selectivity to CO₂ production. This effect may be attributed to the existence of well dispersed copper oxide species strongly interacting with the ceria surface, which may decrease the activation energy of soot oxidation. A conceivable mechanism of this synergetic effect was proposed.     

CeO2掺杂对CuO/沸石催化剂催化氧化VOCs活性的影响

研究CeO2改性得到的CuO/CeO2/沸石催化剂,进行催化氧化（燃烧）销毁乙醇、丙酮、甲苯和苯的实验,并用TPR和XPS对所制备的催化剂进行表征.研究结果表明：使用CuO/CeO2/沸石作为催化剂时,四种VOCs（挥发性有机物）催化燃烧的起燃和完全燃烧温度都明显低于当使用CuO /沸石作为催化剂时四种VOCs催化燃烧的起燃和完全燃烧温度,这表明CuO/CeO2/沸石催化剂的活性明显高于CuO/沸石催化剂的活性.TPR分析表明CeO2的添加有助于增强催化剂中Cu的还原性;XPS表征分析显示,CeO2的添加增加了铜在表面的分布,并且引起Cu 2p3/2的结合能由933.8eV 变到932.8eV 和 933.4eV, 在催化剂表面呈现出Cu2＋和Cu＋的形式.此外,在VOCs催化燃烧过程中,稀土Ce存在有部分还原变价过程（Ce^4 ＋ →Ce^3 ＋ ） ,也使催化剂的活性得到提高.     

Effect of steam and carbon dioxide pretreatments on methane decomposition and carbon gasification over doped-ceria supported nickel catalyst

Effects of steam (H₂O) and carbon dioxide (CO₂) pretreatments on methane (CH₄) decomposition and carbon gasification over doped-ceria supported nickel catalysts have been studied from 400 to 500 °C. The doped ceria employed were gadolinia-doped ceria and samaria-doped ceria. Results indicate that a drastic increase of both H₂O and CO₂ dissociation activities occurs as the temperature increases from 450 to 500 °C. The formation of the surface hydroxyl species during H₂O treatment inhibits the followed CH₄ decomposition. CO but no CO₂ was formed during CH₄ reaction after H₂O treatment. Carbon deposition during CH₄ decomposition is quite large but can be removed via gasification with afterward CO₂ treatment. However, some of the deposited carbon species is in a form which can not be removed with CO₂ treatment but can be removed with O₂ treatment. And, higher values of the oxygen-ion conductivity and the density of the surface oxygen vacancies lead to higher activities for all dissociation and decomposition reactions.     

铜掺杂Zr_0.4Ce_0.6O_2复合氧化物催化剂性能的研究

研究了铜掺杂 Zr0 .4 Ce0 .6O2 复合氧化物的还原性和催化性能 .结果表明 ,铜掺杂能显著提高该复合氧化物中氧化铈的还原性 ,降低氧化铜的还原温度 ,也能提高对 CO氧化的催化活性 ,这说明在铜与锆铈复合氧化物之间存在较强的相互作用 .焙烧处理对催化剂样品的性能亦有一定影响     

Study of SO2 adsorption and thermal regeneration over activated carbon-supported copper oxide catalysts

The mechanisms of SO₂ adsorption and regeneration over activated carbon-supported copper oxide sorbent/catalysts were analyzed. Studies were carried out in a fixed-bed reactor equipped with a non-dispersive infrared gas analyzer to detect the reaction products and by using X-ray powder diffraction (XRPD) and temperature-programmed desorption (TPD) experiments to characterize the nature of the sulfate species and surface oxygen complexes. The results indicate that SO₂ was catalytically oxidized to SO₃ over a copper phase in the presence of gaseous oxygen, and then reacted with a copper site to form a sulfate linked to copper without desorption into the gas phase. The activated carbon support did not participate in this sulfation reaction. After the adsorption of SO₂, the exhausted sorbent/catalysts could be regenerated by direct heat treatment in inert gas at temperatures between 260 and 480 °C, while the neighboring surface oxygen complexes on the carbon surface were acting as the reducing agents to reduce CuSO₄ to Cu. During the subsequent adsorption process, the copper is rapidly oxidized by oxygen in the flue gas.     

On the structure dependence of CO oxidation over CeO2 nanocrystals with well-defined surface planes

CO oxidation is a model reaction for probing the redox property of ceria-based catalysts. In this study, CO oxidation was investigated over ceria nanocrystals with defined surface planes (nanoshapes) including rods ({1 1 0} + {1 0 0}), cubes ({1 0 0}), and octahedra ({1 1 1}). To understand the strong dependence of CO oxidation observed on these different ceria nanoshapes, in situ techniques including infrared and Raman spectroscopy coupled with online mass spectrometer, and temperature-programmed reduction (TPR) were employed to reveal how CO interacts with the different ceria surfaces, while the mobility of ceria lattice oxygen was investigated via oxygen isotopic exchange experiment. CO adsorption at room temperature leads to strongly bonded carbonate species on the more reactive surfaces of rods and cubes but weakly bonded ones on the rather inert octahedra surface. CO-TPR, proceeding via several channels including CO removal of lattice oxygen, surface water–gas shift reaction, and CO disproportionation reaction, reveals that the reducibility of these ceria nanoshapes is in line with their CO oxidation activity, i.e., rods > cubes > octahedra. The mobility of lattice oxygen also shows similar dependence. It is suggested that surface oxygen vacancy formation energy, defect sites, and coordinatively unsaturated sites on ceria play a direct role in facilitating both CO interaction with ceria surface and the reactivity and mobility of lattice oxygen. The oxygen vacancy formation energy, nature and amount of the defect and low coordination sites are intrinsically affected by the surface planes of the ceria nanoshapes. Several reaction pathways for CO oxidation over the ceria nanoshapes are proposed, and certain types of carbonates, especially those associated with reduced ceria surface, are considered among the reaction intermediates to form CO₂, while the majority of carbonate species observed under CO oxidation condition are believed to be spectators.     

Noble metal catalysts supported on gadolinium doped ceria used for natural gas reforming in fuel cell applications

An attractive possibility to simplify a fuel cell system would be the use of a sulfur-tolerant reforming catalyst. In an effort to find such a catalyst, platinum, rhodium and ruthenium catalysts supported on ceria doped with 20% gadolinium and on pure ceria were synthesized and characterized. A temperature-programmed reduction study of the reduction behavior of the catalysts showed that the doping of ceria with gadolinium enhances the low temperature reduction, while the high temperature reduction is suppressed. The activity as well as the stability of the catalysts can be correlated with the reducibility of the materials. The most stable catalyst, rhodium supported on gadolinium doped ceria, shows promising sulfur-tolerance.     

Pore orientation of the gadolinia‐doped ceria cathode interlayer for a tubular SOFC using dip‐coating

An active region of cathode interlayer in a tubular solid oxide fuel cell (SOFC) is structurally analyzed using a dual‐beam focused ion beam/scanning electron microscope (FIB/SEM). The GDC (10 mol% gadolinia‐doped ceria) cathode interlayer (about 1 μm in thickness) is dip‐coated, and then sintered on YSZ (8 mol% yttria‐stabilized zirconia) electrolyte. At 1150°C sintering temperature, the pores oriented more along the axial direction than the radial direction. The anisotropy of pore shape is accounted for the withdrawal force during the dip‐coating of the GDC interlayer.     

Evaluation of carbon monoxide oxidation over CeO2/Co3O4 catalysts: Effect of ceria loading

Modification of cobaltic oxide (obtained from the reduction of high-valence cobalt oxide and assigned as R230, S_BET = 100 m² g⁻¹) with different loading of ceria was proceeded using the impregnation method (assigned as CeX/R230, X = 4, 12, 20, 35 and 50 wt%). The CeX/R230 catalysts were characterized by X-ray diffraction (XRD), nitrogen adsorption at −196 °C, temperature-programmed reduction (TPR) and transmission electron microscopy (TEM). Their catalytic activities towards the CO oxidation were studied in a continuous flow micro-reactor. The results revealed that the optimal modification, i.e., Ce20/R230, can increase the surface area (S_BET = 109 m² g⁻¹) of cobaltic oxide, further weaken the bond strength of CoO and lower the activation of CO oxidation among CeX/R230 catalysts due to the combined effect of cobaltic oxide and ceria. The Ce20/R230 catalyst exhibited the best catalytic activity in CO oxidation with T₅₀ (temperature for 50% CO conversion) at 88 °C.     

Oxides of copper, ceria promoted copper, manganese and copper manganese on Al2O3 for the combustion of CO, ethyl acetate and ethanol

Combustion of CO, ethyl acetate and ethanol was studied over CuO_x/Al₂O₃, CuO_x–CeO₂/Al₂O₃, CuMn₂O₄/Al₂O₃ and Mn₂O₃/Al₂O₃ catalysts. It was found that modification of the alumina with ceria before subsequent copper oxide deposition increases the activity for combustion of CO substantially, but the effect of ceria was small on the combustion of ethyl acetate and ethanol. The activity increases with the CuO_x loading until crystalline CuO particles are formed, which contribute little to the total active surface. The CuO_x–CeO₂/Al₂O₃ catalyst is more active than the CuMn₂O₄/Al₂O₃ catalyst for the oxidation of CO but the CuMn₂O₄/Al₂O₃ catalyst is more active for the combustion of ethyl acetate and ethanol.

Thermal ageing and water vapour in the feed caused a modest decrease in activity and did not affect the CuO_x–CeO₂/Al₂O₃ and CuMn₂O₄/Al₂O₃ catalysts differently. In addition, no difference in intermediates formed over the two catalysts was observed.

Characterisation with XRD, FT-Raman and TPR indicates that the copper oxide is present as a copper aluminate surface phase on alumina at low loading. At high loading, bulk CuO crystallites are present as well. Modification of the alumina with ceria before the copper oxide deposition gives well dispersed copper oxide species and bulk CuO crystallites associated to the ceria, in addition to the two copper oxide species on the bare alumina. The distribution of copper species depends on the ceria and copper oxide loading. The alumina supported copper manganese oxide and manganese oxide catalysts consist mainly of crystalline CuMn₂O₄ and Mn₂O₃, respectively, on Al₂O₃.     

Effect of NiO content on structural, surface and catalytic characteristics of nano-crystalline NiO/CeO2 system

The NiO/CeO₂ nano-composite catalysts containing different nickel content prepared by impregnation method have been characterized by XRD and TEM. The surface and catalytic properties of Ni/Ce mixed oxide solids were determined by nitrogen adsorption at −196 °C and catalytic conversion of isopropanol at different temperatures. These composites can be described as a mixture of nickel oxide and ceria modified by the insertion of a part of nickel in the ceria lattice. The size of the nickel oxide varies considerably from clusters to a crystallized material, depending on the amount of nickel oxide. From the characterization of the composites, it was concluded: at low Ni loading, the ceria surface is gradually covered with the dispersed NiO species. At higher loading, highly dispersed NiO, well crystalline nickel oxide and Ni-Ce-O solid solution coexist.It was verified that the structural, morphological, surface and catalytic properties could be influenced by nickel loading. This treatment led to a slightly increase in the crystallite size of ceria particles. On the other hand, the augmentation in the nickel content brought about an increase in the crystallite size, lattice constant and unit cell volume of nickel oxide. The nickel loading brought about an increase in the formation of Ni-Ce-O solid solution with subsequent creation of oxygen vacancies.     

Pressureless sintering of yttria-gadolinia co-stabilized zirconia

Zirconia ceramics partially stabilized with yttria and gadolinia [(3-x)Y,xGd-TZP; x = 0–2] were manufactured by intensive co-milling of zirconia and stabilizer oxides, spray granulation, axial pressing and pressureless sintering at 1300–1400 °C. Microstructure, phase composition and mechanical properties were determined. Stabilizer re-distribution in the materials at higher sintering temperatures was monitored by XRD. Substitution of yttria for gadolinia reduces the stabilizer content in the tetragonal phase, increases the tetragonality of the materials and induces higher transformability and toughness. The hardness is thereby reduced. In accordance with thermodynamic considerations the cubic content increases with increasing gadolinia content.