Strong metal-support interactions between highly dispersed Cu^(+) species and ceria via mix-MOF pyrolysis toward promoted water-gas shift reaction

The modulation of metal-support interfacial interaction is significant but challenging in the design of high-efficiency and high-stability supported catalysts.Here,we report a synthetic strategy to upgrade Cu-CeO_(2)interfacial interaction by the pyrolysis of mixed metal-organic framework(MOF)structure.The obtained highly dispersed Cu/CeO_(2)-MOF catalyst via this strategy was used to catalyze water-gas shift reaction(WGSR),which exhibited high activity of 40.5μmolCOgcat^(-1).s^(-1)at 300℃and high stability of about 120 h.Based on comprehensive studies of electronic structure,pyrolysis strategy has significant effect on enhancing metal-support interaction and then stabilizing interfacial Cu^(+)species under reaction conditions.Abundant Cu^(+)species and generated oxygen vacancies over Cu/CeO_(2)-MOF catalyst played a key role in CO molecule activation and H2O molecule dissociation,respectively.Both collaborated closely and then promoted WGSR catalytic performance in comparison with traditio nal supported catalysts.This study shall offer a robust approach to harvest highly dispersed catalysts with finely-tuned metal-support interactions for stabilizing the most interfacial active metal species in diverse heterogeneous catalytic reactions.

Atomic-layered Au clusters on α-MoC as catalysts for the low-temperature water-gas shift reaction

Subject Code:B03With the support by the National Natural Science Foundation of China,a collaborative study by the research groups led by Prof.Ma Ding(马丁)from Peking University,Senior Scientist JoséA.Rodriguez from Brookhaven National Laboratory and Prof.Shi Chuan(石川)from Dalian University of

Atomically dispersed copper species on ceria for the low-temperature water-gas shift reaction

The structure of copper species,dispersed on nanostructured ceria(particles,rods and cubes),was analyzed by scanning transmission electron microscopy(STEM)and X-ray photoelectron spectroscopy(XPS).It was interestingly found that the density of surface oxygen vacancies(or defect sites),induced by the shape of ceria,determined the geometrical structure and the chemical state of copper species.Atomically dispersed species and monolayers containing few to tens of atoms were formed on ceria particles and rods owing to the enriched anchoring sites,but copper clusters/particles co-existed,together with the highly dispersed atoms and monolayers,on cubic ceria.The atomically dispersed copper sites and monolayers interacted strongly with ceria,involving a remarkable charge transfer from copper to ceria at their interfaces.The activity for the low-temperature watergas shift reaction of the Cu/CeO_(2) catalysts was associated with the fraction of the positively-charged copper atoms,demonstrating that the active sites could be tuned by dispersing Cu species on shape-controlled ceria particles.

Effects of CeO_2 on structure and properties of Ni-Mn-K/bauxite catalysts for water-gas shift reaction

Multiple-metal catalysts （Ni-Mn-Ce-K/bauxite） for Water-Gas Shift （WGS） reaction were prepared by impregnation, and the catalytic structure and properties were investigated by N2 physical, XRD, H2-TPR, and CO-TPD. The results indicated that the addition of 7.5% CeO2 improved the activity of the WGS reaction obviously, and also increased the specific surface area and pore volume of the catalysts. The addition of CeO2 decreases the reduction temperature, enhanced the adsorption and activation of H2O2, and improved the adsorption content of CO. Besides, active sites were not changed and the number of active sites on catalysts did not increase obviously.

Copper Promoted Au/ZnO-CuO Catalysts for Low Temperature Water-gas Shift Reaction

Various copper promoted Au/ZnO-CuO catalysts with different atomic ratios of Cu to Zn prepared by means of co-precipitation were tested for the low temperature water-gas shift（WGS） reaction. The catalytic activity of the catalyst depends largely on the ratio of Cu to Zn. The addition of an appropriate amount of copper can considerably improve both the catalytic activity and the stability of the catalyst in comparison with those of copper-free Au/ZnO cata- lysts. The enhanced reducibility of copper oxide in the Au/ZnO-CuO ternary-component catalysts, which was confirmed by H2-TPR, may be related to the high activity and stability of the catalyst for the low temperature WGS reaction.

Effects of the partial replacement of La by M(M=Ce,Ca and Sr) in La_(2-x)M_xCuO_4 perovskites on catalysis of the water-gas shift reaction

The performance of La2-x M x CuO4 perovskites （where M=Ce,Ca or Sr） as catalysts for the water-gas shift reaction was investigated at 290℃ and 360℃.The catalysts were characterized by EDS,XRD,N2 adsorption-desorption,XPS and XANES.The XRD results showed that all the perovskites exhibited a single phase （the presence of perovskite structure）,suggesting the incorporation of metals in the perovskite structure.The XPS and XANES results showed the presence of Cu2＋ on the surface.The perovskites that exhibited the best catalytic performance were La 2 x Ce x CuO 4 perovskites,with CO conversions of 85% 90%.Moreover,these perovskites have higher surface areas and larger amounts of Cu on the surface.And Ce has a higher filled energy level than the other metals,increasing the energy of the valence band of Ce and providing more electrons for the reaction.Besides,the La1.80Ca0.20CuO4 perovskite showed a good catalytic performance.

Preparation and characterization of Cu-Ce-La mixed oxide as water-gas shift catalyst for fuel cells application

Cu-Ce-La mixed oxides were prepared by three precipitation methods （coprecipitation, homogeneous precipitation, and deposition precipitation） with variable precipitators and characterized using X-ray diffraction, BET, temperature-programmed reduction, and catalytic reaction for the water-gas shift. The Cu-Ce-La mixed oxide prepared by coprecipitation method with NaOH as precipitator presented the highest activity and thermal stability. Copper ion substituted quadrevalent ceria entered CeO2 （111） framework was in favor of activity and thermal stability of catalyst. The crystallinity of fresh catalysts increased with the reduction process. La^3＋ or Ce^4＋ substituted copper ion entered the CeO2 framework during reduction process. The coexistence of surface copper oxide （crystalline） and pure bulk crystalline copper oxide both contributed to the high activity and thermal stability of Cu-Ce-La mixes oxide catalyst.

Effects of ZrO_2 Content on Structure and Performance of Cu/CeO_2-ZrO_2 Catalysts for Water-Gas Shift Reaction

Cu/CeO2-ZrO2 catalysts for water-gas shift （WGS） reaction were prepared with co-precipitation method, and the influence of ZrO2 content on the catalytic structure and properties was investigated by the techniques of N2 physical adsorption analysis, XRD and H2-TPR. The results indicate that the BET surface areas of the catalysts are increased in varying degrees due to the presence of ZrO2. With increasing ZrO2 content, the pore size distribution is centered on 1.9 nm. ZrO2 can efficiently restrain the growth of Cu crystal particles. The appropriate amount of ZrO2 in the Cu/CeO2 catalysts can help the catalyst keep better copper dispersion in the WGS reaction, which can lead to both higher catalytic activity and better thermal stability. When ZrO2 content is 10% （atom fraction）, Cu/CeO2-Zr02 catalyst reaches a CO conversion rate of 73.7% at the reaction temperature of 200℃.

Three-dimensionally ordered macro-porous Pt/TiO_2 catalyst used for water-gas shift reaction

Three-dimensionally ordered macro-porous （3DOM） Pt/TiO2 catalysts were prepared by template and impregnation methods, and the resultant samples were characterized by using TG-DTA, XRD, SEM, TEM, and TPR techniques. The catalytic performance for water-gas shift （WGS） reaction was tested, and the influences of some conditions, such as reduction temperature of catalysts, the amount of Pt loadings and space velocity on catalytic performance were investigated. It was shown that Pt particles were homogeneously dispersed on 3DOM TiO2. The reduction of TiO2 surface was important for the catalytic performance. The activity test results showed that the 3DOM Pt/TiO2 catalysts exhibited very good catalytic performance for WGS reaction even at high space velocity, which was owing to the better mass transfer of 3DOM porous structure besides the high intrinsic activity of Pt/TiO2.

Potassium-decorated active carbon supported Co-Mo-based catalyst for water-gas shift reaction

The effect of potassium-decoration was studied on the activity of water-gas shift （WGS） reaction over the Co-Mo-based catalysts supported on active carbon （AC）, which was prepared by incipient wetness co-impregnation method. The decoration of potassium on active carbon in advance enhances the activities of the CoMo-K/AC catalysts for WGS reaction. Highest activity （about 92% conversion） was obtained at 250 ？ C for the catalyst with an optimum K 2 O/AC weight ratio in the range from 0.12 to 0.15. The catalysts were characterized by TPR and EPR, and the results show that activated carbon decorated with potassium makes Co-Mo species highly dispersed, and thus easily reduced and sulfurized. XRD results show that an appropriate content of potassium-decoration on active carbon supports may favors the formation of highly dispersed Co 9 S 8 -type structures which are situated on the edge or a site in contact with MoS 2 , K-Mo-O-S, Mo-S-K phase. Those active species are responsible for the high activity of CoMo-K/AC catalysts.

Influence of Gas Components on the Formation of Carbonyl Sulfide over Water-Gas Shift Catalyst B303Q

Water-gas shift reaction catalyst at lower temperature （200-400 ℃） may improve the conversion of carbon monoxide. But carbonyl sulfide was found to be present over the sulfided cobaltmolybdenum/alumina catalyst for water-gas shift reaction. The influences of temperature, space velocity, and gas components on the formation of carbonyl sulfide over sulfided cobalt-molybdenum/alumina catalyst B303Q at 200-400 ℃ were studied in a tubular fixed-bed quartz-glass reactor under simulated water-gas shift conditions. The experimental results showed that the yield of carbonyl sulfide over B303Q catalyst reached a maximum at 220 ℃ with the increase in temperature, sharply decreased with the increase in space velocity and the content of water vapor, increased with the increase in the content of carbon monoxide and carbon dioxide, and its yield increased and then reached a stable value with the increase in the content of hydrogen and hydrogen sulfide. The formation mechanism of carbonyl sulfide over B303Q catalyst at 200-400 ℃ was discussed on the basis of how these factors influence the formation of COS. The yield of carbonyl sulfide over B303Q catalyst at 200-400 ℃ was the combined result of two reactions, that is, COS was first produced by the reaction of carbon monoxide with hydrogen sulfide, and then the as-produced COS was converted to hydrogen sulfide and carbon dioxide by hydrolysis. The mechanism of COS formation is assumed as follows： sulfur atoms in the Co9Ss-MoS2/Al2O3 crystal lattice were easily removed and formed carbonyl sulfide with CO, and then hydrogen sulfide in the water-gas shift gas reacted with the crystal lattice oxygen atoms in CoO-MoOa/Al2O3 to form Co9S8-MoS2/Al2O3. This mechanism for the formation of COS over water-gas shift catalyst B303Q is in accordance with the Mars-Van Krevelen＇s redox mechanism over metal sulfide.

Effect of yttrium addition on water-gas shift reaction over CuO/CeO_2 catalysts

This paper presented a study on the role of yttrium addition to CuO/CeO2 catalyst for water-gas shift reaction. A single-step co-precipitation method was used for preparation of a series of yttrium doped CuO/CeO2 catalysts with yttrium content in the range of 0-5wt.%. Properties of the obtained samples were characterized and analyzed by X-ray diffraction （XRD）, Raman spectroscopy, H2-TPR, cyclic voltammetry （CV） and the BET method. The results revealed that catalytic activity was increased with the yttrium content at first, but then decreased with the further increase of yttrium content. Herein, CuO/CeO2 catalyst doped with 2wt.% of yttrium showed the highest catalytic activity （CO conversion reaches 93.4% at 250 ℃） and thermal stability for WGS reaction. The catalytic activity was correlated with the surface area, the area of peak γ of H2-TPR profile （i.e., the reduction of surface copper oxide （crystalline forms） interacted with surface oxygen vacancies on ceria）, and the area of peak C2 and A1 （Cu^0→←Cu^2＋ in cyclic voltammetry process）, respectively. Besides, Raman spectra provided evidences for a synergistic Cu-Ovacancy interaction, and it was indicated that doping yttrium may facilitate the formation of oxygen vacancies on ceria.

Direct identification of the carbonate intermediate during water-gas shift reaction at Pt-NiO interfaces using surface-enhanced Raman spectroscopy

Noble metal-reducible oxide interfaces have been regarded as one of the most active sites for water-gas shift reaction.However,the molecular reaction mechanism of water-gas shift reaction at these interfaces still remains unclear.Herein,water-gas shift reaction at Pt-NiO interfaces has been in-situ explored using surface-enhanced Raman spectroscopy by construction of Au@Pt@NiO nanostructures.Direct Raman spectroscopic evidence demonstrates that water-gas shift reaction at Pt-NiO interfaces proceeds via an associative mechanism with the carbonate species as a key intermediate.The carbonate species is generated through the reaction of adsorbed CO with gaseous water,and its decomposition is a slow step in water-gas shift reaction.Moreover,the Pt-NiO interfaces would promote the formation of this carbonate intermediate,thus leading to a higher activity compared with pure Pt.This spectral information deepens the fundamental understanding of the reaction mechanism of water-gas shift reaction,which would promote the design of more efficient catalysts.

A Modified Co-precipitation Method to Prepare Cu/ZnO/Al2O3 Catalyst and Its Application in Low Temperature Water-gas Shift(LT-WGS)Reaction

A modified co-precipitation method for the production of Cu/ZnO/Al2O3 complex was studied. The modification was that part of Al was introduced by adding Al^（3＋） into Cu^（2＋）/Zn^（2＋） solution, and the rest of Al was added after co-precipitation step in the form of pseudo-boehmite. The prepared samples were characterized by different techniques such as X-ray diffraction, N2 adsorption, H2-N2O titration, temperature programmed reduction and scanning electron microscopy. X-ray diffraction characterizations revealed that Al^（3＋） can be doped in aurichalcite lattice, and the maximum doping amount of Al^（3＋） was 5.0% of total Cu and Zn atoms. The Cu/ZnO/Al2O3 sample produced by the modified method, in which co-precipitated Al^（3＋） was 2.5% of total Cu and Zn atoms showed much better activity and stability in water-gas shift reaction than commercial sample. The high Cu surface area（26.1 m^2/g） obtained by decompositon of doped aurichalcite is believed to be responsible for the activity enhancement. The stability was enhanced mainly because of the support effect of γ-Al2O3, which was decomposed from pseudo-boehmite in the calcination step.

Insight into the Role of Isolated Gold Atoms-Ceria Conjunction in Catalyzing the Water-Gas Shift Reaction

As the promising catalysts for the water-gas shift(WGS)reaction,the activity of Au-CeO_(2) composites is susceptible to the aggregation size and electronic state of Au species.Previous reports were extensively focused on the discrepancy between nonmetallic Au and metallic Au nanoparticles,whereas the understanding of the authentic role of the isolated Au atoms was limited.Herein,we investigated the catalytic behavior and structural information over two types of Au/CeO_(2) catalysts,in which the predominant conjunctions were isolated Au1-CeO_(2) and Aun-CeO_(2),respectively.Based on comprehensive characterizations,particularly by in-situ Raman and in-situ DRIFTS,we found that the isolated Au atoms were responsible for enhancing the reducibility of the CeO_(2) matrix.The CO adsorption ability on the isolated Au sites was significantly inferior to clustered Au atoms,especially at relatively high temperatures(>200°C).As a result,the boosted O vacancy on the isolated Au1-CeO_(2) conjunctions could improve the H2O activation ability for the Au-CeO_(2) catalysts and demonstrate a comparable activity to the clustered Aun-CeO_(2) sites.This work might deepen understanding of the catalytic function for the isolated Au1 site within Au/CeO_(2) systems while catalyzing the WGS reaction.

Theoretical and experimental investigations on single-atom catalysis:Pt_(1)/FeO_(x) for water-gas shift reaction

Oxide-supported metal single-atom catalysts(SACs)have exhibited excellent catalytic performance for water-gas shift(WGS)reaction.Here,we report the single-atom catalyst Pt1/FeOx exhibits excellent medium temperature catalytic performance for WGS reactions by the density functional theory(DFT)calculations and experimental results.The calculations indicate that H_(2)O molecules are easily dissociated at oxygen vacancies,and the formed*OH and*O are adsorbed on Pt1 single atoms and the adjacent O atoms,respectively.After studying four possible reaction mechanisms,it is found that the optimal WGS reaction pathway is proceeded along the carboxyl mechanism(pathway III),in which the formation of*COOH intermediates can promote the stability of Pt_(1)/FeO_(x) SAC and the easier occurrence of WGS reaction.The energy barrier of the rate-determining step during the entire reaction cycle is only 1.16 eV,showing the high activity for the medium temperature WGS reaction on Pt_(1)/FeO_(x) SAC,which was verified by experimental results.Moreover,the calculated turnover frequencies(TOFs)of CO_(2)and H_(2)formation on Pt1/FeOx at 610 K(337℃)can reach up to 1.14×10^(-3)s^(-1)·site^(-1)through carboxyl mechanism.In this work,we further expand the application potential of Pt1/FeOx SAC in WGS reaction.

Water gas shift activity of Co-Mo/MgO-Al_2O_3 catalysts presulfided with ammonium sulfide

Co-Mo/MgO-Al2O3 catalyst was presulfided with ammonium sulfide in aqueous solution and activated with synthesis gas for water gas shift reaction. The assay results indicate that the presulfided Co-Mo/MgO-Al2O3 catalyst exhibits an excellent catalytic activity and stability. XRD and EPR characterization results show that the O-S exchange might occur during the impregnation, leading to the formation of （NH4）2MoS4 （or （NH4）zMoxSy） precursor, which was then thermally decomposed and reduced to MoS2. The higher catalytic performance is attributed to an optimization formation of active Co-Mo sulfides, consisting of well dispersed MoS2 and Co-Mo-S phase due to the redispersion of Co sulfide particles over the edges of newly formed MoS2 crystallites.

Effect of precipitants on Ni-CeO_2 catalysts prepared by a co-precipitation method for the reverse water-gas shift reaction

A series of Ni-CeO2 catalysts were prepared by co-precipitation method with Na2CO3, NaOH, and mixed precipitant （Na2CO3：NaOH; 1：1 ratio） as precipitant, respectively. The effect of the precipitants on the catalytic performance, physical and chemical properties of Ni-CeO2 catalysts was investigated with the aid of X-ray diffraction （XRD）, Bmmaner-Emmett-Teller method （BET）, Fou- rier-transform infrared spectroscopy （FT-IR）, thermogravimetry （TG）, and H2-TPR characterizations. The Ni-CeO2 catalysts were exam- ined with respect to their catalytic performance for the reverse water-gas shift reaction, and their catalytic activities were ranked as： Ni-CeO2-CP （Na2CO3：NaOH=I：I）〉Ni-CeO2-CP（Na2CO3）〉Ni-CeO2-CP（NaOH）- Correlating to the characteristic results, it was found that the catalyst prepared by co-precipitation with mixed precipitant （Na2CO3：NaOH; 1：1 ratio） as precipitant hadthe most amount of oxygen vacancies accompanied with highly dispersed Ni particles, which made the corresponding Ni-CeO2-CP（Na2CO3：NaOH=I： 1） catalyst exhibit the highest catalytic activity. While the precipitant of Na2CO3 or NaOH resulted in less or no oxygen vacancies in Ni-CeO2 catalysts. As a result, Ni-CeO2-CP（Na2CO3） and Ni-CeO2-CP（NaOH） catalysts presented poor catalytic performance.

Influence of preparation method on performance of Ni-CeO_2 catalysts for reverse water-gas shift reaction

This study investigated 1 wt.% Ni-CeO2 catalysts that were prepared using co-precipitation, deposition-precipitation, and impregnation methods for the reverse water-gas shift （RWGS） reaction. Characterizations of the catalyst samples were conducted by Brumauer-Emmett-Teller （BET）, atomic absorption spectrophotometer （AAS）, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, high-resolution transmission electron microscopy （HR-TEM） and temperature programmed reduction （TPR）. The results showed that the Ni-CeO2 catalyst prepared using the co-precipitation method exhibited the best catalytic performance. In the Ni-CeO2 catalyst prepared using co-precipitation method, a combination of highly dispersed NiO and abundant oxygen vacancies was assumed to play a crucial role in determining the catalytic activity and selectivity of the RWGS reaction.

Effect of doping rare earth oxide on performance of copper-manganese catalysts for water-gas shift reaction

Rare earth-doped copper-manganese mixed oxide catalysts were prepared by coprecipitation and mechanical mixing using copper sulfate, manganese sulfate, and rare-earth oxides REO （REO indicates La2O3, CeO2, Y2O3, or Pr6O11） as raw materials. The samples were characterized by X-ray diffraction （XRD）, temperature-programmed reduction （TPR）, temperature-programmed reduc-tion of oxidized surfaces （s-TPR）, and temperature-programmed desorption （TPD）. Catalytic activities were tested for a water-gas shift reaction. Doping rare earth oxides did not alter the crystal structure of the original copper-manganese mixed oxides but changed the interplanar spacing, adsorption performance and reaction performance. Doping with La2O3 enhanced the activity and stability of Cu-Mn mixed oxides because of high copper distribution and fine reduction. Doping with CeO2 and Y2O3 also decreased the reduc-tion temperatures of the samples to different degrees while improving the dispersion of Cu on the surface, thus, catalytic activity was better than that of undoped Cu-Mn sample. The Pr6O11-doped sample was difficult to reduce, the dispersion of surface coppers was lowered, resulting in poor activity.