The activation of CO_(2)molecules is a fundamental step for their effective utilization.Constructing highdensity oxygen vacancies on the surface of reducible oxides is pivotal for the activation of CO_(2).In this work...The activation of CO_(2)molecules is a fundamental step for their effective utilization.Constructing highdensity oxygen vacancies on the surface of reducible oxides is pivotal for the activation of CO_(2).In this work,we prepared a series of 0.5PtxCe/Al_(2)O_(3)(x=1,5,10,or 20)catalysts with varying Ce loading and 0.5 wt%of Pt for the reverse water gas shift(RWGS)reaction.The size of CeO_(2)particle increases with Ce loading.Remarkably,the 0.5Pt5Ce/Al_(2)O_(3) catalyst with an average CeO_(2)particle size of 5.5 nm exhibits a very high CO_(2)conversion rate(116.4×10^(-5)mol_(CO_(2))/(g_(cat)·s))and CO selectivity(96.1%)at 600℃.Our experimental findings reveal that the small-size CeO_(2)in 0.5Pt5Ce/Al_(2)O_(3) possesses a greater capacity to generate reactive oxygen vacancies,promoting the adsorption and activation of CO_(2).In addition,the oxygen vacancies are cyclically generated and consumed during the reaction,which contributes to the elevated catalytic performance of the catalyst.This work provides a general strategy to construct rich oxygen vacancies on CeO_(2)for designing high-performance catalysts in C_(1) chemistry.展开更多
The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift （RWGS） reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activ...The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift （RWGS） reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activity, selectivity, and stability for RWGS reaction. Characterizations of the catalyst samples were conducted by XRD and TPR. The results indicated that, in Ni-CeO2 catalysts, there were three kinds of nickel, nickel ions in ceria lattice, highly dispersed NiO and bulk NiO. Oxygen vacancies were formed in CeO2 lattice due to the incorporation of Ni^2＋ ions into ceria lattice. Oxygen vacancies formed in ceria lattice and highly dispersed Ni were key active components for RWGS, and bulk Ni was key active component for methanation of CO2.展开更多
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 th...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.展开更多
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 catalyti...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.展开更多
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 P...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.展开更多
In reverse water gas shift （RWGS） reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were...In reverse water gas shift （RWGS） reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction （XRD）, Brunauer-Emmett-Teller （BET） method, inductively coupled plasma atomic emission spectrometer （ICP-AES）, temperature programmed reduction （H2-TPR）, CO chemisorption, energy dispersive X-ray （EDX） and scanning electron microscopy （SEM） techniques. Kinetic properties of all catalysts were investigated in a batch re- actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/AlzO3 catalyst enhances its activity as compared to Fe/AlaO3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/AlzO3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fez（MoO4）3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fez（MoO4）3 phase has low reducibility, therefore the Fe2（MoO4）3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.展开更多
The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to amm...The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature catalysts have shown promising results, including high selectivity, high shift rates, and higher activity potential. Additionally, significant progress has been made in removing trace CO through the redox reaction in electrolytic cell. This paper reviews the development of WGS reaction catalysts, including the reaction mechanism, catalyst design, and innovative research methods. The catalyst plays a crucial role in the WGS reaction, and this paper provides an instant of catalyst design under different conditions. The progress of catalysts is closely related to the development of advanced characterization techniques.Furthermore, modifying the catalyst surface to enhance activity and significantly increase reaction kinetics is a current research direction. This review goals to stimulate a better understanding of catalyst design, performance optimization, and driving mechanisms, leading to further progress in this field.展开更多
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-desorpt...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.展开更多
The performance of La2-xCexCu1-yZnyO4 perovskites as catalysts for the high temperature water-gas shift reaction （HT-WGSR） was investigated. The catalysts were characterized by EDS, XRD, BET surface area, TPR, and X...The performance of La2-xCexCu1-yZnyO4 perovskites as catalysts for the high temperature water-gas shift reaction （HT-WGSR） was investigated. The catalysts were characterized by EDS, XRD, BET surface area, TPR, and XANES. The results showed that all the perovskites exhibited the La2CuO4 orthorhombic structure, so the Pechini method is suitable for the preparation of pure perovskite. However, the La1.90Ce0.10CuO4 perovskite alone, when calcined at 350/700℃, also showed a （La0.935Ce0.065）2CuO4 perovskite with tetragonal struc- ture, which produced a surface area higher than the other perovskites. The perovskites that exhibited the best catalytic performance were those calcined at 350/700℃ and, among these, La1.90Ce0.10CuO4 was outstanding, probably because of the high surface area associated with the presence of the （La0.935Ce0.065）2CuO4 perovskite with tetragonal structure and orthorhombic La2CuO4 phase.展开更多
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 o...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.展开更多
The water gas shift reaction is of vital significance for the generation and transition of energy due to the application in hydrogen production and industries such as ammonia synthesis and fuel cells.The influence of ...The water gas shift reaction is of vital significance for the generation and transition of energy due to the application in hydrogen production and industries such as ammonia synthesis and fuel cells.The influence of support doping and bimetallic alloying on the catalytic performance of Pt/Ce O_(2)-based nanocatalysts in water gas shift reaction was reported in this work.Various lanthanide ions and 3d transition metals were respectively introduced into the Ce O_(2)support or Pt to form Pt/Ce O_(2):Ln(Ln=La,Nd,Gd,Tb,Yb)and Pt M/Ce O_(2)(M=Fe,Co,Ni)nanocatalysts.The sample of Pt/Ce O_(2):Tb showed the highest activity(TOF at 200℃=0.051 s^(-1))among the Pt/Ce O_(2):Ln and the undoped Pt/Ce O_(2)catalysts.Besides,the sample of Pt Fe/Ce O_(2)exhibited the highest activity(TOF at 200℃=0.12 s^(-1))among Pt M/Ce O_(2)catalysts.The results of the multiple characterizations indicated that the catalytic activity of Pt/Ce O_(2):Ln catalysts was closely correlated with the amount of oxygen vacancies in doped ceria support.However,the different activity of Pt M/Ce O_(2)bimetallic catalysts was owing to the various Pt oxidation states of the bimetals dispersed on ceria.The study of the reaction pathway indicated that both the samples of Pt/Ce O_(2)and Pt/Ce O_(2):Tb catalyzed the reaction through the formate pathway,and the enhanced activity of the latter derived from the increased concentration of oxygen vacancies along with promoted water dissociation.As for the sample of Pt Fe/Ce O_(2),its catalytic mechanism was the carboxyl route with a higher reaction rate due to the moderate valence of Pt along with improved CO activation.展开更多
The preparation of the iron-based catalysts promoted by cobalt with a small amount of copper and aluminum for the high temperature shift reaction （HTS） with different sequences of adding catalyst raw materials durin...The preparation of the iron-based catalysts promoted by cobalt with a small amount of copper and aluminum for the high temperature shift reaction （HTS） with different sequences of adding catalyst raw materials during neutralization and precipitation was investigated. XRD, BET and particle size distribution （PSD） were used to characterize the prepared catalysts. It was found that the catalyst crystals were all γ-Fe2O3, and the intermediate of the catalyst after aging was Fe3O4. The crystallographic form of the catalyst and its intermediate was not affected by the addition sequence in the neutralization and precipitation process. The results showed that the specific surface area and the particle size of the catalysts depended on the addition sequence to the mother liquor. Cobalt with a small amount of copper and aluminum could increase the specific surface area and decrease the particle size of catalysts.展开更多
Based on formate and direct oxidation mechanisms,three Langmuir-Hinshelwood-Hougen-Watson （LHHW） kinetic models of the water-gasshift （WGS） reaction over a nano-structured iron catalyst under Fischer-Tropsch synth...Based on formate and direct oxidation mechanisms,three Langmuir-Hinshelwood-Hougen-Watson （LHHW） kinetic models of the water-gasshift （WGS） reaction over a nano-structured iron catalyst under Fischer-Tropsch synthesis （FTS） reaction conditions were derived and compared with those over the conventional catalyst.The conventional and nanostructured Fe/Cu/La/Si catalysts were prepared by co-precipitation of Fe and Cu nitrates in aqueous media and water-oil micro-emulsion,respectively.The WGS kinetic data were measured by experiments over a wide range of reaction conditions and comparisons were also made for various rate equations.WGS rate expressions based on the formate mechanism with the assumption that the formation of formate is rate determining step were found to be the best.展开更多
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 rem...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.展开更多
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)i...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.展开更多
Reverse water gas shift(RWGS)reaction is a crucial process in CO_(2)utilization.Herein,Ni-and NiCe-containing hexagonal mesoporous silica(Ni-HMS and NiCe-HMS)catalysts were synthesized using an insitu one-pot method a...Reverse water gas shift(RWGS)reaction is a crucial process in CO_(2)utilization.Herein,Ni-and NiCe-containing hexagonal mesoporous silica(Ni-HMS and NiCe-HMS)catalysts were synthesized using an insitu one-pot method and applied for RWGS reaction.At certain reaction temperatures 500-750℃,Ni-HMS samples displayed a higher selectivity to the preferable CO than that of conventionally impregnated Ni/HMS catalyst.This could be originated from the smaller NiO nanoparticles over Ni-HMS catalyst.NiCe-HMS exhibited higher activity compared to Ni-HMS.The catalysts were characterized by means of TEM,XPS,XRD,H_(2)-TPR,CO_(2)-TPD,EPR and N_(2) adsorption-desortion technology.It was found that introduction of Ce created high concentration of oxygen vacancies,served as the active site for activating CO_(2).Also,this work analyzed the effect of the H_(2)/CO_(2)molar ratio on the best NiCe-HMS.When reaction gas H_(2)/CO_(2)molar ratio was 4 significantly decreased the selectivity to CO at low temperature,but triggered a higher CO_(2)conversion which is close to the equilibrium.展开更多
Thermal decomposition of formic acid on SiO2, CeO2 and γ-Al2O3 was studied as an elementary step of reverse water–gas shit reaction（RWGS） over supported Au catalysts. γ-Al2O3 showed the highest CO selectivity amo...Thermal decomposition of formic acid on SiO2, CeO2 and γ-Al2O3 was studied as an elementary step of reverse water–gas shit reaction（RWGS） over supported Au catalysts. γ-Al2O3 showed the highest CO selectivity among the tested oxides in the decomposition of formic acid. Infrared spectroscopy showed the formation of four formate species on γ-Al2O3： three η~1-type and one μ~2-type species, and these formates decomposed to CO at 473 K or higher. Au-loaded γ-Al2O3 samples were prepared by a depositionprecipitation method and used as catalysts for RWGS. The supported Au catalyst gave CO with high selectivity over 99% from CO2 and H2, which is attributed to the formation of formates on Au and subsequent decomposition to CO on γ-Al2O3.展开更多
The utilization of pure hydrogen as an energy source in fuel cells gave rise to renewed interest in developing active and stable water-gas shift catalysts. Gold catalysts have proven to be very efficient for water-gas...The utilization of pure hydrogen as an energy source in fuel cells gave rise to renewed interest in developing active and stable water-gas shift catalysts. Gold catalysts have proven to be very efficient for water-gas shift reaction at low temperature. The aim of the present study was to investigate the effect of:(i) different preparation methods(impregnation and coprecipitation) to obtain a modified ceria support,and(ii) the amount of Y_2 O_3(1.0 wt%, 2.5 wt%, 5.0 wt% and 7.5 wt%) as dopant on the water-gas shift activity of Au/CeO_2 catalysts. An extended characterization by means of S_(BET), XRD, HRTEM/HAADF, FTIR,H_2-TPR and CO-TPR measurements in combination with careful evaluation of the catalyst behavior allowed to shed light on the parameters governing the water-gas shift activity. The catalysts show very high activity(>90% CO conversion) in the temperature range 180-220 ℃,with a slightly better performance of the gold catalysts on supports prepared by impregnation. The decreased activity with increasing Y_2 O_3 concentration is related to the hindering of oxygen mobility due to ordering of surface oxygen vacancies in vicinity of segregated Y^(3+). The effect of catalyst pre-treatments and the stability of the best performing samples were examined as well.展开更多
The reverse water–gas shift(RWGS)reaction combined with Fischer–Tropsch synthesis establishes a promising tandem catalytic system for transforming CO_(2)into valuable chemicals and fuels[1,2].However,the techno-econ...The reverse water–gas shift(RWGS)reaction combined with Fischer–Tropsch synthesis establishes a promising tandem catalytic system for transforming CO_(2)into valuable chemicals and fuels[1,2].However,the techno-economic assessment suggests that the RWGS reaction becomes viable and economically competitive only when catalysts with 100%CO selectivity(thus eliminating the downstream separation step),high activity,sufficiently long operational durability,and ideally produced from earth-abundant materials and energy-efficient routes,are available[3].展开更多
Reverse water-gas shift reaction represents a strategic pathway for CO_(2) utilization.Despite its potential,reverse water-gas shift reaction via conventional thermal-catalysis faces several challenges,including low e...Reverse water-gas shift reaction represents a strategic pathway for CO_(2) utilization.Despite its potential,reverse water-gas shift reaction via conventional thermal-catalysis faces several challenges,including low equilibrium conversion rates due to thermodynamic constraints,high energy consumption,and insufficient product selectivity.Here,this study demonstrates an evident synergetic effect between plasma and Ag/ZnO,on enhancing reverse water-gas shift reaction.The plasma catalytic system achieved significantly improved performance with a remarkable CO_(2) conversion rate of 76.5%,a high CO selectivity of 96.8% and a CO yield of 74.1%,along with an energy efficiency as high as 0.19 mmol·kJ^(-1),surpassing the plasma alone system and ZnO catalytic systems.Results from X-ray photoelectron spectroscopy and Auger electron spectroscopy confirm the presence of electronic metal-support interactions between Ag and ZnO,which facilitates the formation of electron-deficient Ag sites and partially reduced ZnOx species.These reactive sites,along with oxygen vacancies created during reduction treatment,enhance the adsorption and activation of H_(2) and CO_(2),offering a dominant plasma-assisted surface reaction pathway for the improved reverse water-gas shift reaction.These findings underscore the crucial role of electronic metal-support interactions in manipulating surface environments to facilitate efficient plasma-assisted catalytic reactions,with significant implications for the rational design of catalysts capable of converting CO_(2) efficiently under mild conditions.展开更多
基金Project supported by the National Science Fund for Distinguished Young Scholars of China(22225110)the National Key Research and Development Program of China(2021YFA1501103)+1 种基金the National Science Foundation of China(22075166,22271177)the Young Scholars Program of Shandong University。
文摘The activation of CO_(2)molecules is a fundamental step for their effective utilization.Constructing highdensity oxygen vacancies on the surface of reducible oxides is pivotal for the activation of CO_(2).In this work,we prepared a series of 0.5PtxCe/Al_(2)O_(3)(x=1,5,10,or 20)catalysts with varying Ce loading and 0.5 wt%of Pt for the reverse water gas shift(RWGS)reaction.The size of CeO_(2)particle increases with Ce loading.Remarkably,the 0.5Pt5Ce/Al_(2)O_(3) catalyst with an average CeO_(2)particle size of 5.5 nm exhibits a very high CO_(2)conversion rate(116.4×10^(-5)mol_(CO_(2))/(g_(cat)·s))and CO selectivity(96.1%)at 600℃.Our experimental findings reveal that the small-size CeO_(2)in 0.5Pt5Ce/Al_(2)O_(3) possesses a greater capacity to generate reactive oxygen vacancies,promoting the adsorption and activation of CO_(2).In addition,the oxygen vacancies are cyclically generated and consumed during the reaction,which contributes to the elevated catalytic performance of the catalyst.This work provides a general strategy to construct rich oxygen vacancies on CeO_(2)for designing high-performance catalysts in C_(1) chemistry.
基金Project supported by the National Natural Science Foundation of China (20476079)
文摘The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift （RWGS） reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activity, selectivity, and stability for RWGS reaction. Characterizations of the catalyst samples were conducted by XRD and TPR. The results indicated that, in Ni-CeO2 catalysts, there were three kinds of nickel, nickel ions in ceria lattice, highly dispersed NiO and bulk NiO. Oxygen vacancies were formed in CeO2 lattice due to the incorporation of Ni^2＋ ions into ceria lattice. Oxygen vacancies formed in ceria lattice and highly dispersed Ni were key active components for RWGS, and bulk Ni was key active component for methanation of CO2.
基金supported by the Foundation of Natural Science of Zhejiang Province(Y4110220)Foundation of the Zhejiang Provincial Department of Education(Y200908245)
文摘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.
基金Project supported by Natural Science Foundation of Zhejiang Province(Y4110220)Foundation of the Zhejiang Provincial Department of Education(Y200908245)Foundation of the Dinghai Academy of Science and Technology(201006)
文摘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.
基金Project supported by National Natural Science Foundation of China(21066008,21266017)Inner Mongolia Science and Technology Plan Project(20101502)
文摘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.
基金Supported by the Iranian Nano Technology Initiative Council and Petroleum University of Technology
文摘In reverse water gas shift （RWGS） reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction （XRD）, Brunauer-Emmett-Teller （BET） method, inductively coupled plasma atomic emission spectrometer （ICP-AES）, temperature programmed reduction （H2-TPR）, CO chemisorption, energy dispersive X-ray （EDX） and scanning electron microscopy （SEM） techniques. Kinetic properties of all catalysts were investigated in a batch re- actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/AlzO3 catalyst enhances its activity as compared to Fe/AlaO3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/AlzO3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fez（MoO4）3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fez（MoO4）3 phase has low reducibility, therefore the Fe2（MoO4）3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.
基金financially supported by the National Natural Science Foundation of China (22279118, 22279117, 22075254,31901272)the Top-Notch Talent Program of Henan Agricultural University (30501034)。
文摘The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature catalysts have shown promising results, including high selectivity, high shift rates, and higher activity potential. Additionally, significant progress has been made in removing trace CO through the redox reaction in electrolytic cell. This paper reviews the development of WGS reaction catalysts, including the reaction mechanism, catalyst design, and innovative research methods. The catalyst plays a crucial role in the WGS reaction, and this paper provides an instant of catalyst design under different conditions. The progress of catalysts is closely related to the development of advanced characterization techniques.Furthermore, modifying the catalyst surface to enhance activity and significantly increase reaction kinetics is a current research direction. This review goals to stimulate a better understanding of catalyst design, performance optimization, and driving mechanisms, leading to further progress in this field.
文摘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.
基金supported by Fundaco de Amparo àPesquisa do Estado de So Paulo
文摘The performance of La2-xCexCu1-yZnyO4 perovskites as catalysts for the high temperature water-gas shift reaction （HT-WGSR） was investigated. The catalysts were characterized by EDS, XRD, BET surface area, TPR, and XANES. The results showed that all the perovskites exhibited the La2CuO4 orthorhombic structure, so the Pechini method is suitable for the preparation of pure perovskite. However, the La1.90Ce0.10CuO4 perovskite alone, when calcined at 350/700℃, also showed a （La0.935Ce0.065）2CuO4 perovskite with tetragonal struc- ture, which produced a surface area higher than the other perovskites. The perovskites that exhibited the best catalytic performance were those calcined at 350/700℃ and, among these, La1.90Ce0.10CuO4 was outstanding, probably because of the high surface area associated with the presence of the （La0.935Ce0.065）2CuO4 perovskite with tetragonal structure and orthorhombic La2CuO4 phase.
文摘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.
基金financial support from the National Natural Science Foundation of China(21832001 and 21771009)the Beijing National Laboratory for Molecular Sciences(BNLMSCXXM-202104)。
文摘The water gas shift reaction is of vital significance for the generation and transition of energy due to the application in hydrogen production and industries such as ammonia synthesis and fuel cells.The influence of support doping and bimetallic alloying on the catalytic performance of Pt/Ce O_(2)-based nanocatalysts in water gas shift reaction was reported in this work.Various lanthanide ions and 3d transition metals were respectively introduced into the Ce O_(2)support or Pt to form Pt/Ce O_(2):Ln(Ln=La,Nd,Gd,Tb,Yb)and Pt M/Ce O_(2)(M=Fe,Co,Ni)nanocatalysts.The sample of Pt/Ce O_(2):Tb showed the highest activity(TOF at 200℃=0.051 s^(-1))among the Pt/Ce O_(2):Ln and the undoped Pt/Ce O_(2)catalysts.Besides,the sample of Pt Fe/Ce O_(2)exhibited the highest activity(TOF at 200℃=0.12 s^(-1))among Pt M/Ce O_(2)catalysts.The results of the multiple characterizations indicated that the catalytic activity of Pt/Ce O_(2):Ln catalysts was closely correlated with the amount of oxygen vacancies in doped ceria support.However,the different activity of Pt M/Ce O_(2)bimetallic catalysts was owing to the various Pt oxidation states of the bimetals dispersed on ceria.The study of the reaction pathway indicated that both the samples of Pt/Ce O_(2)and Pt/Ce O_(2):Tb catalyzed the reaction through the formate pathway,and the enhanced activity of the latter derived from the increased concentration of oxygen vacancies along with promoted water dissociation.As for the sample of Pt Fe/Ce O_(2),its catalytic mechanism was the carboxyl route with a higher reaction rate due to the moderate valence of Pt along with improved CO activation.
文摘The preparation of the iron-based catalysts promoted by cobalt with a small amount of copper and aluminum for the high temperature shift reaction （HTS） with different sequences of adding catalyst raw materials during neutralization and precipitation was investigated. XRD, BET and particle size distribution （PSD） were used to characterize the prepared catalysts. It was found that the catalyst crystals were all γ-Fe2O3, and the intermediate of the catalyst after aging was Fe3O4. The crystallographic form of the catalyst and its intermediate was not affected by the addition sequence in the neutralization and precipitation process. The results showed that the specific surface area and the particle size of the catalysts depended on the addition sequence to the mother liquor. Cobalt with a small amount of copper and aluminum could increase the specific surface area and decrease the particle size of catalysts.
文摘Based on formate and direct oxidation mechanisms,three Langmuir-Hinshelwood-Hougen-Watson （LHHW） kinetic models of the water-gasshift （WGS） reaction over a nano-structured iron catalyst under Fischer-Tropsch synthesis （FTS） reaction conditions were derived and compared with those over the conventional catalyst.The conventional and nanostructured Fe/Cu/La/Si catalysts were prepared by co-precipitation of Fe and Cu nitrates in aqueous media and water-oil micro-emulsion,respectively.The WGS kinetic data were measured by experiments over a wide range of reaction conditions and comparisons were also made for various rate equations.WGS rate expressions based on the formate mechanism with the assumption that the formation of formate is rate determining step were found to be the best.
文摘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.
基金sponsored by the National Key R&D Program of China(2021YFA1501100)the National Natural Science Foundation of China(21832001 and 22293042)the Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-202104)。
文摘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.
基金the Chengdu University of Technology Teachers Development Research Fund (No. 10912-2019KYQD07266)National Natural Science Foundation of China (No. 21806015) for financial support
文摘Reverse water gas shift(RWGS)reaction is a crucial process in CO_(2)utilization.Herein,Ni-and NiCe-containing hexagonal mesoporous silica(Ni-HMS and NiCe-HMS)catalysts were synthesized using an insitu one-pot method and applied for RWGS reaction.At certain reaction temperatures 500-750℃,Ni-HMS samples displayed a higher selectivity to the preferable CO than that of conventionally impregnated Ni/HMS catalyst.This could be originated from the smaller NiO nanoparticles over Ni-HMS catalyst.NiCe-HMS exhibited higher activity compared to Ni-HMS.The catalysts were characterized by means of TEM,XPS,XRD,H_(2)-TPR,CO_(2)-TPD,EPR and N_(2) adsorption-desortion technology.It was found that introduction of Ce created high concentration of oxygen vacancies,served as the active site for activating CO_(2).Also,this work analyzed the effect of the H_(2)/CO_(2)molar ratio on the best NiCe-HMS.When reaction gas H_(2)/CO_(2)molar ratio was 4 significantly decreased the selectivity to CO at low temperature,but triggered a higher CO_(2)conversion which is close to the equilibrium.
文摘Thermal decomposition of formic acid on SiO2, CeO2 and γ-Al2O3 was studied as an elementary step of reverse water–gas shit reaction（RWGS） over supported Au catalysts. γ-Al2O3 showed the highest CO selectivity among the tested oxides in the decomposition of formic acid. Infrared spectroscopy showed the formation of four formate species on γ-Al2O3： three η~1-type and one μ~2-type species, and these formates decomposed to CO at 473 K or higher. Au-loaded γ-Al2O3 samples were prepared by a depositionprecipitation method and used as catalysts for RWGS. The supported Au catalyst gave CO with high selectivity over 99% from CO2 and H2, which is attributed to the formation of formates on Au and subsequent decomposition to CO on γ-Al2O3.
基金supported by the Bulgarian National Science Fund(ContractдH09/5/2016)the CONACYT PDCPN 1216 and the University of Turin(Ricerca Locale 2016-2017)
文摘The utilization of pure hydrogen as an energy source in fuel cells gave rise to renewed interest in developing active and stable water-gas shift catalysts. Gold catalysts have proven to be very efficient for water-gas shift reaction at low temperature. The aim of the present study was to investigate the effect of:(i) different preparation methods(impregnation and coprecipitation) to obtain a modified ceria support,and(ii) the amount of Y_2 O_3(1.0 wt%, 2.5 wt%, 5.0 wt% and 7.5 wt%) as dopant on the water-gas shift activity of Au/CeO_2 catalysts. An extended characterization by means of S_(BET), XRD, HRTEM/HAADF, FTIR,H_2-TPR and CO-TPR measurements in combination with careful evaluation of the catalyst behavior allowed to shed light on the parameters governing the water-gas shift activity. The catalysts show very high activity(>90% CO conversion) in the temperature range 180-220 ℃,with a slightly better performance of the gold catalysts on supports prepared by impregnation. The decreased activity with increasing Y_2 O_3 concentration is related to the hindering of oxygen mobility due to ordering of surface oxygen vacancies in vicinity of segregated Y^(3+). The effect of catalyst pre-treatments and the stability of the best performing samples were examined as well.
文摘The reverse water–gas shift(RWGS)reaction combined with Fischer–Tropsch synthesis establishes a promising tandem catalytic system for transforming CO_(2)into valuable chemicals and fuels[1,2].However,the techno-economic assessment suggests that the RWGS reaction becomes viable and economically competitive only when catalysts with 100%CO selectivity(thus eliminating the downstream separation step),high activity,sufficiently long operational durability,and ideally produced from earth-abundant materials and energy-efficient routes,are available[3].
基金the Natural Science Foundation of Jiangxi Province(Grant No.20232BAB214018)the Research Projects of Ganjiang Innovation Academy(Grant No.E355F0050)of the Chinese Academy of Sciences+1 种基金the National Natural Science Foundation of China(Grant No.W2431016)the research fund of Key Laboratory of Rare Earth,Ganjiang Innovation Academy,Chinese Academy of Sciences.
文摘Reverse water-gas shift reaction represents a strategic pathway for CO_(2) utilization.Despite its potential,reverse water-gas shift reaction via conventional thermal-catalysis faces several challenges,including low equilibrium conversion rates due to thermodynamic constraints,high energy consumption,and insufficient product selectivity.Here,this study demonstrates an evident synergetic effect between plasma and Ag/ZnO,on enhancing reverse water-gas shift reaction.The plasma catalytic system achieved significantly improved performance with a remarkable CO_(2) conversion rate of 76.5%,a high CO selectivity of 96.8% and a CO yield of 74.1%,along with an energy efficiency as high as 0.19 mmol·kJ^(-1),surpassing the plasma alone system and ZnO catalytic systems.Results from X-ray photoelectron spectroscopy and Auger electron spectroscopy confirm the presence of electronic metal-support interactions between Ag and ZnO,which facilitates the formation of electron-deficient Ag sites and partially reduced ZnOx species.These reactive sites,along with oxygen vacancies created during reduction treatment,enhance the adsorption and activation of H_(2) and CO_(2),offering a dominant plasma-assisted surface reaction pathway for the improved reverse water-gas shift reaction.These findings underscore the crucial role of electronic metal-support interactions in manipulating surface environments to facilitate efficient plasma-assisted catalytic reactions,with significant implications for the rational design of catalysts capable of converting CO_(2) efficiently under mild conditions.
