Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the effica...Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the efficacy of SACs remains limited for certain reactions requiring simultaneous activation of multiple reactants over metallic active sites.Herein,we report an atomically dispersed Pt1Ru1 dual-atom pair site anchored on nanodiamond@graphene(ND@G)for CO oxidation.The Pt1Ru1 dual-atom catalyst shows an exceptional turnover frequency(TOF)of 17.6.10^(-2)s^(-1)at significantly lower temperature(30℃),achieving a tenfold increase in TOF compared to singleatom Pt1/ND@G catalyst(1.5.10^(-2)s^(-1))and surpassing to previously reported Pt-based catalysts under similar conditions.Moreover,the catalyst demonstrates excellent stability,maintaining its activity for 40 h at 80℃without significant deactivation.The superior catalytic performance of Pt-Ru dual-atom catalysts is attributed to the synergistic effect between Pt and Ru atoms with enhanced metallicity for improving simultaneous adsorption and activation of CO and O_(2),and the tuning of conventional competitive reactant adsorption into a non-competitive pathway over dual-atom pair sites.The present work manifests the advantages of dual-atom pair sites in heterogeneous catalysis and paves the way for precise design of catalysts at the atomic scale.展开更多
The development of efficient low-load platinum catalysts for CO oxidation is critical for large-scale industrial applications and environmental protection.In this study,a strategy of N_(2)treatment triggered the self-...The development of efficient low-load platinum catalysts for CO oxidation is critical for large-scale industrial applications and environmental protection.In this study,a strategy of N_(2)treatment triggered the self-reforming into fully exposed Pt cluster catalysts was proposed.By adjusting the coordination environment of Pt species on the defect support through N_(2)treatment,the CO catalytic activity was significantly enhanced,achieving complete CO oxidation at 130℃with a Pt loading of only 0.1 wt.%.The turnover frequency of N_(2)-treated Pt_(FEC)/Ti-D at 160℃was 18.3 times that of untreated Pt_(SA)/Ti-D.Comprehensive characterization results indicated that the N_(2)treatment of the Pt single-atom defect catalyst facilitated the reconfiguration and evolution of the defect structure,leading to the aggregation of Pt single atoms into fully exposed Pt clusters.Notably,these fully exposed Pt clusters exhibited a reduced coordination of Pt–O in the first coordination shell compared to single atoms,which resulted in the formation of Pt–Pt metal coordination.This unique coordination structure enhanced the adsorption and activation of CO and O_(2)on the catalyst,thereby resulting in exceptionally low-temperature CO oxidation activity.This work demonstrates a promising strategy for the design,synthesis,and industrial application of efficient low-platinum load catalysts.展开更多
A series of Au/Co_(x)Fe_(3-x)O_(4) catalysts was synthesized using the sol-deposition method by depositing 2–5 nm Au particles on Fe-doped Co_(3)O_(4).Co_(2)FeO_(4),with a Co/Fe molar ratio of 2:1,exhibited higher sp...A series of Au/Co_(x)Fe_(3-x)O_(4) catalysts was synthesized using the sol-deposition method by depositing 2–5 nm Au particles on Fe-doped Co_(3)O_(4).Co_(2)FeO_(4),with a Co/Fe molar ratio of 2:1,exhibited higher specific surface area,Co^(3+)/Co^(2+)ratio,and oxygen vacancy content compared to Co_(3)O_(4).As a result,it displayed better performance in CO oxidation,achieving a total conversion temperature(T100)of 96℃.Au greatly improved the catalytic efficiency of all Co_(x)Fe_(3-x)O_(4) samples,with the 0.2%Au/Co_(2)FeO_(4) catalyst achieving a further decrease in T100 to 73℃.Stability tests conducted at room temperature on the 1%Au/Co_(x)Fe_(3-x)O_(4) catalysts demonstrated a slowed deactivation rate after Fe-doping.The reaction pathway for CO oxidation catalyzed by Au/Co_(2)FeO_(4) followed the Mars-van Krevelen mechanism.展开更多
Nanometer SnO2 particles were synthesized by sol-gel dialytic processes and used as a support to prepare CuO supported catalysts via a deposition-precipitation method. The samples were characterized by means of TG-DTA...Nanometer SnO2 particles were synthesized by sol-gel dialytic processes and used as a support to prepare CuO supported catalysts via a deposition-precipitation method. The samples were characterized by means of TG-DTA, XRD, H2-TPR and XPS. The catalytic activity of the CuO/TiO2-SnO2 catalysts was markedly depended on the loading of CuO, and the optimum CuO loading was 8 wt.% （Tloo = 80 ℃）. The CuO/TiO2-SnO2 catalysts exhibited much higher catalytic activity than the CuO/TiO2 and CuO/SnO2 catalysts. H2-TPR result indicated that a large amount of CuO formed the active site for CO oxidation in 8 wt.% CuO/TiO2-SnO2 catalyst.展开更多
Low‐temperature CO oxidation is important for both fundamental studies and practical applica‐tions. Supported gold catalysts are generally regarded as the most active catalysts for low‐temperature CO oxidation. The...Low‐temperature CO oxidation is important for both fundamental studies and practical applica‐tions. Supported gold catalysts are generally regarded as the most active catalysts for low‐temperature CO oxidation. The active sites are traditionally believed to be Au nanoclusters or nanoparticles in the size range of 0.5–5 nm. Only in the last few years have single‐atom Au catalysts been proved to be active for CO oxidation. Recent advances in both experimental and theoretical studies on single‐atom Au catalysts unambiguously demonstrated that when dispersed on suitable oxide supports the Au single atoms can be extremely active for CO oxidation. In this mini‐review, recent advances in the development of Au single‐atom catalysts are discussed, with the aim of illus‐trating their unique catalytic features during CO oxidation.展开更多
High active and stable gold catalysts supported on crystalline Fe203 and CeO2/Fe2O3 were prepared via the deposition-precipitation method. The catalyst with a Au load of 1.0% calcined at 180 ℃ showed a CO conversion ...High active and stable gold catalysts supported on crystalline Fe203 and CeO2/Fe2O3 were prepared via the deposition-precipitation method. The catalyst with a Au load of 1.0% calcined at 180 ℃ showed a CO conversion of 100% at -8.9℃, while Au/CeO2/Fe2O3 converted CO completely at -16.1 ℃. Even having been calcined at 500 ℃, Au/Fe2O3 still exhibited significant catalytic activity, achieving full conversion of CO at 61.6℃. The catalyst with a low Au load of 0.5% could convert CO completely at room temperature and kept the activity unchanged for at least 150 h. N2 adsorption-desorption measurements show that the crystalline supports possessed a high specific surface area of about 200 m2/g. Characterizations of X-ray diffraction and transmission electron microscopy indicate that gold species were highly dispersed as nano or sub-nano particles on the supports. Even after the catalyst was calcined at 500 ℃, the Au particles remained in a nano-size of about 6--10 nm. X-ray photoelectron spectra reveal that the supported Au existed in metallic state Au0. The modification of Au/Fe2O3 by CeO2 proved to be beneficial to the inhibition of crystallization of Fe2O3 and the stabilization of gold particles in dispersed state, consequently promoting catalytic activity.展开更多
Mixed iron-cobalt oxide （Co/Fe molar ratio = 1/5） are prepared using a simple co-precipitation procedure and studied for the catalytic oxidation of carbon monoxide. In particular, the effects of a range of preparati...Mixed iron-cobalt oxide （Co/Fe molar ratio = 1/5） are prepared using a simple co-precipitation procedure and studied for the catalytic oxidation of carbon monoxide. In particular, the effects of a range of preparation variables such as pH value when precipitation, aging temperature, precipitation agent type and aging time are investigated on the catalytic performance of synthesized Fe-Co oxides in CO oxidation reaction. In addition, the preparation factors were optimized by Taguchi design method. The optimized sample was characterized by XRD, N2 adsortion/desorption, TEM and TGA/DTA techniques. The results reveal that the optimized sample shows a mesoporous structure with a narrow pore size distribution centered in the range of 2-7 nm. The sample prepared under optimized conditions has high activity and stability toward removal of carbon monoxide at lower temperatures. It is shown that different preparation variables influence the catalytic performance of Fe-Co oxide in CO oxidation reaction.展开更多
CeO2 was synthesized via sol-gel process and used as supporter to prepare CuO/CeO2, Cu/CeO2 catalysts by impregnation method. The catalytic properties and characterization of CeO2, CuO/CeO2 and Cu/CeO2 catalysts were ...CeO2 was synthesized via sol-gel process and used as supporter to prepare CuO/CeO2, Cu/CeO2 catalysts by impregnation method. The catalytic properties and characterization of CeO2, CuO/CeO2 and Cu/CeO2 catalysts were examined by means of a microreactor-GC system, HRTEM, XRD, TPR and XPS techniques. The results show that CuO has not catalytic activity and the activity of CeO2 is quite low for CO oxidation. However, the catalytic activity of CuO/CeO2 and Cu/ CeO2 catalysts increases significantly. Furthermore, the activity of CuO/CeO2 is higher than that of Cu/CeO2 catalysts.展开更多
The effects of CeO2 contents and silica carrier porosity with their pore diameters ranging from 5.2 nm to 12.5 nm of CuO-CeO2/SiO2 cata-lysts in CO oxidation were investigated.The catalysts were characterized by N2 ad...The effects of CeO2 contents and silica carrier porosity with their pore diameters ranging from 5.2 nm to 12.5 nm of CuO-CeO2/SiO2 cata-lysts in CO oxidation were investigated.The catalysts were characterized by N2 adsorption/desorption at low temperature,X-ray diffraction （XRD）,temperature-programmed reduction by H2 （H2-TPR）,oxygen temperature programmed desorption （O2-TPD） and X-ray photoelectron spectroscopy （XPS）.The results suggested that,the ceria content and the porosity of SiO2 carrier possessed great impacts on the structures and catalytic performances of CuO-CeO2/SiO2 catalysts.When appropriate content of CeO2 （Ce content 8 wt%） was added,the catalytic activity was greatly enhanced.In the catalyst supported on silica carrier with larger pore diameter,higher dispersion of CuO was observed,better agglomeration-resistant capacity was displayed and more lattice oxygen could be found,thus the CuO-CeO2 supported on Si-1 showed higher catalytic activity for low-temperature CO oxidation.展开更多
La2O3 doped Fe2O3 support was prepared by co-precipitation method,and gold was loaded by deposition-precipitation.Thermal stability of gold catalyst was enhanced considerably by La2O3 doping.Even when calcined at 500 ...La2O3 doped Fe2O3 support was prepared by co-precipitation method,and gold was loaded by deposition-precipitation.Thermal stability of gold catalyst was enhanced considerably by La2O3 doping.Even when calcined at 500 oC for 12 h,the catalyst doped with La2O3 could convert 90% of CO at 28.9 oC,while the catalyst without La2O3 doping achieved 90% CO conversion at 43.5 oC.Characterization techniques,such as N2 adsorption-desorption,X-ray diffraction(XRD),transmission electron microscopic(TEM) and thermogravime...展开更多
Cold plasma generated by dielectric barrier discharge （DBD） at atmospheric pressure was adopted for preparation of commercial TiO2 Degussa P25 supported Au catalysts （Au/P25- P） with the assistance of the depositi...Cold plasma generated by dielectric barrier discharge （DBD） at atmospheric pressure was adopted for preparation of commercial TiO2 Degussa P25 supported Au catalysts （Au/P25- P） with the assistance of the deposition-precipitation procedure. The influences of the plasma reduction time and calcination on the performance of the Au/P25-P catalysts were investigated. CO oxidation was performed to investigate the catalytic activity of the Au/P25 catalysts. The results show that DBD cold plasma for the fabrication of Au/P25-P catalysts is a fast process, and Au/P25-P （4 min） exhibited the highest CO oxidation activity due to the complete reduction of Au compounds and less consumption of oxygen vacancies. In order to form more oxygen vacancies active species, Au/P25-P was calcined to obtain Au/P25-PC catalysts. Interestingly, Au/P25- PC exhibited the highest activity for CO oxidation among the Au/P25 samples. The results of transmission electron microscopy （TEM） indicated that the smaller size and high distribution of Au nanoparticles are the mean reasons for a high performance of Au/P25-PC. Atmospheric- pressure DBD cold plasma was proved to be of great efficiency in preparing high performance supported Au catalysts.展开更多
In this work, we have reported the influence of the addition of base （KOH） on the physicochemical property of ceria synthesized by alcohothermal process, and the alcohothermal mechanism was also put forward. Further...In this work, we have reported the influence of the addition of base （KOH） on the physicochemical property of ceria synthesized by alcohothermal process, and the alcohothermal mechanism was also put forward. Furthermore, the prepared CeO2 was used as the support to prepare CuO/CeO2 catalysts via the wet impregnation method. The samples were characterized by N2 adsorption-desorption, X-ray powder diffraction （XRD）, high resolution transmission electron microscopy （HRTEM）, and temperatureprogrammed reduction by H2 （H2-TPR）. The catalytic properties of the CuO/CeO2 catalysts for lowtemperature CO oxidation were studied using a microreactor-GC system. The crystal size of CeO2-A was much smaller than that of CeO2-B, and the corresponding copper oxide catalysts exhibited higher catalytic activity than that of the CeO2-B-supported catalysts under the same reaction conditions. The alcohothermal mechanism indicated that KOH plays a key role in determining the physicochemical and catalytic properties of ceria-based materials.展开更多
Development of active and stable catalysts for low-temperature CO oxidation has long been regarded as a hot topic.In this contribution,we used CeO_(2) with high-density surface pits as support to prepare an active and...Development of active and stable catalysts for low-temperature CO oxidation has long been regarded as a hot topic.In this contribution,we used CeO_(2) with high-density surface pits as support to prepare an active and stable Au/CeO_(2) catalyst by an adsorption-deposition method.The obtained 0.05 wt%Au/CeO_(2)-TD(where TD represents thermal decomposition)can maintain its activity at 80℃ for more than 20 h or even after calcination at 800℃ for 2 h.The characterization results showed that the high-density surface pits on CeO_(2)-TD play a decisive role in the stabilization of Au and enhancement of the redox property.This work may provide a new strategy to improve the stability of supported metal catalysts by a simple and conventional method.展开更多
Supported Au catalysts for low-temperature CO oxidation were prepared by solvated metal atom impregnation (SMAI) and conventional impregnation (Cl). X-ray photoelectron spectroscopy (XPS) investigations indicated that...Supported Au catalysts for low-temperature CO oxidation were prepared by solvated metal atom impregnation (SMAI) and conventional impregnation (Cl). X-ray photoelectron spectroscopy (XPS) investigations indicated that the elemental gold in all the samples was in the metallic state, XRD measurements showed that the mean diameters of Au particles prepared by SMAI were smaller than those prepared by Cl with the same gold content. Catalytic tests showed that the SMAI catalyst had higher CO oxidation activity than the CI catalyst with the same compositions. Both SMAI and Cl catalysts exhibited high activity in low temperature CO oxidation. Full CO conversion was obtained at 323-383K.展开更多
Au/Al2O3 catalyst was prepared by a modified anion impregnation method and investigated with respect to its initial activity and stability for low-temperature CO oxidation.The activity changes of the catalyst were exa...Au/Al2O3 catalyst was prepared by a modified anion impregnation method and investigated with respect to its initial activity and stability for low-temperature CO oxidation.The activity changes of the catalyst were examined after separate treatment in CO＋O2 or CO2 ＋O2 .Furthermore,in situ FT-IR studies were performed to investigate the species on the surface when CO or CO＋O2 or CO2 ＋O2 was selected separately as adsorption gas.The results showed that Au/Al2O3 catalyst exhibited very high initial activity,but the catalytic activity was found to decrease gradually during CO oxidation with time on stream.And also,the activity of the catalyst declined after treatment in CO＋O2 or CO2 ＋O2 .The formation and accumulation of carbonate-like species during CO oxidation or treatment in CO＋O2 or CO2 ＋O2 might be mainly responsible for the activity decrease,which was reversible.展开更多
This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0...This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.展开更多
Electrochemical reaction is emerging as a powerful approach for glucose detection and biomass conversion.However,it has been rarely explored for glucose detection and biomass conversion into valueadded chemicals.Previ...Electrochemical reaction is emerging as a powerful approach for glucose detection and biomass conversion.However,it has been rarely explored for glucose detection and biomass conversion into valueadded chemicals.Previously reported glucose oxidase reduction(GOR)catalysts exhibit issues such as low activity,limited detection range,poor sensitivity,and overreliance on noble metals.Here,we employ an impregnation method to load transition metal nickel onto carbon nanotubes(CNT)and fabricated Ni/CNT30 catalyst via a discharge process.Ni/CNT30 catalyst exhibits a remarkably high catalytic activity of up to 3336.7μA·cm^(-2)·mmol^(-1)·L,a detection limit of 2.43μmol·L^(-1),outstanding stability,and excellent resistance to impurities and interference,surpassing other noble metal-based and oxide-based materials.Hence,this material provides a new approach for the preparation of glucose sensors to achieve precise mobile measurement of glucose concentration and biofuel cells in future.展开更多
Over recent decades,fuel cell technologies have emerged as viable solutions to address the energy and environmental challenges stemming from fossil fuel dependence.Especially,ammonia has gained increasing attention as...Over recent decades,fuel cell technologies have emerged as viable solutions to address the energy and environmental challenges stemming from fossil fuel dependence.Especially,ammonia has gained increasing attention as an attractive alternative to hydrogen,offering comparable energy density while maintaining carbon-free characteristics,along with superior storage and transport properties that give direct ammonia fuel cells(DAFCs)distinct safety advantages over hydrogen-based systems.Central to this technology is the anodic ammonia oxidation reaction(AOR),where platinum(Pt)remains the most efficient catalyst after years of intensive research.This review offers a comprehensive overview of Ptbased AOR electrocatalysts with potential for application in low-temperature DAFCs.Following an introductory section highlighting key historical developments and catalytic breakthroughs,a fundamental understanding of low-temperature DAFC operation and AOR mechanisms is systematically presented.Subsequently,it outlines the advancements in Pt-based catalysts from simple monometallic systems to sophisticated multimetallic alloys and composites,highlighting material innovations and performance enhancements.Afterward,key challenges and future research directions for advancing AOR electrocatalysts are identified,with the aim of providing valuable guidance for developing practical,highperformance,and low-temperature DAFC systems.展开更多
α-Bi2O3 powders were prepared from nanometer Bi powders through low-temperature oxidation at less than 873.15 K. XRD, SEM, TEM and HRTEM were used to characterize the structure and morphology of Bi powders and Bi2O3 ...α-Bi2O3 powders were prepared from nanometer Bi powders through low-temperature oxidation at less than 873.15 K. XRD, SEM, TEM and HRTEM were used to characterize the structure and morphology of Bi powders and Bi2O3 particles. Kinetic studies on the bismuth oxidation at low-temperatures were carried out by TGA method. The results show that bismuth beads should be reunited and oxidized to become irregular Bi2O3 powders. The bismuth oxidation follows shrinking core model, and its controlling mechanism varies at different reaction time. Within 0-10 min, the kinetics is controlled by chemical reaction, after that it is controlled by O2 diffusion in the solid α-Bi2O3 layer. The apparent activation energy is determined as 55.19 kJ/mol in liquid-phase oxidation.展开更多
Co3O4 catalysts prepared with different precipitants（NH3·H2O,KOH,NH4HCO3,K2CO3 and KHCO3）were investigated for the oxidation of formaldehyde（HCHO）.Among these,KHCO3-precipitated Co3O4（KHCO3-Co） was the most...Co3O4 catalysts prepared with different precipitants（NH3·H2O,KOH,NH4HCO3,K2CO3 and KHCO3）were investigated for the oxidation of formaldehyde（HCHO）.Among these,KHCO3-precipitated Co3O4（KHCO3-Co） was the most active low-temperature catalyst,and was able to completely oxidize HCHO at the 100-ppm level to CO2 at 90℃.In situ diffuse reflectance infrared spectroscopy demonstrated that hydroxyl groups on the catalyst surface were regenerated by K~＋ and CO3^（2-）,thus promoting the oxidation of HCHO.Moreover,H2-temperature programmed reduction and X-ray photoelectron spectroscopy showed that employing KHCO3 as the precipitant increased the Co^3＋/Co^2＋molar ratio on the surface of the Co3O4 catalyst,thus further promoting oxidation.Structural characterization revealed that catalysts precipitated with carbonate or bicarbonate reagents exhibited greater specific surface areas and pore volumes.Overall,these data suggest that the high activity observed during the Co3O4 catalyzed oxidation of HCHO can be primarily attributed to the presence of K~＋ and CO3^（2-） on the Co3O4 surface and the favorable Co^3＋/Co^2＋ ratio.展开更多
基金supported by the National Key R&D Program of China (2021YFA1502802)the National Natural Science Foundation of China (U21B2092, 22202213, 22402210, 22502215, 22502214, 22572200, and 22579171)+3 种基金the International Partnership Program of Chinese Academy of Sciences (172GJHZ2022028MI)the Shenyang Bureau of Science and Technology (24-213-3-25)the Natural Science Foundation of Liaoning Province (2025BS0153)Zhongke Technology Achievement Transfer and Transformation Center of Henan Province 2025119
文摘Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the efficacy of SACs remains limited for certain reactions requiring simultaneous activation of multiple reactants over metallic active sites.Herein,we report an atomically dispersed Pt1Ru1 dual-atom pair site anchored on nanodiamond@graphene(ND@G)for CO oxidation.The Pt1Ru1 dual-atom catalyst shows an exceptional turnover frequency(TOF)of 17.6.10^(-2)s^(-1)at significantly lower temperature(30℃),achieving a tenfold increase in TOF compared to singleatom Pt1/ND@G catalyst(1.5.10^(-2)s^(-1))and surpassing to previously reported Pt-based catalysts under similar conditions.Moreover,the catalyst demonstrates excellent stability,maintaining its activity for 40 h at 80℃without significant deactivation.The superior catalytic performance of Pt-Ru dual-atom catalysts is attributed to the synergistic effect between Pt and Ru atoms with enhanced metallicity for improving simultaneous adsorption and activation of CO and O_(2),and the tuning of conventional competitive reactant adsorption into a non-competitive pathway over dual-atom pair sites.The present work manifests the advantages of dual-atom pair sites in heterogeneous catalysis and paves the way for precise design of catalysts at the atomic scale.
基金supported by the National Natural Science Foundation of China(52170118,52322004,52230002)the China Postdoctoral Science Foundation(2024M763296).
文摘The development of efficient low-load platinum catalysts for CO oxidation is critical for large-scale industrial applications and environmental protection.In this study,a strategy of N_(2)treatment triggered the self-reforming into fully exposed Pt cluster catalysts was proposed.By adjusting the coordination environment of Pt species on the defect support through N_(2)treatment,the CO catalytic activity was significantly enhanced,achieving complete CO oxidation at 130℃with a Pt loading of only 0.1 wt.%.The turnover frequency of N_(2)-treated Pt_(FEC)/Ti-D at 160℃was 18.3 times that of untreated Pt_(SA)/Ti-D.Comprehensive characterization results indicated that the N_(2)treatment of the Pt single-atom defect catalyst facilitated the reconfiguration and evolution of the defect structure,leading to the aggregation of Pt single atoms into fully exposed Pt clusters.Notably,these fully exposed Pt clusters exhibited a reduced coordination of Pt–O in the first coordination shell compared to single atoms,which resulted in the formation of Pt–Pt metal coordination.This unique coordination structure enhanced the adsorption and activation of CO and O_(2)on the catalyst,thereby resulting in exceptionally low-temperature CO oxidation activity.This work demonstrates a promising strategy for the design,synthesis,and industrial application of efficient low-platinum load catalysts.
基金supported by the Fundamental Research Program of Shanxi Province of China(202203021211103,202303021212172,202403021211196).
文摘A series of Au/Co_(x)Fe_(3-x)O_(4) catalysts was synthesized using the sol-deposition method by depositing 2–5 nm Au particles on Fe-doped Co_(3)O_(4).Co_(2)FeO_(4),with a Co/Fe molar ratio of 2:1,exhibited higher specific surface area,Co^(3+)/Co^(2+)ratio,and oxygen vacancy content compared to Co_(3)O_(4).As a result,it displayed better performance in CO oxidation,achieving a total conversion temperature(T100)of 96℃.Au greatly improved the catalytic efficiency of all Co_(x)Fe_(3-x)O_(4) samples,with the 0.2%Au/Co_(2)FeO_(4) catalyst achieving a further decrease in T100 to 73℃.Stability tests conducted at room temperature on the 1%Au/Co_(x)Fe_(3-x)O_(4) catalysts demonstrated a slowed deactivation rate after Fe-doping.The reaction pathway for CO oxidation catalyzed by Au/Co_(2)FeO_(4) followed the Mars-van Krevelen mechanism.
基金supported by the National Natural Science Foundation of China (20771061 and 20871071)the 973 Program (2005CB623607)Science and Technology Commission Foundation of Tianjin (08JCYBJC00100 and 09JCYBJC03600)
文摘Nanometer SnO2 particles were synthesized by sol-gel dialytic processes and used as a support to prepare CuO supported catalysts via a deposition-precipitation method. The samples were characterized by means of TG-DTA, XRD, H2-TPR and XPS. The catalytic activity of the CuO/TiO2-SnO2 catalysts was markedly depended on the loading of CuO, and the optimum CuO loading was 8 wt.% （Tloo = 80 ℃）. The CuO/TiO2-SnO2 catalysts exhibited much higher catalytic activity than the CuO/TiO2 and CuO/SnO2 catalysts. H2-TPR result indicated that a large amount of CuO formed the active site for CO oxidation in 8 wt.% CuO/TiO2-SnO2 catalyst.
文摘Low‐temperature CO oxidation is important for both fundamental studies and practical applica‐tions. Supported gold catalysts are generally regarded as the most active catalysts for low‐temperature CO oxidation. The active sites are traditionally believed to be Au nanoclusters or nanoparticles in the size range of 0.5–5 nm. Only in the last few years have single‐atom Au catalysts been proved to be active for CO oxidation. Recent advances in both experimental and theoretical studies on single‐atom Au catalysts unambiguously demonstrated that when dispersed on suitable oxide supports the Au single atoms can be extremely active for CO oxidation. In this mini‐review, recent advances in the development of Au single‐atom catalysts are discussed, with the aim of illus‐trating their unique catalytic features during CO oxidation.
基金Supported by the Henkel Professorship of Tongji University,China
文摘High active and stable gold catalysts supported on crystalline Fe203 and CeO2/Fe2O3 were prepared via the deposition-precipitation method. The catalyst with a Au load of 1.0% calcined at 180 ℃ showed a CO conversion of 100% at -8.9℃, while Au/CeO2/Fe2O3 converted CO completely at -16.1 ℃. Even having been calcined at 500 ℃, Au/Fe2O3 still exhibited significant catalytic activity, achieving full conversion of CO at 61.6℃. The catalyst with a low Au load of 0.5% could convert CO completely at room temperature and kept the activity unchanged for at least 150 h. N2 adsorption-desorption measurements show that the crystalline supports possessed a high specific surface area of about 200 m2/g. Characterizations of X-ray diffraction and transmission electron microscopy indicate that gold species were highly dispersed as nano or sub-nano particles on the supports. Even after the catalyst was calcined at 500 ℃, the Au particles remained in a nano-size of about 6--10 nm. X-ray photoelectron spectra reveal that the supported Au existed in metallic state Au0. The modification of Au/Fe2O3 by CeO2 proved to be beneficial to the inhibition of crystallization of Fe2O3 and the stabilization of gold particles in dispersed state, consequently promoting catalytic activity.
基金supported by the University of Kashan (Grant No.158426/3)
文摘Mixed iron-cobalt oxide （Co/Fe molar ratio = 1/5） are prepared using a simple co-precipitation procedure and studied for the catalytic oxidation of carbon monoxide. In particular, the effects of a range of preparation variables such as pH value when precipitation, aging temperature, precipitation agent type and aging time are investigated on the catalytic performance of synthesized Fe-Co oxides in CO oxidation reaction. In addition, the preparation factors were optimized by Taguchi design method. The optimized sample was characterized by XRD, N2 adsortion/desorption, TEM and TGA/DTA techniques. The results reveal that the optimized sample shows a mesoporous structure with a narrow pore size distribution centered in the range of 2-7 nm. The sample prepared under optimized conditions has high activity and stability toward removal of carbon monoxide at lower temperatures. It is shown that different preparation variables influence the catalytic performance of Fe-Co oxide in CO oxidation reaction.
基金Projected supported by the National Natural Science Foundation of China (20271028) and Tianjin Natural Science Foundation(033602511)
文摘CeO2 was synthesized via sol-gel process and used as supporter to prepare CuO/CeO2, Cu/CeO2 catalysts by impregnation method. The catalytic properties and characterization of CeO2, CuO/CeO2 and Cu/CeO2 catalysts were examined by means of a microreactor-GC system, HRTEM, XRD, TPR and XPS techniques. The results show that CuO has not catalytic activity and the activity of CeO2 is quite low for CO oxidation. However, the catalytic activity of CuO/CeO2 and Cu/ CeO2 catalysts increases significantly. Furthermore, the activity of CuO/CeO2 is higher than that of Cu/CeO2 catalysts.
基金supported by the National Natural Science Foundation of China(20590360)New Century Excellent Talent Project of China(NCET-05-0783)
文摘The effects of CeO2 contents and silica carrier porosity with their pore diameters ranging from 5.2 nm to 12.5 nm of CuO-CeO2/SiO2 cata-lysts in CO oxidation were investigated.The catalysts were characterized by N2 adsorption/desorption at low temperature,X-ray diffraction （XRD）,temperature-programmed reduction by H2 （H2-TPR）,oxygen temperature programmed desorption （O2-TPD） and X-ray photoelectron spectroscopy （XPS）.The results suggested that,the ceria content and the porosity of SiO2 carrier possessed great impacts on the structures and catalytic performances of CuO-CeO2/SiO2 catalysts.When appropriate content of CeO2 （Ce content 8 wt%） was added,the catalytic activity was greatly enhanced.In the catalyst supported on silica carrier with larger pore diameter,higher dispersion of CuO was observed,better agglomeration-resistant capacity was displayed and more lattice oxygen could be found,thus the CuO-CeO2 supported on Si-1 showed higher catalytic activity for low-temperature CO oxidation.
基金supported by the Henkel Professorship of Tongji University
文摘La2O3 doped Fe2O3 support was prepared by co-precipitation method,and gold was loaded by deposition-precipitation.Thermal stability of gold catalyst was enhanced considerably by La2O3 doping.Even when calcined at 500 oC for 12 h,the catalyst doped with La2O3 could convert 90% of CO at 28.9 oC,while the catalyst without La2O3 doping achieved 90% CO conversion at 43.5 oC.Characterization techniques,such as N2 adsorption-desorption,X-ray diffraction(XRD),transmission electron microscopic(TEM) and thermogravime...
基金supported by National Natural Science Foundation of China(Nos.11505019,21173028)the Science and Technology Research Project of Liaoning Provincial Education Department(No.L2013464)+1 种基金the Scientific Research Foundation for the Doctor of Liaoning Province(No.20131004)the Dalian Jinzhou New District Science and Technology Plan Project(No.KJCX-ZTPY-2014-0001)
文摘Cold plasma generated by dielectric barrier discharge （DBD） at atmospheric pressure was adopted for preparation of commercial TiO2 Degussa P25 supported Au catalysts （Au/P25- P） with the assistance of the deposition-precipitation procedure. The influences of the plasma reduction time and calcination on the performance of the Au/P25-P catalysts were investigated. CO oxidation was performed to investigate the catalytic activity of the Au/P25 catalysts. The results show that DBD cold plasma for the fabrication of Au/P25-P catalysts is a fast process, and Au/P25-P （4 min） exhibited the highest CO oxidation activity due to the complete reduction of Au compounds and less consumption of oxygen vacancies. In order to form more oxygen vacancies active species, Au/P25-P was calcined to obtain Au/P25-PC catalysts. Interestingly, Au/P25- PC exhibited the highest activity for CO oxidation among the Au/P25 samples. The results of transmission electron microscopy （TEM） indicated that the smaller size and high distribution of Au nanoparticles are the mean reasons for a high performance of Au/P25-PC. Atmospheric- pressure DBD cold plasma was proved to be of great efficiency in preparing high performance supported Au catalysts.
文摘In this work, we have reported the influence of the addition of base （KOH） on the physicochemical property of ceria synthesized by alcohothermal process, and the alcohothermal mechanism was also put forward. Furthermore, the prepared CeO2 was used as the support to prepare CuO/CeO2 catalysts via the wet impregnation method. The samples were characterized by N2 adsorption-desorption, X-ray powder diffraction （XRD）, high resolution transmission electron microscopy （HRTEM）, and temperatureprogrammed reduction by H2 （H2-TPR）. The catalytic properties of the CuO/CeO2 catalysts for lowtemperature CO oxidation were studied using a microreactor-GC system. The crystal size of CeO2-A was much smaller than that of CeO2-B, and the corresponding copper oxide catalysts exhibited higher catalytic activity than that of the CeO2-B-supported catalysts under the same reaction conditions. The alcohothermal mechanism indicated that KOH plays a key role in determining the physicochemical and catalytic properties of ceria-based materials.
基金financially supported by the National Key Research and Development Program of China(No.2016YFC0204300)the National Natural Science Foundation of China(Nos.21571061,21333003 and 21908079)Pujiang Program of the Shanghai Municipal Human Resources and Social Security Bureau(No.18PJD011)。
文摘Development of active and stable catalysts for low-temperature CO oxidation has long been regarded as a hot topic.In this contribution,we used CeO_(2) with high-density surface pits as support to prepare an active and stable Au/CeO_(2) catalyst by an adsorption-deposition method.The obtained 0.05 wt%Au/CeO_(2)-TD(where TD represents thermal decomposition)can maintain its activity at 80℃ for more than 20 h or even after calcination at 800℃ for 2 h.The characterization results showed that the high-density surface pits on CeO_(2)-TD play a decisive role in the stabilization of Au and enhancement of the redox property.This work may provide a new strategy to improve the stability of supported metal catalysts by a simple and conventional method.
基金This project is supported by the Natural Science Foundation of Tianjin (No. 983603611)
文摘Supported Au catalysts for low-temperature CO oxidation were prepared by solvated metal atom impregnation (SMAI) and conventional impregnation (Cl). X-ray photoelectron spectroscopy (XPS) investigations indicated that the elemental gold in all the samples was in the metallic state, XRD measurements showed that the mean diameters of Au particles prepared by SMAI were smaller than those prepared by Cl with the same gold content. Catalytic tests showed that the SMAI catalyst had higher CO oxidation activity than the CI catalyst with the same compositions. Both SMAI and Cl catalysts exhibited high activity in low temperature CO oxidation. Full CO conversion was obtained at 323-383K.
基金supported by the Science and Research Reward Fund Program of Shandong Excellent Young Scientist of China (2007BS04033)
文摘Au/Al2O3 catalyst was prepared by a modified anion impregnation method and investigated with respect to its initial activity and stability for low-temperature CO oxidation.The activity changes of the catalyst were examined after separate treatment in CO＋O2 or CO2 ＋O2 .Furthermore,in situ FT-IR studies were performed to investigate the species on the surface when CO or CO＋O2 or CO2 ＋O2 was selected separately as adsorption gas.The results showed that Au/Al2O3 catalyst exhibited very high initial activity,but the catalytic activity was found to decrease gradually during CO oxidation with time on stream.And also,the activity of the catalyst declined after treatment in CO＋O2 or CO2 ＋O2 .The formation and accumulation of carbonate-like species during CO oxidation or treatment in CO＋O2 or CO2 ＋O2 might be mainly responsible for the activity decrease,which was reversible.
基金financially supported by the National Natural Science Foundation of China(No.22309067)the Open Project Program of the State Key Laboratory of Materials-Oriented Chemical Engineering,China(No.KL21-05)the Marine Equipment and Technology Institute,Jiangsu University of Science and Technology,China(No.XTCX202404)。
文摘This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.
基金supported by the National Natural Science Foundation of China(22408225 and 22478241)the Postdoctoral Fellowship Program of CPSF(GZC20240999).
文摘Electrochemical reaction is emerging as a powerful approach for glucose detection and biomass conversion.However,it has been rarely explored for glucose detection and biomass conversion into valueadded chemicals.Previously reported glucose oxidase reduction(GOR)catalysts exhibit issues such as low activity,limited detection range,poor sensitivity,and overreliance on noble metals.Here,we employ an impregnation method to load transition metal nickel onto carbon nanotubes(CNT)and fabricated Ni/CNT30 catalyst via a discharge process.Ni/CNT30 catalyst exhibits a remarkably high catalytic activity of up to 3336.7μA·cm^(-2)·mmol^(-1)·L,a detection limit of 2.43μmol·L^(-1),outstanding stability,and excellent resistance to impurities and interference,surpassing other noble metal-based and oxide-based materials.Hence,this material provides a new approach for the preparation of glucose sensors to achieve precise mobile measurement of glucose concentration and biofuel cells in future.
基金supported by the National Natural Science Foundation of China(No.52401284)the Natural Science Foundation of Jiangsu Province(No.BK20240957)+1 种基金the Key Research and Development Program of Nantong(No.GZ2024005)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX25_3677)。
文摘Over recent decades,fuel cell technologies have emerged as viable solutions to address the energy and environmental challenges stemming from fossil fuel dependence.Especially,ammonia has gained increasing attention as an attractive alternative to hydrogen,offering comparable energy density while maintaining carbon-free characteristics,along with superior storage and transport properties that give direct ammonia fuel cells(DAFCs)distinct safety advantages over hydrogen-based systems.Central to this technology is the anodic ammonia oxidation reaction(AOR),where platinum(Pt)remains the most efficient catalyst after years of intensive research.This review offers a comprehensive overview of Ptbased AOR electrocatalysts with potential for application in low-temperature DAFCs.Following an introductory section highlighting key historical developments and catalytic breakthroughs,a fundamental understanding of low-temperature DAFC operation and AOR mechanisms is systematically presented.Subsequently,it outlines the advancements in Pt-based catalysts from simple monometallic systems to sophisticated multimetallic alloys and composites,highlighting material innovations and performance enhancements.Afterward,key challenges and future research directions for advancing AOR electrocatalysts are identified,with the aim of providing valuable guidance for developing practical,highperformance,and low-temperature DAFC systems.
基金Project (2006BAB02B05-04- 01/02) supported by the National Key Technologies R&D Program of China
文摘α-Bi2O3 powders were prepared from nanometer Bi powders through low-temperature oxidation at less than 873.15 K. XRD, SEM, TEM and HRTEM were used to characterize the structure and morphology of Bi powders and Bi2O3 particles. Kinetic studies on the bismuth oxidation at low-temperatures were carried out by TGA method. The results show that bismuth beads should be reunited and oxidized to become irregular Bi2O3 powders. The bismuth oxidation follows shrinking core model, and its controlling mechanism varies at different reaction time. Within 0-10 min, the kinetics is controlled by chemical reaction, after that it is controlled by O2 diffusion in the solid α-Bi2O3 layer. The apparent activation energy is determined as 55.19 kJ/mol in liquid-phase oxidation.
基金supported by the National Natural Science Foundation of China(21577088)~~
文摘Co3O4 catalysts prepared with different precipitants（NH3·H2O,KOH,NH4HCO3,K2CO3 and KHCO3）were investigated for the oxidation of formaldehyde（HCHO）.Among these,KHCO3-precipitated Co3O4（KHCO3-Co） was the most active low-temperature catalyst,and was able to completely oxidize HCHO at the 100-ppm level to CO2 at 90℃.In situ diffuse reflectance infrared spectroscopy demonstrated that hydroxyl groups on the catalyst surface were regenerated by K~＋ and CO3^（2-）,thus promoting the oxidation of HCHO.Moreover,H2-temperature programmed reduction and X-ray photoelectron spectroscopy showed that employing KHCO3 as the precipitant increased the Co^3＋/Co^2＋molar ratio on the surface of the Co3O4 catalyst,thus further promoting oxidation.Structural characterization revealed that catalysts precipitated with carbonate or bicarbonate reagents exhibited greater specific surface areas and pore volumes.Overall,these data suggest that the high activity observed during the Co3O4 catalyzed oxidation of HCHO can be primarily attributed to the presence of K~＋ and CO3^（2-） on the Co3O4 surface and the favorable Co^3＋/Co^2＋ ratio.
