The development of efficient and cost-effective non-precious-metal single-atom catalysts(SACs)is crucial for advancing the practical application of electrocatalytic CO2 reduction(CO2RR).However,identifying highl...The development of efficient and cost-effective non-precious-metal single-atom catalysts(SACs)is crucial for advancing the practical application of electrocatalytic CO2 reduction(CO2RR).However,identifying highly active metal atoms and designing catalysts with uniform active center structures remain significant challenges.To address this,we developed a generic pyrolysis method to synthesize a series of transition metal-based SACs with atomically dispersed metal anchored on carbon nitride support(M-C3N4,M=Fe,Ni,Cu).Benefiting from the unique electronic structure of the Fe-N4 sites supported on C3N4,the Fe-C3N4 catalyst demonstrated exceptional performance,achieving a CO Faradaic efficiency of 99.6%and maintaining excellent stability.Theoretical calculations indicate that the Fe site exhibits a relatively stronger interaction with the*COOH intermediate,thereby helping to lower the energy barrier of the CO2 protonation process.This study provides valuable theoretical insights and practical synthesis strategies for designing high-performance non-precious-metal SACs for CO2RR.展开更多
Mesostructured Co3O4-CeO2 composite was found to be an effective catalytic material for the complete oxidation of benzene.The Co3O4-CeO2 catalysts with different Co/Ce ratios(mol/mol)were prepared via the nanocasting ...Mesostructured Co3O4-CeO2 composite was found to be an effective catalytic material for the complete oxidation of benzene.The Co3O4-CeO2 catalysts with different Co/Ce ratios(mol/mol)were prepared via the nanocasting method and the mesostructure was replicated from two-dimensional(2D)hexagonal SBA-15 and three-dimensional(3D)cubic KIT-6 silicas,respectively.All the obtained Co3O4-CeO2 catalysts exhibited the similar symmetry with the parent silicas and well ordered mesostructures.The Co3O4-CeO2 catalysts with 2D mesostructure showed lower catalytic activities than the corresponding 3D materials.The Co3O4-CeO2 catalyst nanocasted from KIT-6 and with the Co/Ce ratio of 16/1 possessed the best catalytic benzene oxidation activity due to larger quantities of surface hydroxyl groups and surface oxygenated species.The mesostructured Co3O4-CeO2 material thus shows great potential as a promising eco-environmental catalyst for benzene effective elimination.展开更多
Propylene,a readily accessible and economically viable light olefin,has garnered substantial interest for its potential conversion into valuable higher olefins through oligomerization processes.The distribution of pro...Propylene,a readily accessible and economically viable light olefin,has garnered substantial interest for its potential conversion into valuable higher olefins through oligomerization processes.The distribution of products is profoundly influenced by the catalyst structure.In this study,Fe2O3-doped NiSO4/Al2O3 catalysts have been meticulously developed to facilitate the selective trimerization of propylene under mild conditions.Significantly,the 0.25Fe2O3-NiSO4/Al2O3 catalyst demonstrates an enhanced reaction rate(48.5 mmolC3/(gcat.·h)),alongside a high yield of C9(~32.2%),significantly surpassing the performance of the NiSO4/Al2O3 catalyst(C9:~24.1%).The incorporation of Fe2O3 modifies the migration process of sulfate ions,altering the Lewis acidity of the electron-deficient Ni and Fe sites on the catalyst and resulting a shift in product distribution from a Schulz-Flory distribution to a Poisson distribution.This shift is primarily ascribed to the heightened energy barrier for theβ-H elimination reaction in the C6 alkyl intermediates on the doped catalyst,further promoting polymerization to yield a greater quantity of Type II C9.Furthermore,the validation of the Cossee-Arlman mechanism within the reaction pathway has been confirmed.It is noteworthy that the 0.25Fe2O3-NiSO4/Al2O3 catalyst exhibits remarkable stability exceeding 80 h in the selective trimerization of propylene.These research findings significantly enhance our understanding of the mechanisms underlying olefin oligomerization reactions and provide invaluable insights for the development of more effective catalysts.展开更多
1.Indroduction In light of the global transition toward carbon neutrality,the development of mild-condition ammonia synthesis technologies has gained significant attention as a promising solution to address the inhere...1.Indroduction In light of the global transition toward carbon neutrality,the development of mild-condition ammonia synthesis technologies has gained significant attention as a promising solution to address the inherent limitations of the traditional Haber-Bosch approach,which remains highly energy-intensive due to the extreme operation conditions(above 350℃ and over 10 MPa)required to activate the robust N≡N bond(945 kJ mol-1).Furthermore,the process is carbon-intensive,as its primary hydrogen source is derived from hydrocarbon reforming with high carbon emissions[1,2].展开更多
2,5-dimethyfuran(DMF), which is produced from 5-hydroxymethyfurfural(HMF) by hydrodeoxygenation(HDO), is a high quality fuel due to the high heating value, the high octane number and the suitable boiling point. Select...2,5-dimethyfuran(DMF), which is produced from 5-hydroxymethyfurfural(HMF) by hydrodeoxygenation(HDO), is a high quality fuel due to the high heating value, the high octane number and the suitable boiling point. Selective hydrogenation of HMF into liquid fuel DMF has been widely researched. In this paper, Co_3O_4 catalyst was prepared by co-precipitation and was reduced at different temperatures to form Co–CoO_x catalysts. The characterization of catalysts was tested by XRD, TEM, XPS, TPR, BET and NH3-TPD.Co–CoO_x possessed a high amount of Co metal and CoO_x acidic sites, wherein Co worked as the active hydrogenation sites and CoO_x acted as the acid promoter to facilitate the selective HDO of HMF to DMF.The synergistic effect of Co–CoO_x is the key for HDO of HMF, obtaining 83.3% of DMF yield at 170 °C, 12 h and the reduction temperature of 400 °C. This method not only saves the catalyst cost, but also promotes the utilization of biomass energy.展开更多
CeO2-Co3O4 catalysts for low-temperature CO oxidation were prepared by a co-precipitation method.In combination with the characterization methods of N2 adsorption/desorption,XRD,temperature-programmed reduction(TPR),a...CeO2-Co3O4 catalysts for low-temperature CO oxidation were prepared by a co-precipitation method.In combination with the characterization methods of N2 adsorption/desorption,XRD,temperature-programmed reduction(TPR),and FT-IR,the influence of the cerium content on the catalytic performance of CeO2-Co3O4 was investigated.The results indicate that the prepared CeO2-Co3O4 catalysts exhibit a better activity than that of pure CeO2 or pure Co3O4.The catalyst with the Ce/Co atomic ratio 1:16 exhibits the best activity,which converts 77%of CO at room temperature and completely oxidizes CO at 45℃.展开更多
The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO2 from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonizatio...The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO2 from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonization.However,steelwork off-gases typically contain various impurities,including H2S,which can deactivate commercial methanol synthesis catalysts,Cu/ZnO/Al2O3(CZA).Reverse water-gas shift(RWGS)reaction is the predominant side reaction in CO2 hydrogenation to methanol which can occur at ambient pressure,enabling the decouple of RWGS from methanol production at high pressure.Then,a series of activated CZA catalysts has been in-situ pretreated in 400 ppm H2S/Ar at 250℃and tested for both RWGS reaction at ambient pressure and CO2 hydrogenation to methanol at high pressure.An innovative decoupling strategy was employed to isolate the RWGS reaction from the methanol synthesis process,enabling the investigation of the evolution of active site structures and the poisoning mechanism through elemental analysis,X-ray Diffraction,X-ray Photoelectron Spectroscopy,Fourier Transform Infrared Spectroscopy,Temperature Programmed Reduction and CO2 Temperature Programmed Desorption.The results indicate that there are different dynamic migration behaviors of ZnOx in the two reaction systems,leading to different poisoning mechanisms.These interesting findings are beneficial to develop sulfur resistant and durable highly efficient catalysts for CO2 hydrogenation to methanol,promoting the carbon emission reduction in steel industry.展开更多
基金funded by the National Natural Science Foundation of China(Nos.22508135,22278169)the Natural Science Foundation of Anhui Province(No.2508085QB067)+3 种基金the Key Foundation of the Educational Commission of Anhui Province(No.2022AH050376)the Excellent Scientific Research and Innovation Team of Education Department of Anhui Province(No.2022AH010028)the National Innovation and Entrepreneurship Training Program for College Students,China(No.202410373008)Guangxi University Engineering Research Center of Hydrogen/Heat/Electricity-Related Energy Materials and Sensors。
摘要The development of efficient and cost-effective non-precious-metal single-atom catalysts(SACs)is crucial for advancing the practical application of electrocatalytic CO2 reduction(CO2RR).However,identifying highly active metal atoms and designing catalysts with uniform active center structures remain significant challenges.To address this,we developed a generic pyrolysis method to synthesize a series of transition metal-based SACs with atomically dispersed metal anchored on carbon nitride support(M-C3N4,M=Fe,Ni,Cu).Benefiting from the unique electronic structure of the Fe-N4 sites supported on C3N4,the Fe-C3N4 catalyst demonstrated exceptional performance,achieving a CO Faradaic efficiency of 99.6%and maintaining excellent stability.Theoretical calculations indicate that the Fe site exhibits a relatively stronger interaction with the*COOH intermediate,thereby helping to lower the energy barrier of the CO2 protonation process.This study provides valuable theoretical insights and practical synthesis strategies for designing high-performance non-precious-metal SACs for CO2RR.
基金supported by the National Natural Science Funds for Distinguished Young Scholar(No.20725723)the National Basic Research Program of China(No.2010CB732300)the National High Technology Research and Development Program of China(No.2006AA06A310)
摘要Mesostructured Co3O4-CeO2 composite was found to be an effective catalytic material for the complete oxidation of benzene.The Co3O4-CeO2 catalysts with different Co/Ce ratios(mol/mol)were prepared via the nanocasting method and the mesostructure was replicated from two-dimensional(2D)hexagonal SBA-15 and three-dimensional(3D)cubic KIT-6 silicas,respectively.All the obtained Co3O4-CeO2 catalysts exhibited the similar symmetry with the parent silicas and well ordered mesostructures.The Co3O4-CeO2 catalysts with 2D mesostructure showed lower catalytic activities than the corresponding 3D materials.The Co3O4-CeO2 catalyst nanocasted from KIT-6 and with the Co/Ce ratio of 16/1 possessed the best catalytic benzene oxidation activity due to larger quantities of surface hydroxyl groups and surface oxygenated species.The mesostructured Co3O4-CeO2 material thus shows great potential as a promising eco-environmental catalyst for benzene effective elimination.
摘要Propylene,a readily accessible and economically viable light olefin,has garnered substantial interest for its potential conversion into valuable higher olefins through oligomerization processes.The distribution of products is profoundly influenced by the catalyst structure.In this study,Fe2O3-doped NiSO4/Al2O3 catalysts have been meticulously developed to facilitate the selective trimerization of propylene under mild conditions.Significantly,the 0.25Fe2O3-NiSO4/Al2O3 catalyst demonstrates an enhanced reaction rate(48.5 mmolC3/(gcat.·h)),alongside a high yield of C9(~32.2%),significantly surpassing the performance of the NiSO4/Al2O3 catalyst(C9:~24.1%).The incorporation of Fe2O3 modifies the migration process of sulfate ions,altering the Lewis acidity of the electron-deficient Ni and Fe sites on the catalyst and resulting a shift in product distribution from a Schulz-Flory distribution to a Poisson distribution.This shift is primarily ascribed to the heightened energy barrier for theβ-H elimination reaction in the C6 alkyl intermediates on the doped catalyst,further promoting polymerization to yield a greater quantity of Type II C9.Furthermore,the validation of the Cossee-Arlman mechanism within the reaction pathway has been confirmed.It is noteworthy that the 0.25Fe2O3-NiSO4/Al2O3 catalyst exhibits remarkable stability exceeding 80 h in the selective trimerization of propylene.These research findings significantly enhance our understanding of the mechanisms underlying olefin oligomerization reactions and provide invaluable insights for the development of more effective catalysts.
基金the financial support from the National Natural Science Foundation of China(Nos.22588201,22225204 to D.D.,22472169 to L.Y.,and 22427801 to W.L.)the Outstanding Member of CAS Youth Innovation Promotion Association(No.Y2023053 to W.L.)the DICP&SIA Joint Project(No.UN202401 to W.L.)。
摘要1.Indroduction In light of the global transition toward carbon neutrality,the development of mild-condition ammonia synthesis technologies has gained significant attention as a promising solution to address the inherent limitations of the traditional Haber-Bosch approach,which remains highly energy-intensive due to the extreme operation conditions(above 350℃ and over 10 MPa)required to activate the robust N≡N bond(945 kJ mol-1).Furthermore,the process is carbon-intensive,as its primary hydrogen source is derived from hydrocarbon reforming with high carbon emissions[1,2].
基金financially supported by the National Natural Science Foundation of China(51576199 and 51536009)the Natural Science Fund of Guangdong Province(2017A030308010)
摘要2,5-dimethyfuran(DMF), which is produced from 5-hydroxymethyfurfural(HMF) by hydrodeoxygenation(HDO), is a high quality fuel due to the high heating value, the high octane number and the suitable boiling point. Selective hydrogenation of HMF into liquid fuel DMF has been widely researched. In this paper, Co_3O_4 catalyst was prepared by co-precipitation and was reduced at different temperatures to form Co–CoO_x catalysts. The characterization of catalysts was tested by XRD, TEM, XPS, TPR, BET and NH3-TPD.Co–CoO_x possessed a high amount of Co metal and CoO_x acidic sites, wherein Co worked as the active hydrogenation sites and CoO_x acted as the acid promoter to facilitate the selective HDO of HMF to DMF.The synergistic effect of Co–CoO_x is the key for HDO of HMF, obtaining 83.3% of DMF yield at 170 °C, 12 h and the reduction temperature of 400 °C. This method not only saves the catalyst cost, but also promotes the utilization of biomass energy.
基金supported by the National Basic Research Program of China(2004CB719500)the Key Project of Knowledge Innovation of Chinese Academy of Sciencos(KZCX3-SW-430)
摘要CeO2-Co3O4 catalysts for low-temperature CO oxidation were prepared by a co-precipitation method.In combination with the characterization methods of N2 adsorption/desorption,XRD,temperature-programmed reduction(TPR),and FT-IR,the influence of the cerium content on the catalytic performance of CeO2-Co3O4 was investigated.The results indicate that the prepared CeO2-Co3O4 catalysts exhibit a better activity than that of pure CeO2 or pure Co3O4.The catalyst with the Ce/Co atomic ratio 1:16 exhibits the best activity,which converts 77%of CO at room temperature and completely oxidizes CO at 45℃.
基金supported by the National Natural Science Foundation of China(Nos.22276060 and 21976059)Guangdong Basic and Applied Basic Research Foundation(No.2024A1515012636)China Scholarship Council Scholarship(No.201906155006)。
摘要The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO2 from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonization.However,steelwork off-gases typically contain various impurities,including H2S,which can deactivate commercial methanol synthesis catalysts,Cu/ZnO/Al2O3(CZA).Reverse water-gas shift(RWGS)reaction is the predominant side reaction in CO2 hydrogenation to methanol which can occur at ambient pressure,enabling the decouple of RWGS from methanol production at high pressure.Then,a series of activated CZA catalysts has been in-situ pretreated in 400 ppm H2S/Ar at 250℃and tested for both RWGS reaction at ambient pressure and CO2 hydrogenation to methanol at high pressure.An innovative decoupling strategy was employed to isolate the RWGS reaction from the methanol synthesis process,enabling the investigation of the evolution of active site structures and the poisoning mechanism through elemental analysis,X-ray Diffraction,X-ray Photoelectron Spectroscopy,Fourier Transform Infrared Spectroscopy,Temperature Programmed Reduction and CO2 Temperature Programmed Desorption.The results indicate that there are different dynamic migration behaviors of ZnOx in the two reaction systems,leading to different poisoning mechanisms.These interesting findings are beneficial to develop sulfur resistant and durable highly efficient catalysts for CO2 hydrogenation to methanol,promoting the carbon emission reduction in steel industry.