Photocatalytic conversion of CO_(2)into a special chemical fuel with high yield and selectivity is still a major challenge.Herein,a 3 D hierarchical Ni Al-LDH/Ti_(3)C_(2)MXene(LDH/TC)nanocomposite is constructed throu...Photocatalytic conversion of CO_(2)into a special chemical fuel with high yield and selectivity is still a major challenge.Herein,a 3 D hierarchical Ni Al-LDH/Ti_(3)C_(2)MXene(LDH/TC)nanocomposite is constructed through in situ loading of Ti_(3)C_(2)nanosheets on the Ni Al-LDH scaffold during the hydrothermal process.The formation of a uniform and well-defined 2 D/2 D heterogeneous interface can be realized by optimizing the ratio of Ti_(3)C_(2)and the precursors for Ni Al-LDH.The 3 D hierarchical scaffold with high specific surface area contributes to the favourable photon adsorption and utilization.The intimate contact between Ti_(3)C_(2)and Ni Al-LDH with numerous interfaces effectively promotes the separation of the photoinduced electron-hole pairs in Ni Al-LDH.Together with the highly exposed oxidation-reduction active sites and the enhanced CO_(2)capture and activation.The maximum photocatalytic CO production rate on Ni AlLDH/Ti_(3)C_(2)reaches 11.82 lmol g^(-1)h^(-1)with 92%selectivity and superior stability.This work provides an effective approach for the development of an ideal photocatalyst by collaborative utilization of materials with different dimensionalities.展开更多
Artificial photosynthesis is considered to be a promising approach for energy storage and global warming mitigation.However,the suboptimal selectivity of products and the low conversion efficiency of CO_(2)persist as ...Artificial photosynthesis is considered to be a promising approach for energy storage and global warming mitigation.However,the suboptimal selectivity of products and the low conversion efficiency of CO_(2)persist as challenges,driving continuous interest in improving catalytic design.Herein,a metal-organic framework(MOF)modified with a conductive polymer was constructed.The resulting composite,named TiFe-BTC/PoPD(BTC:1,3,5-benzenetricarboxylate;PoPD:poly-o-phenylenediamine),served as a highly efficient and selective photocatalyst for the conversion of CO_(2)to CO under visible light.Interestingly,thanks to the synergistic promotion of pressure and conductive polymer,the TiFe-BTC/PoPD achieved a remarkable CO evolution rate of 7.178 mmol/g/h and demonstrated excellent selectivity of over 99%for CO at 6.0 MPa CO_(2).Thus,this approach resulted in∼70-fold increase in the evolution rate compared with that of TiFe-BTC at ambient pressure(0.1 MPa).Experimental characterizations,combined with theoretical calculations further revealed that high-pressure CO_(2)effectively suppressed H2 evolution,thereby enhancing CO production and promoting high selectivity.This finding illustrated a straightforward strategy for an efficient photoconversion of CO_(2)to CO by subtly leveraging the synergistic effect of high-pressure CO_(2)and polymer-modified MOF photocatalyst.展开更多
Elements from the right side of the periodic table,including cations with d^(10) and s^(0)p^(0) configurations,have been shown to improve photocatalytic activity in various photocatalysts either as dopants or principa...Elements from the right side of the periodic table,including cations with d^(10) and s^(0)p^(0) configurations,have been shown to improve photocatalytic activity in various photocatalysts either as dopants or principal elements.This study introduces the first medium-and high-entropy oxide photocatalysts accommodating only d^(10) and s^(0)p^(0) cations.The designated oxides,AlZnGaO_4 and AlZnGaSnBiO_(7.5)(dual-phase heterostructure of AlZnGaO_4 and 1/2Sn_(2)Bi_(2)O_(7)),demonstrate good optical properties and promising photocatalytic activity for water conversion to hydrogen and CO_(2) conversion to methane compared to entropy-stabilized cations containing only d^(0) or d^(0)+d^(10) configurations.The good activity of these oxides was ascribed to their high work function,which was supported by experimental analysis and firstprinciples calculations.Moreover,AlZnGaSnBiO_(7.5) exhibited enhanced activity compared to AlZnGaO_4due to the creation of type Ⅱ heterojunctions and resultant higher charge carrier separation and lifetime.This study introduces the significance of d^(10)+s^(0)p^(0) cationic configuratio n,high work fu nction,and inherent heterojunctions on the design of advanced high-entropy photocatalysts with high photocatalytic activity.展开更多
Herein,the catalysts of ultrathin g-C_(3)N_(4)surface-modified hollow spherical Bi2MoO6(g-C_(3)N_(4)/Bi2MoO6,abbreviated as CN/BMO)were fabricated by the co-solvothermal method.The variable valence Mo^(5+)/Mo^(6+)ioni...Herein,the catalysts of ultrathin g-C_(3)N_(4)surface-modified hollow spherical Bi2MoO6(g-C_(3)N_(4)/Bi2MoO6,abbreviated as CN/BMO)were fabricated by the co-solvothermal method.The variable valence Mo^(5+)/Mo^(6+)ionic bridge in CN/BMO catalysts can boost the rapid transfer of photogenerated electrons from Bi2MoO6to g-C_(3)N_(4).And the synergy effect of g-C_(3)N_(4)and Bi2MoO6components remarkably enhance CO_(2)adsorption capability.CN/BMO-2 catalyst has the best performances for visible light-driven CO_(2)reduction compared with single Bi2MoO6and g-C_(3)N_(4),i.e.,its amount and selectivity of CO product are 139.50μmol g-1and 96.88%for 9 h,respectively.Based on the results of characterizations and density functional theory calculation,the photocatalytic mechanism for CO_(2)reduction is proposed.The high-efficient separation efficiency of photogenerated electron-hole pairs,induced by variable valence Mo^(5+)/Mo^(6+)ionic bridge,can boost the rate-limiting steps(COOH*-to-CO*and CO*desorption)of selective visible light-driven CO_(2)conversion into CO.It inspires the establishment of efficient photocatalysts for CO_(2)conversion.展开更多
基金the National Natural Science Foundation of China(51303083)the National Natural Science Foundation of China for Excellent Young Scholars(51922050)+2 种基金the Natural Science Foundation of Jiangsu Province(BK20191293)the China Postdoctoral Science Foundation(2017m621708)the Fundamental Research Funds for the Central Universities(30920021123)for financial support。
文摘Photocatalytic conversion of CO_(2)into a special chemical fuel with high yield and selectivity is still a major challenge.Herein,a 3 D hierarchical Ni Al-LDH/Ti_(3)C_(2)MXene(LDH/TC)nanocomposite is constructed through in situ loading of Ti_(3)C_(2)nanosheets on the Ni Al-LDH scaffold during the hydrothermal process.The formation of a uniform and well-defined 2 D/2 D heterogeneous interface can be realized by optimizing the ratio of Ti_(3)C_(2)and the precursors for Ni Al-LDH.The 3 D hierarchical scaffold with high specific surface area contributes to the favourable photon adsorption and utilization.The intimate contact between Ti_(3)C_(2)and Ni Al-LDH with numerous interfaces effectively promotes the separation of the photoinduced electron-hole pairs in Ni Al-LDH.Together with the highly exposed oxidation-reduction active sites and the enhanced CO_(2)capture and activation.The maximum photocatalytic CO production rate on Ni AlLDH/Ti_(3)C_(2)reaches 11.82 lmol g^(-1)h^(-1)with 92%selectivity and superior stability.This work provides an effective approach for the development of an ideal photocatalyst by collaborative utilization of materials with different dimensionalities.
基金funding support from the National Natural Science Foundation of China(grant nos.22373080 and 21903066)the President Fund of Xiamen University,China(grant no.20720210046)+2 种基金funding support from the National Natural Science Foundation of China(grant no.22078274)supported by the Fundamental Research Funds for the Central Universities,China(grant no.20720240054)the Natural Science Foundation of Fujian Province,China(grant no.2022J05009).
文摘Artificial photosynthesis is considered to be a promising approach for energy storage and global warming mitigation.However,the suboptimal selectivity of products and the low conversion efficiency of CO_(2)persist as challenges,driving continuous interest in improving catalytic design.Herein,a metal-organic framework(MOF)modified with a conductive polymer was constructed.The resulting composite,named TiFe-BTC/PoPD(BTC:1,3,5-benzenetricarboxylate;PoPD:poly-o-phenylenediamine),served as a highly efficient and selective photocatalyst for the conversion of CO_(2)to CO under visible light.Interestingly,thanks to the synergistic promotion of pressure and conductive polymer,the TiFe-BTC/PoPD achieved a remarkable CO evolution rate of 7.178 mmol/g/h and demonstrated excellent selectivity of over 99%for CO at 6.0 MPa CO_(2).Thus,this approach resulted in∼70-fold increase in the evolution rate compared with that of TiFe-BTC at ambient pressure(0.1 MPa).Experimental characterizations,combined with theoretical calculations further revealed that high-pressure CO_(2)effectively suppressed H2 evolution,thereby enhancing CO production and promoting high selectivity.This finding illustrated a straightforward strategy for an efficient photoconversion of CO_(2)to CO by subtly leveraging the synergistic effect of high-pressure CO_(2)and polymer-modified MOF photocatalyst.
基金supported partially by Mit-sui Chemicals,Inc.,Japanpartially by the Japan Science and Technology Agency (JST),the Establishment of University Fellowships Towards the Creation of Science Technology Innovation (Number: JPMJFS2132)in part by the ASPIRE project of the JST (Number: JPMJAP2332)。
文摘Elements from the right side of the periodic table,including cations with d^(10) and s^(0)p^(0) configurations,have been shown to improve photocatalytic activity in various photocatalysts either as dopants or principal elements.This study introduces the first medium-and high-entropy oxide photocatalysts accommodating only d^(10) and s^(0)p^(0) cations.The designated oxides,AlZnGaO_4 and AlZnGaSnBiO_(7.5)(dual-phase heterostructure of AlZnGaO_4 and 1/2Sn_(2)Bi_(2)O_(7)),demonstrate good optical properties and promising photocatalytic activity for water conversion to hydrogen and CO_(2) conversion to methane compared to entropy-stabilized cations containing only d^(0) or d^(0)+d^(10) configurations.The good activity of these oxides was ascribed to their high work function,which was supported by experimental analysis and firstprinciples calculations.Moreover,AlZnGaSnBiO_(7.5) exhibited enhanced activity compared to AlZnGaO_4due to the creation of type Ⅱ heterojunctions and resultant higher charge carrier separation and lifetime.This study introduces the significance of d^(10)+s^(0)p^(0) cationic configuratio n,high work fu nction,and inherent heterojunctions on the design of advanced high-entropy photocatalysts with high photocatalytic activity.
基金supported by the National Natural Science Foundation of China(21972166)the Beijing Natural Science Foundation(2202045)the National Key Research and Development Program of China(2019YFC1907600)。
文摘Herein,the catalysts of ultrathin g-C_(3)N_(4)surface-modified hollow spherical Bi2MoO6(g-C_(3)N_(4)/Bi2MoO6,abbreviated as CN/BMO)were fabricated by the co-solvothermal method.The variable valence Mo^(5+)/Mo^(6+)ionic bridge in CN/BMO catalysts can boost the rapid transfer of photogenerated electrons from Bi2MoO6to g-C_(3)N_(4).And the synergy effect of g-C_(3)N_(4)and Bi2MoO6components remarkably enhance CO_(2)adsorption capability.CN/BMO-2 catalyst has the best performances for visible light-driven CO_(2)reduction compared with single Bi2MoO6and g-C_(3)N_(4),i.e.,its amount and selectivity of CO product are 139.50μmol g-1and 96.88%for 9 h,respectively.Based on the results of characterizations and density functional theory calculation,the photocatalytic mechanism for CO_(2)reduction is proposed.The high-efficient separation efficiency of photogenerated electron-hole pairs,induced by variable valence Mo^(5+)/Mo^(6+)ionic bridge,can boost the rate-limiting steps(COOH*-to-CO*and CO*desorption)of selective visible light-driven CO_(2)conversion into CO.It inspires the establishment of efficient photocatalysts for CO_(2)conversion.
