Solar-light-driven CO_(2) reduction CO to CH_(4) and C2H6 is a complex process involving multiple elementary reactions and energy barriers.Therefore,achieving high CH_(4) activity and selectivity remains a significant...Solar-light-driven CO_(2) reduction CO to CH_(4) and C2H6 is a complex process involving multiple elementary reactions and energy barriers.Therefore,achieving high CH_(4) activity and selectivity remains a significant challenge.Here,we integrate bifunctional Cu2O and Cu-MOF(MOF=metal-organic framework)core–shell co-catalysts(Cu2O@Cu-MOF)with semiconductor TiO_(2).Experiments and theoretical calculations demonstrate that Cu2O(Cu+facilitates charge separation)and Cu-MOF(Cu2+improves the CO_(2) adsorption and activation)in the core–shell structure have a synergistic effect on photocatalytic CO_(2) reduction,reducing the formation barrier of the key intermediate*COOH and*CHO.The photocatalyst exhibits high CH_(4) yield(366.0μmol·g^(-1)·h^(-1)),efficient electron transfer(3283μmol·g^(-1)·h^(-1))and hydrocarbon selectivity(95.5%),which represents the highest activity of Cu-MOF-based catalysts in photocatalytic CO_(2) reduction reaction.This work provides a strategy for designing efficient photocatalysts from the perspective of precise regulation of components.展开更多
Photocatalytic hydrogen production utilizing abundant solar energy to produce high-calorie, clean, and pollution-free hydrogen is an important approach to solving environmental and resource problems. In this work, a h...Photocatalytic hydrogen production utilizing abundant solar energy to produce high-calorie, clean, and pollution-free hydrogen is an important approach to solving environmental and resource problems. In this work, a high-efficiency flower-like ZnSe/Cu_(0.08)Zn_(0.92)S photocatalyst was constructed through element doping and the formation of a Z-scheme heterojunction. The synergistic effect of Cu doping and the built-in electric field in the heterojunction enhanced light absorption and utilization by the ZnSe/Cu_(0.08)Zn_(0.92)S microflowers, accelerated the separation and transfer of photogenerated electrons and effectively inhibited electron–hole recombination. Thus the photocatalytic hydrogen production ability of the ZnSe/Cu_(0.08)Zn_(0.92)S microflowers was increased significantly. The highly stable ZnSe/Cu_(0.08)Zn_(0.92)S microflowers could provide excellent catalysis of photocatalytic hydrogen production.展开更多
基金supported by the National Natural Science Foundation of China(Nos.51802171,52072197,and 52003136)the Outstanding Youth Foundation of Shandong Province,China(No.ZR2019JQ14)+2 种基金the Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(No.2019KJC004)the Major Scientific and Technological Innovation Project(No.2019JZZY020405)Taishan Scholar Program,and the Major Basic Research Program of Natural Science Foundation of Shandong Province(No.ZR2020ZD09).
文摘Solar-light-driven CO_(2) reduction CO to CH_(4) and C2H6 is a complex process involving multiple elementary reactions and energy barriers.Therefore,achieving high CH_(4) activity and selectivity remains a significant challenge.Here,we integrate bifunctional Cu2O and Cu-MOF(MOF=metal-organic framework)core–shell co-catalysts(Cu2O@Cu-MOF)with semiconductor TiO_(2).Experiments and theoretical calculations demonstrate that Cu2O(Cu+facilitates charge separation)and Cu-MOF(Cu2+improves the CO_(2) adsorption and activation)in the core–shell structure have a synergistic effect on photocatalytic CO_(2) reduction,reducing the formation barrier of the key intermediate*COOH and*CHO.The photocatalyst exhibits high CH_(4) yield(366.0μmol·g^(-1)·h^(-1)),efficient electron transfer(3283μmol·g^(-1)·h^(-1))and hydrocarbon selectivity(95.5%),which represents the highest activity of Cu-MOF-based catalysts in photocatalytic CO_(2) reduction reaction.This work provides a strategy for designing efficient photocatalysts from the perspective of precise regulation of components.
基金This work was supported by National Natural Science Foundation of China(Grant Nos.52003136 and 52072197)Natural Science Foundation of Shandong Province(Grant No.ZR2022ME117)+7 种基金Outstanding Youth Foundation of Shandong Province,China(Grant No.ZR2019JQ14)Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(Grant No.2019KJC004)Major Scientific and Technological Innovation Project(Grant No.2019JZZY020405)Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant No.ZR2020ZD09Taishan Scholar Young Talent Program(Grant No.tsqn201909114)Talent Fund of Shandong Collaborative Innovation Center of Eco-Chemical Engineering(Grant No.XTCXYX33)Open Project of State Key Laboratory of Supramolecular Structure and Materials(Grant No.sklssm2023037)Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(Grant No.2021-K60).
文摘Photocatalytic hydrogen production utilizing abundant solar energy to produce high-calorie, clean, and pollution-free hydrogen is an important approach to solving environmental and resource problems. In this work, a high-efficiency flower-like ZnSe/Cu_(0.08)Zn_(0.92)S photocatalyst was constructed through element doping and the formation of a Z-scheme heterojunction. The synergistic effect of Cu doping and the built-in electric field in the heterojunction enhanced light absorption and utilization by the ZnSe/Cu_(0.08)Zn_(0.92)S microflowers, accelerated the separation and transfer of photogenerated electrons and effectively inhibited electron–hole recombination. Thus the photocatalytic hydrogen production ability of the ZnSe/Cu_(0.08)Zn_(0.92)S microflowers was increased significantly. The highly stable ZnSe/Cu_(0.08)Zn_(0.92)S microflowers could provide excellent catalysis of photocatalytic hydrogen production.
