Inspired by natural chloroplasts to construct Z-scheme heterojunction with efficient charge transfer mechanism for boosting photocatalytic carbon dioxide reduction  

受天然叶绿体启发构建具有高效电荷转移机制的Z型异质结以促进光催化二氧化碳还原

作　　者：LIU Zixuan ZHOU Xiang SONG Tingting YAO Ruiqi ZHAO Zhao LANG Zhongling LI Yingqi TAN Huaqiao WANG Yonghui LI Yangguang 柳子璇;周想;宋婷婷;姚瑞琪;赵钊;郎中玲;李英奇;谭华桥;王永慧;李阳光(东北师范大学化学学院,多酸与网格材料化学教育部重点实验室,吉林长春130024)

机构地区：[1]Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education,Faculty of Chemistry,Northeast Normal University,Changchun 130024,China

出　　处：《分子科学学报》2024年第5期411-420,共10页Journal of Molecular Science

基　　金：supported by the National Natural Science Foundation of China(22071020,22171041,22379024,22205034);the Natural Science Foundation of Jilin Province Science and Technology Department(20230508094RC and 20240101178JC);the Fundamental Research Funds for Central Universities(2412022QD012)

摘　　要：To alleviate the growing serious ecological threats brought by carbon-based fuels,it is a promising approach to construct a Z-scheme heterojunction via simulating the photosynthetic mechanism for solar-driven CO_(2)reduction into high value-added chemical fuels.Herein,we design and prepare a Z-scheme composite photocatalyst based on coupling metalloporphyrin-like Co_(x)-CN with Keggin-type POMs(PMo_(10)V_(2)O_(40)^(5-))by electrostatic interactions.By virtue of the redox property and charge transfer mechanism similar to chlorophyll P700 and P680 in green plants,the composite heterojunction exhibits broadspectrum absorption and strong CO_(2)absorption capacity,as well as the inhibition of the recombination of photo-introduced carriers.Under visible light irradiation,the optimized 0.05PMo_(10)V_(2)/Co_(1)-CN heterojunction shows the highest CO yield of 101.38μmol·g^(-1)·h^(-1),which is increased by about 250 and 9 times compared with those of CN and Co_(1)-CN,respectively,and concomitantly inhibits competitive H_(2) generation.This work provides a promising strategy to develop high-efficiency and low-cost Z-scheme photocatalysts for CO_(2)conversion.为了缓解碳基燃料带来的日益严重的生态威胁,通过模拟光合作用机制来构建Z型异质结提供了一种有前景的方法,以实现太阳能驱动的二氧化碳还原为高附加值化学燃料。本文设计并制备了一种基于静电相互作用将类金属卟啉Co_(x)-CN与Keggin型POM(PMo_(10)V_(2)O_(40)^(5-))偶联的Z机制复合光催化剂。由于其氧化还原性质和电荷转移机制与绿色植物中的叶绿素P700和P680相似,复合异质结表现出宽光谱吸收能力和强CO_(2)吸收能力,并抑制了光生载流子的复合。在可见光照射下,最佳的0.05PMo_(10)V_(2)/Co_(1)-CN异质结显示出最高的CO产量,为101.38μmol·g^(-1)·h^(-1),分别比CN和Co_(1)-CN增加了约250倍和约9倍,同时抑制了竞争性H_(2)的产生。这项工作为开发高效、低成本的Z机制CO_(2)转化光催化剂提供了一种有效的设计策略。

关 键 词：biomimetic Z-scheme heterojunction polyoxometalates metalloporphyrin-like Co-CN nanosheets electrostatic self-assembly photocatalytic CO_(2)reduction 

分 类 号：X701[环境科学与工程—环境工程] O644.1[理学—物理化学] O643.36[理学—化学]