文献类型：期刊文献

英文题名：Boosting Interfacial Charge-Transfer Kinetics for Efficient Overall CO2 Photoreduction via Rational Design of Coordination Spheres on Metal-Organic Frameworks

作者：Fang, Zhi-Bin[1];Liu, Ting-Ting[3];Liu, Junxue[4,5];Jin, Shengye[4,5];Wu, Xin-Ping[3];Gong, Xue-Qing[3];Wang, Kecheng[6];Yin, Qi[1];Liu, Tian-Fu[1,2];Cao, Rong[1,2];Zhou, Hong-Cai[6]

机构：[1]Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China;[2]Univ Chinese Acad Sci, Beijing 100049, Peoples R China;[3]East China Univ Sci & Technol, Ctr Computat Chem, Res Inst Ind Catalysis, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[4]Chinese Acad Sci, State Key Lab Mol React Dynam, Dalian Inst Chem Phys, Dalian 116023, Peoples R China;[5]Chinese Acad Sci, Collaborat Innovat Ctr Chem Energy Mat, Dalian Inst Chem Phys, Dalian 116023, Peoples R China;[6]Texas A&M Univ, Dept Chem, College Stn, TX 77842 USA

年份：2020

卷号：142

期号：28

起止页码：12515

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20203209018988);WOS:【SCI-EXPANDED(收录号:WOS:000551495700067)】；

基金：This work was financially supported by National Natural Science Foundation of China (NSFC, Grant 21802142, 21871267, 21825301 and 21520102001), National Key R&D Program of China (Grant 2018YFA0208600), the Recruitment Program of Global Youth Experts, the CAS Strategic Priority Research Program (Grant XDB20000000), the Key Research Program of Frontier Science CAS (QYZDJ-SSW-SLH045), and the Shanghai Sailing Program (20YF1410000). The authors are grateful to Prof. Gang Xu (FJIRSM) for the instrumental support on gas-sensing tests. The authors thank Prof. Chuan-Fu Sun (FJIRSM), Prof. Teng Zhang (FJIRSM) and Prof. Ping Liu (FZU) for valuable discussions.

语种：英文

外文关键词：Carbon dioxide - Carboxylation - Light - Nickel compounds - Charge transfer - Kinetics - Photocatalytic activity - Spheres

摘要：The recombination of electron-hole pairs severely detracts from the efficiency of photocatalysts. This issue could be addressed in metal-organic frameworks (MOFs) through optimization of the charge-transfer kinetics via rational design of structures at atomic level. Herein, a pyrazolyl porphyrinic Ni-MOF (PCN-601), integrating light harvesters, active catalytic sites, and high surface areas, has been demonstrated as a superior and durable photocatalyst for visible-light-driven overall CO2 reduction with H2O vapor at room temperature. Kinetic studies reveal that the robust coordination spheres of pyrazolyl groups and Ni-oxo clusters endow PCN-601 with proper energy band alignment and ultrafast ligand-to-node electron transfer. Consequently, the CO2-to-CH4 production rate of PCN-601 far exceeds those of the analogous MOFs based on carboxylate porphyrin and the classic Pt/CdS photocatalyst by more than 3- and 20-fold, respectively. The reaction avoids the use of hole scavengers and proceeds in a gaseous phase which can take full advantage of the high gas uptake of MOFs. This work demonstrates that the rational design of coordination spheres in MOF structures not only reconciles the contradiction between reactivity and stability but also greatly promotes the interfacial charge transfer to achieve optimized kinetics, providing guidance for the design of highly efficient MOF photocatalysts.