Stable Heterometallic Cluster-Based Organic Framework Catalysts for Artificial Photosynthesis
Dong, LZ (Dong, Long-Zhang)[ 1 ] ; Zhang, L (Zhang, Lei)[ 1 ] ; Liu, J (Liu, Jiang)[ 1 ]*（刘江）; Huang, Q (Huang, Qing)[ 1 ] ; Lu, M (Lu, Meng)[ 1 ] ; Ji, WX (Ji, Wen-Xin)[ 2 ] ; Lan, YQ (Lan, Ya-Qian)[ 1 ]*（兰亚乾）
[ 1 ] Nanjing Normal Univ, Sch Chem & Mat Sci, Jiangsu Key Lab New Power Batteries, Jiangsu Collaborat Innovat Ctr Biomed Funct Mat, 1 Wenyuan Rd, Nanjing 210023, Peoples R China
[ 2 ] Ningxia Univ, State Key Lab High Efficiency Coal Utilizat & Gre, Yinchuan 750021, Peoples R China
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION，202002,59(7),2659-2663
A series of stable heterometallic Fe2M cluster-based MOFs (NNU-31-M, M=Co, Ni, Zn) photocatalysts are presented. They can achieve the overall conversion of CO2 and H2O into HCOOH and O-2 without the assistance of additional sacrificial agent and photosensitizer. The heterometallic cluster units and photosensitive ligands excited by visible light generate separated electrons and holes. Then, low-valent metal M accepts electrons to reduce CO2, and high-valent Fe uses holes to oxidize H2O. This is the first MOF photocatalyst system to finish artificial photosynthetic full reaction. It is noted that NNU-31-Zn exhibits the highest HCOOH yield of 26.3 mu mol g(-1) h(-1) (selectivity of ca. 100 %). Furthermore, the DFT calculations based on crystal structures demonstrate the photocatalytic reaction mechanism. This work proposes a new strategy for how to design crystalline photocatalyst to realize artificial photosynthetic overall reaction.