|
|||||
|
|
Poly-Hydride [AuI7(PPh3)7H5](SbF6)2 cluster complex: Structure,Transformation, and Electrocatalytic CO2 Reduction Properties |
|
| Authors: | Li Tang Yuting Luo Xiaoshuang Ma Bin Wang Mei Ding Ru Wang Pu Wang Prof Dr Yong Pei Prof Dr Shuxin Wang |
| Institution: | 1. College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao, 266042 P. R. China
These authors contributed equally to this work.;2. Department of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, Xiangtan, Hunan, 411105 P. R. China These authors contributed equally to this work.;3. College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao, 266042 P. R. China;4. Department of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, Xiangtan, Hunan, 411105 P. R. China |
| Abstract: | Hydride AuI bonds are labile due to the mismatch in electric potential of an oxidizing metal and reducing ligand, and therefore the structure and structure–activity relationships of nanoclusters that contain them are seldom studied. Herein, we report the synthesis and characterization of Au7(PPh3)7H5](SbF6)2 (abbrev. Au7H5 2+ ), an Au cluster complex containing five hydride ligands, which decomposed to give Au8(PPh3)7]2+ (abbrev. Au8 2+ ) upon exposure to light (300 to 450 nm). The valence state of AuI and H− was verified by density functional theory (DFT) calculations, NMR, UV/Vis and XPS. The two nanoclusters behaved differently in the electrocatalytic CO2 reduction reaction (CO2RR): Au7H5 2+ exhibited 98.2 % selectivity for H2, whereas Au8 2+ was selective for CO (73.5 %). Further DFT calculations showed that the H− ligand inhibited the CO2RR process compared with the electron-donor H. |
| Keywords: | CO2RR Dehydrogenation Electrocatalytic Hydride Gold(I) Complex Nanocluster |