Affiliation:
1. MOE Key Laboratory of Cluster Science Beijing Key Laboratory of Photoelectroic/Electrophotonic Conversion Materials School of Chemistry and Chemical Engineering Beijing Institute of Technology Beijing 102488 China
2. Hefei National Laboratory for Physical Sciences at the Microscale University of Science and Technology of China Hefei Anhui 230026 China
3. MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage School of Chemistry and Chemical Engineering Harbin Institute of Technology Harbin 150001 China
Abstract
AbstractThe syntheses of atomically precise silver (Ag) clusters stabilized by multidentate lacunary polyoxometalate (POM) ligands have been emerging as a promising but challenging research direction, the combination of redox‐active POM ligands and silver clusters will render them unexpected geometric structures and catalytic properties. Herein, we report the successful construction of two structurally‐new lacunary POM‐stabilized Ag clusters, TBA6H14Ag14(DPPB)4(CH3CN)9[Ag24(Si2W18O66)3] ⋅ 10CH3CN ⋅ 9H2O ({Ag24(Si2W18O66)3}, TBA=tetra‐n‐butylammonium, DPPB=1,4‐Bis(diphenylphosphino)butane) and TBA14H6Ag9Na2(H2O)9[Ag27(Si2W18O66)3] ⋅ 8CH3CN ⋅ 10H2O ({Ag27(Si2W18O66)3}), using a facile one‐pot solvothermal approach. Under otherwise identical synthetic conditions, the molecular structures of two POM‐stabilized Ag clusters could be readily tuned by the addition of different organic ligands. In both compounds, the central trefoil‐propeller‐shaped {Ag24}14+ and {Ag27}17+ clusters bearing 10 delocalized valence electrons are stabilized by three C‐shaped {Si2W18O66} units. The femtosecond/nanosecond transient absorption spectroscopy revealed the rapid charge transfer between {Ag24}14+ core and {Si2W18O66} ligands. Both compounds have been pioneeringly investigated as catalysts for photocatalytic CO2 reduction to HCOOH with a high selectivity.
Funder
National Natural Science Foundation of China
Recruitment Program of Global Experts