Affiliation:
1. Department of Chemistry National Dong Hwa University No. 1, Sec. 2, Da Hsueh Rd. Shoufeng Hualien 97401 Taiwan R. O. C.
2. Univ Rennes CNRS, ISCR-UMR 6226 F-35000 Rennes France
3. Department of Chemistry Yonsei University Seoul 03722 Republic of Korea
4. Neutron Scattering Division Neutron Sciences Directorate Oak Ridge National Laboratory Oak Ridge Tennessee 37831 United States
Abstract
AbstractA structurally precise hydride‐containing Pt‐doped Cu‐rich nanocluster [PtH2Cu14{S2P(OiPr)2}6(CCPh)6] (1) has been synthesized. It consists of a bicapped icosahedral Cu14 cage that encapsulates a linear PtH2 unit. Upon the addition of two equivalents of CF3COOH to 1, two hydrido clusters are isolated. These clusters are [PtHCu11{S2P(OiPr)2}6(CCPh)4] (2), which is a vertex‐missing Cu11 cuboctahedron encaging a PtH moiety, and [PtH2Cu11{S2P(OiPr)2}6(CCPh)3] (3), a distorted 3,3,4,4,4‐pentacapped trigonal prismatic Cu11 cage enclosing a PtH2 unit. The electronic structure of 2, analyzed by Density Functional Theory, is a 2e superatom. The electrocatalytic activities of 1–3 for hydrogen evolution reaction (HER) were compared. Notably, Cluster 2 exhibited an exceptionally excellent HER activity within metal nanoclusters, with an onset potential of −0.03 V (at 10 mA cm−2), a Tafel slope of 39 mV dec−1, and consistent HER activity throughout 3000 cycles in 0.5 M H2SO4. Our study suggests that the accessible central Pt site plays a crucial role in the remarkable HER activity and may provide valuable insights for establishing correlations between catalyst structure and HER activity.
Funder
National Science and Technology Council
National Research Foundation of Korea
Subject
General Chemistry,Catalysis,Organic Chemistry