Hydride‐Containing Pt‐doped Cu‐rich Nanoclusters: Synthesis, Structure, and Electrocatalytic Hydrogen Evolution
Rhone P. Brocha Silalahi, Hao Liang, Yongsung Jo, Jian‐Hong Liao, Tzu‐Hao Chiu, Ying‐Yann Wu, Xiaoping Wang, Samia Kahlal, Qi Wang, Woojun Choi, Dongil Lee, Jean‐Yves Saillard, C. W. Liu
Abstract
Abstract A structurally precise hydride‐containing Pt‐doped Cu‐rich nanocluster [PtH 2 Cu 14 {S 2 P(O i Pr) 2 } 6 (CCPh) 6 ] ( 1 ) has been synthesized. It consists of a bicapped icosahedral Cu 14 cage that encapsulates a linear PtH 2 unit. Upon the addition of two equivalents of CF 3 COOH to 1 , two hydrido clusters are isolated. These clusters are [PtHCu 11 {S 2 P(O i Pr) 2 } 6 (CCPh) 4 ] ( 2 ), which is a vertex‐missing Cu 11 cuboctahedron encaging a PtH moiety, and [PtH 2 Cu 11 {S 2 P(O i Pr) 2 } 6 (CCPh) 3 ] ( 3 ), a distorted 3,3,4,4,4‐pentacapped trigonal prismatic Cu 11 cage enclosing a PtH 2 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 H 2 SO 4 . 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.