Hydride‐containing 2‐Electron Pd/Cu Superatoms as Catalysts for Efficient Electrochemical Hydrogen Evolution

Abstract

The first hydride-containing 2-electron palladium/copper alloys, [PdHCu 11 {S 2 P(O i Pr) 2 } 6 (C�CPh) 4 ] (PdHCu 11 ) and [PdHCu 12 {S 2 P(O i Pr) 2 } 5 {S 2 PO(O i Pr)} (C�CPh) 4 ] (PdHCu 12 ), are synthesized from the reaction of [PdH 2 Cu 14 {S 2 P(O i Pr) 2 } 6 (C�CPh) 6 ] (PdH 2 Cu 14 ) with trifluoroacetic acid (TFA). X-ray diffraction reveals that the PdHCu 11 and PdHCu 12 kernels consist of a central PdH unit encapsulated within a vertex-missing Cu 11 cuboctahedron and complete Cu 12 cuboctahedron, respectively. DFT calculations indicate that both PdHCu 11and PdHCu 12 can be considered as axially-distorted 2electron superatoms. PdHCu 11 shows excellent HER activity, unprecedented within metal nanoclusters, with an onset potential of À 0.05 V (at 10 mA cm À 2 ), a Tafel slope of 40 mV dec À 1 , and consistent HER activity during 1000 cycles in 0.5 M H 2 SO 4 . Our study suggests that the accessible central Pd site is the key to HER activity and may provide guidelines for correlating catalyst structures and HER activity.

Hydride Doping Effects on the Structure and Properties of Eight-Electron Rh/Ag Superatoms: The [RhHx@Ag21–x{S2P(OnPr)2}12] (x = 0–2) Series

“…DFT investigations at the BP86/Def2-TZVP level were performed on compounds 1 – 3 (see Computational Details in the Supporting Information). For the sake of computational limitations, the S 2 P­(O n Pr) 2 ligands were replaced by S 2 PH 2 , a simplification that has been proven reasonable in many previous investigations. ,,− ,,,,,, Selected computed data are given in Tables and . The computed metrics for 1 and 2 (Table ) are in good agreement with their experimental counterparts, with a small overestimation of bond distances.…”

“…All three NCs exhibit strong photoluminescence in the NIR region at 77 K in 2-MeTHF glass. The property of 3 which easily releases H suggests that this cluster could be a good electrocatalyst for hydrogen evolution reactions. , This will be the subject of our future research on these compounds. This work highlights the impact of varying the number of “metallic hydrogen” encapsulated within the superatomic core.…”

Thiacalix[4]arene Etching of an Anisotropic Cu70H22 Intermediate for Accessing Robust Modularly Assembled Copper Nanoclusters

“…33−35 37 It is worth noting that the success of size expansion and core alloying relies on the presence of a relatively stable template, as analogous structures were consistently observed. 38,39 Alternatively, some researchers have proposed that the process directly leads to the formation of another thermodynamically stable metal NC through fragmentation and reassembly; however, substantial empirical evidence supporting this hypothesis is still lacking. 40−42 In this work, we report the synthesis and characterization of a nonspherical high-nuclearity copper-hydride NC [Cl@ Cu 70 H 22 (PhC�C) 29…”

“…Zheng et al introduced Pt 4+ ions into Cu 32 H 8 to obtain Pt 2 Cu 34 . It is worth noting that the success of size expansion and core alloying relies on the presence of a relatively stable template, as analogous structures were consistently observed. , Alternatively, some researchers have proposed that the process directly leads to the formation of another thermodynamically stable metal NC through fragmentation and reassembly; however, substantial empirical evidence supporting this hypothesis is still lacking. − …”

Locating Interstitial Hydrides in MH2@Cu14 (M = Cu, Ag) Clusters by Single-Crystal X-ray Diffraction

“…In recent years, extensive research has been conducted on metal hydrides to explore their potential applications in diverse fields, including organic synthesis, , catalysis, − and hydrogen storage. , Our particular interest is ligand-protected copper hydride clusters, which have garnered significant attention due to their remarkable stability, structural diversity, and unique bonding features. − These copper hydride compounds have emerged as important catalysts for various organic reactions and have shown promise in electrocatalytic CO 2 reduction and electrochemical hydrogen evolution reaction (HER) activity . To gain a comprehensive understanding of the atomic-level structure-property relationship of metal hydrides, single-crystal X-ray diffraction (SC-XRD) is an indispensable and cost-effective technology in comparison to neutron experiments.…”