Hydride-containing 2-Electron Pd/Cu Superatoms as Catalysts for Efficient Electrochemical Hydrogen Evolution.
Angew Chem Int Ed Engl
; 62(16): e202301272, 2023 Apr 11.
Article
em En
| MEDLINE
| ID: mdl-36807455
ABSTRACT
The first hydride-containing 2-electron palladium/copper alloys, [PdHCu11 {S2 P(Oi Pr)2 }6 (C≡CPh)4 ] (PdHCu11 ) and [PdHCu12 {S2 P(Oi Pr)2 }5 {S2 PO(Oi Pr)} (C≡CPh)4 ] (PdHCu12 ), are synthesized from the reaction of [PdH2 Cu14 {S2 P(Oi Pr)2 }6 (C≡CPh)6 ] (PdH2 Cu14 ) with trifluoroacetic acid (TFA). X-ray diffraction reveals that the PdHCu11 and PdHCu12 kernels consist of a central PdH unit encapsulated within a vertex-missing Cu11 cuboctahedron and complete Cu12 cuboctahedron, respectively. DFT calculations indicate that both PdHCu11 and PdHCu12 can be considered as axially-distorted 2-electron superatoms. PdHCu11 shows excellent HER activity, unprecedented within metal nanoclusters, with an onset potential of -0.05â
V (at 10â
mA cm-2 ), a Tafel slope of 40â
mV dec-1 , and consistent HER activity during 1000â
cycles in 0.5â
M H2 SO4 . 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.
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MEDLINE
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En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2023
Tipo de documento:
Article