Publication | Open Access
Hydride‐containing 2‐Electron Pd/Cu Superatoms as Catalysts for Efficient Electrochemical Hydrogen Evolution
53
Citations
34
References
2023
Year
The first hydride-containing 2-electron palladium/copper alloys, [PdHCu<sub>11</sub> {S<sub>2</sub> P(O<sup>i</sup> Pr)<sub>2</sub> }<sub>6</sub> (C≡CPh)<sub>4</sub> ] (PdHCu<sub>11</sub> ) and [PdHCu<sub>12</sub> {S<sub>2</sub> P(O<sup>i</sup> Pr)<sub>2</sub> }<sub>5</sub> {S<sub>2</sub> PO(O<sup>i</sup> Pr)} (C≡CPh)<sub>4</sub> ] (PdHCu<sub>12</sub> ), are synthesized from the reaction of [PdH<sub>2</sub> Cu<sub>14</sub> {S<sub>2</sub> P(O<sup>i</sup> Pr)<sub>2</sub> }<sub>6</sub> (C≡CPh)<sub>6</sub> ] (PdH<sub>2</sub> Cu<sub>14</sub> ) with trifluoroacetic acid (TFA). X-ray diffraction reveals that the PdHCu<sub>11</sub> and PdHCu<sub>12</sub> kernels consist of a central PdH unit encapsulated within a vertex-missing Cu<sub>11</sub> cuboctahedron and complete Cu<sub>12</sub> cuboctahedron, respectively. DFT calculations indicate that both PdHCu<sub>11</sub> and PdHCu<sub>12</sub> can be considered as axially-distorted 2-electron superatoms. PdHCu<sub>11</sub> shows excellent HER activity, unprecedented within metal nanoclusters, with an onset potential of -0.05 V (at 10 mA cm<sup>-2</sup> ), a Tafel slope of 40 mV dec<sup>-1</sup> , and consistent HER activity during 1000 cycles in 0.5 M H<sub>2</sub> SO<sub>4</sub> . 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.
| Year | Citations | |
|---|---|---|
Page 1
Page 1