Heterometallic Electrocatalysts Derived from High-Nuclearity Metal Clusters for Efficient Overall Water Splitting.

Pan, Fu-Chun; Jia, Jun; Gong, Feng; Liu, Yonghui; Liu, Shude; Jun, Seong Chan; Lin, Dunmin; Guo, Yuzheng et al. · ACS Nano · 2024

basic_science · Level V

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Abstract

The development of cost-effective electrocatalysts with an optimal surface affinity for intermediates is essential for sustainable hydrogen fuel production, but this remains insufficient. Here we synthesize Ni<sub>2</sub>P/MoS<sub>2</sub>-CoMo<sub>2</sub>S<sub>4</sub>@C heterometallic electrocatalysts based on the high-nuclearity cluster {Co<sub>24</sub>(TC4A)<sub>6</sub>(MoO<sub>4</sub>)<sub>8</sub>Cl<sub>6</sub>}, in which Ni<sub>2</sub>P nanoparticles were anchored to the surface of the MoS<sub>2</sub>-CoMo<sub>2</sub>S<sub>4</sub>@C nanosheets via strong interfacial interactions. Theoretical calculations revealed that the introduction of Ni<sub>2</sub>P phases induces significant disturbances in the surface electronic configuration of Ni<sub>2</sub>P/MoS<sub>2</sub>-CoMo<sub>2</sub>S<sub>4</sub>@C, resulting in more relaxed d-d orbital electron transfers between the metal atoms. Moreover, continuous electron transport was established by the formation of multiple heterojunction interfaces. The optimized Ni<sub>2</sub>P/MoS<sub>2</sub>-CoMo<sub>2</sub>S<sub>4</sub>@C electrocatalyst exhibited ultralow overpotentials of 198 and 73 mV for oxygen and hydrogen evolution reactions, respectively, in alkaline media, at 10 mA cm<sup>-2</sup>. The alkali electrolyzer constructed using Ni<sub>2</sub>P/MoS<sub>2</sub>-CoMo<sub>2</sub>S<sub>4</sub>@C required a cell voltage of only 1.45 V (10 mA cm<sup>-2</sup>) to drive overall water splitting with excellent long-term stability.