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Updated: Jun 13, 2026

Developing Photosensitizer-Cobaloxime Hybrids for Solar-Driven H2 Production in Aqueous Aerobic Conditions
Published on: October 5, 2019
High-Entropy-Induced Lattice Distortion Activates Dual-Cobalt Site Synergy for Boosted Photo(Electro)Catalytic
Bao-Feng Shan1, Zong-Yan Zhao1, Huiting Huang2
1Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, P. R. China.
Abstract:
High-entropy engineering breaks the activity-stability trade-off in solar water splitting. We design a spinel oxide (CuCoNi)(GaCoCrMnFe)2O4 with lattice distortion (δavg = 3.35%) and stabilized Cotet 2+/Cooct 3+ dual sites. The cocktail effect goes beyond elemental averaging: Cu/Ga harvest light; Co enables dual-site surface catalysis; Ni/Cr induce distortion and local built-in fields; Cu/Mn trigger Jahn-Teller upshifting the d-band center; Fe/Mn balance distortion; multivalent species provide a broad redox window. The material achieves a photocatalytic HER rate of 16.62 µmol∙h-1∙g-1-16.3× that of Co3O4 and 10.8× that of CuGa2O4, alongside <5% decay over 30 h. In photoelectrochemical tests, it delivers 2.03 mA∙cm-2 at 0 VRHE in neutral electrolyte (21.6× and 67.7× the benchmarks) and 7.08 mA∙cm-2 under alkaline conditions with 48% IPCE and 0.56% HC-STH. Distortion-induced dipoles (0.87 D) extend carrier lifetime to 6.95 ns; Cotet 2+ dissociates water (Ea = 0.187 eV) while Cooct 3+ reduces protons (ΔG*H = 0.288 eV); configurational entropy (2.71R) stabilizes the structure. This "entropy-structure-function" strategy offers a generalizable route to durable, high-performance solar fuel catalysts.
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