High-Entropy-Induced Lattice Distortion Activates Dual-Cobalt Site Synergy for Boosted Photo(Electro)Catalytic Hydrogen Evolution.
basic_science · Level V
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- Record sourced from PubMed, PMID 42281268.
- Also identified by DOI 10.1002/adma.73708.
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Abstract
High-entropy engineering breaks the activity-stability trade-off in solar water splitting. We design a spinel oxide (CuCoNi)(GaCoCrMnFe)<sub>2</sub>O<sub>4</sub> with lattice distortion (δ<sub>avg</sub> = 3.35%) and stabilized Co<sub>tet</sub> <sup>2+</sup>/Co<sub>oct</sub> <sup>3+</sup> 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<sup>-1</sup>∙g<sup>-1</sup>-16.3× that of Co<sub>3</sub>O<sub>4</sub> and 10.8× that of CuGa<sub>2</sub>O<sub>4</sub>, alongside <5% decay over 30 h. In photoelectrochemical tests, it delivers 2.03 mA∙cm<sup>-2</sup> at 0 V<sub>RHE</sub> in neutral electrolyte (21.6× and 67.7× the benchmarks) and 7.08 mA∙cm<sup>-2</sup> under alkaline conditions with 48% IPCE and 0.56% HC-STH. Distortion-induced dipoles (0.87 D) extend carrier lifetime to 6.95 ns; Co<sub>tet</sub> <sup>2+</sup> dissociates water (E<sub>a</sub> = 0.187 eV) while Co<sub>oct</sub> <sup>3+</sup> reduces protons (ΔG<sub>*H</sub> = 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.