The self-complementary effect through strong orbital coupling in ultrathin high-entropy alloy nanowires boosting pH-universal multifunctional electrocatalysis

Rational control of the compositions, morphologies and sizes of electrocatalyst are the key factors for achieving high performance of electrocatalytic reactions. Herein, a newly ultrathin PtRuRhCoNi high-entropy alloy nanowires (HEA-NWs) (~1.6 nm) catalyst is designed. The PtRuRhCoNi NWs/C achieved high mass activity of 7.68 A mg−1PtRuRh, ultrahigh C1 selectivity of 78% for ethanol oxidation reaction. For hydrogen evolution reaction, the PtRuRhCoNi NWs/C also reached high mass activity, turnover frequency (11.99 A mg−1PtRuRh, 31.9 s−1, 0.5 M H2SO4 and 8.07 A mg−1PtRuRh, 26.7 s−1, 1 M KOH at −0.05 V vs. RHE) and stability. Theoretical calculations demonstrated that the excellent electroactivity of HEA is benefited by the self-complementary effect through strong orbital coupling, which maximized the electroactivity towards both oxidation and reduction and preferred binding of key intermediate. The design of pH-universal multifunctional catalyst by rational control of the compositions, morphologies and sizes strategy can facilitate the research of advanced catalysts.