Self-complementary effect through d-d orbital coupling in high-entropy alloy nanowires boosting electrocatalytic biomass upgrading

Designing highly active and selective electrocatalytic catalysts to accelerate 5-hydroxymethylfurfural (HMF) oxidation is significant but challenging in biomass upgrading. Herein, the high-entropy alloy AuCuAgPdNi nanowires catalyst with a self-complementary effect via a simple one-pot wet chemical method is reported. Notably, AuCuAgPdNi NWs show excellent activity and selectivity during HMF oxidation with a 2,5-furandicarboxylic acid (FDCA) yield of 95.5 % and a selectivity of 98.4 % at the potential of 1.60 V vs. RHE. Moreover, a flow electrolytic cell is designed to couple the high-performance HMF oxidation reaction (HMFOR) at the anode and the faradaic efficiency of the hydrogen evolution reaction approaching 100 % at the cathode. In-situ Fourier transform infrared (in-situ FTIR) results reveal the relationship between the HMFOR pathway and potential. Theoretical calculation shows that AuCuAgPdNi NWs promote the exchangeability of surface electrons through the self-complementary effect generated by d - d orbital coupling, thus achieving efficient HMFOR. This work provides insights into the innovative synthesis and mechanisms inherent catalytic of high-entropy alloy systems and offers ideas for the value-added conversion of biomass.