Boosting the bifunctional electrocatalytic performance of Co2C via engineering the d-band center and hydrophilicity

Replacing the sluggish oxygen evolution reaction with the oxidation of benzyl alcohol to construct the hybrid water electrolysis system has been attractive for its merits of environmentally friendly and economically efficient. However, the activity of the catalyst to oxidize alcohols needs to be further improved. Tailoring the d-band center (Ed) has been proven as an effective method to promote the hydrogen evolution reaction (HER). How feasible is this strategy in the oxidation of benzyl alcohol? Here, using Co2C as a research platform, the doping nonmetal heteroatom (P, S, N) engineering is adopted to promote its electrocatalytic BA oxidation and HER performance. The results of electrochemical tests show that the P-doped Co2C (P–Co2C) only requires a low potential of 1.33 and 1.38 V vs. RHE to achieve current densities of 20 and 100 mA cm−2 for BA oxidation, which is superior to that of S–Co2C, N–Co2C, and pristine Co2C. The conversation and faradaic efficiency for BA is up to 98.1% and 93.8% during ten consecutive cycle tests. The P–Co2C also exhibited outstanding activity and stability toward HER. The density functional theory (DFT) calculation revealed that specified P doping could modify the d-band center of Co2C approaching the peak of the volcano map (electrochemical overpotentials ∼ Ed). The Gibbs free energy of the BA oxidation was also reduced, thus optimizing the adsorption and desorption process of intermediates. On the other hand, the catalyst surface physical properties of Co2C such as hydrophilicity was promoted by the doped heteroatoms which was favorable for the gas-liquid-solid triphase electrocatalytic reaction. This work offers a facial perception of regulating the d-band to design advanced bifunctional electrocatalysts for organic matter oxidation and HER.