Sulfur and phosphorus co-doping optimized electronic structure and modulated intermediate affinity on PdSP metallene for ethanol-assisted energy-saving H 2 production.

Coupling cathodic hydrogen evolution reaction (HER) and anodic electrochemical oxidation of organic small molecules in a co-electrolysis system could simultaneously realize high-value chemical generation and energy-saving hydrogen production, which, however, require high-performance electrocatalysts. In this work, we developed a one-step solvothermal method to synthesize S, P-co-doped Pd metallene (PdSP metallene) and employed it as a bifunctional electrocatalyst for both the HER and ethanol oxidation reaction (EOR). The co-doping of S and P atoms into Pd metallene could introduce multiple active sites and increase the electrochemically-active surface area. Moreover, the electronic interactions between Pd, S, and P atoms could regulate the electronic structure of the active sites and modulate the intermediate affinity on the resultant PdSP metallene, thus boosting the electrocatalytic HER and EOR performance. In the HER-EOR co-electrolysis system with bifunctional PdSP metallene electrocatalysts, only a 0.88 V of electrolysis voltage was required to fulfill 10 mA cm -2 current density, much lower than that of pure water electrolysis (1.41 V) using the same electrocatalysts.