Tailored work function via activated interfacial electron transfer for boosting hydrogen production coupled with electrochemical glycerol oxidation

Developing high-performance electrocatalysts for glycerol-assisted water splitting is highly imperative for the applications in energy-saving hydrogen production coupled by valorizing biomass-derived feedstocks. Interface engineering, an effective strategy for tuning the interfacial electronic structures, enables the electrochemical performance improvement, while the precise control on interfacial electron transfer still remains challenging. Herein, Mo incorporation is employed to modulate the interfacial electronic structure of Ni 3 S 2 /Ni 3 P, resulting in an activated electron redistribution with more electrons flowing from Ni 3 P to Ni 3 S 2 . The enhanced electron transfer at the Mo-Ni 3 S 2 /Ni 3 P interface further reduces its work function and positively shifts the d -band center closer to Fermi level, promoting OH − and glycerol adsorption. Compared to Ni 3 S 2 /Ni 3 P, the Mo-Ni 3 S 2 /Ni 3 P exhibits superior electrocatalytic performance for both glycerol oxidation and hydrogen evolution reaction. In simulated alkaline seawater with glycerol, a two-electrode system using Mo-Ni 3 S 2 /Ni 3 P as both the anode and cathode achieves a 390 mV reduction in cell voltage to reach 100 mA cm −2 compared to water splitting, accompanied by a Faradaic efficiency above 90% for formate. This work will stimulate the further development of work function-guided design of efficient electrocatalysts for sustainable energy conversion. Enhanced adsorption enabled by a reduced work function through the activated interfacial electron transfer on the Mo-Ni 3 S 2 /Ni 3 P for energy-efficient glycerol-assisted H 2 production. • A Mo incorporated Ni 3 S 2 /Ni 3 P heterostructure was synthesized. • Mo incorporation at the interface actives more electrons to flow from Ni 3 P to Ni 3 S 2 . • The regulated electronic structure reduces the work function and positively shifts the d -band center of Mo-Ni 3 S 2 /Ni 3 P. • The Mo-Ni 3 S 2 /Ni 3 P enables glycerol oxidation assisted hydrogen production in simulated seawater.