Interfacial electronic coupling tunes d-band center in a sulfur-modulated NiFe–Cu catalyst for glycerol electrooxidation

Coupling glycerol oxidation with hydrogen production offers a promising approach to reducing the energy consumption of hydrogen production and upgrading biomass. However, the catalytic performance is often limited by insufficient interfacial charge transfer and poorly defined active sites. Herein, we report a sulfur-modulated NiFe layered double hydroxide catalyst integrated with a Metal-organic frameworks (MOF)-derived Cu framework on nickel foam, in which well-defined heterogeneous interfaces are deliberately constructed to regulate the local electronic structure and catalytic microenvironment. Sulfur incorporation reconstructs the metal coordination environment and induces electron redistribution. As a result, the catalyst exhibits outstanding glycerol oxidation performance toward formate with high selectivity over a broad potential window, along with remarkable durability at high current densities. In situ Fourier transform infrared (FTIR) spectroscopy identifies the key intermediates involved in glycerol oxidation, while density functional theory (DFT) calculations reveal that sulfur-induced electronic coupling lowers the reaction energy barrier and facilitates charge transfer.