Enhanced glycerol valorization via descriptor-guided dual-site engineering in Ni-doped MnO2

Electrocatalytic glycerol oxidation reaction (GOR) presents a sustainable pathway for value-added chemical production but is hindered by unbalanced adsorption kinetics of reactants and a lack of rational catalyst design principles. This study introduces a descriptor-guided dual-site engineering strategy using transition metal (TM) doped α-MnO 2 (Mn, Fe, Co, Ni, Cu, or Zn) as model catalysts. Theoretical analysis identifies two critical electronic descriptors: the TM d -band center, influencing hydroxide (OH − ) adsorption; and the Mn d z 2 orbital center, affecting interactions with C/O intermediates. Among the series, Ni doping fine-tunes electronic coupling within the corner-oxygen-bridged TM–O–Mn moiety, synchronizing the adsorption kinetics of OH − and glycerol. Therefore, Ni-MnO 2 exhibits the highest GOR activity, achieving 50 mA F −1 at merely 1.35 V versus RHE, high formate productivity, and exceptional long-term stability (>88 hours). These insights establish key electronic parameters for catalyst optimization, offering strategic guidance to enhance catalytic activities in complex reactions. • A novel electronic descriptor framework is developed, establishing the d -band center of doped transition metals and the d z 2 orbital center of Mn as robust and predictive indicators of experimentally observed catalytic activity. • A new mechanistic concept—dual-site engineering induced kinetics synchronization—is introduced to elucidate the significantly enhanced performance of Ni-MnO 2 in glycerol oxidation reaction (GOR). • The optimized Ni-MnO 2 electrocatalyst demonstrates ultra-low onset potential, high formate productivity, and remarkable long-term operational stability for GOR.