Product Ligand‐Modification on Ni(OH) 2 for Boosted Electrocatalytic Oxidation of Aromatic Alcohols

ABSTRACT The development of active electrocatalysts for converting biomass‐derived aromatic alcohols into value‐added acids is of great significance. Ni(OH) 2 has been employed as a cost‐effective catalyst, unfortunately, suffering from rather low catalytic activity due to the considerable energy barrier to transform into active NiOOH and the weak interaction with reactants. To address these limitations, a novel “product ligand‐modification” (PLM) strategy has been proposed here simply by adopting the target molecule ligands as modification units, which simultaneously facilitates the Ni(II)/Ni(III) redox kinetics and significantly enriches reactants at the catalytic surface via profound π‐π stacking interaction. The PLM strategy has been demonstrated to exhibit exceptionally high performance in electro‐oxidizing aromatic alcohols into corresponding acids across various product ligand‐Ni(OH) 2 (PL‐Ni(OH) 2 ) catalysts. As a typical paradigm, the aromatic ligand FDCA‐modified Ni(OH) 2 catalyst (termed FDCA‐Ni(OH) 2 ) demonstrates significantly enhanced BHMF electrocatalytic oxidation activity, featuring a BHMF conversion rate of >99.4%, FDCA selectivity and yield of 99.2% and 98.6%, and Faradaic efficiency of 99.0%. Furthermore, FDCA‐Ni(OH) 2 features an excellent stability for over 250 h in a flow electrolyzer to produce FDCA with a >99.0% purity. This PLM strategy offers valuable insights into the performance enhancement of Ni(OH) 2 catalyst for the targeted conversion of aromatic reactants.