Lattice Strain Engineering on Metal‐Organic Frameworks by Ligand Doping to Boost the Electrocatalytic Biomass Valorization

Abstract As an efficient and environmental‐friendly strategy, electrocatalytic oxidation can realize biomass lignin valorization by cleaving its aryl ether bonds to produce value‐added chemicals. However, the complex and polymerized structure of lignin presents challenges in terms of reactant adsorption on the catalyst surface, which hinders further refinement. Herein, NiCo‐based metal‐organic frameworks (MOFs) are employed as the electrocatalyst to enhance the adsorption of reactant molecules through π‐π interaction. More importantly, lattice strain is introduced into the MOFs via curved ligand doping, which enables tuning of the d‐band center of metal active sites to align with the reaction intermediates, leading to stronger adsorption and higher electrocatalytic activity toward bond cleavage within lignin model compounds and native lignin. When 2′‐phenoxyacetophenone is utilized as the model compound, high yields of phenol (76.3%) and acetophenone (21.7%) are achieved, and the conversion rate of the reactants reaches 97%. Following pre‐oxidation of extracted poplar lignin, >10 kinds of phenolic compounds are received using the as‐designed MOFs electrocatalyst, providing ≈12.48% of the monomer, including guaiacol, vanillin, eugenol, etc., and p‐hydroxybenzoic acid dominates all the products. This work presents a promising and deliberately designed electrocatalyst for realizing lignin valorization, making significant strides for the sustainability of this biomass resource.