Product Dynamic Modification Triggering the In Situ Generation of Metastable γ‐NiOOH for Enhanced 2, 5‐Furandicarboxylic Acid Production

ABSTRACT The rational construction of high‐performance electrocatalysts is crucial for environmentally friendly and sustainable electrocatalytic biomass upgrading and hydrogen evolution. Herein, we construct an electrocatalyst of 1, 4‐benzenedicarboxylate (BDC)‐modified Ni(OH) 2 /NiOOH ultrathin nanosheets (Ni(OH) 2 /NiOOH‐BDC) with plentiful oxygen vacancies (O Vs ) derived from Ni‐BDC and observe the in situ dynamic modification of the 2, 5‐furandicarboxylate (FDC) during the electrochemical 5‐hydroxymethylfurfural oxidation reaction (HMFOR). The FDC dynamic modification for Ni(OH) 2 /NiOOH‐BDC significantly boosts the HMFOR performance, achieving almost 100% HMF conversion, with FDCA yield and Faradaic efficiency of 96.36% and 96.18%, respectively. By constructing a membrane electrode assembly (MEA), a FDCA yield of over 93.9% is maintained during 30 consecutive cycles (96.25 h) at 600 mA cm −2 , with a productivity of 73.28 mg cm −2 h −1 and a net income of US$748.69/tonne of FDCA for economic benefits. Experimental and theoretical studies reveal that the unique configuration endows the Ni(OH) 2 /NiOOH‐BDC with fully exposed and easily accessible active sites and high transfer efficiency of electrons and reactants. The BDC/FDC modification tunes the electronic states of Ni species and promotes the in situ formation of highly active γ ‐NiOOH species, while the O Vs facilitate the adsorption/activation of reactants/intermediates, thus boosting the intrinsic activity, lowering the reaction energy barrier, and accelerating the reaction kinetics.