Operando generated copper-based catalyst enabling efficient electrosynthesis of 2,5-bis(hydroxymethyl)furan.

Electrocatalytic upgrading of biomass-derived platform molecules has emerged as a sustainable and environmentally benign route to produce high-value chemicals. The main challenge lies in developing efficient catalysts for the selective activation of designated chemical bonds in the presence of various reducible groups. This work demonstrated a high-efficiency electrochemical conversion of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF), an important industrial synthetic reagent. A highly porous Cu-based catalyst was developed that achieved nearly 100% BHMF selectivity and long-term stability. Through comprehensive operando and ex-situ structural characterizations, an electrochemically generated catalyst with abundant Cu/Cu(2)O interfaces was identified as a catalytically active phase for HMF conversion. Deuterated BHMF, with the potential to produce deuterated drugs, was also synthesized using D(2)O as the deuterium source. Density functional theory calculations show that the Cu/Cu(2)O interface structure exhibits relatively low energy barriers for the hydrogenation of HMF to BHMF. This work provides insights into the origin of electrocatalytic hydrogenation activity and highlights the promising potential of the electrocatalytic synthesis of high-value chemicals.