Furfural, a valuable biomass platform precursor, is subject to multiple challenges in its application to the electrocatalytic hydrogenation (ECH) process due to the strong acidic/basic reaction conditions. A more fundamental challenge resides in the complex surface chemical environment of traditional catalyst systems, which hinders the accurate identification of active sites and consequently leaves a clear theoretical framework lacking for designing catalysts under neutral conditions. Consequently, the development of efficient electrocatalysts for neutral environments is of critical importance. While Ag-Cu bimetallic systems are known to enhance the adsorption of key intermediates in furfural ECH via electronic effects, the atomic-scale origin of this synergy remains unclear. To establish precise structure–property relationships, we employ atomically precise nanoclusters as model catalysts, which offer well-defined chemical environments, ultrasmall size, and recognizable active sites. In this study, the [Ag17Cu12(SSR)12(PPh3)4]3- (SSR=1,3-benzenedithiol) was successfully anchored onto copper foam, achieving high selectivity (71.6%) and faradaic efficiency (67.4%) for furfural conversion under neutral conditions. The conversion and turnover frequency (TOF) reached 100% and 3752.4 h-1, respectively, and represents a state-of-the-art Ag-Cu based catalyst for neutral conditions. The η2(C, O) adsorption mode of furfural at the Cu active site was a significant contributor to its remarkable catalytic activity. This work provides a promising direction for future research in the design of efficient catalysts in neutral conditions.
