Neutral conditions-enabled robust electrocatalytic hydrogenation of biomass-derived furfural using atomically precise nanocluster-based catalysts

Abstract

Furfural, a valuable biomass platform precursor, is subject to multiple challenges in its application to the electrocatalytic hydrogenation (ECH) process due to the strongly 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 lacks a clear theoretical framework 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, [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 the prepared material Ag₁₇Cu₁₂/CuF 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 under neutral conditions.