Electrocatalytic C–C Coupled Oligomerization From Biomass Molecules Through Pd Single‐Atom Interfacial Regulation
Shaowei Yang, Ying Guo, Shixin Fa, Xilin Zeng, Xuefei Zhou, Zhanwei Chen, Haoxi Wang, Zhibei Liao, Hao Jiang, Peng Zhao, Shaojun Guo, Qiuyu Zhang, Hepeng ZhangABSTRACT
Fossil‐derived diesel raises sustainability and air‐quality concerns, motivating biomass‐based alternatives; however, current biodiesel routes suffer from food–fuel competition, poor fuel properties, and energy‐intensive upgrading. Electrocatalytic C─C coupling of biomass molecules followed by hydrodeoxygenation (HDO) offers a cleaner pathway, yet has been limited to dimer formation. Here, we successfully resolved this longstanding bottleneck through construction of Pd 1 Cu single‐atom alloy electrocatalyst, a trimer of 5‐hydroxymethylfurfural is obtained with 44.7% selectivity. The combined oligomer (dimer and trimer) selectivity reaches 95.0% with 93.2% Faradaic efficiency, production rate achieves a record high of ∼50 g g cat −1 h −1 . Subsequent HDO converts the oligomers into heteroatom‐free n‐dodecane and n‐octadecane diesel blendstocks. Operando spectroscopy reveals a surface‐confined ketyl‐radical pathway in which isolated Pd atoms regulate hydrogen‐atom supply and substrate adsorption, favoring C─C coupling over hydrogenation. This work establishes an electricity‐driven route for controlled carbon‐chain growth from biomass platforms.