Pairing Electrocatalytic Reduction and Oxidation of Biomass-Derived 5-Hydroxymethylfurfural into Highly Value-Added Chemicals
Man Zhang, Zhikeng Zheng, Xiaodie Zhang, Zhiwei Jiang, Yong Xue, Ke Li, Xin Tu, Kai Yan
Abstract
High Resolution Image Download MS PowerPoint Slide Simultaneous electrocatalytic reduction and oxidation of 5-hydroxymethylfurfural (HMF) is crucial for biomass refineries. Herein, we report the unprecedentedly high efficiency of the nearly complete conversion of biomass-derived HMF to value-added products, achieving >95% selectivity at −0.4 V vs RHE by pairing electrocatalytic reduction and oxidation (PERO) reactions in a single electrochemical cell. At the cathode, we achieved 99% conversion of HMF to 2,5-dihydroxymethylfuran (DHMF) in ∼99% yield under mild conditions using a PtRu alloy. At the anode, we observed 99% conversion of HMF, nearly perfect selectivity for the oxidative product 2,5-furandicarboxylic acid (FDCA), and 100% Faradaic efficiency on a NiCo(OOH) x nanosheets electrode. The kinetic isotope effect demonstrated that the rate-controlled step was a proton-independent electron transfer process, with minimal impact from substrate concentration variations. After assembling the synchronous reaction cell, the PERO of HMF generated high yields of DHMF (94%) and FDCA (86%), achieving a combined electron efficiency of 131%, nearly doubling the performance of uncoupled cells. This superior performance was attributed to the efficient generation of H* on the PtRu alloy for reduction, alongside the OH* active sites on the NiCo(OOH) x nanosheets electrode for oxidation. This research provides a promising strategy for the sustainable electrocatalytic upgrading of biomass-derived chemicals.