Solar-Driven Paired Electrolysis System: A Green Electrosynthesis Strategy for Valorizing Agroforestry Biomass...

Paired electrolysis represents a more environmentally sustainable and efficient approach for converting agroforestry biomass-derived 5-hydroxymethylfurfural (HMF) and furfural (FUR) into valuable fine chemicals and fuel additives. A critical challenge in developing paired electrolysis systems for furanal compounds is finding the optimal potential matching between the anode and the cathode. One solution is to reduce the potential sensitivity of the anode so that the paired electrolysis system can be regulated only by the cathode potential. In this study, we employed the homogeneous catalyst 4-acetamido-TEMPO (ACT) to facilitate oxidation reaction at the anode, enabling the potential sensitivity of the anode to be reduced. The results displayed the furanal substrates oxidation proceeds through a non-electrochemical chemical reaction with the active oxoammonium cation (ACT⁺), rather than being directly governed by the anode potential. The paired electrolysis system exhibited enhanced catalytic performance, with a total faradaic efficiency of 190.69% and 189.11% in the FUR and HMF paired electrolysis setup, respectively. Furthermore, this system demonstrated excellent stability, maintaining a total faradaic efficiency of over 167.64% after multiple successive cycles. Additionally, the solar-driven paired electrolysis system showed commendable substrate conversion capabilities, achieving a total faradaic efficiency of 187.89%, comparable to that of the electrically driven system. The mechanisms of the ACT electro-oxidation of furanal compounds and the construction of paired electrolysis systems for furanal compounds were proposed and discussed. This work aims to enhance electrical energy efficiency and underscore the potential of paired electrochemical catalysis for sustainable biomass conversion in the green economy.