Rapid synthesis of carbon quantum dot-integrated metal–organic framework nanosheets via electron beam irradiation for selective 5-hydroxymethylfurfural electrooxidation
Qianjia Ni, Mingwan Zhang, Bijun Tang, Weidong Hou, Kang Wang, Huazhang Guo, Jiye Zhang, Tao Han, Minghong Wu, Liang Wang
Abstract
Balancing the adsorption of OH⁻ and 5-hydroxymethylfurfural (HMF) is crucial in optimizing the competing HMF oxidation reaction and oxygen evolution reaction, especially given the polymerization tendency of HMF in alkaline solutions. Herein, we present an innovative approach for rapidly synthesizing a NiFe bimetallic metal-organic framework (MOF) induced by electron-withdrawing carbon quantum dot (EW-CQD) via electron beam irradiation within 2 min. EW-CQD serve as structural regulators, expanding the NiFe-MOF interlayer spacing, increasing reactive site availability, and more effectively balancing the adsorption of OH − and HMF, thereby significantly boosting the oxidation activity of HMF. The resulting EW-CQD-MOF exhibits a low potential of 1.36 V vs. RHE at 10 mA cm⁻ 2 and maintains excellent durability over 120 h. Comprehensive in situ characterization elucidates the HMF oxidation reaction pathway, showing high selectivity towards 2,5-furandicarboxylic acid (FDCA) under ambient conditions, with an impressive HMF conversion rate of 94% and FDCA selectivity of 96% within 6 h. These findings underscore the critical role of structural optimization and adsorption balance in catalytic performance enhancement and offer valuable insights for designing high-efficiency catalysts, advancing sustainable catalytic processes. The ultra-thin NiFe-MOF nanosheets induced by carbon quantum dots have been rapidly prepared by electron beam irradiation. EW-CQD-MOF has high catalytic oxidation activity and excellent stability of 5-hydroxymethylfurfural, which can effectively balance the adsorption of HMF and OH − and highly selective oxidation of 5-hydroxymethylfurfural to 2,5-furan dicarboxylic acid. • NiFe-MOF induced by electron-withdrawing CQDs are rapidly developed via electron beam irradiation within 2 min. • Electron-withdrawing CQDs not only expand the interlayer spacing of NiFe-MOF but also more effectively balance the adsorption of OH - and HMF. • Electron-withdrawing CQDs are more favorable for the formation of MOF nanosheets, and the reaction path of the HMFOR process was revealed.