Huang Xin, Song Jinliang, Hua Manli, Chen Bingfeng, Xie Zhenbing, Liu Huizhen, Zhang Zhanrong, Meng Qinglei, Han Buxing
Beijing National Laboratory for Molecular Science, CAS Key Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences Beijing 100190 China
School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences Beijing 100049 China.
Chem Sci. 2021 Apr 1;12(18):6342-6349. doi: 10.1039/d1sc01231b.
Selective oxidation of biomass-derived furan compounds to maleic acid (MA), an important bulk chemical, is a very attractive strategy for biomass transformation. However, achieving a high MA selectivity remains a great challenge. Herein, we for the first time successfully designed and fabricated Se-doped graphitic carbon nitride nanotubes with a chemical formula of CN-Se. The prepared CN-Se was highly efficient for electrocatalytic oxidation of various biomass-derived furan compounds to generate MA. At ambient conditions, the MA yield could reach 84.2% from the electro-oxidation of furfural. Notably, the substituents on the furan ring significantly affected the selectivity to MA, following the order: carboxyl group > aldehyde group > hydroxyl group. Detailed investigation revealed that Se doping could tune the chemical structure of the materials (, CN-Se and g-CN), thus resulting in the change in catalytic mechanism. The excellent performance of CN-Se originated from the suitable amount of graphitic N and its better electrochemical properties, which significantly boosted the oxidation pathway to MA. This work provides a robust and selective metal-free electrocatalyst for the sustainable synthesis of MA from oxidation of biomass-derived furan compounds.
将生物质衍生的呋喃化合物选择性氧化为马来酸（MA），一种重要的大宗化学品，是生物质转化中极具吸引力的策略。然而，实现高MA选择性仍然是一个巨大挑战。在此，我们首次成功设计并制备了化学式为CN-Se的硒掺杂石墨相氮化碳纳米管。制备的CN-Se对各种生物质衍生的呋喃化合物电催化氧化生成MA具有高效性。在环境条件下，糠醛电氧化的MA产率可达84.2%。值得注意的是，呋喃环上的取代基对MA的选择性有显著影响，顺序为：羧基＞醛基＞羟基。详细研究表明，硒掺杂可调节材料（即CN-Se和g-CN）的化学结构，从而导致催化机理发生变化。CN-Se的优异性能源于适量的石墨态氮及其更好的电化学性质，这显著促进了生成MA的氧化途径。这项工作为从生物质衍生的呋喃化合物氧化可持续合成MA提供了一种稳健且选择性的无金属电催化剂。
