Aerobic oxidation of bio-sourced 2,5-bis(hydroxymethyl)furan (BHMF) to 2, 5-furandicarboxylic acid (FDCA), a renewable and green alternative to petroleum-derived terephthalic acid (TPA), is of great significance in green chemicals production. Herein, hierarchical porous bowl-like nitrogen-rich (nitrated) carbon-supported bimetallic Au-Pd nanocatalysts (AumPdn/ N-BNxC) with different nitrogen content and bimetal nanoparticle sizes were developed and employed for the highly efficient aerobic oxidation of BHMF to FDCA in sodium carbonate aqueous solution. The reaction pathway for catalytic oxidation of BHMF went through the steps of BHMF→HMF→HMFCA→FFCA→FDCA. Kinetics studies showed that the activation energies of BHMF, HMF, HMFCA, and FFCA were 58.1 kJ·moL−1, 39.1 kJ·moL−1, 129.2 kJ·moL−1, and 56.3 kJ·moL−1, respectively, indicating that the oxidation of intermediate HMFCA to FFCA was the rate-determining step. ESR tests proved that the active species was a superoxide radical. Owing to the synergy between the nitrogen-rich carbon support and bimetallic Au-Pd nanoparticles, the Au1Pd1/N-BN2C nanocatalysts exhibited BHMF conversion of 100% and FDCA yield of 95.8% under optimal reaction conditions. Furthermore, the nanocatalysts showed good stability and reusability. This work provides a versatile strategy for the design of heterogeneous catalysts for the highly efficient production of FDCA from BHMF.

中文翻译：

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硝化碳材料负载Au-Pd双金属催化剂从2,5-双(羟甲基)呋喃选择性生产2,5-呋喃二甲酸的机理研究

生物源2,5-双(羟甲基)呋喃(BHMF)有氧氧化为2,5-呋喃二甲酸(FDCA)，是石油衍生对苯二甲酸(TPA)的可再生绿色替代品，在绿色环保领域具有重要意义化学品生产。在此，开发了具有不同氮含量和双金属纳米颗粒尺寸的分级多孔碗状富氮（硝化）碳负载双金属Au-Pd纳米催化剂（AumPdn/N-BNxC），并将其用于BHMF高效有氧氧化为FDCA于碳酸钠水溶液中。 BHMF催化氧化的反应路径为BHMF→HMF→HMFCA→FFCA→FDCA。动力学研究表明，BHMF、HMF、HMFCA和FFCA的活化能分别为58.1 kJ·moL−1、39.1 kJ·moL−1、129.2 kJ·moL−1和56.3 kJ·moL−1，这表明中间体 HMFCA 氧化成 FFCA 是速率决定步骤。 ESR测试证明活性物质是超氧自由基。由于富氮碳载体和双金属Au-Pd纳米颗粒之间的协同作用，Au1Pd1/N-BN2C纳米催化剂在最佳反应条件下表现出100%的BHMF转化率和95.8%的FDCA产率。此外，纳米催化剂表现出良好的稳定性和可重复使用性。这项工作为多相催化剂的设计提供了一种通用策略，用于从 BHMF 高效生产 FDCA。