Pei An, Wang Peng, Zhang Shiyi, Zhang Qinghua, Jiang Xiaoyi, Chen Zhaoxi, Zhou Weiwei, Qin Qizhen, Liu Renfeng, Du Ruian, Li Zhengjian, Qiu Yongcai, Yan Keyou, Gu Lin, Ye Jinyu, Waterhouse Geoffrey I N, Huang Wei-Hsiang, Chen Chi-Liang, Zhao Yun, Chen Guangxu
School of Environment and Energy, State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, South China University of Technology, Guangzhou, China.
Institute of Physics, Chinese Academy of Sciences, Beijing, China.
Nat Commun. 2024 Jul 13;15(1):5899. doi: 10.1038/s41467-024-50325-w.
Challenges in direct catalytic oxidation of biomass-derived aldehyde and alcohol into acid with high activity and selectivity hinder the widespread biomass application. Herein, we demonstrate that a Pd/Ni(OH) catalyst with abundant Ni-O-Pd interfaces allows electrooxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid with a selectivity near 100 % and 2, 5-furandicarboxylic acid yield of 97.3% at 0.6 volts (versus a reversible hydrogen electrode) in 1 M KOH electrolyte under ambient conditions. The rate-determining step of the intermediate oxidation of 5-hydroxymethyl-2-furancarboxylic acid is promoted by the increased OH species and low C-H activation energy barrier at Ni-O-Pd interfaces. Further, the Ni-O-Pd interfaces prevent the agglomeration of Pd nanoparticles during the reaction, greatly improving the stability of the catalyst. In this work, Pd/Ni(OH) catalyst can achieve 100% 5-hydroxymethylfurfural conversion and >90% 2, 5-furandicarboxylic acid selectivity in a flow-cell and work stably over 200 h under a fixed cell voltage of 0.85 V.
将生物质衍生的醛和醇直接催化氧化为具有高活性和选择性的酸的挑战阻碍了生物质的广泛应用。在此，我们证明了一种具有丰富Ni - O - Pd界面的Pd/Ni(OH)催化剂能够在环境条件下，于1 M KOH电解液中，在0.6伏（相对于可逆氢电极）的电位下将5 - 羟甲基糠醛电氧化为2,5 - 呋喃二甲酸，选择性接近100%，2,5 - 呋喃二甲酸产率为97.3%。Ni - O - Pd界面处增加的OH物种和较低的C - H活化能垒促进了5 - 羟甲基 - 2 - 呋喃甲酸中间氧化的速率决定步骤。此外，Ni - O - Pd界面在反应过程中防止了Pd纳米颗粒的团聚，极大地提高了催化剂的稳定性。在这项工作中，Pd/Ni(OH)催化剂在流动池中可实现5 - 羟甲基糠醛100%的转化率和>90%的2,5 - 呋喃二甲酸选择性，并在0.85 V的固定电池电压下稳定工作超过200小时。
