中国科学院大连化学物理研究所徐杰团队报道了氢键结合激活氮掺杂表面O-H键用于生物质羟基化合物的催化氧化。相关研究成果发表在2021年6月14日出版的《德国应用化学》。

分子在特定固体表面的氢键结合是一种很有吸引力的相互作用，可以作为化学键活化、材料定向组装、蛋白质保护等方面的驱动力，但由于缺乏表面氢键的定量表征方法，限制了其应用。

该文中，研究人员用核磁共振技术测定了HBs表面的标准吉布斯自由能变化(ΔG0）。采用通过富电子掺杂氮含量的调整的一系列Co-N-C-n催化剂上的模型生物质平台5-羟甲基糠醛对ΔG0值进行比较，研究了表面对HBs的接受能力。减少ΔG0值有效提高了氮掺杂表面对HBs的接受能力，同时促进OH键的在5-羟甲基糠醛氧化过程中选择性活化。

结果，反应动力学加快，速率常数显著增加。除了优异的催化性能外，氧化反应的转换频率（TOF）值也比报道的非贵金属催化剂要高。

附：英文原文

Title: Hydrogen Binding Initiated Activation of O−H Bonds on a Nitrogen-Doped Surface for Catalytic Oxidation of Biomass Hydroxyl Compounds

Author: Xin Liu, Yang Luo, Hong Ma, Shujing Zhang, Penghua Che, Meiyun Zhang, Jin Gao, Jie Xu

Issue&Volume: 2021-06-14

Abstract: Hydrogen binding of molecules on specific solid surface is an attractive interaction that can be employed as driving force for chemical bond activation, material directed assembly, protein protection, etc. However, the lack of quantitative characterization method for hydrogen bonds (HBs) on surface seriously limits its application. Herein, we measured the standard Gibbs free energy change (ΔG  0  ) of surface HBs using NMR technique. HBs accepting ability of surface was investigated in term of comparing ΔG  0  values by employing model biomass platform 5-hydroxymethylfurfural on a series of Co-N-C-n catalysts with electron-rich doped-nitrogen contents adjusted. Reducing the ΔG  0  effectively improves HBs accepting ability of the nitrogen-doped surface, and promotes the OH bonds selectively initiated activation in the oxidation of 5-hydroxymethylfurfural. As a result, the reaction kinetics is accelerated and the rate constant is significantly increased. In addition to excellent catalytic performance, the turnover frequency (TOF) value for this oxidation is extremely higher than the reported non-noble metal catalysts.

DOI: 10.1002/anie.202103604

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202103604