Non-contact biomimetic mechanism for selective hydrogenation of nitroaromatics on heterogeneous metal nanocatalysts  

作　　者：Wenting Zhou Laiyang Li Ruixuan Qin Jiaxin Zhu Shengjie Liu Shiguang Mo Zaifa Shi Huihuang Fang Pengpeng Ruan Jun Cheng Gang Fu Nanfeng Zheng 

机构地区：[1]State Key Laboratory for Physical Chemistry of Solid Surfaces,Collaborative Innovation Center of Chemistry for Energy Materials,and Department of Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China [2]Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM),Xiamen 361005,China

出　　处：《Science China Chemistry》2022年第4期726-732,共7页中国科学（化学英文版）

基　　金：supported by the National Key Research and Development Program of China(2017YFA0207302);the National Nature Science Foundation of China(21890752,21731005,22072116,92045303);support from the Tencent Foundation through the XPLORER PRIZE;the XAFS Station(BL14W1)of the Shanghai Synchrotron Radiation Facility(SSRF)。

摘　　要：While the enzymatic reduction of unsaturated compounds usually has high specificity,highly selective reduction processes are hardly realized by heterogeneous industrial catalysts,which is critical for the green production of many fine chemicals.Here,we report an unexpected discovery of a biomimetic behavior of dicyandiamide(DICY)-modified Pt nanocatalysts for the green hydrogenation of a wide range of nitroaromatics.We demonstrate that the surface modification by DICY not only prevents the direct contact of nitroaromatic reactants with Pt surface but also induces an effective non-contact hydrogenation mechanism mediated by protons and electrons.In such a process,the DICY layer serves as a“semi-permeable membrane”to allow the permeation of H_(2) molecules for being activated into electrons and protons at the Pt-DICY interface.With the generation of separated protons and electrons,the nitro group with strong electrophilic properties can be hydrogenated through the electron transfer followed by the proton transfer,which is facilitated by the hydrogen bonding network formed by protonated DICY.The unique mechanism makes it highly directional toward the hydrogenation of nitro groups without side reactions.Owing to its capability to largely eliminate the waste generation,the developed Pt-DICY catalysts have been successfully applied for the green industrial production of many important aniline intermediates.

关 键 词：hydrogenation catalysis NITROAROMATICS proton/electron separation non-contact hydrogenation biomimetic mechanism 

分 类 号：TQ246.31[化学工程—有机化工] O643.36[理学—物理化学]