Sun Yafei, Cao Yueqiang, Wang Lili, Mu Xiaotong, Zhao Qingfei, Si Rui, Zhu Xiaojuan, Chen Shangjun, Zhang Bingsen, Chen De, Wan Ying
Key Laboratory of Resource Chemistry of Ministry of Education, Shanghai Key Laboratory of Rare Earth Functional Materials, and Department of Chemistry, Shanghai Normal University, 200234, Shanghai, China.
State Key Laboratory of Chemical Engineering, East China University of Science and Technology, 200237, Shanghai, China.
Nat Commun. 2020 Sep 14;11(1):4600. doi: 10.1038/s41467-020-18322-x.
Supported gold nanoparticles are emerging catalysts for heterogeneous catalytic reactions, including selective hydrogenation. The traditionally used supports such as silica do not favor the heterolytic dissociation of hydrogen on the surface of gold, thus limiting its hydrogenation activity. Here we use gold catalyst particles partially embedded in the pore walls of mesoporous carbon with carbon atoms occupying interstitial sites in the gold lattice. This catalyst allows improved electron transfer from carbon to gold and, when used for the chemoselective hydrogenation of 3-nitrostyrene, gives a three times higher turn-over frequency (TOF) than that for the well-established Au/TiO system. The d electron gain of Au is linearly related to the activation entropy and TOF. The catalyst is stable, and can be recycled ten times with negligible loss of both reaction rate and overall conversion. This strategy paves the way for optimizing noble metal catalysts to give an enhanced hydrogenation catalytic performance.
负载型金纳米颗粒正成为用于多相催化反应（包括选择性氢化反应）的新兴催化剂。传统使用的载体（如二氧化硅）不利于氢气在金表面发生异裂解离，从而限制了其氢化活性。在此，我们使用部分嵌入介孔碳孔壁的金催化剂颗粒，其中碳原子占据金晶格中的间隙位置。这种催化剂能改善从碳到金的电子转移，并且当用于3-硝基苯乙烯的化学选择性氢化反应时，其周转频率（TOF）比成熟的Au/TiO体系高三倍。金的d电子增益与活化熵和TOF呈线性关系。该催化剂稳定，可循环使用十次，反应速率和总转化率的损失可忽略不计。这一策略为优化贵金属催化剂以提高氢化催化性能铺平了道路。
