Lin Lili, Yao Siyu, Gao Rui, Liang Xuan, Yu Qiaolin, Deng Yuchen, Liu Jinjia, Peng Mi, Jiang Zheng, Li Siwei, Li Yong-Wang, Wen Xiao-Dong, Zhou Wu, Ma Ding
Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, College of Engineering and BIC-ESAT, Peking University, Beijing, China.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, China.
Nat Nanotechnol. 2019 Apr;14(4):354-361. doi: 10.1038/s41565-019-0366-5. Epub 2019 Feb 25.
The hydrogenation activity of noble metal, especially platinum (Pt), catalysts can be easily inhibited by the presence of a trace amount of carbon monoxide (CO) in the reaction feeds. Developing CO-resistant hydrogenation catalysts with both high activity and selectivity is of great economic interest for industry as it allows the use of cheap crude hydrogen and avoids costly product separation. Here we show that atomically dispersed Pt over α-molybdenum carbide (α-MoC) constitutes a highly CO-resistant catalyst for the chemoselective hydrogenation of nitrobenzene derivatives. The Pt/α-MoC catalyst shows promising activity in the presence of 5,000 ppm CO, and has a strong chemospecificity towards the hydrogenation of nitro groups. With the assistance of water, high hydrogenation activity can also be achieved using CO and water as a hydrogen source, without sacrificing selectivity and stability. The weakened CO binding over the electron-deficient Pt single atom and a new reaction pathway for nitro group hydrogenation confer high CO resistivity and chemoselectivity on the catalyst.
反应进料中痕量一氧化碳（CO）的存在会轻易抑制贵金属催化剂尤其是铂（Pt）催化剂的氢化活性。开发兼具高活性和选择性的抗CO氢化催化剂对工业具有重大经济意义，因为这允许使用廉价的粗氢气并避免昂贵的产物分离。在此我们表明，原子级分散在α-碳化钼（α-MoC）上的Pt构成了用于硝基苯衍生物化学选择性氢化的高抗CO催化剂。Pt/α-MoC催化剂在存在5000 ppm CO的情况下表现出有前景的活性，并且对硝基氢化具有很强的化学特异性。在水的辅助下，使用CO和水作为氢源也可以实现高氢化活性，而不会牺牲选择性和稳定性。缺电子的Pt单原子上减弱的CO键合以及硝基氢化的新反应途径赋予了催化剂高抗CO性和化学选择性。
