Wei Haisheng, Gao Zhaohua, Cao Liru, Li Kairui, Yan Xiaorui, Liu Tiantian, Zhu Mingyuan, Huang Fei, Fang Xu, Lin Jian
Department College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, Shandong, China.
CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China.
Nanoscale. 2023 Jan 19;15(3):1422-1430. doi: 10.1039/d2nr05518j.
Chemoselective hydrogenation of quinoline and its derivatives under mild reaction conditions still remains a challenging topic, which requires a suitable interaction between reactants and a catalyst to achieve high performance and stability. Herein, FePO-supported Rh single atoms, subnano clusters and nanoparticle catalysts were synthesized and evaluated in the chemoselective hydrogenation of quinoline. The results show that the Rh subnano cluster catalyst with a size of ∼1 nm gives a specific reaction rate of 353 mol mol h and a selectivity of >99% for 1,2,3,4-tetrahydroquinoline under mild conditions of 50 °C and 5 bar H, presenting better performance compared with the Rh single atoms and nanoparticle counterparts. Moreover, the Rh subnano cluster catalyst exhibits good stability and substrate universality for the hydrogenation of various functionalized quinolines. A series of characterization studies demonstrate that the acidic properties of the FePO support favors the adsorption of quinoline while the Rh subnano clusters promote the dissociation of H molecules, and then contribute to the enhanced hydrogenation performance. This work provides an important implication to design efficient Rh-based catalysts for chemoselective hydrogenation under mild conditions.
在温和反应条件下喹啉及其衍生物的化学选择性氢化仍然是一个具有挑战性的课题，这需要反应物与催化剂之间有合适的相互作用以实现高性能和稳定性。在此，合成了负载在FePO上的Rh单原子、亚纳米团簇和纳米颗粒催化剂，并对其在喹啉的化学选择性氢化反应中的性能进行了评估。结果表明，尺寸约为1 nm的Rh亚纳米团簇催化剂在50 °C和5 bar H2的温和条件下，对1,2,3,4-四氢喹啉的比反应速率为353 mol mol-1 h-1，选择性大于99%，与Rh单原子和纳米颗粒催化剂相比表现出更好的性能。此外，Rh亚纳米团簇催化剂对各种功能化喹啉的氢化反应表现出良好的稳定性和底物通用性。一系列表征研究表明，FePO载体的酸性有利于喹啉的吸附，而Rh亚纳米团簇促进H2分子的解离，进而有助于提高氢化性能。这项工作为设计在温和条件下用于化学选择性氢化的高效Rh基催化剂提供了重要启示。
