Li Shangjing, Fan Yafei, Wu Chunhua, Zhuang Changfu, Wang Ying, Li Xuemei, Zhao Jie, Zheng Zhifeng
Key Laboratory of Forest Resources Conservation and Utilization in the Southwest Mountains of China Ministry of Education, School of Chemical Engineering, Southwest Forestry University, Kunming 650224, P. R. China.
Key Laboratory of Bionic Engineering, Ministry of Education, Jilin University, Changchun 130022, P. R. China.
ACS Appl Mater Interfaces. 2021 Feb 24;13(7):8507-8517. doi: 10.1021/acsami.1c01436. Epub 2021 Feb 11.
A multimetal doping strategy has aroused extensive attention in promoting a non-noble catalyst for selective hydrogenation reaction. Herein, a multimetallic catalyst (NiCoZn@CN) with excellent catalytic performance for hydrogenation of furfural (FAL) to furfuryl alcohol (FOL) is prepared through a facile, inexpensive, and efficient pyrolysis method. Using H as a H donor, extremely high selectivity (>99%) with 100% conversion is attained over the optimal NiCoZn@CN-600 catalyst. The subtle synergy between Co and Ni, Zn dopants, which remarkably promotes the performance of the Co-based catalyst, is revealed. In the NiCoZn@CN system, Co is proven to be the main active site, whose content is greatly improved by Ni and Co dopants. Additionally, the Ni dopant could also benefit activation of H and the Zn dopant could enhance metal nanoparticle dispersion and the porous structure of the catalyst. In situ FTIR indicates that the vertical adsorption mode of FAL with the O terminal on NiCoZn@CN-600 ensures a selective hydrogenation process. With a N-doped carbon matrix, NiCoZn@CN-600 shows good cycling stability in five times run. NiCoZn@CN-600 is also competent in the catalytic transfer hydrogenation (CTH) of FOL, affording >99% yield with 2-propanol as a H donor. This study opens an avenue toward rational design of multimetallic doping catalysts with high selectivity for challenging reactions in the conversion of biomass-derived compounds.
一种多金属掺杂策略在促进用于选择性氢化反应的非贵金属催化剂方面引起了广泛关注。在此，通过一种简便、廉价且高效的热解方法制备了一种对糠醛（FAL）加氢制糠醇（FOL）具有优异催化性能的多金属催化剂（NiCoZn@CN）。以H作为氢供体，在最佳的NiCoZn@CN - 600催化剂上实现了100%转化率下极高的选择性（>99%）。揭示了Co与Ni、Zn掺杂剂之间微妙的协同作用，这显著提升了钴基催化剂的性能。在NiCoZn@CN体系中，Co被证明是主要活性位点，其含量通过Ni和Zn掺杂剂得到大幅提高。此外，Ni掺杂剂还有利于H的活化，Zn掺杂剂可增强金属纳米颗粒的分散性以及催化剂的多孔结构。原位FTIR表明，FAL在NiCoZn@CN - 600上以O端垂直吸附模式确保了选择性加氢过程。具有N掺杂碳基体的NiCoZn@CN - 600在五次循环运行中表现出良好的循环稳定性。NiCoZn@CN - 600在以异丙醇作为氢供体的FOL催化转移加氢（CTH）反应中也表现出色，产率>99%。这项研究为合理设计对生物质衍生化合物转化中具有挑战性反应具有高选择性的多金属掺杂催化剂开辟了一条途径。
