Selective Hydrogenation of Furfural over the Co-Based Catalyst: A Subtle Synergy with Ni and Zn Dopants

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 H₂ 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, Co⁰ 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 H₂ 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_aldehyde 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.