Zinc modification of Ni-Ti as efficient Ni_xZn_yTi₁ catalysts with both geometric and electronic improvements for hydrogenation of nitroaromatics

Abstract

The catalytic hydrogenation of nitroaromatics is an environmentally friendly technology for aniline production, and it is crucial to develop noble-metal-free catalysts that can achieve chemoselective hydrogenation of nitroaromatics under mild reaction conditions. In this work, zinc-modified Ni-Ti catalysts (Ni_xZn_yTi₁) were fabricated and applied for the hydrogenation of nitroaromatics hydrogenation. It was found that the introduction of zinc effectively increases the surface Ni density, enhances the electronic effect, and improves the interaction between Ni and TiO₂, resulting in smaller Ni particle size, more oxygen vacancies, higher dispersion and greater concentration of Ni on the catalyst surface. Furthermore, the electron-rich Ni^δ– obtained by electron transfer from Zn and Ti to Ni effectively adsorbs and dissociates hydrogen. The results reveal that Ni_xZn_yTi₁ (Ni_0.5Zn_0.5Ti₁) shows excellent catalytic performance under mild conditions (70 °C and 6 bar). These findings provide a rational strategy for the development of highly active non-noble-metal hydrogenation catalysts.

Key words： bimetal strategy; oxygen vacancy; non-noble metal catalyst; hydrogenation; aromatic nitro compounds

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant Nos. 22078277 and 21908185), Project of Hunan Provincial Education Department (Grant Nos. 19B572 and 20B547), the Collaborative Innovation Center of New Chemical Technologies for Environmental Benignity and Efficient Resource Utilization, and the National Department of Education Engineering Research Centre for Chemical Process Simulation and Optimization.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-021-2072-8 and is accessible for authorized users.

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