Utilizing in situ construction of N-doped hierarchical porous carbon to achieve electronic control of highly dispersed Pd nanoparticles for efficient catalytic hydrogenation of CO2 to formic acid

Abstract

Hydrogenation of CO2 to produce formic acid/formate is a significant pathway for future energy storage and utilization. The development of heterogeneous catalysts with high activity and stability for this process is still a challenge. In this work, the in-situ N-doped hierarchical porous carbon derived from distiller's grains was used as a support for Pd-based catalysts (Pd/NC) to convert CO2 into valuable chemicals while making high-value use of waste biomass. The optimum catalyst, Pd/NC-800, shown exceptional catalytic performance, achieving a turnover frequency (TOF) of 2060h-1 at 100℃, 4MPa in the catalytic CO2 hydrogenation to formate reaction. Comprehensive experimental results and density functional theory calculations indicate that the electronic effect between the pyridine N in the support and the Pd nanoparticles (NPs) can make the Pd surface reach the state of electron enrichment and enhance the metal-support interaction. Moreover, the synthesized material has hierarchical pore structure, which provides abundant Pd anchor location sites and improves mass transfer efficiency. The results not only provide a feasible strategy for the preparation of efficient CO2 hydrogenation catalysts, but also break a new and effective avenue for the resource utilization of distiller's grains.