Highly Dispersed Metal Carbide on ZIF-Derived Pyridinic-N-Doped Carbon for CO2 Enrichment and Selective Hydrogenation

Abstract

Catalytic conversion of CO₂ into chemicals is a critical issue for energy and environmental research. Among such reactions, converting CO₂ into CO has been regarded as a significant foundation to generate a liquid fuels and chemicals on a large scale. In this work, zeolitic imidazolate framework-derived N-doped carbon-supported metal carbide catalysts (M/ZIF-8-C; M=Ni, Fe, Co and Cu) with highly dispersed metal carbide were prepared for selective CO₂ hydrogenation. Under the same metal loadings, catalytic activity for CO₂ hydrogenation to CO follows the order: Ni/ZIF-8-C≈Fe/ZIF-8-C>Co/ZIF-8-C>Cu/ZIF-8-C. These catalysts are composed of carbide or metal supported on pyridinic N sites within the N-doped carbon structure. ZIF-8-derived pyridinic nitrogen and carbide effect CO₂ adsorption, whereas dispersed Ni or Fe carbide and metal species serve as an active site for CO₂ hydrogenation. The supported Ni catalyst exhibits extraordinary catalytic performance, which results from high dispersion of the metal and exposure of the carbide. Based on high-sensitivity low-energy ion scattering (HS-LEIS) and line scan results, density functional theory (DFT) was used to understand reaction mechanism of selective CO₂ hydrogenation over Ni/ZIF-8-C. The product CO is derived mainly from the direct cleavage of C-O bonds in CO₂ * rather than decomposition of COOH*. The CO* desorption energy on Ni/ZIF-8-C is lower than that for further hydrogenation and dissociation. Comparison of Ni/ZIF-8-C with ZIF-8-C indicates that the combined effects of the highly dispersed metal or carbide and weak CO adsorption result in high CO selectivity for CO₂ hydrogenation.

Keywords: adsorption; carbon dioxide; density functional calculations; metal carbides; zeolitic imidazolate frameworks.