Carbon-Phosphorus-Nitrogen Materials as Highly Thermally Stable Catalyst Supports for CO₂ Hydrogenation to Methanol

Abstract

The direct conversion of CO2 into methanol through hydrogenation reactions by heterogeneous catalysts is considered a promising green approach for fuel production. The most researched catalyst for methanol formation is Cu, usually in combination with other metals dispersed on different substrates. However, several challenges, such as the low stability, activity, and selectivity of the catalyst, hinder further progress. Here, we present catalysts consisting of Cu and Fe nanoparticles deposited on lightweight carbon-phosphorous-nitrogen (CPN) materials as the support for CO2 hydrogenation to methanol. Detailed analysis reveals a correlation between the elemental composition of the CPN supports and their CO2 adsorption capability, which benefits CO2 conversion to methanol. The unique elemental composition ensures uniform dispersion of both Cu and Fe nanoparticles on CPN and prevents the oxidation of the Cu active sites during the reaction. The best performing sample of the catalysts exhibits a remarkable methanol production yield of 9.82 mol kgcat –1 h–1 at 250 °C under 20 bar, with good methanol selectivity, negligible CO formation, and good stability for 12 h under harsh conditions.

Direct coupling of two inert CO2 molecules to form a C–C bond on the Cu0 atomic interfaces of the nitrogen-doped graphene-supported Cu4 cluster

“…Nitrogen-doped carbon materials have attracted considerable attention in the field of CO 2 RR because of their adjustable pore structure, high specific surface area, and good electrochemical stability. [32][33][34][35][36][37] Especially in the study of M-N-C catalysts based on metal elements such as Cu, Ni, Fe, and Co, etc., it has been demonstrated that these catalysts have high activity and selectivity for the reduction of CO 2 to CO. [38][39][40][41][42] Among the various reported metals, the carbon-loaded Cu-based catalyst shows high activity in CO 2 RR. [43][44][45][46] These reported catalysts are of particular interest because of their ability to generate large amounts of hydrocarbons, including HCOOH, CH 4 , C 2 H 4 , etc.…”