Converting CO2 Into Natural Gas Within the Autoclave: A Kinetic Study on Hydrogenation of Carbonates in Aqueous Solution

Abstract

AbstractCatalytic conversion of carbon dioxide (CO2) into value‐added chemicals is of pivotal importance, well the cost of capturing CO2 from dilute atmosphere is super challenge. One promising strategy is combining the adsorption and transformation at one step, such as applying alkali solution that could selectively reduce carbonate (CO32−) as consequences of CO2 adsorption. Due to complexity of this system, the mechanistic details on controlling the hydrogenation have not been investigated in depth. Herein, Ru/TiO2 catalyst was applied as a probe to elucidate the mechanism of CO32− activation, in which with thermodynamic and kinetic investigations, a compact Langmuir‐Hinshelwood reaction model was established which suggests that the overall rate of CO32− hydrogenation was controlled by a specific C−O bond rupture elementary step within HCOO− and the Ru surface was mainly covered by CO32− or HCOO− at independent conditions. This assumption was further supported by negligible kinetic isotope effects (kH/kD≈1), similarity on reaction barriers of CO32− and HCOO− hydrogenation (ΔH≠hydr,Na2CO3 and ΔH≠hydr,HCOONa) and a non‐variation of entropy (ΔS≠hydr≈0). More interestingly, the alkalinity of the solution is certainly like a two sides in a sword and could facilitate the adsorption of CO2 while hold back catalysis during CO32− hydrogenation.