CO2 Reforming of Ethanol: Density Functional Theory Calculations, Microkinetic Modeling, and Experimental Studies

Ethanol dry reformation (EDR) is a chemical process for syngas production, which consumes a greenhouse gas and reduces carbon footprint. We present a mechanistic study of EDR over Rh catalyst based on density functional theory (DFT) calculations and microkinetic analysis. Our results show that both the initial decomposition of C2H5OH and the later C–O bond formation are crucial steps on the reaction free energy landscape. The microkinetic model suggests that the α-dehydrogenation of ethanol is the rate-determining step, and the calculated reaction rate (rH2) is 8.23 × 103 s–1. Moreover, factors behind catalyst deactivation were investigated and potential solutions were explored from both theoretical and experimental aspects. The results indicate that additional H2 could potentially mitigate catalyst deactivation by methanation of coke deposited on the catalyst. These computational and experimental efforts further the understanding of the complicated catalytic process and inspire the rational design of EDR catalysts.