Balancing elementary steps enables coke-free dry reforming of methane.

Yu, Jiaqi; Le, Tien; Jing, Dapeng; Stavitski, Eli; Hunter, Nicholas; Lalit, Kanika; Leshchev, Denis; Resasco, Daniel E et al. · Nat Commun · 2023

basic_science · Level V

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Abstract

Balancing kinetics, a crucial priority in catalysis, is frequently achieved by sacrificing activity of elementary steps to suppress side reactions and enhance catalyst stability. Dry reforming of methane (DRM), a process operated at high temperature, usually involves fast C-H activation but sluggish carbon removal, resulting in coke deposition and catalyst deactivation. Studies focused solely on catalyst innovation are insufficient in addressing coke formation efficiently. Herein, we develop coke-free catalysts that balance kinetics of elementary steps for overall thermodynamics optimization. Beginning from a highly active cobalt aluminum oxide (CoAl<sub>2</sub>O<sub>4</sub>) catalyst that is susceptible to severe coke formation, we substitute aluminum (Al) with gallium (Ga), reporting a CoAl<sub>0.5</sub>Ga<sub>1.5</sub>O<sub>4</sub>-R catalyst that performs DRM stably over 1000 hours without observable coke deposition. We find that Ga enhances DRM stability by suppressing C-H activation to balance carbon removal. A series of coke-free DRM catalysts are developed herein by partially substituting Al from CoAl<sub>2</sub>O<sub>4</sub> with other metals.