Design of Single-Atom and Frustrated-Lewis-Pair dual active sites for direct conversion of CH4 and CO2 to acetic acid.

[Display omitted] • A series of SA-FLP dual-active-site catalysts are designed for the conversion of CH 4 and CO 2 to acetic acid. • The SA-FLP dual active sites can concurrently adsorb and activate CH 4 and CO 2. • Ag 1 -FLP catalyst exhibits the best performance in the reaction of CH 4 and CO 2 to acetic acid. Direct conversion of CH 4 and CO 2 into acetic acid is an emerging attractive process but remains a significant challenge due to the inherent stability of both molecules. Hence, developing active and stable catalysts is crucial for the simultaneous activation of CO 2 and CH 4. Herein, we designed the "Single-Atom" - "Frustrated-Lewis-Pair" (SA-FLP) dual-active-site catalysts for the co-conversion of CH 4 and CO 2 to acetic acid based on density functional theory (DFT) calculations. The SA sites were introduced by doping the transition-metal (TM) atoms (TM = Fe, Co, Ni, Cu; Ru, Rh, Pd, Ag; Os, Ir, Pt, Au) into CeO 2 (1 1 0) surface, and the FLP sites were constructed by the regulation of surface oxygen vacancies. Our results demonstrate the introduction of SA into CeO 2 surface could facilitate the formation of oxygen vacancies, and thus promotes the formation of FLP sites. The SA-FLP dual active sites can concurrently activate CH 4 and CO 2 with CH 4 preferentially activated at SA sites and CO 2 preferentially activated at FLP sites. Among the twelve SA-FLP catalysts, Ag 1 -FLP catalyst exhibits the best performance in the reaction of CH 4 and CO 2 to acetic acid with a rate-determining barrier of 1.12 eV and a turnover frequency of 2.52 × 10–3 s−1 at 573 K and 2 bar. This work not only offers a novel catalyst prototype for the co-conversion of CH 4 and CO 2 to acetic acid but also provides insights into developing dual-active-site catalysts on earth-abundant metal oxide materials. [ABSTRACT FROM AUTHOR]