Elucidating the factors controlling the methanol synthesis from CO2 on ZnPd-ZnO/TiO2 catalysts prepared by direct/inverse impregnation

Quilis, Carlos; Mota, Noelia; Pawelec, Barbara; Reddy, Prabhakar; Rodriguez, José A.; Navarro Yerga, Rufino M.

doi:10.1016/j.apcatb.2025.125957

Elucidating the factors controlling the methanol synthesis from CO₂ on ZnPd-ZnO/TiO₂ catalysts prepared by direct/inverse impregnation

Journal Article · Fri Sep 12 00:00:00 EDT 2025 · Applied Catalysis B: Environment and Energy

DOI:https://doi.org/10.1016/j.apcatb.2025.125957· OSTI ID:2589805

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Consejo Superior de Investigaciones Cientificas (CSIC), Madrid (Spain). Instituto de Catálisis y Petroleoquímica (CSIC-ICP); Autonomous Univ. of Madrid (Spain)
Consejo Superior de Investigaciones Cientificas (CSIC), Madrid (Spain). Instituto de Catálisis y Petroleoquímica (CSIC-ICP)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

The direct hydrogenation of CO₂ to methanol over supported ZnPd intermetallic catalysts remains a challenge due to the complex nature of the active sites, which are highly dependent on both the dispersion of ZnPd intermetallics and their proximity to ZnO. This study investigates the effect of the Pd and Zn incorporation order on methanol synthesis over TiO₂-supported ZnPd catalysts. Catalysts were prepared via direct (Pd/Zn), inverse (Zn/Pd), and co-impregnation (Pd+Zn) methods using anatase TiO₂ as the support. Comprehensive characterization by XRD, HRTEM, CO-DRIFTS and XPS revealed that the formation of small and crystalline intermetallic β-ZnPd particles and their interaction with ZnO/ZnO_x depends on the sequence of Pd and Zn incorporation. It was found that, under the reaction conditions, the ZnO_x species plays a critical role in facilitating the formation of the intermetallic ZnPd through the interactions between Pd and ZnO_x. In addition, ZnO_x species have also been shown to modulate key catalytic properties, such as CO₂ activation and methanol selectivity. Specifically, the ZnPd/Pd surface ratio, determined by Pd dispersion and proximity to ZnO/ZnO_x, was shown to determine the methanol production from CO₂ directly or via a CO intermediate. The Pd/Zn catalyst showed superior selectivity due to the in-situ formation of intermetallic species facilitated by Pd-ZnO_x interactions.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0012704

OSTI ID:: 2589805

Report Number(s):: BNL--228996-2025-JAAM

Journal Information:: Applied Catalysis B: Environment and Energy, Journal Name: Applied Catalysis B: Environment and Energy Vol. 382; ISSN 0926-3373

Publisher:: Elsevier BVCopyright Statement

Country of Publication:: United States

Language:: English

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Elucidating the factors controlling the methanol synthesis from CO2 on ZnPd-ZnO/TiO2 catalysts prepared by direct/inverse impregnation

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Elucidating the factors controlling the methanol synthesis from CO₂ on ZnPd-ZnO/TiO₂ catalysts prepared by direct/inverse impregnation