CO2 Methanation on Cu-Cluster Decorated Zirconia Supports with Different Morphology: A Combined Experimental In Situ GIXANES/GISAXS, Ex Situ XPS and Theoretical DFT Study

Halder, Avik; Lenardi, Cristina; Timoshenko, Janis; Mravak, Antonija; Yang, Bing; Kolipaka, Lakshmi K.; Piazzoni, Claudio; Seifert, Sönke; Bonačić-Koutecký, Vlasta; Frenkel, Anatoly I.; Milani, Paolo; Vajda, Stefan

doi:10.1021/acscatal.0c05029

Title: CO₂ Methanation on Cu-Cluster Decorated Zirconia Supports with Different Morphology: A Combined Experimental In Situ GIXANES/GISAXS, Ex Situ XPS and Theoretical DFT Study

Journal Article · Fri May 07 00:00:00 EDT 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c05029· OSTI ID:1864350

Halder, Avik ^[1];

^[2]; Timoshenko, Janis ^[3];

^[4];

^[1];

^[1]; Piazzoni, Claudio ^[2]; Seifert, Sönke ^[1]; Bonačić-Koutecký, Vlasta ^[5];

^[6]; Milani, Paolo ^[2];

^[7]

Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. degli Studi di Milano (Italy)
Stony Brook Univ., NY (United States)
Univ. of Split (Croatia)
Univ. of Split (Croatia); Humboldt Univ. of Berlin (Germany)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Czech Academy of Sciences, Prague (Czech Republic)

We report that subnanometer copper tetramer-zirconia catalysts turn out to be highly efficient for CO₂ hydrogenation and its conversion to methane. The cluster size and substrate morphology are controlled to optimize the catalytic performance. The two types of zirconia supports investigated are prepared by atomic layer deposition (~ 3 nm thick film) and supersonic cluster beam deposition (nanostructured film, ~ 100 nm thick). The substrate plays a crucial role in determining the activity of the catalyst as well as its cyclability over repeated thermal ramps. A temperature-programmed reaction combined with in situ X-ray characterization reveals the correlation between the evolution in the oxidation state and catalytic activity. Ex situ photoelectron spectroscopy indicates Cu clusters with stronger interactions with the nanostructured film, which can be the cause for the higher activity of this catalyst. Density functional theory calculations based on the Cu₄O₂ cluster supported on a ZrOx subunit reveal low activation barriers and provide mechanism for CO₂ hydrogenation and its conversion to methane. Altogether, the results show a new way to tune the catalytic activity of CO₂ hydrogenation catalysts through controlling the morphology of the support at the nanoscale.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); European Union (EU); Horizon 2020 Research and Innovation Programme

Grant/Contract Number:: AC02-06CH11357; SC0001004; KK.01.1.1.01.0003; 810310

OSTI ID:: 1864350

Journal Information:: ACS Catalysis, Vol. 11, Issue 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: CO2 Methanation on Cu-Cluster Decorated Zirconia Supports with Different Morphology: A Combined Experimental In Situ GIXANES/GISAXS, Ex Situ XPS and Theoretical DFT Study

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Title: CO₂ Methanation on Cu-Cluster Decorated Zirconia Supports with Different Morphology: A Combined Experimental In Situ GIXANES/GISAXS, Ex Situ XPS and Theoretical DFT Study