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
| Autor: | Lakshmi Kolipaka, Paolo Milani, Sönke Seifert, Antonija Mravak, Cristina Lenardi, Vlasta Bonačić-Koutecký, Anatoly I. Frenkel, Janis Timoshenko, Claudio Piazzoni, Stefan Vajda, Avik Halder, Bing Yang |
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| Rok vydání: | 2021 |
| Předmět: |
In situ
Materials science 010405 organic chemistry Substrate (chemistry) chemistry.chemical_element CO2conversion copper cluster DFT GISAXS reaction mechanism support effect XANES XPS General Chemistry 010402 general chemistry 01 natural sciences Copper Catalysis 0104 chemical sciences X-ray photoelectron spectroscopy Chemical engineering chemistry Methanation Grazing-incidence small-angle scattering Cubic zirconia |
| Zdroj: | ACS Catalysis |
| ISSN: | 2155-5435 |
| DOI: | 10.1021/acscatal.0c05029 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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