Copper cluster size effect in methanol synthesis from CO2

doi:10.1021/acs.jpcc.7b01835

Title: Copper cluster size effect in methanol synthesis from CO₂

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Abstract

Here, size-selected Cu_n catalysts (n = 3, 4, 20) were synthesized on Al₂O₃ thin films using mass-selected cluster deposition. A systematic study of size and support effects was carried out for CO₂ hydrogenation at atmospheric pressure using a combination of in situ grazing incidence X-ray absorption spectroscopy, catalytic activity measurement, and first-principles calculations. The catalytic activity for methanol synthesis is found to strongly vary as a function of the cluster size; the Cu₄/Al₂O₃ catalyst shows the highest turnover rate for CH₃OH production. With only one atom less than Cu₄, Cu₃ showed less than 50% activity. Density functional theory calculations predict that the activities of the gas-phase Cu clusters increase as the cluster size decreases; however, the stronger charge transfer interaction with Al₂O₃ support for Cu₃ than for Cu₄ leads to remarkably reduced binding strength between the adsorbed intermediates and supported Cu₃, which subsequently results in a less favorable energetic pathway to transform carbon dioxide to methanol.

Authors:

Yang, Bing ^[1]; Liu, Cong ^[1]; Halder, Avik ^[1]; Tyo, Eric C. ^[1];

^[1]; Seifert, Sonke ^[1];

^[1];

^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)

Publication Date:: 2017-05-08

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI Identifier:: 1372481

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 121; Journal Issue: 19; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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                    Yang, Bing, Liu, Cong, Halder, Avik, Tyo, Eric C., Martinson, Alex B. F., Seifert, Sonke, Zapol, Peter, Curtiss, Larry A., and Vajda, Stefan. Copper cluster size effect in methanol synthesis from CO2.  United States: N. p., 2017. 
        Web.  doi:10.1021/acs.jpcc.7b01835.

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                    Yang, Bing, Liu, Cong, Halder, Avik, Tyo, Eric C., Martinson, Alex B. F., Seifert, Sonke, Zapol, Peter, Curtiss, Larry A., & Vajda, Stefan. Copper cluster size effect in methanol synthesis from CO2.  United States.  doi:10.1021/acs.jpcc.7b01835.

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                    Yang, Bing, Liu, Cong, Halder, Avik, Tyo, Eric C., Martinson, Alex B. F., Seifert, Sonke, Zapol, Peter, Curtiss, Larry A., and Vajda, Stefan. Mon .  
        "Copper cluster size effect in methanol synthesis from CO2".  United States.  doi:10.1021/acs.jpcc.7b01835.  https://www.osti.gov/servlets/purl/1372481.

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@article{osti_1372481,

  title        = {Copper cluster size effect in methanol synthesis from CO2},

  author       = {Yang, Bing and Liu, Cong and Halder, Avik and Tyo, Eric C. and Martinson, Alex B. F. and Seifert, Sonke and Zapol, Peter and Curtiss, Larry A. and Vajda, Stefan},

  abstractNote = {Here, size-selected Cun catalysts (n = 3, 4, 20) were synthesized on Al2O3 thin films using mass-selected cluster deposition. A systematic study of size and support effects was carried out for CO2 hydrogenation at atmospheric pressure using a combination of in situ grazing incidence X-ray absorption spectroscopy, catalytic activity measurement, and first-principles calculations. The catalytic activity for methanol synthesis is found to strongly vary as a function of the cluster size; the Cu4/Al2O3 catalyst shows the highest turnover rate for CH3OH production. With only one atom less than Cu4, Cu3 showed less than 50% activity. Density functional theory calculations predict that the activities of the gas-phase Cu clusters increase as the cluster size decreases; however, the stronger charge transfer interaction with Al2O3 support for Cu3 than for Cu4 leads to remarkably reduced binding strength between the adsorbed intermediates and supported Cu3, which subsequently results in a less favorable energetic pathway to transform carbon dioxide to methanol.},

  doi          = {10.1021/acs.jpcc.7b01835},

  journal      = {Journal of Physical Chemistry. C},

  number       = 19,

  volume       = 121,

  place        = {United States},

  year         = {2017},

  month        = {5}

}

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DOI: 10.1021/acs.jpcc.7b01835

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Title: Copper cluster size effect in methanol synthesis from CO2

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Title: Copper cluster size effect in methanol synthesis from CO₂