Copper cluster size effect in methanol synthesis from CO2

doi:10.1021/acs.jpcc.7b01835

Title: Copper cluster size effect in methanol synthesis from CO ₂

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Here, size-selected Cu _n catalysts ( n = 3, 4, 20) were synthesized on Al ₂O ₃ thin films using mass-selected cluster deposition. A systematic study of size and support effects was carried out for CO ₂ 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 Cu ₄/Al ₂O ₃ catalyst shows the highest turnover rate for CH ₃OH production. With only one atom less than Cu ₄, Cu ₃ 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 Al ₂O ₃ support for Cu ₃ than for Cu ₄ leads to remarkably reduced binding strength between the adsorbed intermediates and supported Cu ₃, 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] ; ; Seifert, Sonke ^[1] ; ; ;

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

Publication Date:: 2017-05-08

Grant/Contract Number:: AC02-06CH11357

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

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

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

Country of Publication:: United States

Language:: English

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

OSTI Identifier:: 1372481


                    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.,  
        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. 2017.  
        "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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10.1021/acs.jpcc.7b01835
https://doi.org/10.1021/acs.jpcc.7b01835

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Title: Copper cluster size effect in methanol synthesis from CO 2

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resulting from DOE research funding

Title: Copper cluster size effect in methanol synthesis from CO ₂