Imaging Catalytic Activation of CO2 on Cu2O (110): A First-Principles Study

doi:10.1021/acs.chemmater.7b04803

Title: Imaging Catalytic Activation of CO ₂ on Cu ₂O (110): A First-Principles Study

Abstract

Balancing global energy needs against increasing greenhouse gas emissions requires new methods for efficient CO ₂ reduction. While photoreduction of CO ₂ is a viable approach for fuel generation, the rational design of photocatalysts hinges on precise characterization of the surface catalytic reactions. Cu ₂O is a promising next-generation photocatalyst, but the atomic-scale description of the interaction between CO ₂ and the Cu ₂O surface is largely unknown, and detailed experimental measurements are lacking. In this study, density-functional-theory (DFT) calculations have been performed to identify the Cu ₂O (110) surface stoichiometry that favors CO ₂ reduction. To facilitate interpretation of scanning tunneling microscopy (STM) and X-ray absorption near-edge structures (XANES) measurements, which are useful for characterizing catalytic reactions, we present simulations based on DFT-derived surface morphologies with various adsorbate types. STM and XANES simulations were performed using the Tersoff Hamann approximation and Bethe-Salpeter equation (BSE) approach, respectively. The results provide guidance for observation of CO ₂ reduction reaction on, and rational surface engineering of, Cu ₂O (110). In conclusion, they also demonstrate the effectiveness of computational image and spectroscopy modeling as a predictive tool for surface catalysis characterization.

Authors:

^[1]; Zhang, Rui ^[1];

^[2]; Shirley, Eric L. ^[2];

^[3];

^[1];

^[1]

Argonne National Lab. (ANL), Argonne, IL (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Purdue Univ., West Lafayette, IN (United States)

Publication Date:: 2018-03-05

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:: 1434330

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Chemistry of Materials

Additional Journal Information:: Journal Volume: 30; Journal Issue: 6; Journal ID: ISSN 0897-4756

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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

Citation Formats


                    Li, Liang, Zhang, Rui, Vinson, John, Shirley, Eric L., Greeley, Jeffrey P., Guest, Jeffrey R., and Chan, Maria K. Y. Imaging Catalytic Activation of CO2 on Cu2O (110): A First-Principles Study.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.chemmater.7b04803.

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                    Li, Liang, Zhang, Rui, Vinson, John, Shirley, Eric L., Greeley, Jeffrey P., Guest, Jeffrey R., & Chan, Maria K. Y. Imaging Catalytic Activation of CO2 on Cu2O (110): A First-Principles Study.  United States.  doi:10.1021/acs.chemmater.7b04803.

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                    Li, Liang, Zhang, Rui, Vinson, John, Shirley, Eric L., Greeley, Jeffrey P., Guest, Jeffrey R., and Chan, Maria K. Y. Mon .  
        "Imaging Catalytic Activation of CO2 on Cu2O (110): A First-Principles Study".  United States.  doi:10.1021/acs.chemmater.7b04803.  https://www.osti.gov/servlets/purl/1434330.

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@article{osti_1434330,

  title        = {Imaging Catalytic Activation of CO2 on Cu2O (110): A First-Principles Study},

  author       = {Li, Liang and Zhang, Rui and Vinson, John and Shirley, Eric L. and Greeley, Jeffrey P. and Guest, Jeffrey R. and Chan, Maria K. Y.},

  abstractNote = {Balancing global energy needs against increasing greenhouse gas emissions requires new methods for efficient CO2 reduction. While photoreduction of CO2 is a viable approach for fuel generation, the rational design of photocatalysts hinges on precise characterization of the surface catalytic reactions. Cu2O is a promising next-generation photocatalyst, but the atomic-scale description of the interaction between CO2 and the Cu2O surface is largely unknown, and detailed experimental measurements are lacking. In this study, density-functional-theory (DFT) calculations have been performed to identify the Cu2O (110) surface stoichiometry that favors CO2 reduction. To facilitate interpretation of scanning tunneling microscopy (STM) and X-ray absorption near-edge structures (XANES) measurements, which are useful for characterizing catalytic reactions, we present simulations based on DFT-derived surface morphologies with various adsorbate types. STM and XANES simulations were performed using the Tersoff Hamann approximation and Bethe-Salpeter equation (BSE) approach, respectively. The results provide guidance for observation of CO2 reduction reaction on, and rational surface engineering of, Cu2O (110). In conclusion, they also demonstrate the effectiveness of computational image and spectroscopy modeling as a predictive tool for surface catalysis characterization.},

  doi          = {10.1021/acs.chemmater.7b04803},

  journal      = {Chemistry of Materials},

  number       = 6,

  volume       = 30,

  place        = {United States},

  year         = {2018},

  month        = {3}

}

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DOI: 10.1021/acs.chemmater.7b04803

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Figure 1: (a) Side (left) and top (right) views of the Cu₂O (110) surface slab model. Blue box indicates the size of the primitive cell of the surface. Relaxed structural models of Cu₂O (110) surface with (b) no surface defects, (c) one O vacancy, and additional O atom at (d)more »

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Title: Imaging Catalytic Activation of CO 2 on Cu 2O (110): A First-Principles Study

Abstract

Citation Formats

Figures / Tables:

Title: Imaging Catalytic Activation of CO ₂ on Cu ₂O (110): A First-Principles Study