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Regulating the Product Distribution of CO Reduction by the Atomic-Level Structural Modification of the Cu Electrode Surface

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Abstract

Cu catalyzes the electrochemical reduction of CO2 or CO to an assortment of products, a behavior that is a detriment when only one reduced compound is desired. The present article provides an example in which, through the atomic-level control of the structure of the Cu electrode surface, the yield distribution is regulated to generate only one product. The reaction investigated was the preferential reduction of CO to C2H5OH on Cu at a low overpotential in alkaline solution. Experimental measurements combined electrochemical scanning tunneling microscopy (ECSTM) and differential electrochemical mass spectrometry (DEMS). An atomically ordered Cu(100) surface, prepared from either a single crystal or by Cu(pc)-to-Cu(100) reconstruction, did not produce ethanol. When the surfaces were subjected to monolayer-limited Cu↔Cu2O cycles, only the reconstructed surface underwent an additional structural transformation that spawned the selective production of ethanol at a potential 645 mV lower than that which generates multiple products. Quasi-operando ECSTM indicated transformation to an ordered stepped surface, Cu(S) − [3(100) × (111)], or Cu(511). The non-selective, multiple-product Cu-catalyzed reduction of CO had thus been regulated to yield only one liquid fuel by an atomic-level structural modification of the electrode surface.

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Notes

  1. Other aspects investigated, such as the use of non-aqueous solvent, the employment of reactant concentrators, the influence of electrolyte, the adoption of gas-phase-feed approaches, or the method of product analysis, are deemed not of fundamental significance since those do not alter the free-energy landscape of the electrocatalytic reaction.

  2. Cu is a prodigious scavenger of O2(g); hence, ex situ characterization of an electrode not stringently protected from the environment will invariably encounter several surface layers of Cu2O and CuO [23].

  3. The appreciable cathodic evolution of H2 and the reduction of CO at −1.06 V (SHE) precluded the atomic resolution of the ECSTM images. Hence, the ECSTM experiments at slightly less negative potentials (−0.9 V) to ensure minimal catalytic activities, cannot be rigorously classified as true operando.

  4. It cannot be overemphasized that, whereas the ECSTM images displayed in this paper are only for nanometer-scale domains on the bulk crystal, those are representative of the entire surface because numerous images have been evaluated throughout the macroscopic surface. The protocol has always been that results will be adopted only if satisfactory agreement exists among all the sampled images.

  5. It is not understood at this time, but it is beyond the scope of the present paper, why an ordered Cu(100) layer situated at the top of a Cu(pc) substrate is more pliable than a Cu(100) sheet above a Cu(100) base. It is likely related to the adhesion of various surfaces in contact with one another. For example, the adhesion coefficient of Cu(100)-Cu(100) planes has been reported to be five times larger than that for Cu(111)-Cu(100) surfaces [35].

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Acknowledgments

This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award No. DE-SC0004993.

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Authors and Affiliations

  1. Division of Chemistry and Chemical Engineering, Joint Center for Artificial Photosynthesis, California Institute of Technology, Pasadena, CA, 91125, USA

    Youn-Geun Kim, Alnald Javier, Jack H. Baricuatro & Manuel P. Soriaga

  2. Department of Chemistry, Texas A&M University, College Station, TX, 77843, USA

    Manuel P. Soriaga

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  1. Youn-Geun Kim
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  2. Alnald Javier
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Correspondence to Manuel P. Soriaga.

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Kim, YG., Javier, A., Baricuatro, J.H. et al. Regulating the Product Distribution of CO Reduction by the Atomic-Level Structural Modification of the Cu Electrode Surface. Electrocatalysis 7, 391–399 (2016). https://doi.org/10.1007/s12678-016-0314-1

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