Density Functional Theory and Experimental Surface Science as Complementary Methods for Interfacial-Structure Elucidation and CO2-Reduction Studies

Surface science techniques such as scanning tunneling microscopy (STM), high-resolution electron energy loss spectroscopy (HREELS) and electrochemistry along with computational methods based on density functional theory (DFT) can be employed as complementary methods in determining the interfacial structure of molecules adsorbed on metal surfaces. As an example, the surface geometry, configuration and position of quinone-based, aromatic and simple molecules such as hydroquinone [1], hydroquinone sulfonate [2,3], benzene [4], 2,3-dimethylhydroquinone [5], sulfuric acid [6] and atomic hydrogen [7] adsorbed on bulk Pd and Pd thin-film surfaces have successfully been identified utilizing this technique. This scheme is extremely essential especially in ascertaining structure-composition-function relationships of surface-modified materials and in establishing methods for surface-structure elucidation for surface-reaction mechanistic studies. This approach is also important in studying self-assembled monolayers of species used for electrocatalysis, for instance, iron hydrogenase enzyme analogs immobilized on Au electrode surfaces used for the electrocatalysis of hydrogen gas formation [8-11] in an effort to discover better H2-evolution catalysts.

 

            Theory and experimental surface science may also be employed in CO2-reduction studies particularly on the discovery and development of novel heterogeneous catalysts for the reduction of CO2 to hydrocarbons, alcohols and other oxygenates that are used as fuels. The discovery of Au-on-W near-surface alloy [12] and NiGa alloy [13,14] as alternative CO2-reduction electrocatalysts was achieved utilizing this approach.

 

Understanding the CO2-reduction mechanism can provide clues as well on how the product yield and selectivity can be improved and should assist in the search for the ideal electrocatalyst. Hence, empirical investigations that aid in the elucidation of the mechanism of CO2 reduction to methane, ethylene and ethanol on a Cu electrocatalyst surface were pursued as a supplementary approach to theory by reducing theoretically proposed reduction intermediates in a differential electrochemical mass spectrometry (DEMS) system and comparing the reduction product distribution [15-20].

 

Finally, a parallel implementation of electrochemical STM and DEMS was assembled to determine the operando surface structure of Cu responsible for the selectivity towards the formation of ethanol from CO2 reduction [21-26]. It is therefore vital to obtain insights from theory to rationalize this behavior and consequently allow the prediction of the surface structure necessary to produce a certain product.

 

 

References:

 

1. Javier, A., Kim, Y. G., Baricuatro, J. H., Balbuena, P. B., & Soriaga, M. P. (2012). The Structure of Benzoquinone Chemisorbed on Pd(111): Simulation of EC-STM Images and HREELS Spectra by Density Functional Theory. Electrocatalysis, 3(3-4), 353-359.

2. Javier, A., Li, D., Balbuena, P. B., & Soriaga, M. P. (2010). Density Functional Study of Benzoquinone Sulfonate Adsorbed on a Pd(111) Electrode Surface. Electrocatalysis, 1(2), 159-162.

3. Li, D., Javier, A., & Soriaga, M. P. Chemisorption and Electrochemical Activity of Thiophenols at Well-Defined Pd(111) Surfaces: Studies by LEED, AES, HREELS, and Electrochemistry, The Winnower 2: e142715.59333, 2015, DOI: 10.15200/winn.142715.59333 Li et al. This article is distributed under the terms of the Creative Commons Attribution, 4.

4. Javier, A., Li, D., Balbuena, P. B., & Soriaga, M. P. (2013). Simulation of scanning tunneling microscope image of benzene chemisorbed on a Pd(111) electrode surface by density functional theory. Reports in Electrochemistry, 3, 1-5.

5. Javier, A., Li, D., Cruz, J., Binamira-Soriaga, E., Balbuena, P. B., & Soriaga, M. P. (2014). C–H activation and metalation at electrode surfaces: 2,3-dimethyl-1,4-dihydroxybenzene on Pd(pc) and Pd(111) studied by TLE, HREELS and DFT. Dalton Transactions, 43(39), 14798-14805.

6. Javier, A. C., Kim, Y. G., Soriaga, J. B., Balbuena, P. B., & Soriaga, M. P. (2011). STM and DFT studies of anion adsorption at well-defined surfaces: Pd(111) in sulfuric acid solution. Phil. Sci. Lett, 4, 18-23.

7. Javier, A., Park, Y. S., Balbuena, P. B., & Soriaga, M. P. Adsorption of Hydrogen on Ultrathin Pd Films on a Pt(111) Surface: A Study by Density Functional Theory, The Winnower 3:e145317.73965, 2016, DOI: 10.15200/winn.145317.73965 Javier et al. This article is distributed under the terms of the Creative Commons Attribution, 4.

8. Chmielowiec, B., Saadi, F. H., Baricuatro, J. H., Javier, A., Kim, Y. G., Sun, G., Darensbourg, M. Y., & Soriaga, M. P. (2014). Molecular catalysis that transpires only when the complex is heterogenized: Studies of a hydrogenase complex surface-tethered on polycrystalline and (111)-faceted gold by EC, PM-FT-IRRAS, HREELS, XPS and STM. Journal of Electroanalytical Chemistry, 716, 63-70.

9. Sanabria-Chinchilla, J., Javier, A., Crouthers, D., Baricuatro, J. H., Darensbourg, M. Y., & Soriaga, M. P. (2014). Immobilization-Enabled Proton Reduction Catalysis by a Di-iron Hydrogenase Mimic. Electrocatalysis, 5(1), 5-7.

10. Sanabria-Chinchilla, J., Javier, A., Crouthers, D., Baricuatro, J. H., Darensbourg, M. Y., & Soriaga, M. P. (2014). Addendum to Immobilization-Enabled Proton-Reduction Catalysis by a Di-iron Hydrogenase Mimic. Electrocatalysis, 5(2), 113-113.

11. Javier, A. C. (2013). Integrating Experiment and Theory in Electrochemical Surface Science: Studies on the Molecular Adsorption on Noble-Metal Electrode Surfaces by Density Functional Theory, Electron Spectroscopy, and Electrochemistry (Doctoral dissertation, Texas A&M University).

12. Javier, A., Baricuatro, J. H., Kim, Y. G., & Soriaga, M. P. (2015). Overlayer Au-on-W Near-Surface Alloy for the Selective Electrochemical Reduction of CO2 to Methanol: Empirical (DEMS) Corroboration of a Computational (DFT) Prediction. Electrocatalysis, 6(6), 493-497.

13. Torelli, D. A., Francis, S. A., Crompton, J. C., Javier, A., Thompson, J. R., Brunschwig, B. S., ... & Lewis, N. S. (2016). Nickel–Gallium-Catalyzed Electrochemical Reduction of CO2 to Highly Reduced Products at Low Overpotentials. ACS Catalysis, 6(3), 2100-2104.

14. Francis, S. A., Torelli, D. A., Crompton, J. C., Javier, A., Thompson, J. R., Brunschwig, B. S., ... & Lewis, N. S. (2016, September). Electrochemical Carbon Dioxide Reduction to Hydrocarbons with a Nickel-Gallium Thin Film Catalyst at Low Overpotentials. In Meeting Abstracts (No. 49, pp. 3600-3600). The Electrochemical Society.

15. Javier, A., Chmielowiec, B., Sanabria-Chinchilla, J., Kim, Y. G., Baricuatro, J. H., & Soriaga, M. P. (2015). A DEMS study of the reduction of CO2, CO, and HCHO pre-adsorbed on Cu electrodes: empirical inferences on the CO2RR mechanism. Electrocatalysis, 6(2), 127-131.

16. Javier, A., Baricuatro, J. H., Kim, Y. G., & Soriaga, M. P. (2017). Electrocatalytic Reduction of CO2 on Cu and Au/W Electrode Surfaces: Empirical (DEMS) Confirmation of Computational (DFT) Predictions. ECS Transactions, 75(48), 1-17.

17. Javier, A., Chmielowiec, B., Sanabria-Chinchilla, J., Kim, Y. G., Baricuatro, J. H., & Soriaga, M. P. (2015, July). Empirical Insights into the CO2 Reduction Reaction Mechanism: A Study of the Reduction of CO2, CO and Formaldehyde on Cu Electrodes By Differential Electrochemical Mass Spectrometry. In Meeting Abstracts (No. 39, pp. 1638-1638). The Electrochemical Society.

18. Javier, A., Baricuatro, J., Kim, Y. G., & Soriaga, M. P. (2016). Reduction of CO2 on Cu and Au/W electrode surfaces: A study by differential electrochemical mass spectrometry. In Meeting Abstracts (COLL-263). American Chemical Society.

19. Javier, A., Baricuatro, J. H., Kim, Y. G., & Soriaga, M. P. (2016, April). A Differential Electrochemical Mass Spectrometric (DEMS) Study of the Electrocatalytic Reduction of CO2 on Cu and Au/W Electrode Surfaces. In Meeting Abstracts (No. 38, pp. 1933-1933). The Electrochemical Society.

20. Javier, A., Baricuatro, J. H., Kim, Y. G., & Soriaga, M. P. (2016, September). Electrocatalytic Reduction of CO2 on Cu and Au/W Electrode Surfaces: Empirical (DEMS) Confirmation of Computational (DFT) Predictions. In Meeting Abstracts (No. 46, pp. 3336-3336). The Electrochemical Society.

21. Soriaga, M. P., Baricuatro, J. H., Cummins, K. D., Kim, Y. G., Saadi, F. H., Sun, G., ... & Carim, A. I. (2015). Electrochemical surface science twenty years later: Expeditions into the electrocatalysis of reactions at the core of artificial photosynthesis. Surface Science, 631, 285-294.

22. Kim, Y. G., Baricuatro, J. H., Javier, A., Gregoire, J. M., & Soriaga, M. P. (2014). The evolution of the polycrystalline copper surface, first to Cu(111) and then to Cu(100), at a fixed CO2RR potential: a study by operando EC-STM. Langmuir, 30(50), 15053-15056.

23. Kim, Y. G., Javier, A., Baricuatro, J. H., & Soriaga, M. P. (2016). Regulating the Product Distribution of CO Reduction by the Atomic-Level Structural Modification of the Cu Electrode Surface. Electrocatalysis, 7(5), 391-399.

24. Kim, Y. G., Javier, A., Baricuatro, J. H., Torelli, D., Cummins, K. D., Tsang, C. F., ... & Soriaga, M. P. (2016). Surface reconstruction of pure-Cu single-crystal electrodes under CO-reduction potentials in alkaline solutions: A study by seriatim ECSTM-DEMS. Journal of Electroanalytical Chemistry, 780, 290-295.

25. Kim, Y. G., Baricuatro, J. H., Javier, A., & Soriaga, M. P. (2017). Tuning the CO-Reduction Product Distribution by Structural Modification of the Cu Electrode Surface. ECS Transactions, 75(50), 87-97.

26. Kim, Y. G., Baricuatro, J. H., Javier, A., & Soriaga, M. P. (2016, September). (Invited) Regulating the CO-Reduction Product Distribution by the Atomic-Level Structural Modification of the Cu Electrode Surface. In Meeting Abstracts (No. 49, pp. 3687-3687). The Electrochemical Society.

 

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