Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy

Nature Communications - Tập 7 Số 1
Yifan Huang1, Patricia J. Kooyman2, Marc T. M. Koper1
1Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, PO Box 9502, Leiden, 2300 RA, The Netherlands
2ChemE, Faculty of Applied Sciences, Delft University of Technology, Julianalaan 136, Delft, 2628 BL, The Netherlands

Tóm tắt

AbstractUnderstanding the atomistic details of how platinum surfaces are oxidized under electrochemical conditions is of importance for many electrochemical devices such as fuel cells and electrolysers. Here we use in situ shell-isolated nanoparticle-enhanced Raman spectroscopy to identify the intermediate stages of the electrochemical oxidation of Pt(111) and Pt(100) single crystals in perchloric acid. Density functional theory calculations were carried out to assist in assigning the experimental Raman bands by simulating the vibrational frequencies of possible intermediates and products. The perchlorate anion is suggested to interact with hydroxyl phase formed on the surface. Peroxo-like and superoxo-like two-dimensional (2D) surface oxides and amorphous 3D α-PtO2 are sequentially formed during the anodic polarization. Our measurements elucidate the process of the electrochemical oxidation of platinum single crystals by providing evidence for the structure-sensitive formation of a 2D platinum-(su)peroxide phase. These results may contribute towards a fundamental understanding of the mechanism of degradation of platinum electrocatalysts.

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Tài liệu tham khảo

Andújar, J. M. & Segura, F. Fuel cells: history and updating. A walk along two centuries. Renew. Sust. Energ. Rev. 13, 2309–2322 (2009).

Debe, M. K. Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486, 43–51 (2012).

Zhang, S. et al. A review of platinum-based catalyst layer degradation in proton exchange membrane fuel cells. J. Power Sources 194, 588–600 (2009).

Tremiliosi-Filho, G., Jerkiewicz, G. & Conway, B. E. Characterization and significance of the sequence of stages of oxide film formation at platinum generated by strong anodic polarization. Langmuir 8, 658–667 (1992).

Conway, B. E. Electrochemical oxide film formation at noble metals as a surface-chemical process. Prog. Surf. Sci. 49, 331–452 (1995).

Wakisaka, M., Asizawa, S., Uchida, H. & Watanabe, M. In situ STM observation of morphological changes of the Pt(111) electrode surface during potential cycling in 10 mM HF solution. Phys. Chem. Chem. Phys. 12, 4184–4190 (2010).

Gómez-Marín, A. M. & Feliu, J. M. Pt(111) surface disorder kinetics in perchloric acid solutions and the influence of specific anion adsorption. Electrochim. Acta 82, 558–569 (2012).

Imai, H. et al. In situ and real-time monitoring of oxide growth in a few monolayers at surfaces of platinum nanoparticles in aqueous media. J. Am. Chem. Soc. 131, 6293–6300 (2009).

Siroma, Z., Ishii, K., Yasuda, K., Inaba, M. & Tasaka, A. Stability of platinum particles on a carbon substrate investigated by atomic force microscopy and scanning electron microscopy. J. Power Sources 171, 524–529 (2007).

Mayrhofer, K. J. J. et al. Fuel cell catalyst degradation on the nanoscale. Electrochem. Commun. 10, 1144–1147 (2008).

Topalov, A. A. et al. Dissolution of platinum: limits for the deployment of electrochemical energy conversion? Angew. Chem. Int. Ed. 51, 12613–12615 (2012).

Wu, D. Y., Li, J. F., Ren, B. & Tian, Z. Q. Electrochemical surface-enhanced Raman spectroscopy of nanostructures. Chem. Soc. Rev. 37, 1025–1041 (2008).

Li, J. F. et al. Shell-isolated nanoparticle-enhanced Raman spectroscopy. Nature 464, 392–395 (2010).

Li, J.-F. et al. Extraordinary enhancement of raman scattering from pyridine on single crystal Au and Pt electrodes by shell-isolated Au nanoparticles. J. Am. Chem. Soc. 133, 15922–15925 (2011).

Zhang, M. et al. Extending the shell-isolated nanoparticle-enhanced Raman spectroscopy approach to interfacial ionic liquids at single crystal electrode surfaces. Chem. Commun. 50, 14740–14743 (2014).

Rudnev, A. V., Kuzume, A., Fu, Y. & Wandlowski, T. CO Oxidation on Pt(100): New insights based on combined voltammetric, microscopic and spectroscopic experiments. Electrochim. Acta 133, 132–145 (2014).

Li, C.-Y. et al. In situ monitoring of electrooxidation processes at gold single crystal surfaces using shell-isolated nanoparticle-enhanced raman spectroscopy. J. Am. Chem. Soc. 137, 7648–7651 (2015).

Honesty, N. R. & Gewirth, A. A. Investigating the effect of aging on transpassive behavior of Ni-based alloys in sulfuric acid with shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS). Corros. Sci. 67, 67–74 (2013).

Gao, P., Gosztola, D. & Weaver, M. J. Surface-enhanced raman spectroscopy as a probe of electroorganic reaction pathways. 1. Processes involving adsorbed nitrobenzene, azobenzene, and related species. J. Phys. Chem. 92, 7122–7130 (1988).

Shi, C., Zhang, W., Birke, R. L. & Lombardi, J. R. Detection of short-lived intermediates in electrochemical reactions using time-resolved surface-enhanced Raman spectroscopy. J. Phys. Chem. 94, 4766–4769 (1990).

Pettinger, B., Bao, X., Wilcock, I. C., Muhler, M. & Ertl, G. Surface-enhanced Raman scattering from surface and subsurface oxygen species at microscopically well-defined Ag surfaces. Phys. Rev. Lett. 72, 1561–1564 (1994).

Li, X. & Gewirth, A. A. Peroxide electroreduction on bi-modified au surfaces: vibrational spectroscopy and density functional calculations. J. Am. Chem. Soc. 125, 7086–7099 (2003).

Bae, S.-E., Stewart, K. L. & Gewirth, A. A. Nitrate adsorption and reduction on Cu(100) in acidic solution. J. Am. Chem. Soc. 129, 10171–10180 (2007).

Wang, A. et al. In situ identification of intermediates of benzyl chloride reduction at a silver electrode by SERS coupled with DFT calculations. J. Am. Chem. Soc. 132, 9534–9536 (2010).

Huang, Y. F. et al. Bridging the gap between electrochemical and organometallic activation: benzyl chloride reduction at silver cathodes. J. Am. Chem. Soc. 132, 17199–17210 (2010).

Lai, S. C. S., Kleyn, S. E. F., Rosca, V. & Koper, M. T. M. Mechanism of the dissociation and electrooxidation of ethanol and acetaldehyde on platinum as studied by SERS. J. Phys. Chem. C 112, 19080–19087 (2008).

Clavilier, J. The role of anion on the electrochemical behaviour of a {111} platinum surface; an unusual splitting of the voltammogram in the hydrogen region. J. Electroanal. Chem. 107, 211–216 (1979).

Conway, B. E. & Tilak, B. V. Interfacial processes involving electrocatalytic evolution and oxidation of H2, and the role of chemisorbed H. Electrochim. Acta 47, 3571–3594 (2002).

Nichols, R. J. & Bewick, A. Spectroscopic identification of the adsorbed intermediate in hydrogen evolution on platinum. J. Electroanal. Chem. 243, 445–453 (1988).

Kunimatsu, K., Senzaki, T., Samjeské, G., Tsushima, M. & Osawa, M. Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy. Electrochim. Acta 52, 5715–5724 (2007).

Ogasawara, H. & Ito, M. Hydrogen adsorption on Pt(100), Pt(110), Pt(111) and Pt(1111) electrode surfaces studied by in situ infrared reflection absorption spectroscopy. Chem. Phys. Lett. 221, 213–218 (1994).

Condon, E. U. Production of infrared spectra with electric fields. Phys. Rev. 41, 759–762 (1932).

Lambert, D. K. Vibrational Stark effect of CO on Ni(100), and CO in the aqueous double layer: experiment, theory, and models. J. Chem. Phys. 89, 3847–3860 (1988).

Bishop, D. M. The vibrational Stark effect. J. Chem. Phys. 98, 3179–3184 (1993).

Wasileski, S. A., Koper, M. T. M. & Weaver, M. J. Field-dependent electrode−chemisorbate bonding: sensitivity of vibrational Stark effect and binding energetics to nature of surface coordination. J. Am. Chem. Soc. 124, 2796–2805 (2002).

Oklejas, V., Sjostrom, C. & Harris, J. M. Surface-enhanced raman scattering based vibrational Stark effect as a spatial probe of interfacial electric fields in the diffuse double layer. J. Phys. Chem. B 107, 7788–7794 (2003).

Berná, A., Climent, V. & Feliu, J. M. New understanding of the nature of OH adsorption on Pt(111) electrodes. Electrochem. Commun. 9, 2789–2794 (2007).

Wakisaka, M., Suzuki, H., Mitsui, S., Uchida, H. & Watanabe, M. Identification and quantification of oxygen species adsorbed on Pt(111) single-crystal and polycrystalline Pt electrodes by photoelectron spectroscopy. Langmuir 25, 1897–1900 (2009).

Bondarenko, A. S. et al. The Pt(111)/electrolyte interface under oxygen reduction reaction conditions: an electrochemical impedance spectroscopy study. Langmuir 27, 2058–2066 (2011).

Attard, G. A., Brew, A., Hunter, K., Sharman, J. & Wright, E. Specific adsorption of perchlorate anions on Pt{hkl} single crystal electrodes. Phys. Chem. Chem. Phys. 16, 13689–13698 (2014).

Sandoval-Rojas, A. P., Gómez-Marín, A. M., Suárez-Herrera, M. F., Climent, V. & Feliu, J. M. Role of the interfacial water structure on electrocatalysis: oxygen reduction on Pt(111) in methanesulfonic acid. Catal. Today 262, 95–99 (2016).

Koper, M. T. M. Blank voltammetry of hexagonal surfaces of Pt-group metal electrodes: comparison to density functional theory calculations and ultra-high vacuum experiments on water dissociation. Electrochim. Acta 56, 10645–10651 (2011).

Strmcnik, D. et al. The role of non-covalent interactions in electrocatalytic fuel-cell reactions on platinum. Nat. Chem. 1, 466–472 (2009).

Gland, J. L., Sexton, B. A. & Fisher, G. B. Oxygen interactions with the Pt(111) surface. Surf. Sci. 95, 587–602 (1980).

Schaefer, J. A. & Göpel, W. Identification of surface vibrations on clean and oxygen covered Pt(111) surfaces with high resolution electron energy loss spectroscopy (EELS). J. Electron Spectrosc. Relat. Phenom. 29, 279–285 (1983).

Pankratov, D. A., Sokolov, V. B. & Kiselev, Y. M. Vibrational spectra of platinum superoxo complexes. Russ. J. Inorg. Chem. 45, 1388–1393 (2000).

Panchenko, A., Koper, M. T. M., Shubina, T. E., Mitchell, S. J. & Roduner, E. Ab initio calculations of intermediates of oxygen reduction on low-index platinum surfaces. J. Electrochem. Soc. 151, A2016–A2027 (2004).

Gómez-Marín, A. M., Schouten, K. J. P., Koper, M. T. M. & Feliu, J. M. Interaction of hydrogen peroxide with a Pt(111) electrode. Electrochem. Commun. 22, 153–156 (2012).

Diaz-Morales, O., Calle-Vallejo, F., de Munck, C. & Koper, M. T. M. Electrochemical water splitting by gold: evidence for an oxide decomposition mechanism. Chem. Sci. 4, 2334–2343 (2013).

Diaz-Morales, O., Ferrus-Suspedra, D. & Koper, M. T. M. The importance of nickel oxyhydroxide deprotonation on its activity towards electrochemical water oxidation. Chem. Sci. 7, 2639–2645 (2016).

Koper, M. T. M. Theory of multiple proton-electron transfer reactions and its implications for electrocatalysis. Chem. Sci. 4, 2710–2723 (2013).

Jinnouchi, R., Kodama, K., Suzuki, T. & Morimoto, Y. Kinetically induced irreversibility in electro-oxidation and reduction of Pt surface. J. Chem. Phys. 142, 184709 (2015).

Zhang, Y., Gao, X. & Weaver, M. J. Nature of surface bonding on voltammetrically oxidized noble metals in aqueous media as probed by real-time surface-enhanced Raman spectroscopy. J. Phys. Chem. 97, 8656–8663 (1993).

Graham, G. W., Weber, W. H., McBride, J. R. & Peters, C. R. Raman investigation of simple and complex oxides of platinum. J. Raman Spectrosc. 22, 1–9 (1991).

Marković, N. M. & Ross, P. N. Jr Surface science studies of model fuel cell electrocatalysts. Surf. Sci. Rep. 45, 117–229 (2002).

van der Niet, M. J. T. C., Garcia-Araez, N., Hernández, J., Feliu, J. M. & Koper, M. T. M. Water dissociation on well-defined platinum surfaces: the electrochemical perspective. Catal. Today 202, 105–113 (2013).

Kolb, M. J., Calle-Vallejo, F., Juurlink, L. B. F. & Koper, M. T. M. Density functional theory study of adsorption of H2O, H, O, and OH on stepped platinum surfaces. J. Chem. Phys. 140, 134708 (2014).

Huang, Y. F. et al. Shell-isolated nanoparticle-enhanced Raman spectroscopy of pyridine on smooth silver electrodes. Electrochim. Acta 56, 10652–10657 (2011).

Li, J.-F., Rudnev, A., Fu, Y., Bodappa, N. & Wandlowski, T. In situ SHINERS at electrochemical single-crystal electrode/electrolyte interfaces: tuning preparation strategies and selected applications. ACS Nano 7, 8940–8952 (2013).

Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).

Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 6, 15–50 (1996).

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).

Methfessel, M. & Paxton, A. T. High-precision sampling for Brillouin-zone integration in metals. Phys. Rev. B 40, 3616–3621 (1989).