Abstract
The classic models of metal electrode–electrolyte interfaces generally focus on either covalent interactions between adsorbates and solid surfaces or on long-range electrolyte–metal electrostatic interactions. Here we demonstrate that these traditional models are insufficient. To understand electrocatalytic trends in the oxygen reduction reaction (ORR), the hydrogen oxidation reaction (HOR) and the oxidation of methanol on platinum surfaces in alkaline electrolytes, non-covalent interactions must be considered. We find that non-covalent interactions between hydrated alkali metal cations M+(H2O)x and adsorbed OH (OHad) species increase in the same order as the hydration energies of the corresponding cations (Li+ >> Na+ > K+ > Cs+) and also correspond to an increase in the concentration of OHad–M+(H2O)x clusters at the interface. These trends are inversely proportional to the activities of the ORR, the HOR and the oxidation of methanol on platinum (Cs+ > K+ > Na+ >> Li+), which suggests that the clusters block the platinum active sites for electrocatalytic reactions.
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Acknowledgements
This work, including use of the Center for Nanoscale Materials, was supported by the University of Chicago and Argonne, and the US Department of Energy, Office of Science, Office of Basic Energy Sciences. We acknowledge computer time at the Laboratory Computing Resource Center at Argonne National Laboratory, the National Energy Research Scientific Computing Center and the Molecular Science Computing Facility at Pacific Northwest National Laboratory. K.K. acknowledges financial support from Toyota Central R&D Labs.
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D.S. and N.M. designed the experiments, D.S., K.K. and D.V. performed the experiments, J.G. performed the DFT calculations, D.S., J.G., V.S. and N.M. discussed the results and N.M. wrote the paper.
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Strmcnik, D., Kodama, K., van der Vliet, D. et al. The role of non-covalent interactions in electrocatalytic fuel-cell reactions on platinum. Nature Chem 1, 466–472 (2009). https://doi.org/10.1038/nchem.330
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DOI: https://doi.org/10.1038/nchem.330
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