References: Electrochemical Interfaces, Interfacial Water and CO2 Reduction
Gonella, G. et al. Water at charged interfaces. Nat. Rev. Chem. 5, 466–485 (2021).
Strmcnik, D. et al. The role of noncovalent interactions in electrocatalytic fuel-cell reactions on platinum. Nat. Chem. 1, 466–472 (2009).
Park, S., Shao, Y. Y., Liu, J. & Wang, Y. Oxygen electrocatalysts for water electrolyzers and reversible fuel cells: Status and perspectives. Energy Environ. Sci. 5, 9331–9344 (2012).
Lopes, P. P. et al. Double-layer effects in electrocatalysis: Oxygen reduction and ethanol oxidation on Au(111), Pt(111) and Ir(111) in alkaline media containing Na+ and Li+ cations. Catal. Today 262, 41–47 (2016).
Frumkin, A. N., Nikolaeva-Fedorovich, N. V., Berezina, N. P. & Keis, K. E. The electroreduction of the S2O82− anion. J. Electroanal. Chem. Interfacial Electrochem. 58, 189–201 (1975).
Resasco, J. et al. Promoting effects of alkali metal cations on the electrochemical reduction of carbon dioxide. J. Am. Chem. Soc. 139, 11277–11287 (2017).
Ringe, S. et al. Understanding cation effects in electrochemical CO2 reduction. Energy Environ. Sci. 12, 3001–3014 (2019).
Ludwig, T. et al. Atomistic insights into the influence of cations on binding energies in Cu-catalyzed carbon dioxide reduction. J. Phys. Chem. C 124, 24765–24775 (2020).
Monteiro, M. C. O. et al. Absence of CO2 electroreduction on copper, gold and silver electrodes without metal cations in solution. Nat. Catal. 4, 654–662 (2021).
Gouy, M. Sur la constitution de la charge électrique à la surface d’un électrolyte. J. Phys. Théor. Appl. 9, 457–468 (1910).
Chapman, D. L. A contribution to the theory of electrocapillarity. Lond. Edinb. Dubl. Philos. Mag. J. Sci. 25, 475–481 (1913).
Stern, O. Zur Theorie der elektrolytischen Doppelschicht. Z. Elektrochem. Angew. Phys. Chem. 30, 508–516 (1924).
Grahame, D. C. The electrical double layer and the theory of electrocapillarity. Chem. Rev. 41, 441–501 (1947).
Devanathan, M. A. V. & Tilak, B. V. K. S. R. A. The structure of the electrical double layer at the metal–solution interface. Chem. Rev. 65, 635–684 (1965).
Parsons, R. Electric double layers: Recent experimental and theoretical developments. Chem. Rev. 90, 813–826 (1990).
Zhang, L.-L., Li, C.-K. & Huang, J. A beginner’s guide to modeling electric double layers under equilibrium, nonequilibrium and AC conditions. J. Electrochem. 28, 2108471 (2022).
Conway, B. E. Properties of individual solvated ions and specificity of ion adsorption effects in processes at electrodes. Chem. Soc. Rev. 21, 253–261 (1992).
Ayranci, E. & Conway, B. E. Effect of size, shape and charge on the partial molar volume, compressibility and electrostriction behavior of sulfur and chlorine oxyanions in water. J. Chem. Soc. Faraday Trans. 79, 1357–1372 (1983).
Marcus, Y. Electrostriction of electrolyte solutions. Chem. Rev. 111, 2761–2783 (2011).
Huang, B. et al. Cation- and pH-dependent hydrogen evolution and oxidation reaction kinetics. JACS Au 1, 1674–1687 (2021).
Gu, J. et al. Modulating electric-field distribution by alkali cations for CO2 electroreduction in strongly acidic media. Nat. Catal. 5, 268–276 (2022).
Lee, X.-Y. et al. Mechanism of cations suppressing proton diffusion kinetics in electrocatalysis. Angew. Chem. Int. Ed. 62, e202218669 (2023).
Yao, Y., Delmo, E. P. & Shao, M. The electrode–electrolyte interface during electrochemical CO2 reduction in acidic electrolytes. Angew. Chem. Int. Ed. 64, e202415894 (2024).
Zhang, Z. et al. Probing electrolyte effects on cation-enhanced CO2 reduction on copper in acidic media. Nat. Catal. 7, 807–817 (2024).
Thämer, M., De Marco, L., Ramasesha, K., Mandal, A. & Tokmakoff, A. Ultrafast 2D IR spectroscopy of excess protons in liquid water. Science 350, 78–82 (2015).
Zhu, B. et al. Proton accumulation near the Au electrode–acid interface probed by electrochemical in situ infrared spectroscopy. J. Phys. Chem. C 129, 11958–11966 (2025).
Zhang, Z. et al. Molecular understanding of the critical role of alkali metal cations in initiating CO2 electroreduction on the Cu(100) surface. Nat. Commun. 15, 612 (2024).
Scatena, L. F., Brown, M. G. & Richmond, G. L. Water on hydrophobic surfaces: Weak hydrogen bonding and strong orientational effects. Science 292, 908–912 (2001).
Osawa, M., Tsushima, M., Mogami, H., Samjeské, G. & Yamakata, A. Water structure at the charged platinum–water interface studied by surface-enhanced infrared absorption spectroscopy. J. Phys. Chem. C 112, 4248–4256 (2008).
Wang, Y. H. et al. In situ Raman spectroscopy reveals the structure and dissociation of interfacial water. Nature 600, 81–85 (2021).
Chen, J. & Wang, T. DPχ: A charge-based machine-learning potential validated at the Pt(111)–water electrochemical interface. J. Chem. Theory Comput. 22, 8493–8501 (2026).
Lee, C. et al. In situ probing of charged interfacial water structures on atomically flat surfaces. Nat. Mater. 18, 697–701 (2019).
Meng, S., Xu, L., Wang, E. & Gao, S. Vibrational recognition of hydrogen-bonded water networks on metal surfaces. Phys. Rev. Lett. 89, 176104 (2002).
Yamakata, A., Soeda, H., Ishiyama, S., Osawa, T. & Morita, A. Real-time observation of hydration-shell destruction under electrochemical forces. J. Am. Chem. Soc. 135, 15033–15039 (2013).
Kresse, G. & Furthmüller, J. Efficiency of ab initio total-energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
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).
Hammer, B., Hansen, L. B. & Nørskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew–Burke–Ernzerhof functionals. Phys. Rev. B 59, 7413–7421 (1999).
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).
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