Abstract
Water at solid surfaces is key for many processes ranging from biological signal transduction to membrane separation and renewable energy conversion. However, under realistic conditions, which often include environmental and surface charge variations, the interfacial water structure remains elusive. Here we overcome this limit by combining three-dimensional atomic force microscopy (3D-AFM) and interface-sensitive shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) to characterize the graphite–water interfacial structure in situ. Through correlative analysis of the spatial liquid density maps and vibrational peaks within ≈2 nm of the graphite surface, we find the existence of two interfacial configurations at open circuit potential, a transient state where pristine water exhibits strong hydrogen bond (H-bond) breaking effects, and a steady state with hydrocarbons dominating the interface and weak H-bond breaking in the surrounding water. At sufficiently negative potentials, both states transition into a stable structure featuring pristine water with a broader distribution of H-bond configurations. Our three-state model resolves many long-standing controversies on interfacial water structure.
Data availability
The data that support the findings of this study are available from the corresponding authors upon request. Unprocessed spectroscopic data are provided as Supplementary Data 1. Source data are provided with this paper.
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Acknowledgments
L.K.S.B., F.Z., J.K., Q.A., S.Z., K.S.P., and Y.Z. acknowledge support from the National Science Foundation under Grant No. 2339175, the Beckman Young Investigator Award provided by the Arnold and Mabel Beckman Foundation, and the Sloan Research Fellowship from the Alfred P. Sloan Foundation. L.K.S.B. acknowledges support from the TechnipFMC Educational Fund Fellowship. J.K. was partially supported by a PPG-MRL Graduate Research Assistantship. Q.A. acknowledges support from the PPG-MRL Graduate Research Assistantship program. R.G. acknowledges financial support from Ministerio de Ciencia e Innovación grants PID2022-136851NB-I00/AEI/10.13039/501100011033 and EUR2022-134029, as well as the European Commission Horizon Europe MSCA Doctoral Network NANORAM, Grant No. 101120146. R.G. also acknowledges Zhen Tang for helping to process some AFM images.
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Y.Z. designed the experiments in Urbana. R.G. designed the experiments in Madrid. L.K.S.B., D.M.A., F.Z., Q.A., S.Z., and K.S.P. conducted 3D-AFM experiments and initial analyses. F.Z. and J.K. synthesized Au/SiO2 nanoparticles and performed SHINERS measurements. L.K.S.B. and F.Z. performed electroanalytical measurements. L.K.S.B., D.M.A., and F.Z. conducted in-depth data analyses. Y.Z. and R.G. supervised the work. L.K.S.B., F.Z., R.G., and Y.Z. wrote the manuscript with input from all co-authors.
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Bonagiri, L.K.S., Arvelo, D.M., Zhao, F. et al. Probing the molecular structure at graphite–water interfaces by correlating 3D-AFM and SHINERS. Nat Commun (2026). https://doi.org/10.1038/s41467-026-68667-y
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DOI: https://doi.org/10.1038/s41467-026-68667-y
