Abstract
Unveiling interfaces at sub-nanometer scales is essential for advancing the understanding of complex chemical transformations. However, characterizing solid-liquid interfaces with high dimensional sensitivity and temporal resolution remains challenging, due to their dynamic nature and inaccessibility by conventional probes. Here we present an approach, Pattern-enhanced Resonant Soft X-ray Scattering, to overcome the challenges. Rooted in a “sample-as-optics” philosophy, this technique utilizes precisely engineered line-grating nanopatterns to modulate near-field X-ray illumination, coherently enhancing scattering signals from the line-gratings. We implement the method using Ni line-grating nanopatterns in electrochemical water oxidation. The periodic nanostructures serve as diffractive optical elements to reveal the Ni oxidation gradients and structural dynamics at the electrode-electrolyte interfaces. Finite-element simulations corroborate the observed trends by modeling variations in compositions and structures during electrocatalysis. Through integrating advanced sample design with coherent wave nature of soft X-rays, our approach opens accessible pathways to operando exploring chemical evolution and sub-nanometer dimensional variations simultaneously in electrochemical systems. This non-destructive method is efficient and element-specific, making it valuable for probing chemical and dimensional dynamics with appropriate modeling.
Data availability
The Source data underlying the figures of this study are available with the paper. All raw data generated during the current study are available from the corresponding authors upon request. Source data are provided with this paper.
References
Shadike, Z. et al. Identification of LiH and nanocrystalline LiF in the solid-electrolyte interphase of lithium metal anodes. Nat. Nanotechnol. 16, 549–554 (2021).
Xu, K. Electrolytes, Interfaces and Interphases: Fundamentals and Applications in Batteries (Royal Society of Chemistry, 2023).
Zaera, F. Probing liquid/solid interfaces at the molecular level. Chem. Rev. 112, 2920–2986 (2012).
Xu, Q. et al. Operando X-ray characterization platform to unravel catalyst degradation under accelerated stress testing in CO2 electrolysis. Nat. Nanotechnol. 20, 889–896 (2025).
Gervillié-Mouravieff, C. et al. Non-destructive characterization techniques for battery performance and life-cycle assessment. Nat. Rev. Electr. Eng. 1, 547–558 (2024).
Meirer, F. et al. Spatial and temporal exploration of heterogeneous catalysts with synchrotron radiation. Nat. Rev. Mater. 3, 324–340 (2018).
Zhang, Y. et al. Operando characterization and regulation of metal dissolution and redeposition dynamics near battery electrode surface. Nat. Nanotechnol. 18, 790–797 (2023).
Drnec, J. et al. Battery research needs more reliable, representative and reproducible synchrotron characterizations. Nat. Nanotechnol. 20, 584–587 (2025).
Thirimanne, H. M. et al. High sensitivity organic inorganic hybrid X-ray detectors with direct transduction and broadband response. Nat. Commun. 9, 2926 (2018).
Vaskivskyi, I. et al. A high-efficiency programmable modulator for extreme ultraviolet light with nanometre feature size based on an electronic phase transition. Nat. Photonics 18, 458–463 (2024).
Tan, D. H. S. et al. From nanoscale interface characterization to sustainable energy storage using all-solid-state batteries. Nat. Nanotechnol. 15, 170–180 (2020).
Zhang, Q. et al. Simultaneous synthesis and integration of two-dimensional electronic components. Nat. Electron. 2, 164–170 (2019).
Yang, Y. et al. Operando studies reveal active Cu nanograins for CO2 electroreduction. Nature 614, 262–269 (2023).
Zhang, Q. et al. Atomic dynamics of electrified solid-liquid interfaces in liquid-cell TEM. Nature 630, 643–647 (2024).
Zhang, D. et al. Atomic-resolution transmission electron microscopy of electron beam-sensitive crystalline materials. Science 359, 675–679 (2018).
Lv, J. et al. Low-Dose Electron Microscopy Imaging of Electron Beam-Sensitive Crystalline Materials. Acc. Mater. Res. 3, 552–564 (2022).
Fan, Z. et al. In situ transmission electron microscopy for energy materials and devices. Adv. Mater. 31, e1900608 (2019).
Li, H. et al. Edge-exposed molybdenum disulfide with N-doped carbon hybridization: a hierarchical hollow electrocatalyst for carbon dioxide reduction. Adv. Energy Mater. 9, 1900072 (2019).
Garcia-Esparza, A. T. et al. The electrode-electrolyte interface of Cu via modulation excitation X-ray absorption spectroscopy. Energy Environ. Sci. 18, 4643–4650 (2025).
Favaro, M. et al. Unravelling the electrochemical double layer by direct probing of the solid/liquid interface. Nat. Commun. 7, 12695 (2016).
Li, H. et al. Operando Unveiling of Hydrogen Spillover Mechanisms on Tungsten Oxide Surfaces. J. Am. Chem. Soc. 147, 6472–6479 (2025).
Pushie, M. J. et al. Elemental and chemically specific X-ray fluorescence imaging of biological systems. Chem. Rev. 114, 8499–8541 (2014).
Sakdinawat, A. et al. Nanoscale X-ray imaging. Nat. Photonics 4, 840–848 (2010).
Alcorn, F. M. et al. Time-resolved transmission electron microscopy for nanoscale chemical dynamics. Nat. Rev. Chem. 7, 256–272 (2023).
Bencivenga, F. et al. Nanoscale transient gratings excited and probed by extreme ultraviolet femtosecond pulses. Sci. Adv. 5, eaaw5805 (2019).
Chen, L. X. et al. Deciphering photoinduced catalytic reaction mechanisms in natural and artificial photosynthetic systems on multiple temporal and spatial scales using X-ray probes. Chem. Rev. 124, 5421–5469 (2024).
Wang, Y. et al. Achromatic Fresnel optics for wideband extreme-ultraviolet and X-ray imaging. Nature 424, 50–53 (2003).
Xi, J. Q. et al. Optical thin-film materials with low refractive index for broadband elimination of Fresnel reflection. Nat. Photonics 1, 176–179 (2007).
Liu, F. et al. Resonant soft X-ray scattering for polymer materials. Eur. Polym. J. 81, 555–568 (2016).
Magnussen, O. M. et al. In situ and operando X-ray scattering methods in electrochemistry and electrocatalysis. Chem. Rev. 124, 629–721 (2024).
Hammond, C. The Basics of Crystallography and Diffraction Vol. 21 (Oxford University Press, 2015).
Zhong, W. et al. Probing morphology and chemistry in complex soft materials with in situ resonant soft X-ray scattering. J. Phys. Condens. Mat. 33, 313001 (2021).
Bediako, D. K. et al. Mechanistic studies of the oxygen evolution reaction mediated by a nickel–borate thin film electrocatalyst. J. Am. Chem. Soc. 135, 3662–3674 (2013).
Friebel, D. et al. Identification of highly active fe sites in (Ni,Fe)OOH for electrocatalytic water splitting. J. Am. Chem. Soc. 137, 1305–1313 (2015).
Li, H. et al. Systematic design of superaerophobic nanotube-array electrode comprised of transition-metal sulfides for overall water splitting. Nat. Commun. 9, 2452 (2018).
Yang, Y. et al. Operando resonant soft X-ray scattering studies of chemical environment and interparticle dynamics of Cu nanocatalysts for CO2 electroreduction. J. Am. Chem. Soc. 144, 8927–8931 (2022).
Cauchois, Y. Spectral distribution in the regions of characteristic absorption of various crystals. C. R. Acad. Sci. 242, 100–102 (1956).
Stragier, H. et al. Diffraction anomalous fine structure: a new X-ray structural technique. Phys. Rev. Lett. 69, 3064–3067 (1992).
Renevier, H. et al. Diffraction anomalous fine-structure spectroscopy at beamline BM2 at the European Synchrotron Radiation Facility. J. Synchrotron Rad. 10, 435–444 (2003).
Sunday, D. F. et al. Characterizing patterned block copolymer thin films with soft X-rays. ACS Appl. Mater. Interfaces 9, 31325–31334 (2017).
Yang, Y. et al. Operando methods: a new era of electrochemistry. Curr. Opin. Electrochem. 42, 101403 (2023).
Born, M. et al. Principles of Optics: Electromagnetic Theory of Propagation, Interference and Diffraction of Light (Cambridge University Press, 1999).
Tessier, C. et al. The structure of Ni(OH)2: from the ideal material to the electrochemically active one. J. Electrochem. Soc. 146, 2059–2067 (1999).
Bode, H. et al. Zur kenntnis der nickelhydroxidelektrode—I.Über das nickel (II)-hydroxidhydrat. Electrochim. Acta 11, 1079–1087 (1966).
Landman, A. et al. High performance core/shell Ni/Ni(OH)2 electrospun nanofiber anodes for decoupled water splitting. Adv. Funct. Mater. 31, 2008118 (2021).
Collins, B. A. et al. Resonant soft X-ray scattering in polymer science. J. Polym. Sci. 60, 1199–1243 (2022).
Ferron, T. et al. Spectral analysis for resonant soft X-ray scattering enables measurement of interfacial width in 3D organic nanostructures. Phys. Rev. Lett. 119, 167801 (2017).
Amirjani, A. et al. Finite and boundary element methods for simulating optical properties of plasmonic nanostructures. Plasmonics 17, 1095–1106 (2022).
Monk, P. Finite Element Methods for Maxwell’s Equations (Oxford University Press, 2003).
Shahriari, B. et al. Taking the human out of the loop: a review of bayesian optimization. Proc. IEEE 104, 148–175 (2015).
Mauritz, K. A. et al. Dielectric relaxation studies of ion motions in electrolyte-containing perfluorosulfonate ionomers. 1. Sodium hydroxide and sodium chloride systems. Macromolecules 21, 1324–1333 (1988).
Arya, A. et al. Structural, electrical properties and dielectric relaxations in Na+-ion-conducting solid polymer electrolyte. J. Phys.-Condens. Mat. 30, 165402 (2018).
Lucarini, V. et al. Kramers-Kronig Relations in Optical Materials Research Vol. 110 (Springer, 2005).
Horsley, S. A. R. et al. Spatial Kramers–Kronig relations and the reflection of waves. Nat. Photonics 9, 436–439 (2015).
Dionigi, F. et al. In-situ structure and catalytic mechanism of NiFe and CoFe layered double hydroxides during oxygen evolution. Nat. Commun. 11, 2522 (2020).
Trotochaud, L. et al. Nickel–iron oxyhydroxide oxygen-evolution electrocatalysts: the role of intentional and incidental iron incorporation. J. Am. Chem. Soc. 136, 6744–6753 (2014).
Hou, Z. et al. Lattice-strain engineering for heterogenous electrocatalytic oxygen evolution reaction. Adv. Mater. 35, 2209876 (2023).
Xia, Z. et al. Strain engineering of metal-based nanomaterials for energy electrocatalysis. Chem. Soc. Rev. 48, 3265–3278 (2019).
Wehrens-Dijksma, M. et al. Electrochemical Quartz Microbalance characterization of Ni(OH)2-based thin film electrodes. Electrochim. Acta 51, 3609–3621 (2006).
Al Samarai, M. et al. Elucidation of structure–activity correlations in a nickel manganese oxide oxygen evolution reaction catalyst by Operando Ni L-edge X-ray absorption spectroscopy and 2p3d resonant inelastic X-ray scattering. ACS Appl. Mater. Interfaces 11, 38595–38605 (2019).
Qiao, R. et al. Direct experimental probe of the Ni(II)/Ni(III)/Ni(IV) redox evolution in LiNi0.5Mn1.5O4 electrodes. J. Phys. Chem. C 119, 27228–27233 (2015).
Gann, E. et al. Soft x-ray scattering facility at the Advanced Light Source with real-time data processing and analysis. Rev. Sci. Instrum. 83, 045110 (2012).
Henke, B. L. et al. X-ray interactions: photoabsorption, scattering, transmission, and reflection at E = 50-30,000 eV, Z = 1-92. Atom. Data Nucl. Data 54, 181–342 (1993).
Fernández Herrero, A. et al. Applicability of the Debye-Waller damping factor for the determination of the line-edge roughness of lamellar gratings. Opt. Express 27, 32490–32507 (2019).
Andrle, A. et al. Shape- and element-sensitive reconstruction of periodic nanostructures with grazing incidence X-ray fluorescence analysis and machine learning. Nanomaterials 11, 1647 (2021).
Henn, M.-A. et al. A maximum likelihood approach to the inverse problem of scatterometry. Opt. Express 20, 12771–12786 (2012).
Acknowledgements
C.W., R.R., B.L.F., W.C., B.A.H., K.A., and Q.Z. acknowledge the support from the Center for High Precision Patterning Science (CHiPPS), an Energy Frontier Research Center program funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. J.Y. and H.L. acknowledge the support from the Liquid Sunlight Alliance (LiSA), which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award No. DE-SC0021266. B.A.H. and Z.P. acknowledge the support from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under contract No. DE-AC02-05CH11231, Unlocking Chemical Circularity in Recycling by Controlling Polymer Reactivity across Scales program CUP-LBL-Helms. This research used resources at the Advanced Light Source of Lawrence Berkeley National Laboratory, supported by U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-05CH11231. This work used nanofabrication facilities at the Molecular Foundry of Lawrence Berkeley National Laboratory, supported by U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-05CH11231. The authors acknowledge the National Energy Research Scientific Computing Center (NERSC) provide supercomputer resources to this work for the FEM-based simulations. The authors also acknowledge Dr. Thomas Ferron, Dr. Bernhard Luttgenau and Dr. Zachary Fink from Advanced Light Source of Lawrence Berkeley National Laboratory for their support of the manuscript revision and Dr. Yue Liu from Chemical Sciences Division of Lawrence Berkeley National Laboratory for her support of the characterization of the Ni LGNPs. Y.Y. was partially supported by the Center for Alkaline-Based Energy Solutions (CABES), an Energy Frontier Research Center program supported by the U.S. Department of Energy, under grant No. DE-SC0019445, and was partially supported by the Cornell Atkinson Center for Sustainability and the Kavli Institute at Cornell (KIC) Instrumentation Grant. Y.Y. also acknowledges the support from the Berkeley Miller Research Fellowship.
Author information
Authors and Affiliations
Contributions
H.L., K.A., Q.Z., and I.A.C. contributed equally to this work. C.W. and H.L. supervised this work. I.A.C. and C.W. originated the idea of this work. H.L. led the experimental efforts and manuscript writing. K.A. and G.F. conducted scattering modeling and FEM-based simulations. I.A.C., Z.P. designed and fabricated in-situ cells. H.L. I.A.C., Z.P., and F.Y. carried out operando PE-RSoXS experiments and Y.Y. and H.L. performed the electrochemical measurements. Q.Z., S.D., and W.C. conducted the nanofabrication of Ni LGNPs. H.L., K.A., Q.Z., Z.P., Y.Y., and C.W. performed the data analysis. H.L., K.A., Q.Z., I.A.C., Y.Y., Z.P., A.H., B.A.H., B.L.F., R.R., J.G., W.Y., J.Y., and C.W. co-wrote the manuscript. All authors contributed to the discussion on data interpretation and approved the submission of the manuscript.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Communications thanks Dean DeLongchamp, Longxiang Liu, and the other anonymous reviewer(s) for their contribution to the peer review of this work. A peer review file is available.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Source data
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
About this article
Cite this article
Li, H., Andrle, K., Zhang, Q. et al. Pattern-enhanced Resonant Soft X-ray Scattering for Operando monitoring of electrochemical solid-liquid interfaces. Nat Commun (2026). https://doi.org/10.1038/s41467-026-69852-9
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41467-026-69852-9
