# Near-surface defects break symmetry in water adsorption on CeO2−x(111) https://mdr.nims.go.jp/datasets/9a00ef23-2256-4506-b87e-93d4ce9f141b ## File - [s43246-025-01011-x.pdf](https://mdr.nims.go.jp/filesets/72563cd7-72c1-49a8-8795-7467209a0eb6/download) ([Detail](https://mdr.nims.go.jp/filesets/72563cd7-72c1-49a8-8795-7467209a0eb6.md)) - [43246_2025_1011_MOESM2_ESM-2.pdf](https://mdr.nims.go.jp/filesets/9acb69c8-f897-4ac9-9d0f-00a2289d90da/download) ([Detail](https://mdr.nims.go.jp/filesets/9acb69c8-f897-4ac9-9d0f-00a2289d90da.md)) - [43246_2025_1011_MOESM4_ESM.mp4](https://mdr.nims.go.jp/filesets/5b307c95-e2bb-4a72-b069-f12ffb3bd9c3/download) ([Detail](https://mdr.nims.go.jp/filesets/5b307c95-e2bb-4a72-b069-f12ffb3bd9c3.md)) - [43246_2025_1011_MOESM5_ESM.mp4](https://mdr.nims.go.jp/filesets/dc43fcec-e335-48fa-9bd9-ac7f18ea4040/download) ([Detail](https://mdr.nims.go.jp/filesets/dc43fcec-e335-48fa-9bd9-ac7f18ea4040.md)) - [43246_2025_1011_MOESM6_ESM.mp4](https://mdr.nims.go.jp/filesets/b5948e93-7f1b-4fa8-8b49-43a8153ed8ae/download) ([Detail](https://mdr.nims.go.jp/filesets/b5948e93-7f1b-4fa8-8b49-43a8153ed8ae.md)) - [43246_2025_1011_MOESM7_ESM.mp4](https://mdr.nims.go.jp/filesets/abc70cac-e43b-4bed-9d7d-b5db312241d2/download) ([Detail](https://mdr.nims.go.jp/filesets/abc70cac-e43b-4bed-9d7d-b5db312241d2.md)) ## Id 9a00ef23-2256-4506-b87e-93d4ce9f141b ## Local identifier ## Visibility open_to_public ## State published ## Created at 2026-02-04T02:01:05.584697Z ## Updated at 2026-02-07T23:30:20.128702Z ## Published at 2026-02-07T08:34:49.879241Z ## Doi ## First published url https://doi.org/10.1038/s43246-025-01011-x ## Date published 2026-01-23 ## Recorded date published ## Resource type journal_article ## Manuscript type vor ## Collection ## Title - title: Near-surface defects break symmetry in water adsorption on CeO2−x(111) title_type: original lang: en ## Description - description: Water interactions with oxygen-de cient cerium dioxide (CeO2) surfaces are central to hydrogen production and catalytic redox reactions, but the atomic-scale details of how defects influence adsorption and reactivity remain elusive. Here, we unveil how water adsorbs on partially reduced CeO2−x(111) using atomic force microscopy (AFM) with chemically sensitive, oxygen-terminated probes, combined with first-principles calculations. Our AFM imaging reveals water molecules as sharp, asymmetric boomerang-like features radically departing from the symmetric triangular motifs previously attributed to molecular water. Strikingly, these features localize near subsurface defects. While the experiments are carried out at cryogenic temperatures, water was dosed at room temperature, capturing configurations relevant to initial adsorption events in catalytic processes. Density functional theory identifies Ce3+ sites adjacent to subsurface vacancies as the thermodynamically favored adsorption sites, where defect-induced symmetry breaking governs water orientation. Force spectroscopy and simulations further distinguish Ce3+ from Ce4+ centers through their unique interaction signatures. By resolving how subsurface defects control water adsorption at the atomic scale, this work demonstrates the power of chemically selective AFM for probing site-specific reactivity in oxide catalysts, laying the groundwork for direct investigations of complex systems such as single-atom catalysts, metal-support interfaces, and defect-engineered oxides. description_type: abstract lang: und ## Creator - name: Oscar Custance role: author orcid: https://orcid.org/0000-0001-7931-603X - name: Manuel González Lastre role: author orcid: https://orcid.org/0009-0000-2299-6687 - name: Kyungmin Kim role: author orcid: https://orcid.org/0000-0002-3147-5100 - name: Estefanía Fernández-Villanueva role: author orcid: https://orcid.org/0000-0002-9419-0786 - name: Pablo Pou role: author orcid: https://orcid.org/0000-0002-5854-8218 - name: Masayuki Abe role: author orcid: https://orcid.org/0000-0001-5619-3911 - name: Hossein Sepehri-Amin role: author orcid: https://orcid.org/0000-0002-7856-7897 - name: Shigeki Kawai role: author orcid: https://orcid.org/0000-0003-2128-0120 - name: M. Verónica Ganduglia-Pirovano role: author orcid: https://orcid.org/0000-0003-2408-8898 - name: Ruben Perez role: author orcid: https://orcid.org/0000-0001-5896-541X ## Contact agent ## Publisher organization: Springer Science and Business Media LLC ## Managing organization ## Keyword - subject: scanning probe microscopy schema: not_defined - subject: cerium dioxide schema: not_defined - subject: water schema: not_defined - subject: surface schema: not_defined - subject: thin films schema: not_defined - subject: density functional theory schema: not_defined ## Rights - identifier: https://creativecommons.org/licenses/by-nc-nd/4.0/ ## Other identifier(s) ## Data origin ## Embargo ## Journal - title: Communications Materials issn: '26624443' volume: '7' issue: '1' article_number: '39' ## Conference ## Related item ## Funding - identifier: AG2030 funder_name: NIMS description: Advanced Characterization for Materials Innovation - identifier: AM2100 funder_name: NIMS description: 地方連携創出 - identifier: 19H05789 funder_name: " Japan Society for the Promotion of Science" description: 'Functional Surface Core Analysis: New Materials Science on Nanoscale Structures and Functions of Crystal Defect Cores' - identifier: 21H01812 funder_name: " Japan Society for the Promotion of Science" description: Study of Catalytic Activity of Anatase TiO2 and its Nano-cluster Using Atomic Force Microscopy - identifier: 21K18876 funder_name: " Japan Society for the Promotion of Science" description: Ultrafast Atomic Force Microscopy Imaging of Phase Transition Phenomena on Ice Surface by Machine Learning - identifier: 22H00285 funder_name: " Japan Society for the Promotion of Science" description: Development of high precision on-surface reaction and study of the magnetic property in carbon nanostructures - identifier: 23KJ1516 funder_name: " Japan Society for the Promotion of Science" description: Clarification of Water-Gas-Shift Reaction on Cerium Dioxide surface by using Non-Contact Atomic Force Microscopy - identifier: 24K01350 funder_name: " Japan Society for the Promotion of Science" description: Atomic scale reactivity of small islands of a bimetallic alloy on ceria to small molecules investigated by ultrahigh resolution atomic force microscopy ## Instrument ## Instrument operator ## Instrument managing organization ## Measurement method ## Specimen ## Chemical composition ## Structure for specimen ## Structural feature for specimen ## Specific property for specimen ## Process for specimen treatment ## Computational method ## Energy level/transition state ## Software ## Custom property ## Fileset - id: 72563cd7-72c1-49a8-8795-7467209a0eb6 filename: s43246-025-01011-x.pdf content_type: application/pdf size: 3445424 md5: acf55e0a3cf18aac7de671271de7d7d6 - id: 9acb69c8-f897-4ac9-9d0f-00a2289d90da filename: 43246_2025_1011_MOESM2_ESM-2.pdf content_type: application/pdf size: 22689470 md5: 3c934fdb01fe787d68d44d1f8eb1e5a2 - id: 5b307c95-e2bb-4a72-b069-f12ffb3bd9c3 filename: 43246_2025_1011_MOESM4_ESM.mp4 content_type: video/mp4 size: 198244 md5: 3a4f43b6e9b39178743e2e73cc5daccc - id: dc43fcec-e335-48fa-9bd9-ac7f18ea4040 filename: 43246_2025_1011_MOESM5_ESM.mp4 content_type: video/mp4 size: 204262 md5: be74e4185809e35d5ef430ac48687bbc - id: b5948e93-7f1b-4fa8-8b49-43a8153ed8ae filename: 43246_2025_1011_MOESM6_ESM.mp4 content_type: video/mp4 size: 223736 md5: df0c6039eb82dd9a8172254fc07eaadb - id: abc70cac-e43b-4bed-9d7d-b5db312241d2 filename: 43246_2025_1011_MOESM7_ESM.mp4 content_type: video/mp4 size: 210428 md5: 85313248b7bcfd4cd9c0453913a8876a ## Thumbnail fileset_id: 72563cd7-72c1-49a8-8795-7467209a0eb6 filename: s43246-025-01011-x.pdf