First-Principles Assessment of H[subscript 2]S and H[subscript 2]O Reaction Mechanisms and the Subsequent Hydrogen Absorption on the CeO[subscript 2](111) Surface
The main goal of this study is to assess the resistance of ceria against hydrogen penetration into its bulk, in the context of its application as a protective surface coating against hydrogen embrittlement in metals. We evaluate the reaction mechanisms between the H[subscript 2]S and H[subscript 2]O...
| Main Authors: | , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society (ACS)
2014
|
| Online Access: | http://hdl.handle.net/1721.1/86397 https://orcid.org/0000-0002-2688-5666 |
| _version_ | 1811069768878260224 |
|---|---|
| author | Marrocchelli, Dario Yildiz, Bilge |
| author2 | Massachusetts Institute of Technology. Department of Nuclear Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Nuclear Science and Engineering Marrocchelli, Dario Yildiz, Bilge |
| author_sort | Marrocchelli, Dario |
| collection | MIT |
| description | The main goal of this study is to assess the resistance of ceria against hydrogen penetration into its bulk, in the context of its application as a protective surface coating against hydrogen embrittlement in metals. We evaluate the reaction mechanisms between the H[subscript 2]S and H[subscript 2]O molecules and the CeO[subscript 2](111) surface and their kinetic descriptors, using first principles based calculations in the density functional theory framework. Our approach is validated by performing an extensive comparison with the available experimental data. We predict that hydrogen penetration into CeO[subscript 2](111) is a surface-absorption-limited process with a high-energy barrier (1.67 eV) and endothermicity (1.50 eV), followed by a significantly lower bulk dissolution energy and diffusion barrier (0.67 and 0.52 eV, respectively). We find that the presence of surface vacancies and higher coverages affects significantly the energetics of H[subscript 2]S/H[subscript 2]O adsorption, dissociation, and hydrogen subsurface absorption, facilitating most of these processes and degrading the protectiveness of ceria against hydrogen penetration. The reasons behind these effects are discussed. Overall we expect ceria to hinder the hydrogen incorporation significantly due to the effectively large energy barrier against subsurface absorption, provided vacancy formation is suppressed. |
| first_indexed | 2024-09-23T08:15:46Z |
| format | Article |
| id | mit-1721.1/86397 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T08:15:46Z |
| publishDate | 2014 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/863972022-09-30T08:40:14Z First-Principles Assessment of H[subscript 2]S and H[subscript 2]O Reaction Mechanisms and the Subsequent Hydrogen Absorption on the CeO[subscript 2](111) Surface Marrocchelli, Dario Yildiz, Bilge Massachusetts Institute of Technology. Department of Nuclear Science and Engineering Massachusetts Institute of Technology. Laboratory for Electrochemical Interfaces Yildiz, Bilge Marrocchelli, Dario Yildiz, Bilge The main goal of this study is to assess the resistance of ceria against hydrogen penetration into its bulk, in the context of its application as a protective surface coating against hydrogen embrittlement in metals. We evaluate the reaction mechanisms between the H[subscript 2]S and H[subscript 2]O molecules and the CeO[subscript 2](111) surface and their kinetic descriptors, using first principles based calculations in the density functional theory framework. Our approach is validated by performing an extensive comparison with the available experimental data. We predict that hydrogen penetration into CeO[subscript 2](111) is a surface-absorption-limited process with a high-energy barrier (1.67 eV) and endothermicity (1.50 eV), followed by a significantly lower bulk dissolution energy and diffusion barrier (0.67 and 0.52 eV, respectively). We find that the presence of surface vacancies and higher coverages affects significantly the energetics of H[subscript 2]S/H[subscript 2]O adsorption, dissociation, and hydrogen subsurface absorption, facilitating most of these processes and degrading the protectiveness of ceria against hydrogen penetration. The reasons behind these effects are discussed. Overall we expect ceria to hinder the hydrogen incorporation significantly due to the effectively large energy barrier against subsurface absorption, provided vacancy formation is suppressed. National Science Foundation (U.S.) (TeraGrid Project Research Allocation TG-DMR110004) National Science Foundation (U.S.) (TeraGrid Project Start-up Allocation TG-DMR100098) 2014-05-05T13:23:56Z 2014-05-05T13:23:56Z 2011-12 2011-12 Article http://purl.org/eprint/type/JournalArticle 1932-7447 1932-7455 http://hdl.handle.net/1721.1/86397 Marrocchelli, Dario, and Bilge Yildiz. “ First-Principles Assessment of H 2 S and H 2 O Reaction Mechanisms and the Subsequent Hydrogen Absorption on the CeO 2 (111) Surface .” The Journal of Physical Chemistry C 116, no. 3 (January 26, 2012): 2411–2424. https://orcid.org/0000-0002-2688-5666 en_US http://dx.doi.org/10.1021/jp205573v The Journal of Physical Chemistry C Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) Prof. Yildiz via Chris Sherratt |
| spellingShingle | Marrocchelli, Dario Yildiz, Bilge First-Principles Assessment of H[subscript 2]S and H[subscript 2]O Reaction Mechanisms and the Subsequent Hydrogen Absorption on the CeO[subscript 2](111) Surface |
| title | First-Principles Assessment of H[subscript 2]S and H[subscript 2]O Reaction Mechanisms and the Subsequent Hydrogen Absorption on the CeO[subscript 2](111) Surface |
| title_full | First-Principles Assessment of H[subscript 2]S and H[subscript 2]O Reaction Mechanisms and the Subsequent Hydrogen Absorption on the CeO[subscript 2](111) Surface |
| title_fullStr | First-Principles Assessment of H[subscript 2]S and H[subscript 2]O Reaction Mechanisms and the Subsequent Hydrogen Absorption on the CeO[subscript 2](111) Surface |
| title_full_unstemmed | First-Principles Assessment of H[subscript 2]S and H[subscript 2]O Reaction Mechanisms and the Subsequent Hydrogen Absorption on the CeO[subscript 2](111) Surface |
| title_short | First-Principles Assessment of H[subscript 2]S and H[subscript 2]O Reaction Mechanisms and the Subsequent Hydrogen Absorption on the CeO[subscript 2](111) Surface |
| title_sort | first principles assessment of h subscript 2 s and h subscript 2 o reaction mechanisms and the subsequent hydrogen absorption on the ceo subscript 2 111 surface |
| url | http://hdl.handle.net/1721.1/86397 https://orcid.org/0000-0002-2688-5666 |
| work_keys_str_mv | AT marrocchellidario firstprinciplesassessmentofhsubscript2sandhsubscript2oreactionmechanismsandthesubsequenthydrogenabsorptionontheceosubscript2111surface AT yildizbilge firstprinciplesassessmentofhsubscript2sandhsubscript2oreactionmechanismsandthesubsequenthydrogenabsorptionontheceosubscript2111surface |