On the Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts
We present a detailed theoretical study of the pathway for water oxidation in synthetic ruthenium-based catalysts. As a first step, we consider a recently discovered single center catalyst, where experimental observations suggest a purely single-center mechanism. We find low activation energies (<...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society
2012
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| Online Access: | http://hdl.handle.net/1721.1/69558 https://orcid.org/0000-0001-7111-0176 |
| _version_ | 1811072068255481856 |
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| author | Wang, Lee-Ping Wu, Qin Van Voorhis, Troy |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Wang, Lee-Ping Wu, Qin Van Voorhis, Troy |
| author_sort | Wang, Lee-Ping |
| collection | MIT |
| description | We present a detailed theoretical study of the pathway for water oxidation in synthetic ruthenium-based catalysts. As a first step, we consider a recently discovered single center catalyst, where experimental observations suggest a purely single-center mechanism. We find low activation energies (<5 kcal/mol) for each rearrangement in the catalytic cycle. In the crucial step of O−O bond formation, a solvent water acts as a Lewis base and attacks a highly oxidized RuV=O. Armed with the structures and energetics of the single-center catalyst, we proceed to consider a representative Ru-dimer which was designed to form O2 via coupling between the two centers. We discover a mechanism that proceeds in analogous fashion to the monomer case, with all the most significant steps occurring at a single catalytic center within the dimer. This acid−base mechanism suggests a new set of strategies for the rational design of multicenter catalysts: rather than coordinating the relative orientations of the subunits, one can focus on coordinating solvation-shell water molecules or tuning redox potentials. |
| first_indexed | 2024-09-23T09:00:21Z |
| format | Article |
| id | mit-1721.1/69558 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T09:00:21Z |
| publishDate | 2012 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/695582022-09-26T09:45:33Z On the Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts Wang, Lee-Ping Wu, Qin Van Voorhis, Troy Massachusetts Institute of Technology. Department of Chemistry Van Voorhis, Troy Van Voorhis, Troy Wang, Lee-Ping We present a detailed theoretical study of the pathway for water oxidation in synthetic ruthenium-based catalysts. As a first step, we consider a recently discovered single center catalyst, where experimental observations suggest a purely single-center mechanism. We find low activation energies (<5 kcal/mol) for each rearrangement in the catalytic cycle. In the crucial step of O−O bond formation, a solvent water acts as a Lewis base and attacks a highly oxidized RuV=O. Armed with the structures and energetics of the single-center catalyst, we proceed to consider a representative Ru-dimer which was designed to form O2 via coupling between the two centers. We discover a mechanism that proceeds in analogous fashion to the monomer case, with all the most significant steps occurring at a single catalytic center within the dimer. This acid−base mechanism suggests a new set of strategies for the rational design of multicenter catalysts: rather than coordinating the relative orientations of the subunits, one can focus on coordinating solvation-shell water molecules or tuning redox potentials. Eni S.p.A. (Firm) (Solar Frontiers Research Program) United States. Dept. of Energy (Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886) David & Lucile Packard Foundation 2012-03-02T15:41:32Z 2012-03-02T15:41:32Z 2010-04 2010-01 Article http://purl.org/eprint/type/JournalArticle 0020-1669 1520-510X http://hdl.handle.net/1721.1/69558 Wang, Lee-Ping, Qin Wu, and Troy Van Voorhis. “Acid−Base Mechanism for Ruthenium Water Oxidation Catalysts.” Inorganic Chemistry 49.10 (2010): 4543–4553. https://orcid.org/0000-0001-7111-0176 en_US http://dx.doi.org/10.1021/ic100075k Inorganic Chemistry 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 Prof. Van Voorhis via Erja Kajosalo |
| spellingShingle | Wang, Lee-Ping Wu, Qin Van Voorhis, Troy On the Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts |
| title | On the Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts |
| title_full | On the Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts |
| title_fullStr | On the Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts |
| title_full_unstemmed | On the Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts |
| title_short | On the Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts |
| title_sort | on the acid base mechanism for ruthenium water oxidation catalysts |
| url | http://hdl.handle.net/1721.1/69558 https://orcid.org/0000-0001-7111-0176 |
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