Mechanistic insights into the electrochemical reduction of CO2 to CO on Ni(salphen) complexes
| Main Author: | |
|---|---|
| Publication Date: | 2023 |
| Other Authors: | , , , |
| Format: | Article |
| Language: | eng |
| Source: | Repositórios Científicos de Acesso Aberto de Portugal (RCAAP) |
| Download full: | http://hdl.handle.net/10362/155554 |
Summary: | LA/P/0056/2020. The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project No 022161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC). FCT is acknowledged for PTDCQUI-QIN0252_2021 (PNM). The CARISMA COST action CM1205 is acknowledged. MJC thanks N. A. G. Bandeira for technical assistance. The CATSUS doctoral programme is also acknowledged. Publisher Copyright: © 2023 The Royal Society of Chemistry. |
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Mechanistic insights into the electrochemical reduction of CO2 to CO on Ni(salphen) complexesInorganic ChemistrySDG 13 - Climate ActionLA/P/0056/2020. The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project No 022161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC). FCT is acknowledged for PTDCQUI-QIN0252_2021 (PNM). The CARISMA COST action CM1205 is acknowledged. MJC thanks N. A. G. Bandeira for technical assistance. The CATSUS doctoral programme is also acknowledged. Publisher Copyright: © 2023 The Royal Society of Chemistry.Cyclic voltammetry and bulk electrolysis showed that [Ni(ii)(salphen)] [1], [Ni(ii)(tBu-salphen)] [2], and a binuclear Ni(ii) compound combining salphen and tBu-salphen [3] react with CO2 to yield a metal-carbonyl species that is stable under an oxygen free atmosphere. Upon exposure to air, a stoichiometric amount of CO is released (detected by gas chromatography) and protonation regenerates the initial complex. To shed light on the mechanism of CO2 reduction and O2-dependent CO release by [1], UV-vis, EPR and SEC-IR spectroscopy studies complemented with DFT calculations were performed. It is proposed that the mono reduced [Ni(i)(salphen)]−, 2[1]−, formed a CO2 complex, 2[1(CO2)]−, which was then further reduced to 3[1(CO2)]2−. After addition of two protons, the coordinated CO2 was reduced to CO and released, regenerating 1[1]. Alternatively, 2[1(CO2)]− is protonated and then reduced to the same intermediate as before, continuing the same way. In the second cycle, the CO released competed with CO2 and coordinated to 2[1]− much more strongly, thereby deactivating the system. The new 2[1(CO)]− was reduced to 3[1(CO)]2− which was identified by comparison of experimental spectroscopic (UV-vis, EPR, SEC-IR) data with DFT calculated parameters.LAQV@REQUIMTEDQ - Departamento de QuímicaRUNRealista, S.Costa, Paulo J.Maia, LuísaCalhorda, Maria JoséMartinho, Paulo N.2023-07-19T22:16:01Z2023-072023-07-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article15application/pdfhttp://hdl.handle.net/10362/155554eng2052-1553PURE: 66601061https://doi.org/10.1039/d3qi00424dinfo:eu-repo/semantics/openAccessreponame:Repositórios Científicos de Acesso Aberto de Portugal (RCAAP)instname:FCCN, serviços digitais da FCT – Fundação para a Ciência e a Tecnologiainstacron:RCAAP2024-06-24T01:35:03Zoai:run.unl.pt:10362/155554Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireinfo@rcaap.ptopendoar:https://opendoar.ac.uk/repository/71602025-05-28T17:43:43.409002Repositórios Científicos de Acesso Aberto de Portugal (RCAAP) - FCCN, serviços digitais da FCT – Fundação para a Ciência e a Tecnologiafalse |
| dc.title.none.fl_str_mv |
Mechanistic insights into the electrochemical reduction of CO2 to CO on Ni(salphen) complexes |
| title |
Mechanistic insights into the electrochemical reduction of CO2 to CO on Ni(salphen) complexes |
| spellingShingle |
Mechanistic insights into the electrochemical reduction of CO2 to CO on Ni(salphen) complexes Realista, S. Inorganic Chemistry SDG 13 - Climate Action |
| title_short |
Mechanistic insights into the electrochemical reduction of CO2 to CO on Ni(salphen) complexes |
| title_full |
Mechanistic insights into the electrochemical reduction of CO2 to CO on Ni(salphen) complexes |
| title_fullStr |
Mechanistic insights into the electrochemical reduction of CO2 to CO on Ni(salphen) complexes |
| title_full_unstemmed |
Mechanistic insights into the electrochemical reduction of CO2 to CO on Ni(salphen) complexes |
| title_sort |
Mechanistic insights into the electrochemical reduction of CO2 to CO on Ni(salphen) complexes |
| author |
Realista, S. |
| author_facet |
Realista, S. Costa, Paulo J. Maia, Luísa Calhorda, Maria José Martinho, Paulo N. |
| author_role |
author |
| author2 |
Costa, Paulo J. Maia, Luísa Calhorda, Maria José Martinho, Paulo N. |
| author2_role |
author author author author |
| dc.contributor.none.fl_str_mv |
LAQV@REQUIMTE DQ - Departamento de Química RUN |
| dc.contributor.author.fl_str_mv |
Realista, S. Costa, Paulo J. Maia, Luísa Calhorda, Maria José Martinho, Paulo N. |
| dc.subject.por.fl_str_mv |
Inorganic Chemistry SDG 13 - Climate Action |
| topic |
Inorganic Chemistry SDG 13 - Climate Action |
| description |
LA/P/0056/2020. The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project No 022161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC). FCT is acknowledged for PTDCQUI-QIN0252_2021 (PNM). The CARISMA COST action CM1205 is acknowledged. MJC thanks N. A. G. Bandeira for technical assistance. The CATSUS doctoral programme is also acknowledged. Publisher Copyright: © 2023 The Royal Society of Chemistry. |
| publishDate |
2023 |
| dc.date.none.fl_str_mv |
2023-07-19T22:16:01Z 2023-07 2023-07-01T00:00:00Z |
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info:eu-repo/semantics/publishedVersion |
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info:eu-repo/semantics/article |
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article |
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publishedVersion |
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http://hdl.handle.net/10362/155554 |
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http://hdl.handle.net/10362/155554 |
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eng |
| language |
eng |
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2052-1553 PURE: 66601061 https://doi.org/10.1039/d3qi00424d |
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info:eu-repo/semantics/openAccess |
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openAccess |
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15 application/pdf |
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Repositórios Científicos de Acesso Aberto de Portugal (RCAAP) - FCCN, serviços digitais da FCT – Fundação para a Ciência e a Tecnologia |
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