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Alternating Metal-L...
Alternating Metal-Ligand Coordination Improves Electrocatalytic CO2 Reduction by a Mononuclear Ru Catalyst**
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- Agarwala, Hemlata (författare)
- Uppsala universitet,Molekylär biomimetik,Syntetisk molekylär kemi,Tech Univ Munich TUM, Campus Straubing Biotechnol & Sustainabil,Uferstr, D-94315 Straubing, Germany.
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- Chen, Xiaoyu (författare)
- KTH,Teoretisk kemi och biologi,KTH Royal Inst Technol, Sch Engn Sci Chem Biotechnol & Hlth CBH, Dept Theoret Chem & Biol, S-10691 Stockholm, Sweden.
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- Lyonnet, Julien R. (författare)
- Uppsala universitet,Institutionen för kemi - Ångström,Barcelona Inst Sci & Technol, Inst Chem Res Catalonia ICIQ, Tarragona 43007, Spain.
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- Johnson, Ben A. (författare)
- Uppsala universitet,Institutionen för kemi - Ångström,Tech Univ Munich TUM, Campus Straubing Biotechnol & Sustainabil,Uferstr, D-94315 Straubing, Germany.
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- Ahlquist, Mårten S. G., 1979- (författare)
- KTH,Teoretisk kemi och biologi,KTH Royal Inst Technol, Sch Engn Sci Chem Biotechnol & Hlth CBH, Dept Theoret Chem & Biol, S-10691 Stockholm, Sweden.
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- Ott, Sascha (författare)
- Uppsala universitet,Institutionen för kemi - Ångström
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(creator_code:org_t)
- 2023-03-10
- 2023
- Engelska.
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 62:17
- Relaterad länk:
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https://doi.org/10.1...
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https://uu.diva-port... (primary) (Raw object)
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https://urn.kb.se/re...
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https://doi.org/10.1...
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https://urn.kb.se/re...
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Abstract
Ämnesord
Stäng
- Molecular electrocatalysts for CO2-to-CO conversion often operate at large overpotentials, due to the large barrier for C−O bond cleavage. Illustrated with ruthenium polypyridyl catalysts, we herein propose a mechanistic route that involves one metal center that acts as both Lewis base and Lewis acid at different stages of the catalytic cycle, by density functional theory in corroboration with experimental FTIR. The nucleophilic character of the Ru center manifests itself in the initial attack on CO2 to form [Ru-CO2]0, while its electrophilic character allows for the formation of a 5-membered metallacyclic intermediate, [Ru-CO2CO2]0,c, by addition of a second CO2 molecule and intramolecular cyclization. The calculated activation barrier for C−O bond cleavage via the metallacycle is decreased by 34.9 kcal mol−1 as compared to the non-cyclic adduct in the two electron reduced state of complex 1. Such metallacyclic intermediates in electrocatalytic CO2 reduction offer a new design feature that can be implemented consciously in future catalyst designs.
Ämnesord
- NATURVETENSKAP -- Kemi -- Teoretisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)
- NATURVETENSKAP -- Kemi -- Organisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Organic Chemistry (hsv//eng)
Nyckelord
- CO Reduction 2
- Electrocatalysis
- Metallacyclic Intermediates
- Overpotential
- Polypyridyl Ligands
Publikations- och innehållstyp
- ref (ämneskategori)
- art (ämneskategori)
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