From non-innocent to guilty: on the role of redox-active ligands in the electro-assisted reduction of CO(2)mediated by a cobalt(ll)-polypyridyl complex
| Autor: | K. Abel, Jacques Pécaut, Jennifer Fize, Maylis Orio, Leif Hammarström, Nicolas Queyriaux |
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| Přispěvatelé: | Uppsala University, Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie (CIBEST ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017) |
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Oxide
Energy Engineering and Power Technology chemistry.chemical_element 010402 general chemistry Photochemistry Electrochemistry 01 natural sciences Chloride Physical Chemistry law.invention Catalysis chemistry.chemical_compound law medicine [CHIM.COOR]Chemical Sciences/Coordination chemistry Fysikalisk kemi Electrolysis 010405 organic chemistry Renewable Energy Sustainability and the Environment Ligand Selective catalytic reduction [CHIM.CATA]Chemical Sciences/Catalysis 0104 chemical sciences Fuel Technology chemistry Cobalt medicine.drug |
| Zdroj: | Sustainable Energy & Fuels Sustainable Energy & Fuels, 2020, 4 (7), pp.3668-3676. ⟨10.1039/d0se00570c⟩ Sustainable Energy & Fuels, Royal Society of Chemistry, 2020, 4 (7), pp.3668-3676. ⟨10.1039/d0se00570c⟩ |
| ISSN: | 2398-4902 |
| DOI: | 10.1039/d0se00570c⟩ |
| Popis: | International audience; The electrochemical behavior of [Co(bapbpy)Cl](+)[1-Cl](+), a pentacoordinated polypyridyl cobalt(ii) complex containing a redox-active tetradentate ligand (bapbpy: 6,6 '-bis-(2-aminopyridyl)-2,2 '-bipyridine) has been investigated in DMF. Cyclic voltammograms (CV), recorded in the presence of increasing amounts of chloride anions, highlighted the existence of an equilibrium with the neutral hexacoordinated complex. Under a CO(2)atmosphere, CVs of [Co(bapbpy)Cl](+)exhibit significant current enhancement assigned to CO(2)catalytic reduction. Controlled-potential electrolysis experiments confirmed formation of CO and HCOOH as the only identifiable products. The addition of water or chloride ions was shown to affect the distribution of the products obtained, as well as the faradaic efficiency associated with their electrocatalytic generation. A combination of electrochemical techniques, chemical reductions, spectroscopic measurements (UV-vis and IR) and quantum chemical calculations suggests that the ability of thebapbpyligand to be reduced at moderately negative potentials drastically limits the catalytic performances of [1-Cl](+), by stabilizing the formation of a catalytically-competent CO2-adduct that only slowly reacts with oxide acceptors to evolve towards the desired reduction products. |
| Databáze: | OpenAIRE |
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