Combined X-Ray Absorption Near-Edge Structure and X-ray Photoelectron Study of the Electrocatalytically Active Cobalt(I) Cage Complexes and the Clathrochelate Cobalt(II)- and Cobalt(III)-Containing Precursors and Analogs Full article
| Journal |
The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455 |
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| Output data | Year: 2013, Volume: 117, Number: 6, Pages: 2753-2759 Pages count : 7 DOI: 10.1021/jp3085606 | ||||||
| Tags | Binding energy; Electrocatalysis; Electronic structure; Hydrogen production; Ionization potential; Ligands; Space applications; X ray absorption near edge structure spectroscopy | ||||||
| Authors |
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| Affiliations |
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Funding (6)
| 1 | Russian Foundation for Basic Research | 10-03-00613 |
| 2 | Russian Foundation for Basic Research | 11-03-00986 |
| 3 | Russian Foundation for Basic Research | 12-03-00961 |
| 4 | The Ministry of Education and Science of the Russian Federation | 14.518.11.7022 |
| 5 | Президиум РАН | 7 |
| 6 | Президиум РАН | 18 |
Abstract:
As the catalytic cycle for electrochemical hydrogen generation includes cobalt(I, II, and III)-containing clathrochelate species, we performed a detailed study of their electronic structure. The Co K-edge spectra demonstrated a lowering of the Co 1s ionization potentials from cobalt(III) complexes to their cobalt(II)-containing analogs and then to the cobalt(I) clathrochelates. The absence of pre-edge structure and specific peculiarities suggested a high symmetry of the N6-coordination polyhedra of an encapsulated cobalt(I) ion. The Co 2p core-level spectra contained very weak shakeup satellites, suggesting a hybridization of the cobalt-localized 3d orbitals and the valent orbitals of their encapsulating ligands, while the binding energy Co 2p3/2 increased with a formal oxidation state of an encapsulated cobalt ion(I, II, or III) from 780.5–780.8 eV and 780.9–781.2 eV to 781.8–782.2 eV. The Cl 2p, C 1s, N 1s, O 1s, B 1s, and Co 2p core-level spectra and data of X-ray absorption near edge structure (XANES) proved that both the electronic and spatial structures of the highly conjugated polyene macrobicyclic ligands are affected by the metal-localized redox processes. The nature of these encapsulating ligands influenced the redox characteristics of the caged metallocenters, allowing them to adopt unusual catalytically active oxidation state.
Cite:
Kochubey D.
, Kaichev V.
, Saraev A.
, Tomyn S.
, Belov A.
, Voloshin Y.
Combined X-Ray Absorption Near-Edge Structure and X-ray Photoelectron Study of the Electrocatalytically Active Cobalt(I) Cage Complexes and the Clathrochelate Cobalt(II)- and Cobalt(III)-Containing Precursors and Analogs
The Journal of Physical Chemistry C. 2013. V.117. N6. P.2753-2759. DOI: 10.1021/jp3085606 WOS Scopus РИНЦ ANCAN OpenAlex
Combined X-Ray Absorption Near-Edge Structure and X-ray Photoelectron Study of the Electrocatalytically Active Cobalt(I) Cage Complexes and the Clathrochelate Cobalt(II)- and Cobalt(III)-Containing Precursors and Analogs
The Journal of Physical Chemistry C. 2013. V.117. N6. P.2753-2759. DOI: 10.1021/jp3085606 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Aug 29, 2012 |
| Accepted: | Jan 11, 2013 |
| Published online: | Jan 31, 2013 |
| Published print: | Feb 14, 2013 |
Identifiers:
| Web of science: | WOS:000315181800043 |
| Scopus: | 2-s2.0-84873975724 |
| Elibrary: | 20434364 |
| Chemical Abstracts: | 2013:78437 |
| Chemical Abstracts (print): | 158:315050 |
| OpenAlex: | W2036826659 |