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Probing the Electro...
Probing the Electron Accepting Orbitals of Ni-Centered Hydrogen Evolution Catalysts with Noninnocent Ligands by Ni L-Edge and S K-Edge X-ray Absorption
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- Koroidov, Sergey (author)
- Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA;Stockholm Univ, Dept Phys, AlbaNova Univ Ctr, S-10691 Stockholm, Sweden
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- Hong, Kiryong (author)
- Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA;Korea Res Inst Stand & Sci, Ctr Gas Anal, Div Chem & Med Metrol, Daejeon 34113, South Korea
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- Kjaer, Kasper S. (author)
- Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA;Lund Univ, Dept Chem Phys, POB 124, S-22100 Lund, Sweden
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- Li, Lin (author)
- Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
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- Kunnus, Kristjan (author)
- Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
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- Reinhard, Marco (author)
- Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
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- Hartsock, Robert W. (author)
- Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
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- Amit, Das (author)
- Univ Rochester, Dept Chem, RC Box 270216, Rochester, NY 14627 USA;Univ Wisconsin, Dept Chem, 1101 Univ Ave, Madison, WI 53706 USA
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- Eisenberg, Richard (author)
- Univ Rochester, Dept Chem, RC Box 270216, Rochester, NY 14627 USA
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- Das Pemmaraju, C. (author)
- SLAC Natl Accelerator Lab, Theory Inst Mat & Energy Spectroscopies, Menlo Pk, CA 94025 USA
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- Gaffney, Kelly J. (author)
- Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
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- Cordones, Amy A. (author)
- Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
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(creator_code:org_t)
- 2018-10-11
- 2018
- English.
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In: Inorganic Chemistry. - : AMER CHEMICAL SOC. - 0020-1669 .- 1520-510X. ; 57:21, s. 13167-13175
- Related links:
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https://www.osti.gov...
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
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- The valence electronic structure of several square planar Ni-centered complexes, previously shown to catalyze the hydrogen evolution reaction, are characterized using S K-edge and Ni L-edge X-ray absorption spectroscopy and electronic structure calculations. Measurement of the atomic Ni 3d and S 3p contributions enables assessment of the metal-ligand covalency of the electron accepting valence orbitals and yields insight into the ligand-dependent reaction mechanisms proposed for the catalysts. The electron accepting orbital of the Ni(abt)(2) (abt = 2-aminobenzenethiolate) catalyst is found to have large ligand character (80%), with only 9% S 3p (per S) character, indicating delocalization over the entire abt ligand. Upon two proton-coupled reductions to form the Ni(abt-H)(2) intermediate, the catalyst stores 1.8 electrons on the abt ligand, and the ligand N atoms are protonated, thus supporting its role as an electron and proton reservoir. The electron accepting orbitals of the Ni(abt-H)(2) intermediate and Ni(mpo)(2) (mpo = 2-mercaptopyridyl-N-oxide) catalyst are found to have considerably larger Ni 3d (46-47%) and S 3p (17-18% per S) character, consistent with an orbital localized on the metal-ligand bonds. This finding supports the possibility of metal-based chemistry, resulting in Ni-H bond formation for the reduced Ni(abt-H)(2) intermediate and Ni(mpo)(2) catalyst, a critical reaction intermediate in H-2 generation.
Subject headings
- NATURVETENSKAP -- Kemi -- Oorganisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)
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- ref (subject category)
- art (subject category)
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- By the author/editor
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Koroidov, Sergey
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Hong, Kiryong
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Kjaer, Kasper S.
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Li, Lin
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Kunnus, Kristjan
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Reinhard, Marco
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Hartsock, Robert ...
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Amit, Das
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Eisenberg, Richa ...
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Das Pemmaraju, C ...
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Gaffney, Kelly J ...
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Cordones, Amy A.
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- About the subject
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- NATURAL SCIENCES
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NATURAL SCIENCES
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and Chemical Science ...
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and Inorganic Chemis ...
- Articles in the publication
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Inorganic Chemis ...
- By the university
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Uppsala University