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Probing the Electro...
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Koroidov, SergeyStanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA;Stockholm Univ, Dept Phys, AlbaNova Univ Ctr, S-10691 Stockholm, Sweden
(author)
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
- Article/chapterEnglish2018
Publisher, publication year, extent ...
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2018-10-11
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AMER CHEMICAL SOC,2018
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LIBRIS-ID:oai:DiVA.org:uu-387252
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https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-387252URI
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https://doi.org/10.1021/acs.inorgchem.8b01497DOI
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Language:English
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Summary in:English
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Subject category:ref swepub-contenttype
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Subject category:art swepub-publicationtype
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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.
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Hong, KiryongStanford 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
(author)
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Kjaer, Kasper S.Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA;Lund Univ, Dept Chem Phys, POB 124, S-22100 Lund, Sweden
(author)
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Li, LinStanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA(Swepub:uu)linli826
(author)
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Kunnus, KristjanStanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
(author)
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Reinhard, MarcoStanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
(author)
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Hartsock, Robert W.Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
(author)
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Amit, DasUniv Rochester, Dept Chem, RC Box 270216, Rochester, NY 14627 USA;Univ Wisconsin, Dept Chem, 1101 Univ Ave, Madison, WI 53706 USA
(author)
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Eisenberg, RichardUniv Rochester, Dept Chem, RC Box 270216, Rochester, NY 14627 USA
(author)
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Das Pemmaraju, C.SLAC Natl Accelerator Lab, Theory Inst Mat & Energy Spectroscopies, Menlo Pk, CA 94025 USA
(author)
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Gaffney, Kelly J.Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
(author)
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Cordones, Amy A.Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
(author)
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Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA;Stockholm Univ, Dept Phys, AlbaNova Univ Ctr, S-10691 Stockholm, SwedenStanford 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
(creator_code:org_t)
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In:Inorganic Chemistry: AMER CHEMICAL SOC57:21, s. 13167-131750020-16691520-510X
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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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