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, 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

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2018-10-11
AMER CHEMICAL SOC,2018
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LIBRIS-ID:oai:DiVA.org:uu-387252
https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-387252URI
https://doi.org/10.1021/acs.inorgchem.8b01497DOI

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Language:English
Summary in:English

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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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NATURVETENSKAP Kemi Oorganisk kemi hsv//swe
NATURAL SCIENCES Chemical Sciences Inorganic Chemistry hsv//eng

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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)
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)
Li, LinStanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA(Swepub:uu)linli826 (author)
Kunnus, KristjanStanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA (author)
Reinhard, MarcoStanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA (author)
Hartsock, Robert W.Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA (author)
Amit, DasUniv Rochester, Dept Chem, RC Box 270216, Rochester, NY 14627 USA;Univ Wisconsin, Dept Chem, 1101 Univ Ave, Madison, WI 53706 USA (author)
Eisenberg, RichardUniv Rochester, Dept Chem, RC Box 270216, Rochester, NY 14627 USA (author)
Das Pemmaraju, C.SLAC Natl Accelerator Lab, Theory Inst Mat & Energy Spectroscopies, Menlo Pk, CA 94025 USA (author)
Gaffney, Kelly J.Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA (author)
Cordones, Amy A.Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA (author)
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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