Sökning: onr:"swepub:oai:DiVA.org:uu-387252" >
Probing the Electro...
-
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
(författare)
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
- Artikel/kapitelEngelska2018
Förlag, utgivningsår, omfång ...
-
2018-10-11
-
AMER CHEMICAL SOC,2018
-
printrdacarrier
Nummerbeteckningar
-
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
Kompletterande språkuppgifter
-
Språk:engelska
-
Sammanfattning på:engelska
Ingår i deldatabas
Klassifikation
-
Ämneskategori:ref swepub-contenttype
-
Ämneskategori:art swepub-publicationtype
Anmärkningar
-
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.
Ämnesord och genrebeteckningar
Biuppslag (personer, institutioner, konferenser, titlar ...)
-
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
(författare)
-
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
(författare)
-
Li, LinStanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA(Swepub:uu)linli826
(författare)
-
Kunnus, KristjanStanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
(författare)
-
Reinhard, MarcoStanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
(författare)
-
Hartsock, Robert W.Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
(författare)
-
Amit, DasUniv Rochester, Dept Chem, RC Box 270216, Rochester, NY 14627 USA;Univ Wisconsin, Dept Chem, 1101 Univ Ave, Madison, WI 53706 USA
(författare)
-
Eisenberg, RichardUniv Rochester, Dept Chem, RC Box 270216, Rochester, NY 14627 USA
(författare)
-
Das Pemmaraju, C.SLAC Natl Accelerator Lab, Theory Inst Mat & Energy Spectroscopies, Menlo Pk, CA 94025 USA
(författare)
-
Gaffney, Kelly J.Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
(författare)
-
Cordones, Amy A.Stanford Univ, PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
(författare)
-
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)
Sammanhörande titlar
-
Ingår i:Inorganic Chemistry: AMER CHEMICAL SOC57:21, s. 13167-131750020-16691520-510X
Internetlänk
Hitta via bibliotek
Till lärosätets databas
- Av författaren/redakt...
-
Koroidov, Sergey
-
Hong, Kiryong
-
Kjaer, Kasper S.
-
Li, Lin
-
Kunnus, Kristjan
-
Reinhard, Marco
-
visa fler...
-
Hartsock, Robert ...
-
Amit, Das
-
Eisenberg, Richa ...
-
Das Pemmaraju, C ...
-
Gaffney, Kelly J ...
-
Cordones, Amy A.
-
visa färre...
- Om ämnet
-
- NATURVETENSKAP
-
NATURVETENSKAP
-
och Kemi
-
och Oorganisk kemi
- Artiklar i publikationen
-
Inorganic Chemis ...
- Av lärosätet
-
Uppsala universitet