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

Koroidov, Sergey; Hong, Kiryong; Kjaer, Kasper S.; Li, Lin; Kunnus, Kristjan; Reinhard, Marco; Hartsock, Robert W.; Amit, Das; Eisenberg, Richard; Pemmaraju, C. Das; Gaffney, Kelly J.; Cordones, Amy A.

doi:10.1021/acs.inorgchem.8b01497

Title: 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

Journal Article · 10 October 2018 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.8b01497 · OSTI ID:1490966

Koroidov, Sergey ^[1];

^[2]; Kjaer, Kasper S. ^[3];

^[4]; Kunnus, Kristjan ^[5]; Reinhard, Marco ^[5]; Hartsock, Robert W. ^[5]; Amit, Das ^[6]; Eisenberg, Richard ^[7]; Pemmaraju, C. Das ^[8]; Gaffney, Kelly J. ^[5];

^[5]

Stanford Univ., Stanford, CA (United States); Stockholm Univ., Stockholm (Sweden)
Stanford Univ., Stanford, CA (United States); Korea Research Institute of Standards and Science, Daejeon (Republic of Korea)
Stanford Univ., Stanford, CA (United States); Lund Univ., Lund (Sweden)
Stanford Univ., Stanford, CA (United States); Uppsala Univ., Uppsala (Sweden)
Stanford Univ., Stanford, CA (United States)
Univ. of Rochester, Rochester, NY (United States); Univ. of Wisconsin, Madison, WI (United States)
Univ. of Rochester, Rochester, NY (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

Here, 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 H₂ generation.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-76SF00515; SC0002106

OSTI ID:: 1490966

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 21 Vol. 57; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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