Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; Roubelakis, Manolis M.; Maher, Andrew G.; Lee, Chang Hoon; Chambers, Matthew B.; Hammes-Schiffer, Sharon; Nocera, Daniel G.

doi:10.1073/pnas.1414908111

Title: Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

Journal Article · Wed Oct 08 00:00:00 EDT 2014 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1414908111· OSTI ID:1348826

Bediako, D. Kwabena ^[1]; Solis, Brian H. ^[2]; Dogutan, Dilek K. ^[1]; Roubelakis, Manolis M. ^[1]; Maher, Andrew G. ^[1]; Lee, Chang Hoon ^[1]; Chambers, Matthew B. ^[1]; Hammes-Schiffer, Sharon ^[2]; Nocera, Daniel G. ^[1]

Harvard Univ., Cambridge, MA (United States)
Univ. of Illinois at Urbana-Champaign, Urbana, IL (United States)

Here, the hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring.

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Research Organization:: Harvard Univ., Cambridge, MA (United States)

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

Grant/Contract Number:: SC0009758

OSTI ID:: 1348826

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 111, Issue 42; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 148 works

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