Charge separation related to photocatalytic H2 production from a Ru–apoflavodoxin–Ni biohybrid

Soltau, Sarah R.; Niklas, Jens; Dahlberg, Peter D.; Mulfort, Karen L.; Poluektov, Oleg G.; Utschig, Lisa M.

doi:10.1021/acsenergylett.6b00614

Title: Charge separation related to photocatalytic H₂ production from a Ru–apoflavodoxin–Ni biohybrid

Journal Article · Tue Dec 27 00:00:00 EST 2016 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.6b00614· OSTI ID:1364651

Soltau, Sarah R. ^[1];

^[2]; Dahlberg, Peter D. ^[3]; Mulfort, Karen L. ^[2]; Poluektov, Oleg G. ^[2];

^[2]

Argonne National Lab. (ANL), Argonne, IL (United States); Bridgewater State Univ., Bridgewater, MA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); The Univ. of Chicago, Chicago, IL (United States); Stanford Univ., Stanford, CA (United States)

The direct creation of a fuel from sunlight and water via photochemical energy conversion provides a sustainable method for producing a clean source of energy. Here we report the preparation of a solar fuel biohybrid that embeds a nickel diphosphine hydrogen evolution catalyst into the cofactor binding pocket of the electron shuttle protein, flavodoxin (Fld). The system is made photocatalytic by linking a cysteine residue in Fld to a ruthenium photosensitizer. Importantly, the protein environment enables the otherwise insoluble Ni catalyst to perform photocatalysis in aqueous solution over a pH range of 3.5–12.0, with optimal turnover frequency 410 ± 30 h^–1 and turnover number 620 ± 80 mol H₂/mol hybrid observed at pH 6.2. For the first time, a reversible light-induced charge-separated state involving a Ni(I) intermediate was directly monitored by electron paramagnetic resonance spectroscopy. As a result, transient optical measurements reflect two conformational states, with a Ni(I) state formed in ~1.6 or ~185 μs that persists for several milliseconds as a long-lived charge-separated state facilitated by the protein matrix.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1364651

Journal Information:: ACS Energy Letters, Vol. 2, Issue 1; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 18 works

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Title: Charge separation related to photocatalytic H₂ production from a Ru–apoflavodoxin–Ni biohybrid