Defining Intermediates of Nitrogenase MoFe Protein during N2 Reduction under Photochemical Electron Delivery from CdS Quantum Dots

Chica, Bryant; Ruzicka, Jesse; Kallas, Hayden; Mulder, David W.; Brown, Katherine A.; Peters, John W.; Seefeldt, Lance C.; Dukovic, Gordana; King, Paul W.

doi:10.1021/jacs.0c06343

Defining Intermediates of Nitrogenase MoFe Protein during N₂ Reduction under Photochemical Electron Delivery from CdS Quantum Dots

Journal Article · Mon Jul 27 00:00:00 EDT 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c06343· OSTI ID:1660131

^[1]; Ruzicka, Jesse ^[2]; ^[3]; ^[1]; ^[1]; ^[4]; ^[3]; ^[2]; ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
Univ. of Colorado, Boulder, CO (United States)
Utah State Univ., Logan, UT (United States)
Washington State Univ., Pullman, WA (United States)

Coupling the nitrogenase MoFe protein to light-harvesting semiconductor nanomaterials replaces the natural electron transfer complex with Fe protein and ATP and provides low potential photoexcited electrons for photocatalytic N₂ reduction. A central question is how direct photochemical electron delivery from nanocrystals to MoFe protein is able to support the multi-electron ammonia production reaction. In this study, low photon flux conditions were used to identify the initial reaction intermediates of CdS quantum dot (QD):MoFe protein nitrogenase complexes under photochemical activation. Illumination of CdS QD:MoFe protein complexes led to redox changes in the MoFe protein active site FeMo-co observed as the gradual decline in E0 resting state intensity that was accompanied by an increase in intensity of a new “g_eff = 4.5” EPR signal. The magnetic properties of the g_eff = 4.5 signal support assignment as a reduced S = 3/2 state, and reaction modeling was used to define it as a two-electron reduced “E₂” intermediate. Use of a MoFe protein variant, ß-188^Cys, which poises the P cluster in the oxidized P⁺ state, demonstrated the P cluster can function as a site of photoexcited electron delivery from CdS to MoFe protein. Overall, the results establish the initial steps for how photoexcited CdS delivers electrons into MoFe protein during reduction of N₂ to ammonia, and the role of electron flux in the photochemical reaction cycle.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1660131

Report Number(s):: NREL/JA--2700-77378; MainId:26324; UUID:75dc299c-6924-47b8-aacf-819e0558adad; MainAdminID:15167

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 33 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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