Z-scheme solar water splitting via self-assembly of photosystem I-catalyst hybrids in thylakoid membranes

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

doi:10.1039/C8SC02841A

Title: Z-scheme solar water splitting via self-assembly of photosystem I-catalyst hybrids in thylakoid membranes

Journal Article · Wed Nov 21 00:00:00 EST 2018 · Chemical Science

DOI:https://doi.org/10.1039/C8SC02841A· OSTI ID:1479589

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Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, USA

Nature's solar energy converters, the Photosystem I (PSI) and Photosystem II (PSII) reaction center proteins, flawlessly manage photon capture and conversion processes in plants, algae, and cyanobacteria to drive oxygenic water-splitting and carbon fixation. Herein, we utilize the native photosynthetic Z-scheme electron transport chain to drive hydrogen production from thylakoid membranes by directional electron transport to abiotic catalysts bound at the stromal end of PSI. Pt-nanoparticles readily self-assemble with PSI in spinach and cyanobacterial membranes as evidenced by light-driven H₂ production in the presence of a mediating electron shuttle protein and the sacrificial electron donor sodium ascorbate. EPR characterization confirms placement of the Pt-nanoparticles on the acceptor end of PSI. In the absence of sacrificial reductant, H₂ production at PSI occurs via coupling to light-induced PSII O₂ evolution as confirmed by correlation of catalytic activity to the presence or absence of the PSII inhibitor DCMU. To create a more sustainable system, first-row transition metal molecular cobaloxime and nickel diphosphine catalysts were found to perform photocatalysis when bound in situ to cyanobacterial thylakoid membranes. Thus, the self-assembly of abiotic catalysts with photosynthetic membranes demonstrates a tenable method for accomplishing solar overall water splitting to generate H₂, a renewable and clean fuel. This work benchmarks a significant advance toward improving photosynthetic efficiency for solar fuel production.

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

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1479589

Alternate ID(s):: OSTI ID: 1491804

Journal Information:: Chemical Science, Journal Name: Chemical Science Vol. 9 Journal Issue: 45; ISSN 2041-6520

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

Citation Metrics:

Cited by: 15 works

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Related Subjects

14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Photosystem I
Photosystem II
Z-scheme
biohybrid
hydrogen production
photocatalysis
photosynthesis
solar fuels
thylakoid
water splitting