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

Abstract

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.more » This work benchmarks a significant advance toward improving photosynthetic efficiency for solar fuel production.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1479589
Alternate Identifier(s):
OSTI ID: 1491804
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 45; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
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

Citation Formats

Utschig, Lisa M., Soltau, Sarah R., Mulfort, Karen L., Niklas, Jens, and Poluektov, Oleg G. Z-scheme solar water splitting via self-assembly of photosystem I-catalyst hybrids in thylakoid membranes. United Kingdom: N. p., 2018. Web. doi:10.1039/C8SC02841A.
Utschig, Lisa M., Soltau, Sarah R., Mulfort, Karen L., Niklas, Jens, & Poluektov, Oleg G. Z-scheme solar water splitting via self-assembly of photosystem I-catalyst hybrids in thylakoid membranes. United Kingdom. doi:10.1039/C8SC02841A.
Utschig, Lisa M., Soltau, Sarah R., Mulfort, Karen L., Niklas, Jens, and Poluektov, Oleg G. Wed . "Z-scheme solar water splitting via self-assembly of photosystem I-catalyst hybrids in thylakoid membranes". United Kingdom. doi:10.1039/C8SC02841A.
@article{osti_1479589,
title = {Z-scheme solar water splitting via self-assembly of photosystem I-catalyst hybrids in thylakoid membranes},
author = {Utschig, Lisa M. and Soltau, Sarah R. and Mulfort, Karen L. and Niklas, Jens and Poluektov, Oleg G.},
abstractNote = {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.},
doi = {10.1039/C8SC02841A},
journal = {Chemical Science},
number = 45,
volume = 9,
place = {United Kingdom},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8SC02841A

Citation Metrics:
Cited by: 1 work
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Figures / Tables:

Fig. 1 Fig. 1: Proposed photosynthetic Z-scheme electron transport in thylakoid membranes for H2 production. Photons absorbed by Photosystem II(PSII) are used to oxidize water in the oxygen-evolving complex (OEC) connected to PSII. The extracted electrons are passed on to Photosystem I(PSI)viathe plastoquinone (PQ) pool, the cytochrome b6f complex (Cyt b6f) andmore » the luminal electron transfer proteins plastocyanin (PC) orcytochrome c6 (Cyt c6). Upon light excitation, PSI transfers electrons from the luminal side to the stromal side of the membrane where, in thenative system, the soluble electron transfer protein ferredoxin (Fd) is reduced, transporting electrons to ferredoxin-NADP+ oxidoreductase (FNR)for the reduction of NADP+ to NADPH. In our system, bound catalyst at the acceptor end of PSI hijacks the light-generated electrons meant forFd, utilizing these electrons for H2 production. Protein structures: PSII (2axt), Cyt b6f (2D2C), PC (1bxu), PSI (1JB0).« less

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