Biohybrid architectures for efficient light-to-current conversion based on photosystem I within scalable 3D mesoporous electrodes

Stieger, Kai Ralf; Feifel, Sven C.; Lokstein, Heiko; Hejazi, Mahdi; Zouni, Athina; Lisdat, Fred

doi:10.1039/c6ta07141d

Cited by 70 publications

(127 citation statements)

References 65 publications

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“…The photoaction spectrum normalized to the peak under irradiation agrees well with the absorption spectrum of PSI in solution, which also corresponds to the absorption spectrum measured for a μITO‐PSI‐cyt‐ c electrode prepared by six spin coating steps (Figure a) . The photocurrent intensity increased linearly with an increase in the thickness of the μITO to reach 150 μA cm −2 . The incident light‐to‐current efficiency, that is external quantum efficiency (EQE), exhibits a maximum value of 11 % at a low light intensity, whereas the internal quantum efficiency (IQE) shows a peak value of 30 % as shown in Figure b, where the μITO structure exhibits an inverse opal mesoporous structure with nanoparticle surface roughness .…”

Section: Immobilization Of Photosynthetic Reaction Centers and Model supporting

confidence: 78%

“…The photocurrent intensity increased linearly with an increase in the thickness of the μITO to reach 150 μA cm −2 . The incident light‐to‐current efficiency, that is external quantum efficiency (EQE), exhibits a maximum value of 11 % at a low light intensity, whereas the internal quantum efficiency (IQE) shows a peak value of 30 % as shown in Figure b, where the μITO structure exhibits an inverse opal mesoporous structure with nanoparticle surface roughness . Cyt‐ c is bound to the surface to make the electrical connection of PSI to the μITO electrode surface .…”

Section: Immobilization Of Photosynthetic Reaction Centers and Model mentioning

confidence: 99%

“…The incident light‐to‐current efficiency, that is external quantum efficiency (EQE), exhibits a maximum value of 11 % at a low light intensity, whereas the internal quantum efficiency (IQE) shows a peak value of 30 % as shown in Figure b, where the μITO structure exhibits an inverse opal mesoporous structure with nanoparticle surface roughness . Cyt‐ c is bound to the surface to make the electrical connection of PSI to the μITO electrode surface . Photoexcitation of μITO electrode results in electron transfer from the base ITO electrode composed of sintered ITO nanoparticles (ITO NPs) to cyt‐ c , which then reduces PSI .…”

Section: Immobilization Of Photosynthetic Reaction Centers and Model mentioning

confidence: 99%

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Immobilization of Molecular Catalysts for Enhanced Redox Catalysis

2018

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In the homogenous phase, redox catalysts are often deactivated by bimolecular reactions. For example, the charge‐separated state of photoredox catalysts decayed via bimolecular back electron transfer reactions between the charge‐separated molecules to decrease the lifetimes of the catalytically active species. When photoredox catalysts are immobilized on solid supports, the lifetime of the charge‐separated state was remarkably elongated to enhance the photocatalytic activity. Immobilization of photoredox catalysts on electrodes is required for photocurrent generation, leading to development of solar cells. Metal‐oxygen intermediates, which are active for oxidation of various substrates including water oxidation, are also deactivated via bimolecular reactions to produce inactive forms such as dinuclear metal bis‐μ‐oxo complexes. Immobilization of metal complex catalysts on solid supports prohibits the bimolecular deactivation, enhancing the catalytic activity and stability. This Review focuses on recent development of immobilization of both organic and inorganic molecular catalysts on various supports for enhancement of the catalytic activity, selectivity and stability in thermal and photoinduced redox reactions.

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Section: Immobilization Of Photosynthetic Reaction Centers and Model supporting

confidence: 78%

Section: Immobilization Of Photosynthetic Reaction Centers and Model mentioning

confidence: 99%

Section: Immobilization Of Photosynthetic Reaction Centers and Model mentioning

confidence: 99%

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Immobilization of Molecular Catalysts for Enhanced Redox Catalysis

2018

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“…22 In this model, it was assumed that the only rate limitation was the cyt c -mediated ET on the donor side of the RC. This was valid because ET was optimized on the RC acceptor side by using a sufficiently high concentration of UQ 0 (1.5 mM) in the buffer solution 47 and a rotating disc electrode to mitigate limitations imposed by quinone diffusion, as reported in previous work.…”

Section: Resultsmentioning

confidence: 99%

Cytochrome c Provides an Electron-Funneling Antenna for Efficient Photocurrent Generation in a Reaction Center Biophotocathode

Friebe¹,

Millo²,

Swainsbury

et al. 2017

ACS Appl. Mater. Interfaces

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The high quantum efficiency of photosynthetic reaction centers (RCs) makes them attractive for bioelectronic and biophotovoltaic applications. However, much of the native RC efficiency is lost in communication between surface-bound RCs and electrode materials. The state-of-the-art biophotoelectrodes utilizing cytochrome c (cyt c) as a biological wiring agent have at best approached 32% retained RC quantum efficiency. However, bottlenecks in cyt c-mediated electron transfer have not yet been fully elucidated. In this work, protein film voltammetry in conjunction with photoelectrochemistry is used to show that cyt c acts as an electron-funneling antennae that shuttle electrons from a functionalized rough silver electrode to surface-immobilized RCs. The arrangement of the two proteins on the electrode surface is characterized, revealing that RCs attached directly to the electrode via hydrophobic interactions and that a film of six cyt c per RC electrostatically bound to the electrode. We show that the additional electrical connectivity within a film of cyt c improves the high turnover demands of surface-bound RCs. This results in larger photocurrent onset potentials, positively shifted half-wave reduction potentials, and higher photocurrent densities reaching 100 μA cm–2. These findings are fundamental for the optimization of bioelectronics that utilize the ubiquitous cyt c redox proteins as biological wires to exploit electrode-bound enzymes.

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“…Stieger et al. utilized porous ITO with isolated PSI by wiring T. elongatus ‐derived PSI via cyt c to the surface of 460 nm ITO pores, resulting in a 150 μA cm −2 photocurrent density with an applied potential of 100 mV vs. Ag/AgCl . Additionally, Ciornii et al.…”

Section: Introductionmentioning

confidence: 94%

Photosystem I Multilayers within Porous Indium Tin Oxide Cathodes Enhance Mediated Electron Transfer

et al. 2019

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Understanding and improving charge transfer pathways between extracted Photosystem I (PSI) protein complexes and electrodes is necessary for the development of low‐cost PSI‐based devices for energy conversion. We incorporated PSI multilayers within porous indium tin oxide (ITO) electrodes and observed a greater mediated photocurrent in comparison to multilayers on planar ITO. First, the mediated electron transfer (MET) pathway in the presence of 2,6‐dichlorophenolindophenol (DCPIP) and ascorbate (AscH) was studied via photochronoamperometry on planar ITO. ITO nanoparticles were then used to fabricate two porous electrode morphologies; mesoporous (20–100 nm pores) and macroporous (5 μm pores). PSI multilayers within macroporous ITO cathodes produced 42±5 μA cm−2 of photocurrent, three times the photocurrent produced by mesoporous ITO. Additionally, macroporous cathodes are able to utilize twice as much active surface area, when compared to mesoporous cathodes. Our findings show that MET within PSI multilayers is greater in 5 μm macropores than mesoporous ITO due to both an increase in electrode surface area and the location of PSI complexes within the pores. Improving MET in PSI‐based bioelectrodes has applications including improving the total charge transfer achieved in PSI‐based photoelectrochemical cells or even incorporation in bio‐photocatalytic cells.

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Biohybrid architectures for efficient light-to-current conversion based on photosystem I within scalable 3D mesoporous electrodes

Abstract: A 3D inverse-opal mesoporous scalable electrode utilizing photosystem I with high efficiency for photocurrent generation and providing insights into protein-surface electrochemistry.

Cited by 70 publications

References 65 publications

Immobilization of Molecular Catalysts for Enhanced Redox Catalysis

Immobilization of Molecular Catalysts for Enhanced Redox Catalysis

Cytochrome c Provides an Electron-Funneling Antenna for Efficient Photocurrent Generation in a Reaction Center Biophotocathode

Photosystem I Multilayers within Porous Indium Tin Oxide Cathodes Enhance Mediated Electron Transfer

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