Catalytic Metallopolymers from [2Fe‐2S] Clusters: Artificial Metalloenzymes for Hydrogen Production

Karayilan, Metin; Brezinski, William P.; Clary, Kayla E.; Lichtenberger, Dennis L.; Glass, Richard S.; Pyun, Jeffrey

doi:10.1002/anie.201813776

Cited by 64 publications

(40 citation statements)

References 79 publications

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“…Hydrogen is an ideal fuel with gravimetric energy density up to 142 MJ kg À1 , which is almost three times larger than that of gasoline. 56 More importantly, H 2 combustion produces water with no pollution to the environment. Photocatalytic hydrogen evolution using semiconductors is a sustainable and economical technology to convert solar energy into hydrogen energy.…”

Section: Photocatalytic H 2 Evolutionmentioning

confidence: 99%

Conjugated polymers for visible-light-driven photocatalysis

Dai

Liu

2020

Energy Environ. Sci.

532

341

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Section: Photocatalytic H 2 Evolutionmentioning

confidence: 99%

Conjugated polymers for visible-light-driven photocatalysis

Dai

Liu

2020

Energy Environ. Sci.

532

341

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“…Under visible light excitation, the photoexcited electrons were generated from the conduction band of QDs, photoexcited electrons were rapidly transferred to the active center (H-cluster) through Fe-S clusters (F-clusters) in hydrogenases, realizing proton reduction and H 2 production. [7,[43][44][45]…”

Section: The Possible Electron Transfer Mechanismmentioning

confidence: 99%

A Periplasmic Photosensitized Biohybrid System for Solar Hydrogen Production

Luo

Wang

et al. 2021

Advanced Energy Materials

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inorganic-biohybrid system is of great interest because it merges the advantages of the inorganic photosensitizer with efficient light absorption and hydrogenase with high catalytic efficiency. [5][6][7][8] Accordingly, considerable efforts have been made to fabricate the purified hydrogenase biohybrid systems. [9][10][11][12][13][14][15][16] However, the low yield and complicated purification process of hydrogenase severely restrict the wide application of these biohybrid systems.A novel approach using whole cells expressing hydrogenases as the biocatalyst has shown obvious advantages over purified hydrogenases biohybrid system due to the easy fabrication and high stability. To date, two classes of whole-cell biohybrid systems were pursued, in the form of the extracellular photosensitized biohybrid system and the cytoplasmic photosensitized biohybrid system. [17][18][19][20][21][22][23] In the extracellular photosensitized biohybrid system (Figure S1a, Supporting Information), photoexcited electrons from extracellular photosensitizers were delivered to the hydrogenase in the cell through diffusional redox mediators or membrane-bound redox-active proteins, further realizing the solar hydrogen production. Honda and coworkers pioneered the fabrication of the TiO 2 /Escherichia coli extracellular photosensitized biohybrid system, which showed boosted photocatalytic H 2 production. [17] However, the extracellular photosensitized biohybrid system suffers from the sluggish electron transfer owing to the slow transmembrane process. To address this issue, a cytoplasmic photosensitized biohybrid system had been developed by implanting ultrasmall Au nanoclusters into the cytoplasm of Moorella thermoacetica and therefore realized durable solar-driven CO 2 fixation. [22] In this cytoplasmic photosensitized biohybrid system (Figure S1b, Supporting Information), interfacial electron transfer between the photosensitizer and the enzyme occurred in the cytoplasm, thereby avoiding energy loss during transmembrane electron transfer. This strategy provides new insight for the development of more efficient whole-cell biohybrid systems.It is known that there is a periplasmic space located between the outer membrane and the cytoplasm in the Gram-negative bacterial cell. [24] Compared to the cytoplasm, the periplasm is at a short distance from the outer membrane, where is favorable for light absorption. Furthermore, the narrow space Whole-cell inorganic-biohybrid systems, integrating inorganic photosensitizers with intact living cells, have shown great potential for solar hydrogen production. However, the typical whole cell biohybrid system often suffers from the sluggish kinetics of electron transfer in the transmembrane diffusion process, which severely restrict their photocatalytic activity. Here, a unique periplasmic photosensitized biohybrid system is constructed by translocating CuInS 2 /ZnS quantum dots (QDs) into the Shewanella oneidensis MR-1 (SW) cells that express periplasmic hydrogenases. The photoexcitation and electron tra...

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“…The electro‐ and photocatalytic hydrogen evolution reaction (HER) is at the heart of a H 2 ‐based new energy society . In nature, hydrogenases can mediate the reversible H 2 /H + conversion, but the use of these enzymes suffer from difficulties in their scale‐up preparation and also from their inactivation under aerobic conditions . As a result, developing HER catalysts that are cheap, efficient, and robust has attracted increasing interests …”

Section: Figurementioning

confidence: 99%

Water‐Soluble Polymers with Appending Porphyrins as Bioinspired Catalysts for the Hydrogen Evolution Reaction

et al. 2020

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Molecular design to improve catalyst performance is significant but challenging. In enzymes, residue groups that are close to reaction centers play critical roles in regulating activities. Using this bioinspired strategy, three water‐soluble polymers were designed with appending Co porphyrins and different side‐chain groups to mimic enzyme reaction centers and activity‐controlling residue groups, respectively. With these polymers, high hydrogen evolution efficiency was achieved in neutral aqueous media for electro‐ (turnover frequency >2.3×104 s−1) and photocatalysis (turnover number >2.7×104). Porphyrin units are surrounded and protected by polymer chains, and more importantly, the activity can be tuned with different side‐chain groups. Therefore, instead of revising molecular structures that is difficult from both design and synthesis points of view, polymers can be used to improve molecular solubility and stability and simultaneously regulate activity by using side‐chain groups.

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Catalytic Metallopolymers from [2Fe‐2S] Clusters: Artificial Metalloenzymes for Hydrogen Production

Cited by 64 publications

References 79 publications

Conjugated polymers for visible-light-driven photocatalysis

Conjugated polymers for visible-light-driven photocatalysis

A Periplasmic Photosensitized Biohybrid System for Solar Hydrogen Production

Water‐Soluble Polymers with Appending Porphyrins as Bioinspired Catalysts for the Hydrogen Evolution Reaction

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