Biological Components and Bioelectronic Interfaces of Water Splitting Photoelectrodes for Solar Hydrogen Production

Braun, Artur; Boudoire, Florent; Bora, Debajeet K.; Faccio, Greta; Hu, Yelin; Kröll, Alexandra; Mun, Bongjin Simon; Wilson, Samuel T.

doi:10.1002/chem.201405123

Cited by 10 publications

(9 citation statements)

References 77 publications

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“…16,[74][75][76][77] Only a handful of MOFs have been reported that are capable of performing electrocatalytically driven water oxidation and reduction. Simplistically speaking, an electrocatalytic system eliminates many of the complexities of the Z-scheme, because the cathode (reducing electrode) and the anode (oxidising electrode) mediate direct reduction of H + into dihydrogen and oxidation of OH À into dioxygen respectively, when a sufficient overpotential is applied.…”

Section: Mof Supported Electrocatalytically Driven Water Splittingmentioning

confidence: 99%

Metal organic frameworks for photo-catalytic water splitting

Meyer

Ranocchiari

Bokhoven

2015

Energy Environ. Sci.

292

173

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Metal organic frameworks (MOFs) have recently debuted as participants and solid supports in catalytic water splitting. Their porosity and structural versatility offer a tantalising consolidation of the components needed for solar light harvesting and water splitting. Herein, we describe a selection of relevant contemporary investigations that employ electrocatalysis, chemically introduced redox partners, and photo-catalysts to generate dioxygen and dihydrogen from water. The role of semiconducting MOFs in these systems is addressed, in tandem with band gap control by linker functionalisation and doping. Considered holistically, MOFs offer an impressive physical, spatial and chemical versatility with which to support and sustain water splitting reactions. Major challenges toward practical implementation do remain, but opportunities for development are evidently numerous. Broader contextGrowing experimental and computational evidence suggests that metal organic frameworks (MOFs) can make a meaningful contribution to catalytically promoted water splitting. They offer an impressive physical, spatial, chemical and electronic mutability with which to support and sustain water splitting halfreactions. Their classical features -thermal stability, large surface area, high porosity and modularity -define them as versatile solid supports. Building on a vast library of existing frameworks, post-synthetic modification techniques allow further tailoring of intrinsic MOF properties and functionality. Compelling parallels are now being drawn between semiconductors and a select group of MOFs that are capable of sustaining a photo-generated charge separated state and using the resultant charge carriers to perform chemical transformations. In this perspective we describe a selection of contemporary electrocatalytic, chemically promoted, and photo-catalytic investigations that apply MOFs to water oxidation and reduction half reactions. We highlight successful strategies employed by the scientific community for engineering of catalytic sites, managing redox half-reactions, introducing light sensitisation and band gap tuning -all within the confines of a framework. Major challenges toward practical application certainly remain, but the adaptive nature of MOFs stands to make a poignant contribution to the discourse on photo-catalysed water splitting.Scheme 1 Proton reduction (1) and water oxidation (2) half reactions (NHE, 25 1C, pH 0). ; Tel: +41 (0)56 310 5843 † During the period between submission and revision of our manuscript a couple of examples of water reduction carried out by, or in the presence of MOFs, have appeared in the literature. We refer readers to the papers by: Du et al. concerning a nickel mercaptopyrimidine MOF with a TOF of 10.6 h À1 in the presence of triethylamine and fluorescein under blue light, 124 and Chen et al. describing a photosensitised MOF encapsulating a platinum dihydrogen evolving catalyst (Ru-Pt@UiO-67). 125

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Section: Mof Supported Electrocatalytically Driven Water Splittingmentioning

confidence: 99%

Metal organic frameworks for photo-catalytic water splitting

Meyer

Ranocchiari

Bokhoven

2015

Energy Environ. Sci.

292

173

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“…Indirect photochemical reactions are initiated by substances that absorb radiation and subsequently facilitate other reactions that do not involve the original light-absorbing substance [ 42 ]. For example, excited electrons and holes can be indirectly generated in semiconductors by light of lower energy than the band gap: the semiconductor itself does not absorb this light, but another substance (possibly even another semiconductor) that does absorb this light may be excited, and if this substance is in contact with the semiconductor and has appropriate energy levels, electrons can then be transferred between the excited substance and the semiconductor [ 48 , 68 , 79 – 81 ] (Fig. 3 d).…”

Section: Classification Of Photogeochemical Reactionsmentioning

confidence: 99%

“…The study of photogeochemistry, while purely chemical in nature, may even venture into the domain of biology and identify more of the ways in which compounds derived from living organisms can influence abiotic photochemistry [e.g., 81 ], as well as more of the unique relationships between photochemical reactions and biological metabolism known as photobiocatalysis [ 147 – 149 ].…”

Section: Experimental Approachesmentioning

confidence: 99%

A survey of photogeochemistry

Doane

2017

Geochem Trans

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The participation of sunlight in the natural chemistry of the earth is presented as a unique field of study, from historical observations to prospects for future inquiry. A compilation of known reactions shows the extent of light-driven interactions between naturally occurring components of land, air, and water, and provides the backdrop for an outline of the mechanisms of these phenomena. Catalyzed reactions, uncatalyzed reactions, direct processes, and indirect processes all operate in natural photochemical transformations, many of which are analogous to well-known biological reactions. By overlaying photochemistry and surface geochemistry, complementary approaches can be adopted to identify natural photochemical reactions and discern their significance in the environment.

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“…These photons have deep penetration and therefore can generate holes beyond the depletion layer; hence they recombine fast with the electrons before they arrive to the surface. The performance of pristine hematite can be improved by increasing the semiconductor -electrolyte interface area via nanostructuring [7,39,46], cation doping [43], or by surface functionalization with proteins [8,9,21,28,39,40] which can enhance electron injection into the conduction band.…”

Section: Introductionmentioning

confidence: 99%

Hematite photoanode co-functionalized with self-assembling melanin and C-phycocyanin for solar water splitting at neutral pH

et al. 2017

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Nature provides functional units which can be integrated in inorganic solar cell materials, such as light harvesting antenna proteins and photosynthetic molecular machineries, and thus help in advancing artificial photosynthesis. Their integration needs to address mechanical adhesion, light capture, charge transfer and corrosion resistance. We showed recently how enzymatic polymerization of melanin can immobilize the cyanobacterial light harvesting protein C-phycocyanin on the surface of hematite, a prospective metal oxide photoanode for solar hydrogen production by water splitting in photoelectrochemical cells. After the optimization of the functionalization procedure, in this work we show increased reproducible hydrogen production, measured parallel to the photocurrent on this bio-hybrid electrode in benign neutral pH phosphate. Over 90% increase compared to the photocurrent of the pristine hematite could be achieved. The hydrogen evolution was monitored during the photoelectrochemical measurement in an improved photoelectrochemical cell. The C-phycocyanin-melanin coating on the hematite was shown to exhibit a comb-like fractal pattern. Raman spectroscopy supported the presence of the protein on the hematite anode surface. The stability of the protein coating is demonstrated during the 2 h GC measurement and in an operando 24 h current density measurement.

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Biological Components and Bioelectronic Interfaces of Water Splitting Photoelectrodes for Solar Hydrogen Production

Cited by 10 publications

References 77 publications

Metal organic frameworks for photo-catalytic water splitting

Metal organic frameworks for photo-catalytic water splitting

A survey of photogeochemistry

Hematite photoanode co-functionalized with self-assembling melanin and C-phycocyanin for solar water splitting at neutral pH

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