[FeFe]-Hydrogenase and its organic molecule mimics—Artificial and bioengineering application for hydrogenproduction

Volbeda, 1995, Crystal structure of the nickel–iron hydrogenase from Desulfovibrio gigas, Nature, 373, 580, 10.1038/373580a0 Volbeda, 1996, Structure of the [NiFe] hydrogenase active site:  evidence for biologically uncommon Fe ligands, J. Am. Chem. Soc., 118, 12989, 10.1021/ja962270g Higuchi, 1999, Removal of the bridging ligand atom at the Ni-Fe active site of [NiFe] hydrogenase upon reduction with H2, as revealed by X-ray structure analysis at 1.4 Å resolution, Structure, 7, 549, 10.1016/S0969-2126(99)80071-9 Marr, 2001, Structural mimics for the active site of [NiFe] hydro genase, Coord. Chem. Rev., 219–221, 1055, 10.1016/S0010-8545(01)00396-4 Peters, 1998, X-ray crystal structure of the Fe-only hydrogenase (CpI) from Clostridium pasteurianum to 1.8 angstrom resolution, Science, 282, 1853, 10.1126/science.282.5395.1853 Nicolet, 1999, Desulfovibrio desulfuricans iron hydrogenase: the structure shows unusual coordination to an active site Fe binuclear center, Structure, 7, 13, 10.1016/S0969-2126(99)80005-7 Nicolet, 2001, Crystallographic and FTIR spectroscopic evidence of changes in Fe coordination upon reduction of the active site of the Fe-only hydrogenase from Desulfovibrio desulfuricans, J. Am. Chem. Soc., 123, 1596, 10.1021/ja0020963 Frey, 2002, Hydrogenases: hydrogen-activating enzymes, Chembiochem, 3, 153, 10.1002/1439-7633(20020301)3:2/3<153::AID-CBIC153>3.0.CO;2-B Dodds, 2015, Hydrogen and fuel cell technologies for heating: a review, Int. J. Hydrogen Energy, 40, 2065, 10.1016/j.ijhydene.2014.11.059 Cook, 2010, Solar energy supply and storage for the legacy and nonlegacy worlds, Chem. Rev., 110, 6474, 10.1021/cr100246c Lubitz, 2014, Hydrogenases, Chem. Rev., 114, 4081, 10.1021/cr4005814 Jones, 2002, Direct comparison of the electrocatalytic oxidation of hydrogen by an enzyme and a platinum catalyst, Chem. Commun., 866, 10.1039/b201337a Li, 2016, Synthesis of diiron(I) dithiolato carbonyl complexes, Chem. Rev., 116, 7043, 10.1021/acs.chemrev.5b00669 Schilter, 2016, Hydrogenase enzymes and their synthetic models: the role of metal hydeides, Chem. Rev., 116, 8693, 10.1021/acs.chemrev.6b00180 Lyon, 1999, Carbon monoxide and cyanide ligands in a classical organometallic complex model for Fe-only hydrogenase, Angew. Chem. Int. Ed., 38, 3178, 10.1002/(SICI)1521-3773(19991102)38:21<3178::AID-ANIE3178>3.0.CO;2-4 Schmidt, 1999, First generation analogues of the binuclear site in the Fe-only hydrogenases: Fe2(μ-SR)2(CO)4(CN)22−, J. Am. Chem. Soc., 121, 9736, 10.1021/ja9924187 Le Cloirec, 1999, A di-iron dithiolate possessing structural elements of the carbonyl/cyanide sub-site of the H-centre of Fe-only hydrogenase, Chem. Commun., 2285, 10.1039/a906391i Seyferth, 1980, The dithiobis(tricarbonyliron) dianion: improved preparation and new chemistry, J. Organomet. Chem., 192, C1, 10.1016/S0022-328X(00)93341-2 Seyferth, 1982, Chemistry of .mu.-dithio-bis(tricarbonyliron), a mimic of organic disulfides. 1. Formation of di-.mu.-thiolate-bis(tricarbonyliron) dianion, Organometallics, 1, 125, 10.1021/om00061a022 Freric Gloaguen, 2001, Synthetic and structural studies on [Fe2(SR)2(CN)x(CO)6-x]x− as active site models for Fe-only hydrogenases, J. Am. Chem. Soc., 123, 12518, 10.1021/ja016071v Gloaguen, 2001, Biomimetic hydrogen evolution catalyzed by an iron carbonyl thiolate, J. Am. Chem. Soc., 123, 9476, 10.1021/ja016516f Gloaguen, 2002, Bimetallic carbonyl thiolates as functional models for Fe-only hydrogenases, Inorg. Chem., 41, 6573, 10.1021/ic025838x Nehring, 2003, Dinuclear iron isonitrile complexes:  models for the iron hydrogenase active site, Inorg. Chem., 42, 4288, 10.1021/ic034334b Li, 2005, Influence of tertiary phosphanes on the coordination configurations and electrochemical properties of iron hydrogenase model complexes: crystal structures of [(μ-S2C3H6)Fe2(CO)6–nLn] (L=PMe2Ph, n=1, 2; PPh3, P(OEt)3, n=1), Eur. J. Inorg. Chem., 2506, 10.1002/ejic.200400947 Na, 2006, An approach to water-soluble hydrogenase active site models: synthesis and electrochemistry of diiron dithiolate complexes with 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane ligand(s), J. Organomet. Chem., 691, 5045, 10.1016/j.jorganchem.2006.08.082 Mejia-Rodriguez, 2004, The hydrophilic phosphatriazaadamantane ligand in the development of H2 production electrocatalysts:  iron hydrogenase model complexes, J. Am. Chem. Soc., 126, 12004, 10.1021/ja039394v Hou, 2006, Tris(N-pyrrolidinyl)phosphine substituted diiron dithiolate related to iron-only hydrogenase active site: synthesis, characterization and electrochemical properties, J. Organomet. Chem., 691, 4633, 10.1016/j.jorganchem.2006.07.010 Schwartz, 2006, Dynamic ligation at the first amine-coordinated iron hydrogenase active site mimic, Chem. Commun., 2, 4206, 10.1039/B608260B Hu, 2006, Iron–sulfur carbonyl compounds with unique terminal thioether ligation modelling for the active site of [Fe]-only hydrogenases, Chem. Lett., 35, 840, 10.1246/cl.2006.840 Tard, 2005, Synthesis of the H-cluster framework of iron-only hydrogenase, Nature, 433, 610, 10.1038/nature03298 Chong, 2003, Electrocatalysis of hydrogen production by active site analogues of the iron hydrogenase enzyme: structure/function relationships, Dalt. Trans., 4158, 10.1039/B304283A Felton, 2007, Hydrogen generation from weak acids:  electrochemical and computational studies of a diiron hydrogenase mimic, J. Am. Chem. Soc., 129, 12521, 10.1021/ja073886g Capon, 2004, Electrochemical proton reduction by thiolate-bridged hexacarbonyldiiron clusters, J. Electroanal. Chem., 566, 241, 10.1016/j.jelechem.2003.11.032 Donovan, 2012, Cyclic Voltammetric studies of chlorine-substituted diiron benzenedithiolato hexacarbonyl electrocatalysts inspired by the [FeFe]-hydrogenase active site, Organometallics, 31, 8067, 10.1021/om300938e Schwartz, 2008, Tuning the electronic properties of Fe2(μ-arenedithiolate)(CO)6-n(PMe3)n (n=0, 2) complexes related to the [Fe−Fe]-hydrogenase active site, Comptes Rendus Chim., 11, 875, 10.1016/j.crci.2008.04.001 Schwartz, 2008, Influence of an electron-deficient bridging o-carborane on the electronic properties of an [FeFe] hydrogenase active site model, Dalton Trans., 2379, 10.1039/b802908n Wright, 2009, Diiron proton reduction catalysts possessing electron-rich and electron-poor naphthalene-1, 8-dithiolate ligands, Chem. – Eur. J., 15, 8518, 10.1002/chem.200900989 Wang, 2009, Fluorophenyl-substituted Fe-only hydrogenases active site ADT models: different electrocatalytic process for proton reduction in HOAc and HBF4/Et2O, Dalton Trans., 2712, 10.1039/b818012a Chen, 2010, Synthesis of diiron hydrogenase mimics bearing hydroquinone and related ligands. electrochemical and computational studies of the mechanism of hydrogen production and the role of O–H···S hydrogen bonding, Organometallics, 29, 5330, 10.1021/om100396j Petro, 2008, Photoelectron spectroscopy of dithiolatodiironhexacarbonyl models for the active site of [Fe–Fe] hydrogenases: insight into the reorganization energy of the rotated structure in the enzyme, J. Mol. Struct., 890, 281, 10.1016/j.molstruc.2008.04.024 Charreteur, 2010, Effect of electron-withdrawing dithiolate bridge on the electron-transfer steps in diiron molecules related to [2Fe]H subsite of the [FeFe]-Hydrogenases, Inorg. Chem., 49, 2496, 10.1021/ic902401k Singh, 2009, (I, 0) Mixed-valence state of a diiron complex with pertinence to the [FeFe]-hydrogenase active site: an IR, EPR, and computational study, Inorg. Chem., 48, 10883, 10.1021/ic9016454 Mebi, 2010, Binuclear iron(I) complex containing bridging phenanthrene-4, 5-dithiolate ligand: preparation, spectroscopy, crystal structure, and electrochemistry, Z. Anorg. Allog. Chem., 636, 2550, 10.1002/zaac.201000236 Topf, 2012, Design: synthesis and characterization of a modular bridging ligand platform for bio-inspired hydrogen production, Inorg. Chem. Commun., 21, 147, 10.1016/j.inoche.2012.04.034 Ridley, 2013, Fluorinated models of the iron-only hydrogenase: an electrochemical study of the influence of an electron-withdrawing bridge on the proton reduction overpotential and catalyst stability, J. Electroanal. Chem., 703, 14, 10.1016/j.jelechem.2013.05.018 Gao, 2014, Iron–iron hydrogenase active subunit covalently linking to organic chromophore for light-driven hydrogen evolution, Int. J. Hydrogen Energy, 39, 10434, 10.1016/j.ijhydene.2014.05.003 Trautwein, 2013, The influence of OH groups in [Fe(CO)3]2[(μ-ECH2)2C(CH2OH)2] (E=S: Se) complexes toward the cathodic process, Z. Anorg. Allog. Chem., 639, 1512, 10.1002/zaac.201300106 Goy, 2015, Silicon–heteroaromatic [FeFe] hydrogenase model complexes: insight into protonation, electrochemical properties, and molecular structures, Chem. Eur. J., 21, 5061, 10.1002/chem.201406087 Jiang, 2007, Fe–S complexes containing five-membered heterocycles: novel models for the active site of hydrogenases with unusual low reduction potential, Dalt. Trans., 896, 10.1039/B615037C Thomas, 2007, Synthesis of carboxylic acid-modified [FeFe]-hydrogenase model complexes amenable to surface immobilization, Organometallics, 26, 3976, 10.1021/om7003354 Apfel, 2008, Functionalized sugars as ligands towards water-soluble [Fe-only] hydrogenase models, Eur. J. Inorg. Chem., 5112, 10.1002/ejic.200800720 Harb, 2009, Preparation and characterization of homologous diiron dithiolato, diselenato, and ditellurato complexes: [FeFe]-hydrogenase models, Organometallics, 28, 6666, 10.1021/om900675q De Carcer, 2006, Active-site models for iron hydrogenases:  reduction chemistry of dinuclear iron complexes, Inorg. Chem., 45, 8000, 10.1021/ic0610381 Song, 2009, Synthesis: characterization and electrocatalysis of diiron propanediselenolate derivatives as the active site models of [FeFe]-hydrogenases, J. Inorg. Biochem., 103, 805, 10.1016/j.jinorgbio.2009.02.002 Song, 2013, Synthesis, characterization, and electrochemical properties of diiron propaneditellurolate (PDTe) complexes as active site models of [FeFe]-hydrogenases, Dalt. Trans., 42, 1612, 10.1039/C2DT31976D Harb, 2012, Comparison of S and Se dichalcogenolato [FeFe]-hydrogenase models with central S and Se atoms in the bridgehead chain, Tetrahedron, 68, 10592, 10.1016/j.tet.2012.10.021 Song, 2013, Synthesis, structures, and some properties of diiron oxadiselenolate (ODSe) and thiodiselenolate (TDSe) complexes as models for the active site of [FeFe]-hydrogenases, Organometallics, 32, 3673, 10.1021/om400309j Harb, 2009, Phosphane- and phosphite-substituted diiron diselenolato complexes as models for [FeFe]-hydrogenases, Eur. J. Inorg. Chem., 3414, 10.1002/ejic.200900252 Harb, 2009, Synthesis and characterization of diiron diselenolato complexes including iron hydrogenase models, Organometallics, 28, 1039, 10.1021/om800748p Harb, 2010, Synthesis and characterization of [FeFe]–hydrogenase models with bridging moieties containing (S, Se) and (S, Te), Eur. J. Inorg. Chem., 3976, 10.1002/ejic.201000278 Trautwein, 2015, Steric effect of the dithiolato linker on the reduction mechanism of [Fe2(CO)6{μ-(XCH2)2CRR′}] hydrogenase models (X=S, Se), Dalt. Trans., 44, 18780, 10.1039/C5DT01387A Song, 2008, Synthesis and structural characterization of the mono- and diphosphine-containing diiron propanedithiolate complexes related to [FeFe]-hydrogenases. Biomimetic H2 evolution catalyzed by (μ-PDT)Fe2(CO)4[(Ph2P)2N(n-Pr)], J. Inorg. Biochem., 102, 1973, 10.1016/j.jinorgbio.2008.04.003 Bruschi, 2009, Influence of the [2Fe]H subcluster environment on the properties of key intermediates in the catalytic cycle of [FeFe] hydrogenases: hints for the rational design of synthetic catalysts, Angew. Chem. – Int. Ed., 48, 3503, 10.1002/anie.200900494 Filippi, 2015, DFT Dissection of the reduction step in H2 catalytic production by [FeFe]-hydrogenase-inspired models: can the bridging hydride become more reactive than the terminal isomer?, Inorg. Chem., 54, 9529, 10.1021/acs.inorgchem.5b01495 Zhao, 2001, H/D exchange reactions in dinuclear iron thiolates as activity assay models of Fe-H2ase, J. Am. Chem. Soc., 123, 9710, 10.1021/ja0167046 Dong, 2006, An insight into the protonation property of a diiron azadithiolate complex pertinent to the active site of Fe-only hydrogenases, Chem. Commun., 2, 305, 10.1039/B513270C Van Der Vlugt, 2005, Characterization of a diferrous terminal hydride mechanistically relevant to the Fe-only hydrogenases, J. Am. Chem. Soc., 127, 16012, 10.1021/ja055475a Ezzaher, 2007, Evidence for the formation of terminal hydrides by protonation of an asymmetric iron hydrogenase active site mimic, Inorg. Chem., 46, 3426, 10.1021/ic0703124 Orain, 2007, Use of 1,10-phenanthroline in diiron dithiolate derivatives related to the [Fe-Fe] hydrogenase active site, Dalton Trans., 3754, 10.1039/b709287c Morvan, 2007, N-heterocyclic carbene ligands in nonsymmetric diiron models of hydrogenase active sites, Organometallics, 26, 2042, 10.1021/om061173l Capon, 2005, N-heterocyclic carbene ligands as cyanide mimics in diiron models of the all-iron hydrogenase active site, Organometallics, 24, 2020, 10.1021/om049132h Tye, 2005, Dual electron uptake by simultaneous iron and ligand reduction in an N-heterocyclic carbene substituted [FeFe] Hydrogenase model compound, Organometallics, 44, 5550 Jiang, 2007, Preparation: characteristics and crystal structures of novel N-heterocyclic carbene substituted furan- and pyridine-containing azadithiolate Fe-S complexes, Polyhedron, 26, 1499, 10.1016/j.poly.2006.11.033 Duan, 2007, Carbene–pyridine chelating 2Fe2S hydrogenase model complexes as highly active catalysts for the electrochemical reduction of protons from weak acid (HOAc), Dalt. Trans., 1277, 10.1039/B616645H Becker, 2016, An iron–iron hydrogenase mimic with appended electron reservoir for efficient proton reduction in aqueous media, Sci. Adv., 2, e1501014, 10.1126/sciadv.1501014 Fan, 2001, A capable bridging ligand for fe-only hydrogenase:  density functional calculations of a low-energy route for heterolytic cleavage and formation of dihydrogen, J. Am. Chem. Soc., 123, 3828, 10.1021/ja004120i Schwartz, 2006, Iron hydrogenase active site mimic holding a proton and a hydride, Ott. Chem. Commun., 520, 10.1039/B514280F Eilers, 2007, Ligand versus metal protonation of an iron hydrogenase active site mimic, Chem. – Eur. J., 13, 7075, 10.1002/chem.200700019 Wang, 2007, electrochemical properties and molecular structures of halogen-functionalized diiron azadithiolate complexes related to the active site of iron-only hydrogenases, Dalton Trans., 3812, 10.1039/b706178a Justice, 2007, Chelate control of diiron(I) dithiolates relevant to the [Fe-Fe]- hydrogenase active site, Inorg. Chem., 46, 1655, 10.1021/ic0618706 Justice, 2007, Lewis vs. Brønsted-basicities of diiron dithiolates: spectroscopic detection of the rotated structure and remarkable effects of ethane- vs. propanedithiolate, Chem. Commun., 2019, 10.1039/B700754J Justice, 2007, Unsaturated: mixed-valence diiron dithiolate model for the Hox state of the [FeFe] hydrogenase, Angew. Chem. Int. Ed., 46, 6152, 10.1002/anie.200702224 Justice, 2008, Redox and structural properties of mixed-valence models for the active site of the [FeFe]-hydrogenase: progress and challenges, Inorg. Chem., 47, 7405, 10.1021/ic8007552 Barton, 2008, Terminal hydride in [FeFe]-hydrogenase model has lower potential for H2 production than the isomeric bridging hydride, Inorg. Chem., 47, 2261, 10.1021/ic800030y Dance, 2010, Mimicking nitrogenase, Dalton Trans., 39, 2972, 10.1039/b922606k Olsen, 2009, Hydrogen activation by biomimetic diiron dithiolates Inorg, Chem., 48, 7507 Carroll, 2012, Synthetic models for the active site of the [FeFe]-hydrogenase: catalytic proton reduction and the structure of the doubly protonated intermediate, J. Am. Chem. Soc., 134, 18843, 10.1021/ja309216v Huynh, 2014, Computational investigation of [FeFe]-hydrogenase models: characterization of singly and doubly protonated intermediates and mechanistic insights, Inorg. Chem., 53, 10301, 10.1021/ic5013523 Ott, 2003, Synthesis and structure of a biomimetic model of the iron hydrogenase active site covalently linked to a ruthenium photosensitizer, Angew. Chem. Int. Ed., 42, 3285, 10.1002/anie.200351192 Wolpher, 2003, Synthesis and properties of an iron hydrogenase active site model linked to a ruthenium tris-bipyridine photosensitizer, Inorg. Chem. Commun., 6, 989, 10.1016/S1387-7003(03)00140-0 Li, 2002, Iron carbonyl sulfides, formaldehyde, and amines condense to give the proposed azadithiolate cofactor of the Fe-only hydrogenases, J. Am. Chem. Soc., 124, 726, 10.1021/ja016964n Ott, 2003, Synthesis and structure of a biomimetic model of the iron hydrogenase active site covalently linked to a ruthenium photosensitizer, Angew. Chem. Int. Ed., 42, 3285, 10.1002/anie.200351192 Ekstrom, 2006, Bio-inspired, side-on attachment of a ruthenium photosensitizer to an iron hydrogenase active site model, Dalt. Trans., 4599, 10.1039/B606659C Song, 2006, A biomimetic model for the active site of Iron-only hydrogenases covalently bonded to a porphyrin photosensitizer, Angew. Chem. Int. Ed., 45, 1130, 10.1002/anie.200503602 Li, 2008, Noncovalent assembly of a metalloporphyrin and an iron hydrogenase active-site model: photo-induced electron transfer and hydrogen generation, J. Phys. Chem. B, 112, 8198, 10.1021/jp710498v Kluwer, 2009, Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution, Proc. Natl. Acad. Sci. U. S. A., 106, 10460, 10.1073/pnas.0809666106 Song, 2009, Synthesis, Structure, and photoinduced catalysis of [FeFe]-hydrogenase active site models covalently linked to a porphyrin or metalloporphyrin moiety, Organometallics, 28, 3834, 10.1021/om900141x Samuel, 2010, Ultrafast photodriven intramolecular electron transfer from a zinc porphyrin to a readily reduced diiron hydrogenase model complex, J. Am. Chem. Soc., 132, 8813, 10.1021/ja100016v Poddutoori, 2011, Photoinitiated multistep charge separation in ferrocene–zinc porphyrin–diiron hydrogenase model complex triads, Energy Environ. Sci., 4, 2441, 10.1039/c1ee01334c Wang, 2010, Photocatalytic hydrogen evolution by [FeFe] hydrogenase mimics in homogeneous solution, Chem. – Asian J., 5, 1796, 10.1002/asia.201000087 Wang, 2012, Electron transfer and hydrogen generation from a molecular dyad: platinum(II) alkynyl complex anchored to [FeFe] hydrogenase subsite mimic, Dalt. Trans., 41, 2420, 10.1039/c1dt11923k Cui, 2012, Efficient [FeFe] hydrogenase mimic dyads covalently linking to iridium photosensitizer for photocatalytic hydrogen evolution, Dalt. Trans., 41, 13899, 10.1039/c2dt31618h Goy, 2013, A silicon-heteroaromatic system as photosensitizer for light-driven hydrogen production by hydrogenase mimics, Eur. J. Inorg. Chem., 4466, 10.1002/ejic.201300537 Na, 2007, Intermolecular electron transfer from photogenerated Ru(bpy)3+ to [2Fe2S] model complexes of the iron-only hydrogenase active site, Inorg. Chem., 46, 3813, 10.1021/ic070234k Na, 2008, Visible light-driven electron transfer and hydrogen generation catalyzed by bioinspired [2Fe2S] complexes, Inorg. Chem., 47, 2805, 10.1021/ic702010w Streich, 2010, High-turnover photochemical hydrogen production catalyzed by a model complex of the [FeFe]-hydrogenase active site, Chem. – Eur. J., 16, 60, 10.1002/chem.200902489 Na, 2016, Photochemical hydrogen generation initiated by oxidative quenching of the excited Ru(bpy)32+* by a bio-inspired [2Fe2S] complex, Chem. – Eur. J., 22, 10365, 10.1002/chem.201600541 Zhang, 2010, Homogeneous photocatalytic production of hydrogen from water by a bioinspired [Fe2S2] catalyst with high turnover numbers, Dalt. Trans., 39, 1204, 10.1039/B923159P Lunsford, 2016, Catalysis and mechanism of H2 release from amine-boranes by diiron complexes, Inorg. Chem., 55, 964, 10.1021/acs.inorgchem.5b02601 Ibrahim, 2007, Electropolymeric materials incorporating subsite structures related to iron-only hydrogenase: active ester functionalised poly(pyrroles) for covalent binding of {2Fe3S}-carbonyl/cyanide assemblies, Chem. Commun., 1535, 10.1039/b617399c McGlynn, 2009, Hydrogenase cluster biosynthesis: organometallic chemistry nature's way, Dalt. Trans., 4274, 10.1039/b821432h Tooley, 2015, Toward a tunable synthetic [FeFe] hydrogenase mimic: single-chain nanoparticles functionalized with a single diiron cluster, Polym. Chem., 6, 7646, 10.1039/C5PY01196E Wang, 2010, Photocatalytic hydrogen evolution from rhenium(I) complexes to [FeFe] Hydrogenase mimics in aqueous sds micellar systems: a biomimetic pathway, Langmuir, 26, 9766, 10.1021/la101322s Wang, 2016, Amphiphilic polymeric micelles as microreactors: improving the photocatalytic hydrogen production of the [FeFe]-hydrogenase mimic in water, Chem. Commun., 52, 457, 10.1039/C5CC07499A Li, 2012, Photocatalytic H2 production in aqueous solution with host-guest inclusions formed by insertion of an FeFe-hydrogenase mimic and an organic dye into cyclodextrins, Energy Environ. Sci., 5, 8220, 10.1039/c2ee22109h Li, 2013, Exceptional dendrimer-based mimics of diiron hydrogenase for the photochemical production of hydrogen, Angew. Chem. Int. Ed., 52, 5631, 10.1002/anie.201301289 Jones, 2007, Synthetic hydrogenases incorporation of an iron carbonyl thiolate into a designed peptide, J. Am. Chem. Soc., 129, 14844, 10.1021/ja075116a Roy, 2011, Artificial [FeFe]-hydrogenase: on resin modification of an amino acid to anchor a hexacarbonyldiiron cluster in a peptide framework, Eur. J. Inorg. Chem., 1050, 10.1002/ejic.201000979 Roy, 2012, Photo-induced hydrogen production in a helical peptide incorporating a [FeFe] hydrogenase active site mimic, Chem. Commun., 48, 9816, 10.1039/c2cc34470j Sano, 2011, A hydrogenase model system based on the sequence of cytochrome c: photochemical hydrogen evolution in aqueous media, Chem. Commun., 47, 8229, 10.1039/c1cc11157d Sano, 2012, Photocatalytic hydrogen evolution by a diiron hydrogenase model based on a peptide fragment of cytochrome c556 with an attached diiron carbonyl cluster and an attached ruthenium photosensitizer, J. Inorg. Biochem., 108, 159, 10.1016/j.jinorgbio.2011.07.010 Onoda, 2014, Photoinduced hydrogen evolution catalyzed by a synthetic diiron dithiolate complex embedded within a protein matrix, ACS Catal., 4, 2645, 10.1021/cs500392e Nann, 2010, Water splitting by visible light: a nanophotocathode for hydrogen production, Angew. Chem. Int. Ed., 49, 1574, 10.1002/anie.200906262 Wu, 2014, Enhancement of the efficiency of photocatalytic reduction of protons to hydrogen via molecular assembly, Acc. Chem. Res., 47, 2177, 10.1021/ar500140r Jian, 2016, Comparison of H2 photogeneration by [FeFe]-hydrogenase mimics with CdSe QDs and Ru(bpy)3Cl2 in aqueous solution, Energy. Environ. Sci., 9, 2083, 10.1039/C6EE00629A Wang, 2011, A highly efficient photocatalytic system for hydrogen production by a robust hydrogenase mimic in an aqueous solution, Angew. Chem. Int. Ed., 50, 3193, 10.1002/anie.201006352 Wang, 2013, Exceptional poly(acrylic acid)-based artificial [FeFe]-hydrogenases for photocatalytic h2 production in water, Angew. Chem. Int. Ed., 52, 8134, 10.1002/anie.201303110 Liang, 2015, Branched polyethylenimine improves hydrogen photoproduction from a CdSe quantum dot/[FeFe]-hydrogenase mimic system in neutral aqueous solutions, Chem. – Eur. J., 21, 3187, 10.1002/chem.201406361 Wen, 2016, Secondary coordination sphere accelerates hole transfer for enhanced hydrogen photogeneration from [FeFe]-hydrogenase mimic and CdSe QDs in water, Sci. Rep., 6, 29851, 10.1038/srep29851 Jian, 2013, Chitosan confinement enhances hydrogen photogeneration from a mimic of the diiron subsite of [FeFe]-hydrogenase, Nat. Commun., 4, 2695, 10.1038/ncomms3695 Pullen, 2013, Enhanced photochemical hydrogen production by a molecular diiron catalyst incorporated into a metal–organic framework, J. Am. Chem. Soc., 135, 16997, 10.1021/ja407176p Fei, 2015, Functionalization of robust Zr(IV)-based metal–organic framework films via a postsynthetic ligand exchange, Chem. Commun., 51, 66, 10.1039/C4CC08218D Sasan, 2014, Incorporation of iron hydrogenase active sites into a highly stable metal–organic framework for photocatalytic hydrogen generation, Chem. Commun., 50, 10390, 10.1039/C4CC03946G Nikandrov, 1983, Titanium dioxide as photocatalyst in hydrogen production, Photobiochem. Photobiophys., 6, 101 Cuendet, 1984, Immobilized enzymes on semiconducting powder: photogeneration of hydrogen by TiO2 and CdS bound hydrogenases, Photobiochem. Photobiophys., 7, 331 Cuendet, 1984, Viologen-derivatization of TiO2 particles and light-induced H2 evolution by immobilized hydrogenase, J. Electroanal. Chem. Interfacial. Electrochem., 181, 173, 10.1016/0368-1874(84)83627-8 Cuendet, 1984, Photoreduction of NAD+ to NADH in semiconductor dispersions, Photochem. Photobiol., 39, 609, 10.1111/j.1751-1097.1984.tb03898.x Cuendet, 1986, Light induced H2 evolution in a hydrogenase-TiO2 particle system by direct electron transfer or via Rhodium complexes, Biochimie, 68, 217, 10.1016/S0300-9084(86)81086-0 Polliotto, 2016, Electron transfer and H2 evolution in hybrid systems based on [FeFe]-hydrogenase anchored on modified TiO2, Int. J. Hydrogen Energy, 41, 10547, 10.1016/j.ijhydene.2016.05.002 Honda, 2016, Application to photocatalytic H2 production of a whole-cell reaction by recombinant Escherichia coli cells expressing [FeFe]-hydrogenase and maturases genes, Angew. Chem. Int. Ed., 395, 8045, 10.1002/anie.201600177 Honda, 2017, Inorganic/whole-cell photocatalyst for highly efficient hydrogen production from water, Appl. Catal. B: Environ., 210, 400, 10.1016/j.apcatb.2017.04.015 Wombwell, 2015, [NiFeSe]-hydrogenase chemistry, Acc. Chem. Res., 48, 2858, 10.1021/acs.accounts.5b00326 Reisner, 2009, Visible light-driven H2 production by hydrogenases attached to dye-sensitized TiO2 nanoparticles, J. Am. Chem. Soc., 131, 18457, 10.1021/ja907923r Caputo, 2014, Photocatalytic hydrogen production using polymeric carbon nitride with a hydrogenase and a bioinspired synthetic Ni catalyst, Angew. Chem. Int. Ed., 43, 11722, 10.1002/ange.201406811 Caputo, 2015, Carbon nitride –TiO2 hybrid modified with hydrogenase for visible light driven hydrogen production, Chem. Sci., 6, 5690, 10.1039/C5SC02017D Brown, 2010, Controlled assembly of hydrogenase-CdTe nanocrystal hybrids for solar hydrogen production, J. Am. Chem. Soc., 132, 9672, 10.1021/ja101031r Brown, 2014, Diameter dependent electron transfer kinetics in semiconductor–enzyme complexes, ACS Nano, 8, 10790, 10.1021/nn504561v Brown, 2012, Characterization of photochemical processes for H2 production by CdS Nanorod–[FeFe] hydrogenase complexes, J. Am. Chem. Soc., 134, 5627, 10.1021/ja2116348 Wilker, 2014, Electron transfer kinetics in CdS Nanorod–[FeFe]-hydrogenase complexes and implications for photochemical H2 generation, J. Am. Chem. Soc., 136, 4316, 10.1021/ja413001p Utterback, 2015, Competition between electron transfer, trapping, and recombination in CdS nanorod-hydrogenase complexes, Phys. Chem. Chem. Phys., 17, 5538, 10.1039/C4CP05993J Winkler, 2009, Characterization of the key step for light-driven hydrogen evolution in green algae, J. Biol. Chem., 284, 36620, 10.1074/jbc.M109.053496 Adam, 2017, Sunlight-dependent hydrogen production by photosensitizer/hydrogenase systems, ChemSusChem, 10, 894, 10.1002/cssc.201601523 Pershad, 1999, Catalytic electron transport in chromatium vinosum [NiFe]-Hydrogenase:  application of voltammetry in detecting redox-active centers and establishing that hydrogen oxidation is very fast even at potentials close to the reversible H+/H2 value, Biochemistry, 38, 8992, 10.1021/bi990108v Vincent, 2005, Hydrogen cycling by enzymes: electrocatalysis and implications for future energy technology, Dalt. Trans., 3397, 10.1039/b508520a Goldet, 2009, Electrochemical kinetic investigations of the reactions of [FeFe]-hydrogenases with carbon monoxide and oxygen: comparing the importance of gas tunnels and active-site electronic/redox effects, J. Am. Chem. Soc., 131, 14979, 10.1021/ja905388j McDonald, 2007, Wiring-up hydrogenase with single-walled carbon nanotubes, Nano Lett., 7, 3528, 10.1021/nl072319o Ignatiev, 2008, Raman spectroscopy of charge transfer interactions between single wall carbon nanotubes and [FeFe] hydrogenase, Dalton Trans., 5454 Baffert, 2012, Covalent attachment of FeFe hydrogenases to carbon electrodes for direct electron transfer, Anal. Chem., 84, 7999, 10.1021/ac301812s Krassen, 2011, Tailor-made modification of a gold surface for the chemical binding of a high-activity [FeFe] hydrogenase, Eur. J. Inorg. Chem., 1138, 10.1002/ejic.201001190 Madden, 2012, Catalytic turnover of [FeFe]-hydrogenase based on single-molecule imaging, J. Am. Chem. Soc., 134, 1577, 10.1021/ja207461t Morra, 2011, Direct electrochemistry of an [FeFe]-hydrogenase on a TiO2 Electrode, Chem. Commun., 47, 10566, 10.1039/c1cc14535e Morra, 2015, Hydrogen production at high Faradaic efficiency by a bio-electrode based on TiO2 adsorption of a new [FeFe]-hydrogenase from Clostridium perfringens, Bioelectrochemistry, 106, 258, 10.1016/j.bioelechem.2015.08.001 Hambourger, 2008, [FeFe]-hydrogenase-catalyzed H2 production in a photoelectrochemical biofuel cell, J. Am. Chem. Soc., 120, 2015, 10.1021/ja077691k Lee, 2016, Photoelectrochemical H2 evolution with a hydrogenase immobilized on a TiO2-protected silicon electrode, Angew. Chem. Int. Ed., 55, 5971, 10.1002/anie.201511822 Zhao, 2016, Proton reduction using a hydrogenase-modified nonporous black silicon photo electrode, ACS Appl. Mater. Interfaces, 8, 14481, 10.1021/acsami.6b00189 Mersch, 2015, Wiring of photosystem II to hydrogenase for photoelectrochemical water splitting, J. Am. Chem. Soc., 137, 8541, 10.1021/jacs.5b03737 Felton, 2006, Iron-only hydrogenase mimics. thermodynamic aspects of the use of electrochemistry to evaluate catalytic efficiency for hydrogen generation, Inorg. Chem., 45, 9181, 10.1021/ic060984e