Solar fuels: thermodynamics, candidates, tactics, and figures of merit.

Inorganic chemistry has been and continues to be a central discipline in the field of renewable energy and solar fuels. A fundamental approach to storing solar energy is artificial photosynthesis, whereby uphill chemical reactions are driven by light, e.g. the water gas shift reaction, halogen acid splitting, or water splitting. This article endeavors to define a common context for these research topics, particularly by analyzing the thermodynamic boundaries of photosynthesis. Specifically, the generalized efficiency restrictions on both light absorption and energy storage are expounded, the analogous limitations for several individual photosynthetic strategies are stated, several synthetic catalyst architectures are highlighted, the advantages of molecular and macroscopic approaches are discussed, and key figures of merit are presented.

[1]  A. Maverick,et al.  Solar Chemistry of Metal Complexes , 1981, Science.

[2]  D. Nocera,et al.  A photocycle for hydrogen production from two-electron mixed-valence complexes. , 2005, Journal of the American Chemical Society.

[3]  Allen J. Bard,et al.  Artificial Photosynthesis: Solar Splitting of Water to Hydrogen and Oxygen , 1995 .

[4]  M. Grätzel,et al.  Hydrogen Evolution from Water by Visible Light, a Homogeneous Three Component Test System for Redox Catalysis , 1978 .

[5]  K. Domen,et al.  Photocatalyst releasing hydrogen from water , 2006, Nature.

[6]  G. Stucky,et al.  Photoelectrochemical Hydrogen Production Using New Combinatorial Chemistry Derived Materials , 2004 .

[7]  S. Shinoda,et al.  Photo-enhanced production of hydrogen by liquid-phase catalytic dehydrogenation of propan-2-ol with rhodium–tin chloride complexes , 1978 .

[8]  Susan W. Gersten,et al.  Catalytic oxidation of water by an oxo-bridged ruthenium dimer , 1982 .

[9]  T. Matsubara,et al.  Photocatalysis of tin(II)-coordinated iridium complexes for energy storing with quantum yield higher than unity in 2-propanol dehydrogenation , 1991 .

[10]  A. Tulinsky,et al.  Crystal and molecular structure of anthracene and biphenylene pillared cofacial diporphyrins. , 1986, Journal of the American Chemical Society.

[11]  S. Bernhard,et al.  Structure-activity correlations among iridium(III) photosensitizers in a robust water-reducing system. , 2009, Inorganic chemistry.

[12]  H. Arakawa,et al.  Stoichiometric water splitting into H2 and O2 using a mixture of two different photocatalysts and an IO3-/I- shuttle redox mediator under visible light irradiation. , 2001, Chemical communications.

[13]  T. Meyer,et al.  Mechanism of Water Oxidation by the μ-Oxo Dimer [(bpy)2(H2O)RuIIIORuIII(OH2)(bpy)2]4+ , 2000 .

[14]  J. Lehn,et al.  Hydrogen Generation by Visible Light Irradiation of Aqueous Solutions of Metal Complexes. An approach to the photochemical conversion and storage of solar energy , 1979 .

[15]  Hironori Arakawa,et al.  Direct splitting of water under visible light irradiation with an oxide semiconductor photocatalyst , 2001, Nature.

[16]  S. Shinoda,et al.  Photocatalytic liquid=phase dehydrogenation of cyclohexanol with rhodium porphyrin complex , 1989 .

[17]  A. Tinnemans,et al.  Tetraaza‐macrocyclic cobalt(II) and nickel(II) complexes as electron‐transfer agents in the photo(electro)chemical and electrochemical reduction of carbon dioxide , 2010 .

[18]  R. Ziessel.  Efficient homogeneous photochemical water gas shift reaction catalysed under extremely mild conditions by novel iridium(III) complexes: [(η5-Me5C5)Ir(bpy)Cl]+, [(η5-Me5C5)Ir(bpy)H]+, and [(η5-Me5C5)Ir(phen)Cl]+(bpy = 2,2′-bipyridine; phen = 1,10-phenanthroline) , 1988 .

[19]  Turner,et al.  A monolithic photovoltaic-photoelectrochemical device for hydrogen production via water splitting , 1998, Science.

[20]  D. Nocera,et al.  Four-Electron Photochemistry of Dirhodium Fluorophosphine Compounds , 1999 .

[21]  M. Graetzel,et al.  Artificial photosynthesis: water cleavage into hydrogen and oxygen by visible light , 1981 .

[22]  S. Bernhard,et al.  Homogeneous catalytic system for photoinduced hydrogen production utilizing iridium and rhodium complexes. , 2008, Inorganic chemistry.

[23]  G. Ananyev,et al.  Prospecting for biohydrogen fuel , 2006 .

[24]  R. Ziessel.  Photocatalysis. Mechanistic studies of homogeneous photochemical water gas shift reaction catalyzed under mild conditions by novel cationic iridium(III) complexes , 1993 .

[25]  C. Lecomte,et al.  Synthesis, Characterization, and Reactivity toward Dioxygen of Copper Manganese Cofacial Porphyrins. Crystal and Molecular Structures of a Heterobimetallic Biphenylene-Pillared Cofacial Diporphyrin , 1994 .

[26]  P. Müller,et al.  Efficient homogeneous catalysis in the reduction of CO2 to CO. , 2005, Journal of the American Chemical Society.

[27]  R. Hezel.  Commercial High-Efficiency Silicon Solar Cells , 2009 .

[28]  B. Brunschwig,et al.  Toward photochemical carbon dioxide activation by transition metal complexes , 1994 .

[29]  J. K. Hurst,et al.  A molecular water-oxidation catalyst derived from ruthenium diaqua bis(2,2'-bipyridyl-5,5'-dicarboxylic acid) , 1987 .

[30]  T. Moore,et al.  Solar fuels via artificial photosynthesis. , 2009, Accounts of chemical research.

[31]  A. Harriman,et al.  Metal phthalocyanines and porphyrins as photosensitizers for reduction of water to hydrogen , 1982 .

[32]  Harold C. Urey,et al.  Abundances of the elements , 1956 .

[33]  Homogeneous catalysis of the photoreduction of water. 6. Mediation by polypyridine complexes of ruthenium(II) and cobalt(II) in alkaline media , 1985 .

[34]  J. D. Luttmer,et al.  Electrode materials for hydrobromic acid electrolysis in Texas Instruments' solar chemical converter , 1985 .

[35]  S. Shinoda,et al.  Photocatalytic dehydrogenation of 2-propanol with carbonyl(halogeno)phosphine-rhodium complexes , 1989 .

[36]  S. Bernhard,et al.  Cyclometalated iridium(III) Aquo complexes: efficient and tunable catalysts for the homogeneous oxidation of water. , 2008, Journal of the American Chemical Society.

[37]  T. Mallouk,et al.  Photochemical hydrogen evolution via singlet-state electron-transfer quenching of zinc tetra(N-methyl-4-pyridyl)porphyrin cations in a zeolite L based system , 1987 .

[38]  I. Willner,et al.  Photosensitized electron-transfer reactions in .beta.-cyclodextrin aqueous media: effects on dissociation of ground-state complexes, charge separation, and hydrogen evolution , 1986 .

[39]  K. Tsuge,et al.  Syntheses and redox properties of bis(hydroxoruthenium) complexes with quinone and bipyridine ligands. Water-oxidation catalysis. , 2001, Inorganic chemistry.

[40]  S. Bernhard,et al.  Visible light induced catalytic water reduction without an electron relay. , 2007, Chemistry.

[41]  Y. Chow,et al.  Nonaromatic aminium radicals , 1978 .

[42]  T. Meyer,et al.  Mechanism of Water Oxidation Catalyzed by the μ-Oxo Dimer [(bpy)2(OH2)RuIIIORuIII(OH2)(bpy)2]4+ , 1997 .

[43]  D. Nocera,et al.  Metal-halide bond photoactivation from a PtIII-AuII complex. , 2007, Journal of the American Chemical Society.

[44]  R. Ziessel.  Photocatalysis of the Homogeneous Water‐Gas Shift Reaction under Ambient Conditions by Cationic Iridium (III) Complexes , 1991 .

[45]  T. Yoshida,et al.  ACTIVATION OF WATER MOLECULES. 4. GENERATION OF DIHYDROGEN FROM WATER BY RHODIUM(I) HYDRIDO AND RHODIUM(0) CARBONYL COMPOUNDS , 1980 .

[46]  S. Shinoda,et al.  The mechanisms of photocatalytic dehydrogenation of methanol in the liquid phase with cis-[Rh2Cl2(CO)2(dpm)2] complex catalyst , 1985 .

[47]  On Solar Hydrogen & Nanotechnology. Edited by Lionel Vayssieres. , 2010 .

[48]  Robin Brimblecombe,et al.  Solar driven water oxidation by a bioinspired manganese molecular catalyst. , 2010, Journal of the American Chemical Society.

[49]  Olof Johansson,et al.  The role of colloid formation in the photoinduced H2 production with a Ru(II)-Pd(II) supramolecular complex: a study by GC, XPS, and TEM. , 2008, Journal of the American Chemical Society.

[50]  A. De Vos,et al.  On the thermodynamic limit of photovoltaic energy conversion , 1981 .

[51]  D. Nocera,et al.  Direct Observation of the “Pac-Man” Effect from Dibenzofuran-Bridged Cofacial Bisporphyrins , 2000 .

[52]  D. Nocera,et al.  A RhII-AuII bimetallic core with a direct metal-metal bond. , 2007, Inorganic chemistry.

[53]  R. Thummel,et al.  Preparation and study of a family of dinuclear Ru(II) complexes that catalyze the decomposition of water. , 2008, Inorganic chemistry.

[54]  Gianfranco Scorrano,et al.  Polyoxometalate embedding of a tetraruthenium(IV)-oxo-core by template-directed metalation of [gamma-SiW10O36]8-: a totally inorganic oxygen-evolving catalyst. , 2008, Journal of the American Chemical Society.

[55]  J. D. Luttmer,et al.  Performance predictions for solar-chemical converters based on photoelectrochemical I-V curves , 1985 .

[56]  Jonas I. Goldsmith,et al.  Discovery and high-throughput screening of heteroleptic iridium complexes for photoinduced hydrogen production. , 2005, Journal of the American Chemical Society.

[57]  J. Vekemans,et al.  Highly sustainable catalytic dehydrogenation of alcohols with evolution of hydrogen gas , 2003 .

[58]  George G. Malliaras,et al.  Single-Layer Electroluminescent Devices and Photoinduced Hydrogen Production from an Ionic Iridium(III) Complex , 2005 .

[59]  B. Ward,et al.  Nonbonding steric effect on carbon monoxide and oxygen binding to hemes. Kinetics of ligand binding in iron-copper cofacial diporphyrins and strapped hemes , 1981 .

[60]  Paul Kögerler,et al.  An all-inorganic, stable, and highly active tetraruthenium homogeneous catalyst for water oxidation. , 2008, Angewandte Chemie.

[61]  Thomas S. Teets,et al.  Halogen photoreductive elimination from gold(III) centers. , 2009, Journal of the American Chemical Society.

[62]  E. Fujita,et al.  Molecular approaches to the photocatalytic reduction of carbon dioxide for solar fuels. , 2009, Accounts of chemical research.

[63]  M. Bowker,et al.  Photocatalytic water-gas shift reaction at ambient temperature , 2002 .

[64]  D. Nocera,et al.  A convergent synthetic approach using sterically demanding aryldipyrrylmethanes for tuning the pocket sizes of cofacial bisporphyrins. , 2002, Inorganic chemistry.

[65]  Hongyu Chen,et al.  Homogeneous water oxidation by a di-μ-oxo dimanganese complex in the presence of Ce4+ , 2007 .

[66]  H. Queisser,et al.  Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells , 1961 .

[67]  D. Nocera,et al.  Chlorine photoelimination from a diplatinum core: circumventing the back reaction. , 2009, Journal of the American Chemical Society.

[68]  R. Thummel,et al.  A new family of Ru complexes for water oxidation. , 2005, Journal of the American Chemical Society.

[69]  Brian D. James,et al.  Technoeconomic Analysis of Photoelectrochemical (PEC) Hydrogen Production , 2009 .

[70]  Yasukazu Saito,et al.  Photocatalytic dehydrogenation of secondary alcohols with rhodium porphyrin complex , 1983 .

[71]  Susan W. Gersten,et al.  Structure and redox properties of the water-oxidation catalyst [(bpy)2(OH2)RuORu(OH2)(bpy)2]4+ , 1985 .

[72]  Jordan Peccia,et al.  Challenges in developing biohydrogen as a sustainable energy source: implications for a research agenda. , 2010, Environmental science & technology.

[73]  H. Harima,et al.  Inter-conduction band electron relaxation dynamics in 6H–SiC , 2001 .

[74]  R. Irie,et al.  Reaction mechanism of photocatalysis for the liquid-phase dehydrogenation of 2-propanol with rhodium porphyrin complex , 1984 .

[75]  C. Koval,et al.  Potent catalysis of the electroreduction of oxygen to water by dicobalt porphyrin dimers adsorbed on graphite electrodes , 1979 .

[76]  D. Cole-Hamilton,et al.  Hydrogen production from ethanol catalysed by Group 8 metal complexes , 1989 .

[77]  E. Rideal.  On the Catalytic Dehydrogenation of Alcohols , 1921 .

[78]  R. Irie,et al.  Quantum chemical interpretation of the dihydrogen formation process in photocatalytic 2-propanol dehydrogenation with rhodium porphyrin complex , 1984 .

[79]  T. Meyer,et al.  Redox properties of the oxo-bridged osmium dimer [(bpy)2(OH2)OsIIIOOsIV(OH)(bpy)2]4+. Implications for the oxidation of water to oxygen , 1986 .

[80]  S. Shinoda,et al.  Thermo- and photocatalytic dehydrogenation of 2-propanol with [RuL(SnCl3)5]4− (LCl− or SnCl3−) complexes , 1993 .

[81]  H. Arakawa,et al.  THE PHOTOCATALYTIC DEHYDROGENATION OF 2-PROPANOL BY USING RhCl(PPh3)3 , 1981 .

[82]  M. Kaneko,et al.  Catalytic Activity of Tri(μ-chloro)-Bridged Dinuclear Ruthenium Complex Confined in a Polymer Membrane as an Artificial Model of Photosynthetic Oxygen Evolving Center , 1999 .

[83]  T. Shido,et al.  Photocatalysis of metal clusters in cages: effective photoactivation of the water gas shift reaction catalysed on NaY zeolite-entrapped Pt12 and Pt9 carbonyl clusters , 1992 .

[84]  Dynamics of light-induced water cleavage in colloidal systems , 1981 .