Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes

This review highlights recent developments and future perspectives in carbon dioxide usage for the sustainable production of energy and chemicals and to reduce global warming. We discuss the heterogeneously catalysed hydrogenation, as well as the photocatalytic and electrocatalytic conversion of CO2 to hydrocarbons or oxygenates. Various sources of hydrogen are also reviewed in terms of their CO2 neutrality. Technologies have been developed for large-scale CO2 hydrogenation to methanol or methane. Their industrial application is, however, limited by the high price of renewable hydrogen and the availability of large-volume sources of pure CO2. With regard to the direct electrocatalytic reduction of CO2 to value-added chemicals, substantial advances in electrodes, electrolyte, and reactor design are still required to permit the development of commercial processes. Therefore, in this review particular attention is paid to (i) the design of metal electrodes to improve their performance and (ii) recent developments of alternative approaches such as the application of ionic liquids as electrolytes and of microorganisms as co-catalysts. The most significant improvements both in catalyst and reactor design are needed for the photocatalytic functionalisation of CO2 to become a viable technology that can help in the usage of CO2 as a feedstock for the production of energy and chemicals. Apart from technological aspects and catalytic performance, we also discuss fundamental strategies for the rational design of materials for effective transformations of CO2 to value-added chemicals with the help of H2, electricity and/or light.

[1]  Yongchun Zhang,et al.  Effect of promoter SiO2, TiO2 or SiO2-TiO2 on the performance of CuO-ZnO-Al2O3 catalyst for methanol synthesis from CO2 hydrogenation , 2012 .

[2]  P. Kenis,et al.  Prospects of CO2 Utilization via Direct Heterogeneous Electrochemical Reduction , 2010 .

[3]  K. Hara,et al.  High Efficiency Electrochemical Reduction of Carbon Dioxide under High Pressure on a Gas Diffusion Electrode Containing Pt Catalysts , 1995 .

[4]  L. Palmisano,et al.  Photon absorption by aqueous TiO2 dispersion contained in a stirred photoreactor , 1991 .

[5]  Weitao Yang,et al.  Challenges for density functional theory. , 2012, Chemical reviews.

[6]  Frederick W. Williams,et al.  Heterogeneous catalytic CO2 conversion to value-added hydrocarbons , 2010 .

[7]  Wei Wang,et al.  Recent advances in catalytic hydrogenation of carbon dioxide. , 2011, Chemical Society reviews.

[8]  Zhenpeng Hu,et al.  CO2 methanation on Ru-doped ceria , 2011 .

[9]  N. Alonso‐Vante,et al.  A screening for the photo reduction of carbon dioxide supported on metal oxide catalysts for C1-C3 selectivity , 1999 .

[10]  Ping Liu,et al.  Methanol synthesis from H2 and CO2 on a Mo6S8 cluster: a density functional study. , 2010, The journal of physical chemistry. A.

[11]  Rufino M. Navarro,et al.  Hydrogen production from renewable sources: biomass and photocatalytic opportunities , 2009 .

[12]  A. Bell,et al.  Effects of Zirconia Phase on the Synthesis of Methanol over Zirconia-Supported Copper , 2002 .

[13]  J. Fierro,et al.  Hydrogenation of carbon oxides over promoted Fe-Mn catalysts prepared by the microemulsion methodology , 2006 .

[14]  Wan Mohd Ashri Wan Daud,et al.  Hydrogen production by methane decomposition: A review , 2010 .

[15]  Bruce E Logan,et al.  Direct biological conversion of electrical current into methane by electromethanogenesis. , 2009, Environmental science & technology.

[16]  J. K. Thomas,et al.  Photochemical reduction of carbonate to formaldehyde on TiO2 powder , 1983 .

[17]  Yongqing Zhang,et al.  CO and CO2 hydrogenation study on supported cobalt Fischer-Tropsch synthesis catalysts , 2002 .

[18]  Daniel Escudero,et al.  Progress and challenges in the calculation of electronic excited states. , 2012, Chemphyschem : a European journal of chemical physics and physical chemistry.

[19]  Hongyan Liu,et al.  Effect of Surface Hydroxyls on CO2 Hydrogenation Over Cu/γ-Al2O3 Catalyst: A Theoretical Study , 2011 .

[20]  J. Wu,et al.  Photoreduction of CO2 in an optical-fiber photoreactor: Effects of metals addition and catalyst carrier , 2008 .

[21]  Thomas I. Valdez,et al.  Electrochemical Conversion of Carbon Dioxide to Formate in Alkaline Polymer Electrolyte Membrane Cells , 2011 .

[22]  Takeshi Kobayashi,et al.  Novel CO2 Electrochemical Reduction to Methanol for H2 Storage , 2004 .

[23]  M. Taghizadeh,et al.  Enhancement of stability and activity of Cu/ZnO/Al2O3 catalysts by colloidal silica and metal oxides additives for methanol synthesis from a CO2-rich feed , 2012 .

[24]  Anne C. Co,et al.  A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper , 2006 .

[25]  Y. Ku,et al.  Photocatalytic reduction of carbonate in aqueous solution by UV/TiO2 process , 2004 .

[26]  J. Wu,et al.  Mesoporous TiO2/SBA-15, and Cu/TiO2/SBA-15 Composite Photocatalysts for Photoreduction of CO2 to Methanol , 2009 .

[27]  Daniel L DuBois,et al.  Development of molecular electrocatalysts for CO2 reduction and H2 production/oxidation. , 2009, Accounts of chemical research.

[28]  B. Kroposki,et al.  Renewable hydrogen production , 2008 .

[29]  Jianli Hu,et al.  An overview of hydrogen production technologies , 2009 .

[30]  Alberto E. Cassano,et al.  Modeling of light scattering in photochemical reactors , 1994 .

[31]  T. Maschmeyer,et al.  Catalytic aspects of light-induced hydrogen generation in water with TiO2 and other photocatalysts: a simple and practical way towards a normalization? , 2010, Angewandte Chemie.

[32]  V. Matějka,et al.  Comparison of the pure TiO2 and kaolinite/TiO2 composite as catalyst for CO2 photocatalytic reduction , 2011 .

[33]  Tsunehiro Tanaka,et al.  Photoenhanced reduction of CO2 by H2 over Rh/TiO2: Characterization of supported Rh species by means of infrared and X-ray absorption spectroscopy , 2001 .

[34]  H. Frei Polynuclear Photocatalysts in Nanoporous Silica for Artificial Photosynthesis , 2009 .

[35]  C. Campbell,et al.  Methanol Synthesis and Reverse Water–Gas Shift Kinetics over Cu(110) Model Catalysts: Structural Sensitivity , 1996 .

[36]  J. Nørskov,et al.  The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts , 2012, Science.

[37]  S. Barnett,et al.  Syngas Production By Coelectrolysis of CO2/H2O: The Basis for a Renewable Energy Cycle , 2009 .

[38]  Song Wang,et al.  CO2 hydrogenation to methanol over Cu/ZnO/ZrO2 catalysts prepared via a route of solid-state reaction , 2011 .

[39]  Yoshifumi Suehiro,et al.  Development of synthesis gas production catalyst and process , 2005 .

[40]  Yuichi Ichihashi,et al.  Photocatalytic reduction of CO2 with H2O on various titanium oxide catalysts , 1995 .

[41]  Din Ping Tsai,et al.  CO2 photoreduction using NiO/InTaO4 in optical-fiber reactor for renewable energy , 2010 .

[42]  Craig A. Grimes,et al.  High-rate solar photocatalytic conversion of CO2 and water vapor to hydrocarbon fuels. , 2009, Nano letters.

[43]  Ying Yu,et al.  Preparation of multi-walled carbon nanotube supported TiO2 and its photocatalytic activity in the reduction of CO2 with H2O , 2007 .

[44]  J. Wu Photocatalytic Reduction of Greenhouse Gas CO2 to Fuel , 2009 .

[45]  M. Matsumura,et al.  Crystal faces of rutile and anatase TiO2 particles and their roles in photocatalytic reactions , 2002 .

[46]  J. Wu,et al.  Effects of sol–gel procedures on the photocatalysis of Cu/TiO2 in CO2 photoreduction , 2004 .

[47]  Shaohua Liu,et al.  Photocatalytic reduction of carbon dioxide using sol-gel derived titania-supported CoPc catalysts , 2007, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[48]  Sang-Eon Park,et al.  Photoreduction of Carbondioxide on Surface Functionalized Nanoporous Catalysts , 2005 .

[49]  F. Williams,et al.  C2-C5+ olefin production from CO2 hydrogenation using ceria modified Fe/Mn/K catalysts , 2011 .

[50]  H. Yamashita,et al.  Characterization and photocatalytic reduction of CO2 with H2O on Ti/FSM-16 synthesized by various preparation methods. , 2001, Journal of synchrotron radiation.

[51]  Lucie Obalová,et al.  Effect of silver doping on the TiO2 for photocatalytic reduction of CO2 , 2010 .

[52]  T. Abe,et al.  Preparation and Physical and Electrochemical Properties of Carbon-Supported Pt−Ru (Pt−Ru/C) Samples Using the Polygonal Barrel-Sputtering Method , 2008 .

[53]  M. Halmann,et al.  Photoelectrochemical reduction of aqueous carbon dioxide on p-type gallium phosphide in liquid junction solar cells , 1978, Nature.

[54]  Seng Sing Tan,et al.  Photosynthesis of hydrogen and methane as key components for clean energy system , 2007 .

[55]  John T. S. Irvine,et al.  Electrochemical reduction of CO2 in a proton conducting solid oxide electrolyser , 2011 .

[56]  M. Azuma,et al.  Design of Allory Electrocatalysts for CO 2 Reduction (I).The Selective and Reversible Reduction of CO 2 at Cu-Ni Alloy Electrodes , 1991 .

[57]  Matthew W. Kanan,et al.  Tin oxide dependence of the CO2 reduction efficiency on tin electrodes and enhanced activity for tin/tin oxide thin-film catalysts. , 2012, Journal of the American Chemical Society.

[58]  Aaron J. Sathrum,et al.  Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels. , 2009, Chemical Society reviews.

[59]  Photocatalytic CO2 reduction by TiO2 and related titanium containing solids , 2012 .

[60]  Feng Xu,et al.  Shape selective plate-form Ga(2)O(3) with strong metal-support interaction to overlying Pd for hydrogenation of CO(2) to CH(3)OH. , 2013, Chemical communications.

[61]  Ho-Cheol Kim,et al.  Abundant non-toxic materials for thin film solar cells: Alternative to conventional materials , 2011 .

[62]  Ping Liu,et al.  CO2 Activation and Methanol Synthesis on Novel Au/TiC and Cu/TiC Catalysts. , 2012, The journal of physical chemistry letters.

[63]  Ya‐Ping Sun,et al.  Metal-coated nanoscale TiO2 catalysts for enhanced CO2 photoreduction , 2005 .

[64]  Yong Yang,et al.  Effect of manganese on an iron-based Fischer–Tropsch synthesis catalyst prepared from ferrous sulfate , 2007 .

[65]  F. Saladin,et al.  Photosynthesis of CH4 at a TiO2 surface from gaseous H2O and CO2 , 1995 .

[66]  A. Kudo,et al.  Heterogeneous photocatalyst materials for water splitting. , 2009, Chemical Society reviews.

[67]  G. Chinchen,et al.  Mechanism of methanol synthesis from CO2/CO/H2 mixtures over copper/zinc oxide/alumina catalysts: use of14C-labelled reactants , 1987 .

[68]  Hongyan Liu,et al.  Insights into the effect of surface hydroxyls on CO2 hydrogenation over Pd/γ-Al2O3 catalyst: A computational study , 2012 .

[69]  Somnath C. Roy,et al.  Toward solar fuels: photocatalytic conversion of carbon dioxide to hydrocarbons. , 2010, ACS nano.

[70]  Christopher Graves,et al.  Production of Synthetic Fuels by Co-Electrolysis of Steam and Carbon Dioxide , 2009 .

[71]  M. Malati,et al.  The photocatalysed reduction of aqueous sodium carbonate using platinized titania , 1989 .

[72]  Jacob A. Moulijn,et al.  Functioning devices for solar to fuel conversion , 2012 .

[73]  Donald G Truhlar,et al.  Density functional theory for transition metals and transition metal chemistry. , 2009, Physical chemistry chemical physics : PCCP.

[74]  Gao Qing Lu,et al.  Recent advances in catalysts for methanol synthesis via hydrogenation of CO and CO2 , 2003 .

[75]  Manos Mavrikakis,et al.  Mechanism of Methanol Synthesis on Cu through CO2 and CO Hydrogenation , 2011 .

[76]  S. Yin,et al.  Formaldehyde and methanol formation from reaction of carbon monoxide and hydrogen on neutral Fe2S2 clusters in the gas phase. , 2013, Physical chemistry chemical physics : PCCP.

[77]  J. Fierro,et al.  Hydrogen production reactions from carbon feedstocks: fossil fuels and biomass. , 2007, Chemical reviews.

[78]  Richard L. Kurtz,et al.  Electrochemical Reduction of CO2 to CH3OH at Copper Oxide Surfaces , 2011 .

[79]  J. Wu,et al.  Chemical states of metal-loaded titania in the photoreduction of CO2 , 2004 .

[80]  Emily Barton Cole,et al.  Using a one-electron shuttle for the multielectron reduction of CO2 to methanol: kinetic, mechanistic, and structural insights. , 2010, Journal of the American Chemical Society.

[81]  L. Pfefferle,et al.  Methanation of carbon dioxide on Ni-incorporated MCM-41 catalysts: The influence of catalyst pretreatment and study of steady-state reaction , 2007 .

[82]  T. Abe,et al.  CO2 methanation property of Ru nanoparticle-loaded TiO2 prepared by a polygonal barrel-sputtering method , 2009 .

[83]  Ki-Won Jun,et al.  Fischer–Tropsch Synthesis by Carbon Dioxide Hydrogenation on Fe-Based Catalysts , 2008 .

[84]  J. Wu,et al.  A novel twin reactor for CO2 photoreduction to mimic artificial photosynthesis , 2013 .

[85]  F. Williams,et al.  K and Mn doped iron-based CO2 hydrogenation catalysts: Detection of KAlH4 as part of the catalyst's active phase , 2010 .

[86]  K. C. Waugh,et al.  Synthesis of Methanol , 1988 .

[87]  Andrew A. Peterson,et al.  Activity Descriptors for CO2 Electroreduction to Methane on Transition-Metal Catalysts , 2012 .

[88]  Han Sen Soo,et al.  Visible light-induced hole injection into rectifying molecular wires anchored on Co3O4 and SiO2 nanoparticles. , 2012, Journal of the American Chemical Society.

[89]  Xiaobo Chen,et al.  Semiconductor-based photocatalytic hydrogen generation. , 2010, Chemical reviews.

[90]  Y. Hori,et al.  Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution , 1990 .

[91]  Hiroyuki Takeda,et al.  Development of efficient photocatalytic systems for CO2 reduction using mononuclear and multinuclear metal complexes based on mechanistic studies , 2010 .

[92]  J. Sehested,et al.  Four challenges for nickel steam-reforming catalysts , 2006 .

[93]  Yuhan Sun,et al.  Preparation and activity of Cu/Zn/Al/Zr catalysts via hydrotalcite-containing precursors for methanol synthesis from CO2 hydrogenation , 2012 .

[94]  Andrew A. Peterson,et al.  Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces , 2011 .

[95]  R. Richardson,et al.  A renewable amine for photochemical reduction of CO(2). , 2011, Nature chemistry.

[96]  Eric W. McFarland,et al.  A highly dispersed Pd-Mg/SiO2 catalyst active for methanation of CO2 , 2009 .

[97]  B. Rieger,et al.  Transformation of carbon dioxide with homogeneous transition-metal catalysts: a molecular solution to a global challenge? , 2011, Angewandte Chemie.

[98]  Y. Shimizu,et al.  Photocatalytic reduction of high pressure carbon dioxide using TiO2 powders with a positive hole scavenger , 1998 .

[99]  A. Urakawa,et al.  Impact of K and Ba promoters on CO2 hydrogenation over Cu/Al2O3 catalysts at high pressure , 2013 .

[100]  E. Carter,et al.  Theoretical insights into pyridinium-based photoelectrocatalytic reduction of CO2. , 2012, Journal of the American Chemical Society.

[101]  Matthew W Kanan,et al.  CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. , 2012, Journal of the American Chemical Society.

[102]  P. Kenis,et al.  Ionic Liquid–Mediated Selective Conversion of CO2 to CO at Low Overpotentials , 2011, Science.

[103]  Xiao Jiang,et al.  Effects of mesoporous silica supports and alkaline promoters on activity of Pd catalysts in CO2 hydrogenation for methanol synthesis , 2012 .

[104]  Kamal Kishore,et al.  Photo-catalytic reduction of carbon dioxide to methane using TiO2 as suspension in water , 2004 .

[105]  Carl M. Stoots,et al.  Syngas Production via High-Temperature Coelectrolysis of Steam and Carbon Dioxide , 2009 .

[106]  J. Savéant Molecular catalysis of electrochemical reactions. Mechanistic aspects. , 2008, Chemical reviews.

[107]  N. Dimitrijević,et al.  Synthesizing mixed-phase TiO2 nanocomposites using a hydrothermal method for photo-oxidation and photoreduction applications , 2008 .

[108]  Guo Xiaoming,et al.  Glycine–nitrate combustion synthesis of CuO–ZnO–ZrO2 catalysts for methanol synthesis from CO2 hydrogenation , 2010 .

[109]  Toshio Tsukamoto,et al.  Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media , 1994 .

[110]  H. Lasa,et al.  Experimental evaluation of photon absorption in an aqueous TiO2 slurry reactor , 2002 .

[111]  Yong Zhou,et al.  High-yield synthesis of ultralong and ultrathin Zn2GeO4 nanoribbons toward improved photocatalytic reduction of CO2 into renewable hydrocarbon fuel. , 2010, Journal of the American Chemical Society.

[112]  John Newman,et al.  Design of an Electrochemical Cell Making Syngas ( CO + H2 ) from CO2 and H2O Reduction at Room Temperature , 2007 .

[113]  Christoph Kern,et al.  Considerations concerning the Energy Demand and Energy Mix for Global Welfare and Stable Ecosystems , 2011 .

[114]  Donghai Mei,et al.  Insight into methanol synthesis from CO2 hydrogenation on Cu(111): Complex reaction network and the effects of H2O , 2011 .

[115]  Feng Jiao,et al.  Nanostructured cobalt and manganese oxide clusters as efficient water oxidation catalysts , 2010 .

[116]  Jair A. Lizarazo-Adarme,et al.  Synthesis of methanol and dimethyl ether from syngas over Pd/ZnO/Al2O3 catalysts , 2012 .

[117]  F. Saladin,et al.  Temperature dependence of the photochemical reduction of CO2in the presence of H2Oat the solid/gas interface of TiO2 , 1997 .

[118]  A. Fujishima,et al.  Photoelectrocatalytic reduction of carbon dioxide in aqueous suspensions of semiconductor powders , 1979, Nature.

[119]  Jean-Michel Savéant,et al.  Catalysis of the electrochemical reduction of carbon dioxide. , 2013, Chemical Society reviews.

[120]  G. Guan,et al.  Reduction of carbon dioxide with water under concentrated sunlight using photocatalyst combined with Fe-based catalyst , 2003 .

[121]  B. Stoner,et al.  Cu(II)/Cu(0) electrocatalyzed CO2 and H2O splitting , 2013 .

[122]  N. Sasirekha,et al.  Photocatalytic performance of Ru doped anatase mounted on silica for reduction of carbon dioxide , 2006 .

[123]  Osamu Ishitani,et al.  Photocatalytic reduction of carbon dioxide to methane and acetic acid by an aqueous suspension of metal-deposited TiO2 , 1993 .

[124]  P. Gori-Giorgi,et al.  Density functional theory for strongly-interacting electrons: perspectives for physics and chemistry. , 2010, Physical chemistry chemical physics : PCCP.

[125]  Andrew A. Peterson,et al.  How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels , 2010 .

[126]  Mark A. Johnson,et al.  Vibrational predissociation spectrum of the carbamate radical anion, C(5)H(5)N-CO(2)(-), generated by reaction of pyridine with (CO(2))(m)(-). , 2010, Journal of the American Chemical Society.

[127]  Pratim Biswas,et al.  Photocatalytic reduction of CO2 with H2O on mesoporous silica supported Cu/TiO2 catalysts , 2010 .

[128]  Pingquan Wang,et al.  One-pot synthesis of rutile TiO2 nanoparticle modified anatase TiO2 nanorods toward enhanced photocatalytic reduction of CO2 into hydrocarbon fuels , 2012 .

[129]  H. Frei,et al.  Bimetallic redox sites for photochemical CO2 splitting in mesoporous silicate sieve , 2006 .

[130]  Mauro Majone,et al.  Bioelectrochemical reduction of CO(2) to CH(4) via direct and indirect extracellular electron transfer by a hydrogenophilic methanogenic culture. , 2010, Bioresource technology.

[131]  Q. Ge,et al.  Selective CO2 hydrogenation on the γ-Al2O3 supported bimetallic Co–Cu catalyst , 2012 .

[132]  Song Wang,et al.  The influence of La doping on the catalytic behavior of Cu/ZrO2 for methanol synthesis from CO2 hydrogenation , 2011 .

[133]  Guo-Dong Lin,et al.  Carbon nanotube-supported Pd-ZnO catalyst for hydrogenation of CO2 to methanol , 2009 .

[134]  Zhenshanl Li,et al.  Electrochemical reduction of carbon dioxide in an MFC-MEC system with a layer-by-layer self-assembly carbon nanotube/cobalt phthalocyanine modified electrode. , 2012, Environmental science & technology.

[135]  Lin Zhao,et al.  Electrochemical reduction of CO2 in solid oxide electrolysis cells , 2010 .

[136]  Ronald L. Cook,et al.  On the Electrochemical Reduction of Carbon Dioxide at In Situ Electrodeposited Copper , 1988 .

[137]  M. Anpo,et al.  Photocatalytic Reduction of CO2 with H2O on Ti−β Zeolite Photocatalysts: Effect of the Hydrophobic and Hydrophilic Properties , 2001 .

[138]  Fenglin Liao,et al.  Morphology-dependent interactions of ZnO with Cu nanoparticles at the materials' interface in selective hydrogenation of CO2 to CH3OH. , 2011, Angewandte Chemie.

[139]  M. N. Mahmood,et al.  Use of gas-diffusion electrodes for high-rate electrochemical reduction of carbon dioxide. I. Reduction at lead, indium- and tin-impregnated electrodes , 1987 .

[140]  Hung-Ming Lin,et al.  Photo reduction of CO2 to methanol using optical-fiber photoreactor , 2005 .

[141]  Kwang Myung Cho,et al.  Integrated Electromicrobial Conversion of CO2 to Higher Alcohols , 2012, Science.

[142]  Z. Zou,et al.  Photophysical and photocatalytic properties of ANbO3 (A=Na, K) photocatalysts , 2012 .

[143]  S. Ebbesen,et al.  Co-electrolysis of CO2 and H2O in solid oxide cells: Performance and durability , 2011 .

[144]  Q. Ge,et al.  Adsorption and activation of CO2 over the Cu–Co catalyst supported on partially hydroxylated γ-Al2O3 , 2011 .

[145]  John P. Baltrus,et al.  Visible Light Photoreduction of CO2 Using CdSe/Pt/TiO2 Heterostructured Catalysts , 2009 .

[146]  Debabrata Das,et al.  RECENT DEVELOPMENTS IN BIOLOGICAL HYDROGEN PRODUCTION PROCESSES , 2008 .

[147]  J. Baltrusaitis,et al.  Computational studies of CO2 activation via photochemical reactions with reduced sulfur compounds. , 2012, The journal of physical chemistry. A.

[148]  K. Burke Perspective on density functional theory. , 2012, The Journal of chemical physics.

[149]  G. Italiano,et al.  Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO2 catalysts in the CO2 hydrogenation to CH3OH , 2008 .

[150]  K. Hashimoto,et al.  Low-voltage electrochemical CO2 reduction by bacterial voltage-multiplier circuits. , 2013, Chemical communications.

[151]  Hong-Bin Zhang,et al.  Pd-Decorated CNT-Promoted Pd-Ga2O3 Catalyst for Hydrogenation of CO2 to Methanol , 2011 .

[152]  Xin Li,et al.  Photocatalytic reduction of carbon dioxide to methanol by Cu2O/SiC nanocrystallite under visible light irradiation , 2011 .

[153]  Y. Hori,et al.  Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes , 2003 .

[154]  Anne-Cécile Roger,et al.  Methanation of carbon dioxide over nickel-based Ce0.72Zr0.28O2 mixed oxide catalysts prepared by sol–gel method , 2009 .

[155]  Takashi Tatsumi,et al.  Selective formation of CH3OH in the photocatalytic reduction of CO2 with H2O on titanium oxides highly dispersed within zeolites and mesoporous molecular sieves , 1998 .

[156]  Hubertus V. M. Hamelers,et al.  Microbial electrolysis cells for production of methane from CO2: long‐term performance and perspectives , 2012 .

[157]  Steven L. Suib,et al.  Enhanced electrocatalytic reduction of CO2/H2O to paraformaldehyde at Pt/metal oxide interfaces , 2010 .

[158]  Ning Zhang,et al.  Self-doped SrTiO3−δ photocatalyst with enhanced activity for artificial photosynthesis under visible light , 2011 .

[159]  Frank E. Osterloh,et al.  Inorganic nanostructures for photoelectrochemical and photocatalytic water splitting. , 2013, Chemical Society reviews.

[160]  Frank E. Osterloh,et al.  Inorganic Materials as Catalysts for Photochemical Splitting of Water , 2008 .

[161]  S. Nozaki,et al.  Characterization of self-standing Ti-containing porous silica thin films and their reactivity for the photocatalytic reduction of CO2 with H2O , 2002 .

[162]  Xuelian Liang,et al.  Multi-Walled Carbon Nanotubes as a Novel Promoter of Catalysts for CO/CO2 Hydrogenation to Alcohols , 2009 .

[163]  Siglinda Perathoner,et al.  Towards solar fuels from water and CO2. , 2010, ChemSusChem.

[164]  Andrew B. Bocarsly,et al.  Selective solar-driven reduction of CO2 to methanol using a catalyzed p-GaP based photoelectrochemical cell. , 2008, Journal of the American Chemical Society.

[165]  N. Dimitrijević,et al.  Role of water and carbonates in photocatalytic transformation of CO2 to CH4 on titania. , 2011, Journal of the American Chemical Society.

[166]  E. Carter,et al.  First principles scheme to evaluate band edge positions in potential transition metal oxide photocatalysts and photoelectrodes. , 2011, Physical chemistry chemical physics : PCCP.

[167]  Yu‐Wen Chen,et al.  Photocatalytic reduction of carbon dioxide on NiO/InTaO4 under visible light irradiation , 2007 .

[168]  Waldemar Liebner,et al.  CO2-based methanol and DME – Efficient technologies for industrial scale production , 2011 .

[169]  Robert T McGibbon,et al.  Electrocatalytic carbon dioxide activation: the rate-determining step of pyridinium-catalyzed CO2 reduction. , 2011, ChemSusChem.

[170]  M. Beyer,et al.  Selective formic acid synthesis from nanoscale electrochemistry. , 2010, Angewandte Chemie.

[171]  D. Truhlar,et al.  Improved CO Adsorption Energies, Site Preferences, and Surface Formation Energies from a Meta-Generalized Gradient Approximation Exchange-Correlation Functional, M06-L. , 2012, The journal of physical chemistry letters.

[172]  G. Centi,et al.  Opportunities and prospects in the chemical recycling of carbon dioxide to fuels , 2009 .

[173]  I-Hsiang Tseng,et al.  Photoreduction of CO2 using sol–gel derived titania and titania-supported copper catalysts , 2002 .

[174]  Kohei Inoue,et al.  Photocatalysed reduction of CO2 in aqueous TiO2 suspension mixed with copper powder , 1992 .

[175]  Daniel G Nocera,et al.  Hydrogen production by molecular photocatalysis. , 2007, Chemical reviews.

[176]  Tsunehiro Tanaka,et al.  Adsorbed Species of CO2 and H2 on Ga2O3 for the Photocatalytic Reduction of CO2 , 2010 .

[177]  B. Li,et al.  Ordered mesoporous CeO2-TiO2 composites: Highly efficient photocatalysts for the reduction of CO2 with H2O under simulated solar irradiation , 2013 .

[178]  C. Sequeira,et al.  Selective electrochemical conversion of CO2 to C2 hydrocarbons , 2010 .

[179]  G. Mul,et al.  Mechanistic study of hydrocarbon formation in photocatalytic CO2 reduction over Ti-SBA-15 , 2011 .

[180]  Yao Zheng,et al.  Graphitic carbon nitride materials: controllable synthesis and applications in fuel cells and photocatalysis , 2012 .

[181]  Jian-Guo Yu,et al.  Photocatalytic reduction of CO2 with H2O on Pt-loaded TiO2 catalyst , 2009 .

[182]  CO2 splitting by H2O to CO and O2 under UV light in TiMCM-41 silicate sieve , 2004 .

[183]  Eric J. Dufek,et al.  Operation of a Pressurized System for Continuous Reduction of CO2 , 2012 .

[184]  Eric J. Dufek,et al.  Bench-scale electrochemical system for generation of CO and syn-gas , 2011 .

[185]  J. Nørskov,et al.  Kinetic Implications of Dynamical Changes in Catalyst Morphology during Methanol Synthesis over Cu/ZnO Catalysts , 1997 .

[186]  K. Lackner,et al.  Sustainable hydrocarbon fuels by recycling CO2 and H2O with renewable or nuclear energy , 2011 .

[187]  E. Carter,et al.  Quantum Chemical Benchmarking, Validation, and Prediction of Acidity Constants for Substituted Pyridinium Ions and Pyridinyl Radicals. , 2012, Journal of chemical theory and computation.

[188]  Xiaoze Du,et al.  Numerical investigation on CO2 photocatalytic reduction in optical fiber monolith reactor , 2013 .

[189]  Ying Li,et al.  Copper and iodine co-modified TiO2 nanoparticles for improved activity of CO2 photoreduction with water vapor , 2012 .

[190]  Kazuhiro Takanabe,et al.  Preparation of Inorganic Photocatalytic Materials for Overall Water Splitting , 2012 .

[191]  M. Anpo,et al.  Photocatalytic synthesis of CH4 and CH3OH from CO2 and H2O on highly dispersed active titanium oxide catalysts , 1995 .

[192]  H. Frei,et al.  Direct observation of a hydroperoxide surface intermediate upon visible light-driven water oxidation at an Ir oxide nanocluster catalyst by rapid-scan FT-IR spectroscopy. , 2011, Journal of the American Chemical Society.

[193]  H. Frei,et al.  Mechanistic Study of CO2 Photoreduction in Ti Silicalite Molecular Sieve by FT-IR Spectroscopy , 2000 .

[194]  B. Davis,et al.  Influence of Gas Feed Composition and Pressure on the Catalytic Conversion of CO2 to Hydrocarbons Using a Traditional Cobalt-Based Fischer−Tropsch Catalyst , 2009 .

[195]  G. Mul,et al.  Artificial photosynthesis over crystalline TiO2-based catalysts: fact or fiction? , 2010, Journal of the American Chemical Society.

[196]  Yong Zhou,et al.  A room-temperature reactive-template route to mesoporous ZnGa2O4 with improved photocatalytic activity in reduction of CO2. , 2010, Angewandte Chemie.

[197]  P. Edwards,et al.  Turning carbon dioxide into fuel , 2010, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

[198]  Jinhua Ye,et al.  The Effects of Crystal Structure and Electronic Structure on Photocatalytic H2 Evolution and CO2 Reduction over Two Phases of Perovskite-Structured NaNbO3 , 2012 .

[199]  J. Ho,et al.  Adsorption, Dissociation, and Hydrogenation of CO2 on WC(0001) and WC-Co Alloy Surfaces Investigated with Theoretical Calculations , 2012 .

[200]  M. Grätzel,et al.  Methanation and photo-methanation of carbon dioxide at room temperature and atmospheric pressure , 1987, Nature.