Formic acid as a hydrogen source – recent developments and future trends

Formic acid has recently been suggested as a promising hydrogen storage material. The basic concept is briefly discussed and the recent advances in the development of formic acid dehydrogenation catalysts are shown. Both the state of research for heterogeneous and for homogeneous catalyst systems are reviewed in detail and an outlook on necessary development steps is presented. Formic acid is considered as one of the most promising materials for hydrogen storage today. There are a number of highly active and robust homogeneous catalysts that selectively decompose formic acid to H2 and CO2 near to room temperature. Although the activity and selectivity of heterogeneous catalysts have not yet reached the level of homogeneous systems, this gap is closing.

[1]  M. Wills,et al.  Hydrogen generation from formic acid and alcohols using homogeneous catalysts. , 2010, Chemical Society reviews.

[2]  M. Beller,et al.  Ruthenium-catalyzed hydrogenation of bicarbonate in water. , 2010, ChemSusChem.

[3]  F. Solymosi,et al.  Decomposition and reforming of formic acid on supported Au catalysts: production of CO-free H2 , 2011 .

[4]  R. Puddephatt,et al.  The interconversion of formic acid and hydrogen/carbon dioxide using a binuclear ruthenium complex catalyst , 2000 .

[5]  W. Trogler,et al.  Solvent-dependent reactions of carbon dioxide with a platinum(II) dihydride. Reversible formation of a platinum(II) formatohydride and a cationic platinum(II) dimer, [Pt2H3(PEt3)4][HCO2] , 1982 .

[6]  O. Alfano,et al.  Solar Degradation of Formic Acid: Temperature Effects on the Photo-Fenton Reaction , 2007 .

[7]  Toshiyuki Abe,et al.  A novel example of molecular hydrogen generation from formic Acid at visible-light-responsive photocatalyst. , 2009, ACS applied materials & interfaces.

[8]  G. Smith,et al.  Hydrogen production from formic acid decomposition at room temperature using a Ag-Pd core-shell nanocatalyst. , 2011, Nature nanotechnology.

[9]  Paul J Dyson,et al.  A viable hydrogen-storage system based on selective formic acid decomposition with a ruthenium catalyst. , 2008, Angewandte Chemie.

[10]  Xue-li Li,et al.  Hydrogen generation from formic acid decomposition with a ruthenium catalyst promoted by functionalized ionic liquids. , 2010, ChemSusChem.

[11]  P. Wasserscheid,et al.  Simple and recyclable ionic liquid based system for the selective decomposition of formic acid to hydrogen and carbon dioxide , 2011 .

[12]  J. Dupont,et al.  Decomposition of Formic Acid Catalyzed by a Phosphine‐Free Ruthenium Complex in a Task‐Specific Ionic Liquid , 2010 .

[13]  S. Enthaler,et al.  Carbon dioxide--the hydrogen-storage material of the future? , 2008, ChemSusChem.

[14]  Yi Wu,et al.  Hydrogen production via electrolysis of aqueous formic acid solutions , 2011 .

[15]  F. Joó Breakthroughs in hydrogen storage--formic Acid as a sustainable storage material for hydrogen. , 2008, ChemSusChem.

[16]  F. Solymosi,et al.  Production of CO-Free H2 by Formic Acid Decomposition over Mo2C/Carbon Catalysts , 2010 .

[17]  G. Laurenczy,et al.  A charge/discharge device for chemical hydrogen storage and generation. , 2011, Angewandte Chemie.

[18]  S. Senanayake,et al.  Redox Pathways for HCOOH Decomposition over CeO2 Surfaces , 2008 .

[19]  M. Beller,et al.  Hydrogen generation: catalytic acceleration and control by light. , 2009, Chemical communications.

[20]  S. Strauss,et al.  ChemInform Abstract: RHODIUM(I)‐CATALYZED DECOMPOSITION OF FORMIC ACID , 1979, Chemischer Informationsdienst.

[21]  F. Solymosi,et al.  Production of CO-free H2 from formic acid. A comparative study of the catalytic behavior of Pt metals on a carbon support , 2011 .

[22]  T. Akita,et al.  Synergistic catalysis of metal-organic framework-immobilized Au-Pd nanoparticles in dehydrogenation of formic acid for chemical hydrogen storage. , 2011, Journal of the American Chemical Society.

[23]  G. Clarkson,et al.  Insights into hydrogen generation from formic acid using ruthenium complexes , 2009 .

[24]  Orlando M. Alfano,et al.  Kinetic study of the photo-Fenton degradation of formic acid: Combined effects of temperature and iron concentration , 2009 .

[25]  Takeshi Kobayashi,et al.  Unusually large tunneling effect on highly efficient generation of hydrogen and hydrogen isotopes in pH-selective decomposition of formic acid catalyzed by a heterodinuclear iridium-ruthenium complex in water. , 2010, Journal of the American Chemical Society.

[26]  Umit B. Demirci,et al.  Chemical hydrogen storage: ‘material’ gravimetric capacity versus ‘system’ gravimetric capacity , 2011 .

[27]  M. Beller,et al.  Hydrogen generation at ambient conditions: application in fuel cells. , 2008, ChemSusChem.

[28]  M. Yin,et al.  Novel PdAu@Au/C Core-Shell Catalyst: Superior Activity and Selectivity in Formic Acid Decomposition for Hydrogen Generation , 2010 .

[29]  Changpeng Liu,et al.  Available hydrogen from formic acid decomposed by rare earth elements promoted Pd-Au/C catalysts at low temperature. , 2010, ChemSusChem.

[30]  Robert B. May,et al.  Hydrogen generation from formic acid decomposition by ruthenium carbonyl complexes. Tetraruthenium dodecacarbonyl tetrahydride as an active intermediate. , 2011, ChemSusChem.

[31]  Ulrich Eberle,et al.  Fuel cell vehicles: Status 2007 , 2007 .

[32]  Changpeng Liu,et al.  High-quality hydrogen from the catalyzed decomposition of formic acid by Pd-Au/C and Pd-Ag/C. , 2008, Chemical communications.

[33]  K. Kendall,et al.  A continuous-flow method for the generation of hydrogen from formic acid. , 2010, ChemSusChem.

[34]  Y. Himeda Highly efficient hydrogen evolution by decomposition of formic acid using an iridium catalyst with 4,4′-dihydroxy-2,2′-bipyridine , 2009 .

[35]  Xin-bo Zhang,et al.  Liquid-phase chemical hydrogen storage: catalytic hydrogen generation under ambient conditions. , 2010, ChemSusChem.

[36]  R. Ludwig,et al.  Iron-catalyzed hydrogen production from formic acid. , 2010, Journal of the American Chemical Society.

[37]  M. Ojeda,et al.  Formic acid dehydrogenation on au-based catalysts at near-ambient temperatures. , 2009, Angewandte Chemie.

[38]  T. Schmidt,et al.  Carbon Dioxide and Formic Acid - The couple for an environmental-friendly hydrogen storage? , 2010 .

[39]  M. Beller,et al.  CO2-"neutral" hydrogen storage based on bicarbonates and formates. , 2011, Angewandte Chemie.

[40]  E. Borowiak‐Palen,et al.  Photocatalytic hydrogen generation over alkaline-earth titanates in the presence of electron donors , 2008 .

[41]  J. Falconer,et al.  Effect of water on formic acid photocatalytic decomposition on TiO2 and Pt/TiO2 , 2010 .

[42]  G. Dey,et al.  Photolysis studies on HCOOH and HCOO− in presence of TiO2 photocatalyst as suspension in aqueous medium , 2009 .

[43]  R. Ludwig,et al.  ortho-Metalation of iron(0) tribenzylphosphine complexes: homogeneous catalysts for the generation of hydrogen from formic acid. , 2010, Angewandte Chemie.

[44]  Y. Himeda Conversion of CO2 into Formate by Homogeneously Catalyzed Hydrogenation in Water: Tuning Catalytic Activity and Water Solubility through the Acid–Base Equilibrium of the Ligand , 2007 .

[45]  Kwong‐Yu Chan,et al.  Low activation energy dehydrogenation of aqueous formic acid on platinum-ruthenium-bismuth oxide at near ambient temperature and pressure. , 2009, Chemical communications.

[46]  S. Fukuzumi,et al.  Efficient catalytic decomposition of formic acid for the selective generation of H2 and H/D exchange with a water-soluble rhodium complex in aqueous solution. , 2008, ChemSusChem.

[47]  R. Compton,et al.  Clean, efficient electrolysis of formic acid via formation of eutectic, ionic mixtures with ammonium formate , 2010 .

[48]  P. Dyson,et al.  Influence of water-soluble sulfonated phosphine ligands on ruthenium catalyzed generation of hydrogen from formic acid , 2010 .

[49]  C. Mullins,et al.  Selective decomposition of formic acid on molybdenum carbide: A new reaction pathway , 2010 .

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

[51]  P. Dyson,et al.  Hydrogen storage and delivery: immobilization of a highly active homogeneous catalyst for the decomposition of formic acid to hydrogen and carbon dioxide , 2009 .

[52]  J. O'm. Bockris A hydrogen economy. , 1972 .

[53]  R. Ludwig,et al.  Efficient Dehydrogenation of Formic Acid Using an Iron Catalyst , 2011, Science.

[54]  H. Sugihara,et al.  Half-Sandwich Complexes with 4,7-Dihydroxy-1,10-phenanthroline: Water-Soluble, Highly Efficient Catalysts for Hydrogenation of Bicarbonate Attributable to the Generation of an Oxyanion on the Catalyst Ligand , 2004 .

[55]  Yurii A. Chesalov,et al.  In situ FTIR study of the kinetics of formic acid decomposition on V–Ti oxide catalyst under stationary and non-stationary conditions. Determination of kinetic constants , 2009 .

[56]  J. Yi,et al.  Influence of Aspect Ratio of TiO2 Nanorods on the Photocatalytic Decomposition of Formic Acid , 2009 .

[57]  Ulrich Eberle,et al.  Hydrogen storage: the remaining scientific and technological challenges. , 2007, Physical Chemistry, Chemical Physics - PCCP.

[58]  M. Beller,et al.  Improved hydrogen generation from formic acid , 2009 .

[59]  Heiji Enomoto,et al.  Rapid and highly selective conversion of biomass into value-added products in hydrothermal conditions: chemistry of acid/base-catalysed and oxidation reactions , 2011 .

[60]  Arne Thomas,et al.  Organic materials for hydrogen storage applications: from physisorption on organic solids to chemisorption in organic molecules , 2009 .

[61]  S. Beloshapkin,et al.  Hydrogen from formic acid decomposition over Pd and Au catalysts , 2010 .

[62]  Ning Yan,et al.  Selective formic acid decomposition for high-pressure hydrogen generation: a mechanistic study. , 2009, Chemistry.

[63]  T. Hirose,et al.  Interconversion between formic acid and H(2)/CO(2) using rhodium and ruthenium catalysts for CO(2) fixation and H(2) storage. , 2011, ChemSusChem.

[64]  M. Simões,et al.  Clean hydrogen generation through the electrocatalytic oxidation of formic acid in a Proton Exchange Membrane Electrolysis Cell (PEMEC) , 2012 .

[65]  R. Compton,et al.  Sustainable energy: a review of formic acid electrochemical fuel cells , 2011 .

[66]  Matthias Beller,et al.  Controlled generation of hydrogen from formic acid amine adducts at room temperature and application in H2/O2 fuel cells. , 2008, Angewandte Chemie.

[67]  J. Ibers,et al.  Cis dihydride diphosphine complexes of platium(II) and their dehydrogenation to form dimeric platinum(0) complexes. The structure of [Pt(tert-Bu)2P(CH2)3P(tert-Bu)2]2 , 1978 .

[68]  G. Olah,et al.  Anthropogenic chemical carbon cycle for a sustainable future. , 2011, Journal of the American Chemical Society.

[69]  N. Matubayasi,et al.  Controlling the equilibrium of formic acid with hydrogen and carbon dioxide using ionic liquid. , 2010, The journal of physical chemistry. A.

[70]  Q. Guo,et al.  Selective Decomposition of Formic Acid over Immobilized Catalysts , 2011 .

[71]  G. Huber,et al.  Production of furfural and carboxylic acids from waste aqueous hemicellulose solutions from the pulp and paper and cellulosic ethanol industries , 2011 .

[72]  J. Vohs,et al.  Reaction of Formic Acid on Zn-Modified Pd(111) , 2009 .

[73]  M. Beller,et al.  Catalytic Generation of Hydrogen from Formic acid and its Derivatives: Useful Hydrogen Storage Materials , 2010 .

[74]  J. M. Trillo,et al.  Mechanism of formic acid decomposition on 3d metal oxides , 1971 .

[75]  M. Beller,et al.  Continuous Hydrogen Generation from Formic Acid: Highly Active and Stable Ruthenium Catalysts , 2009 .