Efficient production of hydrogen from formic acid using a covalent triazine framework supported molecular catalyst.

A heterogeneous molecular catalyst based on Ir(III) Cp* (Cp*=pentamethylcyclopentadienyl) attached to a covalent triazine framework (CTF) is reported. It catalyses the production of hydrogen from formic acid with initial turnover frequencies (TOFs) up to 27,000 h(-1) and turnover numbers (TONs) of more than one million in continuous operation. The CTF support, with a Brunauer-Emmett-Teller (BET) surface area of 1800 m(2)  g(-1), was constructed from an optimal 2:1 ratio of biphenyl and pyridine carbonitrile building blocks. Biphenyl building blocks induce mesoporosity and, therefore, facilitate diffusion of reactants and products whereas free pyridinic sites activate formic acid towards β-hydride elimination at the metal, rendering unprecedented rates in hydrogen production. The catalyst is air stable, produces CO-free hydrogen, and is fully recyclable. Hydrogen production rates of more than 60 mol L(-1)  h(-1) were obtained at high catalyst loadings of 16 wt % Ir, making it attractive towards process intensification.

[1]  Huajie Huang,et al.  Palladium nanoparticles supported on graphitic carbon nitride-modified reduced graphene oxide as highly efficient catalysts for formic acid and methanol electrooxidation , 2014 .

[2]  H. Grützmacher,et al.  Molecular catalysts for hydrogen production from alcohols , 2014 .

[3]  P. Burger,et al.  Syntheses and electronic structures of μ-nitrido bridged pyridine, diimine iridium complexes. , 2014, Chemical communications.

[4]  Chang Won Yoon,et al.  Carbon dioxide mediated, reversible chemical hydrogen storage using a Pd nanocatalyst supported on mesoporous graphitic carbon nitride , 2014 .

[5]  F. Kapteijn,et al.  Molecular promoting of aluminum metal-organic framework topology MIL-101 by N,N-dimethylformamide. , 2014, Inorganic chemistry.

[6]  S. Fukuzumi,et al.  Production of hydrogen peroxide as a sustainable solar fuel from water and dioxygen , 2013 .

[7]  Kaixue Wang,et al.  Highly efficient dehydrogenation of formic acid over a palladium-nanoparticle-based Mott-Schottky photocatalyst. , 2013, Angewandte Chemie.

[8]  Kazuhiko Maeda,et al.  A polymeric-semiconductor-metal-complex hybrid photocatalyst for visible-light CO(2) reduction. , 2013, Chemical communications.

[9]  P. Dyson,et al.  Heterogeneous Silica‐Supported Ruthenium Phosphine Catalysts for Selective Formic Acid Decomposition , 2013 .

[10]  Xinzheng Yang.  Mechanistic insights into iron catalyzed dehydrogenation of formic acid: β-hydride elimination vs. direct hydride transfer. , 2013, Dalton transactions.

[11]  T. Meyer,et al.  Selective electrocatalytic reduction of carbon dioxide to formate by a water-soluble iridium pincer catalyst , 2013 .

[12]  T. Zell,et al.  Efficient hydrogen liberation from formic acid catalyzed by a well-defined iron pincer complex under mild conditions. , 2013, Chemistry.

[13]  Q. Jiang,et al.  An efficient CoAuPd/C catalyst for hydrogen generation from formic acid at room temperature. , 2013, Angewandte Chemie.

[14]  J. Mayer,et al.  Catalytic disproportionation of formic acid to generate methanol. , 2013, Angewandte Chemie.

[15]  R. Rodríguez‐Lugo,et al.  A homogeneous transition metal complex for clean hydrogen production from methanol-water mixtures. , 2013, Nature chemistry.

[16]  Shouheng Sun,et al.  Monodisperse AgPd alloy nanoparticles and their superior catalysis for the dehydrogenation of formic acid. , 2013, Angewandte Chemie.

[17]  Arne Thomas,et al.  Covalent triazine frameworks as heterogeneous catalysts for the synthesis of cyclic and linear carbonates from carbon dioxide and epoxides. , 2012, ChemSusChem.

[18]  G. Laurenczy,et al.  Formic acid as a hydrogen source – recent developments and future trends , 2012 .

[19]  Etsuko Fujita,et al.  Reversible hydrogen storage using CO2 and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures , 2012, Nature Chemistry.

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

[21]  F. Gärtner,et al.  Kohlenstoffdioxid‐neutrale Wasserstoffspeicherung basierend auf Bicarbonaten und Formiaten , 2011 .

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

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

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

[25]  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 .

[26]  F. Schüth,et al.  Feste Katalysatoren für die selektive Niedertemperaturoxidation von Methan zu Methanol , 2009 .

[27]  M. Antonietti,et al.  Solid catalysts for the selective low-temperature oxidation of methane to methanol. , 2009, Angewandte Chemie.

[28]  Tom Van Gerven,et al.  Structure, energy, synergy, time - the fundamentals of Process Intensification , 2009 .

[29]  Markus Antonietti,et al.  Toward Tailorable Porous Organic Polymer Networks: A High-Temperature Dynamic Polymerization Scheme Based on Aromatic Nitriles , 2009 .

[30]  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.

[31]  Markus Antonietti,et al.  From microporous regular frameworks to mesoporous materials with ultrahigh surface area: dynamic reorganization of porous polymer networks. , 2008, Journal of the American Chemical Society.

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

[33]  Arne Thomas,et al.  Ionothermalsynthese von porösen kovalenten Triazin‐ Polymernetzwerken , 2008 .

[34]  Markus Antonietti,et al.  Porous, covalent triazine-based frameworks prepared by ionothermal synthesis. , 2008, Angewandte Chemie.

[35]  S. Fukuzumi,et al.  Mechanistic investigation of CO2 hydrogenation by Ru(II) and Ir(III) aqua complexes under acidic conditions: two catalytic systems differing in the nature of the rate determining step. , 2006, Dalton transactions.

[36]  S. Fukuzumi,et al.  Isolation and crystal structure of a water-soluble iridium hydride: a robust and highly active catalyst for acid-catalyzed transfer hydrogenations of carbonyl compounds in acidic media. , 2003, Journal of the American Chemical Society.

[37]  J. M. Ugalde,et al.  Hydrogen-Bonding Interactions between Formic Acid and Pyridine , 2002 .

[38]  Freek Kapteijn,et al.  Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis , 1995 .