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Title: Highly robust hydrogen generation by bio-inspired Ir complexes for dehydrogenation of formic acid in water: Experimental and theoretical mechanistic investigations at different pH

Journal Article · · ACS Catalysis
 [1];  [2];  [2];  [3];  [3];  [4];  [3];  [3];  [2];  [4]
  1. Dalian Univ. of Technology, Panjin (China)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. National Institute of Advanced Industrial Science and Technology, Ibaraki (Japan)
  4. National Institute of Advanced Industrial Science and Technology, Ibaraki (Japan); Japan Science and Technology Agency, Saitama (Japan)
+ Show Author Affiliations

Hydrogen generation from formic acid (FA), one of the most promising hydrogen storage materials, has attracted much attention due to the demand for the development of renewable energy carriers. Catalytic dehydrogenation of FA in an efficient and green manner remains challenging. Here, we report a series of bio-inspired Ir complexes for highly robust and selective hydrogen production from FA in aqueous solutions without organic solvents or additives. One of these complexes bearing an imidazoline moiety (complex 6) achieved a turnover frequency (TOF) of 322,000 h⁻¹ at 100 °C, which is higher than ever reported. The novel catalysts are very stable and applicable in highly concentrated FA. For instance, complex 3 (1 μmol) affords an unprecedented turnover number (TON) of 2,050,000 at 60 °C. Deuterium kinetic isotope effect experiments and density functional theory (DFT) calculations employing a “speciation” approach demonstrated a change in the rate-determining step with increasing solution pH. This study provides not only more insight into the mechanism of dehydrogenation of FA but also offers a new principle for the design of effective homogeneous organometallic catalysts for H₂ generation from FA.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC00112704
OSTI ID:
1213386
Report Number(s):
BNL-108268-2015-JA; R&D Project: CO026; KC0304030
Journal Information:
ACS Catalysis, Vol. 3, Issue 36; ISSN 2155-5435
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 129 works
Citation information provided by
Web of Science

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Cited By (29)

Poly(ethyleneimine)-tethered Ir Complex Catalyst Immobilized in Titanate Nanotubes for Hydrogenation of CO 2 to Formic Acid journal May 2017
Base‐Free Dehydrogenation of Aqueous and Neat Formic Acid with Iridium(III) Cp*(dipyridylamine) Catalysts journal November 2018
Coordination versatility of p-hydroquinone-functionalized dibenzobarrelene-based PC(sp 3 )P pincer ligands journal January 2016
Development of an Iridium-Based Catalyst for High-Pressure Evolution of Hydrogen from Formic Acid journal August 2016
Kinetic Studies on Formic Acid Dehydrogenation Catalyzed by an Iridium Complex towards Insights into the Catalytic Mechanism of High-Pressure Hydrogen Gas Production journal September 2017
Protic N-Heterocyclic Carbene Versus Pyrazole: Rigorous Comparison of Proton- and Electron-Donating Abilities in a Pincer-Type Framework journal September 2016
Cobalt‐Catalyzed Aqueous Dehydrogenation of Formic Acid journal May 2019
Mixed-valence copper( i,ii ) complexes with 4-(1H-pyrazol-1-yl)-6-R-pyrimidines: from ionic structures to coordination polymers journal January 2016
Hydrogen generation from formic acid decomposition on a highly efficient iridium catalyst bearing a diaminoglyoxime ligand journal January 2018
Iridium Complexes with Proton-Responsive Azole-Type Ligands as Effective Catalysts for CO 2 Hydrogenation journal November 2017
Reactivity of Silanes with ( t Bu PONOP)Ruthenium Dichloride: Facile Synthesis of Chloro-Silyl Ruthenium Compounds and Formic Acid Decomposition journal September 2017
Hydrogen Production and Storage on a Formic Acid/Bicarbonate Platform using Water-Soluble N -Heterocyclic Carbene Complexes of Late Transition Metals journal September 2016
Carbon Dioxide Capturing for Purifying Hydrogen Generated by Formic Acid Decomposition journal March 2018
Hydrogen Liberation from Formic Acid Mediated by Efficient Iridium(III) Catalysts Bearing Pyridine-Carboxamide Ligands: Hydrogen Liberation from Formic Acid Mediated by Efficient Iridium(III) Catalysts Bearing Pyridine-Carboxamide Ligands journal April 2018
Efficient Hydrogen Storage and Production Using a Catalyst with an Imidazoline‐Based, Proton‐Responsive Ligand journal December 2016
A Precious Catalyst: Rhodium-Catalyzed Formic Acid Dehydrogenation in Water: A Precious Catalyst: Rhodium-Catalyzed Formic Acid Dehydrogenation in Water journal April 2019
A highly efficient Ir-catalyst for the solventless dehydrogenation of formic acid: the key role of an N-heterocyclic olefin journal January 2018
Dehydrogenation of Formic Acid Catalyzed by Water-Soluble Ruthenium Complexes: X-ray Crystal Structure of a Diruthenium Complex: Dehydrogenation of Formic Acid Catalyzed by Water-Soluble Ruthenium Complexes: X-ray Crystal Structure of a Diruthenium Complex journal January 2019
Bimetallic AgPd Nanoparticles Immobilized on Amine-Functionalized SBA-15 as Efficient Catalysts for Hydrogen Generation from Formic Acid journal December 2016
Hydrogen production from formic acid catalyzed by a phosphine free manganese complex: investigation and mechanistic insights journal January 2020
Half‐sandwich ruthenium complexes with S chiff base ligands bearing a hydroxyl group: Preparation, characterization and catalytic activities journal November 2019
Development of Effective Catalysts for Hydrogen Storage Technology Using Formic Acid journal September 2018
Iridium-catalyzed efficient reduction of ketones in water with formic acid as a hydride donor at low catalyst loading journal January 2018
Carbon Dioxide Hydrogenation and Formic Acid Dehydrogenation Catalyzed by Iridium Complexes Bearing Pyridyl-pyrazole Ligands: Effect of an Electron-donating Substituent on the Pyrazole Ring on the Catalytic Activity and Durability journal November 2018
Mechanistic insights into HCO 2 H dehydrogenation and CO 2 hydrogenation catalyzed by Ir(Cp*) containing tetrahydroxy bipyrimidine ligand: the role of sodium and proton shuttle journal January 2018
Iridium-catalyzed highly efficient chemoselective reduction of aldehydes in water using formic acid as the hydrogen source journal January 2017
Structure–activity relationship study of half-sandwich metal complexes in aqueous transfer hydrogenation catalysis journal January 2020
Streamlined hydrogen production from biomass journal April 2018
Picolinamide‐Based Iridium Catalysts for Dehydrogenation of Formic Acid in Water: Effect of Amide N Substituent on Activity and Stability journal March 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
formic acid dehydrogenation
Ir complexes
mechanism
kinetic isotope effect
pH-dependence