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  4. Hydrogen Storage and Delivery: The Carbon Dioxide – Formic Acid Couple
 
research article

Hydrogen Storage and Delivery: The Carbon Dioxide – Formic Acid Couple

Laurenczy, Gábor  
2011
Chimia

Carbon dioxide and the carbonates, the available natural C-1 sources, can be easily hydrogenated into formic acid and formates in water; the rate of this reduction strongly depends on the pH of the solution. This reaction is catalysed by ruthenium(II) pre-catalyst complexes with a large variety of water-soluble phosphine ligands; high conversions and turnover numbers have been realised. Although ruthenium(II) is predominant in these reactions, the iron(II) - tris[(2-diphenylphosphino)-ethyl]phosPhine (PP3) complex is also active, showing a new perspective to use abundant and inexpensive iron-based compounds in the CO2 reduction. In the catalytic hydrogenation cycles the in situ formed metal hydride complexes play a key role, their structures with several other intermediates have been proven by multinuclear NMR spectroscopy. In the other hand safe and convenient hydrogen storage and supply is the fundamental question for the further development of the hydrogen economy; and carbon dioxide has been recognised to be a viable H-2 vector. Formic acid - containing 4.4 weight % of H-2, that is 53 g hydrogen per litre - is suitable for H-2 storage; we have shown that in aqueous solutions it can be selectively decomposed into CO-free (CO < 10 ppm) CO2 and H-2. The reaction takes place under mild experimental conditions and it is able to generate high pressure H-2 (up to 600 bar). The cleavage of HCOOH is catalysed by several hydrophilic Ru(II) phosphine complexes (meta-trisulfonated triphenylphosphine, mTPPTS, being the most efficient one), either in homogeneous systems or as immobilised catalysts. We have also shown that the iron(II) - hydrido tris[(2-diphenylphosphino)ethyl]phosphine complex catalyses with an exceptionally high rate and efficiency (turnover frequency, TOF = 9425 h(-1) mol(-1); turnover number, TON = 92400) the formic acid cleavage, in environmentally friendly propylene carbonate solution, opening the way to use cheap, non-noble metal based catalysts for this reaction, too.

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Type
research article
DOI
10.2533/chimia.2011.663
Web of Science ID

WOS:000295811300009

Author(s)
Laurenczy, Gábor  
Date Issued

2011

Publisher

Schweizerische Chemische Gesellschaft

Published in
Chimia
Volume

65

Issue

9

Start page

663

End page

666

Subjects

CO2 reduction

•

Formic acid

•

High-pressure H-2 generation

•

Hydrogen storage

•

Iron catalysis

•

Ruthenium catalyst

•

Aqueous-Solution

•

Homogeneous Hydrogenation

•

Catalytic-Hydrogenation

•

Phosphine Complexes

•

Ruthenium Complexes

•

Mild Conditions

•

Amine Adducts

•

Fuel-Cells

•

Water

•

Generation

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCOM  
Available on Infoscience
October 21, 2011
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/71812
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