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Catalytic activation of small molecules: toward applications

English title Catalytic activation of small molecules: toward applications
Applicant Laurenczy Gàbor
Number 117655
Funding scheme Project funding
Research institution Laboratoire de chimie organométallique et médicinale EPFL - SB - ISIC - LCOM
Institution of higher education EPF Lausanne - EPFL
Main discipline Inorganic Chemistry
Start/End 01.10.2007 - 30.09.2010
Approved amount 182'550.00
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Keywords (22)

catalysis in water; hydrogenation; carbon dioxide reduction; aqueous biphasic systems; high pressure FT-IR; aqueous catalysis; ruthenium hydrides; carbon dioxide reduction; reaction mechanism; hydrido carbonate intermediate; high pressure gases; in situ high pressure NMR; water soluble Ru-phosphines; hydrogen storage; high pressure hydrogen generation; formic acid; Ru; Rh; Ir; aqueous CO2 reduction; medium pressure NMR; high pressure H2 generation

Lay Summary (English)

Lead
Lay summary
Aqueous or aqueous/biphasic organometallic catalysis is the basis of several industrial processes. This proposal aims at investigating such catalysis both at fundamental and applied levels. A research project is proposed towards a better understanding of the fundamental aspects of homogeneous catalytic activation of H2, CO2, CO and N2, as well as small organic molecules (HCOOH, alkenes, alkynes, etc.) in various solvents. One drawback of using water or ionic liquids as solvents, however, is the low solubility of the gaseous reactants in these reaction mixtures; therefore elevated pressures are beneficial.
These investigations are based on our experience in aqueous/biphasic organometallic chemistry and in the field of medium/high pressure gas/liquid systems, using FT-IR, UV-vis and NMR spectroscopy in the medium/high pressure domain (up to 2000 bar):
- Further studies on fundamental coordination chemistry of the Ru(II), Rh(I) and Ir(I, III) in aqueous solution will be continued with a variety of catalytically important ligands (phosphines, arenes, small molecules such as H2, CO2, CO, HCOOH, etc). The determined thermodynamic and kinetic data will help to a better understanding of the catalytic processes.
- A vide variety of Ru-, Rh- and Ir- complexes with different ligands will be applied in the reduction of CO2 under medium (up to 100 bar) and high (up to 2000 bar) H2 and CO2 pressure to understand electronic and steric effects in catalytic hydrogenations. The mechanistic investigation will help for a better design of more efficient catalysts.
- The catalytic cycle of CO2 hydrogenation - formic acid decomposition will be studied in details, as HCOOH could be one of the alternatives for hydrogen storage.
- High pressure H2 generation from formic acid will be developed and studied in details.
- Structures of Ru-, Rh- and Ir-hydride/hydrogen complexes in aqueous solution, in ionic liquids and biphasic systems will be determined, as these complexes are supposedly the catalytically active species in hydrogenation and hydroformylation; in order to elucidate reaction mechanisms.
- Several water soluble phosphines complexes of Ru, Rh and Ir will be reacted with H2/D2 at medium and elevated pressures. The influence of the pH, concentrations, co-ligands and other parameters on complex formation will be studied quantitatively.
- The development of medium and high pressure equipments will be continued, according to the requirements of the studies above: continuous pressure monitoring, improved heating and mixing efficiency, applicability of sapphire NMR tubes for oxygen will be improved, construction of a high pressure solid MAS NMR cell is foreseen.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Associated projects

Number Title Start Funding scheme
117348 Study of reaction mechanisms under pressure / high pressure equipment 01.06.2008 R'EQUIP
132411 Catalytic activation of small molecules: towards applications in molecular energy storage 01.10.2010 Project funding
105335 Catalytic activation of small molecules in water, in ionic liquids and in biphasic systems 01.10.2004 Project funding

Abstract

1.Summary Aqueous or aqueous/biphasic organometallic catalysis is the basis of several industrial processes. This proposal aims at investigating such catalysis both at fundamental and applied levels. A research project is proposed towards a better understanding of the fundamental aspects of homogeneous catalytic activation of H2, CO2, CO and N2, as well as small organic molecules (HCOOH, alkenes, alkynes, etc.) in various solvents. One drawback of using water or ionic liquids as solvents, however, is the low solubility of the gaseous reactants in these reaction mixtures; therefore elevated pressures are beneficial.These investigations are based on our experience in aqueous/biphasic organometallic chemistry and in the field of medium/high pressure gas/liquid systems, using FT-IR, UV-vis and NMR spectroscopy in the medium/high pressure domain (up to 2000 bar):- Further studies on fundamental coordination chemistry of the Ru(II), Rh(I) and Ir(I, III) in aqueous solution will be continued with a variety of catalytically important ligands (phosphines, arenes, small molecules such as H2, CO2, CO, HCOOH, etc). The determined thermodynamic and kinetic data will help to a better understanding of the catalytic processes. - A vide variety of Ru-, Rh- and Ir- complexes with different ligands will be applied in the reduction of CO2 under medium (up to 100 bar) and high (up to 2000 bar) H2 and CO2 pressure to understand electronic and steric effects in catalytic hydrogenations. The mechanistic investigation will help for a better design of more efficient catalysts.- The catalytic cycle of CO2 hydrogenation - formic acid decomposition will be studied in details, as HCOOH could be one of the alternatives for hydrogen storage.- High pressure H2 generation from formic acid will be developed and studied in details.- Structures of Ru-, Rh- and Ir-hydride/hydrogen complexes in aqueous solution, in ionic liquids and biphasic systems will be determined, as these complexes are supposedly the catalytically active species in hydrogenation and hydroformylation; in order to elucidate reaction mechanisms.- Several water soluble phosphines complexes of Ru, Rh and Ir will be reacted with H2/D2 at medium and elevated pressures. The influence of the pH, concentrations, co-ligands and other parameters on complex formation will be studied quantitatively. - The development of medium and high pressure equipments will be continued, according to the requirements of the studies above: continuous pressure monitoring, improved heating and mixing efficiency, applicability of sapphire NMR tubes for oxygen will be improved, construction of a high pressure solid MAS NMR cell is foreseen.Catalytic applications will be backed by fundamental synthetic, structural, kinetic, mechanistic studies.
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