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Ionic Liquids and Methine Conversion

Molecular design of new classes of ionic liquids and modeling of ionic liquid properties for novel applications are a significant effort for PEERI.

1. One of major effort in this field at PEERI is to develop specific ionic liquids (IL) for low temperature methane conversion process. In an environment with a powerful catalyst such as Periana's catalyst1 which can react with methane readily a very reaction inert ionic liquid is needed as the reaction media. We are working to develop ionic liquids which are chemical reaction-resistant, acid- and thermo- stable2. Also the ionic liquids should enhance the methane conversion selectively, such as conversion to methanol.

2. Second interest in this field is to design and synthesize ionic liquids which have specific catalytic functions. By study and understanding of chemical reaction mechanism in ionic liquids we try to incorporate or mobilize homogeneous transition-metal complexes or Lewis acids to specifically designed ionic liquids for catalysis reactions such as alkylation of aromatics. These studies involve new IL and transition metal complex synthesis as well as monitoring of reaction kinetics. New compounds are prepared using specialized vacuum line, Schlenk, and glove box techniques, and are usually characterized by multinuclear NMR, UV-Vis, and FT-IR, LC-MS, GC spectrometry and by single crystal X-ray diffraction methods.

3. Other directions include developing functionalized ionic liquids for gas or liquid separation, purification, new materials and for heat transfer media.

Homogeneous Catalysis in Ionic Liquids

Homogeneous catalysis usually takes place in common organic solvents. However, the majority of solvents which are utilized for homogeneous industrial catalysis are volatile organic compounds (VOCs) such as halohydrocarbons, hydrocarbons or ethers. It has been estimated that global expenditures on VOCs approach approximately 30 billion pounds which means the unavoidable escape of vapor from such a large volume of solvents has a tremendous effect on our earth environment. Reaction in ionic liquids will reduce significantly the release of VOCs. Also charged IL solvent properties will play chemistry differently than common organic solvents. At PEER using IL as media for homogeneous catalysis is a main direction in this field.

Catalysis for Low Temperature Natural Gas to Hydrogen Conversion

Hydrogen-fueled fuel cells promise clean, efficient, and sustainable energy that will help world meet its energy needs in the coming century and beyond. The U.S. consumed 7.9 million barrels of gasoline per day in January 2003, and worldwide production of hydrogen is about 100 million kilograms per day. Most of hydrogen is produced from natural gas by steam methane reforming process at very high temperature (900oC). PEER is now engaged in development of low cost and low temperature process for production of hydrogen. Methane is a particularly attractive substrate for such conversions since it is cheap and readily available.

We try to develop unique catalysts and specific reaction media for the process. An organometallic compound Os(amine)43+(2) ,which was previously developed by Li and Taube2, seems close this goal. When 2 is reduced to Os2+, it is endorsed a tremendous ability to quickly grab two hydrogen at room temperature from same carbon center in a hydrocarbon molecular. This could be developed to a catalyst with a specially designed Ionic Liquid reaction media for the methane transformation at low temperature (room temperature or below 200oC):

Catalysis

Develop New Catalysts for Other Important Organic Reactions.

PEERI also is in process of development of many other synthetically important homogeneous organic catalysis reactions such as Grubbs' catalyst or Sharpless' catalyst for reaction in ionic liquids. Work involves the mobilization, stabilization of the catalysts and elucidations of the catalysis mechanism.

Project: Using Ionic Liquids in Selective Hydrocarbon Conversion Processes
Sponsor: U. S. Department of Energy(DOE)
Co-sponsors: ChevronTexaco and Sachem
Project Dates: Start: 07/01/2004; End: 06/30/2008

References
1. Roy.A. Periana, et al.,Science, 1998, 280, 340
2. Zai-Wei Li and Henry Taube,J. Am. Chem. Soc. 1994, 116, p11584-11585.