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Building 134
P.O. Box 5000
Upton, NY 11973-5000
phone 631 344-2345
fax 631 344-3368

managed for the U.S. Department of Energy
by Brookhaven Science Associates, a company
founded by Stony Brook University and Battelle

News Release

Number: 03-57
Released: July 30, 2003
Contact: Karen McNulty Walsh, 631 344-8350 or Mona S. Rowe, 631 344-5056

Scientists Develop Recyclable Catalyst for
Solvent-Free Reactions

Holds promise of less waste and lower cost for manufacturing processes

UPTON, NY — Chemists at the U.S. Department of Energy’s Brookhaven National Laboratory have developed a catalyst that achieves complete conversion of reactants to products and can easily be recovered and reused with no waste. The catalyst, described in the July 31, 2003, issue of Nature, eliminates the need for using solvents in an important step in the synthesis of many organic compounds, such as pharmaceutical agents and agricultural products.

Bullock and DioumaevSuch a complete transformation of reactants to products without the need for additional separation steps is particularly attractive in the manufacture of pharmaceuticals, which must be pure and free from residual metal catalysts. But it should be of interest to all in industry who seek to reduce waste and the cost of manufacturing processes.

“Avoiding the use of solvents is an important way to prevent waste in chemical manufacturing processes,” said Brookhaven chemist Morris Bullock, who led the research. This new catalyst, developed by Vladimir Dioumaev, a postdoc in Bullock’s lab, achieves that goal in two ways:

First, as a homogeneous catalyst, it dissolves in the reactants. That eliminates the need for a solvent to mix the reagents to get the reaction going. Second, it precipitates as a solid at the end of the reaction, so no solvents or additional steps are required to separate the catalyst from the products. “It separates itself. You can simply pour the products into another container and use the catalyst again,” Dioumaev said.

“The concept is simple, but striking the right balance between maintaining catalyst solubility throughout the reaction and precipitation at the end is a diabolical problem,” Bullock said. Homogeneous catalysts usually remain dissolved at the end of the reaction, presenting a problem in recovery of the catalyst. But a catalyst that precipitates before the reaction is over would lead to incomplete conversion of the reactants. The Brookhaven team was trying to develop a catalyst that would retain some solubility in the liquid phase until all the reactants were used up, but which would then precipitate to facilitate recovery and recycling of the catalyst.

The catalyst is soluble in one of the reagents and remains soluble when the other reagent is added. As the reaction goes on, and the product builds up, the catalyst precipitates from the mixture as oil. This oil - liquid clathrate - remains to be an active catalyst, as the reagents are able to penetrate into it. When all the reagents are converted into products, the oily catalyst turns into a sticky solid, which can be easily separated and recycled.

To explore the concept, the scientists investigated a variety of catalysts designed to react ketones, a class of organic molecules, with organic silicon compounds. These reactions, called hydrosilylation reactions, can be used in the manufacture of drugs, pesticides, and other organic compounds. The products of such reactions are also used in the preparation of ceramic materials.

The catalysts they experimented with had been found in their earlier work to dissolve in ketones but form oily precipitates, known as liquid clathrates, from many other solvents. Such an oily phase, they thought, might be ideal for maintaining the ability to catalyze the reaction to completion, because the oil would allow access to the liquid reactants rather than settling out as a solid precipitate would. By experimentally altering the structure of the catalyst, the scientists arrived at a formulation containing the metal tungsten that accomplished their goal.

At first, the catalyst mixes readily with the reactants. Then, as the reaction progresses to near completion, the catalyst begins to precipitate, but remains suspended as an oily liquid clathrate, clearly visible in the tube where the reaction is taking place. “The reagents can penetrate the oil to keep reacting until all the reactants are used up,” Dioumaev said. When that happens, the no-longer-soluble catalyst precipitates out as a solid, which settles to the bottom of the test tube. Analysis revealed that there was essentially no catalyst remaining in the liquid products.

The Brookhaven scientists plan to continue their research to see if this general method of catalyst self-separation using liquid clathrate catalysts can be applied to other reactions. This research often requires knowledge of the molecular structure of the catalyst, and the tungsten catalyst used in this research was deciphered at the National Synchrotron Light Source (NSLS) at Brookhaven Lab. A paper on the structural determination was recently published in Chemical Communications.

This research was funded by the U.S. Department of Energy’s Office of Science, Division of Chemical Sciences.