The presence of unreacted silanes within cured polydimethylsiloxane (PDMS) leads to the reduction of tetrachloropalladate(II) ions, generating encapsulated palladium colloids. The resulting colloids had varied morphology and were typically less than 80 nm in size. The Pd/PDMS vessels, which contained 0.10 +/- 0.01% Pd, were effective catalysts for the hydrogenation of carbon-carbon multiple bonds for at least ten successive runs with no loss of catalytic activity, and the catalyst does not exhibit the same pyrophoric behavior as Pd on carbon after use in hydrogenation reactions. In addition, storage of previously used Pd/PDMS vessels for 6 months in air did not affect the catalytic activity, and the overall morphology of the catalysts after use was the same as those that have not been involved in catalytic reactions. (C) 2011 Elsevier Inc. All rights reserved.