Gold nanoparticles on titanium oxide and titania-silica supports are active for the formation of propylene oxide by the oxidation of propylene with hydrogen and oxygen mixtures. Cyanide treatment of gold supported on titanosilicate zeolite supports (Au/TS-1) yielded unexpected results. Catalysts treated with weak solutions of sodium cyanide resulted in preferential removal of small gold particles, while catalysts treated with strong solutions resulted in dissolution of the gold and re-precipitation as gold (+1) cyanide. X-ray absorption spectroscopy demonstrated that catalysts that produce propylene oxide in the presence of hydrogen and oxygen mixtures had supported gold (+3) oxide nanoparticles of 3 nm size after synthesis, which were reduced to gold metal at reaction conditions. Samples treated with strong solutions of sodium cyanide resulted in supported gold (+1) cyanide particles of large size, 9-11 nm. These particles did not produce propylene oxide but, surprisingly, showed high selectivity toward propylene hydrogenation. Increasing gold (+1) cyanide particle size resulted in a decrease in hydrogenation activity. (C) 2011 Elsevier Inc. All rights reserved.