Catalytic reduction of U(VI) with formic acid in acid solutions on palladium catalysts

The kinetics of catalytic reduction of U(VI) with formic acid in H₂SO₄ solutions in the presence of Pd/SiO₂ catalysts differing in the size of nanocrystallites of the active metal was studied. A decrease in the size of supported Pd particles leads to a decrease in the specific activity of the catalyst, i.e., the catalytic centers located on large crystallites exhibit higher activity. An increase in the Pd percent content on SiO₂ leads to a decrease in the activity of the catalytic centers, which is caused by a considerable increase in the contribution of the side reaction of catalytic decomposition of HCOOH with an increase in the number of active centers in the catalyst grain. The results obtained are interpreted on the basis of the concepts of the energy nonuniformity of the surface atoms and of the reaction mechanism. The results show that the size of Pd nanocrystallites is an important factor of the selectivity of palladium catalysts in the preparation of U(IV) by catalytic reduction with formic acid.