Precious-Metal-Decorated Chromium(IV) Oxide Nanowires as Efficient Catalysts for 2,4-Toluenediamine Synthesis

The catalytic hydrogenation of 2,4-dinitrotoluene (DNT) to 2,4-toluenediamine (TDA) is a key step in the production of polyurethanes; therefore, the development of efficient hydrogenation catalysts for industrial use is of paramount importance. In the present study, chromium(IV) oxide nanowires were decorated by palladium and platinum nanoparticles in a one-step, simple, and fast preparation method to yield highly efficient hydrogenation catalysts for immediate use. The nanoparticles were deposited onto the surface of CrO₂ nanowires by using ultrasonic cavitation and ethanol as a reduction agent. Beneficially, the catalyst became catalytically active right at the end of the preparation and no further treatment was necessary. The activity of the Pd- and Pt-decorated CrO₂ catalysts were compared in the hydrogenation of 2,4-dinitrotoluene (DNT). Both catalysts have shown high activity in the hydrogenation tests. The DNT conversion exceeded 98% in both cases, whereas the 2,4-toluenediamine (TDA) yields were 99.7 n/n% and 98.8 n/n%, with the Pd/CrO₂ and Pt/CrO₂, respectively, at 333 K and 20 bar H₂ pressure. In the case of the Pt/CrO₂ catalyst, 304.08 mol of TDA formed with 1 mol Pt after 1 h hydrogenation. Activation energies were also calculated to be approximately 24 kJ∙mol^-1. Besides their immediate applicability, our catalysts were well dispersible in the reaction medium (methanolic solution of DNT). Moreover, because of their magnetic behavior, the catalysts were easy to handle and remove from the reaction media by using a magnetic field.