Tetraammineplatinum(II) and Tetraamminepalladium(II) Chromates as Precursors of Metal Oxide Catalysts

Abstract

[M(NH₃ )₄ ]A (M=Pt, Pd; A=CrO₄ , Cr₂ O₇ ) and [Pt(NH₃ )₄ (NO₂ )(Cr₂ O₇ )]NO₃ complex salts were synthesized and characterized by a number of physicochemical methods of analysis (IR, single-crystal and powder XRD, and simultaneous thermogravimetry and differential scanning calorimetry with evolved gas analysis mass spectrometry). Thermolysis of the salts obtained in a hydrogen atmosphere proceeds with the partial reduction of chromium to a metallic state and the formation of M_x Cr_1-x (M=Pt, Pd) metal solid solution with a chromium content of up to 22 at % and chromium(III) oxide. The thermal decomposition of salts in an inert and oxidizing atmosphere passes through the formation stage of the MCrO₂ phase with the delafossite structure followed by its subsequent decomposition into chromium(III) oxide and noble metal. Nanosized Pt-Cr₂ O₃ and Pd-Cr₂ O₃ composites obtained by the thermolysis of precursor salts in air at 500 °C and being held at this temperature for 1 h showed a high catalytic activity in the CO total oxidation (TOX) and preferential oxidation in the excess of hydrogen (PROX) processes compared with that of monometallic Pt and Pd powders.