ABSTRACT
The application of composite materials as catalysts for the oxidation of CO and other toxic compounds is a promising approach for air purification. In this work, the composites comprising palladium and ceria components supported on multiwall carbon nanotubes, carbon nanofibers and Sibunit were studied in the reactions of CO and CH4 oxidation. The instrumental methods showed that the defective sites of carbon nanomaterials (CNMs) successfully stabilize the deposited components in a highly-dispersed state: PdO and CeO2 nanoparticles, subnanosized PdOx and PdxCe1-xO2-δ clusters with an amorphous structure, as well as single Pd and Ce atoms, are formed. It was shown that the reactant activation process occurs on palladium species with the participation of oxygen from the ceria lattice. The presence of interblock contacts between PdO and CeO2 nanoparticles has an important effect on oxygen transfer, which consequently affects the catalytic activity. The morphological features of the CNMs, as well as the defect structure, have a strong influence on the particle size and mutual stabilization of the deposited PdO and CeO2 components. The optimal combination of highly dispersed PdOx and PdxCe1-xO2-δ species, as well as PdO nanoparticles in the CNTs-based catalyst, makes it highly effective in both studied oxidation reactions.
ABSTRACT
The composite nanomaterials based on noble metals, reducible oxides, and nanostructured carbon are considered to be perspective catalysts for many useful reactions. In the present work, multi-walled carbon nanotubes (MWCNTs) were used for the preparation of Pd-Ce-Ox/MWCNTs and Pt-Ce-Ox/MWCNTs catalysts comprising the active components (6 wt%Pd, 6 wt%Pt, 20 wt%CeO2) as highly dispersed nanoparticles, clusters, and single atoms. The application of X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) provided analysis of the samples' morphology and structure at the atomic level. For Pd-Ce-Ox/MWCNTs samples, the formation of PdO nanoparticles with an average crystallite size of ~8 nm was shown. Pt-Ce-Ox/MWCNTs catalysts comprised single Pt2+ ions and PtOx clusters less than 1 nm. A comparison of the catalytic properties of the samples showed higher activity of Pd-based catalysts in CO and CH4 oxidation reactions in a low-temperature range (T50 = 100 °C and T50 = 295 °C, respectively). However, oxidative pretreatment of the samples resulted in a remarkable enhancement of CO oxidation activity of Pt-Ce-Ox/MWCNTs catalyst at T < 20 °C (33% of CO conversion at T = 0 °C), while no changes were detected for the Pd-Ce-Ox/MWCNTs sample. The revealed catalytic effect was discussed in terms of the capability of the Pt-Ce-Ox/MWCNTs system to form unique PtOx clusters providing high catalytic activity in low-temperature CO oxidation.
ABSTRACT
The co-crystallisation of [NiEn3](NO3)2 (En = ethylenediamine) with Na2MoO4 and Na2WO4 from a water solution results in the formation of [NiEn3](MoO4)0.5(WO4)0.5 co-crystals. According to the X-ray diffraction analysis of eight single crystals, the parameters of the hexagonal unit cell (space group P-31c, Z = 2) vary in the following intervals: a = 9.2332(3)-9.2566(6); c = 9.9512(12)-9.9753(7) Å with the Mo/W ratio changing from 0.513(3)/0.487(3) to 0.078(4)/0.895(9). The thermal decomposition of [NiEn3](MoO4)0.5(WO4)0.5 individual crystals obtained by co-crystallisation was performed in He and H2 atmospheres. The ex situ X-ray study of thermal decomposition products shows the formation of nanocrystalline refractory alloys and carbide composites containing ternary Ni-Mo-W phases. The formation of carbon-nitride phases at certain stages of heating up to 1000 °C were shown.
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 Mx Cr1-x (M=Pt, Pd) metal solid solution with a chromium content of up to 22â 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 1â 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.
