Nowadays catalytic technologies are widely used to purify indoor and outdoor air from harmful compounds. Recently, Ag–CeO2 composites have found various applications in catalysis due to distinctive physical-chemical properties and relatively low costs as compared to those based on other noble metals. Currently, metal–support interaction is considered the key factor that determines high catalytic performance of silver–ceria composites. Despite thorough investigations, several questions remain debating. Among such issues, there are (1) morphology and size effects of both Ag and CeO2 particles, including their defective structure, (2) chemical and charge state of silver, (3) charge transfer between silver and ceria, (4) role of oxygen vacancies, (5) reducibility of support and the catalyst on the basis thereof. In this review, we consider recent advances and trends on the role of silver–ceria interactions in catalytic performance of Ag/CeO2 composites in low-temperature CO oxidation, soot oxidation, and volatile organic compounds (VOCs) abatement. Promising photo- and electrocatalytic applications of Ag/CeO2 composites are also discussed.
The transformations of oil components from the Zyuzeevskoye field during catalytic aquathermolysis in the presence of a nickel-containing catalyst precursor and hydrogen donors were studied. It was found that the yield of gasoline and diesel fractions increased by more than 36% in the case of catalytic aquathermolysis in the presence of tetralin. The maximum conversion of asphaltenes was achieved with a simultaneous slowing down of coke formation by four times. The calculation of the structural-group parameters of initial asphaltenes and the products of thermal cracking and catalytic aquathermolysis was made, and the hypothetical construction of their molecular structures was proposed. It was established that the phase composition, ratio, and morphology of nickel catalysts after catalytic aquathermolysis (CA) and catalytic aquathermolysis with tetralin (CA+T) depend on the amount of “free” hydrogen and are represented by Ni0.96S and Ni9S8.
Dry reforming of methane with ratio CH4/CO2 = 1 is studied using supported Ni catalysts on SBA-15 modified by CeMnOx mixed oxides with different Ce/Mn ratios (0.25, 1 and 9). The obtained samples are characterized by wide-angle XRD, SAXS, N2 sorption, TPR-H2, TEM, UV–vis and Raman spectroscopies. The SBA-15 modification with CeMnOx decreases the sizes of NiO nanoparticles and enhances the NiO–support interaction. When Ce/Mn = 9, the NiO forms small particles on the surface of large CeO2 particles and/or interacts with CeO2, forming mixed phases. The best catalytic performance (at 650 °C, CH4 and CO2 conversions are 51 and 69%, respectively) is achieved over the Ni/CeMnOx/SBA-15 (9:1) catalyst. The peculiar CeMnOx composition (Ce/Mn = 9) also improves the catalyst stability: In a 24 h stability test, the CH4 conversion decreases by 18 rel.% as compared to a 30 rel.% decrease for unmodified catalyst. The enhanced catalytic stability of Ni/CeMnOx/SBA-15 (9:1) is attributed to the high concentration of reactive peroxo (O−) and superoxo (O2−) species that significantly lower the amount of coke in comparison with Ni-SBA-15 unmodified catalyst (weight loss of 2.7% vs. 42.2%). Ni-SBA-15 modified with equimolar Ce/Mn ratio or Mn excess is less performing. Ni/CeMnOx/SBA-15 (1:4) with the highest content of manganese shows the minimum conversions of reagents in the entire temperature range (X(CO2) = 4–36%, X(CH4) = 8–58%). This finding is possibly attributed to the presence of manganese oxide, which decorates the Ni particles due to its redistribution at the preparation stage.
Novel yttrium-doped CeO2, MnOx, and CeMnOx composites are investigated as catalysts for low-temperature NH3-SCR. The study involves the preparation of unmodified oxide supports using a citrate method followed by modification with Y (2 wt.%) using two approaches, including the one-pot citrate method and incipient wetness impregnation of undoped oxides. The NH3-SCR reaction is studied in a fixed-bed quartz reactor to test the ability of the prepared catalysts in NO reduction. The gas reaction mixture consists of 800 ppm NO, 800 ppm NH3, 10 vol.% O2, and He as a balance gas at a WHSV of 25,000 mL g−1 h−1. The results indicate that undoped CeMnOx mixed oxide exhibits significantly higher deNOx performance compared with undoped and Y-doped MnOx and CeO2 catalysts. Indeed, yttrium presence in CeMnOx promotes the competitive NH3-SCO reaction, reducing the amount of NH3 available for NO reduction and lowering the catalyst activity. Furthermore, the physical-chemical properties of the prepared catalysts are studied using nitrogen adsorption/desorption, XRD, Raman spectroscopy, temperature-programmed reduction with hydrogen, and temperature-programmed desorption of ammonia. This study presents a promising approach to enhancing the performance of NH3-SCR catalysts at low temperatures that can have significant implications for reducing NO emissions.
The present work is focused on nickel catalysts supported on La2O3-CeO2 binary oxides without and with the addition of Cu to the active component for the dry reforming of methane (DRM). The catalysts are characterized using XRD, XRF, TPD-CO2, TPR-H2, and low-temperature N2 adsorption–desorption methods. This work shows the effect of different La:Ce ratios (1:1 and 9:1) and the Cu addition on the structural, acid base, and catalytic properties of Ni-containing systems. The binary LaCeOx oxide at a ratio of La:Ce = 1:1 is characterized by the formation of a solid solution with a fluorite structure, which is preserved upon the introduction of mono- or bimetallic particles. At La:Ce = 9:1, La2O3 segregation from the solid solution structure is observed, and the La excess determines the nature of the precursor of the active component, i.e., lanthanum nickelate. The catalysts based on LaCeOx (1:1) are prone to carbonization during 6 h spent on-stream with the formation of carbon nanotubes. The Cu addition facilitates the reduction of the Cu-Ni catalyst carbonization and increases the number of structural defects in the carbon deposition products. The lanthanum-enriched LaCeOx (9:1) support prevents the accumulation of carbon deposition products on the surface of CuNi/La2O3-CeO2 9:1, providing high DRM activity and an H2/CO ratio of 0.9.
Structure–performance relationships in functional catalysts allow for controlling their performance in a wide range of reaction conditions. Here, the structural and compositional peculiarities in CTAB-templated CeO2-ZrO2-MnOx catalysts prepared by co-precipitation of precursors and their catalytic behavior in CO oxidation and soot combustion are discussed. A complex of physical–chemical methods (low-temperature N2 sorption, XRD, TPR-H2, Raman, HR TEM, XPS) is used to elucidate the features of the formation of interphase boundaries, joint phases, and defects in multicomponent oxide systems. The addition of Mn and/or Zr dopant to ceria is shown to improve its performance in both reactions. Binary Ce-Mn catalysts demonstrate enhanced performance closely followed by the ternary oxide catalysts, which is due the formation of several types of active sites, namely, highly dispersed MnOx species, oxide–oxide interfaces, and oxygen vacancies that can act individually and/or synergistically.