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The volatile organic compounds (VOCx) dangerous for human health are considered great contributors to air pollution. The toxic benzene is extensively applied in the industry. Its complete oxidation is often studied as a model reaction of VOCs combustion since benzene is a very stable organic molecule. Nanosized gold catalysts on Co-doped ceria supports prepared by co-precipitation and mechanochemical mixing are studied. Catalytic tests aimed at complete benzene oxidation and in situ FT-IR measurements are performed. Different catalytic behavior attributed to differences in the structure and the properties of the support is observed. The presence of Co-phase of enhanced redox properties influenced both by gold and modified ceria could be responsible for the high catalytic activity observed at relatively low temperatures in case of mechanochemial mixing mode used. [ABSTRACT FROM AUTHOR]

The production of H2 pure enough for use in fuel cells requires the development of very efficient catalysts for the water-gas shift reaction. Herein, a series of gold catalysts supported on ZnO-promoted CeO2-Al2O3 are presented as interesting systems for the purification of H2 streams through the water-gas shift reaction. The addition of ZnO remarkably promotes the activity of an Au/CeO2/Al2O3 catalyst. This increase in activity is mainly associated with the enhanced oxygen storage capacity exhibited for the Zn-containing solids. High activity and good stability and resistance towards start-up-shut-down situations was found, which makes these catalysts a promising alternative for CO clean-up applications. [ABSTRACT FROM AUTHOR]

Considerable efforts to reduce the harmful emissions of volatile organic compounds (VOCs) have been directed towards the development of highly active and economically viable catalytic materials for complete hydrocarbon oxidation. The present study is focused on the complete benzene oxidation as a probe reaction for VOCs abatement over Co3O4-CeO2 mixed oxides (20, 30, and 40 wt.% of ceria) synthesized by the more sustainable, in terms of less waste, less energy and less hazard, mechanochemical mixing of cerium hydroxide and cobalt hydroxycarbonate precursors. The catalysts were characterized by BET, powder XRD, H2-TPR, UV resonance Raman spectroscopy, and XPS techniques. The mixed oxides exhibited superior catalytic activity in comparison with Co3O4, thus, confirming the promotional role of ceria. The close interaction between Co3O4 and CeO2 phases, induced by mechanochemical treatment, led to strained Co3O4 and CeO2 surface structures. The most significant surface defectiveness was attained for 70 wt.% Co3O4-30 wt.% CeO2. A trend of the highest surface amount of Co3+, Ce3+ and adsorbed oxygen species was evidenced for the sample with this optimal composition. The catalyst exhibited the best performance and 100% benzene conversion was reached at 200 °C (relatively low temperature for noble metal-free oxide catalysts). The catalytic activity at 200 °C was stable without any products of incomplete benzene oxidation. The results showed promising catalytic properties for effective VOCs elimination over low-cost Co3O4-CeO2 mixed oxides synthesized by simple and eco-friendly mechanochemical mixing. [ABSTRACT FROM AUTHOR]

Supported gold on co-precipitated nanosized NiAl layered double hydroxides (LDHs) was studied as an effective catalyst for medium-temperature water–gas shift (WGS) reaction, an industrial catalytic process traditionally applied for the reduction in the amount of CO in the synthesis gas and production of pure hydrogen. The motivation of the present study was to improve the performance of the Au/NiAl catalyst via modification by CeO2. An innovative approach for the direct deposition of ceria (1, 3 or 5 wt.%) on NiAl-LDH, based on the precipitation of Ce3+ ions with 1M NaOH, was developed. The proposed method allows us to obtain the CeO2 phase and to preserve the NiAl layered structure by avoiding the calcination treatment. The synthesis of Au-containing samples was performed through the deposition–precipitation method. The as-prepared and WGS-tested samples were characterized by X-ray powder diffraction, N2-physisorption and X-ray photoelectron spectroscopy in order to clarify the effects of Au and CeO2 loading on the structure, phase composition, textural and electronic properties and activity of the catalysts. The reduction behavior of the studied samples was evaluated by temperature-programmed reduction. The WGS performance of Au/NiAl catalysts was significantly affected by the addition of CeO2. A favorable role of ceria was revealed by comparison of CO conversion degree at 220 °C reached by 3 wt.% CeO2-modified and ceria-free Au/NiAl samples (98.8 and 83.4%, respectively). It can be stated that tuning the properties of Au/NiAl LDH via CeO2 addition offers catalysts with possibilities for practical application owing to innovative synthesis and improved WGS performance. [ABSTRACT FROM AUTHOR]

Abstract: New gold catalysts supported on ceria modified by addition of ZrO2 have been synthesized and tested in the water-gas shift reaction (WGSR) at low temperature, where they displayed better catalytic activity than gold supported on pure ceria, following the trend: AuCe50Zr50>AuCe80Zr20>AuCe. Morphologic, textural, structural and spectroscopic characterisation showed that the addition of zirconia to ceria leads to the formation of mixture of tetragonal ceria–zirconia phases. Moreover, depending on the zirconia amount, a different Au dispersion is observed. Au agglomerates (10–20nm) and nanoparticles (about 2.5nm) have been detected by HRTEM on AuCe80Zr20, while only nanoparticles have been found on AuCe50Zr50. FTIR spectroscopy of CO adsorbed at 120K showed also the presence of Au clusters, more abundant on AuCe50Zr50 than on AuCe80Zr20. However, at low temperature the best catalytic activity of AuCe50Zr50 is correlated not only to the abundance of gold clusters and nanoparticles, but also to the effect of ZrO2 addition that influences the acid/base surface properties of ceria, as successfully demonstrated by adsorption and surface reaction of acetone vapor at room temperature. FTIR measurements performed before and after reaction showed that the carbonate-like species have the lowest stability on the AuCe50Zr50 surface. This feature, along with the presence of a high gold dispersion, makes AuCe50Zr50 the best catalyst in terms of activity and stability. [Copyright &y& Elsevier]

Abstract: Nanosized gold catalysts supported on doped ceria were prepared by deposition–precipitation method. A deep characterization study by HRTEM/EDS, XRD, FT-Raman, TPR and FTIR was undergone in order to investigate the effect of ceria modification by various cations (Sm3+, La3+ and Zn2+) on structural and redox properties of gold catalysts. Doping of ceria affected in different way catalytic activity towards purification of H2 via preferential CO oxidation. The following activity order was observed: Au/Zn–CeO2 >Au/Sm–CeO2 >Au/CeO2 >Au/La–CeO2. The differences in CO oxidation rates were ascribed to different concentration of metallic gold particles on the surface of Au catalysts (as confirmed by the intensity of the band at 2103cm−1 in the FTIR spectra collected during CO–O2 interaction). Gold catalysts on modified ceria showed improved tolerance towards the presence of CO2 and H2O in the PROX feed. The spectroscopic experiments evidence enhanced reactivity when PROX is performed in the presence of H2O already at 90K. [Copyright &y& Elsevier]

Abstract: Mesoporous particles and 1D nanorods of cerium oxides have been prepared by modifying the hydrothermal route of a surfactant-assisted controllable synthesis. Mesoporous cerias were obtained in a sealed glass vessel under continuous stirring, while ceria nanorods were obtained in a Teflon-lined autoclave without stirring. The mesoporous cerias did not show long-range mesoscopic organization, exhibiting a broad mesopore size distribution in the region 8–15nm. A BET surface area of 100m2/g with a total pore volume of 0.33cm3/g is obtained for as-synthesized mesoporous ceria. The ceria nanorods exhibit a cubic crystalline structure after calcination, having the lengths in the range of 150–300nm and diameters in the range of 10–25nm. The growth direction of ceria nanorods is along [110]. A surface area of above 50m2/g is obtained in the calcined nanorods. These synthesized ceria materials were used as supports of nano-sized gold catalysts, prepared by deposition–precipitation method. Their catalytic activity was evaluated by the low-temperature water-gas shift reaction. The gold/mesoporous ceria catalytic system exhibited higher catalytic activity than gold/ceria nanorods. It is revealed that the mesoporous and nanostructured cerias are of much interest as potential supports for gold-based catalysts that are effective for low-temperature water-gas shift reaction. [Copyright &y& Elsevier]

Over the past three decades, supported gold nanoparticles have demonstrated outstanding properties and continue to attract the interest of the scientific community. Several books and comprehensive reviews as well as numerous papers cover a variety of fundamental and applied aspects specific to gold-based catalyst synthesis, characterization by different techniques, relationship among catalyst support features, electronic and structural properties of gold particles, and catalytic activity, reaction mechanism, and theoretical modeling. Among the Au-catalyzed reactions targeting environmental protection and sustainable energy applications, particular attention is paid to pure hydrogen production. The increasing demands for high-purity hydrogen for fuel cell systems caused a renewed interest in the water-gas shift reaction. This well-known industrial process provides an attractive way for hydrogen generation and additional increase of its concentration in the gas mixtures obtained by processes utilizing coal, petroleum, or biomass resources. An effective step for further elimination of CO traces from the reformate stream after water-gas shift unit is the preferential CO oxidation. Developing highly active, stable, and selective catalysts for these two reactions is of primary importance for efficient upgrading of hydrogen purity in fuel cell applications. This review aims to extend the existing knowledge and understanding of the properties of gold-based catalysts for H 2 clean-up reactions. In particular, new approaches and strategies for design of high-performing and cost-effective formulations are addressed. Emphasis is placed on efforts to explore appropriate and economically viable supports with complex composition prepared by various synthesis procedures. Relevance of ceria application as a support for new-generation WGS catalysts is pointed out. The role of the nature of support in catalyst behavior and specifically the existence of an active gold-support interface is highlighted. Long-term stability and tolerance toward start-up/shutdown cycling are discussed. Very recent advances in catalyst design are described focusing on structured catalysts and microchannel reactors. The latest mechanistic aspects of the water-gas shift reaction and preferential CO oxidation over gold-based catalysts from density functional theory calculations are noted because of their essential role in discovering novel highly efficient catalysts.

Fourier transform infrared spectra of CO adsorption from 120 K up to room temperature on two gold catalysts supported on different mixed ceria-titania oxides are discussed in comparison with those obtained on Au/TiO(2) and Au/Fe(2)O(3) reference catalysts provided by the World Gold Council. The spectra of adsorbed CO, run on the different samples before preliminary treatment, are shown and compared with those of the untreated catalysts and of the samples reduced either in CO or in hydrogen. Big differences have been found between the ceria-titania supported samples and the reference ones: unusual absorption bands, irreversible to outgassing, have been detected after CO interaction on the untreated and oxidized ceria containing samples. These absorptions are assigned to CO on Au(n)(+) small clusters stabilized at the ceria defects. By reduction in hydrogen, negatively charged Au(n)(-) species are produced on the same sample. Oxidized small particles are present on the reference catalysts, but only on the untreated samples; after treatment, only metallic step sites are evident.