Novel TiO2-Supported Gold Nanoflowers for Efficient Photocatalytic NOx Abatement.

In this study, we pioneered the synthesis of nanoflower-shaped TiO2-supported Au photocatalysts and investigated their properties. Au nanoflowers (Au NFs) were prepared by a Na-citrate and hydroquinone-based preparation method, followed by wet impregnation of the derived Au NFs on the surface of TiO2 nanorods (TNR). A uniform and homogeneous distribution of Au NFs was observed in the TNR + NF(0.7) sample (lower Na-citrate concentration), while their distribution was heterogeneous in the TNR + NF(1.4) sample (higher Na-citrate concentration). The UV-Vis DR spectra revealed the size- and shape-dependent optical properties of the Au NFs, with the LSPR effect observed in the visible region. The solid-state EPR spectra showed the presence of Ti3+, oxygen vacancies and electron interactions with organic compounds on the catalyst surface. In the case of the TNR + NF(0.7) sample, high photocatalytic activity was observed in the H2-assisted reduction of NO2 to N2 at room temperature under visible-light illumination. In contrast, the TNR + NF(1.4) catalyst as well as the heat-treated samples showed no ability to reduce NO2 under visible light, indicating the presence of deformed Au NFs limiting the LSPR effect. These results emphasized the importance of the choice of synthesis method, as this could strongly influence the photocatalytic activity of the Au NFs.

Hierarchically structured TiO2-based composites for Fenton-type oxidation processes.

A novel hierarchically structured composite aimed as a stable catalyst for the heterogeneous Fenton-type (HFT) oxidation process was developed by using a cost-effective and versatile technique. Prussian Blue nanoparticles (PBNP) were dispersed onto aligned macroporous TiO2 (rutile) monoliths prepared via directional freezing of aqueous dispersions of TiO2 nanoparticles. The catalytic performance was evaluated in the HFT oxidation of an azo dye frequently used as a model contaminant, Orange G (OG). Experiments were carried out in a liquid batch-recycle reactor, in which the liquid flow rate was set to ensure negligible external mass transfer resistance. The catalyst exhibited good activity to form highly oxidative radicals from hydrogen peroxide decomposition, which readily discolored OG. Significant reduction of the time required to attain complete discoloration and improvement in TOC removal were achieved by adjusting operating conditions and oxidant dosage strategies. Almost complete OG conversion at around 90 min and 34.4% of TOC removal after 4 h were achieved by using the best evaluated strategy. The catalyst activity was tested under specific operating conditions and remained unaltered during 42 cycles of 4 h each (total 168 h). The fresh and used PBNP/TiO2 catalysts and the support were thoroughly characterized by several techniques. Results supported the excellent stability exhibited by the catalyst in the OG HFT oxidation.

Highly Porous Cationic Polyelectrolytes via Oil-in-Water Concentrated Emulsions: Synthesis and Adsorption Kinetic Study.

This work merges the fields of highly porous polymers (polymerized high internal phase emulsions, polyHIPEs) and synthetic cationic polyelectrolytes and introduces a new approach toward the synthesis of highly porous cationic polyelectrolytes. Cationic polyelectrolytes based on (3-acrylamidopropyl)-trimethylammonium chloride (AMPTMA) were synthesized directly through the oil-in-water HIPEs. The resulting polyelectrolyte-based polyHIPEs are distinguished by the highly porous morphology as well as high concentration and accessibility of the cationic N-quaternized functional groups. The most efficient AMPTMA-based polyelectrolyte polyHIPE exhibits the total ion-exchange capacity of 3.53 mmol of AgNO3 per gram of dry resin and the water uptake of up to 95 g·g-1, which is a great improvement as compared to the state-of-the-art of polyHIPE absorbents bearing cationic moieties. Results of erythrosine dye adsorption show that chemisorption is a rate-determining step because adsorption follows the pseudo-second-order kinetic model. Multilinearity of the Weber and Morris plots assumes that more than one regime is involved in the diffusion of the erythrosine dye molecules into the polyHIPE structure with the diffusion in between the swollen polymer chains as a rate-limiting step.

Support material dictates the attached biomass characteristics during the immobilization process in anaerobic continuous-flow packed-bed bioreactor.

Hydrogen is considered to be an ideal energy alternative to replace environmentally burdensome fossil fuels. For its long-term production the immobilized biofilm system is the most promising and to choose the right support material the most challenging. In this respect, the anaerobic up-flow bioreactors packed with four most used support materials (polyethylene, polyurethane, activated carbon and expanded clay) were tested to investigate the crucial bacteria sensitive period-the immobilization process. Seven-day-operation was necessary and sufficient to reach metabolic and microbial stability regardless of support material used. The support material had an influence on the microbial metabolic activity as well as on quantity and quality characteristics of the immobilized microbial community, being polyethylene and expanded clay more appropriate as supports among the materials evaluated; this could be attributed to pH alteration. The obtained results suggest that the support material dictates the outcome of the immobilization process in the anaerobic continuous-flow bioreactor.

Biohydrogen Production from Simple Carbohydrates with Optimization of Operating Parameters.

Hydrogen could be alternative energy carrier in the future as well as source for chemical and fuel synthesis due to its high energy content, environmentally friendly technology and zero carbon emissions. In particular, conversion of organic substrates to hydrogen via dark fermentation process is of great interest. The aim of this study was fermentative hydrogen production using anaerobic mixed culture using different carbon sources (mono and disaccharides) and further optimization by varying a number of operating parameters (pH value, temperature, organic loading, mixing intensity). Among all tested mono- and disaccharides, glucose was shown as the preferred carbon source exhibiting hydrogen yield of 1.44 mol H(2)/mol glucose. Further evaluation of selected operating parameters showed that the highest hydrogen yield (1.55 mol H(2)/mol glucose) was obtained at the initial pH value of 6.4, T=37 °C and organic loading of 5 g/L. The obtained results demonstrate that lower hydrogen yield at all other conditions was associated with redirection of metabolic pathways from butyric and acetic (accompanied by H(2) production) to lactic (simultaneous H(2) production is not mandatory) acid production. These results therefore represent an important foundation for the optimization and industrial-scale production of hydrogen from organic substrates.

Adverse effects of bisphenol A on water louse (Asellus aquaticus).

Experiments were performed to study the effects of short and long-term exposure to bisphenol A (BPA) on a freshwater crustacean isopod Asellus aquaticus (L.). Two life stages of isopods were exposed to a range of BPA concentrations, from aqueous and two dietary sources, in the form of with BPA spiked conditioned alder leaf (Alnus glutinosa) discs, or spiked formulated sediment, to determine the relative importance of each source of exposure on the uptake of this contaminant. Several lethal and sublethal endpoints were evaluated in this study to measure the potential effects of BPA on A. aquaticus, including mortality, growth and feeding rate inhibition, mobility inhibition, de-pigmentation and molting disturbances. They signify a correlation to BPA levels and a difference in BPA uptake efficiency from different uptake sources. Results of acute exposure to BPA show a greater sensitivity of test systems using juvenile specimens with a 96 h LC50 of 8.6 mg L(-1) BPA in water medium and a 96 h LC50 of 13.5 mg L(-1) BPA in sediment. In comparison, adult isopods show a 96 h LC50 of 25.1 mg L(-1) BPA in water medium and a 96 h LC50 of 65.1 mg L(-1) BPA in sediment. Observed endpoints of chronic exposures suggest the alder leave discs to be the most efficient uptake source of BPA, in contrast to uptake from water or heterogeneous sediment. Significant (p<0.05) growth inhibition, with a 21d NOEC of 0.5/2.5 mg L(-1) (for juvenile/adult organisms), and feeding rate inhibition, with a 21d NOEC of 0.5/1.0 mg L(-1) (for juvenile/adult organisms), were proven to be the most sensitive toxicity endpoints. An even more sensitive effect turned out to be molting frequency, which was significantly reduced; a 21d NOEC was 1.0 mg L(-1) of BPA for adult organisms and an even lower 21d NOEC of 0.05 mg L(-1) of BPA for juveniles. The observed endpoints are recorded at very low, non-toxic exposure concentrations, indicating that BPA acts as an endocrine disrupting compound, as well as a toxic substance. We also determined the importance of the direct dietary uptake of the pollutants, significant for juveniles as well as adult animals.

Unexpected toxicity to aquatic organisms of some aqueous bisphenol A samples treated by advanced oxidation processes.

In this study, photocatalytic and catalytic wet-air oxidation (CWAO) processes were used to examine removal efficiency of bisphenol A from aqueous samples over several titanate nanotube-based catalysts. Unexpected toxicity of bisphenol A (BPA) samples treated by means of the CWAO process to some tested species was determined. In addition, the CWAO effluent was recycled five- or 10-fold in order to increase the number of interactions between the liquid phase and catalyst. Consequently, the inductively coupled plasma mass spectrometry (ICP-MS) analysis indicated higher concentrations of some toxic metals like chromium, nickel, molybdenum, silver, and zinc in the recycled samples in comparison to both the single-pass sample and the photocatalytically treated solution. The highest toxicity of five- and 10-fold recycled solutions in the CWAO process was observed in water fleas, which could be correlated to high concentrations of chromium, nickel, and silver detected in tested samples. The obtained results clearly demonstrated that aqueous samples treated by means of advanced oxidation processes should always be analyzed using (i) chemical analyses to assess removal of BPA and total organic carbon from treated aqueous samples, as well as (ii) a battery of aquatic organisms from different taxonomic groups to determine possible toxicity.

Correction to "Sustainable In-Water Synthesis of Aliphatic Porous Polyazines: A Versatile Platform for Conjugated Aerogels, PolyHIPEs, or Carbon Foams".

[This corrects the article DOI: 10.1021/acs.macromol.3c00437.].

Highly Porous Polymer Beads Coated with Nanometer-Thick Metal Oxide Films for Photocatalytic Oxidation of Bisphenol A.

Highly porous metal oxide-polymer nanocomposites are attracting considerable interest due to their unique structural and functional features. A porous polymer matrix brings properties such as high porosity and permeability, while the metal oxide phase adds functionality. For the metal oxide phase to perform its function, it must be fully accessible, and this is possible only at the pore surface, but functioning surfaces require controlled engineering, which remains a challenge. Here, highly porous nanocomposite beads based on thin metal oxide nanocoatings and polymerized high internal phase emulsions (polyHIPEs) are demonstrated. By leveraging the unique properties of polyHIPEs, i.e., a three-dimensional (3D) interconnected network of macropores, and high-precision of the atomic-layer-deposition technique (ALD), we were able to homogeneously coat the entire surface of the pores in polyHIPE beads with TiO2-, ZnO-, and Al2O3-based nanocoatings. Parameters such as nanocoating thickness, growth per cycle (GPC), and metal oxide (MO) composition were systematically controlled by varying the number of deposition cycles and dosing time under specific process conditions. The combination of polyHIPE structure and ALD technique proved advantageous, as MO-nanocoatings with thicknesses between 11 ± 3 and 40 ± 9 nm for TiO2 or 31 ± 6 and 74 ± 28 nm for ZnO and Al2O3, respectively, were successfully fabricated. It has been shown that the number of ALD cycles affects both the thickness and crystallinity of the MO nanocoatings. Finally, the potential of ALD-derived TiO2-polyHIPE beads in photocatalytic oxidation of an aqueous bisphenol A (BPA) solution was demonstrated. The beads exhibited about five times higher activity than nanocomposite beads prepared by the conventional (Pickering) method. Such ALD-derived polyHIPE nanocomposites could find wide application in nanotechnology, sensor development, or catalysis.

Winning Combination of Cu and Fe Oxide Clusters with an Alumina Support for Low-Temperature Catalytic Oxidation of Volatile Organic Compounds.

A γ-alumina support functionalized with transition metals is one of the most widely used industrial catalysts for the total oxidation of volatile organic compounds (VOCs) as air pollutants at higher temperatures (280-450 °C). By rational design of a bimetal CuFe-γ-alumina catalyst, synthesized from a dawsonite alumina precursor, the activity in total oxidation of toluene as a model VOC at a lower temperature (200-380 °C) is achieved. A fundamental understanding of the catalyst and the reaction mechanism is elucidated by advanced microscopic and spectroscopic characterizations as well as by temperature-programmed surface techniques. The nature of the metal-support bonding and the optimal abundance between Cu-O-Al and Fe-O-Al species in the catalysts leads to synergistic catalytic activity promoted by small amounts of iron (Fe/Al = 0.005). The change in the metal oxide-cluster alumina interface is related to the nature of the surfaces to which the Cu atoms attach. In the most active catalyst, the CuO6 octahedra are attached to 4 Al atoms, while in the less active catalyst, they are attached to only 3 Al atoms. The oxidation of toluene occurs via the Langmuir-Hinshelwood mechanism. The presented material introduces a prospective family of low-cost and scalable oxidation catalysts with superior efficiency at lower temperatures.

Antioxidant responses and whole-organism changes in Daphnia magna acutely and chronically exposed to endocrine disruptor bisphenol A.

Bisphenol A (BPA) is a well known endocrine disruptor. Significantly less is known about its ability to induce antioxidant defense and oxidative stress in aquatic organisms. This is an interesting subject because BPA can act both as a prooxidant (induces the formation of reactive oxygen species) and an antioxidant. The aim of the present study was to elucidate if BPA induces changes in the activities of antioxidant enzymes catalase (CAT) and glutathione S-transferases (GSTs) and the level of lipid peroxidation in crustacean Daphnia magna. These biomarkers were followed after acute (48h) and chronic (21d) exposure period. Interestingly, CAT and GSTs were changed in the same manner after both exposure durations. The most observable change in daphnids was the increase of GSTs activities, measured with 1,2-chloro-4-dinitrobenzene as a substrate. No GSTs activities with ethacrynic acid and 1,2-dichloro-4-nitrobenzene as substrates were detected. The activity of CAT and the level of lipid peroxidation remained unchanged in daphnids exposed to sublethal concentrations of BPA. The reproduction rate was considerably affected already at 1.73mg/L while the growth was only affected at the highest concentration (13.8mg/L), where also significant mortality was observed.

Conversion and Estrogenicity of 17ß-estradiol During Photolytic/Photocatalytic Oxidation and Catalytic Wet-air Oxidation.

Estrogen 17ß-estradiol (E2), produced by human body and excreted into municipal wastewaters, belongs to the group of endocrine disrupting compounds that are resistant to biological degradation. The aim of this study was to assess the efficiency of E2 removal from aqueous solutions by means of catalytic wet-air oxidation (CWAO) and photolytic/photocatalytic oxidation. CWAO experiments were conducted in a trickle-bed reactor at temperatures up to 230 °C and oxygen partial pressure of 10 bar over TiO2 and Ru/TiO2 solids. Photolytic/photocatalytic oxidation was carried out in a batch slurry reactor employing a TiO2 P-25 (Degussa) catalyst under visible or UV light. HPLC analysis and yeast estrogen screen assay were used to evaluate the removal of E2 and estrogenicity of treated samples. The latter was completely removed during photolytic/photocatalytic oxidation under UV (365 nm) light and photocatalytic oxidation under visible light. In CWAO experiments, complete removal of both E2 and estrogenicity from the feed solution were noticed in the presence of TiO2 and Ru/TiO2 catalysts.

Highly Porous Poly(arylene cyano-vinylene) Beads Derived through the Knoevenagel Condensation of the Oil-in-Oil-in-Oil Double Emulsion Templates.

Conjugated porous polymers through the emulsion-templating polymerization process are typically prepared as monoliths, and the emulsions are cured via metal-catalyzed cross-coupling reactions. Herein, we report the design and synthesis of well-defined, millimeter-sized conjugated porous polymer beads by combining an oil-in-oil-in-oil (O/O/O) double emulsion as a de novo template and an amino-catalyzed Knoevenagel condensation reaction as a polymerization chemistry to cure such emulsions. The 1,4-phenylenediacetonitrile is reacted with aromatic multialdehydes in the presence of piperidine, and a series of metal-free poly(arylene cyano-vinylene) beads are prepared. All beads exhibit 3D-interconnected microcellular morphology and substantial semiconducting properties, such as strong light harvesting ability in the visible light region with electrochemical band gaps in the range of 2.05-2.33 eV. Finally, the promising photocatalytic activity of these conjugated beads is demonstrated for a model sulfoxidation reaction under visible light irradiation, and near quantitative conversions with excellent chemoselectivities (>99%) are obtained.

Isolation, Identification, and Selection of Bacteria With Proof-of-Concept for Bioaugmentation of Whitewater From Wood-Free Paper Mills.

In the wood-free paper industry, whitewater is usually a mixture of additives for paper production. We are currently lacking an efficient, cost-effective purification technology for their removal. In closed whitewater cycles the additives accumulate, causing adverse production problems, such as the formation of slime and pitch. The aim of our study was to find an effective bio-based strategy for whitewater treatment using a selection of indigenous bacterial isolates. We first obtained a large collection of bacterial isolates and then tested them individually by simple plate and spectrophotometric methods for their ability to degrade the papermaking additives, i.e., carbohydrates, resin acids, alkyl ketene dimers, polyvinyl alcohol, latex, and azo and fluorescent dyes. We examined correlation between carbon source use, genera, and inoculum source of isolates using two multivariate methods: principal component analysis and FreeViz projection. Of the 318 bacterial isolates, we selected a consortium of four strains (Xanthomonadales bacterium sp. CST37-CF, Sphingomonas sp. BLA14-CF, Cellulosimicrobium sp. AKD4-BF and Aeromonas sp. RES19-BTP) that degrade the entire spectrum of tested additives by means of dissolved organic carbon measurements. A proof-of-concept study on a pilot scale was then performed by immobilizing the artificial consortium of the four strains and inserting them into a 33-liter, tubular flow-through reactor with a retention time of < 15 h. The consortium caused an 88% reduction in the COD of the whitewater, even after 21 days.

Utilization of high specific surface area CuO-CeO2 catalysts for high temperature processes of hydrogen production: steam re-forming of ethanol and methane dry re-forming.

CuO-CeO(2) mixed oxide catalysts with 10, 15, and 20 mol % CuO content were prepared by the hard template method using KIT-6 silica as a template. The applied synthesis method yields solids with BET surface area in excess of 147 m(2)/g, highly porous nanocrystalline CeO(2) morphology and dispersion of CuO phase between 28 and 40%, corresponding to CuO particle size between 1.3 and 1.9 nm. Increasing the CuO content caused a decrease in dispersion of this phase and a further decrease of surface acid site abundance, determined by NH(3) chemisorption/TPD method, but improved the reducibility extent of CeO(2) (14.5, 16.1 and 24.5% for CuCe10, CuCe15, and CuCe20 catalyst, respectively) and oxygen mobility of prepared powders. It was discovered during ethanol steam re-forming experiments that increasing CuO content is favorable in terms of ethanol conversion but also causes quicker catalyst deactivation, primarily as a result of sintering and loss of CuO dispersion. Reaction temperatures in excess of 550 degrees C strongly promoted ethanol dehydratation reaction, leading to a rise in methane production and extensive coking of the catalyst surface. Coking was slower in the case of CuO-CeO(2) catalysts with a higher CuO content as a result of lower acid site abundance and more pronounced oxygen mobility. Temperatures in excess of 450 degrees C are required for any noticeable CO(2) and CH(4) conversion in methane dry re-forming reaction over CuO-CeO(2) materials. The examined materials displayed steady performance during stability tests at a reaction temperature of 650 degrees C, with catalysts containing 15 and 20 mol % CuO exhibiting the highest activity. Additionally, very low amounts of carbon were deposited on spent catalyst samples.

Visible Light-Driven Photocatalytic Activity of Magnetic Recoverable Ternary ZnFe2O4/rGO/g-C3N4 Nanocomposites.

ZnFe2O4/rGO/g-C3N4 ternary nanocomposite photocatalysts with different ZnFe2O4/g-C3N4 weight ratio (0.5, 0.75, 1) were prepared by a stepwise solvothermal method using ethylene glycol as the solvent. Physicochemical methods such as X-ray diffraction, UV-Vis diffuse reflectance spectroscopy and photoluminescence spectroscopy were applied in order to characterize the composites. The formation of a meso-/macroporous structure with specific surface area between 67 and 77 m2 g?1 was confirmed by N2 adsorption/desorption. The bandgap of the composites was found to be lower (2.30 eV) than that of g-C3N4 (2.7 eV). In contrast to pure g-C3N4, the composites showed no fluorescence, i.e. no recombination of e?/h+ took place. All samples, including pure g-C3N4 and ZnFe2O4, were tested for adsorption and photocatalytic degradation of aqueous malachite green model solutions (10?5 M) under visible light irradiation (? >400 nm). The results show that the prepared nanocomposites have higher absorption and photocatalytic activity than the pristine g-C3N4 and ZnFe2O4 and can be successfully used for water purification from organic azo-dyes.

Evolution of Surface Catalytic Sites on Bimetal Silica-Based Fenton-Like Catalysts for Degradation of Dyes with Different Molecular Charges.

We present here important new findings on the direct synthesis of bimetal Cu-Mn containing porous silica catalyst and the effects of structure-directing agent removal from the prepared nanomaterial on the evolution of surface catalytic sites. The extraction-calcination procedure of the structure-directing agent removal led to the formation of Cu and Mn oxo-clusters and Cu and Mn oxide nanoparticles smaller than 5 nm, while the solely calcination procedure led to the mentioned species and in addition to the appearance of CuO nanoparticles 20 nm in size. Catalysts were tested in the Fenton-like catalytic degradation of dyes with different molecular charge (cationic, anionic, and zwitterionic) as model organic pollutants in wastewater at neutral pH. Significantly faster degradation of cationic and anionic dyes in the first 60 min was observed with the catalyst containing larger CuO nanoparticles (>20 nm) due to the less hindered generation of •OH radicals and slower obstructing of the active sites on the catalysts surface by intermediates. However, this was not found beneficial for zwitterionic dye with no adsorption on the catalysts surface, where the catalyst with smaller Cu species performed better.

Influence of support materials on continuous hydrogen production in anaerobic packed-bed reactor with immobilized hydrogen producing bacteria at acidic conditions.

This study assesses the impact of different support materials (Mutag BioChip™, expanded clay and activated carbon) on microbial hydrogen production in an anaerobic packed-bed reactor (APBR) treating synthetic waste water containing glucose as the main carbon source at low pH value. The APBRs were inoculated with acid pretreated anaerobic sludge and operated at pH value of 4±0.2 and hydraulic retention time (HRT) of 3h. The maximum hydrogen yield of 1.80mol H2/mol glucose was achieved for the APBR packed with Mutag BioChip™ (R1), followed by expanded clay (R2, 1.74mol H2/mol glucose) and activated carbon (R3, 1.46mol H2/mol glucose). It was observed that the investigated support materials influenced the immobilization of hydrogen producing bacteria and consequently hydrogen production performance as well as composition of soluble metabolites. The main metabolic products were acetic acid and butyric acid accompanied with a smaller content of ethanol. The data indicated that in reactors with higher hydrogen yield (R1 and R2), acetate/butyrate (HAc/HBu) ratios were 1.7 and 1.6, respectively, while in the reactor with the lowest hydrogen yield (R3) the obtained HAc/HBu ratio was 4.8. Finally, stable hydrogen and organic acids production throughout the steady-state operation period at low pH values was achieved in all reactors.

Vapor-Phase Hydrogenation of Levulinic Acid to γ-Valerolactone Over Bi-Functional Ni/HZSM-5 Catalyst.

The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) in vapor-phase is economically more viable route if compared to reaction in liquid-phase. To improve the GVL yield in the vapor-phase reaction, the optimization of nickel modified zeolite as bi-functional catalyst (Ni/HZSM-5) was studied. Ni/HZSM-5 materials with fixed Al/Si molar ratio of 0.04 and different nominal Ni/Si molar ratios (from 0.01 to 0.05) were synthesized without the use of organic template and with the most affordable sources of silica and alumina. Materials were characterized by X-ray powder diffraction, SEM-EDX, TEM-EDX, pyridine TPD and DRIFTS, H2-TPR, N2 physisorption and isoelectric point. In the synthesized materials, 61-83% of nickel is present as bulk NiO and increases with nickel content. Additionally, in all catalysts, a small fraction of Ni2+ which strongly interacts with the zeolite support was detected (10-18%), as well as Ni2+ acting as charge compensating cations for Brønsted acid sites (7-21%). Increasing the nickel content in the catalysts leads to a progressive decrease of Brønsted acid sites (BAS) and concomitant increase of Lewis acid sites (LAS). When BAS/LAS is approaching to 1 and at the same time the amount of NiO reducible active sites is around 80%, the bi-functional Ni/HZSM-5-3 catalyst (Ni/Al = 0.59) leads to 99% conversion of LA and 100% selectivity to GVL at 320°C. This catalyst also shows stable levulinic acid hydrogenation to GVL in 3 reaction cycles conducted at 320°C. The concerted action of the following active sites in the catalyst is a key element for its optimized performance: (1) Ni metallic active sites with hydrogenation effect, (2) Lewis acid sites with dehydration effect, and (3) nickel aluminate sites with synergetic and stabilizing effects of all active sites in the catalyst.

Nanostructured Cu(x)Ce1-xO2-y mixed oxide catalysts: characterization and WGS activity tests.

Cu(x)Ce(1-x)O(2-y) mixed oxide catalysts were prepared by different preparation procedures: co-precipitation, the sol-gel peroxide route, and the sol-gel citric acid-assisted route. The resulting solids were investigated by means of XRD, BET, H(2) and CO temperature-programmed reduction (TPR), oxidation (TPO) and desorption (TPD) analyses, and N(2)O pulse selective reaction. It was confirmed that H(2) (CO) consumed for complete reduction of well-dispersed and bulk-like CuO phases to Cu(0), reduction of surface ceria and H(2) (CO) adsorption on the catalyst surface contribute to the total H(2) (CO) consumption. Among catalysts examined, the Cu(0.15)Ce(0.85)O(2-y) mixed oxide sample prepared by means of co-precipitation method exhibits the highest activity and stability for water-gas shift (WGS) pulse reaction in the range of employed operating conditions. WGS activity of copper-ceria mixed oxide catalysts is determined by the extent of surface ceria reduction and dispersion of copper species.