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Acid–base M2+MgAlO and M2+AlO mixed oxides (where M2+ = Mg, Cu, Co, Zn, and Ni) were obtained by thermal decomposition of the corresponding layered double hydroxide (LDH) precursors and used as catalysts for cyclohexanol and benzaldehyde condensation under solvent-free conditions. The catalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), and temperature-programmed desorption of CO2 (TPD-CO2). Gas chromatography–mass spectroscopy (GC/MS) was used for the identification and quantification of the product mixtures. In the reaction of cyclohexanol and benzaldehyde on M2+MgAlO and MgAlO catalysts, a 2,6-dibenzylidene-cyclohexanone was obtained as the main product as a result of consecutive one-pot dehydrogenation of cyclohexanol to cyclohexanone and subsequent Claisen–Schmidt condensation. In the reaction mixture obtained in the presence of NiAlO, CoAlO, and ZnAlO catalysts, a cyclohexyl ester of 6-hydroxyhexanoic acid was detected together with the main product. This is most likely a by-product obtained after the oxidation, ring opening, and subsequent esterification of the cyclohexanol. [ABSTRACT FROM AUTHOR]

Catalytic studies hydrogen production via steam reforming of ethanol (SRE) are essential for process optimization. Likewise, selecting the ideal support for the active phase can be critical to achieve high conversion rates during the catalytic steam reforming process. In this work, copper-based catalysts were synthesized using two different supports, NaY zeolite and Nb2O5/Al2O3 mixed oxides. The materials were prepared using wet impregnation and characterized for their physicochemical properties using different analytical techniques. Differences in the catalyst morphologies were readily attributed to the characteristics of the support. The Cu/NaY catalyst exhibited a higher specific surface area (210.40 m2 g−1) compared to the Cu/Nb2O5/Al2O3 catalyst (26.00 m2 g−1), resulting in a homogeneous metal dispersion over the support surface. The obtained results showed that, at 300 °C, both the Cu/Nb2O5/Al2O3 and Cu/NaY catalysts produced approximately 50% hydrogen and 40% acetaldehyde, but with significant differences in conversion (6% and 56%, respectively). At 450 °C, a greater product distribution and a 10% higher conversion were observed when the catalyst was supported on NaY compared to Nb2O5/Al2O3. Hence, the performance of copper-based catalysts was influenced significantly by the textural properties of the support. [ABSTRACT FROM AUTHOR]

Catalysts based on CoCuMgAl mixed oxides were synthesized and studied in the hydrogenations of furfural and 5-hydroxymethylfurfural under different conditions. The changes in the structural properties of the catalysts at different stages of their preparation were studied using a set of physical methods (XRD, SEM, and TEM). It was shown that the fine regulation of the chemical compositions of the mixed oxides (i.e., changes in the Co/Cu ratio) made it possible to vary the structure, morphology, and catalytic properties of the samples. The phase composition of catalysts with Co/Cu = 1 did not change during the catalytic reaction, although the initial catalysts had a less-homogeneous morphology. 5-hydroxymethylfurfural conversion was higher for the samples with Co/Cu = 1. Furfural conversion increased when raising the Co/Cu ratio. The selectivity toward furfuryl alcohol for the catalyst with Co/Cu = 2 under mild conditions of furfural hydrogenation was more than 99%. The results obtained are important for the development of the scientific foundations of the preparation of hydrogenation catalysts with a fine-tunable composition in order to obtain the desired hydrogenation products. [ABSTRACT FROM AUTHOR]

Single phase CuCoMgAl-layered hydroxides were obtained by making fine adjustment to their composition through changing the (Co + Cu)/Mg = 0.5; 1; 2; 3 and Co/Cu = 0.5; 1; 2 ratios. The rise of Co/Cu in systems contributed to the increase in their thermal stability. CuCoMgAl-catalysts showed high selectivity of carbonyl group hydrogenation in furfural and 5-hydroxymethylfurfural. In furfural hydrogenation, the selectivity to furfuryl alcohol was more than 99%, and in 5-hydroxymethylfurfural hydrogenation, the selectivity to 2,5-hydroxymethyl furfural was 95%. The surface of the samples with different Co/Cu after calcination and reduction was the same and had a «core-shell» structure (TEM). «Core» consisted of Cu and Co metallic particles. «Shell» consisted of CuCoMgAlOx mixed no-stoichiometric spinel oxides. There was no sintering or change in size of the metallic particles after the reaction. For the sample with Co/Cu = 1, their phase composition after reaction remained unchangeable. The increase of Co/Cu led to the formation of an X-ray amorphous phase after the reaction. This suggests the decrease in structural stability of this sample. The obtained results prove the prospects of using bimetallic CoCu-systems for hydrogenation of furan aldehydes, and opens up new directions for further research and improvement. [ABSTRACT FROM AUTHOR]

The increase of consciousness towards global warming and the need to reduce greenhouse gas emissions lead to the necessity of finding alternative applications based on easy-to-use materials in order to control and reduce global CO2 emissions. Layered Double Hydroxides (LDHs) and LDH-derived materials are potentially good adsorbents for CO2, thanks to their low cost, easy synthesis, high sorption capacity, and surface basicity. They have been intensively studied in CO2 capture at high temperature, presenting variable sorption capacities for MgAl LDHs with the same composition, but prepared under different synthesis conditions. The ambient temperature coprecipitation synthesis method is an attractive one-step procedure to synthesize LDHs under mild conditions, with low energy consumption and short synthesis time. The present study is based on the synthesis and characterization of hydrotalcites by a mild-conditions coprecipitation process and the production of derived mixed oxides to be used as CO2 adsorbents. A critical comparison to similar materials is reported. Moreover, the effect of the surface basicity of the derived mixed oxides (measured by adsorption calorimetry) and the CO2 sorption capacity are discussed, showing a linear correlation between the amount of weak and very strong basic sites and the CO2 adsorption behavior. [ABSTRACT FROM AUTHOR]

A rational synthetic approach is introduced to enable hydrogen insertion into oxides by forming a solid solution of a reducible oxide with a less reducible oxide as exemplified with RuO2 and TiO2 (Ru_x, a mixture of x% RuO2 with (100−x)% TiO2). Hydrogen exposure at 250 °C to Ru_x (Ru_x_250R) results in substantial hydrogen incorporation accompanied by lattice strain that in turn induces pronounced activity variations. Here, we demonstrate that hydrogen incorporation in mixed oxides promotes the oxidation catalysis of propane combustion with Ru_60_250R being the catalytically most active catalyst. [ABSTRACT FROM AUTHOR]

CeO2-TiO2 is an important mixed oxide due to its catalytic properties, particularly in heterogeneous photocatalysis. This study presents a straightforward method to obtain 1D TiO2 nanostructures decorated with CeO2 nanoparticles at the surface. As the precursor, we used H2Ti3O7 nanoribbons prepared from sodium titanate nanoribbons by ion exchange. Two cerium sources with an oxidation state of +3 and +4 were used to obtain mixed oxides. HAADF–STEM mapping of the Ce4+-modified nanoribbons revealed a thin continuous layer at the surface of the H2Ti3O7 nanoribbons, while Ce3+ cerium ions intercalated partially between the titanate layers. The phase composition and morphology changes were monitored during calcination between 620 °C and 960 °C. Thermal treatment led to the formation of CeO2 nanoparticles on the surface of the TiO2 nanoribbons, whose size increased with the calcination temperature. The use of Ce4+ raised the temperature required for converting H2Ti3O7 to TiO2-B by approximately 200 °C, and the temperature for the formation of anatase. For the Ce3+ batch, the presence of cerium inhibited the conversion to rutile. Analysis of cerium oxidation states revealed the existence of both +4 and +3 in all calcined samples, regardless of the initial cerium oxidation state. [ABSTRACT FROM AUTHOR]

Ni(Mg)Al-layered hydroxides with molar ratios of (Ni + Mg)/Al = 2, 3, 4 and Ni/(Ni + Mg) = 0.1, 0.3, 0.5, 0.7 were synthesized by mechanochemical activation. It has been proven that the phase composition of the samples was presented by a single hydrotalcite phase up to Ni/(Ni + Mg) = 0.5. For the first time, catalysts based on Ni(Mg)Al-layered hydroxides prepared by a mechanochemical route have been studied in the reaction of furfural hydrogenation. The correlation between furfural conversion, the selectivity of the products, and the composition of the catalysts was established. The effect of phase composition, surface morphology, and microstructure on the activity of the catalysts was shown by XRD, SEM, and TEM. It was found that catalysts with Ni/(Ni + Mg) = 0.5 have the highest furfural conversion. Herewith, the product selectivity can be regulated by the (Ni + Mg)/Al ratio. [ABSTRACT FROM AUTHOR]

Anodic oxides were grown to 50 V on Ta-Nb sputtering deposited alloys, with high Nb content, in acetate ions containing an aqueous solution to study the effect of the anodizing bath composition on anodic layers' dielectric properties. Photoelectrochemical measurements proved the presence of a photocurrent in the band gap of photon energy lower than oxides, due to optical transitions involving localized electronic states as a consequence of acetate ions incorporation. Flat band potential value estimates assessed the insulating nature of the anodic oxides grown in the acetate buffer solution. Differential capacitance measurements showed that the highest capacitance value was measured for the sample grown on Ta-66%Nb. This capacitance value was higher with respect to those estimated for pure Ta and pure Nb anodic layers and with respect to the same alloy anodized in NaOH solution, i.e., acetate-free anodizing bath. [ABSTRACT FROM AUTHOR]

Mixed Ni-Al oxide catalytic precursors with different elemental ratios (20, 50, and 80 wt.% Ni0) were synthesized using green supercritical antisolvent co-precipitation (SAS). The obtained oxide precursors and metal catalysts were characterized in detail by X-ray diffraction (XRD) analysis, atomic pair distribution function (PDF) analysis, CO adsorption, and high-resolution transmission electron microscopy (HRTEM). It was found that the composition and structure of the Ni-Al precursors are related to the Ni content. The mixed Ni1−xAlxO oxide with NiO-based crystal structure was formed in the Ni-enriched sample, whereas the highly dispersed NiAl2O4 spinel was observed in the Al-enriched sample. The obtained metal catalysts were tested in the process of anisole H2-free hydrogenation. 2-PrOH was used as a hydrogen donor. The catalyst with 50 wt.% Ni0 demonstrated the highest activity in the hydrogenation process. [ABSTRACT FROM AUTHOR]

Copper was incorporated into the Ce-Sn and comparative Ce-Zr oxide supports by one-pot precipitation in the presence of CTAB template and by the impregnation of templated Ce-Sn and Ce-Zr oxides. The synthesized Cu-Ce-Sn and Cu-Ce-Zr catalysts were tested in the continuous-flow preferential oxidation of CO in hydrogen excess. The one-pot synthesized tin- and zirconium-doped catalysts demonstrated better CO conversion and CO2 selectivity than their impregnated counterparts. For the tin-modified ternary system that showed the best catalytic performance, the copper content was further optimized. The structure, reducibility, surface chemical state and textural properties of the catalysts were analyzed by SEM-EDX, XRD, H2-TPR, Raman spectroscopy, XPS and TEM. The nonmonotonic changes in the specific surface area, Cu+/Cu2+ ratio and ratio of lattice and non-lattice oxygen with increasing the Cu content are discussed in terms of copper distribution in the catalysts. The influence of the interaction between copper oxide species and the cerium–tin/cerium–zirconium oxide support on the performance of the ternary catalysts was thoroughly analyzed and discussed. [ABSTRACT FROM AUTHOR]

A series of clinoptilolite-supported catalysts, modified with hydrotalcite-like phase (HT) by co-precipitation, were prepared and tested in NH3-SCR reactions. It was found that deposition of HT on clinoptilolite increased conversion of NO within 250–450 °C, and that the positive impact on the catalytic activity was independent of HT loading. The promoting effect of clinoptilolite was attributed to Brönsted acid sites present in the zeolite, which facilitated adsorption and accumulation of ammonia during the catalytic process. Concentration of N2O in the post-reaction gas mixture reached its maximum at 300 °C and the by-product was most likely formed as a consequence of NH4NO3 decomposition or side reaction of NH3 oxidation in the high-temperature region. The gradual elimination of nitrous oxide, noticed as the material with the highest concentration of hydrotalcite phase, was attributed to the abundance of oligomeric iron species and the superior textural parameters of the material. UV-Vis experiments performed on the calcined samples indicated that Fe sites of higher nuclearity were generated by thermal decomposition of the hydrotalcite phase during the catalytic reaction. Therefore, calcination of the materials prior to the catalytic tests was not required to obtain satisfactory overall catalytic performance in NO reductions. [ABSTRACT FROM AUTHOR]

In this study, V2O5/ZrO2 samples loaded with different wt% of V2O5, ranging between 0% and 20% (wt% = 2.5, 3.6, 7.5, 10, and 20), were prepared and studied in the dehydrogenation of 2-butanol in order to investigate their acid-basic properties and to select the most interesting sample, that was identified in the 3.6 wt%V2O5/ZrO2. Such a catalyst was modified by adding phosphate at different atomic ratios (P/V = 0.5, 1, and 2) and further characterized by XRD, SEM-EDX, ESR, UV-Vis-PIR diffuse reflectance. Tests of catalytic dehydrogenation of 2-butanol were also performed. Then, the so-prepared samples were investigated in the oxidative dehydrogenation (ODH) of propane that represents the reaction of main interest in this study. It has been shown that the introduction of 3.6 wt%V2O5 and phosphate in the zirconia matrix enhances the stability of the tetragonal structure, improves acidity, and promotes ODH activity. Compared to the unpromoted 3.6 wt%V2O5/ZrO2 catalyst, the addition of phosphate increases the overall propane conversion from 12% to 20%, and also the propylene selectivity from 54% to near 64%, in the experimental conditions F °C3H8/F°O2/F°total (cm3/min): 3.6/1.8/60 at the temperature of 500 °C. The influence of the reaction mixture on the ODH, in particular the oxygen flow rate, was addressed. Highlights: Phosphorus loaded V2O5/ZrO2 catalysts were prepared and investigated in the oxidative dehydrogenation of propane. Addition of V2O5 and phosphorus to ZrO2 stabilized the tetragonal phase with respect to the monoclinic one. Among the prepared V2O5/ZrO2 samples, the most active catalyst corresponds to 3.6 wt% of V2O5/ ZrO2, The addition of phosphorus to 3.6 wt% V2O5/ZrO2 improves acidity and selectivity to propylene. Correlation between catalysts acidity and oxidative dehydrogenation of propane was observed. [ABSTRACT FROM AUTHOR]

Silica, titania, and mixed silica–titania powders have been used as supports for loading 5 wt% Cu, 5 wt% Ag, and 2.5 wt% Cu-2.5 wt% Ag with the aim of providing a series of nanomaterials with antifouling properties. All the solids were easily prepared by the wetness-impregnation method from commercially available chemical precursors. The resulting materials were characterized by several techniques such as X-ray diffraction analysis, X-ray photoelectron spectroscopy, N2 physisorption, and temperature-programmed reduction measurements. Four selected Cu and Ag SiO2- and TiO2-supported powders were tested as fillers for the preparation of marine antifouling coatings and complex viscosity measurements. Titania-based coatings showed better adhesion than silica-based coatings and the commercial topcoat. The addition of fillers enhances the resin viscosity, suggesting better workability of titania-based coatings than silica-based ones. The ecotoxicological performance of the powders was evaluated by Microtox luminescence tests, using the marine luminescent bacterium Vibrio fisheri. Further investigations of the microbiological activity of such materials were carried out focusing on the bacterial growth of Pseudoalteromonas sp., Alteromonas sp., and Pseudomonas sp. through measurements of optical density at 600 nm (OD600nm). [ABSTRACT FROM AUTHOR]

Recently, catalysts with hydrotalcites and hydrotalcite-derived compounds have attracted particular interest due to their specific properties, mostly well-developed texture, high thermal stability, and favorable acid–base properties. In this work, we report the investigation of ammonia synthesis on barium-promoted cobalt catalysts supported on hydrotalcite-derived Mg-Al mixed oxides with different Mg/Al molar ratios. The obtained catalysts were characterized using TGA-MS, nitrogen physisorption, XRPD, TEM, STEM-EDX, H2-TPD, CO2-TPD, and tested in ammonia synthesis (470 °C, 6.3 MPa, H2/N2 = 3). The studies revealed that the prepared Mg-Al mixed oxides are good candidates as support materials for Co-based catalysts. However, interestingly, the support composition does not influence the activity of Ba/Co/Mg-Al catalysts. The change in Mg/Al molar ratio in the range of 2–5 did not significantly change the catalyst properties. All the catalysts are characterized by similar textural, structural, and chemisorption properties. The similar density of basic sites on the surface of the studied catalysts was reflected in their comparable performance in ammonia synthesis. [ABSTRACT FROM AUTHOR]

The Mn-containing mixed-oxide-supported bismuth oxychloride (BiOCl) catalysts were prepared by calcining their corresponding parent hydrotalcite supported BiOCl. The crystal structure of BiOCl was found to be intact during calcination, while significant differences appeared in the chemical state of Mn and the redox capacities of the catalysts before and after calcination. Compared to the hydrotalcite-supported catalysts, the mixed-oxide-supported BiOCl showed much higher catalytic performance in the oxidation removal of formaldehyde due to the synergetic catalysis of more surface oxygen vacancies and higher surface basicity. The complete removal of formaldehyde could be achieved at 70 °C, and the removal efficiency was maintained more than 90% for 21 h. A possible reaction mechanism was also proposed. [ABSTRACT FROM AUTHOR]

We describe the synthesis of silver loaded on zirconia and its use as an efficient catalyst for a one-pot three-component reaction to synthesize 11 indenopyrimidine derivatives, of which 7 are new compounds. The procedure involves substituted benzaldehydes, indane-1,3-dione, and guanidinium hydrochloride, with ethanol as solvent. The proposed green protocol at room temperature is simple and efficient, giving excellent yields (90–96%) in short reaction times (<30 min). The protocol works well according to the green chemistry principles with respect to high atom economy, no need for column separation, and reusability of the catalyst, which are attractive features. XRD, TEM, SEM, and BET analysis were used to characterize the catalyst materials. [ABSTRACT FROM AUTHOR]

The lithium ion battery (LIB) has proven to be a very reliably used system to store electrical energy, for either mobile or stationary applications. Among others, TiO2-based anodes are the most attractive candidates for building safe and durable lithium ion batteries with high energy density. A variety of TiO2 nanostructures has been thoroughly investigated as anodes in LIBs, e.g., nanoparticles, nanorods, nanoneedles, nanowires, and nanotubes discussed either in their pure form or in composites. In this review, we present the recent developments and breakthroughs demonstrated to synthesize safe, high power, and low cost nanostructured titania-based anodes. The reader is provided with an in-depth review of well-oriented TiO2-based nanotubes fabricated by anodic oxidation. Other strategies for modification of TiO2-based anodes with other elements or materials are also highlighted in this report. [ABSTRACT FROM AUTHOR]

Different lanthanide (Ln)-doped cerium oxides (Ce0.5Ln0.5O1.75, where Ln: Gd, La, Pr, Nd, Sm) were loaded with Cu (20 wt. %) and used as catalysts for the oxidation of ethyl acetate (EtOAc), a common volatile organic compound (VOC). For comparison, both Cu-free (Ce-Ln) and supported Cu (Cu/Ce-Ln) samples were characterized by N2 adsorption at −196 °C, scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed reduction in H2. The following activity sequence, in terms of EtOAc conversion, was found for bare supports: CeO2 ≈ Ce0.5Pr0.5O1.75 > Ce0.5Sm0.5O1.75 > Ce0.5Gd0.5O1.75 > Ce0.5Nd0.5O1.75 > Ce0.5La0.5O1.75. Cu addition improved the catalytic performance, without affecting the activity order. The best catalytic performance was obtained for Cu/CeO2 and Cu/Ce0.5Pr0.5O1.75 samples, both achieving complete EtOAc conversion below ca. 290 °C. A strong correlation was revealed between the catalytic performance and the redox properties of the samples, in terms of reducibility and lattice oxygen availability. Νo particular correlation between the VOC oxidation performance and textural characteristics was found. The obtained results can be explained in terms of a Mars-van Krevelen type redox mechanism involving the participation of weakly bound (easily reduced) lattice oxygen and its consequent replenishment by gas phase oxygen. [ABSTRACT FROM AUTHOR]

In this paper the influence of material composition on the structural, surface and optical properties of HfO2-TiO2 mixed oxide coatings was investigated and discussed. Five sets of thin films were deposited using reactive magnetron sputtering: HfO2, TiO2 and three sets of mixed HfO2-TiO2 coatings with various titanium content. The change in the material composition had a significant influence on the structural, surface and optical properties. All of the deposited coatings, except for (Hf0.55Ti0.45)Ox, were nanocrystalline with crystallites ranging from 6.7 nm to 10.8 nm in size. Scanning electron microscopy measurements revealed that surface of nanocrystalline thin films consisted of grains with different shapes and sizes. Based on optical transmission measurements, it was shown that thin films with higher titanium content were characterized by a higher cut-off wavelength, refractive index and lower optical band gap energy. The porosity and packing density were also determined. [ABSTRACT FROM AUTHOR]

A series of Mn-Co/TiO2 catalysts were prepared by wet impregnation method and evaluated for the oxidation of NO to NO2. The effects of Co amounts and calcination temperature on NO oxidation were investigated in detail. The catalytic oxidation ability in the temperature range of 403-473 K was obviously improved by doping cobalt into Mn/TiO2. These samples were characterized by nitrogen adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM) and hydrogen temperature programmed reduction (H2-TPR). The results indicated that the formation of dispersed Co3O4-CoMnO3 mixed oxides through synergistic interaction between Mn-O and Co-O was directly responsible for the enhanced activities towards NO oxidation at low temperatures. Doping of Co enhanced Mn4+ formation and increased chemical adsorbed oxygen amounts, which also accelerated NO oxidation. [ABSTRACT FROM AUTHOR]

The synthesis of functional nanoparticles via one-step flame spray pyrolysis (FSP), especially those of catalytic nature, has attracted the interests of scientists and engineers, as well as industries. The rapid and high temperature continuous synthesis yields nanoparticles with intrinsic features of active catalysts, that is, high surface area and surface energetics. For these reasons, FSP finds applications in various thermally inducible catalytic reactions. However, the design and synthesis of photocatalysts by FSP requires a knowledge set which is different from that established for thermal catalysts. Unknown to many, this has resulted in frustrations to those entering the field unprepared, especially since FSP appears to be an elegant tool in synthesising oxide nanoparticles of any elemental construct. From simple oxide to doped-oxide, and mixed metal oxide to the in situ deposition of noble metals, this Perspective gives an overview on the development of photocatalysts made by FSP in the last decade that led to a better understanding of the design criteria. Various challenges and opportunities are also highlighted, especially those beyond simple metal oxides, which perhaps contain the greatest potential for the exploitation of photocatalysts design by FSP. [ABSTRACT FROM AUTHOR]

Semiconductor materials are the basis of electronic devices employed in the communication and media industry. In the present work, we report the synthesis and characterization of mixed metal oxides (MOs) as p,n-junction photocatalysts, and demonstrate the correlation between the preparation technique and the properties of the materials. Solid-state UV-visible diffuse reflectance spectroscopy (UV-VIS DRS) allowed for the determination of the light absorption properties and the optical energy gap. X-ray photoelectron spectroscopy (XPS) allowed for the determination of the surface speciation and composition and for the determination of the valence band edge. The opto-electronic behavior was evaluated measuring the photocurrent generated after absorption of chopped visible light in a 3-electrode cell. Scanning electron microscopy (SEM) measurements allowed for auxiliary characterization of size and morphology, showing the formation of composites for the ternary Cu2O-In2O3 p,n-mixed oxide, and even more for the quaternary Cu2O-In2O3-TiO2 MO. Light absorption spectra and photocurrent-time curves mainly depend upon the composition of MOs, while the optical energy gap and defective absorption tail are closely related to the preparation methodology, time and thermal treatment. Qualitative electronic band structures of semiconductors are also presented. [ABSTRACT FROM AUTHOR]

Mixed oxides have received remarkable attention due to the many opportunities to adjust their interesting structural, electrical, catalytic properties, leading to a better, more useful performance compared to the basic metal oxides. In this study, mixed oxides NiO/ZnO/Al2O3 were synthesized in a single step via the ultrasonic spray pyrolysis method using nitrate salts, and the temperature effects of the process were investigated (400, 600, 800 °C). The synthesized samples were characterized by means of scanning electron microscopy, energy-dispersive spectroscopy, X-ray diffraction and Raman spectroscopy analyses. The results showed Al2O3, NiO–Al2O3 and ZnO–Al2O3 systems with spinel phases. Furthermore, the Raman peaks supported the coexistence of oxide phases, which strongly impact the overall properties of nanocomposite. [ABSTRACT FROM AUTHOR]

X-ray Diffraction has been fully exploited as a probe to investigate crystalline materials. However, very little research has been carried out to unveil its potentialities towards amorphous materials. In this work, we demonstrated the capabilities of Grazing Incidence X-ray Diffraction (GIXRD) as a simple and fast tool to obtain quantitative information about the composition of amorphous mixed oxides. In particular, we evidenced that low angle scattering features, associated with local structure parameters, show a significant trend as a function of the oxide composition. This evolution can be quantified by interpolating GIXRD data with a linear combination of basic analytical functions, making it possible to build up GIXRD peak-sample composition calibration curves. As a case study, the present method was demonstrated on Ta 2 O 5 -SiO 2 amorphous films deposited by RF-magnetron sputtering. GIXRD results were validated by independent measurement of the oxide composition using Rutherford Backscattering Spectrometry (RBS). These materials are attracting interest in different industrial sectors and, in particular, in photovoltaics as anti-reflection coatings. Eventually, the optical properties measured by spectroscopic ellipsometry were correlated to the chemical composition of the film. The obtained results highlighted not only a correlation between diffraction features and the composition of amorphous films but also revealed a simple and fast strategy to characterize amorphous thin oxides of industrial interest.

Co-precipitated Ni-Mg-Al hydrotalcite-derived catalyst promoted with vanadium were synthesized with different V loadings (0–4 wt%) and studied in CO2 methanation. The promotion with V significantly changes textural properties (specific surface area and mesoporosity) and improves the dispersion of nickel. Moreover, the vanadium promotion strongly influences the surface basicity by increasing the total number of basic sites. An optimal loading of 2 wt% leads to the highest activity in CO2 methanation, which is directly correlated with specific surface area, as well as the basic properties of the studied catalysts. [ABSTRACT FROM AUTHOR]

Two series of chromium–zirconium mixed oxide catalysts with different Cr/Zr molar ratio are prepared by co-precipitation method. Porous structure of the catalysts is studied by low-temperature N2 adsorption–desorption. Phase composition and chromium states in the catalysts are characterized by X-ray diffraction (XRD), UV-visible spectroscopy, and temperature-programmed reduction with hydrogen (TPR-H2). The mixed catalysts are tested in non-oxidative dehydrogenation of propane at 550 °C. The catalysts synthesized without ageing of precipitate show higher activity in propane dehydrogenation due to the higher content of reducible Cr+5/+6 species due to its stabilization on the ZrO2 surface. [ABSTRACT FROM AUTHOR]

A series of mixed oxides of CuO, CeO2, and SiO2 were prepared by gel combustion and employed for the first time as efficient solid catalysts in a solvent-less liquid-phase cross-dehydrogenative coupling. The facile one-pot catalyst synthesis resulted in highly porous materials presenting large specific surface areas and strong metal–support interactions. The interaction with highly dispersed CeO2 enhanced the redox properties of the CuO species. The CuO-CeO2-SiO2 composites exhibited excellent catalytic performance for the selective coupling between 1,1-diphenylethylene and tetrahydrofuran with a yield up to 85% of 2-(2,2-diphenylvinyl)-tetrahydrofuran in the presence of di-tert-butyl peroxide (DTPB) and KI. Albeit both CuO and CeO2 species are proved to be responsible for the catalytic conversion, a great synergistic improvement in the catalytic activity was obtained by extended contact between the oxide phases by high porosity in comparison with the reactions using individual Cu or Ce catalysts. The activity of the composite catalyst was shown to be highly stable after five successive reaction cycles. Furthermore, the study scope was extended to the synthesis of different derivatives via composite-catalyzed coupling of C(sp2)-H with C(sp3-H) adjacent to a heteroatom. The good yields recorded proved the general validity of this composite for the cross-dehydrogenative coupling reaction rarely performed on solid catalysts. [ABSTRACT FROM AUTHOR]

Hydrotalcites (HTCs) are promising solid base catalysts to produce advanced biofuels by aldol condensation. Their main potential lies in the tunability of their acid-base properties by varying their composition. However, the relationship between the composition of hydrotalcites, their basicity, and their catalytic performance has not yet been fully revealed. Here, we investigate systematically the preparation of HTCs with the general formula of Mg6M3+2(OH)16CO3·4H2O, where M3+ stands for Al, Ga, Fe, and In, while keeping the Mg/M3+ equal to 3. We use an array of analytical methods including XRD, N2 physisorption, CO2-TPD, TGA-MS, FTIR-ATR, and SEM to assess changes in the properties and concluded that the nature of M3+ affected the HTC crystallinity. We show that the basicity of the HTC-derived mixed oxides decreased with the increase in atomic weight of M3+, which was reflected by decreased furfural conversion in its aldol condensation with acetone. We demonstrate that all MgM3+ mixed oxides can be fully rehydrated, which boosted their activity in aldol condensation. Taking all characterization results together, we conclude that the catalytic performance of the rehydrated HTCs is determined by the "host" MgO component, rather than the nature of M3+. [ABSTRACT FROM AUTHOR]

Formaldehyde is a primary chemical in the manufacturing of various consumer products. It is synthesized via partial oxidation of methanol using a mixed oxide iron molybdate catalyst (Fe2(MoO4)3–MoO3). This is one of the standard energy-efficient processes. The mixed oxide iron molybdate catalyst is an attractive commercial catalyst for converting methanol to formaldehyde. However, a detailed phase analysis of each oxide phase and a complete understanding of the catalyst formulation and deactivation studies is required. It is crucial to correctly formulate each oxide phase and influence the synthesis methods precisely. A better tradeoff between support and catalyst and oxygen revival on the catalyst surface is vital to enhance the catalyst's selectivity, stability, and lifetime. This review presents recent advances on iron molybdate's catalytic behaviour for formaldehyde production—a deep recognition of the catalyst and its critical role in the processes are highlighted. Finally, the conclusion and prospects are presented at the end. [ABSTRACT FROM AUTHOR]

In this paper, we present a versatile template-directed colloidal self-assembly method for the fabrication in aqueous phase of composition-tuned mesoporous RuO2@TiO2-SiO2 catalysts. Randomly methylated β-cyclodextrin/Pluronic F127 supramolecular assemblies were used as soft templates, TiO2 colloids as building blocks, and tetraethyl orthosilicate as a silica source. Catalysts were characterized at different stages of their synthesis using dynamic light scattering, N2-adsorption analysis, powder X-ray diffraction, temperature programmed reduction, high-resolution transmission electron microscopy, high-angle annular bright-field and dark-field scanning transmission electron microscopy, together with EDS elemental mapping. Results revealed that both the supramolecular template and the silica loading had a strong impact on the pore characteristics and crystalline structure of the mixed oxides, as well as on the morphology of the RuO2 nanocrystals. Their catalytic performance was then evaluated in the aqueous phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) under mild conditions (50 °C, 50 bar H2). Results showed that the cyclodextrin-derived catalyst displayed almost quantitative LA conversion and 99% GVL yield in less than one hour. Moreover, this catalyst could be reused at least five times without loss of activity. This work offers an effective approach to the utilization of cyclodextrins for engineering the surface morphology of Ru nanocrystals and pore characteristics of TiO2-based materials for catalytic applications in hydrogenation reactions. [ABSTRACT FROM AUTHOR]

Biodiesel, as one of the alternative biofuels replacing the common fossil fuels, is prepared by transesterification of oils and fats. Commonly, the reaction is catalysed by either acidic or basic catalysts. The availability of the active sites to large triglyceride molecules is the key factor of the heterogeneous catalysts. The use of carbon fibres during the synthesis of Mg/Fe layered double hydroxides results in the formation of macropores during the calcination. The amount of carbon fibres showed an important effect on the textural properties of the resulting mixed oxides. The texture was determined by N2-adsorption and Hg-porosity. The catalyst activity in the studied reaction was examined by determination of ester amount by gas chromatography and the activity was compared with unmodified mixed oxides. The highest ester yield (40 wt.%) was achieved by adding 1 wt.% of carbon fibres to the catalyst with the largest size of macropores. [ABSTRACT FROM AUTHOR]

We report the synthesis and characterization of pure ZnO, pure CeO2, and ZnO:CeO2 mixed oxide thin films dip-coated on glass substrates using a sol-gel technique. The structural properties of as-prepared thin film are investigated using the XRD technique. In particular, pure ZnO thin film is found to exhibit a hexagonal structure, while pure CeO2 thin film is found to exhibit a fluorite cubic structure. The diffraction patterns also show the formation of mixed oxide materials containing well-dispersed phases of semi-crystalline nature from both constituent oxides. Furthermore, optical properties of thin films are investigated by performing UV–Vis spectrophotometer measurements. In the visible region, transmittance of all investigated thin films attains values as high as 85%. Moreover, refractive index of pure ZnO film was found to exhibit values ranging between 1.57 and 1.85 while for CeO2 thin film, it exhibits values ranging between 1.73 and 2.25 as the wavelength of incident light decreases from 700 nm to 400 nm. Remarkably, refractive index of ZnO:CeO2 mixed oxide-thin films are tuned by controlling the concentration of CeO2 properly. Mixed oxide-thin films of controllable refractive indices constitute an important class of smart functional materials. We have also investigated the optoelectronic and dispersion properties of ZnO:CeO2 mixed oxide-thin films by employing well-established classical models. The melodramatic boost of optical and optoelectronic properties of ZnO:CeO2 mixed oxide thin films establish a strong ground to modify these properties in a skillful manner enabling their use as key potential candidates for the fabrication of scaled optoelectronic devices and thin film transistors. [ABSTRACT FROM AUTHOR]

Featured Application: Thermal barrier coating is applied to aviation turbines to protect the nickel-based superalloys from melting and thermal cycling. Durability of a thermal barrier coating (TBC) depends strongly on the type of mixed oxide in the thermally grown oxide (TGO) of a TBC. This study aims on discovering the effect of thermal stability in the TGO area containing mixed oxides. Two different bondcoats were studied using high-resolution transmission electron microscopy: high-velocity oxygen fuel (HVOF) and air-plasma spray (APS), under isothermal and thermal cyclic tests at 1400 °C. The HVOF bondcoats were intact until 1079 cycles. In comparison, APS failed at the early stage of thermal cycling at 10 cycles. The phase transformation of topcoat from tetragonal to the undesired monoclinic was observed, leading to TBC failure. The results showed that the presence of transient aluminas found in HVOF bondcoat helps in the slow growth of α-Al2O3. In contrast, the APS bondcoat does not contain transient aluminas and transforms quickly to α-Al2O3 along with spinel and other oxides. This fast growth of mixed oxides causes stress at the interface (topcoat and TGO) and severely affects the TBC durability leading to early failure. Therefore, the mixed oxide with transient aluminas slows down the quick transformation into alpha-aluminas, which provides high thermal stability for a high TBC durability. [ABSTRACT FROM AUTHOR]

Mixed oxides containing zinc and lanthanum were prepared by coprecipitation in alkaline medium, followed by calcination at 400 °C. The initial precipitation product and the calcined form were characterized by Brunauer–Emmett–Teller (BET) method adsorption of nitrogen at −196 °C, Scanning Electron Microscopy/Electron-Probe Microanalysis (SEM/EPM), Ultraviolet—Diffuse Reflectance Spectroscopy (UV-DRS) and Infrared (IR) spectroscopy. The band gap slightly changes from 3.23 eV to 3 eV by calcination. The photocatalytic performance of the solids were investigated in diluted aqueous medium, by using clofibric acid (CA), a stable and toxic molecule used as precursor in some pesticides and drugs, as test compound, possibly found in the wastewaters in low concentrations. The effects of the degradation extent, determined by high performance liquid chromatography (HPLC) and total organic carbon (TOC) measurements, were investigated at different initial concentrations of CA. Within about 60 min the CA degradation is almost total at low concentration values (3 ppm) and reaches over 80% in 180 min for an initial concentration of 50 ppm. Moreover, the CA removal performance of photocatalyst remains excellent after three cycles of use: the removal yield was practically total after 60 min in the first two cycles and reached 95% even in the third cycle. [ABSTRACT FROM AUTHOR]

A set of ex-ZnAl-LDHs catalysts with a molar ratio of Zn/Al in the range of 0.3–1.0 was prepared using co-precipitation and thermal treatment. The samples were characterized using various methods, including X-ray fluorescence spectroscopy (XRF), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy FT-IR, N2 adsorption, Temperature-programmed desorption of CO2 (TPD-CO2) as well as Scanning electron microscopy (SEM-EDS). Catalyst activity and long-term stability measurements were carried out in a high-temperature water–gas shift (HT-WGS) reaction. Mixed oxide catalysts with various Zn/Al molar ratios decorated with potassium showed high activity in the HT-WGS reaction within the temperature range of 330–400 °C. The highest activity was found for the Zn/Al molar ratio of 0.5 corresponding to spinel stoichiometry. However, the catalyst with a stoichiometric spinel molar ratio of Zn/Al (ZnAl_0.5_K) revealed a higher tendency for surface migration and/or vaporization of potassium during overheating at 450 °C. The correlation of the activity results and TPD-CO2 data show that medium basic sites enhance the progress of the HT-WGS reaction. [ABSTRACT FROM AUTHOR]

Thick thermal barrier coatings (TBCs) are the main choice in the aviation industry due to their ability to handle elevated temperature exposure in turbines. However, the efficacy of thick TBCs has not been adequate. This study presents a highly durable, thick top-coat (TC) of Lanthanum–gadolinium–yttria stabilized zirconia (La–Gd–YSZ) on high-velocity oxygen fuel (HVOF)-bond coat (HVOF-BC). Crack propagation was quantitatively assessed using a three-dimensional (3D) measuring laser microscope due to higher reliability in calculating the actual crack length of TBC. The findings revealed the HVOF-BC is highly durable with intact structural composition, while the conventional TBC of atmospheric plasma spraying (APS) bond coat (APS-BC) of the same composition and thickness with identical TC was detached at a crack-susceptible zone. The significant enhancement in HVOF-BC is due to the low mixed-oxides growth rate in thermally grown oxide (TGO) with a uniform and dense protective layer of stable Al2O3 which reduces crack propagation. Meanwhile, the failure in APS-BC can be attributed to the high TGO growth rate and thickness with segmented and unstable Al2O3. Furthermore, detrimental mixed oxides such as spinel Ni(Cr,Al)2O4 and NiO lead to disastrous horizontal and compressive cracks. To that end, we study the effect of TGO growth and crack propagation on HVOF-BC TBCs using APS-BC TBCs as a reference. [ABSTRACT FROM AUTHOR]

A series of NiO–CeO2 mixed oxide catalysts have been synthesized by a modified coprecipitation method at three different pH values (pH = 8, 9, and 10). The NiO–CeO2 mixed oxide samples were characterized by TGA, XRD, inductively coupled plasma atomic emission spectroscopy (ICP-AES), FTIR, Brunauer–Emmett–Teller (BET) surface area, H2 temperature-programmed reduction (H2-TPR), and electron microscopy (high-angle annular dark-field transmission electron microscopy/energy-dispersive X-ray spectroscopy (HAADF-TEM/EDS)). The catalytic activities of the samples for soot oxidation were investigated under loose and tight contact conditions. The catalysts exhibited a high BET surface area with average crystal sizes that varied with the pH values. Electron microscopy results showed the formation of small crystallites (~5 nm) of CeO2 supported on large plate-shaped particles of NiO (~20 nm thick). XRD showed that a proportion of the Ni2+ was incorporated into the ceria network, and it appeared that the amount on Ni2+ that replaced Ce4+ was higher when the synthesis of the mixed oxides was carried out at a lower pH. Among the synthesized catalysts, Ni-Ce-8 (pH = 8) exhibited the best catalytic performance. [ABSTRACT FROM AUTHOR]

Catalyzed oxygen evolution and oxygen reduction reactions (OER and ORR, respectively) are of particular significance in many energy conversion and storage processes. During the last decade, they emerged as potential routes to sustain the ever-growing needs of the future clean energy market. Unfortunately, the state-of-the-art OER and ORR electrocatalysts, which are based on noble metals, are noticeably limited by a generally high activity towards one type of reaction only, high costs and relatively low abundance. Therefore, the development of (bi)functional low-cost non-noble metal or metal-free electrocatalysts is expected to increase the practical energy density and drastically reduce the production costs. Owing to their pore properties and high surface areas, mesoporous materials show high activity towards electrochemical reactions. Among all synthesis methods available for the synthesis of non-noble mesoporous metal oxides, the hard-templating (or nanocasting) approach is one of the most attractive in terms of achieving variable morphology and porosity of the materials. In this review, we thus focus on the recent advances in the design, synthesis, characterization and efficiency of non-noble metal OER and ORR electrocatalysts obtained via the nanocasting route. Critical aspects of these materials and perspectives for future developments are also discussed. [ABSTRACT FROM AUTHOR]

Mixed oxide nanoparticles (MONs, TiO2–ZnO–MgO) obtained by the sol-gel method were characterized by transmission electron microscopy, (TEM, HRTEM, and SAED) and thermogravimetric analysis (TGA/DTGA–DTA). Furthermore, the effect of MONs on microbial growth (growth profiling curve, lethal and sublethal effect) of Escherichia coli, Salmonella paratyphi, Staphylococcus aureus and Listeria monocytogenes, as well as the toxicity against Artemia salina by the lethal concentration test (LC50) were evaluated. MONs exhibited a near-spherical in shape, polycrystalline structure and mean sizes from 17 to 23 nm. The thermal analysis revealed that the anatase phase of MONs is completed around 480–500 °C. The normal growth of all bacteria tested is affected by the MONs presence compared with the control group. MONs also exhibited a reduction on the plate count from 0.58 to 2.10 log CFU/mL with a sublethal cell injury from 17 to 98%. No significant toxicity within 24 h was observed on A. salina. A bacteriostatic effect of MONs on bacteria was evidenced, which was strongly influenced by the type of bacteria, as well as no toxic effects (LC50 >1000 mg/L; TiO2–ZnO (5%)–MgO (5%)) on A. salina were detected. This study demonstrates the potential of MONs for industrial applications. [ABSTRACT FROM AUTHOR]

This study presents the synthesis and characterization of lanthanum-modified alumina supported cerium–manganese mixed oxides, which were prepared by three different methods (coprecipitation, impregnation and citrate-based sol-gel method) followed by calcination at 500 °C. The physicochemical properties of the synthesized materials were investigated by various characterization techniques, namely: nitrogen adsorption-desorption isotherms, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and H2–temperature programmed reduction (TPR). This experimental study demonstrated that the role of the catalytic surface is much more important than the bulk one. Indeed, the incipient impregnation of CeO2–MnOx catalyst, supported on an optimized amount of 4 wt.% La2O3–Al2O3, provided the best results of the catalytic combustion of methane on our catalytic micro-convertors. This is mainly due to: (i) the highest pore size dimensions according to the Brunauer-Emmett-Teller (BET) investigations, (ii) the highest amount of Mn4+ or/and Ce4+ on the surface as revealed by XPS, (iii) the presence of a mixed phase (Ce2MnO6) as shown by X-ray diffraction; and (iv) a higher reducibility of Mn4+ or/and Ce4+ species as displayed by H2–TPR and therefore more reactive oxygen species. [ABSTRACT FROM AUTHOR]

In recent years, the search for solutions for the treatment of water pollution by toxic compounds such as phenols and chlorophenols has been increasing. Phenols and their derivatives are widely used in the manufacture of pesticides, insecticides, paper, and wood preservers, among other things. Chlorophenols are partially biodegradable but not directly photodegradable by sunlight and are extremely toxic—especially 2,4,6-trichlorophenol, which is considered to be potentially carcinogenic. As a viable proposal to be applied in the treatment of water contaminated with 2,4,6-trichlorophenol, this paper presents an application study of the thermally activated Mg/Fe layered double hydroxides as photocatalysts for the mineralization of this contaminant. Activated Mg/Fe layered double hydroxides were characterized by X-ray diffraction, thermal analysis, N2 physisorption, and scanning electron microscopy with X-ray dispersive energy. The results of the photocatalytic degradation of 2,4,6-trichlorophenol in aqueous solution showed good photocatalytic activity, with an efficiency of degradation of up to 93% and mineralization of 82%; degradation values which are higher than that of TiO2-P25, which only reached 18% degradation. The degradation capacity is attributed to the structure of the MgO–MgFe2O4 oxides derived from double laminate hydroxide Mg/Fe. A path of degradation based on a mechanism of superoxide and hollow radicals is proposed. [ABSTRACT FROM AUTHOR]

In this study, xCuO-CeO2 mixed oxide catalysts (Cu weight ratio x = 1.5, 3, 4.5, 6 and 15 wt.%) were prepared using solution combustion synthesis (SCS) and their catalytic activities towards the methane (CH4) oxidation reaction were studied. The combustion synthesis of the pure CeO2 and the CuO-CeO2 solid solution catalysts was performed using copper and/or cerium nitrate salt as an oxidizer and citric acid as a fuel. A variety of standard techniques, including scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy were employed to reveal the microstructural, crystal, thermal and electronic properties that may affect the performance of CH4 oxidation. The CuO subphase was detected in the prepared solid solution and confirmed with XRD and Raman spectroscopy, as indicated by the XRD peaks at diffraction angles of 35.3° and 38.5° and the Ag Raman mode at 289 cm−1, which are characteristics of tenorite CuO. A profound influence of Cu content was evident, not only affecting the structural and electronic properties of the catalysts, but also the performance of catalysts in the CH4 oxidation. The presence of Cu in the CeO2 lattice obviously promoted its catalytic activity for CH4 catalytic oxidation. Among the prepared catalysts, the 6% CuO-CeO2 catalyst demonstrated the highest performance, with T50 = 502 °C and T80 = 556 °C, an activity that is associated with the availability of a fine porous structure and the enhanced surface area of this catalyst. The results demonstrate that nanocrystalline copper-ceria mixed oxide catalysts could serve as an inexpensive and active material for CH4 combustion. [ABSTRACT FROM AUTHOR]

TiO2-ZnO-MgO mixed oxide nanomaterials (MONs) were synthetized via the sol-gel method and characterized by scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), nitrogen physisorption analysis, X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), Fourier transform infrared spectroscopy (FTIR), and color (Luminosity (L), a, b, Chrome, hue) parameters. Furthermore, the antimicrobial activity of the MONs was tested against Escherichia coli (EC), Salmonella paratyphi (SP), Staphylococcus aureus (SA), and Listeria monocytogenes (LM). The MONs presented a semi globular-ovoid shape of ≤100 nm. Samples were classified as mesoporous materials and preserved in the TiO2 anatase phase, with slight changes in the color parameters of the MONs in comparison with pure TiO2. The MONs exhibited antimicrobial activity, and their effect on the tested bacteria was in the following order: EC > SP > SA > LM. Therefore, MONs could be used as antimicrobial agents for industrial applications. [ABSTRACT FROM AUTHOR]

A series of transition metal oxides or mixed oxides supported nano-Au catalysts were prepared for the selective oxidation of glycerol to glyceric acid using 3% H2O2. It was found that the composition and structure of supports significantly influenced the catalytic performance of catalysts. The mesoporous trimetal mixed oxide (CuNiAlO) supported nano-Au catalysts were more active in comparison with the others. In the present catalytic system, the highest glycerol conversion was 90.5%, while the selectivity of glyceric acid could reach 72%. Moreover, the catalytic performance remained after 11 times of reaction. [ABSTRACT FROM AUTHOR]

Low-ordered carbon/layered double hydroxide (LDH) nanocomposites were prepared by rehydration of the oxides produced by calcination of an organic LDH. While the memory effect is a widely recognized effect on oxides produced by inorganic LDH, it is unprecedented from the calcination/rehydration of organic ones. Different temperatures (400, 600, and 1100 °C) were tested on the basis of thermogravimetric data. Water, instead of a carbonate solution, was used for the rehydration, with CO2 available from water itself and/or air to induce a slower process with an easier and better intercalation of the carbonaceous species. The samples were characterized by X-ray powder diffraction (XRPD), infrared in reflection mode (IR), and Raman spectroscopies and scanning electron microscopy (SEM). XRPD indicated the presence of carbonate LDH, and of residuals of unreacted oxides. IR confirmed that the prevailing anion is carbonate, coming from the water used for the rehydration and/or air. Raman data indicated the presence of low-ordered carbonaceous species moieties and SEM and XRPD the absence of separated bulky graphitic sheets, suggesting an intimate mixing of the low ordered carbonaceous phase with reconstructed LDH. Organic LDH gave better memory effect after calcination at 400 °C. Conversely, the carbonaceous species are observed after rehydration of the sample calcined at 600 °C with a reduced memory effect, demonstrating the interference of the carbonaceous phase with LDH reconstruction and the bonding with LDH layers to form a low-ordered carbon/LDH nanocomposite. [ABSTRACT FROM AUTHOR]

Different lanthanide (Ln)-doped cerium oxides (Ce0.5Ln0.5O1.75, where Ln: Gd, La, Pr, Nd, Sm) were loaded with Cu (20 wt. %) and used as catalysts for the oxidation of ethyl acetate (EtOAc), a common volatile organic compound (VOC). For comparison, both Cu-free (Ce-Ln) and supported Cu (Cu/Ce-Ln) samples were characterized by N₂ adsorption at -196 °C, scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed reduction in H₂. The following activity sequence, in terms of EtOAc conversion, was found for bare supports: CeO₂ ≈ Ce0.5Pr0.5O1.75 > Ce0.5Sm0.5O1.75 > Ce0.5Gd0.5O1.75 > Ce0.5Nd0.5O1.75 > Ce0.5La0.5O1.75. Cu addition improved the catalytic performance, without affecting the activity order. The best catalytic performance was obtained for Cu/CeO₂ and Cu/Ce0.5Pr0.5O1.75 samples, both achieving complete EtOAc conversion below ca. 290 °C. A strong correlation was revealed between the catalytic performance and the redox properties of the samples, in terms of reducibility and lattice oxygen availability. Νo particular correlation between the VOC oxidation performance and textural characteristics was found. The obtained results can be explained in terms of a Mars-van Krevelen type redox mechanism involving the participation of weakly bound (easily reduced) lattice oxygen and its consequent replenishment by gas phase oxygen.

The synthesis of functional nanoparticles via one-step flame spray pyrolysis (FSP), especially those of catalytic nature, has attracted the interests of scientists and engineers, as well as industries. The rapid and high temperature continuous synthesis yields nanoparticles with intrinsic features of active catalysts, that is, high surface area and surface energetics. For these reasons, FSP finds applications in various thermally inducible catalytic reactions. However, the design and synthesis of photocatalysts by FSP requires a knowledge set which is different from that established for thermal catalysts. Unknown to many, this has resulted in frustrations to those entering the field unprepared, especially since FSP appears to be an elegant tool in synthesising oxide nanoparticles of any elemental construct. From simple oxide to doped-oxide, and mixed metal oxide to the in situ deposition of noble metals, this Perspective gives an overview on the development of photocatalysts made by FSP in the last decade that led to a better understanding of the design criteria. Various challenges and opportunities are also highlighted, especially those beyond simple metal oxides, which perhaps contain the greatest potential for the exploitation of photocatalysts design by FSP.