Hollow @CuMgAl double layered hydrotalcites and mixed oxides with tunable textural and structural properties, and thus enhanced NH3-NOx-SCR activity.

Well-organized, spherical, mesoporous hollow @CuMgAl-LDHs (layered double hydroxides) are prepared by the controlled removal of the SiO2 from SiO2@CuMgAl-LDH core-shell hybrids that in turn are synthesized via a bottom-up strategy. The materials are prepared with various Cu/Mg molar ratios (Cu/Mg = 0.05-0.50) while keeping the ratio of Cu and Mg constant, (Cu + Mg)/Al = 2. The effect of Cu doping and the silica core removal process (conducted for 4 h at 30 °C using 1 M NaOH) on the chemical composition, morphology, structure, texture and reducibility of the resulting materials are described. @CuMgAl-MOs (mixed oxides) obtained by thermal treatment of the @CuMgAl-LDHs are active and selective catalysts for the selective catalytic reduction of NOx using ammonia, and effectively operate at low temperatures. The N2 yield increases with increased Cu content in the CuMgAl shell, which is associated with the easier reducibility of the Cu species incorporated into the MgAl matrix. @CuMgAl-MOs show better catalytic performance than bulk CuMgAl MOs.

Dehydration of methanol and ethanol over ferrierite originated layered zeolites - the role of acidity and porous structure.

Ferrierites and their delaminated (ITQ-6) and silica intercalated (ITQ-36) forms, with the intended molar Si/Al ratios of zeolite layers of 30 and 50, were synthesized and tested as catalysts of methanol to dimethyl ether (DME) as well as ethanol to diethyl ether (DEE) and ethylene dehydration. It was shown that increased content of acid sites, especially of Brønsted type, resulted in more active catalysts of alcohol dehydration. Brønsted acid sites dominate in ferrierites and their delaminated forms (ITQ-6). Contribution of the Lewis type of acid sites increased in silica pillared ferrierites (ITQ-36) possibly by deposition of aluminium species on the surface of amorphous silica. Conversion of methanol to DME was not limited by internal diffusion of reactants in narrow pores of ferrierite. Such limitation was observed for synthesis of larger DEE molecules over ferrierites. The ITQ-6 catalysts with the opened interlayer structure presented better efficiency in ethanol to DEE conversion due to overcoming these diffusional restrictions. Moreover, selectivity to DEE over ITQ-6 was higher than in the presence of three-dimensional ferrierite.

Selective and efficient catalytic and photocatalytic oxidation of diphenyl sulphide to sulfoxide and sulfone: the role of hydrogen peroxide and TiO2 polymorph.

In this paper, we describe the role of anatase and rutile crystal phases on diphenyl sulphide (Ph2S) catalytic and photocatalytic oxidation. The highly selective and efficient synthesis of diphenyl sulfoxide (Ph2SO) and diphenyl sulfone (Ph2SO2) at titanium dioxide was demonstrated. Ph2S oxidation in the presence of hydrogen peroxide at anatase-TiO2 can take place both as a catalytic and photocatalytic reaction, while at rutile-TiO2 only photocatalytic oxidation is possible. The reaction at anatase leads mainly to Ph2SO2, whereas, in the presence of rutile a complete conversion to Ph2SO is achieved after only 15 min (nearly 100% selectivity). Studies on the mechanistic details revealed a dual role of H2O2. It acts as a substrate in the reaction catalysed only by anatase, but it also plays a key role in alternative photocatalytic oxidation pathways. The presented study shows the applicability of photocatalysis in efficient and selective sulfoxide and sulfone production.

Catalysts Based on Strontium Titanate Doped with Ni/Co/Cu for Dry Reforming of Methane.

Two series of strontium titanates doped with Ni, Co, or Cu with general formula of SrTi1-xMexO3 for Sr-stoichiometric and Sr0.95Ti1-xMexO3 for Sr-non-stoichiometric materials (where Me = Ni, Co or Cu and x were 0.02 and 0.06) were obtained by the wet chemical method. The samples were calcinated at 900, 950, and 1050 °C and characterized in terms of their structural properties (XRD), the possibility of undergoing the reduction and oxidation reactions (TPR/TPOx), and catalytic properties. All obtained materials were multiphase and although the XRD analysis does not confirm the presence of Ni, Co, and Cu oxides (with one exception for Cu-doped sample), the TPR/TPOx profiles show reduction peaks that can be attributed to the reduction of these oxides which may at first appear in an amorphous form. Catalytic tests in dry reforming of methane reaction showed that the highest catalytic activity was achieved for Ni-doped materials (up to 90% of CH4 conversion) while Co and Cu-doped samples showed only a very slight catalytic effect. Additionally, the decrease in methane conversion with an increasing calcination temperature was observed for Ni-doped strontium titanates.

Spherical Al-MCM-41 Doped with Copper by Modified TIE Method as Effective Catalyst for Low-Temperature NH3-SCR.

Aluminum containing silica spherical MCM-41 was synthesized and modified with copper by the template ion-exchange method (TIE) and its modified version, including treatment of the samples with ammonia solution directly after template ion-exchange (TIE-NH3). The obtained samples were characterized with respect to their chemical composition (ICP-OES), structure (XRD), texture (low temperature N2 sorption), morphology (SEM-EDS), form and aggregation of deposited copper species (UV-vis DRS), reducibility of copper species (H2-TPR), and surface acidity (NH3-TPD). The deposition of copper by the TIE-NH3 method resulted in much better dispersion of this metal on the MCM-41 surface comparing to copper introduced by TIE method. It was shown that such highly dispersed copper species, mainly monomeric Cu2+ cations, deposited on aluminum containing silica spheres of MCM-41, are significantly more catalytically effective in the NH3-SCR process than analogous catalysts containing aggregated copper oxide species. The catalysts obtained by the TIE-NH3 method effectively operated in much broader temperature and were less active in the side process of direct ammonia oxidation by oxygen.

Titanium-silicon ferrierites and their delaminated forms modified with copper as effective catalysts for low-temperature NH3-SCR.

Titanium-silicon ferrierites with different Si/Ti ratios and their delaminated forms were modified with copper by ion-exchange. The obtained samples were characterized with respect to their chemical composition (ICP-OES), structure (XRD), texture (N2 sorption), morphology (SEM), form and aggregation of titanium and copper species (UV-vis-DRS), reducibility of deposited copper species (H2-TPR) and surface acidity (NH3-TPD). The porous structure of the zeolitic samples strongly influenced the form and aggregation of deposited copper species. In the case of the three dimensional microporous structure of ferrierites (Ti-FER), copper was deposited mainly in the form of aggregated copper oxide species, in contrast to the open micro- and mesoporous structure of delaminated ferrierites (Ti-ITQ-6), where mainly copper in the form of monomeric cations was identified. It was shown that monomeric copper cations are more catalytically active in NO to NO2 oxidation than aggregated copper oxide species and, therefore, for the low-temperature conversion of nitrogen oxides the fast SCR reaction pathway is more effective for delaminated ferrierites modified with copper (Cu-Ti-ITQ-6) than for microporous three dimensional ferrierite catalysts (Cu-Ti-FER).

Catalytic Performance of Spherical MCM-41 Modified with Copper and Iron as Catalysts of NH3-SCR Process.

Spherical MCM-41 with various copper and iron loadings was prepared by surfactant directed co-condensation method. The obtained samples were characterized with respect to their structure (X-ray diffraction, XRD), texture (N2 sorption), morphology (scanning electron microscopy, SEM), chemical composition (inductively coupled plasma optical emission spectrometry, ICP-OES), surface acidity (temperature programmed desorption of ammonia, NH3-TPD), form, and aggregation of iron and copper species (diffuse reflectance UV-Vis spectroscopy, UV-Vis DRS) as well as their reducibility (temperature programmed reduction with hydrogen, H2-TPR). The spherical MCM-41 samples modified with transition metals were tested as catalysts of selective catalytic reduction of NO with ammonia (NH3-SCR). Copper containing catalysts presented high catalytic activity at low-temperature NH3-SCR with a very high selectivity to nitrogen, which is desired reaction products. Similar results were obtained for iron containing catalysts, however in this case the loadings and forms of iron incorporated into silica samples very strongly influenced catalytic performance of the studied samples. The efficiency of the NH3-SCR process at higher temperatures was significantly limited by the side reaction of direct ammonia oxidation. The reactivity of ammonia molecules chemisorbed on the catalysts surface in NO reduction (NH3-SCR) and their selective oxidation (NH3-SCO) was verified by temperature-programmed surface reactions.

Ferrierite and Its Delaminated Forms Modified with Copper as Effective Catalysts for NH3-SCO Process.

Ferrierites and their delaminated forms (ITQ-6), containing aluminum or titanium in the zeolite framework, were synthetized and modified with copper by an ion-exchange method. The obtained samples were characterized with respect to their chemical composition (ICP-OES), structure (XRD, UV-Vis DRS), textural parameters (N2-sorption), surface acidity (NH3-TPD), form and reducibility of deposited copper species (UV-Vis DRS and H2-TPR). Ferrierites and delaminated ITQ-6 zeolites modified with copper were studied as catalysts for the selective catalytic oxidation of ammonia to dinitrogen (NH3-SCO). It was shown that aggregated copper oxide species, which were preferentially formed on Ti-zeolites, were catalytically active in direct low-temperature ammonia oxidation to NO, while copper introduced into Al-zeolites was present mainly in the form of monomeric copper cations catalytically active in selective reduction of NO by ammonia to dinitrogen. It was postulated that ammonia oxidation in the presence of the studied catalysts proceeds according to the internal-selective catalytic reduction mechanism (i-SCR) and therefore the suitable ratio between aggregated copper oxide species and monomeric copper cations is necessary to obtain active and selective catalysts for the NH3-SCO process. Cu/Al-ITQ-6 presented the best catalytic properties possibly due to the most optimal ratio of these copper species.

MCM-22, MCM-36, and ITQ-2 Zeolites with Different Si/Al Molar Ratios as Effective Catalysts of Methanol and Ethanol Dehydration.

MCM-22, MCM-36, and ITQ-2 zeolites with the intended Si/Al molar ratios of 15, 25, and 50 were synthetized and tested as catalysts for dehydration of methanol to dimethyl ether and dehydration of ethanol to diethyl ether and ethylene. The surface concentration of acid sites was regulated by the synthesis of zeolite precursors with different aluminum content in the zeolite framework, while the influence of porous structure on the overall efficiency of alcohol conversion was analyzed by application of zeolitic materials with different types of porosity-microporous MCM-22 as well as microporous-mesoporous MCM-36 and ITQ-2. The zeolitic samples were characterized with respect to their: chemical composition (ICP-OES), structure (XRD, FT-IR), texture (N2 sorption), and surface acidity (NH3-TPD). Comparison of the catalytic activity of the studied zeolitic catalysts with other reported catalytic systems, including zeolites with the similar Si/Al ratio as well as γ-Al2O3 (one of the commercial catalysts for methanol dehydration), shows a great potential of MCM-22, MCM-36, and ITQ-2 in the reactions of alcohols dehydration.

Catalytic and photocatalytic oxidation of diphenyl sulphide to diphenyl sulfoxide over titanium dioxide doped with vanadium, zinc, and tin.

Samples of TiO2 (P25) doped with zinc, tin, and vanadium, thermally treated at 550 °C for 6 h, were tested as catalysts and photocatalysts for the oxidation of diphenyl sulphide to diphenyl sulfoxide and sulfone, using hydrogen peroxide as an oxidation agent. Thermal treatment of pure TiO2 and its vanadium-doped forms resulted in a decrease of anatase and an increase of rutile content. The opposite effect was observed for TiO2 doped with zinc or tin, where thermal treatment resulted in the rutile to anatase phase transition. The role of V, Zn, and Sn admixtures as TiO2 phase-composition controllers was postulated. The catalytic and photocatalytic activity was found to be influenced more by the rutile and anatase contents of the samples than the presence of admixtures. The rutile-containing samples, TiO2 and V-TiO2, presented much better activity in the catalytic oxidation of diphenyl sulphide compared with the catalysts that only contained the anatase phase, Sn-TiO2 and Zn-TiO2. The reaction efficiency was significantly improved under UV radiation. In this case, the best photocatalytic activity was found for calcined TiO2, containing both anatase and rutile components. An increase in rutile content, observed in the vanadium-doped TiO2, decreased the efficiency of the photocatalytic diphenyl sulphide oxidation. Thus, the presence of both anatase and rutile phases, with their favourable contributions, typical for P25, is necessary for the effective oxidation of Ph2S to Ph2SO. Moreover, it was shown that for the second oxidation stage, Ph2SO to Ph2SO2, the presence of the rutile phase is very important.

Experimental Evidence of the Mechanism of Selective Catalytic Reduction of NO with NH3 over Fe-Containing BEA Zeolites.

Various temperature-programmed techniques were used as tools in mechanistic studies of selective catalytic reduction (SCR) of NO with ammonia in the presence of Fe-containing BEA zeolites. Moreover, FTIR studies of adsorbed NH3 and NO were conducted to determine the interactions of reactants with the catalyst surface. Iron was introduced into BEA zeolite by three different methods: i) two-step post-synthesis; ii) conventional wet impregnation; iii) ion exchange. The catalytic activity was dependent on the method used for iron introduction. The reactivities of NH3 and NO adsorbed on iron-modified zeolites obtained by impregnation and ion-exchange methods were higher than those measured for the catalyst obtained by a two-step post-synthesis method. The activity of Fe-containing zeolites in SCR was related to the form of deposited iron species, as well as to the nature, strength, and concentration of acid sites. Possible reaction pathways of NO reduction over the FeBEA zeolite catalysts were presented and discussed.

Characterization of Co and Fe-MCM-56 catalysts for NH3-SCR and N2O decomposition: An in situ FTIR study.

Two-step preparation of iron and cobalt-containing MCM-56 zeolites has been undertaken to evaluate the influence of their physicochemical properties in the selective catalytic reduction (NH3-SCR or DeNOx) of NO using NH3 as a reductant. Zeolites were prepared by the selective leaching of the framework cations by concentrated HNO3 solution and NH4F/HF mixture and consecutively, introduction of Co and Fe heteroatoms, in quantities below 1wt%. Further calcination allowed to obtain highly dispersed active species. Their evaluation and speciation was realized by adsorption of pyridine and NO, followed by FTIR spectroscopy. Both Fe-MCM-56 zeolites showed excellent activities (maximum NO conversion 92%) with high selectivity to dinitrogen (above 99%) in the high temperature NH3-SCR process. High catalytic activity of Fe-MCM-56 zeolites was assigned to the formation of stable nitrates, delivering NO to react with NH3 at higher temperatures and suppressing the direct NO oxidation. It was found that more nitrates was formed in Fe-MCM-56 (HNO3) than in Fe-MCM-56 (HF/NH4F) and that could compensate for the lower Fe loading, resulting in very similar catalytic activity of both catalysts. At the same time both Co-and Fe-MCM-56 zeolites were moderately active in direct N2O decomposition, with maximum N2O conversion not higher than 80% and activity window starting at 500°C. This phenomenon was expected since both types of catalysts contained well dispersed active centers, not beneficial for this reaction.

DeNOx Abatement over Sonically Prepared Iron-Substituted Y, USY and MFI Zeolite Catalysts in Lean Exhaust Gas Conditions.

Iron-substituted MFI, Y and USY zeolites prepared by two preparation routes-classical ion exchange and the ultrasound modified ion-exchange method-were characterised by micro-Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet (UV)/visible diffuse reflectance spectroscopy (UV/Vis DRS). Ultrasound irradiation, a new technique for the preparation of the metal salt suspension before incorporation to the zeolite structure, was employed. An experimental study of selective catalytic reduction (SCR) of NO with NH3 on both iron-substituted reference zeolite catalysts and those prepared through the application of ultrasound conducted during an ion-exchange process is presented. The prepared zeolite catalysts show high activity and selectivity in SCR deNOx abatement. The MFI-based iron catalysts, especially those prepared via the sonochemical method, revealed superior activity in the deNOx process, with almost 100% selectivity towards N2. The hydrothermal stability test confirmed high stability and activity of MFI-based catalysts in water-rich conditions during the deNOx reaction at 450 °C.

Acid-base treated vermiculite as high performance adsorbent: Insights into the mechanism of cationic dyes adsorption, regeneration, recyclability and stability studies.

Additional treatment with NaOH of acid activated vermiculite results in even higher increase in the adsorption capacity in comparison to samples modified only in acidic solution (first step of activation) with respect to raw material. Optimization of treatment conditions and adsorption capacity for two cationic dyes (methylene blue (MB) and astrazon red (AR)), also as binary mixture, was evaluated. The capacity, based on column studies, increased from 48 ± 2 to 203 ± 4 mg g-1 in the case of methylene blue and from 51 ± 1 to 127 ± 2 mg g-1 in the case of astrazon red on starting and acid-base treated material, respectively. It was shown that adsorption mechanism changes for both cationic dyes after NaOH treatment and it results in decrease of adsorption rate. In binary mixtures methylene blue is bound stronger by adsorbent and astrazon red may be removed in initial stage of adsorption. Extensive studies on desorption/regeneration process proved high efficiency in recyclable use of all materials. Although cation exchange capacity decreases due to acid treatment, after base treatment exchange properties are used more efficiently. On the other hand, increased specific surface area has less significant contribution into the adsorption potential of studied materials. Obtained adsorbents worked efficiently in 7 adsorption-regeneration cycles and loss of adsorption capacity was observed only in two first cycles.

Simultaneous removal of dyes and metal cations using an acid, acid-base and base modified vermiculite as a sustainable and recyclable adsorbent.

The aim of this work was the modification of vermiculite in order to produce a low cost, efficient and sustainable adsorbent for dyes and metals. Three activation methods consisting of acid, base and combined acid/base treatment were applied to improve the of vermiculite's adsorption properties. Adsorbents were tested in single, bi- and tricomponent solutions containing cationic dyes and Cu2+ cations. The raw material showed low adsorption capacity for dyes and metal. The acid/base treated vermiculite had very good adsorption capacity toward dyes while the maximum adsorption capacity for Cu2+ did not change comparing to the starting material. The alkaline treated vermiculite was a good adsorbent for metals, while still being able to remove dyes on the level of the not treated material. Moreover, it was shown that the materials may be regenerated and used in several adsorption-desorption cycles. Furthermore, it was possible to separate adsorbed dyes from metals that were desorbed, using as eluents ethanol/NaCl and 0.05M HNO3, respectively. This opens a possibility for sustainable disposal and neutralization of both of the pollutants or for their further applications in other processes.

The influence of acid treatments over vermiculite based material as adsorbent for cationic textile dyestuffs.

The influence of different acid treatments over vermiculite was evaluated. Equilibrium, kinetic and column studies have been conducted. The results showed that vermiculite first treated with nitric acid and then with citric acid has higher adsorption capacity, presenting maximum adsorption capacities in column experiments: for Astrazon Red (AR), 100.8 ± 0.8 mg g(-1) and 54 ± 1 mg g(-1) for modified and raw material, respectively; for Methylene Blue (MB) 150 ± 4 mg g(-1) and 55 ± 2 mg g(-1) for modified and raw material, respectively. Materials characterization by X-ray diffraction, UV-vis-diffuse reflectance spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, X-ray fluorescence, N2 adsorption and CEC determination, has been performed. The results suggest the existence of exchange of interlayer cations, leaching of metals from vermiculite's sheets and formation of an amorphous phase in the material. Adsorption follows pseudo 2(nd) order model kinetics for both dyestuffs and equilibrium occurs accordingly to Langmuir's model for AR and Freundlich's model for MB. In column systems Yan's model is the best fit. The enhanced properties of acid treated vermiculite offer new perspectives for the use of this adsorbent in wastewater treatment.

Enhancement of Electrochemical Performance of LiMn2O4 Spinel Cathode Material by Synergetic Substitution with Ni and S.

Nickel and sulfur doped lithium manganese spinels with a nominal composition of LiMn2-xNixO4-ySy (0.1 ≤ x ≤ 0.5 and y = 0.01) were synthesized by a xerogel-type sol-gel method followed by subsequent calcinations at 300 and 650 °C in air. The samples were investigated in terms of physicochemical properties using X-ray powder diffraction (XRD), transmission electron microscopy (EDS-TEM), N2 adsorption-desorption measurements (N2-BET), differential scanning calorimetry (DSC), and electrical conductivity studies (EC). Electrochemical characteristics of Li/Li⁺/LiMn2-xNixO4-ySy cells were examined by galvanostatic charge/discharge tests (CELL TEST), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). The XRD showed that for samples calcined at 650 °C containing 0.1 and 0.2 mole of Ni single phase materials of Fd-3m group symmetry and nanoparticles size of around 50 nm were obtained. The energy dispersive X-ray spectroscopy (EDS) mapping confirmed homogenous distribution of nickel and sulfur in the obtained spinel materials. Moreover, it was revealed that the adverse phase transition at around room temperature typical for the stoichiometric spinel was successfully suppressed by Ni and S substitution. Electrochemical results indicated that slight substitution of nickel (x = 0.1) and sulfur (y = 0.01) in the LiMn2O4 enhances the electrochemical performance along with the rate capability and capacity retention.

Catalytic activity of MCM-48-, SBA-15-, MCF-, and MSU-type mesoporous silicas modified with Fe3+ species in the oxidative dehydrogenation of ethylbenzene in the presence of N2O.

MCM-48, SBA-15, MCF, and MSU mesoporous silicas were used as supports for a deposition of Fe oxide species. Iron was introduced using two different methods: the wetness impregnation and the molecular designed dispersion (MDD). The obtained catalysts were characterized with respect to their textural parameters (BET), chemical composition (electron microprobe analysis), and reducibility (TPR). The coordination environment of Fe was determined using EPR and UV-vis/DRS. The samples were tested as catalysts in the oxidative dehydrogenation of ethylbenzene to styrene in the presence of N(2)O. An influence of Fe dispersion and reducibility on the catalytic activity was discussed. Isolated Fe(3+) species appeared to be more selective in the styrene formation, whereas iron oxide clusters showed a higher selectivity in total oxidation of aromatic hydrocarbons. The reaction system was well described by the Mars- van Krevellen mechanism.

Dehydrogenation of ethylbenzene with nitrous oxide in the presence of mesoporous silica materials modified with transition metal oxides.

The novel mesoporous templated silicas (MCM-48, SBA-15, MCF, and MSU) were used as supports for transition metal (Cu, Cr, or Fe) oxides. The catalysts were synthesized using the incipient wetness impregnation, and characterized by low-temperature N2 sorption, DRIFT, photoacoustic IR spectroscopy, UV-vis diffuse reflectance spectroscopy, and temperature-programmed desorption of ammonia. It was shown that the preparation method used results in different distributions and dimensions of the transition metal oxide clusters on the inert support surface. The prepared catalysts were tested in the reaction of oxidative dehydrogenation of ethylbenzene in the presence of nitrous oxide. The iron-containing catalysts showed the highest catalytic activity. The presence of isolated Fe3+ was found to be the most important factor influencing the ethylbenzene conversion. The undesirable effect of the increase in selectivity toward CO2 was observed for the samples with the highest concentrations of acidic surface sites.

Modification of MCM-48-, SBA-15-, MCF-, and MSU-type mesoporous silicas with transition metal oxides using the molecular designed dispersion method.

Four various mesoporous silicas (MCM-48, SBA-15, MCF, and MSU) were modified by the molecular designed dispersion method using Fe(acac)3, Cr(acac)3, and Cu(acac)2 complexes. The deposition was performed at the same concentration of the metal acetylacetonate (acac) complex in a toluene solution. All as-synthesized samples were investigated by diffuse reflectance infrared Fourier transform spectroscopy, Fourier transform infrared photoacoustic spectroscopy, and thermogravimetric analysis. The calcined materials were studied with respect to their textural properties (Brunauer-Emmett-Teller adsorption isotherm) and chemical composition (electron microprobe analysis). It allowed elucidation of the mechanism of interaction between the acac complex and the silanol groups. For the MCM-48, SBA-15, and MCF materials, the formation of hydrogen bonding was found for the chromium- and copper-modified samples, whereas the Fe-containing materials showed the ligand exchange mechanism. The strong interaction of the MSU support and the different acetylacetonate complexes, resulting in a loss of at least one acac ligand, was observed. The mesoporous silicas modified with transition metal oxides were studied by UV-vis-DR spectroscopy. The different metal dispersions were found for the samples containing various transition metal oxides.