Role of lamp type in conventional batch and micro-photoreactor for photocatalytic hydrogen production.

The use of an irradiation source with a homogeneous distribution of irradiation in the volume of the reaction mixture belongs to the essential aspects of heterogeneous photocatalysis. First, the efficacy of six lamps with various radiation intensity and distribution characteristics is contrasted. The topic of discussion is the photocatalytic hydrogen production from a methanol-water solution in the presence of a NiO-TiO2 photocatalyst. The second section is focused on the potential of a micro-photoreactor system-the batch reactor with a micro-reactor with a circulating reaction mixture, in which the photocatalytic reaction takes place using TiO2 immobilized on borosilicate glass. Continuous photocatalytic hydrogen generation from a methanol-water solution is possible in a micro-photoreactor. This system produced 333.7 ± 21.1 µmol H2 (252.8 ± 16.0 mmol.m-2, the hydrogen formation per thin film area) in a reproducible manner during 168 h.

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.

Reconstruction of the ZnAl Mixed Oxides Into the Layered Double Hydroxide Catalysts Active in the Aldol Condensation of Furfural: The Role of ZnO Particles.

A memory effect is the ability to restore the original, lamellar layered double hydroxide structure. Herein, we have described 1) the changes in the structural and basic properties of ZnAl mixed oxides during their transformation into ZnAl-reconstructed LDHs (RE-LDHs); 2) the extraordinary properties of ZnAl RE-LDHs compared to the original ZnAl LDHs; and 3) the changes of basic properties during the interaction of ZnAl RE-LDHs with atmospheric CO2. Aldol condensation was selected as probe reaction to prove the catalytic potential of ZnAl RE-LDHs. We have described a target method for preparing ZnAl RE-LDHs with a large number of basic sites. ZnAl RE-LDHs possess significantly higher furfural conversion in the aldol condensation of furfural than MOs. The structural, textural, and basic properties of the studied materials were described by temperature-programmed analysis, X-ray diffraction, N2 adsorption, temperature-programmed desorption of CO2, and in-situ diffuse reflectance spectroscopy.

Alternative Preparation of Improved NiMo-Alumina Deoxygenation Catalysts.

This investigation deals with NiMo-alumina hydrotreating catalysts effective in the deoxygenation of rapeseed oil. The main goal was to compare catalyst structure and their deoxygenation performance and to link these parameters to reveal important structural information regarding the catalyst's intended use. Catalysts were prepared from different precursors (nickel acetate tetrahydrate/molybdenyl acetylacetonate in ethanol and water vs. nickel nitrate hexahydrate/ammonium heptamolybdate tetrahydrate in water), which resulted in their contrasting structural arrangement. These changes were characterized by elemental composition determination, UV-Vis diffuse reflectance spectroscopy, temperature programmed reduction by hydrogen, nitrogen physisorption at 77 K, scanning and transmission electron microscopies, and deoxygenation of rapeseed oil. The critical aspect of high oxygen elimination was a homogeneous dispersion of NiO and MoO3 phases on the support. It subsequently led to the effective transformation of the oxide form of a catalyst to its active sulfide form well-dispersed on the support. On the other hand, the formation of bulk MoO3 resulted in the separate bulk phase and lower extent of sulfidation.

Successful Immobilization of Lanthanides Doped TiO2 on Inert Foam for Repeatable Hydrogen Generation from Aqueous Ammonia.

We describe the successful possibility of the immobilization of a photocatalyst on foam, which is beneficial from a practical point of view. An immobilized photocatalyst is possible for use in a continuous experiment and can be easily separated from the reactor after the reaction concludes. Parent TiO2, La/TiO2, and Nd/TiO2 photocatalysts (containing 0.1 wt.% of lanthanide) were prepared by the sol-gel method and immobilized on Al2O3/SiO2 foam (VUKOPOR A) by the dip-coating method. The photocatalysts were investigated for the photocatalytic hydrogen generation from an aqueous ammonia solution under UVA light (365 nm). The evolution of hydrogen was compared with photolysis, which was limited to zero. The higher hydrogen generation was observed in the presence of 0.1 wt.% La/TiO2 than in 0.1 wt.% Nd/TiO2. This is, besides other things, related to the higher level of the conduction band, which was observed for 0.1 wt.% La/TiO2. The higher conduction band's position is more effective for hydrogen production from ammonia decomposition.

The Role of Fluorine in F-La/TiO2 Photocatalysts on Photocatalytic Decomposition of Methanol-Water Solution.

F-La/TiO2 photocatalysts were studied in photocatalytic decomposition water-methanol solution. The structural, textural, optical, and electronic properties of F-La/TiO2 photocatalysts were studied by combination of X-ray powder diffraction (XRD), nitrogen physisorption, Ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), Electrochemical impedance spectroscopy (EIS), and X-ray fluorescence (XPS). The production of hydrogen in the presence of 2.8F-La/TiO2 was nearly up to 3 times higher than in the presence of pure TiO2. The photocatalytic performance of F-La/TiO2 increased with increasing photocurrent response and conductivity originating from the higher amount of fluorine presented in the lattice of TiO2.

Physico-Chemical Properties of MgGa Mixed Oxides and Reconstructed Layered Double Hydroxides and Their Performance in Aldol Condensation of Furfural and Acetone.

MgGa layered double hydroxides (Mg/Ga = 2-4) were synthesized and used for the preparation of MgGa mixed oxides and reconstructed hydrotalcites. The properties of the prepared materials were examined by physico-chemical methods (XRD, TGA, NH3-TPD, CO2-TPD, SEM, and DRIFT) and tested in aldol condensation of furfural and acetone. The as-prepared phase-pure MgGa samples possessed hydrotalcite structure, and their calcination resulted in mixed oxides with MgO structure with a small admixture phase characterized by a reflection at 2θ ≈ 36.0°. The interaction of MgGa mixed oxides with pure water resulted in reconstruction of the HTC structure already after 15 s of the rehydration with maximum crystallinity achieved after 60 s. TGA-MS experiments proved a substantial decrease in carbonates in all rehydrated samples compared with their as-prepared counterparts. This allowed suggesting presence of interlayer hydroxyls in the samples. Acido-basic properties of MgGa mixed oxides determined by TPD technique did not correlate with Mg/Ga ratio which was explained by the specific distribution of Ga atoms on the external surface of the samples. CO2-TPD method was also used to evaluate the basic properties of the reconstructed MgGa samples. In these experiments, an intensive peak at T = 450°C on CO2-TPD curve was attributed to the decomposition of carbonates newly formed by CO2 interaction with interlayer carbonates rather than to CO2 desorption from basic sites. Accordingly, CO2-TPD method quantitatively characterized the interlayer hydroxyls only indirectly. Furfural conversion on reconstructed MgGa materials was much larger compared with MgGa mixed oxides confirming that Brønsted basic sites in MgGa catalysts, like MgAl catalysts, were active in the reaction. Mg/Ga ratio in mixed oxides influenced product selectivity which was explained by the difference in textural properties of the samples. In contrast, Mg/Ga ratio in reconstructed catalysts had practically no effect on the composition of reaction products suggesting that the basic sites in these catalysts acted similarly in aldol condensation of acetone with furfural. It was concluded that the properties of MgGa samples resembled in a great extent those of MgAl hydrotalcite-based materials and demonstrated their potential as catalysts for base-catalyzed reactions.

TiO2 and Nitrogen Doped TiO2 Prepared by Different Methods; on the (Micro)structure and Photocatalytic Activity in CO2 Reduction and N2O Decomposition.

TiO2 as nanostructured powders were prepared by (1) sol-gel process and (2) hydrothermal method in combination with (A) the processing by pressurized hot water and methanol or (B) calcination. The subsequent synthesis step was the modification of prepared nanostructured TiO2 with nitrogen using commercial urea. Textural, structural, surface and optical properties of prepared TiO2 and N/TiO2 were characterized by nitrogen physisorption, powder X-ray diffraction, X-ray photoelectron spectroscopy and DR UV-vis spectroscopy. It was revealed that TiO2 and N/TiO2 processed by pressurized fluids showed the highest surface areas. Furthermore, all prepared materials were the mixtures of major anatase phase and minor brookite phase, which was in nanocrystalline or amorphous (as nuclei) form depending on the applied preparation method. All the N/TiO2 materials exhibited enhanced crystallinity with a larger anatase crystallite-size than undoped parent TiO2. The photocatalytic activity of the prepared TiO2 and N/TiO2 was tested in the photocatalytic reduction of CO2 and the photocatalytic decomposition of N2O. The key parameters influencing the photocatalytic activity was the ratio of anatase-to-brookite and character of brookite. The optimum ratio of anatase-to-brookite for the CO2 photocatalytic reduction was determined to be about 83 wt.% of anatase and 17 wt.% of brookite (amorphous-like) (TiO2-SG-C). The presence of nitrogen decreased a bit the photocatalytic activity of tested materials. On the other hand, TiO2-SG-C was the least active in the N2O photocatalytic decomposition. In the case of N2O photocatalytic decomposition, the modification of TiO2 crystallites surface by nitrogen increased the photocatalytic activity of all investigated materials. The maximum N2O conversion (about 63 % after 18 h of illumination) in inert gas was reached over all N/TiO2.

Nd/TiO2 Anatase-Brookite Photocatalysts for Photocatalytic Decomposition of Methanol.

Neodymium enriched TiO2 anatase-brookite powders were prepared by unconventional method via using pressurized hot fluids for TiO2 crystallization and purification. The photocatalysts were tested in the CH3OH photocatalytic decomposition and they were characterized with respect to the textural (nitrogen adsorption), structural (XRD, XPS, and Raman spectroscopies), chemical (XRF), and optical (DR UV-Vis spectroscopy) and photoelectrochemical measurement. All prepared materials were nanocrystalline, had biphasic (anatase- brookite) structure and relatively large specific surface area (125 m2.g-1). The research work indicates that the doping of neodymium on TiO2 photocatalysts significantly enhances the efficiency of photocatalytic reaction. The photocatalytic activity increased with increasing portion of hydroxyl oxygen to the total amount of oxygen species. It was ascertained that the optimal amount of 1 wt% Nd in TiO2 accomplished the increasing of hydrogen production by 70% in comparison with pure TiO2. The neodymium doped on the titanium dioxide act as sites with accumulation of electrons. The higher efficiency of photocatalytic process was achieved due to improved electron-hole separation on the modified TiO2 photocatalysts. This result was confirmed by electrochemical measurements, the most active photocatalysts proved the highest photocurrent responses.

Photocatalytic reduction of carbon dioxide over Cu/TiO2 photocatalysts.

The photocatalytic reduction of CO2 with H2O was investigated using Cu/TiO2 photocatalysts in aqueous solution. For this purpose, Cu/TiO2 photocatalysts (with 0.2, 0.9, 2, 4, and 6 wt.% of Cu) have been synthesized via sol-gel method. The photocatalysts were extensively characterized by means of inductively coupled plasma optical emission spectrometry (ICP-OES), N2 physisorption (BET), XRD, UV-vis DRS, FT-IR, Raman spectroscopy, TEM-EDX, and photoelectrochemical measurements. The as-prepared photocatalysts contain anatase as a major crystalline phase with a crystallite size around 13 nm. By increasing the amount of Cu, specific surface area and band gap energy decreased in addition to the formation of large agglomeration of CuO. Results revealed that the photocatalytic reduction of CO2 decreased in the presence of Cu/TiO2 in comparison to pure TiO2, which might be associated to the formation of CuO phase acting as a recombination center of generated electron-hole pair. Decreasing of photoactivity can also be connected with a very low position of conduction band of photocatalysts with high Cu content, which makes H2 production necessary for CO2 reduction more difficult.

Photocatalytic decomposition of methanol over La/TiO2 materials.

Lanthanum-modified TiO2 photocatalysts (0.2-1.5 wt% La) were investigated in the methanol decomposition in an aqueous solution. The photocatalysts were prepared by the common sol-gel method followed by calcination. The structural (X-ray diffraction, Raman, X-ray photoelectron spectroscopy), textural (N2 physisorption), and optical properties (diffuse reflectance spectroscopy, photoelectrochemical measurements) of all synthetized nanomaterials were correlated with photocatalytic activity. Both pure TiO2 and La-doped TiO2 photocatalysts proved higher yields of hydrogen in comparison to photolysis. The photocatalyst with optimal amount of lanthanum (0.2 wt% La) showed almost two times higher amount of hydrogen produced at the same time as in the presence of pure TiO2. The photocatalytic activity increased with both increasing photocurrent response and decreasing amount of lattice and surface O species. It has been shown that both direct and indirect mechanisms of methanol photocatalytic oxidation participate in the production of hydrogen. Both direct and indirect mechanisms take part in the formation of hydrogen.

Photocatalytic Hydrogen Formation from Ammonia in an Aqueous Solution Over Pt-Enriched TiO2-ZrO2 Photocatalyst.

The aim of this study was to remove ammonia from an aqueous solution by its decomposition to valuable products such as H2 and harmless N2 under UV light. The decomposition of ammonia by photocatalytic process represents an emerging and interesting way of its removal since beside the need of its reduction from the drinking and wastewaters with the respect to its negative impact on human and mammals health, it can lead to generation of hydrogen as an alternative fuel. A laboratory-synthesized Pt/TiO2-ZrO2 photocatalyst was studied and its photocatalytic activity was compared with the activity of commercial TiO2 Evonik P25. The Pt/TiO2-ZrO2 photocatalyst was prepared by combining a sol-gel process controlled within reverse micelles of nonionic surfactant Triton X-114 in cyclohexane, impregnation under vacuum and calcination. Explored photocatalysts were characterized by organic elementary analysis, nitrogen physisorption, XRD, FESEM and UV-Vis spectroscopy. The real platinum content in the Pt/TiO2-ZrO2 photocatalyst was determined by ICP-MS. The photocatalytic decomposition of ammonia was investigated in the time range of 0-12 h. During the first two hours the generation of hydrogen was almost negligible. The generation of hydrogen increased after 4 h of irradiation. Based on time dependences of ammonia decomposition the kinetic rate constants for Pt/TiO2-ZrO2 and TiO2 Evonik P25 photocatalysts were calculated. The ammonia photocatalytic decomposition was described well by the first order kinetic equation. The photocatalytic ammonia decomposition over the platinized TiO2-ZrO2 photocatalyst was proving 2 times higher photocatalytic performance than Evonik P25 (1241 µmol/g(cat) and 665 µmol/g(cat), respectively).

Quantitative LIBS analysis of vanadium in samples of hexagonal mesoporous silica catalysts.

The method for the analysis of vanadium in hexagonal mesoporous silica (V-HMS) catalysts using Laser Induced Breakdown Spectrometry (LIBS) was suggested. Commercially available LIBS spectrometer was calibrated with the aid of authentic V-HMS samples previously analyzed by ICP OES after microwave digestion. Deposition of the sample on the surface of adhesive tape was adopted as a sample preparation method. Strong matrix effect connected with the catalyst preparation technique (1st vanadium added in the process of HMS synthesis, 2nd already synthesised silica matrix was impregnated by vanadium) was observed. The concentration range of V in the set of nine calibration standards was 1.3-4.5% (w/w). Limit of detection was 0.13% (w/w) and it was calculated as a triple standard deviation from five replicated determinations of vanadium in the real sample with a very low vanadium concentration. Comparable results of LIBS and ED XRF were obtained if the same set of standards was used for calibration of both methods and vanadium was measured in the same type of real samples. LIBS calibration constructed using V-HMS-impregnated samples failed for measuring of V-HMS-synthesized samples. LIBS measurements seem to be strongly influenced with different chemical forms of vanadium in impregnated and synthesised samples. The combination of LIBS and ED XRF is able to provide new information about measured samples (in our case for example about procedure of catalyst preparation).