Showing papers in "Catalysts in 2013"
TL;DR: In this paper, a review of the research and application of heterogeneous semiconductor photocatalysis for the treatment of low-level concentrations of pollutants in water and air using titanium dioxide as a “model” semiconductor.
Abstract: Semiconductor heterogeneous photocatalysis, the subject of this review, is a versatile, low-cost and environmentally benign treatment technology for a host of pollutants. These may be of biological, organic and inorganic in origin within water and air. The efficient and successful application of photocatalysis demands that the pollutant, the catalyst and source of illumination are in close proximity or contact with each other. The ability of advanced oxidation technology to remove low levels of persistent organic pollutants as well as microorganisms in water has been widely demonstrated and, progressively, the technology is now being commercialized in many areas of the world including developing nations. This review considers recent developments in the research and application of heterogeneous semiconductor photocatalysis for the treatment of low-level concentrations of pollutants in water and air using titanium dioxide as a “model” semiconductor. The review considers charge transport characteristics on the semiconductor surface, photocatalyst reactor design and organic degradation mechanistic pathways. The effects of photoreactor operating parameters on the photocatalytic process are discussed in addition to mineralization and disinfection kinetics.
995 citations
TL;DR: A comprehensive survey of the different methods available for preparing brookite powders and films is reported in this article, with a focus on the most traditional methods, such as hydrothermal processes at high temperatures and pressures, and to environmentally benign syntheses using water soluble compounds and water as the solvent.
Abstract: Brookite is the least studied TiO2 photocatalyst due to the difficulties usually encountered in order to obtain it as a pure phase. In this review, a comprehensive survey of the different methods available for preparing brookite powders and films is reported. Attention has been paid both to the most traditional methods, such as hydrothermal processes at high temperatures and pressures, and to environmentally benign syntheses using water soluble compounds and water as the solvent. Papers reporting the photocatalytic activity of pure and brookite-based samples have been reviewed.
481 citations
TL;DR: In this article, the significance of recombination of a photoexcited electron and a hole in conduction and valence bands, respectively, of a titania photocatalyst, has been discussed.
Abstract: This short review paper shows the significance of recombination of a photoexcited electron and a hole in conduction and valence bands, respectively, of a titania photocatalyst, since recombination has not yet been fully understood and has not been evaluated adequately during the past several decades of research on heterogeneous photocatalysis.
157 citations
TL;DR: In this article, the authors summarized the very recent progress in the design, synthesis, and characterization of supported bimetallic Ni-based catalysts for steam reforming and compared the performance of these catalysts with other metals (such as Sn, Cu, Co, Mo, Fe, Gd and B).
Abstract: Steam reforming of light hydrocarbons provides a promising method for hydrogen production. Ni-based catalysts are so far the best and the most commonly used catalysts for steam reforming because of their acceptably high activity and significantly lower cost in comparison with alternative precious metal-based catalysts. However, nickel catalysts are susceptible to deactivation from the deposition of carbon, even when operating at steam-to-carbon ratios predicted to be thermodynamically outside of the carbon-forming regime. Reactivity and deactivation by carbon formation can be tuned by modifying Ni surfaces with a second metal, such as Au through alloy formation. In the present review, we summarize the very recent progress in the design, synthesis, and characterization of supported bimetallic Ni-based catalysts for steam reforming. The progress in the modification of Ni with noble metals (such as Au and Ag) is discussed in terms of preparation, characterization and pretreatment methods. Moreover, the comparison with the effects of other metals (such as Sn, Cu, Co, Mo, Fe, Gd and B) is addressed. The differences of catalytic activity, thermal stability and carbon species between bimetallic and monometallic Ni-based catalysts are also briefly shown.
144 citations
TL;DR: In this article, a review of recent results obtained in the field of specific surface-oriented anatase TiO2 crystals preparation is presented, mainly focused on the fluorine-mediated hydrothermal and/or solvothermal processes employed for the synthesis and assembly of anatase micro/nanostructures with dominant {001} facets.
Abstract: Semiconductors crystal facet engineering has become an important strategy for properly tuning and optimizing both the physicochemical properties and the reactivity of photocatalysts. In this review, a concise survey of recent results obtained in the field of specific surface-oriented anatase TiO2 crystals preparation is presented. The attention is mainly focused on the fluorine-mediated hydrothermal and/or solvothermal processes employed for the synthesis and the assembly of anatase micro/nanostructures with dominant {001} facets. Their peculiar photocatalytic properties and potential applications are also presented, with a particular focus on photocatalysis-based environmental clean up and solar energy conversion applications. Finally, the most promising results obtained in the engineering of TiO2 anatase crystal facets obtained by employing alternative, possibly more environmentally friendly methods are critically compared.
108 citations
TL;DR: Comparisons of the inactivation of various species of bacteria and viruses when their suspensions were dropped on the surface of TiO2-coated glass emphasize that effective cleaning and disinfection by photocatalysis in nosocomial settings prevents pathogen transmission.
Abstract: Photocatalytically active titanium dioxide (TiO2) is widely used as a self-cleaning and self-disinfecting material in many applications to keep environments biologically clean. Several studies on the inactivation of bacteria and viruses by photocatalytic reactions have also been reported; however, only few studies evaluated the spectrum of the microbicidal activity with photocatalysis for various species. There is a need to confirm the expected effectiveness of disinfection by photocatalysis against multidrug-resistant bacteria and viruses. In this study, microbicidal activity of photocatalysis was evaluated by comparing the inactivation of various species of bacteria and viruses when their suspensions were dropped on the surface of TiO2-coated glass. Gram-positive bacteria, e.g., methicillin-resistant Staphylococcus aureus, vancomycin-resistant Enterococcus faecalis, and penicillin-resistant Streptococcus pneumoniae, were easily inactivated by photocatalysis, whereas some gram-negative bacteria, e.g., Escherichia coli and multidrug-resistant Pseudomonas aeruginosa, were gradually inactivated by photocatalysis. Influenza virus, an enveloped virus, was significantly inactivated by photocatalysis compared with feline calicivirus, a non-enveloped virus. The effectiveness of microbicidal activity by photocatalysis may depend on the surface structure. However, they are effectively inactivated by photocatalysis on the surface of TiO2-coated glass. Our data emphasize that effective cleaning and disinfection by photocatalysis in nosocomial settings prevents pathogen transmission.
84 citations
TL;DR: In this paper, low temperature fuel cells are expected to come into widespread commercial use in the areas of transportation and stationary and portable power generation, and thus will help solve energy shortage and environmental issues.
Abstract: Low temperature fuel cells are expected to come into widespread commercial use in the areas of transportation and stationary and portable power generation, and thus will help solve energy shortage and environmental issues. [...]
75 citations
TL;DR: In this paper, the results obtained in the selective hydrogenation of citral catalyzed by carbon material supported metals are analyzed and a review of the performance of this type of hydrogenation reaction is presented.
Abstract: The heterogeneously catalyzed selective-hydrogenation of citral is one of the more feasible ways for obtaining its appreciated unsaturated-alcohols, nerol and geraniol, which are present in over 250 essential oils. Thus, citral has very recently come to be produced petro-chemically in very large quantities, and so partial hydrogenation of citral has become a very economical route for the production of these compounds. However, the selective hydrogenation of citral is not easy, because citral is an α,β-unsaturated aldehyde which possesses three double bonds that can be hydrogenated: an isolated C=C bond and the conjugated C=O and C=C bonds. For this reason, in catalyst selection there are several important issues which affect the product selectivity, for example, the active metal and metal particle size which are factors related to the catalyst preparation method, catalyst precursor, or support surface area, as well as other factors such as porosity, the addition of a second catalytic metal, and, of course, the type of catalyst support. About this last one, carbon materials are very interesting supports for this type of hydrogenation reaction due to their unique chemical and textural properties. This review collects and analyzes the results obtained in the selective hydrogenation of citral catalyzed by carbon material supported metals.
63 citations
TL;DR: In this paper, a review of the state-of-the-art in the field of catalysts based on combinations between copper and ceria for preferential oxidation of CO in H2-rich streams is presented.
Abstract: This article reviews work done at authors’ laboratories about catalysts based on combinations between copper and ceria for preferential oxidation of CO in H2-rich streams (CO-PROX). The main focus of this review is the characterization of active sites for the process on the basis of spectroscopic analysis of the systems under reaction conditions (operando techniques). On such a basis, it is exposed the state of the art in this field in connection with results obtained in other laboratories.
60 citations
TL;DR: In this paper, a cross-section of TiO2 compositions for which existing evidence suggests the prospect of improved performance compared to standard Degussa P25 was investigated, and the results suggest that the choice of the photocatalyst should be best made to fit the reactor design and copatalyst mounting constraints such as mass transport, reactive surface, and light field.
Abstract: This study investigates a cross-section of TiO2 compositions for which existing evidence suggests the prospect of improved performance compared to standard Degussa P25. In the context of a program aimed toward a 365 nm LED based photo-reactor, the question is whether a distinctly superior photocatalyst composition for drinking water treatment is now available that would shape design choices. An answer was sought by synthesizing several photocatalysts with reported high reactivity in some context in the literature, and by performing photocatalysts reactivity tests using common pollutants of water system including Natural Organic Matter (NOM) and Emerging Contaminants (ECs) from the pesticide and pharmaceutical classes. 365 nm Light Emitting Diodes (LEDs) were used as the irradiation source. Since LEDs are now available in the UV, we did not examine the TiO2 modifications that bring band gap excitation into the region beyond 400 nm. The results suggest that the choice of the photocatalyst should be best made to fit the reactor design and photocatalyst mounting constraints such as mass transport, reactive surface, and light field. No photocatalyst composition overall, superior for all classes emerged.
53 citations
TL;DR: In this article, the synergistic effect in the catalytic system of ionic liquids (ILs) for the synthesis of cyclic carbonate from carbon dioxide and epoxide is discussed.
Abstract: This review presents the synergistic effect in the catalytic system of ionic liquids (ILs) for the synthesis of cyclic carbonate from carbon dioxide and epoxide. The emphasis of this review is on three aspects: the catalytic system of metal-based ionic liquids, the catalytic system of hydrogen bond-promoted ionic liquids and supported ionic liquids. Metal and ionic liquids show a synergistic effect on the cycloaddition reactions of epoxides. The cations and anions of ionic liquids show a synergistic effect on the cycloaddition reactions. The functional groups in cations or supports combined with the anions have a synergistic effect on the cycloaddition reactions. Synergistic catalytic effects of ILs play an important role of promoting the cycloaddition reactions of epoxides. The design of catalytic system of ionic liquids will be possible if the synergistic effect on a molecular level is understood.
TL;DR: In this article, the formation of strongly chemiluminescent 3-hydroxyphthalic hydrazide by hydroxylation of non-chemiluminecent phthalic hyrazide can be applied as a selective reaction prob...
Abstract: This work demonstrates how formation of strongly chemiluminescent 3-hydroxyphthalic hydrazide by hydroxylation of non-chemiluminescent phthalic hydrazide can be applied as a selective reaction prob ...
TL;DR: In this paper, a variety of primary alcohols and phenols were reacted with acetic anhydride at room temperature in the presence of sodium bicarbonate to produce corresponding esters in good to excellent yields.
Abstract: A variety of primary alcohols and phenols were reacted with acetic anhydride at room temperature in the presence of sodium bicarbonate to produce corresponding esters in good to excellent yields. The acetylation of 4-nitrobenzyl alcohol was also carried out using other bicarbonates and carbonates. The reaction in the presence of cesium bicarbonate and lithium carbonate gave 4-nitrobenzyl acetate in excellent yield, while in the presence of Na2CO3, K2CO3, Cs2CO3, or KHCO3 the yield was in the range of 80%–95%. Calcium carbonate and cobaltous carbonate did not promote the acetylation of 4-ntirobenzyl alcohol using acetic anhydride. The acetylation of 4-nitrobenzyl alcohol was carried out using ethyl acetate, THF, toluene, diethyl ether, dichloromethane and acetonitrile, and gave good yields ranging from 75%–99%. Toluene was the best solvent for the reaction, while diethyl ether was the poorest.
TL;DR: In this paper, the performance of SiO2-supported Pt catalysts under conditions relevant to automotive emissions control was studied, and the results suggest that the sol-gel coating of the catalysts with metal oxides could be an attractive strategy for designing automotive oxidation catalysts, such as low-temperature activity, sulfur tolerance and hydrothermal stability.
Abstract: In this work, we studied how TiO2 and ZrO2 coatings enhance the CO oxidation performance of SiO2-supported Pt catalysts under conditions relevant to automotive emissions control. SiO2 was coated with metal oxides TiO2 or ZrO2 by sol-gel method and the subsequent Pt loading was done by incipient wetness method. The prepared catalysts Pt/TiO2-SiO2 and Pt/ZrO2-SiO2 were compared with Pt/SiO2 and Pt/Al2O3 in fresh, sulfated, and hydrothermally aged states. The structure of the catalysts was characterized with BET, XRD, TEM, EDS, EXAFS, XANES, TPD and TPR to help interpret the CO oxidation performance. Higher dispersion, stability, and oxidation state of Pt were achieved on TiO2-SiO2 and ZrO2-SiO2 supports due to stronger metal-support interaction leading to superior CO oxidation performance compared to Pt/SiO2 and Pt/Al2O3. TiO2 and ZrO2 coatings introduced surface acidity but negligible basicity, which is a likely reason for the weak and low adsorption of SO2. The results suggest that the sol-gel coating of SiO2 with metal oxides could be an attractive strategy for designing automotive oxidation catalysts with enhanced performance such as low-temperature activity, sulfur tolerance, and hydrothermal stability.
TL;DR: In this article, various types of ionic liquids (ILs) were examined for catalytic activity in the pyrolysis of cellulose for the production of levoglucosenone, which is a valuable and versatile compound for the synthesis of a variety of novel compounds.
Abstract: In this study, various types of ionic liquids (ILs) were examined for catalytic activity in the pyrolysis of cellulose for the production of levoglucosenone, which is a valuable and versatile compound for the synthesis of a variety of novel compounds. Cellulose was simply mixed with the ILs and subjected for the pyrolysis, typically at 300 °C, to produce volatile products, including levoglucosenone, separated from the ILs phase. The type of IL anion significantly affected the catalysis, and the use of ILs bearing sulfonate anion resulted in distinguished yields of levoglucosenone and IL recoveries for the reutilization. Detailed thermogravimetric analysis and discussion on properties of ILs revealed the active and thermally stable nature of the sulfonate ILs. Catalytic pyrolysis with those ILs was applied to the conversion of other saccharides composed of glucose molecules, resulting in a preferential formation of levoglucosenone but at low yields as compared to that from cellulose.
TL;DR: In this paper, a gas-solid heterogeneous photooxidation of toluene over TiO2 catalyst was investigated to investigate the factors controlling the catalytic activities, and it was shown that the formation and oxidation behavior of the byproduct compounds depended on the initial concentration of water vapor and water vapor.
Abstract: Gas-solid heterogeneous photooxidation of toluene over TiO2 catalyst was studied to investigate the factors controlling the catalytic activities. The toluene photooxidation behavior on TiO2 was strongly affected by the formation and oxidation behavior of intermediate compounds on TiO2, and their accumulation decreased the reaction rate for toluene photooxidation. The formation and oxidation behavior of the byproduct compounds depended on the initial concentration of toluene and water vapor. In situ Fourier transform infrared (FTIR) studies revealed that water vapor promoted the cleavage of the aromatic ring and facilitated CO2 formation. At the reaction temperature of 300 K, the deposition of Pt on TiO2 suppressed CO formation, whereas catalytic activity was decreased due to the increase in the amount of intermediate compounds. On the other hand, Pt/TiO2 showed higher activity than TiO2 at 353 K, in spite of the increase of the intermediate compounds.
TL;DR: In this paper, the authors presented an "environmental catalyst" possessing both thermocatalytic activity and visible-light activity for the decomposition of organic pollutants. But, their work focused on the degradation of 2-naphthol used as a model water pollutant.
Abstract: The purpose of this study is to present an “environmental catalyst” possessing both thermocatalytic activity and visible-light activity for the decomposition of organic pollutants. Molecule-sized MnOx clusters are highly dispersed on the surface of TiO2 (anatase/rutile = 4/1 w/w, P-25, Degussa) by the chemisorption-calcination cycle technique using Mn(acac)3 complex as a precursor (MnOx/TiO2). The thermo- and photo-catalytic activities of MnOx/TiO2 were studied for the degradation of 2-naphthol used as a model water pollutant. In contrast to the FeOx/TiO2 system, MnOx/TiO2 exhibits high thermocatalytic activity exceeding those of bulk β-β-MnO2 and Mn2O3. Also, visible-light activity is induced by the surface modification of TiO2 with MnOx clusters, whereas its UV-light activity decreases.
TL;DR: A summary of the past decade in the area of asymmetric catalysis in aqueous media for a wide variety of reactions in which ionic liquid and related ammonium salt immobilized organocatalysts are used is provided in this paper.
Abstract: Ionic liquids are organic salts with melting points typically below ambient or reaction temperature. The unique combination of physical properties of ionic liquids, such as lack of measurable vapor pressure, high thermal and chemical stability, make them ideal to be used as reusable homogenous support for catalysts. In addition, the solubility of ionic liquids in various reaction media can be controlled and easily fine-tuned by modification of the structures of their cations and anions. As a result, ionic liquid immobilized organocatalysts are very effective in aqueous media and can be separated easily from organic solvents, as well as aqueous phases by simply adjusting the polarity of the media. Ionic liquid immobilized organocatalysts are not only very versatile compounds that are effective catalysts for a wide spectrum of reactions, but are also environmentally friendly and recyclable organocatalysts. Herein, we provide a summary of the past decade in the area of asymmetric catalysis in aqueous media for a wide variety of reactions in which ionic liquid and related ammonium salt immobilized organocatalysts are used.
TL;DR: In this article, the decoloration reaction of methylene blue (MB) in an aqueous solution was monitored by the absorption intensity of the MB solution, which indicated that the composite thin films of Ag with an amount less than 40 mol% are not effective under vis-irradiation, though they can work as a photocatalyst under UV-IRradiation.
Abstract: The Ag-nanoparticles (Ag-NP)/TiO2 composite thin films with various amounts of Ag (10 mol% ≤ n ≤ 80 mol%) were examined as a potential photocatalyst by decoloration reaction of methylene blue (MB) in an aqueous solution. These composite thin films of ca. 100 nm thickness were fabricated by the MPM at 600 °C in air. The decoloration rates monitored by the absorption intensity of the MB solution indicated that the composite thin films of Ag with an amount less than 40 mol% are not effective under vis-irradiation, though they can work as a photocatalyst under UV-irradiation. Further, the UV-sensitivity of the composite thin films gradually decreased to almost half the level of that of the TiO2 thin film fabricated under the identical conditions when the Ag amount increased from 10 to 40 mol%. Contrarily, the composite thin films of Ag content larger than 50 mol% showed the vis-responsive activity, whose level was slightly lower than the decreased UV-sensitivity. Diffuse reflectance spectra suggested that the vis-responsive activity of the composite thin films is due to the conductivity, localized surface plasmon resonance and surface plasmon resonance of Ag-NP. It was also elucidated that the vis-responsive level of the composite thin films corresponds to their electrical conductivity that depends on the Ag content.
TL;DR: In this article, a synthetic scheme was developed for the large-scale preparation of a dimethylthiophene-fused and tetrahydroquinaldine-linked dimethylcyclopentadienyl titanium complex (2), which is a highperformance homogeneous Ziegler catalyst.
Abstract: A synthetic scheme was developed for the large-scale preparation of a dimethylthiophene-fused and tetrahydroquinaldine-linked dimethylcyclopentadienyl titanium complex (2), which is a high-performance homogeneous Ziegler catalyst. 2,3,4,5-Tetramethyl-4,5-dihydrocyclopenta[b]thiophen-6-one was prepared without chromatography purification on the 40-g scale in a laboratory setting, from which the ligand precursor for 2 was obtained in 65% yield on a 50-g scale in a one-pot without the need for chromatography purification. Metallation was achieved in a high yield (78%) through reaction of the dilithiated compound with TiCl4. Many derivatives were prepared by employing the same synthetic scheme as applied for 2. Among them, the titanium complex prepared from 2-methyl-4,5-dimethyl-6-(2-n-butyl-2,3,4,5-tetrahydroquinolin-8-yl)-4H-cyclopenta[b]thiophene exhibited an exceptionally high activity. Under commercially relevant high-temperature polymerization conditions (160 °C), this compound showed a higher activity than 2 (126 × 106 g/molTi∙h versus 72 × 106 g/molTi∙h), albeit with the formation of a polymer of slightly lower molecular weight (Mw, 159,000 versus 218,000) and with a slightly lower 1-octene content (9.3 mol% versus 12 mol%).
TL;DR: In this paper, sulfate-doped TiO2 was prepared from sol−gel systems containing titaniumalkoxide and sulfuric acid, and the degradation rate during the visible irradiation depended on both the adsorption ability and visible absorption of the photocatalysts samples.
Abstract: Sulfate-doped TiO2 was prepared from sol−gel systems containing titaniumalkoxide and sulfuric acid. The time needed for gelation of the systems was significantlyreduced by ultrasonic irradiation. The doped sulfate was observed by FTIR and XPSmeasurements. Some sulfate ions remained in the TiO2 even after heating at 300−600 °C.The UV and visible photocatalytic activities of the samples were confirmed by thedegradation of trichloroethylene (TCE). The activity of the photocatalyst samples duringthe UV irradiation strongly depended on their crystallinities rather than their specificsurface areas, i.e., adsorption ability. The degradation rate during the visible irradiationdepended on both the adsorption ability and visible absorption of the photocatalystsamples. The visible absorption induced by the sulfate-doping was effective for theTCE degradation.
TL;DR: In this paper, a method for synthesis without protecting groups of bis(indolyl)methanes by the (η3-benzyl)palladium system generated from a palladium catalyst and benzyl alcohol in water is developed.
Abstract: A method for synthesis without protecting groups of bis(indolyl)methanes by the (η3-benzyl)palladium system generated from a palladium catalyst and benzyl alcohol in water is developed. This domino protocol involves C3–H bond activation/benzylation of indole–carboxylic acids and benzylic C–H functionalization. Mechanistic studies indicate that the (η3-benzyl)palladium(II) complex, which is formed via oxidative addition of benzyl alcohol 2 to a Pd(0) species, activates the C–H bond at the C3-position of indole 1. Notably, water plays an important role in our catalytic system for sp3 C–O bond activation and stabilization of OH− by hydration for the smooth generation of the activated Pd(II) cation species, as well as for nucleophilic attack of indoles to hydrated benzyl alcohols.
TL;DR: This review will consider templating in general (including, but not restricted to, those which result in structures having potential as catalysts) before going on to consider firstly catalysis by the gold nanoparticle itself followed byCatalysis by ligands attached to gold nanoparticles, all considered with a focus on biological molecules.
Abstract: This review gives a brief summary of the field of gold nanoparticle interactions with biological molecules, particularly those with possible catalytic relevance. Gold nanoparticles are well known as catalysts in organic chemistry but much is unknown regarding their potential as catalysts of reactions involving biological molecules such as protein and nucleic acids. Biological molecules may be the substrate for catalysis or, if they are the ligand coating the gold particle, may be the catalyst itself. In other cases biological molecules may form a template upon which gold nanoparticles can be precisely arrayed. As relatively little is currently known about the catalytic capabilities of gold nanoparticles in this area, this review will consider templating in general (including, but not restricted to, those which result in structures having potential as catalysts) before going on to consider firstly catalysis by the gold nanoparticle itself followed by catalysis by ligands attached to gold nanoparticles, all considered with a focus on biological molecules.
TL;DR: In this article, the photocatalytic degradation of acridine orange (AO) dye by NaBiO3 photocatalyst under visible light irradiation was investigated systematically.
Abstract: The photocatalytic degradation of acridine orange (AO) dye by NaBiO3 photocatalyst under visible light irradiation was investigated systematically. The NaBiO3 photocatalyst exhibited a higher photocatalytic activity compared to the P25 photocatalyst. After 160 min of photocatalytic reaction, the degradation rate of AO could reach to 99% in appropriate conditions. Factors, such as catalyst dosage, solution pH, initial AO concentration and the presence of anions, were found to influence the degradation rate. To scrutinize the mechanistic details of the dye photodegradation, the intermediates of the processes were separated, identified and characterized by the HPLC-ESI-MS technique. The analytical results indicated that the N-de-methylation degradation of AO dye took place in a stepwise manner to yield mono-, di-, tri- and tetra-N-de-methylated AO species generated during the processes. The probable photodegradation pathways were proposed and discussed.
TL;DR: Sr2−xBaxTa3O10−yNz (x = 0.0, 0.5, 1.0) nanosheets were prepared by exfoliating layered perovskite compounds as discussed by the authors.
Abstract: Sr2−xBaxTa3O10−yNz (x = 0.0, 0.5, 1.0) nanosheets were prepared by exfoliating layered perovskite compounds (CsSr2−xBaxTa3O10−yNz). The Sr1.5Ba0.5Ta3O9.7N0.2 nanosheet showed the highest photocatalytic activity for H2 production from the water/methanol system among the Sr2−xBaxTa3O9.7N0.2 nanosheets prepared. In addition, Rh-loaded Sr1.5Ba0.5Ta3O9.6N0.3 nanosheet showed the photocatalytic activity for oxygen and hydrogen production from water. The ratio of hydrogen to oxygen evolved was around two. These results indicate that the Rh-loaded Sr1.5Ba0.5Ta3O9.6N0.3 nanosheet is a potential catalyst for photocatalytic water splitting.
TL;DR: Pd-catalyzed oxidative amination of alkenes with aniline as primary amines was achieved using molecular oxygen as the sole oxidant, producing (Z)-N-alkenyl-substituted anilines in high yields.
Abstract: In this review, we summarize recent progress from our group with regard to Pd-catalyzed oxidative amination of alkenes with amines. Intermolecular oxidative amination of alkenes with secondary anilines was induced using a palladium-complex catalyst combined with molybdovanadophosphate as a co-catalyst under dioxygen, leading to allylic amines and enamines in good yields with high selectivities. The reaction proceeded efficiently, using molecular oxygen as the terminal oxidant. In addition, palladium-catalyzed oxidative amination of alkenes with anilines as primary amines was achieved using molecular oxygen as the sole oxidant, producing (Z)-N-alkenyl-substituted anilines in high yields.
TL;DR: The article describes the recent work on the rational design of bimetallic NPs in ILs and the development of multifunctional systems involving NPs for a tandem reaction sequence that convert lignin-derived phenolic compounds into fuels.
Abstract: This feature article introduces the strategies on the design of highly efficient nanoparticle (NP) catalytic systems in ionic liquids (ILs). The employment of functional ILs as the media for NP preparation and catalysis could prove advantageous in terms of enhancing both NP stability and catalytic activity. Hydroxyl group functionalized ILs, in particular, exhibited a remarkable promotion effect on a variety of reactions catalyzed by NPs, such as hydrogenation over Rh NPs, hydrodehalogenation over Pt NPs and Suzuki reaction over Pd NPs. In some cases, tailor-made stabilizer is used in addition to keep the NPs sufficiently stable. For example, a carboxylic group modified polyvinylpyrrolidone endows NPs three-fold stabilization, including steric, electrostatic and ligand stabilizations, which leads to excellent stability of the NPs. The catalytic activities of these NPs, on the other hand, are not compromised, as each of these stabilizations is not too strong. Following that, the article describes our recent work on the rational design of bimetallic NPs in ILs and the development of multifunctional systems involving NPs for a tandem reaction sequence that convert lignin-derived phenolic compounds into fuels.
TL;DR: A review of mesoporous silica-based gold catalysts can be found in this paper, where the authors highlight the development of novel mesoporous silica based gold catalyst based on examples.
Abstract: Gold nanoparticles, particularly with the particle size of 2–5 nm, have attracted increasing research attention during the past decades due to their surprisingly high activity in CO and volatile organic compounds (VOCs) oxidation at low temperatures. In particular, CO oxidation below room temperature has been extensively studied on gold nanoparticles supported on several oxides (TiO 2 , Fe 2 O 3 , CeO 2 , etc. ). Recently, mesoporous silica materials (such as SBA-15, MCM-41, MCM-48 and HMS) possessing ordered channel structures and suitable pore diameters, large internal surface areas, thermal stabilities and excellent mechanical properties, have been investigated as suitable hosts for gold nanoparticles. In this review we highlight the development of novel mesoporous silica based gold catalysts based on examples, mostly from recently reported results. Several synthesis methods are described herein. In detail we report: the modification of silica with organic functional groups; the one-pot synthesis with the incorporation of both gold and coupling agent containing functionality for the synthesis of mesoporous silica; the use of cationic gold complexes; the synthesis of silica in the presence of gold colloids or the dispersion of gold colloids protected by ligands or polymers onto silica; the modification of silica by other metal oxides; other conventional preparation methods to form mesoporous silica based gold catalysts. The gold based catalysts prepared as such demonstrate good
TL;DR: In this article, gold nanostars were synthesized by a seed mediated method and covalently self-assembled on 1,5-pentanedithiol modified electrodes. But, their self-assembly time varied by increasing their surface density from 8 h, 16 h, 24 h to 32 h.
Abstract: Gold nanostars of ~70 nm tip to tip distances were synthesized by a seed mediated method and covalently self-assembled on 1,5-pentanedithiol modified electrodes. Electron transfer kinetics at the AuNS/dithiol modified electrodes were studied as a function of AuNS surface density which was varied by increasing their self-assembly time from 8 h, 16 h, 24 h to 32 h. Excellent electrocatalytic properties of AuNSs were observed toward electrochemistry of [Fe(CN)6]4−/3− redox couple. The apparent heterogeneous electron transfer constant, ket, has progressively increased with the surface density of AuNSs bonded to the electrodes from 0.65 × 10−5 cm s−1 (8 h), 1.47 × 10−5 cm s−1 (16 h), 3.95 × 10−5 cm s−1 (24 h) to an excellent 85.0 × 10−5 cm s−1 (32 h). Electrochemical charging of nanostars was confirmed, for the first time, by 79 times increase of double layer capacitance, Cdl, from 0.34 µF (8 h) to 27 µF (32 h). The electrochemical charging of AuNSs had also a strong influence on the electron tunneling process through the 1,5PDT molecules being more efficient at dense layers of AuNSs. The tunneling parameter, β, has decreased from 1.13 A−1 (16 h) to 0.50 A−1 (32 h). The AuNSs were chemically stable toward [Fe(CN)6]4−/3− showing no change in shape after electrochemical measurements.