Spray Deposition Synthesis of Locally Ordered Mesoporous Polycrystalline Titania Films at Low Temperature

A low-temperature spray deposition synthesis was developed to prepare locally hexagonally ordered mesoporous titania films with polycrystalline anatase pore walls in an evaporation-induced self-assembly process. The titania film preparation procedure is conducted completely at temperatures below 50 °C. The effects of spray time, film thickness, synthesis time prior to spray deposition, and aging time at high relative humidity after deposition on the atomic arrangement and the mesoorder of the mesoporous titania were studied. We find the crystallite size to depend on both the synthesis time and aging time of the films, where longer times result in larger crystallites. Using the photocatalytic activity of titania, the structure-directing agent is removed with UV radiation at 43–46 °C. The capability of the prepared films to remove the polymer template increased with longer synthesis and aging times due to the increased crystallinity, which increases the photocatalytic efficiency of the titania films. However, with increasingly longer times, the crystallites grow too large for the mesoorder of the pores to be maintained. This work shows that a scalable spray coating method can be used to prepare locally ordered mesoporous polycrystalline titania films by judiciously tuning the synthesis parameters.

Electrochemically Fabricated Surface-Mesostructured CuNi Bimetallic Catalysts for Hydrogen Production in Alkaline Media

Ni-based bimetallic films with 20 at.% and 45 at.% Cu and mesostructured surfaces were prepared by electrodeposition from an aqueous solution containing micelles of P123 triblock copolymer serving as a structure-directing agent. The pH value of the electrolytic solution had a key effect on both the resulting Cu/Ni ratio and the surface topology. The catalytic activity of the CuNi films toward hydrogen evolution reaction was investigated by cyclic voltammetry (CV) in 1 M KOH electrolyte at room temperature. The Cu45Ni55 film showed the highest activity (even higher than that of a non-mesostructured pure Ni film), which was attributed to the Ni content at the utmost surface, as demonstrated by CV studies, as well as the presence of a highly corrugated surface.

Synthesis of SAPO-34 Nanoplates with High Si/Al Ratio and Improved Acid Site Density

Two-dimensional SAPO-34 molecular sieves were synthesized by microwave hydrothermal process. The concentrations of structure directing agent (SDA), phosphoric acid, and silicon in the gel solution were varied and their effect on phase, shape, and composition of synthesized particles was studied. The synthesized particles were characterized by various techniques using SEM, XRD, BET, EDX, and NH3-TPD. Various morphologies of particles including isotropic, hyper rectangle, and nanoplates were obtained. It was found that the Si/Al ratio of the SAPO-34 particles was in a direct relationship with the density of acid sites. Moreover, the gel composition and preparation affected the chemistry of the synthesized particles. The slow addition of phosphoric acid improved the homogeneity of synthesis gel and resulted in SAPO-34 nanoplates with high density of acid sites, 3.482 mmol/g. The SAPO-34 nanoplates are expected to serve as a high performance catalyst due to the low mass transfer resistance and the high density of active sites.

Investigation into the crystallization of molecular sieve DNL-6

Crystallization of DNL-6, a silicoaluminophosphate (SAPO) based molecular sieve with the RHO topology, was investigated under both the hydrothermal synthesis (HTS) and dry-gel conversion (DGC) conditions. Crystallization of DNL-6 under the HTS conditions is rather fast. But a combination of crystallization under the DGC conditions and reducing reaction temperature slow down the reactions, allowing for intermediates to be captured. Under the DGC conditions, DNL-6 crystallizes through a semi-crystalline layered phase. The nature of this intermediate is aluminophosphate (AlPO) rather than SAPO with most P atoms having a local environment of P(–O–Al)3(OH). The surfactant (cetyltrimethylammonium chloride) used for synthesis appears to be part of the layered intermediate. Si is directly incorporated in the DNL-6 framework via SM II mechanism when the semi-crystalline AlPO phase is transforming to DNL-6 with the assistance of a very small amount of water. Both the structure directing agent and the surfactant play a role in the formation of DNL-6, as they were found within the final synthesized products. SEM data show that hydrothermal synthesis produces a much more crystalline product. The facts that the semi-crystalline layered phase was also observed in the powder X-ray diffraction patterns of the solid samples obtained under the HTS conditions and that the evolution of the local structure around P and Al in the intermediate phases are similar imply that under the reaction conditions employed in the present study, the formation pathways of DNL-6 under the HTS and DGC conditions appear to have some similarities.

Growth Study of Hierarchical Pore SSZ-13 Molecular Sieves with Improved CO2 Adsorption Performance

SSZ-13, with a unique pore structure and excellent thermal stability, showed a potential application in the adsorption and catalysis industry. In this work, Al(NO3)3 was used as an Al source to study the performance and morphology of the zeolite. The zeolite was prepared with an unconventional process by adding an Al source before the structure-directing agent and base. When inorganic oxygen-containing anions were introduced into the unconventional synthesis system, the crystals of the zeolite conform to the unconventional growth mode. The zeolites with large crystals were assembled from small unit nanocrystals. Extending the reaction time, aging time and adding fluoride ions introduced a multistage pore structure on the surface of the molecular sieve, which improved the CO2 adsorption performance. When aging for 24 h, reaction for 96 h, and the amount of fluorine added was 0.05 (F/Si), the sample had the best hierarchical pore structure. The SSZ-13 molecular sieve with an added amount of 0.1 (F/Si) has the highest CO2 adsorption performance. The adsorption amount was 4.55 mmol/g at 1 bar, which is 20.4% higher than that of zeolite SSZ-13 prepared by the conventional process.

Synthesis, Structural Characterization, and Biological Activities of Organically Templated Cobalt Phosphite (H2DAB)[Co(H2PO3)4]·2H2O

A novel hybrid cobalt phosphite, (H2DAB)[Co(H2PO3)4]·2H2O, has been synthesized by using slow evaporation method, in the presence of cobalt nitrate, phosphorous acid and 1,4- dia-minobutane (DAB= 1,4- diaminobutane) as a structure-directing agent. Single crystal X-ray diffraction analysis showed that the compound crystallizes in the P-1(n.2) triclinic space group, with the following unit cell parameters (Å, °) a = 5.4814 (3), b = 7.5515 (4), c = 10.8548 (6), α = 88.001 (4), β = 88.707 (5), γ = 85.126 (5), and V= 447.33 (4) Å3. The crystal structure was built up from cor-ner-sharing [CoO6] octahedra, forming chains parallel to [001], which are interconnected by H2PO3 pseudo-tetrahedral units. The deprotonated cations, residing between the parallel chains, interacted with the inorganic moiety via hydrogen bonds leading thus to the formation of the 3D crystal structure. The Fourier transform infrared spectrum showed characteristic bands corresponding to the phosphite group and the organic amine. The thermal behavior of the compound consisted mainly of the loss of its organic moiety and the water molecules. The biological tests exhibited significant activity against Candida albicans and Escherichia coli strains in all used concentrations, while less inhibitory activity was pronounced against Staphylococcus epidermidis and Saccharomyces cerevisiae, and in the case of multi-cellular organisms, no activity against the nematode model Steinernema feltiae was detected.

Hierarchical Mesoporous SSZ-13 Chabazite Zeolites for Carbon Dioxide Capture

Artificial carbon dioxide capture is an alternative method to remove the carbon dioxide already accumulated in the atmosphere as well as to stop its release at its large-scale emission points at the source, such as at power plants. However, new adsorbents are needed to make the approach feasible. For this purpose, in this study, hierarchical mesoporous-microporous chabazite-type zeolites were synthesised by applying a dual-templating method. The microporous zeolite structure-directing agent N,N,N-trimethyl-1-adamantanammonium hydroxide was combined with an organosilane mesopore-generating template, 3-(trimethoxysilyl)propyl octadecyl dimethyl ammonium chloride. Materials were characterised for their structural and textural properties and tested for their carbon dioxide capture capacity both in their original sodium form and in their proton-exchanged form by means of breakthrough curve analysis and sorption isotherms. The influence of template ratios on their structure, carbon dioxide capture, and capacity have been identified. All mesoporous materials showed fast adsorption-desorption kinetics due to a reduction in the steric limitations via the introduction of a meso range network of pores. The hierarchical zeolites are recyclable with a negligible loss in crystallinity and carbon dioxide capture capacity, which makes them potential materials for larger-scale application.

Exploring the structures, stability, and light absorption properties of three thiostannates synthesised at similar conditions

We present the synthesis, crystal structures and optical properties of three thiostannates prepared by using 1-(2-aminoethyl)piperazine (AEPz) as structure directing agent. Two of the thiostannates are layered materials (AEPz-SnS-1 and AEPz:EtOH-SnS-1) consisting of [Sn3S72−]n sheets with organic cations located in-between. The third compound is a molecular thiostannate (Sn2S6(AEPzH2)2) composed of dimeric Sn2S64− and AEPzH22+. In preparation of the layered compounds, the use of AEPz as the only solvent results in AEPz-SnS-1 with regular hexagonal pores and crystallographically disordered organic cations. In contrast, a mixture of AEPz and absolute ethanol gives AEPz:EtOH-SnS-1 with distorted hexagonal pores and ordered cations between the layers. The influence of cation order on the light absorption properties and the material thermal stability was investigated through thermal treatment of the layered compounds up to 200 °C. Both compounds show colour changes when heated, but cation order results in larger thermal stability. For AEPz-SnS-1, a decreased inter-layer distance and substantial loss of organic matter was observed when heated. However, pair distribution function analysis reveals that the local in-layer thiostannate structure of AEPz-SnS-1 remains unchanged. In contrast, AEPz:EtOH-SnS-1 does not undergo noticeable structural changes by the thermal treatment. All materials are optical semiconductors with band gaps of 3.0–3.1 eV.