Search Results (41)

The migration of the long-lived isotope technetium-99 (half-life 2.1 × 10⁵ years) presents a significant challenge for the deep geological disposal of radioactive waste. This study investigates the immobilization of technetium by carbon steel corrosion products under aerobic and anaerobic conditions simulating the Yeniseysky site (Krasnoyarsk Region, Russia), a proposed location for a Deep Geological Repository (DGR). Over time, the degradation of barrier materials is expected to allow low-salinity solutions to be brought into contact St3 steel, the intended container material for vitrified radioactive waste in the Russian context, leading to crevice corrosion. The findings demonstrate that carbon steel containers act not merely as a physical barrier but also as a chemical barrier by facilitating the reductive immobilization of technetium. The most effective reduction of technetium was observed in the presence of ferrihydrite as a corrosion product under both aerobic and anaerobic conditions, as indicated by distribution coefficient (K_d) values ranging from 1.4 × 10³ to 1.6 × 10³ cm³/g. However, the presence of bentonite clay can diminish the efficiency of this process by adsorbing corrosion products, resulting in a 50% reduction in the distribution coefficients. In contrast, leaching products from aluminophosphate glass and cement had a less pronounced effect on technetium immobilization, causing a decrease in distribution coefficients of no more than 30%. The results of this research can be applied to model the long-term behavior of technetium in the evolving environment of a geological radioactive waste repository. Full article

This article presents a study on the development of amorphous aluminophosphate (Am-AlP) and silico-aluminophosphate (Am-SiAlP) materials for the removal of cadmium (Cd) from wastewater. Cadmium is a toxic heavy metal that poses significant environmental and health risks, and its removal from water sources is crucial. This study explores the synthesis of these materials, focusing on the impact of silicon content on their adsorption properties. The materials were characterized using various techniques, including FTIR, XRD, TGA, and BET analysis, which revealed that the incorporation of silicon increased the surface area and porosity of the adsorbents, enhancing their cadmium removal efficiency. The Am-SiAlP (7.5) sample, with a 7.5 mol% Si content, showed the highest adsorption capacity (52.63 mg g⁻¹) and removal efficiency (93%). Kinetic studies revealed that over 90% of cadmium was removed within the first 30 min, indicating rapid adsorption capabilities. The adsorption process was found to follow a pseudo-second-order kinetic model, indicating chemisorption as the rate-limiting step. The Langmuir isotherm model best described the adsorption, suggesting monolayer adsorption of cadmium on the adsorbent surface. This study also investigated the effect of interfering ions, showing that while the presence of other ions slightly reduced the adsorption efficiency, the Am-SiAlP (7.5) material still performed well. This research concludes that Am-SiAlP materials, particularly Am-SiAlP (7.5), are promising adsorbents for cadmium removal due to their high efficiency, cost-effectiveness, and environmental friendliness. Full article

Microporous alumophosphate molecular sieves AlPO₄-n are promising materials for use in catalysis, gas adsorption, and gas separation. However, AlPO₄-n faces problems such as diffusion limitations that lead to a deterioration in mass transfer. To solve this problem, we studied the crystallization of alumophosphate reaction gels prepared using aluminum isopropoxide and various secondary amines as templates, including diethyl-, di-n-propyl-, diisopropyl-, and di-n-butylamines. Using X-ray diffraction, Ramon spectroscopy, and STEM methods, it has been demonstrated that the reaction gels prepared using DPA, DIPA, and DBA are amorphous xerogels consisting of 5–10 nm nanoparticles. The reaction gel prepared with DEA is a combination of a layered phase and an amorphous aluminophosphate. It has been shown that the use of aluminum iso-propoxide allows the production of AlPO₄-11 in the form of 2–4 µm aggregates consisting of primary AlPO₄-11 nanocrystals. The template was found to exert a significant effect upon both the characteristics of the porous structure and the size of AlPO-11 nanocrystals. A template is proposed for the synthesis of hierarchical AlPO₄-11 with a maximum volume of mesopores. The morphology and crystal size of AlPO₄-11 were found to strongly influence its adsorption properties in the adsorption of octane. Full article

Chromium-substituted aluminophosphate (CrAPO-5) with the AFI crystal structure was prepared for the first time by using microwave conditions at the stage of gel formation and crystallization. This approach allowed the reduction of the time required for the synthesis of CrAPO-5 from 60–70 h to 6 h. CrAPO-5 metal aluminophosphate prepared by microwave-assisted synthesis is studied by UV-visible and IR spectroscopy and X-ray photoelectron spectroscopy. The material is characterized by the presence of Cr³⁺ and Cr²⁺ ions in the framework with predominating Cr³⁺ ions introduced via isomorphous substitution, as well as some minor amounts of extra-framework Cr³⁺ species, which are present presumably in the state of α-Cr₂O₃. The latter species can be partially reduced to Cr²⁺ species in the presence of CO or H₂. XPS study of CrAPO-5 revealed the presence of Cr³⁺ ions in the framework. A TPR experiment showed that the reduction of chromium starts at about 450–500 °C. Full article

Mesoporous cobalt- and/or iron-substituted aluminophosphates were synthesized by a hydrothermal method, followed by pyrolysis and calcination. The substitution of the transition metal elements modified the electronic properties of the samples and the accompanying surface characteristics. The samples showed tunable catalytic activity through the substitution of Fe and/or Co. We have demonstrated that the light-induced photocatalytic 4-nitrophenol reduction reaction can be enhanced through the substitution of Fe and/or Co in aluminophosphates. The induction time associated with the three different types of samples, observed due to the influence of the substituents, allows us to understand the mechanism of the 4-nitrophenol reduction process in our samples. Our work solves the issue associated with the origin of induction time and the enhancement of the catalytic activity of mesoporous aluminophosphates in the 4-nitrophenol reduction reaction through a controlled modification of the electronic properties. Full article

Styryl dyes are generally poor fluorescent molecules inherited from their flexible molecular structures. However, their emissive properties can be boosted by restricting their molecular motions. A tight confinement into inorganic molecular sieves is a good strategy to yield highly fluorescent hybrid systems. In this work, we compare the confinement effect of two Mg-aluminophosphate zeotypes with distinct pore systems (the AEL framework, a one-dimensional channeled structure with elliptical pores of 6.5 Å × 4.0 Å, and the CHA framework, composed of large cavities of 6.7 Å × 10.0 Å connected by eight-ring narrower windows) for the encapsulation of 4-DASPI styryl dye (trans-4-[4-(Dimethylamino)styryl]-1-methylpyridinium iodide). The resultant hybrid systems display significantly improved photophysical features compared to 4-DASPI in solution as a result of tight confinement in both host inorganic frameworks. Molecular simulations reveal a tighter confinement of 4-DASPI in the elliptical channels of AEL, explaining its excellent photophysical properties. On the other hand, a singular arrangement of 4-DASPI dye is found when confined within the cavity-based CHA framework, where the 4-DASPI molecule spans along two adjacent cavities, with each aromatic ring sitting on these adjacent cavities and the polymethine chain residing within the narrower eight-ring window. However, despite the singularity of this host–guest arrangement, it provides less tight confinement for 4-DASPI than AEL, resulting in a slightly lower quantum yield. Full article

It is a challenge to characterize the acid properties of microporous materials in either experiments or theory. This study presents the crystal structure, acid site, acid strength, proton siting, and IR spectra of HSAPO-34 from the SCAN + rVV10 method. The results indicate: the crystal structures of various acid sites of HSAPO-34 deviate from the space group of $\mathrm{R}\overline{3}$; the acid strength inferred from the DPE value likely decreases with the proton binding sites at O(2), O(4), O(1),and O(3), contrary to the stability order in view of the internal energy; the calculated ensemble-averaged DPE is about 1525 kJ/mol at 673.15 K; and the proton siting and the proton distribution are distinctly influenced by the temperature: at low temperatures, the proton is predominantly located at O(3), while it prefers O(2) at high temperatures, and the proton at O(4) assumedly has the least distribution at 273.15–773.15 K. In line with the neutron diffraction experiment, a correction factor of 0.979 is needed to correct for the calculated hydroxyl stretching vibration (ν(O-H)) of HSAPO-34. It seems that the SCAN meta-GGA method, compensating for some drawbacks of the GGA method, could provide satisfying results regarding the acid properties of HSAPO-34. Full article

The use of ionic liquid [emim][Tf₂N] as an additive in polyethersulphone (PES) and nano-sized silico-aluminophosphate-34 (SAPO-34) mixed matrix membrane was studied through the incorporation of different amounts of [emim][Tf₂N] in the membrane composition, as presented in this work, varying from 10 to 40 wt%. Through gas permeation tests using CO₂ and N₂, the membrane composition containing 20 wt% [emim][Tf₂N] led to the highest increase in CO₂ permeability and CO₂/N₂ selectivity. The use of low concentrations of additive (10–20 wt%) promoted a state called antiplasticization; in this state, the permeability was even more regulated by the kinetic diameter of the species which, in this work, permitted achieving a higher CO₂/N₂ selectivity while increasing the CO₂ permeability until an optimal condition. [emim][Tf₂N] also promoted a better dispersion of SAPO-34 particles and an increase in the flexibility of the polymeric matrix when compared to a film with the same composition without [emim][Tf₂N]. Moreover, the characterizations corroborated that the inclusion of [emim][Tf₂N] increased the zeolite dispersion and improved the polymer/zeolite compatibility and membrane flexibility, characterized by a decrease in glass transition temperature, which helped in the fabrication process while presenting a similar thermal resistance and hydrophilicity as neat PES membrane, without affecting the membrane structure, as indicated by FTIR and a contact angle analysis. Full article

The present work concerns proton-conducting composites obtained by replacing the water molecules present in aluminophosphate and silicoaluminophosphate AFI-type molecular sieves (AlPO-5 and SAPO-5) with azole molecules (imidazole or 1,2,4-triazole). Both the introduction of azoles and the generation of Brønsted acid centers by isomorphous substitution in aluminophosphate materials were aimed at improving the proton conductivity of the materials and its stability. In the presented study, AlPO-5 and several SAPO-5 materials differing in silicon content were synthesized. The obtained porous matrices were studied using PXRD, low-temperature nitrogen sorption, TPD-NH₃, FTIR, and SEM. The proton conductivity of composites was measured using impedance spectroscopy. The results show that the increase in silicon content of the porous matrices is accompanied by an increase in their acidity. However, this does not translate into an increase in the conductivity of the azole composites. Triazole composites show lower conductivity and significantly higher activation energies than imidazole composites; however, most triazole composites show much higher stability. The different conductivity values for imidazole and triazole composites may be due to differences in chemical properties of the azoles. Full article

A series of bifunctional catalysts, MoS₂/Al₂O₃ (70 wt.%), zeolite (30 wt.%) (zeolite—ZSM-5, ZSM-12, and ZSM-22), and silica aluminophosphate SAPO-11, were synthesized for hydroconversion of methyl palmitate (10 wt.% in dodecane) in a trickle-bed reactor. Mo loading was about 7 wt.%. Catalysts and supports were characterized by different physical-chemical methods (HRTEM-EDX, SEM-EDX, XRD, N₂ physisorption, and FTIR spectroscopy). Hydroprocessing was performed at a temperature of 250–350 °C, hydrogen pressure of 3.0–5.0 MPa, liquid hourly space velocity (LHSV) of 36 h⁻¹, and an H₂/feed ratio of 600 Nm³/m³. Complete conversion of oxygen-containing compounds was achieved at 310 °C in the presence of MoS₂/Al₂O₃-zeolite catalysts; the selectivity for the conversion of methyl palmitate via the ‘direct’ hydrodeoxygenation (HDO) route was over 85%. The yield of iso-alkanes gradually increases in order: MoS₂/Al₂O₃ < MoS₂/Al₂O₃-ZSM-12 < MoS₂/Al₂O₃-ZSM-5 < MoS₂/Al₂O₃-SAPO-11 < MoS₂/Al₂O₃-ZSM-22. The sample MoS₂/Al₂O₃-ZSM-22 demonstrated the highest yield of iso-alkanes (40%). The hydroisomerization activity of the catalysts was in good correlation with the concentration of Brønsted acid sites in the synthesized supports. Full article

Linde type A (LTA) aluminophosphate is a promising candidate for an energy storage material used for low-temperature solar and waste-heat management. The mechanism of reversible water adsorption, which is the basis for potential industrial applications, is still not clear. In this paper, we provide mechanistic insight into various aspects of the hydration process using molecular modeling methods. Building on accurate DFT calculations and available experimental data, we first refine the existing empirical force-field used in subsequent classical molecular dynamics simulations that captures the relevant physics of the water binding process. We succeed in fully reproducing the experimentally determined X-ray structure factors and use them to estimate the number of water molecules present in the fully hydrated state of the material. Furthermore, we show that the translational and orientational mobility of the confined water is significantly reduced and resembles the dynamics of glassy systems. Full article

Topological indices are invariant numerical quantities of a graph that give facts about the structure of graphs and are found to be very helpful in predicting the physical properties of aluminophosphates. The characteristics of aluminophosphates are similar to the characteristics of zeolites. Two examples of current applications are natural gas dehydration and humidity sensors. Researchers in chemistry and materials science are synthesizing new frameworks. There are many layers and holes in these substances. The technique used to predict natural behaviors among the physicochemical characteristics of chemical molecules in their basic network is known as topological indices. This study explains the vertex version of distance-based topological indices, the entropy of topological indices and their numerical analysis. Full article

The formation of intermediate phases during aging of the reaction gel composition 1.0Al₂O₃•1.0P₂O₅•1.5DPA•40H₂O and its subsequent crystallization into molecular sieves AlPO-11 and AlPO-41 was studied in this work. The initial gels and crystallization products were characterized by XRD; MAS NMR ²⁷Al and ³¹P; scanning electron microscopy (SEM); transmission electron microscopy (TEM); and N₂-physical adsorption. It has been found that the nature of the aluminum source used to prepare the gel has a significant effect on the properties of the resulting intermediate phases. It is shown that by changing the chemical and phase composition of the intermediate aluminophosphate, it is possible to control the morphology and characteristics of the secondary porous structure of the AlPO-11 molecular sieve. The formation of the intermediate phases with a layered structure opens the possibility to synthesize high-phase purity AlPO-41 at the di-n-propylamine/Al₂O₃ ratio = 1.5. The formation mechanisms of AlPO-11 and AlPO-41 are proposed depending on the phase composition of the intermediate phases. Full article

The O-methylation of catechol is an effective method for the industrial production of guaiacol used as an important chemical. However, the low catechol conversion and poor catalyst stability are the most critical issues that need to be addressed. Herein, the O-methylation of catechol with dimethyl carbonate was investigated over aluminophosphate (APO) catalysts, using a continuous-flow system to produce guaiacol. APO catalysts were synthesized with varying P/Al molar ratios and calcination temperatures to study their effects on catalytic performance for the reaction. The physico-chemical properties of the APO catalysts were thoroughly investigated using XRD, NH₃-TPD, CO₂-TPD, FTIR, and Py-FTIR. The P/Al molar ratio and catalyst calcination temperature significantly influenced the structure and texture, as well as the surface acid-base properties of APO. Both the medium acid and medium base sites were observed over APO catalysts, and the Lewis acid sites acted as the main active sites. The APO (P/Al = 0.7) exhibited the highest catalytic activity and excellent stability, due to the suitable medium acid-base pairs. Full article

Aluminophosphate cement (APC) is a new type of hydraulic cementitious material with many potential functions. Microscopic analysis techniques were used to study the effect of anhydrite on the performance and hydration process of APC under standard curing conditions. The results show that adding an appropriate amount of anhydrite promotes the hydration of APC. The highest compressive strength is reached at an anhydrite content of 15 wt.%. As the anhydrite content increases, the APC’s compressive strength decreases. The microscopic analysis of the hydration product morphology shows that the incorporation of anhydrite produces ettringite and other hydration products, improving the microstructure of the cement paste. The mercury intrusion porosimetry results show that the total porosity of the hardened APC paste decreases, and the microstructure becomes denser with an increase in the curing age, resulting in an increase in the compressive strength over time. Full article