Silica materials recovered from photonic industrial waste powder: its extraction, modification, characterization and application

This study explored the possibility of recovering waste powder from photonic industry into two useful resources, sodium fluoride (NaF) and the silica precursor solution. An alkali fusion process was utilized to effectively separate silicate supernatant and the sediment. The obtained sediment contains purified NaF (>90%), which provides further reuse possibility since NaF is widely applied in chemical industry. The supernatant is a valuable silicate source for synthesizing mesoporous silica material such as MCM-41. The MCM-41 produced from the photonic waste powder (PWP), namely MCM-41(PWP), possessed high specific surface areas (1082 m²/g), narrow pore size distributions (2.95 nm) and large pore volumes (0.99 cm³/g). The amine-modified MCM-41(PWP) was further applied as an adsorbent for the capture of CO₂ greenhouse gas. Breakthrough experiments demonstrated that the tetraethylenepentamine (TEPA) functionalized MCM-41(PWP) exhibited an adsorption capacity (82 mg CO₂/g adsorbent) of only slightly less than that of the TEPA/MCM-41 manufactured from pure chemical (97 mg CO₂/g adsorbent), and its capacity is higher than that of TEPA/ZSM-5 zeolite (43 mg CO₂/g adsorbent). The results revealed both the high potential of resource recovery from the photonic solid waste and the cost-effective application of waste-derived mesoporous adsorbent for environmental protection.     

Both initial concentrations of Fe(II) and monovalent cations jointly determine the formation of biogenic iron hydroxysulfate precipitates in acidic sulfate-rich environments

In order to accurately predict the types of biogenic iron hydroxysulfate precipitates in acidic, sulfate-rich environments facilitated by Acidithiobacillus ferrooxidans, different initial concentrations of Fe^2 +, K⁺, Na⁺, and NH₄⁺ are selected and tested in batch experiments for the formation of the precipitates. The critical equations of jarosite formation in FeSO₄–K₂SO₄–H₂O system or FeSO₄–(NH₄)₂SO₄–H₂O system could be described as Y = ? 22120.8077 ? 0.04257x + 0.006170x² (R² = 0.9979) or Y = 0.03540 ? 0.002950x + 7.407E ? 5x² (R² = 0.9934), respectively, where Y is the threshold or critical values of the molar ratio of Fe/K or Fe/NH₄ for jarosite formation, and x (mmol/L) is the initial concentration of Fe(II). Schwertmannite is the sole biogenic secondary ferric mineral when molar ratio of Fe/K or Fe/NH₄ is higher than Y in the system with a given initial Fe(II) concentration. The precipitates are an admixture of schwertmannite and jarosite, or pure jarosite when the Fe/M molar ratio is lower than Y. The crystallinity of the secondary ferric minerals increased with the increase of initial Fe(II) concentration in the medium with a fixed K⁺ concentration. It is observed that the capacity of monovalent cation in promoting jarosite formation is K⁺ > NH₄⁺ > Na⁺, as exhibiting that the capacity of K⁺ in this process is about 75 and 200 times greater than NH₄⁺ and Na⁺, respectively. Obviously, both the initial concentration of Fe(II) and molar ratio of Fe to monovalent cation determine the types of biogenic iron hydroxysulfate precipitates.     

Preparation and characterization of amino-functionalized nano-Fe3O4 magnetic polymer adsorbents for removal of chromium(VI) ions

Four kinds of NH₂-functionalized nano magnetic polymer adsorbents (NH₂-NMPs) coupled with different diamino groups, i.e., ethylenediamine (EDA), diethylenetriamine (DETA), triethylentetramine (TETA), and tetraethylenepentamine (TEPA), named as EDA-NMPs, DETA-NMPs, TETA-NMPs, and TEPA-NMPs, respectively, have been prepared and characterized by transmission electron microscopy (TEM), X-ray diffractometer (XRD), vibrating sample magnetometer (VSM), elementary analyzer (EA), Brunauer, Emmett, Teller surface area analyzer (BET), and Fourier transform infrared spectroscopy (FTIR). The sorptive characteristics of the NH₂-NMPs intended for removal of chromium(VI) was investigated. Batch adsorption studies were carried out to optimize adsorption conditions. The evaluation of the adsorption kinetics, isotherm, and thermodynamics was deeply investigated. The results showed the adsorptive properties of the NH₂-NMPs were highly pH dependent. Adsorption of Cr(VI) reached equilibrium within 30 min. The data of adsorption kinetics obeyed pseudo-second-order rate mechanism well. The adsorption data for Cr(VI) onto NH₂-NMPs were well fitted to the Langmuir isotherm. The maximum adsorption capacities (q _m) of the NH₂-NMPs to Cr(VI) were 136.98, 149.25, 204.08, 370.37 mg g⁻¹, for EDA-NMPs, DETA-NMPs, TETA-NMPs, and TEPA-NMPs, respectively. Thermodynamic parameters like ΔH ^θ, ΔS ^θ, and ΔG ^θ for the adsorption of Cr(VI) onto the NH₂-NMPs have been estimated, which suggested that the adsorption processes of Cr(VI) onto the NH₂-NMPs were endothermic and entropy favored in nature. The adsorption mechanism studies showed that the adsorption of Cr(VI) onto the NH₂-NMPs could be related with electrostatic attraction, ion exchange, and coordination interactions.     

Bi2WO6/NH2-MIL-88B(Fe) heterostructure: An efficient sunlight driven photocatalyst for the degradation of antibiotic tetracycline in aqueous medium

The development of highly efficient sunlight assisted photocatalysts has been acknowledged as a promising strategy for the enhanced degradation of antibiotics. In this work, effectual fabrication of a novel Bi₂WO₆/NH₂-MIL-88B(Fe) heterostructure was carried through solvothermal route. The structural, morphological and compositional analysis was done by employing number of analytical techniques, namely XRD, FTIR, HRTEM, FESEM, XPS, PL and BET surface area. The prepared Bi₂WO₆/NH₂-MIL-88B(Fe) heterostructure was utilized as an efficient photocatalyst towards decomposition of a typical antibiotic tetracycline (TC) in aqueous medium. It was found that Bi₂WO₆/NH₂-MIL-88B(Fe) heterostructure exhibited improved degradation efficiency of about 89.4% within 130 min of solar illumination than pristine NH₂-MIL-88B(Fe) under optimized parameters i.e. initial drug solution of 10 mg/L concentration at pH 4 with 0.35 g/L dose of catalyst. Moreover, adsorption studies, kinetics and isotherms of adsorption on TC were also investigated. Results revealed that adsorption kinetics followed pseudo 2nd order model and isotherm data fitted well with Freundlich model (R² = 0.99803) as compared to Temkin and Langmuir. The ameliorating photocatalytic capability could be primarily accredited to the heterojunction created among Bi₂WO₆ and NH₂-MIL-88B(Fe) which facilitated the charge transfer and thus determines high catalytic efficiency. The enhanced photocatalyic effect was further verified by electrochemical impedance and photocurrent studies. The prepared composite also exhibited longer carrier lifetime (140.72 ns) compared to pure MOF (132.05 ns) and Bi₂WO₆ (136.39 ns). Further, based on the radical trapping investigations, role of superoxide radicals was dominant and detailed mechanism was proposed for the photocatalytic degradation process. The major intermediates formed during the course of reaction were also examined using LCMS analysis. The photodegradation was also carried over simulated hospital wastewater by the prepared heterostructure and 60.5% TOC was obtained under solar light in 390 min. Moreover, the synthesized heterostructure showed good recyclability up to three cycles depicting good stability.     

Thermodynamic and kinetic studies for the adsorption of Hg(II) by nano-TiO2 from aqueous solution

Titanium dioxide nanocrystals were employed, for the first time, for the sorption of Hg(II) ions from aqueous solutions. The effects of varying parameters such as pH, temperature, initial metal concentration, and contact time on the adsorption process were examined. Adsorption equilibrium was established in 420 min and the maximum adsorption of Hg(II) on the TiO₂ was observed to occur at pH 8.0. The adsorption data correlated with Freundlich, Langmuir, Dubinin–Radushkevich (D–R), and Temkin isotherms. The Freundlich isotherm showed the best fit to the equilibrium data. The Pseudo-first order and pseudo-second-order kinetic models were studied to analyze the kinetic data. A second-order kinetic model fit the data with the (k₂ = 2.8126 × 10^?3 g mg^?1min^?1, 303 K). The intraparticle diffusion models were applied to ascertain the rate-controlling step. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) were calculated which showed an endothermic adsorption process. The equilibrium parameter (R_L) indicated that TiO₂ nanocrystals are useful for Hg(II) removal from aqueous solutions.     

Metal-Free Hexagonal Perovskite High-Energetic Materials with NH3OH+/NH2NH3+ as B-Site Cations

Designing and synthesizing more advanced high-energetic materials for practical use via a simple synthetic route are two of the most important issues for the development of energetic materials. Through an elaborate design and rationally selected molecular components, two new metal-free hexagonal perovskite compounds, which are named as DAP-6 and DAP-7 with a general formula of (H₂dabco)B(ClO₄)₃ (H₂dabco²⁺ = 1,4-diazabicyclo[2.2.2]octane-1,4-diium), were fabricated via an easily scaled-up synthetic route using NH₃OH⁺ and NH₂NH₃⁺ as B-site cations, respectively. Compared with their NH₄⁺ analog ((H₂dabco)(NH₄)(ClO₄)₃; DAP-4), which has a cubic perovskite structure, DAP-6 and DAP-7 have higher crystal densities and enthalpies of formation, thus exhibiting higher calculated detonation performances. Specifically, DAP-7 has an ultrahigh thermal stability (decomposition temperatures (T_d) = 375.3 °C), a high detonation velocity (D = 8.883 km·s⁻¹), and a high detonation pressure (P = 35.8 GPa); therefore, it exhibits potential as a heat-resistant explosive. Similarly, DAP-6 has a high thermal stability (T_d = 245.9 °C) and excellent detonation performance (D = 9.123 km·s⁻¹, P = 38.1 GPa). Nevertheless, it also possesses a remarkably high detonation heat (Q = 6.35 kJ·g⁻¹) and specific impulse (I_sp = 265.3 s), which is superior to that of hexanitrohexaazaisowurtzitane (CL-20; Q = 6.23 kJ·g⁻¹, I_sp = 264.8 s). Thus, DAP-6 can serve as a promising high-performance energetic material for practical use.     

Laccase immobilized on methylene blue modified mesoporous silica MCM-41/PVA

The mesoporous silica sieve MCM-41 containing methylene blue (MB) provides a suitable immobilization of biomolecule matrix due to its uniform pore structure, high surface areas, good biocompatibility and nice conductivity. Based on this, a facilely fabricated amperometric biosensor by entrapping laccase into the MB modified MCM-41/PVA composite film has been developed. Laccase from Trametes versicolor is assembled on a composite film of MCM-41 containing MB/PVA modified Au electrode and the electrode is characterized with respect to transmission electron microscopy (TEM) and scanning electron microscopic (SEM), Cyclic voltammetry (CV), response time, detection limit, linear range and activity of laccase. The laccase modified electrode remains good redox behavior in pH 4.95 acetate buffer solution, at room temperature in present of 0.1 mM catechol. The response time (t_90%) of the modified electrode is less than 4 s for catechol. The detection limit is 0.331 µM and the linear detect range is about from 4.0 µM to 87.98 µM for catechol with a correlation coefficient of 0.99913(S/N = 3). The apparent Michaelis–Menten (K_M^app) is estimated using the Lineweaver–Burk equation and the K_M^app value is about 0.256 mM. This work demonstrated that the mesoporous silica MCM-41 containing MB provides a novel support for laccase immobilization and the construction of biosensors with a faster response and better bioactivity.     

Preparation and characterization of epoxy composites filled with functionalized nano-sized MCM-41 particles

Mono-dispersed nano-sized MCM-41 (M (with template)) particles were synthesized by sol–gel reaction. The effect of interface modification on the properties of epoxy composites was investigated. Modifications were carried out either by substituting silanol groups on the surface or in the mesopore channels into amine (M-NH₂), calcinating mixture template in the mesopore channels (M(without template)), or recalcinating them at higher temperature to remove silanol groups (–OH) in the mesopore channels or on the surface (CM). Transmission electron micrograph results showed that the dispersing of MCM-41 nanoparticles was not influenced by the modification, while –NH₂ group indeed modified the mesopore channels or the surface of MCM-41 particle by using IR, XRD, and N₂ adsorption–desorption. In addition, tensile tests suggested that M-NH₂ nanoparticles could simultaneously provide epoxy matrix with strengthening and toughening effects. However, due to the different interfacial structures between the fillers and the matrix, the mechanical properties of the composites filled by M-NH₂ were much better than those of composites filled by MCM-41 (without template), MCM-41 (with mixture template), and CM.     

Compatibilizing effect of mesoporous fillers on the mechanical properties and morphology of polypropylene and polystyrene blend

Polypropylene(PP)/Polystyrene(PS) (PP/PS = 80/20) blend with different types of fillers were prepared by using melt method. Four different types of fillers, namely mesoporous MCM-41 (without template), nano-SiO₂, Polymethylmethacrylate (PMMA)/MCM-41 and PMMA/SiO₂ were considered. For PMMA/MCM-41 filler, the synthesis of the filler consisting of entrapped strand of PMMA within the pores of mesoporous MCM-41 (without template) was described. The mechanical properties of the blend determined as the nano-fillers contents and the different types of blend were found to vary with the different interface between fillers and the matrix. SEM revealed a good interaction between the matrix phases and PMMA/MCM-41 or MCM-41 (without template). The decreased T_g of PS implied that the good adhesion between PP and PS blend was obtained by adding PMMA/MCM-41 nano-filler.     

Thermal stability of Si–MCM-41 in gaseous atmosphere

The thermal stability of Si–MCM-41 in different atmosphere (air, O₂, NH₃, N₂, and Ar) has been investigated in the present work; as-synthesized Si–MCM-41 was heat-treated at 800–1030 °C for 6–12 h in the selected atmosphere. Based on absorption–desorption isotherms and low-angle XRD measurement of the treated samples, it was found that the thermal stability varied greatly in different atmosphere. As-synthesized Si–MCM-41 retained mesoporous structure up to 1010 °C in NH₃, N₂, and Ar environment, but in air and O₂ environment, the highest thermal stable temperature of mesoporous structure in Si–MCM-41 was no more than 900 °C.     

The investigation of MCM-48-type and MCM-41-type mesoporous silica as oral solid dispersion carriers for water insoluble cilostazol

Objective: To explore the suitable application of MCM-41 (Mobil Composition of Matter number forty-one)-type and MCM-48-type mesoporous silica in the oral water insoluble drug delivery system.

Methods: Cilostazol (CLT) as a model drug was loaded into synthesized MCM-48 (Mobil Composition of Matter number forty-eight) and commercial MCM-41 by three common methods. The obtained MCM-41, MCM-48 and CLT-loaded samples were characterized by means of nitrogen adsorption, thermogravimetric analysis, ultraviolet-visible spectrophotometry, scanning electron microscopy, transmission electron microscopy, differential scanning calorimetry and powder X-ray diffractometer.

Results: It was found that solvent evaporation method was preferred according to the drug loading efficiency and the maximum percent cumulative drug dissolution. MCM-48 with 3D cubic pore structure and MCM-41 with 2D long tubular structure are nearly spherical particles in 300–500?nm. Nevertheless, the silica carriers with similar large specific surface areas and concentrating pore size distributions (978.66?m²/g, 3.8?nm for MCM-41 and 1108.04?m²/g, 3.6?nm for MCM-48) exhibited different adsorption behaviors for CLT. The maximum percent cumulative drug release of the two CLT/silica solid dispersion (CLT-MCM-48 and CLT-MCM-41) was 63.41% and 85.78% within 60?min, respectively; while in the subsequent 12?h release experiment, almost 100% cumulative drug release were both obtained. In the pharmacokinetics aspect, the maximum plasma concentrations of CLT-MCM-48 reached 3.63?mg/L by 0.92?h. The AUC_0–∞ values of the CLT-MCM-41 and CLT-MCM-48 were 1.14-fold and 1.73-fold, respectively, compared with the commercial preparation.

Conclusion: Our findings suggest that MCM-41-type and MCM-48-type mesoporous silica have great promise as solid dispersion carriers for sustained and immediate release separately.     

Room temperature synthesis of Si-MCM-41 using polymeric version of ethyl silicate as a source of silica

Synthesis of mesoporous MCM-41 materials at room temperature using less expensive polymeric version of ethyl silicate (40 wt% SiO₂) as a source of silica was established. The influence of crucial synthesis parameters such as molar ratios of H₂O/NH₄OH, NH₄OH/SiO₂ and CTMABr/SiO₂ in gel on the quality of the phase formed was investigated. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and low temperature N₂ adsorption-desorption isotherms have been employed to characterize the products. The magnitude of orderness, textural properties and thermal stability of the Si-MCM-41 samples prepared under identical judiciously pre-controlled synthesis conditions using ethyl silicate and conventional tetraethyl orthosilicate (TEOS) were assessed. Even though, ethyl silicate has proved to be suitable source for the preparation of MCM-41 at room temperature, there exists an optimum value of H₂O/NH₄OH for different NH₄OH/SiO₂ molar ratios in the gel. Changes in the morphology were observed when NH₄OH/SiO₂, H₂O/NH₄OH molar ratios in the gels were changed.     

Synthesis and characterization of CuO containing mesoporous silica spheres

A new series of mesoporous silica spheres containing nanodispersed copper oxides were synthesized in H₂O/EtOH/ammonia solution at room temperature. The mesoporous structures were characterised using X-ray powder diffraction and N₂ adsorption-desorption techniques. Scanning electron micrograph and transmission electron micrograph revealed that the MCM-41 particles have spherical morphologies. The DTA curve of pure MCM-41 exhibited a sharp single exothermic peak between 290°C and 340°C, while a broad peak with several shoulders in the temperature range between 180°C and 380°C was observed for Cu-MCM-41, indicating the possible complexation of Cu²⁺ with surfactants adhering to the inner surfaces of the mesopores. Electron paramagnetic resonance spectra of uncalcined samples revealed that Cu²⁺ ions are in an octahedral or distorted octahedral coordination with nitrogen ligands of the surfactant while in the calcined samples they are coordinated with oxygen of the MCM-41 framework. The redox properties of samples were examined by a temperature-programmed reduction and N₂O passivation method. The results indicate that CuO with increasing particle size could be formed in the mesoporous materials with increasing Cu contents, and this decreased the reducibility of the resulting CuO.     

Hollow MCM-41 microspheres derived from P(St-MMA)/MCM-41 core/shell composite particles

In soap-free latex media, poly(styrene-methyl methacrylate)/MCM-41 core/shell composite microspheres have been fabricated by adding silicate source in batches. In this process, silicate species and the surfactant micelles were self-assembled into 2-dimensional hexagonal arrangement on the surface of P(St-MMA) microspheres. Hollow MCM-41 microspheres were obtained via removing polymer core by solvent. XRD, TEM, IR and N₂ adsorption-desorption analysis were applied to characterize products. The results showed that average diameter and wall thickness of hollow MCM-41 microspheres is about 240 nm and 20 nm, respectively. Results of N₂ adsorption-desorption indicate that hollow MCM-41 microspheres possess a highly ordered mesoporous structure and a narrow pore distribution with a mean value of 2.34 nm.     

Investigation of in vitro permeability and in vivo pharmacokinetic behavior of bare and functionalized MCM-41 and MCM-48 mesoporous silica nanoparticles: a burst and controlled drug release system for raloxifene

In the present work, MCM-41 and MCM-48 type of nanoparticles were successfully engineered. Effect of nanosize and amine functionalization on drug release, in vitro intestinal absorption and in vivo pharmacokinetic behavior was investigated in a comprehensive manner. The tailor-made bare and surface decorated MCM-41 and MCM-48 were synthesized and evaluated for their mesoporous skeleton, pore size, particle size, surface area, zeta potential, etc. by nitrogen sorption, DLS, TEM, etc. Incorporation of raloxifene (RLF) was affirmed using optimized immersion-solvent evaporation technique and its success confirmed by DSC, IR, and XRD analysis. TGA analysis revealed higher %grafting of amine groups on the exterior and larger RLF encapsulation into mesoporous derivate. The detailed in vitro release study revealed SGF to be the most compatible media for RLF showing an initial burst release from pristine nanoparticles and a delayed release from surface coated nanoparticles. Furthermore, release kinetics model data demonstrated Weibull and Higuchi as the best fit models for bare and amine-functionalized nanoparticles respectively. Moreover, an in vitro permeability study on Caco-2 cell line revealed higher absorption by engineered nanoparticle as compared to pure RLF and its marketed formulation. The supremacy in the in vivo pharmacokinetic parameters of RLF-41 and RLF-48 was demonstrated with 3.33 and 3.50 times enhancement in the bioavailability of RLF with respect to RLF suspension. To sum up, the results obtained were superior and promising for synthesized nanoparticles and more precisely for MCM-48 amongst them.     

Synthesis and characterization of a new p-phenylenediammonium dihydrogenmonophosphate [p-NH3C6H4NH3][H2PO4]2

Chemical preparation, crystal structure and NMR spectroscopy of a new organic cation p-phenylenediammonium monophosphate [p-NH₃C₆H₄NH₃][H₂PO₄]₂ are presented. This new compound crystallizes in the orthorhombic system, with the space group Pnma and the following parameters: a = 7.970 (2) Å; b = 22.770 (7) Å; c = 7.000 (7) Å, V = 1270.3 (11) Å³, Z = 4 and D_x = 1.590 g cm⁻³. The crystal structure has been determined and refined to R = 0.043 and R_(w) = 0.057 using 2623 independent reflections. The structural arrangement can be described as inorganic layers of (H₈P₄O₁₆)⁴⁻ units, parallel to (a, c) planes. The organic groups (p-H₃NC₆H₄NH₃)²⁺are anchored between the phosphoric layers to form a three-dimensional infinite network. This compound is also investigated by IR and solid-state ¹H, ¹³C and ³¹P MAS NMR spectroscopies. The ab initio method is used in the calculation of chemical shifts.     

Controllable phase/morphology tailoring of REF3 and NaREF4 (RE = La-Lu,Y), and insights into the up-conversion luminescence of GdF3:Yb3+/Tm3+ spheres

Four typical rare earth fluorides of hexagonal/orthorhombic REF₃ and hexagonal/cubic NaREF₄ (RE = La-Lu, Y, excluding radioactive Pm), have been hydrothermally synthesized from mixed solutions of the rare earth nitrate solutions and ammonium fluoride (NH₄F), in the presence of EDTA-2Na. The phase and the morphology are closely related to the ionic radius of RE³⁺. Large RE³⁺ ions, La³⁺, Ce³⁺, Pr³⁺, Nd³⁺ and Sm³⁺, crystallize in hexagonal REF₃ (nanocrystals), and middle RE³⁺ ions (RE = Eu-Dy) crystallize in orthorhombic REF₃ (micron-sized spheres/polyhedral micro-crystallites). For small RE³⁺ ions, Ho³⁺, Er³⁺, Tm³⁺, Yb³⁺ and Y³⁺, they tend to being incorporated into the host lattice of cubic NaREF₄ (submicron spheres). However, the smallest Lu³⁺ tends to crystallizing in orthorhombic LuF₃. Varying the F^-/RE³⁺ molar ratio (R) and the reaction temperature can efficiently induce the phase/morphology evolution of rare earth fluorides. Increasing R up to 10–30 yielded hexagonal NaREF₄ (RE = Dy, Tb, Gd, Eu, Sm, micron prisms), although the original products were orthorhombic REF₃ (RE = Dy, Tb, Gd, Eu) and hexagonal SmF₃ at R = 5. However, increasing R is inefficient to the phase transition for large RE elements of La, Ce, Pr, Nd. Lowering the reaction temperature from 180 °C to 80 °C gave rise to the phase transition from orthorhombic LuF₃ to cubic NaLuF₄. GdF₃:Yb³⁺,Tm³⁺ spheres exhibited intense blue emission at ~476 nm (¹G₄ → ³H₆ transition of Tm³⁺), deep-red emission at ~646 nm (¹G₄→³F₄ transition of Tm³⁺), and near-infrared emission at ~695 nm (³F_2,3 → ³H₆ transitions of Tm³⁺) under the 980 nm infrared excitation. The intense near-infrared emission under the infrared excitation suggested that they might hold great potential in bio imaging application.     

Synthesis and crystal structures of a new (2,3-(CH3)2C6H3NH3)H2XO4 (X=P,As)

The aim of encapsulation of 2,3-dimethylanilinium cation in (H₂XO₄)_n polymeric anion chains is to build acentric frameworks that are efficient for non-linear optical (NLO) applications. The synthesis and structures of two new inorganic–organic NLO crystals with general formula (2,3-(CH₃)₂C₆H₃NH₃)H₂XO₄ (X=P, As) are reported. The magnitude of their second harmonic generations (SHG) responses was found to be between the KDP and urea. They crystallize with monoclinic unit-cells and are isotopic. We have determined the structure of phosphoric salt. The following unit-cell parameters were found: a=8.866(3) Å, b=5.909(6) Å, c=10.644(5) Å, β=112.44(1)°, V=515.5(5) Å³ and D_X=1.412 g cm⁻³. The space group is P2₁ with Z=2. The structure was refined with R=0.041 (R_w=0.057) for 1652 reflections with I≥3σ(I). It exhibits infinite (H₂PO₄)_nⁿ⁻ chains. The organic groups (2,3-(CH₃)₂C₆H₃NH₃)⁺ are anchored between adjacent polyanions through multiple hydrogen bonds. Chemical preparation, crystal structure, calorimetric and spectroscopic investigation are described.     

Synthesis and characterization of mesoporous Si-MCM-41 materials and their application as solid acid catalysts in some esterification reactions

Mesoporous MCM-41 has been synthesized by sol–gel method at room temperature possessing good thermal stability, high surface area as well as retention of surface area at high temperature. The MCM-41 neutral framework has been modified and put to practical use by incorporating Al³⁺ in the siliceous MCM-41 framework and supporting 12-TPA (12-tungstophosphoric acid) onto MCM-41 by process of anchoring and calcination to induce Brønsted acidity in MCM-41 to yield Al-MCM-41 and 12TPA-MCM-41, respectively. The synthesized materials have been characterized for elemental analysis by ICP-AES, XRD, SEM, TEM, EDX, FT–IR and TGA. Surface area has been determined by BET method and pore size and pore size distribution determined by BJH method. Surface acidity has been evaluated by NH₃-TPD method. The potential use of Al-MCM-41 and 12TPA-MCM-41 as solid acid catalysts has been explored and compared by studying esterification as a model reaction wherein monoesters such as ethyl acetate (EA), propyl acetate (PA), butyl acetate (BA) and benzyl acetate (BzA) have been synthesized, optimizing several parameters such as catalyst amount, reaction time, reaction temperature and mole ratio of reagents.     

H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript> supported on mesoporous MCM-41 and Al–MCM-41 materials: preparation and characterisation

MCM-41 and Al–MCM-41 has been synthesized using cetyl-trimethylammonium bromide (CTAB) surfactant as template and adding the silica precursor to aqueous solutions containing CTAB. The obtained solids were calcined at 600 °C for 4 h. HPW heteropolyacid supported on the mesoporous were prepared using the incipient wetness method. The characterization of materials was performed by X-ray diffraction, Transmission Electron Microscopy, N₂ adsorption, ²⁹Si Cross Polarization–Magic Angle Spinning and ²⁷Al MAS NMR. Results showed that the hexagonal structure is obtained in both cases. The Aluminium species are located inside an extra-framework. The impregnation reduces the surface area of the mesoporous materials especially of the Al–MCM-41 suggesting a participation of aluminium during the impregnation. HPW is well dispersed in the mesoporous materials and is located inside the pores interacting with the silanol group of the pores wall. ²⁷Al MAS NMR measurements have showed that the impregnation causes the removal of the non-framework aluminium.