Ion transport in the microporous titanosilicate ETS-10

Impedance spectroscopy was used to investigate ion transport in the microporous crystalline framework titanosilicate ETS-10 in the frequency range from 1 Hz to 10 MHz. These data were compared to measured data from the microporous aluminosilicate zeolite X. Na-ETS-10 was found to have a lower activation energy for ion conduction than that of NaX, 58.5 kJ/mol compared to 66.8 kJ/mol. However, the dc conductivity and ion hopping rate for Na-ETS-10 were also lower than NaX. This was found to be due to the smaller entropy contribution in Na-ETS-10 because of its high cation site occupancy. This was verified by ion exchanging Na(+) with Cu(2+) in both microporous frameworks. This exchange decreases the cation site occupancy and reduces correlation effects. The exchanged Cu-ETS-10 was found to have both lower activation energy and higher ionic conductivity than CuX. Zeolite X has the highest ion conductivity among the zeolites, and thus the data shown here indicate that ETS-10 has more facile transport of higher valence cations which may be important for ion-exchange, environmental remediation of radionucleotides, and nanofabrication.     

The sorption of some radiocations on microporous titanosilicate ETS-10

The microporous titanosilicate ETS-10 synthesized from gel with following molar composition: 1.0 Na₂O: 1.49 SiO₂ : 0.2 TiO₂ : 0.6 KF : 1.28 HCl : 39.5 H₂O was subjected to sorption of radioactive cations ¹¹⁵Cd²⁺, ²⁰⁴Hg²⁺, ⁶⁰Co²⁺ and ¹³⁷Cs⁺ (M) from aqueous solution, in the absence of ionic competition. The uptake of these cations on the ETS-10 was compared by means of the distribution coefficient (K_d) versus contact time and sorption capacity (R) at equilibrium. The FT-IR spectra of M-ETS-10 sorption products exhibit a modification of the absorption band, principally at 381 cm^-1.     

EXAFS and XANES investigation of the ETS-10 microporous titanosilicate

In this work, we report state-of-the-art analysis of both Ti K-edge high-resolution XANES and EXAFS data collected on the ETS-10 molecular sieve at the GILDA BM8 beamline of the ESRF facility. The interatomic distances and the angles obtained in our EXAFS study are in fair agreement with the single-crystal XRD data of Wang and Jacobson (Chem. Commun. 1999, 973) and with the recent ab initio periodic study of Damin et al. (J. Phys. Chem. B 2004, 108, 1328) Differently from previous EXAFS work (J. Phys. Chem. 1996, 100, 449), our study supports a model of ETS-10 where the Ti atoms are bonded with two equivalent axial oxygen atoms. This model is also able to reproduce the edge and the post-edge region of the XANES spectrum. Conversely, the weak but well-defined pre-edge peak at 4971.3 eV can be explained only by assuming that a fraction of Ti atoms are in a local geometry similar to that of the pentacoordinated Ti sites in the ETS-4 structure. These Ti atoms in ETS-10 should be the terminal of the -Ti-O-Ti-O-Ti- chains, of which the actual number is strongly increased by the high crystal defectivity (Ti vacancies).     

Selective photocatalytic transformations on microporous titanosilicate ETS-10 driven by size and polarity of molecules

Photocatalytic activity of microporous titanosilicate ETS-10 has been studied in water. The photoactivated ETS-10 shows catalytic activity driven by size and polarity of substrates. ETS-10 efficiently catalyzes a conversion of substrates with a size larger than the pore diameter of ETS-10. In contrast, the reactivity of small substrates depends strongly on substrate polarity; less polar substrates show higher reactivity on ETS-10. Electron spin resonance analysis reveals that large substrates or less polar substrates scarcely diffuse inside the highly polarized micropores of ETS-10 and, hence, react efficiently with hydroxyl radicals (*OH) formed on titanol (Ti-OH) groups exposed on the external surface of ETS-10. In contrast, small polar substrates diffuse easily inside the micropores of ETS-10 and scarcely react with *OH, resulting in low reactivity. The photocatalytic activity of ETS-10 is successfully applicable to selective transformations of large reactants or less polar reactants to small polar products, enabling highly selective dehalogenation and hydroxylation of aromatics.     

Impact of photogenerated charge behaviors on luminescence of Eu3+-incorporated microporous titanosilicate ETS-10

A series of Eu³⁺-incorporated ETS-10 samples were successfully prepared based on the traditional ion exchange method. The relationship between photogenerated charge behaviors and luminescent properties has been investigated in detail. It has been demonstrated that as a result of the charge transfer from the titanate quantum wires to Eu³⁺ crystal field states, the host matrix ETS-10 functions as the sensitizer of Eu³⁺ to enhance the red luminescence, while Eu³⁺ cations contribute to the recombination of photogenerated charges. The behavior of photogenerated charges has significant impact on the luminescent properties of Eu³⁺-incorporated ETS-10 materials.     

Effect of operating conditions on the removal of Pb2+ by microporous titanosilicate ETS-10 in a fixed-bed column

The breakthrough behavior of Pb2+ in an ETS-10 fixed bed was experimentally examined at various operating conditions. Results showed that the adsorption amount of Pb2+ ions per unit mass of ETS-10 particles in a column is about 1.68 mmol/g under the experimental conditions. This amount was not markedly affected by the operating conditions because of the rapid adsorption rate of Pb2+ ions on ETS-10. In the presence of competitive metal ions, the amount of Pb2+ adsorbed on ETS-10 was slightly reduced. An overshoot of the effluent concentrations of competitive metal ions Cu2+ and Cd2+ was observed in the adsorption systems of binary and ternary solutions. This is ascribed to the replacement of pre-adsorbed Cu2+ and Cd2+ ions by Pb2+ ions. The ETS-10 column broken up by Pb2+ ions can be regenerated by using an EDTA-Na2 solution and the regenerated column can be reused.     

Competitive adsorption of Pb2+, Cu2+, and Cd2+ ions on microporous titanosilicate ETS-10

In the present study, the competitive adsorption characteristics of binary and ternary heavy metal ions Pb2+, Cu2+, and Cd2+ on microporous titanosilicate ETS-10 were investigated in batch systems. Pure microporous titanosilicate ETS-10 was synthesized with P25 as the Ti source and characterized by the techniques of X-ray diffraction (XRD), field emission-scanning electron microscope (FESEM), nitrogen adsorption, and zeta-potential. Equilibrium and kinetic adsorption data showed that ETS-10 displays a high selectivity toward one metal in a two-component or a three-component system with an affinity order of Pb2+ > Cd2+ > Cu2+. The equilibrium behaviors of heavy metals species with stronger affinity toward ETS-10 can be described by the Langmuir equation while the adsorption kinetics of the metals can be well fitted to a pseudo-second-order (PSO) model.     

Sorption of thallous ion from acidic aqueous solutions onto ETS-10 titanosilicate

The sorption of the thallous ion from aqueous acidic solution (pH = 1.5) onto as-synthesized and modified ETS-10 titanosilicates was studied by using an isotope dilution method and a batch-mode technique. The present results show that the thallium(I) sorption was effective onto all three considered materials and is enhanced by the porosity and acidity modification of the ETS-10 titanosilicate. The best uptake performance was achieved by the meso-ETS-10. This behavior is explained based on the newly created additional mesoporous system and enriching the external surface with silanol groups. Also, the presence of phosphorus enhanced the inherent porosity allowing thus better internal diffusion properties of crystalline material. However, the chemically modified surface seems to have a negative contribution to the kinetic uptake of thallous ion as shown by the positive value of the activation energy E _a, in comparison with the processes more favorable energetically for ETS-10 and meso-ETS-10 materials.     

On the crystallization mechanism of ETS-10 titanosilicate synthesized in gels containing TAABr

Thermal analysis of the products resulted during crystallization of ETS-10 by using starting co gels with molar composition 5.0 Na₂O-3.0 KF-TiO₂-6.4 HCl-TAABr-7.45 SiO₂-197.5 H₂O, where tetralkylammonium (TAA) are tetramethyl (TMA), tetraethyl (TEA), tetrapropyl (TPA) and tetrabutylammonium (TBA), was performed. The effect of TAA⁺ cations (ionic radius in hydrated forms, shapes and hydrophilic/hydrophobic character) on the crystallization of ETS-10 is evident from the induction time, t_i (TMA⁺ ? TEA⁺ < TPA⁺ < TBA⁺), the rate of crystallization, R (TMA⁺ < TEA⁺ < TPA⁺ < TBA⁺), morphology and size of crystallites. Organic cations play a “pore filling” role rather than as a “structure-directing” agent. The relatively flexible molecules of the symmetric tetraalkylammonium cations mixed with alkali cations (Na⁺, K⁺) participate directly at prenucleation and nucleation steps by their interaction with the silicate and titanate in aqueous colloidal dispersion.     

Generation of hierarchical pore systems in the titanosilicate ETS-10 by hydrogen peroxide treatment under microwave irradiation

Supermicropores and well-defined mesopores with an average size of 10 nm were created in ETS-10 structure by post-synthesis treatment with H2O2 under microwave irradiation. Macropores were also formed and the external surface area of the material was increased during the treatment.     

On the influence of ion exchange on the local structure of the titanosilicate ETS-10

The effect of ion exchange with different monovalent cations (NH(4)(+), K(+), Na(+) and Cs(+)) on the local structure of the titanosilicate ETS-10 has been studied by (29)Si MAS NMR and Raman spectroscopy. Although X-ray diffraction shows no significant influence of ion exchange on the long range order, ammonium exchange is found to result in substantial damage to the local structure. Ion exchange experiments with alkali cations under significantly more acidic conditions clearly show that the structural damage brought about by ammonium exchange is not caused by the low pH of the exchange solution. The exchange with potassium and caesium ions also leads to significant changes in the (29)Si NMR and Raman spectra. However, these changes can largely be reversed by sodium back-exchange.     

Purification of waste waters containing 60Co2+, 115mCd2+ and 203Hg2+ radioactive ions by ETS-4 titanosilicate

Summary The sorption of ⁶⁰Co²⁺, ^115mCd²⁺ and ²⁰³Hg²⁺ from diluted solutions (as analogues for radioactive waste waters) on ETS-4 microporous titanosilicate was studied at 277, 293, 313 and 333 K by measuring the sorption kinetics using a batch-method. The sorption of these radiocations was compared by means of the distribution coefficient and of the sorption capacity. The maximum sorption capacities follow the order: ²⁰³Hg²⁺>^115mCd²⁺3⁶⁰Co²⁺. The thermodynamic functions of the sorption processes have been estimated. The increase of the absolute value of DG° with increasing temperatures shows that higher temperatures favor ionic exchange.     

Enhancement of the ETS-10 titanosilicate activity in the shape-selective photocatalytic degradation of large aromatic molecules by controlled defect production

In recent times, it has been shown that the microporous ETS-10 titanosilicate can be used as a shape-selective photocatalyst for the decomposition of aromatic molecules (Chem. Commun. 2001, 2131). Its actual use on practical grounds is however discouraged by its too low activity, when compared with that of TiO(2) photocatalysts. In the present work, we show how an ad hoc mild treatment with HF enhances the activity of ETS-10 toward the photodegradation of large aromatic molecules that are unable to penetrate inside the zeolitic pores, such as 2,5-dichlorophenol, 2,4,5-trichlorophenol, 1,3,5-trihydroxybenzene, and 2,3-dihydroxynaphthalene (DHN). The photoactivity of the acid-treated materials is comparable or even greater than that of the nonselective TiO(2) catalyst. Moreover, the enhancement of the photoactivity is accompanied by a remarkable parallel increase of the shape selectivity, particularly toward DHN (k(DHN)/k(P) = 127, where P = phenol). A complete characterization (by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, ultraviolet-visible spectroscopy, and X-ray aborption spectroscopy techniques) of a set of ETS-10 samples which have undergone a progressively severe HF treatment allows us to propose an explanation of the photocatalytic activity and selectivity of the modified materials.     

Development and characterization of a titanosilicate ETS-10-coated optical fiber reactor towards the photodegradation of methylene blue

An optical fiber reactor (OFR) system containing uniformly distributed quartz fibers coated with titanosilicate ETS-10 crystals was investigated. Optimum ETS-10 film thickness (～1.5 μm) and coating length (15 cm) were determined from the light propagation analysis in a single ETS-10-coated fiber. The nearly constant value of the attenuation coefficient (α ≈ 0.10 cm^?1) for films with different thickness indicated uniform fiber surface coverage with these films. The extinction coefficient, ?, decreased from ～1.6 to ～1.0 μm^?1 with ETS-10 film thickness increasing from ～0.5 to ～1.5 μm, which suggested less contact per unit film thickness between light and ETS-10 crystals inside thicker films, likely due to their lower crystal packing density. Photodegradation of methylene blue (MB) conducted in the OFR showed higher photocatalytic activity for thicker ETS-10 films. Although higher MB photodegradation rates were obtained at higher light intensity, the apparent quantum efficiency, Φ, decreased with increasing light intensity. This is consistent with the charge separation mechanism for MB photodegradation in the UV light range investigated. All ETS-10 samples investigated showed ～4–5 times higher Φ values in the OFR than in the slurry reactor, likely due to the unique light/photocatalyst/reactant contact and high fiber packing density in the OFR.     

Physico-chemical characterisation of zirconium-based self-bonded ETS-4 pellets

This paper reports a study of ETS-4 based self-bonded pellets, with several amounts of Zr moles in initial gel. The following gel composition is used: xNa₂O–0.6KF–1.28xHCl–yZrO₂–0.2TiO₂–1.49SiO₂–39.5H₂O with 0.5 ≤ x ≤ 2.5 and 0.015 ≤ y ≤ 0.12. The characterisation of obtained samples is carried out by XRD, thermal analysis, EDX and SEM. The results point out the possibility to synthesise ETS-4 zeotype with Zr in self-bonded pellets form. The importance of the amount and composition of the amorphous phase is underlined as binder of the ETS-4 crystals. Its amount is bigger at the outer face of the pellets, showing that the crystallisation occurred from the inner to the external face. Zirconium replaces titanium in the structure and its presence reinforces the mechanical resistance of the pellets.     

Adsorption separation performance of H2/CH4 on ETS-4 by concentration pulse chromatography

To exploit an effective adsorbent to separate hydrogen and methane, microporous titanium silicate molecular sieve NaETS-4 was synthesized and modified by strontium. The adsorption characteristics and diffusion behaviors of the prepared titanosilicate molecular sieve were studied by concentration pulse chromatography. And the effects of ion-exchange and dehydration temperature on adsorbent structure and gas diffusion were also discussed. The results showed that the thermal stability and Henry＇s Law constants were enhanced and micropore diffusivity decreased after exchanging Na＋ with Sr2＋. With the increase of dehydration temperature, Henry＇s Law constant and micropore diffusivity of CI-I4 decreased in both NaETS-4 and SrETS-4. While for 1-12 in SrETS-4, the increase of Henry＇s Law constant and the decrease of diffusion rate can be attributed to the shrinks of pore diameter resulting from the relocation of Sr2＋. Correspondingly, the kinetic selectivity of H2/CH4 reached 8.91 indicating its potentiality in separating H2 and CH4.     

Adsorption separation performance of H2/CH4 on ETS-4 by concentration pulse chromatography

To exploit an effective adsorbent to separate hydrogen and methane, microporous titanium silicate molecular sieve NaETS-4 was synthesized and modified by strontium. The adsorption characteristics and diffusion behaviors of the prepared titanosilicate molecular sieve were studied by concentration pulse chromatography. And the effects of ion-exchange and dehydration temperature on adsorbent structure and gas diffusion were also discussed. The results showed that the thermal stability and Henry's Law constants were enhanced and micropore diffusivity decreased after exchanging Na⁺ with Sr²⁺. With the increase of dehydration temperature, Henry's Law constant and micropore diffusivity of CH₄ decreased in both NaETS-4 and SrETS-4. While for H₂ in SrETS-4, the increase of Henry's Law constant and the decrease of diffusion rate can be attributed to the shrinks of pore diameter resulting from the relocation of Sr²⁺. Correspondingly, the kinetic selectivity of H₂/CH₄ reached 8.91 indicating its potentiality in separating H₂ and CH₄.     

Investigating entropy changes during gas adsorption in ETS-4

Energetic heterogeneity has been investigated for Engelhard titanium silicate Na-ETS-4 adsorbent and its Sr-exchanged variant, Sr-ETS-4. Na-ETS-4 was nearly homogeneous, while Sr exchange seemed to induce some degree of energetic heterogeneity in the sample, which diminished upon dehydration at higher temperature. Analysis of the entropy change during adsorption showed that the adsorbate molecules at low as well as moderate loading possess entropy greater than that predicted by the 2-D mobile film model, the excess being attributed to vibrational freedom. The wavelength of this vibration decreased with increasing coverage, as expected. For oxygen, the observed entropy drops in Na-ETS-4 and in Sr-ETS-4 are comparable, whereas, for nitrogen and methane, Sr exchange resulted in a greater entropy drop than in Na-ETS-4, suggesting greater restriction to movement in the Sr-exchanged sample. This study presents a simplistic yet effective understanding of the energetic behavior of the adsorbed molecules in ETS-4 adsorbent. This is vital to a thorough energetic characterization and study of the adsorption phenomenon in these new, promising adsorbents.