Difraction and complementary analysis methods for the design of MFI-type titanosilicalites with catalytic properties

Кузьмичева, Г. М.; Kravchenko, G. V.; Pavlov, Ivan; Vasiliev, Alexander L.; Светогоров, Р. Д.; Храмов, Е. В.; Chumakov, Ratibor G.; Pirutko, Larisa V.

doi:10.1016/j.matchemphys.2023.128054

Cited by 4 publications

(5 citation statements)

References 21 publications

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“…The XRD refinement method has been also applied to evaluate the ion-exchange status of zeolites, and the results show strong correlations between the concentration of exchanged ions in the unit cells and their lattice parameters. − Furthermore, changes in the unit cell were recently found to be directly related to the deactivation of various type of zeolites, such as MFI, FER, and CHA, caused by in the accumulation of carbonaceous deposits during the methanol to hydrocarbon reaction. − XRD has also been used extensively over the other most commonly studied metallosilicate, TS-1 (MFI). The titanium content in TS-1 is reported to influence the transition temperature between orthorhombic and monoclinic phases and also change the unit cell volume. , …”

Section: Introductionmentioning

confidence: 99%

“…The titanium content in TS-1 is reported to influence the transition temperature between orthorhombic and monoclinic phases and also change the unit cell volume. 55,56 Herein, we focus on the effects on the crystal structure change of Sn-Beta materials upon its preparation. The lattice parameters are evaluated by XRD-LeBail fit using a semiempirical model, with both PT and HT Sn-Beta included.…”

Section: Introductionmentioning

confidence: 99%

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Tracking Lattice Distortion Induced by Defects and Framework Tin in Beta Zeotypes

Bai,

Taarning,

Luthra

et al. 2023

J. Phys. Chem. C

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The use of powder X-ray diffraction (PXRD) coupled with lattice parameter refinement is used to investigate the crystal structure of Sn-Beta materials. A newly developed semiempirical PXRD model with a reduced tetragonal unit cell is applied to obtain the characteristic crystallographic features. There is a robust correlation between lattice parameters and the concentration of tin and defects for materials prepared via hydrothermal (HT) and postsynthetic (PT) methods. With tin incorporation, PT Sn-Beta samples, which possess a more defective structure, exhibit an extended interlayer distance in the stacking sequence and expansion of the translation symmetry within the layers, leading to larger unit cell dimensions. In contrast, HT Sn-Beta samples, having fewer defects, show a minimal effect of tin site density on the unit cell volume, whereas lattice distortion is directly correlated to the framework tin density. Furthermore, density functional theory (DFT) studies support an identical trend of lattice distortion following the monoisomorphous substitution of T sites from silicon to tin. These findings highlight that PXRD can serve as a rapid and straightforward characterization method to evaluate both framework defects and heteroatom density, offering a novel approach to monitor structural changes and the possibility to evaluate the catalytic properties of heteroatom-incorporated zeotypes.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Tracking Lattice Distortion Induced by Defects and Framework Tin in Beta Zeotypes

Bai,

Taarning,

Luthra

et al. 2023

J. Phys. Chem. C

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“…EDX microanalysis of the obtained zeolite samples using Bruker energy-dispersive X-ray microanalysis (EDX) system (Bruker, USA) [30] was applied for the qualitative analysis of single-phase samples with speci c standard deviations for each element and its content. To detect the presence of a certain element by the EDX microanalysis, its content must be at least 0.1 at.…”

Section: Microstructure Morphology Elemental Compositionmentioning

confidence: 99%

“…%. Moreover, the e ciency of characteristic X-ray radiation detecting by EDX decreases with a decrease in atomic number [30]. Quantitative analysis of even single-phase samples, considering all atoms in the sample composition (for example, impurity atoms from the initial components), cannot be correctly applied to defect structures with vacancies, since the balance of elements in this case cannot be reduced to 100%.…”

Section: Microstructure Morphology Elemental Compositionmentioning

confidence: 99%

“…Moreover, in the HZSM-5 framework voids, there may be water and other atomic formations with a high hydrogen content, which may not be detected by microanalysis. However, the EDX microanalysis application for the qualitative analysis of the samples' composition and the ratio of individual elements content, especially for single-phase regions, can be very successful [30].…”

Section: Microstructure Morphology Elemental Compositionmentioning

confidence: 99%

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Rational Design of Aluminium-containing Zeolites with Typological Structure of HZSM-5 and Catalytic Properties

Domoroshchina,

Kuz’micheva,

Vasiliev

et al. 2024

Preprint

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In this work, the analysis and generalization of data on the elemental, phase and surface composition, crystal structure and microstructure of MFI-type HZSM-5 with Si/Al = 12, 25, 40, 300 were presented. Relationships between HZSM-5 silicate modulus (Si/Al) and pore volume, specific surface, the area of framework voids were established. Data obtained by electron microscopy and energy dispersive X-ray microanalysis explained the discrepancy between HZSM-5 real composition and the initial one. Samples with the maximum content of Brønsted (HZSM-5 with Si/Al = 25) and Lewis (HZSM-5 with Si/Al = 12) acid sites responsible for the catalytic activity were identified using diffuse reflectance Fourier transform infrared spectroscopy. N2O decomposition reaction rate was found to decrease in the row HZSM-5(25) > HZSM-5(12) > HZSM-5(40) > HZSM-5(40)С>>HZSM-5(300). The high N2O decomposition rate demonstrated by HZSM-5(25) makes it promising catalyst. The second phase of iron oxides and the presence of faceted particles {001} oriented in HZSM-5(25) were shown to contribute to its maximum catalytic activity in N2O decomposition. The applied methodology for studying aluminosilicalites with different silicate modules and the revealed correlations can provide a fundamental perspective in studying other zeolites or modifying data.

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Recent Advances in the Synthesis and Application of TS‐1 Zeolite for Green Catalytic Oxidation

Wang,

Duan,

et al. 2024

Advanced Sustainable Systems

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TS‐1 has a unique structure, and TS‐1/H2O2 oxidation system for composition shows excellent catalytic performance in the oxidation of a variety of organic matter. The response conditions of the reaction system are mild, and the ultimate oxidation product is water. It is a typical “green catalytic” system and has received widespread attention from researchers. Here, the synthesis progress of TS‐1 to improve the accessibility and activity of active sites by doping mesoporous and microporous structures into traditional TS‐1 zeolite in recent five years are reviewed, including hydrothermal synthesis, dry gel conversion synthesis, solvent‐free synthesis, microwave assisted synthesis, and isomorphous substitution. Meanwhile, the application of TS‐1/H2O2 system in oxidative desulfurization, ketone ammonia oxidation, olefin epoxidation, and hydroxylation of aromatic hydrocarbons reactions are summarized and discussed. What's more, the reaction mechanism based on TS‐1/H2O2 system is proposed on regarding the isolated skeleton Ti site in titanium‐silicon zeolite as the active central site. Finally, the challenges and future development prospects of TS‐1 zeolite in synthesis and catalytic applications are predicted.

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Difraction and complementary analysis methods for the design of MFI-type titanosilicalites with catalytic properties

Cited by 4 publications

References 21 publications

Tracking Lattice Distortion Induced by Defects and Framework Tin in Beta Zeotypes

Tracking Lattice Distortion Induced by Defects and Framework Tin in Beta Zeotypes

Rational Design of Aluminium-containing Zeolites with Typological Structure of HZSM-5 and Catalytic Properties

Recent Advances in the Synthesis and Application of TS‐1 Zeolite for Green Catalytic Oxidation

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