4.8 Review

A review on titanosilicate-1 (TS-1) catalysts: Research progress of regulating titanium species

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Article Chemistry, Applied

Addition of polyethylene glycol for the synthesis of anatase-free TS-1 zeolites with excellent catalytic activity in 1-hexene epoxidation

Xinyu Chang et al.

Summary: Adding suitable amount of polyethylene glycol (PEG) can effectively inhibit the generation of unfavourable anatase, leading to the formation of anatase-free TS-1 zeolites enriched with tetrahedral framework Ti species, which show significant improvement in catalyzing epoxidation.

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Titanosilicate Epoxidation Catalysts: A Review of Challenges and Opportunities

Valentin Smeets et al.

Summary: Epoxidation reactions are crucial for modern chemistry, with Ti-based titanosilicate catalysts playing a central role in driving more versatile, high-performing, and greener processes. Challenges include improving catalyst performance through better control of active surface species and optimizing particle size, shape, and surface chemistry. Future research directions aim to broaden the application scope of new catalytic materials and enhance catalyst performance.

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Creation of Hierarchical Titanosilicate TS-1 Zeolites

Risheng Bai et al.

Summary: Hierarchical TS-1 zeolites with multiple porosity levels have attracted increasing interest in recent years due to their improved mass transfer efficiency and enhanced accessibility of Ti active sites. Strategies for constructing hierarchical TS-1 zeolites, such as mesoporogen, mesoporogen-free, and demetallization methods, have been developed to address steric and diffusional issues, leading to improved catalytic performances in oxidative desulfurization and epoxidation reactions. Effective characterization methods for Ti species and hierarchical zeolite structures have been described, along with current challenges and future development perspectives for preparing hierarchical TS-1 zeolite catalysts.

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Reversing Titanium Oligomer Formation towards High-Efficiency and Green Synthesis of Titanium-Containing Molecular Sieves

Dong Lin et al.

Summary: The green and efficient synthesis of titanium-containing molecular sieves is hindered by environmentally unfriendly additives and complicated procedures. A new additive-free route has been developed using hydroxyl free radicals generated from ultraviolet irradiation, successfully reversing the formation of titanium oligomers to match hydrolysis rates of titanium and silicon species. This approach shows fantastic catalytic performance for propene epoxidation with H-2 and O-2, opening up new opportunities for high-efficiency, environmentally friendly, and facile production of pure titanium-containing molecular sieves compared to conventional hydrothermal methods.

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Single-crystalline hierarchically-porous TS-1 zeolite catalysts via a solid-phase transformation mechanism

Yuanchao Shao et al.

Summary: Hierarchically porous zeolites are a type of catalyst with improved catalytic performances compared to conventional microporous-only zeolites, due to enhanced mass transportation among meso/macropores. The strategy of controlling growth/crystallization in a solidified hydrogel system allows for the synthesis of TS-1 zeolites with hierarchical porosity, single-crystalline structure, and high catalytic performance in alkene oxidations. This method offers a cost-effective alternative to traditional synthetic methods.

MICROPOROUS AND MESOPOROUS MATERIALS (2021)

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TS-1 zeolite with homogeneous distribution of Ti atoms in the framework: synthesis, crystallization mechanism and its catalytic performance

Zhen Chen et al.

Summary: The homogeneous distribution of titanium atoms in TS-1 zeolite (BUS-TS-1) synthesized under high basicity conditions through a bottom-up strategy leads to better catalytic performance for both olefin and alkane oxidation. Gripper-like silicon species can condense with Ti-OH to form stable Si-O-Ti species, ensuring the phase transfer rates match during crystallization and result in the uniform distribution of Ti atoms. This work offers a useful strategy for synthesizing high-performance catalysts by regulating the distribution of Ti active sites within the TS-1 framework.

JOURNAL OF CATALYSIS (2021)

Article Chemistry, Physical

Competition of propylene hydrogenation and epoxidation over Au-Pd/TS-1 bimetallic catalysts for gas-phase epoxidation of propylene with O2 and H2

Zhishan Li et al.

Summary: The collaboration between Au and Pd in the formation of H2O2 and gas-phase epoxidation of propylene was beneficial, while the introduction of Pd complicated the reaction. Propylene hydrogenation predominantly occurred at Pd sites, while propylene epoxidation occurred at Au-Ti sites. O-2 concentration significantly promoted propylene hydrogenation, and CO could mitigate propylene hydrogenation over Au-Pd/TS-1.

APPLIED CATALYSIS A-GENERAL (2021)

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Gripper-like Silicon Species for Efficient Synthesis of Crystalline Metallosilicates with Spatially Homogeneous Heteroatoms in the Framework

Zhen Chen et al.

Summary: This study presents an efficient strategy for synthesizing crystalline metallosilicates with spatially homogeneous distribution of heteroatoms in zeolite frameworks, through the crystal dissolution and crystallization process (CDC process). The gripper-like silicon species are identified to play a key role in incorporating and distributing heteroatoms effectively during the CDC process. This approach opens up a new perspective for the synthesis of heteroatomic zeolites by controlling the state of silicon species.

CHEMISTRY OF MATERIALS (2021)

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Amino acid-assisted synthesis of TS-1 zeolites containing highly catalytically active TiO6 species

Yuyao Wang et al.

Summary: A novel synthesis method has been developed to tailor the distribution of Ti species in titanosilicate zeolites, achieving high catalytic performance in selective oxidation reactions.

CHINESE JOURNAL OF CATALYSIS (2021)

Article Chemistry, Inorganic & Nuclear

High-efficiency synthesis of enhanced-titanium and anatase-free TS-1 zeolite by using a crystallization modifier

Jiani Zhang et al.

Summary: A high-efficiency strategy using H3BTC as a crystallization modifier was proposed to rapidly synthesize enhanced-Ti TS-1 zeolite without anatase TiO2. The Ti species enter the TS-1 framework through a transformation mechanism from liquid phase to crystals and in situ transformation of the solid phase, resulting in a significantly increased content of framework Ti and a Si/Ti ratio up to 48.5. In epoxidation reactions, the synthesized TS-1 showed an 8.01% improvement in alkene conversion compared to traditional TS-1, indicating potential for industrial applications.

INORGANIC CHEMISTRY FRONTIERS (2021)

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Synthesis of TS-1 zeolites from a polymer containing titanium and silicon

Jiacheng Xing et al.

Summary: The synthesis of TS-1 zeolites has revolutionized the green oxidation system by using H2O2 as an oxidant, with water as the only byproduct. A high-quality TS-1 zeolite, free of extra-framework Ti species, has been successfully synthesized using a novel polymer containing titanium and silicon. This method ensures a good matching of the hydrolysis rate between the silicon source and titanium source, facilitating the incorporation of titanium into the framework and exhibiting excellent catalytic performance in oxidation reactions.

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In-depth understanding the role of seeds in the synthesis of TS-1

Zhen Chen et al.

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Hierarchical micro-/macroporous TS-1 zeolite epoxidation catalyst prepared by steam assisted crystallization

Valentin Smeets et al.

MICROPOROUS AND MESOPOROUS MATERIALS (2020)

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Controlling the Morphology and Titanium Coordination States of TS-1 Zeolites by Crystal Growth Modifier

Xiaojing Song et al.

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Christopher P. Gordon et al.

NATURE (2020)

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A one-step rapid synthesis of TS-1 zeolites with highly catalytically active mononuclear TiO6 species

Wenjing Xu et al.

JOURNAL OF MATERIALS CHEMISTRY A (2020)

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Temperature-regulated construction of hierarchical titanosilicate zeolites

Yue Song et al.

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Hollow zeolite microspheres as a nest for enzymes: a new route to hybrid heterogeneous catalysts

Valentin Smeets et al.

CHEMICAL SCIENCE (2020)

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Aerosol Route to TiO2-SiO2 Catalysts with Tailored Pore Architecture and High Epoxidation Activity

Valentin Smeets et al.

CHEMISTRY OF MATERIALS (2019)

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Preparation of Efficient TS-1 with Small Particle Size and Enhanced Framework Ti

Mozaffar Shakeri et al.

CHEMISTRYSELECT (2019)

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Synthesis and Characterisation of Hierarchically Structured Titanium Silicalite-1 Zeolites with Large Intracrystalline Macropores

Tobias Weissenberger et al.

CHEMISTRY-A EUROPEAN JOURNAL (2019)

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Cooperative Effects between Hydrophilic Pores and Solvents: Catalytic Consequences of Hydrogen Bonding on Alkene Epoxidation in Zeolites

Daniel T. Bregante et al.

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Nickel-Modified TS-1 Catalyzed the Ammoximation of Methyl Ethyl Ketone

Dandan Yang et al.

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Hollow core-shell structured TS-1@S-1 as an efficient catalyst for alkene epoxidation

J. Wang et al.

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Improving the catalytic performance of TS-1 through Zn(AC)(2) modification

Xiangqing Fang et al.

CATALYSIS COMMUNICATIONS (2018)

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Mesoporous/Microporous Titanium Silicalite with Controllable Pore Diameter for Cyclohexene Epoxidation

Yi Zuo et al.

INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH (2018)

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Propylene oxide inhibits propylene epoxidation over Au/TS-1

James W. Harris et al.

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Synthesis of hierarchical titanium silicalite-1 in the presence of polyquaternium-7 and its application in the hydroxylation of phenol

Zongzhuang Han et al.

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Intermediate-crystallization promoted catalytic activity of titanosilicate zeolites

Risheng Bai et al.

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From 3D to 2D zeolite catalytic materials

J. Prech et al.

CHEMICAL SOCIETY REVIEWS (2018)

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On the synthesis and performance of hierarchical nanoporous TS-1 catalysts

Abdul-Lateef Adedigba et al.

MICROPOROUS AND MESOPOROUS MATERIALS (2017)

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Synthesis of a highly active oxidation catalyst with improved distribution of titanium coordination states

Lizhi Wu et al.

CHEMICAL COMMUNICATIONS (2016)

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Synthesis of TS-1 with Preferably Distributed Ti in Depth Direction of Crystals

Kosuke Takaishi et al.

CHEMISTRY LETTERS (2016)

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Copper-modified TS-1 catalyzed hydroxylation of phenol with hydrogen peroxide as the oxidant

Guoqiang Wu et al.

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Hierarchical TS-1 synthesized effectively by post-modification with TPAOH and ammonium hydroxide

Baorong Wang et al.

RSC ADVANCES (2016)

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Effect of treatment with different bases on the catalytic properties, of TS-1/SiO2 extrudates in propylene epoxidation

Wancang Song et al.

MICROPOROUS AND MESOPOROUS MATERIALS (2015)

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Selective synthesis of dimethyl ketone oxime through ammoximation over Ti-MOR catalyst

Jianghong Ding et al.

APPLIED CATALYSIS A-GENERAL (2014)

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Synthesis and morphology research of framework Ti-rich TS-1 containing no extraframework Ti species in the presence of CO2

Guowei Zhu et al.

INORGANIC CHEMISTRY COMMUNICATIONS (2014)

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Effect of sodium ions in synthesis of titanium silicalite-1 on its catalytic performance for cyclohexanone ammoximation

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FRONTIERS OF CHEMICAL SCIENCE AND ENGINEERING (2014)

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Deng-Gao Huang et al.

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Hydrothermal synthesis of hierarchical titanium silicalite-1 using single template

Li Chen et al.

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Ethanol-assistant synthesis of TS-1 containing no extra-framework Ti species

Deng-Gao Huang et al.

CATALYSIS TODAY (2010)

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Stable Bulky Particles Formed by TS-1 Zeolite Nanocrystals in the Presence of H2O2

Zhichao Shan et al.

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Hierarchical mesoporous zeolites with controllable mesoporosity templated from cationic polymers

Lifeng Wang et al.

MICROPOROUS AND MESOPOROUS MATERIALS (2010)

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Preparation and properties of TS-1 zeolite and film using Sil-1 nanoparticles as seeds

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CHEMICAL ENGINEERING JOURNAL (2009)

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Using Titanium Alkoxide Complex to Synthesize TS-1 and Their Catalytic Performance for Propylene Epoxidation

J. Zhao et al.

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Effect of ammonium salts on the synthesis and catalytic properties of TS-1

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MICROPOROUS AND MESOPOROUS MATERIALS (2009)

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Synthesis, crystallization mechanism, and catalytic properties of titanium-rich TS-1 free of extraframework titanium species

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2007)

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Synthesis, characterization and catalytic performance of titanium silicalite-1 prepared in the presence of nonionic surfactants

Hong Liu et al.

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Synthesis of TS-1 molecular sieves using a new Ti source

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A quantum chemical study of comparison of various propylene epoxidation mechanisms using H2O2 and TS-1 catalyst

David H. Wells et al.

JOURNAL OF PHYSICAL CHEMISTRY B (2006)

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Synthesis of Ti-MWW by a dry-gel conversion method

P Wu et al.

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Evidence of defect-promoted reactivity for epoxidation of propylene in titanosilicate (TS-1) catalysts: A DFT study

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Zeolite (MFI) crystal morphology control using organic structure-directing agents

G Bonilla et al.

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Photochemical and FT-IR probing of the active site of hydrogen peroxide in Ti silicalite sieve

WY Lin et al.

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Effect of sodium ions on propylene epoxidation catalyzed by titanium silicalite

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Ti location in the MFI framework of Ti-silicalite-1:: A neutron powder diffraction study

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