Design of hierarchical TS-1 zeolites using spray-drying for enhanced catalytic activity in cyclic carbonate formation

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials Pub Date : 2025-03-25 DOI:10.1016/j.micromeso.2025.113610

Svitlana Gryn , Mykhailo Kurmach , Pavlo Yaremov , Oleksiy Shvets , Sergei Alekseev , Susanne Wintzheimer , Karl Mandel

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Abstract

Herein we report on the design of hierarchical zeolite supraparticles from hydrothermally-derived 100 nm TS-1 zeolite nanoparticles (NPs) by means of spray-drying. These supraparticles, with a large surface area (up to 678 m²/g), possess a biporous structure that is composed of zeolitic micropores (0.9–1.1 nm) and secondary mesopores. Depending on the synthesis conditions, it is possible to prepare supraparticles, formed by separate NPs and wide (50 nm) interparticular pores or by zeolitic NPs, tightly glued together by amorphous mesoporous titanosilicate. According to the UV–vis spectrometry data and FTIR studies of adsorbed pyridine, the active sites of “separated” supraparticles are presented mainly by Lewis sites associated with [TiO₄] species isolated in the zeolite matrix, while “glued” supraparticles possess a significant fraction of [TiO₅] and [TiO₆] species.

The supraparticles demonstrate sufficiently high catalytic activity in the industrially valuable two-stage synthesis of cyclic carbonate (4-phenyl-1,3-dioxolan-2-one) from styrene and carbon dioxide, in the presence of tert-butyl hydroperoxide as an oxidant and tetrabutylammonium iodide as a co-catalyst. We found that the selectivity to the target cyclic carbonate increased with an external specific surface area growth, probably due to the facilitated withdrawal of reaction products from the zeolite pores.

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分级TS-1沸石喷雾干燥设计提高循环碳酸盐地层催化活性

本文报道了利用水热衍生的100纳米TS-1沸石纳米颗粒（NPs），采用喷雾干燥的方法设计分级沸石超颗粒。这些超颗粒具有较大的表面积（高达678 m2/g），具有由沸石微孔（0.9-1.1 nm）和次级介孔组成的双孔结构。根据不同的合成条件，可以制备由单独的NPs和宽（50 nm）的种间孔或沸石状NPs组成的超颗粒，这些NPs由无定形介孔二氧化钛紧密粘合在一起。根据吸附吡啶的紫外可见光谱和红外光谱研究，“分离”超粒子的活性位点主要是与沸石基质中分离的[TiO4]相关的路易斯位点，而“粘接”超粒子则含有相当比例的[TiO5]和[TiO6]。在过氧化氢叔丁基作为氧化剂和四丁基碘化铵作为助催化剂的情况下，这些超颗粒在苯乙烯和二氧化碳两段合成环碳酸酯（4-苯基-1,3-二氧唑-2- 1）中表现出足够高的催化活性。我们发现对目标环碳酸盐的选择性随着外比表面积的增加而增加，这可能是由于反应产物从沸石孔中更容易退出。

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来源期刊

Microporous and Mesoporous Materials 化学-材料科学：综合

CiteScore

10.70

自引率

5.80%

发文量

649

审稿时长

26 days

期刊介绍： Microporous and Mesoporous Materials covers novel and significant aspects of porous solids classified as either microporous (pore size up to 2 nm) or mesoporous (pore size 2 to 50 nm). The porosity should have a specific impact on the material properties or application. Typical examples are zeolites and zeolite-like materials, pillared materials, clathrasils and clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, or porous metal oxides. Both natural and synthetic porous materials are within the scope of the journal. Topics which are particularly of interest include: All aspects of natural microporous and mesoporous solids The synthesis of crystalline or amorphous porous materials The physico-chemical characterization of microporous and mesoporous solids, especially spectroscopic and microscopic The modification of microporous and mesoporous solids, for example by ion exchange or solid-state reactions All topics related to diffusion of mobile species in the pores of microporous and mesoporous materials Adsorption (and other separation techniques) using microporous or mesoporous adsorbents Catalysis by microporous and mesoporous materials Host/guest interactions Theoretical chemistry and modelling of host/guest interactions All topics related to the application of microporous and mesoporous materials in industrial catalysis, separation technology, environmental protection, electrochemistry, membranes, sensors, optical devices, etc.