Tailoring the textural and component properties of Mo-Bi based catalysts for the selective oxidation of tert-butanol to methacrolein by the assistance of polymethymethacrylate

IF 1.7 4区 化学 Q4 CHEMISTRY, PHYSICAL Reaction Kinetics, Mechanisms and Catalysis Pub Date : 2024-06-05 DOI:10.1007/s11144-024-02672-4
Qiao Yuan, Zhiwei Zhang, Hui Tian, Yingchun Zhao, Lei Wang
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Abstract

Two Mo-Bi based catalysts were prepared with the assistance of PMMA with different sizes, and tested in selective oxidation of tert-butanol to methacrolein. The prepared catalysts, especially C-PM-6 with μm-PMMA, exhibited excellent catalytic performance. Based on the characterization results (BET, MIP, SEM, TEM, XRD, FTIR), the effects of the assistance of PMMA with different sizes were verified. Without modifying the highly active Co6Fe4Mo12Bi1.5Ox phase, the formation of over-oxidation MoO3 phase was effectively inhibited due to the decomposition of PMMA particles. Importantly, the PMMA assistance could develop hierarchical pore structures, especially mesoporous pores of 6 nm for C-PM-6 catalyst, by preventing primary particles’ agglomeration. Therefore, the mesoporous/macroporous specific surface area obviously increased and thus the abundant active sites were exposed. More importantly, in the newly-formed mesopores pores, there happened Knudsen or molecular diffusion with relatively high mass transfer coefficient, avoiding the overoxidation of target product MAL. From the perspective of reaction engineering, our finding may suggest a new way for developing ultra-high performance commercial selective oxidation catalyst.

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在聚甲基丙烯酸甲酯的辅助下调整铋钼基催化剂的质地和组分特性,用于将叔丁醇选择性氧化为甲基丙烯醛
在不同尺寸的 PMMA 的辅助下制备了两种钼-铋催化剂,并在叔丁醇到甲基丙烯醛的选择性氧化中进行了测试。所制备的催化剂,尤其是含有 μm-PMMA 的 C-PM-6 催化剂,表现出优异的催化性能。根据表征结果(BET、MIP、SEM、TEM、XRD、傅立叶变换红外光谱),验证了不同尺寸 PMMA 的辅助效果。在不改变高活性 Co6Fe4Mo12Bi1.5Ox 相的情况下,PMMA 颗粒的分解有效抑制了过氧化 MoO3 相的形成。重要的是,PMMA 助剂可以通过阻止原生颗粒的团聚而形成分层孔隙结构,尤其是 C-PM-6 催化剂的介孔孔隙可达 6 nm。因此,介孔/大孔的比表面积明显增加,从而暴露出丰富的活性位点。更重要的是,在新形成的介孔中,发生了传质系数相对较高的努森扩散或分子扩散,避免了目标产物 MAL 的过氧化。从反应工程学的角度来看,我们的发现可能为开发超高性能商用选择性氧化催化剂提供了一条新途径。 图文摘要
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来源期刊
CiteScore
3.30
自引率
5.60%
发文量
201
审稿时长
2.8 months
期刊介绍: Reaction Kinetics, Mechanisms and Catalysis is a medium for original contributions in the following fields: -kinetics of homogeneous reactions in gas, liquid and solid phase; -Homogeneous catalysis; -Heterogeneous catalysis; -Adsorption in heterogeneous catalysis; -Transport processes related to reaction kinetics and catalysis; -Preparation and study of catalysts; -Reactors and apparatus. Reaction Kinetics, Mechanisms and Catalysis was formerly published under the title Reaction Kinetics and Catalysis Letters.
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