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FROM EXPLORATION TO RATIONAL DESIGN OF SELECTIVE PROPANE DEHYDROGENATION CATALYSTS
Title
FROM EXPLORATION TO RATIONAL DESIGN OF SELECTIVE PROPANE DEHYDROGENATION CATALYSTS
Creator
Hu, Bo
Date
2015, 2015-12
Description
Light olefins, e.g., ethene and propene, are important building blocks of chemical industry for the production of fuels, polymers, lubricants...
Show moreLight olefins, e.g., ethene and propene, are important building blocks of chemical industry for the production of fuels, polymers, lubricants and other fine chemicals. Due to the rapidly increasing production of shale gas, conversion of small alkanes in the shale gas, e.g., ethane and propane, to their corresponding olefins via alkane dehydrogenation could be an important industrial process. This thesis has focused on exploring the novel single site heterogeneous catalysts for selective alkane dehydrogenation and investigating the general principles of rational catalyst design to achieve a better performing (e.g., more active, more stable, highly selective) dehydrogenation catalyst. Based on the observed reactivity of ZnO for olefin hydrogenation and activity of Zn-ZSM-5 catalysts for alkane activation, catalytic properties of isolated Zn2+ were first explored for propane dehydrogenation. The 3-coordinate Zn in single site Zn/SiO2 catalyst was demonstrated to be the catalytically active species that was highly selective for the generation of propene by propane dehydrogenation. DFT calculations revealed that slow β-hydride elimination of alkyl intermediates limited the overall activity of single site Zn/SiO2 catalyst. Thus, single site Co/SiO2 was also prepared in order to take the advantage of fast β-hydride elimination. The higher activity of single site Co/SiO2 emphasized the potential of transition metals for alkane dehydrogenation, and propane dehydrogenation reactivity of transition metals was further explored by investigating single site Fe/SiO2 catalyst. By comparing with metallic Fe nanoparticles and bulk phase Fe oxides catalysts, the 3-coordinate single site Fe2+ was also suggested to be the catalytically active species for selective propane dehydrogenation. However, the catalytic activity of single site Fe/SiO2 catalyst was lower than that of Zn/SiO2. Such result suggested heterolytic cleavage of C-H bonds was slow for transition metals, e.g., Co and Fe, due to their weak Lewis acidity, and it may mitigate the advantages gained in rapid β-hydride elimination. An exploration of ligand effects for improving heterolytic cleavage over single site heterogeneous catalysts was performed. The strength of metal oxygen bond governed by ligand electron donating effects and ligand basicity were found to be the critical chemical descriptors for a facile heterolytic cleavage. Those observed principles of ligand effects would lead to a new strategy of rational catalyst design for a superior dehydrogenation catalyst.
Ph.D. in Chemistry, December 2015
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Control Surface Synthesis of Propane Dehydrogenation Catalysts
Title
Control Surface Synthesis of Propane Dehydrogenation Catalysts
Creator
Zhao, Yiqing
Date
2019
Description
Alkane dehydrogenation is one of the primary chemical reactions to convert light alkanes into light olefins. The conversion of small alkanes...
Show moreAlkane dehydrogenation is one of the primary chemical reactions to convert light alkanes into light olefins. The conversion of small alkanes to alkenes by dehydrogenation reactions is important for polymer and chemical industrial process because it makes direct producing the possible alkenes. Controlled synthesis of single-site catalysts are still challenges. This makes tuning of the catalysts structure and active sites difficult. We developed method of Zirconium modified SiO2 to support single-site catalysts. My research is focusing on the synthesis new single-site heterogeneous catalysts for high selectivity alkane dehydrogenation reaction and the general principles to design better preformed catalysts (e.g., more active, more selective, more stable) for dehydrogenation reaction, especially on propane dehydrogenation. The study described in this thesis was conducted to understand how zirconium ions can modify the electronic properties and catalytic performance.In this study, with the Zr promoted cobalt catalysts show high propane conversion and propene selectivity compared to the previous reported Co/SiO2 catalyst by our group previous work. The Co/Zr/SiO2 material exhibited good catalytic activity, stability and high propylene selectivity which can reach up to 97% for catalytic propane dehydrogenation at 550 ℃. The catalyst was characterized by TEM, STEM, EPR, DRIFTS, UV-vis, XANES and EXAFS for synthesized material, under reaction conditions and post reaction samples. We hypothesized the reason behind is due to the π donation of Zr will lead to ease of heterolytic cleavage of the propane by have a lower metal-oxygen bond dissociation energy in the rate-determining step which is consistent with the previous calculations found that weaker catalyst-oxygen bonds led to facile heterolytic cleavage. A varieties of single-site Ga catalysts supported on Zr modified SiO2 were synthesized by different methods. The Ga/Zr/SiO2 catalysts prepared by the difference method also exhibit higher or similar activity and selectivity. Those catalysts have more isolated active sites show that rational catalyst design method, such as surface organometallic chemistry synthesize, can be applied in heterogeneous systems using homogeneous catalyst design method. But the origin of those effects is unclear, some discussion of possible origins of observation of catalysts behavior are discussed in Chapter 4. And we will do more characterization to find the origins behind.
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