Imidazolium-Based Organic Structure Directing Agents for the Synthesis of Microporous Materials

The central theme of this thesis is the use of imidazolium-based organic structure directing agents (OSDAs) in microporous materials synthesis. Imidazoliums are advantageous OSDAs as they are relatively inexpensive and simple to prepare, show robust stability under microporous material synthesis conditions, have led to a wide range of products, and have many permutations in structure that can be explored. The work I present involves the use of mono-, di-, and triquaternary imidazolium-based OSDAs in a wide variety of microporous material syntheses. Much of this work was motivated by successful computational predictions (Chapter 2) that led me to continue to explore these types of OSDAs. Some of the important discoveries with these OSDAs include the following: 1) Experimental evaluation and confirmation of a computational method that predicted a new OSDA for pure-silica STW, a desired framework containing helical pores that was previously very difficult to synthesize. 2) Discovery of a number of new imidazolium OSDAs to synthesize zeolite RTH, a zeolite desired for both the methanol-to-olefins reaction as well as NOX reduction in exhaust gases. This discovery enables the use of RTH for many additional investigations as the previous OSDA used to make this framework was difficult to synthesize, such that no large scale preparations would be practical. 3) The synthesis of pure-silica RTH by topotactic condensation from a layered precursor (denoted CIT-10), that can also be pillared to make a new framework material with an expanded pore system, denoted CIT-11, that can be calcined to form a new microporous material, denoted CIT-12. CIT-10 is also interesting since it is the first layered material to contain 8 membered rings through the layers, making it potentially useful in separations if delamination methods can be developed. 4) The synthesis of a new microporous material, denoted CIT-7 (framework code CSV) that contains a 2-dimensional system of 8 and 10 membered rings with a large cage at channel intersections. This material is especially important since it can be synthesized as a pure-silica framework under low-water, fluoride-mediated synthesis conditions, and as an aluminosilicate material under hydroxide mediated conditions. 5) The synthesis of high-silica heulandite (HEU) by topotactic condensation as well as direct synthesis, demonstrating new, more hydrothermally stable compositions of a previously known framework. 6) The synthesis of germanosilicate and aluminophosphate LTA using a triquaternary OSDA. All of these materials show the diverse range of products that can be formed from OSDAs that can be prepared by straightforward syntheses and have made many of these materials accessible for the first time under facile zeolite synthesis conditions.

Processes controlling the quantities of biogenic materials in lakes and reservoirs subject to cultural eutrophication

The processes which control the growth, composition, succession and loss from suspension of phytoplankton algae are briefly reviewed, with special reference to function in eutrophic reservoir systems. The ecology of larger algal biomasses supported by high nutrient loading rates are more likely to be subject to physical (wash-out, underwater light penetration, thermal stability and mixing) than to chemical constraints. Sudden changes in the interactions between physical factors temporarily impair the growth of dominant algal species, and advance the succession. Certain algae may be cropped heavily, but selectively, by zooplankton feeding, but they are rarely the species which cause problems in waterworks practice. Grazing, however, does influence succession. A deeper understanding of the operation of loss control mechanism is urgently required. Potentially, manipulation of the physical environment provides an important means of alleviating day-to-day algal problems in eutrophic reservoirs; in terms of cost effectiveness these may prove to be more attractive than reducing nutrient loads at source.

固着磨料加工工艺对磷酸盐钕玻璃亚表面缺陷的影响

散粒磨料研磨与固着磨料研磨是光学研磨加工过程中的两种主要手段,但两者材料去除的机制不同。目前针对高功率固体激光装置中的主要工作物质——磷酸盐激光钕玻璃的亚表面缺陷(SSD)研究相对较少,因此在实验的基础上,通过系统地研究固着磨料对磷酸盐激光钕玻璃的研磨工艺过程,分析了多种因素,如磨料粒径、载荷大小、机床转速,以及结合剂材料与冷却液等对钕玻璃亚表面缺陷形成的影响,并与散粒磨料研磨工艺所产生的亚表面缺陷进行了比较,对关键工艺参数进行定量,为高质量钕玻璃制造工艺的选型以及进一步优化亚表面缺陷提供了重要的参考数据。