摘要
有机/无机杂化多孔材料是一类新型的多孔材料,在催化、分离、吸附、主客体化学和功能材料等领域都有巨大的潜在应用价值,是当今材料和催化等众多领域的一个研究热点。
本论文的工作主要集中在两个方面,一是采用模板辅助合成法制备了三种新型的多孔甲基膦酸盐;二是采用水热合成方法,制备了两种新型六方管状1-羟基乙叉-1,1-二膦酸盐。综合采用EDX,GC-MS,EPMA,FTIR,NMR,TG,DTA,XRD,氮气物理吸附-脱附和X-射线单晶衍射等方法对制得的材料进行了表征和结构测定,得到了一些有意义的结果。
首次利用甲基膦酸二丁酯(DBMP)作为模板剂成功合成了多孔甲基膦酸盐,并发展了两种有效的脱除模板剂的方法,即低压热处理法和水热处理法。采用这两种方法,可以在不破坏有机/无机杂化骨架的前提下高效地除掉中间产物中包含的模板剂,制得多孔甲基膦酸盐。观察到脱除模板剂的方法对产品的结构有很大的影响。
采用水热合成法,首次合成出两种新型六棱柱形管状1-羟基乙叉-1,1-二膦酸盐(DLES-Alt 和DLES-CrAl)晶体。用X-射线单晶衍射法解析了它们的晶体结构。两者的结构相近,都呈层状结构。平行于ab 平面的层板包含六边形骨架结构,其中含有”三叶草”型手性结构单元。证实1-羟基乙叉-1,1-二膦酸配体(hedp)中的季碳为手性碳原子。考察了合成条件对DLES-Alt 晶体形貌和结构的影响。在不同条件下得到几种具有不同形貌的1-羟基乙叉-1,1-二膦酸铝钠系列晶体,DLES-Alt,DLES-Alp,DLES-Als 和DLES-Alts,并成功地解析了它们的结构。另外,还合成了1-羟基乙叉-1,1-二膦酸铬钠(DLES-Cr)和四水合乙二胺1-羟基乙叉-1,1-二膦酸二钠盐(SDP-2)这两个新晶体。在前述的七种新晶体中,hedp 表现出四种未见报道的新配位形式。
Organic-inorganic hybrid materials are novel porous materials. They have lots ofpotential utilizations in the field of catalysis, separation, sorption, host-guestchemistry and functional materials. Therefore, the materials have drawn muchattention in recently years.
The thesis focused on the two main subjects. Firstly, three novelmetal-methylphosphonates were synthesized by using template-assisted method;secondly, two novel hexagonal tubular metal 1-hydroxyethylidenediphosphonateswere synthesized by utilizing hydrothermal technology. The synthesized materialswere characterized by EDX, GC-MS, EPMA, FTIR, NMR, TG, DTA, XRD, nitrogenadsorption-desorption measurements and X-ray single-crystal diffraction. Someinteresting results were obtained.
DBMP (dibutyl methylphosphonate) could be used as template for synthesizingporous methylphosphonates. The incorporated template could be removed efficientlyfrom the as-synthesized precursor by evaporation in vacuum or by hydrothermaltreatment without destroying the hybrid structures. The post-synthesis treatment hasgreat effects on the structures of the products.
Two novel hexagonal tubular metal 1-hydroxyethylidenediphosphonates,DLES-Alt and DLES-CrAl, were synthesized by using hydrothermal technology.Their structures were determined by single-crystal X-ray diffraction. They areisostructural with layered crystal structures, propeller-like chiral motifs, andhexagonal rings along [001]. Moreover, there is a chiral quaternary carbon in the1-hydroxyethylidenediphosphonic (hedp) ligand. Several new crystals with differentmorphologies have been synthesized in different reaction conditions. The newcrystals are designated as DLES-Alt,DLES-Alp,DLES-Als and DLES-Alts,respectively. The order of cell dimension is DLES-Als > DLES-Alts > DLES-Alt >DLES-Alp. Furthermore, another two novel crystals of chrominium1-hydroxyethylidenediphosphonate (DLES-Cr) and NH3CH2CH2NH3) Na2(hedp)·4H2O (SDP-2) were synthesized successfully. In the above seven new crystals,hedp shows four novel coordination modes.
引文
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