采用离子热合成方法,在草酸/四丙基溴化铵离子型低共熔混合物中对磷酸锆骨架材料的合成进行了系统地研究,通过改变反应条件合成了2种不同的磷酸锆,α-Zr（HPO4）2？H2O和（NH4）Zr2（PO4）3.体系中的四丙基季铵阳离子对磷酸锆骨架没有体现出模板作用,后者是在较高的反应温度下（220℃）以四丙基季铵离子的热分解产物（NH＋4）作为模板而生成.通过向该体系中添加少量的氮杂环化合物（哌嗪）,合成了一种三维开放骨架的8-元环磷酸锆微孔材料,位于孔道中的质子化哌嗪起到模板作用并平衡骨架负电荷.研究结果表明,草酸/四丙基溴化铵低共熔混合物可以作为一种离子热反应介质,通过向体系中引入少量的有机碱可以起到模板作用来诱导磷酸锆骨架的生成.%By ionothermal synthesis method,a series of syntheses have been performed in an attempt to synthesize novel zirconium phosphate materials in an oxalic acid/tetrapropyl ammonium bromide ionic eutectic mixture.The two different zirconium phosphate materials,α-Zr（HPO4）2oH2O and（NH4）Zr2（PO4）3 have been achieved by changing the synthetic conditions,tetrapropyl ammonium cation could not play its template role to form a new zirconium phosphate and the latter was synthesized at a high temperature（220 ℃） by templating the cation in situ generated from the ionothermal decomposition of the tetrapropyl ammonium（TPA） component.However,after adding a small amount of N-containing heterocyclic compound（piperazine）,a known open-framework zirconium phosphate with 8-ring pore channels was obtained.The protonated piperazine not only plays a template role to form the zirconium phosphate framework but also acts as counter-ions to balance the anion framework.The used deep-eutectic solvent,therefore,can be used as an excellent ionic reaction medium to synthesize zirconium phosphate materials,the organic amine could be added to the initial reaction mixture to induce zirconium phosphate framework.
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