CN109518274B - 一种具有二维纳米孔腔结构的十二钨酸盐晶体材料及其制备方法 - Google Patents
一种具有二维纳米孔腔结构的十二钨酸盐晶体材料及其制备方法 Download PDFInfo
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Abstract
Description
技术领域
本发明属于金属氧簇合物材料及其制备技术领域,具体是涉及一种具有二维纳米孔腔结构的十二钨酸盐晶体材料及其制备方法。
背景技术
某些过渡金属(如钒、钼和钨)在其高氧化态下能够形成多金属氧簇合物。这类物质由于其特有的结构通常具有一些优良的特性,如导电性、磁性及催化性等,在分析、临床诊断、催化、生化、医药及材料科学等方面具有广泛应用。随着多金属氧酸盐化学研究进展,人们对有机-无机杂化的多金属氧酸盐的研究越来越多,这其中就包括一个重要家族杂化多钨氧酸盐。目前在这一研究领域最新的挑战是如何利用基本的构筑模块构建期望的结构,以便获得具有纳米尺寸或独特性能的有机-无机杂化材料。
在多金属氧簇合物中,根据多金属氧簇阴离子中所含元素的种类不同,可将该类化合物分为两类:同多化合物和杂多化合物。前者主要是由单一的金属氧簇阴离子组成,后者为由除氧以外两种或两种以上杂元素形成的金属团簇。多金属氧酸盐化合物的基本结构主要是由[MOn](M=V,Mo,W)多面体组成的。如多钒氧簇合物,最基本的结构单元为[VO4]四面体、[VO5]四角单锥和[VO6]八面体;多钼氧簇合物,最基本的结构单元为[MoO4]四面体、[MoO5]四角单锥、[MoO6]八面体和[MoO7]五角双锥;多钨氧簇合物,最基本的结构单元有[WO5]四角单锥和[WO6]八面体等。这些多面体以共点、共边或共面等方式连接形成多金属氧簇合物。
催化活性是这类材料一个重要的共性。与其它催化材料相比,其催化活性更高,催化的化学反应条件一般较温和,本身的毒性小,催化副产物少,因而这类材料很快成为一种新型绿色催化剂。近来的研究表明,多钨氧簇合物表现出优异的催化特性,但是对于由碱金属构筑的有机-无机杂化的杂多钨酸盐簇合物研究不多,特别是具有二维纳米孔腔结构的这类晶体材料更是少有研究。因此设计与制备此类材料是一件很有意义的工作。
发明内容
本发明要解决的技术问题是克服现有技术的缺陷,提出了一种具有二维纳米孔腔结构的十二钨酸盐晶体材料及其制备方法。
为解决本发明的技术问题,所采用的技术方案为:一种具有二维纳米孔腔结构的十二钨酸盐晶体材料,其化学式为(NH4)Na2K(C3H5N2)6[H2W12O42]·8H2O;其省略铵离子和水分子的单晶结构式如图1所示;该晶体属于三斜晶系,空间群为P-1,晶胞参数为 α=82.1590(10)°,β=87.7150(10)°,γ=84.0480(10)°,Z=1,Dc=3.787g/cm3。
上述具有二维纳米孔腔结构的十二钨酸盐晶体材料采用水热合成法制备,将0.06~0.11重量份钨酸钠、0.09~0.12重量份钨酸、0.05~0.08重量份咪唑、0.03~0.05重量份氯化铵、0.03~0.06重量份氯化钾和15~20重量份水均匀混合配制成反应底物,反应底物在反应容器中水热合成制得具有二维纳米孔腔结构的十二钨酸盐晶体材料,水热合成温度至少为160℃,水热合成时间至少为48h。
本发明相对于现有技术的有益效果是:
其一,通过单晶衍射仪对制得的目标产物进行检测,由其结果可知该目标产物的晶体化学式为(NH4)Na2K(C3H5N2)6[H2W12O42]·8H2O,属于三斜晶系,空间群为P-1,晶胞参数为α=82.1590(10)°,β=87.7150(10)°,γ=84.0480(10)°,Z=1,Dc=3.787g/cm3。该目标产物命名为具有二维纳米孔腔结构的十二钨酸盐晶体材料。
其二,根据化学式(NH4)Na2K(C3H5N2)6[H2W12O42]·8H2O计算出化合物中H、C、N的含量:H 1.48%,C 6.11%,N 5.14%。经过元素分析,表明该晶体材料中H、C、N的含量分别为1.45%,C 6.21%,N 5.37%,这一结果与理论计算相符。
其三,二维纳米孔腔结构的十二钨酸盐晶体材料的制备通过水热合成法实现,合成方法简单易操作,反应收率较高。
其四,具有二维纳米孔腔结构的十二钨酸盐晶体材料的制备方法中水热合成温度至少为160℃,否则无法制备该晶体材料。
其五,制备的具有二维纳米孔腔结构的十二钨酸盐晶体材料,可广泛应用于催化材料领域,例如其在双氧水氧化环戊烯制备戊二醛时起到催化作用,可以使产物产率达到60%以上,表现出了良好的催化活性。
作为有益效果的进一步体现:其一,水热合成的时间为48~72h,水热合成的温度为160~180℃,有利于获得更高产率的二维纳米孔腔结构的十二钨酸盐晶体材料。其二,水热合成开始前将反应溶液温度自室温升温至水热合成温度的速率为1~2℃/min,水热合成结束后自水热合成温度降温至室温的速率为0.2~0.3℃/min,有利于获得形态较好的十二钨酸盐晶体材料。其三,反应容器为置于烘箱中的高压釜,且水热合成开始前的升温、水热合成过程中的保温以及水热合成结束后的降温是通过烘箱进行调控,水热合成反应在高压釜中进行可使水处于亚临界和超临界状态下,此时反应处于分子水平,反应性提高,因此采用高压釜比采用其它设备可更好地制备出该类晶体材料。烘箱可以方便地调整水热反应的温度,也可以使得水热反应釜保持合适的升温、降温速度。
附图说明
以下结合实施例和附图对本发明作出进一步的详述。
图1是本发明制得的目标产物的单晶结构图(铵离子和水分子省略)。
图2是本发明制得产物结构式中由钠、钾离子和钨氧簇阴离子构筑的二维层状结构示意图。
具体实施方式
首先从市场购得或用常规方法制得:
钨酸钠、钨酸、咪唑、氯化铵、氯化钾、蒸馏水、50mL烧瓶、磁力搅拌器、25mL高压釜、烘箱。
接着,
实施例1
①、称量钨酸钠0.06g、钨酸0.12g、咪唑0.08g、氯化铵0.04g、氯化钾0.03g于50mL烧瓶中,并加入18mL蒸馏水,将烧瓶放置于磁力搅拌器上搅拌混合20分钟,得混合溶液。
②、将混合均匀的溶液转移至25mL高压釜中。
③、把高压釜放入烘箱中,从室温开始以1℃/min的速率加热至160℃,在此温度下保持72h,然后以0.2℃/min的速率降至室温,得到二维纳米孔腔结构的十二钨酸盐晶体材料,产率约为72%。
通过单晶衍射仪对本实施例制得的目标产物进行晶体结构测定,结果如下:
晶体数据:
晶体结构分析:
请一并参阅图1,结构分析表明,金属簇阴离子内的钨原子可分为三类,一类是与一个端基氧和五个桥氧相连的钨,一类是与两个端基氧和四个桥氧相连的钨,另一类则是不含端基氧只与六个桥氧相连的钨,三者皆是八面体的配位几何[WO6]。根据氧原子与金属的连接方式的不同,氧原子可为三类,端基氧、μ2-和μ3-桥氧。端基W=O键键长范围为0.168(2)~0.185(2)nm,桥氧W-O键长范围为0.170(2)~0.235(2)nm。
请一并参阅图2,多氧金属阴离子簇[H2W12O42]之间通过两个配位水的钠离子连成一维链,链和链之间又通过钾离子连接起来,形成二维的无限扩展结构。有趣的是,在二维的层状结构中邻近的两个钾和四个钠离子将四个多氧金属阴离子簇[H2W12O42]聚集起来,围成一个包含的纳米空腔。
实施例2
①、称量钨酸钠0.11g、钨酸0.09g、咪唑0.07g、氯化铵0.03g、氯化钾0.04g于50mL烧瓶中,并加入20mL蒸馏水,将烧瓶放置于磁力搅拌器上搅拌混合20分钟,得混合溶液。
②、将混合均匀的溶液转移至25mL高压釜中。
③、把高压釜放入烘箱中,从室温开始以1℃/min的速率加热至160℃,在此温度下保持72h,然后以0.26℃/min的速率降至室温,得到如图1和2所示的二维纳米孔腔结构的十二钨酸盐晶体材料,产率约为73%。
实施例3
①、称量钨酸钠0.06g、钨酸0.12g、咪唑0.08g、氯化铵0.04g、氯化钾0.03g于50mL烧瓶中,并加入17mL蒸馏水,将烧瓶放置于磁力搅拌器上搅拌混合20分钟,得混合溶液。
②、将混合均匀的溶液转移至25mL高压釜中。
③、把高压釜放入烘箱中,从室温开始以2℃/min的速率加热至180℃,在此温度下保持48h,然后以0.3℃/min的速率降至室温,得到如图1和2所示的二维纳米孔腔结构的十二钨酸盐晶体材料,产率约为75%。
实施例4
①、称量钨酸钠0.08g、钨酸0.11g、咪唑0.05g、氯化铵0.05g、氯化钾0.06g于50mL烧瓶中,并加入15mL蒸馏水,将烧瓶放置于磁力搅拌器上搅拌混合20分钟,得混合溶液。
②、将混合均匀的溶液转移至25mL高压釜中。
③、把高压釜放入烘箱中,从室温开始以1.5℃/min的速率加热至172℃,在此温度下保持65h,然后以0.2℃/min的速率降至室温,得到如图1和2所示的二维纳米孔腔结构的十二钨酸盐晶体材料,产率约为69%。
实施例5
应用实施例
有机-无机杂化的十二钨酸盐晶体材料在催化双氧水氧化环戊烯制备戊二醛上的应用。
取0.08g研成粉未的十二钨酸盐材料,加入到装有20mL的叔丁醇和8mL环戊烯的圆底烧瓶中,控制反应温度在36℃,滴加15mL的双氧水。反应3h后,将溶液过滤,去除催化剂,进行色谱分析。结果表明所得产物的产率可达61%,表现了较好的催化活性。
以上内容仅仅是对本发明的构思所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (6)
1.一种具有二维纳米孔腔结构的十二钨酸盐晶体材料,其特征在于:
其化学式为(NH4)Na2K(C3H5N2)6[H2W12O42]·8H2O;
其省略铵离子和水分子的单晶结构式为:
金属簇阴离子内的钨原子分为三类,一类是与一个端基氧和五个桥氧相连的钨,一类是与两个端基氧和四个桥氧相连的钨,另一类则是不含端基氧只与六个桥氧相连的钨,三者皆是八面体的配位几何[WO6];根据氧原子与金属的连接方式的不同,氧原子分为三类,端基氧、μ2-和μ3-桥氧;端基W=O键键长范围为0.168(2)~0.185(2)nm,桥氧W-O键长范围为0.170(2)~0.235(2)nm;
2.一种制备如权利要求1所述具有二维纳米孔腔结构的十二钨酸盐晶体材料的方法,采用水热合成法,其特征在于:将0.06~0.11重量份钨酸钠、0.09~0.12重量份钨酸、0.05~0.08重量份咪唑、0.03~0.05重量份氯化铵、0.03~0.06重量份氯化钾和15~20重量份水均匀混合配制成反应底物,反应底物在反应容器中水热合成制得具有二维纳米孔腔结构的十二钨酸盐晶体材料,水热合成温度至少为160℃,水热合成时间至少为48h。
3.如权利要求2所述的制备方法,其特征在于:水热合成的时间为48~72h,水热合成的温度为160~180℃。
4.如权利要求2所述的制备方法,其特征在于:水热合成开始前将反应底物温度自室温升温至水热合成温度的速率为1~2℃/min。
5.如权利要求2所述的制备方法,其特征在于:水热合成结束后自水热合成温度降温至室温的速率为0.2~0.3℃/min。
6.如权利要求2所述的制备方法,其特征在于:所述反应容器为置于烘箱中的高压釜,且水热合成开始前的升温、水热合成过程中的保温以及水热合成结束后的降温是通过烘箱进行调控。
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