CN112191274A - 一种酸刻蚀三维褶皱型空心mof催化剂及其制备方法和应用 - Google Patents
一种酸刻蚀三维褶皱型空心mof催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及了一种酸刻蚀三维褶皱型空心MOF催化剂及其制备方法和应用,所述催化剂以具有三维褶皱的金属有机骨架材料UiO‑66为载体,以酸诱导,制备三维褶皱型空心金属有机框架催化剂。本发明还提供了所述三维褶皱型金属有机框架催化剂的制备方法,在水体系下,采用恒温油浴法一步合成,以及提供了空心结构的制备方法,采用酸刻蚀法,在保留结构完整性的同时将MOF的内部挖空以形成笼状结构,制备过程简单易实施,条件温和,制备得到的催化剂可以同时具备表面褶皱和空心结构,表现出了较为优异的催化加氢性能。
Description
技术领域
本发明涉及催化材料的技术领域,尤其涉及一种酸刻蚀三维褶皱型空心MOF催化剂及其制备方法和应用。
背景技术
金属有机骨架(MOF),是一种由金属中心和功能性有机配体组成的新型的具有规整孔道结构的多孔晶体材料。传统的多孔材料主要包括如沸石分子筛、活性炭等,MOFs与之相比具有超高的比表面积(可超过7000m2/g)、可调控的结构以及永久性的孔隙率(可达0.9cm3/g),这使得MOFs在气体吸附,分离,催化和药物输送等应用领域有很大的发展潜力。
中空MOFs是指具有明确边界和内部空腔的纳米材料。它们的结构特征使其具有低密度,高比表面积,电荷传输距离短以及高容量。中空MOFs作为电极材料,有较大的比表面积,具有大量的电化学活性位点,电极与电解液接触面积大,而且由于薄壳和内部空隙,离子扩散路径较短。中空MOFs用于电催化,可以通过控制壳层孔隙结构来筛分分子或通过控制壳层化学相容性来调节分子扩散,从而提高催化反应的选择性,较大的比表面积提高了催化剂的负载量,增加了催化剂与反应物之间的接触面积。并且非球型的中空MOFs由于其各向异性,使得其在光、电、磁等方面将具有更加新颖的性质。而MOFs表面褶皱的存在更进一步的提高了其比表面积,而且表面褶皱有助于所担载的金属粒子的分散,暴露出更多的活性位点,并且可以提高材料的疏水性。
目前所有文献记载的UiO-66均采用溶剂热反应,合成出的形貌为表面光滑的八面体结构,而本发明采用创新性的方法,在水体系下,通过油浴恒温反应,合成出UiO-66形貌是具有三维褶皱的八面体结构。迄今为止,合成空心MOF的方法主要有模板法和Ostwald熟化法,制备的MOFs多为具有多孔外壳和形状模糊的多晶MOFs。由于在外壳中形成无定形区域或微小晶体,这些MOFs通常结晶度低,热稳定性和化学稳定性差,并且在模板移除、去除杂质或退火后结构可能会坍塌。。
发明内容
本发明提供了一种酸刻蚀三维褶皱型空心MOF催化剂及其制备方法,制备过程简单、条件温和,制备得到的催化剂可以同时具备表面褶皱和空心结构,表现出了较为优异的催化加氢性能。
本发明还提供了所述的催化剂在催化剂在硝基芳烃加氢中的应用,所述的加氢主要针对于硝基芳烃中的硝基苯。
本发明解决上述技术问题所采用的技术方案是:一种酸刻蚀三维褶皱型空心MOF催化剂,其特征在于,所述催化剂以具有三维褶皱的金属有机骨架材料UiO-66为载体,其中UiO-66是在水体系下恒温反应合成,生成三维褶皱,再经过酸刻蚀,形成的空心结构。
按上述方案,所述的金属有机骨架材料UiO-66为Zr基、Hf基或者官能团改性的金属有机骨架材料的一种。
所述的酸刻蚀三维褶皱型空心MOF催化剂的制备方法,其特征在于,包括有以下步骤:
(1)UiO-66-NH2(Zr)或UiO-66-NH2(Hf)的制备:将金属锆盐或铪盐、带有不同取代基的对苯二甲酸、水和乙酸混合,搅拌均匀后,进行油浴恒温反应,冷却,再经纯化得到具有三维褶皱的UiO-66-NH2(Zr)或UiO-66-NH2(Hf);
(2)空心结构的制备:将步骤(1)得到的UiO-66-NH2(Zr)或UiO-66-NH2(Hf)与酸溶液混合,经过水热反应,冷却,经纯化、离心、干燥处理得到所述的具有褶皱的空心UiO-66-NH2(Zr)或UiO-66-NH2(Hf)。
按上述方案,所述的带有不同取代基的对苯二甲酸为2-氨基对苯二甲酸、2-羟基对苯二甲酸、对苯二甲酸磺酸钠、2-溴对苯二甲酸。
按上述方案,步骤(1)中,所述的金属锆盐或铪盐、2-氨基对苯二甲酸、水和乙酸的配比为0.5mmol:0.5mmol:(6~9)ml:(4.5~24)ml。
按上述方案,所述的油浴恒温反应条件为:在水体系下,60~90℃,油浴恒温反应12~36h。
按上述方案,所述的纯化过程具体为:油浴恒温反应的产物经水洗涤3次后,室温下浸入新鲜甲醇三天,每天离心换一次甲醇,再经干燥处理,所述的干燥温度为50~70℃,干燥时间为8~12h。
按上述方案,所述的酸溶液为单酸的水溶液,单酸和水的配比为:6ml:(1~16)ml,所述的水热反应条件为:100~120℃,油浴恒温反应3h,6h或12h。
按上述方案,所述的单酸为甲酸、乙酸、丙酸、丁酸和月桂酸中的任意一种。
按上述方案,步骤(2)中的纯化、离心,干燥过程具体为:
水热反应的产物依次经水、甲醇各纯化三次,离心过滤,再经干燥处理,所述的干燥温度为50~70℃,干燥时间为8~12h。
所述的酸刻蚀三维褶皱型空心MOF催化剂在硝基芳烃加氢中的应用,所述的加氢针对于硝基芳烃中的硝基苯。
本发明公开了所述的催化剂的使用条件:温度为50℃,压力为100kPa。
本发明提供的酸刻蚀空心结构的方法,被证明是一种有效的策略,可以在保留结构完整性的同时将MOF的内部挖空以形成笼状结构,制备过程简单易实施,生成空心结构的同时可以保留微孔的完整度,并且其空心化的程度是可控的,因此是一种非常具有前景的合成方法。
与现有技术相比,本发明具有如下优点:本发明所述催化剂以在水体系下,通过恒温油浴法合成出具有三维褶皱的金属有机骨架材料UiO-66,通过酸溶液刻蚀,生成空心结构。本发明采用创新性的方法,在水体系下,通过油浴恒温反应,合成出UiO-66的形貌是具有三维褶皱的八面体结构,比起传统的溶剂热法合成出表面光滑的UiO-66,褶皱的存在更进一步的提高了其比表面积,而且表面褶皱有助于所担载的金属粒子的分散,暴露出更多的活性位点,并且可以提高材料的疏水性。本发明采用酸刻蚀的方法,保留结构完整性的同时将UiO-66的内部挖空以形成笼状结构,生成空心结构的同时可以保留微孔的完整度,进一步提高了其比表面积以及有利于壳内传质,并且其空心化的程度是可控的。
本发明制备得到的酸刻蚀三维褶皱型空心MOF催化剂在硝基苯加氢反应中表现出了优异的催化性能。
附图说明:
图1为实施例1步骤(1)中制备的三维褶皱型UiO-66-NH2(Zr)和实施例4中制备的传统型UiO-66-NH2(Zr)的XRD表征图;
图2为实施例1步骤(1)中制备的三维褶皱型UiO-66-NH2(Zr);
图3为实施例4中制备的传统型UiO-66-NH2(Zr)的SEM图;
图4为实施例1步骤(2)中制备的三维褶皱型空心UiO-66-NH2(Zr)的SEM图;
图5为实施例1步骤(1)中制备的三维褶皱型UiO-66-NH2(Zr)和步骤(2)三维褶皱型空心UiO-66-NH2(Zr)的氮气吸附曲线;
图6为实施例1步骤(1)中制备的三维褶皱型UiO-66-NH2(Zr)和步骤(2)三维褶皱型空心UiO-66-NH2(Zr)的孔径分布图。
图7为应用例1硝基苯加氢制备苯胺的催化性能曲线。
具体实施方式
下面的实施例将对本发明予以进一步的说明,但本发明的内容完全不限于此。
实施例1
(1)三维褶皱型UiO-66-NH2(Zr)的制备:将116mg氯化锆,90.5mg2-氨基对苯二甲酸,9ml去离子水和6ml乙酸(配比:0.5mmol:0.5mmol:9ml:6ml)加入到50ml圆底烧瓶中,超声搅拌均匀,放到恒温油浴锅中,然后90℃反应24小时。将合成的MOF经水洗涤3次后,室温下浸入新鲜甲醇三天,每天离心换一次甲醇,再经干燥处理,所述的干燥温度为60℃,干燥时间为12h,即可制得纯化后的三维褶皱型UiO-66-NH2(Zr)。
(2)三维褶皱型空心UiO-66-NH2(Zr)的制备:取100mg步骤(1)纯化后的三维褶皱型UiO-66-NH2(Zr),加入11ml 5.76mol/L丙酸溶液,放入反应釜中,超声搅拌均匀,然后100℃反应6h。水热反应的产物经水洗涤3次后,再经干燥处理,所述的干燥温度为60℃,干燥时间为12h。
对实施例1步骤(1)中制备的三维褶皱型UiO-66-NH2(Zr)和实施例4中制备的传统型UiO-66-NH2(Zr)进行XRD测试,测试结果如图1所示。
由图1可知,采用创新性方法制备的三维褶皱型UiO-66-NH2(Zr)和传统型UiO-66-NH2(Zr)的PXRD峰十分吻合,说明形成三维褶皱型UiO-66-NH2(Zr)依然保持着良好的晶形结构。
对实施例1步骤(1)中制备的三维褶皱型UiO-66-NH2(Zr)和实施例4中制备的传统型UiO-66-NH2(Zr)进行SEM测试,测试结果分别如图2、图3所示。
由图2可知,采用创新型的方法在酸水体系下合成的UiO-66-NH2(Zr)呈现具有三维褶皱型的正八面体结构,由图3可知,传统方法合成的UiO-66-NH2(Zr)呈表面光滑的正八面体结构。
对实施例1步骤(2)中制备的三维褶皱型空心UiO-66-NH2(Zr)进行SEM测试,测试结果如图4所示。
由图4可知,采用酸刻蚀的方法能够将三维褶皱型的UiO-66-NH2(Zr)刻蚀出空心结构。
对实施例1步骤(1)中制备的三维褶皱型UiO-66-NH2(Zr)和步骤(2)三维褶皱型空心UiO-66-NH2(Zr)进行氮气吸附测试,测试结果如图5所示。
由图5可知,等温线在酸刻蚀后出现Ⅳ型回滞环,说明酸刻蚀可以使UiO-66-NH2(Zr)产生介孔。
对实施例1步骤(1)中制备的三维褶皱型UiO-66-NH2(Zr)和步骤(2)三维褶皱型空心UiO-66-NH2(Zr)的孔径分布进行测试,测试结果如图6所示。
由图6可知,三维褶皱型UiO-66-NH2(Zr)经过酸刻蚀后出现孔径为4nm左右的介孔。
实施例2
(1)三维褶皱型UiO-66-NH2(Hf)的制备:将160mg氯化铪,90.5mg 2-氨基对苯二甲酸,9ml去离子水和6ml乙酸(配比:0.5mmol:0.5mmol:9ml:6ml)加入到50ml圆底烧瓶中,超声搅拌均匀,放到恒温油浴锅中,然后90℃反应24小时。将合成的MOF经水洗涤3次后,室温下浸入新鲜甲醇三天,每天离心换一次甲醇,再经干燥处理,所述的干燥温度为60℃,干燥时间为12h,即可制得纯化后的三维褶皱型UiO-66-NH2(Hf)。
(2)三维褶皱型空心UiO-66-NH2(Hf)的制备:取100mg步骤(1)纯化后的三维褶皱型UiO-66-NH2(Hf),加入11ml 5.76mol/L丙酸溶液,放入反应釜中,超声搅拌均匀,然后100℃反应6h。水热反应的产物经水洗涤3次后,再经干燥处理,所述的干燥温度为60℃,干燥时间为12h。
实施例3
(1)三维褶皱型UiO-66-Br(Zr)的制备:将116mg氯化锆,122.5mg 2-溴对苯二甲酸,9ml去离子水和6ml乙酸(配比:0.5mmol:0.5mmol:9ml:6ml)加入到50ml圆底烧瓶中,超声搅拌均匀,放到恒温油浴锅中,然后90℃反应24小时。将合成的MOF经水洗涤3次后,室温下浸入新鲜甲醇三天,每天离心换一次甲醇,再经干燥处理,所述的干燥温度为60℃,干燥时间为12h,即可制得纯化后的三维褶皱型UiO-66-Br(Zr)。
(2)三维褶皱型空心UiO-66-Br(Zr)的制备:取100mg步骤(1)纯化后的三维褶皱型UiO-66-Br(Zr),加入11ml 5.76mol/L丙酸溶液,放入反应釜中,超声搅拌均匀,然后100℃反应6h。水热反应的产物经水洗涤3次后,再经干燥处理,所述的干燥温度为60℃,干燥时间为12h。
实施例4
传统型UiO-66-NH2(Zr)的制备:将116mg氯化锆,90.5mg 2-氨基对苯二甲酸,18mlN,N-二甲基甲酰胺和1ml乙酸(配比:0.5mmol:0.5mmol:18ml:1ml)加入到反应釜中,超声搅拌均匀,然后120℃反应24小时。将初始合成的MOF经水洗涤3次后,室温下浸入新鲜甲醇三天,每天离心换一次甲醇,再经干燥处理,所述的干燥温度为60℃,干燥时间为12h,即可制得纯化后的传统型UiO-66-NH2(Zr)。
应用例1硝基苯的加氢反应
为了考察合成的三维褶皱型空心UiO-66-NH2(Zr)催化剂对硝基苯加氢反应的催化效果,取10mg实施例1步骤(2)制备得到的三维褶皱型空心UiO-66-NH2(Zr)催化剂,通过浸渍法担载Pt颗粒,制备成负载量为5wt%三维褶皱型空心UiO-66-NH2(Zr)催化剂,测试其对硝基苯加氢反应的催化效果。
应用例1的测试结果如图7所示。
由图7可知,使用担载Pt的三维褶皱型空心UiO-66-NH2(Zr)充当催化剂时,硝基苯的转化率在反应60分钟后达到95%,而无催化剂时,硝基苯并不发生反应。结果表明,Pt可以负载到三维褶皱型空心UiO-66-NH2(Zr)上,且具有良好催化性能。
需要说明的是,本发明经酸刻蚀,在微孔金属有机骨架材料中形成空心结构和介孔,构成多级孔结构,利用不同碳链长度的羧酸实现孔径可控。且本发明多级孔结构金属有机骨架材料以及多级孔结构金属有机框架催化剂中的金属基也不局限于Zr基,其也可为Hf基,而有机配体为含有-(OH)2、-NH2、-(COOH)2等具有改性作用的官能团的有机物,如对苯二甲酸、2,5-对羟基对苯二甲酸、2-氨基对苯二甲酸等,采用这些有机配体制得的多级孔结构金属有机骨架材料可用化学式表示为UiO-66-(OH)2、UiO-66-NH2、UiO-66-(COOH)2。
以上仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种酸刻蚀三维褶皱型空心MOF催化剂,其特征在于,所述催化剂是以具有三维褶皱的金属有机骨架材料UiO-66为载体,其中UiO-66是在水体系下恒温反应合成,生成三维褶皱,再经过酸刻蚀,形成的空心结构。
2.根据权利要求1所述的酸刻蚀三维褶皱型空心MOF催化剂,其特征在于所述的金属有机骨架材料UiO-66为Zr基、Hf基或者官能团改性的金属有机骨架材料的一种。
3.权利要求1所述的酸刻蚀三维褶皱型空心MOF催化剂的制备方法,其特征在于,包括有以下步骤:
(1)UiO-66-NH2(Zr)或UiO-66-NH2(Hf)的制备:将金属锆盐或铪盐、带有不同取代基的对苯二甲酸、水和乙酸混合,搅拌均匀后,进行油浴恒温反应,冷却,再经纯化得到具有三维褶皱的UiO-66-NH2(Zr)或UiO-66-NH2(Hf);
(2)空心结构的制备:将步骤(1)得到的UiO-66-NH2(Zr)或UiO-66-NH2(Hf)与酸溶液混合,经过水热反应,冷却,经纯化、离心、干燥处理得到所述的具有褶皱的空心UiO-66-NH2(Zr)或UiO-66-NH2(Hf)。
4.根据权利要求3所述的酸刻蚀三维褶皱型空心MOF催化剂的制备方法,其特征在于,所述的带有不同取代基的对苯二甲酸为2-氨基对苯二甲酸、2-羟基对苯二甲酸、对苯二甲酸磺酸钠或2-溴对苯二甲酸。
5.根据权利要求3所述的酸刻蚀三维褶皱型空心MOF催化剂的制备方法,其特征在于,步骤(1)中,所述的金属锆盐或铪盐、带有不同取代基的对苯二甲酸、水和乙酸的配比为0.5mmol:0.5mmol:(6~9)ml:(4.5~24)ml。
6.根据权利要求3所述的酸刻蚀三维褶皱型空心MOF催化剂的制备方法,其特征在于,所述的油浴恒温反应条件为:在水体系下,60~90℃,油浴恒温反应12~36h。
7.根据权利要求3所述的酸刻蚀三维褶皱型空心MOF催化剂的制备方法,其特征在于,所述的纯化过程具体为:油浴恒温反应的产物经水洗涤3次后,室温下浸入新鲜甲醇三天,每天离心换一次甲醇,再经干燥处理,所述的干燥温度为50~70℃,干燥时间为8~12h。
8.根据权利要求3所述的酸刻蚀三维褶皱型空心MOF催化剂的制备方法,其特征在于,所述的酸溶液为单酸的水溶液,单酸和水的配比为:6ml:(1~16)ml,所述的水热反应条件为:100~120℃,油浴恒温反应3h,6h或12h。
9.根据权利要求8所述的酸刻蚀三维褶皱型空心MOF催化剂的制备方法,其特征在于,所述的单酸为甲酸、乙酸、丙酸、丁酸和月桂酸中的任意一种。
10.权利要求1所述的酸刻蚀三维褶皱型空心MOF催化剂在硝基芳烃加氢中的应用,所述的加氢针对于硝基芳烃中的硝基苯。
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