CN106902883A - 一种负载Keggin杂多酸阴离子的金属有机框架材料及其制备方法 - Google Patents
一种负载Keggin杂多酸阴离子的金属有机框架材料及其制备方法 Download PDFInfo
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- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 235000019832 sodium triphosphate Nutrition 0.000 abstract 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 abstract 1
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- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 3
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
一种负载Keggin杂多酸阴离子的金属有机框架材料，化学式为：[Ag8L5](PM12O40)·(H2O)x，式中：L为有机配体分子5‑苯基四氮唑；M为钨或钼中的一种；M为钨时，x=13；M为钼时，x=10。以及一种负载Keggin杂多酸阴离子的金属有机框架材料的制备方法，具体步骤包括：室温条件下，将Keggin型金属磷酸与硝酸银、5‑苯基四氮唑加入溶解量的去离子水中充分搅拌，用稀硝酸调节pH值，转移到高温高压反应釜中，水热条件下，反应72h，冷却到室温，过滤，用蒸馏水冲洗，干燥后得到负载Keggin杂多酸阴离子的金属有机框架材料。本发明制备的催化剂具有催化活性高、利于催化剂的回收的特点。
Description
技术领域
本发明属于光降解催化剂技术领域，具体涉及一种负载Keggin杂多酸阴离子的金属有机框架材料及其制备方法。
背景技术
近几十年来，伴随着工业化进程的加快、资源的过度开发利用和人类活动范围的扩大，环境问题日益引起世界各国的广泛关注。工业和人们日常生活的废水、废气中常常含有大量的有毒难降解的有机污染物，这类难降解的有机污染物可使生态环境遭受严重的破坏。随着国际环境标准要求日益严格化，有机污染的治理技术也得到快速发展。近年来作为新兴的污染治理技术，光催化在环境保护中的应用日益受到人们的重视。光催化是利用光照使半导体光催化剂受到激发，从而在半导体的导带和价带位置分别形成光生电子和空穴，生成的光生电子和空穴随后可参与有机物的光催化降解反应。与现有的治理技术相比，光催化过程用于降解环境有机污染物具有较多的优点。第一，光催化对有机污染物的破坏常常是彻底的，即能将有机污染物完全转化为水、二氧化碳和其它矿物质；第二，即使光催化过程不能使有机物完全矿化，降解的最终产物对环境通常也是无害或者低害的，或能被进一步的生物或化学方法处理而成为无害的产物；第三，到目前为止，光催化过程可部分利用太阳能作为光源，因而运行成本低廉；第四，光催化剂本身的成本相对低廉，且化学性质稳定，对环境不会造成污染。
TiO2作为代表性的光催化材料，它优良的光催化特性已为许多研究者证实，并在净化空气、治理污水等方面有着良好的应用前景。但本身还存在一些不足，如半导体载流子的复合率高、量子效率低，半导体的光吸收波长窄主要在紫外区，利用太阳光的比例低等。就多酸而言，在光照下，多酸发生类似的电荷一空穴对分离，通过自身氧化和产生·OH自由基来实现有机污染物的降解。多酸的吸收峰尽管大都位于紫外区，但其谱带的尾部可延伸到可见光区，通过对多酸组成的改变更换杂原子或配原子等，利用其特殊的空间结构形成独特的反应场，从而有效地调节多酸的光谱性质。多酸作为环境友好的光催化剂，在利用分子氧和太阳能处理环境污染物方面已显示出良好的应用前景。基于此，本发明涉及一种负载杂多酸阴离子的金属有机框架光催化剂的合成及制备方法，成本低廉，方法简单。此外，本发明中的光催化剂材料均对水体中的有机染料分子具有很好的光降解效果，使得本发明更具有创新性、突破性。
发明内容
为了克服现有技术的上述问题，本发明的目的是提供一种负载Keggin杂多酸阴离子的金属有机框架材料及其制备方法。本发明制备的催化剂能够大幅度提高光催化活性物质的比表面积，提升催化活性；同时，将催化剂制备成难溶杂化材料，利于催化剂的回收。
本发明的技术方案是：
一种负载Keggin杂多酸阴离子的金属有机框架材料，其化学式如通式（Ⅰ）所示：
[Ag8L5](PM12O40)·(H2O)x （Ⅰ）
式中：L为有机配体分子5-苯基四氮唑；M为钨或钼中的一种；M为钨时，x=13；M为钼时，x=10。
以及，一种负载Keggin杂多酸阴离子的金属有机框架材料的制备方法，反应方程式如式（Ⅱ）所示
Ag+ ＋ L ＋ H3PM12O40·12H2O＋ H2O → [Ag8L5](PM12O40)·(H2O)x（Ⅱ）
具体步骤包括：
1）室温条件下，将配方量的Keggin型杂多酸与硝酸银、5-苯基四氮唑加入溶解量的去离子水中，搅拌1~2h；
2）充分搅拌后，用稀硝酸调节其pH值调至1.60~2.00；
3）将步骤2）所得溶液转移到高温高压反应釜中，在160℃，水热条件下，反应72h；
4）停止反应，将高温高压反应釜冷却到室温，过滤，用蒸馏水冲洗，干燥后得到负载Keggin杂多酸阴离子的金属有机框架材料。
所述Keggin型杂多酸与硝酸银、5-苯基四氮唑（HL）的配方，1份配方中各组分的摩尔份数为：
Keggin型杂多酸 0.1~0.15份
硝酸银 1份
5-苯基四氮唑（HL） 0.21份
其中，Keggin型杂多酸为H3PW12O40·12H2O或H3PMo12O40·12H2O中的一种。
所述步骤4）中冷却降温过程的降温速度为10℃/h。
本发明中光催化剂材料的优点是：
1）本发明通过把一种具有光催化活性的Keggin型杂多酸阴离子负载到金属有机框架中，将Keggin多阴离子均匀分散，提高了催化剂的比表面积，进而提高其光催化活性。
2）将杂多酸与金属有机框架进行杂化制备成难溶的杂化材料，利于光催化剂的回收。
3）由于该杂化材料中杂多酸阴离子具有光催化活性，且均匀分散，能够高效降解水体中的有机染料分子，在污水处理、有机物降解等应用方面具有巨大的潜力。
附图说明
图1是该光催化剂的结构模型图；图中，a为金属有机框架；b为杂多酸负载的金属有机框架；
图2是实施例1中材料的光催化降解甲基橙的紫外-可见吸收图谱；
图3是实施例2中材料的光催化降解甲基橙的紫外-可见吸收图谱。
具体实施方式
下面给出实施例以对本发明进行具体描述，有必要在此指出的是以下实施例只用于对本发明进行进一步的说明，不能理解为对本发明保护范围的限制，本领域的技术熟练人员根据上述本发明的内容对本发明做出的一些非本质的改进和调整仍属于本发明的保护范围。
实施例1
本实例制备的是磷钨酸负载的金属有机框架材料，合成步骤如下：
[Ag8L5](PW12O40)·(H2O)13 （Ⅲ）的合成：
将H3PW12O40·12H2O (0.30 g, 0.097 mmol)，AgNO3 (0.17 g, 1.00 mmol)，HL (0.03g, 0.21 mmol)以及H2O (10 mL) 制备成混合溶液，放于室温下搅拌1小时，然后用1 M HNO3将pH 调至1.60~2.00 的范围，接着将该混合溶液转移到 18 mL的高温高压反应釜中，放入160℃烘箱中反应三天。反应结束后，以10℃/h 的降温速率将反应釜缓慢冷却到室温，过滤，用蒸馏水冲洗，室温下干燥后得到淡绿色块状晶体，产率为58%。
该化合物测得的红外数据如下：
IR (固态KBr片, cm-1): 3467 (w), 1607 (w), 1457 (m), 1368 (m), 1279 (w),1245 (w), 1156 (w), 1074 (s), 978 (s), 882 (s), 800 (s), 732 (w), 698 (w),595 (w), 506 (m)。
实施例2
本实例制备的是磷钨酸负载的金属有机框架材料，合成步骤如下：
[Ag8L5](PMo12O40)·(H2O)10 （Ⅳ）的合成：
将H3PMo12O40·12H2O (0.30 g, 0.15 mmol) , AgNO3 (0.17 g, 1.00 mmol), HL(0.03 g, 0.21 mmol)以及H2O (10 mL) 制备成混合溶液，放于室温下搅拌2小时，然后用1M HNO3将pH 调至1.60~2.00 的范围，接着将该混合溶液转移到 18 mL的高温高压反应釜中，放入 160℃烘箱中反应三天。反应结束后，以10℃/h 的降温速率将反应釜缓慢冷却到室温，过滤，用蒸馏水冲洗，室温下干燥后得到黄色块状晶体，产率为52%。
该化合物测得的红外数据如下：
IR (固态KBr片，cm-1): 3439 (w), 1607 (w), 1457 (m), 1375 (w), 1286 (w),1238 (w), 1156 (w), 1067 (s), 964 (s), 882 (s), 800 (s), 732 (w), 691 (w),602 (w), 506 (w)。
实施例3
依据实施例1和实施例2分别合成了磷钨酸和磷钼酸多阴离子负载的金属有机框架材料（Ⅲ） 和（Ⅳ），在紫外光照下，对这两种材料的光降解甲基橙的性能进行了测试，实施例1、实施例2所得产物在不同条件下光催化降解甲基橙的紫外-可见吸收图谱如图2、图3所示。
测试结果表明：在酸性条件下，光催化剂材料（Ⅲ）在紫外光照射180 min后，对甲基橙有机污染物的光降解率达到90.66%；光催化剂材料（Ⅳ）在紫外光照射180 min后，对甲基橙有机污染物的光降解率达到93.34%。
Claims (4)
1.一种负载Keggin杂多酸阴离子的金属有机框架材料，其特征在于杂多酸阴离子均匀分散在金属有机框架材料的孔道中，其化学式如通式（Ⅰ）所示：
[Ag8L5](PM12O40)·(H2O)x （Ⅰ）
式中：L为有机配体分子5-苯基四氮唑；M为钨或钼中的一种；M为钨时，x=13；M为钼时，x=10。
2.一种负载Keggin杂多酸阴离子的金属有机框架材料的制备方法，其特征在于，反应方程式如式（Ⅱ）所示
Ag+ ＋ HL ＋ H3PM12O40·12H2O＋ H2O → [Ag8L5](PM12O40)·(H2O)x（Ⅱ）
具体步骤包括：
1）室温条件下，将配方量的Keggin型杂多酸与硝酸银、5-苯基四氮唑加入溶解量的去离子水中，搅拌1~2h；
2）充分搅拌后，用稀硝酸调节其pH值调至1.60~2.00；
3）将步骤2）所得溶液转移到高温高压反应釜中，在160℃，水热条件下，反应72h；
4）停止反应，将高温高压反应釜冷却到室温，过滤，用蒸馏水冲洗，干燥后得到负载Keggin杂多酸阴离子的金属有机框架材料。
3.根据权利要求2所述的一种负载Keggin杂多酸阴离子的金属有机框架材料的制备方法，所述Keggin型杂多酸与硝酸银、5-苯基四氮唑的配方，1份配方中各组分的摩尔份数为：
Keggin型杂多酸 0.1~0.15份
硝酸银 1份
5-苯基四氮唑 0.21份
其中，Keggin型杂多酸为H3PW12O40·12H2O或H3PMo12O40·12H2O中的一种。
4.根据权利要求2所述的一种负载Keggin杂多酸阴离子的金属有机框架材料的制备方法，所述步骤4）中冷却降温过程的降温速度为10℃/h。
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