CN109046456A - 负载型锰-金属有机框架复合材料的制备方法及其应用 - Google Patents
负载型锰-金属有机框架复合材料的制备方法及其应用 Download PDFInfo
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- 229940099607 manganese chloride Drugs 0.000 claims abstract description 5
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
本发明属于一种负载型锰‑金属有机框架复合材料，公开了一种基于多孔锰‑金属有机框架材料负载贵金属（Ag）的复合催化材料及其在催化硝基苯酚和同分异构体还原中的应用。本发明采用两步法合成技术，首先利用有机配体5'‑（3,5‑二羧基苯基）‑[1,1'：3'，1“‑三联苯]‑3,3”，5,5“‑四羧酸(H6L)与氯化锰在N,N‑二甲基乙酰胺与水的混合溶液中自组装得到多孔锰‑金属有机框架材料，然后利用紫外光还原技术，将贵金属纳米颗粒负载到锰‑金属有机框架材料的基体和孔道里，最后得到分布均匀且大小均一的Ag贵金属纳米颗粒。该负载型锰‑金属有机框架复合材料催化剂在催化硝基苯酚和同分异构体还原中表现出不同的催化活性，显示出稳定和优越的催化活性。
Description
技术领域
本发明属于晶态材料及其负载型复合材料制备技术及催化应用领域，具体涉及以锰-金属有机框架材料负载贵金属形成复合材料以后催化还原硝基苯酚和同分异构体的应用
背景技术
金属有机框架材料(MOF)是近十年发展迅速的一种配位聚合物，具有三维的孔结构，一般以金属离子为连接点，有机配位体支撑构成空间3D延伸，是一种新型的晶体多孔材料，包括节点和连接桥。它具有高孔隙率、低密度、大比表面积、孔道规则、孔径可调以及拓扑结构多样性等优点。在催化、储能和分离中都有广泛应用。其中的催化应用中除了金属有机框架材料本身可作为某些有机反应体系或者特定反应的催化剂以外，利用其高比表面积以及规则均匀分布的孔道结构进行贵金属纳米粒子的负载也是催化剂材料设计制备的重要方向之一。
与此同时，对硝基苯酚(4-NP)是工业废水中很难处理的一种含酚类的有机污染物，有毒难降解，降解后的产物是一种重要的化工和西药中间体主要应用于合成解热镇痛剂，扑热息痛剂，石油添加剂等方面。因此，将对环境伤害较大的反应物转化为可以利用的化工中间原料，具有重大经济、社会意义。
发明内容
本发明提供了一种制备多孔锰-金属有机框架材料及其负载型复合材料的方法，并将复合材料应用于催化硝基苯酚和同分异构体还原反应，其制备方法合理简单，催化还原性能稳定，催化还原效率较高。
本发明采用溶剂热法，利用多元羧酸有机配体和锰盐自组装制备形成多孔金属有机框架材料，然后在贵金属盐配置的溶液中利用紫外光还原技术，结合多孔材料限域生长纳米粒子原理，将贵金属纳米颗粒负载到多孔金属有机框架材料的孔道和表面，最后得到了分散性好、催化活性高的负载型金属有机框架复合材料。
为实现上述目的，本发明采用的技术方案为：
(1)将金属盐、H6L(C30H18O12)、N，N-二甲基乙酰胺、HBF4和水混合后超声，得到混合溶液；
(2)将上述步骤(1)得到的混合溶液转移至聚四氟乙烯反应釜中，在100-150℃下进行水热反应(进一步优选为水热反应温度为120℃，水热反应时间为2-3天，得到浅黄色块状晶体；
(3)将上述步骤(2)得到的浅黄色块状晶体用乙醇浸泡，以除去孔道中的残余溶剂分子。
(4)将上述步骤(3)将得到的块状晶体用乙醇清洗干净，干燥，即得到所述锰-金属有机框架材料。
所述的金属盐为氯化锰。
所述的N，N-二甲基乙酰胺、HBF4和去离子水的体积比为1.5-3：0.5-1.5：0.5-1.5，N，N-二甲基乙酰胺、HBF4和去离子水的量浸没于金属盐与H6L即可。氯化锰与配体H6L的质量比为3-3.5:1-1.5。
利用以上步骤所制备的晶态材料作为前驱体负载Ag纳米颗粒催化降解硝基苯酚实验，具体步骤如下：
1)将待负载样品浸入硝酸银水溶液中，室温下静置24小时后，采用功率为300W的汞灯利用紫外光光照还原得到混合液，得到的混合液产物经过滤后，依次采用蒸馏水和无水乙醇分别洗涤三次，得到的产物，将产物在60℃～100℃下真空干燥4-6小时即可得到负载Ag纳米粒子的金属有机框架复合材料。
2)将负载型锰-金属有机框架复合材料按0.15g/L～0.5g/L的比例投加到浓度为14mg/L～25mg/L的硝基类苯酚的溶液中，加入硼氢化钾，反应温度为室温，反应时间为0min～20min，即可完成全部的硝基类苯酚的还原过程。
本发明具有以下优点：
1)本发明所制备的方法相对简单，可控性强；
2)本发明所制备的催化剂材料为负载型锰-金属有机框架复合材料；
3)本发明所制备的催化剂材料具有优异的催化降解的能力；
4)本发明的制备均为实验室常用设备，不需要专门设备，工艺流程简单。
附图说明
图1为本发明所制备晶态材料锰-金属有机框架材料配体的配位环境图。
图2为本发明所制备晶态材料锰-金属有机框架材料的三维层状堆积图。
图3为本发明所制备晶态材料锰-金属有机框架材料的拓扑图。
图4为本发明所制备晶态材料锰-金属有机框架材料的X射线衍射(XRD)图。
图5为本发明所制得的负载型锰-金属有机框架复合材料的扫描电镜mapping图，包括Ag，C，O，Mn四种元素。
图6为本发明所制得的晶态材料锰-金属有机框架材料催化还原对硝基苯酚紫外-可见吸收光谱表征图。
图7为本发明所制得的负载型锰-金属有机框架复合材料催化还原对硝基苯酚紫外-可见吸收光谱表征图。
图8为本发明所制得的负载型锰-金属有机框架复合材料催化还原邻硝基苯酚紫外-可见吸收光谱表征图。
图9为本发明所制得的负载型锰-金属有机框架复合材料催化还原间硝基苯酚紫外-可见吸收光谱表征图。
具体实施方式
下面结合实施例来进一步说明本发明，但本发明要求保护的范围并不局限于实施例表述的范围。
实施例1
取0.15mmol氯化锰、0.05mmolH6L、3mlDMA、0.5mlHBF4和0.5ml水放入烧杯中，进行超声使其反应物均匀分散在溶液中；所得到的均匀混合溶液转移至25ml聚四氟乙烯反应釜中；将装有混合溶液反应釜放至120℃恒温烘箱中反应56h，然后室温下降至室温，可得浅黄色块状晶体；将得到的浅黄色块状晶体用无水乙醇浸泡3天，然后清洗干净，并在60℃下干燥，即得到所述锰-金属有机框架材料，该晶态材料的配体的配位环境图与三维堆积图见图1、图2，，图3是它的6,6链接的拓扑图。
上述制备的锰-金属有机框架材料经过XRD分析，结果见图4，合成的Mn-MOF其特征衍射峰(100)、(101)、(102)、(212)、(210)与模拟Mn-MOF的高度重合性，说明制备了结构规整的锰-金属有机框架材料。
实施例2
1)将实施例1中得到的多孔锰-金属有机框架材料经过溶剂置换出客体分子后作为载体(客体分子主要指晶态材料合成中引入的水分子和DMA分子，由于该材料具备孔道结构，两者在孔道中会有一定的残留)。置换方式为：将晶态材料样品置于乙醇溶液中浸泡48小时，每24小时更换一次乙醇溶液，再在80℃真空干燥6小时。随后取100mg置换过的晶态材料加入到15ml去离子水中，然后加入0.5ml的10mg/L的硝酸银溶液，将上述的混合体系静置24小时。
2)将上述的混合体系转移到光化学反应器的石英试管中，在搅拌的条件下，利用功率为300W的汞灯利用紫外光照射3h，还原得到新的混合体系。
3)得到的产物经过滤分离后，依次采用蒸馏水和无水乙醇分别洗涤三次，得到的产物80℃真空干燥即可得到Ag@Mn-MOF新型复合材料。
上述制备的负载型锰-金属有机框架复合材料(Ag@Mn-MOF)扫描电镜如图5，从电镜mapping照片可看出，Ag元素分布均匀且与C、O、Mn元素基本重合，说明Ag纳米颗粒均匀的分布在锰-金属有机框架材料上。
上述制备的负载型锰-金属有机框架复合材料(Ag@Mn-MOF)催化还原硝基类苯酚性能图见图5、6、7、8，对比可以看出，在催化原硝基类苯酚过程中，负载型锰-金属有机框架复合材料相比于纯晶态材料锰-金属有机框架材料有着更优异的催化活性。
上述的实施例仅为本发明的优选技术方案，而不应视为对于本发明的限制，本申请中的实施例及实施例中的特征在不冲突的情况下，可以相互任意组合。任何熟悉本技术领域的技术人员在本发明的思想和原则之内可轻易想到的变化，替换和改进都应涵盖在本发明的保护范围内。
Claims (8)
1.一种负载型锰-金属有机框架复合材料，其特征在于，该复合材料为Ag负载三维多孔锰-金属有机框架晶态材料(C30H15Mn3O16)，该材料具有规则的多孔结构及高的孔隙率54.3％，所述的Ag的负载量为0.5wt％～50wt％。
2.权利要求1所述的锰-金属有机框架材料的制备方法，其特征在于，包括以下步骤：
(1)将金属锰盐、H6L(C30H18O12)、N，N-二甲基乙酰胺、HBF4和水混合后超声，得到混合溶液；
(2)将上述步骤(1)得到的混合溶液转移至聚四氟乙烯反应釜中，在100-150℃下进行水热反应，得到浅黄色块状晶体；
(3)将上述步骤(2)得到的浅黄色块状晶体用乙醇浸泡数天，以除去孔道中的残余溶剂分子；
(4)将上述步骤(3)得到的浅黄色块状晶体干燥，即得到所述的锰-金属有机框架材料；
(5)取(4)中锰-金属有机框架材料浸入硝酸银水溶液中，室温下静置20-30h后紫外光光照还原得到混合液产物，过滤，洗涤，真空干燥得到负载Ag纳米粒子的锰-金属有机框架复合材料。
3.权利要求2所述的锰-金属有机框架材料的制备方法，其特征在于，N，N-二甲基乙酰胺、HBF4和去离子水的体积比为1.5-3：0.5-1.5：0.5-1.5。
4.权利要求2所述的锰-金属有机框架材料的制备方法，其特征在于，所述的金属锰盐包括氯化锰、硝酸锰；其中金属锰盐与配体H6L(C30H18O12)的质量比为3-3.5:1-1.5。
5.权利要求2所述的锰-金属有机框架材料的制备方法，其特征在于，所述步骤(2)水热反应温度为120℃，水热反应时间为2～3天。
6.权利要求2所述的锰-金属有机框架材料的制备方法，其特征在于，所述步骤(3)洗涤后的产物用无水乙醇浸泡，浸泡总时间为2.5～4天。
7.权利要求1所述的负载型金属有机框架复合材料的制备方法，其特征在于，步骤(5)中，锰-金属有机框架材料：硝酸银：去离子水质量比：4:1～4:1～2。
8.权利要求1-7任一项所述负载型锰-金属有机框架复合材料在催化降解硝基类苯酚及同分异构体的应用。
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