CN108273505B - Co/Co3O4复合材料及其制备方法和应用 - Google Patents
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Abstract
本发明涉及一种Co/Co3O4复合材料及其制备方法和应用。采用的技术方案是：硝酸钴、H3btb超声分散，并将溶液放入到玻璃瓶中，在85℃下静置72h，得到Co6(btb)4(4,4′‑bipy)3复合材料。并将该材料在氮气环境下，800℃煅烧1小时得到Co/Co3O4复合材料。本发明合成的Co/Co3O4复合材料对对硝基苯酚还原反应具有高效的催化活性。
Description
技术领域
本发明属于贵金属催化有机物合成领域，将新型金属有机骨架材料Co6(btb)4(4,4′-bipy)3作为原料，使其煅烧，形成一种新的Co/Co3O4复合材料，催化传统方法很难生成且转化率和选择性都很低的对氨基苯酚。
背景技术
对氨基苯酚是一种重要的有机合成中间体和化工原料，对氨基苯酚是具有多官能团的有机化合物，其分子中的羟基呈弱酸性，氨基呈弱碱性，苯环可进行磺化、硝化、卤化，烃化等反应，因而生成繁多的衍生物，是合成多种有机产品的主要原料。
近年来，贵金属纳米材料一直是催化领域研究的热点，对氨基苯酚用作医药中间体的消费量在我国占总消费量的80％，占世界对氨基苯酚消费量的30％。我国用对氨基苯酚合成的医药类产品有扑热息痛(对乙酰氨基酚)、安妥明(对氯苯氧基甲基丙酸乙醇)、维生素Bl、烟酰胺复合剂、6-羟基喹啉、扑炎痛(对乙酸氨基乙酸水杨酸酯)等。对氨基苯酚的衍生物在国外被制造成名目繁多的解热镇痛药物。
然而现有技术中，采用传统方法制备对氨基苯酚，不仅很难生成，而且转化率和选择性都很低。
发明内容
本发明的目的在于，通过热解晶体生成一种具备孔洞结构的全新Co/Co3O4复合材料。该复合材料在对硝基苯酚还原反应过程中存在选择性催化作用。
本发明采用的技术方案是：一种Co/Co3O4复合材料，制备方法如下：将Co6(btb)4(4,4′- bipy)3在氮气环境下，800℃煅烧1-2h，得到Co/Co3O4复合材料。
上述的Co/Co3O4复合材料，所述的Co6(btb)4(4,4′-bipy)3的制备方法如下：将Co(NO3)2和H3btb置于玻璃瓶中，同时加入N,N-二甲基甲酰胺，超声处理20min，然后将玻璃瓶放入烘箱中，于85℃下，反应72h，反应结束后，移去溶液中的液体，用N,N-二甲基甲酰胺清洗，过滤，将固体颗粒放入真空干燥箱中80℃真空干燥。
上述的Co/Co3O4复合材料在选择性催化对硝基苯酚还原生成对氨基苯酚反应中的应用。方法如下：取一定量的对硝基苯酚和硼氢化钠，溶于蒸馏水中，得混合液；将混合液和Co/Co3O4复合材料置于茄型反应瓶中，不断搅拌，室温反应20min。
本发明的有益效果是：本发明合成的Co/Co3O4复合材料，对对硝基苯酚还原具有选择性催化活性。本发明合成的Co/Co3O4复合材料，合成方法简单，具有良好的重复利用能力。
附图说明
图1是实施例1合成的Co/Co3O4复合材料的XRD图。
图2是实施例1合成的Co/Co3O4复合材料的扫描电镜图。
图3是实施例1合成的Co/Co3O4复合材料的拉曼射线衍射图。
图4是实施例1合成的Co/Co3O4复合材料的氮气吸附图。
图5是实施例1合成的Co/Co3O4复合材料催化对硝基反应14min后反应物的转化率图。
图6是实施例1合成的Co/Co3O4复合材料催化对硝基反应14min第五次时14min后反应物的转化率图。
具体实施方式
实施例1Co/Co3O4复合材料
(一)制备方法
1)Co6(btb)4(4,4′-bipy)3晶体的制备：将0.03g Co(NO3)2和0.01g H3btb置于5ml玻璃瓶中，同时加入2ml N,N-二甲基甲酰胺，超声处理20min，然后将5ml玻璃瓶放入烘箱中，于 85℃下，反应72h，反应结束后，移去溶液中的液体，用N,N-二甲基甲酰胺清洗，过滤，将固体颗粒放入真空干燥箱中80℃真空干燥。
2)Co6(btb)4(4,4′-bipy)3晶体的活化：将Co6(btb)4(4,4′-bipy)3晶体放入真空干燥箱中120℃真空干燥36h，得到活化后的Co6(btb)4(4,4′-bipy)3晶体，氮气条件下保存。
3)将Co6(btb)4(4,4′-bipy)3在氮气环境下，在管式炉中800℃下煅烧1小时，得到Co/Co3O4复合材料。
(二)检测结果
1、将制备的Co/Co3O4复合材料，进行XRD表征，结果如图1所示。由图1可见，本发明合成的Co/Co3O4复合材料结构的完整性。44.2°和51.5°表明Co的特征衍射峰， 35.6°代表着Co/Co3O4特征峰。
2.将得到的Co/Co3O4复合材料，进行透射电子显微镜和X射线衍射仪表征，扫描电镜如图2所示，由图2可见Co/Co3O4复合材料分布很均匀并且具有良好的材料特性。拉曼射线衍射表征结果如图3所示，由图3可见，图3中D带位于1328cm-1是由于碳材料的缺陷与边缘杂化振动模式引起的，G带位于1580cm-1是来源于碳材料中所有sp2杂化碳原子的杂化的面内伸缩振动引起，IG/ID的比例为1.2，碳材料中包含石墨化碳和无定形碳，体现了优良的石墨化程度。由图4可知，Co/Co3O4复合材料吸附表现出IV型BET曲线伴有 H3型滞后环说明此碳材料中存在大量介孔结构，说明在高温碳化过程中MOFs的高比表面积和孔结构可以被保留下来，这非常有利于氧还原反应。
实施例2Co/Co3O4复合材料催化对硝基苯酚还原反应
方法如下：将20ml浓度为50mg/L的对硝基苯酚、0.19g硼氢化钠溶解到30ml水中，得混合液；于混合液中加入实施例1制备的10mgCo/Co3O4复合材料，置于100mL锥形瓶中，将反应装置固定好。在室温下反应，反应14min后，分别取反应液进行紫外-可见光分光光度计进行监测，结果如图5所示。
图5为本发明合成的Co/Co3O4复合材料在反应0min和14min后产物的转化率图。由图5可见，通过紫外分析色谱分析0min时在350nm波长处出现一个吸收峰，此时未有产物生成，当进行到14min时，该吸收消失，此时的反应物完全转换，转换率和选择性为百分之百。
本发明的Co/Co3O4复合材料能够选择性催化对硝基苯酚还原反应，转化率和选择性都很高，有利于反应物的高效利用，并且方便产物的提纯与分离。
实施例3Co/Co3O4复合材料重复性试验
将实施例2反应结束后，分离出Co/Co3O4复合材料，重复实施例2的实验4次。图6是实施例1合成的Co/Co3O4复合材料催化对硝基苯酚还原反应第五次时0min和14 min后产物的转化率图。通过重复试验，反应第五次的Co/Co3O4复合材料转化率95％，对硝基苯酚的选择性为100％，仍然具有良好的催化活性和选择性。证明本发明合成的 Co/Co3O4复合材料具有很好的循环利用性。
Claims (3)
1.一种Co/Co3O4复合材料，其特征在于，制备方法如下：
1）Co6(btb)4(4,4´-bipy)3 晶体的活化：将Co6(btb)4(4,4´-bipy)3晶体放入真空干燥箱中120 oC真空干燥36 h，得到活化后的Co6(btb)4(4,4´-bipy)3晶体，氮气条件下保存；
2）将步骤1）得到的Co6(btb)4(4,4´-bipy)3在氮气环境下，800 ℃煅烧1-2 h，得到Co/Co3O4复合材料。
2.权利要求1所述的Co/Co3O4复合材料在选择性催化对硝基苯酚还原生成对氨基苯酚反应中的应用。
3.根据权利要求2所述的应用，其特征在于，方法如下：取一定量的对硝基苯酚和硼氢化钠，溶于蒸馏水中，得混合液；将混合液和Co/Co3O4复合材料置于茄型反应瓶中，不断搅拌，室温反应20 min。
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| CN106832321A (zh) * | 2017-02-06 | 2017-06-13 | 辽宁大学 | 一种双核Co簇金属有机骨架材料及其合成方法和应用 |
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