CN107715910A - 基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料及其制备方法与应用 - Google Patents
基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料及其制备方法与在光催化降解一氧化氮气体中的应用;首先以双氰胺为原材料高温下煅烧制备片状氮化碳;再以苝四酸二酐和氮化碳为原料,咪唑为溶剂,在高温加热条件下制得苝四酸二酐的氮化碳;苝四酸二酐修饰的氮化碳和氧化石墨烯均匀分散在去离子水中,超声搅拌后转入到反应釜中进行反应,再经过冷冻干燥制得苝四酸二酐修饰氮化碳与氧化石墨烯组成的气凝胶复合材料。本发明通过一系列步骤合成的氮化碳氧化石墨烯气凝胶材料对一氧化氮气体有着很好的光催化效果,且可多次循环使用;并且其具有制备过程简便,易于回收多次利用等优点,在氮氧化物气体处理方面具有工业应用前景。
Description
技术领域
本发明涉及功能材料技术领域,具体涉及到一种基于苝四酸二酐修饰的氮化碳与氧化石墨烯组成的气凝胶复合材料及其制备方法与在一氧化氮光催化处理中的应用。
背景技术
一氧化氮污染是一种典型的气体环境污染。随着中国经济和工业的快速发展,全国汽车数量也在增加。汽车尾气排放到空气中是造成环境污染的主要原因。因此,主要城市的PM 2.5(PM为颗粒物质)的浓度水平远高于国家环境空气质量标准。最近中国经历了严重的严重霾事件,然而氮氧化物(主要包括一氧化氮和二氧化氮)是这些污染事件的罪魁祸首。因此,开发有效和经济的技术来解决一氧化氮污染是一个迫切的问题。目前,已有许多处理一氧化氮的方法,例如物理吸附,生物过滤,热催化还原和选择的催化还原,但这些方法对于在低浓度(十亿分之一级别)水平下一氧化氮的处理是不经济的和低效的。半导体光催化被认为是降解低浓度一氧化氮的有前途的技术,由于其高效率和环保特性,在解决全球能源短缺方面具有潜在的价值,然而,现有处理剂降解一氧化氮的效果远远不能达到人们预期的效果。
发明内容
本发明目的是提供一种基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料及其制备方法,通过双氰胺在高温煅烧条件下进行分子聚合而形成片状氮化碳材料,在利用苝四酸二酐对该氮化碳进行修饰,与氧化石墨烯混合进行水热反应得到水凝胶,再进行冷冻干燥得到苝四酸二酐修饰氮化碳与氧化石墨烯组成的气凝胶复合材料,以实现该材料在一氧化氮的光催化降解方面得到广泛的应用。
为了达到上述目的,本发明具体技术方案如下:
一种基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料的制备方法,包括以下步骤:
(1)以双氰胺为原料,高温煅烧条件下,通过分子聚合作用制备片状氮化碳;
(2)将苝四酸二酐和氮化碳在高温加热条件下反应,咪唑为溶剂,制备苝四酸二酐修饰的氮化碳材料;
(3)将苝四酸二酐修饰的氮化碳和氧化石墨烯均匀分散在去离子水中,进行反应,再经过冷冻干燥,制得苝四酸二酐修饰氮化碳与氧化石墨烯组成的气凝胶复合材料,即基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料。
本发明还公开了一种基于苝四酸二酐修饰的氮化碳/氧化石墨烯水凝胶复合材料的制备方法,包括以下步骤:
(1)以双氰胺为原料,煅烧制备片状氮化碳;
(2)将苝四酸二酐和片状氮化碳在咪唑中反应,制备苝四酸二酐修饰的氮化碳材料;
(3)将苝四酸二酐修饰的氮化碳和氧化石墨烯分散到去离子水中,反应制得基于苝四酸二酐修饰的氮化碳/氧化石墨烯水凝胶复合材料。
上述技术方案中,步骤(1)中,双氰胺放入瓷坩埚中,氩气保护下,在400~700 ℃下煅烧3~6小时,煅烧的升温速率为每分钟2~15 ℃,得到黄色的片状氮化碳,并研磨成粉末,在本发明条件下可以简便高效的得到大量的片状氮化碳。
上述技术方案中,步骤(2)中,将质量比为1:30:120的苝四酸二酐、氮化碳、咪唑加入到烧瓶中,在氮气保护下,油浴加热在到130~160 ℃,反应时间为4~7小时;反应结束后冷却至室温,将将产物转移到碳酸钾水溶液中,回流1~3小时,冷却至室温,离心,用盐酸洗,再用水和乙醇洗至中性,真空干燥3~6小时,该方法可以将苝四酸二酐分子成功地修饰到氮化碳的表面。
上述技术方案中,步骤(3)中,将质量比为3:1的苝四酸二酐修饰的氮化碳和氧化石墨烯分散到水中,超声搅拌2小时,使其分散均匀;将分散均匀的悬浊液转移至反应釜中进行反应,温度为160~200 ℃,时间为5~8小时,反应结束后,自然冷却至室温,制得柱状水凝胶;将水凝胶放在冷冻干燥箱中冷冻干燥1~2天,最后得到氮化碳石墨烯气凝胶,该条件下可以很容易的得到目标产物,且该材料具有很好的导电性能。
本发明以双氰胺为初始原料,高温条件下煅烧制备片状氮化碳;再以苝四酸二酐和氮化碳为原料,咪唑为溶剂,在高温加热条件下制得苝四酸二酐修饰的氮化碳,用碳酸钾,盐酸,水,乙醇洗去反应中的溶剂的杂质;再将苝四酸二酐修饰的氮化碳和氧化石墨烯均匀分散在去离子水中,超声搅拌后转入到反应釜中进行反应,再经过冷冻干燥制得苝四酸二酐修饰氮化碳与氧化石墨烯组成的气凝胶复合材料;可以大大增加该光催化材料对可将光的吸收,具有合适的带隙,且具有很好的导电性,可大大提高光催化性能。因此本发明公开了上述基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料在光催化降解一氧化氮中的应用;同时,本发明还公开了上述基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料在气体污染处理中的应用。
本发明的优点:
1、本发明公开的基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料的制备方法简单,原料易得,而且操作简便,整个过程中没有用到昂贵的设备,对工业化应用十分关键。
2、本发明公开的基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料中,氮化碳光催化降解一氧化氮有着较好地效果,通过对氮化碳材料的改良,可以进一步改善其光催化活性;氧化石墨烯作为导电材料的引入可以大大提高电子传输的效率,进而增加降解效果;气凝胶是通过材料之间的分子作用而形成的宏观材料,有利于光催化剂的回收和重复利用,同时又可以增加对气体的吸附效果,具有很好的应用前景。
3、本发明公开的基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料是一种具有对可将光吸收效率高、催化效果好、性能稳定、可便捷的重复多次利用新型复合材料,对一氧化氮的降解具有高效率的光催化效果,可以用于各种环境下的气体污染的处理。
附图说明
图1 为氮化碳的扫描电镜图(SEM);
图2 为氮化碳的透射电镜图(TEM);
图3 为苝四酸二酐修饰氮化碳的透射电镜图(TEM);
图4 为苝四酸二酐修饰氮化碳与氧化石墨烯组成的气凝胶复合材料的扫描电镜图(SEM);
图5 为苝四酸二酐修饰氮化碳与氧化石墨烯组成的气凝胶复合材料的透射电镜图(TEM);
图6 为降解一氧化氮的效果图;
图7 为苝四酸二酐修饰氮化碳与氧化石墨烯组成的气凝胶复合材料降解一氧化氮的循环图。
具体实施方式
实施例一
氮化碳的制备,具体步骤如下:
10克双氰胺放入瓷坩埚中,氩气保护下,以每分钟10℃的升温速率加热至600℃,煅烧5小时,得到黄色的片状氮化碳,并研磨成粉末;附图1和附图2分别为的氮化碳的SEM图和TEM图,通过图片可以看出氮化碳为薄的片状结构。
苝四酸二酐修饰氮化碳的制备,具体步骤如下:
将0.05克苝四酸二酐、1.0克氮化碳和4.0克咪唑分别加入到圆底烧瓶中,其中咪唑作为溶剂,在高温条件下融化成液体,该反应体系在氮气气体保护下,油浴加热到150℃,反应6小时;待反应结束后,自然冷却至室温,将产物转移到含有150毫升碳酸钾水溶液的烧瓶中,回流2小时,反应结束后自然冷却至室温,将产物离心分离,用盐酸洗以中和剩余的碱液,再用水和乙醇洗至中性,真空干燥5小时,得到苝四酸二酐修饰氮化碳;附图3为苝四酸二酐修饰氮化碳的TEM图,通过图片可以看到其结构也是薄的片状结构。
苝四酸二酐修饰氮化碳与氧化石墨烯组成的气凝胶的制备,具体步骤如下:
将90毫克的苝四酸二酐修饰的氮化碳和30毫克氧化石墨烯分散到20毫升水中,超声搅拌2小时,使其分散均匀,将分散均匀的悬浊液转移至反应釜中进行水热反应,温度为190℃,时间为6小时,反应结束后,自然冷却至室温,制得柱状水凝胶,用去离子水将水凝胶洗三遍;然后将水凝胶放在表面皿中,转移到冷冻干燥箱中冷冻干燥2天,最后得到柱状的基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料;附图4和附图5分别为苝四酸二酐修饰氮化碳石墨烯气凝胶的SEM和TEM图,通过图片可以看出该材料呈大孔状结构,且氮化碳和石墨烯得到了很好的复合。
实施例二
一氧化氮气体的光催化降解,具体步骤如下:
将含有一个石英玻璃的间歇反应器(体积为2.2升)用于一氧化氮的光催化降解;将50毫克基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料放到该间歇反应器中,关闭舱门,将反应器抽真空,调节高纯空气(1升)和一氧化氮(浓度为100 ppm)的流速,使混合气体的流量为2.4 升每分钟,待一氧化氮浓度稳定在600 ppb十五分钟以后,打开氙灯光源,开始进行光降解反应;该基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料光催化剂可多次循环使用,具有很好的稳定性,循环使用4次后,依然有很好的催化效果。
附图6 为苝四酸二酐修饰氮化碳石墨烯气凝胶光催化降解一氧化氮的效果图;附图7 为该光催化材料循环使用效果图。
通过以上分析,说明本发明通过简单步骤合成的苝四酸二酐修饰氮化碳石墨烯气凝胶对一氧化氮气体有着很好的光催化效果;且可以多次循环使用,具有制备过程较为简便,生产原料易得等优点,在一氧化氮气体污染的处理方面具有应用前景。
Claims (10)
1.一种基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料的制备方法,其特征在于,包括以下步骤:
(1)以双氰胺为原料,煅烧制备片状氮化碳;
(2)将苝四酸二酐和片状氮化碳在咪唑中反应,制备苝四酸二酐修饰的氮化碳材料;
(3)将苝四酸二酐修饰的氮化碳和氧化石墨烯分散到去离子水中,反应后经过冷冻干燥,制备基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料。
2.根据权利要求1所述基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料的制备方法,其特征在于:步骤(1)中,所述煅烧的条件为,在氩气保护下于400~700 ℃煅烧3~6小时;煅烧时的升温速率为每分钟2~15 ℃。
3.根据权利要求1所述基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料的制备方法,其特征在于:步骤(2)中,苝四酸二酐、片状氮化碳、咪唑的质量比为1:30:120;所述反应的温度为130~160 ℃,时间为4~7小时。
4.根据权利要求1所述基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料的制备方法,其特征在于:步骤(2)中,反应结束后,将产物加入到碳酸钾水溶液中,回流1~3小时,冷却至室温,然后经过离心、盐酸洗,再分别用水和乙醇洗至中性,最后真空干燥3~6小时,制备苝四酸二酐修饰的氮化碳材料。
5.根据权利要求1所述基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料的制备方法,其特征在于:步骤(3)中,苝四酸二酐修饰的氮化碳和氧化石墨烯的质量比为3:1;分散到去离子水中后进行超声处理,所述反应的温度为160~200 ℃,时间为5~8小时;所述冷冻干燥为在冷冻干燥箱中冷冻1~2天。
6.一种基于苝四酸二酐修饰的氮化碳/氧化石墨烯水凝胶复合材料的制备方法,其特征在于,包括以下步骤:
(1)以双氰胺为原料,煅烧制备片状氮化碳;
(2)将苝四酸二酐和片状氮化碳在咪唑中反应,制备苝四酸二酐修饰的氮化碳材料;
(3)将苝四酸二酐修饰的氮化碳和氧化石墨烯分散到去离子水中,反应制得基于苝四酸二酐修饰的氮化碳/氧化石墨烯水凝胶复合材料。
7.根据权利要求6所述基于苝四酸二酐修饰的氮化碳/氧化石墨烯水凝胶复合材料的制备方法,其特征在于:步骤(1)中,所述煅烧的条件为,在氩气保护下于400~700 ℃煅烧3~6小时,煅烧时的升温速率为每分钟2~15 ℃;步骤(2)中,苝四酸二酐、片状氮化碳、咪唑的质量比为1:30:120,所述反应的温度为130~160 ℃,时间为4~7小时;步骤(3)中,苝四酸二酐修饰的氮化碳和氧化石墨烯的质量比为3:1;分散到去离子水中后进行超声处理,所述反应的温度为160~200 ℃,时间为5~8小时。
8.权利要求6所述基于苝四酸二酐修饰的氮化碳/氧化石墨烯水凝胶复合材料的制备方法制备的基于苝四酸二酐修饰的氮化碳/氧化石墨烯水凝胶复合材料。
9.权利要求1所述基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料的制备方法制备的基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料。
10.权利要求8所述基于苝四酸二酐修饰的氮化碳/氧化石墨烯水凝胶复合材料在一氧化氮光催化处理、在气体污染处理、在制备一氧化氮光催化处理剂或者在制备基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料中的应用;权利要求9所述基于苝四酸二酐修饰的氮化碳/氧化石墨烯气凝胶复合材料在一氧化氮光催化处理、在气体污染处理、在制备一氧化氮光催化处理材料中的应用。
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