CN113861961A - 一种碳量子点负载ZnO颜料的制备方法及其产物的应用 - Google Patents

一种碳量子点负载ZnO颜料的制备方法及其产物的应用 Download PDF

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CN113861961A
CN113861961A CN202111165028.7A CN202111165028A CN113861961A CN 113861961 A CN113861961 A CN 113861961A CN 202111165028 A CN202111165028 A CN 202111165028A CN 113861961 A CN113861961 A CN 113861961A
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吴晓宏
王群
李杨
秦伟
卢松涛
康红军
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Chongqing Research Institute of Harbin Institute of Technology
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Abstract

本发明公开了一种碳量子点负载ZnO颜料的制备方法及其产物的应用,属于热控涂层技术领域。本发明现有氧化锌制备方法存在的形貌尺寸不均一、制备流程繁琐、原材料未能高效利用等问题。本发明以三乙醇胺、超纯水和乙酸锌为原料,采用一步溶剂热法制备出形貌尺寸均一的含碳量子点氧化锌微米球,同时得到了具有荧光效应的碳量子点。本发明制备方法简便。制备出的含碳点氧化锌粒子符合热控涂层高反射高发射的性能要求,因此可作为热控涂层的优异性能颜料;制备的碳量子点可用于荧光打印及铁离子的检测;另外,对原材料实现了100%的高效利用。

Description

一种碳量子点负载ZnO颜料的制备方法及其产物的应用
技术领域
本发明属于热控涂层技术领域,一种碳量子点负载ZnO颜料的制备方法及其产物的应用。
背景技术
氧化锌是一种多功能性的新型无机材料,由于其在催化、磁学、力学等方面具有特殊的功能,另外氧化锌廉价、环保无毒等优点,被广泛应用至光催化、生物医药、化工涂料、电子、热控涂层等领域。以氧化锌为颜料的热控涂层具有可见-近红外波段低太阳吸收、中红外高发射特征及优异的化学稳定性,能够在恶劣的空间环境下保持良好的光学性能,同时可吸收波长385nm以下的紫外光而保护粘结剂,显著提升热控涂层的抗紫外老化性能,延长涂层的使用期限。然而以往制备的氧化锌形貌尺寸难以控制、尺寸不均一,这严重影响了热控涂层的光学稳定性及低吸高发的性能;传统制备的氧化锌形貌多为一维线状、二维片状的纳米粒子,这对于获得性能优异的热控涂层是不利的;以往制备氧化锌的流程繁琐,不易实现规模化的制备;另外均匀微米尺寸的含碳量子点氧化锌对于获得低吸高发的热控涂层具有更佳的抗紫外老化性能。传统制备氧化锌过程的残留产物不能够高效利用,这造成了原材料极大的浪费。碳量子点是一种新型的零维碳基材料,其粒径尺寸为小于10nm,因其具有毒性低、生物兼容性良好等特点,在指纹荧光检测、发光材料、离子检测、细胞检测等领域具有巨大的应用潜力。如何简单、低成本的一步制备含碳量子点氧化锌热控颜料的方法是科研人员急迫解决的问题。
现有技术存在的缺点:
(1)目前制备氧化锌的方法流程繁琐,不易实现规模化地制备;
(2)以往制备的氧化锌形貌尺寸难以控制、尺寸不均一,这严重影响了热控涂层的光学稳定性及低吸高发的性能;
(3)传统制备的氧化锌形貌多为一维线状、二维片状的纳米粒子,这对于获得性能优异的热控涂层是不利的;
(4)另外均匀微米尺寸的含碳量子点氧化锌对于获得低吸高发的热控涂层具有更佳的抗紫外老化性能;
(5)传统制备氧化锌过程的残留产物不能够高效利用,这造成了原材料极大的浪费。
发明内容
本发明现有氧化锌制备方法存在的形貌尺寸不均一、制备流程繁琐、原材料未能高效利用等问题,提供了一种碳量子点负载ZnO颜料的制备方法及其产物的应用。本发明方法制备的含碳量子点氧化锌微球粒子尺寸均一,形貌可控,是作为热控涂层优异的性能颜料;制备过程产生的残留物——碳量子点可用于铁离子检测、防伪识别及荧光打印,实现了原材料的高效利用以及降低了能源消耗。
为了解决上述技术问题,本发明一种碳量子点负载ZnO颜料的制备方法是以三乙醇胺、超纯水和乙酸锌为原料,具体制备方法是按下述步骤进行的:
步骤1、将乙酸锌加到超纯水中,在室温环境下搅拌,得到乙酸锌溶液;
步骤2、向步骤1获得的乙酸锌溶液中加入三乙醇胺,磁力搅拌,得到白色的混合液,转移至反应釜;
步骤3、然后将反应釜置于温度为140℃~180℃烘箱内,反应6h~10h,得到底部沉淀和上层淡黄色澄清液;
步骤4、然后离心,将分离后的沉淀用超纯水进行超声清洗2次-3次,即获得含碳量子点氧化锌微球粒子;分离的淡黄色澄清液,以10000r/min~12000r/min进行2-3次离心,然后进行透析,即得到碳量子点溶液。
进一步地限定,按照质量百分比计,乙酸锌的质量分数为8.4%-9.9%,三乙醇胺的质量分数为15.2%-18.0%,余量为超纯水;并且满足超纯水与三乙醇胺的质量比为4~5:1。
进一步地限定,步骤1中以300~400r/min转速搅拌至少15min。
进一步地限定,步骤2中以600~800r/min转速磁力搅拌至少20min。
进一步地限定,步骤4以6000r/min~8000r/min转速进行离心至少15min。
上述方法制备的含碳量子点氧化锌微球粒子用于制备热控涂层。
上述方法制备的碳量子点溶液用于铁离子检测。
上述方法制备的碳量子点溶液用于防伪识别。
上述方法制备的碳量子点溶液用于荧光打印。
本发明采用一种低毒、价格低廉的三乙醇胺辅助溶剂,乙酸锌作为锌源,二者反应温和不剧烈,三乙醇胺与乙酸锌提供的锌源反应,分子间氢键相互作用促使纳米颗粒聚集,自组装形成含碳量子点氧化锌微米球;则三乙醇胺提供的碳源在高温下形成尺寸均一的具有亮蓝色荧光效应的碳量子点。
本发明采用一步溶剂热法制备出形貌尺寸均一的含碳量子点的氧化锌微米球,同时得到了具有荧光效应的碳量子点,制备方法简便。制备出的含碳量子点氧化锌粒子符合热控涂层高反射高发射的性能要求,因此可作为热控涂层的优异性能颜料;制备的碳量子点可用于荧光打印及铁离子的检测;另外,对原材料实现了100%的高效利用。
本发明改善了现有技术制备氧化锌形貌、尺寸不均的缺点,提供制备的含碳量子的氧化锌形貌尺寸均一,形貌易于制备,易实现规模化生产。
本发明提供了一种符合低吸高发热控涂层性质的氧化锌颜料的制备方法,其一步法流程简单,较少能源消耗,另外,全流程的产生的残留物用来制备具有荧光性质的碳量子点溶液,可用于离子检测、指纹识别等,产物实现了完全的高效利用。
本发明的溶剂热法制备的氧化锌形貌尺寸均一,相比于传统的方法而言,具有条件温和、大规模制备的优点,进行简单的超声清洗就可得到含碳量子点氧化锌微米球,其对于制备高反射高发射热控涂层而言,具有优异的光电性能及化学稳定性(大于200nm)。
本发明采用的是自下而上的溶剂热法获得碳量子点,相比自上而下的方法,自下而上具有反应条件温和、可控、可大规模的制备优势,无需繁琐的纯化步骤,即可得到纯的碳量子点,制备的碳量子点具有强的荧光效应,可用于荧光打印,用于编码防伪识别,另外,制备的碳量子点具有离子选择性和竞争性,可用于三价铁离子的检测。
附图说明
图1是实施例1中含碳量子点氧化锌微球的扫描电镜图;
图2是实施例1中残留产物——碳量子点的透射电镜图;
图3是实施例1中含碳量子点的氧化锌微球颜料制备的无机硅酸钾涂层的太阳反射率;
图4是实施例1中氧化锌微球颜料制备的无机硅酸钾涂层的红外发射率;
图5是实施例1中碳量子点溶液用于十八种离子荧光检测;
图6是碳量子点溶液作为墨水实时打印的荧光照片。
具体实施方式
实施例1:按照质量百分比计,本实施例中一种碳量子点负载ZnO颜料的制备方法是以8.8%的乙酸锌,15.2%三乙醇胺,76%的超纯水为原料;具体制备方法是按下述步骤进行的:
步骤1、将乙酸锌加到超纯水中,在室温环境下以400r/min转速搅拌15min,得到乙酸锌溶液;
步骤2、向步骤1获得的乙酸锌溶液中加入三乙醇胺,以600rpm/min转速磁力搅拌20min,得到白色的混合液,转移至反应釜;
步骤3、然后将反应釜置于温度为180℃烘箱内,反应6h,得到底部沉淀和上层淡黄色澄清液;
步骤4、然后以6000rpm/min转速进行离心15min,将分离后的沉淀用超纯水进行超声清洗3次,即获得含碳量子点氧化锌微球粒子;将分离的淡黄色澄清液以10000r/min进行3次离心,然后进行透析,即得到碳量子点溶液。
本实施例中含碳量子点氧化锌微球的扫描电镜图如图1所示;由图1可以看出制备的含碳量子点氧化锌微球形貌、尺寸均一;
本实施例中残留产物——碳量子点的透射电镜图如图2所示,可知碳量子点尺寸均一;
本实施例中含碳量子点氧化锌微球颜料制备的无机硅酸钾涂层的太阳反射率如图3所示,经计算,在0.3-2.5μm波段的太阳反射率为86.48%;
本实施例中氧化锌微球颜料制备的无机硅酸钾涂层的红外发射率如图4所示,经计算,2.5-0.3μm波段的红外发射率为92.21%;
本实施例中碳量子点溶液用于十八种离子荧光检测如图5所示,由图可知,碳量子点溶液仅对铁离子具有荧光猝灭效应。
本实施例中碳量子点溶液作为墨水实时打印的荧光照片如图6所示,可知,具有优异的荧光效应。

Claims (10)

1.一种碳量子点负载ZnO颜料的制备方法,其特征在于以三乙醇胺、超纯水和乙酸锌为原料,具体制备方法是按下述步骤进行的:
步骤1、将乙酸锌加到超纯水中,在室温环境下搅拌,得到乙酸锌溶液;
步骤2、向步骤1获得的乙酸锌溶液中加入三乙醇胺,磁力搅拌,得到白色的混合液,转移至反应釜;
步骤3、然后将反应釜置于温度为140℃~180℃烘箱内,反应6h~8h,得到底部沉淀和上层淡黄色澄清液;
步骤4、然后离心,将分离后的沉淀用超纯水进行超声清洗2次-3次,即获得碳量子点负载ZnO颜料。
2.根据权利要求1所述的制备方法,其特征在于按照质量百分比计,乙酸锌的质量分数为8.4%-9.9%,三乙醇胺的质量分数为15.2%-18.0%,余量为超纯水;并且满足超纯水与三乙醇胺的质量比为4~5:1。
3.根据权利要求1所述的制备方法,其特征在于步骤1中以300~400r/min转速搅拌至少15min。
4.根据权利要求1所述的制备方法,其特征在于步骤2中以600~800r/min转速磁力搅拌至少20min。
5.根据权利要求1所述的制备方法,其特征在于步骤4以6000r/min~8000r/min转速进行离心至少15min。
6.如权利要求1-5任意一项所述方法制备的碳量子点负载ZnO颜料用于制备热控涂层。
7.碳量子点溶液的制备方法,其特征在于碳量子点溶液的制备方法是将权利要求1-5任意一项步骤4获得的淡黄色澄清液,以10000r/min~12000r/min转速进行3次离心,然后进行透析,即得到碳量子点溶液。
8.如权利要求7方法制备的碳量子点溶液用于铁离子检测。
9.如权利要求7方法制备的碳量子点溶液用于防伪识别。
10.如权利要求7方法制备的碳量子点溶液用于荧光打印。
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