CN114054054B - 一种三元可见光光催化纳米复合材料及其制备方法 - Google Patents
一种三元可见光光催化纳米复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种三元可见光光催化纳米复合材料及其制备方法，属于功能材料技术领域，包括以下步骤：S1、磷掺杂石墨烯量子点的制备以芘和硝酸为原料，制备三硝基芘；将所述三硝基芘加入水，并加入磷源，调整pH至10～11，在180℃进行水热反应，制备磷掺杂石墨烯量子点；S2、制备S1磷掺杂石墨烯量子点水溶液，并与二氧化钛纳米颗粒、硝酸银和碘化钾混合，过滤，干燥，制备三元可见光光催化纳米复合材料；将制作的纳米材料放入甲基橙溶液中在可见光照射下，10分钟催化效率可达99.35％，表现出及其优异的催化性能。
Description
技术领域
本发明属于功能材料技术领域，具体涉及一种三元可见光光催化纳米复合材料及其制备方法。
背景技术
有机染料水污染给人们的健康和生命带来了巨大的隐患，已经成为全球面临的重大挑战。半导体光催化是解决这一问题非常有前景的方法。在半导体多元光催化中，来自环境的多种难降解污染物在紫外线/可见光照射下被分解，已知研究的几种光催化半导体材料中，二氧化钛是最有潜力的一种，具有性能稳定、无毒、成本低等特点，自1972年首次应用于水分解以来，被广泛应用到多个领域。然而，例如宽带隙，载流子高复合率等缺点限制了其光催化效率。且目前制备以二氧化钛为主成分的光催化复合材料，只是在紫外光下能够对水中有机染料污物起到催化降解效果，而在可见光波长区域催化效果很差，对太阳光能量利用率极低，难以大规模商用。
发明内容
为了解决上述技术问题，本发明提供了一种三元可见光光催化纳米复合材料及其制备方法，通过简便的方法将二氧化钛纳米级颗粒与磷掺杂石墨烯量子点，和碘化银结合成纳米复合材料，在二氧化钛表面引入磷掺杂石墨烯量子点是提高二氧化钛光敏化，并与二氧化钛形成P/N节显著提高载流子传输减少与光生电子复合，碘化银与二氧化钛耦合构建一种异质结形成半导体表面之间界面能偏差，可以增加电荷空穴分离效率，并且碘化银对可见光辐射吸收有很强的吸收能力；本发明复合材料可高效利用太阳光用于分解水中不同的有机污染物。
本发明具体是通过如下技术方案来实现的。
本发明的第一个目的是提供一种三元可见光光催化纳米复合材料的制备方法，包括以下步骤：
S1、磷掺杂石墨烯量子点的制备
以芘和硝酸为原料，制备三硝基芘；将所述三硝基芘加入水，并加入磷源，调整pH至10～11，在180℃进行水热反应，制备磷掺杂石墨烯量子点；
S2、制备S1磷掺杂石墨烯量子点水溶液，并与二氧化钛纳米颗粒、硝酸银和碘化钾混合，过滤，干燥，制备三元可见光光催化纳米复合材料。
优选的，S1中，芘与硝酸的用量比为1g：100mL。
优选的，S1中，所述三硝基芘的制备是在80℃下水浴加热回流搅拌12h。
优选的，S1中，所述磷源为十二水磷酸氢二钠。
优选的，S1中，三硝基芘：水：磷源得到用量比为1mg：1mL：0.03g。
优选的，S1中，水热反应的时间是6h。
优选的，S1中，水热反应结束后，使用截留分子量为3500Da透析袋将溶液透析24～36h，之后干燥。
优选的，S2中，原料加入顺利为：将二氧化钛纳米颗粒分散在磷掺杂石墨烯量子点水溶液中，加入硝酸银，混合均匀后，搅拌过程中逐滴加入碘化钾水溶液。
优选的，S2中，磷掺杂石墨烯量子点水溶液的浓度为0.2mg/mL，二氧化钛纳米颗粒：磷掺杂石墨烯量子点水溶液：硝酸银：碘化钾的用量比为0.5g：500mL：0.097g：0.092g。
本发明的第二个目的是提供由上述制备方法制备的三元可见光光催化纳米复合材料。
本发明与现有技术相比具有如下有益效果：
(1)本发明将二氧化钛纳米级颗粒与磷掺杂石墨烯量子点，和碘化银结合成纳米复合材料，在合成纳米复合材料时通过简单的溶解在水中搅拌悬浊液吸附的方式使二氧化钛、磷掺杂石墨烯量子点、碘化银成功的复合成三元纳米材料，并未使用加热等方式，成本低，操作方便。
(2)将制备的纳米材料放入甲基橙溶液中在可见光照射下，10分钟催化效率可达99.35％，表现出及其优异的催化性能。
附图说明
图1为实施例1制备的P25/PCDs/AgI材料的TEM图；
图2为实施例1制备的P25/PCDs/AgI材料的HRTEM图；
图3是实施例1制备的P25/PCDs/AgI材料的FESEM图；
图4是实施例1制备的P25/PCDs/AgI材料的EDS图；
图5是实施例1制备的P25/PCDs/AgI材料的XPS光谱图；
图6是实施例1与对比例1～4材料对甲基橙的催化性能图。
具体实施方式
为了使本领域技术人员更好地理解本发明的技术方案能予以实施，下面结合具体实施例和附图对本发明作进一步说明，但所举实施例不作为对本发明的限定。
下述各实施例中所述实验方法和检测方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可在市场上购买得到。
实施例1
一种三元可见光光催化纳米复合材料的制备方法，包括以下步骤：
(1)将1g芘与100ml硝酸混合后，在80℃下水浴加热回流搅拌12h，将反应物加入500ml纯净水中进行过滤，得到黄色固体为三硝基芘，将40mg三硝基芘放入40ml水中，加入1.2g十二水磷酸氢二钠作为磷源，添加氢氧化钠使混合液PH值达到10，将混合液放置100ml反应釜中，在180℃，加热6h。冷却后，过滤得到溶液，使用3500Da透析袋将溶液透析24小时，将透析后溶液冷却干燥得到磷掺杂石墨烯量子点(PCDs)。
(2)将粉末取取商用级别二氧化钛纳米颗粒(P25)0.5g，分散在500ml，(0.2mg/ml)磷掺杂石墨烯量子点水溶液中快速磁力搅拌0.5h，将0.097g硝酸银放入混和溶液中快速磁力搅拌一小时，后将0.092碘化钾溶解到20ml水中，逐滴加入到混合溶液中，边搅拌边滴入混合溶液发现颜色明显变为黄绿色，后过滤60℃干燥，得到(二氧化钛，磷掺杂石墨烯量子点，碘化银)新型三元优异可见光光催化纳米复合材料(P25/PCDs/AgI)。
实施例2
(1)将1g芘与100ml硝酸混合后，在80℃下水浴加热回流搅拌12h，将反应物加入500ml纯净水中进行过滤，得到黄色固体为三硝基芘，将40mg三硝基芘放入40ml水中，加入1.2g十二水磷酸氢二钠作为磷源，添加氢氧化钠使混合液pH值达到11，将混合液放置100ml反应釜中，在180℃，加热6h。冷却后，过滤得到溶液，使用3500Da透析袋将溶液透析36小时，将透析后溶液冷却干燥得到磷掺杂石墨烯量子点。
(2)将粉末取取商用级别二氧化钛纳米颗粒(P25)0.5g，分散在500ml，(0.2mg/ml)磷掺杂石墨烯量子点水溶液中快速磁力搅拌0.5h，将0.097g硝酸银放入混和溶液中快速磁力搅拌一小时，后将0.092碘化钾溶解到20ml水中，逐滴加入到混合溶液中，边搅拌边滴入混合溶液发现颜色明显变为黄绿色，后过滤60℃干燥，得到(二氧化钛，磷掺杂石墨烯量子点，碘化银)新型三元优异可见光光催化纳米复合材料。
对比例1
将二氧化钛纳米颗粒(P25)分散在500ml实施例1步骤(1)制备的(0.2mg/ml)磷掺杂石墨烯量子点水溶液中快速磁力搅拌0.5h，之后过滤、60℃干燥，制得P25/PCDs材料。
对比例2
将P25与分散在500ml0.2mg/ml纯石墨烯量子点水溶液中快速磁力搅拌0.5h，之后过滤、60℃干燥，制得P25/CDs材料。
对比例3
将P25分散在500ml0.2mg/ml纯石墨烯量子点水溶液中快速磁力搅拌0.5h，将0.097g硝酸银放入混和溶液中快速磁力搅拌一小时，后将0.092碘化钾溶解到20ml水中，逐滴加入到混合溶液中，之后过滤、60℃干燥，制得P25/CDs/AgI材料。
对比例4
二氧化钛纳米颗粒(P25)。
实施例1和实施例2制备的材料性能近似，下面对上述实施例1制备的材料为例，首先对材料进行表征，图1为P25/PCDs/AgI材料的TEM图，图2为P25/PCDs/AgI材料的HRTEM图，由图2可得，三种晶格间距，平面晶格间距0.35nm对应P25，0.231nm对应AgI，0.243对应PCDs，由此证明复合材料的成功合成；图3是材料的FESEM图，由图1和图3可得，材料的TEM和FESEM图像彼此高度吻合，它们显示出纳米复合材料几乎由球形颗粒组成，由于纳米复合材料高度生长，因此观察到颗粒团聚。图4是材料的EDS图，图5是材料的XPS光谱图，由图4和图5可以清晰的看到三元催化剂样品中包含C,P,Ag,I,TI,O元素，说明PCDs、AgI、TIO2，通过物理吸附的方式构建了一种结构稳定的三元光催化剂。
下面再以对比例1～4为对照，对实施例1制备的P25/PCDs/AgI其进行性能表征，具体操作是：
分别取0.1g实施例1和对比例1～4的催化剂放入到10mg/L的甲基橙溶液在黑暗处超声一小时到达吸附平衡。用300w可见光灯照射下，每五分钟过滤取出5ml样品溶液，测试溶液中的甲基橙浓度。具体结果如图6所示，由图6结果可得，与对比例1～4相比，实施例1制备的材料在可见光照射下，10分钟催化效率可达99.35％，表现出及其优异的催化性能。
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内也意图包含这些改动和变型在内。
Claims (9)
1.一种三元可见光光催化纳米复合材料的制备方法，其特征在于，包括以下步骤：
S1、磷掺杂石墨烯量子点的制备
以芘和硝酸为原料，制备三硝基芘；将所述三硝基芘加入水中，并加入磷源，调整pH至10～11，在180℃进行水热反应，制备磷掺杂石墨烯量子点；
S2、将二氧化钛纳米颗粒分散在磷掺杂石墨烯量子点水溶液中，加入硝酸银，混合均匀后，搅拌过程中逐滴加入碘化钾水溶液，过滤，干燥，制备得到由二氧化钛、磷掺杂石墨烯量子点、碘化银复合成的三元可见光光催化纳米复合材料。
2.根据权利要求1所述的三元可见光光催化纳米复合材料的制备方法，其特征在于，S1中，芘与硝酸的用量比为1g：100mL。
3.根据权利要求1所述的三元可见光光催化纳米复合材料的制备方法，其特征在于，S1中，所述三硝基芘的制备是在80℃下水浴加热回流搅拌12h。
4.根据权利要求1所述的三元可见光光催化纳米复合材料的制备方法，其特征在于，S1中，所述磷源为十二水磷酸氢二钠。
5.根据权利要求1所述的三元可见光光催化纳米复合材料的制备方法，其特征在于，S1中，三硝基芘：水：磷源的用量比为1mg：1mL：0.03g。
6.根据权利要求1所述的三元可见光光催化纳米复合材料的制备方法，其特征在于，S1中，水热反应的时间是6h。
7.根据权利要求1所述的三元可见光光催化纳米复合材料的制备方法，其特征在于，S1中，水热反应结束后，使用截留分子量为3500Da透析袋将溶液透析24～36h，之后干燥。
8.根据权利要求1所述的三元可见光光催化纳米复合材料的制备方法，其特征在于，S2中，磷掺杂石墨烯量子点水溶液的浓度为0.2mg/mL，二氧化钛纳米颗粒：磷掺杂石墨烯量子点水溶液：硝酸银：碘化钾的用量比为0.5g：500mL：0.097g：0.092g。
9.根据权利要求1～8任一项所述的制备方法制备的三元可见光光催化纳米复合材料。
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