CN111411412B - 石墨烯-聚丙烯腈基纳米复合材料及其制备方法和应用 - Google Patents
石墨烯-聚丙烯腈基纳米复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及复合材料技术领域，具体来说是石墨烯‑聚丙烯腈基纳米复合材料及其制备方法和应用，石墨烯‑聚丙烯腈基纳米复合材料按照以下方法制成：将石墨烯和丙烯腈单体在引发剂的作用下制备得到了石墨烯‑聚丙烯腈纳米复合材料，然后采用偶联法在石墨烯‑聚丙烯腈纳米复合材料上通过交联剂负载了光催化纳米粒子，再经过静电纺丝法纺丝后，制备得到了石墨烯‑聚丙烯腈基纳米复合材料。本发明不仅制备得到了具有光催化性能的石墨烯‑聚丙烯腈基纳米复合材料，而且能够通过石墨烯和光催化剂的协同效应来分解水体中的有毒有机物，增加水体溶解氧含量，从而实现了污水的净化及处理。
Description
技术领域
本发明涉及复合材料技术领域，具体来说是石墨烯-聚丙烯腈基纳米复合材料及其制备方法和应用。
背景技术
20世纪以来，人们在享受迅速发展的科技所带来的舒适和方便的同时，也品尝着盲目和短视造成的生存环境不断恶化的苦果，环境污染日趋严重。为了适应可持续发展的需要，污染的控制和治理已成为一个亟待解决的问题；在各种环境污染中，最普遍、最重要和影响最大的是水体污染，因而有效的控制和治理污水是环境综合治理的重点，目前污水使用的具有代表性的处理方法主要有：物理法、化学法和微生物处理法，这些方法对污水的治理起重大作用，但是这些技术大部分情况下需通过处理池将污水进行集中化处理，这就需要先将污水引入至处理池内再进行集中处理，而现有技术中并非所有的污水均能够被引入至处理池内，例如湖泊中的污水，因此需要一种便于对无法集种处理的污水进行治理的方法；光催化氧化技术是一门新兴的有广阔应用前景的技术，特别适用无法通过处理池进行集中化处理的污水治理。
目前，石墨烯光催化技术用于污水治理是研究的热点，其治污原理是利用可见光恢复水体自净化，自然光为唯一光源，无需动力装置，无需投加化学试剂或生物菌种。石墨烯(Graphene)是一种新型无机材料，由廉价的石墨制成，其极限模量为1.01TPa，极限强度为116GPa，石墨烯质量轻、比表面积大且具有极好的电子传输性质。
现有技术中还尚未有将石墨烯与光催化材料进行复合形成复合材料，并用于对污水中的化学污染物进行控制和治理。
发明内容
针对上述现有技术的不足，本发明的目的是提供石墨烯-聚丙烯腈基纳米复合材料及其制备方法和应用，本发明不仅制备得到了具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料，而且能够通过光催化剂和石墨烯来分解水体中的有毒有机物，增加水体溶解氧含量，从而实现了污水的净化及处理。
为了达到上述目的，本发明采取的技术方案为：
石墨烯-聚丙烯腈基纳米复合材料，所述石墨烯-聚丙烯腈基纳米复合材料按照以下方法制成：将石墨烯和丙烯腈单体在引发剂的作用下制备得到了石墨烯-聚丙烯腈纳米复合材料，然后采用偶联法在石墨烯-聚丙烯腈纳米复合材料上通过交联剂负载了光催化纳米粒子，再经过静电纺丝法纺丝后，制备得到了具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料。
优选的，所述引发剂为水溶型引发剂或溶剂型引发剂，水溶型引发剂为过硫酸铵或抗坏血酸，溶剂型引发剂为偶氮二异丁腈。
优选的，所述交联剂为甲基三甲氧基硅烷的水溶液或硅溶胶，若交联剂为甲基三甲氧基硅烷的水溶液，则甲基三甲氧基硅烷与水的质量之比为1-2：5。
优选的，所述光催化纳米粒子为TiO2、SnO2、ZrO2、CrSe、WO3、Fe2O3中的一种。
本发明还保护了石墨烯-聚丙烯腈基纳米复合材料的制备方法，包括如下步骤：
(1)石墨烯-聚丙烯腈纳米复合材料的制备：将石墨烯和丙烯腈单体共同加入至溶剂中，再加入引发剂，并在氮气气氛中，于在50-70℃下进行反应，然后冷却至室温，经过滤、洗涤及干燥，得到石墨烯-聚丙烯腈纳米复合材料；
其中，石墨烯与丙烯腈单体的质量比为1:100-1000，引发剂和丙烯腈单体的物质的量之比为3-5：1000；
(2)石墨烯-聚丙烯腈基纳米复合材料的制备：在N,N'-二甲基甲酰胺中加入交联剂，于105-115℃下搅拌回流1-3h后，加入光催化纳米粒子和步骤(1)制备得到的石墨烯-聚丙烯腈纳米复合材料，继续回流3-6h，然后通过静电纺丝法进行纺丝，再经水洗和烘干，制备得到石墨烯-聚丙烯腈基纳米复合材料；
其中，光催化纳米粒子占光催化纳米粒子和石墨烯-聚丙烯腈纳米复合材料总量的8-12wt％，交联剂占光催化纳米粒子和石墨烯-聚丙烯腈纳米复合材料总量的5-10wt％。
优选的，所述步骤(1)中的引发剂若为水溶型引发剂，溶剂为水，在50-70℃下反应2-4h；所述步骤(1)中的引发剂若为溶剂型引发剂，溶剂为N,N'-二甲基甲酰胺或二甲基亚砜，在50-70℃下反应24-48h。
优选的，所述步骤(2)的静电纺丝法的纺丝条件为：纺丝电压15-20KV，注射速度0.6-1.2mm/h，然后将纳米纤维在热牵伸温度为95-100℃下牵伸。
本发明还保护了石墨烯-聚丙烯腈基纳米复合材料在污水净化及处理中的应用。
与现有技术相比，本发明具有的有益效果是：
1、本发明先将石墨烯和丙烯腈在引发剂的作用下制备得到了石墨烯-聚丙烯腈纳米复合材料，石墨烯-聚丙烯腈纳米复合材料的分子量在12×104-30×104，分子量分布在1.5-3.0之间，然后通过偶联法在石墨烯-聚丙烯腈纳米复合材料上负载了光催化纳米粒子，石墨烯-聚丙烯腈纳米复合材料中石墨烯具有比表面积大、吸附速度快及容量大的吸附特点，聚丙烯腈间还有能够使光催化纳米粒子填充的间隙，当石墨烯-聚丙烯腈纳米复合材料与光催化纳米粒子混合时，光催化纳米粒子吸附在石墨烯-聚丙烯腈纳米复合材料上，本发明还加入了交联剂，交联剂使得光催化纳米粒子粘结在石墨烯-聚丙烯腈纳米复合材料上，并保持稳定，避免了纺丝结束后光催化粒子由石墨烯-聚丙烯腈纳米复合材料上掉落，从而潜沉，降低了光催化粒子的光催化性能。
2、石墨烯材料具有优异的性能，但其比表面积大容易发生团聚，这对于石墨烯的应用前景大为不利，因此本发明将石墨烯与丙烯腈进行聚合，有效避免了石墨烯的团聚，实现了石墨烯的均匀分布，且聚丙烯腈具有耐候性、耐日晒性及耐化学试剂腐蚀的优异性能，特别是在无机酸、漂白粉、过氧化氢及一般有机试剂中稳定性极强，因此在对污水进行处理时，聚丙烯腈实现了石墨烯-聚丙烯腈纳米复合材料的结构完整性，为光催化纳米粒子提供了有效的负载基体，使得光催化纳米粒子能够进行长期有效的污水处理，且本发明将复合材料进行了纺丝，在使用时能够织成网状结构，能够将有害物质和藻类“网”住，提高了水体的自净功能，同时便于光催化纳米粒子的回收。
3、本发明选用石墨烯是由于内部石墨烯碳原子的排列方式与石墨单原子层一样，以sp2杂化轨道成键，因此具有强度高且韧性好的特点；另外，石墨烯从物理性质上来讲是一种二维晶体，其电子的运动速度达到光速的1/300，远超过电子在一般导体中的运动速度，因此石墨烯被称为“载荷子”，而光催化纳米粒子表面多相光催化的基本原理是：用能量高于禁带宽度的光照射光催化纳米粒子表面时，价带上的电子被激发，跃迁到导带上，同时在价带产生相应的空穴，此时光催化纳米粒子内部生成电子-空穴对，电子-空穴对迁移到粒子表面不同位置并与吸附半导体表面的反应物发生相应的氧化或还原反应，同时激发态的二氧化钛重新回归到基态，而当光催化纳米粒子负载在石墨烯上时，石墨烯对光催化纳米粒子中电子的传递和跃迁进行辅助，从而提升了光催化纳米粒子的氧化或还原反应效率。
具体实施方式
下面结合本发明实施例1-3，用以较佳的实施例配合详细的说明。
实施例1
具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料的制备方法，包括如下步骤：
(1)石墨烯-聚丙烯腈纳米复合材料的制备：将0.05g石墨烯和5g丙烯腈单体共同加入至50ml水中，加入过硫酸铵，并在氮气气氛中，在50℃下反应4h，然后冷却至室温，经过滤，水洗及在60℃下真空干燥8h，得到石墨烯-聚丙烯腈纳米复合材料；
(2)具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料的制备：在29mL的N,N'-二甲基甲酰胺中加入0.15ml甲基三甲氧基硅烷的水溶液，然后于105℃下搅拌回流3h，然后加入0.25g的Fe2O3光催化纳米粒子和2.83g步骤(1)制备得到的石墨烯-聚丙烯腈纳米复合材料，继续回流6h后，然后在电压为20KV，注射速度为0.6mm/h，静电纺丝制备得到纳米纤维后，在温度为95℃水浴中牵伸，再经水洗和常温烘干，制备得到具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料。
实施例2
具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料的制备方法，包括如下步骤：
(1)石墨烯-聚丙烯腈纳米复合材料的制备：将0.05g石墨烯和10g丙烯腈单体共同加入至50ml的N,N'-二甲基甲酰胺中，加入偶氮二异丁腈，并在氮气气氛中，在60℃下反应48h，得到石墨烯-聚丙烯腈纳米复合溶液；
(2)具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料的制备：在20mL的N,N'-二甲基甲酰胺中加入0.16ml硅溶胶，于110℃下搅拌回流2h，然后加入0.2g的TiO2光催化粒子和1.8g步骤(1)制备得到的石墨烯-聚丙烯腈纳米复合材料形成混合液，继续回流4h后，然后在电压为18KV，注射速度为0.9mm/h，静电纺丝制备得到纳米纤维后，在98℃水浴中牵伸，再经水洗和烘干，制备得到具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料。
实施例3
具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料的制备方法，包括如下步骤：
(1)石墨烯-聚丙烯腈纳米复合材料的制备：将0.05g石墨烯和50g丙烯腈单体共同加入至500ml水中，加入抗坏血酸，并在氮气气氛中，在70℃下反应2h，然后冷却至室温，经过滤，水洗及在60℃下真空干燥12h，得到石墨烯-聚丙烯腈纳米复合材料；
(2)具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料的制备：在250mL的N,N'-二甲基甲酰胺中加入2.8ml甲基三甲氧基硅烷的水溶液，于115℃下搅拌回流1h，然后加入3.4g的SnO2光催化纳米粒子和25g步骤(1)制备得到的石墨烯-聚丙烯腈纳米复合材料形成混合液，继续回流3h后，然后在纺丝电压为15KV，注射速度为1.2mm/h，静电纺丝制备得到纳米纤维后，在100℃水浴中牵伸，再经水洗和烘干，制备得到具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料。
对比例1
实施例2使用的市售的TiO2纳米颗粒。
对比例2
具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料的制备方法，包括如下步骤：
(1)石墨烯-聚丙烯腈纳米复合材料的制备：石墨烯-聚丙烯腈纳米复合材料的制备：将0.05g石墨烯和5g丙烯腈单体共同加入至50ml水中，加入过硫酸铵，并在氮气气氛中，在50℃下反应4h，然后冷却至室温，经过滤，水洗及在60℃下真空干燥8h，得到石墨烯-聚丙烯腈纳米复合材料；
(2)在N,N'-二甲基甲酰胺中加入0.25g的Fe2O3光催化纳米粒子和2.83g步骤(1)制备得到的石墨烯-聚丙烯腈纳米复合材料，回流6h后，在电压为20KV，注射速度为0.6mm/h，静电纺丝制备得到纳米纤维后，在温度为95℃水浴中牵伸，再经水洗和常温烘干，制备得到具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料。
本发明实施例1-实施例3制备得到的石墨烯-聚丙烯腈基纳米复合材料均具有优异的光催化性能，下面对本发明制备得到的石墨烯-聚丙烯腈基纳米复合材料与现有技术的TiO2纳米颗粒及对比例2制备得到的石墨烯-聚丙烯腈基纳米复合材料的性能进行比较，具体研究方法及研究结果如下所示：
研究方法：
对实施例1-实施例3的样品以及对比例1-对比例2的样品进行了光吸收波长和光催化性能测试，其中光催化性能是对罗丹明B模拟的有机废水进行降解，具体为：将实施例1-实施例3和对比例1-对比例2的光催化剂均称取50mg，然后分别放入100mL浓度为10mg/L的罗丹明B模拟水样中加入至石英夹层的反应器中，以150W氙灯作为太阳光源，在转速为500r/min下搅拌辐射60min，采用高效液相色谱法测定水样中罗丹明B的浓度，计算得到光催化降解率，测试数据见表1：
断裂强度及断裂伸长率按照国家技术监督局GB/T 14337-2008标准；
表1实施例1-3与对比例1-2的性能比较
对比例2与实施例1的制备步骤相同，不同之处仅在于对比例2未加入粘结剂，对比例2中虽然石墨烯上接枝了聚丙烯腈，但是聚丙烯腈的强度并不高，致使对比例2制备得到的复合材料的拉伸强度和石墨烯的拉伸强度相差不大；而实施例1-实施例3制备得到的复合材料上还含有粘结剂，因此与现有技术中的石墨烯和对比例2制备得到的样品相比，拉伸强度和断裂伸长率均得到了提升，使得石墨烯-聚丙烯腈纤维具有更加优异的力学性能；另外，相较于对比例1的现有技术的TiO2纳米颗粒，实施例1-实施例3的光吸收波长范围更广，能够有更多的光与复合材料发生相互作用，从而增大了复合材料的光催化效率；本发明还研究了对罗丹明B的光催化效率，结果表明，本发明制备得到的石墨烯-聚丙烯腈基纳米复合材料的光催化效率高于对比例1的现有技术的TiO2纳米颗粒，也高于对比例2制备得到石墨烯-聚丙烯腈基纳米复合材料，说明本发明制备得到的墨烯-聚丙烯腈基纳米复合材料具有更加优异的光催化性能及力学性能。
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，则本发明也意图包含这些改动和变型在内。
Claims (7)
1.分解水体中的有毒有机物的石墨烯-聚丙烯腈基纳米复合材料，其特征在于，所述石墨烯-聚丙烯腈基纳米复合材料按照以下方法制成：将石墨烯和丙烯腈单体在引发剂的作用下制备得到了石墨烯-聚丙烯腈纳米复合材料，然后采用偶联法在石墨烯-聚丙烯腈纳米复合材料上通过交联剂负载了光催化纳米粒子，再经过静电纺丝法纺丝后，制备得到了具有光催化性能的石墨烯-聚丙烯腈基纳米复合材料；
所述光催化纳米粒子为TiO2、SnO2、ZrO2、CrSe、WO3、Fe2O3中的一种。
2.根据权利要求1所述的石墨烯-聚丙烯腈基纳米复合材料，其特征在于，所述引发剂为水溶型引发剂或溶剂型引发剂，水溶型引发剂为过硫酸铵或抗坏血酸，溶剂型引发剂为偶氮二异丁腈。
3.根据权利要求1所述的石墨烯-聚丙烯腈基纳米复合材料，其特征在于，所述交联剂为甲基三甲氧基硅烷的水溶液或硅溶胶，交联剂为甲基三甲氧基硅烷的水溶液，则甲基三甲氧基硅烷与水的质量之比为1-2：5。
4.根据权利要求1所述的石墨烯-聚丙烯腈基纳米复合材料的制备方法，其特征在于，包括如下步骤：
（1）石墨烯-聚丙烯腈纳米复合材料的制备：将石墨烯和丙烯腈单体共同加入至溶剂中，再加入引发剂，并在氮气气氛中，于50-70℃下进行反应，然后冷却至室温，经过滤、洗涤及干燥，得到石墨烯-聚丙烯腈纳米复合材料；
其中，石墨烯与丙烯腈单体的质量比为1:100-1000，引发剂和丙烯腈单体的物质的量之比为3-5：1000；
（2）石墨烯-聚丙烯腈基纳米复合材料的制备：在N,N'-二甲基甲酰胺中加入交联剂，于105-115℃下搅拌回流1-3h后，加入光催化纳米粒子和步骤（1）制备得到的石墨烯-聚丙烯腈纳米复合材料，继续回流3-6h，然后通过静电纺丝法进行纺丝，再经水洗和烘干，制备得到石墨烯-聚丙烯腈基纳米复合材料；
其中，光催化纳米粒子占光催化纳米粒子和石墨烯-聚丙烯腈纳米复合材料总量的8-12wt%，交联剂占光催化纳米粒子和石墨烯-聚丙烯腈纳米复合材料总量的5-10wt%。
5.根据权利要求4所述的石墨烯-聚丙烯腈基纳米复合材料的制备方法，其特征在于，所述步骤（1）中的引发剂为水溶型引发剂，溶剂为水，在50-70℃下反应2-4h；所述步骤（1）中的引发剂为溶剂型引发剂，溶剂为N,N'-二甲基甲酰胺或二甲基亚砜，在50-70℃下反应24-48h。
6.根据权利要求4所述的石墨烯-聚丙烯腈基纳米复合材料的制备方法，其特征在于，所述步骤（2）的静电纺丝法的纺丝条件为：纺丝电压15-20KV，注射速度0.6-1.2mm/h，然后将纳米纤维在热牵伸温度为95-100℃下牵伸。
7.根据权利要求1所述的石墨烯-聚丙烯腈基纳米复合材料在污水净化及处理中的应用，其特征在于，所述应用是分解水体中的有毒有机物。
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