CN112242501A - 一种氧化锌量子点/石墨烯复合材料的制备方法及其应用 - Google Patents
一种氧化锌量子点/石墨烯复合材料的制备方法及其应用 Download PDFInfo
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Abstract
本发明属于功能化纳米材料技术领域，涉及一种氧化锌量子点/石墨烯复合材料及其制备方法及其应用。向石墨、浓硫酸和硝酸钠的混合液中加入高锰酸钾搅拌混匀；冰水浴条件下经去离子水稀释；向所得稀释液中加入双氧水溶液，然后离心收集氧化石墨烯并经水稀释得到氧化石墨烯悬浮液(GO悬浮液)；将金属锌片置于GO悬浮液中，室温下搅拌，得到氢氧化锌/石墨烯中间产物悬浊液；去除锌片后将中间产物悬浊液加热，得到黑色固体沉淀产物即氧化锌量子点/石墨烯复合材料。本发明方法具有操作简便、省时高效、成本低且制备条件温和的优点。
Description
技术领域
本发明属于功能化纳米材料技术领域，涉及一种氧化锌量子点/石墨烯复合材料及其制备方法及其应用。
背景技术
纳米氧化锌作为一种重要的新型无机宽带隙半导体功能材料，具有普通氧化锌所无法达到的特殊性能。例如，由于其具有的表面与界面效应、量子尺寸效应、体积效应和宏观量子隧道效应以及高透明度、高分散性等特点，使其在催化、光学、生物和电化学等领域内展示出诸多独特的优异性能。氧化锌量子点作为一种无毒的材料，具有成为生物标记材料的潜能，氧化锌量子点在受到大于禁带宽度能量的光子照射后会产生电子-空穴对，光生电子具有强还原性，光生空穴具有强氧化性，可以与表面的羟基反应生成氧化锌很高的羟基自由基。氧化锌既具有很强的光催化能力，而且对光稳定，几乎不引起光的散射，耐酸碱，无毒，被认为是极具应用前景的高活性光催化剂之一。由于氧化锌量子点粒径小，表面易于修饰，容易在聚合物基体中分散，因而是一种在光屏蔽领域内较为理想的材料[1]。因此，制备尺寸均一、结构稳定的氧化锌量子点，对其在如橡胶、涂料、塑料、陶瓷、催化剂、化纤、电子、化妆品和电化学储能等行业的应用有极为重要的意义。
石墨烯是由单层碳组成的二维晶格结构，是sp2杂化碳原子构成的高密度原子层排列形成的蜂窝网状结构。因此，石墨烯具备独特的性能，如优异的电荷载流子迁移率、高透明度、优良的柔韧性及优异的热力和机械性能[2]。
制备氧化锌量子点/石墨烯复合材料，目前常用的方法是使用锌盐作为氧化锌量子点的前驱体，通过如溶胶凝胶法、均匀沉淀法、喷雾干燥法以及热分解等方法来制备氧化锌量子点；通过使用各类还原剂或者采用水热等方法，由氧化石墨烯(GO)制备还原氧化石墨烯(RGO)。但是使用溶胶凝胶法成本较高，有些原料对健康有害；利用均匀沉淀法不能避免反应后沉淀和混晶共沉淀现象；使用喷雾干燥法的设备较复杂，占地面积大，一次性投资大且热效率不高；利用热分解法其操作条件对结果影响很大。
现阶段急需一种制备过程简便，成本较低，环保的合成方法改进氧化石墨烯量子点/石墨烯复合材料制备的缺点与不足。
发明内容
本发明在于提供一种氧化锌量子点/石墨烯复合材料及其制备方法。
为了实现上述目的，本发明采用以下的技术方案：
一种氧化锌量子点/石墨烯复合材料的制备方法，向石墨、浓硫酸和硝酸钠的混合液中加入高锰酸钾搅拌混匀；冰水浴条件下经去离子水稀释；向所得稀释液中加入双氧水溶液，然后离心收集氧化石墨烯并经水稀释得到氧化石墨烯悬浮液(GO悬浮液)；将金属锌片置于GO悬浮液中，室温下搅拌，得到氢氧化锌/石墨烯中间产物悬浊液；去除锌片后将中间产物悬浊液加热，得到黑色固体沉淀产物即氧化锌量子点/石墨烯复合材料。
所述金属锌片置于GO悬浮液中，室温下搅拌10-60min，去除锌片后,悬浊液在50-95℃油浴条件下反应0.5-4h，生成黑色固体即氧化锌量子点/石墨烯复合材料。
进一步的说：
(1)将石墨、浓硫酸和硝酸钠按质量比为5-10：50-150：5-10混合(优选比为5：100：5)，搅拌混匀得到混合液；混匀后加入高锰酸钾，继续搅拌均匀；
(2)将上述获得混合液于冰水浴条件下向(1)所得溶液中加入蒸馏水进行稀释搅拌；而后再加入过氧化氢水溶液搅拌；
(3)将上述混合液进行离心洗涤，收集除去所得混合物中的底层沉淀物及上层清液，收集中间层浅色产物，用蒸馏水反复洗涤中间层产物后，收集得到产物氧化石墨烯(GO)备用；
(4)将金属锌片置于经水稀释后的GO悬浮液中，室温条件下搅拌10-60min，而后取出锌片，收集氢氧化锌/石墨烯中间产物悬浊液，备用；
(5)将氢氧化锌/石墨烯中间产物悬浊液在50-95℃条件下搅拌反应0.5-4h，生成黑色固体产物即得到氧化锌量子点/石墨烯复合材料。
所述(1)中高锰酸钾与石墨的质量比为4-1:1，搅拌时间为12-24h。
所述(2)中加入的蒸馏水与浓硫酸的体积比为1-2：1，搅拌时间为12-24h。
所述(2)中加入的过氧化氢水溶液与浓硫酸的体积0.3—1:1；其中，水溶液中过氧化氢的浓度为10-40wt％，搅拌时间为6-24h。
一种方法制备的氧化锌量子点/石墨烯复合材料，按照所述的方法制备所得氧化锌量子点/石墨烯复合材料。
本发明具有以下有益效果：
针对现有技术中氧化锌量子点/石墨烯复合材料制备技术方面存在的制备过程复杂、成本较高、反应条件苛刻等缺点。在本发明中，通过室温常压水相条件下，仅以金属锌和氧化石墨烯水溶液为原料，通过快速搅拌的方法制备氧化锌量子点/石墨烯复合材料的前驱体，然后进行一步热处理，该方法操作简便、高效且制备条件温和。
本方案的优点在于原料廉价且转化率高，操作简便且制备条件温和，仅需要锌片在GO溶液中室温常压条件下搅拌反应即可得到前驱体，前驱体在95℃以下搅拌反应即可得到该材料。
附图说明
图1为本发明实施例提供的氧化锌量子点/石墨烯复合材料的粉体X射线衍射图谱(XRD及与标准物质PDF卡片对照)；
图2为本发明实施例提供的氧化锌量子点/石墨烯复合材料的透射电子显微镜图。
图3为本发明实施例提供的氧化锌量子点/石墨烯复合材料做锂离子电池的电池数据图。
图4是氧化锌量子点/石墨烯(ZnO/RGO)复合材料与用静置方法做出的氧化锌/石墨烯(ZnO@RGO)复合材料的电池数据对比图。
具体实施方式
下面结合附图对本发明作进一步说明。
实施例1
将5.0g石墨、120mL98％浓硫酸和2.5g硝酸钠混合搅拌30min，称取15g高锰酸钾加入上述混合液继续搅拌24h；冰水浴下加入200mL蒸馏水稀释搅拌24h；加入50mL、30wt％的H2O2水溶液搅拌24h；离心分离除去所得混合物中的底层黑色大块沉淀物以及上层清液，收集中间层浅色产物，用蒸馏水反复洗涤收集GO悬浮液(3mg/mL)备用。
将稀释后的GO悬浮液(25.0mL，1.0mg/mL)转移至25mL样品瓶中。将金属锌片置于稀释后的GO悬浮液中，室温常压下搅拌30min，取出锌片，将剩余溶液置于90℃油浴条件下搅拌反应2h，生成黑色固体即氧化锌量子点/石墨烯复合材料。(参见图1和图2)
上述方法在室温搅拌的条件下进行，通过控制金属Zn在悬浮液中的反应时间，部分地还原GO并原位转化为附着在GO片表面上的Zn(OH)2量子点，进而可以很容易的转化为ZnO量子点，加速了GO片上的剩余含氧基团在温和条件下催化脱氢的过程。使得GO片被完全还原以形成微尺寸多孔薄RGO支撑结构，其中在RGO层之间有低于10nm的良好分散的ZnO量子点。
同时由图1氧化锌量子点/石墨烯复合材料的粉体X射线衍射图谱(XRD及与标准物质PDF卡片对照)在大约2θ＝24.3°处出现的宽峰证明了氧化石墨烯已被还原成为石墨烯；在2θ＝31.7°,34.4°,36.3°,47.6°,56.6°,62.9°,66.3°,67.9°,69.1°和72.7°处的尖峰分别对应于ZnO的(100),(002),(101),(102),(110),(103),(200),(112),(201)和(004)衍射晶面，这与标准ZnO(JCPDS#36-1451)的特征峰相吻合，从而证明了氧化锌量子点/石墨烯复合材料是由石墨烯与氧化锌所组成。
由图2氧化锌量子点/石墨烯复合材料的透射电子显微镜图像中明显可见该产物是由褶皱状的石墨烯负载氧化锌量子点所构成的复合物，且可以清楚看到粒径尺寸大小。
实施例2
将5.0g石墨、100mL98％浓硫酸和5g硝酸钠混合搅拌60min，称取10g高锰酸钾加入上述混合液继续搅拌24h；冰水浴下加入250mL蒸馏水稀释搅拌24h；加入80mL、30wt％的H2O2水溶液搅拌24h；离心分离除去所得混合物中的底层黑色大块沉淀物以及上层清液，收集中间层浅色产物，用蒸馏水反复洗涤收集GO悬浮液(1mg/mL)备用。
将稀释后的GO悬浮液(25.0mL，1.0mg/mL)转移至25mL样品瓶中。将金属锌片置于稀释后的GO悬浮液中，室温常压下搅拌30min，取出锌片，将剩余溶液置于80℃油浴条件下搅拌反应3h，生成黑色固体即氧化锌量子点/石墨烯复合材料。
用上述方法同样可以得到在RGO层之间有低于10nm的良好分散的ZnO量子点。
应用例：
将上述实施例获得氧化锌量子点/石墨烯复合材料用作锂离子电池负极材料(即工作电极材料活性材料)，将CR2016扣式电池用于测试复合材料样品的电化学性能，复合材料样品在高纯度氩气填充的手套箱中组装。工作电极由铜箔上的电化学活性材料(80％)，炭黑(10％)和聚偏氟乙烯(PVDF，10％)构成。金属锂片用作反电极和参比电极。电解质为含有浓度为1M的LiPF6的碳酸亚乙酯(EC)和碳酸二甲酯(DMC)和碳酸甲乙酯(EMC)体积比为1：1：1。将微孔聚乙烯膜作为隔膜置于工作电极和反电极之间。在Neware电池测试系统上进行恒电流充电和放电测试，电压范围为0.01至3.00V(相对于Li/Li+)。同时，将锌片放在GO溶液中静置反应收集得到的氧化锌/石墨烯的复合材料(ZnO@RGO)作为对比材料，用同样的方法制作电池并在相同的电流密度下进行测试。
由图3可以看出，氧化锌量子点/石墨烯(ZnO/RGO)在高电流密度1000mA·g-1下，充放电循环700次还能维持在668mA·g-1的高可逆容量，表现出优秀的电池循环性能。
图4可以看出，在200mA·g-1的电流密度下，经过200圈的充放电循环下，用本方法获得的氧化锌量子点/石墨烯(ZnO/RGO)复合材料在锂离子储存方面要优于对照材料氧化锌/石墨烯(ZnO@RGO)。并且第一圈的库伦效率高达97.4％。其优异的电池循环性能可归因于ZnO尺寸小，大而薄的RGO多孔支撑结构。
由上述可见，本发明复合材料的制备原料仅为金属Zn和GO悬浮液，合成路线不需要复杂的方法或苛刻的条件。操作条件温和简便，环保。这种有效的制备氧化锌量子点/石墨烯复合材料的合成方法具有很大的发展前景，对纳米材料的研究及应用具有重要意义。
1.C.G.Tian,Q.Zhang,A.P.Wu,M.J.Jiang,Z.L.Liang,B.J.Jiang and H.G.Fu,Chem.Commun.,2012,48,2858.
2.B.Xu,J.Zhang,Y.Gu,Z.Zhang,W.Al Abdulla,N.A.Kumar and X.S.Zhao,Electrochimica Acta,2016,212,473-480.
Claims (7)
1.一种氧化锌量子点/石墨烯复合材料的制备方法，其特征在于：向石墨、浓硫酸和硝酸钠的混合液中加入高锰酸钾搅拌混匀；冰水浴条件下经去离子水稀释；向所得稀释液中加入双氧水溶液，然后离心收集氧化石墨烯并经水稀释得到氧化石墨烯悬浮液(GO悬浮液)；将金属锌片置于GO悬浮液中，室温下搅拌，得到氢氧化锌/石墨烯中间产物悬浊液；去除锌片后将中间产物悬浊液加热，得到黑色固体沉淀产物即氧化锌量子点/石墨烯复合材料。
2.按权利要求1所述的氧化锌量子点/石墨烯复合材料的制备方法，其特征在于：所述金属锌片置于GO悬浮液中，室温下搅拌10-60min，去除锌片后，悬浊液在50-95℃油浴条件下反应0.5-4h，生成黑色固体即氧化锌量子点/石墨烯复合材料。
3.按权利要求1所述的氧化锌量子点/石墨烯复合材料的制备方法，其特征在于：
(1)将石墨、浓硫酸和硝酸钠按质量比为5-10：50-150：5-10混合，搅拌混匀得到混合液；混匀后加入高锰酸钾，继续搅拌均匀；
(2)将上述获得混合液于冰水浴条件下向(1)所得溶液中加入蒸馏水进行稀释搅拌；而后再加入过氧化氢水溶液搅拌；
(3)将上述混合液进行离心洗涤，收集除去所得混合物中的底层沉淀物及上层清液，收集中间层浅色产物，用蒸馏水反复洗涤中间层产物后，收集得到产物氧化石墨烯(GO)备用；
(4)将金属锌片置于经水稀释后的GO悬浮液中，室温条件下搅拌10-60min，而后取出锌片，收集氢氧化锌/石墨烯中间产物悬浊液备用；
(5)将氢氧化锌/石墨烯中间产物悬浊液在50-95℃条件下搅拌反应0.5-4h，生成黑色固体产物即得到氧化锌量子点/石墨烯复合材料。
4.按权利要求1-3所述的氧化锌量子点/石墨烯复合材料的制备方法，其特征在于：所述(1)中高锰酸钾与石墨的质量比为4-1:1，搅拌时间为12-24h。
5.按权利要求3所述的氧化锌量子点/石墨烯复合材料的制备方法，其特征在于：所述(2)中加入的蒸馏水与浓硫酸的体积比为1-2：1，搅拌时间为12-24h。
6.按权利要求3所述的氧化锌量子点/石墨烯复合材料的制备方法，其特征在于：所述(2)中加入的过氧化氢水溶液与浓硫酸的体积0.3—1:1；其中，水溶液中过氧化氢的浓度为10-40wt％，搅拌时间为6-24h。
7.一种权利要求1所述方法制备的氧化锌量子点/石墨烯复合材料其特征在于，按照权利要求1所述的方法制备所得氧化锌量子点/石墨烯复合材料。
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