CN111320153B - 一种二维层状GeP材料及其制备方法和应用 - Google Patents
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Abstract
本发明属于二维材料领域，并具体公开了一种二维层状GeP材料及其制备方法和应用，制备方法包括如下步骤：S1采用锗单质和红磷制备GeP单晶块体；S2对GeP单晶块体进行电化学剥离得到二维层状GeP材料，电化学剥离时采用0.3mol/L～0.8mol/L的四丁基氨离子液体作为电解液。本发明通过电化学剥离的方法制备出不同厚度的二维层状GeP纳米薄片，从而解决传统制备方法效率低、不易控制的问题，进一步提高制备二维材料制备的均匀性和可控性，制备出的二维材料在储能、生物载药、催化、非线性光学等方面有良好的应用前景。
Description
技术领域
本发明属于二维材料领域，更具体地，涉及一种二维层状GeP材料及其制备方法和应用。
背景技术
自2004年石墨烯单原子层二维材料发现以来，打破了长期以来二维晶体是否存在的争论，随后，一系列关于二维材料的研究掀起热潮。由于石墨烯的零带隙特点，对光的吸收能力差且开关比低，限制了石墨烯在电子学和光电子学领域的应用。近年来，一些具有非零带隙的组多单层或者少层过渡金属硫化物和黑磷等的发现，为光电子学和光电子学领域打开了新的方向。另外，与IV族单质材料不同，V族元素二维半导体如BP(黑磷)具有从0.35至1.73eV的连续可调带隙，与其固有的高空穴迁移率相结合，使其在高性能场效应晶体管(FET)、光电检测器和太阳能电池等领域具有潜在应用。尽管有许多优异的特征，但是BP在空气中欠稳定性在一定程度上限制了其应用。而将其与IV族元素，如C，Si，Ge等进行结合，可以整合IV和V族元素的优势，例如高的稳定性、高空穴迁移率、宽的可调带隙以及面内各向异性。而IV族元素的磷化物，如就Ge的磷化物的化学稳定性来说，GeP(磷化锗晶体)的稳定性高于GeP3，且均比BP具有更好地稳定性。
GeP具有低对称的单斜晶体结构，属于C2/m(No.12)空间群，这种低对称结构确保了GeP的平面各向异性。要得到少层甚至单层的GeP，需要对GeP单晶块体进行剥离，现有的剥离方式通常为机械剥离，通过胶带反复粘贴，但是这样得到的GeP二维材料厚度和层数控制困难，且大小不均匀，较薄处通常散落在较厚的材料周围，制备效率低，不利于收集，且在储能、催化、非线性光学以及药物传递系统应用中存在较大的困难。
发明内容
针对现有技术的以上缺陷或改进需求，本发明提供了一种二维层状GeP材料及其制备方法和应用，其目的在于，对GeP单晶块体进行电化学剥离方法以制备二维层状材料，从而解决传统制备方法效率低、不易控制的问题，进一步提高制备二维材料制备的均匀性和可控性。
为实现上述目的，按照本发明的第一方面，提出了一种二维层状GeP材料的制备方法，包括如下步骤：
S1采用锗单质和红磷制备GeP单晶块体；
S2对GeP单晶块体进行电化学剥离得到二维层状GeP材料，电化学剥离时采用0.3mol/L～0.8mol/L的四丁基氨离子液体作为电解液。
作为进一步优选的，采用二电极法或三电极法对GeP单晶块体进行电化学剥离。
作为进一步优选的，采用二电极法时，以GeP单晶块体为工作电极，Pt电极为对电极，且该工作电极与对电极之间的距离为1cm～1.5cm；采用三电极法时，以GeP单晶块体为工作电极，Pt电极为对电极，甘汞电极为参比电极。
作为进一步优选的，进行电化学剥离时，电压为2V～5V，电化学剥离时间为0.5h～96h。
作为进一步优选的，所述四丁基氨离子液体由六氟磷酸四丁基氨或四丁基碘化铵溶于N,N-二甲基甲酰胺溶液制成。
作为进一步优选的，所述S1中制备GeP单晶块体，具体包括如下步骤：
S11将锗单质、红磷和助熔剂加入瓷舟内混匀，将该瓷舟放入石英管内，并将石英管抽真空后高温封管，所述锗单质和红磷的摩尔比为1:2；
S12将石英管加热至900℃～960℃并保温，再以2℃/min的速度降温至600℃得到GeP单晶块体，然后高温离心，将GeP单晶块体与助熔剂分离，完成GeP单晶块体的制备。
作为进一步优选的，所述助熔剂为Bi或Sn，且助熔剂与锗单质的摩尔比为1:8～1:12。
作为进一步优选的，所述GeP单晶块体的尺寸为：长3mm～10mm，宽1mm～2mm，高0.1mm～0.5mm。
按照本发明的第二方面，提供了一种采用上述方法制备而成的二维层状GeP材料。
作为进一步优选的，该二维层状GeP材料的尺寸为：长50nm～10μm，宽10nm～2μm，厚度4nm～15nm。
按照本发明的第三方面，提供了一种上述二维层状GeP材料在制备电极片或药物传递系统的应用。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，主要具备以下的技术优点：
1.本发明采用的电化学剥离方法，相比于传统机械剥离，一方面可以抑制/缓解剥离过程中单晶块体的粉化和破碎，通过调节电化学参数可以剥离出不同层数、对应于不同厚度的二维层状晶体，提高制备二维材料制备的均匀性和可控性；另一方面电化学剥离可以批量制备二维层状材料，且剥离效率更高。
2.本发明通过对各种晶体生长参数的控制，制得了长3mm～10mm，宽1mm～2mm，高0.1mm～0.5mm的高质量GeP单晶块体，进而通过电化学剥离得到二维层状GeP材料，其在储能、生物载药、催化、非线性光学等方面有良好的应用前景。
附图说明
图1是本发明实施例二维层状GeP材料制备流程图；
图2是本发明实施例电化学剥离的二维层状GeP的光学显微镜(OM)图；
图3是本发明实施例电化学剥离的二维层状GeP的原子力显微镜图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
本发明实施例提供的一种二维层状GeP材料制备方法，如图1所示，包括如下步骤：
S1制备GeP单晶块体：
S11将摩尔比为1:2的锗单质和红磷在研钵中研磨混匀，并放入圆柱形的Al2O3瓷舟内，然后向Al2O3瓷舟内加入助熔剂并混匀；将该瓷舟放入石英管内，并将石英管抽真空后高温封管；优选的，所述助熔剂为Bi或Sn，且助熔剂与锗单质的摩尔比为1:8～1:12；
S12将石英管置于马弗炉中，加热至900℃～960℃，并保温24h，再以2℃/min的速度降温至600℃得到GeP单晶块体，然后高温离心，将GeP单晶块体与助熔剂分离，完成GeP单晶块体的制备；得到的GeP单晶块体的尺寸为：长3mm～10mm，宽1mm～2mm，高0.1mm～0.5mm。
S2剥离二维层状GeP：
S21采用二电极法或三电极法对GeP单晶块体进行电化学剥离得到二维层状GeP，电化学剥离时采用0.3mol/L～0.8mol/L的四丁基氨离子液体作为电解液；优选的，进行电化学剥离时，电压为2V～5V，电化学剥离时间为0.5h～96h；所述四丁基氨离子液体由六氟磷酸四丁基氨或四丁基碘化铵溶于N,N-二甲基甲酰胺溶液制成；
进一步的，采用二电极法时，以GeP单晶块体为工作电极，Pt电极为对电极，且该工作电极与对电极之间的距离为1cm～1.5cm；采用三电极法时，以GeP单晶块体为工作电极，Pt电极为对电极，甘汞电极为参比电极。
S22将剥离下的二维层状GeP依次用所述四丁基氨离子液体和乙醇清洗，得到二维层状GeP材料。
制备得到的二维层状GeP材料的尺寸为：长50nm～10μm，宽10nm～2μm，厚度4nm～15nm，如图2和图3所示，分别为二维层状GeP材料的光学显微镜图和原子力显微镜图。
上述二维层状GeP材料可应用于制备电极片或载药，具体的：
(1)将二维层状GeP与Super P以及CMC粘结剂以质量比75:10:15混合，均匀涂布在集流体上，制备成电极片，对电极采用锂/钠金属，隔膜为celgard2300隔膜，电解液为商业化锂/钠离子电池电解液。
(2)将二维层状GeP用分子量为2000Da的氨基聚乙二醇(PEG-NH2)修饰，通过静电吸附作用进一步提高二维层状GeP的稳定性、生物相容性以及分散性；接着，将PEG修饰的二维层状GeP分散在磷酸盐缓冲液(PBS)中，然后与浓度为1mg/ml的DOX混合搅拌24h，并离心去除多余的DOX，得到载有DOX的二维层状GeP溶液。
以下为具体实施例：
实施例1
S1制备GeP单晶块体：
S11将摩尔比为1:2的锗单质和红磷在研钵中研磨混匀，并放入圆柱形的Al2O3瓷舟内，然后向瓷舟内加入助熔剂Bi并混匀(Bi与锗单质的摩尔比为1:10)，锗采用高纯度Ge粉，P为红磷，Ge、P、Bi混合物的总重量为4g；再将该瓷舟放入石英管内，并将石英管抽真空后高温封管；
S12将石英管置于马弗炉中，加热至900℃并保温24h，再以2℃/min的速度降温至600℃得到GeP单晶块体，然后高温离心，将GeP单晶块体与助熔剂分离，完成GeP单晶块体的制备。
S2剥离二维层状GeP：
S21将六氟磷酸四丁基氨溶于N,N-二甲基甲酰胺溶液，配制成0.5mol/L的四丁基氨离子液体作为电解液；采用二电极法对GeP单晶块体进行电化学剥离得到二维层状GeP，具体以GeP单晶块体为工作电极，Pt电极为对电极，工作电极与对电极之间的距离为1.5cm，电化学剥离电压为3V，电化学剥离时间为10h；
S22将剥离下的二维层状GeP依次用所述四丁基氨离子液体和乙醇清洗各三次，超声分散10min，得到均匀的二维层状GeP材料。
实施例2
S1制备GeP单晶块体：
S11将摩尔比为1:2的锗单质和红磷在研钵中研磨混匀，并放入圆柱形的Al2O3瓷舟内，然后向瓷舟内加入助熔剂Sn并混匀，Ge、P、Sn混合物的总重量为4g；再将该瓷舟放入石英管内，并将石英管抽真空后高温封管；
S12将石英管置于马弗炉中，加热至900℃并保温24h，再以2℃/min的速度降温至600℃得到GeP单晶块体，然后高温离心，将GeP单晶块体与助熔剂分离，完成GeP单晶块体的制备。
S2剥离二维层状GeP：
S21将四丁基碘化铵溶于N,N-二甲基甲酰胺溶液，配制成0.8mol/L的四丁基氨离子液体作为电解液；采用三电极法对GeP单晶块体进行电化学剥离得到二维层状GeP，具体以GeP单晶块体为工作电极，Pt电极为对电极，以甘汞电极作为参比电极，电化学剥离电压为2V，电化学剥离时间为96h；
S22将剥离下的二维层状GeP依次用所述四丁基氨离子液体和乙醇清洗各三次，超声分散10min，得到均匀的二维层状GeP材料。
实施例3
S1制备GeP单晶块体：
S11将摩尔比为1:2的锗单质和红磷在研钵中研磨混匀，并放入圆柱形的Al2O3瓷舟内，然后向瓷舟内加入助熔剂Sn并混匀，Ge、P、Sn混合物的总重量为4g；再将该瓷舟放入石英管内，并将石英管抽真空后高温封管；
S12将石英管置于马弗炉中，加热至900℃并保温24h，再以2℃/min的速度降温至600℃得到GeP单晶块体，然后高温离心，将GeP单晶块体与助熔剂分离，完成GeP单晶块体的制备。
S2剥离二维层状GeP：
S21将四丁基碘化铵溶于N,N-二甲基甲酰胺溶液，配制成0.3mol/L的四丁基氨离子液体作为电解液；采用三电极法对GeP单晶块体进行电化学剥离得到二维层状GeP，具体以GeP单晶块体为工作电极，Pt电极为对电极，以甘汞电极作为参比电极，电化学剥离电压为5V，电化学剥离时间为0.5h；
S22将剥离下的二维层状GeP依次用所述四丁基氨离子液体和乙醇清洗各三次，超声分散10min，得到均匀的二维层状GeP材料。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (6)
1.一种二维层状GeP材料在药物传递系统中的应用，其特征在于，包括如下步骤：
S1 采用锗单质和红磷制备GeP单晶块体；该GeP单晶块体的尺寸为：长3 mm～10mm，宽1mm～2mm，高0.1 mm～0.5mm；
S2 对GeP单晶块体进行电化学剥离得到二维层状GeP材料，电化学剥离时采用0.3mol/L～0.8mol/L的四丁基氨离子液体作为电解液，电化学剥离电压为5V，时间为0.5h；
S3 将二维层状GeP用分子量为2000 Da的氨基聚乙二醇修饰，通过静电吸附作用提高二维层状GeP的稳定性、生物相容性以及分散性；将氨基聚乙二醇修饰的二维层状GeP分散在磷酸盐缓冲液中，然后与浓度为1mg/ml的DOX混合搅拌24h，并离心去除多余的DOX，得到载有DOX的二维层状GeP溶液。
2.如权利要求1所述的二维层状GeP材料在药物传递系统中的应用，其特征在于，采用二电极法或三电极法对GeP单晶块体进行电化学剥离。
3.如权利要求2所述的二维层状GeP材料在药物传递系统中的应用，其特征在于，采用二电极法时，以GeP单晶块体为工作电极，Pt电极为对电极，且该工作电极与对电极之间的距离为1cm～1.5cm；采用三电极法时，以GeP单晶块体为工作电极，Pt电极为对电极，甘汞电极为参比电极。
4.如权利要求1所述的二维层状GeP材料在药物传递系统中的应用，其特征在于，所述四丁基氨离子液体由六氟磷酸四丁基氨或四丁基碘化铵溶于N,N-二甲基甲酰胺溶液制成。
5.如权利要求1所述的二维层状GeP材料在药物传递系统中的应用，其特征在于，所述S1中制备GeP单晶块体，具体包括如下步骤：
S11 将锗单质、红磷和助熔剂加入瓷舟内混匀，将该瓷舟放入石英管内，并将石英管抽真空后高温封管，所述锗单质和红磷的摩尔比为1:2；
S12 将石英管加热至900℃～960℃并保温，再以2℃/min的速度降温至600℃得到GeP单晶块体，然后高温离心，将GeP单晶块体与助熔剂分离，完成GeP单晶块体的制备。
6.如权利要求5所述的二维层状GeP材料在药物传递系统中的应用，其特征在于，所述助熔剂为Bi或Sn，且助熔剂与锗单质的摩尔比为1:8～1:12。
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