CN102320597B - 一种石墨烯的制备方法 - Google Patents
一种石墨烯的制备方法 Download PDFInfo
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Abstract
本发明公开了一种石墨烯的制备方法，该方法包括如下步骤：在溶剂中加入六溴苯和A物质，搅拌成混合液并加热，在100-200℃，反应2-48小时，反应体系为无氧或有氧环境；压力为常压或加压环境；六溴苯、A物质和溶剂的比例为0.1-50mg∶0.05-500mg∶1mL；所述溶剂为二乙二醇二甲醚、二苯醚、乙醚、四氢呋喃、甲苯或苯；所述A物质为CuBr、CuI、CuCl、Cu或Ni。本发明的制备方法具有反应条件温和，工艺简单的优点，且有良好的重现性。其制备的石墨烯为单层石墨烯。本发明的石墨烯作为化学反应原料，催化剂载体，电池电极材料，物理学，微电子学方面具有广泛应用前景。
Description
技术领域
本发明涉及无机化学材料的合成，涉及一种石墨烯的制备方法。
背景技术
石墨烯作为一种新型的碳材料,由于其巨大的比表面积和良好的导电性,是现在热点研究新型碳材料。石墨烯材料的理论比表面积高达2600m2.g-1,具有突出的导热性能(3000W.m-1.K-1),高的电导率(2×102S.m-1)。
石墨烯的合成现一般有以下几种方法。微机械剥离法：2004年Novoselov等[1]用微机械剥离法成功地从高定向热解石墨上剥离并观测到单层石墨烯。这是首次报道得到石墨烯的方法。氧化石墨烯还原法：Horiuchi等[2]将天然石墨氧化,随后经过一系列的纯化，随后将氧化石墨升温到250℃,发现石墨由绝缘体变成了半导体。这可能是由于氧化石墨烯表面的基团在迅速升温过程中分解,导致一部分碳原子由sp3转化为sp2,使得氧化石墨烯的导电性增加。Stankovich等[3,4]研究了石墨的改性和还原。先将鳞片石墨氧化,分散于水中,然后再用水合肼进行还原。还原的氧化石墨的碳原子由sp3结构部分还原成sp2结构。用水合肼还原氧化石墨烯制备石墨烯现在已经成为一直广泛使用的方法。Li[5]等利用还原氧化石墨烯法制备出了在水中稳定分散的石墨烯溶液,并通过微过滤法制备出了石墨烯薄膜。化学气相沉积法：Zhu等[6]通过调整合成碳纳米管的参数,在没有催化剂的情况下用电感耦合频射等离子体化学气相沉积法在多种衬底上生长出了纳米石墨微片。Kim[7]研究组用CVD法在多晶Ni薄膜表面制备了尺寸可达到厘米数量级的石墨烯;Li[8]在Cu箔基底表面上采用CVD成功地制备了大面积、高质量石墨烯。Li等[9]通过甲烷在铜箔表面单晶生长得到了导电性能较好的石墨烯。
然而基于微机械剥离方法制得的石墨烯,产量很低,并且微量的剥离物中掺杂着很多多层石墨片。化学气相沉积法最大的优点是在导电基底上形成石墨烯，为下一步在电子学方面应用提供了可能，但是其工艺条件复杂。氧化石墨烯还原法是一种可行的大规模合成石墨烯的方法,虽然这种方法简便且成本较低,可以制备出大量石墨烯，但是由于氧化石墨并不能够完全被还原,导致其一些物理、化学等性能损失。
近来，Lv Wei等[10]利用氧化石墨在真空中低温热膨胀自身还原大规模制备出了石墨烯，为大规模简易制备石墨烯提供了一个新的方法。Wu ZS等[11]基于对化学剥离方法制备石墨烯过程的分析，他们提出了利用石墨原料的尺寸与结晶度不同来控制石墨烯层数的策略，宏量控制制备出单层、双层和三层占优的高质量石墨烯。Choucair等[12]利用金属钠和乙醇在高压釜中反应获得石墨烯前躯体，然后把得到的前躯体裂解，最后用水冲去钠盐，剩余产物就是石墨烯。
这些方法都为石墨烯的合成提供了新的思路。但是高质量石墨烯的大量合成，可控制备，特别是层数，边缘结构，面积等的调控，是石墨烯制备中尚未完全攻克的难点。利用从下到上的有机合成方法（bottom-up fabrication）制备石墨烯最有可能率先获得突破。
石墨烯可看做是由不含任何不稳定键的苯六元环通过sp2杂化组合而成的二维晶体，所以可以认为稠环芳烃是石墨烯的片段，将稠环芳烃通过一定方法组合在一起即可构成石墨烯。
Qian等[13]运用有机合成法制备了宽度受限，长度可控的石墨烯纳米带.以四溴酰亚胺(tetrabromo-perylene bisimides)作为单体,单体在碘化亚铜和L-脯氨酸的活化下可以发生多分子间的偶联反应,实现了含酰亚胺基团的石墨烯纳米带的高效化学合成。Yan等[14]以二碘四苯基对二氨基联苯(1,4-diiodo-2,3,5,6-tetraphenylbenzene)为原料以Pd(PPh3)4等为催化剂通过偶联反应得前体后在FeCl3,CH2Cl2/CH3NO2作用下环化脱氢制备得到了宽度为12nm的石墨烯带。
Cai等[15]在Au(111)和Ag(111)单晶表面作为基底，以10,10′-二溴-9,9′-联二蒽作为单体，通过脱卤素偶联进而发生环化脱氢作用，生成具有不同拓扑和宽度的、精度达到原子级的石墨烯纳米带。Yan等[16]以3-碘-4-溴苯胺为原料利用逐步Suzuki偶联反应得到聚亚苯基，然后在FeCl3,CH2Cl2/CH3NO2作用下环化脱氢得到大小结构可控的石墨烯量子点。
有机合成法为石墨烯形状，大小和边缘结构的可控制备提供了美好的前景。
参考文献
1.Novoselov K S,Geim A K,Morozov S V,et al.,Electric field effect in atomically thin carbonfilms,Science,2004,306:666-669.
2.Horiuchi S,Gotou T,Fujiwara M,et al.Graphene Sheet Detected in a Carbon Nanofilm,Appl Phys Lett,2004,84:2403-05
3.Stankovich S,Piner R D,Chen X Q,et al.，Stable aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly(sodium 4-styrenesulfonate),J Mater Chem,2006,16:155-1584 .Stankovich S,Piner R D,Nguyen S B,et al.Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets,Carbon,2006,44:3342-47
5.Li D,Muller M B,Gilje S,et al.Processable aqueous dispersions of graphenenanosheets,Nature nanotechnology,2008,3:101-105
6.Zhu M Y,Wang J J,Outlaw R A,et al.Direct current discharge plasma chemical vapordeposition of nano crystalline graphite films on carbon fibers.,Diam RelatMater,2007,16:196-201
7.Kim K.S.;Zhao Y.;Jang H.,et al.,Large-scale pattern growth of graphene films for stretchabletransparent electrodes.,Nature,2009,457:706710
8.Li,X.S.;Cai W.W.;An,J.H.,et al.,Large-Area Synthesis of High-Quality and UniformGraphene Films onCopper Foils.,Science,2009,324(5932):1312-14.
9.L X.S,Magnuson C.W.,Venugopal A.,et al.,Large-Area Graphene Single Crystals Grown byLow-Pressure Chemical Vapor Deposition of Methane on Copper,J.Am.Chem.Soc.2011,133:2816-19.
10.Lv W，Tang DM,He YB,et al.,Low-temperature exfoliated graphenes:vacuum-promotedexfoliation and electrochemical energy storage.,Acs Nano,2009,3:3730-36
11.Wu ZS,Ren WC,Gao LB,et al.,Synthesis of high-quality graphene with a pre-determinednumber of layers,Carbon,2009,47:493-499
12.Choucair M,Thordarson P,St ride J A,Gram-scale production of graphene based onsolvothermal synthesis and sonication.Nat.Nanot echnol.,2009,4:30-33
13.Qian H.L.;Negri F.;Wang C.R.,et al.Fully conjugated tri(perylene bisimides):An approach tothe construction of n-type graphene nanoribbons.JAm Chem Soc,2008,130(52):17970-76
14.Yang XY，Dou X,Rouhanipour A.,,et al.Two-Dimensional Graphene Nanoribbons.J AmChem Soc,2008,130(13):4216-17
15.Cai J.M,Ruffieux P,Jaafar R.,et al,Atomically precise bottom-up fabrication of graphemeanoribbons,Nature,2010,466(22):470-73
16.Yan X,Cui X,Li LS,Synthesis of Large,Stable Colloidal Graphene Quantum Dots withTunable Size,J Am Chem Soc,2010,132,5944-45
发明内容
本发明的目的是提供一种石墨烯的制备方法。
本发明的技术方案概述如下：
一种石墨烯的制备方法，包括如下步骤：在溶剂中加入六溴苯和A物质，搅拌成混合液并加热，在100-200℃，反应2-48小时，反应体系为无氧或有氧环境；压力为常压或加压环境；
六溴苯、A物质和溶剂的比例为0.1-50mg：0.05-500mg：1mL；
所述溶剂为二乙二醇二甲醚、二苯醚、乙醚、四氢呋喃、甲苯或苯；
所述A物质为CuBr、CuI、CuCl、Cu或Ni。
优选的是所述六溴苯和溶剂的比例为0.5-18mg:1mL。
所述A物质和溶剂的比例为0.1-60mg:1mL。
本发明的优点：
本发明的制备方法具有反应条件温和，工艺简单的优点，且有良好的重现性。其制备的石墨烯为单层石墨烯。本发明的石墨烯作为化学反应原料，催化剂载体，电池电极材料，物理学，微电子学方面具有广泛应用前景。
本发明可实现高质量石墨烯的大量合成，可控制备，边缘结构，面积等的调控。
附图说明
图1是本发明的方法制备的石墨烯的TEM图。
图2是本发明的方法制备的石墨烯的HRTEM图。
具体实施方式
下面的实施例是为了使本领域的技术人员能够更好地理解本发明，但不以任何方式限制本发明。
实施例1
将20mL二乙二醇二甲醚置于50mL圆底烧瓶内，再将0.04g的六溴苯（相当于2mg/mL）和0.01gCuBr(相当于0.5mg/mL)加入，搅拌，通高纯Ar气30min后，油浴加热，温度为140℃，反应14小时，保持反应体系的Ar气氛围，一直到反应体系自然冷却至室温，得到石墨烯。见图1和图2。
实施例2
将20mL甲苯置于50mL圆底烧瓶内，再加入六溴苯0.002g（相当于0.1mg/mL），0.001gCuCl(相当于0.05mg/mL)，搅拌，空气条件下，油浴加热，温度为100℃,回流4h，后自然冷却到室温，得到石墨烯。
实施例3
将20mL二乙二醇二甲醚置于50mL圆底烧瓶内，再加入六溴苯1g(相当于50mg/mL)，Cu粉10g（相当于500mg/mL）置于50mL圆底烧瓶中,搅拌，通Ar气30min后，油浴加热至160℃，反应时间为6小时，保持反应体系的Ar气氛围，一直到反应体系自然冷却至室温，得到石墨烯。
实施例4
将20mL乙醚置于25mL高压水热釜中，再加入六溴苯0.2g（相当于10mg/mL）和0.2gCuI(相当于10mg/mL)，加热，温度为100℃，反应30小时后，反应体系自然冷却至室温，得到石墨烯。
实施例5
将20mL苯置于25mL高压水热釜中，再加入六溴苯0.03g（相当于1.5mg/mL）和0.02gCuI(相当于1mg/mL)。加热，温度为120℃，反应48小时后，反应体系自然冷却至室温，得到石墨烯。
实施例6
将20mL二苯醚置于50mL圆底烧瓶内，再加入六溴苯0.08g（相当于4mg/mL），0.04gCuBr(相当于2mg/mL)，搅拌，空气条件下，油浴加热，温度为200℃,回流2h，自然冷却到室温，得到石墨烯。
实施例7
将20mL二乙二醇二甲醚置于50mL圆底烧瓶内，再将0.1g的六溴苯（相当于5mg/mL）和2g Ni(相当于100mg/mL)加入，搅拌，通高纯Ar气30min后，油浴加热，温度为160℃，反应20小时后，保持反应体系的Ar气氛围，一直到反应体系自然冷却至室温，得到石墨烯。实施例2-实施例7的TEM图和HRTEM图与实施例1的TEM图和HRTEM图相似。
Claims (3)
1.一种石墨烯的制备方法，其特征在于包括如下步骤：在溶剂中加入六溴苯和A物质，搅拌成混合液并加热，在100-200℃，反应2-48小时，反应体系为无氧或有氧环境；压力为常压或加压环境；
所述六溴苯、A物质和溶剂的比例为0.1-50mg∶0.05-500mg∶1mL；
所述溶剂为二乙二醇二甲醚、二苯醚、乙醚、四氢呋喃、甲苯或苯；
所述A物质为CuBr、CuI、CuCl、Cu或Ni。
2.根据权利要求1所述的一种石墨烯的制备方法，其特征在于所述六溴苯和溶剂的比例为0.5-18mg∶1mL。
3.根据权利要求1所述的一种石墨烯的制备方法，其特征在于所述A物质和溶剂的比例为0.1-60mg∶1mL。
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