CN107051228B - 一种直接生长超薄多孔石墨烯分离膜的方法 - Google Patents
一种直接生长超薄多孔石墨烯分离膜的方法 Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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Abstract
本发明提供了一种直接生长超薄多孔石墨烯分离膜的方法,属于膜技术领域。把刻蚀剂、有机溶剂和高分子聚合物涂覆在金属箔上,在无氧条件下高温煅烧;去掉金属基底和反应产物,即可得到单层或多层的多孔石墨烯分离膜。或将刻蚀剂的溶液或分散液涂覆在金属箔上,再覆盖一层有机高分子聚合物薄膜,在无氧条件下高温煅烧,去掉金属基底和反应产物,即可得到单层或多层的多孔石墨烯分离膜。本发明公开的方法简单,无需昂贵的设备和药品,成本低;可以直接生长出多孔石墨烯分离膜,不需要事先制备石墨烯原材料;制备出的石墨烯膜孔径可调,具有超高的水通量和和抗不可逆污染的能力。
Description
技术领域
本发明属于膜技术领域,特别涉及一种直接生长具有原子级或分子级厚度的超薄多孔石墨烯分离膜的方法。
背景技术
膜分离技术已广泛应用于食品、医药、生物、环保、化工、冶金、能源、石油、水处理等领域,已成为当今分离科学中最重要的手段之一。水通量是评价分离膜性能的一个非常重要的指标参数。一般地,膜的水通量越高,则分离过程的效率越高,耗能就越低。根据哈根-泊谡叶方程对超滤膜和微滤膜而言,膜通量(J)与其厚度(μ)和孔道曲折度(τ)成反比。由此可见,具有垂直贯通规则孔道结构的超薄分离膜相比较于传统分离膜,其水通量有望数量级别地提高。
石墨烯是由紧密堆积成的二维六方蜂窝状晶格结构的单层碳原子组成,是目前已知最薄、最坚固的材料。计算模拟和实验测定都证实,由单层或少层石墨烯制得的分离膜具有超高的水通量,主要是由于它原子级别的厚度,可以大大减弱水分子过膜时的动力学阻力。据我们所知,目前仅有2篇论文(K.Celebi,J.Buchheim,R.M.Wyss,A.Droudian,P.Gasser,I.Shorubalko,J.-I.Kye,C.Lee,H.G.Park.Ultimate Permeation AcrossAtomically Thin Porous Graphene.Science 2014,344,289;G.L.Wei,X.Quan,S.Chen,H.T.Yu.Superpermeable Atomic-Thin Graphene Membranes with HighSelectivity.ACS Nano,2017,11(2),1920–1926.)报道了厚度只有若干个碳原子层的多孔石墨烯超滤膜,并考察了气体分子或水分子的过膜通量。在K.Celebi的论文里,多孔石墨烯膜的制备用到了光刻技术,活性氧刻蚀技术和聚焦离子束钻孔技术,步骤较为复杂,并依赖昂贵的仪器,成本较高。而G.L.Wei利用碳热反应原理对石墨烯进行二次打孔处理得到多孔石墨烯分离膜,过程相对简单,但仍然需要两次高温过程,耗能较高。鉴于这种超薄多孔石墨烯膜优异的性能和良好的应用前景,探索其的低成本、简单高效、大面积制备技术具有重要意义。
发明内容
本发明主要是针对现有多孔石墨烯膜制备技术存在的缺点,即制备过程成本高,步骤较为繁琐,效率低,而提出一种低成本,简单高效的制备方法。
本发明的基本构思是将高分子聚合物和刻蚀剂涂覆在金属基底上。高温下,高分子聚合物裂解产生的碳原子在金属基底上发生重排生成石墨烯。一方面,刻蚀剂会占有金属基底上的某些位点,而被占有的位点无法生成石墨烯;另一方面,在一定温度下,刻蚀剂可以和石墨烯上的碳原子发生反应,生成的一氧化碳或二氧化碳以气体的形式从石墨烯上脱离。两方面的原因使得生成的石墨烯具有多孔结构,即多孔石墨烯膜。
本发明的技术方案:
一种直接生长超薄多孔石墨烯分离膜的方法,步骤如下:
(1)将刻蚀剂、溶剂A和高分子聚合物的混合物涂覆在金属箔上,在无氧条件下高温煅烧,其中,刻蚀剂、有机高分子聚合物和溶剂A的质量比为1:0.5-50:100-1000;或将刻蚀剂的溶液或分散液涂覆在金属箔上,再覆盖一层有机高分子聚合物薄膜,在无氧条件下高温煅烧,其中,刻蚀剂、有机高分子聚合物和溶剂B或分散剂B的质量比为1:0.5-50:100-1000;所述的高温煅烧为在400-1200℃温度条件下煅烧10分钟到4小时;
其中,所述的溶剂B或分散剂B用于溶解或分散刻蚀剂;
(2)去掉金属箔和反应产物,即得到超薄多孔石墨烯分离膜;所述的超薄多孔石墨烯分离膜为单层、双层或多层。
所述的刻蚀剂为金属氧酸盐、金属硝酸盐和金属氧化物的一种或两种以上混合;所述金属氧酸盐为高锰酸钾、高锰酸锂、高锰酸钠、锰酸钾、锰酸锂、锰酸钠、重铬酸钾、重铬酸钠、重铬酸锂、铬酸钾、铬酸钠、铬酸锂、钼酸锂、钼酸钾、钼酸钠中的一种或两种以上混合;所述的金属硝酸盐为硝酸铜、硝酸铁、硝酸钴、硝酸锰、硝酸镉、硝酸铬的一种或两种以上混合,优选地为硝酸铜和硝酸铁;所述的金属氧化物为氧化铜、氧化亚铜、四氧化三铁、三氧化二铁、氧化铝、氧化铬、二氧化钛、氧化钴、氧化镉、氧化锡的一种或两种以上混合。
所述的高分子聚合物为聚乙烯醇缩丁醛和/或聚甲基丙烯酸甲酯或二者的混合。
所述的溶剂A为甲醇、乙醇、异丙醇、丙酮、氯仿的一种或两种以上混合。
所述的金属箔为铜箔或镍箔。
所述的无氧条件为惰性气体保护或真空;所述的惰性气体为氮气、氩气、氦气、氖气、氪气、氙气、氡气的一种或几种的混合,考虑到经济成本,优选地为氮气和氩气;所述的真空为压力不大于50帕。
所述的刻蚀剂溶液或分散液的质量浓度为0.1%-20%。
去掉金属箔和反应产物的方法为把样品漂浮在0.5~5mol/L FeCl3/0.1~1mol/LHCl溶液或质量分数为0.1~10%的过硫酸铵溶液液面上。
配置刻蚀剂、有机高分子聚合物和溶剂A的溶液或分散液的步骤:在搅拌条件下,聚乙烯醇缩丁醛或聚甲基丙烯酸甲酯溶解在相对应的有机溶剂内,再溶解金属氧酸盐或金属硝酸盐;也可优选地,在搅拌条件下,聚乙烯醇缩丁醛或聚甲基丙烯酸甲酯溶解在相对应的有机溶剂内,再在超声辅助下,金属氧化物分散到上述溶液中。
所述的涂覆方式优选旋转涂膜和浸渍提拉。
配置刻蚀剂的溶液或分散液的步骤:在超声和搅拌条件下,把刻蚀剂溶解或分散到溶剂B或分散剂B中;所述溶剂B或分散剂B优选乙醇和水。
所述的干燥方式优选室温干燥。
有机高分子聚合物薄膜为聚乙烯醇缩丁醛薄膜、聚甲基丙烯酸甲酯薄膜、聚乙烯薄膜或聚四氟乙烯薄膜,优选为家庭用聚乙烯保鲜膜。
本发明的有益效果:本发明的方法简单,无需昂贵的设备和药品,成本较低;可以直接生长出多孔石墨烯分离膜,不需要事先制备石墨烯原材料;制备的石墨烯分离膜孔径可调,并具有超高的水通量和抗不可逆污染的能力。
附图说明
图1为实施例1制备得到的多孔石墨烯样品的拉曼图谱。
图2为实施例1制备得到的多孔石墨烯样品的扫描电镜照片。
图3为实施例2制备得到的多孔石墨烯样品的扫描电镜照片。
图4为实施例5制备得到的多孔石墨烯样品的扫描电镜照片。
具体实施方式
以下结合附图和技术方案,进一步说明本发明的具体实施方式。
实施例1
(1)配制质量比为1:5:200的硝酸铜/聚甲基丙烯酸甲酯/丙酮溶液。
(2)利用旋转涂膜机,把10μL上述溶液以1500r/min的转速旋涂在1cm×1cm的铜箔上。所得样品在总压力为100Pa,氩气流量为400sccm的条件下,以8℃/min升温到800℃并保温1h。随后引入10sccm氢气,总压力和温度保持不变的情况下继续升温到1000℃,再保温30min。最后样品冷却到室温。
(3)用2.5M FeCl3/0.5M HCl刻蚀掉铜基底后,生成的多孔石墨烯转移到其它目标基底上。
用拉曼光谱仪对上述方法制备的多孔石墨烯膜进行了表征,结果如图1所示。图1的谱图中有明显的G峰和2D峰,这些峰是石墨烯典型的特征峰,表明制得的样品材质是石墨烯。用扫描电子显微镜对上述方法制备的多孔石墨烯膜进行了表征,结果如图2所示。图片中有很多黑色斑点,为石墨烯上的孔,平均大小为20nm。测得的纯水通量为约48000L m-2h- 1bar-1。
实施例2
(1)配制质量比为1:2.5:100的硝酸铜/聚甲基丙烯酸甲酯/丙酮溶液。
(2)把10μL上述溶液以1500r/min的转速旋涂在1cm×1cm的铜箔上。所得样品在常压,氩气流量为400sccm的条件下,以8℃/min升温到800℃并保温1h。最后样品冷却到室温。
(3)用2.5M FeCl3/0.5M HCl刻蚀掉铜基底后,生成的多孔石墨烯转移到其它目标基底上。
对上述方法制备的多孔石墨烯膜用扫描电子显微镜表征,结果如图3所示。由图3可知,本发明得到了具有多孔结构的石墨烯分离膜,平均孔径为35nm。测得的纯水通量为约105000L m-2h-1bar-1。
实施例3
(1)配制质量比为1:25:1000的硝酸铁/聚乙烯醇缩丁醛/乙醇溶液。
(2)把20μL上述溶液以1000r/min的转速旋涂在2cm×2cm的镍箔上。所得样品在总压力为50Pa,氩气流量为400sccm的条件下,以8℃/min升温到800℃并保温1h。随后引入10sccm氢气,总压力和温度保持不变的情况下再煅烧30min。最后样品冷却到室温。
(3)用质量分数为2%的过硫酸铵溶液刻蚀掉铜基底后,生成的多孔石墨烯膜转移到其它目标基底上。
实施例4
(1)配制质量比为1:2.5:100的硝酸铜/聚甲基丙烯酸甲酯/丙酮溶液。
(2)把10cm×5cm的铜箔浸没在上述溶液中,然后以1mm/min的速度向上提拉。所得样品在常压,氩气流量为400sccm,温度为1000℃的条件下煅烧10min。随后引入10sccm氢气,总压力和温度保持不变的情况下再煅烧30min。最后样品冷却到室温。
(3)把有石墨烯的一面朝上,并在此面上用刮刀制出一层厚度大概为50μm、质量分数为15%的聚醚砜/N,N-二甲基甲酰胺溶液,随后迅速浸泡到水浴中。用2.5M FeCl3/0.5MHCl刻蚀掉铜基底后,可得到多孔石墨烯/聚醚砜复合膜。
实施例5
(1)配制质量比为1:50的硝酸铁/乙醇溶液。
(2)把20cm×10cm的铜箔平铺到热压设备上,在其上均匀地滴加上述配好的溶液并形成一层薄厚均匀的液膜,随后再覆盖一层家庭用聚乙烯保鲜膜。通过热压工艺,铜箔、硝酸铁和聚乙烯就形成了具有三明治结构的一个整体。所得样品在常压下,氩气流量为800sccm,温度为900℃下煅烧30min。最后样品冷却到室温。
(3)把有石墨烯的一面朝上,并在此面上用刮刀制出一层厚度大概为50μm质量分数为15%的聚偏氟乙烯/聚乙烯吡咯烷酮/N,N-二甲基甲酰胺溶液,随后迅速浸泡到水浴中。用2.5M FeCl3/0.5M HCl刻蚀掉铜基底后,可得到多孔石墨烯/聚偏氟乙烯复合膜。
对上述方法制备的多孔石墨烯膜用扫描电子显微镜表征,结果如图4所示。由图4可知,本发明得到了具有多孔结构的石墨烯/聚偏氟乙烯复合分离膜,平均孔径50nm。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的情况下,还可做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种直接生长超薄多孔石墨烯分离膜的方法,其特征在于,步骤如下:
(1)将刻蚀剂、溶剂A和高分子聚合物的混合物涂覆在金属箔上,在无氧条件下高温煅烧,其中,刻蚀剂、高分子聚合物和溶剂A的质量比为1:0.5-50:100-1000;或将刻蚀剂和溶剂B或分散剂B的溶液或分散液涂覆在金属箔上,再覆盖一层高分子聚合物薄膜,在无氧条件下高温煅烧,其中,刻蚀剂、高分子聚合物和溶剂B或分散剂B的质量比为1:0.5-50:100-1000;所述的高温煅烧为在400-1200℃温度条件下煅烧10分钟到4小时;
其中,所述的溶剂B或分散剂B用于溶解或分散刻蚀剂;
(2)去掉金属箔和反应产物,即得到超薄多孔石墨烯分离膜;所述的超薄多孔石墨烯分离膜为单层或多层。
2.根据权利要求1所述的方法,其特征在于,所述的刻蚀剂为金属氧酸盐、金属硝酸盐和、金属氧化物中的一种或两种以上的混合,刻蚀剂溶液或分散液的质量浓度为0.1%-20%。
3.根据权利要求1或2所述的方法,其特征在于,所述的高分子聚合物为聚乙烯醇缩丁醛和/或聚甲基丙烯酸甲酯。
4.根据权利要求1或2所述的方法,其特征在于,所述的溶剂A为甲醇、乙醇、异丙醇、丙酮、氯仿的一种或两种以上混合;所述的溶剂B或分散剂B为乙醇和/或水。
5.根据权利要求3所述的方法,其特征在于,所述的溶剂A为甲醇、乙醇、异丙醇、丙酮、氯仿的一种或两种以上混合;所述的溶剂B或分散剂B为乙醇和/或水。
6.根据权利要求1所述的方法,其特征在于,所述的金属箔为铜箔或镍箔。
7.根据权利要求3所述的方法,其特征在于,所述的金属箔为铜箔或镍箔。
8.根据权利要求4所述的方法,其特征在于,所述的金属箔为铜箔或镍箔。
9.根据权利要求1或2所述的方法,其特征在于,所述的无氧条件为惰性气体保护或真空。
10.根据权利要求6所述的方法,其特征在于,所述的无氧条件为惰性气体保护或真空。
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CN103265018A (zh) * | 2013-05-21 | 2013-08-28 | 上海大学 | 一种绝缘基底上直接制备石墨烯的方法 |
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Non-Patent Citations (1)
Title |
---|
Superpermeable Atomic-Thin Graphene Membranes with High Selectivity;Gaoliang Wei et al.;《ACS Nano》;20170207;第11卷;第1920-1926页 * |
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