氧化石墨烯液晶相结构的调控及应用进展

doi:10.16085/j.issn.1000-6613.2018-0905

摘要/Abstract

摘要：

氧化石墨烯液晶（GOLCs）是氧化石墨烯薄片分散在水或极性有机溶剂中形成的宏观介晶有序、微观各向异性的液晶相，在自组装膜、储能、液晶显示器和超强纤维等领域展现良好的应用前景。本文首先介绍了氧化石墨烯液晶具有向列相、层状相和手性相等结构特征；具体综述了氧化石墨烯液晶相变的影响因素、调控途径及其原理，包括氧化石墨烯的尺寸及其分布、氧化石墨烯的氧化程度、氧化石墨烯在溶液中的质量/体积分数、溶剂的极性、溶液的pH以及添加盐的种类、浓度，外界施加的电场或磁场；最后简单介绍了氧化石墨烯液晶在电化学及其他方面的潜在应用。本文为调控氧化石墨烯液晶的相结构、开发多功能氧化石墨烯液晶及拓宽氧化石墨烯液晶的应用领域提供了理论指导。

关键词: 液晶, 氧化石墨烯, 相变, 调控途径, 电化学

Abstract:

Graphene oxide liquid crystals (GOLCs) are macroscopic ordered mesocrystalline and miscroscopic anisotropic liquid crystals phase, which can be formed by graphene oxide sheets dispersed in water or polar organic solvents, and hold promise in self-assembled film, energy storage, liquid crystals display and super fibers. Firstly, the phase structure characteristics of graphene oxide liquid crystals with nematic phase, lamellar phase and chirality phase are introduced. The influencing factors, regulation ways and principles of the graphene oxide liquid crystals phase change are reviewed in detail, including the size and size distribution of graphene oxide, oxidation degree of graphene oxide, mass/volume fraction, salt concentration, pH of solution, solvent polarity and externally applied electric or magnetic fields. Finally, the potential applications of graphene oxide liquid crystals in electrochemistry and other applications are introduced. This review may provide theoretical guidance for controlling the phase structure of graphene oxide liquid crystals, developing multifunctional graphene oxide liquid crystals and widening the applications of graphene oxide liquid crystals.

Key words: liquid crystals, graphene oxide, phase change, regulation ways and principles, electrochemistry

中图分类号:

O646

杨绍斌,籍遥函,沈丁. 氧化石墨烯液晶相结构的调控及应用进展[J]. 化工进展, 2019, 38(03): 1443-1451.

Shaobin YANG,Yaohan JI,Ding SHEN. Phase structure control and applications of graphene oxide liquid crystals[J]. Chemical Industry and Engineering Progress, 2019, 38(03): 1443-1451.

图/表 10

图1 氧化石墨烯液晶相的偏光显微图和SEM图像

图2 氧化石墨烯液晶的小角散射图和氧化石墨液晶的偏光显微图

图3 手性氧化石墨烯液晶的冷冻扫描电镜图、偏光显微图及手性模型

表1 氧化石墨烯A-C的平均直径<D>、直径标准差σ D和

GO	DL	σ _D	宽高比
A	1.65	1.28	1600
B	1.22	1.16	1200
C	0.75	0.88	700

图4 GGO溶液的相态与浓度之间的关系

图5 向列相体积分数与GO水溶液浓度之间的关系

图6 氧化石墨烯和氧化石墨的相图

图7 3种不同样品中GOLCs的偏光显微图与厚度和浓度的函数关系

图8 pH分别为2、6和9时向列相体积分数与GO浓度的函数关系

图9 不同NaCl浓度下GO分散体的相图和Zeta电位图

参考文献 52

1	CHUARD T ， DESCHENAUX R . First fullerene[60]-containing thermotropic liquid crystal. preliminary communication[J]. Helvetica Chimica Acta， 1996， 79(3): 736-741.
2	BEHABTU N , LOMEDA J R , GREEN M J , et al . Spontaneous high-concentration dispersions and liquid crystals of graphene[J]. Nature Nanotechnology, 2010, 5(6): 406-411.
3	ZAMORA-LEDEZMA C , PUECH N , ZAKRI C , et al . Liquid crystallinity and dimensions of surfactant-stabilized sheets of reduced graphene oxide[J]. The Journal of Physical Chemistry Letters，2012，3(17): 2425-2430.
4	XU Z ， GAO C . Aqueous liquid crystals of graphene oxide[J]. ACS Nano, 2011, 5(4): 2908-2915.
5	KIM J E， HAN T H , LEE S H, et al . Graphene oxide liquid crystals[J]. Angewandte Chemie International Edition， 2011， 50(13): 3043-3047.
6	JALILI R ， ABOUTALEBI S H ， ESRAFILZADEH D ， et al . Organic solvent-based graphene oxide liquid crystals: a facile route toward the next generation of self-assembled layer-by-layer multifunctional 3D architectures[J]. ACS Nano, 2013，7(5): 3981-3990.
7	DREYER D R , TODD A D ， BIELAWSKI C W . Harnessing the chemistry of graphene oxide[J]. Chemical Society Reviews, 2014, 43(15): 5288-5301.
8	LEE S H，LEE D H，LEE W J，et al . Tailored assembly of carbon nanotubes and graphene[J]. Advanced Functional Materials, 2011, 21(8): 1338-1354.
9	KIM J Y，KIM B H， HWANG J O ，et al . Flexible and transferrable self-assembled nanopatterning on chemically modified graphene[J]. Advanced Materials, 2013，25(9): 1331-1335.
10	YUN J M ，KIM K N，KIM J Y, et al . DNA origami nanopatterning on chemically modified graphene[J]. Angewandte Chemie: International Edition, 2012, 124(4): 936-939.
11	HWANG J O ，LEE D H，KIM J Y，et al . Vertical ZnO nanowires/graphene hybrids for transparent and flexible field emission[J]. Journal of Materials Chemistry，2011，21(10): 3432-3437.
12	LEE D H，LEE J A，LEE W J，et al . Flexible field emission of nitrogen-doped carbon nanotubes/reduced graphene hybrid films[J]. Small，2011，7(1): 95-100.
13	HAN T H ，LEE W J，LEE D H，et al . Peptide/graphene hybrid assembly into core/shell nanowires[J]. Advanced Materials，2010，22(18): 2060-2064.
14	BRODIE B C . Sur le poids atomique du graphite[J]. Ann. Chim. Phys.，1860, 59(466）: e472.
15	STAUDENMAIER L . Verfahren zur darstellung der graphitsäure[J]. European Journal of Inorganic Chemistry，1898，31(2): 1481-1487.
16	HUMMERES Jr W S ， OFFEMAN R E . Preparation of graphitic oxide[J]. Journal of the American Chemical Society，1958，80(6): 1339-1339.
17	DIMIEV A M ， TOUR J M . Mechanism of graphene oxide formation[J]. ACS Nano，2014，8(3): 3060-3068.
18	MARCANO D C ， KOSYNKIN D V ， BERLIN J M ，et al . Improved synthesis of graphene oxide[J]. ACS Nano，2010，4(8): 4806-4814.
19	PENG L ， XU Z ， LIU Z ，et al . An iron-based green approach to 1-h production of single-layer graphene oxide[J]. Nature Communications，2015, 6: 5716.
20	YU C ， WANG C F ， CHEN S . Facile access to graphene oxide from ferro-induced oxidation[J]. Scientific Reports, 2016, 6: 17071.
21	BLUNH D ， PRAEFCKE K ， VILL V ，et al . Amphotropic liquid crystals[M]//PRAEFCKE K, VILI V. Handbook of Liquid Crystals Set., New York: John wiley&sons Inc. 1998: 305-340.
22	童丽萍 . 氧化石墨烯基材料的液晶性与光子晶体研究及在交联酶聚体制备中的应用[D]. 天津：天津大学, 2014.
	TONG L P . Studies on graphene oxide-based materials: liquid crystals, photonic crystals and cross-linked enzyme aggregates[D]. Tianjin: Tianjin University, 2014.
23	SCALIA G ， BÜHLER C VON ， HÄGELE C ，et al . Spontaneous macroscopic carbon nanotube alignment via colloidal suspension in hexagonal columnar lyotropic liquid crystals[J]. Soft Matter，2008，4(3): 570-576.
24	PISULA W ， KASTLER M ， WASSERFALLEN D ，et al . Exceptionally long-range self-assembly of hexa-peri-hexabenzocoronene with dove-tailed alkyl substituents[J]. Journal of the American Chemical Society，2004，126(26): 8074-8075.
25	XU Z , GAO C . Graphene chiral liquid crystals and macroscopic assembled fibres[J]. Nature Communications，2011，2：571.
26	FERNSLER J ， HOUGH L ， SHAO R F ，et al . Giant-block twist grain boundary smectic phases[J]. Proceedings of the National Academy of Sciences，2005，102(40): 14191-14196.
27	ONSAGER L . Anisotropic solutions of colloids[J]. Phys. Rev., 1942, 62(558): 12.
28	ONSAGER L . The effects of shape on the interaction of colloidal particles[J]. Annals of the New York Academy of Sciences，1949，51(14): 627-659.
29	KOOIJ F M VAN DER ， LEKKERKERKER H N . Formation of nematic liquid crystals in suspensions of hard colloidal platelets[J]. The Journal of Physical Chemistry B，1998，102(40): 7829-7832.
30	KOOIJ F M VAN DER ， KASSAPIDOU K ， LEKKERKERKER H N . Liquid crystal phase transitions in suspensions of polydisperse plate-like particles[J].Nature，2000，406(6798): 868-871.
31	ABOUTALEBI S H ， GUDARZI M M ， ZHENG Q B ，et al . Spontaneous formation of liquid crystals in ultralarge graphene oxide dispersions[J]. Advanced Functional Materials，2011，21(15): 2978-2988.
32	DAN B， BEHABTU N ， MARTINEZ A ，et al . Liquid crystals of aqueous, giant graphene oxide flakes[J]. Soft Matter，2011，7(23): 11154-11159.
33	OH J Y， PARK J ， JEONG Y C ，et al . Secondary interactions of graphene oxide on liquid crystal formation and stability[J]. Particle & Particle Systems Characterization，2017，34(9): 16003831.
34	AL-ZANGANA S ， ILIUT M ， TURNER M ，et al . Confinement effects on lyotropic nematic liquid crystal phases of graphene oxide dispersions[J]. 2D Materials，2017，4(4): 0410041-10.
35	TKACZ R ， OLDENBOURG R ， MEHTA S B ，et al . pH dependent isotropic to nematic phase transitions in graphene oxide dispersions reveal droplet liquid crystalline phases[J]. Chemical Communications，2014，50(50): 6668-6671.
36	ZHAO X L ， XU Z ， XIE Y ，et al . Polyelectrolyte-stabilized graphene oxide liquid crystals against salt, pH, and serum[J]. Langmuir，2014，30(13): 3715-3722.
37	HUANG X ， HE J X ， SUN K , et al . Liquid crystal behavior and cytocompatibility of graphene oxide dispersed in sodium alginate solutions[J]. Carbon， 2018, 129: 258-269.
38	SHEN T Z ， HONG S H ， SONG J K . Electro-optical switching of graphene oxide liquid crystals with an extremely large Kerr coefficient[J]. Nature Materials，2014，13(4): 394-399.
39	AHMAD R T M ， HONG S H ， SHEN T Z ，et al . Optimization of particle size for high birefringence and fast switching time in electro-optical switching of graphene oxide dispersions[J]. Optics Express，2015，23(4): 4435-4440.
40	LEE W J， MAITI U N ，LEE J M，et al . Nitrogen-doped carbon nanotubes and graphene composite structures for energy and catalytic applications[J]. Chemical Communications，2014，50(52): 6818-6830.
41	GHOSH D ，KIM S O . Chemically modified graphene based supercapacitors for flexible and miniature devices[J]. Electronic Materials Letters，2015，11(5): 719-734.
42	MAITI U N ，LIM J，LEE K E，et al . Three-dimensional shape engineered, interfacial gelation of reduced graphene oxide for high rate, large capacity supercapacitors[J]. Advanced Materials，2014，26(4): 615-619.
43	CHIDEMBO A T ， ABOUTALEBI S H ， KONSTANTINOV K ，et al . Liquid crystalline dispersions of graphene-oxide-based hybrids: a practical approach towards the next generation of 3D isotropic architectures for energy storage applications[J]. Particle & Particle Systems Characterization，2014，31(4): 465-473.
44	KOU L , LIU Z , HUANG T Q , et al . Wet-spun, porous, orientational graphene hydrogel films for high-performance supercapacitor electrodes[J]. Nanoscale, 2015, 7(9): 4080-4087.
45	WANG B , LIU J Z , ZHAO Y , et al . Role of graphene oxide liquid crystals in hydrothermal reduction and supercapacitor performance[J]. ACS Applied Materials & Interfaces, 2016, 8(34): 22316-22323.
46	SHAIBANI M ， AKBARI A , SHEATH P , et al . Suppressed polysulfide crossover in Li-S batteries through a high-flux graphene oxide membrane supported on a sulfur cathode[J]. ACS Nano, 2016, 10(8): 7768-7779.
47	CHEN W , YAN L . Centimeter-sized dried foam films of graphene: preparation, mechanical and electronic properties[J]. Advanced Materials，2012，24(46): 6229-6233.
48	CHEN W , LI S , CHEN C , et al . Self-assembly and embedding of nanoparticles by in situ reduced graphene for preparation of a 3D graphene/nanoparticle aerogel[J]. Advanced Materials, 2011, 23(47): 5679-5683.
49	SHEN T Z , HONG S H , SONG J K . Effect of centrifugal cleaning on the electro-optic response in the preparation of aqueous graphene-oxide dispersions[J]. Carbon，2014，80：560-564.
50	HE L Q ， YE J ， SHUAI M ，et al . Graphene oxide liquid crystals for reflective displays without polarizing optics[J]. Nanoscale, 2015, 7(5): 1616-1622.
51	许震 . 石墨烯液晶及宏观组织纤维[D]. 杭州: 浙江大学，2013.
	XU Z . Graphene liquid crystals and macroscopically assembled fibers[D]. Hangzhou： Zhejiang University, 2013.
52	XIN G Q , YAO T K ， SUN H T , et al . Highly thermally conductive and mechanically strong graphene fibers[J]. Science, 2015, 349(6252): 1083-1087.

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