层间共价增强石墨烯材料的构筑、性能与应用

doi:10.3866/PKU.WHXB202011059

摘要/Abstract

摘要：

大批量石墨烯可控制备技术的逐渐成熟为实现其宏观组装和应用提供了基础。在众多的组装策略中，调节石墨烯层间的界面相互作用可以直接影响组装体的力学、电学、热学以及渗透等性质，具有重要的意义。石墨烯片层间以共价键连接的层间共价石墨烯材料以其可调的层间距、较强的层间作用力、丰富的功能化、以及可能的原子构型重排等特性，受到了广泛的关注和深入的研究。相比于其他非共价的键合手段，共价连接是一种更为牢固的枢纽。本文中我们将总结讨论层间共价石墨烯材料的构筑方法、性能以及应用。在构筑方法中，依据石墨烯本身的制备方法分为氧化还原法以及化学气相沉积法，而在氧化还原法中，以其宏观材料的形貌分为纸状和纤维状来讨论。接着，我们重点介绍了层间共价对其力学和电学性能的影响，并概述了此类宏观组装体材料的应用。层间共价石墨烯材料继承了石墨烯自身优异的特性，同时也具有宏观组装所赋予的性能，有望在多个领域得到广泛的应用。

关键词: 石墨烯, 共价键, 金刚烯, 组装, 力学性质

Abstract:

The development of large-scale and controlled graphene production lays the foundation for macroscopic assembly. Among the diverse assembly strategies, modulating the interlayer interaction of graphene nanosheets is of vital importance because it determines the mechanical, electrical, thermal, and permeation properties of the macroscopic objects. Depending on the nature and strength of the interlayer interaction, covalent and noncovalent bondings, such as hydrogen bonding, ionic interaction, π-π interaction, and van der Waals force, are classified as two main types of interlayer connection methods, which solely or synergistically link the individual graphene nanosheets for practical macroscopic materials. Among them, the covalent bonding within the interlayer space renders graphene assembly adjusted interlayer distance, strong interlayer interaction, a rich diversity of functionalities, and potential atomic configuration reconstruction, which has attracted considerable research attention. Compared with other noncovalent assembly methods, covalent connections are stronger and thus more stable; however, there are some issues that remain. First, the covalent modification of the graphene surface depends on the defects and/or functional groups, which becomes difficult for graphene films free of surface imperfections. Second, the covalent connection partly alters the sp² hybrid carbon atoms to sp³, resulting in a deteriorated electrical conductivity. Thus, the electrical properties of the macroscopic assembly are far inferior to those of the constituent nanosheets, thereby restricting their applications. Lastly, covalent bonding is naturally rigid, rendering high modulus and strength to the graphene assembly while impairing the toughness. As in certain applications, both high strength and toughness are required; thus, a balanced covalent and noncovalent interaction is required. In this review, we discuss the recent progress in the construction method, properties, and applications of the interlayer covalently connected graphene materials. In the construction method, graphene is classified according to the synthesis method as oxidation-reduction and chemical vapor deposition method, wherein the latter represents graphene without abundant surface bonding sites and is hard to be covalently connected. For the former graphene produced by the oxidation-reduction method, the paper and fiber assembly forms are discussed. Then, the influence of covalent bonding on the mechanical and electrical properties is studied. Note that both the enhancement and potential impairments caused by covalent bonding are addressed. Finally, the applications in electrical devices, energy storage, and ion separation are summarized. The interlayer covalently connected macroscopic graphene material unifies the exceptional properties of graphene and the advantages of assembly strategy and will find applications in related fields. Moreover, it will also inspire the assembly of other graphene-like two-dimensional materials for a richer diversity of applications.

Key words: Graphene, Covalent bond, Diamane, Assembly, Mechanical property

MSC2000:

O641

梁涛, 王斌. 层间共价增强石墨烯材料的构筑、性能与应用[J]. 物理化学学报, 2022, 38(1): 2011059.

Tao Liang, Bin Wang. Interlayer Covalently Enhanced Graphene Materials: Construction, Properties, and Applications[J]. Acta Phys. -Chim. Sin., 2022, 38(1): 2011059.

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Materials	Young’s Modulus/GPa	Tensile Strength /MPa	Strain/%	Reference
Monolayer Graphene	1000	130000	–	²
GO Paper	32	100	0.6	¹⁶
Glutaraldehyde-GO Paper	30.4	101	0.4	¹⁷
Polyallylamine-GO Paper	33.3 ± 2.7	91.9 ± 22.4	0.32 ± 0.08	¹⁹
Boron-GO Paper	127 ± 4	185 ± 30	–	²⁰
PEI Crosslinked GO Paper	103.4	209.9	–	²¹
GO Fiber	5.4	102	6.8–10.1	²⁸
Phenolic Resin-GO Fiber	120	1450	1.8	³⁷
Monolayer GO	207.6 ± 23.4	–	–	⁵⁴
Monolayer rGO	250	–	–	⁵⁶

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