25th Anniversary Article: Carbon Nanotube‐ and Graphene‐Based Transparent Conductive Films for Optoelectronic Devices

Carbon nanotube (CNT)‐ and graphene (G)‐based transparent conductive films (TCFs) are two promising alternatives for commonly‐used indium tin oxide‐based TCFs for future flexible optoelectronic devices. This review comprehensively summarizes recent progress in the fabrication, properties, modification, patterning, and integration of CNT‐ and G‐TCFs into optoelectronic devices. Their potential applications and challenges in optoelectronic devices, such as organic photovoltaic cells, organic light emitting diodes and touch panels, are discussed in detail. More importantly, their key characteristics and advantages for use in these devices are compared. Despite many challenges, CNT‐ and G‐TCFs have demonstrated great potential in various optoelectronic devices and have already been used for some products like touch panels of smartphones. This illustrates the significant opportunities for the industrial use of CNTs and graphene, and hence pushes nanoscience and nanotechnology one step towards practical applications.     

氧化石墨烯及其复合材料对水中放射性核素的吸附

在核能和核技术的快速发展过程及应用中产生了大量放射性废水,其对生态环境会造成潜在的污染,因此对放射性废水处理技术的研究对保护环境有着重要的意义。氧化石墨烯及其复合材料具有比表面积高、官能团丰富、吸附能力强、化学稳定性好等优点,在放射性废水处理领域受到广泛关注。本文综述了近年来有关氧化石墨烯及其复合材料对水中放射性核素吸附的研究现状及进展,介绍了氧化石墨烯及其复合材料对放射性核素的吸附容量、吸附等温模型、吸附热力学、影响因素和吸附机理。最后分析了氧化石墨烯及其复合材料处理放射性核素在辐射稳定性和高吸附选择性等方面面临的问题和挑战,探讨了推动该类材料今后实际放射性废水处理中工程应用的重点研究方向,如完善的产业体系和积极研发相匹配的成套水处理工艺及设备等。     

A Robust and Cost‐Effective Superhydrophobic Graphene Foam for Efficient Oil and Organic Solvent Recovery

Water pollution caused by chemical reagent leaking, industrial wastewater discharging, and crude oil spills has raised global concerns on environmental sustainability, calling for high‐performance absorbent materials for effective treatments. However, low‐cost materials capable of effectively separating oils and organic solvents from water with a high adsorption capacity and good recyclability are rare on the market. Here, a cost‐effective method is reported to fabricate high‐performance graphene modified absorbents through the facile thermal reduction of graphene oxide on the skeletons of melamine foam. By integrating the high porosity, superior elasticity, and mechanical stability of raw sponge with the chemical stability and hydrophobicity of graphene sheets, the as‐fabricated graphene foam not only possesses a rough and superhydrophobic surface, but also exhibits an excellent adsorption performance and extraordinary recyclability for various oils and organic solvents. It is worth mentioning that the superhydrophobic surface also endows the graphene foam with an excellent efficiency for oil/water separation. More importantly, the cost‐effective fabrication method without involving expensive raw materials and sophisticated equipment permits a scale‐up of the graphene foam for pollution disposal. All these features make the graphene foam an ideal candidate for removal and collection of oils and organic solvents from water.     

MXene-based nanomaterials as adsorbents for wastewater treatment: a review on recent trends

The wastewater treatment is a challenging research area to reduce the increasing pressure on limited fresh water resources. Amongst several techniques adopted and practiced, adsorption is one of the most effective and sustainable eco-friendly processes. In recent years, MXene nanomaterials, a new family of transition metal carbides, have gained increasing attention as the potential adsorbent for pollutants due to their unique features such as large surface area with abundant active sites and hydrophilicity. A wide range of pollutants viz. heavy metal ions, organic dyes, radionuclides, and toxic gas molecules have been sensed by 2D MXenes. An inclusive understanding on the adsorptive behavior of MXene-based materials is needed to explain the removal mechanism and effects of different adsorption parameters. This review gives a general overview on recent research progress on MXene materials with special reference to their applications for the adsorptive removal of different pollutants. The general trends in the synthesis of MXenes, their stability and different factors affecting the adsorption process along with the main challenges in understanding the full potential of MXenes for environmental applications are discussed.     

Self‐Assembled Hybrid Materials Based on Organic Nanocrystals and Carbon Nanotubes

Organic crystalline materials are used as dyes/pigments, pharmaceuticals, and active components of photonic and electronic devices. There is great interest in integrating organic crystals with inorganic and carbon nanomaterials to create nanocomposites with enhanced properties. Such efforts are hampered by the difficulties in interfacing organic crystals with dissimilar materials. Here, an approach that employs organic nanocrystallization is presented to fabricate solution‐processed organic nanocrystal/carbon nanotube (ONC/CNT) hybrid materials based on readily available organic dyes (perylene diimides (PDIs)) and carbon nanotubes. The hybrids are prepared by self‐assembly in aqueous media to afford free‐standing films with tunable CNT content. These exhibit excellent conductivities (as high as 5.78 ± 0.56 S m^?1), and high thermal stability that are superior to common polymer/CNT hybrids. The color of the hybrids can be tuned by adding various PDI derivatives. ONC/CNT hybrids represent a novel class of nanocomposites, applicable as optoelectronic and conductive colorant materials.     

Carbon Nanotube–Multilayered Graphene Edge Plane Core–Shell Hybrid Foams for Ultrahigh‐Performance Electromagnetic‐Interference Shielding

Materials with an ultralow density and ultrahigh electromagnetic‐interference (EMI)‐shielding performance are highly desirable in fields of aerospace, portable electronics, and so on. Theoretical work predicts that 3D carbon nanotube (CNT)/graphene hybrids are one of the most promising lightweight EMI shielding materials, owing to their unique nanostructures and extraordinary electronic properties. Herein, for the first time, a lightweight, flexible, and conductive CNT–multilayered graphene edge plane (MLGEP) core–shell hybrid foam is fabricated using chemical vapor deposition. MLGEPs are seamlessly grown on the CNTs, and the hybrid foam exhibits excellent EMI shielding effectiveness which exceeds 38.4 or 47.5 dB in X‐band at 1.6 mm, while the density is merely 0.0058 or 0.0089 g cm^?3, respectively, which far surpasses the best values of reported carbon‐based composite materials. The grafted MLGEPs on CNTs can obviously enhance the penetration losses of microwaves in foams, leading to a greatly improved EMI shielding performance. In addition, the CNT–MLGEP hybrids also exhibit a great potential as nano‐reinforcements for fabricating high‐strength polymer‐based composites. The results provide an alternative approach to fully explore the potentials of CNT and graphene, for developing advanced multifunctional materials.     

Carbon‐Based Functional Materials Derived from Waste for Water Remediation and Energy Storage

Carbon‐based functional materials hold the key for solving global challenges in the areas of water scarcity and the energy crisis. Although carbon nanotubes (CNTs) and graphene have shown promising results in various fields of application, their high preparation cost and low production yield still dramatically hinder their wide practical applications. Therefore, there is an urgent call for preparing carbon‐based functional materials from low‐cost, abundant, and sustainable sources. Recent innovative strategies have been developed to convert various waste materials into valuable carbon‐based functional materials. These waste‐derived carbon‐based functional materials have shown great potential in many applications, especially as sorbents for water remediation and electrodes for energy storage. Here, the research progress in the preparation of waste‐derived carbon‐based functional materials is summarized, along with their applications in water remediation and energy storage; challenges and future research directions in this emerging research field are also discussed.     

氧化石墨烯复合材料吸附铀的研究进展

氧化石墨烯由于具有超大的比表面积、高强度和化学稳定性好等优点,其在环保领域作为含铀废水吸附材料的应用潜能备受关注。本文综述了近年来石墨烯基复合材料吸附水溶液中铀的研究现状及进展,介绍了石墨烯基复合材料对铀的吸附性能,分析了溶液pH值、温度、离子强度、接触时间和吸附剂用量等因素对吸附效果影响的原理,阐述了通过表面络合模型,光谱分析和理论计算等方法探讨氧化石墨烯复合材料的微观形貌结构与铀吸附效果之间的内在联系,最后研究了氧化石墨烯复合材料吸附铀研究中面临的挑战,对石墨烯材料与轴的相互作用机理及其在环保方面的开发应用进行了展望。     

基于纳米材料的气凝胶制备及应用

气凝胶是一种三维多孔材料,具有孔隙率高、比表面积大、密度低等特性。以纳米材料构筑气凝胶可进一步调控孔隙结构、改善机械强度,同时还能赋予气凝胶高导电性、低热导率、高吸附性和隔音吸声等特性,在储能、保温隔热、吸附材料等领域有重要的应用。重点对近年以纳米颗粒、纳米纤维素、碳纳米纤维、碳纳米管、石墨烯等不同形态纳米材料构筑的气凝胶的制备、结构、性能和应用进行了综述,同时展望了气凝胶的发展前景与方向。     

Hybrid Films of Graphene and Carbon Nanotubes for High Performance Chemical and Temperature Sensing Applications

A hybrid composite material of graphene and carbon nanotube (CNT) for high performance chemical and temperature sensors is reported. Integration of 1D and 2D carbon materials into hybrid carbon composites is achieved by coupling graphene and CNT through poly(ionic liquid) (PIL) mediated‐hybridization. The resulting CNT/PIL/graphene hybrid materials are explored as active materials in chemical and temperature sensors. For chemical sensing application, the hybrid composite is integrated into a chemo‐resistive sensor to detect a general class of volatile organic compounds. Compared with the graphene‐only devices, the hybrid film device showed an improved performance with high sensitivity at ppm level, low detection limit, and fast signal response/recovery. To further demonstrate the potential of the hybrid films, a temperature sensor is fabricated. The CNT/PIL/graphene hybrid materials are highly responsive to small temperature gradient with fast response, high sensitivity, and stability, which may offer a new platform for the thermoelectric temperature sensors.     

Recent developments in inorganically filled carbon nanotubes: successes and challenges

Abstract

Carbon nanotubes (CNTs) are a unique class of nanomaterials that can be imagined as rolled graphene sheets. The inner hollow of a CNT provides an extremely small, one-dimensional space for storage of materials. In the last decade, enormous effort has been spent to produce filled CNTs that combine the properties of both the host CNT and the guest filling material. CNTs filled with various inorganic materials such as metals, alloys, semiconductors and insulators have been obtained using different synthesis approaches including capillary filling and chemical vapor deposition. Recently, several potential applications have emerged for these materials, such as the measurement of temperature at the nanoscale, nano-spot welding, and the storage and delivery of extremely small quantities of materials. A clear distinction between this class of materials and other nanostructures is the existence of an enormous interfacial area between the CNT and the filling matter. Theoretical investigations have shown that the lattice mismatch and strong exchange interaction of CNTs with the guest material across the interface should result in reordering of the guest crystal structure and passivation of the surface dangling bonds and thus yielding new and interesting physical properties. Despite preliminary successes, there remain many challenges in realizing applications of CNTs filled with inorganic materials, such as a comprehensive understanding of their growth and physical properties and control of their structural parameters. In this article, we overview research on filled CNT nanomaterials with special emphasis on recent progress and key achievements. We also discuss the future scope and the key challenges emerging out of a decade of intensive research on these fascinating materials.     

Adsorption uptake of synthetic organic chemicals by carbon nanotubes and activated carbons

Carbon nanotubes (CNTs) have shown great promise as high performance materials for adsorbing priority pollutants from water and wastewater. This study compared uptake of two contaminants of interest in drinking water treatment (atrazine and trichloroethylene) by nine different types of carbonaceous adsorbents: three different types of single walled carbon nanotubes (SWNTs), three different sized multi-walled nanotubes (MWNTs), two granular activated carbons (GACs) and a powdered activated carbon (PAC). On a mass basis, the activated carbons exhibited the highest uptake, followed by SWNTs and MWNTs. However, metallic impurities in SWNTs and multiple walls in MWNTs contribute to adsorbent mass but do not contribute commensurate adsorption sites. Therefore, when uptake was normalized by purity (carbon content) and surface area (instead of mass), the isotherms collapsed and much of the CNT data was comparable to the activated carbons, indicating that these two characteristics drive much of the observed differences between activated carbons and CNT materials. For the limited data set here, the Raman D:G ratio as a measure of disordered non-nanotube graphitic components was not a good predictor of adsorption from solution. Uptake of atrazine by MWNTs having a range of lengths and diameters was comparable and their Freundlich isotherms were statistically similar, and we found no impact of solution pH on the adsorption of either atrazine or trichloroethylene in the range of naturally occurring surface water (pH = 5.7-8.3). Experiments were performed using a suite of model aromatic compounds having a range of π-electron energy to investigate the role of π-π electron donor-acceptor interactions on organic compound uptake by SWNTs. For the compounds studied, hydrophobic interactions were the dominant mechanism in the uptake by both SWNTs and activated carbon. However, comparing the uptake of naphthalene and phenanthrene by activated carbon and SWNTs, size exclusion effects appear to be more pronounced with activated carbon materials, perhaps due to smaller pore sizes or larger adsorption surface areas in small pores.     

Nanoenvelopes: Wrapping a Single‐Walled Carbon Nanotube with Graphene using an Atomic Force Microscope

Engineering the morphology and structure of low‐dimensional carbon nanomaterials is important to study their mechanical and electrical properties and even superconductivity. Herein, first the techniques that are used to engineer carbon nanotubes, including manipulation, morphology modification, and fabrication of complex nanostructures, are reviewed. This is followed by a summary of the methods applied to fabricate graphene nanostructures, such as heterostructures and nanoenvelopes of graphene. Lastly, an insight into the applications of low‐dimensional‐carbon‐based electronics is given, such as carbon nanotube (CNT) transistors, graphene‐based nanoenvelopes, and graphene‐contacted CNT field‐effect transistors (FETs), which are promising components in future electronics.     

Carbon–Heteroatom Bond Formation by an Ultrasonic Chemical Reaction for Energy Storage Systems

The direct formation of C? N and C? O bonds from inert gases is essential for chemical/biological processes and energy storage systems. However, its application to carbon nanomaterials for improved energy storage remains technologically challenging. A simple and very fast method to form C? N and C? O bonds in reduced graphene oxide (RGO) and carbon nanotubes (CNTs) by an ultrasonic chemical reaction is described. Electrodes of nitrogen‐ or oxygen‐doped RGO (N‐RGO or O‐RGO, respectively) are fabricated via the fixation between N₂ or O₂ carrier gas molecules and ultrasonically activated RGO. The materials exhibit much higher capacitance after doping (133, 284, and 74 F g^?1 for O‐RGO, N‐RGO, and RGO, respectively). Furthermore, the doped 2D RGO and 1D CNT materials are prepared by layer‐by‐layer deposition using ultrasonic spray to form 3D porous electrodes. These electrodes demonstrate very high specific capacitances (62.8 mF cm^?2 and 621 F g^?1 at 10 mV s^?1 for N‐RGO/N‐CNT at 1:1, v/v), high cycling stability, and structural flexibility.     

Electrokinetic Energy Conversion in Self‐Assembled 2D Nanofluidic Channels with Janus Nanobuilding Blocks

Inspired by the microstructure of nacre, material design, and large‐scale integration of artificial nanofluidic devices step into a completely new stage, termed 2D nanofluidics, in which mass and charge transportation are confined in the interstitial space between reconstructed 2D nanomaterials. However, all the existing 2D nanofluidic systems are reconstituted from homogeneous nanobuilding blocks. Herein, this paper reports the bottom‐up construction of 2D nanofluidic materials with kaolinite‐based Janus nanobuilding blocks, and demonstrates two types of electrokinetic energy conversion through the network of 2D nanochannels. Being different from previous 2D nanofluidic systems, two distinct types of sub‐nanometer‐ and nanometer‐wide fluidic channels of about 6.8 and 13.8 Å are identified in the reconstructed kaolinite membranes (RKM), showing prominent surface‐governed ion transport behaviors and nearly perfect cation‐selectivity. The RKMs exhibit superior capability in osmotic and hydraulic energy conversion, compared to graphene‐based membranes. The mineral‐based 2D nanofluidic system opens up a new avenue to self‐assemble asymmetric 2D nanomaterials for energy, environmental, and healthcare applications.     

Wetting‐Induced Climbing for Transferring Interfacially Assembled Large‐Area Ultrathin Pristine Graphene Film

Owing to inherent 2D structure, marvelous mechanical, electrical, and thermal properties, graphene has great potential as a macroscopic thin film for surface coating, composite, flexible electrode, and sensor. Nevertheless, the production of large‐area graphene‐based thin film from pristine graphene dispersion is severely impeded by its poor solution processability. In this study, a robust wetting‐induced climbing strategy is reported for transferring the interfacially assembled large‐area ultrathin pristine graphene film. This strategy can quickly convert solvent‐exfoliated pristine graphene dispersion into ultrathin graphene film on various substrates with different materials (glass, metal, plastics, and cloth), shapes (film, fiber, and bulk), and hydrophobic/hydrophilic patterns. It is also applicable to nanoparticles, nanofibers, and other exfoliated 2D nanomaterials for fabricating large‐area ultrathin films. Alternate climbing of different ultrathin nanomaterial films allows a layer‐by‐layer transfer, forming a well‐ordered layered composite film with the integration of multiple pristine nanomaterials at nanometer scale. This powerful strategy would greatly promote the development of solvent‐exfoliated pristine nanomaterials from dispersions to macroscopic thin film materials.     

Recent advances in emerging 2D nanomaterials for biosensing and bioimaging applications

The great success of graphene throws new light on discovering more two-dimensional (2D) layered nanomaterials that stem from atomically thin 2D sheets. Compared with a single element of graphene, emerging graphene-like 2D materials composed of multiple elements that possess more versatility, greater flexibility and better functionality with a wide range of potential applications. In this review, we provide insights into the rapidly emerging 2D materials and their biosensing and bioimaging applications in recent three years, including 2D transition metal nanomaterials, graphitic nitride materials, black phosphorus, and emerging 2D organic polymers. We first briefly highlight their unique 2D morphology and physicochemical properties and then focus on their recent applications in electrochemical biosensing, optical biosensing and bioimaging. The challenges and some thoughts on future perspectives in this field are also addressed.     

Cation–π Interactions in Graphene-Containing Systems for Water Treatment and Beyond

Cation–π interactions are common in nature, especially in organisms. Their profound influences in chemistry, physics, and biology have been continuously investigated since they were discovered in 1981. However, the importance of cation–π interactions in materials science, regarding carbonaceous nanomaterials, has just been realized. The interplay between cations and delocalized polarizable π electrons of graphene would bring about significant changes to the intrinsic characteristics of graphene and greatly affect the device performance based on graphene and its derivatives. Here, the cation–π interactions in graphene containing systems for water treatment applications (e.g., separation membranes, adsorbents) are highlighted. The cross-linking effects caused by cation–π interactions contribute to membrane stability and selectivity and enhanced adsorption. Their roles in dominating the performance of graphene-based structures for other specific applications are also discussed. Relevant theoretical modeling and calculations are summarized to offer an in-depth understanding of the underlying mechanisms which can help in designing more functional materials and structures. Perspectives on the potential directions that deserve effort are also presented.     

Hybridized 2D Nanomaterials Toward Highly Efficient Photocatalysis for Degrading Pollutants: Current Status and Future Perspectives

Organic pollutants including industrial dyes and chemicals and agricultural waste have become a major environmental issue in recent years. As an alternative to simple adsorption, photocatalytic decontamination is an efficient and energy‐saving technology to eliminate these pollutants from water environment, utilizing the energy of external light, and unique function of photocatalysts. Having a large specific surface area, numerous active sites, and varied band structures, 2D nanosheets have exhibited promising applications as an efficient photocatalyst for degrading organic pollutants, particularly hybridization with other functional components. The novel hybridization of 2D nanomaterials with various functional species is summarized systematically with emphasis on their enhanced photocatalytic activities and outstanding performances in environmental remediation. First, the mechanism of photocatalytic degradation is given for discussing the advantages/shortcomings of regular 2D materials and identifying the importance of constructing hybrid 2D photocatalysts. An overview of several types of intensively investigated 2D nanomaterials (i.e., graphene, g‐C₃N₄, MoS₂, WO₃, Bi₂O₃, and BiOX) is then given to indicate their hybridized methodologies, synergistic effect, and improved applications in decontamination of organic dyes and other pollutants. Finally, future research directions are rationally suggested based on the current challenges.     

Fabrication of Millimeter‐Long Carbon Tubular Nanostructures Using the Self‐Rolling Process Inherent in Elastic Protein Layers

Millimeter‐long conducting fibers can be fabricated from carbon nanomaterials via a simple method involving the release of a prestrained protein layer. This study shows how a self‐rolling process initiated by polymerization of a micropatterned layer of fibronectin (FN) results in the production of carbon nanomaterial‐based microtubular fibers. The process begins with deposition of carbon nanotube (CNT) or graphene oxide (GO) particles on the FN layer. Before polymerization, particles are discrete and nonconducting, but after polymerization the carbon materials become entangled to form an interconnected conducting network clad by FN. Selective removal of FN using high‐temperature combustion yields freestanding CNT or reduced GO microtubular fibers. The properties of these fibers are characterized using atomic force microscopy and Raman spectroscopy. The data suggest that this method may provide a ready route to rapid design and fabrication of aligned biohybrid nanomaterials potentially useful for future electronic applications.