新型二维纳米材料在电化学领域的应用与发展

以石墨烯为代表的新型二维纳米材料具有独特的结构和优异的电子特性,在电化学各领域具有巨大的应用潜力。 本综述总结了新型二维纳米材料在电化学各领域(能源存储、能源转化和电化学传感)的研究现状和存在的问题。 展望了二维纳米材料在电化学领域的发展趋势。     

EMI shielding and dynamic mechanical analysis of graphene oxide-carbon nanotube-acrylonitrile butadiene styrene hybrid composites

Carbon nanomaterials such as carbon nanotubes (CNTs), graphene and their hybrid have been studied extensively. Despite having excellent properties of CNTs and graphene have not yet been fully realized in the polymer composites. During fabrication agglomeration of CNTs and restacking of graphene is a serious concern that results in the degradation of properties of nanomaterials into the final composites. To improve the dispersion of CNTs and restacking graphene, in the present research work, we focused on the hybridization of graphene oxide and CNTs. Multiwalled carbon nanotubes (MWCNTs), functionalized carbon nanotubes (FCNTs), and graphene oxide-carbon nanotubes (GCNTs) reinforced acrylonitrile butadiene styrene (ABS) composites were prepared separately by vacuum filtration followed by hot compression molding. Further, dynamic mechanical analysis (DMA), and electromagnetic interference (EMI) shielding properties of ABS composites reinforced carbon nanofillers were investigated. The dynamic mechanical properties of polymers strongly depend on the adhesion of fillers and polymer, entanglement density of polymer chains in the presence of carbon fillers. The dynamic mechanical characteristics such as storage, loss modulus, and damping factor of prepared composites were significantly affected by the incorporation of MWCNTs, FCNTs, and GCNTs. Maximum EMI shielding effectiveness of −49.6 dB was achieved for GCNT-ABS composites which were highest compared to MWCNTs-ABS composites (−38.6 dB) and FCNTs-ABS composites (−36.7 dB) in the Ku band (12.4–18 GHz). These results depict the great potential of GCNTs-ABS composites to be used in various applications of efficient heat dissipative EMI shielding materials for electronic devices.     

基于碳纳米材料的毛细管电色谱固定相研究进展

碳纳米材料由于其具有独特的纳米结构、大的比表面积、较强的热稳定性、良好的导电性以及较好的吸附性能等物理化学性质,因而在分析科学、生命科学、材料科学及环境科学等领域得广泛的应用.结合国内外最新文献,对近5年来碳纳米材料在毛细管电色谱新型固定相的制备研究方面进展进行了评述,包括毛细管电色谱的分类及分离机理、毛细管电色谱柱的制备方法和优缺点,碳纳米材料(石墨烯、碳纳米管、氧化石墨烯、还原氧化石墨烯、富勒烯)的结构性质及制备方法、碳纳米材料在毛细管电色谱柱固定相中的应用及作用机理等,并对其在色谱应用领域的方向进行了展望.     

Recent Applications of Carbon Nanomaterials for microRNA Electrochemical Sensing

MicroRNA (miRNA) is an important tumor marker in the human body, and its early detection has a great influence on the survival rate of patients. Although there are many detection methods for miRNA at present such as northern blotting, real-time quantitative polymerase chain reaction, microarrays, and others, electrochemical biosensors have the advantages of low detection cost, small instrument size, simple operation, non-invasive detection and low consumption of reagents and solvents, and thus they play an important role in the early detection of cancer. In addition, with the development of nanotechnology, nano-biosensors show great potential. The application of various nanomaterials in the development of electrochemical biosensor has greatly improved the detection sensitivity of electrochemical biosensor. Among them, carbon nanomaterials which have unique electrical, optical, physical and chemical properties have attracted increasing attention. In particular, they have a large surface area, good biocompatibility and conductivity. Therefore, carbon nanomaterials combined with electrochemical methods can be used to detect miRNA quickly, easily and sensitively. In this review, we systematically review recent applications of different carbon nanomaterials (carbon nanotubes, graphene and its derivatives, graphitic carbon nitride, carbon dots, graphene quantum dots and other carbon nanomaterials) for miRNA electrochemical detection. In addition, we demonstrate the future prospects of electrochemical biosensors modified by carbon nanomaterials for the detection of miRNAs, and some suggestions for their development in the near future.     

《新型二维纳米材料》专辑序言——新型二维纳米材料:掀起未来技术革命

Two-dimensional(2D) nanomaterials possess sheet-like structures with the thickness of nanoscale, but the lateral size is infinite. In 2004, Andre Geim and co-workers at the University of Manchester successfully exfoliated a sheet of graphene from graphite by the micromechanical cleavage technique, which marked the beginning of 2D nanomaterials. Given the ultrahigh carrier mobility, excellent mechanical property, good thermal stability, superior thermal conductivities and huge specific surface area of graphene, it causes general exploration of other graphene-like 2D nanomaterials.===The 2D feature is unique to access unprecedented physical, chemical, electronic and optical properties. For example, the electron confinement in two dimensions makes them ideal candidates for the fundamental study in condensed matter physics and electronic/optoelectronic devices; the large lateral size endows them with huge surface area and high exposure of active sites. Due to their unique properties, 2D nanomaterials have promising applications in energy storage and conversion, electronic devices, catalytic reaction, sensing and biomedicine. By now, nearly 20 types of 2D nanomaterials have been studied, such as graphene, graphitic carbon nitride(g-C₃N₄), transition metal dichalcogenides(TMDs), transition metal carbides/nitrides(MXenes), layered double hydroxides(LDHs), transition metal oxides(TMOs), Ⅲ to Ⅵ layered semiconductor(MX₄), and perovskite-type hybrids(AMX₃).===In this special issue of the novel 2D nanomaterials, we selected 12 related articles in reviews, research papers and brief communications involving supercapacitor, electrochemical catalysis, sensing, battery, fluorescence, water treatment and antiflaming performance of 2D nanomaterials. We hope that readers will have a deep understanding of the current development of 2D nanomaterials, and find it beneficial to their future researches.===Toward this end, I greatly appreciate the outstanding contribution of all authors, as well as the strenuous efforts from the editorial staff members.     

Fabrication of Boron Nitride Nanosheets by Exfoliation

Nanomaterials with layered structures, with their intriguing properties, are of great research interest nowadays. As one of the primary two‐dimensional nanomaterials, the hexagonal boron nitride nanosheet (BNNS, also called white graphene), which is an analogue of graphene, possesses various attractive properties, such as high intrinsic thermal conductivity, excellent chemical and thermal stability, and electrical insulation properties. After being discovered, it has been one of the most intensively studied two‐dimensional non‐carbon nanomaterials and has been applied in a wide range of applications. To support the exploration of applications of BNNSs, exfoliation, as one of the most promising approaches to realize large‐scale production of BNNSs, has been intensively investigated. In this review, methods to yield BNNSs by exfoliation will be summarized and compared with other potential fabrication methods of BNNSs. In addition, the future prospects of the exfoliation of h‐BN will also be discussed.     

Developing Graphene‐Based Nanohybrids for Electrochemical Sensing

Graphene‐based nanohybrid is considered to be the most promising nanomaterial for electrochemical sensing applications due to the defects created on the graphene oxide layers. These defects provide graphene oxide unique properties, such as excellent conductivity, large specific surface area, and electrocatalytic activity. These unique properties encourage scientists to develop novel graphene‐based nanohybrids and improve the sensing efficiency. This review, therefore, addresses this topic by comprehensively discussing the strategies to fabricate novel graphene based nanohybrids with high sensitivity. The combinations of graphene with various nanomaterials, such as metal nanoclusters, metal compound nanoparticles, carbon materials, polymers and peptides, in the direction of electrochemical sensing, were systematically analyzed. Meanwhile, the challenges in the functional design and application of graphene‐based nanohybrids were described and the reasonable solutions were proposed.     

Recent Advances in Composites of Graphene and Layered Double Hydroxides for Water Remediation: A Review

Composites of layered double hydroxides (LDHs) and graphene (G) are exciting nanomaterials because of their unique surface structures and excellent physicochemical properties. Such materials offer the advantages of both components, that is, the large surface area and ample functional groups of graphene and the outstanding layered structure and ion‐exchangeability of layered double hydroxides, whilst effectively avoiding the coagulation of graphene and the instability of pristine layered double hydroxides, and they have been widely investigated for applications in water remediation. This Minireview begins by summarizing the most common methods for the synthesis of G@LDH composites, including hydrothermal treatment, coprecipitation, and in situ growth. Then, we review the adsorption and catalytic ability of G@LDH materials in the removal of contaminants from water, such as heavy metal ions, radionuclides, dyes, and other organic pollutants. Finally, we discuss the challenges and offer a perspective on the directions of future research of G@LDH composites.     

Direct electrolytic exfoliation of graphite with hemin and single-walled carbon nanotube: Creating functional hybrid nanomaterial for hydrogen peroxide detection

We present a new, facile and efficient method to prepare functional graphene (GN) hybrid nanomaterials using direct electrolytic exfoliation of graphite robs in hemin (HN) and single-walled carbon nanotube (SWCNT) solution. During the exfoliation process, HN and SWCNT were simultaneously adsorbed on the surface of GN nanosheets through noncovalent π–π interaction, and then 3D GN–HN–SWCNT hybrid nanomaterials were formed. Due to the synergic effect among GN, HN, and SWCNT, these hybrid nanomaterials possessed excellent electrocatalysis properties and were used to construct novel electrochemical biosensor for H₂O₂ determination. The results displayed a wide linear range of 0.2 μM–0.4 mM and a low detection limit of 0.05 μM. Moreover, the developed sensor was successfully applied for real samples, such as beverages, and showed great promise in routine sensing applications.     

Thin metal nanostructures: synthesis,properties and applications

Two-dimensional nanomaterials, especially graphene and single- or few-layer transition metal dichalcogenide nanosheets, have attracted great research interest in recent years due to their distinctive physical, chemical and electronic properties as well as their great potentials for a broad range of applications. Recently, great efforts have also been devoted to the controlled synthesis of thin nanostructures of metals, one of the most studied traditional materials, for various applications. In this minireview, we review the recent progress in the synthesis and applications of thin metal nanostructures with a focus on metal nanoplates and nanosheets. First of all, various methods for the synthesis of metal nanoplates and nanosheets are summarized. After a brief introduction of their properties, some applications of metal nanoplates and nanosheets, such as catalysis, surface enhanced Raman scattering (SERS), sensing and near-infrared photothermal therapy are described.     

Cytotoxicity Profile of Highly Hydrogenated Graphene

Graphene and its graphene‐related counterparts have been considered the future of advanced nanomaterials owing to their exemplary properties. An increase in their potential applications in the biomedical field has led to serious concerns regarding their safety and impact on health. To understand the toxicity profile for a particular type of graphene utilized in a given application, it is important to recognize the differences between the graphene‐related components and correlate their cellular toxicity effects to the attributed physiochemical properties. In this study, the cytoxicity effects of highly hydrogenated graphene (HHG) and its graphene oxide (GO) counterpart on the basis of in vitro toxicological assessments are reported and the effects correlated with the physiochemical properties of the tested nanomaterials. Upon 24 h exposure to the nanomaterials, a dose‐dependent cellular cytotoxic effect was exhibited and the HHG was observed to be more cytotoxic than its GO control. Detailed characterization revealed an extensive C?H sp³ network on the carbon backbone of HHG with few oxygen‐containing groups, as opposed to the presence of large amounts of oxygen‐containing groups on the GO. It is therefore hypothesized that the preferential adsorption of micronutrients on the surface of the HHG nanomaterial by means of hydrophobic interactions resulted in a reduction in the bioavailability of nutrients required for cellular viability. The nanotoxicological profile of highly hydrogenated graphene is assessed for the first time in our study, thereby paving the way for further evaluation of the toxicity risks involved with the utilization of various graphene‐related nanomaterials in the real world.     

Thin Films and Composites Based on Graphene for Electrochemical Detection of Biologically‐relevant Molecules

Graphene is one of the most studied materials ever, owing to its exceptional electronic, mechanical and thermal properties, which allow for many different types of application. In this review, we shall concentrate on the use of graphene and derivatives for electrochemical sensors and biosensors, where emphasis is placed on the importance of surface functionalization as this permits synergistic combinations with other nanomaterials and biomolecules. In addition to describing recent advances in graphene‐based electroanalytical applications, we discuss a few examples of their use in detecting small biomolecules and in immunosensing for a few diseases using films and composites. Also discussed are the possible methods for mass production of graphene, which is key to low‐cost biosensors for implantable devices and portable systems in point‐of‐care diagnosis.     

A Review of Glucose Biosensors Based on Graphene/Metal Oxide Nanomaterials

In recent years, considerable attention has been paid to developing economical yet rapid glucose sensors using graphene and its composites. Recently, the excellent properties of graphene and metal oxide nanoparticles have been combined to provide a new approach for highly sensitive glucose sensors. This review focuses on the development of graphene functionalized with different nanostructured metal oxides (such as copper oxide, zinc oxide, nickel oxide, titanium dioxide, iron oxide, cobalt oxide, and manganese dioxide) for use as glucose biosensors. Additionally, a brief introduction of the electrochemical principles of glucose biosensors (including amperometric, potentiometric, and conductometric) is presented. Finally, the current status and future prospects are outlined for graphene/metal oxide nanomaterials in glucose sensing.     

Large‐Area Synthesis of Superclean Graphene via Selective Etching of Amorphous Carbon with Carbon Dioxide

Contamination commonly observed on the graphene surface is detrimental to its excellent properties and strongly hinders its application. It is still a great challenge to produce large‐area clean graphene film in a low‐cost manner. Herein, we demonstrate a facile and scalable chemical vapor deposition approach to synthesize meter‐sized samples of superclean graphene with an average cleanness of 99 %, relying on the weak oxidizing ability of CO₂ to etch away the intrinsic contamination, i.e., amorphous carbon. Remarkably, the elimination of amorphous carbon enables a significant reduction of polymer residues in the transfer of graphene films and the fabrication of graphene‐based devices and promises strongly enhanced electrical and optical properties of graphene. The facile synthesis of large‐area superclean graphene would open the pathway for both fundamental research and industrial applications of graphene, where a clean surface is highly needed.     

Incorporations of gold,silver and carbon nanomaterials to kombucha-derived bacterial cellulose: Development of antibacterial leather-like materials

Bacterial cellulose (BC), derived from kombucha scoby have extraordinary organoleptic properties suitable for development of leather-like materials. An improvement in physical and mechanical property is desirable for the practical applications. This work deals with the treatment of BC by incorporations of three different nanomaterials such as gold nanoparticles (AuNP), silver nanoparticles (AgNP) and graphene oxide (GO). Achieving combined benefits via synergic interactions of different nanomaterials is the major objective herein. While graphene oxide can influence some of the parameters related to mechanical properties, silver nanomaterials can offer antibacterial characteristics. Gold nano materials can bridge the BC/silver/graphene oxide as well as provide the desirable aesthetic colour. Different physical chemical and mechanical characteristics were studied in detail. For example, changes in morphology by imaging fiber network were studied using scanning electron microscopy. Fibre properties were studied by Small Angle X-Ray Scattering (SAXS) and X-Ray Diffraction (XRD). Elemental composition was studied by X-ray photoelectron spectroscopy (XPS) analysis and Raman analysis. The improvement of hydrophobicity was studied by Contact angle meter. Thermal analysis was performed using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). A Picture was provided in ESI to show the modified material's leather-like appearances.     

A review on elastic graphene aerogels: Design,preparation, and applications

Graphene aerogels with unique properties, such as ultralow density, super-elasticity, high specific surface area, and excellent thermal stability, have undergone great progress in the past decades. Especially, super-elastic graphene aerogels provide a highly attention-catching platform for developing advanced energy devices, pressure sensors, contaminates adsorbents, and electromagnetic wave shielding and absorption materials, and so forth. In this review, we begin with the introduction and discussion of various fabrication techniques and compare their advantages and disadvantages, focusing on the template-free assembly process and template-assisted assembly process. Then, we summarize the factors influencing the compressibility and elasticity of graphene aerogels, including intrinsic properties of building blocks, constituent materials, and structure design, and their wide applications. At the end, we discuss the current challenges and future prospects of this field.     

刺激响应纳米碳杂化材料

碳纳米管和石墨烯是碳纳米材料的典型代表,其纳米尺度赋予了其优异的光、电、热以及机械性能。然而,这些碳纳米材料间存在较强的范德华力,导致其溶解性差,后续加工处理困难。为提高碳纳米材料的溶解性,通常利用聚合物或其它小分子物质对其进行修饰。而利用刺激响应性聚合物或化合物功能化碳纳米材料,不仅可以提高其溶解性,还可以赋予其环境刺激响应功能。本文主要综述了近年来利用温度、pH、光以及CO2响应聚合物或小分子化合物对碳纳米管和石墨烯进行共价键、非共价键修饰并赋予其环境刺激响应特性的方法、功能和相关应用,展望了修饰得到的纳米碳杂化材料的应用前景及下一步发展方向。     

Nanocarbon-Based Flame Retardant Polymer Nanocomposites

In recent years, nanocarbon materials have attracted the interest of researchers due to their excellent properties. Nanocarbon-based flame retardant polymer composites have enhanced thermal stability and mechanical properties compared with traditional flame retardant composites. In this article, the unique structural features of nanocarbon-based materials and their use in flame retardant polymeric materials are initially introduced. Afterwards, the flame retardant mechanism of nanocarbon materials is described. The main discussions include material components such as graphene, carbon nanotubes, fullerene (in preparing resins), elastomers, plastics, foams, fabrics, and film–matrix materials. Furthermore, the flame retardant properties of carbon nanomaterials and their modified products are summarized. Carbon nanomaterials not only play the role of a flame retardant in composites, but also play an important role in many aspects such as mechanical reinforcement. Finally, the opportunities and challenges for future development of carbon nanomaterials in flame-retardant polymeric materials are briefly discussed.     

基于纳米材料电化学生物传感器的研究进展

近年来,纳米材料在电化学生物传感器领域的研究已成为前沿性的内容.纳米材料具备优异的物理、化学、电催化等性能,加之其量子尺寸效应和表面效应,可将传感器的性能提高到一个新的水平.基于纳米材料的电化学生物传感器呈现出体积更小、速度更快、检测灵敏度更高和可靠性更好等优异性能.该文按照纳米结构的分类,综述了近几年基于以下纳米材料...     

基于石墨烯纳米材料的DNA测序研究进展

设计和研发快速、准确、价廉、高通量的DNA测序方法,对于预防早期疾病和了解相关疾病机理具有非常重要的意义。新型纳米材料石墨烯由于具有独特的结构和性质,在化学和生物科学等领域发挥着重要的作用。该文介绍了DNA测序的研究现状以及应用石墨烯纳米材料的优势,重点阐述了DNA链通过石墨烯纳米孔、石墨烯纳米间隙、石墨烯纳米带时产生不同的电流信号识别碱基序列的原理,同时介绍了DNA链与石墨烯的相互作用对DNA测序的影响,并对DNA测序的研究方向进行了展望。该文为基于石墨烯纳米材料的DNA测序提供了作用原理、理论研究以及检测方法等参考。