Multifunctional Heterogeneous Carbon Nanotube Nanocomposites Assembled by DNA‐Binding Peptide Anchors

Although carbon nanotubes (CNTs) are remarkable materials with many exceptional characteristics, their poor chemical functionality limits their potential applications. Herein, a strategy is proposed for functionalizing CNTs, which can be achieved with any functional group (FG) without degrading their intrinsic structure by using a deoxyribonucleic acid (DNA)‐binding peptide (DBP) anchor. By employing a DBP tagged with a certain FG, such as thiol, biotin, and carboxyl acid, it is possible to introduce any FG with a controlled density on DNA‐wrapped CNTs. Additionally, different types of FGs can be introduced on CNTs simultaneously, using DBPs tagged with different FGs. This method can be used to prepare CNT nanocomposites containing different types of nanoparticles (NPs), such as Au NPs, magnetic NPs, and quantum dots. The CNT nanocomposites decorated with these NPs can be used as reusable catalase‐like nanocomposites with exceptional catalytic activities, owing to the synergistic effects of all the components. Additionally, the unique DBP–DNA interaction allows the on‐demand detachment of the NPs attached to the CNT surface; further, it facilitates a CNT chirality‐specific NP attachment and separation using the sequence‐specific programmable characteristics of oligonucleotides. The proposed method provides a novel chemistry platform for constructing new functional CNTs suitable for diverse applications.     

Functionalized Carbon‐Nanotube Sheet/Bismaleimide Nanocomposites: Mechanical and Electrical Performance Beyond Carbon‐Fiber Composites

Since their discovery in 1991, carbon nanotubes (CNTs) have been considered as the next‐generation reinforcement materials to potentially replace conventional carbon fibers for producing super‐high‐performance lightweight composites. Herein, it is reported that sheets of millimeter‐long multi‐walled CNTs with stretch alignment and epoxidation functionalization reinforce bismaleimide resin, which results in composites with an unprecedentedly high tensile strength of 3081 MPa and modulus of 350 GPa, well exceeding those of state‐of‐the‐art unidirectional carbon‐fiber‐reinforced composites. The results also provide important experimental evidence of the impact of functionalization and the effect of alignment reported previously on the mechanical performance and electrical conductivity of the nanocomposites.     

Defect/Edge‐Selective Functionalization of Carbon Materials by “Direct” Friedel–Crafts Acylation Reaction

Popularly utilized oxidation media, via nitric acid/sulfuric acid mixtures, are too corrosive and oxidizing to preserve structural integrity of highly ordered graphitic materials (carbon nanotubes (CNTs) and graphene). Here, for the most commonly used oxidation method, the important advantages of defect/edge‐selective functionalization of carbon materials (CNTs/graphene/graphite) in a polyphosphoric acid (PPA)/phosphorous pentoxide (P₂O₅) medium are elucidated. The optimized PPA/P₂O₅ medium is a mild acid that is not only less corrosive than popularly utilized oxidation media, but also has a strong capability to drive Friedel–Crafts acylation by covalently modifying carbon materials. With a broader spectrum of functional groups accessible, the PPA/P₂O₅‐driven Friedel–Crafts acylation offers more options for tailoring the properties and processing of carbon materials.     

碳纳米管在聚合物基体中的分散与有序排列研究--(Ⅰ)碳纳米管在聚合物基体中的分散

聚合物/碳纳米管（CNT）纳米复合材料，可将聚合物良好的加工性能和碳纳米管（CNTs）优异的功能化性质结合起来.目前，面临的主要挑战之一是如何提高CNTs在聚合物基体中的分散性.文中综述了优化物理共混、原位聚合和化学修饰等方法在改善CNTs在聚合物基体中分散性方面的最新研究动态。     

Preparation and characterization of carbon nano-onions by nanodiamond annealing and functionalization by radio-frequency Ar/O2 plasma

Carbon nanomaterials can be prepared by several methods having in common that need a carbon source and often require high energies. In this study, we report the synthesis and characterization of carbon nano-onions by annealing of commercially available nanodiamonds and explore for the first time their functionalization with a radio frequency Ar/O₂ plasma. Heat treatment of nanodiamonds at 1200°C for 6 hours under argon atmosphere afforded small spherical carbon nano-onion particles of 3–4 nm diameter and 5–6 graphitic shells. The prepared CNOs were visualized by HRTEM and showed the characteristic XRD and Raman features. The results have been compared with a sample prepared by annealing at 1600°C. Plasma functionalization in Ar/O₂ atmosphere was used to introduce oxygen moieties into the surface of synthesized CNOs. X-ray photoemission spectroscopy showed that oxygen-containing groups like C─O, C═O and O─C═O were introduced on the surface of CNOs, a process that is accompanied by a surface reorganization as evidenced by the change of I_D/I_G ratios in the Raman spectra, indicating a conversion of sp² to sp³ as a result of functionalization in the surface of CNO.     

电场诱导碳纳米管在聚合物中定向有序排列的研究进展

碳纳米管特殊的结构和优异的性能使之成为复合材料增强的首选填料,综述了电场条件下碳纳米管在聚合物中有序排列的研究进展。分析了电场类型、碳纳米管表面官能化、加电时间、碳纳米管尺寸和含量等因素对电场诱导碳纳米管有序排列的影响,讨论了定向有序排列的碳纳米管对复合材料的力学、电学和热学等性能的影响,分析了碳纳米管定向排列机理以及碳纳米管定向程度的表征方法。     

Effect of Carbon Coating on the Physico‐chemical Properties and Toxicity of Copper and Nickel Nanoparticles

The primary aim of these interdisciplinary studies is to investigate the effect of surface carbon coating on the physico‐chemical properties and toxicity of carbon‐coated and noncoated copper and nickel nanoparticles (C‐Cu, Cu, C‐Ni, Ni NPs) in A549 alveolar epithelial cells. Compared to Cu NPs, C‐Cu NPs exhibit protection against surface oxidation, tenfold higher cellular uptake, and fourfold lower release of soluble Cu. The toxicity of C‐Cu NPs and Cu NPs is associated with pronounced damage to mitochondrial function and plasma membrane integrity, respectively. Compared to Cu and C‐Cu NPs, Ni and C‐Ni NPs are less toxic. These studies demonstrate that correlations can be drawn between physico‐chemical properties and resultant toxicity of NPs as a function of surface carbon coating.     

Effects of carbon nanotubes additions on flash ignition characteristics of Fe and Al nanoparticles

The influences of carbon nanotubes (CNTs) additions on the flash ignition characteristics of Iron (Fe) and aluminum (Al) nanoparticles (NPs) were presented. CNTs can be used as the additive to these metal nanoparticles for improving the flash ignition and burning processes. Different mass fractions of CNTs additions were considered. The mixture of Al and CNTs could combust in air with obvious giant flame, whereas the mixture of Fe and CNTs combusted under a relative stable condition with slight red light. The temperature distributions were measured using non-contact optical method and showed that Al NPs mixed with CNTs were burning at a higher temperature level than Fe NPs. Although different mass fractions of CNTs cannot significantly change the overall flash ignition phenomenon, CNTs additions influenced the minimum ignition energy (MIE) of mixtures. The appropriate content of CNTs addition can decrease the Fe NPs MIE significantly. However, the Al NPs MIE decreased all along with the increase of CNTs content. The micro- and nano- structures of Fe and Al NPs with CNTs additions before and after ignitions were examined by scanning electron microscope and high-resolution transmission electron microscopy. It was found that the special thermal conductive characteristics of CNTs and the cross-connected features for metal particles with CNTs caused the enhancement of flash ignition.     

A Functionalized Carbon Surface for High‐Performance Sodium‐Ion Storage

Sodium‐ion batteries (SIBs) are promising for large‐scale energy storage systems and carbon materials are the most likely candidates for their electrodes. The existence of defects in carbon materials is crucial for increasing the sodium storage ability. However, both the reversible capacity and efficiency need to be further improved. Functionalization is a direct and feasible approach to address this issue. Based on the structural changes in carbon materials produced by surface functionalization, three basic categories are defined: heteroatom doping, grafting of functional groups, and the shielding of defects. Heteroatom doping can improve the electrochemical reactivity, and the grafting of functional groups can promote both the diffusion‐controlled bulk process and surface‐confined capacitive process. The shielding of defects can further increase the efficiency and cyclic stability without sacrificing reversible capacity. In this Review, recent progresses in the ways to produce surface functionalization are presented and the related impact on the physical and chemical properties of carbon materials is discussed. Moreover, the critical issues, challenges, and possibilities for future research are summarized.     

Rational Functionalization of Carbon Nanotubes Leading to Electrochemical Devices with Striking Applications

As one‐dimensional carbon nanostructures, carbon nanotubes (CNTs) are a member of the carbon family but they possess very different structural and electronic properties from other kinds of carbon materials frequently used in electrochemistry, such as glassy carbon, graphite, and diamond. Although the past decade has witnessed rapid and substantial progress in both the fundamental understanding of CNT‐oriented electrochemistry and the development of various kinds of electrochemical devices with carbon nanotubes, the increasing demand from both academia and industry requires CNT‐based electrochemical devices with vastly improved properties, such as good reliability and durability, and high performance. As we outline here, the smart functionalization of CNTs and effective methods for the preparation of devices would pave the way to CNT‐based electronic devices with striking applications.     

新型一步法包裹Fe制备磁性碳纳米管

采用柠檬酸络合法制得不同 Fe 含量的 Fe/MgO 催化剂,并将其应用到气相沉积(CVD)过程中制备磁性碳纳米管。由 CVD 法制备碳纳米管(CNTs)的生长机理,利用碳管在生长过程中原位包裹磁性 Fe 金属氧化物颗粒进入管内的现象,使碳纳米管具有磁性,从而一步制得了磁性碳纳米管。将制得的磁性碳纳米管采用透射电子显微镜(TEM)、X 射线衍射仪(XRD)、红外光谱仪(IR)、低温 N2吸附仪(BET)、振动样品磁强计(VSM)等表征方法进行了测试。结果表明通过这种新型的一步法可以成功地原位包裹 Fe 制得碳纳米管,且制得的碳纳米管具有较强磁性和较大的比表面积,表面引入了功能化基团。     

Effects of amino group on the properties of carbon nanotubes

The surfaces of multi-walled carbon nanotubes were grafted with amino functional groups by reacting acyl-chloride-functionalized carbon nanotubes (CNTs) with hexamethylene diamine, which improves the surfactivity of CNTs. The dispersity, surface morphology, and thermogravimetry of acid-treated and amino-functionalized CNTs were investigated. Amino-functionalized CNTs were added into epoxy resin to analyze the effects of amino functional groups on the properties of resin composites. It was found that the properties of CNTs, such as morphology and scale, were not affected by amino functional groups, but the dispersity in water was highly improved. Amino-functionalized CNTs are better dispersed in resin matrix, and the mechanical properties of composites are improved significantly, whereas the conductivity of composites is not enhanced as expected.     

Strong Electrochemiluminescence Emission from Oxidized Multiwalled Carbon Nanotubes

Carbon nanotubes (CNTs) as well‐known nanomaterials are extensively studied and widely applied in various fields. Nitric acid (HNO₃) is often used to treat CNTs for purification purposes and preparing oxidized CNTs for various applications. However, too little attention is paid to investigating the effect of HNO₃ treatment on the optical properties of CNTs. In this work, it is observed for the first time that HNO₃‐oxidized multiwalled carbon nanotubes (ox‐MWCNTs) have strong electrochemiluminescence (ECL) activity, which enables ox‐MWCNTs to become new and good ECL carbon nanomaterials after carbon quantum dots (CQDs) and graphene quantum dots (GQDs). Various characterization technologies, such as transmission electron microscope (TEM), X‐ray photoelectron spectroscopy (XPS), and Raman spectroscopy, are used to reveal the relationship between ECL activity and surface states. The ECL behaviors of ox‐MWCNTs are investigated in detail and a possible ECL mechanism is proposed. Finally, the new ECL nanomaterials of ox‐MWCNTs are envisioned to have promising applications in sensitive ECL sensing and in the study of CNT‐based catalysts.     

Magnetic carbon nanotubes with particle-free surfaces and high drug loading capacity

Open-ended, multi-wall carbon nanotubes (CNTs) with magnetic nanoparticles encapsulated within their graphitic walls (magCNTs) were fabricated by a combined action of templated growth and a ferrofluid catalyst/carbon precursor, and tested as drug hosts. The hybrid nanotubes are stable under extreme pH conditions due to particle protection provided by the graphitic shell. The magCNTs are promising for high capacity drug loading given that the magnetic functionalization did not block any of the active sites available for drug attachment, either from the CNT internal void or on the internal and external surfaces. This is in contrast to typical approaches of loading CNTs with particles that proceed through surface attachment or capillary filling of the tube interior. Additionally, the CNTs exhibit enhanced hydrophilic character, as shown by water adsorption measurements, which make them suitable for biological applications. The morphological and structural characteristics of the hybrid CNTs are evaluated in conjunction to their magnetic properties and ability for drug loading (diaminophenothiazine). The fact that the magnetic functionality is provided from 'inside the walls' can allow for multimode functionalization of the graphitic surfaces and makes the magCNTs promising for targeted therapeutic applications.     

One-step gas-phase construction of carbon-coated Fe3O4 nanoparticle/carbon nanotube composite with enhanced electrochemical energy storage

Carbon nanotubes (CNTs) as superior support materials for functional nanoparticles (NPs) have been widely demonstrated. Nevertheless, the homogeneous loading of these NPs is still frustrated due to the inert surface of CNTs. In this work, a facile gas-phase pyrolysis strategy that the mixture of ferrocene and CNTs are confined in an isolated reactor with rising temperature is developed to fabricate a carbon-coated Fe₃O₄ nanoparticle/carbon nanotube (Fe₃O₄@C/CNT) composite. It is found the ultra-small Fe₃O₄ NPs (<10 nm) enclosed in a thin carbon layer are uniformly anchored on the surface of CNTs. These structural benefits result in the excellent lithium-ion storage performances of the Fe₃O₄@C/CNT composite. It delivers a stable reversible capacity of 861 mA·h·g⁻¹ at the current density of 100 mA·g⁻¹ after 100 cycles. The capacity retention reaches as high as 54.5% even at 6000 mA·g⁻¹. The kinetic analysis indicates that the featured structural modification improves the surface condition of the CNT matrix, and contributes to greatly decreased interface impendence and faster charge transfer. In addition, the post-morphology observation of the tested sample further confirms the robustness of the Fe₃O₄@C/CNT configuration.     

Carbon Nanotubes Disrupt Iron Homeostasis and Induce Anemia of Inflammation through Inflammatory Pathway as a Secondary Effect Distant to Their Portal‐of‐Entry

Although numerous toxicological studies have been performed on carbon nanotubes (CNTs), a few studies have investigated their secondary and indirect effects beyond the primary target tissues/organs. Here, a cascade of events are investigated: the initiating event and the subsequent key events necessary for the development of phenotypes, namely CNT‐induced pro‐inflammatory effects on iron homeostasis and red blood cell formation, which are linked to anemia of inflammation (AI). A panel of CNTs are prepared including pristine multiwall CNTs (P‐MWCNTs), aminated MWCNTs (MWCNTs‐NH₂), polyethylene glycol MWCNTs (MWCNTs‐PEG), polyethyleneimine MWCNTs (MWCNTs‐PEI), and carboxylated MWCNTs (MWCNTs‐COOH). It has been demonstrated that all CNT materials provoke inflammatory cytokine interleukin‐6 (IL‐6) production and stimulate hepcidin induction, associated with disordered iron homeostasis, irrespective of exposure routes including intratracheal, intravenous, and intraperitoneal administration. Meanwhile, PEG and COOH modifications can ameliorate the activation of IL‐6‐hepcidin signaling. Long‐term exposure of MWCNTs results in AI and extramedullary erythropoiesis. Thus, an adverse outcome pathway is identified: MWCNT exposure leads to inflammation, hepatic hepcidin induction, and disordered iron metabolism. Together, the combined data depict the hazardous secondary toxicity of CNTs in incurring anemia through inflammatory pathway. This study will also open a new avenue for future investigations on CNT‐induced indirect and secondary adverse effects.     

Carbon nanotubes with high bone-tissue compatibility and bone-formation acceleration effects

Carbon nanotubes (CNTs) have been used in various fields as composites with other substances or alone to develop highly functional materials. CNTs hold great interest with respect to biomaterials, particularly those to be positioned in contact with bone such as prostheses for arthroplasty, plates or screws for fracture fixation, drug delivery systems, and scaffolding for bone regeneration. Accordingly, bone-tissue compatibility of CNTs and CNT influence on bone formation are important issues, but the effects of CNTs on bone have not been delineated. Here, it is found that multi-walled CNTs adjoining bone induce little local inflammatory reaction, show high bone-tissue compatibility, permit bone repair, become integrated into new bone, and accelerate bone formation stimulated by recombinant human bone morphogenetic protein-2 (rhBMP-2). This study provides an initial investigational basis for CNTs in biomaterials that are used adjacent to bone, including uses to promote bone regeneration. These findings should encourage development of clinical treatment modalities involving CNTs.     

Carbon Nanotubes for Dye‐Sensitized Solar Cells

As one type of emerging photovoltaic cell, dye‐sensitized solar cells (DSSCs) are an attractive potential source of renewable energy due to their eco–friendliness, ease of fabrication, and cost effectiveness. However, in DSSCs, the rarity and high cost of some electrode materials (transparent conducting oxide and platinum) and the inefficient performance caused by slow electron transport, poor light‐harvesting efficiency, and significant charge recombination are critical issues. Recent research has shown that carbon nanotubes (CNTs) are promising candidates to overcome these issues due to their unique electrical, optical, chemical, physical, as well as catalytic properties. This article provides a comprehensive review of the research that has focused on the application of CNTs and their hybrids in transparent conducting electrodes (TCEs), in semiconducting layers, and in counter electrodes of DSSCs. At the end of this review, some important research directions for the future use of CNTs in DSSCs are also provided.     

碳纳米洋葱制备方法的研究进展

碳纳米洋葱是继富勒烯与碳纳米管之后的又一新型碳纳米材料,在润滑剂、磁性材料等领域具有广阔的应用前景.综述了碳纳米洋葱的主要合成方法(电弧放电法、等离子体法、电子束照射法、热处理法、热解法和化学气相沉积法)及其特点,讨论了碳洋葱的形成机理,并简单介绍了碳纳米洋葱的性能及其应用.     

催化裂解天然气于碳毡内低成本合成碳纳米管

基于制备碳/碳(C/C)复合材料的等温化学气相渗透(ICVI)技术,在1010～1100℃用Fe催化裂解工业天然气可在碳毡内原位合成出碳纳米管(CNTs).扫描电镜(SEM)观察结果表明,1060℃合成的CNTs具有较好的覆盖形貌和均匀管径(110～120nm)且纯净度高.高分辨率透射电镜(HRTEM)和Raman光谱测试结果进一步表明,该温度下合成的CNTs结晶度高,与碳纤维间结合力强.