Development and Optimization of Water-Soluble Double-Walled Carbon Nanotubes by Effective Surface Treatment of Inner Walls.

Carbon nanotubes are a significant class of nanomaterials with distinctive properties that have led to their application in a variety of fields, such as polymer composites, medicine, electronics, and material science. However, their nonpolar nature and insolubility in polar solvents limit their applications. To address this issue, highly functionalized and water-soluble double-walled carbon nanotubes (DWNTs) were developed by selectively oxidizing the inner walls of the DWNTs using oleum and nitric acid. The impact of reaction time on the chemical functionalization of DWNTs was investigated under two different reaction durations of 2 and 24 h. The presence of highly oxygenated functional groups resulted in high water solubility, which was confirmed by high- and low-frequency Raman spectroscopy, high-resolution transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) method, and optical spectroscopy. The conductivity of highly water-soluble W-DWNTs (24 h) was 122.65 × 102 S cm-1. After annealing for 12 h at 140 °C, the W-DWNTs retained 72% of their conductivity (88.79 × 102 S cm-1).

All-Gas-Phase Synthesis of Heterolayered Two-Dimensional Nanohybrids Decorated with Metallic Nanocatalysts for Water Splitting.

Herein, a sequential gas-phase process involving air jet milling followed by chemical vapor deposition (CVD), is demonstrated to be an efficient strategy for the fabrication of heterolayered 2D nanohybrids (2DNHs) decorated with nanocatalysts. Tens of grams of the nanohybrids, which is a substantial quantity at the laboratory scale, are produced in the absence of solvents and water, and without the need for an extra purification procedure. Air jet milling enables the development of binary/ternary heterolayered structures consisting of graphene, WSe2 , and/or MoS2 via the gas-phase co-exfoliation of their bulk counterparts. Based on the X-ray photoelectron and Raman spectroscopy data, the heterolayers of the 2DNHs exert chemical and electronic effects on each other, while diminishing the interactions between same-component layers. Moreover, the electrochemically active surface area increases by >190% and the charge transfer resistance decreases by >35%. CVD is performed to introduce Pt and Ru nanoparticles with diameters of a few nanometers as additional electrocatalysts into the 2DNHs. The nanocatalyst-decorated 2DNHs show excellent performance for the production of hydrogen and oxygen gases in water-splitting cells. Notably, the proposed all-gas-phase processes allow for the large-scale production of functional 2DNHs with minimal negative environmental impact, which is crucial for the commercialization of nanomaterials.

Erratum: Anharmonicity and Universal Response of Linear Carbon Chain Mechanical Properties under Hydrostatic Pressure [Phys. Rev. Lett. 125, 105501 (2020)].

This corrects the article DOI: 10.1103/PhysRevLett.125.105501.

Erratum: Anharmonicity and Universal Response of Linear Carbon Chain Mechanical Properties under Hydrostatic Pressure [Phys. Rev. Lett. 125, 105501 (2020)].

This corrects the article DOI: 10.1103/PhysRevLett.125.105501.

Hierarchical Design of Functional, Fibrous, and Microporous Polymer Monoliths for the Molecular Recognition of Diethylstilbestrol.

This paper demonstrates the hierarchical design of functional, fibrous polymer monoliths. The monoliths are composed of conjugated microporous polymers that not only are embedded with heteroatoms but also feature fibrous yet compressible structures due to the in situ self-assembly process that occurs during the polymerization process. Therefore, the doped nitrogen atoms can allow the growth of zeolitic imidazolate framework (ZIF) nanocrystals, which causes the homogeneous encapsulation of individual fibers. The resulting hybrid monoliths exhibit enhanced physical properties as well as catalytic activity, allowing the formation of an additional coating layer via a thiol-epoxy reaction. The deliberate inclusion of template molecules during the reaction forms molecularly imprinted sites on the fibers to afford functional monoliths. As a proof of concept, the hierarchically designed materials are able to show effective recognition properties toward diethylstilbestrol, an endocrine disruptor, taking advantage of the binding sites that selectively capture the analyte molecules and the fibrous morphology that increases the accessibility of these binding sites. We envisage that the incorporation of various heteroatoms or nanocrystals will bring about the bespoke design of advanced monoliths with autonomous functions, leading to smart textile systems.

Thermodynamics of Linear Carbon Chains.

Linear carbon chains (LCCs) are one-dimensional materials with unique properties, including high Debye temperatures and restricted selection rules for phonon interactions. Consequently, their Raman C-band frequency's temperature dependence is a probe to their thermal properties, which are well described within the Debye formalism even at room temperatures. Therefore, with the basis on a semiempirical approach we show how to use the C band to evaluate the LCCs' internal energy, heat capacity, coefficient of thermal expansion, thermal strain, and Grüneisen parameter, providing universal relations for these quantities in terms of the number of carbons atoms and the temperature.

Boron-Doped Edges as Active Sites for Water Adsorption in Activated Carbons.

Investigating the surface properties of heteroatom-doped carbon materials is essential because these versatile materials have found use in a variety of energy and environmental applications; an understanding of these properties would also lead to an improved appreciation of the direct interaction between the reactant and the functionalized surface. Herein, we explore the effect of boron (B) doping on the surface properties of activated carbon (AC) materials based on their water adsorption behavior and oxygen reduction reaction. In the high-temperature B doping process, B-doped AC materials at 1400 °C exhibit an open pore structure with B-O bonds, whereas at a temperature of 1600 °C, a nonporous structure containing a large amount of B-C bonds prevails. The B-O species act as active sites for water adsorption on the carbon surface. On the basis of the isothermal adsorption heat, we suggest that B atoms are present at the pore openings and on the surfaces. The B-O moieties at the open edges improve the electrocatalytic activity, whereas the B-C bonds at the closed edges decrease the electrocatalytic activity because of the stable structure of these bonds. Our findings provide new evidence for the electrocatalytic properties associated with the structure of B-doped edges.

Quantifying Carbon Edge Sites on Depressing Hydrogen Evolution Reaction Activity.

To understand the effect of microstructural characteristics of carbon materials on their electrochemical or electrocatalytic performance, an in-depth study of the edges in carbon materials should be carried out. In this study, catalytically grown platelet-type carbon nanofibers (CNFs) with fully exposed edges were physically and chemically passivated to clarify the relationship between the edge density and the hydrogen evolution reaction (HER) activity. Due to the aligned structure along the fiber axis, the edges on the outer surface of the CNFs were easily modified without using a complex process. The edges on the surface of the CNFs were inactivated by sequentially forming single, double, and multiple loops as the heat treatment temperatures increased. The number of edges within the CNFs was quantitatively measured using temperature-programmed desorption (TPD) up to 1800 °C. The surviving edges on the surface of thermally treated CNFs were identified by chemical functionalization via an amination reaction. We identified a close relationship between the HER activity and the edge density. When evaluating the electrochemical and electrocatalytic activity of carbon materials, it is important to know the portion of the edge surface area with respect to the total surface area and edge ratio.

Anharmonicity and Universal Response of Linear Carbon Chain Mechanical Properties under Hydrostatic Pressure.

Isolated linear carbon chains (LCCs) encapsulated by multiwalled carbon nanotubes are studied under hydrostatic pressure (P) via resonance Raman scattering. The LCCs' spectroscopic signature C band around 1850 cm^{-1} softens linearly with increasing P. A simple anharmonic force-constant model not only describes such softening but also shows that the LCCs' Young's modulus (E), Grüneisen parameter (γ), and strain (ϵ) follow universal P^{-1} and P^{2} laws, respectively. In particular, γ also presents a unified behavior for all LCCs. To the best of our knowledge, these are the first results reported on such isolated systems and the first work to explore universal P-dependent responses for LCCs' E, ϵ, and γ.

Low interfacial contact resistance of Al-graphene composites via interface engineering.

Al-based composites incorporating multilayered graphene sheets were developed via a facile approach. The multilayered graphene sheets were fabricated from the expanded graphite via a simple mechanical exfoliation process. The facile extrusion molding process with Al powder and graphene sheets exfoliated from expended graphite afforded Al-based graphene composite rods. These composites showed enhanced thermal conductivity compared to the pristine Al rods. Moreover, the Al-based multilayered graphene sheet composites exhibited lower interfacial contact resistance between graphene-based electrodes than the pristine Al. With increasing degrees of dispersion, the number of exposed graphene sheets increases, thereby significantly decreasing the interfacial contact resistance between the composite and external graphite electrode.

Rice husk-derived graphene with nano-sized domains and clean edges.

A new synthetic method is demonstrated for transforming rice husks into bulk amounts of graphene through its calcination and chemical activation. The bulk sample consists of crystalline nano-sized graphene and corrugated individual graphene sheets; the material generally contains one, two, or a few layers, and corrugated graphene domains are typically observed in monolayers containing topological defects within the hexagonal lattice and edges. Both types of graphenes exhibit atomically smooth surfaces and edges.

Electrospun Polyvinylidene Fluoride Membranes: Waterproofing and Acoustic Performance for Air and Acoustic Vents in Electronics.

Advancements in electronic devices demand materials capable of exceptional performance in various challenging environments. This study presents polyvinylidene fluoride (PVDF) nonwoven membranes with controlled porosity, created using an air-guided electrospinning method, followed by a calendaring process. These membranes exhibit a combination of water-repellent properties and sound transmission capabilities, making them ideal candidates for use in air and acoustic vents in electronic systems. A key feature of our membrane is the three-dimensional nanostructured pores, ranging from 0.20 to 0.76 µm, with a mean pore size of 0.51 µm, achieved through the formation of randomly arranged long nanofibers. By employing both experimental and theoretical methods, we achieved impressive performance metrics: air permeability of 0.86 cm3/cm2/s, water contact angles up to 139.3°, and breakthrough pressure as low as 0.27 MPa. Our PVDF nonwoven membranes maintain an optimal balance of stiffness, density, and air permeability, leading to exceptionally low sound transmission loss values ranging between -10 and -40 dBV/Pa, all while preserving their structural integrity. These findings contribute to the development of next-generation waterproof and acoustically permeable membranes, offering enhanced performance capabilities in demanding operational scenarios. This work advances the field of nanomaterials, environmental engineering, and acoustic technologies, with the potential to influence the design of future electronic devices.

Surface modification of electrospun polyvinylidene fluoride nanofiber membrane by plasma treatment for protein detection.

Electrospun polyvinylidene fluoride (PVDF) nanofiber membranes have 3-dementional (3-D) open pore channel and hence have excellent application potential in Western blot. In this study we have modified electrospun PVDF nanofiber membrane by argon (Ar) plasma treatment to improve the surface hydrophilic and detection sensitivity. The results showed that the detection sensitivity of the Ar plasma-treated PVDF nanofiber membrane increased with increasing plasma treatment time without the need for a methanol pre-wet step. This suggests that the Ar plasma treated PVDF nanofiber membrane can be useful in Western blot with high sensitivity and without methanol pre-wet step.

Boron-Doped Activated Carbon Supports for Cobalt-Catalyzed Oxygen Evolution in Alkaline Electrolyte.

Activated carbons (ACs) are the most widely used and attractive support materials for electrocatalytic applications because of their significant surface areas, high electrical conductivities, and moderate affinities toward supported metal catalysts. However, the corrosive behavior of ACs at oxidative potentials causes an inevitable reduction in the active surface area of supported catalysts, resulting in the continuous deterioration of their electrocatalytic performance. Therefore, the introduction of corrosion-resistant durable catalyst supports is essential for sustainable and efficient electrocatalysis. Here, we modified ACs to obtain different boron (B)-doped structures via doping-temperature controls to investigate the corrosion resistance of B-doped ACs. With increasing doping temperature, the B-doped ACs exhibited a decreased defect density and enhanced crystallinity owing to the accelerating dopant-induced graphitization. We found that the substitution of B atoms into the carbon lattice improved the structural integrity of the carbon structure, and cyclic voltammetry (CV) tests suggested that the highly B-substituted structures caused electrochemical surface passivation against carbon corrosion. Moreover, B-doped ACs significantly contributed to the increase in loading mass of cobalt (Co)-based catalyst on them and the electrochemical durability toward the oxygen evolution reaction as catalyst-support hybrid. The B22 (B-doped AC obtained at a 2200 °C B-doping temperature)-supported Co catalyst with the lowest oxidation current exhibited a voltage change of 32 mV at a current density of 10 mA/cm2 (ΔEj=10) after 10,000 cycles, which was a factor of ∼7 higher cycle durability and stability than that of the conventional IrO2 catalyst (ΔEj=10 = 205 mV). Here, we propose that surface engineering by B-doping to improve the structural integrity of ACs is an attractive method for designing durable electrocatalytic support materials.

Fabrication of transparent, tough, and conductive shape-memory polyurethane films by incorporating a small amount of high-quality graphene.

We report a mechanically strong, electrically and thermally conductive, and optically transparent shape-memory polyurethane composite which was fabricated by introducing a small amount (0.1 wt%) of high-quality graphene as a filler. Geometrically large (≈4.6 µm(2)), but highly crystallized few-layer graphenes, verified by Raman spectroscopy and transmission electron microscopy, were prepared by the sonication of expandable graphite in an organic solvent. Oxygen- containing functional groups at the edge plane of graphene were crucial for an effective stress transfer from the graphene to polyurethane. Homogeneously dispersed few-layered graphene enabled polyurethane to have a high shape recovery force of 1.8 MPa cm(-3). Graphene, which is intrinsically stretchable up to 10%, will enable high-performance composites to be fabricated at relatively low cost and we thus envisage that such composites may replace carbon nanotubes for various applications in the near future.

Application of carbon fibers to biomaterials: a new era of nano-level control of carbon fibers after 30-years of development.

Carbon fibers are state-of-the-art materials with properties that include being light weight, high strength, and chemically stable, and are applied in various fields including aeronautical science and space science. Investigation of applications of carbon fibers to biomaterials was started 30 or more years ago, and various products have been developed. Because the latest technological progress has realized nano-level control of carbon fibers, applications to biomaterials have also progressed to the age of nano-size. Carbon fibers with diameters in the nano-scale (carbon nanofibers) dramatically improve the functions of conventional biomaterials and make the development of new composite materials possible. Carbon nanofibers also open possibilities for new applications in regenerative medicine and cancer treatment. The first three-dimensional constructions with carbon nanofibers have been realized, and it has been found that the materials could be used as excellent scaffolding for bone tissue regeneration. In this critical review, we summarize the history of carbon fiber application to the biomaterials and describe future perspectives in the new age of nano-level control of carbon fibers (122 references).

Microgels based on 0D-3D carbon materials: Synthetic techniques, properties, applications, and challenges.

Microgels are three-dimensional (3D) colloidal hydrogel particles with outstanding features such as biocompatibility, good mechanical properties, tunable sizes from submicrometer to tens of nanometers, and large surface areas. Because of these unique qualities, microgels have been widely used in various applications. Carbon-based materials (CMs) with various dimensions (0-3D) have recently been investigated as promising candidates for the design and fabrication of microgels because of their large surface area, excellent conductivity, unique chemical stability, and low cost. Here, we provide a critical review of the specific characteristics of CMs that are being incorporated into microgels, as well as the state-of-the art applications of CM-microgels in pollutant adsorption and photodegradation, H2 evoluation, CO2 capture, soil conditioners, water retention, drug delivery, cell encapsulation, and tissue engineering. Advanced preparation techniques for CM-microgel systems are also summarized and discussed. Finally, challenges related to the low colloidal stability of CM-microgels and development strategies are examined. This review shows that CM-microgels have the potential to be widely used in various practical applications.

Optically and biologically active mussel protein-coated double-walled carbon nanotubes.

A method of dispersing strongly bundled double-walled carbon nanotubes (DWNTs) via a homogeneous coating of mussel protein in an aqueous solution is presented. Optical activity, mechanical strength, as well as electrical conductivity coming from the nanotubes and the versatile biological activity from the mussel protein make mussel-coated DWNTs promising as a multifunctional scaffold and for anti-fouling materials.

Surface chemistry in the process of coating mesoporous SiO2 onto carbon nanotubes driven by the formation of Si-O-C bonds.

The deposition of mesoporous silica (SiO(2)) on carbon nanotubes (CNTs) has opened up a wide range of assembling possibilities by exploiting the sidewall of CNTs and organosilane chemistry. The resulting systems may be suitable for applications in catalysis, energy conversion, environmental chemistry, and nanomedicine. However, to promote the condensation of silicon monomers on the nanotube without producing segregated particles, (OR)(4-x)SiO(x)(x-) units must undergo nucleophilic substitution by groups localized on the CNT sidewall during the transesterification reaction. In order to achieve this preferential attachment, we have deposited silica on oxidized carbon nanotubes (single-walled and multiwalled) in a sol-gel process that also involved the use of a soft template (cetyltrimethylammonium bromide, CTAB). In contrast to the simple approach normally used to describe the attachment of inorganic compounds on CNTs, SiO(2) nucleation on the tube is a result of nucleophilic attack mainly by hydroxyl radicals, localized in a very complex surface chemical environment, where various oxygenated groups are covalently bonded to the sidewall and carboxylated carbonaceous fragments (CCFs) are adsorbed on the tubes. Si-O-C covalent bond formation in the SiO(2)-CNT hybrids was observed even after removal of the CCFs with sodium hydroxide. By adding CTAB, and increasing the temperature, time, and initial amount of the catalyst (NH(4)OH) in the synthesis, the SiO(2) coating morphology could be changed from one of nanoparticles to mesoporous shells. Concomitantly, pore ordering was achieved by increasing the amount of CTAB. Furthermore, preferential attachment on the sidewall results mostly in CNTs with uncapped ends, having sites (carboxylic acids) that can be used for further localized reactions.