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Layered double hydroxide (LDH) is considered a highly promising electrode material for supercapacitors (SCs) due to its high theoretical specific capacitance. However, LDH powders often suffer from poor electrical conductivity, structure pulverization, slow charge transport, and insufficient active sites. Herein, a self‐supporting electrode with a Mott–Schottky heterostructure has been designed for high‐performance SCs. The electrode consists of low crystallinity NiCo‐LDH nanosheets and vertical graphene (VG) directly grown on carbon cloth. The LDH was converted from a metal–organic framework (MOF) by the sol–gel method. This self‐supporting electrode provides fast charge transfer, reducing the pulverization effect and energy barrier. The Mott–Schottky heterostructure of LDH@VG regulates electron density and enhances electron transfer, as confirmed by density functional theory calculation. The optimized LDH@VG heterostructure electrode exhibits an excellent areal capacitance of 5513.8 mF cm−2 and rate capability of 82.1%. Furthermore, the fabricated hybrid SC demonstrates excellent energy density of 404.8 μWh cm−2 at 1.6 mW cm−2 and a remarkable cycling life, with a capacitance of 92.0% after 10 000 cycles. This work not only provides a simple dip‐coating and MOF conversion method to synthesize heterojunction‐based electrodes, but also broadens the horizon for designing advanced electrode materials for SCs. [ABSTRACT FROM AUTHOR]

Due to its suitable bandgap and excellent stability, 3C-SiC is being investigated as one of the promising candidates for photoelectrochemical (PEC) water oxidation. However, the limited surface activity and short carrier lifetime prevent 3C-SiC photoanodes from facilitating efficient PEC water splitting. To tackle these problems, this work proposes a plasma technique to control the crystal structure and optical characteristics of 3C-SiC. Nitrogen plasma induces carbon vacancies (Vc) and Si–N bonds, further leading to a narrower bandgap of 3C-SiC. The combination of Vc and N doping enhanced the light trapping capability of the electrode, thereby improving the efficiency of electron–hole pair separation and charge transfer, resulting in an accelerated water oxidation reaction, i.e., photocurrent density (2.50 mA cm−2 at 1.23 VRHE) increased by 7.6 times compared to that of pristine SiC. This work offers an effective strategy for regulating the electronic structure of SiC-based photoanodes by plasma treatment, which may be extended to other photoelectrodes for PEC application. [ABSTRACT FROM AUTHOR]

A composite with shape memory‐assisted self‐healing and piezoresistive sensing ability is presented herein, and its high conductivity is attributed to a small amount of well‐dispersed carbon black (CB). Carboxylic acid groups are introduced into the polyvinyl butyral (PVB) side chain via the ring‐opening reaction of succinic anhydride. Thus, CB is well‐dispersed in the solution owing to simultaneous attraction and electrostatic repulsion. The resulting ink with less than 30 wt.% CB is highly conductive (3.7 S cm−1). In addition, hexamethylene diisocyanate (HDI) is used as a crosslinking agent to promote the reaction between OH and COOH in the side chains of the PVB‐COOH. The dual network consisting of urethane and amide bonds exhibits the shape memory effect. Moreover, the composite is shown to be capable of shape memory‐assisted self‐healing owing to the hydrogen bonds between the dual network and COOH, such that the resistance returns to its initial value, and the healed sample can support a 1 kg weight. The resulting multi‐modal sensing system is shown to detect bio‐signals such as body movements, breathing, and pulse. In summary, the present work provides an effective strategy for the development of conductive composite electrodes for various applications that require adaptability and piezoresistive sensing ability. [ABSTRACT FROM AUTHOR]

We report green light emitting diodes (LEDs) with Au nanoclusters in a micro-hole patterned p-GaN layer (ANCs-MHPP) to improve the light emission efficiency. Low-temperature photoluminescence (PL) and time-resolved PL showed that green LEDs with ANCs-MHPP demonstrated higher internal quantum efficiencies and faster decay times compared to conventional green LEDs. In addition, the opto-electronic performance of green LEDs with ANCs-MHPP was remarkable. These results can be attributed to the exciton–surface plasmon coupling between excitons in multi-quantum wells and surface plasmons of Au nanoclusters and the surface texturing effect caused by the geometrical shape of the micro-hole patterned p-GaN layer. [ABSTRACT FROM AUTHOR]

The demand for high-performance two-dimensional gas barrier materials is increasing owing to their potential for application in optoelectronic devices. These materials can help the devices maintain their properties over a long period. Therefore, in this study, we investigated the gas barrier performance of hexagonal boron nitride (h-BN) monolayers grown on copper foils via electrochemical polishing (ECP). The ECP treatment helped reduce the surface roughness of the copper foils. As a result, the nucleation density was reduced and highly crystalline h-BN monolayers were produced. The gas barrier performance of h-BN monolayers on copper foils with ECP was comparable to that of graphene. Our finding demonstrates the potential of monolayer h-BN as a high-performance and economical gas barrier material for organic-based optoelectronic devices. [ABSTRACT FROM AUTHOR]

Loading level, active material content of the cathode, and the thickness of composite solid electrolyte (CSE) sheets were optimized as 13 mg cm−2, 88 wt%, and 60 μm, respectively, for the development of all-solid lithium batteries (ASLBs) with high energy density. Thin CSE sheets were fabricated by adding PVDF binder with Al-LLZO powder and PEO-Li salt solution. PVDF had effects on the ionic conductivity, strength, and electrochemical stability of the CSE sheet. When the PVDF content was increased to 7 wt%, CSE sheet strength increased from 1.4 to 2.83 MPa, while the electrochemical stability has significantly improved at the range of oxidation and reduction potential. However, the ionic conductivity decreased from 3.7 × 10−4 to 1.73 × 10−4 S cm−1 at 70 °C. Moreover, the surface layer of the composite cathode was smoother than that of normal composition, and the interfacial resistance between the cathode compound layer and Al current collector has also decreased by adding PVDF. As a result of the test, the initial discharge capacity of the coin cell showed 207 mAh g−1 and 2.3 mAh cm−2 at 70 °C. [ABSTRACT FROM AUTHOR]

We demonstrate the synthesis of double-walled carbon nanotubes (DWNTs) with a selectively boron-doped outer tube via the thermal diffusion method. Such selective boron-doping in the outer tubes alters the electronic properties of the outer tubes while keeping the intrinsic properties of the inner tubes intact, thereby resulting in highly enhanced thermoelectric performance of the DWNTs. [ABSTRACT FROM AUTHOR]

Insulating polymers have received little attention in electronic applications. Here, we synthesize a photoresponsive, amphiphilic block copolymer (PEO-b-PVBO) and further control the chain growth of the block segment (PVBO) to obtain different degrees of polymerization (DPs). The benzylidene oxazolone moiety in PEO-b-PVBO facilitated chain-conformational changes due to photoisomerization under visible/ultraviolet (UV) light illumination. Intercalation of the photoresponsive but electrically insulating PEO-b-PVBO into graphene sheets enabled electrical monitoring of the conformational change of the block copolymer at the molecular level. The current change at the microampere level was proportional to the DP of PVBO, demonstrating that the PEO-b-PVBO-intercalated graphene nanohybrid (PGNH) can be used in UV sensors. Additionally, discrete signals at the nanoampere level were separated from the first derivative of the time-dependent current using the fast Fourier transform (FFT). Analysis of the harmonic frequencies using the FFT revealed that the PGNH afforded sawtooth-type current flow mediated by Coulomb blockade oscillation. Block copolymers are electrically insulating and therefore characterization with electrical or electrochemical methods is not possible. Here, the authors demonstrate electrical monitoring of the photoisomerization transition in a benzylidene oxazolone block co-polymer intercalated into graphene sheets. [ABSTRACT FROM AUTHOR]

Insulating polymers have received little attention in electronic applications. Here, we synthesize a photoresponsive, amphiphilic block copolymer (PEO-b-PVBO) and further control the chain growth of the block segment (PVBO) to obtain different degrees of polymerization (DPs). The benzylidene oxazolone moiety in PEO-b-PVBO facilitated chain-conformational changes due to photoisomerization under visible/ultraviolet (UV) light illumination. Intercalation of the photoresponsive but electrically insulating PEO-b-PVBO into graphene sheets enabled electrical monitoring of the conformational change of the block copolymer at the molecular level. The current change at the microampere level was proportional to the DP of PVBO, demonstrating that the PEO-b-PVBO-intercalated graphene nanohybrid (PGNH) can be used in UV sensors. Additionally, discrete signals at the nanoampere level were separated from the first derivative of the time-dependent current using the fast Fourier transform (FFT). Analysis of the harmonic frequencies using the FFT revealed that the PGNH afforded sawtooth-type current flow mediated by Coulomb blockade oscillation. Block copolymers are electrically insulating and therefore characterization with electrical or electrochemical methods is not possible. Here, the authors demonstrate electrical monitoring of the photoisomerization transition in a benzylidene oxazolone block co-polymer intercalated into graphene sheets. [ABSTRACT FROM AUTHOR]

Nitrogen (N)-doped nanostructured carbons have been actively examined as promising alternatives for precious-metal catalysts in various electrochemical energy generation systems. Herein, an effective approach for synthesizing N-doped single-walled carbon nanohorns (SWNHs) with highly electrocatalytic active sites via controlled oxidation followed by N2 plasma is presented. Nanosized holes were created on the conical tips and sidewalls of SWNHs under mild oxidation, and subsequently, the edges of the holes were easily decorated with N atoms. The N atoms were present preferentially in a pyridinic configuration along the edges of the nanosized holes without significant structural change of the SWNHs. The enriched edges decorated with the pyridinic-N atoms at the atomic scale increased the number of active sites for the oxygen reduction reaction, and the inherent spherical three-dimensional feature of the SWNHs provided good electrical conductivity and excellent mass transport. We demonstrated an effective method for promoting the electrocatalytic active sites within N-doped SWNHs by combining defect engineering with the preferential formation of N atoms having a specific configuration. [ABSTRACT FROM AUTHOR]

A unique, thermoplastic polyurethane (TPU)-based, pressure-sensitive nanocomposites were prepared by the solution mixing method. Poly (methyl methacrylate) (PMMA) microbeads (10µm) were coated with multiwall carbon nanotubes (MWCNT) and dispersed in TPU matrix dissolved in tetrahydrofuran. 1, 2, and 5 wt. % of carbon nanofiber (CNF) were also added to the TPU matrix. The influence of MWCNT coated PMMA-microbeads along with different CNF contents on the pressure sensing properties were studied. Electrical and thermal conductivities were measured at different external loads. The prepared nanocomposites showed repeatable and reliable electric response with increasing external load and are suitable as pressure sensors. [ABSTRACT FROM AUTHOR]

ABSTRACT The effects of alignment of polyacrylonitrile (PAN) nanofibers and a two-step drawing process on the mechanical properties of the fibers were evaluated in the current study. The alignment was achieved using a high-speed collector in electrospinning synthesis of the nanofibers. Under optimal two-step drawing conditions (e.g., hot-water and hot-air stretching), the PAN nanofiber felts exhibited large improvements in both alignment and molecular chain-orientation. Large increase in crystallinity, crystallite size, and molecular chain orientation were observed with increasing draw ratio. Optimally, stretched PAN-based nanofibers exhibited 5.3 times higher tensile strength and 6.7 times higher tensile modulus than those of the pristine one. In addition, bulk density of the drawn PAN nanofibers increased from 0.19 to 0.33 g/cm3. Our results show that fully extended and oriented polymer chains are critical in achieving the highest mechanical properties of the electrospun PAN nanofibers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43945. [ABSTRACT FROM AUTHOR]

The low energy density of commercially available activated carbon-based supercapacitors has limited their widespread applications. In the current work, we demonstrated fabrication of carbon nanofiber-based supercapacitors that exhibited ultra-high energy density by rationally tailoring their pore structure in an ionic liquid system. To gain control on the pore structure, three different methods were employed for the synthesis of an electrospinning-derived freestanding carbon nanofiber web. They are incorporation of a pore generator (i.e., tetraethyl orthosilicate) in the electrospinning step, physical activation (e.g., H2O or CO2), and hydrogen treatment. We observed finely tuned pore sizes ranging from 0.734 to 0.831 nm and accompanying changes in BET surface areas ranging from 1160 to 1624 m2 g−1. The entrapped TEOS within the electrospun organic nanofiber web provided high tuning ability of the pore structure in the following carbonization step, and decreased the activation energy of the pore formation. Both high specific capacitance (161 F g−1) and ultra-high energy density (246 W h kg−1) were achieved when the pore size on the surface of carbon nanofibers matched with the ionic size of the electrolyte. Our results demonstrate the importance of a finely tuned pore structure to secure high-temperature operable carbon nanofiber-based supercapacitors with ultrahigh energy density using ionic liquids as electrolytes. [ABSTRACT FROM AUTHOR]

Incorporating heteroatoms into onion-like carbon (OLC, average size ∼5 nm) with a fullerene-like structure and investigating its peculiar properties are fascinating challenges. Here, we present straightforward fabrication of doped OLC samples with a high concentration of boron (0.63–4.57 at%) via a high-temperature thermal diffusion method. The highest proportion of substitutional boron of the boron species reaches 29%, which far exceeds most of the reported boron-doped carbon materials. The influence of boron on the fullerene-like layers and electronic properties of OLC is systematically investigated using Raman spectroscopy with different excitation energies (1.58–3.8 eV) and ultraviolet photoelectron spectroscopy (UPS). The as-prepared boron-doped OLC samples exhibit a perfect four-electron process for the oxygen reduction reaction (ORR), which is similar to commercial Pt/C. It is worth noting that the intrinsic relationship between the electronic properties and catalytic performance of doped samples is explored based on experimental studies instead of theoretical calculations. The results indicate that the lower work function, lower valence band edge and higher density of states (DOSs) of doped OLC are crucial to improve the catalytic performance. Our work can provide valuable information on the design of doped metal-free materials and give new evidence for enhanced ORR activity associated with heteroatom doping and electronic properties. [ABSTRACT FROM AUTHOR]

The hybridization of an electrochemically active metal oxide with electrically conductive carbon nanofibers (CNFs) has been utilized as a solution to overcome the energy density limitation of carbon-based supercapacitors as well as the poor cyclic stability of metal oxides. Herein, we have demonstrated the growth of binary metal oxide nanosheets on the engineered surface of CNFs to fully exploit their electrochemical activity. Metal oxide nanosheets were observed to grow vertically from the surface of CNFs. The high structural toughness of the CNF–metal oxide composite under strong sonication indicated strong interfacial binding strength between the metal oxide and the CNFs. The rationally designed porous CNFs presented a high specific surface area and showed high capacity for adsorbing metal ions, where the active edge sites acted as anchoring sites for the nucleation of metal oxides, thereby leading to the formation of a well dispersed and thin layer structure of binary metal oxide nanosheets. Excellent electrochemical performance (e.g., specific capacitance of 2894.70 F g−1 and energy density of 403.28 W h kg−1) was observed for these binary metal oxide nanosheets, which can be attributed to the large increase in the accessible surface area of the electrochemically active metal oxide nanosheets due to their homogeneous distribution on porous CNFs, as well as the efficient charge transfer from the metal oxide to the CNFs facilitated the improvement in the performance. [ABSTRACT FROM AUTHOR]

Exploring the potential catalytic applications of boron-doped carbon materials is a fascinating challenge. Here we describe that boron-doped onion-like carbon and carbon nanotubes as metal-free catalysts exhibit excellent catalytic activity and stability in nitroarene reduction under a stoichiometric amount of reductant. [ABSTRACT FROM AUTHOR]

Chemically doped graphene has been actively investigated as an electrode material for achieving high-performance electrochemical systems. However, the stability of pure-carbon-rich edges and/or heteroatom-decorated edges, and their effect on the electrochemical performance remain largely unexplored. We found that in a high temperature thermal doping process, the functionalized graphene edges were structurally stable at 1200 °C, whereas the edges at 1500 °C were unstable and coalesced into loops through covalent bond formation between adjacent graphene edges. Interestingly, boron and nitrogen co-doped graphene prepared at 1200 °C showed the largest capacitance in both acidic and alkaline media due to the presence of the BNO moieties along the edge sites. The doped material also showed the best rate capability due to the largely enhanced electrical conductivity originating from the substitutionally doped boron and nitrogen atoms. Our findings regarding the stability of heteroatom-decorated edges without loop formation can now be utilized as a guideline for maximizing the electrochemical activity of graphene in various electrochemical systems. [ABSTRACT FROM AUTHOR]

An effective way of covalently functionalizing graphene with a chitosan polymer via a nitrene chemistry is demonstrated. The biofunctionalized graphene is prepared by the chemical reduction of graphene oxide using a nitrene chemistry, and then covalently grafting chitosan to the graphene surface. The effectiveness of the biofunctionalized graphene as a reinforcing filler (4 wt%) in a chitosan polymer matrix is verified by the dramatic enhancement of the mechanical properties (breaking stress = 330%, Young's modulus = 243%) and the electrical conductivity (0.3 S m−1) without much loss in the elongation-at-break. The reinforcing effect can be explained by both the homogeneous dispersion of graphene within the matrix and the strong bond arising from the intrinsically intimate contact between the graphene and the matrix. The high antimicrobial activity of the biofunctionalized graphene compared with graphene oxide and chemically reduced graphene may be because of the presence of chitosan polymer on the edges of the graphene. The strong, antimicrobial graphene-filled composite film can be used for food packaging and for coating various biomedical devices, where bacterial surface colonization is undesirable. [ABSTRACT FROM AUTHOR]

The electronic interactions between the [Cu(opba)]2− anions (where opba is orthophenylenebis (oxamato)) and single-wall carbon nanotubes (SWCNTs) were investigated by resonance Raman spectroscopy. The opba can form molecular magnets, and the interactions of opba with SWCNTs can produce materials with very different magnetic/electronic properties. It is observed that the electronic interaction shows a dependence on the SWCNT diameter independent of whether they are metallic or semiconducting, although the interaction is stronger for metallic tubes. The interaction also is dependent on the amount of complex that is probably adsorbed on the carbon surface of the SWCNTs. Some charge transfer can be also occurring between the metallic complex and the SWCNTs. Copyright © 2012 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]