Thermal Conductivity of Carbon/Boron Nitride Heteronanotube and Boron Nitride Nanotube Buckypapers: Implications for Thermal Management Composites.

To date, there has been limited reporting on the fabrication and properties of macroscopic sheet assemblies (specifically buckypapers) composed of carbon/boron nitride core-shell heteronanotubes (MWCNT@BNNT) or boron nitride nanotubes (BNNTs). Herein we report the synthesis of MWCNT@BNNTs via a facile method involving Atmospheric Pressure Chemical Vapor Deposition (APCVD) and the safe h-BN precursor ammonia borane. These MWCNT@BNNTs were used as sacrificial templates for BNNT synthesis by thermal oxidation of the core carbon. Buckypaper fabrication was facilitated by facile sonication and filtration steps. To test the thermal conductivity properties of these new buckypapers, in the interest of thermal management applications, we have developed a novel technique of advanced scanning thermal microscopy (SThM) that we call piercing SThM (pSThM). Our measurements show a 14% increase in thermal conductivity of the MWCNT@BNNT buckypaper relative to a control multiwalled carbon nanotube (MWCNT) buckypaper. Meanwhile, our BNNT buckypaper exhibited approximately half the thermal conductivity of the MWCNT control, which we attribute to the turbostratic quality of our BNNTs. To the best of our knowledge, this work achieves the first thermal conductivity measurement of a MWCNT@BNNT buckypaper and of a BNNT buckypaper composed of BNNTs not synthesized by high energy techniques.

GaS:WS2 Heterojunctions for Ultrathin Two-Dimensional Photodetectors with Large Linear Dynamic Range across Broad Wavelengths.

Two-dimensional (2D) photodetectors based on photovoltaic effect or photogating effect can hardly achieve both high photoresponsivity and large linear dynamic range at the same time, which greatly limits many practical applications such as imaging sensors. Here, the conductive-sensitizer strategy, a general design for improving photoresponsivity and linear dynamic range in 2D photodetectors is provided and experimentally demonstrated on vertically stacked bilayer WS2/GaS0.87 under a parallel circuit mode. Owing to successful band alignment engineering, the isotype type-II heterojunction enables efficient charge carrier transfer from WS2, the high-mobility sensitizer, to GaS0.87, the low-mobility channel, under illumination from a broad visible spectrum. The transferred electron charges introduce a reverse electric field which efficiently lowers the band offset between the two materials, facilitating a transition from low-mobility photocarrier transport to high-mobility photocarrier transport with increasing illumination power. We achieved a large linear dynamic range of 73 dB as well as a high and constant photoresponsivity of 13 A/W under green light. X-ray photoelectron spectroscopy, cathodoluminescence, and Kelvin probe force microscopy further identify the key role of defects in monolayer GaS0.87 in engineering the band alignment with monolayer WS2. This work proposes a design route based on band and interface modulation for improving performance of 2D photodetectors and provides deep insights into the important role of strong interlayer coupling in offering heterostructures with desired properties and functions.

Ni2Mn-layered double oxide electrodes in organic electrolyte based supercapacitors.

The development of future mobility (e.g. electric vehicles) requires supercapacitors with high voltage and high energy density. Conventional active carbon-based supercapacitors have almost reached their limit of energy density which is still far below the desired performance. Advanced materials, particularly metal hydroxides/oxides with tailored structure are promising supercapacitor electrodes to push the limit of energy density. To date, research has largely focused on evaluation of these materials in aqueous electrolyte, while this may enable high specific capacitance, it results in low working voltage window and poor cycle stability. Herein, we report the development of Ni2Mn-layered double oxides (Ni2Mn-LDOs) as mixed metal oxide-based supercapacitor electrodes for use in an organic electrolyte. Ni2Mn-LDO obtained by calcination of [Ni0.66Mn0.33(OH)2](CO3)0.175·nH2O at 400 °C produced the best performing Ni2Mn-LDOs with high working voltage of 2.5 V and a specific capacitance of 44 F g-1 (at 1 A g-1). We believe the performance of the Ni2Mn-LDOs is related to its unique porous structure, high surface area and the homogeneous mixed metal oxide network. Ni2Mn-LDO outperforms both the single metal oxides (NiO, MnO2) and the equivalent physical mixture of the two oxides. We propose this performance boost arises from synergy between NiO and MnO x due to a more effective homogeneous network of NiO/MnO x domains in the Ni2Mn-LDO. This work clearly shows the advantage of an LDO over the single component metal oxides as well as the physical mixture of mixed metal oxides and highlights the possibilities of development of further mixed metal oxides-based supercapacitors in organic electrolyte using LDH precursors.

Controlling Defects in Continuous 2D GaS Films for High-Performance Wavelength-Tunable UV-Discriminating Photodetectors.

A chemical vapor deposition method is developed for thickness-controlled (one to four layers), uniform, and continuous films of both defective gallium(II) sulfide (GaS): GaS0.87 and stoichiometric GaS. The unique degradation mechanism of GaS0.87 with X-ray photoelectron spectroscopy and annular dark-field scanning transmission electron microscopy is studied, and it is found that the poor stability and weak optical signal from GaS are strongly related to photo-induced oxidation at defects. An enhanced stability of the stoichiometric GaS is demonstrated under laser and strong UV light, and by controlling defects in GaS, the photoresponse range can be changed from vis-to-UV to UV-discriminating. The stoichiometric GaS is suitable for large-scale, UV-sensitive, high-performance photodetector arrays for information encoding under large vis-light noise, with short response time (<66 ms), excellent UV photoresponsivity (4.7 A W-1 for trilayer GaS), and 26-times increase of signal-to-noise ratio compared with small-bandgap 2D semiconductors. By comprehensive characterizations from atomic-scale structures to large-scale device performances in 2D semiconductors, the study provides insights into the role of defects, the importance of neglected material-quality control, and how to enhance device performance, and both layer-controlled defective GaS0.87 and stoichiometric GaS prove to be promising platforms for study of novel phenomena and new applications.

Ultra-stiff large-area carpets of carbon nanotubes.

Herewith, we report the influence of post-synthesis heat treatment (≤2350 °C and plasma temperatures) on the crystal structure, defect density, purity, alignment and dispersibility of free-standing large-area (several cm(2)) carpets of ultra-long (several mm) vertically aligned multi-wall carbon nanotubes (VA-MWCNTs). VA-MWCNTs were produced in large quantities (20-30 g per batch) using a semi-scaled-up aerosol-assisted chemical vapour deposition (AACVD) setup. Electron and X-ray diffraction showed that the heat treatment at 2350 °C under inert atmosphere purifies, removes residual catalyst particles, and partially aligns adjacent single crystals (crystallites) in polycrystalline MWCNTs. The purification and improvement in the crystallites alignment within the MWCNTs resulted in reduced dispersibility of the VA-MWCNTs in liquid media. High-resolution microscopy revealed that the crystallinity is improved in scales of few tens of nanometres while the point defects remain largely unaffected. The heat treatment also had a marked benefit on the mechanical properties of the carpets. For the first time, we report compression moduli as high as 120 MPa for VA-MWCNT carpets, i.e. an order of magnitude higher than previously reported figures. The application of higher temperatures (arc-discharge plasma, ≥4000 °C) resulted in the formation of a novel graphite-matrix composite reinforced with CVD and arc-discharge-like carbon nanotubes.

Rapid epitaxy-free graphene synthesis on silicidated polycrystalline platinum.

Large-area synthesis of high-quality graphene by chemical vapour deposition on metallic substrates requires polishing or substrate grain enlargement followed by a lengthy growth period. Here we demonstrate a novel substrate processing method for facile synthesis of mm-sized, single-crystal graphene by coating polycrystalline platinum foils with a silicon-containing film. The film reacts with platinum on heating, resulting in the formation of a liquid platinum silicide layer that screens the platinum lattice and fills topographic defects. This reduces the dependence on the surface properties of the catalytic substrate, improving the crystallinity, uniformity and size of graphene domains. At elevated temperatures growth rates of more than an order of magnitude higher (120 µm min(-1)) than typically reported are achieved, allowing savings in costs for consumable materials, energy and time. This generic technique paves the way for using a whole new range of eutectic substrates for the large-area synthesis of 2D materials.

Interfacial electron-shuttling processes across KolliphorEL monolayer grafted electrodes.

Covalently grafted KolliphorEL (a poly(ethylene glycol)-based transporter molecule for hydrophobic water-insoluble drugs; MW, ca. 2486; diameter, ca. 3 nm) at the surface of a glassy-carbon electrode strongly affects the rate of electron transfer for aqueous redox systems such as Fe(CN)6(3-/4-). XPS data confirm monolayer grafting after electrochemical anodization in pure KolliphorEL. On the basis of voltammetry and impedance measurements, the charge transfer process for the Fe(CN)6(3-/4-) probe molecule is completely blocked after KolliphorEL grafting and in the absence of a "guest". However, in the presence of low concentrations of suitable ferrocene derivatives as guests, mediated electron transfer across the monolayer via a shuttle mechanism is observed. The resulting amplification of the ferrocene electroanalytical signal is investigated systematically and compared for five ferrocene derivatives. The low-concentration electron shuttle efficiency decreases in the following sequence: (dimethylaminomethyl)ferrocene > n-butyl ferrocene > ferrocene dimethanol > ferroceneacetonitrile > ferroceneacetic acid.

Amplified electron transfer at poly-ethylene-glycol (PEG) grafted electrodes.

"Amplified" electron transfer is observed purely based on electron transfer kinetic effects at modified carbon surfaces. An anodic attachment methodology is employed to modify the surface of glassy carbon or boron doped diamond electrodes with poly-ethylene glycols (PEGs) for polymerisation degrees of n = 4.5 to 9.1 (PEG200 to PEG400). Voltammetry and impedance data for aqueous Fe(CN)6(3-/4-) suggest systematic PEG structure-dependent effects on the standard rate constant for heterogeneous electron transfer as a function of PEG deposition conditions and average polymer chain length. Tunnel distance coefficients are polymerisation degree dependent and estimated for shorter PEG chains, ß = 0.17 Å(-1) for aqueous Fe(CN)6(3-/4-), consistent with a diffuse water-PEG interface. In contrast, electron transfer to 1,1'-ferrocene-dimethanol (at 1 mM concentration) appears un-impeded by PEG grafts. Mediated or "amplified" electron transfer to Fe(CN)6(3-/4-) based on the 1,1'-ferrocene-dimethanol redox shuttle is observed for both oxidation and reduction with estimated bimolecular rate constants for homogeneous electron transfer of kforward = 4 × 10(5) mol dm(3) s(-1) and kbackward = 1 × 10(5) mol dm(3) s(-1). Digital simulation analysis suggests an additional resistive component within the PEG graft double layer.

Oxygen reduction at sparse arrays of platinum nanoparticles in aqueous acid: hydrogen peroxide as a liberated two electron intermediate.

Electrodeposition methods are used to generate a sparse array of platinum nanoparticles on a glassy carbon electrode. Specifically electrodeposition from a 1 mM solution of H2PtCl6 in 0.5 M H2SO4 leads to surface coverages of 0.46% to 1.96% and nanoparticles of size 29 nm to 136 nm in diameter, using deposition times of 30 and 15 seconds. The reduction of oxygen at an array of 29 nm nanoparticles with a surface coverage of 0.46% showed voltammetric signals with a scan rate dependence consistent with a two electron reduction of O2 to H2O2 with the rate proportional to K0 exp(-α(E-Ef(0))/RT) and formal potential (Ef(0)) of -0.058 V vs. SHE, a standard electrochemical rate constant (k0) of ~10 cm s(-1) and a transfer coefficient (α) of 0.23. At higher Pt nanoparticle coverages, a scan rate dependence consistent with the partial further reduction of H2O2 to water becomes evident.