The application of the surface energy based solubility parameter theory for the rational design of polymer-functionalized MWCNTs

The surface energy based solubility parameters theory was applied to model the degree of polystyrene-functionalisation of MWCNTs in six different organic solvents. The experimental characterization of the polymer-functionalized MWCNTs is consistent with the predictions of this model providing a breakthrough towards the rational design of functionalized MWCNTs based on thermodynamic parameters

Comparison of carbon materials as electrodes for enzyme electrocatalysis:hydrogenase as a case study

We present a study of electrocatalysis by an enzyme adsorbed on a range of carbon materials, with different size, surface area, morphology and graphitic structure, which are either commercially available or prepared via simple, established protocols. We choose as our model enzyme the hydrogenase I from E. coli (Hyd-1), which is an active catalyst for H2 oxidation, is relatively robust and has been demonstrated in H2 fuel cells and H2-driven chemical synthesis. The carbon materials were characterised according to their surface area, surface morphology and graphitic character, and we use the electrocatalytic H2 oxidation current for Hyd-1 adsorbed on these materials to evaluate their effectiveness as enzyme electrodes. Here, we show that a variety of carbon materials are suitable for adsorbing hydrogenases in an electroactive configuration. This unified study provides insight into selection and design of carbon materials for study of redox enzymes and different applications of enzyme electrocatalysis

Time dependent decomposition of ammonia borane for the controlled production of 2D hexagonal boron nitride.

Ammonia borane (AB) is among the most promising precursors for the large-scale synthesis of hexagonal boron nitride (h-BN) by chemical vapour deposition (CVD). Its non-toxic and non-flammable properties make AB particularly attractive for industry. AB decomposition under CVD conditions, however, is complex and hence has hindered tailored h-BN production and its exploitation. To overcome this challenge, we report in-depth decomposition studies of AB under industrially safe growth conditions. In situ mass spectrometry revealed a time and temperature-dependent release of a plethora of NxBy-containing species and, as a result, significant changes of the N:B ratio during h-BN synthesis. Such fluctuations strongly influence the formation and morphology of 2D h-BN. By means of in situ gas monitoring and regulating the precursor temperature over time we achieve uniform release of volatile chemical species over many hours for the first time, paving the way towards the controlled, industrially viable production of h-BN

Rational synthesis of polymer coated inorganic nanoparticles-MWCNT hybrids via solvophobic effects

The efficient synthesis of inorganic nanoparticle-carbon nanotube hybrids requires the development of models and synthetic guidelines that can be used to maximise the interactions between both nanomaterials. Herein we report the application of the Hansen surface energy based solubility parameter theory as a model for the selection of solvents that can maximise the interactions between iron oxide nanoparticles and MWCNTs. To achieve this, we synthesized iron oxide nanoparticle-MWCNT hybrid materials in three different solvents and characterized their composition with TGA. The solvent was found to have a significant impact in the final amount of iron oxide composition of the hybrids. The Hansen surface energy based solubility parameters of MWCNTs were characterized via inverse gas chromatography and were used to evaluate the interactions between the MWCNTs and the solvent media. Under this model we expected that large differences between the Hansen surface energy based solubility parameters of solvents and MWCNTs would be correlated with larger incorporation of iron oxide nanoparticles in the hybrids. The amount of iron oxide nanoparticles found in the hybrids were indeed consistent with the predictions of the Hansen surface energy based solubility parameter theory making it a powerful tool for the design of nanoparticle-carbon nanotube hybrids

WS22D nanosheets in 3D nanoflowers

In this work it has been established that 3D nanoflowers of WS2 synthesized by chemical vapour deposition are composed of few layer WS2 along the edges of the petals. An experimental study to understand the evolution of these nanostructures shows the nucleation and growth along with the compositional changes they undergo

A Graphene Surface Force Balance

We report a method for transferring graphene, grown by chemical vapor deposition, which produces ultraflat graphene surfaces (root-mean-square roughness of 0.19 nm) free from polymer residues over macroscopic areas (>1 cm2). The critical step in preparing such surfaces involves the use of an intermediate mica template, which itself is atomically smooth. We demonstrate the compatibility of these model surfaces with the surface force balance, opening up the possibility of measuring normal and lateral forces, including friction and adhesion, between two graphene sheets either in contact or across a liquid medium. The conductivity of the graphene surfaces allows forces to be measured while controlling the surface potential. This new apparatus, the graphene surface force balance, is expected to be of importance to the future understanding of graphene in applications from lubrication to electrochemical energy storage systems

Multiscale interactions of liquid, bubbles and solid phases in ultrasonic fields revealed by multiphysics modelling and ultrafast X-ray imaging

The volume of fluid (VOF) and continuous surface force (CSF) methods were used to develop a bubble dynamics model for the simulation of bubble oscillation and implosion dynamics under ultrasound. The model was calibrated and validated by the X-ray image data acquired by ultrafast synchrotron X-ray. Coupled bubble interactions with bulk graphite and freely moving particles were also simulated based on the validated model. Simulation and experiments quantified the surface instability developed along the bubble surface under the influence of ultrasound pressure fields. Once the surface instability exceeds a certain amplitude, bubble implosion occurs, creating shock waves and highly deformed, irregular gas-liquid boundaries and smaller bubble fragments. Bubble implosion can produce cyclic impulsive stresses sufficient enough to cause µs fatigue exfoliation of graphite layers. Bubble-particle interaction simulations reveal the underlying mechanisms for efficient particle dispersion or particle wrapping which are all strongly related to the oscillation dynamics of the bubbles and the particle surface properties

Multiscale interactions of liquid, bubbles and solid phases in ultrasonic fields revealed by multiphysics modelling and ultrafast X-ray imaging

The volume of fluid (VOF) and continuous surface force (CSF) methods were used to develop a bubble dynamics model for the simulation of bubble oscillation and implosion dynamics under ultrasound. The model was calibrated and validated by the X-ray image data acquired by ultrafast synchrotron X-ray. Coupled bubble interactions with bulk graphite and freely moving particles were also simulated based on the validated model. Simulation and experiments quantified the surface instability developed along the bubble surface under the influence of ultrasound pressure fields. Once the surface instability exceeds a certain amplitude, bubble implosion occurs, creating shock waves and highly deformed, irregular gas-liquid boundaries and smaller bubble fragments. Bubble implosion can produce cyclic impulsive stresses sufficient enough to cause µs fatigue exfoliation of graphite layers. Bubble-particle interaction simulations reveal the underlying mechanisms for efficient particle dispersion or particle wrapping which are all strongly related to the oscillation dynamics of the bubbles and the particle surface properties

Effects of green solvents and surfactants on the characteristics of few-layer graphene produced by dual-frequency ultrasonic liquid phase exfoliation technique

Nowadays, one of the promising methods for scalable graphene production is ultrasound-aided liquid phase exfoliation (ULPE) of graphite. Two current limiting factors of ULPE are the use of harmful solutions (such as N-Methyl-2-pyrrolidone or Dimethylformamide) and a relatively low graphene yield. In this study, we demonstrate a new dual frequency (20 kHz and 1174 kHz) ULPE approach in various eco-friendly media, which enabled us to produce various few-layer graphene (FLG) solutions of high quality. By implementing sophisticated characterisation techniques consisting of Raman spectroscopy, UV–vis spectroscopy and high-resolution electron microscopy, the final graphene flakes structure was confirmed to correlate the properties of each individual solution. The thinner (∼3 layers) and larger (∼1.5 μm2) flakes were observed while using just water, with the highest yield (11%) of smaller FLG flakes to be achieved in the mixture of water and a surfactant. In order to understand the cavitation mechanism in different solutions, the ULPE process was investigated by acoustic measurements. This study demonstrates the crucial role of ethanol (as a solvent) and surfactants as it regulates the cavitation power and intensity of the ultrasonic field and, thereby, the cavitation effectiveness. It is suggested that the mixture of water, ethanol and a surfactant is the best medium for ULPE process where a high yield of low-defective FLG flakes can be obtained in a solution stable at least for 3 months (around 80%)

Dual frequency ultrasonic cavitation in various liquids: high-speed imaging and acoustic pressure measurements

Ultrasonic cavitation is used in various processes and applications, utilising powerful shock waves and high-speed liquid jets generated by the collapsing bubbles. Typically, a single frequency source is used to produce the desired effects. However, optimisation of the efficiency of ultrasound reactors is necessary to improve cavitation activity in specific applications such as for the exfoliation of two dimensional (2D) materials. This research takes the next step to investigate the effect of a dual frequency transducer system on the bubble dynamics, cavitation zone, pressure fields, acoustic spectra and induced shock waves for four liquids with a range of physical properties. Using ultra-high-speed imaging and synchronised acoustic pressure measurements, the effect of ultrasonic dual frequencies on bubble dynamics was investigated. The addition of a high frequency transducer (1174 kHz) showed that the bubble fragments and satellite bubbles induced from a low frequency transducer (24 kHz) were able to extend their lifecycle, increase spatial distribution, thus, extending the boundaries of the cavitation zone. Furthermore, this combination of ultrasonic frequencies generated higher acoustic pressures (up to 180%) and enhanced the characteristic shock wave peak, indicating more bubble collapses and the generation of additional shock waves. The dual frequency system also enlarged the cavitation cloud size under the sonotrode. These observations specifically delineated the enhancement of cavitation activity using a dual frequency system pivotal for optimisation of existing cavitation-based processing technologies