Highly Uniform Nanodiamond-Graphene Composites Microspheres for Electrocatalytic Hydrogen Evolution.

To progress the clean hydrogen-gas-based energy economy, there is a demand for cost-effective, highly efficient catalysts to facilitate the hydrogen evolution reaction process (HER). Due to the amazing catalytic capabilities of two-dimensional materials, extensive research has been done on these structures. However, most of the described syntheses take a lot of time, are challenging, and are ineffective. The present work demonstrates the performance of the recently reported nanodiamond/graphene composite microsphere ND-GCSs as a catalyst for HER. These spheres were produced via the microwave-irradiation approach. A modified process was adopted to improve the particle size uniformity and yield. The prepared composite spheres showed very interesting catalytic activity for the HER when assembled on a screen-printed carbon electrode. The prepared ND-GCSs@SPCE showed a significant shift of the onset potential to ca. -450 mV and a small Tafel slope value of ca. 85 mV/decade. The electron transfer was drastically enhanced with a tremendous decrease in charge transfer resistance to ca. 265 Ω. The electrocatalyst showed excellent long-term stability for the HER application. Additionally, this novel composite structure might be beneficial for diverse applications including batteries, supercapacitors, catalyst supports, and more.

High conversion continuous flow exfoliation of 2D MoS2.

We report a low-cost and highly efficient process for exfoliating of MoS2 using an energy efficient vortex fluidic device (VFD). This method is high in green chemistry metrics in avoiding the use of auxiliary substances, and the process is scalable, with a conversion of as received MoS2 into 2D sheets at ∼73%.

Sub-micron moulding topological mass transport regimes in angled vortex fluidic flow.

Shear stress in dynamic thin films, as in vortex fluidics, can be harnessed for generating non-equilibrium conditions, but the nature of the fluid flow is not understood. A rapidly rotating inclined tube in the vortex fluidic device (VFD) imparts shear stress (mechanical energy) into a thin film of liquid, depending on the physical characteristics of the liquid and rotational speed, ω, tilt angle, θ, and diameter of the tube. Through understanding that the fluid exhibits resonance behaviours from the confining boundaries of the glass surface and the meniscus that determines the liquid film thickness, we have established specific topological mass transport regimes. These topologies have been established through materials processing, as spinning top flow normal to the surface of the tube, double-helical flow across the thin film, and spicular flow, a transitional region where both effects contribute. The manifestation of mass transport patterns within the film have been observed by monitoring the mixing time, temperature profile, and film thickness against increasing rotational speed, ω. In addition, these flow patterns have unique signatures that enable the morphology of nanomaterials processed in the VFD to be predicted, for example in reversible scrolling and crumbling graphene oxide sheets. Shear-stress induced recrystallisation, crystallisation and polymerisation, at different rotational speeds, provide moulds of high-shear topologies, as 'positive' and 'negative' spicular flow behaviour. 'Molecular drilling' of holes in a thin film of polysulfone demonstrate spatial arrangement of double-helices. The grand sum of the different behavioural regimes is a general fluid flow model that accounts for all processing in the VFD at an optimal tilt angle of 45°, and provides a new concept in the fabrication of novel nanomaterials and controlling the organisation of matter.

High-Yield Continuous-Flow Synthesis of Spheroidal C60@Graphene Composites as Supercapacitors.

Graphene spheres confining fullerene C60 are quantitatively formed under high-shear and continuous-flow processing using a vortex fluidic device (VFD). This involves intense micromixing a colloidal suspension of graphite in DMF and an o-xylene solution of C60 at room temperature in the absence of surfactants and other auxiliary substances. The diameters of the composite spheres, C60@graphene, can be controlled with size distributions ranging from 1.5 to 3.5 µm, depending on the VFD operating parameters, including rotational speed, flow rate, relative ratio of C60 to graphite, and the concentration of fullerene. An electrode of the composite material has high cycle stability, with a high areal capacitance of 103.4 mF cm-2, maintaining its capacitances to 24.7 F g-1 and 86.4 mF cm-2 (83.5%) at a high scan rate of 100 mV s-1.

Vertically aligned laser sliced MWCNTs.

Applications of multi-walled carbon nanotubes (MWCNTs) benefit from the availability of specific lengths of the material while keeping the outer walls pristine, for example, for applications requiring vertically aligned tubes. To this end, a simple and effective continuous flow 'top down' process to control the length of sliced MWCNTs has been developed using a vortex fluidic device (VFD) coupled with a 1064 nm pulse laser, with the process in the absence of chemicals and any auxiliary substances. Three different length distributions of the sliced MWCNTs, centered at 75 ± 2.1 nm, 300 ± 1.8 nm and 550 ± 1.4 nm, have been generated with the length depending on the VFD operating parameters and laser energy, with the processing resulting in a decrease in side wall defects of the material. We also show the ability to vertically self assemble short MWCNTs on a silicon substrate with control of the surface density coverage using a simple dipping and rinsing method.

Continuous flow photolytic reduction of graphene oxide.

Reduced graphene oxide (rGO) is generated from GO dispersed in water under continuous flow in the absence of harsh reducing agents, in a vortex fluidic device, such that the processing is scalable with uniformity of the product. This involves simultaneously UV irradiating (λ = 254 nm, 20 W) the dynamic thin film in the rapidly rotating glass tube in the microfluidic platform. The rGO is comparable to that formed using waste generating chemical based processing, with a film of the material having a resistance of 2.2 × 105 Ω and a remarkably high conductivity of 2 × 104 S cm-1.

Inverted vortex fluidic exfoliation and scrolling of hexagonal-boron nitride.

Exfoliation or scrolling of hexagonal boron nitride (h-BN) occurs in a vortex fluidic device (VFD) operating under continuous flow, with a tilt angle of -45° relative to the horizontal position. This new VFD processing strategy is effective in avoiding the build-up of material that occurs when the device is operated using the conventional tilt angle of +45°, where the h-BN precursor and scrolls are centrifugally held against the wall of the tube. At a tilt angle of -45° the downward flow aided by gravity facilitates material exiting the tube with the exfoliation of h-BN and formation of h-BN scrolls then optimized by systematically varying the other VFD operating parameters, including flow rate and rotational speed, along with concentration of h-BN and the choice of solvent. Water was the most effective solvent, which enhances the green chemistry metrics of the processing.

Vortex fluidic mediated transformation of graphite into highly conducting graphene scrolls.

Two-dimensional graphene has remarkable properties that are revolutionary in many applications. Scrolling monolayer graphene with precise tunability would create further potential for niche applications but this has proved challenging. We have now established the ability to fabricate monolayer graphene scrolls in high yield directly from graphite flakes under non-equilibrium conditions at room temperature in dynamic thin films of liquid. Using conductive atomic force microscopy we demonstrate that the graphene scrolls form highly conducting electrical contacts to highly oriented pyrolytic graphite (HOPG). These highly conducting graphite-graphene contacts are attractive for the fabrication of interconnects in microcircuits and align with the increasing interest in building all sp2-carbon circuits. Above a temperature of 450 °C the scrolls unravel into buckled graphene sheets, and this process is understood on a theoretical basis. These findings augur well for new applications, in particular for incorporating the scrolls into miniaturized electronic devices.

Three-step-in-one synthesis of supercapacitor MWCNT superparamagnetic magnetite composite material under flow.

Composites of multi-walled carbon nanotubes (MWCNTs) and superparamagnetic magnetite nanoparticles, Fe3O4@MWCNT, were synthesized in DMF in a vortex fluidic device (VFD). This involved in situ generation of the iron oxide nanoparticles by laser ablation of bulk iron metal at 1064 nm using a pulsed laser, over the dynamic thin film in the microfluidic platform. The overall processing is a three-step in one operation: (i) slicing MWCNTs, (ii) generating the superparamagnetic nanoparticles and (iii) decorating them on the surface of the MWCNTs. The Fe3O4@MWCNT composites were characterized by transmission electron microscopy, scanning transmission electron microscope, TG analysis, X-ray diffraction and X-ray photoelectron spectroscopy. They were used as an active electrode for supercapacitor measurements, establishing high gravimetric and areal capacitances of 834 F g-1 and 1317.7 mF cm-2 at a scan rate of 10 mV s-1, respectively, which are higher values than those reported using similar materials. In addition, the designer material has a significantly higher specific energy of 115.84 W h kg-1 at a specific power of 2085 W kg-1, thereby showing promise for the material in next-generation energy storage devices.

Controlling the growth of fullerene C60 cones under continuous flow.

Micromixing of an o-xylene solution of C60 with N-N-dimethylformamide (DMF) at room temperature under continuous flow in a vortex fluidic device (VFD) results in the formation of symmetrical right cones in high yield with diameters 0.5 to 2.5 µm, pitch angle 25° to 55° and wall thickness 120 to 310 nm. Their formation is in the absence of surfactants and any other reagents, and is scalable. The cones are formed at specific operating parameters of the VFD, including rotational speed, flow rate and concentration, and varying these results in other structures such as grooved fractals. Other aromatic solvents in place of o-xylene results in the formation of rods, spicules and prisms, respectively for m-xylene, p-xylene and mesitylene.

Laser-Ablated Vortex Fluidic-Mediated Synthesis of Superparamagnetic Magnetite Nanoparticles in Water Under Flow.

Selective formation of only one iron oxide phase is a major challenge in conventional laser ablation process, as is scaling up the process. Herein, superparamagnetic single-phase magnetite nanoparticles of hexagonal and spheroidal-shape, with an average size of ca. 15 nm, are generated by laser ablation of bulk iron metal at 1064 nm in a vortex fluidic device (VFD). This is a one-step continuous flow process, in air at ambient pressure, with in situ uptake of the nanoparticles in the dynamic thin film of water in the VFD. The process minimizes the generation of waste by avoiding the need for any chemicals or surfactants and avoids time-consuming purification steps in reducing any negative impact of the processing on the environment.