MoS2-graphene-CuNi2S4 nanocomposite an efficient electrocatalyst for the hydrogen evolution reaction

We present a facile methodology for the synthesis of a novel 2D-MoS2, graphene and CuNi2S4 (MoS2-g-CuNi2S4) nanocomposite that displays highly efficient electrocatalytic activity towards the production of hydrogen. The intrinsic hydrogen evolution reaction (HER) activity of MoS2 nanosheets was significantly enhanced by increasing the affinity of the active edge sites towards Hþ adsorption using transition metal (Cu and Ni2) dopants, whilst also increasing the edge sites exposure by anchoring them to a graphene frame- work. Detailed XPS analysis reveals a higher percentage of surface exposed S at 17.04%, of which 48.83% is metal bonded S (sulfide). The resultant MoS2-g-CuNi2S4 nanocomposites are immobilized upon screen-printed electrodes (SPEs) and exhibit a HER onset potential and Tafel slope value of -0.05 V (vs. RHE) and 29.3 mV dec-1, respectively. These values are close to that of the polycrystalline Pt electrode (near zero potential (vs. RHE) and 21.0 mV dec-1, respectively) and enhanced over a bare/unmodified SPE (-0.43 V (vs. RHE) and 149.1 mV dec-1, respectively). Given the efficient, HER activity displayed by the novel MoS2-g-CuNi2S4/SPE electrochemical platform and the comparatively low associated cost of production for this nanocomposite, it has potential to be a cost-effective alternative to Pt within electrolyser technologies

Tailoring the electrochemical properties of 2D-hBN via physical linear defects: physicochemical, computational and electrochemical characterisation

Monolayer hexagonal-boron nitride films (2D-hBN) are typically reported within the literature to be electrochemically inactive due to their considerable band gap (ca. 5.2–5.8 eV). It is demonstrated herein that introducing physical linear defects (PLDs) upon the basal plane surface of 2D-hBN gives rise to electrochemically useful signatures. The reason for this transformation from insulator to semiconductor (inferred from physicochemical and computational characterisation) is likely due to full hydrogenation and oxygen passivation of the boron and/or nitrogen at edge sites. This results in a decrease in the band gap (from ca. 6.11 to 2.36/2.84 eV; theoretical calculated values, for the fully hydrogenated oxygen passivation at the N or B respectively). The 2D-hBN films are shown to be tailored through the introduction of PLDs, with the electrochemical behaviour dependent upon the surface coverage of edge plane-sites/defects, which is correlated with electrochemical performance towards redox probes (hexaammineruthenium(III) chloride and Fe2+/3+) and the hydrogen evolution reaction. This manuscript de-convolutes, for the first time, the fundamental electron transfer properties of 2D-hBN, demonstrating that through implementation of PLDs, one can beneficially tailor the electrochemical properties of this nanomateria

Diamine Oxidase-Conjugated Multiwalled Carbon Nanotubes to Facilitate Electrode Surface Homogeneity

Carbon nanomaterials have gained significant interest over recent years in the field of electrochemistry, and they may be limited in their use due to issues with their difficulty in dispersion. Enzymes are prime components for detecting biological molecules and enabling electrochemical interactions, but they may also enhance multiwalled carbon nanotube (MWCNT) dispersion. This study evaluated a MWCNT and diamine oxidase enzyme (DAO)-functionalised screen-printed electrode (SPE) to demonstrate improved methods of MWCNT functionalisation and dispersion. MWCNT morphology and dispersion was determined using UV-Vis spectroscopy (UV-Vis) and scanning electron microscopy (SEM). Carboxyl groups were introduced onto the MWCNT surfaces using acid etching. MWCNT functionalisation was carried out using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) and N-Hydroxysuccinimide (NHS), followed by DAO conjugation and glutaraldehyde (GA) crosslinking. Modified C-MWNCT/EDC-NHS/DAO/GA was drop cast onto SPEs. Modified and unmodified electrodes after MWCNT functionalisation were characterised using optical profilometry (roughness), water contact angle measurements (wettability), Raman spectroscopy and energy dispersive X-ray spectroscopy (EDX) (vibrational modes and elemental composition, respectively). The results demonstrated that the addition of the DAO improved MWCNT homogenous dispersion and the solution demonstrated enhanced stability which remained over two days. Drop casting of C-MWCNT/EDC-NHS/DAO/GA onto carbon screen-printed electrodes increased the surface roughness and wettability. UV-Vis, SEM, Raman and EDX analysis determined the presence of carboxylated MWCNT variants from their non-carboxylated counterparts. Electrochemical analysis demonstrated an efficient electron transfer rate process and a diffusion-controlled redox process. The modification of such electrodes may be utilised for the development of biosensors which could be utilised to support a range of healthcare related fields

In situ addition of graphitic carbon into a NiCo2O4/CoO composite: Enhanced catalysis toward the oxygen evolution reaction

© The Royal Society of Chemistry 2019. We present a rapid, environmentally benign one-pot synthesis technique for the production of a NiCo2O4/CoO and graphite composite that demonstrates efficient electrocatalysis towards the Oxygen Evolution Reaction (OER), in 1.0 M KOH. The NiCo2O4/CoO/graphitic carbon composite that displayed optimal OER catalysis was synthesized by nitrate decomposition in the presence of citric acid (synthesized glycine and sucrose variants displayed inferior electro kinetics towards the OER). Screen-printed electrodes modified with ca. 530 μg cm-2 of the citric acid NiCo2O4/CoO/graphite variant displayed remarkable OER catalysis with an overpotential (η) of +323 mV (vs. RHE) (recorded at 10 mA cm-2), which is superior to that of IrO2 (340 mV) and RuO2 (350 mV). The composite also exhibited a large achievable current density of 77 mA cm-2 (at +1.5 V (vs. RHE)), a high O2 turnover frequency of 1.53 × 10-2 s-1 and good stability over the course of 500 repeat cycles. Clearly, the NiCo2O4/CoO composite has the potential to replace precious metal based catalysts as the anodic material within electrolysers, thereby providing a reduction in the associated costs of hydrogen production via water splitting

Antimicrobial activity of graphene oxide-metal hybrids.

With resistant bacteria on the increase, there is a need for new combinations of antimicrobials/biocidal agents to help control the transmission of such microorganisms. Particulate forms of graphite, graphene oxide (GO) and metal-hybrid compounds (silver-graphene oxide (AgGO) and zinc oxide graphene oxide (ZnOGO)) were fabricated and characterised. X-Ray diffraction and Diffuse Reflectance Infrared Fourier Transform Spectroscopy demonstrated the composition of the compounds. Scanning Electron Microscopy and Energy Dispersive X-Ray Spectroscopy determined the compounds were heterogeneous and irregular in shape and size and that the level of silver in the AgGO sample was 57.9 wt% and the ZnOGO contained 72.65 wt % zinc. The compounds were tested for their antimicrobial activity against four prominent bacteria; Escherichia coli, Staphylococcus aureus, Enterococcus faecium and Klebsiella pneumoniae. AgGO was the most effective antimicrobial (Minimum inhibitory concentration E. coli/Enterococcus faecium 0.125 mg mL−1; S. aureus/K. pneumoniae 0.25 mg mL−1). The addition of Ag enhanced the activity of GO against the bacteria tested, including the generally recalcitrant K. pneumoniae and Enterococcus faecium. These findings demonstrated that GO-metal hybrids have the potential to be utilised as novel antimicrobials or biocides in liquid formulations, biomaterials or coatings for use in the treatment of wounds where medically relevant bacteria are becoming increasingly resistant

Facile synthesis of Ni/NiO nanocomposites: the effect of Ni content in NiO upon the oxygen evolution reaction within alkaline media

We present the facile synthesis of Ni/NiO nanocomposites, via a solution combustion methodology, where the composition of metallic Ni within NiO is controlled by varying the annealing time, from 4 minutes up to 8 hours. The various Ni/NiO nanocomposites are studied via electrically wiring them upon screen-printed graphite macroelectrodes by physical deposition. Subsequently their electrochemical activity, towards the oxygen evolution reaction (OER), is assessed within (ultra-pure) alkaline media (1.0 M KOH). An optimal annealing time of 2 hours is found, which gives rise to an electrochemical oxidation potential (recorded at 10 mA cm-2) of 231 mV (vs. Ag/AgCl 1.46 vs. RHE). These values show the Ni/NiO nanocomposites to be significantly more electrocatalytic than a bare/unmodified SPE (460 mV vs. Ag/AgCl). A remarkable percentage increase (134%) in achievable current density is realised by the former over that of the latter. Tafel analysis and turn over frequency is reported with a likely underlying mechanism for the Ni/NiO nanocomposites towards the OER proposed. In the former case, Tafel analysis is overviewed for general multi-step overall electrochemical reaction processes, which can be used to assist other researchers in determining mechanistic information, such as electron transfer and rate determining steps, when exploring the OER. The optimal Ni/NiO nanocomposite exhibits promising stability at the potential of +231 mV, retaining near 100% of its achievable current density after 28 hours. Due to the facile and rapid fabrication methodology of the Ni/NiO nanocomposites, such an approach is ideally suited towards the mass production of highly active and stable electrocatalysts for application within the anodic catalyst layers of commercial alkaline electrolysers

Diamine Oxidase-Conjugated Multiwalled Carbon Nanotubes to Facilitate Electrode Surface Homogeneity

Carbon nanomaterials have gained significant interest over recent years in the field of electrochemistry, and they may be limited in their use due to issues with their difficulty in dispersion. Enzymes are prime components for detecting biological molecules and enabling electrochemical interactions, but they may also enhance multiwalled carbon nanotube (MWCNT) dispersion. This study evaluated a MWCNT and diamine oxidase enzyme (DAO)-functionalised screen-printed electrode (SPE) to demonstrate improved methods of MWCNT functionalisation and dispersion. MWCNT morphology and dispersion was determined using UV-Vis spectroscopy (UV-Vis) and scanning electron microscopy (SEM). Carboxyl groups were introduced onto the MWCNT surfaces using acid etching. MWCNT functionalisation was carried out using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) and N-Hydroxysuccinimide (NHS), followed by DAO conjugation and glutaraldehyde (GA) crosslinking. Modified C-MWNCT/EDC-NHS/DAO/GA was drop cast onto SPEs. Modified and unmodified electrodes after MWCNT functionalisation were characterised using optical profilometry (roughness), water contact angle measurements (wettability), Raman spectroscopy and energy dispersive X-ray spectroscopy (EDX) (vibrational modes and elemental composition, respectively). The results demonstrated that the addition of the DAO improved MWCNT homogenous dispersion and the solution demonstrated enhanced stability which remained over two days. Drop casting of C-MWCNT/EDC-NHS/DAO/GA onto carbon screen-printed electrodes increased the surface roughness and wettability. UV-Vis, SEM, Raman and EDX analysis determined the presence of carboxylated MWCNT variants from their non-carboxylated counterparts. Electrochemical analysis demonstrated an efficient electron transfer rate process and a diffusion-controlled redox process. The modification of such electrodes may be utilised for the development of biosensors which could be utilised to support a range of healthcare related fields