Electrochemistry of Layered Graphitic Carbon Nitride Synthesised from Various Precursors: Searching for Catalytic Effects.

Graphitic carbon nitride (g-C3 N4 ), synthesised by pyrolysis of different precursors (dicyandiamide, melamine and urea) under varying reaction conditions (air and nitrogen gas) is subjected to electrochemical studies for the elucidation of the inherent catalytic efficiency of the pristine material. Contrary to popular belief, pristine g-C3 N4 shows negligible, if any, enhancement in its electrochemical behaviour in this comprehensive study. Voltammetric analysis reveals g-C3 N4 to display similar catalytic efficiency to the unmodified glassy carbon electrode surface on which the bulk material was deposited. This highlights the non-catalytic nature of the pristine material and challenges the feasibility of using g-C3 N4 as a heterogeneous catalyst to deliver numerous promised applications.

Impact electrochemistry: colloidal metal sulfide detection by cathodic particle coulometry.

The determination of the size and concentration of colloidal nano and microparticles is of paramount importance to modern nanoscience. Application of the particle collision technique on metal and metal oxide nanoparticles has been intensively explored over the past decade owing to its ability to determine the particle size and concentration via reactions including the inherent oxidation or the reduction of nanoparticles as well as surface reactions catalysed by the nanoparticles. Transition metal dichalcogenide particles were previously quantified using the anodic (oxidative) particle coulometry method. Here we show that cathodic (reductive) particle coulometry can be favorably used for the detection of metal sulfide colloidal particles. The detection of sulfides of cobalt and lead was performed using the particle collision technique in this work. The presence of spikes confirmed the viability of detecting new and larger particles from compounds using reductive (cathodic) potentials. Such an expansion of the impact particle coulometry method will be useful and applicable to the determination of concentration and size of colloidal metal sulfide nanoparticles in general.

Impact Electrochemistry of Layered Transition Metal Dichalcogenides.

Layered transition metal dichalcogenides (TMDs) exhibit paramount importance in the electrocatalysis of the hydrogen evolution reaction. It is crucial to determine the size of the electrocatalytic particles as well as to establish their electrocatalytic activity, which occurs at the edges of these particles. Here, we show that individual TMD (MoS2, MoSe2, WS2, or WSe2; in general MX2) nanoparticles impacting an electrode surface provide well-defined current "spikes" in both the cathodic and anodic regions. These spikes originate from direct oxidation of the nanoparticles (from M(4+) to M(6+)) at the anodic region and from the electrocatalytic currents generated upon hydrogen evolution in the cathodic region. The positive correlation between the frequency of the impacts and the concentration of TMD nanoparticles is also demonstrated here, enabling determination of the concentration of TMD nanoparticles in colloidal form. In addition, the size of individual TMD nanoparticles can be evaluated using the charge passed during every spike. The capability of detecting both the "indirect" catalytic effect of an impacting TMD nanoparticle as well as "direct" oxidation indicates that the frequency of impacts in both the "indirect" and "direct" scenarios are comparable. This suggests that all TMD nanoparticles, which are electrochemically oxidizable (thus capable of donating electrons to electrodes), are also capable of catalyzing the hydrogen reduction reaction.

Layered titanium diboride: towards exfoliation and electrochemical applications.

Layered transition metal diborides (TMDB), amongst other refractory metal borides, are commonly employed for material fabrication such as wear- and corrosion-resistant coatings due to their impressive chemical stability and thermal conductivity. In spite of the wide scope of studies carried out on TMDB in the physical field, investigations on its electrochemistry remain limited. Since the physical properties play a vital role in any material's electrochemical behaviour, we explore the viability of the most popular form of titanium boride, layered TiB2, as catalysts for electrochemical energy reactions, including hydrogen evolution and oxygen reduction. Three types of TiB2 were compared in this work - TiB2 separately modified with sodium naphtalenide and butyllithium in an attempt to exfoliate TiB2 and unmodified TiB2. The electrocatalytic activity displayed by all three TiB2 materials provides a wider range of opportunities for the application of TiB2 in material studies.

Iridium- and Osmium-decorated Reduced Graphenes as Promising Catalysts for Hydrogen Evolution.

Renewable energy sources are highly sought after as a result of numerous worldwide problems concerning the environment and the shortage of energy. Currently, the focus in the field is on the development of catalysts that are able to provide water splitting catalysis and energy storage for the hydrogen evolution reaction (HER). While platinum is an excellent material for HER catalysis, it is costly and rare. In this work, we investigated the electrocatalytic abilities of various graphene-metal hybrids to replace platinum for the HER. The graphene materials were doped with 4f metals, namely, iridium, osmium, platinum and rhenium, as well as 3d metals, namely, cobalt, iron and manganese. We discovered that a few hybrids, in particular iridium- and osmium-doped graphenes, have the potential to become competent electrocatalysts owing to their low costs and-more importantly-to their promising electrochemical performances towards the HER. One of the more noteworthy observations of this work is the superiority of these two hybrids over MoS2 , a well-known electrocatalyst for the HER.

Inherent electrochemistry of layered post-transition metal halides: the unexpected effect of potential cycling of PbI2.

The development of two-dimensional nanomaterials has expedited the growth of advanced technological applications. PbI2 is a layered inorganic solid with important and unique properties suitable for applications in the detection of electromagnetic radiation. While the optical and electrical properties of layered PbI2 have been generally established, its electrochemistry has remained largely unexplored. In this work, we examine the inherent electrochemistry of PbI2 in relation to its morphological and structural properties. A direct comparison between commercially available and solution-grown PbI2 showed high similarity in properties based on characterizations by X-ray photoelectron spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The respective layered PbI2 materials also exhibited similar inherent electrochemistry. Electrochemical potential cycling of PbI2 in phosphate buffer resulted in the dissolution of iodide ions from PbI2 to form complex lead-phosphate-chloride with the oxygen groups of the phosphate ions while retaining the hexagonal structure. In the case of KCl solution, the formation of PbO2 was observed.

Magnetic control of electrochemical processes at electrode surface using iron-rich graphene materials with dual functionality.

Metal-doped graphene hybrid materials demonstrate promising capabilities in catalysis and various sensing applications. There also exists great interest for on-demand control of the selectivity of many electrochemical processes. In this work, an iron-doped thermally reduced graphene oxide (Fe-TRGO) was prepared and used to investigate the possibility of a reproducible, magnetically controlled method to modulate electrochemical reactivities through a scalable method. We made use of the presence of both magnetic and electrocatalytic properties in the Fe-TRGOs to induce attraction and removal of the Fe-TRGO material onto and off the working electrode surfaces magnetically, thereby controlling the electrochemical oxidation and reduction processes. The outstanding electrochemical performance of the Fe-TRGO material was evident, with enhanced current signals and lower peak potentials observed upon magnetic activation. Reversible and reproducible cycles of activation and deactivation were obtained as the peak heights and peak potentials remained relatively consistent with no apparent carryover between every step. Both components of Fe-TRGO play an electrocatalytic role in the electrochemical sensing. In the cases of the oxygen reduction reaction and reduction of cumene hydroperoxide, the iron oxide plays the role of an electrocatalyst, while in the cases of ascorbic acid, the enhanced electroactivity originates from the high surface area of the graphene portion in the Fe-TRGO hybrid material. The feasibility of this magnetically switchable method for on-demand sensing and energy production thus brings about potential developments for future electrochemical applications.

Electrochemical tuning of oxygen-containing groups on graphene oxides: towards control of the performance for the analysis of biomarkers.

Graphene materials are very popular in the field of biosensing owing to their distinctive characteristics. However, oxygen-containing groups are known to exist intrinsically in graphene-related materials. These groups influence the electrochemical properties of graphene materials and therefore affect the sensing performance of graphene-based electrodes when used to detect redox active biomarkers. A well-defined carbon/oxygen (C/O) ratio can be obtained upon applying different reduction potentials to graphene oxide (GO) films for a controlled removal of redox active oxygen functionalities. Here, we show that a precise control of the oxygen functionalities on the graphene oxide films allows the tuning of the biosensing capabilities of the electrodes for the analysis of two significant biomarkers, uric acid and ascorbic acid, as well as two DNA bases, guanine and adenine. Both the catalytic properties and the sensitivity of the reduced GO film electrodes (ERGOs) are evaluated by measuring the oxidation potential and the peak current, respectively. We demonstrate that each biomarker requires different optimal conditions which can be easily matched by varying the electrochemical pre-treatment of the sensing GO film.

Detection of biomarkers with graphene nanoplatelets and nanoribbons.

Well-defined graphene nanosheets have become increasingly popular in the electrochemical detection and quantification of small molecules. In this work, the electrochemical oxidation of biomarkers such as uric acid, ascorbic acid, dopamine, NADH and DNA bases, namely guanine and adenine, was performed using cyclic voltammetry and differential pulse voltammetry to compare the electrochemical properties of electrochemically reduced nanoplatelets (ENPs) and electrochemically reduced nanoribbons (ENRs). The graphene materials displayed better electrochemical performances than the bare glassy carbon surface. Between the two graphene materials, the oxidation of biomarkers occurred at lower oxidation potentials on the ENP surface. The sensitivities of the two graphene surfaces varied when different biomarkers were studied. The ENP surface showed enhanced sensitivities for ascorbic acid, while the ENR surface exhibited higher sensitivities for uric acid and dopamine. As for the DNA bases analysed, both guanine and adenine were oxidised at lower potentials on the ENP surface than the ENR surface. The ENP surface displayed a better sensitivity for guanine, whereas the oxidation of adenine was more sensitive on the ENR surface.