Defining the origins of electron transfer at screen-printed graphene-like and graphite electrodes: MoO2 nanowire fabrication on edge plane sites reveals electrochemical insights

© 2016 The Royal Society of Chemistry .Molybdenum (di)oxide (MoO2) nanowires are fabricated onto graphene-like and graphite screen-printed electrodes (SPEs) for the first time, revealing crucial insights into the electrochemical properties of carbon/graphitic based materials. Distinctive patterns observed in the electrochemical process of nanowire decoration show that electron transfer occurs predominantly on edge plane sites when utilising SPEs fabricated/comprised of graphitic materials. Nanowire fabrication along the edge plane sites (and on edge plane like-sites/defects) of graphene/graphite is confirmed with Cyclic Voltammetry, Scanning Electron Microscopy (SEM) and Raman Spectroscopy. Comparison of the heterogeneous electron transfer (HET) rate constants (k°) at unmodified and nanowire coated SPEs show a reduction in the electrochemical reactivity of SPEs when the edge plane sites are effectively blocked/coated with MoO2. Throughout the process, the basal plane sites of the graphene/graphite electrodes remain relatively uncovered; except when the available edge plane sites have been utilised, in which case MoO2 deposition grows from the edge sites covering the entire surface of the electrode. This work clearly illustrates the distinct electron transfer properties of edge and basal plane sites on graphitic materials, indicating favourable electrochemical reactivity at the edge planes in contrast to limited reactivity at the basal plane sites. In addition to providing fundamental insights into the electron transfer properties of graphite and graphene-like SPEs, the reported simple, scalable, and cost effective formation of unique and intriguing MoO2 nanowires realised herein is of significant interest for use in both academic and commercial applications

Recent advances in 2D hexagonal boron nitride (2D-hBN) applied as the basis of electrochemical sensing platforms

2D hexagonal boron nitride (2D-hBN) is a lesser utilised material than other 2D counterparts in electrochemistry due to initial reports of it being non-conductive. As we will demonstrate in this review, this common misconception is being challenged, and researchers are starting to utilise 2D-hBN in the field of electrochemistry, particularly as the basis of electroanalytical sensing platforms. In this critical review, we overview the use of 2D-hBN as an electroanalytical sensing platform summarising recent developments and trends and highlight future developments of this interesting, often overlooked, 2D material

Screen-printed electrodes: Transitioning the laboratory in-to-the field

This short article overviews the use of screen-printed electrodes (SPEs) in the field of electroanalysis and compares their application against traditional laboratory based analytical techniques. Electroanalysis coupled with SPEs can offer low-cost, precise, sensitive, rapid, quantitative information and laboratory equivalent results. The combined use of SPEs and electroanalysis reduces the need of sample transportation and preparation to a centralised laboratory allowing experimentalists to perform the measurements where they are needed the most. We first introduce the basic concepts and principles of analytical techniques to the reader, with particular attention to electroanalysis, and then discuss the application of SPEs to common analytical targets such as food, environmental, forensics, cancer biomarkers and pathogenic monitoring and sensing

Mass-producible 2D-WS2 bulk modified screen printed electrodes towards the hydrogen evolution reaction

© The Royal Society of Chemistry 2019. A screen-printable ink that contained varying percentage mass incorporations of two dimensional tungsten disulphide (2D-WS2) was produced and utilized to fabricate bespoke printed electrodes (2D-WS2-SPEs). These WS2-SPEs were then rigorously tested towards the Hydrogen Evolution Reaction (HER) within an acidic media. The mass incorporation of 2D-WS2 into the 2D-WS2-SPEs was found to critically affect the observed HER catalysis with the larger mass incorporations resulting in more beneficial catalysis. The optimal (largest possible mass of 2D-WS2 incorporation) was the 2D-WS2-SPE40%, which displayed a HER onset potential, Tafel slope value and Turn over Frequency (ToF) of -214 mV (vs. RHE), 51.1 mV dec-1 and 2.20, respectively. These values significantly exceeded the HER catalysis of a bare/unmodified SPE, which had a HER onset and Tafel slope value of -459 mV (vs. RHE) and 118 mV dec-1, respectively. Clearly, indicating a strong electrocatalytic response from the 2D-WS2-SPEs. An investigation of the signal stability of the 2D-WS2-SPEs was conducted by performing 1000 repeat cyclic voltammograms (CVs) using a 2D-WS2-SPE10% as a representative example. The 2D-WS2-SPE10% displayed remarkable stability with no variance in the HER onset potential of ca. -268 mV (vs. RHE) and a 44.4% increase in the achievable current over the duration of the 1000 CVs. The technique utilized to fabricate these 2D-WS2-SPEs can be implemented for a plethora of different materials in order to produce large numbers of uniform and highly reproducible electrodes with bespoke electrochemical signal outputs

Correction to: MoO2 Nanowire Electrochemically Decorated Graphene Additively Manufactured Supercapacitor Platforms (Adv. Energy Mater., (2021), 11, (2100433), 10.1002/10.1002/aenm.202100433)

Adv. Energy Mater. 2021, 11, 2100433 DOI: 10.1002/aenm.202100433 Figure 4 in the originally published article is incorrect in the original manuscript. The correct figure is displayed below. 4 Figure (Figure presented.) SEMs of A,B,C) MoO2-G/AME and D) G/AME. Electrochemical decoration parameters: −1.4 V, 600 s. This error does not affect the conclusions of the report. The authors apologize for any inconvenience caused

Ni−Fe (Oxy)hydroxide Modified Graphene Additive Manufactured (3D-Printed) Electrochemical Platforms as an Efficient Electrocatalyst for the Oxygen Evolution Reaction

© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim We demonstrate that polylactic acid (PLA)/graphene additive manufactured (3D-printed) electrodes (Gr/AMEs) electrodeposited with Ni−Fe (oxy)hydroxide can efficiently catalyse the oxygen evolution reaction (OER). X-ray photoelectron spectroscopy (XPS) depth profiling combined with Atomic Force Microscopy (AFM) and Tip Enhanced Raman Spectroscopy (TERS) deduced the composition and depth of the Ni−Fe (oxy)hydroxide layer. The composition of the resulting electrocatalytic surfaces are tailored through altering the concentrations of nickel and iron within the electrodeposited solutions, which give rise to optimised AMEs OER performance (within 0.1 M KOH). The optimal OER performance was observed from a Ni−Fe (oxy)hydroxide with a 10 % content of Fe, which displayed an OER onset potential and overpotential of+1.47 V (vs. RHE) and 519 mV, respectively. These values arecomparable to that of polycrystalline Iridium (+ 1.43 V (vs. RHE) and ca. 413 mV), as well as being significantly less electropositive than a bare/unmodified AME. This work is essential for those designing, fabricating and modulating additive manufactured electrodes

Glassy Carbon Electrode Modified with Layering of Carbon Black/Poly(Allylamine Hydrochloride) Composite for Multianalyte Determination

© 2020 Wiley-VCH GmbH An electrochemical sensor using glassy carbon electrode modified with carbon black within a poly(allylamine hydrochloride) film is proposed in this work. The novel sensor was characterized by scanning electron microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry using the redox probe Fe(CN)63−/4−. The sensor was applied for the simultaneous determination of dopamine (DA), paracetamol (PAR), amlodipine (AML), and rosuvastatin (RSV). The quantification of all four analytes was carried out by linear sweep voltammetry and presented a linear concentration range for all analytes from 1.0 to 90 μmol L−1, with limit of detection of 0.55, 1.3, 5.7, and 3.0 μmol L−1 for DA, PAR, AML, and RSV, respectively. This sensor was successfully applied in the simultaneous determination of these analytes in environmental, pharmaceutical, and biological samples

The Voltammetric Detection of Cadaverine Using a Diamine Oxidase and Multi-Walled Carbon Nanotube Functionalised Electrochemical Biosensor

Cadaverine is a biomolecule of major healthcare importance in periodontal disease; however, current detection methods remain inefficient. The development of an enzyme biosensor for the detection of cadaverine may provide a cheap, rapid, point-of-care alternative to traditional measurement techniques. This work developed a screen-printed biosensor (SPE) with a diamine oxidase (DAO) and multi-walled carbon nanotube (MWCNT) functionalised electrode which enabled the detection of cadaverine via cyclic voltammetry and differential pulse voltammetry. The MWCNTs were functionalised with DAO using carbodiimide crosslinking with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) and N-Hydroxysuccinimide (NHS), followed by direct covalent conjugation of the enzyme to amide bonds. Cyclic voltammetry results demonstrated a pair of distinct redox peaks for cadaverine with the C-MWCNT/DAO/EDC-NHS/GA SPE and no redox peaks using unmodified SPEs. Differential pulse voltammetry (DPV) was used to isolate the cadaverine oxidation peak and a linear concentration dependence was identified in the range of 3–150 µg/mL. The limit of detection of cadaverine using the C-MWCNT/DAO/EDC-NHS/GA SPE was 0.8 μg/mL, and the biosensor was also found to be effective when tested in artificial saliva which was used as a proof-of-concept model to increase the Technology Readiness Level (TRL) of this device. Thus, the development of a MWCNT based enzymatic biosensor for the voltammetric detection of cadaverine which was also active in the presence of artificial saliva was presented in this study

MoO2 Nanowire Electrochemically Decorated Graphene Additively Manufactured Supercapacitor Platforms

Additively manufactured (AM) supercapacitor platforms are fabricated from bespoke filaments, which are comprised of electro-conductive graphene (20 wt%) incorporated polylactic acid (80 wt%), via fused deposition modeling and denoted as G/AMEs. The G/AMEs are shown to be capable of acting as a template for the electrodeposition of metals/metal oxides, in particular MoO2 nanowires (MoO2-G/AMEs), which are subsequently explored as a capacitor within 1 m H2SO4, 1-butyl-3-methylimidazolium hexafluorophosphate, and 1-butyl-3-methylimidazolium tetrafluoroborate. Optimization of the MoO2-G/AMEs demonstrates capacitance up to 1212 F g–1 when used in a symmetric arrangement. The material science described herein represents a significant enhancement in unlocking AMs potential as a valid manufacturing route for device level capacitance architectures

The Voltammetric Detection of Cadaverine Using a Diamine Oxidase and Multi-Walled Carbon Nanotube Functionalised Electrochemical Biosensor

Cadaverine is a biomolecule of major healthcare importance in periodontal disease; however, current detection methods remain inefficient. The development of an enzyme biosensor for the detection of cadaverine may provide a cheap, rapid, point-of-care alternative to traditional measurement techniques. This work developed a screen-printed biosensor (SPE) with a diamine oxidase (DAO) and multi-walled carbon nanotube (MWCNT) functionalised electrode which enabled the detection of cadaverine via cyclic voltammetry and differential pulse voltammetry. The MWCNTs were functionalised with DAO using carbodiimide crosslinking with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) and N-Hydroxysuccinimide (NHS), followed by direct covalent conjugation of the enzyme to amide bonds. Cyclic voltammetry results demonstrated a pair of distinct redox peaks for cadaverine with the C-MWCNT/DAO/EDC-NHS/GA SPE and no redox peaks using unmodified SPEs. Differential pulse voltammetry (DPV) was used to isolate the cadaverine oxidation peak and a linear concentration dependence was identified in the range of 3–150 µg/mL. The limit of detection of cadaverine using the C-MWCNT/DAO/EDC-NHS/GA SPE was 0.8 μg/mL, and the biosensor was also found to be effective when tested in artificial saliva which was used as a proof-of-concept model to increase the Technology Readiness Level (TRL) of this device. Thus, the development of a MWCNT based enzymatic biosensor for the voltammetric detection of cadaverine which was also active in the presence of artificial saliva was presented in this study