Showing papers on "Cyclic voltammetry published in 2020"

The role of in situ generated morphological motifs and Cu(I) species in C2+ product selectivity during CO2 pulsed electroreduction

Abstract: The efficient electrochemical conversion of CO2 provides a route to fuels and feedstocks. Copper catalysts are well-known to be selective to multicarbon products, although the role played by the surface architecture and the presence of oxides is not fully understood. Here we report improved efficiency towards ethanol by tuning the morphology and oxidation state of the copper catalysts through pulsed CO2 electrolysis. We establish a correlation between the enhanced production of C2+ products (76% ethylene, ethanol and n-propanol at −1.0 V versus the reversible hydrogen electrode) and the presence of (100) terraces, Cu2O and defects on Cu(100). We monitored the evolution of the catalyst morphology by analysis of cyclic voltammetry curves and ex situ atomic force microscopy data, whereas the chemical state of the surface was examined via quasi in situ X-ray photoelectron spectroscopy. We show that the continuous regeneration of defects and Cu(i) species synergistically favours C–C coupling pathways. Carbon dioxide can be reduced electrocatalytically to fuels using copper catalysts, but the key features that determine the selectivity of these materials to specific products remains uncertain. Here Aran–Ais et al. use in situ methods to explore the influence of morphology and oxidation state on the performance of copper catalysts.

Synthesis and Characterization of a NiCo2O4@NiCo2O4 Hierarchical Mesoporous Nanoflake Electrode for Supercapacitor Applications

Abstract: In this study, we synthesized binder-free NiCo2O4@NiCo2O4 nanostructured materials on nickel foam (NF) by combined hydrothermal and cyclic voltammetry deposition techniques followed by calcination at 350 °C to attain high-performance supercapacitors. The hierarchical porous NiCo2O4@NiCo2O4 structure, facilitating faster mass transport, exhibited good cycling stability of 83.6% after 5000 cycles and outstanding specific capacitance of 1398.73 F g−1 at the current density of 2 A·g−1, signifying its potential for energy storage applications. A solid-state supercapacitor was fabricated with the NiCo2O4@NiCo2O4 on NF as the positive electrode and the active carbon (AC) was deposited on NF as the negative electrode, delivering a high energy density of 46.46 Wh kg−1 at the power density of 269.77 W kg−1. This outstanding performance was attributed to its layered morphological characteristics. This study explored the potential application of cyclic voltammetry depositions in preparing binder-free NiCo2O4@NiCo2O4 materials with more uniform architecture for energy storage, in contrast to the traditional galvanostatic deposition methods.

Amorphous versus Crystalline in Water Oxidation Catalysis: A Case Study of NiFe Alloy

Abstract: Catalytic water splitting driven by renewable electricity offers a promising strategy to produce molecular hydrogen, but its efficiency is severely restricted by the sluggish kinetics of the anodic water oxidation reaction. Amorphous catalysts are reported to show better activities of water oxidation than their crystalline counterparts, but little is known about the underlying origin, which retards the development of high-performance amorphous oxygen evolution reaction catalysts. Herein, on the basis of cyclic voltammetry, electrochemical impedance spectroscopy, isotope labeling, and in situ X-ray absorption spectroscopy studies, we demonstrate that an amorphous catalyst can be electrochemically activated to expose active sites in the bulk thanks to the short-range order of the amorphous structure, which greatly increases the number of active sites and thus improves the electrocatalytic activity of the amorphous catalyst in water oxidation.

Fundamentals of fast-scan cyclic voltammetry for dopamine detection

Abstract: Fast-scan cyclic voltammetry (FSCV) is used with carbon-fiber microelectrodes for the real-time detection of neurotransmitters on the subsecond time scale. With FSCV, the potential is ramped up from a holding potential to a switching potential and back, usually at a 400 V s−1 scan rate and a frequency of 10 Hz. The plot of current vs. applied potential, the cyclic voltammogram (CV), has a very different shape for FSCV than for traditional cyclic voltammetry collected at scan rates which are 1000-fold slower. Here, we explore the theory of FSCV, with a focus on dopamine detection. First, we examine the shape of the CVs. Background currents, which are 100-fold higher than faradaic currents, are subtracted out. Peak separation is primarily due to slow electron transfer kinetics, while the symmetrical peak shape is due to exhaustive electrolysis of all the adsorbed neurotransmitters. Second, we explain the origins of the dopamine waveform, and the factors that limit the holding potential (oxygen reduction), switching potential (water oxidation), scan rate (electrode instability), and repetition rate (adsorption). Third, we discuss data analysis, from data visualization with color plots, to the automated algorithms like principal components regression that distinguish dopamine from pH changes. Finally, newer applications are discussed, including optimization of waveforms for analyte selectivity, carbon nanomaterial electrodes that trap dopamine, and basal level measurements that facilitate neurotransmitter measurements on a longer time scale. FSCV theory is complex, but understanding it enables better development of new techniques to monitor neurotransmitters in vivo.

Green-Synthesized Rice-Shaped Copper Oxide Nanoparticles Using Caesalpinia bonducella Seed Extract and Their Applications.

Abstract: Copper oxide nanoparticles (CuO Nps) were synthesized using Caesalpinia bonducella seed extract via a green synthetic pathway and were evaluated for electrocatalytic properties by carrying out electrochemical detection of riboflavin [vitamin B2 (VB2)]. The seeds of C. bonducella are known to have strong antioxidant properties arising due to the presence of various components, including citrulline, phytosterinin, β-carotene, and flavonoids, which serve as reducing, stabilizing, and capping agents. The synthesized CuO Nps were characterized using UV-visible spectroscopy, Fourier transform infrared spectroscopy, thermogravimetrc analysis-differential thermal analysis, X-ray diffraction spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy and further used as a modifier for a graphite electrode surface. The modified electrode was electrochemically characterized by cyclic voltammetry, square-wave voltammetry, and chronoamperometry techniques and then assessed for electrocatalysis by carrying out the detection of VB2. The electrochemical sensor could be used for nanomolar detection of VB2 with an observed linear range of 3.13-56.3 nM with a limit of detection of 1.04 nM. The electrode showed good stability and reproducibility over a period of 120 days. The CuO Nps were further analyzed for antibacterial effect with Gram-positive and Gram-negative bacteria, and in both cases, high antibacterial activity was clearly observed. The newly synthesized nanoparticles, thus, proved to be an interesting material for electrochemical and biological studies.

Applications of Voltammetry in Lithium Ion Battery Research

Abstract: Li ion battery (LIB) is one of the most remarkable energy storage devices currently available in various applications. With a growing demand for high-performance batteries, the role of electrochemical analysis for batteries, especially, electrode reactions are becoming very important and crucial. Among various analytical methods, cyclic voltammetry (CV) is very versatile and widely used in many fields of electrochemistry. Through CV, it is possible to know electrochemical factors affecting the reaction voltage and reversibility, and furthermore, quantitative analysis on Li+ diffusivity as well as intercalation and capacitive reactions, and also anionic redox reaction. However, the explanation or interpretation of the results of CV is often deficient or controversial. In this mini-review, we briefly introduce the principle of cyclic voltammetry and its applications in LIB to bring a better understanding of the electrochemical reaction mechanisms involved in LIB.

Simultaneous determination of ascorbic acid, dopamine, and uric acid using graphene quantum dots/ionic liquid modified screen-printed carbon electrode

Abstract: In this work, graphene quantum dots (GQDs) and ionic liquid (IL) modified screen-printed carbon electrode (GQDs/IL-SPCE) were introduced for the simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA). GQDs were synthesized by directly pyrolyzing citric acid and then dropped onto the surface of IL-SPCE, which was prepared by screen-printing the mixture of IL and carbon ink on a portable substrate. UV–vis spectrophotometry, fluorescence spectrophotometry, transmission electron microscopy (TEM), scanning electron microscopy (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) were used to characterize the synthesized GQDs and the modified electrodes. The GQDs/IL-SPCE exhibited excellent electrocatalytic activity for the oxidation of AA, DA, and UA in the mixture solution. Moreover, the anodic peak responses of these three analytes were also resolved into three well-defined peaks. Under the optimized conditions, the linear response ranges for AA, DA, and UA were 25–400 μM, 0.2–10 μM, and 0.5–20 μM, respectively, with low detection limits (σ/N = 3) of 6.64 μM, 0.06 μM, and 0.03 μM, respectively. The proposed sensor exhibited high sensitivity, low cost and successfully applied for the simultaneous detection of AA, DA, and UA in pharmaceutical products and biological samples.

Comparison of activation processes for 3D printed PLA-graphene electrodes: electrochemical properties and application for sensing of dopamine

Abstract: This paper reports the comparison of the electrochemical properties of 3D PLA-graphene electrodes (PLA-G) under different activation conditions and through different processes. In this work, the performance of the electrodes was evaluated after polishing, electrochemical and chemical treatments and a combination of them. The best results were obtained with hydroxide activation using 1.0 mol L-1 NaOH for 30 min of immersion, which promoted the saponification of PLA exposing the graphene nanoribbon structures. The improvement was more evident also after electrochemical activation, which led to a great increase in surface area, defects, electron transfer rate and amount of edge sites. The analytical performance of the proposed PLA-GNaOH-30-EC electrode was evaluated in the presence of dopamine (DA) by three electrochemical techniques, presenting a broad linear range, and limits of detection of 3.49, 2.17 and 1.67 μmol L-1 were obtained by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV), respectively. The separation and quantification of DA in the presence of AA and UA was also reported. The sensor showed good repeatability and reproducibility and was successfully applied to DA determination in synthetic urine and human serum, showing good recovery, from 88.8 to 98.4%. Therefore, the activation methods were essential for the improvement in the 3D PLA-G electrode properties, allowing graphene surface alteration and electrochemical enhancement in the sensing of molecular targets.

Probing Single-Particle Electrocatalytic Activity at Facet-Controlled Gold Nanocrystals

Abstract: Electrocatalytic reduction reactions (i.e., the hydrogen evolution reaction (HER) and oxygen reduction reaction) at individual, faceted Au nanocubes (NCs) and nano-octahedra (ODs) expressing predominantly {100} and {111} crystal planes on the surface, respectively, were studied by nanoscale voltammetric mapping. Cyclic voltammograms were collected at individual nanoparticles (NPs) with scanning electrochemical cell microscopy (SECCM) and correlated with particle morphology imaged by electron microscopy. Nanoscale measurements from a statistically informative set of individual NPs revealed that Au NCs have superior HER electrocatalytic activity compared to that of Au ODs, in good agreement with macroscale cyclic voltammetry measurements. Au NCs exhibited more particle-to-particle variation in catalytic activity compared to that with Au ODs. The approach of single-particle SECCM imaging coupled with macroscale CV on well-defined NPs provides a powerful toolset for the design and activity assessment of nanoscale electrocatalysts.

Facile preparation of a highly efficient NiZn2O4-NiO nanoflower composite grown on Ni foam as an advanced battery-type electrode material for high-performance electrochemical supercapacitors.

Abstract: The development of combined simple metal oxides and binary metal oxides on a flexible conductor has been needed as a novel approach for energy storage sources. Here, we demonstrate a simple and versatile strategy towards the synthesis of a NiZn2O4-NiO nanoflower array (NFA) composite effectively deposited into a nickel (Ni) foam conductor for energy storing applications to achieve better electrochemical results. The morphology and other physical properties of the as-developed composite were analyzed, and the results suggest that the NiO nanoparticles have been effectively anchored into the binary NiZn2O4 nanoleaves array surface. The composite NiZn2O4-NiO NFAs nanoarchitecture combines superior surface area with huge numbers of active sites to boost electrochemical reactions and excellent transport between electrons and ions, as compared to NiZn2O4 nanoleaf arrays (NLAs). Meanwhile, taking into consideration electrochemical studies, the composite NiZn2O4-NiO NFAs exhibited extraordinary faradaic redox progress, which was different from the metal oxide based electrode profiles. Cyclic voltammetry and galvanostatic charge-discharge plateaus from the NiZn2O4 NLAs and NiZn2O4-NiO NFAs electrodes exhibit faradaic battery-type redox behavior, which is distinct from the profiles of carbon-based materials. As a battery-type electrode, the composite NiZn2O4-NiO NFAs electrode exhibited a greater supercapacitor activity with a higher specific capacitance of 482.7 C g-1 at 1 A g-1 and also yielded the best life-span with up to 98.14% capacity retained after 5000 cycles (vs. 253.4 C g-1 at 1 A g-1 and 91.4% retention of capacity after 5000 cycles for NiZn2O4 NLAs), which was the best result or comparable to recently reported composites of simple metal oxides/binary metal oxides-based electrode materials. Thus, with the above findings, the battery-type NiZn2O4-NiO NFAs electrode material has remarkable application potential and could be effectively applied in other energy storage technologies.

Biomimetic Sn4P3 Anchored on Carbon Nanotubes as an Anode for High-Performance Sodium-Ion Batteries.

Abstract: Recently, Sn4P3 has emerged as a promising anode for sodium-ion batteries (SIBs) due to the high specific capacity. However, the use of Sn4P3 has been impeded by capacity fade and an inferior rate performance. Herein, a biomimetic heterostructure is reported by using a simple hydrothermal reaction followed by thermal treatment. This bottlebrush-like structure consists of a stem-like carbon nanotube (CNT) as the electron expressway and mechanical support; fructus-like Sn4P3 nanoparticles as the active material; and the permeable stoma-like thin carbon coating as the buffer layer. Having benefited from the biomimetic structure, a superior electrochemical performance is obtained in the SIBs. It exhibits a high capacity of 742 mA h g-1 after 150 cycles at 0.2C, and superior rate performance with 449 mA h g-1 at 2C after 500 cycles. Moreover, the sodium storage mechanism is confirmed by cyclic voltammetry and ex situ X-ray diffraction and transmission electron microscopy. In situ electrochemical impedance spectroscopy was adopted to analyze the reaction dynamics. This research represents a further step toward figuring out the inferior electrochemical performance of other metal phosphide materials.

Validated electrochemical immunosensor for ultra-sensitive procalcitonin detection: Carbon electrode modified with gold nanoparticles functionalized sulfur doped MXene as sensor platform and carboxylated graphitic carbon nitride as signal amplification

Abstract: Septicemia, also known as sepsis, refers to a systemic inflammatory response syndrome and becomes the dominant reason of mortality for seriously diseases. Procalcitonin (PCT), the peptide precursor of the hormones, is a key biomarker of septicemia in the diagnosis and detection of bacterial inflammation. In this study, an ultra-sensitive sandwich type electrochemical immunosensor for PCT detection was constructed. Firstly, delaminated sulfur-doped MXene (d-S-Ti3C2TX MXene) modified glassy carbon electrode (GCE) including gold nanoparticles (AuNPs) was utilized as immunosensor platform to increase the amount of PCT antibody1 (Ab1). After that, carboxylated graphitic carbon nitride (c-g-C3N4) was used to label PCT Ab2 as signal amplification. The structure of electrochemical immunosensor was highlighted by x-ray diffraction (XRD) method, scanning electron microscope (SEM), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), fourier transform infrared spectroscopy (FTIR), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Herein, c-g-C3N4 not only has excellent catalytic activity toward H2O2 for signal amplification, but also can be directly utilized as redox probe. The analytical results have revealed that 0.01 - 1.0 pg mL-1 and 2.0 fg mL-1 were found as linearity range and limit of detection (LOD). Furthermore, the validated electrochemical immunosensor was examined in terms of stability, repeatability, reproducibility and reusability. Finally, the immunosensor was applied to plasma samples having high recovery.

In Operando Synchrotron Studies of NH4+ Preintercalated V2O5·nH2O Nanobelts as the Cathode Material for Aqueous Rechargeable Zinc Batteries.

Abstract: NH4+ preintercalated V2O5·nH2O nanobelts with a large interlayer distance of 10.9 A were prepared by the hydrothermal method. The material showed a large specific capacity of 391 mA·h·g-1 at the 500 mA·g-1 current density in aqueous rechargeable zinc batteries. In operando synchrotron X-ray diffraction demonstrated that the material experienced reversible solid-solution reaction and two-phase transition during charge-discharge cycling, accompanied by the reversible formation/decomposition of a ZnSO4Zn3(OH)6·5H2O byproduct. In operando X-ray absorption spectroscopy confirmed the reversible reduction/oxidation of V, together with small changes in the VO6 local structure. The formation of byproduct was attributed to the dehydration of [Zn(H2O)6]2+, which concurrently improved the desolvation of [Zn(H2O)6]2+ into Zn2+. Bond valence sum map analysis and electrochemical impedance spectroscopy demonstrated that the byproduct improved the charge transfer kinetics of the electrode. Cyclic voltammetry and galvanostatic intermittent titration technique showed that the electrode reaction was dominated by ionic intercalation where the discharge capacity in the voltage window of 1.4-0.85 V was attributed to the intercalation of [Zn(H2O)6]2+, followed by the intercalation of Zn2+ at 0.85-0.4 V.