Graphene Quantum Dots‐Based Advanced Electrode Materials: Design,Synthesis and Their Applications in Electrochemical Energy Storage and Electrocatalysis

Graphene quantum dots (GQDs) have aroused great interest in the scientific community in recent years due to their unique physicochemical properties and potential applications in different fields. To date, much research has been conducted on the ingenious design and rational construction of GQDs‐based nanomaterials used as electrode materials and/or electrocatalysts. Despite these efforts, research on the efficient synthesis and application of GQDs‐based nanomaterials is still in the early stages of development and timely updates of recent research progress on new design concepts, synthetic strategies, and significant breakthroughs in GQDs‐based nanomaterials are highly desired. In light of the above, the effect of synthetic methods on the final product of the GQDs, the GQDs synthesis mechanism, and specific perspectives regarding the effect of the unique surface and structural properties of GQDs (e.g., defects, heteroatom doping, surface/edge state, size, conductivity) on the electrochemical energy‐related systems are discussed in‐depth in this review. Additionally, this review also focuses on the design of GQDs‐based composites and their applications in the fields of electrochemical energy storage (e.g., supercapacitors and batteries) and electrocatalysis (e.g., fuel cell, water splitting, CO₂ reduction), along with constructive suggestions for addressing the remaining challenges in the field.     

All‐Hydrocarbon MEA for PEM Water Electrolysis Combining Low Hydrogen Crossover and High Efficiency

Hydrocarbon ionomers bear the potential to significantly lower the material cost and increase the efficiency of proton‐exchange membrane water electrolyzers (PEMWE). However, no fully hydrocarbon membrane electrode assembly (MEA) with a performance comparable to Nafion‐MEAs has been reported. PEMWE‐MEAs are presented comprising sPPS as membrane and electrode binder reaching 3.5 A cm^?2 at 1.8 V and thus clearly outperforming state‐of‐the‐art Nafion‐MEAs (N115 as membrane, 1.5 A cm^?2 at 1.8 V) due to a significantly lower high frequency resistance (57 ± 4 mΩ cm² vs 161 ± 7 mΩ cm²). Additionally, pure sPPS‐membranes show a three times lower gas crossover (<0.3 mA cm^?2) than Nafion N115‐membranes (>1.1 mA cm^?2) in a fully humidified surrogate test. Furthermore, more than 80 h of continuous operation is shown for sPPS‐MEAs in a preliminary durability test (constant current hold at 1 A cm^?2 at 80 °C). These results rely on the unique transport properties of sulfonated poly(phenylene sulfone) (sPPS) that combines high proton conductivity with low gas crossover.     

Spatial localization of electrotactile stimuli on the fingertip in humans

This study was designed to determine the extent to which sensations elicited by discrete electrotactile stimulation can be spatially localized, with a qualitative comparison to mechanical stimulation, in a 2 × 2 electrode array on the fingertip. Electrotactile stimulation was delivered in two modes: (1) same current to all locations (constant) or (2) current adjusted to perceptual threshold of each location (varied). For each stimulus location, subjects were asked to identify the location of the stimulus. Mechanical stimulation of the same locations on the fingerpad was delivered through von Frey hairs (0.07, 0.2 and 0.4 g). The percentage of accurate responses was computed for all stimulation modes. We found that the accuracy of discrimination of stimulus location in both the constant (46%%) and varied (40%%) electrotactile stimulation modes was significantly higher than chance level (25%%; p < 0.01). Furthermore, subjects were significantly more accurate in discriminating electrotactile stimuli in the constant than in the varied mode (p < 0.05). We also found that the accuracy of spatial discrimination was dependent on stimulation site for mechanical, but not electrotactile stimulation. Finally, we found a significant difference in accuracy over the duration of the experiment only for mechanical modes, which may indicate that electrotactile stimuli are less biased over time. These results suggest that, although low in accuracy, human subjects are able to extract spatial information from electrotactile stimuli. Further research is needed to optimize the amount of the information that can be delivered through electrotactile stimulation.     

Binding of Mercurials to Membrane Suspensions and Undenatured Proteins

Binding capacities of membrane suspensions and dissolved compounds for mercurials were titrated by a new potentiometric method. Critical steps included a silver electrode of new design, the use of L-cysteine as a thiol buffer, a nitrogen atmosphere, and pretreatment of samples with equimolar mercurial and cysteine. Titrations had a sharp endpoint, accurate ±26 nmole methylmercury or ±8 nmole mercuric salt. Measurements of binding capacity of bovine serum albumin averaged 93% of the titer predicted for one SH group per molecule; those of human hemoglobin yielded 86-91% of the titer predicted for two SH groups per molecule. Yields dropped with exposure of protein solutions or membrane suspensions to atmospheric oxygen. Brain microsomes had significantly higher binding capacities (per milligram of protein) than red blood cell ghosts. The ratio of endpoint titers of CH₃ HgCl to HgCl₂ averaged 2:1 in assays of cysteine, proteins, and membranes, showing that the assay was free of denaturation artifacts and protein-protein interference. Solutions of EDTA showed measurable binding of Hg²⁺ but not of CH₃ Hg⁺. Satisfactory titrations were also obtained with N-ethylmaleimide.     

Diluents Effect on Inhibiting Dissolution of Organic Electrode for Highly Reversible Li-Ion Batteries

The potential of organic electrodes in lithium-ion batteries (LIBs) is highlighted by their cost-effectiveness and natural abundance. However, the dissolution of the active material in the electrolyte is a major obstacle to their use in LIBs. Although high-concentration electrolytes (HCEs) have been proposed to address this issue, they face challenges such as high viscosity, poor wettability, and suboptimal ion conductivity. Hence, this study introduces diluted electrolytes as non-solvating electrolytes to offset the physical limitations of HCEs and suppress the dissolution of organic electrodes. When a diluted electrolyte is used, perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA)—a notable organic electrode material—demonstrates superior capacity retention and rate performance, achieving 91% of capacity retained at 1000 mA g⁻¹ over 1000 cycles. Through electrochemical and spectroscopic measurements and molecular dynamics simulations, the diluted electrolyte successfully inhibits and demonstrates the dissolution of the active material, preventing capacity loss and the detrimental shuttle effect. This study presents a promising strategy for achieving highly reversible organic electrode-based LIBs through the development of nonsolvating electrolytes.     

Electrochemical behavior of neomycin at DNA-modified gold electrodes

Deoxyribonucleic acid (DNA) modified gold electrodes are prepared by the dry adsorptive method and the electrochemical behavior of neomycin and the influence of Pb(II) are studied by cyclic voltammetry, chronocoulometry, differential pulse voltammetry. It is found that in 0.01 M phosphate-buffered saline (PBS) buffer solutions (pH 7.3) at DNA/Au electrode neomycin exhibits an irreversible cathodic peak (E_p = 0.489 V), which is more positive and less sensitive compared with that at bare gold electrodes (E_p = 0.423 V). In the presence of Pb(II) the peak shifts toward positive with its height increasing. Moreover, the peak height is linear to neomycin concentration over the range of 0.15-57 μM. The interaction of Pb(II)-neomycin complex with calf thymus DNA is also studied by calculating the binding constants (K) of the Pb(II)-neomycin complex to DNA and binding site size (s) from voltammetric data (1.0 × 10⁷ M⁻¹ and 4 bp, respectively).     

Ion selectivity of a poly(3-pentylmethoxythiophene) LB-layer modified carbon-fiber microelectrode as a consequence of the second order filtering in voltcoulometry

Ion selective properties of poly(3-pentylmethoxythiophene) Langmuir-Blodgett film modified carbon-fiber microelectrode are described. The study of the electrode behavior indicates that important features occur if two electrochemical methods, one of them being kinetics sensitive, are used. While in case of the typical steady-state voltammetry the electrode remains sensitive to both the cations and anions, the kinetics-sensitive properties of voltcoulometry based on the second-order filtering scheme disable the observation of anions. As a model system a mixture of copper and dopamine ions is used.     

In vivo measurements of changes in pH triggered by oxalic acid in leaf tissue of transgenic oilseed rape

Oxalic acid (OA), a non-host-specific toxin secreted by Sclerotinia sclerotiorum during pathogenesis, has been demonstrated to be a major phytotoxic and pathogenic factor. Oxalate oxidase (OXO) is an enzyme associated with the detoxification of OA, and hence the introduction of an OXO gene into oilseed rape (Brassica napus L.) to break down OA may be an alternative way of increasing the resistance of the plant to Sclerotinia sclerotiorum. In order to investigate the activation of OXO in transgenic oilseed rape, a convenient and accessible method was used to monitor changes in pH in response to stress induced by OA. The pH sensor, a platinum microcylinder electrode modified using polyaniline film, exhibited a linear response within the pH range from 3 to 7, with a Nernst response slope of 70 mV/pH at room temperature. The linear correlation coefficient was 0.9979. Changes induced by OA in the pH values of leaf tissue of different oilseed rape species from Brassica napus L. were monitored in real time in vivo using this electrode. The results clearly showed that the transgenic oilseed rape was more resistant to OA than non-transgenic oilseed rape.     

Electrochemical consideration on the optimum pH of bilirubin oxidase

Steady-state current-potential curves were obtained for the direct electron transfer (DET) of bilirubin oxidase (BOD) at a highly oriented pyrolytic graphite electrode, and the theoretical analysis based on nonlinear regression enabled us to determine the formal redox potential (E degrees') of BOD in a wide pH range of 2.0 to 8.5. Cyclic voltammetric measurements were also performed for substrates, including p-phenylenediamine (PPD), o-aminophenol (OAP), and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), and their E degrees ' values or the anodic peak potentials (for OAP) were determined at various pH values. The difference in the redox potentials between BOD and substrates (DeltaE degrees') showed a maximum at pH 6.5 to 8.0, pH 6.5 to 8.0, and pH 3.5 to 4.5 for PPD, OAP, and ABTS, respectively. These pH ranges should be thermodynamically most favorable for the electron transfer between BOD and the respective substrates. In practice, the pH ranges showing a maximum DeltaE degrees' corresponded well with the optimum pH values for the O(2) reduction activity of BOD: pH 6.5 to 7.5, pH 8.0 to 8.5, and pH 4.0 for PPD, OAP, and ABTS, respectively. Thus, it was suggested that DeltaE degrees ' should be one of the primary factors determining the activity of BOD with the substrates.     

Disposable biosensor based on enzyme immobilized on Au-chitosan-modified indium tin oxide electrode with flow injection amperometric analysis

Indium tin oxide (ITO) electrode is used to fabricate a novel disposable biosensor combined with flow injection analysis for the rapid determination of H2O2. The biosensor is prepared by entrapping horseradish peroxidase (HRP) enzyme in colloidal gold nanoparticle-modified chitosan membrane (Au-chitosan) to modify the ITO electrode. The biosensor is characterized by scanning electron microscope, atomic force microscope, and electrochemical methods. Parameters affecting the performance of the biosensor, including concentrations of o-phenylenediamine (OPD) and pH of substrate solution, were optimized. Under the optimal experimental conditions, H2O2 could be determined in the linear calibration range from 0.01 to 0.5 mM with a correlation coefficient of 0.997 (n=8). The amperometric response of the biosensor did not show an obvious decrease after the substrates were injected continuously 34 times into the flow cell. The prepared biosensor not only is economic and disposable, due to the low-cost ITO film electrode obtained from industrial mass production, but also is capable with good detection precision, acceptable accuracy, and storage stability for the fabrication in batch.