Electrochemical Graphene Research Articles

Potential pulse sequences for defect-controlled electrochemical graphene exfoliation

Potential pulse sequences for defect-controlled electrochemical graphene exfoliation

UV‐Induced Synthesis of Graphene Supported Iridium Catalyst with Multiple Active Sites for Overall Water Splitting

AbstractCatalysts that can promote the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are in demand for efficient water splitting. Here, a general and practical UV‐induced synthesis of noble metal catalysts supported on reduced electrochemical graphene oxide (M‐rEGO, M = Ir, Pt or Pd) is proposed. The use of EGO with a low degree of oxidation and the generation of the highly reducing isopropanol radical from added isopropanol and acetone are crucial for this one‐step, one‐pot synthesis. Using Ir as a model material, the vacancies of rEGO allow the interaction of undercoordinated C with Ir, forming multiple active Ir species including single atoms (SAs), dual‐atom pairs (DAs) and nanoparticles. This Ir‐rEGO catalyst exhibits overpotentials of only 42.3 and 294 mV to reach 10 mA cm−2 in 0.5 м H2SO4 for HER and 1 м KOH for OER, respectively, at an extremely low Ir loading (2.1 wt%). The water‐splitting cells featuring Ir‐rEGO catalyst outperform those using commercial Pt/C (20 wt%) and RuO2 catalysts in both acidic and alkaline electrolytes. Density functional theory calculations confirm the stabilization of SAs and DAs at the vacancies of graphene lattice as well as the high activity of DAs in both HER and OER.

Gate-Controlled Neuromorphic Functional Transition in an Electrochemical Graphene Transistor.

Neuromorphic devices have attracted significant attention as potential building blocks for the next generation of computing technologies owing to their ability to emulate the functionalities of biological nervous systems. The essential components in artificial neural networks such as synapses and neurons are predominantly implemented by dedicated devices with specific functionalities. In this work, we present a gate-controlled transition of neuromorphic functions between artificial neurons and synapses in monolayer graphene transistors that can be employed as memtransistors or synaptic transistors as required. By harnessing the reliability of reversible electrochemical reactions between carbon atoms and hydrogen ions, we can effectively manipulate the electric conductivity of graphene transistors, resulting in a high on/off resistance ratio, a well-defined set/reset voltage, and a prolonged retention time. Overall, the on-demand switching of neuromorphic functions in a single graphene transistor provides a promising opportunity for developing adaptive neural networks for the upcoming era of artificial intelligence and machine learning.

Graphenization of graphene oxide films for strongly anisotropic thermal conduction and high electromagnetic interference shielding

A macroscopic carbon film that has a “graphenic” structure (defect-free in-plane graphene lattice yet absence of Bernal type graphitic stacking order), may inherit the exotic properties of rotated/slipped few-layer graphene (e.g., high flexibility and anisotropic transport properties). However, the fabrication of such a film remains challenging and unreported. Here we show that the annealing of reduced electrochemical graphene oxide (REGO), which has fewer in-plane defects than the conventional graphene oxide from Hummers’ method, leads to a nearly intact graphene lattice (Raman ID/IG down to 0.03) without restoring the graphitic stacking order (I2D/IG > 1 and a single Lorentzian 2D peak). Atomic resolution transmission electron microscopy verifies the unique graphenic structure with random interlayer rotations. Density functional theory calculations imply the low defect density of REGO can suppress the interplanar interaction between undercoordinated carbon atoms, therefore inhibiting cross-plane migration of vacancies and the consequent establishment of stacking order. The annealed, graphenic REGO film is highly flexible and has an in-plane to cross-plane thermal conductivity ratio of 835 (among the highest reported for anisotropic thermal conductors). This high anisotropic ratio is attributed to the inhibited through-plane heat transport (0.26 W m−1 K−1) by the interlayer rotations and the high in-plane thermal conductivity (218 W m−1 K−1) enabled by intact graphene lattice. The graphenic films show high electromagnetic interference shielding effectiveness of 80.3 dB at a thickness of 53 μm and 42.4 dB at 5.7 μm, with an absolute effectiveness (>70000 dB cm2 g−1) superior to two-dimensional metal carbides (MXenes) and Al foil.

L-Ascorbic Acid Treatment of Electrochemical Graphene Nanosheets: Reduction Optimization and Application for De-Icing, Water Uptake Prevention, and Corrosion Resistance

The aeronautical industry demands facile lightweight and low-cost solutions to address climate crisis challenges. Graphene can be a valid candidate to tackle these functionalities, although its upscalability remains difficult to achieve. Consequently, graphene-related materials (GRM) are gathering massive attention as top-down graphite exfoliation processes at the industrial scale are feasible and often employed. In this work, environmentally friendly produced partially oxidized graphene nanosheets (POGNs) reduced by green solvents such as l-Ascorbic Acid to rGNs are proposed to deliver functional coatings based on a glass fiber composite or coated Al2024 T3 for strategic R&D questions in the aeronautical industry, i.e., low energy production, de-icing, and water uptake. In detail, energy efficiency in rGNs production is assessed via response-surface modeling of the powder conductivity, hence proposing an optimized reduction window. De-Icing functionality is verified by measuring the stable electrothermal property of an rGNs based composite over 24 h, and water uptake is elucidated by evaluating electrochemical and corrosion properties. Moreover, a mathematical model is proposed to depict the relation between the layers' sheet resistance and applied rGNs mass per area, which extends the system to other graphene-related materials, conductive two-dimensional materials, and various substrates. To conclude, the proposed system based on rGNs and epoxy paves the way for future multifunctional coatings, able to enhance the resistance of surfaces, such as airplane wings, in a flight harsh environment.

Two-step thermal treatment of electrochemical graphene oxide films for high-performance electrical heating and electromagnetic interference shielding

Electric heaters have attracted growing interest due to their wide applications in healthcare, smart wear, and aerospace. Contrarily, conventional heaters fail to meet the expectations of flexibility, high temperature, and efficiency. The current protocol focus on the fabrication of a flexible, high-temperature, and high-performance heater through a multi-step strategy. The modified two-step electrochemical exfoliation approach facilitated the formation of electrochemical graphene oxide (EGO). The simple two-step thermal treatment of EGO produced graphene film. The EGO structure exhibits excellent flexibility, good electrical conductivity, and thermal stability after thermal treatment. Consequently, graphene film showed good flexibility and efficient electric heating performance. It only required 13 s to reach 401.2 °C at 3.5 V. Additionally, graphene film displays sufficient heating reliability, stability, and repeatability under heating cycles and prolonged heating. Moreover, it demonstrates electromagnetic interference shielding effectiveness of up to 30383.6 dB cm2/g. Therefore, graphene film has emerged as a promising alternative for developing intelligent clothes, wearable devices, and healthcare devices.

Tafel-Kinetics-Controlled High-Speed Switching in a Electrochemical Graphene Field-Effect Transistor.

Graphene field-effect transistors (FETs) have attracted tremendous attention owing to the single-atomic-layer thickness and high electron mobility for potential applications in next-generation electronics. With regards to switching methodology, the electric-field-induced metal-insulator transition offers a new strategy to produce a large on/off current ratio through reversible electrochemical hydrogenation of the graphene channels. Therefore, the performance of such electrochemical graphene FETs greatly relies on the kinetics of hydrogenation reaction. Here, we show that the switching time can be systemically controlled by the applied gate voltages and geometries of graphene channels. The turn-on and turn-off time display an exponential dependence on the gate voltages, manifesting the dominated Tafel-form kinetics of hydrogenation reaction in a two-dimensional limit. Moreover, the turn-off time is inversely proportional to the channel width but independent of the length, while the turn-on time relies on both the width and length, as well as the off-state gate voltage and duration. Our work improves the response time to the magnitude of tens of microseconds and advances the application of graphene-based electronic devices.

Novel electrolyte additive of graphene oxide for prolonging the lifespan of zinc-ion batteries

Aqueous zinc-ion batteries have attracted the attention of the industry due to their low cost, good environmental friendliness, and competitive gravimetric energy density. However, zinc anodes, similar to lithium, sodium and other alkali metal anodes, are also plagued by dendrite problems. Zinc dendrites can penetrate through polymer membranes, and even glass fiber membranes which seriously hinders the development and application of aqueous zinc-ion batteries. To resolve this issue, certain additives are required. Here we have synthesized an electrochemical graphene oxide with novel electrolyte based on tryptophan, which allows to obtain few-layered sheets with a remarkably uniform morphology, good aqueous solution dispersion, easy preparation and environmental friendliness. We used this electrochemical graphene oxide as an additive to the electrolyte for aqueous zinc-ion batteries. The results of phase-field model combined with experimental characterization revealed that the addition of this material effectively promotes the uniform distribution of the electric field and the Zn-ion concentration field, reduces the nucleation overpotential of Zn metal, and provides a more uniform deposition process on the metal surface and improved cyclability of the aqueous Zn-ion battery. The resultant Zn∣Zn symmetric battery with the electrochemical graphene oxide additive affords a stable Zn anode, which provided service for more than 500 h at 0.2 mA cm−2 and even more than 250 h at 1.0 mA cm−2. The Coulombic efficiency (98.7%) of Zn∣Cu half-cells and thus cyclability of aqueous Zn-ion batteries using electrochemical graphene oxide is significantly better compared to the additive-free electrolyte system. Therefore, our approach paves a promising avenue to foster the practical application of aqueous Zn-ion batteries for energy storage.

Unlocking the energy storage potential of polypyrrole via electrochemical graphene oxide for high performance zinc-ion hybrid supercapacitors

Safe and low-cost zinc-ion hybrid supercapacitors using neutral aqueous electrolytes are promising for large scale and high power energy storage. A key challenge for Zn-ion hybrid supercapacitors is to increase their energy density without sacrificing the high power performance. Herein, we report a Zn-ion hybrid supercapacitor using a polypyrrole/electrochemical graphene oxide (PPy/EGO) composite cathode and aqueous 1 M ZnCl 2 or ZnBr 2 electrolytes. The Zn-PPy/EGO system with an operating cell voltage from 0.5 to 1.5 V exhibited high energy and high power densities of 117.7 and 72.1 Wh kg −1 at 0.34 and 12.4 kW kg −1 , respectively, outperforming the Zn-ion hybrid supercapacitors using carbon cathodes. This high performance is because of the facilitated electronic and ionic transport in the PPy/EGO composite. In brief, the EGO prepared via the electrochemical method we recently reported has good structure integrity and is easily reduced; the porous PPy/EGO composite from co-electrodeposition benefits fast ion diffusion in pores; the small, monovalent halides anions in the zinc halides electrolytes are highly mobile in bulk PPy for fast solid-phase anion insertion/de-insertion. Electrochemical characterization and ex-situ X-ray photoelectron spectroscopy confirmed the anion-dominated charge storage mechanism of PPy/EGO cathode in Zn-PPy/EGO system. • PPy/EGO composite electrodes were prepared by one-step co-electrodeposition. • Mildly oxidized EGO with less disrupted structure benefits electron conduction. • Porous structure of PPy/EGO composite electrode facilitate ion diffusion. • Zn-PPy/EGO system using ZnCl 2 or ZnBr 2 electrolyte show record high performance.

Laser solid-phase synthesis of single-atom catalysts

Single-atom catalysts (SACs) with atomically dispersed catalytic sites have shown outstanding catalytic performance in a variety of reactions. However, the development of facile and high-yield techniques for the fabrication of SACs remains challenging. In this paper, we report a laser-induced solid-phase strategy for the synthesis of Pt SACs on graphene support. Simply by rapid laser scanning/irradiation of a freeze-dried electrochemical graphene oxide (EGO) film loaded with chloroplatinic acid (H2PtCl6), we enabled simultaneous pyrolysis of H2PtCl6 into SACs and reduction/graphitization of EGO into graphene. The rapid freezing of EGO hydrogel film infused with H2PtCl6 solution in liquid nitrogen and the subsequent ice sublimation by freeze-drying were essential to achieve the atomically dispersed Pt. Nanosecond pulsed infrared (IR; 1064 nm) and picosecond pulsed ultraviolet (UV; 355 nm) lasers were used to investigate the effects of laser wavelength and pulse duration on the SACs formation mechanism. The atomically dispersed Pt on graphene support exhibited a small overpotential of −42.3 mV at −10 mA cm−2 for hydrogen evolution reaction and a mass activity tenfold higher than that of the commercial Pt/C catalyst. This method is simple, fast and potentially versatile, and scalable for the mass production of SACs.

Thermo-electro-rheological behaviour of vanadium electrolyte-based electrochemical graphene oxide nanofluid designed for redox flow battery

The use of electrolyte-based nanofluid is a new approach for enhancing the performance of Vanadium Redox Flow Batteries (VRFBs). This paper, for the first time in the literature, presents an experimental study to comprehensively investigate the rheological behaviour, electrical conductivity, and thermal conductivity of a newly prepared electrochemical graphene oxide (EGO)/ vanadium (IV) electrolyte-based nanofluid in different weight concentration and bulk temperatures. SEM, FT-IR and X-ray Diffraction (XRD) characterizations were performed and different functional groups, smooth 2D layered structures, and low crystallinity were detected in our tailored oxidation EGO which are amongst the enhancing features for VRFBs electrode materials. It was observed that the optimum weight concentration of nanoparticles in the electrolyte-based nanofluid is 0.05 wt% with strong colloidal stability, enhanced electrical and thermal conductivities, and an optimal viscosity. The maximum feasible enhancements in electrical and thermal conductivities that were achieved were 12%, and 4%, respectively, which can positively affect the performance of flow battery in terms of electrochemical activity on the electrode surface and thermal management of the flow battery system. In addition, the rheological evaluation showed that the behaviour of the electrolyte-based nanofluid tends to change from Newtonian to non-Newtonian for weight concentrations higher than 0.05%. The results obtained from rheological behaviour can provide useful insights in choosing an optimum pumping system of the flow batteries working with electrolyte-based nanofluid.

Facile Synthesis of Boron-Doped Reduced Electrochemical Graphene Oxide for Sodium Ion Battery Anode

Facile Synthesis of Boron-Doped Reduced Electrochemical Graphene Oxide for Sodium Ion Battery Anode

High sensitivity and flexible fabric strain sensor based on electrochemical graphene

In this study, electrochemical graphene (ECG) was chosen to be attached to a polyester fabric with a knitted structure as a flexible fabric strain sensor through a cloth dyeing method. According to scanning electron microscopy observation and Raman scattering spectroscopy measurements, ECG was successfully attached to the fabric structure. The electromechanical performance and strain sensing properties of the graphene-based flexible strain sensor were evaluated. The resistance change and gauge factor of different ECG attached as a fabric strain sensor were quantified. The gauge factor of the fabric strain sensor with less ECG is greater than that of the fabric strain sensor with more ECG. The high gauge factor of 47 was achieved in a strain range from 0% to 2%. The fabricated strain sensor exhibited high sensitivity, fast response time and good repeatability. The fabricated ECG fabric strain sensor could be used to detect tiny physiological signals and human motion.

Facile, Electrochemical Chlorination of Graphene from an Aqueous NaCl Solution.

We report a facile approach to directly chlorinate graphene from an aqueous sodium chloride solution under ambient conditions. By applying a moderate anodic voltage to substrate-supported monolayer graphene, the resultant chlorine radicals generated at the graphene surface enable efficient chlorination: X-ray photoelectron spectrum confirms the formation of C-Cl bonds, and reaction voltage-tunable Cl:C atomic ratios of up to 17% are achieved. In comparison, we find the corresponding electrochemical graphene bromination and iodination reactions much less viable. Electrical and Raman characterizations show substantial p-doping for the chlorinated graphene, yet good basal-plane integrity and electrical properties are maintained. Interference reflection microscopy and pH-dependent experiments next help elucidate the competition between the radical-mediated electrochemical chlorination and oxidation in the process, and rationalize acidic conditions for optimal chlorination. Reaction in a mixed NaCl-NaN3 solution shows the electrochemical chlorination to be fully suppressed by azidation, yet a sequential, two-step chlorination-azidation approach permits facile bifunctionalization.

Non-enzymatic and highly sensitive lactose detection utilizing graphene field-effect transistors

Field-effect transistor (FET) biosensors based on low-dimensional materials are capable of highly sensitive and specific label-free detection of various analytes. In this work, a FET biosensor based on graphene decorated with gold nanoparticles (Au NPs) was fabricated for lactose detection in a liquid-gate measurement configuration. This graphene device is functionalized with a carbohydrate recognition domain (CRD) of the human galectin-3 (hGal-3) protein to detect the presence of lactose from the donor effect of lectin – glycan affinity binding on the graphene. Although the detection of lactose is important because of its ubiquitous presence in food and for disease related applications (lactose intolerance condition), in this work we exploit the lectin/carbohydrate interaction to develop a device that in principle could specifically detect very low concentrations of any carbohydrate. The biosensor achieved an effective response to lactose concentrations over a dynamic range from 1 fM to 1 pM (10−15 to 10−12 mol L−1) with a detection limit of 200 aM, a significant enhancement over previous electrochemical graphene devices. The FET sensor response is also specific to lactose at aM concentrations, indicating the potential of a combined lectin and graphene FET (G-FET) sensor to detect carbohydrates at high sensitivity and specificity for disease diagnosis.

Laser Assisted Solution Synthesis of High Performance Graphene Supported Electrocatalysts

AbstractSimple, yet versatile, methods to functionalize graphene flakes with metal (oxide) nanoparticles are in demand, particularly for the development of advanced catalysts. Herein, based on light‐induced electrochemistry, a laser‐assisted, continuous, solution route for the simultaneous reduction and modification of graphene oxide with catalytic nanoparticles is reported. Electrochemical graphene oxide (EGO) is used as starting material and electron–hole pair source due to its low degree of oxidation, which imparts structural integrity and an ability to withstand photodegradation. Simply illuminating a solution stream containing EGO and metal salt (e.g., H2PtCl6 or RuCl3) with a 248 nm wavelength laser produces reduced EGO (rEGO, oxygen content 4.0 at%) flakes, decorated with Pt (≈2.0 nm) or RuO2 (≈2.8 nm) nanoparticles. The RuO2–rEGO flakes exhibit superior catalytic activity for the oxygen evolution reaction, requiring a small overpotential of 225 mV to reach a current density of 10 mA cm−2. The Pt–rEGO flakes (10.2 wt% of Pt) show enhanced mass activity for the hydrogen evolution reaction, and similar performance for oxygen reduction reaction compared to a commercial 20 wt% Pt/C catalyst. This simple production method is also used to deposit PtPd alloy and MnOx nanoparticles on rEGO, demonstrating its versatility in synthesizing functional nanoparticle‐modified graphene materials.

Investigation of sulfuric acid intercalation into thermally expanded graphite in order to optimize the synthesis of electrochemical graphene oxide

This paper is devoted to a detailed study of the electrochemical intercalation of sulfuric acid into the foil structure based on thermally expanded graphite, as the decisive stage in the process of producing electrochemical graphene oxide. In the work, the potentials of individual areas of anodic polarization were determined, passing without destroying the carbon electrode. The diffusion control characteristic of the entire range of intercalation potentials is shown. The effective capacities, characteristic times, and acid consumption for the electrochemical intercalation process are evaluated. The minimum termination potential of the intercalation process is found. It is shown that limiting the anodic polarization of thermally expanded graphite at the minimum potential for the termination of intercalation can significantly reduce the energy consumption of the entire method for producing electrochemical graphene oxide. A comparison is made of electrochemical graphene oxide with graphene oxide, obtained by a modified Hammers method, by a number of physicochemical methods.

The role of electrolyte acid concentration in the electrochemical exfoliation of graphite: Mechanism and synthesis of electrochemical graphene oxide

Electrochemistry has emerged as a major route for graphene and graphene oxide synthesis from graphite. Anodic graphite oxidation is commonly used with dilute mineral acid or aqueous salt electrolytes. In this system, the electrolyte acid concentration appears to be a critical parameter. However, the effect of the acid concentration, particularly at low concentrations, is still not fully understood. To address this issue, we used a packed bed electrochemical reactor to synthesize seven different electrochemical graphite oxide (EGO) products in 2–16 M sulfuric acid. Detailed XRD, XPS, Raman, conductivity and optical microscopy analysis of the products was carried out. We found dilute acid (<10 M) graphite oxides were less crystalline and less oxidized than those produced in stronger acids. The oxygen evolution reaction at the graphite surface appears to affect the structural changes, oxidation mechanism, and electrochemical corrosion of the anode. EGO conductivity is also strongly affected by the electrolyte’s acidity. We show that well oxidized, yet reasonably conductive, single layer graphene oxide can be produced from 7.1 M acid. These results broaden our understanding of graphite electrochemistry and will serve to inform future electrochemical graphene synthesis efforts.

Amperometric sensor for dopamine based on surface-graphenization pencil graphite electrode prepared by in-situ electrochemical delamination.

A surface-graphenized pencil graphite electrode (SGPGE) served as an amperometric sensor for dopamine (DA). It was prepared through a one-step in-situ electrochemical graphene delamination. The graphite particles on the outer surface of the pencil graphite electrode (PGE) were delaminated by controlling the electrochemical delaminating conditions such as the applied anodic voltage and polarization duration, as well as the kind ofelectrolytes. The best conditions were identified by scanning electron microscopy, Raman spectra, cyclic voltammetry and differential pulse voltammetry (DPV). As a result, the electrode was endowed with an optimum combination of graphene delamination efficiency and electrochemical activity. The electrochemical treatment activates the surface sensing sitesandimproves the sensing performance. The NaOH-teated anodically graphenized electrode was used to sense dopamine by DPV. The bestoxidation voltage of dopamine is ataround 0.17V (vs. SCE). The electrode respondsy to dopamine in the ranges of 0.15 to 45μM, the detection limit is 8.2nM (S/N = 3), andthe sensitivity is 20.81μAμM-1cm-2. In real human urine samples, the sensor exhibited detection recoveries of 97.4-98.8% and low relative standard deviations of 3.49-3.92%. Graphical abstract Schematic presentation of a surface-graphenized pencil graphite electrode (SGPGE) for detecting dopamine. It was prepared by a one-step in situ electrochemical graphene delamination.

Hollow ZnO microspheres functionalized with electrochemical graphene oxide for the photodegradation of salicylic acid.

Hollow ZnO microspheres were successfully synthesized by a hydrothermal method and then functionalized with graphene oxide (GO) flakes, previously obtained through electrochemical oxidation. Their photocatalytic activity toward the photodegradation of salicylic acid under UV light irradiation was evaluated by UV-Vis spectroscopy. Unfunctionalized microspheres and ZnO functionalized with chemically oxidized graphene were also studied as comparative terms. The hybrid materials of ZnO with both electrochemical and chemical GO gave a similar photodegradation yield of ∼28% against 18% of the non-functionalized microspheres. The similar degradation yields and rate constants obtained with the two GO synthetic methods indicate that electrochemical oxidation of GO represents an eco-friendly option over traditional methods for photocatalytic degradation systems.