Electrochemical Exfoliation Research Articles

Spatially Confined Radical Addition Reaction for Electrochemical Synthesis of Carboxylated Graphene and its Applications in Water Desalination and Splitting.

Due to the chemical stability of graphene, synthesis of carboxylated graphene still remains challenging during the electrochemical exfoliation of graphite. In this work, a spatially confined radical addition reaction which occurs in the sub-nanometer scaled interlayers of the expanded graphene sheets for the electrochemical synthesis of highly stable carboxylated graphene is reported. Here, formate anions act as both intercalation ions and co-reactant acid for the confinement of electro-generated carboxylic radical (●COOH) in the sub-nanometer scaled interlayers, which facilitates the radical addition reaction on graphene sheets. The controllable carboxylation of graphene is realized by tuning the concentration of formate anions in the electrolyte solution. The high crystallinity of the obtained product indicates the occurrence of spatially confined ●COOH addition reaction between the sub-nanometer interlayers of expanded graphite. In addition, the carboxylated graphene have been used for water desalination and hydrogen/oxygen reduction reaction. Therefore, this work provides a new method for the in situ preparation of functionalized graphene through the electrolysis and its applications in water desalination and hydrogen/oxygen reduction reactions.

Recycling waste carbon fibers for solar-driven clean water production by one-step electrochemical process

Waste carbon fibers (WCF), as a co-product of carbon-based textile material, presented a high recycling value. However, it is difficult to utilize the short carbon fibers by traditional process, recycling and using these WCF effectively has thus attracted increasing attention. Herein, we propose a novel strategy that utilizes simultaneous electrochemical exfoliation and deposition processes to convert WCF into photothermal materials. Stainless steel felt (SS) was selected as the substrate to verify this strategy. Through this strategy, the reduced graphene oxide-coated SS (rGO-SS) was obtained. The 2D solar-driven interfacial evaporator based on rGO-SS enabled stable evaporation in actual wastewater with an excellent rate of 1.44 ∼ 1.50 kg m−2 h−1 under 1 sun. Additionally, by constructing a 3D evaporation structure, rGO-SS performed a high evaporation rate of ∼16.88 kg m−2 h−1 under 1 sun. Finally, this work proposes a novel method for the waste carbon fibers and gives new insights into fabricating a novel solar-driven interfacial evaporator.

Engineering Charge Density Waves by Stackingtronics in Tantalum Disulfide.

In the realm of condensed matter physics and materials science, charge density waves (CDWs) have emerged as a captivating way to modulate correlated electronic phases and electron oscillations in quantum materials. However, collectively and efficiently tuning CDW order is a formidable challenge. Herein, we introduced a novel way to modulate the CDW order in 1T-TaS2 via stacking engineering. By introducing shear strain during the electrochemical exfoliation, the thermodynamically stable AA-stacked TaS2 consecutively transform into metastable ABC stacking, resulting in unique 3a × 1a CDW order. By decoupling atom coordinates, we atomically deciphered the 3D subtle structural variations in trilayer samples. As suggested by density functional theory (DFT) calculations, the origin of CDWs is presumably due to collective excitations and charge modulation. Therefore, our works shed light on a new avenue to collectively modulate the CDW order via stackingtronics and unveiled novel mechanisms for triggering CDW formation via charge modulation.

Zinc-Carbon Battery Recycling for Investigating Carbon Materials for Supercapacitor Applications.

In this paper, carbon materials, including graphene nanosheets and carbon nanoparticles, were prepared from spent zinc-carbon batteries by the following two simple methods: electrochemical exfoliation and ultrasonication. Here, graphene nanosheets were synthesized by electrochemical exfoliation in 0.5 M H2SO4 by using a direct current power supply with two carbon rods from spent zinc-carbon batteries. Carbon nanoparticles were prepared by fast ultrasonication in a low-cost, green solution of DI water and ethanol. Graphene nanosheets in this study have high quality, large scale, and good electrochemical ability, while carbon nanoparticles have a unique nanosize and a good specific surface area. These carbon materials were applied for electrochemical measurements for supercapacitor studies and showed excellent stability at different temperatures. Moreover, electric double-layer capacitor devices based on graphene nanosheets and carbon nanoparticles were also used in electrochemical studies with strong stability and good electrochemical capability.

Features of Few-Layer Phosphorene Structure Synthesis by Plasma-Assisted Electrochemical Exfoliation of Black Phosphorus

Features of Few-Layer Phosphorene Structure Synthesis by Plasma-Assisted Electrochemical Exfoliation of Black Phosphorus

Prototyping a wearable and stretchable graphene-on-PDMS sensor for strain detection on human body physiological and joint movements.

In the era of wearable electronic devices, which are quite popular nowadays, our research is focused on flexible as well as stretchable strain sensors, which are gaining humongous popularity because of recent advances in nanocomposites and their microstructures. Sensors that are stretchable and flexible based on graphene can be a prospective 'gateway' over the considerable biomedical speciality. The scientific community still faces a great problem in developing versatile and user-friendly graphene-based wearable strain sensors that satisfy the prerequisites of susceptible, ample range of sensing, and recoverable structural deformations. In this paper, we report the fabrication, development, detailed experimental analysis and electronic interfacing of a robust but simple PDMS/graphene/PDMS (PGP) multilayer strain sensor by drop casting conductive graphene ink as the sensing material onto a PDMS substrate. Electrochemical exfoliation of graphite leads to the production of abundant, fast and economical graphene. The PGP sensor selective to strain has a broad strain range of ⁓60%, with a maximum gauge factor of 850, detection of human physiological motion and personalized health monitoring, and the versatility to detect stretching with great sensitivity, recovery and repeatability. Additionally, recoverable structural deformation is demonstrated by the PGP strain sensors, and the sensor response is quite rapid for various ranges of frequency disturbances. The structural designation of graphene's overlap and crack structure is responsible for the resistance variations that give rise to the remarkable strain detection properties of this sensor. The comprehensive detection of resistance change resulting from different human body joints and physiological movements demonstrates that the PGP strain sensor is an effective choice for advanced biomedical and therapeutic electronic device utility.

Improvement Synthesis of Graphene Oxide Yield in Two Steps of Intercalation and Oxidation of Flexible Graphite Foil by Electrochemical Exfoliation

Synthesis of high quality and quantity of graphene by cost-effective methods are highly desirable for various application. In electrochemical exfoliation, graphite foil has been used as carbon source for the synthesis of high yield of graphene flakes. Electrochemical exfoliation is one of the faster and cheaper method to synthesize graphene sheets. In this work, five different types of concentration of sulphuric acid were used for electrochemical exfoliation. The electrochemical cell design where graphite foil as anode and copper foil as cathode which were connected to DC power supply of 5V. To examine the morphology scanning electron microscope (SEM) was employed in which the sheet structures with large lateral dimension and thin graphene flakes. Furthermore, X-ray diffraction (XRD) revealed that exfoliated graphene samples showed a significant peak at about 2θ = 26º corresponded to graphite.

Exfoliation of Graphite into Graphene Oxide and Reduction by Plant Extract to Synthesize Graphene

Graphene oxide (GO) is a demand material in industrial field for many applications such as electronic devices, capacitor and sensor. This is due to its unique structures and excellent properties. The GO sheets were exfoliated from graphite rod in electrochemical exfoliation. To reduce GO, an electrochemical reduction of GO using green tea was carried out in this research. The conventional chemical reduction method consumed highly toxic and strongly hazardous chemicals such as hydrazine to reduce GO to reduced GO (RGO). Therefore, a green synthesis method was proposed by using green tea leaves extract as the reducing agent to synthesize RGO. Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) results show that low amount of oxygen-containing functional groups was remained after green tea reduction due to weak reduction capability by green tea. In addition, EDX indicates that oxygen content of GO was decreased from 23.23 to 16.89 Mass% after green tea reduction.

A Review of the Effect of Different Electrolytes on the Synthesis of Graphene Sheets by Electrochemical Exfoliation

Graphene oxide (GO) possess some excellent properties that fulfil various applications. Hummers’ method has been used in GO synthesis for years but some issues such as high-cost GO synthesis, the use of toxic chemicals and low yield of GO are still remains and concerned. In addition, this method spends very long time to be completed and subjected to thorough cleaning process to remove toxic chemicals. On the other hand, the electrochemical method saves time, has no explosion risk, releases no toxic gases, and keep safe environmental. The demand of GO supply is crucial particularly important in applications such as energy storage in automobiles thus, a large scale and cheap production of GO is needed. It is reported that the electrochemical synthesis of GO has more benefits such as rapid synthesis, low cost and environmentally friendly than Hummers’ method, therefore, the impact of different electrolytes is important to be studied. Herein, various research works about the electrochemical synthesis of GO are reviewed, precisely involving the anodic exfoliation of graphite, exfoliation mechanism and effects of exfoliation parameters.

Study on the quenching sensitivity of corrosion properties in 7199 aluminum alloy

This study used electrochemical corrosion, intergranular corrosion (IGC), and exfoliation corrosion tests, as well as microscopic observations of the microstructure and first-principles calculations, to investigate the effect of different quenching rates on the microstructure and corrosion properties of the 7199 alloy. The results show that as the quenching rate decreases, the size, Zn, and Mg content of precipitated phases at grain boundaries (GBs), as well as the width of the precipitation-free zone (PFZ), increase, resulting in a decrease in corrosion properties. During slow quenching, the η phase (MgZn2) at the GBs continuously absorbs surrounding Zn and Mg atoms, causing Zn and Mg atom depletion near the GBs. This results in the formation of a wide PFZ. Enlargement of the η phase and PFZ at the GBs leads to anodic dissolution channels, allowing for rapid corrosion expansion along the GBs. Additionally, at slow quenching rates, not only does the η phase precipitate at the subgrain boundaries (SGBs) but also the T and S phases. In corrosive environments, the η phase is more prone to corrosion than the T and S phases. Electron work function calculations show that the S phase has the highest corrosion potential, whereas the η phase has the lowest. As a result, SGBs containing T and S phases are unlikely to serve as corrosion pathways. Corrosion preferentially extends along SGBs containing η phases.

High Potential Electrochemical Synthesis of Thermally Reduced Graphene Nanomaterial

In this study, we provide electrochemical techniques for synthesizing thermally reduced graphene nanomaterial that have high potential, low defects, cost-effectiveness, and ecological sustainability. The electrochemical exfoliation is carried out by employing a 195 W DC (voltage = 60[Formula: see text]V and current = 3.25 A) power source at a maximum electrolyte temperature of about 92.5∘C within the aqueous suspension of 2[Formula: see text]M of sulfuric acid (H2SO[Formula: see text]. Thereafter, the synthesized nanomaterial was treated in the weak piranha [combination of sulfuric acid and hydrogen peroxide (H2O[Formula: see text]] solution using an electrochemical technique inside the water bath sonicator at 80∘C. X-ray diffraction (XRD) analysis shows the peak of diffraction to the (002) plane of the reduced graphene oxide (RGO) samples emerges at around 2[Formula: see text] and 26.56∘ with an interplanar distance of 3.40 Å and 3.54 Å. According to the XRD data, after the high-temperature thermal reduction phase, the structure of the crystals and interplanar separation were recovered. The size of the crystallite of RGO produced under H2SO4 conditions was discovered to be greater than the crystallite size of graphene oxide produced under piranha solution conditions. The Raman analysis results show that the degree of disorder of the graphene synthesized within the H2O2 was higher than in comparison to the graphene synthesized in H2SO4. Field emission scanning electron microscopy (FE-SEM) results show that graphene synthesized in the presence of H2O2 has a thin and porous microstructure in comparison to H2SO4 with no significant effect on the presence of the availability of the C/O ratio. The atomic force microscopy (AFM) analysis indicates that the surface roughness of the graphene synthesized in the H2O2 was higher than that of the H2SO4. The Fourier transform infrared spectroscopy (FT-IR spectroscopy) analytical results show that the majority of the functional groups have been eliminated within the samples.

Morphological and Thermal Characterization of Low-Cost Graphene Produced by Electrochemical Exfoliation Method

The low-cost and mass production of graphene has gained importance in recent years. The electrochemical exfoliation method, one of the graphene production methods, is an efficient technique used to obtain low-cost-effective and large quantities of graphene nanosheets. Exfoliation parameters affect the properties of exfoliated graphene nanosheets. In this study, graphene production is fabricated by the method of exfoliation using electrolyte and voltage parameters. For this, a pen tip was used instead of pure platinum, which is very expensive, at the cathode. The structural research was done by X-ray diffraction spectroscopy (XRD), Raman spectroscopy and Fourier Transform Infrared Spectrometer (F-TIR). Morphological analyses were carried out by Scanning Electron Microscopy (SEM). The number of layers and crystallite of graphene layers were estimated. The obtained results were compared with the results of the other similar studies. Analysis results show that low-cost multilayer graphene can be produced by the electrochemical exfoliation method with the electrical parameters.

Growth and physical-chemical characterization of manganese oxide and graphene-manganese oxide films for potential applications in energy store devices

The need for progress in the development of energy supply devices such as batteries and large capacitors has led to the improvement and innovation of these devices so that they can store energy efficiently, and additionally, they must be small, light, with low production costs, and friendly to the environment. For these reasons, in this investigation results of the characterization of physical and chemical behaviors of graphene-manganese oxide and copper and manganese oxide-copper systems are studied. The graphene was synthesized through the electrochemical exfoliation technique and deposited as a film on common glass and silicon substrates via the spray technique, and over this film, Mn2O3 films were deposited through spin coating. The Raman results showed the presence of peaks D and G, located at 1534 and 1597 cm−1, respectively. XPS analysis demonstrated that the graphene is made up of three layers. TEM studies determined that the graphene is polycrystalline, and XRD established the manganese oxide coatings’ growth along the (222) and (440) planes of Mn2O3. The optical behavior indicated that the absorbance of the graphene-Mn2O3 system decreases the energy gap in 0.8 eV concerning Mn2O3 films. The voltage-current measurements suggest that the density current in the discharge process of the Mn2O3–Cu electrode system was improved approximately 3-fold with the graphene-Mn2O3–Cu electrode system. The obtained results conclude that the addition of graphene to manganese oxide coatings increases their electrochemical performance, so graphene-manganese oxide could be used in energy storage devices.

Solution-processed 2D van der Waals networks: Fabrication strategies, properties, and scalable device applications

Solution-based processing of two-dimensional (2D) materials has garnered significant interest as a facile and versatile route for the large-scalable production of 2D material films. Despite the benefits in process, these films were not considered suitable for device applications during the early stages of research because their electronic properties were far from those of 2D materials obtained through micromechanical exfoliation or chemical vapor deposition. Due to the small lateral dimensions and polydisperse thickness of constituent 2D nanosheets, the resulting film tends to be porous and exhibits numerous inter-sheet junctions, primarily contacting edge-to-edge. This nanosheet morphology leads to poor electrical conductivity of the network, and also hinders the film functioning as a semiconductor or an insulator. To produce ultrathin 2D nanosheets with narrow thickness distribution and large lateral sizes, various chemical exfoliation strategies have been explored, but these are limited by long process times, involvement of harsh chemicals, and/or undesired structural damage or phase changes. Recent breakthroughs in electrochemical exfoliation using tetraalkylammonium intercalants enabled the production of high-quality 2D nanosheets with structural characteristics favorable for producing ultrathin, conformal films of 2D materials, which allow for scalable production of high-performance electronic components that can readily be assembled into functional devices via solution-processing. In this review article, we aim to offer an extensive introduction solution-based processing techniques for acquiring 2D nanosheets, their subsequent assembly into thin films, and their diverse applications, primarily focusing on electronics and optoelectronics but also extending to other fields. Remaining challenges and potential avenues for advancement will also be discussed.

Electrochemical Exfoliation and Growth of Nickel–Cobalt Layered Double Hydroxides@Black Phosphorus Hetero‐Nanostructure Textiles for Robust Foldable Supercapacitors

AbstractAdvanced innovation of flexible electrode with adequate redox activity and stably mechanical endurance that promotes charges kinetic migration and faradaic storage is pivotal for textile‐based supercapacitors (T‐SCs). Herein, this study reports a high‐performance T‐SCs electrode based on nickel–cobalt layered double hydroxides@black phosphorus (NiCo‐LDHs@BP) on a conductive silk (c‐silk) textile (NiCo‐LDHs@BP/c‐silk). Under negative voltage‐induced electrochemical exfoliation, the Ni2+ and Co2+ are embedded into bulk BP framework to form exfoliated BP nanosheets, and the NiCo‐LDHs are in situ grown within the BP networks, generating 3D NiCo‐LDHs@BP hetero‐nanostructure. Significantly, the NiCo‐LDHs@BP exhibits a large space‐charge area, enhanced adsorption energy for OH− and accelerated charges transfer/storage as confirmed using density functional theory calculations. Additionally, the T‐SCs electrode is fabricated by loading the blended NiCo‐LDHs@BP, sericin, and carbon nanotubes on fibroin textile via a silk reconstruction strategy, producing large area production, superior mechanical flexibility, and impressive electrochemical performance. The resultant NiCo‐LDHs@BP/c‐silk electrode exhibits large specific capacitance of 1291.3 F g−1 and considerable rate capacity in 1 M KOH electrolyte. Furthermore, the flexible solid‐state asymmetric T‐SCs deliver high specific areal energy density of 279.6 µWh cm−2 and robust folding capability (85.6% capacitance retention after 5000 folding cycles), which successfully power wearable watch and heart rate meter devices.

Knot Architecture for Biocompatible and Semiconducting 2D Electronic Fiber Transistors.

Wearable devices have generally been rigid due to their reliance on silicon-based technologies, while future wearables will utilize flexible components for example transistors within microprocessors to manage data. Two-dimensional (2D) semiconducting flakes have yet to be investigated in fiber transistors but can offer a route toward high-mobility, biocompatible, and flexible fiber-based devices. Here, the electrochemical exfoliation of semiconducting 2D flakes of tungsten diselenide (WSe2) and molybdenum disulfide (MoS2) is shown to achieve homogeneous coatings onto the surface of polyester fibers. The high aspect ratio (>100) of the flake yields aligned and conformal flake-to-flake junctions on polyester fibers enabling transistors with mobilities μ ≈1 cm2 V-1 s-1 and a current on/off ratio, Ion/Ioff ≈102-104. Furthermore, the cytotoxic effects of the MoS2 and WSe2 flakes with human keratinocyte cells are investigated and found to be biocompatible. As an additional step, a unique transistor 'knot' architecture is created by leveraging the fiber diameter to establish the length of the transistor channel, facilitating a route to scale down transistor channel dimensions (≈100 µm) and utilize it to make a MoS2 fiber transistor with a human hair that achieves mobilities as high as μ ≈15 cm2 V-1 s-1.

Synthesis and Characterization of Graphene Nanoplatelets Fabricated by Electrochemical Exfoliation Method for Conductive Adhesive

Synthesis and Characterization of Graphene Nanoplatelets Fabricated by Electrochemical Exfoliation Method for Conductive Adhesive

Synthesis of Graphene from Pencils Graphite Via Electrochemical Exfoliation Method as a Cu-Foil Coating on the Anode-Free Lithium-Ion Battery

The Anode-free Li-ion Battery (AFLB) is an alternative to a new Li-ion battery model that offers high energy density at the same battery size as conventional models. Uncontrolled dendrite growth inactive the lithium deposition, resulting in decreased specific capacity, shortened lifecycle, and reduced coulombic efficiency. This work reported the utilization of graphene derived from pencil graphite for coating Cu foil as a current collector in AFLBs, to mitigate the formation of lithium dendrites and enhance battery capacity. The graphene-coated Cu foil exhibits a specific capacity of 143 mAh/g, representing a 20 mAh/g increase compared to batteries lacking a graphene coating. The coulombic efficiency of the battery with graphene coating in the charging and discharging process for three cycles is 84.53% in the 1<sup>st</sup> cycle, 101.44% in the 2<sup>nd</sup> cycle, and 98.58% in the 3<sup>rd</sup> cycle.

Harnessing Graphene-Modified Electrode Sensitivity for Enhanced Ciprofloxacin Detection.

Increased evidence has documented a direct association between Ciprofloxacin (CFX) intake and significant disruption to the normal functions of connective tissues, leading to severe health conditions (such as tendonitis, tendon rupture and retinal detachment). Additionally, CFX is recognized as a potential emerging pollutant, as it seems to impact both animal and human food chains, resulting in severe health implications. Consequently, there is a compelling need for the precise, swift and selective detection of this fluoroquinolone-class antibiotic. Herein, we present a novel graphene-based electrochemical sensor designed for Ciprofloxacin (CFX) detection and discuss its practical utility. The graphene material was synthesized using a relatively straightforward and cost-effective approach involving the electrochemical exfoliation of graphite, through a pulsing current, in 0.05 M sodium sulphate (Na2SO4), 0.05 M boric acid (H3BO3) and 0.05 M sodium chloride (NaCl) solution. The resulting material underwent systematic characterization using scanning electron microscopy/energy dispersive X-ray analysis, X-ray powder diffraction and Raman spectroscopy. Subsequently, it was employed in the fabrication of modified glassy carbon surfaces (EGr/GC). Linear Sweep Voltammetry studies revealed that CFX experiences an irreversible oxidation process on the sensor surface at approximately 1.05 V. Under optimal conditions, the limit of quantification was found to be 0.33 × 10-8 M, with a corresponding limit of detection of 0.1 × 10-8 M. Additionally, the developed sensor's practical suitability was assessed using commercially available pharmaceutical products.

Synthesis of highly efficient ternary phase graphene/Bi/SnO2 photocatalyst for degradation of organic dye pollutants

In this work, graphene nanosheets (GNs) are prepared from graphite rods obtained from waste dry-cell batteries using the electrochemical exfoliation (ECE) method. Then GNs used as a matrix to modify tin oxide (SnO2) and Bismuth (Bi) nanoparticles to prepare a binary phase SnO2@G and ternary-phase Bi@SnO2@G nanocomposite materials by wet-chemical method and used as a photocatalysts for degradation of organic dye pollutants. XRD diffraction pattern clearly confirmed the presence of tetragonal crystal system of SnO2 which was maintaining its structure in SnO2@G and G/Bi/SnO2. The stretching and bending vibrations of the functional groups were analyzed using FTIR analysis. FESEM images demonstrated the surface morphology and the texture of the as synthesized sample. Raman Spectroscopic investigation was carried out to confirm the in-plane blending of SnO2 and graphene inside the composite matrix. The as-prepared ternary-phase Bi@SnO2@G-based photocatalyst showed high degradation efficiency of 99.6% and 94.5% for direct blue (DB) and methyl blue (MB) dyes, respectively, under visible light irradiation by (i) minimizing the hole and electron recombination, (ii) providing a high surface area, and (iii) reducing the band gap energy. This study provides an effective, low-cost, and smart approach for producing GNs on a wide scale from battery waste along with nanohybrid composites with high photocatalytic efficiency.