Electrochemical Exfoliation of Graphite to Graphene-Based Nanomaterials

Here, we report on a new automated electrochemical process for the production of graphene oxide (GO) from graphite though electrochemical exfoliation. The effects of the electrolyte and applied voltage were investigated and optimized. The morphology, structure and composition of the electrochemically exfoliated GO (EGO) were probed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX) spectroscopy, X-ray photoelectron spectroscopy (XPS), FTIR spectroscopy and Raman spectroscopy. Important metrics such as the oxygen content (25.3 at.%), defect density (I_D/I_G = 0.85) and number of layers of the formed EGO were determined. The EGO was also compared with the GO prepared using the traditional chemical method, demonstrating the effectiveness of the automated electrochemical process. The electrochemical properties of the EGO, CGO and other carbon-based materials were further investigated and compared. The automated electrochemical exfoliation of natural graphite powder demonstrated in the present study does not require any binders; it is facile, cost-effective and easy to scale up for a large-scale production of graphene-based nanomaterials for various applications.     

One Pot Synthesis of Graphene through Microwave Assisted Liquid Exfoliation of Graphite in Different Solvents

This study presents an easy and quick method for the synthesis of graphene from graphite in a set of solvents, including n-Hexadecane (n-Hexa), dimethylsulfoxide (DMSO), sodium hydroxide (NaOH), 1-octanol (OCTA), perchloric acid (PA), N,N-Dimethylformamide (DMF), ethylene glycol (EG), and ethylene diamine (ED), via microwave (MW) energy. The properties of final products were determined by X-ray diffraction spectroscopy (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) spectroscopy, and the four-point probe technique. The XRD spectra of most of the MW-assisted graphene products showed peaks at 2θ = 26.5° and 54°. Layer numbers extend from 2 and 25, and the leading comes about were gotten by having two-layered products, named as graphene synthesized in dimethylsulfoxide (G-DMSO), graphene synthesized in ethylene glycol (G-EG), and graphene synthesized in 1-octanol (G-OCTA). G-DMF has the highest electrical conductivity with 22 S/m. The electrical conductivity is higher when the dipole moment of the used solvent is between 2 and 4 Debye (D). The FTIR spectra of most of the MW-assisted graphene products are in line with commercial graphene (CG). The UV-Vis spectra of all MW-assisted graphene products showed a peak at 223 nm referring to characteristic sp2 C=C bonds and 273 nm relating to the n → π * transition of C-O bonds.     

Highly Hydrogenated Graphene through Microwave Exfoliation of Graphite Oxide in Hydrogen Plasma: Towards Electrochemical Applications

Hydrogenated graphenes exhibit a variety of properties with potential applications in devices, ranging from a tunable band gap to fluorescence, ferromagnetism, and the storage of hydrogen. We utilize a one‐step microwave‐irradiation process in hydrogen plasma to create highly hydrogenated graphene from graphite oxides. The procedure serves the dual purposes of deoxygenation and concurrent hydrogenation of the carbon backbone. The effectiveness of the hydrogenation process is investigated on three different graphite oxides (GOs), which are synthesized by using the Staudenmaier, Hofmann, and Hummers methods. A systematic characterization of our hydrogenated graphenes is performed using UV/Vis spectroscopy, SEM, AFM, Raman spectroscopy, FTIR spectroscopy, X‐ray photoelectron spectroscopy (XPS), combustible elemental analysis, and electrical conductivity measurements. The highest hydrogenation extent is observed in hydrogenated graphene produced from the Hummers‐method GO, with a hydrogen content of 19 atomic % in the final product. In terms of the removal of oxygen groups, microwave exfoliation yields graphenes with very similar oxygen contents despite differences in their parent GOs. In addition, we examine the prospective application of hydrogenated graphenes as electrochemical transducers through a cyclic voltammetry (CV) study. The highly hydrogenated graphenes exhibit fast heterogeneous electron‐transfer rates, suggestive of their suitability for electrochemical applications in electrodes, supercapacitors, batteries, and sensors.     

Comparative Study of Graphite and the Products of Its Electrochemical Exfoliation

Russian Journal of Electrochemistry - A comparative study of electrochemical characteristics of graphite electrodes and precipitates of suspensions produced by the graphite exfoliation is carried...     

Bipolar Electrochemical Exfoliation of Graphite for Synthesizing Electrocatalysts of Oxygen Reduction

Russian Journal of Electrochemistry - A nanocomposite of few-layer graphene structures with cobalt oxides is synthesized for the first time in an aqueous electrolyte containing Co2+ ions by the...     

Graphite Composite Electrode in Voltammetry

Abstract

Graphite composite electrode (CCE30), composed from 30% of graphite powder and 70% of epoxy resin, was tested. Determination of aminocompounds, oxidation of adenine and guanine, and determination of manganese by differential pulse voltammetry (DPV) and direct current voltammetry (DCV) was tested in positive potential area.     

机械剥离石墨烯修饰电极检测食品接触材料中双酚A的迁移量

采用机械剥离石墨烯修饰电极快速检测食品接触材料中双酚A的迁移量。X射线电子衍射表征显示机械剥离石墨烯表面不存在含氧官能团,与化学还原石墨烯相比,机械剥离石墨烯对双酚A具有更好的电催化性能,降低了双酚A的氧化过电位,提高了电流响应。在优化的试验条件下,双酚A的浓度在1.0×10-7~1.5×10-5mol·L-1范围内与氧化峰电流呈线性关系,检出限(3S/N)为3.0×10-8mol·L-1。采用该电极对食品模拟物中的双酚A进行检测,加标回收率在85.1%~104%之间,测定值的相对标准偏差(n=6)在2.7%~5.9%之间。     

PEG在微波诱导下对高岭石插层及剥片的研究

利用微波能量，快速制备了高岭石/DMSO插层复合物，并以其为前驱体，在熔融状态，微波诱导聚乙二醇(PEG)置换出高岭石层间的DMSO，微波继续协同PEG作用，可以实现其对高岭石的剥片。同时提出了微波作用机理和微波条件下插层物对高岭石的剥片机理。采用X-射线衍射、FTIR光谱、TG-DTA、TEM等技术对插层复合物进行了表征。     

Poly(methyl methacrylate)-Assisted Exfoliation of Graphite and Its Use in Acrylonitrile-Butadiene-Styrene Composites

One of the applications of graphene in which its scalable production is of utmost importance is the development of polymer composites. Among the techniques used to produce graphene flakes, the liquid-phase exfoliation (LPE) of graphite stands out due to its versatility and scalability. However, solvents suitable for the LPE process are generally toxic and have a high boiling point, making the processing challenging. The use of low boiling point solvents could be convenient for the processing, due to the easiness of their removal. In this study, the use of poly(methyl methacrylate) (PMMA) as a stabilizing agent is proposed for the production of graphene flakes in a low boiling point solvent, that is, acetone. The graphene dispersions produced in the mixture acetone-PMMA have higher concentration, +175 %, and contain a higher percentage of few-layer graphene flakes (<5 layers), that is, +60 %, compared to the dispersions prepared in acetone. The as-produced graphene dispersions are used to develop graphene/acrylonitrile-butadiene-styrene composites. The mechanical properties of the pristine polymer are improved, that is, +22 % in the Young's modulus, by adding 0.01 wt. % of graphene flakes. Moreover, a decrease of ≈20 % in the oxygen permeability is obtained by using 0.1 wt. % of graphene flakes filler, compared to the unloaded matrix.     

Freestanding Nanolayers of a Wide-Gap Topological Insulator through Liquid-Phase Exfoliation

The layered salt Bi₁₄Rh₃I₉ is a weak three-dimensional (3D) topological insulator (TI), that is, a stack of two-dimensional (2D) TIs. It has a wide non-trivial band gap of 210 meV, which is generated by strong spin-orbit coupling, and possesses protected electronic edge-states. In the structure, charged layers of (Bi₄Rh)₃I]²⁺ honeycombs and Bi₂I₈]²⁻ chains alternate. The non-trivial topology of Bi₁₄Rh₃I₉ is an inherent property of the 2D intermetallic fragment. Here, the exfoliation of Bi₁₄Rh₃I₉ was performed using two different chemical approaches: (a) through a reaction with n-butyllithium and poly(vinylpyrrolidone), (b) through a reaction with betaine in dimethylformamide at 55 °C. The former yielded few-layer sheets of the new compound Bi₁₂Rh₃I, while the latter led to crystalline sheets of Bi₁₄Rh₃I₉ with a thickness down to 5 nm and edge-lengths up to several ten microns. X-ray diffraction and electron microscopy proved that the structure of Bi₁₄Rh₃I₉ remained intact. Thus, it was assumed that the particles are still TIs. Dispersions of these flakes now allow for next steps towards the envisioned applications in nanoelectronics, such as the study of quantum coherence in deposited films, the combination with superconducting particles or films for the generation of Majorana fermions, or studies on their behavior under the influence of magnetic or electric fields or in contact with various materials occurring in devices. The method presented generally allows to exfoliate layers with high specific charges and thus the use of layered starting materials beyond van der Waals crystals.     

碳酸钙/镍复合导电材料的原位合成及其抗静电性能

利用胶棉膜作为活性模板,制备出方解石型碳酸钙组装球,在其表面上将镍进行原位还原反应,首次成功获得了碳酸钙/镍复合导电材料,通过TEM、XRD、FT-IR和TG-DTA等测试技术对产物结构及性能进行了表征,并将产物应用于抗静电领域,制备成的抗静电涂料与用纯镍粉制备的涂料具有同等抗静电性能(电阻率为1.2×106 Ω·cm),并可以节省60%的镍。 该复合材料在导电和抗静电等领域具有应用前景,能够节省对镍的消耗。     

Towards Antimonene and 2D Antimony Telluride through Electrochemical Exfoliation

Two-dimensional (2D) layered antimony (Sb) and antimony telluride (Sb₂Te₃) are two valuable materials for optoelectronic devices and thermoelectric applications. Preparing high-quality sheets of these materials is the initial phase to promote their expected issues. Herein, micrometer-sized few-to-multilayered sheets of Sb and Sb₂Te₃ have been obtained by electrochemical exfoliation. The layered rhombohedral Sb was exfoliated in Na₂SO₄ and Li₂SO₄ electrolytes by anodic–cationic intercalation, and Sb₂Te₃ was exfoliated in Na₂SO₄. These findings are important contributions for the solution-based room-temperature electrochemical exfoliation, which is stable under glove-box-free conditions, to further improve the production of high-quality exfoliated sheets.     

聚合物石墨复合电极用于壬基酚的分析

以甲基丙烯酸甲酯(MMA)预聚物作为石墨粉的粘合剂,制备了一种电化学性能优越的聚合物石墨复合电极(PMMA-CPE),该电极能有效改善传统碳糊电极(CPE)的机械强度,提高检测重现性和电极表面电子传递速率。采用循环伏安法、计时库仑法研究了壬基酚(nP)在PMMA-CPE上的电化学行为,并考察了支持电解质、扫速、pH值等对测定的影响。实验结果表明nP在PMMA-CPE上是受吸附控制的完全不可逆的2电子2质子的电极过程。在最优条件下,采用安培检测法测得nP的氧化峰电流与其浓度在5.0×10-8～7.0×10-7mol/L和9.0×10-7～3.0×10-5mol/L范围内呈良好的线性关系,检出限(S/N=3)为6.62×10-9mol/L。该方法简便、快速,用于实际水样及土壤样品中痕量nP的分析检测,加标回收率为94%～103%。     

纳米碳与石墨碳复合材料的电化学性能

在天然石墨(NG)中掺杂不同比例的碳纳米管(CNT)得到纳米碳与石墨碳的复合材料.电化学测试结果表明,在NG中掺杂质量分数为10%的CNT所得复合材料的电化学性能最好.经过20次充放电循环,该复合材料的放电容量比同样条件下的石墨提高15.9%.纳米碳管的中空式结构和不易塌陷的特点使复合材料的充放电容量和循环稳定性明显提高.     

长链烷基季铵盐插层氧化石墨的结构变化

基于改进的Hummers法制备氧化石墨(GO),并以长链烷基季铵盐(C_nTAB)对其进行插层处理;通过改变C_nTAB的链长、浓度,得到系列C_nTAB/GO插层复合物。采用XRD和元素分析对产物的最大底面间距及C_nTAB插入量进行表征。结果表明,随着C_nTAB链长的增长、C_nTAB浓度的增大,C_nTAB/GO插层复合物的最大底面间距逐渐增大。C_nTAB通过离子键作用和疏水键作用插入到GO层间,在GO片层上的吸附规律符合修正型(Modified)Langmuir模型,即C_nTAB以单分子层吸附在GO片层上。根据C_nTAB/GO插层复合物最大底面间距及C_nTAB插入量的变化规律分析,得出C_nTAB在GO层间的排布模式有单层平躺模式、类双层平躺模式、单层倾斜模式和单层直立模式。     

Exfoliation of Graphite into Graphene in Polar Solvents Mediated by Amphiphilic Hexa‐peri‐hexabenzocoronene

A water‐soluble surfactant consisting of hexa‐peri‐hexabenzocoronene (HBC) as hydrophobic aromatic core and hydrophilic carboxy substituents was synthesized. It exhibited a self‐assembled nanofiber structure in the solid state. Profiting from the π interactions between the large aromatic core of HBC and graphene, the surfactant mediated the exfoliation of graphite into graphene in polar solvents, which was further stabilized by the bulky hydrophilic carboxylic groups. A graphene dispersion with a concentration as high as 1.1 mg L^?1 containing 2–6 multilayer nanosheets was obtained. The lateral size of the graphene sheets was in the range of 100–500 nm based on atomic force microscope (AFM) and transmission electron microscope (TEM) measurements.     

Sn-SnSb/石墨复合材料的制备及电化学性能

以柠檬酸钠为配位剂、NaBH4为还原剂，将Sn(Ⅱ)和Sb(Ⅲ)盐在水溶液中共还原制得Sn-SnSb合金。X射线衍射和扫描电镜的测试结果表明：所得合金为多相合金，颗粒大小约200 nm。将该合金粉和石墨按质量比4∶1经机械球磨形成Sn-SnSb/石墨复合材料，将其作为锂离子电池阳极材料进行电化学性能测试，结果表明，该复合材料可逆容量超过600 mAh·g^-1，具有良好的循环性能，15次循环内的稳定比容量为461 mAh·g^-1，而纯Sn-SnSb合金粉15次循环后充电比容量为337 mAh·g^-1。     

红磷/石墨复合材料的制备及电化学性能

研究了一种先通过机械球磨和水热法制得的亚微米红磷,再通过球磨亚微米红磷与石墨得到的块状亚微米红磷/石墨复合材料(smRP/G),并利用扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱分析(XPS)、循环伏安法(CV)等手段其进行了表征。 相对比普通红磷,亚微米红磷更容易通过球磨与石墨复合,能有效提升石墨材料的储锂容量。 为红磷在锂离子电池负极材料上的应用提供了一种思路。 在少量添加红磷的条件下,当红磷质量分数为3%时smRP/G表现最佳(3%smRP/G)。 在100 mA/g电流密度下展示出了1417 mA·h/g的首次放电容量,首次库伦效率67.4%。 并在循环200圈后依然保持着700 mA·h/g的可逆循环容量。