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1.
While great progress has been achieved in the synthesis of ordered mesoporous carbons in the past decade, it still remains a challenge to prepare highly graphitic frameworks with ordered mesoporosity and high surface area. Reported herein is a simple synthetic methodology, based on the conversion of self‐assembled superlattices of Fe3O4 nanocrystals, to fabricate highly ordered mesoporous graphene frameworks (MGFs) with ultrathin pore walls consisting of three to six stacking graphene layers. The MGFs possess face‐centered‐cubic symmetry with interconnected mesoporosity, tunable pore width, and high surface area. Because of their unique architectures and superior structural durability, the MGFs exhibit excellent cycling stability and rate performance when used as anode materials for lithium‐ion batteries, thus retaining a specific capacity of 520 mAh g?1 at a current density of 300 mA g?1 after 400 cycles.  相似文献   

2.
A facile method for the large‐scale synthesis of SnO2 nanocrystal/graphene composites by using coarse metallic Sn particles and cheap graphite oxide (GO) as raw materials is demonstrated. This method uses simple ball milling to realize a mechanochemical reaction between Sn particles and GO. After the reaction, the initial coarse Sn particles with sizes of 3–30 μm are converted to SnO2 nanocrystals (approximately 4 nm) while GO is reduced to graphene. Composite with different grinding times (1 h 20 min, 2 h 20 min or 8 h 20 min, abbreviated to 1, 2 or 8 h below) and raw material ratios (Sn:GO, 1:2, 1:1, 2:1, w/w) are investigated by X‐ray diffraction, X‐ray photoelectron spectroscopy, field‐emission scanning electron microscopy and transmission electron microscopy. The as‐prepared SnO2/graphene composite with a grinding time of 8 h and raw material ratio of 1:1 forms micrometer‐sized architected chips composed of composite sheets, and demonstrates a high tap density of 1.53 g cm?3. By using such composites as anode material for LIBs, a high specific capacity of 891 mA h g?1 is achieved even after 50 cycles at 100 mA g?1.  相似文献   

3.
A highly oriented mesoporous graphitic carbon nanospring (OGCS) with graphitic layers that are perpendicular to the axis is prepared by hydrothermal treatment of epoxy resin at 500 °C and annealing at 1400 °C. Water plays an important role in not only forming the graphitic carbon nanospring with a high [002] orientation and a large amount of active edge‐plane sites, but also in the generation of the mesoporous structure, which facilitate fast K‐ion adsorption and diffusion. In situ and ex situ measurements confirm that OGCS undergoes K‐adsorption in mesopores and then K‐intercalation in the graphite layer to form KC8 with a low discharge voltage. The spring‐like nanostructure can expand one‐dimensionally along the axial direction to accommodate the volume variation. The OGCS electrode thus shows a much better K‐storage performance than that of unoriented graphitic carbon.  相似文献   

4.
We present in this report a new type of particles with micrometer-order sizes, which we called giant graphitic balls (GG balls). The GG balls are produced by CO2 laser ablation of graphite together with single-wall carbon nanohorns. They have graphitic structures whose layers tend to align parallel with the GG-ball surfaces, resulting in polygonal-like arrangements. Comparing the GG-ball structure with that of the previously reported polygonal graphite-particles, the growth mechanism of the GG ball is discussed briefly.  相似文献   

5.
Thin‐layer 2D materials have been attracting enormous interest, and various processes have been investigated to obtain these materials efficiently. In view of their practical applications, the most desirable source for the preparation of these thin‐layer materials is the pristine bulk materials with stacked layers, such as pristine graphite. There are many options in terms of conditions for the exfoliation of thin‐layer materials, and these include wet and dry processes, with or without additives, and the kind of solvent. In this context, we found that the versatile exfoliant hexahydroxytriphenylene works efficiently for the exfoliation of typical 2D materials such as graphene, MoS2, and hexagonal boron nitride (h‐BN) by both wet and dry processes by using sonication and ball milling, respectively, in aqueous and organic solvents. As for graphene, stable dispersions with relatively high concentrations (up to 0.28 mg mL?1) in water and tetrahydrofuran were obtained from graphite in the presence of hexahydroxytriphenylene by a wet process with the use of bath sonication and by a dry process involving ball milling. Especially, most of the graphite was exfoliated and dispersed as thin‐layer graphene in both aqueous and organic solvents through ball milling, even on a large scale (47–86 % yield). In addition, the exfoliant was easily removed from the precipitated composite by heat treatment without disturbing the graphene structure. Bulk MoS2 and h‐BN were also exfoliated by both wet and dry processes. Similar to graphene, dispersions of MoS2 and h‐BN of high concentrations in water and DMF were produced in high yields through ball milling.  相似文献   

6.
Graphitic materials with intercalated sites are considered as the mostly used positive electrode materials in nonaqueous Al batteries. Unlike the small‐size cations, the intercalation/de‐intercalation of large‐size anions into/out of graphite would induce large volume expansion and micro‐structure reconfiguration, leading to unexpected coulombic efficiency in the full cells (<95% within initial several cycles). For understanding the irreversible processes induced by anion intercalation/de‐intercalation (AlCl4), here the kinetics of first two cycles for the Al‐graphite batteries have been systematically studied. To study kinetics behaviors at representative states, a combined method upon galvanostatic intermittent titration technique and electrochemical impedance spectroscopy has been carried out. The achieved diffusion coefficients of the positive electrodes assembled with different graphite sizes suggest that size effect also plays a critical role in determining the electrochemical kinetics in the mass transport in both electrolyte and graphitic layers as well as in interface reaction. The morphologies and micro‐structures of the post‐cycled graphite electrodes have been also experimentally studied, which also well supports the irreversible intercalation/de‐intercalation behaviors in graphite electrodes. The results offer a significant platform to well understand the essential factors in tailoring coulombic efficiency from a kinetic view, which would be helpful in promoting the graphite electrodes in Al batteries.  相似文献   

7.
Pristine and Co‐doped LiMnPO4 have been synthesized by the sol‐gel method using glycine as a chelating agent and the carbon composites were obtained by the wet ball mill method. The advantage of this method is that it does not require an inert atmosphere (economically viable) and facilitates a shorter time for synthesis. The LiCo0.09Mn0.91PO4/C nanocomposites exhibit the highest coulombic efficiency of 99 %, delivering a capacity of approximately 160 mAhg?1 and retain a capacity of 96.3 % over the investigated 50 cycles when cycled between 3–4.9 V at a charge/discharge rate of 0.1 C.  相似文献   

8.
A cyclic voltammetry method is used to show that the process of reduction of sodium (and, possibly, lithium) out of melts of corresponding chlorides on the molybdenum, glassy-carbon, and graphite electrodes is complicated by the process of dissolution of the corresponding alkali metal in the melt. A notion called “reversibility of material balance” is introduced. The notion reflects the ratio of the amount of substance that undergoes oxidation in the anodic half-cycle of a voltammetric curve to the amount of substance that is deposited in the cathodic half-cycle of the curve. The adsorption of sodium and lithium on glassy carbon and graphite plays an important role in the process of reduction, leading to an increase in the reversibility of the process. This is pronounced especially strongly at potential scan rates below 1 V s?1. The sodium intercalation into graphite leads to a decrease in the reversibility of the process of reduction, the more so at potential scan rates below 0.03 V s?1. However, the intercalation of lithium (probably because of its small atomic radius) does not exert practically any influence on the reversibility of process at the above potential scan rates.  相似文献   

9.
An array of carbon composite electrodes embedded in a 96 well microtitration plate was fabricated and applied for DPV determination of the environmental pollutant triclosan (5‐chloro‐2‐(2,4‐dichlorophenoxy)‐phenol). For the preparation of composite electrodes, graphite and glassy carbon conductive microparticles were tested in combination with several types of polymers as nonconductive binders. For the measurements, combinations of graphitic carbon particles with polystyrene (C‐PS) and with polycarbonate (C‐PC) were selected. The achieved limit of detection was 0.49 µmol L?1 for C‐PS electrodes and 0.25 µmol L?1 for C‐PC electrodes in the selected optimum medium. The method was successfully applied for practical samples of river water and toothpaste.  相似文献   

10.
氧化石墨的谱学表征及分析   总被引:1,自引:2,他引:1  
采用改进的Hummers法,通过改变氧化剂用量获得不同氧化程度的氧化石墨,用X射线衍射(XRD)、红外光谱(FTIR)和拉曼光谱(Raman)对产物进行结构和谱学特性的表征,并结合数学分析软件对部分红外和拉曼数据进行分峰拟合。结果表明,石墨经氧化后形成了含有C-OH、-COOH和C-O-C等官能团的石墨层间化合物;氧化剂用量较少时,石墨片层插层氧化不完全,产物的结构中仍存在未被氧化的原石墨周期性结构;随着氧化剂用量的增加,氧化石墨产物的XRD图中原石墨(002)衍射峰逐渐消失,结构中含氧官能团的量逐渐增加,产物的亲水性也逐渐增强;通过对红外光谱的拟合发现,氧化石墨样品在3 198 cm-1附近有一个红外吸收峰,应归属于C-OH中OH的伸缩振动;随着氧化剂用量的增加,所得氧化石墨产物的拉曼光谱中D峰与G峰的强度积分比R(ID/IG)逐渐增大,产物结构中sp2平面域的平均尺寸逐渐减小。  相似文献   

11.
Graphene, as a single layer of graphite, is currently the focal point of research into condensed matter owing to its promising properties, such as exceptional mechanical strength, high thermal conductivity, large specific surface area, and ultrahigh electron‐transport properties. Therefore, various physical and chemical synthetic procedures to prepare graphene and/or graphene nanoplatelets have been rapidly developed. Specifically, the synthesis of edge‐selectively functionalized graphene (EFG) has been recently reported by using simple and scalable approaches, such as “direct” Friedel‐Crafts acylation reactions in a mild acidic medium and a mechanochemical ball‐milling process. In these approaches, chemical functionalization predominantly take place at the edges of the graphitic layers via the covalent attachment of targeted organic “molecular wedges”. In addition, the distortion of the crystalline structures in the basal plane, which is beneficial for preserving the unique properties of the graphitic framework, can be minimized. In addition, the efficient exfoliation of graphene can be achieved, owing to the strong repulsive forces from the covalently linked wedges and strong shear forces during the reaction. Furthermore, EFG shows promising potential in many useful applications, such as highly conductive large‐area films, metal‐free electrocatalysts for the oxygen‐reduction reaction (ORR), and as additives in composite materials with enhanced properties. Herein, we summarize the recent progress and general aspects of EFG, including synthesis, reaction mechanism, properties, and applications.  相似文献   

12.
Four vanadium oxide layers on mineral TiO2(001)‐anatase supports with different thickness (3–33 Å) were prepared with reactive d.c. magnetron sputtering and were extensively studied with photoelectron spectroscopy. Al Kα radiation and 150 eV synchrotron radiation were used as excitation sources. The evolution of the 2p, 3s and 3p core level line shapes of V and Ti as a function of the vanadium oxide thickness was studied, as well as the O1s and O2s core lines and the valence band. All the V2p spectra of the deposited vanadium oxide layers consist of at least 60% V5+, the rest being V4+. The V3p region is complicated by multiplet splitting, which prevents the determination of the vanadium oxidation state. The V3p multiplet splitting is different for the two excitation energies. No reduction of the titania support surface due to the vanadium oxide deposition was observed. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

13.

In present work, we describe the synthesis of graphite intercalation compounds with perrhenic acid (HReO4-GIC) through the anodic oxidation of graphite in aqueous perrhenic acid solution and their thermal exfoliation. Due to electrochemical treatment of graphite in perrhenic acid solution, ReO4 ions are intercalated into interlayer spaces of graphite. Anodic oxidation of graphite in HReO4 solution leads to the formation of 3-stage GIC. Simultaneously, some amount of perrhenic acid becomes deposited on the graphite surface and edges. In the next step, thermal treatment of the previously synthesized GIC was performed, causing both the exfoliation of graphitic structure and transformation of perrhenic acid into rhenium oxides on the surface of graphene layers. The yielded product was exfoliated graphite-ReO2/ReO3 composite. The obtained composite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy. Additionally, specific surface area of the exfoliated materials was measured.

  相似文献   

14.
A superfine expanded graphite (s‐EG) fiber material was investigated as an anode material for lithium‐based batteries. The fibers were prepared by decomposition of dicarbon monofluoride‐intercalated graphite. The high resolution transmission electron microscopy (HRTEM) images showed the fiber thickness in range of 2–3 nm with several microns in length. Lithium storage capacity in this material was measured in lithium half cells. High lithium storage capacity of about 1000 mAh · g–1 at a rate of C/10, corresponding to Li3C6 composition was obtained. The material showed fairly good rate capability exhibiting lithium storage capabilities even at 60C. As a effect of ball milling, the s‐EG showed crystallographic ordering in the sample with reduced the lithium storage capacity corresponding to composition of LiC6. A simple mathematical relation to account for the excess lithium storage capacity in this material is put forward.  相似文献   

15.
In this work, we present the application of an exfoliated graphite electrode modified with gold nanoparticles (AuNPs) for the detection of As(III) in acidic media. Gold nanoparticles were deposited on the surface of an exfoliated graphite electrode by electrodeposition at a potential window of ?0.2 V to 1.2 V. This was followed by activation in 0.5 M H2SO4 with 10 cycles from 0.6 V to 1.4 V. The modification of exfoliated graphite (EG) showed an increased electroactive surface area of the electrode and improved peak current output in a Fe(CN)63?/4? redox probe. EG‐AuNPs electrode was used to detect As(III) in 1.0 M HNO3 using square wave anodic stripping voltammetry (SWASV) technique at optimum conditions of pH 3, deposition potential of ?0.8 V, deposition time of 180 s, frequency of 5 Hz and pulse amplitude of 50 mV. The EG‐AuNPs electrode detected As(III) in solution to a limit of 0.58 ppb with regression of 0.9993. The method reported is simple, cheap and possesses good reproducibility. The developed electrochemical sensor was applied in the detection of As (III) in an industrial real water sample. The results of the real water sample analysis from the developed method are comparable with the inductively coupled plasma – optical emission spectroscopy (ICP‐OES) results.  相似文献   

16.
采用"自上而下"方法制备了具有少片层、小尺寸特征且晶型结构完美的石墨材料,通过增加离子嵌入位点的方式,突破传统石墨作为正极材料的固有容量限制,提升铝离子电池的电化学储能性能。扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)等测试结果表明,该方法可以在不破坏石墨材料本身结构的前提下,有效实现对石墨片层的剥离,并且可以通过调节球磨时间的方式实现对石墨片层厚度和尺寸的调控。电化学测试结果表明,在3C的大电流密度下,以剥离的石墨材料为正极的铝离子电池放电容量可以达到93 mAh·g-1,在10C的高倍率下,放电容量仍保持在68 mAh·g-1,并显示出优异的循环性能。另外,该方法制备工艺简单、成本低廉,为促进高容量、长寿命铝离子电池的商业化应用打下了良好的基础。  相似文献   

17.
In this work, dual‐column capillary microextraction (CME) system consisting of N‐(2‐aminoethyl)‐3‐aminopropyltrimethoxysilane (AAPTS)‐silica coated capillary (C1) and 3‐mercaptopropyl trimethoxysilane (MPTS)‐silica coated capillary (C2) was developed for sequential separation/preconcentration of arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid [MMA(V)] and dimethylarsinic acid [DMA(V)] in the extracts of human hair followed by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV‐ICP‐MS) detection with iridium as permanent modifier. Various experimental parameters affecting the dual‐column microextraction of different As species had been investigated in detail. It was found that at pH 9, As(V) and MMA could be quantitatively retained by C1 and only As(III) could be quantitatively retained by C2. With the aid of valve switching, As(V)/MMA(V) retained on C1 and As(III) retained on C2 could be sequentially desorbed by 10 µl of 0.01 mol l?1 HNO3 [for As(V)], 0.1 mol l?1 HNO3 [for MMA(V)] and 0.2 mol l?1 HNO3‐3% thiourea (m/v) [for As(III)], respectively, the eluents were immediately introduced into the Ir‐coated graphite tubes for further ETV‐ICP‐MS detection. With two‐step ETV pyrolysis program, Cl? in the sample matrix could be in situ removed, and the total As in the human hair extracts or digested solution could be interference‐free, determined by ETV‐ICP‐MS. DMA(V) in the human hair extracts was obtained by subtraction of total As in the human hair extracts from other three As species. Under the optimized conditions, the detection limits (3 σ) of the method were 3.9 pg ml?1 for As(III), 2.7 pg ml?1 for As(V), 2.6 pg ml?1 for MMA(V) and 124 pg ml?1 for total As with the relative standard deviations less than 7.0% (C = 0.1 ng ml?1, n = 7), and the enrichment factor was 286, 262 and 260 for As(III), As(V) and MMA(V), respectively. The developed method was successfully applied for the speciation of arsenic in the extracts of human hair. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

18.
Two 2D covalent organic frameworks (COFs) linked by vinylene (?CH=CH?) groups (V‐COF‐1 and V‐COF‐2) are synthesized by exploiting the electron deficient nature of the aromatic s‐triazine unit of C3‐symmetric 2,4,6‐trimethyl‐s‐triazine (TMT). The acidic terminal methyl hydrogens of TMT can easily be abstracted by a base, resulting in a stabilized carbanion, which further undergoes aldol condensation with multitopic aryl aldehydes to be reticulated into extended crystalline frameworks (V‐COFs). Both V‐COF‐1 (with terepthalaldehyde (TA)) and V‐COF‐2 (with 1,3,5‐tris(p‐formylphenyl)benzene (TFPB)) are polycrystalline and exhibit permanent porosity and BET surface areas of 1341 m2 g?1 and 627 m2 g?1, respectively. Owing to the close proximity (3.52 Å) of the pre‐organized vinylene linkages within adjacent 2D layers stacked in eclipsed fashion, [2+2] photo‐cycloadditon in V‐COF‐1 formed covalent crosslinks between the COF layers.  相似文献   

19.
A detailed study of the electrochemical oxidation of Benzo[a]pyrene (BaP) at the glassy carbon and pencil graphite electrodes was carried out in aqueous and nonaqueous media. Using square‐wave stripping mode, the compound yielded a well‐defined voltammetric response at pencil graphite electrode in acetate buffer, pH 4.8 at +1.13 V (vs. Ag/AgCl) (a preconcentration step being carried out at a fixed potential of +0.70 V for 180 s). The process could be used to determine BaP concentrations in the range 0.25–1.25 μM, with a detection limit of 0.027 μM (6.82 μg L?1). The applicability to assay of spiked human urine samples was also illustrated.  相似文献   

20.
Numerous carbonaceous materials have been studied as anodes of lithium ion batteries during the past several years[1 ̄4].Graphite was favored for battery applications because it exhibits a high specific capac- ity, low working potential close to that of l…  相似文献   

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