2020 Vol. 35, No. 6

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2020, 35(6): .
Abstract(88) PDF(281)
Abstract:
A review of graphynes: properties, applications and synthesis
LI Xu, LI Bao-hua, HE Yan-bing, KANG Fei-yu
2020, 35(6): 619-629. doi: 10.1016/S1872-5805(20)60518-2
Abstract(1492) PDF(516)
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Graphyne, a kind of sp-sp2 hybrid all-carbon two-dimensional material, is currently one of the most interesting carbon allotropes besides graphene. It has potential applications and characteristic properties because of its unique electronic structure. First, the concept and properties of graphyne are summarized, then the characteristic properties of graphynes and their potential applications are reviewed, before some methods and ways to synthesize the two-dimensional structures are proposed, and finally a short perspective on the study of graphynes is given.
Recent progress on the design of hollow carbon spheres to host sulfur in room-temperature sodium-sulfur batteries
YANG Jia-ying, HAN Hao-jie, Hlib Repich, ZHI Ri-cheng, QU Chang-zhen, KONG Long, Stefan Kaskel, WANG Hong-qiang, XU Fei, LI He-jun
2020, 35(6): 630-645. doi: 10.1016/S1872-5805(20)60519-4
Abstract(2915) PDF(400)
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Room-temperature sodium-sulfur (RT-Na/S) batteries are an important class of rechargeable batteries with a high theoretical capacity of 1 675 mAh g-1 and energy density up to 1 276 Wh kg-1 (based on Na2S). They are recognized as attractive next-generation high-energy-density devices for large-scale energy storage owing to the abundance and low cost of sodium and sulfur. However, similar to the working principle in lithium-sulfur batteries, they suffer from some basic problems such as the poor conductivity of elemental sulfur, a large volume change during charge-discharge cycling and a serious shuttle effect caused by sodium polysulfide dissolution. Moreover, the shuttle effect and volume change seem more pronounced in RT-Na/S batteries, which further decreases their performance and seriously hinders the progress towards their practical application. A fast growth in designing porous carbons, especially hollow carbon spheres (HCSs), as a sulfur host to address these problems has been seen in recent years, due to their unique structural features such as a large void space, a permeable shell, and simple functionalization. This review summarizes recent progress in HCS-based materials as the sulfur hosts in RT-Na/S batteries. Beginning with a brief introduction to RT-Na/S batteries, carbon hosts and design strategies for preparing HCSs, particular emphasis is placed on manipulating the pore structure, heteroatom doping and decoration with metal species with the aim of alleviating the "shuttle effect" and thus improving the performance. Finally, perspectives on current challenges and future research directions are discussed.
A review on the preparation and applications of coal-based fluorescent carbon dots
CAI Ting-ting, LIU Bin, PANG Er-nan, REN Wei-jie, LI Shi-jia, HU Sheng-liang
2020, 35(6): 646-666. doi: 10.1016/S1872-5805(20)60520-0
Abstract(1210) PDF(351)
Abstract:
Deep processing and functional applications of coal are important strategies to overcome the bottleneck of current coal applications. In recent years, the fluorescent carbon dots (CDs), a new member of the carbon nanomaterials family, have shown great application prospects in biological imaging, chemical sensing and photocatalysis owing to their excellent biocompatibility, non-toxicity, tunable fluorescence emission, outstanding energy storage performance and other unique properties. Coal and coal-derived materials contain large amounts of crystallite structure and condensed aromatic ring clusters, which are connected by the densely distributed carbon-oxygen bonds. The linkage can be broken by chemical, electrochemical or physical methods to obtain fluorescent CDs. Therefore, the coal and coal-derived materials with wide distribution, large reserves and low price are ideal source materials for preparation of CDs. Herein, we summarize the preparation methods of CDs from coal together with their merits and demerits. Meanwhile, the effects of the type of coal and coal-derived materials and preparation conditions on the properties of fluorescent CDs are analyzed. Furthermore, the properties and applications of coal-based CDs and their nanocomposites in chemical detection, biological imaging and photocatalysis are outlined with emphasis on the formation of heterogeneous structures in nanocomposites based on CDs. Finally, the future development of coal-based CDs is prospected. It is expected that this review will provide key information for the preparation and applications of coal-based CDs, thus providing an economical and sustainable choice for the comprehensive utilization of coal.
The use of carbon materials in persulfate-based advanced oxidation processes: A review
XIAO Peng-fei, AN Lu, WU De-dong
2020, 35(6): 667-683. doi: 10.1016/S1872-5805(20)60521-2
Abstract(1820) PDF(291)
Abstract:
With their unique nanostructure, excellent conductivity, chemical stability and adsorption properties, carbon materials have a wide range of application possibilities in the field of catalysis, and are expected to become a new generation of green non-metallic catalysts. In recent years, worldwide research on the applications of various carbon materials in the advanced oxidation technology using activated persulfate (PS) has developed rapidly. Here, theoretical and applied research progress on graphene-based materials, carbon nanotubes, carbon fibers, porous carbons, carbon aerogels, carbon microspheres, carbon nanobubbles and carbon quantum dots as heterogeneous catalysts to activate peroxymonosulfate and peroxydisulfate are reviewed. The preparation methods and structural characteristics of the carbon catalysts, the relationship between their structure and activity in the activation of PS, the paths for the generation of free radicals and non-free radicals, and the uses of carbon materials in the degradation of pollutants by activated PS are summarized. Finally, the challenges of poor stability, environmental risks and high costs of carbon catalysts in practical applications and their solutions are pointed out, with the aim of providing references for the further applications of carbon materials in advanced oxidation technologies.
Construction of three-dimensional all-carbon C60/graphene hybrids and their use as electrodes for high performance supercapacitors
CHENG Lei, LI Xing-juan, LI Jing, QIU Han-xun, XUE Yu-hua, Kuznetsova-Iren Evgenyevna, Vladimir Kolesov, CHEN Cheng-meng, YANG Jun-he
2020, 35(6): 684-695. doi: 10.1016/S1872-5805(20)60522-4
Abstract(780) PDF(144)
Abstract:
Control of the three-dimensional (3D) pore structure of all-carbon C60/graphene hybrids was conducted by introducing C60 molecules into graphene laminates by a simple hydrothermal method to improve their performance as electrodes in supercapacitors. Results indicate that the strong π-π interaction between carbon hexagons in C60 and graphene skeletons favors the self-assembly of the 3D pore structure of the C60/graphene hybrids under hydrothermal conditions. The addition of C60 molecules gives the hybrids a hierarchical pore structure and redox-active sites, which contribute remarkably to the improved electrochemical performance. A specific capacitance of 332.3 F·g-1 at a current density of 1 A·g-1 was obtained in a 6 mol·L-1 potassium hydroxide solution for a hybrid optimized by an orthogonal experimental design method, which is 54.5% higher than that of the graphene without C60. This finding indicates that the all-carbon hybrids may be used as more competitive and promising electrodes for the fabrication of high performance supercapacitors.
A lithium ion-imprinted adsorbent using magnetic carbon nanospheres as a support for the selective recovery of lithium ions
LIANG Qi, ZHANG Er-hui, YAN Guang, YANG Yong-zhen, LIU Wei-feng, LIU Xu-guang
2020, 35(6): 696-706. doi: 10.1016/S1872-5805(20)60533-9
Abstract(590) PDF(132)
Abstract:
A magnetic carbon-based lithium ion-imprinted material (Li+-IIP-Fe3O4@C) with a high Li+ adsorption selectivity was designed and prepared by a surface ion imprinting method, using magnetic carbon nanospheres (Fe3O4@C) as the carrier and 2-hydroxymethyl-12-crown-4 as the adsorption unit. First, Fe3O4@C was silanized by γ-methacryloxypropyltrimethoxysilane to obtain Si-Fe3O4@C which was then functionalized with methacrylic acid (MAA), followed by polymerization to obtain PMAA-Fe3O4@C with a regular morphology and a high degree of MAA grafting. Finally, 2-hydroxymethyl-12-crown-4 was grafted onto the surface of PMAA-Fe3O4@C in the presence of LiClO4 under catalysis by p-toluenesulfonic acid. This was cross-linked by ethylene glycol dimethacrylate and eluted by a HNO3 solution to obtain Li+-IIP-Fe3O4@C. The kinetic adsorption and isothermal adsorption results for this material show that the adsorption of Li+ conforms to a pseudo-second-order kinetic model and has Langmuir isotherms. The maximum adsorption capacity of Li+-IIP-Fe3O4@C for Li+ is 22.26 mg/g at 25 ℃. The selection factors of Li+ against Na+, K+ and Mg2+ are 8.06, 5.72, and 2.75, respectively. The Li+ adsorption capacity of Li+-IIP-Fe3O4@C decreases by only 8.8% after six adsorption-desorption cycles, demonstrating an excellent regeneration capability and making it very useful for lithium recovery.
The preparation of super lightweight magnetic Fe3O4/graphene/carbon aerogels and their use in electromagnetic interference shielding
ZHANG En-shuang, LEI Chao-shuai, LI Jian, LIU Yuan-yuan, GAO Yu-zhi, LU Tong, LI Wen-jing, ZHANG Hao
2020, 35(6): 707-715. doi: 10.1016/S1872-5805(20)60524-8
Abstract(577) PDF(106)
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Magnetic Fe3O4/graphene/carbon aerogels were prepared by the sol-gel method, followed by supercritical drying and pyrolysis. The microstructures, electrical properties and electromagnetic interference shielding performance of the aerogels were investigated. The aerogels were crushed into a fine powder with a bimodal particle size distribution (~0.1 and 10 μm) and released into a chamber to a particle concentration of 1 g m-3 at room temperature under atmosphere pressure using a dispensing device, where electromagnetic interference shielding was tested. Results indicate that the composite aerogels have high conductivity and a hierarchical pore structure with a density as low as 0.015 g cm-3. The concentration of the fine powder in the chamber decreased with time and levelled off above 20 min. The shielding is dominated by the particles that are difficult to settle due to their perturbation by air. The shielding for the visible wave band of the composite aerogels in powder form initially and after the release for 30 min are above 99.90% and 98.77%, respectively. Those for 3-5 μm and 8-12 μm infrared light are respectively 99.55% and 99.35% initially, and 99.05% and 96.79% after the release for 30 min. For the millimeter wave band, the shielding ratios initially and after the release for 30 min are above 83.68% and 82.54%, respectively.
Synthesis of narrow graphene nanoribbons by a metal-catalyzed axial unzipping method
WANG Kai, ZHOU Qing-ping, CHEN Zhi-gang, CHEN You-xin, HE Zhi-yan, JIANG Sheng-hao, CHEN Jie, CHEN Chang-xin
2020, 35(6): 716-721. doi: 10.19869/j.ncm.1007-8827.20200012
Abstract(553) PDF(113)
Abstract:
Narrow graphene nanoribbons (GNRs) have great prospects for use in electronic and optoelectronic devices owing to their sizable band gap. However, there has been no good way to prepare high-quality GNRs with a narrow width. Here, a method is reported to prepare narrow, high-quality GNRs and single-wall carbon nanotube (SWCNT)/GNR intramolecular heterojunctions by the metal-catalyzed axial unzipping of SWCNTs, using sputtered Pd as the catalyst at 750 and 800 ℃ under a mixed gas flow of Ar and H2. The unzipping process parameters were optimized. It was found that the unzipping rate of SWCNTs can be adjusted by controlling the hydrogen flow rate. The prepared narrow GNRs and GNR/SWCNT intramolecular heterojunctions are promising for use in next-generation electronic and optoelectronic devices.
Effects of the degree of oxidation of pitch fibers on their stabilization and carbonization behaviors
PENG Yuan-shuo, YANG Jian-xiao, SHI Kui, GUO Jian-guang, ZHU Hui, LI Xuan-ke
2020, 35(6): 722-730. doi: 10.1016/S1872-5805(20)60515-7
Abstract(877) PDF(154)
Abstract:
The stabilization of isotropic pitch-derived fibers (IPFs) and mesophase pitch-derived fibers (MPFs) in air was performed at different heating rates and with different final stabilization temperatures. The stabilized fibers (SFs) and carbon fibers (CFs) were characterized by elemental analysis, FT-IR, TG-MS and SEM to investigate the influence of the degree of oxidation of the SFs on the microstructures and mechanical properties of the CFs. Results showed that a slow heating rate during stabilization was beneficial to the oxidative cross-linking of PFs, and the corresponding CFs had a higher carbonization yield and tensile strength at the lower heating rate. When both IPF and MPF were stabilized at 270 ℃, the two resulting CFs all reached their optimal performance. In addition, the FTIR peak intensity ratio of the C=O band at about 1 700 cm-1 to the C=C band at 1 600 cm-1 of the SFs had a good relationship to the carbonization yield and tensile strength of the CFs, and this can be used to optimize the degree of oxidation of the SFs. Moreover, insufficiently stabilized fibers released a great deal of H2 and CH4, causing some porosity in the resulting CFs with a low tensile strength, especially for the insufficiently stabilized IPCF. While over-stabilized fibers released a large amount of CO and CO2, causing cracked textures in the corresponding CFs, especially in the over-stabilized MPCF. Therefore, this research into the stabilization and carbonization behaviors of pitch fibers has great significance for improving the mechanical properties of pitch-based CFs.
Synthesis of a rGO/NiO composite with a hierarchical pore structure by self-assembly and its electrochemical performance as a supercapacitor electrode
YUAN Shu-xia, YANG Ming-hui, LU Chun-xiang, WANG Xiao-min
2020, 35(6): 731-738. doi: 10.1016/S1872-5805(20)60525-X
Abstract(508) PDF(123)
Abstract:
A GO/Ni(HCO3)2 composite was synthesized by the self-assembly of layer Ni(HCO3)2 and GO in a mixed suspension under sonication, followed by heat treatment to obtain rGO/NiO for use as the electrode material of supercapacitors. The structural change from the GO/Ni(HCO3)2 to the rGO/NiO was investigated by XRD, SEM, and nitrogen adsorption. Results indicate that the rGO/NiO has a specific surface area of 121.3 m2 g-1 and pore volume of 0.26 cm3 g-1, and a hierarchical porous structure with a pore size range of 2-100 nm. The high specific surface area and the hierarchical porous structure give the rGO/NiO composite a high specific capacitance of 919 F g-1 (0.5 A g-1) and an excellent rate capability with a capacitance retention rate of 71% when the current density increases from 0.5 to 5 A g-1. The specific capacitance retains 91% of its original value after cycling at a current density of 2 A g-1 for 3 000 cycles, indicating good stability.
Permeation of water, ammonia and dichloromethane through graphene oxide/polymeric matrix composite membranes
Ali Asghar Zomorodkia, Saeed Bazgir, Davood Zaarei, Mohsen Gorji, Mehdi Ardjmand
2020, 35(6): 739-751. doi: 10.1016/S1872-5805(20)60514-5
Abstract(430) PDF(92)
Abstract:
The permeation of polar molecules (water and ammonia), non-polar dichloromethane and a mixture of ammonia and dichloromethane through graphene oxide (GO)/polymer matrix composite membranes was investigated. Results indicated that a hydrophilic poly(2-acrylamido -2 -methyl propane sulfonic acid) (PAMPS) based membrane had the highest permeability for water and ammonia due to the high hydrophilicity of the polymer matrix while a hydrophobic polyurethane (PU)-based membrane had the best permeation performance for dichloromethane and the worst performance for water and ammonia. Adding the GO to PU or PAMPS polymers increases the negative charge due to the negatively charged nature of GO caused by its oxygen-containing functional groups, which increases the amounts of absorbed water and ammonia due to the positive charge of the hydrogen atoms in these two molecules.
Effects of fiber and matrix properties on the compressive strength of carbon fiber reinforced polymer composites
LI Ai-jun, ZHANG Jun-jun, ZHANG Fang-zhou, LI Long, ZHU Shi-peng, YANG Yun-hua
2020, 35(6): 752-761. doi: 10.1016/S1872-5805(20)60526-1
Abstract(609) PDF(114)
Abstract:
The axial compressive strength of carbon fiber reinforced polymer composites (CFRP) is significantly lower than the tensile strength, which hinders its wide applications. The failure mechanism of CFRP under unidirectional compression parallel to the fiber alignment direction is complex, but research on this issue is limited. In order to understand this mechanism more deeply and intuitively, a two-dimensional microscopic numerical model is proposed. The influences of various properties of the fiber and matrix on the compressive strength of CFRP are investigated, including the axial elastic modulus of the fiber (Ef1), the transverse elastic modulus of the fiber(Ef2), the shear modulus of the fiber (Gf12), the elastic modulus of the matrix (Em), the proportional strength limit of the matrix (σp), the yield strength of the matrix (σs) and the degree of initial fiber misalignment. Results show that the model is capable of explaining the failure mechanism of CFRP under a unidirectional compressive load. Shear stress plays an important role in the compressive failure process. The localization of shear stress caused by initial fiber misalignment leads to plastic yield of the matrix and finally a kink band. Changes in these properties directly affect the concentration of shear stress in the defect areas, thereby affecting the compressive strength of the CFRP. When the values of Ef1, Ef2, Gf12,Em, σp, σs are separately increased by 10% or the degree of initial fiber misalignment is decreased by 10%, the compressive strength of CFRP is increased by 2.33%, 0, 0.39%, 3.38%, 1.17%, 2.30% and 2.52% respectively. Em has the greatest influence on the compressive strength of CFRP, followed by the initial fiber misalignment. The effects of the plastic properties of the matrix on the compressive strength of CFRP are obvious.
The preparation and gas separation performance of graphene/polyimide carbon membranes
HOU Min-chen, LI Lin, LU Yun-hua, RAN Xu, SONG Cheng-Wen, WANG Chun-lei, LIANG Chang-hai, WANG Tong-hua
2020, 35(6): 762-768. doi: 10.19869/j.ncm.1007-8827.20180067
Abstract(711) PDF(107)
Abstract:
Graphene/polyimide carbon membranes were prepared by an in-situ polymerization method, in which the 9,9'-bis(4-aminophenyl)fluorine (FDA), 9,9'-bis(3-amino-4-hydroxyphenyl)fluorine (BisAHPF) and 4,4'- (hexafluoroisopropylidene)diphthalic anhydride (6FDA) were used as the monomers and graphene oxide (GO) as the pore size regulator. FTIR, XPS, XRD, TGA, N2 adsorption and gas permeability tests were used to characterize the microstructures and properties of GO and the graphene/polyimide carbon membranes. The effect of the GO content on the microstructure and gas separation performance of the carbon membranes were investigated. Results show that the incorporation of GO into the polyimide significantly increases the total pore volume of the carbon membranes, especially the volume of ultramicropores smaller than 0.6 nm, as well as improving the thermal stability of the membranes. Compared with the polyimide carbon membrane without GO, the graphene/polyimide carbon membranes have an obvious increase in the CO2 selectivity with a high gas permeability and the selectivity increased with GO loading. The gas permeability of pure CO2 for the graphene/polyimide carbon membrane with a GO loading of 0.5 wt.% is 8 760 Barrer and its CO2 selectivities against N2 (CO2/N2) and CH4(CO2/CH4) are 52 and 53, respectively, which are 32%, and 39% higher than that of the pure carbon membrane.
Preparation and dielectric and mechanical properties of fluorine-functionalized graphene oxide/polyimide nanocomposites
XING Rui-guang, ZHUANG Xiao-xu, WANG Bo, LI Ya-nan, ZHANG Bang-wen
2020, 35(6): 769-775. doi: 10.19869/j.ncm.1007-8827.20180129
Abstract(522) PDF(101)
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Fluorine-functionalized graphene oxide was obtained by reacting pentafluoroaniline with graphene oxide. Fluorine-functionalized graphene oxide/polyimide nanocomposites were prepared by an in-situ polymerization method using 4,4-diaminodiphenyl ether and pyromellitic dianhydride as the monomers and N,N-dimethylacetamide as the dispersing solvent. The dielectric constant and mechanical properties of the nanocomposites were investigated. Results indicate that when the fluorine-functionalized graphene oxide content is increased from 0 to 2 wt%, the dielectric constant of the nanocomposite decreases from 3.61 to 2.8 and the tensile strength increases from 11.75 to 14.2 MPa.
Mechanical properties of unidirectional carbon fiber composites based on domestic T800H carbon fiber, M40J graphite fiber and their mixtures
PENG Gong-qiu, LI Ke, ZHONG Xiang-yu, LI Guo-li, LI Wei-dong, BAO Jian-wen, WANG Jin
2020, 35(6): 776-784. doi: 10.19869/j.ncm.1007-8827.20190172
Abstract(911) PDF(128)
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Three unidirectional carbon fiber composites impregnated with molten epoxy resin were prepared from T800H carbon fiber, M40J graphite fiber, and their mixtures containing alternating and parallel tows of 12 K fibers with a volume ratio of 1∶1. Their tensile strength and modulus in directions parallel (0°) and perpendicular (90°) to fiber axis as well as the compressive strength in quasi-isotropic(＋45°/0°/-45°/90°)4S after a drop weight impact according to ASTM 7136/7137 were investigated. Results indicate that the 0° tensile modulus of the mixed composite observes the laws of mixing, the 0° tensile strength and inter-laminar shear stress negatively deviate from the laws of mixing, and the 90° tensile strength and the compressive strength positively deviate from the laws of mixing. Compared with the T800H composite, the 0° tensile modulus of the hybrid is increased by 13%. Compared with the M40J composite, the compressive strength of the hybrid is increased by 35%. The hybrid composite has both a high tensile modulus and a high compressive strength.
Dynamic compressive properties of unidirectional composites made of TG800 carbon fiber and epoxy resin
PAN Yue-xiu, BAO Jia-wei, WANG Fan-wen, ZHANG Ling-dong, WANG Yang-wei, CHENG Xing-wang, YANG Yun-hua
2020, 35(6): 785-792. doi: 10.19869/j.ncm.1007-8827.20200128
Abstract(985) PDF(136)
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The dynamic compressive properties of unidirectional composites made of TG800 carbon fibers and an epoxy resin were tested by the split Hopkinson pressure bar method. Effects of the fiber diameter and surface treatment by anodic oxidation on the dynamic compressive properties and fracture failure modes of the composites were investigated by SEM combined with numerical simulation. Results indicated that the TG800/epoxy resin composites had a brittle fracture behavior and strength increased as strain rate, interface strength or fiber diameter increased during dynamic compressive property testing. With strong interfacial bonding enabled by the surface treatment, when the fiber diameter was increased from 5 to 6 μm the dynamic compressive strength increased by about 18% and the primary failure mode changed from fiber breakage and debonding between fiber and resin to plastic deformation of the resin and debonding between fiber and resin. When 5.4 μm diameter fibers were used, a comparison of weak (not oxidized) versus strong interfacial bonding, showed that the dynamic compressive strength for the former was about 6% lower, and the failure mode of the latter was fiber breakage, plastic deformation of the resin, and debonding between fiber while the former was only debonding between fiber and resin.
A comparative analysis of polyacrylonitrile-based carbon fibers: (I) Microstructures
LI Deng-hua, LU Chun-xiang, HAO Jun-jie, WANG Hui-min
2020, 35(6): 793-801. doi: 10.1016/S1872-5805(20)60527-3
Abstract(680) PDF(349)
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X-ray wide angle diffraction/small angle scattering, Raman spectroscopy and high resolution transmission electron microscopy were used to characterize the crystalline structure, pore structure, radial structural heterogeneity, degree of graphitization, internal residual stress, crystalline orientation and fractal phenomena of various grades (T and MJ) of polyacrylonitrile-based carbon fibers made by Toray Inc, Japan. Results showed that compared with the T series fibers, the MJ series fibers had a significantly lower internal residual stress, better structural orientation and a much higher degree of graphitization, but the dimensions of the microvoids and the radial inhomogeneity were increased, which revealed the significant influence of graphitization conditions in making MJ series fibers on the microstructures of carbon fibers.
A comparative analysis of polyacrylonitrile-based carbon fibers: (Ⅱ) Relationship between the microstructures and properties
HAO Jun-jie, LU Chun-xiang, LI Deng-hua
2020, 35(6): 802-810. doi: 10.1016/S1872-5805(20)60528-5
Abstract(611) PDF(139)
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The relationships between the mechanical properties and the microstructures of typical polyacrylonitrile-based carbon fibers were studied on the basis of the elastic wrinkle model and Griffith microcrack theory. The effects of microcrystallite structure and its preferred orientation on tensile modulus, the effects of microvoids and mass density changes on the tensile strength, and the effects of internal residual compressive stress on the strain to failure, were analyzed, based on which the structural factors played a key role in determining the mechanical properties of the fibers.

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