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2022年  第37卷  第6期

目录
2022 年 6 期中文目次
2022, 37(6): 1-1.
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2022 年 6 期英文目次
2022, 37(6): 1-7.
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综合评述
Review of chemical recycling and reuse of carbon fiber reinforced epoxy resin composites
TIAN Zi-shang, WANG Yu-qi, HOU Xiang-lin
2022, 37(6): 1021-1045. doi: 10.1016/S1872-5805(22)60652-8
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Carbon fiber-reinforced epoxy resin composites (CFRCs) have been used in the transportation and aerospace fields because of their excellent mechanical properties. The recycling of CFRCs has attracted attention worldwide in recent years. Chemical recycling is a promising method, which can selectively destroy specific resin bonds to achieve controllable degradation. Matrix epoxy resins are degraded into monomers or oligomers, and the high-value carbon fibers can be recycled. First, we summarize progress on chemical recovery methods, mainly super- and subcritical fluids, oxidation, alcoholysis and electrochemical recycling etc. Then, we briefly introduce the synthesis and depolymerization mechanism of recyclable thermosetting resins by the insertion of reversible chemical bonds into the resin to prepare recyclable resins, which is beneficial for the recycling and reuse of components in CFRCs. Finally, possible developments in the chemical recycling of CFRCs and the preparation of high-performance recyclable epoxy resins are proposed.
A comprehensive review of the 3D printing of sp2 carbons: Materials, properties and applications
Satendra Kumar, Manoj Goswami, Netrapal Singh, Sathish Natarajan, Surender Kumar
2022, 37(6): 1046-1065. doi: 10.1016/S1872-5805(22)60651-6
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Three dimensional (3D) printing is a modern technology that has the possibility to transform existing production methods. It offers a novel production method of layered manufacturing and layer-by-layer stacking, which radically simplifies the manufacturing process and enables large-scale customizable production. However, there are still numerous problems with this new technology. Except for pure graphene, sp2 carbons can be 3D printed with little difficulty because of their hydrophilicity. The hydrophobic nature of pure graphene makes it difficult to print and process in water-based media, but advances in capillary inks allow for the 3D printing of pure graphene. This review focuses on the most recent developments in the 3D printing of sp2 carbons. A concise overview of 3D printing technologies is presented, followed by a summary of 3D printed sp2 carbons and their diverse applications. Finally, prospects and opportunities for this new field are discussed.

Electrospun carbon nanofibers for use in the capacitive desalination of water
Bethwel K Tarus, Yusufu A C Jande, Karoli N Njau
2022, 37(6): 1066-1088. doi: 10.1016/S1872-5805(22)60645-0
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Capacitive deionization (CDI) has rapidly become a promising approach for water desalination. The technique removes salt from water by applying an electric potential between two porous electrodes to cause adsorption of charged species on the electrode surfaces. The nature of CDI favors the use of nanostructured porous carbon materials with high specific surface areas and appropriate surface functional groups. Electrospun carbon nanofibers (CNFs) are ideal as they have a high specific surface area and surface characteristics for doping/grafting with electroactive agents. Compared with powdered materials, CNF electrodes are free-standing and don’t require binders that increase resistivity. CNFs with an appropriate distribution of mesopores and micropores have better desalination performance. Compositing CNFs with faradaic materials improve ion storage by adding pseudocapacitance to the electric double layer capacitance. The use of electrospun CNFs as electrodes for CDI is summarized with emphasis on the major precursor materials used in their preparation and structure modification, and their relations to the performance in salt electrosorption.

石墨炔:一种新型二维炭材料的合成、改性与应用
张婷, 王宇晶, 于灵敏, 士丽敏, 柴守宁, 何炽
2022, 37(6): 1089-1115. doi: 10.1016/S1872-5805(22)60653-X
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石墨炔是一类由sp和sp2杂化碳原子共同组成的新型二维材料。高度共轭及碳环大小可调的分子结构赋予石墨炔特异的物理化学性能,也为其功能化改性及应用提供了便利。近十年来,关于石墨炔的理论及实验研究正在广泛开展,在多个领域取得了一系列重要进展。本文首先对石墨炔性质进行了简要介绍,总结了不同形貌石墨炔的主要合成方法,包括Glaser-Hay交叉偶联、化学气相沉积法、范德华外延生长法、爆炸法、界面限域合成法及双极电化学法等。然后,对金属、非金属原子掺杂、修饰改性及其对石墨炔性能影响的理论计算和实验研究进行了综述;并就石墨炔基材料在环境、能源、生物医学等主要领域的研究进展进行了阐述和总结。最后,探讨了石墨炔发展亟待解决的问题和面临挑战。该综述能够为开展石墨炔相关研究提供有价值的前沿信息和方法参考。
研究论文
Incorporating TiO2 nanoparticles into the multichannels of electrospun carbon fibers to increase the adsorption of polysulfides in room temperature sodium-sulfur batteries
YE Xin, LI Zhi-qi, SUN Hao, WU Ming-xia, AN Zhong-xun, PANG Yue-peng, YANG Jun-he, ZHENG Shi-you
2022, 37(6): 1116-1124. doi: 10.1016/S1872-5805(22)60607-3
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With the rapid development of electric vehicles and large-scale power grids, lithium-ion batteries inevitably face the problem that their limited energy density and high cost cannot meet the growing demand. Room temperature sodium-sulfur (RT Na-S) batteries, which have the potential to replace lithium-ion batteries, have become a focus of attention. However, the challenging problem of their poor cycling performance cause by the “shuttle effect” of the reaction intermediates (sodium polysulfides) needs to be addressed. We report a method to incorporate TiO2 nano particles into the multichannels of electrospun carbon fibers (TiO2@MCCFs) to stabilize the sulfur compounds and produce high-performance RT Na-S batteries. The TiO2@MCCFs were prepared by electrospinning followed by heat treatment, and were infiltrated by molten sulfur to fabricate S/TiO2@MCCF cathode materials. The addition of the TiO2 nanoparticles increases the affinity of cathode materials for polysulfides and promotes the conversion of polysulfides to lower order products. This was verified by DFT calculations. A S/TiO2@MCCF cathode with a S content of 54% has improved electrochemical rate and cycling performance, with a specific capacity of 445.1 mAh g−1 after 100 cycles at 0.1 A g−1 and a nearly 100% Coulombic efficiency. Even at 2 A g−1, the cathode still has a capacity of 300.5 mAh g−1 after 500 cycles. This work provides a new way to construct high performance RT Na-S battery cathodes.
Microstructures and electrochemical properties of coconut shell-based hard carbons as anode materials for potassium ion batteries
HUANG Tao, PENG Da-chun, CHEN Zui, XIA Xiao-hong, CHEN Yu-xi, LIU Hong-bo
2022, 37(6): 1125-1134. doi: 10.1016/S1872-5805(21)60069-0
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Hard carbons have recently attracted wide interest as anode materials for potassium ion batteries (PIBs) because of their high reversible capacity. But, their high preparation cost and poor cycling stability prevent their practical use. Coconut shell-derived hard carbons (CSHCs) were prepared from waste biomass coconut shell using a one-step carbonization method, and were used as anode materials for potassium ion batteries. The effects of the carbonization temperature on the microstructures and electrochemical properties of the CSHCs were investigated by X-ray diffraction, nitrogen adsorption, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and cyclic voltammetry, etc. Results indicate that the CSHC carbonized at 1 000 °C (CSHC-10) has a suitable graphite microcrystal size, pore structure and surface defect content, and has the best electrochemical performance. Specifically, it has a high reversible specific capacity of 254 mAh·g−1 at 30 mA·g−1 with an initial Coulombic efficiency of 75.0%, and the capacity retention rates are 87.5% after 100 cycles and 75.9% after 400 cycles at 100 mA·g−1, demonstrating its excellent potassium storage performance.
Oxygen-incorporated carbon nitride porous nanosheets for highly efficient photoelectrocatalytic CO2 reduction to formate
WANG Hong-zhi, ZHAO Yue-zhu, YANG Zhong-xue, BI Xin-ze, WANG Zhao-liang, WU Ming-bo
2022, 37(6): 1135-1144. doi: 10.1016/S1872-5805(22)60619-X
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Using CO2 as a renewable carbon source for the production of high-value-added fuels and chemicals has recently received global attention. The photoelectrocatalytic (PEC) CO2 reduction reaction (CO2RR) is one of the most realistic and attractive ways of achieving this, and can be realized effectively under sunlight illumination at a low overpotential. Oxygen-incorporated carbon nitride porous nanosheets (CNs) were synthesized from urea or melamine by annealing in nitrogen or N2/O2 gas mixtures. They were used as the photoanode with Bi2CuO4 as the photocathode to realize PEC CO2 reduction to the formate. The electrical conductivity and the photoelectric response of the CNs were modified by changing the oxygen source. Oxygen in CNs obtained from an oxygen-containing precursor improved the conductivity because of its greater electronegativity, whereas oxygen in CNs obtained from the calcination atmosphere had a lower photoelectric response due to a down shift of the energy band structure. The CN prepared by annealing urea, which served as the source of oxygen and nitrogen, at 550 °C for 2 h in nitrogen is the best. It has a photocurrent density of 587 μA cm−2 and an activity of PEC CO2 reduction to the formate of 273.56 µmol cm−2 h−1, which is nearly 19 times higher than a conventional sample. The CN sample shows excellent stability with the photocurrent remaining constant for 24 h. This work provides a new way to achieve efficient catalysts for PEC CO2 reduction to the formate, which may be expanded to different PEC reactions using different cathode catalysts.
咖啡渣成型制备生物质炭及其CH4/N2分离性能
高雨舟, 徐爽, 王成通, 张雪洁, 刘汝帅, 陆安慧
2022, 37(6): 1145-1153. doi: 10.1016/S1872-5805(22)60626-7
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本文以咖啡渣为原料,硅酸钠为黏结剂和造孔剂,通过挤条成型技术制备柱状炭前驱体,经高温炭化活化和碱洗除硅,获得高强度柱状多孔炭吸附剂(CGCs),研究其CH4/N2的吸附分离性能。红外光谱分析结果显示9wt%硅酸钠溶液与原料质量比为1.5的样品CGC-1.5含有丰富的含氧官能团。CGCs的比表面积和孔容积随着前驱体中硅酸钠含量的增加而增大,其中CGC-1.5的比表面积为527 m2·g−1,总孔容为0.33 cm3·g−1。氮吸附等温线和CO2吸附等温线分析结果表明CGCs含有丰富的微孔、介孔以及大孔(个别样品),微孔主要集中在0.48 nm左右。在298 K和0.1 MPa条件下CGC-1.5对CH4的平衡吸附量为0.87 mmol·g−1,CH4/N2 (3/7)的IAST分离选择性达到10.3,优于多数生物质基多孔炭固体吸附剂和晶态材料。双组份动态穿透测试结果证实该材料在常压和加压条件均具有优异的CH4/N2动态分离性能,298 K时0.11 MPa和0.5 MPa条件下的动态选择性分别达到10.4和17.9,经10次吸-脱附循环测试,吸附量保持不变。CGC-1.5的机械强度高达123 N·cm−1,具有潜在的工业应用前景。
A flexible hard carbon microsphere/MXene film as a high-performance anode for sodium-ion storage
CAO Hai-liang, YANG Liang-tao, ZHAO Min, LIU Pei-zhi, GUO Chun-li, XU Bing-she, GUO Jun-jie
2022, 37(6): 1154-1162. doi: 10.1016/S1872-5805(22)60616-4
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Hard carbon is considered the most promising anode material for sodium-ion batteries, but its volume change during sodiation/desodiation limits its cycle life. Hard carbon microspheres (HCSs) with no binder were composited with a MXene film to form an electrode and its sodium storage properties were studied. The microspheres were prepared using Shanxi aged vinegar as a liquid carbon source. Two-dimensional Ti3C2Tx MXene (T is a functional group) was used as a multifunctional conductive binder to fabricate the flexible electrodes. Remarkably, because of the three-dimensional conductive network, the HCS/Ti3C2Tx film electrode has a high capacity of 346 mAh g−1, excellent rate performance and outstanding cycling stability over 1 000 cycles. This remarkable electrochemical performance indicates that the flexible film is a very promising anode for next-generation sodium-ion batteries.
Preparation and lithium storage of anthracite-based graphite anode materials
LI Yuan, TIAN Xiao-dong, SONG Yan, YANG Tao, WU Shi-jie, LIU Zhan-jun
2022, 37(6): 1163-1171. doi: 10.1016/S1872-5805(21)60057-4
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Several graphite samples with different microstructures were prepared from anthracite using industrial silicon powders as catalyst. The mechanism of the catalytic reaction and the electrochemical properties of the prepared coal-based graphite in lithium anodes were investigated. The correlation between the microstructure and the properties of the graphite is discussed. Results show that the sample with 5% silicon (G-2800-5%) has the best lithium storage. It has the well-developed graphitic structure with a degree of graphitization of 91.5% as determined from the interlayer spacing. When used as an anode material, a high reversible capacity of 369.0 mAh g−1 was achieved at 0.1 A g−1 and its reversible capacity was 209.0 mAh g−1 at a current density of 1 A g−1. It also exhibits good cycling stability with a capacity retention of 92.2% after 200 cycles at 0.2 A g−1. The highly developed graphite structure, which is favorable for the formation of a stable SEI and therefore reduces lithium ion loss, is responsible for the superior electrochemical performance.
Coal-based graphene as a promoter of TiO2 catalytic activity for the photocatalytic degradation of organic dyes
LIU Guo-yang, LI Ke-ke, JIA Jia, ZHANG Ya-ting
2022, 37(6): 1172-1182. doi: 10.1016/S1872-5805(21)60047-1
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Graphene oxide (GO) obtained from coal-based graphite by the Hummers method was hydrothermally treated to obtain reduced GO (rGO). TiO2 was mixed with aqueous suspensions of GO and rGO and dried at 70 oC to obtain GO-TiO2 and rGO-TiO2 with 95% (mass fraction) TiO2. TiO2 was also combined with a GO suspension by hydrothermal treatment to obtain rGO-hTiO2 with 95% TiO2. The three hybrids were used as catalysts for the photocatalytic degradation of rhodamine B (Rh B) and methyl orange (MO). Of the three materials, rGO-hTiO2 had the highest catalytic activity for the degradation of Rh B and MO under visible light irradiation. The reasons for having the best catalytic activity are that the incorporation of rGO into TiO2 helps increase its adsorption capacities for Rh B and MO as evidenced by adsorption in dark, and a narrowing of the TiO2 band gap as revealed by diffuse UV reflectance spectroscopy. This reduces the rate of recombination of electron–hole pairs by there being intimate contact between the TiO2 particles and rGO, forming Ti-O-C bonds as confirmed by XPS, with the TiO2 particles being uniformly decorated on the rGO sheets.
炭纸衬底上化学气相沉积直立型二维过渡金属硫化物及其电催化产氢性能
王克, 汤飞, 姚孝璋, HitanshuKumar, 干林
2022, 37(6): 1183-1192. doi: 10.1016/S1872-5805(21)60078-1
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以MoS2为代表的二维过渡金属硫化物近年来在电催化水分解产氢反应中表现出良好的电催化活性而受到广泛关注。但二维过渡金属硫化物的导电性一般较差、且催化活性位常在有限的边缘位置,成为限制其催化性能的重要因素。本文通过化学气相沉积方法研究了在炭纸基底上直接生长3种过渡金属硫化物(MoS2、NbS2和WS2)构筑一体化催化电极,以提高整个电极的导电性。通过优化生长工艺,实现了炭纸表面3种过渡金属硫化物的直立型生长并对电催化产氢反应表现出良好的催化性能,尤其是WS2表现出新颖的纳米片/纳米纤维层次结构,其对产氢反应表现出最佳的催化性能。在此基础上,对炭纸上生长的过渡金属硫化物通过阴极电化学活化处理的方式引入硫缺陷,从而提高其HER活性。结合透射电子显微镜和原位电化学拉曼光谱仪研究了二维过渡金属硫化物在电化学活化前后的结构变化尤其是所产生的硫缺陷的微观结构,为其产氢性能的提升提供合理的解释。
Ni(OH)2/石墨相氮化碳/石墨烯三元复合材料的制备及电化学性能
刘斌, 王艳敏, 马倩, 崔金龙, 张永强, 赫文秀
2022, 37(6): 1193-1200. doi: 10.1016/S1872-5805(22)60625-5
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通过水热法获得Ni(OH)2/石墨相氮化碳(g-C3N4)/石墨烯(RGO)三元复合材料,研究了Ni(OH)2∶g-C3N4∶RGO质量比对复合材料物理结构以及电化学性能的影响。通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)、傅里叶转换红外光谱仪(FT-IR)、氮气物理吸脱附仪、透射电子显微镜(TEM)等方法来反应材料的微观结构以及还原程度,使用循环伏安(CV)、恒流充放电(GCD)及电化学交流阻抗(EIS)测试电极材料的电化学性能。结果表明:当Ni(OH)2∶g-C3N4∶RGO=16∶1∶1(质量比)时电极材料呈3D相互交错的片状结构,氧化峰和还原峰的电位差ΔE为0.218 V。在1 A/g的电流密度下,复合材料的比电容为516.9 F/g,充放电3000次循环后,容量保持率达74.3%,显示出良好的电化学性能。