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doi: 10.1016/S1872-5805(24)60827-9
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近年来，光热驱动的海水淡化技术被认为是最具潜力的解决当下全球淡水资源短缺难题的方法之一。其中，太阳能界面水蒸发（SVG）是海水淡化效率的核心过程，其利用了太阳能作为唯一的能源输入，是保证光热海水淡化技术具有能量转换效率高、设备简单、成本效益高的关键。在所有高效SVG候选材料中，三维整体式碳基光热转换材料具有成本低、吸光效率高、结构可调性好、水蒸发速率高、无二次污染等优点。基于此，本综述首先简述了SVG 的基本原理，以此为依据介绍了高效 SVG 材料的工作机制和设计原则，最后系统归纳和概述了四种不同类型的三维整体式碳基光热转换材料的研究进展。所以本综述为未来三维整体式碳基光热转换材料的构建及其在SVG领域的应用研究提供理论基础和研究指导。
近年来，光热驱动的海水淡化技术被认为是最具潜力的解决当下全球淡水资源短缺难题的方法之一。其中，太阳能界面水蒸发（SVG）是海水淡化效率的核心过程，其利用了太阳能作为唯一的能源输入，是保证光热海水淡化技术具有能量转换效率高、设备简单、成本效益高的关键。在所有高效SVG候选材料中，三维整体式碳基光热转换材料具有成本低、吸光效率高、结构可调性好、水蒸发速率高、无二次污染等优点。基于此，本综述首先简述了SVG 的基本原理，以此为依据介绍了高效 SVG 材料的工作机制和设计原则，最后系统归纳和概述了四种不同类型的三维整体式碳基光热转换材料的研究进展。所以本综述为未来三维整体式碳基光热转换材料的构建及其在SVG领域的应用研究提供理论基础和研究指导。
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doi: 10.1016/S1872-5805(24)60826-7
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The mesophase-pitch-based carbon fibers (MPCFs) were prepared though controlling spinning temperature under a constant extrusion quantity using an industrial equipment in order to investigate the influence of spinning temperature on their microstructure mechanical properties and thermal conductivities. The results show that the microstructure of MPCFs shifts from ‘folded radial-split’ structure to ‘radial-split’ structure and presents a better graphite microcrystalline development as the spinning temperature increasing from 309 °C to 320 °C. Meanwhile, the thermal conductivity and tensile strength increase from 704 W·m−1·K−1 and 2.16 GPa to 1078 W·m−1·K−1 and 3.23 GPa, respectively. The lower viscosity of mesophase pitch and the weaker die-swell effect at the spinneret in the higher spinning temperature contribute to maintaining the orientation of mesophase pitch molecule forming in the spinneret, which plays a positive role in preparing MPCFs with larger crystal size and higher crystal orientation.
The mesophase-pitch-based carbon fibers (MPCFs) were prepared though controlling spinning temperature under a constant extrusion quantity using an industrial equipment in order to investigate the influence of spinning temperature on their microstructure mechanical properties and thermal conductivities. The results show that the microstructure of MPCFs shifts from ‘folded radial-split’ structure to ‘radial-split’ structure and presents a better graphite microcrystalline development as the spinning temperature increasing from 309 °C to 320 °C. Meanwhile, the thermal conductivity and tensile strength increase from 704 W·m−1·K−1 and 2.16 GPa to 1078 W·m−1·K−1 and 3.23 GPa, respectively. The lower viscosity of mesophase pitch and the weaker die-swell effect at the spinneret in the higher spinning temperature contribute to maintaining the orientation of mesophase pitch molecule forming in the spinneret, which plays a positive role in preparing MPCFs with larger crystal size and higher crystal orientation.
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doi: 10.1016/S1872-5805(24)60825-5
摘要:
锂硫电池因其高能量密度和低成本而成为最有发展前景的电化学储能器件之一。然而，多硫化物的“穿梭效应”、硫导电率低是锂硫电池商业化进程面临的主要挑战。本工作中，以九水合硝酸铁（Fe(NO)3·9H2O）为铁源，氟化铵（NH4F）为表面活性剂，通过简单的水热及煅烧处理制备了Fe2O3纳米棒修饰炭布（CC）的柔性Fe2O3/CC复合材料。其中，Fe2O3中介孔的存在有利于电解质的渗透和充放电过程中锂离子的传输和扩散，同时其密集阵列暴露出的丰富活性位点可以实现多硫化物的高效吸附和快速转化，降低多硫化物的穿梭效应。电化学分析显示：Fe2O3/CC正极在0.1 C（1 C=1672 mA g−1）的电流密度下具有1250 mAh g−1的高放电比容量，经过100圈循环后比容量保持在789 mAh g−1。在2 C的倍率下循环1000圈后仍能实现576 mAh g−1的放电比容量，容量保持率为70%，明显优于对比样品。上述结果表明，Fe2O3/CC能够很好地抑制多硫化物的穿梭，提高电池倍率性能和循环稳定性。
锂硫电池因其高能量密度和低成本而成为最有发展前景的电化学储能器件之一。然而，多硫化物的“穿梭效应”、硫导电率低是锂硫电池商业化进程面临的主要挑战。本工作中，以九水合硝酸铁（Fe(NO)3·9H2O）为铁源，氟化铵（NH4F）为表面活性剂，通过简单的水热及煅烧处理制备了Fe2O3纳米棒修饰炭布（CC）的柔性Fe2O3/CC复合材料。其中，Fe2O3中介孔的存在有利于电解质的渗透和充放电过程中锂离子的传输和扩散，同时其密集阵列暴露出的丰富活性位点可以实现多硫化物的高效吸附和快速转化，降低多硫化物的穿梭效应。电化学分析显示：Fe2O3/CC正极在0.1 C（1 C=1672 mA g−1）的电流密度下具有1250 mAh g−1的高放电比容量，经过100圈循环后比容量保持在789 mAh g−1。在2 C的倍率下循环1000圈后仍能实现576 mAh g−1的放电比容量，容量保持率为70%，明显优于对比样品。上述结果表明，Fe2O3/CC能够很好地抑制多硫化物的穿梭，提高电池倍率性能和循环稳定性。
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doi: 10.1016/S1872-5805(24)60823-1
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The high power density and excellent cyclic performance of micro-supercapacitors (MSCs) have garnered significant interest and offer a broad array of potential applications. However, there are still challenges in preparing MSCs electrodes with extremely high area capacitance and energy density. In this study, reduced graphene oxide aerogel (GA) and MoS2 were used as materials, combined with 3D printing and surface modification methods, and MSCs electrodes with ultra-high area capacitance and energy density were successfully constructed. Through 3D printing technology, we obtained electrodes with stable macro structure and GA crosslinked micropore structure. In addition, we used the solution method to load molybdenum disulfide nanosheets on the surface of the 3D printed electrode, further improving the electrochemical performance. The surface capacitance of the prepared electrode reached 3.99 F cm−2, the power density was 194 µW cm−2, and the energy density was 1997 mWh cm−2, showing excellent electrochemical performance and cycle stability. This research provides a simple and efficient method for preparing micro supercapacitor electrodes with high surface capacitance and high energy density, making them ideal for portable electronic devices. This research has important innovative significance in the field of MSCs electrodes.
The high power density and excellent cyclic performance of micro-supercapacitors (MSCs) have garnered significant interest and offer a broad array of potential applications. However, there are still challenges in preparing MSCs electrodes with extremely high area capacitance and energy density. In this study, reduced graphene oxide aerogel (GA) and MoS2 were used as materials, combined with 3D printing and surface modification methods, and MSCs electrodes with ultra-high area capacitance and energy density were successfully constructed. Through 3D printing technology, we obtained electrodes with stable macro structure and GA crosslinked micropore structure. In addition, we used the solution method to load molybdenum disulfide nanosheets on the surface of the 3D printed electrode, further improving the electrochemical performance. The surface capacitance of the prepared electrode reached 3.99 F cm−2, the power density was 194 µW cm−2, and the energy density was 1997 mWh cm−2, showing excellent electrochemical performance and cycle stability. This research provides a simple and efficient method for preparing micro supercapacitor electrodes with high surface capacitance and high energy density, making them ideal for portable electronic devices. This research has important innovative significance in the field of MSCs electrodes.
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doi: 10.1016/S1872-5805(24)60824-3
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Designing efficient and robust catalysts for hydrogen evolution reaction (HER) is imperative for saline water electrolysis technology. Herein, NC@CoxP@NF catalyst composed of CoxP nanowires array cooperated with N-doped carbon nanosheets (NC) on Ni foam (NF) has been fabricated through in-situ growth strategies. In the preparation process, Co(OH)2 nanowires were in-situ transformed into Co-MOF nanosheets on NF via the dissolution-coordination process of endogenous Co2+ and 2-methylimidazole. Cactus-like microstructure endows NC@CoxP@NF with the exposure of abundant active sites and ion transport channels, promoting the HER catalytic reaction kinetics. Furthermore, the alternating growth of nanowires and free-standing nanosheets in hierarchical interconnected NC@CoxP@NF, further strengthening its structural stability. Most importantly, the formation of surface polyanions (phosphate) and NC nanosheets protective layer improve the anti-corrosive properties of catalysts. Ultimately, the NC@CoxP@NF-10 shows excellent performance, requiring the overpotentials of 107 and 133 mV for HER to achieve 10 mA cm−2 in 1.0 M KOH and 1.0 M KOH + 0.5 M NaCl, respectively. This in-situ transformation strategy provides new ideas to construct the highly-efficient HER catalysts for saline water electrolysis.
Designing efficient and robust catalysts for hydrogen evolution reaction (HER) is imperative for saline water electrolysis technology. Herein, NC@CoxP@NF catalyst composed of CoxP nanowires array cooperated with N-doped carbon nanosheets (NC) on Ni foam (NF) has been fabricated through in-situ growth strategies. In the preparation process, Co(OH)2 nanowires were in-situ transformed into Co-MOF nanosheets on NF via the dissolution-coordination process of endogenous Co2+ and 2-methylimidazole. Cactus-like microstructure endows NC@CoxP@NF with the exposure of abundant active sites and ion transport channels, promoting the HER catalytic reaction kinetics. Furthermore, the alternating growth of nanowires and free-standing nanosheets in hierarchical interconnected NC@CoxP@NF, further strengthening its structural stability. Most importantly, the formation of surface polyanions (phosphate) and NC nanosheets protective layer improve the anti-corrosive properties of catalysts. Ultimately, the NC@CoxP@NF-10 shows excellent performance, requiring the overpotentials of 107 and 133 mV for HER to achieve 10 mA cm−2 in 1.0 M KOH and 1.0 M KOH + 0.5 M NaCl, respectively. This in-situ transformation strategy provides new ideas to construct the highly-efficient HER catalysts for saline water electrolysis.
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doi: 10.1016/S1872-5805(23)60741-3
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It is meaningful to find a toughener with a low dosage and effective improvement of interlaminar toughness in carbon fiber composites. In this paper, the toughening effect of phenolphthalein-based poly (ether sulfone) (PES-C) on E51/ DETDA epoxy and its carbon fiber composites (CFCs) was investigated. The SEM results showed that PES-C/epoxy blends formed sea-island phase and bicontinuous phase structure, which were associated with reaction-induced phase separation. After adding 15 phr PES-C, the glass transition temperature (Tg) of blends was increased by 51.5 °C. Meanwhile, the flexural strength, impact strength and fracture toughness of the blends were improved by 41.1%, 186.2% and 42.7%, respectively. These improvements could be attributed to the phase separation structure of the PES-C/epoxy system. Moreover, PES-C film was used to improve the mode-II fracture toughness (GIIC) of CFCs. GIIC value of the 7 μm PES-C film toughened laminate was improved by 80.3% than that of control laminate. The increase in GIIC could be attributed to cohesive failure and plastic deformation in the interleaving region.
It is meaningful to find a toughener with a low dosage and effective improvement of interlaminar toughness in carbon fiber composites. In this paper, the toughening effect of phenolphthalein-based poly (ether sulfone) (PES-C) on E51/ DETDA epoxy and its carbon fiber composites (CFCs) was investigated. The SEM results showed that PES-C/epoxy blends formed sea-island phase and bicontinuous phase structure, which were associated with reaction-induced phase separation. After adding 15 phr PES-C, the glass transition temperature (Tg) of blends was increased by 51.5 °C. Meanwhile, the flexural strength, impact strength and fracture toughness of the blends were improved by 41.1%, 186.2% and 42.7%, respectively. These improvements could be attributed to the phase separation structure of the PES-C/epoxy system. Moreover, PES-C film was used to improve the mode-II fracture toughness (GIIC) of CFCs. GIIC value of the 7 μm PES-C film toughened laminate was improved by 80.3% than that of control laminate. The increase in GIIC could be attributed to cohesive failure and plastic deformation in the interleaving region.
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doi: 10.1016/S1872-5805(22)60646-2
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Interfacial adhesion between carbon fiber (CF) and polyetherketoneketone (PEKK) is a key factor that affects the mechanical performances of their composites. Therefore, it is of great importance to impregnate PEKK into CF bundles as efficiently as possible. Here we report that owing to the high dissolubility, PEKK can be introduced onto CF surfaces via a wet strategy. The excellent wettability of PEKK guarantees a full covering and tight binding on CFs, making it possible to evaluate the interfacial shear strength (IFSS) with the microdroplet method. Furthermore, the interior of CF bundles can be completely and uniformly filled with PEKK by the solution impregnation, leading to a high interlaminar shear strength (ILSS). The maximum IFSS and ILSS can reach 107.8 and 99.3 MPa, respectively. Such superior shear properties are ascribed to the formation of amorphous PEKK confined in the limited spacing between CFs.
Interfacial adhesion between carbon fiber (CF) and polyetherketoneketone (PEKK) is a key factor that affects the mechanical performances of their composites. Therefore, it is of great importance to impregnate PEKK into CF bundles as efficiently as possible. Here we report that owing to the high dissolubility, PEKK can be introduced onto CF surfaces via a wet strategy. The excellent wettability of PEKK guarantees a full covering and tight binding on CFs, making it possible to evaluate the interfacial shear strength (IFSS) with the microdroplet method. Furthermore, the interior of CF bundles can be completely and uniformly filled with PEKK by the solution impregnation, leading to a high interlaminar shear strength (ILSS). The maximum IFSS and ILSS can reach 107.8 and 99.3 MPa, respectively. Such superior shear properties are ascribed to the formation of amorphous PEKK confined in the limited spacing between CFs.
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doi: 10.1016/S1872-5805(22)60643-7
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Polyether ether ketone (PEEK) has favorable mechanical properties. However, its high melt viscosity limits its applications because it is hard to process. In this study, PEEK nanocomposites modified with carbon nanotubes (CNTs) and polyether imide (PEI) were prepared using a direct wet powder blending method. The melt viscosity of the nanocomposites decreased by approximately 50%. Under optimal conditions, the addition of CNTs and PEI resulted in a synergistic increase in the toughness of the nanocomposites. The elongation at break increased by 129%, and the fracture energy increased by 97%. The uniformly dispersed CNTs/PEI powder reduces the processing difficulty of PEEK nanocomposites without affecting the heat resistance. The nanocomposites prepared by this method have lower melt viscosity. This improvement of the properties of PEEK would facilitate its use in the preparation of thermoplastic composites by powder impregnation or laser sintering technology.
Polyether ether ketone (PEEK) has favorable mechanical properties. However, its high melt viscosity limits its applications because it is hard to process. In this study, PEEK nanocomposites modified with carbon nanotubes (CNTs) and polyether imide (PEI) were prepared using a direct wet powder blending method. The melt viscosity of the nanocomposites decreased by approximately 50%. Under optimal conditions, the addition of CNTs and PEI resulted in a synergistic increase in the toughness of the nanocomposites. The elongation at break increased by 129%, and the fracture energy increased by 97%. The uniformly dispersed CNTs/PEI powder reduces the processing difficulty of PEEK nanocomposites without affecting the heat resistance. The nanocomposites prepared by this method have lower melt viscosity. This improvement of the properties of PEEK would facilitate its use in the preparation of thermoplastic composites by powder impregnation or laser sintering technology.
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doi: 10.1016/S1872-5805(22)60597-3
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To obtain excellent carbonaceous precursors, the oxidation reaction mechanism and kinetics of ethylene tar were investigated. The oxidation process of ethylene tar was divided into three stages (350-550 K, 550-700 K and 700-900 K) according to the thermogravimetric curve. To reveal the oxidation reaction mechanism of ethylene tar, the components of evolved gases at different stages were further analyzed online by mass spectrometry and infrared technology. Then, based on the thermogravimetric curve of ethylene tar at different reaction temperatures, the whole reaction process was divided into four parts to perform kinetics simulation calculation. With the help of the iso-conversional method (Coats-Redfern) to analyze the linear regression rates (R2) between 17 common reaction kinetics models and experimental data, the optimal reaction kinetics model for expressing oxidation process of ethylene tar was determined. The results show that: (1) In the oxidation process, the side chains of aromatic compounds firstly react with oxygen to form alcohols and aldehydes, leaving peroxy-radicals to aromatic rings. After that, the aromatic compounds with peroxy-radicals undergo polymerization/condensation reaction to form larger molecular. (2) The fourth-order of reaction model is adopted to describe the first three parts of the oxidation process, and the activation energies are 47.330 kJ·mol−1, 18.689 kJ·mol−1 and 9.004 kJ·mol−1 respectively. The three-dimensional diffusion model is applied to the fourth part of the oxidation process, and the activation energy is 88.369 kJ·mol−1.
To obtain excellent carbonaceous precursors, the oxidation reaction mechanism and kinetics of ethylene tar were investigated. The oxidation process of ethylene tar was divided into three stages (350-550 K, 550-700 K and 700-900 K) according to the thermogravimetric curve. To reveal the oxidation reaction mechanism of ethylene tar, the components of evolved gases at different stages were further analyzed online by mass spectrometry and infrared technology. Then, based on the thermogravimetric curve of ethylene tar at different reaction temperatures, the whole reaction process was divided into four parts to perform kinetics simulation calculation. With the help of the iso-conversional method (Coats-Redfern) to analyze the linear regression rates (R2) between 17 common reaction kinetics models and experimental data, the optimal reaction kinetics model for expressing oxidation process of ethylene tar was determined. The results show that: (1) In the oxidation process, the side chains of aromatic compounds firstly react with oxygen to form alcohols and aldehydes, leaving peroxy-radicals to aromatic rings. After that, the aromatic compounds with peroxy-radicals undergo polymerization/condensation reaction to form larger molecular. (2) The fourth-order of reaction model is adopted to describe the first three parts of the oxidation process, and the activation energies are 47.330 kJ·mol−1, 18.689 kJ·mol−1 and 9.004 kJ·mol−1 respectively. The three-dimensional diffusion model is applied to the fourth part of the oxidation process, and the activation energy is 88.369 kJ·mol−1.
2023, 38(6): 997-1017.
doi: 10.1016/S1872-5805(23)60785-1
摘要:
Solar-driven interfacial vapor generation (SIVG) is increasingly used for fresh water production, having the advantages of low energy consumption, eco-friendliness, and high efficiency. Carbon-based photothermal materials (CPTMs) can introduce temperature and salinity gradients in the SIVG process because of their outstanding photothermal conversion properties, which have given SIVG great potential for both steam and power generation. Various kinds of CPTMs for clean water and electricity generation are discussed in this review. The basic principles and key performance indices of SIVG are first described and the photothermal and SIVG performance of various CPTMs including graphene oxides, carbon nanotubes, carbon dots and carbonized biomass are then summarized. Finally, current research concerning water/electricity cogeneration and ways to deal with the problems encountered are presented, to provide some guidelines for the use of multifunctional CPTMs for simultaneous steam and electricity generation.
Solar-driven interfacial vapor generation (SIVG) is increasingly used for fresh water production, having the advantages of low energy consumption, eco-friendliness, and high efficiency. Carbon-based photothermal materials (CPTMs) can introduce temperature and salinity gradients in the SIVG process because of their outstanding photothermal conversion properties, which have given SIVG great potential for both steam and power generation. Various kinds of CPTMs for clean water and electricity generation are discussed in this review. The basic principles and key performance indices of SIVG are first described and the photothermal and SIVG performance of various CPTMs including graphene oxides, carbon nanotubes, carbon dots and carbonized biomass are then summarized. Finally, current research concerning water/electricity cogeneration and ways to deal with the problems encountered are presented, to provide some guidelines for the use of multifunctional CPTMs for simultaneous steam and electricity generation.
2023, 38(6): 1018-1034.
doi: 10.1016/S1872-5805(23)60784-X
摘要:
金属空气电池作为高效的能源转换与存储装置，受到人们广泛关注。然而，阴极反应动力学缓慢及贵金属高昂的成本等一系列问题严重制约了金属空气电池的实用化进程。生物质炭材料因其特殊的电化学性能、环境效益和经济价值，已成为开发高性能金属空气电池阴极材料的重要选择。近年来，生物质炭材料在材料制备和微观结构设计等方面取得了较大进展。本文综述了生物质炭材料在金属空气电池阴极应用的最新研究进展，并从反应机理、合成策略和多维结构（一维、二维和三维）的角度深入阐述其对电催化性能的影响。最后，进一步讨论了生物质炭材料面临的挑战和未来的发展方向。这篇综述为生物质炭材料的结构设计提供了新的视角，旨在为开发高效、廉价和稳定的金属空气电池阴极催化剂提供参考和借鉴。
金属空气电池作为高效的能源转换与存储装置，受到人们广泛关注。然而，阴极反应动力学缓慢及贵金属高昂的成本等一系列问题严重制约了金属空气电池的实用化进程。生物质炭材料因其特殊的电化学性能、环境效益和经济价值，已成为开发高性能金属空气电池阴极材料的重要选择。近年来，生物质炭材料在材料制备和微观结构设计等方面取得了较大进展。本文综述了生物质炭材料在金属空气电池阴极应用的最新研究进展，并从反应机理、合成策略和多维结构（一维、二维和三维）的角度深入阐述其对电催化性能的影响。最后，进一步讨论了生物质炭材料面临的挑战和未来的发展方向。这篇综述为生物质炭材料的结构设计提供了新的视角，旨在为开发高效、廉价和稳定的金属空气电池阴极催化剂提供参考和借鉴。
2023, 38(6): 1035-1049.
doi: 10.1016/S1872-5805(23)60780-2
摘要:
Advanced electromagnetic absorbing materials (EAMs) with strong absorption and a wide effective absorption bandwidth (EAB), using innovative microstructural design and suitable multicomponents remain a persistent challenge. Here, we report the production of a material by the hydrothermal reduction of a mixture of graphene oxide (GO), Ni(NO3)2·6H2O, and Co(NO3)2·6H2O, resulting in reduced GO (RGO) with a self-assembled 3D mesh structure filled with NiCo2(CO3)3 . The unique microstructure of this assembly not only solves the problem of NiCo2(CO3)3 particles agglomerating but also changes the electromagnetic parameters, thereby improving the impedance matching and attenuation ability. High electromagnetic wave absorption (EMA) was achieved by combining the 3D interconnected mesh structure and the various interfaces between NiCo2(CO3)3 and RGO. The minimal reflection loss (RLmin) was −58.5 dB at 2.3 mm, and the EAB was 6.5 GHz. The excellent EMA performance of the aerogel can be attributed to the multiple reflection, scattering, and relaxation process of the porous 3D structure as well as the strong polarization of the interfacial matrix.n of the interfacial matrix.
Advanced electromagnetic absorbing materials (EAMs) with strong absorption and a wide effective absorption bandwidth (EAB), using innovative microstructural design and suitable multicomponents remain a persistent challenge. Here, we report the production of a material by the hydrothermal reduction of a mixture of graphene oxide (GO), Ni(NO3)2·6H2O, and Co(NO3)2·6H2O, resulting in reduced GO (RGO) with a self-assembled 3D mesh structure filled with NiCo2(CO3)3 . The unique microstructure of this assembly not only solves the problem of NiCo2(CO3)3 particles agglomerating but also changes the electromagnetic parameters, thereby improving the impedance matching and attenuation ability. High electromagnetic wave absorption (EMA) was achieved by combining the 3D interconnected mesh structure and the various interfaces between NiCo2(CO3)3 and RGO. The minimal reflection loss (RLmin) was −58.5 dB at 2.3 mm, and the EAB was 6.5 GHz. The excellent EMA performance of the aerogel can be attributed to the multiple reflection, scattering, and relaxation process of the porous 3D structure as well as the strong polarization of the interfacial matrix.n of the interfacial matrix.
2023, 38(6): 1050-1058.
doi: 10.1016/S1872-5805(23)60752-8
摘要:
多孔炭电极的表面改性与优化是实现超级电容器优异性能的关键。本文以煤化学工业的固体副产物为碳源，利用二维层状双氢氧化物（MgAl-LDH）的刚性约束作用耦合KOH活化工艺成功制备了二维富氧多孔炭纳米材料（OPCN）。系统研究了炭化温度对OPCN样品微观结构和表面特性的影响，通过SEM、TEM、氮气吸脱附测试以及元素分析等表征手段对炭材料的结构/组成和表面特性进行分析表明，经700 °C炭化获得的炭材料样品（OPCN-700）具有较高的氧质量分数（24.4%）和大的比表面积（2 388 m2 g−1），并表现出良好的润湿性。同时，OPCN-700样品丰富的微孔和二维纳米片结构为电解质离子提供了有效的储存和传输途径。作为超级电容器的电极材料，在电流密度为0.5 A g−1时，其比电容高达382 F g−1，并呈现出优异的倍率性能和循环稳定性。该技术策略为富氧原子掺杂二维多孔炭材料的可控制备与水系储能器件的设计构建提供了新思路。
多孔炭电极的表面改性与优化是实现超级电容器优异性能的关键。本文以煤化学工业的固体副产物为碳源，利用二维层状双氢氧化物（MgAl-LDH）的刚性约束作用耦合KOH活化工艺成功制备了二维富氧多孔炭纳米材料（OPCN）。系统研究了炭化温度对OPCN样品微观结构和表面特性的影响，通过SEM、TEM、氮气吸脱附测试以及元素分析等表征手段对炭材料的结构/组成和表面特性进行分析表明，经700 °C炭化获得的炭材料样品（OPCN-700）具有较高的氧质量分数（24.4%）和大的比表面积（2 388 m2 g−1），并表现出良好的润湿性。同时，OPCN-700样品丰富的微孔和二维纳米片结构为电解质离子提供了有效的储存和传输途径。作为超级电容器的电极材料，在电流密度为0.5 A g−1时，其比电容高达382 F g−1，并呈现出优异的倍率性能和循环稳定性。该技术策略为富氧原子掺杂二维多孔炭材料的可控制备与水系储能器件的设计构建提供了新思路。
2023, 38(6): 1059-1069.
doi: 10.1016/S1872-5805(23)60782-6
摘要:
Molybdenum selenide (MoSe2) has been regarded as an advanced electrocatalyst for the hydrogen evolution reaction (HER). However, its electrocatalytic performance is far inferior to platinum (Pt). Combining semiconductors with metals to construct Mott-Schottky heterojunctions has been considered as an effective method to enhance HER activity. In this work, we report a typical Mott-Schottky heterojunction composed of metal Co and semiconductor MoSe2 on carbon nanotubes (Co/MoSe2@CNT), prepared by a sol-gel process followed by thermal reduction. The characterization and theoretical calculations show that a Co/MoSe2 Mott-Schottky heterojunction can cause electron redistribution at the interface and form a built-in electric field, which not only optimizes the free energy of hydrogen atom adsorption, but also improves the charge transfer efficiency during hydrogen evolution. Thus, the Co/MoSe2@CNT has excellent catalytic activity with a low overpotential of 185 mV at 10 mA cm−2 and a small Tafel slope of 69 mV dec−1. This work provides a new strategy for constructing Co/MoSe2 Mott-Schottky heterojunctions and highlights the Mott-Schottky effect, which may inspire the future development of more attractive Mott-Schottky electrocatalysts for H2 production.
Molybdenum selenide (MoSe2) has been regarded as an advanced electrocatalyst for the hydrogen evolution reaction (HER). However, its electrocatalytic performance is far inferior to platinum (Pt). Combining semiconductors with metals to construct Mott-Schottky heterojunctions has been considered as an effective method to enhance HER activity. In this work, we report a typical Mott-Schottky heterojunction composed of metal Co and semiconductor MoSe2 on carbon nanotubes (Co/MoSe2@CNT), prepared by a sol-gel process followed by thermal reduction. The characterization and theoretical calculations show that a Co/MoSe2 Mott-Schottky heterojunction can cause electron redistribution at the interface and form a built-in electric field, which not only optimizes the free energy of hydrogen atom adsorption, but also improves the charge transfer efficiency during hydrogen evolution. Thus, the Co/MoSe2@CNT has excellent catalytic activity with a low overpotential of 185 mV at 10 mA cm−2 and a small Tafel slope of 69 mV dec−1. This work provides a new strategy for constructing Co/MoSe2 Mott-Schottky heterojunctions and highlights the Mott-Schottky effect, which may inspire the future development of more attractive Mott-Schottky electrocatalysts for H2 production.
2023, 38(6): 1070-1079.
doi: 10.1016/S1872-5805(23)60783-8
摘要:
A commercial polypropylene (PP) separator was modified by a one-dimensional carbon nanotube (CNT) and two-dimensional montmorillonite (MMT) hybrid material (CNT-MMT). Because of the high electron conductivity of the CNTs, and the strong polysulfide (LiPS) adsorption ability and easy lithium ion transport through MMT, the interconnected porous CNT-MMT interlayer with excellent structural integrity strongly suppresses LiPS shuttling while maintaining high lithium-ion transport, producing a high utilization of the active sulfur. Lithium-sulfur batteries assembled with this interlayer have a high lithium-ion diffusion coefficient, a high discharge capacity and stable cycling performance. They had an initial specific capacity of 1373 mAh g−1 at 0.1 C, and a stable cycling performance with a low decay rate of 0.062% per cycle at 1 C after 500 cycles.
A commercial polypropylene (PP) separator was modified by a one-dimensional carbon nanotube (CNT) and two-dimensional montmorillonite (MMT) hybrid material (CNT-MMT). Because of the high electron conductivity of the CNTs, and the strong polysulfide (LiPS) adsorption ability and easy lithium ion transport through MMT, the interconnected porous CNT-MMT interlayer with excellent structural integrity strongly suppresses LiPS shuttling while maintaining high lithium-ion transport, producing a high utilization of the active sulfur. Lithium-sulfur batteries assembled with this interlayer have a high lithium-ion diffusion coefficient, a high discharge capacity and stable cycling performance. They had an initial specific capacity of 1373 mAh g−1 at 0.1 C, and a stable cycling performance with a low decay rate of 0.062% per cycle at 1 C after 500 cycles.
2023, 38(6): 1080-1091.
doi: 10.1016/S1872-5805(23)60781-4
摘要:
Because of their high electrochemical activity, good structural stability, and abundant active sites, multi-metal sulfide/carbon (MMS/C) composites are of tremendous interest in diverse fields, including catalysis, energy, sensing, and environmental science. However, their cumbersome, inefficient, and environmentally unfriendly synthesis is hindering their practical application. We report a straightforward and universal method for their production which is based on homogeneous multi-phase interface engineering. The method has enabled the production of 14 different MMS/C composites, as examples, with well-organized composite structures, different components, and dense heterointerfaces. Because of their composition and structure, a typical composite has efficient, fast, and persistent lithium-ion storage. A ZnS-Co9S8/C composite anode showed a remarkable rate performance and an excellent capacity of 651 mAh·g−1 at 0.1 A·g−1 after 600 cycles. This work is expected to pave the way for the easy fabrication of MMS/C composites.
Because of their high electrochemical activity, good structural stability, and abundant active sites, multi-metal sulfide/carbon (MMS/C) composites are of tremendous interest in diverse fields, including catalysis, energy, sensing, and environmental science. However, their cumbersome, inefficient, and environmentally unfriendly synthesis is hindering their practical application. We report a straightforward and universal method for their production which is based on homogeneous multi-phase interface engineering. The method has enabled the production of 14 different MMS/C composites, as examples, with well-organized composite structures, different components, and dense heterointerfaces. Because of their composition and structure, a typical composite has efficient, fast, and persistent lithium-ion storage. A ZnS-Co9S8/C composite anode showed a remarkable rate performance and an excellent capacity of 651 mAh·g−1 at 0.1 A·g−1 after 600 cycles. This work is expected to pave the way for the easy fabrication of MMS/C composites.
2023, 38(6): 1092-1103.
doi: 10.1016/S1872-5805(23)60772-3
摘要:
An electrochemical sensor for Cu(II) based on ion-imprinted polymers was prepared by combining surface imprinting with electrochemical polymerization deposition. The sensor was modified by ion-imprinted magnetic carbon nanospheres with a specific selectivity and sensitivity for Cu(II). The morphology and structure of the materials were characterized and analyzed. Sensors with the imprinted electrode had a stronger selectivity and higher sensitivity towards Cu(II) compared with their original counterparts. Within relative concentrations of Cu(II) from 10−6 to 10−10 mol L−1, the detection limit of the sensor was as low as 5.138×10−16 mol L−1 (S/N=3). The sensor is resistant to interference, and has good reproducibility, and stability, making it excellent for the electrochemical detection of metal ions.
An electrochemical sensor for Cu(II) based on ion-imprinted polymers was prepared by combining surface imprinting with electrochemical polymerization deposition. The sensor was modified by ion-imprinted magnetic carbon nanospheres with a specific selectivity and sensitivity for Cu(II). The morphology and structure of the materials were characterized and analyzed. Sensors with the imprinted electrode had a stronger selectivity and higher sensitivity towards Cu(II) compared with their original counterparts. Within relative concentrations of Cu(II) from 10−6 to 10−10 mol L−1, the detection limit of the sensor was as low as 5.138×10−16 mol L−1 (S/N=3). The sensor is resistant to interference, and has good reproducibility, and stability, making it excellent for the electrochemical detection of metal ions.
2023, 38(6): 1104-1115.
doi: 10.1016/S1872-5805(23)60706-1
摘要:
We report a method for the of coal-based fluorescent carbon dots (CDs) at room temperature using a mixture of hydrogen peroxide (H2O2) and formic acid (HCOOH) as the oxidant instead of concentrated HNO3 or H2SO4. The CDs have an excitation dependent behavior with a high quantum yield (QY) of approximately 7.2%. The CDs are water soluble and have excellent photo-stability, good resistance to salt solutions, and are insensitive to pH in a range of 2.0-12.0. The CDs were used as a very sensitive probe for the turn-off sensing of Fe3+ ion with a detection limit as low as 600 nmol/L and a detection range from 2 to 100 μmol/L. This work provides a way for the high value-added utilization of coal.
We report a method for the of coal-based fluorescent carbon dots (CDs) at room temperature using a mixture of hydrogen peroxide (H2O2) and formic acid (HCOOH) as the oxidant instead of concentrated HNO3 or H2SO4. The CDs have an excitation dependent behavior with a high quantum yield (QY) of approximately 7.2%. The CDs are water soluble and have excellent photo-stability, good resistance to salt solutions, and are insensitive to pH in a range of 2.0-12.0. The CDs were used as a very sensitive probe for the turn-off sensing of Fe3+ ion with a detection limit as low as 600 nmol/L and a detection range from 2 to 100 μmol/L. This work provides a way for the high value-added utilization of coal.
2023, 38(6): 1116-1126.
doi: 10.1016/S1872-5805(23)60720-6
摘要:
The interfacial shear strength (IFSS) between carbon fibers (CFs) and the matrix is crucial to the performance of CF-reinforced polymer composites. To evaluate the contribution of mechanical interlocking and chemical anchoring at the interfaces of a polyacrylonitrile-based CF (TORAYCA T800SC-12000-10E)-reinforced epoxy resin (EP: bisphenol A type epoxy resin and tetrafunctional epoxy resin) composites, the surface roughness and content of oxygen-containing functional groups of the CFs were respectively altered by ammonia treatment and electrochemical oxidation. The results showed that ammonia treatment increased the surface roughness without much change to the surface elemental composition, while electrochemical oxidation increased the number of surface oxygen groups without changing the surface roughness. The IFSS of CF/EP composites was tested by the micro-droplet method. The relationships between IFSS, and surface roughness and oxygen content were obtained by linear fitting. The results showed that in the interfacial bonding of CF to epoxy resin, the contribution of chemical anchoring to the IFSS is larger than that of mechanical interlocking.
The interfacial shear strength (IFSS) between carbon fibers (CFs) and the matrix is crucial to the performance of CF-reinforced polymer composites. To evaluate the contribution of mechanical interlocking and chemical anchoring at the interfaces of a polyacrylonitrile-based CF (TORAYCA T800SC-12000-10E)-reinforced epoxy resin (EP: bisphenol A type epoxy resin and tetrafunctional epoxy resin) composites, the surface roughness and content of oxygen-containing functional groups of the CFs were respectively altered by ammonia treatment and electrochemical oxidation. The results showed that ammonia treatment increased the surface roughness without much change to the surface elemental composition, while electrochemical oxidation increased the number of surface oxygen groups without changing the surface roughness. The IFSS of CF/EP composites was tested by the micro-droplet method. The relationships between IFSS, and surface roughness and oxygen content were obtained by linear fitting. The results showed that in the interfacial bonding of CF to epoxy resin, the contribution of chemical anchoring to the IFSS is larger than that of mechanical interlocking.
2023, 38(6): 1127-1134.
doi: 10.1016/S1872-5805(23)60732-2
摘要:
Carbon/carbon-silicon carbide (C/C-SiC) composites were prepared by impregnation, hot-pressing with curing, carbonization at 800 oC and high-temperature heat treatment (800-1600 oC) using a 2D laminated carbon cloth as the reinforcing filler, and furfurone resin mixed with silicon, carbon from furfurone resin and SiC powders as the matrix. The effects of the addition of the three powders as well as subsequent chemical vapor infiltration (CVI) by methane on the density, microstructure and bend strength of the composites were investigated by scanning electron microscopy, density measurements, X-ray diffraction and mechanical testing. Both the SiC powders formed by the reaction at 1600 oC between the added Si and C particles and the added SiC powder, play a role in the reinforcement of the materials. In three-point bending, the composites had a pseudoplastic fracture mode and showed interlaminar cracking. After 10 h CVI with methane, pyrolytic carbon was formed at the interface between some of the carbon fibers and the resin carbon matrix, which produced maximum increases in the density and flexural strength of the composites of 4.98% and 38.86%, respectively.
Carbon/carbon-silicon carbide (C/C-SiC) composites were prepared by impregnation, hot-pressing with curing, carbonization at 800 oC and high-temperature heat treatment (800-1600 oC) using a 2D laminated carbon cloth as the reinforcing filler, and furfurone resin mixed with silicon, carbon from furfurone resin and SiC powders as the matrix. The effects of the addition of the three powders as well as subsequent chemical vapor infiltration (CVI) by methane on the density, microstructure and bend strength of the composites were investigated by scanning electron microscopy, density measurements, X-ray diffraction and mechanical testing. Both the SiC powders formed by the reaction at 1600 oC between the added Si and C particles and the added SiC powder, play a role in the reinforcement of the materials. In three-point bending, the composites had a pseudoplastic fracture mode and showed interlaminar cracking. After 10 h CVI with methane, pyrolytic carbon was formed at the interface between some of the carbon fibers and the resin carbon matrix, which produced maximum increases in the density and flexural strength of the composites of 4.98% and 38.86%, respectively.
2023, 38(6): 1135-1142.
doi: 10.1016/S1872-5805(23)60712-7
摘要:
碳纳米管选用（CNT）作为拉曼应力传感器，通过建立拉曼光谱mapping技术研究了经多次低温循环（−198~25 °C，0~300次）的炭纤维增强聚酰亚胺复合薄膜（CF/CNT-PI）的界面微观应力变化。研究发现：聚酰亚胺薄膜（CNT-PI）即使经300次低温循环，树脂内部应力依然为~175 MPa，循环次数对树脂内部应力影响较小，表明该材料具有良好的耐低温性。进一步研究了炭纤维（CF）增强的CNT-PI薄膜的内应力变化，获得了炭纤维、界面、树脂基体区域的微观应力mapping分布，发现CF区域的受力大于基体部分，表明CF在该体系中起到了对应力最主要载体的作用，并发挥了良好的增强效果。在循环次数<250次时，微观应力变化不大；但当循环次数高达300次时，炭纤维及界面区域应力值分别提高了21%和12.9%，应力在材料内部的集中增大会降低材料的力学性能。本研究有效地定量了外界温度循环变化下复合材料的增强材料、基体及界面的微观应力分布，这为检测复合材料服役过程中的使用安全性提供了一种理论依据与评判手段。
碳纳米管选用（CNT）作为拉曼应力传感器，通过建立拉曼光谱mapping技术研究了经多次低温循环（−198~25 °C，0~300次）的炭纤维增强聚酰亚胺复合薄膜（CF/CNT-PI）的界面微观应力变化。研究发现：聚酰亚胺薄膜（CNT-PI）即使经300次低温循环，树脂内部应力依然为~175 MPa，循环次数对树脂内部应力影响较小，表明该材料具有良好的耐低温性。进一步研究了炭纤维（CF）增强的CNT-PI薄膜的内应力变化，获得了炭纤维、界面、树脂基体区域的微观应力mapping分布，发现CF区域的受力大于基体部分，表明CF在该体系中起到了对应力最主要载体的作用，并发挥了良好的增强效果。在循环次数<250次时，微观应力变化不大；但当循环次数高达300次时，炭纤维及界面区域应力值分别提高了21%和12.9%，应力在材料内部的集中增大会降低材料的力学性能。本研究有效地定量了外界温度循环变化下复合材料的增强材料、基体及界面的微观应力分布，这为检测复合材料服役过程中的使用安全性提供了一种理论依据与评判手段。
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