CVD 法制备三维石墨烯的电化学储能性能

维石墨烯是由二维石墨烯构成的三维网络结构,多孔的网络结构赋予了三维石墨烯超大的比表面积、超高的机械强度以及优异的电子传输通道. 因其优异的性能,三维石墨烯及其复合材料已经广泛地应用于能源、化学和生物等研究领域. 在三维石墨烯的合成方法中,化学气相沉积法由于制备的三维石墨烯具有高纯度、良好结晶性和优异的机械性能而备受推崇. 本文结合当前研究热点,综述了化学气相沉积法制备三维石墨烯及其复合材料在电化学储能领域（铝电池、锂离子电池、锂-硫电池、钠离子电池、金属-空气电池、超级电容器）中的应用,并简要评述当前化学气相沉积法制备三维石墨烯在应用中所面临的挑战及发展前景.     

三维多孔泡沫石墨烯的制备与应用研究进展

泡沫石墨烯是一种新型的碳基化工材料,具有独特的三维连通网络结构和优异的力学、热学、电学和化学稳定性能。本文综述了三维多孔泡沫石墨烯的制备与应用研究进展,主要介绍其水热法和化学气相沉淀制备法以及其作为催化材料、检测材料及电极材料的应用研究现状,并探讨了该领域亟待解决的重要问题和未来发展前景。     

三维石墨烯的制备及其在电化学生物传感器中的研究现状

三维石墨烯具有多孔网络结构、大的比表面积、高的导电性、优异机械性能和良好的生物相容性,作为电化学生物传感器电极材料在检测生物分子方面表现出优异的性能,是一种非常理想的电化学生物传感器电极材料。本文综述了三维石墨烯的制备方法及其在电化学生物传感器中最新的研究进展。     

氧化石墨烯和石墨烯在催化领域中的应用研究进展

石墨烯具有独特的二维平面结构,其导电性能好,比表面积大,耐酸碱,耐高温.基于石墨烯的优异特性,本文作者从材料的合成和结构等方面对石墨烯基催化剂的研制及其催化性能进行了评述.介绍了石墨烯催化体系的类型和机理,对石墨烯催化中存在的问题进行了简单分析,并对石墨烯在催化领域的应用前景进行了展望.     

石墨烯/高分子复合薄膜的制备及应用

石墨烯是一种单原子厚度的二维碳纳米材料,具有优异的光、电、热和力学性能,以及巨大的比表面积.石墨烯与高分子之间能够通过共价或非共价作用(氢键、π-π作用、静电作用等)进行复合.这些相互作用既增加了石墨烯在高分子中的溶解性或分散性,也可以提高复合材料的性能或拓展其功能.目前常用的制备石墨烯高分子复合材料的方法有溶液混合、熔融共混和原位聚合等.该类复合材料可以通过蒸发溶剂、溶液涂覆、真空抽滤、层层自组装等途径加工成相应的复合膜.石墨烯高分子复合薄膜在制备高强度结构材料、超级电容器、光伏器件、锂离子电池负极材料以及传感器等方面具有重要的应用价值.本文综述了近年来石墨烯高分子复合薄膜的制备和应用方面的研究进展,并对该领域进行了展望.     

三维石墨烯基材料的制备、结构与性能

石墨烯具有单层碳原子组成的六方晶系晶体结构及独特的电学、化学、力学和热学性质。然而,由于石墨烯片层之间较强的π-π键和范德华力,导致易团聚或堆积,使其比表面积大幅减小,严重损害其性能。解决上述问题的最有效方法之一是构建具有多孔结构的三维石墨烯基材料,不仅保留了石墨烯优秀的导电性能和力学性能等本征特性,而且获得密度低、比表面积大、孔隙率高等结构优点,进而满足吸附剂、催化剂载体、生物传感器及电池与超级电容器电极材料等先进功能材料领域的应用需要。因此,开发三维石墨烯基材料的先进制备方法成为本领域研究的热点方向。本文综述了三维石墨烯基材料的现有制备方法,包括自组装法(水热还原法、化学还原法及冷冻干燥法)、模板法(胶体模板法、模板辅助化学气相沉积法及模板辅助水热还原法)和3D打印法(直写成型法、喷墨打印法、熔融沉积成型法、光固化成型法、选区激光烧结法及选区激光熔融法),总结了上述方法的优点及当前存在的主要问题,并且对三维石墨烯基材料制备技术的发展方向进行了展望。     

功能型单层石墨烯的热剥离法制备及其超电容性能

以氧化石墨(GO)作为前驱体,在两种不同热剥离温度下制备了两类功能型单层石墨烯.其中第一类功能型单层石墨烯通过在较低温度及空气气氛下热剥离GO制备;第二类功能型单层石墨烯通过在氮气保护下高温热剥离GO得到;利用氮气吸附-脱附方法测定了两类样品的比表面积,利用电化学测试方法分析了其超电容性能.结果表明,通过低温热剥离的方式即可以有效剥离GO;两类样品均具有较高的BET比表面积.低温热剥离GO所制备的功能型单层石墨烯在2 mol/L KOH体系中的最大比电容值约为220 F/g;而通过高温热剥离GO所制备的功能型单层石墨烯虽然同样具有较高的BET比表面积,但其最大比电容值下降至约150 F/g.这表明通过低温热剥离GO所制备的功能型单层石墨烯具有更优异的超电容性能.     

石墨烯气凝胶的可控组装

石墨烯气凝胶一般是由石墨烯片层经过湿法化学组装或气相化学生长获得的一种具有连通多孔网络结构的石墨烯三维宏观体材料,表现出极高的比表面积、良好的导电性以及优异的机械性能等,在电化学储能、吸附、催化以及传感等领域有着极为重要的应用。本文从石墨烯气凝胶的结构设计与组装策略出发,综述了近年来石墨烯纳米结构单元在石墨烯气凝胶材料（氧化石墨烯、还原氧化石墨烯、化学气相沉积（CVD）石墨烯、以及复合气凝胶等）中的组装行为,并对石墨烯气凝胶目前的现状及今后发展方向做了简要评述。     

石墨烯纤维：制备、性能与应用

石墨烯纤维是一种由石墨烯片层紧密有序排列而成的一维宏观组装材料。通过合理的结构设计和可控制备,石墨烯纤维能够将石墨烯在微观尺度的优异性能有效传递至宏观尺度,展现出优异的力学、电学、热学等性能,从而应用于功能织物、传感、能源等领域。目前,石墨烯纤维主要通过湿法纺丝、限域水热组装等方法制备得到,其性能可以通过对材料体系和制备工艺的优化而进一步提升。本文首先介绍了石墨烯纤维的制备方法,然后详细阐述了石墨烯纤维的性能,讨论了其性能提升策略,并总结了石墨烯纤维的应用,最后对石墨烯纤维的未来发展、挑战和前景进行了展望。     

介孔硅复合氧化石墨烯多孔材料的制备及其CO2吸附性能研究

以P123为模板剂,以TEOS为硅源,以氧化石墨烯为复合组分,采用溶胶-凝胶法和自组装法制备了具有较大比表面积的介孔硅复合氧化石墨烯三维多孔材料（MSM/GOs）,进一步通过物理浸渍聚乙烯亚胺（PEI）制备了固态胺吸附材料。利用扫描电子显微镜（SEM）、氮气吸附-脱附曲线、元素分析等方法表征复合材料的结构和形貌,研究了氧化石墨烯添加量对材料的比表面积和胺化效果的影响以及吸附温度对其吸附CO₂性能的影响。研究结果表明,氧化石墨烯的引入能显著提高介孔硅复合氧化石墨烯多孔材料的比表面积,当GO添加量为4.5wt%时,其比表面积可高达841m²/g。高的比表面积有利于提高材料的氨基含量。在30wt%PEI的物理浸渍胺化后,MSM/GO-4.5@30%PEI拥有最大含氮量（9.59wt%）和CO₂吸附量（1.70mmol/g）。得益于良好的多孔基体和有机胺的均匀分布,MSM/GO-4.5@30%PEI在不同温度下的吸附量较稳定,循环再生吸附后仍能保持初始吸附量的80%。动力学研究表明,准一级模型和Avrami模型均能较好地拟合其吸...     

3D石墨烯基气凝胶的制备及在超级电容器中的应用

超级电容器作为一种新型的能源存储装置,由于其较高的功率密度、优良的充放电特性、超长的循环寿命,使其在移动电源,新能源汽车等众多领域具有非常广泛的应用前景。3D石墨烯基气凝胶具有多孔结构、大的比表面积、高的导电率、优异的机械性能和电子传输能力,它一直被认为是超级电容器的理想电极材料。本文综述了3D石墨烯基气凝胶的制备方法及其在超级电容器中的应用现状,并展望了其在超级电容器中的应用前景。     

石墨烯空心微球制备方法的研究进展

石墨烯被认为是一种颇具潜力的新型材料,具有优异的导电性能、力学性能以及大的比表面积,但石墨烯极易因为片层间的分子间作用力以及π-π作用而发生堆叠团聚。 构筑三维空心微球结构不仅能够有效阻止石墨烯片团聚,从而保证大的比表面积与优异的性质,还具有结构规整、尺寸可调的独特优势。 本文对近年来石墨烯空心微球的制备方法进行了阐述,主要按照模板法与无模板法两大类进行了整理与分析,又将模板法分为硬模板法与软模板法两类来叙述,对石墨烯空心微球的制备过程中应用到的多种技术进行了介绍与举例,并分别对硬模板法、软模板法、无模板法各自的优缺点进行了分析与总结。     

三维MXene多孔结构的构建与应用研究进展

MXene作为一种新型二维（2D）纳米材料以其独特的高导电性、高电化学表面活性等特性在多个领域引起了广泛关注。然而,MXene纳米片在自组装过程中出现的紧密堆叠现象导致比表面积急剧下降,降低了活性表面积,从而严重阻碍了它们在能源储存、电磁屏蔽、吸附等领域的潜在应用。构建三维多孔结构是解决MXene组装过程中自堆叠问题的一种有效途径,而且通过不同的组装方法可以实现对多孔宏观结构组成成分、孔径分布以及孔径大小的调控,使得MXene多孔材料在机械性能、电学性能以及光热转换性能等方面得到更好的调整,从而满足不同应用领域的需求。本综述以Ti₃C₂T_x MXene为主要研究材料总结了各种多孔MXene宏观结构的制备方法,讨论了其在电池/超级电容器、电磁屏蔽与吸收、海水淡化、光催化以及传感和环境修复等方面的应用,阐述了MXene多孔结构在各种应用中的贡献与意义,并针对MXene多孔结构的制备、结构调控和应用等方面的机遇和挑战作了论述。     

生物质羟基磷灰石作为模板制备三维石墨烯

As a new 2D material with excellent chemical stability, good electric conductivity, and high specific surface area, graphene has been widely used in energy storage and conversion devices. However, 2D graphene layers are easily stacked, which may significantly reduce the surface area and degrade the excellent electrical properties of graphene. To avoid this, one of the most effective methods is to construct 3D graphene (3DG) with specific porous microstructures. Chemical vapor deposition (CVD) is an important method for the synthesis of high-quality 3DG, where templates play a defining role in controlling the structure and cost of 3DG. Metallic materials with 3D microstructures, such as nickel foam, have proven to be useful as substrates for the growth of high-quality 3DG. However, metal substrates are usually expensive, and the pickling solution generated after etching may cause environmental problems. Therefore, non-metallic substrate materials with lower costs have been investigated for the preparation of 3DG. Herein, we developed a novel template material, mammal bone ashes, for the CVD preparation of 3DG. Mammal bone ash is an inexpensive and abundant biomass hydroxyapatite. During the high-temperature CVD reaction, the bone ash powders were slightly sintered to form a continuous porous structure with graphene coating. The morphology of 3DG is inherited from the microstructure of bone ash templates. After removing the bone ash template with hydrochloric acid, the template-grown 3DG was obtained with a unique bicontinuous structure, i.e. both the graphene framework and the void space were continuous. In addition, the pickling solution of the bone ash templates after etching was exactly the same as that for the raw materials for the production of phosphoric acid to achieve high atom utilization. We further optimized the graphitization degrees, layer number, and porous morphology of 3DGs. The microstructure evolution of 3DG is highly relevant to the layer thickness and uniformity of graphene layers. A short growth time would lead to a non-uniform and thin layer of graphene, which is not able to support a complex 3D porous structure. In contrast, a uniform graphene layer with proper thickness is capable of forming a robust 3D architecture. In addition, the facile CVD method can be extended to a series of metal phosphate templates, including tricalcium phosphate [Ca₃(PO₄)₂], trimagnesium phosphate [Mg₃(PO₄)₂], and aluminum phosphate [AlPO₄]. 3DG with bicontinuous morphology is promising as a conductive frame material in electrochemical energy storage devices. As an illustration, high-performance Li-S batteries were fabricated by the uniform composition of an S cathode on 3DG. In comparison with heavily stacked 2D graphene sheets in reduced graphene oxide / S composite, the non-flat structure of 3DGs remained unchanged even after the harsh melt-diffusion process of high-viscosity liquid sulfur. The resulting 3DG/S cathode delivered a high specific capacity of ~550 mAh∙g^-1 at a high current rate (2C). Our work opens an avenue to the low-cost and high-utility production of 3D graphene, which could be integrated with the well-developed phosphorus chemical industry.     

石墨烯基纤维电容器的可控制备及应用

超级电容器又名电化学电容器,是一种绿色储能器件。 超级电容器的研究,从根本上讲是寻找比表面积大且可以被充分利用的电极材料。 石墨烯作为sp²杂化碳质材料的基元单位,具有独特的二维结构和优异的物化特性,使得其在超级电容器领域具有巨大的应用潜力,其中石墨烯纤维超级电容器受到了研究工作者越来越广泛的关注。 本文通过对一维石墨烯纤维的自组装以及与制备材料的共组装来作为超级电容器的电极材料,对其可控制备进行了系统的归纳和总结,可控构建独特的电极材料,使其性能得以优化,组装出高性能的超级电容器,并对相关领域的发展趋势做了展望。     

Porous graphene-based electrodes: Advances in electrochemical sensing of environmental contaminants

Extravagant toxins release at an uncontrollable scale due to the continuous embarking of organic and inorganic contaminants has become a severe threat to the ecosystem’s healthy sustainability. The timely monitoring and determination of the environmental contaminants are crucial to take proper steps for environmental remediation. Among advanced nanomaterials, graphene is one of the extensively explored electrode materials for sensing environmental toxins. However, the graphene sheets' agglomeration due to weak wander Waals forces and the π–π interactions compromise its unique inherent features. The integration of graphene into porous structures can facilitate in exploiting its intrinsic properties. Graphene porous network offers highly conductive multiplexed pathways with a well-defined porous structure that provides a better diffusion of the electrolyte along with analytes to encounter the active electrode material. The pores in the 2D sheet or 3D architecture of graphene provide extensive active sites for various analytes' interaction. Rationally designed porous graphene-based materials and nanocomposites are promising advanced electrode materials for trace level quantification of environmental toxins. Herein, we critically discuss the advances in developing the porous graphene and its composites-based electrodes for electrochemical sensing of the environmental toxins.     

基于碳纳米材料的毛细管电色谱固定相研究进展

碳纳米材料由于其具有独特的纳米结构、大的比表面积、较强的热稳定性、良好的导电性以及较好的吸附性能等物理化学性质,因而在分析科学、生命科学、材料科学及环境科学等领域得广泛的应用.结合国内外最新文献,对近5年来碳纳米材料在毛细管电色谱新型固定相的制备研究方面进展进行了评述,包括毛细管电色谱的分类及分离机理、毛细管电色谱柱的制备方法和优缺点,碳纳米材料(石墨烯、碳纳米管、氧化石墨烯、还原氧化石墨烯、富勒烯)的结构性质及制备方法、碳纳米材料在毛细管电色谱柱固定相中的应用及作用机理等,并对其在色谱应用领域的方向进行了展望.     

A novel approach to synthesize porous graphene by the transformation and deoxidation of oxygen-containing functional groups

In this study, impurity-free porous graphene (PG) with intrinsic pore structure was synthesized through a facile acid-alkali etching-assisted sonication approach. The pore structure appears on the surface of graphene sheets due to intrinsic defects of graphene. The PG possessed an extremely high specific surface area of 2184 m²/g, the size of ∼5 μm and layer numbers of 3–8. Additionally, PG contained micropores and mesopores simultaneously, with an average pore diameter of approximately 3 nm. The effects of acid, alkali, and ultrasound treatment on PG preparation were elucidated by transmission electron microscopy and fourier transform infrared spectroscopy. First, in an acidic solution, oxygen-containing functional groups (hydroxyls, carboxyl, and epoxides) were formed due to the hydrolysis of sulfate and continuous transformations of these functional groups on graphene oxide. Second, under the synergistic effects of alkali and ultrasound treatment, PG was obtained due to the loss of carboxyl and epoxide groups. A new route for preparing PG was provided by the proposed method.     

A novel approach to synthesize porous graphene by the transformation and deoxidation of oxygen-containing functional groups

The impurity-free porous graphene prepared by acid-alkali etching-assisted sonication approach possessed the size of~5 μm, layer numbers of 3-8 and an average pore diameter of approximately 3 nm. In an acidic solution, oxygen-containing functional groups were formed due to the hydrolysis of sulfate and continuous transformations, and then under the synergistic effects of alkali and ultrasound treatment, porous graphene was obtained due to the loss of oxygen-containing functional groups.