介孔炭的直接制备及其电化学性能研究

以柠檬酸镁为原料,采用直接碳化法制备介孔炭电极材料。N2吸附测试表明,所制备多孔炭的比表面积达2 000 m2·g-1左右,介孔孔容和平均孔径随着炭化温度的升高而增加,当炭化温度大于800℃时,能够制备出以介孔结构为主的多孔炭材料。电化学测试表明,MgC-800和MgC-900具有优异的电化学电容特性。与硬模板法制备的OMC相比,MgC-800和MgC-900在实验电流密度范围内具有更大的比电容值,这应当归功于它们巨大的比表面积以及有利于电解质离子扩散的介孔结构。     

微孔-介孔多级孔炭材料的制备及电化学电容性能研究

采用有机-有机自组装法, 并结合后活化法制备了一类具有微孔-介孔复合孔结构的多级孔炭材料(HPC), 并研究了这类材料的电化学电容性能. 孔结构测试表明, 采用KOH后活化法可以在介孔炭的孔壁上控制性地生成微孔. 电化学测试表明, 与文献中报道的硬模板法制备的介孔炭相比, HPC具有更好的电化学电容性能. 在100 mV/s的快速电压扫描速率下, 它的比电容值能达到168.9 F/g. 更值得指出的是, HPC的高频电容性能非常优异, 在1 Hz时的比电容值高达180 F/g, 这一数值优于任何其它类的电极材料. HPC优异的电化学电容性能应当归功于它特殊的多级孔结构, 有助于电解质离子在孔道内的快速扩散.     

柚子皮衍生的分级多孔碳作为高性能超级电容器的电极材料

使用CTAB作为软模板,水热处理柚子皮,再以碳化和KOH活化过程得到了分级多孔碳(HPC),这种分级多孔碳材料的比表面积高达1 813 m~2·g~(-1),相比于没有水热步骤制备的多孔碳(PC),拥有更加丰富的介孔结构和更大的比表面积。XPS分析结果表明HPC的氧掺杂量更高,会比PC贡献更大的赝电容。三电极测试体系中,HPC的比电容达到285 F·g~(-1)(0.5 A·g~(-1),1 mol·L~(-1)KOH)。同时,组装的两电极对称超级电容器拥有很好的倍率性能,循环12 000次充放电后,比电容依旧保留99%。HPC拥有这样优异的性能归结于较大的比表面积,高氧掺杂量和合理的孔径分布的协同作用。     

超级电容器炭电极材料的研究

炭电极材料是超级电容器的核心,该领域的研究近年来相当活跃,活性炭粉、活性炭纤维、碳凝胶、碳纳米管、玻态炭、模板炭、碳化物衍生炭、石墨烯等各种多孔炭材料用作超级电容器电极材料的研究都有报道.本文概述了我们近年来在超级电容器炭电极材料方面的研究工作,主要介绍了强碱化学活化制备活性炭电极材料、纳米CaCO3模板法制备介孔炭电...     

纤维素纳米晶模板法制备多级孔炭材料及其电化学性能

以纤维素纳米晶(CNC)为模板,酚醛树脂为碳源,KOH为活化剂,通过高温碳化制备了多级孔炭材料.采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)等手段对合成的一系列炭材料进行了表征.结果表明,前驱体中CNC的降解会形成与CNC直径相当的介孔,KOH活化则会导致炭材料产生大量的微孔和大孔,以及部分4 nm左右较小尺度的介孔,所制备炭材料呈现明显的多级孔特性,其比表面积达554.7 m²/g,总孔体积为0.323 cm³/g.以CNC为模板,KOH活化的炭材料作为电极材料时,在1.0 A/g电流密度下其比电容达202.8 F/g,当电流密度升高至40.0 A/g时,其电容保持率仍达69%,表明该炭材料具有优异的倍率性能;由该电极材料组装的超级电容器在10000次充放电循环后,电容保持率达95%以上,具有良好的循环稳定性.     

有序介孔炭的合成及液相有机大分子吸附性能研究

分别采用有序介孔氧化硅SBA-15和NaY分子筛为硬模板合成了系列有序介孔炭OMC和微孔炭CFY. N₂静态吸附测试表明, 所合成的介孔炭具有丰富的介孔结构和集中的介孔分布. 以亚甲基蓝为探针分子, 研究其在有序介孔炭OMC和微孔炭CFY上的吸附行为. 研究结果表明, 有序介孔炭中大于3.5 nm的大介孔孔容是决定亚甲基蓝吸附容量和吸附速率的关键因素. 吸附动力学理论研究表明, 准二级动力学方程可以很好地描述亚甲基蓝分子在介孔炭上吸附动力学行为.     

HY分子筛为模板合成的微孔炭及其电化学电容性能

以HY分子筛为模板, 采用糠醇浸渍炭化法和糠醇浸渍-乙腈气相沉积炭化法制备了多种微孔炭材料, 分别标记为PFA系列和AN系列, 并研究了其电化学电容性能. X射线衍射(XRD)测试表明AN系列炭材料较好地复制了HY分子筛模板的孔结构有序性. X射线光电子能谱仪(XPS)测试表明, 乙腈气相沉积在炭材料中引入丰富的含氮官能团. 氮气吸附测试表明, 炭材料是典型的微孔材料, 具有较高的比表面积, 较窄的孔径分布范围. 电化学测试表明, AN系列炭材料电容性能较好, 并具有明显的赝电容, 其中AN8的比电容最大可达210 F·g^-1. AN系列炭材料的电容保持率与材料的导电性和介孔率有关.     

金属有机框架-有序介孔碳修饰的玻碳电极用于测定8-羟基脱氧鸟苷北大核心CSCD

通过水热法制备了金属有机框架材料(ZIF-8),采用ZIF-8和有序介孔碳(OMC)修饰玻碳电极(GCE),采用循环伏安法和交流阻抗法对此修饰电极(ZIF-8/OMC/GCE)的电化学性能进行了研究。结果表明,经过修饰可增大裸玻碳电极的有效表面积、改善电极的电催化活性。利用差分脉冲伏安法研究了8-羟基脱氧鸟苷在ZIF-8/OMC/GCE上的电化学特性。结果表明,此修饰电极的电流响应值与8-羟基脱氧鸟苷的浓度在0.35~350μmol·L-1内呈线性关系,检出限(3S/N)为0.22μmol·L-1。采用修饰电极测定人尿样中的8-羟基脱氧鸟苷,加标回收率在90.1%~108%之间。     

KOH添加方式对煤基活性泡沫炭电化学性能的影响

以强黏性炼焦煤为原料,经常压自发泡法制得的煤基泡沫炭(NCF)为碳基底,KOH为活化剂,采用机械混合、水溶液浸渍、乙醇浸渍三种不同的方式制备煤基活性泡沫炭(HPCs),并将其用作双电层电容器的电极材料,研究了KOH添加方式对其微观结构和电化学性能的影响。结果表明,KOH分散度和附着性对煤基活性泡沫炭孔隙结构的生成、晶体结构、表面化学性质以及电化学性能有显著影响。煤基泡沫炭本身具有三维连通泡孔结构,有利于活化剂(KOH)深入材料的泡孔内部并为其提供大量附着位点,增大活化剂与碳基体的接触面积进而发生高效的活化。KOH水溶液的流动性较好,可以使K⁺更有效地穿插在NCF的泡孔结构中,在活化过程中作用于缺陷部位,在碳基体内部基质上产生更多的微孔以及介孔结构,有效地放大了活化效果。KOH水溶液浸渍泡沫炭材料制得的ACF-W样品拥有最高的比表面积(3098.35 m²/g)、总孔体积(1.68 cm³/g)、介孔体积比(59.13%),将其用作电极材料表现出优异的比电容(310 F/g)以及循环稳定性。     

超级电容器炭电极材料孔结构对其性能的影响

采用无瓶颈的系列酚醛树脂活性炭为电极材料，用氮吸附和恒流充、放电，以及交流阻抗法，研究孔径和孔表面积等孔结构对其性能的影响.结果表明，活性炭电极材料双电层电容与微孔(孔宽度< 2.0 nm)表面和外孔(孔宽度 >2.0 nm)表面都有关系，但主要取决于微孔表面双电层电容.微孔表面比电容为21.4 μF•cm－2，外孔表面比电容< 10 μF•cm－2.外孔表面比电容较低可能是由于空间电荷层的影响.微孔孔径较大的炭材料具有高比电容和良好的高倍率放电的特性.     

不同碳源对多孔球形LiFePO4/C复合材料的影响

采用喷雾干燥-碳热还原法(SDCTM),分别研究了无机和有机碳源对锂离子正极材料LiFePO4/C形貌、结构及其充放电性能的影响。结果表明:以无机碳源炭黑制备的LiFePO4/C呈不规则球形,一次颗粒粒径在800nm左右,比表面积为2m2·g-1,0.1C放电比容量为107.3mAh·g-1。而以有机碳源制备的LiFePO4/C,其形貌较为规则,呈多孔球形结构,具有较高的比表面积和放电比容量。其中,以柠檬酸为碳源制备的多孔球形LiFePO4/C复合材料,其孔径均在50nm左右,比表面积可达32m2·g-1;在室温下,0.1C和10C首次放电比容量分别为158.8和87.2mAh·g-1,具有优异的循环性能和高倍率充放电性能。     

Nitrogen-Doped Porous Carbon Materials Derived from Graphene Oxide/Melamine Resin Composites for CO2 Adsorption

CO₂ adsorption in porous carbon materials has attracted great interests for alleviating emission of post-combustion CO₂. In this work, a novel nitrogen-doped porous carbon material was fabricated by carbonizing the precursor of melamine-resorcinol-formaldehyde resin/graphene oxide (MR/GO) composites with KOH as the activation agent. Detailed characterization results revealed that the fabricated MR(0.25)/GO-500 porous carbon (0.25 represented the amount of GO added in wt.% and 500 denoted activation temperature in °C) had well-defined pore size distribution, high specific surface area (1264 m²·g⁻¹) and high nitrogen content (6.92 wt.%), which was mainly composed of the pyridinic-N and pyrrolic-N species. Batch adsorption experiments demonstrated that the fabricated MR(0.25)/GO-500 porous carbon delivered excellent CO₂ adsorption ability of 5.21 mmol·g⁻¹ at 298.15 K and 500 kPa, and such porous carbon also exhibited fast adsorption kinetics, high selectivity of CO₂/N₂ and good recyclability. With the inherent microstructure features of high surface area and abundant N adsorption sites species, the MR/GO-derived porous carbon materials offer a potentially promising adsorbent for practical CO₂ capture.     

New method for development of carbon clad silica phases for liquid chromatography: Part I. Preparation of carbon phases

Owing to its combination of unique selectivity and mechanical strength, commercial carbon clad zirconia (C/ZrO₂) has been widely used for many applications, including fast two-dimensional liquid chromatography (2DLC). However, the low surface area available (only 20–30 m²/g for commercial porous ZrO₂) limits its retentivity. We have recently addressed this limitation by developing a carbon phase coated on the high surface area of HPLC grade alumina (C/Al₂O₃). This material provides higher retentivity and comparable selectivity, but its use is still limited by how few HPLC quality types of alumina particles (e.g., particle size, surface area, and pore size) are available. In this work, we have developed useful carbon phases on silica particles, which are available in various particle sizes, pore sizes and forms of HPLC grade. To make the carbon phase on silica, we first treat the silica surface with a monolayer or less of metal cations that bind to deprotonated silanols to provide catalytic sites for carbon deposition. After Al (III) treatment, a carbon phase is formed on the silica surface by chemical vapor deposition at 700 °C using hexane as the carbon source. The amount of Al (III) on the surface was varied to assess its effect on carbon deposition, and the carbon loading was varied at different Al (III) levels to assess its effect on the chromatographic properties of the various carbon adsorbents. We observed that use of a concentration of Al (III) corresponding to a full monolayer leads to the most uniform carbon coating. A carbon coating sufficient to cover all the Al (III) sites, required about 4–5 monolayers in this work, provided the best chromatographic performance. The resulting carbon phases behave as reversed phases with reasonable efficiency (50,000–79,000 plates/m) for non-aromatic test species.     

Surface Chemistry and Structure of Silicon Oxycarbide Gels and Glasses

In this study, the surface chemistry and structure of methyl-substituted silica gels and porous oxycarbide glasses were investigated. FTIR was used to measure the relative concentration of Si−CH₃ and Si−OH as a function of the degree of methyl-substitution and the pyrolysis temperature. The gels and glasses were further heated, dehydrated or hydrated, in situ, within the FTIR spectrometer. In the temperature range of 800–850°C, high surface area oxycarbide glasses were created with no detectable surface hydroxyl groups. Oxycarbide glasses synthesized in argon at 700°C displayed a weak band for surface hydroxyl groups and reversible physisorption of water, while those synthesized at 850/900°C showed a complete absence of surface hydroxyl groups and the formation of vicinal silanols upon chemisorption of water. Isolated silanols were observed upon heat treatment in vacuum. Formation of aromatic carbon species was found to correlate with the decomposition of the methyl groups. The oxycarbide surface is quite stable to densification (presumably due to elemental carbon on the pore surfaces). In the absence of oxygen, porous silicon oxycarbide glass powders maintain surface areas >200 m²/g at 1200°C. However, oxidizing species in the atmosphere deplete the aromatic carbon species, and the glasses lose surface area.     

花生壳基多孔碳负载Pd-Co催化剂应用于碱性介质中电氧化甲醇

以花生壳为原料,经KOH活化制备花生壳基多孔碳（HC）。氮气吸附-脱附研究表明,所获得的多孔碳的总表面积高达1 645 m²·g^-1。采用浸渍还原法制备了以HC为载体的Pd-Co/HC催化剂。X射线衍射（XRD）和X射线光电子能谱（XPS）分析表明,催化剂中的Co主要以Co和CoO的形式存在,Co进入Pd的晶格并形成Pd-Co合金。Pd-Co/HC_0.5-700的透射电子显微镜（TEM）结果显示,Pd-Co纳米颗粒具有较小粒径（约4 nm）且成功地分散在HC上。Pd-Co/HC_0.5-700在碱性介质中电催化氧化甲醇时表现出优秀的电催化活性、稳定性和CO耐受性,这种显著的高性能可以归因于生物质载体大的表面积和Co的成功掺杂。     

花生壳基多孔碳负载Pd-Co催化剂应用于碱性介质中电氧化甲醇

以花生壳为原料,经KOH活化制备花生壳基多孔碳(HC)。氮气吸附-脱附研究表明,所获得的多孔碳的总表面积高达1 645 m²·g^-1。采用浸渍还原法制备了以HC为载体的Pd-Co/HC催化剂。X射线衍射(XRD)和X射线光电子能谱(XPS)分析表明,催化剂中的Co主要以Co和Co O的形式存在,Co进入Pd的晶格并形成Pd-Co合金。Pd-Co/HC_0.5-700的透射电子显微镜(TEM)结果显示,Pd-Co纳米颗粒具有较小粒径(约4 nm)且成功地分散在HC上。Pd-Co/HC_0.5-700在碱性介质中电催化氧化甲醇时表现出优秀的电催化活性、稳定性和CO耐受性,这种显著的高性能可以归因于生物质载体大的表面积和Co的成功掺杂。     

Synthesis of High‐Surface‐Area Nitrogen‐Doped Porous Carbon Microflowers and Their Efficient Carbon Dioxide Capture Performance

Sustainable carbon materials have received particular attention in CO₂ capture and storage owing to their abundant pore structures and controllable pore parameters. Here, we report high‐surface‐area hierarchically porous N‐doped carbon microflowers, which were assembled from porous nanosheets by a three‐step route: soft‐template‐assisted self‐assembly, thermal decomposition, and KOH activation. The hydrazine hydrate used in our experiment serves as not only a nitrogen source, but also a structure‐directing agent. The activation process was carried out under low (KOH/carbon=2), mild (KOH/carbon=4) and severe (KOH/carbon=6) activation conditions. The mild activated N‐doped carbon microflowers (A‐NCF‐4) have a hierarchically porous structure, high specific surface area (2309 m² g^?1), desirable micropore size below 1 nm, and importantly large micropore volume (0.95 cm³ g^?1). The remarkably high CO₂ adsorption capacities of 6.52 and 19.32 mmol g^?1 were achieved with this sample at 0 °C (273 K) and two pressures, 1 bar and 20 bar, respectively. Furthermore, this sample also exhibits excellent stability during cyclic operations and good separation selectivity for CO₂ over N₂.     

植物基多孔炭材料在超级电容器中的应用

植物基多孔炭具有发达的孔结构、大的表面积、较为成熟的制备工艺、丰富的来源、低廉的价格,是目前商业应用范围最广的超级电容器电极材料。然而在实际应用中仍然存在着质量/体积比容量较低、倍率性能差等问题。本文针对先进电容器件的高能量密度、优异功率性能的要求,首先介绍了近年来发展的植物基多孔炭的制备方法,讨论了植物前驱体的组成和结构对其产物结构的影响以及与其电化学性能之间的构效关系,特别总结了近年来植物基超大比表面积多孔炭、中孔炭、层次化多孔炭的制备方法和电容储能性能。针对大比表面积多孔炭用于超级电容器时的体积性能不佳这一关键问题,本文还总结了提高植物基多孔炭体积电化学性能的方法。最后,对植物基多孔电极材料存在的问题进行了分析与总结,并展望了其研究前景。     

Adsorption of carbon dioxide-methane mixtures in porous carbons: effect of surface chemistry

A combined experimental and molecular simulation study of the coadsorption of CO₂ and CH₄ in porous carbons is reported. We address the effect of surface chemistry by considering a numerical model of disordered porous carbons which has been modified to include heterochemistry (with a chemical composition consistent with that of the experimental sample). We discuss how realistic the numerical sample is by comparing its pore size distribution (PSD), specific surface area, porous volume, and porosity with those for the experimental sample. We also discuss the different criteria used to estimate the latter properties from a geometrical analysis. We demonstrate the ability of the MP method to estimate PSD of porous carbons from nitrogen adsorption isotherms. Both the experimental and simulated coadsorption isotherms resemble those obtained for pure gases (type I in the IUPAC classification). On the other hand, only the porous carbon including the heterogroups allows simulating quantitatively the selectivity of the experimental adsorbent for different carbon dioxide/methane mixtures. This result shows that taking into account the heterochemistry present in porous carbons is crucial to represent correctly adsorption selectivities in such hydrophobic samples. We also show that the adsorbed solution theory describes quantitatively the simulated and experimental coadsorption isotherms without any parameter adjustment.     

百香果皮基原位氮掺杂多孔碳/硫复合正极的制备及储锂性能

以生物质百香果皮为碳源,KHCO₃为活化剂,采用同步活化碳化方法制备原位氮掺杂的分级多孔碳材料,将其与单质硫复合制得多孔碳/硫正极材料。通过X射线衍射（XRD）、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）等表征技术对制备材料的物相组成、微观形貌、比表面积及孔结构进行研究分析。同时,利用紫外可见吸收光谱研究了多孔碳对多硫化物的吸附作用,用恒电流充放电测试了不同硫含量（60%~80%）的多孔碳/硫复合正极材料的电化学性能。结果表明,制得的多孔碳材料为无定型,具有1 093 m²·g^-1的高比表面积和0.63 cm³·g^-1的孔容;丰富的多孔结构和原位氮掺杂对多硫化物的物理化学协同吸附作用,有效降低了锂硫电池的“穿梭效应”,提高了电池的放电比容量和循环性能。硫含量为60%的多孔碳/硫复合材料,在0.05C和0.2C倍率下可释放1 057.7和763.4 mAh·g^-1的高初始放电比容量,在1C的高倍率下循环300次后的保持率为75%。