氧化锰表面改性活性炭电极材料的电化学特性

用Mn(NO3)2溶液浸渍-高温热解法对普通活性炭进行表面改性处理以改善其电化学性能. 采用氮气吸附、SEM、XRD等方法研究改性活性炭的比表面积、孔结构、形貌和氧化锰的晶体结构; 用循环伏安、恒流充放电、交流阻抗等电化学方法研究了改性活性炭电极构成的电化学电容器的性能. 结果表明, Mn(NO3)2热解产生的多价态氧化锰有法拉第赝电容效应, 尤其是立方晶形结构的α-Mn2O3, 与活性炭的双电层电容构成了复合电容, 因而改性炭材料的比电容有明显的提高, 其质量比电容达到254 F·g-1, 比未改性炭的165 F·g-1提高了54%. 改性炭电极电化学电容器具有优异的充放电可逆性和稳定性, 而且等效串联电阻较小, 只有0.40 Ω; 经2000次循环的长期测试, 容量保持率几乎达到100%.     

高能量密度和功率密度炭电极材料

以核桃壳为原料, 采用同步物理-化学活化法制备活性炭(AC). 用氮气吸附法和傅立叶红外光谱(FTIR), 对活性炭的孔结构和表面官能团进行了分析. 以活性炭为电极材料制备炭电极, 6 mol·L-1 KOH溶液为电解液组装成超级电容器, 利用恒电流充放电、循环伏安、交流阻抗等电化学测试方法研究其电化学性能及其与活性炭材料结构的关系. 结果表明, 实验电容器的内电阻、漏电流小, 循环充放电稳定性好, 容量保持率高; 活性炭的比电容随比表面积的增加而增大, 且与BET比表面积呈线性相关; 孔径在1.5-4 nm之间的孔表面有利于形成有效的双电层. 中等比表面积1197 m2·g-1炭样的比电容高达292 F·g-1, 80 mA充放电时, 电容器能量密度高达7.3 Wh·kg-1, 功率密度超过770 W·kg-1,峰值功率密度为5.1 W·g-1.     

电化学双电层电容器用新型炭材料及其应用前景

活性炭是目前使用最为广泛的一种电化学双电层电容器（EDLC）的电极材料,但其固有的缺点制约了EDLC性能的进一步提高。用新型高性能炭电极材料可使EDLC比能量和比功率性能进一步提高。这些新型炭材料包括基于石墨层状结构的纳米门炭,基于碳纳米管阵列结构的毛皮炭,通过高温置换反应制备的骨架炭以及电极可整体成型的纳米孔玻态炭。本文介绍了这些炭材料的电化学特性及其在电化学双电层电容器中的应用,指出用这4种新型炭材料制备EDLC的比能量或比功率性能远高于目前活性炭基EDLC,具有良好的应用前景。     

硝酸改性活性炭上氧/氮官能团对脱汞性能的促进作用

采用硝酸氧化手段对活性炭进行了表面处理, 并在固定床反应器上测试了其脱除单质汞的性能. 研究表明, 在模拟烟气中硝酸改性活性炭能有效脱除单质汞. 采用元素分析、Brunauer-Emmett-Teller (BET)比表面积、扫描电子显微镜(SEM)、拉曼(Raman)光谱、Boehm滴定、程序升温脱附(TPD)和X射线光电子能谱(XPS)等手段研究了活性炭表面官能团对其脱汞性能的影响. 结果表明: 硝酸氧化处理能同时增加活性炭表面含氧官能团和含氮官能团的含量. 与改性活性炭的物理性质相比, 其化学性质对脱汞性能的影响更大, 单质汞主要被改性活性炭氧化为HgO而去除. 在脱汞反应中, 羰基、酯基和酸酐等含氧官能团可能是活性吸附位点, 反应后这些官能团被还原为羟基或者醚基; 而吡咯等含氮官能团可能是活性催化位点. 此外, 基于上述表征结果提出了硝酸改性活性炭表面官能团的脱汞机制.     

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.     

水热法硼磷改性多孔炭及其电化学性能研究

采用水热法硼磷改性椰壳多孔炭,并对其电化学性能进行研究。通过X射线衍射、红外光谱以及氮气吸脱附表征改性前后多孔炭的结构和性能;将多孔炭制作电化学电容器负极,通过恒流充放电、循环伏安以及交流阻抗测试分析其电化学性能。结果表明,水热法硼磷改性使多孔炭的微观结构及组成发生了一定变化,比电容等电化学性能有明显的提高。渗硼剂为氧化硼,渗硼量为15(wt)%时,比电容达108 F/g,比原始样增长了92%;渗硼剂为硼酸,渗硼量为25(wt)%时,比电容达到98 F/g,比原始样增长了83%。     

超级电容器用中孔炭复合电极材料研究进展

超级电容器是一类利用电化学双电层或电极材料在电极/溶液界面发生的氧化还原反应来存储能量的装置,除兼有常规电容器功率密度大和二次电池能量密度高的特点外,还具有可逆性好和循环寿命长等优点.本文重点介绍了近几年国内外对中孔炭材料、表面官能团修饰中孔炭材料、中孔炭-金属氧化物、中孔炭-导电聚合物等几类电极材料的研究现状;并且展望了超级电容器用中孔炭及其复合电极材料的当前研究热点和发展前景.     

电弧放电法制备石墨烯的硝酸改性及其电化学性能增强

采用电弧放电法大规模制备了层数少, 导电率高, 结晶性好的石墨烯纳米片(GNSs). 通过扫描电镜(SEM)和透射电镜(TEM)表征发现制得的石墨烯形貌良好. 然而电化学测试表明GNSs作为电极材料的电容性能不好. 为了增加材料表面电化学反应活性点, 促进GNSs在水系电解液中的润湿性, 我们对所制备的GNSs表面进行了硝酸改性处理. 结果显示硝酸处理后的石墨烯纳米片(H-GNSs)表面新增了较多的含氧氮官能团,其亲水性得到了显著提高. 对H-GNSs的电化学研究表明: 硝酸改性处理后的GNSs在2 mol·L^-1 KOH溶液中电流密度为0.5 A·g^-1时, 比电容可达65.5 F·g^-1, 约为改性前的30 倍; 此外, H-GNSs作为电极材料连续进行2000次充放电测试后还展示出了良好的循环稳定性, 是一种潜在的超级电容器电极材料.     

可调有序介孔炭在有机和硫酸电解液中的电容性质

采用硬模板法, 掺杂硼酸制备了一系列有序介孔炭材料, 并研究了其在有机和硫酸电解液中的电容性质. 结构分析表明, 该类炭材料具有平行排列的有序介孔孔道, 随硼酸摩尔分数从0增大至50%, 炭材料孔径尺寸从3.3 nm增大至5.7 nm, 表面含氧量从2.0%增大至5.2%(摩尔分数). 电化学测试表明, 在有机电解液中, 炭材料的电容性能主要是双电层电容, 含氧官能团没有引入明显的赝电容. 在硫酸电解液中, 掺杂5%硼酸制备的有序介孔炭材料BOMC-5的质量比电容值最大, 为140.9 F·g^-1; 随含氧量增大, 炭材料单位面积比电容值增大, 掺杂50%硼酸制备的炭材料BOMC-50的单位面积比电容值达到0.17 F·m^-2, 说明含氧官能团在硫酸电解液中引入明显的赝电容. 炭材料的表面化学性质决定了材料表面与电解液的浸润性, 是影响炭材料比电容保持率的主要因素.     

炭载体改性对炭载Pd催化剂电催化性能的影响

研究了硝酸和氨水改性处理对活性炭表面基团、炭载Pd纳米粒子的形态及其对甲酸氧化电催化性能的影响.傅里叶变换红外(FT-IR)光谱、X射线光电子能谱(XPS)及Boehm滴定结果表明,硝酸和氨水处理分别增加了活性炭表面含氧基团和含氮基团的含量.透射电镜(TEM)及电化学测试显示,活性炭经硝酸处理后,表面负载的Pd粒子粒径降低,催化剂对甲酸氧化活性和稳定性提高.进一步用氨水处理后,Pd粒子的粒径没有明显变化,但催化剂中Pd0的含量增加,催化剂性能进一步提高.     

Surface Modification and Performance of Activated Carbon Electrode Material

A commercial activated carbon was modified by surface treatment using three chemicals, nitric acid, hydrogen peroxide, and ammonia, respectively. The modified carbons were characterized by N₂ adsorption-desorption isotherms and FTIR spectroscopy. The resultant carbon electrode-based electric double-layer capacitors (EDLCs) were assembled with 6 mol·L⁻¹ KOH as the electrolyte. The influence of surface modification on the performance of EDLCs was studied by galvanostatic charge-discharge, cyclic voltammetry, and alternating current impedance. The surface modification resulted in no big decrease in specific surface area and little decrease in average pore size, and introduced functional groups, such as hydroxyl, carbonyl, and amidogen, on the carbon surface. These functional groups significantly improved the wettability and reduced the resistance of the activated carbon. As a result, the specific capacitance of the carbon modified with 65% HNO₃ reached 250 F·g⁻¹, 72.4% higher than that of original carbon. The leakage current of testing EDLCs decreased unexpectedly to 3-18 μA, only 0.8%-4.9% that of the original carbon electrode-based EDLC (371 μA).     

A novel carbon electrode material for highly improved EDLC performance

Porous materials, developed by grafting functional groups through chemical surface modification with a surfactant, represent an innovative concept in energy storage. This work reports, in detail, the first practical realization of a novel carbon electrode based on grafting of vinyltrimethoxysilane (vtmos) functional group for energy storage in electric double layer capacitor (EDLC). Surface modification with surfactant vtmos enhances the hydrophobisation of activated carbon and the affinity toward propylene carbonate (PC) solvent, which improves the wettability of activated carbon in the electrolyte solution based on PC solvent, resulting in not only a lower resistance to the transport of electrolyte ions within micropores of activated carbon but also more usable surface area for the formation of electric double layer, and accordingly, higher specific capacitance, energy density, and power capability available from the capacitor based on modified carbon. Especially, the effects from surface modification become superior at higher discharge rate, at which much better EDLC performance (i.e., much higher energy density and power capability) has been achieved by the modified carbon, suggesting that the modified carbon is a novel and very promising electrode material of EDLC for large current applications where both high energy density and power capability are required.     

活性炭纤维吸附脱除NO过程中NO氧化路径分析

在小型固定床吸附实验台上开展了黏胶基活性炭纤维吸附脱除NO的实验研究。采用H₂O₂溶液浸渍以及热处理方法对活性炭纤维表面进行修饰,以获得表面孔隙结构接近而含氧官能团含量不同的样品;考察样品在惰性氮气气氛、含氧气氛下吸附脱除NO的效果,以及表面含氧含氮官能团的变化规律。探讨了含氧官能团在NO催化氧化过程中的作用及含氧气氛下O₂对于NO转化为NO₂的影响,分析了活性炭纤维表面吸附的NO向NO₂的主要转化途径。结果表明,在氮气气氛下活性炭纤维表面C-O官能团对吸附态的NO起到氧化作用,吸附态NO被C-O官能团氧化生成-NO₂官能团;在含氧气氛下活性炭纤维吸附NO后表面出现-NO₂、-NO₃官能团,通过长时间实验测定三种样品在含氧气氛下对NO吸附的效果,发现三种样品稳定时催化氧化效果一致,表明含氧官能团对初始NO的物理吸附影响较大,而对整个吸附过程影响较小。吸附在活性炭纤维表面上的NO与环境气氛中的游离态O₂发生氧化反应是NO转变为NO₂的主要途径。     

Highly active catalyst for vinyl acetate synthesis by modified activated carbon

A new zinc acetate catalyst which was prepared from modified activated carbon exhibited extreme activity towards the synthesis of vinyl acetate.The activated carbon was modified by nitric acid,vitriol and peroxyacetic acid(PAA).The effect on specific area, structure,pH and surface acidity groups of carriers by modification was discussed.Amount of carbonyl and carboxyl groups in activated carbon was increased by peroxyacetic acid treatment.The productivity of the new catalyst was 14.58%higher than that of...     

乙炔法合成醋酸乙烯催化剂载体表面羧基与羰基作用机理的研究

比较了硝酸、硫酸、过氧乙酸改性对载体比表面积、孔结构、pH值以及载体表面基团的影响. 研究了过氧乙酸(PAA)改性条件对催化剂活性的影响. 改性提高了活性炭表面羧基和羰基的含量, 由在最佳PAA改性条件下制备的乙炔法合成醋酸乙烯催化剂生产能力比未经过氧乙酸改性活性炭制备的催化剂提高了14.58%. 得到了过氧乙酸改性后活性炭表面羧基和羰基总量(m)和合成醋酸乙烯催化剂生产能力(P)之间的关系为P＝1.83＋2.26×10－3×e3.17m, 并讨论了催化剂表面羧基与羰基提高催化剂活性的机理.     

Acid/Base-treated activated carbons: characterization of functional groups and metal adsorptive properties

Surface modification of activated carbons by various physicochemical methods directs an attractive approach for improvement of heavy metal uptake from aqueous solutions. Activated carbons were modified with HCl and HNO3 optionally followed by NaOH. The effects of surface modifications on the properties of the carbons were studied by the specific surface area, carbon pH, and total acidity capacity as well as by scanning electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The modifications bring about substantial variation in the chemical properties whereas the physical properties remain nearly unchanged. NaOH causes an increase in the content of hydroxyl groups, while the HCl treatment results in an increase in the amount of single-bonded oxygen functional groups such as phenols, ethers, and lactones. The HNO3 modification generates a large number of surface functional groups such as carbonyl, carboxyl, and nitrate groups. The HNO3 modification significantly increases the copper adsorption, while the HCl treatment slightly reduces the copper uptake. Most of the copper ions are adsorbed rapidly in the first 2 h; the adsorption equilibrium is established in around 8 h. An intraparticle diffusion model successfully describes the kinetics of copper adsorption onto the carbons.     

Phenobarbital interactions with derivatized activated carbon surfaces

The interactions between phenobarbital and activated carbon surfaces were studied in detail in this work. This was accomplished by utilizing different reagents to manipulate the surface polar functional group compositions of different activated carbons, and determining how those modifications changed phenobarbital adsorption. Oxidation of an activated carbon surface caused a systematic decrease in the basal carbon surface, resulting in a concurrent systematic decrease in the non-specific adsorption of phenobarbital. Even more interesting, it was shown for the first time that chemical reduction of some of the carbonyl-containing functional groups on the activated carbon surface caused a significant increase in the specific adsorption of phenobarbital without any significant effect on the non-specific adsorption. These results support the notion that the OH groups on activated carbon surfaces are the specific adsorption sites for phenobarbital from aqueous solutions, and that the basal carbon surface is the region where non-specific adsorption takes place.     

Secondary Activation of Commercial Activated Carbon and its Application in Electric Double Layer Capacitor

The cheap commercial activated carbon (AC) was improved through the secondary activation under steam in the presence of FeCl2 catalyst in the temperature range of 800-950℃ and its application in electric double layer capacitors(EDLCs) with organic electrolyte was studied. The re-acivation of AC results in the increases in both specific capacitance and high rate capability of DELCs. For AC treated under optimized conditions, its discharge specific capacitance increases up to 55.65F/g, an increase of about 33% as compared to the original AC, and the high rate capability was increased significantly.The good performances of EDLC with improved AC were correlated to the increasing mesoporous ratio.     

Electrochemical behavior of activated carbon electrodes in electric double layer capacitors with tetrametylammonium bis(oxalato)borate electrolyte synthesized by microwave irradiation

The electrochemical behavior of electric double layer capacitors (EDLCs) with tetramethylammonium bis(oxalato)borate electrolyte and electrodes based on various activated carbons (ACs) was studied. Tetraalkylammonium bis(oxalate)borate salts were synthesized by means of microwave (MW) irradiation. The specific conductivities of salt solutions were determined. It was shown that the efficiency of electric double layer capacitors increases with an increase in specific surface area and a decrease in the purity of carbon materials.     

A New Approach for Controlling Mesoporosity in Activated Carbon by the Consecutive Process of Air Oxidation,Thermal Destruction of Surface Functional Groups,and Carbon Activation (the OTA Method)

A new and simple method, based entirely on a physical approach, was proposed to produce activated carbon from longan fruit seed with controlled mesoporosity. This method, referred to as the OTA, consisted of three consecutive steps of (1) air oxidation of initial microporous activated carbon of about 30% char burn-off to introduce oxygen surface functional groups, (2) the thermal destruction of the functional groups by heating the oxidized carbon in a nitrogen atmosphere at a high temperature to increase the surface reactivity due to increased surface defects by bond disruption, and (3) the final reactivation of the resulting carbon in carbon dioxide. The formation of mesopores was achieved through the enlargement of the original micropores after heat treatment via the CO₂ gasification, and at the same time new micropores were also produced, resulting in a larger increase in the percentage of mesopore volume and the total specific surface area, in comparison with the production of activated carbon by the conventional two-step activation method using the same activation time and temperature. For the activation temperatures of 850 and 900 °C and the activation time of up to 240 min, it was found that the porous properties of activated carbon increased with the increase in activation time and temperature for both preparation methods. A maximum volume of mesopores of 0.474 cm³/g, which accounts for 44.1% of the total pore volume, and a maximum BET surface area of 1773 m²/g was achieved using three cycles of the OTA method at the activation temperature of 850 °C and 60 min activation time for each preparation cycle. The two-step activation method yielded activated carbon with a maximum mesopore volume of 0.270 cm³/g (33.0% of total pore volume) and surface area of 1499 m²/g when the activation temperature of 900 °C and a comparable activation time of 240 min were employed. Production of activated carbon by the OTA method is superior to the two-step activation method for better and more precise control of mesopore development.