Effects of nitrogen-doped carbon nanotubes on the discharge performance of Li-air batteries

Carbon nanotubes (CNTs) and nitrogen-doped carbon nanotubes (N-CNTs) were synthesized using a floating catalyst chemical vapor deposition method and characterized by scanning electron microscopy (SEM), transmission electron microscopy, Raman and X-ray photoelectron spectroscopy. The study found that the as-prepared CNTs and N-CNTs showed different discharge capacity as cathode materials in Li-air battery. To further study the reason why N-doping improves the electrochemical performance exceptionally, the discharge products on the two kinds of nanotubes were detected by SEM, XRD and Raman. SEM study showed, for the first time, that more uniform distribution of discharge products on the surface of CNTs arising from N-doping affected the boost of discharge capacity, a result which was discussed in detail. In comparison to non-doped CNTs, nitrogen doping was considered to be a promising way to improve the performance of carbon based cathode material for Li-air batteries.     

Graphitic mesoporous carbon as a support of promoted Rh catalysts for hydrogenation of carbon monoxide to ethanol

Graphitic mesoporous carbon (GMC), prepared through high-temperature graphitization of soft-templated amorphous mesoporous carbon (AMC), was used as the support for Mn, Li, and Fe triple-promoted Rh catalysts for CO hydrogenation to ethanol. The use of GMC results in C₂H₅OH selectivity and formation rate comparable to nonporous SiO₂ support along with a significant inhibition on the formation of undesired CH₄ and light hydrocarbons at the expense of appreciable amounts of CO₂ produced. The better catalytic performance of promoted-Rh/GMC than those supported on other carbon allotropes (AMC and non-porous graphitic carbon black) seems to be associated with the specific graphitic structure and mesoporosity of GMC. The surface modification of GMC by wet oxidation leads to considerable increases in C₂H₅OH selectivity and formation rate. The modified GMC as a support shows substantially greater CO₂-free selectivity for C₂H₅OH than the SiO₂.     

改性活性碳纤维对苯胺吸附特性分析

开展了等离子体改性活性碳纤维对苯胺吸附性能的理论和实验研究。通过改变等离子体改性功率和改性时间,探寻最佳改性条件;采用BET、XPS、FTIR、热重测试对改性前后活性碳纤维理化特性进行了表征分析。结果表明,在等离子改性功率为22W,时间为3min时为最佳改性条件;改性后的活性碳纤维对水溶液中苯胺的去除率可达79.3%,去除率提高了8%。微观上等离子体改性使得活性碳纤维表面含氧官能团含量增加,增强对溶液中苯胺的吸附效果。吸附实验结果表明,改性前后活性碳纤维对苯胺的吸附在溶液pH为6时,吸附效果最佳;但达到同一去除率时改性活性碳纤维的速度更快,并且平衡吸附容量也更大。采用准一级和准二级动力学模型对该吸附过程进行描述,其改性前后均用准二级动力学拟合效果更好,表明活性碳纤维结构的特殊性使其对苯胺的吸附以化学吸附为主。活性碳纤维的等离子体改性提高了其对水溶液中苯胺的吸附速度和容量,增强去除效果降低了苯胺对环境的危害。     

Functionalized activated carbon for the adsorptive removal of perchlorate from water solutions

Two types of activated carbon, namely, Filtrasorb 400 and Nuchar SA, were functionalized by quaternary ammonium salts (quats), as to enhance perchlorate adsorption. Results showed that the adsorption of quats on Nuchar SA increased with increase in chain length (hydrophobicity) of quats. Filtrasorb 400, however, had limited uptake of long-chain quats such as dodecyltrimethylammonium and hexadecyltrimethylammoium (HDTMA). Results indicated that perchlorate removal by the functionalized activated carbon was directly related to the chain length of the modifying quats. Perchlorate removal by functionalized activated carbon increased with increase in chain length of the modifying quats and became less pH-dependent. Modified Nuchar SA had higher overall perchlorate removal capacity than the modified Filtrasorb F400, but was more strongly affected by pH than Filtrasorb 400. Activated carbon treated with HDTMA exhibited the best perchlorate removal capacity among all quats studied. Results indicated that tailoring the activated carbon surface with HDTMA rendered the activated carbon surface positively charged, which resulted in substantial increase in perchlorate removal compared to unfunctionalized activated carbons.     

活性炭负载金属氧化物常温脱除低浓度NO

在活性炭上负载了金属氧化物用于低浓度NO在常温下的脱除。活性炭在使用之前经过了氧化预处理,经过硝酸氧化处理后,活性炭表面的羰基和硝基数量均增加,对NO的脱除能力显著提高。在硝酸处理后的活性炭上负载了金属氧化物,其中Ce和Co负载的样品对NO的脱除效果最佳,与未负载的样品相比脱除量提高了约8倍。进一步研究发现被脱除的NO最终以金属硝酸盐的形式存在,说明NO在通过催化氧化吸附剂层时首先被氧化生成NO2,之后NO2与负载的金属氧化物反应生成了金属硝酸盐。     

表面改性活性炭吸附CS2及微波场中再生的研究

利用浸渍法探讨氧化物和含氮物质表面改性活性炭对CS2吸附性能的影响,通过boehm滴定和FT-IR分析结果证明:双氧水改性使活性炭表面碱性基团数增多,CS2动态吸附量增大;氨水和乙二胺改性活性炭,其表面碱性基团数增多,并引入含氮官能团,提高了CS2吸附容量。建立微波再生正交实验,确定微波再生最优实验条件:微波功率110 W、辐射时间2 min、载气流量250 mL/min时,活性炭再生综合率最大。对改性活性炭进行TG-DSC热分析,为活性炭微波热再生提供可靠参考依据。实验结果证明:双氧水、氨水、乙二胺改性可提高活性炭综合再生恢复率,硝酸改性对活性炭再生不利。     

High capacity supercapacitors based on modified activated carbon aerogel

Carbon aerogel derived from a modified resorcinol–formaldehyde (RF) method without supercritical drying step was activated under CO₂ flow and further modified with a surfactant sodium oleate solution. Carbon aerogel, activated carbon aerogel (ACA) and modified activated carbon aerogel (MACA) were characterized by Brunaver, Emmett and Teller(BET) surface measurement, constant-current charge–discharge and cyclic voltammetry(CV). It was found that the specific surface area of the ACA was twice that without activation. At relatively low discharge rates the specific capacitance and energy delivered from the capacitor were improved greatly by the activation of carbon aerogel. To apply the ACA at high discharge rate, a surface modification was introduced. After the surface modification the wettability of the organic electrolyte based on non-polar organic solvent (i.e. propylene carbonate) to the ACA was improved greatly and, as a result, the internal resistance of the capacitor decreased and the specific capacitance and energy delivered increased at all the test discharge rates. The effects from the modification become more marked at higher discharge rates, i.e. at 48mAcm^–2, the energy delivered increased by ca. 70%, which indicates the MACA more suitable as electrode material in electric double-layer capacitors (EDLCs) for high current applications.     

Modification of activated carbon with a silane coupling agent under ultrasonic conditions for the advanced treatment of wastewater with dressing chemicals

Fresh activated carbon (FAC) was oxidised by nitric acid and then the silane coupling agent was grafted onto the surface of FAC under ultrasonic conditions to obtain modified activated carbon (MAC). The chemical oxygen demand was used as the main evaluation index in the wastewater. The effects of benzene, aniline, 2‐mercaptobenzothiazole and methylene blue on the adsorption mechanism and performance of FAC prior and postmodification were investigated by different adsorption models. All of them fitted the Langmuir monomolecular adsorption model. The adsorption capacity of MAC was 1.07, 1.12, 1.56 and 0.62 times that of FAC, respectively, which had a better adsorption effect on hydrophobic organic compounds. The maximum adsorption capacity increased due to the existence of competitive adsorption in multicomponent absorption. Texture properties of activated carbon were characterised by scanning electron microscopy, Fourier Transform‐infrared and Brunauer–Emmett–Teller theory, which show that the surface morphology became spongy, and that Si–O–C and Si–O infrared peaks appeared. In addition to the mesopore volume, the specific surface area, pore volume and micropore volume decreased slightly after the modification.     

活性炭用于柴油深度脱硫研究进展

综述了活性炭作为吸附剂和催化剂在柴油深度脱硫方面应用的新进展。通过表面热氧化和负载金属离子对活性炭表面进行化学性能改性,有效提高对柴油中噻吩类硫化物的吸附性能。活性炭作为催化剂,能有效催化过氧化氢和氧化柴油中的噻吩类硫化物而达到催化氧化脱硫。活性炭在柴油深度脱硫方面具有广阔的应用前景,但要真正实现其在脱硫上的工业化应用,尚需加强其表面化学性能改性、再生、吸附和催化氧化机理等方面的研究。     

TiO2 photocatalyst deposition by MOCVD on activated carbon

Activated carbon modified by HNO₃ was used as the support during the production of TiO₂ by metal organic chemical vapor deposition (MOCVD). The HNO₃ modification increased mesopores surface area of activated carbon indicating the size of pores increased. The concentration of surface oxygen bearing groups on the HNO₃ modified activated carbon was much higher than that of the original activated carbon. It was found that a modification of activated carbon by 6 mol/L HNO₃ increased the deposition rate of TiO₂ by 4.5 times. The modification of activated carbon by HNO₃ significantly raised the photocatalytic activity of TiO₂ resulting from the formation of smaller-sized TiO₂ particles well dispersed confirmed by the results of XRD patterns and N₂ adsorption-desorption isotherms.     

Effects of chemical modification of petroleum cokes on the properties of the resulting activated carbon

Activated carbons have been prepared from petroleum cokes by the combination of a chemical treatment with HClO₄ or H₂O₂ and a chemical activation with KOH at a constant KOH/coke ratio of 3/1. The influence of different chemical treatments on the properties of the activated carbon precursors and final carbons activated with KOH was invested by using XRD, FTIR, and BET techniques. XRD results indicated that the value of interplanar distance d₀₀₂ increased by chemical treatment and the disappearance of the peak corresponding to 0 0 2 faces correlated to high specific surface area. FTIR studies showed that chemical modification promoted the formation of surface oxygen functionalities. Significant effects on BET surface area, pore texture and iodine adsorption capacity were evidenced. The results show that chemical modification prior to activation dramatically increased the BET surface area and total pore volume of the resulting activated carbon. Modified petroleum coke based activated carbon with chemical activation had higher specific surface area (2336 m²/g) and better iodine adsorption value (1998 mg/g).     

活性炭表面含氧官能团对水中卤乙酸吸附去除的影响

为了改善极性、亲水性卤乙酸(HAAs)分子在非极性、疏水性活性炭上的吸附性能,利用N₂等温吸附实验、X射线光电子能谱实验（XPS）、HAAs等温吸附实验等方法,对几种不同产地的活性炭孔隙结构、表面元素形态结构组成,以及HAAs吸附性能进行了研究,考察了活性炭孔结构及含氧官能团对HAAs吸附性能的影响.活性炭表面含氧官能团对HAAs的吸附性能影响显著,当活性炭表面含氧官能团组成较小时,其HAAs吸附能力较强.     

Effect of ZnO loading to activated carbon on Pb(II) adsorption from aqueous solution

The effect of zinc oxide loading to granular activated carbon on Pb(II) adsorption from aqueous solution was studied in comparison with zinc oxide particles and oxidized activated carbon. Cu(II), Cd(II) and nitrobenzene were used as reference adsorbates to investigate the adsorption. The BET surface area and point of zero charge (pH_PZC) in the aqueous solution were measured for the adsorbents. The adsorption isotherms were examined to characterize the adsorption of heavy metals and organic molecules. The heavy metal adsorption was improved by both the zinc oxide loading and the oxidation of activated carbon. In contrast, the adsorption of nitrobenzene was considerably reduced by the oxidation, and slightly decreased by the zinc oxide loading. The zinc oxide loading to the activated carbon was found to be effectively used for the Pb(II) adsorption whereas only a part of surface functional groups was used for the zinc oxide particles and the oxidized activated carbon. From the experimental results, the surface functional groups responsible for the Pb(II) adsorption on the zinc oxide loaded activated carbon were considered to be hydroxyl groups that formed on the oxide, while those on the oxidized activated carbon were considered to be carboxylic groups.     

Surface modification of a granular activated carbon by citric acid for enhancement of copper adsorption

In this study, citric acid was used to modify a commercially available activated carbon to improve copper ion adsorption from aqueous solutions. The carbon was modified with 1.0 M citric acid, followed by an optional step of reaction with 1.0 M sodium hydroxide. It was found that the surface modification reduced the specific surface area by 34% and point of zero charge (pH_pzc) of the carbon by 0.5 units. Equilibrium results showed that citric acid modification increased the adsorption capacity to 14.92 mg Cu/g, which was 140% higher than the unmodified carbon. Higher initial solution pH resulted in higher copper adsorption. The chemical surface modification adversely affected the copper adsorption rate. Adsorption kinetic mechanisms were investigated with an intraparticle diffusion model. It was found that the modification did not change both external diffusion and intraparticle diffusion.     

Adsorption of l-histidine over mesoporous carbon molecular sieves

Mesoporous carbon, CMK-3, was prepared by large pore hexagonal mesoporous silica SBA-15. The structural order and textural properties of all the materials were studied by XRD, HRTEM, and nitrogen adsorption. Adsorption of l-histidine (His) over various porous adsorbents such as CMK-3, SBA-15, and activated carbon was studied from solutions with different pH. His adsorption was observed to be pH dependent with maximum adsorption near the isoelectric point of the amino acid. CMK-3 showed a larger amount of His adsorption as compared to SBA-15 and the conventional adsorbent, namely activated carbon. CMK-3 registers the total adsorption capacity of ca. 1350 μmol g⁻¹ which is ca. 12 times higher than the adsorption capacity of SBA-15. This large difference could be mainly due to the stronger hydrophobic interaction between the non-polar side chains of amino acids and the hydrophobic surface of the mesoporous carbon as compared to mesoporous silica. The influence of ionic strengths on the adsorption of His was also studied and the results are discussed. Nitrogen adsorption of CMK-3 after His adsorption confirmed that His molecules are tightly packed inside the mesopores.     

Surface modification of carbonaceous materials for EDLCs application

In this study, carbonaceous materials such as activated carbon and activated carbon aerogel were chemically modified with a surfactant sodium oleate in order to improve their specific capacitance and energy storage in electrochemical double-layer capacitors (EDLCs). Optimal conditions for surface modification of activated carbon have been examined as a surfactant solution concentration of 0.25 wt.% together with a time of 24 h for treatment at 25 °C. Specific capacitance and energy density can be improved significantly by surface modification of carbon materials. The enhancement in specific capacitance and energy density is mainly attributable to improvement in wettability of carbon materials, which results in a higher usable surface area and a smaller internal resistance. The effects from surface modification become more marked at higher discharge rates, at which the internal resistance has a more important impact on the energy delivery. A two times energy density of the original carbon could be achieved for the modified carbon materials at a high discharge rate, which indicates that the modified carbons are more suitable in EDLCs for high current applications. In addition, the modified carbon materials possess excellent cycle stability (the capacity decay was only 4% after 20,000 cycles).     

活性炭吸附甲烷和甲苯的分子模拟研究

以石墨片微元构建的多孔碳材料作为活性炭的结构模型,采用巨正则蒙特卡罗方法(GCMC)和分子动力学方法(MD),从分子层面研究甲烷和甲苯在活性炭中的吸附和扩散特性. 结果表明,石墨片微元大小对多孔碳材料吸附甲烷和甲苯有一定影响,37个碳环构成的多孔碳材料是最佳的吸附结构;甲烷气体在活性炭材料中扩散较快,甲苯在活性炭中扩散较慢,随碳环碳原子数增加,气体在多孔碳材料中的自扩散系数逐渐增大;引入基团会使最优密度向高密度方向偏移,用不同基团表面改性的吸附量顺序为羟基>氨基>羧基>未改性,基团引入会改善材料的孔结构,有利于吸附量的增加.     

活性炭吸附处理含酚废水的研究进展

含酚废水对环境和生物有较大危害,是一种常见的化工废水。活性炭作为良好的吸附剂被广泛用于污水处理,也常被用于吸附处理含酚废水。最新的研究集中于开发利用各种含碳原材料,并探究活性炭制备和改性方法,以改善活性炭对酚类的吸附性能。部分机理研究则关注活性炭的孔隙结构和表面官能团及其对吸附酚类性能的影响。本文从活性炭的制备和改性出发,归纳整理活性炭吸附酚类的特性和机理,分析吸附过程的主要影响因素,并对研究发展方向进行推论和展望。分析表明含碳量高的原材料适合制备活性炭,尤其是含碳废弃物。活性炭的苯酚吸附性能受比表面积和表面官能团的共同影响,这对于活性炭的制备和改性有指导意义。活性炭吸附苯酚的具体应用中,需要控制粒度、pH、温度、吸附时间和竞争吸附等影响因素。     

Electrochemical and physical chemical properties of sp carbon microrods

We investigated sp² carbon microrods resulting from the reaction of lithium with hexachlorobenzene. The material exhibits high surface area (200-340 m²/g, depending on heat treatment) and a reversible lithium storage capacity in excess of 500 mA h/g. The discharge/charge behavior of the material resembles that of high specific capacity non-graphitic carbon. Without distinguishable plateaus, the reversible intercalation of lithium occurs at a broad potential window below 1 V vs. Li/Li⁺. A possible mechanism for the rod formation, based on SEM results, is briefly considered.     

改性活性炭的表面特性及其对苯酚的吸附性能

研究了表面改性对活性炭吸附苯酚性能的影响。研究发现,硫酸氧化可增加活性炭表面酸性基团的含量,提高了活性炭的表面亲水性,降低pHPZC值,因而对吸附水中的苯酚的性能产生明显影响,降低了对苯酚的吸附。