K_2CO_3活化制备花椒籽废渣的活性炭及其对对硝基苯酚的吸附性能

采用花椒籽废渣(RPS)为原料,K_2CO_3为活化剂制备了花椒籽废渣活性炭(KAC),以期实现农业废弃物的再利用。采用傅里叶变换红外光谱仪(FTIR)、扫描电子显微镜(SEM)、热重分析仪(TGA)、能量散射光谱(EDS)、X射线衍射仪(XRD)和气体吸附法等技术手段对其进行表征。分析了浸渍比(m(K_2CO_3)∶m(RPS))、浸渍时间、活化温度和活化时间对制备花椒籽废渣活性炭的影响,并且测试了花椒籽废渣活性炭对对硝基苯酚的吸附行为。研究结果表明,在浸渍比为0.8,浸渍时间为12 h,活化温度为550℃,活化时间为60min的条件下,活性炭的产率为29.3%,比表面积为1210 m~2/g,碘值为1002 mg/g,对亚甲基蓝的平衡吸附容量为362 mg/g,灰分为2.2%,水分为6.6%。对对硝基苯酚的吸附性能研究表明,293 K,pH=8.0,吸附180min后可达到吸附平衡,对硝基苯酚的吸附容量为406 mg/g,吸附可用Langmuir等温方程较好模拟,吸附为自发的放热过程。动力学研究表明该吸附符合准二级动力学模型。K_2CO_3活化法制备花椒籽废渣活性炭原料廉价,工艺简单,制得的活性炭吸附性能优异,具有较好的应用前景。     

A Novel Hollow Carbon@MnO2 Electrospun Nanofiber Adsorbent for Efficient Removal of Pb2+ in Wastewater

Lead ion(Pb²⁺) is one of the most hazardous heavy metal ions in aquatic environments. Carbon materials and manganese dio-xide(MnO₂) have been shown to be prospective adsorbents to cope with the lead pollution. In this study, a novel hollow carbon@MnO₂ composite nanofiber adsorbent was prepared by the combination of electrospinning and carbonization. The PAN nanofiber membrane is subjected to a pre-oxidation and carbonization process, and then the obtained carbon nanofibers react with KMnO₄ solution during the hydrothermal process to develop the hollow carbon@MnO₂ nanofibers. The hollow carbon@MnO₂ nanofibers displayed a higher adsorption capacity of Pb²⁺ than carbon and MnO₂/PDA/PAN nanofibers. The maximum adsorption capacity toward Pb²⁺ by hollow carbon@MnO₂ nanofibers was 460.83 mg/g. After 5 adsorption-desorption cycles, the carbon@MnO₂nanofibers had a good recyclability and the removal efficiency remained 81.47%. Moreover, the removal efficiency of the hollow composite nanofibers for Pb²⁺ from real wastewater could reach 94.37%. This work shows a strategy for synthetics of the hollow carbon@MnO₂ nanofibers, which exhibits a promising potential in actual wastewater treatment.     

微波辐射紫茎泽兰制备优质活性炭的研究

以紫茎泽兰为原料,碳酸钾为活化剂,采用超声波浸渍,微波辐射法制备活性炭.研究了浸渍方式与时间、微波功率、微波辐射时间、剂料比对活性炭吸附性能和得率的影响.得到了本实验条件下的优化工艺条件:超声波浸渍20min、120℃脱水2h,微波功率700W、微波辐射时间12min、剂料比1.25∶1.优化工艺条件下制备的活性炭碘吸附值为1470.27mg/g,亚甲基蓝吸附值为300mL/g,得率为16.35%.浸渍时间极大的缩短,微波辐射时间只有传统法活化时间的1/15左右,活性炭的吸附指标超过了国标GB/T 13803.1-1999和GB/T 13803.2-1999一级品的标准,其中碘吸附值是国家一级标准的1.47倍,亚甲基蓝吸附值是国家一级标准的2.73倍.同时,测定了该活性炭氮吸附,其BET比表面积为1540.97m2/g,总孔容为0.7393mL/g,并通过DFT表征了活性炭的孔径分布,结果表明该活性炭为微孔型活性炭.     

Porous Silicon Carbide/Carbon Composite Microspherules for Methane Storage

Porous silicon carbide/carbon(SiC/C)microspherules were prepared by the controlled heating treatment of polymer and silica hybrid precursors over 1000℃in Ar/H_2 stream.The resultant SiC/C composite shows improved physical properties such as excellent mechanical strength,regular physical form, and high packing density.Such improvement overcomes the main inherent problems encountered when using activated carbons as absorbents without sacrificing porosity properties.N_2 sorption analysis shows that the SiC/C composite has a BET surface area of 1793 m~2/g and a pore volume of 0.92 ml/g.Methane adsorption isotherm is determined by the conventional volumetric method at 25℃and up to 7.0 MPa.On volumetric basis,the SiC/C composite microspherules show methane storage of 145(V/V)at 3.5 MPa and 25℃.The combination of excellent physical properties and porosity properties in this SiC/C composite lends a great possibility to develop a competitive storage system for natural gas.     

Facile preparation of hierarchically porous carbon using diatomite as both template and catalyst and methylene blue adsorption of carbon products

Hierarchically porous carbons were prepared using a facile preparation method in which diatomite was utilized as both template and catalyst. The porous structures of the carbon products and their formation mechanisms were investigated. The macroporosity and microporosity of the diatomite-templated carbons were derived from replication of diatom shell and structure-reconfiguration of the carbon film, respectively. The macroporosity of carbons was strongly dependent on the original morphology of the diatomite template. The macroporous structure composed of carbon plates connected by the pillar- and tube-like macropores resulted from the replication of the central and edge pores of the diatom shells with disk-shaped morphology, respectively. And another macroporous carbon tubes were also replicated from canoe-shaped diatom shells. The acidity of diatomite dramatically affected the porosity of the carbons, more acid sites of diatomite template resulted in higher surface area and pore volume of the carbon products. The diatomite-templated carbons exhibited higher adsorption capacity for methylene blue than the commercial activated carbon (CAC), although the specific surface area was much smaller than that of CAC, due to the hierarchical porosity of diatomite-templated carbons. And the carbons were readily reclaimed and regenerated.     

含磷活性炭作为双电层电容器电极材料的电化学性能

采用磷酸活化和磷酸改性制备了不同种类的含磷活性炭,采用元素分析、X射线光电子能谱(XPS)和氮气吸附等手段分析了活性炭的元素含量、表面化学性质和孔隙结构,采用恒电流充放电、循环伏安和交流阻抗分别考察了活性炭在KOH和H₂SO₄电解质溶液中作为超级电容器电极材料的电化学性能,采用自由截距多元线性回归拟合统计分析研究了活性炭电极比电容量的影响因素,应用三电极体系分析了磷元素对活性炭电化学性能的影响机理。研究结果表明,活性炭掺杂的磷引入了赝电容,提高了活性炭电极的比电容量,磷元素含量为5.88%(w)的活性炭的比电容量在0.1 A·g^-1下达到185 F·g^-1。统计分析结果显示,活性炭的中孔有利于电解质离子向微孔内的扩散。在6 mol·L^-1 KOH电解质溶液中,孔径在1.10-1.61 nm、2.12-2.43nm及3.94-4.37 nm范围内是电解质离子在活性炭孔隙内部形成双电层的主要场所;在1 mol·L^-1 H₂SO₄电解质溶液中,孔径在0.67-0.72 nm范围内有利于双电层电容的形成。     

电化学双电层电容器电极材料——豌豆荚基活性炭的制备与表征

以豌豆荚为碳源、ZnCl₂或KOH为活化剂制备了活性炭, 并用作双电层电容器的电极材料. 采用比表面及孔隙度分析仪表征了豌豆荚基活性炭的孔结构. 通过KOH或ZnCl₂活化后, 活性炭比表面积从1.69 m²·g^-1增大到2237或621 m²·g^-1. 采用循环伏安法和恒流充放电测试技术表征了豌豆荚基活性炭的电化学特性. 结果表明: 在6 mol·L^-1 KOH溶液中经KOH活化处理的活性炭的质量比电容高达297.5 F·g^-1, 并具有良好的充放电稳定性, 在5 A·g^-1的高电流密度下循环充放电500次后, 质量比电容仅衰减8.6%.     

Porosity characteristics and pore developments of various particle sizes palm kernel shells activated carbon (PKSAC) and its potential applications

The adsorption behaviour and the micro- and mesopore size distributions of commercial palm kernel shell activated carbons (PKSAC) and other commercial activated carbon are characterized. The results showed that PKSAC are predominantly microporous materials, where micropores account 68–79% of total porosity. On the other hand, commercial activated carbons: Norit SX Plus, Calgon 12×40, and Shirasagi “A” activated carbons contained high mesopore fraction ranging from 33 to 52%. The analysis showed that the degree of mesoporosity of PKSAC is increased steadily with the decrease of particle size. This is due to the presence of channels interconnect the smaller pores in the interior of smaller particle size PKSAC. The smaller size PKSAC particle that is highly mesoporous has preformed better on the adsorption of larger molecules such as methylene blue. On the other hand, bigger size PKSAC particle has better performance on the adsorption of smaller adsorbates such as iodine.     

Comparisons of porous and adsorption properties of carbons activated by steam and KOH

In this work, fir woods and pistachio shells were used as source materials to prepare porous carbons, which were activated by physical (steam) and chemical (KOH) methods. Pore properties of these activated carbons including the BET surface area, pore volume, pore size distribution, and pore diameter were first characterized by a t-plot method based on N(2) adsorption isotherms. Highly porous activated carbons with BET surface area up to 1009-1096 m(2)/g were obtained. The steam and KOH activation methods produced carbons with mesopore content in the range 9-15 and 33-49%, respectively. The adsorption equilibria and kinetics of tannic acid, methylene blue, 4-chlorophenol, and phenol from water on such carbons at 30 degrees C were then investigated to check their chemical characteristics. The Freundlich equation gave a better fit to all adsorption isotherms than the Langmuir equation. On the other hand, the intraparticle diffusion model could best follow all adsorption processes. In comparison with KOH-activated carbons, it was shown that the rate of external surface adsorption with steam-activated carbons was significantly higher but the rate of intraparticle diffusion was much lower.     

Preparation of Corn Stalk-Walnut Shell Mix-based Activated Carbon and Its Adsorption of Malachite Green

The mix-based activated carbon derived from corn stalk and walnut shell was prepared by chemical activation method using phosphoric acid as the activator. The optimized conditions for preparation were obtained by the orthogonal experiment, the characterizations of the activated carbon were performed by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy(FTIR), Boehm's titration method and nitrogen adsorption. For the prepared mix-based activated carbon, the highest iodine number, methylene blue number and BET surface area are 720.5 mg/g, 195.0 mg/g and 1187 m²/g, respectively, and the pores are mainly mesopores. The mix-based activated carbon shows the higher adsorption capacity for malachite green than the raw materials, the activated carbons prepared only from corn stalk or walnut shell and the commercial activated carbon. The kinetics and thermodynamics of the adsorption can be satisfactorily described by the pseudo-second-order kinetic model and the Langmuir isotherm model, separately.     

Porous Organic Frameworks-derived Porous Carbons with Outstanding Gas Adsorption Performance

A series of porous carbon materials was synthesized via high temperature pyrolysis from well-defined and thermally stable precursors, namely porous organic frameworks(POFs), in inert atmosphere. The porous carbon materials showed enhanced gas adsorption capacities together with increased heat of adsorption and stronger affinity between the frameworks and the gases as compared to the precursor materials. To exemplify, sample C-POF-TBBP-1000 with a high BET surface area of 1290 m²/g can adsorb 2.8 mmol/g CH₄(273 K, 101.325 kPa), 5.4 mmol/g CO₂(273 K, 101.325 kPa) and 2.2% H₂(mass fraction, 77 K, 101.325 kPa), thereby surpassing most other porous adsorbent materials reported till date. The study highlights the potential of porous carbons derived from novel porous organic framework structures for gas adsorption applications.     

The physical and surface chemical characteristics of activated carbons and the adsorption of methylene blue from wastewater

Adsorption of a basic dye, methylene blue, from aqueous solutions onto as-received activated carbons and acid-treated carbons was investigated. The physical and surface chemical properties of the activated carbons were characterized using BET-N(2) adsorption, X-ray photoelectron spectroscopy (XPS), and mass titration. It was found that acid treatment had little effect on carbon textural characteristics but significantly changed the surface chemical properties, resulting in an adverse effect on dye adsorption. The physical properties of activated carbon, such as surface area and pore volume, have little effect on dye adsorption, while the pore size distribution and the surface chemical characteristics play important roles in dye adsorption. The pH value of the solution also influences the adsorption capacity significantly. For methylene blue, a higher pH of solution favors the adsorption capacity. The kinetic adsorption of methylene blue on all carbons follows a pseudo-second-order equation.     

Evaluation of dithiocarbamates and beta-diketones as chelating agents in supercritical fluid extraction of Cd, Pb, and Hg from solid samples

The use of four dithiocarbamates and three fluorinated β-diketones as potential chelating agents for three transition metal ions (Cd²⁺, Pb²⁺, and Hg²⁺) extracted from spiked sand and filter paper samples by supercritical fluid extraction (SFE) was investigated. The extractions were performed at 45°C and 250 atm for spiked sand samples and at 60°C and 200 atm for filter paper samples using supercritical carbon dioxide modified with 5% methanol. At 250 atm and using carbon dioxide modified with 5% methanol, the recoveries of Cd²⁺, Pb²⁺, and Hg²⁺ ions from spiked sand samples were 95% with lithium bis(trifluoroethyl)dithiocarbamate (LiFDDC) as the chelating agent; they ranged from 83–97% with diethylammonium diethyldithiocarbamate and from 87–97% with sodium di-ethyldithiocarbamate as chelating agents, and from 68–96% with trifluoracetylacetone, hexafluoroacetylacetone, and thenoylfluoroacetone as chelating agents. Ammonium pyrrolidinedithiocarbamate was not effective in the chelation SFE of Cd²⁺, Pb²⁺, and Hg²⁺ ions from either spiked sand or spiked filter paper samples under the extraction conditions used. Supercritical carbon dioxide alone gave consistently lower analyte recoveries than supercritical carbon dioxide modified with 5% methanol. The results suggest that the solubility of the metal chelate in the supercritical fluid plays a more important role than the solubility of the chelating agent in the supercritical fluid, as long as sufficient chelating agent is present in the fluid phase. Fluorination of the chelating agent, as in the case of LiFDDC, increases the solubility of the metal chelate, and subsequently enhances the extraction efficiency for the metal ions.     

Porous structure and thermal properties of carbon adsorbents from pitch–polymer compositions

The study results of porous structure and thermal properties of carbon adsorbents (AC) obtained from pitch–polymer compositions were presented. The compositions were carbonized and activated with steam, potassium hydroxide, and magnesium and potassium carbonates. For the obtained AC, the thermal analysis and the determination of adsorption value of iodine and porous structure by adsorption/desorption of nitrogen at 77 K were carried out. The possibility of obtained activated carbons from pitch–polymer compositions was demonstrated. The use of untypical feedstock, as an effect of combination of bituminous substance with polymeric waste and improvement of the methods of production, creates the potential possibility to produce carbon adsorbents of interesting properties and porous structure.     

铁酸锰/腐植酸复合材料制备及其对亚甲基蓝吸附性能

采用化学共沉淀法合成了一种腐植酸(Humic Acid,HA)包覆铁酸锰型磁性复合材料(MnFe₂O₄/HA)。采用扫描电子显微镜(SEM)、粉末X射线衍射(XRD)和傅里叶变换红外光谱(FT-IR)等技术手段对其进行表征和分析表明,合成产物颗粒大小约200 nm,具有典型的尖晶石结构,腐植酸成功包覆在MnFe₂O₄颗粒表面,饱和磁化强度为34.01 A·m²/kg,在外界低磁场作用下30 s内便可从水溶液分离。 MnFe₂O₄/HA对亚甲基蓝的吸附是一个准二级动力学过程,在2 h达到平衡,较好的符合Langmuir吸附模型。 与MnFe₂O₄相比其对亚甲基蓝的吸附能力显著增强,室温下pH=9时最大吸附量可以达到29.94 mg/g。 MnFe₂O₄/HA可以作为一种有效去除水体中亚甲基蓝污染物的吸附材料。     

Transition metal binding properties of the redox-active 1,4,7,10,13,16-hexa(ferrocenylmethyl)-1,4,7,10,13,16-hexaazacyclooctadecane and its electrochemical behaviour in a non-aqueous solvent

Solution studies to elucidate the coordination behaviour and the electrochemical response of the ferrocene-functionalized polyazamacrocycle 1,4,7,10,13,16-hexa(ferrocenylmethyl)-1,4,7,10,13,16-hexaazacyclooctadecane (L¹) by potentiometric methods and electrochemical techniques have been carried out. Potentiometric methods in the presence of Cd²⁺, Hg²⁺, Pb²⁺ and Zn²⁺ were carried out in 1,4-dioxane/water (70:30 v/v, 25°C, 0.1 mol dm⁻³ KNO₃). Electrochemical studies were carried out in acetonitrile/dichloromethane (50:50 v/v, 25°C, 0.1 mol dm⁻³ TBAClO₄) in the presence of transition metal ions and anions.     

几种植物基活性炭材料的表面结构与吸附性能比较——(II)表面化学结构与吸附性能研究

用X-射线光电子能谱对3种植物基活性炭材料:椰壳活性炭 (CAC4)、剑麻茎基活性炭(SSAC)和剑麻基活性碳纤维 (SACF) 的表面化学结构进行了表征,并研究和对比了它们的吸附性能,包括对碘、苯酚和亚甲基蓝的液相吸附性能,对有机蒸汽的吸附性能以及对Au3+的还原吸附性能等。结果表明,3个样品表面均含有多种含氧官能团,吸附能力SACF>SSAC> CAC4。样品的吸附性能主要取决于自身孔结构,与其表面化学结构也有密切的关系。     

氮硫双掺杂活性炭材料的制备和电容性能

以头发和蔗糖为原料, 通过水热碳化和KOH活化两步法制备了氮硫双掺杂微孔炭材料. 利用扫描电子显微镜, 透射电子显微镜, 氮气吸脱附, X射线光电子能谱, 电子能谱和傅里叶交换红外光谱等手段系统表征了所制备活性炭材料的微观形貌, 孔隙结构和表面化学性质. 并在6 mol·L^-1 KOH溶液中研究了所制备活性炭材料的电容性能. 氮气吸脱附测试表明, 所制备活性炭材料的比表面积最高可达1849.4 m²·g^-1, 孔道以微孔为主. 所制备活性炭材料氮元素含量为1.6%-2.5% (原子分数(x))), 硫元素含量为0.2%-0.5% (x). 由于N、O、S官能团的协同作用, 所制备碳材料表现出明显的赝电容. 活性炭材料的比电容值最高可达200 F·g^-1, 对应的能量密度为6.9 Wh·kg^-1. 功率密度达到10000 W·kg^-1时, 能量密度仍达到4.1 Wh·kg^-1. 本文的工作表明以生物质为原料可以方便制备氮硫双掺杂活性炭电极材料.     

离子强度对膨润土/木质素磺酸钠接枝丙烯酰胺-马来酸酐复合吸附树脂吸附Pb2+/Cu2+的影响

为揭示外加电解质离子强度对重金属离子吸附的影响规律与内在机制, 制备了膨润土/木质素磺酸钠接枝丙烯酰胺-马来酸酐复合吸附树脂(BLPAMA), 研究了外加电解质离子强度对BLPAMA吸附单一和二元Pb²⁺/Cu²⁺的影响规律, 以及有、无外加0.2 mol/L NaNO₃时BLPAMA对二元Pb²⁺/Cu²⁺的吸附等温线、吸附热力学及吸附动力学。 结果表明, 在单一Pb²⁺或Cu²⁺溶液中, 随离子强度增加, Pb²⁺和Cu²⁺吸附量降低;在二元Pb²⁺/Cu²⁺溶液中, 随离子强度增加, Pb²⁺吸附量降低而Cu²⁺吸附量提高。     

Facile Synthesis of Fe-based MOFs(Fe-BTC) as Efficient Adsorbent for Water Purifications

Fe-based metal-organic frameworks(Fe-BTC) were successfully synthesized in a large scale by using a simple one-pot method at room temperature. To understand its composition, texture and morphology, the as-synthesized material was analyzed systematically. Moreover, based on the adsorption property for anionic organic dyes(methyl orange, Congo red), cationic organic dves(methylene blue, rhodamine B) and heavy metal ions(Pb^2+) in aqueous solutions, it was revealed that the obtained Fe-BTC showed excellent capacities and adsorption rates tor different adsorbates. Besides the general adsorption eftect derived from the numerous pores and large specific surface area, the electrostatic forces and Л-Л interactions between benzene rings are believed to play significant roles in the large uptakes of this Fe-BTC sample. And the existence of mesopores in Fe-BTC might accelerate the adsorption.