Nitrogen and hydrogen adsorption of activated carbon fibers modified by fluorination

In this study, activated carbon fibers (ACFs) were surface modified with fluorine and mixed oxygen and fluorine gas to investigate the relationship between changes in surface properties by nitrogen and hydrogen adsorption capacity. The changes in surface properties of modified activated carbon fibers were investigated using X-ray photoelectron spectroscopy (XPS) and compared before and after surface treatment. The specific surface area and pore structures were characterized by the nitrogen adsorption isotherm at liquid nitrogen temperature. Hydrogen adsorption isotherms were obtained at 77 K and 1 bar by a volumetric method. The hydrogen adsorption capacity of fluorinated activated carbon fibers was the smallest of all samples. However, the bulk density in this sample was largest. This result could be explained by virial coefficients. The interaction of hydrogen-surface carbon increased with fluorination as the first virial coefficient. Also, the best fit adsorption model was found to explain the adsorption mechanism using a nonlinear curve fit. According to the goodness-of-fit, the Langmuir–Freundlich isotherm model was in good agreement with experimental data from this study.     

The adsorption properties of surface modified activated carbon fibers for hydrogen storages

In this study, activated carbon fibers (ACFs) with high surface area and pore volume have been modified by Ni doping and fluorination. The surface modified ACFs were characterized by BET surface area, SEM/EDS, XRD, and Raman spectroscopy. The changes in pore structure and surface properties of these modified ACFs were correlated with hydrogen storage capabilities. After fluorination treatment, although the micropore volume of ACF was decreased, amounts of hydrogen storage were found to increase. Additionally, micropore volume on ACFs was found to be unchanged with Ni doping, hydrogen storage capacities were considerably increased due to the effect of catalytic activation of nickel. Though fluorination of ACFs increases hydrogen affinity, the effect of catalytic activation of nickel is more prominent, and thus led to better hydrogen storage. Hence, it was concluded that hydrogen storage capacity was related to micropore volumes, Pore size distribution (PSD) and surface properties of ACFs as well as specific surface areas.     

酚醛基活性碳纤维

酚醛树脂属于难石墨化碳，适宜制造活性碳纤维(ACF)，其特点是碳化活化收率高，制品强度高，比表面积大，孔径分布属于单峰形，吸附容量大；细孔入口形状属于狭缝形，吸脱速度快；制品柔软，深加工性好，它除用于治理环境污染外，还可用于制作防化防毒服和制造超级电容器等。     

Continuous hydrogen evolution from cyclohexanes over platinum catalysts supported on activated carbon fibers

The continuous production of hydrogen from cyclohexanes is achieved effectively using Pt/ACF (ACF = activated carbon fiber) catalysts in a fixed-bed flow reactor. The Pt catalysts are more effective than a Pd/ACF catalyst for the reaction. Besides cyclohexane, methylcyclohexane, 1,4-dimethylcyclohexane, and p-menthane can also be employed as hydrogen source in the reaction system.     

Single Pd atoms in activated carbon fibers and their contribution to hydrogen storage

Palladium-modified activated carbon fibers (Pd-ACF) were synthesized by melt-spinning, carbonization and activation of an isotropic pitch carbon precursor premixed with an organometallic Pd compound. The hydrogen uptake at 25 °C and 20 bar on Pd-ACF exceeded the expected capacity based solely on Pd hydride formation and hydrogen physisorption on the microporous carbon support. Aberration-corrected scanning transmission electron microscopy (STEM) with sub-Ångstrom spatial resolution provided unambiguous identification of isolated Pd atoms occurring in the carbon matrix that coexist with larger Pd particles. First principles calculations revealed that each single Pd atom can form Kubas-type complexes by binding up to three H₂ molecules in the pressure range of adsorption measurements. Based on Pd atom concentration determined from STEM images, the contribution of various mechanisms to the excess hydrogen uptake measured experimentally was evaluated. With consideration of Kubas binding as a viable mechanism (along with hydride formation and physisorption to carbon support) the role of hydrogen spillover in this system may be smaller than previously thought.     

铁盐改性活性炭纤维常温脱除硫化氢的研究

研究了铁盐改性活性炭纤维(ACF)在常温下脱除硫化氢的性能及其影响因素.发现热处理后的硝酸铁改性ACF在常温下有较好的吸附性能(能够将氮气中9.5×10-4体积分数的H2S脱除到1×10-7体积分数以下),尤其是吸附剂CI-5H623的硫容量达到383.56 mg(H2S)/g(ACF);影响吸附性能的主要因素是吸附剂的含氧活性基团、湿度、孔结构和比表面积.氧化铁担载量和吸附剂的酸碱性对吸附硫化氢也有一定的影响.     

STEM imaging of single Pd atoms in activated carbon fibers considered for hydrogen storage

Aberration corrected scanning transmission electron microscopy was used to demonstrate the feasibility of imaging individual Pd atoms that are highly dispersed throughout the volume of activated carbon fibers. Simultaneous acquisition of high-angle annular dark-field and bright-field images allows correlation of the location of single Pd atoms with microstructural features of the carbon host material. Sub-Ångström imaging conditions revealed that 18 wt% of the total Pd content is dispersed as single Pd atoms in three re-occurring local structural arrangements. The identified structural configurations may represent effective storage sites for molecular hydrogen through Kubas complex formation as discussed in detail in the preceding article.     

活化温度对聚丙烯腈基活性中空炭纤维结构和吸附性能的影响

用质量分数为4%的磷酸氢氨溶液预处理聚丙烯腈(PAN)中空纤维,经预氧化及炭化后,用二氧化碳气体在不同温度下活化40 min,得到PAN基活性中空炭纤维(PAN-ACHF)。考察了活化温度对PAN-ACHF的比表面积、孔径分布、形态和吸附性能的影响。结果表明,随着活化温度的升高,PAN-ACHF表面的孔逐渐加深,且数目逐渐增多,比表面积逐渐增大;当活化温度为900℃时,BET比表面积最大为1 422 m2/g,中孔的比表面积也达到最大,为1 234 m2/g,且孔径主要集中在2~5 nm;PAN-ACHF对肌酐和VB12的吸附率都随着活化温度的升高而增大,当活化温度为900℃时,PAN-ACHF对肌酐和VB12的吸附率都达到最大值.分别为99%和84%。     

活性炭纤维用于苦卤脱色的研究

采用活性炭纤维（ACF）对海盐苦卤进行吸附脱色实验.通过动态吸附实验,探讨了活性炭用量、溶液流速、温度、浓度、pH对脱色率的影响.确定活性炭纤维对苦卤溶液脱色的最佳工艺条件为：温度20 ℃,苦卤溶液浓度（以溶液中X-计）为2 mol/L,溶液pH＝6,动态吸附流速为6 mL/min.在此条件下,苦卤脱色率大于98%.活性炭纤维对海盐苦卤的饱和吸附量比颗粒活性炭大10倍.吸附后的活性炭纤维加热到120 ℃并抽真空进行脱附,可循环使用18次以上.     

以纸巾为模板制备活性炭纤维

以纸巾为前驱体通过NaOH化学活化制备活性炭纤维,扫描电镜观测其微观结构为多孔纤维状。通过活性炭纤维对亚甲基蓝的吸附实验研究活性炭纤维吸附动力学,Pseudo-second-order方程比Pseudo-first-order方程更适于吸附数据模型,相关系数高达0.998,所制备活性炭纤维对亚甲基蓝最大平衡吸附量为200mg/g。     

Properties of differently shaped activated carbon fibers

Differently shaped carbon fibers (R-, I-, C-, Y-, and X-type) were prepared from melt-spinning of reformed naphtha cracking bottom oil precursors through various shaped spinnerets. These carbon fibers were activated by steam and activation properties were compared. The decrease of hydraulic radius resulted in the extending of the external surface area of carbon fibers. Activation energy and rate of differently shaped carbon fibers were affected by external surface area. Especially, the activation rate of tetralobal carbon fibers (X-type) appeared much larger than other shaped carbon fibers due to the smallest hydraulic radius. Adsorption capacity of tetralobal activated carbon fibers was also larger than other shaped activated carbon fibers.     

Preparation and characterization of silicon carbide fibers from activated carbon fibers

Silicon carbide fibers were prepared by the reaction between activated carbon fibers and silicon monoxide generated from a mixture of silicon and silicon dioxide at temperatures from 1200 to 1300°C in an inert atmosphere of argon. The reaction was completed at temperatures as low as 1200°C, which means that activated carbon fibers had a high reactivity. The resulting sample maintained the original morphology of the starting material, which was an advantage because of the difficulty in post shaping silicon carbide, and led to a silicon carbide fiber with high specific surface area. The resulting samples were characterized by powder X-ray diffraction, thermal gravimetric analysis, and by nitrogen adsorption measurements at 77.4 K to obtain surface area and pore size distributions. The morphology of the resulting sample was observed by scanning electron microscopy and the electronic structure was investigated by Fourier transformation infrared spectroscopy and X-ray photoelectron spectroscopy techniques.     

Preparation and characterization of trilobal activated carbon fibers

The objective of this research was to evaluate the effectiveness of several different methods for controlling the pore size and pore size distribution in activated carbon fibers. Variables studied included fiber shape, activation time, and the addition of small amounts of silver nitrate. Pure isotropic pitch and the same isotropic pitch containing 1 wt.% silver were melt spun to form fibers with round and trilobal cross sections. These fibers were then stabilized, carbonized, and activated in carbon dioxide. Field emission scanning electron microscopy (FE SEM), electron dispersive spectra (EDS), and wavelength dispersive spectra (WDS) were used to monitor the size and distribution of the silver particles in the fibers before and after activation. Each of these analyses showed that the distribution of silver particles was extremely uniform before and after activation. The fibers were also weighed before and after activation to determine the percent burn-off. The BET specific surface areas of the activated fibers were determined from N₂ adsorption isotherms measured at −196 °C. The results showed that round and trilobal fibers with equivalent cross-sectional areas yielded similar burn-off values and specific surface areas after activation. Also, activation rates were found to be independent of CO₂ flow rate. The porosity of the activated fibers depended on the total time of activation and the cross-sectional area of fibers. The N₂ adsorption measurements showed that the activated fibers had extremely high specific surface areas (greater than 3000 m²/g) and high degrees of meso- and macro-porosity. FE SEM was also used to investigate surface texture and size of pore openings on the surfaces of the activated fibers. The photos showed that silver particles generated surface macro- and mesopores, in agreement with the inferences from N₂ adsorption measurements.     

酚醛基活性炭纤维的研究进展

从酚醛树脂的合成经纺丝成纤制得酚醛纤维,再将酚醛纤维经碳化、活化最终制得酚醛基活性炭纤维(PACF)的工艺过程综述了PACF的研究进展;其中重点介绍了酚醛树脂的成纤方法:熔融纺丝法、离心纺丝法、湿法纺丝法以及酚醛纤维的化学活化法和物理活化法;阐述了PACF的结构性能以及在吸附领域、超级电容器、高效集热材料,抗菌纤维等方面的应用;展望了PACF的发展前景,指出降低生产成本,避开溶液固化过程、降低污染、拓展应用范围是PACF在未来一段时期内的研究方向。     

Preparation of activated carbon fibers from polyvinyl chloride

Waste polyvinyl chloride (PVC) contains high content of chlorine, which is believed to liberate dioxine at its combustion. Efficient removal of chlorine from PVC achieved by selecting the heat-treatment conditions provided free-chlorine PVC based pitch by a two-stage heat-treatment process. The obtained pitch (softening point: 218 °C) was spun, stabilized, carbonized and activated to prepare activated carbon fibers (ACF) whose DeSO_x activity was tested preliminarily and found comparable to other ACF.     

Oxidative dehydrogenation of ethylbenzene on activated carbon fibers

Activated carbon fibers from different precursors and with different degrees of activation were used as catalysts for the oxidative dehydrogenation of ethylbenzene. Within each group, the fibers exhibited similar surface chemistries, so that the observed catalytic performances could be interpreted exclusively in terms of their textural properties. Analysis of the catalytic results highlighted common trends. In particular, the fibers with an average micropore width larger than 1.2 nm were found to be the best catalysts for this reaction.     

Characterization of activated carbon fibers using argon adsorption

In this paper, we present results of the internal structure (pore size and pore wall thickness distributions) of a series of activated carbon fibers with different degrees of burn-off, determined from interpretation of argon adsorption data at 87 K using infinite and finite wall thickness models. The latter approach has recently been developed in our laboratory. The results show that while the low bun-off samples have nearly uniform pore size (<0.6 nm), the pore size distribution of the high burn-off samples becomes broader, with a significant increase in proportion of larger pores. The results of pore wall thickness distribution are generally consistent with development of porosity with increasing degree of burn-off. Further they show good correspondence with X-ray diffraction.     

Conversion of polyacrylonitrile fibers to activated carbon fibers: Effect of activation

Polyacrylonitrile (PAN)-based activated carbon fibers were developed with the idea of increasing their potential and efficiency in industrial applications. The PAN-based fibers were first oxidized in air in a continuous multistage stabilization process, and then subjected to a continuous, low temperature carbonization and activation treatment in a mixture of steam and argon. The effect of the activation condition on the specific surface area, elemental composition, as well as the morphological structure of activated carbon fibers was studied. The surface area of the carbon fibers increased remarkably after the steam activation. It was found that steam activation promoted the elimination of nitrogen from the fiber. The bulk oxygen content of the fibers increased upon activation, probably due to formation of carbon-oxygen functionalities on the surface of the activated carbon fibers. The surface oxygen level of activated carbon fibers was greater than the bulk analysis of oxygen. It was observed that activation decayed the order of the carbon structure. © 1996 John Wiley & Sons, Inc.     

聚丙烯腈基活性碳纤维吸附CO2的性能

以国产聚丙烯腈(PAN)基碳纤维为原料,采用KOH为活化剂制备PAN基活性碳纤维。测定了不同ACF样品的CO2吸附量,并通过氮气吸附、碘吸附以及红外光谱对所得活性碳纤维的比表面积、孔结构及表面官能团进行表征。研究了活化温度、活化时间和表面改性对活性碳纤维CO2吸附量的影响。结果表明,活化温度是影响活性碳纤维CO2吸附量的主要因素。当活化温度为850℃时,所得活性碳纤维BET比表面积为1235m2/g,微孔比表面积为745 m2/g,在吸附温度为273 K、吸附相对压力P/P0为1时,CO2的吸附量达到87.29 mL/g。