Adsorption of ammonia and water on functionalized edge-rich carbon nanofibers

The preparation, characterization and ammonia and water adsorption properties of edge-rich carbon nanofibers (CNFs) were studied, including platelet CNFs (PCNFs) and cup-stacked CNFs (CSCNFs). Since PCNFs and CSCNFs have many chemically active exposed edges, functionalization by oxidizing the edges was carried out by ozone stream and by nitric acid. Transmission electron microscopy, N₂ adsorption isotherms and temperature-programmed desorption analysis showed that the nitric acid treatment partly destroyed the graphite structure of the PCNFs and created acid functional groups and micropores, whereas the ozone treatment created functional groups without damaging the structure. Ammonia adsorption isotherms clarified that NH₃ adsorption on PCNFs and CSCNFs occurred mainly on oxygen-containing groups, whereas the adsorption on activated carbon fibers (ACFs) occurred on both oxygen-containing groups and the carbon surface without the functional groups, and the CSCNFs showed larger amounts of adsorbed ammonia compared to the PCNFs. Especially at a relatively low pressure range (<0.2 atm), the PCNFs/CSCNFs/ACFs showed the same ammonia adsorption mechanism; that is, the one-to-one interaction between oxygen atoms in the functional groups and hydrogen atoms in ammonia molecules. In addition, the adsorption on the ACFs appeared to occur mainly by interaction with the carbon surface at relatively high pressure (0.3–1.0 atm). Our experimental results and previous findings suggest that NH₃ adsorption on PCNFs is due mainly to NH…O hydrogen bonding between oxygen-containing groups and ammonia rather than to chemical bonding.     

活性炭纤维填充床脱除水中酚类化合物及填充床的再生初探

研究了活性炭纤维填充床脱除水中酚类化合物及其填充床的再生方法。结果表明当平衡浓度变化范围为0到0.8kg/m^3时,吸附等温线符合Langmuir型;用乙醇或热的NaOH稀溶液可再生被酚饱和的活性炭纤维填充床,再生效率达90％以上,建立了考虑轴向弥散、纤维内扩散和外膜传质阻力的填充床数学模型,模型由正交配置方法离散,Gear方法求解以预测穿透曲线。模型预测值与实验数据吻合较好,结果确认轴向弥散是影响活性炭纤维填充床穿透曲线的主要因素。     

Surface control of activated carbon fiber by growth of carbon nanofiber

Carbon nanofiber/activated carbon fiber (CNF/ACF) composites with multifunctional surfaces were prepared through catalytic growth of CNFs on an ACF. Because of selective deposition of catalyst particles in ACF micropores, partial oxidation of ACF after catalyst impregnation was a critical step to control the surface area of the CNF/ACF composites, of which the surface functions can be synergistically performed by both the microporous surface of ACF and free edges of CNFs. CNF/ACF composites of this study are expected to provide an improved performance in SOx or NOx removal.     

Chemoselective hydrogenation of nitroarenes with carbon nanofiber-supported platinum and palladium nanoparticles

Platinum and palladium nanoparticles supported on three types of carbon nanofibers (CNFs) are synthesized and used as catalysts in the hydrogenation of nitroarenes. Nanosized platinum particles dispersed on platelet-type CNF efficiently catalyze the reduction of functionalized nitroarenes to the corresponding substituted anilines in high turnover numbers with other functional groups remaining intact.     

Ru/CNFs 催化剂催化氨分解制氢

 研究了鱼骨式碳纤维 (CNFs) 和管式碳纤维 (CNTs) 负载 Ru 催化剂的氨分解反应活性. 结果表明, Ru/CNFs 催化剂上氨分解活性高于 Ru/CNTs 催化剂. 通过改变 Ru 负载量或载体表面的含氧基团来调节 Ru 的粒径. Ru 的活性位随着 Ru 颗粒尺寸的增大而增加. CNFs 上的含氧基团对 Ru 颗粒的氨分解活性影响很大. 在相同粒径的 Ru 颗粒上, CNFs 表面的含氧基团增加了 Ru 的活性.     

Ammonia removal of activated carbon fibers produced by oxyfluorination

In this study, activated carbon fibers (ACFs) were produced by an oxyfluorination treatment to enhance the capacity of ammonia gas removal. The introduction of polar groups, such as CF, CO, and COOH, on the ACFs was confirmed by a XPS analysis, and N2/77 K adsorption isotherm characteristics including specific surface area and total and micropore volumes were studied by the BET and t-plot methods. The ammonia-removal efficiency was confirmed by a gas-detecting tube technique. As a result, the specific surface area and micropore volume of ACFs were slightly destroyed as the surface treatment time was increased. However, the oxyfluorinated ACFs led to an increase of fluorine and oxygen-containing polar functional groups in ACF surfaces, resulting in an increase in the ammonia-removal efficiency of the ACFs produced.     

Influence of anodic treatment on heavy metal ion removal by activated carbon fibers

In this work, the effect of electrochemical oxidation treatment on activated carbon fibers (ACFs) was studied in the context of Cr(VI), Cu(II), and Ni(II) adsorption behavior. Ten weight percent phosphoric acid (A-ACFs) and ammonia (B-ACFs) were used for acidic and basic electrolytes, respectively. Surface properties of ACFs were determined by X-ray photoelectron spectroscopy (XPS). The specific surface area and the pore structure were evaluated from nitrogen adsorption data at 77 K. As a result, the electrochemical oxidation treatment led to an increase in the amount of oxygen-containing functional groups. Also, the adsorption capacity of the electrochemically oxidized ACFs was improved in the order B-ACFs > A-ACFs > untreated-ACFs, in spite of a decrease in specific surface area which resulted from pore blocking by functional groups and pore destruction by acidic electrolyte. It was clearly found that the heavy metal ions were largely influenced by the functional groups on the ACF surfaces.     

Relation between the charge efficiency of activated carbon fiber and its desalination performance

Four types of activated carbon fibers (ACFs) with different specific surface areas (SSA) were used as electrode materials for water desalination using capacitive deionization (CDI). The carbon fibers were characterized by scanning electron microscopy and N(2) adsorption at 77 K, and the CDI process was investigated by studying the salt adsorption, charge transfer, and also the charge efficiency of the electric double layers that are formed within the micropores inside the carbon electrodes. It is found that the physical adsorption capacity of NaCl by the ACFs increases with increasing Brunauer-Emmett-Teller (BET) surface area of the fibers. However, the two ACF materials with the highest BET surface area have the lowest electrosorptive capability. Experiments indicate that the charge efficiency of the double layers is a key property of the ACF-based electrodes because the ACF material which has the maximum charge efficiency also shows the highest salt adsorption capacity for CDI.     

Adsorption of phenol on supercritically activated carbon fibres: effect of texture and surface chemistry

The influence of texture and surface chemistry on the phenol adsorption capacity of activated carbon fibres (ACFs) was studied. ACFs were prepared by carbonization of a phenolic textile fibre under nitrogen flow, followed by activation with H(2)O and CO(2) (under atmospheric pressure and supercritical state). The materials were characterised by N(2) and CO(2) adsorption, and by temperature programmed desorption studies. A strong correlation between the amount of adsorbed phenol and the micropore volume has been observed. The relationship between surface oxygen concentration and amount of physisorbed and chemisorbed phenol was assessed, and it was shown that higher amounts of surface oxygen groups decreased the phenol chemisorption capacity of ACFs.     

纳米碳纤维的表面性质和微结构对氧还原催化活性的影响

采用超声处理的方法分别对管式纳米碳纤维(t-CNF)和鱼骨式纳米碳纤维(f-CNF)进行了表面化学处理. XPS结果表明, 在混酸(浓硫酸+浓硝酸)和氨水中进行超声化学处理可以在CNF表面分别引入含氧官能团和含氮官能团. 电化学测试结果表明, 2种不同微结构CNF的氧还原催化活性都遵循相同的趋势, 即CNF-P相似文献   

Chemoselective Hydrogenation of Functionalized Nitroarenes and Imines by Using Carbon Nanofiber‐Supported Iridium Nanoparticles

The reaction of three types of carbon nanofibers (CNFs; platelet: CNF‐P, tubular: CNF‐T, herringbone: CNF‐H) with Ir₄(CO)₁₂ in mesitylene at 165 °C provided the corresponding CNF‐supported iridium nanoparticles, Ir/CNFs (Ir content=2.3–2.6 wt. %). Transmission electron microscopy (TEM) studies of these Ir/CNF samples revealed that size‐controlled Ir nanoparticles (average particle size of 1.1–1.5 nm) existed on the CNFs. Among the three Ir/CNF samples, Ir/CNF‐T showed an excellent catalytic activity and chemoselectivity towards hydrogenation of functionalized nitroarenes and imines; the corresponding aniline derivatives were obtained with high turnover numbers at ambient temperature under 10 atm of H₂, and the catalyst is reusable. Ir/CNF‐T was also effective for the reductive N‐alkylation of anilines with carbonyl compounds.     

Adsorption of lead(II) from aqueous solution onto several types of activated carbon fibers

In this work, the adsorption of Pb(II) from aqueous solution was investigated on various types of activated carbon fibers (ACFs) manufactured from polyacrylonitrile and phenolic resin. The textural and physicochemical properties of the ACFs were determined by the N₂-BET method and acid-base titration. The experimental adsorption equilibrium data of Pb(II) on the ACFs were obtained in a batch adsorber, and the Langmuir isotherm model better fitted the experimental data. The effects of the type of ACF and precursor of ACF, solution pH and temperature upon the adsorption of Pb(II) on the ACFs were examined in detail. The adsorption capacity was highly dependent upon the precursor of ACF. The Pb(II) adsorption capacity of the ACFs augmented when the solution pH and temperature were increased from 2 to 4 and from 288 to 308 K, respectively. The effect of the pH was attributed to the interactions between the surface of the ACF and Pb²⁺ ions present in the water solution. The Pb(II) adsorption capacity of the ACFs was enhanced by oxidation with HNO₃ solution and the enhancement factor was between 1.1 and 1.4. The reversibility of the adsorption of Pb(II) was investigated by first adsorbing Pb(II) on an ACF and then desorbing the Pb(II). It was noticed that Pb(II) was substantially desorbed from ACF while reducing the solution pH to 2. It was concluded that the Pb(II) was mainly adsorbed on the ACFs by chemisorption, electrostatic interactions and ion exchange.     

Efficient electrochemical incineration of phenol on activated carbon fiber as a new type of particulates

The feasibility of activated carbon fibers (ACFs) used as a new type of particle electrodes in 3-dimensional (3D) electrode for the electrochemical degradation of phenol wastewater was investigated for the first time. The surface morphology, textual properties and electrochemical behaviors of ACF were studied by scanning electron microscopy (SEM), N₂-BET sorption and cyclic voltammograms (CVs), respectively. Compared with the commercialized granular activated carbon (GAC), ACF particle electrodes exhibited higher electrochemical oxidation performance on the mineralization of target pollutant. The identification of intermediates indicated most of oxidation products were adsorbed onto the ACFs. The detection of hydrogen peroxide and hydroxyl radicals in the reaction system suggested that the reaction mechanism was direct anodic oxidation of pollutant on ACFs if the cathode did not contact the ACFs. The operative parameters including initial concentration of substrate, applied current density and the initial aqueous pH have been scientifically studied in search of the optimum condition. Based upon the obtained results, the ACFs longevity was tested in solution at pH 2.0, revealing relatively high electrooxidation capacity and long catalyst lifetime of ACFs in acid solution.     

Electrospun fibers from poly(methyl methacrylate)/vapor grown carbon nanofibers

Electrospinning has been used to obtain poly(methyl methacrylate) (PMMA) microfibers and nanofibers and PMMA/vapor grown carbon nanofibers (VGCNFs or CNFs) composite fibers with micrometer and nanometer size diameters. Thermogravimetric analysis (TGA) indicated that addition of CNFs caused a decrease in the thermal stability of the composite fibers. Scanning electron microscopy (SEM) was used to confirm the micro‐ and nano‐ nature of the fibers and transmission electron microscopy (TEM) was utilized to confirm the presence of CNFs embedded within the polymer matrix and along the surface. Copyright © 2006 John Wiley & Sons, Ltd.     

Formaldehyde removal by Rayon-based activated carbon fibers modified by <Emphasis Type="Italic">P</Emphasis>-aminobenzoic acid

We impregnated Rayon-based activated carbon fibers (ACFs) by p-aminobenzoic acid (PABA) and systematically investigated their porous structure, surface chemistry, and formaldehyde removal behavior. Using standard nitrogen adsorption analysis, we found that the specific surface area, the micropore volume, and the total pore volume decreased with increasing concentration of PABA. Through elemental analysis and X-ray photoelectron spectroscopy, it was found that some nitrogen-containing functional groups presented on the surface of modified Rayon ACFs. The modified Rayon-based ACFs showed much higher adsorption capacity and longer breakthrough time for formaldehyde than did as-prepared Rayon-based ACF. We proposed that the improvement of formaldehyde removal by modified ACFs was attributed to the combined effects of physisorption contributed by pore structures and chemisorption contributed by the N-containing functional groups, whereas there was only physisorption between the as-prepared ACF and formaldehyde molecules.     

Enhanced Conductivity and mechanical properties of polyimide based nanocomposite materials with carbon nanofibers via carbonization of electrospun polyimide fibers

Carbon nanofibers (CNF) have been obtained by the thermal treatment of the electrospun polyimide fibers in our present work. The carbon structure and surface morphology of the as-received CNFs were investigated using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. Investigations of the nanocomposite materials fabricated using these CNFs as conductive fillers and polyimide as matrix show that the presence of CNFs can improve both the mechanical and electrical properties of the material. The conductivity of the nanocomposite films increases with increases in the CNF content and a percolation threshold of about 6.3 vol % (0.0785 in weight fraction) is calculated according to percolation theory.     

Non Thermal Plasma Functionalized 2D Carbon–Carbon Composites as Supports for Co Nanoparticles

Novel two-dimensional carbon–carbon composites made of carbon nanofibers (CNFs) supported on a carbon preform were functionalized by non thermal plasma treatment (room temperature, atmospheric pressure, humid air), before being used as supports for metallic cobalt nanoparticles. It was shown that the degree of functionalization of the carbon nanofibers depends on the plasma power input, the treatment time and the CNF loading. The size of the cobalt nanoparticles generated after subsequent reduction of the Co-containing plasma treated CNF/C composites under hydrogen flow seems to be independent of the amount of supported cobalt. Changes in surface characteristics were analyzed using thermogravimetric analyses coupled to a mass spectrometer, X-ray photoelectron spectroscopy analyses and Raman spectroscopy. Transmission electron microscopy was used to complementary characterize the final size, dispersion and location of the so generated Co nanoparticles.     

Electrochemical capacitances of well-defined carbon surfaces

Reported is the capacitive behavior of homogeneous and well-defined surfaces of pristine carbon nanofibers (CNFs) and surface-modified CNFs. The capacitances of the well-defined CNFs were measured with cyclic voltammetry to correlate the surface structure with capacitance. Among the studied pristine CNFs, the edge surfaces of platelet CNFs (PCNF) and herringbone CNFs were more effective in capacitive charging than the basal plane surface of tubular CNF by a factor of 3-5. Graphitization of PCNF (GPCNF) changed the edge surface of PCNF into a domelike basal plane surface, and the corresponding capacitances decreased from 12.5 to 3.2 F/g. A chemical oxidation of the GPCNF, however, recovered a clear edge surface by removal of the curved basal planes to increase the capacitance to 5.6 F/g. The difference in the contribution of the edge surface and basal-plane surface to the capacitance of CNF was discussed in terms of the anisotropic conductivity of graphitic materials.     

A simple method for the preparation of activated carbon fibers coated with graphite nanofibers

A simple method is described for the preparation of activated carbon fibers (ACFs) coated with graphite nanofibers (GNFs). Low-pressure-plasma mixed-gas (Ar/O2) treatment of the ACFs led to the growth of GNFs on their surface. The growth was greater at higher power inputs, and from TEM observations the GNFs were seen to be of herringbone type. It was found that the N2 adsorption capacity of the ACFs did not sharply decrease, and that volume resistivity of the ACFs enhanced as a result of this treatment.     

Growth and characterization of pyrene crystals on carbon nanofibers

Pyrene crystals were grown on carbon nanofibers (CNFs) by dispersing pyrene polycrystals and CNFs in water during ultrasonic irradiation, and they were characterized by scanning electron microscopy, X-ray diffractometry (XRD) and spectroscopy. The XRD measurements indicated that the orientation and size of the pyrene crystals on the CNF aggregates were different from that of the added pyrene polycrystals. Based on the spectroscopic properties of the pyrene crystals on the CNFs, the pyrene crystals on the CNF aggregates and on the individual CNFs were determined to be polycrystals and single crystals, respectively. These results indicate that pyrene crystals are produced on the CNFs by recrystallization of the added pyrene polycrystals and their crystal states depend on the aggregation state of the CNFs.