Fluorination effect of activated carbon electrodes on the electrochemical performance of electric double layer capacitors

The surface of phenol-based activated carbon (AC) was fluorinated at room temperature with different F₂:N₂ gas mixtures for use as an electrode material in an electric double-layer capacitor (EDLC). The effect of surface fluorination on EDLC electrochemical performance was investigated. The specific capacitance of the fluorinated AC-based EDLC was measured in a 1 M H₂SO₄ electrolyte, in which it was observed that the specific capacitances increased from 375 and 145 F g⁻¹ to 491 and 212 F g⁻¹ with the scan rates of 2 and 50 mV s⁻¹, respectively, in comparison to those of an unfluorinated AC-based EDLC when the fluorination process was optimized via 0.2 bar partial F₂ gas pressure. This enhancement in capacitance can be attributed to the synergistic effect of increased polarization on the AC surface, specific surface area, and micro and mesopore volumes, all of which were induced by the fluorination process. The observed increase in polarization was derived from a highly electronegative fluorine functional group that emerged due to the fluorination process. The increased surface area and pore volume of the AC was derived from the physical function of the fluorine functional group.     

Self-regeneration of activated carbon modified with palladium catalyst for electrochemical dechlorination

Catalyst regeneration and the retention of high catalytic activity are still the critical issues in environmental application.A novel fluidized gas-liquid-solid electrochemical reactor was developed to simultaneously remove chlorinated pollutants and in situ regenerate the spent catalyst.Activated carbon modified with palladium catalyst (AC-Pd) was prepared for electrochemical dechlorination.For the 4-chloropbenol wastewater of initial concentration 200 mg L~(-1),the removal efficiency could nearly reach 100% in less than 30 min.Catalytic activity of AC-Pd catalyst was preserved effectively even in consecutive cycling run without special regeneration.OH radicals,generated by electrochemical reaction,played a critical role in self-regeneration of AC-Pd.High catalytic activity of spent AC-Pd catalyst provided an attractive alternative in wastewater treatment.     

Textural characteristics, surface chemistry and oxidation of activated carbon

Numerous researches were reviewed and interpreted to depict a comprehensive illustration of activated carbon and its behavior towards oxidation. Activated carbon as one of the most important adsorbents is tried to be described in this review paper by terms of its "Textural Characteristics" and "Surface Chemistry". These two terms, coupled with each other, are responsible for behavior of activated carbon in adsorption processes and in catalytic applications. Although as-prepared activated carbons are usually non-selective and their surfaces suffer from lack of enough reactive groups, their different aspects may be improved and developed by diverse types of modifications. Oxidation is one of the most conventional modifications used for activated carbons. It may be used as a final modification or as a pre-modification followed by further treatment. In this paper, methods of oxidation of activated carbon and other graphene-layer carbon materials are introduced and wet oxidation as an extensively-used category of oxidation is discussed in more detail.     

蒙脱石化学修饰电极的制备与电化学特性

用预交换法和掺入法将某些荷阳电物(NR, MB)与荷阴电物[IC, Fe(CN)~6^3-]吸附在蒙脱石膜中制备化学修饰电极(CME)。对不同电性的吸附物, 用预交换法制备的CME在支持电解质溶液中显示不同的伏安响应。被吸附物在蒙脱石膜内的电活性浓度(c*)和总浓度(c~t)之比值较小, 说明被吸附物中只有小部分表现有电化学特性。X衍射实验表明荷阳电的吸附物可能通过离子交换吸附而嵌入蒙脱石层间。吸收光谱实验亦表明荷阳电物与蒙脱石间有强的化学吸附作用。根据蒙脱石中各种不同的吸附位置, 讨论了被吸附物对电化学响应的不同贡献。     

四氟硼酸改性活性炭的制备及其吸附脱除二苯并噻吩性能

采用浸渍法制备了四氟硼酸(HBF₄)改性活性炭,并研究了其对模拟油中二苯并噻吩(DBT)的吸附脱除性能。利用傅里叶红外光谱(FT-IR)、差示热分析仪(TG-DTA)、X射线光电子能谱(XPS)以及N₂吸附技术对吸附剂的表面态和孔结构进行了表征,考察了四氟硼酸浓度、热处理温度以及模拟油中DBT浓度对吸附脱硫效果的影响。结果表明,经质量分数0.5%的HBF₄溶液浸渍、140 ℃热处理后,在剂油比1:100条件下,活性炭的吸附容量为352 mg/g,较未改性活性炭提高了72.5%。     

Effects of the thermal decomposition of surface oxygen species on the chemical and catalytic properties of activated carbon supported Pt catalysts

Several carbon supported Pt catalysts were prepared by varying surface properties of support and tested for methylene chloride oxidation. They were investigated by BET, TPD, pH analysis and XPS. The Pt species would stabilize when the surface carbon was pregraphitized due to the π sites of basal plane. This revised version was published online in June 2006 with corrections to the Cover Date.     

Preparation and electrochemical performance of activated carbon thin films with polyethylene oxide-salt addition for electrochemical capacitor applications

The effect of polymer–salt addition in the activated carbon electrode for electric double-layer capacitor (EDLC) has been investigated. A series of composite thin film electrode consisting of activated carbon, carbon black, polytetrafluoroethylene and polymer–salt complex (polyethyleneoxide–LiClO₄) with an appropriate weight ratio were prepared and examined their performance for EDLCs using 1 mol L⁻¹ LiClO₄ in ethylene carbonate:diethylcarbonate electrolyte solution. The electrochemical capacitance performances of these electrodes with different compositions were characterized by cyclic voltammetry, galvanostatic charge–discharge cycling, and AC impedance measurements. By comparison, the best results were obtained with a composite electrode rich in polymer–salt additive (132 F g⁻¹ at 100 mA g⁻¹ of galvanostatic experiment). In general, the polymer–salt-containing electrode had shown improved performance over activated carbon electrodes without polymer–salt at high current density.     

Adsorption of methyl mercaptan on surface modified activated carbon

The influence of surface modification of activated carbon on the adsorption of methyl mercaptan in N(2) was investigated. The modification of the activated carbon was carried out by treatment with HNO(3)/H(2)SO(4) solutions, heat-treatment in Ar, and adsorption of cetylamine. Acid-treatment increased the adsorption of methyl mercaptan compared with the original activated carbon, and the adsorbed amounts increased with ratio of H(2)SO(4) in HNO(3)/H(2)SO(4) solutions. This result suggests that hydrogen bonding between acidic groups formed by acid-treatment and thiol groups of methyl mercaptan plays a role in adsorption of methyl mercaptan on activated carbon.     

壳聚糖基多孔碳材料的制备及其超级电容性能

以胶态SiO₂纳米粒子为模板,壳聚糖为碳源,ZnCl2为活化剂,制备了具有不同比表面积和孔体积的氮掺杂介孔碳。采用多种表征手段对碳材料的微观形貌、比表面积和孔道结构进行了表征,探究了壳聚糖与SiO₂纳米粒子的比例以及ZnCl2活化剂对碳材料孔体积和比表面积的影响。结果表明,在未使用活化剂时碳材料(CSi-1.75)的孔体积高达4.53 cm³·g^-1,但其比表面积最小(729 m²·g^-1);使用ZnCl₂作为活化剂制备的碳材料(CSi-1.75-Zn)比表面积为1032 m²·g^-1,但其孔体积下降到1.99 cm³·g^-1,且具有最多的吡啶氮和吡咯氮。在以6.0 mol·L^-1 KOH为电解液的三电极体系中,当电流密度为0.5 A·g^-1时,CSi-1.75-Zn的比电容为344 F·g^-1,而CSi-1.75的比电容仅为255 F·g^-1。这表明碳材料的比表面积对超级电容性能影响最大,而孔体积影响较小。电容贡献分析结果表明,相对于CSi-1.75,CSi-1.75-Zn的双电层电容和赝电容都得到了提高,这表明更大的比表面积和更多的吡啶氮和吡咯氮有利于提高碳材料的超级电容性能。     

壳聚糖基多孔碳材料的制备及其超级电容性能

以胶态SiO₂纳米粒子为模板,壳聚糖为碳源,ZnCl₂为活化剂,制备了具有不同比表面积和孔体积的氮掺杂介孔碳。采用多种表征手段对碳材料的微观形貌、比表面积和孔道结构进行了表征,探究了壳聚糖与SiO₂纳米粒子的比例以及ZnCl₂活化剂对碳材料孔体积和比表面积的影响。结果表明,在未使用活化剂时碳材料(CSi-1.75)的孔体积高达4.53 cm³·g^-1,但其比表面积最小(729 m²·g^-1);使用ZnCl₂作为活化剂制备的碳材料(CSi-1.75-Zn)比表面积为1 032 m²·g^-1,但其孔体积下降到1.99 cm³·g^-1,且具有最多的吡啶氮和吡咯氮。在以6.0 mol·L^-1KOH为电解液的三电极体系中,当电流密度为0.5 A·g^-1时,CSi-1.75...     

Adsorption of water vapor on modified activated carbons

Summary The adsorption isotherms of water vapor on modified activated carbons are measured in order to study the role of various surface groups in the primary adsorption of water molecules on these adsorbents. These adsorption isotherms are analysed by means of the Dubinin-Serpinsky and Jovanovic equations, which take into account the special features of water vapor adsorption on microporous activated carbons. Numerical analysis of the measured adsorption isotherms by means of the above mentioned equations showed their limited applicability for interpreting adsorption mechanism of water molecules on activated carbons.

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Adsorption von Wasserdampf auf modifizierter Aktivkohle

Zusammenfassung Die Adsorptionsisothermen von Wasserdampf auf modifizierter Aktivkohle wurden gemessen, um die Rolle verschiedener Oberflächentypen auf die Primäradsorption von Wassermolekülen auf diesen Adsorbenzien zu untersuchen. Die Adsorptionsisothermen wurden mittels der Dubinin-Serpinsky- und Jovanovic-Gleichungen analysiert, welche die speziellen Eigenheiten von Wasser auf mikroporöser Aktivkohle berücksichtigen. Die numerische Analyse der gemessenen Adsorptionsisothermen mittles der genannten Gleichungen zeigte ihre limitierte Anwendbarkeit zur Interpretation von Adsorptionsmechanismen von Wassermolekülen auf modifizierter Aktivkohle.

     

A hybrid nonaqueous electrochemical supercapacitor using nano-sized iron oxyhydroxide and activated carbon

A beta-iron oxyhydroxide (FeOOH) was synthesized via a hydrolyzing route and investigated as a lithium intercalation host. It delivers a capacity of about 170 mAh/g and exhibits good cycling performance when charged/discharged in the voltage range from 1.6 V to 3.3 V. For the first time we have confirmed that FeOOH is suitable for using it as a negative electrode for hybrid electrochemical supercapacitor assembled with an activated carbon positive electrode in 1.0 M LiPF₆ ethylene carbonate/dimethyl carbonate (EC/DMC, 1:2 in volume) solution. The cell reveals a slightly sloping voltage profile from 0 V to 2.8 V and gives an estimated specific energy of 45 Wh/kg based on the total weight of two electrode materials, approximately two times of carbon/carbon electrochemical double layer capacitors. The hybrid supercapacitor shows a good cycling performance, it remains approximately 96% of initial capacity after 800 cycles at a charge/discharge rate of 4 C. The capacitor also shows a desirable rate capability, even at 10 C discharge rate, it holds 80% of capacity compared with that at 1 C discharge rate.     

Adsorption of urea onto granular activated alumina: A comparative study with granular activated carbon

ABSTRACT

This study investigated the ability of granular activated alumina to remove urea from wastewater through adsorption, and compared its performance with granular activated carbon. XRF, EDX, XRD, and TGA were used to investigate the adsorbents. The removal of urea as a function of pH value was studied. The point of zero charge for activated alumina was found to be 8.8, while that for activated carbon was found to be 7.1. The experimental data of the adsorption process were explored by fitting to different kinetic models to determine the adsorption kinetics and mechanisms. Then, the equilibrium data were examined by fitting to various two-parameter and three-parameter isotherm models. Results showed that the removal efficiency increased with the increasing pH value. The maximum removal efficiencies were 24% and 31% for granular activated alumina and granular activated carbon, respectively, at pH?=?9.0. Kinetic studies showed that adsorption of urea onto both activated alumina and activated carbon can be expressed by pseudo second order kinetics. Equilibrium studies showed that the adsorption isotherms could be expressed by the Redlich-Peterson isotherm and Temkin isotherm for activated alumina and activated carbon, respectively. Adsorbents were investigated using FTIR and SEM, and results showed the occurrence of adsorption.     

Electrochemical behavior of glassy carbon electrodes modified by electrochemical oxidation

Glassy carbon electrodes were modified electrochemically by pretreatment in sulfate, phosphate or carbonate solutions by means of cycling the potential well into the positive limit of the solvent. Electrodes treated in this manner were then used to incorporate and concentrate a variety of redox species that were either cations or aromatic containing compounds, including Ru(bpy)²⁺₃, Ru(NH₃)³⁺₆, Cu(NH₃)²⁺₄, ferrocene, methylviologen, 1,4-benzoquinone, anthraquinone-2-sulfonate, riboflavin, flavin mononucleotide (FMN) and flavin adenine dinucleotide (FAD). Surface-equivalent concentrations ranged from 5 × 10^?9 to 1 × 10^?7 mol cm^?2 for electrodes pretreated for 10 min in sulfuric acid. An E_1/2 vs. pH study of 1,4-benzoquinone, riboflavin, FMN and FAD in modified electrodes shows that the pK_a values shift toward higher pH (nearly 2 pH units). Results concerning the incorporation of redox compounds detected only by mediation with other electroactive complexes and the study of the modified electrodes in electrocatalysis are also discussed.     

Electrochemical characteristics of conductive carbon cement as matrix for chemically modified electrodes

Conductive carbon cement (CCC) was evaluated as matrix material for the preparation of electrodes bulk-modified with electrocatalysts. For pure CCC electrodes the background current characteristics were examined. In acidic or neutral phosphate buffers the useful electrode potential range was from −0.3 to + 1.0 V vs. SCE, while in 0.1 mol 1⁻¹ NaOH it was from −0.3 to + 0.7 V. The electrochemical reversibility of CCC electrodes was examined by measuring the standard rate constants for the reduction of hexacyanoferrate (III) and the oxidation of hydroquinone, using cyclic voltammetry (CV) and rotating disk experiments. The reversibility of a CCC electrode was comparable with that of a freshly polished glassy carbon electrode and better than that of carbon paste electrodes. CCC was used as matrix for the preparation of electrodes bulk-modified with cuprous oxide and cobalt phthalocyanine (CoPC). With a Cu₂O-CCC electrode the oxidation potential of glucose, which shows sluggish kinetics at unmodified carbon electrodes, was strongly reduced. The kinetics of the mediated glucose oxidation has been studied with a rotating disk electrode. It was shown that at glucose concentrations higher than approximately 1 mmol l⁻¹ the electrochemical regeneration of the catalyst becomes rate-determining. The Cu₂O-CCC modified electrode has been applied with a constant potential in flow-injection analysis for the determination of glucose. The long-term stability of the electrode was studied; repeated injections of a glucose solution during a period of 6 h yielded a relative standard deviation of the peak height of 1.8% (n = 57). In CV experiments the electrocatalytic activity of CoPC was shown for the oxidation of various compounds such as penicillamine, hydrazine and bile acids. Application of the CoPC-CCC electrode for the detection of bile acids in flow-through detection with a constant or pulsed potential failed, due to a rapid deactivation of the electrode.     

Palladium catalysts supported on activated carbon with different textural and surface chemical properties

A commercial activated carbon was used as catalyst support in Pd/AC catalysts. The effects of the different surface oxygen groups and textural properties of the carbon supports on the metal dispersion of the supported catalysts were analyzed.     

Surface modification by graphene oxide:An efficient strategy to improve the performance of activated carbon based supercapacitors

An efficient and cost-effective strategy to modificate the surface of active carbon (AC), form a 3D-conductive network, and therefore improve the electrochemical performance of AC based supercapacitor was developed.     

Chemically modified activated carbon with S-benzyldithiocarbazate as a new solid-phase extractant for preconcentration of mercury prior to ICP-AES determination

A new sorbent S-benzyldithiocarbazate (SBDTC) modified activated carbon (AC-SBDTC) was prepared and studied for preconcentration for trace mercury(II) prior to inductively coupled plasma atom emission spectrometry (ICP-AES). The experimental conditions were optimised with respect to different experimental parameters using both batch and column procedures in detail. The optimum pH value for the separation of Hg(II) on the new sorbent was 3, while the adsorption equilibrium was achieved in less than 5?min. Complete elution of the adsorbed metal ions from the sorbent surface was carried out using 5?mL of 0.25?mol?L^?1 of HCl and 2% CS(NH₂)₂. Common coexisting ions did not interfere with the determination. The maximum static adsorption capacity of the sorbent under optimum conditions was found to be 0.55?mmol?g^?1. The detection limit of the present method was found to be 0.09?ng?mL^?1, and the relative standard deviation (RSD) was lower than 2.0%. The procedure was validated by analysing the certified reference river sediment material (GBW 08301, China), the results obtained were in good agreement with standard values. This sorbent was successfully employed in the separation and preconcentration of trace Hg(II) from the natural water samples yielding 80-fold concentration factor.     

Interaction of activated carbon electrodes with sulfuric acid solutions

Impedance and potentiodynamic studies have been carried out to investigate reversible processes on the surface of electrodes based on activated carbon (AC). Relationships have been found between the reversible capacity and true resistance, on the one hand, and the potential, on the other. Stoichiometric characteristics of AC charging in sulfuric acid have been obtained. A mechanism of the reversible surface process is suggested. It is concluded that Faraday pseudocapacity makes a considerable contribution to charging of AC electrolytes. The amount of gas liberated in the course of AC wetting in electrolyte has been measured. It is assumed that the amount of liberated gas depends on the amount of active oxygen involved in the current-forming reaction. Based on the data obtained, a redox surface reaction is substantiated in general form.