Plasma Modification of Activated Carbon Fibers for Adsorption of SO_2

Viscose-based activated carbon fibers （VACFs） were treated by a dielectric-barrier discharge plasma under the feed gas of N2. The surface functional groups of VACFs were modified to improve the adsorption and catalysis capacity for SO2. The surface properties of the untreated and plasma-treated VACFs were diagnosed by SEM, BET, FTIR, and XPS, and the adsorption capacities of VACFs for SO2 were also compared and discussed. The results show that after the plasma treatment, the external surface of VACFs was etched and became rougher, while the surface area and the total pore volume decreased. FTIR and XPS revealed that nitrogen atoms were introduced onto the VACFs surface and the distribution of functional groups on the VACFs surface was changed remarkably. The adsorption characteristic of SO2 indicates that the plasmatreated VACFs have better adsorption capacity than the original VACFs due to the nitrogen functional groups and new functional groups formed in modification, which is beneficial to the adsorption of SO2.

Effect of acidic surface functional groups on Cr(Ⅵ) removal by activated carbon from aqueous solution

The activated carbon with high surface area was prepared by KOH activation.It was further modified by H2SO4 and HNO3 to introduce more surface functional groups.The pore structure of the activated carbons before and after modification was analyzed based on the nitrogen adsorption isotherms.The morphology of those activated carbons was characterized using scanning electronic microscopy （SEM）.The surface functional groups were determined by Fourier transform infrared spectroscopy （FTIR）.The quantity of those groups was measured by the Boehm titration method.Cr（VI） removal by the activated carbons from aqueous solution was investigated at different pH values.The results show that compared with H2SO4,HNO3 destructs the original pore of the activated carbon more seriously and induces more acidic surface functional groups on the activated carbon.The pH value of the solution plays a key role in the Cr（VI） removal.The ability of reducing Cr（VI） to Cr（III） by the activated carbons is relative to the acidic surface functional groups.At higher pH values,the Cr（VI） removal ratio is improved by increasing the acidic surface functional groups of the activated carbons.At lower pH values,however,the acidic surface functional groups almost have no effect on the Cr（VI） removal by the activated carbon from aqueous solution.

Surface functional groups and redox property of modified activated carbons

A series of activated carbons（ACs） were prepared using HNO_3,H_2O_2 and steam as activation agents with the aim to introduce functional groups to carbon surface in the ACs preparation process.The effects of concentration of activation agent,activation time on the surface functional groups and redox property of ACs were characterized by Temperature Program Desorption（TPD） and Cyclic Voltammetry（CV）.Results showed that lactone groups of ACs activated by HNO_3 increase with activation time,and the carboxyl groups increase with the concentration of HNO_3.Carbonyl/quinine groups of ACs activated by H_2O_2 increase with the activation time and the concentration of H_2O_2,although the acidic groups decrease with the concentration of H_2O_2.The redox property reflected by CV at 0 and 0.5 V is different with any kinds of oxygen functional groups characterized by TPD,but it is consistent with the SO_2 catalytic oxidization /oxidation properties indicated by TPR.

A REVIEW OF OXYGEN-CONTAINING SURFACE GROUPS AND SURFACE MODIFICATION OF ACTIVATED CARBON

This review focused on the recent reports related to the function, characterization and modification of oxygen-containing surface groups of activated carbon (AC). The Oxygen-containing surface groups were briefly described, and the most frequently used techniques for characterization of the oxygen-containing surface groups on ACs were also briefly stated. A detailed discussion of the effects of the oxygen-containing surface groups on the adsorptive capacity of AC was given. The recent progresses in modification of the oxygen-containing surface groups of AC were also reviewed.

Enhancement of gaseous mercury(Hg^0) adsorption for the modified activated carbons by surface acid oxygen function groups

This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simulated flue gas at 140 ℃. These surface acid oxygen function groups were identified by Boehm titration, Fourier transformation infrared spectrum, temperature programmed desorption and X-ray photoelectron spectroscopy. It indicates that the carboxyl, lactone and phenolic were formed when the benzoic acid is loaded on the surface of activated carbons. Among the surface acid oxygen function groups, the carboxyl groups enhance the adsorption capacities of Hg^0 for activated carbons to a greater extent.

Highly active catalyst for vinyl acetate synthesis by modified activated carbon

A new zinc acetate catalyst which was prepared from modified activated carbon exhibited extreme activity towards the synthesis of vinyl acetate. The activated carbon was modified by nitric acid, vitriol and peroxyacetic acid （PAA）. The effect on specific area, structure, pH and surface acidity groups of carders by modification was discussed. Amount of carbonyl and carboxyl groups in activated carbon was increased by peroxyacetic acid treatment. The productivity of the new catalyst was 14.58% higher than that of catalyst prepared using untreated activated carbon. The relationship between amount of carbonyl and carboxyl groups （m） and catalyst productivity （P） was P = 1.83 ＋ 2.26 × 10^-3＊e^3.17m. Reaction mechanism was proposed. C 2009 Liang Rong Feng. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Construction of efficient active sites through cyano‐modified graphitic carbon nitride for photocatalytic CO_(2) reduction

The active site amount of photocatalysts,being the key factors in photocatalytic reactions,directly affects the photocatalytic performance of the photocatalyst.Pristine graphitic carbon nitride(g‐C_(3)N_(4))exhibits moderate photocatalytic activity due to insufficient active sites.In this study,cyano‐modified porous g‐C_(3)N_(4)nanosheets(MCN‐0.5)were synthesized through molecular self‐assembly and alkali‐assisted strategies.The cyano group acted as the active site of the photocatalytic reaction,because the good electron‐withdrawing property of the cyano group promoted carrier separation.Benefiting from the effect of the active sites,MCN‐0.5 exhibited significantly enhanced photocatalytic activity for CO2 reduction under visible light irradiation.Notably,the photocatalytic activity of MCN‐0.5 was significantly reduced when the cyano groups were removed by hydrochloric acid(HCl)treatment,further verifying the role of cyano groups as active sites.The photoreduction of Pt nanoparticles provided an intuitive indication that the introduction of cyano groups provided more active sites for the photocatalytic reaction.Furthermore,the controlled experiments showed that g‐C_(3)N_(4)grafted with cyano groups using melamine as the precursor exhibited enhanced photocatalytic activity,which proved the versatility of the strategy for enhancing the activity of g‐C_(3)N_(4)via cyano group modification.In situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations were used to investigate the mechanism of enhanced photocatalytic activity for CO2 reduction by cyano‐modified g‐C_(3)N_(4).This work provides a promising route for promoting efficient solar energy conversion by designing active sites in photocatalysts.

Surface modification of coconut-based activated carbon by SDS and its effects on Pb^(2+) adsorption

Coconut-based activated carbons were modified with sodium dodecyl sulfate (SDS). The activated carbons, which were modified by different concentrations of SDS, were characterized by acid/base titrations, textural analysis (BET), atomic absorption spectrochemical analysis and Zeta potential measurements. The effects of SDS modification on Pb2+ absorption were studied further. The results indicate that after the modification of SDS, there are new functional groups on the surface of modified activated carbons and the number of functional group has changed remarkably, the total acidity decreases observably, but the total alkalinity increases dramatically. With the increase of surface load with SDS, the Pb2+ adsorption mass of activated carbons increases and the optimal pH for Pb2+ adsorption of the SDS modified activated carbons is 5. The experimental data are simulated better by Freundlich isotherm model for the modified activated carbons, and the experimental data are simulated better by Langmuir isotherm model for unmodified ones.

微波加热对活性炭表面基团及其对SO_2吸附性能的影响

采用了微波加热技术 ,通过在不同微波功率和辐射时间条件下对不同粒径活性炭进行改性 ,研究了改性前后活性炭的表面化学基团、元素组成的变化 ,以及对SO2 吸附性能的影响。结果表明 ,经过微波改性后活性炭的SO2 吸附性能大为提高 ,微波功率是影响改性活性炭脱硫性能的主要因素。活性炭经微波热处理后 ,酸性基团发生分解 ,表面含氧量减少 ,碱性特征增强 ,是吸附性能增加的主要原因之一。

活性炭催化剂上SO_2转化活性中心的研究

研究了用不同原料及不同方法制备的活性炭催化剂物化性质变化及其与SO_2转化为SO_3的催化活性的关系。结果表明,催化剂的活性主要取决于其表面性质,而与其孔结构等物理性质无明显关系。XPS和TPD结果认为,催化剂表面上存在有五种数量不等的基团,即(酮基),(烯酮基),其中,含氧基团=C=O为SH_2转化为SO_3的活性中心,可以经改质手段使糠醛渣活性炭上该基团数量增加,从而可提高催化活性。

微波加热改性活性炭及其对SO_2吸附性能的影响

在惰性气体N2氛围下,对活性炭进行不同功率的微波加热改性。通过N2吸附等温线、元素分析、Boehm滴定表征微波加热对活性炭孔隙结构和表面化学性质的影响,分析微波加热改性对活性炭吸附烟气中SO2的影响机制。结果表明,微波加热改性降低了活性炭的比表面积和孔隙容积;降低了活性炭表面酸性官能团的数量,增加了活性炭表面碱性官能团的数量。微波加热改性提高活性炭对SO2的吸附量,归结于其对活性炭表面化学性质的影响。微波加热改性活性炭,以CO形式释放的含氧官能团分解,在活性炭表面形成活性中心,促进活性炭对SO2的吸附和催化氧化。

微波再生对活性炭循环吸附SO_2的影响

研究了脱硫活性炭的微波再生及其对烟气中SO2的循环吸附特性。通过扫描电镜、N2吸附、元素分析、Boehm滴定等表征了微波再生对活性炭孔隙结构和表面化学性质的影响,分析了微波再生对活性炭循环吸附烟气中SO2的影响规律。结果表明,微波再生是脱硫活性炭再生的有效手段,在合适的再生功率下,经过多次循环吸附/再生后,活性炭仍然保持较高的吸附容量,吸附17次后再生活性炭仍然高于原始活性炭,但同时由于再生过程中存在C与H2SO4的反应,活性炭存在明显的烧失现象。初次再生后,活性炭的表面酸性官能团在高温下基本完全分解,碱性官能团含量上升,活性炭的SO2吸附容量明显提高;多次吸附/再生循环后,再生反应起到了活化的作用,使活性炭的孔结构变狭长,微孔比表面积和微孔容积呈上升趋势,同时酸性和碱性官能团基本保持稳定,活性炭的SO2吸附容量逐渐增加。

Preparation and SO2 Adsorption Behavior of Coconut Shell-Based Activated Carbon via Microwave-Assisted Oxidant Activation

A series of oxidants supported on coconut shell-based activated carbon(CAC) through microwave irradiation were prepared and characterized using scanning electron microscopy(SEM), N_2 adsorption/desorption analysis, and X-ray photoelectron spectroscopy(XPS). The SO_2 adsorption capacities and rates were evaluated by adsorption tests performed in a fixed bed reactor with a simulated flue gas, and the adsorption isotherm models were validated against the experimental results. The findings revealed that the SO_2 adsorption capacity decreased in the following order: MW-K_2Cr_2O_7-CAC > MWKMnO_4-CAC > MW-H_2O_2-CAC > MW-CAC. The SO_2 adsorption capacities and adsorption rates of the samples increased with an increasing oxidizability of the oxidants owing to the increment of mean pore size and oxygen-containing functional groups. In addition, a high initial SO_2 concentration and a low bed temperature could positively affect the SO2 adsorption. Finally, the Langmuir model validated that SO_2 was mainly adsorbed through chemical adsorption on the sample surfaces.

Investigation on the Key Factors and the Solution for pH Value Decrease in Carbon Filter in O3-BAC Process＊

An investigation was carried out to eliminate the decrease of effluent pH value in carbon filter in O3-biological activated carbon process. The influence factors were examined in a pilot test, and pH was adjusted in the pilot and waterworks. Results show that the carbon filter is an acid-base buffer system and the activated carbon is the key factor. Chemical functional groups on activated carbon surface present acid-base properties to buffer the water but decrease with time, so that effluent pH value decreases. The effects of ozone dosage, CO2 in the carbon filter, and the filter influent quality are negligible. A new method to adjust pH is developed: the activated carbon is first modified by soaking in sodium hydroxide solution to make its pH reach the desired value, and then the pH value of inflow is controlled to certain value by dosing lime in sand filter influent. The method is economical and effective.

Acid/Base Treatment of Monolithic Activated Carbon for Coating Silver with Tunable Morphology

Silver coatings on the exterior surface of monolithic activated carbon（MAC） with different morphology were prepared by directly immersing MAC into [Ag（NH3）2]NO3 solution. Acid and base treatments were employed to modify the surface oxygenic groups of MAC, respectively. The MACs＇ Brunauer-EmmettTeller（BET） surface area, surface groups, and silver coating morphology were characterized by N2 adsorption, elemental analysis（EA）, X-ray photoelectron spectroscopy（XPS）, and scanning electron microscopy（SEM）, respectively. The coating morphology was found to be closely related to the surface area and surface functional groups of MAC. For a raw MAC which contained a variety of oxygenic groups, HNO3 treatment enhanced the relative amount of highly oxidized groups such as carboxyl and carbonates, which disfavored the deposition of silver particles. By contrast, Na OH treatment significantly improved the amount of carbonyl groups, which in turn improved the deposition amount of silver. Importantly, lamella silver was produced on raw MAC while Na OH treatment resulted in granular particles because of the capping effect of carbonyl groups. At appropriate [Ag（NH3）2]NO3 concentrations, silver nanoparticles smaller than 100 nm were homogeneously dispersed on Na OH-treated MAC. The successful tuning of the size and morphology of silver coatings on MAC is promising for novel applications in air purification and for antibacterial or aesthetic purposes.

Catalytic Pyrolyses of Rayon and the Effect on Activated Carbon Fiber

The catalytic pyrolyses of rayon have been studied respectively by thermo-gravimetric analysis (TGA) when rayon was treated with phosphoric acid (PA), three ammonium phosphate salts and ammonium sulfate (AS). The air is favorable to the catalysis of dibasic ammonium phosphate (DAP), but not to those of ADP, PA, AP, and AS obviously. It is put forward that a peak’s shape character can be described with the ratio of height to half-height-width (H/W /2) of the peak on a differential thermo-gravimetric (DTG) curve. A flat cracking peak, presenting a more moderate dehydration reaction, has a smaller ratio and could lead to higher carbonization and activation yields. The experimental results prove this view. According to expectation, the order of catalysis is: DAP≥ADP>PA> APAS no catalyst.

Mechanism study on the influence of surface properties on the synthesis of dimethyl carbonate from CO_(2)and methanol over ceria catalysts

The direct synthesis of dimethyl carbonate(DMC)from CO_(2)and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes.Herein,a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO_(2)and methanol,and the structure-performance relationship was investigated in detail.Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts.In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)studies indicated that the adsorption rate of methanol is slower than that of CO_(2)and the methanol activation state largely influences the formation of key intermediate.Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO_(2),the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation.Moreover,with the use of 2-cyanopyridine as a dehydration reagent,the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.

Enhanced Capacitive Characteristics of Activated Carbon by Secondary Activation

The effect of the improvement of commercial activated carbon(AC) on its specific capacitance and high rate capability of double layer(dl) charging/discharging process has been studied. The improvement of AC was carried out \%via\% a secondary activation under steam in the presence of catalyst NiCl\-2, and the suitable condition was found to be a heat treatment at about 875 ℃ for 1 h. Under those conditions, the discharge specific capacitance of the improved AC increases up to 53.67 F/g, showing an increase of about 25% as compared with that of as-received AC. The good rectangular-shaped voltammograms and A.C. impedance spectra prove that the high rate capability of the capacitor made of the improved AC is enhanced significantly. The capacitance resistance(RC) time constant of the capacitor containing the improved AC is 1\^74 s, which is much lower than that of the one containing as-received AC(an RC value of 4.73 s). It is noted that both kinds of AC samples show a similar specific surface area and pore size distribution, but some changes have taken place in the carbon surface groups, especially a decrease in the concentration of surface carbonyl groups after the improvement, which have been verified by means of X-photoelectron spectroscopy. Accordingly, it is suggested that the decrease in the concentration of surface carbonyl groups for the improved AC is beneficial to the organic electrolyte ion penetrating into the pores, thus leading to the increase in both the specific capacitance and high rate capability of the supercapacitor.

Characteristics of Chemical Modified Activated Carbons from Bamboo Scaffolding

In this study, bamboo scaffolding was used to produce activated carbon by carbonization at 600 ℃ and 900 ℃with the purge of nitrogen. The 600 ℃ char was then further modified chemically by acids and alkalis by reflux for 6 hours. The produced chars were then characterized by nitrogen adsorption isotherm, He pyncometry, pH, elemental analysis and Boehm titration. For most of the chemically modified carbons, the micropore surface areas and volumes have increased compared with the 600 ~C char, while the mesopore surface areas and volumes slightly decreased, which may have been due to the dissolving of some of the permeated inorganic matter and oxidizing deposited carbon that blocks the pore openings. For the acidic modified carbons, larger amounts of acidic groups were present in the carbons after being activated by phosphoric acid, phosphoric acid furth, er treated with 2 mol-L-1nitric-acid, and calcium hydroxide. Although carbon treated with 2 mol.L-1 and 5 mol·L-1 nitric acid also produced high acidity, the surface areas and pore volumes were relatively low, due to the destruction of pores by nitric acid oxidation. The reduction of porosity may impair the adsorption capacity.

基于响应曲面法优化氮掺杂活性炭的制备和CO_(2)吸附性能研究

氮掺杂活性炭制备过程中影响其性能的因素极其复杂,单一因素的定性分析无法满足对制备条件的准确调控,而多因素耦合量化分析可以弥补不足。以煤焦油沥青为原料,采用KOH活化法,与尿素共热解制备氮掺杂活性炭,通过响应曲面法(RSM)进行建模,以量化分析多因素耦合作用对活性炭产率和不同温度下(25℃,50℃和75℃)对CO_(2)吸附性能的影响,同时优化制备工艺参数,并且在此实验设计基础上利用线性拟合方法预测不同温度下CO_(2)吸附量的相关性。结果表明:对活性炭产率的影响由大到小的单因素依次为掺氮比(尿素与煤沥青的质量比)、活化温度、碱碳比(KOH与煤沥青的质量比)、活化时间,活化温度和活化时间的耦合作用影响最显著,碱碳比是影响活性炭CO_(2)吸附量最为关键的因素,但随吸附温度升高其他因素影响显著性增强;不同温度下CO_(2)吸附量可以进行相互预测,且相邻温度下CO_(2)吸附量之间的预测效果更好;得到的最佳制备条件为活化温度650℃、活化时间1.25 h、碱碳比2.5、掺氮比0.3,相应的活性炭产率可达59.316%,在25℃,50℃和75℃下CO_(2)吸附量分别为3.474 mmol/g,2.355 mmol/g,1.358 mmol/g。