介孔碳及其铁改性材料吸附水中对硝基苯酚
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摘要
采用水热合成法以F127为模板剂制备介孔碳材料(MC),一步合成法引入Fe(NO_3)_3·9H_2O得到铁改性介孔碳材料(Fe/MC-x,x为合成原料中铁源与间苯二酚的摩尔比,x=0.5、1.0、1.5),对改性前后的材料进行TEM、N_2吸-脱附、XRD及FI-TR表征,通过考察吸附剂量、吸附等温线、吸附动力学对其吸附水中对硝基苯酚(p-NP)进行了研究。结果表明,所得MC和Fe/MC-x的孔径分布集中于3～4nm,比表面积分别为643.6、635.6、636.0和587.2 m~2/g。实验条件下,Fe/MC-x的吸附性能优于MC,其中Fe/MC-1.0有最大吸附量220.35mg/g,对应去除率为92.33%;平衡吸附量均与初始浓度呈正相关,与吸附剂投加量呈负相关,高温不利于吸附,p-NP在MC和Fe/MC-x上的吸附行为符合Freundlich模型;改性行为加快了吸附速率,吸附过程符合准二级动力学模型,主要为化学吸附控制吸附速率。
Mesoporous carbon(MC)was prepared in the approach of hydrothermal synthesis,with F127 as template.Iron(Ⅲ)nitrate nonahydrate(Fe(NO_3)_3·9H_2O)was added into the synthesis system to prepare Fe-modified mesoporous carbon(Fe/MC-x,x is the molar ratio of Fe to resorcinol,x=0.5,1.0,1.5)by one-step method.TEM,N_2 adsorption-desorption,XRD and FT-IR were used to characterize the textural properties of MC and Fe/MC-x(x=0.5,1.0,1.5).The adsorption behavior of p-nitrophenol(p-NP)by these materials in aqueous solution was investigated,including the dosage of the adsorbent,adsorption isotherm and adsorption kinetics.Results show that the pore sizes of MC and Fe/MC-xare around 3-4nm,and the BET specific surface areas are 643.6m~2/g(for MC)and 635.6m~2/g(for Fe/MC-0.5),636.0m~2/g(for Fe/MC-1.0)and 587.2m~2/g(for Fe/MC-1.5),respectively.The adsorption performance of Fe/MC-xis better than MC and Fe/MC-1.0 has the highest adsorption capacity of 220.35 mg/g under the experimental conditions,and the corresponding removal rate is 92.33%.For these two kinds of materials,the equilibrium adsorption capacities are positively related to the initial concentration,and negatively related to the dosage of the adsorbent.High temperature is unfavorable for adsorption.p-NP adsorption by MC and Fe/MC-x fits well with the Freundlich adsorption isotherms,the adsorption rates are accelerated by the modification.The adsoption processes are described well using pseudo-second-order kinetics,and the main control processes of adsorption rates are chemical adsoption.
Mesoporous carbon(MC)was prepared in the approach of hydrothermal synthesis,with F127 as template.Iron(Ⅲ)nitrate nonahydrate(Fe(NO_3)_3·9H_2O)was added into the synthesis system to prepare Fe-modified mesoporous carbon(Fe/MC-x,x is the molar ratio of Fe to resorcinol,x=0.5,1.0,1.5)by one-step method.TEM,N_2 adsorption-desorption,XRD and FT-IR were used to characterize the textural properties of MC and Fe/MC-x(x=0.5,1.0,1.5).The adsorption behavior of p-nitrophenol(p-NP)by these materials in aqueous solution was investigated,including the dosage of the adsorbent,adsorption isotherm and adsorption kinetics.Results show that the pore sizes of MC and Fe/MC-xare around 3-4nm,and the BET specific surface areas are 643.6m~2/g(for MC)and 635.6m~2/g(for Fe/MC-0.5),636.0m~2/g(for Fe/MC-1.0)and 587.2m~2/g(for Fe/MC-1.5),respectively.The adsorption performance of Fe/MC-xis better than MC and Fe/MC-1.0 has the highest adsorption capacity of 220.35 mg/g under the experimental conditions,and the corresponding removal rate is 92.33%.For these two kinds of materials,the equilibrium adsorption capacities are positively related to the initial concentration,and negatively related to the dosage of the adsorbent.High temperature is unfavorable for adsorption.p-NP adsorption by MC and Fe/MC-x fits well with the Freundlich adsorption isotherms,the adsorption rates are accelerated by the modification.The adsoption processes are described well using pseudo-second-order kinetics,and the main control processes of adsorption rates are chemical adsoption.
引文
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[29]窦建芝,刘金芝,王慧,等.花生壳活性炭吸附苯酚及对硝基苯酚[J].常熟理工学院学报,2011,25(2):47-51.(DOU Jianzhi,LIU Jinzhi,WANG Hui,et al.Adsorption of phenol and 4-nitrophenol on activated carbon derived from peanut hull[J].Journal of Changshu Institute Technology,2011,25(2):47-51.)
[2]查飞,曾慧崇,常玥.氧化石墨对对硝基苯酚的吸附行为[J].科技导报,2014,32(6):34-39.(ZHA Fei,ZENG Huichong,CHANG Yue.Adsorption properties of graphite oxide for p-nitrophenol[J].Science&Technology Review,2014,32(6):34-39.)
[3]张鲜.工业污水中硝基苯酚三种异构体含量的测定与去除方法研究[D].沈阳:沈阳师范大学,2013.
[4]汪艳霞.US/Fenton试剂法处理对硝基苯酚的研究[J].太原大学学报,2013,14(3):145-147.(WANGYanxia.Degradation of p-nitrophenol by US/Fenton reagent method[J].Journal of Taiyuan University,2013,14(3):145-147.)
[5]BHATNAGAR A,SILLANPAA M.Utilization of agro-industrial and municipal waste materials as potential adsorbents for water treatment:A review[J].Chemical Engineering Journal,2010,157(2/3):277-296.
[6]ZHANG Wenjun,WANG Xu,LI Qiang.Research progress of phenol-containing wastewater treatment technology[J].Industral Water Wastewaters,2011,42(1):4-7.
[7]DEHGHANI M H,MAHVI A H,RASTKARI N,et al.Adsorption of bisphenol A(BPA)from aqueous solutions by carbon nanotubes:Kinetic and equilibrium studies[J].Desalination&Water Treatment,2015,54(1):84-92.
[8]KAKAVANDI B,JAHANGIRI-RAD M,RAFIEE M,et al.Development of response surface methodology for optimization of phenol and p-chlorophenol adsorption on magnetic recoverable carbon[J].Microporous&Mesoporous Materials,2016,231(5):192-206.
[9]LIU L,DENG Q F,BAO A,et al.Synthesis of ordered mesoporous carbon materials and their catalytic performance in dehydrogenation of propane to propylene[J].Catalysis Today,2012,186(1):35-41.
[10]LIU L,DENG Q F,AGULA B,et al.Ordered mesoporous carbon catalyst for dehydrogenation of propane to propylene[J].Catalysis Communications,2011,16(1):81-85.
[11]FANG Y,GU D,ZOU Y,et al.A low-concentration hydrothermal synthesis of biocompatible ordered mesoporous carbon nanospheres with tunable and uniform size[J].Angewandte Chemie,2010,49(43):7987-7991.
[12]HUANG Y,CAI H,FENG D,et al.One-step hydrothermal synthesis of ordered mesostructured carbonaceous monoliths with hierarchical porosities[J].Chemical Communications,2008,23(23):2641-2643.
[13]周文,程治良,全学军,等.Fe/AC催化过氧化氢降解双酚A[J].化工学报,2013,64(3):936-942.(ZHOUWen,CHENG Zhiliang,QUAN Xuejun,et al.Catalytic wet oxidation of bisphenol A with hydrogen peroxide over Fe/AC catalyst[J].CIESC Journal,2013,64(3):936-942.)
[14]徐小妹.载铁有序介孔碳Fenton催化剂的制备及性能研究[D].南京:南京理工大学,2014.
[15]张鲜,王莹,高薇,等.紫外可见分光光度法测定污水中间-硝基苯酚的含量[J].沈阳师范大学学报(自然科学版),2012,30(4):531-533.(ZHANG Xian,WANGYing,GAO Wei,et al.Determination of intermediate Meta nitropheno content in sewage by ultraviolet visible spectrophotometry[J].Journal of Shenyang Normal University(Natural Science),2012,30(4):531-533.)
[16]张双,刘芳,李佳蔓,等.氮改性介孔碳的制备及其对水中壬基酚聚氧乙烯醚的吸附[J].石油学报(石油加工),2017,33(3):471-479.(ZHANG Shuang,LIUFang,LI Jiaman,et al.Synthesis of N-modified mesoporous carbon and the adsorption performance for nonylphenol ethoxylates from water[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(3):471-479.)
[17]WEI J,LIANG Y,ZHANG X,et al.Controllable synthesis of mesoporous carbon nanospheres and Fe-N/carbon nanospheres as efficient oxygen reduction electrocatalysts[J].Nanoscale,2015,7(14):6247-6254.
[18]LIU L,DENG Q F,AGULA B,et al.Ordered mesoporous carbon catalyst for dehydrogenation of propane to propylene[J].Catalysis Communications,2011,16(1):81-85.
[19]LI J,GU J,LI H,et al.Synthesis of highly ordered Fe-containing mesoporous carbon materials using soft templating routes[J].Microporous&Mesoporous Materials,2010,128(1-3):144-149.
[20]NAM S,TRATNYEK P G.Reduction of azo dyes with zero-valent iron[J].Water Research,2000,34(6):1837-1845.
[21]BINIAK S,SZYMAN'SKI G,SIEDLEWSKI J,et al.The characterization of activated carbons with oxygen and nitrogen surface groups[J].Carbon,1997,35(12):1799-1810.
[22]GUO Y,ROEKSTRAW D A.Physical and chemical properties of carbons synthesized from xylan,cellulose,and Kraft lignin by H3PO4 activation[J].Carbon,2006,44(8):1464-1475.
[23]FANNING P E,VANNICE M A.ADRIFTS study of the formation of surface groups on carbon by oxidation[J].Carbon,1993,31(5):721-730.
[24]贾建国,李闯,朱春来,等.活性炭的硝酸表面改性及其吸附性能[J].炭素技术,2009,28(6):11-15.(JIAJianguo,LI Chuang,ZHU Chunlai,et al.Surface modification and adsorption property of activated carbon by HNO3[J].Carben Techniques,2009,28(6):11-15.)
[25]GONG C,CHEN D,JIAO X.Continuous hollowα-Fe2O3andα-Fe fibers prepared by the sol-gel method[J].J Mater Chem,2002,12(6):1844-1847.
[26]王正芳.载铁活性炭的制备及对P(V)的吸附性能研究[D].南京:南京大学,2011.
[27]谢红梅,高涛涛,唐旭,等.Fe改性活性炭对水中对硝基苯酚的吸附性能研究[J].西南师范大学学报(自然科学版),2012,37(10):118-122.(XIE Hongmei,GAO Taotao,TANG Xu,et al.Study on the adsorption of p-nitrophenol on water by Fe-modified activated carbon[J].Journal of Southwest China Normal University(Natural Science Edition),2012,37(10):118-122.)
[28]王家宏,尹小龙.双酚A在不同碳材料上的吸附热力学与动力学研究[J].陕西科技大学学报,2015,(2):27-33.(WANG Jiahong,YIN Xiaolong.Study on adsorption thermodynamics and kinetic of bisphenol A on different carbon materials[J].Joural of Shanxi University of Science&Technology,2015,(2):27-33.)
[29]窦建芝,刘金芝,王慧,等.花生壳活性炭吸附苯酚及对硝基苯酚[J].常熟理工学院学报,2011,25(2):47-51.(DOU Jianzhi,LIU Jinzhi,WANG Hui,et al.Adsorption of phenol and 4-nitrophenol on activated carbon derived from peanut hull[J].Journal of Changshu Institute Technology,2011,25(2):47-51.)