生物质基碳材料的制备及其在电芬顿降解体系中的应用
|
摘要
偶氮类染料因其色度高、毒性大的特点,借助传统处理方法很难对其进行有效降解。高级氧化技术中的阴极电芬顿法利用H_2O_2和Fe~(2+)生成氧化能力较强的羟基自由基(·OH),从而实现水体中偶氮染料的高效降解。该研究选取生活中常见且蛋白质含量较高的韭苔为前驱体,以KHCO_3为活化剂,高温热解制备生物质基碳电极材料(CS-R),并成功应用于电芬顿法降解甲基红(MR)体系。经过对所制备得到的系列样品进行优化筛选,CS-3表现出良好的氧还原性能,其作为阴极电催化剂对MR染料的降解效率在60min时达到了99%。研究结果表明,高的比表面积、氮含量、石墨化程度和超亲水性对于生物质基碳材料的电芬顿降解性能至关重要,这为电芬顿体系阴极材料的选择、制备提供了技术指导。
Azo dyes,as one of the serious dyestuff are difficult to degrade among the various pollutants owing to their high colority and toxicity.The electro-Fenton process consists of two parts,(1)the in-situ electrogeneration of H_2O_2 by two-electron reduction of oxygen,(2)the reaction of H2 O2 with Fe2+to form a strong oxidant·OH,which unselectively attacks organic pollutants.Herein,biomass-derived carbon materials fabricated from chives stem(CS)were used as cathode electrocatalysts to degrade the targeted methyl red(MR)dye.The model sample CS-3 exhibited superior oxygen reduction reaction performance as the EF cathode catalyst and the degradation efficiency of MR reached 99% merely within 60 min.This research demonstrates that the high specific surface area,degree of graphitization,content of N and superhydrophilicity play crucial roles in the electroFenton degradation performance of the carbon materials,which provides guidance for the electro-Fenton electrode materials optimizing.
Azo dyes,as one of the serious dyestuff are difficult to degrade among the various pollutants owing to their high colority and toxicity.The electro-Fenton process consists of two parts,(1)the in-situ electrogeneration of H_2O_2 by two-electron reduction of oxygen,(2)the reaction of H2 O2 with Fe2+to form a strong oxidant·OH,which unselectively attacks organic pollutants.Herein,biomass-derived carbon materials fabricated from chives stem(CS)were used as cathode electrocatalysts to degrade the targeted methyl red(MR)dye.The model sample CS-3 exhibited superior oxygen reduction reaction performance as the EF cathode catalyst and the degradation efficiency of MR reached 99% merely within 60 min.This research demonstrates that the high specific surface area,degree of graphitization,content of N and superhydrophilicity play crucial roles in the electroFenton degradation performance of the carbon materials,which provides guidance for the electro-Fenton electrode materials optimizing.
引文
[1] Xu Xiangrong,Li Huabin,Wang Wenhua,et al.Degradation of dyes in aqueous solutions by the Fenton process[J].Chemosphere,2004,57(7):595-600.
[2] Marc H M,Silvio C,Gun-Young P,et al.Oxidation of pharmaceuticals during ozonation and advanced oxidation processes[J].Environmental Science&Technology,2003,37(5):1016-1024.
[3] Souza S M A G U D,Eliane F,Souza A A U D.Toxicity of textile dyes and their degradation by the enzyme horseradish peroxidase(HRP)[J].Journal of Hazardous Materials,2007,147(3):1073-1078.
[4] Ahmed M J.Preparation of activated carbons from date(phoenix dactylifera L)palm stones and application for wastewater treatments:review[J].Process Safety&Environmental Protection,2016,102:168-182.
[5] Bensalah N,Alfaro M A Q,Martínez-Huitle C A.Electrochemical treatment of synthetic wastewaters containing alphazurine A dye[J].Chemical Engineering Journal,2009,149(1):348-352.
[6] Gao Shuyan,Su Jingzhen,Wang Miao,et al.Electrochemical oxidation degradation of azobenzene dye self-powered by multilayer-linkage triboelectric nanogenerator[J].Nano Energy,2016,30:52-58.
[7] Abdoulaye T,Ignasi S,Antonio G J,et al.Effect of anions on electrochemical degradation of azo dye carmoisine(Acid Red 14)using a BDD anode and air-diffusion cathode[J].Separation&Purification Technology,2015,140:43-52.
[8] Richardson S D,Kimura S Y.Emerging environmental contaminants:challenges facing our next generation and potential engineering solutions[J].Environmental Technology&Innovation,2017,8:40-56.
[9] Poza-Nogueiras V,Rosales E,Pazos M,et al.Current advances and trends in electro-Fenton process using heterogeneous catalysts-a review[J].Chemosphere,2018,201:399-416.
[10] Gong Yuexiang,Li Jiuyi,Zhang Yanyu,et al.Partial degradation of levofloxacin for biodegradability improvement by electro-Fenton process using an activated carbon fiber felt cathode[J].Journal of Hazardous Materials,2016,304:320-328.
[11] Nidheesh P V,Gandhimathi R.Trends in electro-Fenton process for water and wastewater treatment:an overview[J].Desalination,2012,299(4):1-15.
[12] Chen Ye,Wang Miao,Tian Miao,et al.An innovative electro-Fenton degradation system self-powered by triboelectric nanogenerator using biomass-derived carbon materials as cathode catalyst[J].Nano Energy,2017,42:314-321.
[13] Cao Linyuan,Liu Yanlan,Zhang Baohua,et al.In situ controllable growth of prussian blue nanocubes on reduced graphene oxide:facile synthesis and their application as enhanced nanoelectrocatalyst for H2O2reduction[J].ACS Applied Materials&Interfaces,2010,2(8):2339-2346.
[14] Martínez-Huitle C A,Rodrigo M A,Sirés I,et al.Single and coupled electrochemical processes and reactors for the abatement of organic water pollutants:a critical review[J].Chemical Reviews,2015,115(24):13362-13407.
[15] Zhou Lei,Hu Zhongxin,Zhang Chao,et al.Electrogeneration of hydrogen peroxide for electro-Fenton system by oxygen reduction using chemically modified graphite felt cathode[J].Separation and Purification Technology,2013,111(12):131-136.
[16] Yu Fangke,Chen Yang,Ma Hongrui.Ultrahigh yield of hydrogen peroxide and effective diclofenac degradation on graphite felt cathode loading with CNT and carbon black:an electro-generation mechanism and degradation pathway[J].New Journal of Chemistry,2018,42(6):4485-4494.
[17] Irmak S,Yavuz H I,Erbatur O.Degradation of 4-chloro-2-methylphenol in aqueous solution by electro-Fenton and photoelectro-Fenton processes[J].Applied Catalysis B:Environmental,2006,63(3):243-248.
[18] Gao Shuyan,Wang Miao,Chen Ye,et al.An advanced electro-Fenton degradation system with triboelectric nanogenerator as electric supply and biomass-derived carbon materials as cathode catalyst[J].Nano Energy,2018,45:21-27.
[19] Luo Rui,Liu Chao,Li Jiansheng,et al.Deep-eutectic solvents derived nitrogen-doped graphitic carbon as a superior electrocatalyst for oxygen reduction[J].ACS Applied Materials&Interfaces,2017,9(38):32737-32744.
[20] Gao Shuyan,Geng Keran,Liu Haiying,et al.Transforming organic-rich amaranthus waste into nitrogen-doped carbon with superior performance of the oxygen reduction reaction[J].Energy&Environmental Science,2015,8(1):221-229.
[21] Gao Shuyan,Li Xiaoge,Li Lingyu,et al.A versatile biomass derived carbon material for oxygen reduction reaction,supercapacitors and oil/water separation[J].Nano Energy,2017,33:334-342.
[22] Gao Shuyan,Wei Xianjun,Fan Hao,et al.Nitrogendoped carbon shell structure derived from natural leaves as a potential catalyst for oxygen reduction reaction[J].Nano Energy,2015,13:518-526.
[23] Gao Shuyan,Fan Baofa,Feng Rui,et al.N-doped-carbon-coated Fe3O4from metal-organic framework as efficient electrocatalyst for ORR[J].Nano Energy,2017,40:462-470.
[24] Cho S H,Shin K H,Jang J.Enhanced electrochemical performance of highly porous supercapacitor electrodes based on solution processed polyaniline thin films[J].ACS Applied Materials&Interfaces,2013,5(18):9186-9193.
[25] Wang Shuguang,Wang Haifeng,Zhang Rui,et al.Egg yolk-derived carbon:achieving excellent fluorescent carbon dots and high performance lithium-ion batteries[J].Journal of Alloys and Compounds,2018,746:567-575.
[26] Zhang Zhenping,Gao Xinjin,Dou Meiling,et al.Biomass derived N-doped porous carbon supported single Fe atoms as superior electrocatalysts for oxygen reduction[J].Small,2017,13(22):1604290.
[27] Liu Jiandong,Ma Xiaohong,Yang Lina,et al.In situ green oxidation synthesis of Ti 3+and N self-doped SrTiOxNy nanoparticles with enhanced photocatalytic activity under visible light[J].RSC Advances,2018,8(13):7142-7151.
[28] Gao Shuyan,Chen Ye,Su Jingzhen,et al.Triboelectric nanogenerator powered electrochemical degradation of organic pollutant using Pt-free carbon materials[J].ACS Nano,2017,11(4):3965-3972.
[29] Xu He,Wu Chengke,Wei Xianjun,et al.Hierarchically porous carbon materials with controllable proportion of micropore area by dual-activator synthesis for high-performance supercapacitors[J].Journal of Materials Chemistry A,2018,6:15340-15347.
[30] Gao Shuyan,Liu Haiying,Geng Keran,et al.Honeysuckles-derived porous nitrogen,sulfur,dual-doped carbon as high-performance metal-free oxygen electroreduction catalyst[J].Nano Energy,2015,12:785-793.
[31] Huang Senchuan,Meng Yuying,He Shiman,et al.N-,O-,and S-tridoped carbon-encapsulated Co9S8 nanomaterials:efficient bifunctional electrocatalysts for overall water splitting[J].Advanced Functional Materials,2017,27(17):1606585.
[32] Huang Hui,Wei Xianjun,Gao Shuyan.Nitrogen-doped porous carbon derived from malachium aquaticum biomass as a highly efficient electrocatalyst for oxygen reduction reaction[J].Electrochimica Acta,2016,220:427-435.
[2] Marc H M,Silvio C,Gun-Young P,et al.Oxidation of pharmaceuticals during ozonation and advanced oxidation processes[J].Environmental Science&Technology,2003,37(5):1016-1024.
[3] Souza S M A G U D,Eliane F,Souza A A U D.Toxicity of textile dyes and their degradation by the enzyme horseradish peroxidase(HRP)[J].Journal of Hazardous Materials,2007,147(3):1073-1078.
[4] Ahmed M J.Preparation of activated carbons from date(phoenix dactylifera L)palm stones and application for wastewater treatments:review[J].Process Safety&Environmental Protection,2016,102:168-182.
[5] Bensalah N,Alfaro M A Q,Martínez-Huitle C A.Electrochemical treatment of synthetic wastewaters containing alphazurine A dye[J].Chemical Engineering Journal,2009,149(1):348-352.
[6] Gao Shuyan,Su Jingzhen,Wang Miao,et al.Electrochemical oxidation degradation of azobenzene dye self-powered by multilayer-linkage triboelectric nanogenerator[J].Nano Energy,2016,30:52-58.
[7] Abdoulaye T,Ignasi S,Antonio G J,et al.Effect of anions on electrochemical degradation of azo dye carmoisine(Acid Red 14)using a BDD anode and air-diffusion cathode[J].Separation&Purification Technology,2015,140:43-52.
[8] Richardson S D,Kimura S Y.Emerging environmental contaminants:challenges facing our next generation and potential engineering solutions[J].Environmental Technology&Innovation,2017,8:40-56.
[9] Poza-Nogueiras V,Rosales E,Pazos M,et al.Current advances and trends in electro-Fenton process using heterogeneous catalysts-a review[J].Chemosphere,2018,201:399-416.
[10] Gong Yuexiang,Li Jiuyi,Zhang Yanyu,et al.Partial degradation of levofloxacin for biodegradability improvement by electro-Fenton process using an activated carbon fiber felt cathode[J].Journal of Hazardous Materials,2016,304:320-328.
[11] Nidheesh P V,Gandhimathi R.Trends in electro-Fenton process for water and wastewater treatment:an overview[J].Desalination,2012,299(4):1-15.
[12] Chen Ye,Wang Miao,Tian Miao,et al.An innovative electro-Fenton degradation system self-powered by triboelectric nanogenerator using biomass-derived carbon materials as cathode catalyst[J].Nano Energy,2017,42:314-321.
[13] Cao Linyuan,Liu Yanlan,Zhang Baohua,et al.In situ controllable growth of prussian blue nanocubes on reduced graphene oxide:facile synthesis and their application as enhanced nanoelectrocatalyst for H2O2reduction[J].ACS Applied Materials&Interfaces,2010,2(8):2339-2346.
[14] Martínez-Huitle C A,Rodrigo M A,Sirés I,et al.Single and coupled electrochemical processes and reactors for the abatement of organic water pollutants:a critical review[J].Chemical Reviews,2015,115(24):13362-13407.
[15] Zhou Lei,Hu Zhongxin,Zhang Chao,et al.Electrogeneration of hydrogen peroxide for electro-Fenton system by oxygen reduction using chemically modified graphite felt cathode[J].Separation and Purification Technology,2013,111(12):131-136.
[16] Yu Fangke,Chen Yang,Ma Hongrui.Ultrahigh yield of hydrogen peroxide and effective diclofenac degradation on graphite felt cathode loading with CNT and carbon black:an electro-generation mechanism and degradation pathway[J].New Journal of Chemistry,2018,42(6):4485-4494.
[17] Irmak S,Yavuz H I,Erbatur O.Degradation of 4-chloro-2-methylphenol in aqueous solution by electro-Fenton and photoelectro-Fenton processes[J].Applied Catalysis B:Environmental,2006,63(3):243-248.
[18] Gao Shuyan,Wang Miao,Chen Ye,et al.An advanced electro-Fenton degradation system with triboelectric nanogenerator as electric supply and biomass-derived carbon materials as cathode catalyst[J].Nano Energy,2018,45:21-27.
[19] Luo Rui,Liu Chao,Li Jiansheng,et al.Deep-eutectic solvents derived nitrogen-doped graphitic carbon as a superior electrocatalyst for oxygen reduction[J].ACS Applied Materials&Interfaces,2017,9(38):32737-32744.
[20] Gao Shuyan,Geng Keran,Liu Haiying,et al.Transforming organic-rich amaranthus waste into nitrogen-doped carbon with superior performance of the oxygen reduction reaction[J].Energy&Environmental Science,2015,8(1):221-229.
[21] Gao Shuyan,Li Xiaoge,Li Lingyu,et al.A versatile biomass derived carbon material for oxygen reduction reaction,supercapacitors and oil/water separation[J].Nano Energy,2017,33:334-342.
[22] Gao Shuyan,Wei Xianjun,Fan Hao,et al.Nitrogendoped carbon shell structure derived from natural leaves as a potential catalyst for oxygen reduction reaction[J].Nano Energy,2015,13:518-526.
[23] Gao Shuyan,Fan Baofa,Feng Rui,et al.N-doped-carbon-coated Fe3O4from metal-organic framework as efficient electrocatalyst for ORR[J].Nano Energy,2017,40:462-470.
[24] Cho S H,Shin K H,Jang J.Enhanced electrochemical performance of highly porous supercapacitor electrodes based on solution processed polyaniline thin films[J].ACS Applied Materials&Interfaces,2013,5(18):9186-9193.
[25] Wang Shuguang,Wang Haifeng,Zhang Rui,et al.Egg yolk-derived carbon:achieving excellent fluorescent carbon dots and high performance lithium-ion batteries[J].Journal of Alloys and Compounds,2018,746:567-575.
[26] Zhang Zhenping,Gao Xinjin,Dou Meiling,et al.Biomass derived N-doped porous carbon supported single Fe atoms as superior electrocatalysts for oxygen reduction[J].Small,2017,13(22):1604290.
[27] Liu Jiandong,Ma Xiaohong,Yang Lina,et al.In situ green oxidation synthesis of Ti 3+and N self-doped SrTiOxNy nanoparticles with enhanced photocatalytic activity under visible light[J].RSC Advances,2018,8(13):7142-7151.
[28] Gao Shuyan,Chen Ye,Su Jingzhen,et al.Triboelectric nanogenerator powered electrochemical degradation of organic pollutant using Pt-free carbon materials[J].ACS Nano,2017,11(4):3965-3972.
[29] Xu He,Wu Chengke,Wei Xianjun,et al.Hierarchically porous carbon materials with controllable proportion of micropore area by dual-activator synthesis for high-performance supercapacitors[J].Journal of Materials Chemistry A,2018,6:15340-15347.
[30] Gao Shuyan,Liu Haiying,Geng Keran,et al.Honeysuckles-derived porous nitrogen,sulfur,dual-doped carbon as high-performance metal-free oxygen electroreduction catalyst[J].Nano Energy,2015,12:785-793.
[31] Huang Senchuan,Meng Yuying,He Shiman,et al.N-,O-,and S-tridoped carbon-encapsulated Co9S8 nanomaterials:efficient bifunctional electrocatalysts for overall water splitting[J].Advanced Functional Materials,2017,27(17):1606585.
[32] Huang Hui,Wei Xianjun,Gao Shuyan.Nitrogen-doped porous carbon derived from malachium aquaticum biomass as a highly efficient electrocatalyst for oxygen reduction reaction[J].Electrochimica Acta,2016,220:427-435.