碱溶液中DMPO-OH加合物EPR信号形成研究
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摘要
为考察碱溶液中DMPO-OH加合物的形成情况及其影响因素,以NaOH溶液为对象,利用EPR(electron paramagneticresonance,电子顺磁共振)技术,通过DMPO (5,5-二甲基-1-吡咯啉-N-氧化物)自旋捕获,对不同条件下NaOH溶液中DMPO-OH加合物的形成及变化规律进行研究,探讨DMPO-OH加合物的生成过程及降解过程反应机制.结果表明:①将DMPO添加到碱溶液中后,在EPR内检测到典型的DMPO-OH四重特征峰(1∶2∶2∶1),说明碱溶液中形成了DMPO-OH加合物.②紫外光激发下,碱溶液体系能产生更强的DMPO-OH加合物特征信号,暗反应体系次之,可见光条件下最弱.③体系中DMPO-OH加合物的生成与碱溶液浓度密切相关,当c(NaOH)由0. 001 mol/L增至2 mol/L时,DMPO-OH加合物的EPR信号峰呈先增后减最终几乎消失的变化趋势.④紫外光照时间对体系中DMPO-OH加合物的存在影响显著,随着光照时间的延长,DMPO-OH加合物的浓度并没有逐渐增高,而是更加倾向于逐渐降低的趋势,这可能是由于形成的DMPO-OH加合物在短时间内被淬灭或分解.⑤碱溶液中DMPO-OH加合物的生成过程为瞬态过程,降解过程占主导,并且紫外光在其生成及降解过程中发挥了重要作用.研究显示,当c(DMPO)为350 mmol/L、c(NaOH)为0. 1 mol/L、紫外光照时间为15 min时,碱溶液中DMPO-OH加合物的EPR信号最佳.
To investigate the DMPO-OH adduct formation condition and its influencing factors in alkali solution,the DMPO-OH adducts in NaOH solution under different conditions were measured by an electron paramagnetic resonance( EPR),and 5,5-dimethyl-1-pyrroline N-oxide( DMPO) was used as the spin trapping compound. The results showed that:( 1) The typical quadruple peak of the DMPO-OH( 1 ∶2 ∶2 ∶1) could be detected by EPR after adding DMPO to the alkali solution,indicating the formation of DMPO-OH adduct would take place in the alkali solution.( 2) For the alkali solution system,a stronger characteristic signal of DMPO-OH adducts could be observed under UV-irradiation,followed by the dark reactions and the weakest under the visible light.( 3) The formation of DMPO-OH adduct was closely related to the c( NaOH). When the c( NaOH) increased from 0. 001 mol/L to 2 mol/L,the EPR signal peak of DMPO-OH adduct was firstly strengthened and then weakened,and eventually disappeared.( 4) The presence of DMPO-OH adduct in the system was affected prominently by the UV-irradiation time. It did not increase gradually,but tended to decrease gradually with the increase of UVirradiation time,which could be attributed to the quenching or degradation of the formed DMPO-OH adduct.( 5) The degradation process of DMPO-OH adduct in alkali solution was dominant and its generation process was a transient response,UV light played a significant role in its formation and degradation processes. The optimum formation conditions of the DMPO-OH adduct in alkali solution were determined as c( DMPO) 350 mmol/L,c( NaOH) 0. 1 mol/L and UV-irradiation time 15 min via the univariate experiments.
To investigate the DMPO-OH adduct formation condition and its influencing factors in alkali solution,the DMPO-OH adducts in NaOH solution under different conditions were measured by an electron paramagnetic resonance( EPR),and 5,5-dimethyl-1-pyrroline N-oxide( DMPO) was used as the spin trapping compound. The results showed that:( 1) The typical quadruple peak of the DMPO-OH( 1 ∶2 ∶2 ∶1) could be detected by EPR after adding DMPO to the alkali solution,indicating the formation of DMPO-OH adduct would take place in the alkali solution.( 2) For the alkali solution system,a stronger characteristic signal of DMPO-OH adducts could be observed under UV-irradiation,followed by the dark reactions and the weakest under the visible light.( 3) The formation of DMPO-OH adduct was closely related to the c( NaOH). When the c( NaOH) increased from 0. 001 mol/L to 2 mol/L,the EPR signal peak of DMPO-OH adduct was firstly strengthened and then weakened,and eventually disappeared.( 4) The presence of DMPO-OH adduct in the system was affected prominently by the UV-irradiation time. It did not increase gradually,but tended to decrease gradually with the increase of UVirradiation time,which could be attributed to the quenching or degradation of the formed DMPO-OH adduct.( 5) The degradation process of DMPO-OH adduct in alkali solution was dominant and its generation process was a transient response,UV light played a significant role in its formation and degradation processes. The optimum formation conditions of the DMPO-OH adduct in alkali solution were determined as c( DMPO) 350 mmol/L,c( NaOH) 0. 1 mol/L and UV-irradiation time 15 min via the univariate experiments.
引文
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[11]余双菊.羟基自由基的特性及检测方法比较[J].广东化工,2010,37(9):141-143.YU Shuangju.The specifity of hydroxyl free radicaland and the methods to detect it[J].Guangdong Chemical Industry,2010,37(9):141-143.
[12]HAN S K,HWANG T M,YOON Y,et al.Evidence of singlet oxygen and hydroxyl radical formation in aqueous goethite suspension using spin-trapping electron paramagnetic resonance(EPR)[J].Chemosphere,2011,84(8):1095-1101.
[13]ROESSLER M M,SALVADIRI E.Principles and applications of EPR spectroscopy in the chemical sciences[J].Chemical Society Reviews,2018,47(8):2534-2553.
[14]KANIGARIDOU Y,PETALA A,FRONTISTIS Z,et al.Solar photocatalytic degradation of bisphenol A with CuOx/BiVO4:insights into the unexpectedly favorable effect of bicarbonates[J].Chemical Engineering Journal,2017,318:39-49.
[15]JIANG Guobin,XU Li,CAO Fuliang,et al.Electron paramagnetic resonance(EPR)studies on free radical scavenging capacity of EGB and EGB cigarette[J].Spectroscopy&Spectral Analysis,2017,37(4):1322-1328.
[16]阳海,黎源,徐淼,等.Fe2+-S2O82--EDTA体系中自由基离子对啶虫脒的氧化降解[J].环境科学研究,2014,27(3):321-327.YANG Hai,LI Yuan,XU Miao,et al.Chemical oxidation degradation of acetamiprid by radical Ions in Fe2+-S2O82--EDTAaqueous solution[J].Research of Environmental Sciences,2014,27(3):321-327.
[17]MIURA Y,UEDA J I,OZAWA T.Formation of the DMPO-OHadduct from Ti(IV)and DMPO in aqueous solution:the first ESRevidence[J].Inorganica Chimica Acta,1995,234(234):169-171.
[18]NOSAKA Y,KOMORI S,YAWATA K,et al.Photocatalytic·OHradical formation in Ti O2aqueous suspension studied by several detection methods[J].Physical Chemistry Chemical Physics,2003,5(20):4731-4735.
[19]杨德敏,夏宏,程方平.臭氧法深度氧化处理页岩气钻井废水[J].水处理技术,2016(2):88-91.YANG Demin,XIA Hong,CHENG Fangping.Advanced treatment of shale gas drilling wastewater by ozonation[J].Technology of Water Treatment,2016(2):88-91.
[20]于丽花,薛娟琴,罗瑶,等.电解液条件对苯酚降解及羟自由基生成的影响[J].环境工程学报,2016(8):4043-4048.YU Lihua,XUE Juanqin,LUO Yao,et al.Influences of conditions of electrolyte solution on phenol degradation and hydroxyl radical generation[J].Chinese Journal of Environmental Engineering,2016(8):4043-4048.
[21]TIAN Guipeng,WU Qianyuan,LI Ang,et al.Enhanced decomposition of 1,4-dioxane in water by ozonation under alkaline condition[J].Water Science&Technology,2014,70(12):1934-1940.
[22]IM J K,ZOH K D.Application of response surface method to carbamazepine removal in photo-ozonation reaction under alkaline condition[J].Water Science&Technology,2013,67(1):74-81.
[23]SALEM M A,ABDEL-HALIM S T,EL-SAWY E H M,et al.Kinetics of degradation of allura red,ponceau 4R and carmosine dyes with potassium ferrioxalate complex in the presence of H2O2[J].Chemosphere,2009,76(8):1088-1093.
[24]李福勤,冉光阳,张晨星.高负硬度矿井水脱碱处理工艺研究[J].工业用水与废水,2017,48(2):15-17.LI Fuqin,RAN Guangyang,ZHANG Chenxing.Study on dealkalization of high negative hardness mine water[J].Industrial Water&Wastewater,2017,48(2):15-17.
[25]FONTMORIN J M,BURGOS-CASTILLO R C,TANG W Z,et al.Stability of 5,5-dimethyl-1-pyrroline-N-oxide as a spin-trap for quantification of hydroxyl radicals in processes based on Fenton reaction[J].Water Research,2016,99:24-32.
[26]高迎新,张昱,杨敏,等.Fe3+或Fe2+均相催化H2O2生成羟基自由基的规律[J].环境科学,2006,27(2):305-309.GAO Yingxin,ZHANG Yu,YANG Min,et al.Comparison of hydroxyl radical production rates in H2O2solution under homogeneous catalysis of Fe3+or Fe2+[J].Environmental Science,2006,27(2):305-309.
[27]KUBO M,SEKIGUCHI K,SHIBASAKI-KITAKAWA N,et al.Kinetic model for formation of DMPO-OH in water under ultrasonic irradiation using EPR spin trapping method[J].Research on Chemical Intermediates,2012,38(9):2191-2204.
[28]NAGARAJAN S,SKILLEN N C,FINA F,et al.Comparative assessment of visible light and UV active photocatalysts by hydroxyl radical quantification[J].Journal of Photochemistry&Photobiology A:Chemistry,2017,334:13-19.
[29]WU Bingdang,YANG Minghui,YIN Ran,et al.Applicability of light sources and the inner filter effect in UV/acetylacetone and UV/H2O2processes[J].Journal of Hazardous Materials,2017,335:100-107.
[30]刘瑞芹,姚思德,谢雷东,等.用电子自旋共振技术研究三种紫外光光源照射真丝绸产生的自由基[J].辐射研究与辐射工艺学报,2008,26(1):9-12.LIU Ruiqin,YAO Side,XIE Leidong,et al.Electron-spin resonance studies of radicals produced on silk fabrics irradiated by three kinds of UV light sources[J].Journal of Radiation Research and Radiation Processing,2008,26(1):9-12.
[31]CHANG Chenyu,HSIEH Y H,CHENG Kaiyuan,et al.Effect of pHon Fenton process using estimation of hydroxyl radical with salicylic acid as trapping reagent[J].Water Science&Technology,2008,58(4):873-879.
[32]SHOJI T,LI Linxiang,ABE Y,et al.DMPO-OH radical formation from 5,5-dimethyl-1-pyrroline N-oxide(DMPO)in hot water[J].Analytical Sciences,2007,23(2):219-221.
[33]LI Linxiang,ABE Y,KANAGAWA K,et al.Distinguishing the 5,5-dimethyl-1-pyrroline N-oxide(DMPO)-OH radical quenching effect from the hydroxyl radical scavenging effect in the ESR spintrapping method[J].Analytica Chimica Acta,2004,512(1):121-124.
[2]MOUSSAVI G,POURAKBAR M,AGHAYANI E,et al.Investigating the aerated VUV/PS process simultaneously generating hydroxyl and sulfate radicals for the oxidation of cyanide in aqueous solution and industrial wastewater[J].Chemical Engineering Journal,2018,350:673-680.
[3]JIANG Feng,QIU Bin,SUN Dezhi.Advanced degradation of refractory pollutants in incineration leachate by UV/peroxymonosulfate[J].Chemical Engineering Journal,2018,349:338-346.
[4]王仕文,张连波,谢陈鑫.臭氧耦合电催化氧化污水深度处理技术的工业应用[J].广东化工,2018,45(9):154-156.Wang Shiwen,ZHANG Lianbo,XIE Chenxin.The industrial application of ozone coupled electro catalytic oxidation technology in advanced treatment of sewage[J].Guangdong Chemical Industry,2018,45(9):154-156.
[5]CHENG Min,ZENG Guangming,HUANG Danlian,et al.Efficient degradation of sulfamethazine in simulated and real wastewater at slightly basic p H values using Co-SAM-SCS/H2O2Fenton-like system[J].Water Research,2018,138:7-18.
[6]XIONG Qing,LUO Mingliang,BAO Xiaoming,et al.Using photocatalytic oxidation and analytic techniques to remediate lab wastewater containing methanol[J].Journal of Chemical Education,2018,95(1):131-135.
[7]LI Zhipeng,LIU Feng,YOU Hong,et al.Advanced treatment of biologically pretreated coal chemical industry wastewater using the catalytic ozonation process combined with a gas-liquid-solid internal circulating fluidized bed reactor[J].Water Science&Technology,2018,77(7):1931-1941.
[8]ABID M F,ALWAN G M,ABDUL R,et al.Study on catalytic wet air oxidation process for phenol degradation in synthetic wastewater using trickle bed reactor[J].Arabian Journal for Science&Engineering,2016,41(7):2659-2670.
[9]王静,邢梦林,邰超,等.不同光谱区间日光照射下水体成分的光致羟基自由基生成研究[J].环境化学,2015,34(12):2162-2169.WANG Jing,XING Menglin,TAI Chao,et al.Generation of hydroxyl radical from water constituents under different spectra bands of sunlight[J].Environmental Chemistry,2015,34(12):2162-2169.
[10]陈日耀,郑曦.电生成羟基自由基及其对染料降解脱色的研究[J].环境科学研究,2002,15(1):16-19.CHEN Riyao,ZHENG Xi.Studies of electro-generated hydroxyl radical and its using in degradation and decolorization of dyes[J].Research of Environmental Sciences,2002,15(1):16-19.
[11]余双菊.羟基自由基的特性及检测方法比较[J].广东化工,2010,37(9):141-143.YU Shuangju.The specifity of hydroxyl free radicaland and the methods to detect it[J].Guangdong Chemical Industry,2010,37(9):141-143.
[12]HAN S K,HWANG T M,YOON Y,et al.Evidence of singlet oxygen and hydroxyl radical formation in aqueous goethite suspension using spin-trapping electron paramagnetic resonance(EPR)[J].Chemosphere,2011,84(8):1095-1101.
[13]ROESSLER M M,SALVADIRI E.Principles and applications of EPR spectroscopy in the chemical sciences[J].Chemical Society Reviews,2018,47(8):2534-2553.
[14]KANIGARIDOU Y,PETALA A,FRONTISTIS Z,et al.Solar photocatalytic degradation of bisphenol A with CuOx/BiVO4:insights into the unexpectedly favorable effect of bicarbonates[J].Chemical Engineering Journal,2017,318:39-49.
[15]JIANG Guobin,XU Li,CAO Fuliang,et al.Electron paramagnetic resonance(EPR)studies on free radical scavenging capacity of EGB and EGB cigarette[J].Spectroscopy&Spectral Analysis,2017,37(4):1322-1328.
[16]阳海,黎源,徐淼,等.Fe2+-S2O82--EDTA体系中自由基离子对啶虫脒的氧化降解[J].环境科学研究,2014,27(3):321-327.YANG Hai,LI Yuan,XU Miao,et al.Chemical oxidation degradation of acetamiprid by radical Ions in Fe2+-S2O82--EDTAaqueous solution[J].Research of Environmental Sciences,2014,27(3):321-327.
[17]MIURA Y,UEDA J I,OZAWA T.Formation of the DMPO-OHadduct from Ti(IV)and DMPO in aqueous solution:the first ESRevidence[J].Inorganica Chimica Acta,1995,234(234):169-171.
[18]NOSAKA Y,KOMORI S,YAWATA K,et al.Photocatalytic·OHradical formation in Ti O2aqueous suspension studied by several detection methods[J].Physical Chemistry Chemical Physics,2003,5(20):4731-4735.
[19]杨德敏,夏宏,程方平.臭氧法深度氧化处理页岩气钻井废水[J].水处理技术,2016(2):88-91.YANG Demin,XIA Hong,CHENG Fangping.Advanced treatment of shale gas drilling wastewater by ozonation[J].Technology of Water Treatment,2016(2):88-91.
[20]于丽花,薛娟琴,罗瑶,等.电解液条件对苯酚降解及羟自由基生成的影响[J].环境工程学报,2016(8):4043-4048.YU Lihua,XUE Juanqin,LUO Yao,et al.Influences of conditions of electrolyte solution on phenol degradation and hydroxyl radical generation[J].Chinese Journal of Environmental Engineering,2016(8):4043-4048.
[21]TIAN Guipeng,WU Qianyuan,LI Ang,et al.Enhanced decomposition of 1,4-dioxane in water by ozonation under alkaline condition[J].Water Science&Technology,2014,70(12):1934-1940.
[22]IM J K,ZOH K D.Application of response surface method to carbamazepine removal in photo-ozonation reaction under alkaline condition[J].Water Science&Technology,2013,67(1):74-81.
[23]SALEM M A,ABDEL-HALIM S T,EL-SAWY E H M,et al.Kinetics of degradation of allura red,ponceau 4R and carmosine dyes with potassium ferrioxalate complex in the presence of H2O2[J].Chemosphere,2009,76(8):1088-1093.
[24]李福勤,冉光阳,张晨星.高负硬度矿井水脱碱处理工艺研究[J].工业用水与废水,2017,48(2):15-17.LI Fuqin,RAN Guangyang,ZHANG Chenxing.Study on dealkalization of high negative hardness mine water[J].Industrial Water&Wastewater,2017,48(2):15-17.
[25]FONTMORIN J M,BURGOS-CASTILLO R C,TANG W Z,et al.Stability of 5,5-dimethyl-1-pyrroline-N-oxide as a spin-trap for quantification of hydroxyl radicals in processes based on Fenton reaction[J].Water Research,2016,99:24-32.
[26]高迎新,张昱,杨敏,等.Fe3+或Fe2+均相催化H2O2生成羟基自由基的规律[J].环境科学,2006,27(2):305-309.GAO Yingxin,ZHANG Yu,YANG Min,et al.Comparison of hydroxyl radical production rates in H2O2solution under homogeneous catalysis of Fe3+or Fe2+[J].Environmental Science,2006,27(2):305-309.
[27]KUBO M,SEKIGUCHI K,SHIBASAKI-KITAKAWA N,et al.Kinetic model for formation of DMPO-OH in water under ultrasonic irradiation using EPR spin trapping method[J].Research on Chemical Intermediates,2012,38(9):2191-2204.
[28]NAGARAJAN S,SKILLEN N C,FINA F,et al.Comparative assessment of visible light and UV active photocatalysts by hydroxyl radical quantification[J].Journal of Photochemistry&Photobiology A:Chemistry,2017,334:13-19.
[29]WU Bingdang,YANG Minghui,YIN Ran,et al.Applicability of light sources and the inner filter effect in UV/acetylacetone and UV/H2O2processes[J].Journal of Hazardous Materials,2017,335:100-107.
[30]刘瑞芹,姚思德,谢雷东,等.用电子自旋共振技术研究三种紫外光光源照射真丝绸产生的自由基[J].辐射研究与辐射工艺学报,2008,26(1):9-12.LIU Ruiqin,YAO Side,XIE Leidong,et al.Electron-spin resonance studies of radicals produced on silk fabrics irradiated by three kinds of UV light sources[J].Journal of Radiation Research and Radiation Processing,2008,26(1):9-12.
[31]CHANG Chenyu,HSIEH Y H,CHENG Kaiyuan,et al.Effect of pHon Fenton process using estimation of hydroxyl radical with salicylic acid as trapping reagent[J].Water Science&Technology,2008,58(4):873-879.
[32]SHOJI T,LI Linxiang,ABE Y,et al.DMPO-OH radical formation from 5,5-dimethyl-1-pyrroline N-oxide(DMPO)in hot water[J].Analytical Sciences,2007,23(2):219-221.
[33]LI Linxiang,ABE Y,KANAGAWA K,et al.Distinguishing the 5,5-dimethyl-1-pyrroline N-oxide(DMPO)-OH radical quenching effect from the hydroxyl radical scavenging effect in the ESR spintrapping method[J].Analytica Chimica Acta,2004,512(1):121-124.
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