铁(Ⅲ)席夫碱配合物的合成及其对新型环境污染物酞酸丁酯的降解性能
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摘要
通过水杨醛(salicylideimine,SA)与四乙烯五胺(tetraethylenepentamine,TEPA)缩合反应合成了四乙烯五胺水杨醛亚胺席夫碱配体ST [ST=N, N’-tetraethylenepentaminebis(salicylideimine)],进一步与铁(Ⅲ)配位得到双核铁(Ⅲ)配合物[Fe_2(ST)(H_2O)_4]Cl_4[简写为Fe_2(ST)]。通过元素分析(EA)、红外光谱(FTIR)、紫外可见光谱(UV-Vis)等手段对其进行了表征。以其为催化剂,考察了在双氧水作用下,可见光降解水中新型环境污染物酞酸丁酯(DBP)的性能。结果表明,pH在3.5～8.0范围内,Fe_2(ST)的浓度大于5.5 mmol/L,H_2O_2的浓度大于8.2 mmol/L,10 min内催化体系可以实现对浓度小于20.0 mg/L的DBP 99%以上的降解。监测了加入H_2O_2前后的反应体系电子光谱随时间的变化,结果表明催化剂的活性位点可能为μ-N桥联的双核Fe(Ⅲ)活性中心,形成了有利于H_2O_2活化的过渡态。催化体系在循环使用10次后,对DBP的降解率仍可达95%。Fe2(ST)是具有优异潜力的水中酞酸丁酯污染物的绿色催化剂。
Schiff base ligand(ST = N, N'-tetraethylene pentaminebis(salicylideimine) was prepared by condensation reaction of salicylaldehyde(SA) and tetraethylenepentamine(TEPA), and further coordinated with iron(Ⅲ) via coordination reaction to form a binuclear iron(Ⅲ) complex, [Fe_2(ST)(H_2 O)_4]Cl_4(abbreviated as Fe_2(ST)). It was characterized by elemental analysis(EA), Fourier transform infrared spectrometer(FTIR), and ultraviolet-visible spectroscopy(UV-vis), etc. It was used as catalyst for the degradation of emerging contaminants, e. g., dibutyl phthalate(DBP) under visible light with hydrogen peroxide solution as oxidant. The results show that at pH 3.5～8.0,with the initial concentration of Fe_2(ST) complex larger than 5.5 mmol/L, and that of H_2O_2 larger than 8.2 mmol/L,the degradation of DBP at initial concentration less than 20.0 mg/L can be reached to almost 99% within 10 minutes. The catalytic reaction system has been monitored by electronic spectrum before or after adding H_2O_2 at different time intervals. The results show the catalytic activity site may be a μ-N-bridged binuclear Fe(Ⅲ) center and a di-Fe(Ⅲ)-H_2O_2 transition-state might be formed. The Fe_2(ST) can be reused after regeneration for at least 10 times with degradation percentage of DBP over 95%. The Fe_2(ST) is a potentially effective and green catalyst for the degradation of DBP.
Schiff base ligand(ST = N, N'-tetraethylene pentaminebis(salicylideimine) was prepared by condensation reaction of salicylaldehyde(SA) and tetraethylenepentamine(TEPA), and further coordinated with iron(Ⅲ) via coordination reaction to form a binuclear iron(Ⅲ) complex, [Fe_2(ST)(H_2 O)_4]Cl_4(abbreviated as Fe_2(ST)). It was characterized by elemental analysis(EA), Fourier transform infrared spectrometer(FTIR), and ultraviolet-visible spectroscopy(UV-vis), etc. It was used as catalyst for the degradation of emerging contaminants, e. g., dibutyl phthalate(DBP) under visible light with hydrogen peroxide solution as oxidant. The results show that at pH 3.5～8.0,with the initial concentration of Fe_2(ST) complex larger than 5.5 mmol/L, and that of H_2O_2 larger than 8.2 mmol/L,the degradation of DBP at initial concentration less than 20.0 mg/L can be reached to almost 99% within 10 minutes. The catalytic reaction system has been monitored by electronic spectrum before or after adding H_2O_2 at different time intervals. The results show the catalytic activity site may be a μ-N-bridged binuclear Fe(Ⅲ) center and a di-Fe(Ⅲ)-H_2O_2 transition-state might be formed. The Fe_2(ST) can be reused after regeneration for at least 10 times with degradation percentage of DBP over 95%. The Fe_2(ST) is a potentially effective and green catalyst for the degradation of DBP.
引文
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[11]蒋琦,姜哲昊,陈荣,等. Fe(Ⅲ)-Salen功能化纳米Fe3O4复合材料的合成及其对三氯苯的催化降解性能[J].环境化学,2017,36(8):1744-1751.
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[19]王磊,程慧敏,苏凡,等.三螺旋N-N桥连的双核Co(Ⅲ)配合物的合成、结构和性质[J].无机化学学报,2014,30(1):163-168.
[20]王滨松,张杰,黄君礼.UV/Fe(C2O4)33-/H2O2系统羟自由基生成规律[J].哈尔滨工业大学学报,2007,39(2):255-257.
[21] LEE C H, YOON J. Determination of quantum yields forthe photolysis of Fe(Ⅲ)-hydroxo complexes in aqueoussolution using a novel kinetic method[J]. Chemosphere,2004,57(10):1449-1458.
[22]焦利敏,黄鑫,廖学品,等.胶原纤维负载铁Fe(Ⅲ)催化剂对邻苯二甲酸二甲酯的光助催化降解[J].化工学报,2011,69(12):3419-3427.
[23]王军良,徐超,庄晓伟,等.水中邻苯二甲酸酯污染现状及高级氧化降解技术研究[J].工业水处理,2011,31(4):5-10.
[2] GEISSEN V, MOL H, KLUMPP E, et al. Emerging pollut?ants in the environment:A challenge for water resourcemanagement[J].International Soil and Water ConservationResearch,2015,3:57-65.
[3] RICHARDSON S D, KIMURA S Y. Water analysis:Emerg?ing contaminants and current issues[J].Analytic Chemistry,2016, 88(1):546-582.
[4] VRIJHEID M, CASAS M, GASCON M, et al. Environmen?talpollutantsandchildhealth-Areviewofrecentconcerns[J].International Journal of Hygiene and EnvironmentalHealth,2016,219(4/5):331-342.
[5] SHEN H Y. Simultaneous screening and determinationeight phthalates in plastic products for food use by sonica?tion-assisted extraction/GC-MS methods[J].Talanta,2005,66(3):734-739.
[6]于云江,叶昊,杨彦,等.太湖流域(苏南地区)经口介质中邻苯二甲酸酯的生物有效性及人体暴露评估[J].环境化学,2014,33(2):194-205.
[7] DONG H R, ZENG G M, TANG L, et al. An overview onlimitations of TiO2-based particles for photocatalytic degra?dation of organic pollutants and the corresponding counter?measures[J].Water research,2015,79:128-146.
[8] LEGRINI O, OLIVERS E, BRAUN A M. Photochemicalprocesses for water treatment[J].Chemical Review,1993,93(2):671-698.
[9]杨军,谢晟瑜,陈扬,等.μ-H2O-桥联均相铁(Ⅲ)催化剂的合成及其对邻苯二甲酸二丁酯的降解性能[J].环境化学,2016,35(9):1745-1752.
[10] HU M Q,WANG Y, XIONG Z G, et al. Iodine-sensitizeddegradation of 2,4,6-trichlorophenol under visible light[J].Environmental Science&Technology,2012,46(16):9005-9011.
[11]蒋琦,姜哲昊,陈荣,等. Fe(Ⅲ)-Salen功能化纳米Fe3O4复合材料的合成及其对三氯苯的催化降解性能[J].环境化学,2017,36(8):1744-1751.
[12] HUA Y J, WANG C T, LIU J Y. Visible photocatalyticdegradation of Rhodamine B using Fe(Ⅲ)-substitutedphosphotungstic heteropolyanion[J]. Journal of MolecularCatalysis A:Chemical,2012,365:8-14.
[13] WANG S B. A Comparative study of Fenton and Fenton-like reaction kinetics in decolourisation of wastewater[J].Dyes and Pigments,2008,76(3):714-720.
[14] GOLDSTEIN S, MEYERSTEIN D. Comments on themechanism of the“Fenton-Like”reaction[J].Accounts ofChemical Research,1999,32(7):547-549.
[15] NEVENS E, BAEYENS J. A review of classic Fenton’speroxidation as an advanced oxidation technique[J].Jour?nal of Hazardous Materials,2003,98(1/2/3):33-50.
[16] HU M Q, XU Y M. Visible light induced degradation ofchlorophenols in the presence of H2O2and iron substitut?ed polyoxotungstate[J].Chemical Engineering Journal,2014,246:299-305.
[17] GEARY W J. The use of conductivity measurements inorganic solvents for the characterisation of coordinationcompounds[J].Coordination Chemistry Reviews,1971,7(1):81-122.
[18]毛春晖,赵毓,李永强,等.N-桥连芳基吡咯类衍生物的合成、晶体结构及杀虫杀螨活性研究[J].有机化学,2009,29(6):929-935.
[19]王磊,程慧敏,苏凡,等.三螺旋N-N桥连的双核Co(Ⅲ)配合物的合成、结构和性质[J].无机化学学报,2014,30(1):163-168.
[20]王滨松,张杰,黄君礼.UV/Fe(C2O4)33-/H2O2系统羟自由基生成规律[J].哈尔滨工业大学学报,2007,39(2):255-257.
[21] LEE C H, YOON J. Determination of quantum yields forthe photolysis of Fe(Ⅲ)-hydroxo complexes in aqueoussolution using a novel kinetic method[J]. Chemosphere,2004,57(10):1449-1458.
[22]焦利敏,黄鑫,廖学品,等.胶原纤维负载铁Fe(Ⅲ)催化剂对邻苯二甲酸二甲酯的光助催化降解[J].化工学报,2011,69(12):3419-3427.
[23]王军良,徐超,庄晓伟,等.水中邻苯二甲酸酯污染现状及高级氧化降解技术研究[J].工业水处理,2011,31(4):5-10.
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