不同调节剂制备MOF-Fe的性质及对Se(Ⅳ)的吸附性能
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摘要
以HF、HCl、H_2O和Na Ac溶液为调节剂合成了4种MOF-Fe样品,用X射线衍射(XRD)、透射电镜(TEM)、N_2等温吸附-脱附、综合热分析(TG/DTG和DTA)和质子电位滴定研究了4种样品的结构与表面性质,以及对亚硒酸根(Se(Ⅳ))等温吸附特性。MOF-Fe(HF)、MOF-Fe(HCl)、MOF-Fe(H_2O)和MOF-Fe(Na Ac)四种样品均具有八面体MIL-100(Fe)的晶体结构,但它们的结晶度和晶面取向略有差异。4种样品的比表面积分别为1 683、1 517、1 641和1 734 m~2·g~(-1),其总孔体积依次降低,微孔孔径分别为1.27、1.22、1.22和1.17 nm。MOF-Fe(HF)样品的脱羧基失重峰温度最高(415℃),苯环碳化失重峰温度最低(462℃);MOF-Fe(HCl)、MOF-Fe(H_2O)和MOF-Fe(Na Ac)样品出现了因氧化铁被碳还原所致的失重平台(566~716℃)。样品悬浮液从p H=6.0降到3.0时,消耗H~+的量表现为MOF-Fe(H_2O)>MOF-Fe(HCl)>MOF-Fe(HF)=MOF-Fe(Na Ac),它们的电荷零点(p H_(ZPC))依次为3.1、3.5、3.6和3.5。MOF-Fe(Na Ac)、MOF-Fe(HCl)、MOF-Fe(H_2O)和MOF-Fe(HF)对Se(Ⅳ)的吸附亲和力依次减小,它们对Se(Ⅳ)的吸附容量(Q_m)分别为77.69、107.07、117.40和87.15 mg·g~(-1)。显著性分析显示,MOF-Fe的羟基密度与样品吸附Se(Ⅳ)的Q_m显著正相关。研究结果表明,MOF-Fe样品的结构热稳定性和羟基/配位水分子等活性位点密度受合成样品时加入的调节剂影响,用HF作为调节剂合成MOF-Fe样品有利于提高样品中羧基与苯环之间的C-C键合强度和热分解产物的稳定性,降低苯环碳化温度;HCl和H_2O作为调节剂有利于提高样品的活性位点密度,可提高MOF-Fe样品对Se(Ⅳ)吸附容量。
MOF-Fe samples were prepared with HF,HCl,H_2O and Na Ac as conditioning agents by hydrothermal method.The characteristics of the samples were studied by X-ray diffraction(XRD),Transmission electron microscope(TEM),N_2adsorption/desorption,thermal analysis(TG/DTG and DTA)and proton potentiometric titration.Isothermal adsorption experiments of selenite(Se(Ⅳ))on the samples were carried out.Crystal structure of all samples are same as MIL-100(Fe),and the morphology are octahedral,while the crystallinities and crystal orientations are different.The BET surface area are 1 683,1 517,1 641 and 1 734 m~2·g~(-1),respectively,and total pore volumes of the samples are decreased orderly.The micropore diameter are 1.27,1.22,1.22 and 1.17 nm for MOF-Fe(HF),MOF-Fe(HCl),MOF-Fe(H_2O)and MOF-Fe(Na Ac).The temperature of decarboxylation of MOF-Fe(HF)is highest(415℃),while its carbonization temperature for benzene ring is lowest(462℃)compared with the others.A weight loss caused by redox between iron oxide and carbon appears in MOF-Fe(HCl),MOF-Fe(H_2O)and MOF-Fe(Na Ac).The sequence of H~+consumed during the process of proton potentiometric titrations for samples is MOF-Fe(H_2O)>MOF-Fe(HCl)>MOF-Fe(HF)=MOF-Fe(Na Ac),and p H value of zero point charge(p H_(ZPC))are 3.1,3.5,3.6 and 3.5 accordingly.The sequence about the affinity of adsorption for Se(Ⅳ)on samples is MOF-Fe(Na Ac)>MOF-Fe(HCl)>MOF-Fe(H_2O)>MOF-Fe(HF),and the maximum adsorption capacities(Q_m)are77.69,107.07,117.40 and 87.15 mg·g~(-1)correspondingly.The Q_mof Se(Ⅳ)on samples have positive correlation with density of hydroxyl for samples observably.This study reveals that the thermostability and density of active site of MOF-Fe are influenced by the conditioning agent when MOF-Fe was prepared.The HF could increase the strength of C-C between carboxyl and benzene ring,decrease carbonization temperature of benzene ring of MOF-Fe,and improve the thermostability of iron oxides after heating.While HCl and H_2O could improve the density of active site in samples,then the Q_mof Se(Ⅳ)adsorbed on MOF-Fe could be increased.
MOF-Fe samples were prepared with HF,HCl,H_2O and Na Ac as conditioning agents by hydrothermal method.The characteristics of the samples were studied by X-ray diffraction(XRD),Transmission electron microscope(TEM),N_2adsorption/desorption,thermal analysis(TG/DTG and DTA)and proton potentiometric titration.Isothermal adsorption experiments of selenite(Se(Ⅳ))on the samples were carried out.Crystal structure of all samples are same as MIL-100(Fe),and the morphology are octahedral,while the crystallinities and crystal orientations are different.The BET surface area are 1 683,1 517,1 641 and 1 734 m~2·g~(-1),respectively,and total pore volumes of the samples are decreased orderly.The micropore diameter are 1.27,1.22,1.22 and 1.17 nm for MOF-Fe(HF),MOF-Fe(HCl),MOF-Fe(H_2O)and MOF-Fe(Na Ac).The temperature of decarboxylation of MOF-Fe(HF)is highest(415℃),while its carbonization temperature for benzene ring is lowest(462℃)compared with the others.A weight loss caused by redox between iron oxide and carbon appears in MOF-Fe(HCl),MOF-Fe(H_2O)and MOF-Fe(Na Ac).The sequence of H~+consumed during the process of proton potentiometric titrations for samples is MOF-Fe(H_2O)>MOF-Fe(HCl)>MOF-Fe(HF)=MOF-Fe(Na Ac),and p H value of zero point charge(p H_(ZPC))are 3.1,3.5,3.6 and 3.5 accordingly.The sequence about the affinity of adsorption for Se(Ⅳ)on samples is MOF-Fe(Na Ac)>MOF-Fe(HCl)>MOF-Fe(H_2O)>MOF-Fe(HF),and the maximum adsorption capacities(Q_m)are77.69,107.07,117.40 and 87.15 mg·g~(-1)correspondingly.The Q_mof Se(Ⅳ)on samples have positive correlation with density of hydroxyl for samples observably.This study reveals that the thermostability and density of active site of MOF-Fe are influenced by the conditioning agent when MOF-Fe was prepared.The HF could increase the strength of C-C between carboxyl and benzene ring,decrease carbonization temperature of benzene ring of MOF-Fe,and improve the thermostability of iron oxides after heating.While HCl and H_2O could improve the density of active site in samples,then the Q_mof Se(Ⅳ)adsorbed on MOF-Fe could be increased.
引文
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[3]Fernández-Martínez A,Charlet L.Rev.Environ.Sci.Biotechnol.,2009,8(1):81-110
[4]GB 3838-2002,Environmental Quality Standards for Surface Water(地表水环境质量标准).2002.
[5]ZHU Jian-Ming(朱建明),QIN Hai-Bo(秦海波),LI Lu(李璐),et al.Acta Scientiae Circumstantiae(环境科学学报),2008,28(4):772-777
[6]Santos S,Ungureanu G,Boaventura R,et al.Sci.Total Environ.,2015,521-522:246-260
[7]WANG Lin(王琳),SHI Yong-Sheng(施永生).Treatment of Waster Water Contain Selenium(含硒水处理).Beijing:Chemistry Industry Press,2005.
[8]Hu B W,Ye F,Jin C G,et al.Chemosphere,2017,184:408-416
[9]Xia X F,Ling L,Zhang W X.Chemosphere,2017,168:1597-1603
[10]Chan Y T,Kuan W H,Chen T Y,et al.Water Res.,2009,43(17):4412-4420
[11]Ma Z Y,Shan C,Liang J L,et al.Chemosphere,2018,193:134-141
[12]Rosi N L,Eckert J,Eddaoudi M,et al.Science,2003,300(5622):1127-1129
[13]Sun J K,Xu Q.Energy Environ.Sci.,2014,7(7):2071-2100
[14]Alezi D,Belmabkhout Y,Suyetin M,et al.J.Am.Chem.Soc.,2015,137(41):13308-13318
[15]Cao X H,Zheng B,Shi W H,et al.Adv.Mater.,2015,27(32):4695-4701
[16]Chen Q S,Sun J L,Li P,et al.J.Am.Chem.Soc.,2016,138(43):14242-14245
[17]HUANG Gang(黄刚),CHEN Yu-Zhen(陈玉贞),JIANG HaiLong(江海龙).Acta Chim.Sinica(化学学报),2016,74(02):113-129
[18]Guo H L,Zhu Y Z,Wang S,et al.Chem.Mater.,2012,24(3):444-450
[19]Cheng X Q,Zhang A F,Hou K K,et al.Dalton Trans.,2013,42:13698-13705
[20]Liu Y L,Gao P F,Huang C Z,et al.Sci.China Ser.B:Chem.,2015,58(10):1553-1560
[21]Kumar P,Pournara A,Kim K H,et al.Prog.Mater.Sci.,2017,86:25-74
[22]Patra S,Sene S,Mousty C,et al.ACS Appl.Mater.Interfaces,2016,8(31):20012-20022
[23]Bghadra B N,Jhung S H.ACS Appl.Mater.Interfaces,2016,8(10):6770-6777
[24]Zhu N N,Liu X H,Li T,et al.Inorg.Chem.,2017,56(5):3414-3420
[25]Liu X C,Zhou Y Y,Zhang J C,et al.ACS Appl.Mater.Interfaces,2017,9(24):20255-20275
[26]Song G Q,Wang Z Q,Wang L,et al.Chin.J.Catal.,2014,35(2):185-195
[27]Lee Y R,Kim J,Ahn W S.Korean J.Chem.Eng.,2013,30(9):1667-1680
[28]ZHANG Su(张素),WANG Hai-Shui(王海水).Chinese J.Inorg.Chem.(无机化学学报),2013,29(1):31-35
[29]ZHAO Xin-Hua(赵新华),CHEN Lin(陈玲),CAO Yong-Ge(曹永革),et al.Foundation of Solid-State Inorganic Chemistry and the Design Synthesis of Novel Materials(固体无机化学基础及新材料的设计合成).Beijing:Higher Education
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[31]Zhang L.Thesis for the Doctorate of Michigan Technological University.2011.
[32]JIANG Wu-Feng(蒋武锋),ZHAO Shuo(赵朔),HAO Su-Ju(郝素菊),et al.Chinese Journal of Process Engineering(过程工程学报),2017,17(2):362-366
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[34]Kuang L Y,Liu Y Y,Fu D D,et al.J.Colloid Interface Sci.,2017,490:259-269
[35]Hajjaji W,Ganiyu S O,Tobaldi D M,et al.Appl.Clay Sci.,2013,83-84:91-98
[36]Chen L,Ji T,Mu L W,et al.J.Environ.Manage.,2017,196:168-177