陸思嘉,馬曉雁*,李青松,宋亞麗,余 齊,朱麗丹

金屬有機(jī)骨架HKUST-1對(duì)水中微量氨基酸的吸附性能

陸思嘉1,馬曉雁1*,李青松2,宋亞麗3,余 齊1,朱麗丹1

(1.浙江工業(yè)大學(xué)建筑工程學(xué)院,浙江 杭州 310014；2.廈門(mén)理工學(xué)院水資源環(huán)境研究所,福建省農(nóng)村污水處理與用水安全工程研究中心,福建 廈門(mén) 361005；3.浙江科技學(xué)院建筑工程學(xué)院,浙江 杭州 310023)

采用溶劑熱法制備金屬有機(jī)骨架HKUST-1,選取水源水中檢出率較高的酪氨酸(Tyr)、苯丙氨酸(Phe)和色氨酸(Trp)為目標(biāo)物,開(kāi)展了HKUST-1吸附微量氨基酸性能的研究.利用XRD和FTIR技術(shù)對(duì)吸附劑HKUST-1進(jìn)行了表征和分析,通過(guò)吸附動(dòng)力學(xué)、吸附等溫線(xiàn)和吸附熱力學(xué)的研究探討HKUST-1吸附氨基酸的機(jī)理.結(jié)果表明,HKUST-1具有高結(jié)晶度,對(duì)酪氨酸、苯丙氨酸和色氨酸有較好的去除效果,飽和吸附容量分別可達(dá)248.65,143.67,140.09mg/g;吸附過(guò)程符合Langmuir吸附等溫線(xiàn)模型和Lagergren準(zhǔn)二級(jí)動(dòng)力學(xué)模型;吸附熱力學(xué)結(jié)果表明,HKUST-1去除氨基酸的過(guò)程為吸熱反應(yīng);高吸附容量主要?dú)w因于靜電相互作用、氫鍵和π-π相互作用.

HKUST-1；吸附；消毒副產(chǎn)物前體物；氨基酸；飲用水處理

近年來(lái),隨著飲用水中含氮消毒副產(chǎn)物(N- DBPs)的不斷檢出,其前體物的識(shí)別及N-DBPs的產(chǎn)生機(jī)理成為研究的熱點(diǎn)[1-2].水源水中溶解性有機(jī)氮(DON)是凈水工藝過(guò)程中典型N-DBPs的主要前體物[3].氨基酸是含氮有機(jī)物的重要組成部分,廣泛存在于地表水源中[4],氨基酸在氯消毒過(guò)程中可產(chǎn)生多種N-DBPs[5].盡管N-DBPs檢出濃度通常較含碳消毒副產(chǎn)物(C-DBPs)低1個(gè)數(shù)量級(jí),但其具有更高的遺傳毒性和基因毒性[2],因此其控制技術(shù)備受關(guān)注.前體物減量化是控制N-DBPs的重要途徑之一.目前氨基酸等溶解性有機(jī)氮控制研究相對(duì)較少,常規(guī)的飲用水處理工藝對(duì)氨基酸的去除效果欠佳[6],生物過(guò)濾過(guò)程中只有50%的游離氨基酸能被去除[7];經(jīng)過(guò)化學(xué)預(yù)處理、沉淀和過(guò)濾后,只有25%的游離氨基酸在飲用水中被去除[8].常規(guī)及部分深度給水處理工藝對(duì)氨基酸類(lèi)前體物的控制能力不足.

吸附是提高常規(guī)工藝去除水中有機(jī)污染物能力的有效方法[9].金屬有機(jī)骨架材料(MOF)是一種新型多功能吸附劑,具有孔隙率高,孔徑均勻可調(diào),比表面積大等諸多優(yōu)點(diǎn)[10].HKUST-1是一種銅基MOF,由1,3,5-苯三甲酸和Cu2+團(tuán)簇絡(luò)合形成的三維結(jié)構(gòu)具有典型的孔籠-孔道結(jié)構(gòu)[11],是熱力學(xué)穩(wěn)定的MOF之一.與傳統(tǒng)的吸附劑相比,由于具有易合成,高表面積,大孔體積和不飽和金屬位點(diǎn)等優(yōu)點(diǎn),在吸附方面展現(xiàn)出了很好的應(yīng)用前景[12].Lin等[13]和Azhar等[14]分別采用HKUST-1 吸附去除對(duì)硝基苯酚和磺胺類(lèi)抗生素,吸附容量分別可達(dá)400, 384mg/ g,高于活性炭、多壁碳納米管和沸石的吸附容量.芳香族氨基酸與硝基苯酚和磺胺類(lèi)抗生素具有類(lèi)似的結(jié)構(gòu)和性質(zhì),推測(cè)HKUST-1 對(duì)芳香族氨基酸可能具有較好的吸附效果,因此本文嘗試以酪氨酸(Tyr)、苯丙氨酸(Phe)和色氨酸(Trp)作為典型DBPs前體物,考察HKUST-1對(duì)Tyr、Phe和Trp的吸附效果,擬合了吸附等溫線(xiàn)和吸附動(dòng)力學(xué)模型,探討了吸附機(jī)理,以期為水中微量氨基酸的吸附去除提供基礎(chǔ)理論.

1 材料與方法

1.1 試劑與儀器

酪氨酸(Tyr)、苯丙氨酸(Phe)和色氨酸(Trp)標(biāo)準(zhǔn)品(純度99%,北京百靈威科技有限公司);三水硝酸銅(Cu(NO3)2·3H2O,純度99%,阿拉丁試劑有限公司);1,3,5-苯三甲酸(H3BTC,純度98%,阿拉丁試劑有限公司);異硫氰酸苯酯(PITC,純度98%,阿拉丁試劑有限公司);無(wú)水乙酸鈉(純度399%,上海凌峰化學(xué)試劑有限公司);三乙胺(純度399.0%,上海凌峰化學(xué)試劑有限公司);甲醇和乙腈(HPLC級(jí),德國(guó)CNW).

高效液相色譜儀(LC-20AT,島津,日本),色譜柱inertSustain C18柱(5μm×4.6mm×250mm);干燥箱(DHG-9001A,一恒,上海);往復(fù)式水浴恒溫振蕩器(SHA-C,賓都,湖南);恒溫往復(fù)式搖床(KS130B,IKA,德國(guó)).

1.2 液相色譜條件

柱溫35℃,紫外檢測(cè)器波長(zhǎng)254nm,進(jìn)樣量10μL,流速1mL/min,流動(dòng)相A為甲醇-乙腈-水(體積比20:60:20),流動(dòng)相B為0.1mol/L乙酸鈉-乙腈(體積比93:7),用冰乙酸調(diào)節(jié)pH值至6.5.梯度洗脫程序見(jiàn)表1.以保留時(shí)間定性,峰面積定量.進(jìn)樣前所有的分析純?cè)噭┯?.45μm微孔濾膜過(guò)濾.

表1 酪氨酸、苯丙氨酸和色氨酸的含量測(cè)定中流動(dòng)相梯度洗脫程序

1.3 HKSUT-1的合成

首先將0.88g的三水硝酸銅Cu(NO3)2·3H2O溶解于12mL純水中,形成溶液A.0.42g1,3,5-苯三甲酸(H3BTC)溶解于12mL乙醇中,形成溶液B.將溶液A和B混合,環(huán)境溫度下攪拌1h后,將混合物倒入襯有聚四氟乙烯的高壓釜中,并置于120℃的烘箱中24h,混合物冷卻后,通過(guò)真空抽濾得到藍(lán)色晶體,采用水和乙醇混合液(體積比1:1)洗滌后,晶體在120℃下干燥16h后保存在60℃的烘箱中.

1.4 HKSUT-1的表征方法

采用傅里葉紅外光譜FTIR衰減全反射(ATR)技術(shù)研究金屬簇與有機(jī)配體的連接,500~4000cm-1掃描光譜,分辨率為4cm-1.采用X射線(xiàn)衍射儀(X’Pert Pro)對(duì)HKSUT-1材料進(jìn)行衍射,獲得材料種類(lèi)、結(jié)晶度及晶體粒徑等信息.以金屬銅為靶材,Ni濾玻片,入射線(xiàn)波長(zhǎng)0.15418nm,管壓40kV,管流40mA;廣角:5~60°,狹縫DS=0.5°;RS=8mm;掃描步長(zhǎng)0.02°,掃描速率0.1s/步.

1.5 氨基酸衍生化

衍生試劑A:1mol/L三乙胺-乙腈;衍生試劑B:0.1mol/L PITC-乙腈.取200μL樣品,加入衍生試劑A、B各100μL,混勻后靜置30min.加入400μL正己烷,振搖混勻后,離心5min棄上層.再加入400μL正己烷萃取,離心5min,抽取下層,用0.45μm濾膜過(guò)濾,用于色譜分析.

1.6 吸附試驗(yàn)

精確稱(chēng)取一定量的Tyr、Phe和Trp將其溶解于0.1mol/L HCl中,配制成1g/L的標(biāo)準(zhǔn)儲(chǔ)備液.定量取氨基酸標(biāo)準(zhǔn)儲(chǔ)備液,用0.1mol/L鹽酸逐級(jí)稀釋,配制成50mL不同濃度(10~150mg/L)的工作溶液.

吸附動(dòng)力學(xué)試驗(yàn):初始質(zhì)量濃度為100mg/L的Tyr、Phe和Trp標(biāo)準(zhǔn)溶液50mL于250mL具塞錐形瓶中,同時(shí)投加25mg HKUST-1,在溫度298K、轉(zhuǎn)速160r/min的條件下,置于水浴恒溫振蕩器進(jìn)行振蕩,在設(shè)置的一系列采樣點(diǎn)(2,5,20,30,40,90, 120min)測(cè)定氨基酸的濃度.做3組平行試驗(yàn),結(jié)果取平均值.

吸附平衡試驗(yàn):不同質(zhì)量濃度(10~150mg/L)的Tyr、Phe和Trp標(biāo)準(zhǔn)溶液各50mL于250mL具塞錐形瓶中,同時(shí)投加25mg HKUST-1,在溫度298K、轉(zhuǎn)速160r/min的條件下吸附120min.做3組平行試驗(yàn),結(jié)果取平均值.

HKUST-1對(duì)3種氨基酸的平衡吸附容量e按式(1)計(jì)算:

e=(0-e)′/(1)

式中:e為吸附容量,mg/g;0和e分別為吸附前和吸附平衡時(shí)溶液的濃度,mg/L;為溶液體積,mL;為吸附劑的質(zhì)量,g.

2 結(jié)果與討論

2.1 HKUST-1的結(jié)晶特征及價(jià)鍵類(lèi)型

圖1 HKUST-1吸附氨基酸后的FTIR光譜

FTIR光譜(圖1)顯示了HKUST-1吸附劑中苯三甲酸和Cu2+的配位.730cm-1的吸收峰是由晶體中銅離子團(tuán)簇的Cu—O伸縮振動(dòng)引起;1300~1700cm-1的吸收峰是羧酸官能團(tuán)中的C—O振動(dòng)峰,其中1445cm-1是O=C—O的對(duì)稱(chēng)伸縮振動(dòng)引起,而1621cm-1處是由于O=C—O不對(duì)稱(chēng)的伸縮振動(dòng);1373和1565cm-1處的吸收峰是C=C的振動(dòng)峰,表明BTC插層進(jìn)入HKUST-1;3417cm-1寬吸收峰是H-O伸縮振動(dòng)峰.

如圖2所示,在2=5~50°范圍內(nèi)觀(guān)察到樣品(圖2a)均有與標(biāo)準(zhǔn)的HKUST-1(圖2b)相對(duì)應(yīng)的特征衍射峰[15].尖銳而明顯的峰顯示出HKUST-1的高結(jié)晶度,說(shuō)明制備的樣品具有微孔結(jié)晶框架.

2.2 HKUST-1對(duì)氨基酸的吸附機(jī)理

2.2.1 吸附等溫線(xiàn) 由圖3,圖4可知,Langmuir吸附等溫線(xiàn)模型能更加準(zhǔn)確的描述HKUST-1吸附氨基酸的過(guò)程.表明氨基酸在HKUST-1上的吸附為單分子層吸附.吸附劑表面的每個(gè)活性位點(diǎn)上可以吸附一定數(shù)量的氨基酸分子;當(dāng)吸附達(dá)到飽和時(shí),活性位點(diǎn)均被占滿(mǎn),其吸附量達(dá)到最大值,繼續(xù)接觸吸附量則不再增加[16].

根據(jù)分離因子L可以判斷吸附劑是否能有效吸附吸附質(zhì),當(dāng)0

如表2和圖5所示,在所討論的溫度范圍內(nèi),隨著初始濃度的增大,HKUST-1對(duì)氨基酸的吸附量逐漸增加,Tyr、Phe和Trp平衡濃度達(dá)到20mg/L時(shí),吸附基本達(dá)到飽和.氨基酸最大吸附容量和吸附速率隨溫度升高而增加.在298K,HKUST-1對(duì)酪氨酸、苯丙氨酸和色氨酸的吸附容量分別為248.65,143.67, 140.09mg/g,在333K時(shí)可高達(dá)409.93,254.56, 257.46mg/g.HKUST-1對(duì)于Tyr、Phe和Trp的吸附速率分別從0.387,0.256,0.191L/mg增長(zhǎng)到0.628, 0.489,0.533L/mg.Azhar等[14]研究發(fā)現(xiàn),HKUST-1吸附與氨基酸具有類(lèi)似結(jié)構(gòu)的磺胺氯噠嗪時(shí),最大吸附容量和吸附常數(shù)隨溫度升高而增加.在298K時(shí),吸附容量為384mg/g,在318K時(shí)可高達(dá)526mg/g.

表2 HKUST-1吸附氨基酸的等溫吸附模型參數(shù)

2.2.2 吸附動(dòng)力學(xué) 由圖6可知,在反應(yīng)開(kāi)始前20min,HKUST-1的吸附速率快,呈線(xiàn)性吸附,吸附量可達(dá)161.48~207.94mg/g.隨著反應(yīng)進(jìn)行,吸附速率逐漸變慢,吸附量緩慢上升,當(dāng)反應(yīng)進(jìn)行到90min,基本到達(dá)吸附平衡,HKUST-1對(duì)于Tyr、Phe和Trp的平衡吸附量分別為219.40,179.52,207.80mg/g.

圖6 氨基酸吸附量隨接觸時(shí)間的變化

由圖6、圖7及表3可知,HKUST-1吸附氨基酸的過(guò)程更符合準(zhǔn)二級(jí)動(dòng)力學(xué)模型,Tyr、Phe和Trp的理論吸附容量分別為222.22,181.82,208.33mg/g,速率常數(shù)分別為0.005,0.004,0.002g/(mg·min).準(zhǔn)二級(jí)動(dòng)力學(xué)主要用于描述化學(xué)吸附通過(guò)共享或交換吸附劑與吸附質(zhì)之間的電子,形成共價(jià)鍵和離子交換[17],表明HKUST-1吸附氨基酸以化學(xué)吸附為主.

2.2.3 吸附熱力學(xué) 根據(jù)HKUST-1不同溫度下(298,313,333K)對(duì)水中氨基酸的吸附平衡數(shù)據(jù),計(jì)算出不同溫度條件下的d,再計(jì)算出相對(duì)應(yīng)溫度條件下的標(biāo)準(zhǔn)吉普斯自由能Δ0,最后對(duì)lnd和1/關(guān)系進(jìn)行線(xiàn)性擬合(圖8),通過(guò)直線(xiàn)的斜率和截距可分別算出吸附反應(yīng)所對(duì)應(yīng)Δ0和Δ0,結(jié)果見(jiàn)表4.

表3 HKUST-1吸附氨基酸的準(zhǔn)一級(jí)、二級(jí)反應(yīng)動(dòng)力學(xué)參數(shù)

圖8 范特霍夫方程估算HKUST-1吸附Tyr、Phe和Trp的ΔH°和ΔS°圖

由表4可知,在不同溫度條件下(298,313, 333K),D0均為負(fù)值,同時(shí)隨著溫度升高,D0越來(lái)越小,表明吸附過(guò)程是自發(fā)進(jìn)行,自發(fā)程度隨著溫度的升高越來(lái)越大[18].D0均為正值,說(shuō)明HKUST-1對(duì)氨基酸的吸附是吸熱反應(yīng),即升溫有利于HKUST-1吸附氨基酸.在固液吸附體系中,同時(shí)存在吸附和解吸的過(guò)程.實(shí)驗(yàn)結(jié)果的D0為正值,即HKUST-1對(duì)氨基酸的吸附為熵增反應(yīng),體系的混亂程度大.說(shuō)明由于吸附水分子的置換所引起的熵的增加大于氨基酸吸附所引起的熵值降低[20].同時(shí),通過(guò)去除水分子加強(qiáng)了HKUST-1中不飽和金屬位點(diǎn)的存在[21],有利于氨基酸的吸附.

表4 HKUST-1吸附Tyr、Phe和Trp的熱力學(xué)參數(shù)

2.2.4 吸附機(jī)理 由于HKUST-1的金屬部位部分帶正電[22],這些金屬部位可以通過(guò)靜電相互作用與陰離子部位相互作用.Tyr、Phe和Trp的結(jié)構(gòu)中包含苯環(huán)、羧基(—COOH)和氨基(—NH2)基團(tuán).—NH2中N—H共價(jià)鍵是極性的,使N原子帶負(fù)電.雖然HKUST-1中的配位不飽和位點(diǎn)可以被溶液中的水占據(jù),但HKUST-1和氨基酸之間的靜電相互作用可以取代水分子[23].因此,該陰離子位點(diǎn)可以被吸引到HKUST-1的帶正電荷的金屬位點(diǎn),從而將氨基酸吸附到HKUST-1.

基于FTIR結(jié)果(圖2),HKUST-1吸附氨基酸后,吸收峰發(fā)生了相應(yīng)的轉(zhuǎn)變.C=C的振動(dòng)峰從1565cm-1的吸收峰變?yōu)?456cm-1的吸收峰,表明了苯環(huán)間的π-π相互作用,變化幅度較小表明π-π相互作用較弱.在3510cm-1處的NH2和3087cm-1處的H-O的吸收峰消失,以及1445cm-1處COO吸收峰的移動(dòng)表明氨基酸中的NH2和HKUST-1簇的氧形成的氫鍵吸引而導(dǎo)致伸縮.Tyr相對(duì)于其他2種氨基酸的高吸附容量歸因于自身還存在的酚羥基,酚羥基中的氫可與HKUST-1中的含孤對(duì)電子的氧原子形成氫鍵[24],從而更利于吸附.因此HKUST-1對(duì)Tyr、Phe和Trp較好的吸附效果歸因于靜電相互作用,氫鍵和π-π相互作用.

3 結(jié)論

3.1 溶劑熱法制備的HKUST-1對(duì)酪氨酸、苯丙氨酸和色氨酸有較好的吸附效果.

3.2 Langmuir吸附等溫線(xiàn)模型能更加準(zhǔn)確的描述其吸附特性.298K時(shí),HKUST-1對(duì)3種氨基酸吸附容量分別為248.65,143.67,140.09mg/g,吸附速率常數(shù)分別為0.005,0.004,0.002g/(mg·min); Lagergren準(zhǔn)二級(jí)動(dòng)力學(xué)模型能更好的描述HKUST-1對(duì)水中Tyr、Phe和Trp的吸附動(dòng)力學(xué);吸附熱力學(xué)的結(jié)果表明HKUST-1吸附水中3種氨基酸為吸熱過(guò)程,溫度的升高有利于吸附反應(yīng).

3.3 靜電相互作用、氫鍵和π-π相互作用是HKUST-1吸附水中Tyr、Phe和Trp的主要機(jī)制.

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Adsorption properties of micropollutants amino acids on metallic organic framework HKUST-1 in aqueoussystem.

LU Si-jia1, MA Xiao-yan1*, LI Qing-song2, SONG Ya-li3, YU Qi1, ZHU Li-dan1

(1.College of Civil Engineering and Architecture, Zhejiang University of Technology, Hangzhou 310014, China；2.Fujian Engineering and Research Center of Rural Sewage Treatment and Water Safety, Water Resources and Environmental Institute, Xiamen University of Technology, Xiamen 361005, China；3.School of Civil Enginneering and Architecture, Zhejiang University of Science and Technology, Hangzhou 310023, China)., 2019,39(7)：2847~2853

The metal organic framework HKUST-1 was prepared by solvothermal method. The tyrosine (Tyr), phenylalanine (phe) and tryptophan (Tyr) which were detected frequently in water source were selected as the targets, and their adsorption on HKUST-1 was investigated. The adsorbent characteristic of HKUST-1was analyzed by XRD and FTIR techniques. The adsorption mechanism of amino acids on HKUST-1 was investigated by adsorption kinetics, isotherms and thermodynamics. HKUST-1 had high crystallinity and good removal effects on tyrosine, phenylalanine and tryptophan, saturated adsorption capacity was up to 248.65,143.67 and 140.09mg/g; the adsorption process was in accordance with the Langmuir adsorption isotherm model and the Lagergren quasi-secondary kinetic model; adsorption thermodynamics results showed that HKUST-1 removed amino acids as an endothermic reaction; high adsorption capacity was mainly attributed to electrostatic interaction, hydrogen bonding and π-π interaction.

HKUST-1；adsorption；disinfection by-product precursors；amino acid；drinking water treatment

X52

A

1000-6923(2019)07-2847-07

陸思嘉(1994-),女,浙江杭州人,浙江工業(yè)大學(xué)碩士研究生,主要從事飲用水污染控制研究.

2018-12-06

浙江省自然科學(xué)基金資助項(xiàng)目(LY19E080019);福建省農(nóng)村污水處理與用水安全工程研究中心開(kāi)放課題(RST201803);國(guó)家自然科學(xué)基金資助項(xiàng)目(51678527)

* 責(zé)任作者, 教授, mayaner@zjut.deu.cn