Xử lý rodamine B trong nước trên xúc tác hydrotalcite chứa Ti

I HC QUC GIA H NI TRNG I HC KHOA HC T NHIấN KHOA HểA HC Hunh Th Thỳy Hoa X Lí RHODAMINE B TRONG NC TRấN XC TC HYDROTALCITE CHA Ti Lun Thc s Húa hc Ngnh Húa hc Mụi trng H Ni - 2016 I HC QUC GIA H NI TRNG I HC KHOA HC T NHIấN KHOA HểA HC Hunh Th Thỳy Hoa X Lí RHODAMINE B TRONG NC TRấN XC TC HYDROTALCITE CHA Ti Lun Thc s Húa hc Ngnh Húa hc Mụi trng Mó s: 60440120 Cỏn b hng dn: PGS TS Nguyn Tin Tho H Ni - 2016 LI CM N Vi lũng bit n sõu sc nht, tụi xin chõn thnh cm n PGS.TS Nguyn Tin Tho ó hng dn tụi tn tỡnh sut quỏ trỡnh hon thnh lun Tụi xin chõn thnh cm n cỏc thy, cụ v cỏc cỏn b phũng thớ nghim Khoa Húa hc - B mụn Húa hc Du m v Phũng thớ nghim Húa Mụi trng, Trng HKHTN- HQG H Ni ó dy d, ng viờn, giỳp tụi sut quỏ trỡnh hc ti trng v to iu kin thun li cho tụi hon thin lun Cui cựng, tụi xin by t lũng bit n ti gia ỡnh v bn bố, nhng ngi luụn ng viờn v to iu kin thun li tụi hon thin lun Trõn trng cm n! H Ni, ngy thỏng nm 2016 Tỏc gi Hunh Th Thỳy Hoa MC LC LI CM N M U 10 Chng I - TNG QUAN 12 1.1 Gii thiu v hydrotalcite 12 1.2 c im hydrotalcite 13 1.2.1 Cụng thc 13 1.2.2 c im cu trỳc 13 1.2.3 c im 14 1.3 Tớnh cht 16 1.3.1 Tớnh cht trao i anion 16 1.3.2 Tớnh cht hp ph 18 1.4 Phng phỏp iu ch hydrotalcite 19 1.4.1 Phng phỏp ng kt ta 19 1.4.2 nh hng ca pH 19 1.4.3 nh hng ca nhit 21 1.4.4 Gi húa kt ta 21 1.4.5 Ra kt ta 21 1.4.6 Lm khụ cht kt ta v gel 22 1.5 ng dng ca hydrotalcite 22 1.5.1 Xỳc tỏc 22 1.5.2 ng dng lm cht hp ph v trao i ion 23 1.6 Phn ng oxi húa rhodamine B 23 1.6.1 Kh nng x lý hp cht hu c nc bng xỳc tỏc hydrotalcite Zn-Ti 23 1.6.2 Rhodamine B 24 1.6.3 C ch ca phn ng oxi húa RhoB s dng xỳc tỏc quang Zn/TiLDHs 25 Chng II THC NGHIM 26 2.1.Tng hp Zn/Ti-LDHs 26 2.2 Nghiờn cu c trng xỳc tỏc bng cỏc phng phỏp vt lý 26 2.2.1 Phng phỏp nhiu x tia X (XRD) 26 2.2.2 Phng phỏp tỏn x nng lng tia X (EDS) 28 2.2.3 Phng phỏp ph hng ngoi (IR) 29 2.2.4 Phng phỏp hin vi in t quột (SEM) 29 2.2.5 Phng phỏp hin vi in t tru n qua E 30 2.2.6 Phng phỏp hp ph - gii hp ph (BET) 30 2.3 Phn ng oxi húa rhodamine B 36 2.4 Xõy dng ng chun, o hp th quang ca dung dch Rhodamine B theo phng phỏp trc quang (UV Vis) 36 2.4.1 Nguyờn tc 36 2.4.2 Xõy dng ng chun 37 Chng III KT QU V THO LUN 39 3.1 c trng ca mu xỳc tỏc Zn/Ti-LDHs 39 3.1.1 Ph XRD 39 3.1.2 Kt qu EDS 40 3.1.3 Kt qu UV-Vis cht rn 42 3.1.4 nh SEM ca cỏc mu xỳc tỏc 43 3.1.5 nh TEM ca vt liu 44 3.1.6 Kt qu hp ph - gii hp ph nit 45 3.1.7.Kt qu ph IR 47 3.2 Nghiờn cu hot tớnh quang xỳc tỏc ca Zn/Ti-LDHs cho phn ng phõn hy RhoB 48 3.2.1 nh hng ca oxi, xỳc tỏc v ỏnh sỏng n phn ng quang húa oxy húa RhoB 48 3.2.2 Kho sỏt nh hng ca t l s mol Zn2+/Ti4+ 49 3.2.3 Kho sỏt nh hng ca hm lng xỳc tỏc 50 3.2.4 nh hng ca pH 52 3.2.5 Thu hi v tỏi sinh xỳc tỏc 53 KT LUN 55 TI LIU THAM KHO 56 DANH MC HèNH Hỡnh 1.1 Khoỏng s t hydrotalcite 12 Hỡnh 1.2 Cu trỳc ca hydrotalcite km-titan 14 Hỡnh 1.3 Hỡnh dng lp brucite (a) v cu trỳc lp ca hydrotalcite (b) 15 Hỡnh 1.4 Giỏ tr L ph thuc vo bỏn kớnh anion 15 Hỡnh 1.5 Giỏ tr L ph thuc vo dng hỡnh hc ca anion 16 Hỡnh 1.6 Quỏ trỡnh trao i anion 18 Hỡnh 1.7 Phõn t rhodamine B 25 Hỡnh 2.1 Hỡnh cỏc mt phn x nhiu x tia X 27 Hỡnh 2.2 Cỏc kiu ng hp ph-gii hp ng nhit theo IUPAC 34 Hỡnh 2.3 ng chun rhodamine B 38 Hỡnh 3.1: Kt qu ph XRD ca cỏc mu LDHs Zn-Ti- CO32 (trc phn ng) vi t l Zn/Ti thay i 40 Hỡnh 3.2: Ph EDS ca cỏc mu vt liu LDHs Zn-Ti- CO32- 41 Hỡnh 3.3: Kt qu ph UV-Vis cht rn cỏc mu LDLs Zn-Ti- CO32- 42 Hinh 3.4 nh SEM mu xỳc tỏc MT5-0(a) v MT 5-1(b) 43 Hinh3.5 nh SEM ca mu xỳc tỏc MT5-2(c) v MT5-3(d) 43 Hỡnh 3.6: Kt qu TEM ca vt liu MT 5-1 44 Hỡnh 3.7 ng hp ph - gii hp nit ca mu xỳc tỏc MT5-1 v MT5-3 45 Hỡnh 3.8a S phõn b mao qun BJH ca mu MT5-1 46 Hỡnh 3.8b S phõn b mao qun BJH ca mu MT5-3 46 Hỡnh 3.9: Ph IR ca cỏc mu xỳc tỏc Zn/Ti-LDHs 47 Hỡnh 3.10: nh hng ca cỏc tỏc nhõn n phn ng quang húa 48 Hỡnh 3.11: Kho sỏt s nh hng ca t l Zn2+/Ti4+ 49 Hỡnh 3.12: nh hng ca hm lng xỳc tỏc 50 Hỡnh 3.13: nh hng ca hm lng xỳc tỏc (MT 5-0.5) lờn suy thoỏi quang 51 Hỡnh 3.14: Kho sỏt nh hng ca pH 52 Hỡnh 3.15: Kho sỏt suy thoỏi quang Rhodamine B vi cỏc pH thay i gi 53 Hỡnh 3.15: Kt qu x lý rhodamine B sau ln tỏi sinh xỳc tỏc 53 Hỡnh 3.16 Ph IR ca mu xỳc tỏc MT5-1 trc v sau phn ng 54 DANH MC BNG Bng 2.1: Cỏc mu hydrotalcite km- titan iu ch c 26 Bng 2.2 S ph thuc ca hp th quang theo nng Rhodamine B 37 Bng 3.1 Cụng thc d kin ca cỏc mu xỳc tỏc hydrotalcite km-titan 39 Bng 3.2: Thnh phn % nguyờn t cỏc vt liu Zn/Ti-LDHs thu c v cụng thc d kin 41 Bng 3.3: S thay i ca bc súng hp th cc i 42 Bng 3.4 Cỏc tỏc nhõn nh hng ti phn ng quang xỳc tỏc Error! Bookmark not defined DANH MC CC T VIT TT Kớ hiu vit tt Tờn ca kớ hiu vit tt RhoB Rhodamine B HT Zn-Ti Hydrotalcite km-titan Zn/Ti-LDHs Zn/Ti- Layer Double Hydrotalcites H vt liu lp km-titan Hydrotalcite c iu ch ch yu bng phng phỏp ng kt ta nhng pH phự hp, t dung dch hn hp mui cha cỏc cation kim loi cn thit, cỏc vt liu hydrotalcite cú b mt ln, cú cu trỳc l xp, cú kh nng trao i ion v cỏc t nh cht khỏc nh: húa hc, quang hc, xỳc tỏc, in t Do ú nú c ng dng nhiu cỏc lnh vc khỏc nh: cht mang, cht hp ph, xỳc tỏc mng chn lc ion [5] 1.2 c im hydrotalcite 1.2.1 Cụng thc Hydrotalcite l hn hp cỏc hidroxit ca cỏc kim loi húa tr II v kim loi húa tr III, IV cú cụng thc tng quỏt l [1,10,15,32]: [M2+1-xM3+/4+x(OH)2]x+[An-x/n].mH2O Trong ú: - M2+: Kim loi húa tr II nh Mg, Ni, Zn, Ca - M3+/4+: Kim loi húa tr III/IV nh Al, Fe, Cr, Co,Ce, Ti - An-: anion nh: F-, Cl-, NO3-, SO42-, CO32- - Giỏ tr x t 0,2-0,33 vi x = M3+/4+/(M2++ M3+/4+) Cỏc hydroxit kim loi to thnh lp a din mang in t ch dng cu trỳc trung hũa v in, cỏc anion c xen vo cỏc khong trng gia hai lp a din 1.2.2 c im cu trỳc Hydrotalcite km-titan cú cụng thc tng quỏt: [(Zn1-yTiy(OH)2)+y.(A2y/nn-)2y-].mH2O, ú A l anion CO32- Hydrotalcite km-titan cú cu trỳc dng lp, bao gm: Lp hiroxit: l hn hp ca cỏc hiroxit ca km húa tr (II) v titan húa tr (IV), cú cu trỳc bỏt din m nh l cỏc nhúm OH -, tõm l cỏc cation kim loi húa tr (II) v (IV), cu trỳc ca chỳng tng t nh cu trỳc brucite t nhiờn [1,6,23] Cu trỳc ny c sp t theo dng lc giỏc kh t c 13 Lp hiroxit cú dng [(Zn1-yTiy(OH)2)]y+ ú mt phn Zn(II) c thay th bng Ti(IV) hiroxit mang in t ch dng v c bự bi ion CO32-chốn gia hai lp Mt lng ln cỏc ion húa tr hai, bn vi t l khỏc cú th thay th M2+ cu trỳc hirotanxit dn n cỏc dn xut hirotanxit [5,21,40] Lp xen gia: [(A2y/nn-)2y-].mH2O l cỏc anion mang in tớch õm v cỏc phõn t nc nm xen gia lp hiroxit trung h a lp in tớch dng Lp hiroxit liờn kt vi lp xen gia bng lc hỳt tnh in Liờn kt gia cỏc phõn t nc v cỏc anion lp xen gia l liờn kt hiro Cỏc anion v cỏc phõn t nc lp xen gia c phõn b mt cỏch ngu nhiờn v cú th di chuyn t khụng nh hng, cỏc anion khỏc cú th thờm vo hoc loi b cỏc anion lp xen gia m khụng lm thay i tớnh cht ca hirotanxit (hỡnh 1.2) [16,21,34] Lp xen gia [An-x/n].mH2O l cỏc anion mang in tớch õm v cỏc phõn t nc nm xen gia lp hidroxit trung hũa lp in t ch dng [1] Hỡnh 1.2 mụ t cu trỳc v lp anion (A-)nm gia hai lp hidroxit Hinh 1.2 Cu trỳc ca hydrotalcite km-titan 1.2.3 c im Lp xen gia nm gia hai lp hidroxit c th luõn phiờn xp chng lờn nhau, lm cho hydrotalcite cú cu trỳc lp (hỡnh 1.2) Lp hidroxit liờn kt vi lp xen gia bng lc hỳt tnh in Liờn kt gia cỏc phõn t nc v cỏc anion lp xen gia l liờn kt hidro Cỏc anion v cỏc phõn t nc lp xen gia c phõn b mt cỏch ngu nhiờn v cú th di chuyn t khụng nh hng, cỏc anion khỏc cú th 14 thờm vo hoc loi b cỏc anion lp xen gia m khụng lm thay i tớnh cht ca hydrotalcite (hỡnh 1.3) [17,20,29] Hinh 1.3 Hỡnh dng lp brucite (a) v cu trỳc lp ca hydrotalcite (b) Khụng cú gii hn cỏc loi anion lp xen gia, nhiờn tng hp hydrotalcite dựng hp ph ngi ta thng dựng anion cacbonat, cũn tng hp hydrotalcite dựng trao i ion, thụng thng lp anion xen gia l Cl-, Br- Tựy thuc vo bn cht ca cỏc cation, anion m s lng lp xen gia v k ch thc hỡnh thỏi ca chỳng thay i to nờn vt liu cú nhng c tớnh riờng [15,26,33] Khong cỏch gia hai lp hidroxit L = 3-4 , c xỏc nh bi k ch thc ca cỏc anion, giỏ tr L ph thuc vo: - Bỏn kớnh ca anion: Anion cú bỏn kớnh cng ln thỡ khong cỏch lp xen gia L cng ln (hỡnh 1.4) Hỡnh 1.4 Giỏ tr L ph thuc vo bỏn kớnh anion 15 - Cu to khụng gian ca anion Anion NO3- xen gia lp hidroxit cú cu to khụng gian khỏc nờn khong cỏch (L) gia hai lp hidorxit cú cỏc giỏ tr khỏc (hỡnh 1.5) [15] Hỡnh 1.5 Giỏ tr L ph thuc vo dng hỡnh hc ca anion 1.3 Tớnh cht Khong khụng gian gia cỏc lp hidroxit cha cỏc anion v cỏc phõn t nc sp xp mt cỏch hn n iu ny ó to mt s tớnh cht c trng ca cỏc dng hydrotalcite [13,15] 1.3.1 Tớnh cht trao i anion õy l mt nhng tớnh cht quan trng ca hp cht hidroxit kộp, dng cu trỳc ny cú th trao i mt lng ln anion bờn bng nhng anion khỏc cỏc trng thỏi khỏc [26,34] Quỏ trỡnh trao i anion cú th dn n thay i giỏ tr ca khong cỏch (L) ca cỏc lp trung gian gia hai lp hidroxit k cn S thay i ph thuc vo hỡnh dng v in tớch ca cỏc anion trao i (hỡnh 1.6) Do cu trỳc lp v s an xen anion, hydrotalcite cú phõn tỏn v kh nng trao i anion cao [16,29] Phn ng trao i anion thng dng cõn bng: [M2+M3+A] + A = [M2+M3+A] + A 16 A: anion lp xen gia A: anion cn trao i hoc vit dng rỳt gn: HT-A + A- = HT-AA; HT-A: HT cú anion xen gia A; HTAA: HT cú anion xen gia cựng tn ti, lỳc ny quỏ trỡnh trao i xy khụng hon ton, A khụng trao i ht vi A S trao i thun li vi cỏc anion cú mt in tớch cao S trao i anion hydrotalcite ph thuc vo cỏc yu t sau: - S tng tỏc tnh in ca lp hydrotalcite t ch in dng vi anion xen gia v nng lng t cỏc anion cn trao i - i lc trao i ca lp hidroxit vi cỏc anion cn trao i dung dch v ỏi lc ca lp hidroxit vi anion lp xen gia [11,15,30] - Cu to ca ion cn trao i (A) - Hng s cõn bng trao i tng bỏn k nh anion trao i gim, trao i ion s thun li vi cỏc anion dung dch cú nng cao - Anion húa tr II c u tiờn hn anion húa tr I v thi gian trao i cng nhanh hn - S trao i ion cũn cú s u tiờn i vi cỏc ion cú mng li tinh th vt liu cht hp ph rn hoc cú cu to ging vi mt nhng ion to mng li tớnh cht ca cht hp ph, ú s hp ph c xem l s kt tinh - Kh nng trao i anion cũn ph thuc vo pH ca dung dch cha anion [15,20,34] 17 Hinh 1.6 Quỏ trinh trao i anion 1.3.2 Tớnh cht hp ph S hp ph cỏc anion cú th dn n s tỏi to li cu trỳc lp ca hydrotalcite sau x lý hydrotalcite nhit cao Tớnh cht hp ph th hin rt tt i vi HT/CO32- HT/CO32- sau nung nhit nht nh s cú kh nng hp ph tt hn lỳc cha nung Khi ú HT/CO32- b mt cỏc phõn t nc lp xen gia v khớ CO2 thoỏt hỡnh thnh tõm baz O2- cú cu trỳc kiu M2+1-xM3+/4+xO1+x/2 Hn hp oxit ny cú kh nng tỏi to li cu trỳc lp tip xỳc vi dung dch cỏc anion khỏc [15,31,34] Hydrotalcite hp ph vi cỏc anion hỡnh thnh lp xen gia, hydrotalcite khụng cú kh nng trao i cation vi Mg v Al cỏc tm bỏt din lc liờn kt to phc ln Cỏc hydrotalcite hp ph mụi trng nc nờn chu nhiu tỏc ng ca yu t mụi trng nh pH, cỏc ion v hp cht l Cỏc yu t nh hng n quỏ trỡnh hp ph cng ging nh cỏc yu t nh hng n quỏ trỡnh trao i ion: nhit nung, t l kim loi, pH [20,29] 18 1.4 Phng phỏp iu ch hydrotalcite Do hydrotalcite cú ng dng rng rói cỏc lnh vc khỏc nờn cú nhiu cụng trỡnh nghiờn cu iu ch theo phng phỏp khỏc nh: phng phỏp mui baz, phng phỏp mui oxit, phng phỏp ng kt ta, phng phỏp xõy dng li cu trỳc ú phng phỏp ng kt ta to cỏc tinh th hydrotalcite tt nht v cú nhiu u im c s dng ph bin [15,33] 1.4.1 Phng phỏp ng kt ta Phng phỏp ny tng hp hydrotalcite t hai mui kim loi húa tr (II) v (III): Cho hn hp mui kim loi vo mui ca kim loi kim cú t nh baz, hn hp dung dch c gi c nh khong pH nht nh quỏ trỡnh iu ch Cỏc cht tham gia phn ng phi c khuy trn vi tc khụng i sut quỏ trỡnh phn ng u im ca phng phỏp ng kt ta pH c nh: - Tinh th cú k ch thc ng u v cú ng nht cao - Tinh th cú cu trỳc bn vng - t ln cht - Din tớch b mt ln - T trng nh Ngoi ra, cu trỳc v tớnh cht húa lý ca sn phm hydrotalcite cũn ph thuc vo nhiu yu t nh : Phng phỏp kt ta, bn cht v nng ca cht phn ng, pH kt ta, nhit v thi gian gi húa, tinh khit, kt ta v sy khụ [17] 1.4.2 nh hng ca pH Kt ta vi pH tng: pH c iu chnh bi dung dch hn hp mui kim loi v dung dch baz ca kim loi kim hoc mui cacbonat ca kim loi kim [18,20] Vớ d, h [Zn-Cr-Cl] ó c iu ch bng cỏch thờm dung dch NaOH vi nng khụng i vo hn hp dung dch ZnCl2 v CrCl3 19 MT5-1 400 800 1200 151 136 831 465 MT5-1 SP 1600 2000 2400 S súng (cm-1) 2800 3200 3600 4000 Hỡnh 3.16 Ph IR ca mu xỳc tỏc MT5-1 trc v sau phn ng SP Hỡnh 3.16 ch rng ph IR trc v sau phn ng ca mu MT5-1 cỏc dao ng c trng cho liờn kt gn nh khụng thay i tr cỏc dao ng 3200-3600 cm-1 (c trng cho liờn kt O-H) v 1200 1600 cm-1 b gim khỏ mnh v cng 54 KT LUN Qua thi gian tin hnh thc nghim tng hp xỳc tỏc Zn/Ti-LDHs v nghiờn cu ng dng quang xỳc tỏc x lý phm mu Rho , chỳng tụi ó nhn c cỏc kt qu nh sau: ó tng hp c xỳc tỏc hydrotalcite Zn-Ti theo cỏc t l mol Zn/Ti khỏc v nghiờn cu c trng cu trỳc xỳc tỏc bng cỏc phng phỏp vt lý: nhiu x Rnghen (XRD), EDS, ph hng ngoi IR, kớnh hin vi in t quột (SEM), kớnh hin vi in t truyn qua (TEM) v phng phỏp ng nhit hp ph- gii hp ph (BET) Cỏc mu xỳc tỏc iu ch cú cu trỳc hydrotalcite, din tớch b mt ln Tin hnh nghiờn cu quỏ trỡnh x lý Rhodamine B trờn cỏc mu xỳc tỏc hydrotalcite Zn-Ti tng hp iu kin phn ng khỏc Kt qu cho thy quỏ trỡnh oxi húa Rhodamine B ph thuc vo t l Zn:Ti, hm lng xỳc tỏc, thi gian phn ng, cỏc tỏc nhõn oxi húa Mu xỳc tỏc MT5-1 vi t l Zn:Ti=5:1 cho hiu sut x lý v thu hi tỏi sinh tt nht: Hiu sut x lý 100 mL dung dch Rho 20mg/L t 98% sau gi, 0,3g xỳc tỏc, pH = 6, chiu sỏng bng búng ốn compact 20W, nhit phũng Cỏc kt qu nghiờn cu bc u cho thy cú th ng dng hydrotalcite Zn-Ti lm vt liu xỳc tỏc quang loi b phm nhum Rho mụi trng nc Vic thay th ng hỡnh Zn2+ bng Ti4+ gúp phn ci thin ỏng k kh nng quang xỳc tỏc ca vt liu Zn-Ti hydrotalcite Hot tớnh xỳc tỏc ph thuc vo hm lng Ti mng tinh 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Bng 2.1: Cỏc mu hydrotalcite km- titan iu ch c 26 Bng 2.2 S ph thuc ca hp th quang theo nng Rhodamine B 37 Bng 3.1 Cụng thc d kin ca cỏc mu xỳc tỏc hydrotalcite km-titan 39 Bng 3.2: Thnh... nhit hp ph- gii hp ph (BET) Cỏc mu xỳc tỏc iu ch cú cu trỳc hydrotalcite, din tớch b mt ln Tin hnh nghiờn cu quỏ trỡnh x lý Rhodamine B trờn cỏc mu xỳc tỏc hydrotalcite Zn -Ti tng hp iu kin phn