B GIO DC V O TO

TRNG I HC QUY NHN

NGUYN DUY TH

CNG LUN VN THC S

NGHIN CU CH TO MNG TRN C S GRAPHEN

V NH GI MT S C TNH CA MNG

Chuyn ngnh : Ha l thuyt v ha l

M s : 06.44.01.19

Kha : 19 (2016-2018)

Ngi hng dn khoa hc:

1/ PGS.TS. NGUYN TH VNG HON

2/ TS. NG HNG NH THU

Bnh nh - Nm 2017
M U
1. L DO CHN TI...4
2. TNG QUAN TI LIU V TNH HNH NGHIN CU TI..5
3. MC TIU NGHIN CU ................................................................................. 7
4. I TNG V PHM VI NGHIN CU ................................................... 7
5. PHNG PHP NGHIN CU ....................................................................... 8
6. NI DUNG NGHIN CU
B CC CA LUN VN ................................................................................... 9
Chng 1: TNG QUAN TI LIU......................................................................... 9
Chng 2: PHNG PHP NGHIN CU V THC NGHIM1
Chng 3: KT QU V THO LUN24
KT LUN
TI LIU THAM KHO........................................................................................
K HOCH NGHIN CU ...................................................................................

2
 M U
1. L DO CHN TI
Cng ngh mng c bit n t rt lu trong nhiu lnh vc, c bit trong
lc tch cht. u im ca k thut lc mng l c th tch c cc cu t c kch
thc ht n c phn t v ion m khng cn s dng n ha cht khc, cc cu
t cn tch khng phi chuyn pha, nng lng tiu tn tng i thp, iu kin
vn hnh qu trnh n gin, l phng php tch hiu qu, tc x l rt cao,
dng chy nhanh, thn thin vi mi trng. Bn cnh mng to thnh c bn
c hc cao nn d dng cho vic thu hi v ti s dng mng [1-4].
C th ni vt liu mng trn c s graphen (graphen v graphen oxit) trn
nn polysulfon l th h mng mi cc k hiu qu trong qu trnh tch, lc cht.
Bn cnh nhng hiu qu t c ca cng ngh mng trong nhng lnh vc ny
c bit n, vic nghin cu ch to mng trn c s graphen v nh gi cc
c tnh ca mng c chng ti quan tm. Mt trong nhng vn c quan
tm khi nghin cu cc c tnh ca mng ny l s dng mng nh l mng xc tc
ng dng cho qu trnh phn hy hoc chuyn ha mt s hp cht hu c c hi
trong mi trng nc. Cc hp cht hu c c hi gy nhim mi trng nc
c th k n l thuc nhum, cc hp cht cha phenol, thuc tr su, thuc dit
c, d lng khng sinh trong thy, hi sn v tht gia sc, gia cm. S xut hin
d lng khng sinh trong nui trng thy sn cng nh hi sn thuc h quinolon,
mt h khng sinh c ph tc dng dit khun rng, hiu qu cao nn chng c
s dng rng ri trong vic iu tr, cha bnh. Hu qu l gim hiu qu ca cc
khng sinh quinolon i vi cc chng vi khun gy kh khn v tn km trong
iu tr bnh. Nhng cht gy nhim c th c tch t sinh hc, tc ng bt
li n s tn ti ca sinh vt di nc, h ng thc vt cng nh nh hng
rt ln ti sc khe con ngi. V vy, bn cnh vic nng cao thc bo v
mi trng ca con ngi, sit cht cng tc qun l mi trng th vic tm ra
phng php nhm gim thiu hoc loi b chng ra khi cc ngun nc b
nhim c ngha ht sc to ln.
Xut pht t nhng l do trn ti chn ti Nghin cu ch to mng trn
c s graphen v nh gi mt s c tnh ca mng
y l mt hng nghin cu rt mi cha c cc nh nghin cu trn th
gii cng nh trong nc cp ti. Hy vng, vi nh hng nghin cu mang
tnh cht thm d t vic ch to mng n kho st, nh gi cc tnh nng ca
mng m ti la chn bc u mang li nhng kt qu ng k nhm gp phn
trong vic khai thc nhng u im ca cng ngh mng phc v cc nhu cu kinh
3
t - dn sinh.
2. TNG QUAN TNH HNH NGHIN CU TI
C th ni thnh tu ni bt nht trong lnh vc khoa hc vt liu nhng nm
u th k 21 l vic tch thnh cng graphen n lp t graphit cng nh vic ch
to, c lp, nhn dng v xc nh c tnh ca graphen c cng b bi hai nh
khoa hc vt l gc Nga, Andre K. Geim v Konstantin S. Novoselov. S pht trin
trong lnh vc nghin cu vt liu graphen v cc tnh cht cng nh ng dng thc
t ca graphen ngy cng nhn c s quan tm khng ch vi cng ng cc nh
nghin cu hn lm m c i vi cng ng cc nh nghin cu cng ngh.
Graphen v vt liu trn c s graphen m c bit l graphen oxit c nhiu
u im nh din tch b mt ln, c cha rt nhiu nhm chc ha hc hot ng
m c bit l cc gc cha oxi hot ng. V vy chng c xem l vt liu nn
l tng, thun li cho vic gn cht hoc phn tn cc phn t kim loi, oxit kim
loi, cc hp cht ha hc khc, to nn nhng t hp c cc tnh cht mi, tnh linh
ng cao ca electron trn b mt graphen vi bn c hc, bn nhit c ci
thin. Cho n nay, graphen v vt liu trn c s graphen c xem l loi vt liu
c kh nng ng dng rng ri trong nhiu lnh vc khc nhau v chng c nhiu
c tnh khc thng so vi cc vt liu nano ang c bit hin nay, c bit
trong lnh vc lu tr nng lng, pin v acquy ion Li, pin mt tri vi cht mu
cm nhy quang DSSC, cng ngh sinh hc, y sinh hc, vt liu polymer
nanocomposit [5-11]. Ngoi ra, chng cn c xem xt ng dng trong lnh vc
iu ch vt liu mi, xc tc hp ph y ha hn i vi cc qu trnh x l
nhim, lm sch mi trng.
K t khi lnh vc nghin cu v cng ngh mng pht trin, cng ngh
mng lc trn c s vt liu graphen (graphen v graphen oxit) trn nn polysulfon
nhn c s quan tm c bit ca cc nh khoa hc. c nhiu cng trnh cng
b v kh nng ng dng ca mng ny trong vic tch, lc mui; tch du t nh
du/ nc theo c ch hp ph chn lc [12-14]. Tuy vy, y ch l nhng kt qu
khm ph ban u cn phi tip tc nghin cu v pht trin.
trong nc, nhiu nghin cu v t ng h p vt liu graphen v graphen oxit
bin tnh ng dng x l asen v mt s kim loi nng cng nh cc hp cht
hu c c hi kh phn hy trong mi trng nc c cng b [30-34]. Tuy
nhin vic nghin cu cng ngh mng trn c s vt liu ny cn rt hn ch ang
bc s khai, c bit l mng xc tc phn hy hoc chuyn ha mt s hp
cht hu c c hi trong nc.

4
3. MC TIU NGHIN CU
- Ch to vt liu mng trn c s graphen (graphen v graphen oxit bin tnh).
- nh gi mt s c tnh ca mng.
4. I TNG V PHM VI NGHIN CU
4.1. i tng nghin cu
- Vt liu graphen, graphen oxit v vt liu bin tnh.
- Vt liu mng trn c s graphen v graphen oxit bin tnh.
- Ngun nc cha hp cht hu c kh phn hy (d lng khng sinh trong cc
mu nc c pha ch hoc nc nui tm).
4.2. Phm vi nghin cu
- Bc u nghin cu tng hp mng v cc yu t nh hng n cht lng
mng tng hp quy m phng th nghim.
- nh gi mt s c tnh ca mng, c bit l thm d kh nng tch loi cc
thnh phn gy nhim nc (hp cht hu c kh phn hy).
5. PHNG PHP NGHIN CU
- c ti liu lin quan n vn nghin cu, t nh hng cho ni dung
nghin cu.
- Tng hp graphen v vt liu trn c s graphen bng phng php ha hc.
- Ch to mng graphen v graphen oxit (GO) bin tnh trn nn polysulfon (PSF)
theo phng php o pha.
- Cc d lng khng sinh thuc h quinolon trong mu nc c pha ch (hoc
nc nui tm) c xc nh bng phng php trc quang hay phng php in
di mao qun.
6. NI DUNG NGHIN CU
6.1. Tng hp vt liu
- Tng hp graphen v graphen oxit (GO) bin tnh;
- Tng hp mng trn c s graphen v GO bin tnh trn nn polysulfon. Nghin
cu cc yu t nh hng n qu trnh to mng (m bo c cc tnh nng ca
mng nh thm t, kch thc l ca mng)
6.2. nh gi c tnh mng
- nh gi c tnh b mt ca mng: o gc thm t; Ph hng ngoi phn x
(FTIR - ATR); Hin vi lc nguyn t (AFM); nh chp hin vi in t qut (SEM)
- nh gi c tnh tch, lc ca mng: lu gi; Nng sut lc; Mc duy tr
nng sut lc ( gim nng sut lc theo thi gian).
- nh gi kh nng chng tc nghn ca mng: duy tr nng sut lc theo thi
gian; H s tc mng.
5
6.3. Thm d kh nng x l d lng khng sinh trong cc mu nc
B CC CA LUN VN
Chng 1: TNG QUAN TI LIU
1.1. Tng quan v graphen oxit v graphen
1.1.1. Tng quan v graphen oxit (GO)
Graphit oxit, trc y gi l oxit graphitic hoc axit graphitic, l mt hp cht
ca carbon, oxy v hydro thu c bng cch x l graphit vi cht oxy ha mnh. Cc
sn phm oxy ha l mt lng ln hn hp mu vng rn vi t l C:O trong khong
t 2,1 n 2,9, m vn gi c cu trc lp ca than ch nhng vi khong cch ln
hn nhiu v khng lin tc. Sau khi oxi ho graphit, ngi ta siu m tch lp
graphit to ra cc vy graphen oxit.
C th m t cu trc ca mt lp vy graphen oxit nh hnh 1.1.

Hnh 1.1. Cu trc ca mt lp vy graphen oxit

c im cu trc quan trng nht ca sn phm ny l lun c mt cc
nhm chc cha oxi hot ng. Cc nhm chc cha oxi ph bin nht trn GO l
nhm hydroxyl (C-OH), carboxyl (-COOH), epoxid (C-O-C), keton (C=O) v cc
hp cht cha C-O v C=O khc nh lactol, peroxid, anhydrid Cc nhm chc
ny c kh nng to lin kt hydro vi cc phn t nc v vy m graphen oxit c
kh nng phn tn tt trong nc v cc dung mi hu c phn cc khc. Tuy
nhin, cu trc chi tit ca GO vn cn l mt vn bn lun v ph thuc nhiu
vo nhiu yu t nh nguyn liu u s dng ch to, cc iu kin thc hin
(thi gian, nhit , ha cht,...) qu trnh oxi ha a n nhng kt qu khc
nhau nht nh v c tnh sn phm [15 -18]. Graphen oxit c din tch b mt
ring ln v c kh nng phn tn tt trong dung mi phn cc nn c s dng
lm cht nn tng hp mt s vt liu mi.
Mc d GO c nghin cu trong hn mt th k, cc cu trc ha hc
chnh xc ca GO vn cn cha r rng. Bn cht ca cc nhm chc oxy v cch
gn kt trn mng li cacbon l rt quan trng c c mt cu trc GO chnh

6
xc [14 -15]. Cu trc ca GO ph thuc nhiu vo phng php tng hp v c
a ra bi nhiu nh nghin cu khc nhau th hin trong hnh 1.2.

Hnh 1.2. Cu trc xut ca GO bi cc nh nghin cu [15]

Trong s m hnh ca Lerf Klinowski ph bin hn c. Theo [19], graphit sau
khi oxi ha, trn mt phng nm ngang ca cc lp c cc nhm hydroxyl, epoxy v
trn cc gc ca mt phng nm ngang c th hnh thnh cc nhm chc carbonyl
hoc carboxylic. Ayrat. M v cng s [20] xut mt m hnh GO mi, tn gi
l DSM (Dynamic Structural Model). Ngc li vi tt c cc m hnh xut
trc y, nhm tc gi khng xem xt cc GO nh mt cu trc tnh vi mt tp
hp cc nhm chc. Thay vo , h cho rng cc nhm chc mi lin tc pht
trin v bin i. Vai tr quan trng trong tt c nhng bin i thuc v nc kt
hp vo GO chuyn i c cu ca n, v sau ri khi cu trc thng qua cc
phn ng khc nhau. ng lc ca s bin i l tch t ca in tch m trn lp
GO, c n nh bng s cng hng v hnh thnh ca mt lp. Cc vng thm,
cc ni i, cc nhm epoxy c cho l nm trn mng li cacbon gn nh
phng, trong khi cacbon ni vi nhm OH hi lch so vi cu trc t din dn n
cu trc lp hi cong. Cc nhm chc c cho l nm c trn ln di cc lp GO.
V mi lp u cha cc nhm chc c oxi mang in tnh m, do c lc y
xut hin gia cc lp, ng thi lm cho GO th hin tnh a nc v trng c
trong nc. Hn na, vic to lin kt hydro gia cc lp graphen oxit thng qua
cc nhm hydroxyl, epoxi v nc khin cc khong cch gia cc tm GO c
ni rng ng k hn so vi graphit (0,65- 0,75 nm so vi 0,34 nm, c xc nh
thng qua gin XRD) [15].

7
 Hnh 1.3. Lin kt hydro gia cc lp graphit oxit [15]
Graphit sau khi oxi ha to thnh graphen oxit mang nhiu nhm chc cha
oxi hot ng nh carboxyl (-COOH), hydroxyl (-OH), keton (C=O), epoxid (C-O-
C). Tuy nhin tng kh nng hot ng ca vt liu cn bin tnh b mt gn
cc nhm chc khc ln b mt ca vt liu. C hai cch bin tnh GO: bin tnh
khng thng qua v thng qua to lin kt ha hc.
Nguyn tc ca phng php ny da vo s tng tc ca GO vi cc tc
nhn bin tnh khc nhau m khng thng qua vic to lin kt. Nhng tng tc
bao gm: tng tc v cc cht kh khng phn cc (cht kh nh trng hp,
hydrocarbon), tng tc H-, tng tc -, tng tc cation-, tng tc anion-,
tng tc cation-.

Hnh 1.4. Bin tnh GO khng thng qua lin kt bng PEG-OPE [21]
Khc vi bin tnh khng to lin kt, vic bin tnh GO bng cch to cc
lin kt ha hc vi cc nhm chc hu c vn c pht trin cho nhiu mc ch
khc nhau. Trong chnh lm tng kh nng phn tn ca GO trong cc dung mi
thng thng ngay khi va bin tnh. Phng php ny da vo kh nng ca cc
tc nhn bin tnh v cu trc ha hc ca graphen oxit.
Tm li, c nhiu phng php bin tnh GO nhng ty theo mc ch s
dng cho nhng ng dng khc nhau. Vic bin tnh GO phi m bo gi li cu
trc lin hp ca chng nn cn phi chn la tc nhn bin tnh va h tr kh
nng phn tn trong dung mi va khng to lin kt vi cc nhm chc trn b mt
GO.

8
1.1.2. Graphen
S pht trin trong lnh vc nghin cu vt liu graphen v cc tnh cht
cng nh ng dng thc t ca graphen v vt liu trn c s graphen ngy cng
nhn c s quan tm khng ch vi cng ng cc nh nghin cu hn lm m c
i vi cng ng cc nh khoa hc cng ngh.
Graphen l lp nguyn t cacbon c b dy mt nguyn t c xp cht
trong mt mng lc gic, sp xp cht st nhau theo cu trc hnh t ong hai chiu
(2D) vi khong cch gia hai nguyn t cacbon l 0,142 nm, khong cch gia cc
mt phng lc gic l 3,35 v lin kt vi nhau bi nhng lin kt sp2. y l loi
vt liu c xem mng nht trong s tt c cc dng vt liu [22].

Mt phng y
Cc lp graphen
Trc C

Mt phng cnh

Hnh 1.5. Cu trc graphit ca graphen

C th hnh dung lp mng graphen c to thnh t cc nguyn t cacbon
sp xp theo cu trc lc gic trn cng mt mt phng, hay cn c gi l cu
trc t ong. Do ch c 6 in t to thnh lp v ca nguyn t cacbon nn ch c
bn in t phn b trng thi 2s v 2p ng vai tr quan trng trong vic lin kt
ha hc gia cc nguyn t vi nhau. Cc trng thi 2s v 2p ca nguyn t cacbon
lai ha vi nhau to thnh 3 trng thi sp, cc trng thi ny nh hng theo ba
phng to vi nhau mt gc 120o. Mi trng thi sp ca nguyn t cacbon ny xen
ph vi mt trng thi sp ca nguyn t cacbon khc hnh thnh nn lin kt cng
ha tr sigma () bn vng. Chnh cc lin kt ny quy nh cu trc mng tinh
th graphen hnh dng t ong v l gii ti sao graphen rt bn vng v mt c
hc v tr v mt ha hc trong mt phng mng.
Ngoi cc lin kt sigma, gia hai nguyn t cacbon ln cn cn tn ti mt
lin kt pi () khc km bn vng hn hnh thnh do s xen ph ca cc orbitan pz
khng b lai ha vi cc orbitan s. Do lin kt ny yu v c nh hng khng

9
gian vung gc vi cc orbitan sp nn cc in t tham gia lin kt ny rt linh
ng v quy nh tnh cht in v quang ca graphen [23].
Hnh 1.6 l m hnh ha cc lin kt ca mt nguyn t cacbon trong mng
graphen.

Hnh 1.6. Cc lin kt ca nguyn tcacbon trong mng graphen

V tnh cht, graphen c mt s tnh cht c v tnh cht in k l. N l vt
dn mng nht, rt cng chc v mt c hc, trong sut v d un, kh nng dn
in, dn nhit rt cao, din tch b mt rt ln, ln n 2600 m2/g v trong sut
gn nh hon ton. Ngoi nhng tnh cht trn graphen tng hp c c tnh cht
rt c bit. Chuyn ng ca cc electron rt nhanh, electron dng nh khng c
khi lng v chuyn ng gn bng vn tc nh sng. Electron trong graphen c
vn tc ln gp 100 ln electron trong silicon [24, 25].
thu c graphen ngi ta s dng cc tc nhn kh nh hyrazin,
imetylhyrazin, hyroquinon, NaBH4, axit ascorbic hoc bng cc phng php
nhit, phng php in ha hoc phng php quang xc tc kh ha cc
nhm chc cha oxi trn b mt graphen oxit, sn phm thu c giai on ny
chnh l graphen c kh ha (rGO) t graphen oxit. chnh l graphen nhng
sn phm graphen ny hon ton khng ging vi graphen nguyn gc nh sn
phm thu c khi tch t graphit bng phng php c hc v rGO cn cha mt
phn cc nhm chc ha hc cha c kh. Chnh v vy, graphen c kh ha
t graphen oxit cn c gi l graphen mang nhm chc.

Hnh 1.7. S qu trnh ch to graphen bng phng php kh ha graphen oxit

10
 Graphen oxit c kh (rGO) l sn phm cui cng ca qu trnh ch to
graphen, cc nhm chc cha oxi trn b mt GO ni chung c ly i phn
ln do qu trnh kh GO bng cc tc nhn khc nhau. Cc nhm chc cha oxi
mc khc nhau ty theo phng php v iu kin thc hin, th hin t s
C:O trong rGO c th tng khong 10:1 n 12:1 v th hin phn mng carbon t
lin kt sp3 khi lin kt vi nhm cha oxi tr v carbon lin kt sp2 thun C-C. T
l phn carbon sp2 c khi phc li rt quan trng, v chng quyt nh tnh cht
ca rGO cng gn vi tnh cht ca graphen nguyn khai, c bit tnh cht quang
v in ca vt liu.
S hin din cc nhm chc ha hc ni trn khi oxi ha graphit v mang
trn graphen oxit lm cho b mt ca GO mang in tch m cao nh gip cho
GO tr thnh vt liu i nc v d phn tn trong mi trng nc, khng b kt
lng.
Mi tc nhn kh c hot tnh vi mt nhm chc nht nh v hiu qu kh
ca cc tc nhn l khc nhau. V d vi hydrazin c hot tnh kh mnh vi nhm
epoxy v cacboxylic trong iu kin kh 80 100 oC, t l C: O ~ 10,3 : 1, c ch
kh ca hydrazin c minh ha bi Hnh 1.8.

Hnh 1.8. C ch kh nhm epoxy ca hydrazin [15]

C th nhn thy hydrazin d dng phn ng vi cc nhm chc
epoxy trn b mt mng ca GO hnh thnh nn hydrazin alcohol, cc nhm ny
khng bn s chuyn ha nhanh thnh aminoaziridine, sau cc nhm
aminoaziridine ny c loi b nhit khong 80 - 100 oC hnh thnh nn
lin kt i, khi phc li mng li ca rGO ti v tr . Tc nhn kh NaBH4 cho
thy hiu qu hn so vi hydrazin, n hiu qu cao
vi nhm C=O, hiu qu thp vi nhm epoxy v cacboxylic, nhit kh khong
80 oC, t l C:O ~ 13,4 : 1 cao hn so vi hydrazin C:O ~ 6,2 : 1 [19].
Trong thc t, khi cn c c graphen vi mt lng nht nh, ch c
phng php ha hc qua giai on to thnh GO v kh ha GO mi c kh nng
p ng c. V vy, qu trnh kh ha GO c c sn phm rGO c tnh cht
gn nht vi graphen nguyn khai c xem l qu trnh quan trng nht v l ch
hng ti cui cng ca tt c cc phng php kh ha nu trn.

11
1.1.3. Tm hot ng ca graphen v graphen oxit
Cc hp cht hu c c th c hp ph trn cc ht nano hay vt liu cu
trc nano thng qua nhng tng tc sau: tng tc in t, lin kt hydro, s xp
chng lin kt - , lc phn tn, lin kt cho - nhn v hiu ng k nc [26].
Trong trng hp ca graphen, h thng in t bt i xng ng vai tr ch o
trong vic hnh thnh mnh m ca lin kt tng tc - ca s chng xp vi mt
s cht hu c c cha vng thm. Tng tc cation - cng ng gp vo qu
trnh hp ph [26]. Tng tc ny b chi phi bi s phn cc cation, lc tnh in
gia cc cation v cu trc in t aromatic giu electron [27].
Graphen oxit, GO mang nhiu nhm chc do vy hnh thnh t cc lin kt
hydro hay s tng tc in t vi cc hp cht hu c c cha oxi v nit. Cc
nhm chc cha oxy phn cc ca GO lm cho vt liu ny c xu hng a nc.
GO phn tn tt trong nc v c th b tch lp trong nhiu loi dung mi [15]. S
hin din ca cc nhm chc hot ng nh cacbonyl, epoxy, hydroxyl trn b mt
ca GO cho php n tng tc vi rt nhiu cc phn t tri di trn b mt bin
tnh. Hn na, nhng nhm hot ng ny ca GO cng c th lin kt vi cc ion
kim loi nng c mt trong dung dch thng qua phc b mt, hoc tng tc tnh
in gia b mt m GO v cc cation kim loi, cht mu do n cng c th s
dng tch cc ion t dung dch [26].
Qu trnh hp ph cc ion kim loi v hp cht hu c trn graphen v GO
thng ph thuc nhiu vo pH v bn cht ca cc cht hu c (s vng thm
trong cu trc) [28, 29]. Khi gi tr pH thp c li cho vic ion ha ca cc nhm
chc cha oxi trn b mt GO. Do in t trn b mt GO l m nn s tng tc
tnh in gia cc ion kim loi v GO tr nn mnh hn. Khi gi tr pH cao,
cchydroxit kim loi c th hnh thnh kt ta hay nhm anion s chim u th v
vy xy ra hiu ng y gia anion v b mt GO. Do , cn tm ra gi tr pH ti
u nng cao hiu qu ca qu trnh hp ph.
1.2. Gii thiu v mng lc
1.2.1. Gii thiu chung
1.2.2. nh ngha v mng v cc qu trnh mng
1.2.2.1. Cc qu trnh mng ng lc p sut
1.2.2.2. C ch tch mng
1.2.3. ng dng ca cng ngh mng trong x l nc
1.2.4. Gii thiu mng graphen v graphen oxit trn nn polysulfon (rGO, GO/
PSF) v ng dng

12
1.3. Tng quan v khng sinh nhm quinolon
1.3.1. Gii thiu
1.3.1.1. Cu to ca khng sinh nhm quinolon
1.3.1.2. C ch tc dng v c tnh
1.3.2. Tnh hnh s dng v tn d khng sinh nhm quinolon
1.3.3. Cc phng php xc nh hm lng cc cht khng sinh nhm
quinolon
1.3.3.1. Phng php min dch enzym
1.3.3.2. Phng php vi sinh vt
1.3.3.3. Phng php ha l (Sc k lng; in ha ha tan; in di mao qun;
Phng php trc quang)
Chng 2: PHNG PHP NGHIN CU V THC NGHIM
2.1. Phng php nghin cu
2.2. Thc nghim
2.2.1. Thit b, ha cht
2.2.1.1. Thit b, dng c
- Thit b: T sy; my khuy t gia nhit; cn phn tch in t; my rung siu m;
my o pH; My li tm; Thit b ch to mng ph quay (spin coating).

Thit b ch to mng theo phng php ph quay (Spin Coating)

Phng php ph quay c m t trong hnh v. Dung dch sol c nh git ln
v cho quay. Di tc dng ca lc ly tm, dung dch s lan u trn v to
thnh mng mng.

- Dng c thy tinh: cc thy tinh cc loi; bnh nh mc; pipet cc loi...; nhit
k; giy bc, giy lc; phu lc; ci m no; giy o pH.

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2.2.1.2. Ha cht
Bng 2.1. Cc loi ha cht chnh s dng trong ti.
Tn ha cht Ngun gc
Graphit bt Merck
NaNO3 KMnO4 Vit Nam
H2SO4 98%, H2O2 30% Merck
HCl 36,5%, C2H5OH Trung Quc
NaNO2, Na2CO3, NaOH Vit Nam
Polysulfon (PSF) Merck
Dung mi DMP Trung Quc
Khng sinh thuc h Quinolon (7 loi Trung Quc
khng sinh ph bin trong nc nui tm:
CPFX, DNFX, ERFX, SRFX, DFLX, OA,
FMQ)

2.2.2. Tng hp vt liu

2.2.2.1. Tng hp graphen oxit
Graphen oxit c tng hp da trn phng php Hummers bin tnh, quy
trnh nh sau: cho 1g graphit cacbon; 0,5g NaNO3 v 23ml H2SO4 vo cc thy tinh
chu nhit, lm lnh hn hp (0 - 50C) v khuy u trn my khuy t. Nng
nhit ln 150C v khuy trong 2 gi, cho t t tng lng nh kt hp vi khuy
u lin tc 3 gam KMnO4, sau nng tip nhit n 400C trong 1 gi. Thm
46 ml nc ct v nng nhit ln n 980C. Sau cho thm 15ml H2O2 30%
vo hn hp khuy trong 1 gi. Sau ngui t nhin, lc ra sn phm nhiu
ln bng axit HCl 5% (bng cch cho mu vo mt th tch nht nh axit HCl 5%
khuy nh trong nhiu gi nhit phng sau lc, gn. Lm nh vy 3 ln.
Cui cng ra mu bng nc ct n pH = 7.
thu c graphen oxit, sn phm graphit oxit c tch lp bng k thut
siu m vi dung mi nc. Sn phm c sy nhit 80 0C trong khong thi
gian 12 gi, thu c graphen oxit c mu nu en.
2.2.2.2. Ch to graphen oxit dng kh (graphen)
Cho 1g GO v 300ml H2O cho vo cc 1L, khuy mnh hn hp nh sng
siu m trong 1 gi. Nng nhit ln 800C ng thi khuy nh. Sau khi nhit
t n 800C, cho t t hydrazin vo hn hp (va cho va khuy) v khuy tip
trong vng 20 gi nhit 800C. Lc, ra hn hp bng 120ml C2H5OH. Sy kh

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trong t sy chn khng 800C trong 12 gi. Thu c rGO - graphen oxit kh
(rGO) dng bt mn, en.
2.2.2.3. Tng hp mng trn c s graphen v GO bin tnh trn nn polysulfon
* Tng hp mng graphen oxit (GO) trn nn polysulfon (PSF) theo phng
php o pha
Trc khi ch to mng GO/PSF, PSF v GO c sy kh trong t sy chn
khng 60oC trong 4 h.
- Ha tan PSF trong dung mi DMF, t l PSF thay i t 5, 10, 15 v 25% trng
lng, dung mi DMF: 95, 90, 85 v 75% trng lng. Rung siu m trong 1h
c dung dch polyme ng nht (dung dch 1).
- Graphen oxit vi nhng lng khc nhau (0; 0,5; 1,0 v 2% trng lng PSF)
c ha tan trong dung mi DMP bng cch kt hp rung siu m trong 1h, tip
n khuy nh nhit phng trong 24h (dung dch 2).
- Cho t t (rt chm) dung dch 2 vo dung dch 1, khuy u lin tc trong 24h
nhit phng, thu c dung dch ng nht ca graphen v dung dch polymer
(dung dch c dung dch 3).
- Ch to mng (theo phng php ph quay, spin coating)
Dung dch sol (dung dch 3) c nh git ln thy tinh ca thit b to
mng. Theo phng php ph quay, di tc dng ca lc ly tm, dung dch s lan
u trn v to thnh mng mng. Cho mng tip xc vi khng kh ch trong 20
giy, sau a tm thy tinh c cn mng vo chu nc ct DI (nc
ion). yn trong chu nc DI 10 pht, sau dng dao mng lch nh mng,
cho n khi thy mng c bc hn khi tm knh. Dng nc ct DI ra sch
mng nhiu ln loi lng d dung mi, thu c mng GO/PSF. Bo qun
mng trong nc ion.
C th hnh dung qu trnh ph quay gm 3 giai on xy ra lin tip:

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Giai on 1 (Fluid dispense): dung dch c nh git ln . Lng dung dch s
dng thng nhiu hn lng dung dch cn thit hnh thnh mng.
Giai on 2 (Ramp-up, spreading): c gia tc n vn tc quay cn thit. Mt
phn dung dch b vng ra khi . nht dung dch quyt nh dy mng.
quay vi vn tc khng i, dung dch tip tc chy lan trn di tc dng ca
nht v lc ly tm.
Giai on 3 (Evaporation): s bay hi dung mi quy t nh dy mng. tip
tc quay vi vn tc khng i nhng dng chy nht khng ng k.
Theo Meyerhofer, do dung mi bay hi ra khi mng, nht dung dch tng dn
n s gel ha ca dung dch sol trn b mt .
dy mng thu c t phng php ph quay kh ng u.
* Nghin cu cc yu t nh hng n qu trnh to mng
Ngoi vic nghin cu t l dung mi DMF ha tan PSF, t l GO v dung
mi DMF cn nghin cu nh hng ca pH v cc nh hng n thng s c
trng mng ( nht ca dung dch, tc quay, thi gian quay).
* Tng t i vi qu trnh tng hp mng graphen trn nn polysulfon
(PSF)
2.2.2.4. Tng hp mng xc tc trn c s graphen v GO bin tnh trn nn
polysulfon
- Chun b dung dch 1: Ha tan PSF trong dung mi DMF, lng PSF c thay
i trong qu trnh ha tan.
- Chun b dung dch 2:
Ly m gam GO ha tan trong 100 mL etanol v 20 mL nc ct, siu m trong 2
gi, sau lm lnh hn hp nhit 0-50C. Tip n thm t t tng git 2 mL
TiCl4 (99%, d= 1,73g/mL) vo hn hp trn bng cch nh t t tng git, dung
dch thu c c mu nu. Ch hn hp trn lun lun c lm lnh v khuy t
lin tc trnh s thy phn TiCl4. Cho hn hp trn vo Autocle v tin hnh
thy nhit 180 oC trong 12 gi. Sn phm thu c ra nhiu ln bng nc ct,
sau sy kh 80 oC trong 6 gi. Lng GO dng trong qu trnh tng hp thay
i t 0,05 0,5 % khi lng. Cc mu c k hiu l TiO2-rGO(x), vi x = 0,05;
0,1; 0,5) tng ng.
Dung dch ca hn hp TiO2-rGO (x) c ha tan vo dung mi vi lng thch
hp, kt hp rung siu m trong 1h. Tip n khuy nh nhit phng trong
24h, thu c dung dch 2.

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- Cho t t (rt chm) dung dch 2 vo dung dch 1, khuy u lin tc trong 24h
nhit phng, thu c dung dch ng nht ca TiO2-rGO (x) v dung dch
polymer (dung dch c dung dch 3).
- Ch to mng theo phng php ph quay tng t nh mc 2.2.2.3. Sn phm
thu c mng TiO2-rGO (x)/ PSF
2.2.3. Cc thng s nh gi
2.2.3.1. nh gi c tnh b mt ca mng
- o gc thm t
- Ph hng ngoi phn x (FTIR - ATR)
- Hin vi lc nguyn t (AFM)
- nh chp hin vi in t qut (SEM)
2.2.3.2. nh gi c tnh tch lc ca mng
- lu gi
- Nng sut lc
- Mc duy tr nng sut lc ( gim nng sut lc theo thi gian)
2.2.3.3. nh gi kh nng chng tc nghn ca mng
- duy tr nng sut lc theo thi gian
- H s tc mng
2.2.4. nh gi kh nng tch loi cc d lng khng sinh trong nc nui
tm bi mng trn c s graphen v graphen oxit bin tnh
2.2.5. Thm d kh nng chuyn ha d lng khng sinh trong nc nui
tm bi mng xc tc trn c s graphen v graphen oxit bin tnh

Chng 3: KT QU V THO LUN

KT LUN

17
K HOCH NGHIN CU
Thi gian Cng vic
T thng 11/ 2017 n thng iu ch graphen v GO, GO bin tnh (TiO2-rGO)
1/ 2018
T thng 1/ 2018 n thng - Ch to mng trn c s graphen v GO bin tnh
2/ 2018 trn nn polysulfon
- c trng tnh nng ca mng
T thng 2/ 2018 n thng ng dng cc vt liu mng ch to c cho qu
6/ 2018 trnh x l hp cht hu c kh phn hy (d lng
khng sinh trong cc mu nc c pha ch hoc
nc nui tm).
Thng 7/2018 Phn tch, nh gi kt qu v hon thnh lun vn

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