Nghiên cứu biến tính vật liệu SBA-15 làm chất hấp phụ và xúc tác quang phân hủy một số hợp chất hữu cơ ô nhiễm trong môi trường nước

ĐẠI HỌC HUẾ
TRƯỜNG ĐẠI HỌC KHOA HỌC






TRẦN THỊ THU PHƯƠNG





: NGHIÊN CỨU BIẾN TÍNH VẬT LIỆU SBA-15
LÀM CHẤT HẤP PHỤ VÀ XÚC TÁC QUANG
PHÂN HỦY MỘT SỐ HỢP CHẤT HỮU CƠ Ô NHIỄM
TRONG MÔI TRƯỜNG NƯỚC





CHUYÊN NGÀNH: HÓA LÝ THUYẾT VÀ HÓA LÝ
MÃ SỐ: 62 44 01 19

NGƯỜI HƯỚNG DẪN: 1. PGS.TS VÕ VIỄN
2. TS TRƯƠNG QUÝ TÙNG









HUẾ, 2015
iii

MC LC

Trang ph  i
L ii
Mc lc iii
Danh m vit tt vi
Bu m
Danh mng viii
Danh m ix
M U 1
U 4
1.1. Vt liu mao qu 4
1.2. Gii thiu v vt liu mao qu-15 5
1.2.1. Tng hp 5
1.2.2. Bi 7
 loi hoc oxit kim lot liu 7

1.2.2.2. G mt mao qun 9
1.2.3. ng dng 12
1.2.3.1. Hp ph 12
1.2.3.2. Cht n 13
 13
u ch vt liu mi 13
1.3. Mt s u v cht liu SBA-15 14
1.4. Hp ph 16
1.4.1. Hp ph i s hp ph 16
ng hc hp ph 17
ng nhit hp ph 18
1.5.  20
 ca phn  20
t li 22
1.5.2.1 k 22
1.5.2.2. Vt li
2
23
1.5.2.3 Vt liu  quang CdS-TiO
2
26
iv

1.6. Mt s hp cht h dng trong lu
U 32
2.1. M 32
2.2. Ni dung 32
2.2.1. Tng hp vt liu 32
2.2.2. Th nghit hp ph  32
2.3. Tng hp vt liu 33

t 33
2.3.2. Tng hp SBA-15 34
2.3.3. 
2
O
3
-SBA-15 34
2.3.4. Tng hp xCO-SBA-15 34
2.3.5. Tng hp vt liu nZnO/SBA-15 35
2.3.6. Pha t-15 36
2.3.7. Tng hp vt liu nTiO
2
-CdS/SBA-15 36
t liu 37
2.4.1. Nhiu x tia X (X-ray Diffraction, XRD) 37
   ng nhit hp ph - kh hp ph  
Adsorption and Desorption Isotherms  BET) 39
2.4.3. Ph hng ngoi (IR) 41
t 42
2.4.5. Hin t  43
2.4.6. Hin t truyn qua (TEM) 44
2.4.7. Ph t ngoi  kh kin (Ultraviolet-Visible Spectroscopy, UV-vis) 46
2.4.8. Ph n t tia X (X-ray photoelectron spectroscopy-XPS) 47
2.4.9. n 49
t hp ph  49
2.5.1. u hp ph  49
2.5.2. Kha 3N-30ZnO/SBA-i vi MB 50
2.5.3. Kha nTiO
2
-CdS/SBA-i vi MO 50

T QU O LUN 51
3.1. Tng hp vt liu hp ph t hp ph 51
3.1.1. Tng hp vt liu hp ph 51
3.1.1.1. Tng hp vt liu SBA-
2
O
3
-SBA-15 51
v

3.1.1.2. Tng hp SBA-15 ch 60
3.1.1.2.1. ng ca thi gian thc TEOS 61
3.1.1.2.2. ng ca t l mol MPS 64
t hp ph ca vt liu 69
3.1.2.1. Kh p ph ol ca vt liu SBA-
15n, 2,7Fe
2
O
3
-SBA-15 -SBA-15-1h 71
t hp ph -15n 75
3.1.2.2.1. Khng hp ph 75
3.1.2.2.2. ng cp ph 76
3.1.2.2.3. ng hc hp ph MB trong dung dSBA-15n . 77
3.1.2.2.4. ng nhit hp ph -15n 79
t hp ph 
2
O
3
-SBA-15 82

3.1.2.3.1. Khng hp ph 82
3.1.2.3.2. ng ca pH 83
ng hc hp ph ARS trong dung d2,7Fe
2
O
3
-SBA-15 85
3.1.2.3.4. ng nhit hp ph 2,7Fe
2
O
3
-SBA-15 87
t hp ph -SBA-15-1h 88
3.1.2.4.1. Khng hp ph 88
3.1.2.4.2. ng ca pH 89
3.1.2.4.3ng hc hp ph phenol trong dung dch bng 10CO-SBA-15-1h 90
3.1.2.4.4. ng nhit hp ph phenol  10CO-SBA-15-1h 92
3.2. Tng hp vt li 94
3.2.1. Tng hp vt liu kN-nZnO-SBA-u kh  94
3.2.1.1. Tng hp vt liu nZnO/SBA-15 94
3.2.1.2. Tng hp vt liu kN-30ZnO/SBA-15 98
u kh a vt liu 3N-30ZnO/SBA-15 106
3.2.2. Tng hp vt liu nTiO
2
-CdS/SBA-u kh  109
3.2.2.1. Tng hp vt liu nTiO
2
-CdS/SBA-15 109
u kh a nTiO
2

-CdS/SBA-15 119
3.2.2.2.1. Kh a vt liu nTiO
2
-CdS/SBA-MO 119
 b 125
KT LUN 127
U THAM KHO 129
vi

DANH M 141

1

M U

ng xi
sng ci  m u. Chm ch yc sinh ra t
n sn xut ci. Trong s
m, c thi t n xu
ngun m t. So vp chp
cht hc hc th 
bii vt c th, u x p cht h
c hp thit.  gii quyt
v  giu k thung
hc, gii hp ph nhit, loi bng sinh hp ph t pha
l p ph 
cu rp, d v thi.
Vt liu mao qut t (MQTBTT)  mt l
c mao qun rng nht, ha hn nhiu ting d
vc hp ph i din trong s t liu SBA-c

 trt t cao, d tng hc mao qun  c,
ng mao qu u ca nhic
[105]. Mao qun rt cng knh d 
 ti-u li th
 vi vt liu vi mao qung h ln [25].
Viu bit liu MQTBTT -
     c nhi      gii. Tuy
 Vit hn ch 
u tc to ra vt liu oxit silic MQTBTT chi,
oxit kim loi chuyn tip ph [2], [3], [6], [14]. Trong khi
 t s u cht
lic ht s  k 
S Thng s [11], [12], Nguyn Th ng s [4nh
2

Th ng s u bi vt liu mao qun SBA-15,
SBA-16 bp ph i
ng vt li
      -15, mt trong nh i din ca vt liu
MQTBTTt nhit vt liu nn hp
d c bit c hp ph n
t nhi v t liu SBA-15.
u bi u ch t liu mi vc
ng, x  nhi
v thi s  m  vic x p
cht hc hc bng k thut hp ph ho
 v ti  
n SBA-t cht n ng nhm
mt hp ph ng dng x p cht h
c hc. Pha hop ph 

2
O
3
, mt oxit kim loi
ng vi vt liu Fe
2
O
3
-SBA-c h
ng vi CO-SBA-    p ph
c chn d kh a pha hot b hp
phi vng -ZnO/SBA-
   hai ch  n CdS-TiO
2
(TiO
2
-CdS/SBA- 
t cht c kin. TiO
2

u nhiu nhc 
 dt ch ho
 ngo  s d kin, vic bin
n pht ra. Hai pha ho c thit
k dt lin ch
ho ngoi tr  kin: (i) giảm năng
lượng vùng cấm i vghép với một chất bán dẫn khác
 ho kin,  t cm quang.
i vi TiO
2

, ch  i vt hc hi
c ch u trong lum nhum. Ni dung
a lun 
3

- Bi mt vt liu mao qu-15 bng oxit st 
cacbonyl, nhm to ra vt lit b m ci thin kh 
hp ph ca vt lii vi mt s cht hc hc nhum
c. T t mi quan h git b mt ca vt liu
hp ph t b hp ph c tho lun.
- u tng hp vt liu ZnO pha t-15
(N-ZnO/SBA-15)  composit TiO
2
-A-15 (TiO
2
-CdS/SBA-
15) ng dng  quang trong phn y xanh metylen (MB) 
metyl da cam (MO).
Cấu trúc của luận án gồm các phần sau:
- M u
- u
- u
- t qu o lun
- Kt lun
- Danh mn lu
- u tham kho
- Ph lc

4


TU

1.1. Vt liu mao qu trt t
c nhng hn ch v c mao qun ca vt liu mao qun nh
(vi mao qun), nhit lic
mao qun l u vt liu mao qu. Tuy
rong lch s tng hp vt liu MQTBTT, hai ct mc ln  k 
th nht, vc c
mt h vt liu mc mao qun t n 20 nm bng vic s dng cht
hong b mng chng c21u kin tng
hn cht ca cht hong b mt, bn cht ca cht phn ng, nhi
tng h 
     -41), c    -48), c  p
(MCM-t s  u v bin
m kh ng dng ca h vt li99]. n th 
th k  n cZhao ng s v vic s d
ng cht ng c)  tng hp h vt liu
SBA-15 [105]. Vt liu vc ln
 4 lc mao qu m ln

2
/g. Mm ca h vt liu SBA-c mao qun ln,
ng mao qun nhiy nhi, h vt liu
SBA- m ra mi trong vic ng dt liu mao qun
trong thc tich s tng hp vt liu MQTBTT gn lin vi vic
n c mao qu cht
i nh amin hoc mu, mao
quc t. Nhng ch l
t hong b mt cetyltrimethylamonium bromua,  to ra mao qun

c l n 2-3 nmi ch
5

nhng polyme poly(ethylen oxit)-poly(propylen oxit)-   
quc t .
-15

Zhao ng s [105 mt loi vt liu m
SBA- vt liu silic dioxit MQTBTT i xng lc tng hp
b s dn poly(ethylen oxit)-poly(propylen
oxit)-poly(ethylen oxit) (Pluronic, EO
y
PO
x
EO
y
ng ch 
n nm trong khong 2- 
th n 6 nm. SBA-c tng hp b  
Pluronic P123 (EO
20
PO
70
EO
20
)  nhi t 35
o
n 80
o
i ta nhn thy

rng khi n c gel silic dioxit tc li,
khi n  i 0,5% ch      -15
c tng pH < 1 (vi axit HCl, HBr, HI, H
2
SO
4
). T
pH t 2-n ca silic  t
silic dioxit gel. T    ng 7, ch     
  t t t    
ng ngun cung cp cho
viu ch SBA-15.
Theo Zhao ng s [104], [105 ca s t-
hp cht trung gian (S
o
H
+
)(X
-
I
+
) S
o
t hong b mt (triblock
copolymer), H
+
X
-
I
+

u Si-OH b 
 cht hong b mt b c t chi dng mt cu
ng cht hp v
cation oxit silic bi s kt hp ca nh
van der Waals. Bng vic s dng ph c ng t n t (electron
paramagnetic resonance), Ruthstein ng s [79 c
ca SBA-n thy nhi
nha oxit silic, phn tr
6

cn x  m m chui ca
  c mao
qu  thng vi mao qun trong
ng SBA-15 do PEO t

1.  ngh cho c-15 sau phn ng  50
o
C
c khi thy nhit.
  a SBA-   c ki     d  ng
ng cht ph n ly mnh to
ng si, ng, cc st trng.
 ng nhit hp ph-kh hp ph  77K
a SBA-u ch s d

. ng nhit hp ph-kh hp ph (b), XRD (c) ca SBA-15
[105].
7

1.2

MCM-ng tng hp ca SBA-
nh (pH < 1),  i  dng t 
kim lo-15  dioxit  ng v mt
 m nhng ng di vi vt li
 mt ct sc cn thi
ng gii quyt v i hoc oxit kim loi hot
liu, (ii) g hb mt mao qun.
1.2i hoc oxit kim loi t liu
   i hoc oxit kim loi  t li   t s 
 bin sau:
a. Tổng hợp thuỷ nhiệt trực tiếp
p chi kim lo
t hn ch  ng
axit mnh, ion kim long  dng t   
ng kim lo  ng thp [76], [106].
b. Ngâm tẩm với các hợp chất kim loại
TT
     TT 

 
 [27], [89].
   , b   m vi tetramineplatinium(II)nitrate
Pt(NH
3
)
4
(NO
3
)
2

 ting s 61 u ch 
si nano b- thun cht ca tin cht kim loi
 u king dioxit silic, ht nano hay s
th u khi ch cn mt lt. M  v
t nano Fe
2
O
3
trong SBA-c tng hp
8

     m vi dung dch Fe(NO
3
)
3
  y   
723K [96]m ru qu  p cht
kim lon vt lin phi thc hiu kin
t n c s c ht.
c. Trao đổi ion của chất ĐHCT với cation kim loại chuyển tiếp
 -
t vi oxit silic. Do vy,  cht liu
MQTBTT  d thay th cation ca ch
loi chuyn ting hi (Al
3+
, Ti
4+
, Sn
4+
nh x

ti b mn, bi vi ph
ca ch  c thay th    
4+
   qun. Bng
 m
mao qun [44],[95].
i vi vt liu Fe-SBA-15, cn nay  tp trung
u v tng hp [23], [58], [86], 2], [94], [89ng dng
c hp ph ng dt hp ph kim loi nng [56], hp
ph phot phat [43], hay hp ph ng thu92n
  u bi SBA-15 bng Fe(III) ng dng hp
ph p cht hc nhu
 Vit hin mt s  t
liu SBA-15. Chng h 
trong mng SBA- n 
 [9], ho Nguyn Hng s u o
hp cht liu mao qu-SBA-15 [8].
Trong lu u bi-15 bng oxit st, hy
vng t b mt ca vt liu SBA-15  ci thin kh p ph
ca vt liu i vc nhum thu Alizarin
Red S (ARS).
9

1.2.2.2. G mt mao qun
    rt nhiu      u g  
b mt mao qun SBA-15u  
 --NH
2
). Lch s g
xu nhu ch mt ca vt liu MCM-41 [15

 g  mt SBA-15ng
hp trc titng hp.
a. Tổng hợp trực tiếp
i ta ng s d bi
NH
2
-(CH
2
)
3
-Si(C
2
H
5
O)
3
     g 
amin, hoc (CH
3
O)
3
-Si(CH
2
)
3
-SH ((3-mercaptopropyl)trimethoxysilane, MPTMS)
 g   i vi tng hp trc ti i ta tr  t n i
ngun cung cn  b thy

t qu n mt sn phc

c gn  m to sn ph c minh
ha  .

3.  to sn phm bing thi [26] (
chc NH
2
).
-1 
    ], [97].        

             
10



3


3



ng

 khi
.
b. Biến tính sau tổng hợp
 bi   ng h i ta d    khoa h   
mt mao qun ca SBA-   -   c gn
bi phn ng gi          (3-

Aminopropyl)triethoxysilane hoc (3-Mercaptopropyl)trimethoxysilanea
-OH b mt. Phn  xy r sau:

4.  phn ng bing hp [35].
Bing hc thc hi
- Phương pháp ghép
              
   ). Oxit silic
11

 -

 
18]:




5.   [87].
- Phương pháp phủ


12


).


7].

. 
 [87].

  
 

 . 


1.2
1.2.3.1. Hp ph
SBA-15 vi di mt l n 800 m
2
c mao
qun ru r t liu hp phc bit, SBA-
c 
13

nh [13ng th to ra hai h mao qu
c lp v 
mi h mao qun t t b m  gi cho b
m  mt vi mao quc [7],
[13]. Chng s [25 ra rng vt liu SBA-15 vi
 t b mt     p s
dng hp ph   c nhum    c. Vi nh i
ng cn hp ph c th g
mt SBA-15.
1.2.3.2. Cht n
Nh  bn nhiy nhi-15
ru kin khc nghi,

-c tm ZrO
2
t nn cho h 
2


2
 
 chuyn lc to CO
2
[78]. Nhng
u mi nht cho thy ch-WS
2
t nn SBA-15 cho hiu
su nh b
          a toluen so vi ch   -
Mo/Al
2
O
3
m [90].
1.2
Do b-
t nhiu kim loc th nghi thay th ng
i ca SBA-15 nhm to hon [90], [96], [102].
1.2u ch vt liu mi
 -t h thng mao quu vi
 m trong khong 2      n  
ng cho vic tt liu nano. Nu khin cho phn ng xy ra
trong h thng mao qun phc nano bi mao qun s

14

n ch s n ht. Mt s  tng h
khi s dng h thng mao qu
 bi ion [95] hoc  mt bi
c kh i
[81], hong vi mt chn phm
 i hoc bi
y  dng khi (bulk). Bu ch c
nhng chn  dng nano vi nh  ng
dng [101].
1.3. -15
         -   
1.7).

Hinh 1.7. -15 [80].
15

Bng 1.1. Th  vt liu SBA-15, aminopropyl-SBA-15
mercaptopropyl-SBA-15  alkyl-SBA-15 theo ISI 
29/5/2013)
c
u

n
SBA-15
aminopropyl-
SBA-15
mercaptopropyl-
SBA-15

Alkyl-
SBA-15
S 
5207
103
26
36
Bng 1.1 cho thy vt liu SBA-15   u s    
u, k t khi vt ling s 
n 2013   quc t s  v vt liu
ch-SBA-15, mercaptopropyl-SBA-1-SBA-15)
u 3 v Tng hp [19],
[63], [82], [42], [65]; ng d t hp ph t mang [47], [66], [82],
[93]; [29], [70], [74]. , SBA- hp
ph thuc nhum  c. Chen ng s 
SBA-15 bng multicarboxylic hyperbranched polyglyc hp ph thuc
nhum thu      i n    c
[30]. Kt qu ch ra rng vt liu SBA-15- p ph i vi
cation thuc nhu  ng hp ph c  i vi met   5
mmolp ph ng nhit hp ph L
ng hc biu kin bc hai. TronAnbia ng s [17-
15 bng 
2
s dng 3-aminopropyl- 
hp ph a SBA-
2
-SBA-15. Kt qu cho thy NH
2
-SBA-
 p ph n SBA-c cho  t ca


2
a vt ling thi x -
baz gi
2
. Cotea ng s [31] 
dng SBA- hp ph  ri thu hi bng
t qu cho thy SBA- p ph
tt polyphenol, m ra mng ng dng mi, s dng SBA-15 trong vic chit
p ch   s dng trong y hc.
16

N vy, theo hiu bit c ,     u
ch   t liu SBA-15 b   vi vi  3-
methacryloxypropyl trimethoxysilane t ngun cung c 
s dng cht hp ph.  kt qu u, tham kh
 , trong lu ti mt SBA-15
ng  tng hp vt liu hp ph: (i) bi mt bi oxit st, vi hy
v mt vt liu s  p ph 
anion thuc nhum; (ii) bi mt bng 
cht b mt vt liu nhng kh p ph p cht hc
hng khp ph trong luMB (cation
thuc nhum), phenol (hp chS (anion thuc nhum).
1.4. H
1.4.1
Dn cht ca lc hp phbit hp ph vp
ph c. Hp ph vi lc vp
ph i lc mang bn chc (lc cc). ,
s hp ph ca than ho  i v       CO
2

, C
2
H
5
OH,
H
2
 (gp ph p ph v hp ph ca cht rn
i vi Ag
+
trong dung dp ph  mt
mng tinh th hp chc AgI.
Do lc hp ph yu, hp ph vhun nghch. Khi nhi c
 gi hp ph giy hp ph vng tin
 nhi thp (th a cht b hp ph). Hp ph v
th p ph p ho lp ho. S
hp ph vt, nhit hp ph rt nhp ph
ng nhit t     ln vi nhit t      c,
khong chng 0,5 - 5 kcal/mol. Trng gia b mt cht hp ph 
pha cha cht b hp ph c thit lp mng
17

ng hoi vp ph vt
p ph yu.
p ph n cht ca mt phn p
ph t thun nghch (rc hin s kh hp ph). Khi nhit
  phn  hp ph p ph c
ng xy ra  nhi cao, nhit hp ph ln, kho
u ng nhit ca phn ng nhing s
hu b hp ph u so vng h hp

ph. Hp ph c xi chng hon, gn
b ng ho a phn      thu  
gi trong cht b hp ph  mt cht rn.
1.4.2
ng hc s d ng hc c
hp ph t hc nhi s d:
u kin bc nhbiu kin bc hai [17], [25], [30].
ng cht h b hp ph q
t
(mg.g
-1
) ti thm
t c:

0 t
t
s
( C C )V
q
m


(1.4)
C
0
C
t
l ca cht h  ti
thm t, mg.L
-1

,
V  ch cht h, L,
m
s
ng ca cht hp ph, g.
u kin bc nht (The Pseudo-First Order Equation) i
 [52] c biu dii dng:

1
()
t
et
dq
k q q
dt
(1.5)
18

q
e
q
t
lng hp ph ti th
ng cht h hp ph ti thm t (mg.g
-1
), k
1
ng s t biu kin
bc nht (thi gian
-1

n s y , kt hp vu kin


1
ln( ) ln( )
e t e
q q q k t  
(1.6)
Nu t hp ph    ng hc biu kin bc nhng
biu din ln(q
e
- q
t
) theo t s ng thng, t  dm c ng
thc vi trc tung s c k
1
q
e
.
u kin bc hai (The Pseudo-c Ho
[40] n dt qu u s hp ph kim loi n 
ng:

2
2
()
t
et
dq
k q q

dt

(1.7)
q
e
q
t
lng hp ph ti th
ng cht h hp ph ti thm t (mg.g
-1
), k
2
ng s t biu kin
bc hai (g.mg
-1
.thi gian
-1
n s ri lt hp vu kin
 cng tuy

2
2
1
t e e
tt
q k q q

(1.8)
Nu s hp ph ng hc biu kin b th biu
din s ph thuc ca t/q

t
theo t ) s ng thng, t 
dm vi tr 
1.4.3 
Ma ving nhit hp ph  ca s
kt hp ca cht b hp ph t hp phi ct h
i vi cht hp ph. ng nhit hp ph ph bin nh  trng
bng hp ph 17], [25], [30].
19

ng nhit hp ph Langmuir d thuyt s hp ph 
lt b hp ph t l t c 
hp ph   mt cht hp ph      i vi cht b hp ph.
ng nhit hp ph Langmuir trong pha ldng:


=









(1.9)
 chuyn v dng tuy
1 1 1 1
q K q C q

e m e m
L

(1.10)
  q
m
  ng hp ph c i (mg/g), q
e
  ng hp
ph ti thng (mg/g), Ce  cht b hp ph ti th
bng (mg/L), K
L
ng s hp ph c c
hp ph.
ng nhit Freundlich d thuyt cho rng b mt cht hp
ph ng nht vp ph c nhau v s ng
hp ph. Quan h ging hp ph  ng ca cht
b hp ph c biu din b   1) vi dng tuy  
 (1.12).

1/ n
e F e
q K C
(1.11)

1
ln ln ln
e F e
q K C
n


(1.12)
q
e
ng hp ph ti thng (mg/g), C
e
ng
 cht b hp ph ti thm ng (mg/l), K
F
(mg.g
1
(L mg
1
)
1/n
) ng s
hp ph Freundlich, 1/n (n > 1) h s p ph - b hp ph.
 ca K
F
= q
e
khi C
e
 K
F
 s d so
 p ph ca mt h  K
F
li h
 p ph cao.

20

D2) K
F
/n  t t  dc
m vi trc tung c th biu din quan h lnq
e
theo lnC
e
.
1.5. 
1.5.1.  ca phn 
Trong h hc  n nhng phn ng xy
ng ca ch c nh ng ca 
 t chn
ng xy ra. i vi cht chn, k 
n s to ra cn t - l tr i electron
git b hp ph  mtu nn. 
t trong nh . Trong khong
 l c ng dng
rc bit quan trng trong x ng.
n t ca kim loi bao gm m vi
nh      c x   c g    
(Valance band      m nh    l   ng
c gn (Condutance Band  c chia
i mt h c gmng
m E
g
 ch gi
kha vt liu d  v

m. Vt lit lit trung gian gia
vt liu d ln (lng
m E
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 ca vt li t qua
 m nh   n, tr  t d   u ki  
nhng ch
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lc li nhng ch
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thp
dn.
Nhng ch
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th 
ng ln