TP CH KHOA HC V CNG NGH

Tp 48, s 1, 2010

Tr. 105-112

KHONG HA METYL DA CAM BNG HIU NG FENTON IN

HA S DNG CATT COMPOSIT POLYPYRROL/OXIT
NGUYN TH L HIN, HONG TH M HNH

1. M U
Cc cht mu h azo hu ht u c cu to mch cacbon phc tp, cng knh, kh b phn
hu bng cc phng php truyn thng: sinh hc, vt l, ho hc... Fenton in ho l mt trong
cc phng php oxy ha tin tin c kh nng khong ha cc hp cht mu h azo vi hiu
qu cao v ha hn nhiu trin vng trong vic x l nc thi cng nghip dt nhum cha cht
mang mu [1 - 3]. Fenton in ha l qu trnh kh oxy ha tan trn in cc catt to ra H2O2,
H2O2 sinh ra c kh nng xy ha kim loi chuyn tip nh Fe2+, Co2+, Cu+... c mt trong dung
dch to gc OH. Cc gc HO to thnh c tnh oxi ho rt mnh, c th oxi ho hon ton hu
ht cc hp cht hu c c hi to thnh CO2 v H2O.
Hiu sut ca phn ng Fenton in ha ph thuc vo rt nhiu yu t, trong vt liu
lm in cc catt l mt trong cc yu t quan trng nht, quyt nh tc to H2O2, l tc
nhn oxy ha trong h Fenton. Cc nghin cu trc y ch ra rng in cc composit trn
c s polypyrol v oxit phc hp cu trc spinel Cu1,5Mn1,5O4 (Ppy/Cu1,5Mn1,5O4) cho kh nng
xc tc in ha phn ng kh oxy to H2O2 vi hiu sut cao trong mi trng axit pH = 3 [4],
cho php ng dng nh in cc catt khong ha phenol [5], methyl [6]... bng phng
php Fenton in ha. Trong khun kh bi bo ny, chng ti kho st qu trnh khong ha
metyl da cam (MO) - mt hp cht diazo in hnh kh phn hy v c hi bng hiu ng
Fenton in ha trn in cc catt composit Ppy/Cu1,5Mn1,5O4.
2. IU KIN THC NGHIM
Cc qu trnh in ha c thc hin trong bnh in ha h ba in cc vi in cc lm
vic l graphit ph mng Ppy cha hoc khng cha oxit Cu1,5Mn1,5O4, din tch 5 cm2, in cc
i l li platin v in cc so snh l calomen bo ha KCl, trn thit b Autolab (H Lan)
c t ti Vin K thut nhit i.
in cc polyme dn c tng hp trn nn cacbon bng phng php in ha trong
dung dch KCl 0,5 M, Ppy 0,1 M c hoc khng cha oxit Cu1,5Mn1,5O4, ti mt dng
2 mA/cm2 vi in tch tng hp l 2 C/cm2 [5].
Qu trnh x l metyl da cam bng hiu ng Fenton in ha c thc hin trong dung
dch Na2SO4 0,05 M, Fe2+ 1 mM pH=3 cha metyl da cam nng 1,53 mM, ti mt dng
in 1 mA/cm2. Dung dch c sc oxy vi tc 0,5 l/pht.
S suy gim cc hp cht hu c trong qu trnh x l c xc nh nh ph hp th UVVis v nhu cu oxy ha hc (COD).
Hiu sut phn hy metyl da cam () c tnh thng qua hp ph (A) nh sau:

105

 (%) =

vi : Ao - hp ph ti thi im ban u (t = 0) v At
hp th ti thi im t

Ao At
.100%
Ao

Hiu sut dng in ca qu trnh khong ha (H) c tnh thng qua bin thin COD
trong qu trnh x l, theo cng thc sau:
H(%)

COD.V .F
8Q

= vi: COD - bin thin ch s COD [g/l], V - Th tch dung dch

in phn [l], F - Hng s Faraday, Q - in tch qua bnh [C].

Cc ha cht s dng trong nghin cu ny u c tinh khit cao (PA).

3. KT QU V THO LUN
3.1. Ph UV-Vis ca metyl da cam
Theo biu thc ca nh lut Buger-Lambert-Beer, nng cht hp th t l thun vi
hp th. Do , nghin cu s bin thin nng metyl da cam trong sut qu trnh x l
bng hiu ng Fenton in ha s dng cc in cc catt khc nhau, chng ti o ph UVVis nh c biu din trn hnh 1, 2 v 3.
16h

thi
gian x
l
0h
1h
3h
5h
7h
9h
11 h
13 h

0h

Hnh 1. Ph UV Vis ca dung dch metyl da cam

ti cc thi im x l khc nhau s dng in cc catt cacbon

Trong dung dch axit (pH < pK), metyl da cam tn ti dng cation, v vy s y v ht
electron c tng cng, h lin hp c m rng, do xy ra hiu ng thm mu, hay
chuyn dch , bc sng hp th cc i chuyn dch v pha bc sng di hn. Ti thi
im ban u (t = 0), ph UV - Vis ca metyl da cam ti pH 3 c c trng bi mt di sng
trong vng nhn thy vi hp th cc i 501 1 nm. y l vng hp th mu xanh da tri,
chnh v vy dung dch metyl da cam ti pH 3 c mu - l mu b ca mu xanh da tri. Hp
th cc i ny tng ng vi s chuyn mc * ca electron lin kt i - N = N trong metyl da cam. Ngoi ra chng ta cn c th quan st c cc di ph khc trong vng
106

t ngoi cc bc sng 275 1 v 320 1 nm tng ng vi s chuyn mc * ca

electron cc lin kt lin hp trong dn sut ca vng thm benzen nh vi lin kt - N =
N - (h thng lin hp ban u).
thi gian
x l
0h
1h
3h
5h
7h
9h
11 h
13 h
15 h

16h
13h

0h

Hnh 2. Ph UV Vis ca dung dch metyl da cam

ti cc thi im x l khc nhau s dng in cc catt cacbon ph Ppy

5h
15 h-24h

1h

0h

thi gian
x l
0h
1h
3h
5h
7h
9h
11 h
13 h
15 h
17 h
19 h
21 h
24 h

Hnh 3. Ph UV Vis ca dung dch metyl da cam ti cc thi im x l khc nhau

s dng in cc catt cacbon ph Ppy(Cu1,5Mn1,5O4)/Ppy

Trong qu trnh x l, i vi c ba in cc catt, cng pic ti 501 nm gim lin tc

v rt nhanh theo thi gian in phn, tng ng vi s phn hy cu trc - N = N -, nguyn
nhn dn ti s mt mu dn ca dung dch in phn. Cng vi s gim cng pic ti 501
nm, cc pic c trng cho hp th ca electron ca ni i lin hp trong vng thm cng
107

gim dn; ng thi xut hin thm pic mi bc sng 2291 nm vi cng ln dn. Kt
qu ny ch ra rng: gc OH u tin tn cng vo nhm mang mu azo, m lin kt N =
N , phn hy h thng cu trc lin hp , gy ra s mt mu ca dung dch. Pic ti 229 nm
c d on l do s chuyn mc * ca vng thm benzen khi h thng lin hp di ban
u b ph v, dn ti s chuyn dch v pha bc sng ngn hn.
So snh ph UV - Vis ca cc dung dch metyl da cam c x l sau cng mt khong
thi gian vi cc in cc catt khc nhau cho thy s phn hy ca metyl da cam khi s dng
in cc cacbon ph Ppy(Cu1,5Mn1,5O4)/Ppy l tt nht, c th hin bi cng cc pic hp
th bc sng 501, 275 v 320 nm gim nhanh nht. Ch sau 2 gi x l khng cn xut
hin pic 275 v 320 nm, thay vo l pic 229 nm c trng cho s hnh thnh sn phm
trung gian, chng t h thng lin hp ban u b gy gn nh hon ton hay qu trnh
khong ha metyl da cam xy ra mnh nht. Cng hp th sn phm trung gian ca in cc
cacbon ph Ppy(Cu1,5Mn1,5O4)/Ppy ny ti bc sng 229 nm cng nh nht chng t hiu qu
cao ca qu trnh khong ha metyl da cam. Sau 15 gi x l vi in cc catt cacbon ph
Ppy(Cu1,5Mn1,5O4)/Ppy, pic hp th tng ng vi lin kt azo ti bc sng 501 nm gn nh
bin mt hon ton, cho php khng nh metyl da cam b phn hu. Kt qu ny cng c
nhn bit rt r bng s mt mu dn ca dung dch metyl da cam theo thi gian x l nh c
biu din trn hnh 4. Tuy nhin, sau x l c th vn tn ti mt phn sn phn trung gian di
dng cc axit cacboxylic mch thng tng ng vi cc pic hp th bc sng ngn hn, gn
vng t ngoi.

Mu cha x l

Sau x l 8 gi

Sau x l 16 gi

Sau x l 24 gi

Hnh 4. S mt mu ca metyl da cam 1,53 mM theo thi gian trong qu trnh x l trn in catt
cacbon ph Ppy(Cu1,5Mn1,5O4)/Ppy bng hiu ng Fenton in ha

T cng hp ph cc i bc sng 501 nm trn ph UV - Vis cho php xc nh

c nng metyl da cam trong dung dch nh phng php ng chun.
Hnh 5 biu din s bin thin nng metyl da cam theo thi gian x l cho thy khi s
dng in cc catt ph mng Ppy(Cu1,5Mn1,5O4)/Ppy, tc suy gim nng metyl da cam
l ln nht. Sau 7 gi x l, nng metyl da cam ban u l 1,53 mM gim xung ch cn 0,2
mM, trong khi i vi in cc cacbon ph Ppy nng ch gim xung 1,11 mM v in cc
cacbon l 1,22 mM. Kt qu ny cho thy vic s dng in cc Ppy(Cu1,5Mn1,5O4)/Ppy cho
hiu qu x l metyl da cam ti u nht.
S bin thin hiu sut phn hy metyl da cam theo thi gian in phn c th hin trn hnh
6. Cc kt qu thu c ch ra rng hiu sut phn hy metyl da cam tng nhanh theo thi gian
in phn. Sau 7 gi x l, hiu sut phn hu metyl da cam t 6,7% i vi in cc cacbon, 14%
i vi in cc cacbon ph Ppy v t ti 35,6% i vi in cc cacbon ph
108

Ppy(Cu1,5Mn1,5O4)/Ppy. iu ny mt ln na khng nh c tnh xc tc vt tri ca in cc

Ppy(Cu1,5Mn1,5O4)/Ppy so vi in cc cacbon c v khng c mng Ppy vng mt oxit, l c s
cho ng dng vo x l nhim mi trng, c bit l mi trng nc.
1.6
1.4
1.2

C (mM)

1.0
0.8
0.6
0.4
0.2
0.0

t (h)

Hnh 5. S bin thin nng metyl da cam theo thi gian in phn s dng cc in cc C (),
C/Ppy (o), C/ Ppy(Cu1,5Mn1,5O4)/Ppy ().
40
35
30

(%)

25
20
15
10
5
0
0

t (h)

Hnh 6. Hiu sut phn hy metyl da cam theo thi gian in phn s dng dng cc in cc C (),
C/Ppy (o), C/ Ppy(Cu1,5Mn1,5O4)/Ppy ().

3.2. Kt qu phn tch COD

Trong qu trnh Fenton in ho, dung dch metyl da cam c ly mu v phn tch COD.
suy gim COD theo thi gian x l cho php khng nh dung dch cha metyl da cam b
khong ho (hnh 7).

109

1000

COD (mg/l)

800

600

400

200

10

12

14

16

18

t (h)

Hnh 7. S suy gim COD phn hy metyl da cam theo thi gian, s dng cc in cc C (),
C/Ppy (o), C/ Ppy(Cu1,5Mn1,5O4)/Ppy ()

i vi c ba loi in cc catt, suy gim ch s COD ln cho thy tc x l metyl

da cam trn cc in cc ny kh cao: Sau 16h x l (tng ng vi Q = 0,08 C/cm2), suy
gim COD t 550 mgO2/l i vi in cc C, 650 mgO2/l vi C/Ppy v 900 mgO2/l vi in
cc C/Ppy(Cu1,5Mn1,5O4)/Ppy. Ti cng mt thi im gi tr in lng Q nh nhau, s suy
gim ch s COD khi s dng cc in cc khc nhau c sp xp theo th t tng dn nh
sau: in cc cacbon, cacbon ph Ppy v ln nht l in cc cacbon ph Ppy(Cu1,5Mn1,5O4)/Ppy.
1400
1200

H (%)

1000
800
600
400
200
0

10

12

14

16

18

t (h)

Hnh 8. Bin thin hiu sut dng in phn hy hon ton metyl da cam theo thi gian,
s dng cc in cc C (), C/Ppy (o), C/ Ppy(Cu1,5Mn1,5O4)/Ppy ().

Hnh 8 biu din s bin thin hiu sut dng in khong ho hon ton metyl da cam
theo thi gian x l bng hiu ng Fenton in ha.
i vi c ba in cc, hiu sut dng in khong ho hon ton metyl da cam u rt
cao, c bit l ti cc thi im u x l khi nng ca metyl da cam trong dung dch cn
110

tng i ln: Sau 1 gi x l, hiu sut dng t 1050% vi in cc catt cacbon, 1116% vi
in cc cacbon ph Ppy v 1313% vi in cc cacbon ph Ppy(Cu1,5Mn1,5O4)/Ppy. Cc gi tr
hiu sut ny cho php khng nh khi dng in chy qua bnh in ha, bn cnh hiu ng
Fenton in ha, cng mt lc c th xy ra nhiu qu trnh ng thi nh oxi ha trc tip
metyl da cam trn in cc ant hoc oxi ha gin tip metyl da cam nh cc tc nhn oxi ha
mnh sinh ra trn in cc ant, ng thi c th sinh ra cc gc c kh nng tip tc khi mo
cho cc phn ng oxy ho metyl da cam v cc sn phm trung gian, do dn n hiu sut
qu trnh x l rt cao.
Theo thi gian, hm lng metyl da cam gim dn dn ti gim dn hiu sut ca qu trnh
in phn. Hiu sut x l metyl da cam trn cc in cc cng c sp xp theo th t tng
dn nh sau: in cc cacbon, in cc cacbon ph Ppy v cao nht l in cc cacbon ph
Ppy(Cu1,5Mn1,5O4)/Ppy. Kt qu ny khng nh in cc Ppy(Cu1,5Mn1,5O4)/Ppy vi s kt hp
gia Ppy c tnh dn in cao vi oxit phc hp, cu trc spinel Cu1,5Mn1,5O4, c hot tnh xc
tc rt tt cho phn ng kh O2 to H2O2, do lm tng tc v hiu sut ca phn ng
khong ho metyl da cam bng hiu ng Fenton in ho so vi in cc catt cacbon c v
khng c mng Ppy.
4. KT LUN
Phng php Fenton in ha cho php khong ha metyl da cam mt hp cht diazo
in hnh, c hi. So vi in cc cacbon v in cc cacbon ph Ppy, in cc catt composit
trn c s Ppy dn in v oxit cu trc spinel Cu1,5Mn1,5O4 c kh nng xc tc tt cho phn
ng kh oxy to hydroperoxit, cho php tng hiu qu x l cht mu metyl da cam bng hiu
ng Fenton in ha. Vi mt dng p t 1 mA/cm2, trong dung dch Na2SO4 0,05M sc
oxy, cha Fe2+ 1mM, metyl da cam 1,53 mM b phn hu v mt mu hon ton sau 15 h x
l vi hiu sut dng in rt cao (trn 100%). Kt qu ny cho php m ra trin vng ng dng
hiu ng Fenton in ha trong vic x l cc hp cht hu c c hi kh phn hu, c nng
cao (khng x l c bng cc phng php truyn thng) nhm gim thiu nhim mi
trng v tit kim nng lng.
TI LIU THAM KHO
1. Guoquan Zhang, Fenglin Yang, Mingming Gao, Xiaohong Fang, and Lifen Liu - ElectroFenton degradation of azo dye using polypyrrole/anthraquinonedisulphonate composite
film modified graphite cathode in acidic aqueous solutions, Electrochimica Acta 53 (2008)
5155-5161.
2. J. M. Peralta-Hernandez, Yunny Meas-Vong, Francisco J. Rodrguez, Thomas W.
Chapman, Manuel I. Maldonado, Luis A. Godnez - Comparison of hydrogen peroxidebased processes for treating dye-containing wastewater: Decolorization and destruction of
Orange II azo dye in dilute solution, Dyes and Pigments 76 (2008) 656-662.
3. Minghua Zhou, Qinghong Yu, Lecheng Lei, Geoff Barton - Electro-Fenton method for the
removel of methyl red in an efficient electrochemical system, Separation and Purification
Tech. 57 (2007) 380.
4. H. Nguyen Cong, K. El Abbassi, P. Chartier - Electrocatalysis of oxygene Reduction on
Polypyrrole/Mixed Valence Spinel Oxide Nanoparticles, Journal of the Electrochem. Soc.
149 (2002) A525.
111

5. Nguyn Hng Thi, Nguyn Th L Hin - Ppy(oxit phc hp spinel) tng hp in ho

trn graphit ng dng lm in cc catt trong x l mi trng nh hiu ng Fenton in
ho, Tp ch Ha hc 47 (1) (2009).
6. Nguyn Th L Hin, Trn Th Ti - Khong ha metyl bng phng php Fenton
in ha, To ch Ha hc, Tp ch Ho hc 47 (2) (2009) 207-212.
SUMMARY
MINERALISATION OF METHYL ORANGE BY ELECTRO-FENTON PROCESS
USING A POLYPYRROLE/OXIT COMPOSITE CATHODE
To promote treatment efficiency, an efficient undivided electrochemical system using a Ppy
(Cu1,5Mn1,5O4) composite film on graphite cathode with high production rate of hydrogen
peroxide was applied to the electro-Fenton oxidation of a model azo dye, methyl orange (MO).
The decrease of MO concentration and treatment efficiency during the electro-Fenton process
was investigated by UV-Vis spectra and COD analyses. The results obtained confirme that using
the cathode of PPy(Cu1,5Mn1,5O4) allowe treating MO wiht very high efficiency. A solution of
1,53mM MO could be mineralized nearly totally by a electrical charge of 0.08 A.h with a very
high current yield.
a ch:
Trung tm ng dng v Chuyn giao cng ngh,
Vin Du kh Vit Nam.

112

Nhn bi ngy 12 thng 9 nm 2008