J . C h e m . S c i. Vo l. 1 2 7 , N o . 3 , M a r c h 2 0 1 5 , p p . 5 3 7 5 4 6 . c I n d i a n A c a d e m y o f S c i e n c e s .

D O I 1 0 .1 0 0 7 /s1 2 0 3 9 -0 1 5 -0 8 0 6 -1

M a n g a n e s e z in c fe r r ite n a n o p a r tic le s a s e f c ie n t c a ta ly s ts fo r w e t
p e r o x id e o x id a tio n o f o r g a n ic a q u e o u s w a s te s

M A N J U K U R I A N a n d D I V YA S N A I R
D e p a rtm e n t o f C h e m is try , M a r A th a n a s iu s Co lle g e , Ko th a m a n g a la m , 6 8 6 6 6 6 , In d ia
e -m a il: m k @m a c o lle g e .in

M S re c eiv ed 6 M arch 2 0 1 4 ; rev is ed 2 0 S e p tem b e r 2 0 1 4 ; a cc e p ted 2 4 S e p tem b e r 2 0 1 4

A b s t r a c t . M a n g a n e s e s u b s titu te d z in c n a n o p a r tic le s , M n x Z n 1 x F e 2 O 4 ( x = 0 .0 , 0 .2 5 , 0 .5 , 0 .7 5 , 1 .0 ) p r e p a r e d
b y s o l g e l me th o d w e re fo u n d to b e e f c ie n t c a ta ly s ts fo r w e t p e ro x id e o x id a tio n o f 4 -c h lo r o p h en o l. Co mp lete
d e g ra d a tio n o f th e ta rg e t p o llu ta n t o c c u rre d w ith in 9 0 m in a t 7 0 C . Z in c s u b s titu tio n e n h a n c e d th e c a ta ly tic
e f c ie n c y a n d th e u n s u b s titu te d Z n F e 2 O 4 o x id iz e d th e ta rg e t c o m p o u n d c o m p le te ly w ith in 4 5 m in . S tu d ie s o n
th e e ffe c t o f re a c tio n v a ria b le s re v e a le d th a t o n ly a s m a ll a m o u n t o f th e o x id a n t, H 2 O2 (3 4 m L ) is re q u ire d fo r
c o m p le te d eg ra d a tio n o f 4 -c h lo ro p h e n o l. M o re th a n 8 0 % o f 4 -c h lo ro p h e n o l w a s re mo v e d a t c a ta ly s t c o n c e n tra -
tio n s o f 1 0 0 m g /L . D ire c t c o rre la tio n b e tw e e n th e a m o u n t o f c a ta ly s t p re s e n t a n d th e ex te n t o f d e g ra d a tio n o f
4 -c h lo ro p h en o l w a s o b s e rv e d , ru lin g o u t h e s te ro g e n e o u s -h o m o g e n e o u s m e c h a n is m . T h e c a ta ly s ts a re re u s a b le
a n d c o m p lete d e g ra d a tio n o f ta rg e t p o llu ta n t o c c u rre d a fte r v e s u c c e s s iv e ru n s . T h e ex te n t o f iro n le a c h in g
w a s f a irly lo w a f te r v e c o n s e c u tiv e c y c le s in d ic a tin g th e m e c h a n is m to b e h e te r o g e n e o u s .
K e y w o r d s. S p in e l f e r r ite s ; c a ta ly tic a c tiv ity ; w e t p e r o x id e o x id a tio n ; 4 - c h lo ro p h e n o l; w a te r tr e a tm e n t.

1 . I n t r o d u c t io n
S u s ta in a b le w a s te w a te r m a n a g e m e n t a n d r e u s e o f
in d u s tria l wa ste w a te r a re c ritic a l iss u e s fo r th e d ev e lo p -
m e n t o f h u m a n a c tiv itie s a n d e n v iro n m e n t c o n s e rv a tio n .
T h e tre a tm e n t a n d s a fe d is p o sa l o f h a z a rd o u s o rg a n ic
w a s te m a te ria l in a n e n v ir o n m e n ta lly a c c e p ta b le m a n n e r
a n d a t a r e a s o n a b le c o s t is a to p ic o f g re a t im p o rta n c e .
B io lo g ic a l p ro c e s s e s a re e m p lo y e d a s b a s e lin e tre a t-
m e n t f o r m o s t o rg a n ic wa s te in wa te r sin c e th e y fu l l
th e tw o c r ite ria m e n tio n e d b e fo re . Ho w ev e r, th e se p ro -
c e s s e s d o n o t a lw a y s g iv e s a tis f a c to r y r e s u lts , s in c e
m a n y o rg a n ic c o m p o u n d s a re in h ib ito r y , to x ic o r re s is -
ta n t to b io lo g ic a l tre a tme n t. In s o m e c a s e s , ev e n in b io -
lo g ic a l s y s te m s a d a p te d fo r th e to x ic ity , h ig h v a r ia tio n
o f o rg a n ic c h a rg e c a n g e n e ra te n e g a tiv e e ff e c ts d u r-
in g tr e a tm e n t, c a u s in g th e e m iss io n o f u n d e s ira b le
a m o u n ts o f to x ic p ro d u c ts in th e tre a te d w a ste wa te r.
C o u p lin g c h e m ic a l p r e -o x id a tio n w ith b io lo g ic a l p o st
tre a tm e n t wo u ld b e b e n e c ia l s in c e it c a n le a d to
in c reased treatme n t efcien cies. No wa d ay s, ch emical
o x id a tio n p ro c e s se s a re fo c u s e d o n g iv in g p a r tia lly
o x id iz e d e f u e n ts c o n ta in in g re a d ily b io d eg ra d a b le
c o m p o u n d s th a t a llo w its c o m b in a tio n w ith b io lo g i-
c a l tr e a tm e n t. A d v a n c e d O x id a tio n P ro c e s s e s (AO P s ),
d e n e d a s a q u e o u s p h a se o x id a tio n p ro c e s s e s b a se d o n
th e u s e o f h y d r o x y l r a d ic a l a s o x id a n t a r e a ttr a c tiv e
c h e m ic a l te c h n iq u e s fo r th e d e stru c tio n o f o rg a n ic p o l-
l u t a n t s d u r i n g w a t e r t r e a t m e n t .1 ,2 W e t A i r O x i d a t i o n
( WAO ) a n d We t P e r o x id e O x id a tio n ( W P O ) a r e tw o
m a jo r te c h n iq u e s th a t c o m e u n d e r th is c a teg o ry . In We t
A ir O x id a tio n , th e d eg ra d a tio n ra te is s tro n g ly lim ite d
b y th e m a s s tra n s fe r o f m o lec u la r o x y g e n fr o m th e
g a s to th e liq u id p h a s e . We t P ero x id e O x id a tio n ta k e s
a d v a n ta g e o f u s in g h y d ro g e n p e ro x id e a s th e liq u id
o x id a n t, w h ic h a v o id s g a s -liq u id m a s s tra n s fe r lim ita -
tio n s . T h e s e v e r e o p e r a tio n c o n d itio n s o f WAO m a k e it
m o r e c a p ita l in te n siv e wh e r e a s W P O d e m a n d s a lo w e r
ca p ital. In WPO, h y d ro x y l rad icals can b e p ro d u ce d
fr o m H 2 O 2 u s in g h o m o g e n e o u s m e th o d s s u c h a s F e n to n
r e a c tio n 3 ,4 o r h e te r o g e n e o u s c a ta ly s ts lik e m e ta l o x id e s ,
c l a y s , s u p p o r t e d m e t a l c a t a l y s t s , e t c .5 ,6 A p p l i c a t i o n o f
h o m o g e n e o u s F e n to n re a c tio n d e m a n d s a c id i c a tio n o f
th e w a te r (o p tim a l p H a ro u n d 3 ) a n d in v o lv e s a d d itio n a l
c o n ta m in a tio n o f th e tre a te d wate r b y iro n a n d m in e ra l
a c id s . H e te ro g e n e o u s c a ta ly tic w e t p e ro x id e o x id a tio n
h as sev eral ad v a n tag es o v e r th e classica l h o mo g en eo u s
F e n to n lik e p ro c e s s e s s u c h a s e n h a n c e m e n t o f c a ta ly tic
a c tiv ity , la c k o f s e c o n d a ry p o llu tio n a n d th e p o s s ib ility
o f r e u s e o f c a ta ly s t in s u c c e s s iv e c y c le s .
C h lo ro p h e n o ls (C P s) a re a g ro u p o f p rio rity to x ic
p o llu ta n ts lis te d b y th e U S E PA in th e C le a n Wa te r Ac t
a n d b y th e E u ro p e a n U n io n D ec is io n , d u e to th e ir h ig h

Fo r co rresp o n d en ce to x ic ity a n d lo w b io d eg ra d a b ility . T h e y a r e r e le a se d

5 3 7
5 3 8 M a n ju Ku r ia n a n d D iv y a S N a ir
in to wa te r a s wa s te g e n e ra te d fr o m in d u stria l a c tiv itie s
lik e p e tro c h e m ic a l, p h arm a c e u tic a l, w o o d p r e se rv in g ,
p la stic , p e s tic id e a n d h e rb ic id e u s e .7 T h ey c a n a lso
b e p ro d u c e d b y e n v iro n m e n ta l d e g ra d a tio n o f m o re
c o m p lex m o le c u le s lik e c h lo ro p h e n o x y a c e tic a c id s a n d
c h lo r o b e n z e n e s . D u e to th e ir n u m e ro u s o rig in s , c h lo ro -
p h e n o ls c a n b e f o u n d in g ro u n d w a te r, w a stew a te r a n d
s o ils a n d ev e n in tro p h ic c h a in o f p la c e s w ith v e ry lo w
p o llu tio n lev e ls . In p e o p le , d ev e lo p m e n ta l, b e h av io u ra l,
n e u ro lo g ic , e n d o c r in a l, re p ro d u c tiv e a n d im m u n o lo g ic
a d v e rs e h e a lth e ffe c ts h av e b e e n lin k e d to th e se c o m -
p o u n d s a s th ey a r e c o n s id e re d to a c t a s u n c o u p le rs
to o x id a tiv e d e p h o s p h o r y la tio n .8 T h e y p e r s is t f o r lo n g
p e rio d s o f tim e in th e e n v iro n m e n t a n d c a n b e b io -
m a g n i e d th r o u g h th e fo o d c h a in . Th e im p o rta n c e o f
p h e n o lic in d u s tr ia l e f u e n ts b e sid e s fro m th e ir p o te n -
tia l to x ic ity is in c re a se d b y th e h ig h q u a n titie s th a t a re
d is p o se d ev e n tu a lly . A m o n g c h lo ro p h e n o ls , th o s e w ith
c h l o r i n e i n t h e 4 th p o s i t i o n a r e m o r e t o x i c t h a n o t h e r s .
B io lo g ic a l tre a tm e n t h as lo w re m o v a l e f c ie n c y a n d
th e rm a l a n d c h e m ic a l tre a tm e n ts h av e b e e n d ev e lo p e d
in th e la st few y e a rs fo r th e d e to x i c a tio n o f th e s e
o rg a n ic p o llu ta n ts.
F e rrite s a re c e ra m ic fe rro m a g n e tic m a te ria ls w ith
g e n e r a l c h e m i c a l f o r m u l a M I I F e I2 I I O 4 w h e r e M r e p r e -
s e n ts a m e ta llic c a tio n lik e F e , M n , M g , N i, C o , Z n , C u ,
A l o r a m ix tu r e o f th e se . T h ey c ry s ta lliz e in to th e s p in e l
s tr u c tu re in w h ic h , th e s ite s o c c u p ie d b y th e c a tio n s
a re o f two ty p e s : te tra h e d ra l (T d ) a n d o c ta h e d r a l (O h )
s ite s . S p in e l f e r r ite s h a v e b e e n in te n s iv e ly s tu d ie d d u e
to th e ir a p p lic a b ility in b ro a d a re a s lik e h ig h d e n s ity
in f o rm a tio n s to ra g e sy s te m s , fe rro u id te c h n o lo g y ,
m a g n e to c a lo ric re frig e ra tio n , m e d ic a l d ia g n o s tic s , g a s
s e n s o r s , g u id e d d r u g d e liv e r y , e tc ., o w in g to u n iq u e
c h a ra c te ris tic s lik e la rg e m a g n e to c ry s ta llin e a n iso tro p y ,
h ig h c o e r c iv ity , h ig h C u r ie te m p e r a tu r e , la rg e m a g -
n e to s tr ic tiv e c o e f c ie n t, c h e m ic a l s ta b ility , c o r r o s io n
r e s i s t a n c e a n d m e c h a n i c a l h a r d n e s s .9 ,1 0 R e c e n t l y f e r r i t e
re s e a r c h h a s b e e n sh ifte d to wa rd s d e v e lo p in g th e s e
m a te r ia ls in n a n o m e tric s c a le s a s th e p e rfo rm a n c e in
th e ir c o n v e n tio n a l b u lk p re p a ra tio n ro u te s is r e a c h in g
th e ir lim its d u e to th e ir h ig h e r e le c tr ic a l c o n d u c tiv ity
a n d d o m a in wa ll re s o n a n c e . T h e y h av e w e ll-e s ta b lish e d
c a ta ly tic p ro p e rtie s a lso fo r re a c tio n s lik e d e c o m p o si-
tio n o f a lc o h o ls a n d h y d r o d e s u lp h u riz a tio n o f p e tro -
le u m c ru d e . Th e s e p ro p e rtie s d e p e n d o n th e c h a rg e o n
th e c a tio n , th e n a tu re o f th e m e ta llic c a tio n a n d th e
s ite d is trib u tio n o f c a tio n s a m o n g T d a n d O h s ite s .
I n s p in e ls , th e o c ta h e d ra l s ite s a r e a lm o s t e x c lu s iv e ly
e x p o s e d in th e c ry s ta llite s a n d c a ta ly tic a c tiv ity is
m a in ly d u e to o c ta h e d r a l c a tio n s .1 1 S in c e th e f e r r ite
n a n o p a r tic le s a re m a g n etic , th e s e c a n b e e a s ily re m o v e d
fro m th e r e a c tio n m ix tu re a fte r c a ta ly s is b y m a g n e tic
m e th o d s . P r o s p e c tiv e a p p lic a tio n s o f f e r r ite s a s g r e e n
o x id a tio n c a ta ly s ts fo r th e re m o v a l o f p e rs iste n t o rg a n ic
p o llu ta n ts c a n b e p re d ic te d d u e to th e th e rm a l sta b ility
a n d th e v a ria b le o x id a tio n s ta tes o f th e m e ta l io n s .
Th e p re s e n t p a p e r p ro b e s th e fe a s ib ility o f u sin g
m ix e d fe rr ite n a n o p a rtic le s fo r th e d eg ra d a tio n o f
o rg a n ic a q u e o u s wa ste s u s in g p e r o x id e o x id a tio n ta k -
in g 4 -c h lo ro p h e n o l a s th e m o d el c o m p o u n d . A s e rie s o f
f e r r o s p in e ls v iz . M n x Z n 1 x F e 2 O 4 ( x = 0 , 0 .2 5 , 0 .5 , 0 .7 5
a n d 1 ) wa s p re p a re d b y so l-g e l au to c o m b u s tio n m e th o d
u s in g e th y le n e g ly c o l a s th e g e la tin g a g e n t. L iq u id
p h a s e c a ta ly tic p e ro x id e o x id a tio n o f 4 -c h lo ro p h e n o l
u n d e r m ild c o n d itio n s wa s stu d ie d in d e ta il u s in g
b o th G a s C h r o m a to g ra p h y (G C) a n d C h e m ic a l O x y g e n
D e m a n d ( C O D ) m e a s u re m e n ts. T h e p ro c e s s w a s o p ti-
m iz e d w ith r e s p e c t to d iffe re n t re a c tio n v a ria b le s lik e
tim e , te m p e r a tu re , 4 -c h lo ro p h en o l c o n c e n tra tio n , p e r-
o x id e c o n c e n tra tio n a n d c a ta ly s t c o n c e n tra tio n . Th e
r e u s a b ility o f th e c a ta ly s ts f o r v e c o n s e c u tiv e c y c le s
w a s in v e stig a te d a n d th e p o s sib ility o f ir o n le a c h in g
w a s c h e c k e d u s in g A to m ic Ab s o r p tio n S p e c tro m e te r
(A A S ) . T h e p re p a re d c a ta ly s ts w e re c h a ra c te riz e d b y
X -ra y D iffra c tio n (X R D ) a n d Tra n s m is s io n E le c tro n
M ic ro sc o p y (T EM ) a n d X -r a y Flu o r e sc e n c e ( XR F ).
2 . E x p e r im e n ta l
Pu re ( 9 9 .9 % ) F e ( N O 3 ) 3 .9 H 2 O , Z n ( N O 3 ) 2 .6 H 2 O ,
M n ( N O 3 ) 2 .6 H 2 O a n d e th y le n e g ly c o l f r o m M e r c k ,
In d ia w e re u se d a s s ta rtin g ma te r ia ls w ith o u t fu rth e r
p u ri c a tio n . Th e m ix e d s p in e ls o f Mn x Z n 1 x F e 2 O 4
( x = 0 , 0 .2 5 , 0 .5 , 0 .7 5 , 1 .0 ) w e r e p r e p a r e d b y th e
s o l- g e l a u to c o m b u s tio n m e th o d . R e q u ire d s to ic h io -
m e tr ic r a tio o f F e ( N O 3 ) 3 .9 H 2 O , M n ( N O 3 ) 2 .6 H 2 O a n d
Z n ( N O 3 ) 2 .6 H 2 O w e r e d is s o lv e d in m in im u m a m o u n t
o f eth y len e g ly c o l at ro o m temp eratu re an d h eated at
6 0 C to o b ta in a w e t g e l. Th is g e l d r ie d a t 1 2 0 C se lf-
ig n ited to fo rm a u ffy p ro d u c t wh ich was calcin e d
a t 4 0 0 C fo r 4 h to a c h ie v e tran s fo rm a tio n in to sp in e l
p h a s e . T h e fe rrite p o w d e r was th e n s iev e d th ro u g h
a 9 0 m m m e s h . Th e p r e p a red fe rrite c o m p o sitio n s
w e r e Z n F e 2 O 4 , M n 0 .2 5 Z n 0 .7 5 F e 2 O 4 , M n 0 .5 Z n 0 .5 F e 2 O 4 ,
M n 0 .7 5 Z n 0 .2 5 F e 2 O 4 a n d M n F e 2 O 4 .
P h a s e id e n ti c a tio n o f th e p re p a re d p a rtic le s w e re
p erfo rmed u sin g Bru k er AXS D8 Ad v a n ce X-ra y
d i f f r a c t o m e t e r w i t h C u K ( = 1 . 5 4 0 6 A ) a s t h e r a d i a -
tio n so u rc e . T h e av e ra g e c ry s tallite s iz e (D ) o f th e fe r-
rite p a rtic le s wa s d e te rm in e d fro m X- ra y d iffra c to g ra m s
u s i n g t h e D e b y e - S c h e r e r f o r m u l a : D ( h k l) = 0 . 9 / c o s
w h e r e , D ( h k l) i s t h e a v e r a g e c r y s t a l l i t e s i z e ( n m ) , i s
th e w av e le n g th (n m ), is th e fu ll w id th a t h a lf m a x -
im u m (ra d ia n ) a n d is th e Bra g g a n g le . T h e la ttic e
 M a n g a n e s e z in c fe r r ite n a n o p a r tic le s a s e f c ie n t c a ta ly s ts
p a ra m e te r a wa s c a lcu la te d u sin g th e re la tio n , a =
d ( h 2 + k 2 + l2 ) 1/2 . S in c e e a c h p r im itiv e u n it c e ll o f th e
s p in e l s tr u c tu re c o n ta in s 8 m o le c u le s; X -ra y d e n s ity
(d x ) w a s c a lc u la te d a cc o r d in g to th e re la tio n d x =
8 M/Na3 wh ere, N is Av o g ad ro n u mb er an d M is mo lec-
u la r w e ig h t o f th e s a m p le . T h e m e a s u r e d d e n s ity o r b u lk
d e n s ity ( d B) w a s c a lc u la te d f r o m m a s s a n d b u lk v o lu m e
o f th e sa m p le p e lle ts u sin g th e fo rm u la , d B = m / r2 h
w h e re , m is th e m a ss o f th e s a m p le ta k e n , r is th e ra d iu s
o f th e sa m p le p e lle t a n d h is th e h e ig h t o f th e p e lle t.
F ro m th e b u lk d e n sity an d X -ra y d e n s ity , p o ro s ity , P o f
th e fe rrite n a n o p a rtic le wa s d e te rm in e d u s in g th e re la -
tio n , P = 1 - (d B/d X) . Th e p a r tic le siz e , d is trib u tio n o f
n a n o p a r tic le s a n d su rfa ce m o rp h o lo g y w e re c o n rm e d
u s i n g P H I L I P S M o d e l C M 2 0 0 T r a n s m? i s s i o n E l e c t r o n
M ic r o s c o p e w ith a r e s o lu tio n o f 2 .4 A w ith th e h e lp
o f Im a g e J s o ftwa re . S to ic h io m e try o f p r e p a re d c a ta -
ly sts was v eried u sin g Bru k er PIONEER mo d el X-ray
u o re s c e n c e s p e c tr o m e te r.
We t p e r o x id e o x id atio n o f 4 - c h lo ro p h e n o l wa s
s tu d ie d in liq u id p h a s e , in a 2 5 0 m L two - n e c k e d ro u n d
b o tto m e d a sk e q u ip p ed w ith a wa te r c o n d e n s e r, th e r-
m o m e te r a n d m a g n e tic stirre r. T h e re a c tio n m ix tu re
wa s a llo w e d to e q u ilib ra te a t 7 0 C p rio r to th e in itia -
tio n o f th e re a c tio n . Liq u id sa m p le s w e re p e rio d ic a lly
w ith d r a w n f r o m th e r e a c tio n m ix tu r e a n d q u a n tita tiv e ly
a n a ly z e d u s in g P e rk in E lm e r C la ru s 5 8 0 Ga s C h ro -
m a to g ra p h o p e ra tio n a l with a n E lite -5 c a p illa r y c o lu m n
a n d F la m e Io n iz a tio n D ete c to r. T h e p ro d u c ts w e re id e n -
ti e d b y G C M S a n a ly s is o n a Va r ia n 1 2 0 0 L S in g le
Q u a d ru p o le u sin g H e as th e c a rrie r g a s . T h e re m o v a l
(% ) w a s c a lc u la te d a s th e to ta l a m o u n t o f c h lo ro p h e -
n o l tra n sf o r m e d in to p ro d u c ts . T h e e x te n t o f o x id a tio n
wa s a ls o s tu d ie d u s in g C h e m ic a l O x y g e n D e m a n d m e a -
s u r e m e n ts e m p lo y in g s tan d a rd d ic h ro m a te m e th o d . T h e
e rr o r p e rc e n ta g e b e tw ee n th e re s u lts o f a n a ly s is wa s
le s s th a n 5 % . T h e in u e n c e o f v a rio u s r e a c tio n v a ri-
a b le s lik e n a tu re o f th e ca ta ly s t a n d its d o s a g e , s u b stra te
c o n c e n tra tio n , re a c tio n te m p e ra tu re , tim e , o x id a n t c o n -
c e n tra tio n e tc wa s s tu d ie d in d e ta il. T h e re u s a b ility o f
th e c a ta ly s t wa s c h e c k e d fo r v e c o n s e c u tiv e c y c le s a n d
th e a m o u n t o f iro n le a c h e d d u r in g th is wa s q u a n ti e d
u sin g P e rk in E lm e r A n a ly st 7 0 0 A to m ic A b s o r p tio n
Sp ectro p h o to meter.
3 . R e s u lts a n d D is c u ss io n
3 .1 C h a ra c te riz a tio n o f m a n g a n e s e z in c n a n o fe r rite s
R e c o rd in g X -ra y d iffra c tio n p a tte rn o f p o w d e re d p o ly -
c ry s ta llin e s a m p le s b y p o w d e r d iffr a c to m e te r m e th o d
h a s m a n y a p p lic a tio n s lik e q u a lita tiv e p h a s e a n a ly sis ,
5 3 9
q u a n tita tiv e p h a s e a n a ly s is , d e te r m in a tio n o f u n it c e ll
p a ra m e te rs , stu d y o f p r e fe rre d o r ie n ta tio n a n d d e te rm i-
n a tio n o f p a rtic le siz e . X -ra y d iffra c to g ra m s o f th e m a n -
g a n e s e z in c fe rrite s a g re e c lo s ely w ith th e sta n d a rd v a l-
u e s g iv e n in th e J C P D S d a ta c ard s (7 9 -1 1 5 0 , 5 2 -0 2 7 8 ),
c o n rm in g th e s in g le p h a se s p in e l fo rm a tio n ( g u re 1 ).
We ll-d e n e d a n d b ro a d d iffra ctio n p e a k s c o rre sp o n d -
in g to c h a ra c te ris tic c r y s ta llo g ra p h ic p la n e s lik e ( 2 2 0 ),
(3 1 1 ), (4 0 0 ) , (4 2 2 ), (5 1 1 ) a n d (4 4 0 ) o f th e s p in e l s tru c -
tu re c a n b e o b se rv e d in th e g u re s . T h e s tro n g e s t re e c -
tio n c o m e s fro m th e (3 1 1 ) p la n e , w h ic h c o rre s p o n d s
to c u b ic sp in e l s tru c tu re . T h e m ix e d f e rro s p in e ls a re
tre a te d a s s o lid s o lu tio n s o b ta in e d b y th e s u b s titu tio n
o f m a n g a n e s e fe r rite s w ith z in c io n s . In in te rp re tin g th e
X R D p ro le o f s u c h su b s titu tio n s , th e s u b s titu tio n a l s ite
c a n b e c o n s id e r e d a s o c c u p ie d b y a c o m p o site a to m
m a d e u p o f a p p r o p ria te p o rtio n s o f th e in v o lv e d a to m s ,
s t a ti s tic a ll y .1 2 ,1 3 H e n c e t h e X R D p r o l e o f th e s u b s t i-
tu te d s a m p le s is e x p e c te d to b e in te rm e d ia te b e tw e e n
th o s e o f th e p u re s u b s ta n c e s . X RD p a tte rn s o f th e m ix e d
fe rrite s a re id e n tic a l with th o se o f m a n g a n e s e f e rrite
p ro v in g th a t z in c su b stitu tio n d o e s n o t c h a n g e th e sp in e l
fe rrite s tru c tu re o f m a n g a n e se fe r rite .
Th e d iffe re n t p a r a m e te rs c a lc u la te d f ro m X R D p r o -
le is ta b u la te d in ta b le 1 . Th e av e ra g e c ry sta llite siz e
o f th e m a n g a n e se z in c fe r rite sy s te m s is fo u n d to b e in
th e r a n g e o f 1 3 .3 2 3 .9 n m . T h e s u b s titu tio n o f z in c in
M n F e 2 O4 c o rre s p o n d s to a lin e a r d e c re a se in p a rtic le
s iz e , w h ic h s u g g e s ts th e f o r m a tio n o f a c o m p o s itio n a lly
h o m o g e n e o u s s o lid so lu tio n . Th is wa s p ro b a b ly d u e to
th e re a c tio n c o n d itio n s , wh ic h fav o u re d th e fo rm a tio n
o f n e w n u c le i p r e v e n tin g f u r th e r g r o w th o f p a r tic le s
F ig u r e 1 . X -ra y p ro le o f M n x Zn (1 x ) F e 2 O 4 ( x = 0 .0 , 0 .2 5 ,
0 .5 , 0 .7 5 , 1 .0 ) .
5 4 0 M a n ju Ku r ia n a n d D iv y a S N a ir
T a b le 1 . D a ta o n c ry s ta llite s iz e (D ), la ttic e c o n s ta n t (a ), X -ra y d e n s ity (d x ) , b u lk
d e n s ity (d B) a n d p o ro s ity (P ) o f th e p re p a re d fe rrite s a m p le s o b ta in e d fro m X -ra y
d iffra c to g ra m s .
C ry s ta llite s iz e D (n m )
S a m p le XRD TEM
Mn Fe2O4 2 3 .9 2 1
M n 0 .7 5 Z n 0 .2 5 F e 2 O 4 1 3 .5 2 0
M n 0 .5 Z n 0 .5 F e 2 O 4 1 3 .3 1 9
M n 0 .2 5 Z n 0 .7 5 F e 2 O 4 1 5 .9 1 7
Zn Fe2O4 2 3 .1 1 4
w h e n th e z in c c o n c e n tra tio n w a s in c r e a s e d . Ve g a r d s
law is a lin e a r re la tio n c o rr e la tin g th e la ttic e p a r a m e te rs
a n d th e c o m p o s itio n o f th e s o lid so lu tio n .14 L a ttic e
p a ra m e te r in c r e a s e s lin e a rly w ith in th e ra n g e o f 8 .3 1
8 . 4 3 A , w i t h a n i n c r e a s e i n c o n c e n t r a t i o n o f z i n c ,
o b e y in g Ve g a r d s la w. T h e o b s e r v e d la ttic e p a r a m e te r
is h ig h e r f o r Z n F e 2 O4 w h ic h c o u ld b e a ttrib u te d to
th e r e p la c e m e n t o f s m a lle r s iz e d iro n c a tio n b y la rg e r
s iz e d z in c c a tio n . A s a re s u lt, th e s iz e o f th e u n it c e ll
is in c re a se d . X -ra y d e n s ity , b u lk d e n s ity a n d p o r o s ity
o f d iffe re n t c o m p o s itio n s d o n o t s h o w a n y s ig n i c a n t
c h a n g e w ith z in c c o n te n t.
T h e p a rtic le s iz e o b ta in e d fro m X -ra y d iffra c tio n
p ro le is g e n e ra lly la rg e r th a n th e s iz e o b ta in e d fro m
Tra n s m is s io n E le c tro n M ic r o g ra p h s b e c a u s e X -ra y
in te n s ity is p ro p o rtio n a l to th e a v e ra g e p a r tic le v o lu m e ,
w h ile th e p a rtic le s iz e o b ta in e d fro m T E M im a g e s re p -
re s e n ts th e a v e ra g e ra d iu s. M o re o v e r, th e s iz e d is tri-
b u tio n s o b ta in e d fr o m T E M im a g e s a re re stric te d to
p rim a ry p a rtic le s a n d d o n o t in c lu d e s e c o n d a r y p a rti-
c le s fo rm e d b y e p ita x ial a tta c h m e n t. S e c o n d a ry p a r ti-
c le s a re fo rm e d fro m in te g e r m u ltip le s o f p rim a ry p a r-
tic le s a n d c a n h a v e a s ig n i c a n t in u e n c e o n th e v o l-
u m e d is tr ib u tio n , e v e n a t r e la tiv e ly lo w c o n c e n tr a tio n .1 5
Tra n s m is s io n E le c tro n Mic ro g ra p h s o f th e p re p a re d
Mn 1 x Z n x F e 2 O 4 sa m p le s a re g iv e n in g u re 2 (a e ).
T h e p a rtic le s iz e d a ta a n d th e ir d istrib u tio n c a n b e
o b ta in e d b y h is to g ra m m e th o d b y c o u n tin g m o re th a n
2 0 p a r tic le s fro m e a c h m ic ro g ra p h a n d re p re s e n tin g in
a g r a p h ic a l f o rm a t. I n th is m e th o d , th e p a rtic le s iz e a n d
its d is trib u tio n is p re s en te d in th e fo rm o f a n u m b e r-
f r e q u e n c y h is to g r a m .1 6 F ig u r e 3 ( a e ) s h o w s th e n u m -
b e r fre q u e n cy h is to g ra m s o f p a rtic le s iz e d a ta o f d if-
fe r e n t c o m p o sitio n s o f M n a n d Zn in lin e a r s c a le . An
a d v a n ta g e o f th is k in d o f p lo ttin g m e th o d is th a t it is
e a s ie r to n d a b e tte r d istrib u tio n o f n a n o p a rtic le s. F ro m
h is to g ra m m e th o d , it is fo u n d th a t th e p a rtic le s iz e o f
d iff e re n t c o m p o s itio n s o f m a n g a n e s e a n d z in c fe rr ite
n a n o c a ta ly s ts v a ry b e twe e n 1 2 2 2 n m a n d p a rtic le s iz e
v a ry lin e a rly w ith in c re as e in m a n g a n e se c o n c e n tra tio n
(ta b le 1 ).
a ( A ) d x (g /m 3 ) d B (g /m 3 ) P (%)
1 8 .3 1 5 .3 4 3 .2 4 3 9 .3 2
1 8 .3 5 5 .3 2 2 .9 8 4 3 .9 8
1 8 .3 7 5 .3 4 3 .0 6 4 2 .6 9
1 8 .4 0 5 .3 4 3 .2 5 3 9 .1 3
2 8 .4 3 5 .3 3 4 .0 1 2 4 .7 1
Ele m e n ta l c o m p o sitio n a n a ly s is o f th e s y n th e s iz e d
fe rrite n a n o c a ta ly s ts is im p o rta n t s in c e th e n a tu re
a n d th e c o n c e n tra tio n o f d iffe re n t e le m e n ts p re s e n t
c a n d e te rm in e th e s u rfa c e m o rp h o lo g y w h ic h in tu rn
c a n a ffe c t th e ir c a ta ly tic a c tiv itie s. T h e e x p e rim e n ta l
a n d e x p e c te d v a lu e s re g a rd in g th e s to ic h io m e try o f
m a n g a n e se z in c fe rrite c a ta ly sts u s in g X -ra y u o re s-
c e n c e (X R F ) stu d ie s a r e ta b u late d in ta b le 2 . It is c le a r
fr o m th e ta b le th a t th e e le me n ta l c o m p o sitio n o f
M n 0 .2 5 Z n 0 .7 5 F e 2 O 4 , M n 0 .5 Z n 0 .5 F e 2 O 4 a n d M n 0 .7 5 Z n 0 .2 5
F e 2 O 4 a re n o t in c lo s e a g re e me n t w ith th e ir d e s ire d
c o m p o s itio n . T h is is a n a n o m alo u s b e h a v io u r in c o m -
p a ris o n w ith th e re s u lts o b ta in e d in th e c a s e o f c o b a lt
s u b s titu tio n in Z n F e 2 O 4 w h ic h is e x p la in e d in o u r p re -
v io u s p a p e r.1 7 I n th e p r e s e n t c a s e , a la rg e d is c r e p a n c y
is o b s e r v e d b e twe e n th e ex p erim e n ta l a n d e x p e c te d
v a l u e s o f M n 0 .2 5 Z n 0 .7 5 F e 2 O 4 , M n 0 .5 Z n 0 .5 F e 2 O 4 a n d
M n 0 .7 5 Z n 0 .2 5 F e 2 O 4 s a m p l e s . T h i s m a y b e d u e t o t h e f a c t
th a t s u b s titu tio n o f M n in Z n Fe 2 O 4 is fo u n d to b e d if-
c u lt d u e to th e sig n i c a n t v a ria tio n in a to m ic r a d ii o f
man g a n ese an d zin c .
3 .2 E ffe c t o f r e a c tio n v a r ia b le s in th e w e t p e r o x id e
o x id a tio n o f 4 -c h lo ro p h e n o l
T h e re a c tio n v a ria b le s lik e te m p e ra tu re , 4 -c h lo ro p h e n o l
c o n c e n tr a tio n , c a ta ly s t c o n c e n tr a tio n a n d o x id a n t c o n -
c e n tr a tio n c a n a ff e c t th e o x id a tio n a c tiv ity o f th e c a ta -
ly sts to a c o n s id e ra b le e x te n t. He n c e , th e e ffe c t o f th e s e
v a r i a b l e s w a s s t u d i e d i n d e t a i l u s i n g M n 0 .2 5 Z n 0 .7 5 F e 2 O 4
a s th e re fe re n c e c a ta ly s t. Th e sta b ility o f th e c a ta ly s ts
to wa rd s th e re a c tio n c o n d itio n s a s w e ll a s th e ex te n t
o f iro n le a c h in g in to th e a q u eo u s m e d iu m w e re a ls o
in v e s tig a te d .
Th e in u e n c e o f in itia l c o n ce n tra tio n o f 4 -c h lo ro p -
h e n o l in w a te r w a s s tu d ie d b y k e e p in g th e a m o u n t o f
c a ta ly s t a s 5 0 0 m g /L , h y d ro g e n p e ro x id e a s 4 m L a n d
tim e a s 7 5 m in . 2 5 m L so lu tio n s o f 4 -c h lo ro p h e n o l w ith
c o n c e n tr a tio n r a n g in g f r o m 0 .7 5 1 .7 5 g /L w e r e u s e d .
T h e r e s u lts o f th e s tu d y c o n d u c te d a t 7 0 C a r e g iv e n
in g u r e 4 a . A s e x p e c te d , c o m p le te d e g r a d a tio n o f
 M a n g a n e s e z in c fe r r ite n a n o p a r tic le s a s e f c ie n t c a ta ly s ts 5 4 1

F ig u r e 2 . (a -e ). Tra n sm is s io n E le c tro n M ic ro g ra p h s o f M n x Z n (1 X) F e 2 O 4 ( x = 0 .0 , 0 .2 5 , 0 .5 , 0 .7 5 , 1 .0 ) n a n o p a r tic le s .

5 4 2 M a n ju Ku r ia n a n d D iv y a S N a ir

F ig u r e 3 . (a -e ). T E M -H is to g ra m s o f M n x Z n (1 x ) Fe2O 4 (x = 0 .0 , 0 .2 5 , 0 .5 , 0 .7 5 , 1 .0 ) n a n o p a r tic le s .

4 -c h lo ro p h e n o l o c c u rs at lo w c o n c e n tra tio n s . I n crease th a t c o n v e rs io n s a re c a lc u lated as weig h t p erc en tag e o f

in th e targ et co mp o u n d c o n cen tra tio n d e c re a ses th e u n re a c te d c h lo ro p h e n o l.
d eg rad atio n rate. Th ese resu lts a re su p p o rted b y COD A se rie s o f w e t p e ro x id e o x id a tio n s w e r e p e r f o r m e d
me asu re men ts. Th e d ecrease in c h lo ro p h en o l co n v er- in th e te m p e ra tu re r a n g e o f 2 5 7 0 C k e e p in g th e
s io n a t h ig h c o n c e n tra tio n s c a n b e a ttrib u te d to th e fact a m o u n t o f c a ta ly s t a s 5 0 0 m g /L a n d h y d ro g e n p e ro x id e
 M a n g a n e s e z in c fe r r ite n a n o p a r tic le s a s e f c ie n t c a ta ly s ts 5 4 3

T a b le 2 . E le m e n ta l c o m p o s itio n o f M n x Z n 1 x F e 2 O 4 ( x - 0 .0 , 0 .2 5 , 0 .5 , 0 .7 5 , 1 .0 )
n a n o p artic le s b y X -R a y F lu o re s c e n c e s p e c tro s c o p y .

E x p e rim e n ta l v a lu e E x p e c te d v a lu e
Cataly st Zn Mn Fe O Zn Mn Fe O
Zn Fe2O4 0 .9 9 0 1 .9 9 4 1 0 2 4
M n 0 .2 5 Z n 0 .7 5 F e 2 O 4 0 .1 2 0 .9 2 1 .9 7 3 .9 9 0 .7 5 0 .2 5 2 4
M n 0 .5 Z n 0 .5 F e 2 O 4 0 .3 6 0 .6 6 1 .9 9 3 .9 9 0 .5 0 .5 2 4
M n 0 .7 5 Z n 0 .2 5 F e 2 O 4 0 .3 5 0 .6 5 2 .0 4 .0 0 .7 5 0 .2 5 2 4
Mn Fe2O4 0 0 .8 3 2 .1 4 .0 0 1 2 4

a s 4 m L . F ig u re 4 b re p re s e n ts th e in u e n c e o f re a c tio n
te m p e ra tu re o n c h lo r o p h e n o l c o n v e rs io n a n d C O D
re m o v a l a t 7 5 m in . It c a n b e o b s e rv e d th a t te m -
p e ra tu re h a s a m a rk e d in u e n c e o n ta rg e t p o llu ta n t
re m o v a l. T h e c a ta ly tic e f c ie n cy is m o r e p ro n o u n c e d
ev e n a t lo w e r te m p e ra tu re s . A t 2 5 C , c o n v e rs io n
o f ch lo ro p h en o l is ab o v e 9 0 %. Ho wev er, th e COD
re m o v a l is in th e ra n g e o f 3 5 5 5 % , in d ic a tin g th e p re s -
e n c e o f p e rs iste n t o rg a n ic in te rm e d ia te s in th e re a c tio n
m ix tu re .
A d ju s tin g th e o x id a n t d o s e is a c ritic a l f e a tu r e in w e t
p e ro x id e o x id a tio n p ro ce s se s sin c e H2 O 2 c o n su m p tio n
is a d e te rm in in g c o m p o n e n t o f th e tre a tm e n t c o st. T h e
effe ct o f o x id an t d o sa g e was re so lv ed b y ch an g in g th e
a m o u n t o f o x id a n t in th e ra n g e o f 1 5 m L a n d k e e p in g
th e a m o u n t o f c a ta ly s t c o n s ta n t a s 5 0 0 m g /L. F ig u re 4 c
d e p ic ts th e re s u lts in 7 5 m in a t 7 0 C . It c a n b e o b s e rv e d
th a t a s th e d o s a g e o f o x id iz in g a g e n t in c re a s e s, h ig h e r
ta rg e t p o llu ta n t r e m o v a l is a c h iev e d . T h e re s u lts fro m
G C a n a ly s is a re s u b sta n tia te d b y C O D r e s u lts a s w e ll.
In th e p re s e n t stu d y , o n ly s m all a m o u n ts o f th e o x i-
d a n t ( 3 4 m L ) a re re q u ir e d fo r c o m p le te d e g ra d a tio n o f
4 -c h lo ro p h e n o l, c o m p a re d to rep o rte d lite ra tu re ,18 th u s
re d u cin g th e c o st o f treatme n t p ro c ess. Ag ain , a t lo wer
o x id a n t c o n c e n tra tio n s, C O D re m o v a l is lo w, in d ic a t-
in g th e p re s e n c e o f in te rm e d ia te s p e rs is tin g in th e
re a c tio n m ix tu re th a t g e ts o x id iz e d a t h ig h e r o x id a n t
d o sa g e s. T h e in c re a se in o x id a n t c o n c e n tr a tio n h a s b e e n
re p o rte d to in c re a s e th e d e e p o x id a tio n o f p ro d u c e d
in te rm e d ia te s to p o ly m e ric p ro d u c ts. T h e h ig h c o n c e n -
tra tio n o f h y d ro g e n p e ro x id e c a n a ls o a c c e le r a te se lf-
d e c o m p o s itio n o f th e o x id a n t, r e d u c in g th e c o n v e rs io n

F ig u r e 4 . E f c ie n c y o f ca ta ly tic o x id a tio n o f c h lo ro p h e n o l u n d e r re a c tio n c o n d itio n s : C a ta ly s t 5 0 0 m g /L , H 2 O 2 (3 0 % v /v )

4 mL, ch lo r o p h e n o l- 1 g /L (2 5 m L ), Te m p e r a tu r e - 7 0 o C . Va r ia tio n o f , ( a ) c h lr o p h e n o l, ( b ) Te m p e r a tu r e , (c ) H y d r o g e n p e r o x -
id e 3 0 % (v /v ) a n d (d ) c a taly s t. F ille d m a rk e rs re p re s e n t % re m o v a l o f c h lo ro p h e n o l fro m G C a n d u n lle d m a rk e rs re p re s e n t
% remo v al o f COD.
5 4 4 M a n ju Ku r ia n a n d D iv y a S N a ir
o f c h lo ro p h e n o l. S ev e ra l a u th o r s h av e re p o rte d d e c re a s e
i n t h e r e a c t i o n r a t e a t h i g h o x i d a n t c o n c e n t r a t i o n s .1 9 ,2 0
H o w ev e r, th is e ff e c t is n o t o b s e rv e d in th e p re s e n t c a s e .
T h e c o n c e n tra tio n o f c a ta ly st u s e d fo r th e liq u id
p h a se w e t p e ro x id e o x id a tio n is a n im p o r ta n t p a ra m e te r
d e te rm in in g th e e f c ie n cy o f th e c a ta ly s t. Th e r e su lts
o f th e stu d ie s o n th e in u e n c e o f c a ta ly s t c o n c e n tra tio n
a t 7 0 C in 7 5 m in , b y k e e p in g th e a m o u n t o f h y d ro -
g e n p e ro x id e a s 4 m L is g iv e n in g u re 4 d . It c a n
b e s e e n th a t th e re is a d ire c t c o rr e la tio n b e tw e e n th e
a m o u n t o f c a ta ly s t p re s en t a n d th e e x te n t o f d eg ra d a tio n
o f 4 -c h lo ro p h e n o l. M o re th a n 8 0 % o f th e ta rg e t p o llu -
ta n t is re m o v e d a t lo w c a ta ly s t c o n c e n tra tio n s o f ev e n
1 0 0 m g /L . H o w ev e r, a t lo w c a ta ly s t c o n c e n tra tio n s, th e
re d u c tio n in C OD is o n ly a b o u t 1 5 3 0 % in d ic a tin g th e
p re s e n c e o f o rg a n ic d e g r a d a tio n p ro d u c ts p e rs is tin g in
th e sy s te m . Th e s y m b io tic d e p e n d e n c e b e tw e e n e f -
c ie n cy a n d c a ta ly tic m a ss in d ic a te s th a t th e p ro c e s s ru n s
o n th e su rfa c e o f th e c a ta ly s t. H av in g in m in d th a t th e
e x p e rim e n ts a re c a rrie d o u t w ith c a ta ly st fra c tio n s o f
n a n o m e tric siz e , it c a n b e a s su m e d th a t th e o u te r s u r-
fa c e o f th e c a ta ly st g ra in is u se d to a g re a t e x te n t. In
m a n y r e p o r ts th e r e w a s a n e g a tiv e d e p e n d e n c e o f r a te
o n c a ta ly s t c o n c e n tr a tio n su g g e s tin g th e o c c u rr e n c e o f
te r m in a tio n s te p s o n th e c a ta ly s t s u r f a c e .2 1 ,2 2 H o w e v e r ,
th is was n o t o b serv ed in th e p resen t case.
T h e ex p e rim e n ta l c o n d itio n s o p tim iz e d fo r e c o n o m -
ic a l, c o m p le te a n d e f cie n t r e m o v a l o f ta rg e t p o llu ta n t
fro m wa te r a r e 4 -C P ( 1 g /L ) to h y d ro g e n p e ro x id e in
th e r a tio o f 2 5 m L to 4 m L , c a ta ly s t d o s a g e , 0 .5 g a n d
te m p e ra tu re , 7 0 C .
3 .3 E ffe c t o f tim e in th e W P O o f 4 - C P
T h e o b je c tiv e o f th is ex p e rim e n ta l re s e a rc h is to e v a l-
u a te th e e f c ie n c y o f mix e d m a n g a n e s e z in c f e rrite s
to w a rd s w e t p e ro x id e o x id a tio n o f o rg a n ic p o llu ta n ts
ta k in g 4 - c h lo ro p h e n o l a s th e m o d e l c o m p o u n d . T h e
c a ta ly tic a c tiv ity o f d iffe r e n t c o m p o s itio n s o f n a n o f e r-
rite s to w a rd s th e d e g ra d a tio n o f 4 -c h lo ro p h e n o l w ith
h y d ro g e n p e ro x id e wa s s tu d ie d b y k e e p in g th e a m o u n t
o f c a ta ly s t a s 5 0 0 mg /L a n d h y d ro g e n p e ro x id e
a s 4 m L . T h e r e su lts o f th e in v e stig a tio n a t 7 0 C a re
p re s e n te d in g u re 5 . C o m p le te d e g r a d a tio n o f 4 -
c h lo r o p h e n o l o c c u rs w ith in 9 0 m in with th e c a ta ly s ts
u n d e r s tu d y . Z in c s u b stitu tio n e n h a n c e s th e c a ta ly tic
e f c ie n c y o f m a n g a n e se fe rr ite a n d th e u n s u b s titu te d
Z n F e 2 O 4 o x id is e s th e ta rg e t c o m p o u n d c o m p le te ly
w ith in 4 5 m in . T h is tr e n d in o x id a tio n a c tiv ity w a s
fo llo w e d b y C O D m e a su r e m e n ts o f th e re a c tio n m ix -
tu r e a ls o . C O D is a m o re im p o rta n t p a ra m e te r
th a n c h lo ro p h e n o l c o n v e rs io n sin c e it m e a su re s th e
c o n ta m in a n t a b a te m e n t c o n s id e rin g th e to x ic n a tu re o f
F ig u r e 5 . We t p e ro x id e o x id a tio n o f 4 -c h lo ro p h e n o l o v e r
M n x Z n (1 x ) F e 2 O 4 ( x = 0 .0 , 0 .2 5 , 0 .5 , 0 .7 5 , 1 .0 ) . R e a c tio n
C o n d itio n s : H 2 O 2 (3 0 % v /v ) 4 m L , c a ta ly s t- 5 0 0 m g /L ,
c h lo ro p h e n o l- 1 g /L (2 5 m L ), Te m p e ra tu re - 7 0 C . F ille d
mark ers rep resen t % remo v al o f ch lo ro p h en o l fro m GC an d
u n lle d m a rk e rs jo in e d b y d o tte d lin e s re p re s e n t % re m o v a l
o f COD.
th e in te rm e d ia te s a n d p r o d u c ts fo rm e d . T h e re s u lts o f
C OD m e a s u r e m e n ts c o n rm th e re s u lts o b ta in e d b y
G C a n a ly s is . A n o th e r sig n i c an t o b se rv a tio n f ro m th e
g u re is th a t th e d e g ra d a tio n o f 4 -c h lo ro p h e n o l a n d
C OD re d u c tio n is slo w d u rin g th e in itia l p e rio d s o f th e
re a c tio n a n d a s tim e a d v a n c e s, it a c c e le ra te s . G e n e r-
a lly , c a ta ly se d w e t o x id a tio n s p r e se n t s im ila r f e a tu r e s
in c o n c e n tra tio n -tim e p ro le s . I n sev e ra l a p p lic a tio n s ,
th e s e p ro c e s s e s h a v e a slo w c o n v e rs io n ra te in th e in i-
tia l in d u c tio n p e rio d f o llo w e d b y a fa s te r s ta g e n a lly
in c re a s in g to to ta l d eg ra d a tio n o f o rg a n ic c o m p o u n d s .
T h e in itia l in d u c tio n p e rio d is a ttrib u te d to th e tim e
n e c e ss a ry to re a c h a c ritic a l co n c e n tra tio n o f o rg a n ic
ra d icals.
F e rrite s a r e c e ra m ic fe r ro ma g n e tic m a te r ia ls w ith
g e n e ra l c h e m ic a l f o rm u la MF e2 O 4 w h e re M re p re s e n ts
a m e ta llic c a tio n lik e F e , Mn , Mg , N i, C o , Z n , C u , A l
o r a m ix tu r e o f th e s e . T h e y c ry s ta lliz e in to th e sp in e l
s tru c tu re in w h ic h , th e site s o c c u p ie d b y th e c a tio n s
a r e o f two ty p e s : te tr a h e d ra l (A ) a n d o c ta h e d r a l (B )
s ite s . B a s e d o n th e p a rtia l o cc u p a n cy o f th e s e s ite s ,
s p in e ls a r e d iv id e d in to th r e e ; a ) n o r m a l s p in e l in w h ic h
M o c c u p ie s A s ite s a n d F e , B s ite s, b ) in v e rse sp in e l
in w h ic h M o c c u p ie s B site s to g e th e r w ith h a lf o f F e
a to m s , th e o th e r h a lf b e in g o n A s ite s a n d c ) m ix e d o r
ra n d o m sp in el in wh ich b o th M an d Fe o ccu p y b o th
A a n d B s ite s . In s p in e l fe r rite s th e o c ta h e d ra l s ite s ,
ra th e r th a n te tr a h e d ra l s ite s a re m o re ex p o se d in th e
o u te r s u r fa c e a n d h e n c e th e o c ta h e d r a l c a tio n s a r e c o n -
s id e re d to b e re s p o n s ib le fo r c ata ly tic a c tiv ity , w h ic h is
 M a n g a n e s e z in c fe r r ite n a n o p a r tic le s a s e f c ie n t c a ta ly s ts 5 4 5

e s s e n tia lly a su rfa c e p h e n o m e n a . Z n F e 2 O 4 is a n o rm a l T a b le 3 . S ta b ility o f cataly s t to ward s wet p e ro x id e

s p in e l in w h ic h th e te tra h e d ra l s ite s a re lle d b y Z n 2+ o x id a tio n .
io n s a n d th e o c ta h e d r a l s ite s b y F e 3 + io n s e x c lu s iv e ly . No . o f % remo v al o f 4 -CP % re d u c tio n Amo u n t o f Fe
It c a n b e sa fe ly d e d u c ed th a t F e 3+ /F e 2+ re d o x c o u p le cy cles fro m water o f COD le a c h e d (p p m )
p la y s a s ig n i c a n t ro le in th e w e t p e ro x id e o x id a tio n
re a c tio n s a n d h e n c e th e h ig h e r a c tiv ity o f Zn F e 2 O 4 . 1 1 0 0 9 5 .9 1 .2
H o w ev e r, in m ix e d sp in e l fe rrite s, a s th e c o n c e n tra - 2 1 0 0 9 4 .8 1 .1
3 1 0 0 9 4 .5 3 .2
tio n o f th e d iv a le n t m e ta l io n s in c r e a s e s , it g iv e s r is e 4 1 0 0 9 1 .8 3 .7
to c h a n g e s in c a tio n d is tr ib u tio n in th e c ry sta l la ttic e 5 1 0 0 8 4 .8 4 .5
w ith o u t a ffe c tin g th e sp in e l fe rr ite stru c tu r e . With p ro -
g r e s s iv e a d d itio n o f M n to Z n F e 2 O 4 , th e n o r m a l s p in e l R e a c t i o n C o n d i t i o n s : C a t a l y s t - M n 0 .2 5 Z n 0 .7 5 F e 2 O 4 , H 2 O 2
(3 0 % v /v ) 4 m L , c a ta ly s t- 5 0 0 m g /L , c h lo ro p h e n o l- 1 g /L
s tr u c tu re g e ts c o n v e rte d to in v e rs e s p in e l s tru c tu re in
(2 5 mL), Temp eratu re- 7 0 C
w h ic h M n 2+ io n s p a rtially s u b s titu te th e F e 3+ io n s in
th e o c ta h e d ra l s ite s. T h e su b s titu tio n o f M n in to th e
s p in e l s tru c tu re o f Z n F e 2 O 4 is v e ry sm a ll a s c o n rm e d o f s tr o n g ly a d s o r b e d re a c tio n p r o d u c ts o r b y -p r o d u c ts
b y X -ra y u o re s c e n c e . T h e re p la c e m e n t o f a c tiv e F e 3+ c a n b lo c k p a rt o f th e s u rfa c e , th u s p ro d u c in g a g e n -
io n s b y Mn 2+ io n s o ccu rs to a small ex ten t o n ly a n d u in e d e a c tiv a tio n w h ic h u ltim a te ly fa v o u r s s u r fa c e o v e r
h e n c e th e c a ta ly tic a c tiv ity is n o t m u c h a ff e c te d b y m a n - o x i d a t i o n r e s u l t i n g i n a m u c h g r e a t e r d e a c t i v a t i o n . 2 4 ,2 5
g a n e s e s u b s titu tio n g iv in g a lm o s t s im ila r r e d u c tio n in H e n c e , th e re u s a b ility o f th e p re p a r e d s y s te m s w a s
C O D v a lu e ( g u re 5 ). Als o , r e d o x n a tu re o f Mn is c o n - c h e c k e d b y r e ta in in g a c a ta ly st b a tc h a n d u s in g it fo r
s id e r a b ly lo w c o m p a r e d to F e , th e o x id a tio n a c tiv ity s ev e ra l c y c le s w ith o u t tre a tm e n t b e tw e e n c y c le s. T h e
d e c r e a s e s w ith s u c c e s s iv e a d d itio n o f M n to Z n F e 2 O 4 . c a ta ly s t a n d re a c ta n ts w e re p la c e d in th e re a c to r fo llo w -
We t p e r o x id e o x id a tio n o f c h lo ro p h e n o ls h a s b e e n in g th e p ro c e d u r e p r ev io u sly d e sc r ib e d . It is in te re s t-
re p o rte d to o c c u r o v e r s ev e ra l c a ta ly sts . A lF e p illa re d in g to n o te th a t th e a c tiv ity o f th e c a ta ly s ts re m a in s th e
clay s g av e 7 0 % remo v al o f 4 -ch lo ro p h en o l a t 5 0 C s a m e a fte r v e su c c e ss iv e ru n s (ta b le 1 ) . T h e c a ta ly s t
w h e n a 1 2 5 p p m a q u e o u s s o lu tio n w a s u s e d .6 2 m M re m o v e d a b o u t 8 5 % o f th e C O D ev e n o n its fth c y c le .
s o lu tio n o f 4 - c h lo ro p h e n o l wa s c o m p le te ly d eg ra d e d Ap p lic a tio n o f h e te ro g e n e o u s c a ta ly sts in p u ri c a -
u sin g h y d r o ta lc ite /c la y co m p o s ite u sin g 4 0 m M H 2 O 2 a t tio n o f w a ste w a te r re q u ire s th at th e y b e sta b le to w a rd s
4 0 C1 . Co mp lete remo v al o f 4 -c h lo ro p h en o l o ccu rred at m e ta l io n ex c h a n g e b e tw e e n th e c a ta ly st a n d th e liq u id
1 0 0 C w ith 2 .5 c m 3 o f H 2 O 2 a n d a n in itia l c o n c e n tr a tio n p h a s e u n d e r th e o p e ra tin g c o n d itio n s . C o n tin u o u s a n d
o f 5 0 0 p p m a f te r 9 0 m in in th e a b s e n c e o f a c a ta ly s t.23 g r a d u a l le a c h in g c a n le a d to d e a c tiv a tio n o f th e c a ta ly s t.
S ev e ra l c o m p o u n d s lik e n a p h th a le n e , o u re n e , a c e - It is a lso im p o rta n t to m a k e s u re th a t th e re a c tio n a s w e ll
n a p h th a le n e , c h ry se n e , e tc ., h a v e b e e n re p o rte d a s p ro d - a s th e c a ta ly s ts d o n o t c a u s e a n y k in d o f f u r th e r p o llu -
u c ts in w e t p e ro x id e o x id a tio n o f 4 -c h lo ro p h e n o l in tio n in w a te r. L e a c h in g s tu d ie s a re a lso v a lu a b le in th e
l it e r a tu r e .9 ,2 2 Z h o u e t a l. r e p o r te d b e n z o q u i n o n e a n d t h e s e n s e th a t th ey c a n p ro v id e in s ig h ts to th e m e c h a n is m o f
c h lo r in a te d b e n z o q u in o n e s a s in te rm e d ia te p ro d u c ts .1 th e re a c tio n , w h e th e r h o m o g e n e o u s o r h e te ro g e n e o u s .
In o u r s tu d y , tr ia c e to n e p e ro x id e is th e m a jo r in te r- T h e iro n c o n c e n tra tio n in th e liq u id p h a se a fte r o n e
m e d ia te id e n ti e d b y GC MS a n a ly s is . O th e r p ro d u c ts h o u r r e a c tio n wa s r e p e a te d ly me a su re d u s in g A to m ic
o b s e rv e d in tra c e s a re a c e to n e , 4 h y d ro x y 4 m e th y l A b s o r p tio n S p e c tro m e te r a n d th e r e s u lts a re p re s e n te d
2 p e n ta n o n e , 2 ,5 h e x a n e d io n e , x y le n e s a n d b e n z o - in ta b le 3 . Fo r m a n g a n e s e z in c fe rrite n a n o p a r tic le s , th e
q u in o n e . T h e p re s e n c e o f tria c e to n e p e ro x id e c a n b e a m o u n t o f iro n le a c h e d re m a in s a b o u t 1 p p m in tw o
d u e to th e c o n v e rs io n o f a c e to n e b y e x c e s s h y d ro - c o n s e c u tiv e ru n s a n d th e n it in c re a s e s to a b o u t 4 p p m .
g e n p e ro x id e p re s e n t in th e re a c tio n m ix tu re , w h ic h It c a n b e c o n c lu d e d th a t iro n le a c h in g is fa ir ly lo w a fte r
p ro d u c e s th e p o ly m e r in p re se n c e o f a c id ic c a ta ly s ts v e c o n s e c u tiv e c y c le s in d ic a tin g th e m e c h a n is m to b e
lik e fe r rite s . Th u s , th e ta rg e t p o llu ta n t is c o m p le te ly h etero g en eo u s.
re m o v e d a s sim p le o rg a n ic in te rm e d ia te s w h ic h in tu rn
a re o x id iz e d c o m p le te ly .
4 . C o n c lu s io n s
3 .4 S ta b ility o f th e c a ta ly s t
Wet Pero x id e Ox id atio n ap p ears to b e a p ro m is in g te c h -
C a ta ly tic s ta b ility is a n im p o rta n t fa c to r o f c o n tin u in g n o lo g y fo r th e r e m o v a l o f c h lo ro p h e n o ls f ro m w a s te
c o n c e r n f o r in d u s tr ia l a p p lic a tio n s a n d w a s g iv e n water sin ce c o mp lete remo v al o f th e targ et co mp o u n d
u tm o st im p o rta n c e in th e p re se n t stu d y . T h e p re s e n c e c a n b e a c h ie v e d a t m ild c o n d itio n s (7 0 C, 4 mL o f
5 4 6 M a n ju Ku r ia n a n d D iv y a S N a ir
H 2 O 2 ) . M a n g a n e s e z in c fe rrite n a n o p a rtic le s a c t a s e f -
c ie n t c a ta ly s ts fo r th e o x id a tio n o f 4 -c h lo ro p h e n o l in
p re s e n c e o f h y d r o g e n p e ro x id e a s o x id a n t. C o m p le te
re m o v a l o f th e ta rg e t co m p o u n d w a s a c h iev e d w ith in
4 5 m in a t 7 0 C o v e r zin c f e rrite c a ta ly st w ith m o re
th a n 9 9 % re d u c tio n in C O D . O n ly sm a ll a m o u n ts o f
th e o x id a n t (3 4 m L ) a re r e q u ire d fo r c o m p le te d e g ra -
d a tio n o f 4 -c h lo ro p h e n o l, th u s re d u c in g th e c o st o f
tre a tm e n t p r o c e ss . D ire ct c o rre la tio n e x is ts b e tw e e n th e
a m o u n t o f c a ta ly s t p re se n t a n d th e e x te n t o f d e g ra d a -
tio n o f 4 -c h lo ro p h e n o l ru lin g o u t th e h e te ro g e n e o u s -
h o m o g e n e o u s m e c h a n ism . Mo re th a n 8 0 % o f th e ta r-
g e t p o llu ta n t wa s r e m o v e d a t a c a ta ly st c o n c e n tra tio n a s
lo w a s 1 0 0 m g /L . T h e c a ta ly s ts a re re u s a b le a fte r v e
s u c c e s siv e ru n s. T h e e x te n t o f iro n le a c h in g is fa irly
lo w a fte r v e c o n se c u tiv e c y c le s in d ic a tin g th a t th e
m e c h a n is m is h e te ro g e n e o u s .
A c k n o w le d g e m e n t
F in a n c ia l a s sis ta n c e fro m th e D e p a r tm e n t o f S c ie n c e
a n d Te c h n o lo g y , I n d ia th r o u g h F a s t T r a c k S c h e m e f o r
Yo u n g S c ie n tis ts is g r a te f u lly a c k n o w le d g e d .
R e fe r e n c e s
1 . Z h o u S , G u C , Q ia n Z, X u J a n d X ia C 2 0 1 1 J. C o llo id
In te r fa c e S c i. 3 5 7 4 4 7
2 . Ku ria n M , J o y M a n d R a j D 2 0 1 2 J. Po ro u s M a te r. 1 9
6 3 3
3 . Kwo n B G, Lee D S, Kan g N a n d Yo o n J 1 9 9 9 Wa te r
Res. 3 3 2 1 1 0
4 . Lu M 2 0 0 0 Ch emo sp h ere 4 0 1 2 5
5 . K u r ia n M , E ld h o s e A a n d T h a s le e n a b i R M 2 0 1 2 I n te r.
J. En viro n . Res . 6 6 6 9
6 . C a trin e s c u C , A rs e n e D a n d Te o d o s iu C 2 0 1 1 A p p l.
C a ta l. B : E n v iro n . 1 0 1 4 5 1
7 . K a ith L H a n d Te llia r d W A 1 9 7 9 E n v iro n . S c i. Te c h n o l.
1 3 4 1 6
8 . Te ra d a H 1 9 9 0 E n v iro n . H e a lth Pe r s p e c t. 8 7 2 1 3
9 . W a n g J H , L iu Y C , L i u D C , Yu Y W a n d G u o F B 2 0 0 9
J . M a g n . M a g n . M a te r. 3 2 1 3 6 4 6
1 0 . S ilv a V J , C o rn e jo D R , M o relli M R a n d G a m a L 2 0 0 8
J . M a g n . M a g n . M a te r. 3 2 0 3 7 0
1 1 . R a m a n k u tty C G , S u g u n a n S a n d T h o m a s B 2 0 0 2 J. Mo l
C a ta l A : Ch e m . 1 8 7 1 0 5
1 2 . D e n t G la s s e r L S 1 9 7 7 In C r y s ta llo g ra p h y a n d Its
A p p lic a tio n s ( N e w Yo r k : Va n N o s tr a n d R e in h o ld ) p . 1 1 4
1 3 . Ku rian M an d Nair D S 2 0 1 3 J. S a u d i Ch em. S o c. 1 7 3 4 5
1 4 . W h is to C In X -r a y M e th o d s 1 9 9 1 F E P ric h a rd (E d .)
( N e w Yo r k : Wile y ) 1 4 2
1 5 . Ay y a p p a n S, Mah ad ev an S, Ch an d ramo h an P,
S r in iv a s a n M P, P h ilip J a n d Ra j B 2 0 1 0 J. P h y s . C h e m .
1 1 4 6 3 3 4
1 6 . P h o k h a r a tk u l P, C h a is r iy a S , S o m k u a r n p a n it S ,
P h a ib o o n S a n d K im p a n C 2 0 0 7 I n te r. J . C o m p u t. I n fo .
S y s . C o n tr. E n g . 1 2 5 3 9
1 7 . K u ria n M a n d N a ir D S 2 0 1 4 J. E n v iro n . C h e m . E n g . 2
6 3
1 8 . H a m o u d i S , S a y a ri A , Be lk a c e m i K , B o n n e v io t L a n d
L a r a c h i F 2 0 0 0 C a ta l. To d a y 6 2 3 7 9
1 9 . K u ria n M a n d B a b u R 2 0 1 3 J . E n v iro n . C h e m . E n g .
1 8 6
2 0 . S a d a n a A a n d K a tz e r J R 1 9 7 4 J. C a ta l. 3 5 1 4 0
2 1 . Ku rian M an d Su g u n an S 2 0 0 6 Ch em. En g . J. 1 1 5 1 3 9
2 2 . L in K .S a n d Wa n g H P 2 0 0 0 L a n g m u ir 1 6 2 6 2 7
2 3 . M o lin a V G , L o p e z A ria s M , F lo rc z y k M , Ch a m a rro E
a n d E s p lu g a s S 2 0 0 5 Wa te r Re s . 3 9 7 9 5
2 4 . M a lla t T a n d B a ik e r A 1 9 9 4 C a ta l. To d a y 1 9 2 4 7
2 5 . F o r z a tti P a n d L ie tti P 1 9 9 9 Ca ta l. To d a y 5 2 1 6 5
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