Multicomponent click reactions catalysed by copper(I) oxide nanoparticles (Cu2ONPs) derived using Oryza sativa

Article abstract of DOI:10.1007/s12039-020-01774-5

Abstract: A procedure for the expedient synthesis of well-characterized Cu(I) oxide nanoparticles (Cu₂ONPs) from Cu(II) salts by employing Rice (Oryza sativa) as a cheap and ready source of reducing as well as stabilizing agent has been demonstrated. The judicious choice of rice as a catalyst has helped in the symbiotic combination of two events: viz., acidic hydrolysis of starch to form glucose and the subsequent formal reduction of Cu²⁺ by the in-situ generated monosaccharide reducing sugar (glucose) under the alkaline condition to produce Cu₂O. Further, rice was also found to be effectively stabilizing the nanoparticles from agglomeration. Optical and microscopic techniques were suitably employed for the characterization of the nanoparticles of approximately 10 nm size. Furthermore, the specifically generated nanoparticles were found to be active catalysts in an aqueous medium for Azide-alkyne Huisgen cycloaddition (Click reaction) under base free condition via one-pot multi-component addition for the synthesis of mono-, bis- and tris-1,2,3-triazoles in good to excellent yields. Graphic abstract: Cu₂ONPs synthesized using hydrolysed Rice, an active catalyst for synthesis of mono-, bis- and tris-1,4-disubstituted 1,2,3-triazoles via one pot multicomponent reactions in water.[Figure not available: see fulltext.].

Full text of DOI:10.1007/s12039-020-01774-5

J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 8 3
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REGULAR ARTICLE
Multicomponent click reactions catalysed by copper(I) oxide
nanoparticles (Cu2ONPs) derived using Oryza sativa
*
R A N D H I R R A I a n d D I L L I P K U M A R C H A N D
D e p ar t m e n t o f C h e m i s t ry , I n d i a n I n s ti t u t e o f T e c h n o l o g y M a d r a s , C h e n n a i 6 0 0 0 3 6 , I n d i a
E - m a i l : d i l l i p @ i i t m . a c . i n
M S r e c e i v e d 2 5 N o ve m b e r 2 01 9 ; r e v i s e d 1 0 J a n u a r y 2 0 2 0; a c c e p t e d 1 3 J a n u a r y 2 0 2 0
Abstract. A p r o c e d u r e f o r t h e e x p e d i e n t s y n t h e s i s o f w e l l - c h a r a c t e r i z e d C u ( I ) o x i d e n a n o p a r t i c l e s ( C u
2
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O N P s ) f ro m C u ( II ) s a l t s b y e m p l o y i n g R ic e ( Oryza sativa) a s a c h e a p a n d r e a d y s o u r c e o f r e d u c i n g a s w e l l a s
s t ab i l i z i n g a g e n t h a s b e e n d e m o n s t r a t e d . T h e j u d i c i o u s c h o ic e o f r i c e a s a c a t a l y s t h a s h e l p e d i n t h e s y m b io t i c
c o mb i n a t i o n o f t w o e v e n t s : viz., a c i d i c h y d r o l y s i s o f s t a r c h t o f o r m g l u c o s e a n d t h e s u b s e q u e n t f or m a l
2
?
r e d u c t i o n o f C u b y t h e in-situ g e n e r a t e d m o n o s a c c h a r id e r e d u c i n g s u g a r ( g lu c o s e ) u n d e r t h e a lk a li n e
c o nd i t i o n t o p r o d u c e C u O . F u r t h e r , r i c e w a s a l s o f o u n d t o b e e f f e c t i v e l y s t a b i l iz in g t h e n a n o p a r t i c l es f ro m
2
a g gl o m e r a t i o n . O p t i c a l a n d m i c ro s c o p i c t e c h n i q u e s w e r e s u i t a b l y e m p l o y e d f o r t h e c h a r a c t e r i z a t io n o f t he
n a no p a r t i c l e s o f a p p r o x i m a t e l y 1 0 n m s i z e . F u r t h e r m o r e , t h e s p e c ifi c a l l y g e n e r a t e d n a n o p a r t i c l e s w e r e f ou n d
t o b e a c t i v e c a t a l y s t s i n a n a q u e o u s m e d i u m f o r A z i d e - a l k y n e H u is g e n c y c lo a d d i t io n ( C l ic k r e a c t i o n ) u nd er
b a se f re e c o n d i t i o n via o n e - p o t m u l t i- c o m p o n e n t a d d it i o n f o r t h e s y n t h e s i s o f m o n o - , b i s - a n d t r i s - 1 ,2 , 3 -
t r i a zo l e s i n g o o d t o e x c e l l e n t y i e l d s .
Keywords. R i c e ; c u p r o u s o x i d e ; m o n o - t r i a z o le s ; b i s - t r i a z o l e s ; t r i s - t r i a z o l e s .
1
6
1 7
e t c h i n g , r ev er s e m i c el l a r , s u p er s a t u r at i o n a n d
1 8
1. Introduction
1 9
m i c r o p l a s m i c m et h o d s . F o r m o r e t h an a c en t u r y , i t
I n t h e l a s t f e w d e c a d e s , s y nt h e s i s a n d a p p l i c a t i o n o f
c u p r o u s o x i d e n a no p a r ti c l e s ( C u O N P s ) h a v e b e e n a
i s w e l l k n o w n t h at a t b a s i c p H C u ( II ) s a l t s u n d e r g o
r ed u c t i o n t o f o r m C u O i n t h e p r e s e n c e o f a
2
2
g r e a t p o i nt o f i n t e re s t f ro m a n e c o n om ic p e rs p ec t i v e ;
C u O , a p - t y pe s e m ic o n du c t o r h a v i n g a b a nd g a p o f
r e d u c i n g s u g ar ; a p r o t o c o l w i d el y i n u s e f o r t h e
a n a l y t i c al d e t e r mi n a t i o n o f g l u c o s e c o m m o n l y
2
2 0
k n o w n a s F eh l i n g r ea c t i o n . A d d i n g t o t h e l i s t o f
1 . 9 – 2 . 2 e V a b s o r b s l ig h t i n t he v is ib l e r a n g e o f t h e
e l ec t r o m ag ne t i c s p e c t r u m a n d h a s b e e n w i de l y u s e d i n
m et h o d s d e s c r i b e d e ar l i e r, a n d a s a n o f f - s p i n o f t h e
s a m e o l d b a s i c c h e mi s t r y , r es ea r c h e rs h a v e a d v a n -
t a g e o u s l y r e -a p p l i e d t h e s a m e p r o t o c o l f o r t h e g e n -
1
t h e s o l a r e n e r g y c on v e r s io n , w a t e r s p l it t i n g , h y d ro -
2
3
g e n e v o l u t i o n f r o m a m m o n i a - bo r a n e , g a s s e n s i n g ,
4
5
c at a l y s i s, t e m p l a t in g , l it h iu m - io n b a t te ri e s , C O
6
7
e ra t i o n o f C u O n a n o p ar t i cl e s u s i n g g l u c o s e a s t h e
2
8
o x i d a t i o n , m e t a l -i n s ul a to r- m e t a l r e s i s ti v e s w i t c h i n g
9
m e m o r y , a n d s e ve ra l o t h e r s a p pl i c a ti o n s . D u e t o i t s
2 1
r ed u c i n g a g e n t . S u c ce e d i n g l y , s e v e r al o t h e r r e d u c -
2 1 e ,2 2
i n g a g e n t s s u c h a s a s c o r b i c a ci d ,
2 3
h y d r a zi n e
h y d ra t e, s o d i u m b o r o h y d r i d e, a n d l e a f e x t r a c t s o f
2 4
e co n o m i ca l a v a i l a b i li t y , f u n c t io n a l d i v e r s i ty a n d l o w
t o x i c i t y, s y n t he s i s o f C u O N P s a s a f u n c t io n a l n a n o -
2 5
2 6
2
Tridax procumbens, l i g n i n h a v e b e e n i n t r o d u c e d .
A l t h o u g h m o s t o f t h es e p r o c e d u r e s i n v o l v i n g r e d u c -
i n g s u g ar s w e re c ar r i e d o u t a t r e l a t i v el y m i l d e r
r e ac t i o n c o n d i t i o n s w h i l e c o m p a re d t o o t h e r m e t h o d s
s u c h a s h y d ro t h e r ma l o r e l e c t r o c h e mi ca l d e p o s i t i o n ,
t h ey s t i l l r e q u i r e t h e i n v o l v em e n t o f c o o r d i n a t i n g
a g e n t s , s u r f a ct an t s a n d s t ab i l i ze r s e i t h er a s s t a b i l i z i n g
o r a s m o r p h o l o g y d i re c t i n g a g e n t s . T h e r e f o r e ,
m a t e r i a l h a v e b e e n p u r s u e d e n t hu s i a s t ic a l l y a l l o v e r
t h e w o r l d.
I n r e c e n t y e a r s , t h e p r e p a ra t i o n o f s i z e a n d m o r -
p h o l o g y s p e c i fi c C u O N P s h a s b e e n d e v e lo p e d b y
2
1 0
e m pl o y i n g v a r i o u s m e th o d s s u c h a s h y d r o t h e rm a l ,
1 2
1 1
1 3
w e t c h e m i ca l ,
1 4
s o l vo th e r m a l ,
e l e c t r o c h e m ic a l d e p o s i t io n s ,
p o l y o l ,
1 5
m i c ro -
o x i d a t i v e
w a v e ,
* F o r c o r re s p o n d e n c e
Electronic supplementary material: The online version of this article (https://doi.org/10.1007/s12039-020-01774-5) contains supple-
mentary material, which is available to authorized users.

8 3 P a g e 2 o f 1 2
J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 8 3
w a s d i s p e r s e d i n d i s t i l le d w a t e r b y s o n i c a t i o n a nd t he
s i li c o n w a f e r / T E M g r id s w e r e d i p p e d i n t o i t w i t h h el p o f
f o r c e p s a n d l if te d i t o f f , a l l o w e d i t t o a i r d r y . F E - S E M
a r o b us t p r e p a r a t i v e m e th o d d e v o i d o f o r w i t h m i n -
i m a l u s e e n v i r o nm e n tal ly b e ni g n a d d i t i ve s i s h i g h l y
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i m a g e s o f C u O N Ps w e r e r e c o r d e d w i t h a F E G - Q u a n ta
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d en t d isc ove ry of az id e- al ky ne cy cloa ddi tio n ( CuA AC )
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2
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b y S har pl es s a n d M e l da l h as d ra wn immen se a tt en -
ti on t ow ard s ut il iza ti on o f v ar io us c op pe r( I) s al ts a s
h ig hl y a ct iv e c ata ly st s f or th is vit al or ga ni c t ra ns fo rma -
ti on . Cu AA C ha s be en i nc re as in gl y ap pl ie d fo r t he f ac il e
m o n o c h r o m a t i c A l K a s o u r c e ( 1 4 8 6 . 6 e V ) . T he rm a l
p r o p e r t i e s o f s y n t h e si s e d C u O N P s w e r e s t u d i e d o n T G A 7
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( P e r k i n E l m e r ) a n d D S C 7 ( P e r k i n E l m e r ) . H N M R a nd
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r e a c ti o n s w e r e r e c o r d e d o n a B r u k e r A v a n c e 4 0 0 M H z
N M R o r B r u k e r A v a n c e 5 0 0 M H z N M R i n s t r u m e n t s . H R
m a s s o f u n r e p o r te d c o m p o u n d s w a s r e c o r d e d u s i n g H i g h-
R e s o l u t i o n Q - T o f M a s s .
2 9
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sy nth es es of ag ro ch emi ca ls , p ha rma ce ut ic al s, p oly -
3 1
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m e r s a nd ma ny ot he r fu ncti on al ma te ri al s d u e t o i t s
re li ab il ity , sp ec ifi ci ty a nd b io co mpa ti bi lit y. S ome o f th e
2 8
p ro mine nt C u( I) s yste ms f or az id e- al ky ne cy clo ad di -
3 3
ti on (A AC) in cl ud es , C uS O - as co rb at e sy stem, l i g an ds
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( d o u b l e d d i s t i l l e d ) w a s t a k e n i n a 1 0 0 m L r o u n d b o t t o m
fl a s k f o l l o w e d b y s l o w a d d i t i o n o f 1 . 0 m L c o n c . H S O .
3 9
c op pe r- iro n na no pa rt ic le s, m a g n e t i c n a n o - F e O @ -
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T iO / Cu O , gr ap hen e s up po rt ed Cu O n a n o p a r t i c l e s ,
4
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c ha rc oa l su ppo rt ed C u O n a n o p a r t i c l e s , a n d C u O
2
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T h e m i x t u r e w a s h e a t e d a t 1 0 0 °C f o r o n e h o u r w i t h
c o n t i n u o u s s t i r r i n g . 1 0 m L o f 5 N N a O H ( a q ) w a s a d d e d
d r o p w i s e t o n e u t r a l i z e ( p H = 7 , c h e c k e d u s i n g p H p a p e r )
t h e a c i d . 1 . 2 5 g C u S O . 5 H O d i s s o l v e d i n 2 0 m L w a t e r
4
3
mic ro /n an opa rti cl es . A ll t he ab ov e c opp er -b as ed ca ta -
ly st s sh ow go od a ct iv ity t ow ard s AA C r ea ct io ns , ho w-
e ve r, th ey sti ll r eq ui re e xt er na l ad di ti on o f ad diti ve s su ch
a s a su rf ac ta nt, co ord in ati ng a ge nt , p ol yme rs or so lid
s u p p o rt m a t er ia l.
4
2
w a s a d d e d t o t h e a b o v e r e a c t i o n m i x t u r e f o l l o w e d b y
a d d i t i o n o f 2 . 5 m L o f 5 N N a O H . S t i r r i n g w a s c o n t i n u e d
a t t h e s a m e t e m p e r a t u r e f o r a n o t h e r o n e h o u r w h e n t h e
I n t h i s s t u d y , w e r e p o rt t he s y n t h e s is o f a s u r f a ct an t
( o r p o l y m e r ) f r e e C u O N P s b y m a k i ng u s e o f e as i l y
y e l l o w c o l o u r e d p r o d u c t ( C u O N P s ) w a s o b s e r v e d t o b e
2
2
f o r m e d . T h e r e a c t i o n m i x t u r e w a s t h e n c o o l e d t o r o o m
t e m p e r a t u r e a n d t h e p r o d u c t w a s c o l l e c t e d b y c e n t r i f u -
g a t i o n , a f t e r b e i n g w a s h e d w i t h w a t e r t w i c e a n d d r i e d
u n d e r v a c u u m a t r o o m t e m p e r a t u r e .
a cc e s s i b le h o m e- a v a i l a b le r ic e a s a d u a l f u n c t i o n i n g
a g e n t , b o t h a s a n in-situ g e ne ra te d s o u r c e o f r ed u c i n g
a n d s t a b i l i zi ng a g e n t s . F u rt h e r, t h e s y nt h e s i z e d C u
2
-
O N P s h a v e b e e n e m pl o y e d a s a n e f fi c i e n t c a t al y s t i n
t h r e e- co m p o n e n t c l i c k r e a c t io n s f o r t he s y n t h es i s o f
r e g i o- se l e ct i ve 1 , 4 - d i s u b s t it u t ed 1 , 2 , 3 -t r i a z ol e s i n
w a t e r . T h e s u b s t r a te s c o p e i nc lu d e s s y n t h e s is o f m o n o -
, b i s - a n d t r i s - 1 , 4 - d i s u b s t it u te d 1 , 2 , 3 -t r i a z ol e s w i t h
g o o d t o e x c e l l e n t y i e ld s .
2 . 3 General procedure for the one-pot synthesis
of mono-1,2,3-triazoles
I n a 5 0 m L r o u n d - b o t t o m e d fl a s k b e n z y l b r o m i d e ( 1
m m o l , 1 e q u i v . ) , N a N ( 1 . 2 m m o l , 1 . 2 e q u v . ) , a t e r m i n a l
3
a l k y n e ( 1 . 2 m m o l , 1 . 2 e q u v . ) a n d 5 m g C u O N P s w e r e
2
p l a c e d i n w a t e r ( 1 0 m L ) . T h e m i x t u r e w a s m a g n e t i c a l l y
s t i r r e d u n d e r r e fl u x ( 1 0 0 °C ) f o r 3 0 m i n . T h e p r o g r e s s o f
t h e r e a c t i o n w a s m o n i t o r e d b y T L C o r b y v i s u a l
i n s p e c t i o n o f t h e f o r m a t i o n o f s o l i d p r o d u c t s . A f t e r
c o m p l e t i o n o f t h e r e a c t i o n , t h e m i x t u r e w a s c o o l e d t o
r o o m t e m p e r a t u r e a n d t h e s o l u t i o n w a s d e c a n t e d . T o t h e
l e f t o v e r r e s i d u e , e t h y l a c e t a t e ( 2 9 1 0 m L ) w a s a d d e d ,
o r g a n i c m a t e r i a l d i s s o l v e d i n i t a n d c a t a l y s t w a s r e c o v -
e r e d b y c e n t r i f u g a t i o n . T h e s o l u t i o n w a s e v a p o r a t e d t o
d r y n e s s u s i n g a r o t a r y e v a p o r a t o r , a n d t h e c r u d e p r o d u c t
t h u s o b t a i n e d w a s p u r i fi e d b y s h o r t c o l u m n c h r o m a t o g -
r a p h y w i t h s i l i c a g e l . T h e i d e n t i t i e s o f t h e i s o l a t e d
c o m p o u n d s w e r e c o n fi r m e d b y e i t h e r m a t c h i n g t h e
s p e c t r o s c o p i c d a t a o f t h e c o m p o u n d s a l r e a d y r e p o r t e d i n
t h e l i t e r a t u r e a n d u n r e p o r t e d c o m p o u n d s w e r e f u r t h e r
c o n fi r m e d b y r e c o r d i n g H R M S .
2. Experimental
2 . 1 Materials and Physical measurements
C u S O . 5 H O w a s p u r c h a s e d f ro m F i n a r C h e m i c a l s , I n d ia .
4
2
N aO H f r o m M er c k , I n d i a , C o n c . H S O f ro m F i s c h e r
2
4
S c i e nt i fi c , I n d i a. O r g a n i c p r e c u r s o rs w e r e p u r c h a s e d f r o m
S ig m a A l d r i c h. C o m m o n s o l v e n t s w e r e o b t a i n e d f r o m
S R L , I n d i a a n d u s e d w i t h o u t f u r t h e r p u r i fi c a t i o n . D o u b l e
d i st i l l e d w a t er w a s u s e d a s a s o l v e n t f o r t h e s y n t h e s i s o f
C u O N P s a nd f o r c a rr y i n g o u t A AC r e a c t i o n s . U V - v i s
2
s pe c tr a o f s am p l e w e r e r e c o rd e d u s i n g J A SC O V - 6 5 0 B io
i n st r u m en t . P o w de r X R D p a t t e r n s w e re o b t a i n e d u s i n g a
B r u k er D 8 A v a n c e i n s t r u m e n t . C u O NP s s a m p l e s u i t -
2
a b l e f o r F E - S E M a n d T E M s t u d i e s w e r e p r e p a r e d b y t h e
d i p a nd l i f t - o f f m et h o d s . I n a t y p i c a l p r o c e d u r e , t h e s a m p l e

J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 8 3
P
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3
Scheme 1. P ro p o s e d m e c h a n i s m f o r t h e f o r m a t i o n o f C u O N Ps u s i n g h y d r o l y s e d r i c e .
2
2 . 4 General procedure for the one-pot synthesis
of mono-1,2,3-triazoles bearing one free acetylene
2 . 7 General procedure for the synthesis of tris-
1,2,3-triazoles
I n a 5 0 m L r o u n d - b o t t o m e d fl a s k b e n z y l h a l i d e ( 1 m m o l , I n a r o u n d - b o t t o m e d fl a s k 1 , 3 , 5 - t r i s ( b r o m o m e t h y l ) be nz e n e
1 e q ui v ) , N a N ( 1 . 2 m m o l , 1 . 2 e q u i v . ), d i e t h y n y l b e n z e n e ( 0 .5 m m o l . 1 e q u iv . ) , N a N , ( 1 .8 m m o l , 1 . 8 e q u v .) , t er m i n a l
( 1 m m o l , 1 e q ui v . ) a n d 5 m g C u O NP s w e r e t a k e n a l o n g a l k y n e ( 1 .8 m m o l , 1 . 8 e q u iv .) a n d 5 m g C u O N P s w e re
3
3
2
2
w i t h 1 0 m L w a t er . T h e m i x t u r e w a s m a g n e t i c a l l y s t ir r e d t a k e n i n w a t e r ( 1 0 m L ) . T h e m i x t u r e w a s m a g n e t i ca l l y
u n d e r r e fl u x c on di t i o n ( 1 0 0 °C ) f o r 3 0 m i n . P ro g r e s s o f t h e s t ir r e d u n d e r r e fl u x ( 1 0 0 °C ) f o r 1 2 0 m i n . M o n it o r i n g t he
r e a c t i o n w a s m o n it o r e d b y T L C a n d a f t e r c o m p l e ti o n o f p r o g r e s s o f t h e r e a c t io n a n d e x t r a c ti o n o f p r o d u c t s w a s
r e a c t i o n p r o d u c t s
c h r o m at o g r a p h y .
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2 . 5 General procedure for the synthesis of bis-
1,2,3-triazoles (Method-1)
I n a 5 0 m L r o u n d - b o t t o m e d fl a s k , b e n z y l b r o m i de ( 3
m m o l . ) , N a N ( 3 .6 m m o l , 1 . 2 e q u iv .) , t e r m i n a l a l k yn e ( 3. 6
3
0
m m o l , 1 . 2 e q u i v . ) a n d 1 5 m g C u O N Ps w e r e p l a c ed i n
2
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1 e q ui v . ) , N a N , ( 1 . 2 m m o l , 1 . 2 e q u i v . ) , t e rm i n a l a l k y n e
( 1. 2 m m ol , 1 . 2 e qu i v . ) a n d 5 m g C u O NP s w e r e t a k e n i n
3
r e fl u x ( 1 0 0 °C ) f o r 3 0 m i n . A f te r c o m p le t io n o f t he fi r s t
r e a c ti o n r u n , t h e p r o d u c t w a s e x t r a c t e d i n e t h y l a c e t at e a nd
p u r i fie d b y c o l u m n c h r o m a t o g r a p h y t o o b t a i n t he p ur e
p r o d u c t . T h e a q u e o u s l a y e r w h ic h w a s c o l l e c t e d b y p ha s e
s e p a r a t i o n w a s c e n tr i f u g e d f o r 3 0 m i n a t 2 5 0 0 r p m a nd t he
c a t a l y s t w a s r e u s e d f o r n e x t r u n . F o l l o w i n g t h e s a m e p ro -
c e d u r e , t h e s u b s e q u e n t e x p e r i m e n t a l r u n s w e r e p e r f or m e d
a n d t h e c a t a l y s t w a s r e u s e d u p t o f o u r c y c le s .
2
w a t er ( 1 0 m L ) . T h e m i x t u re w a s m a g n e t i c a l l y s t i rr e d u n d e r
r e fl u x ( 1 0 0 °C ) f o r 6 0 m i n . T h e p r o g r e s s o f t h e r e a c ti o n w a s
m on i t o r e d b y t h e f o r m a t i o n o f s o l i d o n t h e w a l l o f t h e
r e a c t io n c o nt a in e r . A ft e r c o m p l e t i o n o f t h e r e a c t i o n , t h e
m ix t u r e w a s c oo l e d t o r o o m t e m p e r a t u r e a n d t h e s o l u t io n
w as d e ca n t ed . T h e l e ft o v e r r e s i d u e w a s w a s h e d w i t h d i l .
N H C l : N H s o l u t i o n ( 2 9 1 0 m L ) w h e r e u p o n c o p p e r g o t
4
3
r e m ov ed a s b l u e c o l o u r c o p p e r - a m i n e s p e c i e s f o l l o w e d b y
w a s hi n g w i t h e th y l a c e t a t e ( 2 9 1 0 m L ) a n d t h e r e m a i n i n g
s o li d p r o d u c t w a s d r i e d u n d e r v a c u u m .
3. Results and Discussion
3
.
1
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2
2 . 6 General procedure for the synthesis of bis-
1,2,3-triazoles (Method-2)
M a j o r c h e mi ca l c o n s t i t u en t o f r i c e i s s t ar c h , a p o l y m e r
o f g l u c o s e , t h at i s a r e d u c i n g s u g ar . R ed u c i n g s u g a r
c o n t en t o f r i c e w a s a n a l y s ed b y a d o p t i n g d i n i t r o sa l i -
c y l i c a ci d ( D N S ) p r o t o c o l . S ch em e S 1 ( S u p p l e -
m en t a ry I n f o r m at i o n ) g i v e s t h e s u m m ar y o f t h e
r e ac t i o n a n d c o n d i t i o n f o r e s t i ma t i o n o f s u g ar c o n t e n t
T h e a bo ve - m en t i o n e d p r o c e d u r e w a s f o l l o w e d u s i n g 1 , 3 -
d i e t h y n y l b en z en e o r 1 , 4 - d i e t h y n y l b e n z e n e ( 0 . 5 m m o l , 1
e q u iv . ) , b e n zy l b r o mi d e ( 1 . 2 m m o l , 1 . 2 e q u i v . ) s o d i u m
4
4
a z i d e ( 1 . 2 m m o l , 1 . 2 e q u i v . ) a n d 5 m g C u O N P s .
2

8
3
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2
J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 8 3
Figure 1. C h a r a ct e r i s t i c f e a t u r e o f s y n t h e s i z e d C u O N P s ( a ) U V - V i s s p e c t r u m o f C u O N Ps , ( b ) P o w d e r X R D p a t te r n o f
2
2
C u O N P s , ( c ) X P S s u r v e y s p e c t r u m , ( d ) X PS h i g h - r e s o lu ti o n C u 2 p s p e c t r u m , ( e ) X P S h i g h - r e s o l u t i o n O 1 s s p ec t ru m ,
2
( f) S E M i m ag e o f C u O NP s a n d ( g ) T E M i m a g e o f C u O N Ps .
2
2
2 ?
i n r i c e. C u O N P s w a s s y nt h e s i s e d b y c r o s s - fe r t i l i z i n g a d d i t i o n o f C u ( a q ) w i t h c o n t i n u o u s s t i r r i n g a n d t h e n
t h e c o n c e p t s o f a c i d ic h y d r o l y s i s o f s t a rc h t o g i v e t r e a t m en t w i t h N a O H ( a q ) t o i n cr e a s e t h e p H ( 8 – 9 ) t o
2
2 ?
g l u c o s e a n d t h e p ro p e rt y o f a l k a l i n e C u ( a q ) t o b a s i c ( Sc h e m e 1 ) .
u n d e r g o r e d u c t i o n i n t he p re s e n c e o f g lu c o s e. O n
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a ci d i c a g i t a t i o n, ( 1 0 0 °C ) g ly c o s i d i c b o n d s o f s t ar c h t u rn ed t o y e l l o w i n d i c a t i n g t h e f o r m at i o n o f C u O NP s.
2
2
?
( r i c e ) u n d e r g o c l e a v a g e t o g iv e i ts c o n s t i t u e n t H y d ro l y s e d r i c e e x h i b i t ed d u al r o l e , r e d u c t i o n o f C u
m o n o s ac ch a r i d e ( gl u c o s e ) . A f te r o n e h o u r h y d r o l y s i s s p e c i e s a t b a s i c p H a n d s t ab i l i za t i o n s o f f o r me d C u
2
-
2 ?
o f r i c e, t h e r e a c t i o n m i x t u re w a s b r o ug h t u p t o n e u t ra l O N P s . B ef o r e a d d i n g C u ( aq ) t o n e u t ra l h y d r o l y se d
p H b y s l o w a d di t i o n o f N a O H ( a q ) f ol l ow ed b y r i c e m i x t u r e, 1 m L s a m p l e w a s c o l l ec t e d a n d H R- M S

J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 8 3
P a g e 5 o f 1 2 8 3
w a s r e c o r d e d w h i c h s h o w s t h e e x i s t e n c e o f g l u c o s e i n
t h e r e a c t i o n m i x t u re ( F i gu re S 2 a ) . A f te r i s o l a t i n g
C u O N P s , t h e r e m a in in g a q u e o u s p h a s e w a s n e u t ra l -
2
i z ed b y s l o w a d d i t i o n o f d il u te H S O a n d a g a i n H R -
2
4
M S w a s r e c o r d e d , w h i c h s h o w s t he e x i s t e n c e o f g l u -
c o n i c a c i d ( F i g u r e S 2 b) t ha t i s t he o x i d i s e d p r o d u ct o f
g l u c o se . T h e s e r e s u l t s c l e a r ly i n d i c a t e t h a t g l u c o s e
2?
f r o m h y d r o l ys ed r ic e r e d u c e s C u ( a q ) t o a f f or d C u O
2
a n d i t - s e l f g e t s o x i d is e d .
V a r i ou s m e t h od s f or s y nt h e s i s o f C u O N P s w e re
2
d e v e l o p e d b y m a n y r e s e a r c h e r s w h i c h i nv o l v e d t h e
u s e o f c o m m e r c i a l s t a bi li z in g a g e n ts ( s u r f a ct an t s ,
p o l y m e r s o r l i g a n ds ) o r r e d u c in g a g e n t s ( N a BH ,
4
1 0 – 1 8
H y d r a z i n e h y d r a t e , a s c o rb ic a c i d , e t c . ) o r b o t h .
D u et al., s y n t h e s iz e d C u O N P s w i t h t he s i z e a b o u t
4 0 0 – 6 0 0 n m i n w a t e r: e t h y l e n e g l y c o l ( 1: 1 ) s o l v e n t b y
Figure 2. T G A a n d D e r i v a t i v e w e i g h t l o s s c ur ve o f
C u O N P s .
2
2
1 9
m i c r o p l a s m a m et ho d . L i et al. , s y nt h e s i z e d C u
C ar b o n ( C 1 s ) , N i t r o g e n ( N 1 s ) , o x y g e n ( O 1 s ) a n d
c o p p e r ( Cu 2 p ) , r e s p e ct i v e l y . D e t e ct i o n o f C u 2 p a n d
2 -
O N P s u s i n g l i g n in a s b o t h r e d u c i n g a n d c a p p i n g
a g e n t s , w i t h p a r t i c l e s i z e i n t he r a n g e o f 1 0 0 – 2 0 0
2 6
n m . I n o u r c a s e , w i th o u t m a ki n g u s e o f a n y c o m -
3 / 2
C u 2 p
p e a k s p o s i t i o n a t 9 3 2 . 6 3 a n d 9 5 2 . 4 1 e V
1 / 2
r e s p e ct i v e l y , i n d i c a t e t h e e x i s t e n c e o f c u p r o u s i o n
( Cu ?) a n d O 1 s c o r e l e v e l p e a k a t 5 3 0 . 2 7 e V c om b i n e d
t o g e t h e r c o n fi r m, t h e s a m p l e w a s C u O a n d t h e r e su l t s
m e r c i a l s t a b i l i zi ng a g e n ts a n d r e d u c in g a g e n ts , w e g o t
h o m o g e n e o u s p a r t i c l e s s i z e d i s tr i bu ti o n i n t he r an g e o f
9 – 1 0 n m . H e n c e , t h e m e th od s d e ve l o p e d i n t h e p r e s e n t
2
a r e i n g o o d a g r e em e n t w i t h t h e d a t a i n t h e l i t er a -
2 3 b , 2 6 ,4 8
c as e f o r t h e s y n t h e s is o f C u O N P s a r e e c on o m i c a l a n d
2
t u re .
S E M i m a g e ( Fi g u r e 1 f ) a n d T E M i m a g e
t h e s i z e d i st r i b u t i o n i s h o m o g e n e o u s .
( Fi g u r e 1g ) s h o w h o mo g en eo u s p a r t i cl e s i ze d i st ri b u -
t i o n o f a v e ra g e p a r t i c l e s i ze o f 9 – 1 0 n m . T h e r m o -
g r a v i m e t r i c a n a l y s i s ( T G A ) c u r v e a n d d e r i v a t i v e o f
w e i g h t a s a f u n c t i o n o f t e m p e ra t u r e s h o w a s m a l l
w e i g h t l o s s 2 . 5 % a t 1 4 7 °C a n d t o t a l w e i g h t l o s s t i l l
2 2 8 °C a p p e a r t o b e a r o u n d 4 . 2 % , w h i ch m ay b e d u e t o
t h e p r e s e n c e o f l o w m o l e c u l a r w e i g h t b i o c he m i c al
c o n t en t o f r i c e . M a j o r c ar b o h y d ra t e c o n t en t l o s s w as
o b s er v ed i n t h e r a n g e o f 2 5 0 – 4 5 0 °C , a t o t a l o f 1 4 . 4 %
( Fi g u r e 2) .
3 . 2 Characterization of synthesised Cu2ONPs
T h e U V - V i s s p e c tr u m o f C u O N P s ( F i gu re 1a ) s h o w s
2
a c h a ra c t er i s ti c a b s o rp t i o n f ea t u r e a t 4 78 n m , b l u e s h i f t
4 5
c o m p ar ed t o b u l k C u O . T h i s b lu e s h i ft i n t h e U V -
2
v i s i b l e a b s o r p t i o n s p e c t ru m i s t h e c o nfi rm a t i o n f o r
n a n o - s i z e d p a r t i c l e s w i t h a n i nc re a s e i n t he b a n d g ap t o
2 . 5 9 e V c o m p ar e d t o t h e t h e o r e t ic a l d i r e c t b an d g a p ,
2 . 1 3 7 e V ( b u l k C u O ) . T h e b a n d g a p m e a s u re m en t w a s
2
d o n e b y u s i n g t h e f or m u l a E = h c /k w h e r e h i s t h e
P l a n c k ’ s c o n s t a n t , c i s t he s p e e d o f l ig h t a n d k i s t h e
g
3 . 3 Catalytic study using synthesised Cu2ONPs
towards 1,2,3-triazole formation
w a v e l e n g t h a t w h i c h t he s y nt h e s i s e d C u O N P s s h o w a
2
c h a r a c t e r i s t i c a b s or p ti on p ic k . T h e a b s o r p ti o n p e a k a t
3 6 9 n m c o r r e s p o n ds t o p a r ti c l e s i z e o f d im e ns i o n 2 – 3
n m a n d t h e p e a k s a t 2 6 3 n m a n d 3 4 0 n m c o r re s p o n d t o
M a n y r e s ea r c h e rs h a v e s y n t h e s i ze d m o n o - , b i s - a n d
t r is - 1 , 2 , 3 - t r ia z o le s u s in g C u O N P s a n d C u O b a s ed
2
2
3 5 d
c at a l y s t s . Z h a n g et al. , L op e z - Ru i z et al. , Z h a n g
4 2
´
4 3 c
4 6 ,4 7
4 3 a
O - C u - O a n d C u -O - C u c h a r g e t ra ns fe r b a n d s .
et al. , a n d J i an g et al., h a v e s y n t h e s i ze d m o n o -
1 , 4 -d i s u b s t i t u t e d 1 , 2 , 3 - t r i a z o l e s via c y c l o a d d it i o n o f
4 0
c h o s e n o r g a n i c a zi d e s a n d a ce t y l e n e s . N e ma t i et al.,
P o w d e r X - R ay d i ff r a c t i o n ( F i g u re 1b ) s h o w s t h e e n t i re
c h a r a c t e r i s t i c B r a g g’ s r e fl e c t i o n a t a p pr o p r i a t e 2h,
( 1 1 0 ) , ( 1 1 1 ) , ( 2 0 0 ) , ( 2 2 0) , ( 3 1 1) a n d ( 2 2 2 ). T h e
o b t a i n e d X R D r e s u l t s a r e c o ns is t e n t w i t h t he v a l u es i n
4 1 c
4 3 b
4 3 d
R o y et al. , T s a i et al., a n d C h a n d a et al., h a v e
s y n t h e s i ze d m o n o - 1 , 4 - d i s u b s t i t u t e d 1 , 2 , 3 - t r i a z ol es via
o n e- p o t m u l t i c o m p o n e n t r e ac t i o n s . S y n t h e s i s o f b i s -
a n d t r i s - 1 , 2 , 3 - t ri a zol e h a v e b e e n r e p o r t e d v i a c l i c k
t h e s t a n d a r d J o i n t C o m m i t te e o n P o w d e r D i f f r ac t i o n
2 1 d
S t a n d a r d s ( J C P D S N o . 0 5 - 0 6 6 7 ).
s y n t h e s i s ed C u O N P s w a s f ur th e r c o n f o r m e d b y X P S,
V
a
l
a
n
c
e
s
t
a
t
e
o
f
4 1 a ,4 3 b
r ea c t i o n b e t w e e n o r g a n i c a zi d e s a n d a ce t y l e n e s .
H e re , r i c e -m e d i a t e d s y n t h e s i s ed C u O N P s w a s u s e d a s
2
X - r a y p h o t o e l e ct r on s p e c t ro s c o p y ( F i gu re 1c – e ). I n
t h e f u l l s c a n s p e c t ru m , b i n d i n g e n e r g y p e a k a p p e a rs
a r o u n d 2 8 2 , 4 0 1 , 5 3 1 a n d 9 3 3 e V c o r re s p o n d i n g t o
2
a n e ffi c i e n t c at al y s t f o r t h e s y n t h e s i s o f a l l t h e t h r e e
m o n o - , b i s - a n d t r i s - 1 , 2 , 3 -t r i a z o l es i n w a t e r via o n e -

8 3 P a g e 6 o f 1 2
J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 8 3
Table 1. C u O N P s c a t a l y s e d a z i d e -a l k y n e c y c l o a d d i t io n t o p r e p a r e m o n o - t r i a z o l e s u s i n g i n - s i t u g e n e r a t e d b e n zy l a zi d e
2
a
a n d t er mi n a l a lk y n e
Table 2. S y n t h e s i s o f m o n o - t r i a z o l e s b e a r i n g o n e f r e e a c e t y l e n e g r o u p o n s u b s t r a t e v i a o n e - p o t m u l t i c o m p o n e n t r ea ct i o n
c a t a l y s ed b y C u O N Ps .
a
2
p o t m ul t i c o m po ne n t r e a c t io n s . T h e s y nt h e s i z e d b i s - p r o d u c t s w e r e o b t a i n e d . I n t h e c as e o f m o n o t r i a z o l e
a n d t r i s - 1 , 2 , 3 - t r i a z o le c a n b e u s e d a s p o l y d e n t a t e s y n t h e s i s e d p r o d u ct , t h e c at a l y s t r ec o v er y w a s v e r y
l i g a n d s f o r r e s e a r c h i n s u pr a m o l e c u l a r c o or d i n a t i o n m u c h f e as i b l e , a s t h e p r o d u ct w e re s o l u b l e i n e t h y l
c h e m i s t r y . 5 m g o f C u O N P s w a s u s e d i n e ac h a ce t a t e. A f t e r c o m p l e t i o n o f t h e r e ac t i o n , t h e p r o d u c t
2
t r a n sf o r m a t i o n . G o o d t o t h e e x c e l le n t y i e ld s o f d e s i re d w a s e x t r a c t e d i n e t h y l a ce t a t e, d r i e d b y a d d i n g

J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 8 3
P
a
g
e
7
o
f
1
2
8
3
Table 3. S y n t h e s i s o f b i s - t r i a z o l e s ( m e t h o d - 1 ) via o n e - p o t m u l t i c o m p o n e n t r e a c ti o n c a t a l y s e d b y C u O N Ps a
2
Table 4. S y n t h e s i s o f b i s - t r i a z o l e s ( m e t h o d - 2 ) via o n e - p o t m u l t ic o m p o n e n t r e a c ti o n c a t a l y s e d b y C u O N Ps a
2
a n h y d r o u s s o d i um s u l p h a t e a n d p u r ifi e d b y c o l u mn o n e i t h er o f t h e s u b s t r a t e d i d n o t a ff e c t t h e p r o d u c t
c h r o ma t og r a ph y . F o r m o no t ri a z ol e p r o du ct s , i n f o r ma t i o n . T h e t r i az o l es 3n a n d 3o o f T a b l e 1 a n d t h e
a l m o s t a l l c a s es t h e r e a c t io ns p ro c e e d e d s m oo t h l y t o t r i az o l es 6d, 6e, 6i a n d 6j o f T a b l e 2 , w e r e p r e p a r e d
c o mp l et i on w i t h i n 3 0 m i n . T h e p re s e n c e o f h e t e r o r i n g u s i n g t h e f r ee b a s e s 4 - ( c h l o r o m e t h yl ) p y ri d i n e a n d
a n d f u n c t i o na l g r o u p ( -C H , - O C H , - N O , - C N , e t c . ) 3 - ( c h l o r o m e t h y l ) p yr i d i n e t h at w e re e x t r a c t e d f r o m
3
3
2

8
3
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g
e
8
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f
1
2
J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 8 3
Table 5. S y n t h e s i s o f t r i s - t r i a z o l e s via o n e - p o t m u l t ic o m p o n e n t r e a c t io n c a t a l y s e d b y C u O N Ps a
2
Table 6. R ec y cl i n g o f c a t a l y s t
t h e i r h y d r o c h l or i de s a l ts . H e x -5 - yn e -1 - o l ( T a b l e 1 , r e ac t i o n c o n s t i t u en t s , i t ’ s b e c o m e e as i e r t o i s o l a t e t h e
e n t r y 3 v ) g a v e l e s s e r y ie ld , m a y b e f re e h y d ro x y l g r o u p c at a l y s t a f t e r e ac h c y c l e w i t h m i n i ma l l o s s . W e s u c -
r e a c t s w i t h b e n z y l b r o m id e a s a c o m p e t i ti ve s u b s t r a t e c es s f u l l y r eu s e d t h e c at al y s t u p t o f o u r c y c l e s w i t h o u t
a g a i n st s o d i u m a z i de . I n c a s e o f b is -t r ia z o l e s ( T a b l e s 3 s i g n i fi c a n t l o s s o f p r o d u ct y i el d ( T a b l e 6 ) . T h e
a n d 4 ) a n d t r i s - t r ia z o le s ( T a b l e 5) , a s t he d e s i re d d e c re a s e o f y i el d i n s u c c e s s i v e c y c l e s m ay b e a t t r i b -
p r o d u c t w e r e i n s o l u b l e i n l ig h t a n d v o l a t i le s o l v e n t t h e u t ed t o t h e a g g l o me r a t i o n o f n a n o p ar t i cl e s a s o b se r v e d
p r o d u c t i s o l a t i o n w e r e a t t he c o s t o f c a t a l ys t r e c o v e r y i n T E M i m a g e ( Fi g u r e 3) a f t e r t h e fi rs t c y c l e .
b u t i t w a s f r e e f r o m p u r ifi c a ti on t e c hn iq ue . F o r t h e
s
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n
t
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s
i
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,
2
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r e u s e d u p t o f o u r c y c l e s ( T a b le 6) . W i th a n i nc r e a s e i n
t h e n u m b e r o f r e c y c li n g o f c a t a l ys t, a d e c r e a s e i n t h e
y i e l d o f p r o d u c t w a s o b s e rv e d . F o r p r a c t ic a l a p p l i c a- W e h a v e s y n t h e s i ze d C u O N P s w i t h h o m o g e n e o u s
4. Conclusions
2
t i o n , r e u s a b i l it y o f c a t a l ys t i s a v it a l p a r a m e t e r . T o p a r t i cl e s i ze d i s t r i b u t i o n ( 9 – 1 0 n m ) u s i n g r i c e a s a
s t u d y t h i s p a r a me t e r , a n e w s e t o f t he r e a c t i o n w a s s o u rc e o f r ed u c i n g a n d s t ab i l i zi n g a g e n t s b y c r o ss -
p e r f o r m e d b y i n c r e a s i ng t he r e a c t io n c o n s t i t u en t s f er t i l i z i n g t h e c o n c e p t o f a ci d i c h y d r o l y s i s o f s t a r ch
( b e n z y l b r o m i d e , s o d i u m a z i de , p h e n y l a c e t y l en e, ( p o l y s a cc h ar i d es ) t o g i v e c o r re s p o n d i n g m o n o sa c c h a -
C u O N P s a n d w a t e r) b y t h r e e -f o l d . B y i nc re a s i n g t h e r i d e ( g l u co s e ) a n d F eh l i n g r ea c t i o n s . T h e c a t a l y t i c
2

J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 8 3
P a g e 9 o f 1 2 8 3
V i n y l A r e n e s w i t h C y c l ic E t h e r s Bull. Korean Chem.
Soc. 31 3 5 0 9 ; ( c ) K i m J Y , P a r k J C , K i m A , K im A Y ,
L e e H J , S o n g H a n d P a r k K H 2 0 0 9 C u O N a n o c ub e-
2
C a t a ly z e d C r o s s - Co u p l i n g o f A r y l H a l i d e s w i t h P h e no l s
via U l l m a n n C o u p l i n g Eur. J. Inorg. Chem. 2009 4 21 9;
( d ) J a m m i S , K r i s h n a m o o r th y S , S a h a P , K u n d u D S ,
S a k t h i v e l S , A l i M A , P a u l R a n d P u n n iy a m u r th y T 2 00 9
R e u s a b l e C u O - N a n o p a r t ic le - Ca t a l y z e d A m i d a t io n o f
2
A r y l I o d i d e s Synlett 2009 3 3 2 3 ; ( e ) Z h a i Z , G u o X , J i a o
Z , J i n G a n d G u o X - Y 2 0 1 4 G r a p h e n e - s u p p o r t e d C u O
2
n a n o p a r t i c l e s : a n e f fi c i e n t h e t e r o g e n e o u s c a t a l y s t f or C –
O c r o s s - c o u p l i n g o f a r y l i o d i d e s w i t h p h e n o l s Catal. Sci.
´
Technol. 4 4 1 9 6 ; ( f ) C h a h d o u r a F , P r a d e l C a n d G o m e z
M 2 0 1 4 C o p p e r ( I ) O x id e N a n o p a r t ic le s i n G l y ce r o l: A
C o n v e n i e n t C a t a ly s t f o r C r o s s - C o u p li n g a n d A z i de –
A l k y n e C y c l o a d d i t i o n P r o c e s s e s ChemCatChem 6 2 92 9 ;
( g ) K u ma r B , S a h a S , G a n g u l y A a n d G a n g u l i A K 2 01 4
Figure 3. T E M i m a g e o f C u O NP s a f t e r fi rs t r e c y c l i n g .
2
A f a c il e l o w t e m p e r a t u r e ( 3 5 0 °C ) s y n t h e si s o f C u O
2
n a n o p a r t i c l e s a n d t h e i r e l e c t r o c a t a ly t i c a n d p ho t o c at -
a l y t i c p r o p e r t i e s RSC Adv. 4 1 2 0 4 3 ; ( h ) X u Y , W a ng H ,
a ct i vi t y o f s y n t he s i s e d C u O N P s w a s e x p l o r ed
2
t o w a r d s t h e s y n t he s i s o f m o n o -1 , 4 -d is u b s t it u te d 1 , 2 , 3 -
t r i a z o l e s , b i s- 1 ,4 - di s u b st it u te d 1 , 2 , 3 -t r i z ol e s a n d t r i s -
1 , 4 - di s u b s t i t u t ed 1 , 2, 3 - tr ia z o l e s via o n e - p o t m u l t i -
c o m p on en t c l i c k r e a c t io n s , i n g o o d t o e x c e ll e nt y i el d s .
T h e c a t a l ys t w a s r e c y c l e d u p t o f o u r c y c l e s w i t h o u t
s i g n i fi c an t l o s s i n y i e ld s . T h e s y n t h e s iz e d b i s - 1 , 4 - d i s -
u b s t i t u t ed 1 , 2 , 3 - t ri z o l e s a n d t ri s -1 , 4 - d i s u b s t i t u t ed
1 , 2 , 3 - t r i a zo l es c a n b e u s e d a s p o l y d e n t a t e l ig a n d s f o r
r e s e a r c h i n s u p r a m o le c u la r c h e m is tr y .
Y u Y , T i a n L , Z h a o W a n d Z h a n g B 2 0 1 1 C u O
2
N a n o c r y s t a l s: S u r f a c t a n t - F r e e R o o m - T e m p e r a t u r e M o r-
p h o lo g y M o d u l a t e d S y n t h e s i s a n d S h a p e - D e p en de n t
H e t e r o g e n e o u s O r g a n i c C a t a ly ti c A c t i v i t ie s J. Phys.
Chem. C 115 1 5 2 8 8 ; ( i ) H o J Y a n d H u a n g M H 2 00 9
S y n t h e s i s o f S u b m i c r o m e t e r - S i z e d C u O C r y s t a ls w i t h
2
M o r p h o l o g i c a l E v o l u t i o n f r o m C u b i c t o H ex a po d
S t r u c t u r e s a n d T h e i r C o m p a r a t i v e P h o t o c a t a l y t i c A c t iv -
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T s a i H , Z h a n g S , W u G a n d W a n n g H L 2 0 1 3 S t ru c tu r e-
D e p e n d e n t E l e c t r o c a ta l y t i c P r o p e r t ie s o f C u O
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C h a r a c t e r i z a t i o n , F o r m a t i o n M e c h a n i s m , a n d P h o t oc a t-
a l y t ic P r o p e r t ie s Eur. J. Inorg. Chem. 2 6 4 0
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