United S ta tes P a tent [ 1 9 1

N is h ik i et a l .
4 , 9 2 7 , 8 0 0
Ma y 2 2 , 1 9 9 0
[ 1 1 ] P a tent N umber:
[ 4 5 ] Da te o f P a tent:
[ 5 4 ] ELECTRODE CATALYS T AN D METHOD
FOR P RODUCTION THEREOF
[ 7 5 ] Inv ento rs : Yo s h ino ri N is h ik i; S h uj i N a k a ma ts u,
bo th o f K a na g a w a ; Ta k a yuk i
S h ima mune, To k yo , a l l o f J a p a n
[ 7 3 ] As s ig nee: P ermel ec El ec tro de Ltd. , K a na g a w a ,
J a p a n
[ 2 1 ] Ap p l . N o . : 2 7 6 , 7 0 3
[ 2 2 ] Fil ed: N o v . 2 8 , 1 9 8 8
[ 3 0 ] Fo reig n Ap p l ic a tio n P rio rity Da ta
N o v . 2 7 , 1 9 8 7 [ J P ] J a p a n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 2 -2 9 7 6 7 3
[ 5 1 ] Int. Cl . 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B0 1 J 2 3 /0 0
[ 5 2 ] US . Cl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 0 2 /3 4 9 ; 2 0 4 / 5 6 . 1 ;
2 0 4 /2 9 0 R; 2 0 4 /2 9 1 ; 2 0 4 /2 9 4 ; 2 0 4 /2 8 2
[ 5 8 ] Fiel d o f S ea rc h . . . . . . . . . . . . . . . . . . 2 0 4 /5 6 . 1 , 2 8 2 , 2 9 0 R,
2 0 4 /2 8 3 , 2 9 1 , \ 2 9 4 , 2 9 6 , 2 0 , 2 1 ; 5 0 2 /3 4 9
[ 5 6 ] Ref erenc es Cited
U. S . P ATEN T DOCUMEN TS
4 , 0 2 6 , 7 8 6 5 /1 9 7 7 Fuk uba ya s h i et a 1 . . . . . . . . . . . . . . 2 0 4 /2 9 1
4 , 0 6 4 , 0 3 5 1 2 /1 9 7 7 Fuk a s a w a . . . . . . . . . . . . . . . . . . . 2 0 4 /2 9 1
4 , 3 1 6 , 7 8 2 2 /1 9 8 2 Fo l l er et a l . . . . . . . . . . . . . . . . . . . . . . . . . 2 0 4 /1 2 9
4 , 5 1 0 , 0 3 4 4 /1 9 8 5 Oh s h ima et a l . .
FOREIGN P ATEN T DOCUMEN TS
2 1 3 3 7 2 9 1 2 /1 9 7 2 Fra nc e .
3 2 2 3 1 9 6 9 /1 9 8 8 J a p a n.
1 3 7 8 7 0 3 1 2 /1 9 7 4 United K ing do m .
OTHER P UBLICATION S
P a tent Abs tra c ts o f J a p a n, p . 3 1 5 C4 7 6 , J P -A-6 2 1 9 7 1 1 5 .
P rima ry Ex a miner-J o h n F. N iebl ing
As s is ta nt Ex a miner-K a th ryn Go rg o s
Atto rney, Ag ent, o r Firm-S ug h rue, Mio n, Z inn,
Ma c p ea k & S ea s
[ 5 7 ] ABS TRACT
An el ec tro de c a ta l ys t c o mp ris ing a l ea d dio x ide el ec tri
c a l l y dep o s ited l a yer, th e l a yer h a v ing p a rtic l es c o nta in
ing B-l ea d dio x ide p o w der dis p ers ed th erein, a nd a
meth o d f o r p ro duc ing th e el ec tro de c a ta l ys t a re dis
c l o s ed. Th e p a rtic l es c o nta in , B-l ea d dio x ide p o w der
a nd o p tio na l l y a n el ec tro l ytic c o c a ta l ys t s el ec ted f ro m
P TFE, a g a r, g el a tin, a p er? uo ro io n ex c h a ng e res in a nd
th e l ik e. Th e p res ent el ec tro de c a ta l ys t is us ef ul f o r
p ro duc tio n o f o zo ne by el ec tro l ys is o f w a ter a nd f o r
p ro duc tio n o f p ero x ides by el ec tro l ys is o f a q ueo us s o l u
tio ns .
1 6 Cl a ims , N o Dra w ing s
4 , 9 2 7 , 8 0 0
1
ELECTRODE CATALYS T AN D METHOD FOR
P RODUCTION THEREOF
FIELD OF THE IN VEN TION
Th e p res ent inv entio n rel a tes to a n el ec tro de c a ta l ys t
f o r el ec tro l ys is a nd a meth o d f o r th e p ro duc tio n
th ereo f , w h ic h is us ef ul f o r el ec tro l ytic o x ida tio n rea c
tio ns a t h ig h el ec tric p o tentia l s inc l uding p ro duc tio n o f
o zo ne by th e el ec tro l ys is o f w a ter, p ro duc tio n o f p ero x
ides by el ec tro l ys is o f a q ueo us s o l utio ns a nd el ec tro l ytic
o x ida tio n o f o rg a nic ma teria l .
BACK GROUN D OF THE IN VEN TION
Th e rec ent trend in th e el ec tro l ytic indus try is to
emp l o y a n el ec tro de c o mp ris ing a s ubs tra te h a v ing h ig h
s ta bil ity under a no de c o nditio ns , e. g . , tita nium a nd tita
nium a l l o ys , c o a ted w ith a n el ec tro de c a ta l ys t s ub
s ta nc e, p a rtic ul a rl y th e o x ides o f th e p l a tinum g ro up
meta l s , in p l a c e o f s o l ubl e el ec tro des a s ex emp l i? ed by
c a rbo n. Th is el ec tro de, c a l l ed a dimens io na l l y s ta bl e
a no de (DS A) o r a dimens io na l l y s ta bl e el ec tro de
(DS E), is us ed in a v a riety o f indus tria l el ec tro l ytic
p ro c es s es inc l uding p ro duc tio n o f o x yg en g a s by el ec
tro l ys is o f w a ter a nd p ro duc tio n o f h a l o g en o r a l k a l i
h ydro x ide by el ec tro l ys is o f a n a q ueo us s o l utio n o f
meta l h a l ide, bec a us e o f its ex c el l ent el ec tro l ytic c h a r
a c teris tic s a nd dura bil ity, a s des c ribed in US . P a t. N o s .
3 , 7 1 1 , 3 8 5 a nd 3 , 6 3 2 , 4 9 8 .
Th e a no de s ubs ta nc e p l a ys a n imp o rta nt ro l e in p ro
duc tio n o f o zo ne g a s a nd p ero x ides util izing th e a no dic
el ec tro l ytic rea c tio n a nd in o rg a nic el ec tro l ys is . In th e
el ec tro l ytic rea c tio n f o r th e p ro duc tio n o f o zo ne g a s ,
th e el ec tric p o tentia l is h ig h , a nd ev en if DS A is us ed,
l o w p o tentia l el ec tro l ytic rea c tio ns p redo mina te. Th us ,
DS A is uns uita bl e f o r th e el ec tro l ytic p ro duc tio n o f
o zo ne g a s , a nd o nl y a tita nium el ec tro de c o a ted w ith
p l a tinum is util ized.
In th e el ec tro l ys is f o r th e p ro duc tio n o f o zo ne g a s , a n
a no dic c a ta l ytic s ubs ta nc e w h ic h c a n be us ed in p l a c e o f
DS A w ith a n inc rea s e in th e ef ? c ienc y o f o p era tio n is
needed. Th us , v a rio us inv es tig a tio ns h a v e been ma de
no t o nl y in reg a rd to el ec tro de c a ta l ys ts but a l s o w ith
res p ec t to th e el ec tro de a nd c el l s truc ture w h ere l ea d,
l ea d o x ide, c a rbo n, etc . a re us ed a s el ec tro de s ubs ta nc es ,
a s J . El ec . Ch em. S o c , 1 3 2 p . 3 6 7 f f . (1 9 8 5 ) a nd US . P a t.
N o . 4 , 4 1 6 , 7 4 7 .
In th e us e o f a n el ec tro de c o nta ining l ea d dio x ide f o r
th e p ro duc tio n o f o zo ne, dura bil ity a nd mec h a nic a l
s treng th o f th e el ec tro de a re p o o r a nd th e l ea d dio x ide
el ec tro de c a ta l ys t h a s a rel a tiv el y h ig h el ec tro l ytic v o l t
a g e w h ic h inc rea s es th e a mo unt o f el ec tric p o w er c o n
s umed.
Th e p res ent inv ento rs h a v e p ro p o s ed v a rio us im
p ro v ements o f th e l ea d dio x ide-c o a ted el ec tro de. Ho w
ev er, th e imp ro v ed el ec tro des p rev io us l y p ro p o s ed by
th e p res ent inv ento rs a re s til l no t s a tis f a c to ry in th a t a
dec rea s e in el ec tro l ytic v o l ta g e a s c riba bl e to th e ef f i
c ienc y o f th e c a ta l ys t its el f w a s ins uf f ic ient, w h il e a n
inc rea s e in c urrent ef f ic ienc y c o ul d no t be a c h iev ed
bec a us e th e ma teria l to be el ec tro l yzed in a n el ec tro
l ytic s o l utio n is no t in s uf f ic ient c o nta c t w ith th e a c tiv e
s ubs ta nc e o n th e el ec tro de. Furth ermo re, if th e el ec
tro de a c tiv e s ubs ta nc e is to o dens e, g a s is dra w n ins uf ?
c ientl y res ul ting in a h ig h er el ec tro l ytic v o l ta g e.
1 5
2 0
3 0
3 5
4 5
5 5
6 5
2
S UMMARY OF THE IN VEN TION
An o bj ec tiv e o f th e p res ent inv entio n is to p ro v ide a
l ea d dio x ide el ec tro de c a ta l ys t h a v ing th e des ired a c tiv
ity a nd l o w er el ec tro l ytic v o l ta g e, a nd a meth o d f o r th e
p ro duc tio n th ereo f .
Th e p res ent inv entio n rel a tes to a n el ec tro de c a ta l ys t
c o mp ris ing a s l ea d dio x ide el ec tric a l l y dep o s ited l a yer
h a v ing ? ne p a rtic l es c o nta ining B-l ea d dio x ide p o w der
dis p ers ed th erein.
Th e p res ent inv entio n a l s o rel a tes to a n el ec tro de
c a ta l ys t c o mp ris ing a s ubs tra te f o r el ec tric dep o s itio n
a nd a l ea d dio x ide el ec tric a l l y dep o s ited l a yer h a v ing
? ne p a rtic l es c o nta ining B-l ea d dio x ide p o w der dis
p ers ed th erein.
Th e p res ent inv entio n rel a tes to a meth o d f o r p ro duc
ing th e el ec tro de c a ta l ys t w h ic h c o mp ris es el ec tro l yz
ing a s ubs tra te f o r el ec tric dep o s itio n in a n a q ueo us l ea d
nitra te s o l utio n h a v ing ? ne p a rtic l es c o nta ining B-l ea d
dio x ide p o w der s us p ended th erein to f o rm a l ea d dio x
ide el ec tric a l l y dep o s ited l a yer o n th e s ubs tra te, th e
l a yer h a v ing p a rtic l es c o nta ining B-l ea d dio x ide p o w der
dis p ers ed th erein, a nd th en s ep a ra ting th e l ea d dio x ide
el ec tric a l l y dep o s ited l a yer f ro m th e s ubs tra te f o r el ec
tric dep o s itio n.
Th e p res ent inv entio n a l s o rel a tes to a meth o d f o r
p ro duc ing th e el ec tro de c a ta l ys t w h ic h c o mp ris es el ec
tro l yzing a s ubs tra te f o r el ec tric dep o s itio n in a n a q ue
o us l ea d nitra te s o l utio n h a v ing ? ne p a rtic l es c o nta ining
B-l ea d dio x ide p o w der s us p ended th erein to f o rm a l ea d
dio x ide el ec tric a l l y dep o s ited l a yer o n th e s ubs tra te, th e
l a yer h a v ing p a rtic l es c o nta ining B-l ea d dio x ide p o w der
dis p ers ed th erein.
DETAILED DES CRIP TION OF THE
IN VEN TION
Th e p res ent inv entio n is ba s ed o n f inding th a t a l ea d
dio x ide c a ta l ys t l a yer f o rmed by el ec tro dep o s itio n o n a
s ubs tra te h a s a h ig h er s treng th a nd o p era tes a t a l o w er
el ec tro l ytic v o l ta g e a s c o mp a red to a l ea d dio x ide c a ta
l ys t l a yer o n a s ubs tra te f o rmed by a c o nv entio na l tec h
niq ue s uc h a s th e h o t p res s meth o d.
Th e l ea d dio x ide c a ta l ys t l a yer f o rmed by th e el ec tro
dep o s itio n o f th e p res ent inv entio n is dens er th a n a l ea d
dio x ide c a ta l ys t f o rmed by th e c o nv entio na l h o t p res s
meth o d a nd th us th e s treng th o f th e c a ta l ys t its el f is
inc rea s ed. Furth ermo re, by inc o rp o ra ting , B-l ea d dio x
ide p o w der into th e c a ta l ys t, g a s remo v a l is enh a nc ed
a nd th e el ec tro l ytic v o l ta g e is dec rea s ed w h il e s treng th
o f th e c a ta l ys t is ma inta ined.
Th e el ec tro de c a ta l ys t o f th e p res ent inv entio n is
f o rmed by el ec tric a l l y dep o s iting a l a yer o f l ea d dio x ide
o n a s ubs tra te s urf a c e. S ubs tra tes th a t ma y be us ed in
th e p res ent inv entio n inc l ude th o s e c o nv entio na l l y us ed
a s a n el ec tro de s ubs tra te s uc h a s v a l v e meta l s (e. g . ,
tita nium, zirc o nium, nio bium a nd ta nta l um) a nd a l l o ys
th ereo f , w h ic h a re s uita bl e f o r us e in th e f o rm o f p l a te,
ba r a nd p o ro us mes h a nd w h ic h a re ea s y to h a ndl e a nd
h a v e g o o d dura bil ity. Th es e s ubs tra tes a re us ed a s a
unita ry a s s embl y w ith th e el ec tro de c a ta l ys t l a yer.
In th e p res ent inv entio n, a n io n ex c h a ng e membra ne
w h ic h is a s o l id p o l ymer el ec tro l yte (S P E) (e. g . , ? uo ri
na ted h ydro c a rbo n res in-ba s ed io n ex c h a ng e mem
bra nes ) a nd v a rio us el ec tric ity c o l l ec to rs c a n a l s o be
us ed f o r th e s ubs tra te. In th e c a s e, el ec tric ity c o l l ec to rs
h a v ing a n a tta c h ed c a ta l ys t l a yer a nd S P E el ec tro des
c a n be f o rmed by a s ing l e s tep , a nd th us , a n o p era tio n o f
s ep a ra tel y f o rming a n el ec tro de c a ta l ys t a nd th en ? x ing
4 , 9 2 7 , 8 0 0
3
it o n th e membra ne o r el ec tric ity c o l l ec to r, a s is c o n
v entio na l l y p erf o rmed, ma y be o mitted.
In th e p res ent inv entio n, a s th e s ubs tra te, v a rio us ? ne
p a rtic l es a c ting a s nuc l ei f o r th e g ro w th o f l ea d dio x ide
el ec tric a l l y dep o s ited l a yer c a n a l s o be us ed. Ca ta l ys t
p a rtic l es f o rmed in' th is ma nner c a n be us ed a s c a ta l ys ts
f o r v a rio us rea c tio ns . In a dditio n, a f ter th e f o rma tio n o f
th e l ea d dio x ide el ec tric a l l y dep o s ited l a yer o n a s uit
a bl e s ubs tra te, th e c a ta l ys t l a yer ma y be p eel ed a p a rt
f ro m th e s ubs tra te a nd us ed a s s uc h in v a rio us rea c tio n.
N o n-l imiting c o nditio ns in th e el ec tro dep o s itio n f o r
f o rma tio n o f th e l ea d dio x ide l a yer o nto th e s ubs tra tes
a re a s f o l l o w s : a 3 0 0 to 5 0 0 g /l a q ueo us l ea d nitra te
s o l utio n ma y be us ed a s a n el ec tro l ytic s o l utio n, a nd th e
el ec tro dep o s itio n ma y be c a rried o ut a t a temp era ture o f
4 0 to 6 0 C. , a l iq uid p H o f no t mo re th a n 3 a nd a
c urrent dens ity o f l to 1 0 A/dmz. Under s uc h c o ndi
tio ns , B-l ea d dio x ide is ma inl y el ec tric a l l y dep o s ited o n
th e s ubs tra te.
Th e l ea d dio x ide el ec tric a l l y dep o s ited l a yer f o rmed
by th e a bo v e el ec tro dep o s itio n p ro c es s c o nta ins ? ne
p a rtic l es w h ic h a re c o mp o s ed ma inl y o f B-l ea d dio x ide
p o w der. Th e B-l ea d dio x ide h a s inh erent c a ta l ytic a c
tiv ity, h a s g o o d c o rro s io n res is ta nc e in v a rio us s o l utio ns
s uc h a s s tro ng a c ids (e. g . , s ul f uric a c id) a nd f urth er h a s
ex c el l ent el ec tric a l c o nduc tiv ity a bo ut 1 0 * 4 (1 c m). Th e
a -l ea d dio x ide is uns uita bl e bec a us e it is inf erio r in c o r
ro s io n res is ta nc e a nd el ec tric a l c o nduc tiv ity to B-l ea d
dio x ide.
Th e B-l ea d dio x ide ? ne p a rtic l e dia meter a re no t
p a rtic ul a rl y l imited in th e p res ent inv entio n, but th e
p a rtic l e dia meter is p ref era bl y s ma l l er th a n th a t p a s s ing
th ro ug h 1 0 0 mes h (Tyl er mes h ; h erea f ter th e s a me), i. e. ,
1 5 0 p , o r l es s , s o a s to o bta in a ? rm s urf a c e. In th e c a s e
o f p a rtic l es h a v ing a p a rtic l e dia meter s ma l l er th a n th a t
p a s s ing th ro ug h 3 4 5 mes h , i. e. , 4 0 p . o r l es s , it is p re
f erred th a t th e s ma l l er p a rtic l es h o t c o ns titute mo re
th a n 5 0 % o f th e to ta l w eig h t o f p a rtic l es . If th e p ro p o r
tio n o f th e p a rtic l es h a v ing a p a rtic l e dia meter s ma l l er
th a n a bo ut 4 0 p . is g rea ter th a n 5 0 %, ? rmnes s is in
c rea s ed a t th e ex p ens e o f p o ro s ity.
Th e dis p ers ed f ine p a rtic l es in th e l ea d dio x ide el ec
tric a l l y dep o s ited l a yer g enera l l y c o nta in no t l es s th a n
2 0 w t % o f B-l ea d dio x ide p o w der, a nd th ey ma y c o n
s is t o f B-l ea d dio x ide p o w der. Dep ending o n its us e, a n
el ec tro l ytic c o c a ta l ys t c a n be c o nta ined a s th e dis p ers ed
f ine p a rtic l es , s uc h a s a ? uo rine res in (e. g . , p o l ytetra ? u
o ro eth yl ene (P TFE)), a g a r, g el a tin, a p er? uo ro io n
ex c h a ng e res in, c a rbo n f l uo ride, c a rbo n, a nd o x ides o f
a t l ea s t o ne o f tita nium, zirc o nium, nio bium a nd ta nta
l um. Fo r ex a mp l e, p a rtic l es o f a ? uo rine res in, a p er
? uo ro s ul f o nic a c id-typ e io n ex c h a ng e res in, a nd c a rbo n
? uo ride a re s uita bl e f o r p ro duc tio n o f o zo ne. Fo r p ro
duc tio n o f p ero x ides , th e o x ides o f tita nium, zirc o nium,
nio bium, a nd ta nta l um a re s uita bl e f o r us e a s el ec tro l ytic
c o c a ta l ys ts . Fo r o rg a nic el ec tro l ytic o x ida tio ns , c a rbo n,
a s w el l a s th o s e des c ribed a bo v e, is s uita bl e.
Th e p ro p o rtio n o f th e dis p ers ed p a rtic l es c o nta ining
B-l ea d dio x ide p o w der in th e to ta l el ec tric a l l y dep o s ited
l a yer is p ref era bl y f ro m 5 to 7 0 v o l %. If l es s th a n 5 v o l
%, th e ef f ec t o f ex tens io n o f s urf a c e a rea due to reduc
tio n in p o ro s ity is ins uf ? c ient. On th e o th er h a nd, if in
ex c es s o f 7 0 v o l %, th e mec h a nic a l s treng th ma y be
reduc ed.
Th e a bo v e p a rtic l es c a n be inc o rp o ra ted in th e l ea d
dio x ide el ec tric a l l y dep o s ited l a yer by s us p ens io n p l a t
ing in w h ic h el ec tro dep o s itio n is c a rried o ut by s us
p ending B-l ea d dio x ide p o w der a nd el ec tro l ytic c o c a ta
2 5
3 0
3 5
4 5
6 0
4
l ys t p a rtic l es in th e a bo v e el ec tro l ytic s o l utio n. Al terna
tiv el y, a p a s te c o nta ining th e a bo v e p a rtic l es is c o a ted
f o l l o w ed by el ec tro dep o s itio n o f l ea d dio x ide a nd th is
p ro c es s ma y be rep ea ted.
Th e el ec tro de c a ta l ys t o f th e p res ent inv entio n is
f o rmed o n a s ubs tra te. Dep ending o n th e typ e o f th e
s ubs tra te, th e c a ta l ys t c a n h a v e v a rio us f o rms . Wh en a
c o nv entio na l el ec tro de s ubs tra te s uc h a s tita nium is
us ed a s th e s ubs tra te, th e el ec tro de c a ta l ys t o f th e p res
ent inv entio n is f o rmed o n th e s urf a c e th ereo f to p ro
v ide a n el ec tro de s truc ture; w h en a n io n ex c h a ng e
membra ne is us ed a s th e s ubs tra te, th e el ec tro de c a ta l ys t
c a n be us ed a s a S P E typ e el ec tro de c a ta l ys t; w h en a n
el ec tric c o l l ec to r is us ed a s th e s ubs tra te, th e el ec tro de
c a ta l ys t o f th e p res ent inv entio n is us ed a s , f o r ex a mp l e,
a zero g a p -typ e el ec tro de in w h ic h th e c a ta l ys t l a yer is
bro ug h t into c l o s e c o nta c t w ith a n io n ex c h a ng e mem
bra ne; a nd w h en ? ne p a rtic l e nuc l ei a re us ed a s th e
s ubs tra te, l ea d dio x ide is el ec tric a l l y dep o s ited o n th e
nuc l ei s urf a c e to f o rm c a ta l ys t p a rtic l es .
In th e c a s e w h ere a s ubs tra te merel y f o r a l l o w ing l ea d
dio x ide to be el ec tric a l l y dep o s ited th ereo n is us ed, th e
el ec tric a l l y dep o s ited l a yer is p eel ed a p a rt f ro m th e
s ubs tra te a nd c a n be us ed a s s uc h o r a f ter p ul v eriza tio n
in v a rio us el ec tro de rea c tio ns . Th e c a ta l ys t, in s uc h
f o rm, is p a rtic ul a rl y s uita bl e f o r us e in p ro duc tio n o f
o zo ne by w a ter el ec tro l ys is , in p ro duc tio n o f p ero x ides
by el ec tro l ys is o r a q ueo us s o l utio ns , a nd in o rg a nic
el ec tro l ytic o x ida tio n s uc h a s dec o mp o s itio n o f p h eno l ,
nitril e, a nd th e l ik e.
In th e el ec tro de c a ta l ys t o f th e p res ent inv entio n, a
l ea d dio x ide el ec tric a l l y dep o s ited l a yer in w h ic h ? ne
p a rtic l es c o nta ining B-l ea d dio x ide p o w der is dis p ers ed,
is f o rmed o n a s ubs tra te. As el ec tro de a c tiv e s ubs ta nc es ,
th e B-l ea d dio x ide p o w der h a s a h ig h er o v erv o l ta g e (by
a bo ut 5 0 0 mV) th a n th e p l a tinum g ro up meta l o x ides
a nd th e l ik e. Th us , th e el ec tro de c a ta l ys t o f th e p res ent
inv entio n is us ef ul f o r p ro duc tio n o f o zo ne by el ec tro l y
s is o f w a ter, p ro duc tio n o f p ero x ides by el ec tro l ys is o f
a q ueo us s o l utio ns , o rg a nic el ec tro l ytic o x ida tio n a nd
o th er el ec tro l ys is , w h ic h a re c a rried o ut a t h ig h el ec tro
l ytic o v erv o l ta g e a s c o mp a red to th e el ec tro l ys is o f
a l k a l i h a l ide f o r th e p ro duc tio n o f a l k a l i h ydro x ide a nd
el ec tro l ys is o f w a ter to f o rm o x yg en a nd h ydro g en.
S inc e th e el ec tric a l l y dep o s ited l a yer h a s a th ree di
mens io na l ex tens io n, th e c o nta c t betw een a rea c ta nt a nd
th e el ec tro de a c tiv e s ubs ta nc e is inc rea s ed, w h ic h in
c rea s es c urrent ef ? c ienc y a nd dec rea s es c el l v o l ta g e.
S inc e th e el ec tric a l l y dep o s ited l a yer c o nta ins p a rti
c l es , th e deg ree o f p o ro s ity c a n be a dj us ted by v a rying
th e dens ity o f th e dep o s ited l a yer a nd th e deg ree o f g a s
remo v a l c a n, th us , be c o ntro l l ed. An a p p a ra tus s uita bl e
f o r g a s remo v a l c a n be rea dil y a s s embl ed.
S inc e th e l ea d dio x ide l a yer is mo re dens l y f o rmed o n
th e s ubs tra te by el ec tro dep o s itio n, th e el ec tro l ytic a l l y
dep o s ited l a yer is s tro ng er th a n a l ea d dio x ide c a ta l ys t
l a yer f o rmed by th e c o nv entio na l h o t p res s meth o d.
Furth ermo re, th e el ec tro l ytic v o l ta g e c a n be dec rea s ed.
Th e f o l l o w ing a re no n-l imiting ex a mp l es o f th e p res
ent inv entio n.
EXAMP LE 1
An ex p a nded mes h ma de o f p ure tita nium a nd h a v ing
a th ic k nes s o f 1 . 5 mm w a s s mo o th ed a nd a tta c h ed by
res is ta nc e w el ding to a mes h a l s o ma de o f tita nium
h a v ing a th ic k nes s o f 0 . 3 mm. Th is a s s embl y s erv ed a s a
s ubs tra te. Th is s ubs tra te w a s deg rea s ed a nd w a s h ed in a
bo il ing 2 0 % a q ueo us h ydro c h l o ric a c id s o l utio n. Af ter
4 , 9 2 7 , 8 0 0
5
th e a bo v e p retrea tment, a n a q ueo us h ydro c h l o ric a c id
s o l utio n c o nta ining p l a tinum: tita nium: ta nta l um in p ro
p o rtio ns o f 5 0 :4 0 :1 0 (mo l %) res p ec tiv el y w a s a p p l ied
to th e s urf a c e o f th e s ubs tra te us ing a brus h . Th e c o a ted
a s s embl y w a s ba k ed a t 5 5 0 C. f o r 1 0 minutes in ? o w ing
a ir to p ro v ide a n o x ide underl ying l a yer o f p l a tinum
tita nium-ta nta l um. Th is o p era tio n w a s rep ea ted f o ur
times .
On th e a bo v e underl ying l a yer, a l ea d dio x ide l a yer
c o nta ining B-l ea d dio x ide p o w der w a s el ec tric a l l y de
p o s ited under th e f o l l o w ing c o nditio ns .
An a q ueo us l ea d nitra te s o l utio n w a s ? rs t el ec tro
l yzed to f o rm B-l ea d dio x ide, w h ic h w a s th en g ro und
f o r 2 4 h o urs in a n a g a te mo rta r a nd s c reened to c o l l ec t
p a rtic l es h a v ing a dia meter o f no t g rea ter th a n 1 0 0 it.
An a q ueo us el ec tro dep o s itio n s o l utio n c o nta ining 4 0 0
g /l o f l ea d nitra te w a s p rep a red, a nd th e a bo v e s c reened
B-l ea d dio x ide p o w der w a s a dded th ereto in a n a mo unt
o f 3 w t %. Wh il e th e el ec tro dep o s itio n s o l utio n w a s
v ig o ro us l y s tirred s o a s no t to p rec ip ita te th e B-l ea d
l ea d dio x ide p a rtic l es , el ec tro l ys is w a s c a rried o ut f o r
a bo ut 4 h o urs us ing th e s ubs tra te w ith th e underl ying
l a yer p ro v ided th ereo n a s a n a no de a t a c urrent dens ity
o f 4 A/dm2 to f o rm a c o a ting o n th e s ubs tra te h a v ing a n
a p p a rent th ic k nes s o f a bo ut 2 mm. During el ec tro l ys is ,
th e temp era ture w a s 6 5 C. a nd th e p H o f th e s o l utio n
w a s 1 to 2 .
Fo r c o mp a ris o n, a s a c o a ting l a yer w a s f o rmed in th e
s a me ma nner a s a bo v e ex c ep t th a t , B-l ea d dio x ide p a rti
c l es w ere no t s us p ended in th e a q ueo us l ea d nitra te
s o l utio n. Th e a p p a rent th ic k nes s o f th e c o a ting l a yer
w a s a bo ut 0 . 8 mm, a nd th e inc rea s e in th e w eig h t f o l
l o w ing el ec tro l ytic c o a ting w a s a bo ut o ne-h a l f . Th us , it
w a s f o und th a t th e p a rtic l e c o ntent in th e c o a ting l a yer
p rev io us l y p rep a red us ing th e B-l ea d dio x ide p a rtic l e
s us p ended el ec tro dep o s itio n s o l utio n w a s a bo ut 5 0 w t
% o f th e to ta l c o a ting , a nd th e c o a ting l a yer w a s p o
ro us .
With th e s ubs tra te in c l o s e c o nta c t w ith a p erf l uo ro
s ul f o nic a c id typ e io n ex c h a ng e membra ne, (ma nuf a c
tured by du Fo nt a nd s o l d under th e tra dema rk N a
? o n) w h ere th e s ubs tra te s erv ed a s a n a no de a nd a
p l a tinum net s erv ed a s a c a th o de, el ec tro l ys is w a s c a r
ried o ut a t a temp era ture o f 1 0 C. a nd a c urrent dens ity
o f 1 0 0 A/dm2 us ing a mix ture o f 5 % h ydro f l uo ric a c id
a nd a 1 5 % a q ueo us s ul f uric a c id s o l utio n a s a n el ec tro
l yte. In th e c a s e o f th e el ec tro de h a v ing el ec tric a l l y
dep o s ited B-l ea d dio x ide, th e c urrent ef f ic ienc y a nd
el ec tro l ytic v o l ta g e in th e g enera tio n o f o zo ne w ere
1 6 % a nd 3 . 6 V, res p ec tiv el y. In th e c a s e o f th e c o mp a r
a tiv e el ec tro de, th e c urrent ef f ic ienc y a nd th e el ec tro
l ytic v o l ta g e w ere 1 0 % a nd 4 . 2 V, res p ec tiv el y.
COMP ARATIVE EXAMP LE 1
A s ubs tra te h a v ing a n underl ying l a yer w a s p ro duc ed
in th e s a me ma nner a s in Ex a mp l e 1 . On th e s ubs tra te,
B-l ea d dio x ide p o w der h a v ing a dia meter o f 2 0 to 1 0 0 p .
w a s h o t p res s ed f o r 1 0 minutes under a p res s ure o f 1 0 0
k g /c m2 a t a temp era ture o f 1 2 0 C. to f o rm a l ea d dio x
ide a tta c h ed l a yer.
Us ing th e el ec tro de s ubs tra te w ith th e h o t p res s ed
l a yer, o zo ne p ro duc tio n w a s c a rried o ut under th e s a me
c o nditio ns a s in Ex a mp l e 1 . Th e c urrent ef ? c ienc y a nd
th e el ec tro l ytic v o l ta g e w ere 8 % a nd 5 V, res p ec tiv el y.
EXAMP LE 2
On a tita nium s ubs tra te h a v ing a n underl ying l a yer a s
p ro duc ed in th e s a me ma nner a s in Ex a mp l e 1 , a B-l ea d
1 5
2 0
2 5
3 0
3 5
4 0
4 5
5 0
6 5
6
dio x ide l a yer w a s f o rmed a t 7 0 C. f o r 3 0 minutes a t a
c urrent dens ity o f 4 A/dm2 us ing 4 0 0 g /l o f a n a q ueo us
l ea d nitra te s o l utio n a s a n el ec tro l yte. Th erea f ter, us ing
a mix ture o f 1 0 1 1 1 1 /1 o f a n a q ueo us p o l ytetra ? uo ro eth yl ~
ene (P TFE) s us p ens io n a nd 4 0 0 g /l o f a n a q ueo us l ea d
nitra te s o l utio n w ith B-l ea d dio x ide ? ne p a rtic l es s us
p ended th erein a s a n el ec tro l yte, a , B-l ea d dio x ide l a yer
w a s el ec tric a l l y dep o s ited o n th e a bo v e s ubs tra te a t 7 0
C. f o r 3 0 minutes a t a c urrent dens ity o f 4 A/dmZ . Th e
a bo v e tw o o p era tio ns w ere ea c h rep ea ted f o ur times to
o bta in a c o a ting h a v ing a th ic k nes s o f a bo ut 1 . 5 mm.
Th e el ec tro de w ith th e c o a ting p ro v ided th ereo n w a s
bro ug h t into c l o s e c o nta c t w ith a p erf l uo ro s ul f o nic a c id
typ e io n ex c h a ng e membra ne. Us ing th e res ul ting s ub
s tra te a s s embl y a s a n a no de, el ec tro l ys is w a s c a rried o ut
a t a c urrent dens ity o f 1 0 0 A/dm2 us ing a n a q ueo us
s ul f uric a c id s o l utio n c o nta ining a s ma l l a mo unt o f
s il ic a f l uo ric a c id a s a n el ec tro l yte. Fo r c o mp a ris o n,
el ec tro l ys is w a s c a rried o ut under th e s a me c o nditio ns
a s a bo v e us ing th e s a me c o mp a ra tiv e el ec tro de a s de~
s c ribed in Ex a mp l e 1 .
Fo r th e el ec tro de o f th is ex a mp l e c o mp ris ing a n el ec
tric a l l y dep o s ited l a yer o f B-l ea d dio x ide a nd P TFE
c o c a ta l ys t, th e c urrent ef ? c ienc y f o r g enera tio n o f
o zo ne a t th e a no de w a s 1 6 %. On th e o th er h a nd, in th e
c a s e o f th e c o mp a ra tiv e el ec tro de, th e c urrent ef f i
c ienc y w a s 8 %.
EXAMP LE 3
An el ec tro de w ith a n el ec tric a l l y dep o s ited l ea d dio x
ide l a yer c o a ted th ereo n w a s p ro duc ed in th e s a me
ma nner a s in Ex a mp l e 1 ex c ep t th a t B-l ea d dio x ide
p o w der c o nta ining 1 0 v o l % zirc o nium o x ide a nd p a s s
ing th ro ug h a 2 5 0 mes h s c reen w a s us ed in p l a c e o f th e
B-l ea d dio x ide p o w der.
Us ing a 5 c m X5 c m el ec tro de th us p rep a red a s a n
a no de, 3 l iters o f a g o l d p l a ting w a s te c o nta ining 5 , 0 0 0
p p m o f c ya n w a s el ec tro l yzed a t a c urrent dens ity o f 1 0
A/dm2 to dec o mp o s e c ya n io ns . Fo r c o mp a ris o n, el ec
tro l ys is w a s c a rried o ut us ing a p l a tinum p l a ted tita nium
el ec tro de a s a n a no de.
Af ter 1 0 minutes o f el ec tro l ys is , th e c o nc entra tio n o f
c ya n in th e w a s te w a s dec rea s ed to 5 0 0 p p m in . th e c a s e
o f th e p res ent el ec tro l ys is . On th e o th er h a nd, th e c ya n
c o nc entra tio n in th e c o mp a ra tiv e el ec tro l ys is w a s 2 , 2 0 0
p p m.
EXAMP LE 4
Th e s urf a c e o f a c o mmerc ia l l y a v a il a bl e p erf l uo ro s ul
f o nic a c id typ e c a tio n ex c h a ng e membra ne (ma nuf a c
tured by du Fo nt a nd s o l d under th e tra de na me N a ? o n
1 1 7 ) w a s ro ug h ened us ing #1 0 0 0 emery p a p er. Th e io n
ex c h a ng e membra ne w a s th en dip p ed in a 5 w t % a q ue
o us s o l utio n o f nitric a c id to c o nv ert th e s ul f o nic -a c id
g ro up th ereo f into th e H typ e. Th is io n ex c h a ng e mem
bra ne w a s inc o rp o ra ted in a tw o c h a mber el ec tro l ytic
c el l a s a dia p h ra g m. In o ne o f th e c h a mbers , 5 g /l o f a n
a q ueo us s o l utio n o f c h l o ro p l a tinic a c id w a s intro duc ed,
a nd in th e o th er c h a mber, 1 0 g /l o f a n a q ueo us h ydra
zine s o l utio n w a s intro duc ed. By a l l o w ing th e s o l utio ns
to s ta nd f o r 2 4 h o urs , a p l a tinum l a yer w a s f o rmed o n
o ne s ide o f th e dia p h ra g m.
Indep endentl y, B-l ea d dio x ide p rep a red by th e el ec
tro l ytic meth o d o f th e p res ent inv entio n w a s g ro und in
a n a g a te mo rta r. Th e ? ne p a rtic l es o f , B-l ea d dio x ide
o bta ined by p a s s ing th ro ug h a 2 5 0 mes h s c reen w ere
k nea ded in c o mbina tio n w ith a n a q ueo us P TFE s us p en
s io n (p ro duc ed by Mits ui Fl uo ro c h emic a l Co . , Ltd.
4 , 9 2 7 , 8 0 0
7
under th e tra de na me 3 0 ] ; P TFE c o ntent 1 w t %) a nd
a p erf l uo ro io n ex c h a ng e res in to p rep a re a p a s te. Th is
p a s te w a s brus h c o a ted o n th e o p p o s ite s ide o f th e mem
bra ne o n w h ic h th e p l a tinium w a s dep o s ited, a l l o w ed to
s ta nd, s mo o th ed a nd th en h ea t p res s ed a t a temp era ture
o f 1 6 0 C. to f o rm a l ea d dio x ide a tta c h ed l a yer.
Th e io n ex c h a ng e membra ne th us -p rep a red w ith p l a t
inum a tta c h ed o n o ne s ide a nd , B-l ea d dio x ide o n th e
o th er w a s a g a in p l a c ed into th e tw o c h a mber el ec tro
l ytic c el l . In th e c h a mber f a c ing th e , B-l ea d dio x ide s ide
a t th e membra ne, 4 0 0 g /l o f a n a q ueo us l ea d nitra te
s o l utio n w a s intro duc ed. Us ing th e p l a tinum o n th e io n
ex c h a ng e membra ne a s a c a th o de a nd a tita nium p l a te
p l a c ed in c o nta c t w ith th e B-l ea d dio x ide a tta c h ed l a yer
a s a n a no de, el ec tro l ys is w a s c a rried o ut f o r 2 h o urs a t
6 0 C. a t 2 A/dm2 to f o rm a n el ec tric a l l y dep o s ited l ea d
dio x ide l a yer.
El ec tric c o l l ec to rs o f p o ro us nic k el w ith p l a tinum
p l a ted o n th e s urf a c e th ereo f us ed a t th e c a th o de s ide,
a nd a tita nium mes h w ith B-l ea d dio x ide c o a ted th ereo n
us ed a t th e a no de (l ea d dio x ide) s ide w ere p l a c ed in
c o nta c t w ith th e a bo v e el ec tro de s truc ture. Deio nized
w a ter w a s intro duc ed in a t th e a no de s ide a nd el ec tro
l yzed. At 2 0 C. , a nd a c urrent. dens ity 1 0 0 A/dmz,
o x yg en g a s c o nta ining 1 4 % o zo ne w a s o bta ined. Th e
c el l v o l ta g e during el ec tro l ys is w a s 3 . 7 V.
COMP ARATIVE EXAMP LE 2
Ozo ne w a s g enera ted under th e s a me c o nditio ns a s in
Ex a mp l e 4 , us ing a n io n ex c h a ng e membra ne in w h ic h
th e f o rma tio n o f a n el ec tric a l l y dep o s itedl a yer us ing a n
a q ueo us l ea d nitra te s o l utio n w a s o mitted. Onl y th e l ea d
dio x ide a tta c h ed l a yer w a s f o rmed. Ox yg en g a s c o nta in
ing 9 % o zo ne w a s o bta ined. Th e c el l v o l ta g e during
el ec tro l ys is w a s 5 . 1 V.
EXAMP LE 5
An io n ex c h a ng e membra ne w ith p l a tinum a tta c h ed
to o ne s ide th ereo f w a s p rep a red in th e s a me ma nner a s
in Ex a mp l e 4 . B-l ea d dio x ide p a s s ing th ro ug h a 3 4 5
mes h s c reen w a s k nea ded w ith eth yl a l c o h o l to p rep a re
a p a s te. Th is p a s te w a s c o a ted o n th e o p p o s ite s ide o f
th e io n ex c h a ng e membra ne rel a tiv e to th e p l a tinium
dep o s ited s ide, dried a t ro o m temp era ture, s mo o th ed
a nd th en p res s ed a t a temp era ture o f 1 6 0 C. Furth er
mo re, a l ea d dio x ide el ec tric a l l y dep o s ited l a yer w a s
f o rmed by el ec tro l ys is in th e s a me ma nner a s in Ex a m
p l e l . Th e s o l id el ec tro l yte s ing l e el ec tro de s truc ture
th us p ro duc ed w a s inc o rp o ra ted in th e s a me el ec tro
l ytic c el l a s in Ex a mp l e 1 , a nd deio nized w a ter w a s
intro duc ed in th e a no de c h a mber a nd el ec tro l yzed.
Under c o nditio ns o f temp era ture 2 0 C. a nd c urrent
dens ity 1 0 0 A/dmz, o x yg en g a s c o nta ining 1 2 % o zo ne
w a s o bta ined. Th e c el l v o l ta g e during el ec tro l ys is w a s
4 . 2 V.
EXAMP LE 6
Th e io n ex c h a ng e membra ne o f Ex a mp l e 4 w a s a c ti
v a ted by s p uttering a rg o n io ns to th e s urf a c e th ereo f .
Th e io n ex c h a ng e membra ne w a s c o nv erted into th e H
typ e by dip p ing in a 5 w t % a q ueo us nitric a c id s o l utio n
a nd th en inc o rp o ra ted a s th e dia p h ra g m o f th e tw o
c h a mber el ec tro l ytic c el l . A p l a tinum c o a ting w a s
f o rmed o n o ne s ide in th e s a me ma nner a s in Ex a mp l e 4 .
B-l ea d dio x ide ? ne p a rtic l es o bta ined by el ec tro l ys is
a nd a mix ture o f tita nium o x ide a nd zirc o nium o x ide
p a rtic l es w ere trea ted in v a c uum a t 1 , 1 0 0 C. f o r 6 h o urs
to o bta in p a rtia l l y reduc ed ? ne p a rtic l es . Th es e p a rti
2 0
2 5
3 0
3 5
4 0
4 5
5 0
5 5
6 5
8
c l es w ere k nea ded w ith a n a q ueo us P TFE s us p ens io n to
p rep a re a p a s te. Th is p a s te w a s c o a ted o n th e io n ex
c h a ng e membra ne in th e s a me ma nner a s in Ex a mp l e 1
to f o rm a n a tta c h ed l a yer.
Th e io n ex c h a ng e membra ne th us p rep a red w a s in
c o rp o ra ted in th e tw o c h a mber el ec tro l ytic c el l . At th e
B-l ea d dio x ide l a yer s ide, 4 0 0 g /l o f a n a q ueo us l ea d
nitra te s o l utio n c o nta ining a s us p ens io n o f ? ne p a rtic l es
o f th e s a me c o mp o s itio n a s th e p a s te w a s intro duc ed. At
6 5 C. a nd 2 A/dmz, a n el ec tric a l l y dep o s ited l a yer o f
B-l ea d dio x ide c o nta ining th e a bo v e ? ne p a rtic l es w a s
f o rmed o n th e a tta c h ed l a yer c o nta ining B-l ea d dio x ide
to th ereby p ro duc e a s o l id el ec tro l yte typ e el ec tro de
s truc ture.
Th e el ec tro de s truc ture th us p rep a red w a s inc o rp o
ra ted in a n el ec tro l ytic c el l in th e s a me ma nner a s in
Ex a mp l e 4 , a nd deio nized w a ter w a s el ec tro l yzed. At
2 0 C. a nd a c urrent dens ity 1 0 0 A/dm2 , o x yg en g a s
c o nta ining 1 6 % o f o zo ne w a s o bta ined f ro m th e a no de
c o mp a rtment. Th e c el l v o l ta g e during el ec tro l ys is w a s
3 . 6 V.
EXAMP LE 7
A f ine mes h (l o ng dia meter: 2 . 5 mm; s h o rt dia meter:
1 . 6 mm) h a v ing a th ic k nes s o f 0 3 mm w a s w el ded to th e
s urf a c e o f a n ex p a nded mes h o f p ure tita nium h a v ing a
th ic k nes s o f 1 . 5 mm to f o rm a n el ec tric c o l l ec to r. Th is
el ec tric c o l l ec to r w a s w el ded to a f l a ng e ma de o f tita
nium p l a te. Th is w el ded a s s embl y w a s deg rea s ed a nd
w a s h ed w ith a bo il ing 2 0 w t % a q ueo us h ydro c h l o ric
a c id s o l utio n f o r 3 minutes to c a rry o ut p re-trea tment. A
c o a ting o f p l a tinum-tita nium-ta nta l um in p ro p o rtio ns o f
2 5 -6 0 -1 5 mo l % res p ec tiv el y w a s th en f o rmed o n th e
tita nium p l a te by th e th erma l dec o mp o s itio n meth o d o f
Ex a mp l e 1 to f o rm a n underl ying o x ide l a yer.
Us ing a s o l utio n o f l ea d o x ide in a 3 0 w t % a q ueo us
s o dium h ydro x ide s o l utio n a s a n el ec tro l yte a nd th e
tita nium mes h w ith th e underl ying l a yer f o rmed
th ereo n a s a n a no de, el ec tro l ys is w a s c a rried o ut f o r 3 0
minutes a t 4 0 C. a nd a c urrent o f l A/dm2 to f o rm a
c o a ting l a yer o f a -l ea d dio x ide o n th e a bo v e el ec tric
c o l l ec to r.
A c o mmerc ia l l y a v a il a bl e p erf l uo ro s ul f o nic a c id typ e
c a tio n ex c h a ng e membra ne (N a ? o n 1 1 7 ), th e s urf a c e o f
w h ic h -w a s ro ug h ened w ith #1 0 0 0 emery p a p er, w a s
us ed a s a s o l id el ec tro l yte. On o ne s ide o f th e io n ex
c h a ng e membra ne, a s o l utio n p rep a red by dis s o l v ing
c h l o ro p l a tinic a c id in is o p ro p yl a l c o h o l (p l a tinum c o n
tent 5 0 g /l ) w a s a p p l ied us ing a brus h . Th e s o l utio n th us
a p p l ied w a s th erma l l y dec o mp o s ed a t 2 5 0 C. to f o rm a
p l a tinum c o a ting l a yer o n o ne s ide o f th e membra ne.
Th e io n ex c h a ng e membra ne w a s p l a c ed in a tw o
c h a mber el ec tro l ytic c el l . At th e p l a tinum s ide, p o ro us
nic k el (ma nuf a c tured by S umito mo El ec tric indus tries ,
Ltd. a nd s o l d under th e tra de na me Cel met) w ith
p l a tinum a p p l ied th ereo n w a s emp l o yed a s a n el ec tric
c o l l ec to r. At th e o p p o s ite c h a mber, th e el ec tric c o l l ec
to r p ro duc ed a s des c ribed a bo v e w a s p l a c ed in c o nta c t
w ith th e a bo v e io n ex c h a ng e membra ne , B-l ea d dio x ide
p o w der p rep a red by el ec tro l ys is a nd p a s s ed th ro ug h a
2 5 0 mes h s c reen w a s s us p ended in a n a q ueo us l ea d
nitra te s o l utio n a nd P TFE w a s f urth er a dded th ereto in
a n a mo unt o f 1 w t %. Us ing 4 0 0 g /l o f th e a bo v e a q ue
o us l ea d nitra te s o l utio n a s a n el ec tro l yte w ith th e a bo v e
tita nium el ec tric c o l l ec to r a s a n a no de a nd th e p l a tinum
c o a ted nic k el a s a c a th o de, el ec tro l ys is w a s c a rried o ut
a t a c urrent dens ity o f 2 A/dm2 a nd a temp era ture o f 6 0
C.
4 , 9 2 7 , 8 0 0
- 9
Af ter 8 h o urs o f el ec tro l ys is , a p o ro us l ea d dio x ide
el ec tric a l l y dep o s ited l a yer h a v ing th e to ta l th ic k nes s o f
a bo ut 2 mm w a s f o rmed. In th e l ea d dio x ide el ec tric a l l y
dep o s ited l a yer, a s w el l a s in th e dis p ers ed B-l ea d dio x
ide, w h ite ? bers c o ns idered to be P TFE w ere o bs erv ed.
Th e io n ex c h a ng e membra ne a nd th e el ec tric c o l l ec to r
w ere c o mbined to g eth er w ith th e l ea d dio x ide l a yer to
f o rm a n a s s embl y.
Th e a s s embl y w a s w a s h ed, a nd deio nized w a ter w a s
p l a c ed in th e el ec tro l ytic c el l . With th e l ea d dio x ide
l a yer s ide a s a n a no de, el ec tro l ys is w a s c a rried o ut a t 2 0
C. a nd a c urrent dens ity o f 1 0 0 A/dm2 . Fro m th e a no de
s ide, o x yg en c o nta ining 1 4 % o zo ne w a s o bta ined. Th e
c el l v o l ta g e during el ec tro l ys is w a s 3 . 6 V.
COMP ARATIVE EXAMP LE 3
Up o n p ro duc tio n o f o zo ne under th e s a me c o nditio ns
a s in Ex a mp l e 7 o mitting th e f o rma tio n o f th e el ec tri
c a l l y dep o s ited l a yer us ing th e a q ueo us l ea d nitra te
s o l utio n a nd w h erein th e el ec tric c o l l ec to r-a tta c h ed
l a yer-io n ex c h a ng e membra ne w ere c o mbined into o ne
bo dy by th e h o t p res s ing , o x yg en g a s c o nta ining 8 %
o zo ne w a s o bta ined. Th e c el l v o l ta g e during el ec tro l y
s is w a s 6 V.
EXAMP LE 8
In th e s a me ma nner a s p ro v ided in Ex a mp l e 7 , a n io n
ex c h a ng e membra ne w ith p l a tinum a tta c h ed to th e o ne
s ide th ereo f a nd a n a no de c o l l ec to r w ith a n underl ying
l a yer p ro v ided th ereto w ere p rep a red. Th e io n ex
c h a ng e membra ne w a s inc o rp o ra ted in th is c h a mber
el ec tro l ytic c el l . Th e a no de c o l l ec to r w ith a n B-l ea d
dio x ide l a yer f o rmed th ereo n w a s p l a c ed a t a dis ta nc e o f
0 . 5 to 1 mm f ro m th e io n ex c h a ng e membra ne. In th e
a no de c o mp a rtment, a 4 0 0 g /l a q ueo us l ea d nitra te
s o l utio n w a s intro duc ed c o nta ining a s us p ens io n o f [ 3
l ea d dio x ide p o w der s eiv ed th ro ug h a 2 0 0 mes h s c reen
a nd a s o bta ined by el ec tro l ys is . Us ing th e a no de c o l l ec
to r a s a n a no de a nd p l a c ing a p l a tinum c o l l ec to r p re
p a red in Ex a mp l e 7 a s a c a th o de, el ec tro l ys is w a s c a r
ried o ut f o r 6 h o urs a t 6 0 C. a nd a c urrent dens ity o f 4
A/dmz. An el ec tro de a s s embl y in w h ic h th e a no de
c o l l ec to r a nd th e io n ex c h a ng e membra ne w ere c o m
bined into o ne bo dy by th e l ea d dio x ide el ec tric a l l y
dep o s ited l a yer w a s th us o bta ined.
Deio nized w a ter w a s intro duc ed in bo th th e a no de
c o mp a rtment a nd th e c a th o de c o mp a rtment o f th e el ec
tro l ytic c el l a nd el ec tro l yzed a t 2 0 C. a nd 1 0 0 A/dm2
to o bta in o x yg en g a s c o nta ining 1 4 % o f o zo ne. Th e c el l
v o l ta g e during el ec tro l ys is w a s 3 . 7 V.
EXAMP LE 9
An io n ex c h a ng e membra ne s ubj ec ted to p retrea t
ment in th e s a me ma nner a s in Ex a mp l e 7 w a s inc o rp o
ra ted in a tw o c h a mber el ec tro l ytic c el l a s a dia p h ra g m.
In o ne c o mp a rtment, a 5 g /l a q ueo us c h l o ro p l a tinic a c id
s o l utio n w a s intro duc ed, a nd in th e o th er c o mp a rtment,
a 1 0 g /l a q ueo us h ydra zine s o l utio n w a s intro duc ed.
Af ter 2 4 h o urs , a p l a tinum l a yer w a s th us f o rmed o n o ne
s ide o f th e io n ex c h a ng e membra ne.
Th e io n ex c h a ng e membra ne w a s th o ro ug h l y w a s h ed
a nd inc o rp o ra ted in a tw o c h a mber el ec tro l ytic c el l a s a
dia p h ra g m. P o ro us nic k el w ith a p l a tinum c o a ting
f o rmed th ereo n w a s p l a c ed in c o nta c t w ith th e p l a tinum
membra ne l a yer. At th e o th er c o mp a rtment, a n el ec tric
c o l l ec to r w ith a l ea d dio x ide l a yer f o rmed o n th e s ur
f a c e th ereo f a s f a bric a ted in Ex a mp l e 1 w a s p l a c ed in
c o nta c t w ith th e io n ex c h a ng e membra ne. _
1 5
2 5
3 0
3 5
4 5
5 0
5 5
6 0
6 5
1 0
In th e el ec tro l ytic c o mp a rtment a t th e o p p o s ite s ide
o f th e p l a tinum l a yer, a 4 0 0 g /l a q ueo us l ea d nitra te
s o l utio n c o nta ining 1 0 g /l o f B-l ea d o x ide a nd 1 0 1 1 1 1 /1 o f
a p er? uo ro io n ex c h a ng e res in s o l utio n w a s intro duc ed.
An el ec tric p o tentia l w a s a p p l ied to th e el ec tric c o l l ec
to rs w ith th e p l a tinum s ide s erv ing a s th e c a th o de f o r 4
h o urs a t a c urrent dens ity o f 4 A/dm2 . A l ea d dio x ide
l a yer c o nta ining p a rtic l es ma inl y (8 0 w t % o r mo re) o f
B-l ea d dio x ide p a rtic l es w a s el ec tric a l l y dep o s ited, to
f o rm a n el ec tro de a s s embl y in w h ic h th e io n ex c h a ng e
membra ne a nd th e a no de c o l l ec to r w ere c o mbined to
g eth er into o ne unit.
Th e el ec tro l ytic s o l utio n w a s w ith dra w n f ro m th e
el ec tro l ytic c el l a nd th e c el l w a s th en th o ro ug h l y
w a s h ed. Th en, deio nized w a ter w a s intro duc ed into th e
c el l a s a n el ec tro l ytic s o l utio n. El ec tro l ys is w a s c a rried
o ut a t a c urrent dens ity o f 1 0 0 A/dmZ . Fro m th e a no de
c o mp a rtment, o x yg en g a s c o nta ining 1 6 % o zo ne w a s
o bta ined. Th e c el l v o l ta g e during el ec tro l ys is w a s 3 . 6
V.
EXAMP LE 1 0
An el ec tro l ytic a s s embl y w a s p ro duc ed in th e s a me
ma nner a s in Ex a mp l e 9 ex c ep t th a t a mix ture o f B-l ea d
dio x ide a nd c a rbo n f l uo ride w a s us ed a s th e s us p ens io n.
Th e el ec tro l ytic a s s embl y w a s inc o rp o ra ted in a n el ec
tro l ytic c el l , a nd deio nized w a ter w a s intro duc ed in th e
a no de c o mp a rtment a nd el ec tro l yzed a t 5 0 A/dmz.
Fro m th e a no de c o mp a rtment, o x yg en g a s c o nta ining
a bo ut 9 % o zo ne w a s o bta ined. Th e c el l v o l ta g e during
el ec tro l ys is w a s 3 . 3 V.
EXAMP LE 1 1
A c o mmerc ia l l y a v a il a bl e p er? uo ro s ul f o nic a c id typ e
c a tio nic ex c h a ng e membra ne (N a ? o n 1 1 7 ), a f ter ro ug h
ening th e s urf a c e th ereo f w ith #1 0 0 0 emery p a p er, w a s
dip p ed in a 5 w t % a q ueo us nitric a c id s o l utio n to c o n
v ert th e s ul f o nic a c id g ro up into th e H typ e a nd th en
inc o rp o ra ted in a tw o c h a mber el ec tro l ytic c el l a s a
dia p h ra g m. In o ne c o mp a rtment, a 5 g /l a q ueo us c h l o
ro p l a tinic a c id s o l utio n w a s intro duc ed, a nd in th e o th er
c o mp a rtment, a 1 0 g /l a q ueo us h ydra zine s o l utio n w a s
intro duc ed. Th e s o l utio ns w ere th en a l l o w ed to s ta nd to
f o rm a p l a tinum l a yer o n o ne s ide o f th e membra ne.
B-l ea d dio x ide p rep a red by th e el ec tro l ytic meth o d o f
Ex a mp l e 1 w a s g ro und in a n a g a te mo rta r to o bta in a
p o w der s eiv ed th ro ug h a 2 5 0 mes h s c reen. Th is p o w der
w a s k nea ded a l o ng w ith a n a q ueo us P TFE s us p ens io n
(3 0 ] ) a nd a p er? uo ro io n ex c h a ng e res in to f o rm a p a s te.
Th is p a s te w a s a p p l ied w ith a brus h o n th e s ide o f th e
io n ex c h a ng e membra ne o p p o s ite to th e s ide o n w h ic h
p l a tinum w a s dep o s ited. Th e a p p l ied p a s te w a s a l l o w ed
to s ta nd a t ro o m temp era ture a nd s mo o th ed a nd th en
h ea t p res s ed a t a temp era ture o f 1 6 0 C. to f o rm a n
a tta c h ed l a yer.
An el ec tric c o l l ec to r o n w h ic h a n underl ying l a yer
h a d been f o rmed in th e s a me ma nner a s in Ex a mp l e 7
w a s c o a ted w ith a -l ea d dio x ide in th e s a me ma nner a s in
Ex a mp l e 7 .
Th e a bo v e io n ex c h a ng e membra ne w a s inc o rp o ra ted
in a tw o c h a mber el ec tro l ytic c el l . P o ro us nic k el w ith
p l a tinum-c o a ted th ereo n (Cel met) w a s bro ug h t into
c l o s e c o nta c t w ith th e p l a tinum s ide o f th e io n ex c h a ng e
membra ne. At th e o th er s ide, th e a bo v e p rep a red el ec
tric c o l l ec to r w a s bro ug h t into c l o s e c o nta c t w ith th e
B-l ea d dio x ide a tta c h ed l a yer o n th e io n ex c h a ng e mem
bra ne. A 4 0 0 g /l a q ueo us l ea d nitra te s o l utio n w a s
a dded to th e l ea d dio x ide s ide, a nd el ec tro l ys is w a s
4 , 9 2 7 , 8 0 0
1 1
c a rried o ut f o r 4 h o urs a t a c urrent dens ity o f 4 A/dm2
us ing th e tita nium el ec tric c o l l ec to r c o a ted w ith l ea d
dio x ide a s a n a no de. An el ec tro de a s s embl y w a s th us
o bta ined in w h ic h th e io n ex c h a ng e membra ne a nd th e
el ec tric c o l l ec to r w ere c o mbined to g eth er in o ne unit.
Th e el ec tro l ytic s o l utio n w a s w ith dra w n f ro m th e
el ec tro l ytic c el l , a nd th e c el l w a s th en th o ro ug h l y
' w a s h ed w ith deio nized w a ter. Deio nized w a ter w a s
th en a dded to th e l ea d dio x ide c o mp a rtment a nd el ec
tric ity w a s p a s s ed th ereth ro ug h a t a c urrent dens ity o f
1 0 0 A/dmz. Th e l iq uid temp era ture w a s 2 0 C. a nd th e
el ec tro l ytic v o l ta g e w a s 3 . 6 V. Ox yg en g a s c o nta ining
1 6 % o zo ne w a s th us o bta ined f ro m th e a no de s ide.
EXAMP LE 1 2
An el ec tro de a s s embl y w a s p ro duc ed in th e s a me
ma nner a s a n Ex a mp l e 1 1 ex c ep t th a t a mix ture o f a 1
g /l a q ueo us s us p ens io n o f P TFE a nd a 4 0 0 g /l a q ueo us
l ea d nitra te s o l utio n c o nta ining , B-l ea d dio x ide ? ne p a r
tic l es c o nta ining ta nta l um o x ide w a s us ed a s th e el ec tro
l ytic s o l utio n in f o rma tio n o f th e el ec tric a l l y dep o s ited
l ea d dio x ide l a yer.
Th e el ec tro de a s s embl y th us f o rmed w a s inc o rp o
ra ted into a tw o c h a mber el ec tro l ytic c el l . Deio nized
w a ter w a s a dded to th e l ea d dio x ide c h a mber a nd el ec
tro l ys is w a s c a rried a t a c urrent dens ity o f l 0 0 A/dm2
us ing th e l ea d dio x ide a s th e a no de. Th e el ec tro l ytic
v o l ta g e w a s 3 . 5 V, a nd o x yg en g a s c o nta ining 1 5 %
o zo ne w a s o bta ined f ro m th e a no de s ide.
Wh il e th e inv entio n h a s been des c ribed in deta il a nd
w ith ref erenc e to s p ec i? c embo diments th ereo f , it w il l
be a p p a rent to o ne s k il l ed in th e a rt th a t v a rio us c h a ng es
a nd mo di? c a tio ns c a n be ma de th erein w ith o ut dep a rt
ing f ro m th e s p irit a nd s c o p e th ereo f .
Wh a t is c l a imed is :
1 . An el ec tro de c a ta l ys t c o mp ris ing a l ea d dio x ide
el ec tric a l l y dep o s ited l a yer, s a id l a yer h a v ing p a rtic l es
c o nta ining , B-l ea d dio x ide p o w der dis p ers ed th erein.
2 . An el ec tro de c a ta l ys t a s in c l a im 1 , w h erein th e
dis p ers ed p a rtic l es c o mp ris e a mix ture o f B-l ea d dio x ide
p o w der a nd el ec tro l ytic c o c a ta l ys t p a rtic l es .
3 . An el ec tro de c a ta l ys t a s in c l a im 2 , w h erein th e
el ec tro l ytic c o c a ta l ys t is a t l ea s t o ne s el ec ted f ro m th e
g ro up c o ns is ting o f p o l ytetra ? uo ro eth yl ene, a g a r, g el a
tin, a p erf l uo ro io n ex c h a ng e res in, c a rbo n ? uo ride,
c a rbo n, a nd o x ides o f o ne o r mo re o f tita nium, zirc o
nium, nio bium a nd ta nta l um.
1 5
2 5
4 0
4 5
5 5
6 0
6 5
1 2
4 . An el ec tro de c a ta l ys t a s in c l a im 1 , w h erein th e
dis p ers ed p a rtic l es c o ns titute f ro m 5 to 7 0 % by v o l ume
o f th e to ta l l ea d dio x ide el ec tric a l l y dep o s ited l a yer.
5 . An el ec tro de c a ta l ys t c o mp ris ing a s ubs tra te f o r
el ec tro dep o s itio n a nd a l ea d dio x ide el ec tric a l l y dep o s
ited l a yer o n th e s ubs tra te, s a id l a yer h a v ing p a rtic l es
c o nta ining B-l ea d dio x ide p o w der dis p ers ed th erein.
6 . An el ec tro de c a ta l ys t a s in c l a im 5 , w h erein th e
dis p ers ed p a rtic l es c o mp ris e a mix ture o f , B-l ea d dio x ide
p o w der a nd el ec tro l ytic c o c a ta l ys t p a rtic l es .
7 . An el ec tro de c a ta l ys t a s in c l a im 6 , w h erein th e
el ec tro l ytic c o c a ta l ys t is a t l ea s t o ne s el ec ted f ro m th e
g ro up c o ns is ting o f p o l ytetra f l uo ro eth yl ene, a g a r, g el a
tin, a p er? uo ro io n ex c h a ng e res in, c a rbo n ? uo ride,
c a rbo n, a nd o x ides o f o ne o r mo re o f tita nium, zirc o
nium, nio bium a nd ta nta l um.
8 . An el ec tro de c a ta l ys t a s in c l a im 5 , w h erein th e
dis p ers ed p a rtic l es c o ns titute f ro m 5 to 7 0 % by v o l ume
o f th e to ta l l ea d dio x ide el ec tric a l l y dep o s ited l a yer.
9 . An el ec tro de c a ta l ys t a s in c l a im 5 , w h erein th e
s ubs tra te f o r el ec tro dep o s itio n is a n io n ex c h a ng e mem
bra ne.
1 0 . An el ec tro de c a ta l ys t a s in c l a im 5 , w h erein th e
s ubs tra te f o r el ec tro dep o s itio n is a n el ec tric c o l l ec to r.
1 1 . An el ec tro de c a ta l ys t a s in c l a im 5 , w h erein th e
s ubs tra te f o r el ec tro dep o s itio n is a nuc l eus f o r th e
g ro w th o f th e el ec tric a l l y dep o s ited l a yer.
1 2 . A meth o d f o r p ro duc ing a l ea d dio x ide el ec tro de
c a ta l ys t, w h ic h c o mp ris es el ec tro l yzing a s ubs tra te f o r
dep o s itio n in a n a q ueo us l ea d nitra te s o l utio n h a v ing
p a rtic l es c o nta ining B-l ea d dio x ide p o w der s us p ended
th erein to f o rm a l ea d dio x ide el ec tric a l l y dep o s ited
l a yer o n s a id s ubs tra te, s a id l a yer h a v ing p a rtic l es c o n
ta ining B-l ea d dio x ide p o w der dis p ers ed th erein; a nd
th erea f ter s ep a ra ting th e l ea d dio x ide el ec tric a l l y dep o s
ited l a yer f ro m th e s ubs tra te.
1 3 . A meth o d f o r p ro duc ing a l ea d dio x ide el ec tro de
c a ta l ys t, w h ic h c o mp ris es el ec tro l yzing a s ubs tra te f o r
el ec tro dep o s itio n in a n a q ueo us l ea d nitra te s o l utio n
h a v ing p a rtic l es c o nta ining B-l ea d dio x ide p o w der s us
p ended th erein to th ereby f o rm a l ea d dio x ide el ec tri
c a l l y dep o s ited l a yer o n s a id s ubs tra te, s a id l a yer h a v ing
p a rtic l es c o nta ining , B-l ea d dio x ide p o w der dis p ers ed
th erein.
1 4 . A meth o d a s in c l a im 1 3 , w h erein th e s ubs tra te f o r
el ec tro dep o s itio n is a n io n ex c h a ng e membra ne.
1 5 . A meth o d a s in c l a im 1 3 , w h erein th e s ubs tra te f o r
el ec tro dep o s itio n is a n el ec tric c o l l ec to r.
1 6 . A meth o d a s in c l a im 1 3 , w h erein th e s ubs tra te f o r
el ec tro dep o s itio n is a nuc l eus f o r g ro w th o f th e el ec tri
c a l l y dep o s ited l a yer.
* * * = 1 !