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Journal of Catalysis 227 (2004) 109116 www. elsevier.

com /locate/c at
!actors res"onsi#le for t$e activity of alumina surfaces in t$e catalytic
e"o%i&ation of cis'cyclooctene wit$ a(ueous )
2
*
2
+o#erto +inal&i, -lf .c$uc$ar&t

Instituto de Qumica, Universidade Estadual de Campinas, PO Box 6154, 1!"4#$%1 Campinas#&P, Bra'il
+eceive& 7 /ay 20040 revise& 22 June 20040 acce"te& 24 June 2004
1vaila#le online 29 July 2004
Abstract
2$e structural, te%tural, an& c$emical "ro"erties as well as t$e $y&ro"$ilicity of four &ifferent sol3el aluminas were &etermine& #y
&ifferent met$o&s an& com"are& wit$ t$eir activity in t$e catalytic e"o%i&ation of cis'cyclooctene wit$ a(ueous )
2
*
2
. 4t was foun& t$at
t$e $y&ro"$ilicity of t$e ( 'alumina surface is t$e "rinci"al factor res"onsi#le for t$e &ifference in catalytic activity. 2$e $y&ro"$ilicity of
( 'alumina s$oul& #e sufficient to 3uarantee a fast reaction wit$ $y&ro3en "ero%i&e on t$e surface #ut s$oul& not to #e too $i3$ in or&er to
allow t$e a""roac$ of olefin to t$e active sites.
2004 5lsevier 4nc. 1ll ri3$ts reserve&.
)e*+ords, .ol3el alumina0 2e%tural "ro"erties0 C$emical "ro"erties0 .urface $y&ro"$ilicity0 Catalytic e"o%i&ation0 )y&ro3en "ero%i&e
1. Introduction
2$e term alumina em#races a lar3e num#er of &ifferent
"ro&ucts $avin3 a wi&e variety of "ro"erties an& a""lica'
tions 617. 4n catalysis, alumina is ty"ically use& as a su""ort
or as a catalyst for a variety of &ifferent reactions 61,27.
)owever, as t$e term alumina &oes not refer to only one
com"oun& #ut to a series of aluminum o%i&es an& $y&ro%'
i&es, factors suc$ as stoic$iometry, crystallo3ra"$ic "$ase,
an& crystallinity must #e consi&ere& in or&er to ac$ieve
suit' a#le catalyst "ro"erties. -sually, for catalytic
a""lications, it is necessary to activate t$e alumina, w$ic$
is &one #y t$ermal &e$y&ration of aluminum $y&ro%i&e or
o%y$y&ro%'
i&e in a tem"erature ran3e of 280 to 900

C. 4n t$is
&e'
$y&ration a lar3e num#er of transition aluminas is forme&,
w$ose structures can #e i&entifie& #y t$eir :+; "attern.
4n t$e tem"erature ran3e of 280 to 600

C, ( '3rou"
alumi'
nas are o#taine&, w$ic$ inclu&e t$e - , . , /, an& (
forms. 2$eir "rinci"al c$aracteristics are lower
crystallinities an& more e%tensive "orous structures of t$e
aluminum o%i&e
<
Corres"on&in3 aut$or. !a%= >88 19 ?799?02?.
E#mail address, ulf@i( m. unica m " . # r (-. .c$uc$ar&t).
wit$ lar3e surface areas 617. 4n alumina activation many
factors, suc$ as "recursor ty"e, structural "ro"erties (crys'
tallinity, crystallite siAe, an& im"urities), mo&e of $eatin3,
an& final tem"erature, affect t$e structural "ro"erties of t$e
transition aluminas an& mo&ify t$eir reactivities in or3anic
reactions 6287. Bit$ res"ect to catalytic e"o%i&ation, alu'
mina was s$own to #e an efficient catalyst for a variety of
nucleo"$ilic olefins, suc$ as linear, cyclic an& su#stitute&
olefins an& ter"enes 6697. 1mon3 t$e a&vanta3es of usin3
alumina as an e"o%i&ation catalyst is t$at it is a
non"ollutin3 com"oun& an& t$at it is "ossi#le to use t$e
environmentally frien&ly o%i&ant $y&ro3en "ero%i&e. 2$e
activation of $y&ro' 3en "ero%i&e occurs "ro#a#ly t$rou3$
t$e reaction of weaC aci&ic sites (1l*)) of t$e alumina
surface to form $y' &ro"ero%i&e 3rou"s, w$ic$ are
res"onsi#le for t$e transfer of o%y3en to t$e olefin 697.
)owever, t$e "ro"erties w$ic$ t$e alumina re(uires to
$ave 3oo& catalytic activity are not yet well un&erstoo&.
2$e ( 'aluminas "re"are& #y &ifferent sol3el routes s$ow
&ifferent catalytic activities in t$e e"o%' i&ation of
cyclo$e%ene an& (& )'limonene usin3 an$y&rous )
2
*
2
in
et$yl acetate an& t$e ( 'alumina "re"are& from alu' minum
sec'#uto%i&e, usin3 o%alic aci& as 3elation catalyst, s$owe&
a si3nificant $i3$er e"o%i&ation activity com"are&
0021'9817/D see front matter 2004 5lsevier 4nc. 1ll ri3$ts
reserve&. &oi=10.1016/.cat.2004.06.029
3 01 0inaldi, U1 &c2uc2ardt 3 4ournal o5 Catal*sis 66% 76!!48 1!$9116
to commercial alumina 6?7. )owever, &ifferent ty"es of
com' mercial c$romato3ra"$ic aluminas (aci&ic, neutral,
an& #a' sic) $a& similar catalytic #e$aviors in t$e
e"o%i&ation of :'"inene 667. 2$e yiel& of e"o%i&es in t$e
alumina'catalyAe& e"o%i&ation is not affecte& #y t$e
e%c$an3e of an$y&rous )
2
*
2
#y a(ueous 70 wtE )
2
*
2
,
w$ic$, on t$e ot$er $an&, im"roves t$e lifetime an& t$e
"ro&uctivity of t$e catalyst 697. 4n t$e "resent stu&y, we
synt$esiAe& ultra"ure ( 'alumina via t$e sol3el route 6?7
an& evaluate& t$e influence of struc' tural, te%tural, an&
c$emical "ro"erties an& t$e amount of water on t$e (
'alumina surface on its catalytic activity in t$e e"o%i&ation
of cis'cyclooctene.
2. Experimental
6111 &*nt2esis o5 t2e
catal*sts
611111 ( #;l
6
O

#1
2$e "recursor of ( '1l
2
*
?
'1, Foe$mite'1, was "re'
"are& #y mi%in3 aluminum iso'"ro"o%i&e (9.?9 3, 1l&ric$,
< 99199E) wit$ nitric aci& (2.2 mG, 9 mol G
1
, /ercC,
".a.)
an& &eioniAe& water (?.2 mG) at 78

C for ?0 min. Ho
$omo'
3eneous solution was o#taine&. 2$e 3elatinous "reci"itate
was &rie& for ? &ays in air. 2$e Foe$mite'1 was treate&
un&er a flow of synt$etic air at 100, 200, an& 400

C, se'
(uentially, for 24 $ eac$, 3eneratin3 ( '1l
2
*
?
'1.
611161 ( #;l
6
O

#6
2$e "recursor of ( '1l
2
*
?
'2, Foe$mite'2, was "re"are&
#y t$e uncatalyAe& $y&rolysis of aluminum iso'"ro"o%i&e
(9.12 3, 1l&ric$, < 99199E) in &eioniAate& water (22.? mG)
at 98

C for 1 $. 1fter t$is "erio&, nitric aci& (0.?9
mG,
9 mol G
1
, /ercC, ".a.) was a&&e& for "e"tiAation an& t$e
sol reflu%e& for 12 $. 2$e water was remove& #y
&istillation
".a.). 2o t$is solution was a&&e& un&er vi3orous stirrin3
an a(ueous solution of o%alic aci& (7.8 mG, 0.78 mol G
1
,
.ynt$, ".a.). 2$e 3el was &rie& at 70

C for 24 $ an& t$en


t$e Foe$mite'4 was treate& un&er a flow of synt$etic air at
100, 200, an& 400

C, se(uentially, for 24 $ eac$,


3eneratin3
( '1l
2
*
?
'
4.
6161 Catal*st
c2aracteri'ation
616111 =#0a* po+er
di55raction
:'ray &iffraction "atterns were &etermine& wit$ a .$i'
ma&Au :;'?1 &iffractometer, usin3 Cu): ra&iation an&
2> from 8 to 90
o
, wit$ ste" siAes of 0.02
o
an& countin3
times of ? s. 2$e a""arent crystallite siAe of Foe$mite'1 to
Foe$mite'4, synt$esiAe& #y t$e &ifferent sol3el routes,
was &etermine& usin3 .c$errerIs e(uation an& t$e 020
reflection of t$e #oe$mite sam"les. Corun&um wit$ a
crystallite siAe of
1 Jm was use& as internal
stan&ar&.
616161 &ur5ace area
anal*sis
2$e nitro3en a&sor"tion&esor"tion isot$erms of ( '
1l
2
*
?
'1 to ( '1l
2
*
?
'4 were measure& on a
/icrometrics 1.1K 2010 e(ui"ment. 2$e surface area was
&etermine& #y a&sor"tion&esor"tion of nitro3en at 77 L.
2$e "ore volume an& avera3e "ore &iameter were
calculate& usin3 t$e F52 met$o&.
61611 ?emperature#pro@rammed desorption o5
ammonia and carAon dioxide
2$e tem"erature'"ro3ramme& &esor"tion (2K;) e%"er'
iments were carrie& out in a la#'#uilt e(ui"ment usin3 a
t$ermal con&uctivity &etector (2C;). 2y"ically, 100.0 m3
of ( 'alumina was treate& un&er a flow of nitro3en (?0 mG
an& t$e soli& was &rie& at 70

C in an oven for 24 $ to re'


min
1
) at 400

C for 1 $. 2$e sam"le was allowe& to cool


move resi&ual water. 2$e Foe$mite'2 was treate& un&er a
flow of synt$etic air at 100, 200, an& 400

C, se(uentially,
to 100

C un&er a flow of nitro3en. 2$e a&sor"tion of t$e
"ro#e molecule (ammonia or car#on &io%i&e) was accom'
for 24 $ eac$, 3eneratin3 ( '1l
2
*
?
'2.
"lis$e& at 100

C for 1 $ usin3 a flow of ?0 mG min


1
of a
61111 ( #;l
6
O

#
3aseous mi%ture of 10E (v3v) of t$e "ro#e molecule in ni'
tro3en. 2$e e%cess of t$e "ro#e molecule was remove& #y
2$e "recursor of ( '1l
2
*
?
'?, Foe$mite'?, was o#taine&
a flow of ?0 mG min
1
of nitro3en for 1 $ at 100

C. 1f'
#y t$e $y&rolysis of aluminum iso'"ro"o%i&e (10.2 3,
1l&ric$, < 99199E) &issolve& in iso"ro"anol (18 mG,
/ercC, ".a.), catalyAe& #y an a(ueous solution of o%alic
aci&
(7.8 mG, 0.78 mol G
1
, .ynt$, ".a.) un&er vi3orous
stirrin3.
2$e mi%ture was reflu%e& for ? $. 2$e 3el was &rie& at 70

C
for 24 $ an& t$en t$e Foe$mite'? was treate& un&er a flow
of synt$etic air at 100, 200, an& 400

C, se(uentially, for
24 $
eac$, 3eneratin3 ( '1l
2
*
?
'
?.
611141 ( #;l
6
O

#4
2$e "recursor of ( '1l
2
*
?
'4, Foe$mite'4, was "re"are&
4 01 0inaldi, U1 &c2uc2ardt 3 4ournal o5 Catal*sis 66% 76!!48 1!$9116
usin3 t$e same "roce&ure as for Foe$mite'?, #ut
su#stitutin3
aluminum iso'"ro"o%i&e #y aluminum sec'#uto%i&e (10.0
3, 1l&ric$, 99.99E) &issolve& in sec'#utanol (18 mG,
Metec,
terwar&, t$e sam"le was $eate& to 900

C at a $eatin3
rate
of 10

C min
1
an& t$e &esor#e& "ro#e molecule
(uantifie&
usin3 t$e 2C; &etector. FlanC 2K; e%"eriments were &one
for all ( 'aluminas an& t$eir results were su#tracte& from
t$e 2K; curves o#taine& for t$e &esor#e& "ro#e molecules.
616141 ?2ermo@ravimetric
anal*sis
2$ermo3ravimetric (2N) analyses of Foe$mite'1 to
Foe$mite'4 were carrie& out un&er an o%i&ative
atmos"$ere
(synt$etic air, 100 mG min
1
) usin3 a 21 /icrometrics
2980 2N1 instrument wit$ a $eatin3 rate of 10

C min
1
in t$e ran3e of ?0900

C. !or 2N analyses of ( '1l


2
*
?
'1
to
( '1l
2
*
?
'4 a $eatin3 rate of 20

C min
1
in t$e
tem"erature
ran3e of 28978

C was
use&.
616151 Elemental
anal*sis
5lemental analyses were carrie& out usin3 a KerCin'
5lmer .eries 44 C)H ./* 1nalyAer /o&el 2400. .am"les
of Foe$mite'1 to Foe$mite'4 an& ( '1l
2
*
?
'1 to ( '1l
2
*
?
'4 were mi%e& wit$ an o%i&ant mi%ture (K#
?
*
4
/Ha!, 1=7)
an& t$e elemental analysis was "erforme& #y com#ustin3
t$e
sam"les at 928

C. 2$e analyses were &one in
tri"licate.
616161 Qualitative =#ra* 5luorescence
anal*sis
2$e ( '1l
2
*
?
'1 to ( '1l
2
*
?
'4 sam"les were
analyAe& #y :'ray fluorescence, usin3 a .$ima&Au ener3y'
&is"ersive :'ray s"ectrometer, /o&el 5;:'700, a 10'mm
collimator, an& a +$ :'ray tu#e at 18 CM (for Ha to .c) an&
80 CM (for 2i to -), un&er vacuum.
611 Catal*tic
reactions
2$e a(ueous solution of $y&ro3en "ero%i&e (70 wtE)
was su""lie& #y KerO%i&os &o Frasil ..1. (.olvay) an& was
use& wit$out furt$er treatment. 2$e ot$er rea3ents were
also use& wit$out furt$er treatment.
1 mi%ture of cyclooctene (10 mmol, 1cros, 98E), $y'
&ro3en "ero%i&e (20 mmol), &i'n'#utyl et$er (8 mmol, in'
ternal stan&ar&, !luCa, < 99E), an& et$yl acetate (10 mG,
/ercC, ".a.) was $eate& un&er reflu% wit$ ma3netic stirrin3
for 1 $. 1 sam"le was taCen for NC analysis (#lanC) an& t$e
reaction starte& #y a&&ition of t$e ( 'alumina (200.0 m3).
.am"les were taCen at &ifferent reaction times an& treate&
wit$ a few milli3rams of man3anese &io%i&e, for &ecom"o'
sition of t$e "ero%i&es, an& t$en wit$ an$y&rous so&ium
sul' fate, to remove resi&ual water. 2$e sam"les were
analyAe& usin3 a )ewlett'KacCar& )K 8990 .eries 44 3as
c$romato' 3ra"$ e(ui""e& wit$ an 1lltec$ 12'B1:
ca"illary column
(20 m 0128 mm 0128 Jm film t$icCness) an& a flame
ion'
iAation &etector (!4;). 2$e cyclooctene e"o%i&e was (uan'
tifie& usin3 a cali#ration curve o#taine& wit$ a stan&ar& so'
lution. .electivity is always 3iven wit$ res"ect to converte&
cyclooctene.
3. Results and discussion
2$e &ifferent routes of sol3el synt$esis yiel& #oe$mites
wit$ &ifferent crystallinities 6107. 2$e fast $y&rolysis of t$e
aluminum iso"ro"o%i&e, use& in t$e synt$esis of Foe$mi'
te'1, resulte& in a material wit$ very "oor crystallinity.
2$e noncatalyAe& $y&rolysis of aluminum iso"ro"o%i&e
fol' lowe& #y "e"tiAation in nitric aci& resulte& in a $i3$er
crys' tallinity (Foe$mite'2). Foe$mite'? an& Foe$mite'4,
w$ic$ were synt$esiAe& #y $y&rolysis of aluminum
iso"ro"o%i&e an& sec'#uto%i&e, res"ectively, wit$ o%alic
aci& as 3elation catalyst, were o#taine& wit$ interme&iate
crystallinities. 2$e :+; "atterns of t$ese ("seu&o)'
#oe$mites are s$own in !i3. 1.
2$e a""arent crystallite siAes of t$e #oe$mites,
estimate& usin3 .c$errerIs e(uation, are s$own in 2a#le 1.
Foe$mite'2
!i3. 1. Kow&er :+; "attern of t$e #oe$mites synt$esiAe& #y &ifferent sol
3el routes.
2a#le 1
1""arent crystallite siAes of t$e #oe$mites synt$esiAe& #y &ifferent sol3el
routes
.oli& d s"acin3 (nm) 1""arent crystallite siAe (nm)
Foe$mite'1 01629 n1&1
Foe$mite'2 01644 811
Foe$mite'? 01649 418
Foe$mite'4 01680 417
n.&., not &etermine&.
to Foe$mite'4 are nanocrystalline soli&s 6117. 2$e a""arent
crystallite siAe was not estimate& for Foe$mite'1, as t$is
ma' terial is more amor"$ous t$an crystalline. 2$us it was
not "ossi#le to measure t$e wi&t$ at $alf $ei3$t of t$e 020
re' flection.
2$e t$ermo3ravimetric curves of t$e #oe$mites synt$e'
siAe& #y t$e &ifferent routes are s$own in !i3. 2. 1ccor&'
in3 to t$ese 2N curves, t$e #oe$mites $ave four re3ions
of wei3$t loss= (i) room tem"erature to ca. 120

C, &ue to
&esor"tion of "$ysically #on&e& water an& resi&ual solvent0
(ii) ca. 120 to ?00

C, corres"on&in3 to &esor"tion of
c$emi'
cally #on&e& water an& or3anic molecules #etween t$e
inter' layers0 (iii) ca. ?00 to 800

C, corres"on&in3 to
&e$y&ro%y'
lation &urin3 t$e "$ase transition of #oe$mite to ( 'alumina
an& t$e #urnin3 of resi&ual or3anic material0 (iv) a#ove
800

C, &ue to &e$y&ration of ( 'alumina an& "osterior
"$ase
transitions (( B > 'alumina)
611,127.
2$e t$ermal #e$avior of t$e #oe$mites &e"en&s stron3ly
on its crystallinity an& on t$e crystallite siAe 61,1?7.
Foe$mi' te'1 an& Foe$mite'2 $ave a similar "rofile of
wei3$t loss. )owever, &ue to t$e lar3er crystallite siAe of
Foe$mite'2 (2a' #le 1), t$e &esor"tion of c$emically
#on&e& water is slower, as can #e seen #y t$e smaller
wei3$t loss in t$e secon& re' 3ion. 2$e conversion of
#oe$mite to ( '1l
2
*
?
consists in &e$y&ro%ylation of t$e
s"ace #etween t$e #oe$mite &ou#le layers. 4n lar3er
crystallites of #oe$mite, t$is is more &if'
2a#le 2
!i3. 2. 2N curves of t$e #oe$mites. !i3. ?. :+; "attern of t$e aluminas calcine& at 400

C.
Car#on assay for t$e #oe$mites #efore an& after calcination at 400

C
.oli& Car#on assay (E)
Fefore calcination 1fter calcination
Foe$mite'1 117 016
Foe$mite'2 211 016
Foe$mite'? 814 111
Foe$mite'4 819 019
ficult #ecause t$e c$emisor#e& water an& or3anic
molecules $ave lon3er &iffusion "at$s, w$ic$ su""ress t$e
"$ase transi' tion of #oe$mite to ( 'alumina 61?7. 2$e
$i3$er wei3$t losses o#serve& for Foe$mite'? an&
Foe$mite'4 in t$e secon& an& t$ir& re3ion are &ue to
&ecom"osition of o%alic aci& &urin3 t$e t$ermal treatment.
5lemental analyses of t$e #oe$mites
as "re"are& an& after calcination at 400

C s$ow (2a#le 2)
t$at almost all or3anic material was remove& &urin3 cal'
cination, since t$e car#on assay for t$e calcine& materials
is com"ara#le to t$e instrumental error of t$e e(ui"ment
(018E for car#on).
Foe$mite'1 to Foe$mite'4 were transforme& into
( '1l
2
*
?
'1 to ( '1l
2
*
?
'4, res"ectively, after calcination
at
400

C as s$own #y t$e ty"ical :+; "atterns in !i3. ?
6147.
2$e :+; "atterns s$ow very #roa& "eaCs in&icatin3 small
crystallite siAes an&/or not well crystalliAe& materials.
( '1l
2
*
?
'1, ( '1l
2
*
?
'2, an& ( '1l
2
*
?
'4 e%$i#it a
similar :+; "attern0 $owever, ( '1l
2
*
?
'? is #etter
&escri#e& as an amor"$ous soli&, as in&icate& #y a #roa&
#an& at 2> #etween
20 an& 40

. 2$e crystallite siAe of t$e calcine& ( 'aluminas


were not calculate& &ue to t$e a#sence of well'&efine&
"eaCs #elow 2> = 40

.
;es"ite t$e similarities of t$e :+; "attern of ( '1l
2
*
?
'
1, ( '1l
2
*
?
'2, an& ( '1l
2
*
?
'4 t$eir activities in t$e
e"o%i'
&ation of cis'cyclooctene are totally &ifferent, as s$own in
!i3. 4. 2$e structural c$aracteristics of t$e ( 'alumina &o
not seem to $ave any &irect correlation wit$ t$eir catalytic
ac' tivity. 2$e most active alumina is ( '1l
2
*
?
'4, w$ic$
3ives a
!i3. 4. 1lumina'catalyAe& e"o%i&ation of cis'cyclooctene. +eaction con&i'
tions= 200 m3 of ( 'alumina, 10 mmol of cyclooctene, 20 mmol of
$y&ro3en "ero%i&e, un&er reflu%.
yiel& of cyclooctene e"o%i&e of ca. 68E after 6 $, followe&
#y alumina ( '1l
2
*
?
'? (ca. 48E), ( '1l
2
*
?
'1 (ca. ?0E),
an& ( '1l
2
*
?
'1 (ca. 20E). 2$e #lanC reaction wit$out
catalyst 3ives a yiel& of ca. 7E, in&icatin3 t$at alumina is
really catalyAin3 t$e e"o%i&ation. !or all reactions t$e
selectivity for cyclooctene e"o%i&e was $i3$er t$an 99E.
2$e same se' lectivity was o#serve& for more straine&
e"o%i&es, suc$ as cyclo$e%ene e"o%i&e 6?,97 an& (& )'
limonene e"o%i&es 6?7, in&icatin3 t$at t$ere are no stron3
aci& sites on t$e alumina surface un&er t$e reaction
con&itions use& 697. 2$e catalytic activity of t$e (
'aluminas is not &ue to im"urities. 1s al' rea&y note&, t$e
car#on content of t$e calcine& aluminas is low an&
&is"ersive :'ray fluorescence analyses s$owe& only traces
of iron, in low ""m (uantities, so low t$at no re"ro'
&uci#le results coul& #e o#taine&.
!i3. 8. Hitro3en a&sor"tion&esor"tion isot$erms at 77 L of t$e ( 'aluminas.
2$e te%tural "ro"erties of t$e catalysts are anot$er rel'
evant factor for t$e catalytic activity of alumina, since t$e
a&sor"tion&esor"tion isot$erms at 77 L, w$ic$ are s$own
in t$e !i3. 8.
1&sor"tion isot$erms of ty"e 44 were o#serve& for
( '1l
2
*
?
'1, ( '1l
2
*
?
'?, an& ( '1l
2
*
?
'4, in&icatin3 t$at
t$ey are non"orous soli&s. )owever, t$ese isot$erms $ave a
ty"e )? $ysteresis, in&icatin3 t$at nonstructural meso"ores
are "resent, w$ic$ are forme& #y "article "acCin3. 2$is
ty"e of $ysteresis is foun& for slit's$a"e& "ores #etween
"late' liCe "articles, w$ic$ are so lar3e t$at ca"illary
con&ensation
$a""ens only at a relative "ressure close to P 3P
0
= 1 6167.
)owever, ( '1l
2
*
?
'2 $as a ty"e 4M isot$erm wit$ a
ty"e
)2 $ysteresis, in&icatin3 t$e e%istence of inC #ottle's$a"e&
meso"ores. 2$e surface area (;
F52
), "ore volume, an&
avera3e "ore &iameter of t$e aluminas are 3iven in 2a'
#le ?.
2$e lower catalytic activity of ( '1l
2
*
?
'1 can #e
&irectly relate& to its small surface area, w$en com"are&
wit$ t$e more active ( '1l
2
*
?
'? an& ( '1l
2
*
?
'4.
)owever, alumina ( '1l
2
*
?
'2 $as a sli3$tly lar3er surface
area t$an ( '1l
2
*
?
'? an& ( '1l
2
*
?
'4 an& its e"o%i&e
yiel& is only ? mmol after
6 $. *n t$e ot$er $an&, 1l
2
*
?
'2 is a meso"orous
material wit$out slit's$a"e& "ores #etween t$e "late'liCe
"articles as
2a#le ?
2e%tural "ro"erties of aluminas calcine& at 400

C
( '1l
2
*
?
'4
a
296 1129 1910
a
Honstructural "orosity.
o#serve& for ( '1l
2
*
?
'1, ( '1l
2
*
?
'?, an& ( '1l
2
*
?
'4.
2$e lower yiel& of e"o%i&e for ( '1l
2
*
?
'2 is "ro#a#ly
&ue to t$e entra"ment of water in t$e inC #ottle's$a"e&
meso"ores &urin3 t$e reaction, not allowin3 t$e a""roac$
of t$e $y' &ro"$o#ic olefin to t$e active sites. 2$e surface
area an& "orous system of ( '1l
2
*
?
'? an& ( '1l
2
*
?
'4 are
very sim' ilar. )owever, after 6 $ t$e yiel& of e"o%i&e is ca.
6.8 mmol for alumina ( '1l
2
*
?
'4 an& only ca. 4.8 mmol
for alumina ( '1l
2
*
?
'?, in&icatin3 t$at t$e catalytic
activity of t$e alu' mina cannot #e totally e%"laine& #y its
te%tural "ro"erties.
4n or&er to analyAe t$e aci&ic an& #asic "ro"erties of t$e
( 'aluminas we "erforme& tem"erature'"ro3ramme&
&esor"' tion of ammonia an& car#on &io%i&e (2K;'H)
?
an& 2K;' C*
2
, res"ectively). !i3. 6 s$ows t$e "rofiles of
t$e 2K;' H)
?
curves for ( '1l
2
*
?
'1, ( '1l
2
*
?
'2, (
'1l
2
*
?
'?, an& ( '1l
2
*
?
'4.
2$e stren3t$ of interaction #etween ammonia an& t$e
aci&ic sites &etermines t$e &esor"tion tem"erature. )ow'
num#er of active sites, t$eir 3eometry, an& t$eir reactivity 1lumina ;
F52
Kore volume 1vera3e "ore
&e"en& mainly on t$e 3eometry of t$e voi& s"ace insi&e
(m
2
3
1
) (cm
?
3
1
) &iameter (nm)
t$e "articles, as well as #etween t$em 6187. 2$e te%tural ( '1l
2
*
?
'1
a
14? 0184 1811
"ro"erties of t$ese ( 'aluminas were &etermine& #y nitro3en
( '1l
2
*
?
'2
( '1l
2
*
?
'?
a
??0
299
01?7
1141
?19
1916
!i3. 7. 2K;'C*
2
"rofiles for aluminas calcine& at 400

C.
2a#le 4
!i3. 6. 2K;'H)
?
"rofiles for aluminas calcine& at 400

C.
only stron3 #asic sites, 3ivin3 similar 2K; "rofiles. )ow'
ever, t$ese #asic sites are PneutraliAe&Q un&er reaction
con&i' tions #y et$yl acetate or small amounts of acetic aci&
w$ic$
may #e forme& #y $y&rolysis of t$e solvent 627. 2$erefore,
;istri#ution of aci&ic sites on t$e alumina surfaces
1lumina 1mount of aci&ic sites, a.u.33 (relative amount, E)
t$e "artici"ation of t$ese sites in t$e catalytic e"o%i&ations
is #elieve& to #e unim"ortant un&er t$ese reaction
con&itions.
BeaC to mo&erate
aci&ic sites
a
.tron3 aci&ic sites
#
2otal "er 3ram
2$e aci&ic an& #asic "ro"erties of t$e ( 'alumina
surfaces, &etermine& #y t$e 2K; e%"eriments, are only
vali& for a
( '1l
2
*
?
'1 24? (60) 161 (40)
404
( '1l
2
*
?
'2 281 (69) 119 (?2)
?69
( '1l
2
*
?
'? 264 (60) 176 (40)
440
( '1l
2
*
?
'4 ?6? (64) 209 (?6)
871
;esor"tion tem"eratures=
a
100880

C an&
#
880900

C.
ever, #esi&es its c$emical nature, t$e stren3t$ of t$e aci&ic
sites &e"en&s also on t$e nei3$#ors t$at surroun& it 617,197.
!or crystalline soli&s, t$ese nei3$#ors are t$e same in all
&i' rections of t$e lattice, creatin3 aci&ic an& #asic sites
wit$ &istinct stren3t$s, as was s$own #y Keri 6197 an&
LnRAin3er an& +atnasamy 647. *n t$e ot$er $an&, for
"oorly crys' talline or amor"$ous soli&s, t$e nei3$#ors are
not t$e same, creatin3 a wi&e ran3e of stren3t$s of
&ifferent aci&ic an& #asic sites. 2$erefore, t$e "oorly
crystalline structures of t$e ( 'aluminas (!i3. ?) are t$e
reason for t$e very #roa& an& su"erim"ose& "eaCs in t$e
2K;'H)
?
"rofiles t$at are s$own in !i3. 6. 2a#le 4 s$ows
t$e &istri#ution of aci&ic sites on t$e alumina surfaces.
.ur"risin3ly, t$e relative amounts of aci&ic sites wit$
&ifferent aci& stren3t$s are sim' ilar for all t$ese (
'aluminas. 4n contrast, t$e total amounts of aci&ic sites are
&ifferent an& can #e &irectly correlate& wit$ t$e activity in
t$e e"o%i&ation of cis'cyclooctene for ( '1l
2
*
?
'2, (
'1l
2
*
?
'?, an& ( '1l
2
*
?
'4. )owever, ( '1l
2
*
?
'1,
w$ic$ $as more aci&ic sites t$an ( '1l
2
*
?
'2, s$ows
lower activity.
2$e sol3el routes for t$e "re"aration of ( 'alumina "re'
cursors also create &ifferent "o"ulations of #asic sites on
t$e ( 'alumina surfaces, as can #e seen in t$e 2K;'C*
2
"rofiles s$own in !i3. 7. Ho #asic sites are o#serve& on t$e
( '1l
2
*
?
'
1 surface. *n t$e ot$er $an&, ( '1l
2
*
?
'1 s$ows weaC as
well
as stron3 #asic sites an& ( '1l
2
*
?
'? an& ( '1l
2
*
?
'4
"ossess
Pcleane&Q surface, o#taine& in t$e "retreatment ($eatin3 at
400

C for 1 $) use& in t$e 2K; e%"eriments. 2$e alumina


surface un&er reaction con&itions, $owever, is com"letely
re' $y&rate& as a(ueous )
2
*
2
is use&. 2$us t$e Gewis aci&
sites,
*1l
+
*, are transforme& into FrSnste& aci& sites, 1l
*) or 1l*)
2
+
. 2$e aci& stren3t$ of t$ese sites is weaC
to
mo&erate, as stron3 aci& sites are e%"ecte& to react wit$ t$e
e"o%i&e formin3 rin3'o"ene& #y'"ro&ucts, w$ic$ were not
o#serve&.
1n im"ortant factor t$at may restrict t$e reactivity of t$e
alumina surface is its $y&ro"$ilicity. 4t is Cnown t$at t$e
e"o%i&ation catalyst use& in&ustrially #y .$ell for t$e "ro'
&uction of "ro"ylene o%i&e (2i(4M)/.i*
2
) cannot #e use&
wit$ )
2
*
2
, #ecause t$is woul& create a water layer on its
surface, maCin3 t$e a""roac$ of t$e olefin &ifficult an&
"oi' sonin3 t$e active sites (2i(4M)) 67,207. Karticularly
effective 2i(4M)/.i*
2
catalysts are o#taine& w$en t$e
&e"osition of ti' tanium(4M) on silica is followe& #y
furt$er treatment wit$ an or3anic silylatin3 a3ent to
remove t$e resi&ual FrSnste& aci&ity arisin3 from .i*)
6217. 4n contrast, t$e remarC' a#le reactivity of 2.'1 in
catalytic e"o%i&ation wit$ a(ueous
?0 wtE )
2
*
2
is &ue to t$e $y&ro"$o#icity of its surface
t$at allows t$e a""roac$ of t$e olefin to t$e active sites
even in t$e "resence of water 677.
2$e surface of t$e calcine& alumina, w$en e%"ose& to
wa' ter (from atmos"$eric air or from t$e reaction
mi%ture), un' &er3oes re$y&ration. 2$e e%tension of t$is
"rocess &e"en&s on t$e structural an& te%tural "ro"erties of
t$e alumina. 2$er' mo3ravimetric analyses of t$e (
'aluminas as use& in t$e
catalytic reactions (calcine& at 400

C an& re$y&rate& in
air)
were carrie& out in or&er to evaluate t$e amount of "$ysical
an& c$emically #on&e& water on t$eir surfaces (!i3. 9).
!i3. 9. 2N curves of aluminas calcine& at 400

C.
2$e wei3$t loss o#serve& for alumina calcine& at 400

C
(!i3. 9) can #e assi3ne& to t$e &esor"tion of "$ysically (u"
to ca. 200

C) an& c$emically (a#ove 200



C) #on&e&
wa'
ter from t$e surface. 2$ese values are only a""ro%imate, as
ot$er com"oun&s may also #e evolve&0 $owever, &eviations
s$oul& #e small as t$e car#on content is low an&
statistically t$e same for all ( 'aluminas use& in t$is stu&y
(2a#le 2). *n t$e ot$er $an&, t$e amount of water evolve&
cannot #e &i' rectly correlate& to t$e $y&ro"$ilicity of t$e
alumina surfaces as t$e surface areas vary consi&era#ly
(2a#le ?). 1 #etter way is to consi&er t$e amount of
water &esor#e& "er unit of surface area of t$e alumina.
2$e num#er of t$e water molecules "er s(uare nanometer
of t$e alumina surface was
calculate& usin3
ties= ( '1l
2
*
?
'1 < ( '1l
2
*
?
'? < ( '1l
2
*
?
'2 < ( '1l
2
*
?
'4. 2$e $i3$ly $y&ro%ylate& surface of ( '1l
2
*
?
'1
(?7.4
)
2
*3nm
2
) is #elieve& to #e t$e res"onsi#le factor for its
lowest catalytic activity, as t$e water layer forme& #ecomes
a Cinetic #arrier for olefin a""roac$ to t$e active sites on
t$e surface. Consi&erin3 t$e ( 'aluminas wit$ t$e same
non' "orous surfaces (( '1l
2
*
?
'1, ( '1l
2
*
?
'?, an& (
'1l
2
*
?
'4), t$e catalytic activity can #e &irectly relate& to
t$e "o"ula' tion of water on t$e surface. )owever, alt$ou3$
( '1l
2
*
?
'2 is less $y&ro"$ilic t$an ( '1l
2
*
?
'?, its
catalytic activity is low, "ro#a#ly &ue to its inC #ottle'
s$a"e& meso"ores, w$ic$ entra" water &urin3 t$e reaction,
t$us stron3ly re&ucin3 t$e active surface area of t$e
alumina.
2$e values o#taine& for t$e &e$y&ration of t$e (
'alumina surface at 200

C are in t$e same or&er of
ma3nitu&e as
t$ose &etermine& #y ;e Foer et al. 6227 an& Keri 62?7
for ( 'alumina after evacuation at 28

C for 100 $ or
af' ter &ryin3 at 120

C (1? an& 9.28 water molecules
"er
1 nm
2
, res"ectively). 1roun& 200

C, a""ro%imately
all
"$ysically a&sor#e& water is li#erate& an& t$e aluminas
( '1l
2
*
?
'2, ( '1l
2
*
?
'?, an& ( '1l
2
*
?
'4 $ave
a""ro%imately t$e same "o"ulation of water on t$eir
surface. 4n con' trast, ( '1l
2
*
?
'1 $as muc$ more water
on its surface. 2$e
C 728

C83 C 7200

C8 ratio is a""ro%imately t$e same
for
( '1l
2
*
?
'2, ( '1l
2
*
?
'?, an& ( '1l
2
*
?
'4 ( 219)0 $owever,
it
is muc$ lower for ( '1l
2
*
?
'1 (1.9) w$ic$ is muc$ more
$y'
&ro"$ilic an&, t$erefore, stron3ly #in&s water on its
surface.
2$is result is certainly very interestin3, as in an earlier
"a"er 667 we sur"risin3ly foun& t$at commercial c$romato'
3ra"$ic aluminas of &ifferent ty"es (weaCly aci&ic, aci&ic,
neutral an& #asic) s$owe& similar catalytic activities in t$e
e"o%i&ation of :'"inene. 2$e reasons for t$is result are
m
C 7?

C8 =
)
2
*
1
;
F52

D
1
,
m
i
(1)
now well un&erstoo& as all commercial aluminas use& were
FrocCmann 3ra&e 4 6247, w$ic$ means t$at t$e $y&ro"$ilic'
ities of t$ese aluminas were a""ro%imately t$e same. )ow'
w$ere C 7?

C8 is t$e num#er of water molecules "er
s(uare
nanometer of alumina surface at a 3iven tem"erature0 m
is t$e wei3$t loss in 3rams at a 3iven tem"erature (3)0 m
i
is
t$e initial wei3$t of t$e alumina sam"le (3)0 E
)
2
*
is t$e
mo'
lar mass of water (19.018? 3 mol
1
)0 D
1
is t$e 1vo3a&ro
constant (61022 10
2?
mol
1
)0 ;
F52
is t$e surface area &e'
termine& #y t$e F52 met$o& (nm
2
3
1
).
2$e values of C 728

C8 an& C 7200

C8 of t$e
calcine&
aluminas, as well as t$e "arameters use& in t$e calculations,
are 3iven in 2a#le 8.
1nalyAin3 t$e values of C 728

C8, it is "ossi#le to
or&er
t$e re$y&rate& ( 'aluminas accor&in3 to t$eir
$y&ro"$ilici'
ever, t$e alumina "re"are& from aluminum sec'#uto%i&e,
us' in3 o%alic aci& as 3elation catalyst, s$owe& a #etter
catalytic activity in t$e e"o%i&ation of cyclo$e%ene, cis'
cyclooctene, an& (& )'limonene com"are& wit$
commercial alumina 6?7 &ue to t$e lower $y&ro"$ilicity of
its surface.
4. Conclusions
2$e structural "ro"erties of t$e ( 'aluminas &o not seem
to #e very im"ortant for t$eir activities in t$e catalytic
e"o%' i&ation of cis'cyclooctene wit$ a(ueous )
2
*
2
. 2$e
te%tural
E
2a#le 8
Hum#er of water molecules "er nm
2
of alumina surface
1lumina m
initial
m
? =200

C
m
final
Bater molecules "er nm
C728

C8
(m3) (m3) (m3) C728

C8 C 7200

C8 C 7200

C8
( '1l
2
*
?
'1 121892 111622 101879 ?714 1914 119
( '1l
2
*
?
'2 281280 221194 201846 1919 616 219
( '1l
2
*
?
'? 9190? 71698 71096 2216 910 219
( '1l
2
*
?
'4 91182 91?99 71990 1612 618 218
2
"ro"erties, $owever, are im"ortant0 t$e ( 'aluminas s$oul&
$ave a lar3e surface area an& an o"en structure. 1n o"en
structure is im"ortant in or&er to avoi& t$e entra"ment of
water in t$e "orous system, w$at maCes t$e &iffusion of t$e
olefin to active sites &ifficult. 2$e relations$i" of aci&ic
"ro"' erties, suc$ as FrRnste& aci&ity, wit$ te%tural
"ro"erties can #e e%"resse& in terms of t$e $y&ro"$ilicity
of t$e surface, w$ic$ s$oul& #e sufficient to 3uarantee a
fast reaction wit$ $y&ro3en "ero%i&e formin3 1l**)
3rou"s on t$e surface, #ut s$oul& not #e too $i3$ in or&er
to allow a fast a""roac$ of t$e olefin to t$e active sites for
t$e o%y3en transfer to t$e olefin. -n&er t$e con&itions use&
in t$is stu&y, t$e sol3el alumina ( '1l
2
*
?
'4 #est fulfills
t$ese re(uirements.
Acknowledgments
Be t$anC Krof. )eloysa /artins &e Carval$o 1n&ra&e
(4T/-!F1) for t$e use of t$e 2K; instrument an& Krof. 4ris
2orriani (4!NB/-H4C1/K) for $el"ful su33estions on t$e
;+: analyses. Be are 3rateful to t$e !un&aUVo &e 1m"aro
W Kes(uisa &o 5sta&o &e .Vo Kaulo (!1K5.K) an& t$e Con'
sel$o Hacional &e Kes(uisa e ;esenvolvimento (CHK() for
fellows$i"s an& financial su""ort.
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1 G Y14?/1ct iv ate&Y1lu m in a. $ tm l .