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Synthesis and characterization of SBA-15 materials functionalized
with olefinic groups and subsequent modification through oxidation
procedures
R. van Griekena, J. Iglesiasb, V. Moralesaand R.A. Garcaa*
aDepartment of Chemical and Environmental Technology, ESCET, Universidad Rey
Juan Carlos, C/ Tulipn s/n, !"## $%stoles, $adrid, Spain
&Department of Chemical and Energy Technology, ESCET, Universidad Rey Juan
Carlos, C/ Tulipn s/n, !"## $%stoles, $adrid, Spain
Published on:
Microporous and Mesoporous Maerials !"! #$%!%& "$!'""%
doi:!%.!%!().+icro+eso.$%!%.%!.%!%
* o -ho+ correspondence should be addressed.
raael.garcia/urc.es
Ph. 0"1 2! 133 4%3(. 5a6 0"1 2! 133 4%(3
!
http://dx.doi.org/10.1016/j.micromeso.2010.01.010mailto:[email protected]:[email protected]://dx.doi.org/10.1016/j.micromeso.2010.01.0108/11/2019 Micmat 4488 Final
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Abstract
he s7nhesis o alken7l'89A'! +aerials has been carried ou hrough dieren
+ehodologies. he direc's7nhesis +ehod used or he uncionali;aion o 89A'!
involving he co'condensaion o he alken7l'silicon precursor ogeher -ih silicon
alko6ides is clearl7 superior han an7 oher pos's7nheic pah-a7, even i acid
caal7ss are used o drive he pos's7nheic graing o olein groups. he direc'
s7nhesis +ehodolog7 has been deepl7 sudied -ihin his -ork, involving he
inluence o he silica precursor preh7drol7sis i+e, and he loading o dieren olein'
silanes on he ?8. he +odiicaion o hese alken7l
groups hrough o6idaion can be acco+plished hrough pos's7nheic o6idaion o he
oleinic group or even hrough an in'siu +ehodolog7 -here he o6idan @ h7drogen
pero6ide @ is added ogeher -ih he res o he precursor ino he s7nhesis gel o lead
co+plee o6idaion o he double bonds o-ards gl7colic uncionaliies. he resulan
+aerials sho- poenial as h7drophilic adsorbens and caal7ic suppors.
Keywords ?rganic uncionali;aion, 89A'!, olein groups, in'siu o6idaion,
gl7cols.
$
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1! "ntroduction
he s7nhesis o +esosrucured +aerials !,$B has received +uch aenion since heir
discover7 in earl7 2%Cs because o he high poenial o hese solids in +an7 ields. he
high surace area and pore volu+e values ogeher -ih he narro- pore si;e disribuion
inheren o hese +aerials "B +ake he+ speciall7 aracive o be used as suppors or
heerogeneous caal7sis 1,B, adsorbens (B, suppors or chro+aograph7 saionar7
phases 4,3B, and +an7 ohers. hus, +esosrucured +aerials have been uncionali;ed
-ih boh inorganic and organic species in order o provide addiional ph7sico'che+ical
properies o he silica paren +aerial. Inorganic species such as sals, +eals or +eal
o6ides 2,!%B are usuall7 incorporaed o he srucure o +esoporous +aerials
searching a speciic caal7ic acivi7, -hereas organic species !!,!$B are 7picall7
suppored looking or special ph7sical or che+ical properies in he solids, such as
h7drophobici7)h7drophilici7, che+ical aini7 and reacivi7 and also caal7ic
acivi7 !"B.
?rganic uncionali;aion o +esosrucured +aerials can be acco+plished b7 -o +ain
roues: pos's7nheic surace ransor+aions and direc s7nhesis procedures !!B.
Pos's7nheic surace uncionali;aion is usuall7 carried ou hrough graing
procedures. ?her +ehods, such as h7drosil7laion !1B can also be e+plo7ed, hough
hese are less -idespread han surace graing. Pos's7nhesis uncionali;aion usuall7
akes advanage o he surace reacive groups, -hich are liable o be +odiied -ih
several organic +oieies o be anchored ono he silica surace. In his +ehod boh he
sil7laion o silica and he phosphorilaion o +eal o6ides can be included. he pos'
s7nheic +ehodologies usuall7 leads o lo- uncionali;aion degrees ogeher -ih a
lo- dispersion o he uncionali7, since he a+oun o organic loading incorporaion is
li+ied b7 he iniial densi7 o surace silanols groups. ?n he oher hand is
"
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condensaion roues. In his case, he a+oun o organosilane -as kep belo- $% =+ole
regarding he silica source. Alhough he ordering degree o he uncionali;ed +aerials
-as good, i -as even beer or 89A'! 7pe sa+ples. Haer, Ehong et al. $!B
described a si+ilar +ehodolog7 or he preparaion o vin7l'89A'! +aerials -ih
higher uncionali7 loadings. o-ever, he sa+ples prepared -ih higher loadings han
$% +ole= o organosilane uncionali7 displa7ed poor orderings. ang et al. $$B
repored a -a7 o overco+e his li+i in he a+oun o oleinic groups -ihou causing
da+ages on he +esosrucure hrough he use o MgEl$in he s7nhesis +edia. 5inall7,
Dao et al. $"B have repored he s7nhesis o cubic 89A'! +aerials conaining vin7l
uncionaliies, hough he porous srucure -as readil7 blocked
8everal ransor+aions o double bonds ino oher organic uncionaliies have been
applied o he +odiicaion o olein'uncionali;ed +esosrucured +aerials. hus,
bro+inaions $1,$B, sulonaion $(B, h7droboraions $('$3B or o6idaions $3,$2B
have been peror+ed over olein uncionaliies suppored ono +esosrucured
+aerials. hus, Asea et al. $2B +odiied vin7l'MEM'1! 7pe +aerials hrough a
pos's7nhesis ransor+aion in -o sages including he epo6idaion o olein groups
-ih +EP9A ollo-ed b7 he acid h7drol7sis o he o6iranes o produce gl7colic
uncionaliies. erein -e repor he s7nhesis o 89A'! 7pe +aerials uncionali;ed
-ih high loadings o oleinic groups and heir subse
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#! $xperimental
$.! Maerials and +ehods. Pluronic P!$" #P>?$%'PP?4%'P>?$% Aldrich& -as used as
srucure direcing agen or he preparaion o 89A'! 7pe +esosrucured +aerials.
eraeh7l orhosilicae #>?8, Aldrich&, vin7lri+eho67silane #V>8, Aldrich& and
buen7lrieho67silane #9>8, Aldrich& -ere used as silicon precursors or he pure
siliceous and organicall7 +odiied +esoporous +aerials respecivel7 and -ere used as
received. oluene #8charlab& -as disilled ro+ sodiu+ prior o be used as solven or
he graing uncionali;aion. 7drogen pero6ide "% =-. in -aer -as used as
o6idaion agen, boh in he pos's7nheic and in'siu o6idaions. hen used, organic
loading reers o he +olar raio organosilicon precursor o silica or silica precursor in
he s7nhesis o olein uncionali;ed +aerials hrough pos's7nheic graing or co'
condensaion procedures respecivel7.
$.$ 87nhesis o 89A'! pure silica. he s7nhesis o pure siliceous 89A'! +aerials
-as acco+plished hrough he +ehod repored b7 Khao et al$B. In a 7pical s7nhesis
1 g o pluronic P!$" -ere dissolved in !$ +H o a?8 -ere added in a single sep. he soluion -as
hen vigorousl7 sirred or $% hour a 1%LE and h7droher+all7 aged a !%%LE or
anoher $1 hours. he produc -as hen recovered b7 ilraion and air dried. 5inall7,
suracan -as re+oved ro+ inside he porous srucure b7 calcinaion in saic air a
%LE or hours o give he produc as a -hie po-der.
$." 87nhesis o vin7l' and buen7l'89A'! +aerials. 89A'! 7pe +aerials -ere
uncionali;ed -ih vin7l and buen7l uncionalies using alken7lrialko67 silanes as
oleinic saring precursors. he uncionali;aion o 89A'! +aerials -as carried ou
b7 -o dieren -a7s. he irs roue involves he co'condensaion o he oleinic
(
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saring +aerial -ih eraeh7l orhosilicae. he second sraeg7 -as he pos's7nheic
+odiicaion o a pure siliceous +aerial hrough a graing sep.
'#'(Co)condensation. his s7nhesis +ehod is a +odiied version o he procedure
above described or he preparaion o pure siliceous +aerial. hus, aer he addiion
o he >?8 o he -ar+ soluion conaining he srucure direcing agen, he alken7l
uncionali7 saring precursor -as added o he s7nhesis +edia. A his poin -o
dieren s7nhesis variables -ere evaluaed: he preh7drol7sis i+e or >?8 and he
+olar raio alken7l precursor ) orhosilicae. hus, >?8 -as preh7droli;ed, because
he srong eec his para+eer sho-s boh in he incorporaion o organic
uncionaliies in 89A'! +aerials and +ainl7 in he ordering degree o inal +aerials
"%,"!B. hus, his para+eer -as varied in he range ro+ % @ si+ulaneous addiion o
>?8 and alken7l uncionali7 @ up o 2% +in, -hereas he +olar raio alken7l saring
precursor o >?8 -as varied ro+ %.$ o !.%. he resulan suspensions hus obained
-ere sirred or a period o $% h a 1%LE, and h7droher+all7 aged a !%%LE in an
auoclave under auogenous pressure. he solid -as hen recovered b7 ilraion and air
dr7ed. he suracan re+oval -as peror+ed b7 e6racion -ih ehanol in a si+ilar
-a7 o ha repored b7 Khao et al. $B. 7picall7, ! g o as'+ade +aerial -as reaed
-ih !%% +H o ehanol under relu6 overnigh. he solids -ere hen recovered b7
ilraion -hile sill -ar+ and horoughl7 -ashed -ih resh ehanol beore air dried.
'#' *rafting. he pos's7nheic uncionali;aion o pure silica 89A'! +aerials -as
acco+plished b7 +eans o her+al and caal7ic graing. hus, a suiable a+oun o
89A'! +aerial @ 7picall7 $ g @ previousl7 ougassed a !(%LE under high vacuu+
overnigh, -as suspended in dr7 oluene. he alken7lrialko67 silane precursor -as hen
added o he resulan suspension and sirred or ! hour o allo- he diusion o he
organic uncionali7 in he porous srucure o he +aerial ollo-ed b7 relu6ing
4
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during $1 hours. I caal7ic, he graing procedure -as carried ou in presence o p'
oluene sulonic acid #P8A& in he relu6ing +ediu+ @ +olar raio alken7l precursor o
P8A o 1% @, accordingl7 o he procedure repored b7 Garcia et al. !B. he solids
-ere hen recovered b7 ilraion and -ashed -ih oluene in a 8oh6le apparaus
overnigh. Aer ilraion under vacuu+ he resulan +aerials -ere hen dr7ed a
!$%LE overnigh.
$.1 ?6idaion o oleinic groups. he o6idaion o he olein uncionaliies o gl7colic
groups -as carried ou in -o dieren -a7s, aer he s7nhesis o he olein'
uncionali;ed +aerials and si+ulaneousl7 during he preparaion o he +aerial,
called in'siu o6idaion. In boh cases h7drogen pero6ide -as used as o6idi;ing agen.
hus, or he pos's7nhesis o6idaion, ! g o olein uncionali;ed 89A'! +aerial -as
suspended in $%% +H o aceone and h7drogen pero6ide -as added in a +olar raio
$?$) double bonds :!. he suspension -as hen -ar+ed up o LE and sirred or
$1 hours beore recovering he +aerial b7 ilraion. hen, he +aerial -as -ashed
-ih resh aceone and dried. ?n he oher hand, in'siu o6idaion -as carried ou
hrough he addiion o h7drogen pero6ide o he s7nhesis +ediu+ during he
preparaion o he uncionali;ed +aerial hrough he co'condensaion pah-a7. In his
case, a si+ilar procedure o ha described b7 Margolese et al. "$B or he preparaion
o sulonic acid uncionali;ed +esoporous 89A'! +aerials -as used. his +ehod is
he sa+e as above described unless in his case an a
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nirogen adsorpion'desorpion recorded a 44D -ere ac
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unsuccessul because he sabili;aion o negaive charges b7 silicon ao+s a bea
posiion desabili;es he olein group -hich is re+oved during he suracan e6racion
sep -ih ehanol. Oieren s7nhesis variables -ere sudied o achieve high organic
uncionali;aion degrees, al-a7s preserving -ell ordered +esosrucures. able ! liss
he uncionali;aion procedures and s7nhesis condiions assa7ed in he preparaion o
vin7l' and buen7l'89A'! +aerials as -ell as heir ph7sicoche+ical properies.
#'('( +inyl)S-)(. materials
he s7nhesis o olein'uncionali;ed 89A'! 7pe +aerials -as irsl7 acco+plished
b7 reaing a pure silica sa+ple -ih vin7l rieho67silane hrough dieren graing
+ehods. hus, 89A'! +aerial -as reaed -ih he vin7l precursor boh in presence
and absence o P8A as graing caal7s. 9oh rea+ens led o re+arkable changes on
he original e6ural properies +easured or he paren pure siliceous +aerial #see
able !, sa+ples 8% o 8$ ' igure !&. hus, he surace area and pore volu+e greal7
decreased -hen graing vin7l uncionaliies, -hereas he observed reducion on he
pore si;e -as +uch lo-er. Addiionall7, he dierences be-een he silica suppor and
he reaed +aerials are greaer or he sa+ple prepared hrough caal7ic graing
#able !, sa+ple 8$&. 8everal conclusions can be derived ro+ hese dierences:
5irsl7, he loss o surace area and pore volu+e -ihou he conse
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solid sae $28i MA8 FMR e6peri+ens. 5igure $ depics he silicon specru+ sho-ing
dieren species presen in boh he uncionali;ed sa+ples and he pure silica paren
+aerial. he area belo- he curves calculaed ro+ deconvoluion o $28i FMR specra
represens he nu+ber o silicon ao+s o each species. -o dieren groups can be
disinguished in he $28i FMR specra, locaed in he regions around '(( pp+ and '!%%
pp+ che+ical shi. he irs one is aribued o he presence o silicon ao+s, -hich
are silicon species direcl7 bonded o carbon ao+s co+ing ro+ he olein precursor.
signals, he second 7pe o silicon ao+s, resuled ro+ he h7drol7sis and condensaion
o he >?8 silicon precursor, sho- hree dieren kinds o silicon environ+ens. he
irs class corresponds o silicon ao+s direcl7 bonded o oher silicon ao+s b7 o67gen
bridges. he nu+ber o hese bonds can be 1 #1species, !!% pp+&, " #"species,
!%% pp+& or $ #$ species, 2% pp+&, he coordinaion sphere being co+pleed
-ih h7dro67l groups. hus, being he a+oun o groups direcl7 relaed o he
presence o vin7l uncionaliies, he uncionali;aion degree can be calculaed as he
he raio be-een he area calculaed or groups reerred o he area belo- plus
groups. In his -a7, he incorporaion eicienc7 can be calculaed as he
uncionali;aion degree reerred o he iniial a+oun o organic loading added ino he
s7nhesis gel. o-ever, he vin7l incorporaion degree reached -hen using P8A as
graing caal7s is +uch higher han ha obained hrough he her+al graing,
according o he higher area belo- he curves corresponding o groups in he or+er
#see able !, sa+ples 8! and 8$&.
he s7nhesis o 89A'! +aerials uncionali;ed -ih vin7l groups -as also peror+ed
hrough a co'condensaion pah-a7. his s7nhesis -as opi+i;ed b7 +eans o sud7ing
dieren variables, like he preh7drol7sis i+e or >?8 beore he addiion o he vin7l
source. he inluence o his para+eer -as assessed on he e6ural para+eers, he
!!
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ordering degree achieved on he inal +esosrucured +aerials as -ell as on he
incorporaion eicienc7 o he vin7l group. 5igure " displa7s he inluence o
preh7drol7sis i+e or >?8 on he nirogen adsorpion'desorpion isoher+s #5igure
"A& and N'ra7 diracion paerns o he inal sa+ples #5igure "9&. All he +aerials
displa7 he classical 7pe IV isoher+s, accordingl7 o he I.Q.P.A.E. classiicaion,
eauring a pronounced seep region due o capillar7 condensaion a relaive pressure
P)P%%.('%.4, characerisic o +esosrucured +aerials. ih regards o he eec o
he >?8 preh7drol7sis i+e on he e6ural properies o he vin7l uncionali;ed 89A'
! +aerials, increasing his para+eer resuls in lo-er values or oal pore volu+e and
surace area, -hereas he pore si;e slighl7 increases #8ee able !&. 9esides, unlike
sa+ple 8" @ prepared -ihou preh7drol7;ing he >?8 source @ he sa+ples displa7
seep ! h7seresis loops in he isoher+s 7pical ro+ large pores in +esosrucured
sa+ples -ih narro- pore si;e disribuions #5igure "A inside&. In conras sa+ple 8"
sho-s less pronounced slope on he h7seresis loops -hich leads o a -ide pore si;e
disribuion suggesing he +aerial probabl7 does no possess a considerable e6en o
pore ordering.
his behaviour can be e6plained considering he ineracion be-een he precursor o
he vin7l group and he suracan +icelles. 8ince vin7l precursor is a h7drophobic
uncionali7, is ineracion -ih he +icelles is +os likel7, bearing in +ind is organic
naure. his ineracion could disor +icelles because o he srong aini7 and he
possible peneraion o vin7l groups inside he suracan +icelles. his disorion is
avoided -hen preh7drol7;ing he >?8 precursor, since he h7drol7sis o he alko6ide
groups o >?8 occurs si+ulaneousl7 o he condensaion o silicon species, hough a
dieren raes. his previous sep o he addiion o he oleinic subsrae creaes a il+
o silica around he +icelles providing so+e addiional sabili7 agains he srong
!$
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ineracion -ih he vin7l group. Alhough he silica is readil7 or+ed once >?8 has
been added o he s7nhesis +ediu+, he coverage o +icelles is no co+plee in earl7
sages, and hus vin7l uncionaliies can +igrae hrough he or+ing silica la7er o
inerac -ih he suracan, hough he longer preh7drol7sis i+e, he +ore diicul
access o vin7l groups o he +icelles. In his -a7, larger preh7drol7sis i+es lead o
so+e-ha lo-er incorporaion eicienc7 o vin7l groups, as i can be saed ro+ daa
colleced ro+ $28i MA8 FMR anal7ses #8ee able !&. 8a+ple 8(, prepared -ih a
>?8 preh7drol7sis i+e o 2% +inues, displa7 lo-er concenraion o vin7l groups
han he oher +aerials #able !, sa+ples 8"'8&, probabl7 because hindered access o
he vin7l silane precursor o he +icelles.
he above +enioned conclusions are suppored b7 NRO anal7ses. N'ra7 diracion
paerns recorded or sa+ples 8" o 8( have been depiced in igure "9. All he sa+ples,
unless sa+ple 8" because o he above +enioned reasons, displa7 he 7pical
diracion paern o a +esosrucured +aerial -ih a he6agonal p(++c arra7 o pores.
he raio be-een he inensiies obained or !!% and !%% diracions can provide an
appro6i+aion o he ordering degree o he sa+ple, being higher -hen higher raio is
achieved. hus, sa+ple 8" displa7 a +uch poorer ordering degree han he oher
+aerials since he !!% diracion is co+pleel7 +issed. hen increasing he >?8
preh7drol7sis i+e, he raio be-een inensiies gro-s, -hich +eans a beer ordering
degree #5igure "9 inses&. his ac suppors he conclusions abou he ineracion o he
organic groups and he suracan +icelles.
hen co+paring he pos's7nhesis uncionali;aion procedure -ih he co'
condensaion +ehod #8ee able !&, i is noe-orh7 ha unlike he direc s7nhesis $1B,
he graing procedure do no lead o co+plee i++obili;aion o he saring vin7l
precursor. hus, he incorporaion eicienc7 is no !%%=, hough he caal7;ed graing
!"
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leads +uch higher incorporaion o olein species han her+al graing, +ore han
-ice, as alread7 described. 9esides, i should be considered he anchoring poins or he
i++obili;aion o he alken7l uncionaliies are li+ied -hen using he graing
procedure since hose are co+pleel7 dependen on he a+oun o accessible silanol
groups. ?n he conrar7, he i++obili;aion o he organic groups hrough direc'
s7nhesis is no li+ied in his +aer and in his -a7, his +ehod sho- a higher
poenial o achieve large uncionali;aion degrees on he inal +aerials @ al+os !%%=
incorporaion #8ee able !, sa+ples 8"'8&. hus, he res o he research -as carried
ou using he co'condensaion +ehod as uncionali;aion echni?8 preh7drol7sis i+e leads o beer ordered +aerials bu lo-er
incorporaion o vin7l uncionali7, he s7nhesis condiions used in he res o he
invesigaion here repored -ere seleced b7 co+pro+ising boh acs. hus, (% +inues
-ere seleced as he proper i+e or preh7drol7;ing >?8 because al+os oal
incorporaion o vin7l groups is achieved #22=&, -hile keeping highl7 ordered
+esosrucured +aerials.
Anoher i+poran para+eer sudied in he preparaion o vin7l'uncionali;ed 89A'!
+aerials, once he opi+al >?8 preh7drol7sis i+e -as i6ed, -as he +a6i+un
organic loading ha he 89A'! srucure can acco++odae keeping a high ordering
degree. 5or his purpose, several loadings o vin7lri+eho67silane -ere used, ranging
ro+ !%= o %= o organosilane o >?8 on a +olar basis #able !, sa+ples 8, 84'
82&. Firogen adsorpion'desorpion ess revealed he dra+aic inluence o he
organosilicon a+oun on he inal e6ural properies o he vin7l'uncionali;ed
+aerials. hus, increasing he organic loading pro+oes a grea decrease on he surace
area, pore si;e and pore volu+e. hose reducions are +ore inense insoar as he
organic conen increases, probabl7 as conse
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large organic loadings. his ac is easil7 assessed hrough nirogen adsorpion'
desorpion e6peri+ens #see igure 1#A&&. hereas lo- organic loading leads o -ell
srucured +aerials, increasing he a+oun o vin7lri+eho67silane causes no onl7 a
grea decrease on all he e6ural properies, bu he shape o he isoher+ is also shied.
hus, ro+ sa+ple 8, conaining !%= +ole o vin7l uncionaliies, o sa+ple 82 @
%= loading o vin7l silane @ he h7seresis loops beco+e -ider, indicaing he parial
desrucion o order in he +aerial. ih regards o he pore si;e disribuions, no onl7
he +a6i+u+ o he disribuions are displaced o-ards lo-er pore si;e bu also he area
belo- he curves decrease -hen higher loading o vin7l uncionaliies are used. hese
acs sugges he incorporaion o he organic uncionaliies akes place inside he
+esopores. he increase o he organic loading sho-s so+e conse
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-all hickness. his resul suppors he above +enioned conclusions abou he
incorporaion o he organic uncionali7 ono he surace o +esopores, and increasing
hereore he si;e o he pore -alls.
ih regards o he incorporaion eicienc7 o he organic uncionali7 ono he inal
+aerials, igure depics he $28i FMR e6peri+ens carried ou on sa+ples 84'82, as
-ell as !"E FMR specru+ recorded or sa+ple 82. As in he case o he vin7l'89A'!
+aerials prepared hrough he graing procedures, he sa+ples prepared -ih dieren
organic loadings also displa7 boh and silicon groups. he area belo- groups
increase -hen higher loadings are used. he deconvoluion o he $28i FMR curves
gives surprising resuls since, regardless o he a+oun o vin7lri+eho67silane used in
he s7nhesis o he +aerials, al+os !%%= o he organic uncionali7 precursor is
inall7 incorporaed o he +esosrucured +aerials. his is a ?8 +olar raio @. Regarding he !"E FMR specru+, eriar7 carbons
locaed a vin7l double bonds are clearl7 visible, de+onsraing he iniial oleinic
uncionali7 srucure is -ell preserved during he s7nhesis o hese +aerials.
8econdar7 signals, such as hose corresponding o re+aining suracan aer e6racion
-ih ehanol, are also visible @ ! and (% pp+ che+ical shi @ bu, in his case, heir
lo- inensi7 suggess ha he srucure direcing agen is presen in lo-
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As resul o his sud7 abou he inluence o he organic loading on he inal properies
o vin7l'89A'! +aerials, i can be concluded ha he incorporaion o vin7lsilane
uncionaliies can be achieved in !%%= eicienc7, regardless he iniial a+oun o he
oleinic group in he s7nhesis +edia. hese +aerials sho- raher good srucure
ordering, even or such high a+ouns o vin7l loading as hose used or he preparaion
o sa+ple 82 @ -hich displa7 good +esosrucure as sho-ed in >M i+ages depiced
in igure (. ih regards o he e6ural and srucural properies, he uncionali;ed
+aerials sho-ed high surace areas, pore volu+e and pore si;es, hough shied o
lo-er values -hen high loadings -ere used. Increasing he a+oun o oleinic
uncionaliies also led o increasing values or he pore -all hickness @ up o 2 n+ or
he +aerial prepared ro+ %:% vin7lri+eho67silane:>?8 +i6ure #sa+ple 82& @.
#'(' utenyl)S-)(. materials
?nce he sud7 abou he incorporaion o vin7lsilane uncionaliies ino he srucure o
89A'! +aerials revealed he possibili7 o incorporae high loadings o his
uncionali7, he sa+e sud7 -as carried ou or larger oleinic groups. In his case,
buen7l#ri+eho67&silane -as used as larger oleinic subsrae. he a+oun o
buen7l#ri+eho67&silane -as varied in he range $% o %= +ole -ih regards o
>?8. able ! liss he e6ural and srucural properies o buen7l'89A'! +aerials
#8a+ples 8!%'8!$&. I see+s here is no correlaion be-een he a+oun o saring
organosilane co+pound and he e6ural and srucural properies o he inal +aerials,
e6cep ha he oal pore volu+e di+inishes -hen increasing he loading o he oleinic
subsrae indicaing he porosi7 o inal sa+ples beco+es lo-er. o-ever, he nirogen
adsorpion'desorpion isoher+s #igure 4#A&& clearl7 la7 in he 7pe IV group
accordingl7 o he I.Q.P.A.E. classiicaion, sho-ing ! h7seresis loops, characerisic
!4
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ro+ +esosrucured +aerials. Fo grea dierences can be observed in he nirogen
adsorpion isoher+s corresponding o he dieren buen7l'uncionali;ed 89A'!
+aerials, hough he decreasing on he +a6i+u+ adsorbed volu+e are clearl7 eviden
insoar as he a+oun o oleinic subsrae is increased. Regarding he pore si;e #igure
4#A& inside&, all he +aerials displa7
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esed +aerials, and being he sa+ple -ih he highes incorporaion degree, onl7 sho-s
slighl7 +ore han %= incorporaion eicienc7 -hich is al+os hal o ha
incorporaed on he sa+e +aerials -hen using vin7l uncionaliies. 5igure 4#O&
displa7s he !"E FMR specru+ recorded or sa+ple 8!$. As in he case o vin7l'
uncionali;ed +aerials, he olein double bonds are clearl7 visible #!"E !$% pp+&,
ogheher -ih he signals corresponding o he res o he carbons a he buen7l +oie7.
9esides, signals locaed a ! and ( pp+, aribued o he presence o suracan, are
also visible, indicaing he eicienc7 o he suracan e6racion sep is no co+plee.
his could be relaed o he srong aini7 be-een he h7drophobic oleinic
uncionali7 and he organic srucure direcing agen, -hich diiculs he re+oval o
he e+plae as observed in oher h7brid organic'inorganic 89A'! 7pe +aerials
"","1B. Feverheless, buen7l'uncionali;ed +esosrucured 89A'! +aerials, as in
he case o vin7l uncionali;aion, displa7 good +esoscopic ordering, as i can be easil7
observed in R>M +icrophoographs #igure 3&, -here he 7pical hone7co+b
srucure o 89A'! +aerial is clearl7 visible or sa+ple 8!$, conaining he highes
a+oun o buen7l groups loading a+ong he esed +aerials.
As conclusion ro+ his sud7 i can be noiced ha buen7l 89A'! +aerials can be
prepared -ih high loadings o oleinic groups, hough he incorporaion o hese
uncionaliies o he inal +esosrucured +aerials is lo-er han uncionali;aion
degrees achieved -ih s+aller oleins such as vin7l groups. Alhough NRO paerns
reveal a +uch lo-er ordering degree in hese +aerials han in vin7l'89A'! sa+ples,
>M i+ages conir+ he good +esoscopic srucure o inal sa+ple.
!2
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".$ ?6idaion o oleinic groups incorporaed o 89A'! +aerials
?nce he opi+al condiions or he preparaion o olein'uncionali;ed 89A'!
+aerials have been deer+ined or boh he vin7l and buen7l groups, he sud7 on he
o6idaion o hese oleins o-ards gl7colic uncionaliies -as ackled. Feverhless, his
invesigaion -as carried ou or sa+ples prepared -ih S+oderaeC oleinic groups
loadings #""= b7 +ole& in order o ensure a high o6idaion e6en over he i++obili;ed
double bond uncionaliies. hus, dieren o6idaion sraegies -ere esed or
o6idi;ing olein subsraes. 5irs, a pos's7nheic sraeg7, based on a evenuall7
o6idaion once he vin7l and buen7l 89A'! +aerials have been prepared, such as ha
repored b7 ?;in et al. $2B, using +'chloro perben;oic acid #+EP9A& as o6idan.
8econdl7, a direc s7nhesis +ehod -as also esed, consising on he preparaion o
olein'uncionali;ed 89A'! +aerials in presence o h7drogen pero6ide as o6idan. In
his -a7, he double bonds a he organic uncionaliies are o6idi;ed in'siu during he
s7nhesis sep and hus, no pos's7nheic +odiicaions are re
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co+paring he un+odiied +aerial and he subse
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epo6ide groups leading o he ring aperure o-ards gl7cols. In his sense, i can be
concluded he e6ension o he o6idaion reacion is
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resonances in he range (%'4% pp+ are clearl7 inense on he specra recorded or
sa+ple 8!1 and in he range %'( pp+ or sa+ple 8!(. hese acs indicae he
presence o gl7colic uncionaliies, +ore han o6irane groups, -hich usuall7 displa7
lo-er carbon che+ical shis. hus, hese resuls suppor he above +enioned
conclusions abou he opening o he o6irane groups because acid h7drol7sis o he
sa+e. 9esides, his resul conir+s he good peror+ance o he in'siu o6idaion
+ehod in co+parison o oher pos's7nheic o6idaion +ehodologies, such as he
epo6idaion o double bonds -ih +ea'chloro perben;oic acid, o lead ho+ogeneous
+esosrucured +aerials sho-ing high conen o gl7colic groups. he so prepared
+aerials displa7 high poenial or he heerogeni;aion o dieren +eal species as
-ell as adsorbens or he selecive reenion o polar subsances.
'onclusions
he s7nheses o alken7l'uncionali;ed 89A'! have been carried ou boh b7 pos'
s7nheic graing and co'condensaion +ehodologies. hereas he or+er leads o
parial incorporaion o he oleinic subsrae, even i acid caal7s as P8A is used, he
direc s7nhesis +ehod ensures al+os oal incorporaion as -ell as achieving high
uncionali;aion degrees. Vin7l pendan groups can be incorporaed in a ver7 eicien
+anner ono he surace o 89A'! +aerial, hough parial preh7drol7sis o he >?8
saring +aerial has o be peror+ed in order o preserve he good +esoscopic ordering
o he +aerial. o-ever, using he direc's7nhesis procedure allo-s incorporaing
vin7l'silane loading, as high as %= o he alken7l group reerred o >?8. ?n he
conrar7, larger alken7l uncionaliies, such as buen7l organic groups, are +ore
diicul o be incorporaed, and lo-er uncionali;aion degrees are achieved. 5inall7,
he o6idaion o hese double bonds o-ards gl7col7c groups is easil7 achieved hrough
$"
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he in'siu o6idaion o he alken7l groups, involving he use o h7drogen pero6ide in
he s7nhesis +edia o he alken7l'89A'! +aerials. his ne- s7nhesis procedure, in
-hich he uncionali;aion and +odiicaion o he organic groups aached o 89A'!
+aerial is clearl7 +ore eicien han oher previousl7 repored +ehodologies such as
he pos's7nheic o6idaion -ih +EP9A as o6idan.
Ac(nowledgements!
he EIET is kindl7 ackno-ledged or heir inancial suppor hrough he proecs
E$%%'%$"4 and E$%%3'%2%2)PP.
$1
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!1B . Dugia, . iguchi, Ehe+. He. " #$%%(& 2%(.
!B F. Garcia, >. 9enio, J. Gu;+Wn, P. ie+blo, V. Morales, R.A. Garca,
Microporous Mesoporous Maer., !%( #$%%4& !$2.
!(B G.>. 5r76ell, Inorg. Ehe+. Eo++un., 2 #$%%(& !!1!.
!4B 8. Niang, T. Khang, . Nin, E. Hi, Ehe+. Eo++un. #$%%$& $(2(
!3B . Khang, T. 8un, D. Te, P. Khang, T. ang, J. Maer. Ehe+. ! #$%%& "!3!.
!2B M. Druk, . Asea, M. Jaroniec, G.A. ?;in, J. A+. Ehe+. 8oc. !$1 #$%%$& ("3".
$%B T.. ang, E.M. Tang, 9. Kibro-ius, 9. 8plieho, M. Hindn, 5. 8chUh, Ehe+.
Maer. ! #$%%"& %$2.
$!B A.8.M. Ehong, N.8. Khao, A.. Dusedo, 8.K. iao, Microporous Mesoporous
Maer. 4$ #$%%1& "".
$$B T. ang, 9. Kibro-ius, E.'M. Tang, 9. 8plieho, 5. 8chUh, Ehe+. Eo++un. !
#$%%1& 1(.
$"B .'M. Dao, J.'O. u. E.'E. Eheng, A.8.. Ehiang, Microporous Mesoporous
Maer. 33 #$%%(& "!2.
$1B M.. Hi+, E.5. 9lanord, A. 8ein. J. A+. Ehe+. 8oc. !!2 #!224& 1%2%.
$B M.. Hi+, A. 8ein, Ehe+. Maer. !! #!222& "$3.
$(B I. Oa;, 5. Mohino, . 9lasco, >. 8asre, J. Pre;'Pariene, Microporous
Mesoporous Maer. 3% #$%%& "".
$4B H.M. Ru-isch, P. OUrichen, R. Riedel, Pol7hedron, !2 #$%%%& "$".
$3B . Asea, M. Druk, M.J. MacHachlan, F. Eoo+bs, . Gronde7, M. Jaroniec, G.A.
?;in, J. A+. Ehe+. 8oc. !$", $%%!, 3$%.
$2B . Asea, M. Druk, M.J. MacHachlan, F. Eoo+bs, . Gronde7, M. Jaroniec, G.A.
?;in, Adv. 5unc. Maer. !! #$%%!& 114.
$(
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"%B N. ang, D.8.D. Hin, J.E.E. Ehan, 8. Eheng, J. Ph7s. Ehe+. 9 !%2 #$%%& !4(".
"!B N. ang, 8. Eheng, J.E.E. Ehan, J. Ph7s. Ehe+. E !!! #$%%4& $!(.
"$B D. Dao, . Mukai7a+a, Ehe+. He. !3 #!232& $$"".
""B J.A. Melero, J. Iglesias, J.M. Arsuaga, J. 8ain;'Pardo, P. de 5ruos, 8. 9lW;
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)igure ,! #A& F$adsorpion desorpion isoher+s and pore si;es disribuions #inse&,
#9& NRO paerns #E& $28i FMR specra and #O& !"E MA8'EP FMR specra colleced
or buen7l'uncionali;ed 89A'! +aerials sho-ing dieren olein loadings.
)igure ! >M i+ages colleced or buen7l'uncionali;ed sa+ple 8!$.
)igure .! 5IR specra recorded or vin7l'uncionali;ed 89A'! +aerials, paren
+aerial, aer o6idaion -ih +EP9A and prepared in presence o $?$.
)igure 1/! $28i FMR specra recorded or #A& vin7l' and #9& buen7l'uncionali;ed
89A'! +aerials. 5ro+ boon o op: paren +aerials, poss7nhesis o6idaion -ih
+EP9A and prepared in presence o $?$.
)igure 11! !"E MA8'EP FMR specra recorded or #A& vin7l' and #9& buen7l'
uncionali;ed 89A'! +aerials. 5ro+ boon o op: paren +aerials, poss7nhesis
o6idaion -ih +EP9A and prepared in presence o $?$.
$2
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5igure !
R. van Grieken e al
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5igure $
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5igure
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5igure 2
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5igure !%
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