Micmat 4488 Final

8/11/2019 Micmat 4488 Final

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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.2010.01.010


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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

$"


24/40

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


25/40


26/40

!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.

$(


27/40

"%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;


28/40


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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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Documents

Micmat 4488 Final