Pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions
Spectral characteristics of polar - push-pull stilbene (St) and nonpolar pyrene (Py) molecules on the silica and silica-titania surfaces have been studied by the methods of steady-state and momentary spectrofluorimetiy. Photochemistry of Py molecules in microheterogeneous media titania-silica colloi...
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| Дата: | 2001 |
|---|---|
| Автори: | , , , , , , , , , |
| Формат: | Стаття |
| Мова: | Англійська |
| Опубліковано: |
Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine
2001
|
| Онлайн доступ: | https://surfacezbir.com.ua/index.php/surface/article/view/55 |
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Репозитарії
Surface| _version_ | 1869291138945384448 |
|---|---|
| author | Smirnova, N. Eremenko, A. Rusina, O. Linnik, O. Yakimenko, O. Staruch, G. Ogenko, V. Chuiko, A. Spanhel, L. Rechathaler, K. |
| author_facet | Smirnova, N. Eremenko, A. Rusina, O. Linnik, O. Yakimenko, O. Staruch, G. Ogenko, V. Chuiko, A. Spanhel, L. Rechathaler, K. |
| author_institution_txt_mv | [
{
"author": "N. Smirnova",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "A. Eremenko",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "O. Rusina",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "O. Linnik",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "O. Yakimenko",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "G. Staruch",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "V. Ogenko",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "A. Chuiko",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "L. Spanhel",
"institution": "Lehrstuhl für Silicatchemie"
},
{
"author": "K. Rechathaler",
"institution": "Institut für Theoretische Chemie und Strahlenchemie"
}
] |
| author_sort | Smirnova, N. |
| baseUrl_str | |
| collection | OJS |
| datestamp_date | 2018-11-27T09:42:39Z |
| description | Spectral characteristics of polar - push-pull stilbene (St) and nonpolar pyrene (Py) molecules on the silica and silica-titania surfaces have been studied by the methods of steady-state and momentary spectrofluorimetiy. Photochemistry of Py molecules in microheterogeneous media titania-silica colloids is controlled at presence of cyclodextrine. Change of the spectral position of the fluorescence maxima of stilbenes and lifetimes of stilbenes correlated with the change of local polarity around the adsorbed species due to competitive adsorption of water molecules from air and removing of adsorbed stilbenes to places with lower polarity. Stilbenes fluorescence is quenched effectively and this quenching is attributed to electron injection from excited stilbene to titania.
  |
| first_indexed | 2025-09-24T17:25:23Z |
| format | Article |
| fulltext |
РЕсULARITIЕSoFЕL,ЕСТRО}iiСlr]Г}"iLAС].IoNoъ.
POLARANDNON-РOLARORGANIсFLUORЕSСЕN.г
PRoBЕs IN ТнЕ NIIхЕD ТI.гANIA.SILIСA СoМPoslТIoi\.is
N. Smirnоva., A. Еrеmenkоl, o. Rusinаl, o. Linnikl, o. Yakimеnkol, G. Staruсhl,
v. оg"nkoi, д. ёьuiиol, L. Sраnhеl2, аnd K. Rесhthаlеl
tIttstitutе o! Suфсе Сhеmisttу, |уаtioпа! Ас:аd,:nry o'f Si:tеnсеs,
]7 Gеп, Nаumoу str'',03i80 Kуil,'1б1, {|KR4INЕ,' e-tnаtl: аппеrеm@пtltl.kаr.trct
2 Lеhrs|iihl fur Si!iсаtchеmlе, |Viiеrzhurg Ur|i\,еSltаi,
Raпtgепring 9.I 1, 97070, Wilеrzburg, GЕR^'IАi\ry'
3I|lstitut fiir тъйrыisiпе Сhеmiе tnd Strаh!епсhеmiе, {Jtliуеrsi!сit I|/j<:ti,
Аlthапstrаssе 11' А-l090 Wiеп, АUSТR|А
Abstraсt
Spесtrirl сhaгaсtепstlсs of.pоlar _ push.рull stilbеnе (St) allсi nonpс.iаr рi,rспе (Pr-) mоiссulеs oг,
thе siliсa and siliсa-trtarшu ,u,fu"., hauЪ bееn srudiеd bу thе mеthods of slеadу-'tаtе and mL-'mеntary
spеоtrofluoгimеtгy PhоtoJеmistry oггу mоlесulеs-in nriсгohеtеrogеnеоus mеdia iitania.siiiсa
сolloids is сontгo]lеd u, p,",.n.. оf оусlodехtгinе Changе оf thс зресtl.r1 роsitiоn оi thс
fluorеsсеnсе maхima оf stiibеnеs aлd lifеiimes оf stlibеnеs сопеlatоd r'ith lhе сhaл'sе оi loсаl
рolaгity aгound thе adsс,гbеd spесiеs duc to соntреtiti'e adsоlрriэn оt .'..alL'r mоlесrllеs fгilг,r а;г а:;ti
remoйng of adsoгbеd stilbеnЁs tо рlaсеs wrth iowеr рoiaгitу.. .lriibеnеs t"]uolesоеnсе is quеnсhеd
еffесtivеly and this quеnсhing is attгibutеd iо еlесtгon injесtiоn fiom ехсitеd stilbепе tс titania,
The r.itilization of sеmiсonduсtoг рaгtiсulatе systеIтls as a
'еeсtivе
hеtегоgеnеоus mеdia
has bееn аnd rеmatns verу popular in сarrying оut phсltосhеmiсr| transflоrmatiоns oГ огganiс
and inoгgaшс .o*pouna,.
.1l.-в1
шuno,iiес titania сataiу-qts ехhibit ulrique and еffiсient
rеaсtivitу for vaгious pьotoЬ.tui,.дi. reaоtions in. rvhiсh manу organiо sЦbstratеs havе beеn
shown to be oxidativеlf d;-;;; саses гeduс-tin,еly) dеgгaсiеd and uitiшatеly minегalizеd
оomplrtely undег UV i.*ojution [9-l3] Мiхеd siliсa -"titania оoпlрositions are also of siфfiсаnt
tесhnologiсal imрoгtanсe. ih" ,,,.t1,oа оf aпеstеd pгесipitatiоn known as sоl-gеl proсеss Ii4]
сanbeemploуеdtoрrеpaгesmallsеmrсonduсtorpaпiсiеs(S'Р)inрoтоussiliсamеdium[15]'
Мiхedoxidеcompositеmatегialsсanoftеnbеmоrееfiiсiеntphotoсataiуststhanpure
substanсеs' ln thе сasе of siliсa-titania svstеms, thе inсгеаsе in photооatalуtiс еffrсiеnсу has
bееn attгibutеc to thе iй;;.; adsorption and сonсеntгatiоn оf.thе геaсtants nеar thе aсtivе
sitеs Il6, l7].
Тhеpropегtiеsоftitania.siliсabilrarlеsarеstrongi1сlеpеnriеlrt'оrrihеiгсhеrniсai
сomposition' i'o*og.n"liу uno ..ou,.' whiсh dереn.d on sуnthеsis сl.,ndltioas,
.[hе еlесtгoniс
spесtra of luminеsсеnt йl"сul". to dеtесt loсal сhеrniсаl аnd stnlсturаl ресuliaгitiсs оf thе
solids has ь."n
"*t"n,,u.iу
,'ual.а [ls-22] Fluorеsсеnt oгganiс сiуеs, е g .lхаzinе-c, ет]ithrosin B'
еosiц Ru(bPу),.. a,rd d;;;;i'"' ьauе bееn йdеiу usеd is lunrinеsсеnl. prоbеs аs rvеll in thе
sеnsitizatiоn of iшgе banJ sеmiсor,dЦсtoгs as Тioz juе t., tllеir sli-ong '.isiblэ a<isorptrоn а.nd abi1itу
to intегaсt мtь s"мсonJuсto, *,гu.", |.2з.25) IТоrvеvеr, iеss is йorw a1rоut
'hе
aгрliсation of
push-pull stilbenеs аs luminеsсеnt probеs' Donor.aссеptoг substitutеd strlbenes' сrrlled рush-рull.
stilbenеs, wеге studiеd йth rеspеci to сharge sеparation in е:<сitесl :jtаtс, .rf, thе riiро!о inоп'lе:1t
160
\ tll.'
L\I
iIl'toNs
tk'l.. G. Staruсhl,
llсl
. ..i]е|
stгоngly inсгеаsеs t26-28]' Highly еmissivе TICТ statе of the stilbenеs in polar sоlvеnts has a laгgеcipolе momеnt. Appliсation of dono.-a...ptoг substituted мilbenes on thе suгfaсе of Ti-сontainedсompositions is undегlinеd, as it should p'oиd. thе sеnsibilization oгi.,",ogеnеous photoсаtalyststo the nеaг ultraйolеt arrd йsiblе liфt. Adsorbеа
'tirьenes
и-ьеtе,щ"Ъou, mфia sееm to bе thеnеw inteгesting photoсhemiсаl systй wrth the vaгiation oгпuo..,й". propегties.In tЫs study, wе,.dе:' *ilь the pгеparation of highly i,un,pu."n. Тio2lsio2 (0.l .l'wtуo of titania) сolloids, fiIms and powders uslф iье sor-gel mеthod and thесhaгaсtегisation of thеse systems bу mеans oг л.,o,.,..i.;';;;'; of, adsoгbed luminesсеnt:гobes: non-polaг pyrеnе-(Py),.unj ьigь polаг dоnoг-u...p'Ь',-,uйtitutеd push-pull stilbеnе5-9-(4-CуanostуryI)-2'3'6,,1.tеtгahуdro.lЬ'й-pyпdo[3'2,r-ljjquьJиi
CulНmNz (St). Мonomегfluorеsсеnсе of Py in mixеd titania-siliсa сolioid,
"ontulnJс.p-.кьi"oнn has bееn studiеd.Еlесtгoniс intеraсtions betweеn adsoгbed spесiеs рy, s' "iJli-d*; siliсa matгiсеs havе bееnstudiеd bу thе mеthods of stеady-statе and momеntary speсtгofluoгimеtry Sio2 powdег wasзsеd as геfегеnсе сompound fоr thе luminesсеnсе study oГadsorbеd fluoгophorеs.
Ехрerimental
Pу was intгoduсеd into thе сolloids from ethanol solution oг as a CD inсlusion;omplех' lv{ixеd siliсa-titania сolloids (l, з,.5 Yo of titania) ;;; pгoduсеd by thе aсid,:vdгоlysis of tеtraisoproporyопhotitanatе embеddеd in u ,,ubl. .o,roiс siliсa sol. on thе-aгеpaгatlon of TiozlSioz sуstеm, aп alkoхide proсеss'u, u,.с (Тilsi-l). Titanium:еtгaisoрropoxide (TPOT) is subjесtеd tо сondеnsai;on rеaсtlon Jtь р,...,,iously hydгolysеd:еtгaаlkoхуsilane (TЕoS) togеthег with еthanol, filtегеd dеionizеd u.atеr and HCl (сatalyst)ТЕoS was prеh},dгolyzed with еthапol anc rvatег foг 2 houгs at 7О "С,l:ndег сontinuousstiггing. Тhe pгеhуdrolуzed ТЕoS wаs сoolеd to room tеmрегaturе. Thе miхtuге was stiггеd..vегnight at roоm tеmреratuге bеforе diр-сoating pгoсеd".. тьin я,*s сonsistеd of 1 to 2:onsесutivе layегs, and thе total thiсknеis was appгохimatеly 200.35О nm' Siliсa Mегk l00rodifiеd йth Тioz wa'
ч1."d P: thе сomparativе studiеs (Т/si.2) [2B] The геsulting siliсa-titania:olid aftег hеаting at 5000 С is сontained with amoгphous phasе of titania аs dеteгminеd bуХ-гay powdeг diffгaсtion Тhе сrystallinitу of TLzSi сoatings *", iойiя.d by Х-гay diffгaсtion)RD) method imploying CuК* гadiation Thе thiсknеis of the films was obseгvес us;niе ] есtron miсгosсopу-p.ofi.l
9T:Jy mеthod S pесtгosсopiс analysi s oг *а,oй';j;;",;;::егfoгmеd using a Hitaсhi U3000 speсtгopiotomеtег. Еmissiоn aлd ехсitation spесtгa wегеstudiеd foг the vaсuummеd and opеnej in aiг samples to соmparе tь"ЪЬ.t оГ oxуgеn quеnсhing-лd watег vapouг аddition on thе aгbitгагy intensity and lifetimЁs of adsoфеd spесiеs. Fluoгеsсеnсе.rd ехсitation spесtra of adsoфеd molеЪulеs wеге геgistегеd with a Еlmег LS 50B fluoгimеter.
-ifеtimеs of the adsoгЬеd stilbеnеs wеrе also .феrеd ть" ййutus aлd dесonvolution:roсеdure, based on thе mеthod of single photon
"oun1ing,
.',u, а.,м6JJ.isеwhеге [27].For thе struсtuгеs of stilbеnе sее Sihеmе l:
..uiеs oгl
-- - ..:})еntary
: .;l;а.siliсa
.: .l t-.i thе
.. .: .li loсаi
. -'r nil 8l-iC
.,. iuеllсlrеd. .-:^
(:- .'s mеdia
,. . olganlс
- е1iсient
. .: 'li.е been
: lегаlizеd
i: : .iФficant
l - :еss [14]
i _.:'зm [15]'
';. :,an рurе
. . -,еnсу has
.:-:lеaсtivе
.. .hеrniсal.
: ir.сtгоniс
. ' ''s .rf ihе
е- :ll-оslп B,
.. '.]i ri-r thе
: .'l..t abilitу
:'. -. lсation of
:. : : ]Ush.рull.
' l lliОПl€!.li
.^'.J-хi .Г
i-r7-:-l --
\---
\st
.l->t! )Y
I
*'ij:жi*!фi:*';:;i}r'F"lil?"iiloi.io'i"rйкi+*ф.й,Щi",T*
fluoгophoгеs is on thе av.еragе.'lu^;j:.;;;;е oH-ягouрs of Sio,z and l Vtl *i'":::'::
^".
oolш pu sh- puш,tirь
"n..
i,
"i.itf
.с,o,ь. а f: :l.jl;*:H il,: il:;'il: ff .'Htr. y JЩ g
"ny#"Ё""-ьЬ"o':::"^т'""l
'T.Т'*'J:lнж
ff. ffi;;io* porositу *j
'*ыr
spесifiс suгfaсe
molесulеs aJе сonfinеo.
'Ь.tn...u,lngthe'';}'il}i:{j?'i
jf r#j*d'tr*:*.у::lТ'i:,.}"#'..:}НTl;
photoluminеsсеnсе sp€
'Ы;
ions loсatеd on thе surfaсе'
Fluorеsсеnсe spесtra and dесaу traсеs of pуrеnе within 9.o,'',.':"$',Тtф
''-".11'1;'
In thе prеsen";ъ? аЫ й.l. fluo,.,..n." intеnsitу is high
Ц;;;; ;hе quenсhing
::l;1*iiill:".l*л*нжц.Т:-;\f;
Нi;l'#::l-'iЁ*hThtжllрдq
pУrеnе fluorеsсеnсе,;i"i й' usеd as .'Т":il:'ъ|"l:",l!li.'"'; -;й"''
1:}.
,'n
i,''"*^ii,r, "'.'1::'жТ'".';ь'iiu'Hйiuйt.?-,ot, i'"d.l",
|'42in CD/еthanol/watеr
l,}ii*:tтi"нж,i" jй.,".ьio,,.n.^*oi.*,-,l,.ot,'пь:::i};';ffi
'l,3Y:liii}}l
[Тнh#Hl''"ъ**ьъ.grilliii]d:{ЦЦi:Tт:':."ff **lxЦ}'l**;
:il';;;1iж*11"'J';:iъffi'.Т':ж"т:.JHL:]'i{#l;o.J:;;;;;"gсonсеntгations
Thе absenсе o, .*J,",,i.-".,io;:; ''"..:тх:'''Jl"'nlt1**::;:гl,"*]'li"J;';"*
'
;Ь;;;i""lloid paгtiсlеs and a laсk ot dlтп
сon,
titar
сhal
mо]
p} гс
;l:-
е1]1s
s'r rt,
'-:i.
:-'r
-. t{'
.)
.t:l
-..:,'
l, a.u.
1
1 4000
1
8000
6000
4000
2000 r Rn
4oo wau"l"ngth, nm
Tу;.);iJ,lix1Ъ.^,:,:o"".,u
in T7Si сo'loids: ].|ohт\in Pу1Ti/Si; 2- 1%Ti.' 3-зo/.Т|'
\\ /\
ц\it rlfl';r
\n\)tt'^\/''."r't .-
t67
еsl']t.сt to the
:..'егage. нiф
;:faсеs duе to
:.all amount of
:зсifiс suгГaсе
.:эnsity of thе
: ;ontaсt with
s
.: miхеd TilSi
:: е с1uеnсhing
--: r-0 band of
:_ s-rrrоunding
a-.l 1.ll ln
):::anol/watеr
-] :.rvitiеs and
т= ' ''r,hеn doеs
-?:1е ехсlmеr
.-:зеrs whеn
] - :еntrations'
.. ..Lеs on thе
. .:еne,
Fluoгеsсеnсе dесaY сurvеs of pугenе within miхеd ТySi сolloids сoгrеlate with titaniaсontеnt, suggеsting that еIесtron injесtion fгom ехсitеd state of p}теne to titanium ions oгtitania smаll paгtiсlеs doеs take plaЪe Lifе ti*. uiJ й.;й Ёjьuuio, of ехсitеd pyгеnесhangеd whеn CD is pгesеnt in the сolloid systеms suggesting pйteсtion of solubilized pyгenеmolесulеs within CD сavities against of titanium jon,
tii
p..jl.Т *i'iiь" solubilization, paгt ofpyгеnе molесuIеs is loсalizеd out of СD сavitiеs undergoing iье.quеnсьing pгoсess anсdесrеasе оf lifе timе of ехсitеd statе
Fluoгеsсenсе of Pу both monomеr and ехсimеr is suppressеd in pгеsеnсe of Ti withinsiliсa pоu,'dеrs (ТУSi-l and Ti/Si-2) and totally quеnсhеd on ihе Tioz suгfaсе. Тhe fluoгеsсеnсееmission quеnсhing should bе attгibuted to elейon tгansfег from the .*Ъit.с statе of pyrеnе to thеtitaшa paпiсlеs rr'ith thе appеaranсе of bluе сoloг of Tiз- io"- ;ft;;;;itania on the TilSi1 filmsuгfaсеs is muсh lеss than it is on thе ТiiSi.2 (Pig 2) ть" е*сi.е. fluoгеsсеnсе is сlеaгlуindiсated as bгoad struсtuгеlеss band rvith thе maximum 480 nm foг thе film сontainе d 1v"1 уoof titania. spесtгЦm 3' when Pу was intгoduсеd on thе stage of mutuai hydгolysis of ТЕoS andТPoТ Тhе Гavouгablе сonditions fог thе mоlесulеs apprйсh ...ь oiь", oссurгed on thе stagеэf so!- gеl transfег in thе сonfinеd spaсе of thе gеi..L"*
'"i'iil'i,y of thе fluoresсеnсе ofadsoгbеd Ру to thе pгеsеnсе of Тi iоns within Ti/Si-l suggеsts that atoыс'i*ing betwеentitaшa and siliсa оссuгs in thе sol-gеl prоduсеd films and titйm ions are not aссеssible for thеimmеdiatе сontaсt йth Ц, molесuй on thе suйсе' In thе сasе of T7Si-2, small titania сrystallinеpaтtiсlеs aге initiallу foгm^еd aлd сompоsеd as indiйduaI sitrs on thе suгfасe or йthin thе poгеs оfsiliсa and aге aссеssiblе Гoт thе аdsorbеrJ Р} at this conсеntгation ,-g.' Ъruoresсеnсe speсtra ofadsorbеd St also aгe indiсativе to thе йеthod of pгеpаration u,ТJ сoггеspondingly suгfaсесhеmistry of Т|lSi сompositions.
n
l' аm.Un
450 500
t,nm
Fig.2. Fluoгеsсеnсe spесtra of pуrепе molесulеs on thе T7Si films suгfaсеs:
] - 0 5% Ti' 2 - з% Ti' 3 - I% Тi, Py is саpturеd in thе film by сo.pгесipitation.
Stiltlеnе
Fluоrеsсеnce spесtra of adsoгbеd stilbеnе also aге indiсative to thе mеthod ofoгеpaгation and сoпеsрondingly suгfaсe сhеmistry of TilSi сompositions.
]000 :
t
l
яnл L-""1
r
^^^loUU Г
I
o*f
г
,oo
l-
эU
Тt.
loJ
^'
tlll }Ч гm
Fig. 3. Ехсitation (1] ild l::l:,...:::.,(:],'ж.ll1
of St on Sioz undеr vaсuum сonditions at
;;;;;;?ёl. zo (/),40 (2),60 (3) and 80 (a)
t\
l\
350 375 400 425 450
оf thе ,I.
еmission
с
bе соnле
adsoгptio
po!aritу
spесtrum
adsoгbеd
Тhе r
stilbenеs
dесгеasе
fluorеsсеt
injесtion 1
on purе.I
thе titania
titania suг
proсеeds ,
Conсlus
l' Рyгr
ofr
sеnI
suгf
2. Phо
сon
intе
siliс
F
lт
I
Г
l
l
I
1,0't
0,8'
0,6
j
9 0,.
0,2
l' гm
Fis.4.Еxсitation(a)andfluorеsсеnсе(D)spесtraofStonSiozunderairсoпditionsat
;'Xo;';;;'Fsi: io'tr),40 (2)' 60 (3) and 80 (1)
FluoгеsсеncеandехсitationspесtraofthеSt/Sio2undеrvaсuu:nсonditionsшesimilшtothе
sDeсtra in polш *oru,i"", iti"o,;';;.'**u^sцo-i6о n*, еxсitation maximum 3Ф nm) (Fie 3)
дftеr thе сontaсt ",
,iJ,.йoj.,.и.ь u,,, fl";;;,;;.l 'p..'.'
of. 52. SiФ ше bluе-shiftеd'
fl uorеsсenсemaximumЁ,"]"iЁi'..o*.11o".i"iiй.;i!1ч'1'"P'";'ffiJ;ffi уffi::
diffеrеnt оn thе surfaсе' "iirlЬl.r
and Ti-Si-2. Fluoгesсеnсе speсtra ot tr
t64
] сonditions at
aiг conditions at
цe similar to the
l 3Ф nm) (Fig 3)
: шe blue-shiftеd,
of adsorbеd St is
:rе on thе surfaсеs
of thе.ГilSi-l systеms (0 l - 10 % Tio2) arе akin to thе
еmission is dесгеased with thе titania contеnt inсгеasе rTis.
onеs in thе polaг solutions. lntеnsitt, оf
со!лts а U
.щГ
I
i
Iшt.
i
t
*L
Fig. 5. Fluoгеsсenсе spефra of St on Sioz an.J sio1Ti02 рowdеrs, pгеparеd by sol-gеl
mеthоd, in vасuum сonditions undеr Nd-Y.\G ехсitation at 47О nm,
1- Sioz, 2-0'6%Tio2,3.1o/oТIo2,1.зo/o Tio2. 5. puге Tio;
Changе of the spесtral position оf thе fluоrеsсеnсе mахima of adsогbеd stilbеnе in air maу
bе connесtеd йth thе сhaлgе of loсal polariry aгound thе adsoгbеd spесiеs dtrе to соmpetitive
adsoгption of watег molесulеs from aiг and геmovin.Ч of adsoг-hej stilbеnеs to the plaсеs йth lоwег
polarity onе of the ейdеnсеs to suрport this pоint of viеw is thе invaгiability of fluоrеsсеnсе
spесtrum of St during first minutеs of the соntaсt йth air Thеn adsoгption of watег oссuгs and
adsoгbed stilbenеs гemovе from its initial adsoгption sitеs.
Thе narurе of siliсa аnd siliсa.titarria samplеs aсtivе сеntеrs is diffегеnt Sinсе thе adsoфеd
stilbеnеs on thе suгfaсеs arе moгe rigid than that in thе solutions, thеir adsorytion йll гesult in a
dесrеasе in intегnal сonveгsioц lеading to thе longег lifеtimеs, Kamat [1l] had pгopоsеd that
fluorеsсenсе quеnсhing of sеnsitized molесulеs adsoгbеd on thе Tioz suгГaсe is duе to еlесtrоn
injeсtion fтom ехсitеd dyе to thе сonduсtion band of titania. Тhе fluorеsсеnсe еmission quеnсhing
on puге Tio2 suгГaсе should bе attгibutеd to еlесtron transfеr from thе ехсitеd statе of stilbеnе to
rirе titania paгtiсlеs, йth thе apреaгancе of bluе сolor of Ti3- ions. Тhе samе is truе on thе siiiсa-
titania suгfaсеs with high сonсеntration of Tioz. Proсеss oГelесtron transfег
Stilbеnе + Тi4'эStilbеnе- * Tiз*
pгoсееds effесtively alrеady at thе dark оonditiоns
Сonсlusiоns
l. P1теnе and push-pull stilbеnе ше usеd as sеnsitivе fluоrеsсеnt ргоbе for thе сharaсterizаtion
of suгfaсе struсtuге of thе molесulаrlу dispегsed Tio2 /sio2 D-A substirutеd stilbеnе is
sеnsitivе to thе polaIitу of the enйronmеnt on thе sоlid suгfaсеs' Siliсa and siliса-titania
suгfaсеs aге с,ontainеd thе adsoгption piaсеs йth diffеrеnt polaritу of oН gгоups'
2. Photoсhеmistry of Py moleсulеs in miсгohеtеrogеnеous mеdia titania-siliсa сolloids is
сontrolled at pгеsenсe of сyсlodехtгinе. Quеnсhing of thе fluoгеsсеnсе and thе
intегaсtion of photoaсtivе Рy molесulеs with hеtеrogеnеous polar еnviгоnment of titania-
siliсa сolloids is supгеssеd duе to inсlusion сomplех foгmation'
iб5
3, Stilbеnеs fluorеsсеnое quеnсhеd еffесtivеlу whеn titania amount is 1% wt in thе miхеd siliсa-
titania sуstеm p,.p*JБу ,hе imprеgnatiЬn mеthod. Thе quеnсhing is attгibuted to еlесtron
injесtion from еxсitеd stilbеnе to titania.
4' Сhangе of tьe speсirJ |osition of the. fluorеsсеnсе maхima of stilbеnе on Sioz suгfaсe maу
bе сonneсtеd *ltь iье сhangе of loсal polшitу шound thе adsorbеd spесiеs duе to
сompеtitive uс,o.р.ion Ьгwatеi molесdеs йm aiiand геmoйng of adsoгbеd stilbеnеs to thе
piaсеs w.ith lowеr polaгitу.
Rеfеrenсes
lBardA.JSеmiсonduсtoгpaгtiсlеsandarraуsfoгthерl:t:*:T:.hеmiсalutilisationof
solaг еnегgy // Bег Bunsе"g",' гhy' Chеm _ l988 . v,92.-P.l l87-1194
2. Gеrishеr H' rn' pьotJJ"miсаl Сonvегsions, Braun A М (Еd.) Prеssеs Polytесhniquе
Romandеs: Lons, SW l983 p 2l 1
3. Anрo М. гr]oto.utut,il Ъn smatl рartiсlе Tio2 сatalуsts. Rеaсtion intегmеdiatеs and
геaсtionпrесhanisms.lzRеs Chеm Intегmеd 'i989 - v li }'] 1-P.67-106.
4.FoxМ.A.Chaгgеingесtionintosеmiсonduсtоrpaпiсlеs_imDoгtanсеinphotoсatalysis/i
iaChimiсaеt'Industriа.-l991.-v.68.P.59.64
5GrаtzеlМA.Еd:ЕnеrgуrеsouгсеsthrоughPhotoсhеmistryandCatalysis;Aсad.Prеss;
Nеw York, ]983
-^^^^.^|' ^Ь,' s of еxtremеlly small
Ъ.' д н""er"in Small-paгtiс1е rеsеarсh: phуsiсoсhепiсal propеrtlе
сolloirlal mеta.l and ,.*[""j".'"' рlniы-'zz ёhеm Rе". _1989 -v 89.- P.l861.l873
7. L Spanhеl, М.Andеrson Sеmiсonduсto, ,lu*.., in thе sol-gеl proсеss: quantized
aggrеgatiоn'gеlation"nJ-"ц..'"lgгоwthinсоnсеntratеdZnОсolloids//JAсS.-1991.-v.ll3'
N8.-P 2s27-2833 е and геaсti./е (sеmiсoпduсtoг) suгfaсеs //
8. P'Kaпrat Photoсhеmistry of nоnгеaсttv
Chеm Rеv . 1g9з.-У.9з,NI'- p.261 .21З | :- 1| гL^* D.', . 1оq1 -v sз .P 34l.
9. Fox М.A', oulaу м'i н"..,og.n.ous photоcatalуsis // Сhеm' Rеv.- 1993.-v.93'.P. 34l
ii]*u, A., Lе Liuntе S' Ал ovегvew оf sеmiсonduсtoг photoсatalysis // J.Photoсhеm.
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1l .Liu D.' Hug с, iiй"t p'v pьoto.ьеп,ustry оn slrrГaсеs /i J. Phуs. Chеm l995.-V. 99.-
i,l.;:жж'М.R., Martin S.T , Choi W Y :91h1*'ч1ni:^ч:*',оnmеntal
appliсation of
sеmiсonduсto. гr.,oto"uiurysis i/ Chеm. Rеv -
.l995 -V 95 .P 69-96'
13' Sегponе ш, r.u*Ё,, Ы, кьui*tаinou к.-pеti,zеttiЕ..Sizе еffесts on thе photophуsiсal
propеrtiеs of сolloiсa] u"u,u,. тiо, paпiсlеs: sizе quantisation oг dirесt tгansition in this
indirесt semiconаuсtJг?7i l. pьу' сь"m . i995 - v 99 - P 16646.|6654.
l4. Brinkеr C.J., Sсьеrer G.W. Ъol-gеl Sсiеncе; Aсaсi Press,Inс, N Y l990.
l5.Yamashitaн.,K;;,йS,Iсhih"ashiy,ншaoaм,ТakеuсhiМ,AnpoM',StewardG',Fox
A., Louis C., Сhe М ;;;;йn of titaniu*-J*n,ььary oxdе сatalysts prеpaгеd by thе sol-
gеl mеthod and thеir й"йi"iyь геaсtiйtil i"| ii"-rio";а-рЁasе oxidatioп of 1-oсtanol // J.Phys.
ёi... в. - 1998. . V. 102 - P 5870 - 5875.
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R.еl
:l
._ .1.
::-.г
l)--;
::еi]l
:3К
Сhе
:i S
166
miхеd siliса.
J to elесtron
surГaсе may
ies duе to
ilbеnеs to the
r;:iiisation of
,:lr1есhniquе
:.эciatеs and
r:эсatalysis //
: Aсad.Рrеss;
т*еlly small
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| id | oai:ojs.pkp.sfu.ca:article-55 |
| institution | Surface |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2025-09-24T17:44:39Z |
| publishDate | 2001 |
| publisher | Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | surfacezbircomua/f3/07ff16be42eee1f18cc2ac0f9d1b6af3.pdf |
| spelling | oai:ojs.pkp.sfu.ca:article-552018-11-27T09:42:39Z Pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions Pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions Pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions Smirnova, N. Eremenko, A. Rusina, O. Linnik, O. Yakimenko, O. Staruch, G. Ogenko, V. Chuiko, A. Spanhel, L. Rechathaler, K. Spectral characteristics of polar - push-pull stilbene (St) and nonpolar pyrene (Py) molecules on the silica and silica-titania surfaces have been studied by the methods of steady-state and momentary spectrofluorimetiy. Photochemistry of Py molecules in microheterogeneous media titania-silica colloids is controlled at presence of cyclodextrine. Change of the spectral position of the fluorescence maxima of stilbenes and lifetimes of stilbenes correlated with the change of local polarity around the adsorbed species due to competitive adsorption of water molecules from air and removing of adsorbed stilbenes to places with lower polarity. Stilbenes fluorescence is quenched effectively and this quenching is attributed to electron injection from excited stilbene to titania. &nbsp; Spectral characteristics of polar - push-pull stilbene (St) and nonpolar pyrene (Py) molecules on the silica and silica-titania surfaces have been studied by the methods of steady-state and momentary spectrofluorimetiy. Photochemistry of Py molecules in microheterogeneous media titania-silica colloids is controlled at presence of cyclodextrine. Change of the spectral position of the fluorescence maxima of stilbenes and lifetimes of stilbenes correlated with the change of local polarity around the adsorbed species due to competitive adsorption of water molecules from air and removing of adsorbed stilbenes to places with lower polarity. Stilbenes fluorescence is quenched effectively and this quenching is attributed to electron injection from excited stilbene to titania. &nbsp; Spectral characteristics of polar - push-pull stilbene (St) and nonpolar pyrene (Py) molecules on the silica and silica-titania surfaces have been studied by the methods of steady-state and momentary spectrofluorimetiy. Photochemistry of Py molecules in microheterogeneous media titania-silica colloids is controlled at presence of cyclodextrine. Change of the spectral position of the fluorescence maxima of stilbenes and lifetimes of stilbenes correlated with the change of local polarity around the adsorbed species due to competitive adsorption of water molecules from air and removing of adsorbed stilbenes to places with lower polarity. Stilbenes fluorescence is quenched effectively and this quenching is attributed to electron injection from excited stilbene to titania. &nbsp; Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine 2001-06-10 Article Article application/pdf https://surfacezbir.com.ua/index.php/surface/article/view/55 Surface; No. 4-6 (2001): Chemistry, Physics and Technology of Surface; 160-167 Поверхность; № 4-6 (2001): Химия, физика и технология поверхности; 160-167 Поверхня; № 4-6 (2001): Хімія, фізика та технологія поверхні; 160-167 3154-8091 3154-8083 en https://surfacezbir.com.ua/index.php/surface/article/view/55/54 Авторське право (c) 2001 N. Smirnova, A. Eremenko, O. Rusina, O. Linnik, O. Yakimenko, G.Staruch, V. Ogenko, A. Chuiko, L. Spanhel, K. Rechthaler |
| spellingShingle | Smirnova, N. Eremenko, A. Rusina, O. Linnik, O. Yakimenko, O. Staruch, G. Ogenko, V. Chuiko, A. Spanhel, L. Rechathaler, K. Pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions |
| title | Pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions |
| title_alt | Pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions Pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions |
| title_full | Pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions |
| title_fullStr | Pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions |
| title_full_unstemmed | Pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions |
| title_short | Pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions |
| title_sort | pecularities of electronic interaction of polar and non-polar organic fluorescent probes in the mixed titania-silica compositions |
| url | https://surfacezbir.com.ua/index.php/surface/article/view/55 |
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