Clen. MdteL mO\ 20, 4739 474a
!]39
Low Temperature Synthesis of Nanocrystallized Titanium Oxides
with Layered or Tridimensional Frameworks, from
[fiEO1r(H2O)24]Cls.HCl.7H2O Hydrolysis
Chia-Erh Liu,i Annabelle Rouet,l Hari Sùtrisno,t i Eric puzenat,l,$ Ilélène Tenisse,t
Luc Brohaa.* r and Mireille Richard-Plouet*.r
.les Maftnaw Je@ RM'L Uniùetsitë .k Nûie' CNRS 2, tue de Ia Houssilière 8p32229, 44322
NANTES Ceder, Frar.e, Depdftnteit of Chentisrr!, Frcul.! oJ Mathet@tic dnà Ndtûrdl kidce,,
yoglakatta State Uûiqetsit,r, Kat@tgwlang, 55261 fogydkana, Indowsid, dkd IRCELYON lasiitut ile
ret herchei sù la .dtdûîc et I'enuircnnewht àe Ltou, UMR 5256 CNRS-U|\ pr.tite Lwn2 Atp"tæ Alben Einncn\ 69629 Vi
Ceàù. Frd
l^ntut
ft
"urba:ine
Re.eiùed March 11, 2008. Rerise.l
Man^cipt
Receit e.l May 5, 2008
A low-tempemture âqueous chemical glo*'tÏ proc€ss wâs developed ro Foduce nanomeric ritaûiùm
oxide wiù cotrùolled size and structurâl vÂri€ry- cende hydrolysis of a commercial TiOCl, sôlùtioq in
a controlled relative humidity, leâds to ûe fomation ôf single crysrals of ITisOrr(HrO),4lCls. HCI . ?HrO.
UDdù aulogenous pressure ât 120'C, the hydrolysis of the latrer by reûamerhylamonium hydroxide
(noted TMAOH) is mÂtuly govemed by the R = TiÆMÀOH molar mrio and thus by the pH value. Tvo
values are particùlarly importanr R
8/9 and 8/17. The form€r con€sponds ro ihe bâlance of dre Ci
jons of the titdium oxychlolid€ hydrare by TMA+ carions and the laner ro the sroichiometric nrio fol
ùe fômation oi a lÂyered oxo-hydmnde CIMA)rTiror-,(CO:XOH)z.nHzO, x = 0.?, which is obrained
under bâsic condirions. Above R
8/9, thar is, in an acidic mediunr the solvothermal neârnent at 120
oC direcdy leâds
to rhe crystellizarion of anatase and rh€n rurile when rhË pH decreases. For inrermediare
R values, the amorphous dried solid is rcqu:rËd to be rirsed and dried at I 10 "C to lead to the crysrêUizarion
of nmometric riÉniâ, either datase or brookiie. TEM snrdies show thal titaria nênopadictes dhibit
sup€rctluctures involving a doubting of rhe cell paramerers rhâr could oiginate from rhe âdsorprion of
caÉonâte, hydrogen carbonare, or hydmxyl groups on rhe nanocrysiallte smfâce. trurirg evaporaiion of
i]le solvent, these crysrallites can sef-assemble to form micromeEic plâtelers,
:
:
Introducdon
Among the technologies ftâking use of the properties of
litanium oxide, the photoÂctiviry of TiO, is certÂinly one of
the mosr aûactive properties. The cretion of an electronhole pâir under UV inâdiâtion on TiO, and rhe chemical or
elecFon ûânsfer reâctions which follow âIe ât the hean of
lhe deveioprnent of pholodevices. Furthermore, in addirion
to the panicular applications connecred ro the exploirario.
of this propeny. sùch ês oxidârion photocatâlysis of orgadc
molecules, waterspiitting, ùd superhydrophiliciry, dtùium
dioxjde also Rnds applicarions in pholovoltaic dcvices. The
dye-sensitized solar ceils (DSSC)' consist of â ndosûucb.,red
iilm oi titaniùm dioxidÈ (Iiôt coated otr a subsrare of
conducrive glass. In such delices, ûe crucial role of rhe TiO
lÂyer deposited on the Eansparent conducriv€ electrode has
been demonstxated.2 The layer is reqùired on ûe one hând
r
+ti
Cfrlspûding
740 37 39 96,
p: e-mail niÊi]lriched@ùrs-im.n, Èt
+33 240 31 39 95, L,B.: c mail lrc.bmbm @cùùfrn fr
Àurhds. M.R.
fu
r.t +33 2,10 37 39 35, flr +13 240 3? 39 95.
I UnileNùé d€ Nantes C\RS.
r YôCysld, Shlc Unirdrily.
I UMR t256 cNRSrrn,FÊ,a
(r)
(2)
i
L,i
Tolb$. M :
civ.t. M tlr4t
Ma.210t.
t:t,
>
450 "C). This may be â
drawbâck regâding adhesion of
severe
ûr liln
on .he substrdl€
and nay also desEoy the initial self-orgùization.
Àmong the diffeienr synlheses, the ùse lcEamerhyl- or
teirâbuq,lanmoûium hydroxide to pmmore hydrolysis Ând
condensation of Ti alkoxides leads to remÂrkable rcsùlrs
regarding the control of rhe moryhology of riÉnia. In
pfflicùlar, Chenseddine and Moritz have lepo{ed rhar
alalase can be groqn either b( nsùrod, or spheres usrng
TMAOH to hyd.ùlyze Ti isopropoxide ùrder reflux !o
(l)
t
1601.
high tempe.ature (?'
rvnn
o'R.Câi. B.: (nârzêI, M. l\';ùrc !991,353,131.
(.) 6rgg, B. A.r richor !.iFeffie, S-; Fields, C, L.J' PÀ)s Cnm.
1001, 10J, 1422. O) Nogueiia. A, F i Loqqo, C: De Pâo!, M A
Coo.A Chen. Reu. ?,04, 2a8, 1a55. cl spi.dffirna, s, SmAid,
G., Kotr.lik,
to be dense to Âvoid any shor circuits between rhe electsolyre
ând the electrode and on the olher hand ro be nanosnucBred
to enllanc€ the collecdon of chÂrgc calriers. ln ùis particular
applicatioq a thin dense titania layer has ùus been oprimized.
Several methods have been reponed including sprây pyrolysi{3 electrodeposition,'?" dip coating,a and eyaporÂrion
jnduced self:assembly leading to a rnesoporous tiraniaflm 5
GeDerally, crysÉlùzitrg tirania requi.es thermal treÂtsneût at
4l
Kriiger, L: Plass, R ; Piccn.ùi, M.; C àu elj M,i Bæùt U ,4ppl
n01. 79, 2085.
Hd.l. : Medier. D,: aù.ne. Y. B.: Sinrr. C, Sp,!!.J, L
I2t
\
Chttu zn'J6,I, O2.
\5r (âl Hou K,Tiû,E.
Gmsso.
LI
L - BiM,7 Zl€o.D..Huee.C,J.tltar.rl
,'' Lr.elle-Belù u.8., t'ren; P.: so,chs,
P, BLL.. P: mbei- 5: Cù.llel F.: BorrcE, C;
t-h.ù.2405. 15 tÀ a
C: Bcll.liue
Pr)t
D.; Sarchez. C. Cà.u. M"ls. 2j06,.18,6152.
10.1021/cû800716f CCc: 540.?5 () 2008 Amricân Chemical Sociéty
Pùblistr.d on Web O6/24t2008