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20, 4739

474a

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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

l^ntut

.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

Lwn-2 Atp"tæ Alben

Einncn\

69629

Vi

"urba:ine Ceàù.

Frd

ft

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

electron-hole 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

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

pyroly-si{3

electrodeposition,'?"

dip

coating,a

and

eyaporÂrion jnduced self:assembly leading to a rnesoporous

tiraniaflm

5

GeDerally, crysÉlùzitrg _{tirania requi.es thermal treÂtsneût at}

high

tempe.ature

(?'

>

450 "C). This

may

be â

severe

drawbâck

regâding

adhesion

of

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

r _{Cfrlspûding Àurhds. M.R.} p: _{e-mail niÊi]lriched@ùrs-im.n, Èt}

+ti

740 37 39 96,

fu

+33 240 31 39 95, L,B.: c mail lrc.bmbm @cùùfrn fr

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 rvnn}

(r)

o'R.Câi. B.: (nârzêI, M. l\';ùrc !991,353,131.

(2) (.) 6rgg, B. A.r richor

!.iFeffie,

S-; Fields, C, L.J' PÀ)s Cnm.

t

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,

i

L,i Tolb$. M :

civ.t.

M tlr4t

Ma.210t.

t:t,

1601.

(l)

Kriiger, L: Plass, R ; Piccn.ùi, M.; C àu elj M,i Bæùt U ,4ppl

Pr)t

I2t

n01. 79, 2085.

4l

Hd.l.

\

: Medier. D,: aù.ne. Y. B.: Sinrr. C, Sp,!!.J,

L

L

I

Chttu zn'J6,I, O2.

\5r (âl Hou

K,Tiû,E.

L -

BiM,7

Zl€o.D..Huee.C,J.tltar.rl

t-h.ù.2405. 15 tÀ

a

,''

Lr.elle-Belù

u.8.,

t'ren; P.: so,chs,

C: Bcll.liue P, BLL..

P:

mbei-

5: Cù.llel F.: BorrcE, C;

Gmsso. D.; Sarchez. C. Cà.u.

M"ls.

2j06,.18,6152.