- [(MoOx) n]

.
,
, ,
3-5, 6, 7 (ODH)
.

?

.

, ,
situ Raman
. ,



, -
.
3,

,

.
,

--.
.
3
((4)) (4))

.

2. 1
().
( , /
() , ..)
.
()

-
. ()


- . ()
. ,


,
, .

(,
) , ( , /)
() Al2O3, ZrO2 , TiO2- SiO2.

2005 .
( DFT)
(Raman, IR) (DRUV/Vis) .
Raman,
. /2
() Raman
(VI)
HKMoXOYZ/TiO2 ( )
( )

DFT .
2.1 H DFT
(80%) (110)
(17%) (100) -Al2O3 ,
/ .
, , OQMo(O
Al)4 (110) -Al2O3,
(OQ)2Mo(OAl)2 (OQ)2Mo(
OAl) OQMo(OAl)3
(100). DFT
MoOx -
(110),
(100) -Al2O3.
,
.
, 10101018 cm -1
nMoQO OQMo(
OAl)4 (110), 995cm-1 OQMo(OAl)3
(100). MoOx/g-

Al2O3 . 23, Al
(110)
Al-O -;
- 4 Al-O-Mo
= ( 1,71)
1010-1018cm-1 . dft

(110) , (100)g-Al2O3. 25
(110) (MoOx)2
(OQMo)2O2x2, --, 6 5
CNMo = 5,6 ( 5).
- (OQMo) (OQ) 2MoO2x 3 -
(OQMo)2O2x2 - --,3, 4 5
CNMo = 4 (100).2,3 , ,
DFT 23,25 (MoOx)n Al2O3. DFT MoO3/gAl2O3
OQMo(OAl)4
(110).
nMoQO 10-15cm-1
.
- 770-880 cm -1
nMoOMo, 500-635 nMoO
Mo,s ().

MoO3/TiO2 (anatase

(100) (101).26-28*.
DFT 29* (101)
OQMo (-O-Ti) 3
MoOx . TiO2,
(101) (100) C4v
C3v OQMo(OTi)3 . (OQ)2Mo(OTi)2 .,
(001). 1004cm -1 .
60cm -1
2 .29*.
Mo2O6 Mo4O12 .30,31*.
. , DFT
(.. Mo4O12,
) CNMo
4 5 ( 6).31*.
30,31*
. ,

)2
( ).
OQMo(OTi)3 (101)

 2 ,
-. 30* , (MoOx)n (1)
.31*
. 32*.

. ,

. (.. )
.

MoO3/SiO2

MoOx MoO3/SiO2

. 33*.
(1%wt) MoO3/SiO2
.34*. 35*
OQMo(OSi)4 dioxo
(OQ)2Mo(OSi)2

2. DFT,36* , ,
, ( )
, .
,

.36*. ,

.
, ,
MoO3/SiO2 ( 6)
1000cm-1 MoQO
, 960-990cm-1 Vs() Vas
() OQMoQO. ,
DFT
MoO3/SiO2 37*
.
,
, Vs, OQMoQO, 1000cm-1 , 989cm-1
nMoQO37*.
, 38* DFT
MoOx/silica . (NEXAFS)
MoOx/SBA-15
, (OQ)2Mo(OSi)2
OQMo(OSi)4, .38*.

 MoOx
39*
, .

.
4 , (VI)
(apoys;ia H2). , ,
, - ,
.39*.
1000-1027cm-1 nMoQO, 9871002 cm1 for ns,OQMoQO and 939975 cm1 for
nas,OQMoQO.39*.
1 , , DFT
MoOx , g-Al2O3, TiO2-anatase SiO2.
, DFT

. ,
.
,
. , Fievez et al.40*
DFT
.
(SiO2,
Al2O3, TiO2, ZrO2). TOFs

.40* ,
;
,
40*.

3 Molecular vibrational spectroscopy

(Raman, IR)
3.1 Combination of in situ vibrational (Raman and IR)
spectroscopies and structural implications

IR Raman
,
.
. 41* Raman FTIR

.42--44*. ,

.

, ' (.. Cl4MoQO,

F4MoQO, Cl2Mo (QO) 2, Br2Mo (QO) 2, )
MQO
MQO
. ,

 MoQO (MoOx)n
,
( mono- - , ..),

QO. ,
( )

Q . ,

MoQO
MoOx,
M. , H3SiMo12O40
(1006 cm1)45* MoO2(SO4)2 Mo(QO)2 (
957 939 cm-1 918 895 cm-1 , ,
) 46*
. 1 , ,
-
- (M= V, Nb,W)
(VO, NbO) (NbO2, WO2) .
-
1000cm-1

( =) ( 1)
Raman
IR . , (2)
. ns
( Rman IR) nas (
Rmana IR) (nsnas) 10-30cm -1 .41*


. ,

M(QO)2
, 0== 90. 43,53,54*
=
() IR ;
,
( )
.
, Raman nR,MoQO,10 IR IR,MoQO,20

, oMoQO xMoQO
.

(1)
(2)

.41*
3.2 Combination of in situ Raman spectra with
18O/16O isotope exchange and structural implications

-
Raman IR
.
(Rman / IR)
18 43,44*


55*. (
Raman 18O )42*
= ( = 16 =18

(18/161) () =
( 18/161) 41*.
, Raman

. 49*. DFT
MoO3/SiO2 18/16 ,
,

. 35*.

56*.
,
= .
- =16 =18
, nMQ16O/nMQ18O
: 41*
(3)
mi . -
1.0513.
, (Rman IR)
= OQMoO3 of C3v
OQMoO4 of C4v .

 -- . ,
= ( - )
. , ( )

C3v C4v. ,
DFT, . ,
( )

( )
() --.

Experimental procedures in in situ Raman

spectroscopy and 18O/16O isotope exchange
experiments
4.1 Catalyst characteristics

2 MoO3/Al2O3,
MoO3/ZrO2 MoO3/TiO2 ,
18O/16O
Raman
. (1.11.8 Mo nm2)
( 6 nm 2) .
.
,47*,48. xMoO3/SyOz (S = Al, Zr, Ti),
x Mo (Mo nm2).
3 MoO3/TiO2(P25)
EDF( - )
(VI) - ( 7).
TiO2/P25 90% 10%
. 3 ,
pH ( ),
%.., .
xMoTi %.. .

4.2 In situ Raman spectroscopy

Raman 57*

.

(2). U
Raman ( )

 25-430C ( 2b).
488nm
49mW Raman.
.
90 ( ),
0,85 m Spex 1403 oyw -20
opoy cyxuhke apo RCA PMT
Labspec.
In situ Raman spectroscopy and 18O/16O exchange. 100mg

(2)
. Raman
450 162 (99,999%) 1
15cm3/min. ,
4,5%H2/N2 15 min at a 50 cm3/ min 2%
18O2/He (Messer) 15 min a 10 cm3/ min.
Raman 2% 18O2/He .
,
(18O / 16O )
182. /
2% 16O2/He .
15
90% 450 .
Temperature dependent evolution of Raman spectra obtained
for wet pastes. -
Raman HKMoXOY
Z/TiO2 ( , 7),
U-, ( 2)
Raman. Raman
(15 cm3 min1) O2, ,
MoVI.
,
2.
Raman 25-430 ,
Raman 25
.

4.3 In situ FTIR spectroscopy

Fourier IR 16O2

at 450 1C Nicolet 740 (DRIFT)

(Spectra Tech), MCTB
KBr. DRIFT 30 cm3 min1.

5 Mo(VI) solution Raman spectra and

solution speciation

\(VI) Raman

. (VI)
32*. ,
MoO4 2, HMoO4, MoO3 (H2O) 3,

H2Mo6O21 4, Mo7 O24 6, HMo7O24 5, Mo8O26 4 H3Mo8O28 5.

,
pH
.
CMo(VI) , =2102 ,

TiO2/P25 EDF (bl;epe periox;h 7).
SA1 ESI. (
)32* pH 9-6
42.
(1-4) 2
:
Gvib = A1(n1) + E(n2) + 2F2(n3 + n4)

Raman, F2 IR;
, 1 3
2 4 . Raman
Raman
:n1(A1) B 897 cm1, n2(E) B 317 cm1, n3(F2) B 837 cm1, and
n4(F2)B317 cm1. ,
,

. ,
Raman.
-

 .
13*. 7246
(B1.7 )
-(=)2 . ,
(;)
. 302
445 ( ) , 218 242
545 628 -- --
. 13*.
. 3 Raman
(VI) 3102 pH , 9 4.

(VI) 0,1.58*.
pH 9-6 ( a-d)
42 (
' 897 835).
pH=5 ( 3e) 950cm1
(=)2-
-.
(
950 897 cm-1 3e) .
3f, pH 4, 897cm-1 ,
950cm-1 954cm-1 907 cm-1
( stretchings)
.
Raman 3
( SA1 ESI). SA1 (ESI)
pH 9-6,
42. pH=5, 246 7245
42, pH=4
(Mo7O24 6, HMo7O24
5, Mo8O26 4 H3Mo8O28 5 H2Mo6O21 4) .

' 954 907cm-1
3f.


Raman.
raman. Raman
.

6 Configuration, molecular structure and

vibrational properties of supported (MoOx)n
sites on c-Al2O3, ZrO2, TiO2 and SiO2
(x)n
(SiO2, G-Al2O3, ZrO2, TiO2)
. 19*.


( )
() () [()] - . 13,20. ,
SiO2 ,

, 59*
. ,

- (.. Al2O3, ZrO2, TiO2)

() .13*.
/
, 60*
UV-vis
. ,

akra;ivn (Eg)
(VI)
--
4,19.
, ,
() G-Al2O3, -ZrO2 (), TiO2
() SiO2 .
Al2O3, ZrO2 TiO2

; ,
SiO2 .
6.1 In situ vibrational (Raman, IR) spectroscopy and in situ
Raman/18O isotope exchange studies of supported MoO3 on
c-Al2O3, m-ZrO2 and TiO2(anatase)
6.1.1 Spectroscopic results
3/Al2O3 47*. 4 5
Raman FTIR Ramana O18
450 (1,1 nm 2 , . 4)
(3,9 nm 2, 5) 3/g-Al2O3.
= Rman 162
: 994cm1 1.1 Mo nm2 ( 4) 1002 cm1
3,9 nm2 ( 5). , --
() 162: 850 855cm1, ,

 ( 4 5).
-- . 13,34,43,44,53,6172*. = FTIR
162: 1970cm1 1,1 nm2 ( 4) 1984 cm1 3,9
nm2 Mo ( 5).
30 ()
4,5% 2/2 2% 182/e: ) =16 (994 1002 cm1)
947cm1 1,1 nm2 ( 4b) 950 cm1
3,9 nm2 ( 5b) =18
(); ) (=); )
-- 825cm1 1.1 nm2 ( 4b) 818cm1
3,9Mo nm2 ( 5Ab); ) -
=16 (994cm1) ( 4Ab)
( ) ( 999cm1) ( 5 Ab).
47* 3/ZrO2. Raman/ FTIR
Raman/ 18O 3/ZrO2 ,
(1,7 nm2) (5,2 nm2) 450
6 7 . ZrO2
Raman ,
(). = Raman
162 : 985cm1 1,7 nm2 (
6Aa) 995 cm1 5,2 nm2 ( 7Aa). 1000cm1
( 6Aa). --
162: 837 850cm1, ,
( 6Aa 7Aa). , -
FTIR 162: 1950cm1 1,7 mn2 ( 6)
1965cm1 5,2 nm2 ( 7).
8,
Raman
- 4.5% H2/N2 2%182/He, .
: ) =16 ( 985 995 cm1)
=18 936cm1
1.7nm2 ( 6Ab 8A) 943cm1 5,2Mo nm2 ( 7Ab 8B)
=16; )
=; ) --
810cm1 ( 6Ab 8A) 817cm1
( 7Ab 8B); ) =16
985 983cm1 ( 6Ab 8A) 995 990
cm1 ( 7Ab 8B) 8.
=16
, . ,
18 ( 8)
.
3/TiO2 48,73* 9-11
3/TiO2. 9 10 Raman FTIR
450 162 1.8nm2 ( 9a ) 5.9
nm2 (' 10 Aa ) . rman
35 30 18/16 ( 4.5%2/2) / 2%
182/He) 9Aa 10Ab, . 11
Raman
. TiO2 ()
, ().
Raman 994cm1 =
162 ( 9Aa 10Aa), 937cm1
-- Raman 5.9 nm2
( 10Aa). FTIR
1965 cm1 ( 9 10).
( ), 18
rman 944 cm1,
=16 988 987 cm1 ,
, ( 9Ab 10Ab).
18/16 11,
Raman 1,8 5,9 Mo nm2
. ,

 - 16
944cm1 MoO18 ( 5 11 1
11).
()
(Raman FTIR) 162. 1
( Raman IR) ()
-l2O3, m-ZrO2 TiO2 () ()1-1.8 Mo nm2 (4-6Monm2) .
3 (.. Al2
(MoO4) 3, Zr(MoO4)2 )

(),
4-5 nm2 .22,61* .
=
Raman FTIR

() . ,
, IR 18 25cm1

Raman; , ( )

u=2' u=0. -,
.
Raman, ,
=1'0, IR , , =2'0,
( ) , =,
( -)
(1) (2). 1: 0,01
=
1005-1022cm1,
(). ,
(1) (2) ;
Raman, nR, Mo=O,1'0,
IR, nIR, Mo=O,2'0, ()
Raman IR M=O.
()
(
6,1,3).
,
() (g-Al2O3, m-ZrO2 TiO2 ), (..
, / ) ,
/ . () 4-7,9
10
.
3/Al2O3 47. ()
=(--Al)3 (CNMo=4) O=Mo(o-O-Al)4
(CNMo=5)
() ( 850cm1 - )
-AlO3 ( 4).
/ Al2O3 ( 5), Raman --
= (

 4Aa 5Aa). =(--Al)4

DFT, 23*
(110) -Al2O3
. ()
DFT,
.25*. (C) 4 5
(1)
.
19*,
4 5, 0+2(--l)2
, 850cm1 (, )
--Al. , 850cm1
(
-- ) 19*.
3/ZrO1 . 47*. ( )
ZrO2 ,
837cm1 -- ( 6Aa).
( 7Aa ) , --
, ZrO2
. ,9,22*

=(--Zr)4 CNMo=5. (c) 6 7

.

(=)2-(--Zr02
(0.55 nm2) (0
nsO=Mo-O 970cm1) .19*.
3/TiO2 48,73*. ()
TiO2
( 9),
-- 925cm1, (
) .

C3v,
DFT29* (101)
TiO2. , 937cm1 --
Raman ( 10Aa),

() ,
(..2,3). (c) 10
5
. , LIII-edge XANES


-
.61*.
( / )
CNMo 4 5 ( 6) DFT
30,31*. ,

Raman

 (--)
UV
.74*.
()
,
937cm1 -- ,
994cm1 =.
6.1.3 Interpretations and structural implications of vibrational
isotope effects
18/16 .

3 -Al2O3, m-ZrO2 TiO2-
47,48,73&
()
(-Al2O3, m-ZrO2 TiO2- )
(1.1-1.8nm2) (4-6nm2).
Raman 18/16

( ) 3/ZrO2 .53*.



Raman FTIR ( ).

DFT () '
() MoO3/g-Al2O3 23,25* MoO3/TiO2 ().
29-31*. ,
4-11
.
,
, 18/16
=
=16
=18 ,
( Raman/IR
)
3.2. 5 (3 3 )
=16
=18.
()

+
(3) 1.5013. 4
5 ,

=18. ,

-18- ( 8 9 5)

--.
raman -

 =16.
.
=16
5 5. ,
1.1 nm2 3/g-Al2O3 ,
(
18/16)

. ,
Raman

;
30 35
162 =16
( 2 5)

,
Raman
18/16 ( 8 11). ,
(
2 5 6 5)
18/16
, .
16 16
=16 18 (
--, 2 1
--, 1 1)

=16.
!8 (
) (
) ( )
18. , -18(-) / -18(-)
18/16
( , )
=16,
.

.

18/16
=16 .
1.1nm2 O3/Al2O3 (
=16)
() (
-- ) , ,

- -Al2O3.75*. 3cm1 ( 1002
999 cm1 ) 3,9Mo
nm2 MoO3/Al2O3
() ()
-- 18/16 ( 5).
ZrO2

 ;
2cm1 (985-993cm1)
5cm1 (995-990cm1)

18/16 --.
,
() () ZrO2.
3/@
()
=(--)3 .
8 10, =16

6cm1 7cm1 ( 994 988 987 cm1
35 30
, ).
, 11
Raman 2% 182/He
(2)/ (182) ,
. =16 (
1 cm1)
2cm1 5 (

994 cm1 11 ).
=16)
() () =16
18/16
16 =16.
,
DFT, 30*
2
--
- , 12(). 2

=.30*. , 18/16
, 12().
, =(--)3
18.16
, 12() 12().
,
=16. 18
,
(
) 18 =18-.
-18-() ,
( ).
18/16 (
12 ()-())
=16
(6-7cm1) =16
.

6.2 In situ spectroscopic studies of molecular structure of

SiO2-supported molybdena
Raman
()
SiO2
.76*. -
, , ,
.
2005 ,
3/Sio@
= . (2005) DFT
2.3
.

Raman
=(--Si)4
SiO2.77*
Raman
EXAFS/XANES
() SiO2
=(--Si)4
nMo=O 978-990cm1 61,78,79*
CNMo 4,5 6 .
Raman X (XAS)
= 984cm1 AB
(O=)2Mo(-OSi)2 MoOx
.34*. Raman
XANES EXAFS
de;igmatow Ox/SiO2 80*
=
988cm1


. , , DFT
35*
(=)2(-Si)2. ,
(Raman, IR, UVVis) 45*
Raman 18/16 49*
,
( g
UV-VIs DRS , 4)

(=)2(--Si)2 (ns,OQMoQO =
976991 cm1, nas,OQMoQO = B965975 cm1)
=(--Si)4
( nMo=O) 1020cm1.

, Rman, DRUV-Vis X (XAS),

()
0.20.8Mo nm2.81*. ()
4 6 . 81*.

500C
/
.82.
, , ,

967cm1 NAS,o=Mo=O,
991cm1 nMo=O
nsO-Mo-O
10-30cm1
nas,O=Mo=O. 82*
45 49,
967/991cm1
nasO=Mo=O/nsO=Mo=O (=)2(-Si)2 .


MoO3/MOy/SiO2 (M=Al,Zr,Ti) , 3
SiO2.83*. Raman
UV-Vis DRS

()
(y). / SiO2
3
.
oy () MoOx
SiO2.
/


. 83*.
7 Temperature-dependent evolution of the
configuration of Mo(VI) oxo-species on TiO2:
from the impregnation solution to the
calcined catalyst material
(VI)
pH Raman
5.

, 32*

KMoXOYZ/TiO2 ()
()
pH
(VI) 3 102.
Raman
HKMoXOY () .
,
pH
9, 6 4 13().
Raman 13.
Mo(VI)
-
Mo(VI) .32*.
, Mo(VI)
()

.
, 13 (),
Tio2(P25)
()

.

LevenbergMarquardt. pH=9
924cm1
870cm1,

MoO42 (897 835cm1, ,
3a). , (I)

MoO42 (II)
pH
oy for;ea 2(25) protvni;onetai,32*
MoO42
()
[Ti2OH O-MoO3]. H-
- ,

( MoO42)
.
pH=6
B939cm1
940,924
875cm1. pH,

[Ti-O-MoO3]
MoO4
' '

 H- .

3
.
, pH=6 Ti-OMoO3 ( 940cm1) Ti2Oh OMoO3 ( 924cm1).

875cm1.
pH ( pH=4),
Raman HkMoXOYZ/TiO2
950cm1
TiO2(P25).
( TiO2(P25)
) 955 (), 940 ( ),
924 (), 908 875 cm1. 940 924cm1
( ) Ti-O-MoO3
() Ti2OH O-MoO3 ( )
Mo-O; 875cm1
.
955cm1 908cm1
-Mo(=O)2- en;vsevn
Mo(VI) ,
3f
.


32*.
'-'
Raman,
Raman
924cm1 ( Ti2OH...O-MoO3),
940cm1( Ti=O=MoO3) 955cm1 (
(VI) ) Raman
HkMoxOYZ/TiO2 ( pH=9,8,7,6,5
4) pH .
( 14)

pH Cmo(VI),=3
102. ( )

.
. 15 Raman
( O2)

( 3).

 [Ti-OMoO3] [(Ti-O)2-Mo(=O)2]
[(Ti-O)3-Mo=O]
Mo=O 992-995cm1( 15).

() =.
( --
, 920cm1)
( 15).
( 14)
/
/
MoOx/TiO2 (EDF) 32*

.
,
,
Ti,

. '' ''

Raman
.84,85*. ,

,

(MoOx)n ' ,
.
Mox(.. )
Tammann
(TTAM=B12 Tf,Mox Tf,MOx ..
, MoO3 7961C ). , TTAM

/
,

Vox/Al2O3
5501 ( TTAM V2O5 ..:
690C).87*.
(
EDF 32*)

. 88*. , TTAM
. ,
-
T<Ttam
/.

8 Concluding remarks and future

perspectives
,
,
(MoOx)n g-Al2O3, m-ZrO2,
TiO2() SiO2.
/ (
2005 )

.
(RAMAN,IR, DR-UV)
DFT
,
(MoOx)n
.
Raman
IR 18/16
. (DFT)
. (MoOx)n
,

,
/.



.18*.

.

/

.