J. CHEM. SOC. FARADAY TRANS.

, 1994, 90(8), 1161-1170

1161

Spectroscopic Characterization of Magnesium Vanadate Catalysts

Part 1.-Vibrational Characterization of Mg,(VOJ2 Mg2V20, and MgV20, Powders
Guido Busca* and Gabriele Ricchiardi lstituto di Chimica, Facolta di lngegneria, Universita P.le Kennedy, 1-16129 Genova, Italy D. Siew Hew Sam Elf Atochem, Centre de Recherche de l'Est BP 1005, F-57501 Saint-Avold Cedex, France Jean-Claude Volta lnstitut de Recherches sur la Catalyse, CNRS,Avenue A . Einstein, F49626 Villeurbanne Cedex, France

The IR and Raman spectra of Mg orthovanadate Mg,(VO,), , Mg pyrovanadate M , , , gVO and Mg metavanadate MgV,O, powders are reported, described and discussed on the basis of the crystal structures of these phases and of the optical activity of the fundamental vibrational modes predicted with the use of the correlation method. The IR-active combinations are also discussed. The structural and vibrational features of these compounds are discussed in relation to those of other V-based oxidic catalytic materials.

The magnesium oxide-vanadium oxide system has been the object of attention recently because it presents promising catalytic activity in the oxidative dehydrogenation of hydrocarbons, such as alkanes (propane and butanel-') and ethylbenzene.6 Processes allowing the production of light alkenes (ethene, propene and butenes) and butadiene by oxydehydrogenation of the corresponding alkanes are becoming very attractive because of the availability of very cheap, light alkanes from natural gas. Our research groups have been previously involved in investigations concerning other vanadia-based catalysts extensively used in industry in partial oxidation processes such as the V,O,-P,O, systems for maleic anhydride synthesis from b ~ t a n e and ~V,O,-TiO, ~' systems for phthalic anhydride synthesis from o-~ylene.~.' fundamental investiA gation of the structure and chemistry of these systems can allow an interpretation of the role of the components additional to V 2 0 5 (phosphorus, titania and magnesium), in governing activity and selectivity. Attempts in this direction have already been proposed.' ' , 1 2 Several authors have investigated the solid-state chemistry of the MgO-V205 ~ y s t e m . ' ~ -Most of them'3.14*'7con'~ sider that only three stable compounds appear in this phase diagram : the orthovanadate, Mg,(VO,), , the pyrovanadate, Mg,V,O, , and the metavanadate, MgV206. Moreover, both Mg,V,O, and MgV,06 exhibit the phenomenon of polym~rphism.'~.''.'~ In the present paper a bulk vibrational characterization of V-Mg-0 catalysts is reported. The materials investigated here appear to X-ray diffraction (XRD) analysis to be almost pure Mg orthovanadate [Mg,(VO,),], Mg pyrovanadate (Mg,V,O,) and Mg metavanadate (MgV206).3The catalytic activity of these materials has also already been described.,

the 60VMgO precursor (58.5% V 2 0 5 w/w) by calcination in air for 49 h at 898 K, 60 h and 913 K, 15 h at 1023 K and 15 h at 1073 K. Mg pyrovanadate, Mg2V207, was prepared from the 69VMg0 precursor (66.4% V 2 0 5 w/w) by calcination in air for 6 h at 923 K and 6 h at 973 K. The metavanadate, MgV206, was prepared from the 82VMg0 precursor (79.8% V,O, w/w) by calcination in air for 6 h at 873 K and 24 h at 973 K. The XRD analyses (Siemens goniometer equipped with a quartz front monocromator, Cu-Ka radiation) showed quite pure phases except for Mg metavanadate, which presented traces of Mg p y r ~ v a n a d a t e . ~ Spectroscopic Measurements The IR spectra were recorded using a Nicolet Magna 750 Fourier-transform instrument. The skeletal spectra in the region above 400 cm- were recorded with KBr pressed discs and with a KBr beam splitter, while those in the far-infrared (FIR) region (400-50 cm-') were recorded using the powder deposited on polyethylene discs, and with a 'solid substrate' beam splitter. The spectra of the overtone region (above lo00 cm- ') were recorded using pressed discs of the pure powders, outgassed at 673 K in a heatablebiquid-nitrogen-cooled cell connected to a conventional gas-handling system. The laser Raman spectra were recorded on a Dilor Omars 89 spectrophotometer equipped with an intensified photodiode array detector. The emission line at 514.5 nm from an Ar+ ion laser (Spectra Physics, mod. 124) was used for excitation. The power of the incident beam on the samples were 36 mW. The aquisition time was adjusted according to the intensity of the Raman scattering. 100 spectra were accumulated in order to improve the signal-to-noise ratio. The wavenumber values obtained from the spectra were accurate to within about 2 cm-'. To reduce both thermal and photodegradation of samples, the laser beam was scanned on the sample surface by means of a rotatory lens. The scattered light was collected in back-scattering geometry.

'

Experimental
Catalyst Preparation The three pure magnesium vanadates were obtained by VMgO precursors generated by adding an appropriate amount of Mg(OH), to a basic aqueous solution (1% NH,OH) containing NH,VO,. The solid was then dried under vacuum at 373 K and immediately calcined at 823 K for 6 h to avoid any carbonation. Mg orthovanadate, Mg3(V0,), , was then prepared from

Results
The structures of the three Mg vanadates, deduced from literature are shown schematically in Fig. 1 , 2 and 3. In the case of the pyrovanadate (Mg2V,07), according to the X R D pattern and to ref. 17, the structure has been assumed

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J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90

Table 1 V-0 distances (A)in metal vanadates (from ref. 18-22)
compound Mg3(V0,), Mg,V,O, triclinic Co,V,O, monoclinic MgV,O,
v205

ref.

I1

I11

IV

VI

18 19 I I1 20 I I1 21 22

1.70" 1.63' 1.68" 1.63' 1.69" 1.66" 1.58'

1.70" 1.70" 1.71" 1.71" 1.70" 1.67" 1.77'

1.72" 1.71d 1.74d 1.72" 1.70" 1.85h 1.88'

1.81b 1.82' 1.78' 1.85' 1.84' 1.85' 1.88'

2.87/ 2.44/ 2.11' 2.02' 2.57g 2.83'

" V-0-Mg,

Fig. 1 Scheme of the structure of Mg,(V04),, from ref. 18, On the right: the coordination of the vanadate ion. Symbols : black spheres, V; white spheres, Mg; grey spheres, oxygen.

terminal oxygen coordinating two bivalent cations. V-O- Mg, terminal oxygen coordinating three bivalent cations. V-0-Mg terminal oxygen coordinating one bivalent cation. Asymmetric V,O-Mg,: like a but acting as weak fifth ligand to another V atom. ' Nearly symmetric V,O-Mg. V-0-V nearly symmetric bridge. Asymmetric V,O-Mg: like c but acting as weak sixth ligand to another V atom. Asymmetric V,O-V. V--. . .V terminal oxygen acting as weak sixth ligand to another V atom. In pyrovanadates the two V atoms (I and 11) are not equivalent.

The FTIR, FT-FIR and laser-Raman spectra (1200-50 cm-') are summarized in Fig. 4, 5, 6 and 7. The positions of the observed bands are summarized in Table 2. Interpretation of the spectra was achieved using the correlation method, as reported in ref. 23 and 24.

The Orthovanadate, MgJVO,,),

C

The orthorhombic magnesium orthovanadate (Fig. 1) belongs to the D i 8 = Cmca space group,18 with a = 6.053 A, b = 11.442 c = 8.330 8, and four molecular units per unit cell. The crystallographic unit cell contains two Bravais cells,

1 ,

Fig. 2 Scheme of the structure of monoclinic Co,V,O, from ref. 20, assumed to be isostructural with monoclinic Mg,V,O,. On the right: pairs of V,O:- ions. Symbols: black spheres, V; white spheres, Mg; grey spheres, oxygen.

[010] t
1200 1000

800

600

400

200

waven umberjcm-

'

Fig. 4 FTIR (a), FT-FIR (b) and laser Raman (c) spectra of Mg3(V04)2 powder

0.9 0.8 0.7 0.6 0.5 -

Fig. 3 Scheme of the structure of MgV,O,, from ref. 21. On the right: structure of the [(V,0,)2-], sheets. Symbols: black spheres, V; white spheres, Mg; grey spheres, oxygen.

0.40.3:
4

to be the same as that of Co,V,O, ,2o both being monoclinic (space group P2Jc = Cz,). In Table 1 the V-0 distances present in the relevant structures are summarized, also including those of triclinic Mg,V,O, l 9 and of V,O,, 2 2 for the sake of completeness.

.............................................

1200

1000

800

600

400

200

waven umber/cm -

'

Fig. 5 FTIR (a), FT-FIR (b) and laser Raman (c) spectra of Mg,V,O, powder

J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90

0.60 0.55

1163

0.50
0

0.45 0.40 0.35 0.30 1200

molecular units placed in C, symmetry sites, coordinated through ionic bonds to Mg2+ cations. For each VOZmolecular ion, nine internal vibrational modes are expected, which corresponds to 36 modes for the entire Bravais cell. The assignments of the remaining 39 optical modes are summarized in Table 3. The free V0:- ion is tetrahedral (T', point group) and correspondingly the following irreducible representation is valid :

1000

800

600

400

200

wavenumber/cm-

'

Fig. 6 FTIR (a), FT-FIR (b) and laser Raman (c) spectra of MgV,O, powder. The peaks marked with stars belong to Mg,V,O, impunties.

The A, mode is the symmetric stretching vl, while the E mode is the symmetric bending v 2 . The two F, modes correspond to the asymmetric stretching (v,) and the asymmetric deformation (v,). In our case, one oxygen atom is bonded to V with a longer bond than the other three, so the symmetry is near C3", the two F, modes being split into A, + E. When the symmetry is lowered to C , , the site symmetry in our case, the degeneracies are completely broken and the irreducible representation changes to the following:

rCsVOa + 3A" = 6A'

where all modes are both IR- and Raman-active. Under the factor group D,, each A' mode gives rise to A,(R) + B3,(R) B,,,(IR) B,,(IR) modes, while each A" mode gives rise to B,,(R) B,,(R) A,(inactive) B,,(IR). According to these correlations, the symmetric stretching d of the V0:- ions (v,, A, in T point group) gives rise in the Mg orthovanadate to four modes [A,(R) + B3,(R) + B,,,(IR) B2,(1R)], while the asymmetric stretching ( v 3 , F, in & point group) gives rise to 12 modes [2A,(R) + 2B,,(R) 2B1,(IR) 2B,,(IR) B2,(R) + B,,(R) + AJinactive) + B3J1R)]. Accordingly, also the number and activities of the vibrational modes arising from the asymmetric and symmetric deformation modes of the VOZ- entity, as well as from the other lattice modes, can be predicted. The distribution of the fundamental modes of Mg,(VO,), is summarized in Table 3. According to the above discussion, we can attempt some assignments of the observed IR and Raman spectra of Mg orthovanadate. In the region above 500 cm-' we expect the presence of bands arising from the stretchings of VO, tetrahedra. The symmetric stretching (v,) of the isolated orthovanadate ion is expected and is reported to correspond to the strongest Raman peak, quoted at 827 cm- for the free ion in aqueous solution.25For the free ion this band is IR-inactive. According to the above discussion, under coupling of the four VO, unities in the Bravais cell, this mode is expected to split into two strong Raman peaks and two weak IR bands. So, we assign the two strongest Raman peaks in the spectrum of Mg orthovanadate, at 862 and 827 cm-', to the two components of the symmetric stretching mode. The strongest peak at higher frequency is assigned to the totally symmetric A, mode, the other being assigned to the B,, mode, i.e. to a mode that is symmetric with respect to the x, z symmetry plane and antisymmetric with respect to the x, y and y , z planes. It seems reasonable to assign the weak but sharp IR peak at 833 cm- to the two corresponding IR active modes with B,, and B,, symmetries, that are symmetric with respect to the x, y and x, z symmetry planes, respectively, and antisymmetric with respect to the others. These modes could be superimposed upon each other, and are almost coincident with the Raman-active B,, mode, assuming that the three symmetry planes are equivalent, which is, obviously, not true. The frequency of these three modes, near 830 cm-', and also the 'centre of gravity' of the four components assigned to modes arising from v1 (837 cm- ') are very near to the wavenumber of v1 of the unperturbed vanadate ion (827 cm- ').

e
0

al m C

+ +

2400

2200

2000 1800

1600 1400

1200

wavenumber/cm-'

'

Fig. 7 FTIR spectra in the overtone region: Mg3(V0,), (a), Mg,V,O, (b),MgV,O, (c)and V,O, (d)powders

each one containing two molecular units, i.e. 26 atoms. Accordingly, 78 total modes are expected, three of which correspond to the acoustical modes and 75 are vibrational models. Two different types of octahedrally coordinated Mg ions are present while the tetrahedrally coordinated V atoms are all equivalent. The VOi- ions have C , symmetry, although approaching a symmetric tetrahedral configuration. According to factor group analysis we can obtain the following irreducible representation for the optical modes of Mg,(VO,),:

to added. Consequently, we expect 31 IR-active modes and 36 Raman-active modes. The vibrational structure of Mg,(VO,), can be discussed by considering covalently bonded VO: - vanadate ions as

+ 8AJinactive) + 12B,,(IR) + 11B2,(1R)+ 8B,,(IR) which the acoustic modes (Blu + B,, + B,,) should be

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J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90

Table 2 Position of the observed vibrational bands for the Mg vanadate powders
Mg,(V04)2 IR fundamentals
915 861 833 730 sh 687 610 br sh 827 724 w 862 vw 690 897 sh 881 sh

Mg2V20, assignment IR
975 sh 968 917 880 sh 840
VO, str.

MgV20, assignment IR Raman assignment

Raman

Raman

923 888 840 sh

VO str.

asVOV str." VO, str.

818 770 sh 690 668 575 462 439 402 379 362 325 sh 3 14 302 sh 285

VOV str.
570

695 sh 655 620 575 sh 552 430 383 350 br 302 286
440

485 473 415 394 370 336 320 29 1 248 205 171 156 136

473 448 41 1 39 1 35 1 344 330 308 vw 290 275 245 br 235 vw 200

V 0 4 def. + lattice

242 220 198 190

145 137 122 130 1933 1910 915 + 881 862 861 861 + 827 862 + 485 1790 1694 1615 1430 1210 1116

440 410 403 377 354 335 316 305 282 268 243 228 216 198 181 165 155 145 131 113

332 309 268

VO, def. + lattice

212 198
150

204 174 149

IR combination
1790 1720 1672 1347

975 + 948 968 + 948 917 + 873 873 818 845 + 840 845 + 770 818 620 630 575 569 + 575

1867 1780

+ + +

655 655 + 552 732 695 + 440 923 + 888 923 + 840

+ +

1408 1208 1117

731 695 695 523 731 + 383

+ +

str., stretch; def., deformation; sh, sharp; br, broad; as, asymmetric; vw, very weak. Very asymmetric VOV bridges.

Table 3 Distribution and assignments of the fundamental modes of orthorhombic Mg3(V04),

vo4
symmetry activity total
10

origin internal
6 3 3 6 3 6 6 3 36
v1

acoustical

optical
10 8 7 11 8 12 11 8 75

lattice
3 3 2 4 3 5 4 3 27

librational
1 2 2 1 2 1 1 2 12

v2

v3

v,

2
1 1

8 7 11 8 13 12 9 78

2 1 2 2 1 12

2 1 1 2 1 2 2
1

12

J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90

1165

The asymmetric stretching mode (v,) corresponds to the strongest IR band for the isolated V0:- ion, and is also Raman-active, although weak, at 780 ern- '. 2 5 This mode is expected to give rise to five strong IR bands and six weak Raman peaks in our case. We must consequently assign the two very strong IR bands, both showing multiplicity, centred at 861 and 687 cm-', with components at 915, 740 and 610 em-' to the IR-active modes arising from v 3 . The weak Raman peaks at 897, 881 and 724 em-' should be assigned to three of the six expected weak Raman-active modes arising from the splitting of the asymmetric stretching mode, v 3 . To attempt an identification of these modes we recall that among the four oxygen atoms that are bonded to vanadium, only two are equivalent, according to the C , site symmetry. One of the two in-plane V-0 bonds is definitely longer than the others. So, we propose that the main cause of splitting of the asymmetric stretching mode is internal to the vanadate ion, due to the non-equivalence of the V-0 bonds. This allows us to explain why the splitting of v 3 is much stronger than that of v,, which is only due to the crystal structure effect, i.e. to the copresence of four equivalent units in the Bravais cell, whose vibrations are coupled. As shown in Table 4, if one V - 0 bond is longer than the others (C," symmetry) the triply degenerate v 3 mode (F, in & point group) splits into two components (A, + E). If only two oxygens are equivalent, as in our case ( C , site symmetry), the E mode further splits into A' + A", and the A, mode becomes A'. The last mode is expected to fall at frequencies even higher than the symmetric stretching mode. The A" modes arising from the E mode in C,, can be expected at lower frequency. Each A' mode under D,, point group produces four components [A,(R) + B,,(R) + B,,(IR) + B3,(1R)]. So, we assign the IR bands at 915 and 861 em-' to the B,, B,, modes and the Raman shoulders at 897 and 881 em-' to the A, + B,, modes, all arising from the high-frequency A' component of v , . The 'centre of gravity' of both pairs of bands is near 888 cm-l, which can be assigned to this component of the asymmetric stretching mode, modified by lattice effects. As a consequence, we can assign the Raman peak at 724 em-' and an extremely weak feature that can be envisaged near 680 em-' to the remaining four Raman-active modes arising from the asymmetric stretching of the shorter V-0

bonds, probably superimposed in pairs, although it is possible that some of them are too weak to be detected, and lie at lower frequency. The IR bands at 740, 687 em-' are assigned to the corresponding IR-active components of the asymmetric stretching mode, a third one probably being superimposed on them and undetectable. The centre of gravity of these modes is near 720-700 cm-', which can be taken as the value of the asymmetric stretching mode under C,, symmetry, modified by crystal effects. A summary of our assignments for the stretching modes is given in Table 4. Even more complex would be the assignment of the many peaks observed in both IR and Raman spectra below 500 em-',to the deformation modes of vanadate ions and to the rotational and translational lattice modes. We will limit ourselves to the observation that we detect at least 15 Raman and 15 IR bands in the region 500-100 cm-', in contrast to the expected 28 Raman-active and 24 IR-active modes. This may be due to the superimposition of different components. The IR spectrum is apparently composed of a weakly split medium-intensity band at 485,473 ern- and of a very broad absorption centred near 400 em-',on which at least 13 components are superimposed. The former split absorption is assigned to a component arising from the v4 asymmetric deformation mode, also IR-active for the symmetric V0:anion, while the latter broad adsorption agrees, because of its position and broadness, with the assignment to lattice modes mainly involving stretching modes of MgO, octahedra.,, From our tentative assignments, we can attempt some conclusions. Comparison of the spectra we report here with those reported by other authors for the same ~ o m p o ~ n shows -good~ agreement, but with nond ~ ~ ~ ~ ~ ~ ~ negligible differences. For example, we do not detect at all of the weak IR component reported both by Hanuza et d 6and by Baran and AymoninoZ7at 962 cm-', which is likely to be due to an impurity arising from Mg2V,07 (see below). Similarly, the Raman spectrum of Mg3(V04), reported by Owen and Kung28 clearly shows additional peaks at 948 and 900 em-', also likely to be due to Mg,V,O, impurities. Moreover, the interpretation of the spectra of Mg3(V04), we propose here shows some marked differences from the previous based on an imperfect knowledge of the structure. Comparison of our spectra with those reported for the compounds Ca,(VO,),, Sr,(VO,), and Ba,(V04),,2i27929*30

Table 4 Scheme for assignment of the dundamental stretching bands of orthorhombicMg3(VOJ2 (an- I ) and their IR-active combinations site symmetry factor group

915 881 862 861 861 + 827 862 + 485

+ +

1790 1720 1672 1347 915 897

IR IR IR

IR
IR
R

88 1 862 86 1 833, 827 740 724 687 (690)

R R IR IR R

IR R IR R

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J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90

which are not isostructural with Mg3(V04), , clearly points to the effect of the crystal structure and symmetry on the vibrational spectra. This makes unreliable simple correlations on the position of bands with, e.g. catalytic activity, for nonisostructural compounds, such as those proposed in ref. 2 and 31.

and consequently, 63 optical modes are expected, which are either IR- (A,) or Raman-active (BJ. The V 2 0 , 4 - ions are bent, with a nearly staggered trans orientation of the oxygens of the VO, units. So, the ion symmetry is near C , . Factor group analysis for the unit cell of triclinic Mg,V,O, leads to the following irreducible representation:

rap, = 33Ag(R)+ 30A,(IR)

The Pyrovanadate, Mg,V,O,
Mg pyrovanadate is polymorphic, showing at least three different structures at ordinary pressure. 14*' According to Clark and Morley,', the form stable at room temperature is ; monoclinic (Fig. 3), belonging to the P2,/c = ch space group, with a = 6.605 8,, b = 8.415 8, and c = 9.487 8, and /3 = 100.61", and with four molecules per unit cell. Although the structure of this form has not been refined, it is thought to be isostructural with Ni and Co divanadates, whose structures have been studied in detail.20 Mg,V,O, transforms near 1000 K to a triclinic form, whose structure has been refined by Gopal and Ca1v0.l~A further phase transformation occurs at even higher temperatures. 14v1 Triclinic magnesium pyrovanadate belongs to the Pi = Ci space group with a = 13.767 A, b = 5.414 8, and c = 4.912 A, a = 81.42", /3 = 100.61", y = 130.33", and with two molecular units per unit cell. The triclinic structure of Mg,V,O,, as well as that of several other bivalent divanadates, can be termed thortveitite-like, being closely related to that of the mineral thortveitite, Sc,Si,O, (C2/m = cih space group), because in both cases sheets of M,O, plyanions are present. However, the structure of triclinic Mg,V,O, differs in many respects from that of thortveitite owing to the geometry of the M-0-M bridge of the M,O, anions (linear in thortveitite and bent in Mg pyrovanadate) and because of the coordination of the vanadium ions, which is approaching five-fold owing to weak interactions with the oxygens of the nearest pyrovanadate ions. The structure of monoclinic Mg,V,O, , assumed to be the same as that of monoclinic C0,V207, as proposed by Clark and Morley,17 is not thortveitite-like because the M 2 0 7entities do not form sheets. The unit cell of the monoclinic structure contains 44 atoms, and consequently, 129 optical modes are expected. The V,074- ions are bent, with a nearly eclipsed cis orientation of the oxygens of the VO, tetrahedra. So, the ion symmetry is near C,,. Factor group analysis for the unit cell of monoclinic Mg,V,07 leads to the following irreducible representation : to which the acoustic modes 3A, should be added. Since the volume of the monoclinic unit cell is nearly double that of the triclinic unit cell (both primitive), the two structures could, in principle, be distinguishable by vibrational spectroscopies, because for the former structure the number of bands should be nearly double that for the latter. However, if the A,B coupling for the monoclinic compound is sufficiently small, only half of the bands appear because they are superimposed in pairs. So, the two structures are indistinguishable by vibrational spctroscopy. This is probably what occurs for our monoclinic Mg,V,O, , where nearly 30 IR and Raman components, instead of 66 Raman and 63 IR, are observed. In Table 5 the assignments of the vibrational modes to lattice modes and internal vibrations of the pyrovanadate groups are also reported for both structures. These groups approach C,, symmetry in the monoclinic structure, for which the following irreducible representation is obtained :

rc.vv207 = 7 A , +

4A2 + 6B1+ 4 ~ ,

rapt = 33Ag(R)+ 33Bg(R)+ 32A,(IR)

+ 31B,(IR)

to which the acoustic modes A, + 2B, should be added. The unit cell of the triclinic structure contains 22 atoms,

Among these 21 vibrational modes of isolated V , 0 7 ions, 17 are IR-active (A,, B, and B, symmetry modes) and 14 are Raman-active (A,, B, and B,). Under site symmetry C , , all modes become A and all split into Ag(R)+ B,(R) + A,(IR) + BJIR) under the factor grup Ci. Of these 21 modes, six are terminal V-0 stretchings, 12 terminal bendings, two bridge stretchings and one bridge bending. Note that of the six terminal V-0 bonds, one each side is particularly short, while the other four are equivalent to each other and to the shorter three bonds of the orthovandate ion in Mg3(V04), (see Table 1). To attempt an assignment of the observed bands we can again divide the spectrum at 500 cm-'. Above this frequency we expect only V-0 stretching modes. Above this frequency we detect eight well resolved IR bands and seven well resolved Raman peaks. It seems reasonable to assign the IR bands at 668 cm- and at 575 cm- as well as the Raman bands at 620 and 570 cm- to the asymmetric and symmetric stretching modes of the V-0-V bridge. This assignment agrees with that of Pedregosa et d J 2 higher-frequency comThe ponents of these bands in both the IR and Raman spectra are clearly split (690, 668 cm-' in IR, 630, 620 cm-' in Raman)

',

Table 5 Distribution and assignments for the fundamental modes of monoclinic and triclinic Mg,V,O,
v20,

terminal V - 0 internal stretch bend

v-0-v
stretch bend

symmetry

activity

total

acoustical

optical

lattice

librational

monoclinic, S.G. P2Jc R A, R B , IR A, Bu IR total triclinic, S.G. Pi R A, IR A, total

33 33 33 33 132 33 33 66

33 33 32 31 129 33 30 63

9 9 8 7 33 9
6
15

21 21 21 21 84 21 21 42

6 6 6 6 24 6 6 12

12 12 12
12

48 12 12 24

J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90

1167

and this can be taken as evidence for the A,-B, and A,-B, splittings, respectively. The bands in the region 1000-700 cm- should be due to terminal V - 0 stretching modes. In both the IR and Raman spectra we observe two sharp bands just above 900 cm-, but their intensity ratio is inverted in the two spectra. Moreover, this pair of bands is stronger than the bands in the region 900-700 cm- in the Raman spectrum, while the reverse is found for the IR spectrum. It seems reasonable to assign the strongest Raman mode (902 cm-) to the totally symmetric stretch, which has the character of a symmetric stretch of the two shortest V-0 bonds. Consequently, the weaker mode at higher frequency (948 cm-) can be assigned to the asymmetric stretching of the two shorter V-0 bonds. The same modes origmate the IR bands at 917 and 968 cm- respectively, whose intensity ratio is, accordingly, the inverse of that in the Raman case. The weak splitting of the band at 968 cm- can be further evidence for the weak A,-B, splitting. The remaining bands, located in the 930-700 cm- region, are assigned to stretching modes of the longer terminal V-0 bonds. Five components can be distinguished in the IR spectrum, as expected assuming no A,-B, splitting, while only two are found in the Raman spectrum, perhaps owing to the very weak strength of some of them. The region below 500 cm- shows a split IR band at 462, 439 cm-, similar to that observed at 485 and 473 cm- in the case of the orthovanadate, assigned to a deformation mode of the VO, entities. The components in the region 450100 cm- are assigned to lattice modes and to deformations of the pyrovanadate ions. According to this interpretation of the spectrum in the V - 0 stretching region, we have very weak A,-B, and A,-B, splittings, while A , A , and B,-B, splittings are significant (up to 40 cm-), as evidenced by the separation of the IR and Raman modes. This might be due to the particular association in centrosymmetric pairs of the pyrovanadate ions in the structure of monoclinic Mg2V20, (see Fig. 3), whose vibrations are consequently strongly coupled. Note that the IR spectrum we report here for Mg,V,O, is consistent, although not entirely correspondent, with that discussed by Pedregosa et aL3 and with that reported by Pate1 et but both the IR and Raman spectra are definitely different from those reported by Hanuza et a/.,, which correspond to a mixture of phases. On the other hand, the Raman spectra reported by Stencel for a-Mg,V,O, (monoclinic polymorph) and by Hardcastle and Wachs3 for #?-Mg2V20, (triclinic polymorph) are instead due to mixtures of aMg,V,O, and MgV,O,. The IR spectrum we report here does not compare well with those of the other alkaline-earthmetal pyrovanadates which, in fact, are not isostructural with monoclinic MgV,O, .

forming infinite anionic [(V,0,)2 -1, layers parallel to the (001) face. Inside the layers, zig-zag chains of edge-shared VO, octahedra may be distinguished along the [OlO] direction. Factor group analysis allows us to obtain the following irreducible representation for the optical modes of Mg metavanadate :

+ 4B,(R) + 4A,(IR) + 8B,(IR) to which the acoustic modes (A, + 2B,) should be added.
rapt = 8A,(R)
To divide the optical modes into lattice and internal V-0 vibrations with known physical meaning, we must divide the vibrations associated with motions of Mg ions (A, 2B,) from those associated with internal vibrations of the [(v206)], polymeric layered molecular anion lying in the (020) plane of the unit cell (with Mg ions assumed to be at the corners). For this layer, 21 internal vibrations are expected, whose distribution among symmetry species, obtained by the difference spectra, is reported in Table 6. The three oxygen atoms of each VO, unit, two of which are present in the smallest Bravais cell, are of three different types. O(1) is bonded to a single V with a short V-0 bond ) (1.666 A , but also bridges two Mg ions; O(I1) bridges two V atoms very asymmetrically with one very short (1.671 A) and one very long (2.671 A) V - 0 bond, but also coordinates one Mg ions; O(II1) triply bridges V atoms with bonds of intermediate length. To simplify the structure, we can neglect the sixth weakest coordination at the vanadium ions, so that the O(I1) atoms become terminally bonded to V atoms like O(I), and the zig-zag chains of edge-shared V 0 6 octahedra along the [OlO] direction are separated from each other. The structure of one chain is reported in Fig. 5. In this view, the 24 optical modes of the structure are divided into 20 internal vibrations, one rotational mode along the b axis of the [v,06]z- chains and three lattice translational modes. The vibrations associated with the weak bonds we have artifically broken become rotations of the chains. Each V ion is now pentacoordinated, with two short terminal V-0 bonds located in the symmetry plane of the unit cell, parallel to the (010) plane, and three longer V-OV, bonds with O(II1) atoms in a plane parallel to the [OlO] direction. We can now divide the vibrations associated with VO, units with short V-0 bonds from those associated with the motions of the O(II1) atoms in the (V,O,), layers. Our 24 total modes are now constituted by three lattice vibrations, one rotation of the V,O, chains, eight modes of the V,O, network involving O(II1) forming a chain along the b axis, and finally, six out-of-plane deformations, two in-plane deformations and four stretchings of VO, short-bond units. The symmetry species and activity of these modes can be found in Table 6. The observed spectra of the Mg metavanadate are comparatively simpler than those discussed above for the orthoand meta-vanadate, owing to the smaller size of the unit cell. The Raman spectrum shows 12 very well resolved bands, just as expected. The IR spectrum is much less well resolved, but also shows almost 12 components, as expected. However, we also observe in the IR spectrum weak components arising from Mg,V,O, impurities. Above 800 cm- we observe two Raman bands and two IR bands, which are assigned to the stretching modes of the VO, units. The strongest Raman mode at 923 cm- certainly arises from the symmetric stretching mode of V 0 2 , while that at 836 cm- arises from the asymmetric mode. By analogy, the IR band at 888 cm- is due to the IR-active component arising from the symmetric stretching mode, while that at 840

The Metavanadate MgV,O, Monoclinic magnesium metavanadate (Fig. 5 ) is isomorphous with the brannerite mineral having the formula (Th,U)Ti,O, : both belong to the C2/m = Czh space group,2 with two molecular units per crystallographic cell. The unit cell dimensions are a = 9.279 A,b = 3.502 A,c = 6.731 A,#? = 111.77. This phase transforms near 535C into a pseudobrannerite-type form, and at high pressure into a cou1ombite-type form. The smallest Bravais cell of the brannerite structure contains one molecule only, i.e. nine atoms. Accordingly, 27 total modes are expected of which three are acoustical modes and 24 optical modes. The structure consists of both Mg2+ ions and V5+ ions in octahedral coordination, and of three different types of oxygen atom, each tricoordinated. VO, octahedra are linked by three edges,

1168

J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90

Table 6 Assignments for the fundamental optical modes of monoclinic MgV'O,
(VO,)+
a

cv 2
op
1

0 2Ia

symmetry

activity

total

acoustical
0
0 1 2

optical
8 4 4

Mg
0 0

[V,06]'-

(internal)
8 4 3

stretch
2 0 0

ip
1

int.
4 1

rot.
0

4%
B* A, B"
total

8
4 5 10

R
IR IR

8
24

1 2

6 21

2
4

0 0 1 2

2 2 1 6

1 2
8

1 0 0
1

27

The vibrations of the planar polymeric macroanion [v,06]'- have been divided into those of the bent (VO,)' units and those of the [V,O,] polymeric zig-zag chains. ip, in-plane deformations of V 0 2 units (short bonds); op, out-of-plane deformations of VO, units (short bonds).

The spectrum of Mg3(V0,), is composed of a triplet at cm-' is assigned to the IR-active mode arising from the 1790, 1720 and 1697 cm-' and of a further strong band at asymmetric stretching. This agrees with the stronger intensity 1347 cm-'. The triplet clearly corresponds to the comof the former band. We can recall that only one of the V - 0 bination modes of the bands arising from the splitting of v1 bonds is a true terminal bond (although the oxygen is coordi(symmetric stretching of the V0:- anion) as well as of the nated to two Mg ions), the other being a very asymmetric highest-frequency components of v3 (asymmetric stretching of V-0-V. An alternative, more rigorous assignment for the VO:-), while the band at 1347 cm-' could be due to a compeaks at 923 cm-' (Raman) and at 888 cm-' (IR) is to the bination of the Raman-active mode at 862 cm- arising from asymmetric and symmetric stretchings of the two true terminthe symmetric stretching vl, which the IR mode at 485 cm- ', al V-0 bonds, one per VO, unit. The IR and Raman peaks, probably arising from the deformation mode v4. Note also almost coincident near 840 cm- are consequently assigned an additional very weak, sharp band at 1964 cm- ', which is to the stretching of the very asymmetric V-0-V bridging due to a surface vibration (see Part 2 of this series).37 system, involving O(I1). The spectrum of the pyrovanadate shows a very characterIn the region 800-500 cm-' we observe two peaks in the istic sharp doublet at 1933, 1910 cm-'. These two comRaman spectrum at 731 and 523 cm-', and a complex IR ponents necessarily arise from the two crossed combinations absorption with the most intense bands at 655 and 552 cmof the two superimposed Raman-active and two weakly and probably two other components at 695 and 620 cm-'. resolved IR-active modes arising from the stretchings of the These bands are assigned to the stretching motions of the shorter V - 0 bonds. The theoretical values of these modes V20, network with triply bridging O(II1) atoms. These are 1923 and 1916 cm- The strong band in the intermediate assignments find confirmation from the assignments of the IR region, composed of at least three bands, is due to comand Raman spectra of V205.34*35 total, six modes are In binations of VO, terminal stretchings. The broad, weak band observed, as expected. near 1430 cm-' is assigned to a combination involving a At lower frequencies, a band almost coincident in the IR V-0-V asymmetric stretching and a VO, stretching. and Raman spectra is observed (430 cm-' in IR, 440 cm-' in Finally, the two strong harmonics at 1210 and 1116 cm-' Raman). This band can be assigned to the two components of can be assigned to crossed combinations of the Raman- and the in-plane deformation mode of the VO, unit. IR-active V-0-V stretching modes. Note that the IR spectrum of the Mg metavanadate differs The overtone region of the spectrum of Mg metavanadate significatly from those of the orthovanadate and of the pyroshows, besides weak components arising from Mg2V,0, vanadate (as well as those of many Mg2+ compounds) impurities, five main bands. The low-frequency pair of bands because of the absence of a strong, broad absorption in the looks similar to that already discussed for Mg,V,O, and also 450-350 cm- ' region. This can be related to the observation, observed for V 2 0 5 , although at higher frequencies in this reported by Mocala and Z i o l k ~ w s k ithat in this compound ,~~ case (1276, 1200 cm-'). These bands, absent for the orthovaMg ions occupy more space than usual, probably because of nadate, should arise from modes involving bridging oxygens. the particular lack of elasticity of the layered macroanion. So, Also, the band near 1400 cm-' certainly involves VO, the MgO, octahedra are unusually expanded, and the stretchings, while the band at 1780 cm-' is assigned to comMg-0 bond order is unusually low. We found less well binations of terminal V-0 stretchings. The highestdefined absorptions at lower frequencies than usual, as frequency component, instead, cannot be assigned to a binary expected. combination. The most reasonable assignment is to a ternary The IR spectrum we report here does not compare well with those reported previously for the same c ~ m p o u n d ~ ? combination of IR-active modes, or of two Raman modes ~~ plus one IR mode. and with those of other alkaline-earth-metal metavanaIn Fig. 7 the spectrum in the overtone region of V 2 0 5 is dates,29 while the Raman spectrum corresponds entirely with also reported. The two strong bands at 1276 and 1200 cm- ' that reported by Sten~el.'~ and the shoulder near 1350 cm-' can be assigned to combinations of the fundamental m o d e ~ arising~from stretch~ ~ , IR Spectra in the 'First Overtone' Region ings of the V-0-V and VO, entities at 820 cm- ' (IR), 703 cm-' (R), 600 cm-' (IR) and 528 cm-' (R) in the following The IR spectra of pressed discs of the pure Mg vanadate manner: 703 cm-' (R) + 520 cm-' (IR) = 1123 cm-'; 703 powders (and of V 2 0 5 for comparison) in the region of the cm-' (R)+600 cm-' (IR)= 1303 cm-'; 528 cm-' first overtones of the skeletal vibrations are reported in Fig. (R) + 820 cm-' (IR) = 1348 cm-'. At higher frequencies two 7. Since all of the structures we are dealing with are centrostrong bands are observed at 2020 and 1975 cm-'. In presymmetric, all IR-active first harmonic bands should be assigned to binary combinations of one Raman-active (or vious publications by Busca et u1.38,39a weak shoulder in the middle was envisaged, but is probably non-existent. This inactive) mode and one IR-active (or inactive) mode. The doublet, considered to be a triplet, was erroneously attributed positions of the observed harmonic bands and tentative to the summation and combination modes of two V - 0 assignments are reported in Table 2.

',

',

',

'.

J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90

1169

stretchings. In reality, four short V=O bonds are present in the Bravais cell of V,O, (Prnrnn = D i i space group, 2 = 2). Consequently, four V=O fundamental stretching modes are present, two of which are Raman-active (Ag, B l g , almost coincident near 994 cm- 34) and two IR-active (Bz,, 1035 cm-, B3,, 995 cm-). The IR spectrum in the overtone region is consequently constituted by four combinations, superimposed in pairs, expected near 2027 and at 1990 cmboth B,, B3,, and just found at 2020 and 1975 cm-. In conclusion, the IR spectra in the first overtone region are characteristic of the single phases as well as of the structural units they contain, and can be used to detect the state and the phase purity of the active catalyst phases during IR adsorption experiments using pure powder pressed discs, as already proposed.38 The observed harmonic bands can be assigned according to the assignments of the fundamental modes, and allow us to propose some correlations. Note that the stretching modes of short terminal V-0 bonds give rise to sharp strong combination modes, in the region 2050-1800 cm-. Broader and multiple combination bands are found in the region 1900-1500 cm- arising from the different asymmetric and symmetric stretching modes of terminal VO, entities. Single and triple bridges, V-0-V and V30, give rise to strong and relatively sharp bands in the region 15001 O cm-. The strength of these combination modes is OO related to the covalency of the V-0 bonds. When only lowoxidation-state cations are involved in similar structures, these modes are very weak or even absent.

hedral vanadylic coordination, in contrast with Mg orthovanadate where it is definitely tetrahedral. The same concept is useful when the surface species on vanadia catalysts supported on metal oxides are considered. One can expect that the acid-base character of the metal oxide strongly influences the nature of the surface species in this sense. This concept agrees with the observation that basic dopants on V,O,-TiO, decrease the vanadylic character of the surface vanadium oxide species, with a decreasing V=O bond order4 and a significant effect on the catalytic behaviour. The IR and Raman spectra presented and discussed here represent reference data which allow a better structural characterization of real catalysts, generally polyphasic, as well as of materials where other techniques (e.g. XRD) cannot give definite information, such as highly amorphous catalysts, MgO-V,O, glasses: and monolayer-type supported catalysts. In particular, comparison with the present data was useful for the identification of surface species observed on vanadia-titania catalysts.43 Laser Raman experiments were performed at Ecole Centrale de Lyon. We thank Dr. R. Olier for his kind assistance. Part of this work was supported by MURST (Rome, Italy).

References
1 2 M. A. Chaar, D. Patel, M. C. Kung and H. H. Kung, J. Catal., 1987,105,483. K. Seshan, H. M. Swaan, R. H. H. Smits, J. G. VanOmmen and J. R. H. Ross, in New Developments in Selective Oxidation, ed. G. Centi and F. Trifiro, Elsevier, Amsterdam, 1990, p. 505. D. Siew Hew Sam, V. Soenen and J. C. Volta, J. Catal., 1990, 123,417. D. Bhattacharyya, S. K. Bej and M. S. Rao, Appl. Catal. A , General, 1992,87,29. R. Burch and E. M. Crabb, Appl. Catal. A, General, 1993, 100, 111. J. Hanuza, B. Jezowska-Trzebiatowska and W. Oganowski, J . Mol. Catal., 1985,29, 109. G. Busca, F. Cavani, G. Centi and F. Trifiro, J. Catal., 1986, 99, 400. J. C. Volta, K. Bere, Y. J. Zhang and R. Olier, in Catalytic Selectiue Oxidation, ed. T. Oyama and J. Hightower, American Chemical Society, Washington, DC, 1993, pp. 217-230. G. Busca, in ref. 8, pp. 168-182. V,0,-Ti02 Eurocat standard catalyst, ed. G. C. Bond and J. C. Vedrine, Catal. Today, in the press. P. M. Michalakos, M. C. Kung, I. Jahan and H. H. Kung, J. Catal., 1993, 140, 226. G. Busca, G. Ramis and V. Lorenzelli, in New Deuelopments in Selective Oxidation, ed. V. Cortes Corberan and J. L. G. Fierro, Elsevier, Amsterdam, in the press. R. Kohlmuller and J. Perraud, Bull. SOC.Chim. Fr., 1964,3, 645. R. Wollast and A. Tazairt, Silicates Ind., 1969,34,42. E. I. Speranskaya, Inorg. Muter., Engl. Trans., 1971,7, 1611. R. C. Kerby and J. R. Wilson, Can. J . Chem., 1973,51, 1032. G. M. Clark and R. Morley, J. Solid State Chem., 1976, 16,429. N. Krishnamakhari and C. Calvo, Can. J . Chem., 1971,49,1630. R. Gopal and C. Calvo, Acta Crystallogr., Sect. B, 1974, 30, 249 1. E. E. Sauerbrei, R. Faggiani and C. Calvo, Acta Crystallogr., Sect. B,1974,30, 2907. H. N . Ng and C. Calvo, Can. J. Chem., 1972,50,3619. H. G. Bechman, F. R. Ahmed and W. H. Z. Barnes, 2. Kristallogr., 1961, 115, 110. W. G. Fateley, F. R. Dollish, N. T. McDevitt and F. F. Bentley, Infrared and Raman Selection Rules for Molecular and Lattice Vibration: The Correlation Method, Wiley, New York, 1972. J. C. Decius and R. M. Hexter, Molecular Vibrations in Crystals, McGraw-Hill, New York, 1977. J. M. Stencel, Raman Spectroscopy for Catalysis, Van Nostrand, New York, 1990. P. Tarte, Spectrochim. Acta, 1962, 18,467. E. J. Baran and P. J. Aymonino, 2. Anorg. Allg. Chem., 1969, 365, 211.

Discussion
The analyses of the structures of the stable compounds in the MgO-V,O, system show a progressive modification of the coordination sphere of vanadium. While the coordination at vanadium is an asymmetrically distorted octahedron with one very short V-0 bond and one very long bond in VO,, in the case of magnesium metavanadate the structure is similar but with the shortest bond being longer (two nearly equivalent V - 0 bonds) and the longest bond shorter (Table 1). In the triclinic magnesium pyrovanadate, vanadium is nearly pentacoordinated, with a fairly symmetric tetrahedron entertaining a fifth weak coordination. The situation is similar in the monoclinic magnesium pyrovanadate (assumed to be isostructural with monoclinic C0,V207) where the existence of a fifth coordination at vanadium is also suspected.22 In the case of the magnesium orthovanadate the structure is definitely tetrahedral, which implies a further expansion of the shorter V - 0 bonds. This confirms the existence of vanadylic nature in V,O,, of a VO, unit in MgV,O, (although one of the terminal oxygens actually bridges to another V ion), and the presence of four almost equivalent bonds in Mg3(V04),. In Mg,V,07 the tetrahedra are more asymmetric. This situation looks similar to that observed in aqueous solution, where at low pH the VO; ion and polyoxovanadates with nearly octahedrally coordinated vanadium are observed, which convert to isolated tetrahedral pyrovanadates and later to orthovanadate ions with increasing P H . ~ Therefore, this progressive evolution observed in the solid state for the VMgO (MgO-V,O,) system can be attributed to the increasing basic character of the compound caused by increasing the nominal MgO content. The extension to the solid state of this conclusion valid for oxovanadium species in solution, provides a potentially useful concept when real catalysts and materials are taken into consideration. Accordingly, we note that vanadia compounds mixed with acidic components (as in the cases of V,O,-MOO, and V,O,-P,O, catalysts) have vanadium in a nearly octa-

3
4 5 6 7

8
9 10
11

12

13 14 15 16 17 18 19
20 21 22 23 24 25 26 27

1170 28 29 30 31 32 33 34
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J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90

37 G. Ramis, G. Busca and V. Lorenzelli, J. Chem. SOC., F a r d a y Trans., 1994,!40, in the press. 38 G. Busca and J. C. Lavalley, Spectrochim. Acta, Part A, 1986,42, 443. 39 G. Busca, G. Ramis and V. Lorenzelli, J. Mol. Catal., 1989, 50, 231. 40 W. P. Griffth and P. J. B. Lesniak, J. Chem. SOC.A, 1969, 1066. 41 G. Ramis, G. Busca and F. Bregani, Catal. Lett., 1993, 18,299. 42 A. Tsuzuki, K. Kani, K. Watari and Y. Torii, J. Muter. Sci., 1993,28,4063. 43 L. Lietti, P. Forzatti, G. Ramis and G. Busca, Appl. Catal. B, Environmental, 1993,3, 13.

35
36

Paper 3/06456E; Received 28th October, 1993