3973
IRSTUDYOF OXYGENSPECIESIN VANADIUM PENTOXIDE
Infrared Spectroscopic Study of Oxygen Sp.ecies in Vanadium Pentoxide with Reference to Its Activity in Catalytic Oxidation by Yoshiya Kera and Kom Hirota Department of Chemistry, Faculty of Science, Osaka University, Toyonaka, Osaka, J a p a n (Received February $7, 1969)
To clarify the nature of the exchangeable oxygen in vanadium pentoxide catalyst during the oxidation reaction, an infrared technique combined with the lSOtracer technique was applied to the samples isotopically substituted by treatment with carbon dioxide-180. The bonds appearing at 1019 and 818 cm-l can be identified to be the V=O and V-0-V groups, respectively, because the corresponding shift of both bonds appeared by isotopic substitution. Exchange experiments between gaseous carbon dioxide and vanadium pentoxide were carried out at 290, 370, 410, and 450°,and the 1 8 0 balance was investigated,taking the intensity of the above infrared bands into account. Thus, the behavior of the oxygen species at the surface and in the bulk could be determined; (a) Direct exchange of the oxygen on the surfaceV=O groups with gaseous oxygen is very rapid at the initial stage of reaction. (b) Oxygen exchange between V=O and V-0-V groups may occur rapidly near the lattice dislocations on the (010) surface as well as on other surfaces. (c) The exchange within the V-0-V net plane is the easiest of all the processes, so that it becomes predominant in the reaction even at the intermediate stage. (d) The exchange between the V=O and v-0-V groups on the surfaces is important from the standpoint of catalytic oxidation.
Experimental Section
m2/g from the BET method, using carbon dioxide as adsorbate at -78". . Procedure of Experiment E . To determine the ir band due to the exchangeable oxygen, the 180-substituted powders were prepared by the isotopic exchange reaction of carbon dioxide-I80 (including oxygen-lsO (10: 13)) with the powders. The scheme of this exchange process has been previously studied' and is examined in more detail in this paper. The apparatus is shown in Figure 1. The procedure was similar to that of experiment Bin the previous paper. After the substitution, the oxide powders were taken out of the reaction tube, and their ir spectra were measured, using a Japan Spectroscopic Co., Type DS-402G1 apparatus. Procedure of Experiment F . For the sake of determining the relation between the ir bands and the isotopic exchange reaction on the catalyst, the ir spectra of the oxide were investigated as a function of the progress of the exchange reaction between carbon dioxide-'*O and the oxide. The apparatus shown in Figure 2 was used with the following procedure. Four side tubes, each accompanying a tap, were attached to a main reaction tube R. (Only two side tubes are shown in Figure 2 . ) Each side tube was charged with oxide powders for measurement of the infrared spectra. The total amount of the oxide was 34 mg for each experiment, 1.5 mg in each side tube, and 28 mg in the main tube, which was attached in order to
Catalyst. The same lot of vanadium pentoxide powders as in the previous paper' (Mitsuwa Chemical Co., special grade) was used without any treatment. Surface area of the powders was determined to be 2.5
(1) K. Hirota, Y.Kera, and 8. Teratani, J. Phya. Chem., 72, 3133 (1968). (2) Y . Kera, S. Teratani, and K. Hirota, Bull. Chem. Soc. Jap., 40, 2458 (1967).
According to our "triangular" reaction scheme' for carbon monoxide oxidation over vanadium pentoxide powders, oxygen atoms in the V=O groups projecting from the V-0-V net planes of the oxide are repeatedly regenerated by new ones. However, it mas shown also that such exchangeable oxygen species are not restricted to the V=O groups on the surface, but the oxygen species in the oxide bulk relate to the reaction. Therefore, the behavior of oxygen has to be clarified in the oxidation scheme, even though such a scheme has been implicitly accepted without any direct evidence by most of the researchers. As reported preliminarily,2 a new band appeared at 962 cm-1 in the infrared spectra of the oxide substituted by isotopic oxygen l80,so that the 1019-cm-1 band was confirmed to be the stretching vibration of the V=O group, projecting perpendicularly to the V-0-V net plane, i e . , the (010) plane. There is also the possibility of finding additional isotopic bands produced by oxygen species in the oxide. It is the object of the present report to investigate the behavior of various oxygen species in vanadium pentoxide and to establish their role in the catalytic oxidation in more detail by using an ir technique in combination with the lSO tracer technique and also to discuss the relation between the exchangeability of oxygen and the catalytic activity of the oxide.
Volume 79, Number 11 November 1969
3974
YOSHIYA KERAAND Kozo HIROTA
vacuum and ss spectrometer
C
--3
Figure 1. Reaction apparatus: R, reaction tube; G, gas reservoir; S, sampling part; B, Dry Ice-acetone bath; F, electric furnace; C, chromel-alumel thermocouple; J, joint; T, trap.
t O
l
I
1200
'
I
1100
.
'
"
" .
1000 900 800 Wavelength, Cm-'.
I
700
'
1 1
1
600
Figure 3. The change in the ir spectrum of the oxide with degree of pulverization. Curve A shows the ir spectrum observed after the first pulverization, B after repeating the pulverization, and C after again repeating the pulverization.
Figure 2. Reaction apparatus: R, reaction tube; G, gas reservoir; SI,sampling part; S2, sampling tube; MI, M2, mercury manometer; T, Toepler pump; C, calcium chloride tube; J, joint; N, the collecting part of the reacting gas.
reduce any change in composition incurred upon the removal of a part of the catalyst for analysis. Prior to each experiment, a calcium chloride tube, which had an open end to the air, was attached to the joint J. Then, R was heated with an electric furnace at 490" for 1 hr and then was degassed with a mercury diffusion pump at 490" for 2 hr, until the degree of vacuum reached about 10-5 mm, according to an ionization gauge. The reaction temperature was regulated to be constant within =t1". After the above-mentioned treatment, a constant amount of carbon dioxide labeled with l80was introduced with a Toepler pump, and the reaction was begun. At a given time, about 1y0of the gas reacting in R was removed in the part SI (ca. 1cm8)for the analysis, and a side tube was simultaneously taken away from the system successively for the infrared measurement. Before the side tube was removed, the reaction gas was collected in the part S by immersing the part in liquid nitrogen to prevent a part of the reaction gas from being lost to the system. Gaseous Reactant. A mixture of oxygen and carbon dioxide, both containing ca. GO atom yo leO, was used in experiment E. Carbon dioxide-'*O used in experiment F was prepared from the carbon monoxide-180,which was obtained by contacting the gaseous oxygen-'*O with active charcoal at about 900". By allowing gaseous oxygen-180 to react with carbon monoxide-180 at The Journal of Physical Chemistru
350" on a platinum black catalyst, carbon dioxide-l80 was prepared. The concentration of l80 in carbon dioxide thus obtained was about 38 atom %, and the gas was mass spectroscopically free from other substances. The oxygen-180 used in both experiments was prepared by our laboratory as in the previous papera3 For the isotopic analysis, a Hitachi Co. Type RMU-5B apparatus was used. I r Measurement. Ir absorption spectra of vanadium pentoxide powders were measured by the KBr disk method over the range from 400 or 650 to 1200 cm-l. To determine quantitatively the l80concentration in the V=O group, a '(compensation method" was adopted by inserting the untreated oxide powders in the optical path of the reference light. The samples for the KBr disk method were prepared by pulverizing a mixture of the oxide and KBr powders in an agate mortar and pressing them in the usual way. The shape of the I r spectrum changed gradually as shown by curves A, B, and C in Figure 3, depending on the degree of the pulverization. The integrated absorption intensities of the band at 1019 cm-l of these three spectra are approximately equal, in spite of the absorbances at the band maxima being different for the different cases. Most measurements were done on the samples, corresponding to the A curve, and the baseline a was assumed to be approximately linear. The absorbance of the band at 1019 cm-l was determined for various concentrations of the oxide powders, in order to (3) K. Hirota, Y. Kobayashi, M. Takahashi, and Y . Yoshikawa, Iso-
topes Radiation (Tokyo), 2, 235 (1959).
3975
IRSTUDY OF OXYGEN SPECIESIN VANADIUM PENTOXIDE
I
I
Substltutlon I j
Substltutlon
,
I
I
I
I
I
100
/J L D J
t
Substitution m
1019
$18
490'C
I
0
C
200
b
I
300
Time, hr.
Figure 4. Changes of 1 8 0 concentration in oxygen and carbon dioxide during the '80-substituted reaction of vanadium pentoxide. Circles indicate carbon dioxide and squares oxygen.
draw a calibration curve for the concentration of oxide in the disk. A linear relationship was confirmed well over the concentration range from 0.007 to 0.7 (mg of V20;/200 mg of KBr). However, the compensation was carried out in the present experiment by adjusting the concentration of the oxide in the range between 0.4 and 0.6 (mg of V2O5/2O0mg of KBr). The ' 8 0 concentration in the V-0-V groups was investigated as in the V=O group, as will be explained in experiment E-2, but the attempt was unsuccessful.
Results Experiment E-1 . Identification of the Stretching B a n d Ascribable to the V=O Group. Vanadium pentoxide powders were treated with a mixture of oxygen and carbon dioxide, both gases containing ca. 60 atom % of l80,for 88 hr a t 370" (substitution I). Such treatment was repeated for 160 hr at the same temperature (substitution 11) with a fresh mixture and again for 24 hr a t 490" (substitution 111). Changes of l80concentration in both gases during the treatment are shown in Figure 4, with time as the abscissa. '*O concentration in carbon dioxide (circles) decreases rapidly, while that in oxygen (squares) did not change at 370", as can be expected by the result of Figure 4 in the previous research.' However, a decrease of l8O concentration was observed a t 490" on oxygen also, while the isotopic composition of the gaseous oxygen (1 6 0 2 : 1601g0 : did not change as below 490". The infrared spectra of the samples after the three substitution treatments are shown by curves B, C, and D, respectively, in Figure 5, where curve A is the spectrum without such treatment. The spectra B, C, and D did not change even after keeping the sample in air for several months. Comparing these spectra, a new band appeared in the
1
1
1200
1
1000
1
1
I
800
I
600
I
I
500
400
C h4-I
Figure 5. Change in the ir spectra by repetition of the 1 8 0 substitution. A shows the spectrum without substitution, B the spectrum obtained after substitution I, C after substitution 11, and D after substitution 111.
treated samples at 962 cm-' near the strong band a t 1019 cm-I. Its intensity becomes stronger with repetition of the treatment. Also, a weak shoulder band often appeared at ca. 985 cm-l, as already reported .4 Eichhoff and Weigels and -19iller and Cousins6investigated both ir and Raman spectrum of VOC1, and assigned the strong sharp band observable at 1035 em-1 to the V=O stretching vibration. Several authors7J report that a strong sharp band of this kind also appears near 1000 cm-' on some vanadyl compounds. Since vanadium pentoxide crystal contains the vanadyl group in its structure, they ascribed the 1 0 2 0 - ~ m -band ~ in vanadium pentoxide to the V=O stretching vibration. The same assignment is adopted for the 1019cm-1 band in the present paper. Then, under the assumption that the oxygen atom forms a bond with an atom of infinite mass, the isotopic band produced by l80 substitution was calculated. The value thus calculated, 961 cm-I, coincides well with the observed, 962 cm-'. The above assumption is plausible due to the reason that the V=O groups project perpendicularly to the V-0-T7 net plane, considering the crystal structure of this oxide (Figure 6).9 Hence the stretching vibrational mode of the V=O (4) M. Adachi, T. Imanaka, and S. Teranishi, Nippon Kagaku Zasshi, 89, 446 (1968). (5) H. I. EichhofT and F. Weigel, 2. Anorg. A l b . Chem., 275, 267 (1954). (6) R. A. Miller and L. R. Cousins, J. Chem. Phys., 26, 329 (1957). (7) C. G. Barraclough, J. Lewis, and R.S. Nyholm, J. Chem. SOC., 3552 (1959). (8) L. D. Frederickson, Jr., and D. M.€Iansen, Anal. Chem., 35, 818 (1963). (9) A. Bystrom, K. A. Wilhelmi, and 0. Brotnen, Acta Chem. &and., 4, 1119 (1950).
Volume 73, Number 11 November 1969
TOSHIYA KERAAND Kozo HIROTA
3976
9 1
Ib
a
9 Q
Q
L
Figure 6 (a) Projection of the structure on the (001) plane of VzOE: small circles denote V atoms; large circles 0 atoms. The figure denotes the height of the atoms in fractions of c. Superimposed oxygen atoms are symmetrically displaced; The cell dimensions: a = 11.519, b = 4.373, c = 3.564 A. (b) Projection of the structure for the (010) plane of V206.
groups can approximately be regarded as independent of the other vibrational modes, and the 1019- and 962cm-' bands can be conclusively assigned to the V="O and V='80 stretching vibrations, respectively. However, the assignment of the weak band at 985 cm-I is difficult at the present stage of investigation. Figure 4 shows that the 180-exchangereaction probably reaches equilibrium by both substitution treatments I and I1 at 370" but that further exchange occurred by elevating the reaction temperature to 490" in substitution 111. The above findings seem to indicate that '80 concentration is not homogenized so easily in vanadium pentoxide powders at the lower temperature; i e . , the isotopic exchange of oxygen species in the inner bulk is a slow process. As shown in Fighes 4 and 5, in spite of the fact that the l80concentration in the gaseous reactant after the substitution I11 becomes lower than that after the substitutions I and 11, the 962-cm-' band of the former samples is much more intense than that of the latter sample. This result suggests that the oxygen in the V=O groups becomes much more mobile with rising The Journal of Physical Chemistry
& 1.88 A j
Figure 7. The coordination around one vanadium atom. Solid lines correspond to the five strong V-0 bonds, and the dotted line shows the sixth, much weaker bond; bond lengths are in angstroms.
temperature. Such peculiar behavior of oxygen in the catalyst will be reported in more detail (experiment F). Experiment E-2. Identification of the Stretching Band Assignable to the V-0-V Groups. In Figure 5, there appear two broad bands at shorter wavelengths (ca. 800 and 500-600 cm-l). However, an isotopic shift of the band could not be confirmed in all the curves, presumably because the band is a composite one and becomes too broad. This may be plausible, considering that there are three kinds of V,-0 distances in the net plane--1.77, 1.88, and 2.02 A-as Figure 7 showsle where the 01 atom belongs to the V=O group and 02 and 0 3 belong to the V-0-V groups. The small circle denotes the vanadium atom. Siebert'O measured Raman spectrum of the tetrahedral V04-3 ion in aqueous solution and assigned the bands at 870 and 825 cm-1 to be of the symmetric and asymmetric stretching modes, respectively. Barraclough, Lewis, and Nyholm7 compared ir spectra of various tetrahedral anions (Cr02 -, M004~-,MnOh-, and VOq3-) with one another and indicated that the mode of their metal-oxygen stretching vibration is not simple, but is triply degenerate, so that a slight distortion from tetrahedral symmetry can lead to a broad band actually observable in the 800-900-cm-' region. Now, vanadium pentoxide can be regarded as polymeric, and its structure may be viewed as a distorted V06 trigonal-bipyramide sharing four corners, according to the X-ray datas,l1 (cf. Figure 6). They considered, therefore, that the broad band at 825 cm-' represents the stretching vibration of the V-0-V group in the lattice layer, corresponding to the (010) plane. To estimate the nature of the 818-cm-l band in Figure 5, the band produced by its isotopic shift was investigated by the compensation method. Compensated spectra (111) of l80-enriched samples by substitution are shown with dotted curves in Figure 8. (10) H.Siebert, Z.Anorg. Allg. Chem., 275,225 (1954). (11) H.G.Baohmann, F. R. Ahmed, and W. H. Barnes, 2.Kristallogr., 115, 110 (1961).
3977
IRSTUDYOF OXYGENSPECIES IN VANADIUM PENTOXIDE 100
$i
z.
e
m 0
II
'5.0 .-
.i c
.-
50
w
6
e k-
0
m
I a,.4
450"
I
9-
a,
E
01
D
1
01
I
1200
I
1100
I
1000
I
I
I
900
800
700
Wavelength, Cm-'
I I 600
.
Figure 8. I r spectrum of the 180-substituted vanadium pentoxide powders and their compensated spectra. The solid curve shows the ir spectrum of the 180-substituted powders, and the dotted curves then compensated spectra.
The attempt was successful to some extent, because a new band always appeared at ca. 780 cm-I. However, since the position of the appearing band was different and the base line and the form of the compensated spectra changed from experiment to experiment, it became difficult to carry out the quantitative analysis on the band. Under the assumption that the reduced mass of this unknown group giving the band is approximately equal to that of a V-0-V bond, the isotopic shift due to l80substitution for ' 6 0 was again calculated, and 47 cm-I was obtained. If this is correct, the corresponding band should be observed at 771 cm-' in the l80substituted substance. Experimentally, the mean maximal position of the compensated band in both spectra shown by dotted curves in Figure 8 is ca. 780 cm-'. Thus, the calculated value is larger by 12% (9 cm-l) than the observed value. This somewhat large discrepancy indicates that the oxygen giving the SlS-cm-' band cannot be regarded as a simple V-0-V bonding state, and this bonding state is different in nature from that of the band at 1019 cm-l. Therefore, the band near the 818-cm-' band may be ascribed to the V-0-V stretching vibrational mode. Such failure in quantibative explanation of this band seems to be due to the situation that contrary to the stretching vibration of the V=O group, the stretching vibration of each V-0 group depends in a complicated way on many other vibrations in the V-0-V plane. Experiment F. Distribution of l80among the Various Lattice Oxygens in V a n a d i u m Pentoxide during the E x change Reaction. 1. Degree of l80 Distribution in the V=O Group. The isotopic exchange reaction between
50
100
150
200 250 Time, hr.
Figure 9. Temperature effect of the degree of in the V=O group.
300
distribution
carbon dioxide and vanadium pentoxide was carried out at 290, 370, 410, and 450" the pressures of carbon dioxidebeing 18.8, 18.4, 17.1,and 21.0 mm, respectively. The course of the reaction at the four temperatures can be shown by the l80concentration in carbon dioxide vs. reaction time, necessary data being given in Table I. Due to experiment E-1, the linearity of the calibration curve of the 1019-cm-' band was confirmed, so that the absorbance of the 1019-cm-' band in the uncompensated sample (log (10/1)1019) and that of the 962-cm-' band in the compensated (log (10/1)962) can be regarded as proportional, respectively, to the amount of the V=l60 and V=l80 groups existing in the sample. Therefore, under the plausible assumption that an isotope effect does not exist in the extinction coefficient of both bands, the percentage of V=l80 groups V=l80 %, in Table I can be calculated by eq 1
Hereafter, the degree of l8O distribution in the V=O group will be estimated by V='80%. In Figure 9, these values are plotted vs. reaction time at the four temperatures. The data indicated by arrows, lying on the dotted lines, were obtained by heat treatment of the samples in a vacuum at the same temperature. The result shows that the higher the temperature, the larger the V=l80 %, and that the value increases by heating the samples in a vacuum after the exchange reaction, due to migration of l80from other combined states. 2. Degree of l80Distribution in the V-0-V Groups. As mentioned in experiment E-11, direct estimation of Volume 78, Number 11 November 1060
3978
YOSHIYA KERAAND Kozo HIROTA
Table I : Distribution of '80in Vanadium Pentoxide during the Exchange Reaction Expt
F-a (450")
F-b (410')
F-c (370")
180L,
Time, hr
so,, %
101s atoms
0 2 6 12 46
39.9 32.5 27.1 21.2 13.5
24 68
----
V=180--
%
lox* atoms
11.7 19.6 28.0 35.5
2.6 3.7 3.9 5.4
... ...
35.5 35.5
0 4 8 14 71
34.2 30.4 27.1 23.5 12.8
75 0 10.5 21 47 89 183
65 175
----
V-IQ-V----
%
1018 atoms
5.8 7.7 7.9 9.6
1.8 3.7 6.6 9.5
5.9 11.9 20.1 25.9
6.3 6.5
11.4 11.8
8.8 8.7
24.2 23.8
4.9 8.9 13.1 23.5
1.0 1.5 1.7 2.2
2.2 3 (0 3.4 3.9
0.8 1.9 3.2 7.3
2.7 5.9 9.7 19.6
...
23.5
2.4
4.2
7.2
19.3
40.9 35.0 30.6 27.0 24.0 17.7
8.1 13.8 18.2 21.3 27.3
0.9 1.1 1.3 2.0 2.2
2.0 2.2 2.7 3.7 3.9
1.9 3.7 5.2 6.2 8.7
6.1 11.6 15.5 17.6 23.4
27.3 27.3
2.1 2.8
3.8 5.1
8.7 8.3
23.5 22.3
...
...
F-d (290')
0 36.6 42 30.0 9.3 0.3 0.7 2.6 8.6 90 24.0 17.4 0.3 0.7 5.3 16.7 213 22.9 18.1 0.5 1.0 5.7 17.1 a Data below the dotted lines a t each temperature were obtained by keeping the catalyst in a vacuum after the measurement just above the dotted lines.
l80 concentration in the V-0-V groups was difficult. However, the l80concentration in the groups can be determined indirectly from the material balance of lSO atoms disappearing from the gaseous phase and of l80atoms going into the V=O groups in the oxide lattice. They are given in the fourth and sixth columns in Table I, where OL denotes the total oxygen species in the oxide. Oxygen in crystalline vanadium pentoxide may be classified roughly into two kinds : oxygen in the V=O group and that in the net plane of the V-0-V groups, even though a t least two types of V-0 bond exist in the V-0-V net planeg,l1(cf. Figures 6 and 7). Therefore, it can be considered that l80atoms which disappear from the gaseous phase during the exchange reaction migrate into the oxide lattice and distribute themselves between oxygen species in the V=O groups and those in the V-0-V net planes (V-0-V groups). From this, the amounts of V-lS0-V are calculated by eq 2, using the data in Table I (V-180-V)
=
('SOL)
- (V=180)
The percentage of V-l*O-V groups, V-180-V The Journal of Physical Chemistry
(2)
%, which
will be called the degree of lSOdistribution in this group hereafter, is given by eq 3
v-'SO-v %
= (V-'*O-V)/(V-O-V)tot,l
x
100 (3)
Thus calculated values are given in the last two columns in Table I. To show clearly the change of the V-'*O-V % during the course of the exchange at each temperature, Figure 10 was prepared, where V-'80-V % is plotted against the total '*OL atoms. Equilibrium l*O concentration of the isotopic exchange reaction and mean '*O concentration in the oxide are described by horizontal lines at the top of the figure and a straight line drawn from the origin, respectively. Conversions in the exchange reactions can be calculated by the ratios of the two concentrations in Figure 10, and the conversions thus obtained in the first and the last measurements at each temperature are as follows: 24 and 81% at 450"; 14 and 72% at 410"; 19 and 66% at 370" ; 24 and 48% at 290". The values indicate that the data obtained in the present experiment give information about the inner bulk, rather than the surface layer of the oxide. Now, by comparing each curve in Figure 10 with the
3979
IRSTUDYOF OXYGENSPECIESIN VANADIUM PENTOXIDE
>
m, 1.0
equil. value
-----
----.-.
I
0
I
> m
0)
f
/I
.-C
> 0
290'
0
m
c
ean IeO - concentration in the oxide
G)
L
G) m
0
0
1.o
2.0 3.0 x 1019 atoms.
4.0
100
Discussion Considering the nature of exchange reactions, it will be assumed in the present discussion that the crystal structure of vanadium pentoxide is invariant during the reaction. Of course, various latrtice imperfections always exist, and they can change to some extent by chemical or thermal treatment, as esr signals of the oxide indicate.12 To demonstrate how the lSOdistribution between the V=O and V-0-V groups changes during the exchange reaction, Figures 11 and 12 were drawn up, in which ratios of the V=lSO 70to the V-lsO-V % are plotted against time and the total amount of l 8 0 ~ respectively. , The ratios were calculated by using the values in Table I. Based on both figures, the behavior of the oxygen species in the oxide during the exchange reaction can be discussed.
300
Figure 11. Changes in the 1 8 0 distribution between the V=O and V-0-V groups with reaction time.
1. Behavior of Oxygen Species on the Surface. In the previous paper,' the isotopic exchange of carbon dioxide with gaseous oxygen proceeds rapidly by eq 4
0
Figure 10. Temperature effect of the degree of '*O distribution in the V-0-V groups.
curve of the mean '*O concentration in the oxide, it is understood that the V-0-V % is larger than the V='SO %, except for the initial stage a t higher temperature, because nearly all the curves fall above the straight line of mean I8O concentration. Moreover, the lower the temperature, the larger the degree of '*O distribution in the V-0-V groups, if the total amount of the l80 atoms going into the catalyst is made equal. The result indicates a difference in behavior of oxygen between the V=O and V-0-V groups.
200 Time, hr.
II I,I 0 'SO -v I -----V-I1 C
0
CO'*O
+ -V-_--11 v-.
--v----JTI1 + 180
c
COa (4)
At the same time, migration of ISO into the oxide bulk was pointed out as a slower process. The former rapid process can be estimated by Figure 11 in which the ratios decrease markedly with time in the initial stage a t each temperature, except the run a t 290°, because if the initial ratio is estimated by extrapolating it to t = 0, very large values are obtained, especially a t 410 and 450". However, it is noteworthy that the curves show a tendency to decrease from initial values above unity immediately to the values below 0.5, especially in the runs at 410 and 450". In the first experimental points of each temperature, conversions of the exchange were about 15-25%, as indicated by the result of expt F-2. They are too large by about a factor of lo2if only the V=O group in the surface (010) plane relates to the reaction under the assumption that the oxide is com(12) K. Tarama, 8. Teranishi, S. Yoshida, and H. Yoahida, Bull. Chem. SOC.Jap., 34, 1196 (1961); K. Hirota and K. Kuwata, ibid., 36,229 (1963); E. Gillis and E. Boesman, Phvs. Status Solids,14,337 (1966). Volume 73,Number 11 November 1969
YOSHIYA KERAAND Kozo HIROTA
3980
1.5
L
s
> I
0
m I >
1 1.0
8 0 m
II
> 0.5
1.o
2 .o
3.0
4.0
x ior9atoms.
Figure 12. Changes in the l80distribution between the V=O and V-0-V groups plotted against the total amount of I8O, going into the oxide.
posed of cubic particles (see Appendix). This indicates that they contain already information from the inner bulk to some extent. 2. Behavior of Oxygen Species in the Oxide. According to Figure 12, the ratios of V=l80 to V-'*O-V % change with the total amount of ~*OL,and the curves have a minimum, whose value remarkably depends on the reaction temperature. hforeover, the higher the temperature, the more the minimal region of the curves shifts toward the larger value of l80~. Since the isotope effect might be so small that the equilibrium ratio is approximately unity, the findings obtained from Figure 12 can be explained by the difference in the temperature effects on the exchangeability of oxygen in the V=O and V-0-V groups. Specifically the activation energy for the exchange of the V-0-V groups is somewhat smaller than for the V=O groups in the bulk. Additional support to the above conclusion seems to be given by the increase of the dotted lines after the heat treatment in Figure 9, because this tendency indicates that the equilibration of l80 occurred from the V-0-V groups to the V=O group. In the exchange of oxygen species in the oxide bulk with those on the surface layer, three kinds of processes need to be considered: (I) exchange in the V-0-V net plane itself; (11) exchange parallel to the V-0-V net planes via V=O groups; (111)exchange perpendicular to the net plane. Process I involves only the V-OV groups, while process I1 involves only V=O groups. The Journal of Physical Chemistry
On the other hand, in process I11 oxygens of both the V=O and V-0-V groups, participate so that process 111 has to include two steps: the exchange of oxygens in the V=O groups with each other and the repeated exchange of the oxygens in the V=O groups with those in the V-0-V groups. Therefore, the conclusion reached in the last paragraph on the inner exchange points to a smaller activation energy for process I. From the structural standpoint, Gillis indicated that the diffusion of oxygen in the directions [OOl] and [OlO] may be more favorable, because there are channels which are large enough for an oxygen atom to go through in the V Z Ocrystal, ~ in both dire~ti0ns.l~Based on this fact, he proposed a mechanism of phase transition between V Z Oand ~ VeOlsin which only oxygens in the V=O groups take part. However, Gillis' proposition on the behavior of oxygen in the oxide is not supported by the present conclusion, because it can be regarded as the faster diffusion of oxygens in the V=O groups in the directions [OOl] and [OlO], corresponding to processes I1 and 111,respectively. 3. Oxygen Exchange between the V=O and the V-0-V Groups. Process I11 can be realized by repeated oxygen exchange between the V=O and the V-0-V groups, though not so quickly as process I. This possibility was already pointed out by the increase of the dotted line curves in Figure 9. The possibility of some sort of process I11 in the reaction scheme must therefore be admitted. Of course, if this process is considered to be faster than process I, the experimental line shown in Figure 11 cannot be explained, because otherwise the ratios (V=l80 %/V-'*O-V %) must decrease asymptotically to unity from the initial value. Nevertheless, this exchange reaction has to be regarded as important in catalysis, as will be explained. From the structural standpoint (6. Figure 6), it seems plausible that not only are the oxygen species in the V=O group on the (010) surface easily exchangeable, but also all the oxygen species in the V-0-V groups on the (100) and (001) surface. Ketelaar found that the cleavage along the (010) plane was perfect, and that cleavage along (100) could also occur, but only with difficulty along the (001) plane.14 On the basis of the Ketelaar's finding, the oxygen in the V=O group may be different in nature from that in the V-0-V groups on the (010) surface, but both groups may be the same in nature on the (001) and (100) surfaces, because the cleavage plane of the crystal may not be smooth in both (100) and (001) planes. However, with an electron microscope, Gillis and Renault clearly observed the gradual growth of some dislocations even on the (010) surface of a single vanadium pentoxide crystal under evacuation. l5 (13) E. Gillis, Compt. Rend., 258,4765 (1964). (14) J. A. A. Ketelaar, Nature, 137, 316 (1936). (15) E. Gillis and G. Renault, Compt. Rend., 262B, 1215 (1966).
IRSTUDY OF OXYGENSPECIES IN VANADIUM PENTOXIDE On the basis of both structural investigations, it seems plausible that the oxygen in the V=O and V-0-V groups on the (010) surface are equivalent in their activity near the dislocations. That is, the oxygen near the dislocations can exchange between V=O and V-0-V groups easily on the (010) plane, as for the (100) and (001) surfaces. The (100) and (001) surfaces can be simply regarded as consisting of numerous dislocations. 4. General Scheme of the Oxygen Exchange and Catalyst Activity. From the above discussion, the isotopic exchange of gaseous oxygen with the oxide begins mainly at the V=O groups belonging to all the surface planes. The exchange in the V-0-V net plane, however, proceeds the fastest of all the exchange processes in the bulk, as the second stage of total reaction. It means that the exchange between the V=O groups and the V-0-V groups is comparatively slow, but such an exchange process may not be neglected in the catalytic oxidation. studied the adsorption of formic Teranishi, et acid on vanadium pentoxide by using the ir technique and proposed a dynamic model in which the V=O and V-0-V groups on the (010) plane were converted into each other by adsorption and desorption of the reactant. This scheme may be understood from the above explanation, based on the role of the dislocations. The above conclusion is noteworthy in connection with the catalytic activity of vanadium pentoxide, because even though the V=O group projecting from the (010) surface has often been regarded as the active site, the active group probably exists near the dislocations. Besides, the oxygen species on the (100) and (001) surfaces may also have similar catalytic activity,
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according to the discussion in the last paragraph of section 3. This proposition will be a subject of future investigation.
Acknowledgment. The authors wish to express their sincere thanks to Professor S. Teranishi and Dr. Shousuke Teratani for their valuable discussions. Appendix The Amounts of Oxygen Existing on the Surface of the Vanadium Oxide at the Initial Stage. Under the assumption that each particle of the vanadium oxide has a cubic form, the following two relations will exist among the length of an edge of the cube (z), the specific density ( p ) , the surface area per gram ( S ) , and the number of particles per gram (n)
n.xa
1
= - 6.nax2 =
PI
S
(AI)
From eq A1
x = -6
PS Adopting 3.36 g/cma as p and 2.5 X lo4cm2/goas8, x of the oxide used is calculated to be about 7100 A by eq A2. Therefore, using the value of 4.37 as the layer interval between two (010) planes (cf. Figure 6), each particle can be estimated to consist of about 1600 layers. This means that the order of magnitude of easily exchangeable oxygen species existing only in the surface layer is ca. or 0.1% of the total oxygen in the particle. This val3e is much smaller than the 15-25% conversion noted earlier in this paper.
Volume 7% Number 11 November 1969
