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J. Chem. SOC.,Faradaji Trans. I , 1989, 85(12), 4167-4177

Intercalation Mechanism of Nitrogenated Bases into V,O, Xerogel

B. Casal and E. Ruiz-Hitzky*
Downloaded by google on 25 May 2011 Published on 01 January 1989 on http://pubs.rsc.org | doi:10.1039/F19898504167

Instituto de Ciencia de Materiales, CSIC, clSerrano 115 bis, 28006 Madrid, Spain

M. Crespin and D. Tinet

Centre de Recherche sur les Solides a Organisation Cristalline Imparfaite, CNRS, l b rue de la Fe'rollerie, 45045 Orlkans, France

J. C. Galvan
Centro de Investigaciones Metalurgicas, CSIC, clGregorio del Amo 8, 28003 Madrid, Spain
It has been shown by i.r. and XPS techniques that protonation of nitrogenated bases (ammonia, pyridine and pyrazine) is the major process that occurs on adsorption of these compounds in the intracrystalline environment of V,O; 1.5 H,O xerogel. At room temperature the intercalation process takes place mainly by a proton-transfer reaction involving protons inherent to the solid and interlayer water molecules. Thermal treatment of the intercalated compounds gives rise to coordination of guest species to vanadium ions included in the host lattice, and VV/-VIv transformations are found to different extents depending on the nature of the intercalated molecules. The protons of the solid and the interlayer water appear to be the origin of the protonic conductivity on the V,O; 1.5 H,O xerogel, as shown by the impedance spectra. The V5+/V4+ couples formed in the intercalation process produce the electronic conductivity detected when the bases are intercalated in the layered solid.

Nitrogenated bases have successfully been intercalated as guest species in topotactic reactions involving layered transition-metal oxides and chalcogenides as host lattices. Several approaches to explain the intercalation mechanism and the host-guest interactions have been reported, the most recent studies showing the eventual participation of the guest species in redox processes involving transition elements of the solids.'-5 Moreover, related compounds such as the hydrated phases of layered metal oxides and chalcogenides can also act as solid Brransted acids, inducing the spontaneous protonation of the adsorbed species.' In this way we have reported, in an initial study by i.r. spectroscopy, the protonation of ammonia and pyridine in the interlayer space of lamellar V,O, - 1.5 H,O. In the present work we have tried to study in detail the intercalation of nitrogenated bases into vanadium pentoxide xerogel, in an attempt to correlate physico-chemical properties of the solid, such as the conductivity, with the intercalation mechanisms involved. Ammonia, pyridine and pyrazine have been selected as model molecules.

Materials

Experimental

V,O, xerogel was prepared as described elsewhere. The ammonia, pyridine (py) and pyrazine (pz) used were high-purity commercial reagents (Merck). Ammonia was adsorbed from the gas phase at room temperature or at 450 K on the V,O, xerogel.
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Pyridine and pyrazine were adsorbed from a dilute chloroform solution ( mol dmV3), washing with the same solvent in order to eliminate an excess of the reactants. Typical compositions obtained from the elemental analysis were : for V205/py,C = 6.1 %, N = 1.4% (C/N ratio, experimental = 4.4, calculated = 4.3); for V205/pz, C = 5.3 %, N = 3.1 % (C/N ratio, experimental = 1.7, calculated = 1.7). The intercalation process was controlled by determination of the basal spacing (interlayer distances) deduced from the X-ray diffractograms: starting V,O, - 1.5 H 2 0 , dL= 1.15 nm; V,O,/NH,, dL= 1.05 nm; V205/py, dL = 1.30 nm; V205/pz, dL = 1.30 nm.
Infrared and XPS Spectroscopies

1.r. spectra were recorded using a Perkin-Elmer 580B double-beam spectrophotometer coupled to an M-3500 PE data station. Thermal treatment was carried out in a conventional Pyrex glass cell for i.r. studies in vacuo Torrt). XPS spectra were recorded on a Vacuum Generators ESCA LAB MK I1 spectrometer, with a hemispherical analyser. Mg K,. ( E = 1253.6eV) or AL K, ( E = 1486.6eV) radiation was used. The system was coupled to the data station where the spectral data were accumulated. According to an empirical relation proposed by Seah and Denchs it is possible to estimate the mean path covered by the ejected electrons in the sample. If the angle between the plane defined by the V205film and the axis of the analyser is 90, the mean path of the ejected electrons associated with the V 2 p O 1s and N 1s levels corresponds to a depth of ca. 20 monolayers of V205.By decreasing this angle it is possible to restrain the surface analysis to only a few layers of the sample (estimated to be ca. 3 for a suitable signal/noise ratio). Thus, by convenient tilting of the sample we can infer details of the bulk and surface compositions.

A.C. Impedance Measurements

The electrical conductivity was measured at 298 K with a Solartron 1174 .frequency response analyser (FRA) connected to a Solartron 1286 electrochemical interface. The system was connected to a data station for collection and analysis of the impedance data. The applied signal amplitude was 50 mV in the frequency range 1 MHz-10 mHz. Cylindrical pellets (diameter, 6 mm; thickness, 650 pm) used for the measurements were made by pressing samples in the form of films, in this way the system is preferentially orientated, the current flux being perpendicular to the plane defined by the layered materials. The pellets were placed in a specially constructed cell, which allowed temperature control and maintenance of a dynamic vacuum during the measurements. Two identical electrodes were formed by sputtering of a silver-chromium mixture over the two opposite flat surfaces of the samples. The current was collected by means of platinum grids pressed against the two electrodes.

Results and Discussion

Infrared and XPS Spectroscopies

Full protonation of ammonia and pyridine molecules was produced spontaneously, as has been shown by i.r. spectroscopy when these molecules are adsorbed in the interlayer space of V205 1.5 H 2 0 at room temperature. Similar experiments carried out with pyrazine, a less basic molecule containing two nitrogen atoms per molecule, revealed that partial protonation occurs, as indicated by the presence of i.r. characteristic bands of pyrazine coexisting with bands attributed to protonated pyrazine (table 1). So the i.r.

1 Torr x 101325/760 Pa.

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B. Casal et al.
Table 1. Observed frequencies (cm-l) in the 1700-1 100 cm-' region for pyrazine (pz), protonated pyrazine (H+-pz) and the pz/V205 intercalation compound
PZ"
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4169

H+-pzb
-

PZ/V,O, 1620 (b)

-

assignment

1482 (m) 1412 (vs)

-

1583 (vs) 1483 (m) 1460 (vs)

-

1485 (m) 14 I8 (w) 1380 (w)

-

6(H-0-H) ring vibrations'. lo ring vibration^'^^^

ring vibrationsg* lo
-

1335 (w) 1178 (vw) 1149 (vs)

1367 (w)
-

1174 (vs)
-

1 1 74 (vs)
-

ring vibrations'~lo 6(CH)( ?> 6(CH)'- lo

= medium,

In CHCl, solution; in KBr pellets. b = broad, m w = weak, vs = very strong, vw = very weak.

0.1a.u
1620
1485

wavenumber/cm-

'

Fig. 1. 1.r. spectra (1800-1 100 cm-I region) of adsorbed pyrazine in V 2 0 5xerogel (a) and treated in vacuum (lo-, Torr) at 393 (b),473 (c) and 573 K (4.

spectrum (1800-1000 cm-' region) of adsorbed pyrazine exhibits [fig. l(a)] bands centred at 1485, 1418 and 1174 cm-l. The last of these also appears as an intense band in the i.r. spectrum of pyrazine hydrochloride, whereas it is weak (shoulder) in the corresponding i.r. spectrum of pyrazine. Two conceivable situations must be taken into account : (i) a proportion of molecules

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Nitrogenated Bases and V,O, Xerogel

1486 1531
I

1603

445

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wavenumber/cm-

'

Fig. 2. 1.r. spectra (180&1100 cm-' region) of pyridine/V,O, intercalates treated in vacuum at different temperatures: 293 (a), 393 (b), 453 (c) and 553 K (6).

are protonated, the remainder probably being adsorbed by coordination to vanadium ions in the host lattice, and (ii) only one of the two nitrogen atoms of all the adsorbed molecules is protonated. In order to evaluate the proportion of protonated species to clarify this situation we have examined the intercalation compounds by XPS: the emission spectrum of the N 1s level gives two peaks with maxima at ca. 402 and 400 eV, assigned to protonated and unprotonated nitrogen atoms in an N+-H/N proportion close to 1/3. This fact suggests that in the intracrystalline environment neutral and protonated pyrazine coexist approximately in a 1 : 1 molecular ratio. The corresponding XPS analysis of the pyridine intercalation compounds also indicates the presence of both protonated and unprotonated forms, the ratio being close to that found for pyrazine intercalates. This result disagrees with the i.r. data because only the bands corresponding to pyridinium ionsll, l2 are detected [fig. 2(a)].Therefore, we must suppose that the experimental requirements for XPS analysis (high vacuum and X-ray radiation) favour the loss of water molecules, inducing the formation of the free base which can then coordinate to vanadium ions in the host lattice (see the mechanism paragraph). To clarify this circumstance we have analysed the evolution of the infrared spectra of pyridine intercalation compounds treated at increasing temperatures under dynamic vacuum (fig. 2). The most significant observation is the development of the band at 1445 cm-l characteristic of coordinated pyridine.13 Samples treated at ca. 500 K, and afterwards at room temperature, exposed for several hours to an atmosphere do with a relative humidity ca. 90 YO, not change their i.r. spectroscopic features. Parallel experiments carried out on the pyrazine intercalation complexes produce a strong diminution in intensity of the 1174 cm-' band assigned to protonated species, with a simultaneous increase in the intensity of the 1418 cm-' band in the spectral region studied (see fig. 1). It is difficult to assign the latter band : considering that it appears at a frequency near to that observed in pure pyrazineg it should be associated with coordinated pyrazine, but due to its tendency to be decomposed (in an oxidation process) by the host lattice, as we discuss below, this band could alternatively be related ,-, to S,, vibrations of ammonium ions produced as a mainly decomposition species.

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energy/eV

Fig. 3. XP spectra (N Is, 0 1s and V 2p; levels) of: starting V,O, xerogel (a) and its intercalation compounds of ammonia (b), pyridine ( c ) and pyrazine (6)treated in vacuum at 450-500 K. The signal at 402 eV in spectrum (a) corresponds to a small quantity of NH,+formed by contamination with ammonia.

The XPS spectra of the V,O,/py and V,O,/pz intercalation compounds treated at ca. 500 K (fig. 3) show (N 1s level) that even at high temperatures a mixture of protonated and coordinated intercalated species coexist. Nevertheless, according to i.r. data (fig. 1) a tendency to decompose is observed in the intercalated pyrazine (formation of bands at 1735 and 1716 cm-', probably associated with oxidation by-products) and is supported by XPS analysis showing a partial loss of the quantity of the intercalated molecules. The XP spectral evidence at the time of the formation of VIV [fig. 3 ( 4 ] indicates that a relatively high quantity (ca. 30%) of the original Vv has been reduced. To a lesser extent, the reduction of Vv is also found in the intercalation of This result shows the greater stability pyridine [fig. 3 (c)], the proportion being ca. 10 YO. of intracrystalline pyridine/pyridinium species towards oxidation, compared to the intercalated pyrazine. Intercalation of a stronger base such as ammonia gives a high degree of protonated species at room temperature indicated by the intense i.r. absorption bands corresponding exclusively to NH,+ions7,l4and by XPS analysis (up to 90% of protonated nitrogen atoms). In this case, the reduction of the Vv is ca. 9 % . More drastic conditions (treatment at 450 K for several hours at an NH, pressure of 1.01 x lo5 Pa) do not change appreciably the percentage of VIV formed in comparison with adsorption under mild conditions, where the XP spectra indicate an important increase in the amount of ammonia adsorbed. In both cases, the adsorbed NH, molecules replace the water initially present in the V,O, xerogel. Thus, one can imagine that a solid-gas reaction between ammonia and V,O, takes place, giving clusters of ammonium vanadate species

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Table 2. XPS analysis of surface (S) and bulk (B) V,05 xerogel and its ammonia, pyridine (py) and pyrazine (pz) intercalated compounds, treated for 1 h under different experimental conditions

treatment
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V4+ V5+ O(V) OH H20 N

N+
0.07 0.18

0 0

5' 2 ' gel 2.00 4.95 0.76 0.50

0 0

s
B 450 K, vac.

2.00 4.99 1.14 0.73

V25/NH3

0.20 1.80 4.97 0.73 0.24 1.63 2.69 0.44 1.56 4.71 1.38 0.57 2.13 1.17
V,05/PY 0.22 1.78 4.75 1.10 0.54 0.19 0.39

B
500 K, vac.

0.29 1.71 4.84 1.56 0.88 0.32 0.40

V,O,/PZ 0.61 1.40 4.50 1.38 0.57 0.43 0.25

B
500 K, vac.

0.64 1.36 4.86 2.28 0.88 0.77 0.32

together with NH, molecules trapped in the system, as deduced by XPS (37% of unprotonated species) and according also with the observations of Masbah described elsewhere.l5 On the other hand, XPS analysis while tilting the samples, i.e. changing the orientation of the films towards the axis of the analyser, provides information about the compositions in the surface and in the bulk (see Experimental). In this way, the analysis of the pyridine and pyrazine intercalation compounds prepared at room temperature gives a similar content of guest species in the surface and the bulk in contrast to the corresponding ammonia intercalates. Therefore, the N/V ratio deduced from XPS is twice as large in the bulk as in the surface for intercalation of NH, at room temperature. In samples treated at 450 I, significant heterogeneities are also found. The most S remarkable observation concerning these systems is undoubtedly the heterogeneity of the distribution of the reduced vanadium. Thus the extent of the reduction in the surface is two or three times larger than in the bulk (table 2). Impedance Spectra The protonic conductivity of the V,O;nH,O systems has been recently reported by Barboux et a1.16 showing a correlation between the conductivity values and the water content of the system. Fig. 4 shows the impedance spectra of V,O, xerogel (a), and its pyridine (c) and pyrazine (e) intercalation compounds registered at 298 K from samples equilibrated at 55 % relative humidity. Subsequent vacuum treatment at that f, temperature gave the corresponding impedance spectra shown in fig. 4(b), ( d ) and c ) respectively. As we have already discussed, remarkable heterogeneities in the composition of the ammonium intercalation compounds are detected by XPS analysis ; therefore, those systems are excluded in the present study. In fig. 4(a), the Nyquist plot is composed of a capacitive arc followed by a linear impedance at low frequency which can be interpreted in terms of an electrical equivalent circuit as indicated in table 3. From the characteristic frequency & = 250 Hz) the value calculated for Cdl is , ,

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0
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10

z /lo4 R
(4

z/lo4 R

5
2110~ R

10

z 1103 R

2 z/104 R

Fig. 4. Nyquist plots and equivalent circuits proposed for V,O, - 1.5 H,O (a), (b) and its pyridine (c), ( d )and pyrazine (e), (f) intercalation compounds. (a), (c) and (e): measurements carried out at 298 K on samples exposed to the atmosphere ;(b),( d ) and (f) : measurements on the same samples, at the same temperature, but under dynamic vacuum.

Table 3. Component values of the equivalent circuits deduced from the impedance spectra measured at 298 K for V,05.-1.5H,O and its pyridine (py) and pyrazine (pz) intercalation compounds treated 1 h under different experimental conditions
treatments
-

component values
= 144 Ri= 1.01 x

R,

a, R,= 722 a, c, = 8.8 x 10-7 F

lo6 SZ, Cg= 1.58 x 10-l' F

V,O, - 1.5 H,O

vacuum

Re/'
-

Ri/ kSZ
v25/PY 66.2 82.9 7.73

Cg/PF
60.5 48.3 41 .O

vacuum 408 K, vac. 573 K, vac. 573 K, vac. exposed to air

-

5.68 6.40 1.87 1.96 1.33

vacuum 408 K, vac. 573 K, vac. 573 K, vac. exposed to air

9.80 3.44 7.04 5.83 6.40

v25/Pz 17.7 26.6 19.5

__

71.4 30.0 52.0

-

3x F crnw2, which is close to the usual values found for the electrochemical double layer? The linear impedance is ascribed to a diffusion tail (Warburg impedance, Z,), which is theoretically predicted for mass transport phenomena; in our case this is attributed to the diffusion of H+ ions due to the concentration changes occurring near the electrode caused by the alternating character of the electrical signal. In the equivalent

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circuit of our system an electrolytic resistance Re of relatively low value (144 Q) can be ascribed to the presence of mobile ionic species, essentially H+ ions associated with the acidic character of the hydrated solid. Comparable results have been found in the conductivity measurements of other hydrated phases of transition-metal oxides. l 8 Finally, this model assumes the existence of a charge transfer resistance R,disposed in parallel with the Cdl element, related to the transfer of electrical charge in the electrolyte/electrode interface. When the sample is subjected to vacuum, dramatic changes are produced in the impedance spectrum [fig. 4(b)]. Thus, in the Nyquist plot, a single arc intersecting the origin of the axis and the absence of the diffusion tail are the most salient features which distinguish this case from the above. The assigned equivalent circuit consists of one capacitance in parallel with a resistance, the values of these F ; Ri = 1.01 x lo6 Q) being notably different from those components (C, = 1.58 x obtained from the starting hydrated V,05. These observations can be explained by the great loss of intergrain water responsible for the propagation of the electrical signal across an ionic resistance, associated with the remaining interstitial water (microporous water, including the interlamellar water), and a capacitance, related to the intrinsic dielectric properties of the solid material. The relative permittivity E, can be calculated from the expression E, = C,d/SE,, where C, is the geometrical capacitance, d and S are the thickness and the surface area of the sample, respectively, and E, is the vacuum permittivity. The corresponding value is E, = 39.32. The intercalation of pyridine and pyrazine, determined from the impedance measurements in air, causes similar qualitative effects on the Nyquist plot to those observed when the starting V,O, - 1.5 H,O is subjected to vacuum conditions, but a new resistance component (RL) introduced in the proposed model [fig. 4(c)-(f); table 31. We is assume that this element involves the contribution of the electronic conductivity of the solid, which is enhanced by the formation of V4+ions caused by the intercalation of the organic bases. It is known that V5+/V4+ couples support the electronic conductivity in amorphous V,05 thin films.lgThis interpretation is consistent with results obtained after treatment at temperatures up to ca. 500 K (in vacuo) of the V205/py and V,05/pz intercalation compounds, the capacitance component being completely eliminated and only the electronic resistance remaining, which corresponds to the modified vanadium pentoxide. It is noteworthy that after thermal treatment in vucuo the exposure of the samples to the atmosphere does not change their electronic conductivity behaviour, the RL values remaining almost unaltered (table 3). This fact agrees with the spectroscopic observations that we have reported above, showing the irreversibility of the dehydration process, Mechanism We have shown that the intercalation of nitrogenated molecular bases into the lamellar hydrated V,O, gives mainly protonated species, which can regenerate by thermal/ vacuum treatment to a variable extent, their unprotonated forms following a reversible process. The protonation of the bases has two origins: (i) protons initially present in the xerogel compensating the negative charge (almost 0.2e per vanadium) of the V 2 0 5 xeroge120 (it may be remembered that this solid proceeds from a polymerization of decavanadic acid; so a certain quantity of protons remain in the xerogel which can be expressed as V205(0,4-) H,O+ 1.1 H,O), and/or (ii) protons due to dissociation of - 0.4 water molecules coordinated to Vv of the host lattice, with the subsequent formation of OH groups to assure the neutrality of the electric charge in the system, as we have proposed elsewhere.

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41 75

1
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+ x : B

+
[1.5H2O + (x-0.4) B]

+C(1.5-y) H20 + (x-0.4-y)

(11)
~ ~~~

+ y (BH + OH-)]

Scheme 1.

This situation is illustrated in scheme 1 , where the protonation due to both (i) and (ii) paths are represented as different (I and 11) components in the total reaction; x and y correspond to the molar amount of the base (B:) intercalated and the protonated molecules formed by dissociation of water molecules [path (ii)], respectively. Thus, for pyridine and without thermal or vacuum treatment the value of the expression (x-0.4-y) is close to zero (full protonation), while for pyrazine this expression has a positive value as was detected by i.r. spectroscopy. This follows from the greater basicity of pyridine (pK, = 5.25) compared with pyrazine (pK, = 0.65), and consequently the higher tendency of the former to be protonated. An important aspect, for the present not conclusively resolved, is the mechanism of reduction of Vv which is enhanced by the thermal/vacuum treatment. In fact, it has been reported21 that, in the starting xerogel, cycles of hydration-dehydration provide, although to a minor extent, a reduction to VIV.Nevertheless, a dependence on the nature of the base appears to be clear in our case. Schollhorn explained the reduction of transition-metal dichalcogenides (S2Ta) when ammonia and pyridine are intercalated, postulating the oxidation of these bases to nitrogen and bypyridine, r e ~ p e c t i v e l y .In. ~ ~ our case this situation can be disregarded, as evidenced by the spectroscopic results obtained from intercalation of the hypo thetical products of condensation of pyridine, 4,4- and 2,2-bypyridine, which show i.r. absorption spectra with significant differences to those obtained by intercalation of pyridine followed by thermal treatment. Neither i.r. nor XPS data support the possibility of reduction via oxidative dimerization of the intercalated heterocycle. An alternative explanation would be the existence of a charge transfer (like in benzidine-V,O, compounds22)between the base and the host lattice, but in our case these mechanisms cannot explain the loss of oxygen shown by XPS. Thus, in a first approach we can tentatively accept that the hydroxyls formed according to scheme 1 (part 11), can act in a redox process (simultaneously to an acid-base reaction) favoured when a thermal or vacuum treatment is applied, i.e. the water molecules tend to be eliminated from the system. In this way, at the same time that a proportion of BH+ species are deprotonated, a fraction of Vv could be reduced (scheme 2), in agreement with the i.r. and the XPS results. According to quantum-chemical calculations, VIV centres are more suitable sites than Vv for coordination with pyridine in vanadium p e n t o ~ i d e24 ~ ~ ~ we can assume that in thermally treated V,O,/py intercalation . Then, compounds, pyridine molecules must be coordinated to the original VIV centres. This situation is well supported by XPS results (table 2), which indicate that the VIV/N(coord.) ratio is close to 1, either in bulk or surface analysis. This ratio is not achieved in the V,OJpz compounds, So we must suppose that an additional process involving the oxidation of the intercalated species to N-oxides takes place together with the postulated

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B:

B H+

"2O
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Scheme 2.

reduction via OH groups. This process could be of special importance in the case of the V,O,/pz compounds (30% of Vv reduced to VIV) where the i.r. spectra of samples thermally treated show bands probably due to an oxidative decomposition of pyrazine to products of unknown nature, as indicated above. On the other hand, we can conceive also of the thermal activation producing the cleavage of V-0-V bonds generating new hydroxyls (V-0-H groups) simultaneous to the reduction of Vv to V'"), and according to the quantitative XPS results shown in table 2. Finally, in those systems where protons or protonated bases coexist the protonic conduction is probably due to a Grotthuss (transport of protons through water molecules). When water content decreases, a point is reached where there are not enough links (through water molecules) between proton or protonated bases and the ionic conduction suddenly disappears (percolation phenomenon), as shown by the a.c. results.

Concluding Remarks
It appears that the intercalation process of the selected nitrogenated bases into lamellar hydrated V205proceeds mainly through proton transfer reactions between the free base and: (i) protons compensating the negative charge of W2O5]layers, associated with intergrain water molecules, (ii) protons originated by dissociation of water molecules in the interlayer space coordinated to Vv of the host lattice. The partial deprotonation of guest species observed after thermal/vacuum treatment of the intercalation compounds allows us to suppose that the regeneration of the base is produced by the reversibility of the reaction involving component I1 represented in scheme 1. Under these conditions, the loss of water molecules from the system is accompanied by the coordination of the unprotonated base to the vanadium atoms. The reduction of a fraction of the Vv observed by XPS, in particular when thermal/vacuum treatments are applied, is a difficult point to explain. Several factors can be invoked such as: redox processes involving hydroxyl groups created by dissociation of the interlayer water molecules, or an oxidation of the intercalated guest molecules, especially in the pyrazine intercalate compounds. The role of the interlayer water and the protons inherent to the V205xerogel appears to be essential in the origin of the ionic conductivity found in the V20, xerogel. Thus the intercalation of pyridine and pyrazine produces protonated and coordinated species in the interlayer space of the host V,05, replaces partially the intracrystalline water and induces the partial reduction of Vv to VIV, reflected by the significant changes in the mechanism of the conductivity, as shown by the corresponding impedance spectra.

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This work was partially supported by the CICYT of Spain. The authors thank Dr R. Ramirez for helpful discussions.
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