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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.
4167

which allowed temperature control and maintenance of a dynamic vacuum during the measurements. N = 3. washing with the same solvent in order to eliminate an excess of the reactants. .View Online 4168 Nitrogenated Bases and V205Xerogel Downloaded by google on 25 May 2011 Published on 01 January 1989 on http://pubs.4. The current was collected by means of platinum grids pressed against the two electrodes. 650 pm) used for the measurements were made by pressing samples in the form of films.5 H 2 0 at room temperature. Thermal treatment was carried out in a conventional Pyrex glass cell for i..By decreasing this angle it is possible to restrain the surface analysis to only a few layers of the sample (estimated to be ca. dL= 1. Infrared and XPS Spectroscopies 1.7).4% (C/N ratio. The system was coupled to the data station where the spectral data were accumulated. N = 1. experimental = 1. The intercalation process was controlled by determination of the basal spacing (interlayer distances) deduced from the X-ray diffractograms: starting V. studies in vacuo Torrt). The pellets were placed in a specially constructed cell. a less basic molecule containing two nitrogen atoms per molecule. t 1 Torr x 101325/760 Pa.7. Mg K.rsc.3). C = 5. 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. Thus.30 nm. Results and Discussion Infrared and XPS Spectroscopies Full protonation of ammonia and pyridine molecules was produced spontaneously.org | doi:10. thickness. spectra were recorded using a Perkin-Elmer 580B double-beam spectrophotometer coupled to an M-3500 PE data station. A. for V205/pz.r.30 nm. Cylindrical pellets (diameter. calculated = 4. 6 mm.frequency response analyser (FRA) connected to a Solartron 1286 electrochemical interface.1.r. If the angle between the plane defined by the V205film and the axis of the analyser is 90°. dL = 1. experimental = 4. in this way the system is preferentially orientated. with a hemispherical analyser.1 %.05 nm.. Impedance Measurements The electrical conductivity was measured at 298 K with a Solartron 1174 .6eV) or AL K.5 H 2 0 . 3 for a suitable signal/noise ratio). calculated = 1. the current flux being perpendicular to the plane defined by the layered materials.r. 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.1039/F19898504167 Pyridine and pyrazine were adsorbed from a dilute chloroform solution ( mol dmV3).r. characteristic bands of pyrazine coexisting with bands attributed to protonated pyrazine (table 1). So the i. .r./NH. dL = 1. XPS spectra were recorded on a Vacuum Generators ESCA LAB MK I1 spectrometer. spectroscopy when these molecules are adsorbed in the interlayer space of V205 1.3 %.O.15 nm.6eV) radiation was used. as has been shown by i. 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. as indicated by the presence of i. 20 ‘monolayers’ of V205. by convenient tilting of the sample we can infer details of the ‘bulk ’ and ‘ surface ’ compositions. Two identical electrodes were formed by sputtering of a silver-chromium mixture over the two opposite flat surfaces of the samples.C = 6. V. dL= 1.C. ( E = 1253. ( E = 1486. Typical compositions obtained from the elemental analysis were : for V205/py.1 % (C/N ratio.’ Similar experiments carried out with pyrazine. V205/py. V205/pz. revealed that partial protonation occurs.O.

1. Observed frequencies (cm-l) in the 1700-1 100 cm-' region for pyrazine (pz).1a. protonated pyrazine (H+-pz) and the pz/V205 intercalation compound PZ" Downloaded by google on 25 May 2011 Published on 01 January 1989 on http://pubs. spectra (1800-1 100 cm-I region) of adsorbed pyrazine in V 2 0 5xerogel (a) and treated in vacuum (lo-.O. The last of these also appears as an intense band in the i.r. Table 1. Casal et al. l(a)] bands centred at 1485. vs = very strong.u 1620 1485 L wavenumber/cm- ' J Fig.View Online B.lo = medium.r.r.1039/F19898504167 4169 H+-pzb - PZ/V. spectrum of pyrazine. m w = weak. solution. Torr) at 393 (b). In CHCl.org | doi:10. spectrum (1800-1000 cm-' region) of adsorbed pyrazine exhibits [fig. Two conceivable situations must be taken into account : (i) a proportion of molecules . 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)'. b = broad. 1418 and 1174 cm-l. 1. whereas it is weak (shoulder) in the corresponding i. spectrum of pyrazine hydrochloride. I 0.473 (c) and 573 K (4.rsc. 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'. vw = very weak. in KBr pellets.

This result disagrees with the i.org | doi:10. 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.r. 402 and 400 eV.rsc. 2). 500 K. data because only the bands corresponding to pyridinium ionsll. 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. the ratio being close to that found for pyrazine intercalates. 2. 1. to S. the remainder probably being adsorbed by coordination to vanadium ions in the host lattice.r.r. This fact suggests that in the intracrystalline environment neutral and protonated pyrazine coexist approximately in a 1 : 1 molecular ratio. not change their i. 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). but due to its tendency to be decomposed (in an oxidation process) by the host lattice. Parallel experiments carried out on the pyrazine intercalation complexes produce a strong diminution in intensity of the 1174 cm-' band assigned to protonated species. exposed for several hours to an atmosphere do with a relative humidity ca.-.1039/F19898504167 wavenumber/cm- ' Fig. and afterwards at room temperature. assigned to protonated and unprotonated nitrogen atoms in an N+-H/N proportion close to 1/3.. and (ii) only one of the two nitrogen atoms of all the adsorbed molecules is protonated. spectra (180&1100 cm-' region) of pyridine/V. 90 YO. The corresponding XPS analysis of the pyridine intercalation compounds also indicates the presence of both protonated and unprotonated forms. 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.O. . 393 (b). this band could alternatively be related . 453 (c) and 553 K (6). l2 are detected [fig. The most significant observation is the development of the band at 1445 cm-l characteristic of coordinated pyridine.View Online 41 70 Nitrogenated Bases and V. intercalates treated in vacuum at different temperatures: 293 (a). 2(a)]. as we discuss below. Xerogel 1486 1531 I 1603 I 445 Downloaded by google on 25 May 2011 Published on 01 January 1989 on http://pubs.O.Therefore. spectroscopic features. 1).13 Samples treated at ca. vibrations of ammonium ions produced as a mainly decomposition species. with a simultaneous increase in the intensity of the 1418 cm-' band in the spectral region studied (see fig. are protonated.

the reduction of the Vv is ca. XP spectra (N Is.View Online B. the adsorbed NH. Nevertheless. pressure of 1.O.O. the proportion being ca.01 x lo5 Pa) do not change appreciably the percentage of VIV formed in comparison with adsorption under mild conditions. Thus. 30%) of the original Vv has been reduced. 3 (c)]. The signal at 402 eV in spectrum (a) corresponds to a small quantity of NH.O. 4171 Downloaded by google on 25 May 2011 Published on 01 January 1989 on http://pubs. molecules replace the water initially present in the V. giving clusters of ammonium vanadate species .l4and by XPS analysis (up to 90% of protonated nitrogen atoms). compared to the intercalated pyrazine. one can imagine that a solid-gas reaction between ammonia and V.r. 3) show (N 1s level) that even at high temperatures a mixture of protonated and coordinated intercalated species coexist. 500 K (fig.rsc. where the XP spectra indicate an important increase in the amount of ammonia adsorbed. Casal et al. 10 YO. xerogel. the reduction of Vv is also found in the intercalation of This result shows the greater stability pyridine [fig.org | doi:10.r.O./py and V. In this case. 3 ( 4 ] indicates that a relatively high quantity (ca.+ions7. xerogel (a) and its intercalation compounds of ammonia (b). according to i. The XPS spectra of the V. More drastic conditions (treatment at 450 K for several hours at an NH. 0 1s and V 2p. 1) a tendency to decompose is observed in the intercalated pyrazine (formation of bands at 1735 and 1716 cm-'.1039/F19898504167 energy/eV Fig. levels) of: starting V. data (fig. Intercalation of a stronger base such as ammonia gives a high degree of protonated species at room temperature indicated by the intense i. The XP spectral evidence at the time of the formation of VIV [fig. probably associated with oxidation by-products) and is supported by XPS analysis showing a partial loss of the quantity of the intercalated molecules. absorption bands corresponding exclusively to NH. 9 % . pyridine ( c ) and pyrazine (6)treated in vacuum at 450-500 K./pz intercalation compounds treated at ca. In both cases. of intracrystalline pyridine/pyridinium species towards oxidation. takes place. To a lesser extent.O. 3.+formed by contamination with ammonia.

From the characteristic frequency & = 250 Hz) the value calculated for Cdl is . therefore.16 showing a correlation between the conductivity values and the water content of the system.05 xerogel and its ammonia.57 2. 4 shows the impedance spectra of V. changing the orientation of the films towards the axis of the analyser. 4(a). In samples treated at 450 I.38 0.54 0. the N/V ratio deduced from XPS is twice as large in the bulk as in the surface for intercalation of NH.17 V. XPS analysis of surface (S) and bulk (B) V.24 1.99 1.61 1. remarkable heterogeneities in the composition of the ammonium intercalation compounds are detected by XPS analysis . 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 3.40 4. Impedance Spectra The protonic conductivity of the V.95 0.O systems has been recently reported by Barboux et a1. Thus the extent of the reduction in the surface is two or three times larger than in the bulk (table 2).32 0. ( d ) and c ) respectively. treated for 1 h under different experimental conditions treatment Downloaded by google on 25 May 2011 Published on 01 January 1989 on http://pubs.07 0.13 1.39 S B 500 K.73 V2°5/NH3 0. Fig. and its pyridine (c) and pyrazine (e) intercalation compounds registered at 298 K from samples equilibrated at 55 % relative humidity.56 4./PZ 0.57 0.28 0.e. .O. vac.71 1. In this way. temperature gave the corresponding impedance spectra shown in fig. S 0.20 1. molecules trapped in the system.10 0.73 0. significant heterogeneities are also found.19 0.84 1.40 V.29 1.org | doi:10.38 0.50 0 0 s B 450 K.05/PY 0.50 1. S 0.1039/F19898504167 V4+ V5+ O(V) OH H20 N N+ 0. In fig. Subsequent vacuum treatment at that f. as deduced by XPS (37% of unprotonated species) and according also with the observations of Masbah described elsewhere.nH.76 0. xerogel (a).56 0.32 together with NH.69 0. at room temperature. As we have already discussed. provides information about the compositions in the surface and in the bulk (see Experimental).O. vac.25 B 500 K.88 0. .44 1.71 4.O.View Online 4172 Nitrogenated Bases and V 2 0 5Xerogel Table 2.80 4. XPS analysis while tilting the samples.97 0. vac.00 4.00 4. 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. pyridine (py) and pyrazine (pz) intercalated compounds.77 0.36 4. 4(b).63 2.rsc.78 4. The most S remarkable observation concerning these systems is undoubtedly the heterogeneity of the distribution of the reduced vanadium. i.88 0.64 1.14 0.43 0. those systems are excluded in the present study. 2. Therefore.86 2.75 1.22 1.18 - B 0 0 5' 2 ' gel 2.l5 On the other hand.

4173 0 Downloaded by google on 25 May 2011 Published on 01 January 1989 on http://pubs.O. which is theoretically predicted for mass transport phenomena.O and its pyridine (py) and pyrazine (pz) intercalation compounds treated 1 h under different experimental conditions treatments - component values = 144 Ri= 1.O vacuum 408 K. exposed to air 9.58 x 10-l' F V. (b) and its pyridine (c). which is close to the usual values found for the electrochemical double layer? The linear impedance is ascribed to a diffusion tail (Warburg impedance.9 7.5 48.44 7. vac.80 3.3 41 . exposed to air - 5.05. 573 K. Nyquist plots and equivalent circuits proposed for V.1.2 82. 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.40 v2°5/Pz 17. (c) and (e): measurements carried out at 298 K on samples exposed to the atmosphere .5 __ 71. vac. (f) intercalation compounds. 4.8 x 10-7 F lo6 SZ.33 vacuum 408 K. R.68 6. Casal et al. Cg= 1. .40 1. (a).5H.1.04 5.7 26. a.5 H.01 x R. vac.(b).O (a).O vacuum Re/' - Ri/ kSZ v2°5/PY 66. ( d )and pyrazine (e). Z.0 - 3x F crnw2. Component values of the equivalent circuits deduced from the impedance spectra measured at 298 K for V. 573 K. vac.rsc. Table 3.View Online B. 573 K.1039/F19898504167 (b) 5 10 z /lo4 R (4 z/lo4 R 0 1 2 0 5 2110~ R 10 1 z 1103 R 2 z/104 R 3 Fig.-1.org | doi:10.( d ) and (f) : measurements on the same samples.= 722 a.5 H.4 30.83 6. . at the same temperature.73 Cg/PF 60. In the equivalent . 573 K.87 1.6 19. vac. = 8.0 52.).96 1. c.O. vac. but under dynamic vacuum.

O+ 1. 500 K (in vacuo) of the V205/py and V. showing the irreversibility of the dehydration process.1. The corresponding value is E. When the sample is subjected to vacuum. This fact agrees with the spectroscopic observations that we have reported above.View Online 4174 Nitrogenated Bases and V205Xerogel Downloaded by google on 25 May 2011 Published on 01 January 1989 on http://pubs.O). = C. where C. dramatic changes are produced in the impedance spectrum [fig.lgThis interpretation is consistent with results obtained after treatment at temperatures up to ca. and/or (ii) protons due to dissociation of . related to the transfer of electrical charge in the electrolyte/electrode interface. It is known that V5+/V4+ couples support the electronic conductivity in amorphous V. can be calculated from the expression E. These observations can be explained by the great loss of intergrain water responsible for the propagation of the electrical signal across an ionic resistance. and E. and a capacitance. = 39.O is subjected to vacuum conditions. Mechanism We have shown that the intercalation of nitrogenated molecular bases into the lamellar hydrated V. Comparable results have been found in the conductivity measurements of other hydrated phases of transition-metal oxides.4 water molecules coordinated to Vv of the host lattice.rsc.32. with the subsequent formation of OH groups to assure the neutrality of the electric charge in the system.05. the values of these F . We is assume that this element involves the contribution of the electronic conductivity of the solid.2e per vanadium) of the V 2 0 5 xeroge120 (it may be remembered that this solid proceeds from a polymerization of decavanadic acid. 4(b)]. table 31. gives mainly protonated species. which corresponds to the modified vanadium pentoxide. Ri = 1.5 H. causes similar qualitative effects on the Nyquist plot to those observed when the starting V.disposed in parallel with the Cdl element.O. The relative permittivity E. the RL values remaining almost unaltered (table 3).1039/F19898504167 circuit of our system an electrolytic resistance Re of relatively low value (144 Q) can be ascribed to the presence of mobile ionic species. this model assumes the existence of a charge transfer resistance R. is the geometrical capacitance. 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 assigned equivalent circuit consists of one capacitance in parallel with a resistance.58 x obtained from the starting hydrated V. which is enhanced by the formation of V4+ions caused by the intercalation of the organic bases. so a certain quantity of protons remain in the xerogel which can be expressed as V205(0. = 1. l 8 Finally.01 x lo6 Q) being notably different from those components (C. which can regenerate by thermal/ vacuum treatment to a variable extent.org | doi:10.1 H.’ . related to the intrinsic dielectric properties of the solid material. their unprotonated forms following a reversible process.0. . Thus. in the Nyquist plot. determined from the impedance measurements in air. The protonation of the bases has two origins: (i) protons initially present in the xerogel compensating the negative charge (almost 0. as we have proposed elsewhere. but a new resistance component (RL) introduced in the proposed model [fig.05/pz intercalation compounds. essentially H+ ions associated with the acidic character of the hydrated solid.05 thin films. the capacitance component being completely eliminated and only the electronic resistance remaining. 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. respectively.O.d/SE. including the interlamellar water). d and S are the thickness and the surface area of the sample. is the vacuum permittivity. The intercalation of pyridine and pyrazine.4-) H. associated with the remaining interstitial water (microporous water.. 4(c)-(f).

O. Thus.rsc. 4. postulating the oxidation of these bases to nitrogen and bypyridine. This situation is well supported by XPS results (table 2). the water molecules tend to be eliminated from the system.In.OJpz compounds. where the protonation due to both (i) and (ii) paths are represented as different (I and 11) components in the total reaction. can act in a redox process (simultaneously to an acid-base reaction) favoured when a thermal or vacuum treatment is applied. a dependence on the nature of the base appears to be clear in our case. spectroscopy. Then. and consequently the higher tendency of the former to be protonated. pyridine molecules must be coordinated to the original VIV centres. which show i.25) compared with pyrazine (pK.View Online B. = 5. is the mechanism of reduction of Vv which is enhanced by the thermal/vacuum treatment.e. So we must suppose that an additional process involving the oxidation of the intercalated species to N-oxides takes place together with the postulated . In this way. r e ~ p e c t i v e l y . respectively. in the starting xerogel. although to a minor extent. nor XPS data support the possibility of reduction via oxidative dimerization of the intercalated heterocycle. 41 75 1 Downloaded by google on 25 May 2011 Published on 01 January 1989 on http://pubs. while for pyrazine this expression has a positive value as was detected by i.O. absorption spectra with significant differences to those obtained by intercalation of pyridine followed by thermal treatment.4-y) is close to zero (full protonation). and the XPS results.org | doi:10. compounds.r.r. An alternative explanation would be the existence of a charge transfer (like in benzidine-V.r. This follows from the greater basicity of pyridine (pK. a reduction to VIV./py intercalation .Nevertheless. Casal et al. Schollhorn explained the reduction of transition-metal dichalcogenides (S2Ta) when ammonia and pyridine are intercalated. compounds22)between the base and the host lattice. in agreement with the i.2’-bypyridine. Thus. An important aspect. as evidenced by the spectroscopic results obtained from intercalation of the hypo thetical products of condensation of pyridine. in a first approach we can tentatively accept that the hydroxyls formed according to scheme 1 (part 11). a fraction of Vv could be reduced (scheme 2). which indicate that the VIV/N(coord. = 0. it has been reported21 that.4) B] +C(1. This ratio is not achieved in the V.r.4’. for the present not conclusively resolved. for pyridine and without thermal or vacuum treatment the value of the expression (x-0.5-y) H20 + (x-0. either in bulk or surface analysis. Neither i. 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. cycles of hydration-dehydration provide.) ratio is close to 1. but in our case these mechanisms cannot explain the loss of oxygen shown by XPS.65).5H2O + (x-0. ~ ~ our case this situation can be disregarded.and 2. In fact. According to quantum-chemical calculations.4-y) (11) ~ ~~~ B + y (BH’ + OH-)] Scheme 1. This situation is illustrated in scheme 1 . at the same time that a proportion of BH+ species are deprotonated.1039/F19898504167 + x : B + [1. i. 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)].

and according to the quantitative XPS results shown in table 2. 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'"). the loss of water molecules from the system is accompanied by the coordination of the unprotonated base to the vanadium atoms. as shown by the corresponding impedance spectra. Finally. especially in the pyrazine intercalate compounds. reflected by the significant changes in the mechanism of the conductivity. 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. spectra of samples thermally treated show bands probably due to an oxidative decomposition of pyrazine to products of unknown nature.View Online 4176 Nitrogenated Bases and V205Xerogel B: B H+ "2O Downloaded by google on 25 May 2011 Published on 01 January 1989 on http://pubs. The reduction of a fraction of the Vv observed by XPS. replaces partially the intracrystalline water and induces the partial reduction of Vv to VIV. as indicated above. On the other hand. xerogel. (ii) protons originated by dissociation of water molecules in the interlayer space coordinated to Vv of the host lattice. reduction via OH groups.05. in particular when thermal/vacuum treatments are applied. 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. This process could be of special importance in the case of the V.1039/F19898504167 Scheme 2. 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). results. as shown by the a. . in those systems where protons or protonated bases coexist the protonic conduction is probably due to a Grotthuss (transport of protons through water molecules). associated with intergrain water molecules./pz compounds (30% of Vv reduced to VIV) where the i. Thus the intercalation of pyridine and pyrazine produces protonated and coordinated species in the interlayer space of the host V. is a difficult point to explain. When water content decreases. or an oxidation of the intercalated guest molecules. Several factors can be invoked such as: redox processes involving hydroxyl groups created by dissociation of the interlayer water molecules.c.org | doi:10. Under these conditions.r. 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.rsc.O.

Chem. Lord. Dench. ed. Engl. P. Reddy (Reverti. Innes. React. Barcelona. Livage. 761. 19 J. 14. A. 2 R. A. Masbah. Morineau and J.. J. P. J.. 113. Paper 9/00386J. Schollhorn. J. 36. Shimanskaya. 983. K. Angew. Rabenau and W. Scaife and D. V. J. Casal et al. 1982). Bull. Acrivos. Chem. Simmons and K. Livage. N. Int. Lett. 2. 5 A. P. Audieres. I. 11 N. Kinet. H. Gallais. 1982. Crespin and D. Inorg. 14 K. ed. Amsterdam. Davies and D. Seah and W.. Nucl. Van Damme. in Adsorption and Catalysis on Oxide Surfaces. 2009. 1985. Babonneau. Michaud and J. 190. Phys.Erre. 10 R. ed. p. S . Shafer. 4177 This work was partially supported by the CICYT of Spain. Reidel.. 1988. J. Whittingham and A. 82 1597. Golender and M. Infrared Spectra of Inorganic and Coordination Compoundr (John Wiley. 1986. 22 R. L. in Intercalated Layered Materials. 13. SOC. 208.rsc. E. 1988. in Inclusion Compounds. Weppner. Bullot. Orleans. 366. 13 E.. Phys. D. 82.. S . 0. London. Jacobson (Academic Press. Bond (Elsevier.. 371. ed. K. 23 L. A. Surf. 17 Electroquimica Moderna. (Univ. 1985).. J. Krogh Andersen. Reidel. Anderson. F. 25 K. Parry. 6 R. 1984). V. New York. L. Levy. Ramirez for helpful discussions. Chim. Chem. 2. M. 1980. A. Chichester. Skou. Gautthier and J. Barboux. Chim. 9-10. A. J. Interface Anal. 1979). Livage. Sharp. 986. ed. Ed. D. in press. A. 8 M. 1963). 1. Ph. C. 1989 Downloaded by google on 25 May 2011 Published on 01 January 1989 on http://pubs. 1980. M. A. 24 A. 12 D. 2. 20 F. M. 9.Schollhorn. Millers. Lett. 1980. 1987). Whittingham and A. Casal. 315. 21. Chem. The authors thank Dr R. J. p. Marston and F. Chem. Dordrecht. 21 B. 229. Bockris and A. 0 . MacNicols (Academic Press. 181. 9 J.1039/F19898504167 . Ed. Masbah. ed. 7 E. 1963. F. 381. Dordrecht. vol. Can. Thesis. p. W. 18 E. Ruiz-Hitzky and B. P. 33. 16 P. New York. 1979). J. ed. 19. 79. Levy (D. R. Soc. Schollhorn. Nutall. 1957. 7. 3 R. (D. A. Catal.M. Kreuer. W. J. Int. M. Caral. Acta. Specrrochim. Solid State Ionics. M. E. Josieu and J. 1982). 1981. 0. Appl. D. Agnew. Krogh Andersen and E. Eng. in Intercalation Chemistry. 1964. chap. 1961. References 1 G.org | doi:10. V.. Barboux. S. Faraday Trans. p. Atwood. vol. Gill. J. M. Fr.. Nakamoto. Jacobson. Holland. Subba Rao and M. 27. Araki. F. D. D. G.View Online B. 4 J. Solid State Ionics. J. M. Solid State Ionics. 1961. Jacobson (Academic Press. Holland. C. R. Livage. 1979. 18. in Intercalated Layered Materials. I . 1. 1980). 221. Spectrosc. p. J. Received 24th January. 15 H.D. in Intercalation Chemistry. Cook. H. 85. Mol. 99. 39.. 27. Che and G.