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Applied Catalysis A: General 205 (2001) 201–214

Structure and activity of Sn-Mo-O catalysts: partial oxidation of methanol
N. Graciela Valente, Luis A. Arrúa, Luis E. Cadús∗
INTEQUI, Instituto de Investigaciones en Tecnolog´a Qu´mica (UNSL–CONICET), Chacabuco y Pedernera, 5700 San Luis, Argentina ı ı Received 22 October 1999; received in revised form 24 March 2000; accepted 29 March 2000

Abstract This work deals with the catalytic behavior of a series of Sn-Mo-O catalysts in the partial oxidation of methanol. The catalysts of different Sn:Mo ratios, were prepared by co-precipitation and they were investigated by means of dynamic experiments, test reactions (methanol–formaldehyde partial oxidation, isopropyl alcohol decomposition) and physico-chemical characterization (XRD, BET, TPD of NH3 , TPR, XPS and EPR). It was observed that interdispersion between MoO3 and SnO2 favors a superficial architecture in which the Sn-Mo interaction plays a major role modifying the reactivity of the lattice oxygens and the reducibility of Mo ions and, therefore, the catalytic behavior. The partial oxidation of methanol induces a reordering of the catalyst structural organization leading to a Mo surface enrichment. The absence of chemical shifts for Sn (XPS) suggests that the O–Mo bond is mainly responsible for the methanol reaction. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Methanol partial oxidation; Mo-Sn catalysts; Methyl formate

1. Introduction The first part of the present work on the Sn-Mo-O catalytic system focused on the catalytic behavior of mechanical mixtures of pure Sn and Mo oxides [1]. Various systems based on multicomponent oxides have been the object of study in the oxydehydrogenation (ODH) methanol reaction. In particular, Ai has worked on MoO3 -Bi2 O3 -P2 O5 [2], SnO2 -V2 O5 [3], SnO2 -P2 O5 and SnO2 -MoO3 [4] catalysts. It is well-known that in several reactions catalysts based on multicomponent oxides exhibit a better performance than component oxides separately. This has been accounted for in the literature by means of mechanisms, such as Remote Control by spill over species
∗ Corresponding author. Fax: +54-2652-426711. E-mail address: lcadus@unsl.edu.ar (L.E. Cad´ s). u

[5] as well as by means of physico-chemical characterizations. However, the role of component oxides in these catalysts is not yet completely understood. The state of the catalyst surface (composition, chemical state of the metals, surface structure, etc.) cannot usually be studied during the catalytic reaction. Besides, the superficial composition in interdispersed systems might be different than that of the bulk and may change in the course of the reaction. An important factor to be considered in a study based on a reaction of oxidative dehydrogenation is the characteristics of the absorbed oxygen species as well as their capacity to migrate in the lattice of the oxide used as catalyst or in its boundary. A further factor to be taken into account is the lability of the metal–oxygen bonds. Some authors have proposed that both the acid base properties of the metal oxide and the strength of the metal–oxygen bond are

0926-860X/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 0 ) 0 0 5 6 5 - 2

0001%). for example. Ai [7] has attributed this activity to the presence of acid and base sites distributed on the catalyst in some particular way. the increase of activity in the ODH of MeOH can be attributed to changes in the reducibility of the supported Mo. Catalyst preparation 2. However. and SnCl2 ·2H2 O (May and Baker AR grade with As<0. the proposed mechanisms [11] indicate that the proton and electron transfer between the alcohol and the catalyst is important. test reactions and physico-chemical characterization. obtained by co-precipitation. Experimental 2. The possibilities of the presence of an amorphous phase or contamination of one phase by another cannot be left out. Taking into account the complexity of the system. These observations are of great value for catalysts based on mixed oxides.1. However. MoO3 was prepared by dissolving ammonia heptamolybdate in distilled water. SnO2 is not a good catalyst for ODH of methanol due to its low activity. We will try to explain the solid reactivity and the catalyst activity and selectivity according to the possible mechanisms of methanol reaction. Therefore.202 N. [10] as regards a close relation between structure and activity should be supplemented with explanations that take into account the observations on mechanical mixtures. Valente et al. In order to understand the behavior of this catalyst. in MoO3 catalysts supported on SnO2 . urea was added and stirred for 15 min. However. it is possible to reach a stable architecture towards which a system of mechanical mixtures might tend. Valente et al. in studies performed by XPS. The obtained suspension was then filtered and washed with a very dilute NH3 solution in order to eliminate Cl− (complete elimination was checked with AgNO3 . have suggested the possibility that SnMoO2 coexists with MoO3 in samples treated at temperatures of 873 K. the solid obtained was dried at 373 K overnight in a vacuum oven and then calcined at 823 K for 8 h. / Applied Catalysis A: General 205 (2001) 201–214 directly responsible for catalytic activity [6]. these authors concluded that the Mo sites are the active sites for the reaction. Therefore. Weng and Wolf [8]. SnO2 was prepared from SnCl2 and urea.0005%. Preparation of pure oxides The reagents used were (NH4 )6 Mo7 O24 ·4H2 O (Merck AR grade with Fe<0. [1] obtained excellent results with mechanical mixtures prepared under conditions such that the interactions between molybdenum and tin oxides were minimal. this author does not offer a description of the surface that could allow one to identify phases and account for active sites. The formation of mixed oxides was not observable by the characterization techniques used.001%). by means of dynamic experiments.001% and Cu<0. Thus. [9] have noted that. The purpose of the present work is to determine the possible physico-chemical transformations of the catalyst. The preparation of catalysts with different Sn:Mo atomic ratios by co-precipitation of their respective precursors had the objective of achieving close contact between the phases of such elements. in the ODH of methanol.5 with magnetic stirring. These transformations might be related with the reaction of the adsorbed phases through the oxidation–reduction cycles of the catalytic process (dynamic feature).1. By observing the turnover frequency of methanol oxidation versus the Mo surface concentration.G. In this way. In fact. it becomes necessary to investigate the physico-chemical properties of the involved phases by mean of catalyst characterization after different pre-treatments. they observed formation of large isolated crystals with the consequent increase of acidity while the turnover frequency remains constant. additional factors as the extent of Mo reduction and the influence of tin oxide on such reduction should be included together with geometrical considerations. In this way. Then. At Mo loadings higher than those of the monolayer. Pb<0. it would be possible to know the probable surface reordering.1. After evaporation of the solvent at 323 K and reduced pressure. Niwa et al. such as MoO3 improves its catalytic behavior. changes in the structure cause modifications in the catalytic behavior. 2. [10] had prepared and described a catalyst which consisted of a monolayer of MoO3 supported on SnO2 . Niwa et al. the observation by Niwa et al. a series of measurements were performed. which is significantly hotter than typical conditions employed for alcohol dehydrogenation. The description of this system might correspond to complex catalyst whose structure is difficult to determine. combination with other metallic oxides. Previously. SnCl2 was dissolved in NH4 OH solution at pH 8.

1 K. 7:3. / Applied Catalysis A: General 205 (2001) 201–214 203 solution). YMe (0. The reaction was carried out at 363 and 373 K in a fixed-bed continuous flow reactor under atmospheric pressure. dimethyl ether (DME). Catalytic test 2. weight of catalyst to total gas flow rate ratio. Other by-products. The flows of O2 and He were controlled by Matheson mass flow controllers. X-ray diffraction (XRD) XRD patterns were obtained by using a Rigaku diffractometer operated at 30 kV and 20 mA by employing Ni-filtered Cu K radiation (λ=0. formaldehyde (FA). The total gas feed rate was 28 sccm. FA+MeOH. ensuring temperature variations lower than 0.3. In both cases after the pre-treatment.5.1.14 and 0. 3:7. such as dimethoxymethane (DMM) and CO were not detected.2.3.51418 nm).N. He was flowed for 5 min and the reaction was studied under the usual conditions 2. 2. MeOH. Catalyst characterization 2. The solvent was evaporated by using a rotary evaporator at 323 K and at reduced pressure. the solid was dried at 373 K overnight and calcined in air at 823 K for 8 h. the solid obtained was dried at 373 K and then calcined at 823 K for 8 h. 60 and 90 min.2.18) and oxygen YO2 (0. 2. FA+O2 +MeOH. After evaporation of the solvent in a rotating vessel at about 323 K and reduced pressure. the precipitate was mixed with a saturated solution of (NH4 )6 Mo7 O24 ·4H2 O in adequate amounts so as to obtain different Sn:Mo molar ratios.G. After being filtered and washed.3. 30.2. 2. The independent variables investigated were molar fractions of methanol. Selective oxidation of methanol Selective oxidation of methanol was measured under atmospheric pressure in a conventional fixed bed reactor equipped with a jacket furnace.5% IPA and the balance helium.1. MeOH was fed from a saturator that was immersed in a water bath.2. the following catalysts were prepared: 0:1. Analyses of products were made by on-line gas chromatography (KONIC-3000) with a thermal conductivity detector by using Porapak T and 5 Å molecular sieve columns.% H2 in He was fed for 15. 448 and 473 K.1. 2. The catalysts were referred to by their Sn:Mo atomic ratios. The reaction temperatures were 433. Valente et al.3. respectively. Catalytic activity on catalysts subjected to pre-treatments The 7:3 catalyst was subjected to different reducing conditions using MeOH and H2 and also to oxidizing conditions.% MeOH in He was fed for 60 min. FA+O2 . 1:1.2. The catalysts were prepared by precipitating tin hydroxide in excess of urea in aqueous ammonia solution at pH 8.8 and 2.9.0 g) was held in place by a glass–wool sandwich. The solid was subjected to the following conditions: (1) oxidizing conditions: MeOH+O2 and (2) reducing conditions: (i) A 5 vol.7 g of 7:3 catalysts. when the steady state was essentially reached. The feed was a mixture of MeOH. A Micromeritics Accusorb 2100 E was used. Surface area Specific surface areas (SBET . Thus. W/FV (0. The working temperature was 453 K. 2.2. methyl formate (MF). m2 g−1 ) of all samples were determined from nitrogen adsorption isotherms at 77 K by the BET method. The experiments at different contact times (W/FV ) were carried out with 0. T (453 and 463 K).3256 kPa. Catalytic evaluation feeding FA Measurements were performed with 7:3 catalyst at 453 K using the different feed conditions listed as follows: FA. 45.2. The catalyst (W=1.5 molar ratio. The catalytic measurements were obtained after running the reaction for at least 2 h. The reactor temperature was measured and controlled by a PID controller with a coaxial thermocouple. O2 and He at 2. Then. water and CO2 were the only measurable reaction products. The feed consisted of 4. The total gas flow rate was 30 sccm and pressure was 93. In all cases. . 1.3.3. Preparation of Sn-Mo catalysts The reagents used were the same as those for pure oxides preparation. 1:0.07) of feed.5:1:10. MeOH+O2 .7 g cat s cm−3 ) and reaction temperatures. (ii) A 18 vol. Decomposition of isopropyl alcohol (IPA) Decomposition of IPA was used for determining the acid–base properties of the samples. 2. Its temperature was controlled by means of a Lauda RCSR20C cryostat.

3. becoming closer to that of SnO2 . The 7:3 catalyst was also evaluated by EPR after being pre-treated at 453 K with: (i) 5% H2 /N2 mixture. 2.75 27.75 MeOH/O2 /He mixture. 3.3. (ii) 18% MeOH/He mixture.6. 2.5 vol.36 21. Ratios of atomic concentration in the outer layers of the samples were expressed as the corresponding XPS area ratios by using the effective ionization cross section of ejected electrons tabu- lated by Scofield and the formulas given by Seah and Dench [12]. 3.G. Samples of ca. Temperature programmed desorption The results for the different catalysts are shown in Fig.7 GHz and 100 kHz magnetic field modulation. Temperature programmed desorption (TPD) TPD was performed with a dynamic apparatus and detection by thermal conductivity connected to a data acquisition system. a PC for data retrieval. was pressed. For all catalysts. independent of the tin load. All the catalysts were evaluated prior and after being subjected to reaction conditions.7. / Applied Catalysis A: General 205 (2001) 201–214 The flow rate was 40 sccm and the conversion of IPA was <15% in all experiments. Temperature programmed reduction (TPR) TPR studies were performed in a conventional unit. The spectrum exhibited two well-defined peaks.1. 40 sccm (15 min). 7:3 and 1:0 catalysts Sn:Mo 0:1 3:7 1:1 7:3 1:0 SBET (m2 g−1 ) 1.4.3. the area corresponding to the first peak would correspond Table 1 Specific surface area (SBET ) of fresh 0:1. The samples were subsequently contacted with a 30 sccm flow of 4. as fine powder. 1.75 MeOH/O2 /He mixture. The SBET exhibited by co-precipitated catalysts was greater than that of pure MoO3 . The surface area increased as the Sn:Mo ratio increased from 3:7 to 7:3. Results 3. The apparatus consisted of a gas handling system with mass flow controllers (Mathesson). (iv) 0. 40 sccm (30 min) and then treated with 5% H2 /He.6 eV. 1:1. After that. 2. X-ray diffraction X-ray diffractograms are shown in Fig. cooled at room temperature. to a final temperature of 1000 K. model CN 2010). only two phases were observed. In this case. 40 sccm (15 min).53 30. a tubular reactor. 2. corresponding to orthorhombic MoO3 and SnO2 (cassiterite). 2. a furnace and various cold traps.3. using NH3 as probe molecule. helium was admitted at room temperature to remove oxygen.18:0.6 eV). at a rate of 10 K min−1 .204 N.2. Total acidity could be calculated by integrating the area under the peaks.18:0.3. When the amount of MoO3 was increased from 7:3 to 3:7.07:0. 3.% O2 in He at 600◦ C for 30 min and then. 40 sccm (30 min). (iii) 0.7. The sample. the intensity ratio of the MoO3 -SnO2 peaks was higher and crystallinity of SnO2 decreased.% H2 in N2 and heated. X-ray photoelectron spectroscopy (XPS) XPS spectra were obtained with a Shimadzu spectrometer employing a Mg K X-ray excitation source (hν=1253. 3. Valente et al. Electron paramagnetic resonance (EPR) The EPR measurements were obtained with a Bruker spectrometer at room temperature and a Klystron frequency of 9. while hydrogen consumption was monitored by a thermal conductivity detector after removing the water formed. 80 mg were first oxidized in a 30 sccm flow of 20 vol. Product analysis was performed by gas chromatography using a Carbowax 20 M on Chromosorb W column and a thermal conductivity detector. Referencing was performed both before and after a complete set of spectra had been obtained. a linear temperature programmer (Omega. the following order was found 1:1>3:7>7:3.74 14.5.39 . The reported binding energies were referenced to C1s at 284.07:0. However. Surface area (SBET ) The specific surface areas (m2 g−1 ) obtained for the different catalysts are shown in Table 1.

1:1 and 7:3 catalysts. 1. Fig. X-ray diagram of fresh 3:7. . To compare: (− − −) SnO2 (JCPDS 21-1250) and (—) MoO3 (JCPDS 5-508). TPD of NH3 of fresh catalysts: (−·−·−) 3:7. / Applied Catalysis A: General 205 (2001) 201–214 205 Fig. Valente et al.G. 2.N. (· · ·) 1:1 and (—) 7:3.

to physisorption (up to ≈400 K). During TPD of catalysts with 4 wt. In the used 3:7 catalyst. It can be observed that there appears to be a peak with lower reduction temperature (around 700 K) common to all catalysts.206 N. Also.4. This peak was assigned to acidic sites of MoO3 . the higher being the one corresponding to the 3:7 catalyst (850 K). Valente et al. but a new desorption peak between 600–700 K was observed. As a consequence. a signal with a g . the N2 signal was not found. the acidity was evaluated by integration of the ammonia desorption peaks between 400 and 700 K. The spectra of the used catalysts showed a resonance signal with an average g value of 1. the same authors did not observe the N2 signal.925. 3. However. Temperature programmed reduction The TPR results (Fig. which could indicate an axial symmetrical environment. Catalyst 1:1 exhibited a value of 843 K while that of Sn:Mo=7:3 was 808 K. showing the order 1:1∼ =3:7>7:3. 3) showed that the binary catalysts (SnO2 -MoO3 ) have enhanced reducibili- ties compared with the pure oxides. Studying a mixed (massive) MoO3 -SnO2 catalyst. The reduction temperature of the main peak was different for each catalysts. Niwa et al.% of MoO3 or more. catalyst 7:3 exhibited a shoulder at ≈643 K. [9]. 3. it can be observed that fresh catalysts exhibited a different g value (1. / Applied Catalysis A: General 205 (2001) 201–214 Fig.96).% of MoO3 . which would indicate lower anisotropy in the system caused by a reordering of the ions Mo5+ during the reaction. (− − −) SnO2 and (−··−··−) MoO3 . 4. in this study. (—) 7:3. because pure MoO3 does not show this desorption peak. corresponding to paramagnetic species attributed to Mo5+ ions. is the possible ammonia decomposition on the solid surface. which are present only when MoO3 is in close contact with SnO2 . Another aspect that has to be considered in the interpretation of ammonia desorption experiments. Used catalysts showed a sharper signal.5. Electronic paramagnetic resonance The results obtained by EPR for the different catalysts prior (fresh) and after being subjected to reaction conditions (used) are shown in Fig.G. (· · ·) 1:1. TPR of fresh catalysts: (−·−·−) 3:7. 3. which showed very low reducibilities. which can mask the ammonia TPD data.700–800 K during TPD of NH3 from pure SnO2 and MoO3 supported on SnO2 catalysts with less than 4 wt. observed a N2 signal by mass spectroscopy at ca.

5. might indicate the presence of Mo5+ in addition to Mo6+ . EPR spectra of fresh and used catalysts: (−·−·−) 3:7. the surfaces are still enriched in Mo.34 – – 2. In a previous study on mechanical mixtures. Table 2 Binding energies and Sn:Mo atomic surface ratios of fresh and used 3:7.42 0.1 232.30 0.1 232.8 486.18 0. The results obtained are shown in Fig. Mo6+ was reduced to Mo4+ (MoO2 ). 1:1.G.33 2.9 486. average value of 2.925 was observed.0 232.48 0. and 7:3 catalysts.50 0.18 0. which is attributed to an unpaired Mo5+ electron. 4.0 232.70 0. The difference of ≈1 eV. X-ray photoelectron spectroscopy The results are presented in Table 2.30 0. the concentrations .8 486.00 1.0017 assigned to O− species was observed [13]. overall. from XPS measurements Catalyst Mo:(Mo +Sn) bulk Binding energies (eV) Mo 3d5/2 Sn 3d5/2 7:3 Fresh 7:3 Used 1:1 Fresh 1:1 Used 3:7 Fresh 3:7 Used MoO3 SnO2 0. giving a lower Mo5+ signal. It cannot be discarded that when strong reducing agents such as H2 were used. the line widths of the peak corresponding to Mo 3d5/2 exhibited a small shoulder that might indicate the existence of more than one species. 3.0 233. Valente et al. and binding energies of fresh MoO3 and SnO2 . / Applied Catalysis A: General 205 (2001) 201–214 207 could be compared from their respective intensities. In all the spectra.N. Taking into account that the bandwidths are similar. Thus.42 – – Sn:Mo surface Sn:Mo bulk Fig. (· · ·) 1:1 and (—) 7:3. The binding energies corresponding to Mo 3d5/2 were lower in all mixed catalysts compared to pure molybdenum oxide. The surfaces of the 1:1 and 3:7 catalysts showed enrichment in Sn when compared to the starting materials.9 486. Catalyst 7:3 was subjected to a series of oxidizing and reducing pre-treatments and subsequently characterized by EPR. being similar to those obtained for pure tin oxide.20 0.70 – – 232. In fact.33 1.50 0. The binding energy values of Sn 3d5/2 were also independent of the catalyst composition and did not change after catalytic test. However.8 – 486. It was attributed to the MeOH reaction or to some of the intermediates on the catalyst surface [1]. These =H results indicate that the reacting mixture that included oxygen generated a more generalized reduction from Mo6+ to Mo5+ .2 232. The surface atomic ratios did not match the expected value from the bulk composition. an increase in the concentration of Mo5+ species was observed after the catalyst was subjected to the reacting atmosphere.8 486. a resonance signal with a g value of 1.9 1. The spectra were normalized on the base of sample weight at equal measurement conditions. The binding energy for Mo 3d5/2 in the mixed catalysts was independent of the catalyst composition and did not change significantly after catalytic test.00 0. according to pre-treatment.1 – 486.6.24 1. the intensities followed the order (MeOH+O2 )>MeOH∼ 2 . compared to the bulk.

Its advantage lies in the fact that it can be applied to low specific surface area catalysts for which the spectroscopic techniques cannot provide reliable data [14]. 3:7. Assuming that propene formation rate is a measure of the surface acidity.18×10−4 – – – – Rates of acetone production (mol m−2 min−1 ) – 2.208 N.28×10−5 (mol m−2 1:1 1. This reaction cannot distinguish between the Brönsted and Lewis sites.G. EPR spectra of 7:3 catalyst after different treatments: (−·−·−) H2 .97×10−6 1. 3. (· · ·) MeOH and (—) MeOH+O2 .7.02×10−6 Rate of acetone production to rate of propene production ratio – 0. 1:1. Table 3 Isopropyl alcohol decomposition on catalysts 0:1.21 0.70×10−5 3.24 0.97×10−5 3. then the acidity order of the catalysts is as follows: 1:1∼ =3:7>7:3.84×10−5 2. as suggested by Ai [4]. The propene and acetone production rates together with their respective ratios are shown in Table 3.16 0.23×10−6 – 4. / Applied Catalysis A: General 205 (2001) 201–214 Fig.12×10−4 1. 7:3 and 1:0 Treaction (K) Sn:Mo 7:3 363 373 363 373 363 373 Rates of propene production – 1.19 – 0.02×10−5 – 1.46×10−6 4.36 0. The IPA decomposition proceeds by two parallel routes: dehydration to propene on acidic sites and dehydrogenation to acetone on redox (basic sites).65×10−6 5. 5. Valente et al.07×10−5 min−1 ) 3:7 1. IPA decomposition test This test gives information about the surface acid–base properties of the catalysts.22 .44×10−6 5.

This catalyst also showed the lowest selectivities to DME and CO2 (16 and 12%. all the catalysts showed strong increase of conversion with temperature.18. the moles of methanol converted were slightly smaller than in the case of YMeOH 0.G. it was observed that at low W/FV values. accompanying the decrease of DME selectivities. respec- tively. The results of catalytic evaluation of Sn:Mo=7:3 at different contact times (W/FV ) are shown in Table 4.9 g s cm−3 and YMeOH 0. 1:1 and 7:3 catalysts: ( ) MeOH conversion. respectively). Catalytic activity of 3:7. As expected. the main product was MF at the expense of FA. The reason could be attributed to a lower YO2 :YMeOH ratio present when YMeOH of 0. Under all conditions (except for W/Fv 0.N.14). When working with YMeOH of 0. the basicity of the catalysts shows a reverse order to that found for acidity. / Applied Catalysis A: General 205 (2001) 201–214 209 If the activation energy of the propene formation is considered as a measure of surface acidity [15]. the MF and FA selectivities showed a slight dependence with the temperature. the same trend is found. a decrease of conversion was observed.18 was used.14. ( ) MF selectivity. ( ) FA selectivity. 6. ( ) DME selectivity and ( ) CO2 selectivity. The ratio of dehydrogenation rate (to acetone) to the dehydration rate (to propene) has been regarded [4] as a measure of basicity. Assuming this correlation. However. Valente et al. selectivity to FA was the highest. Table 5 shows the results obtained by feeding reagents and products in different orders. 3. while CO2 selectivities clearly increase as the temperature increases. 6. By feeding only FA. while at elevated W/FV values.8. . For a MeOH molar fraction (YMeOH ) of 0. a small amount of MF was observed. the main product was MF. DME and CO2 as a function of reaction temperature for the different catalysts are shown in Fig.14. Catalytic activity The results of methanol conversion (X) and selectivities to MF. which might come from a dimerization reaction of FA by a Tischenko type mechanism. FA. This effect was immediately suppressed by incorporation of O2 into the feed. Irrespective of the catalysts. The subsequent incorporation of MeOH caused high Fig. It is worth to mention that the 7:3 catalyst showed the highest conversion (64% at 498 K) with MF and FA selectivities in the order of 48 and 21%.

48 SFA 27. In fact. decreasing with operation time until reaching constant values.87 SCO2 1. [16] note that after catalytic evaluation. by comparing the XRD intensities of the mixed catalysts with pure oxides MoO3 and SnO2 .026 47.14:0.14:0. The TPR data showed that the reducibilities of the pure oxides were very low.7 0. DME might form via dehydration on acid sites.79 1.79 49. / Applied Catalysis A: General 205 (2001) 201–214 Table 4 Catalytic activity of catalyst 7:3 as a function of W/FV (g cat s cm−3 ) at 453 and 463 K W/FV 2.07 0.61 52.04 29. Oxygen in the feed is necessary for DME production.9 2. For catalyst 7:3. the acid sites on the surface of these catalysts were poisoned or destroyed.07 0.07 0.80 32.49 20.04 69. a clear decrease of SnO2 crystallinity was observed as molybdenum loading was increased.354 30. Valente et al.07 0.8 32. No new XRD peak was observed.40 0 X correspond to conversion of methanol.57 1.135 27.18:0.07 Xa 38. When the catalyst was treated with H2 prior to MeOH ODH.18:0.55 46. the changes in the surface area of catalysts SnO2 -MoO3 with composition do not follow a linear trend.14 SFM 47. Bañares et al.9 2.7 1.32 22. The changes exhibited by binary oxides with respect to pure oxides indicate that this catalyst is more complex than a simple mixture of oxides. The catalytic activity studies of the catalyst 7:3 subjected to different pre-treatments under reducing conditions with MeOH and H2 and under oxidizing conditions can be summarized as follows. which is shown by the elevated initial activity of the catalyst.14:0.210 N. which differ from the data Table 5 Catalytic activity of catalyst 7:3 at 453 K using different feed conditions Feed FA FA+O2 FA+O2 +MeOH FA+MeOH MeOH+O2 MeOH Results MF is produced (Tischenko reaction) MF production is not observed High MeOH conversion and high MF yield The MeOH conversion and the MF yield decrease proportionally The observed products are MF (the highest yield).18:0.98 19.38 35. higher MoO3 crystallization might occur.9 0.042 22.51 41.58 47.06 0 0 1.00 47.07 0.35 33.68 42.764 81. or became too weak to produce MeOH dehydration.98 15. which was proportional to the MeOH concentration in the feed.14:0. This might indicate that.22 20. Discussion The X-ray diffractograms only show the crystalline phases corresponding to SnO2 and MoO3 .9 2. The methanol pre-treatment did not show any observable effect on the methanol ODH.7 1.5 0 0 1.09 19.376 33.7 1.38 45.8 0.07 0.07 23. after treatment with methanol. 4.07 0.G. When only MeOH was fed. a decrease in conversion with time on stream was observed with an accompanying decay in MF yield.07 0.95 37.07 0. activity and more MF production.24 24.15 36.21 0 2.7 1.7 0.81 19. By feeding MeOH and FA without the presence of O2 . indicating the absence of definite Sn-Mo mixed oxide compounds.96 30. the initial activity was high.33 22.33 22.18:0.07 0.12 60.15 43.9 a T (K) 453 453 453 453 453 453 463 463 463 463 463 463 YMeOH :YO2 0.045 44.18:0. This might indicate that MeOH–FA constitutes a probable route of MF formation.14:0. no activity was observed and consequently there was no DME formation.98 28. FA and DME DME production is not observed .69 42.18:0. the MoO3 :SnO2 intensity ratio fell below that expected by a linear calculation based on its relative atomic ratio. The reducing atmosphere (H2 ) might have favored the formation of catalytically active sites.14:0.34 44.823 SDME 24.35 26.24 27.07 0.15 41. However.56 39.

MoO3 loses the 0. The reordering of surface atoms might influence product distribution in a structure-sensitive reaction. it is probable that in these massive catalysts both MoO3 and SnO2 undergo reduction simultaneously over a wide temperature range. exhibiting an average g of 1.925 assigned to Mo5+ . This is consistent with the XRD results that indicate a strong Sn-Mo interaction. while MoO3 is selective to products of partial oxidation although its activity is relatively low. Further characterizations are required in order to more accurately describe these interactions. 700 and 808 K. the spectra show a single g value. Mo5+ appears to be in an axial symmetrical environment. In used samples. Three temperature maxima can be distinguished. the EPR spectra of catalyst pre-treated with MeOH and O2 and then treated with H2 . However. reveals a favorable balance to the reduced state. all of which are lower than the single maximum exhibited by catalyst 3:7 at 850 K. [9]. In a previous work [1]. These authors observed reduction of pure SnO2 above 663 K. at 643. The TPR of the co-precipitated catalysts exhibited large peaks of hydrogen consumption. Additionally. For catalyst 7:3. it is not possible to determine when the MoO3 reduction finished and the SnO2 reduction began. [9] on the formation of Mo5+ when molybdenum is impregnated on Sn. which are characterized by their low surface areas. showed that the Mo5+ signal remains almost constant. the reduction of these massive catalysts. Thus. after H2 treatment. indicating lower anisotropy related to a possible reordering of the coordination sphere of surface Mo5+ . and 0. Taking into account that these catalysts are evaluated in the selective oxidation of methanol at temperatures at 500 K or below. but with a lower amount of consumed hydrogen. The existence of the coupled pair Mo5+ –Mo6+ . Mo5+ might be part of the Mo6+ arrays in its crystalline structure. is that interdispersion between MoO3 and SnO2 favors a superficial architecture in which the Sn-Mo interaction plays a major role. In the former. 0. it can be inferred that SnO2 facilitates that reduction. / Applied Catalysis A: General 205 (2001) 201–214 211 reported by Niwa et al. The EPR results indicate the presence of Mo5+ in the fresh catalysts. presumed necessary to maintain activity. The spectra obtained by EPR both for fresh and used samples indicate that the intensities of the signals attributed to paramagnetic species are similar. One first conclusion to be drawn from the SBET . Moreover. which is produced under reaction conditions. is very stable to subsequent reductions even under 5% H2 /N2 mixture. There exists a probable preferential ordering by close contact between phases. indicating that their reducibilities are strongly enhanced compared with the pure oxides. . According to these observations. is far to be quantitative. This observation would agree with reports by Niwa et al. In addition. It is surprising to observe from the EPR results that. From these data it is clear that the reducibilities of the massive (co-precipitated) catalysts are strongly enhanced respect to the pure oxides.N. Mo5+ . which is close to that obtained for catalyst 1:1 (843 K). and the combination of the tin and molybdenum oxides confers to the system different characteristics from those of pure phases separately. catalyst 7:3 presents a lower concentration of Mo5+ species than the one subjected to reaction (MeOH+O2 ). in spite of the treatment with hydrogen.195 nm. When the support is SnO2 . Pure MoO3 does not suffer an appreciable reduction with H2 neither does it exhibit signal by EPR. From these TPR data. on the other hand. any observation after the test reaction indicates changes in the surface. in which the reaction occurs.G. Niwa et al.195 nm bond. The maximum reduction temperature observed is different for the three catalysts and follows the order: T7:3 <T1:1 <T3:7 . a marked decrease of reduction temperature was observed. Since this is a very active catalyst. it could be thought that such activity is due to its structure. XRD and TPR results.167. Combination of these component oxides leads to higher activities and selectivities for partial oxidations as observed for other mixed oxide catalysts.173. we stated that SnO2 shows high deep oxidation activities. probably produced by the high calcination temperature [17]. there is a clear difference between fresh and used catalysts. observation by XAFS reveals that MoO3 keeps its original structure and the lengths of the Mo–O bonds of the MoO4 unit are 0. The TPR results indicate that the Mo load determines the system reducibility. Valente et al. the strength of the metal–oxygen bonds in these three catalysts should be significantly different. Although EPR is a bulk technique. [9] noted that when MoO3 is impregnated on alumina. This might indicate that. since two g values can be identified. the more valuable information is obtained from the reduction trends observed below 700–750 K. having the order 7:3>1:1>3:7.

The signal corresponding to Sn3+ was not observed in any of the catalysts. the formation of MF is significant for Mo loadings on SnO2 under 3%. According to Niwa et al. Catalysts 1:1 and 3:7. The partial conclusions derived from the EPR results might be summarized as follows: • In Sn-Mo catalysts. [9]. could have similar superficial architecture to that of until 3% Mo loadings.4 eV when it passes from Sn4+ to Sn2+ . which does not give an EPR signal. it can be postulated that the reaction of methanol ODH plays a major role in the redefinition of the catalytic surface final architecture.212 N. All the catalysts showed a Sn:Mo surface atomic ratio lower than those of the bulk. or its reduction to Mo4+ . at low Mo loadings. Okamoto et al. This phenomenon was not observed on the tin spectrum. the catalyst surface is strongly altered by the test reaction (methanol ODH). the Mo5+ produced under reaction conditions is very stable to subsequent reduction even under severe conditions. as indicated by the changes in the surface atomic ratio measured by XPS. It is evident that the results of this work cannot be interpreted independently of those obtained for mechanical mixtures. which would indicate a slight reduction of Mo6+ during the reaction. however. However. We found that at Mo:(Mo+Sn)=0. [18] for fresh catalysts. This suggests that there may be oxygen exchange between the supported oxide and the support.2 eV range. It has been observed [18] that Sn suffers a chemical shift of at least 0. it might be to Mo4+ .7 catalysts. With the help of XPS. the strength of the . indicating a surface enrichment of Mo. The binding energies are not modified in any of the analyzed catalysts after being tested in the methanol ODH reaction. after catalytic test. According to Niwa et al. on the other hand. This one can be actually observed by EPR. which induces a superficial enrichment of Sn without reaching the bulk values. ZrO2 and Al2 O3 supported MoO3 . even though the binding energy values are also independent of composition. [10]. we attempted to account for this surface change which does not appear to involve a solid state reaction but substantially modifies the physicochemical characteristics of the surface. the Mo–O bond in MoO3 supported on SnO2 and on Fe2 O3 . The first conclusion stated above would indicate the existence of a particular architecture at atomic level.5 atomic ratios. • At high Mo loadings. the characteristics are similar to those reported by Okamoto et al. It can be postulated that oxygen diffuses not in the SnO2 lattice but in the boundary between SnO2 and MoO3 . Mechanical mixtures of Sn and Mo oxides showed higher activities and selectivities than the pure oxides [1]. According to the above comments. It could be supposed that the catalysts studied in this paper which show significant MF yields. while loadings of 4% or above produce almost exclusively FA. reduction is more difficult.G. The Sn:Mo surface atomic ratio of used 3:7 catalyst is relatively close to that of bulk Sn:Mo atomic ratio. Line widths of level Mo3d show a small shoulder. • Sn facilitates reduction. which could be Mo5+ . / Applied Catalysis A: General 205 (2001) 201–214 The lower intensity of the EPR signal for 3:7 catalyst might indicate its greater stability to reduction. After catalytic test. is that of 7:3. differences in the preparation method contribute to the formation of a more crystalline MoO3 in close contact with SnO2 . the possibilities of Mo dissolution in the Sn lattice are low. or else. [18] for Mo:(Mo+Sn)=0. In these systems. is weaker than in TiO2 . In brief. A further partial conclusion to be proposed is that since no chemical shifts are detected for Sn (XPS). The strength of the Mo–O bond can be influenced by the metal–oxygen bond of the support. the only surface atomic ratio. Valente et al. the bond of oxygen to molybdenum may be the main specie responsible for alcohol dehydrogenation. which remains practically unaltered. [18] observed a similar behavior and attributed it to an exclusion effect due to MoO3 crystallization. since this reaction is very sensitive to operation conditions. they are ≈1 eV below those of pure molybdenum oxide. and when reduction occurs. Probably. For Mo 3d5/2 . a fast replacement in the reduced site from the support [19]. The shift in the maximum of BE Mo 3d5/2 for the binary catalysts with respect to pure oxides (from 233 to ≈232 eV) would indicate the formation of an intermediary between Mo6+ and Mo4+ . The binding energy values for Sn obtained by XPS were independent of the catalyst composition and matched the values for pure oxide SnO2 within a ±0. It must be made clear that this might not be so in terms of strictly defined compositions and that it is not easy to compare data obtained from methanol ODH. suffer major changes increasing the Sn:Mo surface atomic ratio. Our results for Sn:Mo surface atomic ratio obtained by XPS for used catalysts are close to those obtained by Okamoto et al.

The surfaces of the 1:1 and 3:7 catalysts. According to the strength of the sites. The close combination of SnO2 and MoO3 modifies the reactivity of the lattice oxygens and the reducibility of Mo ions. MeOH or some of its derivatives (FA) would be responsible for producing catalytically active sites (Mo5+ ) and impeding their reoxidation by O2 . molybdenum is probably included in the tin oxide lattice. In fact. Conclusions The ODH methanol reaction induces a reordering of the catalyst structure (EPR). considering that the combination of the metal oxides contributes to the modification of the acid properties. For Mo loadings above Sn:Mo=7:3. as indicated by the changes in the superficial atomic ratio measured by XPS. the surfaces are still enriched in Mo. overall. FA would be retained to form an intermediary that would finally be released as MF. Mo would segregate forming crystalline MoO3 and giving a more acidic catalyst capable of activating methanol by mechanisms other than ODH. the segregation of MoO3 both during the catalyst preparation process and after the reaction modifies the product distribution due to changes in the reaction mechanisms. Cδ+ –Oδ− –Hδ+ . Both the results from sequential feed of reagents and/or products and from EPR after MeOH and O2 treatment would indicate that the reaction is involved in regeneration of Mo5+ centers. In fact. However. If impregnated catalysts were used. It can be concluded that in catalysts with low Mo content. from FA with methoxy species contributed by MeOH. Molybdenum is probably included in the tin oxide lattice favoring the subsequent stability of the Mo5+ ions formed. which results in different catalytic behaviors. in these co-precipitated catalysts. 5. The formation of MF would take place by reaction in series. the presence of O2 notably increases the yield to MF. However. it was observed that dimerization practically does not contribute to MF formation and that MeOH is necessary for its formation. Finally. in an attempt to elucidate the behavior of the catalytic system under study.N. since it can be considered as a distorted form of MoO3 species. a series of tests were performed for catalyst Sn:Mo=7:3 with different feed sequences of reagents and products. The interaction between both elements and their relative proportions determine the crystalline ordering. The decomposition of IPA indicates that the catalyst possesses associated acid and basic sites and isolated acid sites From these results any clear correlation with methanol conversion or with the product distribution in the methanol ODH was found. it is clear the increase of the DME yield in 1:1 and 3:7 catalysts. compared to the bulk. The surface atomic ratios of fresh catalysts did not match the expected value from the bulk composition. which can be identified as reducible due to their low co-ordination number. therefore. Considering that MeOH is a molecule with a highly electronegative oxygen atom and. oxygen is necessary for the MF formation mechanism. However. the catalytic properties. the reaction plays a major role in redefining the final architecture of the catalytic surface. it is susceptible to be activated by acid and basic sites of metallic oxides.G. Activity and selectivity could be described in terms of the acid–base properties of the catalyst. and therefore. after methanol ODH. The synthesis method here used results in high dispersion of Sn and Mo oxides. Valente et al. / Applied Catalysis A: General 205 (2001) 201–214 213 metal–oxygen bonds in the three catalysts here studied are different. By feeding FA. showing in all cases Mo enrichment. These results are coherent with the higher acidity observed by the IPA test reaction and ammonia TPD in these catalysts. the reducibility observed in the MoO3 on monolayer could be correlated with its structure. The possible surface transformation of the catalyst by the reaction constitutes the main limitation of . exhibits well differentiated electron donor and acceptor characteristics. after catalytic test. The DME is produced by dehydration in acid sites. without discarding a small contribution by FA dimerization (Tischenko). When high quantities of molybdenum are used. since at higher W/FV values MF selectivity is increased at the expense of FA. The absence of chemical shifts for Sn (XPS) suggests that the O–Mo bond is the main responsible for alcohol dehydrogenation. favoring the subsequent stability of the formed Mo5+ ions. showed enrichment in Sn when compared to the starting materials. This is corroborated by the activity measurements for different W/FV . except for the above mentioned of DME yield.

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