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ELSEVIER Applied Catalysis A: General 201 (2000) 271-279 APPLIED i ; CATALYSIS GENERAL worwaleevierconoctapeata Heat of adsorption of carbon monoxide on a Ru/Al,03 catalyst using adsorption equilibrium conditions at high temperatures Olivier Dulaurent, Mostafa Nawdali, Abdennour Bourane, Daniel Bianchi* Laboratoire d’Applcaion de la Chimie 8 Enironnement (LACE), UMR S63, Universié Claude Bernard, Lyon, Bat. 308, “43 Bd du 11 Novembre 1918, 68622 Vilewranne, France Received 21 October 1999; received revised form 9 January 200; seeped 13 Jabuary 2000 Abstract ‘The adsorption of CO on areduced 3.5%RWA,Os catalyst has been studied by means of FTIR spectroscopy between 298 and 740 K ata constant paral pressure P,=1000 Pa, At 300 K, three adsorbed species were detected on the Ru particles: a linear CO species (strong IR band at 2087 em“), abridged CO species weak IR band at 1750 cm™) and a gem-600 K, the curve @=/(T,) isin very good agreement with Temkin's adsorption ‘model. Moreover, it is shown tha, in the range 300-720, the curve agrees well with an adsorption model considering (a) an immobile adsorbed species; and (b) 2 linear decrease in the heat of adsorption withthe increase in 8. This leads for the linear CO species to the heat of adsorption Za, at various coverages 8: from Ep=175 kJ mol”! at 6=0 to E\=115kI mol”! at 8=1, This procedure for the determination ofthe heat of adsorption of CO on Ru particles is simple (it requires a single isobar) and accurate (£51) mol), It constitutes a well adapted tool to study the modifications of this parameter with the ‘method of preparation ofthe catalyst (precursor, support, particle size). © 2000 Elsevier Science B.Y. Al rights reserved. Keywords: Carbon mocoxide; Cemisorpton; Ruthenium: FTIR; Hest of adSorton; Adsorption model 1. Introduction ‘The heats of adsorption of the adsorbed species (denoted as ) and their evolution with coverage 8 (denoted Ey with 0<8<1) constitute a source of characterization of the CO/metal system because the values of Es quantify the coverage of the sites under adsorption equilibrium. However, this parameter is rarely studied on supported metal catalysts due to experimental difficulties, For instance, temperature programmed desorption (TPD) methods that allow * Corresponding author Email ales: daniel bisneh@univ-yon.f (D. Bianchi) the determination of the desorption activation energy (equal to 6) on monocrystals is not well adapted for supported metal catalysts because it is difficult to achieve TPD experimental conditions free ofthe influ- ence of diffusion and readsorption [1]. This explains the interest in microcalorimetric methods [2,3], which provide either the integral or the differential heat of adsorption. However, in the case of the formation of, several CO adsorbed species, this method provides an average of the heats of adsorption. The Ey values can be also determined using the Clausius-Ciapeyron equation from the adsorbed CO quantities measured {or various adsorption pressures P, and temperatures Ty [45]. The accuracy of the experimental method 0826.860%008 ~ see front raster © 2000 Elsevier Sconce B.V. All rights reserved Pll: $0926-860X(00)00447-6 am ©. Dulawrent et. /Appied Catalysis A: General 201 (2000) 271-279 providing the adsorbed quamtties must be very high, otherwise the values of the heats of adsorption are strongly affected. Moreover, the analytical methods ‘must be able to differentiate the amount of each ad- sorbed species, otherwise, at best, only an average of the heats of adsorption can be obtained. This is the ‘case for monocrystals and supported model particles using IRAS spectroscopy. This analytical method per- mits characterization of each adsorbed CO species by their IR bands and the isosteric heats of adsorption of ‘well identified adsorbed species have besn determined {6,7]. We have shown previously [8] that an IR cell in transmission mode (which is an alternative to the DRIFT cell [9}) enables the study of the adsorbed CO species on supported metal catalysts at the adsorption equilibrium in wide pressure and temperature ranges. Jn the case of P-containing catalysts and for a linear CO species (8,10) it has been shown that the FTIR spectra show the evolution of @ as a function of Pa and Ta. The curves @=f(Ta) at various constant pressures Py enable the determination of the isosteric heats of adsorption of CO at various coverages [10]. More- ‘over, it has been shown [8,10] that these values are in ‘good agreement with those obtained from an adsorp- tion model which assumes (a) an immobile adsorbed CO species; and (b) that Zp decreases linearly with the increase in This last procedure to determine Eg which is very simple (a single isobar) and accurate (&+51d mol!) is applied in the present study to measure Ey for the linear CO species formed over a 3.5%RWAROs catalyst. The heats of adsorption of CO on Ru-containing solids have been studied less than on Pt and Pd-containing solids. The Ep values ‘ound in the present study are compared withthe data im the literature on Ru monocrystals and supported Ru catalysts. The present results and those obtained previously on Pt-containing catalysts [8,10] show that the described procedure can be easily applied to different supported metal catalysts 2. Experimental ‘A 35%RWAROs (in wi%) catalyst was pre- pared using the incipient wetness method. Alu- mina (Degussa C -AlzO3) was impregnated with an appropriate amount of an aqueous solution of 'RuNO(NOs)3-2H20 (Johnson Matthey), After drying for 24h at room temperature and then 12h at 383K, the solid was treated in air 12h at 623K, leading to a BET surface area of 90m? g-!. The metal content was obtained using the inductively coupled plasma technique after the dissolution of the catalyst with an acid solution. For the FTIR study, the catalyst was ‘compressed to form a disk (®=1.8cm, m=40-90mg) which was placed in the sample holder of a small internal volume stainless steel IR cell described else- where [8] allowing in situ teatments (293-900K) of the solid, at atmospheric pressure, with a gas flow rate in the range of 150-2000em? min-!, Be- fore the adsorption of CO, the solid was treated in situ 20cm? min~) according to the follow- ing procedure: He, 298K-+He, 383K-+Ha, 383K (Uh)+H, 523K, (1h)—>H, 713K (2h)+He, 713K (Gmin)->He, 298K. After this treatment, the metal- lic dispersion determined by ireversible hydrogen chemisorption at 383K using a volumetric method (ASAP 2000 Micromertic) and assuming a ratio HIM=I was 43%, in agreement with the data in the literature on supported Ru catalysts prepared with a ‘precursor without any chlorine [11,12]. The same pel- let of catalyst was used for several experiments, and before each CO adsorption, the pellet was treated ac- cording to the following procedure: He, 713K-+02, 713K (10min)->He, 713K (10min)->Ha, 713K (Ah)+He, 713K (0 min)-+He, 300K-> 1% CO/He (otal pressure=1 atm, flow rate=200cm? min~!)—» ‘increase in the edsorption temperature (5-10 K min!) up to 720K, while the FTIR spectra of the adsorbed species were recorded periodically. After the highest adsorption temperature, the solid was cooled down to a temperature T inthe presence of 1%CO/He and the spectrum was compared with the one recorded at a similar temperature inthe course of the heating stage. ‘This enabled the detection of the modifications of the catalyst during CO adsorption at high temperatures, such a the poisoning ofthe surface by carbon deposi- tion coming from the dissociation/dsproportionation reaction of CO: 2CO->Cass+CO2- 3. Results Fig. 1 shows the FTIR spectra recorded on the reduced 3.5%RWA}O3 catalyst in the course of the adsorption (196CO/He) in the range 300~720K. (0. Dalaurent eta. /Applied Coalysis A: General 201 (2000) 271-279 mm 7500 "2000 ‘Wavenumber (ex) Fig. 1. FTIR spectra recorded on 3.5%RWANOs in the couse ‘ofthe CO adsorption at various temperatures with an adsorption [essue Pes=1000Pa: (2) 300K; (0) 445K; (6) 618K; (4) 663K; (© 694K; © 708K. Spectrum a recorded at 300K shows a strong IR band 382047 em™"! and a weak IR band at 1750em~! which are ascribed to a linear (noted L) and a bridged (noted B) CO species, respectively [13-15]. A weak IR band is also detected at 2135em™' which must be ascribed to one of the two IR bands of the gemdicarbonyl or tmulicarbonyl species (denoted by G/M) probably ‘on Rut (16). The strong IR band of the L species ‘overlaps the second IR band of the G/M species at =2080em™! [16]. The G/M species are probably formed by the CO-induced oxidation of some Ru? sites (15,16). The increase in Ta (Fig. 1, spectrum b) leads to the increase in the intensity of the IR band ‘of the L species for temperatures lower than around 450K alongside a shift to 2039cm™! at 445 K, while ‘a shoulder is detected at 1960.cm-!. The IR bands of the B and GIM species decrease but without any sig- niffcant shift. For higher temperatures the recorded spectra lead to the following observations: (a) the IR band of the L species shifts to lower wavenumbers (2023¢m™! at 618K) without any change in its TR band area for T,<618K; (b) the IR band of the G/M species disappears at 558K without any shift; (c) the IR band area of the L species decreases for temper- atures higher than 618K alongside a shift to lower wavenumbers (2008cm™! at 663K, 1995em™! at 694K and 1990cm~! at 708K); (4) the position of the shoulder at 1960cm™" is not modified in the range ‘358-708 K; and (¢) the IR band of the B species dis- appears at 670K. The results in Fig. 1 show thatthe ruthenium surface is modified by CO adsorption (in- crease inthe intensity of the IR band of the L species and detection of the shoulder at 1960cm™"), The ori- gin of this modification is not within the scope of the present study, but it can be due, for instance, to a re- ‘construction of the surface of the ruthenium particles ‘or to the dissociation/disproportionation of CO lea ing to adsorbed carbon and may be adsorbed oxygen. If after the heating from 300 to 450K, the catalyst was cooled in the presence of 1%CO/He, the surface area of the IR band remained constant, indicating that the modifications of the surface were ireversible. Fig. 2 compares the FTIR spectra at 300K before heating to 708K in 1%CO/He (spectrum a) and after cooling from 708K in 1%CO/He (spectrum b). Some other IR bands at 1598, 1440 and 1230cm™ (not shown) are detected in spectrum b, atributed to adsorbed car- Donate species on the AlzOs support due to the COz ‘coming from the disproportionation reaction. Itcan be ‘observed (Fig. 2) thatthe carbon deposition leads to a shift ofthe L species IR band detected at 2020cm-! in spectrum b but has a limited influence on the IR band area (decrease by 5% as compared to the spectrum a). However, the IR band area decreases by 22% in comparison with the highest IR band area (for T,*500K). The absence of the IR bands of the G/M species in spectrum b indicates the disappearance of the sites in the course of the adsorption at high tem- peratures. An IR band at ~1960cm™! after adsorption of CO on Ru-containing solids is rarely mentioned | oa Absorbance 3000 1800 ‘Wavenumber(em-1) Fig. 2. Comparison ofthe FTIR spectra at 300K before and after ‘nang at 708K: (a) before: and (b) aftr eating mm (©. Dulawent ete. /Applied Catalysis A: General 201 (2000) 271-279 Absorbance venanber 1) Fig. 3. FTIR spectra on 3.5%RwAlO; during desorption in he- lium at 648K: (a) in he presence of 1%CO/He: (b}{6) during, Aesorption: (8) 305; (€) 3m; (2) Sin; (e) Orn [16]. Two IR bands at 2045 and 1965 cm™1 have been ‘observed after the decomposition in vacuum of sev- eral Ru carbonyl complexes adsorbed on Al2Os [17] and after the CO/H reaction on a 1%RWAIzO3 cata- Iyst [18]. On the present catalyst, the hydrogenation of the adsorbed CO species at 478K leads to the de- tection of two IR bands of similar intensities at 2045 and 1965cm™! [19]. These two IR bands have been ascribed to a complex structure involving Ru and the alumina support {17,18}. In Fig. 1, the shoulder at 1960¢m~" is not associated with a second IR band of similar intensity at a higher wavenumber. However, it is shown below (Fig. 3) that the desorption of the L species at high temperatures leads to the detec- tion of a weak IR band at 2047cm™} which may be associated with the shoulder at 1960cm~! and this probably indicates a new G/M species (16] formed in the course of CO adsorption at high temperatures. ‘The change, with the adsorption temperature Ts, in the coverage 6 of the Ru sites by the L species in the presence ofthe 1%CO/He mixture can be obtained, as. achieved previously on Pt-containing catalysts (8,10), using the ratio @=A/Ay, with A being the IR band area at Ta and Au being the highest IR band area and as- suming (2) a linear relationship between the intensity of the IR band and the quantity of the linear CO species ture as studied by Rasband and Hecker (20) on vari- ‘ous Rh/SiO2 catalysts. There is a controversy on the above assumption (a), In particular, on monocrystals, the linear relationship between the area of the IR band and the coverage is mainly observed for 9<0.5. How- ‘ever, on a PA/SiO> catalyst, Hicks et al. [21] have ob- served thatthe curve (integrated absorbance for the IR bands of adsorbed CO species)=f(the amount of CO ‘on the surface) was a straight line until the saturation ofthe surface. Using the analytical method of (20,21), Srinivas and Chuang [22] have observed on Rh/SiO2 catalysts thatthe IR absorption coefficients (Aco) for the linear and bridged CO species were approximately constant as a function of different parameters (the er- ror in calculating Aco was of 20%) and they used these values to determine the amount of each adsorbed species under hydroformylation reaction at 513K. In recent study [23] on a PUAI2Os catalyst and for an adsorption temperature >520K, we have observed the same values forthe coverage of the linear CO species using either FTIR measurements (with the above as- ‘sumptions) or a carbon mass balance with amass spec- trometer. The determination of @ was achieved with- out any difficulty on various Pt-containing catalysts, {8.10}. However, on the ruthenium catalyst, this pro- cedure cannot be applied without an initial treatment of the spectra due to the appearance ofthe shoulder at 1960em™" attributed to a new adsorbed species. Ona PVAIOs catalyst, we have observed [10] the appear- ‘ance of a new linear CO species during the adsorption ‘at high temperatures. However, on this solid, the two linear CO species have similar heats of adsorption. On the Ru surface, the adsorbed species revealed by the shoulder at 1960cm™! is more stable at high temper- ature than the L species. This is clearly observed in Fig. 3 which shows the evolution of the FTIR spectra at 648K during the desorption in He according to the switch 1%CO/He->He. It can be observed thet the IR band decreases rapidly during the first minutes (des- ‘orption of the L species), leading to the detection of a ‘weak IR band at 2047 cm? (spectrum ¢). This IR band alongside the IR band at 1960cm~' indicates probably the formation of a new G/M species [16] in the course of the CO adsorption. After 10min, the remaining IR bands decrease very slowly with time on stream in He (without any shift in their postions), indicating an adsorbed species with a very low rate of desorption. ‘This allows us to follow the evolution of the cover- ‘age of the L species with the adsorption temperature after subtraction of the contribution of the new G/M 0. Dulaurent eta. /Appied Coalysis A: General 201 (2000) 271-279 ns Absorbance ‘waveninter rt) Fig. 4. Teatment ofthe FTIR spectra before the determination of the coverage ofthe L spies: a) in ICOVHe at 445K; () afer desorption 10min in He a 648K; (2) afer the subracion 2—xb- species to the spectra in Fig, 1. For instance, spectrum ain Fig. 4 was recorded at 445K in the presence of 1%CO/He and spectrum b was recorded at 648 K after 10min in He (same as spectrum ein Fig. 3). Spectrum cin Fig. 4 was obtained by the subtraction (spectrum a-x(spectrum b)) where x is selected to eliminate the shoulder at 1960.cm™t. Note thatthe above procedure ‘can be used without any difficulty because the position of the IR band at 1960cm-" is constant whatever the temperature. Fig. 5 shows (curve a) the evolution of the coverage of the L species with Ta using the spec- tra in Fig, 1 and after the aforementioned subtraction procedure. The coverage 040.02 is obtained using as ‘Aut the surface area of the IR band at 500K. The in- creasing section of curve a corresponds tothe increase in the IR band of the L species due to the modifica- tions of the Ru particles. For 7,>620K, 8 decreases according toa straight line. Note that we have shown in Fig. 2 that there is a poisoning of the sites due to ‘carbon deposition after heating at 708K. Curve adoes ‘not take into account this decrease and the coverages at high adsorption temperatures are slightly underes- timated. A correction can be made using as Ay the surface area of the IR band recorded at 300K after cooling in 1%CO/He (Fig. 2). This leads to a higher coverage indicated in Fig. 5 by the symbol © for the adsorption temperature T,=708 K. The other values of @ are not corrected because we have not determined for each temperature the exact contribution of C de- position to the decrease in the IR band. However, if oats 4s CO species ‘Coverage ofthe ‘2 7 empire Fig. 5. Bvoluion ofthe coverage of the linear CO species with ‘he adsorption temperature (Py=10007a): @, (2) experimental data (D eomected coverage, Se the text (b) theoretical coverage sccording 10 the adsorption model with £y=115KImoI~" and Eq=16SEI mol"; c) theoreteal curve with Ey=115 Kh mol and pat 75ki ma after adsorption at 650K, the solid is cooled down to 500K, the spectra before and after the heating stage ae similar (no strong effect of C deposition), ‘The low intensity of the IR band of the B species does not allow us to determine with accuracy the evo- lution ofthe coverage ofthis species. Itcan, however, ‘be noted in Fig | thatthe IR band at 1750cm™ is no longer detected at around 663K. This is not due to C ‘deposition because this IR band is detected on spec- trum bin Fig, 2. The disappearance of the bridged CO species at 663 K clearly indicates thatthe heat of ad- sorption of this species is lower than the one of the linear CO species. The disappearance of the IR band of the GM species on spectrum b in Fig. 2 indicates thatthe decrease in the IR band during the increase in , is not only due to the heat of adsorption but also ‘due to the modifications ofthe catalyst. The adsorbed species formed in the course of the adsorption and characterized by the IR bands at 2047 and 1960em™! hs the highest heat of adsorption (almost stable in He ‘at 648K). This high stability has been previously re- ported (17] and we have noted, on our Ru catalyst, its low reactivity with hydrogen at T>S00K [19]. In Section 4, the results in Fig, 5 are used forthe determination of the heats of adsorption of the linear CO species at several coverages. 26 (0. Dularent et al “Applied Catalysis A: General 201 (2000) 271-279 4. Discussion 4.1, Heats of adsorption of the L species as a function ofthe coverage The curve O=f(7a) in Fig. 5is very similar to those observed previously on Pt-containing catalysts [8,10]. ‘We have shown that this curve corresponds to an ad- sorption model which considers a linear decrease in ease in 9 (Eg=Ep~a). This assump- ‘an expression of the coverage given by (8.10) and references therein): RTa, (1+ Lor o=2e"(GoR) 2 ‘where AE is the difference in the heats of adsorption at @=0 (Bp) and 9=1 (B}), and Lo and Ly are the adsorption coefficients at 00 and =. The Temkin equation (4,5) is obtained assuming (LoP,):>1 and (LiPa)«1 in expression (1): Ra @ = elnLoP) @ an expression of the adsorption coeffi : Lo=A exp(Eo/RTa)s (the pre-exponential factor Ais assumed independent of Ty) expression (2) leads to expression (3): a BE ‘This shows that, ata given partial pressure Pa. 6 varies linearly with T, according toa straight ine (the ‘Temkin approximations correspond to the linear frac- tion of the isobar as observed in Fig. 5). Expression (@) shows that the linear section of the isobar must intercept the @ axis in Fo/AE. Fig, 6 shows thet this value is Ep/SE=2.97:40.1 (straight line involving the corrected coverage @ at 708K) and indicates that there is an important difference between Eo and Ey. It can be assumed, as found on Pt catalysts [8,10], thatthe L species is immobile and thet the adsorption coefficient is provided by the statistical thermodynam- ‘es assuming the loss of three degrees of translation: @ R xnaro| Tht ae o Kami? TROP \ RT, with h being Planck's constant, k Bolztmann's con- stant, m the weight ofthe molecule (28% 10"? ky/6.02 po? Coverage ofthe linear CO species ‘Temperature (K) Fig. 6. Us of Temkin’ equation for the determination of Ey/AE: (©, (a experimental data (C conected coverage; ()staight Tne cousderng the near section ofthe isobar and determination of EAE from expression (3). x10%), Ey and Ey the activation energies of des- ‘orption and adsorption, respectively, while Ea—E, is the heat of adsorption. Expression (4) pro- vides a pre-exponential factor of 2.9x10~! Pav! at 600K. Considering expression (3), it can be observed that the slope of the straight line in Fig. 6 enables the determination of AZ assum- ing A=29x10-9Pav!: AB=SSKImol~!. This leads to Eo=(2.970.1)x55=1645k mol"! and E\=10925ksmol~!. ‘The above E; and Ep values are obtained using ‘Temkin's approximations. However, as achieved pre- viously on Pt catalysts [8,10], Zo and Ey can be determined without these approximations consider- ing (a) the experimental curve a in Fig. 4; (b) the theoretical coverage provided by expression (1); and (©) the adsorption coefficient of expression (4). It is only required that we find By and Eo leading the experimental data, Curve b in Fig. 5 is ob- tained using E=115 kJ mol"! and Ep=165 1 mol. Curve ¢ is obtained using Ey=115kSmot~! and Fy=175k5mol" to involve the corrected cover- age at 708K. It is this set of values (not strongly different than the one found with Temkin’s ap- proximations) which is compared with the data in the literature, Note that (a) £, and Eo lead to EglQE=175/(175-115)=2.14 in agreement with 2.97 determined above with expression (3); (b) the ©. Dulauren eta. Applied Catalysis A: General 201 (2000) 271-279 m ‘determination of Bp using the above procedure is very accurate because modification of few KImol~! (5k mol~!) of Eo or/and Ey gives a theoretical curve significantly different from the experimental data, as shown by the comparison of curves b and ¢ in Fig. 5 for a difference of 10kI mol"! on Eo. The following conclusions can be derived from the above discussion: the adsorption of the L species can bbe described by an adsorption model considering an bile adsorbed species with a heat of adsorption ‘decreasing with the increase in the coverage according to a linear relationship from Eo=175 KJ mol” at 8=0, to E,=115kJmol™! at @=1. These conclusions are compared with the data in the literature on various Ru-containing solids: monocrystals and supported Ru catalysts. However, it must be noted that, in both cases, this metal has been less studied as compared to Pt and Pa. 4.2. Comparison of the heat of adsorption of the L species with the data in the literature In a recent study, Rotaris etal. [24] determined the heat of adsorption of CO (L species) on Ru(1 010) ing the TPD method. Two mathematical treatments ‘of the TPD spectra at several coverages allowed the authors to find Ep and the pre-exponential factor v, assuming a first-order rate equation. They observed that the initial heat of adsorption (60.05) was Ep=140kI mol! with v=10"* s~!, Ep decreased al- most linearly with the increase in the coverage (as observed here) to E1=50kImol™!, alongside a de- crease in the pre-exponential v=10°s~! at 81. On the same monocrystal, Lauth et al. (25] reported for the L species Ho=150i3 mol~) and £~10013 mol! with v=10!5s-! (independent of @) in agreement with the values found in the present study. How- ever, in (25], the decrease from Ep to Ey was not a straight line Gump at 905), In the same study, the authors determined the isosteric heat of adsorption: 157kJmol™! in the range 8=0—-0.5. Note that, in 125}, the authors found that the heat of adsorption of the B species was around 90kImo!~!, a value lower than that of the L species in agreement withthe ‘observations in Fig 1 (the IR band at 1750cm™! dis- appears at a lower temperature than the IR band ofthe L species). On Ru(00 1, it was reported [26] thatthe isosteric heat of adsorption as well as the desorption activation energy (v=2x10"%s~!) of the L species were 160k mol! at 90, rising to 1754S mol”? at 0.3 and decreasing to 110k mol! st =07. It ap- ‘ears thatthe aforementioned Eo values, inthe range 140-160kI mol~!, are in teasonable agreement with Ey=175%Imol™ found in the present stud, taking ino account the differences (2) in the solids involved in the comparison and (b) in the analytical methods. ‘A study (25] reports 2 linearly decreasing profile for Ey with the increase in 8, as found inthis sud. ‘As mentioned in Section 1, the TPD procedure is ‘not well adapted to determine Ey on supported metal catalysts due to the difficulties of obtaining exper ‘mental conditions free of the influence of diffusion and readsorption {1}. This explains the interest in microcalorimetric methods to determine this param- eter (2). Londhe and Gupta (27] reported (using a Calvet-type heat flow microcalorimeter) the differen tial heat of adsorption of CO at low coverages over a fine Ru powder and over a 4.S%RwTiOp reduced catalyst at 475K: 120 and 130k) mol™, respectively, in agreement with previous studies summarized by TToyoshima and Somorjai [28]. Guerrero-Ruiz (29] using a similar procedure indicated a differential heat of adsorption of =140KImol™! at @%0 over Rufgraphited carbon black catalysis. The above Eo values 120-140K mol"! are significantly lower than Ey=175KImol~! found in the present study. This ray be explained considering that the mirocalori- metric methods provide an average of the heats of adsorption of the various adsorbed species formed daring CO adsorption (L, B and G/M species). In par- ticular, the contribution of the B species (901 mot! in (25]) must lead to heat of adsorption values lower using microcalorimetry 2s compared to the Ey val- ues of the L species. Note that the LIB ratio (not determined) isnot equal to the ratio between the in- tensites of the IR bands ofthe L and B species (Fig. 1). For instance, Vannice and Twu [30] have shown fon 2.15PVAI20s that the extinction coeficient a1, of the L species was higher than the eg of the B species with a ratio e1/ep=13. It isthe contribution Of the heat of adsorption of the B species which probably lead to Zp values lower using microcal metric measurements as compared to the Ep value determined for the L species in the present study. Moreover, as commented by Londhe and Gupta (27), the calorimetric measurements can be influenced mm (0. Dalewent et al /Applied Catalysis A: General 201 (2000) 271-279 ‘Tote 1 “Heats of adsorption of CO on various Ru-contsining solids at low and high coverages Sous Heat of adsorption eat of adsorption at ‘Analycal at ow coverage (RI mol igh coverage QKmot“!) method aco) 10 TeD (lop 3 Ru(10i0) 30 PD (106s! 23 u(10i0) 130 100 ‘TPD (05-4) pa Ry(001) 160 TPD @x10!8s-) 5) Ru(001) 10 Isosterc 5) 4 5%RUTIOn 10 Calorimetry Ra Ro powder 129 Calorimetry Ps Rac 40 Clorimeny ps) 35GRWANOS 115 us FTIR and adsorption model This work ‘Vale of fequeney factor. (Gn particular with the increase in the adsorption temperature) by other endothermic and exothermic surface reactions linked to the CO adsorption such 5 2T02+CO4—>Ti203+COrg, AH=+8010 mol! and 2COsis->Cats+COrg, AH=—180KI mol"? (27). Similarly, the various reactions involved in the corro- sive CO adsorption (formation of the GM species) (16] must contribute to the calorimetric signal. These aforementioned difficulties are prevented using the procedure described in the present study which is only influenced by the evolution of the sites (recon- struction of the Ru particles and poisoning by the C deposition). However, this problem can be taken into account as presented in Fig. 5 and it has been shown that neglecting the poisoning of the sites only leads to a slight underestimation (—10kJ mol™!) of Ep It seems thatthe slight discrepancy between the values of the present study and those of studies using calorimetric measurements may be explained by the fact that we determine the heat of adsorption of a specific adsorbed species (L species), while the mi- crocalorimetric measurement provides an average of the heats of adsorption of the various species formed by adsorption of CO. Table 1 summarizes the litera- ture data on the heats of adsorption of CO on various Ru-containing solids. In comelation with the catalytic activity of the Ru catalysts in the various reactions involving CO, it ‘must be underscored that the modifications of the Ru particles in the course of CO adsorption lead to a new adsorbed species (IR bands at 2047 and 1960cm~) with a heat of adsorption strongly higher than that of the adsorbed species formed at 300K. Using the present procedure and considering that the ‘coverage of this species is around 1 at 708K in the presence of the 1%CO/He mixture (weak decrease in the IR bands during the desorption in Fig. 6), its heat of adsorption Ej at @=1 must by higher than 150KI mol", 5. Conclusions ‘This study on the adsorption of CO on a 3.55%¢Ru/ ‘Alz0s catalyst has shown that the IR spectra of the adsorbed CO species recorded at the adsorption equilibrium conditions (P,=1000Pa, Ta in the range 300-720K) can be used to determine the evolution of the coverage @ of the linear CO species with Ta. ‘The curve 0=f(T,) allows us to determine the evolu- tion of the heat of adsorption Ep of this species with 8 using an adsorption model which considers (a) a linear decrease in Ea with the increase in 6; and (b) fan immobile adsorbed species. This model fits very well the experimental data with Ep=17510 mol~! and E,=115KI mol"! at 6=0 and @=1, respectively. ‘These values are in reasonable agreement with those found in the literature, taking into account the disad- vantages of each analytical method, ‘The procedure used in the present study based on an adsorption model is valid forthe determination of the heats of adsorption of various adsorbed species formed ‘on Pt-containing catalysts (linear CO species) [8,10] 0. Dulauren etal /Appied Cotes A: General 20! (2000) 271-279 29 and Pé-containing catalysts (linear and bridged CO species) [31] as well as on the present 3.5%Rw/AlOs catalyst. Acknowledgements ‘We acknowledge with pleasure the FAURECIA CCompagny, Bois sur Pré, Bavans, France, for is finan- cial support and the MERT (Ministre de Education Nationale, de la Recherche et de la Technologie) for the research fellowship of A. Bourane. References 1) RA, Demnia, RJ. Gort, J. Catal, 90 (1984) 3. 1B) N. Cardona Marine, 1.A. 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