The noxious effect on the environment due to different volatile organic compounds (VOCs) vented in the manufacturing and

chemical industrial plants makes their removal imperative. Thus, complete elimination or, at least, abatement below the levels fixed by environmental regulations is a major concern in developed countries. The abatement of VOCs, present in concentrations as low as 1000 ppm in air streams, can be achieved by catalytic combustion, especially for not very high flow rates [1]. During the combustion, organics are converted into harmless products such as water vapour and carbon dioxide; in some cases hydrochloric acid among others is produced, depending on the source of the organic compound [217]. The catalytic combustion of VOCs can be achieved in the temperature range 300500 C, which is much lower than the temperatures required in the incineration, usually above 1000 C. The thermal (non-catalytic) Corresponding author. Tel.: +34-94-6014069; fax: +34-94-6014179. E-mail address: iaparerp@bi.ehu.es (P.L. Arias). URL: http://www.icp.csic.es/eac/index.htm. combustion is highly energy-demanding since it must often be supplemented with fuel to maintain a flame in a dilute VOCs gas stream. The most common catalysts employed for VOCs abatement are noble metals (Pt, Pd and Rh) and transition metal oxides (Mn2O3, NiO, Cr2O3, V2O5) dispersed on high surface area supports such as alumina, silica and titania [6,18,19]. Pt/Al2O3 catalysts are widely used because they provide high activity and good stability. Hinz et al. [20] reported propane oxidation with and without SO2 in the feed stream over 1% Pt/Al2O3 catalyst and observed that in the absence of SO2 propane tracts in the sequence propane > propene > ethane > CO. However, in the presence of SO2, the principal first step was the breaking of a CC bond producing ethane and a C1 fragment, which was oxidized further to CO and eventually CO2. Formaldehyde and methanol have been widely used in oxidation studies of VOCs because of their simple chemical structure which yields CO2, and water, depending on the catalyst type and reaction conditions. Partial oxidation of methanol over MoO3 was reported by Farneth et al. [21], who determined the Arrhenius parameters and the number 0926-3373/$ see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.apcatb.2004.01.024 84 M.C. Alvarez-Galvan et al. / Applied Catalysis B: Environmental 51 (2004) 8391 of active sites for the rate-limiting CH bond cleavage. The reaction rate derived with these parameters were used to predict reaction rates and resulted in good agreement with the reaction data. Recently, Yao et al. [22] studied the kinetics of methanol oxidation on silica in the temperature

range 400600 C and found that methanol was primarily oxidized to formaldehyde and then CO, while CO2 was formed mainly from the dehydrogenation of an intermediate formate species. In addition, the catalytic combustion of propane/methanol [23] and ethanol/methanol [24] mixtures have been investigated. The application of catalytic oxidation to control the emissions of VOCs is not obvious because it cannot achieve complete oxidation to yield the desired product (CO2) at low temperature. The development of new catalysts for low temperature complete oxidation of VOCs to produce CO2 is a subject of continuous interest. Although supported noble metals are preferred in general for their high activity, the efficiency of a catalysts depends to a great extent on the nature of the VOC to be combusted and the catalyst behaviour cannot be predicted a priori [13]. This is illustrated by the fact that some metal oxides can be more active than the noble metals [4]. In addition, noble metals are more expensive and less resistant to poisoning [3], and a combination of noble metals and metal oxides may make it possible to lower the amount of noble metals and favourable synergetic effects for activity and stability may also be achieved [25]. Any new development of catalytic methods for cleaning indoor air under conditions of low energy demand has to be analysed in detail in terms of the efficiency of the catalysts, reaction kinetics and stability. Formaldehyde is one of the most important indoor contaminant. It is produced in the production of isolating material, furniture, wood, exhaust gases, disinfectants, as additive in water-based paints and it is a constituent of tobacco smoke. Long-term exposition of humans to indoor air containing a few ppm of formaldehyde may cause adverse effects on health [10]. The present study provides information about methanol/ formaldehyde oxidation on Mn/Al2O3 and Pd-Mn/Al2O3 catalysts to provide a better understanding of the VOC oxidation catalysis. The main objective of the present work was to investigate the effectiveness of Mn/Al2O3 catalysts in the combustion of methanol/formaldehyde, and how their performance is affected by the incorporation of small amounts of palladium to the base Mn/Al2O3 composition. Activity is explained in terms of the manganese phases present on the surface and also of the dispersion degree of the active phases of manganese (and palladium) oxides. Pag 83 84 Applied Catalysis B: Environmental 51 (2004) 8391 Formaldehyde/methanol combustion on alumina-supported manganese-palladium oxide catalyst M.C. lvarez-Galvn a, B. Pawelec a, V.A. de la

Cinetica oxidarii formaldehidei Most studies involving reactions of HZCO(g) with metal surfaces have been carried dut in nltrahi~l vacuum (WV). Reaction of D,CO with Pt crystal surfaces was studied by Gdowski et al. [5] in the absence of oxygeti using molecular beam relaxation spectroscopy (MBRS). CO and D, were the only products and CO desorption was the rate-limiting step. The observations of Gdowski et +l. and others [6,7 ] * suggest a possible mechanism for H,CO oxidation on Pt - dissociation to CO(a) and H(a) followed by reaction with O(a) to produ& HzO(g) and COz(g). Alternative mechanisms might involve additio?l of atomic cixygeiz to HzCO or The desor@xx act&&ion ener,oy of 66 kJ mol-i used in our H&O coverage calculation represents the value reported -by Abbas and Madis [7j_for thi: 012 state of H&O, corrected

an HCO intermediate to produce H&00(a) or HCOO(a) species which decompose yielding CO,(g). An analogous mechanism has been proposed by Bowker and Madix [8] for acetaldehyde oxidation on Cu( 110) in UHV where temperature-programmed reaction spectrometry (TPRS) provided evidence for an adsorbed acetate intermediate which decomposed near 590 K yielding mostly CH4 and CO2. Our experiments were carried out at pressures above 10 Pa where spectroscopic identification of surface species is difficult on low-surface-area samples. Thus we rely on kinetic evidence, particutarly similarities between H,CO and CO oxidation kinetics, to propose the dissociative mechanism for H,CO oxidation_. Pag 89 ~imila~ties between H,CO and CO oxidation provide evidence for 3 mechanism of H,CO oxidation involving dissociation to CO(a) and H(a) followed by reaction with O(a) to form CO2 and H,O. Similarities include (1) low- and hip-temperature kinetic regimes with sharp transition between regimes, (2) a decrease in AT, with decreasing 9, (3) negative-order kinetics in the ~rboll-contain~~lg species (CO or H2CO) and positive-order kinetics in 02 in the low-temperature regime, (4) comparable apparent activation energies in the low-temperature regime. Rates were too low in the lolv-tem~rat~re regime to determine either she reaction orders or the activation energy for CO oxidation_

Thus, %-noted below, we rely on the large body of published CO oxidation data on Pt to draw analogies (3) and (4)The sharp transition between low- and bigh-temperature kinetic regimes is widely documented and well underst&od for CO oxidation on both bulk [13--X9]
and highly dispersed [20] Pt catalysts. Briefly, the 91

Pag 92.

Consider the steady-state oxidation for H,CO on Pt at fate rf&o at a given temperature in the regime of HzCO inhibition. We wish to determine the effective CO pressure PCo(eff) required for the same rate rCo (=rllzco) under otherwise identical reaction conditions. For identical rates, the surface will Ilave the same CO and 0 coverages regardless of whether CO or H,CO is used, assuming the dissociative mechanism for H,CO oxidation. Thus CO and H,CO osidation are assumed to differ ouly by the kinetics of reaction steps leading to CO(a), i.e. CO oxidation : $6 CO(g) + s- CO(a). If&O oxidatiott : (A.]) I I,CO(g) + s, iY,CO piCS \ $CW, IIZCO kdiss I-12CO(a) 2co* CO(a), (A-2) [Sl (A.3) [71 where S rcprcscuts au open site for adsorption and whcrc H(a) formed by dissociation of H,CO is assumed to react rapidly with O(a) to form H-,0. Furthermore, H,CO dissociation is assumed to reqiire only one S site. The model wily dcscribcs reaction at low (b and low tcmpcralures where the CO dcsorption rate is ncgligible and where CO? and ii20 are the only products olH,CO osidation. For both CO and t12CO osidation, the reactiou of CO(a) aud O(a) is given by CO(a) + O(a)2 CO,(g). (A .4) In tlic low-tcmpcrature regime, CO(a) is ia excess of other adsorbed species and 0,. the coverage of vacant sites, is approsimated by I - U,,. Baiance equations for CO(a) in steady-state CO oxidation and both CO(a) and H2CO(a) in steady-state H,CO oxidation can be derived from (A.l) and (A.3) (CO osidation) and (AZ). (A.3), and (A.4) (H,CO osidation). Each set of balance equations is solved for k;E,CO k:>O / (k dHeS& O PC0 (e w) = + k$Co 1 k3dS co

Pli,co: (A-5) where the numerator term k#~cok$~~o/(kj!,~~o -Ikg& o ) is the effective rate constant for dis pag 93 Volume 111, number 1,2 CHEMICAL PHYSICS LETTERS 26 October 1984 FO~ALDEHYD~ OXIDATION ON Pt: KINETIC EVIDENCE FOR ADSORBED CARBON MONOXIDE INTERMEDI[ATE R.W. MCCABE and D.F. McCREADY Physical CYierMtr~~D epartment. General Motors Research Laboratories. ItorrpIz,~ tlichigon4 8090-P&i-i. USA Received 12 July 1984

Cinetica oxidarii dimetileterului

Dimethyl ether (DME; CH3OCH3) can be produced from C1 feedstocks by one-step processes and is emerging as a replacement for liquefied petroleum gas (LPG) and diesel fuel in developing countries [1,2]. Several studies have described homogeneous DME pyrolysis and oxidation pathways that proceed via free-radical chain cycles [37]. These homogeneous reactions become detectable at 500600 K and form predominately CO, CH4, HCHO, and HCOOH at these low temperatures, with CO2 and H2O forming exclusively above 1000 K [8]. Catalytic routes decrease the temperature required for complete oxidation [9,10] and minimize NOx and CO emissions ubiquitous in homogeneous reactions, making it possible to use DME as a clean fuel in power generation, food preparation, and space * Corresponding author. E-mail address: iglesia@berkeley.edu (E. Iglesia). heating applications. Catalytic DME combustion on Pt clusters forms H2O and CO2 as the only detectable products at much lower temperatures (423 K) than homogeneous combustion (>1000 K); homogeneous pathways also form NOx at the higher temperatures required for complete combustion [8]. We have recently described the details of DME combustion pathways on supported Pt clusters [8]. DME combustion turnover rates are limited by CH bond activation in chemisorbed DME, a step that forms methoxy methyl intermediates, on site pairs consisting of chemisorbed oxygen atoms (O*) with vicinal vacancy sites (*) present on surfaces nearly saturated with O* [8]. DME turnover rates depend on reactant (DME, O2) and product (CO2, H2O) concentrations, as well as on Pt cluster size, because such factors determine the density of (O*)(*) site pairs required to abstract H atoms from

adsorbed DME molecules in kinetically relevant steps. Acidic supports, such as -Al2O3, lead to bifunctional pathways involving DME reactions with H2O formed in combustion steps 0021-9517/$ Pag 49 Table 1 Treatment conditions, metal dispersion, average crystallite diameter, and DME turnover rates (1% DME conversion)a Catalyst Treatment Metal dispersion Crystallite diameter (nm)b DME turnover ratec Dry air H2 0.8 wt% Pt/Al2O3 823 K, 5 h 723 K, 2 h 0.99 1.2 0.10 0.9 wt% Pt/Al2O3 823 K, 5 h 723 K, 2 h 0.75 1.6 0.19 0.9 wt% Pt/Al2O3 823 K, 5 h 873 K, 2 h 0.52 2.2 0.33 1.0 wt% Pt/ZrO2 823 K, 5 h 823 K, 2 h 0.42 2.7 0.51 1.0 wt% Pt/ZrO2 823 K, 5 h 873 K, 2 h 0.36 3.2 0.56 1.1 wt% Pt/ZrO2 823 K, 5 h 873 K, 2 h 0.44 2.5 0.31 0.4 wt% Pd/Al2O3 823 K, 5 h 773 K, 2 h 0.51 2.2 0.10 0.7 wt% Pd/Al2O3 823 K, 5 h 773 K, 2 h 0.39 2.9 0.11 0.7 wt% Pd/Al2O3 823 K, 5 h 973 K, 2 h 0.23 4.9 0.15 0.9 wt% Pd/ZrO2 823 K, 5 h 773 K, 2 h 0.17 6.5 0.15 0.9 wt% Rh/Al2O3 873 K, 5 h 873 K, 2 h 0.81 1.3 0.01 0.9 wt% Rh/Al2O3 1023 K, 5 h 873 K, 2 h 0.42 2.6 0.02 0.9 wt% Rh/Al2O3 1123 K, 5 h 873 K, 2 h 0.12 9.1 0.08 a 473 K, 2 kPa DME, 20 kPa O2, balance He. b Estimated from fractional metal dispersion assuming hemispherical clusters. c Moles DME/g atom surface metal s (1% DME conversion). to form CH3OH, which reacts with O2 much faster than DME on Pt clusters [11]. The identity and size of metal clusters strongly influence the rates and selectivities of catalytic reactions [1217]. Specifically, reactions of CH4 with H2O or CO2 on metal clusters, also limited by CH bond activation steps, occur with the highest turnover rates on Pd [12], whereas the reactivity of other noble metals decreases in the sequence Pt > Ir > Rh [13]. In contrast, Pt shows higher reactivity than Pd for combustion of higher hydrocarbons [1417]. Here we report DME combustion rates on Pd, Rh, and Pt clusters on -Al2O3 and ZrO2 supports with a range of metal dispersions (0.120.99) and cluster sizes (110 nm). DME combustion turnover rates increased with increasing cluster size on all catalysts. For a given metal dispersion, the turnover rates were highest on Pt clusters and lowest on Rh clusters. We also extend our previous mechanistic studies on Pt to Pd clusters by providing kinetic and isotopic evidence for the involvement of (O*)(*) site pairs in kinetically relevant steps involving the activation of CH bonds in molecularly adsorbed DME. (pag 50)

3.1. Dimethyl ether combustion rates on supported Pd clusters Pd, Rh, and Pt metal clusters chemisorb O2 dissociatively at ambient temperature [8,2022]. Pt clusters have been shown to be present as metals by X-ray absorption near-edge spectroscopy (XANES) during DME combustion at 473 K [8]. These conclusions are consistent with the reported bulk oxidation of Pt clusters to PtO2 in O2 at only above 750 K, because the formation of superficial oxide protects the bulk metal from further oxidation [8,2325]. But Pd and Rh clusters easily form their respective bulk oxides at the temperature (473 K) used here for DME catalytic combustion in the presence of O2 [2022]. In contrast, the reductant provided by the co-reactant decreases oxygen chemical potentials at surfaces and typically prevents the formation of bulk oxides. Surfaceenhanced Raman spectra during methanol oxidation on Pd and Rh ultrathin films (about three to five monolayers) on gold substrates [2628] at conditions similar to those used here for DME catalytic combustion (<573 K, 3 kPa CH3OH, 80 kPa O2) have shown that the bulk of those thin films remains metallic during catalysis. Therefore, we assume that Pd and Rh clusters also remained metallic during DME oxidation. Fig. 1 shows DME turnover rates as a function of residence time at 473 K on 0.9 wt% Pd/ZrO2 (0.17 dispersion) catalysts with different intrapellet dilution ratios at pellet diameters ranging from 250 to 450 m. Intrapellet dilution ratios (2:1 6:1) did not influence DME combustion rates, indicating that measured rates were not corrupted by intrapellet temperature or concentration gradients, ubiquitous in combustion catalysis. Much larger dilution ratios (50:1) were required for Pt-based catalysts, because of their higher reactivity in DME combustion reactions [8]. On Pt catalysts, the inhibition of combustion rates by H2O was rigorously excluded from the reported turnover rates by measuring rates as a function of residence time and extrapolating these rates to zero conversion. H2O inhibition effects on Pd-based catalysts were much stronger and detectable even at very low conversions (0.44.8%); as a result, they contributed to measured rates even after these rates were extrapolated to zero DME conversion. Strong inhibition by H2O also was prevalent for CH4 combustion on PdOx/ZrO2 catalysts, because of significant coverage by chemisorbed OH* intermediates formed via quasi-equilibrated dissociative chemisorption of H2O by products of combustion reactions [22]. Fig. 1. DME combustion turnover rate as a function of residence time on 0.9 wt% Pd/ZrO2 (60 mg, 0.17 dispersion) at 473 K for different SiO2:catalyst intrapellet dilution ratios. 2 kPa DME, 20 kPa O2, balance He; (!) 250450 m, 6:1; (2) 250450 m, 2:1; (dashed line) calculated DME turnover rates by interpolating average partial pressure of reactants and products using kinetic rate expressions obtained when OH* species are the most abundant surface intermediates. Scheme 1. Reaction pathways for DME combustion on supported Pt and Pd clusters.

The effects of DME, O2, and H2O concentrations on DME turnover rates on Pd clusters are described by a rate equation (Eq. (4)) derived from the sequence of elementary steps shown in Scheme 1, with the assumptions that (OH*) species are the most abundant surface intermediates (MASI) and that their coverage is determined by quasi-equilibrated hydroxyl recombination steps. The dashed line in Fig. 1 reflects the effects of residence time on DME conversion predicted by this model as a result of the concurrent changes in the prevailing H2O concentration with increasing DME conversion. The kinetic response of DME combustion rates to DME and O2 partial pressures was measured at 473 K on Pd/ZrO2 (0.9 wt%, 0.17 dispersion) with added H2O (5 kPa), so as to remove uncertainties introduced by water concentration gradients that otherwise would prevail along the catalyst bed. Fig. 2 shows the effects of DME and O2 pressures on combustion turnover rates measured at low DME conversions (<1.5%) and constant flow rates (330 cm3 g1 s1). For comparison, the figure also shows the kinetic response of DME combustion rates for 1.0 wt% Pt/ZrO2 (0.42 dispersion). On both catalysts, DME turnover rates were proportional to DME concentrations and nearly independent of O2 pressures, but this was the case for Pt based catalysts only when H2O was present at significant concentrations due to its presence in the DMEO2 reactant stream. DME turnover rates decreased with increasing H2O pressure on 0.9 wt% Pd/ZrO2 (Fig. 3). A negative kinetic order in H2O (0.8 0.2) was found by regressing the data (dashed curve) in Fig. 3 to a simple, albeit nonrigorous, power law kinetic equation. The dashed curves in Figs. 2 and 3 show that DME combustion turnover rates on Pd catalysts can be described accurately by r = k(DME) (1) 1(O2)0(H2O)1. This kinetic response to changes in DME, O2, and H2O concentrations was similar to that found for CH4 combustion rates The kinetic response of the DME combustion rate on Pd/ZrO2 to DME and O2 pressures was similar to that measured on Pt/ZrO2 with H2O present. These similarities suggest a mechanistic resemblance, but also a much stronger H2O inhibition effect on Pd than on Pt clusters. The elementary steps are similar to those previously proposed for Pt-based catalysts (Scheme 1, [8]) consist of a catalytic sequence in which oxygen atoms in DME interact with vacancies on Pd surfaces (*) (step 1.1). Vicinal oxygen species (O*) then abstract H atoms from chemisorbed DME molecules in kinetically relevant steps without any intervening DME dissociation steps that would form methoxide species (step 1.2); these hydrogen abstraction steps are consistent with isotopic measurements and with density functional theory calculations on Pt catalysts [8]. The

quasi-equilibrated desorption of OH* species from surfaces of Pd clusters to form water (step 1.3) and of chemisorbed CO2 (step 1.4) then complete a catalytic cycle by forming vacancies (*) required for DME chemisorption; these vacancies are ultimately replaced by chemisorbed oxygen in irreversible step 1.5. In turn, the reversible dissociation and strong binding of water molecules as OH* cause the strong kinetic inhibition observed. A pseudo-steady-state treatment of the sequence in Scheme 1 leads to the rate equation (2). The terms in the denominator reflect the relative concentrations of the various adsorbed species [*, O*, adsorbed DME (DME*), OH*, and CO2*]; derivation details have been given previously [8].When O* species are the most abundant surface intermediates, this equation becomes r = (3) 4.5(K1k2[DME])2 k5[O2] as found on Pt catalysts at low H2O concentrations [8]. On the Pd catalysts, the turnover rates did not obey this kinetic dependence, even without added H2O or at low DME conversions (<5%). The observed inhibition effects of water led us to consider OH* species as MASI, which led instead to a simplified version of Eq. (2), r = (4) K1k2K3[DME] [H2O] . Equation 2 o scrii din articol (pag 51 52) Journal of Catalysis 252 (2007) 4956 www.elsevier.com/locate/jcat Dimethyl ether combustion catalyzed by supported Pd, Rh, and Pt clusters: Site requirements and reaction pathways Akio Ishikawa, Enrique Iglesia Department of Chemical Engineering, University of California, Berkeley, CA 94720, USA Received 13 June 2007; revised 27 August 2007; accepted 28 August 2007 Abstract