J. Phys. Chem.

C 2010, 114, 2062120628

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Kinetics of NO + H+ + NO3- f NO2 + HNO2 on BaNa-Y: Evidence for a Diffusion-Limited A + B f 0 Reaction on a Surface
Aditya Savara and Eric Weitz*
Department of Chemistry and the Institute for Catalysis in Energy Processes, Northwestern UniVersity, 2145 Sheridan Road, EVanston, Illinois 60208, United States ReceiVed: June 3, 2010; ReVised Manuscript ReceiVed: October 6, 2010

The reaction NO + NO3- + H+ f NO2 + HNO2 on BaNa-Y, between 100 and 300 C, displays evidence for low dimensionality diffusion-limited kinetics that can be modeled as an A + B f 0 reaction (DLAB0 reaction), where H+ and NO3- are A and B, and the diffusion of H+ is rate-limiting. DLAB0 reactions are described by fractal kinetics when the reactants are conned to dimensionalities e4. Appropriate plots (alpha plots) of the depletion of surface nitrates versus time show evidence for a time regime in the kinetics that is termed the Zeldovich regime, during which reaction occurs at the edges of segregated regions of reactants. The Zeldovich regime manifests itself as a linear region in alpha plots, with a slope characteristic of the dimensionality to which the reactants are conned. Here alpha is 0.5. The end time of the Zeldovich regime, f, was obtained by spline-tting the kinetic data to extract the linear region of the alpha plot. Less reactive or unreactive nitrates remain at the end-time. The experimental data are consistent with the theoretical prediction that both f and [NO3-] at f are independent of [NO3-]0, the initial concentration of NO3-. There is an observed inverse dependence of f on [NO], which can be rationalized by incorporating [NO] as a coefcient, p, for the probability of a reaction following each encounter of H+ and NO3-, rather than directly into keff. The activation energy for the surface diffusion of H+ is calculated to be 30 ( 30 kJ/mol from the temperature dependence of f, which is within the expected range for such a process. Reaction-limited models with up to three site types were also considered, but did not provide physically realistic results. To our knowledge, this is only the second instance of kinetic evidence for a DLAB0 reaction on a surface, and the rst opportunity to experimentally test predictions for f for a chemical reaction.
I. Introduction Kinetic studies of catalytic processes are often performed in ow-reactors which simplify the reaction kinetics by operating under steady state conditions. However, these steady state conditions can also mask fundamental phenomena that can be more easily elucidated in time-dependent experiments in static reactors.1 For several decades there have been predictions that unusual cases of kinetic behavior could occur for reactions on surfaces due to a lack of rapid mixing of reactants.2-4 Here we present evidence of one such phenomenon which would not be apparent under steady-state conditions, kinetic evidence for a diffusion-limited A + B f 0 reaction. These types of reactions are annihilation/elimination reactions, where, in the present case, the 0 represents elimination because the products do not further participate in the reaction system. BaNa-Y and related heterogeneous catalysts have shown potential for practical application in on-board, low temperature, reduction of nitrogen oxides (NOx) from diesel vehicle exhaust.5 More details will be given about BaNa-Y (and zeolites in general) in section III. For the purposes of the introduction, BaNa-Y can be considered a solid upon which NOx reduction reactions can occur. HNO3 is present in all realistic low temperature NOx streams6,7 and, as shown in eq 1, it dissociatively adsorbs on the surfaces of BaNa-Y and related catalysts to produce H+ and NO3-5,8-11
Part of the Mark A. Ratner Festschrift. * To whom correspondence should be addressed. E-mail: weitz@ northwestern.edu.

HNO3(g) f NO3-(ads) + H+(ads)

(1)

We have previously shown that these thermally stable nitrates are reduced to less thermally stable nitrites by NO (eq 2), and that this reaction with NO plays a pivotal role in the overall mechanism for the catalytic reduction of NOx.9,12-14

NO(g) + NO3-(ads) + H+(ads) f NO2(g) + HNO2(g) (2)

An important topic is then to elucidate the kinetics of eq 2. To do this, we performed experiments in a static reactor as a function of temperature and initial nitrate coverage in the presence of an excess of NO, and monitored the depletion of surface nitrates with time. Two different batches of BaNa-Y zeolites were used, as well as a sample of Na-Y, another deNOx catalyst from the same homologous series of catalysts.15 Several kinetic models are considered. The kinetics of reaction 2 displays evidence for a lower dimensional diffusion-limited A + B f 0 reaction (DLAB0 reaction) on BaNa-Y. In this model, H+ and NO3- are A and B, and H+ is mobile. During depletion of reactants, theory and simulations predict that a region of time will arise termed the Zeldovich regime, during which reactant depletion leads to growing segregated regions of reactants, after which the reaction continues at the edges of these regions.3,4,16-19 It is important to note that the DLAB0 kinetics of the Zeldovich regime, and the periods leading up to the Zeldovich regime, occur even when only one of the reactants

10.1021/jp105110b 2010 American Chemical Society Published on Web 10/29/2010

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Savara and Weitz infrared transmission through the sample varies between experiments. Integrated areas of IR absorbance peaks were used as a quantitative measurement of the surface nitrates on BaNa-Y and Na-Y. The standard tangential baseline method was used for integration of surface nitrate peaks.31,32 Details of the peak integration procedure are included in the Supporting Information. Experiments were conducted at temperatures between 100 and 300 C. Initial nitrate coverages and NO pressures were varied by up to a factor of 10. The full ranges of conditions employed are provided in Table S.1 of the Supporting Information. III. Theory Relevant to the Kinetic Analysis A. Internal Surface Area of BaNa-Y. Details about the general properties and structures of zeolites can be found in texts on zeolites.33,34 However, there are several properties of BaNa-Y that are directly relevant to the present study. BaNa-Y is a faujasite zeolite, which consists of three-dimensional microporous aluminosilicate crystals where the pores have an average diameter of 7.4 33 - signicantly larger than the molecular diameters of the reactants and products in this study. The surface of BaNa-Y refers to the area of these internal pore walls, as this surface area is much larger than that of the exterior surface of the crystals. Values between 2 and 3 are common for the fractal dimension of the internal surface, and are usually determined by adsorption isotherms.35,36 The zeolite pores contain dispersed charge compensating cations at regular intervals - here, Ba2+ and Na+ - which are part of the crystal structure. In this study, the Ba2+ and Na+ ions are the binding sites for the nitrates.30 B. Expected Kinetics of Reaction in the Absence of Diffusion Limitations. When NO reduces the surface nitrates, the operative rate equation will be dependent on whether or not H+ is involved in the rate-limiting step. If the reaction rate is not diffusion-controlled and H+ is not involved in the rate limiting step, then the rate of depletion is expected to be given by

(A or B) is mobile.20-22 The Zeldovich regime is characterized by the appearance of a linear region in alpha plots (described Section III.C) with a slope, R, which is related to the number of dimensions that the reactants are conned to (for a 2D surface, R ) 0.5 in the Zeldovich regime). In the present study, the data in the R plots are spline-tted to obtain an end time for the Zeldovich regime, f, for various initial conditions. Theoretical predictions for the relationships between f and the concentration of the nitrates at time f can thus be tested. To our knowledge, the present study is the rst opportunity to experimentally test the predictions for f for a chemical reaction. Only a very limited number of systems have been found and characterized that exhibit DLAB0 kinetics in chemical reactions,23-28 of which only one has been a surface reaction.27,28 There has also been a recent paper in which the kinetics of a surface process was described via a different fractal kinetic model, and which involved mobility limitations for electron-hole transport.29 Several features are observed in the kinetics of reaction (eq 2) which deviate from the expectations for reaction-limited kinetics, and which are consistent with a DLAB0 model. These features are discussed explicitly as part of the kinetic analysis presented in this work. We note that it may also be possible for another diffusion limited model, in conjunction with very specic distributions of sites, to produce the observed features in the kinetics, but that such a situation would have to produce the observed kinetics over the wide variety of conditions studied. We are not aware of another kinetic model that produces the features observed in the kinetics reported in this study. In the experiments reported in this work, four parameters were varied: the NO concentration, the reaction temperature, the initial nitrate coverage, and the Ba/Na ratio (the cations upon which the nitrates adsorb). As will be discussed in detail, there is evidence that this system meets the mechanistic requirements for a DLAB0 reaction, and the data are consistent with the expected behavior for DLAB0 kinetics. II. Experimental Section Na-Y was obtained from Aldrich (Aldrich #33,444-8) with a nominal Si/Al ratio of 2.5. BaNa-Y was prepared by a 3-fold wet ion-exchange with a 0.1 M Ba(NO3)2 solution at ambient temperature. During each ion-exchange, the slurry was stirred for 24 h followed by vacuum ltration and rinsing with deionized water. Experiments were run using two BaNa-Y samples obtained by this method (BaNa-Y-1 and BaNa-Y2), and one Na-Y sample, which was used as obtained from Aldrich. Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) showed the BaNa-Y samples to have the composition: Si/Al ) 2.62 and Ba/Al ) 0.181 for BaNa-Y-1 and Si/Al ) 2.06 and Ba/Al ) 0.176 for BaNa-Y-2. The reaction cell and sample preparation are described elsewhere.5 The reaction setup allows in situ FTIR spectra to be recorded for both surface and gas phase species. Subsequent to sample preparation and calcining under vacuum to remove zeolitic water, the zeolite sample was heated/cooled to the desired temperature and kept at that temperature for >1 h prior to experiments. HNO3 gas (<2 Torr) was introduced to the reactor, forming chemisorbed surface nitrates on the zeolite.9,30 The remaining HNO3 gas, as well as weakly bound surface nitrates, were evacuated prior to experiments. Subsequently, a stoichiometric excess of NO gas was introduced to the reactor and in situ FTIR spectra were recorded to monitor the depletion of surface nitrates as a function of time. The noise level varies between measurements because the infrared beam path and

-d[NO3-]/dt ) k[NO][NO3-] ) kobs[NO3-]

(3)

If H+ is involved in the rate-limiting step, and the reaction is not diffusion-controlled, [H+] ) [NO3-] at all times by stoichiometry, and the rate of depletion is expected to be given by

-d[NO3-]/dt ) k[NO][H+][NO3-] ) kobs[NO3-]2

(4)
The observed kinetics do not match predictions based on either eq 3 or eq 4. It was possible to t the experimentally obtained nitrate depletion curves using either two parallel rstorder processes (each described by eq 3) and assuming that some nitrates are unreactive, or using a second-order process (eq 4) and assuming that some nitrates are unreactive - the results of these ts are shown in the Supporting Information. As shown in the Supporting Information, the temperature dependence of the rate constants obtained by tting the depletion of nitrates with either rst-order or second-order models (and assuming that not all nitrates are reactive) yields low, but not implausible activation energies for the reaction (<40 kJ/mol), but these ts result in pre-exponentials that are too small to be reective of a realistic elementary surface reaction (<102 s-1). For either a

Diffusion-Limited A + B f 0 Reaction rst-order or second-order surface reaction, a realistic preexponential using these units would fall in the range of 109-1019 s-1.37,38 Rather than being described by eq 3 and 4, at all temperatures studied, the observed kinetics for nitrate depletion are characteristic of a stretched exponential. A stretched exponential is given by exp(-ktc) rather than exp(-kt):39 a rapid depletion is observed at short times with a slower decrease at long times, relative to what would be expected from eqs 3 and 4. The stretched exponential form and the inability of rst-order or second-order models to adequately describe the nitrate depletion are both expected for diffusion-limited reactions, and the apparent low activation energy for reaction is also consistent with a diffusion-limited reaction. A Taylor-Weinberg type analysis40-42 was also performed for the rst-order and secondorder models, in which both the activation energy and preexponential for the rate constant are functions of the nitrate coverage. The results of this analysis (given in the Supporting Information) also support the conclusion that the reaction under study is diffusion-limited, as the Taylor-Weinberg analysis yielded unrealistically low preexponentials coupled with very low (in some cases even negative) activation energies, as a function of coverage. The Taylor-Weinberg analysis also showed that these parameters did not vary in a continuous fashion with nitrate coverage. As will be shown, the observed rate constant for nitrate depletion can instead be described as a function of the time elapsed from the start of reaction; which is consistent with a diffusion-limited model. There are two obvious possibilities that could lead to a diffusion-limited reaction: the diffusion of NO into the zeolite crystals or the surface diffusion of a reactant(s). The possibility that diffusion of NO into the zeolite is rate-limiting due to mass transport limitations of NO has previously been shown to be unlikely and would not explain the slow depletion of nitrates at very long times.43,44 The expected behavior for diffusion-limitations originating from the mobility of the surface species is described below. C. Expected Kinetics with Diffusion-Limited Depletion of Surface Species. For the observed kinetics to be limited by the diffusion of a reactant on the surface, at least one reactant must be mobile at the temperatures of this study. From eq 1, NO3and H+ are the two species produced on the catalyst surface from the dissociative adsorption of HNO3. These nitrates are bound to the Na+ and Ba2+ cations in Na-Y and BaNa-Y, respectively, whereas the H+ coordinates with framework oxygens of the zeolite lattice.9,11,45,46 The reverse of the adsorption process, the associative desorption of H+ + NO3-, has been estimated in our prior work to have an activation energy between 160 and 190 kJ/mol on BaNa-Y and between 100 and 200 kJ/mol on Na-Y.30,47 DFT calculations yield adsorption enthalpies in agreement with these desorption activation energies.11 These DFT calculations also yielded clues for the factors governing the strength of the adsorption energies. In the DFT calculations, the enthalpies for both molecular and dissociative adsorption of HNO3 were calculated, and it was found that in both cases the adsorption enthalpies were similar and that in both cases a chemical bond formed between a nitrate oxygen and the Ba2+ cation.11 The similarities between the two cases of molecular and dissociative adsorption, in terms of both the binding enthalpy and geometry, suggest that the energetics for adsorption is dominated by the interaction of the nitrate oxygens with Ba 2+ (e.g., > 150 kJ/mol), with a relatively small contribution from the H+ interaction with the zeolite framework. We thus assume that the nitrates are unlikely to have a low enough activation energy for diffusion to be mobile reactants

J. Phys. Chem. C, Vol. 114, No. 48, 2010 20623 at these temperatures (<40 kJ/mol), as empirically the activation energy for diffusion on metal oxides is typically 0.30-0.5 times the desorption activation energy.48 However, the protons on the surface, H+, may be capable of hopping between oxygen atoms of the zeolite framework with an activation energy that is compatible with what is observed (i.e., < 40 kJ/mol). These protons, which are produced from the dissociation of HNO3, might be expected to have a lower activation energy for hopping than what would be expected for the framework chargecompensating protons present in acid-zeolites, which are covalently bound to framework oxygens and have a hopping activation energy of between 20 and 90 kJ/mol.49-53 Thus, as reported in Section V.D, the protons generated in this study would be expected to have an activation energy for hopping which is low enough for proton mobility to occur at the temperatures employed in this work. If the protons from HNO3 dissociation are mobile enough to diffuse at the experimental temperatures and are a necessary participant in the reduction of nitrates by NO (eq 2), then the reduction mechanism can be described (for example) by

H++NO3- h complex complex + NO f HNO2 + NO2

(5) (6)

Other mechanistic variations which would also be consistent with DLAB0 kinetics are included in the Supporting Information (all variations include H+ being the mobile species, while NO3is immobile). Inclusion of [H+] into the rate equation then leads to an apparent second order dependence on nitrates, due to the fact that by stoichiometry [NO3-] ) [H+] at all times:

rate ) keff[NO][H+][NO3-] ) kobs[NO3-]2

(7)

We note that residual water should not introduce additional H+ as experimental data suggests that water is adsorbed molecularly on Na-Y,54 and DFT calculations also indicate that H2O dissociation is not favored on Ba-Y in the experimental temperature range.11 Subsequent to reaction (eq 6), the reaction products, HNO2 and NO2, rapidly leave the surface.9 The set of chemical reactions described above, eqs 5 and 6, is then an example of an A + B f 0 reaction: H+ and NO3- are A and B, the products are 0 because they leave the surface, and the effect of NO is incorporated into kobs. If the reaction is diffusion-limited by the mobility of reactants on a surface, the above situation becomes a special case of diffusion-limited fractal kinetics: a lower dimensional diffusion-limited A + B f 0 reaction (DLAB0 reaction) with [H+]0 ) [NO3-]0.4,16,55-58 DLAB0 kinetics will occur even if only H+ is mobile while NO3- remains xed at adsorption sites.20-22 After formation of H+ and NO3- on the surface, the H+ may diffuse and form a random initial distribution prior to introduction of NO. The physical picture that corresponds to DLAB0 reactions has been described elsewhere.3,16,17,59 In essence, segregated regions of A and B are formed in the absence of mixing as a result of reactive depletion of one reactant; that is, regions are formed where only A is left after all the B in that region has been depleted, and regions are formed where only B is left after all the A in that region has been depleted. These regions form when there is a lack of mixing due to mobility constraints, followed by continued reaction at the edges of the segregated regions.

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Savara and Weitz

Figure 1. Several R plots with slopes corresponding to R ) 0.5 provided for comparison. (a) BaNa-Y-1, [NO3-]0 ) 14.7 au, [NO] ) 1.2 Torr, 250 C. (b) BaNa-Y-1, [NO3-]0 ) 11.1 au, [NO] ) 13.4 Torr, 250 C. (c) BaNa-Y-2, [NO3-]0 ) 5.97 au, [NO] ) 1.9 Torr. (d) Na-Y, [NO3-]0 ) 6.63 au, [NO] ) 2.2. More alpha plots are provided in the Supporting Information.

In diffusion-limited reactions in unmixed systems, rate equations are often characterizable by a time dependent rate coefcient, k(t).3,4,60 The time-dependent rate coefcient can lead to a stretched exponential, in which the depletion of reactants is extremely slow at long times. In the case of a DLAB0 reaction with [H+]0 ) [NO3-]0, there is a time period during the reaction that is referred to as to as the Zeldovich regime, in which the rate is given by4,16-19

rate ) d[NO3-]/dt ) -k(t)[NO3-]2 ) -kobstR-1[NO3-]2 (8)

where kobstR-1 is the rate coefcient, t is the time, and kobs is the experimentally obtained pseudosecond-order rate constant for reaction. The variable R is characteristic of the system, and is given by R ) d/4 for d e 4, where d is the number of dimensions the reactants are restricted to.4,16-19 In general, faujasites have been found to have a surface fractal dimension between 1.5 and 2.5.61-64 Experiments with gas adsorption have found that d ) 2.03 for the Na-Y surface.62,63 The fractal dimensionality of the surface would not be expected to change substantially between BaNa-Y and Na-Y, as both the Ba cations and Na cations are small relative to the internal volume of the zeolite.65 Thus, we use d 2 for all samples, yielding R 0.5. Integrating eq 8 and manipulating yields

log10(1/[NO3-] - 1/[NO3-]0) ) R log10 t + constant

(9)
where [NO3-]0 is the initial nitrate coverage. Plotting log10(1/ [NO3-] - 1/[NO3-]0) vs log10(t) yields an R plot, where the slope is R. Figure 1 shows several examples of r plots obtained in this work, and r plots for the complete set of experiments are provided in the Supporting Information, with slopes of R ) 0.5 shown for comparison. In contrast, the kinetics expected

for a system with well-mixed reactants would exhibit alpha plots with a slope of 1.0.17 It is expected that a diffusion limited system will not exhibit the Zeldovich regime if the initial reactant concentration is below the critical concentration. In such a case an alpha plot would still pass through a point with a slope of 0.5, but in such a case we would not expect to see a prolonged roughly linear regime with a slope of 0.5. In the present case, the approach to a slope of 0 at very long times could be due to a small percentage of much more stable nitrates that react very slowly with NO at these temperatures. This possibility is discussed further in section V. Few systems have been found and characterized that exhibit DLAB0 chemical reactions,23-26 with only one of those cases occurring on a surface.27,28 In prior experimental studies23 and simulations,17,18 theoretical slopes were displayed for comparison alongside the data on R plots without a determination of the beginning and end-times of the Zeldovich regime by tting. In the current study, it was possible to t the R plots to obtain the end-times of the Zeldovich regime, f, to provide experimental conrmation of some theoretical predictions for a DLAB0 reaction. Theoretical work predicts there will be a transitional period during which the segregated regions must grow in size prior to the onset-time of the Zeldovich regime, 0.17,18 At long times, the segregated regions become depleted of reactants, and the diffusion-limited fractal kinetics ends. This corresponds to the end-time of the Zeldovich regime, f.17,18 In the present work, we are able to observe some of the theoretical predictions for f for the rst time for a surface chemical reaction. IV. Results Figure 1 shows several examples of r plots obtained in this work. Custom tting-programs which employed piecewise spline-tting methods, similar to the tangential lines approach utilized in the literature,17,66 were used to spline-t the linear region of the R plots in order to extract 0 and f. Fits were

Diffusion-Limited A + B f 0 Reaction

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TABLE 1: Relationships and Predictions for f17
relationship 1 2b 3 4
a 2

prediction f L /D f is independent of keff f is independent of [NO3-]0 [NO3-] at f is independent of [NO3-]0

a L is a length-scale characteristic of the system, related in this case to crystal size. D is the diffusion coefcient of H+ at a given temperature. b keff is the effective intrinsic rate constant for the reaction, keff is not identical to kobs in eqs 3 and 8.

Figure 2. Relationship between [NO3-]0 and f for all experiments.

Figure 3. Relationship between [NO] and f for all experiments.

a function of the experimental conditions (e.g., the NO concentration, the distribution of sites occupied, the sample used, and potentially other factors, will all affect the time and/or coverage at which the end-time occurs). However, f could be obtained with order-of-magnitude accuracy from tting of the data. Figure 2 shows the relationship between log10([NO3-]0/ a.u.) and log10(f), where a.u. are the units of the nitrate concentration, [NO3-]. Figure 3 shows the relationship between the log10([NO]/torr) and log10(f). Figure 4 shows a bar graph with the initial nitrate coverage and the corresponding nitrate coverage at the time of f. A table with these data and the conditions for each data point are provided in the Supporting Information. V. Discussion A. Theoretical Predictions for f. Theoretical derivations have yielded the predictions shown in Table 1 for f, which are listed as relationships 1-4.17 It is important to note that the relationships in Table 1 are only accurate at the order-of magnitude level, and that some scatter in the values for f is expected to occur as a result of differences in initial concentrations, differences in crystal sizes (lattice size), due to our tting method, and potentially due to differences between experiments (e.g., NO concentration, the distribution of sites occupied, the temperature, and the sample used). The details about possible experimental sources of scatter in the values observed for f, due to differences between samples, are described in the Supporting Information. Additionally, prior theoretical work has not been performed on the specic type of reaction mechanism in this study (eqs 5 and 6), and thus does not provide an explicit formulation for analysis which includes the role of [NO]. The role of [NO] will be discussed further in Section V.C. Figure 2 shows that, as predicted by relationship 3 of Table 1, f is independent of [NO3-]0 for each substrate studied: the slope of log10(f) vs log10([NO3-]0/a.u.) is 0. Figure S.6 of the Supporting Information shows log10(f) vs [NO3-]0/a.u.,

performed with an unconstrained slope (typically resulting in R between 0.4 and 0.6), as well as with a slope constrained to R ) 0.5 (details are provided in the Supporting Information). 0 could not be determined due to noise and uctuation at early times (the rst few seconds). The relatively high level of noise (scatter) at early times results from the small difference between the two terms in the argument of the log function: log10(1/[NO3-] - 1/[NO3-]0) during initial times, where the number of data points is too few for averaging (this aspect of the log-scale averaging required has been discussed previously23,67). The uctuations (waviness) which occur during the rst few seconds are due to the time required for equilibration of pressure and temperature after NO introduction. Finding an appropriate spline-tting procedure is not a trivial problem to solve for experimental data, which normally has some degree of noise associated with it. In the present case this is further complicated by the fact that (a) the signal-tonoise ratio varies as a function of time in the alpha plots (due to the decreasing signal from the reactant, the time-dependent averaging, and the log-scale axes in the alpha plots), (b) the signal-to-noise ratio changes between measurements, and (c) the piecewise nature of the alpha plot is expected to change as

Figure 4. Comparison between [NO3-]0 and [NO3-] at f for all experiments. The vertical bars represent [NO3-]0 next to their respective [NO3-] at f for each experiment (in a.u.), grouped by substrate and sorted by descending [NO3-]0. Light bars: [NO3-]0. Dark bars: [NO3-] at f.

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Savara and Weitz the relatively high end-time coverages to the existence of lessreactive nitrates. We note that this long-time approach to a slope of 0 is also consistent with simulations in which the immobile species has an initial concentration less than or equal to the mobile species21,22 (as is the case with the present interpretation). Thus, both effects go in the same direction, and the fact that the minority species are immobile (the nitrates) may also contribute to the observed long-time behavior in the alpha plots. Regarding the second issue: when starting with an initial coverage which is lower than the critical coverage, the Zeldovich regime should not be observed. In such cases, the alpha-plots should still pass through a slope of 0.5, but without a prolonged region at this slope. For BaNa-Y-1 and BaNa-Y2, several of the experiments had initial coverages beneath the effective end-time coverages (7 and 5 a.u., respectively). For these experiments, if the Zeldovich regime is absent, then we should see evidence of this since the ntf7 and ntf8 algorithms should yield systematically different values as a function of coverage. Yet, by all measures, the ntf7 and ntf8 tting algorithms return values for the lower coverage experiments which are in line with higher initial coverages. How can this be explained? The assumptions being made about the initial conditions have to be considered in more detail. As a rst approximation, the lower coverage experiments would be expected to have (a) an H+ concentration equal to the total NO3concentration and (b) it could be imagined that a nitrate distribution consisting almost entirely of nitrates on strongly binding sites, based on the rationale that such sites are more thermodynamically stable and thus would be lled rst. However, the second part of that assumption is not expected to be operative for the systems under study. Since the nitrates are not mobile, the distribution of nitrates will be determined by (1) where the nitric acid adsorbed rst (likely a stochastic distribution) and (2) affected by which nitrates desorb rst. Consequently, the lower coverages will not consist entirely of strongly bound nitrates (less reactive nitrates), and as long as a sufciently high coverage of active nitrates is present, the Zeldovich regime will still be observed. This is our interpretation: that the low coverage cases still include a sufciently high concentration of reactive nitrates to observe the Zeldovich regime, which is not surprising for this specic system. C. Effects of [NO] on f. The theoretical work17 which yielded the relations shown in Table 1 has not been performed for the type of reaction mechanism in this study (eqs 5 and 6) and thus does not provide a formulation for analysis which includes the role of [NO]. Given that [NO] can be incorporated into kobs in eq 8, relationship 2 of Table 1 might lead one to believe that f should be independent of [NO]. However, Figure 3 shows that the values obtained by tting for f are inversely dependent on [NO]. To investigate the source of this inverse dependence, we must look at the factors which govern the endtime of the Zeldovich regime. The end-time of the Zeldovich regime, f, occurs when the segregated regions reach a critical size, which is system specic (length-scale L in Rel. 1 of Table 1).17 As such, f is the time it takes for a reactant to clear out a segregated area comparable to this critical size, which is calculated based on order-ofmagnitude estimates related to the reactant diffusion radius, r.17,57,59,68-70 The equation for the root-mean-square-displacement is r21/2 ) (4Dt)1/2 for d )2,71 and the average displacement is given by r ) (4Dt)1/2 which gives rise to relationship 1 of Table 1 when r L.17,68,69 However, relationship 2 of Table 1 is arrived at by assuming that k f and that every encounter between A and B results in reaction (that the probability of

where it is also apparent that log10(f) is not correlated with [NO3-]0/a.u. The critical coverage at which the Zeldovich regime ends (and consequently when the end-time occurs) may be substrate dependent (based on relationship 1of Table 1), since the critical length-scale for the segregated regions, L, is expected to depend on substrate characteristics such as the crystallite size.17 Accordingly, there are differences in the concentrations at the end-time between substrates in Figure 2, but for each substrate, the slope is 0 in this log-log plot. In contrast, for a well-mixed system, an end-time for observable reaction would be expected to be dependent on the initial concentrations of reactants (e.g., the slope in Figure 2 would be positive if the reaction was pseudorst order). Figure 2 includes data points from multiple temperatures, and there was no obvious relationship between the f values and the temperature of experiment (not shown). Based on relationship 1 of Table 1, the lack of a signicant temperature dependence is consistent with the activation energy for H+ mobility being very low (e.g., <40 kJ/mol). This activation energy is further analyzed in Section V.D. From Rel. 4 of Table 1, the value of [NO3-] at f should be independent of [NO3-]0 for a given sample. This is observed experimentally in Figure 4, with effective end-time coverage values of 7, 5, and 3 a.u. for [NO3-] at f, for BaNa-Y1, BaNa-Y-2, and Na-1, respectively. This is an important experimental conrmation of the theoretical predictions: that at a xed time, f, the concentration of [NO3-] arrived at is the same, independent of the initial concentration, provided that the initial concentration is higher than the critical coverage. This is a distinction from what would occur in well-mixed systems, where performing multiple experiments with different initial concentrations would not result in two different experiments reaching identical reactant concentrations after a xed amount of time. It is worth noting that ts using reaction-limited rstorder or second-order kinetics with the assumption that less reactive nitrates remain at long times do not result in consistent values for the amount of remaining nitrates at the end-time (shown in the Supporting Information). This is in contrast to the data in Figure 4, where the DLAB0 model gives consistent values for the remaining nitrates at the end-times, provided that the initial coverage is greater than a critical coverage. B. Nitrates Remaining at the End Time. Two aspects of the quantity of nitrates at the end-time which should be commented on further are (1) the magnitude of the nitrate coverage observed at the end-time relative to the initial coverage and (2) the kinetic behavior observed when the initial coverage is lower than the effective end-time coverages in Figure 4 (7, 5, and 3 a.u., as described in the previous paragraph). Regarding the rst issue, typically, when DLAB0 kinetics are observed in simulations, the quantity of reactants at the endtime is one or more orders of magnitude lower than the initial concentration. In comparison to these simulations, the quantity of nitrates remaining at the end-times here is relatively high compared to the initial concentrations. However, as rst mentioned in Section III.C, there may be less-reactive nitrates remaining at the end-time. This explains the slope of 0 observed at long times in our alpha plots due to the fact that [H+]0 * [NO3-]0 when these less-reactive nitrates are subtracted.23 These less-reactive nitrates could be due to nitrates on more strongly binding sites (or less accessible sites). There is evidence from temperature programmed desorption for more stable surface nitrates on these catalysts (at similar site coverages as the remaining nitrates in this study), which have been interpreted as nitrates adsorbed on more strongly binding sites.30,47 Thus, we ascribe both the long-time behavior in the alpha-plots and

Diffusion-Limited A + B f 0 Reaction reaction, p, is 1). In this system, H+ and NO3- cannot react in the absence of NO (eq 2). Thus, the probability that any encounter between H+ and NO3- will be followed by reaction to produce the nal products (eqs 5 and 6), peff, must actually include [NO] as a coefcient. Though there is no work we are aware of that explicitly evaluates the effects of reaction probabilities on the end-time of the Zeldovich regime for a DLAB0 reaction, some theoretical work has been done on related types of systems for nite reaction probabilities.72-76 If the probability of reaction in an encounter is not 1, then the area of the segregated regions where NO3- has been removed at time t, due to the diffusion of H+, will be proportional to the effective probability of reaction, and thus to [NO] (peff ) p[NO]). In effect, a lower probability of reaction should result in a longer time-scale for the segregated regions to reach the length-scale L. Accordingly, f should be inversely proportional to [NO], as is observed. This is one example where diffusion-limited systems behave differently from reaction-limited systems, specically for the effective intrinsic rate constant for reaction, as peffk ) keff for reactionlimited kinetics, but peffk * keff for DLAB0 kinetics. D. Conditions Required for Observing DLAB0 Reactions. Surface processes involving associative diffusion limited desorption can be expected to display DLAB0 kinetics. As described in Section III.B, the H+ on the surface must be sufciently mobile at these temperatures for a DLAB0 mechanism to occur. It was possible to estimate the activation energy for diffusion using relationship 1 of Table 1 and the end times of the Zeldovich regime, f, yielding Ea) 30 ( 30 kJ/mol (see the Supporting Information for details). This activation energy is, as expected, low enough for H+ to be mobile at the experimental temperatures, and, as described in section III.B, it is near the lower end of the range for the activation energies for hopping of charge compensating protons in zeolites. Further, the mobility of the protons on the surface between sites is expected to be described by a random walk process. In previous studies, good agreement was found for random walk models in describing the hopping of reactants between surface sites for (1) bimolecular luminescence quenching in NaY77 and (2) excimer emission from bimolecular encounters of silanol-bound uorescent probes on silica.78 For proton hopping, the most chemically similar situation which we are aware of is the direct measurement of diffusion coefcients for surface protons hopping along rows of oxygens on TiO2.79 In the study of proton diffusion on TiO2, the time dependence of the displacement between geminal pairs was also found to be described by a 1D random walk. In addition to the requirements listed explicitly in Section III.B, another requirement to observe DLAB0 kinetics is adequate premixing of reactants A and B prior to the start of reaction (at time 0 of measurement). Ideally, the reactants could be premixed, and the reaction could subsequently be turned on. Several routes to achieving an on switch have been proposed. Recently, Monson et al. achieved an on switch by caging Ca2+ during premixing, and then photolyzing the cage molecules to initiate the reaction.23 Ovchinnikov et al. suggested utilizing special cases of dissociation reactions (C f A + B) which can be initiated by heat or photolysis, followed by cooling to suppress dissociation while monitoring the reverse reaction (association).80 Toussaint et al. suggested shifting an association equilibrium A + B h C toward the reactants by cooling, followed by raising the temperature.68 The present case fulls a fourth class of an on switch for a DLAB0 reaction: bimolecular reactions with a pre-equilibrium and a third reactant,

J. Phys. Chem. C, Vol. 114, No. 48, 2010 20627 in this case NO, which is involved either in the pre-equilibrium or in the rate-limiting step, whereby introduction of the third reactant after premixing acts as the on switch. VI. Conclusions The reduction of chemisorbed surface nitrates on BaNa-Y (and Na-Y) by NO

NO + NO3-+H+ f NO2 + HNO2

(2)

displays kinetic evidence for a diffusion-limited A + B f 0 reaction at temperatures between 100 and 300 C. In this analysis, the reaction is rate-limited by the surface diffusion of the H+, while the NO3- is immobile. Unreactive (or less rapidly reacting) nitrates are also present, presumably adsorbed on more strongly binding sites. The presence of linear regions in R plots with R 0.5 (gure 2), as predicted for a DLAB0 reaction on a surface with dimensionality of 2, provides evidence for the kinetic region termed the Zeldovich regime during which reaction occurs at the fringes of segregated regions of reactants. The end-times for the Zeldovich regime, f, was obtained through spline-tting of the alpha plots for different experimental conditions. The values obtained for f match the theoretical prediction that f is independent of [NO3-]0. As predicted by theory, the concentration of nitrates at time f is the same regardless of initial conditions, and thus also independent of [NO3-]0. There is an inverse dependence of f on [NO], which can be rationalized by including [NO] as a coefcient for the probability of reaction per H+ and NO3- encounter, p. The effect of [NO] on f is unlike that in reaction-limited kinetics. In diffusion-limited kinetics the effects of reaction probability cannot simply be incorporated as a multiplicative coefcient for the effective rate-constant, keff. The values obtained for f were used to calculate the activation energy for H+ diffusion, yielding 30 ( 30 kJ/mol, which is within the expected range. To our knowledge, this is the second study that provides kinetic evidence for a DLAB0 chemical reaction on a surface, and the rst opportunity to test theoretical predictions for f experimentally with a DLAB0 chemical reaction. Acknowledgment. This work was supported by the Chemical Sciences, Geosciences and Biosciences Division, Ofce of Basic Energy Sciences, Ofce of Science, U.S. Department of Energy (DE-FG02-03-ER15457), at the Northwestern University Institute for Catalysis in Energy Processes. A.S. thanks Steven Githens for aid during writing of the spline-tting programs. Supporting Information Available: Surface nitrate IR peak integration, the experimental conditions tested, the tting programs and tting results, and additional discussion about the pre-exponential and activation energy for diffusion. This material is available free of charge via the Internet at http://pubs.acs.org. References and Notes
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