Sarayute
Chansai
*a,
Robbie
Burch
a,
Christopher
Hardacre
a,
Harry
Oh
b and
William S.
Epling
c
aCenTACat, School of Chemistry and Chemical Engineering, Queen's University Belfast, Belfast, BT9 5AG, N. Ireland, UK. E-mail: s.chansai@qub.ac.uk
bDepartment of Chemical Engineering, University of Waterloo, 200 University Ave W, Waterloo, ON, Canada
cDepartment of Chemical and Biomolecular Engineering, University of Houston, 4800 Calhoun Road, Houston, TX 77204, USA
First published on 21st June 2013
Enhancing the low temperature activity of diesel oxidation catalysts is important for cold-start conditions and the possible importance of nitrate species in oxidation reactions has been proposed although definitive evidence has not been reported. To investigate the possible role of surface nitrates, their adsorption and reactivity on a Pt-based diesel oxidation catalyst have been investigated using the Short Time on Stream (STOS) transient kinetic technique. The results provide for the first time definitive evidence for the oxidation of propene by some of these nitrate-type species.
Recent evidence14,15 has pointed to the possibility that NO2 is also involved in the oxidation of CO and hydrocarbons over the DOC. Under certain circumstances, NO2 has been shown to be preferentially consumed relative to O2 in the oxidation reaction.14,15 This leads to no NO2 observed until all, or most, of the CO and hydrocarbons are oxidized and it is only after they are combusted is NO2 observed. Katare and co-workers22 also showed that as a DOC is thermally aged, this effect becomes more pronounced since the activity of the catalyst for the oxidation of CO and hydrocarbon drops. The definitive elucidation of the role of species such as surface nitrates for alumina-supported catalysts lies in the difficulty in differentiating between active and spectator surface species that build up during catalyst exposure to reactants.23–25 As an example, Chansai et al.24 have observed nitrates species of different reactivities during H2-enhanced hydrocarbon SCR of NOx over Ag-based catalysts. Upon exposure to NOx, a significant amount of nitrate species can form on Pt/Al2O3 catalysts, and as mentioned above, some of these surface nitrates may participate in hydrocarbon oxidation. To confirm the involvement of some types of surface nitrates, the Short Time on Stream (STOS) DRIFTS technique23–25 was used to study the mechanistic details of the reaction between surface nitrates and C3H6 during the oxidation of the hydrocarbon.
In situ DRIFTS measurements were performed with a Bruker Vertex 70 FTIR spectrometer equipped with a liquid N2-cooled detector. 25 mg of the 1.0% Pt/Al2O3 catalyst sample was placed in a ceramic crucible in the DRIFTS cell. The exit lines were connected to a Hiden Analytical HPR20 quadrupole mass spectrometer in order to monitor the changes of gas phase species.
Prior to the experiments, the catalyst was pre-treated by heating in Ar with a total flow rate of 50 cm3 min−1 up to 300 °C for 1 h and then cooled down in flowing Ar to 250 °C. The IR spectrum of the Pt/Al2O3 catalyst at 250 °C under flowing Ar was taken as a background. Two 4-way VICI valves were installed to allow us to switch between two gas mixtures. The first was used to switch between Ar and the gas feed and the second was used for switching between other gas components, for example, switching between NO + O2 and C3H6. Kr was used a tracer for the switching experiments. The concentrations of the reactants used were: 500 ppm NO, 5% O2, 500 ppm C3H6, 0.5% Kr (when added) and Ar balance. The total flow rate was 50 cm3 min−1.
Three different sets of transient switching experiments were performed. The first two sets of experiments were carried out using the short time on stream (STOS) technique.24,25 In these experiments the catalyst is only exposed to reactants for the shortest time possible (typically tens of seconds) so that any adsorption on the support is minimised and it is easier to distinguish between potential reactant intermediates, at or near the active metal, from those, mostly inactive, species which have similar infrared spectra, and are located at a larger distance from the active metal. In these STOS experiments we switched between NO–O2 and C3H6–Kr, or between NO–O2 and C3H6–O2–Kr. The catalyst was exposed to the NO–O2 gas feed for 1 min at 250 °C before performing fast cycling transient switches from one gas mixture to another every 1 min. For comparison, in a final set of experiments, we show a conventional long time on stream procedure using an NO–O2 feed for 90 min, after which Ar was used to purge for 5 min before replacing this with the C3H6 feed. This allows us to compare the results from a conventional long exposure experiment with those from a STOS experiment.
In all cases, the in situ DRIFTS spectra were recorded with a resolution of 4 cm−1 and with the accumulation of 16 scans every 10 s during transient switches. The DRIFTS spectra were analyzed by the OPUS software. For the gas phase analysis, the following mass-to-charge (m/z) ratios were monitored as a function of time: 27 (C3H6), 28 (N2 and CO), 30 (NO), 32 (O2), 44 (N2O and CO2), 46 (NO2) and 82 (Kr). The results for gaseous CO, N2 (m/z = 28), NO2 (m/z = 46) are not reported because; (1) the MS signal of m/z = 46 was not observed as NO2 nearly 100% fragments to m/z = 30 and therefore, the MS signal at m/z = 30 is assigned to either NO or NOx; and (2) because CO2 (m/z = 44) is formed throughout the experiments and can be fragmented into m/z = 28 which then severely overlaps with the signals for CO and N2.
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Fig. 1 Changes in the gas phase species obtained from the STOS experiment when switching from NO + O2 to C3H6: outlet 14NOx and C3H6 concentrations as a function of time on stream during the 1st cycle of 60 s switches between NO–O2 and C3H6 over 1% Pt/Al2O3 at 250 °C. Feed conditions: 500 ppm NO, 500 ppm C3H6, 5% O2, Kr (when added) and Ar balance. |
The NO signal gradually increased over the course of the first minute and the total amount of NOx adsorbed was calculated to be 40.9 μmol gcat−1 (see Table 1). When the C3H6 was introduced, even in the absence of gaseous O2, it was found that the C3H6 was completely consumed for at least 10 s. The total amount of C3H6 consumed was calculated to be 18.9 μmol gcat−1 over the course of 1 min. At the same time, CO2 was formed and NO was released. The amount of NOx released and CO2 produced is 9.8 and 23.3 μmol gcat−1, respectively. The amount of CO2 production was significantly smaller than that calculated from the C3H6 consumption using the stoichiometric reaction of 3 moles of CO2 (56 μmol gcat−1) being formed from 1 mole of C3H6. As we shall see later from the DRIFTS experiments, some of the “missing” carbon can be accounted for by formation of CO and by carboxylate and formate species adsorbed on the support.
Cycle no. | NO + O2 | C3H6 | NO + O2 | C3H6 + O2 | ||||
---|---|---|---|---|---|---|---|---|
NOx adsorption | NOx desorption | C3H6 consumption | CO2 formation | NOx adsorption | NOx desorption | C3H6 consumption | CO2 formation | |
a All the calculated values are reported in μmol gcat−1. | ||||||||
1 | 40.9 | 9.8 | 18.9 | 23.3 | 39.8 | 7.2 | 46.4 | 127.9 |
10 | 32.8 | 10.1 | 18.6 | 23.9 | 26.2 | 7.7 | 46.4 | 129.4 |
These data indicate that some of the C3H6 or an intermediate species was adsorbed on the catalyst. Further evidence for this can be seen in Fig. 1 when replacing C3H6 with NO–O2. A sharp peak in CO2 production (31.5 μmol gcat−1) was observed which is due to the O2(g) + CxHy(ads) reaction, and the oxidation of CO(ads) and NCO(ads). In combination with the amount of CO2 formed during the NO–O2 pulse, this now accounts for all the carbon introduced during the C3H6 pulse.
The amount of NOx adsorbed in the second cycle (see Fig. 1) was less than the amount adsorbed in the first cycle, which indicates that not all of the NO that was adsorbed in the first cycle was removed by the propene. Nevertheless, a significant amount of NO still adsorbed in the second cycle. Therefore under these STOS conditions, the results indicate that C3H6 was indeed reacting with adsorbed NOx species. As well as reaction with the adsorbed NOx, some of the propene can react with PtOx formed on exposure to the NO–O2 mixture. It should be noted that in this switching apparatus, we can monitor the Kr switch to show that there is very little leakage of gaseous oxygen from the NO–O2 pulse to the C3H6 pulse and so very little of the C3H6 removed will be due to the O2 + C3H6 reaction. Also, Fig. 1 shows that CO2 formation took place for at least 40 s, compared with the disappearance of O2 which is rapid (<12 s (not shown)) on removal of the NO–O2 from the feed. Overall, we can confidently attribute some propene oxidation to a reaction with previously adsorbed species, of which a nitrate-type species is the most probable.
Clear confirmation that adsorbed NOx was removed when C3H6 was added is seen in Fig. 2, which shows the corresponding DRIFTS spectra for these STOS experiments. When the NO–O2 mixture was introduced to the catalyst for the first minute, the bands at 1230 cm−1 (nitrites) and at 1308 and 1545 cm−1 (nitrates) increased steadily.29–35 On the other hand, when the NO–O2 stream was replaced by C3H6 these bands decreased in intensity and essentially disappeared after 1 min of exposure to C3H6. It is observed that nitrates (1308 cm−1) react with C3H6 slightly faster than nitrites (1230 cm−1). This is probably due to the fact that in a short period of 1 min a small amount of nitrates are adsorbed weakly and very close to the Pt interfaces and then can react quickly when replacing the NO–O2 mixture with C3H6, whereas nitrites are formed quickly under the NO–O2 feed, allowing some to be adsorbed slightly further away from the Pt on the support.34,35 However, there are no observable changes in the band at 1545 cm−1 due to the fact that it is swamped with bands due to carboxylate-type species forming in the same region.33–36 New IR bands also appeared at 2016 and 2097, which are assigned to CO adsorbed on Pt,37–39 and at 2246 cm−1, which is assigned to adsorbed NCO species.40–42 Overall, it seems clear that C3H6 reacted with adsorbed NOx, which was probably in the form of a surface nitrate or nitrite.
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Fig. 2 Changes in the surface species corresponding to Fig. 1 obtained from the DRIFTS-MS system as a function of time on stream during the 1st cycle of 60 s switches. (A) Switch from Ar to NO + O2 and (B) switch from NO + O2 to C3H6 over 1% Pt/Al2O3 at 250 °C. Feed conditions: 500 ppm NO, 500 ppm C3H6, 5% O2, Kr (when added) and Ar balance. |
Repeating the STOS experiment for more of the two-minute cycles, the results in the data for the tenth cycle are shown in Fig. 3.
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Fig. 3 Changes in the gas phase species obtained from the STOS experiment when switching from NO + O2 to C3H6: outlet 14NOx and C3H6 concentrations as a function of time on stream during the 10th cycle of 60 s switches between NO–O2 and C3H6 over 1% Pt/Al2O3 at 250 °C. Feed conditions: 500 ppm NO, 500 ppm C3H6, 5% O2, Kr (when added) and Ar balance. |
Qualitatively, these kinetic results look similar to those seen for the first cycle, and almost identical to the results for the second cycle, as shown in Fig. 1, so again it appears that there is reaction between gaseous propene and adsorbed nitrate-type species. However, see Table 1, the calculated amount of NOx adsorbed from the NO–O2 feed is 32.8 μmol gcat−1 during the 10th cycle, compared with 40.9 μmol gcat−1 from the first cycle. Thus, as we increase the number of cycles we find that less nitrates are formed so presumably only a fraction of the adsorbed nitrates is being reduced by propene and the total amount of residual nitrate-type species has increased with each cycle. The amount of NOx released and the amount of C3H6 consumed remained about the same at 10.1 and 18.6 μmol gcat−1, respectively. However, the DRIFTS experiments presented in Fig. 4 for the 10th cycle appear to be contrast with this information.
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Fig. 4 Changes in the surface species corresponding to Fig. 3 and obtained from the DRIFTS-MS system as a function of time on stream during the 10th cycle of 60 s switches. (A) Switch from C3H6 to NO + O2 and (B) switch from NO + O2 to C3H6 over 1% Pt/Al2O3 at 250 °C. Feed conditions: 500 ppm NO, 500 ppm C3H6, 5% O2, Kr (when added) and Ar balance. |
The DRIFTS results in Fig. 4 show how the amount of retained surface nitrates changed as we increased the number of two-minute cycles. By the tenth two-minute cycle, there was essentially no change in the DRIFTS spectra. No significant changes in the nitrate bands were observed either on exposure to the NO–O2 mixture or to the C3H6. The surface had apparently become saturated with essentially inactive nitrate and nitrite species. The band at 1457 cm−1 and the unresolved bands between 1397 and 1370 cm−1, that are attributed to acetate-type species and formate-type species, respectively,33–36 showed a similar lack of change when the gas atmosphere was changed. Note, however, that the bands attributed to CO (2097 and 2016 cm−1) were removed by the NO–O2 pulse which is consistent with oxidation of intermediate CO adsorbed on the Pt and the reoxidation of the Pt during this pulse.
It is clear that exposure of the catalyst to the reaction mixtures for as little as 20 minutes in total took the experiment beyond the point where active surface species can be detected and their concentrations monitored. Already the active nitrates, as previously seen to be reactive under the STOS conditions and shown in Fig. 2, were swamped by spectroscopically similar inactive species, presumably due to nitrates that formed on the support but which are not close enough to the metal to be catalytically important. These species were inactive, or at least had an activity that was much lower than that found for the “active” intermediates observed in the first cycle. These STOS experiments showed that there was a reaction between adsorbed nitrate-type species and gaseous propene. However, the ability to detect and monitor these surface reactions was lost after only a few two-minute cycles of the reactants.
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Fig. 5 Changes in the gas phase species obtained from the STOS experiment when switching from NO + O2 to C3H6 + O2: outlet 14NOx and C3H6 concentrations as a function of time on stream during the 1st cycle of 60 s switches between NO–O2 and C3H6–O2 over Pt/Al2O3 at 250 °C. Feed conditions: 500 ppm NO, 500 ppm C3H6, 5% O2, Kr (when added) and Ar balance. |
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Fig. 6 Changes in the surface species corresponding to Fig. 5 and obtained from the DRIFTS-MS system as a function of time on stream during the 1st cycle of 60 s switches. (A) Switch from Ar to NO + O2 and (B) switch from NO + O2 to C3H6 + O2 over 1% Pt/Al2O3 at 250 °C. Feed conditions: 500 ppm NO, 500 ppm C3H6, 5% O2, Kr (when added) and Ar balance. |
Importantly, as shown in Table 1, the amount of NOx desorbed under the C3H6 + O2 feed in the first cycle when O2 was present with the C3H6 is 7.2 μmol gcat−1 which contrasts with the 9.8 μmol gcat−1 of NOx desorbed when O2 was not added to the C3H6. This would seem to indicate that there is less direct reaction between adsorbed NO and the C3H6 in the case where there is O2 in the gas phase. If correct, this would indicate that either the reoxidation of the Pt by O2, followed by the reaction between PtOx and C3H6 is faster than the direct reaction between C3H6 and adsorbed NOx, or that the nitrate species are more stable in the presence of O2. The latter is consistent with literature describing NOx adsorption on Pt/Ba/Al2O3 materials.43,44
Further evidence that there is still some reaction with adsorbed NOx can be seen in the DRIFTS spectra shown in Fig. 6. These results for the first two-minute cycle show that when replacing NO–O2 with C3H6–O2, surface nitrites (1230 cm−1) and nitrates (1308 cm−1) were removed. It was also observed that carboxylate peaks (1458 and 1583 cm−1) appeared from the partial oxidation of C3H6 by O2 or NOx. This demonstrates that nitrate stability is not limiting the reaction.
During the 10th cycle, Fig. 7 and Table 1 show that the amount of NOx adsorption (26.2 μmol gcat−1) under the NO–O2 feed becomes smaller due to more adsorbed NO being retained from the earlier cycles (compare cycle 1 in Fig. 5), and/or because of some residual oxidation of the Pt blocking NOx uptake.
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Fig. 7 Changes in the gas phase species obtained from the STOS experiment when switching from NO + O2 to C3H6 + O2: outlet 14NOx and C3H6 concentrations as a function of time on stream during the 10th cycle of 60 s switches between NO + O2 and C3H6 + O2 over 1% Pt/Al2O3 at 250 °C. Feed conditions: 500 ppm NO, 500 ppm C3H6, 5% O2, Kr (when added) and Ar balance. |
Again, it is seen that, when replacing with C3H6–O2, the NO signal slowly decreased and the amount of NOx desorbed was 7.7 μmol gcat−1, which is the same within experimental error to the amount seen in the first cycle. However, there was no significant change in the infrared bands for the nitrates as can be seen in Fig. 8.
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Fig. 8 Changes in the surface species corresponding to Fig. 7 and obtained from the DRIFTS-MS system as a function of time on stream during the 10th cycle of 60 s switches. (A) Switch from C3H6 + O2 to NO + O2 and (B) switch from NO + O2 to C3H6 + O2 over 1% Pt/Al2O3 at 250 °C. Feed conditions: 500 ppm NO, 500 ppm C3H6, 5% O2, Kr (when added) and Ar balance. |
Once again, in this case with O2 added to the C3H6, we find that even after as few as ten two-minute exposures to the reaction mixtures it becomes impossible to obtain any useful information from the DRIFTS results. On the other hand, using the STOS technique we can clearly demonstrate the removal of adsorbed nitrates, and the production of gaseous NOx, when a C3H6–O2 mixture was passed over a Pt catalyst that had previously been exposed to a NO–O2 mixture. These results also help clarify an apparent discrepancy in previous data.45 These showed for propene oxidation that the activation energy associated with nitrates as oxidant is significantly lower than that for O2 as oxidant but there were only slight improvements in the rate of propene oxidation when nitrates were present.45 These STOS data indicate that this is due to the relatively small amount of reactive nitrates (likely residing near the Pt) compared to the abundant nitrate species that form over the support.
In addition, Fig. 9A clearly shows that after switching to C3H6 both gas phase NOx and CO2 were rapidly released due to the interaction between adsorbed NOx and C3H6. However, it is important to note that although changes in the gas phase species were observed, which demonstrate that some adsorbed nitrate-type species were reacting with C3H6, the DRIFT spectra in Fig. 9B were unchanged even after 30 min exposure to C3H6. Clearly, under these “traditional” transient experimental conditions virtually all the infrared detectable nitrates and nitrites were inactive.
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Fig. 9 Changes in (A) gas phase and (B) surface species obtained from a “conventional” steady state (long time on stream) transient experiment as a function of time on stream over the course of 30 min under C3H6 flow over 1% Pt/Al2O3 at 250 °C. Feed conditions: 500 ppm NO, 500 ppm C3H6, 5% O2, Kr (when added) and Ar balance. |
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c3cy00349c |
This journal is © The Royal Society of Chemistry 2013 |