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Abstract
A series of Mo2C catalysts have been investigated for the hydrogenation and ring opening of naphthalene. At 573 K and 3 MPa H2, bulk Mo2C
showed no selectivity for ring-opening products (ROP) and, although treating the bulk catalysts in oxygen increased stability and naphthalene
conversion, ROP selectivity remained low. Supporting the Mo2C on HY zeolites significantly increased the hydrogenation of naphthalene and the
subsequent formation of ROP, as compared to the HY zeolites alone or the bulk materials. ROP yields were dependent upon the HY zeolite
SiO2:Al2O3 ratio and the Mo2C loading, the optimum loading being dependent upon the zeolite acidity. The maximum ROP yield of 33 wt.% was
obtained with 7.4 wt.% Mo2C supported on HY zeolite of moderate acidity (SiO2:Al2O3 ratio of 12) and the yield is comparable to yields reported
for noble metal catalysts on acidic supports. The Mo2C/HY zeolite bifunctional catalysts are most effective for ring opening of naphthalene when
the acidity is adjusted to an intermediate level that limits deactivation and the Mo2C loading provides sufficient hydrogenation capability to achieve
high conversion to the primary product tetralin.
# 2007 Elsevier B.V. All rights reserved.
[10]). The acid function plays another important rolenamely respectively, were used as the supports. Prior to use, Y2, which
as a catalyst for isomerization reactions, especially C6 ! C5 was in the ammonia form, was calcined at 773 K for 3 h to
ring shrinkage since it is well established that hydrogenolysis of convert it to the hydrogen form. Y1 and Y3 were used as
C5 cycloparaffins is easier than C6 cycloparaffins [1]. supplied. After impregnation, the catalysts were dried at 373 K
Metal carbides and nitrides are known to have good for at least 20 h and then calcined at 773 K for 5 h. The calcined
hydrogenolysis activities and a number of studies have reported catalysts were placed in a quartz tubular reactor and heated at a
on their activity for various alkane hydrogenolysis reactions. rate of 5 K/min from room temperature to 973 K in
Neylon et al. [11] reported activities of Mo2N for n-butane 330 ml (STP)/min of H2/CH4 (1:1). The final temperature
hydrogenolysis similar to that of Pt-Sn/Al2O3. Activities of was held for 3 h before rapidly cooling the sample to room
Mo2C were lower. Other studies have reported on metal carbide temperature in a flow of H2 (150 ml (STP)/min). The catalyst
hydrogenolysis activities [12] and have shown that exposing was subsequently passivated by exposing it to a mixture of 2%
these catalysts to oxygen to produce an oxycarbide, results in a O2 in He at a flowrate of 100 ml (STP)/min for a period of 1 h.
reduction in catalyst hydrogenolysis activity in favor of These catalysts are designated Mo2C(i)/Yj, where i is the
isomerization [13,14]. These experiments were conducted nominal Mo content (wt.%) and j is the zeolite.
using cyclohexane and cyclopentane. Furthermore, ring
enlargement reactions (the reverse of that desired in SRO) 2.2. Catalyst characterization
have been shown to be catalysed by metal oxycarbides [13].
Metal oxycarbides have also been shown to have good The passivated catalysts were characterized by powder X-
selectivity for alkane reforming [15,16] via acid catalysis. ray diffraction (XRD), X-ray photoelectron spectroscopy
All of these reactions are of potential importance to selective (XPS), temperature-programmed desorption (TPD) of n-
ring opening of cycloparaffins, yet none of these studies have propylamine, CO pulse chemisorption and BET surface area
investigated the isomerization and/or hydrogenolysis of C5 and analysis. XRD analyses were performed on the passivated
C6 cycloparaffins. The metal carbides have been shown to be catalysts using a Siemens D500 Cu Ka X-ray source of
resistant to sulphur and have been proposed as HDN and HDS wavelength, 1.54 A. The analysis was performed using a scan
catalysts. At the lower temperature of SRO, it is expected that range of 3708 with a step size of 0.048 and step time of 2 s. The
these materials could operate in the presence of sulphur, but this phase identification was carried out after subtraction of the
needs to be proven experimentally. background using standard software. Crystallite size (dc)
In the present study, both bulk and supported Mo2C catalysts estimates were made using the Scherrer equation, dc = Kl/
have been investigated as catalysts for the vapor-phase b cos u where the constant K was taken to be 0.9, l is the
hydrogenation and SRO of naphthalene at 3.0 MPa H2. wavelength of radiation, b is the peak width in radians and u is
Naphthalene was chosen as a model reactant since it can the angle of diffraction.
undergo hydrogenation, isomerization and ring-opening reac- XPS analysis was done using a Leybold Max 200
tions. spectrometer using Al Ka radiation as the photon source,
generated at 15 kV and 20 mA. The pass energy was set at
2. Experimental 192 eV for the survey scan and at 48 eV for the narrow scan.
The catalysts were analysed after the passivation step without
2.1. Catalyst preparation further treatment and all XPS spectra were corrected to the C 1s
peak at 285.0 eV.
Bulk Mo2C was synthesized by temperature-programmed Transmission electron microscope (TEM) images were
reaction. Approximately 2 g of MoO3 (MoO3, +99.5%, Sigma generated using a Fei Tecnai 20 scanning transmission electron
Aldrich) was placed in a quartz tubular reactor and heated at a microscope operating at 200 kV. Catalyst samples were ground
rate of 5 K/min from room temperature to 973 K in to a fine powder, dispersed in ethanol and sonicated for 2 h. A
330 ml (STP)/min of H2/CH4 (1:1). The final temperature drop of the catalyst suspension was placed on a 200 mesh
was held for 3 h before rapidly cooling the sample to room copper grid coated with formvar and carbon, and left to dry
temperature in a flow of H2 (150 ml (STP)/min). The catalyst before analysis.
was subsequently passivated by exposing it to a mixture of 2% The catalyst Brnsted acid sites were titrated by n-propyl
O2 in He at a flowrate of 100 ml (STP)/min for a period of 17 h. amine (n-PA) temperature-programmed desorption. The TPD
Oxidized samples were also prepared by passivating the was conducted in a stainless steel reactor (i.d. = 9 mm)
catalyst at 623 K for 1 h (Mo2C-O623) and at 648 K for 1 h containing 0.5 g of catalyst that was pre-treated at 773 K for
(Mo2C-O648). 1 h in 10% H2 in Ar at a flowrate of 60 ml (STP)/min. The
Mo2C catalysts supported on HY zeolite, with Mo loadings sample was cooled to 383 K. A flow of He (30 ml/min)
of 2, 5, 7 and 10 wt.% were prepared by wet impregnation of the saturated at room temperature with n-propyl amine (Aldrich,
zeolite using an ammonium heptamolybdate tetrahydrate 99.8%) passed through heated gas lines to the reactor
(MoO3 81.083.0%, Sigma) aqueous solution containing the containing the pre-treated catalyst. After a 2 h adsorption at
required amount of Mo. Three commercial zeolite Y samples 383 K, the reactor was flushed in pure He at a flowrate of
(CBV720 (Y1), CBV712 (Y2), CBV400 (Y3), Zeolyst 30 ml (STP)/min for 1 h to ensure that physically adsorbed n-
International), with SiO2/Al2O3 ratios of 30, 12 and 5.1, PA was removed. The chemisorbed n-PA was then desorbed by
S.J. Ardakani et al. / Applied Catalysis A: General 324 (2007) 919 11
Table 1
Physico-chemical properties of the bulk molybdenum carbide catalysts
Catalyst Passivation SBET (m2/g) Crystallite size (nm) Total aciditya (mmol/g) CO uptake (mmol/g)
Time (h) Temperature (K)
Mo2C 17 300 8.5 9.3 0.020 1
Mo2C-O623 1 623 3.9 15.2 0.002 4
Mo2C-O648 1 648 1.9 14.4 0.002 2
a
Total acidity measured by TPD of n-propylamine.
properties of the bulk Mo2C are also shown in Table 1. Both support, the acidity remained relatively constant as the Mo
the CO chemisorption and total acidity as determined by n-PA loading increased.
TPD are expectedly low on all the bulk catalysts. The CO Table 2 also reports the surface composition of the zeolite-
adsorption data of Table 1 suggests that about 0.02% of the supported Mo2C catalysts, as determined by XPS. Note that as
total Mo is available at the surface of the bulk Mo2C. the Mo loading increased the surface Mo concentration also
Treatment in oxygen at elevated temperature decreased the increased. Furthermore, the Si/Al ratio varied according to the
acidity. Nonetheless for all bulk catalysts the acidity was very nominal composition of the zeolite support, but there was no
low. consistent trend in how the ratio changed as the Mo loading
X-ray diffractograms for the HY zeolites and the Mo2C increased, and this observation is consistent with the acidity
supported on the zeolites are presented in Fig. 2. These data data measured by n-PA TPD. The Mo 3d region of the XPS
show that the zeolite structure was preserved during the spectra are plotted in Figs. 3 and 4. In all cases, peaks at
carburization process and there was no discernable difference 228.7, 232.2232.5 and 235.9236.4 eV were evident. The
between the diffractograms obtained for the zeolites and the low BE peak at 228.7 eV was assigned to the Mo 3d5/2 BE
Mo2C supported on the zeolite. Furthermore, the presence of associated with Mo2C, in agreement with [17], whereas the
molybdenum carbide was not apparent from the XRD data. The higher BE peaks correspond to Mo 3d5/2 and 3d3/2 BE for
measured physico-chemical properties of the Mo2C(i)/Yj MoO3 [18,19]. The XPS data provide evidence for the
catalysts are shown in Table 2. The BET areas of the presence of Mo2C on the supported catalyst, and given that
Mo2C(i)/Yj catalysts all decreased with increased Mo loading. this phase was not apparent from the XRD diffractograms of
The total acidity of the zeolites followed the expected trend of the same catalysts, we conclude that the Mo2C was well
increased acidity (Y1 < Y2 < Y3) with decreasing SiO2/Al2O3 dispersed on the zeolite.
ratio (Y1 = 30; Y2 = 12; Y3 = 5.1), and upon addition of the The TEM data of Fig. 5 also show the presence of well-
Mo2C, a further decrease in acidity occurred. In all cases the dispersed Mo2C on the support. The estimated particle size of
acidity of the zeolite-supported Mo2C catalyst was much the Mo2C is 10 nm, although a relatively wide particle size
greater than the bulk catalysts. For any particular zeolite distribution is apparent.
Table 2
Physico-chemical properties of the zeolite-supported molybdenum carbide catalysts
Sample Mo2C loading nominal (wt.%) SBET (m2/g) Total aciditya (mmol/g) XPS
Mo/(Si + Al) (%) Si/Al
Zeolite Y1 711 0.84
Mo2C(2)/Y1 2.1 658 1.0 20.3
Mo2C(5)/Y1 5.3 574 0.75 2.5 13.4
Mo2C(7)/Y1 7.4 483 0.39 8.1 18.0
Zeolite Y2 726 1.48
Mo2C(2)/Y2 2.1 562 0.69 1.2 3.7
Mo2C(5)/Y2 5.3 500 0.78 1.7 5.6
Mo2C(7)/Y2 7.4 443 0.71 6.7 4.0
Mo2C(10)/Y2 10.6 344 0.62
Zeolite Y3 604 1.87
Mo2C(5)/Y3 5.3 497 0.78 2.8 1.7
a
Total acidity measured by TPD of n-propylamine.
Table 3
Naphthalene conversion and product selectivities of the bulk catalysts at 573 K and 3 MPa H2 after 2 and 5 h time-on-stream
Catalyst Conversion (wt.%) Selectivity
2h 5h Tetralin (wt.%) Decalin (wt.%) Other Products (wt.%)
2h 5h 2h 5h 2h 5h
Bulk Mo2C 91 51 94 99 6 1 0 0
Bulk Mo2C-O623 87 97 64 71 34 24 2 5
Bulk Mo2C-O648 91 97 71 81 22 12 7 7
Fig. 7. Naphthalene conversion (A) and product selectivities (BD) obtained on () zeolite Y2, (&) Mo2C(2)/Y2, (*) Mo2C(5)/Y2, (^) Mo2C(7)/Y2 and (~)
Mo2C(10)/Y2. Reaction conditions: 573 K, 3.0 MPa H2, SV = 7.27 h1, H2/naphthalene = 30 mol/mol.
S.J. Ardakani et al. / Applied Catalysis A: General 324 (2007) 919 15
Fig. 8. Naphthalene conversion (A) and product selectivities (BD) obtained on () zeolite Y1, (&) Mo2C(2)/Y1, (*) Mo2C(5)/Y1 and (^) Mo2C(7)/Y1. Reaction
conditions: 573 K, 3.0 MPa H2, SV = 7.27 h1, H2/naphthalene = 30 mol/mol.
Fig. 9. Naphthalene conversion (A) and product selectivities (BD) obtained on () zeolite Y3 and (*) Mo2C(5)/Y3. Reaction conditions: 573 K, 3.0 MPa H2,
SV = 7.27 h1, H2/naphthalene = 30 mol/mol.
16 S.J. Ardakani et al. / Applied Catalysis A: General 324 (2007) 919
Fig. 10. ROP yields at 2 and 5 h time-on-stream for Mo2C supported on (*) Y1, (&) Y2 and (~) Y3. Reaction conditions: 573 K, 3.0 MPa H2, SV = 7.27 h1, H2/
naphthalene = 30 mol/mol.
their selectivity will depend on the level of conversion, which in for all temperatures, indicative of a terminal product from a
the present work was dependent upon the catalyst, the process series of reactions. The above observations are consistent with a
conditions and the time-on-stream because of the significant reaction scheme, proposed in the literature [1], for naphthalene.
deactivation observed for some of the catalysts. Hence, the Accordingly, naphthalene undergoes hydrogenation as the first
effect of Mo2C loading among the different catalysts, shown in step toward ring opening. A subsequent set of hydrogenation,
Fig. 10, is based on ROP yield, defined as the product of the isomerization, hydrogenolysis and cracking reactions yield
naphthalene conversion and ROP selectivity. Fig. 10 compares ring-opening products, heavy products, cracked products and
the ROP yields among the different catalysts after 2 h time-on- coke. Note that although the rate of catalyst deactivation was
stream and 5 h time-on-stream. Overall, the optimum Mo2C dependent upon the operating conditions (SV and temperature),
loading was dependent upon the support, with the optimum similar trends to those shown in Fig. 11 were observed after the
loading generally increasing as the zeolite acidity increased, first 2 h time-on-stream. Consequently, the trends shown in
assuming the trend shown by the limited data for Y3 can be Fig. 11 do allow one to deduce the sequence of reactions that
extrapolated to higher loadings. For the catalysts examined in leads to the various products, even though the conversion data
the present study, the highest ROP yield occurred for the are marginally influenced by deactivation.
Mo2C(5)/Y1 and the Mo2C(7)/Y2 catalysts. Finally, the thio-resistence of Mo2C(5)/Y2 catalyst was
Fig. 11 shows the effect of reaction temperature and investigated by adding 1000 ppmw dibenzothiophene (DBT) to
residence time (1/SV in Fig. 11) on the naphthalene conversion the naphthalene feed and the results are shown in Fig. 12. The
and product distribution over the Mo2C(5)/Y1 catalyst, after 5 h data show that the naphthalene conversion decreased with
time-on-stream. The changes in space velocity (SV) were a addition of the DBT, whereas the ROP selectivity and tetralin
result of changes in both liquid and gas (H2) flow such that the selectivity was not much affected after 5 h time-on-stream.
H2:reactant ratio remained fixed. The data of Fig. 11 show that
at low temperature (553 K), the conversion increased with 4. Discussion
increased residence time, whereas at 573 and 613 K, the
conversion reached a plateau at higher residence times. The Although Mo2C catalysts have been shown to have good
conversion data are clearly influenced by the equilibrium hydrogenation and hydrogenolysis activities [12], the present
conversion established between naphthalene and tetralin at study shows that their ability as bulk catalysts to hydrogenate
higher temperature [6]. The decrease in tetralin selectivity with naphthalene is limited. Partial oxidation increased the
increased temperature and contact time, shown in Fig. 11, naphthalene hydrogenation rate (after 5 h time-on-stream),
confirmed this assertion. The ROP selectivity increased with but no ring-opening reactions occurred. The catalyst char-
temperature and the effect of residence time was most acterization data confirmed the presence of Mo2C and oxygen
significant at low temperature. The increased ROP selectivity treatment at elevated temperature all but removed the acidity.
with increased residence time observed at 553 K is in The acidity of the bulk catalysts was an order of magnitude
agreement with ROP being generated by secondary reactions. lower than that of the HY zeolites and this apparently limits
At higher temperature (>553 K), further reaction of ROP acid catalysed ring opening via C6 ! C5 isomerization and
occurred, decreasing selectivity to the desired product at higher hence no ROP were observed with the bulk catalysts.
residence time. Tetralin selectivity showed a decreasing trend Mo2C supported on HY zeolites significantly increased both
with temperature and as the contact time increased, the initial the hydrogenation and ring opening of naphthalene compared
hydrogenation of naphthalene to tetralin also decreased. The to the bulk materials. The presence of Mo2C in the supported
selectivity to heavy products also increased with residence time catalysts was confirmed by XPS, and the Mo2C particle size (as
S.J. Ardakani et al. / Applied Catalysis A: General 324 (2007) 919 17
Fig. 11. Effect of residence time (1/SV) on naphthalene conversion and product selectivities over the Mo2C(5)/Y1 catalyst at 5 h time-on-stream for (*) 553 K, (&)
573 K and (~) 613 K and 3.0 MPa H2, H2/naphthalene = 30 mol/mol.
determined by TEM) indicated that the crystallites were others on noble metal catalysts supported on various acidic
supported on the HY zeolite rather than anchored within the supports [410].
micro-pores of the zeolite. A similar conclusion has been The mechanism for naphthalene hydrogenation and ring
reported for Mo2C supported on ZSM-5 zeolite [20]. By using opening on bifunctional catalysts has been discussed in the
HY as the support, the acidity of the catalysts was increased. literature [1]. Hydrogenation can occur via conventional metal
The HY zeolites alone converted naphthalene to heavy products catalysed hydrogenation or by acid site induced hydrogenation
and tetralin, but the conversion decreased very rapidly, likely involving migration of spillover hydrogen from metal sites. The
due to coke formation that is a consequence of acid catalysed latter mechanism has been invoked to explain increased
polymerization reactions [1]. For all three HY zeolites, hydrogenation activity of metal catalysts on acidic supports.
naphthalene conversion, ring-opening selectivity and tetralin Subsequent reactions of tetralin include acid catalysed
selectivity increased significantly with the addition of the isomerization and ring opening or metal catalysed hydrogena-
Mo2C. Furthermore, there was a corresponding decrease in tion or hydrogenolysis. In the present study, all of the HY
selectivity to heavy products, consistent with the decrease in zeolites showed significant conversion of naphthalene, albeit
acidity observed upon addition of Mo2C to the HY zeolites. The with rapid catalyst deactivation and loss in conversion. The
comparison of data among the supports and the Mo2C catalysts, conversion was primarily to heavy products and tetralin, the
however, clearly shows that both the Mo2C and the HY zeolite latter most likely a consequence of hydride transfer reactions
are required to obtain significant catalyst activity and stability, linked to the acid catalysed polymerization reactions that lead
and that there is an optimum Mo loading that is dependent on to heavy products and coke deposits. In the presence of a
the HY zeolite. A moderate acidity provides the appropriate monofunctional acid catalyst and at typical cracking conditions
compromise between too much cracking or polymerization but the direct attack of a Brnsted acid site is assumed to be the
sufficient ring opening to obtain a catalyst with reasonable ring- initial activation step in the conversion of naphthalene [2123].
opening selectivity. The initial yield of ROP obtained on For the Mo2C(5)/Y1 catalyst, the change in tetralin
Mo2C(5)/Y1 and Mo2C(7)/Y2 is comparable to that reported by selectivity with residence time shown in the data of Fig. 11
18 S.J. Ardakani et al. / Applied Catalysis A: General 324 (2007) 919
Fig. 12. Naphthalene conversion and product selectivities over the Mo2C(5)/Y1 catalyst in the presence of DBT: (&) 0 ppm and (&) 1000 ppm DBT. Reaction
conditions: 573 K, 3.0 MPa H2, SV = 7.27 h1, H2/naphthalene = 30 mol/mol.
confirm that tetralin is a primary product and that ring-opening genolysis on the Mo2C. If deactivation is primarily associated
products and heavy products are formed by secondary reaction. with the catalyst acid sites because of acid catalysed
At 573 K, the ROP selectivity decreased as residence time polymerization reactions, then ROP selectivity would decrease
increased, a consequence of conversion of the ROP to HP. The as the acid sites are deactivated and the selectivity to tetralin
product distribution obtained was consistent with a bifunctional would increase as less teralin were converted to ROP.
catalyst reaction mechanism proposed by others using metal
catalysts supported on acidic zeolites [1]. 5. Conclusion
An interesting feature of the bifunctional catalysts is also
revealed by the deactivation profiles shown in Figs. 7 and 8. In Naphthalene conversion over Mo2C supported on HY
the case of HY zeolites, as the activity declined, the selectivity zeolite catalysts is shown to have ROP yields comparable to
to heavy products increased, whereas selectivity to tetralin and noble metal catalysts dispersed on acidic supports. The
ROP decreased with time-on-stream. In the case of the catalysts are bifunctional with hydrogenation/hydrogenolysis
Mo2C(i)/Zj catalysts, however, the rate of deactivation was far activity provided by the Mo2C and isomerization, ring opening,
lower than in the case of the corresponding HY zeolite, the cracking and polymerization occurring on acid sites associated
selectivity to tetralin increased and the heavy product with the HY zeolite. The acid strength and Mo loading are both
selectivity remained unchanged with time-on-stream. The data contributing factors to the control of product selectivity, with
suggest that in the presence of Mo2C, the hydrogenation of moderate acidity required to limit heavy product and coke
naphthalene to tetralin is readily achieved (as reported for metal formation. Preliminary data also showed that the thio-tolerance
catalysts) and this reaction is not much affected by coke of these catalysts was significant, with the Mo2C(5)/Z2 catalyst
formation on acid sites. The tetralin can undergo acid catalysed showing almost no effect in the presence of 1000 ppmw of DBT
isomerization and ring opening or hydrogenation and hydro- after 5 h time-on-stream.
S.J. Ardakani et al. / Applied Catalysis A: General 324 (2007) 919 19
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