Beruflich Dokumente
Kultur Dokumente
Abstract
Nickel- and palladiumnickel catalysts supported on silicaalumina have been studied in the simultaneous hydrogena-
tion of naphthalene and toluene. These catalysts were characterised by means of X-ray diffraction, CO chemisorption,
temperature-programmed reduction, NH3 temperature-programmed desorption, diffuse reflectance spectroscopy, Fourier
transform infrared spectroscopy of adsorbed CO and X-ray photoelectron spectroscopy techniques. All the catalysts studied
showed higher initial intrinsic activity in the hydrogenation of toluene than of naphthalene. Regarding the hydrogenation of
toluene, the 1Pd8Ni/SA sample displayed the strongest resistance to deactivation by coke precursors as compared with the
Ni-free 1Pd/SA catalyst. For the 1Pd8Ni catalyst, the characterisation data pointed not only to a high degree of reducibility
of nickel but also the greatest exposure of Pd species. Both findings appear to be related to the development of nickel hy-
drosilicate species at the support interface. Indeed, a better resistance towards deactivation was obtained by Pd incorporation
and by increasing Ni-loading.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Aromatics hydrogenation; Nickel and palladium catalysts; Silicaalumina support
0926-860X/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 4 8 9 - 1
18 V.L. Barrio et al. / Applied Catalysis A: General 242 (2003) 1730
Table 1
Chemical compositiona , textural propertiesb and metal dispersionc of Pd/SA, Ni/SA and NiPd/SA catalysts
Catalyst Metal contenta Dc (%) BETb (m2 /g) dp b (nm) VN2 b (cm3 (CN)g1 )
Ni (wt.%) Pd (wt.%)
Optima 3300DV instrument. Samples were solu- is an easily reducible oxide, even at room temperature,
bilised in a mixture of HF, HCl and HNO3 at 363 K all temperature-programmed reduction experiments
and homogenised in a microwave oven. Diffuse re- were carried out after sample (0.05 g) conditioning (air
flectance UV-Vis spectroscopy was performed on treatment at 473 K for 0.5 h) and further exposure to
the calcined samples using a Shimadzu-UV-2100 the 10% H2 /Ar mixture (air liquide, 99.996% purity;
spectrophotometer. The calcined samples were also flow 60 ml/min) at temperatures from 263 to 1173 K.
characterised by X-ray diffractometry according to Temperature was increased at a rate of 15 K/min and
the step-scanning procedure (step size 0.02 ), using a the amount of H2 consumed was determined with a
computerised Seifert 3000 diffractometer, with Cu K thermal conductivity detector (TCD). A cooling trap
( = 0.15406 nm) radiation, and a PW 2200 Bragg placed between the sample and the detector retained
Brentano /2 goniometer equipped with a bent the water formed during the reduction process.
graphite monochromator and an automatic slit. Scan- Temperature-programmed desorption of ammonia
ning 2 angles ranged from 10 to 70 . Line-broadening measurements were carried out with the same appara-
measurements were carried out using the NiO peak tus described for temperature-programmed reduction.
(43.35 in 2). The full-width at half-maximum The sample (0.050 g) was pretreated in an He (air liq-
(FWHM) of these peaks was corrected for instrumen- uide) stream at 383 K for 1 h and then reduced in a 10%
tal broadening (b). Diffuse reflectance spectra (DRS) H2 /Ar flow at 673 K for 1 h. After cooling down to
of the finely ground calcined samples were recorded 473 K, the reduced sample was ammonia-saturated in
in the 240800 nm range with a Shimadzu UV-2100 a stream of 5% NH3 /He (air liquide) flow (50 ml/min)
spectrophotometer, using BaSO4 as a reference and for 1 h. Thereafter, after catalyst equilibration in a he-
converted to the SchusterKubelkaMunk function. lium flow at 400 K for 0.5 h, the ammonia was des-
The textural properties of the calcined catalysts orbed using a linear heating rate of 10 K/min from 400
were evaluated from the N2 (air liquide, 99.994%) to 873 K. The water evolved was trapped in a KOH
adsorptiondesorption isotherms obtained at 77 K trap placed just before the TCD. In order to determine
over the whole range of relative pressures, using a the total acidity of the catalyst from its NH3 desorp-
Micromeritics ASAP-2000 apparatus, for samples tion profile, the area under the curve was integrated.
previously outgassed at 413 K for 18 h. A value of A semiquantitative comparison of the strength distri-
0.1620 nm2 was taken for the cross-section of the bution was achieved by Gaussian deconvolution of the
physically adsorbed N2 molecule. BET specific areas peaks. Medium and strong acidities were defined as
were computed from these isotherms by applying the areas under the peaks at the lowest and highest
the BET method over the 0.0050.25 P/P0 range. In desorption temperatures, respectively.
all cases, correlation coefficients above 0.999 were The infrared spectra of chemisorbed CO were
obtained. recorded with a Nicolet 5ZDX Fourier Transform
Volumetric CO chemisorption isotherms at 303 K spectrophotometer, working with a resolution of
were obtained in order to estimate metal dispersion. 4 cm1 over the entire spectral range and averaged
Before measurements, the sample was reduced under over 100 scans. The samples, in the form of self-
H2 at 673 K for 1 h and then outgassed at 105 mbar. supporting wafers (thickness ca. 10 mg/cm2 ), were
In order to avoid sintering of the Pd0 particles, the reduced in flowing hydrogen at 673 K for 1 h, and
1Pd sample was reduced at 573 K. After cooling the then outgassed under vacuum at the same tempera-
sample to room temperature, CO was admitted and ture for 1 h. After admission of CO at room tempera-
the adsorption isotherm was measured. The monolayer ture (30 mbar), the fraction of physically adsorbed
adsorption capacity was obtained by extrapolation to molecules was removed by outgassing at room temper-
zero-pressure the linear part of the isotherm. In the ature for 15 min. Net infrared spectra of chemisorbed
calculation of the dispersion, the stoichiometry of CO CO were obtained after subtraction of the background
to either Pd or Ni was assumed to be unity. spectrum of the solid.
Temperature-programmed reduction profiles were The photoelectron spectra of the fresh, reduced and
obtained on a semiautomatic Micromeritics TPD/TPR used catalysts were recorded on a VG Escalab 200R
2900 apparatus interfaced with a computer. Since PdO electron spectrometer equipped with a hemispherical
20 V.L. Barrio et al. / Applied Catalysis A: General 242 (2003) 1730
lower and Ni species interact strongly with the sup- in NiO generates the latter). Considering the support
port surface, re-dispersion of the nickel phase during composition (28% of Al2 O3 only) and calcination
consecutive impregnation with the palladium salt did temperature (723 K), it is more likely that the nickel
not occur. hydrosilicate would be formed [14], although the
formation of the nickel aluminate cannot be excluded.
3.3. UV-Vis diffuse reflectance analysis
3.4. Temperature-programmed reduction
In order to confirm the identity of the nickel
The temperature-programmed reduction profiles
species and the formation of nickel hydrosilicate, the
of the Ni/SA and PdNi/SA catalysts are shown
UV-Vis diffuse reflectance spectra of Ni/SA cata-
in Fig. 2A and B, respectively. The temperature-
lysts are obtained. Fig. 1 shows the UV-Vis diffuse
programmed reduction profile of the bare SA, also
reflectance spectroscopy profiles for the representa-
tive 4Ni and 8Ni catalysts in the visible range. Both
catalysts showed two distinctive major bands at 370
and 650 nm, and a minor one at around 530 nm.
Since a similar band was observed for NiO obtained
by decomposition of nickel nitrate [12], the band at
370 nm was attributed to the octahedral coordinated
Ni2+ ions. Considering the diffuse reflectance spec-
troscopy study of Houalla and Delmon [12] on the
Ni/silicaalumina catalyst with several alumina con-
tents, we ascribed a band at 650 nm as being due to
Ni2+ in a tetrahedral environment, and the band at
530 nm as being due to Ni3+ (the excess of oxygen
included for comparison, exhibits two overlapping catalysts (typical of NiO) shows a broader reduction
peaks of about 947 and 1087 K, associated with the re- peak, which is consistent with a more heterogeneous
duction of oxidic impurities. Temperature-programmed distribution of oxidic nickel species.
reduction profiles of the 4Ni and 8Ni catalysts show
a broad peak with a maximum at around 800 K with 3.5. Temperature-programmed desorption of
a shoulder around 900 K. Considering the UV-Vis ammonia
diffuse reflectance spectra (Fig. 1), the peak at 800 K
and its shoulder at around 900 K can tentatively be Ammonia temperature-programmed desorption is a
assigned to the reduction of Ni2+ species in the oc- commonly used technique for the titration of surface
tahedral and tetrahedral coordination, respectively, acid sites. It is generally accepted that ammonia is an
the latter interacting with the support more strongly excellent probe molecule for testing the acidic prop-
than the former. As can be seen, the increase in erties of solid catalysts since its strong basicity and
Ni content leads to an increase in the intensity of small molecular size allow the detection of acidic sites
the peaks around 800 K and 900 K. Thus, the ex- located even in very narrow pores [17]. The strength
tent of formation of a nickel hydrosilicate/aluminate of an acid site can be related to the corresponding
increases upon raising the Ni content, and this in- desorption temperature, while the total amount of
crease is larger for binary samples. For the 1Pd8Ni ammonia desorption after saturation coverage permits
sample, it is suggested that NiO particles placed quantification of the number of acid sites at the surface.
on the nickel hydrosilicate/aluminate phase are The temperature-programmed desorption profiles are
dominant. given in Fig. 3. Experimental curves were analysed by
From temperature-programme reduction data, the a mathematical fitting program and deconvoluted into
formation of PdNi alloy is excluded since after Pd Gaussian functions. The area of the components, ex-
incorporation onto Ni catalysts no lowering in the NiO pressed as moles of ammonia per gram of catalyst, is
reduction temperature did occur. This can be expected given in Table 2. Thus, temperature-programmed des-
considering that palladium has a lower surface tension orption peaks at two temperature ranges of 529640
and a larger atomic radius than Ni as well as the Ni and 700900 K can be ascribed to ammonia adsorbed
is in large excess compared to Pd. As a consequence, on middle- and high-strength acid sites, respectively.
Pd tends to be expelled out of the Ni matrix leading Middle-temperature acid sites were split into two
to a strong Pd segregation [9]. groups of acid sites: the first from 529 to 576 K and
Temperature-programmed reduction profiles of the the second ones from 601 to 640 K.
Pd-containing catalysts show an H2 -consumption In comparison with the SA support, the total
peak at 327 K and a negative one at 355 K. The for- acidity of the catalysts after metal incorporation
mer comes from the reduction of the Pd oxide species diminishes and strong acidity almost completely
[15] while the latter is usually ascribed to the desorp- disappears, due to the exchange of H+ by Ni2+
tion of hydrogen from the decomposition of a bulk
palladium hydride formed through H-diffusion into Table 2
the Pd crystallites [16]. For the binary systems both Total acidity and distribution of the acidic sites for Pd/SA, Ni/SA
peaks are much more intense than in the 1Pd sample, and PdNi/SA catalystsa
suggesting that the structure and/or location of the Catalyst Acid amount (mmol NH3 /gcat )
PdO phase changes in the presence of nickel. For the
T536576 K T601650 K T702711 K
1Pd4Ni catalyst, the maximum of this peak appears
at almost the same temperature, indicating a similar Bare SA 5.3 5.8
1Pd 3.8
particle size of PdO particles. For the 1Pd8Ni cat-
4Ni 3.1 3.4
alyst, the peak of Pd reduction is also larger than in 8Ni 2.9 4.3
its 1Pd4Ni counterpart. Moreover, the shift in the 1Pd4Ni 1.0 1.0
temperature maximum (350 versus 327 K) points to a 1Pd8Ni 0.7 1.5
stronger interaction between Pd species and the sup- a
As measured by the temperature-programmed desorption of
port. In addition, the second peak of the bimetallic ammonia.
V.L. Barrio et al. / Applied Catalysis A: General 242 (2003) 1730 23
Fig. 3. Normalised NH3 temperature-programmed desorption profiles of reduced 1Pd/SA, Ni/ASA, 1PdNi/SA catalysts and bare support.
For the sake of comparison, profiles have been deconvoluted.
24 V.L. Barrio et al. / Applied Catalysis A: General 242 (2003) 1730
during the impregnation step or to some interaction respectively [19]. The bridged form is characteristic
between the metals and H+ along the calcination of the carbonyl (Pd2 CO) species on the (1 0 0) planes
step. It was noted that this decrease did not correlate of the metal crystal [20]. In comparison with the 1Pd
with the amount of metal incorporated. As a general sample, the IR spectra of the 1Pd8Ni catalyst show
trend, the proportion of weak middle-temperature the less intense band shifted from 2107 to 2097 cm1 .
acid sites decreases with increasing metal contents Weakly adsorbed CO, giving a band in the region
whereas the strong middle-temperature acidity fol- 20702090 cm1 , has been reported for Ni/Al2 O3 and
lows the opposite trend. According to these results, the attributed to CO held by isolated Ni0 atoms or at Ni
middle-temperature acidity in the 536676 K range sites adjacent to oxygen atoms or oxide support [21].
might well be associated to acid sites on the support Considering TPR data, the most likely explanation is
and the middle-strength acidity in the 601650 K that 1Pd8Ni catalyst contains NiO crystallites, which
range could be ascribed to Brnsted-type acidity on are stabilized against reduction in hydrogen. There-
Ni [18]. Compared with the monometallic catalysts, fore, its band at 2097 cm1 may be attributed to CO
the bimetallic ones show the peak maximum of Ni2+ adsorbed at nickel hydrosilicate species.
acidity shifted toward a higher temperature, and this For 1Pd and 1Pd8Ni samples, the most apparent
shift increases with the increase in Ni contents. This difference in region 20631700 cm1 is the general
indicates a higher strength of this type of acidic site increase in the intensity of bands assigned to bridging/
in the bimetallic systems. multisite adsorption. The bands at 1987 and 1880 cm1
could be indicative of the two- and three-fold, respec-
3.6. Fourier transform infrared spectroscopy tively, bridging sites of the CO bonded on the Ni0
of the CO probe [22]. Similarly, the strong band at 1842 cm1 and
much weaker band at 1731 cm1 may be assigned to
The infrared spectra of adsorbed CO on the reduced CO multisite adsorbed on Pd0 or Ni0 phases.
(673 K, 1 h) 1Pd and 1Pd8Ni samples are shown
in Fig. 4. At saturation coverage, the spectra of the 3.7. X-ray photoelectron spectroscopy
1Pd sample displays an intense absorption band at
2107 cm1 and a less intense one at 1959 cm1 , cor- Photoelectron spectra of Si 2p, Al 2p, Ni 2p and Pd
responding to carbon monoxide bonded to the surface 3d core-levels were recorded from reduced and used
of palladium atoms in linear and bridged structures, samples. The binding energies and peak percentages
are summarised in Table 3. The binding energies of
Si 2p and Al 2p were observed in all the samples
at 74.5 and 102.5 eV, respectively. For the reduced
sample, the Ni 2p3/2 profile exhibits three peaks: one
at 852.8 eV, due to metallic Ni0 species; the second
one at 855.4 eV, ascribed to unreduced Ni2+ species,
and the third oneat ca. 860 eVis the satellite of the
second one. This satellite has also been considered for
quantification [23]. Additionally, the Pd 3d5/2 profile
displays a single peak at 335.0 eV, characteristic of
Pd0 [24]. Noticeably, for used Pd-containing catalysts
this peak is shifted toward higher binding energies
(from 335.0 to 335.8 eV). By contrast, in comparison
with the 1Pd4Ni sample, the peak indicative of Ni0
species in the 1Pd8Ni sample is shifted toward lower
binding energies (from 852.7 to 851.5 eV), indicating
a higher electron density in the reduced Ni species. It
Fig. 4. Fourier Transform infrared spectra of adsorbed CO for can also be noted that, with palladium incorporation,
1Pd/SA and 1Pd8Ni/SA catalysts. the reducibility of the nickel species increases from
V.L. Barrio et al. / Applied Catalysis A: General 242 (2003) 1730 25
Table 3
Binding energies (eV) of core electrons and surface atomic ratios of reduced (fresh) and used Pd/SA, Ni/SA and PdNi/SA catalystsa
Catalyst Ni 2p3/2 Pd 3d5/2 Ni/(Al + Si) atomic ratio Pd/(Al + Si) atomic ratio
Fig. 7. Effect of the reaction time on selectivity in the hydrogenation of naphthalene (tetralin and trans-decalin formation) and toluene
conversion on the 1Pd4Ni/SA catalyst. Reaction conditions as in Fig. 5.
V.L. Barrio et al. / Applied Catalysis A: General 242 (2003) 1730 27
Fig. 8. Effect of the reaction time on selectivity in the hydrogenation of naphthalene (tetralin and trans-decalin formation) and toluene
conversion on the 1Pd8Ni/SA catalyst. Reaction conditions as in Fig. 5.
For the hydrogenation of naphthalene at 548 K, the As seen in Fig. 7, the main product in the hydro-
selectivities toward tetralin and trans-decalin forma- genation of naphthalene over the 1Pd4Ni/SA cata-
tion for the most active 1Pd4Ni/SA, 1Pd8NiSA and lyst is tetralin. A similar type of behaviour is observed
1Pd/SA catalysts are plotted in Figs. 79, respectively. for the 4Ni/SA catalyst (data not shown). Under the
Fig. 9. Effect of the reaction time on selectivity in the hydrogenation of naphthalene (tetralin and trans-decalin formation) and toluene
conversion on the 1Pd/SA catalyst. Reaction conditions as in Fig. 5.
28 V.L. Barrio et al. / Applied Catalysis A: General 242 (2003) 1730
Contrary to TOFt=0 values, all catalysts showed Considering additional activity from acid sites
greater specific reaction rates in the hydrogenation of [3,3134], the differences in activity expressed as the
toluene than naphthalene (Fig. 10(a)). For toluene, the initial reaction rates and in TOFt=0 suggest that both
initial intrinsic activity ranking is: 1Pd8Ni/SA > metal and acid sites of silicaalumina may be in-
8Ni/SA 1Pd/SA
4Ni/SA > 1Pd4Ni/SA
volved in the rate-determining step of the hydrogena-
SA, whereas for naphthalene the reactivity of all the tion of toluene [37]. Indeed, contrary to naphthalene,
catalysts is very similar. On comparing the activities the bare SA was active in hydrogenation of toluene.
of both the 1Pd/SA and 8Ni/SA catalysts with the bi- However, in this study no exists correlation between
nary 1Pd8Ni/SA one, the absence of a synergy ef- the ammonia temperature-programmed desorption
fect is evident. A similar absence of a synergy effect data (Table 2) and the trend in catalytic activity
was observed for the silica-supported PdNi systems (Fig. 10(a)). Moreover, the reduction temperature of
tested for the hydrogenation of 1,3-butadiene [8]. the Ni species after Pd incorporation did not change
Considering Ni-containing catalysts, several expla- (Fig. 2). Thus, the additional activity from hydrogen
nations can be advanced to explain the greater reaction spilled over from metal to the acid sites where toluene
rate of the 1Pd8Ni/SA catalyst in the hydrogenation can be adsorbed is hardly possible. This is due to the
of toluene at steady-state: (i) electronic modification formation of large amount of a nickel hydrosilicate
of the metal particles [10]; (ii), the absence of sinter- phase, which modifies the environment of the acid
ing of the metal phases; (iii) additional activity from sites to a considerable extent.
acid sites [3134]; and (iv), increasing resistance to Finally, considering the greater resistance to deacti-
poisoning of the metal sites of the catalysts by coke vation of the 1Pd8Ni/SA catalyst, it can tentatively be
precursors [810]. assumed that as a consequence of the stronger metal-
Considering point (i), the IR spectra of adsorbed lic character of Ni atoms the hydrogenation of ad-
CO and X-ray photoelectron spectroscopy data of sorbed coke precursors may be favoured. Despite this,
the 1Pd8Ni/SA catalyst rule out the participation of the stronger metallic character of Ni0 is produced dur-
electronic modification of Pd atoms by surrounding ing on-stream operation, and this was not seen in the
Ni atoms. The limited modification of the electronic reduced samples. Since 1Pd8Ni/SA catalyst shows
structure of the PdNi/SiO2 catalyst, which have no resistance to deactivation only for 7 h, and after this
effect on the reactivity, were also observed by Re- run time a dramatic inhibition in activity occurs, some
nouprez et al. [8]. Moreover, the similar Ni/(Al + Si) changes in the structure of the catalyst after coke sat-
atomic ratio for the reduced and used 1Pd8Ni/SA uration must occur. This could be explained in terms
catalyst precludes its deactivation due to the sintering of the notion that a drastic decay in the conversion of
of Ni particles. Since the temperature-programmed toluene would be accompanied by a parallel decrease
reduction measurements point to the presence of in selectivity toward decalin formation. Noticeably,
nickel hydrosilicate phases in all the samples, their this decrease in hydrogenation capability was accom-
role could be similar to that of a NiAl2 O4 phase panied by parallel increase in the metallic character
[35]. This phase is considered to act as a support for of Ni0 . Since the X-ray photoelectron spectroscopy
Ni phases [35], providing a stabilising effect while data confirmed a decrease in the exposure of Pd atoms
maintains a very low reactivity [6,36]. Since for the during the reaction, in agreement with the findings of
reduced and used catalysts, the Ni surface exposure Renouprez et al. [8], we can tentatively propose that
measured correlates well with hydrogenation activity, during on-stream reaction the Pd atoms migrate to
the initial formation of nickel hydrosilicate/aluminate the sites where coke is preferentially adsorbed. Since
could inhibit the sintering of nickel species. The only coke formation starts on low coordination metal sites
exception is the 1Pd4Ni catalyst. This is because of [8] and their surroundings and then continues on the
the longer period needed for its stabilisation during support [38], the strong resistance to the deactivation
on-stream operation (100 h; the rest of the catalysts would be related to Pd incorporation and nickel hy-
only required 24 h). As a consequence, this sample drosilicate formation, which might inhibit the growth
simultaneously presents a large amount of coke on of coke precursors at the support interface. Since Pd
the surface. exhibits a greater hydrogenation ability than Ni, once
30 V.L. Barrio et al. / Applied Catalysis A: General 242 (2003) 1730
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