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Molecular Catalysis xxx (xxxx) xxxx

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Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat

Factors influencing selectivity in the liquid-phase phenol


hydrodeoxygenation over ZSM-5 supported Pt/Ir and Pt+Ir catalysts
B. Paweleca,*, C.V. Loriceraa, C. Geantetb, N. Motaa, J.L.G. Fierroa, R.M. Navarroa,*
a
Institute of Catalysis and Petroleum Chemistry, CSIC, Cantoblanco, 28049 Madrid, Spain
b
Research Institute on Catalysis and Environment Lyon (IRCELYON), CNRS: UMR5256-University Claude Bernard-Lyon (UCBL), France

A R T I C LE I N FO A B S T R A C T

Keywords: The effect of partial Pt substitution by Ir on the catalytic response of bimetallic Pt-Ir/ZSM-5 (Pt/Ir = 1) catalyst
Bio-oils in the liquid-phase hydrodeoxygenation (HDO) of phenol was investigated. To evaluate the catalyst intrinsic
Phenol activity, the ZSM-5 supported Pt, Ir and Pt + Ir catalysts were prepared with similar total metal loading (ca. 3 wt.
Hydrodeoxygenation %) and acidity. The catalysts were characterized by several physical and chemical techniques and tested in the
Pt/Ir
HDO of phenol reaction carried out in a batch reactor at T = 200 °C under H2 pressure of 3.0 MPa. For all the
ZSM-5
catalysts, the phenol transformation mainly proceeds via hydrogenation + dehydration (HYD reaction route)
leading to cyclohexane as the main product (selectivity 60–96%). Partial substitution of Pt by Ir in catalyst
formulation (Pt50-Ir50/ZSM-5) enhances both activity and selectivity toward O-free products. This was asso-
ciated to Ir surface enrichment (from HRTEM). The Ir/ZMS-5 and Pt50-It50/ZMS-5 catalysts having well dis-
persed Ir nanoparticles were more selective toward dehydration than Pt/ZSM-5 having Pt species with a broad
size distribution range. The catalyst activity-structure correlation suggests that the dehydration of cyclohexanol
(intermediate product) can occur at the interface between the metal and acid sites of the support.

Introduction range products over bifunctional Pt/HBeta [9]. Similarly, in the case of
Pd catalysts, the acidity of parent HBeta and ZSM-5 zeolites affected the
Bio-oils are alternative feed stocks for fossil fuels. These bio-oils are initial rates of HDO of benzophenone to the desired diphenylmethane
chemically and thermally unstable due to the high content of oxyge- [10]. However, the acid function should be moderate because strong
nated compounds. In addition, they exhibit an acidic nature and a acidity favors catalyst deactivation via coking [11]. The synergy of the
tendency to polymerization. To solve these problems, bio-oils have to support acid function and the metal function in the catalytic HDO of m-
be upgraded and traditional hydrodeoxygenation (HDO) process al- cresol was observed [11].
ready existing within the petroleum refining infrastructure can be em- Considering the metal function, the first catalysts studied for the
ployed [1–5]. In this process the oxygenated compounds can be re- HDO reaction were based on the metal sulphides, which were pre-
moved via hydrogenation in the presence of a catalyst. As the content of viously used by the petroleum refining industry for the removal of
phenolic compounds in bio-oils represent nearly one quarter of the total sulphur compounds from crude oil [7]. However, the reactivity of metal
O-containing compounds, phenolic compounds are often used as a sulphides is lowered in the presence of water due to formation of sur-
model compounds of bio-oils [4]. A general overview of the catalysts face oxides [12]. To maintain the catalyst stability, sulphur species
[1–6], reaction conditions [7] and mechanisms of HDO reactions of bio- should be introduced into reactor [12]. By contrast, noble metals are
oils are summarized in a few excellent reviews [1–8]. more resistant toward deactivation by H2O and they exhibit better
The catalysts tailored for the HDO reaction are bifunctional; this hydrogenation activity at a lower hydrogen pressure and temperatures
means that they exhibit metal and acid sites both needed for hydro- [8]. Thus, the catalysts based on noble metals seem to be a good option
genation of aromatic ring and for O-removal via dehydration, respec- for the substitution of metal sulphides in the catalyst formulation. In
tively [2]. Thus, there is significant experimental evidence that the this sense, our previous study demonstrated that the incorporation of a
acidic supports promote HDO reaction [8–11]. For example, it was low amount of Pt or Ir to RuS2/SBA-15 catalyst improved the activity
found that the support acidic function of the HBeta zeolite catalyzed the for phenol HDO [13].
reaction of trans alkylation “during the anisole conversion to gasoline- Many noble metals (Ru, Pt, Ir, Rh, Pd) supported on reducible


Corresponding authors.
E-mail addresses: bgarcia@icp.csic.es (B. Pawelec), r.navarro@icp.csic.es (R.M. Navarro).

https://doi.org/10.1016/j.mcat.2019.110669
Received 8 July 2019; Received in revised form 6 October 2019; Accepted 9 October 2019
2468-8231/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: B. Pawelec, et al., Molecular Catalysis, https://doi.org/10.1016/j.mcat.2019.110669
B. Pawelec, et al. Molecular Catalysis xxx (xxxx) xxxx

oxides (CeO2, TiO2, ZrO2) and non-reducible substrates (zeolites, silica, wetness impregnation method using an aqueous solution of IrCl3 ·H2O
alumina, carbon) have been tested in the HDO of phenolic model and H2PtCl6 ·6H2O, respectively. The bimetallic Pt50-Ir50/Z catalyst
compounds [11,14–29]. Among the different noble metals, Pt and Ru- was similarly prepared by simultaneous impregnation with an aqueous
based catalysts are the most studied [11,15–20,26] whereas the HDO solution of both precursors. The nominal metal loadings of the mono-
activities of the Ir-based catalysts are scarcely reported [21–25]. For metallic Pt/Z and Ir catalysts were 3 wt. %, whereas of the bimetallic
example, a homogeneous Ir catalyst was successfully employed in the Pt50-Ir50/Z catalyst were 1.5 wt. % Ir and 1.5 wt. % Pt. Then, im-
HDO of 2,5-hexadione [22] confirming that Ir can be active for CeO pregnates were dried overnight in air at 110 °C and finally calcined at
bond hydrogenolysis [21]. However, a heterogeneous Ir/ZrO2 catalyst 400 °C for 3 h.
tested in HDO of guaiacol exhibited dominant cyclohexanol formation
suggesting that only partial deoxygenation occurs [23]. Therefore, it Characterization techniques
seems that there is some confusion in literature concerning the Ir in-
trinsic deoxygenation activity. To clarify this inconsistency, the aim of The elemental analysis of the oxide precursors was determined by
this work was to study the effect of partial substitution of Pt by Ir (Pt50- Total Reflection X-ray Fluorescence (TRXF) technique on an EXTRA-II
Ir50) on the catalyst selectivity in phenol HDO reaction. TXRF Spectrometer (Rich & Seifert, Germany). Their textural properties
Generally, the HDO activity can be enhanced using bimetallic cat- of the calcined catalysts were determined from the N2 adsorption-des-
alyst formulation, as it was demonstrated with carbon supported Pt-Cr orption isotherms at −196 °C on a Micromeritics TriStar 3000 appa-
and Pt-V catalysts when tested in the selective phenol transformation to ratus. The catalysts were previously degassed at 270 °C for 5 h.
cyclohexanone [20]. The Ir-Re/γ-Al2O3 catalyst tested in the HDO of Temperature-programmed reduction (TPR) was carried out in a
isoeugenol was found to be more effective than the Pt-Re/γ-Al2O3 [24]. Micromeritics TPR/TPD 2900 instrument. Details of the procedure can
This was linked not only to the high iridium dispersion but also to be found elsewhere [34]. The X-ray diffraction of the fresh reduced
formation of the IrRe active phase [24]. Similarly, the Ir–ReOx/SiO2 catalysts was performed on a Seifert 3000 diffractometer, using Ni-fil-
catalyst was active and selective toward glycerol hydrogenolysis [25] tered CuKα radiation (40 kV, 40 mA). The acidity of the calcined cat-
and hydrogenation of unsaturated aldehydes to unsaturated alcohols alysts was evaluated by the temperature-programmed desorption of
under low H2 pressure (0.8 MPa) and low temperature (30 °C) [26]. An NH3 technique (TPD-NH3) using the same Micromeritics TPR/TPD
update of the heterogeneous catalysts employed for bio-oil and model 2900 instrument. The X-ray Photoelectron Spectroscopy (XPS) analysis
compounds upgrading has been recently reviewed by Ruddy et al. [6]. of the spent catalysts was carried out in a VG Escalab 200R spectro-
Concerning the support, recent studies have shown that zeolites are meter equipped with a Mg Kα X-ray source (hν = 1253.6 eV) and
better substrates than alumina or silica in hydrodeoxygenation of hemispherical electron analyser. The binding energy of C1s peak at
phenol due to their regular pore system and moderate acidity [26,27]. 284.8 eV was used as reference. Transmission electron microscopy
Among the various zeolites tested for the conversion of biomass, the (TEM) combined with energy-dispersive X-ray (EDX) microanalysis of
best results were obtained with medium pore zeolites, such as acidic spent catalysts was performed using a JEOL JEM 2000FX microscope
ZSM-5 zeolite [9]. This is due to the ability of this zeolite to allow the working at 200 kV.
entrance of the molecules present in the bio-liquids, and also to its
medium acidity, and high hydrothermal stability [27,29,30]. In addi- Catalytic activity
tion, ZSM-5 zeolite exhibits an appropriate 2D pore network comprising
interconnecting straight (0.53 nm x 0.56 nm) and sinusoidal channels Phenol HDO reaction was studied in a batch reactor (300 mL, T =
(0.55 nm x 0.51 nm), which allows the shape selectivity [9]. After me- 200 °C, reaction time: 5 h and total hydrogen pressure: 3.0 MPa). The
sopore incorporation, the hierarchical mesoporous structure can be autoclave reactor was provided with a mechanical stirrer (900 rpm) for
obtained [30]. Pt and Pd catalysts supported on mesoporous ZSM-5 the maximum dispersion of gas in a liquid system. The hydrogen
zeolite were found to be active in the gas-phase dibenzofuran hydro- pressure was maintained constant through the experiment by means of
deoxygenation [29] and liquid-phase HDO of m-cresol [30] respec- a pressure regulator valve. The reagent (10.6 mmol phenol), was dis-
tively, whereas mesoporous ZSM-5 zeolite was active in the HDO of solved in a non-polar tetralin solvent (80 mL). Hexadecane was used as
dibenzofuran [26]. the internal standard. Prior to reaction, the catalyst (100 mg) was ac-
In line with the above, this work was undertaken with the aim to tivated ex-situ by reduction in a flow of H2 in N2 (10:1 M) at 350 °C for
enlarge our previous investigation on the ring-opening with Pt-Ir cat- 3 h. For the experiments, first the catalyst was added to phenol-tetralin
alysts [31,32] by comparing the catalytic behaviour of ZSM-5-sup- solution and carefully mixed. After the phenol-catalyst solution was
ported bimetallic (Pt50-Ir50/Z) with the monometallic Pt/Z and Ir/Z loaded in the evacuated autoclave, it was swept by N2 to remove all air
catalysts in the liquid-phase phenol HDO. To the best of our knowledge, in the reactor. Then, the N2 was replaced by H2 and the reactor was
the use of the bimetallic Pt-Ir/ZSM-5 catalyst for O-removal from bio- pressurized to 3 MPa. Then, the temperature was raised to the final
oils or phenol HDO reaction has not been reported yet. This is probably reaction temperature of 200 °C and the experiment was continued for
because the preparation of bimetallic Pt-Ir catalysts having a homo- 5 h. The products of the reaction were analysed with a Hewlett-Packard
geneous dispersion of both metals is difficult due to the Ostwald ri- 5890A chromatograph equipped with a flame ionization detector (FID)
pening during the catalyst thermal activation treatment [31,33]. In and a DB-1 capillary column (30 m x0.450 mm x2.55 μm thick) to a
order to study the migration of Pt/Ir particles, the bimetallic Pt50-Ir50/ temperature of 250 °C. More details of the procedure can be found
Z catalyst was prepared with the same nominal Pt and Ir loadings (Pt/ elsewhere [35].
Ir = 1) by wet co-impregnation of the zeolite. Structural and surface
studies have been conducted with the aim to establish some connec- Results and discussion
tions between catalyst structure and HDO performance.
Characterization of the calcined catalysts
Experimental
The Pt and Ir loadings of the oxide precursors, determined by XRXF
Catalyst preparation spectrometry, are presented in Table 1. The metal content of all the
catalysts is lower than of the theoretical one (3 wt. %). Considering the
Commercial ZSM-5 zeolite (labelled hereafter as Z; Si/Al = 19; Akzo total metal loading, the observed trend is: Pt/Z (2.7 wt. %) > Pt50-
Nobel; Sweden) was used to support Ir, Pt and Pt50-Ir50 catalysts. The Ir50/Z (2.0 wt.%) > Ir/Z (2.3 wt. %).
monometallic Pt/Z and Ir/Z catalysts were prepared by the incipient The textural properties of bare ZSM-5 zeolite before and after metal

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B. Pawelec, et al. Molecular Catalysis xxx (xxxx) xxxx

Table 1 combination of a type I and type IV isotherm which are typical for
Metal loading and textural properties of the calcined catalysts. hierarchical materials having both micro- and mesoporous structure.
Catalyst Pta Ira SBETb Smicroc Vtotalb Vmicroc Similar type of isotherm was reported for alkaline-treated ZSM-5 zeolite
(wt.%) (wt. (m2/g) (m2/g) (cm3/g) (cm3/g) by Groen et al. [39]. In contrast to the parent ZSM-5 (Fig. 1A), the N2
%) adsorption-desorption isotherms of the Pt50-Ir50/Z catalyst shows one
hysteresis loop characteristic of a percolation effect caused by ink-bottle
Z – – 358 74 0.22 0.04
Pt/Z 2.7 – 309 209 0.22 0.11
type pores [40,41]. The presence of mesopores is inferred from the
Pt50-Ir50/Z 1.1 0.9 319 213 0.23 0.11 strong increase in N2 uptake at higher pressures [40], which is sup-
Ir/Z – 2.3 323 213 0.23 0.11 ported by the t-plot data (Table 1). External surface and surface
a
roughness might contribute to mesoporosity [41]. The formation of
As determined by Total Reflection X-Ray Fluorescence.
b
mesopores probably occurs during zeolite drying before impregnation
Specific surface area determined by BET method and total pore volume
that would introduce intracrystal mesoporosity.
adsorbed at P/P0 = 0.98 (from N2 physisorption at −196 °C).
Fig. 2B shows the BJH adsorption pore-size distribution for all ZSM-
c
As determined by N2 physisorption at −196 °C using t-plot method.
5 supported catalysts. A narrow peak at about 1.5 nm is associated to
the tensile strength effect [36,39,42]. This is due to the fact that the
loading were evaluated using N2 physisorption. N2 nitrogen ad-
BJH method is only suited for mesoporous materials having pore sizes
sorption–desorption isotherms and pore size distributions (PSDs) for
larger than ca. 2 nm [42], consequently, this peak is not further con-
parent ZSM-5 are shown in Fig. 1A. The N2 isotherms exhibits two
sidered. For all calcined catalysts, the broad pore size distribution in the
hysteresis loops; the low pressure hysteresis in the relative pressure
10–30 nm range (centered at 10.9 nm) suggests the presence of meso-
ranges from 0.1 to 0.3 and the high-pressure hysteresis above relative
pores. The contribution of mesoporosity is a consequence of the ex-
pressure of 0.5. Similar isotherm was observed for ZSM-5 with high Si/
ternal surface and roughness [41]. Noticeably, the contribution of the
Al ratio by Thommes et al. [36]. Taking into account that the pore
mesoporosity to overall catalyst porous structure is small being all
filling occurs at relative pressure > 0.35, it was hypothesized that such
catalysts mainly microporous, as deduced from the comparison of the
hysteresis behavior indicates phase transition of the zeolite framework
Smicro and Vmicro values derived from t-plot (Table 1). A non-homo-
(between its monoclinic and orthorhombic) [37]. Since our ZSM-5
geneous active phase dispersion on the support surface was confirmed
zeolite contains a moderate Si/Al atomic ratio of 19, this explanation is
by HRTEM (vide infra).
no so convincing. Instead it can be associated to the so-called “breathing
effect” frequently reported for MOFs materials. At the low pressure re-
gion when adsorbate molecules are introduced, the framework of ZSM-
Reduction behavior from TPR studies
5 starts contracting while inhaling, yielding decreasing framework
stress. As the pressure increases, the framework stress is increased
The reduction behaviour of the Pt and Ir oxide species on the surface
causing the elastic expansion of the sample [38]. This stress-based
of the ZSM-5 zeolite was studied by a temperature-programmed re-
model implies that two distinctive states of framework might exist in
duction technique. The TPR profiles of the oxide precursors are illu-
the parent ZSM-5. Pore size distributions, derived from adsorption
strated in Fig. 3. The TPR profile of Ir/Z catalyst exhibit a small peak at
branch of isotherm by BJH method, yielded 2 peaks at approximately
148 °C which is likely originated by the reduction of small clusters of
13.5 and 30.6 nm (inlet of Fig. 1A).
IrOx deposited on the zeolite surface, whereas the intermediate strong
The morphology of the bare ZSM-5 zeolite was confirmed by TEM.
peak at around 216 °C could be attributed to the iridium oxide species
Fig. 1(B) displays the HRTEM image of this zeolite showing its [011]
interacting strongly with the support. Finally, a small broad peak with
lattice planes (JCPDS 00-042-0024). The specific BET surface area
maxima around 350 °C comes likely from the reduction of the Ir ions
(SBET) of bare ZSM-5 zeolite was high (358 m2/g). The metal loading
located at exchanged positions within the zeolite structure [43]. With
into the ZSM-5 substrate resulted in a very small decrease in the specific
regard to the Pt/Z catalyst, one intense peak at 452 °C originates from
surface area suggesting that the main location of the noble metals is on
the reduction of the Pt2+ species strongly interacting with the support,
the external part of the zeolite crystals. This point will be discussed here
whereas a broad peak with maxima around 784 °C is usually attributed
after.
to the reduction of platinum species placed at exchange positions of
Fig. 2A displays N2 isotherms of the representative Pt50-Ir50/Z
ZSM-5 zeolite [44]. A shoulder observed at about 367 °C could be at-
catalyst. As can be seen, the isotherm of this bimetallic catalyst is a
tributed to the platinum oxide species interacting weakly with the

Fig. 1. Nitrogen adsorption-desorption isotherm (-195 °C) (A) and HRTEM image obtained on pure ZSM-5 zeolite (B). The BJH adsorption pore-size distribution is
plotted as an inlet of Fig. 1(A).

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B. Pawelec, et al. Molecular Catalysis xxx (xxxx) xxxx

Fig. 2. N2 adsorption-desorption isotherms of the calcined Pt50-Ir50/Z (A) and BJH adsorption pore-size distributions of all ZSM-5 supported catalysts (B).

trichloride (IrCl3·3H2O) needs to be heated and vigorously stirred to


solubilize it. Under these conditions the anion PtCl62− and polar IrCl3
precursor species are hydrated and thus surrounded by water ligands
held in place by ion–dipole and dipole–dipole interactions, respectively
[47]. When zeolite is contacted with the impregnant aqueous metal
solutions, a lower interaction between zeolite and PtCl62− anion is
weaken that in the case of Clδ− when using the IrCl3 precursor. As a
consequence, the TPR peak corresponding to the reduction of the Pt
species is shifted towards lower temperature, which is generally con-
sidered as proof of a lower metal-support interaction.

Investigation of catalyst acidity

The acidity of calcined catalysts was evaluated by NH3-TPD ex-


periments. The ammonia desorption profiles, displayed in Fig. 4, shown
main peaks at about 181 °C and 391 °C which can be ascribed to weak
and strong Brønsted acid sites, respectively. The latter acid sites are
associated with framework aluminium atoms whose distribution
throughout the zeolite lattice is often no uniform [48]. It is likely that
the weak acid sites are located on the surface, whereas the strong acid
sites are placed in the deepest part of the zeolite crystals [49]. As seen

Fig. 3. TPR profiles of oxide precursors: (a), Pt/Z: (b), Pt/50-Ir50/Z) and (c), Ir/
Z.

support. As expected, the binary Pt50-Ir50/Z catalyst exhibits many


more peaks than the monometallic ones, which are observed at tem-
perature maxima of 99, 230, 367 and 443 °C (shoulder). The two former
peaks are due to the reduction of IrOx species whereas the two latter
peaks can be associated with the reduction of Pt(II) species.
It can be seen that the peak associated with the reduction of Pt2+
species strongly interacting with support (443 °C) is downward shifted
with respect to that of the monometallic Pt/Z catalyst (452 °C). This
shift suggests that the addition of iridium promotes the reduction of the
platinum species in the binary Pt50-Ir50/Z catalyst, as it was observed
for the Pt50-Ir50/γ-Al2O3 catalysts prepared by wet impregnation [45].
It is likely that the interaction between Pt and Ir metals originated just
during the incipient wetness impregnation when the metal precursors
are spatially well-distributed on the substrate [46]. In addition, this
could be explained by taking into consideration that hexachloroplatinic
acid (H2PtCl6·6H2O) is easily dissolved in water, whereas iridium Fig. 4. NH3-TPD profiles of the calcined catalysts.

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B. Pawelec, et al. Molecular Catalysis xxx (xxxx) xxxx

Fig. 5. Wide-angle X-ray diffraction patterns of the fresh reduced catalysts: (a),
pristine zeolite; (b), Pt50-Ir50/Z; (c), Pt/Z and (d), Ir/Z.

Fig. 6. Ir 4f-Al 2p core level spectra of the spent Pt50-Ir50/Z (a) and Ir/Z (b)
in Fig. 4, all ZSM-5 supported catalysts exhibited very similar acidity catalysts.
and acid sites distribution. Thus, considering the experimental error of
the TPD-NH3 measurements (5%), the total acidity value remains al- composition and oxidation state of the elements of the spent catalysts.
most unchanged upon metal loading. This is expected because all cat- Fig. 6 displays the XPS spectra of Ir(Pt) 4f–Al 2p. As expected, all the
alysts are supported on the same support material and their total metal catalysts showed Si 2p and Al 2p peaks with a BE at 103 ± 0.1 eV and
loading is very similar (ca. 3 wt.%). 75.0 eV respectively, corresponding to the framework Si and Al species
of the ZSM-5 zeolite [53].
Crystallite structure The binding energies (BE) of core electrons and surface atomic ra-
tios are summarized in Tables 2 and 3, respectively. For the Pt-con-
Fig. 5 shows the wide-angle XRD patterns of the fresh reduced taining catalysts, the Pt 4d5/2 core level was also recorded. The BE of Pt
catalysts and pristine ZSM-5 zeolite. The presence of the low-angle 4d5/2 level at 314.7 eV is indicative of the presence of metallic Pt spe-
diffraction peaks (2θ < 10°) suggest that metal incorporation does not cies only [54]. For the Pt50-Ir50/Z catalyst, the Pt 4f7/2 level at ca.
affect crystallinity of the base zeolite to a great extent. The pristine 71.1 eV is associated with Pt0 [55] while for the Ir/Z and Pt50-Ir50/Z
zeolite and all the ZSM-5-supported catalysts exhibited typical diffrac- catalysts the Ir 4f7/2 level at a BE of 61.0 eV and 60.6 eV, respectively,
tion lines at 2θ angles of 7.9°, 8.8°, 14.8°, 15.6°, 23.3° and 23.7°, which are close to that reported for Ir0 species (60.9 eV) [56]. A similar BE
are characteristic of the zeolite substrate (JCPDS 00-042-0024). For the value was reported previously for a freshly reduced Pt-Ir/Al2O3 catalyst
Ir/Z catalyst, only the diffraction lines of the zeolite substrates were (61.2 eV) [57]. The downward shift in the BE of Ir 4f7/2 peak in Pt50-
observed indicating that the size of the Ir crystallites were below the Ir50/Z catalyst with respect to that of Ir/Z one would suggests the
XRD detection limit (< 4 nm) or its dispersion is very high. Conversely, formation of a Pt-Ir alloy in the bimetallic system. However, taking into
both Pt/Z and Pt50-Ir50/Z catalysts show additional diffraction lines at account the quite similar electronegativity of both elements, Ir (2.20)
ca. 39.8° and 81.3° originated by metallic Pt with a cubic crystallite and Pt (2.28), the charge transfer from iridium to platinum is hardly
structure (JCPDS 00-004-0802). For the binary Pt50-Ir50/Z catalyst, possible.
the planes (111), (200) and (220) suggest the presence of a single-phase Considering the quantitative Pt/Si and Ir/Si atomic ratios (Table 3),
disordered structure. However, the formation of binary Pt-Ir alloy is total metal exposure follows the trend: Ir/Z > Pt50-Ir50/Z = Pt/Z.
hardly possible because the temperature miscibility limit for the Pt50- Noticeably, Ir/Z catalyst exhibits higher Ir surface exposure than both
Ir50 composition is very high (close to 960 °C) [50]. the Pt-containing catalysts. By comparing surface Pt/Si and Ir/Si ratios
The average Pt0 crystallite sizes of Pt/Z catalyst, calculated by ap- with the bulk ratios in Fig. 7, it appears that Ir is location on the outer
plying the Debye-Scherrer's equation to the most intense diffraction line surface of both the Ir/Z and Pt50-Ir50/Z catalysts. In contrast, the
at 2θ angle of 39.8°, was much larger than that of the Pt50-Ir50/Z larger bulk Pt/Si atomic ratios with respect to surface Pt/Si ratios for
catalyst (44.5 nm vs. 35.1 nm). This calculation allows concluding that both Pt and Pt50-Ir50/Z catalysts strongly suggest the preferential Pt
Pt dispersion on the binary catalyst is enhanced with respect to its location within the inner crystalline structure of ZSM-5. For the binary
monometallic Pt/Z counterpart. As the fresh reduced catalysts were catalyst, the XPS Ir/Pt atomic ratio of 6 clearly suggests a six-fold larger
characterized by XRD, it is more likely that the growing of Pt metal Ir than Pt surface exposure.
particles could occur during catalyst calcination and/or reduction. In The location of metal particles in the spent catalysts was examined
line with this, there are literature reports showing that agglomeration also by HRTEM. Fig. 8 displays HRTEM images of the ZSM-5 supported
and size change of Pt nanoparticles on these supports occur during the catalysts. The binary Pt50-Ir50/Z catalyst exhibits globular shape par-
reaction conditions [51]. To obtain Pt particles without changing the ticles of a size much larger than the pore diameter together with very
nanoparticle’s size and morphology during the catalyst pretreatment
and/or reaction conditions, the colloid deposition method could be Table 2
more effective method for catalyst preparation, as it was argued by Binding energy (eV) of core electrons of the spent catalysts.
Kaidanovych et al. [52].
Catalyst Si 2p Al 2p Pt 4d5/2 Pt 4d7/2 Ir 4f7/2

Ir/Z 103.0 75.0 – – 61.0


Surface analysis of spent catalysts
Pt50-Ir50/Z 102.9 74.9 314.7 71.1 60.6
Pt/Z 103.1 75.0 314.7 – –
Photoelectron spectroscopy was used to evaluate both surface

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B. Pawelec, et al. Molecular Catalysis xxx (xxxx) xxxx

Table 3 having active phase well dispersed on the support surface. In contrast,
Surface atomic ratios of the spent catalysts. the other monometallic Pt contains large Pt0 crystallites located on the
Catalyst Si/Al at Ir/Si XPS (Bulk) Pt/Si XPS(Bulk) (Pt + Ir)/Si XPS support surface together with the small Pt0 particles located within the
XPS zeolite pores. Thus, it can be pointed out that Pt particles show higher
mobility than Ir ones on the zeolite carrier, which can be linked to their
Ir/Z 17.0 0.016 (0.008) – 0.016
different metal-support interaction (from TPR). These results agree with
Pt/Z 16.5 – 0.007(0.009) 0.007
Pt50-Ir50/Z 16.9 0.006(0.003) 0.001(0.004) 0.007
those obtained previously from Ir-Pd/SiO2-Al2O3 [31] and Ir-Pd/γ-
Al2O3 [33] systems showing that Pd species exhibit a greater mobility
than Ir over SiO2-Al2O3 and γ-Al2O3 substrates.

Catalyst activity

The performance of the catalysts was evaluated in the liquid-phase


phenol HDO reaction in the presence of a non-polar solvent (tetralin).
Activity data, in terms of HDO conversion, are presented in Table 4. The
HDO conversion follows the trend: Pt50-Ir50/Z (36%) > Ir/Z
(32%) > Pt/Z (23%). However, taking into consideration the catalyst
intrinsic activity expressed as the moles of phenol transformed per
moles of metal and per second, this trend is different: Pt50-Ir50/
Z > Pt/Z > Ir/Z.
The reaction products detected by GC analysis were: cyclohexanol,
cyclohexane, benzene and methylcyclohexane. The main product with
all the ZSM-5-supported catalysts was cyclohexane (selectivity of 60–96
%), which is the most desired product. Considering the products
Fig. 7. Bulk Pt(Ir)/Si atomic ratios (from TXRF) against XPS surface Pt(Ir)/Si formed, the possible reaction scheme is shown in Fig. 9. As seen in this
atomic ratios of spent catalysts. figure, the reaction scheme for phenol hydrogenolysis includes two
reaction routes: (1) hydrogenation of aromatic ring of phenol (HYD
small Ir0/Pt0 particles. The local EDS analysis (not shown here) with route) to cyclohexanol + dehydration of cyclohexanol to cyclohexane;
electronic spot of 10 and 20 nm pointed out to a non-homogeneous Pt and (2) direct hydrogenolysis (DDO route) of C–O bond of phenol to
and Ir dispersion, in agreement with XPS (vide supra). The mean par- benzene + hydrogenation of benzene to cyclohexane. Phenol can be
ticle size calculated from various HRTEM images of Pt50-Ir50/Z, Ir/Z converted to benzene by the direct deoxygenation (DDO) reaction
and Pt/Z catalysts are 9.1, 3.1 and 2.7 nm, respectively. As expected, pathway, and/or can be converted to cyclohexanol via the aromatic
much smaller crystalline particles was obtained from TEM images than ring hydrogenation (HYD route). For both Pt/Z and Pt50-Ir50/Z cata-
from XRD data. This is because the smallest crystalline particles are not lysts, the formation of cyclohexanol suggests that the phenol HDO re-
detected by XRD (detection limit below 4 nm) but still visible in TEM action proceeds mainly via a hydrogenation pathway. As compared to
images. However, both XRD and HRTEM techniques strongly suggests both Ir/Z and Pt50-Ir50/Z, Pt/Z catalyst shows partially inhibited de-
the formation of large Pt0 crystallites on the surface of the bimetallic hydration reaction, as deduced from its highest selectivity toward cy-
catalyst. In contrast with this catalyst, the monometallic Ir/Z one ex- clohexanol (Table 4). In contrast to the Ir/Z, the Ir/ZrO2 catalyst tested
hibits small Ir crystallites homogeneously dispersed on the support in HDO of guaiacol exhibited dominant cyclohexanol formation sug-
surface. Finally, the TEM image of the Pt/Z catalyst indicates the gesting that only partial deoxygenation occurs [23]. Noticeably, the
nonhomogeneous Pt0 species dispersion and a much lower density of Pt partial substitution of Pt by Ir in the catalyst formulation (Pt50-Ir50/Z)
nanoparticles on the support surface, as also revealed by XPS results. enhanced cyclohexanol dehydration to cyclohexane.
The schematic representation of the Pt and Ir species location within Both Ir/Z and Pt/Z catalysts were the only ones able to generate a
the zeolite body and on its surface deduced from the overall catalyst small amount of methylcyclopentane (4% and 2%, respectively) sug-
characterization is visualized in Fig. 9. As seen, the bimetallic Pt50- gesting the involvement of the acid function in the reaction mechanism.
Ir50/Z exhibits smallest Ir0 particles and largest Pt0 crystallites located Taking into account the similar acidity and acid sites distribution of all
on the outer zeolite surface together with small Pt0 particles located catalysts, the highest formation of methylcyclopentane on the Ir/Z
within the zeolite pores. On the other hand, the Ir/Z is unique catalyst catalyst could be explained considering the high hydrogenation/dehy-
drogenation activity of Ir [56] and the large metal surface exposure

Fig. 8. TEM micrographs of the ZSM-supported spent catalysts.

6
B. Pawelec, et al. Molecular Catalysis xxx (xxxx) xxxx

Fig. 9. Schematic representation of the Pt and Ir species location within the ZSM-5 zeolite body and on its surface.

Table 4 catalyst with respect to Pt/Z counterpart is the interesting feature of


HDO conversion and selectivity (at 60% phenol conversion) for HDO of phenol this work because this reaction is generally considered as an acid-cat-
over ZSM-5-supported catalysts (Reaction conditions were: batch reactor, alyzed reaction [11]. The selectivity results strongly suggest that the
T = 200 °C, PH2 = 3.0 MPa). well dispersed Ir nanoparticles can be more selective toward dehydra-
Ir/Z Pt/Z Pt50-Ir50/Z tion reaction than Pt species with a broad size distribution. This is
because hydrogen can be easily activated and cleaved at the metal-
a
HDO conv. (%) 32.0 23.0 36.0 support interface region, as it was demonstrated in the field of SRO for
rate (molPhenol molMetal−1 s−1)c 0.028 0.054 0.066
the binary Pt-Ir/HY system [60]. Thus, in contrast to the work by
Methylcyclopentaneb (%) 4 2 0
Benzeneb (%) 0 6 0 Postman et al. [61], Ir/Z catalyst having well dispersed Ir nanoparticles
Cyclohexaneb (%) 96 60 95 was found to be more effective toward dehydration reaction than Pt/Z
Cyclohexanolb (%) 0 32 5 counterpart. Indeed, one might expect that the well-dispersed Ir atoms
a
possessing electron donor/acceptor properties could facilitate the hy-
At reaction time of 5 h.
b drogen spillover mechanism [62]. Thus, both hydrogen spill over me-
Reaction conditions were: a batch reactor, T = 200 °C, PH2 = 3.0 MPa.
c chanism and a larger intrinsic activity of Ir than Pt for cleavage of
At 5 h per metal surface exposure (from XPS).
unsubstituted CeC bonds of the naphthenic compounds would explain
the largest selectivity of Ir/Z catalyst toward metylcyclopentane in
(Table 3). For all catalysts studied, the preferential selectivity towards
agreement with literature reports [32. 62, 63]. The results presented
HYD route products (94–100% selectivity) strongly suggests participa-
here agree with those reported previously for ring-opening of Pt5-Ir95/
tion of the metallic function rather than the acidic function.
CeO2-Al2O3 catalyst indicating that activity of this catalyst is governed
by the accessibility of metallic Ir sites on the surface [32]. Taking into
Relationship between activity and structure
consideration the literature reports [64,65] and the enhanced hydrogen
activation originated by a largest Ir surface exposure (from XPS), a low
It is well established that bifunctional catalysts having both acid and
coke formation on the Ir/Z catalyst can be expected.
metal sites are suited for HDO reactions: the metal sites are needed for
Finally, the lowest selectivity of Pt/Z catalyst toward CO-bond
hydrogenation/dehydrogenation, whereas the acid sites of the support
scission can be explained considering the absence of the formation of Pt
are required for dehydration, bond breaking, and isomerization [57].
(211) phase, as confirmed by XRD, and the steric inhibition of hydrogen
There is synergy between the support acid function and the metal
adsorption on Pt0 sites located deeply in the channels of the Pt/Z cat-
function, as it was confirmed recently for the HDO of m-cresol over Pt
alyst, as deduced from Fig. 7. Pt(211) plane having step sites is known
catalyst supported on γ-Al2O3 modified by acid treatment [11]. In this
to play a crucial role in C–O bond cleavage, as it was recently confirmed
work, all catalysts exhibit similar acidity, as confirmed by TPD-NH3
by a combined density functional theory (DFT) calculation and micro-
(Fig. 4). Thus, the catalyst acidity did not mask the effect of its metal
kinetic model for Pt (211) and Ir (211) metals tested in ethanol HDO
function. However, the similar acidity of the catalysts did not preclude
reaction [66]. Similarly, the DFT calculation indicated that Rh (211)
the existence of synergy between their acid and metal functions.
crystal plane was more active than Rh (111) for CO-bond cleavage in
The best catalytic response of the bimetallic Pt50-Ir50/Z catalyst in
the HDO of phenol [67].
the liquid-phase hydrodoxygenation with respect its monometallic Pt/Z
and Ir/Z counterparts having the same total metal loading and the same
acidity evidenced the positive ‘geometric’ effect of the simultaneous Conclusions
presence of both metals on the surface. Catalysts characterization by
combined XRD, XPS and HRTEM strongly suggest that the main factors The results presented in this work underline the factors influencing
influencing on catalytic behavior are the intrinsic activities of Ir and Pt the performance of noble metals (Pt, Ir) supported on ZSM-5 zeolite in
phases and their dispersion. Taking into account the ability of acidic the liquid-phase hydrodeoxygenation of phenol. It was found that the
supports to contribute to the activity of a catalyst for both aromatic catalyst activity was strongly influenced by the metal species exposure
hydrogenation [58] and dehydration reactions [59], it is hypothesized being acidic catalyst function similar for all catalysts studied. The use of
that reaction might occur at the interface of metal and acidic support. In a binary Pt50-Ir50/Z catalyst formulation was shown to have some
such case, the HDO reaction mechanism might involve phenol ad- advantage with respect to the monometallic Pt/Z and Ir/Z catalysts.
sorption on the interface between Ir(Pt) metal surface and support Partial substitution of Pt by Ir in the catalyst formulation (Pt50-Ir50/
whereas the heterolytic dissociation of H2 into H+ and H– take place on ZSM-5) enhances activity and selectivity toward O-free products which
the metal nanoparticles. However, further kinetic studies are needed for was associated with the surface enrichment of Ir species (from XPS and
clarify the reaction mechanism. HRTEM). Pt species exhibited higher mobility than the Ir ones over the
The larger extent of dehydration of cyclohexanol observed with Ir/Z zeolite carrier. As a consequence, the Ir/Z catalyst having a larger metal

7
B. Pawelec, et al. Molecular Catalysis xxx (xxxx) xxxx

surface exposure exhibited a greater activity and selectivity toward Mo or use of an acidic support, Appl. Catal. A: Gen. 580 (2019) 93–101.
HDO products than its Pt/Z homolog. Ir was more effective for dehy- [20] S.T. Srinivas, L. Jhansi Lakshmi, P. Kanta Rao, Selectivity dependence on the al-
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Declaration of Competing Interest [22] R.J. Sullivan, E. Latifi, B.K.M. Chung, D.V. Soldatov, M. Schlaf,
Hydrodeoxygenation of 2,5-hexanedione and 2,5-dimethylfuran by water, air and
The authors declare that they have no known competing financial acid-stable homogeneous ruthenium and iridium catalysts, ACS Catal. 4 (2014)
4116–4128.
interests or personal relationships that could have appeared to influ- [23] M. Alda-Onggar, P. Mäki-Arvela, A. Aho, I.L. Simakova, D.Y. Murzin,
ence the work reported in this paper. Hydrodeoxygenation of phenolic model compounds over zirconia supported Ir and
Ni-catalysts, React. Kinet. Mech. Catal. 126 (2019) 737–759.
[24] M. Alda-Onggar, P. Mäki-Arvela, K. Eränen, A. Aho, J. Hemming, P. Paturi,
Acknowledgments
M. Peurla, M. Lindblad, I.L. Simakova, D.Y. Murzin, Hydrodeoxygenation of iso-
eugenol over alumina-supported Ir, Pt, and Re catalysts, ACS Sustain. Chem. Eng. 6
Financial support given by CAM (BIOTRES-CM; P2018/EMT-4344 (2018) 16205–16218.
project) is gratefully acknowledged. This work was also partially sup- [25] Y. Amada, Y. Shinmi, S. Koso, T. Kubota, Y. Nakagawa, K. Tomishige, Reaction
mechanism of the glycerol hydrogenolysis to 1,3-propanediol over Ir–ReOx/SiO2
ported by the Spanish Ministry of Science, Innovation and Universities, catalyst, Appl. Catal., B: Environ. 105 (2011) 117–127.
through project CTQ2016-76505-C3-1-R project. The authors would [26] M. Tamura, K. Tokonami, Y. Nakagawa, K. Tomishige, Rapid synthesis of un-
like to thank Dr. Malcolm Yates (ICP-CSIC) for the heplful discussion of saturated alcohols under mild conditions by highly selective hydrogenation, Chem.
Commun. (Camb.) 49 (2013) 7034–7036.
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