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Catalysis Today: Anna Maria Venezia, Valeria La Parola, Leonarda Francesca Liotta
Catalysis Today: Anna Maria Venezia, Valeria La Parola, Leonarda Francesca Liotta
Catalysis Today: Anna Maria Venezia, Valeria La Parola, Leonarda Francesca Liotta
Catalysis Today
journal homepage: www.elsevier.com/locate/cattod
a r t i c l e i n f o a b s t r a c t
Article history: Heterogeneous catalysts, investigated by several techniques, such as XRD, XPS, TEM, TPR/TPO, able to
Received 14 September 2016 ascertain their structural, chemical, electronic and morphology properties are reviewed with respect
Received in revised form 2 November 2016 to selected results obtained by the group during approximately the last twenty ve years. The eld of
Accepted 6 November 2016
application covers different catalytic processes such as alkene hydrogenation over noble metal cata-
Available online 22 November 2016
lysts, hydrodesulfurization (HDS) and environmental catalysis. In particular the following subjects are
described: the peculiarity of a support like pumice, in relation to the hydrogenation activity of the sup-
Keywords:
ported noble metals; supported gold and supported gold containing alloy catalysts for different types
Diene hydrogenation
HDS catalysts
of reactions; the importance of the CoMoS precursors and the structure of bimetallic PdAu and PtAu for
Au/CeO2 hydrotreating processes; the effect of a sulfatable oxide, such as TiO2 , on the CH4 oxidation activity of
CO oxidation supported Pd catalysts; different preparation methods inuencing signicantly the catalytic behavior of
Pd-Au catalysts supported nickel catalysts for methane conversion processes. The reviewing of the different case studies
CH4 oxidation illustrates the importance of the interaction between support and active metals ultimately determining
the surface distribution of the active sites and their nal catalytic activity.
2016 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cattod.2016.11.004
0920-5861/ 2016 Elsevier B.V. All rights reserved.
A.M. Venezia et al. / Catalysis Today 285 (2017) 114124 115
istry, the texture and the morphology of the supports are also Table 1
Metal loadings of different pumice supported Pd catalysts, (wt.-%), surface metal
important. It is generally acknowledged that a high surface area
coverage (f) and diameters, d () of particles as derived by SAXS.
support is positive for the catalyst activity, allowing for a better
metal dispersion. However the use of a low surface area support, Samplea Pd (wt%) f db
when suitable syntheses succeed in making catalysts with high W0 0.05 0.005 18
metal dispersion, can improve the supported metal signal of a sur- W1 0.20 0.01 22
face technique like XPS, therefore allowing a better understanding W2 0.11 0.006 29
W3 0.39 0.02 35
of the experimental results [4].
W4 0.61 0.03 35
A way to enhance the catalytic behavior of a metal active species W5 0.86 0.04 40
is to add a second metal producing the so called alloying effect W6 0.37 0.01 50
[14,20]. Beside the main catalyst components, small amount of ele- W7 1.05 0.02 81
ments may be naturally present in the support or may be purposely From Venezia et al. [13] with permission.
added, acting as structural or as chemical promoter [2123].
Since none of the above effects works independently of each
other, for a better understanding of their role, we had tried to sep- 2.3. Catalytic activity
arate them by appropriate design of the catalysts. Obviously the
nature of the probing reaction must govern the selection of the Different reactor set ups which are described in the published
catalysts. The main achievements of our research activity carried papers were used. Dienes hydrogenations were performed in liquid
out during the last 25 years are summarized in the present review phase batch reactors, whereas gas phase reactions of CO, methane
article. Due to space limitations we will leave out some recent and VOC oxidation were carried out in plug ow reactors.
work related to biomass valorization [2427]. Different study cases
are grouped under two important types of test reactions, the cat- 3. Results and discussion
alytic hydrogenation and the catalytic oxidation. Hydrotreating
reaction, hydrodesulfurization (HDS) and hydrodearomatization 3.1. Hydrogenation
(HDA), although involving hydrogenation steps are treated sep-
arately because of the different target and the peculiarity of the 3.1.1. Monometallic catalysts
active sites. For each typology of reaction the importance of the Pumice, a natural stone of volcanic origin found in the nearby
support nature, with and without modiers, the structure of the island of Lipari, was used as catalyst support. Several studies related
active site, as single or multi-metal, will be demonstrated. to the catalytic effects of the supported metal particle sizes and
the alkali promotion have been published [13,3540]. After a mild
acid treatment, the material, an amorphous aluminosilicate, had
a reproducible nal composition of 85% of SiO2 , 7% of Al2 O3 with
2. Experimental
minor amounts of Na2 O and K2 O [36]. Being characterized by a
low surface area (5 m2 /g) it was crucial to adopt metal sup-
2.1. Support and catalyst preparation
porting procedures able to maximize the metal dispersion. In this
sense very good results were achieved using a procedure leading
Different types of oxides, either commercially available either
to an allyl intermediates with Pd(3 -C3 H5 )2 precursor [29]. The
laboratory made were used as catalyst support. Sol-gel, co-
obtained series of pumice supported catalysts (w series) with dif-
precipitation or hydrothermal syntheses were employed when
ferent amounts of noble metal are listed in Table 1 along with the
a particular control of the morphology, chemical and electronic
surface metal coverage (f) calculated as f = x/(1-x) pd dS00 , where
properties was needed. The anchoring of the active metal was per-
x was the palladium weight fraction in the nal catalyst, pd the
formed through a variety of procedures, depending on the nal
density of palladium, d the palladium particle diameter derived
objective and application. Just to cite a few examples, in order
by SAXS measurements and S0 the support specic surface area
to obtain a high dispersion of palladium particle over a low sur-
[13]. These catalysts were tested in the selective hydrogenation
face area support, an organometallic procedure, derived from the
of 1,3-cyclooctadiene (1,3-COD) to mono-ene in liquid phase [29].
Yermakovs method, with the diallyl Pd(3 -C3 H5 )2 precursor was
Surprisingly, the catalysts behaved quite differently from classical
adopted [28,29]; gold catalysts required a carefully pH controlled
catalysts of Pd over pure alumina or silica [12]. In those cases a dras-
deposition precipitation method [30]; solvated metal atom depo-
tic decrease of the activity in terms of TOF was observed for metal
sition (SMAD) procedure was modied to attain high dispersed
dispersion higher than 20% (particle size smaller than 60 ). Such
gold particles [30,31]; CoMo catalysts were prepared by classical
behavior was explained with the rapid loss of metallic character of
impregnation and also by ligand (NTA) assisted procedures [32]; the
the palladium crystallites associated to a positive chemical shift of
preparation of bimetallic particles with different degree of alloy-
the Pd 3d photoelectron peaks in the X-ray photoelectron spectra
ing and different core-shell structures involved also a preferential
(XPS). On the contrary, the pumice supported catalysts exhibited a
interaction with appropriate functional groups previously attached
constant turnover frequency (TOF) for metal particles larger than
to the supports [33]; furthermore, microwave assisted procedures
3040 and progressively smaller values as the dimensions of the
were used in the latest investigations [34].
particles decreased below 30 [29]. At the same time a negative
Pd 3d chemical shift was observed [40]. A lowering of the bind-
ing energy with the increase of the metal dispersion suggested the
2.2. Catalyst characterization presence of another effect, opposite to the loss of metallic character.
XPS of the valence band and X-ray excited O KLL Auger transi-
The catalysts, before and after the catalytic tests were char- tion revealed an interaction between pumice and metal, consistent
acterized by several structural and surface techniques. The most with an electron transfer from the support to the metal [39,40].
commonly used ones were XRD, SAXS, XPS, TPR/TPO, TGA/DTA, Through the combination of core electron binding energy shifts
SEM,TEM, FT-IR. Temperature programmed desorption of ammo- and Auger transition shifts it was possible to calculate the Auger
nia (NH3 -TPD) was used for the determination of the oxide support parameters, which, being independent on the charging and energy
acidity. reference, yielded more reliable information on the charge distri-
116 A.M. Venezia et al. / Catalysis Today 285 (2017) 114124
Fig. 1. Palladium Auger parameters and Turnover frequencies (TOF) relative to the selective hydrogen reduction of the 1,3-COD to mono-ene versus palladium particle size.
From Venezia et al. [13] with permission.
bution over the supported metal [41]. As shown in Fig. 1, a direct brought about by varying its near neighbor atoms. For the Pd-Cu
correlation existed between the Auger parameters and the TOFs for system, the importance of the chemical state of copper in control-
the 1,3-COD hydrogenation both plotted versus palladium particle ling the catalytic behavior of palladium in two different reactions
size. Therefore, the decrease of the activity with high metal dis- was demonstrated. After a mild catalyst reduction at room tem-
persion was related to the inhibited activation of the electron rich perature, copper, which in accord with the Cu 2p3/2 XP spectra
diene when the electron density on the supported metal became shown in Fig. 2 was present as CuO, caused a depletion of the
too high. By comparison with alkali free silica or alumina catalysts, electron density at the palladium atoms [43]. Assuming a pref-
the presence of sodium and potassium in the structure of pumice erential localization of the CuO on the support, with consequent
was considered responsible for such behavior. Such ndings were invariance of the palladium active site distribution, the electronic
reproduced with synthetic pumice containing various amount of an density change, in accord with the structure insensitivity of the
alkali metal, prepared by sol-gel procedure [22,23,42]. It was sug- reaction, did not affect the conversion rate, whereas it increased
gested that the alkali ions would increase the electron density at the selectivity to styrene as shown in Fig. 3. The preferential forma-
the metal particle through the formation of an electron donor com- tion of the monoalkene was ascribable to a structure sensitivity of
posite metal-oxygen- Na. The mechanism was essentially the same the subsequent hydrogenation of styrene to ethylbenzene inhibited
either when the alkali ions were added as surface dopants or when by the electron deciency of the palladium particles. After reduc-
they were inside the support structure. However, when sodium tion at 623 K, the catalytic active sites changed with formation of
ions were deposited at the surface the decrease of the ensemble metallic copper and Cu-Pd alloyed particles. Due to the ensemble
size due to the partial coverage of the palladium active sites reduced size variation with dilution of the palladium sites by copper, the
the positive effect of the increased electron density on palladium conversion rate decreased. Different behavior was observed in the
and therefore the activity of the catalyst [22]. The synthetic mate- hydrogenation reaction of the but-1-ene. In this case the presence
rials with similar structural and chemical properties as the natural of CuO, by decreasing the electron density over palladium, caused
pumice were characterized by larger surface area. To this respect a decrease of the hydrogenation rate and an increase of the isomer-
it was conrmed that the procedure of the metal deposition did ization selectivity to but-2-ene reecting the structure sensitivity
not have much relevance when dealing with the large surface area of the reaction [43]. In contrast, after the catalyst reduction, in the
supports, differently from the low surface area support like pumice, presence of metallic copper, the re-establishment of the electronic
for which only the allyl procedure allowed to obtain very small density restored the typical hydrogenation rate of the monometal-
supported metal particles [22]. lic palladium catalyst. However, the concurrent decrease of the
The electronic effects related to the use of pumice as support ensemble size, needed for multiply adsorbed alkylidene species,
for nickel were investigated in the hydrogenation of CO as function favored the selectivity towards isomerization requiring, on the con-
of different catalyst calcination temperature [37,38]. A combined trary, only one metal centre according to the intramolecular shift
TPR, XRD and XPS characterization ascertained that the presence mechanism [44,45].
of alkali ions in the support structure and their temperature driven
surface segregation inhibited both the activity and the C2+ selectiv-
ity, probably through a dilution ensemble effect. 3.2. Hydrotreating
Fig. 4. Variation of the thiophene HDS rate constant, k, versus wt% Na for the ASA
and the SiO2 -supported catalysts. Samples prepared from both cobalt precursors,
CoCl2 and Co(NO3 )2 are included (reaction conditions: 5.2vol% thiophene in H2 at
25.7 ml min1 , T = 603 K). From Venezia et al. [48] with permission.
Fig. 6. TPR proles of catalysts without sodium on different supports. From La Parola et al. [51] with permission.
structural order of the hexagonal framework, post synthesis alu- when, above a certain amount of acid sites, formation of coke would
mination of the mesoporous silica was performed by simple Al3+ prevail.
ions impregnation. As shown in Fig. 10, very small amount of Al3+
ions produced a large increase of the conversion. Above 0.5 wt% 3.3. Oxidation
of doping ions lower initial conversions and quicker deactivation
were obtained. A bi-functional mechanism as sketched in Fig. 11 3.3.1. CO oxidation over Au catalysts
was invoked. The acid sites, created on the supports by post alu- The remarkable results published by Haruta more than 25 years
mination, interacted with the electron rich thiophene molecules. ago [63] has driven a large academic and industrial interest in the
Being close to the activated hydrogen over Pd particles, hydrogena- development of gold catalysts for low temperature oxidation reac-
tion by the spillover hydrogen, followed by the C S bond breaking tion, particularly relevant to environmental catalysis [6470]. In
would occur. However the efciency of this process is nullied particular, the effect of the supports and of different preparation
120 A.M. Venezia et al. / Catalysis Today 285 (2017) 114124
20
16
k (ml*gPd s )
-1 -1
12
0
0 20 40 60 80 100
wt% Au
Fig. 7. Variation in the thiophene HDS rate constant, obtained at 613 K, versus
weight percent of Au for the ASA supported Aux Pdy catalysts (reaction conditions: Fig. 10. Thiophene conversion curve as a function of time for three selected samples
5.2 vol% thiophene in H2 at 25.7 ml min1 ; T = 613 K). From Venezia et al. [53] with (reaction conditions: 5.3 vol% thiophene in H2 ; WHSV = 7500 h1 ; T = 613 K). From
permission. Venezia et al. [62] with permission.
Fig. 14. Pd 3d XP spectra of PdAu/HMS after the 3rd run (including the overnight
SO2 treatment). From Venezia et al. [77] with permission.
and without carbon buildup, the right balance between the two
different factors should be taken into account.
4. Conclusion
Fig. 16. TPR proles of the differently prepared nickel catalysts and corresponding Acknowledgment
supports. From Pantaleo et al. [34] with permission.
Financial support by CNR (Progetto Finalizzato Chimica Fine
II, MURST (40% and 60%) European Community for COST Action
D15 and D36 and CM0903, NATO Grant ESP.CLG. No. 984160 are
kindly acknowledged. Special thanks go to Prof. Giulio Deganello
who intitiated us to the catalysis world.
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