DOI: 10.1002/cctc.
201000097
Embedded Ru@ZrO2 Catalysts for H2 Production by
Ammonia Decomposition
Barbara Lorenzut,[a] Tiziano Montini,*[a] Claudiu C. Pavel,[b] Massimiliano Comotti,[b]
Francesco Vizza,[c] Claudio Bianchini,[c] and Paolo Fornasiero[a]
Ammonia can be used as fuel in internal combustion engines
(ICEs). In this case, a flame accelerator, such as hydrogen, is
needed. H2 can be produced on-board by partial decomposi-
tion of ammonia. In this work, ruthenium nanoparticles were
embedded into a lanthanum-stabilized zirconia (LSZ) support
to obtain active and stable heterogeneous catalysts for NH3
decomposition. The effects of the preparation of both Ru
nanoparticles and LSZ support were investigated. The embed-
ded catalysts present high metal dispersion and good metal
Introduction
Interest in nonconventional fuels has significantly increased
over the last few years because of environmental issues, as
well as the irreversible decrease in fossil-fuel reservoirs.[1] Sever-
al alternatives to fossil fuels are under investigation worldwide,
for example, renewable fuels, obtained from second- and
third-generation biomasses, and H2 in combination with fuel
cells. A third, less investigated alternative is ammonia (NH3).[2–4]
Ammonia is an interesting energy vector, as it can be used
either for the production of H2 (NH3 has an H2 content of
17.7 wt %, higher than that of methanol) or as an ultimate fuel
in internal combustion engines (ICEs). In this respect, the use
of ammonia as a fuel for ICEs is attracting increasing interest.
Ammonia-fuelled engines can operate by slightly modifying
conventional spark ignition engines. However, owing to its
high autoignition temperature (651 8C), ammonia needs a
flame accelerator, such as hydrogen, to burn efficiently.
Therefore, ammonia must be, in part, decomposed to H2/N2
mixtures, to maintain acceptable combustion in an engine. A
minimum of 5 vol % of H2 is required in the gas stream for a
normal ICE operation, whereas a higher H2 content is
beneficial during the starting procedure.[5]
Hydrogen can be produced from ammonia by endothermic
decomposition, accordingly a process favored at high-
temperature and low-pressure operating conditions [Eq. (1)]:
2 NH3 ! N2 þ 3 H2 DH ¼ 92 kJ mol1 ð1Þ
Notably, the waste heat from the ICE can be used to sustain
the endothermic reaction of H2 production needed for the
operation of the system.
In this context, the development of heterogeneous catalysts
that are active in the temperature range of 400–600 8C is a
must to design an efficient ammonia-fuelled ICE. In this way,
1096  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
accessibility. Despite the relatively low metal loading (3 wt %),
activity was very high in the temperature range 400–600 8C.
The activity of the reference catalysts prepared by using
classical impregnation was significantly lower under the same
working conditions. Although many factors contribute to the
final catalyst performances, the data reported confirm that the
embedding strategy minimizes the undesirable sintering of the
Ru nanoparticles, leading to promising and stable catalytic
activity.
the waste heat produced by the ICE could be used to heat the
NH3 decomposition reactor. Many different metals have been
tested as active catalysts for ammonia decomposition; particu-
larly active are group VIII metals (Fe, Ni, Ru, Ir, Co, Pt).[6] The
catalytic activities are generally very low below 600 8C, even for
Ru, which generates the most active systems. The performance
of Ru-based nanosized catalysts is strongly affected by the
nature of the support[7–9] and by the mean crystallite size, with
an optimum size around 2 nm.[10, 11] Unfortunately, Ru-based
catalysts usually exhibit quite low metal dispersion. For this
reason, increasing efforts are being made to reduce the metal
particle size.[12]
Graphitic carbons and carbon nanotubes (CNTs) are very at-
tractive supports for Ru catalysts,[9, 13] although their high cost
may limit large-scale use. NH3 can be completely decomposed
over K-promoted Ru(5 wt %)/CNT catalyst at relatively low tem-
perature (450–500 8C) and even at high space velocity.[14] The
good performance of Ru/CNT catalyst is related to a) the pres-
ence of COOH and OH groups on the CNT surface, responsible
for an effective anchoring of Ru entities, and b) the confine-
ment effect of Ru nanoparticles inside the CNT pores (with an
[a] Dr. B. Lorenzut, Dr. T. Montini, Prof. P. Fornasiero
Department of Chemistry, ICCOM-CNR Trieste Research Unit
INSTM Trieste Research Unit, CENMAT
University of Trieste, via L. Giorgieri 1, 34127 Trieste (Italy)
Fax: (+ 39) 040-558-3903
E-mail: tmontini@units.it
[b] Dr. C. C. Pavel, Dr. M. Comotti
ACTA SpA, via di Lavoria loc. 56G, 56040 Crespina (PI) (Italy)
[c] Dr. F. Vizza, Dr. C. Bianchini
Institute of Chemistry of Organometallic Compounds, ICCOM-CNR
via Madonna del Piano 10, 50019 Sesto Fiorentino (Italy)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cctc.201000097.
ChemCatChem 2010, 2, 1096 – 1106
Embedded Ru@ZrO2 Catalysts

inner diameter of 3–10 nm). Although the catalyst shows a ZrO2-based oxides were obtained. The performances of the
good stability of the catalytic activity, carbon stability against embedded catalysts were compared to those of catalysts
gasification has not been reported.[9, 14] prepared by conventional impregnation methods (Ru/LSZ).
Basic oxides are more efficient as supports for Ru catalysts,
as compared to acidic oxides.[6] Zheng et al.[10] reported that
Ru(5 wt %)/Al2O3 facilitates the complete conversion of ammo- Results and Discussion
nia at 550 8C, whereas Choudhary et al.[7] obtained the com-
Catalytic activity for NH3 decomposition
plete conversion of NH3 only at 650 8C by using Ru(10 wt %)/
SiO2 under similar reaction conditions. Zhang et al.[15] reported The activities of prereduced embedded or impregnated
that a Ru(2.8 wt %)/MgO catalyst, prepared by the polyol Ru(3 wt %)-LSZ catalysts for NH3 decomposition are shown in
reduction method, shows approximately 80 % NH3 conversion Figure 1. Before catalytic activity experiments, the samples
at 500 8C. The complete conversion was achieved by the use of
Cs, as the promoter, deposited by impregnation. Yin et al.[16] re-
ported that high NH3 conversion can be achieved by using a
superbasic support, such as ZrO(OH)2 gel digested by heating
in a refluxing KOH aqueous solution (denoted as K-ZrO2-KOH).
This support is amorphous and contains significant amount of
K and Si. Ru (loading  5 wt %) was deposited on this support,
with a high metal dispersion, from either [Ru(acac)3] or
RuCl3.[32] This study provided evidence of the poisoning effect
of residual chloride ions. Ru/K-ZrO2-KOH from [Ru(acac)3]
shows a very good stability at 350 8C under severe reaction
conditions (high space velocity) within a 300 h period, with
rapid aging at higher temperatures (up to 600 8C).
We report herein the preparation and the functional and
structural/morphological characterization of an active and
stable lanthanum-stabilized zirconia (LSZ)-based catalyst
containing 3 wt % Ru. The catalysts were prepared by an
innovative synthetic method that allows the encapsulation of
an active metal phase inside a porous oxide matrix, which
generally avoids sintering of the metal, as well as catalyst deac-
tivation, during the reaction. The adopted embedding strategy
is largely reported in the literature for the preparation of Figure 1. Catalytic activity of NH3 decomposition on Ru-LSZ catalysts.
heterogeneous catalysts with peculiar activity and stability.[17] Pretreatment: reduction in situ in flowing H2 (35 mL min1) at 800 8C for 3 h.
Conditions: a) GHSV = 4000 mL g1 h1; b) GHSV = 30 000 mL g1 h1.
Heterogeneous catalysts comprising embedded Ru nanopar-
ticles were previously described for a variety of supports,
preparation methods, and test reactions.[18–21] The embedding
methodology was successfully employed by our group in were fully reduced in H2 flow at 800 8C for 3 h. This protocol
other processes involved in the H2 production, such as guarantees full metal reduction and serves as aging
methane partial oxidation[22, 23] and ethanol steam pretreatment of the samples, to avoid transient phenomena
reforming.[24, 25] during activity experiments. Catalytic tests were performed at
Two different embedding strategies were adopted in this atmospheric pressure and with pure NH3. Both high and low
study to prepare Ru@LSZ catalysts. Ru nanoparticles were syn- space velocities were investigated. The samples prepared by
thesized by reduction of RuCl3 in the presence of two different the embedding method showed higher activity compared to
protecting agents. In the first case, Ru nanoparticles were the samples prepared by classical impregnation. Over the
prepared by alcohol reduction in the presence of a polymer embedded catalysts, NH3 conversion started above 300 8C,
(polyvinyl pyrrolidone, PVP), obtaining a deep purple metal whereas over the impregnated catalysts the reaction started at
nanoparticle suspensions (DP method).[26] In the second case, 400 8C. The NH3 conversion over Ru@LSZ-DP was slightly
Ru nanoparticles, formed by NaBH4 reduction were protected higher than over Ru@LSZ-NaBH4. One may readily observe sig-
by N-hexadecyl-N-(2-hydroxyethyl)-N,N-dimethyl ammonium nificant differences in the ammonia conversion over the whole
bromide, a cationic surfactant denoted as HEAC16Br (NaBH4 range of temperatures investigated: The light-off temperatures
method).[27] The preparation conditions were chosen to obtain (T50—defined as the temperature corresponding to a 50 %
protected Ru nanoparticles with a mean dimension of 2.5 nm NH3 conversion) for the embedded catalysts were at least
if the DP method[26] was used and of 3 nm if the NaBH4 200 8C lower than those employed for the corresponding
method[27] was used. Around the nanoparticles, mixed La and impregnated samples. Two reactivity cycles were performed on
Zr hydroxides were deposited by coprecipitation. After various the various catalysts, without evidencing any appreciable
post-synthesis treatments, Ru nanoparticles embedded in the deactivation.

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Tests on other Ru-based catalysts under comparable
reaction conditions have been reported (GHSV =
30 000 mL g1 h1).[9, 10, 15] Ru@LSZ-DP promotes ammonia con-
version to the same extent as the K-promoted catalyst
Ru(5 wt %)/CNTs reported by Yin et al.,[9] which is one of the
most active catalysts ever reported. Notably, the metal
loadings in our embedded catalysts are lower than that of the
catalysts usually employed for NH3 decomposition. An attempt
to further decrease the Ru metal loading to 1 wt % was investi-
gated using the DP method. Unfortunately, the activity was
significantly lower with respect to Ru@LSZ-DP, with a NH3 con-
version of 40 % at 500 8C (GHSV = 30 000 mL g1 h1). On the
other hand, no improvement was observed on increasing the
Ru loading to 5 wt %.
An important issue for any new heterogeneous catalyst is
the stability of the material under prolonged exposure to the
reaction mixture. To this purpose, the performance of the em-
bedded Ru@LSZ catalysts and of the corresponding reference
impregnated Ru/LSZ-NaBH4 were investigated over a period of
120 h at 500 8C (Figure 2). This temperature can be easily
reached during the operation of an NH3 decomposition reactor
Figure 2. Stability of Ru-LSZ catalysts during NH3 decomposition for.
Pretreatment: reduction in situ in flowing H2 (35 mL min1) at 800 8C for 3 h.
Conditions: a) GHSV = 4000 mL g1 h1; b) GHSV = 30 000 mL g1 h1.
by using the waste heat from an ICE and, at the same time,
allows us to obtain high NH3 conversion under the experimen-
tal conditions adopted in this study. The stability of the Ru/
LSZ-DP catalyst was not studied, owing to its very low activity.
All the catalysts showed NH3 conversion comparable to that
during the run-up experiments at 500 8C (Figure 1). Analysis of
Figure 2 reveals that the NH3 conversion remains almost
constant for all the catalysts over the period of the stability
test.
To investigate more realistic conditions, reactivity tests were
also performed by using technical ammonia, that contains
approximately 3000 ppm of H2O, 50 ppm of O2 and 10 ppm of
1098 www.chemcatchem.org  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
T. Montini et al.
hydrocarbons. Identical activity and stability results were
obtained, indicating that small impurities in the feedstock have
a negligible effect on the catalytic performance.
Temperature-programmed reduction
The reduction properties of the as prepared samples were
examined by temperature-programmed reduction (TPR) under
a H2(5 %)/Ar flow (Figure 3).
Figure 3. Temperature programmed reduction (TPR) profiles: a) Ru@LSZ-DP;
b) Ru@LSZ-NaBH4 ; c) Ru/LSZ-DP; d) Ru/LSZ-NaBH4.
As a general characteristic, all the samples, both embedded
and impregnated, revealed multiple reduction processes at
low temperature (below 250 8C). The positions of the reduction
maxima are strongly dependent on the reaction conditions
(mass of catalysts, gas flow and composition, heating rate).
However, it is usually accepted that the reduction at low
temperature is ascribable to a highly dispersed RuOx species,
whereas at higher temperature the reduction of well crystal-
lized RuO2 particles is operative.[28] Moreover, the reduction
temperature is affected by the nature of the support.[29, 30] Con-
sistently, the different H2 consumption at low temperature of
the samples based on identical supports can be justified by
considering a different size and distribution of the RuOx
particles.
A reduction peak at high temperature (600–700 8C) was de-
tected, especially for the samples prepared by the DP method.
The reduction of RuOx species in this temperature range has
not to date been reported in the literature. Although this
reduction process might be partially ascribed to an artifact (ori-
ginated by an over-pressure on the sample, owing to the com-
pression of the sample), the reduction of RuOx species strongly
interacting with the support or almost fully embedded into
the oxide matrix appears as a reasonable explanation for the
H2 consumption at high temperatures. Indeed, the high
temperature peak was more pronounced in the samples that
have lower specific surface areas (see below) for which the
ChemCatChem 2010, 2, 1096 – 1106
Embedded Ru@ZrO2 Catalysts

contribution of such an over-pressure artifact should be

minimal. Quantification of H2 consumed during TPR was per-
formed by integrating the TPR peak and comparing the ob-
tained areas, which are very similar in all cases, with the value
obtained using CuO as standard. The results indicate that the
H2 consumption is consistent with a Ru amount very close to
the nominal 3 wt %, present in the form of RuO2, confirming
that the reduction processes are essentially related to RuOx
species. The presence of metal oxide species strongly interact-
ing with the support has already been reported for catalysts
prepared by the embedding approach.[22]
Consistent with the TPR results, a pretreatment in H2 flow
(35 mL min1) at 800 8C for 3 h was applied to all the materials
to fully reduce the metal species before the reactivity test. This
pretreatment serves as an activation treatment and as an
aging process, because the samples were not subjected to any
thermal treatment above 500 8C.
Figure 4. Powder XRD patterns: a) Ru@LSZ-DP; b) Ru@LSZ-NaBH4 ; c) Ru/LSZ-
DP; d) Ru/LSZ-NaBH4 after activation pretreatment (reduction in H2 flow at
Structural characterization
800 8C for 3 h).
Powder XRD analysis of the samples after different thermo-
chemical treatments have given evidence for great differences
among the various materials studied. aration method and treatment, different crystalline phases
The XRD patterns of the samples after calcination at 500 8C were observed. The analysis of each XRD pattern (Figures S2–
are shown in Figure S1 (see the Supporting Information). The S5 in the Supporting Information) allows for a semi-quan-
XRD patterns of the calcined samples are dominated by broad titative determination of the structure and composition of the
reflections attributable to the LSZ support. The presence of various phases. Summarized in Table 1 are the crystal phases
amorphous materials cannot be ruled out (especially in identified and the mean crystallite size for each phase, whereas
Figure S1, traces b and c). RuO2 reflections were generally weak the crystallographic parameters (from the Rietveld refinements)
and very sharp, indicating the presence of very large RuO2 par- are reported in Tables S1–S4 (see the Supporting Information).
ticles (crystallite size 30–100 nm). In the case of the Ru/LSZ-DP The samples prepared by the DP method (either embedded
sample, the presence of NaCl is evident, likely originated or impregnated) are composed of a complex mixture of
during the synthesis of the catalyst by reaction of chloride phases. The XRD pattern of the reduced Ru@LSZ-DP sample
from RuCl3 with impurities of sodium. (Figure S2 and Table S1 in the Supporting Information) is domi-
XRD patterns of the samples after standard activation in H2 nated by the tetragonal structure (space group P42/nmc) of the
(800 8C for 3 h) are shown in Figure 4. Depending on the prep- LSZ. An increase of the cell parameters with respect to those

Table 1. Results from the analysis of the XRD patterns of embedded (Ru@LSZ) and impregnated (Ru/LSZ) samples.

Samples Activated[a] After run-up[b] After stability tests[c]

Phase Loading [wt %] CS[d] [nm] Phase Loading [wt %] CS[d] [nm] Phase Loading [wt %] CS[d] [nm]
Ru@LSZ-DP[e] tetragonal LSZ 46.5 16 tetragonal LSZ 54.2 17 tetragonal LSZ 12.0 17
cubic LSZ 14.9 13 cubic LSZ 27.7 12 cubic LSZ 28.6 16
Na2ZrO3 38.6 42 Na2ZrO3 18.1 37 Na2ZrO3 59.4 31

Ru@LSZ-NaBH4 tetragonal LSZ 99.5 13 tetragonal LSZ 99.3 14 tetragonal LSZ 99.3 13
Ru 0.5 120 Ru 0.7 105 Ru 0.7 120

Ru/LSZ-DP[e] tetragonal LSZ 44.7 25 tetragonal LSZ 44.5 25

cubic LSZ 10.2 58 cubic LSZ 12.7 58 – – –
monoclinic ZrO2 41.7 69 monoclinic ZrO2 39.9 64
Ru 3.4 70 Ru 2.9 79

Ru/LSZ-NaBH4 tetragonal LSZ 96.8 14 tetragonal LSZ 96.6 15 tetragonal LSZ 96.5 15
Ru 3.2 78 Ru 3.4 71 Ru 3.5 73

[a] After standard activation pretreatment (reduction in H2 flow at 800 8C for 3 h); [b] activated sample after 2 cycles under NH3 decomposition conditions
(GHSV = 30 000 mL g1 h1); [c] activated sample after stability tests under NH3 decomposition conditions (GHSV = 30 000 mL g1 h1) for 110 h at 500 8C;
[d] CS = crystallite size calculated applying Scherrer’s equation; [e] Rietveld results for these samples are semi-quantitative, since the exact composition of
the phases is not known and some reflections are not clearly identified.

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of pure tetragonal ZrO2 (JCPDS n8 50-1089: a = 0.35984 nm,
c = 0.51520 nm) and thepvery ffiffiffi low tetragonal distortion (from
the cell parameters, c/(a 2) of 1.005 can be calculated) clearly
prove the incorporation of La into the ZrO2 oxide, as a result
of the larger ionic radius of LaIII with respect to ZrIV (for a 8-
fold coordinated site, 0.130 nm and 0.098 nm, respectively).[31]
The XRD pattern of the reduced Ru@LSZ-DP reveals also the
presence of monoclinic Na2ZrO3 and of a cubic LSZ phase with
fluoritic structure. The cell parameters of Na2ZrO3 are close to
those of the pure monoclinic phase (JCPDS no. 35-0770: a =
0.56233 nm, b = 0.97491 nm, c = 1.11270 nm, b = 99.9838). The
formation of Na2ZrO3 is an indication of the presence of large
amounts of Na + adsorbed on the solid material as a conse-
quence of the precipitation of the La/Zr mixed hydroxides with
NaOH. The presence of Na + in the material may also affect the
structure of the tetragonal LSZ phase, reducing the tetragonal
distortion.[32] Finally, accordingly to the empirical formula pro-
posed by Kim,[33] from the value of the cell parameter of the
cubic LSZ phase (0.5309 nm), it is possible to calculate the
composition of Zr1xLaxO2x/2. (x = 0.385), which indicates that
an enrichment in La with respect to the nominal composition
of the LSZ oxide has occurred. However, the inclusion of Na +
as an impurity in the La site, resulting in the formation of a
cubic doped-ZrO2,[32] cannot be ruled out. Notably, no reflec-
tion clearly related to Ru-based phases was detected, suggest-
ing that Ru is present as highly dispersed nanoparticles. This
feature is in good agreement with the high catalytic activity
demonstrated by this sample. Zheng et al.[10] reported that the
maximum reaction rate for NH3 decomposition is observed
when Ru nanoparticles of approximately 2 nm are present on
the catalyst. Moreover, Na2ZrO3 or Na + may act as promoters
for the reaction, as is well known for basic oxide supports[15, 16]
and/or the presence of alkali metals as promoters[9, 14–16] may
have a beneficial effect on Ru catalysts. To demonstrate the
effect of Na + or Na2ZrO3 on the catalytic performance of
Ru@LSZ-DP, several attempts were made to reduce the pres-
ence of Na + by washing the gel with diluted HNO3 (1 %) and
to reintroduce sodium by impregnating the washed material
with NaNO3 (soaking the catalyst powder into a 2 m aqueous
solution of NaNO3). After washing, a lower catalytic activity
was observed (Figure S6 in the Supporting Information). The
XRD pattern of the reduced sample (Figure S7 in the
Supporting Information) shows the formation of a solid
solution La2O3ZrO2 with tetragonal structure and of large Ru
crystallites (167 nm). This observation can be attributed to the
possible Ru redispersion during the washing treatment. After
impregnation of the washed material with NaNO3, a
further decrease of the catalytic activity was observed
(Figure S6). The XRD pattern of the activated sample shows
the presence of tetragonal LSZ, monoclinic ZrO2, metallic Ru
(mean crystallite size of 124 nm) and of a cubic phase with pat-
terns compatible with those of Na2O (although its cell parame-
ter is strongly reduced with respect to the theoretical value of
Na2O, 0.5392 vs 0.555 nm). Moreover, a strong sintering of the
material is observed, as a result of the phase separation and/or
pore blocking induced by NaNO3 impregnation.
1100 www.chemcatchem.org  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
T. Montini et al.
The situation of the activated Ru/LSZ-DP (prepared by im-
pregnation) is more complex than that of the corresponding
embedded sample (Figure S4 and Table S3 in the Supporting
Information). The oxide support is composed of a mixture of
tetragonal LSZ (major phase), monoclinic ZrO2 and cubic LSZ.
The latter phase is featured by a cell parameter shorter than
that of the corresponding phase observed for the reduced
Ru@LSZ-DP, suggesting a different degree of substitution of Zr
with La and/or Na. Moreover, a non-stoichiometric NaCl-
derived phase was included to better fit the XRD pattern,
although a significant lengthening of the cell parameter was
observed. Only minor reflections remain unidentified. Notably,
in this sample, clear and sharp reflections related to metal Ru
are present, indicating the presence of very large Ru particles
(ca. 70 nm). The presence of unknown amounts of Na-based
compound precludes the quantification of the other species.
The XRD analysis of the samples prepared following the
NaBH4 method is significantly less complex (see the Supporting
Information; Figure S3 and Table S2 for the embedded
Ru@LSZ-NaBH4 ; Figure S5 and Table S4 for the impregnated
Ru/LSZ-NaBH4). A solid solution of ZrO2 and La2O3 with a tet-
ragonal structure (designed as tetragonal LSZ) constitutes the
oxide support. No reflections related to cubic LSZ, monoclinic
ZrO2 or monoclinic Na2ZrO3 were detected. This result suggests
that the washing procedure adopted to remove the bromide
ions and the excess of surfactant used for the preparation of
the Ru nanoparticles is also effective for the elimination of the
Na + impurities. Notably, the catalytic activity of Ru@LSZ-NaBH4
was only slightly lower than that of Ru@LSZ-DP. Weak, but very
sharp, reflections assigned to metallic Ru were also observed.
In the case of the impregnated Ru/LSZ-NaBH4 sample, the Riet-
veld analysis accounts for a 3.2 wt % of Ru (instead of the nom-
inal 3 wt %) with very large crystallites (ca. 78 nm). In contrast,
the amount of Ru estimated for the embedded Ru@LSZ-NaBH4
is quite low (0.5 wt %). Furthermore, very large Ru crystallites
were observed (ca. 120 nm). The low amount of Ru estimated
by the Rietveld analysis, in conjunction with the good catalytic
activity and the acceptable Ru accessibility (see H2 chemisorp-
tion section) suggests the presence of a large number of
highly dispersed Ru nanoparticles that are not detectable by
XRD. A partial redissolution of some small Ru nanoparticles
during the washing procedure cannot be excluded. The re-
deposition of Ru on the external surface of the material might
account for the presence of these large Ru particles. In fact, a
significant sintering of the noble metal redeposited on the
external surface of the support and, therefore not protected,
may occur during the calcination and reduction steps.
After aging under NH3 decomposition, only minor modifica-
tions of the structural properties of the catalysts were evi-
denced. The XRD patterns of the samples after aging under
run-up experiments are shown in Figure 5, left (the results of
the Rietveld analysis are presented in Figures S8–S11 and
Tables S5–S8 in the Supporting Information), whereas, after the
stability test the samples exhibit the XRD pattern shown in Fig-
ure 5, right (the results of the Rietveld analysis are presented in
Figures S12–S14 and Tables S9–S11 in the Supporting Informa-
tion). Notably, no significant difference in the Ru crystallite size
ChemCatChem 2010, 2, 1096 – 1106
Embedded Ru@ZrO2 Catalysts

method. In the latter samples, the supports are homogeneous

Figure 5. Powder XRD patterns after run-up experiments (left) and after sta-
bility tests (right): a) Ru@LSZ-DP; b) Ru@LSZ-NaBH4 ; c) Ru/LSZ-DP; d) Ru/LSZ-
NaBH4 after aging under NH3 decomposition.
was observed. Only for Ru@LSZ-DP, we observed that, after
run-up experiments (up to 800 8C), the amount of Na2ZrO3 de-
creased to form tetragonal and cubic LSZ. In contrast, after the
stability test (prolonged exposure to NH3 at 500 8C), the
amount of tetragonal LSZ decreased to form Na2ZrO3 and
cubic LSZ. Nevertheless, the activity and stability results
suggest that the evolution of the phases in the oxide does not
appreciably influence the catalytic activity and the dimensions
of the Ru nanoparticles.
Textural characterization
The results of the textural characterization of the calcined sam-
ples are summarized in Table 2. All the samples gave rise to
type IV isotherms with hysteresis loops typical of mesoporous
materials.[34] The t-plot analysis reveals that the microporous
volume is always negligible. After all of the thermochemical
treatments considered, the samples prepared by the DP
method showed lower surface area and pore volume, as well
as larger pores than the samples prepared by the NaBH4
and their better textural properties (Table 2) are attributed to
the stabilizing effect of the formation of ZrO2La2O3 solid solu-
tion. Moreover, in the preparation of the NaBH4 samples, the
precipitate was carefully washed to remove Br and Na + ions,
as well as the excess of surfactant, whereas in the DP method
the excess of PVP was removed only by filtration of the
mother liquor. The deep sintering of the DP materials might
be the result of the presence of a various crystallographic
phases and of a possible local over-heating consequent to the
combustion of the residual polymer. Finally, in the NaBH4 prep-
aration method, the large amount of a cationic surfactant
(HEAC16Br) can act as directing agent during the gel forma-
tion, leading to a material with high surface area similarly to
that previously reported for ZrO2-based materials.[35, 36]
After standard activation pretreatment (reduction in H2 flow
at 800 8C for 3 h), all the samples underwent a significant de-
crease of the surface area and of the pore volume, as a result
of sintering phenomena induced by the reduction at high
temperature. Despite its good catalytic activity (Figure 1), the
embedded Ru@LSZ-DP sample exhibits a low surface area
(Table 2). On the other hand, the embedded Ru@LSZ-NaBH4
sample shows a lower decrease of the surface area and of the
pore volume, owing to the higher thermal stability of the tet-
ragonal ZrO2-La2O3 solid solution. Comparable surface areas
were observed for the embedded catalysts and the respective
impregnated samples. These results suggest that the catalytic
activity is mainly influenced by the Ru crystallite size, and not
by the surface area of the support.
Finally, the textural properties of the samples were only
marginally affected by the aging under NH3 decomposition,
during both run-up tests and long term stability tests.
Static and dynamic H2 chemisorption
H2 chemisorption experiments were performed with the aim of
further investigating the accessibility of the metal nanopar-
ticles to NH3. The measurements were performed both under
static and dynamic conditions in order to better evaluate the
accessibility of Ru. It is important to underline that, unlike
most metals, the determination of the Ru dispersion by chemi-

Table 2. N2 physisorption results for embedded (Ru@LSZ) and impregnated (Ru/LSZ) samples.

Samples Calcined[a] Activated[b] After run-up[c] After stability tests[d]

SSA[e] dM[f] CPV[g] SSA[e] dM[f] CPV[g] SSA[e] dM[f] CPV[g] SSA[e] dM[f] CPV[g]
[m2 g1] [nm] [mL g1] [m2 g1] [nm] [mL g1] [m2 g1] [nm] [mL g1] 2 1
[m g ] [nm] [mL g1]
Ru@LSZ-DP 56 15, 26[h] 0.46 12 59 0.08 12 59 0.08 8 62 0.04
Ru@LSZ-NaBH4 171 7 0.35 57 13 0.27 52 18 0.28 51 15 0.27
Ru/LSZ-DP 45 10 0.15 5 55 0.05 6 59 0.06 – – –
Ru/LSZ-NaBH4 144 7 0.35 50 16 0.30 51 18 0.32 47 15 0.29
LSZ-DP 46 10 0.15 2 52 0.01 – – – – – –
LSZ-NaBH4 144 7 0.35 62 11 0.31 – – – – – –

[a] After calcination in air at 500 8C for 5 h; [b] after standard activation pretreatment (reduction in H2 flow at 800 8C for 3 h); [c] after 2 cycles under NH3
decomposition conditions (GHSV = 30 000 mL g1 h1); [d] after stability tests under NH3 decomposition conditions (GHSV = 30 000 mL g1 h1) for 110 h at
500 8C; [e] SSA = specific surface area; [f] dM = maxima of the pore distribution calculated by BJH analysis of the desorption branch of the N2 isotherm;
[g] CPV = cumulative pore volume; [h] bimodal distribution.

ChemCatChem 2010, 2, 1096 – 1106  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemcatchem.org 1101
 T. Montini et al.

sorption is particularly difficult, as the H2 adsorption kinetics over through the support, a realistic determination of the Ru
are quite slow. Many attempts to establish the best experimen- particle size can be achieved also by dynamic H2
tal conditions for the determination of the Ru dispersion by chemisorption.
chemisorptions have been reported in the literature.[37, 38] Okal
et al.[37] demonstrated that, operating at 100 8C and with an
Temperature-programmed surface reaction
equilibration time of at least 1 h, static H2 chemisorption ex-
periments provide reliable values of the Ru dispersion. Similar Temperature-programmed surface reactions (TPSR) of adsorbed
experimental conditions were used in this study (Table 3). ammonia were conducted to further investigate the differen-
ces in the samples considered
(Figure 6). After saturation of
Table 3. H2 chemisorption results for embedded (Ru@LSZ) and impregnated (Ru/LSZ) samples after standard the surface with NH3 at 110 8C,
activation pretreatment (H2 reduction at 800 8C for 3 h). the desorption of various spe-
Sample Static H2 chemisorption [a]
Dynamic H2 chemisorption [b] cies was observed. The main
H/Ru[c] Area[d] [m2 g1] PS[e] [nm] H/Ru[c] Area[d] [m2 g1] PS[e] [nm] species detected during the
Ru@LSZ-DP 0.262 2.87 5.0 0.053 0.58 25.4
heating ramp were H2, N2, NH3,
Ru@LSZ-NaBH4 0.190 2.08 7.0 0.129 1.49 10.3 and H2O (from the support).
Ru/LSZ-DP 0.026 0.29 75.1 0.002 0.03 574 No significant evolution of
Ru/LSZ-NaBH4 0.040 0.44 32.9 0.043 0.47 31.0 species other than H2O (not re-
[a] Static chemisorption was measured on the samples at 100 8C in the 25–400 torr pressure range. The reversi- ported) was observed for the
ble adsorption was subtracted by the double isotherm method; [b] dynamic chemisorption was performed at Ru/LSZ-DP sample, which pos-
100 8C using pulses of H2 (73 mL) with N2 as the carrier gas (75 mL min1); [c] calculated using a H/Ru = 1:1 stoi-
sesses a low surface area
chiometry; [d] Metal surface area per gram of catalyst; [e] PS = article size.
(5 m2 g1) and very low metal

The sample Ru@LSZ-DP shows a relatively high static H2

chemisorption capability, suggesting the presence of small Ru
nanoparticles, in agreement with the absence of reflections re-
lated to Ru in the XRD pattern (Figure 4, trace a). Nevertheless,
a lower H/Ru ratio was shown by a dynamic H2 chemisorption
experiment. In all the other cases, the results obtained using
the two techniques were comparable and in good agreement
with the indication obtained from the XRD patterns of the cor-
responding reduced samples. The relatively high H/Ru ratio for
the activated Ru@LSZ-NaBH4 is another indication of the
presence of an appreciable amount of small Ru nanoparticles,
partially embedded into LSZ, together with a fraction of large
Ru particles (see the XRD data).
Static H2 chemisorption experiments have shown that the
Ru nanoparticles are accessible to the gas phase reagents, evi-
dencing that the embedding preparation does not result in a
Figure 6. Temperature-programmed surface reaction (TPSR) experiments
complete occlusion of the metal phase. Furthermore, the em- after NH3 adsorption at 110 8C on a) Ru@LSZ-DP, b) Ru@LSZ-NaBH4, c) Ru/
bedded catalysts present the highest Ru dispersion and the LSZ-DP, and d) Ru/LSZ-NaBH4. 1 torr = 133.322 Pa.
highest catalytic activity. On the other hand, the impregnated
samples exhibit a very low metal surface area (Table 3), large
Ru crystallites (from XRD), and the worst catalytic performance. dispersion (H/Ru = 0.026 by static H2 chemisorption). These re-
In the case of the Ru@LSZ-DP sample, for which static H2 sults suggest that the amount of NH3 adsorbed on this materi-
chemisorption suggests the presence of very small Ru nano- al is negligible, in agreement with the very low activity of this
particles, dynamic H2 chemisorption reveals a H/Ru ratio signifi- catalyst. In contrast, the samples with either a high surface
cantly lower than that obtained by the static technique. De- area (Ru/LSZ-NaBH4), or a high metal dispersion (Ru@LSZ-DP),
spite the presence of large pores in this sample, this result or both (Ru@LSZ-NaBH4), showed significant desorption of H2,
could be attributed to gas diffusional limitations. On the other N2, and NH3. The relative amounts of the desorbed compounds
hand, an effect of the small Ru particle size in the H2 adsorp- reflect the characteristics of the investigated samples, suggest-
tion kinetics cannot be ruled out. Rather, a better agreement ing that H2 and N2 are produced from the decomposition of
between the two techniques was obtained when very large Ru ammonia adsorbed on the Ru nanoparticles, whereas the des-
particles were present, as in the impregnated samples. In the orbed NH3 is derived from ammonia adsorbed on the support.
case of Ru@LSZ-NaBH4, for which H2 can be easily adsorbed on Notably, TPSR experiments on the embedded samples show
the large particles and transferred to the smaller ones by spill- the prevalence of the reaction products (H2 and N2), in agree-

1102 www.chemcatchem.org  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemCatChem 2010, 2, 1096 – 1106
Embedded Ru@ZrO2 Catalysts
ment with their high metal dispersion and catalytic activity.
Moreover, Ru@LSZ-NaBH4 desorbs larger quantities of the
products, owing to its higher surface area with respect to
Ru@LSZ-DP. Finally, Ru/LSZ-NaBH4 shows the prevalence of NH3
as desorbed product, accordingly with the high surface area
and low metal dispersion.
The trend in the peak temperature of the different species
(corresponding to the temperature of the maximum of the de-
sorption peak) is consistent with the catalytic performance of
the materials, as well as with their morphological characteris-
tics. The samples prepared by the NaBH4 method showed peak
temperatures of 385 8C for H2, 325 8C for N2, and 250 8C for
NH3. The highest intensity observed for Ru@LSZ-NaBH4 can be
ascribed to the higher metal dispersion, which favors the NH3
adsorption. On the other hand, Ru@LSZ-DP, which is the most
active, showed lower peak temperatures (345 8C for H2, 270 8C
for N2, and 260 8C for NH3). The decrease of the desorption
temperatures for Ru@LSZ-DP compared to Ru@LSZ-NaBH4 may
be related to the presence of Na2ZrO3, in view of the well
known promotional effect of either basic supports[15, 16] or alkali
metal promoters[9, 14–16] on the activity of Ru catalysts. In a
study of the dissociative chemisorption and associative desorp-
tion of N2 on Ru/MgO catalysts, Hinrichsen et al.[39] showed
that, after impregnation with CsNO3, the temperature for N2
desorption from a surface previously saturated with N atoms
(from N2 dissociation) strongly decreased. Moreover, studying
Ru/CNT catalysts for NH3 decomposition, Wang et al.[40] report-
ed that the promotional effect of a modifier can comprise i) an
enhancement of the combinative desorption of nitrogen
atoms and ii) a decrease of the apparent activation energy of
the decomposition reaction. The best promoters for Ru/CNT
catalysts are K, Na, and Li from nitrates, hydroxides or carbo-
nates[40] and their action is an electronic effect on the Ru nano-
particles, like reported for other catalysts for NH3 synthesis.[41–46]
Conversely, electron-withdrawing groups (such as halogens or
sulfates) can act as inhibitors.[40] In this respect, it is not
surprising that the catalyst Ru/LSZ-DP, which comprises a
very complicated mixtures of phases, including chloride ions,
exhibits a very low activity and neither H2 nor N2 desorption
was observed in the TPSR experiments.
Conclusions
The influence of the synthetic method on the catalytic activity
of Ru-based catalysts for ammonia decomposition has been in-
vestigated. Active and stable catalysts were prepared by em-
bedding preformed Ru nanoparticles (protected by a polymer
or a cationic surfactant) into a La-doped ZrO2 (LSZ) support
formed by coprecipitation. The activity of the embedded cata-
lysts was significantly higher than that of reference catalysts
prepared by Ru impregnation of similar supports. Depending
on the preparation method, the oxide support was composed
either of a ZrO2La2O3 solid solution, with tetragonal structure
and high surface area, or of a complex mixture of phases (such
as tetragonal and cubic LSZ, monoclinic ZrO2 and Na2ZrO3),
with small surface areas, derived from the presence of
considerable amounts of a Na-based impurity (owing to the
ChemCatChem 2010, 2, 1096 – 1106  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
precipitation step with NaOH). Notably, the factor governing
the activity of the catalysts was the dispersion of the Ru
nanoparticles. Catalysts prepared by embedding preformed
nanoparticles contained small Ru nanoparticles (as shown by
XRD and chemisorption). As expected, the catalysts prepared
by the impregnation method underwent a significant sintering
of the metal phase, leading to significantly lower conversions.
Temperature-programmed surface reaction experiments with
ammonia were consistent with the catalytic activity results, in-
dicating that high H2 and N2 desorption took place only when
Ru was dispersed as very small nanoparticles.
Experimental Section
Preparation of the catalysts
The catalyst preparation was designed to optimize the perfor-
mance for the ammonia decomposition reaction. A nominal metal
loading of 3 wt % was used for all samples. The preparation of
Ru@LSZ involved with the preparation of colloidal Ru nanoparticles
as first step. LSZ was deposited around the Ru nanoparticles by a
precipitation technique. The two preparation methods differ for
preparation of colloidal Ru nanoparticles.
Deep purple (DP) Method: Preparation of Ru@LSZ-DP
Colloidal Ru nanoparticles were prepared by a reflux method using
poly(N-vinyl-2-pyrrolidone) (PVP) as protecting agent.[26] The
chosen methodology allows modulation of the mean dimension of
the Ru nanoparticles by varying the experimental conditions, such
as the Ru concentration, the PVP/Ru molar ratio and, most impor-
tantly, the molecular weight of the boiling alcohol. In fact, the in-
crease of the molecular weight and the boiling point of the solvent
alcohol resulted in a decrease of the mean dimension of the Ru
nanoparticles. On the other hand, high boiling alcohols are hardly
removable by evaporation and the solubility of metal oxide precur-
sors are low. For the preparation of these samples, ethanol was se-
lected as solvent, leading to very small colloidal Ru nanoparticles
as a deep purple (DP) suspension.
In a 250 mL bottom flask, PVP K30 (0.989 g, 8.9 mmol as monomer-
ic unit) and RuCl3·x H2O (0.233 g, 0.89 mmol Ru) were dissolved in
ethanol (120 mL) under stirring to form a dark red solution. After
heating at reflux for 24 h, a deep purple colloidal suspension was
obtained, according to the procedure reported by Zhang et al.[26]
Under the experimental conditions adopted (VP/Ru = 10, PVP mo-
lecular weight  40 000 g mol1, ethanol as solvent and reducing
agent, reflux time of 24 h), Ru nanoparticles with a mean diameter
of 2.5 nm were obtained. Before the deposition of LSZ around the
nanoparticles, ethanol was evaporated at reduced pressure and
the PVP-protected nanoparticles were resuspended in water
(50 mL).
The La2O3-stabilized ZrO2 (LSZ) was deposited around the metal
nanoparticles by a co-precipitation method. The aqueous Ru
nanoparticles suspension was added under vigorous stirring to an
aqueous solution of ZrO(NO3)2·x H2O (5.77 g, 99 %, Aldrich) and
La(NO3)3·6 H2O (1.01 g, 99.9 %, Aldrich) in water (250 mL). The metal
solution comprising the protected Ru nanoparticles was added
dropwise to an aqueous solution of NaOH (220 mL, 2.5 m). The ob-
tained precipitate was stirred for 2 h and then filtered and briefly
washed with water on the filter. The solid obtained was suspended
in 2-propanol (300 mL) and heated at reflux for 4 h to stabilize the
www.chemcatchem.org 1103

texture of the oxide matrix.[47, 48] After filtration, the solid was dried
at 120 8C overnight and calcined in a static oven at 500 8C for 5 h
with heating and cooling rates of 1 8C min1.
NaBH4 method: Preparation of Ru@LSZ-NaBH4
Metal nanoparticles were synthesized by reduction of RhCl3 with
NaBH4 in an aqueous solution containing cationic surfactants. The
Ru nanoparticles were protected against aggregation by entrap-
ment inside the hydrophobic environment of the micelles formed
by the surfactants. N-Hexadecyl-N-(2-hydroxyethyl)-N,N-dimethyl
ammonium bromide (HEAC16Br) was used as protecting agent.
The use of HEAC16X (X = Cl or Br) as protecting agent for metal
nanoparticles preparation has been extensively reported for differ-
ent noble metals, such as Rh,[49, 50] Ir,[51] Pt,[52] Pd,[53] and Ru.[27]
Moreover, Rh nanoparticles protected by HEAC16Br have already
been used as building blocks for the preparation of embedded cat-
alysts.[22, 24, 25]
The cationic surfactant HEAC16Br was prepared by reaction of
1-bromohexadecane (99 %, Fluka) with a 30 % excess of N,N-dime-
thylethanolamine (99 %, Fluka) in absolute ethanol (Aldrich) at
reflux for 1 h,[54] and purified by crystallization in absolute etha-
nol,[55] yield 70–80 %, m.p. 200–210 8C. The 1H and 13C NMR spectra
are in agreement with those reported in Ref. [50]).
The preparation of HEAC16Br-protected Ru nanoparticles was
carried out as follows. A solution of surfactant HEAC16Br (3.262 g,
8.3 mmol) and NaBH4 (84 mg, 2.2 mmol) in water (210 mL) and a
solution of RuCl3·x H2O (0.233 g, 0.89 mmol Ru) in water (52 mL)
were thermostated at 20 8C for at least 1 h. Then, the solution con-
taining HEAC16Br and NaBH4 was quickly added under vigorous
stirring to the Ru solution to obtain an aqueous Ru colloidal sus-
pension. The reduction occurs instantaneously, revealed by the im-
mediate color change from yellow-brown to black. The suspension
is then stirred for 2 h to decompose the excess of the reducing
agent. Ru nanoparticles with a mean dimension of 3.0 nm are
reported following this preparation.[27]
The La2O3-stabilized ZrO2 (LSZ) was deposited around the metal
nanoparticles by a co-precipitation method, as previously de-
scribed. The aqueous Ru nanoparticles suspension was added
under vigorous stirring to an aqueous solution of ZrO(NO3)2·x H2O
(5.77 g, 99 %, Aldrich) and La(NO3)3·6 H2O (1.01 g, 99.9 %, Aldrich) in
water (250 mL). The metal solution comprising the protected Ru
nanoparticles was added dropwise into an aqueous solution of
NaOH (220 mL, 2.5 m). The obtained precipitate was stirred for 2 h
and then filtered. In this case, the precipitate was washed by sus-
pending the solid into a NH4NO3/NH4OH buffer solution (200 mL,
pH 10), in order to remove the bromide ions involved in the syn-
thesis. Finally, the solid obtained was suspended in 2-propanol
(300 mL) and heated at reflux for 4 h in order to stabilize the tex-
ture of the oxide matrix.[47, 48] After filtration, the solid was dried at
120 8C overnight and calcined in a static oven at 500 8C for 5 h
with heating and cooling rates of 1 8C min1.
For comparison, reference impregnated samples Ru/LSZ were pre-
pared. The LSZ supports were synthesized using the already de-
scribed procedures, without the Ru nanoparticles. After calcination
at 500 8C for 5 h, the metal was deposited by conventional
impregnation, by dispersing the support into an ethanol solution
containing the appropriate amount of RuCl3·x H2O. After stirring for
1 h and evaporation of the solvent under reduced pressure, the
samples were dried at 120 8C overnight and finally calcined at
400 8C for 5 h (heating rate = 3 8C min1).
1104 www.chemcatchem.org  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
T. Montini et al.
Catalytic activity evaluation
Catalytic experiments were conducted in a U-shaped 8 mm ID
quartz reactor under atmospheric pressure. Pure ammonia (transis-
tor grade purity) was used as reactant. The mass of catalysts and
the gas flow rates were adjusted in order to test the samples
under different conditions: GHSV = 4000 mL g1 h1 (250 mg of cat-
alyst and 16.1 mL min1 of NH3) and GHSV = 30 000 mL g1 h1
(100 mg of catalysts and 51.0 mL min1 of NH3).
Before any experiment, the calcined materials were activated by re-
duction in H2 flow (35 mL min1) at 800 8C for 3 h. After reduction,
H2 was removed by Ar flow (35 mL min1) for 30 min and the tem-
perature was decreased to 250 8C. Then, NH3 was introduced into
the reactor, and the system was stabilized for 30 min. The catalytic
activity was evaluated every 50 8C from 250 to 800 8C. The gaseous
mixture was analyzed three times at each temperature. The cata-
lyst was subjected to two activity cycles to verify the stability after
the reaction at high temperature. For the stability test, after activa-
tion by H2 reduction at 800 8C, the samples were cooled at 500 8C
under Ar flow (35 mL min1). After stabilization of the temperature,
NH3 was introduced into the reactor and the gaseous mixture
released by the reactor was analyzed every hour.
On-line GC analysis was performed with a Shimadzu 2010 gas-
chromatograph equipped with a TCD (AGC Instruments) equipped
with Au filaments to avoid the corrosion by NH3. Two packed col-
umns with Ar as carrier were used. A Molsieve 5 A column was
used for the separation of H2 and N2 while a Porapak Q column
was used for the separation of NH3 from permanent gases (H2 and
N2). The analysis of the gases was performed by the alternative
injection of the mixture into the columns by use of a 10-way valve
equipped with 2 loops.
The NH3 conversion was calculated on the bases of the following
reaction:
2 NH3 !N2 + 3 H2
Catalyst characterization
The BET surface areas, pore volumes, and average pore diameters
of the catalysts were measured by N2 physisorption at liquid-
nitrogen temperature by using a Micromeritics ASAP 2020.
Approximately 200 mg of the catalyst, previously degassed at
350 8C for 18 h, were used for each analysis.
The metal dispersion was estimated by static H2 chemisorption at
100 8C by using a Micromeritics ASAP 2020 C instrument according
to the indication reported by Okal et al.[37] Prior to the H2 adsopr-
tion, the catalysts were reduced at 800 8C for 3 h flowing H2
(35 mL min1) and degassed at 800 8C for 5 min and at 400 8C for
3 h. The H2 adsorption isotherms were recorded in the 3.3–
53.3 kPa pressure range with an equilibration time of at least 1 h
for each point. The total H2 adsorption was evaluated in the first
isotherm. After that, the sample was evacuated at 100 8C for 5 min
and a second isotherm was recorded. The chemisorbed H2 was de-
termined by extrapolation to zero pressure of the linear part of the
adsorption isotherm after removing the so called reversible hydro-
gen adsorption (“double isotherm” procedure) and assuming a
chemisorption stoichiometry of H/Ru = 1:1.
Hydrogen chemisorption experiments in dynamic conditions were
performed at 100 8C by using a ChemBET Pulsar Automatic Chemi-
sorption Analyzer from Quantachrome Instruments. Before H2 ad-
sorption measurement, the catalyst (150 mg) was placed in a tubu-
ChemCatChem 2010, 2, 1096 – 1106
Embedded Ru@ZrO2 Catalysts
lar quartz reactor and pretreated by drying at 450 8C in He for 1 h,
then reducing in 5 % H2/Ar at 800 8C for 2 h, evacuation at the
same temperature in He for 1.5 h, and finally cooling to 100 8C in
He. The pulse adsorption of hydrogen was monitored by using a
thermal conductivity detector (TCD). To ensure optimum sensitivity,
nitrogen was used as carrier gas. Prior starting the analysis, the
TCD detector was stabilized in 75 mL min1 N2 flow for 2 h at
100 8C. Then, pulses of pure H2 (73 mL) were introduced until
saturation. Metal surface area and average crystallite size were
calculated assuming the stoichiometry H/Ru = 1:1.
Powder X-ray diffraction (XRD) patterns of the samples after
various treatments were recorded by using a computer-controlled
Philips X’Pert diffractometer using CuKa radiation (l = 0.15406 nm).
The data were collected in the 2 q range 10–1008 with steps of
0.028. The Rietveld analysis were performed using the software
PowderCell. Owing to the complexity of some samples, the mean
crystallite sizes were calculated applying the Scherrer’s equation to
the main reflection of each phase.
Temperature programmed reduction (TPR) experiments were per-
formed on approximately 35 mg samples of the calcined materials.
The samples were pretreated at 400 8C for 1 h by pulsing O2 in an
Ar flow every 75 s, then purged with Ar at 400 8C for 15 min and
cooled to room temperature. H2(5 %)/Ar was admitted into the
reactor and the flow was allowed to stabilize for 30 min, before
increasing the temperature to 1000 8C with a heating rate of
10 8C min1. The H2 uptake was monitored using a thermal
conductivity detector (TCD).
Temperature programmed surface reactions (TPSR) were conducted
in a home-made flow apparatus by using a mass spectrometer
Hiden HPR20 as analyzer. In a typical NH3-TPSR experiment, the
sample (ca. 0.25 g) was loaded in U-shaped quartz microreactor.
The samples were reduced in flowing H2 (35 mL min1) at 800 8C
for 3 h. After this treatment, the adsorbed H2 was removed by
purging the system with Ar at 800 8C for 30 min. Afterwards, the
samples were cooled at 110 8C under the inert gas flow. For NH3
adsorption, the reduced samples were saturated flowing
NH3(10 %)/Ar (50 mL min1) at 110 8C for 30 min. After NH3 adsorp-
tion, the sample was flushed in Ar flow at 110 8C for 1 h to remove
physically adsorbed NH3. The NH3 TPSR profile for each sample was
recorded by increasing the temperature from 110 to 800 8C at a
heating rate of 20 8C min1 under a flow of Ar (50 mL min1). The
desorbed products were analyzed by means of a mass spectrome-
ter operating in the electron impact mode with a ionization energy
of 35 eV. The desorbed species were identified on the basis of the
intensity of various mass fragments: m/z = 2 for H2, m/z = 28 for N2
and m/z = 16 for NH3 (the parent peak, m/z = 17, is superimposed
with the cracking pattern of desorbed water).
Acknowledgements
Prof. M. Graziani (University of Trieste) is gratefully acknowledged
for the kind collaboration and the helpful discussion. BL thanks
Acta SpA for financially support her Ph.D. position. University of
Trieste, Acta SpA, ICCOM-CNR, INSTM, CENMAT and PRIN2007 “2nd
generation sustainable processes for the hydrogen production
from renewable sources” are gratefully acknowledged for
financial support.
ChemCatChem 2010, 2, 1096 – 1106  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Keywords: ammonia · decomposition · heterogeneous
catalysis · nanoparticles · ruthenium
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