Catalysis Letters (2022) 152:1170–1181

https://doi.org/10.1007/s10562-021-03709-2

Ru Nanoparticles on ­Pr2O3 as an Efficient Catalyst for Hydrogen

Production from Ammonia Decomposition
Xilun Zhang1,2 · Lin Liu1 · Ji Feng1,2 · Xiaohua Ju1 · Jiemin Wang1,3 · Teng He1 · Ping Chen1

Received: 19 February 2021 / Accepted: 11 June 2021 / Published online: 29 June 2021
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2021

Abstract
Development of efficient catalysts for ammonia decomposition is crucial for hydrogen production from ammonia. Herein,
Ru nanoparticles (NPs) highly dispersed on P ­ r2O3 (Ru/Pr2O3) were prepared and investigated as catalyst for ammonia
decomposition reaction. Under relatively high weight hourly space velocity (WHSV = 30,000 mL ­gcat−1 ­h−1), the Ru/Pr2O3
achieves a ­H2 production rate of 20.9 mmol ­gcat−1 ­min−1 at 450 °C, which is superior to Ru/Pr6O11 and many other typical
oxides supported Ru catalysts. Detailed characterization results demonstrate that P ­ r2O3 has high density of basic sites, abun-
dant oxygen vacancies, and strong interaction with Ru, which can modulate electronic properties of Ru NPs and enhance
the intrinsic activity of the catalyst, making the catalyst highly active for ammonia decomposition. Moreover, the Ru/Pr2O3
catalyst also exhibits excellent stability and can maintain its high activity for over 100 h. The use of P
­ r2O3 as support offers
opportunity to improve the catalytic performance of Ru-based catalysts for ammonia decomposition.
Graphic Abstract
The high density of basic sites, abundant oxygen vacancies of ­Pr2O3, and the strong metal–support interaction effectively
promote the electron donation to Ru nanoparticles, enabling the superior catalytic performance of Ru/Pr2O3 for ammonia
decomposition.

Keywords Ru nanoparticles · Pr2O3 · Ammonia decomposition · Hydrogen production · Metal–support interaction ·

Electron transfer

* Lin Liu
liulin@dicp.ac.cn
* Ping Chen
pchen@dicp.ac.cn
Extended author information available on the last page of the article

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Ru Nanoparticles on ­Pr2O3 as an Efficient Catalyst for Hydrogen Production from Ammonia…
1 Introduction
Hydrogen is one of the most promising energy carriers
for building a more sustainable future energy system. Up
to now, storage of ­H2 through economic and sustainable
way is still a major challenge in the scientific community
[1–3]. Ammonia ­(NH3) plays an important role in the earth
ecosystem, providing a nitrogen source for manmade ferti-
lizers and serving as a precursor of various fibers and dyes
[4]. In recent years, ammonia attracts increasing attention
as a carbon-free H­ 2 carrier for its high content of hydrogen
(17.7 wt%), high density of energy (ca. 3 kWh ­kg−1), and
the ease of storage and transportation [5, 6]. ­NH3 decom-
position reaction, a critical step for utilization of N ­ H3 as
­H 2 feedstock for proton-exchange membrane fuel cells
(PEMFC), can only be achieved in the presence of efficient
catalysts [7–9]. Because of high activity at relatively low
temperatures (400–500 °C), high degree of metal disper-
sion and excellent stability, supported Ru-based catalysts
have been widely used as efficient catalysts in ­NH3 decom-
position reaction during the past 30 years [10, 11].
NH3 decomposition on Ru-based catalysts has been rec-
ognized to be a structure sensitive reaction. In Ru-based
catalytic systems, the size and structure of catalytically
active Ru particles greatly affect the catalytic perfor-
mances of catalysts. Meanwhile, the surface property and
structure of support can also influence the catalytic per-
formances of supported Ru catalysts significantly [12–15].
Thus, discovering new kinds of oxide supports that can
effectively disperse and anchor Ru particles is one of
the major concerns for design of efficient Ru-based N ­ H3
decomposition catalysts. In recent years, a variety of metal
oxides including MgO, ­SiO2, ­Al2O3, ­TiO2, ­ZrO2, ­CeO2,
Mg–Al mixed oxide, barium hexaaluminate, and perovs-
kite material have been investigated as supports of Ru-
based catalysts for ­NH3 decomposition [16–23]. The role
of oxide supports is mainly to immobilize the active com-
ponent and improve the metal dispersion. Additionally,
the metal–support interaction has significant impact on the
geometric structures and electric properties of metal cata-
lysts and plays a vital role in tuning the catalytic behavior
of supported metal catalysts [24].
Owing to the interactions between the localized 4f elec-
trons and delocalized conduction bands, rare earth oxides
such as ­La2O3, ­CeO2 and Y ­ 2O3 have attracted increasing
attention as supports of catalysts for N ­ H3 decomposition
[20, 25–28]. As one of the important rare earth materials,
praseodymium oxides with unique optical and electrical
properties have been studied for application in materials
with higher electrical conductivity, oxygen-storage com-
ponents, pigments, and catalysis [29–32]. Praseodymium
oxides have a series of stoichiometrically defined P ­ r nO2n−2
1171
(n = 4, 7, 9, 10, 11, 12, ∞) structure, and the extreme cases
are ­Pr2O3 and ­PrO2 [33, 34]. Among these different stoi-
chiometric praseodymium oxides, ­Pr6O11 is the most stable
phase at ambient temperature in air. Due to the multiple
valence states and oxygen-deficient structures, praseo-
dymium oxides have been widely used as catalysts, sup-
ports, and dopants in a variety of catalytic reactions (e.g.,
CO oxidation, ­CO2 methanation, synthesis of ethane and
ethylene, automotive emission control, ammonia synthesis
and decomposition) [35–40]. Over the past few decades,
many studies have shown that the surface property and
structure of oxide support can profoundly affect catalytic
performance of supported Ru catalysts in N ­ H3 decomposi-
tion. Therefore, tuning the phases of praseodymium oxides
may offer new opportunity for improving the catalytic per-
formance of supported Ru catalysts.
In this work, highly dispersed Ru nanoparticles anchored
on ­Pr2O3 and ­Pr6O11 were prepared and investigated in ­NH3
decomposition reaction. The obtained Ru/Pr 2O3 shows
remarkably enhanced catalytic activity in comparison with
that of the Ru/Pr6O11. The structures of the Ru nanoparticles
in Ru/Pr2O3 and Ru/Pr6O11 catalysts were characterized by
a variety of complementary techniques including X-ray dif-
fraction (XRD), transmission electron microscopy (TEM),
electron paramagnetic resonance (EPR), X-ray photoelec-
tron spectroscopy (XPS) and X-ray absorption spectroscopy
(XAS). Structure analyses and characterizations revealed
that the synergy between the surface basic sites, oxygen
vacancies of ­Pr2O3, and the strong interaction between Ru
NPs and P ­ r2O3 remarkably enhanced the intrinsic activity of
Ru NPs in Ru/Pr2O3 for ­NH3 decomposition.
2 Experimental
2.1 Materials
Praseodymium nitrate hexahydrate (Pr(NO3)3·6H2O) was
purchased from Aladdin Co., Ltd. Ruthenium chloride
hydrate ­RuCl3·xH2O was purchased from Shanghai Tuosi
chemical Co., Ltd. Potassium bicarbonate (­ KHCO3), urea
(CO(NH2)2) and nitric acid (­ HNO3) were all obtained from
Sinopharm Chemical Reagent Co. Ltd. All chemical rea-
gents in this work were analytical grade and used as received
without further purification.
2.2 Preparation of ­PrCO3OH Support Precursor
The ­PrCO3OH support precursor was prepared as following
steps. First, 4.35 g of Pr(NO3)3·6H2O and 3.0 g of K
­ HCO3
were dissolved in 100 ml deionized water, respectively.
Then the Pr(NO3)3·6H2O solution was added dropwise into
the ­KHCO3 solution under stirring at room temperature,
13
1172
followed by an additional stirring for 1 h with the formation
of a milky slurry. The product was filtered and washed with
deionized water for three times at least and dried at 80 °C
for 8 h to obtain ­PrCO3OH support precursor.
2.3 Preparation of the Catalysts
Ru/Pr2O3 catalyst with different Ru contents of 1–5 wt%
were prepared by deposition–precipitation method. In a typi-
cal synthesis of 5% Ru/Pr2O3 sample, 1.356 g of ­PrCO3OH
support precursor was added into 2 mL of R ­ uCl3·xH2O aque-
ous solution (molar ratio of R­ uCl3: ­HNO3 = 1:1, 51.36 g/L),
and then dispersed into 60 ml of deionized water with stir-
ring. Subsequently, 5.94 g of urea (molar ratio of ­RuCl3:
urea = 1:200) was added into the suspension. The mixture
was refluxed at 80 °C for 8 h and aged at room tempera-
ture for 12 h with stirring. The dark precipitate was sepa-
rated by filtration and washed by deionized water to neu-
tral. The obtained sample were dried at 80 °C overnight.
The Ru/Pr2O3 catalyst was obtained after the dried sample
was reduced at 550 °C in an ­NH3 flow (25 mL/min) for
2 h. Unless noted, Ru/Pr2O3 refers to the sample with a Ru
content of 5 wt%.
For the 5% Ru/Pr6O11 catalysts, prior to the preparation
of the catalyst, the P­ rCO3OH support precursor was calci-
nated in air at 500 °C and the P ­ rCO3OH was decomposed
into ­Pr6O11. Then the obtained P ­ r6O11 was used as support.
The Ru/Pr6O11 catalysts was prepared by incipient wetness
impregnation method with acetone as solvent. Typically,
0.1351 g of R ­ uCl3·xH2O was dissolved in 5 mL of acetone.
1.0 g of obtained P ­ r6O11 was added into the solution and
stirred for 1 h. Then the solvent was removed and the sample
was dried at 80 °C overnight. The Ru/Pr6O11 catalyst was
obtained after the dried sample was reduced at 550 °C in an
­NH3 flow (25 mL/min) for 2 h. Normally, Ru/Pr6O11 also
refers to the sample with a Ru content of 5 wt%.
2.4 Catalytic Performance Evaluation
Catalytic ­NH3 decomposition reaction was performed in a
continuous fixed-bed flow quartz reactor under atmospheric
pressure. 50 mg of the reduced catalyst (40–60 mesh) was
placed in the central section of reactor. Catalytic perfor-
mance evaluation was carried out in pure N­ H3 with a flow
rate of 25 mL ­min−1 (WHSV = 30,000 mL ­gcat−1 ­h−1) in the
range of 300–550 °C. Gas product analysis was conducted
on a gas chromatograph (Agilent, 7890B) equipped with a
TCD detector and Poropak N column by using ­H2 as carrier
gas.
The conversion of ­NH3 (CNH3) was calculated as the given
equation below:
13
X. Zhang et al.
ANH3,in − ANH3,out
CNH3 (%) =
ANH3,in
where ANH3,in and ANH3,out is the total amount of ­NH3 in inlet
and outlet, respectively.
The ­H2 production rate was calculated form the N­ H3 con-
version (CNH3) by the equation below:
WHSV × CNH3 × 1.5
H2 production rate (mmol g−1 min−1 ) =
cat Vm × 60
where WHSV is the weight hourly space velocity (30,000 mL
­gcat−1 ­h−1), CNH3 is the conversion of N
­ H3, Vm is molar vol-
ume of gas at 25 °C and 1 atm (24.45 mL ­mmol−1).
TOF H2 was calculated from the H ­ 2 production rate
divided by the exposed surface of the Ru atoms:
H2 production rate × 10−3
TOFH2 (s−1 ) =
60 × Ru content × DRu ∕Ruat
where D Ru is Ru dispersion of the catalyst deter-
mined by TEM statistical analysis, H ­ 2 production
rate (mmol ­g cat −1 ­m in −1 ), Ru at is molar mass of Ru
(101.07 g ­mol−1).
2.5 Catalyst Characterization
The actual Ru contents of the sample were determined by
inductively coupled plasma optical emission spectroscopy
(ICP-OES, Optima 7300DV, Perkin-Elmer, USA). X-ray
diffraction (XRD) patterns were recorded on a PANalytical
X’Pert with Cu-Kα radiation (λ = 1.5418 Å) at 40 kV and
40 mA. Nitrogen physisorption was undertaken at − 196 °C
with a QUADRASORB SI (Quantachrome, USA) ana-
lyzer. The samples were degassed at 300 °C for 6 h before
the measurements. The surface areas were determined by
Brunauer–Emmett–Teller (BET) method. Scanning elec-
tron microscopy (SEM) was performed on a JEOL JSM-
7800F instrument. Transmission electron microscopy (TEM)
and high-resolution transmission electron microscopic
(HRTEM) images were obtained on a JEOL JEM-2100X at
200 kV. The dispersion of Ru particles (DRu) was calculated
using the equation by Borodziński and Bonarowska [41]:
√
dat × 3.32
DRu = 1.23
for 0.2 ≤ DRu ≤ 0.92
dTEM
dat × 5.01
DRu =
dTEM
for DRu < 0.2
where dat is the atomic diameter of Ru (0.269 nm).
Temperature-programmed desorption of ­CO2 ­(CO2-TPD)
was performed on an AutoChem 2920 instrument. Prior to
Ru Nanoparticles on ­Pr2O3 as an Efficient Catalyst for Hydrogen Production from Ammonia… 1173

the experiment, 50 mg of sample was reduced in a pure

­ 2 flow at 500 °C for 2 h, purged in a He flow for another
H
1 h, and cooled to 50 °C. Then pure C­ O2 was adsorbed for
30 min. After purging the physisorbed C­ O2 in a He flow for
30 min, the sample was heated from 50 to 800 °C with a
ramping rate of 10 °C/min.
The electron paramagnetic resonance (EPR) spectra
were recorded on a Bruker A200 spectrometer operated at
the X-band frequency. The X-ray absorption fine structure
(XAFS) spectra at Ru K edge (22,117 eV) were collected at
the BL14W1 beamline of Shanghai Synchrotron Radiation
Facility (SSRF) using a Si (311) double-crystal monochro-
mator. The samples were sealed with KAPTON film to avoid
air contamination before test. The spectra were recorded at
room temperature under transmission mode and the energy
was calibrated by using Ru foil. k2-weighted Fourier trans-
form EXAFS (FT-EXAFS) were analyzed using carried out
Athena and Artemis Software. Wavelet transform EXAFS
(WT-EXAFS) was analyzed by Morlet wavelets with opti-
mum resolution. Surface chemical states of catalysts were
characterized by X-ray photoelectron spectroscopy (XPS)
using an Escalab 250 Xi X-ray photoelectron spectrometer
(Thermo Scientific) with nonmonochromatic Al Ka radia-
tion. The binding energy was calibrated according to the
XPS peak at carbon 1s at 284.8 eV.

3 Results and Discussion

Praseodymium carbonate hydroxide ­(PrCO3OH) and ­Pr6O11

derived from P ­ rCO3OH were used as supports to prepare
Ru/Pr2O3 and Ru/Pr6O11 catalysts, respectively. The crystal
structure of the supports and catalysts after N­ H3 decomposi-
tion reaction were analyzed by XRD (Fig. 1). The diffraction
peaks of Ru/Pr2O3 can be indexed into a hexagonal P ­ r 2O 3
phase (JCPDS Card No. 06-0410, Fig. 1a). No feature peaks
corresponding to the ruthenium species can be found in the
XRD patterns, indicating the high dispersion of Ru NPs on
the surface of P ­ r2O3 support. For the Ru/Pr6O11, relatively
weak peaks at 41.6° and 44.5° associated with the (002) and
(101) reflections of Ru metal (JCPDS Card No. 01-1256)
can be observed in addition to the characteristic diffraction
peaks associated with cubic ­Pr6O11 phase (JCPDS Card No.
42-1121, Fig. 1b). The diffraction peaks of metallic Ru sug-
gest the relatively larger Ru NPs in Ru/Pr6O11. It is also
worth to be noted that the characteristic diffraction peaks
of ­Pr6O11 support in Ru/Pr6O11 shift towards lower angle in
compared with that of pure P ­ r6O11 support, which could be
attributed to the lattice expansion of ­Pr6O11 under reducing
atmosphere. Because the ionic radius of ­Pr3+ (0.1126 nm)
is larger than that of ­Pr4+ (0.096 nm), some part of ­Pr4+ was
reduced to P­ r3+ during the reduction, resulting in the lattice
expansion of ­Pr6O11 [42]. However, due to the shift of peaks
Fig. 1  XRD pattens of Ru/Pr2O3 and Ru/Pr6O11 catalysts. Standard
patterns of Ru, P
­ r2O3 and ­Pr6O11 were included as references
is only 0.5°–1.0°, the bulk phase of cubic ­Pr6O11 structure in
Ru/Pr6O11 were still maintained, indicating its highly crys-
talline structure. There are some additional weak peaks not
assigned to P­ r6O11 or Ru, including the peaks at 25.6°, 31.1°,
and 34.5°. These additional peaks should be associated with
other phases of praseodymium oxides with a mixture of P ­ r3+
4+
and ­Pr [34]. Due to the weak intensity of these peaks and
the complex phases of praseodymium oxides, these peaks
are difficult to be attributed to the individual phase. The
physical properties of the catalysts are shown in Table 1, the
­Pr2O3 exhibits higher BET surface area than that of ­Pr6O11,
which may be beneficial for the dispersion of Ru NPs. The
actual Ru content was determined with ICP-OES analysis.
Ru contents in these two samples are close to the desired 5
wt% Ru mass loading.

13
1174 X. Zhang et al.

Table 1  Physical properties of the Ru/Pr2O3 and Ru/Pr6O11 catalysts mildly endothermic nature of ­NH3 decomposition reaction.
Samples Ru content BET Mean Dispersion (%) a For the catalysts with similar Ru content, the 5% Ru/Pr2O3
(wt%) surface area particle size catalyst shows significantly higher catalytic activity than
­(m2/g) (nm)a 5% Ru/Pr6O11 in the whole temperature range. The activ-
ity of 5% Ru/Pr6O11 could only be detected at the tempera-
Ru/Pr2O3 4.8 30.1 2.0 52.0
tures above 350 °C. By contrast, 5% Ru/Pr2O3 exhibits an
Ru/Pr6O11 4.7 18.1 6.6 20.4
obvious ­NH3 conversion of 6.13% corresponding to a ­H2
a
Mean particle size and dispersion of Ru NPs were determined by production rate of 1.9 mmol ­gcat−1 ­min−1 at the tempera-
TEM study using the equation of Borodziński and Bonarowska [41] ture as low as 300 °C. Furthermore, the N ­ H3 conversion
of 5% Ru/Pr6O11 at 450 °C is only 16.6% with a ­H2 pro-
The activities of praseodymium oxide supported Ru NPs duction rate of 5.1 mmol ­gcat−1 ­min−1, which is at a com-
catalysts in N
­ H3 decomposition reaction were evaluated, parable level with the activity of previously reported Ru/
and the temperature-dependence of activities of Ru/Pr2O3 Pr6O11 (3.1 mmol ­gcat−1 ­min−1) in the literature at the same
and Ru/Pr6O11 catalysts results are presented in Fig. 2a. temperature [39]. However, 5% Ru/Pr2O3 gives a ­NH3 con-
For all the samples, the ­NH3 conversion increases with version as high as 68.2% at 450 °C, 4.1 times that of the 5%
increase of reaction temperature, agreeing well with the Ru/Pr6O11 at the same temperature. The activities of Ru/

Fig. 2  a Temperature-dependence of ­NH3 decomposition activities
of Ru/Pr2O3 with different Ru contents and 5% Ru/Pr6O11 catalysts.
b Influence of WHSV on the ­NH3 conversion and ­H2 production rate
of 5% Ru/Pr2O3 catalyst for ­NH3 decomposition at different tempera-
ture. c Long-term stability tests of 5% Ru/Pr2O3 catalyst at 450 and
500 °C, respectively. d Arrhenius plots and apparent activation ener-
gies of Ru/Pr2O3 with different Ru contents and 5% Ru/Pr6O11 cata-
lysts for N
­ H3 decomposition

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Ru Nanoparticles on ­Pr2O3 as an Efficient Catalyst for Hydrogen Production from Ammonia…
Pr2O3 catalysts with different Ru contents were also evalu-
ated. As shown in Fig. 2a, ­NH3 conversion increases with
the increase of Ru content from 1 to 5 wt%. Specifically, the
­H2 production rate at 450 °C shows linear increase from 3.6
to 20.9 mmol ­gcat−1 ­min−1 with the increase of Ru content
from 1 to 5% (Fig. S1). Remarkably, 2% Ru/Pr2O3 even gives
higher activity than that of the 5% Ru/Pr6O11, manifesting
the superior catalytic activity of Ru/Pr2O3 catalyst. A com-
parison of activity of Ru/Pr2O3 catalyst with those of the typ-
ical supported Ru catalysts for N ­ H3 decomposition reported
in literatures is listed in Table S1. The activity of 5% Ru/
Pr2O3 is not only significantly higher than that of 5% Ru/
Pr6O11 but also outperforms most of the promoter-free effi-
cient Ru catalysts under similar reaction conditions. Under
identical reaction conditions, the 5% Ru/Pr2O3 at 450 °C
achieves a ­H2 production rate of 20.9 mmol ­gcat−1 ­min−1,
comparable with that of the highly efficient Ru/c–MgO
catalyst [43].
The weight hourly space velocity (WHSV) is a significant
factor for practical application [44]. The influence of WHSV
on the ­NH3 decomposition activity was also investigated.
As shown in Fig. 2b, ­NH3 conversion decreases with the
increase of WHSV over 5% Ru/Pr2O3 at the temperature of
450, 475 and 500 °C as a result of decrease in the residence
time of the N­ H3 over the catalyst bed [45]. By contrast, the
increase of WHSV results in a remarkable increase of H ­ 2
production rate. For example, at 500 °C, the ­H2 production
rate increases from 5.1 to 50 mmol ­gcat−1 ­min−1 with WHSV
increasing from 5000 to 100,000 mL ­gcat−1 ­h−1. Further-
more, the long-term stability is critical for evaluating the
catalytic performance of the catalyst in ­NH3 decomposition.
Here, two sets of stability test of 5% Ru/Pr2O3 catalyst were
carried out at 450 and 500 °C with relatively high space
velocity of 30,000 mL ­gcat−1 ­h−1, respectively. As shown in
Fig. 2c, both of the ­NH3 conversions at 450 and 500 °C over
5% Ru/Pr2O3 remain almost constant during the test period
of 100 h, evidencing the high stability of 5% Ru/Pr2O3 cata-
lyst, which is crucial for the potential application of 5% Ru/
Pr2O3 for application in ­COx-free hydrogen production from
­NH3 decomposition.
To clarify the origin of high activity of Ru/Pr2O3 catalyst,
the apparent activation energies (Ea) of different catalysts
were calculated based on H ­ 2 production rates far away from
the equilibrium value. Figure 2d shows Arrhenius plots of
5% Ru/Pr6O11 and Ru/Pr2O3 catalysts with different Ru con-
tents. Correlating well with the catalytic activity results, a
remarkable decrease in the Ea value can be observed for
5% Ru/Pr2O3 (61.9 kJ ­mol−1) in comparison with that of
the 5% Ru/Pr6O11 (87.2 kJ ­mol−1). For the Ru/Pr2O3 with
different Ru contents, the apparent activation energies are
in the range of 57.7–66.3 kJ ­mol−1. The Ea of 3% Ru/Pr2O3
(57.7 kJ ­mol−1) is one of the lowest Ea values for Ru-based
­NH3 decomposition catalysts in the literatures (Table S1).
1175
Additionally, the similar Ea values elucidate the similar
structure of active sites in Ru/Pr2O3 catalysts.
The morphology and structure of the catalysts were ana-
lyzed by SEM and TEM. As shown in Fig. 3a, ­Pr2O3 displays
a well-defined petal-like structure with a diameter of ca.
2.0 μm, in which many exposed defects could be observed
on the surface. The TEM image demonstrated that the ­Pr2O3
support in Ru/Pr2O3 possess good crystallinity. Interplanar
spacings of 0.30 nm, corresponding to the lattice fringes
of the (002) facet of P ­ r2O3, can be clearly identified in the
TEM image of Ru/Pr2O3 (Fig. 3b). Meanwhile, the P ­ r2O 3
exhibits higher BET surface area than that of ­Pr6O11, which
also should be beneficial for dispersion of Ru NPs (Table 1).
To confirm this, TEM was applied to investigate the parti-
cle size distribution of Ru NPs of the catalysts. As the low
contrast of Ru and Pr elements in the TEM images, it is chal-
lenging to distinguish the Ru NPs from the more condensed
praseodymium oxide support. Thus, the Ru NPs can only
be determined from the NPs distributed on the edge of the
support. By counting ca. 100 Ru NPs from different TEM
images in various regions (Fig. S2 and S3), the particle size
distribution and average diameter of Ru NPs of Ru/Pr2O3
and Ru/Pr6O11 samples can be preliminarily estimated. The
average particle size of Ru NPs in Ru/Pr2O3 is ca. 2.0 nm
(Fig. 3c), which is much smaller than that of the Ru/Pr6O11
(6.6 nm, Fig. 3f). The dispersion of Ru NPs are shown
in Table 1, the Ru dispersion of Ru/P2O3 is about 52.0%,
which is much higher than that of the Ru/Pr6O11 (20.4%).
It reveals that the use of P­ r2O3 support as support leads to
much enhanced dispersion of Ru, which is in line with the
superior catalytic activity of Ru/Pr2O3 catalyst. Furthermore,
HRTEM image of Ru/Pr2O3 reveals that highly dispersed
Ru NPs are embedded in support and partially covered by
­Pr2O3 (inset of Fig. 3b), indicating the strong metal–support
interaction between Ru NPs and ­Pr2O3.
Currently, the B5 sites on the surface of Ru particles have
been widely accepted as the active sites of Ru-based cata-
lysts for ­NH3 decomposition [14, 46, 47]. Many theoretical
and experimental results demonstrate that the amount of
B5 sites on the Ru NPs is highly dependent on the particle
size of Ru NPs. The maximum probability for B5 sites is of
1.8–2.5 nm in Ru particle size. For the particles larger than
the optimal size region, the probability for B5 sites decrease
monotonically [46]. As a result, the Ru NPs on P ­ r2O3 with
an optimal particle size of 2.0 nm are expected to show much
enhanced concentration of B5 sites on the surface, agreeing
well the superior catalytic performance.
Ru catalyzed ­NH3 synthesis is recognized to be a structure
sensitive reaction, and the ­TOFH2 value usually increases
with the increase of size of Ru nanoparticles. A rise in TOF
over promoted Ru/Al2O3 and AC-supported Ru catalysts has
been observed with the increase of size of Ru particles [48,
49]. Additionally, it has been found that ­NH3 decomposition
13
1176 X. Zhang et al.

Fig. 3  Representative SEM, TEM images and Ru particle size distributions of Ru/Pr2O3 (a–c) and Ru/Pr6O11 (d–f) catalysts after N
­ H3 decompo-
sition reaction

on Ru/γ-Al2O3 catalysts is also highly structure sensitive,

with ­TOFH2 values increasing by almost 2 orders of magni-
tude as the particle size increases from 0.8 to 7.5 nm [15].
Different from the Ru-based catalyst systems reported in
the previous studies, 5% Ru/Pr2O3 with a relatively small
particle size of Ru NPs shows much higher ­TOFH2 value
than that of the 5% Ru/Pr6O11 catalyst under identical reac-
tion conditions. For example, 5% Ru/Pr6O11 with an average
Ru particle size of 6.6 nm gives a ­TOFH2 value of 0.89 ­s−1
at 450 °C. For 5% Ru/Pr2O3, the average Ru particle size
is only 2.1 nm. However, a remarkably increased ­TOFH2
value of 1.41 ­s−1 can be observed, which is 1.6 times that
of the 5% Ru/Pr6O11 (Fig. 4). In comparison with that of
the 5% Ru/Pr6O11, the Ru NPs in 5% Ru/Pr2O3 sample not
only show much enhanced catalytic activity but also show
much enhanced intrinsic activity for ­NH3 decomposition.
The remarkably increased ­TOFH2 value over 5% Ru/Pr2O3
catalyst indicates that another factor is highly related with
Fig. 4  TOFH2 values of 5% Ru/Pr2O3 and 5% Ru/Pr6O11 catalysts as a
the intrinsic activity instead of particle size effect.
function of reaction temperature in ­NH3 decomposition
As both of the P ­ r2O3 and ­Pr6O11 are derived from same
­PrCO3OH precursor, the superior intrinsic activity of Ru/
Pr2O3 catalyst may arise from the difference of surface
properties of supports. The C ­ O2-TPD measurement was

13
Ru Nanoparticles on ­Pr2O3 as an Efficient Catalyst for Hydrogen Production from Ammonia… 1177

Pr2O3 sample possesses significantly higher density of sur-

Fig. 5  CO2-TPD profiles of Ru/Pr2O3 and Ru/Pr6O11 catalysts
conducted to study the basic properties of the Ru/Pr2O3 and
Ru/Pr6O11 samples. Figure 5 displays the C ­ O2 desorption
profiles of Ru/Pr2O3 and Ru/Pr6O11. The Ru/Pr6O11 sam-
ple shows a weak ­CO2 desorption peaks at ca. 80 °C and
another peak at ca. 621 °C. However, three ­CO2 desorp-
tion peaks at ca. 80, 300, and 711 °C can be observed for
Ru/Pr2O3, which are corresponding to the weak, medium,
and strong basic sites of the ­Pr2O3 support. Generally, the
amount of C ­ O2 desorption indicates the number of basic
sites and the temperature of the desorption is related to the
strength of the basic sites [50]. The desorption temperature
of strong basic sites over Ru/Pr2O3 (711 °C) is higher than
that of Ru/Pr6O11 (621 °C), and the amount of C ­ O2 desorp-
tion over Ru/Pr2O3 (671.9 μmol ­g−1) is 2.4 times that of Ru/
Pr6O11 (227.5 μmol ­g−1). The density of basic sites (per unit
surface area) was calculated by the integral method based
on the area of the corresponding desorption peaks [51]. As
shown in Table 2, the quantified results suggest that the Ru/
face basic sites than that of the Ru/Pr6O11. The density of
medium and strong basic sites of Ru/Pr2O3 sample is about
21.66 μmol ­m−2, which is much higher than that of Ru/
Pr6O11 (12.57 μmol ­m−2). The higher amount of strong basic
sites of Ru/Pr2O3 is beneficial for promoting the electron
donation to Ru surface, which may account for the superior
activity of Ru/Pr2O3 catalyst [52, 53].
Metal oxides are frequently used as catalysts and cata-
lyst supports in the field of heterogeneous catalysis. The
oxygen vacancies and F centers, surface hydroxyl groups
and reduction behavior of oxides strongly affect the sur-
face properties of metal oxides [54]. As one of the most
interesting catalytic structures, the oxygen vacancies on
the surface of ceria play a critical role in regulating the
catalytic performances of ceria nanostructured materials in
a variety of reactions (e.g., CO oxidation, water gas shift
reaction, hydrogenation of CO/CO2) [55–58]. Besides the
ceria, praseodymia with multiple valence states also has
an oxygen-deficient structure [59]. To further understand
the surface properties of Ru/Pr2O3, EPR characterization
was performed to probe the density of oxygen vacancies
of Ru/Pr2O3 and Ru/Pr6O11 samples. Here, EPR spectrum
of Ru/Pr2O3 shows a symmetrical and sharp EPR signal at
g = 2.003 (Fig. 6). According to the literature, the signal
at g = 2.003 can be ascribed to the electron trapped on the
oxygen vacancy [60]. The strong signal at g = 2.003 for
Ru/Pr2O3 demonstrates the presence of a large amount of
oxygen vacancies in the Ru/Pr2O 3 sample. By contrast,
only a very weak EPR signal corresponding to the oxygen
vacancies can be observed in the EPR spectrum of Ru/

Table 2  The amount and density of basic sites in Ru/Pr2O3 and Ru/
Pr6O11 catalysts determined by C
­ O2-TPD
Sample Peak temperature Adsorption of Density of
(°C) ­CO2 basic sites
(μmol ­g−1) (μmol ­m−2)

Ru/Pr2O3 80 19.9 0.66

300 337.3 11.21
711.4 314.7 10.45
Total 617.9 22.32
Ru/Pr6O11 80 – –
621 227.6 12.57
Total 227.6 12.57
Fig. 6  X‐band EPR spectra of Ru/Pr2O3 and Ru/Pr6O11 catalysts

13
1178
Pr6O11 at the same g value, implying that only a very small
amount of oxygen vacancies presents in Ru/Pr6O11 sample.
The EPR results confirm the existence of abundant oxygen
vacancies in the Ru/Pr2O3, which could promote the elec-
tron transfer from ­Pr2O3 support to Ru surface [50, 61].
Here, EXAFS and XANES spectroscopies were per-
formed to gain a deep insight of the structure of the Ru
NPs in Ru/Pr2O3 and Ru/Pr6O11 samples. Similar peaks at
∼ 2.4 Å, associated with Ru–Ru scattering in the first coor-
dination shell of metallic Ru, can be observed in the EXAFS
spectra of Ru/Pr2O3 and Ru/Pr6O11 (Fig. 7a). Analogous to
FT, wavelet transform (WT) is a mathematical complete
transformation of EXAFS signals. It not only provides radial
distance resolution but also resolve in k space [62]. As shown
in Fig. S4, the maximum intensity of WTs for Ru/Pr2O3
and Ru/Pr6O11 samples are located at ca. 8.8 Å−1, which
is assigned to Ru–Ru scattering, demonstrating the metal-
lic state of Ru species in the two samples. In comparison
with that of the Ru foil, the intensities of peak from the first
shell Ru–Ru scattering show obvious decrease for the Ru/
Pr2O3 and Ru/Pr6O11 samples, demonstrating the nanopar-
ticle form of the Ru species in the catalysts. The Ru K-edge
XANES spectra of Ru/Pr2O3 and Ru/Pr6O11 are shown in
Fig. 7b, with Ru and ­RuO2 as references. The XANES spec-
tra of Ru/Pr2O3 and Ru/Pr6O11 are located between the Ru
foil and R­ uO2, but closer to that of the Ru foil, indicating
the metallic Ru are dominant species in these two samples.
Compared with Ru/Pr6O11, a shift of edge energy towards Ru
foil could be observed in Ru/Pr2O3, revealing the Ru/Pr2O3
possesses relatively higher electron density than that of the
Ru/Pr6O11 [63, 64]. The EPR results confirm the presence
of oxygen vacancies in Ru/Pr2O3, which can promote the
electron transfer form ­Pr2O3 support to Ru NPs through the
Fig. 7  a Fourier transforms of k2-weighted Ru K-edge EXAFS spectra and b Ru K-edge XANES spectra for Ru foil, R
Pr6O11 catalysts
13
X. Zhang et al.
interaction between the ­Pr2O3 support and Ru NPs, causing
the higher electron density of Ru NPs in Ru/Pr2O3.
The surface composition of the catalysts and the chemical
states of the elements were investigated by XPS technique.
Figure 8a shows the Pr 3d XPS spectra of Ru/Pr2O3 and Ru/
Pr6O11 catalysts after N­ H3 decomposition reaction. The Pr
­3d5/2 and ­3d3/2 peaks of Ru/Pr6O11 shift to higher binding
energies than that of Ru/Pr2O3, centered at ca. 935.1 and
955.1 eV, respectively, which can be assigned to ­Pr4+ [65].
The satellite peaks at lower binding energy indicates the
existence of P­ r3+, suggesting the coexistence of P ­ r3+ and
4+
­Pr in Ru/Pr6O11 [66]. For Ru/Pr2O3 sample, the Pr ­3d5/2
and ­3d3/2 peaks are located at ca. 933.6 and 954.1 eV respec-
tively, in agreement with the binding energies of P ­ r3+ in
3+
­Pr2O3, which suggests the Pr mainly exists as P ­ r in Ru/
Pr2O3 [67, 68]. The XPS analyses of the valence states of
Pr are consistent with the XRD results, in which the bulk
phases of Ru/Pr2O3 and Ru/Pr6O11 are ­Pr2O3 and P ­ r6O11,
respectively.
Understanding the origin of the high intrinsic activity
of Ru NPs on P ­ r2O3 and ­Pr6O11 is particularly important.
On the different substrates, the active chemical state of the
Ru species may vary greatly. The electron structure of Ru
NPs has a significant impact on the catalytic activity of N ­ H3
decomposition. We suppose that the strong interaction at the
Ru–support interface can tune the electronic structure of Ru
NPs and thus make the catalyst superior active in the ­NH3
decomposition reaction. To check this, XPS was employed
to investigate the chemical state of Ru species in Ru/Pr2O3
and Ru/Pr6O11 catalysts. Due to the overlap of Ru 3­ d3/2 and
C 1s peak at c.a. 284.8 eV, Ru chemical state was deter-
mined by XPS analyses of Ru 3p core level spectra. Fig-
ure 8b illustrates the Ru ­3p3/2 XPS spectra of Ru/Pr2O3 and
­ uO2, Ru/Pr2O3 and Ru/
Ru Nanoparticles on ­Pr2O3 as an Efficient Catalyst for Hydrogen Production from Ammonia…
Fig. 8  XPS analyses of Ru/Pr2O3 and Ru/Pr6O11 catalysts: a Pr 3d core level spectra; b Ru 3­ p3/2 core level spectra; c relative abundance (%) of
the Ru species in Ru 3­ p3/2 spectra
Ru/Pr6O11 samples. It can be found that the binding energy
of Ru 3­ p3/2 of Ru/Pr2O3 is obviously lower than that of Ru/
Pr6O11. The Ru ­3p3/2 region could be deconvoluted into two
peaks of metallic ­Ru0 (ca. 462.2 eV) [48, 69] and R ­ un+ (ca.
463.7–464.4 eV) [70, 71]. The partially positive charge ­Run+
species can be attributed to the Ru species located at the
interface between Ru NPs and support. The relative contents
of different Ru species are shown in Fig. 8c. The relative
content of R­ u0 in Ru/Pr2O3 (63.5%) is much higher than that
of Ru/Pr6O11 (41.7%), demonstrating the significant increase
of electron density of Ru NPs in Ru/Pr2O3, which is consist-
ent with the result of XANES.
Generally, many different factors such as the dispersion,
size and morphology of Ru NPs, interaction between Ru NPs
and support, and surface property of support can influence
the intrinsic catalytic activity of supported Ru catalysts. It
is well-known that the B5 site on the surface of metallic
Ru species is recognized as the active site for decomposi-
tion of N­ H3 [14, 46, 47]. Hence, the percentage of metallic
Ru species is vital to the catalytic decomposition of ­NH3.
High percentages of metallic Ru species could lead to much
enhanced catalytic activity. For the Ru/Pr2O3 with high per-
centage of metallic Ru species, much enhanced T ­ OFH2 can
be observed even the sample has a relatively small particle
size, revealing the superior intrinsic activity of Ru/Pr2O3
sample (Fig. 4). The C ­ O2-TPD and EPR results show the
presence of high density of basic sites and oxygen vacancies
in Ru/Pr2O3 sample respectively, which can facilitate the
electron transfer from P ­ r2O3 support to Ru NPs, leading to
the increase of the electron density of Ru NPs in Ru/Pr2O3.
The electron-rich Ru surface could enhance the recombina-
tive desorption of adsorbed nitrogen and improve the ­NH3
decomposition activity. Thus, it is worthwhile to empha-
size the critical role of surface basic properties and oxygen
vacancies of ­Pr2O3 support in modulating the electronic
structure of Ru/Pr2O3 catalyst. The modulated electronic
1179
structure makes the metallic Ru species in Ru/Pr2O3 highly
active in N
­ H3 decomposition, which is responsible for its
superior intrinsic activity in ­NH3 decomposition.
4 Conclusion
In summary, this work demonstrates that P ­ r2O3 is a superior
support for preparation of highly efficient and stable Ru/
Pr2O3 catalysts for N­ H3 decomposition. The high density
of basic sites, abundant oxygen vacancies of P ­ r2O3, and the
strong metal–support interaction can not only render the
high dispersion of Ru NPs on the ­Pr2O3 surface, but also
benefit for the electron donation to the Ru NPs, leading to
the increase of electron density of Ru NPs in Ru/Pr2O3. As
a result, Ru/Pr2O3 exhibits superior catalytic activity and
stability in ­NH3 decomposition reaction. We anticipate that
these finding could provide an insightful understanding of
the role of the support on the catalytic behavior and open
opportunities to develop highly efficient catalysts for N­ H3
decomposition.
Supplementary Information The online version contains supplemen-
tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 10562-0​ 21-0​ 3709-2.
Acknowledgements This work was supported by the Strategic
Priority Research Program of the Chinese Academy of Sciences
(XDA21010208), the Light Source Fund of Dalian Institute of Chemi-
cal Physics, Chinese Academy of Sciences (DICP DCLS201701), and
the K. C. Wong Education Foundation (GJTD-2018-06).
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Authors and Affiliations

Xilun Zhang1,2 · Lin Liu1 · Ji Feng1,2 · Xiaohua Ju1 · Jiemin Wang1,3 · Teng He1 · Ping Chen1

1 3
Dalian National Laboratory for Clean Energy, State Key Zhang Dayu School of Chemistry, Dalian University
Laboratory of Catalysis, Dalian Institute of Chemical of Technology, Dalian 116024, China
Physics, Chinese Academy of Sciences, Dalian 116023,
China
2
University of Chinese Academy of Sciences, Beijing 100049,
China

13