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Covalent triazine-based framework as an efficient

catalyst support for ammonia decomposition
Cite this: RSC Adv., 2015, 5, 3605
Fei Chang,ab Jianping Guo,ab Guotao Wu,a Lin Liu,a Miao Zhang,ab Teng He,a
Peikun Wang,ab Pei Yuab and Ping Chen*ac
Published on 05 December 2014. Downloaded on 3/14/2024 2:51:12 AM.

Received 21st October 2014
Accepted 2nd December 2014
DOI: 10.1039/c4ra12816h
www.rsc.org/advances
The covalent triazine-based framework (CTF), a new type of nitrogen-containing microporous polymer,
was employed as a catalyst support for ammonia decomposition. Either in terms of NH3 conversion rate
or turnover frequency, Ru/CTF-1 has a highly enhanced performance compared to Ru/CNTs, which rank
as one of the best un-promoted catalysts reported so far. The compositional and structural information
of Ru/CTF-1 and Ru/CNTs catalysts have been characterized by ICP, N2 physisorption, XRD, TEM, XPS,
and NH3-TPD techniques. Ru particles on CTF-1 and CNTs are ca. 3 nm in diameter and have a similar
degree of dispersion. However, the binding energy of Ru 3p electrons is ca. 0.6 eV less for Ru/CTF-1
than that for Ru/CNTs showing significant increase in electron density in the former, which is likely due
to the interaction between the nitrogen-rich groups of CTF-1 and the Ru nanoparticles. Moreover, the
presence of CTF-1 enhances the chemisorption of NH3, which, together with the increased electron
density of Ru, may facilitate the competitive chemisorption of NH3 and recombinative desorption of
adsorbed nitrogen via lowered activation energy and thus, enable faster reaction rate.

strong anchoring points for the metal and behave as electron

1. Introduction
There is increasing interest in employing ammonia as an energy
carrier.1 Ammonia decomposition to COx-free hydrogen, an
ideal fuel for PEM (proton exchange membrane) fuel cells,2,3 can
be effectively catalyzed by the group VIII transition metals,
among which the supported ruthenium catalysts have the
highest activity.4,5 Au et al. investigated the effects of a number
of supports and demonstrated the overall performance is in the
order of CNTs > MgO > TiO2 z AC z Al2O3.6 Similar results
were also reported by Zhu et al.7 Multi-walled Carbon Nano-
tubes (MWCNTs) have a surface area greater than 100 m2 g
1
and have relatively good graphitic degree.8 However, there are
electron-withdrawing groups (–COOH, –OH) on the surface of
CNTs, which may affect the electronic structure of Ru.9–12 By
using Morse potential method, Bell et al. demonstrated that the
rate limiting step for ammonia decomposition on Ru surface is
the recombinative desorption of adsorbed nitrogen atoms,13
which can be promoted by the electropositive elements such as
alkalis.7 On the other hand, increasing the charge density of
CNTs or CNFs (Carbon Nanobers) by doping surface nitrogen
groups also leads to a signicantly improved activity in
ammonia decomposition.14–16 As nitrogen atoms can serve as
a
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian-116023, P. R. China
b
University of Chinese Academy of Sciences, Beijing-100049, P. R. China
c
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian-116023, P. R. China. E-mail: pchen@dicp.ac.cn; Fax:
+86-411-8437-9583
donors, the superior catalytic behaviors of nitrogen-containing
carbon materials have been identied in different catalytic
reactions.17–20
Covalent triazine-based frameworks (CTFs), representing a
new type of nitrogen-containing microporous polymers, were
rst synthesized by Thomas et al. through the reversible ion-
othermal trimerization of aromatic nitriles in molten ZnCl2.21
CTFs have relatively high chemical and thermal stabilities due
to the covalently bonded structure. Previous work indicates that
CTFs are more stable than N-doped CNTs under hydrophilic
and hydrophobic conditions.22 More importantly, CTFs possess
some interesting properties such as large surface area, basicity
and high degree of graphitization which make them attractive
candidates for gas capture/storage and catalysis.23–30 As the
content of nitrogen functional groups in CTFs overweighs that
of N-doped CNTs, Pd supported on CTFs has a higher activity
and stability in the alcohol oxidation reaction than on N-doped
CNTs.22 Due to the plenty of nitrogen base sites, CTFs have been
used as an efficient metal-free base catalyst directly to synthe-
size organic carbonates.26 By a simple combination of CTFs and
Pt precursor, a highly active solid catalyst for methane selective
oxidation has also been demonstrated.25
Previous reports on using CTFs as support are mainly for
oxidative reaction. Herein, we investigate the performance of
CTF-1, a crystalline triazine-based organic framework with
hexagonal packing of pores,21 in a reductive process, i.e.,
ammonia decomposition. The catalytic activity of Ru/CTF-1 was
measured and compared with the benchmark Ru/CNTs. Our

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results show that, either in terms of NH3 conversion rate or
turnover frequency, the performance of Ru/CTF-1 is signi-
cantly superior to that of Ru/CNTs under the same conditions.
The electron density of the Ru on CTF-1 is greater than that on
CNTs, which facilitates the recombinative desorption of adsor-
bed nitrogen atoms. The stronger NH3 adsorption energy on Ru/
CTF-1 surface may enhance the interaction of reactant with the
ruthenium active sites and improve the ammonia decomposi-
tion activity.
2. Experimental
Catalyst preparation
CTF was prepared according to the procedure reported in
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literature.21 2,6-Dicyanopyridine (DCP) and ZnCl2 in a molar
ratio of 1/5 were ball milled at 60 rpm for 0.5 h. Then the
mixture was transferred into an ampoule under Ar atmosphere.
The ampoule was sealed, evacuated and heated at 673 K for 40
h. Aer cooling down to room temperature, the ampoule was
opened and the reaction mixture was grounded and washed
with diluted HCl solution and water for several times to remove
ZnCl2. Finally the black powder product was dried in Ar ow at
573 K for 3 h.
CNTs were pre-treated in aqueous HNO3 solution and
calcined in an Ar ow at 573 K for 3 h.
Ru/CTF-1 and Ru/CNTs catalysts were prepared by tradi-
tional wetness incipient impregnation with RuCl3 as precursor
and acetone as solvent. Aer drying in air for 12 h, catalysts were
calcined in an Ar ow at 573 K for 3 h.
Catalytic test
The catalytic activity was evaluated on a continuous ow quartz
reactor. Catalyst sample of 30 mg was placed in the central
section of the reactor and was tested under a ow of pure NH3
(gas ow rate ¼ 30 mL min
1, 15 mL min
1, 10 mL min
1) or a
ow of diluted NH3 (5 vol% NH3/Ar, gas ow rate ¼
30 mL min
1). Prior to the measurement, Ru/CTF-1 and Ru/
CNTs catalysts were reduced in pure NH3 at 673 K for 2 h and
773 K for 3 h, respectively. The effluent gasses were analyzed by
a gas chromatograph equipped with a thermal conductivity
detector (TCD) and a Porapak Q column, using hydrogen as the
carrier gas.
Catalyst characterization
The actual Ru loadings of the catalysts were determined by
inductively coupled plasma spectrometry (ICP-OES, optima
7300DV, Perkin-Elmer, USA).
X-ray diffraction (XRD) patterns were recorded on a PAN-
alytical X'pert diffractometer with monochromatized Cu-Ka
radiation (l ¼ 0.154 nm) at a setting of 40 kV and 40 mA.
Transmission electron microscope (TEM) images of the
samples were taken on a JEM-2100 at 200 kV.
The specic surface area was measured on Autosorb-1
system (Quantachrome, USA) by N2 adsorption isotherm
through BET method.
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The X-ray photoelectron spectroscopy (XPS) measurement
was performed using an Escalab 250 Xi X-ray photoelectron
spectrometer (Thermo Scientic) with nonmonochromatic AlKa
radiation (photon energy, 1486.6 eV). Small amount of Argon
was injected into the sample by a weak sputtering under a very
low ion current prior to the measurement. The binding energies
were calibrated with reference to the Ar 2p (242.0 eV).
The temperature programmed desorption of ammonia (NH3-
TPD) measurement was carried out on a home-made system
combining a quartz reactor and a mass spectrometer to record
the signal of NH3. The catalyst samples were reduced at 673 K in
pure H2 for 2 h, and then the gas ow was switched to Ar for
purging at 773 K for 2 h. Aer that the samples were cooled
down to room temperature, where NH3 adsorption was per-
formed. Physically adsorbed NH3 was removed by Ar at 373 K for
1 h. Then the temperature programmed desorption was carried
out by heating the samples from 373 K to 723 K at a rate of
5 K min
1.
3. Results and discussion
Ru/CTF-1 and Ru/CNTs catalysts with different Ru loadings
were prepared by traditional wetness incipient impregnation
using RuCl3 as precursor and acetone as solvent, where the
actual Ru loading was measured by ICP-OES (Table 1). The XRD
characterizations of the Ru/CTF-1 catalyst samples only show
the sheetlike structure of CTF-1 with (100) and (001) diffractions
at ca. 7.0 and 25.1 respectively (Fig. 1d–f),21 evidencing the
high dispersion of Ru on CTF-1, probably resulting from the
strong metal–support interaction. The 2 wt% and 1 wt% Ru/
CNTs catalysts also show no diffraction related to ruthenium
metal. The diffraction peaks at 26.5 and 42.5 are attributed to
CNTs (Fig. 1a–c), respectively, consistent with the results
reported by Au et al.6
Transmission electron microscope (TEM) observation
together with statistical analyses by counting 100 particles show
that the particle size distributions of Ru supported on CTF-1
and CNTs are similar, between 1 nm and 5 nm (Fig. 2, insets),
and the average Ru particle size of Ru/CTF-1 catalysts is slightly
smaller than that of Ru/CNTs catalysts, but all of them are
around 3 nm (Table 1) showing that Ru can be well dispersed on
CTF-1 as well as on CNT. Because of the micropore size of CTF-1
is about 1.5 nm, which is smaller than the average Ru particle
size, we believe the majority of Ru particles are located outside
the micropores. However, the largely shrunken surface area of
Ru/CTF-1 (see Table 1) compared with the pristine CTF-1 (SBET
¼ 734.7 m2 g
1) indicates the blockage of the channels by Ru
particles, anchoring at the openings of the CTF-1 channels. For
the Ru/CNTs catalysts, Ru particles are essentially located on
the external surface of CNTs. The degree of dispersion was
calculated according to the spherical model proposed by
Anderson (see Table 1),31 which shows that the dispersions of
Ru in 1 wt% Ru/CNTs and 2 wt% Ru/CNTs catalysts are ca.
41.2%. With various functional groups (such as –COOH, –OH)
bonded to the surface, CNTs can effectively anchor and disperse
Ru nanoparticles.7 Dispersions of the 1 wt% Ru/CTF-1 and 2
wt% Ru/CTF-1 catalysts are 44.5% and 44.0% respectively,
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Table 1 Properties and activities of CTF-1 and CNTs supported Ru catalysts

Catalyst Ru loadinga [%] SBETb [m2 g
1] Particle sizec [nm] Dispersiond [%] TOFe [s
1] Eaf [kJ mol
1]

1 wt% Ru/CTF-1 0.82 654.6 2.9 45.5 0.58 69.1

2 wt% Ru/CTF-1 1.81 614.1 3.0 44.0 0.40 67.1
1 wt% Ru/CNTs 0.76 80.3 3.2 41.2 0.19 88.5
2 wt% Ru/CNTs 1.95 67.6 3.2 41.2 0.21 87.3
a
Ru actual loading was determined by ICP-OES. b Specic surface area was determined by N2 physisorption, using BET method. c Statistical results
of TEM images. d Dispersion was calculated employing spherical model proposed by Anderson.31 e TOF values were measured under 5 vol% NH3/Ar
ow at 673 K. f Activation energy was measured under pure NH3 ow at 623–723 K.

N atoms in CTF-1 are essentially in sp2 hybridization. Their

lone electron pairs are effective Lewis bases which can affect the
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electronic structure of Ru attached to them. As can be seen in

Fig. 1 XRD patterns of (a) CNTs; (b) 1 wt% Ru/CNTs; (c) 2 wt% Ru/
CNTs; (d) CTF-1; (e) 1 wt% Ru/CTF-1 and (f) 2 wt% Ru/CTF-1.
which are slightly higher than those of the Ru/CNTs catalysts.
Chan-Thaw et al. reported that Pd NPs (nanoparticles) can be
xed on CTF-1 through the interaction with its nitrogen
groups.22 Here we also attribute the high dispersion of Ru on
CTF-1 to such a metal–support interaction.
Fig. 3, the electron binding energy of Ru 3p3/2 of pre-reduced
2 wt% Ru/CNTs is at ca. 461.6 eV, evidencing the metallic
state of Ru in the catalyst. The electron binding energy of Ru
3p3/2 in 2 wt% Ru/CTF-1 is, interestingly, 0.6 eV smaller than
that in 2 wt% Ru/CNTs. In other words, the electron density of
Ru on CTF-1 is greater than that on CNTs.
The chemisorption of NH3 on catalysts was investigated by
temperature-programmed desorption (TPD) technique. Fig. 4
shows the TPD proles of the supported Ru catalysts and the
supports themselves upon absorbing NH3 at ambient temper-
ature followed by pre-heat treatment at 373 K. For neat CNTs
and CTF-1 supports, little NH3 can be detected during the
testing history. However, for CNTs and CTF-1 supported Ru
catalysts, NH3 desorption can be observed in the temperature
range of 400–500 K and 400–650 K, respectively. The NH3
desorption peak temperature of Ru/CTF-1 is at ca. 503 K, which
is about 55 K higher than that of Ru/CNTs revealing stronger
interaction between NH3 and Ru/CTF-1. Such a stronger
chemisorption may facilitate the competitive chemisorption of
NH3 molecules onto the active sites leading to an increased

Fig. 2 TEM images of Ru-based catalysts. (a) 1 wt% Ru/CTF-1; (b) 2 wt% Ru/CTF-1; (c) 1 wt% Ru/CNTs and (d) 2 wt% Ru/CNTs. Insets: Ru particle
size distributions.

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Fig. 3 XPS spectra of the ruthenium 3p3/2 region of (a) 2 wt% Ru/CTF-1;
(b) 2 wt% Ru/CNTs.
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Fig. 4 NH3-TPD profiles of (a) CNTs; (b) CTF-1; (c) 2 wt% Ru/CNTs and
(d) 2 wt% Ru/CTF-1.
chance of reaction. Furthermore, the amount of desorbed NH3
from Ru/CTF-1 is obviously more than that of Ru/CNTs, which
indicates more suitable sites for the strong adsorption of NH3
on the surface of Ru/CTF-1.
To minimize the effect of heat and mass transport during the
endothermic ammonia decomposition reaction, a diluted
Fig. 5 Ammonia decomposition reaction activity test with 2 wt% Ru/CTF-1 (-); 2 wt% Ru/CNTs (B); 1 wt% Ru/CTF-1 (:) and 1 wt% Ru/CNTs
(P). (a) Reaction conditions: catalyst (30 mg), 5 vol% NH3/Ar (flow rate ¼ 30 mL min
1); (b) reaction conditions: catalyst (30 mg), pure NH3 (for 2
wt% Ru/CTF-1 and 2 wt% Ru/CNTs, flow rate ¼ 15 mL min
1, GHSV ¼ 30 000 mL h
1 gcat
1; for 1 wt% Ru/CTF-1 and 1 wt% Ru/CNTs, flow rate ¼
10 mL min
1, GHSV ¼ 20 000 mL h
1 gcat
1).
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ammonia (5 vol% NH3/Ar) ow was used as the reactant to
uncover the intrinsic activities of the CTF-1 and CNTs supported
Ru catalysts. Fig. 5a illustrates the NH3 conversion as a function
of reaction temperature. The NH3 conversion of 2 wt% Ru/CNTs
and 1 wt% Ru/CNTs is negligible at temperatures below 623 K.
However, much higher conversion rates were observed on the
CTF-1 supported catalysts. At 623 K, NH3 conversion rates over 1
wt% and 2 wt% Ru/CTF-1 is ca. 8.0 and 3.3 times higher than
those of 1 wt% and 2 wt% Ru/CNTs, respectively. In higher
temperature range, the catalytic activities of Ru/CTF-1 catalysts
keep on overweighing those of the Ru/CNTs catalysts. It should
be noted that the 1 wt% Ru/CTF-1 catalyst is even superior to
2 wt% Ru/CNTs under the same reaction condition. The turn-
over frequency (TOF) values (see Table 1) calculated from the
hydrogen formation rate (mol gcat
1 s
1) per surface exposed Ru
atom number per gram catalyst (mol gcat
1) show that at 673 K,
the TOF over 2 wt% Ru/CTF-1 is ca. 2.0 times higher than that
over 2 wt% Ru/CNTs. For the 1 wt% Ru based catalysts, it is 3.1
times.
Under a ow of pure NH3, the ammonia conversion rates
over the Ru/CTF-1 are 1.5–2.5 times higher than those over Ru/
CNTs in the temperature range of 598–723 K (see Fig. 5b). The
turnover frequency values as a function of reaction temperature
are shown in Fig. 6. Ruthenium loading has little inuence
upon TOF for the same kind of catalysts. The apparent activa-
tion energy of Ru/CTF-1 obtained from the Arrhenius plots is
about 20 kJ mol
1 lower than that of Ru/CNTs (Fig. 7).
For Ru based catalysts, the B5 sites (ve member sites on the
steps of Ru (0001) plane) are regarded generally as the active
sites for ammonia synthesis and decomposition.32,33 The
amounts of B5 sites are structural sensitive and depend
signicantly on the size and dispersion of Ru particles. Previous
investigations by Kowalczyk et al. showed that the maximum
concentration of B5 sites was achieved when the Ru particle size
is in the range of 1.8–2.5 nm.34 In our work, the Ru particle sizes
of Ru/CTF-1 and Ru/CNTs catalysts are near the optimal range.
Considering the similar Ru particle sizes and dispersions of all
the CTF-1 and CNTs supported catalysts, the differences in
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Fig. 6 Turnover frequency of 1 wt% Ru/CNTs (P); 1 wt% Ru/CTF-1
(C); 2 wt% Ru/CNTs (O) and 2 wt% Ru/CTF-1 (-) under pure NH3
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flow at 598–723 K.
Fig. 7 Arrhenius plots of 1 wt% Ru/CNTs (P); 1 wt% Ru/CTF-1 (:); 2
wt% Ru/CNTs (C) and 2 wt% Ru/CTF-1 (,). The temperature range
(648–723 K) used for the determination of apparent activation ener-
gies was based on NH3 conversion values far away from the equilib-
rium values. The calculated average values and deviation errors of the
Arrhenius plots were listed.
activity (NH3 conversion rate and TOF) may not be ascribed to
the particle size effect.
Bell et al. demonstrated that the rate limiting step of
ammonia decomposition over Ru catalysts at relatively lower
temperature is the recombinative desorption of adsorbed
nitrogen atoms.13 At higher temperatures, the cleavage of N–H
bond will be the rate-limiting step as proposed by Tsai and
Weinberg.35 Bradford et al. suggested that both cleavage of N–H
bond and recombinative desorption of adsorbed nitrogen
atoms are kinetically slow on well-dispersed Ru.36 Support or
additive which can facilitate electron feedback to the anti-
bonding orbital of the transient metal–nitrogen bond should
be benecial for these steps.2 Compared with activated carbon,
MgO, Al2O3 and TiO2, CNTs is the best support for ammonia
decomposition because of its high metal dispersion and good
degree of graphitization, which is benecial for the electron
transfer between support and Ru.11 Such an electron transfer
process can be enhanced upon using CTF-1 as support due to
the fact that the surface of CTF-1 is rich in nitrogen groups,
leading to the increase in electron donation to Ru, which is
evidenced by the downshi of binding energy of Ru 3p
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electrons. The increase in electron density on Ru surface, as
discussed above, may lead to the decrease in the kinetic barrier
for the recombinative removal of surface nitrogen atoms, which
is also in accordance with the decrease in Ea measurements (i.e.,
Ea of Ru/CTF-1 is ca. 20 kJ mol
1 lower than that of Ru/CNTs).
NH3 and H2 have reaction orders of 0.69 and
1.6, respec-
tively, over well dispersed Ru at 663 K.36 The negative reaction
order for H2 shows its inhibition to ammonia decomposition,
which can be attributed to the hindrance of surface sites by the
strongly chemisorbed hydrogen.37 Our NH3-TPD proles show
that NH3 adsorption energy on Ru/CTF-1 is stronger than that
on Ru/CNTs, which may, to a certain extent, enhance the chance
of NH3 to interact with the ruthenium active sites and facilitate
the activation of N–H bond, thus further improve the ammonia
decomposition activity.
4. Conclusions
CTF-1, a kind of novel nitrogen-containing microporous poly-
mer, is a superior support for Ru catalyst. The Ru/CTF-1 shows
much better performance in ammonia decomposition than Ru/
CNTs, which ranks one of the best un-promoted catalyst
reported so far. Besides the high dispersion of Ru nanoparticles
over CTF-1, we ascribe the improved performance to the rich
nitrogen groups on CTF-1, which can anchor Ru nanoparticles
and transfer electrons to Ru. The enhanced electron density of
Ru surface is benecial for the recombinative desorption of
adsorbed nitrogen atoms. Nitrogen groups on CTF-1 play an
important role as an electron donor to Ru and improve the
catalytic activity.
Acknowledgements
The authors would like to acknowledge the nancial supports
from Project of National Natural Science Funds for Distin-
guished Young Scholars (51225206), 973 Project
(2010CB631304) and the National Natural Science foundation of
China (21133004 and 21273187).
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