Catalysis Communications 5 (2004) 35–39

www.elsevier.com/locate/catcom

A novel plasma-treated Pt/NaZSM-5 catalyst

for NO reduction by methane
Yue-Ping Zhang a, Pei-Sheng Ma b, Xinli Zhu b, Chang-Jun Liu b,*
, Yutian Shen c

a
Department of Chemistry, Tianjin University, Tianjin 300072, PR China
b
ABB Plasma Greenhouse Gas Chemistry Laboratory, Key Laboratory of Green Chemical Technology and School of Chemical Engineering,
Tianjin University, Tianjin 300072, PR China
c
Analysis Center, Heibei University of Technology, Tianjin 300130, PR China
Received 14 July 2003; received in revised form 6 November 2003; accepted 6 November 2003
Published online: 3 December 2003

Abstract

A novel catalyst preparation for NO reduction by CH4 has been conducted using a glow discharge plasma treatment followed by
calcinations thermally. Such plasma prepared Pt/NaZSM-5 catalyst exhibits a high dispersion of metal active species. A remarkable
improvement in the activity and stability, compared to the catalysts prepared conventionally, has been achieved. Especially, an
excellent low temperature activity over the plasma-treated Pt/NaZSM-5 catalyst has been obtained. For example, the conventional
0.1 wt% Pt/NaZSM-5 catalyst shows no activity at temperatures below 673 K, while at 673 K, the NO conversion to nitrogen
reaches 61.3% over the plasma-treated 0.1 wt% Pt/NaZSM-5 catalyst. The initiated temperature for the plasma-treated 0.1 wt% Pt/
NaZSM-5 catalyst can be as low as 548 K.
Ó 2003 Elsevier B.V. All rights reserved.

Keywords: Glow discharge; Plasma; Pt/NaZSM-5; NO reduction; Methane

1. Introduction developed glow discharge catalyst treatment technology

Zeolite supported noble metal catalysts have been
extensively employed for NOx reduction, catalytic
combustion of hydrocarbons, isomerization, hydrode-
sulfurization and so on. The catalytic performance of
these zeolite-supported catalysts is mostly dependent on
the preparation of the catalyst, which determines the
acidity, dispersion, activity and stability of the catalyst.
A sufficiently intense acidity and a high dispersion of
metal active species are normally required. We recently
have developed a glow discharge plasma catalyst treat-
ment followed by calcination thermally, which can lead
to a remarkable enhancement in the acidity and a sig-
nificant improvement in the dispersion and stability of
catalysts prepared by impregnation [1–3]. One of the
objectives of this work is to extend the application of the
*
Corresponding author. Tel./fax: +86-22-27890078.
E-mail address: changliu@public.tpt.tj.cn (C.-J. Liu).
for NO reduction by hydrocarbons.
As we have seen, an intensive investigation has been
conducted to reduce nitrogen oxides that are extremely
harmful pollutants [4–17]. The reported investigations
include catalytic reduction by hydrocarbons [5–9], by
plasmas [10,11] and by the combination of plasma and
catalytic reduction [12–16]. The catalytic reduction has a
higher selectivity but the lifetime of catalysts needs to be
improved. The previous investigations have confirmed
that the catalyst for NO reduction is structure-sensitive
catalyst [9,17–19]. The preparation and reaction condi-
tions have a significant influence on the performance of
the catalyst. Plasma conversion shows a high conversion
rate for removing nitrogen oxides (NOx ). But the poor
selectivity limits its application. The combination of
plasma and heterogeneous catalyst has been found re-
cently to be a promising technology for NOx reduction.
In general, the investigated combination includes single
stage plasma catalytic reactor system and two-step
plasma catalytic reactor system. The first reactor system

1566-7367/$ - see front matter Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2003.11.006
36 Y.-P. Zhang et al. / Catalysis Communications 5 (2004) 35–39
employs a direct interaction between catalyst and plasma
species during NOx reduction. The catalyst normally
must show some field-dependent structural and elec-
tronic properties that can respond effectively to the in-
fluence of plasmas. The two-step system normally uses
plasma in the first step to convert NO to other nitrogen
oxides that are easier to be converted catalytically in the
second step. Evidently, for either single stage or two-
step combination technology, a good catalyst is more
important. However, it still remains as a challenge to
find such good catalyst. In this work, we report a dif-
ferent technology: the plasma is used first to prepare
catalyst and then the prepared catalyst is applied for NO
reduction. The experiment confirms that a better cata-
lyst has been achieved. A remarkable improvement both
in catalytic activity and stability has been achieved by
this plasma treatment.
2. Experimental
Pt/NaZSM-5 catalysts were prepared by the conven-
tional incipient wetness impregnation method. The
support NaZSM-5 was commercially obtained (SiO2 /
Al2 O3 ¼ 50; made in Nankai University Catalyst Plant,
Tianjin, China) and was applied as received. For the
preparation of Pt/NaZSM-5 catalysts, the support was
first impregnated in an aqueous solution of chloroplat-
inic acid (H2 PtCl6 ) for 18 h. After impregnation, the
resulted sample was dried at 383 K for 8 h. The obtained
sample was then divided into two parts: one for calci-
nation thermally at 773 K for 4 h and the other for
plasma treatment at room temperature for 30 min be-
fore further calcination thermally at 773 K for another
4 h.
We have successfully utilized a dc glow discharge for
plasma treatment of catalyst (for partial oxidation of
methane to syngas [1] and for methane combustion
[2,3]). The setup for the glow discharge treatment has
also been described in detailed previously [2,3,20].
During the plasma treatment, the catalyst powder (40–
60 mesh) was held in a container that is placed in the
discharge tube. The glow discharge [20], one of the
conventional cold plasma phenomena, is initiated by a
dc high voltage generator at low pressure. The catalyst
was located in the ‘‘positive column’’ of glow discharge
[20] that was generated at 100–150 Pa using argon as the
plasma-forming gas. The applied voltage (ca. 500 V) to
the electrode was measured using a high voltage probe
(Tektronix P6015A) with a Tektronix TDS210 digital
real-time oscilloscope.
The catalytic NO reduction by methane was carried
out in a quartz tube reactor. The inner diameter of the
quartz tube is 6 mm. The catalyst loaded is 0.1 g. The
feed gas contained 4237.2 ppm NO, 7927.6 ppm CH4
and helium make the balance. The total flow rate was
kept at 100 ml/min (GHSV ¼ 47,922 h
1 ). Before reac-
tion, the catalyst was pretreated at 773 K under the
flowing He at a flow rate of 20 ml/min for 1 h. Then the
temperature was reduced to 473 K and the gas helium
was replaced by the gaseous reactant (feed gas). The
reaction temperature was controlled automatically by a
temperature controller.
The feed gas and the effluent were analyzed by a GC
(Agilent 4890D) with a TCD detector using a column of
HP-Plot Molecular Sieve 5A. The column ID is 0.53 mm
and the length is 15 m. From the GC analysis, NO was
mostly converted into nitrogen. A small amount of N2 O
was also detected. In this work, we use a NO conversion
to N2 to evaluate the catalytic activity of NO reduction
by methane:
NO conversion to N2
¼ NO conversion  N2 selectivity
To understand the plasma-enhanced activity and
stability, a TEM characterization of the used zeolite
catalysts has been conducted using a JEM-100CX TEM
system. Using a Micromeritics TPD/TPR 2900 analyzer,
H2 chemisorption was carried out to calculate the metal
dispersion. During the operation of hydrogen chemi-
sorption, a dynamic pulse technique was employed with
flowing argon at a flow rate of 20 ml/min and with
pulses of hydrogen/argon (5/95) mixture. After loading
the catalyst, the sample was outgassed by heating at a
temperature increase rate of 15 °C/min in a flowing
hydrogen/argon mixture (30 ml/min with the H2 /Ar
ratio of 10/90) up to 200 °C. The sample was held for ca.
1 h. Then the sample was cooled to 50 °C in flowing
argon (20 ml/min). The objective of the choice of 50 °C is
to avoid the hydrogen spillover. The acidity of the ze-
olite was determined by IR-pyridine adsorption, carried
out with a Bruker Vector22 IR spectrometer. To do so,
the catalysts were first pressed into a wafer (8 mm ID, 20
mg) and placed in a quartz cell. The sample was then
pretreated at 400 °C and 10
3 Pa for 1 h in order to
remove adsorbed water and other contaminates. After
that, the sample was cooled to room temperature. A 2
ml pyridine was injected into the vacuum system to
conduct the adsorption for 30 min. The excess and
physisorbed pyridine was desorbed at 200 °C. The IR
spectra were recorded in the range from 1800 to 1300
cm
1 at room temperature.
3. Results and discussion
In the following discussions, the conventional cata-
lyst is referred to as Pt/NaZSM-5(C) and the plasma
prepared catalyst is referred to as Pt/NaZSM-5(P).
Fig. 1 presents a comparison of the catalytic activity
(NO ! N2 ) between 0.1 wt% Pt/NaZSM-5(C) and 0.1
 Y.-P. Zhang et al. / Catalysis Communications 5 (2004) 35–39 37

NO Conversion to N2 (%) 100 A remarkable improvement in the stability of 0.1

80
60
40
20
0 catalyst. As shown in Fig. 2, 0.1 wt% Pt/NaZSM-5(C)
673
Fig. 1. Comparison of activity of 0.1 wt% Pt/NaZSM-5(T) and Pt/
NaZSM-5(P). Reaction time: 60 min; j, Pt/NaZSM-5(T) and m, Pt/
NaZSM-5(P).
wt% Pt/NaZSM-5(P). Evidently, the catalyst 0.1 wt% Pt/
NaZSM-5(P) owns a much better activity at lower
temperatures. 0.1 wt% Pt/NaZSM-5(C) shows no ac-
tivity at temperatures below 693 K. This means that 0.1
wt% Pt/NaZSM-5(C) needs a higher temperature to be
activated. The initiated temperature for 0.1 wt% Pt/
NaZSM-5(P) is as low as 548 K. At 693 K, the NO
conversion to nitrogen reaches 61.3% over 0.1 wt% Pt/
NaZSM-5(P). The catalyst 0.1 wt% Pt/NaZSM-5(P)
shows a much better low temperature activity. At higher
temperatures (>748 K), there is a little difference in the
activity between the two catalysts.
100
90
NO Conversion to N 2 (%)
wt% Pt/NaZSM-5 catalyst has been observed, as shown
in Fig. 2. With the increase in the reaction time, the
selectivity over 0.1 wt% Pt/NaZSM-5(P) does not
change significantly, but the selectivity over 0.1 wt% Pt/
NaZSM-5(C) decreases quickly. In addition, a re-
markable improvement in the stability of Pt/NaZSM-5
catalyst has also been observed with the plasma-treated
693 713 733 753 773 deactivates very quickly (after 60 min), while the deac-
tivation rate of 0.1 wt% Pt/NaZSM-5(P) is much less
Temperature (K)
than that of 0.1 wt% Pt/NaZSM-5(C). Even after 1500
min, the NO conversion to N2 over 0.1 wt% Pt/
NaZSM-5(P) can be as high as 64.9%. The plasma-
treated catalyst shows an excellent resistance towards
deactivation.
As discussed in Section 1, the catalyst for NO re-
duction is structure-sensitive catalyst. The preparation
has a significant influence on this kind of catalyst. From
the remarkable improvement in the catalytic activity, the
plasma treatment must have induced a remarkable
change in the catalyst structure. Upon H2 chemisorp-
tion, the dispersion of 0.1 wt% Pt/NaZSM-5(P) is higher
than that of 0.1 wt% Pt/NaZSM-5(C). The size of active
Pt species is 1.8 nm for 0.1 wt% Pt/NaZSM-5(P), while it
is 27.0 nm for 0.1 wt% Pt/NaZSM-5(C), as shown in
Table 1. Table 1 also presents the dispersion of palla-
dium of the two catalysts. It can be seen clearly that the
dispersion of 0.1 wt% Pt/NaZSM-5(P) is as high as
63.3%, but the dispersion of 0.1 wt% Pt/NaZSM-5(C) is
only 4.2%. The hydrogen chemisorption also indicates
that the surface area of Pt of plasma prepared catalyst is
281.8 m2 /g metal that is much higher than the surface

80 area of the conventional catalyst. A highly dispersed Pt/

70
NaZSM-5 catalyst has been achieved by using of glow
60
50
discharge treatment. Moreover, it can be seen from
40 Table 1 that the increase order in dispersion is Pt/
30 NaZSM-5(C) – the sample just after plasma treatment –
20 Pt/NaZSM-5(P). This means that the plasma treatment
10 leads to an improvement in the dispersion of Pt parti-
0 cles, while the calcinations of the plasma-treated sample
0 500 1000 1500
induces a further improvement in the dispersion. This is
Time (min.) a direct evidence for the change in the catalyst structure
Fig. 2. The NO conversion to N2 versus time over 0.1 wt% Pt/NaZSM-
by plasmas.
5 catalysts. Reaction temperature: 748 K; j, Pt/NaZSM-5(T) and m, We previously confirmed that the plasma-enhanced
Pt/NaZSM-5(P). acidity has a significant effect on the metal dispersion of

Table 1
The results of H2 -chemisorption
0.1 wt% Pt/NaZSM-5(C) 0.1 wt% Pt/NaZSM-5(P) Plasma-treated 0.1 wt% Pt/NaZSM-5
without calcination
Pt dispersion 4.2 63.3 10.2
Surface area of Pt (m2 /g sample) 0.02 0.28 0.05
Surface area of Pt (m2 /g metal) 18.5 281.8 45.3
Diameter of Pt particle (nm) 27.0 1.8 11.0
38 Y.-P. Zhang et al. / Catalysis Communications 5 (2004) 35–39
Table 2
Acid site amount based on the IR-pyridine adsorption
0.1 wt% Pt/NaZSM-5(C)
Lewis acid (mmol/g) 1.944
Br€
onsted acid (mmol/g) 0.0332
Fig. 3. (a) TEM image of used 0.1 wt% Pt/NaZSM-5(C), taken from
the 360-min stability test. (b) TEM image of used 0.1 wt% Pt/NaZSM-
5(P), taken from the 1470-min stability test. TEM images of used Pt/
NaZSM-5 catalysts.
catalysts prepared by the glow discharge plasma treat-
ment followed by calcination thermally [19,20]. It is
the plasma-enhanced acidity that stabilizes the highly
dispersed active metal species. Okumura and Niwa [21]
reported a regulation of the dispersion of PdO through
the interaction with acid sites of zeolite. They found that
the dispersed PdO was generated on ZSM-5 upon the
0.1 wt% Pt/NaZSM-5(P) The increased amount of acidic sites (%)
2.147 10
0.0369 11
oxidation treatment. The degree of dispersion was de-
pendent on the acid amount of ZSM-5 support. In this
work, we also observe plasma-enhanced acidities with
the 0.1 wt% Pt/NaZSM-5 catalysts, as shown in Table 2.
From Table 2, the sample with plasma treatment has a
11% increase in the Br€onsted acidity and a 10% increase
in the Lewis acidity. The increased amount of acid sites
would play a very important role in the plasma-
enhanced dispersion of metal species.
Fig. 3 presents two TEM images of the used 0.1 wt%
Pt/NaZSM-5(C) and 0.1 wt% Pt/NaZSM-5(P) catalysts.
From these TEM images, one can clearly see that the
used Pt/NaZSM-5(C) catalyst shows some large parti-
cles (around several 10 nm in the size) after 360-min
reaction. While, the used Pt/NaZSM-5(P) keeps uniform
in the dispersion of active species even after 1470-min
reaction. The TEM characterization demonstrates that
the plasma-enhanced preparation leads to a better Pt/
NaZSM-5 catalyst for NO reduction by methane.
4. Conclusion
The present investigation demonstrates that the glow
discharge treatment followed by the calcination ther-
mally leads to a better catalyst preparation of the
structure-sensitive catalyst for NO reduction by meth-
ane. TEM characterization and H2 pulse chemisorption
confirm that the plasma treatment leads to a higher and
stable dispersion of active species over the support. A
better activity and a significantly enhanced stability of
the catalysts have been achieved this way, which must
lead to a remarkable improvement in the NO reduction
by methane.
Acknowledgements
The authors are grateful for supports from the Na-
tional Natural Science Foundation of China (under the
contract number 20225618). Part of equipment applied
was donated by ABB Switzerland Ltd., which is also
very much appreciated.
References
[1] J.-G. Wang, C.-J. Liu, Y.-P. Zhang, X.-L. Zhu, J.-J. Zou, K.-L.
Yu, B. Eliasson, Chem. Lett. (2002) 1068.
 Y.-P. Zhang et al. / Catalysis Communications 5 (2004) 35–39
[2] C.-J. Liu, K.-L. Yu, Y.-P. Zhang, X.-L. Zhu, F. He, B. Eliasson,
Catal. Commun. 4 (2003) 303.
[3] C.-J. Liu, K.-L. Yu, X.-L. Zhu, Y.-P. Zhang, F. He, B. Eliasson,
Appl. Catal. B (accepted).
[4] K. Shimizu, A. Satsuma, T. Hattori, Catal. Surv. Jpn. 4 (2000)
115.
[5] C.J. Loughran, D.E. Resasco, Appl. Catal. B 5 (1995) 351.
[6] U.S. Ozkan, M.W. Kumthekar, G. Karakas, Catal. Today 40
(1998) 3.
[7] S. Xie, M.P. Rosynek, J.H. Lunsford, J. Catal. 188 (1999) 32.
[8] B.J. Adelman, W.M.H. Sachtler, Appl. Catal. B 14 (1997) 1.
[9] I. Balint, A. Miyazaki, K.-I. Aika, Appl. Catal. B 37 (2002) 217.
[10] J. Luo, S.L. Suib, M. Marquez, Y. Hayashi, H. Matsumoto, J.
Phys. Chem. A 102 (1998) 7954.
[11] H.H. Kim, G. Prieto, K. Takashima, S. Katsura, A. Mizuno, J.
Electrostat. 55 (2002) 25.
39
[12] H.H. Kim, K. Takashima, S. Katsura, A. Mizuno, J. Phys. D 34
(2001) 604.
[13] B.S. Rajanikanth, V. Ravi, Plasma Sci. Technol. 4 (2002)
1399.
[14] H. Miessner, K.-P. Francke, R. Rudolph, Th. Hammer, Catal.
Today 75 (2002) 325.
[15] H.-S. Roh, Y.-K. Park, S.-E. Park, Chem. Lett. (2000) 578.
[16] K.-P. Francke, H. Miessner, R. Rudolph, Catal. Today 59 (2000)
411.
[17] G.A. Somorjai, Appl. Surf. Sci. 121/122 (1997) 1.
[18] I. Balint, A. Miyazaki, K.-I. Aika, Chem. Commun. (2002)
1044.
[19] R. Burch, P. Fornasiero, B.W.L. Southward, Chem. Commun.
(1998) 625.
[20] C.-J. Liu, G.P. Vissokov, B.W. Jang, Catal. Today 72 (2002) 173.
[21] K. Okumura, M. Niwa, J. Phys. Chem. B104 (2000) 9670.