Catalysis Today 90 (2004) 39–42

Influence of the precursors kind of catalysts on

the course of a denox reaction
Dobiesław Nazimek∗ , Wiesława Ćwikła-Bundyra
Faculty of Chemistry, University of Marie Curie-Skłodowska, 3 Marie Curie-Skłodowska Sq., 20-031 Lublin, Poland

Available online 7 June 2004

Abstract

Many investigations of the approach to NO removal show that the preparation of catalysts and the precursor type both influence the course
of the nitrogen oxide reduction by carbon oxide. Catalytic reduction of NO to nitrogen was carried out over supported platinum and palladium
catalysts that were derived from chlorides and nitrates as the precursors. The effect of the kind of precursor and the activation conditions on
the performance of Pt and Pd/Al2 O3 preparation has been studied. The activity was largely dependent not only on the kind of metal support
used but also on the precursors. The Pd supported catalyst derived from Pd(NO3 )2 was much more active within 773 K temperature than the
catalyst prepared from PdCl2 . The activity measurements for the Pt catalysts show that the catalyst prepared from H2 PtCl6 was more active.
The highest activity was revealed by the Pd/Al2 O3 obtained from nitrates. The kind of metal cation bounded with carboxyls of EDTA and the
kind of geometric structure of contact agent are important factors in generating supported catalysts.
© 2004 Elsevier B.V. All rights reserved.

Keywords: NO reduction by CO; Pd/Al2 O3 ; Pt/Al2 O3 catalysts; Catalyst precursor type

1. Introduction can be modified by the double impregnation method

[8,10].
Nitrogen oxide removal is a very important industrial pro- Mallet et al. has shown that the type of precursor of Pt
cess. The catalytic reduction of nitrogen oxides by carbon catalysts influences the magnitude of redox potential, which
oxide may offer an attractive alternative to the other method. changes under the influence of the size of Pt crystallites [4].
This paper aims at shedding light on the roles of Pd and Pt The size of the metal crystallite obtained will depend on
in the nitrogen oxide reduction by carbon oxide by compar- many factors: the concentration of metal ions in the impreg-
ing the activity. Interest in new approaches to NO removal nation solution, the presence of other ions, the time of ex-
were demonstrated that just as the type of precursor used the position and the kind of support [9]. Beyond the preparation
preparation of catalysts plays an important role. A detailed method the character of the substance used as a catalyst is
description of the problem has been given [1,2] and it was also important. The rate of following reaction changes with
proved that the double impregnation method [3] of obtaining the kind of catalysts precursor.
as well as treating catalysts precursors have a great influence We presented the preparation of Pt and Pd contact agent
on the catalysts’ properties. This paper investigates the in- supported over ␥-Al2 O3 and properties of these catalysts
fluence of the precursors of Pt and Pd catalysts on the course using nitrogen oxide conversion as a model reaction.
of a NO + CO reaction. In the many works concerned with
platinum [4,5] and palladium [6,7] as catalysts of denox
reactions a lot of attention has been paid to the size of metal 2. Experimental
crystallites and their arrangement on a surface support. The
study of the influence of metal dispersion on the course the The catalysts investigated, i.e. Pt/Al2 O3 and Pd/Al2 O3 ,
discussed reaction has proved that the qualities of catalysts supported on ␥-Al2 O3 obtained from St. Gobain, France
(Stotal = 82.4 m2 /g), were prepared via following methods:
∗Corresponding author. Tel.: +48-81-537-5515. • Platinum catalysts were obtained by the double impregna-
E-mail address: nazimek@hermes.umcs.lublin.pl (D. Nazimek). tion of alumina support. The Al2 O3 support was exposed

0920-5861/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cattod.2004.04.006
40 D. Nazimek, W. Ćwikła-Bundyra / Catalysis Today 90 (2004) 39–42

to activation in 0.1 M EDTA disodium salt solution at the degree of NO conversion (iso-X) [8,11]. In this way, the
temperature of 343 K for 30 min. After that time the ac- functions r = f (X) obtained at T = constant served as a
tivated forms of the support were dried at 383 K in air basis for plotting the dependence of the reaction rate for sev-
for 45 min. Next, the active support was impregnated at eral conversion degree. The reaction was carried out with a
343 K with Pt(NO3 )2 or H2 PtCl6 , respectively. NO:CO molar ratio of 1:1 (1500 ppm of NO and 1500 ppm
• Palladium catalysts were obtained by the double impreg- of CO) at a temperature of 773 K. The reaction products
nation of alumina support too. The Al2 O3 support was ex- were analyzed chromatographically using a Chrompack gas
posed to activation in 0.1 M EDTA disodium salt solution chromatograph with a PC computer as an integrator. The de-
at the temperature of 343 K for 30 min. After that time gree of nitrogen oxide conversion was calculated from the
the activated forms of the support were dried at 383 K in equation
air for 45 min. Next, the active support was impregnated
CNO
0 −C
NO
at 343 K with Pd(NO3 )2 or PdCl2 solution, respectively. XNO = (2)
CNO
0
All obtained catalysts were calcinated at 773 K for 1 h
in air. After calcination in air catalysts were reduced with where CNO 0 is the concentration of NO at the inlet
hydrogen at a temperature of 773 K for 3 h. (1500 ppm) and CNO the concentration of NO at the outlet.
The reaction rate were calculated using the following
equation, valid for a gradientless reactor [10]:
3. Methods
((CNO
0 −C
NO )/CNO )F
0
r (mol/gcatal. h) = (3)
The content of platinum or palladium introduced to the W
catalysts was measured with the X-ray fluorescence (XRF) where F is the final volumetric rate and W the catalysts
method in the Department of Analytical Laboratory, Faculty weight.
of Chemistry of UMCS. The total surface area of the cata-
lysts was determined from argon adsorption at the temper-
ature of liquid nitrogen by the BET method in a volumetric 4. Results and discussion
apparatus ensuring a vacuum of at least 10−5 mm Hg. The
same apparatus was used for the determination of the active Results obtained from adsorption measurements together
surface areas of the catalysts from the amounts of hydrogen with other physicochemical properties of platinum and pal-
(for Pt catalysts) or carbon monoxide (for Pd catalysts) ad- ladium catalysts are presented in Table 1. To make the task
sorbed at room temperature. The active surface area was cal- clear, each type of precursor is discussed separately.
culated assuming hydrogen binding stoichiometry to be 1:1 The data in Table 1 show that catalysts show great dif-
and the surface area covered by one hydrogen atom being ference either on the metal loading, the active surface or
8.9 Å2 [11]. Carbon oxide adsorption was measured assum- crystallites size.
ing the binding stoichiometry to be 1:1 with a carbon monox- Fig. 1 show a comparison of activities of Pt/Al2 O3 prepa-
ide molecule occupying an area of 8.9 Å2 [12], too. The rations obtained from different precursors, i.e. H2 PtCl6 and
mean dimensions of the metal crystallites were determined Pt(NO3 )2 .
by X-ray line broadening studies over the range 20–44.4◦ , Fig. 2 show a comparison of activities of Pd/Al2 O3 prepa-
after Warren, by using a DRON-2 diffractometer employing rations obtained from different precursors, i.e. PdCl2 and
a Cu K␣ radiation source, and also from chemisorption mea- Pd(NO3 )2 .
surements. The average crystallite size was calculated from The kind of platinum or palladium precursors was estab-
the results of hydrogen chemisorption from the equation lished to have a significant effect other catalysts activity.
Figs. 3 and 4 show reaction rate of reduction NO on re-
6 × 104
d (nm) = (1) counted on gram of metal.
SPt,Pd × γPt,Pd In general, the preparations obtained on the basis of plat-
where SPt,Pd is the surface area of 1 g of the platinum or pal- inumchloric acid were more active than those based on plat-
ladium catalysts and γ Pt,Pd is the specific gravity of rhodium inum nitrate. It was found to have significant effect on the
or platinum (Pt (21.5 g/cm3 ) and Pd (12.0 g/cm3 )), assum-
ing that a platinum and palladium crystallite is a sphere. For Table 1
the calculation of the average particle size of Pt or Pd, 100% The physicochemical properties of catalysts
metal reduction was assumed. Sample (type of Metal loading Active surface Crystallite
Measurements of the rates of NO reduction by CO were precursor) (wt.%) area (m2 /g) size (nm)
carried out in a gradientless reactor based on the one de- Pt/Al2 O3 (H2 PtCl6 ) 1.07 5.23 4.9
scribed in [10]. All kinetic experiments were carried out in Pt/Al2 O3 (Pt(NO3 )2 ) 1.22 1.21 18.9
an atmosphere of helium, determining isothermally the re- Pd/Al2 O3 (PdCl2 ) 0.27 1.74 107
Pd/Al2 O3 (Pd(NO3 )2 ) 0.30 6.19 26.9
lationship between the reaction rate of NO reduction and
 D. Nazimek, W. Ćwikła-Bundyra / Catalysis Today 90 (2004) 39–42 41

0,03 25
0,025
20
0,02
15 80%
0,015
80% 60%
0,01 10
60%
0,005 5
60%
0 60% 0
1 80% 80%
2 1
3 2
4

Fig. 1. The rate of a NO + CO reaction over Pt/Al2 O3 obtained from Fig. 4. The rate of a NO + CO reaction in mol/gPd h over Pd/Al2 O3
H2 PtCl6 (1, 2) and from Pt(NO3 )2 (3, 4) at T = 773 K and XNO = 60 or obtained from PdCl2 (1) and from Pd(NO3 )2 (2) at T = 773 K and
80% (1, 3—reaction rate on gram of catalyst (mol/gcatal. h); 2, 4—reaction XNO = 60 or 80%.
rate on m2 surface (mol/m2 h)).

0,06
0,06 0,05
0,05 0,04
0,03
0,04
0,02
0,03 80% 0,01
0,02 60% 0
0,01 1 2 60%
3
0 60% 4
1 80%
2 3 Fig. 5. The rate of a NO + CO reaction in mol/gcatal. h on Pt/Al2 O3
4 (1—obtained from H2 PtCl6 ; 2—obtained from Pt(NO3 )2 ) and on
Pd/Al2 O3 (3—obtained from PdCl2 ; 4—obtained from Pd(NO3 )2 ) at
Fig. 2. The reaction rate of a NO + CO reaction over Pd/Al2 O3 ob-
T = 773 K and XNO = 60%.
tained from PdCl2 (1, 2) and from Pd(NO3 )2 (3, 4) at T = 773 K and
XNO = 60 or 80% (1, 3—reaction rate on gram of catalyst (mol/gcatal. h);
2, 4—reaction rate on m2 surface (mol/m2 h).
Then we compare rates of reaction between NO and CO
on the Pt and Pd catalysts obtained from NO3 − and Cl−
activity of the chlorine series preparation for palladium, for precursor we can state that the rate is the biggest for Pd cata-
which a drastic decrease in activity was noted. lysts obtained from Pd(NO3 )2 , at nitrogen oxide conversion
Fig. 5 shows a comparison of activities of the chlorine 60% and in temperature 773 K.
and nitrate series for both platinum and palladium catalysts In Table 2 relative rate of reduction of nitrogen oxide
at conversion degree 60%. by carbon oxide by two kinds of precursor were compared.
The catalysts Pd which were obtained from Pd(NO3 )2 Value of rate of reaction for both series have shown that
show the greater rate on recounted on m2 or gram of metal the activities of the nitrate series were higher for palladium
in comparison to PdCl2 . catalysts.
The results have shown that the preparations obtained on
the basis of chlorides have much better catalytic properties
for platinum than palladium catalysts.
3
Analyzing the course of nitrogen oxide reduction on Pt
2,5 catalysts it is necessary to mention that the bigger rate
2 is obtained on these which were received from H2 PtCl6 .
80%
1,5
60%
Table 2
1
The relative rates of the NO + CO reaction for platinum and palladium
0,5 60% catalysts at conversion degree 60%
0 80% Precursors Relative rate of reaction
1 r (mol/g h)Pd/r r (mol/m2 h)Pd/r r (mol/gPd h)/
2
(mol/g h)Pt (mol/m2 h)Pt r(mol/gPt h)
Fig. 3. The rate of a NO+CO reaction in mol/gPt h over Pt/Al2 O3 obtained Nitrate 2.42 0.55 10.05
from H2 PtCl6 (1) and from Pt(NO3 )2 (2) at T = 773 K and XNO = 60 Chloride 0.44 1.14 1.5
or 80%.
42 D. Nazimek, W. Ćwikła-Bundyra / Catalysis Today 90 (2004) 39–42

As far as it concerned Pt catalysts obtained from H2 PtCl6 • The course of the reaction between NO and CO depends
and Pt(NO3 )2 there were the significant differences in rate on the kind of precursors for both catalysts.
counted into gram of Pt, but there were hardly any differ- • For the platinum catalysts obtained from H2 PtCl6 as well
ences on the m2 surface or on gram of catalysts. According as from Pt(NO3 )2 insignificant differents in the activity of
to the work [13] impregnation solutions including chloride reduction NO reaction were observed.
can cause corrosion processes but they are less receptive on • Palladium catalyst obtained from Pd(NO3 )2 show more
the influence of water decreasing metals activity. The cat- activity than the catalyst obtained from PdCl2 and both
alysts received from Pt(NO3 )2 show more stability in re- platinum catalysts.
duction of nitrogen oxide process in examining temperature
773 K and they have more accessible active centers, which
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