Top Catal (2009) 52:21082111 DOI 10.

1007/s11244-009-9387-x

ORIGINAL PAPER

Arc Plasma Processing of Pt and Pd Catalysts Supported on c-Al2O3 Powders

S. Hinokuma K. Murakami K. Uemura M. Matsuda K. Ikeue N. Tsukahara M. Machida

Published online: 22 July 2009 Springer Science+Business Media, LLC 2009

Abstract Direct deposition of Pt and Pd nanoparticles onto c-Al2O3 powders was studied by using a pulsed arc plasma process under vacuum to use them as an automotive catalyst. As deposited Pt catalyst exhibited a higher metal dispersion and thus a higher catalytic activity for CO oxidation, compared to the conventional Pt/Al2O3 prepared by wet impregnation. In contrast, Pd/Al2O3 prepared by the arc plasma method was less active because of its metallic state of Pd with a lower dispersion. A weak interaction between precious metals and c-Al2O3 is not enough for thermal stabilization of as deposited nanoparticles during ageing in a stream of 10% H2O in air at 900 C. Keywords Arc plasma process Precious metal catalysts Automobile catalysts

metals being used per unit catalytic converter steadily increased during 1990s [5]. The development of technology that lessens the amount of precious metals without any deterioration in performance fully commenced in the last decade. Even after 2000, however, the demand for Pt and Pd for automobile gas purication has further increased to being currently more than 50% of total demand [1]. An innovative approach is therefore required to minimize the amount of precious metals. In this work, a novel dry process for the supported precious metal catalysts has been studied as an alternative catalyst preparation method. Unlike the conventional catalyst preparation using a wet impregnation process, nanoparticles of Pt and/or Pd were deposited directly from ingot metals onto the support powders (c-Al2O3) by means of an arc plasma process to study their microstructure and catalytic activity.

1 Introduction Precious metals play a key role in efciently removing the noxious components in auto exhaust such as nitrogen oxide (NOx), hydrocarbon (HC), and carbon monoxide (CO) [15]. Not only to achieve a higher conversion efciency but also to prolong its lifespan, the amount of precious 2 Experimental Section 0.4 wt% Pt or Pd loaded catalysts were prepared using a pulsed cathodic arc plasma source (Ulvac Inc., ARL-300) with a Pt or Pt cathode ([10 mm, Furuya Metals, Co. Ltd.) under vacuum as shown in Fig. 1. The arc pulse with a period of 0.2 ms and current amplitude of 2 kA was generated with a frequency of 2 Hz. The plasma from the cathode entered into a container which contains powders of a catalyst support, 3 wt% La-added c-Al2O3 (BET surface area: 134 m2 g-1), under mechanical stirring at ambient temperature. As prepared catalyst sometimes contained very large grains (more than several lm) of Pt or Pd, which were molten metallic droplets generated by the arc plasma. Therefore, the sedimentation in water was applied to remove them before use. The loading amount of Pt/Pd was

S. Hinokuma K. Murakami K. Uemura M. Matsuda K. Ikeue N. Tsukahara M. Machida (&) Department of Nano Science and Technology, Graduate School of Science and Engineering, Kumamoto University, 2-39-1Kurokami, Kumamoto 860-8555, Japan e-mail: machida@chem.kumamoto-u.ac.jp N. Tsukahara Tsukuba Institute for Super Materials, Ulvac, Inc., 5-9-6 Toukoudai, Tsukuba 300-2635, Japan

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Arc power supply

trigger power supply

He (balance) supplied at 100 cm3 min-1 (W/F = 5.0 9 10-4 g min cm-3). The efuent gas was analyzed using a Pfeiffer GSD30101 mass spectroscopy and a Horiba VA3000 NDIR gas analyzer.

condenser anode trigger electrode insulator cathode

3 Results and Discussion The XRD patterns of as prepared 0.4 wt% Pt and/or Pd/Al2O3 showed broad reections ascribable only to c-Al2O3. Reections from Pt or Pd could not be observed because of their low loading amount. Thus, the structure of precious metals was observed by using TEM. Figure 2a shows a TEM image of as prepared 0.4 wt% Pt/Al2O3(apg), where Pt particles can be observed as black deposits as highlighted by white arrows. Almost all the Pt particles were less than 5 nm and were dispersed on Al2O3 particles of several ten nanometers. As shown in the distribution of metal particle size (Fig. 2c), Pt/Al2O3(apg) showed a narrow distribution with an average Pt particle size of 2.5 nm, compared to Pd with a wider distribution and a larger average of 6.8 nm. The particle sizes of Pt/Pd were also determined by means of the H2O2 titration on the assumption of spherical particles. The calculated particle sizes of Pt (1.9 nm) and Pd (2.7 nm) are smaller than those measured by TEM, probably because of the presence of very small particles, which could not be identied in the TEM images. Figure 2b shows a TEM image of 0.4 wt% Pt/Al2O3(apg) after thermal ageing in 10% H2O/air at 900 C for 25 h. Appearance of several large grains of Pt with a diameter of about 20 nm, which were totally absent in the as deposited catalyst, indicates low thermal stability of the present system. Similar grain growth was also observed for Pd/Al2O3(apg) after the thermal ageing. Table 1 compares the metal dispersion for the two different preparation methods. Although the arc plasma method attained higher Pt dispersion (60%), it was soon decreased to 23% after thermal ageing. In case of Pd catalyst, on the other hand, wet impregnation yielded higher dispersion not only for as prepared, but also for aged catalysts. The XPS measurement showed that both Pt/Al2O3(apg) and Pt/Al2O3(imp) contained Pt in its metallic state. However, this is not the case of Pd catalysts as shown in the Pd3d XPS spectra (Fig. 3). For the Pd/Al2O3(imp) catalyst, the binding energy of Pd3d5/2 at 337.5 eV implies that almost all the surface Pd species should be Pd2? (PdO). This is consistent with the fact that PdO is thermodynamically stable at B780 C in air, whereas metallic Pd becomes stable at [780 C. By contrast, the XPS spectrum of Pd/Al2O3(apg) exhibited the presence of metallic Pd (335.8 eV) in addition to Pd2?. The higher fraction of metallic Pd (60%) rather than Pd2? (40%) is

Pt or Pd Plasma

catalyst support
stirring mechanism
Fig. 1 Schematic illustration of arc plasma process for the deposition of precious metals

controlled by the number of pulses (0.4 wt% loading by about 10000 shots). The catalysts were also prepared by a conventional wet impregnation method using aqueous solutions of Pt(NH3)2(NO2)2 and Pd(NO3)2 and subsequent heating at 600 C for 3 h in air. The catalysts prepared by arc plasma and impregnation methods are denoted as apg and imp, respectively. Powder X-ray diffraction (XRD) measurement was performed using monochromated CuKa radiation (30 kV, 20 mA, Rigaku Multiex). High-resolution TEM observation was performed in a FEI TECNAI F20 electron microscope operating at 200 kV. The XPS spectra were measured on a VG Sigmaprobe spectrometer using AlKa radiation (15 kV, 7 mA). The metal dispersion and particle size of Pt/Pd were determined by the H2O2 titration according to our previous report [6]. Catalytic reaction test for CO oxidation was carried out in a ow microreactor. Prior to the catalytic test, as prepared catalysts were pretreated in a stream of 10% H2O/air at 900 C for 25 h. Catalytic tests were carried out in a ow reactor at atmospheric pressure. As prepared 50 mg of catalyst (1020 mesh) was xed in a quartz tube ([6 mm) by quartz wool at both ends of the catalyst bed. Temperature dependence of catalytic activity was evaluated by heating the catalyst bed from room temperature to 600 C at constant rate of 10 C min-1 with supplying a simulated exhaust gas mixture containing CO (0.1%), O2 (1.25%) and

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2110 Fig. 2 TEM photograph of 0.4 wt% Pt/Al2O3(apg) a as prepared and b after ageing in 10% H2O/air at 900 C for 25 h. c Particles size distribution of as prepared 0.4 wt% Pt/ Al2O3(apg) and 0.4 wt% Pd/Al2O3(apg)

Top Catal (2009) 52:21082111

(a)
Al2O3

(b)

Pt

Pt

Al2O3

5 nm

50 nm

(c)

Pt/Al2O3(apg)
average 2.5 nm

Pd/Al2O3(apg)
average 6.8 nm

Fraction / %

Particle size / nm
Table 1 Metal dispersion of catalysts as prepared and after ageing Ageing Dispersion/% Pt apg imp None H2O/air, 900 C, 25 h None H2O/air, 900 C, 25 h 60 23 38 11 Pd 41 24 36

Particle size / nm

Pd0 Pd2+

typical for the arc plasma process, which was carried out in vacuum. Figure 4 compares the CO oxidation activity of supported Pt and Pd catalysts before and after thermal ageing in 10% H2O/air at 900 C for 25 h. Light-off of a stream of 0.1% CO, 1.25% O2 and He balance was observed at 120 C for as prepared Pt/Al2O3(apg), compared to 200 C required for Pt/Al2O3(imp). The Pt nanoparticles of as prepared by arc plasma process provided excellent catalytic performance due to its higher Pt dispersion (Table 1). After thermal ageing, however, the deactivation occurred as an increase of the light-off temperature, which was much more obvious for Pt/Al2O3(apg). The catalytic behavior of as prepared Pd was found to be different; the light-off

Intensity / a.u.

57

apg

imp

355

350

345

340

335

330

Binding energy / eV
Fig. 3 Pd3d XPS of 0.4 wt% Pd/Al2O3(apg) and 0.4 wt% Pd/ Al2O3(imp)

started at lower temperature \150 C and Pd/Al2O3(apg) was less active than Pd/Al2O3(imp). In addition to the lower metallic dispersion (Table 1), the abundance of

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plasma processing of Pd catalysts will next be conducted in the presence of O2.

4 Conclusions The present study demonstrates that arc plasma processing is able to prepare highly dispersed nanoparticles of precious metals onto catalyst support powders, which may be applied to automobile catalytic reactions. The merit of this process is to enable the one-step deposition of precious metal catalysts from ingot metals, compared to the multistep preparation of conventional wet impregnation. However, the low thermal stability of as deposited Pt/Pd posed a problem, which should be overcome by the use of support materials enabling stronger interactions with precious metals.
Acknowledgment This study was supported by Elements Science and Technology Project from MEXT Japan.

References
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Fig. 4 Catalytic activity for CO oxidation over 0.4 wt% Pt/Al2O3 and 0.4 wt% Pd/Al2O3 a as prepared and b after ageing in 10% H2O/ air at 900 C for 25 h. Reaction conditions: 0.1% CO, 1.25% O2, He balance, W/F = 5.0 9 10-4 g min cm-3

metallic Pd in Pd/Al2O3(apg) should be associated with the lower catalytic performance, because Pd becomes an active oxidation catalyst in the form of PdO rather than in the metallic state [79]. To overcome this problem, the arc

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