Carbon 43 (2005) 15121516 www.elsevier.

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Eect of heat treatment of activated carbon supports on the loading and activity of Pt catalyst
Min Kang a, Youn-Sang Bae b, Chang-Ha Lee
a b

b,*

LCD R&D Center, Samsung Electronics Co., Ltd., Yongin 449-711, Korea Department of Chemical Engineering, Yonsei University, Seoul 120-749, Korea Received 10 April 2003; accepted 26 January 2005 Available online 5 March 2005

Abstract The study has been done on the eect of heat treatment of activated carbon at 15731773 K on its structural and electronic properties as a catalyst support. The X-ray diraction result indicated that a partly graphitized structure was formed when the activated carbon was heated to a high temperature (1673 K). From the X-ray photoelectron spectroscopy result, it was found that Pt0 concentration was increased, but PtO and PtO2 concentrations were decreased with an increase in the heat treatment temperature. From the van Dams model applied to this result, it might be concluded that more p-sites are created as the heat treatment temperature becomes higher. From the CO-chemisorption result, the highest loading was observed in case of Pt/AC1673 sample. This improved loading ability could be explained by the special interaction of the graphitic planes (p-sites) with the metal particles. Based on the catalytic activity, CO-chemisorption and XPS results, it is concluded that the well-loaded Pt0 species mainly contribute to the catalytic activity. Moreover, it was found that dierent degrees of graphitization of heat treated activated carbon could cause dierent surface Pt0 and improve the resistance of carbon support against gasication under air oxidation. 2005 Elsevier Ltd. All rights reserved.
Keywords: Activated carbon; Catalyst support; Heat treatment; X-ray photoelectron spectroscopy

1. Introduction Catalysts made of noble metal supported by activated carbon are of considerable interest due to their applications in various processes such as purication of terephthalic acid and destruction of volatile organic compound (VOC) [16]. The porous structure and surface chemistry of activated carbon are important properties in connection with its adsorbent behavior [715]. Since most carbon supported catalysts suer from carbon burn-o in the case of gas phase oxidation (>500 K), it is important to provide long-term stability by

Corresponding author. Tel.: +82 2 2123 2762; fax: +82 2 312 6401. E-mail address: leech@yonsei.ac.kr (C.-H. Lee).

keeping them from gasifying to carbon dioxide. In order to improve the resistance of carbon supports to gasication under air oxidation conditions, many studies have been carried out [9,1618]. Coloma et al. [16] reported that the formation of partial graphitization made the surface of carbon more resistant to air oxidation due to the p-complex structures (p-sites) in the carbon basal planes. These p-sites are developed when oxygen surface complexes are removed from the surface of activated carbon, e.g., by heat treatment in an inert atmosphere [1618]. These delocalized p electrons have been used to account for the basicity of carbons without (or with a small amount) of oxygen surface groups [16]. This work investigated the activity and stability of various Pt/activated carbon catalysts in CO oxidation. The carbon supports and catalysts were characterized by BET, XPS, and CO-chemisorption. From these

0008-6223/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2005.01.035

M. Kang et al. / Carbon 43 (2005) 15121516

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results, the eects of heat treatment at dierent temperatures on the pore structure, the surface concentration of Pt0, and the catalyst loading (or dispersion) of activated carbon were studied. In particular, the formation of p sites under various heat treatment conditions was investigated.

2. Experimental 2.1. Preparation of activated carbon supports and catalysts The activated carbon (AC) used as parental material was obtained from the Norit Corp. (Norit ROX 0.8). The AC was washed with 2 M HCl solution for 12 h under reux for the purpose of removing sulfur and some ash, and then washed with distilled water under reux for 6 h. This treated AC was dried at 383 K overnight. The AC was evacuated at 573 K for 10 h, and then heated to a nal temperature (1573, 1673 and 1773 K, respectively) in the condition of oxygen-free dried nitrogen. After the sample was maintained at the nal temperature for 1 h, it was cooled to room temperature. In this study, the samples prepared at three dierent nal temperatures were referred to as AC1573, AC1673 and AC1773, respectively. Catalysts were prepared via the incipient wetness method aiming for 2 wt.% Pt on the AC using purchased precursor salt, H2PtCl6 xH2O. The impregnated catalysts were dried in the nitrogen condition at 393 K for 24 h to remove water and then calcined at 633 K for 12 h in the nitrogen condition to prevent the carbon support from burning o. 2.2. Characterization Nitrogen adsorption isotherms at the temperature of liquid nitrogen were obtained by a standard method. The samples were preliminarily outgassed at 573 K for 3 h in a stream of helium. The range of relative pressures (P/P0) varied from 0.0009 to 0.95; the equilibration time was 10 s. The overall volume of micropores (WODR) and the standard free energy of adsorption (E0) were calculated from the adsorption isotherms using the DubininRadushkevich equation [19]. The micropore surface area (SDR) and average pore diameters (LDR) were calculated according to the following semi-empirical relations (Eqs. (1) and (2)) proposed by Stoeckli [20]. S DR m2 =g 2000W 0 cm3 =g=LDR nm LDR nm 10:8=E0 11:4E0 kJ=mol 1 2

XPS was carried out with an aluminum anode as unmonochromatized X-ray source (1486.6 eV run at 10 kV and 15 mA, xed analyzer transmission). Metal loading was probed in a conventional ow system with a thermal conductivity detector, using hydrogen as a carrier gas. A short-time reduction of the catalysts was made in situ (heating the sample to 373 K in owing hydrogen for 510 min, followed by cooling to ambient temperature). Several pulses of CO (4.0 lmol) were then injected in 1-min interval. For the measurements, 3080 mg of catalyst was taken and 24 injections of CO were proved to be sucient for saturation. The stoichiometric coecient was assumed to be unity. 2.3. Activity test The carbon monoxide oxidation tests were performed under a stoichiometric condition in 1% CO/N2 and 0.5% O2/N2 at a xed space velocity of 3 103 h1. Each run utilized approximately 1 g of catalyst with 80120 mesh particles. The analyses of euent gases were performed with an on-line gas chromatography with a TCD and Carboxen-1000 column (60/80 mesh, 15 ft 1/8 in. stainless steel). At each reaction temperature, the reaction continued for about 2 h to achieve steady-state activity. The activity measurement was conducted in an ascending temperature manner so that the light-o behavior was recorded. The catalytic activity was ranked based on the light-o temperature (T50) at which 50% conversion occurred. In case of the stability test, a long-term time on the stream (TOS) experiment using carbon monoxide oxidation test was performed under the stoichiometric condition of 1% CO/N2 and 0.5% O2/N2 at a xed space velocity of 3 103 h1 and 450 K.

3. Results and discussion Fig. 1 shows the adsorption isotherms of the raw AC and those treated at 1573 (AC1573), 1673 (AC1673) and 1773 K (AC1773), respectively. The microstructure parameters of these materials obtained by analyzing the shape of the isotherm are presented in Table 1. The treatment of the carbon at 1573 K resulted in the increase in the mean size of the micropores (0.77 nm for AC and 1.21 nm for AC1573) while its volume (0.30 cm3/g) remained close to that of the untreated carbon (0.32 cm3/g). The inner surface area (SDR) of AC1573 was decreased by about 40% compared with that of the AC sample. The carbon treated at the highest temperature (1773 K) showed a dramatic decrease in the volume of micropores by about 90%, from 0.32 cm3/g (AC) to 0.037 cm3/g (AC1773). Therefore, the internal surface area (SDR) of AC1773 (64 m2/g) was less than 10% of

X-ray diraction experiments were performed on a standard diractometer using CuKa radiation. The calcined samples were scanned in the 2h range of 1080.

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M. Kang et al. / Carbon 43 (2005) 15121516

300 AC

C(002)
AC1573

Vads (cm3 at STP)

Intensity (a.u.)

200

AC1673

AC1673

100

AC1573

AC1773

AC

0 0.0 0.2 0.4 0.6 0.8 1.0

P/P0
Fig. 1. Nitrogen adsorption isotherms (77 K) of the heat-treated ACs.

10

20

30

40

50

60

70

2
Fig. 2. XRD proles of the heat-treated ACs at dierent temperatures.

Table 1 Characterization of the pore structure of the ACs investigated Carbon materials AC WODR (cm /g) SDR (m2/g) LDR (nm) E0 (kJ/mol)
3

Table 2 Peak position of Pt 4f and relative abundance of dierent Pt species determined from XPS measurements on the Pt/AC systems Pt 4f7/2 (eV) Pt/AC Pt/AC1573 Pt/AC1673 Pt/AC1773 71.55 71.55 71.55 71.55 Pt 4f/C 1sa 1.34 1.45 1.42 0.56 Pt 4f5/2 (eV) 74.65 74.8 74.75 74.75 Pt0 (%) 58.4 64.7 75.2 78.0 PtO (%) 27.8 23.8 18.3 12.4 PtO2 (%) 13.8 11.5 6.5 9.6

AC1573 0.30 540 1.21 19.8

AC1673 0.19 237 1.22 19.6

AC1773 0.037 64 1.22 19.5

0.32 854 0.77 26.0

that of the AC sample. The average size of the micropores (LDR = 1.22 nm) was identical to that of other samples, AC1573 and AC1673. The results of the XRD studies of raw and thermally treated carbon supports are presented in Fig. 2. The XRD patterns show that the structures of the AC and AC1573 materials are nearly amorphous. In the AC1673, a distinct ordering of the atomic structure could be observed. The result indicates that the partly graphitized structure was formed when the activated carbon was heated to high temperature (1673 K). A model for describing the chemistry of the impregnation of hexachloroplatinic acid on a carbon support has been proposed, in which two types of ligand sites for the Pt precursor were assumed: (1) oxygen-containing functional groups on the basal plane edges and (2) p-complex structures in the carbon basal plane [16,21]. In this study, this model was applied to predict the impregnation of Pt precursors on the AC samples. The XPS peak position and the area obtained from the t are listed in Table 2. The corresponding individual doublets and their calculated superposition are included in Fig. 3. The oxidation state of active metal is

a Determined by XPS corrected for atomic sensitivity factors (area) [22].

at least in part responsible for the catalytic behavior. The broad Pt 4f5/2/4f7/2 doublets apparently represent a superposition of contribution from several oxidation states. For the analysis of the oxidation of active Pt, each composite peak shape was deconvoluted into three-doublet binding energies. The deconvolution procedure should follow the requirement that both the Pt 4f band position and the multiplet splitting must be consistent with the characteristic ranges of each species. As a test, the intensity ratio for the doublet components of a given species was not xed during the t. The oxidation state of Pt appears to be important in determining the catalytic activity. Thus, the concentration of Pt0 was calculated by the XPS deconvolution procedure; 58.4% for Pt/AC, 64.7% for Pt/AC1573, 75.2% for Pt/AC1673, and 78% for Pt/AC1773. This result indicates that Pt0 concentration increases with an increase in the heat treatment temperature. On the other hand, as shown in Table 2, the concentrations of PtO and PtO2 decreased as the heat treatment temperature

M. Kang et al. / Carbon 43 (2005) 15121516

AC
Pt
0

1515

Intensity (a.u.)

AC1573

AC1673

68

70

72

74

76

78

80

Binding energy (eV)

Fig. 3. Curve t of the XPS 4f spectra of the Pt/AC systems.

increased. From the van Dams model, two types of ligand sites for the Pt precursor were presented on a carbon support: oxygen-containing functional groups and p-complex structures (p-sites) [21]. PtO and PtO2 may have been formed on the oxygen-containing functional groups while Pt0 on the p-sites. When the heat treatment temperature was increased, the Pt0 concentration increased while the PtO and PtO2 concentrations decreased. From this result, it may be concluded that more p-sites were created as the heat treatment temperature became higher. Table 3 presents the loading and the average particle size of Pt catalysts on the AC determined by CO-chemisorption. The highest loading was obtained from the Pt/ AC1673 sample. This increased loading ability can be explained by the special interaction of the graphitic planes (p-sites) with the metal particles [16]. Since the density of p-electrons on the metal was increased by the heat treatment, such high loading of Pt catalysts may be observed on the Pt/AC1673 sample. The lower loading of Pt/AC1773 is closely related to the texture of AC1773 (SDR = 64 m2/g, WODR = 0.037 cm3/g) as mentioned in Table 1. Since most of the Pt particles
Table 3 CO-chemisorption results of the Pt/AC systems CO-chemisorption (ml CO/g catalyst) Pt/AC Pt/AC1573 Pt/AC1673 Pt/AC1773
a

are located in the pore region, moderate surface area and porosity are essential for better metal loading. In the case of the Pt/AC catalyst, the surface oxygen groups can participate in the genesis of the catalysts favoring the sintering of metal particles. However, it appears that when the thermally unstable surface oxygen groups (e.g., carboxyl group) decompose during the calcination step (633 K), the re-loading of metal particles takes place. H2-chemisorption was attempted to measure the loading of Pt. However, no reliable data could be obtained, possibly due to the strong hydrogen adsorption of activated carbon. Fig. 4 shows the light-o curves of the Pt/AC systems. Their activity increased with the heat treatment from Pt/ AC to Pt/AC1673. In addition, the activity of Pt/ AC1673 was higher than that of the Pt-based conventional catalysts. The order of carbon monoxide oxidation activity was consistent with the loading and surface concentration of Pt as well as with the fraction of Pt0. The Pt/AC1773 gives the lowest activity due to the lowest surface area and the surface concentration of Pt. Based on the catalytic activity, CO-chemisorption and XPS results, it is concluded that the well-loaded Pt0 species mainly contribute to catalytic activity. The stability of Pt/AC is critical in applications because carbon can be burned-o in the air. The total carbon monoxide oxidation of the Pt/AC1673, which showed highest activity and CO-chemisorption in this study, was carried out continuously with 1% CO gas at 450 K for more than 80 h. The degree of oxidation was measured by the weight change of the Pt/AC1673 [5]. The weight of the Pt/AC1673 was almost unchanged

100

80

Pt/AC1673 Pt/AC1573 Pt/AC Pt/AC1773 Conventional catalyst

Conversion to CO2 (%)

60

40

20

Loading (%) 13.6 10.5 15.4 9.3

dp (nm) 8.3 (10.3)a 10.7 7.3 12.0

1.43 1.07 1.82 0.98

300

350

400

450

500

Temperature (K)

Before calcination (633 K).

Fig. 4. CO conversion light-o curves of the Pt/AC systems. The reaction gas mixture consisted of 1% CO/N2 and 0.5% O2/N2 at GHSV = 3000 h1.

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after the reaction. It implies that the Pt/AC1673, which has the best physical and chemical properties in this study, is considerably stable for a long time under the oxidizing condition. It seems that the partially graphitized surface of AC1673 contributes to enhancing the resistance to air oxidation. Acknowledgment This work was supported by Korea Research Foundation Grant (KRF-2001-005-E00031).

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