Catal Lett DOI 10.

1007/s10562-010-0384-2

Inuence of Preparation Methods on the Performance of Metal Phosphate-Supported Gold Catalysts in CO Oxidation
Zhen Ma Hongfeng Yin Sheng Dai

Received: 25 April 2010 / Accepted: 26 May 2010 Springer Science+Business Media, LLC 2010

Abstract The inuence of different preparation methods on the performance of metal phosphate-supported gold catalysts in CO oxidation was surveyed. A series of metal phosphate-supported gold catalysts (Au/MPO, M = Al, Ca, Fe, Zn, La, Eu, Ho) were prepared by depositing dodecanethiol-capped gold nanoparticles on the supports, or by using Au(en)2Cl3 as the precursor, and these catalysts were tested in CO oxidation. The catalytic data were compared with the data obtained in our previous work employing catalysts prepared by depositionprecipitation (Ma et al. Catal Lett 126:20). It was found that only Au/LaPO is always active whereas Au/AlPO, Au/Ca PO, and Au/ZnPO are always not particularly active, regardless of the preparation methods. These catalysts were characterized by TEM, and it was found that the size of gold nanoparticles is not the only factor that determines the activity. Both catalyst supports and preparation methods are important factors. Keywords Gold Metal phosphate CO oxidation

1 Introduction Catalysis by supported gold nanoparticles has been extensively investigated recently [18]. Supports usually used
Z. Ma H. Yin S. Dai (&) Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA e-mail: dais@ornl.gov Z. Ma (&) Department of Environmental Science and Engineering, Fudan University, Shanghai 200433, Peoples Republic of China e-mail: zhenma@fudan.edu.cn

are oxides, such as TiO2, Al2O3, CeO2, SiO2, and ZrO2. However, metal salts have been seldom used as supports for making gold catalysts [920]. Our group recently developed an array of metal phosphate-based gold catalysts by depositionprecipitation [21]. It was found that 200 Cpretreated Au/MPO (M = Ca, Fe, Co, Y, La, Pr, Nd, Sm, Eu, Ho, Er) showed high CO conversions when the reaction temperature was below 50 C, and 500 C-pretreated Au/MPO (M = Ca, Y, La, Pr, Nd, Sm, Eu, Ho, Er) showed high CO conversions below 100 C [21]. The reaction mechanisms on Au/FePO4 were subsequently studied by in situ FTIR spectroscopy coupled with downstream mass spectrometry, and two reaction channels were identied [22]. It should be emphasized that all of these metal phosphate-supported gold catalysts were prepared by using depositionprecipitation. It is therefore worthwhile to study whether other preparation methods can lead to the same active catalysts, i.e., whether the performance of metal phosphate-supported gold catalysts is inuenced by the preparation methods or not. Colloidal deposition is sometimes used to prepare gold catalysts on oxide and carbon supports [2333]. Our group recently used dodecanethiol-capped gold nanoparticles (denoted as Au(SR) in this paper) to prepare Au/SiO2, Au/TiO2, and Au/C catalysts, and demonstrated that there catalysts, after thermal activation in O2-He, could be active for CO oxidation below room temperature [34]. The catalytic activity could be promoted by treating these as-synthesized catalysts by an aqueous KMnO4 or K2MnO4 solution, followed by drying and pretreatment in O2He at 300 C [34]. Another method for the preparation of gold catalysts is to use Au(en)2Cl3 (en = ethylenediamine) as the precursor. Gold catalysts made via the latter method include Au/NaHY [35], Au/TiO2 [36], Au/C [37], and Au/ SiO2 [3841]. In the current work, we rst loaded Au(SR)

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CO Conversion / %

on several typical metal phosphates, and tested the performance of the resulting catalysts in CO oxidation. We also attempted to use Au(en)2Cl3 as the precursor to prepare goldon-phosphate catalysts. Surprisingly, different preparation methods are different in terms of making active catalysts.

Au(SR)/La-P-O, effect of different pretreatment temperatures

100
pretreated at 500 C
pretreated at 300 C

50

2 Experimental AlPO4, [Ca5(OH)(PO4)3]x, FePO42H2O, Zn3(PO4)2, LaPO4xH2O, EuPO4xH2O, and HoPO4 were obtained from Aldrich. Dodecanethiol-capped gold nanoparticles (denoted as Au(SR)) were synthesized using HAuCl43H2O, dodecanethiol, and NaBH4 according to the literature [34, 42]. The average gold particle size (1.8 nm) was calculated from the XRD results by Scherrers equation. Au(SR)/phosphate samples were prepared via direct colloidal deposition. In a typical synthesis, gold nanoparticles (60 mg) was dispersed into 30 mL hexane and stirred for 10 min, followed by the addition of 2.0 g phosphate support. The suspension was stirred vigorously for 1 h and stirred slowly in open air to evaporate solvent. The remaining solid was dried in a vacuum oven at 60 C for 10 h. Au(en)2Cl3 precursor was synthesized using HAuCl4 3H2O and ethylenediamine [38, 40]. To synthesize Au(en)2Cl3/phosphate, 0.08 g Au(en)2Cl3 was dissolved in 100 mL H2O, the pH of the solution was adjusted to 10 with 1 M NaOH solution, and 2.0 g phosphate support was added. The pH value was re-adjusted to approximately 10 by an aqueous NaOH solution. The suspension was stirred at 6065 C for 2 h, then ltered, thoroughly washed with H2O, and dried in a vacuum oven at 70 C for 5 h. CO oxidation was tested in a plug-ow microreactor (Altamira AMI 200). Unless otherwise specied, 50 mg catalyst was loaded into a U-shaped quartz tube (4 mm i.d.) supported by quartz wool. The catalyst was pretreated online in owing 8% O2 (balance He) at 200 or 500 C for 2.5 h. The catalyst was cooled down before the gas was switched to the reaction mixture (37 cm3/min of 1% CO in air), and the reaction temperature was varied by immersing the U-shaped tube in cold-bath or a furnace. A portion of the product gas stream was extracted periodically with an automatic sampling valve, and analyzed using a dual-column gas chromatograph with a thermal conductivity detector. TEM images were taken on a Hitachi HD-2000 STEM operating at 200 kV.

re-tested after being tested as it is

as-synthesized (tested as it is)

0 0 100 200 300 400 500

Reaction Temperature / C

Fig. 1 CO conversions on Au(SR)/LaPO pretreated at different temperatures

below 200 C. The CO conversion increases when the reaction temperature is above 200 C and then levels off above 250 C. The temperature required for 50% conversion (T50) value is 242 C. However, the spent catalyst becomes quite active (T50 = 39 C) when the spent catalyst is cooled down and re-tested in CO oxidation. We believe that the presence of residual organic moieties in the as-synthesized catalyst makes the catalyst less active whereas the removal of residual species during the course of temperature ramping (reaction testing) can lead to the increased activity of the catalyst. To verify the above assertion, we pretreated the catalyst at 300 or 500 C, and found that the pretreated catalyst is quite active (T50 = 24 and 22 C, respectively). We additionally studied the thermal behaviour of Au(SR)/LaPO in air by TG/DTG (Fig. 2). The process is composed of multiple steps, and it is estimated that a pretreatment at 300 C under owing O2He in our reactor for 1 h can at least remove adsorbed water and some residual organic species.
100 99 98 97 0.04 0.06

TG/DTG of Au(SR)/La-P-O under Air

96 95 94 93 92 0.02

3 Results Figure 1 shows the CO conversions over Au(SR)/LaPO without or with pretreatment under different conditions. The as-synthesized Au(SR)/LaPO shows no activity

91 90 0 100 200 300 400 500 600 700 800

0.00

Temperature / C

Fig. 2 TG/DTG data of Au(SR)/LaPO under air

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Deriv. Weight / % C

Weight / %

-1

Metal Phosphate-Supported Gold Catalysts in CO Oxidation

To compare the activity more quantitatively, specic rates were calculated based on the CO concentration (1 mol%), ow rate (37 ml/min), CO conversions at 25 C from the conversion curves, the amount of catalyst put into the reactor (50 mg), and gold loadings measured by EDX (4.4 wt% Au, Table 1). For instance, the CO conversions of as-synthesized, retested, 300 C-pretreated, and 500 Cpretreated Au(SR)/LaPO samples at 25 C are 0, 28, 53, and 63%, respectively. Therefore, the specic rates at 25 C are calculated as 0, 0.12, 0.22, and 0.26 mol g-1 h-1, respectively. For comparison, the 200 C-preAu treated and 500 C-pretreated Au/LaPO (0.50 wt% Au) samples prepared by depositionprecipitation show 36 and 37% conversions, corresponding to specic rates of 1.3 and 1.3 mol g-1 h-1 at 25 C [21]. Au To know whether other metal phosphate-based gold catalysts are active in CO oxidation, we loaded gold on several typical metal phosphates and pretreated these catalysts at 300 or 500 C prior to reaction testing. As shown in Fig. 3, gold nanoparticles supported on AlPO, CaP O, FePO, ZnPO, EuPO, and HoPO are much less active than those supported on LaPO, regardless of the pretreatment temperature. In particular, the former catalysts are not active at room temperature. In comparison to our previous data on CO oxidation over Au/MPO prepared by depositionprecipitation [21], the key observations regarding the observed light-off curves are given in order: (1) Our previous work shows that Au/LaPO is active for CO oxidation [21], and the current work shows that Au(SR)/LaPO is also active. (2) Our previous work shows that Au/AlPO, Au/CaPO, and Au/ZnPO are relatively inactive for CO oxidation [21], and the current work shows that Au(SR)/AlPO, Au(SR)/CaPO, and Au(SR)/ZnPO are not active as well. (3) Our previous
Table 1 Elemental analysis results for as-synthesized gold catalysts Au (wt%) Au(SR)/AlPO Au(SR)/CaPO Au(SR)/FePO Au(SR)/ZnPO Au(SR)/LaPO Au(SR)/EuPO Au(SR)/HoPO Au(en)Cl3/AlPO Au(en)Cl3/CaPO Au(en)Cl3/FePO Au(en)Cl3/ZnPO Au(en)Cl3/LaPO Au(en)Cl3/EuPO Au(en)Cl3/HoPO 5.1 3.5 5.8 3.1 4.4 4.0 2.4 3.9 2.0 4.7 2.1 1.7 3.0 1.5 Metal (wt%) 22.1 (Al) 35.5 (Ca) 31.1 (Fe) 51.3 (Zn) 52.0 (La) 54.2 (Eu) 63.0 (Ho) 24.2 (Al) 18.2 (Ca) 30.2 (Fe) 50.1 (Zn) 49.5 (La) 56.5 (Eu) 63.2 (Ho) P (wt%) 21.5 18.2 18.1 14.6 10.8 10.5 18.8 22.8 37.5 14.5 15.2 11.7 10.2 9.5

A
100

Catalysts pretreated at 300 C

Au(SR)/La-P-O

CO Conversion / %

Au(SR)/Fe-P-O Au(SR)/Al-P-O

50
Au(SR)/Ho-P-O

Au(SR)/Ca-P-O Au(SR)/Eu-P-O

Au(SR)/Zn-P-O

B
100

Catalysts pretreated at 500 C

CO Conversion / %

Au(SR)/La-P-O Au(SR)/Fe-P-O

50

Au(SR)/Al-P-O

Au(SR)/Ho-P-O Au(SR)/Zn-P-O Au(SR)/Ca-P-O

0 0 100 200 300

Au(SR)/Eu-P-O

400

500

Reaction Temperature / C

Fig. 3 CO conversions on Au(SR)/MPO catalysts pretreated at 300 or 500 C

work shows that Au/FePO, Au/EuPO, and Au/HoP O are active for CO oxidation below room temperature, whereas the current work shows that Au(SR)/FePO, Au(SR)/EuPO, and Au(SR)/HoPO are much less active. Interestingly, Eu and Ho belong to the same rare earth group as La, whereas the catalysts made by replacing La by Eu or Ho are not active. Recently, it was reported that residual sulphur in catalysts prepared using thiol-capped gold nanoparticles may inuence the catalytic activity in CO oxidation [33]. Nevertheless, the extent of inuence as a function of different supports has not been established yet. Figure 4 shows the TEM data on several typical catalysts collected after pretreatment at 500 C and subsequent reaction testing. Finely divided small gold nanoparticles are well dispersed on AlPO, FePO, and HoPO catalysts. Therefore, the low activity of Au(SR)/AlPO, Au(SR)/FePO, and Au(SR)/HoPO is not because there are no small gold nanoparticles on support surfaces. On the other hand, active Au(SR)/LaPO has well dispersed small gold nanoparticles. Our group recently developed Au/SiO2 catalysts by using Au(en)2Cl3 as the precursor [38, 40]. The chloride in Au(en)2Cl3 can be displaced by hydroxide in aqueous NaOH, leading to the release of chloride into the aqueous

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Z. Ma et al. Fig. 4 Z-contrast TEM images of Au(SR)/AlPO, Au(SR)/ FePO, Au(SR)/LaPO, and Au(SR)/HoPO catalysts collected after pretreatment at 500 C and subsequent reaction testing. The scale bars represent 60 nm consistently

solution. The released chloride can be washed away by water, and the presence of residual chloride is minimal in Au/SiO2 [38]. In the current work, we also investigated the using of Au(en)2Cl3 in making metal phosphate-supported catalysts. As shown in Fig. 5, only Au(en)2Cl3/LaPO and Au(en)2Cl3/HoPO show signicant CO conversions at 200 C, whereas other catalysts are not active at this temperature. There are dips in the conversion curves of these two active catalysts, and this phenomenon has been also seen in our previous work [21]. Overall, the catalytic

Catalysts pretreated at 500 C

Au(en)2Cl3/Ca P O

100
Au(en)2Cl3/La P O

Au(en)2Cl3/Al P O

activity of Au(en)2Cl3/LaPO is much lower than that of Au(SR)/LaPO. Figure 6 shows the TEM data of catalysts collected after pretreatment at 500 C and subsequent reaction testing. Au(en)2Cl3/AlPO and Au(en)2Cl3/FePO have small gold nanoparticles, but we already know that they are not active for CO oxidation below 200 C. On the other hand, Au(en)2Cl3/LaPO and Au(en)2Cl3/HoPO have relatively bigger gold nanoparticles. In particular, the size of gold nanoparticles in Au(en)2Cl3/LaPO is much bigger than the one in Au(SR)/LaPO, probably due to the inuence of residual chloride which facilitates the sintering of gold nanoparticles. That may be the reason why Au(en)2Cl3/LaPO shows much lower catalytic activity compared with Au(SR)/LaPO.

CO Oxidation / %

Au(en)2Cl3/Ho P O

4 Discussion and Conclusions

Au(en)2Cl3/ Fe P O

50
Au(en)2Cl3/Eu P O

Au(en)2Cl3/Zn P O

0 0 100 200 300 400 500

Reaction Temperature / C

Fig. 5 CO conversions on Au(en)2Cl3/MPO catalysts pretreated at 500 C

The preparation methods are very important for obtaining active metal phosphate-supported gold catalysts, and the support effect also matters. (1) Gold nanoparticles supported on AlPO, CaPO, and ZnPO always show low activity in CO oxidation, no matter whether these catalysts are prepared by depositionprecipitation, colloidal deposition, or using Au(en)2Cl3 as the precursor. (2) Gold nanoparticles supported on LaPO are always active for CO oxidation, no matter whether the catalyst is prepared by

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Metal Phosphate-Supported Gold Catalysts in CO Oxidation Fig. 6 Z-contrast TEM images of Au(en)2Cl3/AlPO, Au(en)2Cl3/FePO, Au(en)2Cl3/LaPO, and Au(en)2Cl3/HoPO catalysts collected after pretreatment at 500 C and subsequent reaction testing. The scale bars represent 60 nm consistently

depositionprecipitation, colloidal deposition, or using Au(en)2Cl3 as the precursor. (3) Gold nanoparticles supported on FePO, EuPO, and HoPO show some activity in CO oxidation when the catalysts are made by depositionprecipitation, whereas the catalysts are not quite active when they are prepared by colloidal deposition or using Au(en)2Cl3 as the precursor. Therefore, deposition precipitation may be the best method to make metal phosphate-supported gold catalysts active for CO oxidation. It should be mentioned that the nature of active sites and reaction mechanisms are highly debated in the literature, and metallic gold, ionic gold, and the interface between gold nanoparticles and the support have been proposed to be the active sites [4, 5, 8]. Overbury and co-workers recently studied CO oxidation on Au/FePO using infrared spectroscopy, and concluded that metallic gold is more important for this reaction [22]. They also identied two reaction channels for this specic catalyst. However, the fact that two reaction channels occur on Au/FePO does not guarantee that the same thing happens on other phosphate-based gold catalysts. It would be interesting to study why gold catalysts based on LaPO support are active whereas gold catalysts based on AlPO, CaPO, or Zn PO support are not active. Is the difference due to different oxidation states of gold, to the adsorption and activation of oxygen, or to acidbase properties of different supports? In-depth experiments aiming at elucidating the

nature of active sites and reaction mechanisms are still needed in the future. In particular, infrared spectroscopy [22, 43, 44], XANES [45, 46], and in-situ XPS [47, 48] may provide such possibilities.
Acknowledgements Research sponsored by the Division of Chemical Sciences, Ofce of Basic Energy Sciences, U.S. Department of Energy under contract DE-AC05-00OR22725 with Oak Ridge National Laboratory, managed and operated by UT-Battelle, LLC. This research was also supported by the appointment for H.F. Yin to the ORNL Research Associates Program, administered by Oak Ridge Associated Universities.

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