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Green preparation and catalytic application of Pd nanoparticles

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4] nanoparticles. such as Au [2–4]. such as the Heck. Metal nanoparticles are of importance due to their remarkable properties and potential applications in a variety of areas. optics and magnetics. The UV/vis absorption spectroscopy. which would add to the environmental and economic burden. Preparation of Pd nanoparticles In a typical synthesis. For Pd nanoparticles. as the capping agent to fabricate Pt nanoparticles [7] and as the reducing agent to prepare Ag [5] and Pd [9] nanoparticles.edu.1. Nanjing 210093. Suzuki. 1. there remains a significant challenge to design and prepare Pd nanoparticles in a green strategy. the Pd nanoparticles exhibited good catalytic properties in the degradation of azo dyes. transmission electron microscopy (TEM). To achieve the above-mentioned aims of green nanoscience. many metal nanomaterials have been successfully synthesized under the guidance of green chemistry principles. 10]. The reaction was performed under room temperature and normal pressure. Further. they are widely employed in the field of hydrogen sensing and surface-enhanced Raman spectroscopy (SERS) [21–23]. Herein.org/Nano/19/305603 Abstract A green strategy for the facile preparation and effective stabilization of Pd nanoparticles has been developed by using D-glucose as the reducing and stabilizing agents. there is much room for exploring their potential properties in the fields of environmental protection.1088/0957-4484/19/30/305603 Green preparation and catalytic application of Pd nanoparticles Lang Xu.iop. we present a facile green strategy to synthesize and stabilize monodisperse Pd nanoparticles by using Dglucose as the reducing and stabilizing agents. an aqueous solution of H2 PdCl4 (5 ml. which could be applied in the treatment of wastewater. in final form 29 April 2008 Published 12 June 2008 Online at stacks. Ag [5. and enhancing the material and energy efficiency of safe chemical processes [1]. Over recent years. It is well known that Pd nanoparticles have wide-ranging applications.cn Received 7 April 2008. Thus green nanoscience aims at using environmentally benign and economically viable reagents or solvents. Furthermore. Fourier transform infrared spectroscopy (FT-IR) and zeta potential measurements were used to characterize the as-prepared Pd nanoparticles. However. 0. sensors. the majority of organic capping agents are toxic and expensive. reductant and stabilizing agent should be considered from ‘green’ perspectives in the preparation of metal nanoparticles [2]. they serve as the vital catalyst in C–C coupling reactions. the solvent. capping agents. Pt [7. Moreover.00 . the Pd nanoparticles showed good catalytic activity in the decolourization reaction of azo dyes. As a kind of noble metal. The effect of D-glucose concentration and pH value on the size distribution and stability was also discussed. 8] and Pd [9. Stille and Ullmann reactions [19. People’s Republic of China E-mail: jjzhu@nju. Xing-Cai Wu and Jun-Jie Zhu1 Key Lab of Analytical Chemistry for Life Science (MOE). Sonogashira. Most of the synthetic procedures have depended on organic 1 Author to whom any correspondence should be addressed. Pd nanoparticles with different sizes and shapes have been prepared by various chemical processes [11–15]. 6]. For instance. Nanjing University. designing inherently safe nanomaterials for reduced biological and ecological detriment. to prevent the agglomeration of metal nanoparticles [16–18]. such as catalysis. School of Chemistry and Chemical Engineering.IOP PUBLISHING Nanotechnology 19 (2008) 305603 (6pp) NANOTECHNOLOGY doi:10. It was found that the D-glucose concentration and pH value had an important effect on the size distribution and stability of the nanoparticles.06 M) was mixed with an aqueous solution of D-glucose 1 © 2008 IOP Publishing Ltd Printed in the UK 0957-4484/08/305603+06$30. electronics. Introduction The worldwide demand for environmentally friendly and sustainable methods to prepare nanomaterials requires the application of green chemistry principles. To date. nontoxic and inexpensive D-glucose was utilized as both the reducing and capping agents to synthesize Au [2. Still. such as surfactants and ligands. Experimental details 2. 20]. x-ray diffraction (XRD). Pd has attracted much attention. 2. In some cases.

After the addition of NaOH aqueous solution. This absorption band could be ascribed to the LMCT band of mixed chlorohydroxypalladium (II) species. The purpose of the dialysis operation was to remove excess nonbonded D-glucose and isolated ions. 2 The D-glucose concentration and pH value have a significant effect on the size distribution and stability of the Pd nanoparticles.0 with different D-glucose concentrations (i.0. The semipermeable membrane used in the dialysis was prepared in the laboratory by the volatilization of collodion. Moreover.3. the decrease and disappearance of these two peaks was concomitant with the appearance of a new absorption band at 280 nm. Effect of D-glucose and pH 3. Catalytic decolourization reaction of azo dyes The decolourization reaction of azo dyes catalyzed by the Pd nanoparticles was performed in a standard quartz cell with a 1 cm path length and approximately 3 ml volume. 05-0681). [PdCl2 (OH)2 ]2− and [PdCl3 (OH)]2− [24]. The reaction equation for the preparation of Pd nanoparticles. The control experiments were carried out in the same manner except for the addition of Pd nanoparticles.541 80 A).2 ml. and the intensity of this band increased with the increase in pH until the latter reached a value of 7. an aqueous solution of NaOH (1. The UV/vis absorption spectra of the Pd nanoparticles prepared in 0. two absorption peaks at 206 and 235 nm were observed. Figure 2(a) shows the representative TEM image of Pd nanoparticles prepared in 0.2. The average diameter of Pd nanoparticles could be calculated as 4. To confirm that the band at 270 nm was indeed caused by Pd nanoparticles.05. Figure 1. the UV/vis absorption spectra were recorded on a Shimadzu UV-3600 spectrophotometer before and after adding the Pd nanoparticles.0 M) was continuously added dropwise to the reaction system under moderate stirring.0 was dialyzed. which reached a maximum at pH 5.6 M). Afterwards. 2. The reaction evolution could be monitored by the UV/vis absorption spectroscopy. Characterization of Pd nanoparticles The process of Pd nanoparticle formation was accurately monitored by a Shimadzu UV-3600 spectrophotometer at a certain pH value. The pH values of the colloidal Pd solution were precisely measured by a Rex PHS-3B pH meter. 0. The XRD pattern was recorded on a Philips X’pert diffractometer equipped with a Cu Kα radiation source (λ = ˚ The FT-IR spectra were obtained using a Bruker 1. 0.Nanotechnology 19 (2008) 305603 CHO C OH C H + 2OH + Pd 2 C OH C OH CH 2 OH COOH C OH C H C OH C OH CH 2 OH L Xu et al H HO H H H HO H H + H 2 O + Pd 0 Scheme 1. vector 22 spectrometer. 0.5 and . which indicates the high monodispersion of Pd nanoparticles. all the diffraction peaks of the XRD pattern (figure 3) could be indexed to the pure face-centred cubic phase of palladium (JCPDS card no.8 ± 0. With the continuous addition of NaOH aqueous solution. as shown in figure 1. The samples for XRD and FT-IR measurements were prepared by dialyzing and drying the Pd nanoparticle dispersion. which matched with the value measured from the TEM images. The histogram of Pd nanoparticle size distribution is also provided in figure 2(b). The result showed that the as-obtained colloids were pure facecentred cubic palladium.e. Before the addition of NaOH aqueous solution.1. 2. The average diameter of Pd nanoparticles is 3. Scheme 1 shows the reaction equation.0.0. dried and analysed by XRD. The absorption band at 270 nm should be assigned to the Pd nanoparticles. Subsequently.075 mM) in the quartz cell.3 nm. that is. which could be assigned to the ligand-to-metal charge transfer (LMCT) band of the [PdCl3 (H2 O)]− complex [24].1 nm from the XRD pattern using the Scherrer equation. the colloidal dispersion prepared at pH 7. 0. four samples of Pd nanoparticles were prepared at pH 7.2. First.3.8 ml. (25 ml. The measurements of zeta potential were performed at relevant pH values on a Brookhaven 90 plus zeta potential analyzer. The samples for TEM studies were prepared by drying a drop of aqueous Pd nanoparticle dispersion on a piece of carbon-coated copper grid under ambient conditions. Pd (II) was reduced to Pd (0) by D-glucose. All aqueous solutions were prepared using deionized water from a Milli-Q water system (18 M cm). an aqueous solution of NaBH4 (0. It could be observed that the as-prepared Pd nanoparticles have a rather narrow size distribution.5 M D-glucose at pH 7. Results and discussion 3. The TEM images were recorded on a Philips Tecnai-12 transmission electron microscopy. Characterization of Pd nanoparticles Pd nanoparticles were prepared by using D-glucose to reduce H2 PdCl4 with the addition of NaOH. 0. 3. 30 mM) was mixed with an aqueous solution of an azo dye (2. To study the effect of D-glucose concentration.5 M D-glucose at different pH values.

8 ± 0. respectively. Similarly. (b).5.2 ± 2.0 (scale bar represents 50 nm) and (b) the corresponding size distribution histogram. When the pH value was below 5.2 nm. Nevertheless. no visible agglomeration was found.5 M D-glucose at pH 7.5. This band could be assigned to OH stretching. when the pH value is excessively high (e. 3.8 ± 0.0 and 9. pH 12). and their average diameters are 6. (b) would form within a few days. thus preventing aggregation and enhancing stability for Pd nanoparticles. The dominant high-frequency shift for D-glucose-stabilized Pd nanoparticles suggests the presence of intermolecular hydrogen bonding [2]. Hence. hydrogen bonding could form between the hydroxylated surface of the Pd nanoparticles and hydroxyl groups on D-glucose. The result was shown in figures 4(b). 1427 and 1231 cm−1 could be attributed to νas (CO3 ).3 nm. (e). the agglomeration of Pd nanoparticles could be obviously observed in figure 4(d) and Pd nanoparticles turned unstable because the aggregation .3. 3. the zeta potential was measured to study the surface charges of the as-prepared Pd nanoparticles at 3 Figure 2. respectively.g. the further increase in D-glucose concentration would have no prominent impact on the size distribution and stability of Pd nanoparticles. Pd aggregation would appear within a few days.8 ± 0. the agglomeration of Pd nanoparticles was observed as shown in figure 4(a).1 ± 3.3 nm and 3. four samples of Pd nanoparticles were prepared in 0. owing to the saturability of hydrogen bonding. when the D-glucose concentration was above 0. The presence of hydrogen bonding could be confirmed by comparing the FT-IR spectrum of Dglucose-stabilized Pd nanoparticles (figure 5(a)) with that of pure D-glucose (figure 5(b)). νs (CO3 ) and δ(HO) modes of bicarbonate. The XRD pattern of Pd nanoparticles. Figures 4(a). whereas it is at 3460 cm−1 for D-glucose-stabilized Pd nanoparticles.05 M.5. 3. suggesting that Pd nanoparticles became unstable again at comparatively higher pH values. when the pH value was above 6. 6. to research the effect of pH value. Additionally. 7.4 nm.3 M. Therefore.5 nm. 3. 2(a) and 4(f) represent their respective TEM images and relevant size distribution histograms. 3.5 M D-glucose at different pH values (i. When the Dglucose concentration was below 0.5.3 nm and 3. (a) The representative TEM image of Pd nanoparticles prepared in 0. 2(a) and 4(c). Figures 4(d). Since hydroxyl groups are present on the surface of Pd nanoparticles. respectively [25]. Further. 2(a) and 4(f). hydroxyl and bicarbonate groups were chemisorbed on the surface of the Pd nanoparticles.6 M). Their average diameters are 5.8 ± 0. and the stability of Pd nanoparticles was strengthened because no aggregation was observed for several months. On the other hand. in which a strong band at 3460 cm−1 is observed.4 nm. Figure 5(a) shows the FT-IR spectrum of Pd nanoparticles. The OH stretching band is at 3305 cm−1 for pure D-glucose.8 ± 0.e. the higher the D-glucose concentration is. On the other hand. 2(a) and 4(c) show their respective TEM images and corresponding size distribution histograms. 0. The mechanism of D-glucose and the pH effect The surface of the as-prepared Pd nanoparticles was studied by FT-IR analysis.3 nm.0). the more hydrogen bonds will form between the hydroxylated surface of Pd nanoparticles and hydroxyl groups of D-glucose. The mechanism of Dglucose concentration and the pH effect on Pd nanoparticles is discussed below. pH 5. The other three bands at 1630. the Pd size distribution became narrow due to the absence of agglomeration as shown in figures 4(e).Nanotechnology 19 (2008) 305603 L Xu et al (a) Figure 3.8 ± 0.

Nanotechnology 19 (2008) 305603 L Xu et al Figure 4. . when the pH value is below 6.6 M D-glucose at pH 7.0. Herein.5.5 and –O− at pH > 6. Furthermore. the absolute value of the zeta potential declined as pH decreased. (d) at pH 5. (b) in 0. based on the measurement of the zeta potential.0.5 to 10. when the pH value was above 10. the surface of Pd nanoparticles should mainly have –OH at pH < 6.0.3 M D-glucose at pH 7.5 M D-glucose. Figure 5. Previous measurement of the 4 zeta potential of Au nanoparticles against pH has confirmed the existence of an equilibrium between –OH and –O− dictated by the pH value [3].5 in 0. (c) in 0.0.0. –O− is predominant. the measurement of the zeta potential was in accordance with the observation concerning the effect of pH value mentioned above. FT-IR spectra of (a) D-glucose-stabilized Pd nanoparticles and (b) pure D-glucose. when the pH value varied from 6. Therefore. the absolute value of the zeta potential decreased. As shown in figure 6. (e) at pH 6.0 in 0. In other words. the absolute value of the zeta potential remained almost constant. otherwise.5 [3]. It is well known that the absolute value of the zeta potential is proportional to the colloidal stability. when the pH is below the pK value. Figure 6. Here. different pH values.5 in 0. The plot of zeta potential value against pH.5 M D-glucose (scale bar represents 50 nm).05 M D-glucose at pH 7.5 M D-glucose. (f) at pH 9. The TEM images of Pd nanoparticles prepared (a) in 0. The insets represent the relevant size distribution histograms. Such equilibrium shifting is determined by the pH value relative to the pK value of the hydroxylated surface of Pd nanoparticles. –OH is predominant. and such a constant value reached the maximum. the measurement of the zeta potential of the as-prepared Pd nanoparticles can also demonstrate the presence of the pH-dependent equilibrium between –OH and –O− on the surface of Pd nanoparticles.

and the as-prepared Pd nanoparticles can increase the decolourization reaction rate of different species of azo dyes. suggesting that the decolourization of Congo red proceeded rather slowly in the mere presence of the strong reducing agent NaBH4 . the comparatively higher pH value (e. which could be assigned to the conjugated system formed by the –N=N– bonds of Congo red.g. On the other hand.4. after the addition of the Pd nanoparticles. thereby strengthening the kinetic stability of Pd nanoparticles.43 [26]. Figure 8. it was rational to presume that the NaBH4 concentration remained constant throughout the reaction. a kind of azo dye with two –N=N– bonds.0) would destroy the stability of the Pd nanoparticle owing to the coagulation effect of excess electrolyte. The catalytic mechanism of Pd nanoparticles probably consists in the efficient Pdnanoparticle-mediated electron transfer from borohydride ions to azo bonds. 4. The visible absorption spectra in figure 7 could precisely monitor the process of the catalytic decolourization reaction. Catalytic function of Pd nanoparticles The as-prepared Pd nanoparticles could be effectively used to catalyze the decolourization reaction of azo dyes. A is the absorption intensity of Congo red at 493 nm. As a representative case. Figure 8 shows that this was the case because a plot of ln A versus reaction time was found to be linear. the colour soon faded. The monodisperse Pd nanoparticles were prepared by using an aqueous solution of .44 × 10−5 s−1 .05 mM). 3. which could be ascribed to the breakage of –N=N– bonds. The plot of ln A versus reaction time for the decolourization of Congo red catalyzed by Pd nanoparticles. After the addition of Pd nanoparticles. Compared to Congo red. It could be deduced that Pd nanoparticles accelerated the decolourization of Congo red with the increase in reaction rate constant by more than 103 times. the catalytic activity of Pd nanoparticles was first investigated in the decolourization of Congo red.0. D-glucose would possess –OH groups at pH < 12. The real-time visible absorption spectra for the decolourization of Congo red in the presence of Pd nanoparticles as a catalyst.5 to 10. as listed in table 1. The red colour of Congo red is attributed to this maximum absorption band. no colour change could be visibly observed for a long time. the abundance of –O− at the high pH value would increase the electrostatic repulsion between negatively charged nanoparticles. However. largely reducing the harm to the environment [27]. All of the decolourization reactions are first order with respect to the corresponding azo dyes. When an aqueous solution of NaBH4 was added to Congo red solution. Before the addition of Pd nanoparticles. the hydrogen bonding between the Pd nanoparticle surface and D-glucose is strong enough to limit aggregation and stabilize Pd nanoparticles for a long period. To demonstrate the Pd nanoparticles have a universal catalytic activity in the decolourization reaction of azo dyes. Thus the decolourization reaction should be of first order with respect to Congo red. Since the concentration of NaBH4 (2 mM) in the reaction system was much larger than that of Congo red (0. Conclusion In summary. indicating the remarkable catalytic effect of Pd nanoparticles on the decolourization reaction of Congo red. the reaction rate constant of the control experiment without the catalyst was obtained in the same manner as mentioned above except for the addition of Pd nanoparticles and it was 3. pH 12.Nanotechnology 19 (2008) 305603 L Xu et al Figure 7. which could be used to monitor the decolourization reaction. for the reason that it is much more effective for the hydrogen bonding interaction between –O− on the Pd nanoparticle surface and –OH of D-glucose than between two –OH groups. for its pK value is 12. the predominance of –OH at the low pH value leads to a weak hydrogen bonding interaction. there was the maximum absorption band 5 centred at 493 nm. various kinds of azo dyes were studied under the same conditions described above. So at the high pH value. the absorption band at 493 nm decreased and disappeared. whereas it is weak when –OH is dominant at low pH values (lower than 5. Therefore.0) when –O− is dominant on the surface of Pd nanoparticles.5). Moreover. For comparison. we present a facile green method for the synthesis and stabilization of Pd nanoparticles. Conversely. The reaction rate constant was calculated as 3. which fails to effectively prevent the aggregation of Pd nanoparticles. its degradation products become inclined to biodegradation and mineralization. hydrogen bonding is strong at high pH values (ranging from 6.61 × 10−2 s−1 .

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