Preparation of Bismuth Nanoparticles in Aqueous Solution and Its

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Preparation of Bismuth Nanoparticles in Aqueous Solution and Its Catalytic Performance for the Reduction of 4‑Nitrophenol Fengling Xia,† Xiaoyang Xu,† Xichuan Li,† Lei Zhang,† Li Zhang,† Haixia Qiu,† Wei Wang,‡ Yu Liu,*,† and Jianping Gao† †

School of Science, and ‡School of Chemical Engineering & Technology, Tianjin University, Tianjin 300072, P R China ABSTRACT: A simple method to fabricate Bi nanoparticles by using redox reactions between sodium borohydride and ammonium bismuth citrate in the presence of soluble starch in water phase was developed. The results show that soluble starch is better than PVP in stabilizing Bi nanoparticles. The as-prepared Bi nanoparticles were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, energy-dispersive X-ray, and powder X-ray diffraction. The catalytic performance of the Bi nanoparticles for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of sodium borohydride was studied. The effects of sodium borohydride concentration, initial 4-NP concentration, catalyst dose, and reduction temperature were also investigated.

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INTRODUCTION Metal nanosized materials have attracted much attention during the past decades because of their unique properties. They have made use of their extensive potential applications in optics, magnetics, catalysts, and biomedicine, etc.1−4 Among these metal elements, bismuth is particularly interesting because it can transit from a semimetal to a semiconductor as its crystallite size is small enough.5,6 The nanoscale bismuth has also attracted a great deal of interest because of its potential applications in X-ray radiation therapy, catalysts, thermoelectricity, and optical uses.7−10 Bi nanoparticles (BiNPs) electrodes have been applied in the detection of heavy metal ions as a substitute for Bi film.11 In addition, bismuth compounds, such as BiPO4,12 BiVO4,13 Bi2O3,14 and Bi2S3 nanoparticles,15 were also reported over the past decades as novel catalysts for photodegradation of environmental pollutants. Several approaches have been employed to fabricate BiNPs including thermal plasma,16 an electrochemical method,17 a gas condensation method,18 and solution phase chemical methods. The latter is the most popular method, which often involves the reduction of relevant metal salts with various reductants in the presence of morphology-controlling surfactants. However, BiNPs are usually prepared in organic solvents, which present potential challenges for the environment. Kim group used sodium borohydride and poly(vinylpyrrolidone) (PVP) as a reducing agent and dispersant to prepare BiNPs with average diameters of 6−13 nm in N,N-dimethylformamide.19 Li et al. synthesized bismuth nanospheres by reducing bismuth nitrate in the ethylene glycol phase in the presence of PVP.20 The preparation of BiNPs in aqueous solution is rarely reported because the bismuth salt is insoluble, and the prepared BiNPs can be easily hydrolyzed and oxidized in water. So the capping agents are necessary to obtain stable BiNPs dispersion.21,22 As is known, the production and application of nitrophenol compounds can cause environmental pollution. The most common method to reduce or eradicate the polluter is the reduction of nitrophenol to aminophenol catalyzed by noble metal nanoparticles, such as sliver,23 gold,24 palladium,25 and platinum.26 Recently, Bi nanoparticles have been employed in © 2014 American Chemical Society

the electrochemical detection of phenolic compounds. It exhibited good analytical performances to phenolic compounds in terms of sensitivity, detection limit, reproducibility, and fabrication.27,28 However, to the best of our knowledge, no report about using BiNPs as a catalyst in the chemical reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) has been reported. Here, ammonium bismuth citrate was used to synthesize BiNPs in aqueous solution by reduction with sodium borohydride. “Green” soluble starch serves to stabilize the BiNPs and prevent them from aggregation. The catalytic performance of BiNPs for the reduction of 4-NP to 4-AP in aqueous solution under mild conditions was studied. The factors like sodium borohydride concentration, initial 4-NP concentration, catalyst dose, and reduction temperature that affect the catalytic activity were also investigated. The BiNPs are expected to be a potential efficient heterogeneous catalyst in industrial applications.

2. EXPERIMENTAL SECTION Materials. Ammonium bismuth citrate (ABC), sodium borohydride (NaBH4), PVP, and soluble starch were all from Aldrich and used as received. Synthesis of Bismuth Nanoparticles. The BiNPs were synthesized according to the following procedure: 0.2 mmol ABC was dissolved in 20 mL of distilled water, then 1.0 mL of soluble starch solution (10g/L) was added to the above solution with magnetic stirring at 25 °C. After 20 min, NaBH4 aqueous solution (10 mL of 1.0 M) was added by droplet, and the colorless solution turned to black quickly. The mixture was allowed to react for another 2 h after NaBH4 aqueous solution was completely dripped off. The as-prepared nanoparticles were purified by centrifuging and rinsing with distilled water and alcohol. After being dried in vacuum oven for 24 h, the obtained Received: Revised: Accepted: Published: 10576

March 17, 2014 May 31, 2014 June 3, 2014 June 3, 2014 dx.doi.org/10.1021/ie501142a | Ind. Eng. Chem. Res. 2014, 53, 10576−10582

Industrial & Engineering Chemistry Research

Article

dark powders were kept in a vacuum desiccator for further characterization. Characterization. The X-ray diffraction (XRD) pattern of the sample was measured using an X-ray diffractometer (BDX3300) with a reference target, Cu Kα radiation (λ = 0.154 nm) voltage, 30 kV, and current, 30 mA. The sample was measured from 20° to 70° with steps of 4°/min. The samples for transmission electron microscopy (TEM) were prepared by placing drops of a diluted BiNPs aqueous suspension onto a carbon-coated Cu grid and then dried under ambient conditions prior to being introduced into the TEM chamber. TEM observation and energy dispersive X-ray spectroscopy (EDX) measurements were performed using a Philips Tecnai G2F20 microscope at 200 kV. Fourier transform infrared (FTIR) spectra of the samples were measured with a PerkinElmer Paragon-1000 FTIR spectrometer in the range of 500−4000 cm−1. Each FTIR spectrum was the average of 20 scans. Thermogravimetric analysis was performed on a Rigaku-TD-TDA analyzer at a heating rate of 10 °C/min in the air atmosphere. The analysis was performed on approximately 5 mg of the sample from room temperature to 600 °C. Evaluation of Catalytic Activity of BiNPs in Reduction of 4-NP by NaBH4. The catalytic activity of BiNPs in the reduction of 4-NP by NaBH4 was investigated.29 For the catalytic reduction of 4-NP, fresh NaBH4 (0.5 mL, 33.4 g/L) was mixed with an aqueous solution of 4-NP (2.5 mL, 0.21g/L). After the solution changed from light yellow to deep yellow, 0.5 mL of BiNPs (2g/L) was added. Since the UV absorbance of 4-NP is linearly proportional to its concentration in the solution, the ratio of the absorbance at time t (At) to that at t = 0 (A0) is equal to the concentration ratio ct/c0 of 4-NP. Consequently, the conversion progress can be directly measured using the absorption intensity. A TU-1901 spectrophotometer (Panaflo, Japan) was employed to monitor the progress of the conversion of 4-NP to 4-AP at room temperature.

This XRD pattern indicates that under current synthetic conditions, the resulting product is elemental bismuth but not bismuth oxide. However, from the XRD peak intensity and half peak width of (012) can be concluded that the crystallinity of BiNPs prepared by PVP is bad. In addition, after a period of time, the prepared BiNPs solution precipitated out of solution and became white (Figure 2a), which indicate that PVP could not prevent surface oxidation.

Figure 2. Photographs of BiNPs dispersion prepared in the presence of (a) PVP for 1, 3, 7, 14 days; (b) soluble starch for 10, 20, 30, 60 days; and (c) no dispersant.

A number of researchers have used it as a stabilizer for starch in preparing easily oxidized nanoparticles, such as Fe and Cu.31,32 However, the mechanism of the antioxidation action of the starch was not specified. Here, Figure 2b shows that the BiNPs dispersion could retain black and have no visible precipitation in about two months. We think it may be related to the functional groups on starch macromolecules. Soluble starch contains a large number of hydroxyl groups so that it can combine with Bi3+ easily and form a denser layer of starch on the surface of the BiNPs. In addition, as is known, starch is used as reducing agent,33,34 so it can prevent the BiNPs from oxidating to some degree. In addition, BiNPs were also prepared without soluble starch, and this BiNPs dispersion is shown in Figure 2c. The BiNPs quickly precipitated and settled on the bottom, and the upper solution became colorless, indicating that soluble starch has an effect on the stability of the dispersion of BiNPs. Therefore, soluble starch can be used as antioxidant and stabilizer in the BiNPs preparation. Figure 3 shows the morphology of the BiNPs prepared in the above condition. The BiNPs were dialyzed against water before using the TEM measurement. The BiNPs prepared in the presence of soluble starch (Figure 3a−c) are small and their size is in range of 10−20 nm in diameter, while those prepared without soluble starch (Figure 3d) have a bigger size. In addition, BiNPs prepared in the presence of soluble starch are less aggregated as compared with those prepared without soluble starch. The high solution TEM (HRTEM) image of the BiNPs in Figure 3c clearly show lattice fringes with a lattice spacing of about 0.32 nm, which indexes to the (012) spacing of rhombohedral Bi. The EDX spectrum of the small BiNPs is shown in Figure 3e. The strong bismuth peaks and weak oxygen peak indicates that BiNPs were not oxidized. The carbon and oxygen peaks may be generated from the soluble starch and grid. FTIR spectra of soluble starch and soluble starch-stabilized BiNPs are shown in Figure 4. The BiNPs were washed with distilled water and absolute ethanol several times and dried in vacuum oven for 24 h before FTIR measurement. As seen in Figure 4, the peaks at about 3447 and 3420 cm−1 were found for neat starch and BiNPs. The small shift can be attributed to the increased strength of hydrogen bonds between the soluble starch and surface of the BiNPs.35 The peaks at around 2928 cm−1 are from C−H stretching vibrations from the CH2 groups of the soluble starch.36 The peaks at 985 and 1165 cm−1

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RESULTS AND DISCUSSION To prevent aggregation of small nanoparticles, dispersant or stabilizer is usually applied. The dispersant may be small molecules or macromolecules. The macromolecules PVP and soluble starch were used in preparation of BiNPs. Their representative X-ray diffraction patterns were measured and illustrated in Figure 1. It can be seen that all of the diffraction

Figure 1. XRD pattern of BiNPs.

peaks belong to the pure rhombohedral phase of Bi (JCPDS No. 05-0519), and this corresponds to that of other reports.30 10577

dx.doi.org/10.1021/ie501142a | Ind. Eng. Chem. Res. 2014, 53, 10576−10582


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Figure 3. TEM images of (a, b) BiNPs prepared in the presence of soluble starch; (c) HRTEM of BiNPs; (d) TEM images of the BiNPs prepared without soluble starch; and (e) EDX spectrum of the BiNPs.

mass loss around 100 °C is the result of the evaporation of adsorbed water, and the mass loss between 250 and 350 °C is mainly due to the decomposition of starch macromolecules. As for BiNPs, except for the two mass losses resulted from the evaporation of adsorbed water and decomposition of starch, there is a mass increase in the temperature of 420−600 °C (inset in Figure 5), which can be assigned to the oxidation of BiNPs. The oxidizing temperature is higher than that of other reports,21,37 and it can indicate that the soluble starch can

are assigned to the C−O bond stretching of C−O−C and C−O−H groups in starch, respectively. It is seen that the peak at 985 cm−1 shifts to 1022 cm−1 in the BiNPs spectra, which can be attributed to the interaction of BiNPs and starch. These results indicate that some starch molecules are adsorbed on the surface of BiNPs. Figure 5 displays the TGA curves of soluble starch and BiNPs at a heating rate of 10 °C/min in the air atmosphere. For soluble starch (Figure 5a), there are two major mass losses: the 10578



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Figure 4. FTIR spectra of (a) pure soluble starch and (b) BiNPs.

Figure 7. (a) Photographs and (b) UV−vis absorption spectra of 4-NP before and after reduction catalyzed by BiNPs.

addition, the TGA curve indicates that the weight loss corresponding to starch decomposition is about 10%, so the C content is about 4.77%, which is less than the result of EDX (5.69%). This is because EDX can only scan a few areas of the product, and the thickness of the starch layer is not equal. The catalytic reduction of 4-NP to 4-AP with an excess amount of NaBH4 has often been used as a model reaction to evaluate the catalytic performance of metal nanoparticles. The reduction of 4-NP to 4-AP using aqueous NaBH4 is thermodynamically favorable (E0 for 4-NP/4-AP = −0.76 V and H3BO3/BH4− = −1.33 V versus NHE), but the kinetic barrier due to large potential difference between donor and acceptor molecules decreases the feasibility of this reaction.38 So, in the reduction process, the metal particles start the catalytic reduction by relaying electrons from the donor BH4− to the acceptor 4-NP which is adsorbed on the catalysts.38 The catalytic reduction is schematically presented in Figure 6. Here, this reaction was used to investigate the catalytic activity of BiNPs. Since the amount of BiNPs was very small, it had no effect on the absorption spectra of 4-NP. To establish an energy saving and environmentally friendly process, room temperature and distilled water were chosen as the reaction conditions. Before reaction, the original absorption peak of 4-NP is centered at 317 nm. After the immediate addition of NaBH4, the color of solution changed from pale yellow to yellow (Figure 7a). Meanwhile, a new absorption peak occurring at 400 nm was attributed to the formation of 4-nitrophenolate ion in the alkaline medium caused by NaBH4 (Figure 7b).39 Without adding catalyst, the reduction will not proceed, and the maximum absorption peak remains unaltered. After BiNPs were added, the intensity of absorption peak at 400 nm decreased, and at the same time, a new absorption peak for 4-AP appeared at 300 nm. The UV−vis spectra also show an isosbestic point between the two absorption bands, indicating that the nitro compound was gradually converted to aminophenol without the observation of any side reactions.40,41 After completion of the reaction, the peak at 400 nm completely disappeared.

Figure 5. TGA curves of soluble starch and BiNPs.

Figure 6. Mechanism of 4-nitrophenol reduction catalyzed by BiNPs.

prevent available surface oxidation. These results indicate that the residual starch could not be completely removed further. In 10579



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Figure 8. (a) Time-dependent UV−vis absorption spectra for the reduction of 4-nitrophenol with BiNPs; (b) plot of absorbance at 400 nm versus the reduction time.

The reduction of 4-NP to 4-AP can be achieved in the presence of NaBH4 without using any catalyst, but it requires about 430 min. When BiNPs was added, the reaction was complete in about 120 s. Figure 8a shows the typical evolution of the UV−vis spectra during the reduction with BiNPs catalyst. It is clearly seen that the absorption band of 4-NP decreases while the absorption band of 4-AP increases as the reaction proceeds. The reaction kinetics can be easily monitored from the time-dependent absorption spectra. The concentration of NaBH4 is high compared with that of 4-NP, so the reaction can be assumed to follow pseudo-first order reaction kinetics.42 Thus, the pseudo-first order rate constant of the reaction (K) can be calculated from the equation ln (At/A0) = Kt, where A0 and At are the absorbance values of 4-NP initially and at time t, respectively. The plot of ln(At/A0) versus t (s) is linear in the presence of the BiNPs. The rate constant calculated from the slope of the plot is 0.02751 s−1. To compare our results with other metal catalysts reported in the literature, we calculated the ratio of the rate constant K to the total weight of the catalyst, k = K/m, which is called the activity factor. The k of the BiNPs was k = 0.02751 s−1/1.0 mg = 27.51 s−1 g−1, which is higher than previously reported values for GO-Au (2.26 s−1 g−1)43 and Ag/TiO2 (6.49 s−1 g−1).44 These results show that BiNPs have as good a catalytic performance as noble metal catalysts. As is known, the rate of a chemical reaction depends on the concentration of reactants and reaction temperature.45 Here, linear plots of ln(At/A0) versus time have been obtained in the different concentrations of 4-NP, BiNPs, and NaBH4. Initial concentrations of 1, 1.5, 2, and 2.5 mM were chosen to study the effect of 4-NP on the reduction, and the results are shown in Figure 9a. When the 4-NP concentration was increased, the rate constant was observed to decrease. This phenomenon is abnormal, since increasing reactant concentration usually makes reaction occur more rapidly. The unexpected phenomenon can be explained with the reaction mechanism. A high concentration of 4-NP leads to nearly full coverage of the surface of the BiNPs with 4-NP, which restricts the electron transform from NaBH4 to 4-NP,29 so catalytic action of NaBH4 is restrained. Figure 9b shows the effect of NaBH4 concentrations on the reduction of 4-NP. The rate constant tended to increase as the concentration of NaBH4 was increased. In addition, the influence of catalyst dosage on the reaction rate is similar to that of NaBH4 as shown in Figure 9c. The rate constant increased with high amount of BiNPs.

Figure 9. Plots of ln(At/A0) versus time for the reduction of 4-NP in different concentrations of (a) 4-NP, (b)NaBH4, and (c) dosage of BiNPs. 10580



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The reduction was also conducted at different temperatures of 298, 323, and 343 K. The rate constants at different temperatures were calculated from linear plots of (c/c0) versus time (Figure 10a). It could be observed that the catalytic

Figure 11. Resusability of BiNPs as catalyst for the reduction of 4-NP.

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CONCLUSION A simple method has been developed to fabricate BiNPs through redox reactions between NaBH4 and ABC in the water phase by using soluble starch as the dispersant. The presence of soluble starch ensures preparation of stable BiNPs dispersion. The as-prepared BiNPs were 10−20 nm in diameter with a rhombohedral phase and they exhibited excellent catalytic performance for the reduction of 4-NP. The activity factor (27.51 s−1 g−1) was even higher than some noble metal nanoparticles (GO-Au, 2.26 s−1 g−1; Ag/TiO2, 6.49 s−1 g−1). The high catalytic activity and low cost make BiNPs attractive as another new nanoparticle for use in environmental protection applications.

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AUTHOR INFORMATION

Corresponding Author

*Fax: +86 22 274 034 75. E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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Figure 10. (a) Plot of (c/c0) versus time, (b) plot of ln k versus 1/T for 4-NP reduction at different temperatures in the presence BiNPs. Conditions: [4-NP) = 1.5 mM; [BiNPs) = 2g/L; [NaBH4) = 1.08 M.

ACKNOWLEDGMENTS This work was supported by the National Science Foundation of China (51202158, 21074089 and 21276181).

activity of the BiNPs decreased with decreasing catalytic temperature. The activation energy (Ea) is an empirical parameter for all chemical reactions that shows the temperature dependency of the rate constant for a catalysis reaction.38 The Arminius equation shows the relationship between rate constant and reaction temperature:

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ln k = ln A − Ea /RT where A is a constant known as the Arrhenius factor, k is the rate constant of the reaction at temperature T (in Kelvin), and R is the universal gas constant. The catalytic reduction of 4-NP was studied at three different temperatures 298, 323, and 343 K. It was observed that the plot of ln k versus 1/T is linear for 4-NP reduction and the value of k increases with the increase in temperature (Figure 10b). The activation energy calculated from the slope of the straight line was 2.65 kJ/mol, which is lower than 33.8 and 24.59 kJ/mol reported by other researchers.46,47 Reusability and stability are important factors for a good catalyst. To investigate the reusability of the catalyst, BiNPs were recycled by centrifugation. The same catalyst was utilized repeatedly up to five times for the reduction reaction. As illustrated in Figure 11, for BiNPs, the reaction time increased with the number of recycle times. The decrease in catalytic activity may be attributed to the aggregation of BiNPs and the adsorption of reaction product on BiNPs. 10581



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