Preparation of Bismuth Nanoparticles in Aqueous Solution Andv

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Article
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, Wei Wang, Yu Liu, and Jianping Gao
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/ie501142a • Publication Date (Web): 03 Jun 2014
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Page 1 of 26 Industrial & Engineering Chemistry Research
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4 Preparation of bismuth nanoparticles in aqueous solution and its
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6 catalytic performance for the reduction of 4–nitrophenol
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8 Fengling Xia1, Xiaoyang Xu1, Xichuan Li1, Lei Zhang1, Li Zhang1, Wei Wang2, Yu
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10 Liu1*, Jianping Gao1
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School of Science, 2School of Chemical Engineering & Technology, Tianjin
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13 University, Tianjin 300072, P R China
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Abstract
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18 A simple method to fabricate Bi nanoparticles by using redox reactions between
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sodium borohydride and ammonium bismuth citrate with presence of souble starch in
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23 water phase was developed. The results show that soluble starch is better than PVP in
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stabilizing Bi nanoparticles. The as-prepared Bi nanoparticles were characterized by
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28 Fourier Transform infrared spectroscopy, transmission electron microscopy,
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energy-dispersive X-ray, powder X-ray diffraction. The catalytic performance of the
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33 Bi nanoparticles for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP)
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in the presence of sodium borohydride was studied. The effect of sodium borohydride
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38 concentration, initial 4-NP concentration, catalyst dose, and reduction temperature
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41 was also investigated.
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43 Key words: Bi nanoparticles, soluble starch, reduction, p-nitrophenol
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46 Introduction
47 Metal nanosized materials have attracted much attention during the past decades
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50 as their unique properties. They have been made use of their extensive potential
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52 applications in optics, magnetic, catalyst, biomedicine etc.1-4.Among of these metal
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54 elements, bismuth is particularly interesting because it can transit from a semimetal to
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56 a semiconductor as its crystallite size is small enough.5, 6 Recently, the nanoscale
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ACS Paragon Plus Environment
Industrial & Engineering Chemistry Research Page 2 of 26
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3 bismuth is also attracting a great deal of interest due to its potential applications in
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5 X-ray radiation therapy, catalysts, thermoelectricity and optical.7-10 Bi nanoparticles
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(BiNPs) electrodes have been applied in the detection of heavy metal ions as a
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10 substitute for Bi film.11 In addition, bismuth compounds, such as BiPO412, BiVO413,
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12 Bi2O314 and Bi2S3 nanoparticles15, were also reported over the past decades as novel
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14 catalysts for photodegradation of environmental pollute.
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17 Several approaches have been employed to fabricate BiNPs including thermal
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20 plasma16, electrochemical method17, gas condensation method18 and solution phase
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22 chemical methods. The latter is the most popular method, which often involves the
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25 reduction of relevant metal salts with various reductants in the presence of
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27 morphology-controlling surfactants. However, BiNPs are usually prepared in organic
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30 solvents, which present potential challenges for environment. Kim group used sodium
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32 borohydride and poly (vinylpyrrolidone) (PVP) as a reducing agent and dispersant to
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35 prepare BiNPs with average diameters of 6-13 nm in N, N-dimethylformamide.19 Li et
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37 al synthesized bismuth nanospheres by reducing bismuth nitrate in ethylene glycol
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40 phase in the presence of PVP.20 Preparation of BiNPs in aqueous solution is rarely
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42 reported because the bismuth salt is insoluble and the prepared BiNPs easily be
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45 hydrolyzed and oxidized in water. So the capping agents are necessary to obtain stable
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47 BiNPs dispersion. 21, 22
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50 As we all known, the production and application of nitrophenol compounds can
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52 cause environmental pollution. The most common method to reduce or eradicate the
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55 polluter is reduction of nitrophenol to aminophenol caltlyzed by noble metal
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57 nanoparticles, such as sliver 23
, gold 24, palladium 25
and platinum 26. Recently, Bi
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4 nanoparticles have been employed in the electrochemical detection of phenolic
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6 compounds. It exhibited good analytical performances to phenolic compounds in
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9 terms of sensitivity, detection limit, reproducibility and fabrication. However, to
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11 the best of our knowledge, no report about using BiNPs as catalyst in the chemical
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14 reduction of 4-nitrophenol (4-NP) to 4- aminophenol (4-AP) has been reported.
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16 Here, ammonium bismuth citrate was used to synthesize BiNPs in aqueous
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19 solution by reducing with sodium borohydride. “Green” soluble starch serves to
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21 stabilize the BiNPs and prevent them from aggregation. The catalytic performance of
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24 BiNPs for the reduction of 4-NP to 4-AP in aqueous solution under mild conditions
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26 was studied. The factors like sodium borohydride concentration, initial 4-NP
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29 concentration, catalyst dose, and reduction temperature that affect the catalytic
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31 activity were also investigated. The BiNPs are expected to be a potential efficient
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34 heterogeneous catalyst in industrial applications.
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2. Experimental
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39 Materials
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Ammonium bismuth citrate (ABC), sodium borohydride (NaBH4), PVP and
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44 soluble starch were all from Aldrich and used as received.
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Synthesis of bismuth nanoparticles
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49 The BiNPs were synthesized according to the following procedure: 0.2mmol
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ABC was dissolved in 20mL of distilled water, then 1.0mL soluble starch solution
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54 (10g/L) was added to the above solution with magnetic stirring at 25°C. After 20min,
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NaBH4 aqueous solution (10mL of 1.0M) was added by droplet, and the colorless
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4 solution turned to black quickly. The mixture was allowed to react for another 2h after
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6 NaBH4 aqueous solution was completely dripped off. The as-prepared nanoparticles
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9 were purified by centrifuging and rinsing with distilled water and alcohol. After being
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11 dried in vacuum oven for 24h, the obtained dark powders were kept in a vacuum
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14 dessicator for further characterization.
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16 Characterization
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18 The X-ray diffraction (XRD) pattern of the sample was measured using an x-ray
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20 diffractometer (BDX3300) with a reference target, Cu Kα radiation (λ=0.154nm)
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voltage, 30 kV, and current, 30 mA. The sample was measured from 10° to 70° with
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25 steps of 4°/min. The samples for transmission electron microscopy (TEM) were
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27 prepared by placing drops of a diluted BiNPs aqueous suspension onto carbon coated
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29 Cu grid and then dried under ambient conditions prior to being introduced into the
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TEM chamber. TEM observation and energy dispersive X-ray spectroscopy (EDX)
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34 measurement were performed using a Philips Tecnai G2F20 microscope at 200 KV.
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36 Fourier transform infrared (FTIR) spectra of the samples were measured with a
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38 Perkin-Elmer Paragon-1000 FTIR spectrometer in the range of 500-4000 cm−1. Each
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40 FTIR spectrum was the average of 20 scans. Thermogravimetric analysis was
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performed on a Rigaku-TD-TDA analyzer at a heating rate of 10 °C/ min in the air
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45 atmosphere. The analysis was performed on approximately 5 mg of the sample from
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47 room temperature to 600 °C.
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49 Evaluation of catalytic activity of BiNPs in redcution of 4-NP by NaBH4
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The catalytic activity of BiNPs in reduction of 4-NP by NaBH4 was
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54 investigated.29 For the catalytic reduction of 4-NP, fresh NaBH4 (0.5mL, 33.4g/L) was
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56 mixed with an aqueous solution of 4-NP (2.5mL, 0.21g/L). After the solution changed
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58 from light yellow to deep yellow, 0.5mL BiNPs (2g/L) was added. Since the UV
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3 absorbance of 4-NP is linearly proportional to its concentration in the solution, the
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5 ratio of the absorbance at time t (At) to that at t = 0 (A0) is equal to the concentration
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ratio ct/c0 of 4-NP. Consequently, the conversion progress can be directly measured
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10 using the absorption intensity. A TU-1901 spectrophotometer (Panaflo®, Japan) was
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12 employed to monitor the progress of the conversion of 4-NP to 4-AP at room
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14 temperature.
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17 Results and discussion
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20 In order to prevent aggregation of small nanoparrticles, dispersant or stabilizer is
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22 usually applied. The dispersant may be small molecules or macromolecules. The
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25 macromolecules PVP and soluble starch were used in preparation of BiNPs. Their
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27 representative X-ray diffraction pattern were measured and illustrated in Figure 1. It
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30 can be seen that all of the diffraction peaks belonging to pure rhombohedral phase of
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Bi (JCPDS No. 05-0519), and this is corresponding to other report. This XRD
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35 pattern indicates that under current synthetic conditions, the resulting product is
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37 elemental bismuth but not bismuch oxide. However, from the XRD peak intensity and
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40 half peak width of (012) can be concluded that the crystallinity of BiNPs prepared by
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42 PVP is bad. In addition, placed a period of time, the prepared BiNPs solution
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45 precipitated out of solution and became white (Figure 2a), which indicate that PVP
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47 could not prevent surface oxidation.
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50 For starch, a number of researchers have used it as the stabilizer in preparing the
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52 easily oxidized nanoparticles, such as Fe and Cu.31, 32 However, the mechanism of
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55 anti-oxidation action of starch was not specified. Here, Figure 2b show the BiNPs
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57 dispersion could retain black and have no visible precipitation in about two months.
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4 We think it may be related to the functional groups on starch macromolecules.
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6 Soluble starch contains large number of hydroxyl groups so that it can combine with
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9 Bi3+ easily and form a denser layer of starch on the surface of the BiNPs. In addition,
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11 as we all known, starch were used as reducing agent33, 34, so it can prevent the BiNPs
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14 from oxidating in some degree. In addition, BiNPs were also prepared without soluble
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16 starch and the BiNPs dispersion was shown in Figure 2c. The BiNPs quickly
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19 precipitated and settled on the bottom, and the upper solution became colorless,
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21 indicating that soluble starch has effect on the stability of BiNPs dispersion.
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24 Therefore, soluble starch can be used as antioxidant and stabilizer in preparing of
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48 Figure 1. XRD pattern of BiNPs
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4 a b c
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15 Figure 2. Photographs of BiNPs dispersion prepared in the presence of (a) PVP for
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1, 3, 7, 14 days; (b) soluble starch for 10, 20, 30, 60 days; and (c) no dispersant
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23 Figure 3 show the morphology of the BiNPs prepared in the above condition.
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25 The BiNPs were dialyzed against water before using TEM measurement. The BiNPs
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28 prepared in the presence of soluble starch (Figure 3a-c) are small and their size is in
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30 range of 10-20nm in diameter, while those prepared without soluble starch (Figure 3d)
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33 have a bigger size. In addition, BiNPs prepared in the presence of soluble starch are
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35 less aggregated as compared with those prepared without soluble starch. The high
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38 solution TEM (HRTEM) image of the BiNPs in Figure 3c clearly show lattice fringes
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40 with a lattice spacing of about 0.32 nm, which indexes to the (012) spacing of
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43 rhombohedral Bi. The EDX spectrum of the small BiNPs is shown in Figure 3e. The
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45 strong bismuth peaks and weak oxygen peak indicates that BiNPs were not oxidized.
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48 The carbon and oxygen peaks may be generated from the soluble starch and grid.
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Figure 3. TEM images of (a, b) BiNPs prepared in the presence of soluble starch; (c)
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54 HRTEM of BiNPs; (d) TEM images of the BiNPs prepared without soluble starch;
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and (e) EDX spectrum of the BiNPs.
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5 FTIR spectra of soluble starch and soluble starch stabilized BiNPs are shown in
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Figure 4. The BiNPs were washed with distilled water and absolute ethanol several
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10 times and dried in vacuum oven for 24h before FTIR measurement. As seen in Figure
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4, the peaks at about 3447 cm-1 and 3420 cm-1 were found for neat starch and BiNPs.
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15 The small shift can be attributed to the increased strength of hydrogen bonds between
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the soluble starch and surface of the BiNPs. 35 The peaks at around 2928 cm-1 are from
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20 C-H stretching vibrations from the CH2 groups of the soluble starch.36 The peaks at
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23 985 and 1165 cm-1 are assigned to the C-O bond stretching of C-O-C and C-O-H
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25 groups in starch respectively. It is seen that the peak at 985 cm-1 shifts to 1022cm-1 in
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28 the BiNPs spectra, which can be attributed to the interaction of BiNPs and starch.
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30 These results indicate that some starch molecules are adsorbed on the surface of
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54 Figure 4. FTIR spectra of (a) pure soluble starch and (b) BiNPs
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4 Figure 5 displays the TGA curves of soluble starch and BiNPs at a heating rate
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6 of 10°C/min in the air atmosphere. For soluble starch (Figure 5a) , there are two major
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9 mass losses: the mass loss around 100 °C is the result of the evaporation of adsorbed
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11 water, and the mass loss between 250 and 350 °C is mainly due to the decomposition
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14 of starch macromolecules. As for BiNPs, except for the two mass losses resulted from
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16 the evaporation of adsorbed water and decomposition of starch, there is a mass
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19 increase in the temperature of 420-600°C (inset in Figure 5), which can be assigned to
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21 the oxidation of BiNPs. The oxidizing temperature is high than other reports 21, 37, and
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24 it can indicate that the soluble starch can prevent surface oxidation availably. These
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26 results indicate that the residual starch could not be completely removed further. In
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29 addition, the TGA curve indicates that the weight loss corresponding to starch
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31 decomposition is about 10%, so the C content is about 4.77%, which is less than the
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34 result of EDX (5.69%). This is because EDX can only scan a few area of product, and
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36 the thickness of the starch layer is not equality.
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25 Figure 5. TGA curves of soluble starch and BiNPs
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30 The catalytic reduction of 4-NP to 4-AP with an excess amount of NaBH4 has
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33 often been used as a model reaction to evaluate the catalytic performance of metal
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35 nanoparticles. The reduction of 4-NP to 4-AP using aqueous NaBH4 is
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38 thermodynamically favorable (E0 for 4-NP/ 4-AP =-0.76 V and H3BO3/BH4- =-1.33 V
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40 versus NHE), but the kinetic barrier due to large potential difference between donor
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43 and acceptor molecules decreases the feasibility of this reaction.38 So, in the reduction
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45 process, the metal particles start the catalytic reduction by relaying electrons from the
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48 donor BH4- to the acceptor 4-NP which is adsorbed on the catalysts.38 The catalytic
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50 reduction is schematically presented in Figure 6.
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-
12 H2O H
NaBH4 NaBH3- H NaBH3OH + H
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+
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15 O
16 HO NO2 HO N
17 O
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20 O O
21 HO N H HO N
H
22 O H OH2
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24 -H2O
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26 O H O
27 HO N H HO N
28 H H
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31 -H2O
32 OH2 H
33 HO N H HO N
34 H H
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37 =BiNPs
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39 Figure 6. Mechanism of 4-nitrophenol reduction catalyzed by BiNPs
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Here, this reaction was used to investigate the catalytic activity of BiNPs. Since
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44 the amount of BiNPs was very small, it had no effect on the absorption spectra of
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4-NP. In order to establish an energy saving and environmentally friendly process,
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49 room temperature and distilled water were chosen as the reaction conditions. Before
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reaction, the original absorption peak of 4-NP is centered at 317 nm. After immediate
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54 addition of NaBH4, the color of solution changed from pale yellow to yellow (Figure
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7a). Meanwhile, a new absorption peak occurred at 400 nm was attributed to the
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4 formation of 4-nitrophenolate ion in the alkaline medium caused by NaBH4 (Figure
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7b). Without adding catalyst, the reduction will not proceed, the maximum
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9 absorption peak remains unaltered. After BiNPs were added, the intensity of
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11 absorption peak at 400 nm decreased, and at the same time, a new absorption peak for
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14 4-AP appeared at 300 nm. The UV-vis spectra also show an isosbestic point between
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16 the two absorption bands, indicating that the nitro compound was gradually converted
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19 to aminophenol without the observation of any side reactions.40, 41 After completion of
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21 the reaction, the peak at 400nm was completely disappeared.
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24 a
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1.4 4-NP+NaBH4
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Abs
0.8 4-NP
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0.4
46 4-AP
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0.0
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51 Wavelength (nm)
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54 Figure 7. (a) Photographs and (b) UV/Vis absorption spectra of 4-NP before and after
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reduction catalyzed by BiNPs
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4 The reduction of 4-NP to 4-AP can be achieved in the presence of NaBH4
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6 without using any catalyst, but it requires about 430 min. When BiNPs was added, the
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9 reaction was complete in about 120s. Figure 8a shows the typical evolution of the
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11 UV-vis spectra during the reduction with BiNPs catalyst. It is clearly seen that the
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14 absorption band of 4-NP decreases while the absorption band of 4-AP increases as the
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16 reaction proceeds. The reaction kinetics can be easily monitored from the
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19 time-dependent absorption spectra. The concentration of NaBH4 is high compared
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21 with that of 4-NP, so the reaction can be assumed to follow pseudo-first order reaction
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24 kinetics.42 Thus, the pseudo-first order rate constant of the reaction (K) can be
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26 calculated from the equation ln (At/A0) = Kt, where A0 and At are the absorbance
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29 values of 4-NP initially and at time t, respectively. The plot of ln(At/A0) versus t(s) is
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31 linear in the presence of the BiNPs. The rate constant calculated from the slope of the
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34 plot is 0.02751s-1. In order to compare our results with other metal catalysts reported
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36 in the literature, we calculated the ratio of the rate constant K to the total weight of the
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39 catalyst, k= K/m, which is called the activity factor. The k of the BiNPs was
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k=0.02751s-1/1.0mg=27.51s-1g-1, which is higher than previously reported values for
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44 GO-Au (2.26 s-1g-1) 43 and Ag/TiO2 (6.49 s-1g-1) 44. These results show that BiNPs has
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good catalytic performance like noble metal catalysts.
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16 Figure 8. (a) Time-dependent UV/Vis absorption spectra for the reduction of
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19 4-nitrophenol with BiNPs; (b) The plot of absorbance at 400 nm versus the reduction
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21 time
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24 As we all known, the rate of a chemical reaction depends on the concentration of
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26 reactants and reaction temperature.45 Here, linear plots of ln(At/A0) versus time have
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29 been obtained in the different concentrations of 4-NP, BiNPs and NaBH4. Initial
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31 concentration of 1, 1.5, 2, and 2.5mM were chosen to study the effect of 4-NP on the
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34 reduction, and the results are shown in Figure 9a. When 4-NP concentration was
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36 increased, the rate constant was observed to decrease. This phenomenon is abnormal,
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39 since increasing reactant concentration usually makes reaction more rapidly. The
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unexpected phenomenon can be explained with the reaction mechanism. High
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44 concentration of 4-NP leads to nearly full coverage of the surface of the BiNPs with
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4-NP, which restricts the electron transform from NaBH4 to 4-NP, so catalytic
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49 action of NaBH4 is restrained. Figure 9b shows effect of NaBH4 concentrations on the
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reduction of 4-NP. The rate constant tended to increase as the concentration of NaBH4
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54 was increased. In addition, the influence of catalyst dosage on the reaction rate is
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similar to that of NaBH4 as shown in Figure 9c. The rate constant increased with high
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23 Figure 9. Plots of ln(At/A0) versus time for the reduction of 4-NP in different
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28 The reduction was also conducted at different temperatures of 298, 323, and
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30 343K. The rate constants at different temperatures were calculated from linear plots of
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33 (c/c0) versus time (Figure 10a). It could be observed that the catalytic activity of the
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35 BiNPs decreased with decreasing catalytic temperature. Activation energy (Ea) is an
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38 empirical parameter for all chemical reactions, which shows the temperature
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40 dependency of the rate constant for a catalysis reaction.38 The Arminius equation
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43 shows relationship between rate constant and reaction temperature:
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45 lnk = lnA - Ea/RT
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48 Where, A is a constant known as the Arrhenius factor, k is the rate constant of the
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50 reaction at temperature T (in Kelvin), and R is the universal gas constant. The
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53 catalytic reduction of 4-NP was studied at three different temperatures 298, 323, 343K.
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55 It was observed that the plot of lnk versus 1/T is linear for 4-NP reduction and the
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58 value of k increases with the increase in temperature (Figure 10b). The activation
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4 energy calculated from the slope of the straight line was 2.65kJ/mol, which is lower
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6 than 33.8 and 24.59 kJ/mol reported by other researchers. 46, 47
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Figure 10. (a) Plot of (c/c0) versus time, (b) plot of lnk versus 1/T for 4-NP reduction
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49 at different temperatures in the presence BiNPs. Conditions: [4-NP) = 1.5mM; [BiNPs)
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=2g/L; [NaBH4) =1.08M.
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54 Reusability and stability are important factors for a good catalyst. In order to
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investigate the reusability of the catalyst, BiNPs was recycled by centrifugation. The
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4 same catalyst was utilized repeatedly up to five times for the reduction reaction. As
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6 illustrated in Figure 11, for BiNPs, the reaction time increased with the number of
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9 recycle times. The decrease in catalytic activity may be attributed to the aggregation
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11 of BiNPs and the adsorption of reaction product on BiNPs.
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33 Figure 11. Resusability of BiNPs as catalyst for the reduction of 4-NP
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38 Conclusion
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40 A simple method has been developed to fabricate BiNPs through redox reactions
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43 between NaBH4 and ABC in water phase by using soluble starch as the dispersant.
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45 The presence of soluble starch ensures preparation of stable BiNPs dispersion. The
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48 as-prepared BiNPs were 10-20nm in diameter with a rhombohedral phase and they
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50 exhibited excellent catalytic performance for the reduction of 4-NP. The activity
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53 factor (27.51s-1g-1) was even higher than some noble metal nanoparticles (GO-Au:
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55 2.26 s-1g-1, Ag/TiO2: 6.49 s-1g-1). The high catalytic activity and low cost make BiNPs
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58 become another new nanoparticles for use in environmental protection applications.
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4 AUTHOR INFORMATION
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6 Corresponding Author
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9 * Corresponding author: Fax: +86 22 274 034 75
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11 E-mail addresses: tjly@tju.edu.cn (Y Liu)
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14 Ackowledgement
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16 This work was supported by the National Science Foundation of China (51202158,
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19 21074089 and 21276181).
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21 Reference
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