Solvent: A Key in Digestive Ripening for Monodisperse Au Nanoparticles
- Peng Wang†1,
- Xuan Qi†1,
- Xuemin Zhang1,
- Tieqiang Wang1,
- Yunong Li1,
- Kai Zhang1,
- Shuang Zhao1Email author,
- Jun Zhou1, 2Email author and
- Yu Fu1Email author
© The Author(s). 2017
Received: 7 November 2016
Accepted: 14 December 2016
Published: 9 January 2017
This work has mainly investigated the influence of the solvent on the nanoparticles distribution in digestive ripening. The experiments suggested that the solvents played a key role in digestive ripening of Au nanoparticles (Au NPs). For the benzol solvents, the resulting size distribution of Au NPs was inversely related to the solvent polarity. It may be interpreted by the low Gibbs free energy of nanoparticles in the high polarity medium, which was supposedly in favor of reducing the nanoparticles distribution. Through digestive ripening in the highly polar benzol solvent of p-chlorotoluene, monodisperse Au NPs with relative standard deviation (RSD) of 4.8% were achieved. This indicated that digestive ripening was an effective and practical way to prepare high-quality nanoparticles, which holds great promise for the nanoscience and nanotechnology.
Au nanoparticles (Au NPs) and their self-assemblies have drawn intense attentions due to their unique properties and potential applications [1, 2], such as catalysts , electronic and optoelectronic nanodevices , biosensors , and biomedicine . For fully implementing the functions of Au NPs, the uniform size distribution is of key significance. The monodisperse nanoparticles (relative standard deviation less than 5.0%) show unique properties and higher performances compared with the corresponding polydisperse ones [7, 8]. Unfortunately, it is hard to prepare monodisperse Au NPs with simple synthesis process and common starting materials [9–11]. Therefore, a great deal of effort has been made to obtain monodisperse Au NPs . One main strategy is direct alteration of the synthesis method, including selection of special metal sources and reduction agents, introduction of nanoparticle seeds, addition of surfactants, and so on. However, although the monodisperse Au NPs have been achieved by direct synthesis , it suffers from high-cost of starting materials, tedious separation and unsatisfied repeatability. An alternative approach to preparing monodisperse Au NPs is post-treatment of the prepared ones, which could detour the issue.
Digestive ripening, discovered by Lin , is an effective post-treatment method. It is carried on by refluxing a nanoparticle suspension with an excess amount of capping agents (called as digestive ripening agents (DRA)), which could cause the shrink of large particles and the growth of small particles to achieve an equilibrium size at a stable state [11, 12]. A distinct feature of digestive ripening is that it can obtain high reproducibility and yield with fine control . The effect factors on digestive ripening, including capping agent, temperature, refluxing time, field effect, and the length of digestive ripening agent, have been explored [11, 16–20]. Solvent is an important participant in digestive ripening. Moreover, the study has shown the solvent plays a vital role in the synthesis process, which implied the effect of the solvent on digestive ripening would be remarkable. However, the related work has been rarely reported. In addition, thus far the monodisperse Au nanoparticles obtained by digestive ripening mainly came from the system reported by Lin . In that system, the original Au nanoparticles were synthesized by a surfactant-assisted method. Its process was tedious and the yield was low, that substantially weakened the advantage of digestive ripening.
Based on the above consideration, digestive ripening of Au NPsin different solvents was investigated in this work. The experiments showed that there was no obviously development in size distribution of Au NPs in the solvents of linear hydrocarbon. However, there was a dramatic change when benzol solvents were used. Moreover, the distribution was closely related with the solvent polarity. The higher the polarity of the used solvent is, the lower the RSD of the resulting nanoparticles is. When a highly polar benzol of p-chlorotoluene was used as the reflux solvent, RSD of the Au NPs after digestive ripening could reach as low as 4.8%, with which the superlattices could be assembled. Additionally, it is worth to emphasize that the original preparation of the Au NPs in our study was fast, low-costed, and surfactant-free. Combined with the simple synthesis method, the work offered a promising approach to facile fabrication of the monodisperse Au nanoparticles.
Synthesis of Initial Au NPs
The DDT-capped gold NPs was synthesized according to the literature . Firstly, 50 mM AuCl4 −/H+ solution was prepared by dissolving HAuCl4·4H2O with the same molar amount of HCl in aqueous. 50 mM BH4 −/OH− solution was made by dissolving NaBH4 with the same molar amount of NaOH in aqueous. Secondly, 475 μL of AuCl4 −/H+ solution was diluted with 47 mL DI water. Then, BH4 −/OH− (2.125 mL of 50 mM) was added to the solution under magnetically stirring, followed by heating for 3–4 min at boiling temperature of water. After it was cooled to room temperature, acetone (32 mL), hexane (38 mL), and DDT (0.5 μL) was introduced into the solution and mixed vigorously by hands for about 1 min to transfer Au NPs to the organic phase. Finally, the mixed solution was separated by a separating funnel, and the initial Au NPs were obtained.
Digestive Ripening of Au NPs
In a typical digestive ripening, a batch of as-prepared Au NPs solution was evaporated for about 35 °C by rotary evaporation to get rid of the solvent. And then, the dried Au NPs were re-dispersed in 10 mL different solvents (n-hexane, toluene, m-xylene, p-xylene, chlorobenzene, p-chlorotoluene and n-octane) with the addition of 2.5 μL DDT, respectively. Those colloids were refluxed at boiling point of different solvents and then slowly cooled down. The whole process of digestive ripening was completed.
Results and Discussion
A summary of Au NPs reflux in different solvents
Particle size (nm)
Temperature of boiling point (°C)
Dielectric constant (20 °C)25
3.66 ± 0.45
3.47 ± 0.48
3.42 ± 0.57
3.92 ± 0.48
3.99 ± 0.43
4.00 ± 0.38
In digestive ripening of the Au NPs, there were two possible factors that could play the vital role. The first possible one was the digestive ripening temperature, i.e., the reflux temperature of the solvent. However, as shown in Table 1, there was not a direct relationship between the reflux temperature and the size distribution. For example, the reflux temperatures of p-xylene, m-xylene, and chlorobenzene were almost the same, but the size distribution of the Au NPs after digestive ripening in them was completely different, ranging from 9.5 to 17%. For the other solvents, including n-hexane, toluene, and n-octane, the distribution also varied with the reflux temperatures at random suggesting that the digestive ripening temperature was not directly related with the size distribution.
The second possible factor could be the physical property of the solvent. The solvent we used in digestive ripening can be classified into two categories: linear solvents and benzol solvents. As shown in Table 1, the linear solvents (n-hexane, n-octane) could not remarkably improve the nanoparticles distribution. This was likely because the flexible chain of linear solvents could intertwine with the flexible chain of DDT coated on the nanopartcles, which reduced the etching degree of the Au NPs in digestive ripening. As a result, the monodisperse Au NPs was hard to obtain. On the contrary, the size distribution may dramatically be improved after digestive ripening in benzol solvents (p-xylene, m-xylene, toluene, and chlorobenzene). RSD could decrease from the initial 15 to 9.5% after 4 h reflux in chlorobenzene. Moreover, it was found that the size distribution was inversely related to the polarity of solvents. As shown in Table 1, with the increase of dielectric constants (representing the solvent polarity ) of the solvents, the size distribution of the Au NPs after digestive ripening was decreased gradually.
The influence of the solvents polarity on the size distribution could be explained by the following arguments. The polydispersity of the nanoparticles is supposed to stem from the random inhomogeneity of the reflux system, which was caused by the uncontrolled environmental disturbance. So, the nanoparticles polydispersity should be determined by the relative environmental disturbance to the nanoparticles energy. Low relative disturbance means that the influence of the environmental disturbance to the nanoparticles is weak, leading to narrow distribution. In our case, for digestive ripening in different solvents, the intensity of the disturbance should be in the same level. Therefore, the energy of the nanoparticles in different solvents is the key factor to the polydispersity. The lower the nanoparticles energy is, the lower the relative environmental disturbance is. That indicates weak influence of the environments and low polydispersity.
where σ is the interface free energy of the particle, z is the number of charges, r is the particle radius, and k is a constant related to the dielectric constants (ε) of the medium, as expressed in Eq. 2. In our study, the nanoparticles’ radius was almost the same. Therefore, the dielectric constant of the solvent was the main factor. Because of the inverse proportion of the dielectric constant to the free energy, the Au NPs in the solvent with higher polarity were more stable and could have lower polydispersity.
To verify the hypothesis, we designed two scenarios. One was the addition of new DDT to the system during the digestive ripening process; the other was reducing the digestive ripening temperature. In the first one, 2.5 μL new DDT was added to the solution of the Au NPs after reflux at 136 °C for 12 h, followed by another 12 h reflux. As shown in Additional file 1: Figure S1, the size distribution was only 7.0%, much lower than that of Au NPs after continuous reflux for 24 h. It suggested the new DDT took effective digestive ripening, implying the original DDT in the solution lost its effectiveness. In the other case, the heating temperature was decreased from 136 to 70 °C. As shown in Additional file 1: Figure S2 and Figure S3. The equilibrium time of digestive ripening can be achieved in 20 h, and afterwards, the size distribution of Au NPs nearly kept constant at least for another 12 h. It suggested that it was the high temperature that damaged the DDT. The two experiments confirmed the assumption and moreover demonstrated that the temperature and time made a difference to digestive ripening.
This work was focused on the influence of the solvents on the size distribution of the nanoparticles in digestive ripening. The experiments indicated that for the benzol solvents, the distribution could decrease remarkably with the increase of the polarity. This could be interpreted by the Gibbs free energy of a spherically charged particle. Higher solvent polarity could lead to lower energy of the nanoparticles, which may consequently reduce the polydispersity of the nanoparticles. Through adjusting the solvent polarity, the high-quality Au NPs with 4.8% relative standard deviation and corresponding supperlattices have been achieved. Verifying the effectiveness of the method in synthesis and self-assembly. Combined with simple and facile synthesis method, the digestive ripening in an appropriate solvent could be a promising and practical approach to obtain monodispersed nanoparicles, having great potential in the nanoscience.
This work was supported by the National Natural Science Foundation of China (Grant no. 21404021, 21503037, 51601032), the Doctoral Scientific Research Foundation of Liaoning Province (20141013, 201501149), Fundamental Research Funds for the Central Universities (N130205001, N150504004, N150504005, N140502001, N142004001, N140503001), and the Open Project of the State Key Laboratory of Supra molecular Structure and Materials (SKLSSM201609).
A task of the work was formulated by JZ and YF. PW carried out the synthesis of monodisperse Au nanoparticles and drafted the manuscript. XQ provided the guidance and assistance for the whole work. XMZ, TQW, and KZ took part in the characterization of Au nanoparticles. SZ participated in the data analysis and data interpretation. YNL created the figures. All authors read and approved the final manuscript.
The authors declare that they have no competing interests.
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- Daniel M-C, Astruc D (2004) Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. Chem Rev 104:293–346View ArticleGoogle Scholar
- Gong J, Li G, Tang Z (2012) Self-assembly of noble metal nanocrystals: fabrication, optical property, and application. Nano Today 7:564–585View ArticleGoogle Scholar
- Prati L, Villa A (2013) Gold colloids: from quasi-homogeneous to heterogeneous catalytic systems. Acc Chem Res 47:855–863View ArticleGoogle Scholar
- Talapin DV, Lee J-S, Kovalenko MV, Shevchenko EV (2009) Prospects of colloidal nanocrystals for electronic and optoelectronic applications. Chem Rev 110:389–458View ArticleGoogle Scholar
- Saha K, Agasti SS, Kim C, Li X, Rotello VM (2012) Gold nanoparticles in chemical and biological sensing. Chem Rev 112:2739–2779View ArticleGoogle Scholar
- Dreaden EC, Alkilany AM, Huang X, Murphy CJ, El-Sayed MA (2012) The golden age: gold nanoparticles for biomedicine. Chem Soc Rev 41:2740–2779View ArticleGoogle Scholar
- Cui H, Feng Y, Ren W, Zeng T, Lv H, Pan Y (2009) Strategies of large scale synthesis of monodisperse nanoparticles. Recent Pat Nanotechnol 3:32–41View ArticleGoogle Scholar
- Park J, Joo J, Kwon SG, Jang Y, Hyeon T (2007) Synthesis of monodisperse spherical nanocrystals. Angew Chem Int Ed 46:4630–4660View ArticleGoogle Scholar
- Li Y, Liu S, Yao T, Sun Z, Jiang Z, Huang Y, Cheng H, Huang Y, Jiang Y, Xie Z (2012) Controllable synthesis of gold nanoparticles with ultrasmall size and high monodispersity via continuous supplement of precursor. Dalton Trans 41:11725–11730View ArticleGoogle Scholar
- Tsunoyama H, Sakurai H, Negishi Y, Tsukuda T (2005) Size-specific catalytic activity of polymer-stabilized gold nanoclusters for aerobic alcohol oxidation in water. J Am Chem Soc 127:9374–9375View ArticleGoogle Scholar
- Lin M-L, Yang F, Lee S (2014) Digestive ripening for self-assembly of thiol-capped gold nanoparticles: the effects of adding dodecanethiol and reflux-heating. Colloids Surf A Physicochem Eng Asp 448:16–22View ArticleGoogle Scholar
- Yang Y, Yan Y, Wang W, Li J (2008) Precise size control of hydrophobic gold nanoparticles using cooperative effect of refluxing ripening and seeding growth. Nanotechnology 19:175603View ArticleGoogle Scholar
- Zheng N, Fan J, Stucky GD (2006) One-step one-phase synthesis of monodisperse noble-metallic nanoparticles and their colloidal crystals. J Am Chem Soc 128:6550–6551View ArticleGoogle Scholar
- Lin XM, Sorensen CM, Klabunde KJ (2000) Digestive ripening, nanophase segregation and superlattice formation in gold nanocrystal colloids. J Nanopart Res 2:157–164View ArticleGoogle Scholar
- Bhaskar SP, Vijayan M, Jagirdar BR (2014) Size modulation of colloidal Au nanoparticles via digestive ripening in conjunction with a solvated metal atom dispersion method: an insight into mechanism. J Phys Chem C 118:18214–18225View ArticleGoogle Scholar
- Prasad B, Stoeva SI, Sorensen CM, Klabunde KJ (2002) Digestive ripening of thiolated gold nanoparticles: the effect of alkyl chain length. Langmuir 18:7515–7520View ArticleGoogle Scholar
- Prasad B, Stoeva SI, Sorensen CM, Klabunde KJ (2003) Digestive-ripening agents for gold nanoparticles: alternatives to thiols. Chem Mater 15:935–942View ArticleGoogle Scholar
- Sahu P, Prasad B (2013) Fine control of nanoparticle sizes and size distributions: temperature and ligand effects on the digestive ripening process. Nanoscale 5:1768–1771View ArticleGoogle Scholar
- Sahu P, Prasad BL (2014) Time and temperature effects on the digestive ripening of gold nanoparticles: is there a crossover from digestive ripening to Ostwald ripening? Langmuir 30:10143–10150View ArticleGoogle Scholar
- Wu B-H, Yang H-Y, Huang H-Q, Chen G-X, Zheng N-F (2013) Solvent effect on the synthesis of monodisperse amine-capped Au nanoparticles. Chin Chem Lett 24:457–462View ArticleGoogle Scholar
- Martin MN, Basham JI, Chando P, Eah S-K (2010) Charged gold nanoparticles in non-polar solvents: 10-min synthesis and 2D self-assembly. Langmuir 26:7410–7417View ArticleGoogle Scholar
- Liu Y, Zhang W, Li S, Cui C, Wu J, Chen H, Huo F (2014) Designable yolk–shell nanoparticle@ MOF petalous heterostructures. Chem Mater 26:1119–1125View ArticleGoogle Scholar
- Lee D-K, Park S-I, Lee JK, Hwang N-M (2007) A theoretical model for digestive ripening. Acta Mater 55:5281–5288View ArticleGoogle Scholar
- Sidhaye DS, Prasad B (2011) Many manifestations of digestive ripening: monodispersity, superlattices and nanomachining. New J Chem 35:755–763View ArticleGoogle Scholar
- Dean JA (1999) Lange’s Handbook of Chem. McGraw-Hill, Inc., New YorkGoogle Scholar