Microreaction continuous synthesis of gold nanoparticles

doi:10.11949/0438-1157.20210014

Abstract

Abstract:

Gold nanoparticles have characteristic ultraviolet-visible absorption spectra, and they are widely used in the field of analysis and detection. In order to break through the technical limitations of batch stirring reaction to prepare gold nanoparticles, a continuous-flow microreaction method was proposed. This method implemented rapid and uniform mixing of HAuCl₄ and Na₃Ct aqueous solutions under acidic conditions with the help of threaded pipes, introduced an inert solvent to avoid particle deposition in the reactor, and used a membrane phase separator to complete the oil-water online phase separation, achieving continuous and stable preparation of gold nanoparticles. The influences of the reactant molar ratio, concentration, residence time, water-oil volume ratio, pH and other factors on the particle size distribution and absorption spectrum were investigated, and the narrow size distributed gold nanoparticles with average sizes of 20—24 nm and dispersion factors of <10% were successfully prepared.

Key words: microreactor, mixing, nanoparticle, continuous synthesis, flow chemistry

摘要：

金纳米颗粒具有特征性紫外-可见吸收光谱，在分析检测领域被广泛应用。为了突破间歇搅拌反应制备金纳米颗粒的技术局限，提出了一种连续流微反应方法。该方法在酸性条件下借助螺纹管实施HAuCl₄和Na₃Ct水溶液的快速均匀混合，引入惰性溶剂避免颗粒在反应器内沉积，利用膜分相装置完成油水在线相分离，实现了金纳米颗粒的连续稳定制备。探索了反应物摩尔比、浓度、停留时间、水油体积比、pH等因素对于颗粒粒径分布和吸收光谱的影响规律，成功制备了平均粒径20~24 nm、分散因子小于10%的窄分布金纳米颗粒。

关键词: 微反应器, 混合, 纳米粒子, 连续合成, 流动化学

CLC Number:

TQ 025.5

DONG Xiaorui, WANG Kai, LUO Guangsheng. Microreaction continuous synthesis of gold nanoparticles[J]. CIESC Journal, 2021, 72(7): 3823-3831.

董晓锐, 王凯, 骆广生. 金纳米颗粒的微反应连续合成[J]. 化工学报, 2021, 72(7): 3823-3831.

Figures/Tables 9

Fig.1 Experimental platform for the microreaction continuous synthesis of gold nanoparticles

Fig.2 Effect of Na3Ct/ HAuCl4 molar ratio on the characteristic absorption peak of Au particles and the TEM images of narrow-distributed Au particles

Table 1 pH of the reaction system and particle size distribution results

$n N a 3 C t$ / $n H A u C l 4$	pH (25℃)	Q_total=400 μl·min^-1		Q_total=800 μl·min^-1
$n N a 3 C t$ / $n H A u C l 4$	pH (25℃)	d₅₀ / nm	PDI/%	d₅₀/nm	PDI/%
1.5	4.8	27.3	34.8	28.2	31.1
2.0	5.2	28.4	23.2	28	23.4
2.5	5.6	25.3	10.7	25	12.7
3.0	5.8	23.7	7.7	23	5.9
3.5	6.2	24.2	7.3	22.9	6.5

Table 1 pH of the reaction system and particle size distribution results

$n N a 3 C t$ / $n H A u C l 4$	pH (25℃)	Q_total=400 μl·min^-1		Q_total=800 μl·min^-1
$n N a 3 C t$ / $n H A u C l 4$	pH (25℃)	d₅₀ / nm	PDI/%	d₅₀/nm	PDI/%
1.5	4.8	27.3	34.8	28.2	31.1
2.0	5.2	28.4	23.2	28	23.4
2.5	5.6	25.3	10.7	25	12.7
3.0	5.8	23.7	7.7	23	5.9
3.5	6.2	24.2	7.3	22.9	6.5

Fig.3 Effect of HAuCl4 and Na3Ct concentrations on the characteristic absorption peak of Au particles

Table 2 Particle size distribution in experiments with different reactant concentrations

$C H A u C l 4$ /(mmol·L^-1)	pH (25℃)	Q_total=400 μl·min^-1
$C H A u C l 4$ /(mmol·L^-1)	pH (25℃)	d₅₀ / nm	PDI/%
0.5	6.2	23.2	7.3
1.0	5.8	21.9	10.1
2.5	5.5	24.7	29.0
5.0	5.3	26.2	34.1

Table 2 Particle size distribution in experiments with different reactant concentrations

$C H A u C l 4$ /(mmol·L^-1)	pH (25℃)	Q_total=400 μl·min^-1
$C H A u C l 4$ /(mmol·L^-1)	pH (25℃)	d₅₀ / nm	PDI/%
0.5	6.2	23.2	7.3
1.0	5.8	21.9	10.1
2.5	5.5	24.7	29.0
5.0	5.3	26.2	34.1

Fig.4 Continuous microreaction synthesis experiment in single-phase flow system

Fig.5 Comparison of absorption spectra of representative product particles of single-phase and two-phase reactions

Fig.6 The influences of different reaction conditions on the characteristic absorption peaks of Au nanoparticles

Fig.7 TEM images of representative product particles

References 39

1	Daniel M C, Astruc D. Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology[J]. Chemical Reviews, 2004, 104(1): 293-346.
2	Al-Johani H, Abou-Hamad E, Jedidi A, et al. The structure and binding mode of citrate in the stabilization of gold nanoparticles[J]. Nature Chemistry, 2017, 9(9): 890-895.
3	Lohse S E, Eller J R, Sivapalan S T, et al. A simple millifluidic benchtop reactor system for the high-throughput synthesis and functionalization of gold nanoparticles with different sizes and shapes[J]. ACS Nano, 2013, 7(5): 4135-4150.
4	Dasog M, Hou W B, Scott R W J. Controlled growth and catalytic activity of gold monolayer protected clusters in presence of borohydride salts[J]. Chemical Communications, 2011, 47(30): 8569.
5	Zhang Y L, McKelvie I D, Cattrall R W, et al. Colorimetric detection based on localised surface plasmon resonance of gold nanoparticles: merits, inherent shortcomings and future prospects[J]. Talanta, 2016, 152: 410-422.
6	Boleininger J, Kurz A, Reuss V, et al. Microfluidic continuous flow synthesis of rod-shaped gold and silver nanocrystals[J]. Physical Chemistry Chemical Physics, 2006, 8(33): 3824-3827.
7	Du H, Chen R Y, Du J J, et al. Gold nanoparticle-based colorimetric recognition of creatinine with good selectivity and sensitivity[J]. Industrial & Engineering Chemistry Research, 2016, 55(48): 12334-12340.
8	Wang Y, Zeiri O, Raula M, et al. Host-guest chemistry with water-soluble gold nanoparticle supraspheres[J]. Nature Nanotechnology, 2017, 12(2): 170-176.
9	Li X K, Wang J E, Sun L L, et al. Gold nanoparticle-based colorimetric assay for selective detection of aluminium cation on living cellular surfaces[J]. Chemical Communications, 2010, 46(6): 988-990.
10	Yuan Z Q, Hu C C, Chang H T, et al. Gold nanoparticles as sensitive optical probes[J]. The Analyst, 2016, 141(5): 1611-1626.
11	Yue G Z, Su S, Li N, et al. Gold nanoparticles as sensors in the colorimetric and fluorescence detection of chemical warfare agents[J]. Coordination Chemistry Reviews, 2016, 311: 75-84.
12	Pacławski K, Streszewski B, Jaworski W, et al. Gold nanoparticles formation via gold(Ⅲ) chloride complex ions reduction with glucose in the batch and in the flow microreactor systems[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2012, 413: 208-215.
13	Sebastián V, Lee S, Zhou C, et al. One-step continuous synthesis of biocompatible gold nanorods for optical coherence tomography[J]. Chemical Communications, 2012, 48(53): 6654-6656.
14	Huang H, du Toit H, Ben-Jaber S, et al. Rapid synthesis of gold nanoparticles with carbon monoxide in a microfluidic segmented flow system[J]. Reaction Chemistry & Engineering, 2019, 4(5): 884-890.
15	Azubel M, Kornberg R D. Synthesis of water-soluble, thiolate-protected gold nanoparticles uniform in size[J]. Nano Letters, 2016, 16(5): 3348-3351.
16	Turkevich J, Stevenson P C, Hillier J. A study of the nucleation and growth processes in the synthesis of colloidal gold[J]. Discussions of the Faraday Society, 1951, 11: 55.
17	Bandulasena M V, Vladisavljević G T, Odunmbaku O G, et al. Continuous synthesis of PVP stabilized biocompatible gold nanoparticles with a controlled size using a 3D glass capillary microfluidic device[J]. Chemical Engineering Science, 2017, 171: 233-243.
18	Ji X H, Song X N, Li J, et al. Size control of gold nanocrystals in citrate reduction: the third role of citrate[J]. Journal of the American Chemical Society, 2007, 129(45): 13939-13948.
19	Jia L F, He T, Li Z P, et al. Monolayer-protected gold nanoparticle surface-bound catalysts: preparation and application[J]. Chinese Journal of Catalysis, 2010, 31(11/12): 1307-1315.
20	Li X M, Paraschiv V, Huskens J, et al. Sulfonic acid-functionalized gold nanoparticles: a colloid-bound catalyst for soft lithographic application on self-assembled monolayers[J]. Journal of the American Chemical Society, 2003, 125(14): 4279-4284.
21	Lévy R, Thanh N T K, Doty R C, et al. Rational and combinatorial design of peptide capping ligands for gold nanoparticles[J]. Journal of the American Chemical Society, 2004, 126(32): 10076-10084.
22	Jung Y L, Park J H, Kim M I, et al. Label-free colorimetric detection of biological thiols based on target-triggered inhibition of photoinduced formation of AuNPs[J]. Nanotechnology, 2016, 27(5): 055501.
23	Llevot A, Astruc D. Applications of vectorized gold nanoparticles to the diagnosis and therapy of cancer[J]. Chemical Society Reviews, 2012, 41(1): 242-257.
24	Pan L J, Tu J W, Ma H T, et al. Controllable synthesis of nanocrystals in droplet reactors[J]. Lab on a Chip, 2018, 18(1): 41-56.
25	Niu G D, Ruditskiy A, Vara M, et al. Toward continuous and scalable production of colloidal nanocrystals by switching from batch to droplet reactors[J]. Chemical Society Reviews, 2015, 44(16): 5806-5820.
26	Sui J S, Yan J Y, Liu D, et al. Continuous synthesis of nanocrystals via flow chemistry technology[J]. Small, 2020, 16(15): 1902828.
27	Uson L, Sebastian V, Arruebo M, et al. Continuous microfluidic synthesis and functionalization of gold nanorods[J]. Chemical Engineering Journal, 2016, 285: 286-292.
28	Sebastian Cabeza V, Kuhn S, Kulkarni A A, et al. Size-controlled flow synthesis of gold nanoparticles using a segmented flow microfluidic platform[J]. Langmuir, 2012, 28(17): 7007-7013.
29	Du L, Wang Y J, Ren Z Q, et al. Preparation of Au nanocolloids by in situ dispersion and their applications in surface-enhanced Raman scattering (SERS) films[J]. Industrial & Engineering Chemistry Research, 2016, 55(24): 6783-6791.
30	Wagner J, Köhler J M. Continuous synthesis of gold nanoparticles in a microreactor[J]. Nano Letters, 2005, 5(4): 685-691.
31	Ftouni J, Penhoat M, Addad A, et al. Highly controlled synthesis of nanometric gold particles by citrate reduction using the short mixing, heating and quenching times achievable in a microfluidic device[J]. Nanoscale, 2012, 4(15): 4450-4454.
32	Baber R, Mazzei L, Thanh N T K, et al. An engineering approach to synthesis of gold and silver nanoparticles by controlling hydrodynamics and mixing based on a coaxial flow reactor[J]. Nanoscale, 2017, 9(37): 14149-14161.
33	Huang H, Toit H D, Besenhard M O, et al. Continuous flow synthesis of ultrasmall gold nanoparticles in a microreactor using trisodium citrate and their SERS performance[J]. Chemical Engineering Science, 2018, 189: 422-430.
34	Bayazit M K, Yue J, Cao E H, et al. Controllable synthesis of gold nanoparticles in aqueous solution by microwave assisted flow chemistry[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(12): 6435-6442.
35	du Toit H, MacDonald T J, Huang H, et al. Continuous flow synthesis of citrate capped gold nanoparticles using UV induced nucleation[J]. RSC Advances, 2017, 7(16): 9632-9638.
36	Wang K, Zhang H M, Shen Y, et al. Thermoformed fluoropolymer tubing for in-line mixing[J]. Reaction Chemistry & Engineering, 2018, 3(5): 707-713.
37	Adamo A, Heider P L, Weeranoppanant N, et al. Membrane-based, liquid-liquid separator with integrated pressure control[J]. Industrial & Engineering Chemistry Research, 2013, 52(31): 10802-10808.
38	Song J, Zhang S L, Wang K, et al. Synthesis of million molecular weight polyacrylamide with droplet flow microreactors[J]. Journal of the Taiwan Institute of Chemical Engineers, 2019, 98: 78-84.
39	Wang K, Luo G S. Microflow extraction: a review of recent development[J]. Chemical Engineering Science, 2017, 169: 18-33.

[1]	Xianheng YI, Wu ZHOU, Xiaoshu CAI, Tianyi CAI. Measurable range of nanoparticle concentration using optical fiber backward dynamic light scattering [J]. CIESC Journal, 2023, 74(8): 3320-3328.
[2]	Rubin ZENG, Zhongjie SHEN, Qinfeng LIANG, Jianliang XU, Zhenghua DAI, Haifeng LIU. Study of the sintering mechanism of Fe₂O₃ nanoparticles based on molecular dynamics simulation [J]. CIESC Journal, 2023, 74(8): 3353-3365.
[3]	Erqi WANG, Shuzhou PENG, Zhen YANG, Yuanyuan DUAN. Evaluation of vapor-liquid equilibrium models for mixtures containing HFOs [J]. CIESC Journal, 2023, 74(8): 3216-3225.
[4]	Kexin HUANG, Tong LI, Anqi LI, Mei LIN. Mode decomposition of flow field in T-junction with rotating impeller [J]. CIESC Journal, 2023, 74(7): 2848-2857.
[5]	Yong LI, Jiaqi GAO, Chao DU, Yali ZHAO, Boqiong LI, Qianqian SHEN, Husheng JIA, Jinbo XUE. Construction of Ni@C@TiO₂ core-shell dual-heterojunctions for advanced photo-thermal catalytic hydrogen generation [J]. CIESC Journal, 2023, 74(6): 2458-2467.
[6]	Juhui CHEN, Qian ZHANG, Lingfeng SHU, Dan LI, Xin XU, Xiaogang LIU, Chenxi ZHAO, Xifeng CAO. Study on flow characteristics of nanoparticles in a rotating fluidized bed based on DEM method [J]. CIESC Journal, 2023, 74(6): 2374-2381.
[7]	Jiawei FU, Shuaishuai CHEN, Kailun FANG, Xin JIANG. Advantage of microreactor on the synthesis of high-activity Cu-Mn catalyst by co-precipitation [J]. CIESC Journal, 2023, 74(2): 776-783.
[8]	Xingyu YANG, You MA, Chunying ZHU, Taotao FU, Youguang MA. Study on liquid-liquid distribution in comb parallel microchannels [J]. CIESC Journal, 2023, 74(2): 698-706.
[9]	Chenghao ZHANG, Jing LUO, Jisong ZHANG. Advances in continuous aerobic oxidation based on nitroxyl radical catalyst in microreactors [J]. CIESC Journal, 2023, 74(2): 511-524.
[10]	Mengbo ZHANG, Linjin LOU, Yirong FENG, Yuting ZHENG, Haomiao ZHANG, Jingdai WANG, Yongrong YANG. Research progress on synthesis of alkylaluminoxanes [J]. CIESC Journal, 2023, 74(2): 525-534.
[11]	Yu XIE, Min ZHANG, Weiguo HU, Yujun WANG, Guangsheng LUO. Study on efficient dissolution of D-7-ACA using membrane dispersion microreactor [J]. CIESC Journal, 2023, 74(2): 748-755.
[12]	Xintong HUANG, Yuhao GENG, Hengyuan LIU, Zhuo CHEN, Jianhong XU. Research progress on new functional nanoparticles prepared by microfluidic technology [J]. CIESC Journal, 2023, 74(1): 355-364.
[13]	Guojuan QU, Tao JIANG, Tao LIU, Xiang MA. Modulating luminescent behaviors of Au nanoclusters via supramolecular strategies [J]. CIESC Journal, 2023, 74(1): 397-407.
[14]	Wei ZHANG, Haoyang LI, Chungang XU, Xiaosen LI. Research progress on the microscopic mechanism and analytical methods of gas hydrate formation [J]. CIESC Journal, 2022, 73(9): 3815-3827.
[15]	Feng LIU, Quan WANG, Panyu WU, Guo WEI, Xiang HE. Effect of internal phase particle size on vibration resistance of on-site mixed emulsion explosive matrix [J]. CIESC Journal, 2022, 73(9): 4217-4225.