金纳米颗粒的微反应连续合成

doi:10.11949/0438-1157.20210014

摘要/Abstract

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

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

中图分类号:

TQ 025.5

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.

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

图/表 9

图1 金纳米颗粒微反应连续合成实验平台

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

图2 Na3Ct/ HAuCl4摩尔比对金颗粒特征吸收峰的影响和窄分布金颗粒的透射电镜照片

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

表1 反应体系pH和颗粒粒径分布结果

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

表1 反应体系pH和颗粒粒径分布结果

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

图3 HAuCl4和Na3Ct浓度对金颗粒特征吸收峰的影响(实验条件：QHAuCl4 = QNa3Ct = 200 μl·min-1，τ = 9.8 min，nNa3Ct/nHAuCl4 = 3.5)

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

表2 不同反应物浓度实验的颗粒粒径分布

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

表2 不同反应物浓度实验的颗粒粒径分布

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

图4 单相流体系连续微反应合成实验(实验条件：QHAuCl4 = QNa3Ct = 400 μl·min-1，CHAuCl4 = 0.5 mmol·L-1，nNa3Ct/nHAuCl4 = 3.0，τ = 4.9 min)

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

图5 单相与两相反应代表性产物颗粒的吸收光谱对比（实验条件：CHAuCl4 = 0.5 mmol·L-1，nNa3Ct/nHAuCl4 = 3.0，τ = 4.9 min，单相反应QHAuCl4 = QNa3Ct = 400 μl·min-1；两相反应QHAuCl4 = QNa3Ct= 300 μl·min-1，?QC10H22 = 200 μl·min-1）

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

图6 不同反应条件对金纳米颗粒特征吸收峰的影响

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

图7 代表性产物颗粒的透射电镜照片

Fig.7 TEM images of representative product particles

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