以Cu(Ac)2-Zn(Ac)2溶液为水相的W/O微液滴尺度的有效调控

doi:10.16085/j.issn.1000-6613.2023-1408

摘要/Abstract

摘要：

微乳液常被用来制备纳米材料，而对微液滴尺寸的有效调控对于纳米材料制备至关重要。本文研究了在Triton X-100微乳液体系中，以Cu(Ac)₂-Zn(Ac)₂电解质水溶液为水相时，微液滴尺度的变化情况。实验结果表明：在4~12nm的范围内，可以通过改变微乳液中水含量和电解质溶液种类来调节液滴的大小。在一定范围内，无论是水体系还是电解质溶液体系中，微液滴的平均粒径都随着水含量的增加而增大。电解质溶液中金属离子与水分子之间的作用力不同，导致微液滴的粒径分布呈现出不同的变化。需要注意的是，电解质的加入对于微乳液的外观和稳定性没有影响。在以链状烷烃作为油相形成的Cu(Ac)₂-Zn(Ac)₂电解质微乳液体系中，微液滴的粒径分布更加均匀。最后，本文采用所述的微乳液方法成功制备了CuO-ZnO纳米颗粒。本研究结果对于实现微乳液液滴尺度的可控调节和纳米材料的制备具有重要意义。

关键词: 表面活性剂, 电解质, 微乳液, 微液滴

Abstract:

Microemulsions are commonly used for the preparation of nanomaterials. The controllable regulation of the size of microdroplets is crucial to the preparation of nanomaterials. When Cu(Ac)₂-Zn(Ac)₂ electrolyte aqueous solution was used as the aqueous phase, the variations of microdroplets sizes of W/O microemulsion system of Triton X-100 were studied systematically. The experimental results showed that the droplet size could be regulated in the range of 4—12nm by changing the water content in the microemulsion and the type of electrolyte solution. And within a certain range, the average size of microdroplets increased with the increase of water content in the system. The different forces between metal ions and water molecules in the electrolyte solution also led to different changes in the particle size distribution of the droplets. The addition of electrolyte did not change the appearance and stability of the microemulsion. In the microemulsion systems with chain alkanes as oil phase, the size distribution of microdroplets with Cu(Ac)₂-Zn(Ac)₂ electrolyte aqueous solution as water phase was more uniform. CuO-ZnO nanoparticles were successfully prepared by the proposed microemulsion method. The results were useful to provide a guide for the controllable regulation of microdroplet size and the preparation of nanomaterials.

Key words: surfactants, electrolytes, microemulsion, microdroplet

中图分类号:

TQ311

李浩然, 王岩, 张涛, 吕莉, 唐文翔, 唐盛伟. 以Cu(Ac)₂-Zn(Ac)₂溶液为水相的W/O微液滴尺度的有效调控[J]. 化工进展, 2024, 43(9): 5168-5176.

LI Haoran, WANG Yan, ZHANG Tao, LYU Li, TANG Wenxiang, TANG Shengwei. Controllable regulation of microdroplets size in W/O microemulsion with Cu(Ac)₂-Zn(Ac)₂ solution as aqueous phase[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5168-5176.

图/表 14

图1 微乳液法制备纳米CuO-ZnO实验流程

图2 298.15K条件下Triton X-100/正己醇-环己烷-水- 0.01mol/L Cu(Ac)2-0.01mol/L Zn(Ac)2体系中微乳液液滴粒径

图3 298.15K条件下Triton X-100/正己醇-环己烷-水溶液体系中不同种类电解质溶液对微乳液液滴尺度的影响（Triton X-100∶正己醇=1，乳化剂∶油=4∶6）

图4 298.15K条件下Triton X-100/正己醇-环己烷-水溶液体系中微乳液液滴尺度的稳定性（Triton X-100∶正己醇=1，乳化剂∶油=4∶6，水质量分数为5%）

图5 298.15K条件下微乳液相态变化

图6 水体系与电解质溶液体系中不同助表面活性剂对微液滴尺度分布影响

表1 不同助表面活性剂条件下，水体系与电解质溶液体系中微液滴粒径

醇	体系	平均粒径/nm	D₁₀/nm	D₅₀/nm	D₉₀/nm
正丙醇	水	5.03	2.26	3.77	6.30
正丙醇	盐	6.91	2.56	4.64	8.39
正丁醇	水	6.18	2.76	4.62	7.75
正丁醇	盐	7.86	2.66	5.09	9.76
正戊醇	水	8.02	2.62	4.73	8.54
正戊醇	盐	10.50	3.65	6.90	13.07
正己醇	水	9.06	4.57	7.17	11.25
正己醇	盐	11.97	5.93	9.4	14.86

图7 水体系与电解质溶液体系中油种类对微液滴尺度分布的影响

表2 不同烷烃条件下，水体系与电解质溶液体系中微液滴粒径

烷烃	体系	平均粒径/nm	D_10/nm	D₅₀/nm	D₉₀/nm
环己烷	水	9.06	4.57	7.17	11.25
环己烷	盐	11.97	5.93	9.40	14.86
正己烷	水	5.94	2.40	4.23	7.42
正己烷	盐	6.81	3.37	5.34	8.50
正庚烷	水	9.63	3.52	6.52	13.01
正庚烷	盐	11.31	4.95	7.68	11.93
正辛烷	水	10.85	3.85	7.22	13.48
正辛烷	盐	12.82	5.60	8.70	13.47

图8 水体系与电解质溶液体系中Km对微液滴尺度分布影响

表3 不同Km条件下水体系与电解质溶液体系中微液滴粒径

K_m	体系	平均粒径/nm	D₁₀/nm	D₅₀/nm	D₉₀/nm
1∶1	水	9.06	4.57	7.17	11.25
1∶1	盐	11.97	5.93	9.40	14.86
1∶2	水	6.48	1.72	3.60	7.79
1∶2	盐	10.58	3.06	6.28	12.92
2∶1	水	6.07	2.49	4.35	7.61
2∶1	盐	8.98	3.74	6.49	11.25

图9 前体的TG曲线

图10 微乳液法制得的纳米CuO-ZnO样品的XRD谱图

图11 煅烧产物粒径分布

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以Cu(Ac)₂-Zn(Ac)₂溶液为水相的W/O微液滴尺度的有效调控

Controllable regulation of microdroplets size in W/O microemulsion with Cu(Ac)₂-Zn(Ac)₂ solution as aqueous phase

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