微反应器策略实现γ-CuI的形貌调控

人工晶体学报 ›› 2023, Vol. 52 ›› Issue (10): 1887-1896.

微反应器策略实现γ-CuI的形貌调控

占思进¹, 游立¹, 刘飞¹, 王诗瀚^2,3, 胡国涛^2,3, 杨晓健^2,3, 张丹^2,3, 王先炜⁴

1.贵州大学化学与化工学院,贵阳 550025;
2.中低品位磷矿及共伴生资源高效利用国家重点实验室,贵阳 550025;
3.瓮福(集团)有限责任公司,贵阳 550025;
4.贵阳开磷化肥有限公司,贵阳 550025

收稿日期:2023-04-06 发布日期:2023-10-18
通信作者: 刘飞,博士,教授。E-mail:ce.feiliu@gzu.edu.cn。王诗瀚,工程师。E-mail:wsh8717@qq.com。
作者简介:占思进(1998—),男,湖南省人,硕士研究生。E-mail:457020730@qq.com
基金资助:
瓮福(集团)有限责任公司产学研合作项目(WF-001-2022-JS-00086);贵州省自然科学基金(ZKZD2023004);贵州省教育厅创新群体项目(黔教合KY字[2021]010);贵州大学实验室开放项目(SYSKF2023-008)

Microreactor Strategy for Morphology Modulation of γ-CuI

ZHAN Sijin¹, YOU Li¹, LIU Fei¹, WANG Shihan^2,3, HU Guotao^2,3, YANG Xiaojian^2,3, ZHANG Dan^2,3, WANG Xianwei⁴

1. College of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, China;
2. State Key Laboratory for Efficient Utilization of Medium and Low Grade Phosphate Ore and Associated Resources, Guiyang 550025, China;
3. Wengfu (Group) Co., Ltd., Guiyang 550025, China;
4. Guiyang Kailin Fertilizer Co., Ltd., Guiyang 550025, China

Received:2023-04-06 Published:2023-10-18

摘要/Abstract

摘要： γ-CuI较宽的能带空隙及较高的离子电导率等特点,使其在光能利用和超快闪烁材料领域有着广泛的应用。γ-CuI 的形貌往往对其结构性质有重要的影响,精准地调控其形貌有很大的意义。因此,本文采用微反应法,通过控制不同NH₃·H₂O用量、Cu源、管内反应停留时间及合成温度等因素,结合SEM、XRD和FT-IR等测试手段,对不同合成条件下制备得到的γ-CuI的晶型与形貌进行了研究。并对传统液相沉淀法和微反应法制备的γ-CuI进行了比较。结果表明,当NH₃·H₂O使用量(C_NH₃·H₂O/C_N₂H₄)为0.4、管内停留时间为10 s、反应温度为20 ℃的条件下达到90.5%的最高产率。其中,NH₃·H₂O的使用量对形貌的影响最大,当NH₃·H₂O的使用量为0.4时,合成了形貌均一的棒状γ-CuI。对比不同的铜源,除Cu(CH₃COO)₂·H₂O制备得到棒状的γ-CuI,其余Cu源均主要生成颗粒状γ-CuI。增加管内时间则有助于棒状γ-CuI的形成,但进一步增长时间会导致样品在管内损失。此外,过高的反应温度会导致棒状γ-CuI逐渐向颗粒状γ-CuI转化。

关键词: γ-CuI, N₂H₄·H₂O, 微反应器, 微流控法, 微筛孔板, 形貌调控

Abstract: Owing to its wide energy band gap, fast ionic conductivity at high temperatures, the ability to maintain a stable p-type conductivity at room temperature and poor spin-orbit splitting, γ-CuI is widely used in optical energy applications and ultrafast scintillation materials. The morphology of γ-CuI is determined by its synthesis conditions. In this paper,γ-CuI with different morphology were synthesized by microreaction method through controlling different NH₃·H₂O dosage, Cu source, in-tube reaction residence time, and temperature in the reaction. The crystalline phase and morphology of these γ-CuI were investigated by SEM, XRD and FT-IR. The γ-CuI prepared by the traditional liquid phase precipitation method was taken as a comparison. The results show that, the highest yield of 90.5% is achieved when the amount of NH₃·H₂O used (C_NH₃·H₂O/C_N₂H₄) is 0.4, the residence time in the tube is 10 s, and the reaction temperature is 20 ℃. Among them, the amount of NH₃·H₂O used (which has the greatest effect on the morphology) is 0.4, the rod-shaped γ-CuI with homogeneous morphology is synthesized. Comparing different Cu sources, except for Cu(CH₃COO)₂·H₂O that is prepared to obtain the rod-shaped γ-CuI, all the remaining Cu sources mainly produce the granular γ-CuI. Increasing the in-tube time contribute to the rod-shaped γ-CuI CuI formation, but further increase time will lead to sample loss in the tube. In addition, too high reaction temperature will cause the gradual conversion of rod γ-CuI to granular γ-CuI.

Key words: γ-CuI, N₂H₄·H₂O, microreactor, microfluidic method, microporous sieve plate, morphological control

中图分类号:

占思进, 游立, 刘飞, 王诗瀚, 胡国涛, 杨晓健, 张丹, 王先炜. 微反应器策略实现γ-CuI的形貌调控[J]. 人工晶体学报, 2023, 52(10): 1887-1896.

ZHAN Sijin, YOU Li, LIU Fei, WANG Shihan, HU Guotao, YANG Xiaojian, ZHANG Dan, WANG Xianwei. Microreactor Strategy for Morphology Modulation of γ-CuI[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2023, 52(10): 1887-1896.

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