水热生长碱式硫酸镁纳米线结晶动力学研究

doi:10.11949/0438-1157.20220219

化工学报 ›› 2022, Vol. 73 ›› Issue (7): 3038-3044.DOI: 10.11949/0438-1157.20220219

• 催化、动力学与反应器 • 上一篇下一篇

水热生长碱式硫酸镁纳米线结晶动力学研究

乃学瑛^1,²(),吴鹏^1,^2,³,程远^1,^2,³,肖剑飞^1,^2,³,刘鑫^1,²,董亚萍^1,²

^1.中国科学院青海盐湖研究所，中国科学院盐湖资源综合高效利用重点实验室，青海西宁 810008
^2.青海盐湖资源综合利用技术研究开发中心，青海西宁 810008
^3.中国科学院大学，北京 100049

收稿日期:2022-02-23 修回日期:2022-05-30 出版日期:2022-07-05 发布日期:2022-08-01
通讯作者: 乃学瑛
作者简介:乃学瑛（1973—），女，博士，副研究员， naixy@isl.ac.cn
基金资助:
青海省科技厅项目(2019-ZJ-7029);国家自然科学基金柴达木盐湖化工科学研究联合基金项目(U1607101)

Study on hydrothermal crystallization kinetics of magnesium oxysulfate nanowires

Xueying NAI^1,²(),Peng WU^1,^2,³,Yuan CHENG^1,^2,³,Jianfei XIAO^1,^2,³,Xin LIU^1,²,Yaping DONG^1,²

^1.Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, Qinghai, China
^2.Qinghai Technology Research and Development Center of Comprehensive Utilization of Salt Lake Resources, Xining 810008, Qinghai, China
^3.University of Chinese Academy of Sciences, Beijing 100049, China

Received:2022-02-23 Revised:2022-05-30 Online:2022-07-05 Published:2022-08-01
Contact: Xueying NAI

摘要/Abstract

摘要：

以硫酸镁和氢氧化钠为原料，邻苯二甲酸氢钾为络合剂，采用络合-水热法制备了碱式硫酸镁纳米线；采用宏观动力学方法结合微观结构分析，进行碱式硫酸镁结晶机理研究。通过分析Mg浓度与时间的变化关系曲线，建立结晶动力学方程；然后根据晶体缺陷分析碱式硫酸镁纳米线表面成核机制。实验结果表明：碱式硫酸镁纳米线在140和160℃结晶机理为多核控制表面生长；在180和200℃时结晶机理发生了变化，转变为线性控制表面生长；碱式硫酸镁纳米线的晶格中存在着较多的刃型位错与螺型位错，可以促进其表面成核、快速生长。

关键词: 碱式硫酸镁, 纳米线, 水热, 结晶, 动力学, 成核

Abstract:

Using magnesium sulfate and sodium hydroxide as raw materials and potassium hydrogen phthalate as complexing agent, basic magnesium sulfate nanowires were prepared by complexation-hydrothermal method. The crystallization mechanism of magnesium oxysulfate (MOS) nanowire was investigated, and the crystallization kinetic equations were established by analyzing the concentration of Mg via the hydrothermal synthesis process. Then, the surface nucleation mode of the nanowire was confirmed. The results illustrated the crystallization of the nanowire was controlled by multi-core surface growth mode at 140℃ and 160℃. However, it changed to linear surface growth mode at 180℃ and 200℃. The microstructures of MOS nanowires were investigated by transmission electron microscopy. There are many edge dislocations and screw dislocations in the crystals, their effects in MOS nanowires on growth kinetics are to decrease the two-dimensional nucleation barrier and act as a self-perpetuating step sources.

Key words: magnesium oxysulfate, nanowires, hydrothermal, crystallization, kinetics, nucleation

中图分类号:

O 781

乃学瑛, 吴鹏, 程远, 肖剑飞, 刘鑫, 董亚萍. 水热生长碱式硫酸镁纳米线结晶动力学研究[J]. 化工学报, 2022, 73(7): 3038-3044.

Xueying NAI, Peng WU, Yuan CHENG, Jianfei XIAO, Xin LIU, Yaping DONG. Study on hydrothermal crystallization kinetics of magnesium oxysulfate nanowires[J]. CIESC Journal, 2022, 73(7): 3038-3044.

图/表 6

图1 不同温度下Mg浓度随反应时间变化趋势

Fig.1 Dependence of Mg concentration on reaction time at different temperatures

表1 不同温度下三种动力学模型的拟合结果

Table 1 Outcomes of three dynamic models fitting at different temperatures

动力学模型	140℃		160℃		180℃		200℃
动力学模型	R²	RSS	R²	RSS	R²	RSS	R²	RSS
MA-1	0.9819	0.0022	0.9963	0.0005	0.9421	0.0101	0.9351	0.0102
MA-2	0.8984	0.0060	0.9100	0.0086	0.9790	0.0029	0.9555	0.0058
MA-3	0.5498	0.0201	0.6151	0.0279	0.9068	0.0077	0.9176	0.0081
MA-4	0.2961	0.0326	0.3584	0.0463	0.7054	0.0191	0.8086	0.0160
MB-1	0.4596	0.4900	0.6073	0.1061	0.4346	0.4464	0.4479	0.4680
MB-2	0.4600	0.4871	0.4405	0.5617	0.4345	0.4462	0.4481	0.4689
MB-3	0.4598	0.4947	0.4409	0.5656	0.4351	0.4474	0.4481	0.4716
MB-4	0.4598	0.4947	0.4409	0.5657	0.4349	0.4500	0.4481	0.4715
MC-1	0.8715	0.0059	0.8031	0.0145	0.9979	0.0002	0.9811	0.0021
MC-2	0.4780	0.0202	0.4832	0.0329	0.8782	0.0080	0.9446	0.0043
MC-3	0.2472	0.0323	0.2736	0.0502	0.6510	0.0201	0.8026	0.0122
MC-4	0.1311	0.0418	0.1644	0.0641	0.4218	0.0330	0.6209	0.0208

图2 不同温度的水热条件下结晶动力学方程拟合曲线

Fig.2 Fitting curves of crystallization kinetics equations under hydrothermal processs at different temperatures

图3 MOS纳米线的SEM图(a)和TEM图(b)

Fig.3 SEM (a) and TEM (b) images of MOS nanowire

图4 MOS纳米线的XRD谱图

Fig.4 XRD patterns of MOS nanowire

图5 MOS纳米线透射电镜图片及其反傅里叶变换图(a) MOS纳米线TEM照片及布拉格衍射图;(b) MOS纳米线局部放大照片; (c)~(e)由衍射斑得到的三种不同晶面条纹图

Fig.5 Transmission electron microscopy and the corresponding IFFT images of MOS nanowires(a) transmission electron microscopy and bragg diffraction pattern of MOS nanowires; (b) the partial enlargement image of (a); (c)—(e) the lattice stripe of three different crystal plane group

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水热生长碱式硫酸镁纳米线结晶动力学研究

Study on hydrothermal crystallization kinetics of magnesium oxysulfate nanowires

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