邻苯二甲酸氢钾在制备碱式硫酸镁纳米线过程中的机理研究

doi:10.15541/jim20190020

无机材料学报 ›› 2019, Vol. 34 ›› Issue (11): 1181-1186.DOI: 10.15541/jim20190020 CSTR: 32189.14.10.15541/jim20190020

邻苯二甲酸氢钾在制备碱式硫酸镁纳米线过程中的机理研究

肖剑飞^1,^2,³,乃学瑛^1,²(),苟生莲^1,³,叶俊伟⁴,董亚萍^1,²,李武¹

^1. 中国科学院青海盐湖研究所, 盐湖资源综合高效利用重点实验室, 西宁810008
^2. 青海省盐湖资源综合利用工程技术中心, 西宁810008
^3. 中国科学院大学, 北京100049
^4. 大连理工大学化工学院, 大连116024

收稿日期:2019-01-09 修回日期:2019-03-26 出版日期:2019-11-20 网络出版日期:2019-05-22
作者简介:肖剑飞(1990-), 男, 硕士研究生. E-mail: xiaojianfei166@sina.com
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(U1607101)

Mechanism of Potassium Acid Phthalate in Stimulating Formation of Magnesium Hydroxide Sulfate Hydrate Nanowires

XIAO Jian-Fei^1,^2,³,NAI Xue-Ying^1,²(),GOU Sheng-Lian^1,³,YE Jun-Wei⁴,DONG Ya-Ping^1,²,LI Wu¹

^1. Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, China
^2. Qinghai Engineering and Technology Research Center of Comprehensive Utilization of Salt Lakes Resources , Xining 810008, China
^3. University of Chinese Academy of Sciences, Beijing 100049, China
^4. School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China

Received:2019-01-09 Revised:2019-03-26 Published:2019-11-20 Online:2019-05-22
Supported by:
Qinghai Provincial Science and Technology Department Project(2019-ZJ-7029);NSFC-Qaidam Salt Lake Chemical Science Research United Fund(U1607101)

摘要/Abstract

摘要：

以邻苯二甲酸氢钾(KHpht)作为络合剂, 采用水热法制备出碱式硫酸镁(MOS)纳米线。通过电位滴定法分析了体系中pht ^2-与Mg ²⁺的络合作用, 并采用X射线光电子能谱(XPS)、傅里叶变换红外光谱仪(FT-IR)和透射电子显微镜(TEM)等表征手段对pht ^2-的吸附作用进行了研究。结果表明: pht ^2-与Mg ²⁺发生络合反应, 使得体系中游离的Mg ²⁺浓度大幅降低, 过饱和度也随之降低; MOS晶体表面存在着Mg-pht的化学键合作用, 由于各晶面的晶格排列方式不同, 使得pht ^2-在MOS晶体侧面吸附比例大于纵向生长面, 从而促进了高长径比MOS纳米线的生长。

关键词: 碱式硫酸镁, 纳米线, 邻苯二甲酸氢钾, 络合作用

Abstract:

Magnesium hydroxide sulfate hydrate (MOS) nanowires were prepared with hydrothermal method by using potassium acid phthalate (KHpht) as the complexant. Complexation formed by pht ^2- and Mg ²⁺ in this preparation system was analyzed by potentiometric titration. The effect of pht ^2- adsorption on MOS nanowires was investigated by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectrometer (FT-IR) and transmission electron microscopy (TEM). These results show that pht ^2- complexes with Mg ²⁺ in the reaction system substantially decreases free Mg ²⁺ concentration and solution supersaturation. Chemical bonding between Mg ²⁺ and pht ^2- exists on the surface of MOS crystal. Owing to the different configuration of the crystal lattice, pht ^2- adsorption on the lateral growth plane is more preferential than that on the axial growth plane, resulting in the formation with ratio of MOS nanowires.

Key words: magnesium hydroxide sulfate hydrate, nanowire, potassium acid phthalate, complexation

中图分类号:

O614

肖剑飞, 乃学瑛, 苟生莲, 叶俊伟, 董亚萍, 李武. 邻苯二甲酸氢钾在制备碱式硫酸镁纳米线过程中的机理研究[J]. 无机材料学报, 2019, 34(11): 1181-1186.

XIAO Jian-Fei, NAI Xue-Ying, GOU Sheng-Lian, YE Jun-Wei, DONG Ya-Ping, LI Wu. Mechanism of Potassium Acid Phthalate in Stimulating Formation of Magnesium Hydroxide Sulfate Hydrate Nanowires[J]. Journal of Inorganic Materials, 2019, 34(11): 1181-1186.

图/表 9

图1 MOS纳米线和MOS晶须的XRD图谱

Fig. 1 XRD patterns of MOS whisker and nanowire

图2 MOS晶须(a, c)和MOS纳米线(b, d)的SEM照片

Fig. 2 SEM images of MOS whiskers (a, c) and MOS nanowires (b, d)

图3 NaOH标液滴定KHpht和MgSO4-KHpht混合溶液的滴定曲线

Fig. 3 Titration curves of KHpht and MgSO4-KHpht titrated with NaOH solution

图4 温度为30 ℃时KHpht的电离常数(a)和Mgpht的络合稳定常数(b)

Fig. 4 Ionization constant (a) and complexation stability constant (b) of Mgpht at 30 ℃

图5 30 ℃时料浆中Mg2+浓度随pH的变化(a)及随pht2-/Mgpht的变化(b)

Fig. 5 Concentration of Mg2+ changed with pH (a) and pht2-/Mgpht (b) in slurry at 30 ℃

图6 MOS纳米线和MOS晶须的FT-IR谱图

Fig. 6 FT-IR spectra of MOS nanowires and MOS whiskers

图7 MOS纳米线和MOS晶须的XPS分析谱图

Fig. 7 XPS spectra of MOS nanowires and MOS whiskers (a) Full-scan; (b) Mg1s spectrum; (c) O1s spectrum; (d) S2p spectrum

图8 MOS纳米线的(a)TEM, (b)HRTEM和(c)电子衍射SADE照片

Fig. 8 TEM (a), HRTEM (b) images and SADE patterns (c) of MOS nanowires

图9 MOS纳米线晶体生长示意图

Fig. 9 Growth schematic of the MOS nanowire

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邻苯二甲酸氢钾在制备碱式硫酸镁纳米线过程中的机理研究

Mechanism of Potassium Acid Phthalate in Stimulating Formation of Magnesium Hydroxide Sulfate Hydrate Nanowires

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