非线性光学晶体3BiCl3.7SC(NH2)2的合成及其转化过程

doi:10.12034/j.issn.1009-606X.219125

过程工程学报 ›› 2019, Vol. 19 ›› Issue (5): 1030-1036.DOI: 10.12034/j.issn.1009-606X.219125

非线性光学晶体3BiCl₃.7SC(NH₂)₂的合成及其转化过程

白云鹤¹，裴铁柱¹，张良¹，张宁²，马得佳¹，尹秋响^1,3,4，谢闯^1,3,4*

1. 天津大学化工学院，天津 300072 2. 山东益丰生化环保股份有限公司，山东滨州 256500 3. 天津大学国家工业结晶工程技术研究中心，天津 300072 4. 天津化学化工协同创新中心，天津 300072

收稿日期:2019-01-22 修回日期:2019-03-14 出版日期:2019-10-22 发布日期:2019-10-22
通讯作者: 谢闯 acxie@tju.edu.cn

Synthesis and crystal conversion processes of nonlinear optical crystal 3BiCl₃.7SC(NH₂)₂

Yunhe BAI¹, Tiezhu PEI¹, Liang ZHANG¹, Ning ZHANG², Dejia MA¹, Qiuxiang YIN^1,3,4, Chuang XIE^1,3,4*

1. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China 2. Shandong Efirm Biochemistry and Environmental Protection Co., Ltd., Binzhou, Shandong 256500, China 3. National Engineering Research Center of Industrial Crystallization Technology, Tianjin University, Tianjin 300072, China 4. National Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China

Received:2019-01-22 Revised:2019-03-14 Online:2019-10-22 Published:2019-10-22

摘要/Abstract

摘要： 针对金属有机配合物非线性光学晶体3BiCl3?7SC(NH2)2 (DCBPB)合成过程中伴生BiCl3?3SC(NH2)2 (β-BTC)的问题，以硫脲与氯化铋为原料，在甲酸?水体系中研究了溶剂配比、反应温度、反应物配比等因素对DCBPB纯度的影响，对反应条件进行了优化，并基于XRD特征峰面积标准曲线法研究了β-BTC与DCBPB之间的转化过程。结果表明，甲酸抑制氯化铋水解且选择性生成DCBPB，氯化铋与硫脲摩尔配比大于1:3时可选择性生成DCBPB。合成过程先生成β-BTC，再由β-BTC转化为DCBPB，甲酸?水体系中氯化铋水解发生在β-BTC生成过程中，且不可避免，导致基于氯化铋直接合成只能获得最高含量为89.91wt%的DCBPB晶体。β-BTC向DCBPB转化率极高且无水解，可获得DCBPB含量大于98wt%的晶体。

关键词: 非线性光学晶体, 氯化铋, 硫脲, 金属有机配合物

Abstract: Semi-organic nonlinear optical (NLO) materials attract growing attention due to its balanced properties and potential applications in various fields. Thiourea-coordinating metal-organic NLO material is one of the famous semi-organic systems. In our previous work, new 3BiCl3?7SC(NH2)2 (DCBPB) NLO crystals which exhibits excellent fluorescence properties and better optical transmission properties than other reported complexes of thiourea and bismuth(Ⅲ) chloride were synthesized. However, during the synthesis of DCBPB, the coexistence of BiCl3?3SC(NH2)2 (β-BTC) was found to be difficult to avoid. In order to improve the quality of the synthesized DCBPB crystals, the effects of solvent ratio, reaction temperature, and reagent ratio on the purity of DCBPB using thiourea and bismuth(III) chloride as reagents in formic acid?water solvent system were investigated. The results showed that formic acid not only depressed the hydrolysis of bismuth(III) chloride, but also improved the selectivity of DCBPB. A high selectivity of DCBPB could be achieved when the molar ratio of bismuth(III) chloride to thiourea was larger than 1:3. The reaction temperature shouldn′t exceed 50℃ to avoid side reactions. The optimization of the synthesis indicated that the hydrolysis of bismuth(III) chloride was inevitable and the highest purity of DCBPB was 89.91wt%. A two-step mechanism of DCBPB synthesis was found which included the formation of β-BTC and the conversion of β-BTC to DCBPB. Furthermore, the conversion between β-BTC and DCBPB in formic acid aqueous solution was investigated based on XRD characteristic peak area correlation. The results showed that β-BTC almost completely converted to DCBPB and no hydrolysis of bismuth(III) was detected during the conversion, a high purity of more than 98wt% was achieved via conversion of β-BTC to DCBPB in formic acid.

Key words: NLO, Bismuth chloride, Thiourea, Organometallic Coordination Complex

白云鹤裴铁柱张良张宁马得佳尹秋响谢闯. 非线性光学晶体3BiCl₃.7SC(NH₂)₂的合成及其转化过程[J]. 过程工程学报, 2019, 19(5): 1030-1036.

Yunhe BAI Tiezhu PEI Liang ZHANG Ning ZHANG Dejia MA Qiuxiang YIN Chuang XIE. Synthesis and crystal conversion processes of nonlinear optical crystal 3BiCl₃.7SC(NH₂)₂[J]. Chin. J. Process Eng., 2019, 19(5): 1030-1036.

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非线性光学晶体3BiCl₃.7SC(NH₂)₂的合成及其转化过程

Synthesis and crystal conversion processes of nonlinear optical crystal 3BiCl₃.7SC(NH₂)₂

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