杂化钙钛矿(HOC2H4NH3)2CuCl4的制备与表征

doi:10.15541/jim20160701

无机材料学报 ›› 2017, Vol. 32 ›› Issue (10): 1063-1067.DOI: 10.15541/jim20160701 CSTR: 32189.14.10.15541/jim20160701

杂化钙钛矿(HOC₂H₄NH₃)₂CuCl₄的制备与表征

杨志胜¹, 柯蔚芳², 王艳香¹, 黄丽群¹, 郭平春¹, 朱华³

(景德镇陶瓷大学 1. 材料科学与工程学院; 2. 陶瓷美术学院; 3. 机电学院, 景德镇333403)

收稿日期:2016-12-27 修回日期:2017-02-14 出版日期:2017-10-20 网络出版日期:2017-09-21
基金资助:
国家自然科学基金(51403090, 51462015);江西省教育厅青年自然科学基金(GJJ150897);景德镇陶瓷大学博士科研启动项目(2010);江西省高等学校大学生创新创业计划项目(2017)

Preparation and Characterization of a Novel Hybrid Perovskite (HOC₂H₄NH₃)₂CuCl₄

YANG Zhi-Sheng¹, KE Wei-Fang², WANG Yan-Xiang¹, HUANG Li-Qun¹, GUO Ping-Chun¹, ZHU Hua³

(1. Department of Materials Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333403, China; 2. Department of Ceramic Art, Jingdezhen Ceramic Institute, Jingdezhen 333403, China; 3. Department of Mechanical and Electrical Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333403, China)

Received:2016-12-27 Revised:2017-02-14 Published:2017-10-20 Online:2017-09-21
Supported by:
National Natural Science Foundation of China(51403090, 51462015);Youth Natural Science Foundation of Education Department of Jiangxi Province (GJJ150897);Doctoral Research Project of Jingdezhen Ceramic Institute(2010);Innovation and Entrepreneurship Program of College Students in Jiangxi Province (2017)

摘要/Abstract

摘要：

采用低温溶液法合成了新型层状有序的含有羟基的有机/无机杂化钙钛矿材料(HOC₂H₄NH₃)₂CuCl₄, 采用元素分析、红外光谱、紫外-可见光吸收光谱、X射线衍射和X射线吸收精细结构等手段对其结构与性能进行了表征。结果表明:该材料通过无机框架诱导有机组分有序排列, 形成了规则的层状结构, 有序性高。该杂化钙钛矿材料的分解温度为212℃, 电阻率为2.86×10⁶ Ω·cm, 比不含羟基杂化钙钛矿的电阻率低两个数量级。紫外-可见光吸收光谱显示285 nm左右有一归因于电子从Cl(3p)价带顶跃迁到Cu(4s)导带底而产生的吸收峰。X射线吸收精细结构谱图表明: 二维层状杂化钙钛矿晶体中的Cu²⁺与6个Cl^-形成八面体配位, Cu-Cl键长为0.191 nm, 层间距为1.099 nm。

null

关键词: 有机/无机杂化, 钙钛矿, 晶体结构

Abstract:

A novel organic-inorganic hybrid material containing hydroxyl, (HOC₂H₄NH₃)₂CuCl₄ with perovskite structure, was synthesized by low-temperature solution method. The structure and properties of the hybrid material were characterized by elemental analysis, IR, UV-Vis absorption spectrum, X-ray diffraction, and X-ray absorption fine structure techniques. The result reveals that the hybrid material (HOC₂H₄NH₃)₂CuCl₄ is well-ordered and in two-dimensional layered frame, and the organic component is in orderly arrangement induced by inorganic framework. The decomposition temperature of the hybrid material is about 212℃, and the resistance of the hybrid material is about 2.86×10⁶ Ω·cm, which is two orders of magnitude less than hybrid perovskite without hydroxyl. UV-Vis spectra shows that the crystal has a new absorption peak at about 285 nm which is attributed to the electronic transitions from the top of the valence band of Cl (3p) to the bottom of the conduction band of Cu (4s). XAFS result shows that Cu²⁺with six Cl^- forms octahedral coordination in the hybrid layered crystal with layer spacing of 1.099 nm, and the Cu-Cl bond length is about 0.191 nm.

Key words: organic-inorganic hybrid, perovskite, crystal structure

中图分类号:

O614

杨志胜, 柯蔚芳, 王艳香, 黄丽群, 郭平春, 朱华. 杂化钙钛矿(HOC₂H₄NH₃)₂CuCl₄的制备与表征[J]. 无机材料学报, 2017, 32(10): 1063-1067.

YANG Zhi-Sheng, KE Wei-Fang, WANG Yan-Xiang, HUANG Li-Qun, GUO Ping-Chun, ZHU Hua. Preparation and Characterization of a Novel Hybrid Perovskite (HOC₂H₄NH₃)₂CuCl₄[J]. Journal of Inorganic Materials, 2017, 32(10): 1063-1067.

图/表 9

图1 (HOC2H4NH3)2CuCl4的红外光谱图

Fig. 1 FT-IR spectrum of (HOC2H4NH3)2CuCl4

图2 (HOC2H4NH3)2CuCl4的紫外-可见光光谱图

Fig. 2 UV-Vis spectrum of (HOC2H4NH3)2CuCl4

图3 (HOC2H4NH3)2CuCl4粉末的XRD图谱

Fig. 3 XRD pattern of (HOC2H4NH3)2CuCl4 powder

图4 层状(HOC2H4NH3)2CuCl4中有机链的结构和取向示意图

Fig. 4 Schematic illustration of the structure and orientation in the layered (HOC2H4NH3)2CuCl4 hybrid

表1 (HOC2H4NH3)2CuCl4的EXAFS拟合参数

Table 1 EXAFS fitting parameters of (HOC2H4NH3)2CuCl4

Sample	Bond	N	R/nm	σ²/nm²
(HOC₂H₄NH₃)₂CuCl₄	Cu-Cl	6.0±0.5	0.191±0.001	4.8×10^-5

图5 (HOC2H4NH3)2CuCl4的Cu的K边XANES谱

Fig. 5 XANES spectrum of Cu K-edge in (HOC2H4NH3)2 CuCl4

图6 (HOC2H4NH3)2CuCl4的Cu边傅里叶变换的EXAFS谱

Fig. 6 Fourier transforms of EXAFS spectrum of Cu edge in (HOC2H4NH3)2CuCl4

图7 (HOC2H4NH3)2CuCl4晶体(100)面示意图

Fig. 7 Schematic representation of single-layer (100)-oriented (HOC2H4NH3)2CuCl4 perovskites

图8 (HOC2H4NH3)2CuCl4的TGA和DSC曲线

Fig. 8 TGA and DSC curves of (HOC2H4NH3)2CuCl4

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杂化钙钛矿(HOC₂H₄NH₃)₂CuCl₄的制备与表征

Preparation and Characterization of a Novel Hybrid Perovskite (HOC₂H₄NH₃)₂CuCl₄

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