In situ Alkylation Regulation of the Structure and Properties of Inorganic-Organic Hybrid Perovskite-Like Materials※

doi:10.6023/A21120573

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (4): 460-466.DOI: 10.6023/A21120573 Previous Articles Next Articles

Special Issue: 中国科学院青年创新促进会合辑

Article

原位烷基化调控无机-有机杂化类钙钛矿材料的结构及其性能^※

梁广玲^a^,^b^,^c, 叶晓亮^b^,^c, 王观娥^a^,^b^,^c^,^*(), 徐刚^b^,^c

a 福建师范大学化学与材料学院福州 350007
b 中国科学院福建物质结构研究所结构化学国家重点实验室福州 350002
c 中国科学院大学北京 100049

投稿日期:2021-12-22 发布日期:2022-02-15
通讯作者: 王观娥
作者简介:
^※ 庆祝中国科学院青年创新促进会十年华诞.
基金资助:
国家自然科学基金(91961115); 国家自然科学基金(21975254); 国家自然科学基金(21905280); 中国科学院青年创新促进会(2018342)

In situ Alkylation Regulation of the Structure and Properties of Inorganic-Organic Hybrid Perovskite-Like Materials^※

Guang-ling Liang^a^,^b^,^c, Xiao-liang Ye^b^,^c, Guan-E Wang^a^,^b^,^c(), Gang Xu^b^,^c

a College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007
b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002
c University of Chinese Academy of Sciences, Beijing 100049

Received:2021-12-22 Published:2022-02-15
Contact: Guan-E Wang
About author:
^※ Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Natural Science Foundation of China(91961115); National Natural Science Foundation of China(21975254); National Natural Science Foundation of China(21905280); Youth Innovation Promotion Association of Chinese Academy of Sciences(2018342)

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Abstract

Inorganic-organic hybrid perovskite-like materials have attracted widespread attention due to their tunable structure and unique optoelectronic properties. By simply changing the size of the organic cations, the structural dimensions of inorganic-organic hybrid perovskite-like materials can be adjusted. However, most of the research were carried out by selecting different types of organic cationic ligands, which is not conducive to the study of structure-activity relationship. Herein, by choosing different alkylation solvents, the control of dimensions and performance of inorganic-organic hybrid perovskite-like materials was realized when the reaction precursors were consistent. Two new inorganic-organic hybrid materials were synthesized in situ by a simple one-step hydrothermal method, that were two-dimensional (2D) [(Me₃)ODA(Me₃)]₃Pb₅I₁₆ (1) and one-dimensional (1D) [H(Et₂)ODA(Et₂)H]Pb₂I₆•H₂O (2) (ODA=4,4-diaminodiphenyl ether). Compound 1 is consisted by 2D inorganic perovskite-like network layers and [(Me₃)ODA(Me₃)]²⁺ organic dications, while compound 2 is composed by 1D inorganic perovskite-like chains, [H(Et₂)ODA(Et₂)H]²⁺ and water molecules. Compound 1 and 2 showed different structures and exhibited different stability, optoelectronics, and humidity sensitivity. The methylated compound 1 showed an obvious photoelectric response under visible light illumination (400~790 nm), and the ethylated compound 2 exhibited no photoelectric response. Compound 2 presented better stability to water and organic solvents compared to compound 1, which can be as an ideal candidate in fabricating smart and efficient sensors for humidity detection. The chemiresistive humidity sensor based on compound 2 showed an investigated response in the wide relative humidity (RH) (10%~100%) at room temperature. The sensor showed a high sensitivity in the range of 10%~100% RH and good cycle stability. It displayed 10⁵-fold increase toward 100% RH. The sensing mechanism of the compound 2 based humidity sensor was further studied by direct current (DC) instantaneous reverse polarity method, which proved that the moisture responsiveness was dominated by electronic conduction, and the free transmission of electrons dominated the change of material's conductivity.

Key words: inorganic-organic hybrid, structure control, photoelectric response, humidity sensing

Cite this article

Guang-ling Liang, Xiao-liang Ye, Guan-E Wang, Gang Xu. In situ Alkylation Regulation of the Structure and Properties of Inorganic-Organic Hybrid Perovskite-Like Materials^※[J]. Acta Chimica Sinica, 2022, 80(4): 460-466.

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Fig. & Tab. 5

Figure 1. (a) Coordination mode of the smallest asymmetric unit of Pb5I166–, (b) 2D layered structure consisted of Pb5I166–, (c) 3D stacking of [(Me3)ODA(Me3)]3Pb5I16, (d) coordination mode of the smallest asymmetric unit of Pb2I62–, (e) 1D chain structure comprised of Pb2I62– and (f) 3D stacking of [H(Et2)ODA(Et2)H]Pb2I6•H2O (for clarity, the H atom is omitted)

Figure 2. Simulated and experimental PXRD patterns of (a) compound 1 and (b) compound 2, and their PXRD patterns after immersing in different solvents at room temperature for 2 h

Figure 3. I-V Curves of (a) compound 1 and (b) compound 2 in the range of 30~130 ℃, (c) temperature-dependent conductivity results of compound 1 and compound 2 (ln σ-1000/T) and (d) the optical band gap of compound 1 and compound 2

Figure 4. (a) Photocurrent response of compound 1 and compound 2 to light with different wavelengths (400~700 nm) and (b) cyclic stability of the photocurrent of compound 1 at 550 nm

Figure 5. Humidity response characteristics of the sensor based on compound 2 at room temperature (a) response-recovery curve at 10%~100% RH; (b) response-RH% plot; (c) response-recovery curve for four consecutive cycles at 70% RH; (d) current-time curves of the sensor at 40%~100% RH obtained by using DC instantaneous reverse polarity experiments

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原位烷基化调控无机-有机杂化类钙钛矿材料的结构及其性能^※

In situ Alkylation Regulation of the Structure and Properties of Inorganic-Organic Hybrid Perovskite-Like Materials^※

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References 40

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原位烷基化调控无机-有机杂化类钙钛矿材料的结构及其性能※

In situ Alkylation Regulation of the Structure and Properties of Inorganic-Organic Hybrid Perovskite-Like Materials※

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 5

References 40

Related Articles 3

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Comments

原位烷基化调控无机-有机杂化类钙钛矿材料的结构及其性能^※

In situ Alkylation Regulation of the Structure and Properties of Inorganic-Organic Hybrid Perovskite-Like Materials^※