磷腈-紫精聚合物的合成与电致变色性能

doi:10.7503/cjcu20190541

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (6): 1399.doi: 10.7503/cjcu20190541

• 材料化学 • 上一篇

磷腈-紫精聚合物的合成与电致变色性能

孙孟莹^1,²,吕景春^1,²,徐红^1,²,张琳萍^1,²,钟毅^1,²,陈支泽^1,²,隋晓锋^1,²,毛志平^1,^2,^3,^*()

^1. 东华大学生态纺织教育部重点实验室, 上海 201620
^2. 化学化工与生物工程学院, 上海 201620
^3. 国家染整工程技术研究中心, 上海 201620

收稿日期:2019-10-21 出版日期:2020-06-10 发布日期:2020-04-16
通讯作者: 毛志平 E-mail:zhpmao@dhu.edu.cn
基金资助:
国家自然科学基金(21872025)

Synthesis and Electrochromic Performance of Phosphazene-viologen Polymer ^†

SUN Mengying^1,²,Lü Jingchun^1,²,XU Hong^1,²,ZHANG Linping^1,²,ZHONG Yi^1,²,CHEN Zhize^1,²,SUI Xiaofeng^1,²,MAO Zhiping^1,^2,^3,^*()

^1. Key Lab of Science and Technology of Eco-textile, Ministry of Education, Shanghai 201620, China
^2. College of Chemistry, Chemical Engineering and Biotechnology, Shanghai 201620, China
^3. National Engineering Research Center for Dyeing and Finishing of Textiles, Donghua University, Shanghai 201620, China

Received:2019-10-21 Online:2020-06-10 Published:2020-04-16
Contact: Zhiping MAO E-mail:zhpmao@dhu.edu.cn
Supported by:
† National Natural Science Foundation of China(21872025)

摘要/Abstract

摘要：

以六氯环三磷腈作为核心、紫精为电致变色活性基, 合成了一种新型有机-无机杂化电致变色材料——六(1-乙基-4,4'-联吡啶-甲基苯氧基)环三磷腈(PHV ²⁺). 通过傅里叶变换红外光谱(FTIR)、 X射线衍射(XRD)及核磁共振氢谱( ¹H NMR)表征了PHV ²⁺的结构. 优良的水溶性使得该化合物可以通过简单的方法构造一个以聚乙烯醇(PVA)为凝胶基质的电致变色水凝胶, 具有成本低廉及无毒害的优点. 以氟掺杂氧化锡(FTO)涂层玻璃作为电极材料, PHV ²⁺作为电致变色材料制备了PHV ²⁺/PVA/KCl电致变色器件(PHV ²⁺/PVA/KCl ECD). 该电致变色器件在2.1 V电压下由淡黄色变为紫色, 颜色变化明显, 并且该颜色变化可以循环500次; 器件在526 nm处的光学对比度达到62.19%. 良好的电致变色性质使该化合物在电致变色器件方面具有潜在应用价值.

关键词: 紫精, 磷腈, 电致变色, 聚乙烯醇凝胶电解质

Abstract:

Electrochromic materials have attracted considerable attention due to their versatile applications in academic and industrial areas. In this work, a novel organic-inorganic hybrid electrochromic material(denoted as PHV ²⁺) was synthesized, which contains six viologen moieties and a hexachlorocyclotriphosphazene core. The structure of the polymer was characterized by Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD) and nuclear magnetic resonance. The water solubility makes it possible to construct an electrochromic hydrogel with polyvinyl alcohol by a simple method, which has the advantages of low cost and no toxicity. The electrochromic device made of this polymer exhibits good electrochromic properties with good cyclic stability. The device undergoes a noticeably yellowish-purple color change at a voltage of 2.1 V. The optical contrast of the device is 62.19% at 526 nm. This electrochromic polymer shows its potential in electrochromic application.

Key words: Viologen, Phosphazene, Electrochromism, Polyvinyl alcohol gel electrolyte

中图分类号:

O621.3
O631

TrendMD:

孙孟莹,吕景春,徐红,张琳萍,钟毅,陈支泽,隋晓锋,毛志平. 磷腈-紫精聚合物的合成与电致变色性能. 高等学校化学学报, 2020, 41(6): 1399.

SUN Mengying,Lü Jingchun,XU Hong,ZHANG Linping,ZHONG Yi,CHEN Zhize,SUI Xiaofeng,MAO Zhiping. Synthesis and Electrochromic Performance of Phosphazene-viologen Polymer ^†. Chem. J. Chinese Universities, 2020, 41(6): 1399.

图/表 13

Scheme 1 Schematic illustration of ECD architecture

Scheme 2 Synthetic routes of PHV2+

Scheme 3 Preparation process of PHV2+/PVA/KCl EC gel(A) and assembly process of PHV2+/PVA/KCl ECD(B)

Fig.1 FTIR spectra(A) and XRD patterns(B) of HCTP-CH2Cl(a), EBV+(b) and PHV2+(c)

Fig.2 1H NMR spectrum of PHV2+

Fig.3 TG(A) and DTG(B) curves of HCTP-CH2Cl(a), EBV+(b) and PHV2+(c)

Table 1 Thermogravimetric data of HCTP-CH2Cl, EBV+ and PHV2+ under nitrogen atmosphere

Sample	$T a 5 %$ /℃	$T b max$ /℃	Residue at T_max(%)	Mass loss rate at T_max(%·min^-1)	Residue at 600 ℃(%)
HCTP-CH₂Cl	290	346	88.45	3.83	66.36
EBV⁺	180	277	30.83	23.61	2.12
PHV²⁺	220	265	64.37	6.32	29.48

Table 1 Thermogravimetric data of HCTP-CH2Cl, EBV+ and PHV2+ under nitrogen atmosphere

Sample	$T a 5 %$ /℃	$T b max$ /℃	Residue at T_max(%)	Mass loss rate at T_max(%·min^-1)	Residue at 600 ℃(%)
HCTP-CH₂Cl	290	346	88.45	3.83	66.36
EBV⁺	180	277	30.83	23.61	2.12
PHV²⁺	220	265	64.37	6.32	29.48

Fig.4 SEM images of PVA(A) and PHV2+/PVA/KCl EC(B) gels

Fig.5 EDX mapping of the N(A), P(B), Br(C), Cl(D) elements in PHV2+/PVA/KCl EC gel

Fig.6 UV-Vis absorbance responses of PHV2+/PVA/KCl ECD under different voltages Insets: images of PHV2+/PVA/KCl ECD in the colored and bleached states.

Fig.7 UV-Vis transmittance spectra at different PHV2+ concentrations

Fig.8 Switching time for PHV2+/PVA/KCl ECD(A) and cycle stability of PHV2+/PVA/KCl ECDs(B) at 526 nm Insets: image of PHV2+/PVA/KCl ECD in the state of colored and bleached.

Fig.9 Chronoamperometry curve of PHV2+/ PVA/KCl ECD at 526 nm

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磷腈-紫精聚合物的合成与电致变色性能

Synthesis and Electrochromic Performance of Phosphazene-viologen Polymer ^†

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磷腈-紫精聚合物的合成与电致变色性能

Synthesis and Electrochromic Performance of Phosphazene-viologen Polymer †

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Synthesis and Electrochromic Performance of Phosphazene-viologen Polymer ^†