纳米纤维素/聚3,4-乙撑二氧噻吩复合薄膜的制备及电致变色性能

doi:10.7503/cjcu20160904

摘要/Abstract

摘要：

以棉浆粕为原料, 采用硫酸溶胀结合超声波处理的方法制备了纳米纤维素(NC). 在纳米纤维素的水分散液中加入3,4-乙撑二氧噻吩单体, 以过硫酸铵为氧化剂, 采用原位化学氧化法制得了纳米纤维素/聚3,4-乙撑二氧噻吩(NC/PEDOT)纳米复合物. 对NC和NC/PEDOT复合物进行扫描电镜、透射电镜和红外光谱分析. 将纳米复合物的水分散液滴涂在氧化铟锡(ITO)玻璃表面形成复合薄膜, 考察不同纳米纤维素含量对NC/PEDOT复合薄膜电致变色性能的影响. 结果表明, NC呈棒状, 平均直径为20 nm, 长度为100~300 nm; NC/PEDOT复合物中PEDOT均匀包覆在NC表面形成核壳结构, 平均直径为30 nm; 复合薄膜中当NC含量为60%时, 其电致变色性能最好, 具有最高的对比度(24.4%), 最短的响应时间(1 s), 最高的着色效率(51.8 cm²/C).

关键词: 纳米纤维素, 聚3,4-乙撑二氧噻吩, 化学氧化法, 复合薄膜, 电致变色性能

Abstract:

Nano biomaterials based on renewable resources have been of growing interest due to the recent advances in the field of nano technological applications. Nano cellulose(NC) was extracted by swelling cotton pulp, following with the ultrasonic treatment. The composites of poly(3,4-ethylenedioxythiophene)(PEDOT) with NC inclusions at different loadings were prepared using in situ polymerization with ammonium peroxydisulfate(APS) as oxidant in nanocellulose aqueous suspension. NC and NC/PEDOT composites were characterized. The thin composite films were obtained by drop-coating the composites aqueous suspension to the surface of ITO conducting glass. The results showed that the original NC was rod-like, with average diameter of 20 nm and length range from 100 nm to 300 nm. The NC/PEDOT composites were core-shell structure with average diameter of about 30 nm and PEDOT was uniformly coated on the surface of NC. The electrochromic properties of NC/PEDOT composite films with different NC contents were studied by electrochemical test and spectrophotometery. The NC/PEDOT composite film containing 60% NC showed the highest contrast ratio of 24.4%, the shortest response time of 1 s, and the highest coloration efficiency of 51.8 cm²/C.

Key words: Nano cellulose, Poly(3,4-ethylenedioxythiophene), Chemical oxidation, Thin composite film, Electrochromic property

中图分类号:

TrendMD:

张思航, 何永锋, 付润芳, 蒋洁, 李晴碧, 顾迎春, 陈胜. 纳米纤维素/聚3,4-乙撑二氧噻吩复合薄膜的制备及电致变色性能. 高等学校化学学报, 2017, 38(6): 1090.

ZHANG Sihang, HE Yongfeng, FU Runfang, JIANG Jie, LI Qingbi, GU Yingchun, CHEN Sheng. Preparation and Electrochromic Properties of Nano Cellulose/Poly(3,4-ethylenedioxythiophene) Composite Films^†. Chem. J. Chinese Universities, 2017, 38(6): 1090.

图/表 10

Scheme 1 Schematic illustration of the experiment process

Fig.1 UV-Vis transmittance spectra of NC suspension(a) and swelling cellulose suspension(b)Insets are the images of NC suspension(left) and swelling cellulose suspension(right).

Fig.2 SEM(A) and TEM(B) images of NCInsets are the higher magnification for clarity.

Fig.3 SEM images of PEDOT(A), NPE20(B), NPE40(C) and NPE60(D) Insets are the higher magnification for clarity.

Fig.4 TEM image of NPE60(A) and the magnified TEM image(B)

Fig.5 FTIR spectra of NC(a), PEDOT(b), NPE20(c), NPE40(d) and NPE60(e)

Fig.6 Cyclic voltammograms curves of PEDOT(a),NPE20(b), NPE40(c) and NPE60(d)

Fig.7 UV-Vis absorbance spectra of PEDOT(A), NPE20(B), NPE40(C) and NPE60(D)at different potentialsInsets: Photographic images of PEDOT(A), NPE20(B), NPE40(C), NPE60(D) films at colored state(-0.6 V) and bleached state(0.8 V).

Fig.8 Transmittance variation of PEDOT(a), NPE20(b), NPE40(c) and NPE60(d) for 1—2 switches(A) and 301—302 switches(B) between -0.6 V and 0.8 V

Table 1 Electrochromic parameters obtained at 530 nm for 1 and 300 switches

Sample	NC content(%)	τ_c/s		τ_b/s		T_c(%)		T_b(%)		ΔT(%)		Q/(mC·cm^-2)		CE/(cm²·C^-1)
Sample	NC content(%)	1	300	1	300	1	300	1	300	1	300	1	300	1	300
PEDOT	0	2.0	3.5	2.0	3.0	14.8	17.9	19.4	22.7	4.6	4.8	7.1	4.6	16.5	22.4
NPE20	20	1.5	2.0	1.5	2.5	10.8	12.8	23.4	25.1	12.6	12.3	9.4	5.8	35.7	50.4
NPE40	40	1.5	2.0	1.0	2.0	26.3	31.8	42.7	44.7	16.4	12.9	7.4	4.9	28.4	30.2
NPE60	60	1.0	2.0	1.0	1.5	21.8	29.4	46.2	48.1	24.4	18.7	6.3	4.0	51.8	53.5

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