静电纺丝技术制备聚丙烯腈/铕-脂肪酸相变和发光双功能复合纳米纤维

doi:10.7503/cjcu20150414

摘要/Abstract

摘要：

以不同链长的脂肪酸为配体, 1,10-邻菲啰啉为第二配体, 通过与发光稀土铕离子进行配位, 合成了铕-脂肪酸相变和发光配合物; 再采用静电纺丝技术以聚丙烯腈(PAN)为载体基质, 铕-脂肪酸为相变和发光材料制备了一种新型的相变和发光纳米纤维. 用扫描电镜(SEM)、 X射线能量色散谱仪(EDS)、荧光光谱仪(FL)和差示扫描量热仪(DSC)对相变和发光纳米纤维的性能进行分析. 研究结果显示, 复合纳米纤维的直径在285~600 nm, 在280 nm紫外光激发下, 复合纳米纤维发射出主峰位于580, 593和614 nm的红光, 对应Eu³⁺的⁵D₀-⁷F₀, ⁵D₀-⁷F₁及⁵D₀-⁷F₂跃迁. 相变和发光纳米纤维具有优异的荧光性能及相变功能, 纳米纤维的直径随着铕含量和脂肪酸碳链的增加呈现增大的趋势.

关键词: 铕-脂肪酸, 聚丙烯腈, 相变, 荧光, 静电纺丝, 纳米纤维

Abstract:

Complexes of Eu-fatty acid were synthesized with fatty acid and 1,10-phenanthroline as ligand linked up to rare-earth ion(Eu³⁺) as functional light-emitting group. Then, ultrafine fibers of polyacrylonitrile(PAN)/ Eu-fatty acid composite in which Eu-fatty acid acts as a model phase change luminescence material and PAN acts as a supporting material, were prepared via electro-spinning as phase change and luminescence materials. The properties of the novel phase change and luminescence fiber were characterized by scanning electron microscope(SEM), energy dispersive spectrometer(EDS), fluorospectrophotometer(FL), the differential scanning calorimetry(DSC). FL results suggested that under the excitation of 280 nm ultraviolet, PAN/Eu-MA composite nanofiber emitted the predominant emission peaks at 580, 593 and 614 nm, corresponding to ⁵D₀-⁷F₀, ⁵D₀-⁷F₁, ⁵D₀-⁷F₂ transitions of Eu³⁺, respectively. The composite nanofibers have good phase change properties and excellent luminescent property. With the increasing of Eu³⁺ content and carbon numbers of fatty acid, the average diameters of PAN/Eu-fatty acid composite fibers increases from 285 nm to 600 nm. This technique can be used to prepare other similar phase change and luminescence bifunctional composite nanofibers.

Key words: Eu-Fatty acid composite, Polyacrylonitrile, Phase change, Luminescence, Electro-spinning, Nanofiber

中图分类号:

O631
O614

TrendMD:

师奇松, 赵祎宁, 张鸣春, 靳昕怡, 刘彦池, 杨明山. 静电纺丝技术制备聚丙烯腈/铕-脂肪酸相变和发光双功能复合纳米纤维. 高等学校化学学报, 2015, 36(9): 1807.

SHI Qisong, ZHAO Yining, ZHANG Mingchun, JIN Xinyi, LIU Yanchi, YANG Mingshan. Electrospinning Fabrication of PAN/Eu-fatty Acid Phase Change and Luminescence Bifunctional Composite Nanofibers^†. Chem. J. Chinese Universities, 2015, 36(9): 1807.

图/表 8

Table 1 Material ratios of precursors solution for prepa-ring PAN/Eu-fatty acid composite nanofibers*

Sample	m(Eu-fatty acid)/g
S1(PAN/Eu-SA)	0.34
S2(PAN/Eu-SA)	0.51
S3(PAN/Eu-SA)	0.85
S4 (PAN/Eu-SA)	1.19
S5(PAN/Eu-LA)	0.85
S6(PAN/Eu-MA)	0.85
S7(PAN/Eu-PA)	0.85

Fig.1 SEM images of electrospun PAN/Eu-SA fibers different Eu3+ mass ratios(A) PAN(260 nm); (B) S1(440 nm); (C) S2(453 nm); (D) S3(480 nm); (E) S4(600 nm).

Fig.2 SEM images of electrospun PAN/Eu-fatty acid fibers at different fattyacid(A)PAN/Eu-LA(S5)(285 nm); (B) PAN/Eu-MA(S6)(384 nm); (C) PAN/Eu-PA(S7)(396 nm); (D) PAN/Eu-SA(S3)(480 nm).

Fig.3 EDS spectrum of PAN/Eu-SA(S3) composite nanofibers

Fig.4 Excitation(A) and emission(B) spectra of PAN/Eu-MA composite nanofibers(λem=614 nm, λex=280 nm)

Fig.5 Emission spectra(A) of PAN/Eu-SA composite nanofibers(S1, S2, S3 and S4) with different mass fractions of Eu-SA to PAN(λex=280 nm) and relationship between Eu-SA content and luminescence intensities of peak at 614 nm for PAN/Eu-SA composite nanofibers(B)

Fig.6 DSC curves of PAN/Eu-fatty acid composite fibers a. S3; b. S5; c. S6; d. S7.

Table 2 Melting temperatures(Tm) and melting enthalpies(ΔHm) of electrospun fine composite fibers

Sample	T_m/℃	ΔH_m/(kJ·kg^-1)	Sample	T_m/℃	ΔH_m/(kJ·kg^-1)
S3	64.54	65.91	SA	67.99	192.02
S5	46.34	60.32	LA	49.48	166.93
S6	56.57	65.32	MA	59.27	202.02
S7	57.14	67.48	PA	62.31	207.65

参考文献 31

[1]	Choi Y. I., Yoon Y., Kang J. G., Sohn Y., J. Lumin., 2015, 158, 27—31
[2]	Song L.X., Du P. F., Jiang Q. X., Cao H. B., Xiong J., J. Lumin., 2014, 150, 50—54
[3]	Peng C., Li G. G., Kang X. J., Li C. X., Lin J., J. Colloid Interface Sci., 2011, 355(1), 89—95
[4]	Hirai Y., Nakanishi T., Miyata K., Fushimi K., Hasegawa Y., Mater. Lett., 2014, 130, 91—93
[5]	Izumi C. M. S., Brito H. F., Ferreira A. M. D. C., Constantino V. R. L., Temperini M. L. A., Synth. Met., 2009, 159, 377—384
[6]	Xin S. Y., Wang Y. H., Dong P. Y., Zeng W., Zhang J., J. Mater. Chem. C, 2013, 1, 8156—8160
[7]	Cacciotti I., Bianco A., Pezzotti G., Gusmano G., Chem. Eng. J., 2011, 166,751—764
[8]	Wang Y. H., Wang J. X., Dong X. T., Yu W. S., Liu G. X., Acta Chim. Sinica, 2012, 70, 1576—1582
	(王莹熇, 王进贤, 董相廷, 于文生, 刘桂霞. 化学学报, 2012, 70, 1576—1582)
[9]	Wang Y. H., Wang J. X., Dong X. T., Yu W. S., Liu G. X., Chem. J. Chinese Universities, 2012, 33(8), 1657—1662
	(王莹熇, 王进贤, 董相廷, 于文生, 刘桂霞. 高等学校化学学报, 2012, 33(8), 1657—1662)
[10]	Tang B. T., Cui J. S., Wang Y. M., Jia C., Zhang S. F., Sol. Energy, 2013, 97, 484—492
[11]	Yang H. Z., Feng L. L., Wang C. Y., Zhao W., Li X. G., Eur. Polym. J., 2012, 48, 803—810
[12]	Rady M., Appl. Energ., 2009, 86, 2704—2720
[13]	Cai Y. B., Ke H. Z., Lin L., Fei X. Z., Wei Q. F., Song L., Hu Y., Fong H., Energy Convers Manage., 2012, 64, 245—255
[14]	Chen C. Z., Wang L. G., Huang. Y., Chem. Eng. J., 2009, 150, 269—274
[15]	Zhang H. Z., Wang X. D., Wu D. Z., J. Colloid Interface Sci., 2010, 343, 246—255
[16]	Li M., Wu Z. S., Tan J. M., Appl. Energy., 2012, 92, 456—461
[17]	Chen C. Z., Wang L. G., Huang Y., Mater. Lett., 2009, 63, 569—571
[18]	Huang S. S., Kang X. J., Cheng Z. Y., Ma P. A., Jia Y., Lin J., J. Colloid. Interface Sci., 2012, 387(1), 285—291
[19]	Chen C. Z., Wang L. G., Huang Y., Mater. Lett., 2008, 62, 3515—3517
[20]	Chen C. Z., Wang L. G., Huang Y., Sol. Energ. Mat. Sol., 2008, 92, 1382—1387
[21]	Wen S. P., Zhang X. P., Yao L., Xi M., Zhang L. Q., Fong H., Liu L., J. Mater. Chem. C, 2013, 1, 1613—1617
[22]	Chen H. C., Wang C. T., Liu C. L., Liu Y. C., Chen W. C., J. Polym. Sci. B, 2009, 47, 463—470
[23]	Yang R. Y., Song W. Y., Liu S. S., Qin W. P., Cryst. Eng. Commun., 2012, 14, 7895—7897
[24]	Hou Z. Y., Cheng Z. Y., Li G. G., Wang W. X., Peng C., Li C. X., Ma P. A., Yang D. M., Kang X. J., Lin J., Nanoscale, 2011, 3, 1568—1574
[25]	Zhang C. L., Yu S. H., Chem. Soc. Rev., 2014, 43, 4423—4448
[26]	He Y. T., Wang L. X., Jia D. Z., Zhao H. Y., Chem. J. Chinese Universities, 2015, 36(1), 157—164
	(何一涛, 王鲁香, 贾殿赠, 赵洪洋. 高等学校化学学报, 2015, 36(1), 156—164)
[27]	Kong Z., Lu X. Y., Zhu Y., Jiang L., Chem. J. Chinese Universities, 2015, 36(4), 614—618
	(孔壮, 鹿现永, 朱英, 江雷. 高等学校化学学报, 2015, 36(4), 614—618)
[28]	Shi Q. S., Chen S. K., Liu T. Q., Polymer Materials Science and Engineering, 2014, 30(4), 176—178
	(师奇松, 陈三宽, 刘太奇. 高分子材料科学与工程, 2014, 30(4), 176—178)
[29]	Guo X. M., Wang J. X., Dong X. T., Yu W. S., Liu G. X., Cryst. Eng. Commun., 2014, 16, 5409—5417
[30]	Cai Y.B., Ke H. Z., Dong J., Wei Q. F., Lin J. L., Zhao Y., Song L., Hu Y., Huang F. L., Gao W. D., Fong H., Appl. Energ., 2011, 88, 2106—2112
[31]	Shi Q. S., Liu Z. R., Jin X. Y., Shen Y., Liu Y. C., Mater. Lett., 2015, 147, 113—115