系列水溶性磺酸卟啉的制备、表征及催化性能

doi:10.7503/cjcu20170043

摘要/Abstract

摘要：

改进磺化路线制备了5种取代基及取代位置不同的水溶性磺酸卟啉, 利用氢核磁共振波谱(¹H NMR)、傅里叶变换红外光谱(FTIR)、紫外-可见吸收光谱(UV-Vis)及质谱(MS)等手段对产物进行表征及性质研究. 将该系列卟啉作为光催化剂, 用于催化氧化1,5-萘二酚的反应, 主催化产物为5-羟基-1,4-萘二醌, 转化率为78%~95%. 实验发现, 磺酸基团在苯环上的位置以及取代基的数目、电子效应及立体位阻效应均会对催化结果产生影响, 其中磺酸根的位置至关重要. 动力学研究结果表明该催化氧化过程为一级反应. 探讨了该反应的反应机理.

关键词: 水溶性磺酸卟啉, 1,5-萘二酚, 光催化氧化, 一级反应

Abstract:

A series of water-soluble sulfonated porphyrins with different substituents and substituted positions has been efficiently synthesized by modifying the traditional sulfonation route, and has been characterized by ¹H NMR, Fourier transform infrared spectroscopy(FTIR), ultraviolet-visible spectroscopy(UV-Vis) and mass spectrscopy(MS). These porphyrins were used as photocatalysts for the oxidation of 1,5-dihydroxynaphthalene using H₂O₂ as oxidant. The product was 5-hydroxy-1,4-naphthoquinone with conversion rates ranging from 78% to 95%. The effects of the position of the sulfonic group on the phenyl ring, the number of substituents, the electron and steric hindrance of the substituent groups on the catalytic activities of the porphyrins have been investigated and the results indicate that all these factors can affect the catalytic activities. The catalytic mechanism has been discussed and the kinetic data show that the catalytic process is a first-order reaction.

Key words: Water-soluble sulfonated porphyrin, 1,5-Dihydroxynaphthalene, Photocatalytic oxidation, First-order reaction

中图分类号:

O614
O643

TrendMD:

孙凯芳, 蔡诚, 侯宗胜, 王颖, 任奇志. 系列水溶性磺酸卟啉的制备、表征及催化性能. 高等学校化学学报, 2017, 38(7): 1117.

SUN Kaifang, CAI Cheng, HOU Zongsheng, WANG Ying, REN Qizhi. Synthesis, Characterization and Catalytic Properties of Series of Water-soluble Sulfonated Porphyrins^†. Chem. J. Chinese Universities, 2017, 38(7): 1117.

图/表 10

Fig.1 Schematic view for photooxidation of 1,5-dihydroxynaphthalene catalyzed by water-soluble sulfonated porphyrins using H2O2 as oxidant

Scheme 1 Synthetic routes of series of water-soluble sulfonated porphyrins

Fig.2 Photos of porphyrins before and after the sulfonation

Fig.3 1H NMR spectra of TPP/TPPS(A), TMPP/TMPPS(B), TCPP/TCPPS(C) and TDCPP/TDCPPS(D)

Table 1 IR spectra data(ν˙/cm-1) of water soluble sulfonated porphyrins

TPP	TPPS	TMPP	TMPPS	TCPP	TCPPS	3-TMPP	3-TMPPS	Assignment
3315.6	3298.5	3317.9	3318.2	3315.9	3316.8			ν(N—H)(pyrrole)
			3424.5	3414.2	3427.0	3426.2	3438.7	ν(O—H)
3058.4	2934.2	2921.6	2931.0	3068.0	2970.8	2926.0	2908.1	ν(C—H)
3024.7	2859.8	2833.4	2836.1	2919.3	2920.2	2831.6
1593.7	1653.1	1607.4	1699.6	1596.7	1624.3	1630.0	1637.0	ν(C C)(phenyl)
1556.0	1534.5	1508.7	1591.0	1485.9	1464.8	1592.5
798.8	740.1	800.2	883.5	799.4	880.5	799.8	808.9	ν(C—H)+
698.2			796.9		794.8			δ(C—H)(phenyl)
967.2	910.8	964.5	975.1	964.8	964.2	973.2	977.5	δ(N—H)(pyrrole)
878.1	850.8	841.2	841.6	856.0	810.6	878.4	865.5	π(C—H)(pyrrole)
	1252.4		1173.4		1188.5		1251.9	ν(SO₂)
	1132.9		1151.8		1120.7		1150.7
	1024.4		1091.3		1015.1		1061.8
		1247.2	1248.8			1251.9	1258.0	ν(C—O)(ph—O—C)
				1092.0	1090.0			ν(C—Cl)

Fig.4 UV-Vis spectra(A, B) and fluorescence emission spectra(C, D) of sulfonated porphyrins (A, C) a. TDCPPS; b. TCPPS; c. TMPPS. (B, D) a. TPPS; b. 3-TMPPS.

Fig.5 UV-Vis spectra of 1,5-dihydroxynaphthalene photocatalyzed by TMPPSTime from top to bottom is 0, 5, 10, 15, 20, 25, 30, 45, 60, 90 min.

Fig.6 Conversion rates of 1,5-dihydroxynaphthalene photocatalyzed by water-soluble porphyrins

Table 2 Dynamic data of 1,5-dihydroxynaphthalene photocatalyzed by water-soluble porphyrinsa

Porphyrin	Blank^b	TPPS	TMPPS	TCPPS	3-TMPPS	TDCPPS
10³k/min^-1	3	80	64	18	31	17
Conversion rate(%)	19	91	95	81	92	78

Scheme 2 Mechanism of 1,5-dihydroxynaphthalene photocatalyzed by water-soluble porphyrins

参考文献 32

[1]	Meunier B., de Visser S. P., Shaik S., Chem. Rev., 2004, 104(9), 3947—3980
[2]	Castro K. A., Simões M. M., Neves M. G. P., Catal. Sci. Technol., 2014, 4(1), 129—141
[3]	Hu Y. P., Shan D. L., Lu X. Q., Chem. J. Chinese Universities,2016, 37(6), 1082—1087
	(胡一平, 陕多亮, 卢小泉.高等学校化学学报, 2016, 37(6), 1082—1087)
[4]	Liu S. S., Lu J. F., Wang M. K., J. Electrochem., 2016, 22(4), 340—355
	(刘双双, 鲁建峰, 王鸣魁.电化学, 2016, 22(4), 340—355)
[5]	Tabata M., Nakajima K., Nyarko E., J. Inorg. Biochem., 2000, 78(4), 383—389
[6]	Pedrosa L. F., de Souza M. C., Faustino M. A. F., Australian J. Chem., 2011, 64(7), 939—944
[7]	Monteiro C. J., Pereira M. M., Azenha M. E., Photochem. Photobiol. Sci., 2005, 4(8), 617—624
[8]	Long S. R., Wan Y., Xia A. D., Acta Chim. Sinica,2015, 73(7), 723—728)
	(龙飒然, 宛岩, 夏安东.化学学报, 2015, 73(7), 723—728)
[9]	Nimri S., Keinan E., J. Am. Chem. Soc., 1999, 121(39), 8978—8982
[10]	Steinberg-Yfrach G., Rigaud J. L., Durantini E. N., Nature,1998, 392(6675), 479—482
[11]	D’Oliveira J. C., Al-Sayyed G., Pichat P., Environ. Sci. Technol., 1990, 24(7), 990—996
[12]	Wei B., Zhang Q. L., Liu Y. Z., Chem. Eng., 2016, 44(5), 11—16
	(魏冰, 张巧玲,刘有智.化学工程, 2016, 44(5), 11—16)
[13]	Sun X. J., Appl. Chem. Ind., 2016, 45(5), 866—868
	(孙秀君. 应用化工, 2016,45(5), 866—868)
[14]	Liu Q. Y., Liu L., Cui F. F., Environ. Sci. Technol., 2008, 31(7), 116—119
	(刘琼玉, 刘立, 崔菲菲.环境科学与技术, 2008, 31(7), 116—119)
[15]	Nowakowska M., Kępczyński M., J. Photoch. Photobio.A,1998, 116(3), 251—256
[16]	Skurlatov Y. I., Ernestova L., Vichutinskaya E., J. Photoch. Photobio.A,1997, 107(1), 207—213
[17]	Lente G., Espenson J.H.,Chem. Commun., 2003, (10), 1162—1163
[18]	DeRosa M. C., Crutchley R. J., Coordin. Chem. Rev., 2002, 2(33), 351—371
[19]	Murtinho D., Pineiro M., Pereira M.M., J. Chem. Soc. Perkin Trans. 2, 2000, (12), 2441—2447
[20]	Ren Q.Z., Yao Y., Ding X. J.,Chem. Commun., 2009, (31), 4732—4734
[21]	Liu S. Y., Ren Q. Z., Ding X. J., Chem. J. Chinese Universities,2009, 30(7), 1272—1278
	(刘双艳, 任奇志,丁晓健.高等学校化学学报, 2009, 30(7), 1272—1278)
[22]	Wang Y., Ren Q. Z., Guo L. T., Chem. J. Chinese Universities,2013, 34(7), 1576—1584
	(王颖, 任奇志, 郭琳童.高等学校化学学报, 2013, 34(7), 1576—1584)
[23]	Song X. F., She Y. B., Liu R., Chemical Reagents,2011, 33(3), 193—195
	(宋旭锋, 佘远斌, 刘燃.化学试剂, 2011, 33(3), 193—195)
[24]	Wang T., Han S. T., J. Hebei Normal University (Natural Science Edition), 2007, 4, 488—490
	(王涛, 韩士田. 河北师范大学学报(自然科学版), 2007, 4, 488—490)
[25]	Monteiro C. J., Pereira M. M., Azenha M. E., Photochem. Photobiol. Sci., 2005, 4(8), 617—624
[26]	Jin T. S., Zhang J. S., Wang A. Q., Chinese J. Org. Chem., 2005, 25(3), 335—338
	(靳通收, 张建设, 王爱卿.有机化学, 2005, 25(3), 335—338)
[27]	Shi D. Q., Zhuang Q. Y., Chen J., Chin. J. Org. Chem., 2003, 23(7), 694—696
	(史达清, 庄启亚, 陈景.有机化学, 2003, 23(7), 694—696)
[28]	Tang F. L., Chen X. H., Shang Y. Y., Chemical Reagents,1991, 13(3), 141—144
	(汤福隆, 陈秀华, 尚杨玉.化学试剂, 1991, 13(3), 141—144)
[29]	Wang T., Han S. T., Hebei. J. Ind. Sci. Technol., 2005, 22(4), 239—244
	(王涛,韩士田. 河北工业科技, 2005, 22(4), 239—244)
[30]	Fu X.C., Shen W. X., Yao T. Y., Hou W. H., Physical Chemistry, Higher Education Press, Beijing, 2005
	(傅献彩, 沈文霞, 姚天扬, 侯文华. 物理化学,北京:高等教育出版社, 2005)
[31]	Silva E., Pereira M. M., Burrows H. D., Photochem. Photobiol. Sci., 2004, 3(2), 200—204
[32]	Wu Y. Q., Ouyang R. Z., Chin. J. Chem. Phys., 1999, 12(1), 93—98
	(吴谊群, 欧阳瑞珍. 化学物理学报, 1999, 12(1), 93—98)