Synthesis, Characterization and Catalytic Properties of Series of Water-soluble Sulfonated Porphyrins†

doi:10.7503/cjcu20170043

Abstract

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

CLC Number:

O614
O643

TrendMD:

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

Figures/Tables 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

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