Degradation of Phenol with Persulfate Activated by Surface Modified Activated Carbon†

doi:10.7503/cjcu20160863

Abstract

Abstract:

Original activated carbon(AC0) was modified through nitric acid treatment followed by thermal annealing, as a result, ACNH was obtained. The activated carbon samples(ACs) were used to activate persulfate(PS) for phenol degradation. The ACs before and after modification were characterized by means of nitrogen adsorption isotherm, element analysis, X-ray photoelectron spectroscopy(XPS) and scanning electron microscopy(SEM). Moreover, the effects of the operating conditions, including the dosage of ACNH, PS/phenol mole ratio, the initial concentration of phenol and initial pH, on the phenol degradation in ACNH/PS system were also investigated. The results showed that the catalytic activity of activated carbon for PS activation was significantly enhanced after the modification, and the degradation rate of phenol in ACNH/PS system was 5 times faster than that in AC0/PS system. In addition, it was found that ACNH can be applicable to a wide pH range . The results also showed that C_π, quinone and pyrone have a positive effect on the activation of PS while the carboxyl has an opposite effect.

Key words: Surface modification, Activated carbon, Persulfate, Oxygen-containing functional group, Basic site

CLC Number:

O643

TrendMD:

LIU Zile, ZENG Zequan, YANG Jieyang, CUI Yan, WU Ailian, LI Zhe, HUANG Zhanggen. Degradation of Phenol with Persulfate Activated by Surface Modified Activated Carbon^†[J]. Chem. J. Chinese Universities, 2017, 38(7): 1241.

Figures/Tables 13

Table 1 Physical properties, surface acidity and basicity of the AC samples

Sample	S_BET/ (m²·g^-1)	V_mic/ (cm³·g^-1)	Pore size/nm	pH_pzc	Acidity/ (mmol·g^-1)	Basicity/ (mmol·g^-1)	S_mic/ (m²·g^-1)
AC0	631	0.14	3.05	5.01	1.88	0.52	348.87
ACN	554	0.13	3.03	3.71	2.46	0.20	331.54
ACNH	730	0.16	2.86	7.74	1.45	1.04	396.31

Table 2 Elemental analysis of the AC samples

Sample	Mass fraction(%)
Sample	C	H	O	N	S
AC0	91.16	0.99	4.77	0.55	0.31
ACN	89.74	1.04	6.51	0.75	0.25
ACNH	95.60	0.62	2.26	0.76	0.25

Fig.1 SEM images of AC0(A), ACN(B) and ACNH(C)

Fig.2 Oxygen-containing functional groups on the surface of carbon

Fig.3 XPS spectra of C1s of AC0(A), ACN(B) and ACNH(C)

Table 3 Deconvolution of the C1s XPS profiles of AC samples

Sample	Peak area distribution(%)
Sample	C1(Peak Ⅰ)	C2(Peak Ⅱ)	C3(Peak Ⅲ)	C4(Peak Ⅳ)	C5(Peak Ⅴ)
AC0	67.01	17.32	3.73	5.28	6.66
ACN	63.87	19.77	3.37	6.69	6.30
ACNH	63.58	19.55	5.24	3.49	8.13

Fig.4 XPS spectra of O1s of AC0(A), ACN(B) and ACNH(C)

Table 4 Deconvolution of the O1s XPS profiles of AC samples

Sample	Peak area distribution(%)
Sample	O1(PeakⅠ)	O2(Peak Ⅱ)	O3(Peak Ⅲ)	O4(Peak Ⅳ)	O_2ads+H₂O_ads(Peak Ⅴ)
AC0	21.42	34.73	30.59	11.62	1.65
ACN	18.26	37.85	24.26	17.02	2.61
ACNH	27.56	20.14	31.69	18.69	1.91

Fig.5 Adsorption of phenol by AC samples

Fig.6 Oxidation of phenol by PS in the presence of the AC samples and the kinetic rate constants(inset)

Fig.7 Effects of dosage of ACNH (A), mole ratio of PS/phenol(B), the initial concentration of phenol(C) and the initial pH in the ACNH/PS system(D)(A) Dosage of ACNH/(g·L-1): a. 0; b. 0.16; c. 0.28; d. 0.4; e. 0.48; f. 0.6; (B) molar ratio of PS/phenol: a. PS; b. 0.5∶1; c. 1∶1; d. 2∶1; e. 3∶1; f. 7∶1; g. 15∶1; (C) initial concentration of phenol/(mg·L-1): a. 50; b. 80; c. 100; d. 150; e. 200; (D) pH: a. 3; b. 6; c. 9; d. 11.

Fig.8 Stability of ACNHACNH dosage: 0.4 g/L; molar ratio of PS/phenol: 3∶1; temperature: 25 ℃.

Table 5 Physical properties of fresh ACNH, used ACNH and regenerated ACNH

Sample	S_BET/(m²·g^-1)	Microporous volume/(cm³·g^-1)	Pore size/nm	Micropore area/(m²·g^-1)
Fresh ACNH	631	0.14	3.05	348.87
Used ACNH	275	0.04	4.37	90.58
Regenerated ACNH	435	0.07	3.89	146.98

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