表面改性活性炭活化过硫酸盐降解苯酚

doi:10.7503/cjcu20160863

摘要/Abstract

摘要：

采用硝酸氧化联合高温处理法对活性炭(AC)进行表面改性(样品记为ACNH), 并将其用于活化过硫酸盐(PS)降解苯酚. 通过氮气等温吸附、元素分析、 X射线光电子能谱和扫描电子显微镜等手段对改性前后活性炭的表面性质进行了表征分析. 考察了活性炭投加量、 PS/苯酚摩尔比、苯酚初始浓度和初始pH等条件对苯酚降解率的影响. 结果表明, 改性后活性炭活化PS能力显著提高, 在ACNH/PS体系中苯酚的降解速率是AC0/PS体系中的5倍; ACNH 的pH值适用范围宽; 活性炭表面醌基、吡喃酮结构和碳原子平面层上的离域π电子(C_π)在活化PS过程中起主要作用, 而羧基起抑制作用.

关键词: 表面改性, 活性炭, 过硫酸盐, 含氧官能团, 碱性位点

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

中图分类号:

O643

TrendMD:

刘子乐, 曾泽泉, 杨洁杨, 崔燕, 武爱莲, 李哲, 黄张根. 表面改性活性炭活化过硫酸盐降解苯酚. 高等学校化学学报, 2017, 38(7): 1241.

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^†. Chem. J. Chinese Universities, 2017, 38(7): 1241.

图/表 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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