氮氯共掺杂多孔碳活化过一硫酸盐降解苯酚的性能及机理研究

doi:10.6023/A22050227

摘要/Abstract

杂原子共掺杂碳材料在过硫酸盐活化领域具有广阔的应用前景. 本工作通过两步煅烧法合成了氮氯共掺杂ZIF-8衍生多孔碳材料(NClC), 并以苯酚为目标污染物, 考察其活化过一硫酸盐(PMS)的催化性能, 结果表明, 30 min内, 0.04 g/L NClC900活化0.3 g/L PMS可去除水中97.7%的苯酚(50 mg/L), 且总有机碳去除率可达72.4%; NClC900/PMS体系具备优异的酸碱耐受性(pH=3~9)和抗干扰能力, 无机阴离子和腐植酸对其影响较小, 且该体系还可有效去除水中的染料、抗生素、酚类及农药等有机污染物; 循环实验结果表明, NClC900在重复使用4次后其苯酚去除率可达72.1%; 猝灭实验、电子顺磁共振和电化学分析表明¹O₂和表面结合SO₄^•-是导致苯酚降解的主要活性物种, 而NClC900中的石墨N、C—Cl是产生¹O₂和表面结合SO₄^•-的关键活性位点.

关键词: 过一硫酸盐, 金属有机骨架材料, 共掺杂, 表面结合自由基, 单线态氧

Heteroatomic co-doped carbon materials have broad application prospect in the field of persulfate-based advanced oxidation processes. In this paper, nitrogen and chlorine co-doped ZIF-8 derived porous carbon materials (NClC) were synthesized by a two-step pyrolysis method, as follows: 1.5 g ZIF-8 was transferred to a quartz boat, calcined for 6 h at 800 ℃ with a heating rate of 5 ℃/min in a N₂ atmosphere, and cool naturally to room temperature; the black carbon material obtained was further treated with 0.5 mol/L HCl for 24 h to remove the residual Zn and then dried in a 60 ℃ oven to acquire N-doped porous carbon (NC); subsequently, 1.2 g NH₄Cl was uniformly dissolved in 20 mL ultrapure water, and 0.15 g of the synthesized NC was added; after stirring and reaction for 5 h, the mixture was placed in a 60 ℃ oven to dry overnight; the dried sample was ground to a uniform powder and then calcined for 2 h at 700, 800, 900 or 1000 ℃ in a N₂ atmosphere to obtain NClCX, in which the “X” represents the secondary calcination temperature (℃). Additionally, NC900 was obtained by calcination of NC at 900 ℃ in the same way without any modification. The composition and structure of all carbon materials were characterized by field emission scanning electron microscope (FESEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Raman, BET and X-ray photoelectron spectroscopy (XPS). Phenol was employed as a targeted contaminant to explore the performance of NClCX on PMS activation, and the results showed NClC900 exhibited excellent catalytic performance with 97.7% of phenol and 72.4% of total organic carbon (TOC) removal in 30 min. NClC900/PMS system presented excellent acid-base tolerance and anti-interference ability, which can effectively remove phenol over a broad pH range (pH=3~9) or under the interference of various anions (NO₃^-, Cl^-, H₂PO₄^-, HCO₃^-) and humic acid (HA). Moreover, the NClC900/PMS system performed outstanding feasibility in the removal of dyes, antibiotics, phenols, pesticide and purification of actual contaminated water samples. Cyclic experiments showed that NClC900 had good stability and could remove 72.1% of phenol after repeated use for 4 times. Quenching experiments, electron paramagnetic resonance and electrochemical analysis indicated that ¹O₂ and surface-bound SO₄^•- were the main active species for phenol degradation, and the graphite N, C—Cl of NClC900 were the key active sites for generating of ¹O₂ and surface-bound SO₄^•-.

Key words: peroxymonosulfate, metal-organic frameworks, co-doped, surface-bound radical, singlet oxygen

引用此文

李小娟, 叶梓瑜, 谢书涵, 王永净, 王永好, 吕源财, 林春香. 氮氯共掺杂多孔碳活化过一硫酸盐降解苯酚的性能及机理研究[J]. 化学学报, 2022, 80(9): 1238-1249.

Xiaojuan Li, Ziyu Ye, Shuhan Xie, Yongjing Wang, Yonghao Wang, Yuancai Lv, Chunxiang Lin. Study on Performance and Mechanism of Phenol Degradation through Peroxymonosulfate Activation by Nitrogen/Chlorine Co-doped Porous Carbon Materials[J]. Acta Chimica Sinica, 2022, 80(9): 1238-1249.

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图/表 12

图1. NClCX/PMS体系降解苯酚效果图

Figure 1. Degradation efficiency of phenol by NClCX/PMS system Reaction conditions: [catalyst]=0.04 g/L; [PMS]=0.3 g/L; [phenol]=50 mg/L; pH=7.0

图2. (a) ZIF-8、(b) NC和(c~e) NClCX的FESEM图; (f) NClC900的TEM图; (g~j) NClC900的元素映射图

Figure 2. FESEM images of (a) ZIF-8, (b) NC and (c~e) NClCX; (f) TEM image and (g~j) element mapping of NClC900

图3. NC、NC900和NClCX的(a) XRD谱图; (b) Raman光谱图; (c) N2吸脱附曲线; (d)孔径分布图 NC、NC900和NClCX的(a) XRD谱图; (b) Raman光谱图; (c) N2吸脱附曲线; (d)孔径分布图

Figure 3. (a) XRD patterns; (b) Raman spectra; (c) N2 adsorption and desorption curves and (d) pore size distribution of NC, NC900 and NClCX

Sample	SSA^a/ (m²•g^-1)	TPV^b/ (cm³•g^-1)	APS^b/ nm	V_micro^c/ (cm³•g^-1)	V_meso^c/ (cm³•g^-1)
NC	1060.82	0.23	3.76	0.06	0.17
NC900	1418.02	0.40	3.27	0.12	0.28
NClC700	1101.09	0.24	3.49	0.07	0.13
NClC800	1530.69	0.42	2.86	0.14	0.28
NClC900	2259.60	0.84	2.96	0.25	0.59

表1. NC、NC900和NClCX的结构参数

Table 1. Structural parameters of NC, NC900 and NClCX

图4. (a) NC、NC900和NClCX的XPS总谱图; NClC900的(b) C1s和(c) N1s高分辨率谱图; (d) NClCX的Cl2p高分辨率谱图

Figure 4. (a) The XPS surveys of NC, NC900 and NClCX; the high-resolution (b) C1s and (c) N1s spectra of NClC900; (d) the high-resolution Cl2p spectra of NClCX

Sample	C	N	O	Cl	Zn	C=O	吡啶N	吡咯N	石墨N	氧化N
NC	64.00	15.05	6.87	—	14.08	12.43	32.89	26.32	27.63	13.16
NC900	77.85	7.15	7.55	—	7.45	11.51	36.21	5.17	43.10	15.52
NClC700	62.94	12.36	7.51	1.53	15.66	11.73	46.51	13.49	28.84	11.16
NClC800	68.57	8.35	10.36	2.31	10.41	8.39	42.73	10.26	34.62	12.39
NClC900	83.59	4.33	7.09	1.10	3.59	10.26	31.46	6.57	46.95	15.02

表2. NC、NC900和NClCX中C、N、O、Cl、Zn和C=O以及不同类型N物种的比例(at%)

Table 2. Proportion of C, O, N, Cl, Zn atoms, C=O and various N species in NC, NC900 and NClCX (at%)

图5. (a)不同阴离子和(b) HA对苯酚降解的影响; NClC900/PMS体系对(c)不同水体中的苯酚和(d)不同有机污染物的去除

Figure 5. Effect of (a) various anions and (b) HA on the removal of phenol in the NClC900/PMS system; (c) the removal of phenol in different water bodies and (d) various organic pollutants degradation in the NClC900/PMS system Reaction conditions: [catalyst]=0.04 g/L; [PMS]=0.3 g/L; [phenol]=50 mg/L; pH=7.0

图6. NClC900/PMS/苯酚体系反应(a) 0 min、(b) 1 min、(c) 10 min和(d) 30 min时水样的EEM图

Figure 6. EEM diagrams of samples in NClC900/PMS/Phenol system at (a) 0 min, (b) 1 min, (c) 10 min and (d) 30 min

图7. NClC900/PMS体系中(a)苯酚可能的降解路径和(b)不同水样培养下的大肠杆菌存活率

Figure 7. (a) Possible oxidation pathway of phenol; (b) survival rate of E.coli cultured in different samples of NClC900/PMS system

图8. (a, b)不同猝灭剂对NClC900/PMS体系去除苯酚的影响; (c, d)不同体系的EPR波谱图

Figure 8. (a, b) The effect of different quenchers on phenol removal in NClC900/PMS system; (c, d) EPR spectra of different systems

猝灭剂	ROS	抑制率/ %	ROS贡献值 (A)	ROS贡献率(A/T, %)
50/2000 mmol/L MeOH	(SO₄^•-+•OH)_S	2.6/2.6	SO₄^•-_S=1.3	SO₄^•-_S=0.9
50/2000 mmol/L TBA	•OH_S+C	1.3/5.7	•OH_S=1.3 •OH_C=4.4	•OH_S=0.9 •OH_C=3.1
20 mmol/L KI	(SO₄^•-+•OH)_C	61.2	SO₄^•-_C=56.8	SO₄^•-_C=40.6
20 mmol/L L-histidine	¹O₂	55.0	¹O₂=55.0	¹O₂=39.3
20 mmol/L Na₂CO₃	O₂^•-	21.3	O₂^•-=21.3	O₂^•-=15.2

表3. NClC900/PMS体系中不同活性氧的贡献率

Table 3. The contribution rate of different ROS in the system of NClC900/PMS

图9. (a) NCl900在不同溶液中的LSV曲线; (b) NC、NC900和NClCX的Nyquist图; (c)不同催化体系的LSV曲线

Figure 9. (a) LSV curves of NCl900 in different solution; (b) Nyquist plots of NC, NC900 and NClCX; (c) LSV curves of different catalytic systems

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