Study on Performance and Mechanism of Phenol Degradation through Peroxymonosulfate Activation by Nitrogen/Chlorine Co-doped Porous Carbon Materials

doi:10.6023/A22050227

Abstract

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 12

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

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

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

Table 1. Structural parameters of NC, NC900 and NClCX

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

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

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

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

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

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

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

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

References 40

[1]	Ganiyu S. O.; Sable S.; Gamal El-Din M. Chem. Eng. J. 2022, 429, 132492.
[2]	Liu L.; Chen Z.; Zhang J.; Shan D.; Wu Y.; Bai L.; Wang B. J Water Process Eng. 2021, 42, 102122.
[3]	Luo H.; Fu H.; Yin H.; Lin Q. J. Hazard. Mater. 2022, 426, 128044. doi: 10.1016/j.jhazmat.2021.128044
[4]	Chen X.; Oh W.; Lim T. Chem. Eng. J. 2018, 354, 941. doi: 10.1016/j.cej.2018.08.049
[5]	Luo R.; Wu J.; Zhao J.; Fang D.; Liu Z.; Hu L. Environ. Res. 2022, 204, 112060. doi: 10.1016/j.envres.2021.112060
[6]	Xie J.; Chen L.; Luo X.; Huang L.; Li S.; Gong X. Sep. Purif. Technol. 2022, 281, 119887. doi: 10.1016/j.seppur.2021.119887
[7]	Humphrey N.; Rodriguez R.; Arias G.; Thai E.; Muro E.; Merinov B. V.; Goddard W. A.; Yu T. H. J. Catal. 2020, 381, 295. doi: 10.1016/j.jcat.2019.10.022
[8]	Zhang C.; Bai J.; Ma L.; Lv Y.; Wang F.; Zhang X.; Yuan X.; Hu S. Diam. Relat. Mater. 2018, 87, 215. doi: 10.1016/j.diamond.2018.06.013
[9]	Wu Q.; Liang J.; Yi J.; Shi P.; Huang Y.; Cao R. Science China Materials 2018, 62, 671. doi: 10.1007/s40843-018-9364-5
[10]	Wang N.; Ma W.; Ren Z.; Zhang L.; Qiang R.; Lin K.-Y. A.; Xu P.; Du Y.; Han X. Inorg. Chem. Front. 2018, 5, 1849. doi: 10.1039/C8QI00256H
[11]	Ferrari A. C.; Robertson J. Phys. Rev. B 2000, 61, 14095. doi: 10.1103/PhysRevB.61.14095
[12]	Dresselhaus M. S.; Dresselhaus G.; Saito R.; Jorio A. Phys. Rep. 2005, 409, 47. doi: 10.1016/j.physrep.2004.10.006
[13]	Zhang M.; Luo R.; Wang C.; Zhang W.; Yan X.; Sun X.; Wang L.; Li J. J. Mater. Chem. A 2019, 7, 12547. doi: 10.1039/c9ta02931a
[14]	Yang Y.; Jin H.; Zhang C.; Gan H.; Yi F.; Wang H. J. Alloys Compd. 2020, 821, 153439. doi: 10.1016/j.jallcom.2019.153439
[15]	Tang L.; Liu Y.; Wang J.; Zeng G.; Deng Y.; Dong H.; Feng H.; Wang J.; Peng B. Appl. Catal., B 2018, 231, 1.
[16]	Huang B.; Jiang J.; Huang G.; Yu H. J. Mater. Chem. A 2018, 6, 8978. doi: 10.1039/C8TA02282H
[17]	Zhang J.; Chen P.; Gao W.; Wang W.; Tan F.; Wang X.; Qiao X.; Wong P. K. Sep. Purif. Technol. 2021, 265, 118474. doi: 10.1016/j.seppur.2021.118474
[18]	Chen F.; Cheng X.; Zhao Z.; Wang X. Acta Chim. Sinica 2021, 79, 941.(in Chinese) doi: 10.6023/A21030117
	(陈峰, 程晓琴, 赵振新, 王晓敏, 化学学报, 2021, 79, 941.)
[19]	Wang G.; Chen S.; Quan X.; Yu H.; Zhang Y. Carbon 2017, 115, 730. doi: 10.1016/j.carbon.2017.01.060
[20]	Cheng Z.; Zheng K.; Lin G.; Fang S.; Li L.; Bi J.; Shen J.; Wu L. Nanoscale Adv. 2019, 1, 2674. doi: 10.1039/C9NA00089E
[21]	Bianco G. V.; Sacchetti A.; Milella A.; Grande M.; D’orazio A.; Capezzuto P.; Bruno G. Carbon 2020, 170, 75. doi: 10.1016/j.carbon.2020.07.038
[22]	Ghanbari F.; Moradi M. Chem. Eng. J. 2017, 310, 41. doi: 10.1016/j.cej.2016.10.064
[23]	Abdul Nasir Khan M.; Kwame Klu P.; Wang C.; Zhang W.; Luo R.; Zhang M.; Qi J.; Sun X.; Wang L.; Li J. Chem. Eng. J. 2019, 363, 234. doi: 10.1016/j.cej.2019.01.129
[24]	Ma W.; Wang N.; Tong T.; Zhang L.; Lin K. A.; Han X.; Du Y. Carbon 2018, 137, 291. doi: 10.1016/j.carbon.2018.05.039
[25]	Guan Y.; Ma J.; Ren Y.; Liu Y.; Xiao J.; Lin L.; Zhang C. Water Res. 2013, 47, 5431. doi: 10.1016/j.watres.2013.06.023
[26]	Deng Z.; Yang X.; Xu W. Journal of Tongji University Natural Science, 2009, 37, 354.(in Chinese)
	(邓子峰, 杨晓, 徐伟, 同济大学学报(自然科学版), 2009, 37, 354.)
[27]	Zhang L.; Kanki T.; Sano N.; Toyoda A. Environ. Monit. Assess. 2006, 115, 395. doi: 10.1007/s10661-006-7236-y
[28]	Liang J.; Xu X.; Qamar Zaman W.; Hu X.; Zhao L.; Qiu H.; Cao X. Chem. Eng. J. 2019, 375, 121908. doi: 10.1016/j.cej.2019.121908
[29]	Wang Q.; Li L.; Luo L.; Yang Y.; Yang Z.; Li H.; Zhou Y. Chem. Eng. J. 2019, 376, 120891. doi: 10.1016/j.cej.2019.01.170
[30]	Wu L.; Yu Y.; Zhang Q.; Hong J.; Wang J.; She Y. Appl. Surf. Sci. 2019, 480, 717. doi: 10.1016/j.apsusc.2019.03.034
[31]	Xi T.; Li X.; Zhang Q.; Liu N.; Niu S.; Dong Z.; Lyu C. Front. Env. Sci. Eng. 2021, 15, 11. doi: 10.1007/s11783-020-1303-4
[32]	Cheng X.; Guo H.; Zhang Y.; Wu X.; Liu Y. Water Res. 2017, 113, 80. doi: S0043-1354(17)30091-X pmid: 28199865
[33]	Duan W.; He J.; Wei Z.; Dai Z.; Feng C. Environ. Sci.: Nano 2020, 7, 2982. doi: 10.1039/D0EN00848F
[34]	Pang K.; Sun W.; Ye F.; Yang L.; Pu M.; Yang C.; Zhang Q.; Niu J. J. Hazard. Mater. 2022, 424, 127270. doi: 10.1016/j.jhazmat.2021.127270
[35]	Gul I.; Sayed M.; Shah N. S.; Rehman F.; Khan J. A.; Gul S.; Bibi N.; Iqbal J. Environ. Sci. Pollut. Res. 2021, 28, 23368. doi: 10.1007/s11356-020-11497-2
[36]	Lyu L.; Yu G.; Zhang L.; Hu C.; Sun Y. Environ. Sci. Technol. 2018, 52, 747. doi: 10.1021/acs.est.7b04865
[37]	Li J.; He L.; Jiang J.; Xu Z.; Liu M.; Liu X.; Tong H.; Liu Z.; Qian D. Electrochim. Acta 2020, 353, 136579. doi: 10.1016/j.electacta.2020.136579
[38]	Ma Y.; Liu R.; Meng S.; Niu L.; Yang Z.; Lei Z. Acta Chim. Sinica 2019, 77, 153.(in Chinese) doi: 10.6023/A18090372
	(马亚丽, 刘茹雪, 孟双艳, 牛力同, 杨志旺, 雷自强, 化学学报, 2019, 77, 153.)
[39]	Liu Y.; Miao W.; Fang X.; Tang Y.; Wu D.; Mao S. Chem. Eng. J. 2020, 380, 122584. doi: 10.1016/j.cej.2019.122584
[40]	Guo W.; Yu J.; Dai Z.; Hou W. Acta Chim. Sinica 2019, 77, 1203.(in Chinese) doi: 10.6023/A19080316
	(郭文娟, 于洁, 代昭, 侯伟钊, 化学学报, 2019, 77, 1203.) doi: 10.6023/A19080316

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