Research progress in the application of heteroatom-doped carbonaceous materials for persulfate activation

doi:10.16085/j.issn.1000-6613.2020-0501

Abstract

Abstract:

Various methods have been reported for persulfate activation including the use of heat, UV, ultrasound and transition metals. However, these methods suffer from high energy input or inevitable leaching of toxic metal from metal-based catalysts, which has limited their practical applications. Then, carbonaceous materials have attracted considerable interests as heterogeneous catalysts for persulfate activation owing to their large surface area, unique adsorption property and metal-free nature. Heteroatom (N, S, B, P, etc.) doping can not only break carbonaceous materials’ network inertia to enhance the conductivity, but also can increase the reactive sites, resulting in the improvement of their performance in persulfate activation. In this paper, the persulfate activation mechanisms of carbonaceous materials were introduced, mainly involving free radical pathways, singlet oxygen pathways and surface electron transfer, and those of the heteroatom-doped carbonaceous materials were further discussed. Then, the types and fabrication methods of heteroatomic carbonaceous materials as well as their applications in degradation of organic pollutants were reviewed. Finally, it was proposed that the promotion of stability and reusability and the in-depth study of the mechanisms were the future research directions of heteroatom-doped carbonaceous materials.

Key words: persulfate, radical, heteroatom doping, carbonaceous materials, activation, degradation

摘要：

碳材料因其比表面积高、吸附性能佳，并且能克服加热、紫外光照射、超声等传统活化方式能耗高、金属催化材料产生二次污染的弊端而在活化过硫酸盐降解有机污染物应用中具有潜力。杂原子（N、S、B、P等）掺杂不仅能打破碳材料网络惰性、提高电导率，还能增加反应活性位点，是提升碳材料活化过硫酸盐性能的有效途径。本文介绍了碳材料活化过硫酸盐的机理，主要包括自由基途径、单线态氧途径及表面电子传递，并进一步总结了杂原子掺杂碳材料活化过硫酸盐的机理；然后综述了杂原子碳材料的种类、制备方法及其在有机污染物降解中的应用，最后指出了已有研究存在的不足，并提出杂原子掺杂碳材料稳定性及可重复利用性的提升和降解机制的深入探索是未来研究的方向。

关键词: 过硫酸盐, 自由基, 杂原子掺杂, 碳材料, 活化, 降解

CLC Number:

TB383

Xiaojuan LI, Lanmei YE, Fengzhen LIAO, Ziyu YE, Lizhi YEH. Research progress in the application of heteroatom-doped carbonaceous materials for persulfate activation[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 273-281.

李小娟, 叶兰妹, 廖凤珍, 叶梓瑜, 叶礼志. 杂原子掺杂碳材料活化过硫酸盐技术的研究进展[J]. 化工进展, 2021, 40(1): 273-281.

Figures/Tables 4

References 37

38	DUAN X G, SUN H Q, WANG Y X, et al. N-doping-induced nonradical reaction on single-walled carbon nanotubes for catalytic phenol oxidation[J]. ACS Catalysis, 2015, 5(2): 553-559.
39	MA W J, DU Y C, WANG N, et al. ZIF-8 derived nitrogen-doped porous carbon as metal-free catalyst of peroxymonosulfate activation[J]. Environmental Science and Pollution Research, 2017, 24(19): 16276-16288.
40	LIU Y, MIAO W, FANG X, et al. MOF-derived metal-free N-doped porous carbon mediated peroxydisulfate activation via radical and non-radical pathways: role of graphitic N and C-O[J]. Chemical Engineering Journal, 2020, 380: 122584.
41	GUO Y P, ZENG Z Q, LI Y L, et al. In-situ sulfur-doped carbon as a metal-free catalyst for persulfate activated oxidation of aqueous organics[J]. Catalysis Today, 2018, 307: 12-19.
42	GUO Y P, ZENG Z Q, ZHU Y C, et al. Catalytic oxidation of aqueous organic contaminants by persulfate activated with sulfur-doped hierarchically porous carbon derived from thiophene[J]. Applied Catalysis B: Environmental, 2018, 220: 635-644.
43	WANG Y B, LIU M, ZHAO X, et al. Insights into heterogeneous catalysis of peroxymonosulfate activation by boron-doped ordered mesoporous carbon[J]. Carbon, 2018, 135: 238-247.
44	DUAN X G, INDRAWIRAWAN S, SUN H Q, et al. Effects of nitrogen-, boron-, and phosphorus-doping or codoping on metal-free graphene catalysis[J]. Catalysis Today, 2015, 249: 184-191.
45	YIN R L, GUO W Q, DU J S, et al. Heteroatoms doped graphene for catalytic ozonation of sulfamethoxazole by metal-free catalysis: performances and mechanisms[J]. Chemical Engineering Journal, 2017, 317: 632-639.
46	WANG Q, LI L, LUO L, et al. Activation of persulfate with dual-doped reduced graphene oxide for degradation of alkylphenols[J]. Chemical Engineering Journal, 2019, 376: 120891.
47	TIAN W J, ZHANG H Y, DUAN X G, et al. Nitrogen-and sulfur-codoped hierarchically porous carbon for adsorptive and oxidative removal of pharmaceutical contaminants[J]. ACS Applied Materials and Interfaces, 2016, 8(11): 7184-7193.
48	SUN H Q, WANG Y X, LIU S Z, et al. Facile synthesis of nitrogen doped reduced graphene oxide as a superior metal-free catalyst for oxidation[J]. Chemical Communications, 2013, 49(85): 9914-9916.
49	MA W J, WANG N, TONG T Z, et al. Nitrogen, phosphorus, and sulfur tri-doped hollow carbon shells derived from ZIF-67@poly (cyclotriphosphazene-co-4,4′-sulfonyldiphenol) as a robust catalyst of peroxymonosulfate activation for degradation of bisphenol A[J]. Carbon, 2018, 137: 291-303.
1	WANG J L, WANG S Z. Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants[J]. Chemical Engineering Journal, 2018, 334: 1502-1517.
2	CHEN X, OH W D, LIM T T. Graphene- and CNTs-based carbocatalysts in persulfates activation: material design and catalytic mechanisms[J]. Chemical Engineering Journal, 2018, 354: 941-976.
3	GHANBARI F, MORADI M. Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants: review[J]. Chemical Engineering Journal, 2017, 310: 41-62.
50	WANG G L, CHEN S, QUAN X, et al. Enhanced activation of peroxymonosulfate by nitrogen doped porous carbon for effective removal of organic pollutants[J]. Carbon, 2017, 115: 730-739.
51	DUAN X G, AO Z M, SUN H Q, et al. Nitrogen-doped graphene for generation and evolution of reactive radicals by metal-free catalysis[J]. ACS Applied Materials and Interfaces, 2015, 7(7): 4169-4178.
52	LIANG P, ZHANG C, DUAN X G, et al. N-doped graphene from metal-organic frameworks for catalytic oxidation of p-hydroxylbenzoic acid: N-functionality and mechanism[J]. ACS Sustainable Chemistry and Engineering, 2017, 5(3): 2693-2701.
53	LIANG P, ZHANG C, DUAN X G, et al. An insight into metal organic framework derived N-doped graphene for the oxidative degradation of persistent contaminants: formation mechanism and generation of singlet oxygen from peroxymonosulfate[J]. Environmental Science: Nano, 2017, 4(2): 315-324.
54	LIU H, SUN P, FENG M B, et al. Nitrogen and sulfur co-doped CNT-COOH as an efficient metal-free catalyst for the degradation of UV filter BP-4 based on sulfate radicals[J]. Applied Catalysis B: Environmental, 2016, 187: 1-10.
55	YANG L, ZENG X F, WANG W C, et al. Recent progress in MOF-derived, heteroatom-doped porous carbons as highly efficient electrocatalysts for oxygen reduction reaction in fuel cells[J]. Advanced Functional Materials, 2018, 28(7): 1704537.
56	REN Q, WANG H, LU X F, et al. Recent progress on MOF-derived heteroatom-doped carbon-based electrocatalysts for oxygen reduction reaction[J]. Advanced Science, 2018, 5(3): 1700515.
57	WANG N, MA W J, REN Z Q, et al. Prussian blue analogues derived porous nitrogen-doped carbon microspheres as high-performance metal-free peroxymonosulfate activators for non-radical-dominated degradation of organic pollutants[J]. Journal of Materials Chemistry A, 2018, 6(3): 884-895.
58	WANG N, MA W J, REN Z Q, et al. Template synthesis of nitrogen-doped carbon nanocages-encapsulated carbon nanobubbles as catalyst for activation of peroxymonosulfate[J]. Inorganic Chemistry Frontiers, 2018, 5(8): 1849-1860.
59	HUO X W, ZHOU P, ZHANG J, et al. N, S-doped porous carbons for persulfate activation to remove tetracycline: nonradical mechanism[J]. Journal of Hazardous Materials, 2020, 391: 122055.
60	SUN P, LIU H, ZHAI Z C, et al. Degradation of UV filter BP-1 with nitrogen-doped industrial graphene as a metal-free catalyst of peroxymonosulfate activation[J]. Chemical Engineering Journal, 2019, 356: 262-271.
4	DUAN X G, INDRAWIRAWAN S, KANG J, et al. Synergy of carbocatalytic and heat activation of persulfate for evolution of reactive radicals toward metal-free oxidation[J], Catalysis Today, 2020, 355: 319-324.
5	HUANG K C, ZHAO Z Q, HOAG G E, et al. Degradation of volatile organic compounds with thermally activated persulfate oxidation[J]. Chemosphere, 2005, 61(4): 551-560.
6	AO X W, LIU W J. Degradation of sulfamethoxazole by medium pressure UV and oxidants: peroxymonosulfate, persulfate, and hydrogen peroxide[J]. Chemical Engineering Journal, 2017, 313: 629-637.
7	XU L J, WANG X T, SUN Y, et al. Mechanistic study on the combination of ultrasound and peroxymonosulfate for the decomposition of endocrine disrupting compounds[J]. Ultrasonics Sonochemistry, 2020, 60: 104749.
8	CHUA C K, PUMERA M. Carbocatalysis: the state of “metal-free” catalysis[J]. Chemistry, 2015, 21(36): 12550-12562.
9	HOU J F, YANG S S, WAN H Q, et al. Highly effective catalytic peroxymonosulfate activation on N-doped mesoporous carbon for o-phenylphenol degradation[J]. Chemosphere, 2018, 197: 485-493.
10	MANDAL S, BERA T, DUBEY G, et al. Uses of K₂S₂O₈ in metal catalyzed and metal free oxidative transformations[J]. ACS Catalysis, 2018, 8(6): 5085-5144.
11	DUAN X G, SUN H Q, KANG J, et al. Insights into heterogeneous catalysis of persulfate activation on dimensional-structured nanocarbons[J]. ACS Catalysis, 2015, 5(8): 4629-4636.
12	陈一萍, 夏管商, 郑朝洪, 等. CNTs/PMS高级氧化体系去除水中的环丙沙星[J]. 化工进展， 2019, 38(4): 2037-2045.
	CHEN Y P, XIA G S, ZHENG C H, et al. Degradation of ciprofloxacin by advanced oxidation process with carbon nanotubes/peroxymonosulfate CNTs/PMS[J]. Chemical Industry and Engineering Progress, 2019, 38(4): 2037-2045.
13	YUN E T, YOO H Y, BAE H, et al. Exploring the role of persulfate in the activation process: radical precursor versus electron acceptor[J]. Environmental Science and Technology, 2017, 51(17): 10090-10099.
14	CHENG X, GUO H G, ZHANG Y L, et al. Insights into the mechanism of nonradical reactions of persulfate activated by carbon nanotubes: activation performance and structure-function relationship[J]. Water Research, 2019, 157: 406-414.
15	ZHAO Q, MAO Q, ZHOU Y, et al. Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: a review on heterogeneous catalysts and applications[J]. Chemosphere, 2017, 189: 224-238.
16	OH W D, DONG Z L, Q, LIM T T, et al. Generation of sulfate radical through heterogeneous catalysis for organic contaminants removal: current development, challenges and prospects[J]. Applied Catalysis B: Environmental, 2016, 194: 169-201.
17	LI Y, LIU L D, LIU L, et al. Efficient oxidation of phenol by persulfate using manganite as a catalyst[J]. Journal of Molecular Catalysis A: Chemical, 2016, 411, 264-271.
18	SUN B J, MA W J, WANG N, et al. Polyaniline: a new metal-free catalyst for peroxymonosulfate activation with highly efficient and durable removal of organic pollutants[J]. Environmental Science and Technology, 2019, 53: 9771-9780.
19	RESHETNYAK O V, KOVAL’CHUK E P, SKURSKI P, et al. The origin of luminescence accompanying electrochemical reduction or chemical decomposition of peroxydisulfates[J]. Journal of Luminescence, 2003, 105(1): 27-34.
20	HUANG B C, JIANG J, HUANG G X, et al. Sludge biochar-based catalysts for improved pollutant degradation by activating peroxymonosulfate[J]. Journal of Materials Chemistry A, 2018, 6(19): 8978-8985.
21	WEI M Y, GAO L, LI J, et al. Activation of peroxymonosulfate by graphitic carbon nitride loaded on activated carbon for organic pollutants degradation[J]. Journal of Hazardous Materials, 2016, 316: 60-68.
22	SUN P, LIU H, FENG M B, et al. Nitrogen-sulfur co-doped industrial graphene as an efficient peroxymonosulfate activator: singlet oxygen-dominated catalytic degradation of organic contaminants[J]. Applied Catalysis B: Environmental, 2019, 251: 335-345.
23	CHENG X, GUO H G, ZHANG Y L, et al. Non-photochemical production of singlet oxygen via activation of persulfate by carbon nanotubes[J]. Water Research, 2017, 113: 80-88.
24	HOU J F, XU L X, HAN Y X, et al. Deactivation and regeneration of carbon nanotubes and nitrogen-doped carbon nanotubes in catalytic peroxymonosulfate activation for phenol degradation: variation of surface functionalities[J]. RSC Advances, 2019, 9(2): 974-983.
25	HU P D, SU H R, CHEN Z Y, et al. Selective degradation of organic pollutants using an efficient metal-free catalyst derived from carbonized polypyrrole via peroxymonosulfate activation[J]. Environmental Science and Technology, 2017, 51(19): 11288-11296.
26	HAN C, DUAN X G, ZHANG M J, et al. Role of electronic properties in partition of radical and nonradical processes of carbocatalysis toward peroxymonosulfate activation[J]. Carbon, 2019, 153: 73-80.
27	LEE H, LEE H J, JEONG J, et al. Activation of persulfates by carbon nanotubes: oxidation of organic compounds by nonradical mechanism[J]. Chemical Engineering Journal, 2015, 266: 28-33.
28	TANG L, LIU Y N, WANG J J, et al. Enhanced activation process of persulfate by mesoporous carbon for degradation of aqueous organic pollutants: electron transfer mechanism[J]. Applied Catalysis B: Environmental, 2018, 231: 1-10.
29	DUAN X G, O'DONNELL K, SUN H Q, et al. Sulfur and nitrogen co-doped graphene for metal-free catalytic oxidation reactions[J]. Small, 2015, 11(25): 3036-3044.
30	YUN E T, MOON G H, LEE H, et al. Oxidation of organic pollutants by peroxymonosulfate activated with low-temperature-modified nanodiamonds: understanding the reaction kinetics and mechanism[J]. Applied Catalysis B: Environmental, 2018, 237: 432-441.
31	WANG X B, TANG P, DING C, et al. Simultaneous enhancement of adsorption and peroxymonosulfate activation of nitrogen-doped reduced graphene oxide for bisphenol A removal[J]. Journal of Environmental Chemical Engineering, 2017, 5(5): 4291-4297.
32	WANG J, DUAN X G, DONG Q, et al. Facile synthesis of N-doped 3D graphene aerogel and its excellent performance in catalytic degradation of antibiotic contaminants in water[J]. Carbon, 2019, 144: 781-790.
33	LI D G, DUAN X G, SUN H Q, et al. Facile synthesis of nitrogen-doped graphene via low-temperature pyrolysis: the effects of precursors and annealing ambience on metal-free catalytic oxidation[J]. Carbon, 2017, 115: 649-658.
34	DUAN X G, AO Z M, LI D G, et al. Surface-tailored nanodiamonds as excellent metal-free catalysts for organic oxidation[J]. Carbon, 2016, 103: 404-411.
35	CHEN X, DUAN X G, OH W D, et al. Insights into nitrogen and boron-co-doped graphene toward high-performance peroxymonosulfate activation: maneuverable N-B bonding configurations and oxidation pathways[J]. Applied Catalysis B: Environmental, 2019, 253: 419-432.
36	PAN X X, CHEN J, WU N N, et al. Degradation of aqueous 2,4,4″-trihydroxybenzophenone by persulfate activated with nitrogen doped carbonaceous materials and the formation of dimer products[J]. Water Research, 2018, 143: 176-187.
37	SUN H Q, KWAN C K, SUVOROVA A, et al. Catalytic oxidation of organic pollutants on pristine and surface nitrogen-modified carbon nanotubes with sulfate radicals[J]. Applied Catalysis B: Environmental, 2014, 154/155: 134-141.

单一杂原子掺杂碳材料	掺杂方法	碳基体 /前体	掺杂元素	杂原子源	活化过硫酸盐降解有机污染物效果				机理^①	文献
单一杂原子掺杂碳材料	掺杂方法	碳基体 /前体	掺杂元素	杂原子源	催化剂浓度 /mg·L^-1	过硫酸盐投加量	污染物浓度	降解效果	机理^①	文献
N-SWCNT	液相	SWCNT	N	尿素	200	2.0g·L^-1 PDS	20mg·kg^-1 硝基苯	60min，100%	R	[4]
NMC-850	液相	SBA-15	N	乙二胺和双氰胺	50	1.25g·L^-1 PMS	30mg·L^-1 邻苯基苯酚	150min，81%	¹O₂	[9]
NCNT-550	液相	CNT	N	尿素	100	8mmol·L^-1 PMS	0.106mmol·L^-1 苯酚	20min，100%	¹O₂	[24]
N-ND/PDDA/GO	液相	ND/PDDA/GO	N	NH₃	100	1mmol·L^-1 PMS	0.1mmol·L^-1 4-CP	60min，100%	E	[30]
N-RGO	液相	rGO	N	氨溶液	120	0.8mmol·L^-1 PMS	88mg·L^-1 BPA	7min，100%	R	[31]
N-rGO	液相	rGO	N	三聚氰胺	50	2g·L^-1 PMS	20mg·L^-1 IBP	180min，90%	R	[32]
N-rGO-N₂	液相	rGO	N	尿素	400	6.5mmol·L^-1 PMS	20mg·kg^-1 苯酚	20min，100%	R+¹O₂	[33]
N-AND	液相	AND	N	三聚氰胺	200	6.5mmol·L^-1 PMS	20mg·L^-1 苯酚	45min，100%	R	[34]
N-CNT-35	液相	CNT	N	硝酸铵	200	2g·L^-1 PMS	20mg·kg^-1 苯酚	45min，100%	R	[37]
NoCNT-700	液相	SWCNTs	N	三聚氰胺	100	6.5mmol·L^-1 PMS	20mg·kg^-1 苯酚	20min，100%	R+E	[38]
NG350	液相	rGO	N	硝酸铵	200	2g·L^-1 PMS	20mg·kg^-1 苯酚	180min，85%	R	[44]
G-N	液相	GO	N	硝酸铵	200	2g·L^-1 PMS	20mg·kg^-1 苯酚	45min，100%	—	[48]
NG-700	液相	rGO	N	三聚氰胺	100	6.5mmol·L^-1 PMS	20mg·kg^-1 苯酚	30min，100%	R	[51]
N-G(D)N-G(M) N-G(M)	液相	MIL-100	N	双氰胺三聚氰胺尿素	100	3.25mmol·L^-1 PMS	20mg·kg^-1 PHBA	20min，100% 30min，100% 90min，100%	¹O₂	[52]
N-G(D)	液相	MIL-100	N	双氰胺	100	3.25mmol·L^-1 PMS	50mg·kg^-1 苯酚	30min，100%	¹O₂	[53]
NH₄NO₃-CNT-OH	固相	CNT-OH (0.5∶1)	N	硝酸	100	污染物∶[PDS]= 1∶500	43.48mmol·L^-1 2,4,4-HBP	120min，100%	R	[36]
N-IrGO	固相	IrGO	N	尿素	50	500mg·L^-1 PMS	5mg·L^-1 二苯甲酮-1	60min，100%	¹O₂	[60]
CPPy-F-8	原位	PPy-F	N	聚吡咯	100	3.25mmol·L^-1 PMS	20mg·L^-1 苯酚	120min，97%	R+¹O₂	[25]
NPC-800	原位	ZIF-8	N	2-甲基咪唑	200	0.8g·L^-1 PMS	25mg·L^-1 苯酚	60min，86.1%	R	[39]
N-C-900	原位	ZIF-8	N	2-甲基咪唑	150	5mmol·L^-1 PDS	0.3mmol·L^-1 PCA	120min，＞96.3%	R+¹O₂+E	[40]
ACS-800	原位	聚噻吩	S	噻吩	50	8mmol·L^-1 PDS	40mg·L^-1 4-CP	60min，100%	R	[41]
SDAC-800	原位	聚噻吩	S	噻吩	100	15mmol·L^-1 PDS	80mg·L^-1 4-CP	90min，100%	R+E	[42]
B-OMC	液相	酚醛树脂	B	硼酸	200	1?mmol·L^-1 PMS	20mg·L^-1 BPA	60min，91%	¹O₂	[43]
NPCs	原位	ZIF-8	N	2-甲基咪唑	200	1.6mmol·L^-1 PMS	20mg·kg^-1 苯酚	60min，100%	R	[50]
PNC-800	原位	Zn-Co PBAs	N	钴氰化钾	100	1.0g·L^-1 PMS	100mg·L^-1 MB	10min，100%	R+¹O₂	[57]
CBs@NCCs	原位	Co-Fe PBAs	N	钴氰化钾	60	1.0g·L^-1 PMS	100mg·L^-1 MB	60min，＞95%	R+¹O₂	[58]

单一杂原子掺杂碳材料	掺杂方法	碳基体 /前体	掺杂元素	杂原子源	活化过硫酸盐降解有机污染物效果				机理^①	文献
单一杂原子掺杂碳材料	掺杂方法	碳基体 /前体	掺杂元素	杂原子源	催化剂浓度 /mg·L^-1	过硫酸盐投加量	污染物浓度	降解效果	机理^①	文献
N-SWCNT	液相	SWCNT	N	尿素	200	2.0g·L^-1 PDS	20mg·kg^-1 硝基苯	60min，100%	R	[4]
NMC-850	液相	SBA-15	N	乙二胺和双氰胺	50	1.25g·L^-1 PMS	30mg·L^-1 邻苯基苯酚	150min，81%	¹O₂	[9]
NCNT-550	液相	CNT	N	尿素	100	8mmol·L^-1 PMS	0.106mmol·L^-1 苯酚	20min，100%	¹O₂	[24]
N-ND/PDDA/GO	液相	ND/PDDA/GO	N	NH₃	100	1mmol·L^-1 PMS	0.1mmol·L^-1 4-CP	60min，100%	E	[30]
N-RGO	液相	rGO	N	氨溶液	120	0.8mmol·L^-1 PMS	88mg·L^-1 BPA	7min，100%	R	[31]
N-rGO	液相	rGO	N	三聚氰胺	50	2g·L^-1 PMS	20mg·L^-1 IBP	180min，90%	R	[32]
N-rGO-N₂	液相	rGO	N	尿素	400	6.5mmol·L^-1 PMS	20mg·kg^-1 苯酚	20min，100%	R+¹O₂	[33]
N-AND	液相	AND	N	三聚氰胺	200	6.5mmol·L^-1 PMS	20mg·L^-1 苯酚	45min，100%	R	[34]
N-CNT-35	液相	CNT	N	硝酸铵	200	2g·L^-1 PMS	20mg·kg^-1 苯酚	45min，100%	R	[37]
NoCNT-700	液相	SWCNTs	N	三聚氰胺	100	6.5mmol·L^-1 PMS	20mg·kg^-1 苯酚	20min，100%	R+E	[38]
NG350	液相	rGO	N	硝酸铵	200	2g·L^-1 PMS	20mg·kg^-1 苯酚	180min，85%	R	[44]
G-N	液相	GO	N	硝酸铵	200	2g·L^-1 PMS	20mg·kg^-1 苯酚	45min，100%	—	[48]
NG-700	液相	rGO	N	三聚氰胺	100	6.5mmol·L^-1 PMS	20mg·kg^-1 苯酚	30min，100%	R	[51]
N-G(D)N-G(M) N-G(M)	液相	MIL-100	N	双氰胺三聚氰胺尿素	100	3.25mmol·L^-1 PMS	20mg·kg^-1 PHBA	20min，100% 30min，100% 90min，100%	¹O₂	[52]
N-G(D)	液相	MIL-100	N	双氰胺	100	3.25mmol·L^-1 PMS	50mg·kg^-1 苯酚	30min，100%	¹O₂	[53]
NH₄NO₃-CNT-OH	固相	CNT-OH (0.5∶1)	N	硝酸	100	污染物∶[PDS]= 1∶500	43.48mmol·L^-1 2,4,4-HBP	120min，100%	R	[36]
N-IrGO	固相	IrGO	N	尿素	50	500mg·L^-1 PMS	5mg·L^-1 二苯甲酮-1	60min，100%	¹O₂	[60]
CPPy-F-8	原位	PPy-F	N	聚吡咯	100	3.25mmol·L^-1 PMS	20mg·L^-1 苯酚	120min，97%	R+¹O₂	[25]
NPC-800	原位	ZIF-8	N	2-甲基咪唑	200	0.8g·L^-1 PMS	25mg·L^-1 苯酚	60min，86.1%	R	[39]
N-C-900	原位	ZIF-8	N	2-甲基咪唑	150	5mmol·L^-1 PDS	0.3mmol·L^-1 PCA	120min，＞96.3%	R+¹O₂+E	[40]
ACS-800	原位	聚噻吩	S	噻吩	50	8mmol·L^-1 PDS	40mg·L^-1 4-CP	60min，100%	R	[41]
SDAC-800	原位	聚噻吩	S	噻吩	100	15mmol·L^-1 PDS	80mg·L^-1 4-CP	90min，100%	R+E	[42]
B-OMC	液相	酚醛树脂	B	硼酸	200	1?mmol·L^-1 PMS	20mg·L^-1 BPA	60min，91%	¹O₂	[43]
NPCs	原位	ZIF-8	N	2-甲基咪唑	200	1.6mmol·L^-1 PMS	20mg·kg^-1 苯酚	60min，100%	R	[50]
PNC-800	原位	Zn-Co PBAs	N	钴氰化钾	100	1.0g·L^-1 PMS	100mg·L^-1 MB	10min，100%	R+¹O₂	[57]
CBs@NCCs	原位	Co-Fe PBAs	N	钴氰化钾	60	1.0g·L^-1 PMS	100mg·L^-1 MB	60min，＞95%	R+¹O₂	[58]

杂原子共掺杂碳材料	掺杂方法	碳基体 /前体	掺杂元素	杂原子源	活化过硫酸盐降解有机污染物效果				机理^①	文献
杂原子共掺杂碳材料	掺杂方法	碳基体 /前体	掺杂元素	杂原子源	催化剂浓度 /mg·L^-1	过硫酸盐投加量	污染物浓度	降解效果	机理^①	文献
SNG	液相	rGO	N，S	N：硝酸铵 S：二甲基亚砜	200	6.5mmol·L^-1 PMS	20mg·kg^-1 苯酚	90min，100%	R	[29]
2sNBG-800	液相	rGO	N，B	N：尿素 B：硼酸	200	0.5mmol·L^-1 PMS	10mg·L^-1 SAM	20min，100%	R+E	[35]
N-S-PCs	液相	葡萄糖	N，S	NS：硫脲	50	6.5mmol·L^-1 PDS	20mg·L^-1 磺胺氯哒嗪	20min，100%	R+E	[47]
NPSC-700	液相	ZIF-8	N，P，S	NPS：聚丙腈	60	0.4g·L^-1 PMS	25mg·kg^-1 BPA	30min，90.10%	R	[49]
SNCs	液相	咖啡粉	N，S	NS：L-半胱氨酸	400	2mmol·L^-1 PDS	0.02mmol·L^-1 TeC	60min，100%	¹O₂+E	[59]
i-RGO-NS	固相	rGO	N，S	NS：硫脲	20	307mg·L^-1 PMS	15mg·L^-1 MP	20min，100%	¹O₂	[22]
N,S-rGO	固相	rGO	N，S	NS：硫脲	50	0.9mmol·L^-1 PDS	2mg·L^-1 BPA	20min，100%	R	[46]
NS-CNT-COOH	固相	CNT	N，S	NS：硫脲	100	1.0g·L^-1 PMS	0.01g·L^-1 BP-4	30min，100%	E	[54]

杂原子共掺杂碳材料	掺杂方法	碳基体 /前体	掺杂元素	杂原子源	活化过硫酸盐降解有机污染物效果				机理^①	文献
杂原子共掺杂碳材料	掺杂方法	碳基体 /前体	掺杂元素	杂原子源	催化剂浓度 /mg·L^-1	过硫酸盐投加量	污染物浓度	降解效果	机理^①	文献
SNG	液相	rGO	N，S	N：硝酸铵 S：二甲基亚砜	200	6.5mmol·L^-1 PMS	20mg·kg^-1 苯酚	90min，100%	R	[29]
2sNBG-800	液相	rGO	N，B	N：尿素 B：硼酸	200	0.5mmol·L^-1 PMS	10mg·L^-1 SAM	20min，100%	R+E	[35]
N-S-PCs	液相	葡萄糖	N，S	NS：硫脲	50	6.5mmol·L^-1 PDS	20mg·L^-1 磺胺氯哒嗪	20min，100%	R+E	[47]
NPSC-700	液相	ZIF-8	N，P，S	NPS：聚丙腈	60	0.4g·L^-1 PMS	25mg·kg^-1 BPA	30min，90.10%	R	[49]
SNCs	液相	咖啡粉	N，S	NS：L-半胱氨酸	400	2mmol·L^-1 PDS	0.02mmol·L^-1 TeC	60min，100%	¹O₂+E	[59]
i-RGO-NS	固相	rGO	N，S	NS：硫脲	20	307mg·L^-1 PMS	15mg·L^-1 MP	20min，100%	¹O₂	[22]
N,S-rGO	固相	rGO	N，S	NS：硫脲	50	0.9mmol·L^-1 PDS	2mg·L^-1 BPA	20min，100%	R	[46]
NS-CNT-COOH	固相	CNT	N，S	NS：硫脲	100	1.0g·L^-1 PMS	0.01g·L^-1 BP-4	30min，100%	E	[54]

[1]	CHENG Tao, CUI Ruili, SONG Junnan, ZHANG Tianqi, ZHANG Yunhe, LIANG Shijie, PU Shi. Analysis of impurity deposition and pressure drop increase mechanisms in residue hydrotreating unit [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4616-4627.
[2]	WANG Jingang, ZHANG Jianbo, TANG Xuejiao, LIU Jinpeng, JU Meiting. Research progress on modification of Cu-SSZ-13 catalyst for denitration of automobile exhaust gas [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4636-4648.
[3]	GE Quanqian, XU Mai, LIANG Xian, WANG Fengwu. Research progress on the application of MOFs in photoelectrocatalysis [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4692-4705.
[4]	BAI Zhihua, ZHANG Jun. Oxidative removal of NO in DTPMPA/Fenton system [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4967-4973.
[5]	ZHANG Yaojie, ZHANG Chuanxiang, SUN Yue, ZENG Huihui, JIA Jianbo, JIANG Zhendong. Application of coal-based graphene quantum dots in supercapacitors [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4340-4350.
[6]	CHU Tiantian, LIU Runzhu, DU Gaohua, MA Jiahao, ZHANG Xiao’a, WANG Chengzhong, ZHANG Junying. Preparation and chemical degradability of organoguanidine-catalyzed dehydrogenation type RTV silicone rubbers [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3664-3673.
[7]	XU Peiyao, CHEN Biaoqi, KANKALA Ranjith Kumar, WANG Shibin, CHEN Aizheng. Research progress of nanomaterials for synergistic ferroptosis anticancer therapy [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3684-3694.
[8]	LI Yanling, ZHUO Zhen, CHI Liang, CHEN Xi, SUN Tanglei, LIU Peng, LEI Tingzhou. Research progress on preparation and application of nitrogen-doped biochar [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3720-3735.
[9]	XU Wei, LI Kaijun, SONG Linye, ZHANG Xinghui, YAO Shunhua. Research progress of photocatalysis and co-electrochemical degradation of VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3520-3531.
[10]	GONG Pengcheng, YAN Qun, CHEN Jinfu, WEN Junyu, SU Xiaojie. Properties and mechanism of eriochrome black T degradation by carbon nanotube-cobalt ferrite composites activated persulfate [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3572-3581.
[11]	YANG Jiatian, TANG Jinming, LIANG Zirong, LI Yinhong, HU Huayu, CHEN Yuan. Preparation and application of novel starch-based super absorbent polymer dust suppressant [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3187-3196.
[12]	WANG Jiuheng, RONG Nai, LIU Kaiwei, HAN Long, SHUI Taotao, WU Yan, MU Zhengyong, LIAO Xuqing, MENG Wenjia. Enhanced CO₂ capture performance and strength of cellulose-templated CaO-based pellets with steam reactivation [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3217-3225.
[13]	WU Fengzhen, LIU Zhiwei, XIE Wenjie, YOU Yating, LAI Rouqiong, CHEN Yandan, LIN Guanfeng, LU Beili. Preparation of biomass derived Fe/N co-doped porous carbon and its application for catalytic degradation of Rhodamine B via peroxymonosulfate activation [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3292-3301.
[14]	YANG Hongmei, GAO Tao, YU Tao, QU Chengtun, GAO Jiapeng. Treatment of refractory organics sulfonated phenolic resin with ferrate [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3302-3308.
[15]	HE Chuan, WU Guoxun, LI Ang, ZHANG Fajie, BIAN Zijun, LU Chengzheng, WANG Lipeng, ZHAO Min. Characteristics of calcium and magnesium deactivation and regeneration of waste incineration SCR catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2413-2420.