Single-atom iron catalysts for peroxymonosulfate-based advanced oxidation processes: Coordination structure versus reactive species

doi:10.1016/S1872-2067(23)64611-X

Chinese Journal of Catalysis ›› 2024, Vol. 59: 15-37.DOI: 10.1016/S1872-2067(23)64611-X

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Single-atom iron catalysts for peroxymonosulfate-based advanced oxidation processes: Coordination structure versus reactive species

Cheng Cheng^a^,^b, Wei Ren^b, Hui Zhang^a^,^*(), Xiaoguang Duan^b^,^*(), Shaobin Wang^b^,^*()

^aDepartment of Environmental Science and Engineering, School of Resource and Environmental Sciences, Wuhan University, Wuhan 430079, Hubei, China
^bSchool of Chemical Engineering, The University of Adelaide, Adelaide, SA 5005, Australia

Received:2023-12-30 Accepted:2024-01-23 Online:2024-04-18 Published:2024-04-15
Contact: *E-mail: eeng@whu.edu.cn (H. Zhang), xiaoguang.duan@adelaide.edu.au (X. Duan), shaobin.wang@adelaide.edu.au (S.Wang).
About author:Hui Zhang (School of Resource and Environmental Sciences, Wuhan University) received his Ph.D. degree from South China University of Technology (China) in 1995. Since then, he has been working at Wuhan University and is currently a professor. His research interests focus on environmental chemistry, environmental catalysis and advanced oxidation technologies for environmental remediation. He has published more than 180 refereed journal papers with citation over 18000 and H-index of 77. He was recognized as highly cited researcher (Cross-Field) in 2022 and 2023 by Clarivate and was in the list of highly cited Chinese authors (Environmental Science and Engineering) by Elsevier in 2020, 2021 and 2022. He served as a member of the editorial board of Journal of Hazardous Materials.
Xiaoguang Duan (School of Chemical Engineering, The University of Adelaide, Australia) received his Ph.D. degree from Curtin University in 2016. He is currently an Associate Professor and ARC DECRA Fellow (2021) & ARC Future Fellow (2024). His research areas focus on environmental science, green catalysis, functional materials, advanced water purification technologies, and computational science. He has published over 300 peer-reviewed research papers including over 70 ESI Highly Cited Papers (1%). His publications received >32000 citations and H-index of 93. Based on research excellence, he was awarded the ACS Catalysis ECR Award, and JMCA Emerging Investigator Award. He was awarded the MIT Technology Review Innovators Under 35 (MIT IU35, Asian Pacific) in 2021 and ES&T James J. Morgan Award in 2022. He was recognized as the Global Highly Cited Researcher (Clarivate Analytics) in two fields of 'Environment/Ecology' and 'Chemistry' in 2022-2023, and in 'Cross-Field' in 2020-2021.
Shaobin Wang (School of Chemical Engineering, The University of Adelaide, Australia) received his B. Sc degree from Peking University (China), and Ph.D. degree from The University of Queensland (Australia). He is now a Professor and ARC Laureate Fellow (2023). His research interests focus on nanomaterial synthesis and application for adsorption and catalysis, fuel and energy conversion and environmental remediation. He has published more than 700 refereed journal papers with citation over 88000 and H-index of 164. He was awarded 2012 Thomson Reuters Citation & Innovation Awards in Australia. He is also the Clarivate Analytics Highly Cited Researcher in 'Engineering', and ‘Chemistry’ and 'Environment/Ecology' for 2016-2022. He also served as the editor of Applied Catalysis B, Chemical Engineering Journal Advances, and Journal of Colloid and Interface Science.
Supported by:
The Australian Research Council(DP230102406);The National Natural Science Foundation of China(22061132001);The National Natural Science Foundation of China(52100090);The China Scholarship Council for a one-year research grant at The University of Adelaide(202106270136)

Abstract

Abstract:

Heterogeneous peroxymonosulfate (PMS)-based oxidation technology for water treatment requires innovative catalysts for efficient and selective production of desired reactive oxygen species (ROS), such as free radicals, singlet oxygen, catalyst-PMS* complexes, and high-valent metal-oxo species. Single-atom catalysts are featured with the maximized atom utilization as well as uniform and well-defined active sites, holding a great promise for effective and selective PMS activation. However, the structure-activity/selectivity relationships have not yet been well revealed owing to multiple ROS generation pathways and their complex interplay. Herein, we focus on the mechanisms of PMS activation by single-atom iron catalysts and identify the relationships of the geometric and electronic structures of single atom Fe centers to selective production of different reactive species/pathways. Moreover, in situ/operando techniques to monitor the dynamic evolution of active sites under practical working conditions and design of binuclear metal sites for synergistic catalysis will also be discussed.

Key words: Peroxymonosulfate activation, Single-atom iron catalyst, Radical, Nonradical, Water treatment, Environmental remediation

Cheng Cheng, Wei Ren, Hui Zhang, Xiaoguang Duan, Shaobin Wang. Single-atom iron catalysts for peroxymonosulfate-based advanced oxidation processes: Coordination structure versus reactive species[J]. Chinese Journal of Catalysis, 2024, 59: 15-37.

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Support	Synthetic method	Structure (l_M-N)	Loading (wt%)	PMS conc. Cat. dosage	Pollutant (Conc.)	k_obs (min^-1)	Reactive species	Ref.
N-C	pyrolysis of Fe(OAc)₂-phen complex anchored O-g-C₃N₄ in N₂ at 600 °C	Fe-N₄ (2.00 Å) Fe-Fe N-pyridinic	—	0.4 mmol L^-1 0.1 g L^-1	SMX (10 mg L^-1)	0.24	Surface-bond SO₄^•-/^•OH, ¹O₂	[108]
N-C	pyrolysis of mixture of Fe(acac)₃anchored carbon and DCD in N₂ at 900 °C	Fe-N₄ (2.04 Å) Fe-Fe, N-pyridinic, Fe^II	9.0	0.4 mmol L^-1 0.1 g L^-1	BPA (11.4 mg L^-1)	0.44	SO₄^•-, ^•OH, ¹O₂	[109]
N-C	pyrolysis of FeCl₃ anchored pyrrole-phytic acid hydrogel in N₂ at 700 °C and acid leaching	Fe-N₃-P₁, N-pyridinic, Fe^II	2.32	0.65 mmol L^-1 0.1 g L^-1	BPA (20 mg L^-1)	0.8	SO₄^•-, ^•OH, O₂^•-, ¹O₂	[110]
N-C	pyrolysis of Fe(OAc)₂-phen complex anchored carbon black in N₂ at 600 °C	Fe-N₄ (2.04 Å), N-pyrrolic, Fe^II	1.42	1.5 mmol L^-1 0.1 g L^-1	ACP (7.6 mg L^-1)	—	SO₄^•-, ^•OH	[111]
N-CNT	pyrolysis of mixture of Fe₂(SO₄)₃, melamine, and O-CNT in N₂ at 800 °C and acid leaching	Fe-N₃ (1.97 Å), Fe-Fe N-pyridinic, Fe^II	1.45	0.65 mmol L^-1 0.2 g L^-1	PE (9.4 mg L^-1)	2.59	SO₄^•-, ^•OH	[112]
N-C	pyrolysis of PPh₃ encapsulated Fe-doped ZIF-8 in Ar at 900 °C and acid leaching	Fe-N₃-P₁, Fe-N: 1.90 Å, Fe-P: 2.26 Å, N-pyridinic, Fe^II	0.77	0.5 mmol L^-1 0.1 g L^-1	BPA (10 mg L^-1)	0.397	^•OH	[113]
N-C	pyrolysis of mixture of FePc anchored polystyrene and urea in Ar at 350 and 550 °C	Fe-N₄, N-pyridinic, Fe^II	2.44	1 mmol L^-1 0.03 g L^-1	CP (1.3 mg L^-1)	1.663	O₂^•-, ¹O₂	[114]
N-C	CVD of the pyridine on ferrocene anchored CaO in Ar at 700 °C and acid leaching	Fe-N₄ (1.95 Å), N-pyridinic, Fe^II	0.61	3.25 mmol L^-1 0.025 g L^-1	PE (50 mg L^-1)	2.139	O₂^•-	[115]
N-C	CVD of mixture of Fe(acac)₃ and pyridine on Mg(OH)₂ in Ar at 800 °C and acid leaching	Fe-N₄ (1.99 Å), N-pyridinic, Fe^II	1.23	0.3 mmol L^-1 0.03 g L^-1	SMX (10 mg L^-1)	0.815	O₂^•-	[116]
N-C	pyrolysis of mixture of FeCl₃, glucose, and DCD in Ar at 900 °C	Fe-N₄ (1.97 Å), N-pyridinic, Fe^II	2.45	1 mmol L^-1 0.05 g L^-1	NP (20 mg L^-1)	0.302	O₂^•-, ¹O₂	[117]
N-C	pyrolysis of FeCl₂ and ZnCl₂ anchored silk fibroin in Ar at 900 °C and acid leaching	Fe-N₄, N-pyridinic, Fe^II	0.57	15 mmol L^-1 0.1 g L^-1	BPA (50 mg L^-1)	1.952	O₂^•-, ¹O₂	[118]
N-C	pyrolysis of FeCl₃ anchored COF (TpPa) in N₂ at 700 °C	Fe-N_x	2.14	0.65 mmol L^-1 0.1 g L^-1	Orange II (20 mg L^-1)	—	¹O₂	[119]
N-C	pyrolysis of Fe(acac)₃-phen complex anchored ZIF-8 derived carbon in Ar at 600 °C	Fe-N₄ (1.97 Å), N-pyridinic, Fe^II	0.71	1.3 mmol L^-1 0.2 g L^-1	BPA (25 mg L^-1)	0.104	¹O₂	[27]
N-C	pyrolysis of Fe(acac)₃ encapsulated ZIF-8 in N₂ at 900 °C and acid leaching	Fe-N_x	0.56	0.65 mmol L^-1 0.15 g L^-1	PE (20 mg L^-1)	0.3275	¹O₂	[120]
N-CNT	pyrolysis of mixture of MIL-101(Fe) and ZIF-8 in N₂ at 900 °C and in NH₃ at 950 °C	Fe-N₄ (2.01 Å), N-pyridinic, Fe^II	—	0.5 mmol L^-1 0.002 g L^-1	AO7 (50 mg L^-1)	0.811	¹O₂	[121]
N-C	pyrolysis of mixture of FePc, KHCO₃, and N-doped biochar in N₂ at 900 °C and acid leaching	Fe-N₄ (2.01 Å), N-pyridinic, Fe^II	0.41	1.95 mmol L^-1 0.8 g L^-1	RhB (0.1 g L^-1)	0.661	¹O₂	[122]
N-C	pyrolysis of Fe(acac)₃encapsulated ZIF-8 in N₂ at 900 °C	Fe-N₄ (2.00 Å), N-pyridinic, Fe^II	6.32	1 mmol L^-1 0.1 g L^-1	SSZ (8.0 mg L^-1)	0.095	¹O₂	[123]
N-C	pyrolysis of Fe(NO₃)₃ containing aerogel in N₂ at 800 °C	Fe-N₄ (1.50 Å), N-pyridinic, Fe^II	2.17	1.3 mmol L^-1 0.5 g L^-1	RhB (25 mg L^-1)	19.657	¹O₂	[124]
N-C	pyrolysis of mixture of Fe(OAc)₂-phen complex anchored biochar and melamine in N₂ at 550 and 700 °C and acid leaching	Fe-N₂-O₂, Fe-N: 1.92 Å, Fe-O: 2.01 Å, N-pyridinic, Fe^II	—	0.5 mmol L^-1 0.05 g L^-1	SMX (10 mg L^-1)	0.0862	¹O₂	[125]
ND	pyrolysis of FePc anchored ND in N₂ at 300 °C.	Fe-N₄ (1.96 Å), N-pyridinic, Fe^II	1.0	0.975 mmol L^-1 0.06 g L^-1	TC (15 mg L^-1)	0.283	¹O₂	[126]
N-C	pyrolysis of mixture of Fe(NO₃)₃-glucose complex anchored carbon and melamine in Ar at 800 °C	Fe-N₄ (2.00 Å), N-pyridinic, Fe^II	1.12	2 mmol L^-1 0.05 g L^-1	BPA (22.8 mg L^-1)	1.99	¹O₂, SO₄^•-, ^•OH	[127]
N-C	pyrolysis of Fe(acac)₃encapsulated ZIF-8 in Ar at 900 °C	Fe-N_x	1.52	0.65 mmol L^-1 0.15 g L^-1	SMX (10 mg L^-1)	1.1307	¹O₂, O₂^•-, SO₄^•-, ^•OH, ETP	[128]
N-C	pyrolysis of mixture of K₂FeO₄ and biochar in N₂ at 800 °C and acid leaching	Fe-N₃, N-graphitic	2.4	1.63 mmol L^-1 0.05 g L^-1	PE (20 mg L^-1)	1.096	Catalyst-PMS*	[129]
N-C	pyrolysis of FePc encapsulated ZIF-8 in Ar at 900 °C	Fe-N₄, N-pyridinic, Fe^II	0.88	1.3 mmol L^-1 0.15 g L^-1	BPA (20 mg L^-1)	0.3179	Catalyst-PMS*	[130]
N-C	pyrolysis of mixture of Fe(NO₃)₃-citric acid complex and melamine in N₂ at 800 °C	Fe-N₄ (1.97 Å), N-pyrrolic, Fe^II	4.8	0.5 mmol L^-1 0.1 g L^-1	BPA (22.8 mg L^-1)	8.4	Catalyst-PMS*	[131]
N-C	pyrolysis of FeCl₃ anchored g-C₃N₄-F127 complex in Ar at 600 °C and acid leaching	Fe-N_x	2.67	0.15 mmol L^-1 0.05 g L^-1	BPA (20 mg L^-1)	—	Catalyst-PMS*, ¹O₂	[132]
N-C	pyrolysis of Fe containing Enteromorpha in N₂ at 900 °C and acid leaching	Fe-N₂-O₂, Fe-N: 2.224 Å, Fe-O: 1.979 Å, N-pyridinic, Fe^III	0.82	0.5 mmol L^-1 0.1 g L^-1	ACP (10 mg L^-1)	0.1194	Catalyst-PMS*, Fe^IV=O	[133]
N-C	pyrolysis of Fe-doped ZIF-8 in Ar at 900 °C	Fe-N₄, Fe^III	0.93	1.3 mmol L^-1 0.15 g L^-1	BPA (20 mg L^-1)	0.24	Fe^IV=O	[134]
N-CNT	pyrolysis of ball milled Fe-C₃N₄ and CNT in N₂ at 700 °C	Fe-N₄ (2.01 Å), N-pyridinic, Fe^III	5.81	0.4 mmol L^-1 0.02 g L^-1	BPA (11.4 mg L^-1)	6.14	Fe^IV=O	[135]
O,N-C	pyrolysis of mixture of FeCl₃, DCD, and PMDA in air at 325 °C and acid leaching	Fe-N₂-O₂, Fe-N: 2.06 Å, Fe-O: 2.03 Å, N-pyridinic, Fe^II/Fe^III	0.84	1.0 mmol L^-1 0.5 g L^-1	PE (9.4 mg L^-1)	0.039	Fe^IV=O	[136]
N-C	pyrolysis of FeCl₃ anchored tannic acid-melamine super-molecule in N₂ at 800 °C and acid leaching	Fe-N₄ (2.06 Å), N-pyrrolic, Fe^II	2.4	0.4 mmol L^-1 0.16 g L^-1	BPA (22.8 mg L^-1)	7.44	Fe^IV=O	[137]
N-C	pyrolysis of Fe(NO₃)₃-phen complex anchored SBA-15 in N₂ at 900 °C and alkaline/acid leaching.	Fe-N₄ (1.92 Å), N-pyrrolic, Fe^III	0.62	0.1 mmol L^-1 0.02 g L^-1	BPA (4.6 mg L^-1)	—	Fe^IV=O	[138]
N-C	pyrolysis of Fe(OAc)₂-phen complex anchored nano-MgO in N₂ at 800 °C and acid leaching	Fe-N₅ (2.01 Å), N-pyridinic, Fe^III	1.2	1 mmol L^-1 0.1 g L^-1	SMX (10 mg L^-1)	0.675	Fe^IV=O	[139]
P,S-C	pyrolysis of Fe(NO₃)₃ anchored and PZS polymers coated ZIF-8 in N₂ at 900 °C	Fe-N₄ (1.99 Å), N-pyridinic, Fe^II	—	0.2 mmol L^-1 0.02 g L^-1	OFX (7.2 mg L^-1)	1.68	Fe^V=O	[140]
N-C	pyrolysis of mixture of Fe/Zn-lignin complex and DCD in N₂ at 550 and 950 °C	Fe-N₄ (1.98 Å), N-pyridinic, Fe^III	2.6	1 mmol L^-1 0.1 g L^-1	CQP (10 mg L^-1)	0.128	Fe^V=O	[141]
N-C	pyrolysis of Fe(OAc)₂-phen complex anchored nano-MgO in N₂ at 700 °C and acid leaching.	Fe-N₄ (2.00 Å), N-pyridinic, Fe^II	2.0	0.5 mmol L^-1 0.1 g L^-1	BPA (22.8 mg L^-1)	0.274	Fe^IV=O, Catalyst-PMS*	[142]
N-C	pyrolysis of mixture of Fe-MOF and melamine in in N₂ at 600 °C	Fe-N₄ (2.06 Å), N-pyridinic, Fe^II/Fe^III	5.91	0.5 mmol L^-1 0.2 g L^-1	BPA (20 mg L^-1)	0.357	Fe^V=O, SO₄^•-, ^•OH	[143]

Support	Synthetic method	Structure (l_M-N)	Loading (wt%)	PMS conc. Cat. dosage	Pollutant (Conc.)	k_obs (min^-1)	Reactive species	Ref.
N-C	pyrolysis of Fe(OAc)₂-phen complex anchored O-g-C₃N₄ in N₂ at 600 °C	Fe-N₄ (2.00 Å) Fe-Fe N-pyridinic	—	0.4 mmol L^-1 0.1 g L^-1	SMX (10 mg L^-1)	0.24	Surface-bond SO₄^•-/^•OH, ¹O₂	[108]
N-C	pyrolysis of mixture of Fe(acac)₃anchored carbon and DCD in N₂ at 900 °C	Fe-N₄ (2.04 Å) Fe-Fe, N-pyridinic, Fe^II	9.0	0.4 mmol L^-1 0.1 g L^-1	BPA (11.4 mg L^-1)	0.44	SO₄^•-, ^•OH, ¹O₂	[109]
N-C	pyrolysis of FeCl₃ anchored pyrrole-phytic acid hydrogel in N₂ at 700 °C and acid leaching	Fe-N₃-P₁, N-pyridinic, Fe^II	2.32	0.65 mmol L^-1 0.1 g L^-1	BPA (20 mg L^-1)	0.8	SO₄^•-, ^•OH, O₂^•-, ¹O₂	[110]
N-C	pyrolysis of Fe(OAc)₂-phen complex anchored carbon black in N₂ at 600 °C	Fe-N₄ (2.04 Å), N-pyrrolic, Fe^II	1.42	1.5 mmol L^-1 0.1 g L^-1	ACP (7.6 mg L^-1)	—	SO₄^•-, ^•OH	[111]
N-CNT	pyrolysis of mixture of Fe₂(SO₄)₃, melamine, and O-CNT in N₂ at 800 °C and acid leaching	Fe-N₃ (1.97 Å), Fe-Fe N-pyridinic, Fe^II	1.45	0.65 mmol L^-1 0.2 g L^-1	PE (9.4 mg L^-1)	2.59	SO₄^•-, ^•OH	[112]
N-C	pyrolysis of PPh₃ encapsulated Fe-doped ZIF-8 in Ar at 900 °C and acid leaching	Fe-N₃-P₁, Fe-N: 1.90 Å, Fe-P: 2.26 Å, N-pyridinic, Fe^II	0.77	0.5 mmol L^-1 0.1 g L^-1	BPA (10 mg L^-1)	0.397	^•OH	[113]
N-C	pyrolysis of mixture of FePc anchored polystyrene and urea in Ar at 350 and 550 °C	Fe-N₄, N-pyridinic, Fe^II	2.44	1 mmol L^-1 0.03 g L^-1	CP (1.3 mg L^-1)	1.663	O₂^•-, ¹O₂	[114]
N-C	CVD of the pyridine on ferrocene anchored CaO in Ar at 700 °C and acid leaching	Fe-N₄ (1.95 Å), N-pyridinic, Fe^II	0.61	3.25 mmol L^-1 0.025 g L^-1	PE (50 mg L^-1)	2.139	O₂^•-	[115]
N-C	CVD of mixture of Fe(acac)₃ and pyridine on Mg(OH)₂ in Ar at 800 °C and acid leaching	Fe-N₄ (1.99 Å), N-pyridinic, Fe^II	1.23	0.3 mmol L^-1 0.03 g L^-1	SMX (10 mg L^-1)	0.815	O₂^•-	[116]
N-C	pyrolysis of mixture of FeCl₃, glucose, and DCD in Ar at 900 °C	Fe-N₄ (1.97 Å), N-pyridinic, Fe^II	2.45	1 mmol L^-1 0.05 g L^-1	NP (20 mg L^-1)	0.302	O₂^•-, ¹O₂	[117]
N-C	pyrolysis of FeCl₂ and ZnCl₂ anchored silk fibroin in Ar at 900 °C and acid leaching	Fe-N₄, N-pyridinic, Fe^II	0.57	15 mmol L^-1 0.1 g L^-1	BPA (50 mg L^-1)	1.952	O₂^•-, ¹O₂	[118]
N-C	pyrolysis of FeCl₃ anchored COF (TpPa) in N₂ at 700 °C	Fe-N_x	2.14	0.65 mmol L^-1 0.1 g L^-1	Orange II (20 mg L^-1)	—	¹O₂	[119]
N-C	pyrolysis of Fe(acac)₃-phen complex anchored ZIF-8 derived carbon in Ar at 600 °C	Fe-N₄ (1.97 Å), N-pyridinic, Fe^II	0.71	1.3 mmol L^-1 0.2 g L^-1	BPA (25 mg L^-1)	0.104	¹O₂	[27]
N-C	pyrolysis of Fe(acac)₃ encapsulated ZIF-8 in N₂ at 900 °C and acid leaching	Fe-N_x	0.56	0.65 mmol L^-1 0.15 g L^-1	PE (20 mg L^-1)	0.3275	¹O₂	[120]
N-CNT	pyrolysis of mixture of MIL-101(Fe) and ZIF-8 in N₂ at 900 °C and in NH₃ at 950 °C	Fe-N₄ (2.01 Å), N-pyridinic, Fe^II	—	0.5 mmol L^-1 0.002 g L^-1	AO7 (50 mg L^-1)	0.811	¹O₂	[121]
N-C	pyrolysis of mixture of FePc, KHCO₃, and N-doped biochar in N₂ at 900 °C and acid leaching	Fe-N₄ (2.01 Å), N-pyridinic, Fe^II	0.41	1.95 mmol L^-1 0.8 g L^-1	RhB (0.1 g L^-1)	0.661	¹O₂	[122]
N-C	pyrolysis of Fe(acac)₃encapsulated ZIF-8 in N₂ at 900 °C	Fe-N₄ (2.00 Å), N-pyridinic, Fe^II	6.32	1 mmol L^-1 0.1 g L^-1	SSZ (8.0 mg L^-1)	0.095	¹O₂	[123]
N-C	pyrolysis of Fe(NO₃)₃ containing aerogel in N₂ at 800 °C	Fe-N₄ (1.50 Å), N-pyridinic, Fe^II	2.17	1.3 mmol L^-1 0.5 g L^-1	RhB (25 mg L^-1)	19.657	¹O₂	[124]
N-C	pyrolysis of mixture of Fe(OAc)₂-phen complex anchored biochar and melamine in N₂ at 550 and 700 °C and acid leaching	Fe-N₂-O₂, Fe-N: 1.92 Å, Fe-O: 2.01 Å, N-pyridinic, Fe^II	—	0.5 mmol L^-1 0.05 g L^-1	SMX (10 mg L^-1)	0.0862	¹O₂	[125]
ND	pyrolysis of FePc anchored ND in N₂ at 300 °C.	Fe-N₄ (1.96 Å), N-pyridinic, Fe^II	1.0	0.975 mmol L^-1 0.06 g L^-1	TC (15 mg L^-1)	0.283	¹O₂	[126]
N-C	pyrolysis of mixture of Fe(NO₃)₃-glucose complex anchored carbon and melamine in Ar at 800 °C	Fe-N₄ (2.00 Å), N-pyridinic, Fe^II	1.12	2 mmol L^-1 0.05 g L^-1	BPA (22.8 mg L^-1)	1.99	¹O₂, SO₄^•-, ^•OH	[127]
N-C	pyrolysis of Fe(acac)₃encapsulated ZIF-8 in Ar at 900 °C	Fe-N_x	1.52	0.65 mmol L^-1 0.15 g L^-1	SMX (10 mg L^-1)	1.1307	¹O₂, O₂^•-, SO₄^•-, ^•OH, ETP	[128]
N-C	pyrolysis of mixture of K₂FeO₄ and biochar in N₂ at 800 °C and acid leaching	Fe-N₃, N-graphitic	2.4	1.63 mmol L^-1 0.05 g L^-1	PE (20 mg L^-1)	1.096	Catalyst-PMS*	[129]
N-C	pyrolysis of FePc encapsulated ZIF-8 in Ar at 900 °C	Fe-N₄, N-pyridinic, Fe^II	0.88	1.3 mmol L^-1 0.15 g L^-1	BPA (20 mg L^-1)	0.3179	Catalyst-PMS*	[130]
N-C	pyrolysis of mixture of Fe(NO₃)₃-citric acid complex and melamine in N₂ at 800 °C	Fe-N₄ (1.97 Å), N-pyrrolic, Fe^II	4.8	0.5 mmol L^-1 0.1 g L^-1	BPA (22.8 mg L^-1)	8.4	Catalyst-PMS*	[131]
N-C	pyrolysis of FeCl₃ anchored g-C₃N₄-F127 complex in Ar at 600 °C and acid leaching	Fe-N_x	2.67	0.15 mmol L^-1 0.05 g L^-1	BPA (20 mg L^-1)	—	Catalyst-PMS*, ¹O₂	[132]
N-C	pyrolysis of Fe containing Enteromorpha in N₂ at 900 °C and acid leaching	Fe-N₂-O₂, Fe-N: 2.224 Å, Fe-O: 1.979 Å, N-pyridinic, Fe^III	0.82	0.5 mmol L^-1 0.1 g L^-1	ACP (10 mg L^-1)	0.1194	Catalyst-PMS*, Fe^IV=O	[133]
N-C	pyrolysis of Fe-doped ZIF-8 in Ar at 900 °C	Fe-N₄, Fe^III	0.93	1.3 mmol L^-1 0.15 g L^-1	BPA (20 mg L^-1)	0.24	Fe^IV=O	[134]
N-CNT	pyrolysis of ball milled Fe-C₃N₄ and CNT in N₂ at 700 °C	Fe-N₄ (2.01 Å), N-pyridinic, Fe^III	5.81	0.4 mmol L^-1 0.02 g L^-1	BPA (11.4 mg L^-1)	6.14	Fe^IV=O	[135]
O,N-C	pyrolysis of mixture of FeCl₃, DCD, and PMDA in air at 325 °C and acid leaching	Fe-N₂-O₂, Fe-N: 2.06 Å, Fe-O: 2.03 Å, N-pyridinic, Fe^II/Fe^III	0.84	1.0 mmol L^-1 0.5 g L^-1	PE (9.4 mg L^-1)	0.039	Fe^IV=O	[136]
N-C	pyrolysis of FeCl₃ anchored tannic acid-melamine super-molecule in N₂ at 800 °C and acid leaching	Fe-N₄ (2.06 Å), N-pyrrolic, Fe^II	2.4	0.4 mmol L^-1 0.16 g L^-1	BPA (22.8 mg L^-1)	7.44	Fe^IV=O	[137]
N-C	pyrolysis of Fe(NO₃)₃-phen complex anchored SBA-15 in N₂ at 900 °C and alkaline/acid leaching.	Fe-N₄ (1.92 Å), N-pyrrolic, Fe^III	0.62	0.1 mmol L^-1 0.02 g L^-1	BPA (4.6 mg L^-1)	—	Fe^IV=O	[138]
N-C	pyrolysis of Fe(OAc)₂-phen complex anchored nano-MgO in N₂ at 800 °C and acid leaching	Fe-N₅ (2.01 Å), N-pyridinic, Fe^III	1.2	1 mmol L^-1 0.1 g L^-1	SMX (10 mg L^-1)	0.675	Fe^IV=O	[139]
P,S-C	pyrolysis of Fe(NO₃)₃ anchored and PZS polymers coated ZIF-8 in N₂ at 900 °C	Fe-N₄ (1.99 Å), N-pyridinic, Fe^II	—	0.2 mmol L^-1 0.02 g L^-1	OFX (7.2 mg L^-1)	1.68	Fe^V=O	[140]
N-C	pyrolysis of mixture of Fe/Zn-lignin complex and DCD in N₂ at 550 and 950 °C	Fe-N₄ (1.98 Å), N-pyridinic, Fe^III	2.6	1 mmol L^-1 0.1 g L^-1	CQP (10 mg L^-1)	0.128	Fe^V=O	[141]
N-C	pyrolysis of Fe(OAc)₂-phen complex anchored nano-MgO in N₂ at 700 °C and acid leaching.	Fe-N₄ (2.00 Å), N-pyridinic, Fe^II	2.0	0.5 mmol L^-1 0.1 g L^-1	BPA (22.8 mg L^-1)	0.274	Fe^IV=O, Catalyst-PMS*	[142]
N-C	pyrolysis of mixture of Fe-MOF and melamine in in N₂ at 600 °C	Fe-N₄ (2.06 Å), N-pyridinic, Fe^II/Fe^III	5.91	0.5 mmol L^-1 0.2 g L^-1	BPA (20 mg L^-1)	0.357	Fe^V=O, SO₄^•-, ^•OH	[143]

Single-atom iron catalysts for peroxymonosulfate-based advanced oxidation processes: Coordination structure versus reactive species

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