Unveiling complexities: Reviews on insights into the mechanism of oxygen evolution reaction

doi:10.1016/S1872-2067(25)64653-5

Chinese Journal of Catalysis ›› 2025, Vol. 72: 48-83.DOI: 10.1016/S1872-2067(25)64653-5

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Unveiling complexities: Reviews on insights into the mechanism of oxygen evolution reaction

Pengxiang Zhang^a, Jiawen Wang^a, Tianyu Yang^a, Ruizhe Wang^a, Ruofan Shen^a, Zhikun Peng^a, Yanyan Liu^b^,^*(), Xianli Wu^a^,^*(), Jianchun Jiang^c, Baojun Li^a^,^*()

^aCollege of Chemistry, Zhengzhou University, Zhengzhou 450001, Henan, China
^bCollege of Science, Henan Agricultural University, Zhengzhou 450002, Henan, China
^cInstitute of Chemical Industry of Forest Products, CAF, National Engineering Laboratory for Biomass Chemical Utilization, Key and Open Laboratory on Forest Chemical Engineering, SFA, Nanjing 210042, Jiangsu, China

Received:2024-11-04 Accepted:2025-02-17 Online:2025-05-18 Published:2025-05-20
Contact: *E-mail: lyycarbon@henau.edu.cn (Y. Liu), wuxianli@zzu.edu.cn (X. Wu), lbjfcl@zzu.edu.cn (B. Li).
About author:Yanyan Liu received her Ph.D. degree from the College of Chemistry, Zhengzhou University in 2017. She works currently as a professor for the College of Science of Henan Agricultural University. She has focused research on the microstructure engineering of wooden activated carbon, and the development of highly active and selective catalysts for biomass utilization, oxygen conversion and hydrogen production. She has published more than 60 papers and authorized more than 10 invention patents. Her work provides valuable theoretical and technical support for the large-scale preparation of highly efficient carbon catalysts, and the high-value utilization of forest resources.
Xianli Wu received her Ph.D. degree from Materials Physics and Chemistry of Sun Yat-sen University in 2006. She works currently as a professor and doctoral supervisor for College of Chemistry, Zhengzhou University. Her work is mainly engaged in research of hydrogen energy storage, release and electrolytic water. She has published more than 40 research papers. She is also interested in investigating electrolytes and electrode materials for rechargeable batteries
Baojun Li received his Ph.D. degree from the College of Chemistry, Nanjing University in 2009. He works as a full professor and senior engineer for the College of Chemistry of Zhengzhou University. He devotes into the precise regulation of the structure and properties of condensed matter at atomic-molecular level and the development of catalytic routes for hydrogen production and biomass utility based on metallic compounds. He has published more than 150 papers and authorized more than 20 invention patents.
Supported by:
National Natural Science Foundation of China(22075254);Young Top Talent Program of Zhongyuan-Yingcai-Jihua(30602674)

Abstract

Abstract:

The study of the oxygen evolution reaction (OER) mechanism is vital for advancing our understanding of this pivotal energy conversion process. This review synthesizes recent advancements in OER mechanism, emphasizing the intricate relationship between catalytic mechanisms and catalyst design. This review discusses the connotation and cutting-edge progress of traditional mechanisms such as adsorbate evolution mechanism (AEM) and lattice oxygen mechanism (LOM) as well as emerging pathways including oxide path mechanism (OPM), oxo-oxo coupling mechanism (OCM), and intramolecular oxygen coupling mechanism (IMOC) etc. Innovative research progress on the coexistence and transformation of multiple mechanisms is highlighted, and the intrinsic factors that influence these dynamic processes are summarized. Advanced characterization techniques and theoretical modeling are underscored as indispensable tools for revealing these complex interactions. This review provides guiding principles for mechanism-based catalyst design. Finally, in view of the multidimensional challenges currently faced by OER mechanisms, prospects for future research are given to bridge the gap between mechanism innovation and experimental verification and application. This comprehensive review provides valuable perspectives for advancing clean energy technologies and achieving sustainable development.

Key words: Oxygen evolution reaction, Catalytic mechanism, Catalyst design, Adsorption evolution mechanism, Lattice oxygen mechanism

Pengxiang Zhang, Jiawen Wang, Tianyu Yang, Ruizhe Wang, Ruofan Shen, Zhikun Peng, Yanyan Liu, Xianli Wu, Jianchun Jiang, Baojun Li. Unveiling complexities: Reviews on insights into the mechanism of oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2025, 72: 48-83.

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Figures/Tables 27

Fig. 1. (a) Annual publication trends for "Oxygen evolution reaction" (blue) and "Oxygen evolution reaction" & "Mechanism" (red). (b) Comparative analysis of publications on AEM and LOM in OER research from 2020 to 2024. (c) Network visualization of keywords for "Oxygen evolution reaction" and "Mechanism" papers. (d) Visualization of the time correlation of papers retrieved using the search terms “Oxygen evolution reaction”, “Mechanism”, “Adsorbate evolution reaction” and/or “Lattice oxygen mechanism”. All data are from the Web of Science Core Collection database (SCI-EXPANDED and SSCI) as of December 5, 2024.

Fig. 2. Simplified AEM pathways of OER in acidic (a) and alkaline (b) environments. Chemically inert lattice oxygen and oxygen in the electrolyte are marked in black and red, respectively.

Fig. 3. Several typical LOM pathways involving different sites for OER in acidic and alkaline media. (a) Oxygen vacancy site mechanism (OVSM); (b) single metal site mechanism (SMSM); (c) dual-metal-site mechanism (DMSM).

Fig. 4. (a) Simplified OPM pathway of OER under acidic and alkaline conditions. (b) IMOC and WNC pathways.

Fig. 5. Analysis of OER catalytic mechanism using energy band theory. (a) AEM; (b) LOM.

Fig. 6. Research progress of AEM. (a) Depiction fabrication of (Ru-W)Ox. (b) Inter-doped heterostructures in (Ru-W)Ox. (c) Valence state evolution schematic for Ru sites in RuOx and (Ru-W)Ox during OER. (d) Illustration of regulating the Ru-O bonding environment in RuOx and (Ru-W)Ox. (e) Geometric models and corresponding active sites in the WOx, RuOx, and (Ru-W)Ox inter-doped heterostructure. (f) Adsorption Gibbs free energy for the AEM on Ru active sites in RuOx and (Ru-W)Ox. Reprinted with permission from Ref. [43]. Copyright 2023, John Wiley and Sons. (g) Energy variations as TM Atoms transition from [TMO6] to [TMO3] in TMO6@MoS2. (h) Dynamic OER reaction mechanism at active sites in FeO6@MoS2. (i) Conventional OER reaction mechanism at active sites in CuO6@MoS2. Reprinted with permission from Ref. [44]. Copyright 2022, Royal Society of Chemistry.

Fig. 7. (a) The schematic illustration of a sLOM. (b) The schematic illustration of the dLOM. (c) Comparison of Ni-O and Fe-O on NiFe and MoNiFe (oxy)hydroxide. Reprinted with permission from Ref. [49]. Copyright 2022, Springer Nature. (d) Raman spectra of NiFe and MoNiFe (oxy)hydroxide during CV, showing Ni2+ to Ni3+ transition. (e) Polarization curves for LaSr2.00, LaSr1.95, and LaSr1.90 in 1 mol L-1 KOH. (f) Schematic: Sr deficiency promotes oxygen vacancies, boosting OER catalysis via LOM. Arrows show oxygen ion diffusion. Reprinted with permission from Ref. [50]. Copyright 2022, John Wiley and Sons. With (g) and without (h) TMA+. DFT Calculations: molecular orbitals (i), density of states (j), chemical bonding (k), and energy (l) for Ru-UiO-67-bpydc and RuO2. Reprinted with permission from Ref. [51]. Copyright 2023, Elsevier.

Fig. 8. (a) Schematic of OPM mechanisms. (b) The O-O radical coupling promoted by symmetric dual active sites. (c) Crystalline structure models of RuO2 and α-MnO2 with Ru atoms substituting for the Mn at surface sites. Operando synchrotron FTIR spectra recorded in the potential range of 1.2-1.6 V vs. RHE for 12Ru/MnO2 (d) and commercial RuO2 (e). Reprinted with permission from Ref. [26]. Copyright 2021, Springer Nature. (f) Spin density and planar distribution maps of the spin polarization of the key oxygen intermediates (Co(O*)-Fe(O*)). (g) The parallel arrangement of spin electrons in the oxygen-oxygen coupling of adjacent metal sites facilitates triplet oxygen production. (h) Schematic diagram of the evolution mechanism of dual-site adsorbates coupled with O-O bonding during the for OER process. Reprinted with permission from Ref. [30]. Copyright 2024, Springer Nature.

Fig. 9. (a) OER All possible paths. Reprinted with permission from Ref. [29]. Copyright 2022, Elsevier. (b) Schematic illustration of the possible conventional AEM and OCM [27]. (c) Computed overpotential (η) of the dimers on M’M@NC. (d) Volcano-shaped relationship between the adsorption-free energy of oxygenated intermediates (ΔG*OH-*OH) and the theoretical overpotential (η). Gibbs free energy change of *OH toward *OH-*OH versus *OH → *O + H+ + e? (e) and *OH-*OH → *OH-*O + H+ + e? versus *OH-*OH → *OOH + H+ + e? (f). Insets show the schematic configuration of the different intermediates adsorbed on M′M@NC. Reprinted with permission from Ref. [27]. Copyright 2023, Springer Nature.

Fig. 10. (a) OER Pathway for Co-OEC. (b) Direct intramolecular oxygen coupling of two oxygen radicals generates a bridging peroxo intermediate. (c) Water hydrogen atom abstraction extracts the associated water molecules through oxygen free radicals to generate hydroperoxide intermediates. Reprinted with permission from Ref. [24]. Copyright 2016, American Chemical Society.

Fig. 11. (a) Log-log plot of OER current versus the surface hole (double-layer charge) density. (b) Activation energy of the O-O bond formation step versus the coverage of surface holes. (c) Sequence of four PCET steps at a single site. (d) Mechanism involving two surface holes. (e) Mechanism involving three surface holes. (f) Numbers next to the arrows correspond to the reported reaction steps. Reprinted with permission from Ref. [31]. Copyright 2022, Springer Nature.

Fig. 12. (a) Schematic diagram of the SET-OER mechanism between Ni(OH)2 and NiOOH. (b) The SET-OER pathway consists of a one-electron electrochemical reaction (green) and a thermal reaction (red) that proceed on anode simultaneously. (c) Schematic diagram of traditional OER and SET-OER and atomic structure diagram of NiOOH (001) and NiOOH (100). Reprinted with permission from Ref. [63]. Copyright 2023, Royal Society of Chemistry (d) Schematic diagram of the ACS-OER pathway (red cycle) and the traditional anode OER pathway (blue cycle) at the Ni(OH)2 edge site. Reprinted with permission from Ref. [65]. Copyright 2024, Springer Nature.

Table 1 List of different mechanisms and main research contents reported in existing literature.

Catalyst	Main research content	Electrolyte	Mechanism	Overpotential at j=10	Tafel	Stability Time/j (mA cm^-2)	Ref.
Fe-Ni(OH)₂/C	Fe introduced into Ni(OH₎₂	0.1 mol L^-1 KOH	ACS-OER	—	—	—	[65]
Ru/Ti₄O₇	titanium oxide stabilizes high-valent Ru	0.5 mol L^-1 H₂SO₄	AEM	150	41.26	500 h/10	[66]
Ir_1/CoOOH_sur	iridium single atoms doped into CoOOH lattice CoOOH	1 mol L^-1 KOH	AEM	210	33	24 h/10	[67]
CoOOH-M⁺ (M=Li, Na, K, Cs)	electrolyte cation insertion into CoOOH	1 mol L^-1 (MOH)	AEM	CsOH:355	CsOH: 66	—	[68]
NiFc'_xFc₁₋_x	defective MOFs were constructed by mixing Fc′ and Fc	1 mol L^-1 KOH	AEM	—	45	130 h/500	[69]
MoS₂/NiPS₃	covalently growing MoS₂ nanosheet on electrochemical exfoliated NiPS₃ lamellae	1 mol L^-1 KOH	AEM	296	86 for j=20	50 h/10	[70]
(Ru-W)O_x	inter-doped tungsten-ruthenium oxide heterostructures	0.5 mol L^-1 H₂SO₄	AEM	170	46.2	300 h/10	[43]
FeOOH-NiOOH	Fe-doped NiOOH support	1 mol L^-1 KOH	bifunctional mechanism	—	—	—	[64]
NF-AC-FD-NiO_x-Fe	nanoclusters of γ-FeOOH covalently linked to a γ-NiOOH support	1 mol L^-1 KOH	bifunctional reaction pathway	215	—	18 h/10	[61]
NR-NiOOH	strain-stabilized nonstochiometric nickel oxyhydroxide (NiOOH) nanoribbon light-triggered coupled oxygen evolution mechanism	—	coupled oxygen evolution mechanism (COM)	147	—	—	[34]
Ni_0.8Fe_0.2OOH-Light	Fe-doped NiOOH regulates eg* band broadening	1 mol L^-1 KOH	coupled oxygen evolution mechanism (COM)	—	214	—	[60]
CFS-ACs/CNT	single-domain ferromagnetic catalyst CoFeS_x nanoclusters on carbon nanotubes	1 mol L^-1 KOH	dual-site segmentally synergistic mechanism (DSSM)	270	77.6	633 h/20	[30]
3d-TMO₆@MoS₂	single 3d-TM co-doped with six oxygen atoms of MoS₂ (3d-TMO₆@MoS₂) with hexa-coordinated TM and tri-coordinated TM	—	dynamic active site OER mechanism (DAEM)	180	—	—	[44]
Fe:SrIrO₃	understanding the highly active amorphous IrO_x octahedrons with three basic types of connections through Fe:IrO_x and Fe:SrIrO₃	—	LOM	—	—	—	[71]
MoNiFe (oxy)hydroxide	Mo-doped NiFe-based (oxy) activated lattice oxygen	1 mol L^-1 KOH	LOM	242	23	—	[49]
SrCoO₃	intuitive evidence of the participation of lattice oxygen in the reaction was given through SrCoO₃	0.1 mol L^-1 KOH	LOM	—	—	—	[20]
Ru-UiO-67-bpydc	accelerated LOM pathway by stabilizing atomically isolated Ru oxides on UiO-67-bpydc with strongly coordinating pyridine ligands	0.5 mol L^-1 H₂SO₄	LOM	200	78.3	115 h/10	[51]
LaSr1.90	cation defect manipulation of perovskite surface to enhance LOM	1 mol L^-1 KOH	LOM	0	—	—	[50]
α-Fe₂O₃	study on the multi-hole OER mechanism using α-Fe₂O₃ thin film on SnO₂ model catalyst	—	multisite mechanism	—	—	—	[31]
M’M@NC	large-scale computational exploration of OCM pathways in heteronuclear active sites of diatomic catalysts	—	OCM				[27]
12Ru/MnO₂	enhanced OPM based on Ru atom array patch reconstruction supported on α-MnO₂	0.1 mol L^-1 HClO₄	OPM	161	29.4	200 h/10	[26]
Ru array-Co₃O₄	Ru atoms replace Co atoms on the surface of Co₃O₄ to enhance OPM	0.5 mol L^-1 H₂SO₄	OPM	160	46	1500 h/10	[62]
Cu₂S/CoFeCuOOH	irreversible reconstruction behavior of CoFe LDH catalyst on Cu₂S with dynamic evolution of cobalt	1 mol L^-1 KOH	OVSM	170 for j=20	41	100 h	[72]
Ni(OH)₂/NF	self-circulating catalytic oxygen production of Ni(OH)₂ and NiOOH in Ni(OH)₂ catalyst	12 mol L^-1 kg^-1 KOH	self-circulating electrochemical-thermal (SET-OER)	20	52.6 at 120 °C	15 h/10 and 120 °C	[63]

Table 1 List of different mechanisms and main research contents reported in existing literature.

Catalyst	Main research content	Electrolyte	Mechanism	Overpotential at j=10	Tafel	Stability Time/j (mA cm^-2)	Ref.
Fe-Ni(OH)₂/C	Fe introduced into Ni(OH₎₂	0.1 mol L^-1 KOH	ACS-OER	—	—	—	[65]
Ru/Ti₄O₇	titanium oxide stabilizes high-valent Ru	0.5 mol L^-1 H₂SO₄	AEM	150	41.26	500 h/10	[66]
Ir_1/CoOOH_sur	iridium single atoms doped into CoOOH lattice CoOOH	1 mol L^-1 KOH	AEM	210	33	24 h/10	[67]
CoOOH-M⁺ (M=Li, Na, K, Cs)	electrolyte cation insertion into CoOOH	1 mol L^-1 (MOH)	AEM	CsOH:355	CsOH: 66	—	[68]
NiFc'_xFc₁₋_x	defective MOFs were constructed by mixing Fc′ and Fc	1 mol L^-1 KOH	AEM	—	45	130 h/500	[69]
MoS₂/NiPS₃	covalently growing MoS₂ nanosheet on electrochemical exfoliated NiPS₃ lamellae	1 mol L^-1 KOH	AEM	296	86 for j=20	50 h/10	[70]
(Ru-W)O_x	inter-doped tungsten-ruthenium oxide heterostructures	0.5 mol L^-1 H₂SO₄	AEM	170	46.2	300 h/10	[43]
FeOOH-NiOOH	Fe-doped NiOOH support	1 mol L^-1 KOH	bifunctional mechanism	—	—	—	[64]
NF-AC-FD-NiO_x-Fe	nanoclusters of γ-FeOOH covalently linked to a γ-NiOOH support	1 mol L^-1 KOH	bifunctional reaction pathway	215	—	18 h/10	[61]
NR-NiOOH	strain-stabilized nonstochiometric nickel oxyhydroxide (NiOOH) nanoribbon light-triggered coupled oxygen evolution mechanism	—	coupled oxygen evolution mechanism (COM)	147	—	—	[34]
Ni_0.8Fe_0.2OOH-Light	Fe-doped NiOOH regulates eg* band broadening	1 mol L^-1 KOH	coupled oxygen evolution mechanism (COM)	—	214	—	[60]
CFS-ACs/CNT	single-domain ferromagnetic catalyst CoFeS_x nanoclusters on carbon nanotubes	1 mol L^-1 KOH	dual-site segmentally synergistic mechanism (DSSM)	270	77.6	633 h/20	[30]
3d-TMO₆@MoS₂	single 3d-TM co-doped with six oxygen atoms of MoS₂ (3d-TMO₆@MoS₂) with hexa-coordinated TM and tri-coordinated TM	—	dynamic active site OER mechanism (DAEM)	180	—	—	[44]
Fe:SrIrO₃	understanding the highly active amorphous IrO_x octahedrons with three basic types of connections through Fe:IrO_x and Fe:SrIrO₃	—	LOM	—	—	—	[71]
MoNiFe (oxy)hydroxide	Mo-doped NiFe-based (oxy) activated lattice oxygen	1 mol L^-1 KOH	LOM	242	23	—	[49]
SrCoO₃	intuitive evidence of the participation of lattice oxygen in the reaction was given through SrCoO₃	0.1 mol L^-1 KOH	LOM	—	—	—	[20]
Ru-UiO-67-bpydc	accelerated LOM pathway by stabilizing atomically isolated Ru oxides on UiO-67-bpydc with strongly coordinating pyridine ligands	0.5 mol L^-1 H₂SO₄	LOM	200	78.3	115 h/10	[51]
LaSr1.90	cation defect manipulation of perovskite surface to enhance LOM	1 mol L^-1 KOH	LOM	0	—	—	[50]
α-Fe₂O₃	study on the multi-hole OER mechanism using α-Fe₂O₃ thin film on SnO₂ model catalyst	—	multisite mechanism	—	—	—	[31]
M’M@NC	large-scale computational exploration of OCM pathways in heteronuclear active sites of diatomic catalysts	—	OCM				[27]
12Ru/MnO₂	enhanced OPM based on Ru atom array patch reconstruction supported on α-MnO₂	0.1 mol L^-1 HClO₄	OPM	161	29.4	200 h/10	[26]
Ru array-Co₃O₄	Ru atoms replace Co atoms on the surface of Co₃O₄ to enhance OPM	0.5 mol L^-1 H₂SO₄	OPM	160	46	1500 h/10	[62]
Cu₂S/CoFeCuOOH	irreversible reconstruction behavior of CoFe LDH catalyst on Cu₂S with dynamic evolution of cobalt	1 mol L^-1 KOH	OVSM	170 for j=20	41	100 h	[72]
Ni(OH)₂/NF	self-circulating catalytic oxygen production of Ni(OH)₂ and NiOOH in Ni(OH)₂ catalyst	12 mol L^-1 kg^-1 KOH	self-circulating electrochemical-thermal (SET-OER)	20	52.6 at 120 °C	15 h/10 and 120 °C	[63]

Fig. 13. (a) OER active volcano diagram with the difference of binding energy (ΔGO* - ΔGOH*) as a descriptor of overpotential following AEM (marked with coloed legends) and the corresponding LOM (marked with the red ball). (b) Energy barrier of O-O coupling as a function of the free energy of O* adsorption. (c) Contour map of the energy barrier of O-O coupling versus the overpotential of AEM and LOM, where the dashed line represents equal thermodynamics of AEM and LOM (ηAEM = ηLOM), and the red contour line represents the delineated favorable kinetics range (ΔGO-O = 1.5 eV). Reprinted with permission from Ref. [38]. Copyright 2020, Royal Society of Chemistry. (d) Light-response test of traditional NiOOH and NR-NiOOH using chronoamperometry measurement. (e) Chronoamperometry curve of NR-NiOOH without light irradiation. (f) Operando Ni K-edge XANES spectra of NR-NiOOH subjected to light irradiation. (g) Light-induced electron transfer process with switchable metal and oxygen redox centers for the OER. Reprinted with permission from Ref. [34]. Copyright 2022, Springer Nature. (h) OER catalytic mechanism diagram of Co doped SrIrO3 catalyst. (i) The 18O16O percentage of the samples test by DEMS. (j) Lattice oxygen promote AEM pathway. Reprinted with permission from Ref. [80]. Copyright 2024, Springer Nature.

Fig. 14. Endopathic factors of mechanism conversion.

Fig. 15. (a) Schematic illustration. Integrated management of the dynamics of both active phase and catalysis pathway for spinel oxide NiCo2O4 OER catalysts. Reprinted with permission from Ref. [89]. Copyright 2022, John Wiley and Sons. (b) Schematic of reconstruction of CoFe LDH for OER. Reprinted with permission from Ref. [72]. Copyright 2022, John Wiley and Sons.

Fig. 16. (a) Model of zinc-substituted MO2. (b) Thermodynamic stabilities between O22? and O2? species. (c) Schematic of the chemical recognition of O22? species using TMA+ as a probe. Reprinted with permission from Ref. [58]. Copyright 2019, Springer Nature. (d) AEM and OPM paths of OER on the RuO2:Zn_Vo surface. (e) Free energy diagrams for preferred OER paths on the surfaces of RuO2, RuO2:Zn, and RuO2:Zn_Vo. (f) Differential charge density analysis and Bader charge analysis of RuO2:Zn. (g) PDOS of Ru 4d, O 2p, and Zn 3d for RuO2, RuO2:Zn, and RuO2:Zn_Vo; corresponding d-band centers are denoted by dashed lines. Reprinted with permission from Ref. [90]. Copyright 2023, Springer Nature.

Fig. 17. (a) Schematic diagram of Ir1@NiOOH and mechanism transformation via selective substitution and electrochemical activation. Reprinted with permission from Ref. [93]. Copyright 2024, American Chemical Society.

Fig. 18. (a) Schematic of mechanism conversion on 1D NiFeOx-P and 1D NiFeOx. (b,c) Free energy of OER steps via AEM and LOM mechanisms on (b) NiOOH and (c) P-NiOOH. Reprinted with permission from Ref. [94]. Copyright 2023, John Wiley and Sons. (d) LSV curves for the OER of S-FeOOH/IF, FeOOH/IF, and RuO2/IF. Free energy of OER steps via AEM and LOM mechanisms on FeOOH (e) and S-FeOOH (f). (g) LSV curves of FeOOH and S-FeOOH in 1 mol L-1 KOH and 1 mol L-1 TMAOH. (h) In situ ATR FTIR spectra of S-FeOOH/IF. (i) In situ Raman spectra coupled with isotope experiment using a three-electrode system with S-FeOOH/IF as the working electrode. Reprinted with permission from Ref. [95]. Copyright 2022, John Wiley and Sons.

Fig. 19. (a) Correlation between the computed OER overpotential and O 2p-band center for the AEM (solid line) and LOM (dashed line) for the MO2(110) (M = Ru, Ir) surface. Reprinted with permission from Ref. [99]. Copyright 2020, American Chemical Society. (b) Schematic illustration of the synthetic route to ZnCo2O4-x and ZnCo2O4-xFx. (c) Calculated energy barriers of the *OH transformation to *OOH. (d) Calculated energy barriers of the *O-OH transformation to *OH-OH. Reprinted with permission from Ref. [100]. Copyright 2023, John Wiley and Sons. (e) DEMS signals within four times of LSV at 1.1-1.9 V. (f,g) A two-dimensional activity map for (f) AEM mechanism, (g) LOM-OVS mechanism. (h) Comparisons between calculated overpotential and experiment overpotential relationship. Reprinted with permission from Ref. [102]. Copyright 2023, Springer Nature. Projected density of states (i), the LHB center positions (j) and computed free energies (k) of OER steps. Reprinted with permission from Ref. [77]. Copyright 2023, Springer Nature.

Fig. 20. (a) Charge transfer between IrOx (111) and Zr2ON2 (111). DFT-estimated reaction energy diagram for the OER on Ir with 1ML O* (b) and on IrOx/Zr2ON2 with 1 ML O* (c). Reprinted with permission from Ref. [105]. Copyright 2023, John Wiley and Sons. (d) Model representing both the single-atom type metal-anchoring SAC1 (hollow site above outer oxygen layer) and SAC2 (anchored in outer metal layer). Free energy diagrams for the OER of Ni-Sc3N2O2 in the standard condition: (e) AEM for SAC1; (f) LOM-O for SAC2. Reprinted with permission from Ref. [106]. Copyright 2021, John Wiley and Sons. (g) Schematic illustration of the optimized OER process induced by the Ti4O7 support. Reprinted with permission from Ref. [66]. Copyright 2024, Springer Nature.

Fig. 21. (a) Schematics of OER mechanism changed from AEM to OPM on Cr0.6Ru0.4O2. Reprinted with permission from Ref. [107]. Copyright 2024, American Chemical Society. (b) Schematic diagram of the voltage-dependent IMOC and WNC pathway conversions on Co-oxide catalysts Reprinted with permission from Ref. [23]. Copyright 2021, Elsevier. (c) The main mechanism of OER of nickel-based LDH predicted by microkinetic model with catalyst composition and applied potential profile. Reprinted with permission from Ref. [25]. Copyright 2023, Springer Nature.

Fig. 22. (a) The process and crystallographic representation of CWO delamination into CWO-del-48 through base treatment. (b) Potential and pH dependence of the intermediates in OER for the CWO-del-48. (c) Free energy profiles of CWO and CWO-del-48 in OER pathways. The dynamic involvement of H2O and OH- enables favorable confined AEM (cAEM) and confined OPM (cOPM) reaction pathways in CWO-del-48. Reprinted with permission from Ref. [108]. Copyright 2024, American Association for the Advancement of Science.

Table 2 List of existing literature reports on mechanism transformation and main research contents. (“/” represents the coexistence of mechanisms, “→” represents the transformation of mechanisms).

Catalyst	Main research content	Electrolyte	Mechanism	Overpotential at j=10	Tafel	Stability Time/j (mA cm^-2)	Ref.
ZnCo₂O₄₋_xF_x/ CNTs	F anions are incorporated into oxygen vacancies in ZnCo₂O₄ to activate lattice oxygen	1 mol L^-1 KOH	AEM → LOM	350	59.2	13 h/10	[100]
NiFeO_x-P	P doped nickel-iron mixed oxides promote mechanism transformation	1 mol L^-1 KOH	AEM → LOM	237	27.07	120 h/70	[94]
Ni₁₋_xFe_xCo₂O₄	A-site Fe doping NiCo₂O₄ accelerates phase transition and induces mechanism transformation	1 mol L^-1 KOH	AEM → LOM	239	39	52 h/20	[89]
IrO_x/Zr₂ON₂	Zr₂ON₂-Supported IrO_x and inducing catalytic pathway transformation	0.5 mol L^-1 H₂SO₄	AEM → LOM	255	48.01	5 h/10	[105]
Zn-Cr	Zn-Cr dual metal doping in cobalt spinel oxide improves AEM and LOM	—	AEM/LOM	—	—	—	[38]
Y_1.75C_o0.25 Ru₂O₇₋_δ	Co incorporation in Y₂Ru₂O₇₋_δ enhances AEM/LOM simultaneously	0.5 mol L^-1 H₂SO₄	AEM/LOM	275	61	—	[81]
CWO-del-48	the introduction of soluble tungsten stabilizes the cobalt catalyst and leads to the creation of a layered structure.	0.5 mol L^-1 H₂SO₄	OPM → AEM	288	85	175 h/10	[108]
NiFe-LDH/FeOOH	modulating oxygen defects in (NiFe-LDH)/FeOOH heterostructures to trigger the single-lattice oxygen mechanism.	1.0 mol L^-1 KOH	AEM/sLOM	236	62.05	—	[52]
Zn_0.2Co_0.8OOH	specific zinc-substituted CoOOH leads to mechanism switching	1.0 mol L^-1 KOH	AEM → LOM	241	35.7	40 h/20	[58]
AuSA-MnFeCoNiCu LDH	Au-modified and O-vacancy high-entropy MnFeCoNiCu-LDH triggers LOM	1.0 mol L^-1 KOH	AEM → LOM	213	27.5	700 h/100	[77]
S-FeOOH/IF	S-doped FeOOH layer leads to a mechanism shift	alkaline	AEM → LOM	—	—	—	[95]
py-RuO₂:Zn	Zn-doped RuO₂ nanowire arrays, mechanism transformation	0.5 mol L^-1 H₂SO₄	AEM → OPM	173	41.2	1000 h/10	[90]
Ir₁@NiOOH	single Ir atom anchored in NiOOH drives mechanism transition	1 mol L^-1 KOH	AEM → SMSM → DMSM	142	29	50 h/10	[93]
Co_2.75Fe_0.25O₄	spin manipulation of (hydroxy)hydroxides to promote O-O coupling	1 mol L^-1 KOH	AEM/LOM/	—	—	—	[109]
Rh-RuO₂/G	Rh doping in RuO₂ lattice on graphene	0.5 mol L^-1 H₂SO₄	LOM/OVSM	161	45.8	700 h/50	[102]
Ru_(anc)-Co₃O₄	the spatial localization of single-atom Ru was manipulated by using the metal defect anchors of the support, changing the reaction mechanism	0.5 mol L^-1 H₂SO₄	LOM → AEM → Proton donor−acceptor mechanism (PDAM)	198	49.2	150 h/10	[101]
Ni-Sc₃N₂O₂	simulation analysis of the OER mechanism of MXenes with different layers of late metal doping	—	SAC1 for AEM SAC2 for LOM	—	—	—	[106]
Si-RuO₂-0.1	Si-doped RuO₂	0.1 mol L^-1 HClO₄	suppressing LOM and strengthening AEM	226	33	800 h/10	[92]
MoZnFeCoNi	MoZn- based high entropy alloy, Co-Co† facilitating AEM and Zn-O†-Ni sites enhancing LOM	1 mol L^-1 KOH	dual activation of AEM and LOM	221	48.78	1550 h/100	[110]

Catalyst	Main research content	Electrolyte	Mechanism	Overpotential at j=10	Tafel	Stability Time/j (mA cm^-2)	Ref.
ZnCo₂O₄₋_xF_x/ CNTs	F anions are incorporated into oxygen vacancies in ZnCo₂O₄ to activate lattice oxygen	1 mol L^-1 KOH	AEM → LOM	350	59.2	13 h/10	[100]
NiFeO_x-P	P doped nickel-iron mixed oxides promote mechanism transformation	1 mol L^-1 KOH	AEM → LOM	237	27.07	120 h/70	[94]
Ni₁₋_xFe_xCo₂O₄	A-site Fe doping NiCo₂O₄ accelerates phase transition and induces mechanism transformation	1 mol L^-1 KOH	AEM → LOM	239	39	52 h/20	[89]
IrO_x/Zr₂ON₂	Zr₂ON₂-Supported IrO_x and inducing catalytic pathway transformation	0.5 mol L^-1 H₂SO₄	AEM → LOM	255	48.01	5 h/10	[105]
Zn-Cr	Zn-Cr dual metal doping in cobalt spinel oxide improves AEM and LOM	—	AEM/LOM	—	—	—	[38]
Y_1.75C_o0.25 Ru₂O₇₋_δ	Co incorporation in Y₂Ru₂O₇₋_δ enhances AEM/LOM simultaneously	0.5 mol L^-1 H₂SO₄	AEM/LOM	275	61	—	[81]
CWO-del-48	the introduction of soluble tungsten stabilizes the cobalt catalyst and leads to the creation of a layered structure.	0.5 mol L^-1 H₂SO₄	OPM → AEM	288	85	175 h/10	[108]
NiFe-LDH/FeOOH	modulating oxygen defects in (NiFe-LDH)/FeOOH heterostructures to trigger the single-lattice oxygen mechanism.	1.0 mol L^-1 KOH	AEM/sLOM	236	62.05	—	[52]
Zn_0.2Co_0.8OOH	specific zinc-substituted CoOOH leads to mechanism switching	1.0 mol L^-1 KOH	AEM → LOM	241	35.7	40 h/20	[58]
AuSA-MnFeCoNiCu LDH	Au-modified and O-vacancy high-entropy MnFeCoNiCu-LDH triggers LOM	1.0 mol L^-1 KOH	AEM → LOM	213	27.5	700 h/100	[77]
S-FeOOH/IF	S-doped FeOOH layer leads to a mechanism shift	alkaline	AEM → LOM	—	—	—	[95]
py-RuO₂:Zn	Zn-doped RuO₂ nanowire arrays, mechanism transformation	0.5 mol L^-1 H₂SO₄	AEM → OPM	173	41.2	1000 h/10	[90]
Ir₁@NiOOH	single Ir atom anchored in NiOOH drives mechanism transition	1 mol L^-1 KOH	AEM → SMSM → DMSM	142	29	50 h/10	[93]
Co_2.75Fe_0.25O₄	spin manipulation of (hydroxy)hydroxides to promote O-O coupling	1 mol L^-1 KOH	AEM/LOM/	—	—	—	[109]
Rh-RuO₂/G	Rh doping in RuO₂ lattice on graphene	0.5 mol L^-1 H₂SO₄	LOM/OVSM	161	45.8	700 h/50	[102]
Ru_(anc)-Co₃O₄	the spatial localization of single-atom Ru was manipulated by using the metal defect anchors of the support, changing the reaction mechanism	0.5 mol L^-1 H₂SO₄	LOM → AEM → Proton donor−acceptor mechanism (PDAM)	198	49.2	150 h/10	[101]
Ni-Sc₃N₂O₂	simulation analysis of the OER mechanism of MXenes with different layers of late metal doping	—	SAC1 for AEM SAC2 for LOM	—	—	—	[106]
Si-RuO₂-0.1	Si-doped RuO₂	0.1 mol L^-1 HClO₄	suppressing LOM and strengthening AEM	226	33	800 h/10	[92]
MoZnFeCoNi	MoZn- based high entropy alloy, Co-Co† facilitating AEM and Zn-O†-Ni sites enhancing LOM	1 mol L^-1 KOH	dual activation of AEM and LOM	221	48.78	1550 h/100	[110]

Fig. 23. Schematic diagram of common methods for verifying catalytic mechanisms. Reprinted with permission from Ref. [26]. Copyright 2021, Springer Nature. Reprinted with permission from Ref. [93]. Copyright 2024, American Chemical Society. Reprinted with permission from Ref. [101]. Copyright 2023, American Chemical Society. Reprinted with permission from Ref. [77]. Copyright 2023, Springer Nature. Reprinted with permission from Ref. [101]. Copyright 2023, American Chemical Society. Reprinted with permission from Ref. [31]. Copyright 2022, Springer Nature.

Fig. 24. Illustration of mechanism-guided design principles for OER catalysts.

Fig. 25. Future research prospects of OER mechanism. Reprinted with permission from Ref. [89]. Copyright 2022, John Wiley and Sons. Reprinted with permission from Ref. [101]. Copyright 2023, American Chemical Society. Reprinted with permission from Ref. [109]. Copyright 2024, Springer Nature. Copyright 2022, John Wiley and Sons. Reprinted with permission from Ref. [113]. Copyright 2020, Springer Nature. Copyright 2022, John Wiley and Sons. Reprinted with permission from Ref. [114]. Copyright 2024, Springer Nature.

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Unveiling complexities: Reviews on insights into the mechanism of oxygen evolution reaction

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