Chinese Journal of Catalysis ›› 2026, Vol. 81: 37-68.DOI: 10.1016/S1872-2067(25)64880-7
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Haihong Zhonga, Qianqian Xub, Weiting Yanga, Nicolas Alonso-Vantec, Yongjun Fengb(
)
Received:2025-07-28
Accepted:2025-09-05
Online:2026-02-18
Published:2025-12-26
Contact:
*E-mail: yjfeng@mail.buct.edu.cn (Y. Feng).
About author:Dr. Yongjun Feng, born in January 1976, is a full professor and Ph.D. supervisor in Beijing University of Chemical Technology. In 2022, he was recognized by the National Major Talent Project and the Shandong Mount Taishan Industrial Leading Talent Project. He currently holds the position of Director at the Talent Introduction Office of Beijing University of Chemical Technology, and serves in various esteemed roles such as a member of the International Symposium on Intercalation Compounds Committee (ISIC), a Senior Member of the Chinese Chemical Society, Vice Chairman of the Expert Committee of the China Renewable Resources Industry Technology Innovation Strategy Alliance, and a member of the Anhui Province New Materials Industry Development Strategy Advisory Committee. In January 2007, he earned his Ph.D. in Chemistry from Blaise Pascal University in France, and subsequently pursued postdoctoral research at the University of Poitiers in France. In 2011, he joined the State Key Laboratory of Chemical Resources Engineering (CRE), focusing on the fundamental, applied, and engineering research of intercalated structure functional materials, porous carriers and adsorption materials, and non-noble metal electrocatalytic materials. He has led more than 30 projects entrusted by international, national and enterprise entities, and built 8 sets of industrial plants with a scale of more than 100 tons per year, including 2 under his direct leadership. He has published more than 120 papers in leading international journals as the first author or corresponding author, filed more than 60 national invention patents, of which 46 were granted; and served on the editorial boards of journals including “Applied Clay Science” and “Fine Chemicals.” Multiple patented technologies have been successfully commercialized.
Supported by:Haihong Zhong, Qianqian Xu, Weiting Yang, Nicolas Alonso-Vante, Yongjun Feng. Composition regulation of iron-group transition metal chalcogenides for the oxygen electrocatalysis: Electronic structure and surface reconstruction[J]. Chinese Journal of Catalysis, 2026, 81: 37-68.
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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64880-7
Fig. 1. Schematic illustration of the cascading influence from compositional regulation to electronic structure, surface property, and oxygen electrocatalysis.
Fig. 2. (a) Schematic diagram of four-electron and two-electron ORR pathways. (b,c) volcano plots of various metals for ORR activity. Reprinted with permission from Ref. [30]. Copyright 2004, American Chemical Society. (d) The linear relationship between ΔGOOH* and ΔGOH*. Reprinted with permission from Ref. [31]. Copyright 2022, Elsevier. (e) DOS diagram of spinel oxide and the correlation between OER pathways (AEM versus LOM) and the band centers. Reprinted with permission from Ref. [32]. Copyright 2023, John Wiley and Sons.
Fig. 3. (a) The diagram of d-orbital splitting of Co ions with different oxidation-valence states. (b) Electronic coupling of Co3+-O-Co3+, Co2+-O-Co2+, and Co3+-O-Co2+ three configurations. (c) Charge density difference diagrams of pure Co-S model (left) and Co-S, Co-N4-C coexistence model (right), respectively. (d) PDOS of Co 3d and corresponding d-band centers for the Co@NC, Co-S and Co-S@NC. Reprinted with permission from Ref. [80]. Copyright 2024, John Wiley and Sons. (e) Schematic diagram of the spin states of Co ions in CoN3S1, CoN2S2, and CoN1S3 configurations. (f) DOS of the Co sites. (g) the diagram d-orbital splitting of Co ions based on crystal field theory. Reprinted with permission from Ref. [81]. Copyright 2025, American Chemical Society.
Fig. 4. (a) Difference charge density of Co/NC, Co-Co/NC, Co-Se/NC, and Co-Se/Co/NC four models. (b) DOS of Co. (c) Dissolution potential of Co active sites in Co-Se/NC and Co-Se/Co/NC models. (d) Proposed ORR pathway of the Co-Se/Co/NC. (d) Gibbs free energy at Co, Se (Co-Se) and Co (Co-Se) three sites of the Co-Se/Co/NC for ORR at U = 1.23 V. (e) Schematic diagram of Gibbs free energy on the four electrocatalysts. (f) Crystal orbital Hamilton population (COHP) of Co/NC, Co-Se/NC, and Co-Se/Co/NC models. (g) PDOS of O 2p and Co 3d orbits in the Co-Se/Co/NC model. Reprinted with permission from Ref. [87]. Copyright 2024, John Wiley and Sons.
| Catalyst/counterpart | E1/2 (V vs. RHE) | Eonset (V vs. RHE) | Stability | Ref. |
|---|---|---|---|---|
| Co-S@NC | 0.85 | 0.92 | 221 cycles at 1000 mA g-1 in a Li-O2 battery | [ |
| CoN1S3 | 0.88 | 0.98 | discharge for 20 h in a ZAB | [ |
| CoN3S1 | 0.82 | 0.94 | — | |
| CoN2S2 | 0.87 | 0.97 | — | |
| CoO0.87S0.13/GN | 0.83 | 0.94@0.1 mA cm-2 | after 300 cycles (~300 h), the voltage gap remains 0.77 V in a ZAB | [ |
| CoOxS1.097/G | 0.69 | 0.86@0.1 mA cm-2 | — | |
| Ni0.5Mo0.5OSe | 0.88 | 0.96 | after operating for 300 h, the discharge voltage holds 1.25 V in a ZAB | [ |
| Ni0.75Mo0.25OSe | 0.82 | 0.91 | — | |
| Ni0.25Mo0.75OSe | 0.77 | 0.88 | — | |
| Co-Se/Co/NC | 0.88 | 0.99 | discharging at 10 mA cm-2 for 80 h and at 20 mA cm-2 for 40 h in a ZAB | [ |
| Co-Se/NC | 0.85 | 0.94 | — | |
| Co-Co/NC | 0.81 | 0.90 | — | |
| NixCo9‒xS8@NSC | 0.93 | 0.99 | charge-discharge cycling at 10 mA cm-2 for 160 h (≈960 cycles) in a ZAB | [ |
| NiS@NSC | 0.78 | 0.86 | — | |
| CoS@NSC | 0.81 | 0.87 | — | |
| CoNiFe-S | 0.78 | 0.88 | after 40 h/120 cycles, the voltage gap remains 0.74 V in a ZAB | [ |
Table 1 Summary of ORR performance for reported IGTMC catalysts and the corresponding counterparts in 0.1 mol L-1 KOH solution.
| Catalyst/counterpart | E1/2 (V vs. RHE) | Eonset (V vs. RHE) | Stability | Ref. |
|---|---|---|---|---|
| Co-S@NC | 0.85 | 0.92 | 221 cycles at 1000 mA g-1 in a Li-O2 battery | [ |
| CoN1S3 | 0.88 | 0.98 | discharge for 20 h in a ZAB | [ |
| CoN3S1 | 0.82 | 0.94 | — | |
| CoN2S2 | 0.87 | 0.97 | — | |
| CoO0.87S0.13/GN | 0.83 | 0.94@0.1 mA cm-2 | after 300 cycles (~300 h), the voltage gap remains 0.77 V in a ZAB | [ |
| CoOxS1.097/G | 0.69 | 0.86@0.1 mA cm-2 | — | |
| Ni0.5Mo0.5OSe | 0.88 | 0.96 | after operating for 300 h, the discharge voltage holds 1.25 V in a ZAB | [ |
| Ni0.75Mo0.25OSe | 0.82 | 0.91 | — | |
| Ni0.25Mo0.75OSe | 0.77 | 0.88 | — | |
| Co-Se/Co/NC | 0.88 | 0.99 | discharging at 10 mA cm-2 for 80 h and at 20 mA cm-2 for 40 h in a ZAB | [ |
| Co-Se/NC | 0.85 | 0.94 | — | |
| Co-Co/NC | 0.81 | 0.90 | — | |
| NixCo9‒xS8@NSC | 0.93 | 0.99 | charge-discharge cycling at 10 mA cm-2 for 160 h (≈960 cycles) in a ZAB | [ |
| NiS@NSC | 0.78 | 0.86 | — | |
| CoS@NSC | 0.81 | 0.87 | — | |
| CoNiFe-S | 0.78 | 0.88 | after 40 h/120 cycles, the voltage gap remains 0.74 V in a ZAB | [ |
Fig. 5. (a) DOS diagrams of NiO, NiSe, Ni3Se2 and Ni; normalized CV curves by the BET surface area of the electrocatalyst in 0.1 mol L-1 KOH electrolytes; corresponding Tafel slope plots; Reprinted with permission from Ref. [118]. Copyright 2017, American Chemical Society. (b) Average overpotentials at 10 mA cm-2 of the OER for all the NiSSe electrocatalysts; average half-wave potentials of the ORR; calculated pseudo-ΔE (pΔE) values, presenting an improvement in BOE performance along with increasing Se content. Reprinted with permission from Ref. [119]. copyright 2023, American Chemical Society.
Fig. 6. (a) The adsorption models of *OO, *OOH, *O and *OH intermediates on the Ni(S0.51Se0.49)2@NC; Gibbs free energy diagrams for the ORR and OER on Ni-NiS2, Ni-NiSe2 and Ni-Ni(S0.51Se0.49)2 at different potentials, respectively; ORR and OER pathways of Ni-Ni(S0.51Se0.49)2@NC. Reprinted with permission from Ref. [123]. Copyright 2022, John Wiley and Sons. (b) Schematic structure of CoS and Co(S, Se) electrocatalysts; electron density distribution around Co atoms exposed on (100) surface of CoS and Co(S, Se); Gibbs free energy diagrams of CoS and Co(S, Se) for the OER; the corresponding TDOS. Reprinted with permission from Ref. [124]. Copyright 2021, Elsevier.
Fig. 7. DOS of Co 3d and S 3p orbitals in Co3S4 (a) and HS Co3S4 (b). (c) DOS of eg and t2g orbitals in the Co3S4 and HS Co3S4. (d) The illustration of the band structure of Co 3d orbitals in different configurations; the molecular orbital structure and electron filling of LS Co3S4 and HS Co3S4, respectively. Reprinted with permission from Ref. [134]. Copyright 2025, American Chemical Society.
Fig. 8. (a) Schematic representation of charge density transfer at Ni sites in c-NiSe2, c/a-NiSe2, and CoxNi1-xSe2 based on Bader charge analysis; calculated DOS; Gibbs free energy diagrams of c/a-NiOOH and c/a-Co-NiOOH for the OER; schematic diagrams of rigid band structure for c/a-NiSe2, and CoxNi1?xSe2; Reprinted with permission from Ref. [160]. Copyright 2025, Elsevier. (b) XPS spectra of Se 3d on Fe@CoS/Se2-NRs, Co-Se2, and Fe-Se2; Gibbs free energy diagrams for the OER process at Co sites in the Fe@CoS/Se2-NRs, Co-Se2, and Fe-Se2 (inset: the molecular structure with O adsorption on Co site of Co-Se2); the PDOS of Fe@CoS/Se2-NRs, Co-Se2, and Fe-Se2, respectively. Reprinted with permission from Ref. [161]. Copyright 2022, Elsevier.
Fig. 9. (a) Schematic diagram of the OER process at the Co site of (Fe0.25Co0.75)OOH model in alkaline medium. (b) Difference charge density of the (Fe0.25Co0.75)OOH. (c) DOS of the (Fe0.25Co0.75)OOH. (d) OER polarization curves of CoS2, FeS2, and (FexCo1?x)S2 electrocatalysts in the 1.0 mol L?1 KOH; (e) Comparison of overpotentials at 10 mA cm?2. (f) The corresponding Tafel slope curves. Reprinted with permission from Ref. [164]. Copyright 2014, Royal Society of Chemistry. (g) COHP and PDOS profiles of NiSe2, and FexNi1?xSe2 electrocatalysts. (h) The energy barrier for RDS. Insert: structure models of NiSe2, and FexNi1?xSe2 electrocatalysts. Reprinted with permission from Ref. [170]. Copyright 2023, Elsevier.
| Catalysts/ counterpart | η (mV) | Tafel slop (mV dec‒1) | Stability (V vs. RHE) | Ref. |
|---|---|---|---|---|
| Co-Se1 (mCo:mSe = 1:0.02) | 280@100 mA cm‒2 | 40 | chronoamperometry at 1.57 V for 12 h; 2000 cycles | [ |
| Co-Se4 (mCo:mSe = 1:0.2) | 410@100 mA cm‒2 | 71 | — | |
| Ni3Se2 | — | 46 | — | [ |
| NiSe | — | 72 | — | |
| NiO | — | 136 | — | |
| FeNiOOH(Se)/IF | 222@10 mA cm‒2 279@100 mA cm‒2 | — | chronopotentiometry at 100 mA cm‒2 for 100 h; at 100 mA cm‒2 for 50 h in an electrolyzer | [ |
| FeOOH(Se)/IF | 287@10 mA cm‒2 364@100 mA cm‒2 | 54 | chronoamperometry at 10 mA cm‒2 for 15 h | |
| two-tiered NiSe | 290@10 mA cm‒2 | 77 | — | [ |
| two-tiered Ni(OH)2 | 350@10 mA cm‒2 | 86 | — | |
| Co(S, Se)@GNF | 347@10 mA cm‒2 | 69 | after 10000 cycles, η10 value increases 10 mV | [ |
| CoS@GNF | 400@10 mA cm‒2 | 83 | — | |
| HS Co3S4 | 222@10 mA cm‒2 277@100 mA cm‒2 | 35 | chronopotentiometry at 100 mA cm‒2 for 24 h; at 100 mA cm‒2 for 24 h in an electrolyzer | [ |
| Co3S4 | 287@10 mA cm‒2 431@100 mA cm‒2 | 139 | — | |
| CoS2 HNSs | 290@10 mA cm‒2 | 57 | chronoamperometry at 1.9 V for 10 h in an electrolyzer | [ |
| Co9S8 HNSs | 342@10 mA cm-2 | 104 | — | |
| Co3S4 HNSs | 307@10 mA cm‒2 | 108 | — | |
| (Ni, Co)0.85Se/CFC | 255@10 mA cm‒2 | 79 | chronopotentiometry at 10 mA cm‒2 for 24 h | [ |
| Co0.85Se/CFC | 324@10 mA cm‒2 | 85 | — | |
| CoxNi1‒xSe2@Co(OH)2/NF | 231@10 mA cm‒2 307@100 mA cm‒2 | 54 | chronoamperometry at 0.8 V vs. Hg/HgO for 50 h, current retention of 98.2% | [ |
| NiSe2/NF | 254@10 mA cm‒2 335@100 mA cm‒2 | 72 | chronoamperometry at 0.8 V vs. Hg/HgO for 50 h, current retention of 92.7% | |
| Fe@Co/Se2-NRs | 200@10 mA cm‒2 | 35 | continuous operation at 100 mA cm‒2 for 72 h in an electrolyzer | [ |
| Fe-Se2 | 360@10 mA cm‒2 | 105 | — | |
| Co-Se2 | 250@10 mA cm‒2 | 67 | — | |
| NiCo2S4 | 247@10 mA cm‒2 | 62 | chronoamperometry at 1.6 V for 24 h | [ |
| NiCo3S4 | 264@10 mA cm‒2 | 68 | — | |
| NiCoS4 | 285@10 mA cm‒2 | 79 | — | |
| (Fe0.25Co0.75)S2 | 274@10 mA cm‒2 | 34 | chronopotentiometry at 20 mA cm‒2 for 60 h | [ |
| (Fe0.20Co0.80)S2 | 285@10 mA cm‒2 | 50 | — | |
| (Fe0.33Co0.67)S2 | 292@10 mA cm‒2 | 41 | — | |
| Fe0.4Co0.6Se2 | 270@10 mA cm‒2 | 36 | chronopotentiometry at 10 mA cm‒2 for 24 h | [ |
| Fe0.2Co0.8Se2 | 287@10 mA cm‒2 | 45 | — | |
| Fe0.6Co0.4Se2 | 313@10 mA cm‒2 | 52 | — | |
| FeCoNiS | 164@10 mA cm‒2 | 23 | chronopotentiometry at 10 mA cm‒2 for 800 h and 100 mA cm‒2 for 2200 h | [ |
| FeCoS | 219@10 mA cm‒2 | 28 | — | |
| CoNiS | 216@10 mA cm‒2 | 34 | — | |
| FeNiS | 251@10 mA cm‒2 | 40 | — |
Table 2 Summary of the overpotential, Tafel slope, turn over frequency and stability for reported IGTMC catalysts and the corresponding counterparts in 1.0 mol L?1 KOH or NaOH solution.
| Catalysts/ counterpart | η (mV) | Tafel slop (mV dec‒1) | Stability (V vs. RHE) | Ref. |
|---|---|---|---|---|
| Co-Se1 (mCo:mSe = 1:0.02) | 280@100 mA cm‒2 | 40 | chronoamperometry at 1.57 V for 12 h; 2000 cycles | [ |
| Co-Se4 (mCo:mSe = 1:0.2) | 410@100 mA cm‒2 | 71 | — | |
| Ni3Se2 | — | 46 | — | [ |
| NiSe | — | 72 | — | |
| NiO | — | 136 | — | |
| FeNiOOH(Se)/IF | 222@10 mA cm‒2 279@100 mA cm‒2 | — | chronopotentiometry at 100 mA cm‒2 for 100 h; at 100 mA cm‒2 for 50 h in an electrolyzer | [ |
| FeOOH(Se)/IF | 287@10 mA cm‒2 364@100 mA cm‒2 | 54 | chronoamperometry at 10 mA cm‒2 for 15 h | |
| two-tiered NiSe | 290@10 mA cm‒2 | 77 | — | [ |
| two-tiered Ni(OH)2 | 350@10 mA cm‒2 | 86 | — | |
| Co(S, Se)@GNF | 347@10 mA cm‒2 | 69 | after 10000 cycles, η10 value increases 10 mV | [ |
| CoS@GNF | 400@10 mA cm‒2 | 83 | — | |
| HS Co3S4 | 222@10 mA cm‒2 277@100 mA cm‒2 | 35 | chronopotentiometry at 100 mA cm‒2 for 24 h; at 100 mA cm‒2 for 24 h in an electrolyzer | [ |
| Co3S4 | 287@10 mA cm‒2 431@100 mA cm‒2 | 139 | — | |
| CoS2 HNSs | 290@10 mA cm‒2 | 57 | chronoamperometry at 1.9 V for 10 h in an electrolyzer | [ |
| Co9S8 HNSs | 342@10 mA cm-2 | 104 | — | |
| Co3S4 HNSs | 307@10 mA cm‒2 | 108 | — | |
| (Ni, Co)0.85Se/CFC | 255@10 mA cm‒2 | 79 | chronopotentiometry at 10 mA cm‒2 for 24 h | [ |
| Co0.85Se/CFC | 324@10 mA cm‒2 | 85 | — | |
| CoxNi1‒xSe2@Co(OH)2/NF | 231@10 mA cm‒2 307@100 mA cm‒2 | 54 | chronoamperometry at 0.8 V vs. Hg/HgO for 50 h, current retention of 98.2% | [ |
| NiSe2/NF | 254@10 mA cm‒2 335@100 mA cm‒2 | 72 | chronoamperometry at 0.8 V vs. Hg/HgO for 50 h, current retention of 92.7% | |
| Fe@Co/Se2-NRs | 200@10 mA cm‒2 | 35 | continuous operation at 100 mA cm‒2 for 72 h in an electrolyzer | [ |
| Fe-Se2 | 360@10 mA cm‒2 | 105 | — | |
| Co-Se2 | 250@10 mA cm‒2 | 67 | — | |
| NiCo2S4 | 247@10 mA cm‒2 | 62 | chronoamperometry at 1.6 V for 24 h | [ |
| NiCo3S4 | 264@10 mA cm‒2 | 68 | — | |
| NiCoS4 | 285@10 mA cm‒2 | 79 | — | |
| (Fe0.25Co0.75)S2 | 274@10 mA cm‒2 | 34 | chronopotentiometry at 20 mA cm‒2 for 60 h | [ |
| (Fe0.20Co0.80)S2 | 285@10 mA cm‒2 | 50 | — | |
| (Fe0.33Co0.67)S2 | 292@10 mA cm‒2 | 41 | — | |
| Fe0.4Co0.6Se2 | 270@10 mA cm‒2 | 36 | chronopotentiometry at 10 mA cm‒2 for 24 h | [ |
| Fe0.2Co0.8Se2 | 287@10 mA cm‒2 | 45 | — | |
| Fe0.6Co0.4Se2 | 313@10 mA cm‒2 | 52 | — | |
| FeCoNiS | 164@10 mA cm‒2 | 23 | chronopotentiometry at 10 mA cm‒2 for 800 h and 100 mA cm‒2 for 2200 h | [ |
| FeCoS | 219@10 mA cm‒2 | 28 | — | |
| CoNiS | 216@10 mA cm‒2 | 34 | — | |
| FeNiS | 251@10 mA cm‒2 | 40 | — |
Fig. 10. Schematic diagram of integrated in-situ/operando electrochemical-spectroscopy techniques for monitoring active sites and reaction mechanisms. Reprinted with permission from Ref. [193]. Copyright 2025, Springer Nature.
Fig. 11. (a) The setup of in-situ/operando Raman measurement and digital photo the in-situ test system. Inset: electrochemical cell. Reprinted with permission from Ref. [195]. Copyright 2023, Elsevier. (b) In-situ Raman spectra of Ni0.8Fe0.2Co0.1Se2 electrocatalyst during OER process. (c) Schematic diagram of in-situ transformation and possible active centers (Ni-Fe-Co: active center 1; Ni-Fe-Ni: active center 2 and Ni-Ni-Ni: active center 3). (d) On-line DEMS signals for 18O-labeled Ni0.8Fe0.2Co0.1Se2 during the OER. (e) The AEM; (f) Gibbs free energy diagrams for the OER at three active centers on the (001) surface of (Fe, Co)-doped γ-NiOOH. Reprinted with permission from Ref. [208]. Copyright 2025, Elsevier.
Fig. 12. (a) In-situ Raman spectra of Se-NiS2/CC, NiS2/CC and NiSe2/CC catalysts during OER process; comparison of the potentials required for surface reconstruction to Ni(OH)2 or NiOOH. (b) DFT calculation analysis. Gibbs free energy diagrams for NiOOH/Se-NiS2 and NiOOH/NiS2; PDOS of d-bands of Ni sites in the NiOOH/Se-NiS2 and NiOOH/NiS2; the COHP between S and Ni of NiS2 and Se-NiS2; charge density difference images for NiOOH/Se-NiS2 (upper) and NiOOH/NiS2 (lower); One-dimensional charge density difference between NiOOH and NiS2 (or Se-NiS2). Reprinted with permission from Ref. [209]. Copyright 2023, Elsevier.
Fig. 13. LSV curves and potential-dependent in-situ Raman spectra of Cu(OH)2 (a), Co(OH)2 (b), NiS2 (c), Ni(OH)2 + SO42− (d), NiSe2 (e), Ni(OH)2 + SeO32− (f) under OER conditions. (g) DFT analysis: Gibbs free energy diagrams of NiOOH and NiOOH + SeO4, DOS of Ni 3d orbitals in NiOOH and NiOOH + SeO4; differential charge density of NiOOH + SeO4. (h) Illustration of promoted OER activity of the chalcogenates-adsorbed MOOH on the surface of TMCs. Reprinted with permission from Ref. [212]. Copyright 2020, John Wiley and Sons.
Fig. 14. (a) In-situ XRD patterns of Ni3Se4/UCL-3 during the OER; Gibbs free energy diagrams of UNC, Ni3Se4/UCL-Se (Se atom exposure) and Ni3Se4/UCL-Ni (Ni atom exposure); the corresponding DOS. Reprinted with permission from Ref. [215]. Copyright 2022, Elsevier. (b) Illustration of XRD equipment integrated with a two-electrode electrochemical system; in-situ XRD patterns of c-CoSe2-CoN/NC during the OER; ORR/OER mechanism on the optimized configuration of c-CoSe2-CoN/NC; d-band centers of the CoN, c-CoSe2 and c-CoSe2-CoN; Gibbs free energy diagrams for OER and OER at four active sites, respectively; calculated *OOH adsorption and *OH desorption energy on CoN, c-CoSe2, and c-CoSe2-CoN. Reprinted with permission from Ref. [216]. Copyright 2023, John Wiley and Sons.
Fig. 15. (a) Schematic drawing of a flow electrochemical cell used for in-situ sXAS experiments. Reprinted with permission from Ref. [221]. Copyright 2019, John Wiley and Sons. (b) Summary diagram of structure information for the catalyst obtained by hard/soft-XAS. Reprinted with permission from Ref. [222]. Copyright 2024, Royal Society of Chemistry. (c) Spin state analysis under the OER conditions. Fe K-edge XANES spectra and Fe K-edge FT-EXAFS during OER process with the different potentials (vs. RHE) of OCV, 1.245 and 1.445 V in 1 mol L-1 KOH, respectively; in-situ Raman spectroscopy of CFS-ACs/CNT catalyst; Fe L-edge XANES spectra before and after stability of CFS-ACs/CNT; the orbital interactions between cations and the OER intermediates of Fe and Co during OER process according to the bond order theorem. The red region represents more favorable metal spin-orbit coupling interactions; the schematic diagram of dual-site adsorbate evolution mechanisms for coupled O-O bonding during the OER. Reprinted with permission from Ref. [218]. Copyright 2024, Springer Nature. (d) Operando k3-weighted FT EXAFS spectra of the CoS2 and Fe-OH-CoS2 at the different potentials, respectively. Reprinted with permission from Ref. [219]. Copyright 2024, John Wiley and Sons. (e) Operando XAS characterizations of CoS in 1 mol L-1 KOH for the OER. Operando Co K-edge XANES spectra; 3D contour plots of operando Co K-edge FT-EXAFS spectra; fitting of operando Co K-edge FT-EXAFS spectra. Reprinted with permission from Ref. [220]. Copyright 2024, John Wiley and Sons.
Fig. 16. (a) Operando XAFS spectra on the Co9S8-SWCNT at pH = 7 and 14 for the OER. Reprinted with permission from Ref. [223]. Copyright 2021, Royal Society of Chemistry. (b) Operando XANES and FT-EXAFS spectra of Ni K-edge and the corresponding 2D contour plots for the NiSe2@CNA@CC during chrono-potential treatment at 10 mA cm?2. (I) NiSe2 → Ni(OH)2; (II) NS-Ni(OH)2 → NS-NiOOH; and (III) NiOOH acted as the stable active catalyst for the reaction. Reprinted with permission from Ref. [224]. Copyright 2019, John Wiley and Sons.
Fig. 17. (a) Schematic diagram of in-situ liquid electrochemical transmission electron microscopy (EC-TEM). (I) In-situ EC-TEM holder from Protochips (the inset shows the tip of the holder where the miniaturized electrochemical cell is integrated); (II) In-situ disposable chip positioned at the tip of the sample holder; (III) transversal schematic view of the assembled cell. Reprinted with permission from Ref. [226]. Copyright 2019, American Chemical Society. (b) In-situ TEM observation of CoSx evolution during the OER test. (c) In-situ HRTEM images and corresponding SAED patterns of CoSx evolution to CoOOH alpha phase during the OER. (d) Chronopotentiometry curve of CoSx at a low anodic current density of 0.5 mA cm-2. (e) In-situ FTIR of CoSx with 1 mA anodic current in 1 mol L-1 KOH. Reprinted with permission from Ref. [225]. Copyright 2018, American Chemical Society.
| Electrocatalyst | Active species | Characterization | Ref. |
|---|---|---|---|
| Se-NiS2 | γ-NiOOH | In-situ Raman | [ |
| NiSe2 (NiS2) | NiOOH and SeO32‒ (SO42‒) | In-situ Raman | [ |
| Ni3Se4 | β-NiOOH | In-situ XRD | [ |
| c-CoSe2-CoN | α-CoOOH and γ-NiOOH | In-situ XRD | [ |
| Ni-Fe-S/NCQDs | β-FeOOH/NiOOH | In-situ XRD | [ |
| CoS | CoO2 species | Operando XAS | [ |
| Co9S8 | S-CoOOH | In-situ XAS | [ |
| NiSe2 | NiOOH | In-situ XAS | [ |
| (Ni, Co)3Se4 | γ-(Ni, Co)OOH | In-situ XAS | [ |
| NixFe1‒xSe2 | Ni-Fe-Se-OOH | In-situ XAS | [ |
| NiSe2/CoSe2-N | NiSe2/CoSe2@NiOOH/CoOOH | In-situ XAS | [ |
| CoSx | CoOOH | In-situ TEM | [ |
| CoFeSx | Co-O-O-Fe intermediates | In-situ XAS and Raman | [ |
| Ni0.8Fe0.2Co0.1Se2 | (Fe, Co) doped γ-NiOOH | In-situ Raman and DEMS | [ |
| CeO2-CoS1.97 | CoIV species | Operando Raman and quasi-operando XPS | [ |
| Co9S8@Fe3O4 | CoOOH@Fe3O4 | Operando Raman, FTIR, and XAS | [ |
Table 3 Summary of recent advances in the identifications of active species of IGTMC electrocatalysts for OER in alkaline conditions.
| Electrocatalyst | Active species | Characterization | Ref. |
|---|---|---|---|
| Se-NiS2 | γ-NiOOH | In-situ Raman | [ |
| NiSe2 (NiS2) | NiOOH and SeO32‒ (SO42‒) | In-situ Raman | [ |
| Ni3Se4 | β-NiOOH | In-situ XRD | [ |
| c-CoSe2-CoN | α-CoOOH and γ-NiOOH | In-situ XRD | [ |
| Ni-Fe-S/NCQDs | β-FeOOH/NiOOH | In-situ XRD | [ |
| CoS | CoO2 species | Operando XAS | [ |
| Co9S8 | S-CoOOH | In-situ XAS | [ |
| NiSe2 | NiOOH | In-situ XAS | [ |
| (Ni, Co)3Se4 | γ-(Ni, Co)OOH | In-situ XAS | [ |
| NixFe1‒xSe2 | Ni-Fe-Se-OOH | In-situ XAS | [ |
| NiSe2/CoSe2-N | NiSe2/CoSe2@NiOOH/CoOOH | In-situ XAS | [ |
| CoSx | CoOOH | In-situ TEM | [ |
| CoFeSx | Co-O-O-Fe intermediates | In-situ XAS and Raman | [ |
| Ni0.8Fe0.2Co0.1Se2 | (Fe, Co) doped γ-NiOOH | In-situ Raman and DEMS | [ |
| CeO2-CoS1.97 | CoIV species | Operando Raman and quasi-operando XPS | [ |
| Co9S8@Fe3O4 | CoOOH@Fe3O4 | Operando Raman, FTIR, and XAS | [ |
Fig. 18. Schematic illustration of the surface reconstruction process of chalcogenides during the OER. Reprinted with permission from Ref. [229]. Copyright 2025, Elsevier.
| Technique | Spatial resolution | Temporal resolution | Information probed | Advancement | Critical limitations |
|---|---|---|---|---|---|
| Raman | nm to μm | ms to s | molecular vibration; interfacial adsorbed species; phase | excellent compatibility with aqueous systems; achievable under ambient temperature and pressure | susceptible to fluorescence interference; weak signal intensity; low detection sensitivity |
| XAS | μm to nm | ms to s | valence state; coordination environment | high element specificity; unaffected by phase crystallinity; in-situ tracking of dynamic changes in the chemical state of elements | low spatial resolution; unable to localize microregions; high cost; complex data analysis |
| XRD | μm to mm | s to min | crystal structure, grain size, phase transition kinetics | strong in-situ compatibility (adapts to high/low temperature, electrochemical, and atmospheric sample stages) | insensitive to amorphous phases; the overall average conceals heterogeneities |
| HRTEM | 0.1-1 nm | s to min | directly imaging crystal lattice with real-time atomic resolution | In-situ observation of nanoscale dynamic processes; simultaneous acquisition of morphological and crystal structure information | electron beam damage; poor temporal resolution for fast dynamics |
| FTIR | 1-20 μm | s | molecular functional groups; chemical bond vibrations | In-situ compatibility with atmospheric and low-temperature scenarios; qualitative analysis of chemical composition | severe interference from aqueous systems; limited capability for characterizing inorganic materials |
| EC-MS | none | ms | volatile products of electrochemical reactions; quantitative product yield | direct correlation of electrochemical signals with products; in-situ real-time tracking of electrochemical reaction dynamics | detects only final products; unable to obtain sample structure/ chemical state information |
Table 4 Spatial resolution, temporal resolution, probed information, advancements, and limitations of selected in-situ techniques.
| Technique | Spatial resolution | Temporal resolution | Information probed | Advancement | Critical limitations |
|---|---|---|---|---|---|
| Raman | nm to μm | ms to s | molecular vibration; interfacial adsorbed species; phase | excellent compatibility with aqueous systems; achievable under ambient temperature and pressure | susceptible to fluorescence interference; weak signal intensity; low detection sensitivity |
| XAS | μm to nm | ms to s | valence state; coordination environment | high element specificity; unaffected by phase crystallinity; in-situ tracking of dynamic changes in the chemical state of elements | low spatial resolution; unable to localize microregions; high cost; complex data analysis |
| XRD | μm to mm | s to min | crystal structure, grain size, phase transition kinetics | strong in-situ compatibility (adapts to high/low temperature, electrochemical, and atmospheric sample stages) | insensitive to amorphous phases; the overall average conceals heterogeneities |
| HRTEM | 0.1-1 nm | s to min | directly imaging crystal lattice with real-time atomic resolution | In-situ observation of nanoscale dynamic processes; simultaneous acquisition of morphological and crystal structure information | electron beam damage; poor temporal resolution for fast dynamics |
| FTIR | 1-20 μm | s | molecular functional groups; chemical bond vibrations | In-situ compatibility with atmospheric and low-temperature scenarios; qualitative analysis of chemical composition | severe interference from aqueous systems; limited capability for characterizing inorganic materials |
| EC-MS | none | ms | volatile products of electrochemical reactions; quantitative product yield | direct correlation of electrochemical signals with products; in-situ real-time tracking of electrochemical reaction dynamics | detects only final products; unable to obtain sample structure/ chemical state information |
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