Electrospinning technology combined with MOFs: Bridging the development of high-performance zinc-air batteries

doi:10.1016/S1872-2067(25)64817-0

Chinese Journal of Catalysis ›› 2025, Vol. 79: 32-67.DOI: 10.1016/S1872-2067(25)64817-0

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Electrospinning technology combined with MOFs: Bridging the development of high-performance zinc-air batteries

Haotian Guo^a, Lulu Zhao^a, Xinyu Liu^a, Jing Li^b, Pengfei Wang^a, Zonglin Liu^a, Linlin Wang^a, Jie Shu^c, Tingfeng Yi^a^,^b^,^d^,^*()

^aSchool of Materials Science and Engineering, Northeastern University, Shenyang 110819, Liaoning, China
^bState Key Laboratory of Environmental-Friendly Energy Materials, School of Materials and Chemistry, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China
^cSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, Zhejiang, China
^dKey Laboratory of Dielectric and Electrolyte Functional Material Hebei Province, School of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao 066004, Hebei, China

Received:2025-05-25 Accepted:2025-07-28 Online:2025-12-18 Published:2025-10-27
Contact: Tingfeng Yi
About author:Ting-Feng Yi (School of Resources and Materials, Northeastern University at Qinhuangdao) received M.S. degree in 2004 and Ph.D. degree in 2007 from Harbin Institute of Technology. He joined the Anhui University of Technology as an assistant professor in 2007 and was promoted to a full professorship in 2011. His research focuses on electrocatalysis, water electrolysis and chemical energy conversation, combining experimental investigations with theoretical simulation. He has published over 240 peer-reviewed papers and holds 17 Chinese invention patents and 2 Dutch invention patents. His work has been cited over 11,000 times. In addition, as editor in chief, he also wrote two books: Electrode Materials for Lithium Ion Batteries, and Fundamentals and Applications of Sodium Ion Batteries. He was invited as a member of the Senior Editorial Board of Acta Physico-Chimica Sinica Since 2024.
Supported by:
National Natural Science Foundation of China(52574348);National Natural Science Foundation of China(52374301);Open Project of State Key Laboratory of Environment-friendly Energy Materials(24kfhg06);Natural Science Foundation of Hebei Province(E2024501010);Natural Science Foundation of Hebei Province(B2024501004);Shijiazhuang Basic Research Project(241790667A);Fundamental Research Funds for the Central Universities(N2423013);Performance Subsidy Fund for Key Laboratory of Dielectric, Electrolyte Functional Material Hebei Province(22567627H)

Abstract

Abstract:

Metal-organic frameworks (MOFs) are porous materials formed by the coordination of organic and inorganic components through coordination bonds. MOF-derived materials preserve the large surface area and inherent porosity of their parent structures, while simultaneously offering enhanced electrical conductivity and more efficient charge transport. Studies have shown that integrating electrospinning with MOFs into continuous nanofiber networks can effectively address issues such as MOF structural collapse, low conductivity, and leaching of active sites. Moreover, the electrospinning technique enables fine-tuning of the product’s morphology, architecture, and chemical composition, thereby unlocking new possibilities for advancing high-performance ZABs. This review provides a systematic overview of recent advances in non-precious metal electrocatalysts derived from electrospun-MOF composites and examines the unique advantages of combining electrospinning with MOF precursors in the design of oxygen electrocatalysts. It also investigates the morphological regulation of various fiber structures, including porous, hollow, core-shell, and beaded structures, as well as their influence on the catalytic performance. Finally, the performance enhancement strategies of electrospun-MOF catalyst materials are examined, and the development prospects along with future research directions related to oxygen electrocatalysts based on electrospun nanofibers are emphasized. This thorough review aims to offer meaningful insights and practical guidance for advancing the understanding, design, and fabrication of next-generation devices for energy conversion and storage.

Key words: Zinc-air battery, Oxygen reduction reaction, Oxygen evolution reaction, Electrospinning, Metal-organic frameworks, Nanofibers

Haotian Guo, Lulu Zhao, Xinyu Liu, Jing Li, Pengfei Wang, Zonglin Liu, Linlin Wang, Jie Shu, Tingfeng Yi. Electrospinning technology combined with MOFs: Bridging the development of high-performance zinc-air batteries[J]. Chinese Journal of Catalysis, 2025, 79: 32-67.

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Figures/Tables 15

Scheme 1. Representative timeline of electrospun-MOF composite materials as oxygen electrocatalysts in the field of ZABs. All insets come from the literature. Reproduced with permission from Ref. [49]. Copyright 2020, Elsevier. Reproduced with permission from Ref. [50]. Copyright 2021, Wiley-VCH. Reproduced with permission from Ref. [51]. Copyright 2022, Wiley-VCH. Reproduced with permission from Ref. [52]. Copyright 2023, Elsevier. Reproduced with permission from Ref. [53]. Copyright 2024, Springer Nature. Reproduced with permission from Ref. [54]. Copyright 2025, Oxford University Press.

Scheme 2. Electrospun-MOF composite materials as oxygen electrocatalysts for ZABs.

Fig. 1. (a) electrospinning equipment and a variety of electrospinning. Reproduced with permission from Ref. [60]. Copyright 2016, Royal Society of Chemistry. (b) Surface plot of behavior of axial velocity at 10 cm. (c) Surface plot of the behavior of axial velocity at 20 cm. (d) Representation of axial velocity over time for λBratu = 0.5. Reproduced with permission from Ref. [65]. Copyright 2024, Springer Nature.

Fig. 2. Outlines the systematic synthesis process of the Co-based precursor (a) and SEM images (b). Reproduced with permission from Ref. [73]. Copyright 2025, Royal Society of Chemistry. (c) Reaction pathway of US-MOFNFs. (d) SEM images of MOFs obtained under solvothermal conditions for 6 h. Reproduced with permission from Ref. [75]. Copyright 2025, Elsevier. (e) Schematic diagram depicting the fabrication process of the CoNP/SA-NC/Fe-NCNTs electrocatalyst. (f) The HRTEM patterns of CoNP/SA-NC/Fe-NCNTs catalyst. (g) HAADF-STEM diagrams of CoNP/SA-NC/Fe-NCNTs catalyst. Reproduced with permission from Ref. [77]. Copyright 2025 Wiley-VCH. (h) SEM images of Fe-ZIF-8/ZIF-8. SEM photographs of Fe-8/8-CN (i) and Fe-8-CN (j). Reproduced with permission from Ref. [81]. Copyright 2024, American Chemical Society.

Fig. 3. (a) Illustration depicting the fabrication procedure of MAPC (A). Reproduced with permission from Ref. [94]. Copyright 2024, Elsevier. (b) Schematic diagram depicting the synthesis of MOF@Ru and the detection and adsorption mechanism of AFB1 using a ratiometric fluorescence probe. Reproduced with permission from Ref. [95]. Copyright 2024, Elsevier. (c) Fabrication of BG-PLA NFMs through coaxial electrospinning technique. Reproduced with permission from Ref. [96]. Copyright 2025, Elsevier. (d) Scheme for the synthesis of CoxP@CF-900. Reproduced with permission from Ref. [97]. Copyright 2021, Wiley-VCH. (e) Illustration of the ORR mechanism catalyzed by Ru@FeZn-HNC/CNFs. Reproduced with permission from Ref. [98]. Copyright 2025, Elsevier. (f) Schematic diagram of PMMNFs@Zn/Co-ZIF synthesis. Reproduced with permission from Ref. [99]. Copyright 2023, Elsevier.

Fig. 4. (a) Preparation Process of Fe-ZCNF. (b) High-resolution SEM image. (c) galvanostatic charge-discharge voltage cycling curve at 10 mA cm-2. Reproduced with permission from Ref. [148]. Copyright 2025 Elsevier. (d) Schematic depiction of the fabrication route for ZxNy-CNFs. (e) Galvanostatic cycling stability of ZABs at 5 mA cm-2. Reproduced with permission from Ref. [149]. Copyright 2025, Elsevier. (f) Schematic illustration of the synthesis procedure of FeN4-NFS-CNF. (g) SEM images of FeN4-NFS-CN. (h,i) TEM images of FeN4-NFS-CNF. Reproduced with permission from Ref. [155]. Copyright 2023, Wiley-VCH. (j) Schematic diagram of the synthesis process for NiCo@C@CoMn CNFs. Reproduced with permission from Ref. [156]. Copyright 2025, Elsevier. (k) Galvanostatic charge-discharge cycling curves at 5 mA cm-2, and the insert is the photo of the solid battery with different bending angles. Reproduced with permission from Ref. [51]. Copyright 2022, Wiley-VCH.

Fig. 5. (a) Illustration of the fabrication process for Co-doped flexible carbon nanofiber membranes via the core-shell electrospinning method. Reproduced with permission from Ref. [160]. Copyright 2022, Elsevier. (b) TEM images of the Co-NFs. (c,d) TEM images of the Co-CSNFs. Reproduced with permission from Ref. [161]. Copyright 2023, Elsevier. (e) Stepwise synthesis diagram of CNFs/CoZn-MOF@COF composite. Reproduced with permission from Ref. [163]. Copyright 2024, Elsevier. (f) Schematic of ORR process in bead-like Co-N-C/CNF composite. Reproduced with permission from Ref. [166]. Copyright 2022, Springer Nature. (g,h,i) TEM images of Fe@NC-Ac-2S-800. Reproduced with permission from Ref. [167]. Copyright 2024, Elsevier. (j) Schematic diagram about the beaded Fe, Co-N-C/CNF catalyst for ORR and OER reactions. (k) Schematic illustration about covalent bond hybridization between active centers and ORR (OER) intermediates for Fe, Co-N-C/CNF. Reproduced with permission from Ref. [168]. Copyright 2024, American Chemical Society.

Table 1 Comparison of physical parameters and electrochemical parameters of catalysts with different fiber morphologies.

Catalysts	Voltage (kV)	Electrospinning solution (precursor/polymer/solvent)	Working distance (cm)/temperature (°C)/humidity (%)	Annealing temperature (°C)	Morphology	Active sites	Surface area (BET N₂ adsorption- desorption measurements) (m² g^-1)	E_1/2 [V] (ORR) Pt/C	E_j₌₁₀ [V] (OER)/ RuO₂	Electrolyte ORR/OER 1600 rpm/0 rpm	Peak PC [mW cm^-2] @Window voltage [V]	Cycling stability	Rate performance	Ref.
Fe-ZCNF	22	ZIF-8/ PAN/DMF	15/—/—	900 (N₂, 2 h)	porous	Fe-N_x	1035.5	0.88/ 0.86	1.63/ 1.6	0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH	179.2@ 0.75	>200 h/10 mA cm^-2	Stable discharge voltage plateau at 10-100 mA cm^-2	[148]
ZN₃- CNFs- 900	15	ZnCo-ZIF/ PVP, PAN/DMF	12/18-22/45	900 (N₂, 2 h)	porous	Co-N_x	562.77	0.834/ 0.824	1.695/ 1.692	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	111@ 0.63	400 h/5 mA cm^-2	—	[149]
N-CNT@ MOF-Co/HO-BN/CNFs	18	Co(NO₃)₂/ HO-BN/PAN/DMF	15/	1000 (N₂, 2 h)	porous	Co-N_x	352	0.84/ 0.84	1.51/ 1.49 (IrO₂)	0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH	142.9@ 0.45	>200 h/5 mA cm^-2	—	[150]
FeN₄- NFS-CNF	19	ZnFe-ZIF/ PAN, PMMA/DMF	15/—/—	1000 (N₂, 1 h)	hollow	Fe-N₄	1693.98	0.90/ 0.84	1.50/ 1.57	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	201.5@ 0.6	1000 h /10 mA cm^-2	0.25V gap @10mA cm^-2, Holds 1.14V @50mA cm^-2, Superior to Pt/C	[155]
NiCo@C@CoMnCNFs	15	Ni (Ac)₂, Co (Ac)₂/ PMMA, PVP, PAN/ DMF	15/25-30 /30-40	800 (Ar, 2 h)	hollow	CoMn,NiCo	325.9	0.82/ 0.83	1.628/ 1.738	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	130.3@ 0.59	1650 h/5 mA cm^-2	—	[156]
NiFe@ C@Co CNFs	15	Ni(Ac)₂, Fe(AcAc)₃/ PAN, PMMA/ DMAC	15/25/25	800 (N₂, 2 h)	hollow	Co-N, NiFe-N	209	0.87/ 0.85	1.6/1.599	0.1 mol L^-1 KOH/0.1 mol L^-1 KOH	130@ 0.52	67 h/5 mA cm^-2	—	[51]
Co-N- CCNFMs	20	Zn/Co-ZIFs/ PVP, PAN/DMF	—	500 (Ar, 1 h), 900 (Ar, 1 h)	core- shell	Co-N₄	750.87	0.84/ 0.85	1.559/ >1.599	0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH	61.5@ 0.6	37 h/2 mA cm^-2	Voltage retention = 100% from 1 to 15 mA cm^-2	[160]
Co- CSNFs	18	Co (NO₃)₂·6H₂O/PAN/DMF	—	1000 (N₂, 1h)	core- shell	Co-N_x	—	0.86/ 0.88	—	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	57.48@ 0.58	366 h/-	—	[161]
CNFs/CoZn-MOF@COF	17	2-MeIM /PAN/DMF	19/—/—	800(Ar, 2h)	core- shell	Co-N_x, Zn-N_x	381.26	0.82/ 0.83	1.573/-	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	203.63@ 0.74	180 h/10 mA cm^-2	Outperforms Pt/C in rate performance over the range of 2-50 mA cm^-2	[163]
Co-N-C/CNF	18	ZIF-67 /PAN/DMF	—	800(Ar, 1h)	beaded	Co_NP-N₁-C₂	332.5	0.859/ 0.857	—	0.1 mol L^-1 KOH/-	159@ 0.68	>100 h/10 mA cm^-2	Outperforms Pt/C in rate performance over 2-15 mA cm^-2	[166]
Fe, Co-N-C/CNF	17	Fe, Co-ZIF /PAN/ methanol	18-25/—/—	800(Ar, 1h)	beaded	Fe-N_x, Co-N_x	299.9	0.878/0.857	1.624	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	152@ 0.68	120 h/10 mA cm^-2	—	[168]
CoSe₂@NC@ NCNFs	15	ZIF-67 /PAN/DMF	15/—/—	1000 (Ar)	beaded	Co-N_x-C, CoSe₂	125.6	0.80/ 0.86	1.51/ 1.53	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	126.8@ 0.6	>240 cycles /10 mA cm^-2	Outperforms Pt/C in rate performance over 1-25 mA cm^-2	[169]

Table 1 Comparison of physical parameters and electrochemical parameters of catalysts with different fiber morphologies.

Catalysts	Voltage (kV)	Electrospinning solution (precursor/polymer/solvent)	Working distance (cm)/temperature (°C)/humidity (%)	Annealing temperature (°C)	Morphology	Active sites	Surface area (BET N₂ adsorption- desorption measurements) (m² g^-1)	E_1/2 [V] (ORR) Pt/C	E_j₌₁₀ [V] (OER)/ RuO₂	Electrolyte ORR/OER 1600 rpm/0 rpm	Peak PC [mW cm^-2] @Window voltage [V]	Cycling stability	Rate performance	Ref.
Fe-ZCNF	22	ZIF-8/ PAN/DMF	15/—/—	900 (N₂, 2 h)	porous	Fe-N_x	1035.5	0.88/ 0.86	1.63/ 1.6	0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH	179.2@ 0.75	>200 h/10 mA cm^-2	Stable discharge voltage plateau at 10-100 mA cm^-2	[148]
ZN₃- CNFs- 900	15	ZnCo-ZIF/ PVP, PAN/DMF	12/18-22/45	900 (N₂, 2 h)	porous	Co-N_x	562.77	0.834/ 0.824	1.695/ 1.692	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	111@ 0.63	400 h/5 mA cm^-2	—	[149]
N-CNT@ MOF-Co/HO-BN/CNFs	18	Co(NO₃)₂/ HO-BN/PAN/DMF	15/	1000 (N₂, 2 h)	porous	Co-N_x	352	0.84/ 0.84	1.51/ 1.49 (IrO₂)	0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH	142.9@ 0.45	>200 h/5 mA cm^-2	—	[150]
FeN₄- NFS-CNF	19	ZnFe-ZIF/ PAN, PMMA/DMF	15/—/—	1000 (N₂, 1 h)	hollow	Fe-N₄	1693.98	0.90/ 0.84	1.50/ 1.57	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	201.5@ 0.6	1000 h /10 mA cm^-2	0.25V gap @10mA cm^-2, Holds 1.14V @50mA cm^-2, Superior to Pt/C	[155]
NiCo@C@CoMnCNFs	15	Ni (Ac)₂, Co (Ac)₂/ PMMA, PVP, PAN/ DMF	15/25-30 /30-40	800 (Ar, 2 h)	hollow	CoMn,NiCo	325.9	0.82/ 0.83	1.628/ 1.738	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	130.3@ 0.59	1650 h/5 mA cm^-2	—	[156]
NiFe@ C@Co CNFs	15	Ni(Ac)₂, Fe(AcAc)₃/ PAN, PMMA/ DMAC	15/25/25	800 (N₂, 2 h)	hollow	Co-N, NiFe-N	209	0.87/ 0.85	1.6/1.599	0.1 mol L^-1 KOH/0.1 mol L^-1 KOH	130@ 0.52	67 h/5 mA cm^-2	—	[51]
Co-N- CCNFMs	20	Zn/Co-ZIFs/ PVP, PAN/DMF	—	500 (Ar, 1 h), 900 (Ar, 1 h)	core- shell	Co-N₄	750.87	0.84/ 0.85	1.559/ >1.599	0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH	61.5@ 0.6	37 h/2 mA cm^-2	Voltage retention = 100% from 1 to 15 mA cm^-2	[160]
Co- CSNFs	18	Co (NO₃)₂·6H₂O/PAN/DMF	—	1000 (N₂, 1h)	core- shell	Co-N_x	—	0.86/ 0.88	—	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	57.48@ 0.58	366 h/-	—	[161]
CNFs/CoZn-MOF@COF	17	2-MeIM /PAN/DMF	19/—/—	800(Ar, 2h)	core- shell	Co-N_x, Zn-N_x	381.26	0.82/ 0.83	1.573/-	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	203.63@ 0.74	180 h/10 mA cm^-2	Outperforms Pt/C in rate performance over the range of 2-50 mA cm^-2	[163]
Co-N-C/CNF	18	ZIF-67 /PAN/DMF	—	800(Ar, 1h)	beaded	Co_NP-N₁-C₂	332.5	0.859/ 0.857	—	0.1 mol L^-1 KOH/-	159@ 0.68	>100 h/10 mA cm^-2	Outperforms Pt/C in rate performance over 2-15 mA cm^-2	[166]
Fe, Co-N-C/CNF	17	Fe, Co-ZIF /PAN/ methanol	18-25/—/—	800(Ar, 1h)	beaded	Fe-N_x, Co-N_x	299.9	0.878/0.857	1.624	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	152@ 0.68	120 h/10 mA cm^-2	—	[168]
CoSe₂@NC@ NCNFs	15	ZIF-67 /PAN/DMF	15/—/—	1000 (Ar)	beaded	Co-N_x-C, CoSe₂	125.6	0.80/ 0.86	1.51/ 1.53	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH	126.8@ 0.6	>240 cycles /10 mA cm^-2	Outperforms Pt/C in rate performance over 1-25 mA cm^-2	[169]

Fig. 6. (a) EPR spectra of the Fe-N4-C and Fe-N4/NGC-C. Magnetic susceptibility of Fe-N4-C (b) and Fe-N4/NGC-C (c). Reproduced with permission from Ref. [54]. Copyright 2025, Oxford University Press. (d) ORR polarization curves for the initial and 20000 cycles, respectively. (e) Normalized chronoamperometric curves of FeN4-FeNCP@MCF, FeN4@MCF, and Pt/C catalyst at 0.7 V versus RHE. Reproduced with permission from Ref. [177]. Copyright 2024, Wiley-VCH. (f) AC-HAADF-STEM of Fe SACs@PNCNFs. (g) LSV curves for OER in 0.1 mol L-1 KOH at 1600 rpm. (h) Tafel slopes. Reproduced with permission from Ref. [178]. Copyright 2025, Wiley-VCH. Co K-edge X-ray absorption near-edge structure spectra (i) and FT k2-weighted EXAFS spectra (j) for CoN5/PCNF, CoN4/PCNF and the reference samples of bulk Co, Co3O4, and CoPc. (k) In-situ Raman spectra of CoN5/PCNF recorded at various potentials in O2-saturated 0.1 mol L-1 KOH electrolyte. Reproduced with permission from Ref. [181]. Copyright 2024, Wiley-VCH.

Fig. 7. (a) Adsorption configurations at each key step on the Fe5@FeN4 and Co2Fe2@CoN4 sites in the Co2Fe2@CoN4─Fe5@FeN4 model. Reproduced with permission from Ref. [188]. Copyright 2024, Wiley-VCH. (b) TDOS curves. (c) ORR free energy diagrams of FeN4 site in NiN4-FeN4, and FeN4 site in NiN4-Fe5-FeN4 at 0 and 1.23 V vs. RHE. Reproduced with permission from Ref. [191]. Copyright 2025, Elsevier. (d) Free energy diagram of ORR steps on Fe-N4/Mn-N4 and Fe-N4. (e) Differential charge density of Fe-N4/Mn-N4 and Fe-N4. Reproduced with permission from Ref. [192]. Copyright 2024, Wiley-VCH. (f) Illustration of the formation for ES-Co/Zn-CNZIF with the proposed molecular structure. Reproduced with permission from Ref. [52]. Copyright 2023, Elsevier.

Fig. 8. (a) Geometric structures of single-atom, homo-/hetero-dual-atom, and homo-/hetero-trimetallic atom catalysts (TACs). (b) A smartwatch and a phone that are powered with an FSS-ZAB under the bent condition. Reproduced with permission from Ref. [196]. Copyright 2025, Wiley-VCH. (c) Atomic structures of electrocatalysts. Reproduced with permission from Ref. [197]. Copyright 2024, Elsevier. (d) Illustration of the synthetic process for S/N-CMF@FexCoyNi1-x-y-MOF. Reproduced with permission from Ref. [32]. Copyright 2023, Wiley-VCH. (e) Predictive performance of eight distinct ML regression models to minimize the overpotential. (f) Pearson correlation matrix. (g) Importance feature bar graph. Reproduced with permission from Ref. [200]. Copyright 2025, Wiley-VCH.

Fig. 9. (a) Electrospinning-based synthesis of Co, Ni-SAs/S, N-CNFs membrane catalyst. (b) High-resolution XPS spectra of S 2p orbitals of Co, Ni-SAs/S, N-CNFs. Reproduced with permission from Ref. [218]. Copyright 2024, Elsevier. (c) Synthesis route of ZIF-8 and ZIF-8 derived carbon. (d) Synthesis route of Zn-Im fibers and derived porous carbon fibers. (e) Synthesis route of high-content pyrrole-type Fe-N-C catalyst. Reproduced with permission from Ref. [219]. Copyright 2024, Royal Society of Chemistry. (f) XPS high-resolution energy spectrum of Co 2p. (g) OER polarization curves of different catalysts measured in 1 mol L-1 KOH solution at 1600 r min-1. (h) Overall polarization curves of different catalysts over the entire ORR and OER region. Reproduced with permission from Ref. [220]. Copyright 2023, Wiley-VCH.

Table 2 Summary of electrocatalytic and ZAB performance of electrospun-MOF composites as oxygen catalysts.

Catalysts	ORR and OER performance					ZAB performance						Ref.
Catalysts	E_1/2 [V] (ORR)/ Pt/C	E_j₌₁₀ [V] (OER)/RuO₂	ΔE [V]		Electrolyte ORR/OER 1600 rpm/0 rpm		Electrolyte	OCV [V]	Peak PC [mW cm^-2] @Window voltage [V]	Specific capacity (mAh g^-1)/ Current density (mA cm^-2)	Durability time (h)/ Current density (mA cm^-2)	Ref.
CoNC/ NCNTs@CNF	0.78/0.78	1.62/1.55	0.84/ 0.77		0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH	1.423	260@0.7	—	43/5	[49]
Co/CNWs/CNFs	0.82/0.85	1.64/—	0.82/—		0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.46	304@0.40	823/5	1500/5	[50]
NiFe@C@Co CNFs	0.87/0.85	1.6/1.599	0.73/ 0.749		0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.44	130@0.52	694/5	67/5	[51]
ES-Co/Zn-CN_ZIF	0.857/ 0.834	1.692/1.603	0.835/ 0.769		0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.527	215@0.65	802.6/10	254/10	[52]
CNT@Co- CNF_F50-900	0.871/ 0.866	1.61/ 1.63(Ir/C)	0.74/ 0.764		0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH	1.50	371@0.6	778/10	>130/2	[53]
Fe-N₄/N_GC-C	0.87/ <0.87	—	—		0.1 mol L^-1 KOH/—		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.48	225@0.67	812/10	>1200 cycles /10	[54]
CoNC-HCNFs	0.83/0.83	1.57/1.55	0.74/ 0.72		0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.41	255@-	—	4/1	[99]
Fe-ZCNF	0.88/0.86	1.63/1.6	0.75/ 0.74		0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.59	179.2@ 0.75	788.5/10	>200/10	[148]
ZN₃-CNFs-900	0.834/ 0.824	1.695/1.692	0.861/ 0.868		0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.43	111@0.63	791.6/5	400/5	[149]
N-CNT@MOF-Co/HO-BN/CNFs	0.84/0.84	1.51/1.49 (IrO₂)	0.67/ 0.65		0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.448	142.9@ 0.45	700/5	>200/5	[150]
FeN₄-NFS-CNF	0.90/0.84	1.50/1.57	0.60/ 0.73	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.58	201.5@0.6	802/	1000/10	[155]
NiCo@C@ CoMnCNFs	0.82/0.83	1.628/1.738	0.808/ 0.908	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.44	130.3@ 0.59	798.4/5	1650/5	[156]
Co-CSNFs	0.86/0.88	1.70/1.69	0.84/ 0.81	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH		1.37	57.48@ 0.58	—	366/—	[161]
CNFs/CoZn-MOF@COF	0.82/0.83	1.573/1.592	0.753/ 0.762	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.46	203.63@ 0.74	802.91/10	180/10	[163]
Co-N-C/CNF	0.859/ 0.857	—	—	0.1 mol L^-1 KOH/—		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.452	159@0.68	755/10	>100/10	[166]
Fe, Co-N-C/CNF	0.878/ 0.857	1.624/1.608	0.746/ 0.751	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.426	152@0.68	809.2/10	120/10	[168]
CoSe₂@NC@ NCNFs	0.80/0.86	1.51/1.53	0.71/ 0.67	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.43	126.8@0.6	763.1/10	>240 cycles/ 10	[169]
FeN₄-FeNCP@MCF	0.894/ 0.865	—	—	0.1 mol L^-1 KOH/—		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.489	208.1@ 0.65	—	>350/5	[177]
Fe SACs@PNCNFs	0.89/0.87	1.65/1.61	0.76/ 0.74	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.445	163@0.67	816/ 20	>200/5	[178]
CoN₅/PCNF	0.92/ 0.856	1.53/1.58	0.61/ 0.724	0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.52	273.8@ 0.63	784.2/10	>600/10	[181]
Co, Fe-DACs/ NCs@PCF	0.871/ 0.85	1.588/1.6	0.717/ 0.75	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.552	189.4@0.6	899.4/10	1500/2	[188]
Co_SANi-NCNT/CNF	0.86/0.85	1.47/1.478 (IrO₂)	0.618/ 0.628	0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.54	132.23@ 0.53	803.5/10	120/10	[182]
NiN₄-Fe₅-FeN₄@ PCF	0.878/ 0.861	1.626/1.616	0.748/ 0.755	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.58	—	781.8/10	>900/2	[191]
FeMn-N-C	0.92/0.86	1.6/—	0.68/—	0.1 mol L^-1 KOH/ 1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.494	151@0.63	795/—	700/10	[192]
Co/Zn@NCF	0.84/0.84	1.69/1.69 (IrO₂)	0.85/ 0.85	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 ZnCl₂		1.42	202@0.6	760/10	666/5	[140]
Co,Ni-SAs/S, N-CNFs	0.84/ <0.84	1.82/—	0.98/—	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 ZnCl₂		1.40	175@0.525	762/10	227/5	[218]
Im-Fe-NS-900	0.89/0.84	—	—	0.1 mol L^-1 KOH/—		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.47	68.2@—	—	>90/5	[219]
CoP/CNF	0.78/0.82	1.56/1.54 (IrO₂)	0.78/ 0.72	0.1 mol L^-1 KOH/ 1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.43	164@0.65	780 /10	1200/5	[220]
NPS-HPCNF	0.86/0.83	—	—	0.1 mol L^-1 KOH/—		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.51	210@0.625	795/	>1000/20	[223]

Table 2 Summary of electrocatalytic and ZAB performance of electrospun-MOF composites as oxygen catalysts.

Catalysts	ORR and OER performance					ZAB performance						Ref.
Catalysts	E_1/2 [V] (ORR)/ Pt/C	E_j₌₁₀ [V] (OER)/RuO₂	ΔE [V]		Electrolyte ORR/OER 1600 rpm/0 rpm		Electrolyte	OCV [V]	Peak PC [mW cm^-2] @Window voltage [V]	Specific capacity (mAh g^-1)/ Current density (mA cm^-2)	Durability time (h)/ Current density (mA cm^-2)	Ref.
CoNC/ NCNTs@CNF	0.78/0.78	1.62/1.55	0.84/ 0.77		0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH	1.423	260@0.7	—	43/5	[49]
Co/CNWs/CNFs	0.82/0.85	1.64/—	0.82/—		0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.46	304@0.40	823/5	1500/5	[50]
NiFe@C@Co CNFs	0.87/0.85	1.6/1.599	0.73/ 0.749		0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.44	130@0.52	694/5	67/5	[51]
ES-Co/Zn-CN_ZIF	0.857/ 0.834	1.692/1.603	0.835/ 0.769		0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.527	215@0.65	802.6/10	254/10	[52]
CNT@Co- CNF_F50-900	0.871/ 0.866	1.61/ 1.63(Ir/C)	0.74/ 0.764		0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH	1.50	371@0.6	778/10	>130/2	[53]
Fe-N₄/N_GC-C	0.87/ <0.87	—	—		0.1 mol L^-1 KOH/—		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.48	225@0.67	812/10	>1200 cycles /10	[54]
CoNC-HCNFs	0.83/0.83	1.57/1.55	0.74/ 0.72		0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.41	255@-	—	4/1	[99]
Fe-ZCNF	0.88/0.86	1.63/1.6	0.75/ 0.74		0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.59	179.2@ 0.75	788.5/10	>200/10	[148]
ZN₃-CNFs-900	0.834/ 0.824	1.695/1.692	0.861/ 0.868		0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.43	111@0.63	791.6/5	400/5	[149]
N-CNT@MOF-Co/HO-BN/CNFs	0.84/0.84	1.51/1.49 (IrO₂)	0.67/ 0.65		0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂	1.448	142.9@ 0.45	700/5	>200/5	[150]
FeN₄-NFS-CNF	0.90/0.84	1.50/1.57	0.60/ 0.73	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.58	201.5@0.6	802/	1000/10	[155]
NiCo@C@ CoMnCNFs	0.82/0.83	1.628/1.738	0.808/ 0.908	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.44	130.3@ 0.59	798.4/5	1650/5	[156]
Co-CSNFs	0.86/0.88	1.70/1.69	0.84/ 0.81	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH		1.37	57.48@ 0.58	—	366/—	[161]
CNFs/CoZn-MOF@COF	0.82/0.83	1.573/1.592	0.753/ 0.762	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.46	203.63@ 0.74	802.91/10	180/10	[163]
Co-N-C/CNF	0.859/ 0.857	—	—	0.1 mol L^-1 KOH/—		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.452	159@0.68	755/10	>100/10	[166]
Fe, Co-N-C/CNF	0.878/ 0.857	1.624/1.608	0.746/ 0.751	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.426	152@0.68	809.2/10	120/10	[168]
CoSe₂@NC@ NCNFs	0.80/0.86	1.51/1.53	0.71/ 0.67	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.43	126.8@0.6	763.1/10	>240 cycles/ 10	[169]
FeN₄-FeNCP@MCF	0.894/ 0.865	—	—	0.1 mol L^-1 KOH/—		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.489	208.1@ 0.65	—	>350/5	[177]
Fe SACs@PNCNFs	0.89/0.87	1.65/1.61	0.76/ 0.74	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.445	163@0.67	816/ 20	>200/5	[178]
CoN₅/PCNF	0.92/ 0.856	1.53/1.58	0.61/ 0.724	0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.52	273.8@ 0.63	784.2/10	>600/10	[181]
Co, Fe-DACs/ NCs@PCF	0.871/ 0.85	1.588/1.6	0.717/ 0.75	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.552	189.4@0.6	899.4/10	1500/2	[188]
Co_SANi-NCNT/CNF	0.86/0.85	1.47/1.478 (IrO₂)	0.618/ 0.628	0.1 mol L^-1 KOH/ 1.0 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.54	132.23@ 0.53	803.5/10	120/10	[182]
NiN₄-Fe₅-FeN₄@ PCF	0.878/ 0.861	1.626/1.616	0.748/ 0.755	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.58	—	781.8/10	>900/2	[191]
FeMn-N-C	0.92/0.86	1.6/—	0.68/—	0.1 mol L^-1 KOH/ 1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.494	151@0.63	795/—	700/10	[192]
Co/Zn@NCF	0.84/0.84	1.69/1.69 (IrO₂)	0.85/ 0.85	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 ZnCl₂		1.42	202@0.6	760/10	666/5	[140]
Co,Ni-SAs/S, N-CNFs	0.84/ <0.84	1.82/—	0.98/—	0.1 mol L^-1 KOH/ 0.1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 ZnCl₂		1.40	175@0.525	762/10	227/5	[218]
Im-Fe-NS-900	0.89/0.84	—	—	0.1 mol L^-1 KOH/—		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.47	68.2@—	—	>90/5	[219]
CoP/CNF	0.78/0.82	1.56/1.54 (IrO₂)	0.78/ 0.72	0.1 mol L^-1 KOH/ 1 mol L^-1 KOH		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.43	164@0.65	780 /10	1200/5	[220]
NPS-HPCNF	0.86/0.83	—	—	0.1 mol L^-1 KOH/—		6 mol L^-1 KOH + 0.2 mol L^-1 Zn(Ac)₂		1.51	210@0.625	795/	>1000/20	[223]

Fig. 10. Summary and outlook of electrospun-MOF composites as oxygen electrocatalysts.

Fig. 11. Machine learning flowchart.

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Electrospinning technology combined with MOFs: Bridging the development of high-performance zinc-air batteries

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