Recent advances in metal-organic framework-based electrocatalysts for electrochemical reduction of nitrate to ammonia

doi:10.1016/S1872-2067(26)65269-2

Chinese Journal of Catalysis ›› 2027, Vol. 92: 87-114.DOI: 10.1016/S1872-2067(26)65269-2

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Recent advances in metal-organic framework-based electrocatalysts for electrochemical reduction of nitrate to ammonia

Bo Zhang^a, Yuye Jiao^b, Huijie Cheng^b^,^*(), Jungang Hou^b^,^*()

^a College of Chemistry and Bioengineering, Hunan Institute of Science and Engineering, Yongzhou 425199, Hunan, China
^b State Key Laboratory of Fine Chemical, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China

Received:2026-05-09 Accepted:2026-06-29 Online:2027-01-02 Published:2026-10-30
Contact: *E-mail: hjcheng@dlut.edu.cn (H. Cheng),
jhou@dlut.edu.cn (J. Hou).
About author:Jungang Hou (School of Chemical Engineering, Dalian University of Technology) received his PhD degree from Tianjin University in 2010. He joined the faculty of University of Science and Technology Beijing and was promoted to associate professor in 2013. He worked in Tohoku University as a fellow of Japan Society for the Promotion of Science (JSPS) from 2014 to 2015. Since 2015, he became a full professor in Dalian University of Technology. His research interests focus on photo(electro)catalytic and electrolytic water splitting and CO2 conversion using renewable energy.
Supported by:
National Natural Science Foundation of China(22508109);National Natural Science Foundation of China(22525201);National Natural Science Foundation of China(22372021);National Natural Science Foundation of China(224B2202);National Natural Science Foundation of China(225B2202);Scientific Research Fund of Hunan Provincial Education Department(24B0761);Liaoning Binhai Laboratory(LBLD-2025-05);Fundamental Research Funds for the Central Universities(DUT22LAB602);Fundamental Research Funds for the Central Universities(DUT24BK061);Fundamental Research Funds for the Central Universities(DUTZD25231);Fundamental Research Funds for the Central Universities(DUT25Z2779);Fundamental Research Funds for the Central Universities(DUT25Z3208);Fundamental Research Funds for the Central Universities(DUT25Z2734);Liaoning Joint Project for Technology Research and Development(2024JH2/102600047)

Abstract

Abstract:

Electrocatalytic conversion of nitrate (NO₃^-) to ammonia (NH₃) represents a compelling strategy for mitigating the problem of nitrogen pollution while simultaneously enabling waste valorization, thereby offering a sustainable alternative to the energy-intensive Haber-Bosch process for NH₃ synthesis. Metal-organic frameworks (MOFs), a class of porous materials composed of metal nodes and organic linkers, exhibit periodically extended network structures. Their inherent advantages, including high porosity, well-defined and uniform active sites, and tunable organic functionalities, position them as promising candidates in the field of energy and catalysis. Therefore, a systematic summary of the characteristics and recent research progress of MOF-based materials for the electroreduction reaction of NO₃^- holds significant importance. This review first introduces the current application of pristine MOF materials, MOF-based composites, and MOF-derived materials in the field of NO₃^- electroreduction reaction. It elaborates on the structural characteristics and performance differences of various types of catalysts, revealing the relationship between the catalytic activity and the composition. Subsequently, we highlight and discuss the key strategies for enhancing the performance of NO₃^- electroreduction reaction, thus offering theoretical insights to rationally design the catalysts with high activity and long-term stability. Furthermore, to achieve an in-depth understanding of the mechanism, this review delineates the state-of-the-art techniques employed to probe the structure of catalyst, as well as provide a reliable basis for understanding the reaction pathways of NO₃^- electroreduction reaction. Finally, the significance of MOF-based materials for NO₃^- electroreduction is summarized, and perspectives on their future development are provided.

Key words: Metal-organic frameworks, Reaction pathways, Electrochemical reduction, Ammonia synthesis

Bo Zhang, Yuye Jiao, Huijie Cheng, Jungang Hou. Recent advances in metal-organic framework-based electrocatalysts for electrochemical reduction of nitrate to ammonia[J]. Chinese Journal of Catalysis, 2027, 92: 87-114.

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Figures/Tables 17

Fig. 1. Schematic illustration of the MOF-based materials for NO3-RR.

Fig. 2. Schematic diagram of NO3-RR mechanism.

Fig. 3. (a) Comparation of representative MOF catalysts with Cu-based catalysts. (b) Comparation of representative MOF catalysts with Fe- and Co-based catalysts.

Table 1 Summary of recently reported pristine MOFs, MOF composites, and MOF derivatives for NO3-RR.

Electrocatalyst	Electrolyte	Potential (V vs. RHE)	NH₃ yield	FE (%)	Stability	Ref.
NiCoBDC@HsGDY	1 mol L^‒1 KOH +0.1 mol L^‒1 NO₃^-	-0.34	0.56 mmol h^-1 cm^-2	99.1	16 cycles	[52]
Co-TATB	0.1 mol L^‒1 Na₂SO₄ + 0.1 mol L^‒1 KNO₃	-0.7	122.7 mmol h^-1 g_cat^-1	97.6	8 cycles	[66]
NiMnCoAg-BHT	1 mol L^‒1 KOH + 1 mol L^‒1 KNO₃	-0.8	68 mg h^-1 cm^-2	90.0	15 cycles	[80]
Cu-CA	0.1 mol L^‒1 Na₂SO₄ + 0.1 mol L^‒1 KNO₃	-0.9	286.00 ug h^-1 mg^-1	90.3	10 cycles	[84]
NJUZ-2	0.1 mol L^‒1 Na₂SO₄ + 0.1 mol L^‒1 KNO₃	-0.8	253.7 mmol h^-1 g_cat^-1	98.4	70 h	[85]
HUST-38	0.5 mol L^‒1 K₂SO₄ + 0.1 mol L^‒1 NO₃^-	-0.6	13.38 mg h^-1 mg_cat^-1	95.7	32 cycles	[89]
FeCo PBA HCAs	0.1 mol L^‒1 PBS + 0.1 mol L^‒1 NaNO₃	-0.6	0.105 mmol h^-1 cm^-2	81.01	5 cycles	[92]
Fe₈Zn₁PPc	1 mol L^‒1 NaOH + 0.5 mol L^‒1 NaNO₃	-0.85	2.68 mmol h^-1 cm^-2	99.02	120 h	[94]
Cu₁Co₁HHTP	0.5 mol L^‒1 Na₂SO₄ + 0.1 mol L^‒1 NaNO₃	-0.6	299.9 μmol h^-1 cm^-2	96.4	7 cycles	[95]
Zn₅-NiS₄TP	0.05 mol L^‒1 K₂SO₄ + 0.5 mol L^‒1 KNO₃	-1.2	23477.59 ug h^-1 mg_cat^-1	92.87	20 cycles	[96]
Ni-BDC@Co-HHTP	1 mol L^‒1 NaOH + 0.1 mol L^‒1 NaNO₃	-0.7	11.46 mg h^-1 cm^-2	98.4	10 cycles	[99]
1-Cu’	0.5 mol L^‒1 Na₂SO₄ + 5 mmol L^‒1 NaNO₃	-0.9	66 μmol h^-1 cm^-2	85.5	12 cycles	[104]
CoP/Zn-ZIF	0.5 mol L^‒1 Na₂SO₄ + 0.1 mol L^‒1 NaNO₃	-1	0.89 mmol h^-1 cm^-2	97.2	30 cycles	[110]
Cu@C-800	0.1 mol L^‒1 Na₂SO₄+500 ppm NO₃^-	-0.9	51.7 mmol h^-1 cm^-2	78	—	[112]
CoS_x	1 mol L^‒1 NaOH + 0.1 mol L^‒1 NaNO₃	-0.5	9.1 mg h^-1 cm^-2	93.4	5 cycles	[119]
Cu/Co_0.85Se_VSe	0.1 mol L^‒1 KOH + 0.01 mol L^‒1 NO₃^-	-0.6	2360 ug h^-1 cm^-2	93.5	600 h	[121]
Co-TPA-E	1 mol L^‒1 KOH + 0.1 mol L^‒1 KNO₃	-0.326	1.12 mmol h^-1 cm^-2	99.62	15 cycles	[125]
Cu/NC	0.5 mol L^‒1 Na₂SO₄+200 ppm NO₃^-	-0.7	32300 ug h^-1 mg_cat^-1	100	20 cycles	[129]
Fe-N/P-C	0.1 mol L^‒1 KOH + 0.1 mol L^‒1 KNO₃	-0.4	17980 ug h^-1 mg_cat^-1	90.3	20 cycles	[133]
CoRu/Pd/PCNFs	0.1 mol L^‒1 KOH + 0.1 mol L^‒1 KNO₃	-0.6	78 umol h^-1 mg_cat^-1	98.69	100 h	[140]
Fe-cyano NSs	1 mol L^‒1 KOH + 0.1 mol L^‒1 KNO₃	-0.5	42.1 mg h^-1 mg_cat^-1	90.2	8 cycles	[152]
Cu₉₉Ni₁-DBCO	0.1 mol L^‒1 KHCO₃ + 0.05 mol L^‒1 KNO₃	-1.1	159.4 ug h^-1 mg_cat^-1	80	60 h	[158]

Table 1 Summary of recently reported pristine MOFs, MOF composites, and MOF derivatives for NO3-RR.

Electrocatalyst	Electrolyte	Potential (V vs. RHE)	NH₃ yield	FE (%)	Stability	Ref.
NiCoBDC@HsGDY	1 mol L^‒1 KOH +0.1 mol L^‒1 NO₃^-	-0.34	0.56 mmol h^-1 cm^-2	99.1	16 cycles	[52]
Co-TATB	0.1 mol L^‒1 Na₂SO₄ + 0.1 mol L^‒1 KNO₃	-0.7	122.7 mmol h^-1 g_cat^-1	97.6	8 cycles	[66]
NiMnCoAg-BHT	1 mol L^‒1 KOH + 1 mol L^‒1 KNO₃	-0.8	68 mg h^-1 cm^-2	90.0	15 cycles	[80]
Cu-CA	0.1 mol L^‒1 Na₂SO₄ + 0.1 mol L^‒1 KNO₃	-0.9	286.00 ug h^-1 mg^-1	90.3	10 cycles	[84]
NJUZ-2	0.1 mol L^‒1 Na₂SO₄ + 0.1 mol L^‒1 KNO₃	-0.8	253.7 mmol h^-1 g_cat^-1	98.4	70 h	[85]
HUST-38	0.5 mol L^‒1 K₂SO₄ + 0.1 mol L^‒1 NO₃^-	-0.6	13.38 mg h^-1 mg_cat^-1	95.7	32 cycles	[89]
FeCo PBA HCAs	0.1 mol L^‒1 PBS + 0.1 mol L^‒1 NaNO₃	-0.6	0.105 mmol h^-1 cm^-2	81.01	5 cycles	[92]
Fe₈Zn₁PPc	1 mol L^‒1 NaOH + 0.5 mol L^‒1 NaNO₃	-0.85	2.68 mmol h^-1 cm^-2	99.02	120 h	[94]
Cu₁Co₁HHTP	0.5 mol L^‒1 Na₂SO₄ + 0.1 mol L^‒1 NaNO₃	-0.6	299.9 μmol h^-1 cm^-2	96.4	7 cycles	[95]
Zn₅-NiS₄TP	0.05 mol L^‒1 K₂SO₄ + 0.5 mol L^‒1 KNO₃	-1.2	23477.59 ug h^-1 mg_cat^-1	92.87	20 cycles	[96]
Ni-BDC@Co-HHTP	1 mol L^‒1 NaOH + 0.1 mol L^‒1 NaNO₃	-0.7	11.46 mg h^-1 cm^-2	98.4	10 cycles	[99]
1-Cu’	0.5 mol L^‒1 Na₂SO₄ + 5 mmol L^‒1 NaNO₃	-0.9	66 μmol h^-1 cm^-2	85.5	12 cycles	[104]
CoP/Zn-ZIF	0.5 mol L^‒1 Na₂SO₄ + 0.1 mol L^‒1 NaNO₃	-1	0.89 mmol h^-1 cm^-2	97.2	30 cycles	[110]
Cu@C-800	0.1 mol L^‒1 Na₂SO₄+500 ppm NO₃^-	-0.9	51.7 mmol h^-1 cm^-2	78	—	[112]
CoS_x	1 mol L^‒1 NaOH + 0.1 mol L^‒1 NaNO₃	-0.5	9.1 mg h^-1 cm^-2	93.4	5 cycles	[119]
Cu/Co_0.85Se_VSe	0.1 mol L^‒1 KOH + 0.01 mol L^‒1 NO₃^-	-0.6	2360 ug h^-1 cm^-2	93.5	600 h	[121]
Co-TPA-E	1 mol L^‒1 KOH + 0.1 mol L^‒1 KNO₃	-0.326	1.12 mmol h^-1 cm^-2	99.62	15 cycles	[125]
Cu/NC	0.5 mol L^‒1 Na₂SO₄+200 ppm NO₃^-	-0.7	32300 ug h^-1 mg_cat^-1	100	20 cycles	[129]
Fe-N/P-C	0.1 mol L^‒1 KOH + 0.1 mol L^‒1 KNO₃	-0.4	17980 ug h^-1 mg_cat^-1	90.3	20 cycles	[133]
CoRu/Pd/PCNFs	0.1 mol L^‒1 KOH + 0.1 mol L^‒1 KNO₃	-0.6	78 umol h^-1 mg_cat^-1	98.69	100 h	[140]
Fe-cyano NSs	1 mol L^‒1 KOH + 0.1 mol L^‒1 KNO₃	-0.5	42.1 mg h^-1 mg_cat^-1	90.2	8 cycles	[152]
Cu₉₉Ni₁-DBCO	0.1 mol L^‒1 KHCO₃ + 0.05 mol L^‒1 KNO₃	-1.1	159.4 ug h^-1 mg_cat^-1	80	60 h	[158]

Fig. 4. (a) Schematic representation of the structural assembly process and crystal structures of the high-symmetry coordination MOPs (M = Mn, Fe, or Co). (b) Electrostatic potential (ESP) surface of the Co-TATB model. Reprinted with permission from Ref. [66]. Copyright 2025, American Chemical Society. (c) Schematic illustration of Zn-MOF sample synthesis. (d) Infrared spectra of Zn-MOF and HHTP samples. Reprinted with permission from Ref. [88]. Copyright 2026, Elsevier. (e) Schematic representation of the synthesis, molecular structure, and coordination network within the crystal lattice of HUST-38. Reprinted with permission from Ref. [89]. Copyright 2025, American Chemical Society.

Fig. 5. (a) The computational structure models of FePc-FePc and FePc-ZnPc. (b) FENH3 of FePPc, ZnPPc and Fe8Zn1PPC. Reprinted with permission from Ref. [94], Copyright 2025, John Wiley and Sons. (c) Crystal structure of the ligand and view of the three-dimensional structure in the bc plane and coordination environments of Zn5-NiS4TP. (d) NH3 yield rates and the corresponding FEs-NH3 of the Zn5-NiS4TP, Mn5-NiS4TP and Cd2-NiS4TP at selected potentials in 0.05 mol L-1 K2SO4 with 0.5 mol L-1 KNO3. Reprinted with permission from Ref. [96]. Copyright 2025, John Wiley and Sons. (e) 3D framework of Fe2M-MOF with different trinuclear metal clusters and the H4TPBD ligand. (f) LSV curves of Fe2M-MOFs in 0.05 mol L-1 (pH = 1) H2SO4 with 50 g L-1 KNO3 electrolytes. Reprinted with permission from Ref. [97]. Copyright 2023, John Wiley and Sons.

Fig. 6. (a) Schematic illustration of the joining of ultrathin Ni-MOF nanosheets with few-layered HsGDY-supported Cu single atoms and clusters. (b) FENH3 of NiBDC, HsGDY@Cu and NiBDC@HsGDY@Cu. Reprinted with permission from Ref. [98]. Copyright 2024, John Wiley and Sons. (c) Illustration of NO3‒RR to NH3 production over Ni-BDC@Co-HHTP heterostructured MOF-on-MOF electrocatalyst. (d) LSV curves in 1 mol L‒1 KOH electrolyte with and without NO3‒. (e) The NH3 yield rate and FE of Ni-BDC@Co-HHTP at different potentials. Reprinted with permission from Ref. [99]. Copyright 2024, John Wiley and Sons. (f) Preparation and evolution of the host-guest Cu catalyst through metal ion deposition and in-situ clustering routes. (g) Normalized XANES of 1-Cu’. Reprinted with permission from Ref. [104]. Copyright 2022, American Chemical Society.

Fig. 7. Schematic illustration of taking MOF materials as precursor to prepare metal clusters, metal oxides, metal carbides and single-atom catalysts by means of electrochemical reconstruction or pyrolysis.

Fig. 8. (a) Schematic illustration of the preparation of HKUST-1. Reprinted with permission from Ref. [112], Copyright 2022, American Chemical Society. (b) Schematic illustration of the synthesis process for Cu-N-C-T. (c) Time-course NO2--N proportion. Reprinted with permission from Ref. [114]. Copyright 2020, John Wiley and Sons. (d) Schematic illustration of RuxCoy HNDs synthesis. (e) Tafel slopes of NO3-RR over RuxCoy HNDs. Reprinted with permission from Ref. [117]. Copyright 2023, Springer Nature.

Fig. 9. (a) Synthetic route of Fe3O4@NC-600. Reprinted with permission from Ref. [118]. Copyright 2025, Elsevier. (b) Schematic representation of the synthesis process of cobalt sulfides derived from ZIF-67. Reprinted with permission from Ref. [119]. Copyright 2025, Royal Society of Chemistry. (c) Schematic illustration of the electrocatalytic system for NO3-RR and PET hydrolysate upcycling. Reprinted with permission from Ref. [126]. Copyright 2023, American Chemical Society.

Fig. 10. (a) Schematic illustration of the formation of Cu SACs. (b) The Cu K-edge EXAFS fitting curves of Cu(0.1wt%)/NC. Reprinted with permission from Ref. [131]. Copyright 2023, American Chemical Society. (c) Synthesis and structural characterizations of Fe-N/P-C catalyst. (d) The EDS elemental mappings of Fe-N/P-C. Reprinted with permission from Ref. [133]. Copyright 2023, John Wiley and Sons. (e) Schematic diagram of the EMOFs general synthesis strategy for preparing dual-atom platforms. (f) The 2D atomic resolution map of the Zn-Mn dual-site. Reprinted with permission from Ref. [135]. Copyright 2025, John Wiley and Sons.

Fig. 11. (a) Schematic of the synthesis process for the rich Cu/CoOx@NFs heterogeneous active electrocatalyst. Reprinted with permission from Ref. [144]. Copyright 2024, Elsevier. (b) Synthetic procedure of Co-Fe@Fe2O3. Reprinted with permission from Ref. [147]. Copyright 2022, National Academy of Sciences. (c) Schematic illustration of the preparation of Cu/Pd/CuOx. Reprinted with permission from Ref. [148]. Copyright 2022, Elsevier.

Fig. 12. (a) Supramolecular enhancement of electrochemical NO3-RR catalyzed by embedding 2D molecular cobalt porphyrin into a 3D porous organic cage architecture. (b) NH3 production and TON for various amounts of CoPB-C8 loading at -1.54 V vs. SCE. Reprinted with permission from Ref. [150]. Copyright 2023, John Wiley and Sons. (c) Fe-cyano-R NSs electrocatalysts via directional freezing. Reprinted with permission from Ref. [152]. Copyright 2022, American Chemical Society. (d) Schematic illustration of the synthesis process of MR Co-NC. Reprinted with permission from Ref. [154]. Copyright 2023, Elsevier.

Fig. 13. (a) Top view, and side view of the layer showing the CuO4 and NiO4 nodes. (b) Schematic illustration of NO3-RR selectivity determined by R1 and R2 via the relay electrocatalysis mechanism. (c) NNH4 selectivity over typical samples in Ar-saturated 0.1 mol L‒1 KHCO3 + 0.05 mol L‒1 KNO3 solutions. Reprinted with permission from Ref. [158], Copyright 2025, American Chemical Society. (d) Schematic illustration of the preparation of a Cu/Co-based binary ‘tandem catalyst’. (e) Faradaic efficiencies (FE) for NH3 on CuSP, CoSP and CuCoSP in 0.01 mol L‒1 NO3- and 0.1 mol L‒1 KOH (pH = 13) at various applied potentials. Reprinted with permission from Ref. [159]. Copyright 2022, Springer Nature. (f) Schematic synthesis and structure of MOF-818(Cu)-Co. (g) Charge density difference of *NO adsorbed on MOF-818(Cu) and MOF-818(Cu)-Co. Reprinted with permission from Ref. [160], Copyright 2025, American Chemical Society.

Fig. 14. (a) Schematic diagram of the dynamic dissociation catalytic mechanism for In8 at pH = 2‒3. Reprinted with permission from Ref. [161]. Copyright 2022, American Chemical Society. Crystal structure of Cu3(HITP)2 (b) and Cu3(HHTP)2 (c). Reprinted with permission from Ref. [163]. Copyright 2025, John Wiley and Sons. The ESP for CuBTA (d) and CuTABQ (e). Reprinted with permission from Ref. [165]. Copyright 2023, John Wiley and Sons. (f) Schematic illustration for the preparation of the Zr-BDDB@Hemin. Reprinted with permission from Ref. [168]. Copyright 2025, John Wiley and Sons.

Fig. 15. (a) The structure of nitrate ions and ideal catalytic site following electron back-donation process during N-O activation. (b) Schematic diagram of electron repulsion in eg orbitals. Reprinted with permission from Ref. [169]. Copyright 2025, Elsevier. (c) Bader charge plot of CuPd/CN. (d) Side-view of electron density difference on CuPd/CN. Reprinted with permission from Ref. [170]. Copyright 2022, John Wiley and Sons. (e) PDOS curves of Co 3d in CoNi-MOF and Co-MOF, and the corresponding d-band center values (εd, eV). (f) Projected crystal orbital Hamilton populations for the *NO, *NOH and *NHOH intermediates bonded on the Co site over CoNi-MOF and Co-MOF. Reprinted with permission from Ref. [172]. Copyright 2026, Elsevier.

Fig. 16. (a) Generation of *H on Cu-MOF/Co-MOF@NF surface during EPR detection. Reprinted with permission from Ref. [174]. Copyright 2025, American Chemical Society. In-situ FT-IR spectra for HUST-38 (b) and HUST-39 (c). Reprinted with permission from Ref. [89]. Copyright 2025, American Chemical Society. (d) Online DEMS spectra of Fe8Zn1PPc under different applied potentials in NO3-RR. Reprinted with permission from Ref. [94]. Copyright 2025, John Wiley and Sons. (e,f) In-situ Raman plots of Cu-TCPP/Cu2O/CF with a potential change in pH = 7 environment. Reprinted with permission from Ref. [175]. Copyright 2025, American Chemical Society. (g) XANES spectra of the Fe K-edge. (h) Fitting results of the EXAFS spectra at R space. Reprinted with permission from Ref. [141]. Copyright 2025, Elsevier.

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Recent advances in metal-organic framework-based electrocatalysts for electrochemical reduction of nitrate to ammonia

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