Recent progress in advanced catalysts for electrochemical nitrogen reduction reaction to ammonia

doi:10.1016/S1872-2067(23)64504-8

Chinese Journal of Catalysis ›› 2023, Vol. 52: 50-78.DOI: 10.1016/S1872-2067(23)64504-8

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Recent progress in advanced catalysts for electrochemical nitrogen reduction reaction to ammonia

Yan Hong^,¹, Qi Wang^,¹, Ziwang Kan, Yushuo Zhang, Jing Guo, Siqi Li, Song Liu^*(), Bin Li^*()

College of Chemistry, Chemical Engineering and Resource Utilization, Northeast Forestry University, Harbin 150040, Heilongjiang, China

Received:2023-05-24 Accepted:2023-08-07 Online:2023-09-18 Published:2023-09-25
Contact: *E-mail: carlosliusong@nefu.edu.cn (S. Liu),libinzh62@163.com (B. Li).
About author:Song Liu is a professor at Northeast Forestry University. He received his B.S. degree (2014) from Jilin University and his PhD degree (2020) in catalysis from Dalian Institute of Chemical Physics, Chinese Academy of Sciences. His research interests include design and preparation of efficient biomass-based electrocatalytic materials, mechanism analysis of electrocatalytic reaction and electrocatalytic biomass conversion.
Bin Li is a former professor of Northeast Forestry University, received his master's degree (1989) from the Department of Forestry Engineering of Northeast Forestry University. He received his Ph.D. degree (1997) in Applied Chemistry from Beijing Institute of Technology. His research interests include environment-friendly halogen-free flame retard-antpolymers, functional nanocomposite polymers and biomass and medical polymers.
¹Contribute equally to this work.
Supported by:
National Natural Science Foundation of China(2208048);National Natural Science Foundation of China(62001097);Natural Science Foundation of Heilongjiang Province(YQ2022B001);Young Elite Scientists Sponsorship Program by CAST(YESS20210262);China Postdoctoral Science Foundation-Funded Project(2021M690571);Heilongjiang Postdoctoral Fund(LBH-Z21096);Provincial Natural Science Foundation Joint Guidance Project(LH2020F001);Fundamental Research Funds for the Central Universities(2572020BU04)

Abstract

Abstract:

Due to its use of renewable energy and environmental friendliness, the electrochemical nitrogen reduction process (eNRR) has become a promising substitute for the manufacturing of ammonia. Despite extensive exploration of eNRR catalysts, an optimal catalyst has not been reported to date. Therefore, it is imperative to develop rational catalysts to enhance NH₃ synthesis efficiency. In order to offer suggestions for catalyst design, recent developments in electrocatalysts for eNRR are summarized in this paper. Firstly, the eNRR mechanism is briefly introduced. Secondly, the design strategies of eNRR catalysts were summarized in terms of morphology, structure, vacancies, doping, synergistic effect, heterojunction and single atom. Subsequently, the application of in situ mass spectrometry, in situ infrared, in situ XAS and in situ Raman to the NRR reaction is discussed. The importance of the density-functional theory (DFT) method for the study of reaction energy barriers and catalyst electron-orbital distributions during eNRR catalysis is discussed. Finally, this review presents the potential challenges and future perspectives of eNRR.

Key words: Electrocatalysis, Nitrogen reduction, Structure design, Original characterization, Reaction system

Yan Hong, Qi Wang, Ziwang Kan, Yushuo Zhang, Jing Guo, Siqi Li, Song Liu, Bin Li. Recent progress in advanced catalysts for electrochemical nitrogen reduction reaction to ammonia[J]. Chinese Journal of Catalysis, 2023, 52: 50-78.

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Figures/Tables 19

Fig. 1. Possible initial activation modes and reaction paths in eNRR.

Fig. 2. (a) Overview diagram of nitrogen fixing enzyme. (b) A graphic representation of the nitrogen-fixing enzyme's structure. (c) Schematics of dinitrogen molecular orbitals hybridized by nitrogen atomic orbitals and the electron arrangement of element.

Fig. 3. (a) Schematic diagram of NH4+ quantitative analysis. Spectrophotometric method (b) and ion selective electrode (c) and ion chromatography (d) for the detection of NH4+ in NRR. (e) Comparison of the three methods for NH3 quantification. Reprinted with permission from Ref. [55]. Copyright 2019, John Wiley and Sons. (f,g) Standard curves of different concentrations of 15NH3 by 1H NMR spectra. Reprinted with permission from Ref. [58]. Copyright 2021, John Wiley and Sons.

Fig. 4. (a) LIR comparison between several cathode materials. Reprinted with permission from Ref. [58]. Copyright 2021, John Wiley and Sons. (b) Schematic representation of the chemical properties of proton carriers in lithium-mediated electrocatalytic synthesis of ammonia gas. (c,d) Comparison of TiO2 nano-array electrodes obtained with/without 20 wt% PEG in acidic and alkaline electrolytes. (c,d) Reprinted with permission from Ref. [59]. Copyright 2021, John Wiley and Sons. (e) CV curves of PEBCD/C electrodes in Li2SO4 electrolyte. (f) FTIR spectra of PEBCD before and after Li+ incorporation. Reprinted with permission from Ref. [63]. Copyright 2017, American Chemical Society. (g) N2 adsorption energy on Sb (100). (h) Sb-N and A-N interatomic dimensions for N2 adsorbates, in addition to the appropriately optimized structures. Reprinted with permission from Ref. [61]. Copyright 2022, American Chemical Society.

Fig. 5. Schematic diagram of the different active site designs involved in NRR.

Fig. 6. (a) Geometric model of Au THH NR and exposed 24 facets. Reprinted with permission from Ref. [68]. Copyright 2016, John Wiley and Sons. (b) Schematic diagrams of face-centered cubic PdCu and body-centered cubic PdCu structures. Reprinted with permission from Ref. [69]. Copyright 2020, John Wiley and Sons. (c) TEM image of NPG@ZIF-8 composite. (d) SEM image of Mo/VO2. (e) TEM images of Rh-Se NCs. (f) FE of VO2 and Mo/VO2 at various potentials. (g) Comparative electrochemical properties of different materials. (h) NH3 yields at various applied potentials of Rh-Se NCs/C. (c,g) Reprinted with permission from Ref. [74]. Copyright 2019, Copyright 2020, John Wiley and Sons. (d,f) Reprinted with permission from Ref. [47]. Copyright 2023, Copyright 2020, John Wiley and Sons. (e,h) Reprinted with permission from Ref. [23]. Copyright 2020, John Wiley and Sons.

Fig. 7. (a) Diagram of the interaction between metal and carrier. (b) Charge transfer schematic. (c) Au 4f spectra of Au/CoOx samples after 10 h of electrolysis at -0.5 V vs. RHE. Reprinted with permission from Ref. [76]. Copyright 2019, John Wiley and Sons. (d) Interfacial perimeter schematic. (e) Chemical composition diagram. (f) Schematic diagram of strong metal-carrier interaction (SMSI). (g) Diagrams of the Mo-PTA@CNT schematic. Reprinted with permission from Ref. [79]. Copyright 2021, John Wiley and Sons. (h) N2 molecule adsorption energies on TiO2(B) and Li-TiO2(B) surfaces, respectively. Reprinted with permission from Ref. [81]. Copyright 2022, Elsevier. (i) Average NH3 yields of Au/Fe2(MoO4)3, Fe2(MoO4)3 and Au/C catalysts at different potentials. Reprinted with permission from Ref. [82]. Copyright 2021, John Wiley and Sons.

Fig. 8. (a) Schematic diagram of bimetallic synergy. (b) Schematic diagram of Au6/Ni electrocatalytic reduction of N2 to NH3. (c) Au6/Ni catalyst NH3 production at various potentials. (b,c) Reprinted with permission from Ref. [30]. American Chemical Society. (d) Flow chart for the preparation of core-shell manganese oxide. Reprinted with permission from Ref. [90]. Copyright 2022, American Chemical Society. (e) Schematic diagram of np-Pd3Bi. (f) The mass-normalized NH3 yield rates of commercial Pd/C, np-Pd3Bi, and np-PdBi2 at the applied voltage. (e,f) Reprinted with permission from Ref. [87]. Copyright 2021, John Wiley and Sons.

Fig. 9. (a) Diagram of single atom and particle synergy. (b) Faraday efficiency of Au-Cys-Mo catalysts at different potentials. Reprinted with permission from Ref. [94]. Copyright 2021, John Wiley and Sons. (c) HAADF-STEM images of MoSAs-Mo2C/NCNTs. (d) An illustration showing the morphology of CNT@C3N4-Fe&Cu. (e) Comparison of different materials' Faraday efficiencies at four applied potentials. (f) NH3 yield rate and FE of various samples. (c,f) Reprinted with permission from Ref. [96]. Copyright 2020, John Wiley and Sons. (d,e) Reprinted with permission from Ref. [95]. Copyright 2020, John Wiley and Sons.

Table 1 Recent publications on the application of synergy to electrocatalytic N2 reduction of NH3.

Type	Catalyst	Electrolyte	NH₃ yield	FE (%)	Potential (V vs. RHE)	Ref.
Metal- support interaction	Au/TiO₂	0.01 mol L^-1 HCl	64.6 μg h^-1 mg^-1	29.5	-0.4	[29]
	Au NPs/TiO₂	HCl (pH=1)	21.4 μg h^-1 mg^-1	8.11	-0.2	[33]
	Au/CoO_x	0.05 mol L^-1 H₂SO₄	15.1 μg cm^-2 h^-1	19	-0.5	[76]
	MoS₂/Mo₂C	0.05 mol L^-1 H₂SO₄	1.41 μg cm^-2 h^-1	42	-0.1	[77]
	FeNi₂S₄/NiS	0.1 mol L^-1 KOH	128.39 ± 1.32 µg h^-1cm^-2	28.6 ± 0.18	-0.3	[78]
	Mo-PTA@CNT	0.1 mol L^-1 K₂SO₄	51 ± 1 μg h^-1 mg^-1	83 ± 1	-0.1	[79]
	Au₃Cu@Cu	0.1 mol L^-1 Na₂SO₄	33.97 μg h^-1 mg^-1	21.41	-0.2	[80]
	Li-TiO₂(B)	0.5 mol L^-1 LiClO₄	8.7 μg h^-1 mg^-1	18.2	-0.4	[81]
	Au/Fe₂(MoO₄)₃	0.2 mol L^-1 Na₂SO₄	7.61 μg h^-1 mg^-1	18.79	-0.4	[82]
	Fe/MoS₂	0.1 mol L^-1 Na₂SO₄	12.5 µg h^-1 cm^-2	1.7	-0.1	[83]
Metal- metal interaction	Au₆/Ni	0.05 mol L^-1 H₂SO₄	7.4 μg h^-1 mg^-1	67.8	-0.14	[30]
	RuPt	1.0 mol L^-1 KOH	6.37 × 10⁻¹⁰ mol s^-1 cm^-2	1.1	-0.077	[89]
	CuAu@2LCS	0.1 mol L^-1 HCl	33.9 μg h^-1 mg^-1	24.1	-0.2	[86]
	np-Pd₃Bi	0.05 mol L^-1 H₂SO₄	59.05 ± 2.27 μg h^-1 mg^-1	21.52 ± 0.71	-0.2	[87]
	Fe₃Mo₃C	1 mol L^-1 KOH	13.10 µg h^-1 cm^-2	14.74	-0.5	[91]
	FeNi@CNS	0.1 mol L^-1 Na₂SO₄	16.52 µg h^-1 cm^-2	9.83	-0.2	[92]
Particle-monoatom interaction	Fe-SnO₂	0.1 mol L^-1 HCl	82.7 μg h^-1 mg^-1	20.4	-0.3	[93]
	Au₂₅-Cys-Mo	0.1 mol L^-1 HCl	34.5 μg h^-1 mg^-1	26.5	-0.5	[94]
	CNT@C₃N₄-Fe&Cu	0.25 mol L^-1 LiClO₄	9.86 μg h^-1 mg^-1	34	-0.8	[95]
	MoSAs-Mo₂C/NCNTs	0.005 mol L^-1 H₂SO₄ + 0.1 mol L^-1 K₂SO₄	16.1 µg h^-1 cm^-2	7.1	-0.2	[96]

Fig. 10. (a) Schematic diagram of the doping of metallic and non-metallic atoms in nanomaterials. (b) NH3 yields of different materials such as W18O49 at different potentials. (c) Schematic diagram of Fe doped W18O49 nanowires @CFP. (b,c) Reprinted with permission from Ref. [97]. Copyright 2020, John Wiley and Sons. (d) NPC schematic. Reprinted with permission from Ref. [114]. Copyright 2018, American Chemical Society. (e) NRR for BG is shown graphically. (f) The NH3 production rates of BG-1, BOG, BG-2, and G at different potentials. Reprinted with permission from Ref. [112]. Copyright 2018, Elsevier. (g) Diagram of P-C3N4. Reprinted with permission from Ref. [118]. Copyright 2023, John Wiley and Sons. (h) Diagrammatic representation of the MoS2-7H-catalyzed reduction of N2 to NH3. Reprinted with permission from Ref. [124]. Copyright 2022, Elsevier.

Table 2 Recently published papers on doping engineering for eNRR.

Type	Catalyst	Electrolyte	NH₃ yield	FE (%)	Potential (V vs. RHE)	Ref.
Metal-doping	Fe-W₁₈O₄₉	0.25 mol L^-1 LiClO₄	24.7 μg h^-1 mg_cat^-1	20	-0.15	[97]
	Fe-Ni₂P	0.1 mol L^-1 HCl	88.51 μg h^-1 mg_cat^-1	7.92	-0.3	[98]
	_0.50Fe-Bi₂WO₆	0.05 mol L^-1 H₂SO₄	289 μg h^-1 mg_cat^-1	2	-0.75	[99]
	a-FeB₂ PNSs	0.5 mol L^-1 LiClO₄	39.8 μg h^-1 mg_cat^-1	16.7	-0.3	[100]
B-doping	Boron nanosheets	0.1 mol L^-1 HCl	3.12 μg h^-1 mg_cat^-1	4.84	-0.14	[105]
	BNNRs	0.1 mol L^-1 HCl	26.57 μg h^-1 mg_cat^-1	15.95	-0.75	[108]
	BCN	0.05 mol L^-1 Na₂SO₄	8.39 μg h^-1 mg_cat^-1	9.87	-0.3	[109]
	Eex-COF/NC	0.1 mol L^-1 KOH	12.53 μg h^-1 mg_cat^-1	45.34	-0.2	[110]
	BG	0.05 mol L^-1 H₂SO₄	9.8 μg h^-1 cm^-2	10.8	-0.5	[112]
N-doping	NPC-750	0.05 mol L^-1 H₂SO₄	1.4 mmol g^-1 h^-1	1.42	-0.9	[114]
	C-ZIF-1100	0.1 mol L^-1 KOH	3.4 × 10^-6 mol cm^-2 h^-1	10.2	-0.3	[40]
	CNS	0.25 mol L^-1 LiClO₄	97.18 ± 7.13 µg h^-1 cm^-2	11.56 ± 0.85	-1.19	[115]
P-doping	P-NV-C₃N₄	0.1 mol L^-1 Na₂SO₄	28.67 µg h^-1 mg_cat^-1	22.15	-0.3	[118]
	FL-BP NSs	0.01 mol L^-1 HCl	31.37 µg h^-1 mg_cat^-1	5.07	-0.7	[119]
	Crp NRs/NF	0.1 mol L^-1 Na₂SO₄	15.4 µg h^-1 mg_cat^-1	9.4	-0.2	[111]
S-doping	SDG	0.5 mol L^-1 LiClO₄	28.56 µg h^-1 mg_cat^-1	7.07	-0.85	[120]
	S-NV-C₃N₄	0.5 mol L^-1 LiClO₄	32.7 µg h^-1 mg_cat^-1	14.1	-0.4	[121]
	S-CNS	0.1 mol L^-1 Na₂SO₄	19.07 µg h^-1 mg_cat^-1	7.47	-0.7	[122]
	S-MoS₂	0.5 mol L^-1 H₂SO₄	43.4 ± 3 μg h^-1 mg_cat^-1	16.8 ± 2	-0.3	[123]
	MoS₂-Vs	0.5 mol L^-1 LiClO₄	66.74 μg h^-1 mg_cat^-1	14.68	-0.6	[124]
	Mo-SnS₂/CC	0.5 mol L^-1 LiClO₄	41.3 μg h^-1 mg_cat^-1	20.8	-0.4	[125]

Table 3 A recently published paper on vacancy engineering for eNRR.

Type	Catalyst	Electrolyte	NH₃ yield	FE (%)	Potential (V vs. RHE)	Ref.
Metal vacancies	etched-PdZn/NHCP	0.1 mol L^-1 PBS	5.28 µg h^-1 mg_cat^-1	16.9	-0.2	[126]
	MV-MoN@NC	0.1 mol L^-1 HCl	76.9 µg h^-1 mg_cat^-1	6.9	-0.2	[127]
	Ni-NFV	0.1 mol L^-1 PBS	7.3 µg h^-1 mg_cat^-1	4.4	-0.4	[128]
Oxygen vacancies	α-Fe₂O₃	0.1 mol L^-1 KOH	0.46 µg h^-1 cm^-2	6.04	-0.9	[131]
	TiO₂/CeO₂	0.1 mol L^-1 HCl	8.8 µg h^-1 mg_cat^-1	6.8	-0.25	[132]
	Cu NPs/TiO₂	0.1 mol L^-1 Na₂SO₄	13.6 µg h^-1 mg_cat^-1	17.9	-0.4	[50]
	MoO_3-_x/MXene	0.1 mol L^-1 KOH	95.8 µg h^-1 mg_cat^-1	22.3	-0.4	[133]
	TiO₂-V_(o)	0.1 mol L^-1 HCl	3.0 µg h^-1 mg_cat^-1	6.5	-0.12	[134]
	WO_3-_x(Vo)_H₂	0.5 mol L^-1 H₂SO₄	4.2 µg h^-1 mg_cat^-1	6.8	-0.12	[135]
MvK theoretical vacancies	VN	1 mmol L^-1 H₂SO₄	3.3 × 10^-10 mol s^-1 cm^-2	6.0	-0.1	[136]
MvK theoretical vacancies	Mo₂N	0.1 mol L^-1 HCl	78.4 µg h^-1 mg_cat^-1	4.5	-0.3	[137]

Fig. 11. (a) Schematic diagram of metallic and non-metallic vacancies. (b) Schematic diagram of a layered porous MoN@NC with a large number of Mo vacancies. (c) NH3 yields with different catalysts at -0.2 V vs. RHE. (b,c) Reprinted with permission from Ref. [127]. Copyright 2020, Elsevier. (d) Ni-B and Ni-V system free energy maps have been established. (e) Synthesis process of catalytic nickel nanoflowers. Reprinted with permission from Ref. [128]. Copyright 2022, American Chemical Society. (f) Schematic illustration of the molecular structure of TiO2/CeO2 and the proposed mechanism for electrochemical NRR. (g) Catalysts' Faraday efficiency and NH3 yield at particular voltages. Reprinted with permission from Ref. [132]. Copyright 2023, John Wiley and Sons.

Fig. 12. (a) General schematic of heterogeneous structured catalyst for eNRR. (b) Calculated work function of BNQDs and Ti3C2Tx and differential charge density of BNQDs/Ti3C2Tx. Reprinted with permission from Ref. [140]. Copyright 2022, John Wiley and Sons. (c) Synthesis process of Cu3(HITP)2@h-BN heterojunction. Reprinted with permission from Ref. [141]. Copyright 2023, John Wiley and Sons. (d) HAADF-STEM image of CoxNi3-x(HITP)2/BNSs-P (inset: lattice line scan). Reprinted with permission from Ref. [142]. Copyright 2023, John Wiley and Sons. (e) Electrochemical properties of NiCoP/CoMoP/Co(Mo3Se4)4@C/NF. Reprinted with permission from Ref. [144]. Elsevier.

Table 4 Recent papers on the application of single-atom catalysts to eNRR.

Type	Catalyst	Electrolyte	NH₃ yield	FE (%)	Potential (V vs. RHE)	Ref.
SACs on carbon supports	Au Sac/N-Cs	0.1 mol L^-1 HCl	2.32 μg h^-1 cm^-2	12.3	-0.2	[152]
	Fe-N₃/CNT	0.1 mol L^-1 KOH	34.83 μg h^-1 mg_cat^-1	9.28	-0.2	[159]
	Fe-(O-C₂)₄	0.1 mol L^-1 KOH	32.1 μg h^-1 mg_cat^-1	29.3	-0.1	[168]
	Mo-SAs/AC	0.1 mol L^-1 Na₂SO₄	2.55 ± 0.31 mg h^-1 mg_cat^-1	57.54 ± 6.98	-0.4	[155]
	Fe-N₂O₄	0.1 mol L^-1 HCl	31.9 μg h^-1 mg_cat^-1	11.8	-0.4	[169]
SACs on non-carbon supports	Au_SA/np-MoSe₂	0.1 mol L^-1 Na₂SO₄	30.83 μg h^-1 mg_cat^-1	37.82	-0.3	[171]
	Nb_SA-TiO₂	0.1 mol L^-1 Na₂SO₄	21.17 μg h^-1 mg_cat^-1	9.17	-0.5	[172]
	Ru_1.4Co₃O_4-_x	0.1 mol L^-1 KOH	2.67 mg h^-1 mg_cat^-1	40.2	0	[174]
	Cd/In₂O₃	0.1 mol L^-1 KOH	57.5 μg h^-1 mg_cat^-1	9.6 ± 0.9	-0.43	[175]
	Y@TiO₂	0.1 mol L^-1 HCl	6.3 μg h^-1 mg_cat^-1	11.0	-0.22	[176]
	Bi-TiN	0.1 mol L^-1 Na₂SO₄	76.15 μg h^-1 mg_cat^-1	24.60	-0.8	[177]
Solid-loaded molecular catalysts	FePc-py-CNT	0.1 mol L^-1 HCl	21.7 μg h^-1 mg_cat^-1	22.2	-0.5	[178]
	CoPc NTs	0.1 mol L^-1 HCl	107.9 μg h^-1 mg_cat^-1	27.7	-0.3	[179]
	FeTPPCl	0.1 mol L^-1Na₂SO₄-PBS	18.28 ± 1.6 μg h^-1 mg_cat^-1	16.76 ± 0.9	-0.3	[181]

Fig. 13. (a) Schematic diagram of single atom loading on carbon and non-carbon substrates. (b) Fe-N/C-CNT synthesis is depicted in a schematic. (c) NH3 yield of CNTs, NC-CNTs, and Fe-N/C-CNTs. (b,c) Reprinted with permission from Ref. [159]. Copyright 2019, American Chemical Society. (d) The NC/Bi SAs/TiN/CC the production process can be seen schematically. Reprinted with permission from Ref. [177]. Copyright 2021, John Wiley and Sons. (e) Schematic diagram of Ru-Co3O4-x nanowires. (f) Diagram of AuSA/np-MoSe2. (g) Mass-normalized NH3 yields of the three catalytic materials at each given potential. (h) Partial current density and NH3 yield of Ru1.4Co3O4-x at different potentials. (e,h) Reprinted with permission from Ref. [174]. Copyright 2021, American Chemical Society. (f,g) Reprinted with permission from Ref. [171]. Copyright 2021, John Wiley and Sons.

Fig. 14. (a) Schematic diagram of the original flavor representation means. (b) Raman spectra of MoO3/MoO3-x with time during -0.4 V NRR electrolysis. Reprinted with permission from Ref. [133]. Copyright 2021, John Wiley and Sons. (c) Normalized in-situ Bi L-edge XAS spectra with the electrolyte changed from Ar-saturated to N2-saturated aqueous solutions. Reprinted with permission from Ref. [183]. Copyright 2023, John Wiley and Sons. (d) In-situ FTIR spectra of Ag4Ni2 NCs at -0.2 V. Reprinted with permission from Ref. [49]. Copyright 2022, John Wiley and Sons. (e) Ion current responses to the m/z signal at position 17 under diverse reaction potentials and situations. Reprinted with permission from Ref. [190]. Copyright 2020, John Wiley and Sons.

Fig. 15. (a) Combination volcano diagrams (lines) for the stepped (red) and flat (black) transition metal surfaces for nitrogen reduction with a Heyrovsky-type reaction, without (dotted lines) and with (solid lines) the impact of H-bonds. (b) On a surface doped with B, (111), DFT computed the NRR reaction cycle using an alternate pathway. Reprinted with permission from Ref. [199]. Copyright 2020, American Chemical Society. (c) Schematic illustration: Lewis base lowers the N2 dissociation activating threshold by acting as an electron donor. C, N, and H atoms are each represented by a cyan, red, and grey spherical. Reprinted with permission from Ref. [197]. Copyright 2020, John Wiley and Sons. (d) The atomic structure of CoP nanoparticles. Reprinted with permission from Ref. [204]. Copyright 2022, Elsevier. (e) DFT calculations investigated the NRR catalytic behavior of Bi-based catalysts. Reprinted with permission from Ref. [205]. Copyright 2020, American Chemical Society.

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Recent progress in advanced catalysts for electrochemical nitrogen reduction reaction to ammonia

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