Theoretical Research Progress of Single Atom Catalysts in Electrochemical Synthesis of Ammonia

doi:10.19894/j.issn.1000-0518.220138

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (1): 9-23.DOI: 10.19894/j.issn.1000-0518.220138

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Theoretical Research Progress of Single Atom Catalysts in Electrochemical Synthesis of Ammonia

Rong CAO¹^,², Jie-Zhen XIA¹^,², Man-Hua LIAO¹^,², Lu-Chao ZHAO¹^,², Chen ZHAO¹^,², Qi WU¹^,²()

^1.Department of Physics，Tibet University，Lhasa 850000，China
^2.Institute of Oxygen Supply，Tibet University，Lhasa 850000，China

Received:2022-04-16 Accepted:2022-08-07 Published:2023-01-01 Online:2023-01-28
Contact: Qi WU
About author:wuqi_zangda@163.com
Supported by:
the National Natural Science Foundation of China(22168036);the Central for the Reform and Development of Local Colleges and Universities Funding Project(Zangcaijiaozhi［2021］1-21);Tibet University Postgraduate Students High-Level Talent Training Plan Project(2020-GSP-S039)

Abstract

Abstract:

Ammonia synthesis in the traditional Haber-Bosch process requires large energy consumption and complex plant infrastructure. Driven by the development of renewable energy， electrocatalysts for the nitrogen reduction reaction （NRR） have attracted ever-growing attention and have been considered as the most efficient alternative to the catalyst in the Haber-Bosch process. However， this process suffers from low NH₃ production and Faradaic efficiency. Therefore， the development of more efficient electrocatalysts is crucial for their practical applications. Among the previously reported catalysts， single-atom catalysts （SACs） exhibit significant advantages in efficient utilization of atoms and unsaturated coordination， providing a huge scope for optimizing catalyst performance. In this paper， the theoretical research of single-atom catalysts in electrochemical ammonia synthesis is reviewed， and the performance of three types of single-atom catalysts， namely noble metal catalysts， non-precious metal catalysts and metal-free catalysts， is analyzed in detail， aiming to provide new ideas for the development of electrochemical ammonia synthesis technology.

Key words: Single-atom catalyst, Electrochemical ammonia synthesis, Reaction mechanism, Catalyst activation, Catalyst support

CLC Number:

O643.3

Rong CAO, Jie-Zhen XIA, Man-Hua LIAO, Lu-Chao ZHAO, Chen ZHAO, Qi WU. Theoretical Research Progress of Single Atom Catalysts in Electrochemical Synthesis of Ammonia[J]. Chinese Journal of Applied Chemistry, 2023, 40(1): 9-23.

Figures/Tables 9

References 85

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Classification	Example	Overpotential/V	Mechanism	NH₃ yield rate	FE/%	Electrolyte	Ref.
Precious metal catalyst	Ru/ZrO₂@NC	-0.21	Distal mechanism	3.665 μg/（h·mg）	21	0.1 mol/L HCl	［5］
	Rh SA/GDY	-0.20	Distal mechanism	74.15 μg/（h·cm²）	20.36	0.1 mol/L K₂SO₄	［30］
	Rh₁/MnO₂	—	—	271.8 μg/（h·mg）	73.3	9 mol/L K₂SO₄	［44］
	Pd-TiO₂	-0.5	—	17.4 μg/（h·mg）	12.7	0.1 mol/L Na₂SO₄	［45］
	Pt/NiO	-0.2	—	20.59 μg/（h·mg）	15.56	0.1 mol/L Na₂SO₄	［46］
	Ru₁@T-C₃N₄	-0.94	Distal mechanism	—	—	—	［47］
	Pt/g-C₃N₄	-0.24	Alternating mechanism	—	—	—	［48］
	Au₁/C₃N₄	-0.88	Alternating mechanism	—	—	—	［49］
	Ru SACs/Cu _x O _y	-0.1~-0.2	Distal mechanism	—	—	—	［68］
	Ru@MoS₂	-0.33	Enzymatic mechanism	—	—	—	［69］
Non-precious metal catalyst	Fe-TiO₂	-0.4	Alternating mechanism	25.47 μg/（h·mg）	25.6	0.5 mol/L LiClO₄	［6］
	ZrPP	-0.38	Enzymatic-consecutive hybrid path	—	—	—	［7］
	Mn@C₃N	-0.75	Distal/alternating mechanism	—	—	—	［8］
	W-VSe₂	-0.36	Distal mechanism	—	—	—	［9］
	W@g-C₃N₄	-0.35	Enzymatic mechanism	—	—	—	［32］
	W/g-CN N	-0.29	Distal mechanism	—	—	—	［33］
	Mo@MoS₂	-0.28	Distal mechanism	—	—	—	［34］
	Mn@BCN NTs	-0.1	Distal mechanism	—	—	—	［35］
	Mo/MoS₂	-0.53	Distal/alternating mechanism	—	—	—	［54］
	Mn-MoP	-0.95	Distal/alternating mechanism	—	—	—	［55］
	Mo₁N₃	-0.02	Distal mechanism	—	—	—	［56］
	Mo@BN	-0.19	nzymatic mechanism	—	—	—	［57］
	Mo@BCN	-0.42	Enzymatic mechanism	—	—	—	［58］
	Fe@N-C	-0.63	Distal/alternating/enzymatic mechanism	—	—	—	［59］
	Fe-N₃/graphene	-0.25	Distal/alternating/ enzymatic mechanism	—	—	—	［60］
	Fe-B₂N₂	-0.65	Distal mechanism	—	—	—	［61］
	Mn@g-N₃C₁O₁	-0.29	Distal mechanism	—	—	—	［62］
	W@BP	-0.40	Distal mechanism	—	—	—	［63］
	Ti@N₄-garphene	-0.69	Distal mechanism	—	—	—	［70］
	V@BN	-0.25	Enzymatic mechanism	—	—	—	［71］
	CrB₃C₁-graphene	-0.13	Distal mechanism	—	—	—	［72］
	Mn_SA@V_sN₁	-0.77	Distal mechanism	—	—	—	［73］
	Fe-B₂N₂	－0.65	Distal mechanism	—	—	—	［74］
	FeB₄-graphene	－0.55	Distal mechanism	—	—	—	［75］
	Mo/C₉N₄	－0.40	Distal mechanism	—	—	—	［76］
	Mo-rTCNQ	-0.48	Distal mechanism	—	—	—	［77］
	MoPc/TcPc	-0.33/-0.54	Distal/distal-alternating mechanism	—	—	—	［78］
	Mo-PTA	-0.26	Distal mechanism	—	—	—	［79］
	Mo@MoS₂	-0.28	Distal mechanism	—	—	—	［80］
	W/Ti_2-_x C₂O _y	-0.11/-0.95	Distal mechanism	—	—	—	［81］
	W@g-C₃N₄	-0.35	Enzymatic mechanism	—	—	—	［82］
	W@C₉N₄	-0.25	Distal mechanism	—	—	—	［83］
Non-metallic catalyst	B/g-C₃N₄	-0.20	Enzymatic mechanism	—	—	—	［84］
	B/C₂N	-0.18	Enzymatic mechanism	—	—	—	［85］
	Si-BN	-1.06	Distal/alternating mechanism	—	—	—	［65］
	B@g-C₃N₄	-0.2	Enzymatic mechanism	—	—	—	［66］
	N-doped@MOFs	-0.3	Distal mechanism	3.4×10^-6 mol/（cm²·h）	10.2	0.1 mol/L KOH	［67］

Classification	Example	Overpotential/V	Mechanism	NH₃ yield rate	FE/%	Electrolyte	Ref.
Precious metal catalyst	Ru/ZrO₂@NC	-0.21	Distal mechanism	3.665 μg/（h·mg）	21	0.1 mol/L HCl	［5］
	Rh SA/GDY	-0.20	Distal mechanism	74.15 μg/（h·cm²）	20.36	0.1 mol/L K₂SO₄	［30］
	Rh₁/MnO₂	—	—	271.8 μg/（h·mg）	73.3	9 mol/L K₂SO₄	［44］
	Pd-TiO₂	-0.5	—	17.4 μg/（h·mg）	12.7	0.1 mol/L Na₂SO₄	［45］
	Pt/NiO	-0.2	—	20.59 μg/（h·mg）	15.56	0.1 mol/L Na₂SO₄	［46］
	Ru₁@T-C₃N₄	-0.94	Distal mechanism	—	—	—	［47］
	Pt/g-C₃N₄	-0.24	Alternating mechanism	—	—	—	［48］
	Au₁/C₃N₄	-0.88	Alternating mechanism	—	—	—	［49］
	Ru SACs/Cu _x O _y	-0.1~-0.2	Distal mechanism	—	—	—	［68］
	Ru@MoS₂	-0.33	Enzymatic mechanism	—	—	—	［69］
Non-precious metal catalyst	Fe-TiO₂	-0.4	Alternating mechanism	25.47 μg/（h·mg）	25.6	0.5 mol/L LiClO₄	［6］
	ZrPP	-0.38	Enzymatic-consecutive hybrid path	—	—	—	［7］
	Mn@C₃N	-0.75	Distal/alternating mechanism	—	—	—	［8］
	W-VSe₂	-0.36	Distal mechanism	—	—	—	［9］
	W@g-C₃N₄	-0.35	Enzymatic mechanism	—	—	—	［32］
	W/g-CN N	-0.29	Distal mechanism	—	—	—	［33］
	Mo@MoS₂	-0.28	Distal mechanism	—	—	—	［34］
	Mn@BCN NTs	-0.1	Distal mechanism	—	—	—	［35］
	Mo/MoS₂	-0.53	Distal/alternating mechanism	—	—	—	［54］
	Mn-MoP	-0.95	Distal/alternating mechanism	—	—	—	［55］
	Mo₁N₃	-0.02	Distal mechanism	—	—	—	［56］
	Mo@BN	-0.19	nzymatic mechanism	—	—	—	［57］
	Mo@BCN	-0.42	Enzymatic mechanism	—	—	—	［58］
	Fe@N-C	-0.63	Distal/alternating/enzymatic mechanism	—	—	—	［59］
	Fe-N₃/graphene	-0.25	Distal/alternating/ enzymatic mechanism	—	—	—	［60］
	Fe-B₂N₂	-0.65	Distal mechanism	—	—	—	［61］
	Mn@g-N₃C₁O₁	-0.29	Distal mechanism	—	—	—	［62］
	W@BP	-0.40	Distal mechanism	—	—	—	［63］
	Ti@N₄-garphene	-0.69	Distal mechanism	—	—	—	［70］
	V@BN	-0.25	Enzymatic mechanism	—	—	—	［71］
	CrB₃C₁-graphene	-0.13	Distal mechanism	—	—	—	［72］
	Mn_SA@V_sN₁	-0.77	Distal mechanism	—	—	—	［73］
	Fe-B₂N₂	－0.65	Distal mechanism	—	—	—	［74］
	FeB₄-graphene	－0.55	Distal mechanism	—	—	—	［75］
	Mo/C₉N₄	－0.40	Distal mechanism	—	—	—	［76］
	Mo-rTCNQ	-0.48	Distal mechanism	—	—	—	［77］
	MoPc/TcPc	-0.33/-0.54	Distal/distal-alternating mechanism	—	—	—	［78］
	Mo-PTA	-0.26	Distal mechanism	—	—	—	［79］
	Mo@MoS₂	-0.28	Distal mechanism	—	—	—	［80］
	W/Ti_2-_x C₂O _y	-0.11/-0.95	Distal mechanism	—	—	—	［81］
	W@g-C₃N₄	-0.35	Enzymatic mechanism	—	—	—	［82］
	W@C₉N₄	-0.25	Distal mechanism	—	—	—	［83］
Non-metallic catalyst	B/g-C₃N₄	-0.20	Enzymatic mechanism	—	—	—	［84］
	B/C₂N	-0.18	Enzymatic mechanism	—	—	—	［85］
	Si-BN	-1.06	Distal/alternating mechanism	—	—	—	［65］
	B@g-C₃N₄	-0.2	Enzymatic mechanism	—	—	—	［66］
	N-doped@MOFs	-0.3	Distal mechanism	3.4×10^-6 mol/（cm²·h）	10.2	0.1 mol/L KOH	［67］

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Theoretical Research Progress of Single Atom Catalysts in Electrochemical Synthesis of Ammonia

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