Metal-Based Electrocatalysts for Selective Electrochemical Nitrogen Reduction to Ammonia

Ammonia (NH3) plays a significant role in the manufacture of fertilizers, nitrogen-containing chemical production, and hydrogen storage. The electrochemical nitrogen reduction reaction (e-NRR) is an attractive prospect for achieving clean and sustainable NH3 production, under mild conditions driven by renewable energy. The sluggish cleavage of N≡N bonds and poor selectivity of e-NRR are the primary challenges for e-NRR, over the competitive hydrogen evolution reaction (HER). The rational design of e-NRR electrocatalysts is of vital significance and should be based on a thorough understanding of the structure–activity relationship and mechanism. Among the various explored e-NRR catalysts, metal-based electrocatalysts have drawn increasing attention due to their remarkable performances. This review highlighted the recent progress and developments in metal-based electrocatalysts for e-NRR. Different kinds of metal-based electrocatalysts used in NH3 synthesis (including noble-metal-based catalysts, non-noble-metal-based catalysts, and metal compound catalysts) were introduced. The theoretical screening and the experimental practice of rational metal-based electrocatalyst design with different strategies were systematically summarized. Additionally, the structure–function relationship to improve the NH3 yield was evaluated. Finally, current challenges and perspectives of this burgeoning area were provided. The objective of this review is to provide a comprehensive understanding of metal-based e-NRR electrocatalysts with a focus on enhancing their efficiency in the future.

[1]  Xin Jiao,et al.  Polyphenol-modified zero-valent iron prepared using ball milling technology for hexavalent chromium removal: Kinetics and mechanisms , 2023, Separation and Purification Technology.

[2]  Sungkyun Choi,et al.  Non-noble metal single atom catalysts for electrochemical energy conversion reactions , 2023, Chinese Journal of Catalysis.

[3]  Hao Zheng,et al.  FeCo-ZIF Derived Carbon-Encapsulated Metal Alloy as Efficient Cathode Material for Heterogeneous Electro-Fenton Reaction in 3-electron ORR Pathway: Enhanced Performance in Alkaline Condition , 2023, Separation and Purification Technology.

[4]  Ming-hua Zhou,et al.  Enhanced organic pollutant removal in saline wastewater by a tripolyphosphate-Fe0/H2O2 system: Key role of tripolyphosphate and reactive oxygen species generation. , 2023, Journal of hazardous materials.

[5]  W. Kim,et al.  Overview of emerging catalytic materials for electrochemical green ammonia synthesis and process , 2023, Carbon Energy.

[6]  W. Tarpeh,et al.  Reactive Separation of Ammonia from Wastewater Nitrate via Molecular Electrocatalysis , 2023, Environmental Science & Technology Letters.

[7]  Xiaoquan Lu,et al.  Improving Electrocatalytic Nitrogen Reduction Selectivity and Yield by Suppressing Hydrogen Evolution Reaction via Electronic Metal–Support Interaction , 2023, Advanced Energy Materials.

[8]  S. Krishnamurty,et al.  Can Li Atoms Anchored on Boron and Nitrogen Doped Graphene Catalyze Dinitrogen Molecule to Ammonia? A DFT Study. , 2023, Chemphyschem : a European journal of chemical physics and physical chemistry.

[9]  D. Astruc,et al.  Recent progress in electrocatalytic nitrogen reduction to ammonia (NRR) , 2023, Coordination Chemistry Reviews.

[10]  Mengfan Wang,et al.  Deciphering engineering principle of three-phase interface for advanced gas-involved electrochemical reactions , 2023, Journal of Energy Chemistry.

[11]  B. Ding,et al.  Complementary Design in Multicomponent Electrocatalysts for Electrochemical Nitrogen Reduction: Beyond the Leverage in Activity and Selectivity. , 2023, Angewandte Chemie.

[12]  A. Robertson,et al.  Single-atom catalysts for electrochemical N_2 reduction to NH_3 , 2023, Rare Metals.

[13]  Yaguang Li,et al.  Nitrogen Reduction Reaction: Heteronuclear Double‐Atom Electrocatalysts , 2023, Small Structures.

[14]  E. Antolini,et al.  Conversion of nitrogen to ammonia using a Cu/C electrocatalyst in a polymeric electrolyte reactor , 2022, Electrochemistry Communications.

[15]  Chao Su,et al.  When Nitrogen Reduction Meets Single-Atom Catalysts , 2022, Progress in Materials Science.

[16]  Chenghua Sun,et al.  Recent progress of iron-based electrocatalysts for nitrogen reduction reaction , 2022, Journal of Materials Science & Technology.

[17]  Jit Mukherjee,et al.  Solvothermal synthesis of α–CuPc nanostructures for electrochemical nitrogen fixation under ambient conditions , 2022, Catalysis Today.

[18]  D. Vo,et al.  Electrocatalytic conversion of nitrate waste into ammonia: a review , 2022, Environmental Chemistry Letters.

[19]  J. Gardea-Torresdey,et al.  Outlining Key Perspectives for the Advancement of Electrocatalytic Remediation of Nitrate from Polluted Waters , 2022, ACS ES&T Engineering.

[20]  J. Tour,et al.  Atomic Molybdenum for Synthesis of Ammonia with 50% Faradic Efficiency. , 2022, Small.

[21]  Ya-li Guo,et al.  Unveiling the Synergy of O‐Vacancy and Heterostructure over MoO3‐x/MXene for N2 Electroreduction to NH3 , 2021, Advanced Energy Materials.

[22]  F. Huo,et al.  Rational Synthesis and Regulation of Hollow Structural Materials for Electrocatalytic Nitrogen Reduction Reaction , 2021, Advanced science.

[23]  Chao Su,et al.  Emerging two-dimensional nanomaterials for electrochemical nitrogen reduction. , 2021, Chemical Society reviews.

[24]  Huiyuan Zhu,et al.  Powering the Remediation of the Nitrogen Cycle: Progress and Perspectives of Electrochemical Nitrate Reduction , 2021, Industrial & Engineering Chemistry Research.

[25]  Qinglin Li,et al.  A General Strategy toward Metal Sulfide Nanoparticles Confined in a Sulfur-Doped Ti3 C2 Tx MXene 3D Porous Aerogel for Efficient Ambient N2 Electroreduction. , 2021, Small.

[26]  Ting Huang,et al.  Nanomaterials for the electrochemical nitrogen reduction reaction under ambient conditions , 2021, Nanoscale advances.

[27]  G. Wallace,et al.  Engineering Carbon Materials for Electrochemical Oxygen Reduction Reactions , 2021, Advanced Energy Materials.

[28]  Haihui Wang,et al.  Comprehensive Understanding of the Thriving Ambient Electrochemical Nitrogen Reduction Reaction , 2021, Advanced materials.

[29]  J. Shui,et al.  Molybdenum-based materials for electrocatalytic nitrogen reduction reaction , 2021 .

[30]  Yuping Liu,et al.  Identifying the Dominant Role of Pyridinic-N-Mo Bonding in Synergistic Electrocatalysis for Ambient Nitrogen Reduction. , 2021, ACS nano.

[31]  Y. Chuang,et al.  Enhancement of NH3 Production in Electrochemical N2 Reduction by the Cu-Rich Inner Surfaces of Beveled CuAu Nanoboxes. , 2021, ACS applied materials & interfaces.

[32]  F. Huo,et al.  The Role of Defects in Metal–Organic Frameworks for Nitrogen Reduction Reaction: When Defects Switch to Features , 2021, Advanced Functional Materials.

[33]  Ioannis Katsounaros,et al.  Electrocatalytic Nitrate Reduction for Sustainable Ammonia Production , 2021, Joule.

[34]  Bin Yuan,et al.  Engineering electrocatalyst for low-temperature N2 reduction to ammonia , 2021 .

[35]  Xiayan Wang,et al.  Effect on electrochemical reduction of nitrogen to ammonia under ambient conditions: challenges and opportunities for chemical fuels , 2021 .

[36]  Chuanxin He,et al.  Recent Progress in 2D Catalysts for Photocatalytic and Electrocatalytic Artificial Nitrogen Reduction to Ammonia , 2021, Advanced Energy Materials.

[37]  Shuangpeng Wang,et al.  Development of Electrocatalysts for Efficient Nitrogen Reduction Reaction under Ambient Condition , 2020, Advanced Functional Materials.

[38]  Jason D. Goodpaster,et al.  Competing Effects of pH, Cation Identity, H2O Saturation, and N2 Concentration on the Activity and Selectivity of Electrochemical Reduction of N2 to NH3 on Electrodeposited Cu at Ambient Conditions , 2020 .

[39]  Yachao Zeng,et al.  Restoring the Nitrogen Cycle by Electrochemical Reduction of Nitrate: Progress and Prospects , 2020 .

[40]  Wenping Hu,et al.  Defect engineering for electrochemical nitrogen reduction reaction to ammonia , 2020 .

[41]  Yuantong Gu,et al.  Metal‐Nitrogen‐Doped Carbon Materials as Highly Efficient Catalysts: Progress and Rational Design , 2020, Advanced Science.

[42]  Yuen Wu,et al.  Highly Productive Electrosynthesis of Ammonia by Admolecule-Targeting Single Ag Sites. , 2020, ACS nano.

[43]  D. Cullen,et al.  Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction toward Electrochemical Ammonia Synthesis Using N 2 and H 2 O , 2020, Small Methods.

[44]  Shaobin Wang,et al.  Rational Catalyst Design for N2 Reduction under Ambient Conditions: Strategies toward Enhanced Conversion Efficiency , 2020 .

[45]  M. Leung,et al.  Bimetallic Mo–Co nanoparticles anchored on nitrogen-doped carbon for enhanced electrochemical nitrogen fixation , 2020, Journal of Materials Chemistry A.

[46]  F. Illas,et al.  Facile Heterogeneously Catalyzed Nitrogen Fixation by MXenes , 2020 .

[47]  Junliang Zhang,et al.  Recent advances in catalysts, electrolytes and electrode engineering for the nitrogen reduction reaction under ambient conditions. , 2020, Nanoscale.

[48]  Xien Liu,et al.  Recent Advances in Electrochemical Synthesis of Ammonia through Nitrogen Reduction under Ambient Conditions , 2020, ChemElectroChem.

[49]  Hui Li,et al.  Electrochemical Synthesis of Ammonia from Nitrogen Under Mild Conditions: Current Status and Challenges , 2020, Electrochemical Energy Reviews.

[50]  Xiaofeng Feng,et al.  Understanding the Electrocatalytic Interface for Ambient Ammonia Synthesis , 2020 .

[51]  M. Oschatz,et al.  Overcoming Chemical Inertness under Ambient Conditions: A Critical View on Recent Developments in Ammonia Synthesis via Electrochemical N 2 Reduction by Asking Five Questions , 2020 .

[52]  Xianfu Wang,et al.  Atomic Structure Modification for Electrochemical Nitrogen Reduction to Ammonia , 2019, Advanced Energy Materials.

[53]  S. Pennycook,et al.  Copper Single Atoms Anchored in Porous Nitrogen-Doped Carbon as Efficient pH-Universal Catalysts for the Nitrogen Reduction Reaction , 2019, ACS Catalysis.

[54]  Haihui Wang,et al.  Advanced Non-metallic Catalysts for Electrochemical Nitrogen Reduction under Ambient Conditions. , 2019, Chemistry.

[55]  Xue Zhao,et al.  In situ nano Au triggered by a metal boron organic polymer: efficient electrochemical N2 fixation to NH3 under ambient conditions , 2019, Journal of Materials Chemistry A.

[56]  Geoffrey I N Waterhouse,et al.  Defect Engineering in Photocatalytic Nitrogen Fixation , 2019, ACS Catalysis.

[57]  Tingshuai Li,et al.  Cr3C2 Nanoparticles-Embedded Carbon Nanofiber for Artificial Synthesis of NH3 through N2 Fixation under Ambient Conditions. , 2019, ACS applied materials & interfaces.

[58]  N. Zhang,et al.  Morphology-dependent electrocatalytic nitrogen reduction on Ag triangular nanoplates. , 2019, Chemical communications.

[59]  Abdullah M. Asiri,et al.  An MnO2–Ti3C2Tx MXene nanohybrid: an efficient and durable electrocatalyst toward artificial N2 fixation to NH3 under ambient conditions , 2019, Journal of Materials Chemistry A.

[60]  Ke Chu,et al.  Ambient electrocatalytic nitrogen reduction on a MoO2/graphene hybrid: experimental and DFT studies , 2019, Catalysis Science & Technology.

[61]  Ke Chu,et al.  Boosted Electrocatalytic N2 Reduction on Fluorine-Doped SnO2 Mesoporous Nanosheets. , 2019, Inorganic chemistry.

[62]  Abdullah M. Asiri,et al.  Spinel LiMn2O4 Nanofiber: An Efficient Electrocatalyst for N2 Reduction to NH3 under Ambient Conditions. , 2019, Inorganic chemistry.

[63]  Y. Wan,et al.  Heterogeneous electrocatalysts design for nitrogen reduction reaction under ambient conditions , 2019, Materials Today.

[64]  Cheng Tang,et al.  How to explore ambient electrocatalytic nitrogen reduction reliably and insightfully. , 2019, Chemical Society reviews.

[65]  Adam C. Nielander,et al.  A Versatile Method for Ammonia Detection in a Range of Relevant Electrolytes via Direct Nuclear Magnetic Resonance Techniques , 2019, ACS Catalysis.

[66]  Adam C. Nielander,et al.  A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements , 2019, Nature.

[67]  Abdullah M. Asiri,et al.  Mn3O4 nanoparticles@reduced graphene oxide composite: An efficient electrocatalyst for artificial N2 fixation to NH3 at ambient conditions , 2019, Nano Research.

[68]  Hao Wen,et al.  In Situ Hydrothermal Growth of TiO2 Nanoparticles on a Conductive Ti3C2T x MXene Nanosheet: A Synergistically Active Ti-Based Nanohybrid Electrocatalyst for Enhanced N2 Reduction to NH3 at Ambient Conditions. , 2019, Inorganic chemistry.

[69]  Douglas R. MacFarlane,et al.  Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia , 2019, Nature Catalysis.

[70]  Jinqiu Zhou,et al.  Over 56.55% Faradaic efficiency of ambient ammonia synthesis enabled by positively shifting the reaction potential , 2019, Nature Communications.

[71]  H. Xin,et al.  Atomically Dispersed Molybdenum Catalysts for Efficient Ambient Nitrogen Fixation. , 2019, Angewandte Chemie.

[72]  Haihui Wang,et al.  Efficient Electrocatalytic N2 Fixation with MXene under Ambient Conditions , 2019, Joule.

[73]  Haihui Wang,et al.  Nitrogen Fixation by Ru Single-Atom Electrocatalytic Reduction , 2019, Chem.

[74]  P. Strasser,et al.  Alloy Nanocatalysts for the Electrochemical Oxygen Reduction (ORR) and the Direct Electrochemical Carbon Dioxide Reduction Reaction (CO2RR) , 2018, Advanced materials.

[75]  Qinghua Zhang,et al.  Rational Design of Fe–N/C Hybrid for Enhanced Nitrogen Reduction Electrocatalysis under Ambient Conditions in Aqueous Solution , 2018, ACS Catalysis.

[76]  Gengfeng Zheng,et al.  NbO 2 Electrocatalyst Toward 32% Faradaic Efficiency for N 2 Fixation , 2018, Small Methods.

[77]  Abdullah M. Asiri,et al.  Ambient NH3 synthesis via electrochemical reduction of N2 over cubic sub-micron SnO2 particles. , 2018, Chemical communications.

[78]  Fengli Qu,et al.  Cr2O3 nanofiber: a high-performance electrocatalyst toward artificial N2 fixation to NH3 under ambient conditions. , 2018, Chemical communications.

[79]  Lin Guo,et al.  Photocatalysis and Photoelectrocatalysis Methods of Nitrogen Reduction for Sustainable Ammonia Synthesis , 2018, Small Methods.

[80]  B. Tang,et al.  Electrocatalytic Hydrogenation of N2 to NH3 by MnO: Experimental and Theoretical Investigations , 2018, Advanced science.

[81]  Xuping Sun,et al.  Mn3 O4 Nanocube: An Efficient Electrocatalyst Toward Artificial N2 Fixation to NH3. , 2018, Small.

[82]  Haihui Wang,et al.  Molybdenum Carbide Nanodots Enable Efficient Electrocatalytic Nitrogen Fixation under Ambient Conditions , 2018, Advanced materials.

[83]  Jingguang G. Chen,et al.  Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles. , 2018, Journal of the American Chemical Society.

[84]  Abdullah M. Asiri,et al.  Boosted Electrocatalytic N2 Reduction to NH3 by Defect‐Rich MoS2 Nanoflower , 2018, Advanced Energy Materials.

[85]  Hairong Xue,et al.  Ambient Electrochemical Synthesis of Ammonia from Nitrogen and Water Catalyzed by Flower-Like Gold Microstructures. , 2018, ChemSusChem.

[86]  D. Macfarlane,et al.  Energy-Efficient Nitrogen Reduction to Ammonia at Low Overpotential in Aqueous Electrolyte under Ambient Conditions. , 2018, ChemSusChem.

[87]  Shiping Huang,et al.  Tuning nitrogen reduction reaction activity via controllable Fe magnetic moment: A computational study of single Fe atom supported on defective graphene , 2018, Electrochimica Acta.

[88]  Qiang Xu,et al.  Metal–Organic Frameworks as Platforms for Catalytic Applications , 2018, Advanced materials.

[89]  Jinhua Ye,et al.  Nitrogen Fixation Reaction Derived from Nanostructured Catalytic Materials , 2018, Advanced Functional Materials.

[90]  Jun Wang,et al.  Ambient Electrochemical Ammonia Synthesis with High Selectivity on Fe/Fe Oxide Catalyst , 2018, ACS Catalysis.

[91]  M. El-Sayed,et al.  Electrochemical Synthesis of Ammonia from N2 and H2O under Ambient Conditions Using Pore-Size-Controlled Hollow Gold Nanocatalysts with Tunable Plasmonic Properties. , 2018, The journal of physical chemistry letters.

[92]  Baozhan Zheng,et al.  Enabling Effective Electrocatalytic N2 Conversion to NH3 by the TiO2 Nanosheets Array under Ambient Conditions. , 2018, ACS applied materials & interfaces.

[93]  Qiang Zhang,et al.  Highly Selective Electrochemical Reduction of Dinitrogen to Ammonia at Ambient Temperature and Pressure over Iron Oxide Catalysts. , 2018, Chemistry.

[94]  Xuping Sun,et al.  Ambient N2 fixation to NH3 electrocatalyzed by a spinel Fe3O4 nanorod. , 2018, Nanoscale.

[95]  Qiang Zhang,et al.  A Review of Electrocatalytic Reduction of Dinitrogen to Ammonia under Ambient Conditions , 2018 .

[96]  Xuping Sun,et al.  Electrochemical N2 fixation to NH3 under ambient conditions: Mo2N nanorod as a highly efficient and selective catalyst. , 2018, Chemical communications.

[97]  J. Renner,et al.  The Use of Controls for Consistent and Accurate Measurements of Electrocatalytic Ammonia Synthesis from Dinitrogen , 2018, ACS Catalysis.

[98]  Abdullah M. Asiri,et al.  Efficient Electrochemical N2 Reduction to NH3 on MoN Nanosheets Array under Ambient Conditions , 2018, ACS Sustainable Chemistry & Engineering.

[99]  Xuping Sun,et al.  MoO3 nanosheets for efficient electrocatalytic N2 fixation to NH3 , 2018 .

[100]  Sajanlal R. Panikkanvalappil,et al.  Enhancing the rate of electrochemical nitrogen reduction reaction for ammonia synthesis under ambient conditions using hollow gold nanocages , 2018, Nano Energy.

[101]  C. Maravelias,et al.  Greening Ammonia toward the Solar Ammonia Refinery , 2018, Joule.

[102]  F. Garzon,et al.  Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study. , 2018, Physical chemistry chemical physics : PCCP.

[103]  Bo Tang,et al.  Electrochemical Ammonia Synthesis via Nitrogen Reduction Reaction on a MoS2 Catalyst: Theoretical and Experimental Studies , 2018, Advanced materials.

[104]  Fengli Qu,et al.  Highly efficient electrochemical ammonia synthesis via nitrogen reduction reactions on a VN nanowire array under ambient conditions. , 2018, Chemical communications.

[105]  H. Xin,et al.  Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential , 2018, Nature Communications.

[106]  D. Macfarlane,et al.  Rational Electrode–Electrolyte Design for Efficient Ammonia Electrosynthesis under Ambient Conditions , 2018 .

[107]  Jijun Zhao,et al.  Facile Ammonia Synthesis from Electrocatalytic N2 Reduction under Ambient Conditions on N-Doped Porous Carbon , 2018 .

[108]  Chenghua Sun,et al.  Computational Study of MoN2 Monolayer as Electrochemical Catalysts for Nitrogen Reduction , 2017 .

[109]  Chang Won Yoon,et al.  Electrochemical Synthesis of NH3 at Low Temperature and Atmospheric Pressure Using a γ-Fe2O3 Catalyst , 2017 .

[110]  Younes Abghoui,et al.  Computational Screening of Rutile Oxides for Electrochemical Ammonia Formation , 2017 .

[111]  Zhijiang Wang,et al.  Electrochemical reduction of aqueous nitrogen (N2) at a low overpotential on (110)-oriented Mo nanofilm , 2017 .

[112]  Q. Jiang,et al.  Amorphizing of Au Nanoparticles by CeOx–RGO Hybrid Support towards Highly Efficient Electrocatalyst for N2 Reduction under Ambient Conditions , 2017, Advanced materials.

[113]  Jingxiang Zhao,et al.  Single Mo Atom Supported on Defective Boron Nitride Monolayer as an Efficient Electrocatalyst for Nitrogen Fixation: A Computational Study. , 2017, Journal of the American Chemical Society.

[114]  M. Antonietti,et al.  Efficient Electrocatalytic Reduction of CO2 by Nitrogen-Doped Nanoporous Carbon/Carbon Nanotube Membranes: A Step Towards the Electrochemical CO2 Refinery. , 2017, Angewandte Chemie.

[115]  Younes Abghoui,et al.  Onset potentials for different reaction mechanisms of nitrogen activation to ammonia on transition metal nitride electro-catalysts , 2017 .

[116]  Jun-min Yan,et al.  Au Sub‐Nanoclusters on TiO2 toward Highly Efficient and Selective Electrocatalyst for N2 Conversion to NH3 at Ambient Conditions , 2017, Advanced materials.

[117]  Claudio Ampelli,et al.  Electrocatalytic Synthesis of Ammonia at Room Temperature and Atmospheric Pressure from Water and Nitrogen on a Carbon-Nanotube-Based Electrocatalyst. , 2017, Angewandte Chemie.

[118]  Yi Luo,et al.  Conversion of Dinitrogen to Ammonia by FeN3-Embedded Graphene. , 2016, Journal of the American Chemical Society.

[119]  R. Gebauer,et al.  Nitrogen electrochemically reduced to ammonia with hematite: density-functional insights. , 2015, Physical chemistry chemical physics : PCCP.

[120]  Younes Abghoui,et al.  Enabling electrochemical reduction of nitrogen to ammonia at ambient conditions through rational catalyst design. , 2015, Physical chemistry chemical physics : PCCP.

[121]  Andrew J. Medford,et al.  Departures from the Adsorption Energy Scaling Relations for Metal Carbide Catalysts , 2014 .

[122]  H. Jónsson,et al.  A theoretical evaluation of possible transition metal electro-catalysts for N2 reduction. , 2012, Physical chemistry chemical physics : PCCP.

[123]  Lungang Chen,et al.  A Review on Catalysts for Electrocatalytic and Photocatalytic Reduction of N2 to Ammonia , 2022, Green Chemistry.

[124]  Wenxing Chen,et al.  Atomically dispersed metal catalysts for electrochemical nitrogen reduction reaction , 2022, Journal of Materials Chemistry A.

[125]  J. Liu,et al.  Changing Charge Transfer Mode with Cobalt-Molybdenum Bimetallic Atomic Pairs for Enhanced Nitrogen Fixation , 2022, Journal of Materials Chemistry A.

[126]  Suojiang Zhang,et al.  Recent progress in electrochemical synthesis of ammonia from nitrogen: strategies to improve the catalytic activity and selectivity , 2021, Energy & Environmental Science.

[127]  Xin-bo Zhang,et al.  Electrochemical Reduction of N2 under Ambient Conditions for Artificial N2 Fixation and Renewable Energy Storage Using N2/NH3 Cycle , 2017, Advanced materials.