Citation: BI Yipiao, GONG Xue, YANG Fa, RUAN Mingbo, SONG Ping, XU Weilin. Polyvalent MnO_x/C Electrocatalyst for HighlyEfficient Nitrogen Reduction Reaction[J]. Chinese Journal of Applied Chemistry, ;2020, 37(9): 1048-1055. doi: 10.11944/j.issn.1000-0518.2020.09.200085 shu

Polyvalent MnO_x/C Electrocatalyst for HighlyEfficient Nitrogen Reduction Reaction

BI Yipiao ^a,b ,
GONG Xue ^a ,
YANG Fa ^a,b ,
RUAN Mingbo ^a ,
SONG Ping ^a ,
XU Weilin ^a,b,,

a.
Advanced Power Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
University of Science and Technology of China, Hefei 230026, China

Corresponding author: XU Weilin, weilinxu@ciac.ac.cn
Received Date: 22 March 2020
Revised Date: 15 April 2020
Accepted Date: 7 May 2020

Fund Project: Guangdong Joint Fund U1601211National Natural Science Foundation of China 21433003National Natural Science Foundation of China 2017YF9127900National Natural Science Foundation of China 21721003National Natural Science Foundation of China 2018YFB1502302Supported by the National Science Foundation for Distinguished Young Scholars of China(No.21925205), the Guangdong Joint Fund(No.U1601211), and the National Natural Science Foundation of China(No.21733004, No.21633008, No.2017YFE9127900, No.21721003, No.2018YFB1502302, No.21433003)National Natural Science Foundation of China 21633008National Science Foundation for Distinguished Young Scholars of China 21925205National Natural Science Foundation of China 21733004

Figures(4)

NH₃ plays an important role in human production and life, but the main way to produce NH₃ is still the high energy consumption and high pollution Haber-Bosch process. Electrocatalytic N₂ reduction reaction (ENRR) is considered to be an effective alternative method, however highly efficient catalyst is still a challenging as a result of high bond energy of N≡N. Here, we report an electrocatalyst of polyvalent MnO_x/C which is designed via simple redox reaction for highly efficient production of ammonia (with yield up to 7.8 μg_NH₃/(h·mg_cat) and Faradic efficiency (FE) up to 9.2%) from nitrogen reduction reaction (NRR). The high NRR performance of polyvalent MnO_x/C mainly originates from a synergistic effect among different valence states (Mn²⁺, Mn³⁺, Mn⁴⁺) of Mn for NRR.
- ammonia synthesis,
- electrocatalysis,
- transition metal oxide,
- synergistic effect
1. [1]
  Mukherjee S, Cullen D A, Karakalos S. Metal-Organic Framework-Derived Nitrogen-Doped Highly Disordered Carbon for Electrochemical Ammonia Synthesis Using N₂ and H₂O in Alkaline Electrolytes[J]. Nano Energy, 2018,48:217-226. doi: 10.1016/j.nanoen.2018.03.059
2. [2]
  Lv C, Yan C, Chen G. An Amorphous Noble-Metal-Free Electrocatalyst that Enables Nitrogen Fixation under Ambient Conditions[J]. Angew Chem Int Ed, 2018,57:6073-6076. doi: 10.1002/anie.201801538
3. [3]
  Shipman M A, Symes M D. Recent Progress Towards the Electrosynthesis of Ammonia from Sustainable Resources[J]. Catal Today, 2017,286:57-68. doi: 10.1016/j.cattod.2016.05.008
4. [4]
  Li S J, Bao D, Shi M M. Amorphizing of Au Nanoparticles by CeO_x-RGO Hybrid Support Towards Highly Efficient Electrocatalyst for N₂ Reduction under Ambient Conditions[J]. Adv Mater, 2017,291700001. doi: 10.1002/adma.201700001
5. [5]
  Hao Y, Dong X, Zhai S. Hydrogenated Bismuth Molybdate Nanoframe for Efficient Sunlight-Driven Nitrogen Fixation from Air[J]. Chem-Eur J, 2016,22:18722-18728. doi: 10.1002/chem.201604510
6. [6]
  Burgess B K, Wherland S, Newton W E. Nitrogenase Reactivity:Insight into the Nitrogen-Fixing Process Through Hydrogen-Inhibition and HD-Forming Reactions[J]. Biochemistry, 1981,20:5140-5146. doi: 10.1021/bi00521a007
7. [7]
  Wang L, Xia M, Wang H. Greening Ammonia toward the Solar Ammonia Refinery[J]. Joule, 2018,2:1055-1074. doi: 10.1016/j.joule.2018.04.017
8. [8]
  Zhu D, Zhang L, Ruther R E. Photo-illuminated Diamond as a Solid-state Source of Solvated Electrons in Water for Nitrogen Reduction[J]. Nat Mater, 2013,12:836-841. doi: 10.1038/nmat3696
9. [9]
  Li X, Wang W, Jiang D. Efficient Solar-Driven Nitrogen Fixation over Carbon-Tungstic-Acid Hybrids[J]. Chem-Eur J, 2016,22:13819-13822. doi: 10.1002/chem.201603277
10. [10]
  Guo C, Ran J, Vasileff A. Rational Design of Electrocatalysts and Photo(electro)catalysts for Nitrogen Reduction to Ammonia (NH₃) under Ambient Conditions[J]. Energy Environ Sci, 2018,11:45-56. doi: 10.1039/C7EE02220D
11. [11]
  Yandulov D V, Schrock R R. Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center[J]. Science, 2003,301:76-78. doi: 10.1126/science.1085326
12. [12]
  Murakami T, Nishikiori T, Nohira T. Electrolytic Synthesis of Ammonia in Molten Salts under Atmospheric Pressure[J]. J Am Chem Soc, 2003,125:334-335. doi: 10.1021/ja028891t
13. [13]
  Zhang R, Ren X, Shi X. Enabling Effective Electrocatalytic N₂ Conversion to NH₃ by the TiO₂ Nanosheets Array under Ambient Conditions[J]. ACS Appl Mater Interfaces, 2018,10:28251-28255. doi: 10.1021/acsami.8b06647
14. [14]
  Kyriakou V, Garagounis I, Vasileiou E. Progress in the Electrochemical Synthesis of Ammonia[J]. Catal Today, 2017,286:2-13. doi: 10.1016/j.cattod.2016.06.014
15. [15]
  Singh A R, Rohr B A, Schwalbe J A. Electrochemical Ammonia Synthesis-The Selectivity Challenge[J]. ACS Catal, 2017,7:706-709. doi: 10.1021/acscatal.6b03035
16. [16]
  Lu Y, Yang Y, Zhang T. Photoprompted Hot Electrons from Bulk Cross-Linked Graphene Materials and Their Efficient Catalysis for Atmospheric Ammonia Synthesis[J]. ACS Nano, 2016,10:10507-10515. doi: 10.1021/acsnano.6b06472
17. [17]
  Wang X, Wang W, Qiao M. Atomically Dispersed Au1 Catalyst towards Efficient Electrochemical Synthesis of Ammonia[J]. Sci Bull, 2018,63:1246-1253. doi: 10.1016/j.scib.2018.07.005
18. [18]
  Wang J, Yu L, Hu L. Ambient Ammonia Synthesis via Palladium-Catalyzed Electrohydrogenation of Dinitrogen at Low Overpotential[J]. Nat Commun, 2018,9:1-7. doi: 10.1038/s41467-017-02088-w
19. [19]
  Lin B, Liu Y, Heng L. Morphology Effect of Ceria on the Catalytic Performances of Ru/CeO₂ Catalysts for Ammonia Synthesis[J]. Ind Eng Chem Res, 2018,57:9127-9135. doi: 10.1021/acs.iecr.8b02126
20. [20]
  Wang D, Azofra L M, Harb M. Energy-Efficient Nitrogen Reduction to Ammonia at Low Overpotential in Aqueous Electrolyte under Ambient Conditions[J]. ChemSusChem, 2018,11:3416-3422. doi: 10.1002/cssc.201801632
21. [21]
  Tao H, Choi C, Ding L. Nitrogen Fixation by Ru Single-Atom Electrocatalytic Reduction[J]. Chemistry, 2019,5:204-214. doi: 10.1016/j.chempr.2018.10.007
22. [22]
  Liu H M, Han S H, Zhao Y. Surfactant-Free Atomically Ultrathin Rhodium Nanosheet Nanoassemblies for Efficient Nitrogen Electroreduction[J]. J Mater Chem A, 2018,6:3211-3217. doi: 10.1039/C7TA10866D
23. [23]
  Wang Y, Jia K, Pan Q. Boron-Doped TiO₂ for Efficient Electrocatalytic N₂ Fixation to NH₃ at Ambient Conditions[J]. ACS Sus Chem Eng, 2019,7:117-122. doi: 10.1021/acssuschemeng.8b05332
24. [24]
  Chen S, Perathoner S, Ampelli C. Electrocatalytic Synthesis of Ammonia at Room Temperature and Atmospheric Pressure from Water and Nitrogen on a Carbon-Nanotube-Based Electrocatalyst[J]. Angew Chem, 2017,56:2699-2703. doi: 10.1002/anie.201609533
25. [25]
  Wang M, Liu S, Qian T. Over 56.55% Faradaic Efficiency of Ambient Ammonia Synthesis Enabled by Positively Shifting the Reaction Potentia[J]. Nat Commun, 2019,10:1-8. doi: 10.1038/s41467-018-07882-8
26. [26]
  Cheng H, Ding L X, Chen G F. Molybdenum Carbide Nanodots Enable Efficient Electrocatalytic Nitrogen Fixation under Ambient Conditions[J]. Adv Mater, 2018,301803694. doi: 10.1002/adma.201803694
27. [27]
  Ren X, Cui G, Chen L. Electrochemical N₂ Fixation to NH₃ under Ambient Conditions:Mo₂N Nanorod as a Highly Efficient and Selective Catalyst[J]. Chem Commun, 2018,54:8474-8477. doi: 10.1039/C8CC03627F
28. [28]
  Zhang L, Ji X, Ren X. Electrochemical Ammonia Synthesis via Nitrogen Reduction Reaction on a MoS₂ Catalyst:Theoretical and Experimental Studies[J]. Adv Mater, 2018,301800191. doi: 10.1002/adma.201800191
29. [29]
  Yao Y, Yao Y, Feng Q. Chromium Oxynitride Electrocatalysts for Electrochemical Synthesis of Ammonia under Ambient Conditions[J]. Small Methods, 2019,31800324. doi: 10.1002/smtd.201800324
30. [30]
  Liu Y, Su Y, Quan X. Facile Ammonia Synthesis from Electrocatalytic N₂ Reduction under Ambient Conditions on N-Doped Porous Carbon[J]. ACS Catal, 2018,8:1186-1191. doi: 10.1021/acscatal.7b02165
31. [31]
  Song P, Wang H, Kang L. Electrochemical Nitrogen Reduction to Ammonia at Ambient Conditions on Nitrogen and Phosphorus Co-Doped Porous Carbon[J]. Chem Commun, 2019,55:687-690. doi: 10.1039/C8CC09256G
32. [32]
  Song Y, Johnson D, Peng R. A Physical Catalyst for the Electrolysis of Nitrogen to Ammonia[J]. Sci Adv, 2018,4e1700336. doi: 10.1126/sciadv.1700336
33. [33]
  Jin H, Guo C, Liu X. Emerging Two-Dimensional Nanomaterials for Electrocatalysis[J]. Chem Rev, 2018,118:6337-6408. doi: 10.1021/acs.chemrev.7b00689
34. [34]
  Huang L, Wu J, Han P. NbO₂ Electrocatalyst Toward 32% Faradaic Efficiency for N₂ Fixation[J]. Small Methods, 2019,31800386. doi: 10.1002/smtd.201800386
35. [35]
  Liu Q, Zhang X, Zhang B. Ambient N₂ Fixation to NH₃ Electrocatalyzed by a Spinel Fe₃O₄ Nanorod[J]. Nanoscale, 2018,10:14386-14389. doi: 10.1039/C8NR04524K
36. [36]
  Han J, Ji X, Ren X. MoO₃ Nanosheets for Efficient Electrocatalytic N₂ Fixation to NH₃[J]. J Mater Chem A, 2018,6:12974-12977. doi: 10.1039/C8TA03974G
37. [37]
  Wu X, Xia L, Wang Y. Mn₃O₄ Nanocube:An Efficient Electrocatalyst toward Artificial N₂ Fixation to NH₃[J]. Small, 2018,141803111. doi: 10.1002/smll.201803111
38. [38]
  Wang Z, Gong F, Zhang L. Electrocatalytic Hydrogenation of N₂ to NH₃ by MnO:Experimental and Theoretical Investigations[J]. Adv Sci, 2019,61801182. doi: 10.1002/advs.201801182
39. [39]
  Zhang L, Xie X Y, Wang H. Boosting Electrocatalytic N₂ Reduction by MnO₂ with Oxygen Vacancies[J]. Chem Commun, 2019,55:4627-4630. doi: 10.1039/C9CC00936A
40. [40]
  Roche I, Chainet E, Chatenet M. Carbon-Supported Manganese Oxide Nanoparticles as Electrocatalysts for the Oxygen Reduction Reaction (ORR) in Alkaline Medium:Physical Characterizations and ORR Mechanism[J]. J Phys Chem C, 2007,111:1434-1443.
41. [41]
  Watt G W, Chrisp J D. Spectrophotometric Method for Determination of Hydrazine[J]. Anal Chem, 1952,24:2006-2008. doi: 10.1021/ac60072a044
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Polyvalent MnOx/C Electrocatalyst for HighlyEfficient Nitrogen Reduction Reaction

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通讯作者: 陈斌, bchen63@163.com

Polyvalent MnO_x/C Electrocatalyst for HighlyEfficient Nitrogen Reduction Reaction