主族s区金属Mg电催化N2还原反应的第一性原理计算研究

doi:10.52396/JUST-2021-0126

中国科学技术大学学报 ›› 2021, Vol. 51 ›› Issue (11): 822-830.DOI: 10.52396/JUST-2021-0126

主族s区金属Mg电催化N₂还原反应的第一性原理计算研究

杨康¹, 王长来^1,3, 邓希⁴, 陈乾旺^1,2*

1.合肥微尺度物质科学国家研究中心,中国科学技术大学材料科学与工程系,安徽合肥 230026;
2.中国科学院合肥物质科学研究院,强磁场安徽省实验室,安徽合肥 230031;
3.香港城市大学材料科学与工程系,超金刚石及先进薄膜研究中心,香港 999077;
4.中国科学技术大学化学与材料科学学院,安徽合肥 230026

收稿日期:2021-05-07 修回日期:2021-06-29 出版日期:2021-11-30 发布日期:2022-01-13
通讯作者: *E-mail:cqw@ustc.edu.cn

Tuning main-group s-block metal Mg as a promising single-atom electrocatalyst for N₂ fixation: A DFT study

YANG Kang¹, WANG Changlai^1,3, DENG Xi⁴, CHEN Qianwang^1,2*

1. Hefei National Laboratory for Physical Sciences at the Microscale, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, China;
2. The Anhui High Magnetic Field Laboratory, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China;
3. Department of Materials Science and Engineering, Center of Super-Diamond and Advanced Films (COSDAF), City University of Hong Kong, Hong Kong 999077, China;
4. School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China

Received:2021-05-07 Revised:2021-06-29 Online:2021-11-30 Published:2022-01-13
Contact: * E-mail: cqw@ustc.edu.cn

摘要/Abstract

摘要： 电催化N₂还原反应(NRR)可以在温和的条件下利用可再生的电力将氮气和质子从电解质水溶液转化为氨,被认为是一种非常有前景的替代哈伯法合成氨技术.但是这项技术也面临巨大的挑战,因为N₂分子中的N≡N键非常牢固,需要高活性的催化剂才能将其断裂.和过渡金属相比,主族s区金属在NRR中很少被研究.本文采用第一性原理计算的方法,发现氧掺杂的石墨烯锚定的镁单原子催化剂(Mg-O₄)是一种高活性的NRR电催化剂.理论计算结果表明,N₂分子能有效地被Mg-O₄活化,并通过非解离交替机制被还原成NH₃.此外,分子动力学模拟结果显示Mg-O₄具有高的稳定性.

关键词: 电催化N₂还原反应, 主族金属, 单原子催化剂, 第一性原理计算

Abstract: The electrocatalytic nitrogen reduction reaction (NRR) can transform nitrogen and protons from aqueous electrolytes to ammonia by using renewable electricity under ambient conditions, which is a promising technology to replace the Haber-Bosch process. However, this technology is extremely challenging as it requires highly active electrocatalysts to break the stable triple-bonds of N₂.With p bands,main-group s-block metals have been rarely explored in NRR compared with transition metals.Herein, we employ first-principles calculations to propose a Mg single atom catalyst as a promising high-performance electrocatalyst for NRR, where Mg atom is coordinated with four oxygen atoms within graphene (Mg-O₄). Our results reveal that N₂ can be efficiently activated on Mg-O₄ and reduced into NH₃ through the alternating mechanism. Moreover, ab initio molecular dynamics simulations demonstrate the Mg-O₄structure has high stability.

Key words: electrocatalytic N₂ reduction reaction, main-group metal, single atom catalyst, first-principles calculations

中图分类号:

O643

杨康, 王长来, 邓希, 陈乾旺. 主族s区金属Mg电催化N₂还原反应的第一性原理计算研究[J]. 中国科学技术大学学报, 2021, 51(11): 822-830.

YANG Kang, WANG Changlai, DENG Xi, CHEN Qianwang. Tuning main-group s-block metal Mg as a promising single-atom electrocatalyst for N₂ fixation: A DFT study[J]. Journal of University of Science and Technology of China, 2021, 51(11): 822-830.

参考文献

[1] Chen P Z, Zhang N, Wang S B, et al. Interfacial engineering of cobalt sulfide/graphene hybrids for highly efficient ammonia electrosynthesis. PANS, 2019, 116(14): 6635-6640.
[2] Chen G F, Yuan Y F, Jiang H F, Ren, et al. Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper–molecular solid catalyst. Nat. Energy, 2020, 5: 605-613.
[3] Zhang N, Jalil A, Wu D X, et al. Refining defect states in W₁₈O₄₉ by Mo doping: A strategy for tuning N₂ activation towards solar-driven nitrogen fixation. J. Am. Chem. Soc., 2018, 140(30): 9434-9443.
[4] Suryanto B H, Du H L, Wang, D B, et al. Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia. Nat. Catal., 2019, 2: 290-296.
[5] van der Ham C J, Koper M T, Hetterscheid D G. Challenges in reduction of dinitrogen by proton and electron transfer. Chem. Soc. Rev., 2014, 43: 5183-5191.
[6] Chen J G, Crooks R M, Seefeldt L C, et al. Beyond fossil fuel-driven nitrogen transformations. Science, 2018, 360(6391): eaar6611.
[7] Kitano M, Inoue Y, Yamazaki Y, et al. Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store. Nat. Chem., 2012, 4: 934-940.
[8] Geng Z G, Liu Y, Kong X D, et al. Achieving a record-high yield rate of 120.9 for N₂ electrochemical reduction over Ru single-atom catalysts. Adv. Mater., 2018, 30(40): 1803498.
[9] Soloveichik G. Electrochemical synthesis of ammonia as a potential alternative to the Haber–Bosch process. Nat. Catal., 2019, 2: 377-380.
[10] Lee H K, Koh C S, Lee Y H, et al. Favoring the unfavored: selective electrochemical nitrogen fixation using a reticular chemistry approach. Sci. Adv., 2018, 4(3): eaar3208.
[11] Tao H C, Choi C, Ding L X, et al. Nitrogen fixation by Ru single-atom electrocatalytic reduction. Chem, 2019, 5(1): 204-214.
[12] Liu S S, Qian T, Wang M F, et al. Proton-filtering covalent organic frameworks with superior nitrogen penetration flux promote ambient ammonia synthesis. Nat. Catal., 2021, 4: 322-331.
[13] Luo Y R, Chen G F, Ding L, et al. Efficient electrocatalytic N₂ fixation with MXene under ambient conditions. Joule, 2019, 3(1): 279-289.
[14] Liu Y, Li Q Y, Guo X, et al. A highly efficient metal-free electrocatalyst of F-doped porous carbon toward N₂ electroreduction. Adv. Mater., 2020, 32(24): 1907690.
[15] Tong Y Y, Guo H P, Liu D L, et al. Vacancy engineering of iron-doped W₁₈O₄₉ nanoreactors for low-barrier electrochemical nitrogen reduction. Angew. Chem. Int. Ed., 2020, 59(19): 7356-7361.
[16] Liu Y Y, Han M M, Xiong Q Z, et al. Dramatically enhanced ambient ammonia electrosynthesis performance by in-operando created Li-S interactions on MoS₂ electrocatalyst. Adv. Energy Mater., 2019, 9(14): 1803935.
[17] Zhao Y F, Zhou H, Zhu X R, et al. Simultaneous oxidative and reductive reactions in one system by atomic design. Nat. Catal., 2021, 4: 134-143.
[18] Borah K D, Bhuyan J. Magnesium porphyrins with relevance to chlorophylls. Dalton Trans., 2017, 46: 6497–6509.
[19] Deshpande C N, Ruwe T A, Shawki A, et al. Calcium is an essential cofactor for metal efflux by the ferroportin transporter family. Nat. Commun., 2018, 9: 3075.
[20] Deng D H, Novoselov K S, Fu Q, et al. Catalysis with two-dimensional materials and their heterostructures. Nat. Nanotech., 2016, 11: 218-230.
[21] Fei H L, Dong J C, Wan C Z, et al. Microwave-assisted rapid synthesis of graphene-supported single atomic metals. Adv. Mater., 2018, 30(35): 1802146.
[22] Zhang L Z, Jia Y, Gao G P, et al. Graphene defects trap atomic Ni species for hydrogen and oxygen evolution reactions. Chem, 2018, 4(2): 285-297.
[23] Du Z Z, Chen X J, Hu W, et al. Cobalt in nitrogen-doped graphene as single-atom catalyst for high-sulfur content lithium-sulfur batteries. J. Am. Chem. Soc., 2019, 141(9): 3977-3985.
[24] Hu B, Hu M W, Seefeldt L, et al. Electrochemical dinitrogen reduction to ammonia by Mo₂N: Catalysis or decomposition? ACS Energy Lett., 2019, 4: 1053-1054.
[25] Tang C, Qiao S Z. How to explore ambient electrocatalytic nitrogen reduction reliably and insightfully. Chem. Soc. Rev., 2019, 48: 3166-3180.
[26] Andersen S Z, oli V, Yang S, et al. A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements. Nature, 2019, 570: 504-508.
[27] Kresse G, Hafner J. Ab-initio molecular-dynamics for open-shell transition-metals. Phys. Rev. B, 1993, 48: 13115-13118.
[28] Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys. Rev. Lett., 1996, 77: 3865-3868.
[29] Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B, 1999, 59: 1758-1775.
[30] Maintz S, Deringer V L, Tchougréeff A L, et al. LOBSTER: A tool to extract chemical bonding from plane-wave based DFT. J. Comput. Chemi., 2016, 37: 1030-1035.
[31] Dronskowski R, Bloechl P E. Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations. J. Phys. Chem., 1993, 97: 8617-8624.
[32] Riyaz M, Goel N. Single-atom catalysis using chromium embedded in divacant graphene for conversion of dinitrogen to ammonia. ChemPhysChem, 2019, 20(15): 1954-1959.
[33] Wang J, Huang Z Q, Liu W, et al. Design of N-coordinated dual-metal sites: A stable and active Pt-free catalyst for acidic oxygen reduction reaction. J. Am. Chem. Soc., 2017, 139(48): 17281-17284.
[34] Zheng T T, Jiang K, Ta N, et al. Large-scale and highly selective CO₂ electrocatalytic reduction on nickel single-atom catalyst. Joule, 2019, 3(1): 265-278.
[35] Ling C Y, Niu X H, Li Q, et al. Metal-free single atom catalyst for N₂ fixation driven by visible light. J. Am. Chem. Soc., 2018, 140(43): 14161-14168.
[36] Zheng X N, Yao Y, Wang Y, et al. Tuning the electronic structure of transition metals embedded in nitrogen-doped graphene for electrocatalytic nitrogen reduction: a first-principles study. Nanoscale, 2020, 12: 9696-9707.
[37] Robbins D L, Brock L R, Pilgrim J S, et al. Electronic spectroscopy of the Mg⁺–N₂ complex: evidence for photoinduced activation of N₂. J. Chem. Phys., 1995, 102: 1481-1492.
[38] Legare M A, Belanger-Chabot G, Dewhurst R D, et al. Nitrogen fixation and reduction at boron. Science, 2018, 359(6378): 896-899.
[39] Li X F, Li Q K, Cheng J, et al. Conversion of dinitrogen to ammonia by FeN₃-embedded graphene. J. Am. Chem. Soc., 2016, 138(28): 8706-8709.
[40] Yin H, Li S L, Gan L Y, et al. Pt-embedded in monolayer g-C₃N₄ as a promising single-atom electrocatalyst for ammonia synthesis. J. Mater. Chem. A, 2019, 7: 11908-11914.
[41] Liu S S, Wang M F, Qian T, et al. Facilitating nitrogen accessibility to boron-rich covalent organic frameworks via electrochemical excitation for efficient nitrogen fixation. Nat. Commun., 2019, 10: 3898.
[42] Montoya J H, Tsai C, Vojvodic A, et al. The challenge of electrochemical ammonia synthesis: A new perspective on the role of nitrogen scaling relations. ChemSusChem, 2015, 8(13): 2180-2186.

主族s区金属Mg电催化N₂还原反应的第一性原理计算研究

Tuning main-group s-block metal Mg as a promising single-atom electrocatalyst for N₂ fixation: A DFT study

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 7

编辑推荐

Metrics

本文评价

[1]	刘崇静, 圣蓓蓓, 曹登丰, 陈双明, 宋礼. OER电催化剂的结构重构及同步辐射研究[J]. 中国科学技术大学学报, 2021, 51(11): 787-801.
[2]	江文斌, 刘敬祥, 邱畅, 龙冉, 熊宇杰. 基于金属氧化物的光催化甲烷转化：原理、进展与挑战[J]. 中国科学技术大学学报, 2020, 50(11): 1361-1382.
[3]	徐磊，吴向坤，于同坡，周晓国，刘世林. 二甲醚在13.30～14.30 eV激发能下的光电离解离研究[J]. 中国科学技术大学学报, 2020, 50(5): 629-636.
[4]	夏艺萌，陈昱. 基于E-GAS-AST模型对金融市场的风险度量与回测[J]. 中国科学技术大学学报, 2020, 50(5): 654-668.
[5]	朱巧慧, 梁启鹏, 康宇, 赵云波. 无界DoS攻击下网络控制系统的多路径切换保护[J]. 中国科学技术大学学报, 2021, 51(1): 22-32.
[6]	叶五一, 刘伟博. PWY泡沫检验方法的修正研究及实证分析[J]. 中国科学技术大学学报, 2021, 51(1): 43-52.
[7]	沈迪, 蒋勇, 祝现礼, 李梦婕. 基于CoKriging模型的单室火灾温度预测[J]. 中国科学技术大学学报, 2021, 51(1): 75-86.