二维AuP2材料电催化固氮性能的理论研究

doi:10.11949/0438-1157.20200714

摘要/Abstract

摘要：

通过电化学反应将氮气（N₂）和水（H₂O）在常温常压的条件下转化为氨气（NH₃）是一种绿色环保的合成氨方法。但由于N₂具有非常高的化学惰性，必须借助电催化剂来加速反应的动力学过程。通过密度泛函理论计算揭示出新型二维无机材料AuP₂对N₂电化学还原制NH₃具有很好的催化活性。在二维AuP₂材料中，Au与P之间由于电负性差异发生显著的电荷转移，使带有正电荷的P可作为活性位点促进氮还原。计算表明整个反应的速控步是N₂生成^*NNH的过程，限制电压为1.2 V，催化活性可以跟部分金属催化剂相媲美。为设计高效氮还原电催化剂提供了新的思路。

关键词: 二维材料, AuP₂, 电催化, 氮还原, 密度泛函理论计算

Abstract:

The electrochemical conversion of nitrogen (N₂) and water (H₂O) into ammonia (NH₃) under normal temperature and pressure conditions is a green and environmentally friendly method of ammonia synthesis. However, because N₂ has a very high chemical inertness, an electrocatalyst must be used to accelerate the kinetic process of the reaction. In this paper, we use density functional theory calculations to reveal that AuP₂, a new type of two-dimensional inorganic material, has good catalytic activity for the electrochemical reduction of N₂ to NH₃. In the two-dimensional AuP₂ material, significant charge transfer occurs between Au and P atoms due to the difference in electronegativity, so that positively charged P can be used as an active site to promote nitrogen reduction. Our calculations show that the rate-determining step of the entire reaction is the process of generating ^*NNH from N₂ with a limiting voltage of 1.2 V, and the catalytic activity can be comparable to some metal catalysts. This work provides new ideas for the design of high-efficiency nitrogen reduction electrocatalysts.

Key words: two-dimensional materials, AuP₂, electrocatalysis, nitrogen reduction reaction, density functional theory calculations

中图分类号:

O 643.36

朱晓蓉, 李亚飞. 二维AuP₂材料电催化固氮性能的理论研究[J]. 化工学报, 2020, 71(10): 4820-4825.

Xiaorong ZHU, Yafei LI. Theoretical study on electrocatalytic nitrogen fixation performance of two-dimensional AuP₂[J]. CIESC Journal, 2020, 71(10): 4820-4825.

图/表 5

图1 二维AuP2材料的俯视(a)与侧视(b)图

Fig.1 Top (a) and side (b) views of two-dimensional (2D) AuP2

图2 二维AuP2材料的声子谱(a)与分子动力学模拟结果(b)

Fig.2 Phonon spectrum (a) and the results of MD simulations (b) of 2D AuP2

图3 二维AuP2材料的能带结构(a)与电子态密度(b)

Fig.3 Band structure (a) and density of states (DOS) (b) of 2D AuP2

图4 二维AuP2材料上电化学氮还原的中间体几何结构[(a)~(e)]与自由能变化曲线(f)

Fig.4 Views of intermediates [(a)—(e)] and free energy diagrams (f) of NRR on 2D AuP2

图5 二维AuP2结构表面吸附N2后的总态密度以及Ⅰ型P原子各个轨道的态密度贡献

Fig.5 Total density of state of two-dimensional AuP2 and partial density of state of different orbitals in Ⅰ type P

参考文献 36

1	Deng J, Iñiguez J A, Liu C. Electrocatalytic nitrogen reduction at low temperature[J]. Joule, 2012, 2(5): 846-856.
2	Rosca V, Duca M, de Groot M T, et al. Nitrogen cycle electrocatalysis[J]. Chemical Reviews, 2009, 109(6):2209-2244.
3	Shipman M A, Symes M D. Recent progress towards the electrosynthesis of ammonia from sustainable resources[J]. Catalysis Today, 2017, 286: 57-68.
4	Foster S L, Bakovic S I P, Duda R D, et al. Catalysts for nitrogen reduction to ammonia[J]. Nature Catalysis, 2018, 1(7): 490-500.
5	Suryanto B H R, Du H L, Wang D B, et al. Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia[J]. Nature Catalysis, 2019, 2(4): 290-296.
6	Guo C X, Ran J R, Vasileff A, et al. Rational design of electrocatalysts and photo(electro)catalysts for nitrogen reduction to ammonia (NH₃) under ambient conditions[J]. Energy and Environmental Science, 2018, 11(1): 45-56.
7	Jia H P, Quadrelli E A. Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen[J]. Chemical Society Reviews, 2014, 43(2): 547-564.
8	Egill S, Thomas B, Sigrídur G, et al. A theoretical evaluation of possible transition metal electro-catalysts for N₂ reduction[J]. Physical Chemistry Chemical Physics, 2011, 14(3): 1235-1245.
9	Wang Y, Li Y F. PtTe monolayer: two-dimensional electrocatalyst with high basal plane activity toward oxygen reduction reaction[J]. Journal of the American Chemical Society, 2018, 40(140): 12732-12735
10	Deng D H, Novoselov K S, Fu Q, et al. Catalysis with two-dimensional materials and their heterostructures[J]. Nature Nanotechnology, 2016, 11(3): 218-230.
11	Sun Y F, Gao S, Lei F C, et al. Atomically-thin two-dimensional sheets for understanding active sites in catalysis[J]. Chemical Society Reviews, 2015, 44(3): 623-636.
12	Hong X, Chan K, Tsai C, et al. How doped MoS₂ breaks transition-metal scaling relations for CO₂ electrochemical reduction[J]. ACS Catalysis, 2016, 6(7): 4428-4437.
13	Chou S S, Sai N, Lu P, et al. Understanding catalysis in a multiphasic two-dimensional transition metal dichalcogenide[J]. Nature Communications, 2015, 6(10): 8311-8311.
14	Gong Q F, Ding P, Xu M Q, et al. Structural defects on converted bismuth oxide nanotubes enable highly active electrocatalysis of carbon dioxide reduction[J]. Nature Communications, 2019, 10(1): 2807.
15	Li L Q, Tang C, Xia B Q, et al. Two-dimensional mosaic bismuth nanosheets for highly selective ambient electrocatalytic nitrogen reduction[J]. ACS Catalysis, 2019, 9(4): 2902-2908.
16	Li X H, Li T S, Ma Y J, et al. Boosted electrocatalytic N₂ reduction to NH₃ by defect‐rich MoS₂ nanoflower[J]. Advanced Energy Materials, 2018, 8(30):1801357.
17	Shi M M, Bao D, Li S J, et al. Anchoring PdCu amorphous nanocluster on graphene for electrochemical reduction of N₂ to NH₃ under ambient conditions in aqueous solution[J]. Advanced Energy Materials, 2018, 8(21):1800124.
18	Du Y Q, Jiang C, Xia W, et al. Electrocatalytic reduction of N₂ and nitrogen-incorporation process on dopant-free defect graphene[J]. Journal of Materials Chemistry A, 2020, 8(1): 55-61.
19	Yu X, Han P, Wei Z, et al. Boron-doped graphene for electrocatalytic N₂ reduction[J]. Joule, 2018, 2(8): 1610-1622.
20	He T W, Matta S K, Du A, et al. Single tungsten atom supported on N-doped graphyne as a high-performance electrocatalyst for nitrogen fixation under ambient conditions[J]. Physical Chemistry Chemical Physics, 2019, 21(3): 1546-1551.
21	Zhao J X, Chen Z F. Single Mo atom supported on defective boron nitride monolayer as an efficient electrocatalyst for nitrogen fixation: a computational study[J]. Journal of the American Chemical Society, 2017, 139(36): 12480-12487.
22	Abel M, Clair S, Ourdjini O, et al. Single layer of polymeric Fe-phthalocyanine: an organometallic sheet on metal and thin insulating film[J]. Journal of the American Chemical Society, 2011, 133(5): 1203-1205.
23	Kambe T, Sakamoto R, Hoshiko K, et al. π-conjugated nickel bis(dithiolene) complex nanosheet[J]. Journal of the American Chemical Society, 2013, 135(7): 2462-2465.
24	Song Q L, Jiang S, Hasell T, et al. Porous organic cage thin films and molecular-sieving membranes[J]. Advanced Materials, 2016, 28(13):2629-2637.
25	Xu G Y, Nie P, Dou H, et al. Exploring metal organic frameworks for energy storage in batteries and supercapacitors[J]. Materials Today, 2017, 20(4): 191-209.
26	Wu S, Min H, Shi W, et al. Multicenter metal–organic framework‐based ratiometric fluorescent sensors[J]. Advanced Materials, 2020, 32(3):1805871.
27	Zhu L, Liu X, Jiang H, et al. Metal–organic frameworks for heterogeneous basic catalysis[J]. Chemical Reviews, 2017, 117(12): 8129-8176.
28	Tian H, Zhang J Q, Ho W K, et al. Two-dimensional metal-phosphorus network[J]. Matter, 2020, 2(1):111-118.
29	Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[J]. Physical Review B, 1996, 54(16):11169-11186.
30	Blöchl P E. Projector augmented-wave method[J]. Physical Review B, 1994, 50(24):17953-17979.
31	Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple[J]. Physical Review Letters, 1996, 77(18): 3865-3868.
32	Baroni S, de Gironcoli S, Dal Corso A, et al. Phonons and related crystal properties from density-functional perturbation theory[J]. Reviews of Modern Physics, 2001, 73(2): 515-562.
33	Nørskov J K, Rossmeisl J, Logadottir A A, et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode[J]. Journal of Physical Chemistry B, 2004, 108(46): 17886-17892.
34	Grimme S. Semiempirical GGA-type density functional constructed with a long‐range dispersion correction[J]. Journal of Computational Chemistry, 2006, 27(15): 1787-1799.
35	Mathew K, Sundararaman R, Letchworthweaver K, et al. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways[J]. Journal of Chemical Physics, 2014, 140(8): 084106.
36	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[J]. ChemSusChem, 2015, 8(13): 2180-2186.

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二维AuP₂材料电催化固氮性能的理论研究

Theoretical study on electrocatalytic nitrogen fixation performance of two-dimensional AuP₂

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