AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Single-atom catalysts based on two-dimensional metalloporphyrin monolayers for ammonia synthesis under ambient conditions

Chun-Xiang Huang1,2, Sheng-Yao Lv1,2, Cong Li1, Bin Peng2, Guoliang Li2( ), Li-Ming Yang1( )
Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica; Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education; Hubei Key Laboratory of Materials Chemistry and Service Failure; Hubei Engineering Research Center for Biomaterials and Medical Protective Materials; School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education; Center for Computational Quantum Chemistry, School of Chemistry, South China Normal University, Guangzhou 510006, China
Show Author Information

Graphical Abstract

Four novel metal porphyrin MPP (M = Zr, Nb, Hf and Re) single-atom catalyst candidates with excellent performance for ammonia (NH3) synthesis from electrocatalytic nitrogen reduction reaction (NRR) have been identified through a combination of four-step high-throughput screening and first-principles calculations on a series of 3d, 4d, and 5d transition metals anchored onto porphyrin substrates.

Abstract

We systematically investigated the catalytic performance of 3d, 4d, and 5d transition metals anchored onto two-dimensional extended porphyrin (PP) substrates as nitrogen reduction reaction (NRR) electrocatalysts, employing density functional theory (DFT) calculations and four-step high-throughput screening. Four novel metalloporphyrin (MPP, M = Zr, Nb, Hf, and Re) single-atom catalyst candidates have been identified due to their excellent catalytic performance (low onset potential, high stability, and selectivity). Through comprehensive reaction path search, the maximum Gibbs free energy changes for NRR on the ZrPP (enzymatic-consecutive hybrid path), NbPP (consecutive path), HfPP (enzymatic-consecutive hybrid path), and RePP (distal path) catalysts are 0.38, 0.41, 0.53, and 0.53 eV, respectively. Band structures, projected density of states, and charge/spin distributions show that the high catalytic activity is due to significant orbital hybridizations and charge transfer between N2 and MPP catalysts. We hope our work will promote experimental synthesis of these NRR electrocatalysts and provide new opportunities to the electrochemical conversion of N2 to NH3 under ambient conditions.

Keywords

electrocatalytic nitrogen reduction reactiontwo-dimensional (2D) extended metalloporphyrin (MPP) monolayersingle-atom catalysttwo-dimensional materialshigh-throughput screeningfirst-principles calculations

Electronic Supplementary Material

Download File(s)
12274_2021_4009_MOESM1_ESM.pdf (4.3 MB)

References

1

Zamfirescu, C.; Dincer, I. Using ammonia as a sustainable fuel. J. Power Sources 2008, 185, 459–465.
Crossref Google Scholar
2

Erisman, J. W.; Sutton, M. A.; Galloway, J.; Klimont, Z.; Winiwarter, W. How a century of ammonia synthesis changed the world. Nat. Geosci. 2008, 1, 636–639.
Crossref Google Scholar
3

Galloway, J. N.; Townsend, A. R.; Erisman, J. W.; Bekunda, M.; Cai, Z. C.; Freney, J. R.; Martinelli, L. A.; Seitzinger, S. P.; Sutton, M. A. Transformation of the nitrogen cycle: Recent trends, questions, and potential solutions. Science 2008, 320, 889–892.
Crossref Google Scholar
4

Smil, V. Detonator of the population explosion. Nature 1999, 400, 415.
Crossref Google Scholar
5

Schlögl, R. Catalytic synthesis of ammonia—A “never-ending story”? Angew. Chem., Int. Ed. 2003, 42, 2004–2008.
Crossref Google Scholar
6

Chen, J. G.; Crooks, R. M.; Seefeldt, L. C.; Bren, K. L.; Bullock, R. M.; Darensbourg, M. Y.; Holland, P. L.; Hoffman, B.; Janik, M. J.; Jones, A. K. et al. Beyond fossil fuel-driven nitrogen transformations. Science 2018, 360, eaar6611.
Crossref Google Scholar
7

Pickett, C. J.; Talarmin, J. Electrosynthesis of ammonia. Nature 1985, 317, 652–653.
Crossref Google Scholar
8

Rosca, V.; Duca, M.; de Groot, M. T.; Koper, M. T. M. Nitrogen cycle electrocatalysis. Chem. Rev. 2009, 109, 2209–2244.
Crossref Google Scholar
9

Giddey, S.; Badwal, S. P. S.; Kulkarni, A. Review of electrochemical ammonia production technologies and materials. Int. J. Hydrogen Energy 2013, 38, 14576–14594.
Crossref Google Scholar
10

Zhang, Y.; Du, H. T.; Ma, Y. J.; Ji, L.; Guo, H. R.; Tian, Z. Q.; Chen, H. Y.; Huang, H.; Cui, G. W.; Asiri, A. M. et al. Hexagonal boron nitride nanosheet for effective ambient N2 fixation to NH3. Nano Res. 2019, 12, 919–924.
Crossref Google Scholar
11

Fang, C.; An, W. Single-metal-atom site with high-spin state embedded in defective BN nanosheet promotes electrocatalytic nitrogen reduction. Nano Res. 2021, 14, 4211–4219.
Crossref Google Scholar
12

Nong, W.; Liang, H. K.; Qin, S. H.; Li, Y.; Wang, C. X. Computational design of two-dimensional boron-containing compounds as efficient metal-free electrocatalysts toward nitrogen reduction independent of heteroatom doping. ACS Appl. Mater. Interfaces 2020, 12, 50505–50515.
Crossref Google Scholar
13

Cao, Y. Y.; Gao, Y. J.; Zhou, H.; Chen, X. L.; Hu, H.; Deng, S. W.; Zhong, X.; Zhuang, G. L.; Wang, J. G. Highly efficient ammonia synthesis electrocatalyst: Single Ru atom on naturally nanoporous carbon materials (Adv. Theory Simul. 5/2018). Adv. Theory Simul. 2018, 1, 1870012.
Crossref Google Scholar
14

Yang, T. T.; Tang, S. B.; Li, X. Y.; Sharman, E.; Jiang, J.; Luo, Y. Graphene oxide-supported transition metal catalysts for di-nitrogen reduction. J. Phys. Chem. C 2018, 122, 25441–25446.
Crossref Google Scholar
15

Zhao, W. H.; Zhang, L. F.; Luo, Q. Q.; Hu, Z. P.; Zhang, W. H.; Smith, S.; Yang, J. L. Single Mo1(Cr1) atom on nitrogen-doped graphene enables highly selective electroreduction of nitrogen into ammonia. ACS Catal. 2019, 9, 3419–3425.
Crossref Google Scholar
16

Li, L.; Li, B. H.; Guo, Q. Y.; Li, B. Theoretical screening of single-atom-embedded MoSSe nanosheets for electrocatalytic N2 fixation. J. Phys. Chem. C 2019, 123, 14501–14507.
Crossref Google Scholar
17

Ying, Y. R.; Fan, K.; Luo, X.; Huang, H. T. Predicting two-dimensional pentagonal transition metal monophosphides for efficient electrocatalytic nitrogen reduction. J. Mater. Chem. A 2019, 7, 11444–11451.
Crossref Google Scholar
18

Huang, Y.; Yang, T. T.; Yang, L.; Liu, R.; Zhang, G. Z.; Jiang, J.; Luo, Y.; Lian, P.; Tang, S. B. Graphene-boron nitride hybrid-supported single Mo atom electrocatalysts for efficient nitrogen reduction reaction. J. Mater. Chem. A 2019, 7, 15173–15180.
Crossref Google Scholar
19

Guo, X. Y.; Huang, S. P. Tuning nitrogen reduction reaction activity via controllable Fe magnetic moment: A computational study of single Fe atom supported on defective graphene. Electrochim. Acta 2018, 284, 392–399.
Crossref Google Scholar
20

Ma, B. Y.; Peng, Y.; Ma, D. W.; Deng, Z.; Lu, Z. S. Boron-doped InSe monolayer as a promising electrocatalyst for nitrogen reduction into ammonia at ambient conditions. Appl. Surf. Sci. 2019, 495, 143463.
Crossref Google Scholar
21

Yang, L. M.; Bačić, V.; Popov, I. A.; Boldyrev, A. I.; Heine, T.; Frauenheim, T.; Ganz, E. Two-dimensional Cu2Si monolayer with planar hexacoordinate copper and silicon bonding. J. Am. Chem. Soc. 2015, 137, 2757–2762.
Crossref Google Scholar
22

Song, B. Y.; Zhou, Y.; Yang, H. M.; Liao, J. H.; Yang, L. M.; Yang, X. B.; Ganz, E. Two-dimensional anti-van’t Hoff/Le Bel array AlB6 with high stability, unique motif, triple dirac cones, and superconductivity. J. Am. Chem. Soc. 2019, 141, 3630–3640.
Crossref Google Scholar
23

Yang, L. M.; Popov, I. A.; Frauenheim, T.; Boldyrev, A. I.; Heine, T.; Bačić, V.; Ganz, E. Revealing unusual chemical bonding in planar hyper-coordinate Ni2Ge and quasi-planar Ni2Si two-dimensional crystals. Phys. Chem. Chem. Phys. 2015, 17, 26043–26048.
Crossref Google Scholar
24

Yang, L. M.; Popov, I. A.; Boldyrev, A. I.; Heine, T.; Frauenheim, T.; Ganz, E. Post-anti-van’t Hoff-Le Bel motif in atomically thin germanium-copper alloy film. Phys. Chem. Chem. Phys. 2015, 17, 17545–17551.
Crossref Google Scholar
25

Yang, L. M.; Ganz, E. Adding a new dimension to the chemistry of phosphorus and arsenic. Phys. Chem. Chem. Phys. 2016, 18, 17586–17591.
Crossref Google Scholar
26

Chen, Y. J.; Ji, S. F.; Chen, C.; Peng, Q.; Wang, D. S.; Li, Y. D. Single-atom catalysts: Synthetic strategies and electrochemical applications. Joule 2018, 2, 1242–1264.
Crossref Google Scholar
27

Pan, Y.; Zhang, C.; Liu, Z.; Chen, C.; Li, Y. D. Structural regulation with atomic-level precision: From single-atomic site to diatomic and atomic interface catalysis. Matter 2020, 2, 78–110.
Crossref Google Scholar
28

Wang, A. Q.; Li, J.; Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2018, 2, 65–81.
Crossref Google Scholar
29

Xu, L.; Yang, L. M.; Ganz, E. Electrocatalytic reduction of N2 using metal-doped borophene. ACS Appl. Mater. Interfaces 2021, 13, 14091–14101.
Crossref Google Scholar
30

Ren, C. J.; Jiang, Q. Y.; Lin, W.; Zhang, Y. F.; Huang, S. P.; Ding, K. N. Density functional theory study of single-atom V, Nb, and Ta catalysts on graphene and carbon nitride for selective nitrogen reduction. ACS Appl. Nano Mater. 2020, 3, 5149–5159.
Crossref Google Scholar
31

Maibam, A.; Govindaraja, T.; Selvaraj, K.; Krishnamurty, S. Dinitrogen activation on graphene anchored single atom catalysts: Local site activity or surface phenomena. J. Phys. Chem. C 2019, 123, 27492–27500.
Crossref Google Scholar
32

Liu, X.; Jiao, Y.; Zheng, Y.; Jaroniec, M.; Qiao, S. Z. Building up a picture of the electrocatalytic nitrogen reduction activity of transition metal single-atom catalysts. J. Am. Chem. Soc. 2019, 141, 9664–9672.
Crossref Google Scholar
33

Ma, X. G.; Hu, J. S.; Zheng, M. K.; Li, D.; Lv, H.; He, H.; Huang, C. Y. N2 reduction using single transition-metal atom supported on defective WS2 monolayer as promising catalysts: A DFT study. Appl. Surf. Sci. 2019, 489, 684–692.
Crossref Google Scholar
34

Huang, B.; Li, N.; Ong, W. J.; Zhou, N. G. Single atom-supported MXene: How single-atomic-site catalysts tune the high activity and selectivity of electrochemical nitrogen fixation. J. Mater. Chem. A 2019, 7, 27620–27631.
Crossref Google Scholar
35

Ling, C. Y.; Ouyang, Y. X.; Li, Q.; Bai, X. W.; Mao, X.; Du, A. J.; Wang, J. L. A general two-step strategy-based high-throughput screening of single atom catalysts for nitrogen fixation. Small Methods 2019, 3, 1800376.
Crossref Google Scholar
36

Han, M. M.; Wang, G. Z.; Zhang, H. M.; Zhao, H. J. Theoretical study of single transition metal atom modified MoP as a nitrogen reduction electrocatalyst. Phys. Chem. Chem. Phys. 2019, 21, 5950–5955.
Crossref Google Scholar
37

Zhou, H. Y.; Li, J. C.; Wen, Z.; Jiang, Q. Tuning the catalytic activity of a single Mo atom supported on graphene for nitrogen reduction via Se atom doping. Phys. Chem. Chem. Phys. 2019, 21, 14583–14588.
Crossref Google Scholar
38

Lv, S. Y.; Huang, C. X.; Li, G. L.; Yang, L. M. Electrocatalytic mechanism of N2 reduction reaction by single-atom catalyst rectangular TM-TCNQ monolayers. ACS Appl. Mater. Interfaces 2021, 13, 29641–29653.
Crossref Google Scholar
39

Zhao, M. R.; Song, B. Y.; Yang, L. M. Two-dimensional single-atom catalyst TM3(HAB)2 monolayers for electrocatalytic dinitrogen reduction using hierarchical high-throughput screening. ACS Appl. Mater. Interfaces 2021, 13, 26109–26122.
Crossref Google Scholar
40

Liu, J. H.; Yang, L. M.; Ganz, E. Electrocatalytic reduction of CO2 by two-dimensional transition metal porphyrin sheets. J. Mater. Chem. A 2019, 7, 11944–11952.
Crossref Google Scholar
41

Kresse, G.; Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 1993, 47, 558–561.
Crossref Google Scholar
42

Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758–1775.
Crossref Google Scholar
43

Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132, 154104.
Crossref Google Scholar
44

Perdew, J.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
Crossref Google Scholar
45

Montoya, J. H.; Tsai, C.; Vojvodic, A.; Nørskov, J. K. The challenge of electrochemical ammonia synthesis: A new perspective on the role of nitrogen scaling relations. ChemSusChem 2015, 8, 2180–2186.
Crossref Google Scholar
46

Huang, C. X.; Li, G. L.; Yang, L. M.; Ganz, E. Ammonia synthesis using single-atom catalysts based on two-dimensional organometallic metal phthalocyanine monolayers under ambient conditions. ACS Appl. Mater. Interfaces 2021, 13, 608–621.
Crossref Google Scholar
47

Choi, C.; Back, S.; Kim, N. Y.; Lim, J.; Kim, Y. H.; Jung, Y. Suppression of hydrogen evolution reaction in electrochemical N2 reduction using single-atom catalysts: A computational guideline. ACS Catal. 2018, 8, 7517–7525.
Crossref Google Scholar
48

Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.; Lindqvist, L.; Kitchin, J. R.; Bligaard, T.; Jónsson, H. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 2004, 108, 17886–17892.
Crossref Google Scholar
49
Computational chemistry comparison and benchmark database [Online]. http://cccbdb.nist.gov/. (accessed May 10, 2021).
Nano Research
Volume 15 Issue 5,
May 2022
Pages 4039-4047
DOI: 10.1007/s12274-021-4009-4
Cite this article:
Huang C-X, Lv S-Y, Li C, et al. Single-atom catalysts based on two-dimensional metalloporphyrin monolayers for ammonia synthesis under ambient conditions. Nano Research, 2022, 15(5): 4039-4047. https://doi.org/10.1007/s12274-021-4009-4
Topics:
Biomaterials

1168

Views

70

Crossref

68

Web of Science

70

Scopus

5

CSCD

Altmetrics
Received: 13 May 2021
Revised: 27 October 2021
Accepted: 21 November 2021
Published: 08 February 2022
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
Return