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

Nitrogen reduction reaction on small iron clusters supported by N-doped graphene: A theoretical study of the atomically precise active-site mechanism

Chaonan Cui1,2, Hongchao Zhang1,2, Zhixun Luo1,2( )
Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
University of Chinese Academy of Sciences, Beijing 100049, China
Show Author Information

Graphical Abstract

Abstract

Nonprecious metal catalysts are known of significance for electrochemical N2 reduction reaction (NRR) of which the mechanism has been illustrated by ongoing investigations of single atom catalysis. However, it remains challenging to fully understand the size-dependent synergistic effect of active sites inherited in substantial nanocatalysts. In this work, four types of small iron clusters Fen (n = 1-4) supported on nitrogen-doped graphene sheets are constructed to figure out the size dependence and synergistic effect of active sites for NRR catalytic activities. It is revealed that Fe3 and Fe4 clusters on N4G supports exhibit higher NRR activity than single-iron atom and iron dimer clusters, showing lowered limiting potential and restricted hydrogen evolution reaction (HER) which is a competitive reaction channel. In particular, the Fe4-N4G displays outstanding NRR performance for "side-on" adsorption of N2 with a small limiting potential (-0.45 V). Besides the specific structure and strong interface interaction within the Fe4-N4G itself, the high NRR activity is associated with the unique bonding/antibonding orbital interactions of N-N and N-Fe for the adsorptive N2 and NNH intermediates, as well as relatively large charge transfer between N2 and the cluster Fe4-N4G.

Keywords

N2 reduction reaction (NRR)iron clusterscluster catalysisactive-site mechanismdensity functional theory (DFT)

Electronic Supplementary Material

Download File(s)
12274_2020_2847_MOESM1_ESM.pdf (4.8 MB)

References

[1]
Guo, C. X.; Ran, J. R.; Vasileff, A.; Qiao, S. Z. Rational design of electrocatalysts and photo(electro)catalysts for nitrogen reduction to ammonia (NH3) under ambient conditions. Energy Environ. Sci. 2018, 11, 45-56.
Crossref Google Scholar
[2]
Ashida, Y.; Arashiba, K.; Nakajima, K.; Nishibayashi, Y. Molybdenum-catalysed ammonia production with samarium diiodide and alcohols or water. Nature 2019, 568, 536-540.
Crossref Google Scholar
[3]
Nagaoka, K.; Eboshi, T.; Takeishi, Y.; Tasaki, R.; Honda, K.; Imamura, K.; Sato, K. Carbon-free H2 production from ammonia triggered at room temperature with an acidic RuO2/γ-Al2O3 catalyst. Sci. Adv. 2017, 3, e1602747.
Crossref Google Scholar
[4]
Wang, L.; Xia, M. K.; Wang, H.; Huang, K. F.; Qian, C. X.; Maravelias, C. T.; Ozin, G. A. Greening ammonia toward the solar ammonia refinery. Joule 2018, 2, 1055-1074.
Crossref Google Scholar
[5]
Bhutto, S. M.; Holland, P. L. Dinitrogen activation and functionalization using β-diketiminate iron complexes. Eur. J. Inorg. Chem. 2019, 2019, 1861-1869.
Crossref Google Scholar
[6]
Gong, Y. T.; Wu, J. Z.; Kitano, M.; Wang, J. J.; Ye, T. N.; Li, J.; Kobayashi, Y.; Kishida, K.; Abe, H.; Niwa, Y. et al. Ternary intermetallic LaCoSi as a catalyst for N2 activation. Nat. Catal. 2018, 1, 178-185.
Crossref Google Scholar
[7]
Kobayashi, Y.; Tang, Y.; Kageyama, T.; Yamashita, H.; Masuda, N.; Hosokawa, S.; Kageyama, H. Titanium-based hydrides as heterogeneous catalysts for ammonia synthesis. J. Am. Chem. Soc. 2017, 139, 18240-18246.
Crossref Google Scholar
[8]
Jia, H. L.; Du, A. X.; Zhang, H.; Yang, J. H.; Jiang, R. B.; Wang, J. F.; Zhang, C. Y. Site-selective growth of crystalline ceria with oxygen vacancies on gold nanocrystals for near-infrared nitrogen photofixation. J. Am. Chem. Soc. 2019, 141, 5083-5086.
Crossref Google Scholar
[9]
Shi, M. M.; Bao, D.; Wulan, B. R.; Li, Y. H.; Zhang, Y. F.; Yan, J. M.; Jiang, Q. Au sub-nanoclusters on TiO2 toward highly efficient and selective electrocatalyst for N2 conversion to NH3 at ambient conditions. Adv. Mater. 2017, 29, 1606550.
Crossref Google Scholar
[10]
Cui, X. Y.; Tang, C.; Zhang, Q. A review of electrocatalytic reduction of dinitrogen to ammonia under ambient conditions. Adv. Energy Mater. 2018, 8, 1800369.
Crossref Google Scholar
[11]
Xue, X. L.; Chen, R. P.; Yan, C. Z.; Zhao, P. Y.; Hu, Y.; Zhang, W. J.; Yang, S. Y.; Jin, Z. Review on photocatalytic and electrocatalytic artificial nitrogen fixation for ammonia synthesis at mild conditions: Advances, challenges and perspectives. Nano Res. 2019, 12, 1229-1249.
Crossref Google Scholar
[12]
Wang, F.; Ma, J. Z.; He, G. Z.; Chen, M.; Zhang, C. B.; He, H. Nanosize effect of Al2O3 in Ag/Al2O3 catalyst for the selective catalytic oxidation of ammonia. ACS Catal. 2018, 8, 2670-2682.
Crossref Google Scholar
[13]
Tsuji, Y.; Ogasawara, K.; Kitano, M.; Kishida, K.; Abe, H.; Niwa, Y.; Yokoyama, T.; Hara, M.; Hosono, H. Control of nitrogen activation ability by Co-Mo bimetallic nanoparticle catalysts prepared via sodium naphthalenide-reduction. J. Catal. 2018, 364, 31-39.
Crossref Google Scholar
[14]
Wang, A. Q.; Li, J.; Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2018, 2, 65-81.
Crossref Google Scholar
[15]
Zheng, S. S.; Li, S. N.; Mei, Z. W.; Hu, Z. X.; Chu, M. H.; Liu, J. H.; Chen, X.; Pan, F. Electrochemical nitrogen reduction reaction performance of single-boron catalysts tuned by MXene substrates. J. Phys. Chem. Lett. 2019, 10, 6984-6989.
Crossref Google Scholar
[16]
Zang, W. J.; Yang, T.; Zou, H. Y.; Xi, S. B.; Zhang, H.; Liu, X. M.; Kou, Z. K.; Du, Y. H.; Feng, Y. P.; Shen, L. et al. Copper single atoms anchored in porous nitrogen-doped carbon as efficient pH-universal catalysts for the nitrogen reduction reaction. ACS Catal. 2019, 9, 10166-10173.
Crossref Google Scholar
[17]
He, C.; Wu, Z. Y.; Zhao, L.; Ming, M.; Zhang, Y.; Yi, Y. P.; Hu, J. S. Identification of FeN4 as an efficient active site for electrochemical N2 reduction. ACS Catal. 2019, 9, 7311-7317.
Crossref Google Scholar
[18]
Li, X. F.; Li, Q. K.; Cheng, J.; Liu, L. L.; Yan, Q.; Wu, Y. C.; Zhang, X. H.; Wang, Z. Y.; Qiu, Q.; Luo, Y. Conversion of dinitrogen to ammonia by FeN3-embedded graphene. J. Am. Chem. Soc. 2016, 138, 8706-8709.
Crossref Google Scholar
[19]
Wang, Y.; Cui, X. Q.; Zhao, J. X.; Jia, G. R.; Gu, L.; Zhang, Q. H.; Meng, L. K.; Shi, Z.; Zheng, L. R.; Wang, C. Y. et al. Rational design of Fe-N/C hybrid for enhanced nitrogen reduction electrocatalysis under ambient conditions in aqueous solution. ACS Catal. 2019, 9, 336-344.
Crossref Google Scholar
[20]
Lü, F.; Zhao, S. Z.; Guo, R. J.; He, J.; Peng, X. Y.; Bao, H. H.; Fu, J. T.; Han, L. L.; Qi, G. C.; Luo, J. et al. Nitrogen-coordinated single Fe sites for efficient electrocatalytic N2 fixation in neutral media. Nano Energy 2019, 61, 420-427.
Crossref Google Scholar
[21]
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
[22]
Wei, Z. X.; Zhang, Y. F.; Wang, S. Y.; Wang, C. Y.; Ma, J. M. Fe-doped phosphorene for the nitrogen reduction reaction. J. Mater. Chem. A 2018, 6, 13790-13796.
Crossref Google Scholar
[23]
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
[24]
Georgakilas, V.; Tiwari, J. N.; Kemp, K. C.; Perman, J. A.; Bourlinos, A. B.; Kim, K. S.; Zboril, R. Noncovalent functionalization of graphene and graphene oxide for energy materials, biosensing, catalytic, and biomedical applications. Chem. Rev. 2016, 116, 5464-5519.
Crossref Google Scholar
[25]
Tyo, E. C.; Vajda, S. Catalysis by clusters with precise numbers of atoms. Nat. Nanotechnol. 2015, 10, 577-588.
Crossref Google Scholar
[26]
Cui, C. N.; Luo, Z. X.; Yao, J. N. Enhanced catalysis of Pt3 clusters supported on graphene for N-H bond dissociation. CCS Chem. 2019, 1, 215-225.
Crossref Google Scholar
[27]
An, J. H.; Wang, Y. H.; Lu, J. M.; Zhang, J.; Zhang, Z. X.; Xu, S. T.; Liu, X. Y.; Zhang, T.; Gocyla, M.; Heggen, M. et al. Acid-promoter-free ethylene methoxycarbonylation over Ru-clusters/ceria: The catalysis of interfacial lewis acid-base pair. J. Am. Chem. Soc. 2018, 140, 4172-4181.
Crossref Google Scholar
[28]
Ren, Y.; Yang, Y.; Zhao, Y. X.; He, S. G. Size-dependent reactivity of rhodium cluster anions toward methane. J. Phys. Chem. C 2019, 123, 17035-17042.
Crossref Google Scholar
[29]
Yang, B.; Liu, C.; Halder, A.; Tyo, E. C.; Martinson, A. B. F.; Seifer, S.; Zapol, P.; Curtiss, L. A.; Vajda, S. Copper cluster size effect in methanol synthesis from CO2. J. Phys. Chem. C 2017, 121, 10406-10412.
Crossref Google Scholar
[30]
Kong, J. M.; Lim, A.; Yoon, C.; Jang, J. H.; Ham, H. C.; Han, J.; Nam, S.; Kim, D.; Sung, Y. E.; Choi, J. et al. Electrochemical synthesis of NH3 at low temperature and atmospheric pressure using a γ-Fe2O3 catalyst. ACS Sustainable Chem. Eng. 2017, 5, 10986-10995.
Crossref Google Scholar
[31]
Manjunatha, R.; Karajić, A.; Goldstein, V.; Schechter, A. Electrochemical ammonia generation directly from nitrogen and air using an iron-oxide/titania-based catalyst at ambient conditions. ACS Appl. Mater. Interfaces 2019, 11, 7981-7989.
Crossref Google Scholar
[32]
Xia, L.; Li, B. H.; Zhang, Y.; Zhang, R.; Ji, L.; Chen, H. Y.; Cui, G. W.; Zheng, H. G.; Sun, X. P.; Xie, F. Y. et al. Cr2O3 nanoparticle-reduced graphene oxide hybrid: A highly active electrocatalyst for N2 reduction at ambient conditions. Inorg. Chem. 2019, 58, 2257-2260.
Crossref Google Scholar
[33]
Chen, G. F.; Ren, S. Y.; Zhang, L. L.; Cheng, H.; Luo, Y. R.; Zhu, K. H.; Ding, L. X.; Wang, H. H. Advances in electrocatalytic N2 reduction- strategies to tackle the selectivity challenge. Small Methods 2019, 3, 1800337.
Crossref Google Scholar
[34]
Li, S. J.; Bao, D.; Shi, M. M.; Wulan, B. R.; Yan, J. M.; Jiang, Q. Amorphizing of Au nanoparticles by CeOx-RGO hybrid support towards highly efficient electrocatalyst for N2 reduction under ambient conditions. Adv. Mater. 2017, 29, 1700001.
Crossref Google Scholar
[35]
Nazemi, M.; El-Sayed, M. A. Electrochemical synthesis of ammonia from N2 and H2O under ambient conditions using pore-size-controlled hollow gold nanocatalysts with tunable plasmonic properties. J. Phys. Chem. Lett. 2018, 9, 5160-5166.
Crossref Google Scholar
[36]
Chen, S. M.; Perathoner, S.; Ampelli, C.; Mebrahtu, C.; Su, D. S.; Centi, G. Electrocatalytic synthesis of ammonia at room temperature and atmospheric pressure from water and nitrogen on a carbon-nanotube-based electrocatalyst. Angew. Chem., Int. Ed. 2017, 56, 2699-2703.
Crossref Google Scholar
[37]
Yao, Y.; Zhu, S. Q.; Wang, H. J.; Li, H.; Shao, M. H. A spectroscopic study on the nitrogen electrochemical reduction reaction on gold and platinum surfaces. J. Am. Chem. Soc. 2018, 140, 1496-1501.
Crossref Google Scholar
[38]
Zhao, S. L.; Lu, X. Y.; Wang, L. Z.; Gale, J.; Amal, R. Carbon-based metal-free catalysts for electrocatalytic reduction of nitrogen for synthesis of ammonia at ambient conditions. Adv. Mater. 2019, 31, 1805367.
Crossref Google Scholar
[39]
Tanaka, H.; Nishibayashi, Y.; Yoshizawa, K. Interplay between theory and experiment for ammonia synthesis catalyzed by transition metal complexes. Acc. Chem. Res. 2016, 49, 987-995.
Crossref Google Scholar
[40]
Licht, S.; Cui, B. C.; Wang, B. H.; Li, F. F.; Lau, J.; Liu, S. Z. Ammonia synthesis by N2 and steam electrolysis in molten hydroxide suspensions of nanoscale Fe2O3. Science 2014, 345, 637-640.
Crossref Google Scholar
[41]
Kosaka, F.; Nakamura, T.; Oikawa, A.; Otomo, J. Electrochemical acceleration of ammonia synthesis on Fe-based alkali-promoted electrocatalyst with proton conducting solid electrolyte. ACS Sustainable Chem. Eng. 2017, 5, 10439-10446.
Crossref Google Scholar
[42]
Hu, L.; Khaniya, A.; Wang, J.; Chen, G.; Kaden, W. E.; Feng, X. F. Ambient electrochemical ammonia synthesis with high selectivity on Fe/Fe oxide catalyst. ACS Catal. 2018, 8, 9312-9319.
Crossref Google Scholar
[43]
Qian, J.; An, Q.; Fortunelli, A.; Nielsen, R. J.; Goddard III, W. A. Reaction mechanism and kinetics for ammonia synthesis on the Fe(111) surface. J. Am. Chem. Soc. 2018, 140, 6288-6297.
Crossref Google Scholar
[44]
Li, C.; Fu, Y. S.; Wu, Z.; Xia, J. W.; Wang, X. Sandwich-like reduced graphene oxide/yolk-shell-structured Fe@Fe3O4/carbonized paper as an efficient freestanding electrode for electrochemical synthesis of ammonia directly from H2O and nitrogen. Nanoscale 2019, 11, 12997-13006.
Crossref Google Scholar
[45]
Maheshwari, S.; Rostamikia, G.; Janik, M. J. Elementary kinetics of nitrogen electroreduction on Fe surfaces. J. Chem. Phys. 2019, 150, 041708.
Crossref Google Scholar
[46]
Mou, X. L.; Zhang, B. S.; Li, Y.; Yao, L. D.; Wei, X. J.; Su, D. S.; Shen, W. J. Rod-shaped Fe2O3 as an efficient catalyst for the selective reduction of nitrogen oxide by ammonia. Angew. Chem., Int. Ed. 2012, 51, 2989-2993.
Crossref Google Scholar
[47]
Zhang, L. F.; Zhao, W. H.; Zhang, W. H.; Chen, J.; Hu, Z. P. gt-C3N4 coordinated single atom as an efficient electrocatalyst for nitrogen reduction reaction. Nano Res. 2019, 12, 1181-1186.
Crossref Google Scholar
[48]
Yang, L. M.; Yi, G. P.; Hou, Y. N.; Cheng, H. Y.; Luo, X. B.; Pavlostathis, S. G.; Luo, S. L.; Wang, A. J. Building electrode with three-dimensional macroporous interface from biocompatible polypyrrole and conductive graphene nanosheets to achieve highly efficient microbial electrocatalysis. Biosens. Bioelectron. 2019, 141, 111444.
Crossref Google Scholar
[49]
Luo, Z. X.; Castleman, A. W. Jr.; Khanna, S. N. Reactivity of metal clusters. Chem. Rev. 2016, 116, 14456-14492.
Crossref Google Scholar
[50]
Luo, Z. X.; Castleman, A. W. Special and general superatoms. Acc. Chem. Res. 2014, 47, 2931-2940.
Crossref Google Scholar
[51]
Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169-11186.
Crossref Google Scholar
[52]
Wang, R. B.; Hellman, A. Hybrid functional study of the electro-oxidation of water on pristine and defective hematite (0001). J. Phys. Chem. C 2019, 123, 2820-2827.
Crossref Google Scholar
[53]
Rohling, R. Y.; Tranca, I. C.; Hensen, E. J. M.; Pidko, E. A. Correlations between density-based bond orders and orbital-based bond energies for chemical bonding analysis. J. Phys. Chem. C 2019, 123, 2843-2854.
Crossref Google Scholar
[54]
Maintz, S.; Deringer, V. L.; Tchougreeff, A. L.; Dronskowski, R. LOBSTER: A tool to extract chemical bonding from plane-wave based DFT. J. Comput. Chem. 2016, 37, 1030-1035.
Crossref Google Scholar
[55]
Maintz, S.; Deringer, V. L.; Tchougréeff, A. L.; Dronskowski, R. Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids. J. Comput. Chem. 2013, 34, 2557-2567.
Crossref Google Scholar
[56]
Malko, D.; Kucernak, A.; Lopes, T. In situ electrochemical quantification of active sites in Fe-N/C non-precious metal catalysts. Nat. Commun. 2016, 7, 13285.
Crossref Google Scholar
[57]
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
[58]
Cui, C. N.; Han, J. Y.; Zhu, X. L.; Liu, X.; Wang, H.; Mei, D. H.; Ge, Q. F. Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode. J. Catal. 2016, 343, 257-265.
Crossref Google Scholar
[59]
Psofogiannakis, G.; St-Amant, A.; Ternan, M. Methane oxidation mechanism on Pt(111): A cluster model DFT study. J. Phys. Chem. B 2006, 110, 24593-24605.
Crossref Google Scholar
[60]
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
[61]
Liu, J. C.; Ma, X. L.; Li, Y.; Wang, Y. G.; Xiao, H.; Li, J. Heterogeneous Fe3 single-cluster catalyst for ammonia synthesis via an associative mechanism. Nat. Commun. 2018, 9, 1610.
Crossref Google Scholar
[62]
McWilliams, S. F.; Holland, P. L. Dinitrogen binding and cleavage by multinuclear iron complexes. Acc. Chem. Res. 2015, 48, 2059-2065.
Crossref Google Scholar
[63]
Hoffman, B. M.; Lukoyanov, D.; Yang, Z. Y.; Dean, D. R.; Seefeldt, L. C. Mechanism of nitrogen fixation by nitrogenase: The next stage. Chem. Rev. 2014, 114, 4041-4062.
Crossref Google Scholar
[64]
Liu, C. W.; Li, Q. Y.; Wu, C. Z.; Zhang, J.; Jin, Y. G.; MacFarlane, D. R.; Sun, C. H. Single-boron catalysts for nitrogen reduction reaction. J. Am. Chem. Soc. 2019, 141, 2884-2888.
Crossref Google Scholar
[65]
Lu, Z. Y.; Chen, G. X.; Siahrostami, S.; Chen, Z. H.; Liu, K.; Xie, J.; Liao, L.; Wu, T.; Lin, D. C.; Liu, Y. Y. et al. High-efficiency oxygen reduction to hydrogen peroxide catalysed by oxidized carbon materials. Nat. Catal. 2018, 1, 156-162.
Crossref Google Scholar
[66]
Liu, H. N.; Li, W.; Liu, F.; Pei, Z. Z.; Shi, J.; Wang, Z. J.; He, D. H.; Chen, Y. Homogeneous, heterogeneous, and biological catalysts for electrochemical N2 reduction toward NH3 under ambient conditions. ACS Catal. 2019, 9, 5245-5267.
Crossref Google Scholar
[67]
Van Der Ham, C. J. M.; Koper, M. T.; Hetterscheid, D. G. H. Challenges in reduction of dinitrogen by proton and electron transfer. Chem. Soc. Rev. 2014, 43, 5183-5191.
Crossref Google Scholar
[68]
Skúlason, E.; Bligaard, T.; Gudmundsdóttir, S.; Studt, F.; Rossmeisl, J.; Abild-Pedersen, F.; Vegge, T.; Jónsson, H.; Nørskov, J. K. A theoretical evaluation of possible transition metal electro-catalysts for N2 reduction. Phys. Chem. Chem. Phys. 2012, 14, 1235-1245.
Crossref Google Scholar
[69]
Wang, H. W.; Gu, X. K.; Zheng, X. S.; Pan, H. B.; Zhu, J. F.; Chen, S.; Cao, L. N.; Li, W. X.; Lu, J. L. Disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity. Sci. Adv. 2019, 5, eaat6413.
Crossref Google Scholar
[70]
Ma, X. L.; Liu, J. C.; Xiao, H.; Li, J. Surface single-cluster catalyst for N2-to-NH3 thermal conversion. J. Am. Chem. Soc. 2018, 140, 46-49.
Crossref Google Scholar
[71]
Ling, C. Y.; Bai, X. W.; Ouyang, Y. X.; Du, A. J.; Wang, J. L. Single molybdenum atom anchored on N-doped carbon as a promising electrocatalyst for nitrogen reduction into ammonia at ambient conditions. J. Phys. Chem. C 2018, 122, 16842-16847.
Crossref Google Scholar
[72]
Deringer, V. L.; Tchougreeff, A. L.; Dronskowski, R. Crystal orbital Hamilton population (COHP) analysis as projected from plane-wave basis sets. J. Phys. Chem. A 2011, 115, 5461-5466.
Crossref Google Scholar
[73]
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.
Crossref Google Scholar
[74]
Hao, Y. C.; Guo, Y.; Chen, L. W.; Shu, M.; Wang, X. Y.; Bu, T. A.; Gao, W. Y.; Zhang, N.; Su, X.; Feng, X. et al. Promoting nitrogen electroreduction to ammonia with bismuth nanocrystals and potassium cations in water. Nat. Catal. 2019, 2, 448-456.
Crossref Google Scholar
[75]
Bickelhaupt, F. M.; Nagle, J. K.; Klemm, W. L. Role of s-p orbital mixing in the bonding and properties of second-period diatomic molecules. J. Phys. Chem. A 2008, 112, 2437-2446.
Crossref Google Scholar
Nano Research
Volume 13 Issue 8,
August 2020
Pages 2280-2288
DOI: 10.1007/s12274-020-2847-0
Cite this article:
Cui C, Zhang H, Luo Z. Nitrogen reduction reaction on small iron clusters supported by N-doped graphene: A theoretical study of the atomically precise active-site mechanism. Nano Research, 2020, 13(8): 2280-2288. https://doi.org/10.1007/s12274-020-2847-0
Topics:
Catalyst activityCharge transferDoping (additives)GrapheneHydrogen evolution reaction IronIron compoundsNanocatalystsNitrogen

888

Views

69

Crossref

N/A

Web of Science

67

Scopus

0

CSCD

Altmetrics
Received: 13 February 2020
Revised: 31 March 2020
Accepted: 30 April 2020
Published: 05 August 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
Return