The Adsorption of NH₃ on the FeS₂ (100) Surface: A First-Principles Investigation

Abstract:

Using first-principles calculations, we have investigated the adsorption of NH_x (x =1, 2 or 3) on the FeS₂ (100) surface. The adsorption configurations and adsorption energies were determined. Our calculations showed that the NH_x prefers to adsorb on the surface Fe site via N atom. The NH molecule displays the strongest interaction with the FeS₂ (100) surface among the three adsorbates, while NH₃ is bound relatively weak to the surface. The analysis of the density of states (DOS) showed a strong hybridization between N 2p and Fe 3d states, especially for NH and NH₂ adsorption. The NH₃ adsorption at full coverage was found to be less favoured than at partial coverage because of the steric repulsion among the adsorbates, in agreement with the experiment.

• Periodical: Materials Science Forum (Volume 1001)
• Pages: 22-27
• DOI: https://doi.org/10.4028/www.scientific.net/MSF.1001.22
• Online since: July 2020
• Authors: Chong Liang, Xin Lu Liu, Li Che*, Kun Yang
• Keywords: Adsorption, FeS₂ (100), Spatial Absorption

References

[1] D. Rickard, G.W. Luther, Chemistry of iron sulfides, Chem. Rev. 107 (2007) 514-562.

DOI: 10.1021/cr0503658

[2] R. Hu, H. Zhao, J. Zhang, Q. Liang, Y. Wang, B. Guo, R. Dangol, Y. Zheng, Q. Yan, J. Zhu, Scalable synthesis of a foam-like FeS2 nanostructure by a solution combustion–sulfurization process for high-capacity sodium-ion batteries, Nanoscale 11 (2019) 178-184.

DOI: 10.1039/c8nr06675b

[3] J. Puthussery, S. Seefeld, N. Berry, M. Gibbs, M. Law, Colloidal iron pyrite (FeS2) nanocrystal inks for thin-film photovoltaics, J. Am. Chem. Soc. 133 (2011) 716-719.

DOI: 10.1021/ja1096368

[4] X.Y. Chen, Z.H. Wang, X. Wang, J.X. Wan, J.W. Liu, Y.T. Qian, Single-source approach to cubic FeS2 crystallites and their optical and electrochemical properties, Inorg. Chem. 44 (2005) 951-954.

DOI: 10.1021/ic049049m

[5] R. Murphy, D.R. Strongin, Surface reactivity of pyrite and related sulfides, Surf. Sci. Rep. 64 (2009) 1-45.

[6] C. Morales, E. Flores, S. Yoda, M.A. Nino, D.M.Y. Marero, L. Soriano, J. Rojo, J.R. Ares, I.J. Ferrer, C. Sanchez, An XPS investigation on the influence of the substrate and growth conditions on pyrite thin films surface composition, Appl. Surf. Sci. 492 (2019) 651-660.

DOI: 10.1016/j.apsusc.2019.06.214

[7] K. Andersson, M. Nyberg, H. Ogasawara, D. Nordlund, T. Kendelewicz, C.S. Doyle, G.E. Brown, L.G.M. Pettersson, A. Nilsson, Experimental and theoretical characterization of the structure of defects at the pyrite FeS2 (100) surface, Phys. Rev. B 70 (2004) 195404.

DOI: 10.1103/physrevb.70.195404

[8] Y.N. Zhang, J. Hu, M. Law, R.Q. Wu, Effect of surface stoichiometry on the band gap of the pyrite FeS2 (100) surface, Phys. Rev. B 85 (2012) 085314.

[9] A. Stirling, M. Bernasconi, M. Parrinello, Ab initio simulation of water interaction with the (100) surface of pyrite, J. Chem. Phys. 118 (2003) 8917-8926.

DOI: 10.1063/1.1566936

[10] J. Chen, X. Long, Y. Chen, Comparison of multilayer water adsorption on the hydrophobic galena (PbS) and hydrophilic pyrite (FeS2) surfaces: A DFT Study, J. Phys. Chem. C 118 (2014) 11657-11665.

DOI: 10.1021/jp5000478

[11] M. Sacchi, M.C.E. Galbraith, S.J. Jenkins, The interaction of iron pyrite with oxygen, nitrogen and nitrogen oxides: a first-principles study, Phys. Chem. Chem. Phys. 14 (2012) 3627-3633.

DOI: 10.1039/c2cp23558g

[12] T. Liu, I. Temprano, S.J. Jenkins, D.A. King, S.M. Driver, Low temperature synthesis of NH3 from atomic N and H at the surfaces of FeS2{100} crystals, J. Phys. Chem. C 117 (2013) 10990-10998.

DOI: 10.1021/jp308872y

[13] R. Schlögl, Catalytic Synthesis of Ammonia—A Never-Ending Story",, Angew. Chem. Int. Ed. 42 (2003) 2004-2008.

DOI: 10.1002/anie.200301553

[14] G. Kresse, J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54 (1996) 11169-11186.

DOI: 10.1103/physrevb.54.11169

[15] P.E. Blöchl, Projector augmented-wave method, Phys. Rev. B 50 (1994) 17953-17979.

DOI: 10.1103/physrevb.50.17953

[16] J.P. Perdew, Y. Wang, Accurate and simple analytic representation of the electron-gas correlation energy, Phys. Rev. B 45 (1992) 13244-13249.

DOI: 10.1103/physrevb.45.13244

[17] H.J. Monkhorst, J.D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B 13 (1976) 5188-5192.

DOI: 10.1103/physrevb.13.5188

[18] W. Paszkowicz, J.A. Leiro, Rietveld refinement study of pyrite crystals, J. Alloy. Compd. 401 (2005) 289-295.

DOI: 10.1016/j.jallcom.2005.02.052