Hydrogen Generation from Methane on FeN3 and FeN4 Embedded Graphene Surface Using DFT Method with Grimme-D3 Dispersion Correction

In this article, the catalytic effect of Nx graphene embedded by Fe metal has been conducted for methane (CH4) decomposition reaction using Density Functional Theory (DFT) calculations with Grimme-D3 dispersion correction. Recently, the catalytic activities of TMNx (x=3→4) graphene surfaces on chemical reactions have attracted a lot of attention. In particular, the activities of graphene surfaces can be increased by different numbers of doped nitrogen atoms on the graphene surface. For analyzing the adsorption mechanism, adsorption energy, BBader charge, charge density difference and the partial density of state have been calculated. CH4molecule is attached into FeN3 embedded graphene physically with higher adsorption energy (-0.41 eV) than that of FeN4 graphene. Their charge transfers from the molecule to the surface are quite small 0.0041e^- for FeN3 and 0.0003 e^- for FeN4 graphene.The decomposition of methane has been calculated using the nudged elastic band method. There are the sequential four steps (CHx → CH(x-1)+H, x=4,3,2,1). All reactions in these steps are endothermic. The activation energy of the first hydrogen production from methane (CH4 →CH3 +H) on FeN3 surface is 0.39 eV while the barrier energy is 0.20 eV. However, the same reaction on FeN4 graphene has a quitequite high activation energy same as its barrier energy (1.84 eV), and its initial state switches directly to the final state without the transition state. The activation energies of most steps on FeN3 embedded graphene are much lower than that of FeN4 graphene surface. Therefore, dehydration reactions can occur with lower energy on FeN3 surface. This study can assist to discover a promising catalyst for methane dissociation through their finding.

PDF

___

[1] M.T. Baei, A. Soltani, and S. Hashemian, “Adsorption properties of hydrazine on pristine and Si-doped Al12N12 nano-cage,” Phosphorus, Sulfur, and Silicon and the Related Elements, vol. 191, no. 5, pp. 702-708, 2016.
[2] X. Xin, et al., “Spin states modulation of Four-Nitrogen coordinated Transition-Metal (TMN4) embedded graphene,” Applied Surface Science, vol. 570, pp. 151126, 2021.
[3] A.K. Fajrial et al., “First principles study of oxygen molecule interaction with the graphitic active sites of a boron-doped pyrolyzed Fe–N–C catalyst,” Physical Chemistry Chemical Physics, vol. 19, no. 34, pp. 23497-23504, 2017.
[4] C.W.B. Bezerra, et al., “A review of Fe–N/C and Co–N/C catalysts for the oxygen reduction reaction,” Electrochimica Acta, vol. 53, no. 15, pp. 4937-4951, 2008.
[5] B. Merzougui, et al., “A Pt-free catalyst for oxygen reduction reaction based on Fe–N multiwalled carbon nanotube composites,” Electrochimica Acta, vol. 107, pp. 126-132, 2013.
[6] G. Zhang, et al., “Is iron involved in the lack of stability of Fe/N/C electrocatalysts used to reduce oxygen at the cathode of PEM fuel cells?” Nano Energy, vol. 29, pp. 111-125, 2016.
[7] S. Stariha, et al., “PGM-free Fe-N-C catalysts for oxygen reduction reaction: Catalyst layer design,” Journal of Power Sources, vol. 326, pp. 43-49, 2016.
[8] L. Yu, et al., “Oxygen reduction reaction mechanism on nitrogen-doped graphene: A density functional theory study,” Journal of Catalysis, vol. 282 no. 1, pp. 183-190, 2011.
[9] G. Wu, and P. Zelenay, “Nanostructured Nonprecious Metal Catalysts for Oxygen Reduction Reaction,” Accounts of Chemical Research, vol. 46, no. 8, pp. 1878-1889, 2013.
[10] Z. Lu, et al., “Novel catalytic activity for oxygen reduction reaction on MnN4 embedded graphene: A dispersion-corrected density functional theory study,” Carbon, vol. 84, pp. 500-508, 2015.
[11] L. Ma and X. Chen, “Adsorption of naphthenic acids to the nitrogen-coordinated transition-metal embedded graphene: A DFT study,” Russian Journal of Physical Chemistry B, vol. 10, no. 6, pp. 1027-1031, 2016.
[12] Q.-K. Li, et al., “Cooperative spin transition of monodispersed FeN3 sites within graphene induced by CO adsorption,” Journal of the American Chemical Society, vol. 140, no. 45, pp. 15149-15152, 2018.
[13] H. Bae, et al., “High-throughput screening of metal-porphyrin-like graphenes for selective capture of carbon dioxide,” Scientific reports, vol. 6, no. 1, pp. 1-10, 2016.
[14] C. Hu, et al., “Adsorption and sensing characteristics of air decomposed species onto pyridine-like PdN3-doped CNT: a first-principles study,” Carbon Letters, vol. 32, pp. 109-117, 2022.
[15] X.-F. Li, et al., “Conversion of dinitrogen to ammonia by FeN3-embedded graphene,” Journal of the American Chemical Society, vol. 138, no. 28, pp. 8706-8709, 2016.
[16] T.R. Karl, and K.E. Trenberth, “Modern Global Climate Change,” Science, vol. 302, no. 5651, pp. 1719-1723, 2003.
[17] L. Milich, “The role of methane in global warming: where might mitigation strategies be focused?” Global Environmental Change, vol. 9, no. 3, pp. 179-201, 1999.
[18] A.R. Moss, J.-P. Jouany, and J. Newbold, “Methane production by ruminants: its contribution to global warming,” in Annales de zootechnie. EDP Sciences, vol. 49, no.3, pp. 231-253, 2000.
[19] R. Rossi, et al., “An unusual suicide: asphyxia by methane gas,” The American journal of forensic medicine and pathology, vol. 34, no. 2, pp. 83-85, 2013.
[20] M. Gasparik, et al., “First international inter-laboratory comparison of high-pressure CH4, CO2 and C2H6 sorption isotherms on carbonaceous shales,” International Journal of Coal Geology, vol. 132, pp. 131-146, 2014.
[21] K. Li, et al., “Adsorption of small hydrocarbons on pristine, N-doped and vacancy graphene by DFT study,” Applied Surface Science, vol. 515, p. 146028, 2020.
[22] W. Zhou, et al., “Hydrogen and methane adsorption in metal− organic frameworks: a high-pressure volumetric study,” The Journal of Physical Chemistry C, vol. 111, no. 44, pp. 16131-16137, 2007.
[23] W. Yuan, et al., “Experimental study and modelling of methane adsorption and diffusion in shale,” Fuel, vol. 117, pp. 509-519, 2014.
[24] K. Fan, et al., “Three stages of methane adsorption capacity affected by moisture content,” Fuel, vol. 231, pp. 352-360, 2018.
[25] X. Gao, et al., “Performance of intrinsic and modified graphene for the adsorption of H2S and CH4: a DFT study,” Nanomaterials, vol. 10, no. 2, pp. 299, 2020.
[26] H. Xu, et al., “CO2 adsorption-assisted CH4 desorption on carbon models of coal surface: A DFT study,” Applied Surface Science, vol. 375, pp. 196-206, 2016.
[27] A. Valera-Medina, et al., “Ammonia, Methane and Hydrogen for Gas Turbines,” Energy Procedia, vol. 75, pp. 118-123, 2015.
[28] X. Bai, et al., “Microwave catalytic synthesis of ammonia from methane and nitrogen,” Catalysis Science & Technology, vol. 8, no. 24, pp. 6302-6305, 2018.
[29] H.F. Abbas, and W.M.A. Wan Daud, “Hydrogen production by methane decomposition: A review,” International Journal of Hydrogen Energy, vol. 35, no. 3, pp. 1160-1190, 2010.
[30] A. Akça, “Conversion of methane to methanol on C-doped boron nitride: A DFT study,” Computational and Theoretical Chemistry, vol. 1202, pp. 113291, 2021.
[31] I. Staffell, et al., “The role of hydrogen and fuel cells in the global energy system,” Energy & Environmental Science, vol. 12, no. 2, pp. 463-491, 2019.
[32] H. Council, “Hydrogen scaling up: A sustainable pathway for the global energy transition,” 2017.
[33] E.S. Hanley, J.P. Deane, and B.P.Ó. Gallachóir, “The role of hydrogen in low carbon energy futures–A review of existing perspectives,” Renewable and Sustainable Energy Reviews, vol. 82, pp. 3027-3045, 2018.
[34] S. Dunn, “Hydrogen futures: toward a sustainable energy system,” International Journal of Hydrogen Energy, vol. 27, no. 3, pp. 235-264, 2002.
[35] H. Liu, et al., “A DFT theoretical study of CH4 dissociation on gold-alloyed Ni (111) surface,” Journal of natural gas chemistry, vol. 20, no. 6, pp. 611-617, 2011.
[36] K.F. Andriani, J. Mucelini, and J.L.F. Da Silva, “Methane dehydrogenation on 3d 13-atom transition-metal clusters: A density functional theory investigation combined with Spearman rank correlation analysis,” Fuel, vol. 275, pp. 117790, 2020.
[37] S. Jiang, et al., “Insight into the reaction mechanism of CO2 activation for CH4 reforming over NiO-MgO: A combination of DRIFTS and DFT study,” Applied Surface Science, vol. 416, pp. 59-68, 2017.
[38] Y. Guo, J. Feng, and W. Li, “Effect of the Ni size on CH4/CO2 reforming over Ni/MgO catalyst: A DFT study,” Chinese Journal of Chemical Engineering, vol. 25, no. 10, pp. 1442-1448, 2017.
[39] Y.-P. Guo, W.-Y. Li, and J. Feng, “Reaction pathway of CH4/CO2 reforming over Ni8/MgO (100),” Surface Science, vol. 660, pp. 22-30, 2017.
[40] R. Ghanbari, R. Safaiee, and M. Golshan, “A dispersion-corrected DFT investigation of CH4 adsorption by silver-decorated monolayer graphene in the presence of ambient oxygen molecules,” Applied Surface Science, vol. 457, pp. 303-314, 2018.
[41] MA. Lourenço, et al., “Interaction of CO2 and CH4 with functionalized periodic mesoporous phenylene–silica: Periodic DFT calculations and gas adsorption measurements,” The Journal of Physical Chemistry C, vol. 120, no. 7, pp. 3863-3875, 2016.
[42] A. Akça and İ.Ö. Alp, “The Dissociation Reaction of Methane on Ti-And Co-Embedded Graphene: A Dft Study,” Theory and Research in Science and Mathematics, pp. 45-64, Gece kitaplığı, ISBN. 978-625-7243-77-3, 2020.
[43] G. Roy, and A.P. Chattopadhyay, “Dissociation of methane on Ni4 cluster-A DFT study,” Computational and Theoretical Chemistry, vol. 1106, pp. 7-14, 2017.
[44] J. Li, E. Croiset and L. Ricardez–Sandoval, “Effect of carbon on the Ni catalyzed methane cracking reaction: A DFT study,” Applied Surface Science, vol. 311, pp. 435-442, 2014.
[45] K. Li, et al., “Dissociation mechanisms of CH4 on pristine, N-doped and vacancy graphene by DFT study,” Diamond and Related Materials, vol. 114, p. 108323, 2021.
[46] P. Giannozzi, et al., “QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials,” Journal of Physics: Condensed Matter, vol. 21, no. 39, p. 395502, 2009.
[47] P. Giannozzi, et al., “Advanced capabilities for materials modelling with Quantum ESPRESSO,” Journal of Physics: Condensed Matter, vol. 29, no. 46, pp. 465901, 2017.
[48] W. Kohn and L.J. Sham, “Self-Consistent Equations Including Exchange and Correlation Effects,” Physical Review, vol. 140, no. 4A, pp. 1133-1138, 1965.
[49] P.E. Blöchl, “Projector augmented-wave method,” Physical Review B, vol. 50, no. 24, pp. 17953-17979, 1994.
[50] S. Grimme, J.Antony, S. Ehrlich and H. Krieg, “A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu,” Journal of Chemical Physics, vol. 132, p. 154104, 2010.
[51] X. Cao, X.F. Li and W. Hu, “Tunable Electronic and Magnetic Properties of Graphene‐Embedded Transition Metal‐N4 Complexes: Insight From First‐Principles Calculations,” Chemistry–An Asian Journal, vol. 13, no. 21, pp. 3239-3245, 2018.
[52] G. Mills and H. Jónsson, “Quantum and thermal effects in H2 dissociative adsorption: Evaluation of free energy barriers in multidimensional quantum systems,” Physical Review Letters, vol. 72, no. 7, p. 1124, 1994.
[53] G. Mills, H. Jónsson and G.K. Schenter, “Reversible work transition state theory: application to dissociative adsorption of hydrogen,” Surface Science, vol. 324, no. 2-3, pp. 305-337, 1995.
[54] G. Henkelman, A. Arnaldsson, and H. Jónsson, “A fast and robust algorithm for Bader decomposition of charge density,” Computational Materials Science, vol. 36, no. 3, pp. 354-360, 2006.