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

Year 2022, , 62 - 73, 28.02.2022

Hilal Küçük

https://doi.org/10.16984/saufenbilder.959390

Abstract

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. CH4 molecule 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.

Keywords

CH4 decomposition, methane, single-atom catalysis, FeN3 embedded graphene, FeN4 embedded graphene, dehydrogenation

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