Density Functional Theory Analysis of Catalytic Carbon Dioxide Reduction on Nitrogen-Doped Graphene Surfaces

International Journal of Physics | Vol. 5, No. 4, April 2014 | pp. 25–32

DOI: 10.46882/2014/IJP/000048

Research Article

Title: Density Functional Theory Analysis of Catalytic Carbon Dioxide Reduction on Nitrogen-Doped Graphene Surfaces

Names of Authors: A. L. Silva¹, K. N. Gupta²

Authors’ Affiliations: ¹Institute of Physics, Federal University of Rio Grande do Sul, Porto Alegre 91501-970, Brazil; ²Department of Physics, Indian Institute of Technology Delhi, New Delhi 110016, India

Abstract: Electrochemical reduction of carbon dioxide (CO²) into valuable chemical feedstocks offers a sustainable strategy for carbon recycling. This investigation uses density functional theory calculations to analyze the catalytic performance and reaction mechanisms of CO² reduction on nitrogen-doped graphene surfaces. We modeled three distinct configurations: pyridinic, pyrrolic, and quaternary nitrogen doping. Free energy profiles for intermediate steps leading to formic acid (HCOOH) and carbon monoxide (CO) were computed using the computational hydrogen electrode model. The calculations demonstrate that pyridinic nitrogen sites lower the activation barrier for the initial protonation step (*CO² + H⁺ + e⁻ -> *COOH) to 0.45 eV. This value is significantly lower than the 1.15 eV barrier calculated for pristine graphene surfaces. The overpotential required to trigger selective formic acid production on pyridinic sites was estimated at -0.38 V versus the standard hydrogen electrode. Charge density difference mappings show that nitrogen doping induces localized spin polarization and electron deficiency on adjacent carbon atoms. This electronic reconfiguration stabilizes the adsorbed intermediates. These quantum mechanical insights provide theoretical guidelines for developing metal-free, carbon-based catalysts for efficient greenhouse gas conversion.

Keywords: Carbon dioxide reduction; density functional theory; nitrogen-doped graphene; electrocatalysis; reaction mechanism; overpotential

Manuscript Timeline: Received: January 05, 2014; Revised: February 17, 2014; Accepted: March 04, 2014; Published: April 10, 2014

Citation: Silva, A. L., & Gupta, K. N. (2014). Density Functional Theory Analysis of Catalytic Carbon Dioxide Reduction on Nitrogen-Doped Graphene Surfaces. International Journal of Physics, 5(4), 25–32.

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