Catalyst Engineering for the Selective Reduction of CO2 to CH4: A First-Principles Study on X-MOF-74 (X = Mg, Mn, Fe, Co, Ni, Cu, Zn)

Published

December 14, 2023

Author(s)

Gavin McCarver, Taner N. Yildirim, Wei Zhou

Abstract

The conversion of carbon dioxide (CO2) into more valuable chemical compounds represents a critical objective for addressing environmental challenges and advancing sustainable energy sources. The CO2 reduction reaction (CO2RR) holds promise for transforming CO2 into versatile feedstock materials and fuels. Leveraging first-principles methodologies provides a robust approach to evaluate catalysts and steer experimental efforts. In this study, we examine the CO2RR process using a diverse array of representative cluster models derived from XMOF-74 (where X encompasses Mg, Mn, Fe, Co, Ni, Cu, or Zn) through first-principles methods. Notably, our investigation highlights the Fe-MOF-74 cluster's unique attributes, including favorable CO2 binding and the lowest limiting potential of the studied clusters for converting CO2 to methane (CH4) at 0.32 eV. Our analysis identified critical factors driving the selective CO2RR pathway, enabling the formation CH4 on the Fe-MOF-74 cluster. These factors involve less favorable reduction of hydrogen to H2 and strong binding affinities between the Fe open-metal site and reduction intermediates, effectively curtailing desorption processes of closed-shell intermediates such as formic acid (HCOOH), formaldehyde (CH2O), and methanol (CH3OH), to lead to selective CH4 formation.

Citation

Chemphyschem

Volume

24

Pub Type

Journals

Download Paper

https://doi.org/10.1002/cphc.202300645

Local Download

Keywords

MOF, CO2 Conversion, ab initio, Catalysis

Citation

McCarver, G. , Yildirim, T. and Zhou, W. (2023), Catalyst Engineering for the Selective Reduction of CO2 to CH4: A First-Principles Study on X-MOF-74 (X = Mg, Mn, Fe, Co, Ni, Cu, Zn), Chemphyschem, [online], https://doi.org/10.1002/cphc.202300645, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=956235 (Accessed December 13, 2024)