Oxygen Reduction Reaction Mechanism on the Square Paddle-Wheel Cage Site of TM-BTC (TM=Mn, Fe, Cu) Metal-Organic Framework

Authors

  • Ahmad Nuruddin Advanced Functional Materials Research Group, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia
  • Adhitya Gandaryus Saputro Advanced Functional Materials Research Group, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia
  • Syauqi Abdurrahman Abrori Advanced Functional Materials Research Group, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia
  • Arifin Luthfi Maulana Advanced Functional Materials Research Group, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia
  • Virgiawan Listanto Rahagung Advanced Functional Materials Research Group, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia
  • Mohammad Kemal Agusta Advanced Functional Materials Research Group, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia
  • Fadjar Fathurrahman Advanced Functional Materials Research Group, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia
  • Amrina Mustaqim Engineering Physics Department, Institut Teknologi Sumatera Jl. Terusan Ryacudu, Way Huwi, Lampung 35365, Indonesia
  • Hermawan Kresno Dipojono Advanced Functional Materials Research Group, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia

DOI:

https://doi.org/10.5614/j.math.fund.sci.2022.54.2.2

Keywords:

density functional theory , microkinetic, MOF, oxygen reduction reaction, TM-BTC

Abstract

Our study examined the mechanism of oxygen reduction reactions (ORR) at the square paddle-wheel cage active site of TM-BTC metal-organic frameworks (MOFs), where TM is a transition metal, Mn, Fe, or Cu. We used a combination of density functional theory (DFT) and microkinetic calculations to investigate this mechanism. By using a small cluster for modeling the TM-BTC active site structure, we successfully reproduced the experimental trend of ORR activity in the TM-BTC systems: Mn-BTC > Fe-BTC > Cu-BTC. We also found that the unusual ORR activity trend in experiments for Mn and Fe systems originates from the strength of OH adsorption on these systems. The Mn-BTC system exhibits higher ORR activity than the Fe-BTC system due to its weaker adsorption of OH groups. A very strong OH adsorption makes the final OH reduction step sluggish, hence hindering the ORR process.

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Published

2022-12-28

Issue

Vol. 54 No. 2 (2022)

Section

Articles