First principles investigation of cobalt-phthalocyanine active site tuning via atomic linker immobilization for CO2 electroreduction

Oliver J. Conquest, Tanglaw Roman, Aleksei Marianov, Alena Kochubei, Yijiao Jiang, Catherine Stampfl

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

Abstract

We investigate the CO2 electroreduction reaction (CO2ERR) using first principles calculations, for the active site tuning of cobalt phthalocyanine (CoPc) via distinct atomic linker species which immobilize CoPc on a carbon nanotube (CNT) substrate. Eight different linker species are studied, along with the effect of linker hydrogenation. Superior reaction performance is predicted for the NH, S and PH linkers, which show activated CO2 adsorption. This results from spin polarization causing unoccupied dz2 spin-down states of the cobalt active site at, or above, the Fermi level. Using an ‘on-catalyst’ reaction scheme, calculated activation barriers for COOH formation and CO desorption are lower for the CoPc-PH-CNT system compared to the CoPc-NH-CNT system and CoPc remains attached to PH-CNT throughout the reaction. We thus expect the PH linker system to have similar or better CO2ERR performance compared to the NH and S linker systems but at a slightly higher electrode potential.

Original languageEnglish
Pages (from-to)43-55
Number of pages13
JournalJournal of Catalysis
Volume422
Early online date8 Apr 2023
DOIs
Publication statusPublished - Jun 2023

Keywords

  • Activation barriers
  • Active site
  • Catalyst
  • CO electroreduction
  • Cobalt
  • Density of states
  • DFT
  • First principles
  • Free energy
  • Phthalocyanine

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