Jump to main content
Jump to site search

Issue 43, 2017
Previous Article Next Article

CO2 reduction catalysis by tunable square-planar transition-metal complexes: a theoretical investigation using nitrogen-substituted carbon nanotube models

Author affiliations

Abstract

In this work, using density functional theory, we have characterized the CO2 reduction capabilities of a series of nine transition-metal-chelated nitrogen-substituted carbon nanotube models (TM-4N2v-CNT). Each of the chelated models consists of a four-N-substituted and one vacancy framework to mimic square planar homogeneous catalysts, and is coordinated to Fe, Ru, Os, Co, Rh, Ir, Ni, Pt or Cu. The results are further investigated to search for the possible electrochemical intermediates along the CO2 reduction pathway. We’ve found that all of the tested elements are predicted to favor the hydrogen evolution reaction over CO2 reduction energetically (with the exception of Cu), and that only Group 8 elements are predicted to bind CO effectively and other cases prefer HCOOH formation. The observed CO binding preference could be rationalized via ligand field theory based on the molecular orbitals of the square planar complexes. With a suitable applied voltage to stabilize all of the adsorbed CO intermediates, Ru and Os are predicted to produce CH4, whereas Fe is predicted to produce CH3OH. Increasing the curvature of the CNT could reduce the required potential in the potential-determining step substantially. However, the predicted catalytic sequence is subject to only the selection of a metal center.

Graphical abstract: CO2 reduction catalysis by tunable square-planar transition-metal complexes: a theoretical investigation using nitrogen-substituted carbon nanotube models

Back to tab navigation

Supplementary files

Publication details

The article was received on 04 Sep 2017, accepted on 18 Oct 2017 and first published on 18 Oct 2017


Article type: Paper
DOI: 10.1039/C7CP06024F
Citation: Phys. Chem. Chem. Phys., 2017,19, 29068-29076

  •   Request permissions

    CO2 reduction catalysis by tunable square-planar transition-metal complexes: a theoretical investigation using nitrogen-substituted carbon nanotube models

    Y. Chan and M. Tsai, Phys. Chem. Chem. Phys., 2017, 19, 29068
    DOI: 10.1039/C7CP06024F

Search articles by author

Spotlight

Advertisements