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

Yu Te Chan, Ming Kang Tsai

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3 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)29068-29076
Number of pages9
JournalPhysical Chemistry Chemical Physics
Volume19
Issue number43
DOIs
Publication statusPublished - 2017 Jan 1

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Carbon Nanotubes
Coordination Complexes
Carbon Monoxide
Catalysis
catalysis
Transition metals
Nitrogen
transition metals
carbon nanotubes
nitrogen
Metals
Molecular orbitals
Vacancies
Density functional theory
Hydrogen
molecular orbitals
curvature
density functional theory
Ligands
catalysts

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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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.",
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N2 - 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.

AB - 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.

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