Get 20M+ Full-Text Papers For Less Than $1.50/day. Start a 14-Day Trial for You or Your Team.

Learn More →

Cobalt Quaterpyridine Complexes for Highly Efficient Heterogeneous CO2 Reduction in Aqueous Media

Cobalt Quaterpyridine Complexes for Highly Efficient Heterogeneous CO2 Reduction in Aqueous Media Ligands play a critical role in the electrocatalytic CO2 reduction reaction (CO2RR) based on heterogeneous molecular catalysts. Previous research on heterogeneous molecular electrocatalysis has mainly dealt with N4 ligands with pyrrole as subunits (porphyrin, phthalocyanine, etc.), while ligands constructed from pyridine subunits remain uncommon. The examples for comparing active configurations are few and far between. Herein, the development of new N4 cobalt complexes based on pyridine subunits is explored. After anchoring onto carbon nanotubes, they can exhibit CO2RR activity at a low overpotential of 140 mV, and high activity from ‐0.30 to ‐0.60 V versus reference hydrogen electrode with a selectivity of above 98%. Excellent performance at large current densities can also be observed in a flow cell. In situ attenuated total reflectance‐Fourier transform infrared spectroscopy proves that such electrocatalysts exhibit CO production at lower overpotential and moderate CO adsorption ability over a wide potential range. From density functional theory calculations, it is shown that a pyridine‐based cobalt complex on a carbon substrate can reduce the Gibbs free energy for reactions further than its counterpart pyrrole‐based ones. Further analysis proves that the semimetal behavior of optimized d‐orbitals may facilitate charge transfer and increase the activity. This provides a new insight for understanding catalytically active moieties in heterogeneous molecular catalysts with ligands constructed from pyridine subunits. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Advanced Energy Materials Wiley

Cobalt Quaterpyridine Complexes for Highly Efficient Heterogeneous CO2 Reduction in Aqueous Media

Download PDF
11 pages

Loading next page...
 
/lp/wiley/cobalt-quaterpyridine-complexes-for-highly-efficient-heterogeneous-co2-l2AUhhYlTv
Publisher
Wiley
Copyright
© 2022 Wiley‐VCH GmbH
ISSN
1614-6832
eISSN
1614-6840
DOI
10.1002/aenm.202202108
Publisher site
See Article on Publisher Site

Abstract

Ligands play a critical role in the electrocatalytic CO2 reduction reaction (CO2RR) based on heterogeneous molecular catalysts. Previous research on heterogeneous molecular electrocatalysis has mainly dealt with N4 ligands with pyrrole as subunits (porphyrin, phthalocyanine, etc.), while ligands constructed from pyridine subunits remain uncommon. The examples for comparing active configurations are few and far between. Herein, the development of new N4 cobalt complexes based on pyridine subunits is explored. After anchoring onto carbon nanotubes, they can exhibit CO2RR activity at a low overpotential of 140 mV, and high activity from ‐0.30 to ‐0.60 V versus reference hydrogen electrode with a selectivity of above 98%. Excellent performance at large current densities can also be observed in a flow cell. In situ attenuated total reflectance‐Fourier transform infrared spectroscopy proves that such electrocatalysts exhibit CO production at lower overpotential and moderate CO adsorption ability over a wide potential range. From density functional theory calculations, it is shown that a pyridine‐based cobalt complex on a carbon substrate can reduce the Gibbs free energy for reactions further than its counterpart pyrrole‐based ones. Further analysis proves that the semimetal behavior of optimized d‐orbitals may facilitate charge transfer and increase the activity. This provides a new insight for understanding catalytically active moieties in heterogeneous molecular catalysts with ligands constructed from pyridine subunits.

Journal

Advanced Energy Materials – Wiley

Published: Sep 1, 2022

Keywords: CO 2 conversion; electrocatalytic CO 2 reduction; heterogeneous electrocatalysis; heterogeneous molecular catalysts

References