Issue 16, 2018

Covalent triazine framework modified with coordinatively-unsaturated Co or Ni atoms for CO2 electrochemical reduction

Abstract

The electrochemical reduction of carbon dioxide (CO2) has attracted considerable attention as a means of maintaining the carbon cycle. This process still suffers from poor performance, including low faradaic efficiencies and high overpotential. Herein, we attempted to use coordination number as a control parameter to improve the electrocatalytic performance of metal species that have previously been thought to have no CO2 reduction activity. Covalent triazine frameworks (CTF) modified with coordinatively-unsaturated 3d metal atoms (Co, Ni or Cu) were developed for efficient electroreduction of CO2. Co-CTF and Ni-CTF materials effectively reduced CO2 to CO from −0.5 V versus RHE. The faradaic efficiency of the Ni-CTF during CO formation reached 90% at −0.8 V versus RHE. The performance of Ni-CTF is much higher than that of the corresponding metal-porphyrin (using tetraphenylporphyrin; TPP). First principles calculations demonstrated that the intermediate species (adsorbed COOH) was stabilized on the metal atoms in the CTF due to the low-coordination structure of this support. Thus, the free energy barriers for the formation of adsorbed COOH on the metal atoms in the CTF supports were lower than those on the TPP supports.

Graphical abstract: Covalent triazine framework modified with coordinatively-unsaturated Co or Ni atoms for CO2 electrochemical reduction

Supplementary files

Article information

Article type
Edge Article
Submitted
06 Feb 2018
Accepted
16 Mar 2018
First published
19 Mar 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 3941-3947

Covalent triazine framework modified with coordinatively-unsaturated Co or Ni atoms for CO2 electrochemical reduction

P. Su, K. Iwase, T. Harada, K. Kamiya and S. Nakanishi, Chem. Sci., 2018, 9, 3941 DOI: 10.1039/C8SC00604K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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