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

Panpan Su, Kazuyuki Iwase, Takashi Harada, Kazuhide Kamiya, Shuji Nakanishi

Research output: Contribution to journalArticlepeer-review

69 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)3941-3947
Number of pages7
JournalChemical Science
Volume9
Issue number16
DOIs
Publication statusPublished - 2018

ASJC Scopus subject areas

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Covalent triazine framework modified with coordinatively-unsaturated Co or Ni atoms for CO<sub>2</sub> electrochemical reduction'. Together they form a unique fingerprint.

Cite this