Issue 32, 2024

N/O coordinated s-block potassium atoms as highly active sites for electroreduction of CO2 to CO

Abstract

According to the d-band center theory of transition-metals, s-block main group metals with fewer valence electrons and delocalized s/p-orbitals are considered to exhibit poor electrocatalytic activity. Therefore, single-atom catalysts (SACs) for CO2 electroreduction to CO primarily focus on transition metal and p-block main group metal atoms as active centers. Herein, we prepared a porous carbon material doped with N/O coordinated K atoms using a simple high-temperature solid-phase synthesis method. The synthesized K–N, O/C catalyst demonstrates remarkable CO selectivity with Faraday efficiency (FE) exceeding 90% over a wide potential window between −0.5 V and −0.9 V versus the reversible hydrogen electrode (vs. RHE). Moreover, the catalyst exhibits a maximum FE of 97.8% towards CO at −0.6 V vs. RHE. In situ attenuated total reflectance infrared spectroscopy (ATR-FTIR) confirms the formation of *COOH on the K–N, O/C catalysts. Through Density Functional Theory (DFT) calculations, we screen out the most possible coordination structures. The K–O2 and K-pyrrolic-N2 models show significantly high CO2 reduction activity. Heteroatom doping induces partial overlap of the electronic states of the s and p orbitals of the K atom with the p orbitals of the coordinated O atom or N atom, thus modulating the electronic structure of the K atom into the catalytically active center for the conversion of CO2 to CO.

Graphical abstract: N/O coordinated s-block potassium atoms as highly active sites for electroreduction of CO2 to CO

Supplementary files

Article information

Article type
Paper
Submitted
31 5 2024
Accepted
12 7 2024
First published
22 7 2024

J. Mater. Chem. A, 2024,12, 21058-21065

N/O coordinated s-block potassium atoms as highly active sites for electroreduction of CO2 to CO

Y. Qu, P. Wang, W. Zheng, N. Duan, Y. Yang, T. Hou, C. Bi, D. Wang and Q. Chen, J. Mater. Chem. A, 2024, 12, 21058 DOI: 10.1039/D4TA03780D

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