A Stable Copper-based Metal-Azolate Framework for Efficient Electroreduction of CO₂ to C₂₊ Products

Abstract

Driven by renewable or excess electrical energy, electrochemical CO₂ reduction reaction (eCO₂RR) represents a promising carbon-neutral approach to generating valuable low-carbon fuels by consuming CO₂ and H₂O. C₂₊ products are one of the most economically valuable products among the reduction species of eCO₂RR, but there are still some challenges, such as low selectivity or low current density. In this work, we showed that a copper-based metal-azolate framework (MAF), denoted as MAF-203, exhibits the high performance of eCO₂RR to yield C₂₊ products with the Faradaic efficiency (C₂₊) of 52.5% and a current density of 660 mA/cm² at −1.2 V vs. RHE in a flow cell device under alkaline condition. Controlled experiment, in situ infrared spectroscopy and the density functional theory (DFT) calculations showed that the electron donating effect of methyl substituents on organic ligands of the copper-based MAF could enhance the ligand field and activation of key intermediates (*CO and *CHO species), thus promoting the coupling of *CO and *CHO for yielding C₂₊ products.

Keywords

Metal-organic framework / Carbon dioxide / Electroreduction / C₂₊ product / Metal-azolate framework

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