2D Copper Tetrahydroxyquinone Conductive Metal–Organic Framework for Selective CO₂ Electrocatalysis at Low Overpotentials

Abstract

Metal–organic frameworks (MOFs) are promising materials for electrocatalysis; however, lack of electrical conductivity in the majority of existing MOFs limits their effective utilization in the field. Herein, an excellent catalytic activity of a 2D copper (Cu)‐based conductive MOF, copper tetrahydroxyquinone (CuTHQ), is reported for aqueous CO2 reduction reaction (CO2RR) at low overpotentials. It is revealed that CuTHQ nanoflakes (NFs) with an average lateral size of 140 nm exhibit a negligible overpotential of 16 mV for the activation of this reaction, a high current density of ≈173 mA cm−2 at −0.45 V versus RHE, an average Faradaic efficiency (F.E.) of ≈91% toward CO production, and a remarkable turnover frequency as high as ≈20.82 s−1. In the low overpotential range, the obtained CO formation current density is more than 35 and 25 times higher compared to state‐of‐the‐art MOF and MOF‐derived catalysts, respectively. The operando Cu K‐edge X‐ray absorption near edge spectroscopy and density functional theory calculations reveal the existence of reduced Cu (Cu+) during CO2RR which reversibly returns to Cu2+ after the reaction. The outstanding CO2 catalytic functionality of conductive MOFs (c‐MOFs) can open a way toward high‐energy‐density electrochemical systems.

Crosslinked porous polyimides: structure, properties and applications

“…successfully in this field. 101,[122][123][124][125][126][127] Recent advances show that the photocatalytic CO 2 conversion can be carried out in porous polymers even in the absence of metal atoms; 112,128,129 yet this area has not been explored at all with pPIs to date, and presents a significant opportunity to address global challenges presented by continued and growing human activity and influence on the environment. In particular, recent focus has been placed on the direct conversion of CO 2 to useful chemicals (rather than storage).…”

Two‐dimensional MOFs: Design & Synthesis and Applications

“…The nanosheets have good electrical conductivity and can effectively promote the electrochemical reduction of CO 2 . Amin and coworkers reported the CO 2 RR electrocatalytic activity study of 2D copper based c‐MOF and copper tetrahydroxyquinone (Cu‐THQ) [49] . c‐MOF is an ideal catalyst material, which can significantly improve the product selectivity and energy efficiency of CO 2 RR, making the 2D Cu‐based conductive MOF, Cu‐THQ has excellent catalytic activity.…”

Advances in Understanding the Electrocatalytic Reconstruction Chemistry of Coordination Compounds

“…Electrochemically generated low valence metal centers like Cu (Cu + ), [ 162 ] Mn 0 , [ 163 ] Co I , [ 164 ] Fe 0 , [ 165 ] Ni I , [ 166 ] Ru 0 , [ 167 ] and Re 0[ 168 ] are general case. For example, Majidi et al.…”

“…recently found that there existed reduced Cu (Cu + ) during CO 2 RR for copper tetrahydroxyquinone (Cu‐THQ), which was confirmed by operando Cu K‐edge X‐ray absorption near edge structure (XANES). [ 162 ] Apart from the valance evolution of metal center, the ligand can also be reduced. Wang et al.…”