Deciphering electrochemical interactions in metal–polymer catalysts for CO₂ reduction

Abstract

Polymers play a critical role in catalyst design to stabilize metal nanoparticles on the cathode for electrochemical carbon dioxide reduction reaction (CO2RR). However, electrochemical interactions between the metal and polymer...

In Situ Infrared Spectroscopic Evidence of Enhanced Electrochemical CO2 Reduction and C–C Coupling on Oxide-Derived Copper

“…Subsequently, we performed precise projected density of states (PDOS) calculations to confirm this effect on *CHO adsorption in both catalytic systems, as shown in Figure d,e. The upshift of the d-band center of Cu toward the Fermi level in the OD–Cu system (−2.18 eV) compared with the Cu system (−2.40 eV) indicates its stronger interactions with *CHO. − Moreover, the larger overlapping of the PDOS of the Cu d orbital with that of the s and p orbitals of *CHO in the OD–Cu system further implies the strengthened adsorption of *CHO on the partially oxidized Cu surface. − In addition, the bond length is 1.949 Å for the Cu–C bond in the OD–Cu system, which is shorter than that in the Cu system (1.967 Å), illustrating the stronger Cu–C bond on the partially oxidized Cu surface. As a result, our findings reveal that the electronic structure of the partially positive Cu layer is conducive to the optimal adsorption of *CHO.…”

PTFE nanocoating on Cu nanoparticles through dry processing to enhance electrochemical conversion of CO2 towards multi-carbon products

“…The results indicate that surface modification of Cu by polymers containing oxygen, nitrogen, or fluorine functional groups not only increases the hydrophobicity of the cathode, but also can suppress the competing hydrogen evolution reaction (HER) and help boost C 2+ product selectivity through stabilization of the reaction intermediates. 32–37 For instance, Wei et al coated Cu foil with polyaniline and demonstrated increase of C 2+ product selectivity from 15% to 60% and the reason was ascribed to the increase of intermediate CO coverage on Cu. 34 Wang et al found that polymer addition lowered the energy barrier for CO protonation from 1.14 eV to 0.68 eV despite an increase in ohmic resistance.…”

“…34 Wang et al found that polymer addition lowered the energy barrier for CO protonation from 1.14 eV to 0.68 eV despite an increase in ohmic resistance. 36 García de Arquer et al created a catalyst/ionomer interface to facilitate the transport of reactant, product, and electron, which resulted in a 67% C 2+ product selectivity under a 510 mA cm −2 current density. 33 Only a few theoretical studies have been conducted to understand the effect of polymer coating on the C 2+ product selectivity.…”

“…Currently, most reported methods to prepare a polymer–Cu interface and resultant working electrode utilize excessive amounts of solvents. 33,34,36 Catalyst ink coating is currently the most common fabrication method for preparing the working electrode. Most inks are prepared by dispersing catalyst nanoparticles in isopropanol/water mixture and coated by air brushing or ultrasonic spraying coating.…”

“…Most inks are prepared by dispersing catalyst nanoparticles in isopropanol/water mixture and coated by air brushing or ultrasonic spraying coating. 33,36,39–41 However, insufficient ink stability, inhomogeneous catalyst layers and uncontrollable structures due to complex catalyst dispersion and solvent drying processes are common problems. 42 New methods allowing the controllable fabrication of catalyst layers across different scales simultaneously, thereby bridging interface engineering and sustainable manufacturing, are highly desirable.…”