2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO 2 to Formic Acid

Cho, Jinwon; Medina, Arturo; Saih, Ines; Il Choi, Ji; Drexler, Matthew; Goddard, III, William A.; Alamgir, Faisal M.; Jang, Seung Soon

doi:10.1002/anie.202320268

Title: 2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO ₂ to Formic Acid

Journal Article · Mon Feb 12 00:00:00 EST 2024 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202320268· OSTI ID:2322448

Cho, Jinwon ^[1]; Medina, Arturo ^[1]; Saih, Ines ^[1]; Il Choi, Ji ^[1]; Drexler, Matthew ^[1];

^[2];

^[1];

^[1]

School of materials Science and Engineering Georgia Institute of Technology 771 Ferst Dr. Atlanta GA 30332–0245 USA
Materials and Process Simulation Center California Institute of Technology Pasadena CA 91125 USA

Abstract Efficiently transforming CO ₂ into renewable energy sources is crucial for decarbonization efforts. Formic acid (HCOOH) holds great promise as a hydrogen storage compound due to its high hydrogen density, non‐toxicity, and stability under ambient conditions. However, the electrochemical reduction of CO ₂ (CO ₂ RR) on conventional carbon black‐supported metal catalysts faces challenges such as low stability through dissolution and agglomeration, as well as suffering from high overpotentials and the necessity to overcome the competitive hydrogen evolution reaction (HER). In this study, we modify the physical/chemical properties of metal surfaces by depositing metal monolayers on graphene (M/G) to create highly active and stable electrocatalysts. Strong covalent bonding between graphene and metal is induced by the hybridization of sp and d orbitals, especially the sharp , , and orbitals of metals near the Fermi level, playing a decisive role. Moreover, charge polarization on graphene in M/G enables the deposition of another thin metallic film, forming metal/graphene/metal (M/G/M) structures. Finally, evaluating overpotentials required for CO ₂ reduction to HCOOH, CO, and HER, we find that Pd/G, Pt/G/Ag, and Pt/G/Au exhibit excellent activity and selectivity toward HCOOH production. Our novel 2D hybrid catalyst design methodology may offer insights into enhanced electrochemical reactions through the electronic mixing of metal and other p‐block elements.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0021266

OSTI ID:: 2322448

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Vol. 63 Journal Issue: 12; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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