2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO2 to Formic Acid

Efficiently transforming CO2 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...

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Published in:Angewandte Chemie International Edition 2024-03, Vol.63 (12), p.e202320268-n/a
Main Authors: Cho, Jinwon, Medina, Arturo, Saih, Ines, Il Choi, Ji, Drexler, Matthew, Goddard, William A., Alamgir, Faisal M., Jang, Seung Soon
Format: Article
Language:English
Subjects:
2D Electrocatalysts
Black carbon
Bonding strength
Carbon black
Carbon dioxide
Catalysts
Chemical properties
Chemical reduction
CO2 Reduction
Decarbonization
Density Functional Theory
Electrocatalysts
Electrochemistry
Electrode polarization
Formic acid
Graphene
HER
Hybridization
Hydrogen
Hydrogen evolution reactions
Hydrogen storage
Metal surfaces
Metals
Orbital Hybridization
Orbitals
Palladium
Platinum
Renewable energy sources
Stability
Toxicity
Two dimensional materials
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Summary:Efficiently transforming CO2 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 CO2 (CO2RR) 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 dz2 ${{d}_{{z}^{2}}}$ , dyz ${{d}_{yz}}$ , and dxz ${{d}_{xz}}$ 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 CO2 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. Strong covalent bonding between metal monolayer and graphene driven by the sp and d orbital hybridization, 2D metal/graphene (M/G) system is investigated. The charge transfer from metal to graphene allows for the electrodeposition of another metal film, thus forming metal/graphene/metal (M/G/M) system. These 2D hybrid systems exhibit excellent activity and selectivity toward formic acid production over competitive hydrogen evolution reaction.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202320268