Comprehensive Mechanism for CO Electroreduction on Dual-Atom-Catalyst-Anchored N-Doped Graphene

Area of Science:

• Catalysis
• Computational Chemistry
• Electrochemistry

Background:

• Carbon neutrality is crucial for reducing greenhouse gas emissions.
• Electrocatalytic carbon monoxide reduction (e-CORR) can produce valuable C1 products, but targeted C2 fuel synthesis remains challenging.
• Systematic investigation of C2 fuel production mechanisms via e-CORR is needed.

Purpose of the Study:

• To screen dual-atom catalysts (DACs) for C2 fuel production using first-principles calculations.
• To understand the influence of explicit solvents on e-CORR performance and selectivity.
• To elucidate the mechanism of C-C coupling in e-CORR.

Main Methods:

• First-principles density functional theory (DFT) calculations.
• Screening of various dual-atom catalysts (DACs).
• Inclusion of explicit solvent effects in theoretical models.

Main Results:

• Methanol, ethanol, and ethylene are producible on DAC-Co and DAC-Cu.
• Acetate is selectively produced on DAC-Cu.
• DAC-Co favors methanol and ethylene, while DAC-Cu favors acetate and ethylene.
• Solvent effects significantly impact adsorption, protonation, and dimerization steps.
• Low Integrated Crystal Orbital Hamilton Population (ICOHP) values correlate with facile C-C coupling.

Conclusions:

• DACs offer tunable selectivity for C2 fuel production via e-CORR.
• Solvent inclusion is critical for accurate prediction of e-CORR performance.
• Understanding the mechanism, particularly C-C coupling, guides catalyst design for efficient C2 fuel synthesis.