CO₂ electro-reduction reaction via a two-dimensional TM@TAP single-atom catalyst

Area of Science:

• Materials Science
• Electrochemistry
• Computational Chemistry

Background:

• Electrocatalytic CO2 reduction is crucial for sustainable energy.
• Developing efficient and selective electrocatalysts is a key challenge.
• Monolayer transition metal dichalcogenides offer tunable electronic properties for catalysis.

Purpose of the Study:

• To systematically investigate TM@TAP as electrocatalysts for CO2RR.
• To explore reaction mechanisms and product selectivity.
• To identify highly active and selective catalysts for specific reduction products.

Main Methods:

• First-principles calculations were employed for theoretical screening.
• Consideration of active site blocking by H and OH intermediates.
• Detailed analysis of reaction pathways and limiting potentials.

Main Results:

• Cr@TAP, Zn@TAP, Mo@TAP, and Cd@TAP selectively produce HCOOH.
• Mn@TAP and Rh@TAP favor CO production.
• Fe@TAP yields CH3OH, Co@TAP yields HCHO, and Tc@TAP/Ru@TAP yield CH4.
• Cr@TAP (-0.33 V) and Rh@TAP (-0.28 V) show high activity.
• Fe@TAP demonstrates potential for CH3OH production (-0.51 V).

Conclusions:

• TM@TAP electrocatalysts exhibit diverse selectivities for CO2RR.
• Cr@TAP, Rh@TAP, and Fe@TAP are promising candidates for specific CO2 reduction products.
• The study provides insights for rational design of CO2RR electrocatalysts.