Nitrogen atom

Catalysis

Electrochemistry

Materials science

Embedded system

Transition metal

Biochemistry

Computer science

Inorganic chemistry

Nitrogen

Electrocatalyst

Physical chemistry

Polymer

Redox

Nanotechnology

Organic chemistry

Mathematics

Atom (system on chip)

Geometry

Monolayer

Crystallography

Dimer

Chemistry

Electrode

Monomer

Group (periodic table)

Oxygen reduction reaction

Reduction (mathematics)

Trimer

The Journal of Physical Chemistry C

Low-cost and efficient electrocatalysts are urgently required for the N2 reduction reaction (NRR) to produce NH3 under ambient conditions. By using first-principles calculation, we systematically investigated the NRR catalytic activity of the transition metal (TM, including Mn, Fe, Co, and Ni) monomer-, dimer-, and trimer-anchored graphdiyne (GDY) monolayers. It is shown that most of the TM monomer- and dimer-anchored GDY monolayers have enhanced NRR catalytic activity compared with the Ru(0001) stepped surface. Especially, the Co dimer-anchored GDY monolayer (Co2@GDY) exhibits the best NRR catalytic activity with the onset potential of −0.43 V and a high ability to suppress the competing hydrogen evolution reaction. The high NRR catalytic activity of Co2@GDY could be attributed to the localized electronic states near the Fermi level and the strong electron-donating ability of the GDY monolayer. Furthermore, an approximate linear trend between the predicted onset potential and the N adsorption energy is revealed, which may act as a simple descriptor for the intrinsic NRR catalytic activity of such catalysts. Our findings not only propose an efficient and low-cost double-atom catalyst for NRR but also provide a new clue for designing TM atomic catalysts based on GDY sheets for various electrocatalysis applications.

Computational Evaluation of Electrocatalytic Nitrogen Reduction on TM Single-, Double-, and Triple-Atom Catalysts (TM = Mn, Fe, Co, Ni) Based on Graphdiyne Monolayers