Organic chemistry

Atom (system on chip)

Catalysis

Embedded system

Chemical physics

Chemistry

Molecule

Computer science

Heteronuclear molecule

Journal of the American Chemical Society

Facing the increasingly serious energy and environmental crisis, the development of heteronuclear metal-free double-atom catalysts is a potential strategy to realize efficient catalytic nitrogen reduction with low energy consumption and no pollution because it could combine the advantages of flexible active sites in double-atom catalysts while also being pollution-free and have high Faraday efficiency in metal-free catalysts simultaneously. However, according to the existing mechanism, the finite orbits of other nonmetallic atoms, except the boron atom, reduce the possibility of metal-free catalysis and hinder the development of heteronuclear metal-free double-atom catalysts. Herein, we propose a new "capture-backdonation-recapture" mechanism, which skillfully uses the electron capture-backdonation-recapture between boron, the substrate, and other nonmetallic elements to solve the above problems. Based on this mechanism, by means of the first-principle calculations, the material structure, adsorption energy, catalytic activity, and selectivity of 36 catalysts are systematically investigated to evaluate their catalytic performance. B-Si@BP1 and B-Si@BP3 are selected for their good catalytic performance and low limiting potentials of -0.14 and -0.10 V, respectively. Meanwhile, the "capture-backdonation-recapture" mechanism is also verified by analyzing the results of adsorption energy and electron transfer. Our work broadens the ideas and lays the theoretical foundation for the development of heteronuclear metal-free double-atom catalysts in the future.

“Capture-Backdonation-Recapture” Mechanism for Promoting N<sub>2</sub> Reduction by Heteronuclear Metal-Free Double-Atom Catalysts

“Capture-Backdonation-Recapture” Mechanism for Promoting N2 Reduction by Heteronuclear Metal-Free Double-Atom Catalysts

“Capture-Backdonation-Recapture” Mechanism for Promoting N₂ Reduction by Heteronuclear Metal-Free Double-Atom Catalysts