Electronic Structure and CO₂ Reactivity of Group IV/V/VI Tetraperoxometalates

Area of Science:

• * Inorganic Chemistry
• * Materials Science
• * Environmental Chemistry

Background:

• * Tetraperoxo metal complexes are dioxygen compounds with unique properties.
• * Direct air capture (DAC) is crucial for mitigating climate change.
• * Their application in DAC reactions remains understudied.

Purpose of the Study:

• * To computationally investigate tetraperoxometalate complexes for CO2 capture.
• * To model the reaction mechanism of CO2 capture by [M(O2)4]x- complexes.
• * To identify factors influencing the efficiency of these complexes in DAC.

Main Methods:

• * Density Functional Theory (DFT) calculations were employed.
• * Optimized structures, partial charges, and frontier orbital interactions were analyzed.
• * Reactivity was predicted for complexes with Group IV, V, and VI metal centers.

Main Results:

• * Nine tetraperoxometalate complexes were studied for CO2 capture.
• * [Ti(O2)4]4- demonstrated high efficiency, while [W(O2)4]2- showed low efficiency.
• * Differences in reactivity were rationalized by stabilizing a peroxycarbonate intermediate.

Conclusions:

• * Tetraperoxo metal complexes offer a novel pathway for direct air capture.
• * Titanium and tungsten complexes exhibit distinct efficiencies in CO2 capture.
• * Computational descriptors aid in understanding and designing effective DAC materials.