The High-Effective Catalytic Degradation of Benzo[a]pyrene by Mn-Corrolazine Regulated by Oriented External Electric Field: Insight From DFT Study

Abstract

The degradation of BaP into hydroxybenzo[a]pyrene by Mn-corrolazine and its regulation by an oriented external electronic field (OEEF) were systematically studied using first-principle calculations. Extensive density function calculations showed that the degradation of BaP into hydroxybenzo[a]pyrene by Mn-corrolazine occurs via a three-step process in the absence of OEEF, in which a more toxic and stable epoxide intermediate is generated. However, upon application of OEEF along the intrinsic Mn-O reaction axis, the degradation of BaP into hydroxybenzo[a]pyrene is greatly simplified. The negative charge on the terminal O atom of Mn-OO corrolazine increases with an increase in the OEEF intensity. As the intensity of the OEEF increases over 0.004 a.u., the negatively charged terminal O atom has the ability to directly abstract the positively charged H atom of BaP and the degradation of BaP into hydroxybenzo[a]pyrene can be completed via a one-step process, avoiding the production of more toxic epoxide intermediates.

OEEFs precisely regulating the propane oxidation reaction catalyzed by O–Fe-corrolazine

“…31–40 Due to their unique structural characteristics, high-valent metal corrolazines are widely used in different fields. 41–47 Goldberg's experiments and our theoretical studies indicate that the high-valent O–Mn-corrolazine can oxidize organic substrates directly using O 2 . Recently, our group reported that O–Fe-corrolazine can catalyze methane oxidation under mild conditions through the rebound mechanism and found that the reaction barrier can be effectively regulated by OEEFs.…”

Deciphering structural evolution of adsorbed ˙OH species on Zr-oxo nodes of UiO-66 to modulate methane hydroxylation

“…In contrast, the more Zr oxo -cOOH sites on (cOH) m /UiO-66-H, the lower the activity to produce CH 3 OH is via the rebound reaction. 20,75 The mechanism of H-atom radical/ abstraction methane activation [78][79][80] on Zr-oxo nodes is also proposed (Fig. S6 †).…”

“…Following the cleavage of both the C-H bond of CH 4 and O-the O bond of cOOH* (TS3``), the newly generated cOH quickly rebounds to cCH 3 to form CH 3 OH (P3). [75][76][77] The corresponding potential energy prole indicates that this process requires a relatively high energy barrier of 1.01 eV with an reaction energy of −2.83 eV.…”