Molecular Descriptor for Catalytic Direct Oxidative Transfer Process Based on Thermodynamic State Changes during...

Area of Science:

• Environmental Chemistry
• Catalysis
• Water Treatment

Background:

• Direct oxidative transfer process (DOTP) in heterogeneous catalytic persulfate oxidation (HCPO) is crucial for pollutant degradation.
• Existing molecular descriptors often lack strong correlation with reactivity and mechanisms due to reliance on static properties.

Purpose of the Study:

• To develop novel molecular descriptors based on molecular thermodynamic state changes for improved prediction of reaction rates in HCPO.
• To elucidate the DOTP mechanism in a carbon nanotube/persulfate system and validate the new descriptor's efficacy.

Main Methods:

• Proposed a new descriptor, ΔE2e1p, representing energy change during electron and proton loss.
• Utilized multiscale characterizations to investigate the DOTP mechanism.
• Correlated descriptor values with reaction rates for phenolic and amine pollutants.

Main Results:

• The ΔE2e1p descriptor showed a strong correlation (R² = 0.938) with pollutant reaction rates.
• Demonstrated the critical role of pollutant proton transfer in the DOTP mechanism.
• Validated the broad applicability of ΔE2e1p across various HCPO systems and real water matrices.

Conclusions:

• Molecular thermodynamic state changes provide superior descriptors for HCPO reactivity compared to static properties.
• The ΔE2e1p descriptor offers a practical tool for predicting and optimizing catalytic oxidation processes for water remediation.