Issue 13, 2023

Investigating the electrocatalytic reduction of 2,4,6-tri-nitro-toluene (TNT) using density functional theory methods

Abstract

2,4,6-Trinitrotoluene (TNT) degradation is of interest in environmental remediation, demilitarization, and national security. Electrochemical TNT reduction to 2,4,6-triaminotoluene is potentially energy efficient and operable at ambient conditions. Determining an elementary reduction mechanism and rate limiting steps is needed to rationally develop TNT electroreduction catalysts. Density functional theory methods determine the TNT reduction mechanism for non-catalyzed and late-transition metal catalyzed paths. The non-catalyzed mechanism is limited by slow initial NO2 group reduction. The outer-sphere mechanism is more competitive to electrocatalytic reduction on Au (111) and Fe (110) surfaces, which wasn't observed in our previous work on nitrobenzene electroreduction. An inverse tradeoff between the initial reduction of the NO2-R* group and reduction of surface hydroxyls suggests relative catalytic activity can be tuned by modulating O* affinity. Metal surfaces with intermediate O* affinity (Cu, Pt, Pd, and Ir) are predicted to be the most active late transition-metals towards TNT reduction. We extend our investigation to bimetallics and partially reduced Fe2O3 (0001) surfaces.

Graphical abstract: Investigating the electrocatalytic reduction of 2,4,6-tri-nitro-toluene (TNT) using density functional theory methods

Supplementary files

Article information

Article type
Paper
Submitted
09 apr 2023
Accepted
19 may 2023
First published
25 may 2023

Green Chem., 2023,25, 5097-5112

Author version available

Investigating the electrocatalytic reduction of 2,4,6-tri-nitro-toluene (TNT) using density functional theory methods

A. J. Wong, J. L. Miller, B. Perdue and M. J. Janik, Green Chem., 2023, 25, 5097 DOI: 10.1039/D3GC01144E

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