Experimental and Computational Study of Pyrogenic Carbonaceous Matter Facilitated Hydrolysis of 2,4-Dinitroanisole (DNAN)

Seenthia, Nourin I.; Bylaska, Eric J.; Pignatello, Joseph J.; Tratnyek, Paul G.; Beal, Samuel A.; Xu, Wenqing

doi:10.1021/acs.est.4c01069

Title: Experimental and Computational Study of Pyrogenic Carbonaceous Matter Facilitated Hydrolysis of 2,4-Dinitroanisole (DNAN)

Journal Article · 13 May 2024 · Environmental Science and Technology

DOI: https://doi.org/10.1021/acs.est.4c01069 · OSTI ID:2447969

Seenthia, Nourin I. ^[1];

^[2];

^[3];

^[4]; Beal, Samuel A. ^[5];

^[1]

Villanova Univ., PA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Connecticut Agricultural Experiment Station, New Haven, CT (United States)
Oregon Health & Science Univ., Portland, OR (United States)
US Army Engineer Research & Development Center, Hanover, NH (United States). Cold Regions Research and Engineering Laboratory (CRREL)

This study investigated the reaction pathway of 2,4-dinitroanisole (DNAN) on the pyrogenic carbonaceous matter (PCM) to assess the scope and mechanism of PCM-facilitated surface hydrolysis. DNAN degradation was observed at pH 11.5 and 25 °C with a model PCM, graphite, whereas no significant decay occurred without graphite. Experiments were performed at pH 11.5 due to the lack of DNAN decay at pH below 11.0, which was consistent with previous studies. Graphite exhibited a 1.78-fold enhancement toward DNAN decay at 65 °C and pH 11.5 relative to homogeneous solution by lowering the activation energy for DNAN hydrolysis by 54.3 ± 3.9%. This is supported by our results from the computational modeling using Car–Parrinello simulations by ab initio molecular dynamics/molecular mechanics (AIMD/MM) and DFT free energy simulations, which suggest that PCM effectively lowered the reaction barriers by approximately 8 kcal mol^–1 compared to a homogeneous solution. Quaternary ammonium (QA)-modified activated carbon performed the best among several PCMs by reducing DNAN half-life from 185 to 2.5 days at pH 11.5 and 25 °C while maintaining its reactivity over 10 consecutive additions of DNAN. We propose that PCM can affect the thermodynamics and kinetics of hydrolysis reactions by confining the reaction species near PCM surfaces, thus making them less accessible to solvent molecules and creating an environment with a weaker dielectric constant that favors nucleophilic substitution reactions. Nitrite formation during DNAN decay confirmed a denitration pathway, whereas demethylation, the preferred pathway in homogeneous solution, produces 2,4-dinitrophenol (DNP). Denitration catalyzed by PCM is advantageous to demethylation because nitrite is less toxic than DNAN and DNP. These findings provide critical insights for reactive adsorbent design that has broad implications for catalyst design and pollutant abatement.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2447969

Report Number(s):: PNNL-SA--198028

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 21 Vol. 58; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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2
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
denitration pathway
pyrogenic carbonaceous matter (PCM)
quaternary ammonium (QA) groups
surface-catalyzed hydrolysis

Title: Experimental and Computational Study of Pyrogenic Carbonaceous Matter Facilitated Hydrolysis of 2,4-Dinitroanisole (DNAN)

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