Water Microdroplets-Initiated Methane Oxidation

Song, Xiaowei; Basheer, Chanbasha; Zare, Richard N.

doi:10.1021/jacs.3c08643

Cited by 10 publications

(11 citation statements)

References 56 publications

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“…Alternatively, the H• radical may participate in the process, for the reaction OH – + H 3 O + → •OH + H• + H 2 O is spontaneous in the gas phase (Δ G = −117.1 kcal/mol) and is possible at the surface of a water droplet (estimated to be −21.6 kcal/mol, Table ). There are both direct and indirect pieces of experimental evidence confirming the existence of H• and •OH radicals at the surface of the water microdroplets. ,,,− So, the association of CO 2 and H• to form •COOH was checked and was found to be possible. The calculated association energy was −6.3 kcal/mol in the aqueous phase and 3.6 kcal/mol in the gas phase.…”

Section: Resultsmentioning

confidence: 99%

Molecular Mechanism for Converting Carbon Dioxide Surrounding Water Microdroplets Containing 1,2,3-Triazole to Formic Acid

Gong,

Meng,

Zare

et al. 2024

J. Am. Chem. Soc.

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Spraying water microdroplets containing 1,2,3-triazole (Tz) has been found to effectively convert gas-phase carbon dioxide (CO 2 ), but not predissolved CO 2 , into formic acid (FA). Herein, we elucidate the reaction mechanism at the molecular level through quantum chemistry calculations and ab initio molecular dynamics (AIMD) simulations. Computations suggest a multistep reaction mechanism that initiates from the adsorption of CO 2 by Tz to form a CO 2 -Tz complex (named reactant complex (RC)). Then, the RC either is reduced by electrons that were generated at the air−liquid interface of the water microdroplet and then undergoes intramolecular proton transfer (PT) or switches the reduction and PT steps to form a [HCO 2 -(Tz-H)] − complex (named PC − ). Subsequently, PC − undergoes reduction and the C−N bond dissociates to generate COOH − and [Tz-H] − (m/z = 69). COOH − easily converts to HCOOH and is captured at m/z = 45 in mass spectroscopy. Notably, the intramolecular PT step can be significantly lowered by the oriented electric field at the interface and a water-bridge mechanism. The mechanism is further confirmed by testing multiple azoles. The AIMD simulations reveal a novel proton transfer mechanism where water serves as a transporter and is shown to play an important role dynamically. Moreover, the transient •COOH captured by the experiment is proposed to be partly formed by the reaction with H•, pointing again to the importance of the air−water interface. This work provides valuable insight into the important mechanistic, kinetic, and dynamic features of converting gas-phase CO 2 to valuable products by azoles or amines dissolved in water microdroplets.

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Section: Resultsmentioning

confidence: 99%

Molecular Mechanism for Converting Carbon Dioxide Surrounding Water Microdroplets Containing 1,2,3-Triazole to Formic Acid

Gong,

Meng,

Zare

et al. 2024

J. Am. Chem. Soc.

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“…2e. The produced MeOH in the presence of H˙ can further form a CH 3 ˙ intermediate, 20 which on further reaction with MeOH forms EtOH (confirmed by 1 H NMR) and finally EtOH reacts with ˙OH radicals to produce AcOH (EtOH oxidation pathway). 32 Then the CO reacts with MeOH directly to form AcOH (MeOH carbonylation pathway).…”

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confidence: 93%

“…The presence of CO, MeOH, and EtOH after the reaction supports their significance as intermediates in the selective synthesis of AcOH. 20…”

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confidence: 99%

“…S3, ESI†) and the recent literature. 20,26–32 CO 2 reduction proceeds via two sub-part mechanisms; the first part includes generation of various reactive species and radicals in the presence of H 2 O 2 and Fe 3 O 4 -NPs (Fenton reactions), and thereafter utilization of these reactive species in the formation of AcOH, simultaneously in the second part. It is well-known that H 2 O 2 decomposes into multiple reactive species (HO˙–˙OH, H˙–˙OOH and H + –HO 2 − ) in the presence of iron-based catalysts (Fe 3 O 4 -NP here) and energy (thermal here).…”

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Fenton-mediated thermocatalytic conversion of CO₂ to acetic acid by industrial waste-derived magnetite nanoparticles

Kaushik,

Lamba,

Kumar

et al. 2024

Chem. Commun.

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“…They produce hydroxyl radicals and hydrogen peroxide 25 – 31 , facilitating the acceleration of organic reactions 32 – 34 , all without requiring additional catalysts. Chen et al 27 and Song et al 30 also reported the initiation of accelerated alkane degradation by contact of different alkanes with man-made water microdroplets at room temperature. However, non-catalytic interactions in thermal hydrous systems are still a matter of debate in the geochemical community 5 , 35 .…”

Section: Introductionmentioning

confidence: 98%

Microdroplets initiate organic-inorganic interactions and mass transfer in thermal hydrous geosystems

Yuan,

Jin,

Cao

et al. 2024

Nat Commun

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Organic-inorganic interactions regulate the dynamics of hydrocarbons, water, minerals, CO2, and H2 in thermal rocks, yet their initiation remains debated. To address this, we conducted isotope-tagged and in-situ visual thermal experiments. Isotope-tagged studies revealed extensive H/O transfers in hydrous n-C20H42-H2O-feldspar systems. Visual experiments observed water microdroplets forming at 150–165 °C in oil phases near the water-oil interface without surfactants, persisting until complete miscibility above 350 °C. Electron paramagnetic resonance (EPR) detected hydroxyl free radicals concurrent with microdroplet formation. Here we propose a two-fold mechanism: water-derived and n-C20H42-derived free radicals drive interactions with organic species, while water-derived and mineral-derived ions trigger mineral interactions. These processes, facilitated by microdroplets and bulk water, blur boundaries between organic and inorganic species, enabling extensive interactions and mass transfer. Our findings redefine microscopic interplays between organic and inorganic components, offering insights into diagenetic and hydrous-metamorphic processes, and mass transfer cycles in deep basins and subduction zones.

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Water Microdroplets-Initiated Methane Oxidation

Cited by 10 publications

References 56 publications

Molecular Mechanism for Converting Carbon Dioxide Surrounding Water Microdroplets Containing 1,2,3-Triazole to Formic Acid

Molecular Mechanism for Converting Carbon Dioxide Surrounding Water Microdroplets Containing 1,2,3-Triazole to Formic Acid

Fenton-mediated thermocatalytic conversion of CO₂ to acetic acid by industrial waste-derived magnetite nanoparticles

Microdroplets initiate organic-inorganic interactions and mass transfer in thermal hydrous geosystems

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Water Microdroplets-Initiated Methane Oxidation

Cited by 10 publications

References 56 publications

Molecular Mechanism for Converting Carbon Dioxide Surrounding Water Microdroplets Containing 1,2,3-Triazole to Formic Acid

Molecular Mechanism for Converting Carbon Dioxide Surrounding Water Microdroplets Containing 1,2,3-Triazole to Formic Acid

Fenton-mediated thermocatalytic conversion of CO2 to acetic acid by industrial waste-derived magnetite nanoparticles

Microdroplets initiate organic-inorganic interactions and mass transfer in thermal hydrous geosystems

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Product

Resources

About

Fenton-mediated thermocatalytic conversion of CO₂ to acetic acid by industrial waste-derived magnetite nanoparticles