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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(12), С. 8576 - 8584

Опубликована: Март 15, 2024

Spraying water microdroplets containing 1,2,3-triazole (Tz) has been found to effectively convert gas-phase carbon dioxide (CO2), but not predissolved CO2, into formic acid (FA). Herein, we elucidate the reaction mechanism at molecular level through quantum chemistry calculations and ab initio dynamics (AIMD) simulations. Computations suggest a multistep that initiates from adsorption of CO2 by Tz form CO2-Tz complex (named reactant (RC)). Then, RC either is reduced electrons were generated air–liquid interface microdroplet then undergoes intramolecular proton transfer (PT) or switches reduction PT steps [HCO2-(Tz-H)]− PC–). Subsequently, PC– C–N bond dissociates generate COOH– [Tz-H]− (m/z = 69). easily converts HCOOH captured m/z 45 in mass spectroscopy. Notably, step can be significantly lowered oriented electric field water-bridge mechanism. The further confirmed testing multiple azoles. AIMD simulations reveal novel where serves as transporter shown play an important role dynamically. Moreover, transient •COOH experiment proposed partly formed with H•, pointing again importance air–water interface. This work provides valuable insight mechanistic, kinetic, dynamic features converting products azoles amines dissolved microdroplets.

Язык: Английский

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

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 11, 2024

Abstract Organic-inorganic interactions regulate the dynamics of hydrocarbons, water, minerals, CO 2 , and H in thermal rocks, yet their initiation remains debated. To address this, we conducted isotope-tagged in-situ visual experiments. Isotope-tagged studies revealed extensive H/O transfers hydrous n -C 20 42 -H O-feldspar systems. Visual experiments observed water microdroplets forming at 150–165 °C oil phases near 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 propose a two-fold mechanism: water-derived n- C -derived drive organic species, while mineral-derived ions trigger mineral interactions. These processes, facilitated by bulk blur boundaries between inorganic enabling mass transfer. Our findings redefine microscopic interplays components, offering insights into diagenetic hydrous-metamorphic transfer cycles deep basins subduction zones.

Язык: Английский

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Catalyst-free selective oxidation of C(sp3)-H bonds in toluene on water

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июль 20, 2024

Abstract The anisotropic water interfaces provide an environment to drive various chemical reactions not seen in bulk solutions. However, catalytic by the aqueous are still their infancy, with emphasis being on reaction rate acceleration water. Here, we report that oil-water interface activates and oxidizes C(sp 3 )-H bonds toluene, yielding benzaldehyde high selectivity (>99%) conversion under mild, catalyst-free conditions. Collision at between oil-dissolved toluene hydroxyl radicals spontaneously generated near water-side is responsible for unexpectedly selectivity. Protrusion of free OH groups from interfacial destabilizes transition state OH-addition forming π-hydrogen while H-abstraction remains unchanged effectively activate bonds. Moreover, exposed form hydrogen produced benzaldehyde, suppressing it overoxidized. Our investigation shows has considerable promise chemoselective redox without any catalysts.

Язык: Английский

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Direct Conversion of N₂ and Air to Nitric Acid in Gas–Water Microbubbles

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 24, 2024

We report a simple, direct, and green conversion of air/N

Язык: Английский

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Lignosulfonate‐Derived Conducting Organohydrogel as Anisotrpic Bioadhesive for Motion‐Artifact‐Free Epidermal Bioelectronics

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Авг. 20, 2024

Abstract Gel‐based adhesives show promising prospects in epidermal bioelectronics because of their potential applications physiological signal collection and electrical stimulation. An ideal adhesive should exhibit robust adhesion for lamination poor easy peeling, addition to strain‐insensitivity properties motion‐artifact‐free collection. Here, lignosulfonate‐derived organohydrogel with anisotropic tunable adhesion, together unprecedented are synthesized. The exhibits a high interfacial toughness 728 J m −2 on fresh porcine skin, while the can be screened by covering denatured silk fibroin. an heterogeneity is designed, showing 14.2‐fold difference strength along two different directions on‐demand attachment removal. transform into highly porous structure, which has only 3% resistance increase at 100% strain. lies strong interaction ions 3D enables high‐quality electrophysiological within strain range human skin. expected used bioelectronics, human‐machine interaction, metaverse, beyond.

Язык: Английский

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

Chemical Communications, Год журнала: 2024, Номер 60(25), С. 3449 - 3452

Опубликована: Янв. 1, 2024

Steel industry waste-derived rod-like Fe 3 O 4 -NPs were used for thermo-catalytic reduction of CO 2 to acetic acid in aqueous-H medium. H facilitates the reaction by generating high concentrations OH˙ and +/ ˙, supporting yield.

Язык: Английский

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Mild Diarylmethylation of Indoles through Regioselective 1,6-Hydroarylation of para-Quinone Methides in Microdroplets/Thin Film

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(25), С. 9522 - 9533

Опубликована: Июнь 13, 2024

Язык: Английский

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Heavy Water Microdroplet Surface Enriches the Lighter Isotopologue Impurities

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19050 - 19058

Опубликована: Июль 3, 2024

Water microdroplets promote unusual chemical reactions at the air-water interface. However, interfacial structure of water and its potential influence on processes are still enigmatic. Here, we present evidence in-droplet fractionation isotopologues. Employing a sonic spray, atomized heavy (D

Язык: Английский

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Boosting Reactive Oxygen Species Generation via Contact‐Electro‐Catalysis with Fe^III‐Initiated Self‐cycled Fenton System

Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(1)

Опубликована: Авг. 22, 2024

Contact Electro-Catalysis (CEC) using commercial dielectric materials in contact-separation cycles with water can trigger interfacial electron transfer and induce the generation of reactive oxygen species (ROS). However, inherent hydrophobicity limits effective reaction sites, generated ROS inevitably undergo self-combination to form hydrogen peroxide (H

Язык: Английский

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Oxidation of Ammonia in Water Microdroplets Produces Nitrate and Molecular Hydrogen

Environmental Science & Technology, Год журнала: 2024, Номер 58(36), С. 16196 - 16203

Опубликована: Авг. 23, 2024

Water microdroplets containing dissolved ammonia (30–300 μM) are sprayed through a copper oxide mesh with 200 μm average pore size, resulting in the formation of nitrate (NO3–) and release molecular hydrogen (H2). The products result from redox process that takes place at liquid–solid interface contact electrification, where no external potential is applied. Oxidation initiated by superoxide radical anions (O2–) originate oxygen air surrounding hydroxyl radicals (OH•) originating water–air interface. Two spin traps (TEMPO DMPO) capture these as well NH2OH+•, HNO, NO•, NO2•, NOOH, which detected mass spectrometry. We also directly observed N2O2–• same means. found atom molecule can be set free not only form H• but H2, using residue gas analyzer. oxidation significantly enhanced factor 3 when irradiated ultraviolet light (265 nm, 5 W). 35% 300 μM degraded within 20 μs, conversion rate estimated to 15 nmol·mg–1·h–1.

Язык: Английский

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