Supercooled liquid sulfur microdroplets were directly generated from polysulfide electrochemical oxidation on various metal-containing electrodes. The sulfur droplets remain liquid at 155 °C below sulfur's melting point ( = 115 °C), with fractional supercooling change ( - )/ larger than 0.40. light microscopy captured the rapid merging and shape relaxation of sulfur droplets, indicating their liquid nature. Micropatterned electrode and electrochemical current allow precise control of the location and size of supercooled microdroplets, respectively. Using this platform, we initiated and observed the rapid solidification of supercooled sulfur microdroplets upon crystalline sulfur touching, which confirms supercooled sulfur's metastability at room temperature. In addition, the formation of liquid sulfur in electrochemical cell enriches lithium-sulfur-electrolyte phase diagram and potentially may create new opportunities for high-energy Li-S batteries.
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http://dx.doi.org/10.1073/pnas.1817286116 | DOI Listing |
Environ Sci Technol
October 2024
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
The ozone oxidation, or ozonation, of thiosulfate is an important reaction for wastewater processing, where it is used for remediation of mining effluents, and for studying aerosol chemistry, where its fast reaction rate makes it an excellent model reaction. Although thiosulfate ozonation has been studied since the 1950s, challenges remain in developing a realistic reaction mechanism that can satisfactorily account for all observed products with a sequence of elementary reaction steps. Here, we present novel measurements using trapped microdroplets to study the pH-dependent thiosulfate ozonation kinetics.
View Article and Find Full Text PDFJ Am Chem Soc
March 2024
Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, National Observations and Research Station for Wetland Ecosystems of the Yangtze Estuary, IRDR International Center of Excellence on Risk Interconnectivity and Governance on Weather, Department of Environmental Science & Engineering, Fudan University, Shanghai 200433, Peoples' Republic of China.
The multiphase oxidation of sulfur dioxide (SO) to form sulfate is a complex and important process in the atmosphere. While the conventional photosensitized reaction mainly explored in the bulk medium is reported to be one of the drivers to trigger atmospheric sulfate production, how this scheme functionalizes at the air-water interface (AWI) of aerosol remains an open question. Herein, employing an advanced size-controllable microdroplet-printing device, surface-enhanced Raman scattering (SERS) analysis, nanosecond transient adsorption spectrometer, and molecular level theoretical calculations, we revealed the previously overlooked interfacial role in photosensitized oxidation of SO in humic-like substance (HULIS) aerosol, where a 3-4 orders of magnitude increase in sulfate formation rate was speculated in cloud and aerosol relevant-sized particles relative to the conventional bulk-phase medium.
View Article and Find Full Text PDFMater Horiz
March 2024
Lei Zhang, College of Chemistry, Liaoning University, 66 Chongshan Middle Road, Shenyang 110036, P. R. China.
Solar-driven photocatalytic HO production is greatly impeded by the slow mass transfer and rapid recombination of photogenerated charge carriers for multiphase reactions. Polydopamine (PDA)-coated hollow ZnCdS (ZnCdS@PDA) octahedral cages with sulfur vacancies were constructed as micro-reactors to provide a delimited micro-environment for highly efficient paired HO production through water oxidation coupled with oxygen reduction. At neutral pH, hollow ZnCdS@PDA cages exhibited a high HO production yield of 45.
View Article and Find Full Text PDFPNAS Nexus
November 2023
Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, National Observations and Research Station for Wetland Ecosystems of the Yangtze Estuary, IRDR International Center of Excellence on Risk Interconnectivity and Governance on Weather, Department of Environmental Science and Engineering, Fudan University, Shanghai 200433, P. R. China.
The origin of life on Earth is an enigmatic and intricate conundrum that has yet to be comprehensively resolved despite recent significant developments within the discipline of archaeology and geology. Chemically, metal-sulfide minerals are speculated to serve as an important medium for giving birth in early life, while yet so far direct evidence to support the hypothesis for the highly efficient conversion of inorganic carbon into praxiological biomolecules remains scarce. In this work, we provide an initial indication that sphalerite, employed as a typical mineral, shows its enormous capability for promoting the conversion of inorganic carbon into elementary biomolecule formic acid (HCOOH) in airborne mineral-bearing aerosol microdroplet, which is over two orders of magnitude higher than that of the corresponding conventional bulk-like aqueous phase medium in the environment (e.
View Article and Find Full Text PDFJ Am Soc Mass Spectrom
December 2023
"Sapienza" University of Rome, Department of Chemistry and Drug Technologies P.le Aldo Moro 5, 00185 Rome, Italy.
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