Electrochemical reactions are normally initiated in solution by metal electrodes such as Pt, which are expensive and limited in supply. In this Communication, we demonstrate that an atmospheric-pressure microplasma can act as a gaseous, metal-free electrode to mediate electron-transfer reactions in aqueous solutions. Ferricyanide is reduced to ferrocyanide by plasma electrons, and the reduction rate is found to depend on discharge current. The ability to initiate and control electrochemical reactions at the plasma-liquid interface opens a new direction for electrochemistry based on interactions between gas-phase electrons and ionic solutions.
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http://dx.doi.org/10.1021/ja207547b | DOI Listing |
Angew Chem Int Ed Engl
January 2025
University of Bari: Universita degli Studi di Bari Aldo Moro, Dept. of Pharmacy - Drug Sciences, via E. Orabona 4, 70125, Bari, ITALY.
Strained spiro-heterocycles (SSH) have gained significant attention within the medicinal chemistry community as promising (sp3)-rich bioisosteres for their aromatic and non-spirocyclic counterparts. We herein report access to an unprecedented spiro-heterocycle - 1,5-dioxaspiro[2.3]hexane.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Northeastern University, Corrosion and Protection Center, NO. 3-11, Wenhua Road, Heping District, Shenyang, P. R. China, Shenyang, CHINA.
The dense passive film on 316L stainless steel is the key in its corrosion resistance. Its interactions with an electroactive biofilm are critical in deciphering microbial corrosion. Herein, an in-depth investigation using genetic manipulations and addition of an exogenous electron mediator found that extracellular electron transfer (EET) mediated by the electroactive S.
View Article and Find Full Text PDFChemSusChem
January 2025
Universita degli Studi di Ferrara, Dipartimento di Scienze Chimiche e Farmaceutiche, Via Borsari 46, 44121, Ferrara, ITALY.
Direct photochemical conversion of CO2 into a single carbon-based product currently represents one of the major issues in the catalysis of the CO2 reduction reaction (CO2RR). In this work, we demonstrate that the combination of an organic photosensitizer with a heptacoordinated iron(II) complex allows to attain a noble-metal-free photochemical system capable of efficient and selective conversion of CO2 into CO upon light irradiation in the presence of N,N-diisopropylethylamine (DIPEA) and 2,2,2-trifluoroethanol (TFE) as the electron and proton donor, respectively, with unprecedented performances (ΦCO up to 36%, TONCO > 1000, selectivity > 99%). As shown by transient absorption spectroscopy studies, this can be achieved thanks to the fast rates associated with the electron transfer from the photogenerated reduced dye to the catalyst, which protect the dye from parallel degradation pathways ensuring its stability along the photochemical reaction.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
School of Chemistry and Chemical Engineering, Yangzhou University, Siwangting Road 180, 225002, Yangzhou, China.
As fundamental structural scaffolds in numerous natural products and pharmaceutical molecules, the construction of cyclohexenone architectures has remained a pivotal focus in organic chemistry. However, established strategies to synthesize cyclohexenone derivatives Dowd-Beckwith ring-expansion reaction invariably involve the use of transition metals and photoirradiation. Herein, we present a novel transition-metal- and photoirradiation-free pathway to access such structures from α-iodomethyl β-keto esters with electron-rich arenediazonium salts as inexpensive radical initiators and oxidants under mild reaction conditions.
View Article and Find Full Text PDFACS Phys Chem Au
January 2025
University of Duisburg-Essen, Faculty of Chemistry, Theoretical Catalysis and Electrochemistry, Universitätsstraße 5, Essen 45141, Germany.
The direct conversion of dinitrogen to nitrate is a dream reaction to combine the Haber-Bosch and Ostwald processes as well as steam reforming using electrochemistry in a single process. Regrettably, the corresponding nitrogen oxidation (NOR) reaction is hampered by a selectivity problem, since the oxygen evolution reaction (OER) is both thermodynamically and kinetically favored in the same potential range. This opens the search for the identification of active and selective NOR catalysts to enable nitrate production under anodic reaction conditions.
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