The electrochemical reduction of 1-bromo-4-nitrobenzene (p-BrC6H4NO2) at zinc microelectrodes in the [C4mPyrr][NTf2] ionic liquid was investigated via cyclic voltammetry. The reduction was found to occur via an EC type mechanism, where p-BrC6H4NO2 is first reduced by one electron, quasi-reversibly, to yield the corresponding radical anion. The radical anions then react with the Zn electrode to form arylzinc products. Introduction of carbon dioxide into the system led to reaction with the arylzinc species, fingerprinting the formation of the latter. This method thus demonstrates a proof-of-concept of the formation of functionalised arylzinc species.
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http://dx.doi.org/10.1039/c3cp54861a | DOI Listing |
Phys Chem Chem Phys
January 2025
Department of Chemical Engineering, Northeastern University, Boston, Massachusetts, 02115, USA.
Discovering electrocatalysts that can efficiently convert carbon dioxide (CO) to valuable fuels and feedstocks using excess renewable electricity is an emergent carbon-neutral technology. A single metal atom embedded in doped graphene, , single-atom catalyst (SAC), possesses high activity and selectivity for electrochemical CO reduction (COR) to CO, yet further reduction to hydrocarbons is challenging. Here, using density functional theory calculations, we investigate stability and reactivity of a broad SAC chemical space with various metal centers (3d transition metals) and dopants (2p dopants of B, N, O; 3p dopants of P, S) as electrocatalysts for COR to methane and methanol.
View Article and Find Full Text PDFSmall
January 2025
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi, Delhi, 110016, India.
Crystalline γ-FeO(OH) dominantly possessing ─OH terminals (𝛾-FeO(OH)), polycrystalline γ-FeO(OH) containing multiple ─O, ─OH, and Fe terminals (𝛾-FeO(OH)), and α-FeO majorly containing ─O surface terminals are used as electrocatalysts to study the effect of surface terminals on electrocatalytic nitrate reduction reaction (eNORR) selectivity and stabilization of reaction intermediates. Brunauer-Emmett-Teller analysis and electrochemically determined surface area suggest a high active surface area of 117.79 m g (ECSA: 0.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Fudan University, Laboratory of Advanced Materials, Shanghai, 200433, Shanghai, CHINA.
Tellurium (Te), with its rich valence states (-2 to +6), could endow aqueous batteries with potentially high specific capacity. However, achieving complete and stable hypervalent Te0/Te4+ electrochemistry in an aqueous environment poses significant challenges, owing to the sluggish reduction kinetics, the easy dissolution of Te4+ species, and a controversial energy storage mechanism. Herein, for the first time, we demonstrate an amorphous strategy for robust aqueous TeO2/Te electrochemistry.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Tianjin University, Department of Chemistry, #92, Weijin Road, Nankai District, Department of Chemistry, School of Science, Tianjin University, 300072, Tianjin, CHINA.
Electrochemical reductive deuteration of nitriles is a promising strategy for synthesizing deuterated amines with D2O as the deuterated source. However, this reaction suffers from high overpotentials owing to the sluggish D2O dissociation kinetics and high thermodynamic stability of the C≡N triple bond. Here, low-coordinated copper (LC-Cu) is designed to decrease the overpotential for the electrosynthesis of the precursor of Melatonin-d4, 5-methoxytryptamine-d4, by 100 mV with a 68% yield (Faraday efficiency), which is 4 times greater than that of high-coordinated copper (HC-Cu).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
UESTC: University of Electronic Science and Technology of China, School of Materials and Energy, Chengdu, Sichuan, 611731, Chengdu, CHINA.
The electrochemical reduction of carbon dioxide (CO2) to methane (CH4) presents a promising solution for mitigating CO2 emissions while producing valuable chemical feedstocks. Although single-atom catalysts have shown potential in selectively converting CO2 to CH4, their limited active sites often hinder the realization of high current densities, posing a selectivity-activity dilemma. In this study, we developed a single-atom cobalt (Co) doped copper catalyst (Co1Cu) that achieved a CH4 Faradaic efficiency exceeding 60% with a partial current density of -482.
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