Polar discontinuities and redox reactions provide alternative paths to create two-dimensional electron liquids (2DELs) at oxide interfaces. Herein, we report high mobility 2DELs at interfaces involving SrTiO (STO) achieved using polar LaSrMnO (LSMO) buffer layers to manipulate both polarities and redox reactions from disordered overlayers grown at room temperature. Using resonant X-ray reflectometry experiments, we quantify redox reactions from oxide overlayers on STO as well as polarity induced electronic reconstruction at epitaxial LSMO/STO interfaces. The analysis reveals how these effects can be combined in a STO/LSMO/disordered film trilayer system to yield high mobility modulation doped 2DELs, where the buffer layer undergoes a partial transformation from perovskite to brownmillerite structure. This uncovered interplay between polar discontinuities and redox reactions via buffer layers provides a new approach for the design of functional oxide interfaces.
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http://dx.doi.org/10.1021/acs.nanolett.7b03744 | DOI Listing |
Inorg Chem
January 2025
Testing and Analysis Center, Hebei Normal University, Shijiazhuang 050024, China.
The bipyridyl tantalum complex (2,6-PrCHO)Ta(bipy) () is synthesized by the reaction of (2,6-PrCHO)TaCl () and 2,2'-bipyridine in the presence of excess potassium graphite (KC). Complex coordinates readily with pyridine and 4-(dimethylamino)pyridine (dmap) to form Lewis base adducts (2,6-PrCHO)Ta(bipy)(L) (L = py (), dmap ()), and it exhibits rich redox reactivity toward small molecules: (a) single electron transfer (SET) occurs upon exposure of to phenyl sulfide or selenide dimer, giving the open-shell, bipy-centered radical complexes (2,6-PrCHO)Ta(bipy)(PhE) (E = S (), Se ()). (b) Regioselective C-C σ-bond formation via radical coupling is observed in the SET reaction of and aldehydes, ketones, or imines to furnish insertion products -, namely, sterically more crowded benzophenone, acetophenone, 2,6-dichlorobenzaldehyde, and benzophenone imine couple with C6 or C6' of bipy in , respectively, whereas sterically less hindered benzaldehyde, cyclohexanone, and benzylideneaniline couple with C2 or C2' of bipy, respectively.
View Article and Find Full Text PDFRedox Biochem Chem
December 2024
Department of Biophysics, Medical College of Wisconsin, Milwaukee, United States.
Peroxynitrite (ONOO/ONOOH) is a short-lived but highly reactive species that is formed in the diffusion-controlled reaction between nitric oxide and the superoxide radical anion. It can oxidize certain biomolecules and has been considered as a key cellular oxidant formed under various pathophysiological conditions. It is crucial to selectively detect and quantify ONOO to determine its role in biological processes.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Hangzhou International Innovation Institute, Beihang University, Hangzhou, 311115, P. R. China.
In sodium-ion batteries, the layered transition metal oxides used as cathode often experience interlayer sliding of interlayer spacing and lattice variations during charge/discharge, leading to structural damage and capacity degradation. To address this challenge, a La doping strategy guided by Bayesian optimization has been employed to prepare the high-performance O3-NaNiMnCuLaO (NMCL) cathode material. Density functional theory calculations reveal that the O 2p orbital overlaps with the t orbital of transition metals in NMCL, facilitating the formation of Na-O-La bonds and promoting the oxygen redox reaction kinetics.
View Article and Find Full Text PDFNature
January 2025
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA.
High-throughput experimentation (HTE) has accelerated academic and industrial chemical research in reaction development and drug discovery and has been broadly applied in many domains of organic chemistry. However, application of HTE in electrosynthesis-an enabling tool for chemical synthesis-has been limited by a dearth of suitable standardized reactors. Here we report the development of microelectronic devices, which are produced using standard nanofabrication techniques, to enable wireless electrosynthesis on the microlitre scale.
View Article and Find Full Text PDFNat Commun
January 2025
Department of Materials Science and Engineering, City University of Hong Kong, 83 Tat Chee Avenue, Hong Kong SAR, China.
The growing potential of low-dimensional metal-halide perovskites as conversion-type cathode materials is limited by electrochemically inert B-site cations, diminishing the battery capacity and energy density. Here, we design a benzyltriethylammonium tellurium iodide perovskite, (BzTEA)TeI, as the cathode material, enabling X- and B-site elements with highly reversible chalcogen- and halogen-related redox reactions, respectively. The engineered perovskite can confine active elements, alleviate the shuttle effect and promote the transfer of Cl on its surface.
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