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Lithium-oxygen batteries (LOBs) have received much research interest owing to their ultra-high energy density, but their further development is restricted by the erosion of the Li anode, the degradation of the electrolyte, and especially the sluggish oxygen-involving reactions on the cathode. To facilitate the oxidation of discharge products, halide redox mediators (HRMs), a subclass of soluble additives, have been explored to promote their decomposition. Meanwhile, some other intriguing functions were discovered, like protecting the Li anode and redirecting the discharge pathway to form LiOH. In this Review, after a brief introduction of LOBs and HRMs, the various functions of HRMs, not limited to promoting the oxidation of discharge products, are discussed and summarized. In addition, the challenges and controversies confronted by HRMs in LOBs are highlighted and the future opportunities of HRMs for achieving better LOBs are proposed.
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http://dx.doi.org/10.1021/cbe.4c00025 | DOI Listing |
Inorg Chem
September 2025
Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot 7610001, Israel.
The low-temperature oxidation of alkanes and arenes using molecular oxygen under ambient conditions is still one of the grand challenges of catalysis. Inspired by the alkane hydroxylation activity of the copper-based metalloenzyme, particulate methane monooxygenase, a tetra-copper polyoxometalate, [Cu(HO)(PWO)], was investigated as an electrocatalyst for the cathodic (reductive) oxidation of hydrocarbons with emphasis on oxidation of ethane. Controlled potential electrolysis (CPE) in water at -0.
View Article and Find Full Text PDFWhile organic dye-based photoredox catalysis provides a sustainable platform for inert bond activation, its efficiency remains limited by detrimental back electron transfer (BET) processes. Herein, we present a spin catalysis strategy that addresses this challenge by manipulating the spin kinetics of radical ion pairs (RIPs) using Gd-DOTA as a spin catalyst. In photocatalytic hydrodechlorination of methyl 4-chlorobenzoate, this approach achieved a remarkable spin catalysis effect (SCE) of 70%, accompanied by a 25-fold acceleration in reaction kinetics (65% conversion in 25 min 640 min without spin catalyst).
View Article and Find Full Text PDFNanomicro Lett
September 2025
School of Microelectronics, Northwestern Polytechnical University, Xi'an, 710129, People's Republic of China.
Metal halide perovskites (MHPs) with striking electrical and optical properties have appeared at the forefront of semiconductor materials for photocatalytic redox reactions but still suffer from some intrinsic drawbacks such as inferior stability, severe charge-carrier recombination, and limited active sites. Heterojunctions have recently been widely constructed to improve light absorption, passivate surface for enhanced stability, and promote charge-carrier dynamics of MHPs. However, little attention has been paid to the review of MHPs-based heterojunctions for photocatalytic redox reactions.
View Article and Find Full Text PDFSmall
August 2025
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Kolkata, 741246, India.
Vacancy-ordered Bi-based perovskites, such as CsBiBr (CBB), exhibit relatively high Lewis acidity due to Bi⁺ centers, providing favorable acidic sites for organic transformations. Coupled with their tuneable optoelectronic properties, these features render CBB an efficient photocatalyst for various acid-catalyzed reactions. In this study, CBB is conjugated with a classical Ru(II)-polypyridyl photosensitizer (RuPS) to form a hybrid material, CBB/RuPS, capable of facilitating thermodynamically favourable inner-sphere electron transfer.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University, Tianjin 300387, P. R. China.
We report herein an Fe-catalyzed asymmetric reductive cross-coupling of carbonyl-containing ketimines with unactivated alkyl halides, enabling the efficient synthesis of enantioenriched α-tertiary amino esters and amides. This transformation is promoted by a commercially available iron(II) triflate catalyst in combination with a chiral bisoxazoline-phosphine (NPN) ligand and inexpensive manganese as the reductant. A broad range of primary and secondary alkyl iodides are compatible, affording the desired products in high yields with excellent enantioselectivities and exceptional functional group tolerance.
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