Dual Effects of Metal and Organic Ions Co‐Intercalation Boosting the Kinetics and Stability of Hydrated Vanadate Cathodes for Aqueous Zinc‐Ion Batteries

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(31)

Published: June 28, 2023

Abstract For the development of aqueous zinc‐ion batteries, exploiting vanadium‐based cathode materials with quick kinetics and acceptable cycling stability is crucial. Herein, to achieve these goals, transition metal ions (Zn 2+ ) organic (C 5 H 14 ON + Ch are introduced into layered hydrated V 2 O . The intrinsic high conductivity oxygen vacancies generated through ion pre‐intercalation accelerate electrical mobility by optimizing electronic structure. Zn stabilizes structure expanded interlayer spacing improves ionic diffusivity. synergistic effect pre‐intercalated results in 0.1 , )V 4.92 ·0.56H exhibiting a discharge capacity 473 mAh g −1 at A energy efficiency 88% excellent 91% retention after 2000 cycles 4 Ex situ characterizations density functional theory calculations reveal reversible intercalation mechanism improved electrochemical attributed altered reduced binding between host 2−

Language: Английский

---

Transition-Metal-Catalyzed Silylation and Borylation of C–H Bonds for the Synthesis and Functionalization of Complex Molecules

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11619 - 11663

Published: Sept. 26, 2023

The functionalization of C–H bonds in organic molecules containing functional groups has been one the holy grails catalysis. One synthetically important approach to diverse is catalytic silylation or borylation bonds, which enables a broad array downstream transformations afford structures. Advances both undirected and directed methods for transition-metal-catalyzed have led their rapid adoption early-, mid-, late-stage synthesis complex molecules. In this Review, we review application bioactive molecules, materials, ligands. Overall, aim provide picture state art as applied modification architectures that will spur further development these reactions.

Language: Английский

---

Cu-Catalyzed Diastereo- and Enantioselective Synthesis of Borylated Cyclopropanes with Three Contiguous Stereocenters

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

Direct synthesis of enantioenriched scaffolds with multiple adjacent stereocenters remains an important yet challenging task. Herein, we describe a highly diastereo- and enantioselective Cu-catalyzed alkylboration cyclopropenes, less reactive alkyl iodides as electrophiles, for the efficient tetra-substituted borylated cyclopropanes bearing three consecutive stereocenters. This protocol features mild conditions, broad substrate scope, good functional group tolerance, affording array chiral in to high yields excellent enantioselectivities. Detailed mechanistic experiments kinetic studies were conducted elucidate reaction pathway rate-determining step reaction. DFT calculations revealed that π···π stacking interaction between phenyl groups on phosphorus ligand, along smaller distortion CuL-Bpin part, contributed The synthetic utility was showcased by facile some valuable centers.

Language: Английский

---

Simple Ether‐Directed Enantioselective C(sp³)−H Borylation of Cyclopropanes Enabled by Iridium Catalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(14)

Published: Feb. 10, 2023

Reported here is an efficient and simple ether-directed iridium-catalyzed enantioselective C(sp3 )-H borylation of cyclopropanes. Various functional groups were well-tolerated, affording a vast array chiral cyclopropanes with high enantioselectivities. We also demonstrated that the turnover numbers current reaction could be up to 335.

Language: Английский

---

Facile Access to Cyclopropylboronates via Stereospecific Deborylative Cyclization: A Leaving Group‐Assisted Activation of Geminal Diborons

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 24, 2023

Herein we reported a transition metal-free deborylative cyclization strategy, based on which two routes have been developed, generating racemic and enantioenriched cyclopropylboronates. The of geminal-bis(boronates) bearing leaving group was highly diastereoselective, tolerating few functional groups applicable to heterocycles. When optically active epoxides were used as the starting materials, cyclopropylboronates could be efficiently prepared with >99 % stereospecificity. Mechanistic studies showed that at γ-position played crucial role significantly promoted activation gem-diboron moiety.

Language: Английский

---

2-Aminophenanthroline Ligands Enable Mild, Undirected, Iridium-Catalyzed Borylation of Alkyl C–H Bonds

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7124 - 7129

Published: March 8, 2024

The catalytic, undirected borylation of alkyl C–H bonds typically occurs at high reaction temperatures or with excess substrate, both, because the low reactivity bonds. Here we report a new iridium system comprising 2-anilino-1,10-phenanthroline as ligand that catalyzes little to no induction period and rates. This superior activation profile 2-aminophenanthroline-ligated catalysts leads broader scope, including reactions sensitive substrates, such epoxides glycosidic acetals, enhanced diastereoselectivity, higher yields borylated products. These also enable alkanes, amines, ethers room temperature for first time. Mechanistic studies imply facile N-borylation under conditions complexes containing N-boryl aminophenanthrolines are competent precatalysts reaction.

Language: Английский

---

An Iridium/Aluminum Cooperative Strategy for the β‐C(sp³)‐H Borylation of Saturated Cyclic Amines

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: March 29, 2023

Despite the widespread success in functionalization of C(sp2 )-H bonds, deliberate C(sp3 bonds a highly site- and stereoselective manner remains longstanding challenge. Herein, we report an iridium/aluminum cooperative catalytic system that enables β-selective C-H borylation saturated cyclic amines lactams. Furthermore, have accomplished enantioselective variant using binaphthol-derived chiral aluminum catalysts to forge C-B with high levels stereocontrol. Computational studies suggest formation Lewis pair substrates is crucial lower energy transition state for rate-determining reductive elimination step.

Language: Английский

---

Biocatalytic Enantioselective Reduction of Cyclopropenyl Esters and Ketones Using Ene-Reductases

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 6188 - 6193

Published: April 8, 2024

Enantioselective reduction of cyclopropenyl esters and ketones to optically active cyclopropanes has been achieved by using whole-cell-overexpressing ene-reductases (EREDs). By these enzymes, trans-cyclopropanes were isolated in good yield high enantiomeric excess. A wide range cyclopropane obtained, a variety substituent patterns on the cyclopropenes tolerated.

Language: Английский

---

Mechanistic Insights of Zn‐Ion Storage in Synergistic Vanadium‐Based Composites

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(14)

Published: Dec. 22, 2023

Abstract A novel composite material Na 2 V 6 O 16 ·3H O‐Al x 5 (NVO‐AVO) is designed and synthesized for the first time in aqueous zinc ion battery cathode. The electrochemical behavior elucidated detail using situ ex techniques. NVO‐AVO simple, inexpensive, safe to fabricate contributes synergistic effect of orthorhombic Al (AVO) monoclinic (NVO), composites have fast Zn 2+ kinetics exhibit good properties. At 300 mA g −1 , specific capacity as high 392.5 h even more excitingly, remains a 160.6 after 18 cycles at 5000 which significantly better than stability both NVO AVO. distinctive 3 8 layered structure facilitates diffusion structural water located between layers rapid charge transfer by widening gallery spacing supposing storage sites . In addition, forms [AlO ] octahedral units that enhance play crucial role maintaining long‐term cycling stability. This work supports theoretical basis technical support development extension studies new vanadium‐based electrode materials.

Language: Английский

---

Highly Reversible Aqueous Zinc‐Ion Batteries via Multifunctional Hydrogen‐Bond‐Rich Dulcitol at Lower Temperature

Small, Journal Year: 2025, Volume and Issue: 21(11)

Published: Jan. 31, 2025

Abstract Aqueous zinc‐ion batteries (AZIBs) are considered one of the most promising next‐generation energy storage devices due to cost‐effectiveness and high safety. However, uncontrolled dendrite growth intolerance against low temperatures hinder application AZIBs. Herein, hydrogen‐bonding‐rich dulcitol (DOL) is introduced into ZnSO 4 , which reshaped hydrogen‐bond network in electrolyte optimized solvation sheath structure, effectively reducing amount active water molecules inhibiting hydrogen evolution parasitic reaction at zinc anode. In addition, higher adsorption DOL preferentially adsorbs on surface anode, guiding uniform deposition Zn 2+ formation dendrites. also enhances interaction between free improves resistance freeze electrolyte. Consequently, Zn//Zn symmetric cells assembled with extremely stable cycled for 2000 h 2 mA cm −2 . The NH V O 10 (NVO)//Zn full cell showed more excellent specific capacity 183.07 mAh g −1 after 800 cycles. Even temperature −10 °C, still maintains 155.95 600 This work provides a new strategy subsequent study AZIBs stability temperatures.

Language: Английский

---