The performance of aqueous zinc-iodine batteries (AZIBs) has historically been limited by poor iodine infiltration and slow reaction kinetics at the I2 cathode. To address these issues, developing an effective cathode host that can achieve both high iodine loading and rapid redox kinetics has become a pivotal challenge in the field. In this study, a porphyrin-based covalent organic framework (COF366) was synthesized with tunable in-wall functional groups, which served as an iodine host. The hydroxyl-functionalized version of COF366, designated as COF366-OH, demonstrated a remarkable iodine loading capacity of 52 wt %. This high ratio can be credited to a combination of mechanisms, including physical confinement of iodine and favorable Lewis acid-base interactions with the framework. The resultant synergy from these interactions not only improved iodine immobilization but also reduced voltage polarization and sped up the redox conversion process. As a result, the COF366-OH/I2 cathode exhibited an impressive specific capacity of 157 mAh g-1 after 500 cycles. This performance surpassed that of the pristine COF366, highlighting significant improvements in both rate capability and cycling stability. In situ Raman spectroscopy analyses indicated that I5- was the primary oxidation product formed during the discharge process, which aligns with the strong binding energy observed between COF366-OH and I5-. This robust interaction not only stabilized the I5- species but also effectively mitigated the shuttle effect, thus contributing to a longer cycling life and improved charge-transfer kinetics. This research illustrates a synergistic approach through structural modifications in order to boost the performance of iodine species in AZIBs, showcasing the potential benefits of tailored COFs in energy storage applications.

Activating four-electron iodine chemistry in zinc-iodine (Zn-I2) batteries promises higher energy density, yet remains challenged by polyiodide shuttling and the instability of high-valence I+ species. Here, we demonstrate that a customized NH4Cl-based aqueous electrolyte, coupled with an ion-replenishing Cl-functionalized covalent organic framework (COF-Cl) interlayer, enables long-lived four-electron Zn-I2 batteries. The optimized electrolyte promotes I+-Cl- complexation, while the COF-Cl interlayer immobilizes polyiodides and continuously releases Cl- to stabilize I+ against hydrolysis, collectively ensuring reversible I-/I0/I+ redox conversion. In situ spectroscopic and theoretical analyses reveal accelerated high-valence redox kinetics and strong I+/polyiodide interactions. As a result, the optimized cell delivers high energy density (278 Wh kg- 1), fast kinetics (128 mAh g- 1 at 10 A g- 1), and remarkable cycling durability over 45000 cycles at -5°C with an ultralow decay rate of 0.00039% per cycle, with the strategy further validated in pouch cells under low-temperature conditions. This work establishes an effective ion-replenishing interlayer-electrolyte strategy for robust, high-energy aqueous Zn-I2 batteries.

Manganese-based Prussian blue analogues (MnFePBAs), renowned for their high redox potential and dual redox-active sites, often fail to fully realize their intrinsic performance in zinc-ion batteries (ZIBs). In this work, the underlying causes of the instability of monoclinic K+-containing MnFePBA (KMnFePBA) cathodes in aqueous electrolytes were investigated. To prevent irreversible phase transitions, a lowconcentration, flame-retardant organic electrolyte operable under open-air conditions was developed. Utilizing triethyl phosphate (TEP) as the electrolyte solvent, the KMnFePBA cathode exhibited two distinct redox peaks at approximately 1.83 and 1.70 V, coupled with a high reversible capacity of similar to 130 mA h g-1. The TEP electrolyte offers not only flame-retardant and anti-drying properties but also benefits from the inclusion of trace amounts of water, which enhances the redox kinetics. The optimized electrolyte enables Zn||KMnFePBA batteries to operate reversibly without structural degradation, function effectively across a wide temperature range, and suppress Zn dendrite formation by modulating the zinc-ion solvation structure and interfacial environment. This study presents a practical electrolyte engineering strategy for stabilizing monoclinic MnFePBA cathodes while simultaneously extending the lifespan of Zn anodes in ZIBs. (c) 2025 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Regioselective functionalization of arene C-H bonds stands as a forefront research area in modern synthetic organic chemistry. Among such transformations, C-H allylation represents a fundamentally important strategy for forging C-C bonds, with broad utility in the assembly of structurally diverse organic molecules. Herein, we disclose an unprecedented copper(II)-catalyzed protocol for the ortho-selective C-H allylation of tertiary anilines using unprotected allyl alcohols as alkylating agents. Remarkably, this reaction proceeds without external ligands, additives, or stoichiometric oxidants, thus minimizing synthetic waste and streamlining operational complexity. This reaction tolerated various substituted tertiary anilines and allyl alcohols, affording the corresponding ortho allylation products in moderate to good yields. The reactions were effectively scaled up, affording the corresponding allylation products in good yields. Preliminary mechanistic studies suggest a catalytic cycle involving a π-allylcopper intermediate. This method provides a cost-effective, atom-economical alternative to precious metal-catalyzed allylation reactions.

A facile method for the para selective C–H alkylation of tertiary anilines with cyclopropanol has been developed. By simply tuning the reaction parameters, two distinct product classes, namely phenylpropanoid carbonyls...

In spite of the valuable perspective on rapid accessing α,α-disubstituted α-amino acid derivatives, a three-component reaction of diazo compounds, amines and allyl esters remains as an unexplored challenge, probably because of the fore-seeable side reactions arising from each two reactants. In this work, we describe a novel Xantphos-containing dinuclear palladium complex enabled geminal aminoallylation of diazocarbonyl compounds, which provides a range of quaternary α-amino esters selectively. Direct N-H insertion, allylic alkylation of amino nucleophiles and diene formation were not observed under standard conditions. Mechanistic studies indicated that the Xantphos-containing palladium complex with a Pd/P ratio of 1/1 was optimal to enable the reaction to achieve high selectivity. A relayed pathway via allylation of N-H insertion product or [2,3]-sigmatropic rearrangement of a ylide intermediate was unlikely. We believe that the current strategy on palladium-catalyzed selective carbene difunctionalization could be general to construct quaternary carbon centers, and inspire more transformations in related field.

Nitro groups' high redox activity and electron-withdrawing capabilities increased the specific capacity and voltage plateaus. Additionally, the in situ produced azo bridges increased the conjugation of PTO and hence improved the cycle stability.

Sulfur was typically regarded as a poison to precious metal complex catalysts in hydroformylation of olefins. However, the combination of sulfur and phosphine may present an intriguing interaction with heterogeneous mononuclear complex due to the difference of their electronegativities, and coordination capabilities. Herein, we report a novel sulfur-phosphine co-coordinated heterogeneous Rh mononuclear complex catalyst (Rh1/POPs-PPh3&S), which exhibits an unexpected 1.5-2.0 times catalytic activity for hydroformylation of olefins (C3=, C5=-C8=), in comparison with the solely phosphine-coordinated Rh mononuclear complex catalyst (Rh1/POPs-PPh3). In contrast, sulfur coordination alone leads to severe sulfur poisoning with significantly inhibited catalytic performance. Experimental and theoretical analyses reveal that phosphine coordination promotes catalytic activity via its strong electron-donating ability, while sulfur occupies a coordination site and reduces the electronic density of Rh ions. The synergistical coordination of sulfur and phosphine optimizes the electronic density of active Rh ions and decreases the energy barrier of the rate-determining step of olefin insertion, thus enhancing the hydroformylation activity, regioselectivity and stability of Rh1/POPs-PPh3&S.

Carbon additives, known for their high surface area and excellent electronic conductivity, are commonly employed in battery systems to enhance the electrochemical performance of active materials. Traditionally, however, these additives have been considered electrochemically inert, and their intrinsic properties have largely been overlooked. In this study, the electrochemical behavior of Ketjen black is systematically re-evaluated in aqueous zinc batteries by varying the electrolyte composition and the upper cutoff voltages. Under standard conditions, Ketjen Black EC600J (KB) exhibits typical electric double-layer capacitor behavior, with its capacitance dependent on the applied voltage range. Notably, when the batteries are overcharged, a new pair of redox peaks emerges at ≈1.2/1.4 V, accompanied by a significant increase in capacitance to ≈123 mAh g-1 at a current density of 0.5 A g-1. This overcharge-induced activation is attributed to a preliminary anion intercalation process. Subsequent analysis reveals the presence of a dual-ion intercalation mechanism. Furthermore, KB demonstrates robust cycling stability over 300 cycles in the modified electrolyte, with the specific capacity retaining ≈83 mAh g-1.

High-performance energy storage technologies, with the representatives of rechargeable and redox flow batteries, are required due to the flying development of electrical gadgets and the increase in demand for sustainable energy supply. Nevertheless, most of these batteries are made of inorganic active materials with several critical deficiencies, preventing their further development. Organic nitro compounds (ONCs) are an appealing alternative in this context, providing the advantages of multi-electron redox processes and adjustable battery performance by structural modification. In this review, the utilization of ONCs as the electrode materials of batteries, interfacial layer materials for metal batteries, as well as redox shuttle additives is explored. The authors also go over material design issues, together with the corresponding electrochemical reaction mechanisms, and an overview of related viewpoints and future research directions to facilitate the advancement of this field is provided.

gem-Disubstituted cyclobutanes are essential synthetic building blocks, and the development of synthetic methodologies remains a focal yet challenging frontier in organic chemistry. This study describes a palladium-catalyzed ring enlargement approach for constructing gem-diarylcyclobutanes from arylidenecyclopropanes (ACPs) and anilines. Preliminary mechanistic studies indicated that the protonation of Pd(II) intermediates in a Lewis-acid-maintained acidic environment is crucial for successful reaction progression. Halide ions can inhibit β-hydride elimination while promoting the protonation pathway.

Aqueous zinc-ion batteries (AZIBs) have regained interest due to their inherent safety and costeffectiveness. However, the zinc anode is notorious for side reactions and dendrite growth, which plague the practical application of AZIBs. Adjusting the interfacial pH to reduce the by-products has been proven to be effective in protecting the zinc anode. Nevertheless, the dynamic regulation of the inherently unstable zinc interface during prolonged cycling remains a significant challenge. Herein, zwitterionic N-tris( hydroxymethyl)methylglycine (TMG) integrated with negative -COO and positive NH2 + groups is proposed to stabilize the Zn anode and extend the lifespan as a self-regulating interfacial additive. The anionic portion serves as a trapping site to balance the interfacial pH and thus mitigate the unintended side reactions. Simultaneously, the NH2 + cations are anchored on the zinc surface, forming a water-shielding, zincophilic molecular layer that guides three-dimensional diffusion and promotes uniform electrodeposition. Thus, an average plating efficiency of 99.74% over 3300 cycles at a current density of 2 mA cm 2 is achieved. Notably, the TMG additive actualizes ultralong life in Zn||Zn symmetrical cells (5500 h, exceeding 229 days, 1 mA cm 2/1 mA h cm 2), and enables the Zn||I2 cells to reach capacity retention rate of 89.4% after 1000 cycles at 1 A g 1. (c) 2024 Published by Elsevier B.V. and Science Press on behalf of Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences.

Due to their structural diversity, environmental friendliness, and resource renewability, organic electroactive compounds are versatile hosts for the energy storage of different metal ions. However, the consistency and variety of the energy storage performance and mechanism for the designed organic electrode materials in aqueous electrolytes toward different metal ions have rarely been researched. Here, one type of organic material integrated with anhydride and imide groups was designed and studied in detail. Among the two functional groups, the anhydride carbonyl groups were found to be the dominant contributors during the initial discharge step due to the higher binding energy toward the different metal ions, while the imides were responsible for the second-step coordination with monovalent metal ions. With the increment of the valence of guest metal ions, the activity of the imides decreased and became nearly inactive for the storage of aluminum ions. On the contrary, the anhydride carbonyl groups were always active for the storage of various metal ions and became the capacity contributors when the valence of the metal ions increased. Moreover, similar energy storage behaviors and close potentials were detected during the first discharge step for these different metal ions.

Electrolyte additives that simultaneously regulate Zn2+ solvation and induce robust solid electrolyte interphase (SEI) formation offer an effective approach to suppress dendrite growth, hydrogen evolution, and side reactions in aqueous zinc-ion batteries (AZIBs). Here, fluorinated acetylacetone derivatives are employed to achieve these dual functions at low concentrations. Progressive fluorination enhances electron delocalization and lowers the lowest unoccupied molecular orbital (LUMO), enabling preferential accumulation at the Zn surface. Specifically, hexafluoroacetylacetone (HFAT) forms stable [Zn(H2O)5HFAT]2+ solvation shells, reducing interfacial water activity and promoting Zn2+ desolvation. The lowest LUMO of HFAT further enables its preferential electrochemical reduction, leading to the formation of a gradient cement-brick-like ZnF2-rich SEI that stabilizes Zn deposition and enhances Zn2+ transport. As a result, Zn||Zn symmetric cells exhibit lifespans exceeding 4300 h at 1 mA cm-2/1 mAh cm-2, Zn||Cu cells achieve an average Coulombic efficiency of 99.62% over 1500 cycles, and Zn||I2 full cells retain 125.8 mAh g-1 after 10 000 cycles. This study highlights the potential of fluorine-driven electrolyte design to synergistically optimize solvation structure and interfacial stability for high-performance AZIBs.

The practical application of aqueous zinc-iodine (Zn-I2) batteries is hindered by poor iodine utilization and limited cycling stability, primarily due to the shuttle effect of soluble polyiodide species. In this study, side-group engineering is employed to modulate the electronic structure of hexagonal porous TpPa covalent organic frameworks (COFs). Among the engineered COFs, the nitro-functionalized TpPa COF (TpPa-NO2) outperforms in both I2 utilization and cycling stability, achieving a high specific capacity of ≈183 mAh g‒1 at 0.1 A g‒1 and a remarkable capacity retention of 84.3% after 10 000 cycles at 5 A g‒1. Notably, the TpPa-NO2-based Zn-I2 batteries maintain mitigated polarization and stable operation under harsh conditions, including low temperatures (-5 °C) and high iodine loading (≈15 mg cm‒2). Theoretical simulations reveal that the electronic modulation reduces the TpPa COF's band gap and enhances the affinity for polyiodide species, thus improving the I2 utilization. These findings are further supported by in situ Raman and UV-vis spectroscopy, which identified a dominant I‒/I5 ‒ redox pathway and confirmed suppression of polyiodide dissolution. This work underscores the promise of electronically tailored COFs as advanced cathode hosts for long-life Zn-I2 batteries, offering an effective dual strategy to enhance iodine utilization and mitigate the shuttle effect.

Lithium-metal batteries with solid electrolytes (SEs) have emerged as promising electrochemical energy storage devices due to high energy density and safety. However, inherent challenges of deleterious lithium dendrite growth and poor interfacial stability hinder their practical application. Herein, a new type of room-temperature liquidous Li metal arene complex-Li-Phenanthrene (Phen)-Ether is explored to enable a 3D LiSi@Li-Phen-Ether (3D LSLL) anode with low cost, high safety and high ion/electron-conductivity. Symmetric cells with sulfide SE and 3D LSLL anode deliver an ultra-high critical current density (> 13 mA cm(-2)) and long cycle life (> 1000 h, 0.25 mA cm(-2)). Moreover, full battery (LFP/sulfide SE/3D LSLL) can operate at low-external pressure (0.5 MPa) and ambient temperature by introducing a flexible cathode/sulfide interlayer with high ion conductivity (2 mS cm(-1)). This unprecedented battery configuration demonstrates high-rate (2C) performance and long cycle life (over 300 cycles), which exceeds preciously-reported sulfide SE/lithium batteries at low stack pressures, and may open up a promising route for high-energy-density, cost-effective and safe rechargeable lithium batteries.

A ligand-controlled method for the selective synthesis of indoles and benzofurans from secondary anilines has been discovered. A six-ring palladacycle intermediate may be involved in this process by olefins as a transient directing mediator to give indoles. The indole/benzofuran ratio can be easily tuned by the MPAA ligand. Various substituted secondary anilines were well-tolerated, affording the corresponding products in moderate to good yields. Indole-derived drugs such as JWH-081, BB-22, and ML-098 could be obtained using our new method to achieve their precursors. Preliminary mechanistic studies indicated that BQ is the key factor in avoiding the β-H elimination of insertion species.

A highly ortho-selective C-Ar-H olefination of tertiary anilines without a directing group was developed. This reaction tolerated various substituted arenes and olefin coupling partners, affording ortho-olefination products in moderate to good yields. Preliminary mechanistic studies showed that N-Ac-d-Ala, Ag2CO3, and BQ were the key factors for tuning the regioselectivity from para to ortho. Density functional theory was used to achieve a theoretical understanding of the ortho selectivity.

Alcohols carbonylation is of great importance in industry but remains a challenge to abandon the usage of the halide additives and noble metals. Here we report the realization of direct alcohols heterogeneous carbonylation to carbonyl-containing chemicals, especially in methanol carbonylation, with a remarkable space-time-yield (STY) of 4.74 mol acetyl /kg cat. /h and a durable stability as long as 100 h on Ni@MoS 2 catalyst. Mechanistic analysis reveals that the Mo−Ni dual sites localized at edge sulfur vacancies of Ni@MoS 2 exhibit distinct charge density, which strongly activate CH 3 OH to break its C−O bond and non-dissociatively activate CO. Density functional theory calculations further suggest that the low charge density in Mo−Ni, the Ni site, could significantly lower the barrier for CO migration and nucleophilic attack of methoxy species, and finally leads to the rapid formation of acetyl products. Ni@MoS 2 catalyst could also effectively realize the carbonylation of ethanol, n-propanol and n-butanol to their acyl products, which may demonstrate its universal application for alcohols carbonylation.