Rapid Kinetics Research Articles

Targeting mitochondrial metabolism by the mitotoxin bromoxib in leukemia and lymphoma cells

Abstract Targeting mitochondrial metabolism represents a promising approach for cancer treatment. Here, we investigated the mitotoxic potential of the polybrominated diphenyl ether bromoxib, a natural compound isolated from the marine sponge Dysidea family. We could show that bromoxib comprised strong cytotoxicity in different leukemia and lymphoma cell lines (such as HL60, HPBALL, Jurkat, K562, KOPTK1, MOLT4, SUPB15 and Ramos), but also in solid tumor cell lines (such as glioblastoma cell lines SJ-GBM2 and TP365MG). Bromoxib activated the mitochondrial death pathway as evidenced by the rapid translocation of Bax to the mitochondria and the subsequent mitochondrial release of Smac. Accordingly, bromoxib-induced apoptosis was blocked in caspase 9 deficient Jurkat cells and Jurkat cells overexpressing the antiapoptotic protein Bcl-2. In addition, we could show that bromoxib functioned as an uncoupler of the electron transport chain with similar rapid kinetics as CCCP in terms of dissipation of the mitochondrial membrane potential (ΔΨm), processing of the dynamin-like GTPase OPA1 and subsequent fragmentation of mitochondria. Beyond that, bromoxib strongly abrogated ATP production via glycolysis as well as oxidative phosphorylation (OXPHOS) by targeting electron transport chain complexes II, III, and V (ATP-synthase) in Ramos lymphoma cells. Thus, bromoxib’s potential to act on both cytosolic glycolysis and mitochondrial respiration renders it a promising agent for the treatment of leukemia and lymphoma.

Iodine Boosted Fluoro‐Organic Borate Electrolytes Enabling Fluent Ion‐conductive Solid Electrolyte Interphase for High‐Performance Magnesium Metal Batteries

Rechargeable magnesium batteries are regarded as a promising multi‐valent battery system for low‐cost and sustainable energy storage applications. Boron‐based magnesium salts with terminal substituent fluorinated anions (Mg[B(ORF)4]2, RF = fluorinated alkyl) have exhibited impressive electrochemical stability. Nevertheless, their deployment is hindered by the complicated synthesis routes and the surface passivation of Mg anode. Herein, we report the design of an advanced electrolyte formulation comprised of B(HFIP)3 and I2 in 1,2‐dimethoxyethane (DME), which eventually convert into a Mg[B(HFIP)4]2/DME‐MgI2 electrolyte system upon interacting with Mg anode. The Mg anode reacts with I2 and the electron‐accepting B(HFIP)3, leading to the in‐situ formation of a solid‐electrolyte interphase layer composed of MgF2 and MgI2 species that can facilitate fast and stable Mg plating/stripping. Compared with the pristine Mg[B(HFIP)4]2/DME electrolyte, the Mg[B(HFIP)4]2/DME‐MgI2 electrolyte exhibited superior electrochemical performance including an ultra‐low overpotential (~80 mV), high Coulombic efficiency and a long‐cycling period over 1500 h. In result, the rechargeable magnesium batteries with Mg[B(HFIP)4]2/DME‐MgI2 electrolyte and Mo6S8 cathode show outstanding compatibility, rapid kinetics, and stable cyclability for over 1200 cycles, surpassing all previously reported boron‐based electrolytes. This work introduces a promising halogen‐enhancement strategy for boron‐based Mg‐ion electrolytes and is pivotal for the advancement and optimization of multi‐valent secondary batteries.

Iodine Boosted Fluoro‐Organic Borate Electrolytes Enabling Fluent Ion‐conductive Solid Electrolyte Interphase for High‐Performance Magnesium Metal Batteries

Rechargeable magnesium batteries are regarded as a promising multi‐valent battery system for low‐cost and sustainable energy storage applications. Boron‐based magnesium salts with terminal substituent fluorinated anions (Mg[B(ORF)4]2, RF = fluorinated alkyl) have exhibited impressive electrochemical stability. Nevertheless, their deployment is hindered by the complicated synthesis routes and the surface passivation of Mg anode. Herein, we report the design of an advanced electrolyte formulation comprised of B(HFIP)3 and I2 in 1,2‐dimethoxyethane (DME), which eventually convert into a Mg[B(HFIP)4]2/DME‐MgI2 electrolyte system upon interacting with Mg anode. The Mg anode reacts with I2 and the electron‐accepting B(HFIP)3, leading to the in‐situ formation of a solid‐electrolyte interphase layer composed of MgF2 and MgI2 species that can facilitate fast and stable Mg plating/stripping. Compared with the pristine Mg[B(HFIP)4]2/DME electrolyte, the Mg[B(HFIP)4]2/DME‐MgI2 electrolyte exhibited superior electrochemical performance including an ultra‐low overpotential (~80 mV), high Coulombic efficiency and a long‐cycling period over 1500 h. In result, the rechargeable magnesium batteries with Mg[B(HFIP)4]2/DME‐MgI2 electrolyte and Mo6S8 cathode show outstanding compatibility, rapid kinetics, and stable cyclability for over 1200 cycles, surpassing all previously reported boron‐based electrolytes. This work introduces a promising halogen‐enhancement strategy for boron‐based Mg‐ion electrolytes and is pivotal for the advancement and optimization of multi‐valent secondary batteries.

Fluorinated Squareimines for Molecular Sieving of Aromatic over Aliphatic Compounds

The development of more energy‐efficient separation technologies is essential. Especially the separation of cyclic aliphatic hydrocarbons from their aromatic counterparts remains a significant challenge due to azeotrope formation and similar physical properties, often requiring energy‐intensive processes. Herein, we introduce a novel class of electron‐deficient macrocycles with a unique rectangular structure to optimise π···π interactions within the pore, enabling the highly selective molecular sieving of aromatic compounds from mixtures. Utilising dynamic covalent imine chemistry, the squareimine NDI2F42‐based crystalline functional material is directly obtained from the reaction mixture in a single self‐assembly step in high yields of 84%, alongside the larger NDI2F82 congener, which can be obtained in 69% yield. In vapour sorption and diffusion experiments, NDI2F42 demonstrates rapid adsorption kinetics with selectivities of 97:3 for benzene over cyclohexane and 93:7 for toluene over methylcyclohexane, while single‐crystal and powder X‐ray diffraction studies confirm that the selectivity is primarily governed by directed π···π interactions.

1,8-Diazabicyclo[5.4.0]undec-7-ene as Cyclic Ether Electrolyte Polymerization Inhibition for Wide-Temperature-Range High-Rate Lithium-ion Batteries.

1,3-Dioxolane (DOL), with its broad liquid phase temperature window and low Li+-solvent binding energy, stands out as an ideal solvent candidate for the wide-temperature and high-rate electrolytes. Unfortunately, DOL is susceptible to undergo ring-opening polymerization under common lithium salts, which markedly retards the reaction kinetics. This work introduces the organic basic additive 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) to effectively suppress the polymerization, thus achieving compatibility between LiFSI, LiDFOB lithium salts, and DOL. Furthermore, density functional theory (DFT) calculations are utilized to elucidate the underlying mechanisms of DOL polymerization and to clarify how DBU inhibits its polymerization. The resulting electrolyte, devoid of polymer chain formation, forms a weak solvation structure rich in anions, which demonstrates rapid ion transport kinetics in the bulk electrolyte and excellent electrochemical stability at the electrolyte-electrode interfaces (EEIs) simultaneously. When applied to the LiFePO4||graphite full cell, it exhibits exceptional wide-temperature and high-rate performance, with specific capacities reaching 101.2 mAh g -1 at room temperature (20 C), 36.9 mAh g-1 at -40 °C (0.5 C), and 118.0 mAh g-1 at 60 °C (20 C). This study significantly guides the development of wide-temperature, high-rate electrolytes.

Fluorinated Squareimines for Molecular Sieving of Aromatic over Aliphatic Compounds.

The development of more energy-efficient separation technologies is essential. Especially the separation of cyclic aliphatic hydrocarbons from their aromatic counterparts remains a significant challenge due to azeotrope formation and similar physical properties, often requiring energy-intensive processes. Herein, we introduce a novel class of electron-deficient macrocycles with a unique rectangular structure to optimise π···π interactions within the pore, enabling the highly selective molecular sieving of aromatic compounds from mixtures. Utilising dynamic covalent imine chemistry, the squareimine NDI2F42-based crystalline functional material is directly obtained from the reaction mixture in a single self-assembly step in high yields of 84%, alongside the larger NDI2F82 congener, which can be obtained in 69% yield. In vapour sorption and diffusion experiments, NDI2F42 demonstrates rapid adsorption kinetics with selectivities of 97:3 for benzene over cyclohexane and 93:7 for toluene over methylcyclohexane, while single-crystal and powder X-ray diffraction studies confirm that the selectivity is primarily governed by directed π···π interactions.

Rapid, Controlled Branching Polymerization of Cyanoacrylate via Pathway-Enabled, Site-Specific Branching Initiation.

Controlled branched structures remain a key synthetic limitation for monomeric tissue adhesives because their on-site polymerization that enables adhesion formation requires rapid kinetics, high conversion, and straightforward setup. In this context, site-specific branching initiation by using evolmers is potentially effective for structural control; however, the efficiency and kinetics in current reaction setups persists to be a major challenge. In this paper, an evolmer induces a controlled branching polymerization of cyanoacrylate amid the high monomer reactivity useful in rapid adhesion. The contrasting reactivities between the vinyl and the initiating groups in the evolmer molecule generate a kinetic pathway that favors a control-enabling branching mechanism. Through density functional theory calculations, the reaction pathway toward branching is shown to kinetically favor site-specific initiation by six orders of magnitude than the route toward non-specificity. Reaction monitoring confirms the branching polymerization after the polymerization with the evolmer forms a more compact structure than the linear counterpart. Control of branching density is demonstrated in rapid polymerizations within minutes and in polymerizations completed in an instant. These results provide a template for achieving site-specific branching initiation during adhesion formation and, broadly, where conditions for kinetic control are necessary.

A novel ternary hydrophobic deep eutectic solvent over a wide pH range for lithium recovery

Owing to the crucial role of lithium (Li) in green technology and energy storage, the global demand for Li is constantly increasing. This article provides a new strategy for recovering Li using ternary hydrophobic deep eutectic solvent (HDES). The novel HDES was composed of 2-thiophenyltrifluoroacetone (HTTA), trioctylphosphine oxide (TOPO), and N,N-diethyldecanamide (DDA), and exhibited high efficiency and selectivity for extracting Li from aqueous solutions. This study systematically evaluated the effect of the initial aqueous pH on the Li extraction efficiency, revealing the stable performance of HDES in the pH range 3–13. Compared to the highly alkaline environment required for Li extraction, the pH characteristics of the HDES provide a wider range of applications and a more environmentally friendly alternative. The HDES exhibited rapid extraction kinetics, achieving equilibrium within 10 min and maintaining phase stability without emulsification. The main mechanism of selective Li extraction is the electrostatic interaction between Li(I) and TTA. The interactions between Li(I) and both TOPO and DDA were confirmed by Fourier transform infrared (FT-IR) spectroscopy, thereby improving the selectivity and extraction efficiency. The countercurrent extraction process demonstrated an impressive Li extraction rate of 98.704 % and a Li(I)/Na(I) separation factor of 10643.14 with industrial Li2CO3 mother liquor, highlighting the application potential of the ternary HDES. The excellent performance of the HDES over a wide pH range provides more opportunities for its application, and its high efficiency, selectivity, and environmental characteristics may promote Li recovery.

Redox Mediator as Highly Efficient Charge Storage Electrode Additive for All‐Solid‐State Lithium Metal Batteries

AbstractAll‐solid‐state lithium metal batteries (ASSLBs) have the potential to provide a significant increase in energy density and safety. However, most ASSLBs are still suffering from low cathode loading, poor rate capability, and low attainable energy/power densities, which seriously limit their practical application. Besides developing solid electrolytes with high conductivity, constructing a highly loaded cathode with rapid reaction kinetics is also essential for achieving high‐performance ASSLBs. Herein, the methylamine hydroiodide (CH6NI) is investigated as a functional electrode additive to enable rapid Li+ transport and charge transfer in LiFePO4 (LFP) cathode, whereby the CH6NI serves as a charge storage carrier that facilitates the reaction kinetics during the delithiation and lithiation process of LFP. As a result, the ASSLB assembled with LFP@CH6NI cathode shows excellent cycling stability over 700 cycles at 2 C with a high capacity retention of 87.6%, while the cell with bare LFP cathode shows no capacity at high current rates (≥0.5 C). Moreover, the ASSLB pared with a high active loading cathode (5.6 mg cm−2) still exhibits a high specific capacity of 144.9 mAh g−1 at 0.5 C. This work provides a facile strategy that opens new possibilities for designing high‐loading electrodes for high‐performance ASSLBs.

Covalent Attachment of Functional Proteins to Microfiber Surfaces via a General Strategy for Site-Selective Tetrazine Ligation.

Surface modification of materials with proteins has various biological applications, and hence the methodology for surface modification needs to accommodate a wide range of proteins that differ in structure, size, and function. Presented here is a methodology that uses the Affinity Bioorthogonal Chemistry (ABC) tag, 3-(2-pyridyl)-6-methyltetrazine (PyTz), for the site-selective modification and purification of proteins and subsequent attachment of the protein to trans-cyclooctene (TCO)-functionalized hydrogel microfibers. This method of surface modification is shown to maintain the functionality of the protein after conjugation with proteins of varying size and functionalities, namely, HaloTag, NanoLuc luciferase (NanoLuc), and fibronectin type III domains 9-10 (FNIII 9-10). The method also supports surface modification with multiple proteins, which is shown by the simultaneous conjugation of HaloTag and NanoLuc on the microfiber surface. The ability to control the relative concentrations of multiple proteins presented on the surface is shown with the use of HaloTag and superfolder GFP (sfGFP). This application of the ABC-tagging methodology expands on existing surface modification methods and provides flexibility in the site-selective protein conjugation methods used along with the rapid kinetics of tetrazine ligation.

Differentiation of adsorption and degradation in steroid hormone micropollutants removal using electrochemical carbon nanotube membrane

The growing concern over micropollutants in aquatic ecosystems motivates the development of electrochemical membrane reactors (EMRs) as a sustainable water treatment solution. Nevertheless, the intricate interplay among adsorption/desorption, electrochemical reactions, and byproduct formation within EMR complicates the understanding of their mechanisms. Herein, the degradation of micropollutants using an EMR equipped with carbon nanotube membrane are investigated, employing isotope-labeled steroid hormone micropollutant. The integration of high-performance liquid chromatography with a flow scintillator analyzer and liquid scintillation counting techniques allows to differentiate hormone removal by concurrent adsorption and degradation. Pre-adsorption of hormone is found not to limit its subsequent degradation, attributed to the rapid adsorption kinetics and effective mass transfer of EMR. This analytical approach facilitates determining the limiting factors affecting the hormone degradation under variable conditions. Increasing the voltage from 0.6 to 1.2 V causes the degradation dynamics to transition from being controlled by electron transfer rates to an adsorption-rate-limited regime. These findings unravels some underlying mechanisms of EMR, providing valuable insights for designing electrochemical strategies for micropollutant control.

Cu@Cu31S16 cathode for high-performance aqueous zinc-ion battery

Abstract Among various battery systems, aqueous zinc-ion batteries demonstrate significant potential for large-scale energy storage applications. However, the relatively large radius of zinc ions makes it challenging for them to intercalate into cathode materials, resulting in a limited variety of host materials suitable for Zn2+ storage. Therefore, researching appropriate cathode materials is a crucial component of the practical application of aqueous zinc-ion batteries. In this study, we prepare two binderless, conductor-less, current collector materials Cu@Cu31S16 cathodes, by in-situ etching of copper foil with a polysulfide precursor solution. The results indicate that Cu31S16 not only exhibits excellent stability and conductivity but also features rapid ion migration kinetics and low Zn2+ diffusion barriers.

Application of novel Dy0.06Gd0.02Er0.02Bi1.9O3 oxide ion electrolyte for intermediate-temperature reversible solid oxide cells

Bismuth-based oxides are promising electrolyte materials for Reversible Solid Oxide Cells (RSOCs) due to their high ion conductivity and rapid surface oxygen exchange kinetics. In this work we propose a multi-element doping strategy to obtain a novel Dy0.06Gd0.02Er0.02Bi1.9O3 (DGESB) quaternary oxide bismuth material whose ionic conductivities and crystal structure are characterized by AC impedance and X-ray diffraction technique in the temperature range from 600 to 700 °C. Along with promising structure stability and durability, our novel DGESB showed a remarkable ionic conductivity that is 65 times higher than the commercial yttria-stabilized zirconia (YSZ) electrolyte at 700 °C. With composite electrode of DGESB + LCN (LaCo0.6Ni0.4O3) and DGESB/YSZ bilayer electrolyte consisting of RSOC symmetric cell, which achieves a high peak power density (PPD) of 1.62 W/cm2 in fuel cell mode which is 2.7 times higher than that of YSZ single-layer electrolyte, while the electrolysis current density is as high as 1.66 A/cm2 at 1.3 V under H2/H2O:50/50 in electrolysis mode at the same operation temperature of 700 °C. The electrochemical performance measurements revealed a certain stable operation for 200 h in fuel cell mode. The performance degradation can be attributed to the microstructure evolution at the interface between electrolyte and electrodes. The high ionic conductive DGESB proves to be an excellent intermediate electrolyte layer for improving cell performance in RSOCs

Efficient electrocatalytic oxygen evolution enabled by porous Eu-Ni(PO3)2 nanosheet arrays

Phosphorous compounds have garnered significant interest as catalysts for the oxygen evolution reaction (OER). However, their catalytic performance often falls short, limiting their widespread application in electrocatalysis. The objective of this work is to improve the OER performance of nickel metaphosphate (Ni(PO3)2) by incorporating rare-earth europium (Eu). The prepared Eu-Ni(PO3)2 exhibits significant electron redistribution and features porous nanosheet arrays. The optimized Eu-Ni(PO3)2 exhibits outstanding OER activity, with an overpotential of 273 mV at 10 mA/cm, rapid OER kinetics with a Tafel slope of 39.4 mV/dec, and excellent electrochemical stability. These results surpass the performance of Ni(PO3)2, many reported Ni-based catalysts, and even commercial RuO2. Operando Raman spectroscopy reveals that the improvement of OER performance on Eu-Ni(PO3)2 is due to the accelerated formation of surface NiOOH active species and the enhanced interfacial water enrichment during OER. Density functional theory (DFT) calculations further demonstrate that Eu doping induces electronic modulation between the Eu sites and adjacent O-Ni sites, resulting in an optimized thermodynamic pathway with balanced adsorption energies for key oxygen intermediates, thus alleviating thermodynamic limitations during OER.

A highly water-soluble phenoxazine quaternary ammonium compound catholyte for pH-neutral aqueous organic redox flow batteries

The pH-neutral aqueous redox flow battery (ARFB) is one of the most attractive flow batteries due to its non-corrosiveness, low-cost, and wider electrochemical stability window compared to those with acidic or alkaline electrolytes. However, there are few families of organic redox-active molecules available as catholyte materials for pH-neutral ARFBs. Herein, through incorporation of quaternary ammonium moiety into the redox-active phenoxazine nucleus, an organic catholyte material, N, N, N-trimethyl-2-(10H-phenoxazin-10-yl) ethan-1-aminium chloride (NEt-POZ) is achieved for pH-neutral ARFBs. The NEt-POZ has a high redox potential of 0.79 V versus SHE and rapid redox kinetics (0.23 cm s−1) as well as high water-solubility (∼2.6 M in H2O). Paired with a methyl viologen (MV) anolyte in the pH-neutral aqueous electrolyte, a viologen-phenoxazine ARFB full cell is assembled, which shows an open circuit voltage of ∼1.23 V. However, the results of long-term cycling experiments indicate low Coulomb efficiency and rapid declining capacity of the NEt-POZ catholyte. The mechanism analysis unveils that the unstable doubly oxidized tri-cations (NEt-POZ3+) formed via the disproportionation of radical di-cations (NEt-POZ2+) in solution readily react with chloride anions to form poly-chlorinated derivatives, which precipitate from the catholyte due to their poor water solubility, leading to a rapid decrease in capacity. When there is no chloride present in the electrolyte solution, highly reactive NEt-POZ3+ cations can interact with other counter-anions (such as sulfate and carbonate ions) and even water to form complex adducts.

Gamma radiation induced optimized synthesis of amine functionalised poly-glycidyl methacrylate grafted poly-propylene non-woven fabric and its adsorption behaviour towards aqueous Pb(II)

Comprehensive optimization of the functionalization of polypropylene (PP) non-woven fabric through gamma irradiation-induced graft polymerization of glycidyl methacrylate (GMA), results in a material having high grafting yield. The technique, utilizing a mutual irradiation method, produced poly-GMA (PGMA) grafted PP fabric with a remarkable grafting yield of 125 % in a 1:1 acetone–water mixture, subjected to 25 kGy of total dose at a dose rate of 5 kGyh−1. The enhancement of the amination process utilizing PGMA-grafted PP was investigated with polyamines. Under the optimized conditions, the diethylene triamine (DETA) functionalized variant was identified as an effective adsorbent for aqueous Pb2+ ions. The optimized adsorbent exhibited a high saturation capacity of approximately 230 mgg−1 for Pb2+ ions, demonstrating rapid kinetics at near-neutral pH and 25 °C. This low cost innovative material holds significant promise for effective lead removal from drinking water and industrial wastewater, offering a sustainable economical solution for environmental remediation.

Zinc hexacyanoferrate with open framework for efficient aqueous cobalt ions storage

In this work, we report a high-performance aqueous Co-ion battery with zinc hexacyanoferrate as Co2+ storage material. Owing to the open framework, zinc hexacyanoferrate exhibits excellent electrochemical performance. The reversible capacity of zinc hexacyanoferrate is up to 62.4 mAh g−1 at 5C with ultralow capacity decay (0.0084 % per cycle) within 500 cycles. Even cycled at a higher rate of 10C, zinc hexacyanoferrate still can remain a high capacity retention of 98.8 % after 700 cycles. The excellent electrochemical performance is attributed to the rapid kinetics behavior of Co2+ in the open and stable framework structure. Besides, a joint analysis of in-situ X-ray diffraction, ex-situ Fourier transform infrared spectroscopy and ex-situ X-ray photoelectron spectroscopy verifies the highly reversible structural change of zinc hexacyanoferrate during charge/discharge process. All these evidences suggest that zinc hexacyanoferrate may be a promising host material for Co2+ storage in aqueous rechargeable batteries.

Green and Mild Fabrication of Magnetic Poly(trithiocyanuric acid) Polymers for Rapid and Selective Separation of Mercury(II) Ions in Aqueous Samples

The removal and detection of highly toxic mercury(II) ions (Hg2+) in water used daily is essential for human health and monitoring environmental pollution. Efficient porous organic polymers (POPs) can provide a strong adsorption capacity toward heavy metal ions, although the complex synthetic process and inconvenient phase separation steps limit their application. Hence, a combination of POPs and magnetic nanomaterials was proposed and a new magnetic porous organic polymer adsorbent was fabricated by a green and mild redox reaction in the aqueous phase with trithiocyanuric acid (TA) and its sodium salts acting as reductive monomers and iodine acting as an oxidant. In the preparation steps, no additional harmful organic solvent is required and the byproducts of sodium iodine are generally considered to be non-toxic. The resulting magnetic poly(trithiocyanuric acid) polymers (MPTAPs) are highly porous, have large surface areas, are rich in sulfhydryl groups and show easy magnetic separation ability. The experimental results show that MPTAPs exhibit good adsorption affinity toward Hg2+ with high selectivity, rapid adsorption kinetics (10 min), a large adsorption capacity (211 mg g−1) and wide adsorption applicability under various pH environments (pH 2~8). Additionally, MPTAPs can be reused for up to 10 cycles, and the magnetic separation step of MPTAPs is fast and convenient, reducing energy consumption compared to centrifugation and filtration steps required for non-magnetic adsorbents. These results demonstrate the promising capability of MPTAPs as superior adsorbents for effective adsorption and separation of Hg2+. Based on this, the prepared MPTAPs were adopted as magnetic solid-phase extraction (MSPE) materials for isolation of trace Hg2+ from aqueous samples. Under optimized conditions, the extraction and quantification of trace Hg2+ in water samples were accomplished using inductively coupled plasma mass spectrometry (ICP-MS) detection after MSPE procedures. The proposed MPTAPs-based MSPE-ICP-MS method is efficient, rapid, sensitive and selective for the determination of trace Hg2+, and was successfully employed for the accurate analysis of trace Hg2+ in tap water, wastewater, lake water and river water samples.

Cell-Shearing Chemistry Directed Closed-Pore Regeneration in Biomass-Derived Hard Carbons for Ultrafast Sodium Storage.

The closed-pore structure of hard carbons holds the key to high plateau capacity and rapid diffusion kinetics when applied as sodium-ion battery (SIB) anodes. However, understanding and establishing the structure-electrochemistry relationship still remains a significant challenge. This work, for the first time, introduces an innovative deep eutectic solvent (DES) cell-shearing strategy to precisely tailor the cell structure of natural bamboo and consequently the closed-pore in its derived hard carbons. The DES shearing force effectively modifies the pore architecture by simultaneously shearing and dissolving amorphous components to form closed pore cores with adjustable sizes, as well as disintegrating crystalline cellulose through generation of competing hydrogen bonds to elaborately tune the pore wall thickness and ordering. The optimized closed-pore structure featuring appropriate pore size (∼2 nm) and ultra-thin (1-3 layers) disordered pore walls, exhibits abundant active sites and delivers rapid ion diffusion kinetics and high reaction reversibility. Consequently, a high reversible capacity of 422 mAh g-1 at 30 mA g-1 along with an exceptional rate capability (318.6 mAh g-1 at 6 A g-1) are achieved, outperforming almost all previous reported hard carbons. The new concept of cell-shearing chemistry for closed-pore regeneration significantly advances the applications of biomass materials for energy storage.

Regulating Intermolecular Interactions and Film Formation Kinetics for Record Efficiency in Difluorobenzothiadizole‐Based Organic Solar Cells

AbstractThe difluorobenzothiadizole (ffBT) unit is one of the most classic electron‐accepting building blocks used to construct D‐A copolymers for applications in organic solar cells (OSCs). Historically, ffBT‐based polymers have achieved record power conversion efficiencies (PCEs) in fullerene‐based OSCs owing to their strong temperature‐dependent aggregation (TDA) characteristics. However, their excessive miscibility and rapid aggregation kinetics during film formation have hindered their performance with state‐of‐the‐art non‐fullerene acceptors (NFAs). Herein, we synthesized two ffBT‐based copolymers, PffBT‐2T and PffBT‐4T, incorporating different π‐bridges to modulate intermolecular interactions and aggregation tendencies. Experimental and theoretical studies revealed that PffBT‐4T exhibits reduced electrostatic potential differences and miscibility with L8‐BO compared to PffBT‐2T. This facilitates improved phase separation in the active layer, leading to enhanced molecular packing and optimized morphology. Moreover, PffBT‐4T demonstrated a prolonged nucleation and crystal growth process, leading to enhanced molecular packing and optimized morphology. Consequently, PffBT‐4T‐based devices achieved a remarkable PCE of 17.5 %, setting a new record for ffBT‐based photovoltaic polymers. Our findings underscore the importance of conjugate backbone modulation in controlling aggregation behavior and film formation kinetics, providing valuable insights for the design of high‐performance polymer donors in organic photovoltaics.