ChemSusChem最新文献

The rapid development of electric vehicles and large-scale energy storage is driving the requirements for lithium-ion batteries (LIBs) with high energy density, long cycle life, and enhanced safety. However, the commercial graphite anode (372 mAh g⁻¹) struggles to meet these demands. Transition metal oxides are considered as promising anode alternatives due to higher specific capacity and low cost, while their wide application is limited by volume expansion and low conductivity, resulting in rapid capacity fading and poor rate performance. In 2018, the first application of high-entropy oxides (HEOs) as LIB anodes was reported, which attracted the attention of researchers. HEO anodes exhibit outstanding structural stability and electrochemical reversibility owing to their high-entropy effect, lattice distortion, cocktail effect, and sluggish diffusion. This review summarizes recent works on HEO anodes for LIBs, focusing on their structural types, synthesis methods, and advanced characterization techniques. Moreover, lithium storage mechanisms are discussed. Finally, this article points the challenges of HEO anodes, including low reversible capacity, low initial coulombic efficiency, and unclear reaction mechanisms. In the future, the researchers should focus on computational modeling, machine learning, and advanced in situ characterization to explore the next-generation HEO anodes for LIBs.

The extreme atmospheric persistence of sulfur hexafluoride (SF₆), coupled with its high global warming potential, necessitates effective degradation strategies. Herein, we report a reduction-precipitation platform that simultaneously achieves SF₆ defluorination and in situ fluoride immobilization. Hydrated electrons ($$) generated via photoreduction drive the cleavage of SF bonds, achieving enhanced SF₆ degradation. Crucially, in situ precipitation with calcium salts directly converts the released fluoride ions into fluorite (CaF₂), eliminating secondary pollution. XRD analysis confirmed complete phase transformation to pure CaF₂ within 24 h using either Ca(OH)₂ or CaCl₂ as the calcium source, with fluoride mineralization efficiency exceeding 98%. This integrated approach of reduction and mineralization offers a new solution for managing SF₆ and may offer insights for the degradation of other fluorinated greenhouse gases.

Organic redox-active electrode materials are gaining increasing attention due to their eco-friendliness, abundance, and structural versatility. However, their processing typically depends on poly(vinylidene difluoride) (PVdF) as binder and N-methyl-2-pyrrolidone (NMP) as solvent, both are expensive and hazardous. While aqueous processing methods are well established for inorganic electrodes, their application to organic materials remains largely unexplored. This study investigates the use of water-processable binders, specifically sodium carboxymethyl cellulose (Na-CMC) and styrene-butadiene rubber (SBR) for fabricating poly(3-vinyl-N-methylphenothiazine) electrodes. Key factors influencing electrode performance and microstructure were systematically studied, including the choice of conductive additive, mixing procedures, hot-pressing, and densification. Among these, the selection of conductive additive, mixing method, and room temperature densification at different pressure had the most pronounced impact on electrochemical performance. Electrodes using Na-CMC as the primary binder retained ≈90% of their theoretical capacity over 1000 cycles at 1C rate, comparable to PVdF-based electrodes. While increased densification pressure improved electrode uniformity, it had a detrimental effect on electrochemical performance. Introducing SBR as a co-binder at various weight ratios enhanced mechanical integrity and mitigated the negative effects of high densification pressure, ultimately leading to improved electrochemical performance under these applied operation conditions.

In pursuit of agrivoltaics applications in greenhouses, green-light wavelength-selective organic solar cells (GLWS-OSCs) have emerged as a promising technology that enables simultaneous energy harvesting and crop cultivation. For their practical large-scale fabrication, the development of environmentally benign processing methods, along with achieving high photovoltaic performance, is essential. Herein, to investigate the impact of the dipole moment of nonfullerene acceptors on their suitability for green-solvent processing, we developed a symmetric acceptor, BTz-TT-FA, possessing an intrinsically low dipole moment. BTz-TT-FA shows green-light absorption with a maximum absorption wavelength at 531 nm. The ionization potential and electron affinity were determined to be 5.63 and 3.02 eV, respectively, indicating that BTz-TT-FA possesses appropriate energy levels as an acceptor for use with poly(3-hexylthiophene) (P3HT) as the donor. The P3HT:BTz-TT-FA film shows a high green-light wavelength-selectivity factor of 0.77, thereby maintaining an adequate photosynthetic rate in strawberries. The P3HT:BTz-TT-FA-based OSCs showed superior photovoltaic performance, achieving higher power conversion efficiency under p-xylene-processed conditions, compared to those processed with chlorobenzene. The dependence of the process solvent on film crystallinity, morphology, and miscibility was investigated. These findings highlight the critical role of dipole moment in facilitating green-solvent processing and demonstrate a promising pathway toward the development of sustainable GLWS-OSCs.

Photocatalytic hydrogen peroxide (H₂O₂) production is a promising green and sustainable approach, but achieving high efficiency in pure water systems without the sacrificial agents remains a significant challenge. Here, gold (Au) nanoparticles with varying loadings are photodeposited onto the surface of ZnIn₂S₄ (ZIS) nanoflowers to enhance photocatalytic H₂O₂ production. The optimized Au₁₀₀₀-ZIS sample achieves an exceptional H₂O₂ production rate of 906.13 µmol g⁻¹ h⁻¹ under pure water conditions, along with outstanding cycling stability. Mechanistic studies reveal that multivalent Au nanoparticles serve as efficient electron trapping sites, thereby significantly enhancing the spatial separation of photogenerated charge carriers and facilitating rapid charge transfer. This enhanced charge transfer kinetics facilitates H₂O₂ photosynthesis through a dual-channel process (2-electron oxygen reduction and water oxidation) without any additional sacrificial agent. This study enhances the understanding of the critical role of Au as a cocatalyst in photocatalytic processes and presents a promising strategy for sustainable and efficient H₂O₂ production.

Up to now, researchers have been dedicated to developing oxygen reduction reaction (ORR) catalysts with high activity and durability. Zeolitic imidazolate frameworks (ZIFs) are an excellent choice as precursors for ORR catalysts due to their high specific surface area and abundant active sites. At present, most review papers mainly concentrate on electrocatalysis and degradation. The distinction of this paper lies in starting with ZIFs themselves. First, the synthesis methods and mechanisms of ZIFs are summarized. Then, it elaborates in depth on how ZIFs form hollow structures and the preparation methods of derived single-atom catalyst materials. Finally, the development status of different types of hollow ZIF-derived single-atom materials in the ORR field is reviewed, and the future development trends and directions are prospected.

Metal halide perovskites have shown great promise in the photovoltaic field owing to their outstanding optoelectronic properties. However, defect states at the perovskite/electron transport layer interface significantly increase charge recombination losses, becoming a major bottleneck hindering further improvements in the efficiency of perovskite solar cells. Here, we introduce a multiple-site surface modification strategy using 3,4,5-trifluorobenzoic acid (TFBA) to address interfacial defects and energy-level alignment in inverted perovskite solar cells. TFBA anchors strongly onto the perovskite surface via carboxyl coordination with undercoordinated Pb²⁺ ions and hydrogen bonding with FA⁺ cations, thereby significantly reducing trap-state density and suppressing nonradiative recombination. Meanwhile, the multifluorinated structure further induces n-type band bending, optimizing electron transport and improving energy-level alignment, while also providing interfacial hydrophobicity. As a result, the TFBA-modified device achieved a champion power conversion efficiency (PCE) of 25.54% with an open-circuit voltage (V_OC) of 1.183 V and fill factor (FF) of 85.17%, significantly outperforming the reference device's PCE of 24.41% with a V_OC of 1.149 V and FF of 83.10% in the Cs_0.05FA_0.95PbI₃ perovskite system, while maintaining 85% of its initial PCE after 1,000 h of continuous operational stability testing.

A major obstacle to the commercial application of metal-organic frameworks (MOFs) is that their powder form hinders scalable membrane fabrication and significantly compromises stability under humid conditions. To address these limitations, this study presents a novel, humidity-resistant zeolitic imidazolate framework ZIF-67/alumina composite membrane (MMF) that combines visible-light volatile organic compound (VOC) degradation and CO₂ adsorption in a single, scalable platform. Using an in situ self-conversion strategy, ZIF-67 crystals were directly anchored onto porous alumina, providing strong interfacial bonding, mechanical durability, and efficient mass transport. The MMF exhibited excellent toluene adsorption, as described by the Langmuir model, and achieved 96.4% photocatalytic degradation under visible light. Radical-trapping and Electron spin resonance (ESR) studies confirmed superoxide anions (^.O₂⁻) as the dominant active species. The photocatalytic performance declined at 70–80% relative humidity (RH). To overcome this, ultrathin hydrophobic polysiloxane and perfluorinated polymer coatings minimized water uptake and maintained >92% photocatalytic activity, as supported by water vapor isotherms. Beyond VOC abatement, the MMFs demonstrated promising CO₂ adsorption predominantly by physisorption with higher uptake at low temperature and high pressure, attributed to enhanced pore filling and van der Waals interactions with nitrogen-rich active sites. This work establishes a scalable strategy for MOF-based membranes for simultaneous VOC abatement and CO₂ capture, offering a promising pathway for air-purification technologies.

Lignin and lignin–carbohydrate complexes (LCCs) were isolated using AquaSolv Omni (AqSO). The process involves hydrothermal treatment of wood followed by organic solvent extraction, using a sequential fractionation approach with water-based alkaline (1 wt%), ethanol, and acetone solutions. This strategy allowed for isolating different lignin/LCCs fractions with varying structure and properties. The sequential fractionation approach provided fractions with wide variability of glass transition temperatures ranging from 94°C to 153°C, while demonstrating excellent antioxidant activity with a normalized radical scavenging index up to 13.2 mmol g⁻¹. The incorporation of different lignin/LCCs with high antioxidant activity into lignocellulosic film formulation at 1.5 wt%, in which lignin and cellulose were the sole components, demonstrated superior effectiveness in blocking over 90% of ultraviolet (UV) rays (sun protection factor = 6–12), yet maintaining a high transparency of the resulting film. This study underscores the versatility of lignin and its high potential for integration into applications where strong UV and antioxidant protection are concerned without posing any environmental concern.

Lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) help meet the growing global demand for sustainable energy storage due to their high energy density, portability, and rechargeability. As a key component of secondary battery systems, the anode material largely determines their overall performance. However, commercial graphite is limited by its low theoretical capacity (372 mAh·g⁻¹) and poor Na⁺ storage capacity, necessitating the exploration of alternative anode materials. Among the numerous candidate materials, iron-based compounds (including oxides, sulfides, and porous materials derived from metal–organic frameworks (MOFs)) stand out due to their high theoretical specific capacity, natural abundance, and environmental friendliness. However, severe volume expansion and structural instability during repeated charge–discharge cycles lead to rapid capacity decay, severely hindering their practical application. This review systematically summarizes the recent progress in iron-based compounds as anodes for LIBs and SIBs. The electrochemical properties of iron oxides, iron sulfides, and porous iron-based derivatives are highlighted, with particular attention paid to the challenges posed by volume expansion. Furthermore, a comprehensive analysis of the strategies developed to mitigate volume expansion, such as nanostructure design, carbon composites, hollow/porous structure engineering, and interface optimization, is presented. Finally, current limitations and future research opportunities are outlined, aiming to provide guidance for the rational design of high-performance iron-based anode materials for next-generation rechargeable batteries.