ChemSusChem最新文献

The development of a tavorite structured K- transition metal (TM)- fluorophosphate, having earth-abundant Fe as the only TM, crystallizing in the orthorhombic crystal system and facilitating stable-cum-reversible electrochemical K-extraction/insertion, has been reported here. Synthesized using low-cost precursors, KFePO4F has also been found to be air-stable. Detailed information pertaining to the bonding/structure, including lattice site occupancy, have been obtained via diffraction, Raman spectroscopy and FTIR, with XPS and ESR revealing the oxidation states of Fe in the as-synthesized condition and upon being subjected to electrochemical potassiation/depotassiation. The electrochemical K-insertion/extraction, supported by reversible Fe-redox, leads to a reversible K-storage capacity of ~102 mAh/g (within 1.5-4.0 V), along with a 1st cycle Coulombic efficiency (CE) of ~93% (with CE >99.9% from 2nd cycle). Ex-situ X-ray diffraction, as well as operando synchrotron diffraction during galvanostatic cycling, indicates reversible changes in peak positions upon electrochemical K-extraction/insertion, with no evidence for structural change. When used as cathode material in K-ion 'full' cell (with hard carbon-based anode), a discharge capacity of ~68 mAh/g, along with capacity retention of ~70% after 50 cycles, has been obtained; which confirms that this newly-developed earth-abundant Fe-based potassium fluorophosphate can be utilized for potential application in sustainable battery chemistries, like K-ion batteries.

This study explored the use of amino acid-based ionic liquids to facilitate the conversion of carbon dioxide (CO2) into methanol through catalytic hydrogenation. Combining tetrabutylammonium L-argininate (TBA·Arg) with the ruthenium Ru-MACHO-BH complex, allowed achieving significant yields of methanol under optimized conditions. By systematically varying key reaction parameters, we demonstrate that the TBA·Arg ionic liquid promotes the efficient hydrogenation pathway leading to methanol formation, thus offering a sustainable approach to CO2 valorization. These findings underscore the potential of amino acid-based ionic liquids in catalyzing the transformation of CO2 into valuable chemicals, contributing to carbon mitigation efforts.

Paper-based packaging can offer a sustainable replacement for plastics. However, paper provides a poor barrier to water, oxygen and moisture. This study presents a novel renewable lignocellulosic composite made from a hydrophobic photo-reversible coating deposited onto a cellulose nanofiber film that has improved barrier properties and can be reprocessed. Diglycerol and lignin-derivable aldehyde were reacted to form a tetra-functional monomer with photo-responsive unsaturated double bonds that can be converted to covalent cyclobutane rings to create reversibly crosslinkable network upon UV-irradiation. The photo-responsive compound was applied as a thin coating of thickness 2.7±0.4 μm over cellulose nanofiber (CNF) films of thickness 80±19 μm. The surface of the coated films became hydrophobic with a contact angle (CA) of 93.1±1.7° and displayed a low water vapour transmission rate (WVTR) of 16±2 g/m2/day vs. 30.7±1.5° CA and 81±11 g/m2/day WVTR for uncoated CNF films. The coated film is also oleophobic, an attractive feature for food packaging applications. The reversible photo-reaction enables the crosslinked covalent network to be broken down to unsaturated double bonds once exposed to a higher-energy UV irradiation, allowing reprocessing and recycling. The novel coating was developed using a sustainable green synthesis method (process simple E factor 0.9).

2,5-Dihydroxy-1,4-benzoquinone (DHBQ) is a promising cathode material, but its high solubility in electrolytes leads to rapid capacity degradation. This study investigates the dilithium salt of DHBQ, Li2DHBQ, as a cathode material for lithium-ion batteries (LIBs). Despite minimal solubility, Li2DHBQ cathodes suffer rapid capacity decay due to severe morphological damage within the voltage range of 1.5-3.0 V. To stabilize morphology, we promoted a protective solid electrolyte interphase (SEI) layer on Li2DHBQ particles by lowering the discharge cutoff voltage. Cycling the battery with a 0.5 V discharge cutoff voltage achieved an optimal SEI layer, significantly improving Li2DHBQ's morphological stability. Consequently, the battery maintained 170 mAh g-1 with a low decay rate of 0.16% within a voltage range of 0.5-3.0 V after 200 cycles at 500 mA g-1. Furthermore, initial cycling at a 0.5 V discharge cutoff for 20 cycles to form an SEI layer, followed by cycling at a normal 1.5 V discharge cutoff, retained a higher capacity of 187 mAh g⁻¹ after 200 cycles. This study demonstrates the effectiveness of forming a cathode SEI layer at low discharge voltages as a new approach to stabilizing organic cathode materials.

All-solid-state lithium-ion batteries (ASSLIBs) are attracting significant attention due to their high energy density, conductivity and safety. However, they are expected to generate substantial waste in the near future, leading to resource depletion and environmental pollution. Therefore, it is crucial to achieve green, mild and safe recovery of ASSLIBs. Here, we for the first time to use green deep eutectic solvents (DESs) to effectively recover solid-state electrolytes (SSEs) from ASSLIBs at mild temperature. Results show that Li leaching efficiency can reach up to 87.5% with a superhigh Li/La selectivity of 1902 at a low temperature of 80 oC. Furthermore, 70 anti-solvents are screened to recycle the dissolved SSEs from leachate and 12 anti-solvents could precipitate SSEs from leachate at room temperature. This research opens new possibilities for recovering SSEs from ASSLIBs using the sustainable, cost-effective and safe solvents.

Designing high-performance anodic catalysts to drive glycerol oxidation reaction (GOR) is essential for advancing direct alcohol fuel cells. Coupling Pd with oxophilic materials is an effective strategy to enhance its intrinsic catalytic activity. In this study, we successfully synthesized Pd/Bi₂Te₃ catalysts with tunable compositions, using Bi₂Te₃ as a novel promoter, and applied them to the GOR for the first time. Electrocatalytic tests revealed that the activity of the Pd/Bi₂Te₃ catalysts was closely linked to their compositions. Among these catalysts, the optimized Pd/Bi₂Te₃-20 % showed potential to replace the commercial Pd/C catalyst, exhibiting a peak current density 5.2 times higher than that of the benchmark Pd/C catalyst. Furthermore, improved catalytic stability and faster catalytic kinetics were observed for Pd/Bi₂Te₃-20 %. The synergistic effect between Pd and Bi₂Te₃ is responsible for the high performance of the Pd/Bi₂Te₃-20 % catalyst.

Polyester waste in the environment threatens public health and environmental ecosystems. Chemical recycling of polyester waste offers a dual solution to ensure resource sustainability and ecological restoration. This minireview highlights the traditional recycling methods and novel recycling strategies of polyester plastics. The conventional strategy includes pyrolysis, carbonation, and solvolysis of polyesters for degradation and recycling. Furthermore, the review delves into exploring emerging technologies including hydrogenolysis, electrocatalysis, photothermal, photoreforming, and enzymatic for upcycling polyesters. It emphasizes the selectivity of products during the polyester conversion process and elucidates conversion pathways. More importantly, the separation and purification of the products, the life cycle assessment, and the economic analysis of the overall recycling process are essential for evaluating the environmental and economic viability of chemical recycling of waste polyester plastics. Finally, the review offers perspective into the future challenges and developments of chemical recycling in the polyester economy.

Chlorine-rich lithium argyrodite is considered as a promising superionic conductor electrolyte, but its practical application is limited due to poor air stability and instability toward lithium metal. In this work, BiF₃ is proposed as a multi-functional dopant for electrolyte modification, and the effects on the ionic conductivity, air stability, critical current density, and electrolyte/Li metal interfacial stability are studied. The results show that the doped electrolyte Li_5.54P_0.98Bi_0.02S_4.5Cl_1.44F_0.06 (LPBiSClF_0.06) still maintains a relatively high ionic conductivity of 5.37 mS cm^-1. Additionally, the formation of BiS₄ ^5- unit and LiBiS₂ phase provides high air/moisture resistibility. Meanwhile, the critical current density of the Li/LPBiSClF_0.06/Li cell is increased two-fold (2.1 mA cm^-2). The in-situ formation of LiF and Li-Bi alloy at the lithium metal/electrolyte interface plays a key role in achieving high performance. As a result, the assembled LCO@LNO/LPBiSClF_0.06/Li battery retains 78.4 % of its capacity after 100 cycles at 0.2C.

The acid-base microenvironment of the metal center is crucial for constructing advanced oxygen evolution reaction (OER) electrocatalysts. However, the correlation between acidic site and OER performance remains unclear for cobalt-based catalysts. Herein, Lewis acid sites in hollow cobalt phytate micropolyhedra (M-CoPA, M = Cu, Sr) were synthesized by a cation-exchange strategy, and their OER performances were studied systematically. Experimentally, Lewis acid Cu²⁺ sites with stronger Lewis acidity exhibited superior intrinsic activity and long-term stability in alkaline electrolytes. The spectroscopic and electrochemical studies show Lewis acid sites in hollow cobalt phytate micropolyhedra can modulate the electronic distribution of the adjacent cobalt center and further optimize the adsorption strength of oxygenated species. This study figures out the effect of Lewis acid sites on the OER kinetics and provides an effective way to develop high-efficiency electrocatalysts for energy conversion systems.

Advancing lithium-sulfur battery technology requires addressing both extrinsic cell-fabrication and intrinsic material challenges to improve efficiency, cyclability, and environmental sustainability. A key challenge is the low conductivity of sulfur cathodes, which is typically managed by incorporating conductive carbon materials. These materials enhance the performance of sulfur cathodes by facilitating high sulfur loading and improving polysulfide retention. In line with green chemistry principles and circular economy concepts, this study explores the use of recycled materials-specifically recycled quartz and board-as substrates for graphene coatings in lithium-sulfur cells. Recycled quartz bricks and blocks, predominantly SiO₂, and recycled shelf boards, rich in Al₂O₃, are successfully coated with graphene, which significantly improves polysulfide adsorption and overall battery performance. The graphene-coated quartz exhibits high sulfur loading (8 mg cm^-2), exceptional charge-storage capacity (1,114 mA h g^-1), and long cycle stability (200 cycles) with an energy density of 19 mW h cm^-2. This approach enhances the electrochemical performance of the lithium-sulfur cells and also aligns with sustainability goals by repurposing waste materials and minimizing environmental impact. This novel methodology demonstrates that integrating recycled materials can effectively address key challenges in lithium-sulfur battery technology, advancing both performance and environmental sustainability.