Green Chemistry最新文献

The imperative to selectively recover palladium from complex secondary sources is compounded by the significant technical challenges involved. This study introduces a heteroatom-engineered resorcinol-formaldehyde resin microsphere (Se-RF) with dual N/Se doping, which implements a “bait-and-anchor” strategy for highly efficient Pd(II) recovery from challenging environments. The Se-RF adsorbent significantly outperforms conventional RF resins, owing to its heteroatom-cooperative capture mechanism. The breakthrough lies in: (1) an ultrafast in situ doping polymerization process, facilitated by high-speed stirring, yielding uniform microspheres within 5 min under ambient conditions; (2) the dual role of ammonia as both polymerization catalyst and nitrogen precursor, creating “soft base” sites that enhance electrostatic affinity; and (3) synergistic N/Se binding, endowing the resin with a high Pd(II) uptake capacity of 447 mg g⁻¹ at 318 K and 96.65% recovery efficiency from real waste catalyst leachates, with minimal capacity loss (<5%) over five cycles—far surpassing commercial resins (<40%). In situ FTIR, XPS, Raman, and DFT analyses confirm a cascade capture mechanism: protonated N sites act as electrostatic “bait” for preconcentrating [PdCl₄]²⁻, while Se sites serve as a strong “anchor” via Pd ← N to Pd–Se coordination, enabling effective charge transfer and stable chelation. This work provides a cost-effective and sustainable adsorbent design strategy for precious metal recovery and environmental remediation.

Replacing fossil materials with renewable bio-based alternatives is a pivotal strategy to make the membrane manufacturing industry more sustainable in alignment with the UN Sustainable Development Goals. Poly(ethylene furanoate) (PEF) is a biopolymer synthesized from 2,5-furan dicarboxylic acid, a natural monomer that can be derived from lignocellulosic biomass, with the potential to replace fossil polymers across various fields. However, its high chemical stability makes solubilization challenging, and currently, the most common solvent choices for this purpose are fossil-based solvents such as trifluoroacetic acid and hexafluoro-2-propanol. In this work, we introduce a bio-based solvent alternative to process PEF into porous membranes consisting of a deep eutectic system comprising the natural solids thymol and vanillin. The resulting ultrafiltration membranes exhibited competitive performance in fruit juice clarification. A life cycle assessment showed a lower global warming potential, human toxicity, and fossil depletion for the proposed fabrication protocol compared to a fossil-based counterpart, poly(ethylene terephthalate) solubilized in trifluoroacetic acid. We identified non-solvent production and waste treatment as the primary contributors to the environmental impact of PEF membrane production, and demonstrated the environmental benefits of mitigation strategies such as waste recycling, energy recovery, and the use of a bio-based non-solvent. Our findings expand the alternatives for more sustainable PEF processing in solution and demonstrate the potential of PEF as a high-performance polymer for membrane separation applications.

Electrocatalytic seawater splitting shows immense promise as a green hydrogen production technology; however, the anodic oxygen evolution reaction (OER) confronts formidable challenges arising from the high concentration of chloride ions (Cl⁻) and other impurities in seawater. Herein, we develop a facile two-step immersion corrosion strategy to successfully construct a Ni₃S₂@FeOOH/NF heterojunction electrocatalyst on nickel foam (NF) tailored for industrial alkaline seawater oxidation. Integrating density functional theory (DFT) calculations and experimental characterization, we demonstrate that Ni₃S₂@FeOOH/NF selectively enriches OH⁻ while repelling Cl⁻ during the OER in alkaline seawater electrolytes. Notably, in situ leaching of SO₄²⁻ from the electrode triggers efficient self-reconstruction, facilitating the generation of high-valence metal active sites. The as-fabricated catalyst exhibits remarkable OER performance with a low overpotential of 390.5 mV at 1000 mA cm⁻² in alkaline seawater. Moreover, it maintains exceptional electrochemical stability for over 1000 hours at an industrial current density of 1000 mA cm⁻². This work provides a scalable strategy for constructing self-reconstructing electrocatalysts that promote high-valence metal site formation and efficient Cl⁻ repulsion in alkaline seawater oxidation (ASO).

Direct recycling of spent LiFePO₄ (LFP) cathodes is a sustainable and energy-efficient strategy for recovering valuable materials while preserving the intrinsic olivine structure. Herein, we report a LiI-assisted regeneration approach that achieves electronic structure reconstruction and reinforced Fe–O d–p orbital hybridization, enabling simultaneous repair of structural defects and enhancement of Li⁺ transport kinetics. The reductive I⁻ ions promote Fe³⁺ → Fe²⁺ conversion and effectively eliminate Fe–Li antisite defects, while Li⁺ replenishment restores the stoichiometry of degraded LFP. Density functional theory (DFT) calculations reveal that LiI triggers a downward shift of the Fe 3d band center and an upward shift of the O 2p band center, narrowing their energy separation and strengthening Fe–O covalency. These electronic modifications reduce Li⁺ migration barriers and reconstruct continuous Li⁺ transport channels, as further validated by ab initio molecular dynamics simulations. In situ XRD measurements confirm reduced unit-cell volume fluctuations and enhanced FeO₆–PO₄ framework stability, demonstrating improved structural reversibility during cycling. Benefiting from this coupled structural–electronic reconstruction, regenerated LFP delivers 146.9 mAh g⁻¹ at 1 C and retains 97.4% capacity after 500 cycles, outperforming the spent material. This work proposes a green and low-energy direct regeneration route for cathode materials and provides important theoretical guidance for their efficient repair and regeneration.

Achieving selective alkyne hydrogenation under mild conditions is highly appealing. In this work, cysteamine-modified Pd-based COF (denoted as Pd–TpBpy/Cys COF) was prepared and used as a heterogeneous redox mediator for the electrocatalytic semi-hydrogenation of terminal alkynes with H₂O as a sustainable hydrogen source. Notably, Pd–TpBpy/Cys COF could enable the reaction to proceed at a more positive potential and enhance the catalytic selectivity, which was superior to that of the unmodified Pd-based COF. Mechanistic investigation indicated that the in situ-generated H* by H₂O electrolysis was the key intermediate, and the semi-hydrogenation reaction proceeded through a addition pathway. In addition, good recyclability of the Pd–TpBpy/Cys COF showed its promising application potential.

Alginate, a biopolymer sourced from brown seaweed, is of growing interest for bio-based materials, highlighting the need for sustainable extraction methods tailored to deliver physicochemical properties suitable for material fabrication. This work investigates a low-hazard sodium citrate chelation process that replaces multi-step extraction with a single mild-pH operation for cation removal and alginate isolation. The effects of temperature, time, and citrate concentration on the yield and physicochemical properties were evaluated using the response surface methodology. Optimum conditions (49.5 °C, 1 h, and 0.125 M citrate) resulted in a 21.0 ± 0.6% yield and a high molecular weight (508 ± 18 kDa), a ninefold increase compared to that with non-optimized extraction. The method was reproducible at a 20-fold scale and verified by Fourier-transform infrared spectroscopy analysis. Films derived from the optimized alginate exhibited enhanced flexibility (tensile strain = 11 ± 2%) and lower stiffness (Young's modulus = 2091 ± 236 MPa) relative to those from lower molecular weight commercial alginate. Fourier-transform infrared spectroscopy, differential scanning calorimetry, and scanning electron microscopy showed that the optimized films maintained comparable microstructural density and glass transition temperature to commercial films, with subtle differences in ionic coordination and thermal stability. In terms of environmental assessment, the optimized extraction reduced the total energy use by 62% and global warming potential by 17%, compared to non-optimized extraction. This work advances a scalable, lower impact process consistent with green chemistry principles for producing alginate suitable for bio-based plastics.

Correction for ‘Cesium chemistry enables microporous carbon nanofibers with biomimetic ion transport channels for zinc-ion capacitors’ by Zhenye Yin et al., Green Chem., 2025, 27, 10699–10710, https://doi.org/10.1039/D5GC02376A.

Aliphatic polyesters show potential as substitutes for non-biodegradable materials, helping reduce plastic pollution. However, their synthesis often requires heavy metal catalysts, and conventional polyesters lack property diversity, limiting broader applications. Here, we developed an environment-friendly, multifunctional polyester as a versatile material. Cationic aggregation-mediated multifunctional polyesters have been effectively synthesized through a large-scale melt polycondensation process utilizing a carboxyl back-biting mechanism in the absence of any catalyst. Cationic aggregation in situ acts as a dynamic cross-linking point, enabling a single polymer to exhibit switchable and contrasting properties, transitioning between elasticity, transparency, and water-solubility and rigidity, opacity, and water-insolubility. Meanwhile, the material shows outstanding weldability at room temperature after fracture, and the welded material exhibits mechanical properties similar to the original material due to dynamic cross-linking points. The material exhibits a significantly higher degradation rate compared to traditional polyester, even under seawater conditions. Moreover, the polyester's switchable water solubility allows efficient separation from mixed plastics for closed-loop recycling. Additionally, replacing with antibacterial cations can upcycle the polyester into high-value antibacterial materials, enhancing sustainability. This work provides insights into the design of multifunctional, catalyst-free and sustainable polyesters for a broad range of applications.

Electrocatalytic amino acid synthesis, which uses renewable energy-generated electricity, can overcome the high energy consumption and environmental burden brought by classical methods. Here, we discuss the main steps of electrocatalytic amino acid synthesis and summarize the advanced progress in this field. The electrochemical processes are classified according to different nitrogen sources, namely NH₂OH, NO₃^—, NO, and NH₃. Electrochemical synthesis can directly form C–N bonds under mild conditions through the reduction of nitrogen sources and the combination with carbon sources. However, when nitrogen oxides are used as nitrogen sources, excessive reduction to ammonia can reduce the selectivity of amino acids. Therefore, the rational design of catalysts is crucial to balance the kinetic mismatch and intermediate stability to achieve selective amino acid production. Finally, we provide an outlook on performance improvement strategies for electrochemical amino acid synthesis to encourage further research efforts and development in this field.

The increasing demand for sustainable and cost-effective batteries has accelerated in-depth research on zinc-ion batteries (ZIBs) as an ideal alternative to lithium-ion batteries (LIBs). V₂O₅ is a widely investigated material for charge storage due to its rich electrochemistry; however, the bulky crystalline structure of commercial V₂O₅ hinders its high potential by constraining Zn²⁺ ion migration, causing structural instability and resulting in premature failure. In this study, we present a low-cost, scalable and eco-friendly strategy to synthesize layered V₂O₅via a one-pot process using polyvinyl alcohol (PVA) as a binder, producing a ready-to-coat cathode slurry. Furthermore, we eliminated the use of non-biodegradable and toxic fluorinated plastics, such as polyvinylidene fluoride (PVDF), and solvents, like N-methyl pyrrolidone (NMP), which are traditionally employed for cathode slurry preparation. The material prepared using the proposed method showed an interlayer spacing of 8.4 Å, which significantly improved Zn²⁺ ion migration. Furthermore, PVA-assisted binding improved the electrolyte–active material interphase, resulting in efficient charge transfer. Electrochemical characterization showcased the remarkable cyclability of the proposed cathode material, achieving a capacity of 480 mAh g⁻¹ at 0.5 A g⁻¹ for 100 cycles and an exceptional long-term cyclability of 280 mAh g⁻¹ at 4 A g⁻¹ over 6500 cycles, retaining 98% capacity in the last 6000 cycles. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic intermittent titration technique (GITT) further confirmed highly efficient and favourable charge-transfer kinetics with promising fast charging properties. This study highlights the potential of bilayered V₂O₅ nanostrands and green processing approaches for scalable and sustainable ZIB production, paving the way for next-generation grid-scale energy storage.