To investigate the effect of calcination temperature on the electrochemical lithium-adsorption performance of Prussian blue-derived iron oxides, Prussian blue (PB) synthesized via a hydrothermal method was used as the precursor. A series of iron-oxide materials were obtained by calcination at 350, 550, and 650 °C in air. Scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FT-IR), and N2 adsorption–desorption isotherms were employed to characterize the morphology, crystal phase, and pore structure of the prepared materials. Their electrochemical behaviors, Li+ adsorption capacity, adsorption kinetics, and cycling stability were evaluated in LiCl electrolyte. The results reveal that calcination temperature exerts a significant influence on the pore-structure evolution and crystal-phase transformation of the adsorbents. PB-Fe2O3 (350 °C) delivers the largest specific surface area of 67.52 m2·g−1; PB-Fe2O3 (550 °C) forms a mixed β/γ-Fe2O3 phase while preserving the mesoporous structure; obvious particle agglomeration and pore-structure shrinkage occur for PB-Fe2O3 (650 °C). At −0.9 V (vs. saturated calomel electrode, SCE), the maximum experimentally determined Li+ adsorption capacity of PB-Fe2O3 (550 °C) reaches 132.23 mg·g−1, which is higher than those of pristine PB, PB-Fe2O3 (350 °C), and PB-Fe2O3 (650 °C). Kinetic analyses demonstrate that the Li+ adsorption processes of pristine PB and PB-Fe2O3 (550 °C) can be well described by the pseudo-first-order kinetic model. After 10 charge–discharge cycles, PB-Fe2O3 (550 °C) maintains a capacity retention above 93%, exhibiting favorable short-term cycling stability. Moreover, in a binary Li+/Mg2+ simulated brine, PB-Fe2O3 (550 °C) exhibited preferential Li+ uptake with a Li+/Mg2+ separation factor was 4.07, demonstrating its potential for selective lithium recovery from Mg2+-rich brines. Appropriate calcination can harmonize the pore-structure, crystal-phase, and oxygen-vacancy characteristics of materials, thus improving their electrochemical lithium-adsorption performance. This work provides experimental support for structural regulation and performance optimization of Prussian blue-derived iron oxides for electrochemical lithium adsorption.
In this study, a novel water-insoluble copolymer of oxidized β-cyclodextrin (β-CDO) and phytic acid (PA) was designed, synthesized, and evaluated for the dual adsorption of heavy metals and organic pollutants from wastewater. β-CD was oxidized using the TEMPO/NaOCl system to yield β-CD containing carboxyl functional groups (β-CDO). The copolymer was synthesized via a solvent-free esterification method by heating the reactants at 120 °C, thereby forming phosphate ester linkages between the hydroxyl groups of β-CDO and PA. Five polymers with different ratios were prepared and characterized by FTIR, SEM, and TGA, confirming linkage formation, porous morphology, and good thermal stability of the β-CDO-co-PA copolymer. Polymer E, with a β-CDO-to-PA ratio of 3:1, exhibited outstanding adsorption capabilities. Polymer E removed 99.0% of Pb(II) from a 50 mg/L solution at pH 5 and 30 °C, reaching equilibrium within 30 min. For methylene blue (MB), it showed a removal efficiency greater than 98%, with a Qe value of 196 mg/g at pH 7.0 through β-CD inclusion complexation and electrostatic interactions with PA. In real wastewater, polymer E efficiently removed several heavy metals, including Pb (99.5%), Cr (98.6%), Cu (98.8%), and As (98.5%), through synergistic adsorption, with PA phosphate groups chelating metal ions and β-CD cavities capturing organic contaminants. The adsorption behavior followed pseudo-second-order kinetics, indicating the predominance of chemisorption, and the Langmuir isotherm, indicating monolayer coverage. Polymer E also retained more than 90% efficiency after six regeneration cycles.
Grapevine (Vitis spp.) proteomics is an important tool for investigating berry development, stress responses, dormancy, root adaptation and extracellular defense processes. However, many grapevine tissues and extracellular matrices remain analytically challenging because of relatively low recoverable protein abundance and high levels of interfering compounds, including polyphenols, polysaccharides, sugars, pigments, lipids and structural polymers. This review provides a workflow-oriented overview of analytical strategies used in grapevine proteomics, covering protein extraction and clean-up, fractionation, digestion, mass spectrometry and bioinformatic processing. Matrix-adapted approaches based on TCA/acetone precipitation, phenol extraction and SDS-, urea- or guanidine-containing buffers are considered across major grapevine tissues and extracellular matrices. Gel-based, GeLC and gel-free LC–MS/MS workflows, peptide fractionation, label-free and isobaric quantification, data-independent acquisition (DIA) and post-translational modification (PTM)-oriented strategies are critically compared, with emphasis on their effects on protein recovery, proteome coverage, reproducibility and cross-study comparability. Despite advances in high-resolution LC–MS/MS, fully gel-free bottom-up workflows remain less frequently represented than gel-assisted or protein-level-prefractionated approaches. Future priorities include improved matrix-specific clean-up, workflow standardization, reference materials and quality-control procedures, and more transparent reporting of analytical and bioinformatic parameters.
Nanomaterials offer high specific surface area and tunable surface chemistry. They can be used as promising adsorbents, photocatalysts, and membrane components for wastewater treatment. However, problems of low efficiency and low recyclability limit the practical application of some nanomaterials. This review summarizes their use for inorganic and organic pollutant removal and examines defects. The modification and controllable construction of nanomaterials in terms of defect regulation, pore structure modification, and surface modification are also summarized. Pore and surface engineering strategies are discussed through a structure–property–performance framework. Then, improvements in pore and surface structures are investigated in relation to the controllable construction of nanomaterials. The evidence indicates that performance gains must be evaluated alongside regeneration, active-material leaching, transformation products, and energy demand. Future progress depends on reproducible comparisons, realistic wastewater testing, and recovery-by-design rather than removal efficiency alone.
The efficient beneficiation of low-grade Cu–Ni sulfide ores is challenging because Cu-bearing and Ni-bearing sulfide minerals are finely intergrown with gangue minerals. In this study, the ore composition and mineral liberation characteristics were examined, and different flotation flowsheets were evaluated. A flotation feed containing 80% of particles finer than 0.074 mm was selected by balancing mineral liberation against the adverse effects of excessive fines. After flowsheet optimization, a partially preferential flotation strategy was adopted, in which most Cu was first recovered into a Cu concentrate, and the remaining Cu was recovered together with Ni in a Cu–Ni bulk concentrate. For the closed-circuit flowsheet, an economic Cu concentrate with a Cu grade of 20.65% and Cu recovery of 78.77%, and qualified Cu–Ni bulk concentrates with a Ni grade of 5.43% and Ni recovery of 61.99%, were obtained. The comprehensive recovery rate of Cu was 88%. Partially preferential flotation simplifies the separation flowsheet of Cu–Ni ores while achieving substantial recovery of valuable metals. The technology is highly efficient and economical, and has broad application prospects for the beneficiation of low-grade Cu–Ni sulfide ores.
