Moderate Carbonization and Nanoconfinement Engineering for High-Performance Fluoride Electrosorption in UiO-66(Ce) Derivatives

ACS Applied Materials & Interfaces · 2025-08-11

Efficient and selective removal of fluoride from water remains a critical challenge in environmental remediation. In this work, we report a thermally modulated strategy to enhance the electrosorption performance of cerium-based metal–organic frameworks (UiO-66(Ce)) for fluoride removal. Rather than complete carbonization, controlled partial carbonization at 400 °C was found to be optimal, inducing the in situ formation of well-dispersed CeO2 nanoparticles and the development of interconnected mesoporous channels. The evolution of the pore structure with different thermal treatment temperatures was comprehensively characterized by N2 adsorption–desorption analysis and high-resolution transmission electron microscopy (HRTEM). This approach effectively balances electrical conductivity and active site availability, leveraging a nanoconfinement effect that restricts CeO2 aggregation, preserves active sites, and facilitates efficient ion transport. The optimized UiO-66(Ce)-400 °C material exhibits a high electrosorption capacity of 73.7 mg·g–1, rapid kinetics, and strong fluoride selectivity in the presence of competing anions. Finite element simulations and electrochemical analyses confirm that the synergy between enhanced mesoporosity, conductivity, and active site accessibility drives superior performance. Furthermore, the electrode demonstrates excellent regeneration and stability over five cycles. This study presents a versatile and scalable approach for engineering MOF-derived materials, offering valuable insights into the design of next-generation electrosorption systems for water treatment.

Enhanced fluoride removal through pulsed electrosorption: Optimizing energy efficiency and selectivity in complex water matrices by EDL regulation

Chemical Engineering Journal · 2025-06-08 · 1 citations

Interplay of Structural Properties and Redox Behavior in CeO₂ Nanoparticles: Impact on Reactivity and Bioavailability

Environmental Science & Technology · 2025-02-06 · 10 citations

The environmental redox transformation of CeO2 is crucial for evaluating its ecological risk and understanding the geochemical cycling of cerium (Ce). In this study, we examined the effects of crystallinity on CeO2 dissolution and monitored the structural evolution during redox transformations. The reductive dissolution and reoxidation behavior of CeO2 (100 mg/L) was examined in the presence of 200 μM citrate. Our findings indicate that ligand-induced dissolution is more pronounced in CeO2 with lower crystallinity under both dark and light conditions. This dependence is related to the intensive ligand complexation at oxygen vacancy sites, resulting in a higher complexation of Ce(III) and more efficient photoelectron generation for Ce(IV) reduction. During cyclic dissolution–reprecipitation, CeO2 notably transformed into an amorphous phase, progressively decreasing the crystallinity of the nanoparticles. Consequently, the dissolution fraction of well-crystallized CeO2 increased significantly from 1.2% in the first cycle to 11.4% in the third cycle, suggesting a transition to structures with higher interfacial reactivity. Similar transformation and dissolution behavior was observed in redox oscillations in a soil environment. Additionally, hydroponic exposure experiments with Arabidopsis thaliana, treated with 100 mg/L CeO2 for 7 days, demonstrated increased Ce uptake by roots post-transformation, with a higher proportion of CePO4 detected within the plants. This comprehensive study not only provides vital mechanistic insights into the transformation processes of CeO2 but also aids in assessing the ecological risks associated with engineered CeO2 nanomaterials.

Association of the Ionizable Organic Compound Lamotrigine with Dissolved Humic Acid: Mechanistic Insights and Modeling Optimization

Environmental Science & Technology · 2025-09-22 · 1 citations

The association of ionizable organic compounds (IOCs) with natural organic matter (NOM) plays a critical role in governing their bioavailability and transport in the environment. However, the complexity of these interactions poses a significant challenge to accurately predict their environmental fate. In this study, we investigated the binding mechanisms of the cationic pharmaceutical lamotrigine (LTG) with soil humic acid under different environmental conditions. While LTG–humic acid binding is primarily driven by electrostatic attraction, the conventional NICA–Donnan model failed to accurately capture its pH dependence, which accounts for the binding of LTG-H+ to low-affinity proton sites in humic acid. Incorporating proton cobinding significantly improved model performance across pH, ionic strength, and cation competition scenarios, suggesting that humic acid-bound protons facilitate LTG adsorption. The nonionic interaction between LTG and humic substances was further identified by spectroscopic characterization, revealing hydrogen bonding mechanisms including COOH···N interactions between protonated carboxylic acids and the LTG triazine ring and charge-assisted N+–H···COO– bonding stabilized by electrostatic attraction. Finally, STD-NMR epitope mapping revealed preferential binding at the C–Cl position, indicating a spatially organized, cooperative interaction of hydrogen bonding and electrostatic attraction. These findings integrate molecular-scale insights with model refinement, offering a more robust framework for predicting IOC–NOM interactions in environmental systems.

Activation of bulk MoS2 for simultaneous chromium and copper removal from electroplating wastewater: Mechanisms and performance

Colloids and Surfaces A Physicochemical and Engineering Aspects · 2025-04-02 · 2 citations

Chemisorption contribution of support materials in CO ₂ capture by amine-impregnated adsorbents

Journal of Materials Chemistry A · 2025-01-01 · 5 citations

The support structure in amine-impregnated adsorbents plays an active role in CO 2 chemisorption, rather than merely serving as an inert framework.

Crystalline carbon nitride derived self-assembly composite membranes with enhanced self-cleaning performance toward dye/salt separation

Journal of Environmental Management · 2025-05-30

Selective fluoride removal from groundwater using CNT-CeO2 electrodes in capacitive deionization (CDI)

Chemical Engineering Journal · 2024-01-26 · 45 citations

Robust carbon nitride nanosheet interlayered thin-film nanocomposite membrane for enhanced organic solvent nanofiltration

Separation and Purification Technology · 2024-11-10 · 3 citations

Covalently modified MoS2 for the fabrication of interlayered thin film composite membranes with excellent structural stability against swelling and drying in organic solvent nanofiltration

Journal of Membrane Science · 2024-06-12 · 10 citations