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oai:figshare.com:article/34033201 2026-09-30T14:36:29Z category_1 category_4 category_7 category_12 category_873 category_39 category_734 category_128 portal_63 item_type_6 month_year_09_2026

Experimental and DFT Cross-Validation: Synergistic Adsorption Mechanisms and Water Stability Improvement of Core-Shell Hierarchically Porous Multimetallic MIL-100(Fe)@hollow Ni/Co-BTC Composites for Perfluorooctanoic Acid Removal Heng Lin (261304) ShiYu Wen (25144483) Jiaqian Lv (23183189) Xuan Fang (647180) Jiahui Liu (724342) Na Ma (170078) Wei Dai (95957) Biophysics Biochemistry Medicine Cell Biology Chemical Sciences not elsewhere classified Ecology Biological Sciences not elsewhere classified Hematology uniform elemental composition systematic characterizations confirm providing theoretical support density functional theory calculations fully elucidates persistent organic pollutants electronic structure perspective defined hierarchical pores coordination interactions dominate multiple adsorption mechanisms water stability improvement poor water stability shell structured dual shell provides high dft calculations reveal based composite design synergistic adsorption mechanisms intact hollow core water stability shell structure synergistic roles organic frameworks hydrophobic interactions hollow ni adsorption process adsorption mechanism adsorption kinetics defined core work develops technical reference target molecules study designed structural synergy significantly improve protective barrier practical application pore filling pops ). physical mixtures ligand exchange hydrogen bonding highly efficient free metal fragile ni enhances hydrophobicity electrostatic attraction efficient remediation cyclic reusability Efficient perfluorooctanoic acid (PFOA) capture requires synergistic optimization of adsorption kinetics and capacity. Defect-free metal-organic frameworks (MOFs) with well-defined hierarchical pores are key to addressing this challenge, yet single-component MOFs face inherent limitations including monotonous pores, insufficient unsaturated metal sites, and poor water stability, which restrict their practical application. To overcome these drawbacks, this study designed and synthesized a core-shell structured dual-MOF composite, MIL-100(Fe)-on-(Ni/Co-BTC) (abbreviated as M-on-(NCB)), via a polyvinylpyrrolidone (PVP)-assisted hydrothermal strategy. The composite integrates a hollow Ni/Co-BTC core and a micro–mesoporous MIL-100(Fe) shell: the hollow core constructs diffusion pathways for target molecules and reduces mass transfer resistance; the shell provides high-density Fe active sites, enhances hydrophobicity, and acts as a protective barrier to significantly improve the water stability of the fragile Ni/Co-BTC framework. Systematic characterizations confirm the well-defined core-shell structure, distinct hierarchical pore distribution, uniform elemental composition, and intact hollow core of the composite. Benefiting from structural synergy and multiple adsorption mechanisms, M-on-(NCB) exhibits remarkably superior PFOA adsorption performance relative to single-component MOFs and their physical mixtures. A cross-validation system combining experimental characterizations and density functional theory (DFT) calculations fully elucidates the adsorption mechanism: spectroscopic and zeta potential analyses verify the synergistic roles of electrostatic attraction, ligand exchange, hydrophobic interactions, and pore filling; DFT calculations reveal the nature and strength of each interaction from an electronic structure perspective, confirming that coordination interactions dominate the adsorption process, with electrostatic attraction, hydrogen bonding, and π–CF hydrophobic interactions synergistically enhancing binding. The composite also possesses excellent water stability and cyclic reusability. This work develops a highly efficient and stable PFOA adsorbent via structural innovation, clarifies the adsorption mechanism through experimental–theoretical cross-validation, and proposes a generalizable “structural–functional complementary integration” strategy for MOF-based composite design, providing theoretical support and technical reference for efficient remediation of persistent organic pollutants (POPs). 2026-09-30T00:00:00Z Text Journal contribution 10.1021/acs.langmuir.6c04665.s001 https://figshare.com/articles/journal_contribution/Experimental_and_DFT_Cross-Validation_Synergistic_Adsorption_Mechanisms_and_Water_Stability_Improvement_of_Core-Shell_Hierarchically_Porous_Multimetallic_MIL-100_Fe_hollow_Ni_Co-BTC_Composites_for_Perfluorooctanoic_Acid_Removal/34033201 CC BY-NC 4.0