Self-supported trimetallic NiZnLa nanosheets on hierarchical porous graphene oxide-polymer composite fibers for enhanced phosphate removal from water.

Phosphate-induced water eutrophication has attracted global attention. Fabricating adsorbents with both high phosphate adsorption affinity and accessible separation property is challenging. Herein, PG@NZL, a hierarchical nanocomposite fibrous membrane, was fabricated via in-situ growth of La-doped NiZn-LDH (NiZnLa0.1) over electrospun graphene oxide-polymer composite fibers (PG). The porous surface of the PG fibers provided abundant anchor sites for the vertical self-supported growth of NiZnLa0.1 nanosheets, contributing to a high surface area. The La-doped NiZnLa0.1 trimetallic LDH achieved a much higher adsorption capacity than NiZn-LDH. The negative adsorption energy (-1.45 eV), calculated with DFT, confirmed its spontaneous adsorption potential for phosphate. Interestingly, the PG fibers contributed to oxygen vacancies and the metal center electronic structure evolution of NiZnLa0.1, thus strengthening the coordination with phosphate. Mechanistic analysis revealed that the high adsorption capacity of PG@NZL is attributed to its superior anion exchange property, oxygen vacancies, and inner-sphere complexation. Therefore, the flexible and easily separated PG@NZL nanocomposite fibrous membrane is a promising adsorbent for effectively treating phosphate-bearing wastewater.

Bowknot-like Zr/La bimetallic organic frameworks for enhanced arsenate and phosphate removal: Combined experimental and DFT studies.

Hazardous oxyanions in water bodies are potentially toxic to aquatic life, and the coexistence of multiple anions aggravates the toxicity. Herein, bowknot-like Zr/La bimetallic organic frameworks (Zr/La-BTC) were developed with superior hazardous oxyanion adsorption capacities, i.e., approximately 102 mg/g for arsenate and 159 mg/g for phosphate, respectively. The molar ratio of Zr to La in Zr/La-BTC plays a significant role in the structure and the adsorption efficiencies. Notably, the experiment-derived adsorption capacities of various Zr/La-BTC samples were consistent with their adsorption energies calculated by density-function theory (DFT). Further mechanism analysis revealed that coordination of Zr/La atoms with the target anion groups occurred during adsorption. The positive shift of binding energies in La 3d and Zr 3d XPS spectra and Bader charge analysis unveiled that back-donation interactions dominated the adsorption process. The reliable adsorption selectivity and reusability of 0.1Zr/La-BTC were verified with anion competition experiments and four adsorption-desorption cycles. Overall, this study provides significant insight into the design of high-performance bimetallic organic frameworks for the enhanced removal of hazardous oxyanions from water.