A Bio‐inspired Nano‐pocket Spatial Structure for Targeting Uranyl Capture

Abstract

Biology has evolved excellent spatial structures for high‐selectivity and high‐affinity capture of heavy metals. Inspired by the spatial structure of the superb‐uranyl binding protein SUP, we mimic the spatial structure of SUP in metal–organic frameworks (MOFs). The MOF UiO‐66‐3C4N fabricated by introducing 4‐aminoisophthalic acid into UiO‐66 shows high uranyl adsorption capacity both in simulated seawater and in natural seawater. In natural seawater, UiO‐66‐3C4N exhibits 17.03 times higher uranium extraction capacity than that of vanadium, indicating the high selectivity of the adsorbent. The EXAFS analysis and DFT calculation reveal that UiO‐66‐3C4N forms smaller nano‐pocket for uranyl capture than that of SUP protein, which can both restrict the entrance of the other interfering ions with larger size and reinforce the binding by increasing the coordination interaction, and therefore qualify the nano‐pocket with high affinity and high selectivity to uranyl.

Photoinduced Enhancement of Uranium Extraction from Seawater by MOF/Black Phosphorus Quantum Dots Heterojunction Anchored on Cellulose Nanofiber Aerogel

“…However, these materials are seriously limited because of their relatively low adsorption efficiency and unfavorable marine biofouling. [ 18 ] Because of highly anisotropic charge‐transport, optical‐response properties as well as thickness‐dependent bandgap, black phosphorus (BP) has been widely applied in photocatalysis and photoelectric devices. [ 19 ] Herein, BP@CNF‐MOF adsorbent, in which UiO‐66‐NH 2 /black phosphorus quantum dots (MOF/BPQDs) heterojunctions are anchored on the CNF aerogel surface, are successfully designed and synthesized for uranium extraction from natural seawater.…”

Metal‐Organic‐Framework Based Functional Materials for Uranium Recovery: Performance Optimization and Structure/Functionality‐Activity Relationships

“…Wang et al. incorporated different carboxyl and amino containing ligands into UiO‐66 to fabricate nano‐pockets for UO 2 2+ recovery (Figure 6a) [15a] . Thereinto, UiO‐66‐3C4N with 4‐aminoisophthalic acid integrated into UiO‐66 displayed highest uptake capacity of 190.27 mg/g to uranium in 8 ppm uranium spiked simulated seawater (Figure 6b).…”

“…(c) Uranium selectivity of UiO‐66‐3C4N in natural seawater. (d) DFT calculation of interaction between uranyl and functionalized UiO‐66 [15a] . Reprinted with permission from ref.…”

“…Much effort has been devoted to optimizing the adsorption performance of MOF-based adsorbents including adsorption capacity, adsorption kinetics, selectivity and their practical performance like acid/alkaline stability in uranium-polluted environments and anti-biofouling property in seawater. [15] The development of MOF-based adsorbents for uranium recovery consists of two aspects: firstly, modify the typical MOFs either by grafting functional groups in the framework or integrate other functional materials to form composite. [16] Owing to their outstanding stability, MILs (MIL = Matériaux de l'Institut Lavoisier), UiOs (UiO = University of Oslo) and ZIFs (ZIF = Zeolitic Imidazolate Framework) series of MOFs are the most widely studied MOFs in the uranium capture.…”

Spidroin‐Inspired, High‐Strength, Loofah‐Shaped Protein Fiber for Capturing Uranium from Seawater

“…[13,14] Inspired by the uranium coordination environment of SUP, uranyl binding nano-structures were chemically designed for uranium extraction. [15] Although these SUP-based adsorbents show promising uranium adsorption ability, their microscopic size, low mechanical strength, and complicated preparation techniques, limit their large-scale offshore trials.…”