Spatial Engineering Direct Cooperativity between Binding Sites for Uranium Sequestration

Abstract

Preorganization is a basic design principle used by nature that allows for synergistic pathways to be expressed. Herein, a full account of the conceptual and experimental development from randomly distributed functionalities to a convergent arrangement that facilitates cooperative binding is given, thus conferring exceptional affinity toward the analyte of interest. The resulting material with chelating groups populated adjacently in a spatially locked manner displays up to two orders of magnitude improvement compared to a random and isolated manner using uranium sequestration as a model application. This adsorbent shows exceptional extraction efficiencies, capable of reducing the uranium concentration from 5 ppm to less than 1 ppb within 10 min, even though the system is permeated with high concentrations of competing ions. The efficiency is further supported by its ability to extract uranium from seawater with an uptake capability of 5.01 mg g−1, placing it among the highest‐capacity seawater uranium extraction materials described to date. The concept presented here uncovers a new paradigm in the design of efficient sorbent materials by manipulating the spatial distribution to amplify the cooperation of functions.

Amidoxime Group‐Anchored Single Cobalt Atoms for Anti‐Biofouling during Uranium Extraction from Seawater

“…[15] Numerous adsorbents have been fabricated for extracting uranium from seawater, and many of them exhibit promising uranium extraction capacity in natural seawater under laboratory conditions. [16] However, seawater is highly complex, possessing high ion strength and complicated interfering ions that hinder the extraction of uranium in deficient concentrations. Additionally, seawater contains abundant biofouling of marine microorganisms and other biological entities, limiting the practical application of uranium adsorbents in natural ocean environments.…”

Accelerated Chemical Thermodynamics of Uranium Extraction from Seawater by Plant‐Mimetic Transpiration

“…[ 1 , 4 ] Thus, the sustainable extraction of uranium from seawater is considered a promising approach for the long‐term sustainable development of nuclear power. Many types of uranium adsorbents have been developed for the efficient recovery of uranium from seawater, [ 5 ] including inorganic materials, [ 6 ] synthetic organic molecules/polymers, [ 7 ] natural or modified protein/biomass‐based macromolecules, [ 8 ] and various types of nanostructured adsorbents such as grafted polymeric porous supports, metal–organic frameworks (MOFs), [ 9 ] covalent–organic frameworks (COFs), [ 10 ] porous carbons, [ 11 ] porous aromatic frameworks (PAFs), [ 12 ] and porous organic polymers (POPs). [ 13 ] However, a large number of technical difficulties are associated with the processing of the massive quantities of seawater required for uranium extraction because of the extremely low uranium concentration (3.3 ppb) in seawater.…”

Theory-Guided Design of a Method to Obtain Competitive Balance between U(VI) Adsorption and Swaying Zwitterion-Induced Fouling Resistance on Natural Hemp Fibers

“…DFT calculation was employed to understand the contribution of N and O atoms from the AO group in depth. The resulting six structures showed lower binding energy ( E ads ) than UO 2 (CO 3 ) 3 4− (−31.8 eV), as shown in Figure 6 and Table S6 , indicating greater stability than UO 2 (CO 3 ) 3 4− and the trend of coordination between the adsorption sites and U(VI) ions [ 53 , 54 ]. AO(UO 2 )(CO 3 )(H 2 O) exhibited the lowest E ads (−38.8 eV) among the six structures, and it chelated with the U(VI) ion by the N atom from the amino group and the O atom from the oxime part in the AO group.…”