The sequestration of^(99)Tc represents one of the most challenging tasks in nuclear waste decontamination In the event of a radioactive waste leak,^(99)TcO_(4)^(-)(a main form of^(99)Tc)would spread into the groundwa ...The sequestration of^(99)Tc represents one of the most challenging tasks in nuclear waste decontamination In the event of a radioactive waste leak,^(99)TcO_(4)^(-)(a main form of^(99)Tc)would spread into the groundwa ter,a scenario difficult to address with conventional anion exchange materials like resin and inorganic cationic sorbents.Herein,we present a nickel(II)metal-organic framework(MOF),TNU-143,featuring3D four-fold interpenetrated networks.TNU-143 exhibits efficient ReO_(4)^(-)(a nonradioactive analogue o^(99)TcO_(4)^(–))removal with fast anion exchange kinetics(<1 min),high sorption capacity(844 mg/g for ReO_(4)^(-))and outstanding selectivity over common anions.More importantly,TNU-143 shows superior stability in alkaline solution and can remove 91.6%ReO_(4)^(-)from simulated alkaline high-level waste(HLW)stream with solid-liquid ratio of 40 g/L.The uptake mechanism is elucidated by the single-crystal structure o TNU-143(Re),showing that ReO_(4)^(-)anions are firmly coordinated to nickel cation to result in a 2D lay ered structures.Density functional theory(DFT)calculations confirm the transformation from TNU-143 to TNU-143(Re)is a thermodynamically favorable process.This work presents a new approach to the removal of Re O_(4)^(-)/^(99)TcO_(4)^(-)from alkaline nulcear fuel using MOF sorbents.展开更多
The development of hydrogen-bonded organic frameworks(HOFs)faces significant constraints,primarily attributed to their fragile architectures and limited functionalization capabilities.To overcome these limitations,thi...The development of hydrogen-bonded organic frameworks(HOFs)faces significant constraints,primarily attributed to their fragile architectures and limited functionalization capabilities.To overcome these limitations,this work presents a new polymeron-HOF strategy by covalently tethering armor-like polymers onto the surface of HOFs.The application of this approach not only bolsters the stability of HOFs,but also facilitates the customization of their functional expansion in radionuclide sequestration.The optimized HOF-polymer materials display extraordinary ability in radionuclide sequestration,achieving uptake of I^(-)(0.699 g g^(-1)),IO_(3)^(-)(0.285 g g^(-1))and ReO_(4)^(-)(1.616 g g^(-1),setting a world record),fast adsorption kinetics(~100% removal within 45 s),and exceptional regeneration capability(>30 cycles)under continuous flow conditions.These outstanding performances benefit from the internal porous channels and surface imidazolium polymer coatings of HOFs,as proved by density functional theory calculation and molecular dynamics simulations.This work paves the way for the rational design of HOF-based hybrid materials tailored to versatile applications.展开更多
基金supported by National Natural Science Foundation of China(No.22171210)Research Project of Tianjin Education Commission(No.2023KJ182)Tianjin Research Innovation Project for Postgraduate Students(No.2022BKY200)。
文摘The sequestration of^(99)Tc represents one of the most challenging tasks in nuclear waste decontamination In the event of a radioactive waste leak,^(99)TcO_(4)^(-)(a main form of^(99)Tc)would spread into the groundwa ter,a scenario difficult to address with conventional anion exchange materials like resin and inorganic cationic sorbents.Herein,we present a nickel(II)metal-organic framework(MOF),TNU-143,featuring3D four-fold interpenetrated networks.TNU-143 exhibits efficient ReO_(4)^(-)(a nonradioactive analogue o^(99)TcO_(4)^(–))removal with fast anion exchange kinetics(<1 min),high sorption capacity(844 mg/g for ReO_(4)^(-))and outstanding selectivity over common anions.More importantly,TNU-143 shows superior stability in alkaline solution and can remove 91.6%ReO_(4)^(-)from simulated alkaline high-level waste(HLW)stream with solid-liquid ratio of 40 g/L.The uptake mechanism is elucidated by the single-crystal structure o TNU-143(Re),showing that ReO_(4)^(-)anions are firmly coordinated to nickel cation to result in a 2D lay ered structures.Density functional theory(DFT)calculations confirm the transformation from TNU-143 to TNU-143(Re)is a thermodynamically favorable process.This work presents a new approach to the removal of Re O_(4)^(-)/^(99)TcO_(4)^(-)from alkaline nulcear fuel using MOF sorbents.
基金supported by the National Natural Science Foundation of China(22171210,21771139,U20A20141,U23A20119)CAS Project for Young Scientists in Basic Research(YSBR-039)+1 种基金Tianjin Research Innovation Project for Postgraduate Students(2022BKY200)C?EM,School of Physical Sciences and Technology,Shanghai Tech University(#EM02161943)for the scientific and financial support of EM facilities。
文摘The development of hydrogen-bonded organic frameworks(HOFs)faces significant constraints,primarily attributed to their fragile architectures and limited functionalization capabilities.To overcome these limitations,this work presents a new polymeron-HOF strategy by covalently tethering armor-like polymers onto the surface of HOFs.The application of this approach not only bolsters the stability of HOFs,but also facilitates the customization of their functional expansion in radionuclide sequestration.The optimized HOF-polymer materials display extraordinary ability in radionuclide sequestration,achieving uptake of I^(-)(0.699 g g^(-1)),IO_(3)^(-)(0.285 g g^(-1))and ReO_(4)^(-)(1.616 g g^(-1),setting a world record),fast adsorption kinetics(~100% removal within 45 s),and exceptional regeneration capability(>30 cycles)under continuous flow conditions.These outstanding performances benefit from the internal porous channels and surface imidazolium polymer coatings of HOFs,as proved by density functional theory calculation and molecular dynamics simulations.This work paves the way for the rational design of HOF-based hybrid materials tailored to versatile applications.
