The management of iodine species,notorious for their environmental persistence and health risks,requires innovative materials capable of efficient capture and conversion.Herein,we report the self-assembly and characte...The management of iodine species,notorious for their environmental persistence and health risks,requires innovative materials capable of efficient capture and conversion.Herein,we report the self-assembly and characterization of a Zr-based metal-organic tetrahedron(1)functionalized with redox-active triazatriangulenium(TATA+)panels.The cage exhibits a high binding affinity for triiodide(I_(3)^(-))(ca.10^(6) M^(-1))in methanol.The strong host-vip complexation significantly facilitates the disproportionation hydrolysis of I_(2) to generate I_(3)^(-)andHOI.It also enables photocatalytic aerobic oxidation of I−into I_(3)^(-)within its cavity.Mechanistic investigations revealed the key steps involving vip-to-host photoinduced electron transfer(ET)to generate radicals I^(·)∙and 1∙and ET from 1∙to dioxygen to generate superoxide.Solid-state adsorption experiments showed the rapid removal of I_(2) and I_(3)^(-)from water by 1-NTf_(2) because of the high affinity for polyiodides.Importantly,although solid-state 1-NTf_(2) has no ability to directly adsorb I−from water,we have for the first time developed a light-driven strategy that enables removal of I^(-)−through coupled photooxidation and sequestration.This work highlights the significant potential of integrating photoredox-active moieties within stable metal-organic cages for controlling iodine binding and speciation and opens new avenues to address environmental and energy-related sequestration challenges.展开更多
基金the National Natural Science Foundation of China(22201075,21971069,and 22501086)G.L.acknowledges the China Postdoctoral Science Foundation(2025M770977)the Postdoctoral Fellowship Program of CPSF(GZC20250659).
文摘The management of iodine species,notorious for their environmental persistence and health risks,requires innovative materials capable of efficient capture and conversion.Herein,we report the self-assembly and characterization of a Zr-based metal-organic tetrahedron(1)functionalized with redox-active triazatriangulenium(TATA+)panels.The cage exhibits a high binding affinity for triiodide(I_(3)^(-))(ca.10^(6) M^(-1))in methanol.The strong host-vip complexation significantly facilitates the disproportionation hydrolysis of I_(2) to generate I_(3)^(-)andHOI.It also enables photocatalytic aerobic oxidation of I−into I_(3)^(-)within its cavity.Mechanistic investigations revealed the key steps involving vip-to-host photoinduced electron transfer(ET)to generate radicals I^(·)∙and 1∙and ET from 1∙to dioxygen to generate superoxide.Solid-state adsorption experiments showed the rapid removal of I_(2) and I_(3)^(-)from water by 1-NTf_(2) because of the high affinity for polyiodides.Importantly,although solid-state 1-NTf_(2) has no ability to directly adsorb I−from water,we have for the first time developed a light-driven strategy that enables removal of I^(-)−through coupled photooxidation and sequestration.This work highlights the significant potential of integrating photoredox-active moieties within stable metal-organic cages for controlling iodine binding and speciation and opens new avenues to address environmental and energy-related sequestration challenges.
