The adsorption,degradation,and sensing of chemical warfare agents are highly important.In this work,a new Zr_((IV))-based metal-organic gel(MOG)was designed and synthesized,which demonstrated dualfunctional performanc...The adsorption,degradation,and sensing of chemical warfare agents are highly important.In this work,a new Zr_((IV))-based metal-organic gel(MOG)was designed and synthesized,which demonstrated dualfunctional performance in the degradation of nerve agent simulants and the adsorptive sensing of blister agent simulants.A Zr_((IV))-based MOG,namely,Zr-MOG-taBDC(H_(2)taBDC=2-(1H-1,2,4-triazol-1-yl)terephthalic acid),was synthesized through the thermal transformation of a tetrahedral Zr_((IV))-based metal-organic cage,{[Cp_(3)Zr_(3)(μ_(3)-O)(μ_(2)-OH)_(3)]_(4)(taBDC)_(6)}·(Cl^(-))_(4)(Zr-MOC-taBDC),in a mixed acetonitrile/water solvent system,bypassing the need for tedious anion exchange and high-boiling solvents.The resulting MOG exhibited hierarchical porosity and high stability across a wide pH range(1-11).Catalytic tests revealed that Zr-MOG-taBDC achieved 95.4%degradation efficiency for the nerve agent simulant diethyl phenylphosphonate(DEPPT),with a half-life of 49.5 minutes,outperforming its crystalline MOC precursor.Additionally,the gel demonstrated a high adsorption capacity(0.6 g g^(-1))for the mustard gas simulant 2-chloroethyl ethyl sulfide(CEES),enabling real-time detection via a quartz crystal microbalance(QCM)with a linear response range up to 100 ppm.Mechanistic studies indicated that degradation proceeds via P-S bond cleavage catalyzed by Zr-OH-H_(2)O Lewis acid-base sites,whereas adsorption involves reversible physical and irreversible chemical interactions with triazole groups and Zr-oxo clusters.This work highlights the potential of Zr-MOGs as multifunctional materials for chemical warfare agent mitigation and sensing.展开更多
基金supported by the National Natural Science Foundation of China(grant no.22073032).
文摘The adsorption,degradation,and sensing of chemical warfare agents are highly important.In this work,a new Zr_((IV))-based metal-organic gel(MOG)was designed and synthesized,which demonstrated dualfunctional performance in the degradation of nerve agent simulants and the adsorptive sensing of blister agent simulants.A Zr_((IV))-based MOG,namely,Zr-MOG-taBDC(H_(2)taBDC=2-(1H-1,2,4-triazol-1-yl)terephthalic acid),was synthesized through the thermal transformation of a tetrahedral Zr_((IV))-based metal-organic cage,{[Cp_(3)Zr_(3)(μ_(3)-O)(μ_(2)-OH)_(3)]_(4)(taBDC)_(6)}·(Cl^(-))_(4)(Zr-MOC-taBDC),in a mixed acetonitrile/water solvent system,bypassing the need for tedious anion exchange and high-boiling solvents.The resulting MOG exhibited hierarchical porosity and high stability across a wide pH range(1-11).Catalytic tests revealed that Zr-MOG-taBDC achieved 95.4%degradation efficiency for the nerve agent simulant diethyl phenylphosphonate(DEPPT),with a half-life of 49.5 minutes,outperforming its crystalline MOC precursor.Additionally,the gel demonstrated a high adsorption capacity(0.6 g g^(-1))for the mustard gas simulant 2-chloroethyl ethyl sulfide(CEES),enabling real-time detection via a quartz crystal microbalance(QCM)with a linear response range up to 100 ppm.Mechanistic studies indicated that degradation proceeds via P-S bond cleavage catalyzed by Zr-OH-H_(2)O Lewis acid-base sites,whereas adsorption involves reversible physical and irreversible chemical interactions with triazole groups and Zr-oxo clusters.This work highlights the potential of Zr-MOGs as multifunctional materials for chemical warfare agent mitigation and sensing.
