Mary Wilson
Well-known member
Revised: December 13, 2022
Downloaded: January 13 2023
https://doi.org/10.1021/accountsmr.2c00200
Kaikai Ma,*,# Yuk Ha Cheung,# Kent O. Kirlikovali,# Xiaoliang Wang, Timur Islamoglu, John H. Xin, and Omar K. Farha*
ABSTRACT
The SARS-CoV-2 pandemic outbreak and the unfortunate misuse of toxic chemical warfare agents (CWAs) highlight the importance of developing functional materials to protect against these chemical and pathogen threats. Metal−organic frameworks (MOFs), which comprise a tunable class of crystalline porous materials built from inorganic nodes and organic linkers, have emerged as a class of heterogeneous catalysts capable of rapid detoxi cation of multiple classes of these harmful chemical or biological hazards. In particular, zirconium-based MOFs (Zr-MOFs) feature Lewis acidic nodes that serve as active sites for a wide range of catalytic reactions, including the hydrolysis of organophosphorus nerve agents within seconds in basic aqueous solutions. In addition, postsynthetic modi cation of Zr-MOFs enables the release of active species capable of reacting with and deactivating harmful pathogens. Despite this impressive performance, utilizing Zr- MOFs in powder form is not practical for application in masks or protective uniforms.
To address this challenge, our team sought to develop MOF/ ber composite systems that could be
adapted for use under realistic operating conditions to protect civilians, military personnel, and rst
responders from harmful pathogens and chemical warfare agents. Over the last several years, our group has designed and fabricated reactive and biocidal MOF/ ber composites that e ectively capture and deactivate these toxic species. In this Account, we describe the evolution of these porous and reactive MOF/ ber composites and focus on key design challenges and considerations.
First, we devised a scalable method for the integration of Zr-MOFs onto textile substrates using aqueous precursor solutions and without using pretreated textiles, highlighting the potential scalability of this method. Moving beyond standard textiles, we also developed a microbial synthesis strategy to prepare hierarchically porous MOF/bacterial cellulose nano ber composite sponges that can both capture and detoxify nerve agents when exposed to contaminated gas ows. The mass loading of the MOF in the nano brous composite sponge is up to 90%, a ording higher work capacities compared to those of textile- ber-based composites with relatively lower MOF loadings. Next, we demonstrated that heterogeneous polymeric bases are suitable replacements for volatile liquid bases typically used in solution-phase reactions, and we showed that these composite systems are capable of e ectively hydrolyzing nerve agents in the solid state by using only water that is present as humidity. Moreover, incorporating a reactive dye precursor into the composite a ords a dual function sensing and detoxifying material that changes color from white to orange upon reaction with the byproduct following nerve agent hydrolysis, demonstrating the versatility of this platform for use in decontamination applications. We then created chlorine-loaded MOF/ ber composites that act as biocidal and reactive textiles that are capable of not only detoxifying sulfur-mustard-based chemical warfare agents and simulants but also deactivating both bacteria and the SARS-CoV-2 virus within minutes of exposure. Finally, we synthesized a mixed-metal Ti/Zr-MOF coating on cotton bers to a ord a photoactive biocidal cloth that shows fast and broad-spectrum biocidal performance against viruses and Gram-positive and Gram-negative bacteria under visible light irradiation.
Given the tunable, multifunctional nature of these MOF/ ber composites, we believe that this Account will o er new insights for the rational design and preparation of functional MOF/ ber composites and pave the way toward the development of next-generation reactive and protective textiles.
https://pubs.acs.org/doi/pdf/10.1021/accountsmr.2c00200
Downloaded: January 13 2023
https://doi.org/10.1021/accountsmr.2c00200
Kaikai Ma,*,# Yuk Ha Cheung,# Kent O. Kirlikovali,# Xiaoliang Wang, Timur Islamoglu, John H. Xin, and Omar K. Farha*
ABSTRACT
The SARS-CoV-2 pandemic outbreak and the unfortunate misuse of toxic chemical warfare agents (CWAs) highlight the importance of developing functional materials to protect against these chemical and pathogen threats. Metal−organic frameworks (MOFs), which comprise a tunable class of crystalline porous materials built from inorganic nodes and organic linkers, have emerged as a class of heterogeneous catalysts capable of rapid detoxi cation of multiple classes of these harmful chemical or biological hazards. In particular, zirconium-based MOFs (Zr-MOFs) feature Lewis acidic nodes that serve as active sites for a wide range of catalytic reactions, including the hydrolysis of organophosphorus nerve agents within seconds in basic aqueous solutions. In addition, postsynthetic modi cation of Zr-MOFs enables the release of active species capable of reacting with and deactivating harmful pathogens. Despite this impressive performance, utilizing Zr- MOFs in powder form is not practical for application in masks or protective uniforms.
To address this challenge, our team sought to develop MOF/ ber composite systems that could be
adapted for use under realistic operating conditions to protect civilians, military personnel, and rst
responders from harmful pathogens and chemical warfare agents. Over the last several years, our group has designed and fabricated reactive and biocidal MOF/ ber composites that e ectively capture and deactivate these toxic species. In this Account, we describe the evolution of these porous and reactive MOF/ ber composites and focus on key design challenges and considerations.
First, we devised a scalable method for the integration of Zr-MOFs onto textile substrates using aqueous precursor solutions and without using pretreated textiles, highlighting the potential scalability of this method. Moving beyond standard textiles, we also developed a microbial synthesis strategy to prepare hierarchically porous MOF/bacterial cellulose nano ber composite sponges that can both capture and detoxify nerve agents when exposed to contaminated gas ows. The mass loading of the MOF in the nano brous composite sponge is up to 90%, a ording higher work capacities compared to those of textile- ber-based composites with relatively lower MOF loadings. Next, we demonstrated that heterogeneous polymeric bases are suitable replacements for volatile liquid bases typically used in solution-phase reactions, and we showed that these composite systems are capable of e ectively hydrolyzing nerve agents in the solid state by using only water that is present as humidity. Moreover, incorporating a reactive dye precursor into the composite a ords a dual function sensing and detoxifying material that changes color from white to orange upon reaction with the byproduct following nerve agent hydrolysis, demonstrating the versatility of this platform for use in decontamination applications. We then created chlorine-loaded MOF/ ber composites that act as biocidal and reactive textiles that are capable of not only detoxifying sulfur-mustard-based chemical warfare agents and simulants but also deactivating both bacteria and the SARS-CoV-2 virus within minutes of exposure. Finally, we synthesized a mixed-metal Ti/Zr-MOF coating on cotton bers to a ord a photoactive biocidal cloth that shows fast and broad-spectrum biocidal performance against viruses and Gram-positive and Gram-negative bacteria under visible light irradiation.
Given the tunable, multifunctional nature of these MOF/ ber composites, we believe that this Account will o er new insights for the rational design and preparation of functional MOF/ ber composites and pave the way toward the development of next-generation reactive and protective textiles.
https://pubs.acs.org/doi/pdf/10.1021/accountsmr.2c00200