Tailoring the Pore Size and Functionality of UiO-Type Metal–Organic Frameworks for Optimal Nerve Agent Destruction

Abstract

Evaluation of UiO-66 and UiO-67 metal-organic framework derivatives as catalysts for the degradation of soman, a chemical warfare agent, showed the importance of both the linker size and functionality. The best catalysts yielded half-lives of less than 1 min. Further testing with a nerve agent simulant established that different rate-assessment techniques yield similar values for degradation half-lives.

Swellable functional hypercrosslinked polymer networks for the uptake of chemical warfare agents

“…Toluene (10 mmol) was added to anhydrous 1,2-dichloroethane (10 mL) under a flow of nitrogen, followed by formaldehyde dimethyl acetal (15,16,17,19,20,23,25,27,30,40, or 50 mmol for 1.5, 1.6, 1.7, 1.9, 2, 2.3, 2.5, 2.7, 3, 4, or 5 equivalents of FDA, respectively). An equimolar amount of iron(III) chloride (15,16,17,19,20,23,25,27,30,40, or 50 mmol) was added and the reaction mixture heated at 80°C for 18 hours. After cooling the solid product was removed by filtration and washed with methanol several times.…”

Ultra‐Fast Degradation of Chemical Warfare Agents Using MOF–Nanofiber Kebabs

“…[8][9][10][11][12][13][14][15][16] Theu ltra-high surface area and large porosity make MOFs promising candidates for sorption of CWAs, [8,9] while the metal-containing secondary building units present in MOFs can also function as Lewis-acidic catalytic sites for CWAd estruction. [8][9][10][11][12][13][14][15][16] Theu ltra-high surface area and large porosity make MOFs promising candidates for sorption of CWAs, [8,9] while the metal-containing secondary building units present in MOFs can also function as Lewis-acidic catalytic sites for CWAd estruction.…”

“…[8][9][10][11][12][13][14][15][16] Theu ltra-high surface area and large porosity make MOFs promising candidates for sorption of CWAs, [8,9] while the metal-containing secondary building units present in MOFs can also function as Lewis-acidic catalytic sites for CWAd estruction. [10][11][12][13][14][15][16] While bulk MOF crystals exhibit excellent properties for CWAd estruction, many practical issues still need to be addressed before these materials can be widely used for this application. [10][11][12][13][14][15][16] While bulk MOF crystals exhibit excellent properties for CWAd estruction, many practical issues still need to be addressed before these materials can be widely used for this application.…”

“…[10,12,13,25] We used concentrated HCl as the modulator for the solvothermal synthesis,w hich is similar to reported recipes for these MOFs, [26] but developed our own conditions to achieve optimized growth of MOF thin-films onto nanofiber substrates.S pecifically,0 .343 mmol of ZrCl 4 and 0.343 mmol of dicarboxylic acid linkers (1:1 molar ratio) were dissolved in 20 mL of DMF.D eionized water (25 mL) and concentrated HCl (1.33 mL for UiO-66 and UiO-66-NH 2 , 0.67 mL for UiO-67) were added to the solution. [10,12,13,25] We used concentrated HCl as the modulator for the solvothermal synthesis,w hich is similar to reported recipes for these MOFs, [26] but developed our own conditions to achieve optimized growth of MOF thin-films onto nanofiber substrates.S pecifically,0 .343 mmol of ZrCl 4 and 0.343 mmol of dicarboxylic acid linkers (1:1 molar ratio) were dissolved in 20 mL of DMF.D eionized water (25 mL) and concentrated HCl (1.33 mL for UiO-66 and UiO-66-NH 2 , 0.67 mL for UiO-67) were added to the solution.…”

“…[10,11] We monitored the reaction progress by tracking the increased absorbance at 407 nm, which corresponds to p-nitrophenoxide (Figure 4b (Table S1) showed similar trends to the reported data. [13,14] Foru ntreated PA -6 nanofibers,D MNP shows negligible rate of hydrolysis with an estimated t 1/2 value over 65 h ( Figure S7). Thea mine moiety in UiO-66-NH 2 is thought to function as aB rønsted base to synergistically enhance the catalytic activity, [30] while the large pore size of UiO-67 may allow faster diffusion and/or more access of DMNP molecules into the active sites of the MOF.…”