Method for preparation of size-modulated UiO-66 and catalyst for hydrolysis of chemical warfare agents with enhanced activity prepared thereby
The present invention relates to a method for preparing size-modulated UiO-66, which is achieved by modulating the concentrations of reactants, and a catalyst with improved activity of hydrolyzing chemical warfare agents prepared by the method.
1. A method for preparing catalyst particles of UiO-66, comprising:
providing a first solution comprising ZrCl 4 at a concentration of 0.15 M to 0.5 M, and a second solution comprising terephthalic acid (benzene-1,4-dicarboxylic acid; BDC) at a concentration of 0.1 M to 0.5 M; and
mixing the first solution and the second solution in a volume ratio of 1:1 to 1:3,
wherein the first solution comprises hydrochloric acid in an amount of 8 to 15 moles per mole of ZrCl 4 , and
the catalyst particles of UiO-66 have an average diameter of 50 nm to 400 nm, and hydrolyze or detoxify chemical warfare agents.
2. The method of claim 1 , wherein both the first solution and the second solution are prepared using N,N-dimethylformamide (DMF) as a solvent.
3. The method of claim 1 , wherein the third step is performed at 60° C. to 120° C. for 12 to 48 hours.
4. The method of claim 1 , wherein the catalyst particles of UiO-66 have an average diameter of 100 nm to 190 nm.
5. The method of claim 1 , wherein particles of the UiO-66 have 1.65 to 1.9 missing linker sites on average within a single cluster.
6. The method of claim 1 , wherein particles of the UiO-66 have a specific surface area of 1400 m 2 /g to 1500 m 2 /g.
7. A method for detoxifying chemical warfare agents (CWA) with catalyst particles of UiO-66, the method comprising:
providing a first solution comprising ZrCl 4 at a concentration of 0.15 M to 0.5 M, and a second solution comprising terephthalic acid (benzene-1,4-dicarboxylic acid; BDC) at a concentration of 0.1 M to 0.5 M; and
mixing the first solution and the second solution in a volume ratio of 1:1 to 1:3,
wherein the first solution comprises hydrochloric acid in an amount of 8 to 15 moles per mole of ZrCl 4 for making of the catalyst particles of UiO-66 having an average diameter of 50 nm to 400 nm;
preparing a solution comprising a base and a chemical warfare agent in a water solvent; and
contacting the solution comprising the base and the chemical warfare agent with the catalyst particles of UiO-66, wherein the method of detoxifying has a conversion rate of at least 50% at one minute or less of contact time as measured with a simulated warfare agent, methylparaoxone.
8. The method of claim 7 , wherein the contacting of the solution and the catalyst particles includes a mole ratio of the catalyst particles of UiO-66 to chemical warfare agent of 0.02:1 to 0.05:1.
9. The use of the UiO-66 particles prepared by the method of claim 7 , forming a coating for a fabric including the UiO-66 particles.
10. The use of the UiO-66 particles prepared by the method of claim 7 , forming a molded product including the UiO-66 particles housed in a porous container product of a canister.
11. The use of the UiO-66 particles prepared by the method of claim 7 , forming a molded product including the UiO-66 particles housed in a porous container of a canister for a protective mask.