Hierarchical porous defect UiO-66 material and its preparation method
Provided are a hierarchical porous defect UiO-66 material and a preparation method thereof. The method includes the following steps: mixing a zirconium ion source, a mixed ligand, an organic acid, an organic good solvent, and water to obtain a mixture; and subjecting the mixture to reaction while heating, washing, freeze-drying, and heat treatment in sequence to obtain the hierarchical porous defect UiO-66 material; where hierarchical pores of the hierarchical porous defect UiO-66 material comprise micropores and mesopores; the micropores each have a pore size of not greater than 2 nm; the mesopores each have a pore size of 2 nm to 4 nm; the mixed ligand includes terephthalic acid and a trisubstituted benzene series; and the trisubstituted benzene series is one or two selected from the group consisting of 2-aminoterephthalic acid and 2-aminoisophthalic acid.
1. A method for preparing a hierarchical porous defect UiO-66 material, comprising the following steps:
mixing a zirconium ion source, a mixed ligand, an organic acid, N,N-dimethylformamide (DMF), and water to obtain a mixture; and subjecting the mixture to reaction under heating, washing, freeze-drying, and heat treatment in sequence to obtain the hierarchical porous defect UiO-66 material;
wherein hierarchical pores of the hierarchical porous defect UiO-66 material comprise micropores and mesopores; the micropores each have a pore size of not greater than 2 nm; and the mesopores each have a pore size of 2 nm to 4 nm; and
the mixed ligand comprises terephthalic acid and a trisubstituted benzene series; and the trisubstituted benzene series is one or two selected from the group consisting of 2-aminoterephthalic acid and 2-aminoisophthalic acid.
2. The method of claim 1 , wherein the zirconium ion source is one or two selected from the group consisting of zirconium chloride and zirconium oxychloride; and
the organic acid is one or more selected from the group consisting of formic acid, acetic acid, and benzoic acid.
3. The method of claim 2 , wherein a molar ratio of the zirconium ion source to the mixed ligand is in a range of 1:0.5 to 1:2;
a molar ratio of the zirconium ion source to the DMF is in a range of 1:130 to 1:520;
a molar ratio of the zirconium ion source to the organic acid is in a range of 1:10 to 1:200; and
a molar ratio of the zirconium ion source to the water is in a range of 1:0.5 to 1:2.
4. The method of claim 1 , wherein a molar ratio of the zirconium ion source to the mixed ligand is in a range of 1:0.5 to 1:2;
a molar ratio of the zirconium ion source to the DMF is in a range of 1:130 to 1:520;
a molar ratio of the zirconium ion source to the organic acid is in a range of 1:10 to 1:200; and
a molar ratio of the zirconium ion source to the water is in a range of 1:0.5 to 1:2.
5. The method of claim 1 , wherein a molar ratio of the terephthalic acid to the trisubstituted benzene series is in a range of (0-1): (0-1), excluding 0.
6. The method of claim 1 , wherein the reaction under heating is conducted at a temperature of 120° C. to 160° C. for 24 h to 72 h.
7. The method of claim 1 , wherein the freeze-drying is conducted at a temperature of −60° C. to −40° C. for 18 h to 36 h.
8. The method of claim 1 , wherein the heat treatment is conducted at a temperature of 325° C. to 375° C. for 0.25 h to 4 h.
9. A hierarchical porous defect UiO-66 material prepared by the method of claim 1 , wherein hierarchical pores of the hierarchical porous defect UiO-66 material comprise micropores and mesopores; the micropores each have a pore size of not greater than 2 nm; and the mesopores each have a pore size of 2 nm to 4 nm.
10. The hierarchical porous defect UiO-66 material of claim 9 , wherein the zirconium ion source is one or two selected from the group consisting of zirconium chloride and zirconium oxychloride; and
the organic acid is one or more selected from the group consisting of formic acid, acetic acid, and benzoic acid.
11. The hierarchical porous defect UiO-66 material of claim 9 , wherein a molar ratio of the zirconium ion source to the mixed ligand is in a range of 1:0.5 to 1:2;
a molar ratio of the zirconium ion source to the DMF is in a range of 1:130 to 1:520;
a molar ratio of the zirconium ion source to the organic acid is in a range of 1:10 to 1:200; and
a molar ratio of the zirconium ion source to the water is in a range of 1:0.5 to 1:2.
12. The hierarchical porous defect UiO-66 material of claim 9 , wherein a molar ratio of the terephthalic acid to the trisubstituted benzene series is in a range of (0-1):(0-1), excluding 0.