Method for assembling and synthesizing Cu.SUB.2.O particle-supported porous CuBTC

Abstract

A method for assembling and synthesizing Cu.sub.2O particle-supported porous CuBTC includes the following steps of: 1) dissolving polyvinylpyrrolidone (PVP) in ethanol solution to obtain a PVP-ethanol solution; 2) dissolving copper salt in distilled water, and mixing with trimesic acid, salicylic acid, and the PVP-ethanol solution obtained in step 1) under stirring; and 3) conducting a hydrothermal reaction on the mixed solution obtained in step 2) at 120° C. to obtain Cu.sub.2O particle-supported porous CuBTC. The new method introduces salicylic acid during the synthesis of CuBTC. The salicylic acid, as a ligand precursor, forms a porous CuBTC material through the unsaturated coordination of a ligand under the catalysis of Cu ion. The resulting porous CuBTC supported with ultrafine Cu.sub.2O nanoparticles can adsorb high-energy molecules and exhibit excellent crystallinity, porosity, and stability.

Claims

1. A method for assembling and synthesizing Cu.sub.2O particle-supported porous CuBTC, comprising the following steps of: 1) dissolving 1.4-1.6 g of polyvinylpyrrolidone (PVP) in an ethanol solution to obtain a PVP-ethanol solution; 2) dissolving 2.1-2.2 g of a copper salt in distilled water to obtain a copper salt solution, and mixing the copper salt solution with 0.6-0.7 g of trimesic acid, greater than 0 g to 0.9 g of salicylic acid, and the PVP-ethanol solution obtained in step 1) under stirring to obtain a mixed solution; and 3) conducting a hydrothermal reaction on the mixed solution obtained in step 2) at 120° C. to obtain Cu.sub.2O particle-supported porous CuBTC.

2. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 1, wherein in the hydrothermal reaction in step 3), 0.5-1.5 g of citric acid is dissolved in distilled water to obtain a 0.5-1.5 M citric acid solution; the citric acid solution is mixed with the mixed solution obtained in step 2) under stirring for 0.5-1 h to obtain a mixture, and then the mixture is transferred into a 100 ml hydrothermal reactor; the hydrothermal reactor is sealed and placed in an oven for the hydrothermal reaction at 120° C.

3. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 1, wherein in the hydrothermal reaction in step 3), 1-2 g of tartaric acid is dissolved in distilled water to obtain a 1-2 M tartaric acid solution; the tartaric acid solution is mixed with the mixed solution obtained in step 2) under stirring for 0.5-1 h to obtain a mixture, and then the mixture is transferred into a 100 ml hydrothermal reactor; the hydrothermal reactor is sealed and placed in an oven for the hydrothermal reaction at 120° C.

4. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 1, wherein a mass of the salicylic acid is 0.4-0.5 g.

5. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 1, wherein a mass of the salicylic acid is 0.7-0.8 g.

6. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 1, wherein a mass of the salicylic acid is 0.8-0.9 g.

7. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 1, wherein the copper salt is Cu(NO.sub.3).sub.2.3H.sub.2O.

8. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 1, wherein a molar ratio of the ethanol solution in step 1) to the distilled water in step 2) is 1:1.

9. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to 1, wherein both the ethanol solution in step 1) and the distilled water in step 2) are 30 ml in volume.

10. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to 1, wherein the hydrothermal reaction in step 3) lasts for 12 h.

11. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 2, wherein a mass of the salicylic acid is 0.4-0.5 g.

12. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 3, wherein a mass of the salicylic acid is 0.4-0.5 g.

13. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 2, wherein a mass of the salicylic acid is 0.7-0.8 g.

14. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 3, wherein a mass of the salicylic acid is 0.7-0.8 g.

15. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 2, wherein a mass of the salicylic acid is 0.8-0.9 g.

16. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 3, wherein a mass of the salicylic acid is 0.8-0.9 g.

17. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 2, wherein the copper salt is Cu(NO.sub.3).sub.2.3H.sub.2O.

18. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 3, wherein the copper salt is Cu(NO.sub.3).sub.2.3H.sub.2O.

19. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 2, wherein a molar ratio of the ethanol solution in step 1) to the distilled water in step 2) is 1:1.

20. The method for assembling and synthesizing the Cu.sub.2O particle-supported porous CuBTC according to claim 3, wherein a molar ratio of the ethanol solution in step 1) to the distilled water in step 2) is 1:1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The present invention will be described below in more detail with reference to the examples and the drawings. Particularly:

(2) FIG. 1 is a scanning electron micrograph of the Cu.sub.2O particle-supported porous CuBTC synthesized by the synthetic method provided by the present invention;

(3) FIG. 2 illustrates nitrogen adsorption-desorption isotherms of the Cu.sub.2O particle-supported porous CuBTC with different meso-pore sizes synthesized in Examples 1, 4, 7, and 8 of the present invention;

(4) FIG. 3 illustrates pore size distributions of the Cu.sub.2O particle-supported porous CuBTC with different meso-pore sizes synthesized in Examples 1, 4, 7, and 8 of the present invention; and

(5) FIG. 4 illustrates X-ray diffraction (XRD) patterns of the Cu.sub.2O particle-supported porous CuBTC with different meso-pore sizes synthesized in Examples 1, 4, 7, and 8 of the present invention.

DETAILED DESCRIPTION

(6) Taken in conjunction with the accompanying drawings, the following paragraphs describe the technical solutions in exemplary embodiments of the present invention. The described examples are merely a part rather than all of the examples of the present invention. All other examples obtained by a person of ordinary skill in the art based on the examples of the present invention without creative efforts shall fall within the protection scope of the present invention.

Example 1

(7) A method for assembling and synthesizing a Cu.sub.2O particle-supported porous CuBTC of this example includes the following steps.

(8) 1) 1.4 g of polyvinylpyrrolidone (PVP) was dissolved in 30 ml of ethanol solution to obtain a PVP-ethanol solution.

(9) 2) 2.1 g of Cu(NO.sub.3).sub.2.3H.sub.2O was dissolved in 30 ml of distilled water, and mixed with 0.6 g of trimesic acid, 0 g of salicylic acid, and the PVP-ethanol solution obtained in step 1) under stirring.

(10) 3) A hydrothermal reaction was conducted on the mixed solution obtained in step 2) at 120° C. for 12 h. Specifically, in the hydrothermal reaction, 0.5 g of citric acid was dissolved in distilled water to obtain 0.5 M citric acid solution. The citric acid solution was mixed with the mixtures obtained in steps 1) and 2) under stirring for 0.5 h, and then transferred into a 100 ml hydrothermal reactor; the hydrothermal reactor was sealed and placed in an oven for the hydrothermal reaction at 120° C., to obtain Cu.sub.2O particle-supported porous CuBTC.

Example 2

(11) This example differs from Example 1 only in that: in the hydrothermal reaction, 1 g of citric acid was dissolved in distilled water to obtain 1 M citric acid solution. The above citric acid solution was mixed with the mixtures obtained in steps 1) and 2) under stirring for 0.8 h, and then transferred into a 100 ml hydrothermal reactor. The hydrothermal reactor was sealed and placed in an oven for the hydrothermal reaction at 120° C.

Example 3

(12) This example differs from Example 1 and 2 only in that: in the hydrothermal reaction, 1.5 g of citric acid was dissolved in distilled water to obtain 1.5 M citric acid solution. The above citric acid solution was mixed with the mixtures obtained in steps 1) and 2) under stirring for 1 h, and then transferred into a 100 ml hydrothermal reactor; the hydrothermal reactor was sealed and placed in an oven for the hydrothermal reaction at 120° C.

Example 4

(13) A method for assembling and synthesizing a Cu.sub.2O particle-supported porous CuBTC of this example includes the following steps.

(14) 1) 1.45 g of PVP was dissolved in 30 ml of ethanol solution to obtain a PVP-ethanol solution.

(15) 2) 2.13 g of Cu(NO.sub.3).sub.2.3H.sub.2O was dissolved in 30 ml of distilled water, and mixed with 0.635 g of trimesic acid, 0.45 g of salicylic acid, and the PVP-ethanol solution obtained in step 1) under stirring.

(16) 3) A hydrothermal reaction was conducted on the mixed solution obtained in step 2) at 120° C. for 12 h. Specifically, in the hydrothermal reaction, 1 g of tartaric acid was dissolved in distilled water to obtain 1 M tartaric acid solution. The above tartaric acid solution was mixed with the mixtures obtained in steps 1) and 2) under stirring for 0.5 h, and then transferred into a 100 ml hydrothermal reactor. The hydrothermal reactor was sealed and placed in an oven for the hydrothermal reaction at 120° C., to obtain Cu.sub.2O particle-supported porous CuBTC (1).

Example 5

(17) This example differs from Example 4 only in that: in the hydrothermal reaction, 1.5 g of tartaric acid was dissolved in distilled water to obtain 1.5 M tartaric acid solution. The above tartaric acid solution was mixed with the mixtures obtained in steps 1) and 2) under stirring for 0.8 h, and then transferred into a 100 ml hydrothermal reactor. The hydrothermal reactor was sealed and placed in an oven for the hydrothermal reaction at 120° C.

Example 6

(18) This example differs from Example 4 and 5 only in that: in the hydrothermal reaction, 2 g of tartaric acid was dissolved in distilled water to obtain 2 M tartaric acid solution. The above tartaric acid solution was mixed with the mixtures obtained in steps 1) and 2) under stirring for 0.5-1 h, and then transferred into a 100 ml hydrothermal reactor. The hydrothermal reactor was sealed and placed in an oven for the hydrothermal reaction at 120° C.

Example 7

(19) A method for assembling and synthesizing a Cu.sub.2O particle-supported porous CuBTC of this example includes the following steps.

(20) 1) 1.55 g of PVP was dissolved in 30 ml of ethanol solution to obtain a PVP-ethanol solution.

(21) 2) 2.17 g of Cu(NO.sub.3).sub.2.3H.sub.2O was dissolved in 30 ml of distilled water, and mixed with 0.675 g of trimesic acid, 0.65 g of salicylic acid, and the PVP-ethanol solution obtained in step 1) under stirring.

(22) 3) A hydrothermal reaction was conducted on the mixed solution obtained in step 2) at 120° C. for 12 h to obtain Cu.sub.2O particle-supported porous CuBTC (1.5), and a scanning electron micrograph thereof is shown in FIG. 1.

Example 8

(23) A method for assembling and synthesizing a Cu.sub.2O particle-supported porous CuBTC of this example includes the following steps.

(24) 1) 1.6 g of PVP was dissolved in 30 ml of ethanol solution to obtain a PVP-ethanol solution.

(25) 2) 2.2 g of Cu(NO.sub.3).sub.2.3H.sub.2O was dissolved in 30 ml of distilled water, and mixed with 0.7 g of trimesic acid, 0.85 g of salicylic acid, and the PVP-ethanol solution obtained in step 1) under stirring.

(26) 3) A hydrothermal reaction was conducted on the mixed solution obtained in step 2) at 120° C. for 12 h to obtain Cu.sub.2O particle-supported porous CuBTC (2).

Test Example

(27) Nitrogen adsorption-desorption isotherms, pore size distributions, and XRD patterns were tested for the Cu.sub.2O particle-supported porous CuBTC obtained in Examples 1, 4, 7, and 8 of the present invention. The results are shown in FIGS. 2 to 4.

(28) From FIG. 2, as salicylic acid increases, adsorption-desorption isotherms of the Cu.sub.2O particle-supported porous CuBTC synthesized in all examples transit from microporous pattern to mesoporous pattern gradually. This suggests that as salicylic acid increases, micropores of the synthesized Cu.sub.2O particle-supported porous CuBTC are partly lost, more mesopores are produced, but there is no significant decrease in specific surface area.

(29) From FIG. 3, the pore size of the Cu.sub.2O particle-supported porous CuBTC can be readily adjusted by changing the addition ratio of salicylic acid; from curves of CuBTC (2) and CuBTC (1.5) in FIG. 3, an increase in salicylic acid reduces the defect of decreased pore volume caused by enlargement of the pore size of the synthesized CuBTC, i.e., decreased adsorption rate.

(30) From FIG. 4, each of the Cu.sub.2O particle-supported porous CuBTC synthesized in Examples 1, 4, 7, and 8 of the present invention has the same peak in the XRD patterns, suggesting that crystallinity is retained. Intensities of main diffraction peaks (220) and (222) remain substantially unchanged (JCPDS: 00-062-1183). Specifically, as the addition of salicylic acid increases, the intensity of peak (200) weakens gradually, suggesting that defects originate from the crystal plane of (200).

(31) For the purposes of promoting an understanding of the principles of the invention, specific embodiments have been described. It should nevertheless be understood that the description is intended to be illustrative and not restrictive in character, and that no limitation of the scope of the invention is intended. Any alterations and further modifications in the described components, elements, processes or devices and any further applications of the principles of the invention as described herein, are contemplated as would normally occur to one skilled in the art to which the invention pertains.