Short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst, the preparation method thereof and the use thereof

Abstract

A short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst, and a preparation method and application thereof. The short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst is prepared by mixing pretreated short channel mesoporous carbon with cobalt salt, nickel salt, indium salt and reducing agent with a hydrothermal reaction. The short channel ordered mesoporous carbon is obtained by calcining a short channel ordered mesoporous silica and a carbon source under the protection of nitrogen, wherein the short channel ordered mesoporous silica is prepared by carrying out reactions of sol-gel-hydrothermal-calcination sequentially using a mixture of a surfactant, a hydrochloric acid solution, ammonium fluoride and tetraethyl orthosilicate. The photocatalyst has strong adsorption and visible light catalytic activity on VOCs, and can effectively adsorb and decompose the enriched VOCs in situ on the surface of the catalyst.

Claims

1. A preparation method of a short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst, wherein the preparation method comprises the following steps: S1. adding 0.1-10 g surfactant to 10-120 mL water and concentrated hydrochloric acid solution with a volume ratio of 1-20:1 and stirring at 30-90 C. for 0.5-24 h to obtain a mixed solution A; S2. adding 0.01-0.1 g ammonium fluoride to the mixed solution A obtained in step S1, stirring for 0.5-60 min, then adding 5-50 mL mixed solution of alkane and tetraethyl orthosilicate with a volume ratio of 1-10:1 and stirring at 30-90 C. for 2-72 h to obtain a mixed solution B; S3. loading the mixed solution B obtained in step S2 into a 25-200 mL polytetrafluoroethylene (PTFE) vessel to conduct a hydrothermal reaction at 60-250 C. for 2-72 h; after cooling in the PTFE vessel, collecting the lower layer sediment and calcining it at 300-800 C. for 1-2 h to obtain short channel ordered mesoporous silica; S4. loading the short channel ordered mesoporous silica obtained in step S3, carbon source and water into a crucible with a mass ratio of 1:(10-30):(10-30), and reacting at 50-100 C. for 1-24 h; then calcining them at 300-1000 C. for 1-24 h under the protection of nitrogen gas to obtain short channel ordered mesoporous carbon; S5. mixing the short channel ordered mesoporous carbon obtained in step S4 with water, concentrated sulfuric acid and ammonium persulfate at a mass ratio of 1:(10-30):(2-10): (1-10) at 40-90 C. and stirring them for 1-24 h; collecting the sediments, washing them with water and drying them at 50-180 C. for 1-36 h to obtain pre-treated short channel ordered mesoporous carbon; S6. adding 50-200 mg pre-treated short channel ordered mesoporous carbon obtained in step S5, 20-100 mg cobalt salt, 50-500 mg nickel salt, 60-300 mg indium salt and 30-300 mg reducing agent to a 30-100 mL alcohol solution sequentially; after ultrasonic dispersion for 10-60 min, loading the solution into a 50-200 mL PTFE vessel to carry out a hydrothermal reaction at 60-250 C. for 2-72 h; after cooling in the PTFE vessel, washing the precipitate with water and drying it at 40-80 C. for 3-12 h to obtain the short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst.

2. The preparation method according to claim 1, wherein the surfactant in step S1 is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, polyethylene glycol or cetyltrimethylammonium bromide.

3. The preparation method according to claim 1, wherein the alkane in step S2 is octane, decane or nonane.

4. The preparation method according to claim 1, wherein the carbon source in step S4 is phenol or sucrose.

5. The preparation method according to claim 1, wherein the cobalt salt in step S6 is cobalt chloride, cobalt nitrate or cobalt sulfate; the nickel salt is nickel chloride, nickel nitrate or nickel sulfate; the indium salt is indium chloride, indium nitrate or indium sulfate; and the reducing agent is thiourea, urea or thioacetamide.

6. The preparation method according to claim 1, wherein the alcohol solution in step S6 is ethanol or methanol dissolved in an organic solvent, and the organic solvent is glycerin or t-butanol.

7. The preparation method according to claim 6, wherein the volume ratio of the ethanol or methanol to the organic solvent is 1-10:1.

8. The preparation method according to claim 1, wherein the water in steps S1, S5 and S6 is deionized water.

9. A short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst prepared by the preparation method according to claim 1.

10. A preparation method for a short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst, wherein the preparation method comprises the following steps: S 1. mixing surfactant, water and concentrated hydrochloric acid to obtain a mixed solution A; S2. mixing ammonium fluoride, the mixed solution A, alkane and tetraethyl orthosilicate to obtain a mixed solution B; S3. placing the mixed solution B in a PTFE vessel for hydrothermal reaction, and after cooling, collecting the precipitate and calcining it to obtain short channel ordered mesoporous silica; S4. mixing the short channel ordered mesoporous silica, a carbon source and water for reaction, and calcining the obtained product to obtain short channel ordered mesoporous carbon; S5. mixing the short channel ordered mesoporous carbon, water, concentrated sulfuric acid and ammonium persulfate, collecting the precipitate and washing it by water to obtain pre-treated short channel ordered mesoporous carbon; S6. mixing the pre-treated short channel ordered mesoporous carbon, cobalt salt, nickel salt, indium salt, reducing agent with alcohol solution, and then placing the solution in a PTFE vessel for hydrothermal reaction to obtain the short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst.

11. The preparation method according to claim 10, wherein in step S1, the ratio of the solution obtained from the water and the concentrated hydrochloric acid to the surfactant is (10-120) mL:(0.1-10) g, and the volume ratio of the water to the concentrated hydrochloric acid is (1-20): 1.

12. The preparation method according to claim 10, wherein in step S1, the mixing is carried out by stirring, and the stirring is performed at a temperature of 30-90 C. for 0.5-24 h.

13. The preparation method according to claim 10, wherein in step S2, the process of obtaining the mixed solution B is specifically: mixing the ammonium fluoride with the mixed solution A; after stirring, adding a mixed solution of the alkane and the tetraethyl orthosilicate, and stirring again to obtain the mixed solution B.

14. The preparation method according to claim 13, wherein the ratio of the ammonium fluoride to the mixed solution is (0.01-0.1) g:(5-50) mL; the volume ratio of the alkane and the tetraethyl orthosilicate is (1-10):1; the time of the said stirring is 0.5-60 min, and the said stirring again is conducted at a temperature of 30-90 C. for 2-72 h.

15. The preparation method according to claim 10, wherein in step S3, the hydrothermal reaction is conducted at a temperature of 60-250 C. for 2-72 h; and the calcination is conducted under protective atmosphere at 300-800 C. for 1-2 h.

16. The preparation method according to claim 10, wherein in step S4, the mass ratio of the short channel ordered mesoporous carbon, the carbon source and the water is 1:(10-30):(10-30); the reaction is conducted at a temperature of 50-100 C. for 1-24 h; the calcination is carried out under a protective atmosphere at a temperature of 300-1000 C. for 1-24 h.

17. The preparation method according to claim 10, wherein in step S5, the mass ratio of the short channel ordered mesoporous carbon, the water, the concentrated sulfuric acid and the ammonium persulfate is 1:(10-30):(2-10):(1-10); the mixing is carried out by stirring, and the stirring is conducted at a temperature of 40-90 C. for 1-24 h; and the drying is conducted at a temperature of 50-180 C. for 1-36 h.

18. The preparation method according to claim 10, wherein in step S6, the ratio of the pretreated short channel ordered mesoporous carbon, the cobalt salt, the nickel salt, the indium salt, the reducing agent and the alcohol solution is (50-200) mg:(20-100) mg:(50-500) mg:(60-300) mg:(30-300) mg:(30-100) mL.

19. The preparation method according to claim 10, wherein in step S6, the time of the mixing is 10-60 min, and the hydrothermal reaction is conducted at a temperature of 60-250 C. for 2-72 h.

20. The preparation method according to claim 10, wherein the surfactant in step S1 is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, polyethylene glycol or cetyltrimethylammonium bromide.

21. The preparation method according to claim 10, wherein the alkane in step S2 is octane, decane or nonane.

22. The preparation method according to claim 10, wherein the carbon source in step S4 is phenol or sucrose.

23. The preparation method according to claim 10, wherein the cobalt salt is cobalt chloride, cobalt nitrate or cobalt sulfate; the nickel salt is nickel chloride, nickel nitrate or nickel sulfate; the indium salt is indium chloride, indium nitrate or indium sulfate; and the reducing agent is thiourea, urea or thioacetamide.

24. The preparation method according to claim 10, wherein the alcohol solution in step S6 is ethanol or methanol dissolved in an organic solvent, and the organic solvent is glycerin or t-butanol.

25. The preparation method according to claim 24, wherein the volume ratio of the ethanol or methanol to the organic solvent is 1-10:1.

26. The preparation method according to claim 10, wherein the water in steps S1, S5 and S6 is deionized water.

27. A short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst prepared by the preparation method according to claim 10.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the adsorption kinetics and photocatalytic degradation kinetics curves of gaseous xylene by the short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(2) The content of the present invention is further described below with reference to the accompanying drawings and specific embodiments, but is not to be construed as limiting. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise specified. Unless otherwise stated, the reagents, methods and devices employed in the present invention are routine reagents, methods and devices in the art.

Example 1

(3) 1. Preparation:

(4) S1. adding 0.1 g polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to 10 mL of water and concentrated hydrochloric acid solution with a volume ratio of 20:1, and stirring at 90 C. for 0.5 h to obtain a clear solution;

(5) S2. adding 0.01 g ammonium fluoride to the clear solution obtained in step S1, stirring for 0.5 min, then adding 5 mL mixture of octane and tetraethyl orthosilicate with a volume ratio of 1:1 and stirring at 30 C. for 2 h to obtain a white turbid solution;

(6) S3. loading the white turbid solution obtained in step S2 into a 25 mL PTFE vessel, carrying out a hydrothermal reaction at 60 C. for 72 h; after cooling in the PTFE vessel, collecting the lower layer precipitate and calcining it at 300 C. for 24 h to obtain short channel ordered mesoporous silica;

(7) S4. loading the short channel ordered mesoporous silica obtained in step S3, phenol and water into a crucible at a mass ratio of 1:10:10; after reacting at 50 C. for 1 h, calcining them at 300 C. for 24 h under nitrogen protective atmosphere to obtain short channel ordered mesoporous carbon;

(8) S5. stirring the short channel ordered mesoporous carbon obtained in step S4 with water, concentrated sulfuric acid and ammonium persulfate at a mass ratio of 1:10:10:10 at 40 C. for 24 h; then collecting the precipitate, washing it and drying it at 50 C. for 36 h to obtain pretreated short channel ordered mesoporous carbon;

(9) S6. slowly adding 50 mg pretreated short channel ordered mesoporous carbon obtained in step S5, 20 mg cobalt chloride, 50 mg nickel chloride, 60 mg indium chloride and 30 mg thiourea sequentially to 30 mL alcohol solution (ethanol and glycerol with a volume ratio of 1:1); after ultrasonic dispersion for 10 min, placing them in a 50 mL PTFE vessel and carrying out a hydrothermal reaction at 60 C. for 72 h; after cooling in the PTFE, vessel, washing the precipitate with water and drying it at 40 C. for 12 h to obtain a short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst.

(10) 2. Performance Test:

(11) FIG. 1 shows the adsorption kinetics and photocatalytic degradation kinetics curves of gaseous xylene by the short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst. It can be seen from FIG. 1 that the photocatalyst exhibits good adsorption and photocatalytic activity, wherein the adsorption efficiency of xylene reaches 20.3% within 40 min, and the degradation efficiency of xylene reaches 93.9% within 60 min. The results show that the short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst prepared by the invention is a novel material with high adsorption and photocatalytic activity.

Example 2

(12) S1. adding 10 g polyethylene glycol to 120 mL of water and concentrated hydrochloric acid solution with a volume ratio of 1:1, and stirring at 30 C. for 24 h to obtain a clear solution;

(13) S2. adding 0.01 g ammonium fluoride to the clear solution obtained in step S1, stirring for 60 min, then adding 5 mL mixture of decane and tetraethyl orthosilicate with a volume ratio of 10:1 and stirring at 30 C. for 2 h to obtain a white turbid solution;

(14) S3. loading the white turbid solution obtained in step S2 into a 200 mL PTFE vessel, carrying out a hydrothermal reaction at 250 C. for 2 h; after cooling in the PTFE vessel, collecting the lower layer precipitate and calcining it at 800 C. for 1 h to obtain short channel ordered mesoporous silica;

(15) S4. loading the short channel ordered mesoporous silica obtained in step S3, sucrose and water into a crucible at a mass ratio of 1:30:30; after reacting at 100 C. for 24 h, calcining them at 1000 C. for 1 h under nitrogen protective atmosphere to obtain short channel ordered mesoporous carbon;

(16) S5. stirring the short channel ordered mesoporous carbon obtained in step S4 with water, concentrated sulfuric acid and ammonium persulfate at a mass ratio of 1:30:2:1 at 90 C. for 1 h; then collecting the precipitate, washing it and drying it at 180 C. for 1 h to obtain pretreated short channel ordered mesoporous carbon;

(17) S6. slowly adding 200 mg pretreated short channel ordered mesoporous carbon obtained in step S5, 100 mg cobalt chloride, 500 mg nickel chloride, 300 mg indium chloride and 300 mg urea sequentially to 100 mL alcohol solution (methanol and tert-butanol with a volume ratio of 10:1); after ultrasonic dispersion for 60 min, placing them in a 200 mL PTFE vessel and carrying out a hydrothermal reaction at 250 C. for 2 h; after cooling in the PTFE vessel, washing the precipitate with water and drying it at 80 C. for 3 h to obtain a short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst.

Example 3

(18) S1. adding 2 g cetyltrimethylammonium bromide to 50 mL of water and concentrated hydrochloric acid solution with a volume ratio of 5:1, and stirring at 45 C. for 4 h to obtain a clear solution;

(19) S2. adding 0.05 g ammonium fluoride to the clear solution obtained in step S1, stirring for 30 min, then adding 10 mL mixture of nonane and tetraethyl orthosilicate with a volume ratio of 4:1 and stirring at 4 C. for 12 h to obtain a white turbid solution;

(20) S3. loading the white turbid solution obtained in step S2 into a 100 mL PTFE vessel, carrying out a hydrothermal reaction at 100 C. for 48 h; after cooling in the PTFE vessel, collecting the lower layer precipitate and calcining it at 540 C. for 5 h to obtain short channel ordered mesoporous silica;

(21) S4. loading the short channel ordered mesoporous silica obtained in step S3, sucrose and water into a crucible at a mass ratio of 1:20:20; after reacting at 45 C. for 12 h, calcining them at 900 C. for 4 h under nitrogen protective atmosphere to obtain short channel ordered mesoporous carbon;

(22) S5. stirring the short channel ordered mesoporous carbon obtained in step S4 with water, concentrated sulfuric acid and ammonium persulfate at a mass ratio of 1:15:5:5 at 50 C. for 8 h; then collecting the precipitate, washing it and drying it at 100 C. for 12 h to obtain pretreated short channel ordered mesoporous carbon;

(23) S6. slowly adding 100 mg pretreated short channel ordered mesoporous carbon obtained in step S5, 50 mg cobalt chloride, 200 mg nickel chloride, 250 mg indium chloride and 250 mg urea sequentially to 40 mL alcohol solution (ethanol and tert-butanol with a volume ratio of 5:1); after ultrasonic dispersion for 20 min, placing them in a 100 mL PTFE vessel and carrying out a hydrothermal reaction at 150 C. for 9 h; after cooling in the PTFE vessel, washing the precipitate with water and drying it at 60 C. for 8 h to obtain a short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst.

Example 4

(24) S1. adding 6 g polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to 85 mL of water and concentrated hydrochloric acid solution with a volume ratio of 8:1, and stirring at 35 C. for 3 h to obtain a clear solution;

(25) S2. adding 0.02 g ammonium fluoride to the clear solution obtained in step S1, stirring for 10 min, then adding 25 mL mixture of decane and tetraethyl orthosilicate with a volume ratio of 6:1 and stirring at 35 C. for 24 h to obtain a white turbid solution;

(26) S3. loading the white turbid solution obtained in step S2 into a 150 mL PTFE vessel, carrying out a hydrothermal reaction at 90 C. for 24 h; after cooling in the PTFE vessel, collecting the lower layer precipitate and calcining it at 600 C. for 6 h to obtain short channel ordered mesoporous silica;

(27) S4. loading the short channel ordered mesoporous silica obtained in step S3, phenol and water into a crucible at a mass ratio of 1:15:15; after reacting at 45 C. for 12 h, calcining them at 850 C. for 10 h under nitrogen protective atmosphere to obtain short channel ordered mesoporous carbon;

(28) S5. stirring the short channel ordered mesoporous carbon obtained in step S4 with water, concentrated sulfuric acid and ammonium persulfate at a mass ratio of 1:12:4:2 at 60 C. for 4 h; then collecting the precipitate, washing it and drying it at 100 C. for 6 h to obtain pretreated short channel ordered mesoporous carbon;

(29) S6. slowly adding 150 mg pretreated short channel ordered mesoporous carbon obtained in step S5, 80 mg cobalt chloride, 145 mg nickel chloride, 145 mg indium chloride and 155 mg urea sequentially to 45 mL alcohol solution (methanol and glycerin with a volume ratio of 3:1); after ultrasonic dispersion for 15 min, placing them in a 100 mL PTFE vessel and carrying out a hydrothermal reaction at 180 C. for 10 h; after cooling in the PTFE vessel, washing the precipitate with water and drying it at 50 C. for 12 h to obtain a short channel ordered mesoporous carbon loaded indium cobalt sulfide and indium nickel sulfide ternary composite photocatalyst.

(30) The above-described embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, modifications and simplifications made without departing from the spirit and scope of the invention should be equivalent replacements and be included in the scope of the present invention