CN103990493B - A kind of visible light catalyst for rhodamine B in degradation water and application thereof - Google Patents

A kind of visible light catalyst for rhodamine B in degradation water and application thereof Download PDF

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CN103990493B
CN103990493B CN201410206969.4A CN201410206969A CN103990493B CN 103990493 B CN103990493 B CN 103990493B CN 201410206969 A CN201410206969 A CN 201410206969A CN 103990493 B CN103990493 B CN 103990493B
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rhodamine
visible light
triazole
water
siw
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CN103990493A (en
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师唯
赵秀霞
张少伟
程鹏
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Nankai University
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Abstract

For a visible light catalyst for rhodamine B in degradation water, chemical formula is [Cu i 12(1,2,4-triazole) 8(H 2o) 2] [<i> α </i>-SiW 12o 40] 2H 2o, has a compound of three-dimensional frame structure for the metal organic frame constructed based on polyoxometallate, to there is in four kinds of crystallography independently Cu in this compound iion, by itself and ligand 1,2,4-triazole is interconnected to form the two-dimentional double-ring cation frame structure having three-membered ring and ten-ring and coexist, and [<i> α </i>-SiW 12o 40] 4 –anion is connected to form three-dimensional frame structure with the copper ion of three on two-dimentional dicyclo respectively by its terminal oxygen atom.Advantage of the present invention: this photochemical catalyst preparation method is simple, water stability good and degraded after can recycle; Utilize in photocatalyst for degrading water and use visible ray in rhodamine B, can solar energy be made full use of, technique is simple, cost is low, excellent catalytic effect.

Description

A kind of visible light catalyst for rhodamine B in degradation water and application thereof
Technical field
The invention belongs to photocatalysis technology field, particularly a kind of visible light catalyst for rhodamine B in degradation water and application thereof.
Background technology
Photocatalysis in recent years can directly utilize solar energy to drive the special performances such as reaction as light source using it, and becoming a kind of desirable environmental pollution treatment technology and clear energy sources production technology, it has, and secondary pollution is few, reaction condition is gentle, easy and simple to handle, low power consumption and other advantages.The key element of light-catalyzed reaction is photochemical catalyst.Titanium dioxide is just well known as far back as the 1950's as a kind of common photochemical catalyst, since the clear report delivered on Nature about preparing hydrogen at titanium dioxide electrodes glazing decomposition water in Japanese Scientists rattan island in 1972, cause the extensive concern of the field scholar such as chemistry, physics, material in the world immediately, also worldwide expand simultaneously and be conceived to the decomposition reaction of optically catalytic TiO 2 oxidation of organic compounds, although TiO 2have stability high, active high, can the advantage such as reusing and low cost, but this research finally does not all realize applying widely, main cause is the energy gap comparatively large (3.2ev) of titanium dioxide, and the ultraviolet light being equivalent to only have wavelength to be less than or equal to 387nm just can excite TiO 2produce conduction band electron and valence band hole and be oxidized Sum decomposition organic matter.But the ultraviolet light that wavelength is less than 380nm accounts for earth surface receives sunshine gross energy and be less than 4%.If directly use TiO 2make catalyst, other sunshine of more than 95% just can not be utilized effectively.In addition, due to can TiO be excited in sunshine 2ultraviolet ray intensity all weak, cause directly utilizing sunshine to do the efficiency of the photocatalysis degradation organic contaminant of light source very low; If utilize artificial light source then can produce energy consumption problem again.Therefore, design, synthesize and have stronger photocatalytic activity at visible region, the high stability material of visible light part in sunshine can be utilized, become current photocatalysis most important meaning and challenging problem.
Polyoxometallate is the Polyoxometallate that a class forms primarily of molybdenum and tungsten, and have the character of similar semiconductor light-catalyst, be a kind of wide-band gap material (3.1-4.6eV), absworption peak is mainly in ultra-violet (UV) band, but its bands of a spectrum can extend to visible region.When under the effect in ultraviolet or visible ray, part can be there is and move transition to the lotus of metal, produce oxidability and be greater than 2.5V(vs. standard hydrogen electrode) excitation state, thus most organic pollutants is degraded.As the polyelectron oxidation catalyst of a class strong oxidizing property, its anion structure after the multiple electronics of acquisition still keeps stable.Therefore, polyoxometallate photocatalytic degradation have that toxicity is little, salinity is high, mild condition, stable performance, photolysis efficiency advantages of higher.The great interest of people is also result in recent years in the research in environmental photochemistry field.But polyoxometallate also has the defect of himself, as little in specific area, be difficult to reclaim etc.For this reason, people's modification of catalyst that adopted multiple technologies to carry out, if polyoxometallate and semiconducting compound are (with TiO 2be main) compound.But photoresponse scope is limited (mainly in ultra-violet (UV) band) still, makes it apply and be restricted.
The rise of metal-organic framework (MOFs) material is also for photocatalysis technology is filled with new vitality in recent years, it is the coordination utilized between organic ligand and metal ion, the kind zeolitic material with supermolecule microporous network structure that self assembly is formed, has uncommon geometries, little specific area, relatively mild synthesis condition; But also due to it, there is the features such as structure diversification, uncommon photoelectric effect and numerous operational metal ions, just developing the study hotspot become in the energy, material and life science crossing domain rapidly.In the synthetic technology of MOFs, for organic ligand, wherein coordination mode and the coordination ability of functional group can difference changing by lewis acid and metal ion flexibly; For metal node, metal ion can form the secondary construction unit of metal that check figure is different, linking number is different by the ion large from electronegativity.By the advantage of these two aspects, framework obtains modifying, deriving, thus forms colourful structure type.Just because of its various structures there is adjustability and little specific area, more be conducive to the material designed, synthesis energy gap is adjustable, it is made to have stronger photocatalytic activity at visible region, improve the utilization rate to solar energy, also will have important practical significance to the solution energy, problem of environmental pollution.
Current urgent need a kind of novel low-energy zone width and the good catalysis material of water stability, if polyoxometallate can be combined effectively with metal-organic framework materials, design and expand photoresponse scope and the novel photocatalysis system that can recycle, realize visible light efficient catalytic reaction, to important theory significance be had, simultaneously also for exploitation is efficient, environmental protection, energy-conservation Organic Waste Water Treatment technology provide a kind of new thinking.
Summary of the invention
Object of the present invention is exactly for above-mentioned existing problems, and provide a kind of visible light catalyst for rhodamine B in degradation water and application thereof, the preparation method of this photochemical catalyst is simple, water stability good, and can recycle after degraded; Utilize in the process of rhodamine B in this photocatalyst for degrading water and use visible ray, can solar energy be made full use of, technique is simple, with low cost, excellent catalytic effect.
Technical scheme of the present invention:
For a visible light catalyst for rhodamine B in degradation water, chemical formula is [Cu i 12(1,2,4-triazole) 8(H 2o) 2] [ α-SiW 12o 40] 2H 2o, is a kind of metal organic frame of constructing based on polyoxometallate and has the compound of three-dimensional frame structure, to there is in four kinds of crystallography independently Cu in this compound iion, by itself and ligand 1,2,4-triazole (trz) –be interconnected to form the two-dimentional double-ring cation frame structure [Cu that there is three-membered ring and ten-ring and coexist i 12(1,2,4-triazole) 8(H 2o) 2] 4+, and [ α-SiW 12o 40] 4 –anion by its terminal oxygen atom (O12, O4 and O6) respectively with the Cu1 on two-dimentional dicyclo i, Cu2 iand Cu3 iion is connected, and forms three-dimensional frame structure.
A described preparation method for the visible light catalyst of rhodamine B in degradation water, adopt solvent-thermal method preparation, step is as follows:
1) by nitrate trihydrate copper, 1,2,4-triazole and polyoxometallate Na 10[SiW 9o 34] 18H 2o adds in deionized water and absolute ethyl alcohol mixed solution and obtains mixed liquor, nitrate trihydrate copper, 1,2,4-triazole, Na 10[SiW 9o 34] 18H 2the amount ratio of O and deionized water and absolute ethyl alcohol is 0.05mmol:0.2mmol:0.5mmol:8mL:2mL;
2) after above-mentioned mixed liquor being sealed in reactor, be placed in baking oven constant temperature 72 hours at 170 DEG C of temperature, then slowly room temperature is dropped to the speed of 4 DEG C/h, obtain orange bulk crystals, spend deionized water clean after, at room temperature be evaporated to dry, the visible light catalyst [Cu for rhodamine B in degradation water can be obtained i 12(1,2,4-triazole) 8(H 2o) 2] [ α-SiW 12o 40] 2H 2o.
An application for the prepared visible light catalyst for rhodamine B in degradation water, for organic dyestuff rhodamine B in degradation water, step is as follows:
1) be that the rhodamine B solution of 15mg/L is placed in laminated glass beaker by 100mL concentration, then add visible light catalyst prepared by 15mg, pass into cooling water in interlayer and under dark condition, stir 1 hour to reach adsorption-desorption balance, obtaining mixed system;
2) above-mentioned mixed system is moved in simulated solar Photoreactor, react under room temperature under the simulated solar Photoreactor irradiation that wavelength is greater than 420nm, timing sampling centrifugation obtains supernatant and tests the rhodamine B in solution with ultraviolet specrophotometer (JascoV-570, Japan).
Described simulated solar Photoreactor is made up of 85-1A type magnetic stirring apparatus, 300WPLS-SXE300C xenon lamp, UVcut420 edge filter, black cloth light shield, circulator bath pump and a ventilation by forced draft system, and wherein the distance of xenon source and mixed system liquid level is 10cm.
Advantage of the present invention is: 1) preparation method of this photochemical catalyst is simple, water stability good, and can recycle after degraded; 2) utilize in the process of rhodamine B in photocatalyst for degrading water and use visible ray, can solar energy be made full use of, and technique is simple, with low cost, excellent catalytic effect.
Accompanying drawing explanation
Fig. 1 is the construction unit ball-and-stick model of this visible light catalyst.
Fig. 2 is the tomograph of this visible light catalyst.
Fig. 3 is this visible light catalyst is greater than the radiation of visible light degraded 15mg/L rhodamine B of 420nm situation by wavelength.
Fig. 4 is this visible light catalyst is greater than the radiation of visible light degraded 15mg/L rhodamine B of 420nm recycling property by wavelength.
Detailed description of the invention
Embodiment 1:
For a visible light catalyst for rhodamine B in degradation water, chemical formula is [Cu i 12(1,2,4-triazole) 8(H 2o) 2] [ α-SiW 12o 40] 2H 2o, is a kind of metal organic frame of constructing based on polyoxometallate and has the compound of three-dimensional frame structure, to there is in four kinds of crystallography independently Cu in this compound iion, by itself and ligand 1,2,4-triazole (trz) –be interconnected to form the two-dimentional double-ring cation frame structure [Cu that there is three-membered ring and ten-ring and coexist i 12(1,2,4-triazole) 8(H 2o) 2] 4+, and [ α-SiW 12o 40] 4 –anion by its terminal oxygen atom (O12, O4 and O6) respectively with the Cu1 on two-dimentional dicyclo i, Cu2 iand Cu3 iion is connected, and forms three-dimensional frame structure.
The preparation method of the described visible light catalyst for rhodamine B in degradation water, adopt solvent-thermal method preparation, step is as follows:
1) by 0.048g(0.05mmol) nitrate trihydrate copper, 0.035g(0.2mmol) 1,2,4-triazole and 0.123g(0.5mmol) polyoxometallate Na 10[SiW 9o 34] 18H 2o adds in 23mL polytetrafluoroethylene (PTFE) autoclave, and the mixed solution then adding 8mL deionized water and 2mL absolute ethyl alcohol obtains mixed liquor;
2) after above-mentioned mixed liquor being sealed in reactor, be placed in baking oven constant temperature 72 hours at 170 DEG C of temperature, then slowly room temperature is dropped to the speed of 4 DEG C/h, obtain orange bulk crystals, spend deionized water clean after, at room temperature be evaporated to dry, the visible light catalyst [Cu for rhodamine B in degradation water can be obtained i 12(1,2,4-triazole) 8(H 2o) 2] [ α-SiW 12o 40] 2H 2o.
Fig. 1 is the construction unit ball-and-stick model of this visible light catalyst, shows in figure: to there is in four kinds of crystallography independently Cu in this compound iion by with part trz –be interconnected to form the two-dimentional double-ring cation frame structure [Cu that there is three-membered ring and ten-ring and coexist i 12(trz) 8(H 2o) 2] 4+.And [ α-SiW 12o 40] 4 –anion by its terminal oxygen atom (O12, O4 and O6) respectively with the Cu1 on two-dimentional dicyclo i, Cu2 iand Cu3 iion is connected, and defines three-dimensional frame structure as shown in Figure 2.
The prepared visible light catalyst of rhodamine B in degradation water that is used for is used for organic dyestuff rhodamine B in degradation water, and step is as follows:
1) be that the rhodamine B solution of 15mg/L is placed in laminated glass beaker by 100mL concentration, then add visible light catalyst prepared by 15mg, pass into cooling water in interlayer and under dark condition, stir 1 hour to reach adsorption-desorption balance, obtaining mixed system;
2) above-mentioned mixed system is moved in simulated solar Photoreactor, react under room temperature under the simulated solar Photoreactor irradiation that wavelength is greater than 420nm, simulated solar Photoreactor is by a 85-1A type magnetic stirring apparatus, 300WPLS-SXE300C xenon lamp, UVcut420 edge filter, black cloth light shield, circulator bath pump and ventilation by forced draft system composition, wherein the distance of xenon source and mixed system liquid level is 10cm, open xenon source and adopt edge filter acquisition wavelength to be greater than the visible ray of 420nm, timing sampling centrifugation obtains supernatant and uses ultraviolet specrophotometer (JascoV-570, Japan) rhodamine B in solution is tested.
Fig. 3 is this visible light catalyst is greater than the radiation of visible light degraded 15mg/L rhodamine B of 420nm situation by wavelength.Show in figure: wavelength was greater than the radiation of visible light of 420nm after 6 hours, this photochemical catalyst reaches 88% to the degradation rate of dye, rhodamine B in water.
Fig. 4 is this visible light catalyst is greater than the radiation of visible light degraded 15mg/L rhodamine B of 420nm recycling property by wavelength.Show in figure: after this photochemical catalyst circulation rhodamine B degradation four-wheel, degradation capability is still without obviously weakening.

Claims (4)

1. for a visible light catalyst for rhodamine B in degradation water, it is characterized in that: chemical formula is [Cu i 12(1,2,4-triazole) 8(H 2o) 2] [α-SiW 12o 40] 2H 2o, is a kind of metal organic frame of constructing based on polyoxometallate and has the compound of three-dimensional frame structure, to there is in four kinds of crystallography independently Cu in this compound iion, by itself and ligand 1,2,4-triazole (trz) –be interconnected to form the two-dimentional double-ring cation frame structure [Cu that there is three-membered ring and ten-ring and coexist i 12(1,2,4-triazole) 8(H 2o) 2] 4+, and [α-SiW 12o 40] 4 –anion by its terminal oxygen atom O12, O4 and O6 respectively with the Cu1 on two-dimentional dicyclo i, Cu2 iand Cu3 iion is connected, and forms three-dimensional frame structure.
2., as claimed in claim 1 for a preparation method for the visible light catalyst of rhodamine B in degradation water, it is characterized in that adopting solvent-thermal method preparation, step is as follows:
1) by nitrate trihydrate copper, 1,2,4-triazole and polyoxometallate Na 10[SiW 9o 34] 18H 2o adds in deionized water and absolute ethyl alcohol mixed solution and obtains mixed liquor, nitrate trihydrate copper, 1,2,4-triazole, Na 10[SiW 9o 34] 18H 2the amount ratio of O and deionized water and absolute ethyl alcohol is 0.05mmol:0.2mmol:0.5mmol:8mL:2mL;
2) after above-mentioned mixed liquor being sealed in reactor, be placed in baking oven constant temperature 72 hours at 170 DEG C of temperature, then slowly room temperature is dropped to the speed of 4 DEG C/h, obtain orange bulk crystals, spend deionized water clean after, at room temperature be evaporated to dry, the visible light catalyst [Cu for rhodamine B in degradation water can be obtained i 12(1,2,4-triazole) 8(H 2o) 2] [α-SiW 12o 40] 2H 2o.
3., as claimed in claim 1 for an application for the visible light catalyst of rhodamine B in degradation water, it is characterized in that step is as follows for organic dyestuff rhodamine B in degradation water:
1) be that the rhodamine B solution of 15mg/L is placed in laminated glass beaker by 100mL concentration, then visible light catalyst prepared by 15mg is added, pass into cooling water in interlayer and under dark condition, stir 1 hour to reach adsorption-desorption balance, obtaining mixed system;
2) above-mentioned mixed system is moved in simulated solar Photoreactor, react under room temperature under the simulated solar Photoreactor irradiation that wavelength is greater than 420nm, timing sampling centrifugation obtains supernatant and tests the rhodamine B in solution with ultraviolet specrophotometer.
4. according to claim 3 for the application of the visible light catalyst of rhodamine B in degradation water, it is characterized in that: described simulated solar Photoreactor is made up of 85-1A type magnetic stirring apparatus, 300WPLS-SXE300C xenon lamp, UVcut420 edge filter, black cloth light shield, circulator bath pump and a ventilation by forced draft system, and wherein the distance of xenon source and mixed system liquid level is 10cm.
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