CN103990493A - Visible-light catalyst for degrading rhodamine B in water and application of catalyst - Google Patents

Visible-light catalyst for degrading rhodamine B in water and application of catalyst Download PDF

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CN103990493A
CN103990493A CN201410206969.4A CN201410206969A CN103990493A CN 103990493 A CN103990493 A CN 103990493A CN 201410206969 A CN201410206969 A CN 201410206969A CN 103990493 A CN103990493 A CN 103990493A
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rhodamine
light catalyst
triazole
visible
visible light
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CN103990493B (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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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses a visible-light catalyst for degrading rhodamine B in water. The chemical formula of the visible-light catalyst is shown as [Cu<I>12(1, 2, 4-triazole)8(H2O)2][alpha-SiW12O40].2H2O. The visible-light catalyst is a compound consisting of a metal-organic framework constructed based on a polyoxometallate structure and a three-dimentional framework structure. Four types of Cu<I> ions which are independent on the crystallography exist in the compound; the Cu<I> ions are mutually connected with a ligand 1, 2, 4-triazole to form a two-dimensional bicycle positive ion framework structure with co-existing of a ternary ring and a deca-membered ring; [alpha-SiW12O40]<4-> negative ions are respectively connected to three copper ions on the two-dimensional dual rings through end group oxygen atoms to form the three-dimentional framework structure. The visible-light catalyst has the advantages of simple preparation method and excellent water stability and can be recycled after degrading; the visible light catalyst is used for degrading the rhodamine B in water by using the light catalyst, so that the solar energy can be fully used. The visible-light catalyst is simple in process, low in cost and excellent in catalytic effect.

Description

A kind of visible light catalyst for degradation water rhodamine B and application thereof
Technical field
The invention belongs to photocatalysis technology field, particularly a kind of visible light catalyst for degradation water rhodamine B 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 1972, Japanese scientist rattan island was clear has delivered about the report of preparing hydrogen at titanium dioxide electrodes glazing decomposition water on Nature, cause immediately the field scholar's such as chemistry, physics, material extensive concern in the world, also worldwide launched to be conceived to the decomposition reaction of optically catalytic TiO 2 oxidation of organic compounds, although TiO simultaneously 2have stability high, active high, can reusing and the advantage such as low cost, but this research does not finally all realize application widely, main cause is large (3.2 ev) of energy gap of titanium dioxide, and the ultraviolet light that is equivalent to only have wavelength to be less than or equal to 387 nm just can excite TiO 2produce conduction band electron and valence band hole and be oxidized and decomposing organic matter.Account for earth surface and receive sunshine gross energy and be less than 4% but wavelength is less than the ultraviolet light of 380 nm.If directly use TiO 2make catalyst, other more than 95% sunshine just can not be utilized effectively.In addition, owing to exciting TiO in sunshine 2ultraviolet ray intensity all a little less than, cause the efficiency of the photocatalysis degradation organic contaminant that directly utilizes sunshine to do light source very low; If utilize artificial light source can produce again energy consumption problem.Therefore, design, synthesize at visible region and have stronger photocatalytic activity, can utilize the high stability material of visible light part in sunshine, become the tool important meaning of current photocatalysis and challenging problem.
Polyoxometallate is the Polyoxometallate that a class is mainly made up of molybdenum and tungsten, has the character of similar semiconductor light-catalyst, is a kind of wide-band gap material (3.1-4.6eV), and absworption peak is mainly in ultra-violet (UV) band, but its bands of a spectrum can extend to visible region.When under the effect at ultraviolet or visible ray, part can occur and move transition to the lotus of metal, produce oxidability and be greater than 2.5 V(vs. standard hydrogen electrodes) excitation state, thereby make most organic pollutants 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.Also caused in recent years people's very big interest 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 adopt multiple technologies to carry out the modification of catalyst, if polyoxometallate and semiconducting compound are (with TiO 2be main) compound.But photoresponse scope is limited (mainly in ultra-violet (UV) band) still, and its application is restricted.
The rise of metal-organic framework (MOFs) material is also for photocatalysis technology has injected new vitality in recent years, it is the coordination utilizing between organic ligand and metal ion, the kind zeolitic material with supermolecule microporous network structure that self assembly forms, has uncommon hole shape, little specific area, relatively mild synthesis condition; But also there is the features such as structure diversification, uncommon photoelectric effect and numerous operational metal ions due to it, just developing the study hotspot becoming in the energy, material and life science crossing domain rapidly.In the synthetic technology of MOFs, for organic ligand, wherein the coordination mode of functional group and coordination ability can difference changing by lewis acid and metal ion flexibly; For metal node, the ion that metal ion can be large from electronegativity forms the secondary construction unit of check figure metals different, that linking number is different.By the advantage of this two aspect, framework obtains modifying, deriving, thereby forms colourful structure type.Various and there is adjustability and little specific area just because of its structure, more be conducive to design, the synthetic adjustable material of energy gap, make it 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.
Be badly in need of at present a kind of novel low-energy zone width and the good catalysis material of water stability, if polyoxometallate and metal-organic framework materials can be combined effectively, design the novel photocatalysis system that expands photoresponse scope and can recycle, realize visible light efficient catalytic reaction, to have important theory significance, simultaneously also, environmental protection efficient for developing, 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 a kind of visible light catalyst for degradation water rhodamine B and application thereof are provided, and 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 make full use of solar energy, technique is simple, with low cost, excellent catalytic effect.
Technical scheme of the present invention:
For a visible light catalyst for degradation water rhodamine B, 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 the compound with three-dimensional frame structure, has in four kinds of crystallography independently Cu in this compound iion, by itself and ligand 1,2,4-triazole (trz) –be interconnected to form and there is the two-dimentional double-ring cation frame structure [Cu that three-membered ring and ten-ring coexist i 12(1,2,4-triazole) 8(H 2o) 2] 4+, and [ α-SiW 12o 40] 4 –anion by its end group oxygen atom (O12, O4 and O6) respectively with two-dimentional dicyclo on Cu1 i, Cu2 iand Cu3 iion is connected, and forms three-dimensional frame structure.
A preparation method for the described visible light catalyst for degradation water rhodamine B, adopts solvent-thermal method preparation, and 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) above-mentioned mixed liquor is sealed in after reactor, be placed in baking oven constant temperature 72 hours at 170 DEG C of temperature, then slowly drop to room temperature with the speed of 4 DEG C/h, obtain orange bulk crystals, with after deionized water washes clean, at room temperature be evaporated to dryly, can make the visible light catalyst [Cu for degradation water rhodamine B 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 degradation water rhodamine B, for degradation water organic dyestuff rhodamine B, step is as follows:
1) the rhodamine B solution that is 15mg/L by 100mL concentration is placed in laminated glass beaker, and the visible light catalyst that then adds 15mg to prepare passes into cooling water and under dark condition, stirs 1 hour to reach adsorption-desorption balance in interlayer, obtain mixed system;
2) above-mentioned mixed system is moved in simulated solar Photoreactor, wavelength be greater than 420nm simulated solar Photoreactor irradiate under under room temperature, react, timing sampling centrifugation obtains supernatant and uses ultraviolet specrophotometer (Jasco V-570, Japan) to test the rhodamine B in solution.
Described simulated solar Photoreactor is made up of a 85-1A type magnetic stirring apparatus, 300W PLS-SXE300C xenon lamp, UVcut420 edge filter, black cloth light shield, circulator bath pump and 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 make full use of solar energy, and technique is simple, with low cost, excellent catalytic effect.
Brief description of the drawings
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 degradation water rhodamine B, 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 the compound with three-dimensional frame structure, has in four kinds of crystallography independently Cu in this compound iion, by itself and ligand 1,2,4-triazole (trz) –be interconnected to form and there is the two-dimentional double-ring cation frame structure [Cu that three-membered ring and ten-ring coexist i 12(1,2,4-triazole) 8(H 2o) 2] 4+, and [ α-SiW 12o 40] 4 –anion by its end group oxygen atom (O12, O4 and O6) respectively with two-dimentional dicyclo on Cu1 i, Cu2 iand Cu3 iion is connected, and forms three-dimensional frame structure.
The preparation method of the described visible light catalyst for degradation water rhodamine B, adopts solvent-thermal method preparation, and 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, then adds the mixed solution of 8mL deionized water and 2mL absolute ethyl alcohol to obtain mixed liquor;
2) above-mentioned mixed liquor is sealed in after reactor, be placed in baking oven constant temperature 72 hours at 170 DEG C of temperature, then slowly drop to room temperature with the speed of 4 DEG C/h, obtain orange bulk crystals, with after deionized water washes clean, at room temperature be evaporated to dryly, can make the visible light catalyst [Cu for degradation water rhodamine B 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, in figure, shows: in this compound, have in four kinds of crystallography independently Cu iion by with part trz –be interconnected to form and there is the two-dimentional double-ring cation frame structure [Cu that three-membered ring and ten-ring coexist i 12(trz) 8(H 2o) 2] 4+.And [ α-SiW 12o 40] 4 –anion by its end group oxygen atom (O12, O4 and O6) respectively with two-dimentional dicyclo on Cu1 i, Cu2 iand Cu3 iion is connected, and has formed three-dimensional frame structure as shown in Figure 2.
By the prepared visible light catalyst for degradation water rhodamine B, for degradation water organic dyestuff rhodamine B, step is as follows:
1) the rhodamine B solution that is 15mg/L by 100mL concentration is placed in laminated glass beaker, and the visible light catalyst that then adds 15mg to prepare passes into cooling water and under dark condition, stirs 1 hour to reach adsorption-desorption balance in interlayer, obtain mixed system;
2) above-mentioned mixed system is moved in simulated solar Photoreactor, wavelength be greater than 420nm simulated solar Photoreactor irradiate under under room temperature, react, simulated solar Photoreactor is by a 85-1A type magnetic stirring apparatus, 300W PLS-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 to obtain the visible ray that wavelength is greater than 420nm, timing sampling centrifugation obtains supernatant and uses ultraviolet specrophotometer (Jasco V-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.In figure, show: wavelength was greater than the radiation of visible light of 420nm after 6 hours, and this photochemical catalyst reaches 88% to the degradation rate of dyestuff 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.In figure, show: 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 degradation water rhodamine B, 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 the compound with three-dimensional frame structure, has in four kinds of crystallography independently Cu in this compound iion, by itself and ligand 1,2,4-triazole (trz) –be interconnected to form and there is the two-dimentional double-ring cation frame structure [Cu that three-membered ring and ten-ring coexist i 12(1,2,4-triazole) 8(H 2o) 2] 4+, and [ α-SiW 12o 40] 4 –anion by its end group oxygen atom (O12, O4 and O6) respectively with two-dimentional dicyclo on Cu1 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 degradation water rhodamine B, 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) above-mentioned mixed liquor is sealed in after reactor, be placed in baking oven constant temperature 72 hours at 170 DEG C of temperature, then slowly drop to room temperature with the speed of 4 DEG C/h, obtain orange bulk crystals, with after deionized water washes clean, at room temperature be evaporated to dryly, can make the visible light catalyst [Cu for degradation water rhodamine B 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 degradation water rhodamine B, it is characterized in that step is as follows for degradation water organic dyestuff rhodamine B:
1) the rhodamine B solution that is 15mg/L by 100mL concentration is placed in laminated glass beaker, and the visible light catalyst that then adds 15mg to prepare passes into cooling water and under dark condition, stirs 1 hour to reach adsorption-desorption balance in interlayer, obtain mixed system;
2) above-mentioned mixed system is moved in simulated solar Photoreactor, wavelength be greater than 420nm simulated solar Photoreactor irradiate under under room temperature, react, timing sampling centrifugation obtains supernatant and uses ultraviolet specrophotometer (Jasco V-570, Japan) to test the rhodamine B in solution.
4. according to claim 3 for the application of the visible light catalyst of degradation water rhodamine B, it is characterized in that: described simulated solar Photoreactor is made up of a 85-1A type magnetic stirring apparatus, 300W PLS-SXE300C xenon lamp, UVcut420 edge filter, black cloth light shield, circulator bath pump and ventilation by forced draft system, and wherein the distance of xenon source and mixed system liquid level is 10cm.
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WO2023005143A1 (en) * 2021-07-30 2023-02-02 皖西学院 Two-dimensional supramolecular compound synthesized on the basis of 1,3,5-tri(4-carbonylphenyloxy)benzene, method therefor, and application thereof
US20230173469A1 (en) * 2021-12-03 2023-06-08 Changzhou University Isopoly-molybdic acid coordination polymer catalyst, method of manufacturing the same and application thereof
US11878288B2 (en) * 2021-12-03 2024-01-23 Changzhou University Isopoly-molybdic acid coordination polymer catalyst, method of manufacturing the same and application thereof
CN114790298A (en) * 2022-05-05 2022-07-26 哈尔滨理工大学 Polyacid-based nickel metal organic framework colorimetric sensing material with interpenetrating structure
CN116217950A (en) * 2022-12-15 2023-06-06 天津大学 Metal organic framework eutectic material and application thereof in photocatalytic degradation
CN116217950B (en) * 2022-12-15 2023-08-11 天津大学 Metal organic framework eutectic material and application thereof in photocatalytic degradation

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