CN108160120A - A kind of compounded visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And organic matter degradation application - Google Patents

A kind of compounded visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And organic matter degradation application Download PDF

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CN108160120A
CN108160120A CN201810121771.4A CN201810121771A CN108160120A CN 108160120 A CN108160120 A CN 108160120A CN 201810121771 A CN201810121771 A CN 201810121771A CN 108160120 A CN108160120 A CN 108160120A
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CN108160120B (en
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项敬来
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Donggang Zhike Industrial Park Co ltd
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Abstract

The present invention relates to a kind of compounded visible light photocatalyst, specifically a kind of Ag of modification2CO3/TiO2/UIO‑66‑(COOH)2Visible-light photocatalyst and its degradation application in organic matter rhodamine, formaldehyde.The loaded photocatalyst of the present invention, is widely used, and makes simply, cost is relatively low, and stability is good, and can effectively degrade rhodamine, formaldehyde organic matter in a short time, improve the degradation efficiency of visible light catalyst.

Description

A kind of compounded visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2It is and organic Object degradation application
Technical field
The present invention relates to a kind of compounded visible light photocatalyst, specifically a kind of Ag of modification2CO3/TiO2/ UIO-66- (COOH)2Visible-light photocatalyst and its application.
Background technology
Environmental pollution and energy crisis have gradually jeopardized the existence of the mankind.Photocatalysis technology is considered as that the solution energy and environment are asked Inscribe most effective, most promising method.TiO2Have many advantages, such as that efficient, nontoxic, chemical property is stablized, be that current research is most wide General photochemical catalyst.By doping vario-property or with narrow-band semiconductor it is compound the methods of can improve TiO2Response to visible ray, but Its visible light activity is still very low, also has very big distance apart from practical application.It is therefore desirable to develop with high visible-light activity Novel photocatalyst.
Ag2CO3With very strong visible light photocatalysis active, the application in the fields such as environmental pollution improvement and clean energy resource conversion Prospect is very wide.However, in Photocatalytic Degradation Process, Ag2CO3Easily by photoetch, Ag2CO3Silver ion easily by photoproduction Electron reduction is silver, and catalyst activity is caused to be gradually reduced, seriously constrains its practical application.Therefore, Ag is improved2CO3Light it is steady Qualitative is an important research direction.
Although nano-TiO2Photocatalytic activity it is high, but it easily reunites, and be difficult to detach and recycle in the solution, easily makes Into secondary pollution, and photochemical catalyst easy in inactivation, recycling rate of waterused is low, so seriously constraining the popularization of its photocatalysis technology makes With.In order to solve these problems, researcher is by making nano-TiO2Particulate load is on all very stable carrier of structure and property Realize or carry out metallic element doping, such as silver, it is nonmetallic ion-doped, such as N, C；Rare earth element Re adulterate or Titanium dioxide and other visible light-responded substances progress is compound, such as TdS, ZnO etc., to improve the visible ray of titanium dioxide sound Performance is answered, increases photochemical catalyst energy level.
Nano-TiO2 photocatalyst after load materially increases the specific surface area of TiO2 photochemical catalysts, and To the reunion of crystal grain and the transformation of crystalline phase is inhibited also to have certain positive effect.And since carrier sheet is as activated adoption material Material, porous carrier can adsorb organic pollution first in the dark, reach absorption dissociation equilibrium, then under light illumination, organic contamination More efficient photocatalysis, and then the TiO2 photocatalytic activities improved can occur with TiO2 for object.In addition, nano TiO 2 exists High degree of dispersion on carrier can also improve its utilization rate to light.
The present wide carrier of domestic and international application has silica gel, aluminium oxide, glass fibre, graphene, activated carbon and some days Right mineral such as diatomite, zeolite etc..Because of the pore structure and high stability that zeolite is abundant, become widest for catalyst One of carrier.But zeolite also has many deficiencies, such as poromerics, its limited sorption capacity, particularly molten In liquid, macromolecular solvent is not entered in hole.It would therefore be desirable to a kind of aperture is adjustable, and a kind of load that adjustable extent is wider Body, however this porous materials of MOF just meet the needs studied now very much.At present, only SBA-15 molecular sieves are as nanometer TiO2The research of the carrier of photochemical catalyst causes the extensive concern and interest of domestic and foreign scholars.
TiO2The solid support method of photochemical catalyst can be divided into two major class, when physical load method, second is that chemical load method.Physics is born Load method is not related to chemically reacting, thus experimental implementation is simpler than chemical load method, but the TiO2 loads of chemical load method synthesis The hydrothermal stability of type photochemical catalyst is higher, and chemical property is more stable.
Currently, the chemical method of synthesis coated TiO2/carrier mainly has two kinds of direct synthesis technique and post synthesis method.First synthesis carries Then TiO2 is distributed to silica gel, aluminium oxide, glass fibre, graphite by body material by infusion process, sedimentation or grafting again Alkene, activated carbon or molecular sieve synthesize TiO2/ carriers.The advantages of the method is that the hydrothermal stability of TiO2/ carriers is high, and shortcoming is The dispersibility of TiO2 is poor, and the amount of TiO2 poorly controls.But the more of post synthesis method is still used under normal circumstances, And can by the method for modifying carrier, make up TiO2 dispersibility it is poor the shortcomings that.
In recent years, the research of transition metal or heavy metal to load type titania doping and modification, is increasingly taken seriously, and The photocatalysis effect of load type titania after doping is greatly improved, and application range is also very extensive.There is scholar In order to which load type titania photocatalyst is with good stability, TiO2/SBA-15 is doped with Au elements, The Au/TiO2/SBA-15 being synthesized also has and is doped modified synthesis M/TiO2/SBA-15 light using Ni metal and Bi and urges Agent, but there are still the problem of dispersability of titanium dioxide energy is general, and catalyst cannot be steady in a long-term.
Invention content
MOFs metal organic frameworks are the very rapid coordination polymers of developed recently, have three-dimensional pore structure, generally with gold Category ion is tie point, and organic ligand support extends into space 3D, is that the another class except zeolite and carbon nanotube is important Novel porous materials, have that high voidage, low-density, bigger serface, duct rule, aperture is adjustable etc., and performances, UiO-66 are Rigid MOFs materials with high stability, the stability of MOFs mainly by the stability and metal of inorganic metal unit with The power of binding force determines between ligand.A key of most of MOFs is disadvantageous in that thermal stability is not high, general next It says, the thermal stability of MOFs is at 350-400 DEG C.UiO-66 is a kind of MOF with ultrastability, chemical formula Zr6O4 (OH)4(CO2)12, for its structure collapse temperature higher than 500 DEG C, the inorganic metal unit of high degree of symmetry is carried out in its stability source Zr6O4(OH)4And the Zr6The strong interaction of octahedra core and carboxyl oxygen O in ligand.One Zr6Octahedra core and 12 it is right Phthalic acid ligands form tetrahedron and octahedra two kinds of hole cage, each on eight faces of octahedron cage, It is connected with a tetrahedron cage, this connection mode constantly extends in three dimensions, has so as to be formedThe MOFs in aperture.Separately Outside, chemical stability experiments have shown that, UiO-66 have good water-resistance, acid-resisting.
For overcome the deficiencies in the prior art, the present invention is carboxyl acid modified by the way that carrier UiO-66- (Zr) is carried out first, is formed UiO-66-(COOH)2, increase the specific surface area of carrier UiO-66, increase the spaced point of titanium dioxide, so as to conducive to control point Dissipate performance and TiO2Load capacity.
In order to which UiO-66 is enable preferably to be combined with titanium dioxide, and make to be attached to the titanium dioxide on UiO-66, it is this to replace Transducing keeps the structure of UiO-66 to be basically unchanged, and improve its hydrothermal stability, and sour attachment point, which increases, enables titanium equal Even dispersion.
The application by the metal salt dopping to titanium dioxide, will similary AgCO3 and TiO2 with visible light activity it is compound, Simply and effectively the cooperative photocatalysis performance of the two is played, is formed and had complementary advantages, moreover, in order to which active component is made to be formed well Dispersion, increase photochemical catalyst stability and improve service life, by the metal organic framework UiO- with ultrastability 66 (Zr) carry out acid modification first, improve the carboxylic acid load point of carrier, so as to improve the Active components distribution of catalyst point, make It obtains catalyst in service life with photocatalytic activity simultaneously to optimize, there is presently no similar reports to prepare synthesis photocatalyst structure For Ag2CO3/TiO2/ UIO-66-(COOH)2。
The preparation method of the composite visible light catalyst of the present invention is as follows：
(1) by weight, 5-10 parts of polyvinylpyrrolidones, 80~100 parts of absolute ethyl alcohols, 50~100 parts of butyl titanates are mixed After conjunction, isothermal reaction 2~8 hours, obtain electrostatic spinning solution under 40~90 DEG C of temperature condition, using electrostatic spinning process Electrostatic spinning is carried out to electrostatic spinning solution, obtains TiO2Nanofiber；
(2) TiO that will be obtained2Nanofiber is dried 1-4 hours at 80~100 DEG C, then with 1 DEG C/min of heating speed Rate is heated to 500~1000 DEG C, and constant temperature obtains nano-TiO after 4~8 hours2。
(3) nano-TiO that will be prepared2Ultrasonic disperse adjusts solution ph in water, adds in silver nitrate AgNO3Solution, It stirs evenly, then adds in Na2CO3, precipitation is generated, solid is taken to wash, 100-150 DEG C is dried to obtain Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2：In a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF, surpass Sound disperses 10min-2h, and then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, and stirring is brilliant at 100-150 DEG C Change reaction 10-24 hours, cooling down after the completion of reaction, centrifugal filtration is washed, dry.Each component molar ratio ZrCl4: ligand: Template glacial acetic acid=1: 1-2: 20-30.
(5) using infusion process by Ag2CO3/TiO2It is carried on UIO-66- (COOH)2Porous material obtains Ag2CO3/TiO2/ UIO-66-(COOH)2Composite photo-catalyst.
Ag in compounded visible light photocatalyst2CO3∶TiO2∶UIO-66-(COOH)2Mass ratio be 1-20: 30-50: 20-40.
Preferably, in step (3) silver nitrate a concentration of 0.2-1mol/L, addition 10-20mL/L；Sodium carbonate it is a concentration of 0.5-2mol/L, preferably 0.5-1mol/L.
Preferably, the dipping of step (5) is by the Ag in step (3)2CO3/TiO2Dispersion is in water, adding in UIO-66- (COOH)2Carrier material carries out impregnation 1-30 hours, stands 2-5 hours, washs, dry, the preferred 70-100 of drying temperature ℃。
Uniform titanium dioxide nanofiber is prepared by method of electrostatic spinning first in the present invention, then dries, and grinding is formed Nanometer titanium dioxide micro-sphere particle has good stability of crystal form, has larger draw ratio and smaller diameter, uniformly Pore structure, then further with Ag2CO3The preparation of composite photo-catalyst is carried out, since silver carbonate has the property of pyrolytic Therefore matter, in the two recombination process, needs controlling reaction temperature and drying condition, it is impossible to more than 200 DEG C, moreover, of the invention Simple ion catch electron microscopy is employed, it, can effective shape by the ph and sodium carbonate of control system and the addition concentration of silver nitrate Into silver carbonate product, and the two is mutually promoted the separation of electron-hole, is conducive to quickly generate photoelectron, on this basis, will Ag2CO3/TiO2It is impregnated in carboxyl acid modified UiO-66, due to the hole basket structure of embedded Zr in metal organic framework porous material, Multiple octahedra, tetrahedral three-dimensional structures are formed, Ag can be formed2CO3、TiO2It is embedded in or is carried on carrier and show in spy Accelerate the transmission and generation of photoelectricity ion in fixed three-dimensional structure, improve photocatalysis efficiency.
Moreover, traditional UiO-66, which is modified, is often use-NH2 ,-CH3 etc., the present invention is using ligand 1,2,4,5- benzene tetracarboxylic acids Acid replaces other ligands, and specific ligand is 1,2,4,5- benzene tertacarbonic acids (i.e. H4BETA), i.e., and 1,2,4,5- benzene tetracarboxylic acids.Using Simple hydro-thermal solvent method prepares porous material, with good stability, heat-resisting quantity and hole structural property.
Further, the present invention has also carried out more in-depth study, increases the step of B is adulterated, specific steps：(1) by weight Gauge, after 5-10 parts of polyvinylpyrrolidones, 80~100 parts of absolute ethyl alcohols, 50~100 parts of butyl titanates are mixed, further Addition 2-5mol/L boric acid, isothermal reaction 2~8 hours under 40~90 DEG C of temperature condition, the titanium dioxide for obtaining boracic are quiet Electrospun solution carries out electrostatic spinning to electrostatic spinning solution using electrostatic spinning process, obtains containing B-TiO2Nanofiber；
(2) it will obtain containing B-TiO2Nanofiber is dried hour at 80~100 DEG C, then with 1 DEG C/min of heating speed Rate is heated to 500~1000 DEG C, and constant temperature obtains a nanometer B Uniform Dopeds TiO after 4~8 hours2 (B-TiO2)。
(3) the nanometer B-TiO that will be prepared2Ultrasonic disperse adjusts solution ph in water, adds in silver nitrate AgNO3Solution With stir evenly, then add in Na2CO3, generation precipitation, solid is taken to wash, 100-150 DEG C be dried to obtain it is boron doped Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2：In a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF, surpass Sound disperses 10min-2h, and then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, and stirring is brilliant at 100-150 DEG C Change reaction 10-24 hours, cooling down after the completion of reaction, centrifugal filtration is washed, dry.
(5) Ag for being adulterated B using infusion process2CO3/TiO2It is carried on UIO-66- (COOH)2Porous material will contain boron Ag2CO3/TiO2Dispersion is in water, adding in UIO-66- (COOH)2Carrier material carries out impregnation 1-30 hours, and it is small to stand 2-5 When, washing, 100 DEG C are dried to obtain boron doped Ag2CO3/TiO2/ UIO-66-(COOH)2Composite photo-catalyst.Wherein B is adulterated Amount, with catalyst basic calculation 1-10wt%.
Metal salt silver carbonate is utilized in above-mentioned technical proposal, nonmetallic B ions adulterate simultaneously, synergistic effect, shape can be formed Into strong hole-electron, so as to further improve photocatalytic activity.
The composite photo-catalyst of preparation is applied in the degradation process of organic matter rhodamine and formaldehyde by the present invention, in closed glass It contains in glass case into 3 μ L organic matters culture dishes and coated with photochemical catalyst, concentration of organic gas is 1.8mg/m in case3, 30W days Light lamp Continuous irradiation investigates the degradation rate of rhodamine, formaldehyde.
Specific embodiment
The present invention will be further described in detail with reference to the specific embodiments.
Embodiment 1
(1) by weight, after 5 parts of polyvinylpyrrolidones, 100 parts of absolute ethyl alcohols, 50 parts of butyl titanates being mixed, in 50 temperature Isothermal reaction 3 hours, obtain electrostatic spinning solution under the conditions of degree, and electrostatic is carried out to electrostatic spinning solution using electrostatic spinning process Spinning obtains TiO2Nanofiber；
(2) TiO that will be obtained2Nanofiber is dried 1 hour at 100 DEG C, then is heated with 1 DEG C/min of heating rate To 500 DEG C, constant temperature obtains nano-TiO after 4 hours2.X-ray powder diffraction (XRD) is carried out to products obtained therefrom to test, and is formed sharp Titanium ore type nano-titanium dioxide.
(3) nano-TiO that will be prepared2Ultrasonic disperse adjusts solution ph (7-10) in water, adds in silver nitrate 1mol/L AgNO3Solution 10mL/L, stirs evenly, and then adds in 1mol/L Na2CO3, generation precipitation takes solid to wash, and 100 DEG C dry To Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2：In a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF, surpass Sound disperses 10min-2h, and then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, and stirring is brilliant at 100-150 DEG C Change reaction 10-24 hours, cooling down after the completion of reaction, centrifugal filtration is washed, dry.Wherein each component molar ratio ZrCl4∶ Ligand: template glacial acetic acid=1: 1: 20.
(5) using infusion process by Ag2CO3/TiO2It is carried on UIO-66- (COOH)2Porous material, will be in step (3) Ag2CO3/TiO2Dispersion is in water, adding in UIO-66- (COOH)2Carrier material carries out impregnation 1-30 hours, stands 2-5 Hour, washing, 100 DEG C of dryings obtain Ag2CO3/TiO2/UIO-66-(COOH)2Composite photo-catalyst.Ag2CO3∶TiO2∶UIO- 66-(COOH)2Mass ratio be 15: 45: 40.
Embodiment 2
(1) by weight, after 10 parts of polyvinylpyrrolidones, 100 parts of absolute ethyl alcohols, 100 parts of butyl titanates being mixed, at 60 DEG C Temperature condition under isothermal reaction 6 hours, obtain electrostatic spinning solution, electrostatic spinning solution carried out using electrostatic spinning process Electrostatic spinning obtains TiO2Nanofiber；
(2) TiO that will be obtained2Nanofiber is dried 2 hours at 100 DEG C, then is heated with 1 DEG C/min of heating rate To 900 DEG C, constant temperature obtains nano-TiO after 68 hours2。
(3) nano-TiO that will be prepared2Ultrasonic disperse adjusts solution ph (9-10) in water, adds in 0.5mol/L nitre Sour silver AgNO3Solution 20nl, stirs evenly, and then adds in the Na of 1mol/L2CO3, precipitation is generated, solid is taken to wash, 100-150 DEG C it is dried to obtain Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2：In a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF, surpass Sound disperses 10min-2h, and then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, and stirring is brilliant at 100-150 DEG C Change reaction 10-24 hours, cooling down after the completion of reaction, centrifugal filtration is washed, dry.Wherein each component molar ratio ZrCl4∶ Ligand: template glacial acetic acid=1: 1: 30.
(5) using infusion process by Ag2CO3/TiO2It is carried on UIO-66- (COOH)2Porous material, by Ag2CO3/TiO2Dispersion with In water, UIO-66- (COOH) is added in2Carrier material carries out impregnation 1-30 hours, stands 2-5 hours, and washing, 100 DEG C dry It is dry to obtain Ag2CO3/TiO2/UIO-66-(COOH)2Composite photo-catalyst.Ag2CO3∶TiO2∶UIO-66-(COOH)2Mass ratio It is 20: 40: 40.
Embodiment 3
(1) by weight, after 10 parts of polyvinylpyrrolidones, 80 parts of absolute ethyl alcohols, 80 parts of butyl titanates being mixed, at 80 DEG C Isothermal reaction 2 hours, obtain electrostatic spinning solution under temperature condition, electrostatic spinning solution are carried out using electrostatic spinning process quiet Electrospun obtains TiO2Nanofiber；
(2) TiO that will be obtained2Nanofiber is dried 3 hours, then be heated to 1 DEG C/min of heating rate at 80 DEG C 9000 DEG C, constant temperature obtains nano-TiO after 4 hours2。
(3) nano-TiO that will be prepared2Ultrasonic disperse adjusts solution ph in water, adds in silver nitrate 1mol/L AgNO3Solution 20mL/L, stirs evenly, and then adds in 1mol/L Na2CO3, precipitation is generated, solid is taken to wash, 100-150 DEG C dry It is dry to obtain Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2：In a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF, surpass Sound disperses 10min-2h, and then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, and stirring is brilliant at 100-150 DEG C Change reaction 15 hours, cooling down after the completion of reaction, centrifugal filtration is washed, dry.Wherein each component molar ratio ZrCl4: ligand : template glacial acetic acid=1: 1: 20.
(5) by the Ag in step (3)2CO3/TiO2Dispersion is in water, adding in UIO-66- (COOH)2Carrier material impregnate anti- It answers 10 hours, stands 2 hours, washing, 100 DEG C of dryings obtain Ag2CO3/TiO2/ UIO-66-(COOH)2Composite photo-catalyst. Ag in compounded visible light photocatalyst2CO3∶TiO2∶ UIO-66-(COOH)2Mass ratio be 20: 45: 35.
Embodiment 4
(1) by weight, after 8 parts of polyvinylpyrrolidones, 100 parts of absolute ethyl alcohols, 100 parts of butyl titanates being mixed, further Addition 5mol/L boric acid, isothermal reaction 5 hours under 60 DEG C of temperature condition, the titanium dioxide electrostatic spinning for obtaining boracic are molten Liquid carries out electrostatic spinning to electrostatic spinning solution using electrostatic spinning process, obtains containing B-TiO2Nanofiber；
(2) it will obtain containing B-TiO2Nanofiber is dried 4 hours at 80~100 DEG C, then with 1 DEG C/min of heating Rate is heated to 600 DEG C, and constant temperature obtains a nanometer B Uniform Dopeds TiO after 4~8 hours2(B-TiO2)。
(3) the nanometer B-TiO that will be prepared2Ultrasonic disperse adjusts solution ph in water, adds in 1mol/L silver nitrates AgNO3Solution and, stir evenly, then add in 1mol/L Na2CO3, generation precipitation takes solid to wash, and 100-150 DEG C dry To boron doped Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2：In a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF, surpass Sound disperses 10min-2h, and then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, and stirring is brilliant at 100-150 DEG C Change reaction 10-24 hours, cooling down after the completion of reaction, centrifugal filtration is washed, dry.Wherein each component molar ratio ZrCl4∶ Ligand: template glacial acetic acid=1: 2: 30.
(5) Ag for being adulterated B using infusion process2CO3/TiO2It is carried on UIO-66- (COOH)2Porous material will contain boron Ag2CO3/TiO2Dispersion is in water, adding in UIO-66- (COOH)2Carrier material carries out impregnation 1-30 hours, and it is small to stand 2-5 When, washing, 100 DEG C are dried to obtain boron doped Ag2CO3/TiO2/ UIO-66-(COOH)2Composite photo-catalyst.Wherein B is adulterated Amount, with catalyst basic calculation 10wt%, Ag in composite photo-catalyst2CO3∶TiO2∶UIO-66-(COOH)2Mass ratio be 20 ∶40∶40。
Comparative example 1
Carrier is not used, only prepares Ag2CO3/TiO2Composite photo-catalyst, other experiment parameters are the same as embodiment 1.
Comparative example 2
Using alumina catalyst support, Ag is impregnated2CO3/TiO2Other experiment parameters obtain Ag with embodiment 12CO3/TiO2/Al2O3 Supported composite photocatalyst.
Comparative example 3
Using carrier S BA-15 molecular sieves, Ag is impregnated2CO3/TiO2Other experiment parameters obtain Ag with embodiment 12CO3/TiO2/ SBA-15 supported composite photocatalysts.
Comparative example 4
Using without carboxyl acid modified UiO-66 (Zr) carrier, load stain Ag2CO3/TiO2Other experiment parameters with embodiment 1, Obtain Ag2CO3/TiO2/ UiO-66 supported composite photocatalysts.
Application examples
Embodiment is organic for degradation of organic substances rhodamine, formaldehyde etc. with the compounded visible light photocatalyst prepared by comparative example Object.It contains in closed glass box into 3 μ L organic matters culture dishes and coated with photochemical catalyst, concentration of organic gas is in case 1.8mg/m3, 30W fluorescent lamp Continuous irradiations, rhodamine, formaldehyde degradation rate such as the following table 1.
Have the above results can be seen that the present invention support type visible light composite catalyst it is small in catalyst amount, light application time (it is less than 30min) in the case of short, still the excellent effect with rhodamine, formaldehyde organic matter adsorption rate more than 98%, it can To find out the efficiency that light degradation organic matter is substantially increased for the compound and support modification of nanometer titanium dioxide carbon progress silver carbonate, Have great importance.And catalyst preparation process is simple, is expected to carry out commerical test with promoting.
The above description is merely a specific embodiment, but protection scope of the present invention is not limited thereto, any to be familiar with Those skilled in the art disclosed herein technical scope in, without the variation that creative work is expected or can replace It changes, should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims Protection domain subject to.

Claims (3)

1. a kind of compounded visible light photocatalyst, which is characterized in that the photocatalyst structure is Ag2CO3/TiO2/UIO-66- (COOH)2, specific preparation method is as follows：
(1) by weight, after 10 parts of polyvinylpyrrolidones, 80 parts of absolute ethyl alcohols, 80 parts of butyl titanates being mixed, at 80 DEG C Isothermal reaction 2 hours, obtain electrostatic spinning solution under temperature condition, electrostatic spinning solution are carried out using electrostatic spinning process quiet Electrospun obtains TiO2Nanofiber；
(2) TiO that will be obtained2Nanofiber is dried 3 hours, then be heated to 1 DEG C/min of heating rate at 80 DEG C 9000 DEG C, constant temperature obtains nano-TiO after 4 hours2。
(3) nano-TiO that will be prepared2Ultrasonic disperse adjusts solution ph in water, adds in silver nitrate 1mol/L AgNO3 Solution 20mL/L, stirs evenly, and then adds in 1mol/L Na2CO3, generation precipitation takes solid to wash, and 100-150 DEG C dry To Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2：ZrCl4, glacial acetic acid are dissolved in solvent DMF in a kettle, ultrasound Disperse 10min-2h, then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, stirring, the crystallization at 100-150 DEG C Reaction 15 hours, cooling down after the completion of reaction, centrifugal filtration are washed, dry.Wherein each component molar ratio ZrCl4: ligand: Template glacial acetic acid=1: 1: 20.
(5) by the Ag in step (3)2CO3/TiO2Dispersion is in water, adding in UIO-66- (COOH)2Carrier material impregnate anti- It answers 10 hours, stands 2 hours, washing, 100 DEG C of dryings obtain Ag2CO3/TiO2/UIO-66-(COOH)2Composite photo-catalyst. Ag in compounded visible light photocatalyst2CO3∶TiO2∶UIO-66-(COOH)2Mass ratio be 20: 45: 35.
2. application of the compounded visible light photocatalyst as described in claim 1 in degradation of organic substances rhodamine, formaldehyde etc..
3. application as claimed in claim 2, it is characterised in that：Contain in closed glass box into 3 μ L organic matters culture dishes and Coated with 5g photochemical catalysts, concentration of organic gas is 1.8mg/m in case3, 30W fluorescent lamp Continuous irradiations.
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