CN103611577A - Visible light catalyst for high-efficiently degrading organic dye waste water and preparation method thereof - Google Patents
Visible light catalyst for high-efficiently degrading organic dye waste water and preparation method thereof Download PDFInfo
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- CN103611577A CN103611577A CN201310692149.6A CN201310692149A CN103611577A CN 103611577 A CN103611577 A CN 103611577A CN 201310692149 A CN201310692149 A CN 201310692149A CN 103611577 A CN103611577 A CN 103611577A
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Abstract
The invention relates to a visible light catalyst for high-efficiently degrading organic dye waste water and a preparation method thereof, which belong to the technical field of environment and energy source. The preparation method is characterized by comprising the steps of mixing zinc ferrite and chitosan, cross-linking the mixture through glutaraldehyde so as to obtain a cross-linked chitosan/zinc ferrite compound, growing cuprous oxide on the surface of the cross-linked chitosan/zinc ferrite compound under the low-temperature hydrothermal condition so as to obtain the cuprous oxide/cross-linked chitosan/zinc ferrite triplet composite visible light catalyst. By adopting the novel triplet composite visible light catalyst, multiple coordination functionality of the chitosan, the zinc ferrite and the cuprous oxide can be played, the composite possibility of an electron and an electron hole can be effectively reduced, the apparent band-gap energy of the composite catalyst can be reduced, the spectrum range can be enlarged, the utilization rate of the visible light can be greatly improved, and the treatment effect of the waste water can be enhanced; the visible light catalyst is stable in performance, has no residue, has magnetism and is easily recycled; the waste water treatment process is simple, the cost can be greatly reduced, and the visible light catalyst and the preparation method thereof are an environment-friendly and high-efficient novel material and a novel method respectively.
Description
Technical field
Visible light catalyst of a kind of efficient degradation of organic dye waste water and preparation method thereof, the invention belongs to environment and energy technology field, be specifically related to the preparation of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst and for the treatment of organic dye waste water.
Background technology
Along with developing rapidly of modern industry, the discharge capacity of industrial wastewater is increasing.In all types of industries waste water, waste water from dyestuff is because its colourity is dark, COD is high and contain a large amount of teratogenesis, carcinogenic azo-compound, and serious harm ecological environment, has brought threat to people's life and health, be the reluctant waste water of a class, need new green, efficient treatment technology badly.
Photocatalysis is as a kind of green energy resource technology, because of the extensive concern that disposal ability is strong, reaction condition is gentle, non-secondary pollution has caused Chinese scholars.Photochemical catalyst is a kind of semi-conducting material in essence, and when absorption energy is more than or equal to the light of its band-gap energy, the electrons excite transitions in valence band is to conduction band, thus formation hole-electron pair.These holes and electronics, be to have the carrier of oxidation, reducing power very by force, can decompose being adsorbed on semiconductor surface and chemical substance around, and even mineralising is H
2o and CO
2deng inorganic molecules.At present, what in photocatalysis field, research was comparatively deep is nm TiO 2-base optical catalyst, the feature such as they have stable chemical nature, resistance to wear, fast light burn into cost is low and nontoxic, except being used to, degradation of organic substances and sterilization, to be also widely used at the aspects such as preparation of photodissociation water and solar cell.Yet (3.2eV) is wide for the band-gap energy of titanium dioxide, its excitation wavelength is 387.5nm, belongs to ultraviolet region.And for solar spectrum, main concentration of energy is in 460nm～600nm wave-length coverage, ultraviolet light proportion less than 4%, so titanium dioxide is extremely low to the utilization ratio of sunshine; The recombination probability of the photo-generated carrier of titanium dioxide (electronics and hole) is high, causes quantum efficiency to reduce, and affects photocatalysis efficiency; In addition, while processing waste water, be suspended in that titania nanoparticles in system is easily reunited, inactivation, reaction finishes comparatively difficulty of rear recovery, is difficult to recycle.Therefore,, from making full use of the angle of sunshine, prepare a kind of visible light catalyst that is easy to recycle and reuse, high electricity conversion and all have great importance at the energy and environmental area.
Zinc ferrite (ZnFe
2o
4) be a kind of semiconductor (band-gap energy is 1.9eV), there are the potentiality that transform visible ray, responsive to visible ray.Yet its valence band electromotive force is lower, electricity conversion is low, make it be not suitable for being directly used in photocatalytically degradating organic dye, but zinc ferrite is magnetic, can be by the low-cost recycle and reuse of externally-applied magnetic field, and there is the advantage to visible ray sensitivity.Cuprous oxide, a kind of p-type semiconductor, band-gap energy is 2.17eV, with low cost, is a kind of very promising novel visible catalysis material, starts in the recent period to cause concern.But thereby cuprous oxide has easy reunion greatly to reduce catalysis specific area, affects photocatalysis efficiency; Be difficult to recovery, easily residual; The problems such as recombination probability height that electronics and hole are right.Therefore be necessary photochemical catalyst to carry out composite modified, to being stablized, be easy to the high-performance visible light catalyzing agent of recycle and reuse.
Summary of the invention
The object of the invention is the defect existing for solving prior art, visible light catalyst of a kind of efficient degradation of organic dye waste water and preparation method thereof is provided, to being stablized, be easy to the high-performance visible light catalyzing agent of recycle and reuse, realize green, process organic dye waste water efficiently, at low cost.
Technical scheme of the present invention: visible light catalyst of a kind of efficient degradation of organic dye waste water and preparation method thereof, can be achieved through the following technical solutions: zinc ferrite and chitosan-acetic acid solution are mixed, add glutaraldehyde cross-linking, obtain cross-linked chitosan/zinc ferrite compound; Under low-temperature hydrothermal condition, at cross-linked chitosan/zinc ferrite composite surface growth cuprous oxide, obtain the dendritic spherical cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst in surface, for the processing of organic dye waste water.
Visible light catalyst of a kind of efficient degradation of organic dye waste water and preparation method thereof, comprises the steps:
Nano-magnetic zinc ferrite (ZnFe
2o
4) preparation of crystal: according to document (Shihong Xu, Journal of Physical Chemistry C, 2009,113(6), 2463-2467), adopt hydro-thermal method preparation.For brown crystal, spinel-type, XRD (2 θ): 29.86
o, 35.28
o, 42.61
o, 56.53
o, 61.94
o, see Fig. 3, literature value is: 30.00
o, 35.31
o, 42.91
o, 56.53
o, 62.11
o; FT-IR (KBr): 558cm
-1(Zn-O), 425cm
-1(Fe-O).
The preparation of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst:
(1) preparation of cross-linked chitosan/zinc ferrite compound: shitosan is joined in the aqueous acetic acid of 0.50mol/L, stirring and dissolving, the mass ratio of shitosan and aqueous acetic acid is 1:25～50, obtains chitosan-acetic acid solution; In chitosan-acetic acid solution, add nanometer zinc ferrite, the mass ratio of shitosan and zinc ferrite is 2～8:1; Dispersed with stirring 0.5～2h; To the pH value that slowly drips 10wt% weak aqua ammonia regulator solution in above-mentioned solution, be 7～9, then the glutaraldehyde water solution that drips 25wt% carries out cross-linking reaction, mass ratio 4～the 15:1 of glutaraldehyde water solution and shitosan, at 50～80 ℃, reaction 3～8h, externally-applied magnetic field is separated, and the spherical products obtaining is fully washed by absolute ethyl alcohol, deionized water successively, 50 ℃ of vacuum drying, obtain cross-linked chitosan/zinc ferrite compound;
(2) preparation of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst: by hydrated copper sulfate (CuSO
45H
2o) join in deionized water, be stirred to completely and dissolve, the concentration copper sulfate solution that is 0.05～0.5mol/L, add a certain amount of polyethylene glycol PEG-8000, cross-linked chitosan/zinc ferrite compound, stir 10～20min, after being uniformly dispersed, add the sodium hydrate aqueous solution of 1～5mol/L, stir 30～60min, make Cu (OH)
2precipitation completely; Then, drip while stirring the aqueous ascorbic acid that concentration is 0.1～0.5mol/L, wherein NaOH: hydrated copper sulfate: the mol ratio of ascorbic acid is: 6～4:2:1; The mol ratio of hydrated copper sulfate: PEG-8000 is: 400～600:1; Cross-linked chitosan/zinc ferrite compound: the mass ratio of hydrated copper sulfate is 5～10:1, under room temperature, 100rpm, reaction 2～4h, externally-applied magnetic field is separated, by absolute ethyl alcohol, deionized water, respectively wash 3 times respectively, 50 ℃ of vacuum drying, obtain cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.
The application of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst of preparation, for the treatment of organic dye waste water, comprise the steps: organic dye waste water sample, with NaOH or salt acid for adjusting pH value, be 7～9, cuprous oxide/cross-linked chitosan/zinc ferrite tri compound the visible light catalyst that adds preparation under normal temperature, consumption is: 0.5～1.5g/L, the xenon lamp of 300W of take is light source, by optical filter elimination ultraviolet light part.With ultraviolet-visible spectrophotometry, measure the absorbance of waste water from dyestuff with the variation of light application time, calculate the clearance of organic dyestuff.
The invention has the beneficial effects as follows: compared with prior art, the present invention take cross-linked chitosan three-dimensional network fixedly zinc ferrite compound be core, the dendroid cuprous oxide of surface orientation growth is shell, has prepared the hud typed visible light catalyst of a kind of novel cuprous oxide/cross-linked chitosan/zinc ferrite tri compound.The tri compound visible light catalyst that the present invention is prepared, its dendritic shell is conducive to the intervention of visible ray, effective, the even contact that are conducive to cuprous oxide and zinc ferrite, to strengthen synergy, thereby improve the susceptibility of visible ray and reduce the recombination probability in electronics and hole; Effectively reduce the apparent band-gap energy of composite catalyst, widen spectral region, improve the utilization ratio of visible ray; Its dendritic shell can effectively be avoided the contact area of reunion, increase and dyestuff, improves catalytic efficiency; The adsorption capacity of cross-linked chitosan excellence, can effectively adsorb dyestuff in waste water to catalyst surface, thereby improves the photocatalytic degradation efficiency of dyestuff; Cross-linked chitosan is fixed the three-dimensional network of zinc ferrite and guiding and fixation to shell dendroid cuprous oxide growth, makes that gained tri compound visible light catalyst of the present invention is highly stable, noresidue in waste water; In catalyst, magnetic zinc ferrite makes that this catalyst can facilitate by externally-applied magnetic field, recycling at low cost; Waste water treatment process is simple, can greatly reduce costs, and is a kind of the have green of prospects for commercial application, new material and new method efficiently.Preparation method of the hud typed visible light catalyst of this cuprous oxide/cross-linked chitosan/zinc ferrite tri compound and products thereof belongs to initiative work with application.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 1 gained cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.
Fig. 2 is the FT-IR spectrogram of embodiment 1 gained cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst, cross-linked chitosan/zinc ferrite compound and raw materials of chitosan in the present invention, wherein 1 is raw materials of chitosan, 2 is cross-linked chitosan/zinc ferrite compound, and 3 is cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.
Fig. 3 is the XRD figure of embodiment 1 gained cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst, zinc ferrite and comparative example 1 gained cuprous oxide in the present invention, wherein 1 is zinc ferrite, 2 is cuprous oxide, and 3 is cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.
Fig. 4 is the UV-vis collection of illustrative plates of embodiment 1 gained cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst, zinc ferrite and comparative example 1 gained cuprous oxide in the present invention, wherein 1 is zinc ferrite, 2 is cuprous oxide, and 3 is cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.
Fig. 5 is embodiment 1～4 removal effect figure of gained cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst to rhodamine B in the present invention, and wherein 4 is embodiment 3 catalyst; 3 is embodiment 2 catalyst; 2 is embodiment 1 catalyst; 1 is embodiment 4 catalyst.
Fig. 6 is embodiment 1～4 removal effect figure of gained cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst to methylene blue waste water in the present invention, and wherein 4 is embodiment 3 catalyst; 3 is embodiment 2 catalyst; 2 is embodiment 1 catalyst; 1 is embodiment 4 catalyst.
Fig. 7 is embodiment 1～4 removal effect figure of gained cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst to Methyl Orange in Wastewater in the present invention, and wherein 4 is embodiment 3 catalyst; 3 is embodiment 2 catalyst; 2 is embodiment 1 catalyst; 1 is embodiment 4 catalyst.
Fig. 8 is the embodiment of the present invention 2 and 3 gained cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalysts to methylene blue waste water removal efficiency and recycles the graph of a relation of number of times, and wherein 1 is embodiment 3 catalyst, and 2 is embodiment 2 catalyst.
The specific embodiment
Below in conjunction with embodiment, the invention will be further described, but application of the present invention is not limited to this.
The present embodiment is the preparation of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.Detailed process is: 10g shitosan is joined in the aqueous acetic acid of 250g 0.50mol/L, stirring and dissolving, obtains chitosan-acetic acid solution; In chitosan-acetic acid solution, add 5g nanometer zinc ferrite, dispersed with stirring 0.5h; To the pH value that slowly drips 10wt% weak aqua ammonia regulator solution in above-mentioned solution, be 7, then the glutaraldehyde water solution that drips 40g 25wt% carries out cross-linking reaction, at 50 ℃, reaction 3h, externally-applied magnetic field is separated, the spherical products obtaining is fully washed by absolute ethyl alcohol, deionized water successively, and 50 ℃ of vacuum drying obtain cross-linked chitosan/zinc ferrite compound; Hydrated copper sulfate 0.025mol is joined in 500mL deionized water, be stirred to completely and dissolve, add 0.0625mmol polyethylene glycol PEG-8000,31.2g cross-linked chitosan/zinc ferrite compound, stir 10min, after being uniformly dispersed, the sodium hydrate aqueous solution 50mL that adds 1mol/L, stirs 30min, makes Cu (OH)
2precipitation completely; Then, dripping while stirring concentration is the aqueous ascorbic acid 125mL of 0.1mol/L, under room temperature, 100rpm, reaction 2h, externally-applied magnetic field is separated, by absolute ethyl alcohol, deionized water, respectively wash 3 times respectively, 50 ℃ of vacuum drying, obtain cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.The SEM figure of gained cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst is shown in Fig. 1, FT-IR infrared spectrum is shown in Fig. 2, XRD is shown in Fig. 3, Fig. 4 is shown in by UV-vis collection of illustrative plates, by the known cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst that successfully synthesizes of these characterization results.As shown in Figure 1, this catalyst is spherical, and surface is dendritic cuprous oxide; As shown in Figure 4, cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst that the present invention is prepared, more independent zinc ferrite, cuprous oxide photocatalyst, absorbance improves greatly, and in whole visible region, all there is stronger absorption, greatly widened spectral region; And maximum absorption wavelength concentrates on 500～600nm scope, the concentrated wave-length coverage of solar energy, therefore has higher utilization ratio to visible ray just.
The present embodiment is the preparation of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.Detailed process is: 10g shitosan is joined in the aqueous acetic acid of 300g 0.50mol/L, stirring and dissolving, obtains chitosan-acetic acid solution; In chitosan-acetic acid solution, add 2.5g nanometer zinc ferrite, dispersed with stirring 1h; To the pH value that slowly drips 10wt% weak aqua ammonia regulator solution in above-mentioned solution, be 8, then the glutaraldehyde water solution that drips 70g 25wt% carries out cross-linking reaction, at 60 ℃, reaction 5h, externally-applied magnetic field is separated, the spherical products obtaining is fully washed by absolute ethyl alcohol, deionized water successively, and 50 ℃ of vacuum drying obtain cross-linked chitosan/zinc ferrite compound; Hydrated copper sulfate 0.05mol is joined in 500mL deionized water, be stirred to completely and dissolve, add 0.1111mmol polyethylene glycol PEG-8000,87.5g cross-linked chitosan/zinc ferrite compound, stir 12min, after being uniformly dispersed, the sodium hydrate aqueous solution 63mL that adds 2mol/L, stirs 40min, makes Cu (OH)
2precipitation completely; Then, dripping while stirring concentration is the aqueous ascorbic acid 125mL of 0.2mol/L, under room temperature, 100rpm, reaction 3h, externally-applied magnetic field is separated, by absolute ethyl alcohol, deionized water, respectively wash 3 times respectively, 50 ℃ of vacuum drying, obtain cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.XRD (2 θ) result of gained cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst is: 24.86
o, 30.31
o, 34.88
o, 38.14
o, 42.01
o, 44.81
o, 53.11
o, 61.24
o, 64.05
o, 74.26
o, coincide with Fig. 3 acquired results, known cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst that successfully synthesizes.
The present embodiment is the preparation of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.Detailed process is: 10g shitosan is joined in the aqueous acetic acid of 400g 0.50mol/L, stirring and dissolving, obtains chitosan-acetic acid solution; In chitosan-acetic acid solution, add 1.7g nanometer zinc ferrite, dispersed with stirring 1.5h; To the pH value that slowly drips 10wt% weak aqua ammonia regulator solution in above-mentioned solution, be 9, then the glutaraldehyde water solution that drips 120g 25wt% carries out cross-linking reaction, at 70 ℃, reaction 7h, externally-applied magnetic field is separated, the spherical products obtaining is fully washed by absolute ethyl alcohol, deionized water successively, and 50 ℃ of vacuum drying obtain cross-linked chitosan/zinc ferrite compound; Hydrated copper sulfate 0.15mol is joined in 500mL deionized water, be stirred to completely and dissolve, add 0.3000mmol polyethylene glycol PEG-8000,337.5g cross-linked chitosan/zinc ferrite compound, stir 18min, after being uniformly dispersed, add 3mol/L sodium hydrate aqueous solution 140mL, stir 50min, make Cu (OH)
2precipitation completely; Then, dripping while stirring concentration is the aqueous ascorbic acid 250mL of 0.3mol/L, under room temperature, 100rpm, reaction 4h, externally-applied magnetic field is separated, by absolute ethyl alcohol, deionized water, respectively wash 3 times respectively, 50 ℃ of vacuum drying, obtain cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.XRD (2 θ) result of gained cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst is: 24.86
o, 30.31
o, 34.88
o, 38.14
o, 42.01
o, 44.81
o, 53.11
o, 61.24
o, 64.05
o, 74.26
o, coincide with Fig. 3 acquired results, known cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst that successfully synthesizes.
The present embodiment is the preparation of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.Detailed process is: 10g shitosan is joined in the aqueous acetic acid of 500g 0.50mol/L, stirring and dissolving, obtains chitosan-acetic acid solution; In chitosan-acetic acid solution, add 1.25g nanometer zinc ferrite, dispersed with stirring 2h; To the pH value that slowly drips 10wt% weak aqua ammonia regulator solution in above-mentioned solution, be 9, then the glutaraldehyde water solution that drips 150g 25wt% carries out cross-linking reaction, at 80 ℃, reaction 8h, externally-applied magnetic field is separated, the spherical products obtaining is fully washed by absolute ethyl alcohol, deionized water successively, and 50 ℃ of vacuum drying obtain cross-linked chitosan/zinc ferrite compound; Hydrated copper sulfate 0.25mol is joined in 500mL deionized water, be stirred to completely and dissolve, add 0.4167mmol polyethylene glycol PEG-8000,624.0g cross-linked chitosan/zinc ferrite compound, stir 20min, after being uniformly dispersed, the sodium hydrate aqueous solution 150mL that adds 5mol/L, stirs 60min, makes Cu (OH)
2precipitation completely; Then, dripping while stirring concentration is the aqueous ascorbic acid 250mL of 0.5mol/L, under room temperature, 100rpm, reaction 4h, externally-applied magnetic field is separated, by absolute ethyl alcohol, deionized water, respectively wash 3 times respectively, 50 ℃ of vacuum drying, obtain cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.XRD (2 θ) result of gained cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst is: 24.86
o, 30.31
o, 34.88
o, 38.14
o, 42.01
o, 44.81
o, 53.11
o, 61.24
o, 64.05
o, 74.26
o, coincide with Fig. 3 acquired results, known cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst that successfully synthesizes.
The present embodiment is the application of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst of preparation, the treatment effect of this visible light catalyst of high spot reviews to rhdamine B waste water.Detailed process is: certain printing and dyeing mill's waste water sample, and pH is 8, rhodamine B content is 150mg/L, cuprous oxide/cross-linked chitosan/zinc ferrite tri compound the visible light catalyst that adds preparation under normal temperature, consumption is: 0.5g/L, the xenon lamp of 300W of take is light source, by optical filter elimination ultraviolet light part.With ultraviolet-visible spectrophotometry, measure the absorbance of waste water from dyestuff with the variation of light application time, calculate the clearance of organic dyestuff, the results are shown in Figure 5.As shown in Figure 5: the prepared ternary complex catalyst of the present invention can efficiently utilize visible ray, degradation of dye efficiency is high, embodiment 1～4 gained catalyst all reaches more than 90% clearance in 60min, and wherein embodiment 3 gained catalyst, especially when 50min, have reached 100% clearance.
The present embodiment is the application of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst of preparation, the treatment effect of this visible light catalyst of high spot reviews to methylene blue dye waste water.Detailed process is: certain printing and dyeing mill's waste water sample, pH is 6, hydro-oxidation sodium is adjusted pH to 7, methylene blue count is 50mg/L, cuprous oxide/cross-linked chitosan/zinc ferrite tri compound the visible light catalyst that adds preparation under normal temperature, consumption is: 1.5g/L, the xenon lamp of 300W of take is light source, by optical filter elimination ultraviolet light part.With ultraviolet-visible spectrophotometry, measure the absorbance of waste water from dyestuff with the variation of light application time, calculate the clearance of organic dyestuff, the results are shown in Figure 6.As shown in Figure 6: the prepared ternary complex catalyst of the present invention can efficiently utilize visible ray, degradation of dye efficiency is high, embodiment 1～4 gained catalyst all reaches more than 90% clearance in 45min, and wherein embodiment 3 gained catalyst, especially when 30min, have reached 100% clearance.
Embodiment 7
The present embodiment is the application of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst of preparation, the treatment effect of this visible light catalyst of high spot reviews to methyl orange dye waste water.Detailed process is: preparation 150mg/L methyl orange aqueous solution, pH is about 7, adds cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst of preparation under normal temperature, and consumption is: 1.0g/L, the xenon lamp of 300W of take is light source, by optical filter elimination ultraviolet light part.With ultraviolet-visible spectrophotometry, measure the absorbance of waste water from dyestuff with the variation of light application time, calculate the clearance of organic dyestuff, the results are shown in Figure 7.As shown in Figure 7: the prepared ternary complex catalyst of the present invention can efficiently utilize visible ray, degradation of dye efficiency is high, embodiment 1～4 gained catalyst all reaches more than 90% clearance in 60min, and wherein embodiment 3 gained catalyst, especially when 50min, have reached 100% clearance.
The present embodiment is the application of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst of preparation, the repeat performance of this visible light catalyst of high spot reviews and residual.Detailed process is: all using the methyl blue solution 100mL of 30mg/L as test fluid at every turn, add 0.1g cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst, after illumination 30min, externally-applied magnetic field separating catalyst, the clearance of determined by ultraviolet spectrophotometry methylene blue, Atomic Absorption Spectrometry metal residual, the results are shown in Figure 8.As shown in Figure 8: the prepared ternary complex catalyst of the present invention is reused 20 times, performance remains unchanged substantially, and residual in waste water sample of metal all do not detected for 20 times, therefore prepared tri compound visible light catalyst stable in properties, the efficiency of the present invention is high, can pass through easily externally-applied magnetic field recycling use, greatly reduce costs.
Comparative example 1
This example as a comparison case, is prepared cuprous oxide preparing under the hydrothermal condition that cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst is identical, does performance comparison with cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.Detailed process is: hydrated copper sulfate 0.025mol is joined in 500mL deionized water, be stirred to completely and dissolve, add 0.0625mmol polyethylene glycol PEG-8000, stir 10min, after being uniformly dispersed, add the sodium hydrate aqueous solution 50mL of 1mol/L, stir 30min, make Cu (OH)
2precipitation completely; Then, dripping while stirring concentration is the aqueous ascorbic acid 125mL of 0.1mol/L, under room temperature, 100rpm, reaction 2h, centrifugation solid, respectively washs 3 times by absolute ethyl alcohol, deionized water respectively, 50 ℃ of vacuum drying, obtain cuprous oxide visible light catalyst.The XRD of gained cuprous oxide (2 θ) result is: 37.24
o, 43.05
o, 61.58
o, 73.11
o, see Fig. 3.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (2)
1. visible light catalyst of an efficient degradation of organic dye waste water and preparation method thereof, is characterized in that, comprises the steps:
(1) preparation of cross-linked chitosan/zinc ferrite compound: shitosan is joined in the aqueous acetic acid of 0.50mol/L, stirring and dissolving, the mass ratio of shitosan and aqueous acetic acid is 1:25～50, obtains chitosan-acetic acid solution; In chitosan-acetic acid solution, add nanometer zinc ferrite, the mass ratio of shitosan and zinc ferrite is 2～8:1; Dispersed with stirring 0.5～2h; To the pH value that slowly drips 10wt% weak aqua ammonia regulator solution in above-mentioned solution, be 7～9, then the glutaraldehyde water solution that drips 25wt% carries out cross-linking reaction, mass ratio 4～the 15:1 of glutaraldehyde water solution and shitosan, at 50～80 ℃, reaction 3～8h, externally-applied magnetic field is separated, and the spherical products obtaining is fully washed by absolute ethyl alcohol, deionized water successively, 50 ℃ of vacuum drying, obtain cross-linked chitosan/zinc ferrite compound;
(2) preparation of cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst: by hydrated copper sulfate (CuSO
45H
2o) join in deionized water, be stirred to completely and dissolve, the concentration copper sulfate solution that is 0.05～0.5mol/L, add a certain amount of polyethylene glycol PEG-8000, cross-linked chitosan/zinc ferrite compound, stir 10～20min, after being uniformly dispersed, add the sodium hydrate aqueous solution of 1～5mol/L, stir 30～60min, make Cu (OH)
2precipitation completely; Then, drip while stirring the aqueous ascorbic acid that concentration is 0.1～0.5mol/L, wherein NaOH: hydrated copper sulfate: the mol ratio of ascorbic acid is: 6～4:2:1; The mol ratio of hydrated copper sulfate: PEG-8000 is: 400～600:1; Cross-linked chitosan/zinc ferrite compound: the mass ratio of hydrated copper sulfate is 5～10:1, under room temperature, 100rpm, reaction 2～4h, externally-applied magnetic field is separated, by absolute ethyl alcohol, deionized water, respectively wash 3 times respectively, 50 ℃ of vacuum drying, obtain cuprous oxide/cross-linked chitosan/zinc ferrite tri compound visible light catalyst.
2. the application of cuprous oxide/cross-linked chitosan of preparing by claim 1 method/zinc ferrite tri compound visible light catalyst, is characterized in that, for Organic Dyestuff Wastewater Treatment, the addition of this catalyst is 0.5～1.5g/L.
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| CN201310692149.6A CN103611577B (en) | 2013-12-17 | 2013-12-17 | Visible light catalyst of a kind of efficient degradation of organic dye waste water and preparation method thereof |
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| CN103611577B CN103611577B (en) | 2015-12-09 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106006918A (en) * | 2016-06-17 | 2016-10-12 | 辽宁科技学院 | Chemical wastewater treatment agent |
| CN106000339A (en) * | 2016-06-12 | 2016-10-12 | 苏州科技学院 | Adsorption and degradation agent for organic waste water and preparation method thereof |
| CN107394149A (en) * | 2017-07-13 | 2017-11-24 | 国家纳米科学中心 | Carbon-zinc composite material, preparation method thereof and application of carbon-zinc composite material as electrode material |
| CN107649151A (en) * | 2017-09-22 | 2018-02-02 | 常州大学 | A kind of preparation method of sulfur doping ferrous acid Co catalysts |
| CN108680625A (en) * | 2018-05-07 | 2018-10-19 | 杭州电子科技大学 | The preparation method and applications of cuprous oxide/cobalt acid nickel hollow-core construction composite nano-microsphere |
| CN111715277A (en) * | 2020-06-22 | 2020-09-29 | 江南大学 | Easily-recycled magnetic visible-light-driven photocatalyst and preparation method thereof |
| CN114054028A (en) * | 2021-12-09 | 2022-02-18 | 重庆化工职业学院 | Cu2O/CoFe2O4Preparation method and application of magnetic composite catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106000339A (en) * | 2016-06-12 | 2016-10-12 | 苏州科技学院 | Adsorption and degradation agent for organic waste water and preparation method thereof |
| CN106006918A (en) * | 2016-06-17 | 2016-10-12 | 辽宁科技学院 | Chemical wastewater treatment agent |
| CN107394149A (en) * | 2017-07-13 | 2017-11-24 | 国家纳米科学中心 | Carbon-zinc composite material, preparation method thereof and application of carbon-zinc composite material as electrode material |
| CN107394149B (en) * | 2017-07-13 | 2020-06-30 | 国家纳米科学中心 | Carbon-zinc composite material, preparation method thereof and application of carbon-zinc composite material as electrode material |
| CN107649151A (en) * | 2017-09-22 | 2018-02-02 | 常州大学 | A kind of preparation method of sulfur doping ferrous acid Co catalysts |
| CN108680625A (en) * | 2018-05-07 | 2018-10-19 | 杭州电子科技大学 | The preparation method and applications of cuprous oxide/cobalt acid nickel hollow-core construction composite nano-microsphere |
| CN111715277A (en) * | 2020-06-22 | 2020-09-29 | 江南大学 | Easily-recycled magnetic visible-light-driven photocatalyst and preparation method thereof |
| CN111715277B (en) * | 2020-06-22 | 2021-06-25 | 江南大学 | Easily-recycled magnetic visible-light-driven photocatalyst and preparation method thereof |
| CN114054028A (en) * | 2021-12-09 | 2022-02-18 | 重庆化工职业学院 | Cu2O/CoFe2O4Preparation method and application of magnetic composite catalyst |
| CN114054028B (en) * | 2021-12-09 | 2024-03-08 | 重庆化工职业学院 | Cu (copper) alloy 2 O/CoFe 2 O 4 Preparation method and application of magnetic composite catalyst |
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