CN101733161A - Photochemical preparation method of chitosan loaded metal sulfide photocatalyst - Google Patents
Photochemical preparation method of chitosan loaded metal sulfide photocatalyst Download PDFInfo
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Abstract
The embodiment of the invention provides a preparation method of a chitosan loaded metal sulfide photocatalyst, belonging to the field of preparation of organic and inorganic hybrid photocatalyst materials. The method comprises the following steps of: preparing a chitosan metal ion coordination compound; preparing a precursor solution; carrying out photochemical reaction; post-treating the photocatalyst; and after the photochemical reaction is ended, filtering, washing and drying to obtain the chitosan loaded metal sulfide photocatalyst. The invention has the advantages of simple preparation process, mild reaction condition, good reaction controllability, strong practicability, low equipment requirement and the like. The chitosan loaded metal sulfide photocatalyst can degrade organic matters of methyl orange, methylene blue and the like under ultraviolet light, visible light or natural sun light, and has better application prospect on the aspect of degrading organic pollutants when used as the photocatalyst.
Description
Technical field
The present invention relates to a kind of technology of preparing of photocatalyst material, relate in particular to a kind of photochemical method for preparation of chitosan loaded metal sulfide type photochemical catalyst.
Background technology
Semiconductor alloy sulfide such as CdS, CuS, PbS, ZnS etc. have excellent photocatalytic performance, aspect the high concentrated organic wastewater processing good prospects for application are being arranged.The preparation method of semiconductor alloy sulfide mainly contains at present: the direct reaction method of element (Direct Elemental Reaction), sluggish precipitation (Homogeneous Precipitation), hydrothermal synthesis method, micro emulsion method (Microemulsion) and sol-gel process (Sol-Gel).
In these preparation methods, as a kind of early stage technology of preparing, the direct reaction method of element is eliminated in the research application facet at present substantially because of its energy consumption of reaction height, product particle diameter are big, the more high shortcoming of impurity content.Adopt the more of Preparation by Uniform Precipitation superfines research.Advantages such as it is low that it has device efficiency, and technology is simple, and the doping metals particle is easy, even.Hydrothermal synthesis method is meant in closed reactor (autoclave), adopts the aqueous solution as reaction system, by reaction system is heated to critical-temperature, produces hyperbaric environment and a kind of effective ways of carrying out inorganic synthetic and material preparation in reaction system.This method also only rests on research, development phase at present, and the problem of existence mainly is that complex process equipment, cost are higher, but this method is still a kind of extremely promising method for preparing powder.
In addition, there is more serious photoetch phenomenon in semiconductor alloy sulfide.Semiconductor alloy sulfide also will cause the forfeiture gradually of semiconductor alloy sulfide photo-catalysis function simultaneously organic matter being carried out the secondary heavy metal pollution that photoetch in the photocatalytic degradation process will cause processed water.Therefore semiconductor alloy sulfide and organic high molecular polymer is compound, can improve its photoetch performance to a certain extent.But the preparation technology of present semiconductor alloy sulfide is unfavorable for realizing that the original position of itself and high-molecular organic material is compound.Adopt compound technology of later stage, influence semiconductor alloy sulfide photocatalysis performance on the one hand, in addition, the improvement of its photoetch performance is also not obvious.
Photochemistry is a synthetic important technology of material, mainly is by light absorbing substance, forms excited state molecule, and then relevant chemical reaction takes place and generates a kind of method of certain material.Corresponding to heat chemistry, photochemistry has following characteristics:
1. " reagent " that cleans on only a kind of very special ecology;
2. the photochemical reaction condition is generally than heat chemistry gentleness;
3. photochemical reaction can provide safe industrial production environment, because reaction is basically in room temperature or be lower than under the room temperature and carry out;
4. in routine is synthetic, can shorten synthetic route greatly by inserting a step photochemical reaction;
5. such reaction only is subjected to the control of light, can embody the synthetic flexibility of material by the control of light path, this will provide effective instrument for the mistake functionalization and cheap the synthesizing of the device of material, localize modification, material, and good means also are provided for the original position of semiconductor alloy sulfide and high-molecular organic material is compound.
Shitosan be natural chitin take off the acetyl product, be a kind of natural polysaecharides material that extensively is present in shellfish and insect shell.A large amount of free amino groups and hydroxyl activity group are arranged in its molecular structure, and free amino group wherein has and aliphatic primary amine chemical reaction characteristic much at one, has the function of chelating heavy metal ion.In slightly acidic water solution, have a large amount of-NH in the chitosan molecule structure
3+Group, and become polyelectrolyte class material.About the development and use extremely attention of every field always of shitosan and derivative thereof, particularly its unique adsorption function has obtained deep research especially.Shitosan is to various heavy metal ion, as: Co
2+, Ni
2+, Mn
2+, As
2+, Cr
2+Deng absorption property, to the aspects such as absorption of the small organic molecule matter in the waste water from dyestuff, a large amount of research reports is all arranged both at home and abroad.
Summary of the invention
The object of the present invention is to provide a kind of photochemical method for preparation of chitosan loaded metal sulfide photocatalyst, its technology is simple, cost is low, and the metal sulfide in this photochemical catalyst is scattered between chitosan molecule with the nanometer state.
The objective of the invention is to be achieved through the following technical solutions:
A kind of photochemical method for preparation of chitosan loaded metal sulfide photocatalyst is characterized in that may further comprise the steps:
(1) preparation chitosan metal ion coordination compound particulate: the shitosan and the metal ion that will be under the solution state form complex, using basic solution adjustment complex solution pH value separates out complex to neutrality under stirring, and washing and filtering makes the chitosan metal ion coordination compound particulate;
(2) preparation precursor liquid: the described chitosan metal ion coordination compound microparticulate that will make is mixed with the precursor liquid of chitosan loaded metal sulfide in the aqueous solution that contains the sulphur source;
(3) photochemical reaction: the precursor liquid of the chitosan loaded metal sulfide that makes is positioned under the ultraviolet source stirring reaction 2 ~ 48 hours;
(4) post processing of photochemical catalyst: after photochemical reaction finishes, after filtration, promptly get chitosan loaded metal sulfide photocatalyst after the washing, drying.
Further, step (1) is specially:
Acidic aqueous solution with 0.2～5wt% is a solvent, is solute with slaine, shitosan, and the preparation chitosan concentration is the shitosan acid solution of 5～100g/L, stirs under 30～80 ℃ temperature 1～5 hour, makes chitosan metal ion coordination compound solution;
Dripping concentration in the above-mentioned chitosan metal ion coordination compound solution that makes is the NaOH alkaline solution of 0.1 ~ 0.5mol/L, stir, adjust system pH to neutrality chitosan metal ion coordination compound is separated out, filter, wash, obtain the chitosan metal ion coordination compound particulate;
Step (2) is specially:
With the above-mentioned chitosan metal ion coordination compound microparticulate that makes in deionized water, the consumption of deionized water is 10～100 times of chitosan metal ion coordination compound particulate weight, add the sulphur source then, the ratio of the quality of metal is (0.1～10) in sulphur source and the chitosan metal ion coordination compound particulate: 1, stirring and dissolving under room temperature obtains the precursor liquid of chitosan loaded metal sulfide;
Step (3) is specially:
The above-mentioned chitosan loaded metal sulfide precursor liquid that makes is positioned under the ultraviolet source that wavelength is 254 ~ 365nm, and irradiation intensity is 0.02～3.0mW/cm
2, stirring reaction 2 ~ 48 hours.
The described drying of step (4) is 50～80 ℃ of vacuum constant temperature dryings.
Described acid solution is acetum, salpeter solution, hydrochloric acid solution, citric acid solution etc., comprises the acid solution that shitosan and slaine are dissolved simultaneously.
Described slaine be in chloride, acetate, the nitrate any or several.
Described metal ion be in copper, cobalt, nickel, cadmium, chromium, zinc, lead, silver, tin or the iron ion any or several, total consumption of metal ion is for adding 0.5 ~ 5mmol by every gram shitosan.
The viscosity average molecular weigh of described shitosan is 100,000～800,000, and the deacetylation of described shitosan is 75%～95%.
Described sulphur source is solubility thiosulfates such as sodium thiosulfate, potassium thiosulfate, ATS (Ammonium thiosulphate).
The technical scheme that is provided by the invention described above embodiment as can be seen, embodiment of the present invention utilizes shitosan to Adsorption Properties for Metal Ions, by photochemical method, original position forms metal sulfide between chitosan molecule, obtains chitosan loaded metal sulfide photocatalyst; Shitosan not only plays loading functional and to the defencive function of metal sulfide, and provides organic adsorption function, and the photo-catalysis function of this loaded photocatalyst is strengthened.This method technology is simple, and a kind of new way for preparing the high-molecular organic material loaded metal sulfide is provided, and its reaction condition gentleness is pollution-free environmentally friendly, low for equipment requirements.The prepared chitosan loaded metal sulfide photocatalyst is organic matters such as degrade methyl orange, methylene blue under ultraviolet light, visible light or natural sunshine, have application promise in clinical practice as photochemical catalyst aspect the degradable organic pollutant.
Use the adsorptivity of shitosan to multiple metal ion, by photochemical reaction, original position generates semiconductor alloy sulfide between chitosan molecule, can realize effective load and coating when effectively controlling the metal sulfide size.By photochemical method prepared chitosan loaded metal sulfide, can in the photocatalysis performance that keeps metal sulfide, improve its photoetch performance, but also will the catalysis of this loaded photocatalyst be strengthened in conjunction with shitosan to organic absorption property.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the chitosan loaded CdS photochemical catalyst in the embodiment of the invention;
Fig. 2 is the transmission electron microscope photo of the chitosan loaded CdS photochemical catalyst in the embodiment of the invention.
The specific embodiment
For ease of understanding, the present invention is further illustrated below in conjunction with specific embodiment, but preparation method of the present invention is not subject to these embodiment.
Embodiment of the present invention provides a kind of preparation method of chitosan loaded metal sulfide photocatalyst, utilize shitosan to Adsorption Properties for Metal Ions, by photochemical reaction, prepare a kind of chitosan loaded metal sulfide photocatalyst, metal sulfide original position between chitosan molecule generates in this catalyst, is the nanometer distributions.This method for preparing catalyst specifically may further comprise the steps: the preparation chitosan metal ion coordination compound, make precursor liquid with the aqueous solution in sulfur-bearing source again, carry out light-catalyzed reaction, will obtain chitosan loaded metal sulfide photocatalyst after product filtration, washing, the drying.
Above-mentioned preparation method comprises the steps:
(1) preparation chitosan solution: it is in the acid solution of 0.2～5% (weight ratio) that the shitosan of certain part by weight is dissolved in 100～500 weight portion concentration, regulates pH value to 3～6, and obtaining concentration is 5～100g/L shitosan acid solution;
(2) preparation chitosan metal ion coordination compound: the ratio that adds 0.5～5mmol metal ion in every gram shitosan adds slaine in above-mentioned (1), stirred under 30～80 ℃ temperature 1～5 hour, makes chitosan metal ion coordination compound solution; Under brute force stirred, dripping concentration in this solution was the NaOH solution of 0.1～0.5mol/L, adjusted the pH value of solution value to neutral, and complex is separated out, and through repeatedly washing, filtering, obtained the chitosan metal ion coordination compound particulate;
(3) prepared composition particles in above-mentioned (2) is distributed in 10 ~ 2000ml deionized water, add the sulphur source, the ratio of the amount of metal ion species is (0.1～10) in sulphur source and the chitosan metal ion coordination compound particulate: 1, stirring and dissolving under room temperature obtains the precursor liquid of chitosan loaded metal sulfide;
(4) the described chitosan loaded metal sulfide precursor liquid that makes in above-mentioned (3) being positioned over wavelength is that 254 ~ 365nm, power are under the ultraviolet source of 4 ~ 40w, stirring reaction 2 ~ 48h, the liquid level of uviol lamp and precursor aqueous solution distance is 8～50cm during irradiation, and irradiation intensity is 0.02～3.0mW/cm
2
(5) product that makes in above-mentioned (4) is filtered, be washed to no ion and detect, 50～80 ℃ of freeze-day with constant temperature obtain chitosan loaded metal sulfide photocatalyst.
Among the above-mentioned preparation method used slaine be in chloride, acetate, the nitrate any or several;
The acid solution that adopts is acetum, salpeter solution, hydrochloric acid solution, citric acid solution etc. among the above-mentioned preparation method, comprises the acid solution that shitosan and slaine are dissolved simultaneously;
The metal ion that is adopted among the above-mentioned preparation method be in copper, cobalt, nickel, cadmium, chromium, zinc, lead, silver, tin or the iron ion any or several;
The viscosity average molecular weigh of the shitosan that is adopted among the above-mentioned preparation method is 100,000～1,000,000, and deacetylation is 75%～95%;
The sulphur source of being adopted among the above-mentioned preparation method is solubility thiosulfates such as sodium thiosulfate, potassium thiosulfate, ATS (Ammonium thiosulphate).
The preparation method that the embodiment of the invention provides, compared with prior art the present invention has the following advantages:
(1) provides a kind of new method of original position formation nano metal sulphide between chitosan molecule at normal temperatures;
(2) adopt photochemical method synthetic, utilize the low-power uviol lamp, at room temperature reaction as radiation source, the reaction condition gentleness, pollution-free environmentally friendly, simultaneously owing to do not need follow-up high-temperature calcination, effectively save the energy, reduced the cost of synthesis of nano metal sulfide.
Embodiment 1
Present embodiment provides a kind of preparation method of chitosan loaded CdS photochemical catalyst, is to utilize photochemical method to prepare the method for chitosan loaded CdS photochemical catalyst, is specifically undertaken by following step:
Take by weighing the 5g molecular weight respectively and be 400,000, deacetylation is that 85.5% shitosan and 4.664g Cadmium diacetate dihydrate (17.5mmol) join in the acetum that 200g concentration is 2.5wt%, compound concentration is the chitosan solution of 25g/L, stirs 2.5h down at 50 ℃ and obtains shitosan Cd
2+Complex solution; Dripping concentration under stirring condition in above-mentioned complex solution is the Na0H solution of 0.3mol/L, adjusts near the pH value of solution value to 7.3, with the shitosan Cd that separates out
2+Composition particles filter, wash shitosan Cd
2+The complex particle; Above-mentioned complex particle is scattered in the 100g deionized water, adds 0.724g hypo (3mmol) simultaneously, stirring and dissolving obtains chitosan loaded CdS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 24h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 1.8mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is 60 ℃ of vacuum drying, and obtaining product is chitosan loaded CdS photochemical catalyst.Fig. 1 is the X ray diffracting spectrum of products therefrom, and its diffraction maximum shows in this chitosan loaded CdS photochemical catalyst and contains the CdS crystal.Fig. 2 is the transmission electron micrograph of the chitosan loaded CdS photochemical catalyst that obtains of the embodiment of the invention, can see that sample contains a large amount of CdS crystal grain, and particle size is between 50 ~ 300nm.For the photocatalysis performance of photochemistry sintetics is described, the commercial P-25 photochemical catalyst of selecting German Deggusa company to produce carries out the photocatalysis contrast experiment, the result shows that commercial P-25 photochemical catalyst can make initial concentration at radiation of visible light after one hour be 10mmol/L methyl orange degradation 71.2%, and the CdS-loaded photochemical catalyst of present embodiment prepared chitosan under equal conditions can make methyl orange degradation 86.1% (seeing Table 1).Hence one can see that, and the prepared photochemical catalyst of present embodiment obviously is better than the commercial P-25 photochemical catalyst of using to the photocatalytic activity of methyl orange.
Embodiment 2
Present embodiment provides a kind of preparation method of chitosan loaded CuS photochemical catalyst, is to utilize photochemical method to prepare the method for chitosan loaded CuS photochemical catalyst, is specifically undertaken by following step:
Take by weighing the 3g molecular weight respectively and be 100,000, deacetylation is that 95% shitosan and 3.0836g one nitric hydrate copper (15mmol) join in the hydrochloric acid solution that the 150g mass concentration is 0.2wt%, compound concentration is the chitosan solution of 20g/L, stirs 1h down at 30 ℃ and obtains shitosan Cu
2+Complex solution; Dripping concentration under stirring condition in above-mentioned complex solution is the NaOH solution of 5mol/L, adjusts near the pH value of solution value to 7.3, with the shitosan Cu that separates out
2+Composition particles filter, wash shitosan Cu
2+The complex particle; Above-mentioned complex particle is scattered in the 300g deionized water, adds 2.944g five hydration potassium thiosulfates (10.5mmol) simultaneously, stirring and dissolving obtains chitosan loaded CuS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 2h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 3.0mW/cm
2)); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is 80 ℃ of vacuum drying, and obtaining product is chitosan loaded CuS photochemical catalyst.
Present embodiment provides a kind of preparation method of chitosan loaded NiS photochemical catalyst, is to utilize photochemical method to prepare the method for chitosan loaded NiS photochemical catalyst, is specifically undertaken by following step:
Take by weighing the 2g molecular weight respectively and be 1,000,000, deacetylation is 75% shitosan and 0.2908g Nickelous nitrate hexahydrate (1.0mmol) to join the 400g mass concentration be in 3% the salpeter solution, compound concentration is the chitosan solution of 5g/L, stirs 3h down at 80 ℃ and obtains shitosan Ni
2+Complex solution; Dripping concentration under stirring condition in above-mentioned complex solution is the NaOH solution of 0.1mol/L, adjusts near the pH value of solution value to 7.3, with the shitosan Ni that separates out
2+Composition particles filter, wash shitosan Ni
2+The complex particle; Above-mentioned complex particle is scattered in the 300g deionized water, adds 0.691g ATS (Ammonium thiosulphate) (4.7mmol) simultaneously, stirring and dissolving obtains chitosan loaded NiS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 48h under the uviol lamp, and (irradiation wavelength 365nm, irradiation intensity are 0.02mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is 50 ℃ of vacuum drying, and obtaining product is chitosan loaded NiS photochemical catalyst.
Embodiment 4
Present embodiment provides a kind of preparation method of chitosan loaded ZnS photochemical catalyst, is to utilize photochemical method to prepare the method for chitosan loaded ZnS photochemical catalyst, is specifically undertaken by following step:
Take by weighing the 20g molecular weight respectively and be 200,000, deacetylation is that 91.5% shitosan and 3.841g Zinc diacetate dihydrate (17.5mmol) join in the citric acid solution that the 200g mass concentration is 1.5wt%, compound concentration is the chitosan solution of 100g/L, stirs 5h down at 50 ℃ and obtains shitosan Zn
2+Complex solution; Dripping concentration under stirring condition in above-mentioned complex solution is the NaOH solution of 0.3mol/L, adjusts near the pH value of solution value to 7.3, with the shitosan Zn that separates out
2+Composition particles filter, wash shitosan Zn
2+The complex particle; Above-mentioned complex particle is scattered in the 200g deionized water, adds 43.43g hypo (175mmol) simultaneously, stirring and dissolving obtains chitosan loaded ZnS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 18h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 2.6mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is 60 ℃ of vacuum drying, and obtaining product is chitosan loaded ZnS photochemical catalyst.
Embodiment 5
Present embodiment provides a kind of preparation method of chitosan loaded CoS photochemical catalyst, is to utilize photochemical method to prepare the method for chitosan loaded CoS photochemical catalyst, is specifically undertaken by following step:
Take by weighing the 10g molecular weight respectively and be 500,000, deacetylation is that 88.5% shitosan and 3.5676g CoCL2 (15mmol) join in the acetum that the 200g mass concentration is 1.5wt%, compound concentration is the chitosan solution of 50g/L, stirs 3h down at 50 ℃ and obtains shitosan Co
2+Complex solution; Dripping concentration under stirring condition in above-mentioned complex solution is the NaOH solution of 0.25mol/L, adjusts near the pH value of solution value to 7.3, with the shitosan Co that separates out
2+Composition particles filter, wash shitosan Co
2+The complex particle; Above-mentioned complex particle is scattered in the 100g deionized water, adds 0.3723g hypo (1.5mmol) simultaneously, stirring and dissolving obtains chitosan loaded CoS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 36h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 2.0mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is 70 ℃ of vacuum drying, and obtaining product is chitosan loaded CoS photochemical catalyst.
Embodiment 6
Present embodiment provides a kind of preparation method of chitosan loaded CrS photochemical catalyst, is to utilize photochemical method to prepare the method for chitosan loaded CrS photochemical catalyst, is specifically undertaken by following step:
Take by weighing the 15g molecular weight respectively and be 700,000, deacetylation is that 83.6% shitosan and 9.992g chromium chloride hexahydrate (37.5mmol) join in the hydrochloric acid solution that the 200g mass concentration is 2.0wt%, compound concentration is the chitosan solution of 75g/L, stirs 4h down at 60 ℃ and obtains shitosan Cr
2+Complex solution; Dripping concentration under stirring condition in above-mentioned complex solution is the NaOH solution of 0.25mol/L, adjusts near the pH value of solution value to 7.3, with the shitosan Cr that separates out
2+Composition particles filter, wash shitosan Cr
2+The complex particle; Above-mentioned complex particle is scattered in the 300g deionized water, adds 18.614g hypo (75mmol) simultaneously, stirring and dissolving obtains chitosan loaded CrS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 12h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 2.8mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is 50 ℃ of vacuum drying, and obtaining product is chitosan loaded CrS photochemical catalyst.
Embodiment 7
Present embodiment provides a kind of preparation method of chitosan loaded PbS photochemical catalyst, is to utilize photochemical method to prepare the method for chitosan loaded PbS photochemical catalyst, is specifically undertaken by following step:
Take by weighing the 7g molecular weight respectively and be 150,000, deacetylation is that 92.5% shitosan and 5.1923g lead acetate trihydrate (21.5mmol) join in the acetum that the 200g mass concentration is 1.5wt%, compound concentration is the chitosan solution of 35g/L, stirs 3h down at 40 ℃ and obtains shitosan Pb
2+Complex solution; Dripping concentration under stirring condition in above-mentioned complex solution is the NaOH solution of 0.45mol/L, adjusts near the pH value of solution value to 7.3, with the shitosan Pb that separates out
2+Composition particles filter, wash shitosan Pb
2+The complex particle; Above-mentioned complex particle is scattered in the 150g deionized water, adds 2.668g hypo (10.75mmol) simultaneously, stirring and dissolving obtains chitosan loaded PbS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 24h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 2.8mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is 80 ℃ of vacuum drying, and obtaining product is chitosan loaded PbS photochemical catalyst.
Embodiment 8
Present embodiment provides a kind of chitosan loaded Ag
2The preparation method of S photochemical catalyst is to utilize photochemical method to prepare chitosan loaded Ag
2The method of S photochemical catalyst, specifically undertaken by following step:
Take by weighing the 6g molecular weight respectively and be 400,000, deacetylation is that 89.8% shitosan and 32.089g silver nitrate (12.3mmol) join in the citric acid solution that the 500g mass concentration is 2.3wt%, compound concentration is the chitosan solution of 12g/L, stirs 4h down at 50 ℃ and obtains shitosan Ag
+Complex solution; Dripping concentration under stirring condition in above-mentioned complex solution is the NaOH solution of 0.2mol/L, adjusts near the pH value of solution value to 7.3, with the shitosan Ag that separates out
+Composition particles filter, wash shitosan Ag
+The complex particle; Above-mentioned complex particle is scattered in the 200g deionized water, adds 16.520g hypo (4.1mmol) simultaneously, stirring and dissolving obtains chitosan loaded AgS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 24h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 2.3mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is 60 ℃ of vacuum drying, and obtaining product is chitosan loaded AgS photochemical catalyst.
Embodiment 9
Present embodiment provides a kind of chitosan loaded SnS
2The preparation method of photochemical catalyst is to utilize photochemical method to prepare chitosan loaded SnS
2The method of photochemical catalyst, specifically undertaken by following step:
Take by weighing the 9g molecular weight respectively and be 650,000, deacetylation is that 91.5% shitosan and 12.883g tin acetate (36.3mmol) join in the acetum that the 100g mass concentration is 1.5wt%, compound concentration is the chitosan solution of 90g/L, stirs 3h down at 50 ℃ and obtains shitosan Sn
4+Complex solution; Dripping concentration under stirring condition in above-mentioned complex solution is the NaOH solution of 0.15mol/L, adjusts near the pH value of solution value to 7.3, with the shitosan Sn that separates out
4+Composition particles filter, wash shitosan Sn
4+The complex particle; Above-mentioned complex particle is scattered in the 200g deionized water, adds 1.345g ATS (Ammonium thiosulphate) (9.075mmol) simultaneously, stirring and dissolving obtains chitosan loaded SnS
2Precursor liquid; The precursor aqueous solution that obtains is placed irradiation 36h under the uviol lamp, and (irradiation wavelength 365nm, irradiation intensity are 2.1mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is 70 ℃ of vacuum drying, and obtaining product is chitosan loaded SnS
2Photochemical catalyst.
Embodiment 10
Present embodiment provides a kind of chitosan loaded Fe
2S
3The preparation method of photochemical catalyst is to utilize photochemical method to prepare chitosan loaded Fe
2S
3The method of photochemical catalyst, specifically undertaken by following step:
Take by weighing the 10g molecular weight respectively and be 250,000, deacetylation is that 93.5% shitosan and 5.566g Iron trichloride hexahydrate (20.6mmol) join in the acetum that the 200g mass concentration is 1.5wt%, compound concentration is the chitosan solution of 50g/L, stirs 4h down at 40 ℃ and obtains shitosan Fe
3+Complex solution; Dripping concentration under stirring condition in above-mentioned complex solution is the NaOH solution of 0.4mol/L, adjusts near the pH value of solution value to 7.3, with the shitosan Fe that separates out
3+Composition particles filter, wash shitosan Fe
3+The complex particle; Above-mentioned complex particle is scattered in the 100g deionized water, adds 1.155g five hydration potassium thiosulfates (4.12mmol) simultaneously, stirring and dissolving obtains chitosan loaded Fe
2S
3Precursor liquid; The precursor aqueous solution that obtains is placed irradiation 24h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 1.6mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is 60 ℃ of vacuum drying, and obtaining product is chitosan loaded Fe
2S
3Photochemical catalyst.
The photochemical catalyst that makes below by the commercial P-25 photochemical catalyst of selecting German Deggusa company to produce and various embodiments of the present invention carries out the photocatalysis contrast experiment, and is specific as follows:
Photocatalysis experiment: urge agent to take by weighing 0.05g respectively P-25 and the prepared light of the various embodiments described above, the concentration that is scattered in 200mi is to form dispersion liquid in the methyl orange aqueous solution of 10mg/L, under room temperature, place dark place to have children outside the state plan 10min dispersion liquid, after stirring the 10min clock then, change in the English Photoreactor of column, respectively with the mercury lamp of 300W as ultraviolet source, with the 500W xenon lamp as visible light source, under magnetic agitation with the degradation rate of irradiation 1h as final degradation rate.If under natural daylight, carry out degradation reaction, then will be ultrasonic and stir after dispersion liquid pour in the 250ml beaker, under magnetic agitation, beaker placed under the sunshine direct sample mensuration degradation rate behind the irradiation 1h.The prepared chitosan loaded metal sulfide photocatalytic degradation of each embodiment performance sees Table 1:
Table 1: photocatalyst for degrading methyl orange performance (degradation rate/hour)
| Ultraviolet light | Visible light | Natural daylight | |
| ??P25 | ??99.3 | ??71.2 | ??53.1 |
| Embodiment 1 | ??97.8 | ??86.1 | ??76.3 |
| Embodiment 2 | ??96.5 | ??78.5 | ??65.4 |
| |
??96.2 | ??85.3 | ??78.5 |
| Embodiment 4 | ??98.8 | ??76.2 | ??62.4 |
| Embodiment 5 | ??97.3 | ??85.6 | ??72.6 |
| Embodiment 6 | ??98.1 | ??84.2 | ??77.5 |
| Embodiment 7 | ??98.5 | ??87.1 | ??78.2 |
| Embodiment 8 | ??97.9 | ??81.7 | ??71.8 |
| Embodiment 9 | ??99.1 | ??79.5 | ??69.3 |
| Embodiment 10 | ??98.4 | ??86.2 | ??73.4 |
Annotate: degradation rate (%)=(methyl orange concentration behind the 1-irradiation/predose methyl orange concentration) * 100
As seen from table, the prepared photochemical catalyst of various embodiments of the present invention can be at natural daylight, ultraviolet, and under the visible light degraded methyl orange is all had higher photocatalytic activity, be highly active photochemical catalyst.
In sum, the embodiment of the invention utilizes the photochemistry synthetic technology that a kind of method for preparing the chitosan loaded metal sulfide photocatalyst product is provided, this method technology is simple, the reaction condition gentleness, is easy to control, cleaning and workable, the advantage that cost is low.
The above; only be the preferable specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; the present invention is not caused any restriction because of the succession of each embodiment yet; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (9)
1. the photochemical method for preparation of a chitosan loaded metal sulfide photocatalyst is characterized in that may further comprise the steps:
(1) preparation chitosan metal ion coordination compound particulate: the shitosan and the metal ion that will be under the solution state form complex, using basic solution adjustment complex solution pH value separates out complex to neutrality under stirring, and washing and filtering makes the chitosan metal ion coordination compound particulate;
(2) preparation precursor liquid: the described chitosan metal ion coordination compound microparticulate that will make is mixed with the precursor liquid of chitosan loaded metal sulfide in the aqueous solution that contains the sulphur source;
(3) photochemical reaction: the precursor liquid of the chitosan loaded metal sulfide that makes is positioned under the ultraviolet source stirring reaction 2 ~ 48 hours;
(4) post processing of photochemical catalyst: after photochemical reaction finishes, after filtration, promptly get chitosan loaded metal sulfide photocatalyst after the washing, drying.
2. preparation method according to claim 1 is characterized in that:
Step (1) is specially:
Acidic aqueous solution with 0.2～5wt% is a solvent, is solute with slaine, shitosan, and the preparation chitosan concentration is the shitosan acid solution of 5～100g/L, stirs under 30～80 ℃ temperature 1～5 hour, makes chitosan metal ion coordination compound solution;
Dripping concentration in the above-mentioned chitosan metal ion coordination compound solution that makes is the NaOH alkaline solution of 0.1 ~ 0.5mol/L, stir, adjust system pH to neutrality chitosan metal ion coordination compound is separated out, filter, wash, obtain the chitosan metal ion coordination compound particulate;
Step (2) is specially:
With the above-mentioned chitosan metal ion coordination compound microparticulate that makes in deionized water, the consumption of deionized water is 10～100 times of chitosan metal ion coordination compound particulate weight, add the sulphur source then, the ratio of the quality of metal is (0.1～10) in sulphur source and the chitosan metal ion coordination compound particulate: 1, stirring and dissolving under room temperature obtains the precursor liquid of chitosan loaded metal sulfide;
Step (3) is specially:
The above-mentioned chitosan loaded metal sulfide precursor liquid that makes is positioned under the ultraviolet source that wavelength is 254 ~ 365nm, and irradiation intensity is 0.02～3.0mW/cm
2, stirring reaction 2 ~ 48 hours.
3. preparation method according to claim 2 is characterized in that, the described drying of step (4) is 50～80 ℃ of vacuum constant temperature dryings.
4. preparation method according to claim 2 is characterized in that, described acid solution is acetum, salpeter solution, hydrochloric acid solution or citric acid solution.
5. preparation method according to claim 2 is characterized in that, described slaine is one or more in chloride, acetate, the nitrate.
6. according to each described preparation method of claim 1 to 5, it is characterized in that described metal ion is one or more in copper, cobalt, nickel, cadmium, chromium, zinc, lead, silver, tin or the iron ion, its total consumption is for pressing every gram shitosan 0.5～5mmol.
7. according to each described preparation method of claim 1 to 5, it is characterized in that the viscosity average molecular weigh of described shitosan is 100,000～800,000, the deacetylation of described shitosan is 75%～95%.
8. according to each described preparation method of claim 1 to 5, it is characterized in that described sulphur source is the solubility thiosulfate.
9. preparation method according to claim 8 is characterized in that, described thiosulfate is sodium thiosulfate, potassium thiosulfate or ATS (Ammonium thiosulphate).
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| CN101899701A (en) * | 2010-07-19 | 2010-12-01 | 西南交通大学 | Method for preparing composite material of copper sulfide and titanium dioxide nano-tube |
| CN105862171A (en) * | 2016-04-07 | 2016-08-17 | 中原工学院 | Preparation method of cuprous sulfide/carboxylation chitosan/glass fiber composite conductive fiber |
| CN106556623A (en) * | 2016-08-15 | 2017-04-05 | 华南师范大学 | A kind of gas-liquid interface processing method of semiconductor gas sensor |
| CN107349965A (en) * | 2017-06-16 | 2017-11-17 | 中国科学院上海硅酸盐研究所 | A kind of adsorption photochemical catalysis hydrogel material and its application in the cooperative photocatalysis sewage production hydrogen of heavy metallic poison is reversed |
| CN110586133A (en) * | 2019-09-11 | 2019-12-20 | 天津大学 | Niobium acid-based sulfide composite material and preparation method thereof |
| CN110560014A (en) * | 2019-09-18 | 2019-12-13 | 成都理工大学 | Preparation method and application of ion-imprinted chitosan/cadmium sulfide composite material |
| CN111165235A (en) * | 2019-12-31 | 2020-05-19 | 赵梓权 | Photocatalytic spray type insect-proof antibacterial fresh-keeping liquid and preparation method thereof |
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