CN104588101A - Heterogeneous photocatalytic material with pH responsiveness as well as preparation method and application thereof - Google Patents
Heterogeneous photocatalytic material with pH responsiveness as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a catalyst, in particular to a heterogeneous photocatalytic material with pH responsiveness as well as a preparation method and application thereof. The preparation method comprises the following steps: taking tetra (4-carboxyl-phenyl) metalloporphyrin as a catalytic core and covalently grafting on acrylic acid modified chitosan in the form of an amido bond to prepare acrylic acid modified chitosan grafted metalloporphyrin. The prepared acrylic acid modified chitosan grafted metalloporphyrin heterogeneous photocatalytic material is applied to photocatalytic acid dye wastewater. The catalytic material provided by the invention is a heterogeneous catalyst, has high catalytic efficiency and has the advantages of reducing the production cost and being easy to separate, recover and recycle. Through adjusting the pH value, the pH of the wastewater is neutralized and the separation, recovery and recycle of the catalyst material are realized.
Description
Technical field
The present invention relates to the preparation method and application of catalyst, particularly a kind of there is pH response homogeneous photochemical catalysis material and preparation method and application thereof.
Background technology
China is the country of a serious water shortage, and freshwater resources only have an appointment 2200 cubic metres per capita, is one of 13 countries that water resource is the poorest per capita in the whole world.But while scientific and technological progress, industry high speed development, the water resource quality of China still constantly declines, and water environment is continuous worsening, the social sustainable development of serious threat.Developing rapidly particularly along with textile dyestuff industry, quantity and the kind of dyestuff increase day by day, dyeing waste water, and especially acid dyeing waste water, has become one of major polluting sources of water system environment.The same with common dyeing waste water, acid dyeing waste water also has a lot of reluctant organic matter and higher colourity, and presents acidity, causes high risks to ecological environment and the daily drinking water of resident.Therefore, Acid Dye Wastewater pollution control is in widespread attention as the important topic of field of Environment Protection.
At present, for the method that dyestuff is removed, physisorphtion, bioanalysis, advanced oxidation processes etc. are mainly comprised.Wherein, advanced oxidation processes, particularly photocatalysis oxidation technique, demonstrate good application prospect in dye discoloration is administered.This technology utilizes strong oxidizer, as Fenton, O
3, H
2o
2the hydroxyl free radical (HO) Deng generation under light radiation with Strong oxdiative ability processes waste water, impels a series of organic pollution in sewage to be progressively degraded to Small molecular, finally generates CO
2, H
2o and other ions.
In recent years, the concern of porphyrin and metal porphyrins extremely researcher in photocatalysis treatment toxic organic pollutant.Owing to having more liquid large pi-conjugated structure, under illumination condition, usually can there is the transfer of photoinduced electron in porphyrin.Metalloporphyrin is that metal ion enters the metal complex formed after in porphyrin ring.Generally, the central metal of metalloporphyrin has higher oxidation state, Chang Zuowei electron acceptor in photoelectricity transfer process, and porphyrin part is then as the donor of photoinduced electron.Under illumination condition, photo induced electron transfer to metal center, causes quantity of photogenerated charge to be separated by porphyrin part, creates the electron-hole pair with catalytic oxidative and reproducibility of similar semiconductor, imparts the photocatalysis property of metalloporphyrin.But using metalloporphyrin as photochemical catalyst, its disadvantage is difficult to separation and recovery and recycling from reaction system, not only easily cause waste and high production cost, also can produce secondary pollution to environment water.In addition, metalloporphyrin be easy in course of reaction assemble and oxidized.These all limit the practical application of metalloporphyrin.
Under this background, increasing researcher is devoted to research and how protects metalloporphyrin, is wherein that metalloporphyrin carrier prepares solid supported type metal porphyrin for study hotspot with boiomacromolecule.Shitosan (poly-(Isosorbide-5-Nitrae)-2-amino-2-deoxidation-β-D glucan) has the character of many uniquenesses such as biocompatibility, biologically active, hydrophily, adsorptivity and reproducibility because of it, become one of catalyst ideal carrier.The photocatalysis dye degrades research of shitosan supported metalloporphyrin catalyst rarely has report, but the existing many reports of the application in the oxidation of other catalytic organisms, as " chitosan graft four (p-carboxyl phenyl) metalloporphyrin preparation method and application thereof " patent that publication number is CN103554302A, disclosed (comprise four (p-carboxyl phenyl) Cob altporphyrin with four (p-carboxyl phenyl) metalloporphyrin, four (p-carboxyl phenyl) manganoporphyrin and four (p-carboxyl phenyl) ferriporphyrin) be core catalyst, its amidatioon is grafted on shitosan and obtain chitosan graft four (p-carboxyl phenyl) metalloporphyrin, and be applied to Oxidation Ethylbenzene, produce in acetophenone and DL-1-benzyl carbinol.In this patent, compared with simple metalloporphyrin, metalloporphyrin can be made to be combined with shitosan very securely with amidatioon grafting pattern, and in catalytic oxidation process, difficult drop-off or oxidized and lose catalytic activity, overcome the metalloporphyrin consumption existed in current ethylbenzene oxidation technique more, the reaction time is oversize, pollute the deficiencies such as large.But make its degree of crystallinity high owing to there is a large amount of hydrogen bond between chitosan molecule, dissolubility is in organic solvent limited, and the oxidation reaction of ethylbenzene of chitosan graft four (p-carboxyl phenyl) catalysis of metalloporphyrin is heterogeneous catalytic reaction.And the oxidation reaction of ethylbenzene of simple catalysis of metalloporphyrin is homogeneous reaction.Although heterogeneous catalysis makes catalyst be easier to reclaim, disclosed in this patent " after each stopping catalytic reaction; after waiting for that this catalysis material is separated with reactant mixture natural subsidence; filter; with ethanol washing, then natural air drying, reclaims this catalysis material ", improve the recycling rate of waterused of metalloporphyrin, but heterogeneous catalysis organic matter degradation efficiency is still be not as high as homogeneous catalyst.Therefore, as how application purpose is starting point, prepare combining efficient and be easy to reclaim homogeneous catalysis material be still the problem needing solution at present badly.
Summary of the invention
The present invention is directed to deficiency of the prior art, provide a kind of and there is the chitosan graft metalloporphyrin homogeneous photochemical catalysis material of pH response and the application in Acid Dye Wastewater process thereof.
With four (4-carboxyl phenyl) metalloporphyrin (comprising four (4-carboxyl phenyl) nickel-porphyrin and four (4-carboxyl phenyl) vanadium porphyrin) for catalytic core, with the mode covalence graft of amido link on acrylic acid modified shitosan, prepare acrylic acid modified chitosan graft metalloporphyrin.
Technical scheme of the present invention is:
Have a preparation method for the homogeneous photochemical catalysis material of pH response, comprise the steps, following component mixes according to parts by weight:
Step 1: first add anhydrous ethanol solvent 0.7 part, adds four (p-carboxyl phenyl) metalloporphyrin 0.0008 ~ 0.004 part, after fully dissolving, add ultra-pure water 100 parts, then, add 1.049 ~ 3.147 parts, glacial acetic acid, stir, obtain a kind of mixed solution;
Step 2: add 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) 1 ~ 2 part and N-hydroxy-succinamide (NHS) 2 ~ 5 parts in the mixed solution obtained to step 1 under stirring, reaction 20 ~ 60min, obtains a kind of mixed solution;
Step 3: add 1 ~ 5 part of acrylic acid modified shitosan in the mixed solution obtained to step 2 under stirring, reaction 20 ~ 60min, obtains a kind of mixed solution;
Step 4: mixed solution step 3 obtained is placed in bag filter, and bag filter is placed in ultra-pure water, dialysis 2 ~ 3d;
Step 5: the solution in bag filter step 4 obtained, is placed in-80 DEG C of refrigerators, after snap frozen, puts into vacuum freeze dryer, vacuum drying 2 ~ 3d, obtained acrylic acid modified chitosan graft metalloporphyrin.
Preferably, four described in step 1 (p-carboxyl phenyl) metalloporphyrin is four (4-carboxyl phenyl) nickel-porphyrin and four (4-carboxyl phenyl) vanadium porphyrin.
On the basis of above scheme, the preparation method of the acrylic acid modified shitosan described in step 3, concrete steps are as follows:
1. add ultra-pure water 100 parts, then, add 1.049 ~ 3.147 parts, glacial acetic acid, stir, obtain acetum;
2. add 1 ~ 5 part of Chitosan powder in the acetum 1. obtained to step under stirring, stirred overnight is even, obtains shitosan colloidal solution;
3. under argon shield, slowly dropped to by 1.103 ~ 5.513 parts of acrylic acid in the shitosan colloidal solution that 2. step obtain, 50 DEG C are at the uniform velocity stirred, and reaction 48 ~ 72h, obtains a kind of mixed solution;
4. the mixed solution that 3. step obtains is placed in bag filter, and bag filter is placed in ultra-pure water, dialysis 3 ~ 4d;
5. the solution in bag filter step 4. obtained, is placed in-80 DEG C of refrigerators, after snap frozen, puts into vacuum freeze dryer, vacuum drying 2 ~ 3d, obtains the acrylic acid modified shitosan of white sponge.
Preferably, the bag filter molecular cut off described in step 4 is 5000.
Another object of the present invention is acrylic acid modified chitosan graft metalloporphyrin homogeneous photochemical catalysis material prepared by open a kind of above-mentioned preparation method.
The present invention's the 3rd object is the openly a kind of described application of acrylic acid modified chitosan graft metalloporphyrin homogeneous photochemical catalysis material in photocatalysis Acid Dye Wastewater.
Preferably, application conditions is: be 1 ~ 6 Acid Dye Wastewater by 100ml pH, add in cold-trap, add the acrylic acid modified chitosan graft metalloporphyrin described in 0.1 ~ 1mg and 100 ~ 200 μ l 30% hydrogen peroxide again, mixing speed controls at 500 ~ 1000r/min, and 50 ~ 60min is stirred in darkroom; Again with 500W Halogen lamp LED vertical irradiation cold-trap, control the wavelength >450nm of incident light, optical power density controls at 40 ~ 60mW/cm
2, carry out light-catalyzed reaction, reaction temperature controls at 25 DEG C, and the reaction time controls at 2 ~ 4h; After having reacted, regulate reaction system pH to neutral with 0.1mol/L sodium hydroxide solution, filtering recovering catalyst.
The invention has the beneficial effects as follows:
(1) catalysis material of the present invention is homogeneous catalyst, has efficient catalytic efficiency, and is easy to separation and recovery and recycling
Because acrylic acid modified shitosan itself has pH response, namely in acid condition, for water-soluble; And in neutral conditions, can separate out from water.Therefore, when acrylic acid modified chitosan graft metalloporphyrin is applied to Acid Dye Wastewater process, acrylic acid modified chitosan graft metalloporphyrin is dissolved in dye solution, presents homogeneous catalysis, ensure that catalytic degradation effect.After dyestuff is completely degraded, regulate reaction system pH to neutrality, acrylic acid modified chitosan graft metalloporphyrin is separated out from system, after natural subsidence or centrifugal treating, just can realize separation and recovery and the recycling of catalyst.
(2) metalloporphyrin is by immobilized on acrylic acid modified shitosan, effectively prevents self aggregation and oxidized.After metalloporphyrin is grafted to acrylic acid modified shitosan, is homogeneous catalyst in Acid Dye Wastewater process, ensure that efficient catalytic efficiency, and there is pH response simultaneously, be convenient to separation and recovery and recycling, avoid cost waste and secondary pollution.
(3) preparation feedback of acrylic acid modified chitosan graft metalloporphyrin is in aqueous phase homogeneous reaction, substantially increases reaction efficiency, reduces production cost.
(4) in acid dyes photocatalytic applications, by adjust ph, not only make wastewater pH recover neutral, and achieve separation and recovery and the recycling of catalysis material.
Accompanying drawing explanation
Accompanying drawing 1 is the relation between the turbidity of the catalysis material aqueous solution prepared by the specific embodiment of the invention 1 and pH value;
Accompanying drawing 2 is catalysis material photocatalytic activity curve map prepared by the specific embodiment of the invention 1;
Accompanying drawing 3 is the relation that the present invention specifically implements between the turbidity of the catalysis material aqueous solution of 2 preparations and pH value;
Accompanying drawing 4 is catalysis material photocatalytic activity curve map prepared by the specific embodiment of the invention 2.
Detailed description of the invention
The specific embodiment of the present invention is as follows:
Embodiment 1:
1, the preparation (1 gram/every part) of modification of chitosan grafting four (4-carboxyl phenyl) nickel-porphyrin
In reaction vessel, add ultra-pure water 100 parts, 3.147 parts, glacial acetic acid, 2.5 parts of Chitosan powder, after stirred overnight is even, under argon shield, add 1.986 parts of acrylic acid wherein, 50 DEG C are at the uniform velocity stirred, reaction 72h.Gained mixed solution is placed in bag filter (molecular cut off is 5000), dialysis 3d.Again by the solution in bag filter, vacuum freeze drying 2d, obtains acrylic acid modified shitosan.
Then, in reaction vessel, add anhydrous ethanol solvent 0.7 part, add four (p-carboxyl phenyl) nickel-porphyrin 0.0008 part, after abundant dissolving, add ultra-pure water 100 parts, 3.147 parts, glacial acetic acid, EDC 1 part, NHS 2 parts, stirs, after reaction 40min, add acrylic acid modified shitosan 1 part, reaction 40min.Gained mixed solution is placed in bag filter (molecular cut off is 5000), dialysis 3d.Again by the solution in bag filter, vacuum freeze drying 2d, obtains acrylic acid modified chitosan graft four (p-carboxyl phenyl) nickel-porphyrin.
2, the application of modification of chitosan grafting four (4-carboxyl phenyl) nickel-porphyrin in photocatalysis Acid Dye Wastewater
Application conditions is: be 1 ~ 6 Acid Dye Wastewater by 100ml pH, add in cold-trap, add the acrylic acid modified chitosan graft metalloporphyrin described in 0.1 ~ 1mg and 100 ~ 200 μ l 30% hydrogen peroxide again, mixing speed controls at 500 ~ 1000r/min, and 50 ~ 60min is stirred in darkroom; Again with 500W Halogen lamp LED vertical irradiation cold-trap, control the wavelength >450nm of incident light, optical power density controls at 40 ~ 60mW/cm
2, carry out light-catalyzed reaction, reaction temperature controls at 25 DEG C, and the reaction time controls at 2 ~ 4h; After having reacted, regulate reaction system pH to neutral with 0.1mol/L sodium hydroxide solution, filtering recovering catalyst.
For pH response and the photocatalysis effect of the present invention's acrylic acid modified chitosan graft four (p-carboxyl phenyl) nickel-porphyrin are described, the applicant has done a large amount of experiments, acrylic acid modified chitosan graft four (p-carboxyl phenyl) the nickel-porphyrin pH response adopting embodiment 1 to prepare and photocatalysis experiment, experimental result is as follows:
(1) pH response
Use ultraviolet-visible spectrophotometer, within the scope of pH2-11, analyze the relation between the turbidity (representing with light transmittance) of acrylic acid modified chitosan graft four (p-carboxyl phenyl) the nickel-porphyrin aqueous solution and pH value.
As shown in Figure 1, under the acid condition of pH<6, the light transmittance of acrylic acid modified chitosan graft four (p-carboxyl phenyl) the nickel-porphyrin aqueous solution almost reaches 100% to result, illustrates that now its dissolubility is very good.And when pH is increased in the scope of 6.5-7.5, light transmittance is before this along with the increase of pH significantly reduces, and when about pH=6.9 reaches minimum light transmittance, subsequently, the continuation increase of pH makes light transmittance become again increasing.As pH>7.5, light transmittance is basic fair with light transmittance during pH<6.This illustrates, as pH>6.5, the dissolubility of acrylic acid modified chitosan graft four (p-carboxyl phenyl) nickel-porphyrin sharply reduces.When about pH=6.9 reaches minimal solubility.And when pH be increased to be greater than 6.9 time, dissolubility increases fast.As pH>7.5, its dissolubility is restored substantially.Therefore, when with acrylic acid modified chitosan graft four (p-carboxyl phenyl) nickel-porphyrin as photocatalyst treatment Acid Dye Wastewater time, because this catalyst has extraordinary water-soluble under the acid condition of pH<6, can ensure that light-catalyzed reaction is carried out in homogeneous phase, guarantee finally to obtain higher photocatalysis efficiency.And, after light-catalyzed reaction terminates, by regulation system pH to neutral, the separation and recovery of acrylic acid modified chitosan graft catalysis of metalloporphyrin agent can be realized and reuse, and the pH neutralisation treatment of simultaneously Acid Dye Wastewater, make its pH value reach the standard of waste discharge.
(2) photocatalysis experiment
Added in cold-trap by 100ml acid red (its pH is 4), then add the acrylic acid modified chitosan graft metalloporphyrin of 1mg and 200 μ l 30% hydrogen peroxide, mixing speed controls at 900r/min, and 60min is stirred in darkroom.Again with 500W Halogen lamp LED vertical irradiation cold-trap, control the wavelength >450nm of incident light, optical power density controls at 45mW/cm
2, carry out light-catalyzed reaction, reaction temperature controls at 25 DEG C, and the reaction time controls at 4h.Every sampling in 30 minutes, by the absorbance of ultraviolet-visible spectrophotometer working sample at wavelength 515nm place.According to following formula, calculate the degradation rate of dyestuff.
D＝(A
0-A)/A
0×100％
In formula, D represents degradation rate, A
0represent the initial absorbance at 515nm place, A represents the absorbance at random time point 515nm place.
As shown in Figure 2, along with the increase in reaction time, dye degrades rate increases gradually, and when reaching 4h when reacted, the dyestuff of 83.7% is degraded.
After light-catalyzed reaction experiment terminates, close light source, regulate reaction system pH to neutral, filter with 0.1mol/L sodium hydroxide solution, with milli-Q water, then natural air drying, reclaims catalysis material.Then under the same reaction conditions for acid red dye degraded, such recycling can reach 3 times, and each degradation rate is respectively: 81.7%, 80.2%, 77.9%.
Embodiment 2
1, the preparation (1 gram/every part) of modification of chitosan grafting four (4-carboxyl phenyl) vanadium porphyrin
In reaction vessel, add ultra-pure water 100 parts, 2.098 parts, glacial acetic acid, 2 parts of Chitosan powder, after stirred overnight is even, under argon shield, add 1.589 parts of acrylic acid wherein, 50 DEG C are at the uniform velocity stirred, reaction 72h.Gained mixed solution is placed in bag filter (molecular cut off is 5000), dialysis 3d.Again by the solution in bag filter, vacuum freeze drying 2d, obtains acrylic acid modified shitosan.
Then, in reaction vessel, add anhydrous ethanol solvent 0.7 part, add four (p-carboxyl phenyl) vanadium porphyrin 0.0016 part, after abundant dissolving, add ultra-pure water 100 parts, 2.098 parts, glacial acetic acid, EDC 2 parts, NHS 5 parts, stirs, after reaction 30min, add acrylic acid modified shitosan 2 parts, reaction 50min.Gained mixed solution is placed in bag filter (molecular cut off is 5000), dialysis 3d.Again by the solution in bag filter, vacuum freeze drying 3d, obtains acrylic acid modified chitosan graft four (p-carboxyl phenyl) vanadium porphyrin.
2, the application of modification of chitosan grafting four (4-carboxyl phenyl) vanadium porphyrin in photocatalysis Acid Dye Wastewater
Application conditions is: be 1 ~ 6 Acid Dye Wastewater by 100ml pH, add in cold-trap, add the acrylic acid modified chitosan graft metalloporphyrin described in 0.1 ~ 1mg and 100 ~ 200 μ l 30% hydrogen peroxide again, mixing speed controls at 500 ~ 1000r/min, and 50 ~ 60min is stirred in darkroom; Again with 500W Halogen lamp LED vertical irradiation cold-trap, control the wavelength >450nm of incident light, optical power density controls at 40 ~ 60mW/cm
2, carry out light-catalyzed reaction, reaction temperature controls at 25 DEG C, and the reaction time controls at 2 ~ 4h; After having reacted, regulate reaction system pH to neutral with 0.1mol/L sodium hydroxide solution, filtering recovering catalyst.
For pH response and the photocatalysis effect of the present invention's acrylic acid modified chitosan graft four (p-carboxyl phenyl) vanadium porphyrin are described, the applicant has done a large amount of experiments, acrylic acid modified chitosan graft four (p-carboxyl phenyl) the vanadium porphyrin pH response adopting embodiment 1 to prepare and photocatalysis experiment, experimental result is as follows:
(1) pH response
Use ultraviolet-visible spectrophotometer, within the scope of pH2-11, analyze the relation between the turbidity (representing with light transmittance) of acrylic acid modified chitosan graft four (p-carboxyl phenyl) the vanadium porphyrin aqueous solution and pH value.
As shown in Figure 3, acrylic acid modified chitosan graft four (p-carboxyl phenyl) vanadium porphyrin has similar pH response to acrylic acid modified chitosan graft four (p-carboxyl phenyl) nickel-porphyrin to result.As pH<6, the light transmittance of acrylic acid modified chitosan graft four (p-carboxyl phenyl) the vanadium porphyrin aqueous solution almost reaches 100%; As pH>6, light transmittance significantly reduces along with the increase of pH, and when about pH=6.7 reaches minimum light transmittance, subsequently, the continuation increase of pH makes light transmittance become again increasing.As pH>8.5, light transmittance is basic fair with light transmittance during pH<6.
(2) photocatalysis experiment
Added in cold-trap by 100ml acid red (its pH is 4), then add the acrylic acid modified chitosan graft metalloporphyrin of 1mg and 200 μ l 30% hydrogen peroxide, mixing speed controls at 700r/min, and 60min is stirred in darkroom.Again with 500W Halogen lamp LED vertical irradiation cold-trap, control the wavelength >450nm of incident light, optical power density controls at 45mW/cm
2, carry out light-catalyzed reaction, reaction temperature controls at 25 DEG C, and the reaction time controls at 4h.Every sampling in 30 minutes, by the absorbance of ultraviolet-visible spectrophotometer working sample at wavelength 515nm place, and calculate the degradation rate of dyestuff.
As shown in Figure 4, along with the increase in reaction time, dye degrades rate increases gradually, and when reaching 4h when reacted, the dyestuff of 91.2% is degraded.
After light-catalyzed reaction experiment terminates, close light source, regulate reaction system pH to neutral, filter with 0.1mol/L sodium hydroxide solution, with milli-Q water, then natural air drying, reclaims catalysis material.Then under the same reaction conditions for acid red dye degraded, such recycling can reach 3 times, and each degradation rate is respectively: 91.2%, 88.5%, 79.1%.
The present embodiment is only and further illustrates the present invention, not to inventing any restriction made, all the present invention in fact the simple modification made of content and improve all still belong to technical solution of the present invention protection domain within.
Claims (7)
1. have a preparation method for the homogeneous photochemical catalysis material of pH response, it is characterized in that, comprise the steps, following component mixes according to parts by weight:
Step 1: first add anhydrous ethanol solvent 0.7 part, adds four (p-carboxyl phenyl) metalloporphyrin 0.0008 ~ 0.004 part, after fully dissolving, add ultra-pure water 100 parts, then, add 1.049 ~ 3.147 parts, glacial acetic acid, stir, obtain a kind of mixed solution;
Step 2: add 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride 1 ~ 2 part and N-hydroxy-succinamide 2 ~ 5 parts in the mixed solution obtained to step 1 under stirring, reaction 20 ~ 60min, obtains a kind of mixed solution;
Step 3: add 1 ~ 5 part of acrylic acid modified shitosan in the mixed solution obtained to step 2 under stirring, reaction 20 ~ 60min, obtains a kind of mixed solution;
Step 4: mixed solution step 3 obtained is placed in bag filter, and bag filter is placed in ultra-pure water, dialysis 2 ~ 3d;
Step 5: the solution in bag filter step 4 obtained, is placed in-80 DEG C of refrigerators, after snap frozen, puts into vacuum freeze dryer, vacuum drying 2 ~ 3d, obtained acrylic acid modified chitosan graft metalloporphyrin.
2. the preparation method with the homogeneous photochemical catalysis material of pH response according to claim 1, it is characterized in that, four described in step 1 (p-carboxyl phenyl) metalloporphyrin is four (4-carboxyl phenyl) nickel-porphyrin and four (4-carboxyl phenyl) vanadium porphyrin.
3. the preparation method with the homogeneous photochemical catalysis material of pH response according to claim 1, is characterized in that, the preparation method of the acrylic acid modified shitosan described in step 3, and concrete steps are as follows:
1. add ultra-pure water 100 parts, then, add 1.049 ~ 3.147 parts, glacial acetic acid, stir, obtain acetum;
2. add 1 ~ 5 part of Chitosan powder in the acetum 1. obtained to step under stirring, stirred overnight is even, obtains shitosan colloidal solution;
3. under argon shield, slowly dropped to by 1.103 ~ 5.513 parts of acrylic acid in the shitosan colloidal solution that 2. step obtain, 50 DEG C are at the uniform velocity stirred, and reaction 48 ~ 72h, obtains a kind of mixed solution;
4. the mixed solution that 3. step obtains is placed in bag filter, and bag filter is placed in ultra-pure water, dialysis 3 ~ 4d;
5. the solution in bag filter step 4. obtained, is placed in-80 DEG C of refrigerators, after snap frozen, puts into vacuum freeze dryer, vacuum drying 2 ~ 3d, obtains the acrylic acid modified shitosan of white sponge.
4. the preparation method with the homogeneous photochemical catalysis material of pH response according to claim 1, is characterized in that, the bag filter molecular cut off described in step 4 is 5000.
5. the acrylic acid modified chitosan graft metalloporphyrin homogeneous photochemical catalysis material prepared of a preparation method according to claim 1.
6. the application of an acrylic acid modified chitosan graft metalloporphyrin homogeneous photochemical catalysis material according to claim 5 in photocatalysis Acid Dye Wastewater.
7. the application of acrylic acid modified chitosan graft metalloporphyrin homogeneous photochemical catalysis material according to claim 6 in photocatalysis Acid Dye Wastewater, it is characterized in that, application conditions is: be 1 ~ 6 Acid Dye Wastewater by 100ml pH, add in cold-trap, add the acrylic acid modified chitosan graft metalloporphyrin described in 0.1 ~ 1mg and 100 ~ 200 μ l 30% hydrogen peroxide again, mixing speed controls at 500 ~ 1000r/min, and 50 ~ 60min is stirred in darkroom; Again with 500W Halogen lamp LED vertical irradiation cold-trap, control the wavelength >450nm of incident light, optical power density controls at 40 ~ 60mW/cm
2, carry out light-catalyzed reaction, reaction temperature controls at 25 DEG C, and the reaction time controls at 2 ~ 4h; After having reacted, regulate reaction system pH to neutral with 0.1mol/L sodium hydroxide solution, filtering recovering catalyst.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503886A (en) * | 2015-12-09 | 2016-04-20 | 中国科学院长春光学精密机械与物理研究所 | Nanometer photosensitizer for molecular system near-infrared light triggering water splitting and preparation method of nanometer photosensitizer |
| CN108014850A (en) * | 2017-11-28 | 2018-05-11 | 清华大学 | A kind of preparation method and applications of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst |
| CN108097284A (en) * | 2017-12-18 | 2018-06-01 | 铜仁学院 | A kind of visible light catalytic decomposes water homogeneous catalyst and preparation method thereof |
| CN111514937A (en) * | 2020-05-13 | 2020-08-11 | 中国石油大学(华东) | Preparation method of porphyrin-based metal organic framework material sensitized oxide catalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004022841A1 (en) * | 2002-09-09 | 2004-03-18 | Jung-Eun Seo | Polymer article and method for manufacturing the same |
| CN1853784A (en) * | 2005-04-19 | 2006-11-01 | 中国科学院化学研究所 | Method for degrading organic pollutant by light catalyst and its special solid-phase light catalyst |
| CN102008980A (en) * | 2010-11-02 | 2011-04-13 | 浙江理工大学 | Metalloporphyrin-sensitized titanium dioxide photocatalyst and preparation method thereof |
| CN102380102A (en) * | 2011-11-02 | 2012-03-21 | 东华大学 | Method for preparing environment-responsive mesoporous silicon nanoparticles |
| CN102936297A (en) * | 2012-11-15 | 2013-02-20 | 广西大学 | Porous chitosan metal porphyrin composite and preparation method and application thereof |
| CN103127953A (en) * | 2013-01-28 | 2013-06-05 | 长春理工大学 | Thermosensitivity recyclable metalloporphyrin visible light degradation catalyst and preparation method thereof |
| CN103554302A (en) * | 2013-10-29 | 2014-02-05 | 广西大学 | Preparation method and application for chitosan-grafted quadri(p-carboxylphenyl) metalloporphyrin |
-
2015
- 2015-01-13 CN CN201510016734.3A patent/CN104588101B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004022841A1 (en) * | 2002-09-09 | 2004-03-18 | Jung-Eun Seo | Polymer article and method for manufacturing the same |
| CN1853784A (en) * | 2005-04-19 | 2006-11-01 | 中国科学院化学研究所 | Method for degrading organic pollutant by light catalyst and its special solid-phase light catalyst |
| CN102008980A (en) * | 2010-11-02 | 2011-04-13 | 浙江理工大学 | Metalloporphyrin-sensitized titanium dioxide photocatalyst and preparation method thereof |
| CN102380102A (en) * | 2011-11-02 | 2012-03-21 | 东华大学 | Method for preparing environment-responsive mesoporous silicon nanoparticles |
| CN102936297A (en) * | 2012-11-15 | 2013-02-20 | 广西大学 | Porous chitosan metal porphyrin composite and preparation method and application thereof |
| CN103127953A (en) * | 2013-01-28 | 2013-06-05 | 长春理工大学 | Thermosensitivity recyclable metalloporphyrin visible light degradation catalyst and preparation method thereof |
| CN103554302A (en) * | 2013-10-29 | 2014-02-05 | 广西大学 | Preparation method and application for chitosan-grafted quadri(p-carboxylphenyl) metalloporphyrin |
Non-Patent Citations (2)
| Title |
|---|
| HOSSEIN GHAFURI ET AL: "Synthesis, characterization and photocatalytic activity of Co(III) 5,10,15,20-tetrakis(carboxyphenyl)porphyrin-supported chitosan", 《THE 18TH INT. ELECTRON. CONF. SYNTH. ORG. CHEM.》 * |
| 许晓韡: "聚丙烯酸修饰壳聚糖纳米球锌卟啉结合体的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503886A (en) * | 2015-12-09 | 2016-04-20 | 中国科学院长春光学精密机械与物理研究所 | Nanometer photosensitizer for molecular system near-infrared light triggering water splitting and preparation method of nanometer photosensitizer |
| CN108014850A (en) * | 2017-11-28 | 2018-05-11 | 清华大学 | A kind of preparation method and applications of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst |
| CN108097284A (en) * | 2017-12-18 | 2018-06-01 | 铜仁学院 | A kind of visible light catalytic decomposes water homogeneous catalyst and preparation method thereof |
| CN111514937A (en) * | 2020-05-13 | 2020-08-11 | 中国石油大学(华东) | Preparation method of porphyrin-based metal organic framework material sensitized oxide catalyst |
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