CN102513078A - Preparation method of cobalt protoporphyrin sensitization titanium dioxide hollow microsphere photochemical catalyst - Google Patents
Preparation method of cobalt protoporphyrin sensitization titanium dioxide hollow microsphere photochemical catalyst Download PDFInfo
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- CN102513078A CN102513078A CN2011103880014A CN201110388001A CN102513078A CN 102513078 A CN102513078 A CN 102513078A CN 2011103880014 A CN2011103880014 A CN 2011103880014A CN 201110388001 A CN201110388001 A CN 201110388001A CN 102513078 A CN102513078 A CN 102513078A
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Abstract
The invention discloses a preparation method of a cobalt protoporphyrin sensitization titanium dioxide hollow microsphere photochemical catalyst. The preparation method comprises the following steps: preparing a titanium dioxide hollow microsphere; fully mixing the titanium dioxide hollow microsphere and organic solvent dissolved with cobalt protoporphyrin, wherein the mass ratio of the cobalt protoporphyrin to the titanium dioxide hollow microsphere is 0.05-0.5:100; heating and refluxing the mixture for 2 hours-5 hours in a stirring state, wherein the temperature of heating and refluxing is 80 DEG C-100 DEG C; and drying at the temperature of 60 DEG C-80 DEG C to obtain the photochemical catalyst. The preparation method has simple steps and is easy to realize, and the prepared photochemical catalyst has good photocatalytic performance.
Description
Technical field
The invention belongs to photochemical catalyst preparation method technical field, be specifically related to a kind of preparation method of cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst.
Background technology
Along with the continuous quickening of process of industrialization and the expansion of human lives's scope, water pollution problem is serious day by day, and the discharging of great amount of wastewater makes people's living environment quality go from bad to worse.Wherein, waste water from dyestuff can't natural degradation because color is dark, and concentration is big, becomes a great problem of water treatment field.As the photocatalysis method of one of oxidation technology, be widely used in solving the waste water from dyestuff pollution problem.
In numerous catalysis materials; The anatase titania powder because have that photocatalytic activity height, fast light corrosivity are strong, good stability, environmental friendliness, relative low price, to advantages such as human non-toxic, become application the most extensively and one of the most deep catalysis material of research.But the band gap width of anatase titania powder is 3.2eV, can only absorbing wavelength less than the ultraviolet light of 387nm, to the utilization rate only about 4% of solar energy.At present,, concentrate on mostly on the performance improvement that titanium dioxide is carried out, to widen its response range sunshine to the improvement of photochemical catalyst.The photocatalysis performance that improves titanium dioxide mainly contains: effect coupling and modifying and decorating.Modifying and decorating is method commonly used, comprises that metallic ion-doping modification, noble metal loading modification, semiconductor are composite modified, organic dye sensitized modification etc.Wherein organic dye sensitized modification is to extend one of simple and effective way of titanium dioxide excitation wavelength range.But in the present research, still exist after the dye sensitization titanium dioxide to the absorbability of light with utilize the not high problem of ability.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst, step is simple, realizes that easily the photocatalysis performance of the photochemical catalyst of preparation is good.
The technical scheme that the present invention adopted is that a kind of preparation method of cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst is characterized in that concrete steps are following:
Step 1, preparation titanic oxide hollow microballoon;
Step 2, the titanic oxide hollow microballoon of step 1 preparation and the organic solvent that is dissolved with the cobalt porphyrin are fully mixed; Wherein, The mass ratio of said cobalt porphyrin and titanic oxide hollow microballoon is 0.05～0.5: 100, and with mixture reflux 2h～5h under stirring, the reflux temperature is 80 ℃～100 ℃; Under 60 ℃～80 ℃ temperature, dry again, promptly get;
Wherein, the structural formula of cobalt porphyrin is:
Organic solvent is ethanol, N-, dinethylformamide or chloroform.
Wherein, the concrete steps of step 1 are:
Step 1.1, glucose placed the agitated reactor that deionized water is housed; Isothermal reaction 11h～13h under 120 ℃～150 ℃ temperature after the room temperature cooling, takes out sediment; Use the mixed solution flushing of deionized water and absolute ethyl alcohol; Filter, the solid matter that obtains is dry under 70 ℃～90 ℃ temperature, promptly obtain the carbon ball;
Step 1.2, the carbon ball that step 1.1 is obtained place the agitated reactor that titanium sulfate aqueous solution is housed, and isothermal reaction 22h～26h under 120 ℃～150 ℃ temperature is after the room temperature cooling; Take out sediment; Use the mixed solution flushing of deionized water and absolute ethyl alcohol, filter, with the solid matter that obtains in drying under 70 ℃～90 ℃ temperature; At temperature lower calcination 2h～3h of 530 ℃～560 ℃, promptly get again.
In the step 1.1, the ratio of glucose and deionized water is 1g: 6mL～8mL.
In the step 1.2, the mass ratio of carbon ball and titanium sulfate is 1: 3.5～4.
Preparation method of the present invention is that sensitizer and titanic oxide hollow microballoon are under the synergy of carrier at the cobalt porphyrin, and prepared cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst is compared with existing photochemical catalyst, and the photocatalysis effect significantly improves.Wherein, titanic oxide hollow microballoon is compared with the titanium dioxide of other structures, has the big spy of specific area and becomes, and the surfaces externally and internally of this tiny balloon all can provide the active site position of organic molecular degradation.In addition, utilize hydroxyl and the hydroxyl of titanium dioxide surface in the cobalt porphyrin can form hydrogen bond, effectively avoid porphyrin in reaction loss and form polymer, improved the stability of the cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst of preparation.Test shows that the cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst of the present invention's preparation especially has good degradation effect to methylene blue dye waste water.
Description of drawings
Fig. 1 is the TEM figure of the titanic oxide hollow microballoon among the present invention;
Fig. 2 be the embodiment of the invention 1 preparation titanic oxide hollow microballoon and cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst ultraviolet-spectrogram diffuses;
Fig. 3 is the degradation rate curve map of degradation rate contrast test of the cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst of the embodiment of the invention 1 preparation.
The specific embodiment
Embodiment 1
The preparation method of cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst of the present invention, concrete steps are following:
Step 1, preparation titanic oxide hollow microballoon.Concrete steps are:
Step 1.1,4.5g glucose placed the agitated reactor that the 27mL deionized water is housed; Isothermal reaction 12h under 130 ℃ temperature after the room temperature cooling, takes out sediment; Use the mixed solution of deionized water and absolute ethyl alcohol to wash 4 times; Filter, the solid matter that obtains is dry under 80 ℃ temperature, promptly obtain the carbon ball.
Step 1.2, with the carbon ball that 0.2g step 1.1 obtains, place the agitated reactor that titanium sulfate aqueous solution is housed, wherein; The quality of titanium sulfate is 0.75g in the titanium sulfate aqueous solution, and isothermal reaction 24h under 130 ℃ temperature is after the room temperature cooling; Take out sediment, use the mixed solution of deionized water and absolute ethyl alcohol to wash 3 times, filter; The solid matter that obtains is dry under 80 ℃ temperature, at 550 ℃ temperature lower calcination 2.5h, promptly get titanic oxide hollow microballoon again.The TEM figure of the titanic oxide hollow microballoon that makes is as shown in Figure 1.
Step 2, the alcohol solvent that the titanic oxide hollow microballoon and the 40mL of step 1 preparation is dissolved with the cobalt porphyrin fully mix; Wherein, the quality of titanic oxide hollow microballoon is 1g, and the quality of cobalt porphyrin is 0.8mg; With mixture reflux 2h under stirring; The reflux temperature is 95 ℃, under 80 ℃ of temperature, dries 2h again, promptly gets cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst.
Wherein, the structural formula of cobalt porphyrin is:
As shown in Figure 2, a is the ultraviolet-diffuse reflection spectrum of the titanic oxide hollow microballoon that makes of present embodiment, and b is the ultraviolet-diffuse reflection spectrum of the cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst that makes of present embodiment.Can find out that the cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst of the present invention's preparation is compared than titanic oxide hollow microballoon, and stronger absorbability is arranged in visible-range.
Embodiment 2
The preparation method of cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst of the present invention, concrete steps are following:
Step 1, preparation titanic oxide hollow microballoon.Concrete steps are:
Step 1.1,4.5g glucose placed the agitated reactor that the 30mL deionized water is housed; Isothermal reaction 13h under 120 ℃ temperature after the room temperature cooling, takes out sediment; Use the mixed solution of deionized water and absolute ethyl alcohol to wash 4 times; Filter, the solid matter that obtains is dry under 70 ℃ temperature, promptly obtain the carbon ball.
Step 1.2, with the carbon ball that 0.2g step 1.1 obtains, place the agitated reactor that titanium sulfate aqueous solution is housed, wherein; The quality of titanium sulfate is 0.7g in the titanium sulfate aqueous solution, and isothermal reaction 26h under 120 ℃ temperature is after the room temperature cooling; Take out sediment, use the mixed solution of deionized water and absolute ethyl alcohol to wash 4 times, filter; The solid matter that obtains is dry under 70 ℃ temperature, at 530 ℃ temperature lower calcination 3h, promptly get titanic oxide hollow microballoon again.
Step 2, with the N-that the titanic oxide hollow microballoon and the 50mL of step 1 preparation is dissolved with the cobalt porphyrin, the dinethylformamide solvent fully mixes, wherein; The quality of titanic oxide hollow microballoon is 1g; The quality of cobalt porphyrin is 5mg, and with mixture reflux 5h under stirring, the reflux temperature is 100 ℃; Under 60 ℃ of temperature, dry 3h again, promptly get cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst.
Wherein, the structural formula of cobalt porphyrin is:
Embodiment 3
The preparation method of cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst of the present invention, concrete steps are following:
Step 1, preparation titanic oxide hollow microballoon.Concrete steps are:
Step 1.1,4.5g glucose placed the agitated reactor that the 35mL deionized water is housed; Isothermal reaction 13h under 150 ℃ temperature after the room temperature cooling, takes out sediment; Use the mixed solution of deionized water and absolute ethyl alcohol to wash 5 times; Filter, the solid matter that obtains is dry under 90 ℃ temperature, promptly obtain the carbon ball.
Step 1.2, with the carbon ball that 0.2g step 1.1 obtains, place the agitated reactor that titanium sulfate aqueous solution is housed, wherein; The quality of titanium sulfate is 0.8g in the titanium sulfate aqueous solution, and isothermal reaction 22h under 150 ℃ temperature is after the room temperature cooling; Take out sediment, use the mixed solution of deionized water and absolute ethyl alcohol to wash 3 times, filter; The solid matter that obtains is dry under 90 ℃ temperature, at 560 ℃ temperature lower calcination 2h, promptly get titanic oxide hollow microballoon again.
Step 2, the chloroform solvent that the titanic oxide hollow microballoon and the 60mL of step 1 preparation is dissolved with the cobalt porphyrin fully mix; Wherein, the quality of titanic oxide hollow microballoon is 1g, and the quality of cobalt porphyrin is 0.5mg; With mixture reflux 3h under stirring; The reflux temperature is 80 ℃, under 70 ℃ of temperature, dries 2.5h again, promptly gets cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst.
Wherein, the structural formula of cobalt porphyrin is:
The preparation method of titanic oxide hollow microballoon is simple among the present invention, easy operating.It utilizes the carbon ball to prepare titanic oxide hollow microballoon as template, removes this template through high-temperature calcination, in this process, can make the titania secondary crystallization simultaneously, improves the crystallization degree of titanium dioxide, and then improves the catalytic capability of the photochemical catalyst of preparation.In addition, can prepare the required carbon ball template of titanic oxide hollow microballoon of different size through experiment condition factors such as reaction temperature height, reaction time length in the control step 1.1.The titanic oxide hollow microballoon surfaces externally and internally of different-diameter can also just can be regulated and control for the adsorption surface area that the sensitizer molecule provides; The increase of ordinary circumstance sensitizer adsorbance can improve catalytic effect; But the porphyrin as sensitizer is easy to generate dimer, polymer under the situation of excessive concentration; Reduce its effect, thereby can regulate its surface area size through the size of control carbon ball as sensitizer, also just can control sensitizer its surface excess how much.
Preparation method of the present invention uses titanic oxide hollow microballoon to be load; Compare with the titanium dioxide of other structures; Hollow-core construction has higher specific area; And the characteristic of its internal cavities can be implemented in the inner reflection of light of spheroid, thereby reaches the efficient absorption to light, plays catalytic action efficiently; Again since the most the cobalt porphyrin of sensitizer have very high mole coefficient (being approximately tens0000), mole coefficient is high more, shows the absorbability of light by force more, the photoelectron number that produces during optical excitation is also just many more.Simultaneously ((hydrogen bond action takes place OH), and formation C-O-Ti key is for the transmission of light induced electron provides favourable transmission channel to the hydroxyl that OH) exists with titanium dioxide surface to the hydroxyl on the cobalt porphyrin molecule.Thereby in photocatalytic process; When the optical excitation porphyrin; The photoelectron that produces is transported to the conduction band of titanium dioxide through the C-O-Ti key between porphyrin and the titanium dioxide, and conduction band electron is transferred to the organic molecule of catalyst surface again, makes it that photochemical catalytic oxidation take place; Therefore after the cobalt porphyrin is carried on the titanic oxide hollow microballoon surface, can significantly strengthen the catalytic capability of titanium dioxide.
Comparative Examples 1
Select existing anatase titania powder example 1 as a comparison for use.
Comparative Examples 2
The anatase titania powder is dissolved into the alcohol solvent that is dissolved with the cobalt porphyrin fully to be mixed; Wherein, the quality of titanium ore titanium dioxide powder is 1g, and the quality of cobalt porphyrin is 0.8mg; With mixture reflux 2h under stirring; The reflux temperature is 95 ℃, under 80 ℃ of temperature, dries 2h again, promptly gets cobalt porphyrin sensitization anatase titania photochemical catalyst.
The cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst, the anatase titania powder of Comparative Examples 1 and the cobalt porphyrin sensitization anatase titania photochemical catalyst that Comparative Examples 2 makes that make among the titanic oxide hollow microballoon that step 1 among the embodiment 1 is made, the embodiment 1 take by weighing 0.05g respectively; Adopt the 150W halogen tungsten lamp as light source (under the situation of wave-length coverage 380～820nm); The 50mL5mg/L methylene blue solution of degrading respectively; Change calculations according to dyestuff absorbance before and after the illumination obtains the percentage of degrading, and comparing result is as shown in Figure 3.Wherein, The titanic oxide hollow microballoon absorbance that a makes for step 1 among the embodiment 1 is curve over time; B is the cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst absorbance that makes among the embodiment 1 curve over time; C is the anatase titania powder absorbance curve over time of Comparative Examples 1, and d is the cobalt porphyrin sensitization anatase titania photochemical catalyst absorbance that makes of Comparative Examples 2 curve over time.
As can be seen from Figure 3; Under 150W halogen tungsten lamp illuminate condition, the cobalt porphyrin sensitization titanium dioxide optical catalyst that the cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst of the present invention's preparation and Comparative Examples 2 make all has than the higher catalytic effect of no porphyrin sensitization catalyst.With the halogen tungsten lamp lamp is light source; During degraded 180min; The degradation rate of the cobalt porphyrin sensitization titanic oxide hollow microballoon photocatalyst for degrading methylene blue of invention preparation can reach 87.2%; And the degradation rate of titanic oxide hollow microballoon is merely 67.5%, and is visible, adopt the cobalt porphyrin be sensitizer can remarkable high photochemical catalyst to absorption of visible light.And be carrier with the anatase titania; The degradation rate of cobalt porphyrin sensitization anatase titania photochemical catalyst is merely 68.7%; It is thus clear that with the cobalt porphyrin is sensitizer, employing hollow-core construction titanium dioxide is that the photochemical catalyst of carrier has than the better degradation rate of anatase titania.
Can find out, be that sensitizer and titanic oxide hollow microballoon are under the synergy of carrier at the cobalt porphyrin, and the prepared cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst of the present invention is compared with existing photochemical catalyst, and the photocatalysis effect significantly improves.
Claims (5)
1. the preparation method of a cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalyst is characterized in that concrete steps are following:
Step 1, preparation titanic oxide hollow microballoon;
Step 2, the titanic oxide hollow microballoon of step 1 preparation and the organic solvent that is dissolved with the cobalt porphyrin are fully mixed; Wherein, The mass ratio of said cobalt porphyrin and titanic oxide hollow microballoon is 0.05～0.5: 100, and with mixture reflux 2h～5h under stirring, the reflux temperature is 80 ℃～100 ℃; Under 60 ℃～80 ℃ temperature, dry again, promptly get;
Wherein, the structural formula of cobalt porphyrin is:
2. according to the preparation method of the described cobalt porphyrin of claim 1 sensitization titanic oxide hollow microballoon photochemical catalyst, it is characterized in that said organic solvent is ethanol, N-, dinethylformamide or chloroform.
3. according to the preparation method of claim 1 or 2 described cobalt porphyrin sensitization titanic oxide hollow microballoon photochemical catalysts, it is characterized in that the concrete steps of step 1 are:
Step 1.1, glucose placed the agitated reactor that deionized water is housed; Isothermal reaction 11h～13h under 120 ℃～150 ℃ temperature after the room temperature cooling, takes out sediment; Use the mixed solution flushing of deionized water and absolute ethyl alcohol; Filter, the solid matter that obtains is dry under 70 ℃～90 ℃ temperature, promptly obtain the carbon ball;
Step 1.2, the carbon ball that step 1.1 is obtained place the agitated reactor that titanium sulfate aqueous solution is housed, and isothermal reaction 22h～26h under 120 ℃～150 ℃ temperature is after the room temperature cooling; Take out sediment; Use the mixed solution flushing of deionized water and absolute ethyl alcohol, filter, with the solid matter that obtains in drying under 70 ℃～90 ℃ temperature; At temperature lower calcination 2h～3h of 530 ℃～560 ℃, promptly get again.
4. according to the preparation method of the described cobalt porphyrin of claim 3 sensitization titanic oxide hollow microballoon photochemical catalyst, it is characterized in that the ratio of glucose and deionized water is 1g in the said step 1.1: 6mL～8mL.
5. according to the preparation method of the described cobalt porphyrin of claim 3 sensitization titanic oxide hollow microballoon photochemical catalyst, it is characterized in that the mass ratio of carbon ball and titanium sulfate is 1: 3.5～4 in the said step 1.2.
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Cited By (3)
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| CN108371959A (en) * | 2018-02-08 | 2018-08-07 | 北京科技大学 | A kind of sensitized titanium dioxide photochemical catalyst and its in-situ synthetic method |
| CN108940380A (en) * | 2018-07-27 | 2018-12-07 | 中国石油大学(华东) | A kind of preparation method of the visible light-responded photochemical catalyst based on dye-sensitized titania |
| CN116159593A (en) * | 2023-01-10 | 2023-05-26 | 华能武汉发电有限责任公司 | Modified titanium dioxide and preparation method and application thereof |
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| CN101024170A (en) * | 2007-03-30 | 2007-08-29 | 黄悦 | Photocatalyst product and preparing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108371959A (en) * | 2018-02-08 | 2018-08-07 | 北京科技大学 | A kind of sensitized titanium dioxide photochemical catalyst and its in-situ synthetic method |
| CN108940380A (en) * | 2018-07-27 | 2018-12-07 | 中国石油大学(华东) | A kind of preparation method of the visible light-responded photochemical catalyst based on dye-sensitized titania |
| CN116159593A (en) * | 2023-01-10 | 2023-05-26 | 华能武汉发电有限责任公司 | Modified titanium dioxide and preparation method and application thereof |
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Application publication date: 20120627 |