CN103586088A - Preparation method for selective degradation of hydroquinone composite photocatalyst - Google Patents
Preparation method for selective degradation of hydroquinone composite photocatalyst Download PDFInfo
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- CN103586088A CN103586088A CN201310585409.XA CN201310585409A CN103586088A CN 103586088 A CN103586088 A CN 103586088A CN 201310585409 A CN201310585409 A CN 201310585409A CN 103586088 A CN103586088 A CN 103586088A
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Abstract
The invention discloses a preparation method for selective degradation of hydroquinone composite photocatalyst. The preparation method comprises the following steps: a TiO2 semiconductor material is hydro-thermally synthesized; the surfaces of TiO2 particles are modified; a molecularly imprinted polymer is prepared; template molecules and functional monomers are immobilized onto the surface of semiconductor photocatalyst through a crosslinking trigger manner by using a surface molecularly imprinted technology and a proper polymerization method according to a proper ratio; cavities matched with the template molecules are left on the surface of the polymer after elution; then a circulating system with selectivity to the template molecules, special identification and catalytic degradation is realized; then the purpose of cooperating and promoting the selective photocatalytic degradation of target pollutants is achieved. The preparation method can effectively realize the purposes of selectively identifying, absorbing and catalytically degrading the target pollutants, improves the efficiency of effectively degrading the target pollutants, and has the advantage of stronger selectivity of treating environmental pollutants and waste water.
Description
Technical field
The present invention relates to a kind of material preparation and environmental pollution treatment technology, in particular a kind of preparation method of degradation selectivity hydroquinones composite photo-catalyst.
Background technology
Hydroquinones is a kind of typical industrial chemicals, the main black-and-white development agent as photographic film, also as the raw material of producing anthraquinone dye, azo dyes, also for the preparation of stabilizing agent, antioxidant and the polymerization inhibitor etc. of coating varnish, thereby entered environment very easily, environment especially water body is polluted.The toxicity of hydroquinones is very large, once enter human body, can all cause damage to liver, kidney, central nervous system; In addition, hydroquinones is easily oxidized to benzoquinone, easily and DNA react human body produced to larger harm, have carcinogenic with cause mutagenicity.Therefore, the removing of hydroquinones pollutant in environment is very important.At present, photocatalysis technology has been called the technology that is widely used in wastewater treatment in environment.People carry out modification to semiconductor and composite semiconductor and come processing environment pollution to obtain good effect, but do not have selectively, in the Complex water body that is difficult to coexist at multiple pollutant, target contaminant are removed.In order to improve the selective of photocatalysis technology, molecular imprinting is combined with photocatalysis technology, in the system that can coexist at multi-pollutant, the preferential removal target contaminant of selecting.
Molecular engram is branch superiorities such as collection Polymer Synthesizing, molecular recognition, a bionical bioengineering and frontier branch of science growing up is the technology that preparation has recognition function material.Owing to thering is the advantages such as can be scheduled to selective, identity, molecularly imprinted polymer (molecular imprinted polymer, MIP) is applied to the aspects such as chromatography, environment trace analysis, film separation, chiral material fractionation, biology sensor and receives much attention.
Molecular imprinting is the covalently or non-covalently effect utilizing between template molecule and monomer, through cross-linked polymeric, form polymer, and then with eluent, template molecule is eluted from polymer, in polymer, just formed like this hole matching with polymer, these holes have selective and affine performance to template molecule.Surface molecule print technology is the engram technology type that more has application prospect growing up on molecular imprinting basis, the polymer of preparing by the method has stronger selective, more recognition site, and material Transfer and adsorption dynamics adsorption kinetics faster.In photocatalytic process, it has specific recognition performance to target substance, and then reaches the object of preferential degraded target substance.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of degradation selectivity hydroquinones composite photo-catalyst is provided, realize the process of target contaminant first being adsorbed again to catalytic degradation, and then effectively utilized light source to reach the object of hydroquinones pollutant waste water in effective degraded environment.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
(1) TiO
2the Hydrothermal Synthesis of semi-conducting material
First by Ti (OC
4h
9)
4mix 1:1.25～4 in mass ratio with absolute ethyl alcohol, be uniformly mixed, in whipping process, add distilled water, mixed liquor is joined in reactor, and total liquor capacity is no more than 80% of reactor volume, isothermal reaction 12～36h at 120～160 ℃, it is at room temperature naturally cooling after reaction finishes, the product obtaining is used distilled water and absolute ethyl alcohol alternately to wash 2～5 times, dry under 50～70 ℃ of vacuum after centrifugation, obtains the uniform TiO of particle diameter
2semiconductor micron ball;
(2) TiO
2microparticle surfaces modification
By the TiO of Hydrothermal Synthesis gained
2semiconductor micron ball is distributed in the methanol solution that contains o-phenylenediamine, TiO
2with the mass ratio of o-phenylenediamine be 6:1～3:1, under room temperature, by stirring, make o-phenylenediamine molecule fully be connected to TiO
2the surface of material, has realized at TiO
2surface grafting active group;
(3) preparation of molecularly imprinted polymer
By template molecule hydroquinones and function monomer α-methacrylic acid in mass ratio 1:4～1:15 be dissolved in glutaraldehyde solution, the volume ratio of α-methacrylic acid and glutaraldehyde solution is 1:20～1:40, stir at ambient temperature 2～8h and make its abundant polymerization, then adding mass ratio is crosslinking agent EGDMA and the initiator A IBN of 1:1～1:5, the volume ratio of crosslinking agent EGDMA and mixed solution is 1:30～1:50, the volume ratio of initiator A IBN and mixed solution is 1:60～1:100, and 2～10mL methyl alcohol is as pore-foaming agent, the volume ratio of pore-foaming agent and mixed solution is 1:40～1:60, finally add the TiO after o-phenylenediamine modification in step (2)
2semi-conducting material is as the carrier of imprinted polymer, and said mixture is polymerisation 10～30h at 40～80 ℃ of waters bath with thermostatic control, the solid powder substance obtaining is crossed after grinding to 200 mesh sieves, then use the template molecule of apparatus,Soxhlet's in 70～80 ℃ of water-bath wash-out imprinted polymers of temperature, eluent is methyl alcohol and acetic acid, the volume ratio of methyl alcohol and acetic acid is 9:1～7:3, until can't detect hydroquinones in eluent.
As one of optimal way of the present invention, in described step (1), the liner of reactor is that polytetrafluoroethylene (PTFE) is made.
As one of optimal way of the present invention, described stirring means is magnetic agitation.
Synthetic blank imprinted polymer does not add template molecule hydroquinones in step (2) in the same way.Be used for contrasting.
Utilize surface molecule print technology, select suitable polymerization, template molecule and function monomer are changed to the immobilized surface to semiconductor light-catalyst according to suitable proportioning by crosslinked initiation method, after wash-out, at polymer surfaces, leave the hole matching with template molecule, thereby realized, template molecule is had selectively, specialty identification is the circulating system to its catalytic degradation then, and then reaches object collaborative and promotion selective photocatalysis degraded target contaminant.
The present invention has the following advantages compared to existing technology: the Photocatalytic Degradation Process of molecularly imprinted polymer photochemical catalyst of the present invention can effectively be realized the also object of catalytic degradation is selectively identified, adsorbed to target contaminant, improve the efficiency to effective degraded of target substance, there is stronger selective processing environment pollutant waste water.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of molecular imprinted polymer on surface and the blank imprinted polymer photochemical catalyst of contrast;
Fig. 2 is the solid UV-Vis spectrogram of trace and blank imprinted polymer photochemical catalyst.
The specific embodiment
Below embodiments of the invention are elaborated, the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
(1) TiO
2the Hydrothermal Synthesis of semi-conducting material
First by Ti (OC
4h
9)
4with absolute ethyl alcohol 1:1.25 mixing in mass ratio, at constant speed lower magnetic force, stirring 5h fully mixes both, in whipping process, add appropriate distilled water, mixed liquor is joined in teflon-lined reactor, total liquor capacity is no more than 80% of reactor volume, at 160 ℃ of constant temperature, react 30h, it is at room temperature naturally cooling after reaction finishes, the product obtaining is used distilled water and absolute ethyl alcohol alternately to wash 5 times, centrifugation, finally dry under 70 ℃ of vacuum, finally obtain the uniform TiO2 semiconductor of particle diameter micron ball;
(2) TiO
2microparticle surfaces modification
By the TiO of Hydrothermal Synthesis gained
2semi-conducting material is distributed in a certain amount of methanol solution of o-phenylenediamine, makes TiO
2than for 6:1, under room temperature condition, with constant speed magnetic agitation 10h, make o-phenylenediamine molecule can fully be connected to TiO with the amount of o-phenylenediamine
2the surface of material, has realized at TiO
2surface grafting active group, obtains the TiO through o-phenylenediamine modification
2microballoon;
(3) preparation of molecularly imprinted polymer
By template molecule hydroquinones and function monomer α-methacrylic acid in mass ratio 1:4～1:15 be dissolved in glutaraldehyde solution, the volume ratio of α-methacrylic acid and glutaraldehyde solution is 1:20～1:40, stir at ambient temperature 2～8h and make its abundant polymerization, then adding mass ratio is crosslinking agent EGDMA and the initiator A IBN of 1:1～1:5, the volume ratio of crosslinking agent EGDMA and mixed solution is 1:30～1:50, the volume ratio of initiator A IBN and mixed solution is 1:60～1:100, and 2～10mL methyl alcohol is as pore-foaming agent, the volume ratio of pore-foaming agent and mixed solution is 1:40～1:60, finally add the TiO after o-phenylenediamine modification in step (2)
2semi-conducting material is as the carrier of imprinted polymer, and said mixture is polymerisation 10～30h at 40～80 ℃ of waters bath with thermostatic control, the solid powder substance obtaining is crossed after grinding to 200 mesh sieves, then use the template molecule of apparatus,Soxhlet's in 70～80 ℃ of water-bath wash-out imprinted polymers of temperature, eluent is methyl alcohol and acetic acid, the volume ratio of methyl alcohol and acetic acid is 9:1～7:3, until can't detect hydroquinones in eluent, pattern of descriptive parts molecule is removed completely from imprinted polymer,
As a comparison, with same method, synthesized blank imprinted polymer, except do not add template molecule hydroquinones in polymerization process;
(4) sample of getting preparation in 75mg step (3) carries out photocatalytic degradation test in photochemical reaction instrument, record this photochemical catalyst and under visible ray causes, the antibiotic degradation rate of hydroquinones is reached more than 88% in 60min, this surface molecule print photochemical catalyst has stronger photocatalytic activity.
The method of photocatalytic activity evaluation is: in photo catalysis reactor (light source is purchased from Zhong Jiaojin source, Beijing CEL-S500 solar simulated xenon source), carry out, the hydroquinones simulated wastewater of 100mL variable concentrations is added in reactor and measures its initial value, then add respectively 0.5g/L, 1.0g/L, 1.5g/L, 2.0g/L, the molecularly imprinted polymer of 2.5g/L and blank polymer photochemical catalyst, magnetic agitation is also opened aerator and is passed into air and keep catalyst in suspending or afloat, oxygen in photocatalytic process can be provided, in During Illumination at interval of 10min sample analysis, after centrifugation, get supernatant liquor at ultraviolet-visible spectrophotometer λ
max=289nm place measures absorbance, and degradation rate DC obtains by following formula:
DC=[(A
0-A
i)/A
0]×100%
A wherein
0the absorbance of hydroquinones solution when reaching adsorption equilibrium, A
iabsorbance for the hydroquinones solution of different time sampling and measuring.
As shown in Figure 1, Fig. 1 is the infrared spectrogram of molecular imprinted polymer on surface and the blank imprinted polymer photochemical catalyst of contrast, a, and b, c, d is respectively the TiO after o-phenylenediamine modification
2hydroquinones molecularly imprinted polymer is not before wash-out template molecule, infrared spectrogram after blank imprinted polymer and imprinted polymer wash-out template molecule, as can be seen from the figure in trace process hydroquinones and methacrylic acid because of the disappeared characteristic peak of some functional groups of polymerization, at wash-out, remove after template molecule, these characteristic peaks occur again.
Fig. 2 is the solid UV-Vis spectrogram of trace and blank imprinted polymer photochemical catalyst, and as can be seen from the figure, the optical absorption intensity of the photochemical catalyst after molecular engram polymerization is better than the not TiO of trace
2material, molecular imprinted polymer on surface photochemical catalyst has the absorbability to Uv and visible light preferably, and the trend that the absorption in the photochemical catalyst sample after trace is moved to visible region, illustrates that the polyalcohol catalyst after trace has stronger visible light-responded scope.
Weigh the different templates molecule of equal in quality and the different molecular trace photochemical catalyst of function monomer proportioning, visible light photocatalytic degradation 5mg L
-1hydroquinones solution, other embodiments are identical with embodiment 1, result shows when the mass ratio of hydroquinones and methacrylic acid is 1:8, its photocatalytic degradation hydroquinones is most effective, so, select the imprinted polymer photochemical catalyst of this proportioning to examine or check the selective contrast of itself and blank imprinted polymer.
Embodiment 3
(1) first with synthetic imprinted polymer and blank polyalcohol catalyst, adsorb separately hydroquinones, the catechol of variable concentrations, the solution of phloroglucin.According to following formula, calculate the adsorption capacity of polymer to different plant species:
Q=(C
0-C
e)*V/m
Wherein Q is adsorption capacity (the mg g of adsorbent
-1), C
0, C
ebe respectively hydroquinones and adsorb concentration (the mg L after front and adsorption equilibrium
-1), V is the concentration (L) of hydroquinones solution, m is the quality (g) of adsorbent.
(2) respectively with imprinted polymer and the blank polyalcohol catalyst absorption hydroquinones of same concentrations and the mixed solution of interfering material, through identical adsorption time, centrifugation aaerosol solution, measure the concentration of supernatant, calculate the adsorption capacity of catalyst to different plant species, then calculate its adsorptive selectivity to different material.Result show imprinted polymer photochemical catalyst to the adsorption capacity of hydroquinones apparently higher than the adsorption capacity to catechol and phloroglucin, and blank imprinted polymer is little to three's adsorption capacity difference, illustrates and in trace process, improved the adsorption capacity of imprinted polymer to hydroquinones.
Embodiment 4
(1) by changing the consumption 0.5g L of molecular engram photochemical catalyst
-1, 1.0g L
-1, 1.5g L
-1, 2.0g L
-1, 2.5g L
-1, examine or check the impact of catalyst amounts on photocatalytic degradation, result shows that at catalyst amount be 1.5g L
-1time, its degradation efficiency to hydroquinones is the highest, can reach more than 88%.So selected catalyst amount is 1.5g L in experiment
-1.
(2) use the hydroquinones solution of catalytic degradation variable concentrations under molecularly imprinted polymer photochemical catalyst visible ray, examination is the degradation kinetics of molecular engram photochemical catalyst to hydroquinones when variable concentrations, known by calculating and matching kinetics equation, the process of molecular engram photocatalyst for degrading hydroquinones meets pseudo-first-order kinetic model, when hydroquinones initial concentration is 5mgL
-1time, its average degradation rate to hydroquinones is 0.052min
-1.
Embodiment 5
Use respectively the hydroquinones of imprinted polymer and blank polymer photocatalyst for degrading same concentrations and the mixed solution of interfering material (as catechol, phloroglucin etc.), by calculating the degradation efficiency of different material and then calculating its selectivity factor to different material.
C wherein
0, C
ebe respectively concentration (the mg L after the degraded of hydroquinones initial sum
-1); D is distribution coefficient, D
qUI, D
mbe respectively the distribution coefficient of hydroquinones and interfering material; α is selectivity factor, α
i, α
nbe respectively the selectivity factor of trace and blank polymer photochemical catalyst, α
βit is relative selectivity coefficient.
Experimental result shows, imprinted polymer photochemical catalyst is the material apparently higher than other contrasts to the degradation efficiency of hydroquinones, selectivity factor is also all greater than other interfering materials, and relative selectivity coefficient shows that imprinted polymer photochemical catalyst has good degradation efficiency than blank polymer photochemical catalyst to hydroquinones.Explanation has selective preferably to hydroquinones with the synthetic molecularly imprinted polymer photochemical catalyst of the method, thereby realized the object to the selective catalysis degraded of target substance.
Claims (4)
1. a preparation method for degradation selectivity hydroquinones composite photo-catalyst, is characterized in that, comprises the following steps:
(1) TiO
2the Hydrothermal Synthesis of semi-conducting material
First by Ti (OC
4h
9)
4mix 1:1.25～4 in mass ratio with absolute ethyl alcohol, be uniformly mixed, in whipping process, add distilled water, mixed liquor is joined in reactor, and total liquor capacity is no more than 80% of reactor volume, isothermal reaction 12～36h at 120～160 ℃, it is at room temperature naturally cooling after reaction finishes, the product obtaining is used distilled water and absolute ethyl alcohol alternately to wash 2～5 times, dry under 50～70 ℃ of vacuum after centrifugation, obtains the uniform TiO of particle diameter
2semiconductor micron ball;
(2) TiO
2microparticle surfaces modification
By the TiO of Hydrothermal Synthesis gained
2semiconductor micron ball is distributed in the methanol solution that contains o-phenylenediamine, TiO
2with the mass ratio of o-phenylenediamine be 6:1～3:1, under room temperature, by stirring, make o-phenylenediamine molecule fully be connected to TiO
2the surface of material, has realized at TiO
2surface grafting active group;
(3) preparation of molecularly imprinted polymer
By template molecule hydroquinones and function monomer α-methacrylic acid in mass ratio 1:4～1:15 be dissolved in glutaraldehyde solution, the volume ratio of α-methacrylic acid and glutaraldehyde solution is 1:20～1:40, stir at ambient temperature 2～8h and make its abundant polymerization, then adding mass ratio is crosslinking agent EGDMA and the initiator A IBN of 1:1～1:5, the volume ratio of crosslinking agent EGDMA and mixed solution is 1:30～1:50, the volume ratio of initiator A IBN and mixed solution is 1:60～1:100, and 2～10mL methyl alcohol is as pore-foaming agent, the volume ratio of pore-foaming agent and mixed solution is 1:40～1:60, finally add the TiO after o-phenylenediamine modification in step (2)
2semi-conducting material is as the carrier of imprinted polymer, and said mixture is polymerisation 10～30h at 40～80 ℃ of waters bath with thermostatic control, the solid powder substance obtaining is crossed after grinding to 200 mesh sieves, then use the template molecule of apparatus,Soxhlet's in 70～80 ℃ of water-bath wash-out imprinted polymers of temperature, eluent is methyl alcohol and acetic acid, the volume ratio of methyl alcohol and acetic acid is 9:1～7:3, until can't detect hydroquinones in eluent.
2. the preparation method of a kind of degradation selectivity hydroquinones composite photo-catalyst according to claim 1, is characterized in that, in described step (1), the liner of reactor is that polytetrafluoroethylene (PTFE) is made.
3. the preparation method of a kind of degradation selectivity hydroquinones composite photo-catalyst according to claim 1, is characterized in that, described stirring means is magnetic agitation.
4. the preparation method of a kind of degradation selectivity hydroquinones composite photo-catalyst according to claim 1, is characterized in that, synthetic blank imprinted polymer does not add template molecule hydroquinones in step (2) in the same way.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512964A (en) * | 2016-11-07 | 2017-03-22 | 东南大学 | Preparation method of polyphenol selective ion exchange resin |
| CN106587282A (en) * | 2016-12-08 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Difunctional multi-template molecularly imprinted type photoelectric anode material and preparation method and application |
| CN112844399A (en) * | 2020-12-21 | 2021-05-28 | 南昌航空大学 | Preparation method of group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophore |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319591A (en) * | 2011-07-15 | 2012-01-18 | 江苏大学 | Preparation method of molecular imprinting modification composite photocatalyst with selective degradation |
| CN103120962A (en) * | 2012-12-10 | 2013-05-29 | 江苏大学 | Preparation method and application of molecularly imprinted polymer modified titanium dioxide composite photocatalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319591A (en) * | 2011-07-15 | 2012-01-18 | 江苏大学 | Preparation method of molecular imprinting modification composite photocatalyst with selective degradation |
| CN103120962A (en) * | 2012-12-10 | 2013-05-29 | 江苏大学 | Preparation method and application of molecularly imprinted polymer modified titanium dioxide composite photocatalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512964A (en) * | 2016-11-07 | 2017-03-22 | 东南大学 | Preparation method of polyphenol selective ion exchange resin |
| CN106512964B (en) * | 2016-11-07 | 2019-05-31 | 东南大学 | A kind of preparation method of polyphenol selective ion exchange resin |
| CN106587282A (en) * | 2016-12-08 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Difunctional multi-template molecularly imprinted type photoelectric anode material and preparation method and application |
| CN106587282B (en) * | 2016-12-08 | 2020-02-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Double-functional multi-template molecularly imprinted photoelectric anode material and preparation and application thereof |
| CN112844399A (en) * | 2020-12-21 | 2021-05-28 | 南昌航空大学 | Preparation method of group imprinting conductive organic layer composite photocatalytic material for targeted recognition of toxic pharmacophore |
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