CN102125877B - Method for preparing selectively degraded ciprofloxacin photocatalyst - Google Patents
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- CN102125877B CN102125877B CN 201110000897 CN201110000897A CN102125877B CN 102125877 B CN102125877 B CN 102125877B CN 201110000897 CN201110000897 CN 201110000897 CN 201110000897 A CN201110000897 A CN 201110000897A CN 102125877 B CN102125877 B CN 102125877B
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Abstract
The invention discloses a method for preparing a selectively degraded ciprofloxacin photocatalyst, and belongs to the technical fields of material preparation and environmental pollution treatment. The method comprises the following steps of: (1) hydrothermal synthesis of a ZnS semiconductor material; (2) ZnS surface modification; (3) preparation of a molecular imprinting polymer photocatalyst; and (4) elution of template modules in the imprinting polymer from the obtained solid powdery substance. The photocatalytic degradation process of the molecular imprinting polymer photocatalyst can effectively fulfill the purposes of selective identification, adsorption and catalytic degradation of target pollutants, the effective degradation efficiency of the target substance is improved, and the photocatalyst has the advantage of strong selective treatment of antibiotic wastewater.
Description
Technical field
The present invention relates to a kind of method of utilizing the technological method of surface molecule print to prepare the semiconductor light-catalyst of trace Ciprofloxacin, belong to the technical field of material preparation and environmental pollution improvement.
Background technology
Ciprofloxacin belongs to FQNS, has the characteristics of stronger antibacterial ability and broad-spectrum sterilization and is widely used in aquatic products industry.But its resistance to the action of a drug and side effect thereof also have a strong impact on people's life simultaneously, and the accumulation of low content is easy to generate the resistance to the action of a drug for a long time; Research shows that Ciprofloxacin has serious liver renal toxicity, and direct threats is to people's life and health.So the antibiotic pharmaceutical wastewater of rationally handling in the sanitary wastewater is an important link.At present, photocatalysis technology extensive use study the technology of the wastewater treatment in environment.People carry out modification to semiconductor and composite semiconductor and come the processing environment pollution to obtain good effect, but do not have selectivity, are difficult in the complicated water body of multiple pollutant coexistence, remove object.For improving the selectivity of photocatalysis technology, molecular imprinting is combined with the photoelectrocatalysis technology, can be in the system of multi-pollutant coexistence, target contaminant is removed in preferential selection.
Molecular engram is a branch superiority such as collection Polymer Synthesizing, molecular recognition, a bionical bioengineering and frontier branch of science growing up is that preparation has the technology of recognition function material.Molecular imprinting is the covalently or non-covalently effect that utilizes between template molecule and the monomer; Form polymer through cross-linked polymeric; And then template molecule is eluted from polymer with eluent; In polymer, just formed the hole of mating with polymer phase like this, these holes have selectivity and affine performance to template molecule.Owing to have advantages such as preset selection property, identity; (molecular imprinted polymer MIP) is applied to aspects such as chromatography, environment trace analysis, film separation, chiral material fractionation, biology sensor and receives much attention molecularly imprinted polymer.
The surface molecule print technology is the engram technology type that application prospect is more arranged that on the molecular imprinting basis, grows up; Polymer with the method preparation has stronger selectivity; 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 purpose of preferential degraded target substance.Therefore; We utilize the surface molecule print technology; Select suitable polymerization for use, template molecule and function monomer are changed immobilized surface to semiconductor light-catalyst through crosslinked initiation mode with it according to suitable proportioning, through staying the hole that is complementary with template molecule at polymer surfaces behind the wash-out; Thereby realized that template molecule is had selectivity; Specialty identification realizes the circulating system of absorption degradation once more then to the process of its catalytic degradation after the degraded, and then reaches purpose collaborative and promotion selective photocatalysis degraded target contaminant.
Summary of the invention
The present invention utilizes the surface molecule print technology to be preparation means, prepares a kind of the target contaminant Ciprofloxacin to be had specific optionally composite photo-catalyst.Its advantage is in system, to make up a cyclic process, realized target substance is adsorbed catalytic degradation more earlier, and then the cyclic process of absorption degradation, and then effectively utilize light source to reach the purpose of Ciprofloxacin antibiotic waste water in effective degraded environment.
The technical scheme that the present invention adopts is:
(1) hydro-thermal of ZnS semi-conducting material is synthetic: at first with Zn (COOH)
2And CS (NH
2)
21:2 ~ 5 are dissolved in an amount of distilled water in molar ratio; Stir 2 ~ 10 h at constant speed lower magnetic force both are fully mixed, then mixed solution is joined in the teflon-lined agitated reactor, total liquor capacity is no more than 80% of reactor volume; React 12 ~ 48 h down for 120 ~ 160 ℃ at constant temperature; Cooling naturally at room temperature after reaction finishes, product distilled water that obtains and absolute ethyl alcohol alternately wash for several times, centrifugation; Dry under 50 ~ 70 ℃ of vacuum at last, finally obtain the uniform ZnS semiconductor of particle diameter micron ball;
(2) ZnS surface modification: ZnS semi-conducting material synthetic in (1) is distributed in the methanol solution of acrylamide, makes the amount ratio of ZnS and acrylamide be 6:1 ~ 3:1, under the room temperature condition, with constant speed magnetic agitation 10 ~ 20 h;
(3) preparation of molecularly imprinted polymer photochemical catalyst: the preparation of molecularly imprinted polymer; At first than 1:4 ~ 1:10 be dissolved in the methyl alcohol of certain volume by amount template molecule (Ciprofloxacin) and function monomer (α-Jia Jibingxisuan); Stir 2 ~ 8 h at ambient temperature and make its abundant polymerization; The amount that adds crosslinking agent EGDMA and initiator A IBN then is than being 1:1 ~ 1:3; And small amount of toluene is as pore-foaming agent, adds ZnS semi-conducting material after acrylic amide modified at last as the carrier of imprinted polymer, feeds N
210 min are to remove the O in the solution
2, said mixture is at 50 ~ 80 ℃ of following polymerisation 10 ~ 30 h of water bath with thermostatic control;
(4) solid powder substance that obtains is crossed 200 mesh sieves after grinding, use the template molecule of apparatus,Soxhlet's in 70 ~ 85 ℃ of water-bath wash-outs of temperature imprinted polymer then, eluent is methyl alcohol and acetate, and its volume ratio is 9:1 ~ 7:3.
Step (1) Zn (COOH) wherein
2And CS (NH
2)
2The concentration of the aqueous solution is respectively 0.1 mol L
-1With 0.2 mol L
-1
Wherein concentration is 0.2 mol L in the methanol solution of the middle acrylamide of step (2)
-1
Wherein the concentration of the methanol solution of template molecule (Ciprofloxacin) and function monomer (α-Jia Jibingxisuan) is 0.1 mol L in the step (3)
-1~ 0.25 mol L
-1
Technological merit of the present invention: the photocatalytic degradation process of molecularly imprinted polymer photochemical catalyst can effectively realize the purpose to the identification of target contaminant selectivity, absorption and catalytic degradation; Improved efficient, had the advantage that stronger selectivity is handled antibiotic waste water effective degraded of target substance.
Description of drawings
The infrared spectrogram of Fig. 1 imprinted polymer and blank imprinted polymer photochemical catalyst; A, b, c; D is respectively the ZnS after acrylic amide modified; The Ciprofloxacin molecularly imprinted polymer is (MIP-2) before the wash-out template molecule not, the infrared spectrogram behind blank imprinted polymer and the MIP-2 imprinted polymer wash-out template molecule, as can be seen from the figure in the trace process Ciprofloxacin and α-Jia Jibingxisuan because of the disappeared characteristic peak of some functional groups of polymerization; Behind the wash-out template molecule, these characteristic peaks occur again.
Fig. 2 is the solid UV-Vis spectrogram of MIP-2 and blank imprinted polymer photochemical catalyst; As can be seen from the figure; The optical absorption intensity of MIP-2 photochemical catalyst is better than the not ZnS material of trace; Surface MIP-2 molecularly imprinted polymer photochemical catalyst has preferably ultraviolet and absorption of visible light ability, and the trend that moves to visible region of the absorption in the photochemical catalyst sample behind trace.
The specific embodiment
As a comparison, synthesized blank imprinted polymer, wherein in polymerization process, do not added the template molecule Ciprofloxacin with same method and step.
That utilizes that the present invention adopts that the surface molecule print technology prepares has optionally semiconductor light-catalyst to Ciprofloxacin, and the template molecule Ciprofloxacin is had higher selectivity degradation effect.
Photocatalytic activity is estimated: in DW-01 type photochemical reaction appearance (available from Educational Instrument Factory of Yangzhou University), carry out; The visible lamp irradiation; The certain density Ciprofloxacin simulated wastewater of 100 mL is added in the reactor and measures its initial value; Add a certain amount of trace and blank polymer photochemical catalyst then, magnetic agitation is also opened the aerator bubbling air and is kept catalyst to be in suspending or afloat, the oxygen in the photocatalytic process can be provided; Every interval 10 min sample analysis are got supernatant liquor at ultraviolet-visible spectrophotometer λ in the illumination process after the centrifugation
Max=273nm place measures absorbance, and passes through formula: DC=[(A
0-A
i)/A
0] * 100% is calculated degradation rate, wherein A
0The absorbance of ciprofloxacin solution when reaching adsorption equilibrium, A
iThe absorbance of the ciprofloxacin solution of measuring for timing sampling.
Below in conjunction with the practical implementation instance the present invention is further specified.
Embodiment 1-4:(1) hydro-thermal of ZnS semi-conducting material is synthetic: at first with Zn (COOH)
2And CS (NH
2)
2By amount than 1:2 (6 mmol: 12 mmol) be dissolved in an amount of distilled water; Stir 4 h at constant speed lower magnetic force both are fully mixed, say that then solution joins in the teflon-lined agitated reactor, total liquor capacity is no more than 80% of reactor volume; React 24 h down for 150 ℃ at constant temperature; Cooling naturally at room temperature after reaction finishes, product distilled water that obtains and absolute ethyl alcohol alternately wash for several times, centrifugation; Dry under 60 ℃ of vacuum at last, finally obtain the uniform ZnS semiconductor of particle diameter micron ball.
(2) with a certain amount of ZnS microsphere particle of hydrothermal preparation; Join in a certain amount of methanol solution that is dissolved with acrylamide; The amount that makes ZnS and acrylamide is than being 3:1 (15 mmol: 5 mmol), at room temperature stir 20 h, filter the ZnS particle that obtains after acrylic amide modified then; Drying for standby under the vacuum obtains through acrylic amide modified ZnS microballoon.
(3) with template molecule (Ciprofloxacin) and function monomer (α-Jia Jibingxisuan) in different amount ratio 1:4; 1:6,1:8,1:10 are dissolved in the methanol solution of a certain amount of volume; Stir 4 h at ambient temperature and make its abundant polymerization; Add crosslinking agent EGDMA and initiator A IBN then, the ratio of its amount is 1:3, and (EGDMA 1 mmol and AIBN 3 mmol) and 5 mL toluene are as pore-foaming agent; Add the carrier of the ZnS semi-conducting material of 3 g after acrylic amide modified at last, feed N as imprinted polymer
210 min are to remove the O in the solution
2, with said mixture at 60 ℃ of following polymerisation 24 h of water bath with thermostatic control.The solid powder substance that obtains is crossed 200 mesh sieves after grinding, use the template molecule of apparatus,Soxhlet's in 85 ℃ of water-bath wash-outs of temperature imprinted polymer then, eluent is methyl alcohol and acetate, and its volume ratio is 9:1 (90 mL:10 mL).Press the different material amount proportioning of Ciprofloxacin and α-Jia Jibingxisuan, experiment obtains MIP-1, MIP-2, four kinds of molecular engram photochemical catalysts of MIP-3 and MIP-4 altogether.As a comparison, synthesized blank imprinted polymer, except in polymerization process, not adding the template molecule Ciprofloxacin with same method and step.
(4) sample of getting preparation in the 75 mg steps (3) carries out the photocatalytic degradation test in the photochemical reaction appearance, add 100mL, 20mg L
-1Ciprofloxacin solution in, survey its absorbance with ultraviolet-visible spectrophotometer, and pass through formula: DC%=[(A at 273 nm places
0-A
i)/A
0] * 100% is calculated degradation rate, wherein A
0The absorbance of ciprofloxacin solution when reaching adsorption equilibrium, A
iThe absorbance of the ciprofloxacin solution of measuring for timing sampling.Degradation rate is represented the photocatalytic activity of the catalyst of preparation in (3).
Test one:Synthetic molecular engram photochemical catalyst and blank trace photochemical catalyst in (3) in the weighing example 1, visible light photocatalytic degradation 20 mg L
-1Ciprofloxacin solution, the MIP-2 photochemical catalyst is best to the degradation effect of Ciprofloxacin, under visible light causes, reaches more than 90% in 60 min, explains that this surface molecule print photochemical catalyst has stronger photocatalytic activity to the template molecule Ciprofloxacin.Show that when the ratio of Ciprofloxacin and methacrylic acid was 1:6, its photocatalytic degradation Ciprofloxacin was most effective, so, select MIP-2 imprinted polymer photochemical catalyst to examine or check its selectivity in the experiment and contrast with blank imprinted polymer.
Test two:(1) at first in (3) in the use-case 1 photochemical catalyst of preparation adsorb the Ciprofloxacin of variable concentrations, gatifloxacin, the solution of chloramphenicol separately.Calculate the adsorption capacity of polymer according to formula to different plant species.
Q= (C
0-C
e)*V/m
Wherein
QBe adsorption capacity (the mg g of adsorbent
-1), C
0, C
eBe respectively before the Ciprofloxacin absorption and concentration (the mg L after the adsorption equilibrium
-1), V is the concentration (L) of ciprofloxacin solution, m is the quality (g) of adsorbent.Experimental result shows, generally greater than the adsorption capacity to other materials, but not the trace catalyst is more or less the same to the adsorption capacity of these several kinds of materials the MIP photochemical catalyst to the adsorption capacity of template molecule Ciprofloxacin.
(2) Ciprofloxacin of photochemical catalyst absorption same concentrations of preparation and the mixed solution of interfering material in (3) in the difference use-case 1; Through identical adsorption time; The centrifugation aaerosol solution; Measure the concentration of supernatant, calculate the adsorption capacity of catalyst, calculate its adsorptive selectivity then different material to different plant species according to formula.The result show the MIP-2 photochemical catalyst to the adsorption capacity of Ciprofloxacin apparently higher than its adsorption capacity to gatifloxacin and chloramphenicol; And blank imprinted polymer is little to three's adsorption capacity difference, explains and in the trace process, has improved the adsorption capacity of imprinted polymer to Ciprofloxacin.
Test three:: (1) is through changing consumption (the 0.5 g L of MIP-2 molecular engram photochemical catalyst
-1, 1.0 g L
-1, 1.5 g L
-1, 2.0 g L
-1, 2.5 g L
-1) examining or check the influence of catalyst amounts to photocatalytic degradation, it is 1.5 g L that the result is illustrated in catalyst amount
-1The time, its degradation efficiency to Ciprofloxacin is the highest, can reach more than 95 %.So selected catalyst amount is 1.5 g L in the experiment
-1
(2) with MIP-2 photochemical catalyst catalytic degradation variable concentrations (10,20,30,40,50 mg L under visible light
-1) ciprofloxacin solution; Examination when variable concentrations the molecular engram photochemical catalyst to the degradation kinetics of Ciprofloxacin; Can know through calculating and match kinetics equation; The process of molecular engram photocatalyst for degrading Ciprofloxacin meets the pseudo-first-order kinetic model, when the Ciprofloxacin initial concentration is 20 mg L
-1The time, MIP-2 is 0.042 min to the average degradation rate of Ciprofloxacin
-1
Embodiment 5: the Ciprofloxacin and the interfering material (gatifloxacin of the photocatalyst for degrading same concentrations for preparing in (3) in the use-case 1 respectively; Chloramphenicol) mixed solution is through calculating the degradation efficiency of different material and then calculating its selectivity factor to different material.
E% = 
×100
% (1);
D = 
(2);
α= 
(3);
α γ = 
(4)
C wherein
0, C
eBe respectively concentration (the mg L after the Ciprofloxacin initial sum is degraded
-1); D is a distribution coefficient, D
CIP, D
MBe respectively the distribution coefficient of Ciprofloxacin and interfering material; α is a selectivity factor, α
i, α
nBe respectively the selectivity factor of trace and blank polymer photochemical catalyst, α
rIt is the relative selectivity coefficient.
Experimental result shows, the MIP-2 photochemical catalyst is to the degradation efficiency of the Ciprofloxacin material apparently higher than other contrasts, and selectivity factor is also all greater than other interfering materials, and MIP-2 is respectively 1.26 and 4.37 to the relative selectivity coefficient of gatifloxacin and chloramphenicol.This be since the similarity degree of the molecular structure of gatifloxacin and Ciprofloxacin than the height of chloramphenicol, so selectivity factor is just lower comparatively speaking.Explanation has selectivity preferably with the synthetic MIP-2 molecular engram Ciprofloxacin photochemical catalyst of the method to Ciprofloxacin, thereby has realized the purpose to target substance Ciprofloxacin selectivity catalytic degradation.
Claims (4)
1. the preparation method of selectivity degraded Ciprofloxacin photochemical catalyst, carry out according to following step:
(1) hydro-thermal of ZnS semi-conducting material is synthetic: at first with Zn (COOH)
2And CS (NH
2)
21:2 ~ 5 are dissolved in an amount of distilled water in molar ratio; Stir 2 ~ 10 h at constant speed lower magnetic force both are fully mixed, then mixed solution is joined in the teflon-lined agitated reactor, total liquor capacity is no more than 80% of reactor volume; React 12 ~ 48 h down for 120 ~ 160 ℃ at constant temperature; Cooling naturally at room temperature after reaction finishes, the product that obtains alternately washs for several times centrifugation with distilled water and absolute ethyl alcohol; Dry under 50 ~ 70 ℃ of vacuum at last, finally obtain the uniform ZnS semiconductor of particle diameter micron ball;
(2) ZnS surface modification: ZnS semi-conducting material synthetic in (1) is distributed in the methanol solution of acrylamide, makes the amount ratio of ZnS and acrylamide be 6:1 ~ 3:1, under the room temperature condition, with constant speed magnetic agitation 10 ~ 20 h;
(3) preparation of molecularly imprinted polymer photochemical catalyst: the preparation of molecularly imprinted polymer; At first than 1:4 ~ 1:10 be dissolved in the methyl alcohol of certain volume by amount template molecule Ciprofloxacin and function monomer α-Jia Jibingxisuan; Stir 2 ~ 8 h at ambient temperature and make its abundant polymerization; The amount that adds crosslinking agent EGDMA and initiator A IBN then is than being 1:1 ~ 1:3; And small amount of toluene is as pore-foaming agent, adds ZnS semi-conducting material after acrylic amide modified at last as the carrier of imprinted polymer, feeds N
210 min are to remove the O in the solution
2, said mixture is at 50 ~ 80 ℃ of following polymerisation 10 ~ 30 h of water bath with thermostatic control;
(4) solid powder substance that obtains is crossed 200 mesh sieves after grinding, the template molecule in 70 ~ 85 ℃ of water-bath wash-outs of temperature imprinted polymer then, eluent is methyl alcohol and acetate, its volume ratio is 9:1 ~ 7:3.
2. the preparation method of a kind of selectivity degraded Ciprofloxacin photochemical catalyst according to claim 1 is characterized in that wherein step (1) Zn (COOH)
2And CS (NH
2)
2The concentration of the aqueous solution is respectively 0.1 mol/L and 0.2 mol/L.
3. the preparation method of a kind of selectivity degraded Ciprofloxacin photochemical catalyst according to claim 1 is characterized in that concentration is 0.2mol/L in the methanol solution of acrylamide in the step (2) wherein.
4. the preparation method of a kind of selectivity degraded Ciprofloxacin photochemical catalyst according to claim 1 is characterized in that the concentration of the methanol solution of template molecule Ciprofloxacin and function monomer α-Jia Jibingxisuan in the step (3) wherein is 0.1 mol/L ~ 0.25mol/L.
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| CN102786643B (en) * | 2012-08-08 | 2014-03-12 | 江苏大学 | Preparation method and application of molecularly imprinted polymer of sulfadiazine for controlled catalytic degradation |
| CN103785476B (en) * | 2014-01-15 | 2016-04-06 | 江苏大学 | Based on the preparation method of the surface imprinted CdS composite photo-catalyst of magnetic carbon material |
| CN107522814A (en) * | 2016-06-22 | 2017-12-29 | 张家港市金港镇宏业海绵复合厂 | The preparation method of titanium dioxide optical catalyst |
| CN106955726B (en) * | 2017-02-23 | 2019-05-31 | 江苏大学 | A kind of the molecular engram catalytic membrane and preparation method of degradation selectivity Ciprofloxacin |
| CN107162097B (en) * | 2017-05-10 | 2021-02-02 | 同济大学 | Selective photoelectrocatalysis removal method of low-concentration 17 beta-estradiol in coexisting system |
| 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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| CN1868580A (en) * | 2006-06-23 | 2006-11-29 | 华中科技大学 | Artificial anitibody type composite photocatalyst and its prepn. method |
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