CN102836702A - Transition metal ion imprinting supported M-POPD-TiO2-floating bead composite photocatalyst and preparation method and application thereof - Google Patents
Transition metal ion imprinting supported M-POPD-TiO2-floating bead composite photocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of photocatalyst preparation and relates to a sol-gel-photo-initiation poly-imprinting method, in particular to a transition metal ion imprinting supported M-POPD-TiO2-floating bead composite photocatalyst and a preparation method and application of the transition metal ion imprinting supported M-POPD-TiO2-floating bead composite photocatalyst. The preparation method of the transition metal ion imprinting supported M-POPD-TiO2-floating bead composite photocatalyst is disclosed by the invention; the surface of the activated floating bead of coal ash is coated with titanium dioxide so as to prepare TiO2-floating bead supported photocatalyst; transition metal ion is immobilized on the surface of catalyst by ion imprinting technology without being eluted, thus, a circulating system is formed on the surface of the catalyst; charge transfer is accelerated so as to achieve an aim of cooperating or promoting to degrade organic pollutant in environment by photocatalysis; M-POPD-TiO2-floating bead composite photocatalyst is prepared by the method disclosed by the invention; therefore, effective separation of photoproduction electron and electron-hole pairs is realized; light source can be utilized effectively so as to achieve an application aim of degrading antibiotic waste water in the environment.
Description
Technical field
The invention belongs to the photochemical catalyst preparing technical field, relate to the method for sol-gel-light initiation polymerization trace, particularly a kind of transition metal ions trace support type M-POPD-TiO
2-float bead composite photochemical catalyst.
Background technology
In recent years, constantly detect the medical compounds existence of (comprising antibiotic) in the water environment, can both find the existence of these compounds in surface water, underground water, sewage or even the drinking water.Cause in the medical compounds of environmental pollution that at all antibiotic is owing to its high consumption rate in veterinary science and physianthropy is occupied critical role.Overwhelming majority antibiotic can not be fully absorbed by body, have approximately 90% antibiotic with original shape or metabolin form via the excrement of patient and livestock and poultry, urinate and enter environment.Residual antibiotic in the environment can be induced the generation drug tolerant bacteria; Influence the microorganism in the environment; Thereby destruction balance of ecosystem; Also can influence growth and development of plant, even have influence on human 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, particularly to titanium dioxide (TiO
2) modification all improved its catalytic activity to a great extent, it is active to have solved the light degradation that only is confined to ultraviolet region, makes it can effectively handle pollutants such as waste water in the life, waste gas down at visible light (sunshine).
Conducting polymer has various structure, special mechanism of doping effect, and fine environment stability is easy to preparation and high conductivity.Utilize conducting polymer modified TiO
2, the TiO after the modification
2Photocatalytic activity under visible light increases, this be since conducting polymer to absorption of visible light and can make the effective carrier that photogenerated charge separates.Doped metal ion can change TiO
2Energy gap with reduce the compound of electronics-hole, this helps to improve it to absorption of visible light, suppresses the compound of photo-generated carrier, improves the quantum yield of light-catalyzed reaction, and the efficient of degradable organic pollutant is significantly improved.
Molecular imprinting is the covalently or non-covalently effect that utilizes between template molecule and the monomer, prepare through cross-linked polymeric and wash-out have specific structure, to the affine adsorptivity of template molecule and the technology of identifiability polymer.Therefore; The inventor has introduced the ion blotting technology; Selected transition metal ions is immobilized at catalyst surface and without wash-out with it through the ion blotting technology; Thereby form a circulating system at catalyst surface, accelerated charge shifts, the purpose that makes it reach collaborative or promote the organic pollution in the photocatalytic degradation environment.
Summary of the invention
A kind of transition metal ions trace support type M-POPD-TiO
2-float the preparation method of bead composite photochemical catalyst, be that the bead surface cladding titanium dioxide that floats after flyash is activated makes TiO
2-float the pearl loaded photocatalyst, utilize the ion blotting technology that transition metal ions is immobilized at catalyst surface again.
The pearl that floats of activation of the present invention is that fly ash micro-sphere is floated pearl through what the water flotation obtained, obtains through processing such as rinsing, acidifying, roastings according to usual operation.
TiO of the present invention
2-the preparation of floating the pearl loaded photocatalyst comprises the steps:
Steps A, butyl titanate is mixed with absolute ethyl alcohol and is uniformly dispersed, wherein butyl titanate and absolute ethyl alcohol volume ratio are 1:4;
Step B, in above-mentioned system, dropwise add the mixed liquor of forming by concentrated hydrochloric acid, distilled water and absolute ethyl alcohol; Be stirred to the colloidal sol shape; Make TiO 2 sol, wherein concentrated hydrochloric acid: distilled water: the volume ratio of absolute ethyl alcohol is 1:15:180, and said concentration of hydrochloric acid is 36 ~ 38%;
The pearl that floats of step C, activation that above-mentioned steps is made adds in the TiO 2 sol that step B makes, and is stirred to gel, ageing under the room temperature;
Step D, in air atmosphere with 400 ~ 600 ℃ the calcining 4h, naturally cool to room temperature.
The ion blotting technology of utilizing of the present invention comprises the steps: at catalyst surface transition metal ions is immobilized
Steps A, the TiO that above-mentioned steps is made
2-float the pearl loaded photocatalyst to join in the distilled water solution that contains o-phenylenediamine and transition metal nitrate, and to use concentrated hydrochloric acid adjustment pH value of solution value be 2 ~ 6, wherein said TiO
2-floating the pearl loaded photocatalyst: distilled water: o-phenylenediamine: the ratio of transition metal nitrate is 1g:40 ~ 100mL: 0.0025 ~ 0.3g:0 ~ 0.02g, and wherein said concentrated hydrochloric acid concentration is 36 ~ 38%;
Step B, with after the ultrasonic dispersion of the mixed solution of steps A, the unglazed 24h that leaves standstill;
Step C, under ultraviolet light conditions, reclaim filtering solid particles behind illumination reaction 0 ~ 60min, wherein said ultraviolet light 300W, λ < 420nm;
Step D, with the Na of 0.04mol/L
2CO
3Solution and deionized water are washed till neutrality with solid particle, and use absolute ethyl alcohol drip washing;
Step e, place 60 ℃ vacuum drying chamber to dry step D gained solid particle.
Transition metal nitrate of the present invention can be the mixture of one or several the above-mentioned metal nitrate arbitrary proportions among Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, Mo, Tc, Rh, Pd, Ag, W, Re, the Os.
In a preferred embodiment of the present invention, transition metal nitrate of the present invention can be the mixture of one or several the above-mentioned metal nitrate arbitrary proportions among Zn, Cu, Cr, Fe, Co, the Ni.
Utilize the present invention to adopt sol-gel technology preparing to go out TiO
2-float bead composite photochemical catalyst, with the ion blotting technology it is carried out the ion blotting support type M-POPD-TiO that prepared by surface modification goes out to have higher catalytic activity
2-float bead composite photochemical catalyst, and it is applied to antibiotic degraded in the waste water.
Photocatalytic activity evaluation experimental method
In DW-01 type photochemical reaction appearance (available from Educational Instrument Factory of Yangzhou University), carry out; Visible lamp irradiation adds the antibiotic simulated wastewater in the reactor and measures its initial value, adds composite photo-catalyst then; Magnetic agitation is also opened the aerator bubbling air and is kept catalyst to be in suspending or afloat; Illumination process interval 10min sample analysis, get the absorbance that supernatant liquor is measured antibiotic maximum absorption wave strong point after the centrifugation, and pass through formula:
DC=[（A
0-A
i）/A
0]×100%
Calculate degradation rate, wherein A
0The absorbance of antibiotic solution when reaching adsorption equilibrium, A
iThe absorbance of the antibiotic solution of measuring for timing sampling.
Beneficial effect
Transition metal ions is modified the back photochemical catalyst can effectively improve the right separative efficiency of light induced electron and hole, has electric conductivity after the function monomer polymerization simultaneously, in immobilized transition metal ions, has accelerated the transfer of electronics; Loaded catalyst helps to improve the efficiency of light energy utilization and the rate of recovery of catalyst; Has the advantage of handling antibiotics waste water preferably.Its advantage is the immobilized surface at photochemical catalyst of transition metal ions is made its difficult drop-off; And cyclic process of structure in system; Realize light induced electron and right effectively the separating in hole, can effectively utilize light source, reach the purpose of antibiotic waste water in effective degraded environment.
Description of drawings
Fig. 1 transition metal ions trace support type M-POPD-TiO
2-float the energy dispersion X-ray spectrum (EDS) of bead composite photochemical catalyst;
Fig. 2 transition metal ions trace support type M-POPD-TiO
2-float the sem photograph (SEM) of bead composite photochemical catalyst;
Fig. 3 transition metal ions trace support type M-POPD-TiO
2-float the X-ray diffraction analysis figure (XRD) of bead composite photochemical catalyst;
Fig. 4 TiO
2-float pearl, POPD-TiO
2-float pearl and transition metal ions trace support type M-POPD-TiO
2-float the ultraviolet-visible spectrogram (UV-Vis) of bead composite photochemical catalyst;
Fig. 5 utilizes ion blotting technology preparation transition metal ions trace support type M-POPD-TiO
2-float the generative process sketch map of bead composite photochemical catalyst.
The specific embodiment
Below in conjunction with the practical implementation instance the present invention is elaborated, so that those skilled in the art understand the present invention better, but the present invention is not limited to following examples.
Embodiment 1
(1) fly ash micro-sphere of buying (table mountain Yaomeng power plant) is floated pearl through what the water flotation obtained, obtain the pearl that floats of activation through processing such as rinsing, acidifying, roastings; Butyl titanate and absolute ethyl alcohol at the uniform velocity are stirred to even dispersion by the mixed of 1:4 and with solution, dropwise add the mixed liquor that mixes by the volume ratio of 1:15:180 by concentrated hydrochloric acid, distilled water and absolute ethyl alcohol again, be stirred to the colloidal sol shape fast, make TiO
2Colloidal sol; To pass through pretreated activation and float pearl immersion TiO
2In the colloidal sol, at the uniform velocity stir and, at room temperature in air atmosphere, calcine 4h again after the ageing, naturally cool to room temperature, promptly obtain TiO with 400 ℃ to gel
2-float the pearl loaded photocatalyst;
(2) with the TiO that makes in the above-mentioned steps (1)
2-floating the pearl loaded photocatalyst carries out the photocatalytic degradation test in the photochemical reaction appearance, and the photometry catalyst is to the degradation rate of tetracycline.
(1) fly ash micro-sphere of buying (table mountain Yaomeng power plant) is floated pearl through what the water flotation obtained, obtain the pearl that floats of activation through processing such as rinsing, acidifying, roastings; Butyl titanate and absolute ethyl alcohol at the uniform velocity are stirred to even dispersion by the mixed of 1:4 and with solution, dropwise add the mixed liquor that mixes by the volume ratio of 1:15:180 by concentrated hydrochloric acid, distilled water and absolute ethyl alcohol again, be stirred to the colloidal sol shape fast, make TiO
2Colloidal sol; To pass through pretreated activation and float pearl immersion TiO
2In the colloidal sol, at the uniform velocity stir and, at room temperature in air atmosphere, calcine 4h again after the ageing, naturally cool to room temperature, promptly obtain TiO with 500 ℃ to gel
2-float the pearl loaded photocatalyst;
(2) with the TiO that makes in the above-mentioned steps (1)
2-floating the pearl loaded photocatalyst carries out the photocatalytic degradation test in the photochemical reaction appearance, and the photometry catalyst is to the degradation rate of tetracycline.
Embodiment 3
(1) fly ash micro-sphere of buying (table mountain Yaomeng power plant) is floated pearl through what the water flotation obtained, obtain the pearl that floats of activation through processing such as rinsing, acidifying, roastings; Butyl titanate and absolute ethyl alcohol at the uniform velocity are stirred to even dispersion by the mixed of 1:4 and with solution, dropwise add the mixed liquor that mixes by the volume ratio of 1:15:180 by concentrated hydrochloric acid, distilled water and absolute ethyl alcohol again, be stirred to the colloidal sol shape fast, make TiO
2Colloidal sol; To pass through pretreated activation and float pearl immersion TiO
2In the colloidal sol, at the uniform velocity stir and, at room temperature in air atmosphere, calcine 4h again after the ageing, naturally cool to room temperature, promptly obtain TiO with 600 ℃ to gel
2-float the pearl loaded photocatalyst;
(2) with the TiO that makes in the above-mentioned steps (1)
2-floating the pearl loaded photocatalyst carries out the photocatalytic degradation test in the photochemical reaction appearance, and the photometry catalyst is to the degradation rate of tetracycline.Relatively obtain best calcining heat.
Embodiment 4
(1) fly ash micro-sphere of buying (table mountain Yaomeng power plant) is floated pearl through what the water flotation obtained, obtain the pearl that floats of activation through processing such as rinsing, acidifying, roastings; Butyl titanate and absolute ethyl alcohol at the uniform velocity are stirred to even dispersion by the mixed of 1:4 and with solution, dropwise add the mixed liquor that mixes by the volume ratio of 1:15:180 by concentrated hydrochloric acid, distilled water and absolute ethyl alcohol again, be stirred to the colloidal sol shape fast, make TiO
2Colloidal sol; To pass through pretreated activation and float pearl immersion TiO
2In the colloidal sol, at the uniform velocity stir and, at room temperature in air atmosphere, calcine 4h again after the ageing, naturally cool to room temperature, promptly obtain TiO with 500 ℃ to gel
2-float the pearl loaded photocatalyst;
(2) with the TiO that makes in the above-mentioned steps (1)
2-floating the pearl loaded photocatalyst and join 50mL and contain in the aqueous solution of hydrochloric acid of o-phenylenediamine of 0.0025g, ultrasonic dispersion 5min leaves standstill 24h at no optical condition lower seal, at ultraviolet light conditions (300W, λ<420nm), filtered and recycled solid particle behind the illumination initiation reaction 30min is used 0.04molLNa
2CO
3Solution and deionized water place 60 ℃ of vacuum drying chambers to dry to neutral also with after the absolute ethyl alcohol drip washing solid particle flushing, promptly obtain transition metal ions trace support type M-POPD-TiO
2-float bead composite photochemical catalyst;
(3) with the M-POPD-TiO that makes in the above-mentioned steps (2)
2-floating the pearl loaded photocatalyst carries out the photocatalytic degradation test in the photochemical reaction appearance, and the photometry catalyst is to the degradation rate of tetracycline.
Embodiment 5
(1) fly ash micro-sphere of buying (table mountain Yaomeng power plant) is floated pearl through what the water flotation obtained, obtain the pearl that floats of activation through processing such as rinsing, acidifying, roastings; Butyl titanate and absolute ethyl alcohol at the uniform velocity are stirred to even dispersion by the mixed of 1:4 and with solution, dropwise add the mixed liquor that mixes by the volume ratio of 1:15:180 by concentrated hydrochloric acid, distilled water and absolute ethyl alcohol again, be stirred to the colloidal sol shape fast, make TiO
2Colloidal sol; To pass through pretreated activation and float pearl immersion TiO
2In the colloidal sol, at the uniform velocity stir and, at room temperature in air atmosphere, calcine 4h again after the ageing, naturally cool to room temperature, promptly obtain TiO with 500 ℃ to gel
2-float the pearl loaded photocatalyst;
(2) with the TiO that makes in the above-mentioned steps (1)
2-floating the pearl loaded photocatalyst and join 50mL and contain in the aqueous solution of hydrochloric acid of o-phenylenediamine of 0.05g, ultrasonic dispersion 5min leaves standstill 24h at no optical condition lower seal, at ultraviolet light conditions (300W, λ<420nm), filtered and recycled solid particle behind the illumination initiation reaction 30min is used 0.04molLNa
2CO
3Solution and deionized water place 60 ℃ of vacuum drying chambers to dry to neutral also with after the absolute ethyl alcohol drip washing solid particle flushing, promptly obtain transition metal ions trace support type M-POPD-TiO
2-float bead composite photochemical catalyst;
(3) with the M-POPD-TiO that makes in the above-mentioned steps (2)
2-floating the pearl loaded photocatalyst carries out the photocatalytic degradation test in the photochemical reaction appearance, and the photometry catalyst is to the degradation rate of tetracycline.
Embodiment 6
(1) fly ash micro-sphere of buying (table mountain Yaomeng power plant) is floated pearl through what the water flotation obtained, obtain the pearl that floats of activation through processing such as rinsing, acidifying, roastings; Butyl titanate and absolute ethyl alcohol at the uniform velocity are stirred to even dispersion by the mixed of 1:4 and with solution, dropwise add the mixed liquor that mixes by the volume ratio of 1:15:180 by concentrated hydrochloric acid, distilled water and absolute ethyl alcohol again, be stirred to the colloidal sol shape fast, make TiO
2Colloidal sol; To pass through pretreated activation and float pearl immersion TiO
2In the colloidal sol, at the uniform velocity stir and, at room temperature in air atmosphere, calcine 4h again after the ageing, naturally cool to room temperature, promptly obtain TiO with 500 ℃ to gel
2-float the pearl loaded photocatalyst;
(2) with the TiO that makes in the above-mentioned steps (1)
2-floating the pearl loaded photocatalyst and join 50mL and contain in the aqueous solution of hydrochloric acid of o-phenylenediamine of 0.1g, ultrasonic dispersion 5min leaves standstill 24h at no optical condition lower seal, at ultraviolet light conditions (300W, λ<420nm), filtered and recycled solid particle behind the illumination initiation reaction 30min is used 0.04molLNa
2CO
3Solution and deionized water place 60 ℃ of vacuum drying chambers to dry to neutral also with after the absolute ethyl alcohol drip washing solid particle flushing, promptly obtain transition metal ions trace support type M-POPD-TiO
2-float bead composite photochemical catalyst;
(3) with the M-POPD-TiO that makes in the above-mentioned steps (2)
2-floating the pearl loaded photocatalyst carries out the photocatalytic degradation test in the photochemical reaction appearance, and the photometry catalyst is to the degradation rate of tetracycline.
Embodiment 7
(1) fly ash micro-sphere of buying (table mountain Yaomeng power plant) is floated pearl through what the water flotation obtained, obtain the pearl that floats of activation through processing such as rinsing, acidifying, roastings; Butyl titanate and absolute ethyl alcohol at the uniform velocity are stirred to even dispersion by the mixed of 1:4 and with solution, dropwise add the mixed liquor that mixes by the volume ratio of 1:15:180 by concentrated hydrochloric acid, distilled water and absolute ethyl alcohol again, be stirred to the colloidal sol shape fast, make TiO
2Colloidal sol; To pass through pretreated activation and float pearl immersion TiO
2In the colloidal sol, at the uniform velocity stir and, at room temperature in air atmosphere, calcine 4h again after the ageing, naturally cool to room temperature, promptly obtain TiO with 500 ℃ to gel
2-float the pearl loaded photocatalyst;
(2) with the TiO that makes in the above-mentioned steps (1)
2-floating the pearl loaded photocatalyst and join 50mL and contain in the aqueous solution of hydrochloric acid of o-phenylenediamine of 0.2g, ultrasonic dispersion 5min leaves standstill 24h at no optical condition lower seal, at ultraviolet light conditions (300W, λ<420nm), filtered and recycled solid particle behind the illumination initiation reaction 30min is used 0.04molLNa
2CO
3Solution and deionized water place 60 ℃ of vacuum drying chambers to dry to neutral also with after the absolute ethyl alcohol drip washing solid particle flushing, promptly obtain transition metal ions trace support type M-POPD-TiO
2-float bead composite photochemical catalyst;
(3) with the M-POPD-TiO that makes in the above-mentioned steps (2)
2-floating the pearl loaded photocatalyst carries out the photocatalytic degradation test in the photochemical reaction appearance, and the photometry catalyst is to the degradation rate of tetracycline.
(1) fly ash micro-sphere of buying (table mountain Yaomeng power plant) is floated pearl through what the water flotation obtained, obtain the pearl that floats of activation through processing such as rinsing, acidifying, roastings; Butyl titanate and absolute ethyl alcohol at the uniform velocity are stirred to even dispersion by the mixed of 1:4 and with solution, dropwise add the mixed liquor that mixes by the volume ratio of 1:15:180 by concentrated hydrochloric acid, distilled water and absolute ethyl alcohol again, be stirred to the colloidal sol shape fast, make TiO
2Colloidal sol; To pass through pretreated activation and float pearl immersion TiO
2In the colloidal sol, at the uniform velocity stir and, at room temperature in air atmosphere, calcine 4h again after the ageing, naturally cool to room temperature, promptly obtain TiO with 500 ℃ to gel
2-float the pearl loaded photocatalyst;
(2) with the TiO that makes in the above-mentioned steps (1)
2-floating the pearl loaded photocatalyst and join 50mL and contain in the aqueous solution of hydrochloric acid of o-phenylenediamine of 0.3g, ultrasonic dispersion 5min leaves standstill 24h at no optical condition lower seal, at ultraviolet light conditions (300W, λ<420nm), filtered and recycled solid particle behind the illumination initiation reaction 30min is used 0.04molLNa
2CO
3Solution and deionized water place 60 ℃ of vacuum drying chambers to dry to neutral also with after the absolute ethyl alcohol drip washing solid particle flushing, promptly obtain transition metal ions trace support type M-POPD-TiO
2-float bead composite photochemical catalyst;
(3) with the M-POPD-TiO that makes in the above-mentioned steps (2)
2-floating the pearl loaded photocatalyst carries out the photocatalytic degradation test in the photochemical reaction appearance, and the photometry catalyst is to the degradation rate of tetracycline, and the best applied amount that relatively draws o-phenylenediamine is 0.1g.
Embodiment 9
(1) fly ash micro-sphere of buying (table mountain Yaomeng power plant) is floated pearl through what the water flotation obtained, obtain the pearl that floats of activation through processing such as rinsing, acidifying, roastings; Butyl titanate and absolute ethyl alcohol at the uniform velocity are stirred to even dispersion by the mixed of 1:4 and with solution, dropwise add the mixed liquor that mixes by the volume ratio of 1:15:180 by concentrated hydrochloric acid, distilled water and absolute ethyl alcohol again, be stirred to the colloidal sol shape fast, make TiO
2Colloidal sol; To pass through pretreated activation and float pearl immersion TiO
2In the colloidal sol, at the uniform velocity stir and, at room temperature in air atmosphere, calcine 4h again after the ageing, naturally cool to room temperature, promptly obtain TiO with 500 ℃ to gel
2-float the pearl loaded photocatalyst;
(2) with the TiO that makes in the above-mentioned steps (1)
2-float the pearl loaded photocatalyst and join 50mL and contain in the aqueous hydrochloric acid solution of (0g, 0.001g, 0.002g, 0.005g, 0.01g, 0.02g) transition metal nitrate of o-phenylenediamine and different amounts of 0.1g; Ultrasonic dispersion 5min; Leave standstill 24h at no optical condition lower seal, transition metal nitrate can be the mixture of one or several the above-mentioned metal nitrate arbitrary proportions among Zn, Cu, Cr, Fe, Co, the Ni; At ultraviolet light conditions (300W, λ<420nm), filtered and recycled solid particle behind the illumination initiation reaction 30min is used 0.04molLNa
2CO
3Solution and deionized water place 60 ℃ of vacuum drying chambers to dry to neutral also with after the absolute ethyl alcohol drip washing solid particle flushing, promptly obtain transition metal ions trace support type M-POPD-TiO
2-float bead composite photochemical catalyst.
(3) get each sample M1-M5 (M:Zn of gained in the 0.1g step (2) respectively
2+, Cr
3+, Co
2+, Cu
2+, Fe
3+, Ni
2+) in the photochemical reaction appearance, carrying out the photocatalytic degradation test, the photometry catalyst gets transition metal ions Zn to the degradation rate of tetracycline
2+, Cr
3+, Co
2+, Cu
2+, Fe
3+, Ni
2+Best dosage be respectively 0.001g, 0.001g, 0.002g, 0.005g, 0.002g, 0.02g, and note is made blank, Z1, C1, Co2, Cu3, F2 and N5.
(4): preparing blank, Z1, C1, Co2, Cu3, F2 and N5 with step (3) is photochemical catalyst; It is active to investigate its light degradation to different antibiotic (tetracycline, quadracycline, Ciprofloxacin, terramycin and chloramphenicol) waste water; The result shows that the transition metal ions trace photochemical catalyst of preparation is tetracycline to the active order of different antibiotic light degradation>quadracycline>terramycin>Ciprofloxacin, wherein have only Co2 specific activity quadracycline when the degraded tetracycline low; In addition, 6 kinds of photochemical catalysts all are contrary trend to the degraded of chloramphenicol.
(5): it is best to the degradation effect of tetracycline to draw photochemical catalyst through step (4); Then select tetracycline as the degraded object; Tetracycline to variable concentrations (5 mg/L, 10mg/L, 20mg/L, 30mg/L, 50 mg/L) is degraded, and investigates target substrates concentration to the active influence of trace photocatalyst for degrading.Display density is low more as a result, and the degradation effect of trace photochemical catalyst is good more; The result of 5 mg/L tetracyclines of degrading shows that the active order of the light degradation of prepared transition metal ions trace photochemical catalyst is C1>N5>F2>Cu3>Z5>blank, but along with the activity of these 6 kinds of trace photochemical catalysts of increase of concentration changes.
The explanation of embodiment:
1, calcining heat is at 400 ~ 600 ℃, and this condition is at preparation TiO
2-when floating pearl; Only, temperature just can carry out next step experiment after confirming; So do not have for second step in fact at instance (2) and (3) the inside; The first step finishes the back and has just directly carried out the photocatalytic activity evaluation experimental, because this process only need draw optimum calcining heat, so all select for use the tetracycline of 50mg/L just passable as degradation of contaminant;
2, the applied amount 0.0025 ~ 0.3g of o-phenylenediamine; Confirm just can carry out next step adding transition metal ions after this amount; So in the amount of investigating o-phenylenediamine is need not add transition metal salt, the investigation of photocatalytic activity also only need select for use the tetracycline of 50mg/L just passable as degradation of contaminant.
Illustrate:
Fig. 1 transition metal ions trace support type M-POPD-TiO
2-float EDS and Fig. 2 SEM diagram of bead composite photochemical catalyst, as can be seen from the figure the main component of catalyst sample base material is Al, Si composite oxides, that the top layer covers is TiO
2, and kept the spherical structure of catalyst sample preferably.
Fig. 3 transition metal ions trace support type M-POPD-TiO
2-float the X diffraction diagram of bead composite photochemical catalyst, as can be seen from the figure the ion blotting composite photo-catalyst does not change Detitanium-ore-type TiO
2The diffractive features peak, this and standard Detitanium-ore-type TiO
2 Characteristic diffraction peak 2 θ of crystal=25.5 °, 36.4 °, 48.1 °, 54 ° corresponding, makes TiO in the catalyst sample
2Keep higher photocatalytic activity; Catalyst after the modification has a wide diffraction maximum between 27 °-30 °, this maybe since polymer and metal ion cause; Other diffraction maximums are mainly base material fly ash float composite oxides and produce.
Fig. 4 is TiO
2-float pearl, POPD-TiO
2-float pearl and transition metal ions trace support type M-POPD-TiO
2-float the UV-Vis spectrogram of bead composite photochemical catalyst, as can be seen from the figure, the absorbing properties of the photochemical catalyst behind the trace obviously is better than the not TiO of trace
2-float the pearly-lustre catalyst, show that the composite photo-catalyst of trace iron ion has ultraviolet and visible absorption ability preferably, and tangible red shift has taken place in the photochemical catalyst sample behind the trace.
Fig. 5 is for utilizing ion blotting technology preparation transition metal ions trace support type M-POPD-TiO
2-float the generative process sketch map of bead composite photochemical catalyst.
Claims (8)
1. transition metal ions trace support type M-POPD-TiO
2-float the preparation method of bead composite photochemical catalyst, be that the bead surface cladding titanium dioxide that floats after flyash is activated makes TiO
2-float the pearl loaded photocatalyst, utilize the ion blotting technology that transition metal ions is immobilized at catalyst surface again.
2. a kind of transition metal ions trace support type M-POPD-TiO according to claim 1
2-float the preparation method of bead composite photochemical catalyst, it is characterized in that the pearl that floats of described activation is that fly ash micro-sphere is floated pearl through what the water flotation obtained, obtains through processing such as rinsing, acidifying, roastings according to usual operation.
3. a kind of transition metal ions trace support type M-POPD-TiO according to claim 1
2-float the preparation method of bead composite photochemical catalyst, it is characterized in that described TiO
2-the preparation of floating the pearl loaded photocatalyst comprises the steps:
Steps A, butyl titanate is mixed with absolute ethyl alcohol and is uniformly dispersed, wherein butyl titanate and absolute ethyl alcohol volume ratio are 1:4;
Step B, in above-mentioned system, dropwise add the mixed liquor of being made up of concentrated hydrochloric acid, distilled water and absolute ethyl alcohol, be stirred to the colloidal sol shape, make TiO 2 sol, wherein concentrated hydrochloric acid: distilled water: the volume ratio of absolute ethyl alcohol is 1:15:180;
The pearl that floats of step C, activation that step 2 is made adds in the TiO 2 sol that step B makes, and is stirred to gel, ageing under the room temperature;
Step D, in air atmosphere with 400 ~ 600 ℃ the calcining 5h, naturally cool to room temperature.
4. a kind of transition metal ions trace support type M-POPD-TiO according to claim 1
2-float the preparation method of bead composite photochemical catalyst, it is characterized in that the described ion blotting technology of utilizing comprises the steps: at catalyst surface transition metal ions is immobilized
Steps A, obtained in the above step TiO
2 - cenospheres photocatalytic added to a solution of o-phenylenediamine and a transition metal nitrate in distilled water and treated with concentrated hydrochloric acid adjusting the pH value of 2 to 6, wherein said TiO
2 - cenospheres photocatalytic: Distilled [High Xun 1]? o-phenylenediamine: transition metal nitrate The proportion of salt 1g: 40 ~ 100mL: [High Xun 2]?: 0 ~ 0.02g, concentration of the concentrated hydrochloric acid, 36 to 38%;
Step B, with after the ultrasonic dispersion of the mixed solution of steps A, the unglazed 24h that leaves standstill;
Step C, under ultraviolet light conditions, reclaim filtering solid particles behind illumination reaction 0 ~ 60min, wherein said ultraviolet light 300W, λ < 420nm;
Step D, with the Na of 0.04mol/L
2CO
3Solution and deionized water are washed till neutrality with solid particle, and use absolute ethyl alcohol drip washing;
Step e, place 60 ℃ vacuum drying chamber to dry step D gained solid particle.
5. a kind of transition metal ions trace support type M-POPD-TiO according to claim 4
2-float the preparation method of bead composite photochemical catalyst; It is characterized in that described transition metal nitrate can be the mixture of one or several the above-mentioned metal nitrate arbitrary proportions among Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, Mo, Tc, Rh, Pd, Ag, W, Re, the Os.
6. a kind of transition metal ions trace support type M-POPD-TiO according to claim 5
2-float the preparation method of bead composite photochemical catalyst, it is characterized in that described transition metal nitrate can be the mixture of one or several the above-mentioned metal nitrate arbitrary proportions among Zn, Cu, Cr, Fe, Co, the Ni.
7. the transition metal ions trace support type M-POPD-TiO that makes according to the said preparation method of claim 1
2-float bead composite photochemical catalyst.
8. according to the said transition metal ions trace of claim 7 support type M-POPD-TiO
2-float the bead composite photochemical catalyst antibiotic application of in waste water, degrading.
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| CN101961662A (en) * | 2010-07-29 | 2011-02-02 | 江苏大学 | Method for preparing ion imprinting supported composite photocatalyst |
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| CN101961662A (en) * | 2010-07-29 | 2011-02-02 | 江苏大学 | Method for preparing ion imprinting supported composite photocatalyst |
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