CN102847558B - Method for preparing conjugated polyene/nano titanium dioxide visible-light-induced photocatalyst by taking natural rubber as raw material - Google Patents
Method for preparing conjugated polyene/nano titanium dioxide visible-light-induced photocatalyst by taking natural rubber as raw material Download PDFInfo
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Abstract
The invention relates to a method for preparing a conjugated polyene/nano titanium dioxide visible-light-induced photocatalyst by taking natural rubber as a raw material, belonging to the technical field of photocatalyst new materials for environment purification. The method comprises the following steps: preparing natural rubber/nano titanium dioxide composite particles from natural rubber and nano titanium dioxide taken as raw materials through a solution impregnation composite method; using newly-prepared bromine water to perform bromine addition reaction on natural rubber molecules on the surface of the nano titanium dioxide; then performing heat treatment to remove hydrogen bromide; and doping with iodine to obtain the conjugated polyene/nano titanium dioxide visible-light-induced photocatalyst. The invention has the following advantages: the conventional polymer natural rubber is used as the raw material, the cost is low, and the polymerization process and the polymer molecular weight are easy to control; and the prepared conjugated polyene/nano titanium dioxide visible-light-induced photocatalyst has favorable visible-light-induced photocatalytic activity, and the catalytic degradation effect on pollutants under the irradiation of a common daylight lamp is remarkable. Thus, the invention provides a new way for recovery and reutilization of natural rubber for preparation of environment purification materials.
Description
Technical field
The invention belongs to depollution of environment photochemical catalyst new material technology field, relate to a kind of preparation method of take the visible light catalyst that the conjugated polyene that natural rubber is raw material/titanic oxide nano compound material forms.
Background technology
The survival and development that human society in the water body that is accompanied by process of industrialization and comes and atmosphere pollution serious threat, the common method of processing at present toxic pollutant in water and air mainly contains physisorphtion, chemical method, microbial method etc., but these methods exist, and efficiency is low, energy consumption is high, technique is loaded down with trivial details, purify the limitations such as not thorough, and the processing environment of therefore employing new technology pollutes and has important practical significance.
Nano-TiO
2be a kind of typical N-shaped semi-conducting material, can under illumination effect, produce high mars free radical, the oxidation operation of many difficult degradations can be degraded into carbon dioxide and water, reach the object of eliminating environmental pollution.Compare nano-TiO with other environmental treatment technology
2phase photo catalytic oxidation processes degrading organic pollutants has the advantages such as energy consumption is low, easy and simple to handle, reaction condition is gentle, secondary pollution is few, at sewage disposal, air cleaning, the aspects such as degerming of keeping a public place clean, has a good application prospect.But nano-TiO
2wider forbidden band causes it to only have the ultraviolet light of absorption could produce photocatalytic activity, has greatly limited its extensive use under sunshine; TiO in addition
2light induced electron/hole-recombination probability that photochemical catalyst produces is higher, also affects its photocatalytic degradation ability.In order to improve TiO
2the method taked of visible light catalysis activity mainly contain noble metal loading, transient metal doped, nonmetal doping, organic dye sensitized etc.These methods can improve the visible light catalysis activity of nano titanium oxide more significantly, but also have the shortcomings such as high such as cost, photocatalysis performance is unstable, cause its photocatalytic degradation efficiency still not ideal enough.
Research in recent years finds to have the polymer modification nano-TiO of conjugated structure
2can obviously improve its visible light catalysis activity.This is because polymer molecule has large conjugatedπbond structure, has increased TiO
2absorption to visible ray; In conjugated polymer molecule, the wave function of pi-electron motion is not spherical symmetric simultaneously, in strand direction, there is larger cloud density, valence electron tends to move along strand, make polymer there is certain electric conductivity, thereby can reduce the recombination rate in light induced electron-hole, improve photocatalysis quantum efficiency, improve the photocatalytic activity of compound particle under visible ray.The normal polymer adopting is polyaniline, polypyrrole, polythiophene and derivative thereof.The shortcoming of these polymer is water insoluble and common solvent, is generally method and nano-TiO by in-situ polymerization
2compound, its molecular weight and compound uniformity coefficient are uncontrollable, and cost is higher, is unsuitable for a large amount of production and applications.
The main component of natural rubber is polyisoprene, is the natural polymer that a kind of molecule contains partial double bond, is widely used in the fields such as rubber, dress material, adhesive.The two keys that comprise in molecule very easily with bromine generation addition reaction, the product after addition can carry out again the reaction that removes of hydrogen bromide under hot conditions, obtains the polymer of conjugated polyene structure.About take conjugated polyene and the compound visible light catalytic agent material of preparing of nano titanium oxide that natural rubber is raw material, have not yet to see related documents report.
Summary of the invention
The object of the present invention is to provide a kind of conventional polymer natural rubber that adopts to obtain through processing the preparation method that conjugated polyene decorated nanometer titanium dioxide forms visible light catalyst.Conjugated polyene/titanic oxide nano compound material prepared by the method just can show good photocatalysis performance under common fluorescent lamp irradiates, and the present invention also prepares surrounding purifying material for natural rubber recycling provides an approach.
Thinking of the present invention is, adopting nano titanium oxide and natural rubber is raw material, by solution impregnation composite algorithm, prepare natural rubber/nano titanium oxide composite particles, then utilize bromine addition reaction and dehydrobromination reaction, obtain conjugated polyene/nano-titanium dioxide visible light catalyst.
The present invention is achieved by following technical proposals:
A preparation method for conjugated polyene/nano-titanium dioxide visible light catalyst that the natural rubber of take is raw material, it comprises the following steps:
A. in toluene, add natural rubber, airtight stirring, the toluene solution that to be mixed with containing natural rubber mass concentration be 1g/L～4g/L;
B. to gained in described step a, containing in the toluene solution of natural rubber, add nano-TiO
2, described natural rubber and TiO
2mass ratio be 1:8～20, ultrasonic dispersion 30～40min, then under agitation adsorbs after 3～5h, after filtration, separated, the dry natural rubber/nano-TiO that obtains
2composite particles;
C. by gained natural rubber/nano-TiO in described step b
2composite particles joins in the saturated bromine aqueous solution of new system, controls natural rubber/nano-TiO
2composite particles and bromine aqueous solution mass ratio are 1:20～30, are placed in dark place and soak 8～12h, afterwards by product isolated by filtration, with 500～1000mL distilled water, wash, again by 50～100mL soaked in absolute ethyl alcohol, wash 3 times, be dried to constant weight, obtain brominated polymers/nano titanium oxide composite particles;
D. by gained brominated polymers/nano titanium oxide composite particles heat treatment 3～5h at 80 ℃～120 ℃ in described step c, make brominated polymers remove hydrogen bromide and generate conjugated polyene, obtain conjugated polyene/nano titanium oxide composite particles;
E. gained conjugated polyene/nano titanium oxide composite particles in described steps d is put into the ethanolic solution of counting 0.05～0.09mol/L with iodine concentration, at 60～78 ℃, stir and soak 1～2h, gained produces People's Armed Police's isolated by filtration, and ethanol obtains conjugated polyene/nano TiO 2 visible light catalyst after washing, being dried.
Preferably, the mass ratio of natural rubber described in step b and TiO2 is 1:8～20, and the best is 1:10.
Preferably, the mass concentration of bromine aqueous solution described in step c is 2.8%～3.1%.
Preferably, in described a kind of preparation method of take conjugated polyene/nano-titanium dioxide visible light catalyst that natural rubber is raw material, natural rubber/nano-TiO described in step c
2composite particles and bromine aqueous solution mass ratio are 1:25.Brominated polymers/nano titanium oxide composite particles heat treatment 4h at 100 ℃ in described steps d.
Described a kind of preparation method of take conjugated polyene/nano-titanium dioxide visible light catalyst that natural rubber is raw material, it comprises following concrete steps:
A. take 0.33g natural rubber and be placed in conical flask, add 100mL toluene, airtight, be stirred to natural rubber and dissolve completely, be mixed with the toluene solution containing natural rubber;
B. according to natural rubber and nano-TiO
2mass ratio is the ratio of 1:10, takes 2.0g nano-TiO
2particle add described in 60mL step a containing in the toluene solution of natural rubber, with ultrasonic dispersions of supersonic wave cleaning machine 30min, then stir suction filtration after immersion 4h, filter cake is dried 4h at 100 ℃, obtains natural rubber/nano-TiO
2composite particles;
C. by the natural rubber/nano-TiO of step b gained
2composite particles joins in the bromine aqueous solution that the mass concentration of new system is 3.0%, controls natural rubber/nano-TiO
2the mass ratio of composite particles and bromine aqueous solution is 1:25, and airtight water seal is placed in dark place and soaks 12h, afterwards by product isolated by filtration, and with the washing of 1000mL distilled water, and then with 100mL alcohol immersion, wash 3 times, must bromine Polymer/nano TiO after being dried
2composite particles;
D. by step c gained brominated polymers/nano-TiO
2composite particles heat treatment 4h in the baking oven of 100 ℃, to remove hydrogen bromide, obtains conjugated polyene/nano-TiO
2composite particles;
E. by steps d gained conjugated polyene/nano-TiO
2composite particles is put into the ethanolic solution of counting 0.06mol/L with iodine concentration, at 78.0 ℃, stirs and soaks 60min, and product is separated by filtration, and ethanol obtains conjugated polyene/nano-TiO after washing, being dried
2visible light catalyst.
The advantage that the present invention compared with prior art has is:
(1) adopting conventional polymer natural rubber is raw material, and cost is low, and polymerization process and polymer molecular weight are easily controlled;
(2) prepared conjugated polyene/nano-titanium dioxide visible light catalyst in the absorption intensity of visible region apparently higher than nano-TiO
2, under common fluorescent lamp irradiates, the effect of catalyzing and degrading pollutant methyl orange is remarkable.
(3) for natural rubber recycling, prepare surrounding purifying material an approach is provided.
Accompanying drawing explanation
Fig. 1 is conjugated polyene/nano TiO 2 visible light catalyst of the present invention and commodity nano-TiO
2(P-25) UV-Vis DRS absorption spectrum comparison diagram.
Fig. 2 is conjugated polyene/nano-TiO of the present invention
2visible light catalyst and commodity nano-TiO
2(P-25) photo-catalytic degradation of methyl-orange comparison diagram.
The specific embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1
Take 0.33g natural rubber and be placed in conical flask, add 100mL toluene, airtight, be stirred to natural rubber and dissolve completely.Then take 3.3g nano-TiO
2particle adds in the toluene solution of this natural rubber, with the ultrasonic dispersion of supersonic wave cleaning machine 30min, then suction filtration after stirring immersion 4h, filter cake is dried 4h at 100 ℃, obtains natural rubber/nano-TiO
2composite particles.By dried above-mentioned natural rubber/nano-TiO
2composite particles joins in the bromine aqueous solution that the mass concentration of new system is 3.0%, natural rubber/nano-TiO
2the mass ratio of composite particles and bromine aqueous solution is 1:25, and airtight water seal is placed in dark place and soaks 12h, and afterwards by product isolated by filtration, gained composite particles wash with enough distilled water, and then by alcohol immersion, wash 3 times, must brominated polymers/nano-TiO after being dried
2composite particles, then to remove hydrogen bromide, obtains conjugated polyene/nano-TiO by its heat treatment 4h in the baking oven of 100 ℃
2composite particles.Gained composite particles is put into the ethanolic solution of counting 0.06mol/L with iodine concentration, at 78.0 ℃, stirred and soak 60min, product is separated by filtration, and ethanol obtains conjugated polyene/nano-TiO after washing, being dried
2visible light catalyst.
The performance test of conjugated polyene/nano-titanium dioxide visible light catalyst that the method is prepared is to take methyl orange as model pollutant, and visible light source forms (between light source and reactor, added a cover optical filter filtering the ultraviolet light below 400nm) by two common 36W fluorescent lamps.In open reactor, add the methyl orange solution that 0.10g photochemical catalyst and 100mL concentration are 10mg/L, under dark condition, stirring 1h reaches after adsorption equilibrium, unlatching light source irradiates, regularly from degradation reaction liquid, sample, materialsed high speed centrifugation 15min, with separated light catalyst, is got to supernatant liquor, adopt 723 type spectrophotometers to measure absorbance under 464nm wavelength, by the variation of absorbance, can be calculated the degradation rate of methyl orange, and then obtain the catalytic activity of photochemical catalyst.Experiment records above-mentioned conjugated polyene/nano-TiO
2visible light catalyst is 0.406h to the degradation rate constant of methyl orange
-1, and commodity nano-TiO under the same terms
2(P-25) to the degradation rate constant of methyl orange, be 0.024h
-1, i.e. conjugated polyene/nano-TiO
2visible light catalysis activity is commodity nano-TiOs
216.9 times.
Take 0.50g natural rubber and be placed in conical flask, add 150mL toluene, airtight, be stirred to natural rubber and dissolve completely.Then take 5.0g nano-TiO
2particle adds in the toluene solution of this natural rubber, with the ultrasonic dispersion of supersonic wave cleaning machine 30min, then suction filtration after stirring immersion 4h, filter cake is dried 4h at 100 ℃, obtains natural rubber/nano-TiO
2composite particles.By dried above-mentioned natural rubber/nano-TiO
2composite particles joins in the bromine aqueous solution that the mass concentration of new system is 3.0%, the mass ratio of composite particles and bromine aqueous solution is 1:30, airtight water seal, be placed in dark place and soak 10h, afterwards by product isolated by filtration, gained composite particles washs with enough distilled water, and then by alcohol immersion, wash 3 times, after dry brominated polymers/nano-TiO
2composite particles, then, by its heat treatment 4.5h in the baking oven of 105 ℃, obtains conjugated polyene/nano-TiO
2composite particles.Gained composite particles is put into the ethanolic solution of counting the iodine of 0.07mol/L with iodine concentration, at 70 ℃, stirred and soak 1h, product is separated by filtration, and ethanol obtains conjugated polyene/nano-TiO after washing, being dried
2visible light catalyst.Experiment records the prepared conjugated polyene/nano-TiO of the method
2visible light catalyst is 0.401h to the degradation rate constant of methyl orange
-1, be commodity nano-TiO under the same terms
2(P-25) degradation rate constant (0.024h to methyl orange
-1) 16.7 times.
Take 0.625g natural rubber and be placed in conical flask, add 150mL toluene, airtight, be stirred to natural rubber and dissolve completely.Then take 5.0g nano-TiO
2particle adds in the toluene solution of this natural rubber, with the ultrasonic dispersion of supersonic wave cleaning machine 30min, then suction filtration after stirring immersion 4h, filter cake is dried 4h at 100 ℃, obtains natural rubber/nano-TiO
2composite particles.By dried above-mentioned natural rubber/nano-TiO
2composite particles joins in the bromine aqueous solution that the mass concentration of new system is 3.1%, described natural rubber/nano-TiO
2the mass ratio of composite particles and bromine aqueous solution is 1:30, and airtight water seal is placed in dark place and soaks 10h, and afterwards by product isolated by filtration, gained composite particles wash with enough distilled water, and then by alcohol immersion, wash 3 times, must brominated polymers/nano-TiO after being dried
2composite particles, then, by its heat treatment 4h in the baking oven of 90 ℃, obtains conjugated polyene/nano TiO 2 composite particles.Gained composite particles is put into the ethanolic solution of counting 0.09mol/L with iodine concentration, at 78.0 ℃, stirred and soak 1h, product is separated by filtration, and ethanol obtains conjugated polyene/nano-TiO after washing, being dried
2visible light catalyst.Experiment records the prepared conjugated polyene/nano-TiO of the method
2visible light catalyst is 0.378h to the degradation rate constant of methyl orange
-1, be commodity nano-TiO under the same terms
2(P-25) degradation rate constant (0.024h to methyl orange
-1) 15.8 times.
Embodiment 4
Take 0.10g natural rubber and be placed in conical flask, add 60mL toluene, airtight, be stirred to natural rubber and dissolve completely.Then take 2.0g nano-TiO
2particle adds in the toluene solution of this natural rubber, with the ultrasonic dispersion of supersonic wave cleaning machine 30min, then suction filtration after stirring immersion 4h, filter cake is dried 4h at 100 ℃, obtains natural rubber/nano-TiO
2composite particles.By dried above-mentioned natural rubber/nano-TiO
2composite particles joins in the bromine aqueous solution that the mass concentration of new system is 2.8%, the mass ratio of natural rubber/nano TiO 2 composite particles and bromine aqueous solution is 1:20, airtight water seal, be placed in dark place and soak 10h, afterwards by product isolated by filtration, gained composite particles washs with enough distilled water, and then by alcohol immersion, wash 3 times, after dry, obtain brominated polymers/nano TiO 2 composite particles, then, by its heat treatment 4h in the baking oven of 120 ℃, obtain conjugated polyene/nano TiO 2 composite particles.Gained composite particles is put into the ethanolic solution of counting 0.05mol/L with iodine concentration, at 78.0 ℃, stirred and soak 60min, product is separated by filtration, and ethanol obtains conjugated polyene/nano-TiO after washing, being dried
2visible light catalyst.Experiment records the prepared conjugated polyene/nano-TiO of the method
2visible light catalyst is 0.391h to the degradation rate constant of methyl orange
-1, be commodity nano-TiO under the same terms
2(P-25) degradation rate constant (0.024h to methyl orange
-1) 16.3 times.
If Fig. 1 is conjugated polyene/nano-TiO of the present invention
2visible light catalyst and commodity nano-TiO
2(P-25) UV-Vis DRS absorption spectrum comparison diagram.In figure, curve 1 is commodity nano-TiO
2spectrum, it is the spectrum of mass ratio while being 1:10 and 1:8 that curve 2 and 3 is respectively conjugated polyene/nano titanium oxide.As seen from Figure 1, the prepared conjugated polyene/nano-titanium dioxide visible light catalyst of the present invention in the absorption intensity of visible region apparently higher than nano-TiO
2.
If Fig. 2 is conjugated polyene/nano-TiO of the present invention
2visible light catalyst and commodity nano-TiO
2(P-25) photo-catalytic degradation of methyl-orange effect contrast figure.4 of oblique upper photo-catalytic degradation of methyl-orange design sketch that straight line is the embodiment of the present invention 1 to 4 in figure, the straight line of 4 line belows is general goods nano-TiO
2(P-25) photo-catalytic degradation of methyl-orange design sketch.As seen from Figure 2, conjugated polyene/nano-TiO of the present invention
2the effect of visible light catalyst catalyzing and degrading pollutant methyl orange under common fluorescent lamp irradiates is remarkable.
Claims (6)
1. a preparation method for conjugated polyene/nano-titanium dioxide visible light catalyst that the natural rubber of take is raw material, is characterized in that it comprises the following steps:
A. in toluene, add natural rubber, airtight stirring, the toluene solution that to be mixed with containing natural rubber mass concentration be 1g/L～4g/L;
B. to gained in described step a, containing in the toluene solution of natural rubber, add nano-TiO
2, described natural rubber and TiO
2mass ratio be 1:8～20, ultrasonic dispersion 30～40min, then under agitation adsorbs after 3～5h, after filtration, separated, the dry natural rubber/nano-TiO that obtains
2composite particles;
C. by gained natural rubber/nano-TiO in described step b
2composite particles joins in the saturated bromine aqueous solution of new system, controls natural rubber/nano-TiO
2composite particles and bromine aqueous solution mass ratio are 1:20～30, are placed in dark place and soak 8～12h, afterwards by product isolated by filtration, with 500～1000mL distilled water, wash, again by 50～100mL soaked in absolute ethyl alcohol, wash 3 times, be dried to constant weight, obtain brominated polymers/nano titanium oxide composite particles;
D. by gained brominated polymers/nano titanium oxide composite particles heat treatment 3～5h at 80 ℃～120 ℃ in described step c, make brominated polymers remove hydrogen bromide and generate conjugated polyene, obtain conjugated polyene/nano titanium oxide composite particles;
E. gained conjugated polyene/nano titanium oxide composite particles in described steps d is put into the ethanolic solution of counting 0.05～0.09mol/L with iodine concentration, at 60～78 ℃, stir and soak 1～2h, products therefrom is separated by filtration, and ethanol obtains conjugated polyene/nano-TiO after washing, being dried
2visible light catalyst.
2. a kind of preparation method of take conjugated polyene/nano-titanium dioxide visible light catalyst that natural rubber is raw material as claimed in claim 1, is characterized in that natural rubber described in step b and TiO
2mass ratio be 1:10.
3. a kind of preparation method of take conjugated polyene/nano-titanium dioxide visible light catalyst that natural rubber is raw material as claimed in claim 1, is characterized in that, the mass concentration of bromine aqueous solution described in step c is 2.8%～3.1%.
4. a kind of preparation method of take conjugated polyene/nano-titanium dioxide visible light catalyst that natural rubber is raw material as claimed in claim 1, is characterized in that natural rubber/nano-TiO described in step c
2composite particles and bromine aqueous solution mass ratio are 1:25.
5. a kind of preparation method of take conjugated polyene/nano-titanium dioxide visible light catalyst that natural rubber is raw material as claimed in claim 1, is characterized in that brominated polymers/nano titanium oxide composite particles heat treatment 4h at 100 ℃ in described steps d.
6. a kind of preparation method of take conjugated polyene/nano-titanium dioxide visible light catalyst that natural rubber is raw material as claimed in claim 1, is characterized in that it comprises following concrete steps:
A. take 0.33g natural rubber and be placed in conical flask, add 100mL toluene, airtight, be stirred to natural rubber and dissolve completely, be mixed with the toluene solution containing natural rubber;
B. according to natural rubber and nano-TiO
2mass ratio is the ratio of 1:10, takes 2.0g nano-TiO
2particle add described in 60mL step a containing in the toluene solution of natural rubber, with ultrasonic dispersions of supersonic wave cleaning machine 30min, then stir suction filtration after immersion 4h, filter cake is dried 4h at 100 ℃, obtains natural rubber/nano-TiO
2composite particles;
C. by the natural rubber/nano-TiO of step b gained
2composite particles joins in the bromine aqueous solution that the mass concentration of new system is 3.0%, controls natural rubber/nano-TiO
2the mass ratio of composite particles and bromine aqueous solution is 1:25, and airtight water seal is placed in dark place and soaks 12h, afterwards by product isolated by filtration, and with the washing of 1000mL distilled water, and then with 100mL soaked in absolute ethyl alcohol, wash 3 times, must brominated polymers/nano-TiO after being dried
2composite particles;
D. by step c gained bromine Polymer/nano TiO
2composite particles heat treatment 4h in the baking oven of 100 ℃, to remove hydrogen bromide, obtains conjugated polyene/nano-TiO
2composite particles;
E. by steps d gained conjugated polyene/nano-TiO
2composite particles is put into the ethanolic solution of counting 0.06mol/L with iodine concentration, at 78.0 ℃, stirs and soaks 60min, and product is separated by filtration, and ethanol obtains conjugated polyene/nano-TiO after washing, being dried
2visible light catalyst.
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| Title |
|---|
| 掺杂改性TiO2可见光光催化剂研究的最新进展;赵占中;《硅酸盐通报》;20120229;第31卷(第1期);第92-95页 * |
| 碳掺杂二氧化钛的制备及其可见光催化性能;聂龙辉;《湖北工业大学学报》;20111031;第26卷(第5期);第26-30页 * |
| 聂龙辉.碳掺杂二氧化钛的制备及其可见光催化性能.《湖北工业大学学报》.2011,第26卷(第5期),第26-30页. |
| 赵占中.掺杂改性TiO2可见光光催化剂研究的最新进展.《硅酸盐通报》.2012,第31卷(第1期),第92-95页. |
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