CN103406117B - Preparation of high-selectivity inorganic skeletal biomimic TiO2 photocatalyst by sol-hydrothermal method at low temperature - Google Patents
Preparation of high-selectivity inorganic skeletal biomimic TiO2 photocatalyst by sol-hydrothermal method at low temperature Download PDFInfo
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- CN103406117B CN103406117B CN201310377848.1A CN201310377848A CN103406117B CN 103406117 B CN103406117 B CN 103406117B CN 201310377848 A CN201310377848 A CN 201310377848A CN 103406117 B CN103406117 B CN 103406117B
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Abstract
The invention relates to a method for preparing a high-selectivity inorganic skeletal biomimic TiO2 photocatalyst by a sol-hydrothermal method at a low temperature. The method comprises the following steps of: hydrolyzing an alkoxide of titanium to form an intermediate product with a hydroxyl in the hydrolysis process, forming a molecularly imprinted precursor sol by the hydrolytic intermediate product with the hydroxyl and target organic pollutants under the action of hydrogen bonds and the electrostatic interaction, and stirring at the room temperature and in the hydrothermal process, forming TiO2 through polycondensation of Ti(OH)4 and crystallizing the TiO2; next, by taking the mixed solution of methanol and ammonia water as an eluant, removing the molecules of the template by a Soxhlet extraction method to finally obtain the high-selectivity inorganic skeletal biomimic TiO2 photocatalyst. The method has the outstanding advantages of mild preparation conditions, high mechanical strength of the inorganic skeletal biomimic TiO2 photocatalyst, and good selectivity and high degradation efficiency to the target organic pollutants, and molecular recognition sites are not easy to damage; the method is capable of obviously reducing the concentration of the target pollutants in agricultural reuse water, and simultaneously keeping organic nutritional ingredients in the water to an utmost extent.
Description
Technical field
The present invention relates to the bionical TiO of a kind of inorganic skeleton
2the preparation method of photochemical catalyst, particularly relates to the bionical TiO of inorganic skeleton that a kind of sol-gel self-combustion synthesis low-temperature growth has high selectivity
2the method of photochemical catalyst.
Background technology
China is agricultural irrigation big country, accounts for more than 70% of national water consumption based on the agricultural water of irrigating, but China is again the very short country of water resource.Along with the further raising of national economy and urban life level, agricultural water is constantly tied up by industry and urban water, and agricultural production lack of water is on the rise, particularly the northern area of China, water resource utilizes and almost reaches critical condition, even jeopardizes grain-production safety.While water saving, utilize sanitary sewage and industrial effluent reusing in agricultural irrigation, not only can alleviate agricultural water resources situation in short supply to a certain extent, and a large amount of non-toxic organic things wherein can directly or indirectly for crop growth provides abundant nutrition, the biological effectiveness of soil mineral nutrient is also improved by its coordination, thus save a large amount of chemical fertilizer, reduce agriculture production cost.But, also containing some poisonous and harmful substances in agricultural recycle-water, these poisonous and harmful substances are accumulated in soil, absorbed by crops and by food chain enrichment step by step in vivo, animals and humans can be caused acute and chronic poisoning or produce carcinogenic, teratogenesis, mutagenesis etc., threaten the animal even existence of the mankind and procreation.Therefore, retaining in agriculture recycle-water while Organic nutrient to greatest extent, the poisonous and harmful substance in selective removal water body is a research work with scientific meaning and practical value.
At present, nano-TiO is utilized
2toxic organics in wastewater by photocatalysis has become a research field received much concern, but TiO
2light-catalyzed reaction does not have selective, and the toxic organic pollutant of the Organic nutrient useful to crops and initiation health risk can be degraded simultaneously.In recent years, researcher both domestic and external has started to pay close attention to TiO
2the problem of photocatalysis non-selectivity, and to raising TiO
2selectively do large quantity research.Existing bibliographical information, improves TiO
2the approach of photocatalysis to selectively mainly contains following five aspects: (1) changes TiO by regulating the pH of solution
2the state-of-charge on surface, thus improve TiO
2photochemical catalyst is to the absorption of target contaminant and degradation capability.But this method effectively can only process organic pollution that is positively charged or negative electrical charge.In fact, most organic pollution neutral, the method effectively can not realize the degradation selectivity of electroneutral organic pollution.(2) with special small numerator modified TiO
2surface, passes through nano-TiO
2hydrogen bond between the organic compound of surface graft and target contaminant or hydrophobic lipophilic effect make pollutant at catalyst surface Preferential adsorption, thus make these organic pollutions by degradation selectivity.Research shows, though the method makes TiO
2selectively to increase, but molecular modification TiO
2poor stability, so degradation effect is unsatisfactory.(3) preparation includes the two-region structured light catalyst in adsorption zone and photocatalytic activity district simultaneously, strengthens catalyst to the adsorption capacity of target contaminant by adsorption zone, thus increases the degradation rate of target organic pollution and degrade selective.But the preparation of this two-region structured light catalyst extremely bothers, and selective absorption and degradation capability are also limited.(4) the anatase TiO that particular crystal plane exposes is prepared
2, { the anatase TiO that 001} crystal face exposes
2have higher selective to electronegative organic pollution, but bad to the degradation selectivity ability of electroneutral and positively charged organic pollution.(5) bionical recognition technology is combined with photocatalysis technology, at TiO
2finishing one deck conductive organic molecule imprinted polymer and prepare the biomimetic photocatalysis agent with specific identification performance.Because the configuration of space structure and the template molecule of imprinted cavity, conformation are mated completely, be conducive to target contaminant, on biomimetic photocatalysis agent surface, selective absorption occur, thus make target organic pollution by degradation selectivity.The method not only effectively can process organic pollution that is positively charged or negative electrical charge, effectively can also realize the degradation selectivity of electroneutral organic pollution.In sum, bionical recognition technology combines with photocatalysis technology and to be with a wide range of applications in selective photocatalysis is degraded.
But, the bionical identification photocatalysis technology that bionical recognition technology combines with photocatalysis technology also has the Science and Technology problem of several key to be badly in need of solving: organic imprinted layer of (1) biomimetic photocatalysis agent easily light degradation occurs in photocatalytic process, its molecular recognition site is destroyed, finally causes its selective photocatalysis efficiency not high.(2) hydrophily of biomimetic photocatalysis agent is bad, causes most of target organic pollution not high at the adsorption efficiency on biomimetic photocatalysis agent surface, is unfavorable for that the selective light of target organic pollution urges solution.(3) bionical TiO is prepared in high-temperature calcination
2in process, molecular recognition site is easily destroyed.The present invention utilizes sol-gel self-combustion synthesis low-temperature growth TiO
2the Ti-OH that in process, Titanium alkoxides hydrolysis produces is as trace function monomer, and form compound by the active force such as electrostatic interaction, hydrogen bond and template molecule, the processes such as hydrolysis, condensation that proceed then form the TiO combined with template molecule
2crystal, finally adopts suitable elution, removes wherein template molecule, at TiO
2directly introduce molecular recognition site in the preparation process of photochemical catalyst, a kind of bionical TiO of full-inorganic skeleton with exhibiting high surface hydroxyl can be prepared
2photochemical catalyst.Rigid structure due to low-temperature growth process and inorganic skeleton enhances the stability in trace hole, so the recognition site of biomimetic photocatalysis agent is not easily destroyed.Stable recognition site and a large amount of surface hydroxyls are conducive to the bionical TiO of full-inorganic skeleton
2photochemical catalyst carries out selective absorption to target contaminant and efficient catalytic is degraded, and this overcomes the defect that biomimetic photocatalysis agent exists at present.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, propose the bionical TiO of inorganic skeleton that a kind of sol-gel self-combustion synthesis low-temperature growth has high selectivity
2the method of photochemical catalyst, the bionical TiO of inorganic skeleton prepared by this method
2the imprinted cavity of photochemical catalyst is stablized, and has the ability of higher degradation selectivity target contaminant, can realize the preferential degradation of agriculture reuse organic pollutants, and retain Organic nutrient in agriculture recycle-water to greatest extent.
The object of the invention is to be achieved through the following technical solutions, its preparation methods steps is as follows: with target organic pollution for template molecule, ethanol is solvent, glacial acetic acid is inhibitor, the alkoxide of titanium is function monomer presoma and titanium source, the intermediate product with hydroxyl is produced in the alkoxide hydrolytic process of titanium, with the hydrolysis intermediate product with hydroxyl for function monomer, hydrolysis intermediate product with hydroxyl occurs pre-assembled by hydrogen bond and electrostatic interaction and template molecule, prepare molecular engram precursor colloidal sol, then transfer in inner liner polytetrafluoroethylene reactor and carry out hydro-thermal reaction, reaction temperature 140-240 DEG C, reaction time 12-24 hour.The yellow rigidity TiO combined with template molecule is obtained by polycondensation reaction
2skeleton.Yellow solid product ethanol and deionized water wash three times respectively, then with volume ratio be the methyl alcohol of 1:1 and ammonia water mixture as eluent, remove template molecule by soxhlet extraction, TiO
2skeleton leaves the three-dimensional hole or binding site that match with template molecule size, shape and functional group, obtain the bionical TiO with high selectivity photocatalytic degradation target organic pollution
2photochemical catalyst.
The alkyl oxide of described titanium selects tetrabutyl titanate, metatitanic acid isopropyl ester or isopropyl titanate.
Described target organic pollution comprises methyl orange, 4-nitrophenol, the organic pollutions such as 2-nitrophenol, rhodamine B, orthomonochlorphenol, parachlorphenol.
The mol ratio of described target organic pollution and the alkyl oxide of titanium is 1:20 ~ 1:4.
The eluent that described surname extraction uses is methyl alcohol/ammoniacal liquor mixed solution.
Tetra-n-butyl titanate, absolute ethyl alcohol, the volume ratio of glacial acetic acid and water is 10:19:8:4.
Advantage of the present invention is:
(1) intermediate product with hydroxyl that produces in hydrolytic process of the alkoxide of titanium is as function monomer, does not need to use the organic functions monomer separately adding other.
(2) preparation method of the present invention is hydrothermal reaction at low temperature, and energy consumption is low.
(3) the bionical TiO of inorganic skeleton for preparing of the present invention
2the mechanical strength of photochemical catalyst is high, and recognition site is survivable, better selective.
Accompanying drawing explanation
The inorganic skeleton bionical TiO of Fig. 1 prepared by embodiment 1
2photochemical catalyst (a) and do not add the non-bionical TiO of inorganic skeleton prepared by template molecule
2the XRD collection of illustrative plates of photochemical catalyst comparative sample (b).
The inorganic skeleton bionical TiO of Fig. 2 prepared by embodiment 1
2photochemical catalyst (a) and do not add the non-bionical TiO of inorganic skeleton prepared by template molecule
2photochemical catalyst comparative sample (b) is to the Adsorption thermodynamics curve of 4-nitrophenol.
The inorganic skeleton bionical TiO of Fig. 3 prepared by embodiment 1
2photochemical catalyst (a) and do not add the non-bionical TiO of inorganic skeleton prepared by template molecule
2photochemical catalyst comparative sample (b) is to the curve of adsorption kinetics of 4-nitrophenol.
The inorganic skeleton bionical TiO of Fig. 4 prepared by embodiment 1
2photochemical catalyst (a) and do not add the non-bionical TiO of inorganic skeleton prepared by template molecule
2photochemical catalyst comparative sample (b) is to the kinetics of photocatalytic degradation curve of 4-nitrophenol.
Detailed description of the invention
Below implement to be intended to the present invention instead of limitation of the invention further are described.
Embodiment 1
By 0.4 g 4-nitrophenol, the anhydrous tetra-n-butyl titanate of 20 mL, 26 mL absolute ethyl alcohols and 4mL glacial acetic acid add in beaker A.Separately 12 mL absolute ethyl alcohols, 12 mL glacial acetic acid and 8 mL water are mixed, this mixed liquor is B liquid.B liquid is slowly dripped into A liquid, stirred at ambient temperature solution 3 hours, then to have transferred in polytetrafluoroethyllining lining reactor at 140 DEG C hydro-thermal reaction 12 hours, obtained flaxen solid.Solid product ethanol and deionized water wash three times respectively, then use methyl alcohol: ammoniacal liquor (volume ratio 1:1) mixed liquor, as eluent, removes template molecule by soxhlet extraction, obtain the bionical TiO of inorganic skeleton of white
2photochemical catalyst.As shown in Figure 1,2,3, 4, the bionical TiO of inorganic skeleton for preparing of the present invention
2photochemical catalyst to target organic pollution selective good, degradation efficiency is high.
Embodiment 2
By 0.4 g 2-nitrophenol, the anhydrous tetra-n-butyl titanate of 20 mL, 26 mL absolute ethyl alcohols and 4mL glacial acetic acid add in beaker A.Separately 12 mL absolute ethyl alcohols, 12 mL glacial acetic acid and 8 mL water are mixed, this mixed liquor is B liquid.B liquid is slowly dripped into A liquid, stirred at ambient temperature solution 3 hours, then to have transferred in polytetrafluoroethyllining lining reactor at 140 DEG C hydro-thermal reaction 12 hours, obtained flaxen solid.Solid product ethanol and deionized water wash three times respectively, then use methyl alcohol: ammoniacal liquor (volume ratio 1:1) mixed liquor, as eluent, removes template molecule by soxhlet extraction, obtain the bionical TiO of inorganic skeleton of white
2photochemical catalyst.
Embodiment 3
By 0.79 g 4-nitrophenol, the anhydrous tetra-n-butyl titanate of 20 mL, 26 mL absolute ethyl alcohols and 4mL glacial acetic acid add in beaker A.Separately 12 mL absolute ethyl alcohols, 12 mL glacial acetic acid and 8 mL water are mixed, this mixed liquor is B liquid.B liquid is slowly dripped into A liquid, stirred at ambient temperature solution 3 hours, then to have transferred in polytetrafluoroethyllining lining reactor at 140 DEG C hydro-thermal reaction 12 hours, obtained flaxen solid.Solid product ethanol and deionized water wash three times respectively, then use methyl alcohol: ammoniacal liquor (volume ratio 1:1) mixed liquor, as eluent, removes template molecule by soxhlet extraction, obtain the bionical TiO of inorganic skeleton of white
2photochemical catalyst.
Embodiment 4
By 0.79 g 2-nitrophenol, the anhydrous metatitanic acid isopropyl ester of 20 mL, 26 mL absolute ethyl alcohols and 4mL glacial acetic acid add in beaker A.Separately 12 mL absolute ethyl alcohols, 12 mL glacial acetic acid and 8 mL water are mixed, this mixed liquor is B liquid.B liquid is slowly dripped into A liquid, stirred at ambient temperature solution 3 hours, then to have transferred in polytetrafluoroethyllining lining reactor at 140 DEG C hydro-thermal reaction 12 hours, obtained flaxen solid.Solid product ethanol and deionized water wash three times respectively, then use methyl alcohol: ammoniacal liquor (volume ratio 1:1) mixed liquor, as eluent, removes template molecule by soxhlet extraction, obtain the bionical TiO of inorganic skeleton of white
2photochemical catalyst.
Embodiment 5
By 0.79 g 2-nitrophenol, 20 mL anhydrous isopropyl alcohol titaniums, 26 mL absolute ethyl alcohols and 4mL glacial acetic acid add in beaker A.Separately 12 mL absolute ethyl alcohols, 12 mL glacial acetic acid and 8 mL water are mixed, this mixed liquor is B liquid.B liquid is slowly dripped into A liquid, stirred at ambient temperature solution 3 hours, then to have transferred in polytetrafluoroethyllining lining reactor at 180 DEG C hydro-thermal reaction 5 hours, obtained flaxen solid.Solid product ethanol and deionized water wash three times respectively, then use methyl alcohol: ammoniacal liquor (volume ratio 1:1) mixed liquor, as eluent, removes template molecule by soxhlet extraction, obtain the bionical TiO of inorganic skeleton of white
2photochemical catalyst.
Embodiment 6
By 0.79 g 2-nitrophenol, the anhydrous tetra-n-butyl titanate of 20 mL, 26 mL absolute ethyl alcohols and 4mL glacial acetic acid add in beaker A.Separately 12 mL absolute ethyl alcohols, 12 mL glacial acetic acid and 8 mL water are mixed, this mixed liquor is B liquid.B liquid is slowly dripped into A liquid, stirred at ambient temperature solution 3 hours, then to have transferred in polytetrafluoroethyllining lining reactor at 180 DEG C hydro-thermal reaction 5 hours, obtained flaxen solid.Solid product ethanol and deionized water wash three times respectively, then use methyl alcohol: ammoniacal liquor (volume ratio 1:1) mixed liquor, as eluent, removes template molecule by soxhlet extraction, obtain the bionical TiO of inorganic skeleton of white
2photochemical catalyst.
Embodiment 7
Change the 2-nitrophenol in embodiment 1-6 and 4-nitrophenol into methyl orange, can prepare with methyl orange is the bionical TiO of inorganic skeleton of template
2photochemical catalyst.
Embodiment 8
Change the 2-nitrophenol in embodiment 1-6 and 4-nitrophenol into orthomonochlorphenol, can prepare with orthomonochlorphenol is the bionical TiO of inorganic skeleton of template
2photochemical catalyst.
Embodiment 9
Change the 2-nitrophenol in embodiment 1-6 and 4-nitrophenol into parachlorphenol, can prepare with parachlorphenol is the bionical TiO of inorganic skeleton of template
2photochemical catalyst.
Claims (3)
1. a sol-gel self-combustion synthesis low-temperature growth bionical TiO of inorganic skeleton with high selectivity
2the method of photochemical catalyst, it is characterized in that preparation method's step is as follows: with target organic pollution for template molecule, absolute ethyl alcohol is solvent, glacial acetic acid is inhibitor, the alkoxide of titanium is function monomer presoma and titanium source, the intermediate product with hydroxyl is produced in the alkoxide hydrolytic process of titanium, with the hydrolysis intermediate product with hydroxyl for function monomer, hydrolysis intermediate product with hydroxyl occurs pre-assembled by hydrogen bond and electrostatic interaction and template molecule, prepare molecular engram precursor colloidal sol, then transfer in inner liner polytetrafluoroethylene reactor and carry out hydro-thermal reaction, reaction temperature 140-240 DEG C, reaction time 12-24 hour, the yellow rigidity TiO combined with template molecule is obtained by polycondensation reaction
2skeleton, yellow solid product absolute ethyl alcohol and deionized water wash three times respectively, then use methyl alcohol and ammonia water mixture as eluent, remove template molecule, TiO by soxhlet extraction
2skeleton leaves the three-dimensional hole or binding site that match with template molecule size, shape and functional group, obtain the bionical TiO with high selectivity photocatalytic degradation target organic pollution
2photochemical catalyst, the alkyl oxide of described titanium selects tetrabutyl titanate, isopropyl titanate or isopropyl titanate, described target organic pollution comprises methyl orange, 4-nitrophenol, 2-nitrophenol, rhodamine B, orthomonochlorphenol, parachlorphenol, the mol ratio of described target organic pollution and the alkyl oxide of titanium is 1:20 ~ 1:4.
2. a kind of sol-gel self-combustion synthesis low-temperature growth according to claim 1 bionical TiO of inorganic skeleton with high selectivity
2the method of photochemical catalyst, is characterized in that: the alkoxide of described titanium selects tetrabutyl titanate, and the volume ratio of tetra-n-butyl titanate, absolute ethyl alcohol, glacial acetic acid and water is 10:19:8:4.
3. a kind of sol-gel self-combustion synthesis low-temperature growth according to claim 1 bionical TiO of inorganic skeleton with high selectivity
2the method of photochemical catalyst, is characterized in that: the methyl alcohol that the eluent that described surname extraction uses is 1:1 for volume ratio/ammoniacal liquor mixed solution.
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| CN101607736A (en) * | 2009-04-22 | 2009-12-23 | 湖南大学 | A kind of surface imprinting functionalization TiO 2Nanotube |
| US20100269270A1 (en) * | 2009-04-27 | 2010-10-28 | National Tsing Hua University | Preparation of a nanocomposite photoanode for dye-sensitized solar cells |
| CN102814172A (en) * | 2012-08-21 | 2012-12-12 | 华南师范大学 | Preparation method for molecular imprinting-type photocatalyst and application of molecular imprinting-type photocatalyst |
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| CN101607736A (en) * | 2009-04-22 | 2009-12-23 | 湖南大学 | A kind of surface imprinting functionalization TiO 2Nanotube |
| US20100269270A1 (en) * | 2009-04-27 | 2010-10-28 | National Tsing Hua University | Preparation of a nanocomposite photoanode for dye-sensitized solar cells |
| CN102814172A (en) * | 2012-08-21 | 2012-12-12 | 华南师范大学 | Preparation method for molecular imprinting-type photocatalyst and application of molecular imprinting-type photocatalyst |
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