CN103418334A - Preparation method of highly adsorptive N, I co-doped TiO2porous network powder - Google Patents
Preparation method of highly adsorptive N, I co-doped TiO2porous network powder Download PDFInfo
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Abstract
The invention relates to a preparation method for high-adsorption type N-I co-doped TiO2 porous network powder. The prepared porous powder is used for performing an adsorption removal test on a cationic dye solution to inspect the enrichment performance and the adsorption performance of the N-I co-doped TiO2 porous network structure powder on the cationic dye. The preparation method comprises the following steps: preparing TiO2 gel with different N-I doped amounts by using a raw material comprising NH4I and butyl titanate specifically thourgh a hydrothermal method; ultrasonically dispersing the TiO2 gel in a strong alkali solution with a certain concentration; performing hydrothermal treatment again; centrifugally separating, neutralizing, washing and drying to obtain the N-I co-doped TiO2 porous network structure powder. The N-I co-doped TiO2 porous network structure powder prepared by the method has large specific surface area and has strong selectivity and excellent adsorption ability on the cationic dye. The preparation method is simple and practical, has low cost and provides a new approach and an adsorbent with excellent performance for treating high-concentration cationic dye waste water.
Description
Technical field
The invention belongs to the preparation of nano composite material and the application of field of environment protection thereof.
Background technology
The waste water from dyestuff of textile industry discharge has complex chemical composition, concentration is large, colourity is high, discharge capacity is large, the toxicity high, has become the serious water body environment pollution source of China, so the degradation treatment of waste water from dyestuff is the hot topic of research.Treatment method of printing and dying wastewater has biological treatment, chemical oxidization method, flocculent precipitation, electrolysis, photocatalytic degradation method at present.Wherein absorption method because of its have simple to operate, energy consumption is lower, do not introduce new pollutant and can be from waste water the advantage such as concentration and separation organic pollution, more and more come into one's own, and be used widely.Titanium dioxide, due to advantages such as its stable chemical nature, photocatalysis speed are fast, non-selectivities, has outstanding advantage aspect water pollution control.Recently, relevant TiO
2The absorption of dyestuff has also been received to people's concern, as BeLessi etc. has reported TiO
2Nano particle is to 195 absorption behaviors of reactive brilliant red in solution, studied impact [the BeLessi V of the factors such as concentration, pH of solution on absorption, Romanos G, Boukos N, LambropouLou D, TrapaLis C. RemovaL of Reactive Red 195 from aqueous solutions by adsorption on the surface of TiO
2NanoparticLes [J]. JournaL of Hazardous MateriaLs, 2009,2-3 (170): 836-844.]; Jafari etc. have reported the TiO of different crystalline phases
2The adsorption dynamics adsorption kinetics research of particle to crystal violet, considered impact [Jafari S, Azizian S, the JaLeh B. Adsorption kinetics of methyL violet onto TiO of different crystalline phases on absorption
2NanoparticLes with different phases [J]. ColLoids and Surfaces A:PhysicochemicaL and Engineering Aspects, 2011,1-3 (384): 618-623.]; Pettibone etc. report TiO
2Nano particle, to the organic acid absorption behavior, has been investigated impact [Pettibone J M, Cwiertny D M, Scher M, the Grassian V H. Adsorption of Organic Acids on TiO of reunion, size and the pH value of solution of nano particle
2NanoparticLes:Effects of pH, NanoparticLe Size, and NanoparticLe Aggregation [J]. Langmuir, 2008,24,6659-6667.].Yet, TiO used in above-mentioned report
2Do not carry out the TiO of modification
2.At present, nano-TiO
2Study on the modification be a study hotspot during wastewater by photocatalysis is processed, as to TiO
2Carry out nonmetallic ion as N, the doping such as C or I strengthen TiO
2Photocatalytic activity be emphasis ［ the Ao YH of current research, Xu JJ, Zhang SH, Fu DG. A one-pot method to prepare N-doped titania holLow spheres with high photocataLytic activity under visibLe Light [J]. AppLied Surface Science. 2010,256:2754 – 2758. ］, there is more importantly meaning so study the absorption behavior of nonmetallic ion-doped nano titanium oxide.Up to the present, only reported in document and adopted the hydrolysis calcination method to prepare N, the TiO of I codope
2Nano particle also will be for photocatalytic degradation ［ Zhou Liang, Deng Jian, Zhao Yubao, Liu Wanbing, An Lin, Chen Fei, Preparation and characterization of N – I co-doped nanocrystaL anatase TiO
2With enhanced photocataLytic activity under visibLe-Light irradiation. MateriaLs Chemistry and Physics 117 (2009) 522 – 527 ］, for N, the hydro-thermal method of I codope titanium dioxide porous network structure powder preparation and the absorption of the dye of positive ion be there is no to reported in literature both at home and abroad.
Summary of the invention
The objective of the invention is to propose a kind of novel N, I codope TiO
2The preparation of porous network structure powder and the new method that the dye of positive ion in the dye of positive ion waste water of variable concentrations is removed thereof, for process dye of positive ion waste water provide a kind of new material and newly by way of.The method adopts the secondary hydro-thermal method, adds for the first time a certain amount of ammonium iodide, preparation N during hydro-thermal, the nano titanium oxide gel of I codope, subsequently to strong base solution ultrasonic processing for nanogel, subsequently again after hydrothermal treatment consists, be neutralized to neutrality with acid, obtain a kind of novel N, I codope TiO
2The porous network structure powder, and use it for the removal research of dye of positive ion solution.
Specifically comprise the following steps:
(1) measure the tetrabutyl titanate of certain volume, measure the absolute ethyl alcohol of certain volume, be mixed with the ethanolic solution of tetrabutyl titanate, wherein the concentration of tetrabutyl titanate is 1.7558*10
-4-6.14523*10
-4Mol/L.
(2) mol ratio in ammonium iodide amount and butyl titanate is the 0.1:1-1.5:1 ratio, take the ethanolic solution that a certain amount of ammonium iodide joins above-mentioned tetrabutyl titanate, make mixed solution, proceed to subsequently reactor and carry out hydro-thermal for the first time, the temperature of hydro-thermal is 110-220 ℃, and the hydro-thermal time is 6-24h.Hydro-thermal finishes, centrifugation, and washing, dries and obtains N, and the nano titanium oxide that I adulterates is received gel.
(3) take the above-mentioned N made, the nano titanium oxide of I doping is received gel, join in certain density NaOH solution, the concentration of NaOH is 5-12mol/L, wherein N, it is (0.5-10) with the ratio of NaOH solution that the nano titanium oxide of I doping is received gel: (50-120) g/mL, ultrasonic dispersion, ultrasonic time is 10-120min, proceeds to subsequently in reactor and carries out hydro-thermal for the second time, the temperature of hydro-thermal is 80-150 ℃, and the hydro-thermal time is 6-24h.Hydro-thermal finishes for the second time, centrifugation, with distilled water sedimentation 2-5 time, to precipitate with distilled water and again disperse after centrifugation, with the salpeter solution neutralization, until the pH of the solution of sample is neutral, with distilled water washing 2-5 time, dry, make different N, I codope titanium dioxide porous network structure powder.
One of the present invention is preferably in embodiment, and in step (2), to carry out the hydrothermal temperature of hydro-thermal for the first time be 130-190 ℃ to reactor, and the hydro-thermal time is 12-20h.
One of the present invention is preferably in embodiment, and in step (3), ultrasonic time is 20-90min.
One of the present invention is preferably in embodiment, and carrying out the hydrothermal temperature of hydro-thermal for the second time in reactor in step (3) is 90-140 ℃, and the hydro-thermal time is 10-20h.
This experiment makes N, and the evaluation of I codope titanium dioxide porous network structure powder high absorption property is carried out in thermostat water bath.The certain density dye of positive ion solution of 100mL is joined in conical flask and measures its initial value, dye of positive ion concentration is 10-300mg/L, adsorption temp is 10-35 ℃, then add a certain amount of N, I codope poriferous titanium dioxide nano-powder adsorbent carries out adsorption experiment in thermostat water bath, and the consumption of adsorbent is 50mg/L-2.5g/L.Sample after the absorption certain hour, after centrifugation, supernatant is measured to the absorbance of solution with ultraviolet-visible spectrophotometer in the maximum absorption wave strong point of dyestuff.According to the absorbance before and after absorption, calculate the clearance D:D=(A of dye of positive ion solution
0– A
t)/A
0* 100%, A in formula
0The absorbance of sample while just starting for adsorbing, A
tThe absorbance of sample for the absorption certain hour.Adsorption effect is characterized by the size of the clearance of dye of positive ion solution.
The N that the present invention makes, I codope titanium dioxide porous network structure powder and be to the technique effect that the enrichment of the dyestuff in dye of positive ion waste water and absorption bring:
(1) utilize N source, propiodal and titanium source cheaply to prepare N, I codope titanium dioxide porous network structure powder, it is raw materials used all pollution-free; the technique of method is simple, simple in preparation process, less energy consumption; cost is low, belongs to green synthesis techniques, and can realize the scale preparation.
(2) N, I codope titanium dioxide porous network structure powder is a kind of novel high-efficiency adsorbent.This adsorbent specific area is huge, thereby the few cost of consumption is low; And use N, after I carries out codope, changed the state of charge of kind titanium dioxide surface, can under short period and lower temperature, realize enrichment and the absorption to the dye of positive ion, not only can be used for the enrichment to trace cation dyestuff in environmental wastewater, can process again the dye of positive ion waste water of high concentration, thereby greatly improve the removal efficiency of the dye of positive ion simultaneously.
Innovation of the present invention is:
(1) proposed a kind ofly to prepare N with N source, propiodal and titanium source, the new method of the titanium dioxide compound adsorbent of I codope porous network structure.
(2) new way and the new adsorbent of dye of positive ion waste water solution have been proposed to process, the N made, I codope titanium dioxide porous network structure powder, not only utilized the huge advantage of its porous network shape specific area that structure has, utilize N simultaneously, the I codope, improve the surface charge state.The cooperative effect of pattern and electric charge, improved the capture rate of the dye of positive ion greatly, and efficient low energy realizes the processing of variable concentrations dye of positive ion waste water, effectively reduces the removal cost of the dye of positive ion.
The accompanying drawing explanation
Fig. 1: the EDS figure that makes sample by example 1
Fig. 2: the N made by example 5, I codope titanium dioxide porous network structure powder SEM figure
Fig. 3: the N made by example 7, I codope titanium dioxide porous network structure powder SEM figure.
Fig. 4: the N made by example 8, I codope titanium dioxide porous network structure powder TEM figure.
The specific embodiment:
Below in conjunction with accompanying drawing, optimal way of the present invention is further described
Example 1
1) measure the 3mL tetrabutyl titanate, measure the 50mL absolute ethyl alcohol, be made into the ethanolic solution of tetrabutyl titanate.
2) ammonium iodide that takes 0.123g is in above-mentioned solution, and stirring and dissolving, make the mixed ethanol solution of ammonium iodide and tetrabutyl titanate, and wherein the mol ratio of ammonium iodide and tetrabutyl titanate is 0.1:1.After fully stirring, this solution is transferred in water heating kettle, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 110 ℃, and the hydro-thermal time is 24h.Hydro-thermal finishes, and the centrifugation washing and drying, make N, and the nano titanium oxide of I doping is received gel.
3) take the above-mentioned gel made of above-mentioned 0.5g and add in the NaOH solution of 50mL 5mol/L, ultrasonic 10min, pour in water heating kettle subsequently, carries out hydro-thermal in baking oven, and the temperature of hydro-thermal is 150 ℃, and the hydro-thermal time is 6h.Hydro-thermal finishes, and centrifugation, with distilled water washing 2-5 time, to precipitate with distilled water and again disperse, after the pH that is neutralized to sample solution with dilute nitric acid solution is neutrality, then with distilled water washing 2-5 time, dry under uniform temperature, make N, the titanium dioxide powder of I codope porous network structure.The specific area of sample is 198.57m
2/ g.
4) estimate the absorption property of this sample in 30 ℃ of thermostat water baths.The cationic blue dye solution of 100mL 10mg/L is joined in conical flask, the sample that then adds example 1 to make, the consumption of sample is 50mg/L, carries out adsorption experiment in thermostat water bath, absorption 1h, the cationic blue dyestuff is removed efficiency D and is reached 99.99%.
The N of Figure of description 1 for making by example 1, the characteristic peak of I, as can be known from Figure, Ti, O, N have appearred, in I codope titanium dioxide porous network structure powder EDS figure in spectrogram.Ti and O come from titanium dioxide, and the existence of N and I illustrates N, and I successfully is incorporated into TiO
2In.
Example 2
1) measure the 6mL tetrabutyl titanate, measure the 60mL absolute ethyl alcohol, be made into the ethanolic solution of tetrabutyl titanate.
2) ammonium iodide that takes 0.37g is in above-mentioned solution, and stirring and dissolving, make the mixed ethanol solution of ammonium iodide and tetrabutyl titanate, and wherein the mol ratio of ammonium iodide and butyl titanate is 0.15:1.After fully stirring, this solution is transferred in water heating kettle, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 130 ℃, and the hydro-thermal time is 20h.Hydro-thermal finishes, and the centrifugation washing and drying, make N, the nano titanium oxide gel of I doping.
3) take the above-mentioned N made of 1g, I codope titanium dioxide gel, in beaker, adds in the NaOH solution of 80mL 8mol/L, and ultrasonic 20min, pour in water heating kettle subsequently subsequently, carries out hydro-thermal in baking oven, and the temperature of hydro-thermal is 100 ℃, and the hydro-thermal time is 18h.Hydro-thermal finishes, and centrifugation, with distilled water washing 2-5 time, to precipitate with distilled water and again disperse, after the pH that is neutralized to sample solution with dilute nitric acid solution is neutrality, then with distilled water washing 2-5 time, dry under uniform temperature, make N, the titanium dioxide powder of the porous network shape of I codope.The specific area of sample is 246.50m
2/ g.
4) estimate the absorption property of this sample in 10 ℃ of thermostat water baths.The cationic golden yellow dye solution of 100mL 20mg/L is joined in conical flask, the sample that then adds example 2 to make, the consumption of sample is that 300mg/L carries out adsorption experiment in thermostat water bath, absorption 1h, the cationic golden yellow dyestuff is removed efficiency D and is reached 83.89%.
Example 3
1) measure the 9mL tetrabutyl titanate, measure the 80mL absolute ethyl alcohol, be made into the ethanolic solution of tetrabutyl titanate.
2) ammonium iodide that takes 0.923g is in above-mentioned solution, and stirring and dissolving, make the mixed ethanol solution of ammonium iodide and tetrabutyl titanate, and wherein the mol ratio of ammonium iodide and butyl titanate is 0.25:1.After fully stirring, this solution is transferred in water heating kettle, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 150 ℃, and the hydro-thermal time is 18h.Hydro-thermal finishes, and the centrifugation washing and drying, make N, the nano titanium oxide gel of I doping.
3) take the above-mentioned N made of above-mentioned 1.5g, the nanogel of I codope, in beaker, adds in the NaOH solution of 90mL 9mol/L, ultrasonic 30min, pour in water heating kettle subsequently subsequently, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 90 ℃, and the hydro-thermal time is 20h.Hydro-thermal finishes, and centrifugation, with distilled water washing 2-5 time, to precipitate with distilled water and again disperse, after the pH that is neutralized to sample solution with dilute nitric acid solution is neutrality, then with distilled water washing 2-5 time, dry under uniform temperature, make N, the titanium dioxide powder of the porous network structure of I codope.The specific area of sample is 232.46m
2/ g.
4) estimate the absorption property of this sample in 25 ℃ of thermostat water baths.The cationic flavine dye solution of 100mL 30mg/L is joined in conical flask, then the sample that adds example 3 to make, the addition of sample is 300mg/L, carries out adsorption experiment in thermostat water bath, absorption 1h, the cationic flavine dyestuff is removed efficiency D and is reached 98.83%.
Example 4
1) measure the 12mL tetrabutyl titanate, measure the 100mL absolute ethyl alcohol, be made into the ethanolic solution of tetrabutyl titanate.
2) ammonium iodide that takes 1.728g is in above-mentioned solution, and stirring and dissolving, make the mixed ethanol solution of ammonium iodide and tetrabutyl titanate, and wherein the mol ratio of ammonium iodide and butyl titanate is 0.35:1.After fully stirring, this solution is transferred in water heating kettle, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 160 ℃, and the hydro-thermal time is 18h.Hydro-thermal finishes, and the centrifugation washing and drying, make N, the nano titanium oxide gel of I codope.
3) take the above-mentioned N made of above-mentioned 3g, the nanogel of I codope, in beaker, adds in the NaOH solution of 80mL 10 mol/L, ultrasonic 1h, pour in water heating kettle subsequently subsequently, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 80 ℃, and the hydro-thermal time is 24h.Hydro-thermal finishes, and centrifugation, with distilled water washing 2-5 time, to precipitate with distilled water and again disperse, after the pH that is neutralized to sample solution with dilute nitric acid solution is neutrality, then with distilled water washing 2-5 time, dry under uniform temperature, make N, the titanium dioxide powder of the porous network shape of I codope.The specific area of sample is 230.50m
2/ g.
)Estimate the absorption property of this sample in 25 ℃ of thermostat water baths.The cationic red X-FRL solution of 100mL 40mg/L is joined in conical flask, the sample that then adds example 4 to make, amount of samples is 500mg/L, carries out adsorption experiment in thermostat water bath, absorption 1h, cationic red X-FRL is removed efficiency D and is reached 95.90%.
Example 5
1) measure the 15mL tetrabutyl titanate, measure the 100mL absolute ethyl alcohol, be made into the ethanolic solution of tetrabutyl titanate.
2) ammonium iodide that takes 3.09g is in above-mentioned solution, and stirring and dissolving, make the mixed ethanol solution of ammonium iodide and tetrabutyl titanate, and wherein the mol ratio of ammonium iodide and butyl titanate is 0.5:1.After fully stirring, this solution is transferred in water heating kettle, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 160 ℃, and the hydro-thermal time is 18h.Hydro-thermal finishes, and the centrifugation washing and drying, make N, the nano titanium oxide gel of I doping.
3) take the above-mentioned N made of above-mentioned 3g, the nanogel of I codope, in beaker, adds in the NaOH solution of 80mL 10 mol/L, ultrasonic 70min, pour in water heating kettle subsequently, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 110 ℃, and the hydro-thermal time is 12h.Hydro-thermal finishes, and centrifugation, with distilled water washing 2-5 time, to precipitate with distilled water and again disperse, after the pH that is neutralized to sample solution with dilute nitric acid solution is neutrality, then with distilled water washing 2-5 time, dry under uniform temperature, make the titanium dioxide powder of the porous network structure of codope.The specific area of sample is 298.36m
2/ g.
4) estimate the absorption property of this sample in 15 ℃ of thermostat water baths.The cationic blue dye solution of 80mL 60mg/L is joined in conical flask, the sample that then adds example 5 to make, the addition of sample is 500mg/L, carries out adsorption experiment in thermostat water bath, absorption 1h, the cationic blue dyestuff is removed efficiency D and is reached 99.85%.
The N of Figure of description 2 for making by example 5, I codope porous network structure titanium dioxide powder SEM figure.As can be known from Figure, titanium dioxide is tubular structure, thereby these are run well to interconnect and form a kind of three-dimensional porous network structure.
Example 6
1) measure the 18mL tetrabutyl titanate, measure the 150mL absolute ethyl alcohol, be made into the ethanolic solution of tetrabutyl titanate.
2) ammonium iodide that takes 4.44g is in above-mentioned solution, and stirring and dissolving, make the mixed ethanol solution of ammonium iodide and tetrabutyl titanate, and wherein the mol ratio of ammonium iodide and butyl titanate is 0.6:1.After fully stirring, this solution is transferred in water heating kettle, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 170 ℃, and the hydro-thermal time is 16h.Hydro-thermal finishes, and the centrifugation washing and drying, make N, the nano titanium oxide gel of I doping.
3) take the above-mentioned N made of above-mentioned 4g, the nanogel of I codope, in beaker, adds in the NaOH solution of 90mL 11 mol/L, ultrasonic 80min, pour in water heating kettle subsequently, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 120 ℃, and the hydro-thermal time is 10h.Hydro-thermal finishes, and centrifugation, with distilled water washing 2-5 time, to precipitate with distilled water and again disperse, after the pH that is neutralized to sample solution with dilute nitric acid solution is neutrality, then with distilled water washing 2-5 time, dry under uniform temperature, make the titanium dioxide powder of the porous network shape of codope.The specific area of sample is 280.50m
2/ g.
4) estimate the absorption property of this sample in 20 ℃ of thermostat water baths.The cationic golden yellow dye solution of 100mL 70mg/L is joined in conical flask, the sample that then adds example 6 to make, amount of samples is 600mg/L, carries out adsorption experiment in thermostat water bath, absorption 1h, the cationic golden yellow dyestuff is removed efficiency D and is reached 84.22%.
Example 7
1) measure the 21mL tetrabutyl titanate, measure the 100mL absolute ethyl alcohol, be made into the ethanolic solution of tetrabutyl titanate.
2) ammonium iodide that takes 6.48g is in above-mentioned solution, and stirring and dissolving, make the mixed ethanol solution of ammonium iodide and tetrabutyl titanate, and wherein the mol ratio of ammonium iodide and butyl titanate is 0.75:1.After fully stirring, this solution is transferred in water heating kettle, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 180 ℃, and the hydro-thermal time is 12h.Hydro-thermal finishes, and the centrifugation washing and drying, make N, the nano titanium oxide gel of I doping.
3) take the above-mentioned N made of above-mentioned 5g, the nanogel of I codope, in beaker, adds in the NaOH solution of 100mL 12 mol/L, ultrasonic 90min, pour in water heating kettle subsequently, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 120 ℃, and the hydro-thermal time is 8h.Hydro-thermal finishes, and centrifugation, with distilled water washing 2-5 time, to precipitate with distilled water and again disperse, after the pH that is neutralized to sample solution with dilute nitric acid solution is neutrality, then with distilled water washing 2-5 time, dry under uniform temperature, make the titanium dioxide powder of the porous network structure of codope.The specific area of sample is 239.67m
2/ g.
4) estimate the absorption property of this sample in 25 ℃ of thermostat water baths.The cationic flavine dye solution of 100mL 80mg/L is joined in conical flask, then the sample that adds example 7 to make, the addition of sample is 1g/L, carries out adsorption experiment in thermostat water bath, absorption 1h, the cationic flavine dyestuff is removed efficiency D and is reached 99.15%.
The N of Figure of description 3 for making by example 7, the titanium dioxide powder SEM figure of I codope porous network structure.As can be known from Figure, titanium dioxide is also tubular structure, and these pipes join end to end, thereby forms three-dimensional net structure.
Example 8
1) measure the 24mL tetrabutyl titanate, measure the 150mL absolute ethyl alcohol, be made into the ethanolic solution of tetrabutyl titanate.
2) ammonium iodide that takes 9.87g is in above-mentioned solution, and stirring and dissolving, make the mixed ethanol solution of ammonium iodide and tetrabutyl titanate, and wherein the mol ratio of ammonium iodide and butyl titanate is 1:1.After fully stirring, this solution is transferred in water heating kettle, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 140 ℃, and the hydro-thermal time is 20h.Hydro-thermal finishes, and the centrifugation washing and drying, make N, the nano titanium oxide gel of I doping.
3) take the above-mentioned N made of above-mentioned 8g, the nanogel of I codope, in beaker, adds in the NaOH solution of 100mL 12 mol/L, ultrasonic agitation 1.5h, pour in water heating kettle subsequently, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 100 ℃, and the hydro-thermal time is 24h.Hydro-thermal finishes, and centrifugation, with distilled water washing 2-5 time, to precipitate with distilled water and again disperse, after the pH that is neutralized to sample solution with dilute nitric acid solution is neutrality, then with distilled water washing 2-5 time, dry under uniform temperature, make the titanium dioxide powder of the porous network shape of codope.The specific area of sample is 250.22m
2/ g.
4) estimate the absorption property of this sample in 30 ℃ of thermostat water baths.The cationic blue dye solution of 100mL 160mg/L is joined in conical flask, the sample that then adds example 8 to make, the sample addition is 1.5g/L, carries out adsorption experiment in thermostat water bath, absorption 1h, the cationic blue dyestuff is removed efficiency and is reached 98.73%.
The N of Figure of description 4 for making by example 8, the titanium dioxide powder TEM figure of I codope porous network shape.As can be known from Figure, the titanium dioxide of formation is the tubulose network structure be overlapping.
Example 9
1) measure the 27mL tetrabutyl titanate, measure the 200mL absolute ethyl alcohol, be made into the ethanolic solution of tetrabutyl titanate.
2) ammonium iodide that takes 13.89g is in above-mentioned solution, and stirring and dissolving, make the mixed ethanol solution of ammonium iodide and tetrabutyl titanate, and wherein the mol ratio of ammonium iodide and butyl titanate is 1.25:1.After fully stirring, this solution is transferred in water heating kettle, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 190 ℃, and the hydro-thermal time is 12h.Hydro-thermal finishes, and the centrifugation washing and drying, make N, the nano titanium oxide gel of I doping.
3) take the above-mentioned N made of above-mentioned 10g, the nanogel of I codope, in beaker, adds in the NaOH solution of 120mL 12 mol/L, ultrasonic 2h, pour in water heating kettle subsequently, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 140 ℃, and the hydro-thermal time is 16h.Hydro-thermal finishes, and centrifugation, with distilled water washing 2-5 time, to precipitate with distilled water and again disperse, after the pH that is neutralized to sample solution with dilute nitric acid solution is neutrality, then with distilled water washing 2-5 time, dry under uniform temperature, make the titanium dioxide powder of the porous network shape of codope.The specific area of sample is 215.38m
2/ g.
4) estimate the absorption property of this sample in 15 ℃ of thermostat water baths.The cationic golden yellow dye solution of 100mL 250mg/L is joined in conical flask, then the sample that adds example 9 to make, the addition of sample is 2.5g/L, carries out adsorption experiment in thermostat water bath, absorption 1h, the cationic golden yellow dyestuff is removed efficiency D and is reached 85.68%.
Example 10
1) measure the 30mL tetrabutyl titanate, measure the 300mL absolute ethyl alcohol, be made into the ethanolic solution of tetrabutyl titanate.
2) ammonium iodide that takes 18.516g is in above-mentioned solution, and stirring and dissolving, make the mixed ethanol solution of ammonium iodide and tetrabutyl titanate, and wherein the mol ratio of ammonium iodide and butyl titanate is 1.5:1.After fully stirring, this solution is transferred in water heating kettle, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 220 ℃, and the hydro-thermal time is 6h.Hydro-thermal finishes, and the centrifugation washing and drying, make N, the nano titanium oxide gel of I doping.
3) take the above-mentioned N made of above-mentioned 12g, the nanogel of I codope, in beaker, adds in the NaOH solution of 120mL 10 mol/L, ultrasonic 1.5h, pour in water heating kettle subsequently, carries out hydro-thermal in baking oven, the temperature of hydro-thermal is 100 ℃, and the hydro-thermal time is 18h.Hydro-thermal finishes, and centrifugation, with distilled water washing 2-5 time, to precipitate with distilled water and again disperse, after the pH that is neutralized to sample solution with dilute nitric acid solution is neutrality, then with distilled water washing 2-5 time, dry under uniform temperature, make the titanium dioxide powder of the porous network shape of codope.The specific area of sample is 189.86m
2/ g.
4) estimate the absorption property of this sample in 35 ℃ of thermostat water baths.The cationic golden yellow dye solution of 100mL 300mg/L is joined in conical flask, then the sample that adds example 10 to make, the addition of sample is 2.5g/L, carries out adsorption experiment in thermostat water bath, absorption 1h, the cationic golden yellow dyestuff is removed efficiency D and is reached 83.10%.
Claims (5)
1. one kind high absorbent-type N, I codope TiO
2The preparation method of porous network structure powder is characterized in that carrying out according to following step:
(1) measure tetrabutyl titanate and the absolute ethyl alcohol of certain volume, be mixed with the ethanolic solution of tetrabutyl titanate, wherein the concentration of tetrabutyl titanate is 1.755 * 810
-4-6.14523 * 10
-4Mol/L;
(2) mol ratio in ammonium iodide amount and butyl titanate is the 0.1:1-1.5:1 ratio, take the ethanolic solution that ammonium iodide joins above-mentioned tetrabutyl titanate, make mixed solution, proceed to subsequently reactor and carry out hydro-thermal for the first time, the temperature of hydro-thermal is 110-220 ℃, the hydro-thermal time is 6-24h, hydro-thermal finishes, centrifugation, washing, dry and obtain N, the nano titanium oxide of I doping is received gel;
(3) take the above-mentioned N made, the nano titanium oxide of I doping is received gel, join in NaOH solution, the concentration of NaOH is 5-12mol/L, wherein N, it is (0.5-10) with the ratio of NaOH solution that the nano titanium oxide of I doping is received gel: (50-120) g/mL, ultrasonic dispersion, ultrasonic time is 10-120min, proceeds to subsequently in reactor and carries out hydro-thermal for the second time, the temperature of hydro-thermal is 80-150 ℃, and the hydro-thermal time is 6-24h; Hydro-thermal finishes for the second time, centrifugation, with distilled water sedimentation 2-5 time, to precipitate with distilled water and again disperse after centrifugation, with the salpeter solution neutralization, until the pH of the solution of sample is neutral, with distilled water washing 2-5 time, dry, make different N, I codope titanium dioxide porous network structure powder.
2. high absorbent-type N according to claim 1, I codope TiO
2The preparation method of porous network structure powder, is characterized in that it is 130-190 ℃ that the middle reactor of step (2) carries out the hydrothermal temperature of hydro-thermal for the first time, and the hydro-thermal time is 12-20h.
3. high absorbent-type N according to claim 1, I codope TiO
2The preparation method of porous network structure powder, is characterized in that in step (3), ultrasonic time is 20-90min.
4. high absorbent-type N according to claim 1, I codope TiO
2The preparation method of porous network structure powder, is characterized in that carrying out the hydrothermal temperature of hydro-thermal for the second time in reactor in step (3) is 90-140 ℃, and the hydro-thermal time is 10-20h.
5. high absorbent-type N claimed in claim 1, I codope TiO
2The application of porous network structure powder, is characterized in that can be applicable to process variable concentrations dye of positive ion waste water, and dye of positive ion concentration is 10-300mg/L, and the adsorbent consumption is 50mg/L-2.5g/L, and adsorption temp is 10-35 ℃.
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| CN102274739A (en) * | 2011-05-31 | 2011-12-14 | 中国科学院新疆理化技术研究所 | Copper-nitrogen double-doped titanium dioxide photocatalytic material |
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| CN104475134A (en) * | 2014-12-05 | 2015-04-01 | 江南大学 | Preparation method of iodine-doped titanium dioxide nano catalyst and use of catalyst in heterogeneous catalysis of configuration inversion of trans-carotenoids |
| CN104475134B (en) * | 2014-12-05 | 2016-09-07 | 江南大学 | The purposes that the preparation method of I2 doping nano titania catalyst and heterogeneous catalysis trans-carotenoid configuration thereof convert |
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