CN103332736A - Preparation method of titanium dioxide with multistage pore structure - Google Patents
Preparation method of titanium dioxide with multistage pore structure Download PDFInfo
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- CN103332736A CN103332736A CN2013102321445A CN201310232144A CN103332736A CN 103332736 A CN103332736 A CN 103332736A CN 2013102321445 A CN2013102321445 A CN 2013102321445A CN 201310232144 A CN201310232144 A CN 201310232144A CN 103332736 A CN103332736 A CN 103332736A
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Abstract
The invention relates to a preparation method of titanium dioxide with a multistage pore structure. The preparation method mainly comprises the steps of: by artemia cysts as hard templates, dibutyl phthalate as a precursor, absolute ethyl alcohol as a solvent and glacial acetic acid as a chelating agent, preparing titanium dioxide gel, then stirring to form wet gel, drying the obtained wet gel in a drying box, and calcining in a muffle furnace, thus obtaining the titanium dioxide with the multistage pore structure. The preparation method is low in cost, simple in technique, easy to control and good in repeatability, the titanium dioxide is even in particle size distribution, larger in particles, easy to recover, and can be widely applied to the fields of photocatalysis, food packaging materials, light-sensing materials and the like, and pore walls are mutually communicated.
Description
Technical field
The invention belongs to technical field of function materials, particularly a kind of preparation method of metal oxide.
Background technology
Titanium dioxide is having wide application prospect because of advantages such as its chemical stability is good, catalytic activity is high, cheap and easy to get, nontoxic and excellent semiconductor property aspect the energy and the environment.Utilize the ability of its transparency and scatters ultraviolet, can make packaging material for food, woodenware protective paint and makeup sunscreen etc.; Utilize its photoconductivity and photosensitivity, can develop a kind of TiO
2Sensitive materials; Utilize nano titanium oxide to make catalyzer, can handle organic waste water.But according to the literature, be used for light-catalysed titanium dioxide at present and mostly be nano-powder, exist during application to be easy to run off and reclaim difficult problem, running cost is higher.The poriferous titanium dioxide particle size reaches micron order, is easy to control and recovery during application, and because it has bigger specific surface area and more regular pore passage structure, the surfactivity center is many, is conducive to improve photocatalysis efficiency simultaneously.
The synthetic soft template method that is mainly of present poriferous titanium dioxide, used soft template is mainly tensio-active agent, but the order of the wayward product pore passage structure of this method, and connective bad between the duct.
Summary of the invention
The preparation method that the purpose of this invention is to provide that a kind of cost is low, technology is simple, even aperture distribution, particle are big, can provide the titanium dioxide with multi-stage artery structure of photocatalysis performance.The present invention mainly is to be hard template with the artemia cysts shell, Butyl Phthalate is precursor, dehydrated alcohol is solvent, Glacial acetic acid is sequestrant, after preparing TiO 2 sol, be stirred to the formation wet gel, the wet gel of gained is dry in loft drier, in retort furnace, calcine again, namely obtain having the titanium dioxide of multi-stage artery structure.
Preparation method of the present invention is as follows:
(1) the artemia cysts shell is cleaned up, ball milling was the HCl of 6～12mol/L, the H of 8～18mol/L with concentration respectively after 6 hours
2SO
4, 6～14mol/L HNO
3, 2～6mol/L KOH soak pre-treatment, pretreatment time is every kind of material 2～6h, drying is removed moisture.
(2) Butyl Phthalate is dissolved in the dehydrated alcohol, the speed with 400～800r/min under 50 ℃ stirs 10～30min.The volume ratio of described Butyl Phthalate and dehydrated alcohol is 1:1.7～2.
(3) the artemia cysts shell of the above-mentioned processing of adding in above-mentioned solution, its ratio is to add 0.04～0.06g artemia cysts shell in every milliliter of above-mentioned solution, continues 50 ℃ of constant temperature and stirs 10～30min.
(4) in the above-mentioned solution that has added the artemia cysts shell, dropwise add the mixed solution of dehydrated alcohol, Glacial acetic acid and distilled water.The volume ratio of dehydrated alcohol and Glacial acetic acid is 1:0.15～0.22 in the mixed solution, and the volume ratio of the Butyl Phthalate of distilled water and above-mentioned adding is 0.875～1.5:1, continues 50 ℃ of constant temperature and is stirred to formation colloidal sol, is warming up to 80～100 ℃, is stirred to the formation wet gel.
(5) above-mentioned wet gel is formed xerogel at 80～100 ℃ of loft drier inner drying 6～24h.
(6) above-mentioned xerogel is warming up to 400～800 ℃ with the speed of 1～10 ℃/min in retort furnace and calcines, insulation 4～6h namely makes the titanium dioxide of multi-stage artery structure.
The present invention compared with prior art has following advantage:
1, raw material is easy to get, and the artemia cysts shell all has distribution in the salt lake in each continent, the world in the contour saltwater in salt pan.
2, technology is simple, and repeatability is high, constant product quality.
3, the titanium dioxide that makes has regular multi-stage artery structure, and specific surface area is big, and avtive spot is many, is beneficial to the photocatalytic activity that improves material.
4, the titanium dioxide granule that makes is bigger, reclaims for the treatment of being easy to behind the waste water from dyestuff.Can be widely used in fields such as photochemical catalysis, packaging material for food and sensitive materials.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the multistage pore canal titanium dioxide of the embodiment of the invention 1 preparation.
Fig. 2 is the sem photograph of the multistage pore canal titanium dioxide of the embodiment of the invention 2 preparations.
Fig. 3 is the degradation rate change curve in time of the multistage pore canal titanium dioxide of the embodiment of the invention 4 preparation methylene blue during as photocatalyst.
Embodiment
The artemia cysts shell is cleaned up with a large amount of distilled water, and ball milling was the HCl of 6mol/L, the H of 8mol/L with concentration respectively after 6 hours
2SO
4, 6mol/L HNO
3, 2mol/L KOH soak pre-treatment, soak time is every kind of material 2h, drying is removed moisture; The 5ml Butyl Phthalate is dissolved in the 10ml dehydrated alcohol, and the speed with 400r/min under 50 ℃ stirs 10min; Add the above-mentioned treated artemia cysts shell of 0.6g, continue 50 ℃ of constant temperature and stir 10min; Add 10ml dehydrated alcohol, 2ml Glacial acetic acid and 5ml distilled water, 50 ℃ of constant temperature are stirred to formation colloidal sol, be warming up to 80 ℃, constant temperature is stirred to the formation wet gel, wet gel is put into 80 ℃ of dry 6h of loft drier form xerogel, xerogel is put into retort furnace again and be warming up to 400 ℃ with the speed of 1 ℃/min and calcine, insulation 4h namely makes the titanium dioxide with multi-stage artery structure.The titanium dioxide of the multi-stage artery structure that makes as shown in Figure 1, is the titanium dioxide of pure phase.
Get the multistage pore canal titanium dioxide 30mg of above-mentioned preparation, ultra-sonic dispersion is the methylene blue solution of 10mg/L in 100ml concentration, ultrasonic 20min, dark reaction 30min, every 10min sampling 5ml centrifugation, get supernatant liquid and adopt the ultraviolet-visible absorption spectroscopy method to record the concentration of the series of samples of getting, the degradation rate of 40min methylene blue can reach 90.13% as can be known as calculated.
Embodiment 2
The artemia cysts shell is cleaned up with a large amount of distilled water, and ball milling was the HCl of 9mol/L, the H of 13mol/L with concentration respectively after 6 hours
2SO
4, 10mol/L HNO
3, 4mol/L KOH soak pre-treatment, soak time is every kind of material 4h, drying is removed moisture; The 7.5ml Butyl Phthalate is dissolved in the 13.1ml dehydrated alcohol, and the speed with 600r/min under 50 ℃ stirs 20min; After adding the above-mentioned treated artemia cysts shell of 1.03g, continue 50 ℃ of constant temperature and stir 20min; Add 20ml dehydrated alcohol, 3.3ml Glacial acetic acid and 10ml distilled water, 50 ℃ of constant temperature are stirred to formation colloidal sol, be warming up to 90 ℃, constant temperature is stirred to the formation wet gel, wet gel is put into 90 ℃ of dry 15h of loft drier form xerogel, xerogel is put into retort furnace again and be warming up to 600 ℃ with the speed of 5.5 ℃/min and calcine, insulation 5h namely obtains the titanium dioxide of multi-stage artery structure.As shown in Figure 2, can be observed the multi-stage artery structure of titanium dioxide.
Get the titanium dioxide 30mg of the multi-stage artery structure of above-mentioned preparation, ultra-sonic dispersion is the methylene blue solution of 10mg/L in 100ml concentration, ultrasonic 20min, dark reaction 30min, every 10min sampling 5ml centrifugation, get supernatant liquid and adopt the ultraviolet-visible absorption spectroscopy method to record the concentration of the series of samples of getting, the degradation rate of 30min methylene blue can reach 92.47% as can be known as calculated.
Embodiment 3
The artemia cysts shell is cleaned up with a large amount of distilled water, and ball milling was the HCl of 12mol/L, the H of 18mol/L with concentration respectively after 6 hours
2SO
4, 14mol/L HNO
3, 6mol/L KOH soak pre-treatment, soak time is every kind of material 6h, drying is removed moisture; The 10ml Butyl Phthalate is dissolved in the 17ml dehydrated alcohol, and the speed with 800r/min under 50 ℃ stirs 30min; After adding the above-mentioned artemia cysts shell of handling well of 1.62g, continue 50 ℃ of constant temperature and stir 30min; Add 30ml dehydrated alcohol, 4.5ml Glacial acetic acid and 15ml distilled water, 50 ℃ of constant temperature are stirred to formation colloidal sol, be warming up to 100 ℃, constant temperature is stirred to the formation wet gel, wet gel is put into 100 ℃ of dry 24h of loft drier form xerogel, xerogel is put into retort furnace again and be warming up to 800 ℃ with the speed of 10 ℃/min and calcine, insulation 6h namely obtains the titanium dioxide of multi-stage artery structure.
Get the titanium dioxide 30mg of the multi-stage artery structure of above-mentioned preparation, ultra-sonic dispersion is the methylene blue solution of 10mg/L in 100ml concentration, ultrasonic 20min, dark reaction 30min, every 10min sampling 5ml centrifugation, get supernatant liquid and adopt the ultraviolet-visible absorption spectroscopy method to record the concentration of the series of samples of getting, the degradation rate of 30min methylene blue can reach 92.00% as can be known as calculated.
Embodiment 4
The artemia cysts shell is cleaned up with a large amount of distilled water, and ball milling was the HCl of 10mol/L, the H of 15mol/L with concentration respectively after 6 hours
2SO
4, 12mol/L HNO
3, 5mol/L KOH soak pre-treatment, soak time is every kind of material 5h, drying is removed moisture; The 8ml Butyl Phthalate is dissolved in the 14ml dehydrated alcohol, and the speed with 700r/min under 50 ℃ stirs 25min; After adding the above-mentioned treated artemia cysts shell of 1.21g, continue 50 ℃ of constant temperature and stir 25min; Add 25ml dehydrated alcohol, 5.5ml Glacial acetic acid and 7ml distilled water, 50 ℃ of constant temperature are stirred to formation colloidal sol, be warming up to 90 ℃, constant temperature is stirred to the formation wet gel, wet gel is put into 85 ℃ of dry 18h of loft drier form xerogel, xerogel is put into retort furnace again and be warming up to 450 ℃ with the speed of 4 ℃/min and calcine, insulation 4.5h namely obtains the titanium dioxide of multi-stage artery structure.
Get the titanium dioxide 30mg of the multi-stage artery structure of above-mentioned preparation, ultra-sonic dispersion is the methylene blue solution of 10mg/L in 100ml concentration, ultrasonic 20min, dark reaction 30min, every 10min sampling 5ml centrifugation, get supernatant liquid and adopt the ultraviolet-visible absorption spectroscopy method to record the concentration of the series of samples of getting, the degradation rate of 30min methylene blue can reach 91.88% as can be known as calculated.As shown in Figure 3, be titanium dioxide with the multi-stage artery structure of present embodiment preparation during as catalyzer, the methylene blue degradation rate is curve over time, illustrates that prepared multistage pore canal titanium dioxide possesses extraordinary photocatalytic activity.
Claims (1)
1. the preparation method with titanium dioxide of multi-stage artery structure is characterized in that,
(1) the artemia cysts shell is cleaned up, ball milling was the HCl of 6～12mol/L, the H of 8～18mol/L with concentration respectively after 6 hours
2SO
4, 6～14mol/L HNO
3, 2～6mol/L KOH soak pre-treatment, pretreatment time is every kind of material 2～6h, drying is removed moisture;
(2) Butyl Phthalate is dissolved in the dehydrated alcohol, the speed with 400～800r/min under 50 ℃ stirs 10～30min.The volume ratio of described Butyl Phthalate and dehydrated alcohol is 1:1.7～2;
(3) the artemia cysts shell of the above-mentioned processing of adding in above-mentioned solution, its ratio is to add 0.04～0.06g artemia cysts shell in every milliliter of above-mentioned solution, continues 50 ℃ of constant temperature and stirs 10～30min;
(4) in the above-mentioned solution that has added the artemia cysts shell, dropwise add the mixed solution of dehydrated alcohol, Glacial acetic acid and distilled water, the volume ratio of dehydrated alcohol and Glacial acetic acid is 1:0.15～0.22 in the mixed solution, the volume ratio of the Butyl Phthalate of distilled water and above-mentioned adding is 0.875～1.5:1, continue 50 ℃ of constant temperature and be stirred to formation colloidal sol, be warming up to 80～100 ℃, be stirred to the formation wet gel;
(5) above-mentioned wet gel is formed xerogel at 80～100 ℃ of loft drier inner drying 6～24h;
(6) above-mentioned xerogel is warming up to 400～800 ℃ with the speed of 1～10 ℃/min in retort furnace and calcines, insulation 4～6h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107502259A (en) * | 2017-09-13 | 2017-12-22 | 陈贤尧 | LED encapsulation material that a kind of hardness is high and adhesion strength is excellent and preparation method thereof |
| CN109301226A (en) * | 2018-10-22 | 2019-02-01 | 泉州齐美电子科技有限公司 | A kind of preparation process of the lithium ion battery electrode material modified based on graphene |
| CN115069260A (en) * | 2022-07-29 | 2022-09-20 | 南京工业大学 | Nickel-based hierarchical porous reforming hydrogen production catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481874A (en) * | 2009-01-23 | 2009-07-15 | 东华大学 | Nano metal titanium dioxide sol negative oxygen ion finishing method for fabric |
| CN102249300A (en) * | 2011-05-12 | 2011-11-23 | 陕西鸿禧新材料有限公司 | Preparation method of black titanium dioxide |
| CN103111301A (en) * | 2013-01-29 | 2013-05-22 | 燕山大学 | Preparation method of multiple-duct composite metal oxide |
-
2013
- 2013-06-09 CN CN2013102321445A patent/CN103332736A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481874A (en) * | 2009-01-23 | 2009-07-15 | 东华大学 | Nano metal titanium dioxide sol negative oxygen ion finishing method for fabric |
| CN102249300A (en) * | 2011-05-12 | 2011-11-23 | 陕西鸿禧新材料有限公司 | Preparation method of black titanium dioxide |
| CN103111301A (en) * | 2013-01-29 | 2013-05-22 | 燕山大学 | Preparation method of multiple-duct composite metal oxide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107502259A (en) * | 2017-09-13 | 2017-12-22 | 陈贤尧 | LED encapsulation material that a kind of hardness is high and adhesion strength is excellent and preparation method thereof |
| CN109301226A (en) * | 2018-10-22 | 2019-02-01 | 泉州齐美电子科技有限公司 | A kind of preparation process of the lithium ion battery electrode material modified based on graphene |
| CN115069260A (en) * | 2022-07-29 | 2022-09-20 | 南京工业大学 | Nickel-based hierarchical porous reforming hydrogen production catalyst and preparation method and application thereof |
| CN115069260B (en) * | 2022-07-29 | 2023-05-05 | 南京工业大学 | Nickel-based hierarchical porous reforming hydrogen production catalyst and preparation method and application thereof |
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Application publication date: 20131002 |