CN105399335A - Lanthanum-doped mesoporous bioactive glass, and preparation method and application thereof - Google Patents
Lanthanum-doped mesoporous bioactive glass, and preparation method and application thereof Download PDFInfo
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- CN105399335A CN105399335A CN201510814458.5A CN201510814458A CN105399335A CN 105399335 A CN105399335 A CN 105399335A CN 201510814458 A CN201510814458 A CN 201510814458A CN 105399335 A CN105399335 A CN 105399335A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
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Abstract
The invention relates to a preparation method for a lanthanum-doped ordered mesoporous bioactive glass and application of the glass as an adsorbent and a photocatalyst to the field of water treatment. According to the preparation method, triblock copolymers are used as a surfactant, tetraethoxysilane is used as a silica source, calcium chloride or calcium nitrate is used as a calcium source, phosphoric ether is used as a phosphorus source, and the lanthanum-doped mesoporous bioactive glass is prepared through the sol-gel method by adding nano titanium dioxide particles into a reaction system. The material (namely the glass) comprises components of SiO2, CaO, P2O5 and La2O3, and the ratio of SiO2, CaO, P2O5 to La2O3 is (100-60): (0-35): 5: (0.5-1), the specific surface area of the glass is 200-500 cm<2>/g, and the mesoporous diameters are in the range of 5-50 nm, and are uniform and ordered. The lanthanum-doped mesoporous bioactive glass prepared by the invention has excellent adsorptivity and photocatalytic activity in water, and can be used for removing pollutants in the water environment. The preparation method is mild in condition, simple, feasible, environment-friendly and good in repeatability, and facilitates mass production.
Description
Technical field
The invention belongs to ecological restoration material field, be specifically related to a kind of La doped mesoporous bioglass and preparation method thereof and its application in aquatic ecological restoration as sorbent material and photocatalyst.
Background technology
Bio-vitric is by silicon-dioxide (SiO
2), calcium oxide (CaO), Vanadium Pentoxide in FLAKES (P
2o
5) and sodium oxide (Na
2o) biomaterial being similar to bone structure formed, owing to having good biocompatibility, after Bone Defect Repari and timbering material implant into body, can be combined closely with bone forming, promote Bone Defect Repari quickly and effectively, be thus widely used in bone tissue restoration and Replacing engineering.Mesopore bioactive glass is due to high specific surface area and orderly mesopore orbit, compared to traditional bioglass material, also possess excellent absorption property and germ resistance while improve biocompatibility, therefore had in drug conveying slowly-releasing and apply widely.Chinese patent CN101091807A has prepared the single dispersing bio-vitric nanoparticle with nano pore, and this particle has higher specific surface area and pore volume, has higher biological activity, has very large application prospect in bone tissue restoration and medicine controlled releasing.Chinese patent CN1887361A has prepared a kind of mesoporous biological glass fiber material, and this material has controlled microtexture and macro morphology, has excellent osteogenic activity and cytoactive, can be used for bone renovating material and tissue scaffold design material.But, current this kind of Porous bioglass material is used for the biomedicine field such as bone tissue restoration or medicine controlled releasing, and in environment remediation field, build the porous material with good biological security, can not only effectively remove pollution substance growing in environment, the secondary pollution that the use that can also reduce material brings for environment, therefore develops Biosafety porous material and has great importance in the application in environment remediation field.
Rare earth compound has the physical propertys such as good photoelectromagnetism, is therefore widely used in optical material, magneto-optic memory technique, dielectric materials and chemical sensitisation etc.Rare earth compound can form advanced composite material with other materials, thus gives matrix material good photoelectric properties.Preparation method at present about rear-earth-doped bioactive glass composites have not been reported.Preparation method of the present invention is the lanthanum that adulterates in the building-up process of bio-vitric, obtain the mesoporous bioglass material of La doped, the preparation method of this lanthanum-doped mesoporous bio-vitric still belongs to the first time proposition, prepared material both had absorption property because of the meso-hole structure of bio-vitric, because of the existence of lanthanum compound, there is photocatalytic activity again, be expected to be widely used in environment remediation field.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and application of La doped mesoporous bioglass, this preparation method mild condition, simple, environmental friendliness.The present invention is simple to operate, reproducible, and productive rate is high.
The preparation method of La doped mesoporous bioglass of the present invention, comprises the following steps:
1) tensio-active agent joins in dehydrated alcohol, the solution be uniformly mixed under agitation condition;
2) successively silicon source, calcium source, phosphorus source and solubility lanthanum salt, diluted acid are added in the aqueous solution according to setting ratio;
3) by step 1) gained mixed solution and step 2) gained mixed solution fully mixes, and constant temperature stirs 24 hours;
4) by step 3) gained colloidal sol pours in vessel, and solvent is fully volatilized;
5) 800 DEG C-900 DEG C roasting 6-9 hour, obtain titanium-containing meso-porous bioglass material.
Aforesaid method step 1) in, described tensio-active agent is Pluronic F-127 as hydrophilic block, polycyclic oxypropylene as the triblock copolymer of hydrophobic block, and its molecular formula is EO
npO
meO
n, n=20-140, m=50-100 wherein EO are oxyethylene, and PO is propylene oxide.
Aforesaid method step 2) in, described silicon source is tetraethoxy; Described calcium source is calcium chloride or nitrocalcite; Described phosphorus source is triethyl phosphate; Described solubility lanthanum salt is lanthanum nitrate or Lanthanum trichloride.
Aforesaid method step 1)-4) in, temperature of reaction is room temperature.
The La doped mesoporous bioglass that aforesaid method is obtained, its moiety is (SiO
2)
x-(CaO)
y-(P
2o
5)
z-(La
2o
3)
n, SiO
2: CaO: P
2o
5: La
2o
3mol ratio be (100-60): (0-35): 5: (0.5-1), its specific surface area is 200-500cm
2/ g, mesoporous pore size is 5-50nm, and aperture is homogeneous adjustable.
The La doped mesoporous bioglass prepared by aforesaid method also belongs to protection scope of the present invention.
The removal that above-mentioned La doped mesoporous bioglass is used for pollutent in water surrounding as sorbent material and photocatalyst also belongs to protection scope of the present invention.
Tool of the present invention has the following advantages:
Prepared La doped mesoporous bioglass material has higher specific surface area and homogeneous adjustable mesoporous pore size, have good adsorptivity and photocatalytic activity, and regenerability is good, can be recycled in water.This preparation method mild condition, simple, raw material is inexpensive, reproducible, and productive rate is high, and environmental friendliness is easy to large-scale production.For good technical foundation is set up in the exploitation of ecological restoration material and large-scale production.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the La doped mesoporous bioglass of preparation in the embodiment of the present invention 1.
Fig. 2 is the XRD figure of the La doped mesoporous bioglass of preparation in the embodiment of the present invention 1.
Fig. 3 is the XPS figure of the La doped mesoporous bioglass of preparation in the embodiment of the present invention 1.
Fig. 4 is nitrogen adsorption-desorption curve and the pore size distribution curve of the La doped mesoporous bioglass of preparation in the embodiment of the present invention 1.Wherein, (a) is nitrogen adsorption-desorption curve, and (b) is pore size distribution curve.
Fig. 5 is the adsorption isothermal line of the La doped mesoporous bioglass planar water Methylene Blue of preparation in the embodiment of the present invention 1.
Fig. 6 is the La doped mesoporous bioglass photocatalytic degradation methylene blue catalytic activity comparison diagram of preparation in the embodiment of the present invention 1.
Embodiment
Further illustrate the present invention by the following examples:
Embodiment 1:
4g tensio-active agent P123 joins in 60g dehydrated alcohol, the solution be uniformly mixed under agitation condition; According to SiO
2: CaO: P
2o
5: TiO
2mol ratio be successively tetraethoxy, nitrocalcite, triethyl phosphate, lanthanum nitrate, 0.5M hydrochloric acid soln to be added to the water at 85: 5: 5: 0.5; By above-mentioned two kinds of solution mixing, stir after 24 hours, pour in culture dish by gained colloidal sol, normal temperature places 7 days, and 800 DEG C of roastings 7 hours, obtain La doped bioglass material.
Embodiment 2:
4g tensio-active agent P123 joins in 60g dehydrated alcohol, the solution be uniformly mixed under agitation condition; According to SiO
2: CaO: P
2o
5: TiO
2mol ratio be successively tetraethoxy, nitrocalcite, triethyl phosphate, lanthanum nitrate, 0.5M hydrochloric acid soln to be added to the water at 85: 5: 5: 1; By above-mentioned two kinds of solution mixing, stir after 24 hours, pour in culture dish by gained colloidal sol, normal temperature places 7 days, and 800 DEG C of roastings 7 hours, obtain La doped bioglass material.
Embodiment 3:
4g tensio-active agent P123 joins in 60g dehydrated alcohol, the solution be uniformly mixed under agitation condition; According to SiO
2: CaO: P
2o
5: TiO
2mol ratio be successively tetraethoxy, nitrocalcite, triethyl phosphate, lanthanum nitrate, 0.5M hydrochloric acid soln to be added to the water at 80: 10: 5: 0.5; By above-mentioned two kinds of solution mixing, stir after 24 hours, pour in culture dish by gained colloidal sol, normal temperature places 7 days, and 600 DEG C of roastings 7 hours, obtain La doped bioglass material.
Embodiment 4:
4g tensio-active agent P123 joins in 60g dehydrated alcohol, the solution be uniformly mixed under agitation condition; According to SiO
2: CaO: P
2o
5: TiO
2mol ratio be successively tetraethoxy, nitrocalcite, triethyl phosphate, lanthanum nitrate, 0.5M hydrochloric acid soln to be added to the water at 80: 10: 5: 1; By above-mentioned two kinds of solution mixing, stir after 24 hours, pour in culture dish by gained colloidal sol, normal temperature places 7 days, and 600 DEG C of roastings 7 hours, obtain La doped bioglass material.
Embodiment 5:
4g tensio-active agent P123 joins in 60g dehydrated alcohol, the solution be uniformly mixed under agitation condition; According to SiO
2: CaO: P
2o
5: TiO
2mol ratio be successively tetraethoxy, nitrocalcite, triethyl phosphate, lanthanum nitrate, 0.5M hydrochloric acid soln to be added to the water at 75: 15: 5: 0.5; By above-mentioned two kinds of solution mixing, stir after 24 hours, pour in culture dish by gained colloidal sol, normal temperature places 5 days, and 600 DEG C of roastings 6 hours, obtain La doped bioglass material.
Embodiment 6:
8g tensio-active agent F127 joins in 60g dehydrated alcohol, the solution be uniformly mixed under agitation condition; According to SiO
2: CaO: P
2o
5: TiO
2mol ratio be successively tetraethoxy, nitrocalcite, triethyl phosphate, lanthanum nitrate, 0.5M hydrochloric acid soln to be added to the water at 85: 5: 5: 0.5; By above-mentioned two kinds of solution mixing, stir after 24 hours, pour in culture dish by gained colloidal sol, normal temperature places 7 days, and 600 DEG C of roastings 7 hours, obtain La doped bioglass material.
Embodiment 7:
3.6g tensio-active agent F104 joins in 60g dehydrated alcohol, the solution be uniformly mixed under agitation condition; According to SiO
2: CaO: P
2o
5: TiO
2mol ratio be successively tetraethoxy, nitrocalcite, triethyl phosphate, lanthanum nitrate, 0.5M hydrochloric acid soln to be added to the water at 85: 5: 5: 0.5; By above-mentioned two kinds of solution mixing, stir after 24 hours, pour in culture dish by gained colloidal sol, normal temperature places 7 days, and 600 DEG C of roastings 7 hours, obtain La doped bioglass material.
In the above-described embodiments, P123 is EO
20pO
70eO
20, F127 is EO
106pO
70eO
106, F104 is EO
27pO
61eO
27, wherein EO is oxyethylene, and PO is propylene oxide.
Embodiment 8: the absorption property evaluation of La doped mesoporous bioglass material
Measure La doped mesoporous bioglass obtained in embodiment 2, the methylene blue solution being 20mg/L with the concentration of 25mL mixes, constant temperature 30 DEG C vibration, sample in different time points respectively, supernatant liquor is got after centrifugation, measure methylene blue residual concentration with ultraviolet-visible spectrophotometer, calculate Methylene blue clearance.
Embodiment 9: the photocatalytic activity evaluation of La doped mesoporous bioglass material
Measure La doped mesoporous bioglass obtained in not lanthanum-doped mesoporous bio-vitric obtained in 0.06g embodiment 1 and embodiment 2 respectively, the methylene blue solution being 20mg/L with the concentration of 25mL respectively mixes, be positioned in 24w, 254nm UV-light evaluating apparatus after dark absorption 2h reaches adsorption equilibrium and carry out activity rating, sample after 3h, supernatant liquor is got after centrifugation, measure methylene blue residual concentration with ultraviolet-visible spectrophotometer, calculate Methylene blue clearance.
Claims (7)
1. a preparation method for La doped mesoporous bioglass, comprises the steps:
1) tensio-active agent joins in dehydrated alcohol, the solution be uniformly mixed under agitation condition;
2) successively silicon source, calcium source, phosphorus source, solubility lanthanum salt, diluted acid are added in the aqueous solution according to setting ratio;
3) by step 1) gained mixed solution and step 2) gained mixed solution fully mixes, and constant temperature stirs 24 hours;
4) by step 3) gained colloidal sol pours in vessel, and solvent is fully volatilized;
5) 800 DEG C-900 DEG C roasting 6-9 hour, obtain La doped mesoporous bioglass.
2. method according to claim 1, is characterized in that: described method steps 1) in, described tensio-active agent is Pluronic F-127 as hydrophilic block, polycyclic oxypropylene as the triblock copolymer of hydrophobic block, and its molecular formula is EO
npO
meO
n, n=20-140, m=50-100 wherein EO are oxyethylene, and PO is propylene oxide.
3. method according to claim 1 and 2, is characterized in that: described method steps 2) in, described silicon source is tetraethoxy; Described calcium source is calcium chloride or nitrocalcite; Described phosphorus source is triethyl phosphate; Described solubility lanthanum salt is lanthanum nitrate or Lanthanum trichloride.
4. the method according to any one of claim 1-3, is characterized in that: described method steps 1)-4) in, temperature of reaction is room temperature.
5. the method according to any one of claim 1-4, is characterized in that: described obtained La doped mesoporous bioglass, its moiety is (SiO
2)
x-(CaO)
y-(P
2o
5)
z-(TiO
2)
n, SiO
2: CaO: P
2o
5: La
2o
3mol ratio be (100-60): (0-35): 5: (0.5-1), its specific surface area is 200-500cm
2/ g, mesoporous pore size is 5-50nm, and aperture is homogeneous adjustable.
6. the La doped mesoporous bioglass that method prepares according to any one of claim 1-5.
7. La doped mesoporous bioglass according to claim 6 is used for the removal of pollutent in water surrounding as sorbent material and photocatalyst.
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|---|---|---|---|
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|---|---|---|---|
| CN201510814458.5A CN105399335A (en) | 2015-11-18 | 2015-11-18 | Lanthanum-doped mesoporous bioactive glass, and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673426A (en) * | 2017-01-13 | 2017-05-17 | 上海师范大学 | Porous-microsphere nanoscale bioglass material doped with rare earth element as well as preparation method and application of porous-microsphere nanoscale bioglass material |
| CN107308499A (en) * | 2017-04-19 | 2017-11-03 | 上海师范大学 | Nanometer biological glass/polymer three-dimensional porous material and its preparation method and application |
| CN111268916A (en) * | 2020-03-18 | 2020-06-12 | 四川大学 | Preparation method of selenium-doped silicon-calcium-phosphorus bioactive mesoporous glass powder |
| CN111646703A (en) * | 2020-05-18 | 2020-09-11 | 东华大学 | Fluoride/oxyfluoride fluorescent glass ceramic and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10120540A (en) * | 1996-10-23 | 1998-05-12 | Sunstar Inc | Composition containing biologically active glass for oral cavity |
| CN103626396A (en) * | 2013-12-13 | 2014-03-12 | 天津工业大学 | Preparation method of titanium-containing mesoporous bioglass |
-
2015
- 2015-11-18 CN CN201510814458.5A patent/CN105399335A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10120540A (en) * | 1996-10-23 | 1998-05-12 | Sunstar Inc | Composition containing biologically active glass for oral cavity |
| CN103626396A (en) * | 2013-12-13 | 2014-03-12 | 天津工业大学 | Preparation method of titanium-containing mesoporous bioglass |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673426A (en) * | 2017-01-13 | 2017-05-17 | 上海师范大学 | Porous-microsphere nanoscale bioglass material doped with rare earth element as well as preparation method and application of porous-microsphere nanoscale bioglass material |
| CN107308499A (en) * | 2017-04-19 | 2017-11-03 | 上海师范大学 | Nanometer biological glass/polymer three-dimensional porous material and its preparation method and application |
| CN111268916A (en) * | 2020-03-18 | 2020-06-12 | 四川大学 | Preparation method of selenium-doped silicon-calcium-phosphorus bioactive mesoporous glass powder |
| CN111646703A (en) * | 2020-05-18 | 2020-09-11 | 东华大学 | Fluoride/oxyfluoride fluorescent glass ceramic and preparation method and application thereof |
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