CN1701842A - Ti4+ supported hydroxyapatite nano powder absorbing disinfection material - Google Patents
Ti4+ supported hydroxyapatite nano powder absorbing disinfection material Download PDFInfo
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- CN1701842A CN1701842A CN 200510024794 CN200510024794A CN1701842A CN 1701842 A CN1701842 A CN 1701842A CN 200510024794 CN200510024794 CN 200510024794 CN 200510024794 A CN200510024794 A CN 200510024794A CN 1701842 A CN1701842 A CN 1701842A
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- hydroxyapatite
- disinfection material
- nano powder
- absorbing disinfection
- powder absorbing
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Abstract
一种载Ti4+羟基磷灰石纳米粉体吸附消毒材料，属于材料领域。本发明材料的其化学组成式为：(Ca10－x－yTixRy)(PO4)6(OH)2，其中x＝0.5～6，y＝0.01～0.2，R为Fe3+，Ag+或Ce4+。晶相为羟基磷灰石晶相。晶体结构为六方结构。通过负载Ti4+和少量Fe3+，Ag+或Ce4+离子，通过水热法获得的负载Ti4+的羟基磷灰石吸附消毒材料。本发明具有良好的吸附、光催化杀菌性能，不仅能在紫外线下，而且能在日光下分解污染物。The invention discloses a Ti4 + hydroxyapatite nanometer powder adsorption and disinfection material, which belongs to the field of materials. The chemical composition formula of the material of the present invention is: (Ca 10-x-y Ti x R y )(PO 4 ) 6 (OH) 2 , where x=0.5~6, y=0.01~0.2, R is Fe 3+ , Ag + or Ce 4+ . The crystal phase is hydroxyapatite crystal phase. The crystal structure is hexagonal. By loading Ti 4+ and a small amount of Fe 3+ , Ag + or Ce 4+ ions, the hydroxyapatite adsorption disinfection material loaded with Ti 4+ is obtained by hydrothermal method. The invention has good adsorption and photocatalytic sterilization properties, and can decompose pollutants not only under ultraviolet light but also under sunlight.
Description
Technical field
What the present invention relates to is a kind of nano-powder material, specifically, is a kind of year Ti
4+Hydroxyapatite nano powder absorbing disinfection material belongs to the material technology field.
Background technology
In the modern life, heavy metal ion such as Pb, Cd, Cu, CO, SO
2, NO
xDeng pernicious gas, organic matter volatile matters such as formaldehyde, benzene, organic dyestuff such as methylene blue, rhodamine, pollutant serious harms such as bacterium such as Escherichia coli, staphylococcus aureus human beings'health.The photocatalytic degradation technology has under the normal temperature and pressure just can carry out, and can thoroughly destroy pollutant, does not have secondary pollution and expense or the like advantage.TiO wherein
2Good, the corrosion resistance of photocatalytic activity strong, stability itself is high, price is low relatively and to advantages such as human body avirulences, be acknowledged as best photochemical catalyst.Yet, the first, because the pollutant isoconcentration in the environment is often lower,, cause photocatalytic degradation speed slow so reactant is low in the concentration of catalyst surface enrichment.The second, light-catalyzed reaction is converted into no hazardous substance with pollutant need pass through many intermediate steps usually, and some is extremely harmful material in these intermediate products.The 3rd, TiO
2Photochemical catalyst only when being subjected to the irradiation of ultraviolet light, just may show photocatalytic activity, has influenced its service efficiency.Hydroxyapatite (Ca
10(PO
4)
6(OH)
2) particular structure and composition are arranged, make it very strong suction-operated be arranged to pollutant.Recent findings Ca
10(PO
4)
6(OH)
2Also possess photocatalysis characteristic, correlative study also confirms Ca under the optical excitation
10(PO
4)
6(OH)
2The surface produced sufficient oxygen radical O with strong oxidability
2-, so hydroxyapatite has particular performances as the disinfection material.
Find by prior art documents, people such as M.Wakamura are at Photocatalysis bycalcium hydroxyapatite modified with Ti (IV): Albumin decomposition andbactericidal effect, LANGMUIR, 2003, V19, N8 (APR 15), (the calcium hydroxyapatite protein breakdown and the bactericidal effect of titanium (IV), Langmuir, 2003 are carried in photocatalysis to P3428-3431, V19, N8 P3428-3431) has reported the titanium supported hydroxyapatite that a kind of coprecipitation method prepares, and this material possesses good photo-catalysis function and sterilizing ability, can be in dark surrounds effective kill bacteria, efficient surpasses nano-TiO
2Its weak point is: this titanium supported hydroxyapatite material, Ti
4+Ion concentration is higher, and hydroxyapatite is an amorphous state, and photocatalysis performance reduces significantly, has influenced the application of this material, does not add Fe simultaneously
3+, Ag
+And Ce
4+Element can not demonstrate fully the advantage of titanium supported hydroxyapatite material, and antimicrobial efficiency is lower.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of year Ti is provided
4+Hydroxyapatite nano powder absorbing disinfection material, make it stronger adsorption capacity be arranged to inorganic or organic matter, under ultraviolet ray or solar radiation, can decompose these materials, thereby reach the effect of absorption and decomposing harmful substances, can be applied in fields such as biomaterial, environment-friendly materials and construction materials.
The present invention is achieved through the following technical solutions, by the synthetic Ti that carries of hydro-thermal method
4+The hydroxyapatite absorbing disinfection material, its chemical constitution formula is: (Ca
10-x-yTi
xR
y) (PO
4)
6(OH)
2, x=0.5 ~ 6 wherein, y=0.01 ~ 0.2, R is Fe
3+, Ag
+Or Ce
4+
Ti
4+Hydroxyapatite absorbing disinfection material crystal structure is a hexagonal structure, and crystalline phase is the hydroxyapatite crystalline phase.
Ti is carried in the present invention
4+The preparation method of hydroxyapatite nano powder absorbing disinfection material is by load Ti
4+And small amount of Fe, Ag or Ce are by the load Ti of hydro-thermal method acquisition
4+The hydroxyapatite absorbing disinfection material.
Of the present invention by the synthetic Ti that carries of hydro-thermal method with nanoscale
4+The hydroxyapatite absorbing disinfection material is: at first dispose (Ca+Ti+R) composite solution; Dropping ammonia or acid, the acid-base value of regulator solution through three centrifugations and washing repeatedly, obtains white precipitate A; White precipitate A is put into hydrothermal reaction kettle carry out hydro-thermal reaction; Reactant is taken out in the reaction back, and through three centrifugations and washing repeatedly, drying promptly gets and carries titanium (Ti
4+) absorption of hydroxyapatite complex phase and disinfection nano material.
The present invention is to Pb, Cd, Cu heavy metal ion, CO, SO
2, the NO pernicious gas, formaldehyde, organic matters such as methylene blue have very strong adsorption capacity, directly make or be coated on the relevant carriers, through organic matter and NO pernicious gases such as ultraviolet light or natural light irradiation decomposing formaldehydes, but and deactivation bacterium.
The invention has the beneficial effects as follows: the present invention is at the face coat of construction material, water pollution control, and can be used widely in fields such as air cleaning.The present invention has good adsorption, photo-catalyst performance, can not only be under ultraviolet ray, and can be in decomposing pollutant under the daylight.Have not only that photocatalytic activity is good, corrosion resistance is strong, chemical stability is high, price is relatively low and to advantages such as human body avirulences, utilize the adsorptivity of titanium supported hydroxyapatite simultaneously, the high local concentrations in forming is among a small circle passed through TiO again
2Photocatalytic degradation and the active disinfecting and sterilizing functions of titanium supported hydroxyapatite, these two kinds of complex effects will produce a kind of resultant effect, both can catch harmful virus and bacterium effectively, can make again harmful virus and bacterium at short notice inactivation, kill and finally mineralize and be oxidized to complete harmless CO
2And H
2O can solve continuous use, secondary pollution problem, improves the service efficiency of photochemical catalyst.
The specific embodiment
Embodiment 1
X=0.5, Y=0.2, R=Fe
3+Carry Ti
4+Hydroxyapatite adsorbs a pasteurization material
This example materials outward appearance is ivory buff.With the XRD test, show that its structure is a hexagonal structure, its main compound is hydroxyapatite Ca
10(PO
4)
6(OH)
2X=0.5, Y=0.2, R=Fe
3+Carry Ti
4+Hydroxyapatite adsorbs a pasteurization material, determines the chemical expression formula (Ca of material
9.3Ti
0.5Fe
0.2) (PO
4)
6(OH)
2By the synthetic Ti that carries of hydro-thermal method with nanoscale
4+The hydroxyapatite absorbing disinfection material is at first to dispose (Ca+Ti+Fe) composite solution, with (NH
4) H
2PO
4The solution agitation and dropping is that wherein the mol ratio of (Ca+Ti+Fe)/P is 1.9 in (Ca+Ti+Fe) composite solution of 100 ℃ to temperature.Dropping ammonia or acid then, the acid-base value of regulator solution, remaining on pH value is 8.Through three centrifugations and washing repeatedly, obtain white precipitate A; White precipitate A is put into hydrothermal reaction kettle carry out hydro-thermal reaction, add distilled water, the acid-base value of while regulator solution, remaining on pH value is 8.100 ℃ of hydro-thermal reactions of carrying out 10 hours.Take out reactant behind the final reaction, through three centrifugations and washing repeatedly, drying promptly gets absorption of titanium supported hydroxyapatite complex phase and disinfection nano material.
This material is to heavy metal ion such as Pb, Cd, Cu, CO, SO
2, pernicious gas such as NO, organic matter volatile matters such as formaldehyde, benzene, organic dyestuff such as methylene blue, rhodamine, bacteriums such as Escherichia coli, staphylococcus aureus have very strong adsorption capacity, under sunshine or ultraviolet ray irradiation, Fe
3+Further improve the photocatalysis Decomposition performance of material, very fast organic matters such as degradation of formaldehyde, methylene blue, pernicious gases such as mineralising NO, and can the deactivation bacterium.
Embodiment 2
X=2, Y=0.01, R=Ag
+Carry Ti
4+Hydroxyapatite adsorbs a pasteurization material
This example materials outward appearance is white in color.With the XRD test, show that its structure is a hexagonal structure, its main compound is hydroxyapatite Ca
10(PO
4)
6(OH)
2X=2, Y=0.01, R=Ag
+Carry Ti
4+Hydroxyapatite adsorbs a pasteurization material, determines the chemical expression formula (Ca of material
7.99Ti
2Ag
0.01) (PO
4)
6(OH)
2By the synthetic Ti that carries of hydro-thermal method with nanoscale
4+The hydroxyapatite absorbing disinfection material is at first to dispose (Ca+Ti+Ag) composite solution, with (NH
4) H
2PO
4The solution agitation and dropping is that wherein the mol ratio of (Ca+Ti+Ag)/P is 1.7 in (Ca+Ti+Ag) composite solution of 60 ℃ to temperature.Dropping ammonia or acid then, the acid-base value of regulator solution, remaining on pH value is 14.Through three centrifugations and washing repeatedly, obtain white precipitate A; White precipitate A is put into hydrothermal reaction kettle carry out hydro-thermal reaction, add distilled water, the acid-base value of while regulator solution, remaining on pH value is 14.300 ℃ of hydro-thermal reactions of carrying out 2 hours.Take out reactant behind the final reaction, through three centrifugations and washing repeatedly, drying promptly gets absorption of titanium supported hydroxyapatite complex phase and disinfection nano material.
This material is to heavy metal ion such as Pb, Cd, Cu, CO, SO
2, pernicious gas such as NO, organic matter such as formaldehyde, benzene volatile matter, organic dyestuff such as methylene blue, rhodamine, bacterium such as Escherichia coli, staphylococcus aureus has very strong adsorption capacity, under sunshine or ultraviolet ray irradiation, can degradation of formaldehyde, organic matter such as methylene blue, pernicious gases such as mineralising NO are simultaneously because Ag
+And Ti
4+The active disinfecting and sterilizing functions and the photo-catalysis function of material mutually promote, bacteriums such as Escherichia coli, staphylococcus aureus are had very strong inactivating efficacy.
Embodiment 3
X=6, Y=0.02, R=Ce
4+Carry Ti
4+Hydroxyapatite adsorbs a pasteurization material
This example materials outward appearance is white in color.With the XRD test, show that its structure is a hexagonal structure, its main compound is hydroxyapatite Ca
10(PO
4)
6(OH)
2X=6, Y=0.02, R=Ce
4+Carry Ti
4+Hydroxyapatite adsorbs a pasteurization material, determines the chemical expression formula (Ca of material
3.98Ti
6Ce
0.02) (PO
4)
6(OH)
2By the synthetic Ti that carries of hydro-thermal method with nanoscale
4+The hydroxyapatite absorbing disinfection material is at first to dispose (Ca+Ti+Ce) composite solution, with (NH
4) H
2PO
4The solution agitation and dropping is that wherein the mol ratio of (Ca+Ti+Ce)/P is 1.50 in (Ca+Ti+Ce) composite solution of 20 ℃ to temperature.Dropping ammonia or acid then, the acid-base value of regulator solution, remaining on pH value is 12.Through three centrifugations and washing repeatedly, obtain white precipitate A; White precipitate A is put into hydrothermal reaction kettle carry out hydro-thermal reaction, add distilled water, the acid-base value of while regulator solution, remaining on pH value is 12.200 ℃ of hydro-thermal reactions of carrying out 6 hours.Take out reactant behind the final reaction, through three centrifugations and washing repeatedly, drying promptly gets absorption of titanium supported hydroxyapatite complex phase and disinfection nano material.
This material is to heavy metal ion such as Pb, Cd, Cu, CO, SO
2, pernicious gas such as NO, organic matter such as formaldehyde, benzene volatile matter, organic dyestuff such as methylene blue, rhodamine, bacterium such as Escherichia coli, staphylococcus aureus has very strong adsorption capacity, under sunshine or ultraviolet ray irradiation, can degradation of formaldehyde, organic matter such as methylene blue, pernicious gases such as mineralising NO, and can the deactivation bacterium.Ce
4+And Ti
4+Mutually promote, to organic matters such as degradation of formaldehyde, methylene blues, pernicious gases such as mineralising NO have facilitation preferably.
Claims (3)
1, a kind of year Ti
4+Hydroxyapatite nano powder absorbing disinfection material is characterized in that, its chemical constitution formula is: (Ca
10-x-yTi
xR
y) (PO
4)
6(OH)
2, x=0.5～6 wherein, y=0.01～0.2, R is Fe
3+, Ag
+Or Ce
4+
2, according to claim 1 year Ti
4+Hydroxyapatite nano powder absorbing disinfection material is characterized in that, crystalline phase is the hydroxyapatite crystalline phase.
3, according to claim 1 year Ti
4+Hydroxyapatite nano powder absorbing disinfection material is characterized in that, crystal structure is a hexagonal structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510024794 CN1701842A (en) | 2005-03-31 | 2005-03-31 | Ti4+ supported hydroxyapatite nano powder absorbing disinfection material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510024794 CN1701842A (en) | 2005-03-31 | 2005-03-31 | Ti4+ supported hydroxyapatite nano powder absorbing disinfection material |
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| Publication Number | Publication Date |
|---|---|
| CN1701842A true CN1701842A (en) | 2005-11-30 |
Family
ID=35631906
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7635659B2 (en) * | 2006-03-29 | 2009-12-22 | Fujitsu Limited | Photocatalytic apatite composition as well as production method and article thereof |
| CN101153288B (en) * | 2007-09-29 | 2010-08-11 | 华南理工大学 | Microbial Catalytic Synthesis of Mesoporous Nanopowder Hydroxyapatite |
| WO2013099006A1 (en) * | 2011-12-28 | 2013-07-04 | 富士通株式会社 | Photocatalysts and process for preparing photocatalysts |
| JP2013192996A (en) * | 2012-03-16 | 2013-09-30 | Fujitsu Ltd | Photocatalyst and method of manufacturing photocatalyst |
| CN103537253A (en) * | 2013-10-21 | 2014-01-29 | 哈尔滨工业大学 | Method for preparing mesoporous material from hydroxyapatite |
| JP2014036907A (en) * | 2012-08-10 | 2014-02-27 | Fujitsu Ltd | Photocatalyst, process for producing photocatalyst, and photocatalytic electrode |
| CN107817630A (en) * | 2017-12-07 | 2018-03-20 | 青岛海信电器股份有限公司 | A kind of liquid crystal display device |
| CN111569916A (en) * | 2020-05-11 | 2020-08-25 | 四川大学 | A kind of modified hydroxyapatite denitration catalyst and preparation method thereof |
| CN112516787A (en) * | 2020-10-20 | 2021-03-19 | 俞春亚 | Indoor formaldehyde purification material and preparation method thereof |
-
2005
- 2005-03-31 CN CN 200510024794 patent/CN1701842A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7635659B2 (en) * | 2006-03-29 | 2009-12-22 | Fujitsu Limited | Photocatalytic apatite composition as well as production method and article thereof |
| CN101153288B (en) * | 2007-09-29 | 2010-08-11 | 华南理工大学 | Microbial Catalytic Synthesis of Mesoporous Nanopowder Hydroxyapatite |
| JPWO2013099006A1 (en) * | 2011-12-28 | 2015-04-30 | 富士通株式会社 | Photocatalyst and method for producing photocatalyst |
| WO2013099006A1 (en) * | 2011-12-28 | 2013-07-04 | 富士通株式会社 | Photocatalysts and process for preparing photocatalysts |
| JP2013192996A (en) * | 2012-03-16 | 2013-09-30 | Fujitsu Ltd | Photocatalyst and method of manufacturing photocatalyst |
| JP2014036907A (en) * | 2012-08-10 | 2014-02-27 | Fujitsu Ltd | Photocatalyst, process for producing photocatalyst, and photocatalytic electrode |
| CN103537253A (en) * | 2013-10-21 | 2014-01-29 | 哈尔滨工业大学 | Method for preparing mesoporous material from hydroxyapatite |
| CN103537253B (en) * | 2013-10-21 | 2015-08-05 | 哈尔滨工业大学 | A kind of method of hydroxyapatite preparation mesoporous material |
| CN107817630A (en) * | 2017-12-07 | 2018-03-20 | 青岛海信电器股份有限公司 | A kind of liquid crystal display device |
| CN111569916A (en) * | 2020-05-11 | 2020-08-25 | 四川大学 | A kind of modified hydroxyapatite denitration catalyst and preparation method thereof |
| CN111569916B (en) * | 2020-05-11 | 2021-08-24 | 四川大学 | A kind of modified hydroxyapatite denitration catalyst and preparation method thereof |
| CN112516787A (en) * | 2020-10-20 | 2021-03-19 | 俞春亚 | Indoor formaldehyde purification material and preparation method thereof |
| CN112516787B (en) * | 2020-10-20 | 2022-08-02 | 杭州博华科技创新有限公司 | A kind of indoor formaldehyde purification material and preparation method thereof |
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