CN107161970A - It is a kind of that there is magnesium phosphate nano material of flourishing mesopore orbit structure and preparation method thereof - Google Patents
It is a kind of that there is magnesium phosphate nano material of flourishing mesopore orbit structure and preparation method thereof Download PDFInfo
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- CN107161970A CN107161970A CN201710533389.XA CN201710533389A CN107161970A CN 107161970 A CN107161970 A CN 107161970A CN 201710533389 A CN201710533389 A CN 201710533389A CN 107161970 A CN107161970 A CN 107161970A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/34—Magnesium phosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention belongs to magnesium phosphate preparation field, the preparation method of more particularly to a kind of magnesium phosphate nano material with meso-hole structure.The present invention uses water-soluble magnesium salt as magnesium source, phosphoric acid or water-soluble phosphate as phosphorus source, and magnesium source, phosphorus source are added in aqueous phase solution and are well mixed as solvent by aqueous phase solution according to the ratio of Mg/P mol ratios 0.5 1.5；The pH value for adjusting solution is hydro-thermal reaction 1 24 hours at 7 12,100 200 DEG C, separation, washs and dries gained precipitation the magnesium phosphate nano material with flourishing mesopore orbit structure is made.The mesoporous magnesium phosphate of gained of the invention has high-specific surface area and high absorption capacity, has in fields such as organizational project, drug delivery, modern agriculture, sewage disposals extensively using value.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, in particular it relates to which a kind of have flourishing mesopore orbit structure
Phosphoric acid magnesium material and preparation method thereof, it can be widely applied to organizational project, drug delivery, modern agriculture, sewage disposal etc.
Field.
Background technology
Magnesium phosphate be it is a kind of all have in fields such as organizational project, drug delivery, modern agriculture, wastewater treatments it is commonly used
Ceramic material.
In biological technical field, magnesium ion and phosphate anion are generally considered in body metabolism have important work
With, therefore phosphoric acid magnesium material is considered as a kind of active with good biological, the descendent map material of biocompatibility.
In a particular application, magnesium phosphate be once used for build bone filling bone cement material, the compound rest for preparing organizational project,
Nano-carrier for serving as gene transfection, the degradable carrier for drug delivery.
And in modern agriculture, because magnesium ion is the necessary nutrient of plant growth, the magnesium ion of magnesium phosphate and its
Drug delivery and degradable characteristic, were once used for modern agriculture as fertilizer.
And the magnesium ion in sewage treatment area, magnesium phosphate can exchange to form a huge sum of money with the heavy metal ion in waste water
Belong to phosphate heavy metal and realize fixation.
In summary, magnesium phosphate ceramic material has extensively using potentiality and good economic value.
Mesoporous material refers to a polyporous materials of the aperture between 2-50nm.Mesoporous material have high specific surface area,
The features such as regular pore passage structure, narrow pore-size distribution, pore size continuously adjustabe so that it is in many micro-pore zeolites
Molecular sieve is difficult to the absorption of the macromolecular completed, separation, is especially played a role in catalytic reaction.Moreover, this material has
Sequence duct can be used as " microreactor ", be formed wherein after uniform and stable " object " material of assembling with nanoscale
For " Subjective and Objective material ", small-size effect, the amount that may have due to the host and guest's bulk effect and guest materials between its master, object
Sub- dimensional effect etc. will be allowed to be expected in electrode material, photoelectric device, microelectric technique, chemical sensor, nonlinear optics material
The fields such as material are widely used.It is found that the introducing of meso-hole structure can be carried significantly in the research process of ceramic material
Specific surface area, adsorption capacity, Drug loading capacity, the bioactivity of high ceramic material.
Current mesoporous ceramic material is prepared generally by template, i.e., by triblock copolymer polyoxyethylene-polyoxy third
Alkene-polyoxyethylene (F127), dodecyl sodium sulfate (CTAB), PEO-PPOX-PEO three block
The templates such as copolymer (P123) are compound in ceramic material structure, then go removing template to leave meso-hole structure by high-temperature calcination.
But template used in template has certain toxicity, its residual can pollute the purity of mesoporous hydroxyapatite, and in height
Temperature calcining goes that during removing template particle agglomeration can be caused.Each of which increases the complexity of technique and production cost, and meeting
Cause environmental pollution.Additionally due to magnesium phosphate contains the substantial amounts of crystallization water, this template calcination method can also destroy the knot of magnesium phosphate
Structure.It is therefore on mesoporous magnesium phosphate, especially environmental protection and economy prepares mesoporous magnesium phosphate nano material there is presently no any
Relevant report.
The content of the invention
It is contemplated that breaking through the structural limitation of existing magnesium phosphate ceramic material and the meso-hole structure preparation side of ceramic material
There is provided a kind of magnesium phosphate nano material with meso-hole structure and preparation method and application for the defect of method.
The present invention uses water-soluble magnesium salt and phosphoric acid or water-soluble phosphate for raw material, before being formed in aqueous phase solvent
Body.Then regulated and controled under hydrothermal conditions by the motion of hydrone during the self-assembled growth of phosphoric acid magnesium crystal in magnesium phosphate
The formation of meso-hole structure.
Present invention firstly provides a kind of magnesium phosphate nano material, with meso-hole structure, it, which is prepared by the following method, obtains：
(1) use water-soluble magnesium salt as magnesium source, phosphoric acid or water-soluble phosphate are as phosphorus source, and deionized water is as molten
Agent, magnesium source, phosphorus source are added in aqueous phase solution and are well mixed；
(2) pH value of solution is adjusted, hydro-thermal reaction is carried out, separation, washing and dry gained are precipitated, and being made has prosperity
The magnesium phosphate nano material of mesopore orbit structure.
Water-soluble magnesium salt is to use in the step of magnesium phosphate nano material of the present invention, its above-mentioned preparation method (1)
One or more in magnesia, magnesium hydroxide, magnesium chloride, magnesium nitrate, magnesium gluconate.
Water-soluble phosphate is in boiling water in the step of magnesium phosphate nano material of the present invention, its above-mentioned preparation method (1)
In solvable phosphate, can for diammonium hydrogen phosphate, ammonium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate,
One or more in potassium dihydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate, calgon, phosphorous biomolecule.
Aqueous phase solution is water, containing water-soluble in the step of magnesium phosphate nano material of the present invention, its above-mentioned preparation method (1)
The aqueous solution of property organic solvent or the water soluble organic molecules with hydroxyl/carboxylic group.
In the present invention, ethanol can be added in liquid phase water, glycerine, the water-miscible organic solvent such as Triton X-100,
Glucose can be added, Tea Polyphenols, citric acid, vitamin C etc. has the water soluble organic molecules of hydroxyl/carboxylic group to phosphoric acid
The pattern of magnesium nano material is regulated and controled.
The molar concentration of magnesium ion is 0.001-1 mol/Ls in magnesium source in step (1)；Phosphorus rubs in phosphorus source in step (1)
Your concentration is 0.001-1 mol/Ls；Magnesium phosphorus mol ratio is 0.5-1.5 in step (1):1.
The pH value of regulation solution is 7-12 in the step of magnesium phosphate nano material of the present invention, its above-mentioned preparation method (2).
Hydrothermal temperature is 100-200 DEG C, time 1-24 hour in step (2).
It is preferred that hydrothermal temperature is 120-160 DEG C in step (2), the time is 2-6 hours.
Preferably, the liquid phase of the reaction system is water.
Preferably, the magnesium phosphate nano material with meso-hole structure obtained in the reaction system body can pass through filtering
Method obtain, and cleaned using water.
Preferably, the magnesium phosphate nano material with meso-hole structure of gained can be done under 50-80 DEG C of air atmosphere
It is dry.
On the other hand, the invention provides a kind of magnesium phosphate preparation method of nano material with meso-hole structure, including with
Lower step：
(1) use water-soluble magnesium salt as magnesium source, phosphoric acid or water-soluble phosphate are as phosphorus source, and deionized water is as molten
Agent, magnesium source, phosphorus source are added in aqueous phase solution and are well mixed；
(2) pH value of solution is adjusted, hydro-thermal reaction is carried out, separation, washing and dry gained are precipitated, and being made has prosperity
The magnesium phosphate nano material of mesopore orbit structure.
Wherein, water-soluble magnesium salt is that can use magnesia, magnesium hydroxide, magnesium chloride, magnesium nitrate, grape in step (1)
One or more in saccharic acid magnesium.
Water-soluble phosphate is phosphate solvable in boiling water in step (1), can be diammonium hydrogen phosphate, biphosphate
Ammonium, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate, hexa metaphosphoric acid
One or more in sodium, phosphorous biomolecule.
Aqueous phase solution is that water, the water solubility containing water-miscible organic solvent or with hydroxyl/carboxylic group have in step (1)
The aqueous solution of machine molecule.
In the preparation process in accordance with the present invention, ethanol can be added in liquid phase water, glycerine, the water solubility such as Triton X-100 has
Machine solvent, can also add glucose, and Tea Polyphenols, citric acid, vitamin C etc. has the water-soluble organic of hydroxyl/carboxylic group
Molecule regulates and controls to the pattern of magnesium phosphate nano material.
The molar concentration of magnesium ion is 0.001-1 mol/Ls in magnesium source in step (1)；Phosphorus rubs in phosphorus source in step (1)
Your concentration is 0.001-1 mol/Ls；Magnesium phosphorus mol ratio is 0.5-1.5 in step (1):1.
The pH value of regulation solution is 7-12 in the step of magnesium phosphate nano material of the present invention, its above-mentioned preparation method (2).
Hydrothermal temperature is 100-200 DEG C, time 1-24 hour in step (2).
It is preferred that hydrothermal temperature is 120-160 DEG C in step (2), the time is 2-6 hours.
Preferably, the liquid phase of the reaction system is water.
Preferably, what is obtained in the reaction system body has the magnesium phosphate nano material of flourishing mesopore orbit structure can
To be obtained by the method for filtering, and cleaned using water.
Preferably, the magnesium phosphate nano material with flourishing mesopore orbit structure of gained can be in 50-80 DEG C of air atmosphere
It is dried under enclosing.
Hydro-thermal reaction can be used as microwave and/or ultrasonic wave added progress in step (2).
Present invention also offers obtained magnesium phosphate nano material in organizational project, drug delivery, modern agriculture or dirt
Application in water process.
The beneficial effects of the present invention are magnesium phosphate nano material of the present invention has meso-hole structure, preparation technology of the present invention
It is simple and convenient to operate, it is not necessary to which the equipment of complex and expensive, raw material and intermediate product have no toxic side effect, environment will not be caused
Pollution, is expected to realize industrialized production.The nanometer of the magnesium phosphate with meso-hole structure prepared by preparation method of the present invention
Material all has a good application prospect in fields such as organizational project, drug delivery, modern agriculture, wastewater treatments.
Brief description of the drawings
Fig. 1 is the XRD of magnesium phosphate prepared by embodiment 1, and it mainly includes Mg3(PO4)2.5H2O,Mg2(P2O7).6H2O,
Mg2(PO4)OH,Mg3(PO4)2.22H2The compositions such as O.
Fig. 2 is the TEM figures of magnesium phosphate prepared by embodiment 1, here it is apparent that it has meso-hole structure.
Fig. 3 is the XRD of magnesium phosphate prepared by embodiment 2, and it mainly includes Mg3(PO4)2.5H2O,Mg2(P2O7).6H2O,
Mg2(PO4)OH,Mg3(PO4)2.22H2The compositions such as O.
Fig. 4 is the TEM figures of magnesium phosphate prepared by embodiment 2, here it is apparent that it has meso-hole structure.
Fig. 5 is that the magnesium phosphate that magnesium phosphate prepared by embodiment 2 is prepared with embodiment 1 is shown using adriamycin as aids drug
Drug absorbability behavior difference, control group is to carry the conventional mesoporous hydroxyapatite of medicine, can have mesopore orbit structure
The Drug absorbability ability of magnesium phosphate nano material is far above conventional mesoporous hydroxyapatite nanoparticle.
Fig. 6 is the SEM figures for the magnesium phosphate that embodiment 3 is prepared using Triton X-100 auxiliary, it can be found that with the addition of
Magnesium phosphate is changed into the spheric granules with meso-hole structure after Triton X-100.
Fig. 7 be in embodiment 4 different quality than structure solubility curve of the magnesium phosphate-Cryptotanshinone in simulated gastric fluid,
It can be seen that magnesium phosphate can greatly improve the water solubility of Cryptotanshinone.
Fig. 8 is magnesium phosphate-Cryptotanshinone and hydroxyapatite-hidden of the same vehicle-drug quality than preparation in embodiment 4
Solubility curve of the tanshinone in simulated gastric fluid, it is seen that the dissolving of Cryptotanshinone (CPT) solid dispersion system based on magnesium phosphate
Effect is more preferable.
Fig. 9 is magnesium phosphate prepared by reference examples 1, has irregular pattern not over the magnesium phosphate obtained by hydro-thermal reaction
And lack obvious meso-hole structure.
Embodiment
Technical scheme is further described with reference to embodiment, it should be appreciated that following examples are only used
It is further described, but is not limited thereto in the present invention, it is every technical solution of the present invention to be modified or equivalent
Replace, without departing from the spirit and scope of technical solution of the present invention, all should cover in protection scope of the present invention.Institute of the present invention
It is commercially available to have raw material.
Embodiment 1
0.4g magnesia and 1.2g sodium dihydrogen phosphate are added in the 300mL aqueous solution, stir 5 minutes.Regulation reaction
The pH value of solution is 10, and mixed liquor is placed in hydrothermal reaction kettle, and hydro-thermal heating-up temperature is 120 DEG C, is reacted 4 hours, after reaction
Product is collected by filtration, wash, 60 DEG C be air-dried after obtain powder.By products therefrom carry out X-ray diffraction (XRD) see Fig. 1 and
The materialogy of transmission electron microscope (TEM) is characterized, and sees Fig. 2.As shown in figure 1, the phosphoric acid magnesium material of gained is by a variety of different magnesium substrates
Material is constituted.And in the visible gained phosphoric acid magnesium crystals of Fig. 2 pattern in the form of sheets, with equally distributed meso-hole structure.
Embodiment 2
0.58g magnesium hydroxides and 1.2g sodium dihydrogen phosphate are added to the aqueous solution containing the ascorbic 300mL of 0.01g
In, stir 5 minutes, the pH value of regulation solution is 9.Mixed liquor is placed in hydrothermal reaction kettle, hydro-thermal heating-up temperature is 120 DEG C,
Reaction 4 hours, product is collected by filtration after reaction, wash, 80 DEG C be air-dried after obtain powder.Products therefrom is subjected to X-ray
Diffraction (XRD) is shown in that the materialogy of Fig. 3 and transmission electron microscope (TEM) is characterized, and sees Fig. 4.Compared with Example 1, ascorbic addition changes
Every ratio of phosphoric acid magnesium material is become, but significant changes is had no in topography.
By embodiment 1 and the magnesium phosphate nano material of the gained of embodiment 2 using adriamycin as aids drug, displaying medicine is inhaled
The difference of attached behavior, and, it is seen that with the common mesoporous hydroxyapatite of pharmaceutical carrier as a control group：1) embodiment 2 uses dimension
Raw element C regulates and controls the magnesium phosphate to be formed has the more preferable early stage rate of adsorption than phosphoric acid magnesium material made from embodiment 1；2) embodiment
1 and 2 phosphoric acid magnesium material, it greatly improves the rate of adsorption of aids drug, is as a result shown in Fig. 5 compared with control group.
Embodiment 3
0.4g magnesia and 1.2g sodium dihydrogen phosphate are added in the 300mL aqueous solution, and add 12mL Triton
X-100, is stirred 5 minutes, and the pH value of regulation reaction solution is 10.Mixed liquor is placed in hydrothermal reaction kettle, hydro-thermal heating-up temperature
For 120 DEG C, react 4 hours, product is collected by filtration after reaction, wash, 60 DEG C be air-dried after obtain powder.Products therefrom is entered
Row ESEM (SEM) is characterized, and sees Fig. 6.It can be seen that with the addition of the magnesium phosphate obtained by Triton X-100 is with meso-hole structure
Spherical particle.
Embodiment 4
0.4g magnesia and 1.2g sodium dihydrogen phosphate are added in the 300mL aqueous solution, stir 5 minutes, regulation reaction
The pH value of solution is 10.Mixed liquor is placed in hydrothermal reaction kettle, hydro-thermal heating-up temperature is 120 DEG C, is reacted 4 hours, after reaction
Product is collected by filtration, wash, 60 DEG C be air-dried after obtain powder, preparation process and Parameter Conditions are consistent with embodiment 1.By powder
Body presses 9 with fat-soluble medicine Cryptotanshinone:1,7:1,5:1,3:1 mass ratio passes through rotary evaporation system using alcohol as reaction media
The solid dispersion of standby Cryptotanshinone, products therefrom is named as 9 successively:1SDs,7:1SDs,5:1SDs,3:1SDs.By in people
Simulation release in work gastric juice is it can be seen that can greatly improve Cryptotanshinone using magnesium phosphate as solid dispersion in aqueous phase
In rate of dissolution, so as to obtain more preferable bioavailability, see Fig. 7.Meanwhile, with using 1:The hydroxyl that 9 identical mass ratioes are built
Base apatite-Cryptotanshinone solid dispersion system (CPT-HA (1:9) SDs) compare, use the Cryptotanshinone of magnesium phosphate
(CPT-MgPs(1:9) SDs) dissolution rate significantly improve, see Fig. 8.
Reference examples 1
0.4g magnesia and 1.2g sodium dihydrogen phosphate are added in the 300mL aqueous solution, stir 4 hours.Mistake after reaction
Filter collect product, washing, 60 DEG C be air-dried after obtain powder.Products therefrom is subjected to the materialogy with transmission electron microscope (TEM)
Characterize, see Fig. 9.It can be seen that the magnesium phosphate precipitation pattern without process hydrothermal system is irregular and lacks meso-hole structure.
Embodiment of above is merely to illustrate the present invention, rather than limitation of the present invention.Although with reference to embodiment to this hair
It is bright to be described in detail, it will be understood by those within the art that, to technical scheme carry out it is various combination,
Modification or equivalent substitution, without departure from the spirit and scope of technical solution of the present invention, the right that all should cover in the present invention is wanted
Ask among scope.
Claims (10)
1. a kind of magnesium phosphate nano material, it is characterised in that with meso-hole structure, it, which is prepared by the following method, obtains：
(1) use water-soluble magnesium salt as magnesium source, phosphoric acid or water-soluble phosphate are as phosphorus source, and deionized water, will as solvent
Magnesium source, phosphorus source, which are added in aqueous phase solution, to be well mixed；
(2) pH value of solution is adjusted, hydro-thermal reaction is carried out, separation, washing and dry gained are precipitated, and being made has the mesoporous of prosperity
The magnesium phosphate nano material of pore passage structure.
2. magnesium phosphate nano material as claimed in claim 1, it is characterised in that water-soluble magnesium salt is to adopt in step (1)
With magnesia, magnesium hydroxide, magnesium chloride, magnesium nitrate, magnesium gluconate one or more.
3. magnesium phosphate nano material as claimed in claim 1, it is characterised in that water-soluble phosphate can be in step (1)
Diammonium hydrogen phosphate, ammonium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium pyrophosphate, three
Polyphosphate sodium, calgon, can by the phosphorous biomolecule of pyrohydrolysis one or more.
4. magnesium phosphate nano material as claimed in claim 1, it is characterised in that aqueous phase solution is water, water solubility in step (1)
Organic solvent or the water soluble organic molecules with hydroxyl/carboxylic group.
5. magnesium phosphate nano material as claimed in claim 4, it is characterised in that there is hydroxyl/carboxyl described in step (1)
The water soluble organic molecules of group are glucose, Tea Polyphenols, citric acid or vitamin C.
6. magnesium phosphate nano material as claimed in claim 1, it is characterised in that in step (1) in magnesium source magnesium ion mole
Concentration is 0.001-1 mol/Ls；The molar concentration of phosphorus is 0.001-1 mol/Ls in phosphorus source in step (1)；Magnesium in step (1)
Phosphorus mol ratio is 0.5-1.5：1.
7. magnesium phosphate nano material as claimed in claim 1, it is characterised in that the pH value of regulation reaction solution in step (2)
For 7-12.
8. the magnesium phosphate nano material as described in claim 1-7 is any, it is characterised in that hydrothermal temperature in step (2)
For 100-200 DEG C, time 1-24 hour；It is preferred that hydrothermal temperature is 120-160 DEG C, the time is 2-6 hours.
9. the preparation method of any described magnesium phosphate nano materials of a kind of claims 1-8, it is characterised in that including following
Step：
(1) use water-soluble magnesium salt as magnesium source, phosphoric acid or water-soluble phosphate are as phosphorus source, and deionized water, will as solvent
Magnesium source, phosphorus source, which are added in aqueous phase solution, to be well mixed；
(2) pH value of solution is adjusted, hydro-thermal reaction is carried out, separation, washing and dry gained are precipitated, and being made has meso-hole structure
Magnesium phosphate nano material.
10. the magnesium phosphate nano material as described in claim 1-8 is any is in organizational project, drug delivery, modern agriculture or dirt
Application in water process.
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| CN107698009A (en) * | 2017-10-20 | 2018-02-16 | 东南大学 | A kind of carbon containing magnesium salts material for removing removing heavy metals and its preparation method and application |
| CN108636340A (en) * | 2018-06-12 | 2018-10-12 | 山东大学 | A kind of preparation method of mesoporous magnesia fiber and its application in purification of heavy metal waste water |
| CN110092362A (en) * | 2019-05-08 | 2019-08-06 | 武汉理工大学 | A kind of preparation method of meso-porous nano bata-tricalcium phosphate |
| CN114681669A (en) * | 2022-03-10 | 2022-07-01 | 苏州卓恰医疗科技有限公司 | Modified PMMA bone cement and preparation method thereof |
| CN115152791A (en) * | 2022-07-25 | 2022-10-11 | 大连海事大学 | Non-metal phosphorus-doped MgO antibacterial agent with sheet aggregate morphology and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698009A (en) * | 2017-10-20 | 2018-02-16 | 东南大学 | A kind of carbon containing magnesium salts material for removing removing heavy metals and its preparation method and application |
| CN107698009B (en) * | 2017-10-20 | 2021-03-02 | 东南大学 | Carbon-containing magnesium salt material for removing heavy metals, and preparation method and application thereof |
| CN108636340A (en) * | 2018-06-12 | 2018-10-12 | 山东大学 | A kind of preparation method of mesoporous magnesia fiber and its application in purification of heavy metal waste water |
| CN110092362A (en) * | 2019-05-08 | 2019-08-06 | 武汉理工大学 | A kind of preparation method of meso-porous nano bata-tricalcium phosphate |
| CN114681669A (en) * | 2022-03-10 | 2022-07-01 | 苏州卓恰医疗科技有限公司 | Modified PMMA bone cement and preparation method thereof |
| CN115152791A (en) * | 2022-07-25 | 2022-10-11 | 大连海事大学 | Non-metal phosphorus-doped MgO antibacterial agent with sheet aggregate morphology and preparation method and application thereof |
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