CN109616270A - A kind of phosphorus calcium phase carries CuO nano super paramagnetic material and preparation method thereof - Google Patents
A kind of phosphorus calcium phase carries CuO nano super paramagnetic material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of phosphorus calcium phases to carry CuO nano super paramagnetic material and preparation method thereof.Material prepared by the present invention is made of CuO microcrystal nanometer particle, superparamagnetic nanoparticle and phosphorus calcium phase mesoporous material.Preparation method includes: coprecipitation preparation CuxMyCaz(PO4)6(OH)2The presoma of (M=Fe, Co, Ni, 2x+3y+2z=20), the presoma are washed through washing, centrifugation, alcohol, are dried, calcine under the conditions of high temperature oxidative atmosphere, and obtained phosphorus calcium phase carries CuO super paramagnetic material.Material prepared by the present invention is provided simultaneously with catalysis, protein adsorption, superparamagnetism performance.Preparation method of the present invention solves the homogeneity question of material from molecular scale, and the surface potential energy of CuO nanoparticle is reduced by the crystallization of interface out-phase, realizes being stabilized for nanometer CuO.As material of main part, the presence of nanometer CuO assigns that the material is infrared and microwave absorbing function, phosphorus calcium phase then provide protein adsorption active site, and nanometer ultra paramagnetic particle facilitates the particle has superparamagnetism in external magnetic field, convenient for separation and recovery.
Description
Technical field
The invention belongs to field of new material preparation, be specifically related to a kind of phosphorus calcium phase carry CuO nano super paramagnetic material and its
Preparation method.
Background technique
The oxide CuO of metallic copper (Cu) is led as a kind of important inorganic material in catalysis, superconduction, thermal conductivity, ceramics etc.
It is widely used in domain.Such as catalyst and catalyst carrier and electrode active material；As glass, porcelain
Toner；Optical glass buffing compound；Dyeing wastewater through organic matter catalyst；The catalyst of organic synthesis；The desulfurizing agent of oils, hydrogenation
Agent；It makes artificial gems and other Cu oxides；Manufacture and gas analysis and measurement organic compound for artificial silk
Deng；It is alternatively arranged as the burningrate catalyst of propellant.Nanometer CuO powder has richer because of large specific surface area, particle interface
Active site, have catalytic activity more superior than large scale CuO powder and selectivity and other application performances, such as light inhale
Receipts, thermal resistance, antibacterial, sensing, coating additive etc..But nanometer CuO, since partial size is small, surface potential energy is big, is easy to reunite, be not easy
It saves and places for a long time, and the method for preparing nanometer CuO requires preparation condition high, safety using high temperature and pressure hydro-thermal method
Property it is poor, energy consumption is high, at the same nanometer CuO catalysis use process in be difficult to new life product separate, can not recycle and reuse.
Chinese patent CN101106002A discloses a kind of superparamagnetic material and preparation method thereof of Supported CuO.The material
Material is made of particles with superparamagnetism core/silicon substrate molecular sieve middle layer/CuO nanoparticle, and there are three steps for preparation process: sharp first
Ultra paramagnetic particle is obtained with coprecipitation, then sol-gel method covers one layer of silicon substrate molecular sieve in ultra paramagnetic particle, finally soaks
Stain is in Cu2+In solution, invention product is obtained through high temperature sintering.Whole preparation process is cumbersome, and uncontrollable factor is more, repeatability
Difference.
Chinese patent CN101157035A discloses a kind of CuO/Fe2O3Composite oxide catalysts and preparation method thereof are used
In CO low-temperature oxidation catalytic.Preparation process is template using cetyl trimethylammonium bromide, and industrial application consumption is big, template
Agent needs high-temperature calcination, discharges carbon dioxide, pollutes environment.
Summary of the invention
The present invention aiming at the shortcomings in the prior art, provides a kind of phosphorus calcium phase load nanometer that molecular scale grade dispersibility is excellent
CuO super paramagnetic material and preparation method thereof.The preparation method solves the homogeneity question of material from molecular scale, passes through boundary
Face out-phase crystallizes the surface potential energy for reducing CuO nanoparticle, realizes being stabilized for nanometer CuO.As material of main part, receive
The presence of rice CuO assigns that the material is infrared and microwave absorbing function.Phosphorus calcium phase then provides protein adsorption active site, and nanometer is super
Paramagnetic particle facilitates the particle has superparamagnetism in external magnetic field, and convenient for separation and recovery, whole preparation process is simply high
Effect is suitble to batch to prepare, low in cost.
It is an object of the present invention to provide a kind of material, the material includes CuO microcrystal nanometer particle, superparamagnetic nanometer
Particle and phosphorus calcium phase mesoporous material.
At least one of specifically, the material further includes following 1) -5) described:
1) in the CuO microcrystal nanometer particle, CuO crystal size is 16nm-100nm；
2) chemical component in the superparamagnetic nanoparticle is metal oxide；Again specifically, the metal oxide
Including M3O4, wherein M is any one in Fe, Co or Ni；
3) chemical component of the phosphorus calcium phase mesoporous material includes hydroxyapatite (HA), type alpha tricalcium phosphate (α-TCP), β-
Tricalcium phosphate (β-TCP), and/or calcium metaphosphate (CMP)；
4) in the superparamagnetic nanoparticle, particles with superparamagnetism crystal size is 26-200nm；
5) three kinds of CuO microcrystal nanometer particle, superparamagnetic nanoparticle and phosphorus calcium phase mesoporous material crystal phases are uniformly distributed, and are constituted
Crystallite particle；Again specifically, in the crystallite particle, average particle size 16nm-500nm.
Specifically, the preparation method of any material includes:
Phosphatic solution is added dropwise in the solution of salt containing M, Cu salt and Ca salt, keeps molten with lye during dropwise addition
The pH of liquid taken after 9.0-14.0, reaction reaction product calcine after to obtain the final product；Wherein M salt includes metal salt.
At least one of specifically, the preparation method of the material further includes following 1) -16) described:
1) solvent of the solution includes deionized water；
2) reaction temperature of the reaction is 0 DEG C -99 DEG C；
3) reaction time of the reaction is 30min-168h；
It 4) further include filtering to take solid matter, washing and/or drying after the reaction；Again specifically, the washing includes
Deionized water is washed 3 times, ethanol washing 1 time；The drying includes 30 DEG C of -120 DEG C of dryings；
5) reaction includes being uniformly mixed solution；Again specifically, including stirring；
6) the M salt includes the villaumite and/or nitrate of Fe, Co and/or Ni；
7) the Cu salt includes the villaumite and/or nitrate of Cu；
8) the Ca salt includes the villaumite and/or nitrate of Ca；
9)XM: YCu: ZCaMolar ratio meet X+Y+Z=10 and 2X+3Y+2Z=20；
10) phosphate includes phosphoric acid, disodium-hydrogen, sodium dihydrogen phosphate, potassium phosphate,monobasic, potassium dihydrogen phosphate, phosphorus
At least one of sour sodium, potassium phosphate, monoammonium phosphate, ammonium dihydrogen phosphate and/or ammonium phosphate；
11) lye includes at least one of sodium hydroxide, potassium hydroxide and/or ammonium hydroxide；
12) it is 0.01mol/L-10mol/L that the lye, which includes concentration of lye,；
13) reaction product includes Cux MyCaz(PO4)6(OH)2, wherein M is selected from Fe, Co or Ni, 2x+3y+2z=
20；
14) calcining, which is included in oxidizing atmosphere, calcines；Specifically, being included in air or O2It is calcined in atmosphere；
15) calcining includes that 800K-1300K is calcined；
16) calcining includes calcining 30min-24h.
Of the invention a further object is provides a kind of preparation method, and the preparation method includes: will be phosphatic molten
Drop is added in the solution of salt containing M, Cu salt and Ca salt, keeps the pH of solution in 9.0-14.0, reaction with lye during dropwise addition
After take reaction product calcine after to obtain the final product；Wherein M salt includes metal salt.
At least one of specifically, the preparation method further includes following 1) -16) described:
1) solvent of the solution includes deionized water；
2) reaction temperature of the reaction is 0 DEG C -99 DEG C；
3) reaction time of the reaction is 30min-168h；
It 4) further include filtering to take solid matter, washing and/or drying after the reaction；Again specifically, the washing includes
Deionized water is washed 3 times, ethanol washing 1 time；The drying includes 30 DEG C of -120 DEG C of dryings；
5) reaction includes being uniformly mixed solution；Again specifically, including stirring；
6) the M salt includes the villaumite and/or nitrate of Fe, Co and/or Ni；
7) the Cu salt includes the villaumite and/or nitrate of Cu；
8) the Ca salt includes the villaumite and/or nitrate of Ca；
9)XM: YCu: ZCaMolar ratio meet X+Y+Z=10 and 2X+3Y+2Z=20；
10) phosphate includes phosphoric acid, disodium-hydrogen, sodium dihydrogen phosphate, potassium phosphate,monobasic, potassium dihydrogen phosphate, phosphorus
At least one of sour sodium, potassium phosphate, monoammonium phosphate, ammonium dihydrogen phosphate and/or ammonium phosphate；
11) lye includes at least one of sodium hydroxide, potassium hydroxide and/or ammonium hydroxide；
12) it is 0.01mol/L-10mol/L that the lye, which includes concentration of lye,；
13) reaction product includes Cux MyCaz(PO4)6(OH)2, wherein M is selected from Fe, Co or Ni, 2x+3y+2z=
20；
14) calcining, which is included in oxidizing atmosphere, calcines；Specifically, being included in air or O2It is calcined in atmosphere；
15) calcining includes that 800K-1300K is calcined；
16) calcining includes calcining 30min-24h.
Of the invention a further object is provides the present invention material that any the method is directly prepared.
Of the invention a further object is provides the present invention application of any material.Specifically, the application includes
Following 1) -6) at least one of described:
1) as catalyst or be used to prepare tool catalysis product；
2) as adsorbent or be used to prepare tool adsorption function product；Again specifically, the absorption includes adhesion protein；
3) as infrared absorbing agents or be used to prepare tool infrared absorption function product；
4) as broadband microwave absorption or be used to prepare tool broadband microwave absorbing function product；Again specifically,
The broadband includes 750MHz~20GHz；
5) as superparamagnetic material or it is used to prepare the product with superparamagnetism performance；
6) application in separation and/or recovery process.
It is also another object of the present invention to provide the applications of any the method for the present invention.Specifically, the application includes
Following 1) -5) at least one of described:
1) product or its Related product of tool catalysis are used to prepare；
2) product or its Related product of tool adsorption function are used to prepare；Again specifically, the absorption includes adhesion protein；
3) product or its Related product of tool infrared absorption function are used to prepare；
4) product or its Related product of tool broadband microwave absorbing function are used to prepare；Again specifically, the broadband
Including 750MHz~20GHz；
5) it is used to prepare the product with superparamagnetism performance.
The advantages of the present invention are:
The present invention provides a kind of equally distributed phosphorus calcium phases of three kinds of crystal phases to carry CuO nano super paramagnetic material.The material is same
When have catalysis, protein adsorption, superparamagnetism performance etc..Preparation method provided by the invention solves material from molecular scale
Homogeneity question, the surface potential energy of CuO nanoparticle is reduced by the crystallization of interface out-phase, realizes the stabilization of nanometer CuO
In the presence of.As material of main part, the presence of nanometer CuO assigns that the material is infrared and microwave absorbing function.Phosphorus calcium phase then provides egg
White active adsorption sites, nanometer ultra paramagnetic particle facilitates the particle has superparamagnetism in external magnetic field, convenient for separating back
It receives.Preparation method of the present invention is simple and efficient, and batch is suitble to prepare, low in cost.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present application, constitutes part of this application, not
Constitute the improper restriction to the application.In the accompanying drawings:
Fig. 1 is the super paramagnetic material Fe of Supported CuO prepared by embodiment 13O4The crystal constituent of/CuO/HA material is reflected
Determine result figure.
Fig. 2 is the super paramagnetic material Co of Supported CuO prepared by embodiment 23O4The scanning electron microscope of/CuO/HA material
Result figure.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material as used in the following examples etc., is commercially available unless otherwise specified.
Following embodiments and its illustrate for explanation and understanding the present invention, do not constitute to improper limit of the invention
It is fixed.
Embodiment 1, Fe3O4The synthesis of/CuO/HA
(1) 1.622g iron chloride, 4.0335g copper chloride, 5.550g calcium chloride are weighed and is dissolved in 200mL, 25 DEG C of deionized waters
In, it is sufficiently stirred, obtains solution A；Disodium-hydrogen 8.1654g is weighed, 200mL is dissolved in, in 25 DEG C of deionized waters, sufficiently stirs
It mixes, obtains solution B.
(2) B solution by above-mentioned preparation is added in solution A, is stirred continuously, and adjusts reaction pH with 0.01M sodium hydroxide
And 9.0 are maintained at, keeping reaction temperature is 0 DEG C.FeCu is obtained after 30min4Ca5(PO4)6(OH)2Presoma.Filtering, takes solid-state
Substance is washed 3 times, and ethyl alcohol is washed 1 time, 30 DEG C of dryings, is placed in 800K in air atmosphere and is calcined 30min, obtains the super suitable of Supported CuO
Magnetic material Fe3O4/CuO/HA.Fig. 1 gives the crystal composition result of the super paramagnetic material.
The super paramagnetic material Fe of Supported CuO prepared by embodiment 13O4/ CuO/HA material is used as catalyst, micro- in 10mL
It is tested on type fixed-bed reactor, is used for ethyl alcohol one-step synthesis ethyl acetate.The result shows that under isolation air conditions,
220 DEG C, ethanol conversion reaches 80% when feed rate is 1L/h, and ethyl acetate selectively reaches 50%.
Embodiment 2, Co3O4The synthesis of/CuO/HA
(1) 1.298g cobalt chloride, 4.0335g copper chloride, 5.550g calcium chloride are weighed and is dissolved in 99 DEG C of deionized waters of 200mL
In, it is sufficiently stirred, obtains solution A；Disodium-hydrogen 8.1654g is weighed, is dissolved in 200mL99 DEG C of deionized water, is sufficiently stirred,
Obtain solution B.
(2) B solution by above-mentioned preparation is added in solution A, is stirred continuously, and adjusts reaction pH simultaneously with 10M potassium hydroxide
14.0 are maintained at, keeping reaction temperature is 20 DEG C.CoCu is obtained after 168h4Ca5(PO4)6(OH)2Presoma.Filtering is washed 3 times,
Ethyl alcohol is washed 1 time, 120 DEG C of dryings, is placed in 1300K in air atmosphere and is calcined 4h, obtains the super paramagnetic material Co of Supported CuO3O4/
CuO/HA.Fig. 2 provides the scanning electron microscope result of the super paramagnetic material.
Configure the cell culture fluid containing 10% fetal calf serum, the material that embodiment 2 is prepared (solid-liquid=1g/
It 50mL) is placed in culture solution, magnetic agitation 1h at 37 DEG C, product crosses 0.22 μm of filter membrane, collects filtrate.Double contractings are added into solution
Urea reagent, observation solution whether purpling.The result shows that the haemocyanin in cell culture fluid is adsorbed by material 100% completely, add
Enter after biuret reagent solution not purpling.
Embodiment 3, Ni3O4The synthesis of/CuO/HA
(1) 1.296g nickel chloride, 4.0335g copper chloride, 5.550g calcium chloride are weighed and is dissolved in 30 DEG C of deionized waters of 200mL
In, it is sufficiently stirred, obtains solution A；Disodium-hydrogen 8.1654g is weighed, is dissolved in 30 DEG C of deionized waters of 200mL, sufficiently stirs
It mixes, obtains solution B.
(2) B solution by above-mentioned preparation is added in solution A, is stirred continuously, and is adjusted reaction pH with 2M potassium hydroxide and is protected
It holds 10.0, keeping reaction temperature is 30 DEG C.Obtain 2 presoma of NiCu4Ca5 (PO4) 6 (OH) afterwards for 24 hours.Filtering is washed 3 times,
Ethyl alcohol is washed 1 time, 70 DEG C of dryings, is placed in 1250K in oxygen atmosphere and is calcined 2h, obtains the super paramagnetic material Ni of Supported CuO3O4/CuO/
HA。
Using the superparamagnetism for the material that Hysteresisgraph testing example 3 is prepared, superparamagnetism is to be saturated
The intensity of magnetization indicates that the material saturation magnetization is 66emu/g.
Embodiment 4, Fe3O4The synthesis of/CuO/ α-TCP
(1) 4.866g iron chloride, 2.689g copper chloride, 5.550g calcium chloride is weighed to be dissolved in 300mL50 DEG C of deionized water,
It is sufficiently stirred, obtains solution A；It weighs potassium dihydrogen phosphate 8.214g to be dissolved in 300mL50 DEG C of deionized water, is sufficiently stirred, obtains
Solution B.
(2) B solution by above-mentioned preparation is added in solution A, is stirred continuously, and is adjusted reaction pH with 5M potassium hydroxide and is protected
It holds 9.0 or more, keeping reaction temperature is 60 DEG C.Obtain Fe3Cu2Ca5(PO4)6(OH)2Presoma.Filtering is washed 3 times, ethyl alcohol
It washes 1 time, 60 DEG C of dryings, is placed in 1100K in air atmosphere and calcines 9h, obtain the super paramagnetic material Fe of Supported CuO3O4/CuO/α-
TCP。
It is that effective component makes infrared enamel using the material that embodiment 4 is prepared, it is infrared at 2.5~25 μm tests it
The ir-absorbance of wave band, absorptivity are indicated with normal direction total emissivity.The result shows that normal direction total emissivity is 0.89.
The material being prepared using embodiment 4 is added in styrene high molecular material as additive, is used as wide wave
Section (750MHz~20GHz) microwave absorption, absorption peak represent material to the degree of absorption of microwave.The result shows that material pair
The absorption peak of broadband (750MHz~20GHz) is 40dB.
Embodiment 5, Co3O4The synthesis of/CuO/ α-TCP
(1) 3.895g cobalt chloride, 2.689g copper chloride, 5.550g calcium chloride is weighed to be dissolved in 300mL60 DEG C of deionized water,
It is sufficiently stirred, obtains solution A；It weighs potassium dihydrogen phosphate 8.214g to be dissolved in 300mL60 DEG C of deionized water, is sufficiently stirred, obtains
Solution B.
(2) B solution by above-mentioned preparation is added in solution A, is stirred continuously, and adjusts reaction pH simultaneously with 10M potassium hydroxide
11.0 are maintained at, keeping reaction temperature is 60 DEG C.Co is obtained after 48h3Cu2Ca5(PO4)6(OH)2Presoma.Filtering is washed 3 times,
Ethyl alcohol is washed 1 time, 90 DEG C of dryings, is placed in 1000K calcining in air atmosphere and for 24 hours, is obtained the super paramagnetic material Co of Supported CuO3O4/
CuO/α-TCP。
Embodiment 6, Ni3O4The synthesis of/CuO/ α-TCP
(1) 3.888g nickel chloride, 2.689g copper chloride, 5.550g calcium chloride is weighed to be dissolved in 300mL90 DEG C of deionized water,
It is sufficiently stirred, obtains solution A；It weighs potassium dihydrogen phosphate 8.214g to be dissolved in 300mL90 DEG C of deionized water, is sufficiently stirred, obtains
Solution B.
(2) B solution by above-mentioned preparation is added in solution A, is stirred continuously, and adjusts reaction pH simultaneously with 10M potassium hydroxide
12.0 are maintained at, keeping reaction temperature is 90 DEG C, and Ni is obtained after 76h3Cu2Ca5(PO4)6(OH)2Presoma.Filtering is washed 3 times,
Ethyl alcohol is washed 1 time, 90 DEG C of dryings, is placed in 900K in air atmosphere and is calcined 12h, obtains the super paramagnetic material Ni of Supported CuO3O4/CuO/
α-TCP。
Embodiment 7, Fe3O4The synthesis of/CuO/ β-TCP
(1) 6.488g iron chloride, 2.689g copper chloride, 4.440g calcium chloride is weighed to be dissolved in 400mL99 DEG C of deionized water,
It is sufficiently stirred, obtains solution A；It weighs diammonium hydrogen phosphate 7.924g to be dissolved in 400mL99 DEG C of deionized water, is sufficiently stirred, obtains
Solution B.
(2) B solution by above-mentioned preparation is added in solution A, is stirred continuously, and adjusts reaction pH simultaneously with 10M potassium hydroxide
9.5 are maintained at, keeping reaction temperature is 99 DEG C.Fe is obtained after 2h4Cu2Ca4(PO4)6(OH)2Presoma.Filtering is washed 3 times, second
Alcohol is washed 1 time, 60 DEG C of dryings, is placed in 1280K in air atmosphere and is calcined 3h, obtains the super paramagnetic material Fe of Supported CuO3O4/CuO/β-
TCP。
Embodiment 8, Co3O4The synthesis of/CuO/ β-TCP
(1) 5.194g cobalt chloride, 2.689g copper chloride, 4.440g calcium chloride is weighed to be dissolved in 150mL70 DEG C of deionized water,
It is sufficiently stirred, obtains solution A；It weighs diammonium hydrogen phosphate 7.924g to be dissolved in 150mL70 DEG C of deionized water, is sufficiently stirred, obtains
Solution B.
(2) B solution by above-mentioned preparation is added in solution A, is stirred continuously, and is adjusted reaction pH with 3M potassium hydroxide and is protected
It holds 13.0, keeping reaction temperature is 70 DEG C.Co is obtained after 120h4Cu2Ca4(PO4)6(OH)2Presoma.Filtering is washed 3 times,
Ethyl alcohol is washed 1 time, 55 DEG C of dryings, is placed in 1070K in air atmosphere and is calcined 5h, obtains the super paramagnetic material Co of Supported CuO3O4/CuO/
β-TCP。
Embodiment 9, Ni3O4The synthesis of/CuO/ β-TCP
(1) 5.184g nickel chloride, 2.689g copper chloride, 4.440g calcium chloride is weighed to be dissolved in 250mL80 DEG C of deionized water,
It is sufficiently stirred, obtains solution A；It weighs ammonium dihydrogen phosphate 6.902g to be dissolved in 250mL80 DEG C of deionized water, is sufficiently stirred, obtains
Solution B.
(2) B solution by above-mentioned preparation is added in solution A, is stirred continuously, and is adjusted reaction pH with 7M potassium hydroxide and is protected
It holds 11.5, keeping reaction temperature is 80 DEG C.Obtain Ni4Cu2Ca4(PO4)6(OH)2Presoma.Filtering is washed 3 times, and ethyl alcohol washes 1
Secondary, 60 DEG C of dryings are placed in 970K in air atmosphere and calcine 20h, obtain the super paramagnetic material Ni of Supported CuO3O4/CuO/β-TCP。
Embodiment 10, Fe3O4The synthesis of/CuO/CMP
(1) 4.866g iron chloride, 4.033g copper chloride, 4.440g calcium chloride is weighed to be dissolved in 400mL30 DEG C of deionized water,
It is sufficiently stirred, obtains solution A；It weighs dipotassium hydrogen phosphate 10.451g to be dissolved in 400mL30 DEG C of deionized water, is sufficiently stirred, obtains
Solution B.
(2) B solution by above-mentioned preparation is added in solution A, is stirred continuously, and is adjusted reaction pH with ammonium hydroxide and is maintained at
13.5, keeping reaction temperature is 30 DEG C.Fe is obtained after 66h3Cu3Ca4(PO4)6(OH)2Presoma.Filtering is washed 3 times, and ethyl alcohol is washed
1 time, 60 DEG C of dryings are placed in 850K in air atmosphere and calcine 3h, obtain the super paramagnetic material Fe of Supported CuO3O4/CuO/CMP。
Embodiment 11, Co3O4The synthesis of/CuO/CMP
(1) 3.895g cobalt chloride, 4.033g copper chloride, 4.440g calcium chloride is weighed to be dissolved in 600mL10 DEG C of deionized water,
It is sufficiently stirred, obtains solution A；It weighs dipotassium hydrogen phosphate 10.451g to be dissolved in 600mL10 DEG C of deionized water, is sufficiently stirred, obtains
Solution B.
(2) B solution by above-mentioned preparation is added in solution A, is stirred continuously, and is adjusted reaction pH with ammonium hydroxide and is maintained at
11.2, keeping reaction temperature is 10 DEG C.Obtain Co3Cu3Ca4(PO4)6(OH)2Presoma.Filtering is washed 3 times, and ethyl alcohol is washed 1 time,
60 DEG C of dryings are placed in 880 DEG C of calcining 18h in air atmosphere, obtain the super paramagnetic material Co of Supported CuO3O4/CuO/CMP。
Embodiment 12, Ni3O4The synthesis of/CuO/CMP
(1) 3.888g nickel chloride, 4.033g copper chloride, 4.440g calcium chloride is weighed to be dissolved in 300mL40 DEG C of deionized water,
It is sufficiently stirred, obtains solution A；It weighs potassium phosphate 12.736g to be dissolved in 300mL40 DEG C of deionized water, is sufficiently stirred, obtains solution
B。
(2) B solution by above-mentioned preparation is added in solution A, is stirred continuously, and is adjusted reaction pH with ammonium hydroxide and is maintained at
10.2, keeping reaction temperature is 40 DEG C.Obtain Ni3Cu3Ca4(PO4)6(OH)2Presoma.Filtering is washed 3 times, and ethyl alcohol is washed 1 time,
60 DEG C of dryings are placed in 940 DEG C of calcining 20h in air atmosphere, obtain the super paramagnetic material Ni of Supported CuO3O4/CuO/CMP。
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore limitations on the scope of the patent of the present invention are interpreted as, as long as skill obtained in the form of equivalent substitutions or equivalent transformations
Art scheme should all be fallen within the scope and spirit of the invention.
Claims (10)
1. a kind of material, which is characterized in that the material includes CuO microcrystal nanometer particle, superparamagnetic nanoparticle and phosphorus calcium phase
Mesoporous material.
2. material according to claim 1, which is characterized in that the material further includes following 1) -5) it is described at least
It is a kind of:
1) in the CuO microcrystal nanometer particle, CuO crystal size is 16nm-100nm；
2) chemical component in the superparamagnetic nanoparticle is metal oxide；
Specifically, the metal oxide includes M3O4, wherein M is any one in Fe, Co or Ni；
3) chemical component of the phosphorus calcium phase mesoporous material include hydroxyapatite, type alpha tricalcium phosphate, bata-tricalcium phosphate, and/or
Calcium metaphosphate；
4) in the superparamagnetic nanoparticle, particles with superparamagnetism crystal size is 26-200nm；
5) three kinds of CuO microcrystal nanometer particle, superparamagnetic nanoparticle and phosphorus calcium phase mesoporous material crystal phases are uniformly distributed, and constitute crystallite
Particle；
Specifically, in the crystallite particle, average particle size 16nm-500nm.
3. according to claim 1 and/or 2 any materials, which is characterized in that the preparation method of the material includes:
Phosphatic solution is added dropwise in the solution of salt containing M, Cu salt and Ca salt, keeps solution with lye during dropwise addition
PH taken after 9.0-14.0, reaction reaction product calcine after to obtain the final product；Wherein M salt includes metal salt.
4. material according to claim 3, which is characterized in that the preparation method of the material further includes following 1) -16) institute
At least one of state:
1) solvent of the solution includes deionized water；
2) reaction temperature of the reaction is 0 DEG C -99 DEG C；
3) reaction time of the reaction is 30min-168h；
It 4) further include filtering to take solid matter, washing and/or drying after the reaction；
Specifically, the washing includes that deionized water is washed 3 times, ethanol washing 1 time；
The drying includes 30 DEG C of -120 DEG C of dryings；
5) reaction includes being uniformly mixed solution；
6) the M salt includes the villaumite and/or nitrate of Fe, Co and/or Ni；
7) the Cu salt includes the villaumite and/or nitrate of Cu；
8) the Ca salt includes the villaumite and/or nitrate of Ca；
9)XM: YCu: ZCaMolar ratio meet X+Y+Z=10 and 2X+3Y+2Z=20；
10) phosphate include phosphoric acid, disodium-hydrogen, sodium dihydrogen phosphate, potassium phosphate,monobasic, potassium dihydrogen phosphate, sodium phosphate,
At least one of potassium phosphate, monoammonium phosphate, ammonium dihydrogen phosphate and/or ammonium phosphate；
11) lye includes at least one of sodium hydroxide, potassium hydroxide and/or ammonium hydroxide；
12) it is 0.01mol/L-10mol/L that the lye, which includes concentration of lye,；
13) reaction product includes Cux MyCaz(PO4)6(OH)2, wherein M is selected from Fe, Co or Ni, 2x+3y+2z=20；
14) calcining, which is included in oxidizing atmosphere, calcines；Specifically, being included in air or O2It is calcined in atmosphere；
15) calcining includes that 800K-1300K is calcined；
16) calcining includes calcining 30min-24h.
5. a kind of preparation method of material, which is characterized in that the preparation method includes: to be added dropwise to phosphatic solution to contain
In the solution of M salt, Cu salt and Ca salt, the pH of solution is kept to negate and should produce after 9.0-14.0, reaction with lye during dropwise addition
After object calcining to obtain the final product；Wherein M salt includes metal salt.
6. according to the method described in claim 5, it is characterized in that, the preparation method further includes following 1) -16) it is described in
It is at least one:
1) solvent of the solution includes deionized water；
2) reaction temperature of the reaction is 0 DEG C -99 DEG C；
3) reaction time of the reaction is 30min-168h；
It 4) further include filtering to take solid matter, washing and/or drying after the reaction；
Specifically, the washing includes that deionized water is washed 3 times, ethanol washing 1 time；
The drying includes 30 DEG C of -120 DEG C of dryings；
5) reaction includes being uniformly mixed solution；
6) the M salt includes the villaumite and/or nitrate of Fe, Co and/or Ni；
7) the Cu salt includes the villaumite and/or nitrate of Cu；
8) the Ca salt includes the villaumite and/or nitrate of Ca；
9)XM: YCu: ZCaMolar ratio meet X+Y+Z=10 and 2X+3Y+2Z=20；
10) phosphate include phosphoric acid, disodium-hydrogen, sodium dihydrogen phosphate, potassium phosphate,monobasic, potassium dihydrogen phosphate, sodium phosphate,
At least one of potassium phosphate, monoammonium phosphate, ammonium dihydrogen phosphate and/or ammonium phosphate；
11) lye includes at least one of sodium hydroxide, potassium hydroxide and/or ammonium hydroxide；
12) it is 0.01mol/L-10mol/L that the lye, which includes concentration of lye,；
13) reaction product includes Cux MyCaz(PO4)6(OH)2, wherein M is selected from Fe, Co or Ni, 2x+3y+2z=20；
14) calcining, which is included in oxidizing atmosphere, calcines；Specifically, being included in air or O2It is calcined in atmosphere；
15) calcining includes that 800K-1300K is calcined；
16) calcining includes calcining 30min-24h.
7. the material that claim 5 and/or 6 any the methods are directly prepared.
8. the application of claim 1,2,3,4 and/or 7 any materials.
9. application according to claim 8, which is characterized in that the application includes following 1) -6) it is described at least one
Kind:
1) as catalyst or be used to prepare tool catalysis product；
2) as adsorbent or be used to prepare tool adsorption function product；
Specifically, the absorption includes adhesion protein；
3) as infrared absorbing agents or be used to prepare tool infrared absorption function product；
4) as broadband microwave absorption or be used to prepare tool broadband microwave absorbing function product；
Specifically, the broadband includes 750MHz~20GHz
5) as superparamagnetic material or it is used to prepare the product with superparamagnetism performance；
6) application in separation and/or recovery process.
10. the application of claim 5 and/or 6 any the methods.
At least one of specifically, the application includes following 1) -5) described:
1) product or its Related product of tool catalysis are used to prepare；
2) product or its Related product of tool adsorption function are used to prepare；
Specifically, the absorption includes adhesion protein；
3) product or its Related product of tool infrared absorption function are used to prepare；
4) product or its Related product of tool broadband microwave absorbing function are used to prepare；
Specifically, the broadband includes 750MHz~20GHz
5) it is used to prepare the product with superparamagnetism performance.
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| CN101106002A (en) * | 2007-06-15 | 2008-01-16 | 华南师范大学 | Superparamagnetism material carrying CuO and preparation method thereof |
| CN101721749A (en) * | 2009-12-04 | 2010-06-09 | 北京化工大学 | Ferroferric oxide/calcium phosphate nuclear shell structure nano particle and preparation method thereof |
| CN102329130A (en) * | 2011-09-29 | 2012-01-25 | 四川大学 | Magnetic nanoparticle/calcium phosphate ceramic composite porous material and preparation method thereof |
| CN102614549A (en) * | 2012-03-07 | 2012-08-01 | 北京化工大学 | Ferroferric oxide calcium phosphate nuclear shell magnetic nanoparticle and preparation method thereof by biological mineralization method |
| CN106215196A (en) * | 2016-08-05 | 2016-12-14 | 东北师范大学 | The preparation method of carbon/calcium phosphate/ferroso-ferric oxide composite construction nanoparticle |
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| CN101106002A (en) * | 2007-06-15 | 2008-01-16 | 华南师范大学 | Superparamagnetism material carrying CuO and preparation method thereof |
| CN101721749A (en) * | 2009-12-04 | 2010-06-09 | 北京化工大学 | Ferroferric oxide/calcium phosphate nuclear shell structure nano particle and preparation method thereof |
| CN102329130A (en) * | 2011-09-29 | 2012-01-25 | 四川大学 | Magnetic nanoparticle/calcium phosphate ceramic composite porous material and preparation method thereof |
| CN102614549A (en) * | 2012-03-07 | 2012-08-01 | 北京化工大学 | Ferroferric oxide calcium phosphate nuclear shell magnetic nanoparticle and preparation method thereof by biological mineralization method |
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