CN106076347A - A kind of hollow core shell mould metal silicate/cerium oxide nanoparticles and preparation method thereof - Google Patents
A kind of hollow core shell mould metal silicate/cerium oxide nanoparticles and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to advanced nano composite material and technical field, be specially a kind of hollow core shell mould metal silicate/cerium oxide nanoparticles and preparation method thereof.The present invention is seed grain initially with silicon source presoma Hydrolyze method synthesis pattern, the silica nanosphere of size uniform.Then, utilize chemical precipitation method, use the hydrolysis of ceria presoma, be coated with one layer of uniform ceria at silica surface.Finally, utilize hydro-thermal method, in the basic conditions, add metal precursor, synthesize the hud typed silicate/cerium oxide nanoparticles of metal hollow.This hollow core-shell nano-particle has all first-class advantage of high-specific surface area, high activity metal dispersion, high anti-caking power and pattern, has important application prospect at adsorbing separation and catalytic field etc..The synthetic method that the present invention is reported, it is possible to realize the specific surface area to metal silicate and the control of ceria shell thickness.Synthesis material is easy to get, method is the rapidest, it is possible to realize large batch of synthesis.
Description
Technical field
The invention belongs to advanced nano composite material and technical field, be specifically related to a kind of hollow core shell mould metal metasilicate
Salt/cerium oxide nanoparticles and preparation method thereof.
Technical background
In recent years, nm-class core-and-shell particles is widely used in the fields such as catalysis, medicine, environmental protection and energy storage.This is main
It is owing to core and the shell of core shell nanoparticles can reasonably be designed the selection that include material, shell porosity and hole knot
The control etc. of structure, the application requirement concrete to reach them.Such as: high catalysis activity and high-temperature stability, high medicine
Controlled release precision, high energy storage density etc..
Compared with loaded catalyst, hud typed metal silicate/cerium oxide nanoparticles has higher metal and divides
Divergence, high resistant activity metal sintering ability and the high ability preventing metal loss, it is thus possible to show good urging
Change performance, such as: high catalytic activity, high-temperature stability, high recycling and high carbon accumulation resisting ability etc..But, according to
The author is understood, and there is presently no the report of synthesis about hollow core shell mould metal silicate/cerium oxide nanoparticles.?
The core shell nanoparticles great majority with ceria as shell of report are about noble metal such as Ag, Au, Pt, Pd etc., or
Bad dispersibility, yield are little.(X.Wang,Y.Zhang,S.Song,X.Yang,Z.Wang,R.Jin,H.Zhang,
Angew.Chem.Int.Ed.,55,4542,2016；H.X.Zhong,Y.Wei,Y.Z.Yue,L.H.Zhang,Y.Liu,
Nanotechnology,27,135701,2016；E.T.Saw,U.Oemar,M.L.Ang,K.Hidajat,S.Kawi,
ChemCatChem,7,3358-3367,2015；T.Mitsudome,M.Matoba,T.Mizugaki,K.Jitsukawa,
K.Kaneda,Chem.Eur.J.19,5255–5258,2013；H.Guo,Y.He,Y.Wang,L.Liu,X.Yang,S.Wang,
Z.Huang,Q.Wei,J.Mater.Chem.A,1,7494-7499,2013；J.Qi,J.Chen,G.Li,S.Li,Y.Gao,
Z.Tang,Energy Environ.Sci.,5,8937-8941,2012；C.-M.Fan,L.-F.Zhang,S.-S.Wang,D.-
H.Wang,L.-Q.Lu,A.-W.Xu,Nanoscale,4,6835-6840,2012；Connie Mei YuYeung,Shik Chi
Tsang, J.Mole.Catal.A, 322,17-25,2010.)
Summary of the invention
It is an object of the invention to provide the homogeneous nano-particle of a kind of metal dispersity height, Heat stability is good, pattern and
Its preparation method.This metal silicate/ceria core-shell type nano catalyst combine metal silicate high-specific surface area,
The advantages such as high metal dispersity and the high oxygen migration ability of ceria, the reforming reaction preparation serious at high temperature, carbon distribution is closed
Become in the catalytic reactions such as gas and have broad application prospects.
Technical scheme: the preparation method of a kind of hollow core shell mould metal silicate/cerium oxide nanoparticles:
First, using silicon source presoma Hydrolyze method synthesis pattern, the silica nanosphere of size uniform is seed grain, then, utilizes
Chemical precipitation method, uses the hydrolysis of ceria presoma, at silica surface one layer of uniform ceria of cladding, finally,
Utilize hydro-thermal method, in the basic conditions, add the presoma of metal silicate, synthesize hollow core shell mould metal silicate/dioxy
Change cerium nano-particle, add appropriate solvent washing, centrifugation removing alkalescence, acidic materials, be dried.
Synthesized hollow core-shell nanosphere size is 20nm～900nm, and specific surface area is 20m2.g-1～300m2.g-1,
Control especially by the control size of silica nanosphere, the thickness of ceria shell.
In hollow core-shell nanosphere, the particle diameter of silica nanosphere is 10nm～900nm, and the thickness of ceria is
1nm～50nm.The thickness of the metal silicate of synthesis is 10nm～900nm, and specific surface area is 20m2.g-1～350m2.g-1。
The good dispersion of metal in heretofore described metal silicate.Metallosilicate material can be nisiloy acid
Salt, copper silicate, magnesium silicate, aluminosilicate, ferrosilicate, nickel-magnesium silicate, nickel-copper silicate one therein or several
Kind.
In the present invention, silicon source uses one or more in tetraethyl orthosilicate, methyl silicate, sodium silicate.
In the present invention, the catalyst that presoma hydrolysis in silicon source is used is base catalyst or acidic catalyst.Alkalescence is urged
Agent is one or more in sodium hydroxide, strong aqua ammonia or carbamide.Acidic catalyst is a kind of or several in acetic acid or dilute hydrochloric acid
Kind.
In the present invention, the synthesis temperature of the silicon dioxide of uniform different-grain diameter controls at 0 DEG C～80 DEG C.
In the present invention, ceria presoma is one or more in cerous nitrate, cerium chloride, ammonium ceric nitrate.
In the present invention, the precipitant that chemical precipitation method is used is one or more in sodium hydroxide, strong aqua ammonia.
In the present invention, the synthesis temperature of hydro-thermal method controls at 0 DEG C～220 DEG C.
In the present invention, the alkali in water heat transfer system uses one or more in carbamide, strong aqua ammonia, sodium hydroxide.
PH value controls 8～12.
In the present invention, the presoma of metal silicate is nickel nitrate, Nickel dichloride., copper nitrate, copper chloride, magnesium nitrate, chlorination
One or more in magnesium, ferric nitrate, ferric acetyl acetonade.
In the present invention, solvent uses the mixed solution of alkylol and water.Alkylol therein is methanol, ethanol, isopropanol
One or more.The mass ratio of alkyl alcohol and water is 9:1～1:9.
In the present invention, in the chemical precipitation synthetic system of silicon dioxide/cerium oxide core shell nanoparticles, silicon dioxide
Mass percent is 0.5wt%～15wt%, and the mass percent of ceria presoma is 0.5wt%～5wt%, precipitant
Mass percent be 15wt%～25wt%, other are alcohol water mixed solvent.At hollow core-shell structural metal silicate/dioxy
Change cerium nano-particle Hydrothermal Synthesis system in, the mass percent of silicon dioxide/cerium oxide nano-particle be 0.5wt%～
15wt%, the mass percent of metal silicate presoma is 5wt%～15wt%, and other are aqueous alkali mixed solution, pH value control
System is 8～12.
Beneficial effects of the present invention: the metal silicate that the present invention is reported/ceria core-shell type nano catalyst with
Metal silicate is core, and with ceria as shell, the nucleocapsid structure of formation is hollow uniform nanosphere body.With reported
The synthesis ceria Core-shell Structure Nanoparticles NiCu@CeO in road2(E.T.Saw,U.Oemar,M.L.Ang,K.Hidajat,
S.Kawi, ChemCatChem, 7,3358-3367,2015), Ag@CeO2(H.X.Zhong,Y.Wei,Y.Z.Yue,
L.H.Zhang, Y.Liu, Nanotechnology, 27,135701,2016), Au@CeO2(Qi,J.Chen,G.Li,S.Li,
Y.Gao, Z.Tang, Energy Environ.Sci., 5,8937-8941,2012) method etc. compares, and the present invention is reported
Synthetic method, synthesis material is cheap and easy to get, method is the rapidest, it is possible to realizes large batch of synthesis and realizes metal metasilicate
The specific surface area of salt and the control of ceria shell thickness.High-specific surface area, high activity due to this core shell nanoparticles
The all first-class advantage of metal dispersity, high anti-caking power and pattern, has important at adsorbing separation and catalytic field etc.
Application prospect.
Accompanying drawing explanation
Fig. 1 is hollow core shell mould metal silicate/cerium oxide nanoparticles preparation method；
Fig. 2 is 370nm silicon dioxide transmission electron microscope picture；
Fig. 3 is ceria, silicon dioxide/cerium oxide core shell nanoparticles, nisiloy hydrochlorate/ceria hollow core-shell
The X-ray diffractogram of nano-particle；
Fig. 4 is silicon dioxide/nickel silicate nucleocapsid structure transmission electron microscope picture；
Fig. 5 is Hollow Nickel silicate transmission electron microscope picture；
Fig. 6 is silicon dioxide/nickel silicate/ceria nucleocapsid structure transmission electron microscope picture；
Fig. 7 is hollow copper silicate/SiO2Core shell nanoparticles transmission electron microscope.
Detailed description of the invention
Embodiment 1:
(1) tetraethyl orthosilicate of 20mL is added in the beaker filling 150mL ethanol, stir.At another beaker
In, the ammonia (28wt%) of 100mL ethanol, 50mL water and 6.9mL is stirred.After solution in two beakers is mixed,
24h, centrifugation is reacted at 0 DEG C.Repeatedly wash with the mixed solvent of second alcohol and water, be centrifuged, stand-by after drying at room temperature.Obtain
The particle diameter of silicon dioxide is 450nm (Fig. 2).
(2) weigh silicon dioxide 0.5g ultrasonic disperse that previous step obtains in 50mL ethanol, add 0.1g six liquid glauber salt
Acid cerium.Add 0.18g sodium hydroxide, after stirring 1h, centrifugation.Repeatedly wash with the mixed solvent of second alcohol and water, be centrifuged, room
Temperature is the most stand-by.The silicon dioxide/cerium oxide core shell nanoparticles particle diameter obtained is 455nm, and the thickness of ceria is about
For 5nm.Fig. 3 XRD figure can be seen that the silicon dioxide/cerium oxide crystal phase structure of formation.
(3) silicon dioxide obtained and silicon dioxide/cerium oxide core shell nanoparticles 0.5g ultrasonic disperse are weighed respectively
In 10mL water.Adding carbamide, regulation pH is about 8.Add 0.1g six water nickel nitrate.Control reaction temperature is in room temperature, through not
In the same response time, obtain different nucleocapsid structures.Centrifugation.Repeatedly wash with the mixed solvent of second alcohol and water, be centrifuged, room
Temperature is dried.Fig. 4 is silicon dioxde reaction 10h, the silicon dioxide/nickel silicate core shell nanoparticles obtained.Fig. 5 is silicon dioxide
Reaction 28h, the Hollow Nickel silicate core shell nanoparticles obtained.Silicon dioxide/cerium oxide core shell nanoparticles reaction 15h
After, obtaining Hollow Nickel silicate/ceria core shell nanoparticles, particle diameter is about 455nm, and ceria thickness is about 5nm, than
Surface area is 180m2.g-1。
Embodiment 2:
(1) tetraethyl orthosilicate of 20mL is added in the beaker filling 150mL ethanol, stir.At another beaker
In, the ammonia (28wt%) of 100mL ethanol, 50mL water and 6.9mL is stirred.After solution in two beakers is mixed,
1h, centrifugation is reacted at 0 DEG C.Repeatedly wash with the mixed solvent of second alcohol and water, be centrifuged, stand-by after drying at room temperature.Obtain
The particle diameter of silicon dioxide is 200nm.
(2) weigh silicon dioxide 0.5g ultrasonic disperse that previous step obtains in 30mL ethanol, add 0.1g six liquid glauber salt
Acid cerium.Add 0.05g sodium hydroxide, after stirring 1h, centrifugation.Repeatedly wash with the mixed solvent of second alcohol and water, be centrifuged, room
Temperature is the most stand-by.Obtain silicon dioxide/cerium oxide core shell nanoparticles.Particle diameter is 210nm, and the thickness of ceria is about
10nm。
(3) the silicon dioxide/cerium oxide core shell nanoparticles 0.5g ultrasonic disperse obtained is weighed in 10mL water.Add
Carbamide, regulation pH is about 8.Add 0.1g magnesium nitrate hexahydrate.Control reaction temperature is in room temperature, after reacting 10h, and centrifugation.With
The mixed solvent of second alcohol and water repeatedly washs, is centrifuged, drying at room temperature, obtains hollow magnesium silicate/cerium oxide nanoparticles, grain
Footpath is about 210nm, and ceria thickness is about 10nm, and specific surface area is 117m2.g-1。
Embodiment 3:
(1) tetraethyl orthosilicate of 10mL is added in the beaker filling 150mL ethanol, stir.At another beaker
In, the ammonia (28wt%) of 100mL ethanol, 50mL water and 6.9mL is stirred.After solution in two beakers is mixed,
0.5h, centrifugation is reacted at 0 DEG C.Repeatedly wash with the mixed solvent of second alcohol and water, be centrifuged, stand-by after drying at room temperature.Obtain
SiO2Particle diameter is 50nm.
(2) weigh silicon dioxide 0.3g ultrasonic disperse that previous step obtains in 30mL ethanol, add 0.1g six liquid glauber salt
Acid cerium.Add 0.05g sodium hydroxide, after stirring 1h, centrifugation.Repeatedly wash with the mixed solvent of second alcohol and water, be centrifuged, room
Temperature is the most stand-by.The silicon dioxide/cerium oxide core shell nanoparticles particle diameter obtained is 60nm, and the thickness of ceria is about
10nm。
(3) silicon dioxide obtained and silicon dioxide/cerium oxide core shell nanoparticles 0.5g ultrasonic disperse are weighed respectively
In 10mL water.Adding carbamide, regulation pH is about 8.Add 0.1g Copper nitrate hexahydrate.Control reaction temperature is in room temperature, and reaction is not
After the time, centrifugation.Repeatedly wash with the mixed solvent of second alcohol and water, be centrifuged, drying at room temperature.Silicon dioxide/titanium dioxide
After cerium core shell nanoparticles reaction 10h, obtaining silicon dioxide/copper silicate/ceria core shell nanoparticles, particle diameter is about
60nm, ceria thickness is about 10nm, and specific surface area is 77m2.g-1(Fig. 6).Reaction 20h after, obtain hollow copper silicate/
Cerium oxide nanoparticles, specific surface area is 130m2.g-1.After silicon dioxde reaction 20h, obtain hollow copper silicate nano
Grain (Fig. 7).
Embodiment 4:
(1) tetraethyl orthosilicate of 10mL is added in the beaker filling 100mL ethanol, stir.At another beaker
In, the ammonia (28wt%) of 70mL ethanol, 20mL water and 4.9mL is stirred.After solution in two beakers is mixed,
Room temperature reaction 3h, centrifugation.Repeatedly wash with the mixed solvent of second alcohol and water, be centrifuged, stand-by after drying at room temperature.Two obtained
The particle diameter of silicon oxide is 300nm.
(2) weigh silicon dioxide 0.5g ultrasonic disperse that previous step obtains in 30mL ethanol, add 0.15g six liquid glauber salt
Acid cerium.Add 0.15g sodium hydroxide, after stirring 3h, centrifugation.Repeatedly wash with the mixed solvent of second alcohol and water, be centrifuged, room
Temperature is the most stand-by.The silicon dioxide/cerium oxide core shell nanoparticles particle diameter obtained is 330nm, and the thickness of ceria is about
For 30nm.
(4) the silicon dioxide/cerium oxide core shell nanoparticles 0.5g ultrasonic disperse obtained is weighed in 20mL water.Add
Carbamide, regulation pH is about 9.Add 0.05g six water nickel nitrate and 0.05g magnesium nitrate hexahydrate.Control reaction temperature in room temperature, reaction
After 10h, centrifugation.Repeatedly wash with the mixed solvent of second alcohol and water, be centrifuged, drying at room temperature, obtain Hollow Nickel-magnesium silicic acid
Salt/cerium oxide nanoparticles, particle diameter is about 375nm, and ceria thickness is about 5nm, and specific surface area is 235m2.g-1。
Claims (10)
1. the preparation method of hollow core shell mould metal silicate/cerium oxide nanoparticles, it is characterised in that: first, adopt
It is seed grain with silicon source presoma Hydrolyze method synthesis pattern, the silica nanosphere of size uniform, then, utilizes chemical precipitation
Method, uses the hydrolysis of ceria presoma, is coated with one layer of uniform ceria at silica surface, finally, utilizes hydro-thermal
Method, in the basic conditions, adds the presoma of metal silicate, synthesizes the hud typed silicate/cerium dioxide nano of metal hollow
Granule.
The preparation method of a kind of hollow core shell mould metal silicate/cerium oxide nanoparticles the most according to claim 1,
It is characterized in that: described silicon source presoma is one or more in tetraethyl orthosilicate, methyl silicate, sodium silicate.
The preparation method of a kind of hollow core shell mould metal silicate/cerium oxide nanoparticles the most according to claim 1,
It is characterized in that: the silicon source presoma hydrolyst used is base catalyst or acidic catalyst.
The preparation method of a kind of hollow core shell mould metal silicate/cerium oxide nanoparticles the most according to claim 1,
It is characterized in that: the temperature of silicon source presoma Hydrolyze method synthetic silica controls at 0 DEG C～80 DEG C.
The preparation method of a kind of hollow core shell mould metal silicate/cerium oxide nanoparticles the most according to claim 1,
It is characterized in that: described ceria presoma is one or more in cerous nitrate, cerium chloride, ammonium ceric nitrate.
The preparation method of a kind of hollow core shell mould metal silicate/cerium oxide nanoparticles the most according to claim 1,
It is characterized in that: one or more during precipitant is sodium hydroxide, strong aqua ammonia in described chemical precipitation method.
The preparation method of a kind of hollow core shell mould metal silicate/cerium oxide nanoparticles the most according to claim 1,
It is characterized in that: the synthesis temperature of the hydro-thermal method used controls at 25 DEG C～100 DEG C, and pH value is 8～12.
The preparation method of a kind of hollow core shell mould metal silicate/cerium oxide nanoparticles the most according to claim 1,
It is characterized in that: the alkali in water heat transfer system uses one or more in carbamide, strong aqua ammonia, sodium hydroxide.
The preparation method of a kind of hollow core shell mould metal silicate/cerium oxide nanoparticles the most according to claim 1,
It is characterized in that: the presoma of described metal silicate is nickel nitrate, Nickel dichloride., copper nitrate, copper chloride, magnesium nitrate, chlorination
One or more in magnesium, ferric nitrate, ferric acetyl acetonade.
10. according to the system of a kind of hollow core shell mould metal silicate/cerium oxide nanoparticles one of claim 1-9 Suo Shu
Preparation Method, it is characterised in that: in the chemical precipitation synthetic system of silicon dioxide/cerium oxide core shell nanoparticles, titanium dioxide
Silicon mass percent is 0.5wt%～15wt%, and the mass percent of ceria presoma is 0.5wt%～5wt%, precipitation
The mass percent of agent is 15wt%～25wt%, and other are alcohol water mixed solvent, hollow core-shell structural metal silicate/bis-
In the Hydrothermal Synthesis system of cerium oxide nanoparticles, the mass percent of silicon dioxide/cerium oxide nano-particle is 0.5wt%
～15wt%, the mass percent of metal silicate presoma is 5wt%～15wt%, and other are aqueous alkali mixed solution.
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