CN104707543A - Core-shell type metal oxide and preparation method thereof - Google Patents

Core-shell type metal oxide and preparation method thereof Download PDF

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Publication number
CN104707543A
CN104707543A CN201310690609.1A CN201310690609A CN104707543A CN 104707543 A CN104707543 A CN 104707543A CN 201310690609 A CN201310690609 A CN 201310690609A CN 104707543 A CN104707543 A CN 104707543A
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metal oxide
preparation
metal
shell
core
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CN104707543B (en
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王峰
王敏
徐杰
马继平
张晓辰
于淼
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C01B13/185—Preparing mixtures of oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a core-shell type metal oxide and a preparation method thereof, wherein the core-shell type metal oxide is a nanometer material having a core@gap@shell configuration, the nanometer material is prepared by adopting a metal organic coordination polymer material as a precursor and calcining at a certain temperature, the core and the shell of the nanometer material are the same metal oxide, and the particle size is 50-1000 nm. According to the present invention, the core-shell type metal oxide provides attractive application prospects in the fields of medicine, nonlinear optical devices, electroluminescent devices, catalysis and the like.

Description

A kind of hud typed metal oxide and preparation method thereof
Technical field
The invention belongs to nano material and preparation method thereof, specifically a kind of hud typed metal oxide materials and preparation method thereof.
Background technology
The core-shell type nano material of kernel@space@shell configurations, is also called yolk shell material.Core-shell material has the special characteristic such as optical, electrical and chemical because of the difference of its composition, size and structural arrangement, enjoy the concern of scientist in recent years.Core-shell material generally by center core and be coated on outside shell and form.Nucleocapsid part can be made of a variety of materials, and comprises macromolecule, inorganic matter and metal etc.Sheathing material can change and give that particle is optical, electrical, magnetic, the character such as catalysis and biologically active.Nowadays core-shell material has expanded the crossing domain into many science such as chemistry, physics, biology, materials, and demonstrates tempting application prospect in medicine, device for non-linear optical, electroluminescence device and catalysis etc.
In recent years, core-shell material obtains and studies widely.Mainly contain following methods: one is hard template method, first core A is first wrapped to form A@B nucleocapsid by B.A@B is wrapped up by C again, forms A@B@C core-shell material; Finally by B by dissolve and the method such as calcining is removed.Form A@space@C yolk shell structure; Another kind method is soft mode version method, and core A, under the equimolecular guiding of some surfactants, directly forms A@space@C core-shell material; In addition, yolk shell structure (Chem.Commun., 2011,47,12578-12591) is prepared with methods such as shipbuildings in galvanic replacement, Kirkendall diffusion and bottle in addition.
Although developed a variety of method to prepare core-shell material.The preparation method of metal oxide@space@metal oxide materials remains a challenge.The present invention has developed a kind of new synthetic method, can synthesis of metal oxide@space@metal oxide materials nano material.And the controllable adjustment of size and composition can be realized.This material has a wide range of applications in fields such as catalysis, biology, medicine, fluorescence.
Summary of the invention
Object of the present invention provides a kind of hud typed metal oxide materials and preparation method thereof, specifically metal oxide@space@metal oxide materials, is also called yolk shell material.Nucleocapsid is same metal oxide.Described metal oxide is one or more in Mg, Ni, Zn, In, Y, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu metal oxide.Particle diameter is 50-1000nm.
This material is the metal organic coordination polymer material with spherical morphology is precursor, calcine at a certain temperature, organic component is burnt, material framework shrinkage, material internal and Outer shrink inconsistent, cause the nano material forming metal oxide core@space@metal oxide shell.
The key preparing core-shell material has the metal organic coordination polymer of spherical morphology for precursor.Metal organic coordination polymer be by metal ion with containing the organic molecule of carboxylic group, under certain solvent and temperature, coordination polymerization forms.
The described preparation with the metal organic coordination polymer material of spherical morphology, is characterized in that: described slaine refer in the nitrate of Mg, Ni, Zn, In, Y, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, sulfate, chlorate, acetate one or more.Organic ligand is the rigidity organic molecule containing two carboxylic groups, refer to M-phthalic acid and fragrant cyclosubstituted derivative thereof, 3,5-pyridine dicarboxylic acid and fragrant cyclosubstituted derivative thereof, with one or more (Fig. 1) in 1,5-naphthalene diacid and fragrant cyclosubstituted derivative thereof.Substituting group (R 1-R 6) be F, Cl, Br, I, NO 2, CH 3, OH, OCH 3, NH 2in one or more.
In order to make organic molecule and the full and uniform hybrid reaction of metal salt monomer, need to use suitable dissolution with solvents organic molecule monomer, homogeneous reaction.Described organic solvent is one or more in acetonitrile, dimethyl sulfoxide (DMSO), dioxane, toluene, oxolane and diformamide.
Reaction temperature and time directly affect the speed of coordination polymerization and growth, thus affect the size of material.In order to control material size at nanoscale to micron order, optimal conditions is: reaction temperature is 30-200 DEG C, and the reaction time is 10min-72h;
The concentration of slaine and organic molecule monomer affects reaction rate, and reaction rate speed also directly affects the size of material, simultaneously the final pattern of slaine and organic molecule monomer mole ratio regular meeting direct relation material.In polymerisation, in added raw material, optimal conditions is: the molar concentration of metal and organic molecule is 0.1-100mM; Metal is 0.5-2 with the organic molecule mol ratio containing hydroxy-acid group.
A kind of hud typed metal oxide and preparation method thereof, calcining heat and time effects organic component remove the framework shrinkage with material, directly have influence on the structure of material.After optimizing, calcining heat is 300-1000 DEG C of calcination time is 0.5-24h.
Metal oxide core-shell material prepared by the present invention, having granular size can regulate and control, uniform particle sizes, the features such as good dispersion.
Accompanying drawing explanation
Fig. 1 carboxylic acid organic ligand structural representation.
Fig. 2 materials A stereoscan photograph.
Fig. 3 materials A A transmission electron microscope photo.
Detailed description of the invention
By finite concentration, and the organic molecule of certain slaine and organic carboxyl acid Small molecular ratio is dissolved among solvent, uniform temperature and under the time, and reactive polymeric forms.Slaine is one or more in nitrate in Mg, Ni, Zn, In, Y, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, sulfate, chlorate, acetate.Organic carboxyl acid molecule is M-phthalic acid and fragrant cyclosubstituted derivative thereof, the derivative of 3,5-pyridine dicarboxylic acid and replacement thereof, and one or more in 1,5-naphthalene diacid and fragrant cyclosubstituted derivative thereof.Described organic solvent is one or more in acetonitrile, dimethyl sulfoxide (DMSO), dioxane, toluene, oxolane and diformamide.Obtained metal organic coordination polymer is calcined certain hour at a certain temperature, obtains metal oxide core-shell material.Reaction optimal conditions is: the molar concentration of slaine and organic molecule is 0.1-100mM; Metal is 0.5-2 with the organic molecule mol ratio containing hydroxy-acid group.Reaction temperature is 30-200 DEG C, and the reaction time is 10min-72h.Calcining heat is 300-1000 DEG C, and calcination time is 0.5-24h.
Below by embodiment, method provided by the invention is described in detail, but do not limit the present invention in any form.
The preparation of embodiment 1 materials A
Get 0.3mmol M-phthalic acid and 0.3mmol europium nitrate is dissolved in 20mL dimethyl sulfoxide (DMSO).100 DEG C of reaction 48h.After being cooled to room temperature, centrifugal, the 50mL acetonitrile cleaning of gained solid, dry 24h at 100 DEG C.As shown in Figure 2, can find out that made material particle size is even from ESEM, the well-regulated spherical morphology of tool, particle diameter is about 400nm.
The preparation of embodiment 2 material B-O
The same materials A of preparation method of material B-O, difference is source metal and organic ligand and concentration thereof and mol ratio, reaction temperature, reaction time and reaction dissolvent.Organic ligand is M-phthalic acid, 3,5-pyridine dicarboxylic acids, 1,5-naphthalene diacid and their fragrant nuclear substituted derivatives thereof, and table 1 listed in by preparation condition and the material obtained.
Table 1 material B-O material and preparation condition thereof
The preparation of embodiment 3 materials A A
Materials A is put into tube furnace, under air atmosphere, is heated to 600 DEG C from the lower 10 DEG C of min of room temperature, keep 3h.Obtain core-shell material AA.Can see from Fig. 3 electron microscopic picture, prepared material is spheric granules, has obvious nucleocapsid structure, and in the cavity of shell parcel, have an obvious core, whole grain diameter is about 350nm.
The preparation of embodiment 4 material B B-OO
The preparation method of material B B-OO is with materials A A, and difference is to adopt different metal organic coordination polymer, calcining heat and time.Table 2 listed in by preparation condition and the material obtained.
Table 2 material B B-OO material and preparation condition thereof
Material number Metal organic coordination polymer Temperature/DEG C Time/h Particle diameter/nm
BB B 400 24 250
CC C 500 24 700
DD D 500 12 40
EE E 500 10 120
FF F 500 5 800
GG G 500 5 300
HH H 800 5 40
II I 800 5 250
JJ J 900 3 460
KK K 900 3 80
LL L 900 3 70
MM M 1000 0.5 160
NN N 1000 0.5 180
OO O 1000 0.5 160
Embody rule purposes:
This material can as the catalyst of acid catalyzed reaction.With the condensation reaction of benzaldehyde and methyl alcohol for example:
0.5mmol benzaldehyde, 0.05g catalyst and 5mL methyl alcohol join in reactor, stirred at ambient temperature reaction 4h.Product gas chromatographic analysis.Reaction result is in table 1.As can be seen from Table 4, the hud typed metal oxide materials of the present invention's synthesis is a kind of extraordinary acid catalyst, in the condensation reaction of benzaldehyde and methyl alcohol, show good catalytic effect.
The condensation reaction reaction result of table 3 benzaldehyde and methyl alcohol
Catalyst Yield/%
AA 90
BB 99
CC 98
DD 91
EE 88
FF 99
GG 96
HH 94
II 92
JJ 99
KK 95
LL 96
MM 98
NN 96
OO 99

Claims (7)

1. a hud typed metal oxide, hud typed metal oxide refers to the nano material of kernel space shell configurations, namely with hollow metal oxide for shell, in the hollow chamber of shell, have the metal oxide particle as kernel; The hollow chamber volume of shell is greater than the metal oxide particle volume of kernel;
The core of this material and shell material are same metal oxide, and the particle diameter of hud typed metal oxide is 50-1000nm;
Described metal oxide is one in Mg, Ni, Zn, In, Y, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu metal oxide or more than two kinds.
2. a preparation method for hud typed metal oxide described in claim 1, is characterized in that: this material is the metal organic coordination polymer material with spherical morphology for precursor calcining prepares; Metal organic coordination polymer is that coordination polymerization forms in organic solvent by metal ion and the organic molecule containing carboxylic group; Polymeric reaction temperature is 30-200 DEG C, and the reaction time is 10min-72h.
3. according to preparation method according to claim 2, it is characterized in that: described metal is one in Mg, Ni, Zn, In, Y, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or more than two kinds;
Metal ion presoma is its nitrate, sulfate, chlorate, the one in acetate or more than two kinds.
4. according to preparation according to claim 2, it is characterized in that: the organic molecule containing carboxylic group refers to M-phthalic acid and fragrant cyclosubstituted derivative thereof, 3,5-pyridine dicarboxylic acid and fragrant cyclosubstituted derivative thereof, with the one in 1,5-naphthalene diacid and fragrant cyclosubstituted derivative thereof or more than two kinds;
Substituting group in the cyclosubstituted derivative of above-mentioned virtue on aromatic ring is F, Cl, Br, I, NO 2, CH 3, OH, OCH 3, NH 2in one or more than two kinds, substituent number is 1-6.
5. according to preparation method according to claim 2, it is characterized in that: organic solvent is one or two or more kinds in acetonitrile, dimethyl sulfoxide (DMSO), dioxane, toluene, oxolane and diformamide.
6. according to preparation method according to claim 2, it is characterized in that: in added raw material, the molar concentration of metal and organic molecule is respectively 0.1-100mM; Metal is 0.5-2 with the organic molecule mol ratio containing hydroxy-acid group.
7. according to preparation method according to claim 2, it is characterized in that: the metal organic polymer material calcining heat with spherical morphology is 300-1000 DEG C, and calcination time is 0.5-24h.
CN201310690609.1A 2013-12-13 2013-12-13 A kind of hud typed metal-oxide and preparation method thereof Expired - Fee Related CN104707543B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107413385A (en) * 2017-05-18 2017-12-01 洛阳师范学院 A kind of micropore thulium coordination polymer is as heterogeneous catalysis material and preparation method
CN110787790A (en) * 2019-11-13 2020-02-14 武汉纺织大学 Sea urchin-shaped metal oxide porous photocatalytic material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101066988A (en) * 2007-05-10 2007-11-07 复旦大学 Magnetic metal oxide microsphere in core-shell structure and its prepn process
CN101421034A (en) * 2006-03-10 2009-04-29 韩国化学研究院 Adsorbent for water adsorption and desorption
CN102614818A (en) * 2012-03-27 2012-08-01 复旦大学 Magnetic mesoporous titanium dioxide core-shell type compound microsphere as well as preparation method and application thereof
CN103203207A (en) * 2012-01-12 2013-07-17 安徽大学 Magnetic nano-pore metal-organic framework core-shell material preparation, functionalized design, and application.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101421034A (en) * 2006-03-10 2009-04-29 韩国化学研究院 Adsorbent for water adsorption and desorption
CN101066988A (en) * 2007-05-10 2007-11-07 复旦大学 Magnetic metal oxide microsphere in core-shell structure and its prepn process
CN103203207A (en) * 2012-01-12 2013-07-17 安徽大学 Magnetic nano-pore metal-organic framework core-shell material preparation, functionalized design, and application.
CN102614818A (en) * 2012-03-27 2012-08-01 复旦大学 Magnetic mesoporous titanium dioxide core-shell type compound microsphere as well as preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107413385A (en) * 2017-05-18 2017-12-01 洛阳师范学院 A kind of micropore thulium coordination polymer is as heterogeneous catalysis material and preparation method
CN107413385B (en) * 2017-05-18 2021-03-16 洛阳师范学院 Microporous thulium coordination polymer as heterogeneous catalysis material and preparation method thereof
CN110787790A (en) * 2019-11-13 2020-02-14 武汉纺织大学 Sea urchin-shaped metal oxide porous photocatalytic material and preparation method and application thereof
CN110787790B (en) * 2019-11-13 2022-04-29 武汉纺织大学 Sea urchin-shaped metal oxide porous photocatalytic material and preparation method and application thereof

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