CN105731550A - Preparation method of nano composite metal oxide/mesoporous silica host-guest material - Google Patents

Preparation method of nano composite metal oxide/mesoporous silica host-guest material Download PDF

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Publication number
CN105731550A
CN105731550A CN201610067225.8A CN201610067225A CN105731550A CN 105731550 A CN105731550 A CN 105731550A CN 201610067225 A CN201610067225 A CN 201610067225A CN 105731550 A CN105731550 A CN 105731550A
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composite metal
preparation
metal oxide
nano composite
mesoporous silica
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牛奎
梁力曼
彭飞
侯文龙
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Hebei Normal University of Science and Technology
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Hebei Normal University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/70—Cobaltates containing rare earth, e.g. LaCoO3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0063—Mixed oxides or hydroxides containing zinc
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention discloses a preparation method of a nano composite metal oxide/mesoporous silica host-guest material. A chelated template agent N-hexadecyl ethylenediamine triacetate is adopted as a trapping agent for two kinds of metal ions, and chemical uniformity of different metal ions in a structure unit micelle and high dispersity in a micelle aggregate are realized. Micelle aggregates are mixed to establish a mesoporous silica matrix skeleton for a template; and when the template agent is removed by calcination, different metal ions loaded on the micelle are converted into corresponding composite metal oxides which are stored in a pore channel to obtain the nano composite metal oxide/mesoporous silica host-guest material. The problem that the particle aggregation caused by high surface energy is low-dimensional composite metal oxide synthesis in the processes of precipitation, drying and heat treatment in conventional preparation is eliminated.

Description

A kind of preparation method of nano composite metal oxide/mesoporous silicon oxide Subjective and Objective material
Technical field
The invention belongs to composite porous preparing technical field.A kind of nano composite metal oxide/mesoporous silicon oxide master The preparation method of guest materials.
Background technology
Metal composite oxide is the oxide with single crystalline phase formed with special ratios by two or more metal and oxygen, has Stable crystal structure, unique electromagnetic performance and higher surface acidic-basic property.The metal composite oxide of nanometer scale can show Unique dielectric, ferroelectricity, catalysis, superconduction and magnetoresistive characteristic, therefore becomes the study hotspot of association area scientist.But, preparation is received Rice composite metal oxide material generally uses the heat treatment processes such as high temperature sintering to promote composite precursor progressively crystallization, and this step is brought Secondary crystallization and the dynamic process such as particle agglomeration greatly reduce the specific surface area of nanocrystalline lattice defect density and product, make this Class material loses the characteristic of nanoparticle in actual applications.Based on this, novel in design, synthetic technology simply and easily, manage to press down Make and eliminate precipitation, be dried, the particle agglomeration that causes because of high surface energy in heat treatment process be low-dimensional metal composite oxide synthesis field urgently The problem that need to solve.
Using mesoporous material as host matrix, object nano-metal-oxide is assembled in the duct of mesoporous material, i.e. can utilize duct The excessive gathering of confinement effect suppression nano-particle, reach strictly to control the purpose of guest metal oxide size.At present, lead both at home and abroad Use to immerse in metal ion solution meso-porous matrix and fully adsorb, then realize through a series of processes such as dry, aerobic calcinings Metal-oxide assembling in mesopore orbit.Prior art there is the problem that 1) said method is only applicable to single burning Thing introduces in host matrix, owing to material of main part has uncontrollability to the absorbability of dissimilar metal ion, it is difficult to ensure different metal from Son is scattered in mesopore orbit with the ratio meeting metal composite oxide composition, and this will cause after calcining in duct except composition metal oxidation , also will there is the single metal-oxide that excess metal ion is formed in beyond the region of objective existence；2) to duct by the way of physics or chemisorbed Middle introducing metal ion, it is impossible to realize the homogeneity that dissimilar metal ion is distributed in duct, this is unfavorable for metal composite oxide crystalline phase Formed；3) host matrix is typically very limited to metal biosorption amount, object gold in the composite prepared the most as stated above The introduction volume belonging to oxide is relatively low.
Summary of the invention
In view of above-mentioned present situation, it is an object of the invention to provide the system of a kind of nano composite metal oxide/mesoporous silicon oxide Subjective and Objective material Preparation Method.Realize Chemical uniformity and high dispersion that different metal ion is distributed in duct, reach institute during subsequent calcination Introduce dissimilar metal ion and be completely reformed into the purpose of the single crystalline phase of metal composite oxide, object composition metal oxygen can be greatly improved simultaneously The introduction volume of compound.
It is an object of the invention to be achieved through the following technical solutions: a kind of nano composite metal oxide/mesoporous silicon oxide Subjective and Objective material The preparation method of material, its preparation method includes:
1) at 40～50 DEG C, the N-cetyl ethylenediamine triacetic acid of certain mass is dissolved in sodium hydroxide solution, adds metal The Zn of A, the one kind of Al with metal B of Mg, La, Cu, the mixing salt solution that Co, Fe, Ni are one kind of, acutely The lower regulation of stirring forms the settled solution that pH value is 6～10；
2) under agitation, the settled solution of step (1) will add 3-aminopropyl trimethoxysilane or 3-thmethylpropyl ammonium chloride Trimethoxy silane, treats that solution colour starts to bleach, and is rapidly added a certain amount of tetraethyl orthosilicate, is precipitated after stirring certain time；
3) precipitation obtained after step (2) being aged filters, washs, is placed in Muffle furnace after drying, performs temperature programming, finally Calcine 3～7 hours at 500～600 DEG C, obtain corresponding nano composite metal oxide/mesoporous silicon oxide Subjective and Objective material.
The invention has the beneficial effects as follows:
1, the present invention utilizes coordination compound that N-cetyl ethylenediamine triacetic acid and metal ion formed as synthesizing mesoporous silicon dioxide Template, ensure that metal composite oxide after firing by metal ion Chemical uniformity in micellar aggregates and high dispersion It is present in mesoporous silicon oxide duct with single crystalline phase.
2, compared with prior art, the mesoporous composite material prepared by the present invention can be greatly improved the introducing of object metal composite oxide Amount.Each metallic element does not loses in preparation process, and the composition of combination product complys with the input ratio of raw material, meets the input i.e. green of output Chemistry theory.
3, the N-cetyl ethylenediamine triacetic acid general applicability to metallic ion coordination effect, determining the method can be by numerous calcium Titanium ore type or spinel type composite metal oxide implant mesopore orbit, and in combination product, the size of object metal composite oxide is by main body The strict control of skeleton, it is possible to effectively reduce the particle agglomeration caused because of high surface energy.
Accompanying drawing explanation
Fig. 1 be the present invention by N-cetyl ethylenediamine triacetic acid by La3+With Co2+(mol ratio 1: 1) introduces mesopore orbit Schematic diagram；
Fig. 2 is nanometer LaCoO prepared by Fig. 13The high resolution electron microscopy photo of/mesoporous silicon oxide mesoporous composite material；
Fig. 3 is nanometer LaCoO prepared by Fig. 13The small angle X-ray diffraction figure of/mesoporous silicon oxide mesoporous composite material；
Fig. 4 is nanometer LaCoO prepared by Fig. 13The Wide angle X-ray diffraction figure of/mesoporous silicon oxide mesoporous composite material；
Fig. 5 be another embodiment by N-cetyl ethylenediamine triacetic acid by Zn2+With Fe3+(mol ratio 1: 2) introduces mesoporous hole The schematic diagram in road；
Fig. 6 is nanometer Zn Fe prepared by Fig. 52O4The high resolution electron microscopy photo of/mesoporous silicon oxide mesoporous composite material；
Fig. 7 is nanometer Zn Fe prepared by Fig. 52O4The small angle X-ray diffraction figure of/mesoporous silicon oxide mesoporous composite material；
Fig. 8 is nanometer Zn Fe prepared by Fig. 52O4The Wide angle X-ray diffraction figure of/mesoporous silicon oxide mesoporous composite material.
Detailed description of the invention
Embodiment 1:
1, at 42 DEG C, 0.458g N-cetyl ethylenediamine triacetic acid is dissolved in the sodium hydroxide solution of 0.5mol/L, to Wherein add the mixing salt solution containing 0.216g lanthanum nitrate hexahydrate with 0.145g cabaltous nitrate hexahydrate, be stirred vigorously, with 0.5 The sodium hydroxide solution regulation pH value of mol/L is to 8.0, and the volume of solution is adjusted to 30mL with deionized water, continuously stirred 3 hours；
2, in system, add 0.55mL 3-aminopropyl trimethoxysilane, treat that solution colour starts to bleach, be rapidly added 0.90mL Tetraethyl orthosilicate, stirs and is precipitated for 3 minutes；
3, system is stood 48 hours, then precipitation filtered, wash, be dried, then powder is placed in Muffle furnace, in 600 DEG C Lower calcining i.e. obtains nanometer LaCoO in 6 hours3/ mesoporous silicon oxide mesoporous composite material.
The present invention utilizes sequestering template N-cetyl ethylenediamine triacetic acid as the trapping agent of two metal ion species, respectively obtains tool There is the corresponding multiple tooth coordination compound of high stable constant.The dual surfactant co-mixing system that these complex molecules are constituted spontaneous can be assembled into heat The micellar aggregates that mechanics is stable, the component of formed micelle has concordance, and the ratio of two kinds of metallic elements is tight in single micelle Lattice follow the additional proportion of respective raw material, it is achieved thereby that dissimilar metal ion Chemical uniformity in this construction unit of micelle and High dispersion in micellar aggregates.Therefore, by utilizing N-cetyl ethylenediamine triacetic acid simultaneously as dissimilar metal ion Trapping agent and the template of mesoporous silicon oxide, by two metal ion species to meet combined oxidation while building bulk silica skeleton The ratio of thing composition is incorporated in mesopore orbit, realizes the nano composite metal oxide of single crystalline phase in mesoporous silicon oxide duct after calcining In assembling.
In Fig. 1 of the present invention, give embodiment 1 by N-cetyl ethylenediamine triacetic acid by La3+With Co2+(mol ratio 1: 1) schematic diagram of mesopore orbit is introduced.
In Fig. 2 of the present invention, give nanometer LaCoO of embodiment 1 preparation3The high-resolution of/mesoporous silicon oxide mesoporous composite material Electromicroscopic photograph.
Fig. 3 of the present invention gives nanometer LaCoO of embodiment 1 preparation3The little angle X of/mesoporous silicon oxide mesoporous composite material penetrates Ray diffraction diagram.
In Fig. 4 of the present invention, give nanometer LaCoO of embodiment 1 preparation3The Radix Rumicis X of/mesoporous silicon oxide mesoporous composite material X ray diffration pattern x.
Embodiment 2:
1, at 42 DEG C, 0.458g N-cetyl ethylenediamine triacetic acid is dissolved in the sodium hydroxide solution of 0.5mol/L, to Wherein add the mixing salt solution containing 0.089g zinc nitrate hexahydrate with 0.242g Fe(NO3)39H2O, be stirred vigorously, with 2.0 The sodium hydroxide solution regulation pH value of mol/L is to 10.0, and the volume of solution is adjusted to 35mL with deionized water, continuously stirred 2 hours；
2, in system, add 1.3mL 3-thmethylpropyl ammonium chloride trimethoxy silane, treat that solution colour starts to bleach, add rapidly Enter 2.0mL tetraethyl orthosilicate, continuously stirred 10 minutes；
3, system is stood 48 hours, then precipitation filtered, wash, be dried, then powder is placed in Muffle furnace, in 600 DEG C Lower calcining i.e. obtains nanometer Zn Fe in 3 hours2O4/ mesoporous silicon oxide mesoporous composite material.
In Fig. 5 of the present invention, give embodiment 2 by N-cetyl ethylenediamine triacetic acid by Zn2+With Fe3+(mol ratio 1: 2) schematic diagram of mesopore orbit is introduced.
In Fig. 6 of the present invention, give nanometer Zn Fe of embodiment 2 preparation2O4The high-resolution of/mesoporous silicon oxide mesoporous composite material Electromicroscopic photograph.
In Fig. 7 of the present invention, give nanometer Zn Fe of embodiment 2 preparation2O4The little angle X of/mesoporous silicon oxide mesoporous composite material X ray diffration pattern x.
In Fig. 8 of the present invention, give nanometer Zn Fe of embodiment 2 preparation2O4The Radix Rumicis X of/mesoporous silicon oxide mesoporous composite material X ray diffration pattern x.

Claims (1)

1. a preparation method for nano composite metal oxide/mesoporous silicon oxide Subjective and Objective material, its preparation method includes:
(1) at 40～50 DEG C, the N-cetyl ethylenediamine triacetic acid of certain mass is dissolved in sodium hydroxide solution, adds gold Belong to the Zn of A, the one kind of Al with metal B of Mg, La, Cu, the mixing salt solution that Co, Fe, Ni are one kind of, acute Under strong stirring, regulation forms the settled solution that pH value is 6～10；
(2) under agitation, the settled solution of step (1) will add 3-aminopropyl trimethoxysilane or 3-thmethylpropyl chlorination Ammonium trimethoxy silane, treats that solution colour starts to bleach, and is rapidly added a certain amount of tetraethyl orthosilicate, is sunk after stirring certain time Form sediment；
(3) precipitation obtained after step (2) being aged filters, washs, is placed in Muffle furnace after drying, performs temperature programming, Calcine 3～7 hours at 500～600 DEG C eventually, obtain corresponding nano composite metal oxide/mesoporous silicon oxide Subjective and Objective material.
CN201610067225.8A 2016-01-29 2016-01-29 Preparation method of nano composite metal oxide/mesoporous silica host-guest material Pending CN105731550A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111362887A (en) * 2020-03-27 2020-07-03 天津市长芦化工新材料有限公司 Method for preparing hexafluoropropylene oxide by catalytic oxidation
CN113874318A (en) * 2019-05-08 2021-12-31 柏林工业大学 Method for obtaining mesoporous silica particle-supported metal oxide

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102019431A (en) * 2010-09-30 2011-04-20 大连理工大学 Metallic nano cluster/silicon dioxide hollow nuclear shell structured nanoparticles and preparation method thereof
CN103830734A (en) * 2012-11-20 2014-06-04 东莞市长安东阳光铝业研发有限公司 Preparation method and use of silica/metal composite material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102019431A (en) * 2010-09-30 2011-04-20 大连理工大学 Metallic nano cluster/silicon dioxide hollow nuclear shell structured nanoparticles and preparation method thereof
CN103830734A (en) * 2012-11-20 2014-06-04 东莞市长安东阳光铝业研发有限公司 Preparation method and use of silica/metal composite material

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
ABDÜLHADI BAYKAL等: "Effect of zinc substitution on magneto-optical properties of Mn1-xZnxFe2O4/SiO2 nanocomposites", 《CERAMICS INTERNATIONAL》 *
Effect of zinc substitution on magneto-optical properties of Mn1-xZnxFe2O4/SiO2 nanocomposites;Abdülhadi Baykal等;《Ceramics International》;20140520;13401-13408页 *
KUI NIU等: "Efficient encapsulation of LaCoO3 perovskite in mesoporous silica induced by a chelating template", 《MICROPOROUS AND MESOPOROUS MATERIALS》 *
MUSTAFA COSKUN等: "The effect of SiO2 shell thickness on the magnetic properties of ZnFe2O4 nanoparticles", 《J NANOPART RES》 *
The effect of SiO2 shell thickness on the magnetic properties of ZnFe2O4 nanoparticles;Mustafa Coskun等;《J Nanopart Res》;20140222;2316-1至2316-12页 *
熊纲等: "纳米晶铁酸锌和铁酸斓的合成与表征", 《无机材料学报》 *
纳米晶铁酸锌和铁酸斓的合成与表征;熊纲等;《无机材料学报》;19980831;613-618页 *
纳米铁酸锌(ZnFe2O4)的表面改性;肖旭贤等;《精细化工中间体》;20070630;51-53以及69也 *
肖旭贤等: "纳米铁酸锌(ZnFe2O4)的表面改性", 《精细化工中间体》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113874318A (en) * 2019-05-08 2021-12-31 柏林工业大学 Method for obtaining mesoporous silica particle-supported metal oxide
CN113874318B (en) * 2019-05-08 2024-05-07 柏林工业大学 Method for obtaining mesoporous silica particle-supported metal oxides
CN111362887A (en) * 2020-03-27 2020-07-03 天津市长芦化工新材料有限公司 Method for preparing hexafluoropropylene oxide by catalytic oxidation
CN111362887B (en) * 2020-03-27 2023-06-27 天津市长芦化工新材料有限公司 Method for preparing hexafluoropropylene oxide by catalytic oxidation

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Application publication date: 20160706