CN109019615A - A kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The preparation method of nano particle - Google Patents
A kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The preparation method of nano particle Download PDFInfo
- Publication number
- CN109019615A CN109019615A CN201810992142.9A CN201810992142A CN109019615A CN 109019615 A CN109019615 A CN 109019615A CN 201810992142 A CN201810992142 A CN 201810992142A CN 109019615 A CN109019615 A CN 109019615A
- Authority
- CN
- China
- Prior art keywords
- source
- hydrophilic
- hydrophobic
- mesoporous sio
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The preparation method of particle, include the following steps: first to mix tetraethyl orthosilicate, alkali source and deionized water, 30min is stirred at room temperature, obtain clear solution, it is placed in ice-water bath and is cooled to 0 DEG C, silane coupling reagent BTES is added, solution becomes white flock from clarifying, titanium source butyl titanate is added dropwise, it stirs and is gradually heated to 60 DEG C, rapidly between regulation solution system pH value to 10~11,60 DEG C of constant temperature are stirred 2 hours, using the hydrochloric acid solution of 2M/L by titanium silicon epoxy glue Precipitation, it is filtered, washed and drying process obtains the product.The present invention introduces hydrophobic functional groups using one-step method in situ; under the four-coordination activated state for keeping Ti high degree of dispersion; realize the regulation of material hydrophilic and hydrophobic; synthesis cycle is short, is easy to scale; it is a kind of environmental-friendly synthesis technology without using expensive macromolecular organic amine/ammonium template, reproducible, specific surface area and Kong Rong great.
Description
Technical field
The present invention relates to a kind of order mesoporous SiO2The synthesis of nano particle, especially a kind of hydrophilic and hydrophobic is adjustable to contain Ti
The preparation method of mesoporous silicon oxide.Specifically it is using the binary mixture of tetraethyl orthosilicate and silane coupling reagent
Silicon source is realized living to titanium nano silicon particles titanium simultaneously by the pH value of regulation system and the relative amount of both titanium silicon precursors
The regulation at property center and hydrophilic and hydrophobic, gained mesoporous material show good activity in macromolecular alkene epoxidation.
Background technique
Ordered mesoporous material refers to the mesoporous material of duct rule and ordered arrangement, since the material has regular duct
Structure, biggish specific surface area (~1000m2/ g) and Kong Rong (~1.0ml/g) and can with the aperture size of modulation (2.0~
50nm), extensive research interest is caused in catalysis, absorption and separation field.Wherein, gold is adulterated in ordered mesoporous material
Belong to hetero atom (Ti, Sn, Al etc.), can significantly improve a series of organic reactions catalytic activity (Chem. Commun., 2001,
2190.).
The orderly material of meso-porous nano containing Ti is always the neck since it is with good alkene epoxidation catalytic activity
The research hotspot in domain, specifically how the hydrophilic and hydrophobic of Effective Regulation mesoporous material, be to further increase macromolecular olefin epoxide
Change active key factor (Catalysis Today 248,2015,115-127).Currently, improving dredging for the mesoporous material containing Ti
It is aqueous to be based primarily upon two kinds of strategies.First is that silanization post-processes, by the Ti-MCM-41 of pre-synthesis, silane coupling reagent HMDS, molten
Agent toluene mixes according to a certain percentage, and 120 DEG C are stirred 1 hour, and suction filtration is dried to obtain target product (Applied Catalysis
A:General 507,2015,14-25).But the method use a large amount of toxic organic solvents, cause one to environment
Fixed pollution, and process is cumbersome is unfavorable for further expansion production, meanwhile, it may covering part catalyzing expoxidation of olefines
Ti active site.Second is that the mesopore molecular sieve containing Ti of directly synthesizing methyl functionalization, however the system is added more CTAB and makees
For template, surfactant utilization rate is not high, is unfavorable for sample recycling；Or the higher NaOH system of basicity is used, synthesis
Condition is more harsh, cause more serious environmental pollution (Materials Research Bulletin 103,2018,
38-46).
From above-mentioned report as it can be seen that using low energy consumption, without macromolecular organic amine/ammonium template, be simple to operate and friendly to environment
Method, synthesizing the mesoporous material containing Ti with preferable hydrophobic performance, still there are many problems demands to solve.
Summary of the invention
The purpose of the present invention is to provide a kind of synthesis to have the good hydrophobic mesoporous SiO containing Ti2The side of nano particle
Method, this method have many advantages, such as that easy to operate, at low cost without using macromolecular organic amine/ammonium template, pollution is small.
The object of the present invention is achieved like this:
A kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The synthetic method of particle, this method pass through the pH of preparatory adjustment and control system
Value is matched the hydrolytic condensation rate of organic silicon source and titanium source to greatest extent, old silicon titanium colloidal sol is in addition quickly gathered with dilute hydrochloric acid, is obtained
To the final mesoporous SiO containing Ti2Nano particle.Using tetramethylammonium hydroxide as alkali source, with tetraethyl orthosilicate and silane coupled examination
The binary mixture of agent is silicon source, and the ratio regulation parent-of regulation tetraethyl orthosilicate and silane coupling reagent between the two is hydrophobic
Property；Specific preparation process the following steps are included:
Step 1: tetraethyl orthosilicate, alkali source and deionized water are mixed and are placed in a beaker, room temperature persistently stirs 0.5 hour,
Clear solution is obtained, its ice-water bath is cooled to 0 DEG C, silane coupling reagent BTES is added, solution becomes white flock from clarifying,
Titanium source i.e. butyl titanate is added dropwise, obtains mixed solution；
Step 2: the pH value using 28% ammonium hydroxide adjustment and control system is 10 ~ 11, lasting to stir, and heats and be gradually heated to 60 DEG C,
60 DEG C of constant temperature stir 2 hours, 2.0 Mol/L dilute hydrochloric acid are then added, precipitation of material is precipitated, product is filtered, washed and is done
Dry processing obtains the adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2Nano particle；Wherein:
Silicon source is tetraethyl orthosilicate and silane coupling reagent pair-(γ-triethoxy silicon substrate propyl) tetrasulfide (BTES)
Binary mixture, mass ratio are 1~5: 1；
The alkali source is tetramethylammonium hydroxide (TMAOH)；
Silicon source, titanium source, the molar ratio of alkali source and water are 1: 0.01~0.1: 0.35~0.15: 20~80.
The present invention has the advantages that compared with existing preparation method
(1) in the mesoporous SiO containing Ti2In nano material synthesis, without using macromolecular cationic surfactant as template structure
It builds mesoporous, can greatly reduce macromolecular organic amine/ammonium dosage and reduce environmental pollution to reduce synthesis cost.
(2) silicon source uses binary mixture, and the amount and time that regulation silane coupling reagent (BTES) introduces are effectively matched two
The hydrolytic condensation rate of kind silicon source and titanium source had both guaranteed that silane coupling reagent participated in the synthesis of mesoporous material, while having realized transition
Miscellaneous metallic atom Ti is largely scattered in mesoporous hole wall in the form of four-coordination, is that advantageous item is created in the raising of catalytic activity
Part.
(3) hydrolysis rate of two kinds of silicon sources and titanium source is matched to greatest extent by the pH value of accurate control system simultaneously,
The condensation rate for being gathered old control silicon source using hydrochloric acid, is guaranteed the four-coordination dispersity of Ti, improves the benefit of silicon source to greatest extent
With rate.
(4) it can see from the transmission electron microscope of product characterization, which has irregular multi-stage artery structure, is conducive to
The diffusion of substrate and product in catalysis reaction.
(5) synthetic method of the invention is simple, product ultimate yield is high, at low cost, pollution is small, is easy to scale.
Detailed description of the invention
Fig. 1 is the mesoporous SiO containing Ti that the present invention synthesizes2Scanning electron microscope (SEM) figure of nano particle；
Fig. 2 is the mesoporous SiO containing Ti that the present invention synthesizes2Transmission electron microscope (TEM) figure of nano particle；
Fig. 3 is the mesoporous SiO containing Ti that the present invention synthesizes2Ultraviolet-visible (UV-visible) figure of nano particle.
Specific embodiment
Below by embodiment, the invention will be further described, and purpose, which is only that, more fully understands research of the invention
The protection scope that content is not intended to limit the present invention.
Embodiment 1
0.82g cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt (CTATos) is added to containing 14.4ml deionized water first
Beaker in, 60 DEG C of constant temperature stir 1 hour to clarifying, and obtain solution A；2.82g tetraethyl orthosilicate (TEOS) is added to and is contained
In the beaker for having 12.4ml deionized water and 2.548g tetramethylammonium hydroxide, 0.5 hour is stirred at room temperature, ice-water bath is cooled to
0 DEG C, it is added 1.41g silane coupling reagent BTES, to become milky cotton-shaped by clarifying for solution, and 0.1726g titanium source titanium is added dropwise
Sour four butyl esters (TBOT), the pH value using the rapid adjustment and control system of 28% ammonium hydroxide is 10~11, lasting to stir, and is gradually heated to
60 DEG C, 60 DEG C of constant temperature stir 2 hours, 2.0 Mol/L dilute hydrochloric acid are then added by titanium silicon epoxy glue Precipitation, product passes through
Filter, washing and drying process, obtain the adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2Nano particle.The final scanning electricity of resulting materials
Mirror and transmission electron microscope such as Fig. 1 and Fig. 2.Fig. 3 show the UV-visible spectrum of resulting materials, it can be obtained from the figure that in resulting materials
The co-ordination state of Ti is active four-coordination, is to realize one of active key factor of epoxidation reaction of olefines.
Embodiment 2
Modulation silicon source TEOS/BTES mass ratio is followed successively by 5: 1,4: 1,3: 1,1: 1, other experiment conditions and operation are and embodiment
1 is identical.
Embodiment 3
The amount of TMAOH is added in modulation, and silicon source/alkali source molar ratio is followed successively by 1: 0.35,1: 0.25,1: 0.15,1: 0.1, reduces body
It is basicity, other experiment conditions and operation are same as Example 1.
Claims (1)
1. a kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The synthetic method of particle, which is characterized in that this method includes following tool
Body step:
Step 1: tetraethyl orthosilicate, alkali source and deionized water are mixed and are placed in a beaker, room temperature persistently stirs 0.5 hour,
Clear solution is obtained, its ice-water bath is cooled to 0 DEG C, silane coupling reagent pair-(γ-triethoxy silicon substrate propyl) four sulphur are added
Compound (BTES), solution becomes white flock from clarifying, and titanium source i.e. butyl titanate is added dropwise, obtains mixed solution；
Step 2: the pH value using 28% ammonium hydroxide adjustment and control system is 10 ~ 11, lasting to stir, and heats and be gradually heated to 60 DEG C,
60 DEG C of constant temperature stir 2 hours, 2.0 Mol/L dilute hydrochloric acid are then added by Precipitation, product is filtered, washed and dried dry place
Reason, obtains the adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2Nano particle；Wherein:
Silicon source is tetraethyl orthosilicate and silane coupling reagent pair-(γ-triethoxy silicon substrate propyl) tetrasulfide (BTES)
Binary mixture, mass ratio are 1~5: 1；
The alkali source is tetramethylammonium hydroxide (TMAOH)；
Silicon source, titanium source, the molar ratio of alkali source and water are 1: 0.01~0.1: 0.35~0.15: 20~80.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810992142.9A CN109019615A (en) | 2018-08-29 | 2018-08-29 | A kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The preparation method of nano particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810992142.9A CN109019615A (en) | 2018-08-29 | 2018-08-29 | A kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The preparation method of nano particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109019615A true CN109019615A (en) | 2018-12-18 |
Family
ID=64625954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810992142.9A Pending CN109019615A (en) | 2018-08-29 | 2018-08-29 | A kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The preparation method of nano particle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109019615A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2391224A (en) * | 2002-07-26 | 2004-02-04 | Sutcliffe Speakman Carbons Ltd | Activated carbon treated with silicon-containing compounds |
| WO2005087369A1 (en) * | 2004-03-16 | 2005-09-22 | The Governing Council Of The University Of Toronto | Hybrid porous organic-metal oxide materials |
| CN104147986A (en) * | 2014-07-23 | 2014-11-19 | 中国人民解放军南京军区南京总医院 | Long-chain-thioether-bond-containing mesoporous organic-inorganic hybrid ball of core-hollow-shell structure and preparation method thereof |
| CN104812702A (en) * | 2012-10-01 | 2015-07-29 | 陶氏环球技术有限公司 | Compositions and processes for mesoporous silicas having large pores with narrow diameter distributions |
| CN106378182A (en) * | 2016-08-19 | 2017-02-08 | 青岛文创科技有限公司 | An efficient titanium silicalite molecular sieve catalyst |
| CN106478053A (en) * | 2016-09-22 | 2017-03-08 | 上海宥纳新材料科技有限公司 | A kind of mesoporous composite material and preparation method thereof and the purposes in thermostable heat-isolating material is prepared |
| CN108451910A (en) * | 2018-02-09 | 2018-08-28 | 山西医科大学 | A kind of mesoporous magnetic Fe3O4Nanocomposite and preparation method thereof |
-
2018
- 2018-08-29 CN CN201810992142.9A patent/CN109019615A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2391224A (en) * | 2002-07-26 | 2004-02-04 | Sutcliffe Speakman Carbons Ltd | Activated carbon treated with silicon-containing compounds |
| WO2005087369A1 (en) * | 2004-03-16 | 2005-09-22 | The Governing Council Of The University Of Toronto | Hybrid porous organic-metal oxide materials |
| CN104812702A (en) * | 2012-10-01 | 2015-07-29 | 陶氏环球技术有限公司 | Compositions and processes for mesoporous silicas having large pores with narrow diameter distributions |
| CN104147986A (en) * | 2014-07-23 | 2014-11-19 | 中国人民解放军南京军区南京总医院 | Long-chain-thioether-bond-containing mesoporous organic-inorganic hybrid ball of core-hollow-shell structure and preparation method thereof |
| CN106378182A (en) * | 2016-08-19 | 2017-02-08 | 青岛文创科技有限公司 | An efficient titanium silicalite molecular sieve catalyst |
| CN106478053A (en) * | 2016-09-22 | 2017-03-08 | 上海宥纳新材料科技有限公司 | A kind of mesoporous composite material and preparation method thereof and the purposes in thermostable heat-isolating material is prepared |
| CN108451910A (en) * | 2018-02-09 | 2018-08-28 | 山西医科大学 | A kind of mesoporous magnetic Fe3O4Nanocomposite and preparation method thereof |
Non-Patent Citations (9)
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pandey et al. | Sol–gel derived organic–inorganic hybrid materials: synthesis, characterizations and applications | |
| CN102451740B (en) | Preparation method for nano-Y-shaped molecular sieve/amorphous silicon-aluminum composite material | |
| CN103193237B (en) | Mesoporous silica with yolk-shell structure and preparation method thereof | |
| CN102616795A (en) | Method for preparing pure silicon-based mesoporous silica nanoparticles | |
| CN104312181B (en) | Polyhydroxy lignin/silicon dioxide composite nano particle and preparation method thereof | |
| CN102964881B (en) | Amino/mercapto silane modified silica and preparation method thereof | |
| CN104003409B (en) | A kind of preparation method of controlled monodisperse spherical Large stone nano silicon | |
| US11097242B2 (en) | Wet gel granule of aerogel and preparation method thereof | |
| CN104907582B (en) | A kind of synthetic method of hydroxypropyl methyl cellulose cladding nano silver material | |
| CN103120920B (en) | Preparation method of nest-like core-shell-structure Ag@mTiO2 nano composite material | |
| CN102660154A (en) | Surface modification method for nanometer titanium dioxide | |
| CN102660153A (en) | Method for modifying nanometer titanium dioxide | |
| CN102275936A (en) | Preparation method of mesoporous spherical Sio2 nanoparticles | |
| JP2010195604A (en) | Method for producing surface-reformed porous silica, surface-reformed porous silica, slurry composition for addition to resin, filler for resin, and resin composition | |
| CN107074564B (en) | Hydrophobic silica and method for producing same | |
| CN103641122A (en) | Preparation method for multilevel mesoporous silica nanoparticles | |
| CN106167254B (en) | A kind of metal phosphate and preparation method thereof | |
| CN111868142A (en) | Preparation method of spherical silicon resin powder or connected body thereof and spherical silicon resin powder or connected body thereof obtained by preparation method | |
| CN102614857B (en) | Preparation method of metal ion dosed monodisperse mesoporous silicon dioxide spherical nanoparticles | |
| CN107254211A (en) | High-end water paint modified nano calcium carbonate raw powder's production technology | |
| CN109019615A (en) | A kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The preparation method of nano particle | |
| CN108821296A (en) | A kind of preparation method of mesoporous spherical nano Sio 2 particle | |
| CN110104654A (en) | A kind of Janus type porous silica composite nanoparticle and preparation method thereof | |
| CN106994345B (en) | A kind of particle self assembly TiO2/Fe2O3The preparation method of chain composite granule | |
| CN108993413B (en) | Preparation method of amino modified precipitated silica |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181218 |
|
| WD01 | Invention patent application deemed withdrawn after publication |