CN102909083B - Silane-coupler-hybridized magadiite catalyst carrier material, and preparation method and application thereof - Google Patents
Silane-coupler-hybridized magadiite catalyst carrier material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN102909083B CN102909083B CN201210357235.7A CN201210357235A CN102909083B CN 102909083 B CN102909083 B CN 102909083B CN 201210357235 A CN201210357235 A CN 201210357235A CN 102909083 B CN102909083 B CN 102909083B
- Authority
- CN
- China
- Prior art keywords
- magadiite
- silane
- hydridization
- carrier material
- silane coupler
- 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.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses silane-coupler-hybridized magadiite catalyst carrier material which is made by covalent introduction of amino-terminated silane coupler molecules to the surface of magadiite material. A preparation method includes: firstly, adding Na-magadiite into hydrochloric solution, leaching after ion exchange, washing with distilled water to achieve neutrality, and drying to obtain H-magadiite; secondly, adding the H-magadiite into highly oxidizing solution, leaching after oxidation, washing with distilled water to achieve neutrality, and drying to obtain oxidized magadiite; and thirdly, adding the oxidized magadiite into toluene, adding silane coupler, allowing for backflow for 10-20h, leaching, washing with distilled water to achieve neutrality, and drying to obtain the silane-coupler-hybridized magadiite catalyst carrier material. The silane-coupler-hybridized magadiite catalyst carrier material has high stability and easy dispersibility. After loaded to the silane-coupler-hybridized magadiite catalyst carrier material, the catalyst is evenly dispersed on the surface of carrier. During reuse, shedding and agglomeration of the catalyst are avoided. The preparation method is simple with no need of special equipment, low in production cost and suitable for industrial production.
Description
Technical field
The invention belongs to catalyst carrier material technical field, be specifically related to a kind of silane coupler hydridization magadiite catalyst carrier material, preparation method and application.
Background technology
Nano metal, as a class new catalyst, has the unique texture not available for traditional catalyst and reactivity worth.They have shown unusual catalytic activity and selective in methanol carbonylation, propene hydroformylation reaction, double carbonylation reaction, Heck reaction and numerous reaction such as the selective hydrogenation of multiple reactant and asymmetric hydrogenation; Wherein nano-noble metal also can be used as the excellent electrode catalyst of the effective catalyst of borohydride hydrolytic hydrogen production, used in proton exchange membrane fuel cell and purifying vehicle exhaust catalyst.But noble metal reserves are rare, expensive, it is as widely used catalyst materials in field such as fuel cell, petrochemical industry, purifying vehicle exhaust and chemical industry, must become noble metal move towards the industrialization application bottleneck.How to construct high activity, stable, reusable load type metal nanocatalyst has important practical significance.
Carrier not only affects catalytic performance, and also play decisive action to the price of catalyst and suitability for industrialized production, choosing of carrier is most important.And Magadiite(phyllosilicate) be a kind of resourceful layered clay material, industrially also to accomplish scale production, there is aboundresources, cheap advantage; Also there is good physical and mechanical properties and good chemical resistance simultaneously; Magadiite has tridimensional structure in addition, and specific area is large; Compare with other clay minerals, magadiite can utilize cheap silica synthesize in enormous quantities in laboratory, purity is high, surface easily cutting, has the incomparable advantage of other carriers serving as in catalyst carrier role.
Current, the preparation of most of stratified material carried metal nanocatalyst generally makes carrier and metal nanometre cluster directly combine by physisorption, be not well positioned to meet the industrial demand to catalyst, mainly there is following technical problem: magadiite lamella easily dissociates, and causes separation difficulty; Effectively can not control nano metal in the dispersiveness of carrier surface and size; In catalysis and Reusability process, metal nanoparticle is easily reunited and is come off, and causes catalyst activity to reduce, the lost of life.
Summary of the invention
The object of this invention is to provide a kind of silane coupler hydridization magadiite catalyst carrier material, have high stability and easy separation, catalyst cupport is even, and in Reusability process, catalyst is without coming off and reuniting.
Second object of the present invention is to provide a kind of preparation method of silane coupler hydridization magadiite catalyst carrier material.
3rd object of the present invention is to provide a kind of silane coupler hydridization magadiite catalyst carrier material and is preparing the application in metallic catalyst.
In order to realize above object, the technical solution adopted in the present invention is: a kind of silane coupler hydridization magadiite catalyst carrier material, and this material introduces at magadiite material surface covalency the silane coupled agent molecule that end group is amino.
Described silane coupler is any one in γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane.
A preparation method for silane coupler hydridization magadiite catalyst carrier material, comprises the following steps:
1) Na-magadiite material being added concentration is in the hydrochloric acid solution of 0.5 ~ 2mol/l, and stir 1 ~ 5h, suction filtration, is washed till neutrality with distilled water, obtains H-magadiite after drying;
2) prepare strong oxidizing solution, temperature controls at 80 ~ 95 DEG C, adds dry H-magadiite, oxidation 20 ~ 40min, and suction filtration, is washed till neutrality with distilled water, obtains the magadiite be oxidized after drying;
3) magadiite after oxidation is placed in toluene, adds silane coupler, backflow 10 ~ 20h, suction filtration, is washed till neutrality with distilled water, namely obtains silane coupler hydridization magadiite catalyst carrier material after drying.
In described strong oxidizing solution, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7:3.
Magadiite in step 3) after every 20g oxidation, adds 1 ~ 4ml silane coupler.
A kind of silane coupler hydridization magadiite catalyst carrier material is preparing the application in metallic catalyst.
The method of metal supported catalyst is that silane coupler hydridization magadiite catalyst carrier material is placed in metal salt solution, fully stirs 1 ~ 3h; Add reducing agent to reduce, stop reaction after 2 ~ 5h, suction filtration, is washed till neutrality with distilled water, namely obtains loaded catalyst after drying.
Described slaine is ruthenium trichloride, platinum chloride, palladium bichloride, cobalt chloride, nickel chloride, the one in copper chloride.
The present invention is in order to improve interface bond strength between magadiite carrier material and metallic catalyst and easy separation, chemically construct magadiite hybrid material, realize the chemical bond between hybrid material and metal nanometre cluster, improve the dispersiveness of the nano metal particles of load, stability and separation property.
The present invention using silane coupler by covalent effect together with magadiite surface conjunction as catalyst carrier material, not only can play inorganic material and the composite advantage of organic material, be conducive to the easy separation improving supported catalyst; Improve the bond strength at interface between carrier and nano metal bunch, improve the dispersiveness of nano particle, stop the reunion of nano particle and come off.
Magadiite material after silane coupled, solve magadiite lamella legibility from problem, be separated easily, simplify separation and the recovery process of catalyst; Surface covalency introduces the functional group of Amino End Group, improves the active force of carrier and metal ion, can realize nano metal in the dispersed of carrier surface and size Control; Improve the interface binding power between carrier material and catalyst, make it in catalysis and Reusability process, avoid the reunion of metal nanoparticle and the degree that comes off, effectively improve the stability of loaded catalyst, activity and life-span.
Preparation method's technique of the present invention is simple, and without the need to special installation, production cost is low, is suitable for suitability for industrialized production.
The present invention carries out covalent modified with silane coupler to magadiite carrier surface, as template, and can the growth in situ of inducing metal nano-cluster.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of magadiite material before and after silane coupled hydridization;
(a) H-magadiite, (b) is oxidized magadiite, (c) silane coupled hydridization magadiite material;
Fig. 2 is the elementary analysis of magadiite material before and after silane coupled hydridization;
(a) H-magadiite, (b) is oxidized magadiite, (c) silane coupled hydridization magadiite material;
Fig. 3 is the infared spectrum of magadiite material before and after silane coupled hydridization;
(a) oxidation magadiite, (b) silane coupled hydridization magadiite material;
Fig. 4 is the transmission electron microscope picture of silane coupler hydridization magadiite catalyst carrier load ruthenium nano-cluster;
Fig. 5 is that silane coupler hydridization magadiite catalyst carrier load ruthenium nano-cluster compares with the repeat performance of magadiite direct load ruthenium nano-cluster;
(a) H-magadiite load ruthenium nano-cluster, (b) silane coupled hydridization magadiite material load ruthenium nano-cluster.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further illustrated:
Embodiment 1
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment introduces at magadiite material surface covalency the γ-aminopropyltrimethoxysilane that end group is amino, and preparation method comprises the following steps:
1) the Na-magagiite material of 150g being added 3000ml concentration is in the hydrochloric acid solution of 1mol/l, and stir 3h, suction filtration, is washed till neutrality with distilled water, obtains H-magadiite after drying;
2) volume ratio preparing the concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing solution 500ml of 7:3, and temperature controls, at 85 DEG C, to add the H-magadiite of 100g drying, oxidization time controls at 30min, suction filtration, is washed till neutrality with distilled water, obtains the magadiite be oxidized after drying;
3) magadiite after being oxidized by 20g is placed in 1000ml toluene, adds the γ-aminopropyltrimethoxysilane of 2.5ml, and stop reaction after backflow 15h, suction filtration, is washed till neutrality with distilled water, obtains silane coupled magadiite after drying.
Embodiment 2
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment introduces at magadiite material surface covalency the gamma-aminopropyl-triethoxy-silane that end group is amino, and preparation method comprises the following steps:
1) the Na-magagiite material of 150g being added 3000ml concentration is in the hydrochloric acid solution of 0.5mol/l, and stir 5h, suction filtration, is washed till neutrality with distilled water, obtains H-magadiite after drying;
2) volume ratio preparing the concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing solution 500ml of 7:3, and temperature controls, at 85 DEG C, to add the H-magadiite of 100g drying, oxidization time controls at 30min, suction filtration, is washed till neutrality with distilled water, obtains the magadiite be oxidized after drying;
3) magadiite after being oxidized by 20g is placed in 1000ml toluene, adds the gamma-aminopropyl-triethoxy-silane of 2.5ml, and stop reaction after backflow 15h, suction filtration, is washed till neutrality with distilled water, obtains silane coupled magadiite after drying.
Embodiment 3
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment introduces at magadiite material surface covalency N-β (aminoethyl)-γ-aminopropyltrimethoxysilane that end group is amino, and preparation method comprises the following steps:
1) the Na-magagiite material of 150g being added 3000ml concentration is in the hydrochloric acid solution of 2mol/l, and stir 1h, suction filtration, is washed till neutrality with distilled water, obtains H-magadiite after drying;
2) volume ratio preparing the concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing solution 500ml of 7:3, and temperature controls, at 85 DEG C, to add the H-magadiite of 100g drying, oxidization time controls at 30min, suction filtration, is washed till neutrality with distilled water, obtains the magadiite be oxidized after drying;
3) magadiite after being oxidized by 20g is placed in 1000ml toluene, add N-β (the aminoethyl)-γ-aminopropyltrimethoxysilane of 2.5ml, after backflow 15h, stop reaction, suction filtration, be washed till neutrality with distilled water, after drying, obtain silane coupled magadiite.
Embodiment 4
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment introduces at magadiite material surface covalency N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane that end group is amino, and preparation method comprises the following steps:
1) the Na-magagiite material of 150g being added 3000ml concentration is in the hydrochloric acid solution of 1mol/l, and stir 3h, suction filtration, is washed till neutrality with distilled water, obtains H-magadiite after drying;
2) volume ratio preparing the concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing solution 500ml of 7:3, and temperature controls, at 80 DEG C, to add the H-magadiite of 100g drying, oxidization time controls at 40min, suction filtration, is washed till neutrality with distilled water, obtains the magadiite be oxidized after drying;
3) magadiite after being oxidized by 20g is placed in 1000ml toluene, add N-β (the aminoethyl)-gamma-aminopropyl-triethoxy-silane of 2.5ml, after backflow 15h, stop reaction, suction filtration, be washed till neutrality with distilled water, after drying, obtain silane coupled magadiite.
Embodiment 5
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment introduces at magadiite material surface covalency the γ-aminopropyltrimethoxysilane that end group is amino, and preparation method comprises the following steps:
1) the Na-magagiite material of 150g being added 3000ml concentration is in the hydrochloric acid solution of 1mol/l, and stir 3h, suction filtration, is washed till neutrality with distilled water, obtains H-magadiite after drying;
2) volume ratio preparing the concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing solution 500ml of 7:3, and temperature controls, at 95 DEG C, to add the H-magadiite of 100g drying, oxidization time controls at 20min, suction filtration, is washed till neutrality with distilled water, obtains the magadiite be oxidized after drying;
3) magadiite after being oxidized by 20g is placed in 1000ml toluene, adds the γ-aminopropyltrimethoxysilane of 2.5ml, and stop reaction after backflow 15h, suction filtration, is washed till neutrality with distilled water, obtains silane coupled magadiite after drying.
Embodiment 6
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment introduces at magadiite material surface covalency the γ-aminopropyltrimethoxysilane that end group is amino, and preparation method comprises the following steps:
1) the Na-magagiite material of 150g being added 3000ml concentration is in the hydrochloric acid solution of 1mol/l, and stir 3h, suction filtration, is washed till neutrality with distilled water, obtains H-magadiite after drying;
2) volume ratio preparing the concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing solution 500ml of 7:3, and temperature controls, at 80 DEG C, to add the H-magadiite of 100g drying, oxidization time controls at 40min, suction filtration, is washed till neutrality with distilled water, obtains the magadiite be oxidized after drying;
3) magadiite after being oxidized by 20g is placed in 1000ml toluene, adds the silane coupler γ-aminopropyltrimethoxysilane of 1ml, and stop reaction after backflow 20h, suction filtration, is washed till neutrality with distilled water, obtains silane coupled magadiite after drying.
Embodiment 7
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment introduces at magadiite material surface covalency the γ-aminopropyltrimethoxysilane that end group is amino, and preparation method comprises the following steps:
1) the Na-magagiite material of 150g being added 3000ml concentration is in the hydrochloric acid solution of 1mol/l, and stir 3h, suction filtration, is washed till neutrality with distilled water, obtains H-magadiite after drying;
2) volume ratio preparing the concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing solution 500ml of 7:3, and temperature controls, at 80 DEG C, to add the H-magadiite of 100g drying, oxidization time controls at 40min, suction filtration, is washed till neutrality with distilled water, obtains the magadiite be oxidized after drying;
3) magadiite after being oxidized by 20g is placed in 1000ml toluene, adds the silane coupler γ-aminopropyltrimethoxysilane of 4ml, and stop reaction after backflow 10h, suction filtration, is washed till neutrality with distilled water, obtains silane coupled magadiite after drying.
Fig. 1 is the ESEM pattern contrast figure that embodiment 7 processes magadiite before and after the silane coupled hydridization magadiite that obtains, and in figure, a is H-magadiite, b for oxidation magadiite, c are silane coupled hydridization magadiite.As seen from Figure 1, from H-magadiite to silane coupled magadiite, be the stratiform pattern of " petal-shaped ", technicality is after silane, " petal " get Geng Kai on surface, a skim has obviously been spread on magadiite surface after silane coupled, clearly illustrates that success introduces silane coupling agent layer on magadiite surface.
Fig. 2 is the elementary analysis contrast figure that embodiment 7 processes magadiite before and after the silane coupled hydridization magadiite that obtains, and in figure, a is H-magadiite, b for oxidation magadiite, c are silane coupled hydridization magadiite.As seen from Figure 2, magadiite is after oxidation, and Surface Oxygen constituent content obviously increases, and the mass percent of oxygen element is increased to 60.8% from 57.4% of H-magadiite; And when by after silane coupled, silicone content obviously increases, and the mass percent of element silicon is increased to 42.5% from 33.9% of oxidation magadiite; Show that silane coupler has successfully been incorporated into the surface of magadiite material.
Fig. 3 is the infared spectrum contrast figure that embodiment 7 processes magadiite before and after the silane coupled hydridization magadiite that obtains, and in figure, a is oxidation magadiite, b is silane coupled magadiite.Contrasted from Fig. 3, magadiite is in silane coupled front and back, and significantly difference part is: after magadiite is silane coupled, at 3600cm
-1the H-O base absworption peak disappearance that place is free, simultaneously at 2975cm
-1and 2923cm
-1there is the absorption vibration peak of c h bond in place; On oxidation magadiite, H-O base absworption peak disappears, caused by reacting with silane coupler γ-aminopropyltrimethoxysilane, and after silane there is the absorption vibration peak of c h bond in magadiite, be introduced by silane coupled agent molecule, this also further demonstrates the surface that silane coupler has successfully been incorporated into magadiite material.
Embodiment 8
The present embodiment is that silane coupler hydridization magadiite catalyst carrier material is preparing the application in metallic catalyst, and the method for silane coupler hydridization magadiite catalyst carrier material metal supported catalyst is as follows:
The silane coupler hydridization magadiite catalyst carrier material 10g obtained according to embodiment 7, joins in the cobalt chloride solution of the 0.06mol/l of 50ml, magnetic agitation 2h; Then add excessive potassium borohydride to reduce, after 4h, stop reaction; Suction filtration, is washed till neutrality with distilled water, obtains hybridization carrier magadiite load cobalt catalyst after drying.
Embodiment 9
The present embodiment is that silane coupler hydridization magadiite catalyst carrier material is preparing the application in metallic catalyst, and the method for silane coupler hydridization magadiite catalyst carrier material metal supported catalyst is as follows:
The silane coupler hydridization magadiite catalyst carrier material 10g obtained according to embodiment 7, joins in the ruthenic chloride solution of the 0.06mol/L of 50ml, magnetic agitation 1h; Then add excessive potassium borohydride to reduce, after 2h, stop reaction; Suction filtration, is washed till neutrality with distilled water, obtains the catalyst of hybridization carrier magadiite load ruthenium after drying.
Embodiment 10
The present embodiment is that silane coupler hydridization magadiite catalyst carrier material is preparing the application in metallic catalyst, and the method for silane coupler hydridization magadiite catalyst carrier material metal supported catalyst is as follows:
The silane coupler hydridization magadiite catalyst carrier material 10g obtained according to embodiment 7, joins in the palladium chloride solution of the 0.06mol/L of 50ml, magnetic agitation 3h; Then add excessive potassium borohydride to reduce, after 5h, stop reaction; Suction filtration, is washed till neutrality with distilled water, obtains the catalyst of hybridization carrier magadiite supported palladium after drying.
Embodiment 11
The present embodiment is that H-magadiite is carried out the process of load ruthenium, experimental example in contrast.
According to the condition of embodiment 9, also H-magadiite is carried out the process of load ruthenium, the catalyst after process is tested as the control group of the carrier loaded ruthenium of silane coupled magadiite simultaneously.
Fig. 4 is the transmission electron microscope picture of the silane coupled magadiite hybridization carrier load ruthenium nano-cluster that embodiment 9 obtains.As can be seen from Figure 4, ruthenium nano-cluster after load is positioned at the surface of magadiite, and distribution of particles is even, size uniformity, illustrate that the magadiite after γ-aminopropyltrimethoxysilane coupling is as catalyst carrier, effectively can control the distribution of catalyst and the dimensional homogeneity of particle.
Fig. 5 is the silane coupled magadiite hybridization carrier load ruthenium that obtains of embodiment 9 and embodiment 11 and the catalytic activity of the carrier loaded ruthenium of H-magadiite after reusing 5 times, figure a is that H-magadiite makes carrier, and b is that silane coupled magadiite hybrid material makes carrier.
The method of testing of catalytic activity is: choosing sodium borohydride hydrolysis product hydrogen is catalyst probe reaction, and chemical equation is:
NaBH
4+2H
2O==4H
2+NaBO
2
Under alkaline reactive medium, when not having catalyst, hydrogen output is very little; And add catalyst, then greatly can accelerate the generation of hydrogen; Draining water gathering of gas law is adopted to collect the hydrogen produced.With the measurement foundation of the final productive rate catalytic activity of hydrogen.
The method of testing of replica test is: catalyst after the completion of reaction, suction filtration, dry; And the catalyst that can serve as next time.
As can be seen from Figure 5, when the Na-magadiite of identical load amount and silane coupled hydridization magadiite material acts as catalyst carrier, when first time uses, catalytic activity is close, all reaches more than 98%; And after a number of uses, make the catalyst of carrier with Na-magadiite, catalytic activity reduces gradually, and after reusing 5 times, catalytic activity only remains 60%; And the catalyst of carrier is made with silane coupled hydridization magadiite material, catalytic activity almost remains unchanged, and after reusing 5 times, catalytic activity remains 96%, and the catalytic activity used with first time is close.Repeated experiment illustrates, makees the catalyst of carrier, is reusing in process, effectively prevent coming off and reuniting of catalyst granules, cause catalytic activity almost not reduce with silane coupled hydridization magadiite material.
Claims (8)
1. a silane coupler hydridization magadiite catalyst carrier material, is characterized in that: introducing end group at magadiite material surface covalency is amino silane coupled agent molecule;
Its preparation method comprises the following steps: 1) Na-magadiite material being added concentration is in the hydrochloric acid solution of 0.5 ~ 2mol/L, and stir 1 ~ 5h, suction filtration, is washed till neutrality with distilled water, obtains H-magadiite after drying;
2) prepare strong oxidizing solution, temperature controls at 80 ~ 95 DEG C, adds dry H-magadiite, oxidation 20 ~ 40min, and suction filtration, is washed till neutrality with distilled water, obtains the magadiite be oxidized after drying;
3) magadiite after oxidation is placed in toluene, adds silane coupler, backflow 10 ~ 20h, suction filtration, is washed till neutrality with distilled water, namely obtains silane coupler hydridization magadiite catalyst carrier material after drying.
2. silane coupler hydridization magadiite catalyst carrier material according to claim 1, is characterized in that: described end group to be amino silane coupler be in γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane any one.
3. a preparation method for silane coupler hydridization magadiite catalyst carrier material as defined in claim 1, is characterized in that: comprise the following steps:
1) Na-magadiite material being added concentration is in the hydrochloric acid solution of 0.5 ~ 2mol/L, and stir 1 ~ 5h, suction filtration, is washed till neutrality with distilled water, obtains H-magadiite after drying;
2) prepare strong oxidizing solution, temperature controls at 80 ~ 95 DEG C, adds dry H-magadiite, oxidation 20 ~ 40min, and suction filtration, is washed till neutrality with distilled water, obtains the magadiite be oxidized after drying;
3) magadiite after oxidation is placed in toluene, adds silane coupler, backflow 10 ~ 20h, suction filtration, is washed till neutrality with distilled water, namely obtains silane coupler hydridization magadiite catalyst carrier material after drying.
4. the preparation method of silane coupler hydridization magadiite catalyst carrier material according to claim 3, is characterized in that: step 2) middle strong oxidizing solution, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7:3.
5. the preparation method of silane coupler hydridization magadiite catalyst carrier material according to claim 3, is characterized in that: step 3) in magadiite after every 20g oxidation, add 1 ~ 4mL silane coupler.
6. a silane coupler hydridization magadiite catalyst carrier material as claimed in claim 1 is preparing the application in metallic catalyst.
7. silane coupler hydridization magadiite catalyst carrier material according to claim 6 is preparing the application in metallic catalyst, it is characterized in that: the method for metal supported catalyst is that silane coupler hydridization magadiite catalyst carrier material is placed in metal salt solution, fully stirs 1 ~ 3h; Add reducing agent to reduce, stop reaction after 2 ~ 5h, suction filtration, is washed till neutrality with distilled water, namely obtains loaded catalyst after drying.
8. silane coupler hydridization magadiite catalyst carrier material according to claim 7 is preparing the application in metallic catalyst, it is characterized in that: described slaine is ruthenium trichloride, platinum chloride, palladium bichloride, cobalt chloride, nickel chloride, the one in copper chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210357235.7A CN102909083B (en) | 2012-09-24 | 2012-09-24 | Silane-coupler-hybridized magadiite catalyst carrier material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210357235.7A CN102909083B (en) | 2012-09-24 | 2012-09-24 | Silane-coupler-hybridized magadiite catalyst carrier material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102909083A CN102909083A (en) | 2013-02-06 |
| CN102909083B true CN102909083B (en) | 2015-04-15 |
Family
ID=47607798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210357235.7A Expired - Fee Related CN102909083B (en) | 2012-09-24 | 2012-09-24 | Silane-coupler-hybridized magadiite catalyst carrier material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102909083B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085603B (en) * | 2015-08-26 | 2018-03-02 | 河北大学 | A kind of load type platinum complex oxidant that can be recycled and its preparation method and application |
| CN105858678B (en) * | 2016-02-29 | 2017-12-01 | 华南理工大学 | Receive the preparation method of the hydridization type inierpeneirating network structure material of stone based on wheat hydroxyl silicon |
| CN110449150B (en) * | 2019-07-04 | 2020-11-06 | 中山大学 | Hollow carbon tube array catalyst embedded with nano metal and preparation method and application thereof |
| CN111514848A (en) * | 2020-04-29 | 2020-08-11 | 贵州大学 | Preparation and application of amino-modified aluminum magadiite selective adsorption material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1568703A (en) * | 2003-07-24 | 2005-01-26 | 合肥工业大学 | Attapulgite-argentum nanometer composite antibiotic material and preparation method thereof |
| CN1970607A (en) * | 2006-11-22 | 2007-05-30 | 北京化工大学 | Silane coupling agent modified clay and butadiene styrene rubber nanometer composite material preparation method |
| CN101658782A (en) * | 2009-08-24 | 2010-03-03 | 淮阴师范学院 | Method for preparing adsorbent by modifying attapulgite clay |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100215894A1 (en) * | 2009-02-02 | 2010-08-26 | INVISTA North America S.ar.I | Compositions of surface modified nanoparticles |
-
2012
- 2012-09-24 CN CN201210357235.7A patent/CN102909083B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1568703A (en) * | 2003-07-24 | 2005-01-26 | 合肥工业大学 | Attapulgite-argentum nanometer composite antibiotic material and preparation method thereof |
| CN1970607A (en) * | 2006-11-22 | 2007-05-30 | 北京化工大学 | Silane coupling agent modified clay and butadiene styrene rubber nanometer composite material preparation method |
| CN101658782A (en) * | 2009-08-24 | 2010-03-03 | 淮阴师范学院 | Method for preparing adsorbent by modifying attapulgite clay |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102909083A (en) | 2013-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102671710B (en) | Noble metal nanocatalyst loaded on dendritic macromolecule functionalized graphene and preparation method thereof | |
| CN102489314B (en) | Graphene-loaded double-metal nano particles for methanol and ethanol fuel cells, and preparation method for graphene-loaded double-metal nano particles | |
| CN102911474B (en) | Polyvinylpyrrolidone hybridized graphene catalyst carrier material and preparation method and application thereof | |
| CN106391013A (en) | Catalyst for electrochemically reducing carbon dioxide into carbon monoxide and preparation method of catalyst | |
| CN102909083B (en) | Silane-coupler-hybridized magadiite catalyst carrier material, and preparation method and application thereof | |
| CN109731586B (en) | Preparation method and application of copper-containing metal organic framework-derived hierarchical porous copper phosphide/carbohydrate electrolysis electrocatalyst | |
| CN112473691A (en) | Preparation method of low-platinum hollow polyhedral nano-structured catalyst | |
| CN111939930A (en) | Carbon quantum dot-loaded cobalt-ruthenium alloy composite material and preparation method and application thereof | |
| CN113611874A (en) | Composite carbon carrier alloy catalyst and preparation method and application thereof | |
| CN113555567A (en) | Platinum-carbon catalyst and preparation method thereof | |
| CN112736257A (en) | Embedded porous Fe-NxPreparation method of @ Pd-NC nanorod, nanorod prepared by preparation method and application of nanorod | |
| CN112387290A (en) | Fe3O4Preparation method and application of supported metal nanoparticles | |
| CN103394346A (en) | Preparation method for small-size high-dispersion fuel battery catalyst | |
| CN111584884A (en) | Microwave preparation method of fuel cell binary alloy catalyst | |
| CN111111715B (en) | Fe (Fe) x @Co 1-x P-RGO composite material and in-situ synthesis method and application thereof | |
| CN113909487B (en) | Coiled PtPd nano dendrite and preparation method and application thereof | |
| CN112458483B (en) | Preparation method of NiFe LDH @ Super-P composite electro-catalytic material | |
| CN111804314B (en) | Sugarcoated haw-shaped rhodium-tellurium nanochain catalyst for catalyzing methanol oxidation reaction and preparation method thereof | |
| CN114843535A (en) | Boron-doped palladium-based catalyst for fuel cell and preparation method thereof | |
| CN114807981A (en) | High-efficiency synthesis of H 2 O 2 Preparation method and application of Zn-N-C electrocatalyst | |
| CN112151812B (en) | Preparation method of rhodium/boron-nitrogen co-doped graphene aerogel three-dimensional composite electrode catalyst | |
| CN114232024A (en) | Preparation method of monodisperse nickel-iron nano material for oxygen evolution by electrolyzing water | |
| CN112301361A (en) | Hollow CoS2Oxygen evolution catalyst of microsphere modified nitrogen-doped porous carbon and preparation method thereof | |
| CN115044938B (en) | Dual-template induced high-activity Co/SiO 2 Preparation method and product of NC-CNTs electrocatalytic oxygen evolution material | |
| CN107195911A (en) | The preparation method of ruthenium-oxide bacteria cellulose composite load palladium base fuel-cell catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150415 Termination date: 20160924 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |