CN102909083A - 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
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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 the 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 has the not available unique texture of traditional catalyst and reactivity worth as a class new catalyst.They have shown unusual catalytic activity and selective in numerous reactions such as the selective hydrogenation of methanol carbonylation, propene hydroformylation reaction, double carbonylation reaction, Heck reaction and multiple reactant and asymmetric hydrogenation; Wherein nano-noble metal also can be used as good electrode catalyst and the purifying vehicle exhaust catalyst of effective catalyst, used in proton exchange membrane fuel cell of borohydride hydrolytic hydrogen production.But the noble metal reserves are rare, and are expensive, and the widely used catalyst materials in field such as its battery that acts as a fuel, petrochemical industry, purifying vehicle exhaust and chemical industry must become the bottleneck that noble metal moves towards the industrialization and uses.How to construct high activity, stable, reusable load type metal nanocatalyst has important practical significance.
Carrier not only affects catalytic performance, also price and the suitability for industrialized production of catalyst is played decisive action, and choosing of carrier is most important.And Magadiite(phyllosilicate) is a kind of resourceful layered clay material, industrially also accomplished scale production to have aboundresources, cheap advantage; Also have simultaneously good physical and mechanical properties and good chemical resistance; Magadiite has tridimensional structure in addition, and specific area is large; With other clay minerals relatively, magadiite can utilize in the laboratory cheap silica synthetic in enormous quantities, and purity is high, and easily cutting of surface has the incomparable advantage of other carriers aspect the catalyst carrier role serving as.
Current, the preparation of most of stratified material carried metal nanocatalysts generally directly combines carrier and metal nanometre cluster by physisorption, can not well satisfy industrial demand to catalyst, mainly have following technical problem: the magadiite lamella easily dissociates, and causes separation difficulty; Can not effectively control nano metal in dispersiveness and the size of carrier surface; 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 purpose 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 the Reusability process, catalyst is without coming off and reuniting.
Second purpose of the present invention provides a kind of preparation method of silane coupler hydridization magadiite catalyst carrier material.
The 3rd purpose of the present invention provides the application of a kind of silane coupler hydridization magadiite catalyst carrier material aspect the preparation metallic catalyst.
In order to realize above purpose, the technical solution adopted in the present invention is: a kind of silane coupler hydridization magadiite catalyst carrier material, this material are to introduce end group at magadiite material surface covalency to be amino silane coupled agent molecule.
Described silane coupler is any one in γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (the aminoethyl)-gamma-aminopropyl-triethoxy-silane.
A kind of preparation method of silane coupler hydridization magadiite catalyst carrier material comprises the following steps:
1) the Na-magadiite material being added concentration is in the hydrochloric acid solution of 0.5～2mol/l, stirs 1～5h, and suction filtration is washed till neutrality with distilled water, obtains H-magadiite after the drying;
2) preparation strong oxidizing property solution, temperature is controlled at 80～95 ℃, adds dry H-magadiite, oxidation 20～40min, suction filtration is washed till neutrality with distilled water, obtains the magadiite of oxidation after the drying;
3) magadiite after the oxidation is placed toluene, add silane coupler, the 10～20h that refluxes, suction filtration is washed till neutrality with distilled water, namely gets silane coupler hydridization magadiite catalyst carrier material after the drying.
In the described strong oxidizing property solution, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7:3.
Magadiite in the step 3) after every 20g oxidation adds 1～4ml silane coupler.
The application of a kind of silane coupler hydridization magadiite catalyst carrier material aspect the preparation metallic catalyst.
The method of metal supported catalyst is that silane coupler hydridization magadiite catalyst carrier material is placed metal salt solution, fully stirs 1～3h; Add reducing agent and reduce, stop reaction behind 2～5h, suction filtration is washed till neutrality with distilled water, namely gets loaded catalyst after the drying.
Described slaine is ruthenium trichloride, platinum chloride, palladium bichloride, cobalt chloride, nickel chloride, a kind of in the copper chloride.
The present invention is in order to improve interface bond strength and the easy separation between magadiite carrier material and the metallic catalyst, chemically construct the magadiite hybrid material, realize the chemical bond between hybrid material and the metal nanometre cluster, improve dispersiveness, stability and the separation property of the nano metal particles of load.
The present invention with silane coupler by covalent effect and magadiite surface conjunction together as catalyst carrier material, not only can bring into play the composite advantage of inorganic material and organic material, be conducive to improve the easy separation of supported catalyst; Improve the bond strength at interface between carrier and the nano metal bunch, improve the dispersiveness of nano particle, the reunion of prevention nano particle and coming off.
The Magadiite material after silane coupled, solved magadiite lamella legibility from problem, separate easily, simplified the separation of catalyst and reclaimed technique; The surface covalency has been introduced the amino functional group of end, has improved the active force of carrier and metal ion, can realize that nano metal is in Uniform Dispersion and the size Control of carrier surface; Improve the interface binding power between carrier material and the catalyst, made it in catalysis and Reusability process, avoided the reunion of metal nanoparticle and the degree that comes off, effectively improved stability, activity and the life-span of loaded catalyst.
Preparation method's technique of the present invention is simple, need not special installation, and production cost is low, is suitable for suitability for industrialized production.
The present invention carries out covalent modified to the magadiite carrier surface with silane coupler, as template, can induce the growth in situ of metal nanometre cluster.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of magadiite material before and after silane coupled hydridization;
(a) H-magadiite, (b) oxidation 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) oxidation 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 the repeat performance of silane coupler hydridization magadiite catalyst carrier load ruthenium nano-cluster and the direct load ruthenium of magadiite nano-cluster compares;
(a) H-magadiite load ruthenium nano-cluster, (b) silane coupled hydridization magadiite material load ruthenium nano-cluster.
The specific embodiment
The present invention is further illustrated below in conjunction with the specific embodiment:
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment is to introduce end group at magadiite material surface covalency to be amino γ-aminopropyltrimethoxysilane, and the preparation method comprises the following steps:
1) the Na-magagiite material adding 3000ml concentration with 150g is in the hydrochloric acid solution of 1mol/l, stirs 3h, and suction filtration is washed till neutrality with distilled water, obtains H-magadiite after the drying;
2) volume ratio of the preparation concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing property solution 500ml of 7:3, and temperature is controlled at 85 ℃, adds the H-magadiite of 100g drying, oxidization time is controlled at 30min, suction filtration is washed till neutrality with distilled water, obtains the magadiite of oxidation after the drying;
3) magadiite after the 20g oxidation is placed 1000ml toluene, add the γ-aminopropyltrimethoxysilane of 2.5ml, stop reaction behind the backflow 15h, suction filtration is washed till neutrality with distilled water, obtains silane coupled magadiite after the drying.
Embodiment 2
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment is to introduce end group at magadiite material surface covalency to be amino gamma-aminopropyl-triethoxy-silane, and the preparation method comprises the following steps:
1) the Na-magagiite material adding 3000ml concentration with 150g is in the hydrochloric acid solution of 0.5mol/l, stirs 5h, and suction filtration is washed till neutrality with distilled water, obtains H-magadiite after the drying;
2) volume ratio of the preparation concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing property solution 500ml of 7:3, and temperature is controlled at 85 ℃, adds the H-magadiite of 100g drying, oxidization time is controlled at 30min, suction filtration is washed till neutrality with distilled water, obtains the magadiite of oxidation after the drying;
3) magadiite after the 20g oxidation is placed 1000ml toluene, add the gamma-aminopropyl-triethoxy-silane of 2.5ml, stop reaction behind the backflow 15h, suction filtration is washed till neutrality with distilled water, obtains silane coupled magadiite after the drying.
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment is to introduce end group at magadiite material surface covalency to be amino N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, and the preparation method comprises the following steps:
1) the Na-magagiite material adding 3000ml concentration with 150g is in the hydrochloric acid solution of 2mol/l, stirs 1h, and suction filtration is washed till neutrality with distilled water, obtains H-magadiite after the drying;
2) volume ratio of the preparation concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing property solution 500ml of 7:3, and temperature is controlled at 85 ℃, adds the H-magadiite of 100g drying, oxidization time is controlled at 30min, suction filtration is washed till neutrality with distilled water, obtains the magadiite of oxidation after the drying;
3) magadiite after the 20g oxidation is placed 1000ml toluene, the N-β (aminoethyl) of adding 2.5ml-γ-aminopropyltrimethoxysilane stops reaction, suction filtration behind the backflow 15h, be washed till neutrality with distilled water, obtain silane coupled magadiite after the drying.
Embodiment 4
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment is to introduce end group at magadiite material surface covalency to be amino N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, and the preparation method comprises the following steps:
1) the Na-magagiite material adding 3000ml concentration with 150g is in the hydrochloric acid solution of 1mol/l, stirs 3h, and suction filtration is washed till neutrality with distilled water, obtains H-magadiite after the drying;
2) volume ratio of the preparation concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing property solution 500ml of 7:3, and temperature is controlled at 80 ℃, adds the H-magadiite of 100g drying, oxidization time is controlled at 40min, suction filtration is washed till neutrality with distilled water, obtains the magadiite of oxidation after the drying;
3) magadiite after the 20g oxidation is placed 1000ml toluene, the N-β (aminoethyl) of adding 2.5ml-gamma-aminopropyl-triethoxy-silane stops reaction, suction filtration behind the backflow 15h, be washed till neutrality with distilled water, obtain silane coupled magadiite after the drying.
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment is to introduce end group at magadiite material surface covalency to be amino γ-aminopropyltrimethoxysilane, and the preparation method comprises the following steps:
1) the Na-magagiite material adding 3000ml concentration with 150g is in the hydrochloric acid solution of 1mol/l, stirs 3h, and suction filtration is washed till neutrality with distilled water, obtains H-magadiite after the drying;
2) volume ratio of the preparation concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing property solution 500ml of 7:3, and temperature is controlled at 95 ℃, adds the H-magadiite of 100g drying, oxidization time is controlled at 20min, suction filtration is washed till neutrality with distilled water, obtains the magadiite of oxidation after the drying;
3) magadiite after the 20g oxidation is placed 1000ml toluene, add the γ-aminopropyltrimethoxysilane of 2.5ml, stop reaction behind the backflow 15h, suction filtration is washed till neutrality with distilled water, obtains silane coupled magadiite after the drying.
Embodiment 6
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment is to introduce end group at magadiite material surface covalency to be amino γ-aminopropyltrimethoxysilane, and the preparation method comprises the following steps:
1) the Na-magagiite material adding 3000ml concentration with 150g is in the hydrochloric acid solution of 1mol/l, stirs 3h, and suction filtration is washed till neutrality with distilled water, obtains H-magadiite after the drying;
2) volume ratio of the preparation concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing property solution 500ml of 7:3, and temperature is controlled at 80 ℃, adds the H-magadiite of 100g drying, oxidization time is controlled at 40min, suction filtration is washed till neutrality with distilled water, obtains the magadiite of oxidation after the drying;
3) magadiite after the 20g oxidation is placed 1000ml toluene, add the silane coupler γ-aminopropyltrimethoxysilane of 1ml, stop reaction behind the backflow 20h, suction filtration is washed till neutrality with distilled water, obtains silane coupled magadiite after the drying.
Embodiment 7
The silane coupler hydridization magadiite catalyst carrier material of the present embodiment is to introduce end group at magadiite material surface covalency to be amino γ-aminopropyltrimethoxysilane, and the preparation method comprises the following steps:
1) the Na-magagiite material adding 3000ml concentration with 150g is in the hydrochloric acid solution of 1mol/l, stirs 3h, and suction filtration is washed till neutrality with distilled water, obtains H-magadiite after the drying;
2) volume ratio of the preparation concentrated sulfuric acid and hydrogen peroxide is the strong oxidizing property solution 500ml of 7:3, and temperature is controlled at 80 ℃, adds the H-magadiite of 100g drying, oxidization time is controlled at 40min, suction filtration is washed till neutrality with distilled water, obtains the magadiite of oxidation after the drying;
3) magadiite after the 20g oxidation is placed 1000ml toluene, add the silane coupler γ-aminopropyltrimethoxysilane of 4ml, stop reaction behind the backflow 10h, suction filtration is washed till neutrality with distilled water, obtains silane coupled magadiite after the drying.
Fig. 1 is the ESEM pattern contrast figure that embodiment 7 processes the silane coupled hydridization magadiite front and back magadiite that obtains, and a is H-magadiite among the figure, and b is oxidation magadiite, and c is silane coupled hydridization magadiite.As seen from Figure 1, from H-magadiite to silane coupled magadiite, be the stratiform pattern of " petal-shaped ", after technicality is silane, " petal " on a surface De Gengkai, a skim has obviously been spread on magadiite surface after silane coupled, clearly illustrates that success is at magadiite surface introducing silane coupling agent layer.
Fig. 2 is the elementary analysis contrast figure that embodiment 7 processes the silane coupled hydridization magadiite front and back magadiite that obtains, and a is H-magadiite among the figure, and b is oxidation magadiite, and c is silane coupled hydridization magadiite.As seen from Figure 2, magadiite is after oxidation, and the 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 silane coupler by being incorporated into of success the surface of magadiite material.
Fig. 3 is the infared spectrum contrast figure that embodiment 7 processes the silane coupled hydridization magadiite front and back magadiite that obtains, and a is oxidation magadiite among the figure, and b is silane coupled magadiite.Contrasted as seen by Fig. 3, magadiite significantly distinguishes part and is: after magadiite is silane coupled, at 3600cm in silane coupled front and back
-1The free H-O base absworption peak in place disappears, simultaneously at 2975cm
-1And 2923cm
-1The absorption vibration peak of c h bond has appearred in the place; The upper H-O base of oxidation magadiite absworption peak disappears, because due to reacting with the silane coupler γ-aminopropyltrimethoxysilane, and the absorption vibration peak of c h bond has appearred in magadiite behind the silane, be to be introduced by silane coupled agent molecule, this has proved further that also silane coupler successfully has been incorporated into the surface of magadiite material.
Embodiment 8
The present embodiment is the application of silane coupler hydridization magadiite catalyst carrier material aspect the preparation metallic catalyst, and the method for silane coupler hydridization magadiite catalyst carrier material metal supported catalyst is as follows:
According to the silane coupler hydridization magadiite catalyst carrier material 10g that embodiment 7 obtains, join in the cobalt chloride solution of 0.06mol/l of 50ml magnetic agitation 2h; Then add excessive potassium borohydride and reduce, stop reaction behind the 4h; Suction filtration is washed till neutrality with distilled water, obtains hybridization carrier magadiite load cobalt catalyst after the drying.
Embodiment 9
The present embodiment is the application of silane coupler hydridization magadiite catalyst carrier material aspect the preparation metallic catalyst, and the method for silane coupler hydridization magadiite catalyst carrier material metal supported catalyst is as follows:
According to the silane coupler hydridization magadiite catalyst carrier material 10g that embodiment 7 obtains, join in the ruthenic chloride solution of 0.06mol/L of 50ml magnetic agitation 1h; Then add excessive potassium borohydride and reduce, stop reaction behind the 2h; Suction filtration is washed till neutrality with distilled water, obtains the catalyst of hybridization carrier magadiite load ruthenium after the drying.
Embodiment 10
The present embodiment is the application of silane coupler hydridization magadiite catalyst carrier material aspect the preparation metallic catalyst, and the method for silane coupler hydridization magadiite catalyst carrier material metal supported catalyst is as follows:
According to the silane coupler hydridization magadiite catalyst carrier material 10g that embodiment 7 obtains, join in the palladium chloride solution of 0.06mol/L of 50ml magnetic agitation 3h; Then add excessive potassium borohydride and reduce, stop reaction behind the 5h; Suction filtration is washed till neutrality with distilled water, obtains the catalyst of hybridization carrier magadiite supported palladium after the drying.
Embodiment 11
The present embodiment is H-magadiite to be carried out the load ruthenium process, in contrast experimental example.
According to the condition of embodiment 9, also H-magadiite is carried out the load ruthenium simultaneously and process, the catalyst after the processing is as the control group experiment of the carrier loaded ruthenium of silane coupled magadiite.
Fig. 4 is the transmission electron microscope picture of the silane coupled magadiite hybridization carrier load ruthenium nano-cluster that obtains of embodiment 9.As can be seen from Figure 4, ruthenium nano-cluster after the load is positioned at the surface of magadiite, and distribution of particles is even, the size homogeneous, the magadiite of explanation after the γ-aminopropyltrimethoxysilane coupling can effectively control the distribution of catalyst and the dimensional homogeneity of particle as catalyst carrier.
Fig. 5 is that the silane coupled magadiite hybridization carrier load ruthenium that obtains of embodiment 9 and embodiment 11 and the carrier loaded ruthenium of H-magadiite are in the catalytic activity of reusing after 5 times, figure a is that H-magadiite makes carrier, and b is that silane coupled magadiite hybrid material is made carrier.
The method of testing of catalytic activity is: choosing sodium borohydride hydrolysis product hydrogen is the 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 the adding catalyst then can accelerate the generation of hydrogen greatly; Adopt draining water gathering of gas law to collect the hydrogen that produces.Measurement foundation with the final productive rate catalytic activity of hydrogen.
The method of testing of replica test is: catalyst after reaction finishes, suction filtration, drying; And can serve as next time catalyst.
As can be seen from Figure 5, when the Na-magadiite of identical load amount and silane coupled hydridization magadiite material served as catalyst carrier, when using for the first time, catalytic activity approached, and has all reached more than 98%; And after repeatedly using, make the catalyst of carrier with Na-magadiite, and catalytic activity reduces gradually, and after reusing 5 times, catalytic activity has only kept 60%; And make the catalyst of carrier with silane coupled hydridization magadiite material, and catalytic activity almost remains unchanged, and after reusing 5 times, catalytic activity has kept 96%, approaches with the catalytic activity of using for the first time.The catalyst of carrier is made in repeated experiment explanation with silane coupled hydridization magadiite material, in reusing process, effectively stoped coming off and reuniting of catalyst granules, causes almost not reduction of catalytic activity.
Claims (8)
1. a silane coupler hydridization magadiite catalyst carrier material is characterized in that: introduce end group at magadiite material surface covalency and be amino silane coupled agent molecule.
2. silane coupler hydridization magadiite catalyst carrier material according to claim 1 is characterized in that: described end group is in γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (the aminoethyl)-gamma-aminopropyl-triethoxy-silane any one for amino silane coupler.
3. the preparation method such as silane coupler hydridization magadiite catalyst carrier material according to claim 1 is characterized in that: comprise the following steps:
1) the Na-magadiite material being added concentration is in the hydrochloric acid solution of 0.5～2mol/l, stirs 1～5h, and suction filtration is washed till neutrality with distilled water, obtains H-magadiite after the drying;
2) preparation strong oxidizing property solution, temperature is controlled at 80～95 ℃, adds dry H-magadiite, oxidation 20～40min, suction filtration is washed till neutrality with distilled water, obtains the magadiite of oxidation after the drying;
3) magadiite after the oxidation is placed toluene, add silane coupler, the 10～20h that refluxes, suction filtration is washed till neutrality with distilled water, namely gets silane coupler hydridization magadiite catalyst carrier material after the 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 property 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: the magadiite in the step 3) after every 20g oxidation, adding 1～4ml silane coupler.
6. the application of silane coupler hydridization magadiite catalyst carrier material as claimed in claim 1 aspect the preparation metallic catalyst.
7. the application of silane coupler hydridization magadiite catalyst carrier material according to claim 6 aspect the preparation metallic catalyst, it is characterized in that: the method for metal supported catalyst is that silane coupler hydridization magadiite catalyst carrier material is placed metal salt solution, fully stirs 1～3h; Add reducing agent and reduce, stop reaction behind 2～5h, suction filtration is washed till neutrality with distilled water, namely gets loaded catalyst after the drying.
8. the application of silane coupler hydridization magadiite catalyst carrier material according to claim 7 aspect the preparation metallic catalyst, it is characterized in that: described slaine is ruthenium trichloride, platinum chloride, palladium bichloride, cobalt chloride, nickel chloride, a kind of in the copper chloride.
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