CN103691486B - A kind of preparation method of immobilized metal ion organic complex catalyst - Google Patents
A kind of preparation method of immobilized metal ion organic complex catalyst Download PDFInfo
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- CN103691486B CN103691486B CN201310746265.1A CN201310746265A CN103691486B CN 103691486 B CN103691486 B CN 103691486B CN 201310746265 A CN201310746265 A CN 201310746265A CN 103691486 B CN103691486 B CN 103691486B
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Abstract
The present invention relates to Industrial Catalysis field, particularly a kind of preparation method of immobilized metal ion organic complex catalyst.This preparation method comprises: obtain the active carbon after oxidation; Under organic solvent and water existent condition, the active carbon after oxidation and silane coupler generation Silanization reaction, obtain nitrogenous bidentate ligand active carbon; Get nitrogenous bidentate ligand active carbon and complexing of metal ion, to obtain final product; The mol ratio of water and silane coupler is 1:(1 ~ 3).Utilize preparation method provided by the invention can significantly improve active carbon to metal ion supported quantity.
Description
Technical field
The present invention relates to Industrial Catalysis field, particularly a kind of preparation method of immobilized metal ion organic complex catalyst.
Background technology
Catalyst refers to the chemical reaction rate (can improve and also can reduce) that can change other materials in chemical reaction, and the material that the quality of itself and chemical property all do not change before and after chemical reaction, also be catalyst, it has height selective (or selectivity).
Catalyst type is various, metal ion organic complex catalyst refers to the catalyst being made reactant molecule activate by coordination, at least containing a metal ion or atom in this kind of catalyst, no matter whether parent itself is complex compound, but time in action, catalytic active center occurs with coordination structure, by changing metal-complexing number or dentate, the rarest a kind of reaction molecular enters co-ordination state and is activated, thus promotes the carrying out of reaction.
Metal ion organic complex catalyst has played important effect in organic synthesis, but this kind of catalytic reaction is all homogeneous catalysis system usually, comparatively serious to e-quipment and pipe corrosion, catalyst separation is difficult simultaneously, large multivalent transition metal is poisonous, easily causes environmental pollution.Therefore, use heterogeneous catalytic system industrial, heterogeneous catalysis not only can reduce the loss of catalyst, and catalyst is easily separated and recycles more.In heterogeneous catalytic system, the conventional carriers of immobilized metallo-organic complex catalyst has macromolecule, SiO
2mesopore molecular sieve etc.But macromolecule carrier poor heat stability, mechanical strength is low, mostly is non-porous structure, and specific area is little, and antioxygenic property is poor.In inorganic carrier, SiO
2mesopore molecular sieve, because of the well-regulated pore passage structure of its tool and larger pore volume, higher specific area, excellent chemical stability and heat endurance, is therefore paid close attention to widely.But SiO
2the synthesis of mesopore molecular sieve is the process of a more complicated, and synthesis cost is higher.Meanwhile, SiO
2mesopore molecular sieve needs high-temperature roasting to remove organic formwork agent, and exhibiting high surface silicone hydroxyl also can dehydrating condensation, and cause the organic ligand number that is linked on carrier very limited, catalytic active site is few.Simultaneously because usually need calcining in granulating powders forming process, the organic ligand for complexation of metal ions cannot be retained, so SiO
2mesopore molecular sieve supported metal ion organic complex catalyst cannot be applied in packed bed reactor.
At present, the report adopting active carbon as metal ion organic complex catalyst carrier is had.Compare conventional carriers, active carbon not only has flourishing gap structure and huge specific area, and it is cheap and easy to get, safety non-toxic, mechanical strength is high, wear-resisting, its intrinsic granular texture makes it not be only applicable to paste state bed reactor, and also has advantageous advantage and potential in packed bed reactor.But current reported be that carrier solid-carried catalyst normally adopts physical adsorption process to prepare with active carbon, active component and carrier are only by faint van der Waals interaction, catalyst is connected insecure with carrier, active component very easily runs off, and the method therefore exploring the immobilized metallo-organic complex catalyst of active carbon chemistry is very necessary.
Summary of the invention
In view of this, the invention provides a kind of preparation method of immobilized metal ion organic complex catalyst.This preparation method, by adding a small amount of water in Silanization reaction system, improves the supported quantity of metal ion.
In order to realize foregoing invention object, the invention provides following technical scheme:
The invention provides a kind of preparation method of immobilized metal ion organic complex catalyst, comprise the steps:
Obtain the active carbon after oxidation;
Under organic solvent and water existent condition, the active carbon after oxidation and silane coupler generation Silanization reaction, obtain nitrogenous bidentate ligand active carbon;
Get nitrogenous bidentate ligand active carbon and complexing of metal ion, to obtain final product;
The mol ratio of water and silane coupler is 1:(1 ~ 3).
Silane coupler is relatively more active, easily decomposes in water, so generally not adding water carries out Silanization reaction in Silanization reaction system.The present invention adds a small amount of water in Silanization reaction system, thus silane coupler supported quantity can be improved 10 times, its mechanism is: add a small amount of water be conducive to silane coupler with oxidation after activated carbon surface on phenolic hydroxyl group generation graft reaction, easier by immobilized for silane coupler covalency on absorbent charcoal carrier.
During nitrogenous bidentate ligand active carbon supported metal ion, the mechanism that supported quantity improves is: the lone pair electrons on nitrogen-atoms will enter the unoccupied orbital of metal ion, form coordinate bond, two nitrogen due to bidentate ligand distinguish the other way around chelated metal ions simultaneously, therefore have higher ligand complex ability than monodentate ligand.
In embodiments more provided by the invention, silane coupler is selected from N-[3-(trimethoxy is silica-based)-propyl group] ethylethylenediamine or N, N '-two [(trimethoxy silicon) propyl group]-1,2-cyclohexanediamine.
In embodiments more provided by the invention, nitrogenous bidentate ligand active carbon is the active carbon containing cyclohexanediamine part or the active carbon containing ethylene diamine ligand.
As preferably, Silanization reaction is silanization 12 ~ 48h under 20 ~ 110 DEG C of conditions.
Active carbon is a kind of cheapness, be easy to get, nontoxic porous material, and aperture can regulate in preparation process, has higher mechanical strength, and good wearability and intrinsic grain structure, meet the requirement of packed bed reactor continued operation.In embodiments more provided by the invention, the raw material sources of active carbon are in ature of coal and/or shell.
In embodiments more provided by the invention, shell is selected from a kind of or both the above mixtures in coconut husk, peach-pit shell, almond shell or walnut shell.
In embodiments more provided by the invention, the aperture of active carbon is 1 ~ 200nm.
As preferably, the aperture of active carbon is 2 ~ 100nm.
In embodiments more provided by the invention, the specific area of active carbon is 200 ~ 1600m
2/ g.
In embodiments more provided by the invention, the particle diameter of active carbon is 0.3 ~ 5mm.
Before active carbon and biology enzyme generation covalent bond, a series of means need be adopted to carry out modification to active carbon, first need to be oxidized active carbon, obtain the active carbon after oxidation, make activated carbon surface produce a large amount of phenolic hydroxyl groups, for Silanization reaction.In embodiments more provided by the invention, the reagent that oxidation adopts is nitric acid.
In embodiments more provided by the invention, the mass percentage concentration of nitric acid is 20% ~ 55%.
As preferably, the mass percentage concentration of nitric acid is 30% ~ 55%.
In embodiments more provided by the invention, be oxidized to and be oxidized 3 ~ 8h under the condition of 40 ~ 100 DEG C.
In embodiments more provided by the invention, in the active carbon after oxidation, content of phenolic hydroxyl groups is 0.1 ~ 1mmol/g.
In embodiments more provided by the invention, organic solvent used in Silanization reaction is a kind of or both the above mixtures in isopropyl alcohol, ethanol, ethyl acetate, THF, acetone, acetonitrile, DMF, DMSO, toluene or chloroform.
As preferably, in g/mL, the mass volume ratio of the active carbon after oxidation and silanization coupling agent is 1:(0.1 ~ 1).
In embodiments more provided by the invention, the mass volume ratio of the active carbon after oxidation and silanization coupling agent is 1:0.5.
In other embodiments provided by the invention, the mass volume ratio of the active carbon after oxidation and silanization coupling agent is 3:2.
In embodiments more provided by the invention, in nitrogenous bidentate ligand active carbon and complexing of metal ion process, metal ion is a kind of or both the above mixtures in copper ion, zinc ion, iron ion, palladium ion, cobalt ions or manganese ion.
In embodiments more provided by the invention, in nitrogenous bidentate ligand active carbon and complexing of metal ion process, complexing is specially complexing 24 ~ 48h under the condition of 20 ~ 40 DEG C.
In embodiments more provided by the invention, the solvent of complexing is carrene or benzene.
As preferably, the solvent of complexing is carrene.
Present invention also offers a kind of preparation method of immobilized metal ion organic complex catalyst, comprise the steps:
Obtain the active carbon after oxidation;
Under organic solvent and water existent condition, the active carbon after oxidation and silane coupler generation Silanization reaction, then with nitrogenous bidentate ligand donor generation substitution reaction, obtain nitrogenous bidentate ligand active carbon;
Get nitrogenous bidentate ligand active carbon and complexing of metal ion, to obtain final product;
The mol ratio of water and silane coupler is 1:(1 ~ 3).
Silane coupler is relatively more active, easily decomposes in water, so generally not adding water carries out Silanization reaction in Silanization reaction system.The present invention adds a small amount of water in Silanization reaction system, thus silane coupler supported quantity can be improved 10 times, its mechanism is: add a small amount of water be conducive to silane coupler with oxidation after activated carbon surface on phenolic hydroxyl group generation graft reaction, easier by immobilized for silane coupler covalency on absorbent charcoal carrier.
During nitrogenous bidentate ligand active carbon supported metal ion, the mechanism that supported quantity improves is: the lone pair electrons on nitrogen-atoms will enter the unoccupied orbital of metal ion, form coordinate bond, two nitrogen due to bidentate ligand distinguish the other way around chelated metal ions simultaneously, therefore have higher ligand complex ability than monodentate ligand.
In embodiments more provided by the invention, silane coupler is selected from 3-aminopropyl trimethoxysilane, 3-r-chloropropyl trimethoxyl silane, trichloromethyl silane, 3-chloropropyl triethoxysilane, 2-aminoethyl trimethoxy silane or 4-chloromethyl phenyl trichlorosilane silicon.
When silane coupler is 3-aminopropyl trimethoxysilane, 3-r-chloropropyl trimethoxyl silane, trichloromethyl silane, 3-chloropropyl triethoxysilane, 2-aminoethyl trimethoxy silane or 4-chloromethyl phenyl trichlorosilane silicon, these 6 kinds of silane couplers itself do not have nitrogenous bidentate ligand group, therefore after also needing the nitrogenous bidentate ligand group of further grafting, then supported metal ion.In the present invention, nitrogenous bidentate ligand is provided by nitrogenous bidentate ligand donor.
In embodiments more provided by the invention, nitrogenous bidentate ligand donor is the nitrogenous bidentate ligand donor of ring heptamethylene diamine type or the nitrogenous bidentate ligand donor of malononitrile group type.
In embodiments more provided by the invention, the nitrogenous bidentate ligand donor of ring heptamethylene diamine type is ethylating N-(Propylamino) tropone.
In embodiments more provided by the invention, the nitrogenous bidentate ligand donor of malononitrile group type is NaCH (CN)
2.
Nitrogenous bidentate ligand donor is NaCH (CN)
2time, substitution reaction is: get product and NaCH (CN) that Silanization reaction obtains
2there is substitution reaction.Use NaI as catalyst in addition in reaction system.
When nitrogenous bidentate ligand donor is the nitrogenous bidentate ligand donor of ring heptamethylene diamine type, what obtain after there is substitution reaction is the active carbon containing ring heptamethylene diamine part.
When nitrogenous bidentate ligand donor is the nitrogenous bidentate ligand donor of malononitrile group type, what obtain after there is substitution reaction is the active carbon containing propyl group malononitrile group part or the active carbon containing benzyl malononitrile group part.
As preferably, substitution reaction is specially and replaces 16 ~ 48h under 20 or 90 DEG C of condition.
In embodiments more provided by the invention, the solvent of substitution reaction is the mixed solvent of ethanol and ammoniacal liquor, carrene, toluene or DMF.
As preferably, Silanization reaction is silanization 12 ~ 48h under 20 ~ 110 DEG C of conditions.
Active carbon is a kind of cheapness, be easy to get, nontoxic porous material, and aperture can regulate in preparation process, has higher mechanical strength, and good wearability and intrinsic grain structure, meet the requirement of packed bed reactor continued operation.In embodiments more provided by the invention, the raw material sources of active carbon are in ature of coal and/or shell.
In embodiments more provided by the invention, shell is selected from a kind of or both the above mixtures in coconut husk, peach-pit shell, almond shell or walnut shell.
In embodiments more provided by the invention, the aperture of active carbon is 1 ~ 200nm.
As preferably, the aperture of active carbon is 2 ~ 100nm.
In embodiments more provided by the invention, the specific area of active carbon is 200 ~ 1600m
2/ g.
In embodiments more provided by the invention, the particle diameter of active carbon is 0.3 ~ 5mm.
Before active carbon and biology enzyme generation covalent bond, a series of means need be adopted to carry out modification to active carbon, first need to be oxidized active carbon, obtain the active carbon after oxidation, make activated carbon surface produce a large amount of phenolic hydroxyl groups, for Silanization reaction.In embodiments more provided by the invention, the reagent that oxidation adopts is nitric acid.
In embodiments more provided by the invention, the mass percentage concentration of nitric acid is 20% ~ 55%.
As preferably, the mass percentage concentration of nitric acid is 30% ~ 55%.
In embodiments more provided by the invention, be oxidized to and be oxidized 3 ~ 8h under the condition of 40 ~ 100 DEG C.
In embodiments more provided by the invention, in the active carbon after oxidation, content of phenolic hydroxyl groups is 0.1 ~ 1mmol/g.
In embodiments more provided by the invention, organic solvent used in Silanization reaction is a kind of or both the above mixtures in isopropyl alcohol, ethanol, ethyl acetate, THF, acetone, acetonitrile, DMF, DMSO, toluene or chloroform.
As preferably, in g/mL, the mass volume ratio of the active carbon after oxidation and silanization coupling agent is 1:(0.1 ~ 1).
In embodiments more provided by the invention, the mass volume ratio of the active carbon after oxidation and silanization coupling agent is 1:0.5.
In other embodiments provided by the invention, the mass volume ratio of the active carbon after oxidation and silanization coupling agent is 3:2.
In embodiments more provided by the invention, in nitrogenous bidentate ligand active carbon and complexing of metal ion process, metal ion is a kind of or both the above mixtures in copper ion, zinc ion, iron ion, palladium ion, cobalt ions or manganese ion.
In embodiments more provided by the invention, in nitrogenous bidentate ligand active carbon and complexing of metal ion process, complexing is specially complexing 24 ~ 48h under the condition of 20 ~ 40 DEG C.
In embodiments more provided by the invention, the solvent of complexing is carrene or benzene.
As preferably, the solvent of complexing is carrene.
The invention provides a kind of preparation method of immobilized metal ion organic complex catalyst.This preparation method comprises: obtain the active carbon after oxidation; Under organic solvent and water existent condition, the active carbon after oxidation and silane coupler generation Silanization reaction, obtain nitrogenous bidentate ligand active carbon; Get nitrogenous bidentate ligand active carbon and complexing of metal ion, to obtain final product; The mol ratio of water and silane coupler is 1:(1 ~ 3).By metal ion supported quantity detection experiment, in result display immobilized metal ion organic complex catalyst provided by the invention, the supported quantity of metal ion obtains significant raising (P < 0.05).As can be seen here, in Silanization reaction, add a small amount of water, and use nitrogenous bidentate ligand active carbon complexation of metal ions, metal ion supported quantity can be significantly improved.
Accompanying drawing explanation
Fig. 1 shows the infrared spectrogram that embodiment 1 provides; Wherein, line a shows the walnut nuclear activity charcoal after oxidation, and line b shows the active carbon after silanization, and line c shows the active carbon containing benzyl malononitrile group part;
Fig. 2 shows the infrared spectrogram that embodiment 2 provides; Wherein, line a shows the cocoanut active charcoal after oxidation, and line b shows the active carbon after silanization, and line c shows the active carbon containing propyl group malononitrile group part.
Detailed description of the invention
The invention discloses a kind of preparation method of immobilized metal ion organic complex catalyst, those skilled in the art can use for reference present disclosure, and suitable improving technique parameter realizes.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are all deemed to be included in the present invention.Method of the present invention and application are described by preferred embodiment, related personnel obviously can not depart from content of the present invention, spirit and scope methods and applications as herein described are changed or suitably change with combination, realize and apply the technology of the present invention.
In the preparation method of immobilized metal ion organic complex catalyst provided by the invention, raw materials used medicine or auxiliary material all can be buied by market.
Below in conjunction with embodiment, set forth the present invention further:
The preparation of embodiment 1 immobilized metal ion organic complex catalyst
At 100 DEG C, boil walnut nuclear activity charcoal 3h with 3%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 40%
3react 4h at 85 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the walnut nuclear activity charcoal after oxidation after testing.
With 150mL isopropyl alcohol as solvent; walnut nuclear activity charcoal after being oxidized by 3g and 0.1mL ethanol mix with 2mL4-chloromethyl phenyl trichlorosilane (silane coupler) under nitrogen protection; add deionized water (mol ratio of water and silane coupler is 1:1.5) again; at 80 DEG C of reaction 24h; obtaining the second product, is the active carbon after silanization after testing.
In 200mLDMF, add the active carbon after 2.0g silanization again, under nitrogen protection, add 0.1gNaCH (CN)
2and 0.05gNaI, heat stirring and refluxing 48h at 90 DEG C, suction filtration, solid matter is with carrene surname extraction 24h, and 70 DEG C of vacuum drying, obtain third product, is the active carbon containing benzyl malononitrile group part after testing.
Active carbon 1.5g being contained benzyl malononitrile group part adds 50mL containing 0.4gPd (PhCN)
2cl
2carrene in, stirring reaction 48h at 20 DEG C, suction filtration, solid matter with carrene surname extraction 24h, 70 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
Get above-mentioned the first obtained product, the second product, third product utilize infra-red sepectrometry to detect, result as shown in Figure 1.In Fig. 1, line a shows the walnut nuclear activity charcoal after oxidation, and line b shows the active carbon after silanization, and line c shows the active carbon containing benzyl malononitrile group part.As seen from Figure 1, compare with line a, line b is at 1400cm
-1phenolic hydroxyl group peak obviously weakens, at 727cm
-1there is Ar-O-Si out-of-plane bending vibration peak in place, simultaneously at 773cm
-1there is C-Cl stretching vibration peak in place, in addition, at 1591cm
-1there is the characteristic peak of phenyl ring, show that the success of 4-chloromethyl phenyl trichlorosilane is immobilized on active carbon.Comparing with line b, not only there is the essential characteristic peak of the active carbon after 4-chloromethyl phenyl trichlorosilane in line c, and at 2248cm
-1also having there is-CN stretching vibration peak in place, illustrates in the organic chain that-CN group is successfully grafted in silane.
The preparation of embodiment 2 immobilized metal ion organic complex catalyst
At 100 DEG C, boil cocoanut active charcoal 3h with 3%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 30%
3react 5h at 75 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the cocoanut active charcoal after oxidation after testing.
150mLDMSO is as solvent; cocoanut active charcoal after being oxidized by 3g mixes with the 3-r-chloropropyl trimethoxyl silane (silane coupler) of 2mL under nitrogen protection; add the equimolar deionized water with silane coupler again; stirring reaction 20h at 80 DEG C; and then carry out surname extraction 24h with ethanol; removing unreacted silane reagent, obtain the second product, is the active carbon after silanization after testing.
In 200mLDMF, add the active carbon after 2.0g silanization again, under nitrogen protection, add 0.1gNaCH (CN)
2and 0.05gNaI, heat stirring and refluxing 48h at 90 DEG C, suction filtration, solid matter is with absolute ethyl alcohol surname extraction 24h, and 70 DEG C of vacuum drying, obtain third product, is the active carbon containing propyl group malononitrile group part after testing.
Active carbon 1.5g being contained propyl group malononitrile group part adds 50mL containing 0.3gCuCl
2carrene in, 30 DEG C of stirring reaction 40h, suction filtration, solid matter with carrene surname extraction 48h, 60 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
Get above-mentioned the first obtained product, the second product, third product utilize infra-red sepectrometry to detect, result as shown in Figure 2.In Fig. 2, line a shows the cocoanut active charcoal after oxidation, and line b shows the active carbon after silanization, and line c shows the active carbon containing propyl group malononitrile group part.As seen from Figure 2, compare with line a, line b is at 1400cm
-1phenolic hydroxyl group peak obviously weakens, at 727cm
-1there is Ar-O-Si out-of-plane bending vibration peak in place, simultaneously at 786cm
-1there is C-Cl stretching vibration peak in place, shows that the success of 3-r-chloropropyl trimethoxyl silane is immobilized on active carbon.Comparing with line b, not only there is the essential characteristic peak of active carbon after silanization in line c, and at 2248cm
-1also having there is-CN stretching vibration peak in place, illustrates in the organic chain that-CN group is successfully grafted in silane.
The preparation of embodiment 3 immobilized metal ion organic complex catalyst
At 100 DEG C, boil cocoanut active charcoal 2h with 5%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 20%
3react 4h at 85 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the cocoanut active charcoal after oxidation after testing.
150mL toluene is as solvent; cocoanut active charcoal after being oxidized by 3.0g mixes with the 3-aminopropyl trimethoxysilane (silane coupler) of 1.5mL under nitrogen protection; add a small amount of deionized water (mol ratio of deionized water and silane coupler is 1:1) again; stirring reaction 24h at 110 DEG C; and then carry out surname extraction 24h with ethanol; removing unreacted silane reagent, obtain the second product, is the active carbon after silanization after testing.
The active carbon after 2.0g silanization is added again in 200mL carrene; under nitrogen protection; 3h is stirred in 0 DEG C; then the ethylating N-(Propylamino of 5mL is added) dichloromethane solution of tropone, at 20 DEG C of stirring reaction 16h under nitrogen protection, suction filtration; solid matter is with absolute ethyl alcohol surname extraction 24h; 70 DEG C of vacuum drying, obtain third product, are the active carbon containing ring heptamethylene diamine part after testing.
Active carbon 1.5g being contained ring heptamethylene diamine part adds 50mL containing 0.4gPd (PhCN)
2cl
2carrene in, 20 DEG C of stirring reaction 48h, suction filtration, solid matter with carrene surname extraction 24h, 70 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
The preparation of embodiment 4 immobilized metal ion organic complex catalyst
At 100 DEG C, boil coal mass active carbon 1h with 4%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 35%
3react 4h at 85 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the coal mass active carbon after oxidation after testing.
With 150mL chloroform as solvent; coal mass active carbon after being oxidized by 3g mixes with 2mLN-[3-(trimethoxy is silica-based)-propyl group] ethylethylenediamine (silane coupler) under nitrogen protection; add a small amount of deionized water (mol ratio of water and silane coupler is 1:2) again; at 63 DEG C of reaction 24h; obtaining the second product, is the active carbon containing ethylenediamine ylidene ligands after testing.
Active carbon 1.5g being contained ethylenediamine ylidene ligands adds 50mL containing 0.3gFeCl
2carrene in, 20 DEG C of stirring reaction 24h, suction filtration, solid matter with carrene surname extraction 24h, 60 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
The preparation of embodiment 5 immobilized metal ion organic complex catalyst
At 100 DEG C, boil almond active carbon 1h with 5%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 20%
3react 4h at 85 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the almond active carbon after oxidation after testing.
With the mixed solution of 150mL ethanol and ammoniacal liquor as solvent; by 3g be oxidized after almond active carbon under nitrogen protection with 2mLN; N '-two [(trimethoxy silicon) propyl group]-1; 2-cyclohexanediamine (silane coupler) mixes; add a small amount of deionized water (mol ratio of deionized water and silane coupler is 1:1) again; at 20 DEG C of reaction 48h, obtaining the second product, is the active carbon containing cyclohexanediamine ylidene ligands after testing.
Active carbon 1.5g being contained cyclohexanediamine ylidene ligands adds 50mL containing 0.3gMnCl
2carrene in, 35 DEG C of stirring reaction 24h, suction filtration, solid matter with carrene surname extraction 24h, 80 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
The preparation of embodiment 6 immobilized metal ion organic complex catalyst
At 100 DEG C, boil peach-pit active carbon 3h with 4%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 35%
3react 6h at 75 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the peach-pit active carbon after oxidation after testing.
With 150mL ethyl acetate as solvent; peach-pit active carbon after being oxidized by 3g mixes with the 3-chloropropyl triethoxysilane (silane coupler) of 2mL under nitrogen protection; add a small amount of deionized water (mol ratio of deionized water and silane coupler is 1:3) again; stirring reaction 12h at 80 DEG C; and then carry out surname extraction 24h with carrene; removing unreacted silane reagent, obtain the second product, is the active carbon after silanization after testing.
In 200mL carrene, add the active carbon after 2.0g silanization again, under nitrogen protection, add 0.1gNaCH (CN)
2and 0.05gNaI, heat stirring and refluxing 48h at 90 DEG C, suction filtration, solid matter is with absolute ethyl alcohol surname extraction 24h, and 80 DEG C of vacuum drying, obtain third product, is the active carbon containing propyl group malononitrile group part after testing.
Active carbon 1.5g being contained propyl group malononitrile group part adds 50mL containing 0.4gPd (PhCN)
2cl
2carrene in, 20 DEG C of stirring reaction 48h, suction filtration, solid matter with carrene surname extraction 24h, 60 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.The preparation of embodiment 7 immobilized metal ion organic complex catalyst
At 100 DEG C, boil walnut nuclear activity charcoal 2h with 3%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 40%
3react 5h at 80 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the walnut nuclear activity charcoal after oxidation after testing.
With 150mL acetone as solvent; walnut nuclear activity charcoal after being oxidized by 3g mixes with the 2-aminoethyl trimethoxy silane (silane coupler) of 2mL under nitrogen protection; add the equimolar deionized water with silane reagent again; stirring reaction 24h at 60 DEG C; and then carry out surname extraction 24h with ethanol; removing unreacted silane reagent, obtain the second product, is the active carbon after silanization after testing.
The active carbon after 2.0g silanization is added again in 200mL carrene; under nitrogen protection; 3h is stirred in 0 DEG C; then the ethylating N-(Propylamino of 5mL is added) dichloromethane solution of tropone, at 20 DEG C of stirring reaction 24h under nitrogen protection, suction filtration; solid matter is with absolute ethyl alcohol surname extraction 24h; 60 DEG C of vacuum drying, obtain third product, are the active carbon containing ring heptamethylene diamine part after testing.
Active carbon 1.5g being contained ring heptamethylene diamine part adds 50mL containing 0.3gCuCl
2carrene in, 20 DEG C of stirring reaction 24h, suction filtration, solid matter with carrene surname extraction 24h, 70 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
The preparation of embodiment 8 immobilized metal ion organic complex catalyst
At 100 DEG C, boil cocoanut active charcoal 2h with 4%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 25%
3react 3h at 100 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the cocoanut active charcoal after oxidation after testing.
With 150mLDMF as solvent; cocoanut active charcoal after being oxidized by 3g and 0.1mL ethanol mix with 2mL4-chloromethyl phenyl trichlorosilane (silane coupler) under nitrogen protection; add deionized water (mol ratio of deionized water and silane coupler is 1:1.5) again; at 80 DEG C of reaction 24h; obtaining the second product, is the active carbon after silanization after testing.
In 200mLDMF, add the active carbon after 2.0g silanization again, under nitrogen protection, add 0.1gNaCH (CN)
2and 0.05gNaI, heat stirring and refluxing 48h at 90 DEG C, suction filtration, solid matter is with carrene surname extraction 24h, and 80 DEG C of vacuum drying, obtain third product, is the active carbon containing benzyl malononitrile group part after testing.
Active carbon 1.5g being contained benzyl malononitrile group part adds 50mL containing 0.3gZnCl
2carrene in, 20 DEG C of stirring reaction 48h, suction filtration, solid matter with carrene surname extraction 24h, 70 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
The preparation of embodiment 9 immobilized metal ion organic complex catalyst
At 100 DEG C, boil coal mass active carbon 3h with 5%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 55%
3react 4h at 75 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the coal mass active carbon after oxidation after testing.
With 150mL chloroform as solvent; coal mass active carbon after being oxidized by 3g mixes with 2mLN-[3-(trimethoxy is silica-based)-propyl group] ethylethylenediamine (silane coupler) under nitrogen protection; add deionized water (mol ratio of deionized water and silane coupler is 1:2.5) again; at 63 DEG C of reaction 24h; obtaining the second product, is the active carbon containing ethylenediamine ylidene ligands after testing.
Active carbon 1.5g being contained ethylenediamine ylidene ligands adds 50mL containing 0.20gPd (PhCN)
2cl
2and 0.150gCuCl
2carrene in, 30 DEG C of stirring reaction 24h, suction filtration, solid matter with carrene surname extraction 24h, 60 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
The preparation of embodiment 10 immobilized metal ion organic complex catalyst
At 100 DEG C, boil almond active carbon 5h with 4%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 35%
3react 4h at 90 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the almond active carbon after oxidation after testing.
With the mixed solution of 150mL ethanol and ammoniacal liquor as solvent; by 3g be oxidized after almond active carbon under nitrogen protection with 2mLN; N '-two [(trimethoxy silicon) propyl group]-1; 2-cyclohexanediamine (silane coupler) mixes; add deionized water (deionized water and silane reagent mol ratio are 1:1.2) again; at 20 DEG C of reaction 48h, obtaining the second product, is the active carbon containing cyclohexanediamine ylidene ligands after testing.
Active carbon 1.5g being contained cyclohexanediamine ylidene ligands adds 50mL containing 0.20gCoCl
2and 0.20gZnCl
2carrene in, 30 DEG C of stirring reaction 24h, suction filtration, solid matter with carrene surname extraction 24h, 70 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
The preparation of embodiment 11 immobilized metal ion organic complex catalyst
At 100 DEG C, boil peach-pit active carbon 5h with 3%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 35%
3react 5h at 90 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the peach-pit active carbon after oxidation after testing.
With 150mL toluene as solvent; peach-pit active carbon after being oxidized by 3g mixes with the 3-r-chloropropyl trimethoxyl silane (silane coupler) of 2mL under nitrogen protection; add deionized water (mol ratio of deionized water and silane coupler is 1:1.5) again; stirring reaction 24h at 100 DEG C; and then carry out surname extraction 24h with carrene; removing unreacted silane reagent, obtain the second product, is the active carbon after silanization after testing.
In 200mL carrene, add the active carbon after 2.0g silanization again, under nitrogen protection, add 0.1gNaCH (CN)
2and 0.05gNaI, heat stirring and refluxing 48h at 90 DEG C, suction filtration, solid matter is with absolute ethyl alcohol surname extraction 24h, and 80 DEG C of vacuum drying, obtain third product, is the active carbon containing propyl group malononitrile group part after testing.
Active carbon 1.5g being contained propyl group malononitrile group part adds 50mL containing 0.20gFeCl
2and 0.20gMnCl
2carrene in, 20 DEG C of stirring reaction 48h, suction filtration, solid matter with carrene surname extraction 24h, 60 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
The preparation of embodiment 12 immobilized metal ion organic complex catalyst
At 100 DEG C, boil walnut nuclear activity charcoal 5h with 4%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 45%
3react 4h at 85 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the walnut nuclear activity charcoal after oxidation after testing.
With 150mL chloroform as solvent; walnut nuclear activity charcoal after being oxidized by 3g mixes with 2mLN-[3-(trimethoxy is silica-based)-propyl group] ethylethylenediamine (silane coupler) under nitrogen protection; add deionized water (deionized water and silane reagent mol ratio are 1:1.2) again; at 63 DEG C of reaction 24h; obtaining the second product, is the active carbon containing ethylenediamine ylidene ligands after testing.
Active carbon 1.5g being contained ethylenediamine ylidene ligands adds 50mL containing 0.20gPd (PhCN)
2cl
2and 0.150gCoCl
2carrene in, 30 DEG C of stirring reaction 24h, suction filtration, solid matter with carrene surname extraction 24h, 60 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
The detection of embodiment 13 metal ion supported quantity
The immobilized metal ion organic complex catalyst that Example 1 to 12 is obtained, carries out the detection of supported quantity.The detection of supported quantity adopts ICP-AES (ICP-AES) to detect.Testing result is as shown in table 1.
The supported quantity of table 1 various absorbent charcoal carrier chemistry supported metal ion
From data in table 1, in embodiment 1 to 8, the supported quantity of palladium ion is between (1.4 ± 0.15) % ~ (1.7 ± 0.20) %, the supported quantity of copper ion is 0.7 ± 0.10%, the supported quantity of ferrous ion is 0.8 ± 0.20%, the supported quantity of manganese ion is 0.6 ± 0.15%, and the supported quantity of zinc ion is 1.5 ± 0.10%.In embodiment 9, the supported quantity of palladium ion and copper ion is respectively 0.7 ± 0.10%, 0.4 ± 0.10%; In embodiment 10, the supported quantity of cobalt ions and zinc ion is respectively 0.4 ± 0.20%, 0.3 ± 0.15%; In embodiment 11, the supported quantity of ferrous ion and manganese ion is respectively 0.9 ± 0.10%, 0.7 ± 0.10%; In embodiment 12, the supported quantity of palladium ion and cobalt ions is respectively 1.1 ± 0.15%, 0.8 ± 0.10%.
The preparation of comparative example 1 immobilized metal ion organic complex catalyst
At 100 DEG C, boil cocoanut active charcoal 2h with 4%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 25%
33h is reacted at 100 DEG C, suction filtration in solution, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings.
With 150mLDMF as solvent; cocoanut active charcoal after being oxidized by 3g and 0.1mL ethanol mix with 2mL4-chloromethyl phenyl trichlorosilane (silane coupler) under nitrogen protection, do not add water, at 80 DEG C of reaction 24h; obtaining the second product, is the active carbon after silanization after testing.
In 200mLDMF, add the active carbon after 2.0g silanization again, under nitrogen protection, add 0.1gNaCH (CN)
2and 0.05gNaI, heat stirring and refluxing 48h at 90 DEG C, suction filtration, solid matter is with carrene surname extraction 24h, and 80 DEG C of vacuum drying, obtain third product, is the active carbon containing benzyl malononitrile group part after testing.
Active carbon 1.5g being contained benzyl malononitrile group part adds 50mL containing 0.3gZnCl
2carrene in, 20 DEG C of stirring reaction 48h, suction filtration, solid matter with carrene surname extraction 24h, 70 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
The preparation of comparative example 2 immobilized metal ion organic complex catalyst
At 100 DEG C, boil cocoanut active charcoal 2h with 4%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 25%
33h is reacted at 100 DEG C, suction filtration in solution, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings.
With 150mLDMF as solvent; cocoanut active charcoal after being oxidized by 3g and 0.1mL ethanol mix with 2mL3-aminopropyl trimethoxysilane (silane coupler) under nitrogen protection; add deionized water (water and silane reagent mol ratio are 1:1.5) again; at 80 DEG C of reaction 24h; suction filtration, solid matter with carrene surname extraction 24h, 80 DEG C of vacuum drying; obtaining the second product, is the active carbon containing 3-aminopropyl part after testing.
Active carbon 1.5g being contained 3-aminopropyl part adds 50mL containing 0.3gZnCl
2carrene in, 20 DEG C of stirring reaction 48h, suction filtration, solid matter with carrene surname extraction 24h, 70 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
The detection of comparative example 3 metal ion supported quantity
According to the detection method of metal ion supported quantity in embodiment 13, detect the metal supported quantity of the immobilized metal ion organic complex catalyst that comparative example 1,2 provides.Result is as shown in table 2.
The supported quantity of table 2 various absorbent charcoal carrier chemistry supported metal ion
In the preparation method of comparative example 1, in the process of Silanization reaction, do not add water; In the preparation method of embodiment 8, in the process of Silanization reaction, add a small amount of water; In addition other is consistent.From data in table 2, in comparative example 1, the supported quantity of zinc ion is 0.8 ± 0.10%, and the supported quantity of zinc ion is 1.5 ± 0.10% in embodiment 8, supported quantity has significant difference (P < 0.05), result shows in Silanization reaction, add a small amount of water, can significantly improve metal ion supported quantity.
In the preparation method of comparative example 2, the silane coupler of employing is 3-aminopropyl trimethoxysilane, does not have the nitrogenous bidentate ligand of grafting again, has synthesized the active carbon (monodentate ligand active carbon) of 3-aminopropyl part; In the preparation method of embodiment 8, the silane coupler of employing is 4-chloromethyl phenyl trichlorosilane, again further with NaCH (CN)
2there is substitution reaction with NaI, generate the active carbon containing benzyl malononitrile group part, be nitrogenous bidentate ligand active carbon.In addition other is consistent.From data in table 2, in comparative example 2, the supported quantity of zinc ion is 0.5 ± 0.10%, and the supported quantity of zinc ion is 1.5 ± 0.10% in embodiment 8, supported quantity has significant difference (P < 0.05), result shows to use active carbon (the nitrogenous bidentate ligand active carbon) complexation of metal ions containing benzyl malononitrile group part, can significantly improve metal ion supported quantity.
As can be seen here, in Silanization reaction, add a small amount of water, and use nitrogenous bidentate ligand active carbon complexation of metal ions, metal ion supported quantity can be significantly improved.
The preparation of comparative example 4 immobilized metal ion organic complex catalyst
At 100 DEG C, boil cocoanut active charcoal 3h with 3%HCl, suction filtration, then remove solvable ash content in active carbon duct 4 times by the washed with de-ionized water of boiling.Then by the active carbon after 5.0g cleaning-drying in 200mL mass concentration be the HNO of 30%
3react 5h at 75 DEG C in solution, suction filtration, with cleaning in the deionized water of boiling 4 times, 105 DEG C of dryings, obtain the first product, are the cocoanut active charcoal after oxidation after testing.
150mLDMSO is as solvent; cocoanut active charcoal after being oxidized by 3g mixes with the 3-r-chloropropyl trimethoxyl silane (silane coupler) of 2mL under nitrogen protection; stirring reaction 20h at 80 DEG C; and then carry out surname extraction 24h with ethanol; remove unreacted silane reagent; obtaining the second product, is the active carbon after silanization after testing.
In 200mLDMF, add the active carbon after 2.0g silanization again, under nitrogen protection, add 0.1gNaCH (CN)
2and 0.05gNaI, heat stirring and refluxing 48h at 90 DEG C, suction filtration, solid matter is with absolute ethyl alcohol surname extraction 24h, and 70 DEG C of vacuum drying, obtain third product, is the active carbon containing propyl group malononitrile group part after testing.
Active carbon 1.5g being contained propyl group malononitrile group part adds 50mL containing 0.3gCuCl
2carrene in, 30 DEG C of stirring reaction 40h, suction filtration, solid matter with carrene surname extraction 48h, 60 DEG C of vacuum drying, obtain end-product, be immobilized metal ion organic complex catalyst after testing.
The supported quantity of table 3 absorbent charcoal carrier chemistry supported metal ion
Do not add water in the step that active carbon in the preparation method that comparative example 4 provides after oxidation and silane coupler react, and in example 2, add a small amount of water, in addition other are consistent.From table 3 data, the copper ion supported quantity of comparative example 4 is 0.5 ± 0.15%, and in embodiment 2, the supported quantity of copper ion is 0.7 ± 0.10%, and difference has conspicuousness (P < 0.05).Result shows in Silanization reaction, add a small amount of water, can significantly improve the supported quantity of metal ion.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. a preparation method for immobilized metal ion organic complex catalyst, is characterized in that, comprise the steps:
Obtain the active carbon after oxidation;
In the presence of a solvent, active carbon after described oxidation and silane coupler generation Silanization reaction, obtain nitrogenous bidentate ligand active carbon, described solvent is made up of organic solvent and water, described silane coupler is selected from N-[3-(trimethoxy is silica-based)-propyl group] ethylethylenediamine or N, N '-two [(trimethoxy silicon) propyl group]-1,2-cyclohexanediamine;
Get described nitrogenous bidentate ligand active carbon and complexing of metal ion, to obtain final product;
The mol ratio of described water and described silane coupler is 1:(1 ~ 3).
2. preparation method according to claim 1, is characterized in that, described Silanization reaction is silanization 12 ~ 48h under 20 ~ 110 DEG C of conditions.
3. a preparation method for immobilized metal ion organic complex catalyst, is characterized in that, comprise the steps:
Obtain the active carbon after oxidation;
In the presence of a solvent, active carbon after described oxidation and silane coupler generation Silanization reaction, again with nitrogenous bidentate ligand donor generation substitution reaction, obtain nitrogenous bidentate ligand active carbon, described solvent is made up of organic solvent and water, described nitrogenous bidentate ligand donor is the nitrogenous bidentate ligand donor of ring heptamethylene diamine type or the nitrogenous bidentate ligand donor of malononitrile group type, described silane coupler is selected from 3-aminopropyl trimethoxysilane, 3-r-chloropropyl trimethoxyl silane, trichloromethyl silane, 3-chloropropyl triethoxysilane, 2-aminoethyl trimethoxy silane or 4-chloromethyl phenyl trichlorosilane,
Get described nitrogenous bidentate ligand active carbon and complexing of metal ion, to obtain final product;
In g/mL, the active carbon after described oxidation and the mass volume ratio of silane coupler are 1:(0.1 ~ 1);
The mol ratio of described water and described silane coupler is 1:(1 ~ 3).
4. preparation method according to claim 3, is characterized in that, the nitrogenous bidentate ligand donor of described ring heptamethylene diamine type is ethylating N-(Propylamino) tropone.
5. preparation method according to claim 3, is characterized in that, the nitrogenous bidentate ligand donor of described malononitrile group type is NaCH (CN)
2.
6. preparation method according to claim 3, is characterized in that, described substitution reaction is specially and replaces 16 ~ 48h under 20 or 90 DEG C of conditions.
7. preparation method according to claim 3, is characterized in that, described Silanization reaction is silanization 12 ~ 48h under 20 ~ 110 DEG C of conditions.
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