CN103586074A - Preparation method of fiber loaded metallic nickel/palladium catalyst - Google Patents
Preparation method of fiber loaded metallic nickel/palladium catalyst Download PDFInfo
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- CN103586074A CN103586074A CN201310467358.0A CN201310467358A CN103586074A CN 103586074 A CN103586074 A CN 103586074A CN 201310467358 A CN201310467358 A CN 201310467358A CN 103586074 A CN103586074 A CN 103586074A
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Abstract
The invention relates to a preparation method of a fiber loaded metallic nickel/palladium catalyst. The amino-functionalized polyacrylonitrile fibre is adopted as a carrier, the amino group on the surface of the carrier and metal ions carry out a complexing reaction, so that the metal ions are immobilized on the surface of the fibre carrier, a reducing agent is used for reducing the metal ions, and thus the fiber loading metallic nickel/palladium catalyst is prepared. Due to the coordination action of the amino group on the surface of the fibre carrier, the metal and the carrier can firmly combined together, meanwhile, the electronic combining property of the metal is reduced by means of an electron donating effect of the amino group, and the catalytic activity of the metal is further improved. The method provides a new way for preparing a hybrid metal catalyst, the use ratio of a noble metal is increased, the production process is simple, and the cost is low; the obtained loaded catalyst has good stability and high catalytic activity, can be reused for many times and has relatively high economic benefits and wide application prospects.
Description
Technical field
The present invention relates to a kind of preparation method of novel load mixed metal catalyst.
Background technology
Suzuki coupling reaction is a kind of method of important synthetic biphenyl compound.Suzuki reaction has higher reactivity and selective, good functional group tolerance, the low toxicity of organoboron reagent, and post processing is relatively simple, reaction can be reacted under comparatively gentle condition, the aqueous phase solvent that simultaneous reactions is used is relative environmental protection also, and above advantage makes Suzuki coupling reaction be widely used in the study on the synthesis that dyestuff, medicine intermediate, natural products, agricultural chemicals etc. contain biphenyl group compound.
Suzuki coupling reaction need to add transition metal as catalyst conventionally, and applying maximum transition metal is palladium and nickel.Early stage coupling reaction catalyst is mainly homogeneous palladium catalysts, the reactivity of catalyst is high, but easy poisoning and deactivation, often need in actual use to add hypertoxic organophosphorus ligand to improve the stability of catalyst, and can not reuse, the utilization rate of catalyst is low, lacks economic benefit.Nickel and palladium are the transition metals of same main group, but relatively cheap many of price, metallic nickel can significantly be reduced to the cost of reaction for catalysis Suzuki coupling reaction, but the reactivity of metallic nickel are relatively low, often need complicated part, reaction condition is also relatively harsh.In order to solve above variety of problems, improve the economy of reaction, loaded catalyst arises at the historic moment, and working load type catalyst can significantly improve the utilization rate of noble metal.CN101875011A has announced a kind of TiO
2carrier-supported precious metal palladium and its production and use, the method is used P25 type TiO
2for carrier is prepared a kind of TiO
2loaded palladium catalyst, and the catalyst of system is used for to catalytic Heck coupling reaction, having obtained good reaction effect, the stability of catalyst is also fine.CN1105289A has announced a kind of preparation method of nm-particle Ni-Pd alloy catalyst, and the method, under argon shield, is used electric arc heated nickel, palladium electrode, produces nickel, palladium atom, and atom collides with each other, and generates particle Ni-Pd alloy catalyst.
In order to overcome the shortcoming of Metal Palladium costliness and metallic nickel poor activity, the present invention use simple and reliable method by these two kinds of Metal Supporteds to the polyacrylonitrile fibre of functional amido, obtain that a kind of activity is high, good stability, fiber-loaded metallic nickel/palladium catalyst that reusability is good.
Summary of the invention
The object of the invention is to: adopt simple and reliable method, prepare a kind of good stability, fiber-loaded metallic nickel/palladium catalyst that catalytic activity is high, and catalyst is applied to Suzuki coupling reaction.
Technical scheme of the present invention: adopting the polyacrylonitrile fibre of functional amido is carrier, utilize complexation reaction between the surperficial amido of carrier and metal ion, two metal ion species are loaded on to fiber carrier surface simultaneously, coordination combines metal and carrier securely, the effect of amido supplied for electronic reduces the electron binding energy of metal, further improve its catalytic activity, use reducing agent metal ion to be reduced to little, the highly active metal simple-substance of size, prepare a kind of good stability, the high fiber-loaded metallic nickel/palladium catalyst of catalytic activity.
Concrete steps are as follows:
(1) preparation of fibre metal ion complex, the Ni of compound concentration 0.02mol/L
2+with 0.001mol/L Pd
2+solution, is acid by the pH value of nitric acid, sulfuric acid or hydrochloric acid conditioning solution, gets after 2～30mL, two metal ion species solution mixing, obtains hybrid metal solion; The polyacrylonitrile fibre that takes 0.1 functional amido, is placed in hybrid metal solion, carries out complexation reaction, and the reaction time is 0.5～4 h, and temperature is 25 ℃～55 ℃, and metal ion is fixed on carrier, obtains fibre metal ion complex.
(2) preparation of fiber-loaded metallic nickel/palladium catalyst, distilled water is cleaned the fibre metal ion complex obtaining, be placed in the inferior sodium phosphate of 0.01～1mol/L or 1%～10% hydrazine hydrate reduction solution, recovery time is 0.5～3h, temperature is 45 ℃～75 ℃, and after reduction, distilled water obtains fiber-loaded metallic nickel/palladium catalyst after cleaning.
Fiber-loaded metallic nickel/palladium catalyst prepared by the present invention, belongs to a kind of heterogeneous catalysis, is mainly used in Suzuki coupling reaction, mainly comprises reaction, separation, purification unit process.It is characterized in that reacting in the mixed solvent of second alcohol and water, the volume ratio of second alcohol and water is 1:3～3:1, add a certain proportion of carbonate or phosphate as base reagent, the mol ratio of base reagent and raw material is 1:4～4:1, halogeno-benzene and phenyl boric acid be back flow reaction 1～5 h in 60 ℃～90 ℃ air, and the consumption of catalyst is 0.01～0.1mol%.After reaction finishes, filter to isolate metallic nickel/palladium catalyst after being cooled to room temperature, revolve and steam remaining reactant liquor, use acetic acid ethyl dissolution residue, filter out inorganic salts, revolve after steaming ethyl acetate and obtain the thick product of Suzuki coupling reaction, obtain Suzuki coupling reaction product after using column chromatography purification.The yield of product is: 98%.So the carbonate of above-mentioned reaction or phosphate are sylvite and sodium salt, preferred sylvite.
Fiber-loaded metallic nickel/palladium catalyst prepared by the present invention, active high, good stability, can be repeatedly used.Experiment showed, that catalyst reuses after 6 times, actively obviously do not decline.
Accompanying drawing explanation
The stereoscan photograph of the fiber-loaded metallic nickel/palladium catalyst of Fig. 1;
The energy spectrogram of the fiber-loaded metallic nickel/palladium catalyst of Fig. 2.
The specific embodiment
1. the preparation of fiber-loaded metallic nickel/palladium catalyst, adds the Ni of 20mL 0.02mol/L to 100mL beaker
2+with 2mL 0.002 mol/L Pd
2+solution, salt acid for adjusting pH value is 2, adds the polyacrylonitrile fibre of the functional amido of 0.5g, in the water-bath of 40 ℃, is incubated 1h, needs continuous stirring in insulating process, insulation finishes rear use distilled water to be cleaned, and obtains fibre metal ion complex; Fibre metal ion complex is placed in to the inferior sodium phosphate of 0.02mol/L or 1% hydrazine hydrate solution, at 50 ℃, reduces 1h, stand-by after clean dry.
2. the Suzuki coupling reaction of catalysis halobenzene and phenyl boric acid, in 100mL single port flask, add 11mmol phenyl boric acid, 10mmol halobenzene (iodobenzene or bromobenzene), potash 20mmol, etoh solvent and water 30mL(volume ratio are 2:1), add 0.2g catalyst, be placed in 85 ℃ of oil bath return stirring reaction 2h, be cooled to room temperature, filter to isolate catalyst, revolve and steam the filtrate obtaining, with 80mL acetic acid ethyl dissolution residue, filter out inorganic salts, after revolving steaming ethyl acetate, obtain the thick product of Suzuki coupling reaction, use column chromatography (eluant, eluent is benzinum) purifying to obtain Suzuki coupling reaction product biphenyl, product yield: iodobenzene 99%, bromobenzene 98%.Product is white solid, fusing point 70-71 ℃,
1h NMR (300 MHz, CDCl
3): δ 7.32 (t, J=7.5 Hz, 2H), 7.42 (t, J=7.5 Hz, 4H), 7.58 (d, J=6.9 Hz, 4H).
Claims (6)
1. the preparation method of a fiber-loaded metallic nickel/palladium catalyst, it is characterized in that: adopting the polyacrylonitrile fibre of functional amido is carrier, utilize complexation reaction between the surperficial amido of carrier and metal ion, two metal ion species are loaded on to fiber carrier surface simultaneously, coordination combines metal and carrier securely, the effect of amido supplied for electronic reduces the electron binding energy of metal, further improve its catalytic activity, use reducing agent metal ion to be reduced to little, the highly active metal simple-substance of size, prepare fiber-loaded metallic nickel/palladium catalyst.
2. preparation method according to claim 1, is characterized in that: concrete steps are as follows:
Step 1: the preparation of fibre metal ion complex, the Ni of compound concentration 0.02mol/L
2+with 0.001mol/L Pd
2+solution, is acid by the pH value of nitric acid, sulfuric acid or hydrochloric acid conditioning solution, gets after two metal ion species solution mixing, obtains hybrid metal solion; The polyacrylonitrile fibre of the functional amido taking, is placed in hybrid metal solion, carries out complexation reaction, and metal ion is fixed on carrier, obtains fibre metal ion complex;
Step 2: the preparation of fiber-loaded metallic nickel/palladium catalyst, distilled water is cleaned the fibre metal ion complex obtaining, be placed in inferior sodium phosphate or hydrazine hydrate reduction solution, reduction reaction finishes rear distilled water to be cleaned, and obtains good stability, the high fiber-loaded metallic nickel/palladium catalyst of catalytic activity.
3. according to the preparation method described in claim 1 or 2 any one, it is characterized in that: between carrier fibre and metallic nickel/palladium, be that form with coordinate bond combines, amido supplied for electronic effect simultaneously reduces the electron binding energy of metal, further improves its catalytic activity.
4. according to the preparation method described in claim 1 or 2 any one, it is characterized in that: fiber-loaded metallic nickel/palladium catalyst particle diameter is 60nm.
5. according to the preparation method described in claim 1 or 2 any one, it is characterized in that: fiber-loaded metallic nickel/palladium catalyst catalyst is a kind of hybrid metal heterogeneous catalysis.
6. according to the preparation method described in claim 1 or 2 any one, it is characterized in that: fiber-loaded metallic nickel/palladium catalyst is mainly used in catalysis Suzuki coupling reaction, prepares biphenyl compound.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105618000A (en) * | 2016-01-15 | 2016-06-01 | 辽宁石油化工大学 | Modified cotton fiber adsorbent as well as preparation method and application thereof |
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| US20080087574A1 (en) * | 2006-10-17 | 2008-04-17 | Gaffney Anne M | Bimetallic alkylation catalysts |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20080087574A1 (en) * | 2006-10-17 | 2008-04-17 | Gaffney Anne M | Bimetallic alkylation catalysts |
| CN101081366A (en) * | 2007-02-02 | 2007-12-05 | 中国石油天然气股份有限公司长庆石化分公司 | Pd radicel duplex metal selective hydrogenation catalyzer and method for preparing the same and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105618000A (en) * | 2016-01-15 | 2016-06-01 | 辽宁石油化工大学 | Modified cotton fiber adsorbent as well as preparation method and application thereof |
| CN105618000B (en) * | 2016-01-15 | 2018-02-02 | 辽宁石油化工大学 | A kind of modified cotton fiber adsorbent and its preparation method and application |
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Application publication date: 20140219 |