CN102179248A - Double-layer hollow amorphous alloy nanometer ball as well as preparation method and application thereof - Google Patents
Double-layer hollow amorphous alloy nanometer ball as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a double-layer hollow amorphous alloy nanometer ball which is characterized in that the activity ratio surface area is 20-40 square meters per gram; the diameter of an inner cavity is 240-260 nanometers; the distance between two layers is 40-60 nanometers; the thickness of a ball shell is 10-20 nanometers; the ball shell of the double-layer hollow nanometer ball is made from M-B amorphous alloy nanometer particles with the particle size of 4-6 nanometers; M is a metallic element; and the active specific surface area of the ball is 2-3 times of the active specific surface area of a solid amorphous alloy catalyst. The double-layer hollow amorphous alloy nanometer ball has long catalysis life, can be repeatedly used, has the almost constant catalysis efficiency, can be used as hydrogenation catalyst for the compounds containing unsaturated functional groups such as olefin, alkyne, phenols, nitryl and carbonyl compounds, and also can be used as the catalyst for coupling reaction, such as C-C, C-S, and the like. The double-layer hollow amorphous alloy nanometer ball is prepared by a hard mould plate reverse copying method in combination with a chemical reduction method. The preparation method is simple, the condition is easily controlled and the cost is low.
Description
Technical field
The present invention relates to a kind of double-deck hollow amorphous alloy nano-sphere, and the preparation method of this nanosphere and application, catalyst technical field belonged to.
Background technology
Amorphous alloy is the unordered and new material of shortrange order of a class long-range, and its particular structure feature is given its highly corrosion resistant, high mechanical tenacity and good magnetic, electricity, catalytic performance, also has eco-friendly characteristics simultaneously.Use as catalyst, require amorphous alloy to have higher specific surface area.Be increasing specific surface area, general at present employing chemical reduction method prepares amorphous alloy catalyst.In Journal of Catalysis 150,434～438,1994, once reported KBH with 2.5M
4The aqueous solution is at 298K, be added drop-wise in the 0.1M nickel acetate ethanolic solution under stirring, use ammoniacal liquor and a large amount of distilled water washing precipitation of 6 milliliters of 8M successively, obtain a kind of Ni-B amorphous alloy Ultra-fine Particle Catalysts, this method has become the conventional method of preparation M-B amorphous alloy catalyst; But this method is because metal ion and KBH
4Reduction reaction rapid, heat release is violent, can cause hot-spot, cause the alloying pellet that generates to be reunited easily, so the greatest drawback of this method is that specific area is still big inadequately.Therefore,, how further to improve the specific area of amorphous alloy catalyst, to improve the catalytic activity or the urgent problem of amorphous alloy catalyst as practical catalyst material.
In recent years, the nanometer materials of specific form are owing to they are widely studied showing special performances aspect optics, electricity, magnetics and the catalytic field.It is big that double-deck hollow material has specific area, and density is little, easily reclaims, cost is low, advantages such as Surface Permeability is good, especially show better catalytic performance than common solid in catalysis: at first, double-deck hollow structure can improve the activity of such catalysts specific area significantly; Secondly, double-deck hollow structure catalyst can be dispersed in the reaction system in catalytic process uniformly, and its unique double-layer cavity can be used as nano-reactor, increases mutual contact area; Once more, the double-deck hollow structure catalyst of hundreds of nanometer recycles and reuses easily.Therefore, it is significant how to prepare the research of double-deck hollow structure amorphous alloy catalyst by simple and practical technology.
Summary of the invention
The objective of the invention is for a kind of double-deck hollow amorphous alloy nano-sphere is provided, for existing amorphous alloy catalyst field increases class new varieties.
Another object of the present invention is for preparation method that above-mentioned this nanosphere nanosphere is provided and application.
Purpose of the present invention can be achieved through the following technical solutions.
A kind of double-deck hollow amorphous alloy nano-sphere, its specific activity surface area is 20～40m
2/ g, the internal layer cavity diameter is 240～260nm, and the distance between two-layer is 40～60nm, and the wall thickness of spherical shell is 10～20nm, and the spherical shell of double-deck hollow nanospheres is that the M-B amorphous alloy nano particle of 4～6nm is formed by particle size, and M wherein is a metallic element.
Described M metallic element is selected from any one in nickel, cobalt, iron, ruthenium, palladium and the platinum.
The preparation method of double-deck hollow amorphous alloy nano-sphere of the present invention comprises the steps:
1) with 0.01g/L, add the 3mL metal salt solution and join in the polystyrene hollow ball (0.5g) of sulfonation, ultrasonic 20～60min stirred 12～24 hours down at 0～30 ℃, and is centrifugal, and freeze drying obtains the polystyrene sphere that slaine wraps up;
2) under 0～30 ℃ the metal hydroboron aqueous solution of 0.1～1.0mol/L dropwise is added drop-wise in the polystyrene sphere of slaine parcel of step 1) preparation, wherein: the mol ratio of metal hydroboron and slaine is 4～6: 1;
3) filtration step 2) the middle black particle that generates, freeze drying with DMF or THF dissolved polystyrene bead, is washed respectively 3～5 times with deionized water and absolute ethyl alcohol again, promptly obtains double-deck hollow amorphous alloy nano-sphere.
Described slaine is the organic salt or the inorganic salts of nickel, cobalt, iron, ruthenium, palladium or platinum.Preferred nickel, cobalt, palladium.
Described metal hydroboron is sodium borohydride, potassium borohydride or its mixture.Preferred potassium borohydride.
The product of the present invention's preparation carries out structural characterization by following means: adopt the XRD spectra that obtains on the Japanese Rigaku D/Max-RB type X-ray diffractometer of science to carry out the structures of samples analysis; The appearance structure of the projection electromicroscopic photograph analytic sample that employing obtains under 200kV at Japanese JEOL JEM2010 type high-resolution-ration transmission electric-lens; Adopt the automatic physical adsorption appearance of QuantaChrome Nova4000e type to measure the specific area of catalyst.
Double-deck hollow amorphous alloy nano-sphere provided by the present invention can be used as the hydrogenation catalyst that alkene, alkynes, phenols, nitro, carbonyls etc. contain the unsaturated functional group compound, also can be used as the catalyst of coupling reactions such as C-C, C-S.Especially Sonogashira reaction and iodobenzene and the reaction of benzenethiol prepared in reaction diphenyl sulfide there is tangible catalytic effect.
Activity of such catalysts specific area of the present invention reaches 20～40m
2/ g is 2～3 times of solid amorphous alloy catalyst specific activity surface area; And its long catalytic life, easy to operate can be reused repeatedly and keeps almost constant catalytic efficiency; Can be used as alkene, alkynes, phenols, nitro, carbonyls etc. and contain the hydrogenation catalyst of unsaturated functional group compound, also can be used as the catalyst of coupling reactions such as C-C, C-S.Catalyst of the present invention is prepared from conjunction with chemical reduction method by the reverse reproduction technology of hard template, and preparation technology is simple, condition is easily controlled, with low cost.
Description of drawings
Fig. 1 is the XRD spectra of the sample of embodiment 4 preparations;
Fig. 2 is the TEM photo of the sample of embodiment 4 preparations.
The specific embodiment
The present invention will be further described by the following examples.Only for illustrating the present invention, the present invention is not limited thereto for embodiment.
Agents useful for same is chemical pure in the embodiment of the invention.
Embodiment 1:
1) with the NiCl of 5ml 0.01g/ml
26H
2O solution joins in the polystyrene hollow ball of 0.3g sulfonation, and ultrasonic 20min stirred 24 hours down at 25 ℃, and centrifugal, freeze drying obtains NiCl
2The polystyrene sphere of parcel;
2) under 20 ℃ with the KBH of 0.1mol/L
4The aqueous solution dropwise is added drop-wise to the NiCl of step 1) preparation
2In the polystyrene sphere of parcel, wherein: KBH
4With NiCl
2Mol ratio be 5: 1;
3) filtration step 2) the middle black particle that generates, freeze drying with DMF or THF dissolved polystyrene bead, is washed respectively 3～5 times with deionized water and absolute ethyl alcohol again, promptly obtains double-deck hollow Ni-B amorphous alloy nano-sphere, represents with the Ni-B-bilayer.
Fig. 1 is the XRD spectra of the prepared sample of present embodiment, can determine that from the disperse peak shape of its about 45 ° of positions the sample that makes is an amorphous structure; Fig. 2 is the TEM photo of the prepared sample of present embodiment, visible gained sample is double-deck hollow structure nanosphere from photo, the internal layer cavity diameter is 250nm, distance between two-layer is 40nm, and the spherical shell of double-deck hollow nanospheres is that the amorphous alloy nano particle of 4～6nm is formed by particle size, and the wall thickness of spherical shell is 20nm.
The specific area of being measured catalyst by the automatic physical adsorption appearance of QuantaChrome Nova 4000e type is 25.6m
2/ g.
Embodiment 2:
1) with the NiCl of 3ml 0.05g/ml
26H
2O solution joins in the polystyrene hollow ball of 0.3g sulfonation, and ultrasonic 40min stirred 24 hours down at 0 ℃, and centrifugal, freeze drying obtains NiCl
2The polystyrene sphere of parcel;
2) under 0 ℃ with the KBH of 1.0mol/L
4The aqueous solution dropwise is added drop-wise to the NiCl of step 1) preparation
2In the polystyrene sphere of parcel, wherein: KBH
4With NiCl
2Mol ratio be 5: 1;
3) filtration step 2) the middle black particle that generates, freeze drying with DMF or THF dissolved polystyrene bead, is washed respectively 3～5 times with deionized water and absolute ethyl alcohol again, promptly obtains object.
Can determine that by the XRD spectra of the prepared sample of present embodiment the sample that makes is the amorphous alloy structure; By visible gained sample in the TEM photo of the prepared sample of present embodiment is double-deck hollow structure nanosphere, the internal layer cavity diameter is 245nm, distance between two-layer is 50nm, and the spherical shell of double-deck hollow nanospheres is that the amorphous alloy nano particle of 4～6nm is formed by particle size, and the wall thickness of spherical shell is 15nm.
The specific area of being measured catalyst by the automatic physical adsorption appearance of QuantaChrome Nova 4000e type is 22.5m
2/ g.
Embodiment 3:
1) with the NiCl of 5ml 0.05g/ml
26H
2O solution joins in the polystyrene hollow ball of 0.5g sulfonation, and ultrasonic 60min stirred 24 hours down at 30 ℃, and centrifugal, freeze drying obtains NiCl
2The polystyrene sphere of parcel;
2) under 30 ℃ with the KBH of 1.0mol/L
4The aqueous solution dropwise is added drop-wise to the NiCl of step 1) preparation
2In the polystyrene sphere of parcel, wherein: KBH
4With NiCl
2Mol ratio be 5: 1;
3) filtration step 2) the middle black particle that generates, freeze drying with DMF or THF dissolved polystyrene bead, is washed respectively 3～5 times with deionized water and absolute ethyl alcohol again, promptly obtains object.
Can determine that by the XRD spectra of the prepared sample of present embodiment the sample that makes is the amorphous alloy structure; By visible gained sample in the TEM photo of the prepared sample of present embodiment is double-deck hollow structure nanosphere, the internal layer cavity diameter is 240nm, distance between two-layer is 60nm, and the spherical shell of double-deck hollow nanospheres is that the amorphous alloy nano particle of 4～6nm is formed by particle size, and the wall thickness of spherical shell is 10nm.
The specific area of being measured catalyst by the automatic physical adsorption appearance of QuantaChrome Nova 4000e type is 20.7m
2/ g.
Embodiment 4:
The difference of present embodiment and embodiment 1 is: described slaine is PdCl
2
All the other contents are all described identical with embodiment 1.
As depicted in figs. 1 and 2, the XRD spectra of the prepared sample of present embodiment can determine that the sample that makes is the amorphous alloy structure; Visible gained sample is double-deck hollow structure nanosphere in the TEM photo of the prepared sample of present embodiment, the internal layer cavity diameter is 220nm, diameter between two-layer is 60nm, and the spherical shell of double-deck hollow nanospheres is that the amorphous alloy nano particle of 4～6nm is formed by particle size, and the wall thickness of spherical shell is 15nm.
The specific area of being measured catalyst by the automatic physical adsorption appearance of QuantaChrome Nova 4000e type is 29.9m
2/ g.
Embodiment 5:
The difference of present embodiment and embodiment 1 is: described slaine is CoCl
26H
2O
All the other contents are all described identical with embodiment 1.
Can determine that by the XRD spectra of the prepared sample of present embodiment the sample that makes is the amorphous alloy structure; By visible gained sample in the TEM photo of the prepared sample of present embodiment is double-deck hollow structure nanosphere, the internal layer cavity diameter is 250nm, distance between two-layer is 40nm, and the spherical shell of double-deck hollow nanospheres is that the amorphous alloy nano particle of 4～6nm is formed by particle size, and the wall thickness of spherical shell is 20nm.
The specific area of being measured catalyst by the automatic physical adsorption appearance of QuantaChrome Nova 4000e type is 26.9m
2/ g.
Embodiment 6:
The difference of present embodiment and embodiment 1 is: described slaine is FeCl
3
All the other contents are all described identical with embodiment 1.
Can determine that by the XRD spectra of the prepared sample of present embodiment the sample that makes is the amorphous alloy structure; By visible gained sample in the TEM photo of the prepared sample of present embodiment is double-deck hollow structure nanosphere, the internal layer cavity diameter is 240nm, diameter between two-layer is 50nm, and the spherical shell of double-deck hollow nanospheres is that the amorphous alloy nano particle of 4～6nm is formed by particle size, and the wall thickness of spherical shell is 18nm.
The specific area of being measured catalyst by the automatic physical adsorption appearance of QuantaChrome Nova 4000e type is 19.6m
2/ g.
Embodiment 7:
The difference of present embodiment and embodiment 1 is: described slaine is RuCl
3
All the other contents are all described identical with embodiment 1.
Can determine that by the XRD spectra of the prepared sample of present embodiment the sample that makes is the amorphous alloy structure; By visible gained sample in the TEM photo of the prepared sample of present embodiment is double-deck hollow structure nanosphere, the internal layer cavity diameter is 240nm, diameter between two-layer is 60nm, and the spherical shell of double-deck hollow nanospheres is that the amorphous alloy nano particle of 4～6nm is formed by particle size, and the wall thickness of spherical shell is 17nm.
The specific area of being measured catalyst by the automatic physical adsorption appearance of QuantaChrome Nova 4000e type is 30.8m
2/ g.
Embodiment 8:
The difference of present embodiment and embodiment 1 is: described slaine is K
2PtCl
6
All the other contents are all described identical with embodiment 1.
Can determine that by the XRD spectra of the prepared sample of present embodiment the sample that makes is the amorphous alloy structure; By visible gained sample in the TEM photo of the prepared sample of present embodiment is double-deck hollow structure nanosphere, the internal layer cavity diameter is 240nm, diameter between two-layer is 60nm, and the spherical shell of double-deck hollow nanospheres is that the amorphous alloy nano particle of 4～6nm is formed by particle size, and the wall thickness of spherical shell is 15nm.
The specific area of being measured catalyst by the automatic physical adsorption appearance of QuantaChrome Nova 4000e type is 28.6m
2/ g.
Embodiment 9:
Embodiment 4 is got the C-C coupling reaction that double-deck hollow Pd-B amorphous alloy nano-sphere is used for the Sonogashira type, that is: in the 10ml round-bottomed flask, add catalyst 0.1mg successively, chlorobenzene 1.2mmol, phenylacetylene 1.0mmol, cuprous iodide 0.03mmol, triphenylphosphine 0.2mmol, potash 1.5mmol, water 3ml, heated constant temperature is in 80 ℃ of needed reaction temperatures, the control mixing speed is 800rpm, the product gas chromatographic detection of being furnished with ATSE-54 chromatographic column and hydrogen flame detector, all activity datas are all through repeated experiments more than three times, error range is in 5%, and catalytic performance is shown in Table 1.
Embodiment 10:
4 layers of hollow Pd-B of embodiment amorphous alloy nano-sphere is used for Sonogashira Type C-C coupling reaction, that is: in the 10ml round-bottomed flask, add catalyst 0.1mg successively, bromobenzene 1.2mmol, phenylacetylene 1.0mmol, cuprous iodide 0.03mmol, triphenylphosphine 0.2mmol, potash 1.5mmol, water 3ml, heated constant temperature is in 80 ℃ of needed reaction temperatures, the control mixing speed is 800rpm, the product gas chromatographic detection of being furnished with ATSE-54 chromatographic column and hydrogen flame detector, all activity datas are all through repeated experiments more than three times, error range is in 5%, and catalytic performance is shown in Table 1.
Embodiment 11:
Embodiment 4 is got double-deck hollow Pd-B amorphous alloy nano-sphere be used for Sonogashira Type C-C coupling reaction, that is: in the 10ml round-bottomed flask, add catalyst 0.1mg successively, iodobenzene 1.2mmol, phenylacetylene 1.0mmol, cuprous iodide 0.03mmol, triphenylphosphine 0.2mmol, potash 1.5mmol, water 3ml, heated constant temperature is in 80 ℃ of needed reaction temperatures, the control mixing speed is 800rpm, the product gas chromatographic detection of being furnished with ATSE-54 chromatographic column and hydrogen flame detector, all activity datas are all through repeated experiments more than three times, error range is in 5%, and catalytic performance is shown in Table 1.
Embodiment 12:
The catalyst of reaction system among the embodiment 11 is carried out centrifugation, in the reaction system that is applied to for the second time after the ethanol washing among the embodiment 11.
Present embodiment has verified that double-deck hollow Pd-B amorphous alloy nano-sphere carries out the catalytic performance that uses for the second time, and concrete catalytic performance data are shown in Table 1.
Embodiment 13:
The catalyst of embodiment 12 reaction systems is carried out centrifugation, in the reaction system that is applied to for the third time after the ethanol washing among the embodiment 11.
Present embodiment has been verified the catalytic performance that double-deck hollow Pd-B amorphous alloy nano-sphere uses for the third time, and concrete catalytic performance data are shown in Table 1.
Embodiment 14:
The catalyst of embodiment 13 reaction systems is carried out centrifugation, in the reaction system that the 4th time is applied among the embodiment 11 after the ethanol washing.
Present embodiment has verified that double-deck hollow Pd-B amorphous alloy nano-sphere carries out the catalytic performance that uses for the 4th time, and concrete catalytic performance data are shown in Table 1.
Embodiment 15:
The catalyst of embodiment 14 reaction systems is carried out centrifugation, in the reaction system that the 5th time is applied among the embodiment 11 after the ethanol washing.
Present embodiment has verified that double-deck hollow Pd-B amorphous alloy nano-sphere carries out the catalytic performance that uses for the 5th time, and concrete catalytic performance data are shown in Table 1.
Embodiment 16:
Embodiment 4 is got double-deck hollow Pd-B amorphous alloy nano-sphere be used for the C-S coupling reaction, that is: in the 10ml round-bottomed flask, add catalyst 0.1mg successively, chlorobenzene 1.2mmol, benzenethiol 1.0mmol, triphenylphosphine 0.2mmol, potassium phosphate 1.5mmol, 1.4-six oxygen, two ring 3ml, heated constant temperature is in 110 ℃ of needed reaction temperatures, be reflected in the nitrogen atmosphere and carry out, the control mixing speed is 800rpm, the product gas chromatographic detection of being furnished with ATSE-54 chromatographic column and hydrogen flame detector, all activity datas are all through repeated experiments more than three times, error range is in 5%, and catalytic performance is shown in Table 1.
Embodiment 17:
Embodiment 4 is got double-deck hollow Pd-B amorphous alloy nano-sphere be used for the C-S coupling reaction, that is: in the 10ml round-bottomed flask, add catalyst 0.1mg successively, bromobenzene 1.2mmol, benzenethiol 1.0mmol, triphenylphosphine 0.2mmol, potassium phosphate 1.5mmol, 1.4-six oxygen, two ring 3ml, heated constant temperature is in 110 ℃ of needed reaction temperatures, be reflected in the nitrogen atmosphere and carry out, the control mixing speed is 800rpm, the product gas chromatographic detection of being furnished with ATSE-54 chromatographic column and hydrogen flame detector, all activity datas are all through repeated experiments more than three times, error range is in 5%, and catalytic performance is shown in Table 1.
Embodiment 18:
Embodiment 4 is got double-deck hollow Pd-B amorphous alloy nano-sphere be used for the C-S coupling reaction, that is: in the 10ml round-bottomed flask, add catalyst 0.1mg successively, iodobenzene 1.2mmol, benzenethiol 1.0mmol, triphenylphosphine 0.2mmol, potassium phosphate 1.5mmol, 1.4-six oxygen, two ring 3ml, heated constant temperature is in 110 ℃ of needed reaction temperatures, be reflected in the nitrogen atmosphere and carry out, the control mixing speed is 800rpm, the product gas chromatographic detection of being furnished with ATSE-54 chromatographic column and hydrogen flame detector, all activity datas are all through repeated experiments more than three times, error range is in 5%, and catalytic performance is shown in Table 1.
Check experiment:
1) with PdCl
2Add in the deionized water of certain volume, make PdCl
2Solution concentration is 0.01g/ml, and ultrasonic 20min stirred 10 minutes down at 25 ℃;
2) under 20 ℃ with the KBH of 0.1mol/L
4The aqueous solution dropwise is added drop-wise to the PdCl of step 1) preparation
2In the solution, wherein: KBH
4With PdCl
2Mol ratio be 5: 1;
3) filtration step 2) the middle black particle that generates, wash respectively 3～5 times with deionized water and absolute ethyl alcohol, promptly make solid Pd-B amorphous alloy catalyst, represent with Pd-B-is solid.
This control experiment gained catalyst is respectively applied in embodiment 9, embodiment 10, embodiment 11, embodiment 16, embodiment 17 and embodiment 18 coupling reactions, and its catalytic performance data are shown in Table 1.
Table 1 is the catalytic performance data of catalyst among the embodiment
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have change and change.Within the spirit and principles in the present invention all, any modification of being done, improvement etc. all should be included within protection scope of the present invention.
Claims (9)
1. double-deck hollow amorphous alloy nano-sphere, it is characterized in that: its specific activity surface area is 20～40m
2/ g, the internal layer cavity diameter is 240～260nm, and the distance between two-layer is 40～60nm, and the wall thickness of spherical shell is 10～20nm, and the spherical shell of double-deck hollow nanospheres is that the M-B amorphous alloy nano particle of 4～6nm is formed by particle size, and M wherein is a metallic element.
2. double-deck hollow amorphous alloy nano-sphere according to claim 1 is characterized in that: described M metallic element is selected from any one in nickel, cobalt, iron, ruthenium, palladium and the platinum.
3. a method for preparing the described double-deck hollow amorphous alloy nano-sphere of claim 1 is characterized in that: comprise the steps:
1) with 0.01g/L, the 3mL metal salt solution joins in the polystyrene hollow ball of sulfonation, and ultrasonic 20～60min stirred 12～24 hours down at 0～30 ℃, and is centrifugal, and freeze drying obtains the polystyrene sphere that slaine wraps up;
2) under 0～30 ℃ the metal hydroboron aqueous solution of 0.1～1.0mol/L dropwise is added drop-wise in the polystyrene sphere of slaine parcel of step 1) preparation, wherein: the mol ratio of metal hydroboron and slaine is 4～6: 1;
3) filtration step 2) the middle black particle that generates, freeze drying with DMF or THF dissolved polystyrene bead, is washed respectively 3～5 times with deionized water and absolute ethyl alcohol again, promptly obtains double-deck hollow amorphous alloy nano-sphere.
4. the preparation method of double-deck hollow amorphous alloy nano-sphere according to claim 3 is characterized in that: described slaine is the organic salt or the inorganic salts of nickel, cobalt, iron, ruthenium, palladium and platinum.
5. the preparation method of double-deck hollow amorphous alloy nano-sphere according to claim 4 is characterized in that: described slaine is the organic salt or the inorganic salts of nickel, cobalt and palladium.
6. the preparation method of double-deck hollow amorphous alloy nano-sphere according to claim 3 is characterized in that: described metal hydroboron is one or both mixing in sodium borohydride and the potassium borohydride.
7. the preparation method of double-deck hollow amorphous alloy nano-sphere according to claim 6 is characterized in that: described metal hydroboron is a potassium borohydride.
8. the described described double-deck hollow amorphous alloy nano-sphere of claim 1 is characterized in that: be applied to the hydrogenation catalyst reaction of alkene, alkynes, aromatic hydrocarbons, nitrile, nitro compound, carbonyls; Also be applied to C-C, C-S coupling reaction.
9. the purposes of double-deck hollow amorphous alloy nano-sphere according to claim 8 is characterized in that: be applied to the Sonogashira reaction, and iodobenzene and the reaction of benzenethiol prepared in reaction diphenyl sulfide.
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| CN109529879A (en) * | 2018-12-26 | 2019-03-29 | 盐城锦明药业有限公司 | A kind of PdNi/RGO nanocatalyst and preparation method thereof |
| CN110241438A (en) * | 2018-03-08 | 2019-09-17 | 天津大学 | Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof |
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| CN101380577A (en) * | 2008-10-17 | 2009-03-11 | 上海师范大学 | Hollow amorphous alloy nano-sphere catalyst, preparation method and use thereof |
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| CN110241438A (en) * | 2018-03-08 | 2019-09-17 | 天津大学 | Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof |
| CN109529879A (en) * | 2018-12-26 | 2019-03-29 | 盐城锦明药业有限公司 | A kind of PdNi/RGO nanocatalyst and preparation method thereof |
| CN109529879B (en) * | 2018-12-26 | 2022-04-05 | 盐城师范学院 | PdNi/RGO nano-catalyst and preparation method thereof |
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Application publication date: 20110914 |