CN104561840A - Method for simply preparing amorphous alloy CuB23 nano short tube and application thereof - Google Patents
Method for simply preparing amorphous alloy CuB23 nano short tube and application thereof Download PDFInfo
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- CN104561840A CN104561840A CN201410811941.3A CN201410811941A CN104561840A CN 104561840 A CN104561840 A CN 104561840A CN 201410811941 A CN201410811941 A CN 201410811941A CN 104561840 A CN104561840 A CN 104561840A
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Abstract
The invention discloses a method for simply preparing an amorphous alloy CuB23 nano short tube and application thereof. The method comprises the following steps: (1) adding a copper acetate solution into a NH3.H2O solution with a concentration of 25 percent by weight to obtain a Cu(NH3)42+compound; (2) then adding a KBH4 aqueous solution and polyethylene glycol in the argon protective atmosphere at the temperature of 298K; (3) performing plasma reaction for 5-20 minutes to obtain a target product; (4) washing the product with deionized water for one time, then washing with anhydrous ethanol for three times; (5) storing the product in an ethanol solution for standby. In the Heck-coupling reaction, the CuB23 nano tube is an effective catalyst for substituting Pd and Ni complexes, is cheaper and does not need any ligand. Meanwhile, after being recycled for 10 times, the catalyst has small activity loss and has no crystal shape and structure change.
Description
Technical field
The present invention relates to nano material and catalytic field, relate generally to and utilize liquid phase plasma (SPP, solution plasma process) technology, prepare monodispersed non-crystaline amorphous metal CuB
23the method of nanometer short tube, and its application in the Heck coupling reaction of catalysis low activity halogenated alkane and alkene.
Background technology
Heck intersects that to be coupled be in a mild condition, halogenide or form the reaction of intramolecule C-C key between the sulfonate electric agent of parent and alkene.Due to its in a lot of fields, comprise natural product and fine chemistry synthesis in application, be study one of the most deep organic reaction.Up to the present, the catalyzer that most of catalysis Heck reacts is based on Pd, as Pd title complex and Pd nanoparticle.In these Pd catalyzer, solubility Pd compound, is mainly phosphine-Pd title complex, is to react the most effective catalyzer to Heck.But Pd catalyzer is very expensive, and the title complex of Pd is normally poisonous, therefore uses limited.Therefore the catalyzer latest developments based on Ni, Co, Cu, Fe and its title complex are got up, as novel catalyst replaced Pd.But, except nickel, do not have a kind of catalyzer can match in excellence or beauty with Pd in the versatility of synthesis, especially when relating to the Heck reaction of low activity halogenated alkane.Therefore, catalysis Heck is reacted more efficiently, more cheap catalyzer is anxious to be developed.
Recently, amorphous metal boride (M-B) alloy catalyst with good nanostructure receives much concern, such as, due to their low cost and uncommon performance, isotropic structure, and the unsaturated site of coordination of high density, and chemical stability.Such as, Chen etc. adopt the lytropic liquid crystals (being formed by the nonionic mixed and anion surfactant) with layered structure as template, to obtain the long nanotube of M-B, and in hydrogenation reaction, show excellent catalytic performance.The material of the mesoporous M-B of the preparation such as Li and Tong has good Catalytic Hydrogenation Properties.The hydrolized metal hydroborate of excellent property produces H
2m-B nano flower and hollow ball successfully prepare.The M-B material of different shape has excellent catalytic performance, and that has reported comprises nanometer nuclear shell nano-structure, hollow spindle, nanometer ball, cellular and nano thread structure.Recently, Li etc. develop the Co-B Nano microsphere that efficient catalytic Heck reacts.Copper composition can effectively catalysis Heck react oxime ester class cyclization, meanwhile, B doping Cu catalyzer on hydrogenation and dehydrogenation, there is excellent catalytic activity.Based on these results, we attempt preparing the amorphous Cu-B alloy with good nanostructure and have highly active catalyzer as a kind of novel reacting Heck.As far as we know, the report not using amorphous Cu-B alloy as catalyst Heck to react at present.
Summary of the invention
The invention provides and a kind of simple and easyly prepare non-crystaline amorphous metal CuB
23the method of nanometer short tube and application thereof.
The present invention adopts following technical scheme:
Of the present inventionly simple and easyly prepare non-crystaline amorphous metal CuB
23the concrete steps of the method for nanometer short tube are as follows:
(1) past concentration is the NH of 25wt%
3h
2add copper acetate solution in O solution and obtain Cu (NH
3)
4 2+mixture, NH
3h
2o is 20-60:0.0085ml/mol with the Molar ratio of venus crystals;
(2) then at 298K temperature, in argon atmosphere, KBH is added
4the aqueous solution and polyoxyethylene glycol, KBH
4be 0.5-2:0.0085 with the mol ratio of venus crystals, the mol ratio of polyoxyethylene glycol and venus crystals is 0.001-0.005:0.0085;
(3) add in liquid phase plasma body device, open plasma reaction 5-20min, obtain target product;
(4) product is first washed once with deionized water, then uses absolute ethanol washing three times;
(5) product is saved in ethanolic soln, for subsequent use.
In step (1), preferred NH
3h
2o is 40:0.0085ml/mol with the Molar ratio of venus crystals.
In step (2), preferred KBH
4be 1:0.0085 with the mol ratio of venus crystals.
In step (2), the mol ratio of preferred polyoxyethylene glycol and venus crystals is 0.003:0.0085.
In step (3), adopting tungsten to be positive and negative electrode and tungsten filament diameter is 2mm, and two interelectrode distances are 1mm, and DC pulse high pressure producer voltage is 450V, and the work period is 50%, and frequency is 12kHz.
In step (4), preferably open plasma reaction 10min.
Cu-B alloy prepared by method of the present invention, is made up of Cu and B element, and its ratio is B/Cu=23.01.
CuB of the present invention
23the appearance of alloy is nanometer short tube, and has the mean length of 50nm and the diameter of 10nm, and average wall thickness is about 2nm; Described CuB
23the crystalline structure of alloy is unformed.
Non-crystaline amorphous metal CuB prepared by method of the present invention
23nanometer short tube can be used as the catalyzer of the Heck-coupling reaction of low activity halogenated alkane and alkene.
In Heck-coupling reaction, CuB
23nanotube is the effective catalyst replacing Pd and Ni complex compound, and CuB
23nanotube is more cheap, without any need for part.Meanwhile, after recycling 10 times, loss of catalyst activity is little, and does not have the change of crystal formation and structure.For other organic synthesis, CuB
23short nanotube also exists potential application of force.
Positively effect of the present invention is as follows:
1) by adopting simple solution plasma technique, amorphous nanometer short tube CuB has successfully been synthesized first
23alloy.
2) with conventional CuB
23alloy contrasts, amorphous nanometer short tube CuB
23the specific surface area of alloy is larger.
3) with conventional CuB
23alloy contrasts, amorphous nanometer short tube CuB
23when alloy as catalyst Heck is coupled crosslinked, efficiency is higher.
4) compared with the catalyzer (as Pd) reacted with other catalysis Heck, amorphous nanometer short tube CuB
23alloy as catalyst efficiency is more efficient, cheaper, use are safer.
Accompanying drawing explanation
Fig. 1 is CuB prepared by the embodiment 1 processing 2h under an argon atmosphere
23the XRD figure spectrum of nanometer short tube.
Fig. 2 is CuB prepared by embodiment 1
23nanometer short tube TEM schemes;
The STEM figure of (a) low magnification; B STEM figure that () amplifies; C () SAED collection of illustrative plates, the scale of (b) figure is 5nm.
Fig. 3 is CuB prepared by embodiment 1
23the N of nanotube
2suction-desorption curve.
Fig. 4 (a) is CuB prepared by embodiment
23details in a play not acted out on stage, but told through dialogues high angle circular scanning transmission electron microscope (HAADF-STEM) figure of nanometer short tube; B () compares line according to the B/Cu of details in a play not acted out on stage, but told through dialogues transverse cross-sectional area is elementary composition in (a); C ()-(e) is the EDX spectrum of (a) mid point 1-3.
Fig. 5 is CuB prepared by embodiment 1
23(a) spectrum (b) Cu 2p entirely of nanometer short tube
3/2the XPS collection of illustrative plates of (c) B1s.
Fig. 6 is CuB prepared by embodiment 1
23nanometer short tube catalysis hexanaphthene iodine and methacrylic ester recycle performance figure;
Reaction conditions: 0.01mmol CuB
23nanometer short tube, hexanaphthene ammonium iodide (5.0mmol), methyl acrylate (7.5mmol), sodium carbonate (10.0mmol), NMP (10mL), T=353K, t=12h, stir speed (S.S.) is 800 turns.
Fig. 7 is CuB prepared by embodiment 1
23nanometer short tube recycles (a) details in a play not acted out on stage, but told through dialogues high angle circular scanning transmission electron microscope (HAADF-STEM) figure after 10 times; B () compares line according to the B/Cu of details in a play not acted out on stage, but told through dialogues transverse cross-sectional area is elementary composition in (a); (c) SAED collection of illustrative plates.
Fig. 8 is CuB prepared by embodiment 1
23nanometer short tube recycles the spectrum of the XRD figure after 10 times.
Embodiment
The following examples describe in further detail of the present invention.
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from open commercial sources.
Embodiment 1
Non-crystaline amorphous metal CuB
23the preparations and applicatio of nanometer short tube, mainly comprises the following steps:
1) be the NH of 25% by 40mL concentration
3h
2add 10mL copper acetate solution (0.0085mol) in O solution and obtain Cu (NH
3)
4 2+mixture;
2) then at 298K temperature, in argon atmosphere, 32mL1.0MKBH is added
4the aqueous solution and 0.003M polyoxyethylene glycol;
3) open plasma reaction after 5 minutes, obtain target product;
4) product is first washed once with deionized water, then uses absolute ethanol washing three times;
5) be saved in ethanolic soln, until use;
6) product of preparation is used for the Heck crosslinking reaction of catalysis hexanaphthene iodine and ethylene methacrylic ketone.
Fig. 1 is the CuB of preparation
23the XRD figure spectrum of nanometer short tube, can find out prepared CuB
23nanotube degree of crystallinity is very poor, confirms that it is unformed conclusion.
Fig. 2 a is CuB
23low magnification transmission electron microscope (TEM) image of nanometer short tube, can clearly find out in figure, the CuB obtained
23nanometer short tube has uniform grain size on extensive.Fig. 2 b amplified demonstrates, and nanotube has the mean length of 50nm and the diameter of 10nm, and its average wall thickness is about 2nm.Confirm further according to selected area electron diffraction analysis (Fig. 2 c) viewed haloing, CuB
23nanotube is unbodied.
Fig. 3 is CuB
23the N of nanotube
2suction-desorption test curve (BET), its specific surface area is 84.7m
2g
-1, than the irregular CuB of routine
23alloy (23.2m
2g
-1) higher.
Fig. 4 a is CuB
23details in a play not acted out on stage, but told through dialogues scanning transmission electron microscope (STEM) figure of nanotube, as can be seen from the figure, it is the uniform alloy nano particle of pattern.Be made up of the black high angle annular cross section of Fig. 4 b and point obtain B/Cu=23.01.X-ray scattering energy spectrum (EDS) result of Fig. 4 c-e difference confirms further, and nanometer short tube is only made up of Cu and B.
The x-ray photoelectron power spectrum (XPS) of Fig. 5 shows, at CuB
23in nanometer short tube, Cu and B species exist with element form.
Fig. 6 demonstrates CuB
23the recovery use properties of short nanotube.Recycling after 10 times, its activity only has slightly damaged (8%).
The STEM selected area electron diffraction of Fig. 7 and the X-ray diffraction result of Fig. 8 show, after repeated use, and CuB
23short nanotube does not have obvious crystal formation or structural changes.Also illustrate that CuB
23nanometer short tube catalysis Heck is cross-linked potential commercial applicability.
Embodiment 2
1) be the NH of 25% by 40mL concentration
3h
2add 10mL copper acetate solution (0.0085mol) in O solution and obtain Cu (NH
3)
4 2+mixture;
2) then at 298K temperature, in argon atmosphere, 32mL1.0MKBH is added
4the aqueous solution and 0.003M polyoxyethylene glycol;
3) open plasma reaction after 10 minutes, obtain target product;
4) product is first washed once with deionized water, then uses absolute ethanol washing three times;
5) be saved in ethanolic soln, until use;
6) product of preparation is used for the Heck crosslinking reaction of catalysis hexanaphthene iodine and vinyl cyanide.Embodiment 3
1) be the NH of 25% by 40mL concentration
3h
2add 10mL copper acetate solution (0.0085mol) in O solution and obtain Cu (NH
3)
4 2+mixture;
2) then at 298K temperature, in argon atmosphere, 32mL1.0MKBH is added
4the aqueous solution and 0.003M polyoxyethylene glycol;
3) open plasma reaction after 20 minutes, obtain target product;
4) product is first washed once with deionized water, then uses absolute ethanol washing three times;
5) be saved in ethanolic soln, until use;
6) product of preparation is used for the Heck crosslinking reaction of catalysis pentamethylene iodine and ethylene methacrylic ketone.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (7)
1. simple and easyly prepare non-crystaline amorphous metal CuB for one kind
23the method of nanometer short tube, is characterized in that: the concrete steps of described method are as follows:
(1) past concentration is the NH of 25wt%
3h
2add copper acetate solution in O solution to obtain
Cu (NH
3)
4 2+mixture, NH
3h
2o is 20-60:0.0085ml/mol with the Molar ratio of venus crystals;
(2) then at 298K temperature, in argon atmosphere, KBH is added
4the aqueous solution and polyoxyethylene glycol, KBH
4be 0.5-2:0.0085 with the mol ratio of venus crystals, the mol ratio of polyoxyethylene glycol and venus crystals is 0.001-0.005:0.0085;
(3) add in liquid phase plasma body device, open plasma reaction 5-20min, obtain target product;
(4) product is first washed once with deionized water, then uses absolute ethanol washing three times;
(5) product is saved in ethanolic soln, for subsequent use.
2. simple and easyly as claimed in claim 1 prepare non-crystaline amorphous metal CuB
23the method of nanometer short tube, is characterized in that: in step (1), NH
3h
2o is 40:0.0085ml/mol with the Molar ratio of venus crystals.
3. simple and easyly as claimed in claim 1 prepare non-crystaline amorphous metal CuB
23the method of nanometer short tube, is characterized in that: in step (2), KBH
4be 1:0.0085 with the mol ratio of venus crystals.
4. simple and easyly as claimed in claim 1 prepare non-crystaline amorphous metal CuB
23the method of nanometer short tube, is characterized in that: in step (2), and the mol ratio of polyoxyethylene glycol and venus crystals is 0.003:0.0085.
5. simple and easyly as claimed in claim 1 prepare non-crystaline amorphous metal CuB
23the method of nanometer short tube, is characterized in that: in step (3), and adopting tungsten to be positive and negative electrode and tungsten filament diameter in liquid phase plasma body device is 2mm, two interelectrode distances are 1mm, DC pulse high pressure producer voltage is 450V, and the work period is 50%, and frequency is 12kHz.
6. simple and easyly as claimed in claim 1 prepare non-crystaline amorphous metal CuB
23the method of nanometer short tube, is characterized in that: in step (4), opens plasma reaction 10min.
7. non-crystaline amorphous metal CuB prepared by the method as described in any one of claim 1-6
23nanometer short tube is used as the application of the catalyzer of the Heck-coupling reaction of low activity halogenated alkane and alkene.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106927545A (en) * | 2017-03-29 | 2017-07-07 | 成都理工大学 | The preparation method of the mesoporous amorphous B N O H nano materials of foam-like |
| CN107051370A (en) * | 2017-05-24 | 2017-08-18 | 成都理工大学 | The preparation method of the BN nanometer sheets of amorphous state O doping |
| CN110745838A (en) * | 2019-10-25 | 2020-02-04 | 成都理工大学 | CuB23Preparation method of nanoflower |
| CN110759349A (en) * | 2019-10-30 | 2020-02-07 | 成都理工大学 | Porous CuB23Preparation method of (1) |
| CN110773109A (en) * | 2019-11-01 | 2020-02-11 | 成都理工大学 | Preparation method of boron nitride nanoflower |
| CN116043256A (en) * | 2022-11-11 | 2023-05-02 | 石河子大学 | Preparation method for in-situ synthesis of hydroxyl oxide by solution plasma |
-
2014
- 2014-12-23 CN CN201410811941.3A patent/CN104561840A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| B.J. LIAW ET AL.: "Catalysis of ultrafine CuB catalyst for hydrogenation of olefinic and carbonyl groups", 《APPLIED CATALYSIS A》 * |
| D.G. TONG ET AL.: "Preparation of monodispersed cobalt–boron spherical nanoparticles and their behavior during the catalytic decomposition of hydrous hydrazine", 《MATERIALS RESEARCH BULLETIN》 * |
| FAN YANG ET AL.: "Monodisperse amorphous CuB23 alloy short nanotubes: novel efficient catalysts for Heck coupling of inactivated alkyl halides and alkenes", 《RSC ADVANCES》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106927545A (en) * | 2017-03-29 | 2017-07-07 | 成都理工大学 | The preparation method of the mesoporous amorphous B N O H nano materials of foam-like |
| CN106927545B (en) * | 2017-03-29 | 2020-03-17 | 成都理工大学 | Preparation method of foam mesoporous amorphous B-N-O-H nano material |
| CN107051370A (en) * | 2017-05-24 | 2017-08-18 | 成都理工大学 | The preparation method of the BN nanometer sheets of amorphous state O doping |
| CN107051370B (en) * | 2017-05-24 | 2019-08-09 | 成都理工大学 | The preparation method of the BN nanometer sheet of amorphous state O doping |
| CN110745838A (en) * | 2019-10-25 | 2020-02-04 | 成都理工大学 | CuB23Preparation method of nanoflower |
| CN110759349A (en) * | 2019-10-30 | 2020-02-07 | 成都理工大学 | Porous CuB23Preparation method of (1) |
| CN110773109A (en) * | 2019-11-01 | 2020-02-11 | 成都理工大学 | Preparation method of boron nitride nanoflower |
| CN116043256A (en) * | 2022-11-11 | 2023-05-02 | 石河子大学 | Preparation method for in-situ synthesis of hydroxyl oxide by solution plasma |
| CN116043256B (en) * | 2022-11-11 | 2024-05-07 | 石河子大学 | Preparation method for in-situ synthesis of hydroxyl oxide by solution plasma |
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