CN104607195A - Preparation method and applications of metal/zinc oxide nano heterogeneous array - Google Patents
Preparation method and applications of metal/zinc oxide nano heterogeneous array Download PDFInfo
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Abstract
The invention provides a preparation method and applications of a metal/zinc oxide nano heterogeneous array. A ZnO nanorod array is prepared on the surface of a zinc sheet, and various metal nanoparticles such as Cu, Ag, Au, Pd and Pt can be loaded at the top ends of nanorods in the array in situ. Compared with the prior art, the metal/zinc oxide nano heterogeneous array prepared according to the invention has the following advantages: (1) the array is used for organocatalysis, and easy to recycle; (2) the size and distribution of loaded nanoparticles are easily controlled; (3) because a reducing agent and a surfactant are not used, the surfaces of the nanoparticles are clean, so that the nanoparticles have good catalytic activity; (4) the effective utilization of metal ion precursors is high, and a heterogeneous nucleation phenomenon of the nanoparticles does not occur; and (5) through a subsequent oxidation method, transition metal nanoparticles can be further converted into nanoparticles of metal oxides, so that the type of the nano heterogeneous array can be expanded.
Description
Technical field
The present invention relates to Nano-composite materials method, be specifically related to preparation method and the application of the heterogeneous array of a kind of metal/zinc-oxide nano.
Background technology
Effectively being loaded on carrier by the nano particle with high catalytic activity makes it be uniformly dispersed, and reduces the contact in catalytic reaction process, thus makes it keep good catalytic activity to have great importance.Find in the catalytic activity research of this type of catalyst, the physicochemical properties of the clean level of nano grain surface, crystalline structure, shape and carrier have significant impact to catalytic activity, and this is also one of the study hotspot in current nano-catalytic field.
Usually need to use the methods such as centrifugal or filtration when being separated nanocatalyst, but these methods generally can only for separating of a small amount of reactant liquor, being separated nanocatalyst is fast and effectively one of important problem of facing of nano-catalytic science.In order to not affect the load capacity of nano particle, reduce the difficulty of separation, the method usually adopted nano particle is loaded to the surface that length reaches the one-dimensional nano structure of micron level simultaneously, as CNT, and silicon nanowires etc.As catalytic activity good to Heck coupling reaction after Pd and Rh nano particle being loaded to carbon nano tube surface, after 120 DEG C of reaction 3h, reaction yield can reach 94%, when being 24h with the Pd nano particle reaction time of business under the same terms, productive rate is only 53%.The coupling reaction of Cu nano particle to halogeno-benzene and aniline of silicon nanowires support has extraordinary catalytic activity equally, it is worth mentioning that the bromobenzene that reactivity is not high or chlorobenzene also can react with diphenylamines under the existence of this catalyst.Another kind method be by nanoparticulate dispersed to thin two-dimensional nanostructure as on Graphene or graphene oxide.As taken dodecyl sodium sulfate as surfactant and reducing agent, graphene-supported Pd nano particle has excellent catalytic activity to Suzuki coupling reaction, even under water and air existence condition, catalytic activity is still very high, just can complete whole reaction within 5 minutes.Magnetic nanoparticle is also a kind of carrier of excellent recyclable catalyst, under the effect of outside magnetic field, nano particle can be separated fast and effectively.As loaded to Fe
3o
4and NiFe
2o
4the Pd of nano grain surface shows the activity of good catalysis in all kinds of hydrogenation, and under the effect of outside magnetic field, composite catalyst can all reclaim, and catalytic activity does not significantly reduce in 10 circulations.
Nanometer stick array is a member important in nanostructured big family, it is mainly made up of at different substrates nanometer rods vertical-growth, rank more than its size can reach centimetre, thus have better operability compared to other structure, nowadays it has shown application prospect widely in field of nanometer devices.At present, the method prepared about ZnO and Si nanometer stick array obtains significant progress, this also lays a solid foundation for other purposes of nanometer stick array, and as the carrier as catalyst, reaction substrate can participate in reacting by the nano grain surface of the void diffusion of nanometer rods to load.Nanometer stick array has had the advantage of nano-carrier and block carrier concurrently as the carrier of catalyst, first nano-array forms primarily of the substructure of nanometer rods, these substructures are the same with nano particle can a large amount of nano particle with catalytic activity of load, ensure that the load capacity of catalyst; Secondly, the macro-scale of array structure can reach a centimetre rank usually, and this just improves the comfort level of catalyst recovery greatly.The another one advantage of the catalyst of array-like is exactly, the position of the activated nano particle of tool is fixing, decrease their contacts in catalytic process, make nano particle have stable catalytic activity (because the change of catalyst particle size is very little).Such as: the Si nanometer stick array of load Pd can catalysis various reaction, as Mizoroki-Heck reaction, the catalytic hydrogenation of alkene, the hydrogenolysis of nitrobenzene, α, hydrosilylation of alpha, beta-unsaturated ketone etc., it is worth mentioning that the catalyst after recovery still has very strong catalytic activity.The Si nanometer stick array of Ag nano particle load is also successfully used in higher alcohols to be oxidized to corresponding aldehyde, and in whole course of reaction, show higher reactivity and selective.The ZnO nano-rod array of Cu nano particle load shows good catalytic activity in the process of methyl alcohol conversion hydrogen, this good activity is mainly because Cu nano particle has large specific area, dispersiveness and the stability of Cu nano particle is improve, pretending by factors such as the electronic structure states changing Cu of ZnO and metal in the load on ZnO surface.
In the preparation process of nano heterogeneous array structure in the past, generally need the method for physics or with under the condition of reducing agent, illumination, the presoma of metal reduced, and in nanorod surfaces nucleation, growth.As: when pH value is 9-11, take ethylene glycol as reducing agent, copper nitrate is the array that the ZnO nanorod of Cu nano particle load has successfully been prepared in copper source.The method of ion sputtering is also used to the heterogeneous array of making ZnO-Ag, and the heterogeneous array obtained has good sensitivity to rhodamine in surface Raman enhancement process, reaches 10 in addition to the detection limitation of chlordiphenyl
-11m.Under the irradiation of xenon lamp, in the mixed solution of second alcohol and water, AgNO
3can be reduced into Ag and be deposited on the surface of ZnO nano-rod array, resulting structures under light illumination photoelectric current significantly increases, because the existence of metal nanoparticle, is conducive to being separated of hole and electronics.The shortcoming of these synthetic methods is: the pay(useful) load degree of nano particle is not high, independent nucleation after a certain amount of reducing metal ions; The size of particle is restive, and load time is longer; The reducing agent added in usual preparation process can be adsorbed on the surface of the nano particle of formation and affect the catalytic activity of gained particle.
Summary of the invention
For solving the problems of the technologies described above, the object of the invention is to, the preparation method of the heterogeneous array of a kind of metal/zinc-oxide nano is provided, a kind of short-cut method of metal nanoparticle in the pay(useful) load on ZnO nano-rod array top realizing clean surface.
Present invention also offers the application of the heterogeneous array of a kind of metal/zinc-oxide nano, for organic catalysis.
The preparation method of the heterogeneous array of a kind of metal/zinc-oxide nano provided by the invention, comprises the following steps:
(1), by zinc metal sheet use second alcohol and water after ultrasonic 30 minutes respectively, put into ammoniacal liquor, add thermal response, be cooled to room temperature, washing, 60 DEG C of vacuum drying 2h, obtain highly regular zinc oxide nano array;
(2), by the zinc oxide nano array of zinc metal sheet load put into metal salt solution 5-30s, obtain the heterogeneous array of metal/zinc-oxide nano.
Ammoniacal liquor described in step (1) is: use after the ammoniacal liquor of 6ml mass concentration 25%-28% is diluted to 34ml;
The thermal response that adds described in step (1) is: 110-120 DEG C of reaction 12-15h.
Washing described in step (1) is wash 3-5 time respectively with ultra-pure water and absolute ethyl alcohol.
Metallic solution described in step (2) is CuCl
2,agNO
3, HAuCl
4, Na
2pdCl
4, or H
2ptCl
6solution any one, the concentration of solution used is 5mmol/L.
Obtain the heterogeneous array of metal/zinc-oxide nano described in step (2), comprise Cu/ZnO, the nano heterogeneous array of Ag/ZnO, Au/ZnO, Pd/ZnO, Pt/ZnO.
The application of the heterogeneous array of a kind of metal/zinc-oxide nano provided by the invention, for the application of organic catalysis.
Further, the application of Pt/ZnO provided by the invention nano heterogeneous array catalysis Suzuki coupling reaction, comprises the following steps:
A, be that 1: 1.1: 1.2 mixing is added in 100ml tri-neck round-bottomed flask in molar ratio by halogenated aryl hydrocarbon, phenyl boric acid, potash, then add the 10cm be cut into small pieces
2the nano heterogeneous array of Pd-ZnO of zinc metal sheet load as catalyst, vacuumize rear injection 30ml solvent DMF, 100 DEG C-110 DEG C reaction 6h-24h under argon shield;
B, by product purification, through extraction, dry, concentrated after obtain biphenyl analog derivative by column chromatography for separation.
Reaction equation is:
Halogenated aryl hydrocarbon also comprises adjacent diiodo-benzene, 3-bromopyridine
The present invention, at the array of the surperficial making ZnO nanometer rods of zinc metal sheet, because Zn has very strong reducing power, converts Zn in course of reaction
2+be discharged in solution, the electronics that reaction produces can dissociate to the reduction reaction of the top participation metal ion of array.The various metals nano particles such as Cu, Ag, Au, Pd, Pt can the top loading to nanometer rods in array of original position, size and the distribution situation of nano particle is realized by the concentration regulating and controlling reaction time and precursors, the concentration of reaction time and precursor salt solution and the size of nano particle and dense degree are all direct ratios, slightly conference load is excessive for the concentration of solution used, therefore the concentration of solution used is 5mmol/L, changed the pattern of carried metal nano particle by the time of immersing salting liquid, the pattern that reaction time 5s obtains is best.
The nano heterogeneous array of the Pd/ZnO obtained can the Suzuki of catalysis efficiently coupling reaction.Suzuki coupling reaction in document will use catalyst acetic acid palladium up to 1-5% equivalent (1mol%-5mol%) or palladium bichloride usually, can not reclaim, and with Phosphine ligands, alkali consumption is high (2-2.5 equivalent is best) also.And Pd/ZnO provided by the present invention is measured by ICP, the palladium salt of 0.01mol% is only used in catalysis Suzuki reaction, need part, and catalyst also can be recycled for 2-3 time.
Compared with prior art, the advantage of the heterogeneous array of metal/zinc-oxide nano prepared of the present invention: (1) easily reclaims for organic catalysis; (2) size of the nano particle of load and distribution situation are easy to control; (3) owing to not using reducing agent and surfactant, the clean surface of nano particle, should have good catalytic activity; (4) effective rate of utilization of metal ion presoma is high, and the heterogeneous nucleation phenomenon of nano particle can not occur; (5) by the method for follow-up oxidation, transition metal nanoparticles can be further converted to the nano particle of metal oxide, can expand the kind of nano heterogeneous array.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the zinc oxide nano array of preparation;
Fig. 2 is for putting into CuCl
2the stereoscan photograph of the nano heterogeneous array of Cu/ZnO prepared by solution 5s;
Fig. 3 is for putting into CuCl
2the stereoscan photograph of the nano heterogeneous array of Cu/ZnO prepared by solution 15s;
Fig. 4 A is the stereoscan photograph of the Ag/ZnO nano-heterogeneous structure of preparation;
Fig. 4 B is the stereoscan photograph (amplification) of the Ag/ZnO nano-heterogeneous structure of preparation;
Fig. 5 A is the stereoscan photograph of the Au/ZnO nano-heterogeneous structure of preparation;
Fig. 5 B is the stereoscan photograph (amplification) of the Au/ZnO nano-heterogeneous structure of preparation;
Fig. 6 A is for putting into Na
2pdCl
4the stereoscan photograph of Pd/ZnO nano-heterogeneous structure prepared by solution 5s;
Fig. 6 B is for putting into Na
2pdCl
4the stereoscan photograph (amplification) of Pd/ZnO nano-heterogeneous structure prepared by solution 5s
Fig. 7 is for putting into Na
2pdCl
4electron spectrum (EDS) photo of Pd/ZnO nano-heterogeneous structure prepared by solution 5s;
Fig. 8 is the stereoscan photograph of the Pt/ZnO nano-heterogeneous structure of preparation;
Fig. 9 is the stereoscan photograph (large figure is overall pattern, and little figure is perspective view sheet) of the nano heterogeneous catalyst of Pd/ZnO reclaimed.
Detailed description of the invention
Embodiment 1
A preparation method for the heterogeneous array of metal/zinc-oxide nano, comprises the following steps:
(1), at room temperature, be transferred in the autoclave of 60ml inner liner polytetrafluoroethylene inner bag after the ammoniacal liquor getting the commercially available 25%-28% of 6ml is diluted to 34ml, zinc metal sheet is put into aforesaid reaction vessel with second alcohol and water after ultrasonic 30 minutes respectively, reactor to be put under 120 DEG C of baking ovens heating 15 hours, naturally cool to room temperature subsequently, with ultra-pure water and absolute ethanol washing 3 times, finally in vacuum drying chamber, namely 60 DEG C of dryings obtain highly regular zinc oxide nano array in about 2 hours;
(2), with tweezers clamp the zinc oxide nano array of zinc metal sheet load, immerse the CuCl of 5mmol/L
215s in solution, obtains Cu/ZnO nano-heterogeneous structure.
Embodiment 2
A preparation method for the heterogeneous array of metal/zinc-oxide nano, comprises the following steps:
(1), at room temperature, be transferred in the autoclave of 60ml inner liner polytetrafluoroethylene inner bag after the ammoniacal liquor getting the commercially available 25%-28% of 6ml is diluted to 34ml, zinc metal sheet is put into aforesaid reaction vessel with second alcohol and water after ultrasonic 30 minutes respectively, reactor to be put under 110 DEG C of baking ovens heating 14 hours, naturally cool to room temperature subsequently, with ultra-pure water and absolute ethanol washing 3 times, finally in vacuum drying chamber, namely 60 DEG C of dryings obtain highly regular zinc oxide nano array in about 2 hours;
(2), tweezers clamp the zinc oxide nano array of zinc metal sheet load, immerse the Na of 5mmol/L
2pdCl
45s in solution, obtains Pd/ZnO nano-heterogeneous structure.This heterojunction structure ICP learns that the load capacity of palladium is 0.035mg/cm after measuring
2.
Embodiment 3
A preparation method for the heterogeneous array of metal/zinc-oxide nano, comprises the following steps:
Step (1) is with embodiment 2;
Step (2) clamps the zinc oxide nano array of zinc metal sheet load with tweezers, immerse the HAuCl of 5mmol/L
45s in solution, can obtain the nano heterogeneous array of Au/ZnO easily.
Embodiment 4
A preparation method for the heterogeneous array of metal/zinc-oxide nano, comprises the following steps:
Step (1) is with embodiment 2;
Step (2) clamps the zinc oxide nano array of zinc metal sheet load with tweezers, immerse the AgNO of 5mmol/L
315s in solution, can obtain the nano heterogeneous array of Ag/ZnO easily.
Embodiment 5
A preparation method for the heterogeneous array of metal/zinc-oxide nano, comprises the following steps:
Step (1) is with embodiment 2;
Step (2) clamps the zinc oxide nano array of zinc metal sheet load with tweezers, immerse the H of 5mmol/L
2ptCl
65s in solution, can obtain the nano heterogeneous arrays such as Pt/ZnO easily.
Embodiment 6
An application for the heterogeneous array of metal/zinc-oxide nano, the synthesis of biphenyl, comprises the following steps:
A, get 13mmol phenyl boric acid and 14mmol potash in 100mL tri-neck round-bottomed flask, vacuumize rear logical argon gas state bet emitter and inject 12mmol iodobenzene and 30ml solvent DMF, then add the 10cm being cut into small pieces
2the nano heterogeneous catalyst of Pt/ZnO, at 100 DEG C, stirring reaction is after 6 hours;
B, extracted by product ethyl acetate, drying obtains crude product, and crude product purified by silica gel column chromatography (solvent is benzinum) purifying is obtained white solid and biphenyl, productive rate 99%, and fusing point is 67-69 DEG C.
1H NMR(300MHz,CDCl
3)δ7.57-7.60(m,4H),7.40-7.45(m,4H),7.31-7.36(m,2H)；
13C NMR(75MHz,CDCl
3)δ141.3,128.8,127.3,127.2。
Embodiment 7
An application for the heterogeneous array of metal/zinc-oxide nano, the synthesis of 4-methoxyl biphenyl, comprises the following steps:
A, the 4-methoxyl group iodobenzene getting 12mmol, 13mmol phenyl boric acid and 14mmol potash, in 100mL tri-neck round-bottomed flask, vacuumize rear logical argon gas state bet emitter and inject 30ml solvent DMF, then add the 10cm being cut into small pieces
2the nano heterogeneous catalyst of Pt/ZnO, at 110 DEG C, stirring reaction is after 8 hours;
B, product ethyl acetate to be extracted, drying obtains crude product, by crude product purified by silica gel column chromatography, (solvent volume is than being benzinum: ethyl acetate=20:1) purifying obtains white solid and 4-methoxyl biphenyl, productive rate 99%, and fusing point is 85-87 DEG C.
1H NMR(300MHz,CDCl
3)δ7.51-7.56(m,4H),7.38-7.43(m,2H),7.30-7.32(m,1H),6.96-6.99(m,2H),3.84(s,3H)；
13C NMR(75MHz,CDCl
3)δ159.5,141.2,134.1,129.1,128.6,127.1,127.1,114.6,55.7。
Embodiment 8
An application for the heterogeneous array of metal/zinc-oxide nano, the synthesis of 4-Phenylbenzoic acid ethyl ester, comprises the following steps:
A, get 13mmol phenyl boric acid and 14mmol potash in 100mL tri-neck round-bottomed flask, vacuumize 4-iodo ethyl benzoate and 30ml solvent DMF that rear logical argon gas state bet emitter injects 12mmol, then add the 10cm being cut into small pieces
2the nano heterogeneous catalyst of Pt/ZnO, at 110 DEG C, stirring reaction is after 6 hours;
B, product ethyl acetate to be extracted, drying obtains crude product, by crude product purified by silica gel column chromatography, (solvent volume is than being benzinum: ethyl acetate=20:1) purifying obtains white solid and 4-Phenylbenzoic acid ethyl ester, productive rate 99%, and fusing point is 47-48 DEG C.
1H NMR(300MHz,CDCl
3)δ8.10-8.13(m,2H),7.61-7.67(m,4H),7.39-7.49(m,3H),4.40(q,J＝6.9Hz,2H)，1.41(t,J＝7.2Hz,3H)；
13C NMR(75MHz,CDCl
3)δ166.9，145.9，140.4，130.4，129.6，129.3，128.5，127.7，127.4，61.4，14.8。
Claims (10)
1. a preparation method for the heterogeneous array of metal/zinc-oxide nano, is characterized in that, described preparation method comprises the following steps:
(1), by zinc metal sheet use second alcohol and water after ultrasonic 30 minutes respectively, put into ammoniacal liquor, add thermal response, be cooled to room temperature, washing, 60 DEG C of vacuum drying 2h, obtain highly regular zinc oxide nano array;
(2), by the zinc oxide nano array of zinc metal sheet load put into metal salt solution 5-30s, obtain the heterogeneous array of metal/zinc-oxide nano.
2. preparation method according to claim 1, is characterized in that, the thermal response that adds described in step (1) is: 110-120 DEG C of reaction 12-15h.
3. preparation method according to claim 1, is characterized in that, the ammoniacal liquor described in step (1) is: use after the ammoniacal liquor of 6ml mass concentration 25%-28% is diluted to 34ml.
4. preparation method according to claim 1, is characterized in that, the washing described in step (1) is wash 3-5 time respectively with ultra-pure water and absolute ethyl alcohol.
5. preparation method according to claim 1, is characterized in that, described in step (2), metallic solution is H
2ptCl
6, concentration 5mmol/L.
6. preparation method according to claim 1, is characterized in that, described in step (2), metallic solution is CuCl
2,agNO
3, HAuCl
4, Na
2pdCl
4any one in solution, concentration is 5mmol/L.
7. preparation method according to claim 1, is characterized in that, the heterogeneous array of metal/zinc-oxide nano that obtains described in step (2) is the nano heterogeneous array of Pt/ZnO.
8. preparation method according to claim 1, is characterized in that, described in step (2) obtain the heterogeneous array of metal/zinc-oxide nano be the nano heterogeneous array of Cu/ZnO, Ag/ZnO, Au/ZnO, Pd/ZnO any one.
9. an application for the heterogeneous array of metal/zinc-oxide nano prepared by any one of claim 1-8, is characterized in that, for organic catalysis.
10. application according to claim 9, is characterized in that, the application of Pt/ZnO nano heterogeneous array catalysis Suzuki coupling reaction, comprises the following steps:
A, be that 1: 1.1: 1.2 mixing is added in 100ml tri-neck round-bottomed flask in molar ratio by halogenated aryl hydrocarbon, phenyl boric acid, potash, then add the 10cm be cut into small pieces
2the nano heterogeneous array of Pd-ZnO of zinc metal sheet load as catalyst, vacuumize rear injection 30ml solvent DMF, 100 DEG C-110 DEG C reaction 6h-24h under argon shield;
B, by product purification, through extraction, dry, concentrated after obtain biphenyl analog derivative by column chromatography for separation.
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| CN108375565A (en) * | 2018-01-23 | 2018-08-07 | 中央民族大学 | A kind of nano-cone array composite S RES substrates and preparation method |
| CN108722400A (en) * | 2018-05-28 | 2018-11-02 | 福州大学 | One-dimension zinc oxide/silver/Aurum clusters nano-array optic catalytic composite material and the preparation method and application thereof |
| CN110585475A (en) * | 2019-09-18 | 2019-12-20 | 西南大学 | Light-operated antibacterial degradable zinc alloy suture material and preparation method thereof |
| CN111204793A (en) * | 2020-01-14 | 2020-05-29 | 江苏海洋大学 | Simple and green preparation method of flower-like copper/zinc oxide micro-nano material |
| CN111204794A (en) * | 2020-01-17 | 2020-05-29 | 清华大学 | Preparation method of dendritic hollow zinc oxide nanorod array |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108375565A (en) * | 2018-01-23 | 2018-08-07 | 中央民族大学 | A kind of nano-cone array composite S RES substrates and preparation method |
| CN108722400A (en) * | 2018-05-28 | 2018-11-02 | 福州大学 | One-dimension zinc oxide/silver/Aurum clusters nano-array optic catalytic composite material and the preparation method and application thereof |
| CN110585475A (en) * | 2019-09-18 | 2019-12-20 | 西南大学 | Light-operated antibacterial degradable zinc alloy suture material and preparation method thereof |
| CN111204793A (en) * | 2020-01-14 | 2020-05-29 | 江苏海洋大学 | Simple and green preparation method of flower-like copper/zinc oxide micro-nano material |
| CN111204794A (en) * | 2020-01-17 | 2020-05-29 | 清华大学 | Preparation method of dendritic hollow zinc oxide nanorod array |
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