CN102602983A - Method for solvothermal-method synthesis of zinc oxide nano particle assembly assisted by nitrogen-contained organic micromolecule ligand - Google Patents
Method for solvothermal-method synthesis of zinc oxide nano particle assembly assisted by nitrogen-contained organic micromolecule ligand Download PDFInfo
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Abstract
The invention discloses a method for solvothermal-method synthesis of a zinc oxide nano particle assembly assisted by nitrogen-contained organic micromolecule ligand. Methyl alcohol and ethanol are mixed solvent, and tttmb and m-bitmb serve as ligands; Zn(Ac)2 and NaOH are added into a reaction kettle to directly react for 3 days at the temperature of 65-200DEG C or after the pH (Potential Of Hydrogen) is regulated to 8; and after the mixture is lowered to the room temperature, a product is cleaned and dried in vacuum to obtain product nanometer zinc oxide. With the method, the ratio, the reaction temperature and the pH of a reactant can be regulated to obtain the zinc oxide nano particle assemblies of different appearances. The method for solvothermal-method synthesis of the zinc oxide nano particle assembly assisted by the nitrogen-contained organic micromolecule ligand has the characteristics that the nanometer zinc oxide with the special appearance structure can be controllably synthesized, and the method has a low price, is convenient to operate and is easy to control. The nanometer zinc oxide synthesized with the method has strong adsorption in the near-infrared and has a favorable application value.
Description
Technical field
The present invention relates to a kind of compound method of nano zinc oxide material, relate in particular to the preparation method of the auxiliary solvent-thermal method zinc oxide nano-particle of a kind of nitrogenous organic molecule part assembly.
Background technology
Zinc oxide (ZnO) all has a wide range of applications in fields such as rubber, dyestuff, printing ink, coating, glass, piezoelectric ceramics, photoelectron and daily-use chemical industries as a kind of novel inorganic chemical materials.Nano level zinc oxide material has further improved electricity, the optical property of zinc oxide, as, nanostructure high-specific surface area, small size can improve zinc oxide luminescent frequency and chemical sensitivity.Because quantum confined effect, the exciton concentration in zinc oxide (ZnO) nanostructure strengthens, and luminous intensity can further strengthen.Excellent material behavior makes nano zinc oxide material become a research focus of field of nanometer material technology in recent years; Nano zinc oxide material has good performance, like semiconducting behavior, and piezoelectric property; Photocatalysis performance; Physiologically acceptable performance or the like has applied to electromechanical pickup, nano generator, solar cell, nano laser or the like, has boundless commercial application prospect.
Structure is the basis that nano material is used, and it will influence the performance of nano material on very big aspect.Therefore, controllability ground growth of zinc oxide nano structure is an important directions in the current nano zinc oxide material research with the functional device that acquisition has novel performance aspect preparation.The process method of preparation nano structure of zinc oxide is a lot, and according to having or not chemical reaction to take place to be divided into physics method and chemical method in the preparation process, but the physics method generally is difficult to obtain the zinc oxide of Nano grade.
Chemical method comprises solid phase method, liquid phase method (comprising sol-gel method, the precipitator method, hydrothermal method, microemulsion method etc.) and vapor phase process (chemical gas-phase reaction method and laser chemical vapor deposition method etc.).The zinc oxide one-dimensional nanomaterial of these method preparations has profuse structure and morphology, like zinc oxide nanowire, nano belt, nanotube, nano-rings, nanometer spring, nano-comb, four pin shape nanostructures or the like.Comparatively speaking, the hydro-thermal rule is fairly simple.And the method that obtains this special construction nano zine oxide of hollow ball at present mainly is two kinds: the auxiliary hydrothermal method of thermal evaporation and template.The instrument that thermal evaporation needs is complicated, and influence factor is more, like raw material type, vaporization temperature, collection temperature, catalyst-free and catalyst type, pressure and carrier gas etc. are arranged, makes poor controllability, and production efficiency is low; And the auxiliary hydrothermal method of template needs complicated synthesis technique, must introduce template, and is difficult to the special globosity of structure.
Therefore, provide a kind of simple, cheap synthetic nano zine oxide method to seem particularly important with special construction.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that the nano zine oxide preparation method exists; Aim to provide the method for the auxiliary solvent-thermal method synthesizing zinc oxide of a kind of nitrogenous organic molecule part nanoparticle assembly, Nano/micron zinc oxide that can the controlledly synthesis ad hoc structure, simple to operate; Ratio through the regulation and control reactant; Temperature of reaction, conditions such as pH obtain the nano zine oxide of different-shape, and under the condition that does not need template, have synthesized zinc oxide nano hollow spheres.
Accomplishing the technical scheme of taking of the present invention is: the method for the auxiliary solvent-thermal method synthesizing zinc oxide of a kind of nitrogenous organic molecule part nanoparticle assembly is a mixed solvent with methyl alcohol and ethanol, in reaction kettle, adds Zn (Ac)
2Or its hydrate, press Zn (Ac)
2With tttmb with
mThe mol ratio of-bitmb is that 0.5～5:1:1 adds containing n-donor ligand 1,3,5-three (1-triazol radical-methylene radical)-2,4, and 6-Three methyl Benzene (tttmb) and 1,3-two (1-imidazolyl-methylene radical)-2,4,6-Three methyl Benzene (m-bitmb) is pressed Zn (Ac)
2With the mol ratio of NaOH be that 1:0～2 add NaOH, directly or after regulating Ph=8, reaction 70-75 h reduces to room temperature after scouring reaction product under 65 ℃～200 ℃ conditions, vacuum-drying makes the zinc oxide nano-particle assembly.
In the said method, Zn (Ac)
2Or the mol ratio of its hydrate and NaOH is 1:0～2, do not add or add the NaOH of different ratios, and is like 1:0.2,1:1 or 1:2, relevant with the pattern of zinc oxide nano-particle assembly.
In the said method, in methyl alcohol and the ethanol mixed solvent, methyl alcohol and alcoholic acid volume ratio are 1～3:1.
Reacting required containing n-donor ligand can be according to synthetic (the Hong-Ke Liu of the method in the disclosed document; Cheng-yong Su; Cheng-Ming Qian; Jun Liu, Hai-Yan Tan and Bei-Sheng Kang. Assembly of a twin-cage complex containing a linear array of Pd
3. J. Chem. Soc., Dalton Trans., 2001,1167 – 1168), part one is 1; 3,5-three (1-triazol radical-methylene radical)-2,4,6-Three methyl Benzene (1,3; 5-tris (triazol-1-ylmethyl)-2,4,6-trimethylbenzene abbreviates tttmb as); Part two is 1,3-two (1-imidazolyl-methylene radical)-2,4, the 6-Three methyl Benzene (
1,3-bis (1-imidazo)-1-ylmethyl)-2,4,6-trimethylbenzen abbreviates m-bitmb as).
Zinc oxide nano-particle assembly synthetic method: accurately take by weighing a certain amount of Zn (CH
3COO)
22H
2O, NaOH, tttmb and m-bitmb join it in hydrothermal reaction kettle; Add amount of methanol and ethanol again, regulate Ph=8 directly or with formic acid after, constant temperature is reaction 70-75 h down; Naturally reduce to after the room temperature with absolute ethanol washing product 3-5 time, vacuum-drying is in order to analyze and to characterize.
Change through reaction conditions; Can synthesize the zinc oxide nano-particle assembly that obtains various different-shape structures, typically comprise nano-zinc oxide hollow sphere, have the nanometer rod zinc oxide sphere, six side's sheet assembling nano zinc oxide solid sphere, nano zine oxide ring, the zinc oxide and the fancy zinc oxide ring that are centered on by nano belt.
The zinc oxide nano-particle assembly that has specifically prepared following single shape among the embodiment, preferred concrete reaction conditions is following:
Zn (Ac)
22H
2O, NaOH, tttmb,
mThe molar ratio of-bitmb is 5:1:1:1, adds methanol/ethanol volume ratio 1:1, and what 65 ℃ of reactions obtained is nano-zinc oxide hollow sphere.
Zn (Ac)
22H
2O, NaOH, tttmb,
mThe molar ratio of-bitmb is 2:4:2:2, adds methanol/ethanol volume ratio 1:1, and what 65 ℃ of reactions obtained is the nanometer rod zinc oxide sphere.
Zn (Ac)
22H
2O, NaOH, tttmb,
mThe molar ratio of-bitmb is 5:1:1:1, adds methanol/ethanol volume ratio 3:1, and what 65 ℃ of reactions obtained is the nano zine oxide solid sphere of six side's sheets assembling.
Zn (Ac)
22H
2O, NaOH, tttmb,
mThe molar ratio of-bitmb is 5:1:1:1, adds methanol/ethanol volume ratio 1:1, and what 200 ℃ of reactions obtained is the nano zine oxide ring.
Zn (Ac)
22H
2O, NaOH, tttmb,
mThe molar ratio of-bitmb is 5:1:1:1, adds methanol/ethanol volume ratio 1:1, transfers Ph=8 with formic acid, and what 125 ℃ of reactions obtained is the nano zine oxide that nano belt centers on.
Zn (Ac)
22H
2O, tttmb,
mThe molar ratio of-bitmb is 5:1:1, does not add NaOH, adds methanol/ethanol volume ratio 1:1, transfers Ph=8 with formic acid, and what 125 ℃ of reactions obtained is the fancy nano zine oxide.
Above six kinds of nano zine oxide synthetic products are characterized, like Fig. 1, Fig. 8 and shown in Figure 9.X-Ray powder diagram (a the figure, b, c, d from Fig. 1; E, f correspond respectively to instance 1 to instance 6 resulting samples, ultraviolet; Mark is identical in the Raman spectrogram) can find out that peaks all among the figure have all obtained ownership, and have no the appearance at assorted peak; There are 13 tangible peaks among the figure, can belong to crystal face (100), (002), (101), (102), (110), (103), (200), (112), (201), (004), (202), (104), (203) for hexagonal system zinc oxide.From Fig. 8 UV spectrum collection of illustrative plates (under the room temperature be distributed to absolute ethyl alcohol record zinc oxide), can draw, the absorption peak of six kinds of zinc oxide lays respectively at 366nm, 371nm, 375nm, 356nm, 366nm and 366nm.From Raman spectrum Fig. 9 of six kinds of synthetic product nano zine oxides, can draw, six kinds of wave spectrums have closely similar shape.Can be clear that zinc oxide～331 ,～440 with～1000 cm
1Locate out the peak, correspond respectively to the A1 (TO) of zinc oxide, the mode of vibration of E2 (high) and E1 (2LO).
The invention has the advantages that; Adopt the auxiliary solvent-thermal method nano zine oxide of nitrogenous organic molecule part compound method; Nano/micron zinc oxide assembly that can the controlledly synthesis ad hoc structure, and just can the synthesis of nano-zinc oxide hollow ball under the condition that does not need template.At near infrared absorption is more by force arranged according to present method synthetic nano zine oxide, have good using value.That this method has is simple to operate, controllability strong, characteristics such as low-cost, pollution-free.
Description of drawings
Fig. 1 is the X-Ray powder diagram of instance 1 to 6 synthetic nano zine oxide, and a among the figure, b, c, d, e, f correspond respectively to instance 1 to instance 6 synthetic zinc oxide sample (mark is identical in ultraviolet, the Raman spectrogram).
Fig. 2 is instance 1 synthetic nano-zinc oxide hollow sphere (a) transmission electron microscope figure (TEM) and (b) scanning electron microscope diagram (SEM).
Fig. 3 is instance 2 synthetic nanometer rod zinc oxide sphere (a) transmission electron microscope figure (TEM) and (b) scanning electron microscope diagram (SEM).
Fig. 4 is nano zine oxide solid sphere (a) the transmission electron microscope figure (TEM) of instance 3 synthetic six side's sheets assemblings and (b) scanning electron microscope diagram (SEM).
Fig. 5 is instance 4 synthetic nano zine oxide ring transmission electron microscope figure (TEM).
Fig. 6 is the zinc oxide scanning electron microscope diagram (SEM) that embodiment 5 synthetic nano belt center on.
Fig. 7 is embodiment 6 synthetic fancy nano zine oxide scanning electron microscope diagrams (SEM).
Fig. 8 is the ultraviolet spectrogram of the resulting sample of each instance.
Fig. 9 is the Raman spectrogram of the resultant sample of each instance.
Embodiment
Conjunction with figs. is described the present invention in further detail through embodiment, should be understood that embodiment only is in order to demonstrate the invention, but not limits scope of the present invention by any way.
Accurately take by weighing Zn (Ac)
22H
2O (0.5 mmol), NaOH (0.1 mmol), tttmb (0.1 mmol) and
m-bitmb (0.1 mmol) adds 5ml methyl alcohol in the reaction kettle of 10ml, 5ml ethanol naturally cools to room temperature behind 65 ℃ of constant temperature 3d, and with washing with alcohol product 3-5 time, vacuum-drying obtains white zinc oxide.
Can find out that from TEM and the SEM figure of Fig. 2 the synthetic zinc oxide nano-particle that obtains is monodispersed hollow ball, diameter range is 320-440nm, and is to be assembled by nanoparticle, and each little nanoparticle length approximately is 30nm.
Embodiment 2
The compound method of nano zine oxide and embodiment 1 are basic identical, difference be to add the ratio of sample different: add Zn (Ac)
22H
2O (0.2mmol), tttmb (0.2mmol), m-bitmb (0.2 mmol), NaOH (0.4 mmol).
Can find out that from the TEM of Fig. 3 and SEM figure syntheticly obtain the solid nanometer ball of zinc oxide, the nanometer ball periphery has grown the nanometer rod of different lengths and width, the diameter range of solid sphere is 140-230nm.Along with the increase of m-bitmb concentration, the size of nanometer rod also is tending towards homogeneous.
Embodiment 3
The compound method of nano zine oxide and embodiment 1 are basic identical, difference be to add the ratio of solvent different: add methyl alcohol 6ml, ethanol 2ml.
From the TEM of Fig. 4 and SEM figure, can find out, the synthetic nanometer ball of forming by six side's sheets that obtains, six side's sheets are slick, and the length of side is approximately 100nm, and the diameter range of the nanometer ball of formation is 550-780nm.
The compound method of nano zine oxide and embodiment 1 are basic identical, and difference is that synthesis reaction temperature is different: temperature of reaction is changed into 200 ℃ of constant temperature 3 days.
Can find out that from the TEM of Fig. 5 figure the synthetic zinc oxide that obtains is that external diameter is 980-1370nm, internal diameter is the ring of 360-610nm, and the surface of ring is coarse, and ring is that to be approximately the nanoparticle of 150nm by diameter molecular.
Embodiment 5
Accurately take by weighing Zn (Ac)
22H
2O (0.2 mmol), tttmb (0.4mmol) and
m-bitmb (0.4mmol) NaOH (0.2 mmol) adds 5ml methyl alcohol, 5ml ethanol in the reaction kettle of 30ml; Ultrasonic dissolution; Add formic acid regulator solution pH=8,125 ℃ of constant temperature naturally cooled to room temperature after 3 days, used washing with alcohol product 3-5 time then; Vacuum-drying obtains lurid zinc oxide.
Can find out that from the SEM figure of Fig. 6 the periphery of the synthetic nano zine oxide ball that obtains is to be centered on disorderly by nano belt to form, and the inside of the inside of nano belt and ball is made up of pipe.
Embodiment 6
The compound method of nano zine oxide and embodiment 5 are basic identical, and difference is: do not add NaOH.
From the SEM figure of Fig. 7, can find out that the synthetic nano zine oxide that obtains is a kind of fancy zinc oxide.The fancy structure can be divided into 3 parts, like illustrated a, and b, c is defined as a to level and smooth bottom surface, thinks floral leaf to b, and it (is a) upwards growth, the width and the length of comparison homogeneous is arranged from the bottom; The top that can see floral leaf part (b) from the figure that inserts is sharp; Partly call petal to c, likewise, petal also is to grow from the bottom.From enlarged view can find out petal be opening and also opening be random.
Claims (8)
1. the method for the auxiliary solvent-thermal method synthesizing zinc oxide of a nitrogenous organic molecule part nanoparticle assembly, it is characterized in that: with methyl alcohol and ethanol is mixed solvent, in reaction kettle, adds Zn (Ac)
2Or its hydrate, press Zn (Ac)
2With tttmb with
mThe mol ratio of-bitmb is that 0.5～5:1:1 adds containing n-donor ligand 1,3,5-three (1-triazol radical-methylene radical)-2,4, and 6-Three methyl Benzene (tttmb) and 1,3-two (1-imidazolyl-methylene radical)-2,4,6-Three methyl Benzene (m-bitmb) is pressed Zn (Ac)
2With the mol ratio of NaOH be that 1:0～2 add NaOH, directly or after regulating Ph=8, react 70～75h under 65 ℃～200 ℃ conditions, reduce to room temperature after scouring reaction product, vacuum-drying makes the zinc oxide nano-particle assembly.
2. the method for synthesizing zinc oxide nanoparticle assembly according to claim 1 is characterized in that: in said and methyl alcohol and the ethanol mixed solvent, methyl alcohol and alcoholic acid volume ratio are 1～3:1.
3. the method for synthesizing zinc oxide nanoparticle assembly according to claim 1 is characterized in that: said Zn (Ac)
22H
2O, NaOH, tttmb,
mThe molar ratio of-bitmb is 5:1:1:1, adds methanol/ethanol volume ratio 1:1, and 65 ℃ of reactions make nano-zinc oxide hollow sphere.
4. the method for synthesizing zinc oxide nanoparticle assembly according to claim 1 is characterized in that: said Zn (Ac)
22H
2O, NaOH, tttmb,
mThe molar ratio of-bitmb is 2:4:2:2, adds methanol/ethanol volume ratio 1:1, and 65 ℃ of reactions make the nanometer rod zinc oxide sphere.
5. the method for synthesizing zinc oxide nanoparticle assembly according to claim 1 is characterized in that: said Zn (Ac)
22H
2O, NaOH, tttmb,
mThe molar ratio of-bitmb is 5:1:1:1, adds methanol/ethanol volume ratio 3:1, and 65 ℃ of reactions make the nano zine oxide solid sphere of six side's sheets assembling.
6. the method for synthesizing zinc oxide nanoparticle assembly according to claim 1 is characterized in that: said Zn (Ac)
22H
2O, NaOH, tttmb,
mThe molar ratio of-bitmb is 5:1:1:1, adds methanol/ethanol volume ratio 1:1, and 200 ℃ of reactions make the nano zine oxide ring.
7. the method for synthesizing zinc oxide nanoparticle assembly according to claim 1 is characterized in that: Zn (Ac)
22H
2O, NaOH, tttmb,
mThe molar ratio of-bitmb is 5:1:1:1, adds methanol/ethanol volume ratio 1:1, transfers Ph=8 with formic acid behind the ultrasonic dissolution, and 125 ℃ of reactions make the nano zine oxide that nano belt centers on.
8. the method for synthesizing zinc oxide nanoparticle assembly according to claim 1 is characterized in that: Zn (Ac)
22H
2O, tttmb,
mThe molar ratio of-bitmb is 5:1:1, does not add NaOH, adds methanol/ethanol volume ratio 1:1, transfers Ph=8 with formic acid behind the ultrasonic dissolution, and 125 ℃ of reactions make the fancy nano zine oxide.
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| WO2015000796A1 (en) * | 2013-07-03 | 2015-01-08 | Genes'ink Sas | Nanoparticle-based ink formulations |
| CN107315023A (en) * | 2016-10-09 | 2017-11-03 | 河南理工大学 | Exclusive identifications of one porous MOF to iodide ion |
| CN111517362A (en) * | 2020-05-06 | 2020-08-11 | 南京瑞贝西生物科技有限公司 | Preparation method of mesoporous nano zinc oxide |
| CN112573560A (en) * | 2020-12-31 | 2021-03-30 | 常州市五洲化工有限公司 | Preparation method of high-dispersion zinc oxide |
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Cited By (7)
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| CN111517362A (en) * | 2020-05-06 | 2020-08-11 | 南京瑞贝西生物科技有限公司 | Preparation method of mesoporous nano zinc oxide |
| CN111517362B (en) * | 2020-05-06 | 2022-06-17 | 南京瑞贝西生物科技有限公司 | Preparation method of mesoporous nano zinc oxide |
| CN112573560A (en) * | 2020-12-31 | 2021-03-30 | 常州市五洲化工有限公司 | Preparation method of high-dispersion zinc oxide |
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