CN102602983B - 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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- CN102602983B CN102602983B CN2012101021928A CN201210102192A CN102602983B CN 102602983 B CN102602983 B CN 102602983B CN 2012101021928 A CN2012101021928 A CN 2012101021928A CN 201210102192 A CN201210102192 A CN 201210102192A CN 102602983 B CN102602983 B CN 102602983B
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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 synthetic method of nano zinc oxide material, relate in particular to the preparation method of the auxiliary solvent-thermal method zinc oxide nano-particle assembly of a kind of nitrogenous organic molecule part.
Background technology
Zinc oxide (ZnO), as a kind of novel inorganic chemical materials, 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.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.Due to 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 study hotspot of field of nanometer material technology in recent years, nano zinc oxide material has good performance, as semiconducting behavior, piezoelectric property, photocatalysis performance, physiologically acceptable performance etc., applied to electromechanical pickup, nano generator, solar cell, nano laser etc., has boundless commercial application prospect.
Structure is the basis of Application of micron, and it will affect the performance of nano material on very large aspect.Therefore, controllability ground growth of zinc oxide nano structure, to obtain the functional device with novel performance, is an important directions in current nano zinc oxide material research aspect preparation.The processing method for preparing nano structure of zinc oxide is a lot, and according to having or not chemical reaction to occur to be divided into Physical and chemical method in preparation process, but Physical 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 very abundant structure and morphology, as zinc oxide nanowire, nano belt, nanotube, nano-rings, nanometer spring, nano-comb, four pin shape nanostructures etc.Comparatively speaking, the hydro-thermal rule is fairly simple.And the method that obtains at present this special construction nano zine oxide of hollow ball is mainly two kinds: the hydrothermal method that thermal evaporation and template are auxiliary.The instrument that thermal evaporation needs is complicated, and influence factor is more, as 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 with special construction to seem particularly important.
Summary of the invention
The present invention is directed to nano zine oxide preparation method above shortcomings, aim to provide the method for the auxiliary solvent-thermal method synthesizing zinc oxide nanoparticle assemblies of a kind of nitrogenous organic molecule part, Nano/micron zinc oxide that can the controlledly synthesis ad hoc structure, simple to operate, ratio by the regulation and control reactant, temperature of reaction, the conditions such as pH obtain the nano zine oxide of different-shape, and have synthesized zinc oxide nano hollow spheres under the condition that does not need template.
Completing the technical scheme of taking of the present invention is: the method for the solvent-thermal method synthesizing zinc oxide nanoparticle assemblies that a kind of nitrogenous organic molecule part is auxiliary, take methyl alcohol and ethanol as mixed solvent, adds Zn (Ac) in reactor
2Or its hydrate, press Zn (Ac)
2With tttmb and
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), press 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 under 65 ℃～200 ℃ conditions, be down to washing reaction product after room temperature, vacuum-drying, make the zinc oxide nano-particle assembly.
In described 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 as 1:0.2,1:1 or 1:2, relevant to the pattern of zinc oxide nano-particle assembly.
In described method, in the mixed solvent of methyl alcohol and ethanol, the volume ratio of methyl alcohol and ethanol is 1～3:1.
Reacting required containing n-donor ligand can be according to synthetic (the Hong-Ke Liu of the method in published 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, referred to as tttmb), 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, referred to as m-bitmb).
The method that the zinc oxide nano-particle assembly is synthetic: accurately take a certain amount of Zn (CH
3COO)
22H
2O, NaOH, tttmb and m-bitmb, join it in hydrothermal reaction kettle, add again appropriate methyl alcohol and ethanol, directly or after regulating Ph=8 with formic acid, reaction 70-75 h under constant temperature, naturally use absolute ethanol washing product 3-5 time after being down to room temperature, vacuum-drying, in order to analyze and to characterize.
Change by reaction conditions, can synthesize the zinc oxide nano-particle assembly that obtains various different-shape structures, typically comprise nano-zinc oxide hollow sphere, with nanometer rod zinc oxide sphere, six square piece assembling nano zinc oxide solid sphere, nano zine oxide ring, by nano belt around zinc oxide and fancy zinc oxide ring.
The zinc oxide nano-particle assembly that has specifically prepared following single shape in embodiment, preferred concrete reaction conditions is as follows:
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 nanometer ZnO full sphere of six square pieces assemblings.
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, with formic acid, transfers Ph=8,125 ℃ of reactions obtain be nano belt around nano zine oxide.
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, with formic acid, transfers Ph=8, and what 125 ℃ of reactions obtained is the fancy nano zine oxide.
Above six kinds of nano zine oxide synthetic products are characterized, as Fig. 1, Fig. 8 and shown in Figure 9.X-Ray powder diagram (a figure, b, c, d from Fig. 1, e, f correspond respectively to example 1 to the resulting sample of example 6, ultraviolet, in Raman spectrogram, mark is identical) can find out, peaks all in figure have all obtained ownership, and without any the appearance at assorted peak; There are 13 obvious peaks in figure, can be attributed to crystal face (100), (002), (101), (102), (110), (103), (200), (112), (201), (004), (202), (104), (203) of hexagonal system zinc oxide.Can draw from Fig. 8 UV spectrum collection of illustrative plates (under room temperature, zinc oxide is distributed to dehydrated alcohol and records), the absorption peak of six kinds of zinc oxide lays respectively at 366nm, 371nm, 375nm, 356nm, 366nm and 366nm.Can draw from Raman spectrum Fig. 9 of six kinds of synthetic product nano zine oxides, six kinds of wave spectrums have closely similar shape.Can be clear that zinc oxide～331 ,～440 and～1000 cm
1Locate out 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 synthetic method of nitrogenous organic molecule part, Nano/micron ZnO 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.The nano zine oxide synthetic according to present method has more by force and absorbs near infrared, has good using value.That the method has is simple to operate, controllability strong, the characteristics such as low-cost, pollution-free.
Description of drawings
Fig. 1 is the X-Ray powder diagram of the synthetic nano zine oxide of example 1 to 6, and a in figure, b, c, d, e, f correspond respectively to example 1 to the synthetic zinc oxide sample of example 6 (in ultraviolet, Raman spectrogram, mark is identical).
Fig. 2 is synthetic nano-zinc oxide hollow sphere (a) the transmission electron microscope figure (TEM) of example 1 and (b) scanning electron microscope diagram (SEM).
Fig. 3 is synthetic nanometer rod zinc oxide sphere (a) the transmission electron microscope figure (TEM) of example 2 and (b) scanning electron microscope diagram (SEM).
Fig. 4 is nanometer ZnO full sphere (a) the transmission electron microscope figure (TEM) of six synthetic square pieces assemblings of example 3 and (b) scanning electron microscope diagram (SEM).
Fig. 5 is the synthetic nano zine oxide ring transmission electron microscope figure (TEM) of example 4.
Fig. 6 be the synthetic nano belt of embodiment 5 around zinc oxide scanning electron microscope diagram (SEM).
Fig. 7 is the synthetic fancy nano zine oxide scanning electron microscope diagram (SEM) of embodiment 6.
Fig. 8 is the ultraviolet spectrogram of the resulting sample of each example.
Fig. 9 is the Raman spectrogram of the resulting sample of each example.
Embodiment
Coordinate accompanying drawing to describe in further detail the present invention by embodiment, should be understood that embodiment is only in order to demonstrate the invention, but not limit the scope of the invention by any way.
Embodiment 1
Accurately take Zn (Ac)
22H
2O (0.5 mmol), NaOH (0.1 mmol), tttmb (0.1 mmol) and
m-bitmb (0.1 mmol) in the reactor of 10ml, adds 5ml methyl alcohol, and 5ml ethanol naturally cools to room temperature after 65 ℃ of constant temperature 3d, uses washing with alcohol product 3-5 time, and vacuum-drying obtains white zinc oxide.
Can find out from TEM and the SEM figure of Fig. 2, the synthetic zinc oxide nano-particle that obtains is monodispersed hollow ball, and diameter range is 320-440nm, and is to be assembled by nanoparticle, and each little nanoparticle length is approximately 30nm.
Embodiment 2
The synthetic method of nano zine oxide is substantially the same manner as Example 1, and difference is that the ratio of adding of sample is different: add Zn (Ac)
22H
2O (0.2mmol), tttmb (0.2mmol), m-bitmb (0.2 mmol), NaOH (0.4 mmol).
Can find out from TEM and the SEM figure of Fig. 3, synthesize and obtain the solid nanometer ball of zinc oxide, the nanometer ball periphery has grown the nanometer rod of different lengths and width, and 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 synthetic method of nano zine oxide is substantially the same manner as Example 1, and difference is that the ratio of adding of solvent is different: add methyl alcohol 6ml, ethanol 2ml.
Can find out from the TEM of Fig. 4 and SEM figure, the synthetic nanometer ball that is formed by six square pieces that obtains, six square pieces are smooth, and the length of side is approximately 100nm, and the diameter range of the nanometer ball of formation is 550-780nm.
The synthetic method of nano zine oxide is substantially the same manner as Example 1, and difference is that synthesis reaction temperature is different: temperature of reaction is changed into 200 ℃ of constant temperature 3 days.
Can find out from the TEM figure of Fig. 5, the synthetic zinc oxide that obtains is that external diameter is 980-1370nm, and 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 Zn (Ac)
22H
2O (0.2 mmol), tttmb (0.4mmol) and
m-bitmb (0.4mmol) NaOH (0.2 mmol) is in the reactor of 30ml, add 5ml methyl alcohol, 5ml ethanol, ultrasonic dissolution, add formic acid regulator solution pH=8,125 ℃ of constant temperature naturally cooled to room temperature after 3 days, then used washing with alcohol product 3-5 time, vacuum-drying, obtain lurid zinc oxide.
Can find out from the SEM figure of Fig. 6, the periphery of the synthetic nano zine oxide ball that obtains be by nano belt disorderly around forming, and the inside of the inside of nano belt and ball is molecular by pipe.
Embodiment 6
The synthetic method of nano zine oxide is substantially the same manner as Example 5, and difference is: do not add NaOH.
Can find out from the SEM figure of Fig. 7, the synthetic nano zine oxide that obtains is a kind of fancy zinc oxide.The fancy structure can be divided into 3 parts, a as shown, and b, c, be defined as a to level and smooth bottom surface, and b is thought floral leaf, and it (is a) upwards growth, width and the length of comparison homogeneous is arranged from bottom; The top that can see floral leaf part (b) from the figure that inserts is sharp; C is partly called petal, and similarly, petal is also to grow from 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 nanoparticle assemblies of a nitrogenous organic molecule part is characterized in that:, take methyl alcohol and ethanol as mixed solvent, add Zn (Ac) in reactor
2Or its hydrate, press Zn (Ac)
2With tttmb and
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), press 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, be down to washing reaction product after room temperature, vacuum-drying, make the zinc oxide nano-particle assembly.
2. the method for synthesizing zinc oxide nanoparticle assemblies according to claim 1 is characterized in that: in the mixed solvent of described and methyl alcohol and ethanol, the volume ratio of methyl alcohol and ethanol is 1～3:1.
3. the method for synthesizing zinc oxide nanoparticle assemblies according to claim 1, is characterized in that: described 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 assemblies according to claim 1, is characterized in that: described 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 assemblies according to claim 1, is characterized in that: described 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 nanometer ZnO full sphere of six square piece assemblings.
6. the method for synthesizing zinc oxide nanoparticle assemblies according to claim 1, is characterized in that: described 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 molecular zinc oxide ring of nanoparticle.
7. the method for synthesizing zinc oxide nanoparticle assemblies 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 after ultrasonic dissolution, 125 ℃ of reactions make nano belt around zinc oxide sphere.
8. the method for synthesizing zinc oxide nanoparticle assemblies 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 after ultrasonic dissolution, and 125 ℃ of reactions make fancy nano zine oxide assembly.
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