CN103818974B - Preparation method and product of colloid NiO nanocrystal - Google Patents
Preparation method and product of colloid NiO nanocrystal Download PDFInfo
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- CN103818974B CN103818974B CN201410057476.9A CN201410057476A CN103818974B CN 103818974 B CN103818974 B CN 103818974B CN 201410057476 A CN201410057476 A CN 201410057476A CN 103818974 B CN103818974 B CN 103818974B
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Abstract
The invention discloses a preparation method of colloid NiO nano crystal. The preparation method comprises the steps of mixing nickel carboxylate, a protection ligand, alcohol or amine and an organic solvent; stirring under an inert atmosphere and vacuumizing; heating the mixture in a reactor to a temperature of 100-350 DEG C; and after the reaction, cooling, precipitating with a precipitant and carrying out purification treatment, thereby obtaining the colloid NiO nano crystal. A general formula of nickel carboxylate is (R1-COO)2Ni; a general formula of the protection ligand is (R2-COO)nM, wherein R1 and R2 are independently selected from H, C2-C30 hydrocarbyl or aryl; reactive activity of M<n+> with carboxylate radicals to form carboxylate is lower than that of nickel carboxylate; and n represents the number of carboxylate radicals. The invention also discloses pure phase colloid NiO nanocrystal obtained by the preparation method. The pure phase colloid NiO nanocrystal has the advantages of easy film formation by using a low temperature solution process, and high work function, is expected to be applied in the fields such as organic thin-film solar cells, organic light emitting diodes and quantum dots light emitting diodes.
Description
Technical field
The present invention relates to field of nano material preparation, be specifically related to nanocrystalline preparation method of a kind of colloid NiO and products thereof.
Background technology
NiO is a kind of p-type oxide semiconductor material, there is 3d electronic structure, energy gap under room temperature is 3.6 ~ 4.0eV, and there is adjustable and higher work function, be the desirable hole transport layer material of the photoelectric device such as organic thin film solar cell, Organic Light Emitting Diode, light emitting diode with quantum dots under the gentle higher temperature of preparation room.
The surface atom number of nano NiO is very big with the ratio of body phase atomicity, demonstrate volume effect, quantum size effect, surface effects and macro quanta tunnel effect thus, many performances are better than common NiO, purposes is more extensive, at present, the method preparing nano NiO is a lot, as solid reaction process, chemical precipitation method and sol-gel method etc.
Deng Xiangyi etc. (liquid chemical precipitation legal system is explored for nano NiO. Deng Xiangyi, Xiang Lan, Jin Yong. Harbin Institute of Technology's journal, 34th volume the 2nd phase .) have studied different nickel salt and carry out experimental exploring from the technological process that nano NiO prepared by different precipitation agent, result shows: take nickelous chloride as nickel source, bicarbonate of ammonia is precipitation agent, better for nano NiO effect by liquid chemical precipitation legal system.Optimal processing parameter is: n (NiCl
2): n (NH
4hCO
3) be 1.0:2.0 ~ 2.5, precipitation temperature is 40 DEG C, and sedimentation time is 1.0 ~ 1.5h, and calcining temperature is 400 DEG C, and calcination time is 1h.
Zhao Shengli etc. (preparation that NiO is nanocrystalline and chemical property. Zhao Shengli, Zhao Chongjun, Wen Jiuba, Wang Hongkang. investigation of materials journal, 4th phase in 2008) adopt sol-gel technology to prepare nano NiO powder, with nickel acetate, citric acid, ethylene glycol for raw material is by the gel of esterification-complexation process synthesis, to decompose completely and to form NiO gradually nanocrystalline at 430 DEG C in sintering process.
Publication number is that the Chinese patent literature of CN101985367B discloses a kind of microwave solvothermal legal system for multi-level α-Ni (OH)
2or the method that NiO is nanocrystalline, to adopt any nickel salt to be independent raw material, the liquid saturated monohydroxy alcohol of a kind of normal temperature is separate solvent, in 150 DEG C of temperature of reaction and 15min reaction times, carries out the α-Ni (OH) that solvent thermal reaction obtains size uniformity
2multi-level nanostructure; The porous NiO that can obtain shape reservation through calcining process is nanocrystalline at many levels.
All there is the shortcoming that apparatus expensive or technique overall control are complicated, preparation cost is too high in above-mentioned preparation method, and the nano NiO prepared (or NiO is nanocrystalline) cannot be dissolved in water or organic solvent, strongly limit the application of nano NiO at solution process field of photoelectric devices.
Colloid nanocrystalline (colloidal nanocrystal) not only has the character of solid nano material but also has according to the difference of its surface ligand and be dissolvable in water water and have or the feature of machine solvent, especially its synthesis device and technique are very simple, and cost is very cheap.Therefore, people seek to synthesize the nanocrystalline method of colloid NiO constantly all the time, but it is nanocrystalline to be easy to be reduced to Ni because the colloid NiO obtained in the process that synthesis colloid NiO is nanocrystalline is nanocrystalline, does not have the relevant report to colloid NiO nanocrystalline material or its successful preparation method at present.
Summary of the invention
The invention provides nanocrystalline preparation method of a kind of colloid NiO and products thereof, preparation method is simple, controllability good, with low cost, is easy to suitability for industrialized production; The colloid NiO prepared is nanocrystalline has that productive rate is high, purity is high, the feature of good stability, high crystalline quality, and by the simple switched of ligand species obtain dissolve in different sorts solvent and there is the colloid NiO of different physical properties nanocrystalline.
The invention discloses the preparation method that a kind of colloid NiO is nanocrystalline, comprise the following steps:
1) nickel carboxylate, protection part, alcohol or amine and organic solvent mixing are placed in reactor, stir under inert protective atmosphere and vacuumize;
2) mixture in reactor is heated to 100 ~ 350 DEG C, insulation 30 ~ 200min, through cooling, precipitation agent precipitation, purification processes after reaction, obtains described colloid NiO nanocrystalline;
Described nickel carboxylate has general formula as shown in the formula (I):
(R
1-COO)
2Ni （Ⅰ），
Described protection part has the general formula as shown in formula II:
(R
2-COO)
nM （Ⅱ），
Wherein, R
1with R
2independently selected from H, C
2~ C
30alkyl or aryl, described M
n+be combined the reactive behavior of the carboxylate salt formed with carboxylate radical lower than nickel carboxylate, n is carboxylic acid radical.
It is nanocrystalline that the present invention prepares colloid NiO by simple alcoholysis or aminolysis reaction; the carboxylic metallic salt of low reaction activity is introduced as protection part in building-up process; in reaction process, make it be adsorbed on generate NiO nanocrystal surface to reduce NiO nanocrystalline monolithic reactive behavior; play the object that protection NiO is nanocrystalline; preventing NiO, nanocrystalline in reaction process, be reduced into Ni nanocrystalline, and the colloid NiO obtaining pure phase is thus nanocrystalline.
Described protection part is the carboxylic metallic salt of low reaction activity.In this reaction system, low reaction activity refers to, in identical mol ratio, speed when speed when protecting part to react separately with alcohol or amine when same reaction conditions is reacted separately than nickel carboxylate and alcohol or amine is a lot of slowly, to such an extent as at nickel carboxylate, when protecting part and alcohol or amine to mix reaction, nickel carboxylate and alcohol or amine is only had to react, protection part does not react with alcohol or amine and only plays the nanocrystalline effect being reduced into Ni of the colloidal silica nickel preventing from generating, the speed of speed of reaction can be evaluated by the growing amount of Different periods ester or acid amides in infrared monitoring reaction process.
As preferably, described protection part is fatty acid lithium, sodium soap or lipid acid potassium.In this reaction system, relative to Ni
2+, Li
+, Na
+and K
+the soap formed is the metal-salt of low reaction activity, and therefore the fatty acid metal salt of preferred several metal all can use as protection part.
Further preferably, the fatty acid radical in described protection part is Semen Myristicae acid group, laurate, oleic acid root or stearate radical.
As preferably, described nickel carboxylate is 1 ~ 10:1 with the mol ratio of protection part.
As preferably, described alcohol is C
12~ C
28alkyl alcohol; Described amine is oleyl amine is C
12~ C
30alkylamine.
Described organic solvent one to dissolve all reactants and protection part, and boiling point can not be too low simultaneously; Two is want high temperature safe, simultaneously stable chemical nature, does not participate in reaction.As preferably, described organic solvent is 1-octadecylene, octyl ether or phenyl ether.
As preferably, the mol ratio of described nickel carboxylate and alcohol or amine is 1:1 ~ 10; The concentration of described nickel carboxylate is 0.05 ~ 0.1mol/L.
As preferably, by step 2) described in mixture be heated to 180 ~ 340 DEG C, the reaction times is 30 ~ 200min.
As preferably, step 2) described in precipitation agent be methyl alcohol, ethanol, ethyl acetate or acetone.
The invention also discloses the colloid NiO that the preparation method described in employing obtains nanocrystalline, the nanocrystalline part that is nanocrystalline by NiO and that be adsorbed on its surface of described colloid NiO forms;
Described part can be (R
1-COO)
2ni and/or (R
2-COO)
nm; Described colloid NiO is nanocrystalline is the colloid nanocrystalline of solubility, can be dissolved in different solvents form colloid nanocrystalline solution according to the difference of its surface ligand kind.
By the exchange of the colloid NiO nanocrystal surface ligand species to described solubility, water-soluble or oil-soluble colloid NiO can be obtained respectively nanocrystalline.The nanocrystalline solvability of described colloid NiO is determined by its surface ligand completely, and according to similar dissolve mutually theory, which kind of solvent surface ligand is dissolved in, and colloid NiO is nanocrystalline just can be dissolved in this solvent.
Such as, change the part on surface into hydroxyl by oil-soluble group, nanocrystalline be just transformed into by oil soluble water-soluble.
By the removal of the colloid NiO nanocrystal surface part to described solubility, the NiO that can directly obtain not with part is nanocrystalline, and in order to prepare, highly purified NiO is nanocrystalline provides a kind of direct, easy method.
The common method removing part has:
1) add the strong crystallization solvent of polarity (as methyl alcohol), and adopt high speed centrifugation;
2) heating and calcining at 500 ~ 800 DEG C.
Compared with prior art, tool of the present invention has the following advantages:
Preparation technology of the present invention is simple, cost is lower, reproducible, be easy to suitability for industrialized production, is expected to the various fields such as the organic thin film solar cell based on solution method, Organic Light Emitting Diode, light emitting diode with quantum dots and is applied.
The colloid NiO that the present invention has prepared solubility is first nanocrystalline, and productive rate is high, purity is high, good stability; And obtain by the simple switched of ligand species and dissolve in different sorts solvent and to have the colloid NiO of different physical properties nanocrystalline.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the colloid nanocrystalline that embodiment 1 and comparative example are prepared respectively;
Fig. 2 be embodiment 1 prepare colloid NiO nanocrystalline XPS figure;
Fig. 3 is the nanocrystalline HRTEM picture of colloid NiO prepared by embodiment 1;
Fig. 4 is the nanocrystalline TEM picture of colloid NiO prepared by embodiment 1;
Fig. 5 is the TEM picture of colloid nanocrystalline prepared by comparative example;
Fig. 6 is the FTIR figure of the colloid nanocrystalline prepared respectively in embodiment 1 and comparative example;
Fig. 7 is the nanocrystalline TEM picture of colloid NiO prepared by embodiment 2.
Embodiment
Example below for adopting the inventive method synthesis colloid NiO nanocrystalline, but the present invention is not limited to these embodiments.
Embodiment 1
1) take 1mmol nickel stearate, 0.2mmol protection part lithium stearate (mol ratio is 5:1), the stearyl alcohol of 6mmol and the 1-octadecylene of 10ml and be placed in 50ml reaction flask; under inert protective atmosphere; magnetic agitation is warming up to 50 DEG C, then vacuumizes warm 30min to reaction system.
2) under inert protective atmosphere, temperature is increased to 180 DEG C, insulation 200min, cooled reaction solution to room temperature, then through centrifugal purification, obtains colloid NiO nanocrystalline.
Comparative example
1) take 1mmol nickel stearate, the stearyl alcohol of 6mmol and the 1-octadecylene of 10ml and be placed in 50ml reaction flask, under inert protective atmosphere, magnetic agitation is warming up to 50 DEG C, then vacuumizes warm 30min to reaction system.
2) under inert protective atmosphere, temperature is increased to 180 DEG C, insulation 200min, cooled reaction solution to room temperature, then through centrifugal purification, obtains colloid nanocrystalline.
Fig. 1 is the left figure of embodiment 1() and comparative example (right figure) in the XRD figure spectrum of colloid nanocrystalline for preparing respectively, observe the left figure of Fig. 1 known, in embodiment 1, preparation nanocrystalline is that the NiO of pure phase is nanocrystalline, and the appearance not having Ni nanocrystalline; Observe right figure known, what comparative example prepared is that NiO is nanocrystalline and Ni is nanocrystalline.
Fig. 2 is the nanocrystalline XPS collection of illustrative plates of the colloid NiO for preparing in embodiment 1, solid line is the result directly measured, dotted line is the result to the matching of solid line swarming, what XPS peak position reflected is the information combining energy, theory directly perceived is exactly the information of valence state, this figure illustrates that the Ni in product is+divalent, does not have the Ni of 0 valency, and nickel and oxygen combine and forms NiO.
Fig. 3 is the nanocrystalline HRTEM figure of the colloid NiO for preparing in embodiment 1, observation Fig. 4 is known, spacing is 0.21nm and 0.24nm, respectively { the 200} and { 111} crystal face, the colloid nanocrystalline demonstrating preparation is that colloid NiO is nanocrystalline of corresponding rock salt structure NiO.
Fig. 4,5 is respectively the TEM picture of the colloid nanocrystalline that embodiment 1 and comparative example prepare, comparison diagram 4,5 known, and in embodiment 1, the shape of the colloid nanocrystalline of preparation is irregular particulate state, and the particle not having colloid Ni nanocrystalline occurs; And the macrobead in the TEM figure of the colloid nanocrystalline prepared in comparative example is that colloid Ni is nanocrystalline.
All can be proved by above-mentioned characterization method, colloid nanocrystalline prepared by present method is that the colloid NiO of pure phase is nanocrystalline, and not nanocrystalline containing colloid Ni.
Fig. 6 is the FTIR figure of the colloid nanocrystalline prepared respectively in embodiment 1 and comparative example, in figure, and 1550cm
-1the charateristic avsorption band that place is the stearate radical in nickel stearate or stearate, and at 1560cm in the nanocrystalline FTIR figure of colloid NiO prepared by embodiment 1
-1there is new charateristic avsorption band in place, the charateristic avsorption band of corresponding lithium stearate.
Embodiment 2
1) octyl ether taking 1mmol nickel stearate, 0.4mmol protection part Sodium tetradecanoate (mol ratio is 5:2), 10mmol oleyl amine and 10ml is placed in 50ml reaction flask; under inert protective atmosphere; magnetic agitation is warming up to 90 DEG C, then vacuumizes insulation 30min to reaction system.
2) under inert atmosphere protection, temperature is risen to 260 DEG C, and be incubated 100 minutes, cooled reaction solution to room temperature, then through centrifugal purification, obtains colloid NiO nanocrystalline.Described colloid NiO nanocrystalline TEM figure as shown in Figure 7.
Embodiment 3
1) phenyl ether taking 1mmol nickel stearate, 0.6mmol protection part Potassium ethanoate (mol ratio is 5:3), 5mmol lauryl alcohol and 12ml is placed in 50ml reaction flask; under inert protective atmosphere; magnetic agitation is warming up to 120 DEG C, then vacuumizes insulation 30min to reaction system.
2) under inert atmosphere protection, temperature is risen to 320 DEG C, and be incubated 30min, cooled reaction solution to room temperature, then through centrifugal purification, obtains colloid NiO nanocrystalline.
Embodiment 4
1) take 1mmol nickel stearate, 0.1mmol protection part sodium laurate (mol ratio is 10:1), the trioctylamine of 3mmol and the 1-octadecylene of 10ml and be placed in 50ml reaction flask; under inert protective atmosphere; magnetic agitation is warming up to 80 DEG C, then vacuumizes insulation 30min to reaction system.
2) under inert protective atmosphere, temperature is risen to 280 DEG C, be incubated 80 minutes, cooled reaction solution to room temperature, then through centrifugal purification, obtains colloid NiO nanocrystalline.
Embodiment 5
1) take 1mmol nickel stearate, 0.4mmol protection part sodium oleate (mol ratio is 2.5:1), the stearyl alcohol of 3mmol and the 1-octadecylene of 10ml and be placed in 50ml reaction flask; under inert protective atmosphere; magnetic agitation is warming up to 80 DEG C, then vacuumizes insulation 30min to reaction system.
2) under inert protective atmosphere, temperature is risen to 340 DEG C, be incubated 80 minutes, cooled reaction solution to room temperature, then through centrifugal purification, obtains colloid NiO nanocrystalline.
Claims (7)
1. the preparation method that colloid NiO is nanocrystalline, is characterized in that, comprises the following steps:
1) nickel carboxylate, protection part, alcohol or amine and organic solvent mixing are placed in reactor, stir under inert protective atmosphere and vacuumize;
2) mixture in reactor is heated to 100 ~ 350 DEG C, insulation 30 ~ 200min, through cooling, precipitation agent precipitation, purification processes after reaction, obtains described colloid NiO nanocrystalline;
Described nickel carboxylate has such as formula the general formula shown in (I):
(R
1-COO)
2Ni (Ⅰ)，
Described protection part has the general formula as shown in formula II:
(R
2-COO)
nM (Ⅱ)，
Wherein, R
1with R
2independently selected from H, C
2~ C
30alkyl or aryl, described M
n+be combined the reactive behavior of the carboxylate salt formed with carboxylate radical lower than nickel carboxylate, n is carboxylic acid radical;
Described protection part is fatty acid lithium, sodium soap or lipid acid potassium.
2. the preparation method that colloid NiO according to claim 1 is nanocrystalline, is characterized in that, the fatty acid radical in described protection part is Semen Myristicae acid group, laurate, oleic acid root or stearate radical.
3. the preparation method that the colloid NiO according to the arbitrary claim of claim 1 ~ 2 is nanocrystalline, is characterized in that, described nickel carboxylate is 1 ~ 10:1 with the mol ratio of protection part.
4. the preparation method that colloid NiO according to claim 3 is nanocrystalline, is characterized in that, described alcohol is C
12~ C
28alkyl alcohol; Described amine is C
12~ C
30alkylamine; Described organic solvent is 1-octadecylene, octyl ether or phenyl ether.
5. the preparation method that the colloid NiO according to claim 1 or 4 is nanocrystalline, is characterized in that, the mol ratio of described nickel carboxylate and alcohol or amine is 1:1 ~ 10; The concentration of described nickel carboxylate is 0.05 ~ 0.1mol/L.
6. the preparation method that colloid NiO according to claim 1 is nanocrystalline, is characterized in that, by step 2) described in mixture be heated to 100 ~ 350 DEG C, the reaction times is 30 ~ 200min.
7. the preparation method that colloid NiO according to claim 1 is nanocrystalline, is characterized in that, step 2) described in precipitation agent be methyl alcohol, ethanol, ethyl acetate or acetone.
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| CN105460984A (en) * | 2014-09-05 | 2016-04-06 | 中国科学院兰州化学物理研究所 | Preparation method for nickel hydroxide quantum dot |
| CN104944367A (en) * | 2015-05-08 | 2015-09-30 | 江苏天晟药业有限公司 | Preparation method of ferromagnetic nano material |
| CN106966441B (en) * | 2016-07-14 | 2018-11-02 | 浙江大学 | A kind of preparation method of copper ion doped nickel oxide colloid nanocrystalline and products thereof and its application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985367A (en) * | 2010-07-28 | 2011-03-16 | 中国科学院上海硅酸盐研究所 | Method for preparing multilayer alpha-Ni(OH)2 or NiO nanocrystal by microwave solvothermal method |
| CN102126762A (en) * | 2011-04-28 | 2011-07-20 | 北京化工大学 | Method for preparing NiO nano flowerlike microspheres with surface topography controllable |
-
2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985367A (en) * | 2010-07-28 | 2011-03-16 | 中国科学院上海硅酸盐研究所 | Method for preparing multilayer alpha-Ni(OH)2 or NiO nanocrystal by microwave solvothermal method |
| CN102126762A (en) * | 2011-04-28 | 2011-07-20 | 北京化工大学 | Method for preparing NiO nano flowerlike microspheres with surface topography controllable |
Non-Patent Citations (1)
| Title |
|---|
| "Magnetic Properties of Colloidal Nickelous oxide";James T. Richardson et al.;《Physical Review》;19560601;第102卷(第5期);第1289-1294页 * |
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