CN102887550B - Method for producing mesoporous nickel oxide - Google Patents
Method for producing mesoporous nickel oxide Download PDFInfo
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- CN102887550B CN102887550B CN201210379945.XA CN201210379945A CN102887550B CN 102887550 B CN102887550 B CN 102887550B CN 201210379945 A CN201210379945 A CN 201210379945A CN 102887550 B CN102887550 B CN 102887550B
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Abstract
The invention relates to a method for producing mesoporous nickel oxide, belonging to the technical fields of mesoporous materials. The invention aims to provide a low-production-cost method for producing mesoporous nickel oxide. The method for producing mesoporous nickel oxide uses a surfactant as a template agent, wherein the surfactant is a mixture of an anionic surfactant or cationic surfactant and a nonionic surfactant; and the mol ratio of anionic surfactant to nonionic surfactant in the mixture is (30-50):1, and the mol ratio of cationic surfactant to nonionic surfactant in the mixture is (20-40):1.
Description
Technical field
The method that the present invention relates to produce mesoporous nickel oxide, belongs to technical field of mesoporous materials.
Background technology
Nickel oxide is a kind of rare p-type semi-conductor, has stable and wider band is widely used in the fields such as photoelectric conversion, battery electrode, electrochemical capacitor and high performance catalyst.Mesoporous material has that density is low, porosity is high, specific surface area is large, selectivity and the advantage such as surface properties is good, and mesoporousization of nickel oxide can be expanded to its application in each field greatly.But because nickel is divalent metal, its oxide compound is difficult to spontaneous formation reticulated structure as the tetravalent metal oxide compounds such as titanium, silicon, zirconium, mostly needs to add template to induce presoma pore-forming while therefore producing mesoporous nickel oxide.
Tensio-active agent is one of the most frequently used template of producing in recent years the transition metal oxide with meso-hole structure, all report the correlated results of producing mesoporous nickel oxide with this both at home and abroad, as: punishment is big etc. mesoporous nickel oxide synthetic, characterize and application in electrochemical capacitor. chemical journal, the 63rd the 19th phase of volume in 2005; 1775-1781 discloses a kind of method of producing mesoporous nickel oxide, and it adopts NiCl
26H
2o, SDS, urea are that raw material is produced, and the specific surface area of the mesoporous nickel oxide obtaining is larger, can reach 477m
2g
-1.The mechanism of its pore-forming, according to the capable description of the 1778th page of right hurdle 3-4 reciprocal: " we think that its pore structure forms mechanism reverse micelle synthesis mechanism that is as the criterion ".The crucial part of this mechanism is just to be pre-formed micella template, and its surfactant concentration is far longer than micelle-forming concentration, forms the structure of " water-in-oil ".The 1779th page of capable several factors that form reverse micelle that also explicitly pointed out of left hurdle the 2-4: " surfactant content that (1) is high; (2) only have a small amount of residue free water ", therefore, in documents, the mass ratio of template and water is " SDS: distilled water=24:45 ", the mol ratio of template and distilled water is 1:30.In addition, the mass ratio of its nickel salt and urea is " NiCl
26H
2o: urea=10:76 ", the mol ratio of the two is 1:30.Its main drawback of depositing is as follows:
1, the consumption of the urea of its use (precipitation agent) and tensio-active agent (template) is more, and cost is higher;
2, it is that cost promotes NiO specific surface area by huge template consumption, and the specific surface area of the NiO that produces reaches 477m after 250 DEG C of calcinings
2g
-1, but in the time that calcining temperature is elevated to 300 DEG C and 350 DEG C, specific surface area declines rapidly, is respectively 297m
2g
-1and 217m
2g
-1, in file, there is no the data of higher calcining temperature, but can predict, in the time that calcining temperature is elevated to 400 DEG C, specific surface area can not exceed 200m
2g
-1, the high-temperature stability of the mesoporous nickel oxide that the method is produced is poor.Because lower calcining temperature can make the degree of crystallinity of NiO bad, and then affect the capacitive character of NiO, improve calcining temperature and can reduce again NiO specific surface area, therefore, adopt the method to be difficult to produce the capacitive character, all good mesoporous nickel oxide of specific surface area over-all properties that obtain NiO.
Summary of the invention
Technical problem to be solved by this invention is to provide the method for the mesoporous nickel oxide of production that a kind of production cost is lower.
The method employing tensio-active agent that the present invention produces mesoporous nickel oxide is template, and wherein, described tensio-active agent is the mixture of a kind of and nonionic surface active agent in anion surfactant, cationic surfactant; Wherein, the anion surfactant in mixture and the mol ratio of nonionic surface active agent are 30～50:1, and the cationic surfactant in mixture and the mol ratio of nonionic surface active agent are 20～40:1.All the other steps that the present invention produces the method for mesoporous nickel oxide can adopt existing method.
Wherein, in order to improve the performance of produced mesoporous nickel oxide, the method of the mesoporous nickel oxide of above-mentioned production, anion surfactant in its mixture and the mol ratio of nonionic surface active agent are preferably 40:1, and the cationic surfactant in mixture and the mol ratio of nonionic surface active agent are preferably 30:1.
Further, in order to improve the performance of produced mesoporous nickel oxide, above-mentioned tensio-active agent is preferably the mixture of anion surfactant and nonionic surface active agent.
Wherein, the conventional tensio-active agent of method of producing mesoporous nickel oxide is all suitable for and the present invention, such as: described anion surfactant can be sodium lauryl sulphate (SDS) etc.; Described nonionic surface active agent can be polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer (P123) etc.; Described cationic surfactant can be cetyl trimethylammonium bromide (CTAB) etc.
Further, in order to improve the performance of produced mesoporous nickel oxide, the mol ratio of the nickel in aforesaid method and the integral molar quantity of tensio-active agent is preferably 8～12:1.More preferably 10:1 of the mol ratio of the integral molar quantity of nickel and tensio-active agent.
Wherein, the concrete steps of the method for the mesoporous nickel oxide of above-mentioned production are as follows:
A, get the aqueous solution (can water-soluble nickel salt be all applicable to the present invention) of nickel salt, add urea, be stirred to completely and dissolve; Wherein, the mol ratio of nickel and urea is 1:1～4; The mol ratio of nickel and urea is preferably 1:3
B, in the solution of a step, add tensio-active agent, be stirred to completely and dissolve;
C, by b step gained solution in 80～100 DEG C of insulations, make Precipitation; Generally.80～100 DEG C of insulations can make precipitation substantially separate out completely for about 10～16 hours; Be preferable over 90 DEG C of insulations 14 hours;
D, washing of precipitate, dry, then obtain mesoporous nickel oxide for 1 ~ 3 hour in 400 ~ 450 DEG C of calcinings.
Further, it is higher that the excessive concentration of nickel salt aqueous solution can cause precipitating initial stage degree of supersaturation, this is unfavorable for forming the precipitation of size uniform, the concentration of nickel salt aqueous solution is too low the shortcoming that output is little, consider above-mentioned factor, the concentration of the nickel salt aqueous solution described in a step of aforesaid method is preferably 0.2～0.5molL
-1, the concentration of nickel salt aqueous solution most preferably is 0.25molL
-1.
Wherein, in the d step of aforesaid method, be preferable over 400 DEG C of calcinings and within 2 hours, obtain mesoporous nickel oxide.
Wherein, in above-mentioned d step, can adopt ordinary method dry, such as: in 80 DEG C of baking ovens, be dried 4 hours.
The pore-forming mechanism that the present invention produces the method for mesoporous nickel oxide is: the present invention is based on electric density coupling mechanism.What electric density coupling mechanism was emphasized is inorganic particulate is the charge matching in interface in tensio-active agent, can in the time that surfactant concentration is less than micelle-forming concentration, form meso-hole structure, does not need to be pre-formed micella.The present inventor finds by lot of experiments, the dissimilar single tensio-active agent of same amount to the effect size order of NiO specific surface area is: anionic (SDS) > non-ionic type (P123) > cationic (CTAB), this explanation charged situation of template in body series has tremendous influence, meets the feature of charge matching mechanism.In the present invention, (refer to record in background technology of the present invention method) compared to existing technology,, the content of its tensio-active agent is obviously much lower, differs and approaches 70 times.Therefore, prior art is to adopt different pore-forming mechanism to promote NiO specific surface area taking huge template consumption as cost, and the specific surface area of prepared NiO reaches 477m after 250 DEG C of calcinings
2g
-1, but in the time that calcining temperature is elevated to 300 DEG C and 350 DEG C, specific surface area declines rapidly, is respectively 297m
2g
-1and 217m
2g
-1, in file, there is no the data of higher calcining temperature, but can predict, in the time that calcining temperature is elevated to 400 DEG C, specific surface area can not exceed 200m
2/ g.In documents, high calcining temperature corresponding to specific surface area, and lower calcining temperature can make the degree of crystallinity of NiO bad, and then affect the capacitive character of NiO, therefore reciprocal on the left hurdles of 1780 pages of documents 3-5 is capable shows: " the NiO capacitance characteristic that under 523K, roasting obtains is the poorest; along with the rising of maturing temperature; the capacitance characteristic of NiO improves gradually; the NiO capacitance characteristic that under 623K, roasting obtains is best ", and " 523; 573 and 623K under the ratio electric capacity of the NiO sample that obtains of roasting be respectively 124,106 and 68Fg
-1" (seeing that the 1780th page of right hurdle 7-8 reciprocal is capable).And obtaining specific surface area after 400 DEG C of calcinings under the template consumption much smaller than documents, the inventive method is still greater than 200m
2g
-1niO, there is good thermostability, and the ratio electric capacity that records NiO is greater than 200Fg
-1.
The inventive method production cost is lower, the better heat stability of the mesoporous nickel oxide of producing, and it is higher than electric capacity, and the production that the present invention is mesoporous nickel oxide provides a kind of new method, has broad application prospects.
Embodiment
The method employing tensio-active agent that the present invention produces mesoporous nickel oxide is template, and wherein, described tensio-active agent is the mixture of a kind of and nonionic surface active agent in anion surfactant, cationic surfactant; Wherein, the anion surfactant in mixture and the mol ratio of nonionic surface active agent are 30～50:1, and the cationic surfactant in mixture and the mol ratio of nonionic surface active agent are 20～40:1.All the other steps that the present invention produces the method for mesoporous nickel oxide can adopt existing method.
Wherein, in order to improve the performance of produced mesoporous nickel oxide, the method of the mesoporous nickel oxide of above-mentioned production, anion surfactant in its mixture and the mol ratio of nonionic surface active agent are preferably 40:1, and the cationic surfactant in mixture and the mol ratio of nonionic surface active agent are preferably 30:1.
Further, in order to improve the performance of produced mesoporous nickel oxide, above-mentioned tensio-active agent is preferably the mixture of anion surfactant and nonionic surface active agent.
Wherein, the conventional tensio-active agent of method of producing mesoporous nickel oxide is all suitable for and the present invention, such as: described anion surfactant can be sodium lauryl sulphate (SDS) etc.; Described nonionic surface active agent can be polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer (P123) etc.; Described cationic surfactant can be cetyl trimethylammonium bromide (CTAB) etc.
Further, in order to improve the performance of produced mesoporous nickel oxide, the mol ratio of the nickel in aforesaid method and the integral molar quantity of tensio-active agent is preferably 8～12:1.More preferably 10:1 of the mol ratio of the integral molar quantity of nickel and tensio-active agent.
Wherein, the concrete steps of the method for the mesoporous nickel oxide of above-mentioned production are as follows:
A, get the aqueous solution (can water-soluble nickel salt be all applicable to the present invention) of nickel salt, add urea, be stirred to completely and dissolve; Wherein, the mol ratio of nickel and urea is 1:1～4; The mol ratio of nickel and urea is preferably 1:3
B, in the solution of a step, add tensio-active agent, be stirred to completely and dissolve;
C, by b step gained solution in 80～100 DEG C of insulations, make Precipitation; Generally.80～100 DEG C of insulations can make precipitation substantially separate out completely for about 10～16 hours; Be preferable over 90 DEG C of insulations 14 hours;
D, washing of precipitate, dry, then obtain mesoporous nickel oxide for 1 ~ 3 hour in 400 ~ 450 DEG C of calcinings.
Further, it is higher that the excessive concentration of nickel salt aqueous solution can cause precipitating initial stage degree of supersaturation, this is unfavorable for forming the precipitation of size uniform, the concentration of nickel salt aqueous solution is too low the shortcoming that output is little, consider above-mentioned factor, the concentration of the nickel salt aqueous solution described in a step of aforesaid method is preferably 0.2～0.5molL
-1, the concentration of nickel salt aqueous solution most preferably is 0.25molL
-1.
Wherein, in the d step of aforesaid method, be preferable over 400 DEG C of calcinings and within 2 hours, obtain mesoporous nickel oxide.
Wherein, in above-mentioned d step, can adopt ordinary method dry, such as: in 80 DEG C of baking ovens, be dried 4 hours.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
Embodiment 1 adopts the inventive method to produce mesoporous nickel oxide
Preparation 0.25molL
-1nickel nitrate aqueous solution 100mL, wherein by nickel: urea mol ratio is that 1:3 adds urea, be stirred to completely and dissolve.And then to add complexed surfactant SDS/P123, the mol ratio of nickel and total surfactant be 10:1, wherein SDS:P123 mol ratio is about 40:1, is stirred to equally completely and dissolves.Mixing solutions is transferred to Pressure solution bullet taking tetrafluoroethylene as liner, and (Pressure solution bullet is a kind of reactor that can seal, when it utilizes water or other solvents to heat in closed environment, vapour pressure becomes large and certain pressure is provided, become large degree relevant with the temperature of heating, do not need extra pressurization.Also can adopt other conventional closed reaction vessels.Down together), go, sealing is incubated 14 hours in 90 DEG C of baking ovens.After reaction finishes, in Pressure solution bullet, sedimentable matter is nickel oxide precursor, presoma is repeatedly washed with deionized water and dehydrated alcohol, then in 80 DEG C of baking ovens, is dried 4 hours.Finally, precursor powder is placed in to chamber type electric resistance furnace, in 400 DEG C of calcinings 2 hours, furnace cooling obtained mesoporous nickel oxide.This sample specific surface area 209m
2g
-1, pore volume 0.407cm
3g
-1, mean pore size 7.72nm, the ratio electric capacity of NiO is 258Fg
-1.
Embodiment 2 adopts the inventive method to produce mesoporous nickel oxide
Preparation 0.25molL
-1nickel nitrate aqueous solution 100mL, wherein by nickel: urea mol ratio is that 1:3 adds urea, be stirred to completely and dissolve.And then to add complexed surfactant CTAB/P123, the mol ratio of nickel and total surfactant be 10:1, wherein CTAB:P123 mol ratio is about 30:1, is stirred to equally completely and dissolves.Mixing solutions is transferred in the Pressure solution bullet taking tetrafluoroethylene as liner and is gone, and sealing is incubated 14 hours in 90 DEG C of baking ovens.After reaction finishes, in Pressure solution bullet, sedimentable matter is nickel oxide precursor, presoma is repeatedly washed with deionized water and dehydrated alcohol, then in 80 DEG C of baking ovens, is dried 4 hours.Finally, precursor powder is placed in to chamber type electric resistance furnace, in 400 DEG C of calcinings 2 hours, furnace cooling obtained mesoporous nickel oxide.This sample specific surface area 156m
2g
-1, pore volume 0.266cm
3g
-1, mean pore size 5.26nm, the ratio electric capacity of NiO is 153Fg
-1.
Embodiment 3 adopts the inventive method to produce mesoporous nickel oxide
Press method steps and the processing parameter of embodiment 1, only change composition and the proportioning of tensio-active agent, produce and obtain mesoporous nickel oxide, its performance measurement result is as shown in table 1, in addition, adopt the single tensio-active agent of equimolar amount to prepare mesoporous nickel oxide, result is as shown in table 2.
Table 1
Table 2
| Tensio-active agent | Specific surface area (m 2/g) |
| SDS | 101 |
| P123 | 89 |
| CTAB | 71 |
Can find out from table 1,2, tensio-active agent adopts the mixture of anion surfactant and nonionic surface active agent, or when the mixture of cationic surfactant and nonionic surface active agent, the performance of the mesoporous nickel oxide of producing is best, its specific surface area can reach 156m
2more than/g, the mass ratio of SDS and P123 is that 2:1 is that product performance are best.And the performance of the mesoporous nickel oxide that the specific surface area of the mesoporous nickel oxide that the mixture of employing anion surfactant and cationic surfactant is produced can only be produced with single tensio-active agent (SDS) is suitable.
Claims (7)
1. the method for producing mesoporous nickel oxide, it adopts tensio-active agent is template, it is characterized in that: described tensio-active agent is the mixture of a kind of and nonionic surface active agent in anion surfactant, cationic surfactant; Wherein, the anion surfactant in mixture and the mol ratio of nonionic surface active agent are 30～50:1, and the cationic surfactant in mixture and the mol ratio of nonionic surface active agent are 20～40:1; The mol ratio of the integral molar quantity of nickel and tensio-active agent is 8～12:1;
And the method for producing mesoporous nickel oxide, comprises the steps:
A, get the aqueous solution of nickel salt, add urea, be stirred to completely and dissolve; Wherein, the mol ratio of nickel and urea is 1:1～4;
B, in the solution of a step, add tensio-active agent, be stirred to completely and dissolve;
C, by b step gained solution in 80～100 DEG C of insulations, make Precipitation;
D, washing of precipitate, dry, then obtain mesoporous nickel oxide for 1 ~ 3 hour in 400 ~ 450 DEG C of calcinings;
Wherein, described anion surfactant is sodium lauryl sulphate; Described nonionic surface active agent is polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer; Described cationic surfactant is cetyl trimethylammonium bromide; And the concentration of the nickel salt aqueous solution described in a step is 0.2～0.5 molL
-1.
2. the method for the mesoporous nickel oxide of production according to claim 1, it is characterized in that: the anion surfactant in mixture and the mol ratio of nonionic surface active agent are 40:1, the cationic surfactant in mixture and the mol ratio of nonionic surface active agent are 30:1.
3. the method for the mesoporous nickel oxide of production according to claim 1 and 2, is characterized in that: described tensio-active agent is the mixture of anion surfactant and nonionic surface active agent.
4. the method for the mesoporous nickel oxide of production according to claim 1 and 2, is characterized in that: the mol ratio of the integral molar quantity of nickel and tensio-active agent is 10:1.
5. the method for the mesoporous nickel oxide of production according to claim 1 and 2, is characterized in that: the concentration of the nickel salt aqueous solution described in a step is 0.25 molL
-1.
6. the method for the mesoporous nickel oxide of production according to claim 1 and 2, is characterized in that: the mol ratio of the nickel described in a step and urea is 1:3.
7. the method for the mesoporous nickel oxide of production according to claim 1 and 2, is characterized in that: in d step, within 2 hours, obtain mesoporous nickel oxide in 400 DEG C of calcinings.
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| CN103151182B (en) * | 2013-02-07 | 2016-02-24 | 浙江工业大学 | A kind of nano nickel oxide electrode material and application thereof |
| CN104030371B (en) * | 2014-06-08 | 2016-01-13 | 吕仁江 | The method of the NiO microballoon of the synthesising mesoporous sheet structure composition of a kind of soft template method |
| CN105174320B (en) * | 2015-10-15 | 2017-03-22 | 齐鲁工业大学 | Hexagonal flake-shaped mesoporous nickel oxide and preparation method and application thereof |
| CN108786816B (en) * | 2017-05-02 | 2021-05-25 | 中科榆林能源技术运营有限责任公司 | Mesoporous nickel catalyst and application thereof in polyether amine synthesis |
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| CN101543781A (en) * | 2009-05-04 | 2009-09-30 | 厦门大学 | Catalyst for preparing propylene by oxidizing and dehydrogenating propane and preparation method thereof |
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Non-Patent Citations (4)
| Title |
|---|
| JP特开2009-196870A 2009.09.03 |
| P. Justin et al..Tuning of Capacitance Behavior of NiO Using Anionic, Cationic, and Nonionic Surfactants by Hydrothermal Synthesis.《J. Phys. Chem. C》.2010,第114卷(第11期),5203-5210. |
| Tuning of Capacitance Behavior of NiO Using Anionic, Cationic, and Nonionic Surfactants by Hydrothermal Synthesis;P. Justin et al.;《J. Phys. Chem. C》;20100225;第114卷(第11期);5203-5210 * |
| 汪彩彩 等.介孔CeNiO催化剂的合成及其丙烷氧化脱氢制丙烯反应性能.《物理化学学报(Wuli Huaxue Xuebao)》.2011,第27卷(第10期),2421-2426. * |
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