CN108453265B - Silicon dioxide nanotube confinement nickel nanoparticle and preparation method thereof - Google Patents
Silicon dioxide nanotube confinement nickel nanoparticle and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of advanced nano composite materials and technologies, and particularly relates to a silicon dioxide nanotube confinement nickel nanoparticle and a preparation method thereof. According to the invention, a hydrothermal method is adopted firstly, and a silicon source precursor is synthesized into the multi-wall nickel silicate nanotube as a precursor of the nickel nanoparticles under an alkaline condition. Then, a micro-emulsion method is utilized, silicon dioxide precursors are hydrolyzed, and a uniform silicon dioxide nanotube shell is coated on the surface of the nickel silicate nanotube. And finally, decomposing the nickel silicate nanotube precursor into nickel nanoparticles in situ under a high-temperature reducing atmosphere, and confining the nickel nanoparticles in the shell layer of the silicon dioxide nanotube to form the silicon dioxide nanotube confined nickel nanoparticles. The preparation method can ensure that under the condition of high load capacity, the nickel nano particles are completely confined in the silicon dioxide nano tube, and has the advantages of high specific surface area, high nickel dispersion degree, high sintering resistance and the like.
Description
Technical Field
The invention belongs to the field of advanced nano composite materials and technologies, and particularly relates to a silicon dioxide nanotube confinement nickel nanoparticle and a preparation method thereof.
Background
In recent years, the nanoparticle confinement effect has attracted much attention in the fields of catalysis, medicine, environmental protection, energy storage and the like. This is mainly due to the fact that by confining nanoparticles within a porous support, such as three-dimensional mesoporous silicon including SBA-15 and MCM-41, and one-dimensional nanotubes such as carbon nanotubes and silica nanotubes, these nanoparticles can have very good sintering and agglomeration resistance properties, and also enhance the interaction between the nanoparticles and the support interface, so that these nanoparticles have very good nano-size effects such as: high catalytic activity and special light effect.
In general, due to the presence of surface tension and capillary action, if one chooses a precursor for the nanoparticles and a porous support affinityAll the solvents are stronger, so that the nanoparticle precursor solution can be easily absorbed into the porous carrier, and the nanoparticles with limited domains can be obtained through further treatment. Thus, many researchers have studied the selection of solvents, such as polyethyleneimine, ethylene glycol, toluene, oleic acid, oleylamine, and tetraglyme, among others (D.Kang, H.S. Lim and J.W.Lee, int.J.hydrogen Energ.,2017,42, 11270-.M. driess and a.thomas, ChemCatChem,2015,7, 1280-. In addition, the interaction between the functional groups on the surface of the porous carrier and the nanoparticles prevents the nanoparticles from being completely confined. Especially when the nanoparticle loading is high, a small amount of nanoparticles is always present on the outer surface of the porous support. These small amounts of nanoparticles present on the outer surface of the porous support may cause agglomeration, etc., which affects the overall properties of the material.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provided are a silicon dioxide nanotube confinement nickel nanoparticle and a preparation method thereof. The preparation method can ensure that the complete confinement of the nickel nanoparticles in the silicon dioxide nanotubes is realized under the condition of high nickel nanoparticle loading, and has the advantages of high specific surface area, high nickel dispersion degree, high sintering resistance and the like. When the catalyst is used for catalyzing the reforming reaction of methane and carbon dioxide, the catalyst has high carbon deposition resistance and has important application prospect in other catalysis fields. The preparation method disclosed by the invention can realize the control of the wall thickness and the specific surface area of the silicon dioxide nanotube and can realize the complete confinement of all nickel nanoparticles. The synthesis raw materials are easy to obtain, the method is simple and rapid, and large-batch synthesis can be realized so as to solve the problems in the prior art.
The technical scheme of the invention is as follows: a preparation method of silicon dioxide nanotube confinement nickel nanoparticles comprises the following steps: firstly, forming a nickel silicate nanotube precursor by a hydrothermal synthesis method under an alkaline condition by using a silicon source and a nickel salt precursor; then, hydrolyzing a silicon dioxide precursor under an alkaline condition by using a water/ethanol/surfactant microemulsion method, coating a uniform silicon dioxide shell layer on the surface of the nickel silicate nanotube precursor, adding a solvent for washing, centrifugally separating to remove alkaline and acidic substances, and drying; and finally, decomposing the silicate nanotube precursor into nickel nanoparticles in situ by using a high-temperature reduction method, and completely confining the nickel nanoparticles in the silica nanotube shell layer to synthesize the silica nanotube confined nickel nanoparticles.
The silicon source is one or more of ethyl orthosilicate, methyl orthosilicate and sodium silicate; the nickel precursor is one or more of nickel nitrate, nickel chloride, nickel acetate and nickel acetylacetonate.
The alkali in the hydrothermal synthesis system is one or more of urea, concentrated ammonia water and sodium hydroxide; the pH value is controlled to be 8-12.
The reaction time for preparing the nickel silicate nanotube is controlled to be 10-24 h; the reaction temperature is controlled between 120 ℃ and 220 ℃.
The surfactant in the method for preparing the silicon dioxide nanotube shell microemulsion is a non-ionic surfactant or an ionic surfactant.
The silicon dioxide precursor used for preparing the shell layer of the silicon dioxide nanotube is one or more of tetraethoxysilane, methyl orthosilicate and sodium silicate; the reaction time for preparing the silicon dioxide nanotube shell is controlled to be 1-14 days.
The alkali in the microemulsion system is one or more of urea, concentrated ammonia water and sodium hydroxide.
The temperature of the high-temperature reduction method is controlled to be 500-900 ℃, and the reaction time is 1-5 h; the reducing gas of the high-temperature reduction method is one or more of a mixed gas of 5 percent of hydrogen and nitrogen, a mixed gas of 99.999 percent of hydrogen, 5 percent of carbon monoxide and nitrogen and 99.999 percent of carbon monoxide; the used washing solvent adopts a mixed solution of alkyl alcohol and water; wherein the alkyl alcohol is one or more of methanol, ethanol and isopropanol; the mass ratio of the alkyl alcohol to the water is 9: 1-1: 9.
In a nickel silicate nanotube hydrothermal synthesis system, the mass percent of a nickel salt precursor is 0.5-30 wt%, the mass percent of a silicon source is 0.5-5 wt%, the mass percent of an alkali is 5-50 wt%, and the balance is a water solvent; in a microemulsion system for synthesizing a shell layer of a silicon dioxide nanotube, the mass percent of a silicon dioxide precursor is 0.5-15 wt%, the mass percent of a nickel silicate nanotube is 0.5-50 wt%, the mass percent of alkali is 0.5-10 wt%, the mass percent of a surfactant is 0.5-10 wt%, and the mass percent of other components is an ethanol-water mixed solution, and the pH value is controlled to be 8-12.
The nonionic surfactant is C14H22O(C2H4O) n, n-10-15 and C15H24O(C2H4O) n, n is one or more of 5-10, and the ionic surfactant is alkyl quaternary ammonium salt surfactant CnAnd (3) TAB, wherein n is one or more of 10-15.
The invention has the beneficial effects that: the silicon dioxide nanotube confinement nickel nanoparticle and the preparation method thereof can ensure that the nickel nanoparticle is completely confined in the silicon dioxide nanotube under the condition of high load (20 wt% -30 wt%). It is characterized in that the wall thickness of the silicon dioxide nanotube can be regulated and controlled (3 nm-30 nm) and the specific surface area can be regulated and controlled (100 m)2.g-1~500m2.g-1) And the nickel is highly dispersed (the particle size is between 5 and 8nm), and has the advantages of high sintering resistance and the like. When the catalyst is used for catalyzing the reforming reaction of methane and carbon dioxide, the catalyst has high carbon deposition resistance and has important application prospect in other catalysis fields. The preparation method and the synthetic raw materials reported by the inventionEasy to obtain, simple and rapid in method and capable of realizing large-batch synthesis.
Drawings
FIG. 1 is a schematic diagram of a method for preparing a silica nanotube-confined nickel nanoparticle;
FIG. 2 is a transmission electron micrograph of nickel silicate nanotubes;
FIG. 3 is a transmission electron microscope image of a nickel silicate nanotube @ silica core-shell structured nanotube;
FIG. 4 is a transmission electron microscope image of a silica nanotube confined nickel nanoparticle;
FIG. 5 is a high magnification transmission electron micrograph of a silica nanotube confined nickel nanoparticle;
FIG. 6 is an X-ray diffraction diagram; (a) a nickel silicate nanotube, (b) a nickel silicate nanotube @ silica, (c) a silica nanotube confinement nickel nanoparticle;
FIG. 7 is a transmission electron micrograph of silica nanotube-supported nickel nanoparticles before (a) the carbon dioxide methane reforming reaction and after 70 hours at 700 ℃ reaction (b);
FIG. 8 is a comparative test of activity and stability of carbon dioxide methane reforming at 700 ℃ for 70 hours;
FIG. 9 is a transmission electron micrograph of silica nanotube confined nickel nanoparticles after reaction at 700 ℃ for 70 hours for carbon dioxide methane reforming;
fig. 10 is a thermogram of carbon dioxide methane reforming after 70 hours of reaction at 700 ℃.
Detailed Description
Example 1:
(1) adding 1.9 g of nickel nitrate, 10ml of water, 10ml of ethyl orthosilicate and 10 g of urea into a hydrothermal kettle in sequence, stirring at room temperature for 10 minutes, putting into a thermostat at 200 ℃, reacting for 10 hours, and taking out. After cooling to room temperature, washing with a mixed solvent of ethanol and water for many times, centrifuging, and drying at room temperature to obtain the nickel silicate nanotube (figure 2). The diffraction peak a in the XRD diffraction pattern 6 shows that the prepared nickel silicate nanotube has no other impurity phase.
(2) Putting the nickel silicate nanotube prepared in the previous step into a reactor 2In a 00 ml flask, 100 ml of ethanol, 50 ml of water, 6.9 ml of ammonia (28 wt%), and CTAB (5 g/l) were added in this order and stirred uniformly. Then, 1mL of ethyl orthosilicate was added, and after 24 hours of reaction, the mixture was centrifuged. Washing with a mixed solvent of ethanol and water for several times, centrifuging, drying at room temperature for 12 hours, and calcining at 600 ℃ for 4 hours. The specific surface area of the obtained nickel silicate nanotube @ silicon dioxide nanotube core-shell structure is 180m2.g-1. Wherein, the thickness of the shell layer of the silicon dioxide nanotube is 8nm (figure 3). XRD diffractogram the diffraction pattern of b in fig. 6 shows a diffraction peak of silica at 23.5 °. In addition, nickel silicate has a weak diffraction peak intensity. These all indicate that the nickel silicate nanotube @ silica nanotube core-shell structure was successfully synthesized.
(3) And reducing the nickel silicate nanotube @ silicon dioxide nanotube core-shell structure obtained in the last step by using pure hydrogen at 700 ℃ for 1 hour to obtain the silicon dioxide nanotube confinement nickel nanoparticle (as shown in fig. 4 and 5). In the diffraction pattern c of XRD diffraction pattern 6, the diffraction peak of nickel silicate disappears, and the diffraction peak of nickel appears. This indicates that the nickel silicate is reduced and decomposed in situ to produce nickel nanoparticles after high temperature reduction. The size of the nickel nanoparticles was estimated to be 5.2nm from fig. 4, and the grain size calculated from fig. 6 was 6.8nm, which are consistent.
(4) Preparation of comparative sample: the silica nanotube supported nickel nanoparticle catalyst was prepared by ultrasound assisted impregnation (nickel loading remained the same as the silica nanotube confined nickel nanoparticles) (fig. 7 a). Weighing a certain amount of nickel nitrate and a certain amount of silicon dioxide nanotubes, putting the nickel nitrate and the silicon dioxide nanotubes into a crucible, adding a certain amount of deionized water, carrying out ultrasonic treatment for 20 hours, stirring the mixture in a water bath at 60 ℃ until the mixture is dry, drying the mixture in an oven at 60 ℃ for 12 hours, and calcining the mixture at 700 ℃ for 4 hours. As can be seen from FIG. 7a, most of the nickel is present on the surface of the silica nanotube, and the particle size of the nickel is 11.2 nm.
(5) And (3) comparative test testing: at normal pressure, adding CH4、CO2And He at 1:1:1 (space velocity 36L. g)-1cat·h-1) Respectively introducing a catalyst containing silicon dioxide nanotubes confinement or nickel-loaded nanoparticles for fixationBed reactor (700oC), reaction 70h (FIG. 8). It can be seen that for the silica nanotube confined nickel nanoparticles, the conversion of methane and carbon dioxide drops by about 18%. While the conversion of nickel nanoparticles loaded on silica nanotubes decreased by about 21% (carbon dioxide) and 27% (methane). Comparing the electron microscope images before and after the reaction of the two catalysts (fig. 9 and 4 and fig. 7a and b), it can be seen that the silica nanotube confinement nickel nanoparticles have good anti-sintering performance. From thermogravimetric analysis of fig. 10, it can be seen that the silica nanotube confinement nickel nanoparticles have high carbon deposition resistance.
Example 2:
(1) adding 1.9 g of nickel acetylacetonate, 10ml of water, 10ml of sodium silicate and 10 g of sodium hydroxide into a hydrothermal kettle in sequence, stirring for 10 minutes at room temperature, putting into a thermostat at 180 ℃, reacting for 18 hours, and taking out. After cooling to room temperature, washing and centrifuging for many times by using a mixed solvent of ethanol and water, and drying at room temperature to obtain the nickel silicate nanotube.
(2) The nickel silicate nanotube prepared in the above step is put into a 200 ml flask, and 100 ml of ethanol, 50 ml of water, 20 ml of ammonia (28 wt%) and CTAB (5 g/l in concentration) are sequentially added and stirred uniformly. Then, 10mL of methyl orthosilicate was added, and after 7 days of reaction, the mixture was centrifuged. Washing with a mixed solvent of ethanol and water for several times, centrifuging, drying at room temperature for 12 hours, and calcining at 900 ℃ for 4 hours. The specific surface area of the obtained nickel silicate nanotube @ silicon dioxide nanotube core-shell structure is 250m2.g-1. Wherein the thickness of the shell layer of the silicon dioxide nanotube is 13 nm.
(3) And reducing the nickel silicate nanotube @ silicon dioxide nanotube core-shell structure obtained in the last step by using 5% of carbon monoxide and nitrogen mixed gas at 500 ℃ for 4 hours to obtain the silicon dioxide nanotube confinement nickel nanoparticles.
Example 3:
(1) adding 1.9 g of nickel chloride, 10ml of water, 5 ml of ethyl orthosilicate and 10 g of sodium hydroxide into a hydrothermal kettle in sequence, stirring for 10 minutes at room temperature, putting into a constant temperature box of 120 ℃, reacting for 30 hours, and taking out. After cooling to room temperature, washing and centrifuging for many times by using a mixed solvent of ethanol and water, and drying at room temperature to obtain the nickel silicate nanotube.
(2) The nickel silicate nanotube prepared in the above step was put into a 200 ml flask, and 100 ml of ethanol, 50 ml of water, 2 g of urea (28 wt%), and CTAB (5 g per liter) were sequentially added and stirred uniformly. Then, 30mL of methyl orthosilicate was added, and after reacting for 14 days, the mixture was centrifuged. Washed with a mixed solvent of ethanol and water several times, centrifuged, dried at room temperature for 12 hours, and then calcined at 700 ℃ for 4 hours. The specific surface area of the obtained nickel silicate nanotube @ silicon dioxide nanotube core-shell structure is 320m2.g-1. Wherein the thickness of the shell layer of the silicon dioxide nanotube is 17 nm.
(3) And reducing the nickel silicate nanotube @ silicon dioxide nanotube core-shell structure obtained in the last step by using pure carbon monoxide at 800 ℃ for 5 hours to obtain the silicon dioxide nanotube confinement nickel nanoparticles.
Claims (10)
1. A preparation method of silicon dioxide nanotube confinement nickel nanoparticles is characterized by comprising the following steps: comprises the following steps: firstly, forming a nickel silicate nanotube precursor by a hydrothermal synthesis method under an alkaline condition by using a silicon source and a nickel salt precursor; then, hydrolyzing a silicon dioxide precursor under an alkaline condition by using a microemulsion method in which water, ethanol and a surfactant exist simultaneously, coating a uniform silicon dioxide shell layer on the surface of the nickel silicate nanotube precursor, adding a solvent for washing, centrifugally separating to remove alkaline and acidic substances, drying, and calcining at 600, 700 or 900 ℃ for 4 hours to obtain a nickel silicate nanotube @ silicon dioxide nanotube core-shell structure; and finally, decomposing the nickel silicate nanotube into nickel nano particles in situ by using a high-temperature reduction method, and completely confining the nickel nano particles in the shell layer of the silicon dioxide nanotube to synthesize the silicon dioxide nanotube confined nickel nano particles.
2. The method for preparing silica nanotube-confined nickel nanoparticles according to claim 1, wherein the method comprises the following steps: the silicon source is one or more of ethyl orthosilicate, methyl orthosilicate and sodium silicate; the nickel salt precursor is one or more of nickel nitrate, nickel chloride, nickel acetate and nickel acetylacetonate.
3. The method for preparing silica nanotube-confined nickel nanoparticles according to claim 1, wherein the method comprises the following steps: the alkaline condition in the hydrothermal synthesis method is realized by one or more than one of urea, concentrated ammonia water and sodium hydroxide; the pH value is controlled to be 8-12.
4. The method for preparing silica nanotube-confined nickel nanoparticles according to claim 1, wherein the method comprises the following steps: the reaction time of the nickel silicate nanotube precursor is controlled to be 10-30 h; the reaction temperature is controlled between 120 ℃ and 220 ℃.
5. The method for preparing silica nanotube-confined nickel nanoparticles according to claim 1, wherein the method comprises the following steps: the surfactant in the microemulsion method is a non-ionic surfactant or an ionic surfactant.
6. The method for preparing silica nanotube-confined nickel nanoparticles according to claim 1, wherein the method comprises the following steps: the silicon dioxide precursor used for obtaining the nickel silicate nanotube @ silicon dioxide nanotube core-shell structure is one or more of ethyl orthosilicate, methyl orthosilicate and sodium silicate; the reaction time of the obtained nickel silicate nanotube @ silicon dioxide nanotube core-shell structure is controlled to be 1-14 days.
7. The method for preparing silica nanotube-confined nickel nanoparticles according to claim 1, wherein the method comprises the following steps: the alkaline condition in the microemulsion method is realized by mixing one or more of urea, concentrated ammonia water and sodium hydroxide.
8. The method for preparing silica nanotube-confined nickel nanoparticles according to claim 1, wherein the method comprises the following steps: the temperature of the high-temperature reduction method is controlled to be 500-900 ℃, and the reaction time is 1-5 h; the reducing gas of the high-temperature reduction method is one or more of a mixed gas of 5 percent of hydrogen and nitrogen, a mixed gas of 99.999 percent of hydrogen, 5 percent of carbon monoxide and nitrogen and 99.999 percent of carbon monoxide; the solvent adopted in the solvent washing is a mixed solution of alkyl alcohol and water; wherein the alkyl alcohol is one or more of methanol, ethanol and isopropanol; the mass ratio of the alkyl alcohol to the water is 9: 1-1: 9.
9. The method for preparing silica nanotube-confined nickel nanoparticles according to claim 1, wherein the method comprises the following steps: in the hydrothermal synthesis method of the nickel silicate nanotube precursor, the mass percent of the nickel salt precursor is 0.5-30 wt%, the mass percent of the silicon source is 0.5-5 wt%, the mass percent of the alkali is 5-50 wt%, and the rest is water solvent; in the microemulsion method for synthesizing the nickel silicate nanotube @ silicon dioxide nanotube core-shell structure, the mass percent of a silicon dioxide precursor is 0.5-15 wt%, the mass percent of a nickel silicate nanotube precursor is 0.5-50 wt%, the mass percent of an alkali is 0.5-10 wt%, the mass percent of a surfactant is 0.5-10 wt%, and the other components are ethanol-water mixed solution, and the pH value is controlled to be 8-12.
10. The method for preparing silica nanotube-confined nickel nanoparticles according to claim 5, wherein: the nonionic surfactant is C14H22O(C2H4O) n, n =10 ~ 15 and C15H24O(C2H4O) n, n = 5-10, and the ionic surfactant is alkyl quaternary ammonium salt surfactant CnAnd (3) TAB, wherein n = 10-15, and one or more of the above are mixed.
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CN114405502B (en) * | 2020-10-28 | 2023-05-26 | 中国科学院大连化学物理研究所 | Preparation and application of catalyst with metal supported on inner wall of silica nanotube |
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CN114950456A (en) * | 2022-06-16 | 2022-08-30 | 贵州大学 | Silicon dioxide nanotube confinement nickel-CeO 2 Nanoparticles and method for preparing same |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008021256A3 (en) * | 2006-08-11 | 2008-08-14 | Aqua Resources Corp | Nanoplatelet metal hydroxides and methods of preparing same |
CN101280457A (en) * | 2007-04-03 | 2008-10-08 | 中国科学院理化技术研究所 | Preparation of silicon dioxide nano-tube |
CN104220168A (en) * | 2012-05-11 | 2014-12-17 | Lg化学株式会社 | Method for preparing core-shell particle supported with carrier, and core-shell particle supported with carrier prepared thereby |
CN104843805A (en) * | 2015-04-16 | 2015-08-19 | 电子科技大学 | CNTs@SiO2@Ni/Al-LDH shell structure three-dimensional nanometer material and preparation method thereof |
-
2018
- 2018-04-24 CN CN201810374189.9A patent/CN108453265B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008021256A3 (en) * | 2006-08-11 | 2008-08-14 | Aqua Resources Corp | Nanoplatelet metal hydroxides and methods of preparing same |
CN101280457A (en) * | 2007-04-03 | 2008-10-08 | 中国科学院理化技术研究所 | Preparation of silicon dioxide nano-tube |
CN104220168A (en) * | 2012-05-11 | 2014-12-17 | Lg化学株式会社 | Method for preparing core-shell particle supported with carrier, and core-shell particle supported with carrier prepared thereby |
CN104843805A (en) * | 2015-04-16 | 2015-08-19 | 电子科技大学 | CNTs@SiO2@Ni/Al-LDH shell structure three-dimensional nanometer material and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
Synthesis of Ni@SiO2 Nanotube Particles in a Water-in-Oil Microemulsion Template;Dahlberg, KA等;《CHEMISTRY OF MATERIALS》;20121231;第24卷(第14期);具体实验部分,图1-2 * |
Synthesis of SiO2 Nanotubes and Their Application as Nanoscale Reactors;Hitoshi Ogihara 等;《Chem. Mater.》;20060119;第18卷;全文 * |
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Inventor after: Li Min Inventor after: Li Ziwei Inventor after: Lei Zhen Inventor before: Li Ziwei Inventor before: Li Min Inventor before: Lei Zhen |
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GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210209 |