CN103252237A - Method for preparing mesoporous-shaped alkali nickel silicate/silica nuclear shell microballoon with adjustable indoor room space - Google Patents
Method for preparing mesoporous-shaped alkali nickel silicate/silica nuclear shell microballoon with adjustable indoor room space Download PDFInfo
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- CN103252237A CN103252237A CN2013101718448A CN201310171844A CN103252237A CN 103252237 A CN103252237 A CN 103252237A CN 2013101718448 A CN2013101718448 A CN 2013101718448A CN 201310171844 A CN201310171844 A CN 201310171844A CN 103252237 A CN103252237 A CN 103252237A
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- mesoporous
- silicon
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 52
- 239000003513 alkali Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 24
- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical compound [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-UHFFFAOYSA-N 0.000 title abstract 3
- 239000000839 emulsion Substances 0.000 claims abstract description 40
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 9
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- VIAPNRBXEJNZKV-UHFFFAOYSA-N nickel silicic acid Chemical compound [Ni].[Si](O)(O)(O)O VIAPNRBXEJNZKV-UHFFFAOYSA-N 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 230000000977 initiatory effect Effects 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000002816 nickel compounds Chemical class 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 230000001143 conditioned effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 12
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 7
- 239000010935 stainless steel Substances 0.000 abstract description 7
- 239000004809 Teflon Substances 0.000 abstract 1
- 229920006362 Teflon® Polymers 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000010406 interfacial reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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- Silicon Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a method for preparing a mesoporous-shaped alkali nickel silicate/silica nuclear shell microballoon with an adjustable indoor room space. The method comprises the following steps of (1) putting silica balls prepared by a Stober method into deionized water, and carrying out ultrasonic dispersion to form white emulsion; (2) dissolving nickel acetate into the white emulsion containing the silica balls uniformly; and (3) transferring mixed green emulsion into a stainless steel autoclave with a teflon lining, carrying out heat preservation for 3-28 hours at 150 DEG C-200 DEG C, cooling to room temperature in air, and centrifuging, washing and drying to obtain a light green mesoporous silica/alkali nickel silicate nuclear shell structure. The indoor space between the shell and a nucleus can be adjusted, and the preparation method is simple and is easy to produce in batches.
Description
Technical field
The present invention relates to a kind of mesoporous shape alkali formula silicic acid nickel/silica shell nuclear microballoon and preparation method thereof, particularly a kind of mesoporous shape alkali formula silicic acid nickel of inner chamber space adjustable size/silica shell nuclear microballoon and preparation method thereof.
Background technology
Nickel is regarded as the grand strategy material of the development of the national economy, and its resources effective exploitation and comprehensive utilization are paid attention to by various countries always.Nickel compound containing is a kind of catalytic action catalyst preferably.Ni
2+Have the 3d track, polyelectron oxygen is had the tendency of absorption according to qualifications, other reducing gas is also had activation, and to the O in the reducing gas
2Playing catalytic action, be commonly used in the gasoline hydrocracking, is the hydrocarbon conversion during petrochemical industry is handled, in the processes such as heavy oil hydrogenation.At catalytic field, nickel has higher activity and economic as the catalyst activity component with respect to other metal.Nickel compound containing has good catalytic performance in reactions such as hydrogenation, alkylation, steam transforming.In catalytic process, the existence form of nickel is to its catalytic effect important influence, mesoporous shape alkali formula silicic acid nickel/silica shell nuclear microballoon, and its specific area is big, has that catalytic activity is strong, catalyst carries the high characteristics of capacity.
Summary of the invention
The objective of the invention is to solve the synthetic nucleocapsid spherical structure of present template, at first to utilize surfactant that template surface is carried out modification, and initial action relates to the problem that the number of chemical material participates in reaction, provide a kind of to adopt a kind of template and a kind of initial reactant, by sacrificing template/interfacial reaction, the mesoporous shape alkali formula silicic acid nickel of controlled synthetic inner chamber space adjustable size under hydrothermal condition/silica shell nuclear microballoon and preparation method thereof.This method is the nickel source with the nickel acetate, silica not only is template but also serve as reactant, by sacrificing template/interfacial reaction method, successfully obtain the mesoporous shape alkali formula silicic acid nickel/silica shell nuclear microballoon of inner chamber space adjustable size, the present invention can reach the size of regulating alkali formula silicic acid nickel/silica shell caryosphere inside configuration space by nickel and silicon mol ratio in the adjusting initial action liquid, also can adopt and fix nickel and silicon mol ratio in the suitable initial action liquid, regulate and control the size in alkali formula silicic acid nickel/silica shell caryosphere inside configuration space by the adjusting hydro-thermal reaction time.Preparation technology is simple, and is easy to produce in batches.
For achieving the above object, the present invention is by the following technical solutions:
A kind of method for preparing the mesoporous shape alkali formula silicic acid nickel/silica shell nuclear microballoon of inner chamber space adjustable size, may further comprise the steps: 1, silica spheres is put into deionized water, ultrasonic dispersion forms white emulsion; 2, then nickel compound containing is dissolved in the described white emulsion green mixed emulsion; 3, at last described mixed emulsion is transferred to 150 ℃～200 ℃ insulations down in the autoclave, treat that fully the reaction back is cooled to room temperature in air, reacted described mixed emulsion is centrifugal, washing also obtains mesoporous alkali formula silicic acid nickel/silicon dioxide core-shell structure after the drying.
Preferable, the mol ratio of the silica of adding and the nickel of adding is between 4: 3 to 1: 2.
Preferable, will form white emulsion in the ultrasonic 40ml of the being dispersed in deionized water of 0.1g silica in the step 1.
Preferable, temperature retention time is 3-28h in the step 3.
Preferable, described nickel compound containing is nickel acetate.
Preferable, described silica basis
The method preparation.
Preferable, described autoclave is that liner is the stainless steel autoclave of polytetrafluoroethylene (PTFE).
Preferable, the molar concentration control of described nickel acetate is at 0.030-0.100mol/L.
Described method is by the ratio of nickel in the control initial action liquid with the silicon template, or after the ratio of fixing appropriate nickel and silicon template, regulates and control the size that mesoporous shape alkali formula silicic acid nickel/silica shell is examined the microballoon internal voids by the adjusting hydro-thermal reaction time.
In alkali formula silicic acid nickel of the present invention/silica shell nuclear microballoon, alkali formula silicic acid nickel represents shell, silica representative nuclear.
The mesoporous shape alkali formula silicic acid nickel of inner chamber space adjustable size of the present invention/silica shell nuclear microballoon is confirmed by SEM (SEM) and transmission electron microscope (TEM) respectively.Fig. 1 is SEM photo and the TEM photo of the mesoporous shape alkali formula silicic acid nickel/silica shell nuclear microballoon of typical inner chamber space adjustable size, as can be seen from the figure, products obtained therefrom by size evenly, disperse preferably that spheroidal particle constitutes.Further, we can see clearly that the spherical shell surface has meso-hole structure.The microballoon of several fragmentations has a transportable silica spheres in the spherical shell of fragmentation as can be seen from figure, shows that these microballoons have the mesoporous alkali formula silicic acid nickel/silicon dioxide core-shell structure of space size between adjustable nuclear and the shell.TEM photo from Fig. 1 as can be seen, along with the control of reaction condition, its inner chamber space size of the mesoporous alkali formula of gained silicic acid nickel/silicon dioxide core-shell structure can well be regulated and control.
The present invention can reach the size of regulating alkali formula silicic acid nickel/silica shell caryosphere inside configuration space by nickel and silicon mol ratio in the adjusting initial action liquid, also can adopt and fix nickel and silicon mol ratio in the suitable initial action liquid, regulate and control the size in alkali formula silicic acid nickel/silica shell caryosphere inside configuration space by the adjusting hydro-thermal reaction time.Preparation technology is simple, and is easy to produce in batches.
Description of drawings
Fig. 1 is SEM photo and the TEM photo of the mesoporous shape alkali formula silicic acid nickel/silica shell nuclear microballoon of the inner chamber space adjustable size of the present invention's preparation, and the silicon of initial action and the mol ratio of nickel are 4: 3,1: 1, and 2: 3 and 1: 2;
Fig. 2 is that the silicon of initial action and the mol ratio of nickel are 1: 2 o'clock, and the TEM photo of products obtained therefrom: figure (a) (b), is 3 hours with (d) representing the reaction time respectively (c), 6 hours, and 12 hours and 24 hours.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
The present invention can realize the regulation and control of space size between the shell nuclear by two lines: the ratio of nickel acetate and silica template in (1) control initial action liquid, and it is fully reacted, regulate the size of inner chamber space, as embodiment 1,2,3 and 4.Along with the change of the ratio of nickel acetate and silica template in the initial liquid, the space size increases gradually between the shell nuclear.(2) adopt and to fix silicon and nickel mol ratio in the suitable initial action liquid, as 1: 2, regulate and control the size of internal voids between the shell nuclear by regulating the hydro-thermal reaction time, as embodiment 5.Along with the prolongation in reaction time, the space size increases gradually between the shell nuclear.
Embodiment 1
Concrete steps are as follows:
(1) will adopt
Method [
W, Fink A, Bohn E, Controlled growth of monodisperse silica spheres in micron size range, J. ColloidInterface Sci., 1968,26 (1): 62-69] Zhi Bei 0.1g silica is put into the 40ml deionized water, forms white emulsion through ultrasonic dispersion;
(2) four water nickel acetate uniform dissolution are obtained green emulsion in the white emulsion that contains silica spheres, the mol ratio of silicon and nickel is 4: 3 in the emulsion;
(3) should the green emulsion be transferred in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), 180 ℃ are incubated 24h down, are cooled to room temperature in air, after centrifugal, washing, drying, obtain the mesoporous shape alkali of light green formula silicic acid nickel/silica shell nuclear microballoon;
(4) products therefrom pattern and structure characterize by SEM and TEM, shown in Fig. 1 a and 1b.
Embodiment 2
(1) will adopt
The 0.1g silica of method preparation is put into the 40ml deionized water, forms white emulsion through ultrasonic dispersion;
(2) four water nickel acetate uniform dissolution are obtained green emulsion in the white emulsion that contains silica spheres, the mol ratio of silicon and nickel is 1: 1 in the emulsion;
(3) should the green emulsion be transferred in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), 180 ℃ are incubated 24h down, are cooled to room temperature in air, after centrifugal, washing, drying, obtain the mesoporous shape alkali of light green formula silicic acid nickel/silica shell nuclear microballoon;
(4) products therefrom pattern and structure characterize by SEM and TEM, shown in Fig. 1 c and 1d.
Embodiment 3
(1) will adopt
The 0.1g silica of method preparation is put into the 40ml deionized water, forms white emulsion through ultrasonic dispersion;
(2) four water nickel acetate uniform dissolution are obtained green emulsion in the white emulsion that contains silica spheres, the mol ratio of silicon and nickel is 2: 3 in the emulsion;
(3) should the green emulsion be transferred in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), 180 ℃ are incubated 24h down, are cooled to room temperature in air, after centrifugal, washing, drying, obtain the mesoporous shape alkali of light green formula silicic acid nickel/silica shell nuclear microballoon;
(4) products therefrom pattern and structure characterize by SEM and TEM, shown in Fig. 1 e and 1f.
Embodiment 4
(1) will adopt
The 0.1g silica of method preparation is put into the 40ml deionized water, forms white emulsion through ultrasonic dispersion;
(2) four water nickel acetate uniform dissolution are obtained green emulsion in the white emulsion that contains silica spheres, the mol ratio of silicon and nickel is 1: 2 in the emulsion;
(3) should the green emulsion be transferred in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), 180 ℃ are incubated 24h down, are cooled to room temperature in air, after centrifugal, washing, drying, obtain the mesoporous alkali formula of light green silicic acid nickel hollow ball structure;
(4) products therefrom pattern and structure characterize by SEM and TEM, shown in Fig. 1 g and 1h.
Embodiment 5
(1) will adopt
The 0.1g silica of method preparation is put into the 40ml deionized water, forms white emulsion through ultrasonic dispersion;
(2) four water nickel acetate uniform dissolution are obtained green emulsion in the white emulsion that contains silica spheres, the mol ratio of silicon and nickel is 1: 2 in the emulsion;
(3) should the green emulsion be transferred in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), 180 ℃ are incubated 3h, 6h down, 12h and 24h, in air, be cooled to room temperature, after centrifugal, washing, drying, obtain the mesoporous alkali formula of light green silicic acid nickel/silica shell nuclear micro-sphere structure;
(4) products therefrom pattern and structure characterize by TEM, as shown in Figure 2.Can see clearly that from figure to 2d, it is big that inner chamber space becomes gradually from Fig. 2 a.
Should be understood that, for those of ordinary skills, can be improved according to the above description or conversion, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (7)
1. the method for the mesoporous shape alkali formula silicic acid nickel for preparing the inner chamber space adjustable size/silica shell nuclear microballoon may further comprise the steps:
(1), silica spheres is put into deionized water, ultrasonic dispersion formation white emulsion;
(2), then nickel compound containing is dissolved in the described white emulsion green mixed emulsion;
(3), at last described mixed emulsion is transferred to 150 ℃～200 ℃ insulations down in the autoclave, treat that fully the reaction back is cooled to room temperature in air, reacted described mixed emulsion is centrifugal, washing also obtains mesoporous alkali formula silicic acid nickel/silicon dioxide core-shell structure after the drying.
2. the method for claim 1, wherein described nickel compound containing is nickel acetate.
3. method as claimed in claim 2, wherein, the molar concentration of described nickel acetate is controlled at 0.030-0.100mol/L.
4. the method for claim 1, wherein put into 0.1g silica in every 40ml deionized water in the step (1), and ultrasonic dispersion forms white emulsion.
5. as each described method of claim 1-4, wherein, temperature retention time is 3-28h in the step (3).
6. as each described method of claim 1-4, wherein, the mol ratio of the silicon of adding and the nickel of adding is between 4: 3 to 1: 2.
7. the method for claim 1, wherein fixing mol ratio of silicon and nickel in the initial action liquid is regulated and control the size of internal voids between the shell nuclear by the temperature retention time in regulating step (3) the mesohigh still; Or recently regulate and control the size of internal voids between the shell nuclear by the mole of silicon and nickel in the conditioned reaction liquid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647543A (en) * | 2018-12-20 | 2019-04-19 | 山西大学 | A kind of Ni-based catalyst with core-casing structure and its preparation method and application |
| CN109847765A (en) * | 2019-03-08 | 2019-06-07 | 西北师范大学 | The preparation and the application in evolving hydrogen reaction of CdSNRs@NiSilicate ultrathin nanometer piece composite material |
| CN110240169A (en) * | 2019-07-03 | 2019-09-17 | 山东科技大学 | A kind of three-dimensional petal-shaped alkali formula silicic acid nickel and preparation method thereof |
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| JP2002066335A (en) * | 2000-08-24 | 2002-03-05 | Toyota Central Res & Dev Lab Inc | Dispersed noble metal-containing alumina particle, its preparation process and exhaust gas purification catalyst |
| CN102091625A (en) * | 2010-12-24 | 2011-06-15 | 南京工业大学 | Nickel-based catalyst prepared by solid-phase thermal dispersion and preparation method thereof |
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2013
- 2013-05-06 CN CN2013101718448A patent/CN103252237A/en active Pending
Patent Citations (3)
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| JP2002066335A (en) * | 2000-08-24 | 2002-03-05 | Toyota Central Res & Dev Lab Inc | Dispersed noble metal-containing alumina particle, its preparation process and exhaust gas purification catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647543A (en) * | 2018-12-20 | 2019-04-19 | 山西大学 | A kind of Ni-based catalyst with core-casing structure and its preparation method and application |
| CN109847765A (en) * | 2019-03-08 | 2019-06-07 | 西北师范大学 | The preparation and the application in evolving hydrogen reaction of CdSNRs@NiSilicate ultrathin nanometer piece composite material |
| CN109847765B (en) * | 2019-03-08 | 2021-06-08 | 西北师范大学 | Preparation of CdSNRs @ NiSilicate ultrathin nanosheet composite material and application of composite material in hydrogen evolution reaction |
| CN110240169A (en) * | 2019-07-03 | 2019-09-17 | 山东科技大学 | A kind of three-dimensional petal-shaped alkali formula silicic acid nickel and preparation method thereof |
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Application publication date: 20130821 |