CN1154268A - Multi-step reaction method for preparing media-porousness composite compound of nickel oxide/silicon oxide and nickel/silicon oxide - Google Patents
Multi-step reaction method for preparing media-porousness composite compound of nickel oxide/silicon oxide and nickel/silicon oxide Download PDFInfo
- Publication number
- CN1154268A CN1154268A CN 96117101 CN96117101A CN1154268A CN 1154268 A CN1154268 A CN 1154268A CN 96117101 CN96117101 CN 96117101 CN 96117101 A CN96117101 A CN 96117101A CN 1154268 A CN1154268 A CN 1154268A
- Authority
- CN
- China
- Prior art keywords
- sio
- acid
- nicl
- nio
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
- Silicon Compounds (AREA)
Abstract
Thyl ortho silicate, ethyl alcohol and water are used as raw material to prepare porous silicon dioxide solid by sol-gel method, then immerse the SiO2 solid in NiCl2 solution, take out and wash, immerse in ammonium carbonate solution, mesoporous solid of NiCO3 and SiO2 is obtd.. After sintering, mesoporous complex substance of NiO/SiO2 is obtd.. The invented method is simple, product quality is high, purity higher than 99%. particle distribution is even, the amount of Ni and NiO doped can be controlled.
Description
The present invention prepares nickel oxide/silica (NiO/SiO with the multistep chemical reaction method
2) and nickel/silica (Ni/SiO
2) mesic hole compound.
The research of artificial nano material has continued more than ten years, and its peculiar performance and tempting application prospect have caused the extensive attention of international material scientific circles.The nanoscale that the research of nanometer assembly system and design have new breakthrough and nano-device to interrelate designs or the research of nanometer assembled material has become the popular domain that people extraordinarily pay attention to.And mesic hole compound is current nanometer assembly system important research object, its main design philosophy is to utilize short grained quantum size effect and seep effect, as required the material monolithic performance is cut out, adjustment and control reach the peculiar performance that conventional material does not possess.The preparation of mesic hole compound generally has the diffusion method and the ion-exchange of prefabricated colloid.The diffusion method of prefabricated colloid at first must prepare colloid, with the colloid ion diffusion, obtains complex at last again; Ion-exchange is with ion and ion-exchange, obtains required complex at last.But these reaction unit complexity, operating difficulties, the cycle is long, and gained distribution of particles dimensional homogeneity is poor, and blended amount is wayward.
The object of the invention provides a kind of multistep chemical reaction method and prepares NiO/SiO
2And Ni/SiO
2The method of mesic hole compound, this preparation method is simple, gained distribution of particles good uniformity.
For achieving the above object, the present invention adopts following technical method:
At first first step employing ethyl orthosilicate (TEOS), second alcohol and water are raw material, under the effect of acid catalyst, adjust pH value with ammoniacal liquor, and its scope 2-7 is passed through colloidal sol--gel reaction is prepared the SiO that has hole
2Solid; Second step was the SiO that has hole
2Solid is immersed in NiCl earlier
2In the solution, take out cleaning after, be placed on (NH again
4)
2CO
3The middle immersion makes NiCl
2(NH
4)
2CO
3At SiO
2Hole in fully the reaction, obtain NiCO
3SiO
2Mesoporous solid can obtain NiO/SiO at 300～800 ℃ of temperature lower calcinations again
2Mesic hole compound.
The 3rd step will prepare Ni/SiO
2Mesic hole compound, only need logical hydrogen reducing NiO/SiO
2Mesic hole compound get final product.
The percentage composition of the used ethyl orthosilicate of the present invention is 20～40%; The percentage composition of ethanol is between 50～99%; The content of ammonia is 20～50%; Water is distilled water, and its electrical conductivity is less than 10
-4S.m
-1Acid catalyst concentration is 0.1～4mol/L, mesoporous SiO
2The aperture can control by the concentration of different acid, acid can be hydrochloric acid, phosphoric acid, hydrofluoric acid, perchloric acid also can be nitric acid etc.; NiCl
2Concentration be 0.001～3mol/L; (NH
4)
2CO
3Concentration be 0.01～2mol/L.The volume ratio of ethyl orthosilicate, water, ethanol and acid is (0.5～1): (1～4): (1～4): (0.0006～1); (NH
4)
2CO
3And NiCl
2(0.5～1) in molar ratio: (0.001～0.3); And mesoporous SiO
2The compound quantity of the Ni of NiO in the solid can be passed through NiCl
2Concentration control, in＞350 ℃ temperature, handle NiCO
3SiO
2Mesoporous solid 2～5 hours promptly obtains grayish green, light green NiO/SiO to green (deciding according to blended amount)
2Mesic hole compound, in the atmosphere of hydrogen, hydrogen-pressure remains under the condition of 1～10MPa again, at 300 ℃～800 ℃ following NiO/SiO of temperature
2Reduction can obtain Ni/SiO
2Mesic hole compound.
The advantage of the inventive method is, preparation method is simple, and technology is succinct, and the mesic hole compound output height that makes, pure height (＞99%), and even particle distribution can reach porosity and the specific surface that improves mesic hole compound by the concentration of controlling different acid; Change NiCl
2Concentration control different blended amount.NiO/SiO with the inventive method making
2And Ni/SiO
2Mesic hole compound has good Air-sensitive switch effect, can be used as air-sensitive and dew cell, carried catalyst, the element of nonlinear optics and electricity aspect etc.
The invention will be further described below in conjunction with embodiment:
Embodiment:
1. step 1: at first with ethyl orthosilicate (TEOS), water, ethanol, hydrofluoric acid 1: 2: 2 in molar ratio: mix (0.1～0.05), wherein TEOS content is 20～30%, ethanol is 80～95%, hydrofluoric acid concentration is 1mol/L, stir and add entry and ethanol after 25～35 minutes, make its abundant hydrolysis, add ammoniacal liquor again, its content 30～40%, adjusting pH value is 3～4, after the stirred for several minute, contain air dry in the closed container again, promptly obtain porous SiO after 2 hours through 550 ℃ of following heat treatment
2Solid, its pore-size distribution are at 7～12nm, and porosity is 48%, and specific surface is 720m
2.g
-1
Step 2: a porous SiO who makes set by step
2Solid is immersed in the NiCl of 0.05mol/L
2After 3～6 days, take out and clean for several times in the solution, be placed on (the NH of 0.5～1mol/L then
4)
2CO
3Soaked in the solution 3～6 days, and took out the back, promptly obtain the NiO/SiO of celadon 400 ℃～480 ℃ heat treatments 2 hours
2Mesic hole compound, wherein the compound content of NiO is 16.2% (weight percentage), the NiO particle mean size is 10nm.
Step 3: the NiO/SiO that one, two methods are set by step made
2Mesic hole compound remains under 4～10MPa condition at the hydrogen-pressure flow, adds thermal reduction 1.5h under 400 ℃, get final product Ni/SiO
2Mesic hole compound, wherein the compound content of Ni is 12.7%, the Ni particle mean size is 7nm.
2. step 1: promptly the step 1 by embodiment 1 makes pore-size distribution at 7～12nm, and porosity is 48%, and specific surface is 720m
2.g
-1SiO
2Mesoporous solid.
Step 2: also be the step 2 preparation by embodiment 1, different is to increase NiCl
2Concentration to 0.3mol/L, obtain the NiO/SiO of line green
2Mesic hole compound, wherein the compound quantity of NiO is 9.7%.
Step 3: with the step 3 of embodiment 1, the compound content for preparing Ni is 7.6% Ni/SiO
2Mesic hole compound.
3. step 1: press the step 1 preparation of embodiment 1, but the mol ratio that changes TEOS, water, ethanol, hydrofluoric acid is 1: 2: 2: (0.001～0.1), can make pore-size distribution 4～10nm, porosity is 51%, specific surface is 740m
2.g
-1Porous SiO
2Solid.
Step 2: the compound content that makes NiO by the step 2 of embodiment 1 is the mesoporous NiO/SiO of 14.7% celadon
2Complex.
Step 3: the compound content that makes Ni by the step 3 of embodiment 1 is 11.5% Ni/SiO
2Mesic hole compound.
Can prove clearly that by embodiment 1,2,3 the inventive method can be by changing NiCl
2Concentration control different blended amount, change the mol ratio of TEOS, water, ethanol, hydrofluoric acid, then make the different NiO/SiO in aperture
2And Ni/SiO
2Mesic hole compound.
Claims (5)
1. a multistep reaction method for preparing nickel oxide/silica and nickel/silica is characterized in that, adopts ethyl orthosilicate earlier, the second alcohol and water is a raw material, under the effect of acid catalyst, adjust pH value with ammoniacal liquor, pass through colloidal sol--gel reaction is prepared the SiO that has hole
2Solid; Again with the SiO in hole with holes
2Solid is immersed in NiCl
2In the solution, take out cleaning after, be placed on (NH again
4)
2CO
3The middle immersion makes NiCl
2(NH
4)
2CO
3At SiO
2Hole in fully the reaction, obtain NiCO
3SiO
2Mesoporous solid promptly obtains NiO/SiO at 300 ℃～800 ℃ temperature lower calcinations
2Mesic hole compound, logical again hydrogen reducing NiO/SiO
2Mesic hole compound, promptly obtain Ni/SiO
2Mesic hole compound.
2. the method for claim 1 is characterized in that, the percentage composition of used ethyl orthosilicate is 20～40%, and the percentage composition of ethanol is between 50～99%, and the percentage composition of ammoniacal liquor is 20～50%, and water is distilled water, and its electrical conductivity is less than 10
-4Sm
-1, acid catalyst concentration is 0.1～4mol/L, NiCl
2Concentration be 0.001～3mol/L, (NH
4)
2CO
3Concentration be 0.01～2mol/L.
3. the method for claim 1 is characterized in that, described acid catalyst can be hydrochloric acid, phosphoric acid, perchloric acid, hydrofluoric acid, nitric acid etc.
4. the method for claim 1 is characterized in that, the volume ratio of used ethyl orthosilicate, water, ethanol and acid catalyst is: (0.5～1): (1～4): (1～4): (0.0006～1); (NH
4)
2CO
3And NiCl
2(0.5～1) in molar ratio: (0.001～0.3).
5. the method for claim 1 is characterized in that, can be by changing NiCl
2Concentration control different blended amount; The mol ratio that changes TEOS, water, ethanol, acid can make the mesic hole compound in the different apertures that contain NiO and Ni.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96117101 CN1154268A (en) | 1996-09-18 | 1996-09-18 | Multi-step reaction method for preparing media-porousness composite compound of nickel oxide/silicon oxide and nickel/silicon oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96117101 CN1154268A (en) | 1996-09-18 | 1996-09-18 | Multi-step reaction method for preparing media-porousness composite compound of nickel oxide/silicon oxide and nickel/silicon oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1154268A true CN1154268A (en) | 1997-07-16 |
Family
ID=5124038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96117101 Pending CN1154268A (en) | 1996-09-18 | 1996-09-18 | Multi-step reaction method for preparing media-porousness composite compound of nickel oxide/silicon oxide and nickel/silicon oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1154268A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441293C (en) * | 2005-09-26 | 2008-12-10 | 天津大学 | Supported nickel catalyst for synthesizing chlora aniline by hydrogenation of chloronitrobenzene and its preparation method thereof |
| CN103055913A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Nickel-silicon composite oxide and preparation method thereof |
| CN104549292A (en) * | 2015-03-02 | 2015-04-29 | 天津大学 | Technological method for preparing nickel/silicon dioxide supported catalyst by laser liquid phase |
| CN110013854A (en) * | 2019-05-09 | 2019-07-16 | 福州大学 | The preparation and the application in C5/C9 Petropols catalytic hydrogenation of a kind of load-type nickel series catalysts |
-
1996
- 1996-09-18 CN CN 96117101 patent/CN1154268A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441293C (en) * | 2005-09-26 | 2008-12-10 | 天津大学 | Supported nickel catalyst for synthesizing chlora aniline by hydrogenation of chloronitrobenzene and its preparation method thereof |
| CN103055913A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Nickel-silicon composite oxide and preparation method thereof |
| CN103055913B (en) * | 2011-10-24 | 2015-02-11 | 中国石油化工股份有限公司 | Nickel-silicon composite oxide and preparation method thereof |
| CN104549292A (en) * | 2015-03-02 | 2015-04-29 | 天津大学 | Technological method for preparing nickel/silicon dioxide supported catalyst by laser liquid phase |
| CN110013854A (en) * | 2019-05-09 | 2019-07-16 | 福州大学 | The preparation and the application in C5/C9 Petropols catalytic hydrogenation of a kind of load-type nickel series catalysts |
| CN110013854B (en) * | 2019-05-09 | 2021-06-22 | 福州大学 | Preparation of supported nickel catalyst and application of supported nickel catalyst in catalytic hydrogenation of C5/C9 petroleum resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018113485A1 (en) | Membrane electrode of high power density proton exchange membrane fuel cell and preparation method therefor | |
| CN101116808B (en) | Photocatalysis powder having a negative ion releasing function and method for preparing the same | |
| JP4204272B2 (en) | Fuel cell electrode catalyst and fuel cell | |
| CN101185885A (en) | Method for preparing perovskite type catalyst for methane or methanol recapitalization | |
| CN103855412B (en) | Lithium-air battery positive pole porous carbon materials | |
| CN110797542A (en) | Symmetric solid oxide fuel cell electrode material and preparation method thereof | |
| CN105396601A (en) | Nano catalyst of multi-corner-angle gradient structure and preparation method thereof | |
| CN106058276A (en) | Preparation method of silica-modified multi-spherical-cavity carbon material and application of carbon material to fuel cell membrane electrode | |
| CN109888305A (en) | Dipping solution is improved to the method for solid oxide fuel cell porous cathode skeleton wetability | |
| CN101176841A (en) | Perovskite type catalyzer for methyl hydride or methanol recapitalization and uses thereof | |
| CN101337184A (en) | Composite electrocatalyst capable of increasing cathode mass-transfer performance of fuel cell | |
| CN1154268A (en) | Multi-step reaction method for preparing media-porousness composite compound of nickel oxide/silicon oxide and nickel/silicon oxide | |
| Li et al. | Template-directed synthesis of mesoporous TiO 2 materials for energy conversion and storage | |
| CN110400954A (en) | A method of electrolytic thin-membrane is prepared on clear opening anode support | |
| CN102738482B (en) | Self-humidifying membrane and self-humidifying fuel cell | |
| CN111229194A (en) | (TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2Preparation and use of catalysts | |
| CN112652796B (en) | High-durability hydrogen fuel cell proton exchange membrane and preparation method and application thereof | |
| KR102225354B1 (en) | Manufactuuring method of catalyst support for electrochemical cell using wettability of solvent | |
| KR100392418B1 (en) | Mesoporous Carbon/Metal Oxide Composite Materials And Preparing Method Thereof And Electrochemical Capacitors Using Them | |
| CN106833040A (en) | A kind of titania-doped automatically cleaning composite nano-coating of porous metal and its preparation method and application | |
| CN108187720B (en) | Preparation method of N-Au co-doped composite titanium dioxide nanowire | |
| CN113832495A (en) | Multi-stage structure composite fuel electrode for solid oxide electrolytic cell and preparation method thereof | |
| CN114635150A (en) | Novel solid oxide electrolytic cell oxygen electrode and preparation method thereof | |
| CN1110868C (en) | Preparation of thin electrodes for fuel cells | |
| CN114086196B (en) | Oxygen evolution perovskite catalyst with low overpotential and high stability and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |