CN100586846C - Method for mass preparing hollow nano carbon cages with high quality - Google Patents
Method for mass preparing hollow nano carbon cages with high quality Download PDFInfo
- Publication number
- CN100586846C CN100586846C CN200810023448A CN200810023448A CN100586846C CN 100586846 C CN100586846 C CN 100586846C CN 200810023448 A CN200810023448 A CN 200810023448A CN 200810023448 A CN200810023448 A CN 200810023448A CN 100586846 C CN100586846 C CN 100586846C
- Authority
- CN
- China
- Prior art keywords
- reaction
- hollow nano
- nano cages
- tube
- temperature
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 54
- 229910021392 nanocarbon Inorganic materials 0.000 title 1
- 239000002091 nanocage Substances 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 239000007789 gas Substances 0.000 claims abstract description 64
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 14
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 137
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 50
- 229910052786 argon Inorganic materials 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 230000007935 neutral effect Effects 0.000 claims description 30
- OGWLTJRQYVEDMR-UHFFFAOYSA-F tetramagnesium;tetracarbonate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O OGWLTJRQYVEDMR-UHFFFAOYSA-F 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 230000005587 bubbling Effects 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 239000010935 stainless steel Substances 0.000 claims description 14
- 229960001708 magnesium carbonate Drugs 0.000 claims description 13
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 3
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 2
- 240000005373 Panax quinquefolius Species 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 36
- 239000001117 sulphuric acid Substances 0.000 abstract description 4
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 27
- 239000002245 particle Substances 0.000 description 26
- 230000035484 reaction time Effects 0.000 description 24
- 230000003252 repetitive effect Effects 0.000 description 24
- 238000005201 scrubbing Methods 0.000 description 24
- 238000005303 weighing Methods 0.000 description 24
- 239000012300 argon atmosphere Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
A method for mass production of high-quality hollow carbon nanocages comprises the following steps: 1) light magnesium carbonate or magnesium carbonate is added into a reaction tube and spread evenly,the tube is put into a tubular furnace, air is pumped out of the tube, inert gas such as N2 and Ar is injected; the reaction temperature is increased to 670 DEG C-900 DEG C, (C) source vapor is introduced, and reaction is carried out for 5 to 240 minutes under the protection of 10-500sccm inert gas atmosphere; the (C) source gas is led to the reaction area of the tubular furnace by the inert gasflow, carbonized on the surfaces of nano particles generated in situ, and covered to form a MgO@C structure; after the reaction, the temperature inside the reaction tube drops to the room temperatureunder the protection of the inert gas; 2) powder is collected from the reaction tube, dipped in sufficient hydrochloric acid or sulphuric acid for 5 to 720 minutes to remove the kernel of MgO, filtered, washed to neutrality by using deionized water, and dried to obtain the hollow carbon nanocages; and 3) the magnesium salt filtrate is recycled. The nanocages prepared by the method have high purity, and the price for the precursor is low, thereby facilitating recovery and reuse.
Description
Technical field
The present invention relates to a kind of is precursor with carbonaceous organic materials such as magnesium basic carbonate (or magnesiumcarbonate) and benzene, and the bitter earth nano particle that produces with magnesium basic carbonate or magnesiumcarbonate decomposition in situ is a template, prepares the method for hollow nano cages in high quality in a large number.
Background technology
Character such as the novel structure of carbon fullerene and nanotube and unique light, electricity, magnetic and caused people's extensive attention, and excited people to explore other carbon nano-structured interest (R.H.Baughman, et al.Science 2002,297,787).Hollow nano cages normally prepares the by product that forms in the carbon nanotube process, is covered by the radiance of carbon nanotube and by long-standing neglect.Yet this uniqueness hollow nanostructured has unique physicochemical property, there are some researches show, its be expected to be applied to numerous areas such as catalysis, the energy, separation, optics (Anvar A.Zakhidov, et al.Science 1998,282,897; S.Han, et al.Adv.Mater.2003,15,1922; Ajayan Vinu et al., J.Porous Mater 2006,13,379; J.J.Niu, et al.J.Phys.Chem.C 2007,111,10329).Up to the present, people have been developed several technological lines and have been prepared hollow nano cages, for example: (S.Han, et al.Adv.Mater.2003 such as arc process, laser evaporation method, Plasma Polymerization, chemical vapor deposition method (CVD), supercutical fluid method, 22: 1922; Y.M.Ma, et al.Carbon.2005,8,1667; J.Y.Miao, et al.Carbon 2004,42,813; J.Cao, et al.J.Nanoparticle Res.2004,6,447).A common feature of above-mentioned synthetic method is that synthetic hollow nano cages generally needs template, and the material that is used as template has metallics, high score bulbec and SiO
2(G.Hu, et al., Chem.Commun.2002,1948 such as ball; J.Jang, et al.Chem.Mater.2003,15,2109; J.Jang, et al.Adv.Mater.2002,14,1390).Its principal character is the carbon paste capsule that at first forms core/shell structure, selects for use suitable physico-chemical process that nuclear is removed according to inner nuclear material again, obtains hollow nano cages at last.Also needing to carry out high temperature cabonization for polymer-based nanocages handles.Because above method relates to complicated multistep process, and some technology uses is poisonous or the disagreeableness reagent of environment, so these technologies more or less exist unfavorable factor.
200410024700.0 " method for preparing hollow nano cages in a large number " discloses a kind of a large amount of method for preparing hollow nano cages.Be used for the nano material preparation technical field.At first prepare the solid carbon nanocages: metal carbonyls liquid and the even proportioning of low-carbon (LC) class organic liquid are got reaction soln and place volumetric flask, main reactor heats up, and feeding rare gas element, reaction soln is sprayed into by the main reactor top through electronic peristaltic pump, in main reactor bottoms collector, obtain being enclosed with the solid carbon nanocages of metallics; Prepare hollow nano cages then: the solid carbon nanocages that obtains is placed pure nitric acid or pure nitric acid and distilled water mixing solutions, place ultrasonator to carry out sonic oscillation this miscellany; With the mixture heating up after the vibration, and add the recirculated water reflux cooling; Again with mixture adding distil water dilution, be neutral or near neutral until solution, leave standstill then and make the solid matter deposition and outwell upper liquid, oven dry immediately, hollow nano cages.
200510110213.0 " method for preparing hollow nano cages in a large number " discloses a kind of a large amount of method for preparing hollow nano cages, is used for the nano material preparation technical field.The present invention at first prepares the solid carbon nanocages: metal carbonyls liquid and the even proportioning of low-carbon (LC) class organic liquid are got reaction soln and place volumetric flask, main reactor is heated up, and feeding rare gas element, reaction soln is sprayed into by main reactor end injector through electronic peristaltic pump, in main reactor afterbody product collector, obtain being enclosed with the solid carbon nanocages of metallics; Prepare hollow nano cages then:, place pure hydrochloric acid or pure hydrochloric acid and distilled water mixing solutions to carry out sonic oscillation then with the solid carbon nanocages atmospheric oxidation that obtains; Mixture after the vibration is added deionized water rinsing, filtration, be neutral or approaching neutral, right until solution
After leave standstill and make solid matter deposition and outwell upper liquid, oven dry immediately, hollow nano cages.
200610024088.6 " method of solid-state preparing great amount of hollow nanometer carbon cage " discloses a kind of method of solid-state preparing great amount of hollow nanometer carbon cage, is used for the nano material preparation technical field.The present invention prepares at first in a large number the equally distributed amorphous carbon precursor of iron catalyst particle, then precursor is heat-treated by solid state reaction and obtain hollow nano cages, at last hollow nano cages is carried out subsequent disposal and remove catalyzer, promptly get final product.
Summary of the invention
Simpler, the safer novel method and the new technology path that the purpose of this invention is to provide a large amount of and high-quality preparation hollow nano cages of a kind of original position template.Concrete technical scheme is as follows:
A kind of a large amount of method for preparing hollow nano cages in high quality, step comprises:
1) preparation solid carbon nanocages:
Get magnesium basic carbonate or magnesiumcarbonate and join in the reaction tubes, evenly loose in the shop, puts into tube furnace; Deflating then charges into rare gas element, and Bubbling method is introduced volatility C source steam, and under the protection of 10-500sccm atmosphere of inert gases, temperature of reaction is warmed up to 670 ℃～900 ℃ gradually, reacts 5～240 minutes; Described volatility C source steam is brought the tube furnace reaction zone into through inert gas flow, and bitter earth nano particle surface carbonization of Sheng Chenging and parcel form the MgO@C structure in position;
Above-mentioned reaction finishes the back under the protection of rare gas element, and temperature is reduced to room temperature in the reaction tubes;
2) preparation hollow nano cages:
Collect powder from reaction tubes, place hydrochloric acid or the sulfuric acid of 0.1～10mol/L of capacity to soak 5-720 minute, remove the kernel of MgO, filter, to neutral, oven dry obtains hollow nano cages with deionized water wash.
3) reclaim magnesium salts filtrate:
To step 2) in MgO and the magnesium salts filtrate that obtains of hydrochloric acid or sulfuric acid reaction reclaim.
In the step 1), reaction tubes places the central area of tube furnace.
In the step 1), the molar ratio range of C source steam and rare gas element is 0.01-5.
In the step 1), rare gas element is argon gas or nitrogen.
In the step 1), the best in quality flow of rare gas element is 50-100sccm; Optimum reacting time is 30～60 minutes.
In the step 1), the temperature rise rate of temperature of reaction is per minute 5-50 ℃.
In the step 1), the C source comprises benzene, methane, acetylene or ethanol.
In the step 1), described tube furnace is the temperature control tube furnace.
In the step 1), reaction tubes is silica tube, alundum tube, vitrified pipe or stainless steel tube.
In the step 3), as the magnesium basic carbonate or the magnesiumcarbonate of important precursor, recycling easily can reduce cost this process environmental protection.
Step 2) in, the process middle acid substance of removal template does not have destruction to the structure of nano cages.
Device required for the present invention mainly contains CVD depositing system, gas distributing system and vacuum system three parts and forms, the relation of its each several part is as follows with effect: (1) CVD system comprises that the reaction chamber of being made by silica tube places in the tube furnace, the corundum boat that is placed with magnesium basic carbonate places the reaction chamber center, and the temperature of vitellarium can be regulated and control.(2) gas distributing system is made up of gas circuit and mass flowmeter, is connected to an end of growth room, utilizes it can regulate kind, the input of carbon source.(3) vacuum system is regulated vacuum tightness and reacting gas pressure in the growth room.
The MgO kernel only needs to soak and can remove with hydrochloric acid or dilute sulphuric acid among the present invention.
Hollow nano cages purity height provided by the present invention (not containing other impurity substantially), specific surface area can reach 2000m
2G
-1, pore volume can reach 4.50cm
3G
-1, particle diameter is about 10～50nm, and mesoporous rate is higher than 99%.
Characteristics of the present invention are as follows:
MgO nanoparticle as template is that temperature-rise period decomposes the generation of breaking by magnesium basic carbonate or magnesiumcarbonate, and carbon source is wrapped to form the MgO@C structure in its surperficial carbonization, and kernel MgO removes easily.
Need not use metal catalyst, MgO be template be again catalyzer, it is easy to remove.
The product purity height, free from foreign meter substantially, have advantages such as specific surface area height, big, the mesoporous rate height of pore volume, degree of graphitization be good.
By regulation and control growth temperature, material flow and growth time etc., regulate and control the performance (as specific surface area, pore volume, size distribution etc.) of product.
All can prepare hollow nano cages by changing carbon source.
As the magnesium basic carbonate or the magnesiumcarbonate of important precursor, cheap, recycling easily can reduce cost environmental protection.
Description of drawings
Fig. 1: the synoptic diagram of the temperature control tube furnace of growing nanometer hollow carbon cage of the present invention.
1 stopping valve, 2 mass flowmeters, 3 four-way valves, 4 saturexs, 5 High Temperature Furnaces Heating Apparatuss, 6 thermopairs, 7 temperature controllers, 8 silica tubes, 9 filter screens, 10 vacuumometers, 11 vacuum pumps.
Fig. 2: the process synoptic diagram of hollow nano cages preparation.
Fig. 3: with benzene is precursor, and 700 ℃ are reacted 60min, the TEM photo before and after the acid treatment of product salt, HRTEM photo, the result of EDS down.
Fig. 4: with benzene is precursor, reacts 60min under the differing temps, the TEM photo of product hollow nano cages (a-e is respectively 700,750,800,850,900 ℃).Product hollow nano cages under other temperature is similar with the said temperature product, has not just enumerated one by one.
Fig. 5: with benzene is precursor, and 700 ℃ are reacted 30min, the TEM photo of product hollow nano cages down.
Fig. 6: with benzene is precursor, and 700 ℃ are reacted 40min, the TEM photo of product hollow nano cages down.
Fig. 7: with benzene is precursor, under 700 ℃, and reaction 90min, the TEM photo of product hollow nano cages.
Fig. 8: with benzene is precursor, under 700 ℃, and reaction 120min, the TEM photo of product hollow nano cages.
Fig. 9: with ethanol is precursor, under 700 ℃, and reaction 60min, the TEM photo of product.
Embodiment
Below in conjunction with accompanying drawing and embodiment the inventive method is described.
The method that the present invention prepares hollow nano cages is as follows, and the reaction tubes that will be placed with magnesium basic carbonate or magnesiumcarbonate earlier places above-mentioned growth room, at 10-500sccm Ar or N
2Be heated to 670-900 ℃ under the protection of gas.Then carbon-source gas (as benzene, methane, acetylene or ethanol etc.) is introduced reaction chamber, reaction 5min-240min is at Ar or N
2Be cooled to room temperature under the protection of gas, collect the powder in the silica tube.Place capacity hydrochloric acid or sulfuric acid to stir for some time in this powder, filter, wash, dry, can remove the MgO template.Optimum temps of the present invention is 670-900 ℃, and the flow of Ar or N2 gas is 50-100sccm (a standard cubic centimeter per minute), and growth time is 30-60min.The magnesium salts filtrate that also MgO and hydrochloric acid or sulfuric acid reaction is obtained after reaction finishes is reclaimed.Because this is recovered as existing for knowing technology, does not do too much restriction at this.
The temperature control tube furnace of growing nanometer hollow carbon cage as shown in Figure 1
Embodiment 1 is a precursor with benzene, and temperature of reaction is 670 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the silica tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 670 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, and Bubbling method is introduced benzene vapor, reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (50sccm), collects powder from silica tube, places the dilute hydrochloric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area can reach 2000m
2G
-1, pore volume can reach 4.50cm
3G
-1, particle diameter is about 10～30nm, and mesoporous rate is higher than 99.7%.
Embodiment 2 is a precursor with benzene, and temperature of reaction is 690 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the alundum tube, evenly loose in the shop, puts into the tube furnace central area, then inflated with nitrogen and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 690 ℃ with the temperature rise rate of 10 ℃ of per minutes under nitrogen atmosphere, and Bubbling method is introduced benzene vapor, reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of nitrogen (50sccm), collects powder from alundum tube, places the dilute hydrochloric acid of 0.1mol/L to soak 12 hours, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area can reach 1800m
2G
-1, pore volume can reach 4.10cm
3G
-1, particle diameter is about 10～30nm, and mesoporous rate is higher than 99.7%.
Embodiment 3 is a precursor with benzene, and temperature of reaction is 700 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the vitrified pipe, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 700 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, and Bubbling method is introduced benzene vapor, reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (50sccm), collects powder from vitrified pipe, places the hydrochloric acid of 10mol/L to soak 5 minutes, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.(see Fig. 3, Fig. 4 a) specific surface area can reach 1700m
2G
-1, pore volume can reach 4.00cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 4 is a precursor with benzene, and temperature of reaction is 710 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the vitrified pipe, evenly loose in the shop, puts into the tube furnace central area, then inflated with nitrogen and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 710 ℃ with the temperature rise rate of 10 ℃ of per minutes under nitrogen atmosphere, and Bubbling method is introduced benzene vapor, reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of nitrogen (50sccm), collects powder from vitrified pipe, places the hydrochloric acid of 5mol/L to soak 0.5 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area can reach 1500m
2G
-1, pore volume can reach 3.80cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Take by weighing a certain amount of magnesium basic carbonate and join in the alundum tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 730 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, and Bubbling method is introduced benzene vapor, reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (50sccm), collects powder from alundum tube, places the dilute hydrochloric acid of 1mol/L to soak 0.5 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area can reach 1300m
2G
-1, pore volume can reach 3.00cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 6 is a precursor with benzene, and temperature of reaction is 750 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the vitrified pipe, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 750 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon gas atmosphere is enclosed, and Bubbling method is introduced benzene vapor, reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (50sccm), collects powder from vitrified pipe, places the dilute hydrochloric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.(seeing Fig. 4 b) specific surface area can reach 1200m
2G
-1, pore volume can reach 2.50cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 7 is a precursor with benzene, and temperature of reaction is 800 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesiumcarbonate and join in the vitrified pipe, evenly loose in the shop, puts into the tube furnace central area, then inflated with nitrogen and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 800 ℃ with the temperature rise rate of 10 ℃ of per minutes under nitrogen atmosphere, and Bubbling method is introduced benzene vapor, reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of nitrogen (50sccm), collects powder from vitrified pipe, places the dilute hydrochloric acid of 1mol/L to soak 2 hours, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.(seeing Fig. 4 c) specific surface area 600m
2G
-1, pore volume 1.20cm
3G
-1, particle diameter is about 10～50nm, and mesoporous rate is higher than 99.3%.
Embodiment 8 is a precursor with benzene, and temperature of reaction is 850 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the silica tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 850 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, and Bubbling method is introduced benzene vapor, reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (50sccm), collects powder from silica tube, places the dilute hydrochloric acid of 1mol/L to soak 3 hours, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.(seeing Fig. 4 d) specific surface area 200m
2G
-1, pore volume 0.70cm
3G
-1, particle diameter is about 10～50nm, and mesoporous rate is higher than 99.3%.
Embodiment 9 is a precursor with benzene, and temperature of reaction is 900 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesiumcarbonate and join in the silica tube, evenly loose in the shop, puts into the tube furnace central area, then inflated with nitrogen and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 900 ℃ with the temperature rise rate of 10 ℃ of per minutes under nitrogen atmosphere, and Bubbling method is introduced benzene vapor, reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of nitrogen (50sccm), collects powder from silica tube, places the dilute hydrochloric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.(seeing Fig. 4 e) specific surface area 30m
2G
-1, pore volume 0.10cm
3G
-1, particle diameter is about 10～50nm, and mesoporous rate is higher than 99.3%.
Embodiment 10 is a precursor with benzene, and temperature of reaction is 700 ℃, and the reaction times is 10min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the silica tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 700 ℃ with the temperature rise rate of 5 ℃ of per minutes under argon gas or nitrogen atmosphere, and Bubbling method is introduced benzene vapor, reacts 10 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas or nitrogen (50sccm), collects powder from silica tube, places the dilute hydrochloric acid of 1mol/L to soak 1 hour; filter; to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area can reach 1600m
2G
-1, pore volume can reach 4.00cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 11 is a precursor with benzene, and temperature of reaction is 700 ℃, and the reaction times is 20min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the stainless steel tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 700 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, and Bubbling method is introduced benzene vapor, reacts 20 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (50sccm), collects powder from stainless steel tube, places the dilute sulphuric acid of 0.1mol/L to soak 12 hours, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area can reach 1650m
2G
-1, pore volume can reach 4.10cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 12 is a precursor with benzene, and temperature of reaction is 700 ℃, and the reaction times is 30min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the silica tube, evenly loose in the shop, puts into the tube furnace central area, then inflated with nitrogen and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 700 ℃ with the temperature rise rate of 20 ℃ of per minutes under nitrogen atmosphere, and Bubbling method is introduced benzene vapor, reacts 30 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (50sccm), collects powder from silica tube, places the dilute sulphuric acid of 0.5mol/L to soak 6 hours, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.The (see figure 5) specific surface area can reach 1750m
2G
-1, pore volume can reach 4.00cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 13 is a precursor with benzene, and temperature of reaction is 700 ℃, and the reaction times is 40min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the silica tube, evenly loose in the shop, puts into the tube furnace central area, then inflated with nitrogen and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 700 ℃ with the temperature rise rate of 30 ℃ of per minutes under nitrogen atmosphere, and Bubbling method is introduced benzene vapor, reacts 40 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of nitrogen (50sccm), collects powder from silica tube, places the sulfuric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.The (see figure 6) specific surface area can reach 1600m
2G
-1, pore volume can reach 4.00cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 14 is a precursor with benzene, and temperature of reaction is 700 ℃, and the reaction times is 90min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the silica tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 700 ℃ with the temperature rise rate of 40 ℃ of per minutes under argon atmosphere, and Bubbling method is introduced benzene vapor, reacts 90 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (50sccm), collects powder from silica tube, places the sulfuric acid of 5mol/L to soak 0.5 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.The (see figure 7) specific surface area can reach 1550m
2G
-1, pore volume can reach 4.00cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 15 is a precursor with benzene, and temperature of reaction is 700 ℃, and the reaction times is 120min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the stainless steel tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 700 ℃ with the temperature rise rate of 50 ℃ of per minutes under argon atmosphere, and Bubbling method is introduced benzene vapor, reacts 120 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (50sccm), collects powder from stainless steel tube, places the sulfuric acid of 10mol/L to soak 5 minutes, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.The (see figure 8) specific surface area can reach 1500m
2G
-1, pore volume can reach 4.00cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 16 is a precursor with benzene, and temperature of reaction is 700 ℃, and the reaction times is 30min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the vitrified pipe, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(10sccm) is warmed up to 700 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, and Bubbling method is introduced benzene vapor, reacts 30 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (10sccm), collects powder from vitrified pipe, places the dilute hydrochloric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area can reach 1600m
2G
-1, pore volume can reach 4.10cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 17 is a precursor with benzene, and temperature of reaction is 700 ℃, and the reaction times is 30min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the silica tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(100sccm) is warmed up to 700 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, and Bubbling method is introduced benzene vapor, reacts 30 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (100sccm), collects powder from silica tube, places the dilute hydrochloric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area can reach 1670m
2G
-1, pore volume can reach 4.15cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 18 is a precursor with benzene, and temperature of reaction is 700 ℃, and the reaction times is 30min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the silica tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(500sccm) is warmed up to 700 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, and Bubbling method is introduced benzene vapor, reacts 30 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (500sccm), collects powder from silica tube, places the dilute hydrochloric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area can reach 1600m
2G
-1, pore volume can reach 4.00cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 19 is a precursor with ethanol, and temperature of reaction is 700 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the alundum tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 700 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, and Bubbling method is introduced the ethanol steam, reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (50sccm), collects powder from alundum tube, places the dilute hydrochloric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.The (see figure 9) specific surface area can reach 2000m
2G
-1, pore volume can reach 4.30cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 20 is a precursor with ethanol, and temperature of reaction is 800 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesiumcarbonate and join in the silica tube, evenly loose in the shop, puts into the tube furnace central area, then inflated with nitrogen and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 800 ℃ with the temperature rise rate of 10 ℃ of per minutes under nitrogen atmosphere, and Bubbling method is introduced the ethanol steam, reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of nitrogen (50sccm), collects powder from silica tube, places the dilute hydrochloric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area can reach 900m
2G
-1, pore volume can reach 2.10cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 21 is a precursor with methane, and temperature of reaction is 900 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the stainless steel tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(500sccm) is warmed up to 900 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, introduces methane gas (5sccm), reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (500sccm), collects powder from stainless steel tube, places the dilute hydrochloric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area 50m
2G
-1, pore volume can reach 0.20cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 22 is a precursor with methane, and temperature of reaction is 900 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesiumcarbonate and join in the stainless steel tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 900 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, introduces methane gas (50sccm), reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (50sccm), collects powder from stainless steel tube, places the dilute hydrochloric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area 50m
2G
-1, pore volume can reach 0.20cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 23 is a precursor with acetylene, and temperature of reaction is 700 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesium basic carbonate and join in the stainless steel tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 700 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, introduces acetylene gas (20sccm), reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (100sccm), collects powder from stainless steel tube, places the dilute hydrochloric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area 1200m
2G
-1, pore volume can reach 2.60cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Embodiment 24 is a precursor with acetylene, and temperature of reaction is 800 ℃, and the reaction times is 60min, and the original position template prepares hollow nano cages.
Take by weighing a certain amount of magnesiumcarbonate and join in the stainless steel tube, evenly loose in the shop, puts into the tube furnace central area, then applying argon gas and find time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 800 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon atmosphere, introduces acetylene gas (250sccm), reacts 60 minutes.Reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas (10sccm), collects powder from stainless steel tube, places the dilute hydrochloric acid of 1mol/L to soak 1 hour, filters, and to neutral, 110 ℃ of oven dry obtain hollow nano cages with the deionized water repetitive scrubbing.Specific surface area 800m
2G
-1, pore volume can reach 2.00cm
3G
-1, particle diameter is about 10～40nm, and mesoporous rate is higher than 99.5%.
Claims (8)
1, a kind of a large amount of method for preparing hollow nano cages in high quality is characterized in that step comprises:
1) preparation solid carbon nanocages:
Get magnesium basic carbonate or magnesiumcarbonate and join in the reaction tubes, evenly loose in the shop, puts into tube furnace; Deflating then charges into rare gas element, and Bubbling method is introduced volatility C source steam, and under the protection of 10-500sccm atmosphere of inert gases, temperature of reaction is warmed up to 670 ℃～900 ℃ gradually, reacts 5～240 minutes; Described volatility C source steam is brought the tube furnace reaction zone into through inert gas flow, and bitter earth nano particle surface carbonization of Sheng Chenging and parcel form the MgO@C structure in position;
Described C source steam is benzene, methane, acetylene or ethanol;
Above-mentioned reaction finishes the back under the protection of rare gas element, and temperature is reduced to room temperature in the reaction tubes;
2) preparation hollow nano cages:
Collect powder from reaction tubes, place hydrochloric acid or the sulfuric acid of 0.1～10mol/L of capacity to soak 5～720 minutes, remove the MgO kernel, filter, to neutral, oven dry obtains hollow nano cages with deionized water wash.
2, a large amount of method for preparing hollow nano cages in high quality according to claim 1 is characterized in that in the step 1) that reaction tubes places the central area of tube furnace.
3, a large amount of method for preparing hollow nano cages in high quality according to claim 1 is characterized in that in the step 1), and the molar ratio range of C source steam and rare gas element is 0.01-5.
4, a large amount of method for preparing hollow nano cages in high quality according to claim 1 is characterized in that in the step 1), and the best in quality flow of rare gas element is 50-100sccm; Optimum reacting time is 30-60 minute, and the optimal selection of rare gas element is argon gas or nitrogen.
5, a large amount of method for preparing hollow nano cages in high quality according to claim 1 is characterized in that in the step 1), and the temperature rise rate of temperature of reaction is per minute 5-50 ℃.
6, a large amount of method for preparing hollow nano cages in high quality according to claim 1 is characterized in that in the step 1), and described tube furnace is the temperature control tube furnace.
7, a large amount of method for preparing hollow nano cages in high quality according to claim 1 is characterized in that in the step 1), and reaction tubes is silica tube, alundum tube, vitrified pipe or stainless steel tube.
8, a large amount of method for preparing hollow nano cages in high quality according to claim 1 is characterized in that step 2) after, comprise that also step 3) reclaims magnesium salts filtrate: to step 2) in MgO and the magnesium salts filtrate that obtains of hydrochloric acid or sulfuric acid reaction reclaim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810023448A CN100586846C (en) | 2008-04-14 | 2008-04-14 | Method for mass preparing hollow nano carbon cages with high quality |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810023448A CN100586846C (en) | 2008-04-14 | 2008-04-14 | Method for mass preparing hollow nano carbon cages with high quality |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101284663A CN101284663A (en) | 2008-10-15 |
| CN100586846C true CN100586846C (en) | 2010-02-03 |
Family
ID=40057110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810023448A Expired - Fee Related CN100586846C (en) | 2008-04-14 | 2008-04-14 | Method for mass preparing hollow nano carbon cages with high quality |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100586846C (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530922A (en) * | 2012-03-12 | 2012-07-04 | 南京大学 | Method for preparing nitrogen doping hollow carbon nanocages |
| CN102593425A (en) * | 2012-03-12 | 2012-07-18 | 南京大学 | Method for assembling high-performance lithium ion battery based on hollow carbon nanocage cathode material |
| CN102568856A (en) * | 2012-03-14 | 2012-07-11 | 南京大学 | Method for assembling supercapacitor based on hollow carbon nano cage |
| CN102600835A (en) * | 2012-03-16 | 2012-07-25 | 南京大学 | Preparation method of hollow carbon nanocage loaded platinum-based composite catalysts |
| CN104118859B (en) * | 2013-04-25 | 2016-06-15 | 上饶师范学院 | A kind of method preparing agraphitic carbon nanocages with phenol for predecessor in a large number |
| CN103787305B (en) * | 2014-02-19 | 2015-11-18 | 中国科学院上海硅酸盐研究所 | Combustion method prepares the method for hollow nano cages |
| CN104014377B (en) * | 2014-06-12 | 2016-01-13 | 大连理工大学 | The preparation method of the non-metal catalyst of a kind of room temperature efficiently catalyzing and oxidizing desulfurization |
| CN105819553A (en) * | 2015-03-31 | 2016-08-03 | 南京大学 | Carbon nanocage-doped binary carbon material composite electrode, preparation method thereof and application of composite electrode in electro-adsorption desalting |
| CN104953089A (en) * | 2015-05-26 | 2015-09-30 | 南京大学（苏州）高新技术研究院 | Preparation method of lithium-sulfur battery positive electrode material based on sulfur filled carbon nano cage |
| CN104961119A (en) * | 2015-05-26 | 2015-10-07 | 南京大学（苏州）高新技术研究院 | Preparation method of boron and nitrogen co-doped hollow carbon nanocage |
| CN105609789A (en) * | 2016-03-15 | 2016-05-25 | 南京大学（苏州）高新技术研究院 | Preparation method of York-shell nitrogen-doped carbon nanocage-coated platinum nanoparticles oxygen-reduction electrocatalyst with high methanol tolerance |
| CN105855539B (en) * | 2016-04-13 | 2020-09-01 | 安徽大学 | CoFe for photocatalysis field2Core CoFe2O4Construction method of shell layer nano structure |
| CN108400285B (en) * | 2018-03-09 | 2020-08-07 | 南京大学 | Carbon-based metal-free electrocatalyst for promoting polysulfide conversion in lithium-sulfur battery |
| CN109107599A (en) * | 2018-09-21 | 2019-01-01 | 东华理工大学 | A kind of 3D Gr/g-C3N4Composite material, preparation method and application |
| CN110436459A (en) * | 2019-09-19 | 2019-11-12 | 盐城工学院 | A kind of preparation method being graphitized graded porous carbon |
| CN111393799B (en) * | 2020-04-23 | 2022-11-18 | 江苏大学 | Antifriction wear-resistant carbon nanocage/epoxy resin self-lubricating composite material and preparation method thereof |
| CN113511643B (en) * | 2021-05-14 | 2023-03-21 | 江苏大学 | Method for preparing high-capacitance carbon nanocages in green cycle mode and carbon nanocages |
| CN114141548B (en) * | 2021-11-17 | 2024-01-16 | 南京来璋新材料科技有限公司 | Preparation method of mesostructured carbon-based nanocage for high-performance supercapacitor |
| CN114540867B (en) * | 2022-01-21 | 2023-06-27 | 天津大学 | Nano reactor for acidic electrocatalytic carbon dioxide reduction, preparation method and membrane electrode system |
| CN114914102A (en) * | 2022-06-07 | 2022-08-16 | 南京大学 | Preparation process of collapsed carbon-based nano cage electrode material |
| CN115092908A (en) * | 2022-07-11 | 2022-09-23 | 南京延长反应技术研究院有限公司 | Preparation system and preparation method of carbon nanocages |
-
2008
- 2008-04-14 CN CN200810023448A patent/CN100586846C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101284663A (en) | 2008-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100586846C (en) | Method for mass preparing hollow nano carbon cages with high quality | |
| CN100391831C (en) | Method of preparing carbon nanocages | |
| CN102530922A (en) | Method for preparing nitrogen doping hollow carbon nanocages | |
| CN100506703C (en) | Method of preparing titanium dioxide, tin dioxide and doping composite fiber material thereof | |
| CN102459727B (en) | Method for producing solid carbon by reducing carbon oxides | |
| CN101348249B (en) | Method for preparing carbon nano-tube array on particle interior surface | |
| CN102060284A (en) | Method for preparing nitrogen-phosphorus codoped multi-walled carbon nanotube | |
| CN104961119A (en) | Preparation method of boron and nitrogen co-doped hollow carbon nanocage | |
| CN105036096B (en) | A kind of method that utilization reacting gas vortex prepares high-purity boron nitride nano-tube | |
| CN110052263A (en) | A kind of photocatalytic nanometer fibrous material and its preparation method and application | |
| CN107055510A (en) | A kind of preparation method of metal organic complex nanotube and its derivative porous CNT | |
| CN113277509A (en) | Porous carbon nano material and preparation method thereof | |
| US20100016148A1 (en) | Process for preparing catalyst for synthesis of carbon nanotubes using spray pyrolysis | |
| CN101993057B (en) | Method for preparing carbon hollow sphere | |
| CN105293468A (en) | Method for efficiently preparing sulphur-doped hollow carbon spheres | |
| CN206089049U (en) | Go to carbon nanotube purification system that mixes in succession | |
| CN100567147C (en) | A kind of synthetic method of organic-inorganic composite silicon oxide nano-line | |
| CN101544365B (en) | Method for preparing hollow carbon nano-cage through iodized thermal treatment | |
| CN104118858B (en) | A kind of preparation method of hollow nano cages material | |
| CN105967167A (en) | Method for preparing one-dimensional carbon nano material | |
| CN210104135U (en) | Gas-phase spinning device for continuously preparing silicon nanofibers | |
| CN206033244U (en) | Deposit metal ion's carbon nanotube purification system | |
| Bhattacharjee et al. | Chemical vapour deposition (CVD) technique and the synthesis of carbon nanomaterials (CNMs) | |
| CN205340399U (en) | Novel filter and collect device | |
| CN104030271A (en) | Method for preparing single-handed helical carbon nano tube |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100203 Termination date: 20110414 |