CN106219493A - A kind of efficient storage oxygen sieves composite and preparation method rich in the metallic molecule of delocalized electron - Google Patents
A kind of efficient storage oxygen sieves composite and preparation method rich in the metallic molecule of delocalized electron Download PDFInfo
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- CN106219493A CN106219493A CN201610553537.XA CN201610553537A CN106219493A CN 106219493 A CN106219493 A CN 106219493A CN 201610553537 A CN201610553537 A CN 201610553537A CN 106219493 A CN106219493 A CN 106219493A
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- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0296—Generators releasing in a self-sustaining way pure oxygen from a solid charge, without interaction of it with a fluid nor external heating, e.g. chlorate candles or canisters containing them
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The present invention prepares a kind of molecular sieve rich in delocalized electron possessing efficient storage oxygen performance, and it relates to the modification method for preparing of molecular sieve.Aluminum source, silicon source, sodium hydroxide, directed agents and water are mixed mix homogeneously according to a certain percentage, filters after heated Crystallizing treatment, after being dried by the product filtered, obtain sodium form micro porous molecular sieve through oversintering；Method sodium form micro porous molecular sieve and amine salt solution are exchanged by ion, then calcined obtains white proton type molecular sieve powder；Utilize chemistry gas-solid phase reaction method to be assembled in the duct of molecular sieve by metal ion, obtain metallic molecule sieve composite.The metallic molecule sieve composite that the method obtains has substantial amounts of delocalized electron, at room temperature can effectively store oxygen.The amount of oxygen of this molecular sieves compound material storage can reach 210 mmolg‑1；At a temperature of higher than 300 DEG C, it is possible to effectively discharge the oxygen of storage.
Description
Technical field
The present invention relates to efficient storage oxygen rich in the metal-molecular sieves compound material of delocalized electron and preparation side thereof
Method, a kind of method utilizing metal modified molecular screen material.
Background technology
The exploitation of hydrogen-storing material is closely bound up with the daily life of the mankind.Exploitation to hydrogen-storing material, consumptive is expected
Break away from the constraint of oxygen bottle and directly oxygen uptake；Diver is expected to carry the oxygen cylinder of heaviness and carry out underwater performance；
Vehicle tail gas triple effect catalyst needs to complete CO, NO under excess oxygenxConversion, the storage oxygen technology of catalyst surface then carries
The key of high exhaust gas conversion ratio.Owing to oxygen itself is to exist with gaseous state, oxygen is typically to carry out storing in steel cylinder,
Steel cylinder has quality and greatly and is difficult to a series of shortcomings such as carrying, and storing oxygen the most in the material is the most still a difficult problem.
In recent years hydrogen-storing material is developed mainly with modified cerium oxide (CeO2) material is main.CeO2There is the center of area
Cubic fluorite structure, there is the metallic atom of an eight-coordinate at each cubical center, even if being reduced into CeO2-X (0<x<
0.5), after, its fluorite structure does not changes.Due to CeO22CeO can be quickly carried out2→ Ce2O3+1/2O2 Oxidation-reduction is followed
Ring, thus it is considered to have the storage oxygen/oxygen release ability of uniqueness.Current research focuses primarily upon the modification of transition metal ions
To improve CeO2The oxygen storage capacity of material.The interpolation of foreign ion is (such as Zr4+, Pr4+, La3+Deng), can be with CeO2Formed new
Binary or multivariate solid solution, significantly improve the Oxygen storage capacity of material.H. Vidal et al. (Appl. Catal., B
2001,30,75) CeO of high Ce composition under low temperature and middle temperature it is reported in2-ZrO2System Oxygen storage capacity is preferable.M. Mschida
Et al. (Chem. Mater., 2005,17,1487) find doping metals Zr, Hf and Tb binary solid solution Ce1-xMxO2 (M
=Zr, Hf, Tb) there is oxygen diffusion velocity quickly.Despite significant progress, CeO2The hydrogen-storing material of base still also exists
The porosity of material own is undeveloped, preparation cost is high, the releasing oxygen shortcoming such as not exclusively under complex process, high temperature, which has limited
Their development.
For cerium oxide (CeO2) deficiency of class hydrogen-storing material, this patent have employed a kind of novel rich in delocalized electron point
Son sieve material carries out oxygen storage, which overcomes CeO2The releasing oxygen shortcoming such as not exclusively under the porosity low and high temperature of material, can
To be widely used in oxygen field of storage.Owing to molecular sieve is a kind of alumino-silicate materials with abundant pore passage structure, its hole
Road diameter in nanometer category, this just storage for oxygen provide good genetic prerequisite.Patent of the present invention is rich at molecular sieve
Improve further on the basis of rich duct, by specific gas-solid phase reaction method, different metal ions is introduced, prepare
Metal-molecular sieves compound material containing delocalized electron.The electronics of these delocalizations is dispersed in skeleton and the duct of molecular sieve, energy
Enough oxygen molecules by the external world capture, and produce substantial amounts of superoxide radical storage and are in the duct of molecular sieve so that molecule
Sieve material list reveals efficient oxygen storage performance.The method being different from Typical physical absorption, it is anti-that the present invention uses chemistry
The method answered carries out the storage of oxygen, thus the amount of storage of oxygen is the biggest.Meanwhile, the introducing of guest metal ion, it is possible to point
Son sieve main body produces absorbing synergic effect so that metal-molecular sieves compound material is significantly larger than CeO2The Oxygen storage capacity of class material.
Summary of the invention
The present invention is directed to CeO2The deficiency of class hydrogen-storing material, it is provided that a kind of rich novel electron metal-molecular sieve composite wood
The preparation method of material.The metal ion such as cadmium, zinc is incorporated into the hole of molecular sieve by the method by vacuum chemistry gas-solid phase reaction method
Road, prepares cadmium (the zinc)-molecular sieves compound material containing a large amount of delocalized electrons in duct.As hydrogen-storing material, with the external world
After oxygen contact, oxygen molecule can be captured these electronics generation superoxide radical and be present in the duct of molecular sieve so that gold
Genus-molecular sieves compound material shows efficient oxygen storage performance.Compared with existing cerium oxide hydrogen-storing material, this composite wood
Material has high (210 μm olg of oxygen storage amount-1), under high temperature, release is completely, it is possible to the series of advantages such as recycling.
The present invention is achieved by the following technical solutions:
A kind of efficient storage oxygen is rich in the preparation method of the metal-molecular sieves compound material of delocalized electron, it is characterised in that should
Concretely comprising the following steps of method:
(1) synthesis of sodium form micro porous molecular sieve material:
J, by aluminum source, silicon source, sodium hydroxide and water mix homogeneously, forms directed agents, wherein Na2O、Al2O3、SiO2And H2O rubs
Your proportioning is (5 ~ 7): 1:(7 ~ 9): (130 ~ 180), directed agents is at room temperature aged 12 ~ 24 hours；
K, by aluminum source, silicon source, sodium hydroxide and water mix homogeneously, forms mother solution, wherein Na2O、Al2O3、SiO2And H2O mole
Proportioning is (2 ~ 3): 1:(7 ~ 9): (130 ~ 180)；
Directed agents that step j is formed by l and the mother solution that step k is formed are 1:(4 ~ 5 according to mass ratio) it is sealed in after mix homogeneously
In politef hydrothermal reaction kettle, through crystallization, wash, be dried etc. and to process, i.e. obtain sodium form micro porous molecular sieve；Crystallization temperature
Being 90 ~ 120 DEG C, crystallization time is 24 ~ 36 hours；
(2) preparation of proton type molecular screen material:
Taking in the ammonium salt solution that 0.5g sodium form micro porous molecular sieve joins 200 mL, carrying out ion at a certain temperature, to exchange 12 little
Time, then filter, wash, repeated exchanged 4 times, be further dried, it is thus achieved that white ammonium type molecular sieve powder, after through high-temperature roasting
Obtain white proton type molecular sieve powder；
(3) preparation of metal-molecular sieves compound material:
Proton type molecular sieve powder after roasting and metal simple-substance granule are placed according to certain mol ratio the two of reactor
End, is placed in tube furnace reactor sealing in high vacuum conditions, and utilization chemistry gas-solid reaction method will at a certain temperature
Metal ion is diffused in micro porous molecular sieve, obtains metal-molecular sieves compound material.
Described silicon source is sodium silicate, Ludox, white carbon black, waterglass, preferably waterglass；Source of aluminium be sodium metaaluminate,
Boehmite, aluminum isopropylate. etc., preferably sodium metaaluminate.
Described crystallization temperature is 90 ~ 120 DEG C, preferably 110 DEG C.
Carrying out ion exchange 60 ~ 90 DEG C of temperature ranges, filter and wash after stirring 12 hours, temperature is preferably 80 DEG C,
Repeat to filter and washing step 4 times.
Described ammonium salt solution is that aqueous ammonium chloride solution, aqueous ammonium nitrate solution, ammonium hydroxide aqueous solution or ammonium sulfate are water-soluble
Liquid.
Described high-temperature roasting refers at 400 ~ 1000 DEG C high-temperature roasting under oxygen atmosphere or air atmosphere.
Described metal simple-substance is cadmium metal or metallic zinc；The mol ratio of described molecular sieve and metal simple-substance be (10 ~
15): 1.
The used horminess glass tube that reactor is the airtight one end open in one end or quartz ampoule；Described high vacuum condition
For the vacuum condition higher than 0.02 Pa.
Described chemical gas-solid phase reaction method refers to from room temperature, reactor is started the programming rate liter with 1 ~ 5 DEG C/min
To 400 ~ 650 DEG C and be incubated 5 ~ 20 hours.
A kind of efficient storage oxygen is rich in the metal-molecular sieves compound material of delocalized electron, it is characterised in that according to upper
State arbitrary described method to prepare.
Cadmium (zinc)-molecular sieves compound material that the present invention is prepared by said method maintains the complete structure of molecular sieve
Type.Being placed under oxygen atmosphere by cadmium (zinc)-molecular sieves compound material, every gram of this composite can store 210 mmol oxygen and divide
Son.At a temperature of higher than 300 DEG C, the oxygen molecule stored can discharge completely, and material remains in that high storage oxygen is lived
Property.
The present invention has a following clear advantage:
(1) compared with metal-molecular sieves compound material prepared by traditional method, in metal-molecular screen material prepared by the present invention
Electronics containing a large amount of delocalizations.
(2) compared with existing cerium oxide hydrogen-storing material, the hydrogen-storing material that the present invention provides has oxygen storage capacity high (210
mmolg-1), under high temperature, release is completely, it is possible to the series of advantages such as recycling.
Accompanying drawing explanation
Fig. 1 is the powder X-ray diffractogram of cadmium-molecular sieve (the Cd@Y) composite of the embodiment of the present invention 1 synthesis；
Fig. 2 is the uv-visible absorption spectra of cadmium-molecular sieve (the Cd@Y) composite of the embodiment of the present invention 1 synthesis；
Fig. 3 is the electron spin resonance before and after cadmium-molecular sieve (Cd@Y) the composite storage oxygen of the embodiment of the present invention 1 synthesis
Spectrogram；
Fig. 4 is the powder X-ray diffractogram of zinc-molecular sieve (the Zn@Y) composite of the embodiment of the present invention 3 synthesis.
Detailed description of the invention
Elaborating embodiments of the invention below, the present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following enforcement
Example.
Embodiment 1:
The first step: 2.04 g sodium hydroxide and 1.05 g sodium metaaluminates are dissolved in 10 mL deionized waters, stirring is to clear
Clearly, it is subsequently adding 12.57g waterglass, mix and blend 20 minutes, still aging 12 hours of the directed agents obtained；By 0.07 g
Sodium hydroxide and 6.55 g sodium metaaluminates are dissolved in 66 mL deionized waters, stir to clarify, and are subsequently adding 78.61 g water glass
Glass, strong agitation 20 minutes, until gel mix homogeneously, form mother solution gel.By female to 5 g directed agents after ageing and 20 g
Being sealed in after liquid mix homogeneously in politef hydrothermal reaction kettle, at a temperature of 110 DEG C, crystallization is after 24 hours, through washing,
Drying to obtain sodium form micro porous molecular sieve (NaY).
Second step: claim 5g sodium form micro porous molecular sieve powder to join (1.0 mol/L) in 200 mL ammonium chloride solutions, 80
Carry out ion under DEG C water-bath to exchange 12 hours, then filter, wash, be dried after repeating ion exchange process 4 times, it is thus achieved that white ammonium
Type molecular sieve powder (NH4-Y).Ammonium type molecular sieve powder is placed in high temperature process furnances, slowly heat up under oxygen atmosphere (2 DEG C/
Min) to after 600 DEG C of roastings 10 hours, naturally cool to room temperature and obtain the molecular sieve powder (HY) of white proton type.
3rd step: weigh 1.0 g HY molecular sieves and 0.1g cadmium grain metal simple-substance, be respectively placed in the hard glass of speciality
Reactor two ends.When evacuation, oxygen flame is utilized to make glass reactor seal and depart from vacuum system；Then by this
Vacuum-tight reactor is put in tube furnace, and 450 DEG C are heated 20 hours, utilize chemical vapour deposition technique to be assembled into by cadmium metal
In micro porous molecular sieve, i.e. obtain the compound hydrogen-storing material of metal-molecular sieve (Cd@Y).
Fig. 1 is the X-ray diffraction spectrogram of metal-molecular sieve (Cd Y) composite of embodiment 1 gained, shows metal-molecule
Sieve (Cd Y) material has well-regulated microcellular structure, during wherein cadmium ion has been introduced into the duct of molecular sieve.Fig. 2 be metal-
The uv-visible absorption spectra of molecular sieve (Cd@Y) material, illustrates that the existence of delocalized electron can make material possess good purple
Outer photoresponse.
Embodiment 2:
Under argon shield state, the metal-molecular sieves compound material (Cd@Y) of 0.5 g loads (reactor in glass tubing reactor
Volume: 100 cm3), subsequently to glass tubing evacuation, at room temperature introduce the high purity oxygen gas gas of 1000 mmol.Stand 30
After min, vacuum takes remaining oxygen away.Then raise temperature to 300 DEG C, utilize gas chromatogram that the oxygen discharged quantitatively is divided
Analysis.Under conditions of 300 DEG C, the amount of the oxygen discharged reaches 105 mmol, the metal of i.e. every gram-molecular sieves compound material storage
Oxygen amount is 210 mmol.By storage and complete the metal-molecular sieves compound material (Cd@Y) of releasing oxygen and be again passed through oxygen, gold
Genus-molecular sieves compound material is still able to keep higher activity, illustrates that this material can repeatedly store/releasing oxygen.
Fig. 3 is the electron spin resonance before and after metal-molecular sieve (Cd@Y) the composite storage oxygen of embodiment 1 gained
Spectrogram, it will be clear that after storage oxygen, material can form substantial amounts of superoxide radical ion from spectrogram.This be by
The reason that delocalized electron in material is formed by oxygen capture, creates substantial amounts of superoxide radical and is stored in molecular screen material
In.
Embodiment 3:
Implementation is with embodiment 1, and the difference with embodiment 1 is that metal used is zinc.Weigh 1.0 g HY molecular sieves and
0.1g zinc elemental metals, is respectively placed in the hard glass reactor two ends of speciality.Reactor is connected vacuum system, utilizes oxygen
Flame makes glass reactor seal and departs from vacuum system；Then this vacuum-tight reactor is put in tube furnace, 550 DEG C
Heat 20 hours, utilize chemical vapour deposition technique to be assembled in micro porous molecular sieve by zinc simple substance, i.e. obtain zinc-molecular sieve (Zn@Y)
Compound hydrogen-storing material.Fig. 4 is the powder X-ray diffractogram of zinc-molecular sieve (the Zn@Y) composite of embodiment 3 gained.
Embodiment 4:
Under argon shield state, the zinc-molecular sieves compound material (Zn@Y) of 0.5 g loads (reactor in glass tubing reactor
Volume: 100 cm3).Subsequently to glass tubing evacuation, at room temperature introduce the high purity oxygen gas gas of 1000 mmol.Stand 30
After min, vacuum takes remaining oxygen away.Then raise temperature to 300 DEG C, utilize gas chromatogram that the oxygen discharged quantitatively is divided
Analysis.At 300 DEG C, the amount of the oxygen discharged reaches 96 mmol, then the oxygen storage capacity of every gram of zinc-molecular sieves compound material is 192
mmol。
Claims (10)
1. an efficient storage oxygen is rich in the preparation method of the metal-molecular sieves compound material of delocalized electron, it is characterised in that
Concretely comprising the following steps of the method:
(1) synthesis of sodium form micro porous molecular sieve material:
J, by aluminum source, silicon source, sodium hydroxide and water mix homogeneously, forms directed agents, wherein Na2O、Al2O3、SiO2And H2O rubs
Your proportioning is (5～7): 1:(7～9): (130～180), directed agents is at room temperature aged 12～24 hours；
K, by aluminum source, silicon source, sodium hydroxide and water mix homogeneously, forms mother solution, wherein Na2O、Al2O3、SiO2And H2O mole
Proportioning is (2～3): 1:(7～9): (130～180)；
Directed agents that step j is formed by l and the mother solution that step k is formed are 1:(4～5 according to mass ratio) seal after mix homogeneously
In politef hydrothermal reaction kettle, through crystallization, wash, be dried etc. and to process, i.e. obtain sodium form micro porous molecular sieve；Crystallization temperature
Degree is 90～120 DEG C, and crystallization time is 24～36 hours；
(2) preparation of proton type molecular screen material:
Taking in the ammonium salt solution that 0.5g sodium form micro porous molecular sieve joins 200 mL, carrying out ion at a certain temperature, to exchange 12 little
Time, then filter, wash, repeated exchanged 4 times, be further dried, it is thus achieved that white ammonium type molecular sieve powder, after through high-temperature roasting
Obtain white proton type molecular sieve powder；
(3) preparation of metal-molecular sieves compound material:
Proton type molecular sieve powder after roasting and metal simple-substance granule are placed according to certain mol ratio the two of reactor
End, is placed in tube furnace reactor sealing in high vacuum conditions, and utilization chemistry gas-solid reaction method will at a certain temperature
Metal ion is diffused in micro porous molecular sieve, obtains metal-molecular sieves compound material.
The most according to claim 1, efficient storage oxygen is rich in the preparation side of the metal-molecular sieves compound material of delocalized electron
Method, it is characterised in that described silicon source is sodium silicate, Ludox, white carbon black, waterglass, preferably waterglass；Source of aluminium is inclined aluminum
Acid sodium, boehmite, aluminum isopropylate. etc., preferably sodium metaaluminate.
The most according to claim 1, efficient storage oxygen is rich in the preparation side of the metal-molecular sieves compound material of delocalized electron
Method, it is characterised in that described crystallization temperature is 90～120 DEG C, preferably 110 DEG C.
The most according to claim 1, efficient storage oxygen is rich in the preparation side of the metal-molecular sieves compound material of delocalized electron
Method, it is characterised in that carry out ion exchange 60～90 DEG C of temperature ranges, filters and washs after stirring 12 hours, and temperature is preferred
It is 80 DEG C, repeats to filter and washing step 4 times.
The most according to claim 1, efficient storage oxygen is rich in the preparation side of the metal-molecular sieves compound material of delocalized electron
Method, it is characterised in that described ammonium salt solution is aqueous ammonium chloride solution, aqueous ammonium nitrate solution, ammonium hydroxide aqueous solution or sulphuric acid
Aqueous ammonium.
The most according to claim 1, efficient storage oxygen is rich in the preparation side of the metal-molecular sieves compound material of delocalized electron
Method, it is characterised in that described high-temperature roasting refers at 400～1000 DEG C high-temperature roasting under oxygen atmosphere or air atmosphere.
The most according to claim 1, efficient storage oxygen is rich in the preparation side of the metal-molecular sieves compound material of delocalized electron
Method, it is characterised in that described metal simple-substance is cadmium metal or metallic zinc；The mol ratio of described molecular sieve and metal simple-substance is
(10～15): 1.
The most according to claim 1, efficient storage oxygen is rich in the preparation side of the metal-molecular sieves compound material of delocalized electron
Method, it is characterised in that reactor used is horminess glass tube or the quartz ampoule of the airtight one end open in one end；Described Gao Zhen
Empty condition is the condition that vacuum is higher than 0.02 Pa.
The most according to claim 1, efficient storage oxygen is rich in the preparation side of the metal-molecular sieves compound material of delocalized electron
Method, it is characterised in that described chemical gas-solid phase reaction method refers to start with the intensification of 1～5 DEG C/min reactor from room temperature
Speed rises to 400～650 DEG C and is incubated 5～20 hours.
10. an efficient storage oxygen is rich in the metal-molecular sieves compound material of delocalized electron, it is characterised in that according to upper
Method described in any claim of stating prepares.
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Citations (2)
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| CN104525246A (en) * | 2015-01-22 | 2015-04-22 | 厦门大学 | Preparation method and application of no-template-agent small-grain Zn-ZSM-5 catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525246A (en) * | 2015-01-22 | 2015-04-22 | 厦门大学 | Preparation method and application of no-template-agent small-grain Zn-ZSM-5 catalyst |
| CN105502433A (en) * | 2015-12-16 | 2016-04-20 | 上海英保能源化工科技有限公司 | Preparation method of methanol-to-gasoline catalyst nano Zn-ZSM-5 |
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| 王敬锋: ""基于分子筛的无机多孔材料的制备、表征与功能化研究"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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Application publication date: 20161214 |