CN115259203A - Method for regulating and controlling defects of cerium dioxide by molten salt method - Google Patents
Method for regulating and controlling defects of cerium dioxide by molten salt method Download PDFInfo
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- CN115259203A CN115259203A CN202210839152.5A CN202210839152A CN115259203A CN 115259203 A CN115259203 A CN 115259203A CN 202210839152 A CN202210839152 A CN 202210839152A CN 115259203 A CN115259203 A CN 115259203A
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- molten salt
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- cerium dioxide
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- 150000003839 salts Chemical class 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 38
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000007547 defect Effects 0.000 title claims abstract description 20
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 16
- 230000001276 controlling effect Effects 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000004744 fabric Substances 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000012695 Ce precursor Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 abstract description 16
- 239000001301 oxygen Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 230000007847 structural defect Effects 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 2
- 230000023556 desulfurization Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 description 11
- 229910052684 Cerium Inorganic materials 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- NBFNUZSRUNJKJU-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Ce+3] Chemical compound [O-2].[O-2].[Mn+2].[Ce+3] NBFNUZSRUNJKJU-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- -1 cerium ions Chemical class 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RMAKSEQFVRNWKO-UHFFFAOYSA-N zinc;cerium(3+);oxygen(2-) Chemical compound [O-2].[Zn+2].[Ce+3] RMAKSEQFVRNWKO-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- LQWKWJWJCDXKLK-UHFFFAOYSA-N cerium(3+) manganese(2+) oxygen(2-) Chemical compound [O--].[Mn++].[Ce+3] LQWKWJWJCDXKLK-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
- C01G9/03—Processes of production using dry methods, e.g. vapour phase processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
Abstract
The invention discloses a method for regulating and controlling the defects of cerium dioxide by a molten salt method, which mainly comprises the following steps: and (2) placing the carbon cloth and the low-melting-point salt at a certain temperature, preserving heat for a certain time, adding cerium precursor salt and transition metal precursor salt into the carbon cloth and the low-melting-point salt according to a certain proportion, reacting for a certain time, taking out, cooling to room temperature, and then ultrasonically cleaning and drying. The addition of the low-valence transition metal precursor salt can introduce certain structural defects into the cerium dioxide, form oxygen vacancies and increase reactive sites, thereby improving the performance of the material. The cerium dioxide prepared by the method can be directly used as an electrode material, and has important application in the fields of catalysis, energy, desulfurization, denitrification and the like, which are energy-saving and environment-friendly. The preparation method can rapidly and directly introduce abundant structural defects into the cerium dioxide, increases the reaction activity, is simple and convenient, has short reaction period and is easy to realize control.
Description
Technical Field
The invention relates to a method for regulating and controlling defects of cerium dioxide by a molten salt method and application thereof, and is suitable for the energy-saving and environment-friendly fields of catalysis, energy, desulfurization and denitrification and the like.
Background
The rapid development of global economy not only aggravates the consumption of non-renewable energy and causes energy crisis, but also brings serious environmental pollution due to the exploitation of a large amount of fossil energy. Whether the utilization of solar energy and wind energy which replace fossil energy or the control of atmospheric and water pollution is realized, high-performance energy storage materials and environmental catalytic materials are urgently needed.
Cerium oxide is a rare earth oxide with a high content, and has attracted attention due to its characteristics of environmental friendliness, low price, and multiple valence states. The special oxygen storage performance and the oxidation-reduction characteristic of the catalyst can remove oxynitride in the flue gas, and the catalyst has certain potential in the field of environmental catalysis. In addition, the conversion of two valence states of +3 and +4 can generate charge transfer in an electrochemical reaction for energy storage, and can be used as an electrochemical energy storage electrode material of a fuel cell and a super capacitor.
Oxygen vacancies existing in the material can capture electrons and increase reactive sites, so that a proper method is selected to regulate and control the structural defects in the cerium dioxide, and the catalytic degradation and the electrochemical performance improvement of the cerium dioxide are facilitated. During the synthesis process, transition metal ions and low-valence transition metal ions, such as zinc ions, manganese ions, copper ions and the like in a certain proportion are added to replace cerium ions, rich oxygen vacancies are formed around the cerium ions to achieve charge balance, and the generated oxygen vacancies can be active sites of electrocatalysis or electrochemical reaction, which is beneficial to improving the performance of cerium dioxide.
At present, methods for preparing cerium dioxide and regulating defects mainly comprise a hydrothermal method, a solution combustion method, a coprecipitation method and the like, but the methods have the problems of long preparation period, complex process and the like. For example, patent CN202110949230.2 discloses a method for preparing cerium oxide powder by hydrothermal method and then placing it in PECVD, obtaining cerium oxide with defects after discharge, the prepared cerium oxide being helpful to promote activation of methanol and direct generation of DMC. The invention patent CN202111106446.9 discloses a spherical ferroferric oxide-cerium dioxide composite electrode material with a core-shell structure prepared by a solvothermal method. The invention patent CN202110509610.4 discloses a transition metal composite cerium dioxide nano catalyst prepared by a solution combustion method, which can be used for CO catalytic oxidation. The invention patent CN201910503220.9 discloses a method for regulating and controlling the concentration of oxygen vacancies of monocrystalline cerium dioxide by a hydrothermal method, and the oxygen storage capacity and the catalytic performance of the method can be improved.
The invention discloses a method for regulating and controlling defects of cerium dioxide by a molten salt method, which can introduce abundant oxygen defects into the cerium dioxide, increase reaction active sites, improve charge transfer capacity and enhance catalytic effect. The preparation process is simple and efficient, green and environment-friendly, and the prepared sample has high crystallinity and strong stability.
Disclosure of Invention
The invention aims to provide a method for regulating and controlling the defects of cerium dioxide by a molten salt method.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for regulating and controlling the defect of cerium dioxide by a molten salt method, which comprises the following steps:
1) Cleaning and drying the carbon cloth substrate;
2) Placing the carbon cloth and the low-melting-point salt at a certain temperature and preserving heat for a certain time;
3) Weighing cerium precursor salt and transition metal precursor salt according to a certain proportion;
4) Simultaneously adding cerium precursor salt and transition metal precursor salt into the molten salt to react for a certain time;
5) Taking out, cooling to room temperature, and then ultrasonically cleaning and drying.
Further, the low melting point salt described may be KNO3Or NaNO3The predetermined temperature is above the melting point of the molten salt and below its decomposition temperature, and the temperature is maintained until the molten salt becomes molten.
Further, the described cerium precursor salt may be cerium sulfate, cerium nitrate, cerium chloride, etc., and the transition metal precursor salt may be zinc sulfate, manganese nitrate, copper chloride, etc.
Further, the mass ratio of the described cerium precursor salt to the transition metal precursor salt is in the range of 1.
Further, reaction times in the range of 10 seconds to 120 seconds are described.
The invention provides a method for regulating and controlling the defect of cerium dioxide by a molten salt method, wherein low-valence transition metal ions are added to improve the oxygen vacancy concentration of the cerium dioxide and increase the defect in a matrix material, so that the reaction activity of the material is effectively improved, the preparation method is simple, the raw materials are easy to obtain, and the method has a good application prospect.
Drawings
FIG. 1 is a field emission scanning electron micrograph of pure phase cerium oxide prepared in example 1;
FIG. 2 is a field emission scanning electron micrograph of copper-ceria prepared according to example 2;
FIG. 3 is a field emission scanning electron micrograph of zinc-cerium oxide prepared in example 3;
FIG. 4 is a field emission scanning electron micrograph of manganese-cerium oxide prepared in example 4;
FIG. 5 is a surface scanning elemental map of copper-ceria prepared in example 2 (the images show that (a) is a scanning electron micrograph of copper-ceria field emission, (b) is a surface scanning elemental map of all elements, (c) is a distribution map of cerium, (d) is a distribution map of copper, and (e) is a distribution map of oxygen);
FIG. 6 is a surface scanning elemental map of the zinc-ceria prepared in example 3 (the images show that (a) is a field emission scanning electron micrograph of zinc-ceria, (b) is a surface scanning elemental map of all elements, (c) is a distribution map of cerium, (d) is a distribution map of zinc, and (e) is a distribution map of oxygen);
FIG. 7 is a manganese-cerium dioxide energy spectrum analysis surface scanning element distribution diagram prepared in example 4 (the diagram illustrates that (a) is a manganese-cerium dioxide field emission scanning electron microscope photograph, (b) is a scanning distribution diagram of all elements, (c) is a cerium element distribution diagram, (d) is a manganese element distribution diagram, and (e) is an oxygen element distribution diagram);
FIG. 8 is an X-ray diffraction pattern of the transition metal-cerium oxide prepared in examples 1 to 4 (graphs illustrating that a is the product of example 1, b is the product of example 2, c is the product of example 3, and d is the product of example 4).
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to only the following examples.
Example 1
1) Ultrasonically cleaning 2 x 4cm carbon cloth by using deionized water and ethanol, and drying to obtain a clean substrate;
2) 4g of potassium nitrate is completely melted at 380 ℃ and then put into a carbon cloth to react for 150 seconds;
3) Adding 0.3g of cerium nitrate into a reaction system of carbon cloth and potassium nitrate to react for 90 seconds;
4) Taking out the product obtained in the step 3), cooling to room temperature, and ultrasonically cleaning with deionized water;
5) And putting the product after ultrasonic cleaning into a 60 ℃ drying oven for drying.
FIG. 1 shows SEM pictures showing that ceria is granular and has different sizes, and the diameter of stacked nanoparticles is about 150nm. The X-ray diffraction pattern of the obtained nanomaterial is shown in fig. 8, curve a, and the result shows that cerium oxide is prepared.
Example 2
1) Same as example 1, step 1);
2) Same as example 1, step 2);
3) Simultaneously adding 0.3g of cerium nitrate and 0.03g of copper chloride into a reaction system of carbon cloth and potassium nitrate to react for 90 seconds;
4) Same as example 1, step 4);
5) Same as example 1, step 5).
FIG. 2 shows SEM pictures showing that the Cu-ceria particles are still granular and have different sizes, and the diameter of the stacked nanoparticles is about 95nm. The X-ray diffraction pattern of the obtained nanomaterial is shown as curve b in fig. 8, and the result shows that no diffraction peak of the second phase appears, and the EDS pattern of fig. 4 shows that cerium, copper and oxygen elements are uniformly distributed, and the copper is presumed to be doped into the ceria lattice by combining the two, and the result corresponds to the standard PDF card of pure-phase ceria. The X-ray photoelectron spectroscopy (XPS) analysis result shows that the content of oxygen vacancies in the matrix material is improved after the copper chloride is added.
Example 3
1) Same as example 1, step 1);
2) 5g of sodium nitrate is completely melted at 350 ℃ and then put into a carbon cloth to react for 150 seconds;
3) Simultaneously adding 0.3g of cerium nitrate and 0.03g of zinc sulfate into a reaction system of carbon cloth and sodium nitrate to react for 90 seconds;
4) Same as example 1, step 4);
5) Same as example 1, step 5).
FIG. 3 shows SEM pictures showing that the zinc-cerium oxide particles are still granular and have different sizes, and the diameter of the stacked nanoparticles is about 130nm. The X-ray diffraction pattern of the obtained nanomaterial is shown as curve c in fig. 8, the result shows that no diffraction peak of the second phase appears, and the EDS pattern in fig. 5 shows that cerium, zinc and oxygen elements are uniformly distributed, and the zinc is presumed to be doped into the cerium dioxide crystal lattice by combining the two, and the result corresponds to the standard PDF card of pure-phase cerium dioxide.
Example 4
1) 1) same as example 1, step 1);
2) 5g of sodium nitrate is completely melted at 350 ℃ and then put into a carbon cloth to react for 150 seconds;
3) Simultaneously adding 0.3g of cerium nitrate and 0.03g of manganese nitrate into a reaction system of carbon cloth and sodium nitrate to react for 90 seconds;
4) 4) same as example 1, step 4);
5) 5) same as example 1, step 5).
FIG. 2 shows the difference between the morphology of manganese-cerium dioxide and pure-phase cerium dioxide, and the particle shape is not obvious. The X-ray diffraction pattern of the obtained nanomaterial is shown as curve d in fig. 8, the result shows that no diffraction peak of the second phase appears, and the EDS pattern of fig. 5 shows that cerium, manganese and oxygen elements are uniformly distributed, and the manganese is presumed to be doped into the cerium dioxide crystal lattice by combining the two, and corresponds to the standard PDF card of pure-phase cerium dioxide.
Claims (8)
1. A method for regulating and controlling the defect of cerium dioxide by a molten salt method is characterized by comprising the following main steps:
1) Cleaning and drying the carbon cloth substrate;
2) Placing the carbon cloth and the low-melting-point salt at a certain temperature and keeping the temperature for a certain time;
3) Weighing cerium precursor salt and transition metal precursor salt according to a certain proportion;
4) Simultaneously adding cerium precursor salt and transition metal precursor salt into the molten salt to react for a certain time;
5) Taking out, cooling to room temperature, and ultrasonically cleaning and drying.
2. The method for controlling ceria defects according to claim 1, wherein the low-melting-point salt in step 2) is KNO3Or NaNO3Either one or both of them.
3. The method for controlling the defect of cerium dioxide by the molten salt method as claimed in claim 1, wherein the predetermined temperature in step 2) is higher than the melting point of the molten salt and lower than the decomposition temperature thereof.
4. The method for regulating and controlling the defect of cerium dioxide by the molten salt method according to claim 1, wherein the temperature in step 2) is maintained until the molten salt becomes a molten state.
5. The method for regulating defects of cerium oxide by the molten salt method according to claim 1, wherein the cerium precursor salt in step 3) may be any one or two or more of cerium sulfate, cerium nitrate and cerium chloride.
6. The method for regulating defects of cerium oxide by the molten salt method according to claim 1, wherein the transition metal precursor salt in step 3) may be any one or two or more of zinc sulfate, manganese nitrate and copper chloride.
7. The method for regulating the defect of cerium oxide by the molten salt method according to claim 1, wherein the mass ratio of the cerium precursor salt to the transition metal precursor salt in step 3) is in the range of 1.
8. The method for regulating the defect of cerium oxide by the molten salt method as claimed in claim 1, wherein the reaction time in the step 4) is in the range of 10 seconds to 120 seconds.
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| CN107673391A (en) * | 2017-11-07 | 2018-02-09 | 西安文理学院 | One kind bundle shape ceria metal oxides and preparation method thereof |
| CN110092407A (en) * | 2019-04-11 | 2019-08-06 | 浙江大学 | A kind of method that molten-salt growth method prepares metal oxide or metal hydroxides nano film material |
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| CN107673391A (en) * | 2017-11-07 | 2018-02-09 | 西安文理学院 | One kind bundle shape ceria metal oxides and preparation method thereof |
| CN110092407A (en) * | 2019-04-11 | 2019-08-06 | 浙江大学 | A kind of method that molten-salt growth method prepares metal oxide or metal hydroxides nano film material |
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