CN107473256A - A kind of Ce1‑xZrxO2Nanometer sheet material and preparation method thereof - Google Patents

A kind of Ce1‑xZrxO2Nanometer sheet material and preparation method thereof Download PDF

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CN107473256A
CN107473256A CN201710728604.1A CN201710728604A CN107473256A CN 107473256 A CN107473256 A CN 107473256A CN 201710728604 A CN201710728604 A CN 201710728604A CN 107473256 A CN107473256 A CN 107473256A
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sheet material
water
nanometer sheet
preparation
colloidal sol
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CN107473256B (en
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李志杰
王军强
王治国
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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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
    • 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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • 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
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Abstract

The invention belongs to the preparing technical field of inorganic material, and in particular to a kind of Ce1‑xZrxO2Nanometer sheet material and preparation method thereof.The present invention prepares mixed solution using cerous nitrate, two water zirconyl nitrates and sodium nitrate, then sequentially adds ammoniacal liquor and hydrogen peroxide obtains colloidal sol, then obtain ultra-thin porous Ce by hydro-thermal process1‑xZrxO2Nanometer sheet material.The cerium oxide that the zirconium ion of preparation is modified, forms solid solution structure, is 6~12nm of thickness nano-sheet pattern, piece is interior mesoporous with 1.9~2.5nm of yardstick, and specific surface area is more than 180m2/ g, pore volume are more than 0.50cm3/g；Zr uniform ions are distributed among the lattice of ceria, form solid solution structure.It is easy to industrialization large-scale production, it is not necessary to which high-temperature roasting is handled, and saves the energy, it is not necessary to which surfactant or strong acid and strong base, preparation process are environment-friendly.

Description

A kind of Ce1-xZrxO2Nanometer sheet material and preparation method thereof
Technical field
The invention belongs to the preparing technical field of inorganic material, and in particular to a kind of Ce1-xZrxO2Nanometer sheet material and its system Preparation Method.
Background technology
Cerium oxide is a kind of important rare earth oxide material, has good catalytic activity, outstanding optical property, oxygen Storage capacity and outstanding air-sensitive performance, be widely used in catalyst, oxygen storage material, fuel cell, ultracapacitor, The fields such as polishing agent, gas sensor and electronic ceramics.
Although there is extensive report on the various nanotopographies of cerium oxide at present, such as nano particle, nanofiber, nanometer Line, nano flower etc., but it is less for the report of cerium oxide nano sheet material, and also what is reported is all non-porous pure ceria Nanometer sheet material, a kind of preparation method of cerium oxide nano-plate as disclosed in patent 20081020199.0：Using cerium salt and 16 Alkyl trimethyl ammonium bromide surfactant is prepared for cerium oxide nano-plate by hydro-thermal method, and this cerium oxide nano-plate is square The single-chip of shape, rhombus or hexagon, it is non-porous in piece.Patent 201410529975.3 discloses a kind of cerium oxide nano-plate Preparation method：Reacted using cerous acetate and sodium borohydride as raw material, first obtain CeOHCO3Piece, finally roasting obtain platy cerium oxide Nano material, obtained cerium oxide are 25~30nm of thickness non-porous nano piece.Patent 201610536097.7 discloses one kind The preparation method of hexagon cerium dioxide nano sheet material：Using six water cerous nitrates and boron hydracid sodium, polyvinyl alcohol is for raw material Surfactant, annealed after hydro-thermal reaction to obtain the nonporous silica cerium hexagonal nanosheet that the length of side is 50~60nm.
Nanometer sheet is easily changed in use, and such as crystal grain is grown up to be destroyed with laminated structure.Cerium oxide is received It is a kind of effective means for improving and stablizing its structure and performance that rice piece, which carries out zirconium ion to be modified, and zirconium ion radius and electricity are negative Property and cerium ion it is close, can enter cerium oxide lattice in, and cerium oxide formed solid solution, so as to suppress aoxidize cerium tablet In it is nanocrystalline grow up, keep its high specific surface area and application performance.
Porose platy cerium oxide nanostructured has a bigger specific surface area, and cavernous structure is beneficial to solute or gas Disengaging, the Contact-sorption of gas or solute is more beneficial for, can significantly improve its catalysis, air-sensitive, oxygen storage, battery etc. should Use performance.But at present for porose Ce1-xZrxO2Nanometer sheet material is not reported.
The content of the invention
Problem or deficiency be present for above-mentioned, the invention provides a kind of Ce1-xZrxO2Nanometer sheet material and its preparation side Method, material are nano-sheet pattern, have mesoporous in piece, and specific surface area is big, and Zr uniform ions are distributed in the lattice of ceria Among, solid solution structure is formd, preparation technology does not need high-temperature roasting processing, it is not necessary to surfactant or strong acid and strong base.
The Ce1-xZrxO2Nanometer sheet material is 6~12nm of thickness nano-sheet, and it is 1.9~2.5nm to have yardstick in piece It is mesoporous, its specific surface area is more than 180m2/ g, pore volume are more than 0.50cm3/ g, Zr uniform ion are distributed in the crystalline substance of ceria Among lattice, solid solution structure, x=0.01~0.50 are formd.
Its preparation method, it is specific as follows：
Step 1, by six water cerous nitrates, two water zirconyl nitrates and sodium nitrate add deionized water in, stirring to dissolve, obtain Mixed solution；In mixed solution, the concentration of six water cerous nitrates is 0.050mol/L~0.500mol/L, two water zirconyl nitrates it is dense Spend for 0.005mol/L~0.250mol/L, the concentration of sodium nitrate is 0.03mol/L~0.20mol/L.
Step 2, ammoniacal liquor is added in step 1 resulting solution, (addition of ammoniacal liquor is deionized water volume in step 1 1/5~1/2), stir 5~30min and be changed into milk yellow colloidal sol to solution, then instill hydrogen peroxide, (addition of hydrogen peroxide is step The 1/60~1/20 of deionized water volume in 1), continue 20~40min of stirring, be changed into bronzing to colloidal sol.
Step 3, colloidal sol made from step 2 is transferred in the water heating kettle of polytetrafluoroethyllining lining, the water at 80~120 DEG C Thermal response 14~30 hours.Then the product after hydro-thermal reaction is filtered, at least washed 3 times respectively using deionized water and ethanol Afterwards, in 100~130 DEG C of drying, that is, ultra-thin porous Ce is obtained1-xZrxO2Nanometer sheet material.
The present invention prepares mixed solution using cerous nitrate, two water zirconyl nitrates and sodium nitrate, then sequentially add ammoniacal liquor and Hydrogen peroxide obtains colloidal sol, then obtains ultra-thin porous Ce by hydro-thermal process1-xZrxO2Nanometer sheet material.The zirconium ion of preparation changes Property cerium oxide, form solid solution structure, be very thin nano-sheet pattern, there are in piece a large amount of mesoporous, this material Expect that specific surface area is big, pore volume is big.This special nanostructured can be used for catalyst, oxygen storage material, fuel cell, super The fields such as level capacitor, gas sensor and electronic ceramics.
In summary, the Ce that prepared by the present invention1-xZrxO2Nanometer sheet material, it is 6~12nm of thickness nano-sheet pattern, Mesoporous with 1.9~2.5nm of yardstick in piece, specific surface area is more than 180m2/ g, pore volume are more than 0.50cm3/g；Zr ions are equal It is even to be distributed among the lattice of ceria, form solid solution structure.It is easy to industrialization large-scale production, it is not necessary to which high temperature roasts Burning processing, saves the energy, it is not necessary to which surfactant or strong acid and strong base, preparation process are environment-friendly.
Brief description of the drawings
Fig. 1 is embodiment 1Ce0.94Zr0.06O2The ESEM and transmission electron microscope photo of nanometer sheet material；
Fig. 2 is embodiment 1Ce0.94Zr0.06O2The X-ray diffraction spectrogram of nanometer sheet material.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
Embodiment 1
Step 1, at room temperature, the water cerous nitrates of 4.34g six, the water zirconyl nitrates of 0.23g bis- and 0.43g sodium nitrate are added into 80ml In deionized water, stirring obtains mixed solution to dissolving.
Step 2,20ml ammoniacal liquor is added in step 1 resulting solution, stirred 10 minutes, solution is changed into milk yellow colloidal sol；Again 2ml hydrogen peroxide is instilled, continues stirring 30 minutes, colloidal sol is changed into bronzing.
Step 3 and then step 2 gained colloidal sol is transferred in the water heating kettle of polytetrafluoroethyllining lining, the hydro-thermal at 100 DEG C Reaction 20 hours, naturally cools to room temperature, then filters the product after hydro-thermal reaction, then is distinguished using deionized water and ethanol After washing 3 times, in 110 DEG C of drying, that is, ultra-thin porous Ce is obtained0.94Zr0.06O2Nanometer sheet material.
Ce made from embodiment is detected by AFM (AFM)0.94Zr0.06O2Nanometer sheet material, its thickness are 8nm, piece are interior with mesoporous, the specific surface area 185.4m that substantial amounts of yardstick is 2.1nm2/ g, pore volume 0.51cm3/g；XRD Measurement result shows that it is the single-phase crystal formation of ceria cubic fluorite ore deposit.

Claims (2)

  1. A kind of 1. Ce1-xZrxO2Nanometer sheet material, it is characterised in that：For 6~12nm of thickness nano-sheet, piece is interior to have yardstick For the mesoporous of 1.9~2.5nm, its specific surface area is more than 180m2/ g, pore volume are more than 0.50cm3/ g, Zr uniform ion are distributed in Among the lattice of ceria, solid solution structure, x=0.01~0.50 are formd.
  2. 2. Ce as claimed in claim 11-xZrxO2The preparation method of nanometer sheet material, it is specific as follows：
    Step 1, by six water cerous nitrates, two water zirconyl nitrates and sodium nitrate add deionized water in, stirring to dissolve, mixed Solution；In mixed solution, the concentration of six water cerous nitrates is 0.050mol/L~0.500mol/L, and the concentration of two water zirconyl nitrates is 0.005mol/L~0.250mol/L, the concentration of sodium nitrate is 0.03mol/L~0.20mol/L；
    Step 2, add ammoniacal liquor in step 1 resulting solution, the addition of ammoniacal liquor be deionized water volume in step 1 1/5~ 1/2,5~30min of stirring to solution is changed into milk yellow colloidal sol；Instill hydrogen peroxide again, the addition of hydrogen peroxide be gone in step 1 from The 1/60~1/20 of sub- water volume, continues 20~40min of stirring, is changed into bronzing to colloidal sol；
    Step 3, colloidal sol made from step 2 is transferred in the water heating kettle of polytetrafluoroethyllining lining, hydro-thermal is anti-at 80~120 DEG C Answer 14~30 hours；Then the product after hydro-thermal reaction is filtered, after at least being washed 3 times respectively using deionized water and ethanol, In 100~130 DEG C of drying, that is, obtain ultra-thin porous Ce1-xZrxO2Nanometer sheet material.
CN201710728604.1A 2017-08-23 2017-08-23 A kind of Ce1-xZrxO2Nanometer sheet material and preparation method thereof Expired - Fee Related CN107473256B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109529802A (en) * 2018-11-12 2019-03-29 山东国瓷功能材料股份有限公司 A kind of cerium zirconium compound oxide and its preparation method and application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0614854A1 (en) * 1993-02-10 1994-09-14 Rhone-Poulenc Chimie Process for the synthesis of mixed zirconium und cerium oxides based compositions, the obtained compositions and use thereof
CN102180703A (en) * 2011-03-04 2011-09-14 北京工业大学 Binary material (Zr,Ce)O2 nanodots, and preparation method and application thereof
CN106006703A (en) * 2016-05-25 2016-10-12 中国科学院大学 Method for preparing nano flaky cerium oxide and lanthanum-cerium hydroxysulfate by hydrothermal process
CN106186036A (en) * 2016-07-10 2016-12-07 九江学院 A kind of preparation method of hexagon cerium dioxide nano sheet material
CN106745170A (en) * 2016-12-09 2017-05-31 中南大学 A kind of cobalt doped cerium oxide nano materials of laminated structure and its preparation and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0614854A1 (en) * 1993-02-10 1994-09-14 Rhone-Poulenc Chimie Process for the synthesis of mixed zirconium und cerium oxides based compositions, the obtained compositions and use thereof
CN102180703A (en) * 2011-03-04 2011-09-14 北京工业大学 Binary material (Zr,Ce)O2 nanodots, and preparation method and application thereof
CN106006703A (en) * 2016-05-25 2016-10-12 中国科学院大学 Method for preparing nano flaky cerium oxide and lanthanum-cerium hydroxysulfate by hydrothermal process
CN106186036A (en) * 2016-07-10 2016-12-07 九江学院 A kind of preparation method of hexagon cerium dioxide nano sheet material
CN106745170A (en) * 2016-12-09 2017-05-31 中南大学 A kind of cobalt doped cerium oxide nano materials of laminated structure and its preparation and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109529802A (en) * 2018-11-12 2019-03-29 山东国瓷功能材料股份有限公司 A kind of cerium zirconium compound oxide and its preparation method and application
CN109529802B (en) * 2018-11-12 2021-12-28 山东国瓷功能材料股份有限公司 Cerium-zirconium composite oxide and preparation method and application thereof

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