CN108568297A - Cerium base catalyst with core-casing structure and preparation method thereof - Google Patents
Cerium base catalyst with core-casing structure and preparation method thereof Download PDFInfo
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- CN108568297A CN108568297A CN201710134322.9A CN201710134322A CN108568297A CN 108568297 A CN108568297 A CN 108568297A CN 201710134322 A CN201710134322 A CN 201710134322A CN 108568297 A CN108568297 A CN 108568297A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 25
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 25
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052709 silver Inorganic materials 0.000 claims abstract description 22
- 239000004332 silver Substances 0.000 claims abstract description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 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 17
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 230000009471 action Effects 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 239000002052 molecular layer Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 235000005979 Citrus limon Nutrition 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 239000004071 soot Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 229910001961 silver nitrate Inorganic materials 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000002077 nanosphere Substances 0.000 description 8
- 239000001509 sodium citrate Substances 0.000 description 8
- 235000011083 sodium citrates Nutrition 0.000 description 8
- 235000015165 citric acid Nutrition 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 244000131522 Citrus pyriformis Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910002838 Pt-CeO2 Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- ZAEOWXUVMZSOCH-UHFFFAOYSA-M silver sodium 3-carboxy-3,5-dihydroxy-5-oxopentanoate nitrate Chemical compound [N+](=O)([O-])[O-].[Ag+].C(CC(O)(C(=O)O)CC(=O)O)(=O)[O-].[Na+] ZAEOWXUVMZSOCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B01J35/23—
-
- B01J35/393—
-
- B01J35/396—
Abstract
The present invention discloses cerium base catalyst with core-casing structure and preparation method thereof, using pulse laser synthesis core shell structure, the interaction that the catalyst passes through cerium oxide and silver, enhance the catalytic performance of catalyst, improve the catalytic activity and stability of cerium base catalyst soot particulate, to reduce the discharge of pollutant, atmosphere pollution is reduced.
Description
Technical field
The invention belongs to catalysis technical fields, more particularly, are related to a kind of cerium base catalyst and its synthetic method.
Background technology
Cerium oxide is material a kind of cheap and that purposes is extremely wide, is widely used in luminescent material, UV absorbing material, catalysis
The fields such as agent, the polishing of glass, cleaning catalyst for tail gases of automobiles, electronic ceramics.Recently as the rapid hair of rare earth new material
Exhibition and extensive use, it has been found that nano Ce O2Powder has new excellent properties and application, the preparation of CeO2 nano materials, work(
Can characteristic and application study oneself become the hot spots such as research.
As tail gas catalyzed application, therefore cerium oxide limits cerium oxide due to being easy sintering in the event of high temperatures
Researchers improve the catalytic activity of cerium oxide by various methods.Li Yadong etc. is with Ce (NO3)3It is raw material with propionic acid, in second
CeO is obtained using solvent-thermal method in glycol2Microballoon, the method for then using loaded Ag nano particle, makes its catalysis to CO, NO
Activity greatly improves.Same Li Yadong seminar is by Ce (NO3)3Be dissolved in ethylene glycol, using solvent structure nanosphere and
Nano cubic adds ZrOCl2Solution has synthesized solid solution hollow nano-sphere and nano cubic, and the performance of cerium oxide obtains
It is further to improve.Galen D.Stocky et al. are first prepared for SiO using Shi Tuobaifa2Bead, and prepared as template
Hollow CeO2Bead.Ethylene glycol is solvent, and SiO is prepared using solvent-thermal method2@CeO2Structure reuses NaOH and removes mould
Plate obtains the hollow CeO that shell is 12nm2Bead, research test show that its specific surface area is up to 123m2/g.On this basis,
They adulterate Zr into obtained hollow ball again, are prepared for a series of Ce-Zr-O solid solution, experiment finds that the content highest of Zr can
Keep hollow ball indeformable up to 13wt%.
Ceria and the compound performance that can greatly improve ceria itself and its composite material of other materials.In order to
Its catalytic activity is improved, noble metal nano particles can be made compound with ceria, such as：Pt, Pd, Au etc..Zhang]Et al. system
For spherical Pt@CeO2Nanosphere and hud typed Pt@CeO2Nanosphere, by photocatalytic degradation benzyl carbinol it is demonstrated experimentally that Pt@
CeO2Nanosphere is due to Pt nano-particles and CeO2It comes into full contact with, the Pt@CeO of the transfer ratio ball-type of electronics and charge2Nanosphere
It is good, therefore the catalytic efficiency highest of hud typed nanosphere.The Pt@CeO of two kinds of patterns2The photocatalysis performance of nanosphere will be much
More than Pt-CeO2Compound nano material.Kayama et al. has synthesized the CeO of " rice dumpling " shape using hydro-thermal method2- Ag compounds,
It is first that a certain proportion of cerous nitrate and silver nitrate is soluble in water, a certain amount of ammonium hydroxide is then added, ammonium hydroxide forms silver with silver ion
Ammonia solution and cerous nitrate can generate cerium hydroxide, since the strong oxidizing property of silver-colored ammonium ion can will be very easy to the hydroxide that be aoxidized
Cerium aoxidizes, to generate CeO2- Ag nanometers of " rice dumpling " structures.They have found CeO by testing its catalysis oxidation to CO, NO2-
Ag nanometers of " rice dumpling " structures are significantly larger than the catalytic efficiency of CO, NO common Ag-CeO2.Due to CeO2Most of performances it is outstanding
It is that catalytic performance is related with the intracell Lacking oxygen of ceria, therefore how to improve the intracell Lacking oxygen of ceria and be
One of hot spot of current research.
Invention content
It is an object of the invention to overcome the deficiencies in the prior art, overcome existing regulation and control method and step complicated, are catalyzed
Agent thermal stability is poor, the undesirable disadvantage of catalytic effect, using Laser synthesizing Ag CeO2Nucleocapsid substantially increases catalysis
The oxygen vacancy concentration of agent and the stability of catalyst, promote the research of cerium base catalyst, to further increase catalyst
Catalytic activity and stability, reduce the discharge of pollutant.
The technical purpose of the present invention is achieved by following technical proposals：
Cerium base catalyst with core-casing structure forms cerium oxide nano layer using nano silver as kernel outside nano silver.
Nano-Ag particles 4-8nm of average out to, preferably 5-6nm；Cerium oxide nano layer thickness 1.5-4nm of average out to, preferably
2—3nm。
The preparation method of cerium base catalyst with core-casing structure, carries out as steps described below：
It is 6-7 that cerous nitrate, nano silver and citric acid, which are dispersed in distilled water and adjust pH value using ammonium hydroxide, to swash
Light device, which is located on the water surface and exports millisecond pulse laser signal, acts on solution, and wherein millisecond pulse laser signal parameter is work(
Rate 106w/cm2, voltage 720v, pulsewidth 10ms, 1-10HZ of frequency, wavelength 523nm, 150-350mJ/cm of energy2, laser target
Identity distance is the 0.8-of silver and cerous nitrate total mole number from 5-10mm of the water surface, at least 1 hour action time, the molal quantity of citric acid
1.5；Rate by product from 20-25 degrees Celsius of room temperature with 3-5 DEG C/min is increased to 500-600 DEG C, is protected in air atmosphere
3-5h of temperature is held, so that the nitrate in presoma decomposes completely, is formed using nano silver as kernel, cerium oxide is the cerium of outer layer
Base catalyst with core-casing structure.
In the above-mentioned technical solutions, nano silver is prepared using reduction of sodium citrate silver nitrate, needs to adjust according to reaction
The dosage of whole sodium citrate is in excessive state and specifically, takes the glycerine of volume ratio 4 to 1 so that silver nitrate restores completely
It is mixed into solution with distilled water, silver nitrate and sodium citrate, ultrasonic disperse is added, is placed on constant temperature in 130-140 DEG C of oil bath pans
1-2h of heating stirring is centrifuged, and washing is dried to obtain silver nano-grain.
In the above-mentioned technical solutions, millisecond pulse laser signal parameter is power 106w/cm2, voltage 720v, pulsewidth 10ms,
5-10HZ of frequency, wavelength 523nm, 200-300mJ/cm of energy2, action time is 1.5-2 hours.
In the above-mentioned technical solutions, after being kept the temperature in air atmosphere, room temperature (20 DEG C -25 DEG C) is cooled to the furnace.
In the above-mentioned technical solutions, the molal quantity of citric acid is 0.8-the 1 of silver and cerous nitrate total mole number.
In the above-mentioned technical solutions, due to generating using nano silver as kernel, cerium oxide is that the cerium base nucleocapsid of outer layer is urged
Agent is not strict with the ratio of cerous nitrate and nano silver when cerous nitrate, nano silver and citric acid are dispersed in distilled water
Example, but the quality of general requirement cerous nitrate is more than nano silver, to realize nitrate being uniformly distributed in nano grain surface, preferably
The mass ratio of cerous nitrate and nano silver is (2-4)：1.
The concentration of the absorption oxygen of the catalyst prepared using technical solution of the present invention has significant raising, in sample
Oxygen vacancy concentration be greatly improved, the catalytic performance of catalyst has greatly improved.The present invention is further related to for cerium base
The raising of catalyst performance is effective, and hydrogen reducing temperature is reduced to 200 DEG C from original 400 DEG C, greatly reduces and urges
Agent is catalyzed initial temperature, improves the catalytic activity of catalyst.
Description of the drawings
Fig. 1 is the XRD diagram for the silver nano-grain that embodiment one obtains in the present invention.
Fig. 2 is the XRD diagram for the nucleocapsid catalyst sample that embodiment one obtains in the present invention.
Fig. 3 is TEM the and HRTEM photos for the nucleocapsid catalyst sample that embodiment one obtains in the present invention.
Fig. 4 is TEM the and HRTEM photos for the nucleocapsid catalyst sample that embodiment two obtains in the present invention.
Fig. 5 is the XPS figure comparison diagrams of the sample that embodiment three obtains in the present invention and untreated cerium oxide, is located above
Be untreated cerium oxide, underlying is the sample that embodiment three obtains.
Fig. 6 is the XPS figure comparison diagrams of the sample that example IV obtains in the present invention and untreated cerium oxide, is located above
Be untreated cerium oxide, underlying is the sample that example IV obtains.
Fig. 7 is embodiment one in the present invention, embodiment two, embodiment three, example IV sample and untreated cerium oxide H2-
TPR spectrograms.
Specific implementation mode
The technical solution further illustrated the present invention with reference to specific embodiment.Wherein cerous nitrate, silver nitrate, be purchased from day
Fine chemistry industry research institute is recovered in Tianjin, and deionized water, sodium citrate are purchased from Ke Wei companies of University Of Tianjin, and glycerine, ammonium hydroxide are purchased from day
One factory of Tianjin chemical reagent.XRD：German Brooker D8 type X-ray diffractometers；FEI Co.'s Tecnai G2F20 Flied emissions transmission electricity
Sub- microscope；Perkin-Elmer PHI-1600 type photoelectron spectrographs；Ametek companies LC-D20 on-line mass spectroscopy instrument；H2-
TPR Merck ＆ Co., Inc autochem2920 chemical adsorption instruments.
Embodiment one
The first step takes the distilled water of the glycerine that volume is 40ml and 10ml to be mixed into solution, be added 0.18g silver nitrates and
0.142g sodium citrates, ultrasonic disperse are placed on heated at constant temperature in 135 DEG C of oil bath pans and stir 1h.Centrifugation, washing, is dried to obtain
Silver nano-grain.
Second step weighs 0.2171g cerous nitrates and 0.1078g silver nano-grains are added in distilled water, and 0.26g lemons are added
Lemon acid adjusts pH value to 6.7 with ammonium hydroxide 1mol/L, generates dispersion.Magnetic agitation is acted on using the method for pulsed laser action
Mixed solution 1.5h, by laser head perpendicular to mixed solution be arranged (laser target surface is apart from liquid level 5mm) so that laser action in
Mixed solution obtains product centrifugation, dry.Wherein laser parameter is：Power 106w/cm2, voltage 720v, pulsewidth 10ms, frequency
10Hz, wavelength 523nm, energy 250mJ/cm2。
Third step makes nitrate decompose to obtain catalyst product using high-temperature sintering process, and the complete product of above-mentioned drying is existed
It is sintered in Muffle furnace, is increased to 500 DEG C from room temperature (20 DEG C -25 DEG C) with the rate of 3 DEG C/min, keeps temperature 5h, make presoma
In nitrate decompose completely.It then cools to room temperature (20 DEG C -25 DEG C) with the furnace, finally obtains catalyst.
In the technical solution of the present invention, nano silver is generated using silver nitrate and reduction of sodium citrate, we obtain from attached drawing 1
Silver nano-grain XRD spectrum we can be found that and standard card fit like a glove, 38.1 °, 44.09 °, 64.26 °,
Peak at 77.29 °, 81.31 ° corresponds to (111), (200), (220), (311), (222) crystal face respectively, us are calculated by software
The grain size for obtaining silver nanoparticle is 5nm.From attached drawing 2, we can analyze to obtain in sample XRD diagram and occur respectively from 38 °, 44 °, 64 °
Stronger peak is corresponding with (111) of silver, (200), (220) crystal face, the stronger peak and oxygen occurred at 28 °, 33 °, 47 °, 56 °
Change cerium (111), (200), (220), (311) crystal face are corresponding, illustrate the presence for having silver-colored cerium oxide in sample.It can be with from attached drawing 3
It was found that the nucleocapsid of catalyst of the present invention, preferably, clear-cut texture illustrates that crystallinity is preferable to dispersibility, and Average Particle Diameters are
5-10nm, nano-Ag particles 4-8nm of average out to, 1.5-4nm of cerium oxide nano layer thickness average out to.
Embodiment two
The first step takes the distilled water of the glycerine that volume is 40ml and 10ml to be mixed into solution, be added 0.18g silver nitrates and
0.142g sodium citrates, ultrasonic disperse are placed on heated at constant temperature in 135 DEG C of oil bath pans and stir 1h.Centrifugation, washing, is dried to obtain
Silver nano-grain.
Second step weighs 0.4342g cerous nitrates and 0.1078g silver is added in distilled water, and 0.26g citric acids are added, use ammonia
Water adjusts pH value to 6.7, generates dispersion.Magnetic agitation acts on mixed solution 1.5h using the method for pulsed laser action, obtains
It is centrifuged to product, it is dry.Wherein laser parameter is：Power 106w/cm2, voltage 720v, pulsewidth 10ms, frequency 10Hz, wavelength
523nm, energy 250mJ/cm2。
Third step makes nitrate decompose to obtain catalyst product using high-temperature sintering process, and the complete product of above-mentioned drying is existed
It is sintered in Muffle furnace, is increased to 500 DEG C with the rate of 3 DEG C/min, keeps temperature 5h, the nitrate in presoma is made to divide completely
Solution.It then cools to room temperature (20 DEG C -25 DEG C) with the furnace, finally obtains catalyst.
From attached drawing 4 it is again seen that the structure of nucleocapsid, and clear-cut texture, crystallinity is good, and grain size is 10nm or so.
Embodiment three
The first step takes the distilled water of the glycerine that volume is 40ml and 10ml to be mixed into solution, be added 0.18g silver nitrates and
0.142g sodium citrates, ultrasonic disperse are placed on heated at constant temperature in 135 DEG C of oil bath pans and stir 1h.Centrifugation, washing, is dried to obtain
Silver nano-grain.
Second step weighs 0.2171g cerous nitrates and 0.1078g silver is added in distilled water, and 0.26g citric acids are added, use ammonia
Water adjusts pH value to 6.7, generates dispersion.Magnetic agitation acts on mixed solution 1.5h using the method for pulsed laser action, obtains
It is centrifuged to product, it is dry.Wherein laser parameter is：Power 106w/cm2, voltage 720v, pulsewidth 10ms, frequency 10Hz, wavelength
523nm, energy 350mJ/cm2。
Third step makes nitrate decompose to obtain catalyst product using high-temperature sintering process, and the complete product of above-mentioned drying is existed
It is sintered in Muffle furnace, is increased to 500 DEG C with the rate of 3 DEG C/min, keeps temperature 5h, the nitrate in presoma is made to divide completely
Solution.It then cools to room temperature (20 DEG C -25 DEG C) with the furnace, finally obtains catalyst.
By the absorption oxygen content of contrast sample and untreated cerium oxide, it is found that the absorption oxygen content in sample carries significantly
Height illustrates that the oxygen vacancy concentration in sample increases, to illustrate that the catalytic performance of sample is enhanced.
Example IV
The first step takes the distilled water of the glycerine that volume is 40ml and 10ml to be mixed into solution, be added 0.18g silver nitrates and
0.142g sodium citrates, ultrasonic disperse are placed on heated at constant temperature in 135 DEG C of oil bath pans and stir 1h.Centrifugation, washing, is dried to obtain
Silver nano-grain.
Second step weighs 0.4342g cerous nitrates and 0.1078g silver is added in distilled water, and 0.26g citric acids are added, use ammonia
Water adjusts pH value to 6.7, generates dispersion.Magnetic agitation acts on mixed solution 1.5h using the method for pulsed laser action, obtains
It is centrifuged to product, it is dry.Wherein laser parameter is：Power 106w/cm2, voltage 720v, pulsewidth 10ms, frequency 10Hz, wavelength
523nm, energy 350mJ/cm2。
Third step makes nitrate decompose to obtain catalyst product using high-temperature sintering process, and the complete product of above-mentioned drying is existed
It is sintered in Muffle furnace, is increased to 500 DEG C with the rate of 3 DEG C/min, keeps temperature 5h, the nitrate in presoma is made to divide completely
Solution.It then cools to room temperature (20 DEG C -25 DEG C) with the furnace, finally obtains catalyst.
By the absorption oxygen content of contrast sample and untreated cerium oxide, it is found that the absorption oxygen content in sample carries significantly
Height illustrates that the oxygen vacancy concentration in sample increases, to illustrate that the catalytic performance of sample is enhanced.
Comparative example one, embodiment two, embodiment three, example IV sample and untreated cerium oxide H2- TPR spectrograms I
Find that hydrogen reducing temperature is reduced to 200 DEG C from original 400 DEG C, greatly reduce catalyst initial temperature, improve
The catalytic activity of catalyst.
The adjustment of technological parameter is carried out according to the content of present invention can prepare the catalyst of nucleocapsid, and show basic
Consistent performance.Illustrative description has been done to the present invention above, it should explanation, in the feelings for not departing from core of the invention
Under condition, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work
Each fall within protection scope of the present invention.
Claims (9)
1. cerium base catalyst with core-casing structure, which is characterized in that using nano silver as kernel, form cerium oxide nano outside nano silver
Layer, nano-Ag particles 4-8nm of average out to, cerium oxide nano layer thickness 1.5-4nm of average out to are carried out as steps described below：
It is 6-7 that cerous nitrate, nano silver and citric acid, which are dispersed in distilled water and adjust pH value using ammonium hydroxide, with laser
It on the water surface and exports millisecond pulse laser signal and acts on solution, wherein millisecond pulse laser signal parameter is power
106w/cm2, voltage 720v, pulsewidth 10ms, 1-10HZ of frequency, wavelength 523nm, 150-350mJ/cm of energy2, laser target surface
Apart from 5-10mm of the water surface, at least 1 hour action time, the molal quantity of citric acid is the 0.8-of silver and cerous nitrate total mole number
1.5；Rate by product from 20-25 degrees Celsius of room temperature with 3-5 DEG C/min is increased to 500-600 DEG C, is protected in air atmosphere
3-5h of temperature is held, so that the nitrate in presoma decomposes completely, is formed using nano silver as kernel, cerium oxide is the cerium of outer layer
Base catalyst with core-casing structure.
2. cerium base catalyst with core-casing structure according to claim 1, which is characterized in that nano-Ag particles average out to 5-
6nm；2-3nm of cerium oxide nano layer thickness average out to.
3. cerium base catalyst with core-casing structure according to claim 1, which is characterized in that millisecond pulse laser signal parameter is
Power 106w/cm2, voltage 720v, pulsewidth 10ms, 5-10HZ of frequency, wavelength 523nm, 200-300mJ/cm of energy2, when effect
Between be 1.5-2 hours.
4. cerium base catalyst with core-casing structure according to claim 1, which is characterized in that the molal quantity of citric acid is silver and nitre
0.8-the 1 of sour cerium total mole number.
5. cerium base catalyst with core-casing structure according to claim 1, which is characterized in that the mass ratio of cerous nitrate and nano silver
For (2-4)：1.
6. the preparation method of cerium base catalyst with core-casing structure, which is characterized in that cerous nitrate, nano silver and citric acid are dispersed in
It is 6-7 in distilled water and to adjust pH value using ammonium hydroxide, is located on the water surface with laser and exports millisecond pulse laser signal work
For solution, wherein millisecond pulse laser signal parameter is power 106w/cm2, voltage 720v, pulsewidth 10ms, 1-10HZ of frequency,
Wavelength 523nm, 150-350mJ/cm of energy2, laser target surface is apart from 5-10mm of the water surface, at least 1 hour action time, lemon
The molal quantity of acid is 0.8-the 1.5 of silver and cerous nitrate total mole number；By product from 20-25 degrees Celsius of room temperature with 3-5 DEG C/min
Rate be increased to 500-600 DEG C, in air atmosphere keep 3-5h of temperature so that the nitrate in presoma divides completely
Solution is formed using nano silver as kernel, and cerium oxide is the cerium base catalyst with core-casing structure of outer layer.
7. the preparation method of cerium base catalyst with core-casing structure according to claim 6, which is characterized in that millisecond pulse laser
Signal parameter is power 106w/cm2, voltage 720v, pulsewidth 10ms, 5-10HZ of frequency, wavelength 523nm, 200-300mJ/ of energy
cm2, action time is 1.5-2 hours.
8. the preparation method of cerium base catalyst with core-casing structure according to claim 6, which is characterized in that mole of citric acid
Number is silver and 0.8-the 1 of cerous nitrate total mole number.
9. the preparation method of cerium base catalyst with core-casing structure according to claim 6, which is characterized in that cerous nitrate and nanometer
The mass ratio of silver is (2-4)：1.
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