CN106000400A - Method for preparing three-dimensional rare earth oxide nanorod framework loaded noble metal nanoparticles - Google Patents
Method for preparing three-dimensional rare earth oxide nanorod framework loaded noble metal nanoparticles Download PDFInfo
- Publication number
- CN106000400A CN106000400A CN201610316365.4A CN201610316365A CN106000400A CN 106000400 A CN106000400 A CN 106000400A CN 201610316365 A CN201610316365 A CN 201610316365A CN 106000400 A CN106000400 A CN 106000400A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- noble metal
- earth oxide
- alloy
- nanometer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 25
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 22
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 7
- 239000002073 nanorod Substances 0.000 title abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 8
- 230000007797 corrosion Effects 0.000 claims abstract description 5
- 238000005260 corrosion Methods 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000005266 casting Methods 0.000 claims description 25
- 239000012298 atmosphere Substances 0.000 claims description 21
- 238000007578 melt-quenching technique Methods 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 18
- 238000005275 alloying Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000010970 precious metal Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910002058 ternary alloy Inorganic materials 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 35
- 239000000956 alloy Substances 0.000 abstract description 35
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 238000010791 quenching Methods 0.000 abstract description 4
- 230000000171 quenching effect Effects 0.000 abstract description 4
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000003723 Smelting Methods 0.000 abstract 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000010944 silver (metal) Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000004927 fusion Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000010891 electric arc Methods 0.000 description 6
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- -1 compound rare earth Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
-
- 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
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for preparing three-dimensional rare earth oxide nanorod framework loaded noble metal nanoparticles. Aluminum, rare earth metal and noble metal are prepared into ternary precursor alloy through a smelting method, the alloy is prepared into an alloy strip in a melt quick quenching mode, the alloy strip is subjected to dealloying and corrosion for 8-14 h in an alkaline solution with the mass percentage being 5-20% under the water bath conditions that the temperature is 60-80 DEG C, then the alloy strip is washed with deionized water and alcohol, the cleaned alloy strip is placed in a constant-temperature drying box to be dried for 2 h at the temperature of 50 DEG C, then the alloy strip is forged for 1 h at 300-600 DEG C, and the blocky three-dimensional rare earth oxide nanorod framework loaded noble metal nanoparticles are obtained. Active components are easily controlled through alloy smelting and dealloying by means of control over original components, and active species grow in a three-dimensional framework composed of rare earth oxide nanorods in situ to form a composite material, so the agglomeration tendency can be prevented, the nanoscale state can be maintained, the nano-effect is fully achieved, and the catalysis performance of the composite material can be greatly improved.
Description
Technical field
The present invention relates to the preparation method of composite, particularly to three-dimensional nanometer rare earth oxide rod framework
Supported precious metal nano-particle preparation method.
Background technology
Rare earth oxide is widely used in various urging as catalyst adding ingredient or the carrier of a class excellence
Change in reaction, due to oxygen ability of storing, high oxygen carrying content and cheap price that it is strong.In order to improve rare earth
The catalytic performance of oxide, is generally combined it with the second active phase, forms rare earth oxide and is combined
Material.When active element is lived showing high chemical catalysis when species are prepared as nano material as adding
Property, when reactive nanoparticles is supported on rare earth oxide etc., there is the carrier formation nanometer of catalysis activity especially
During composite, form active interface generation strong interface reciprocal action owing to both catalysis materials combine, can
Embody higher catalysis activity.Particularly it is prepared as bar-shaped when oxide nano rare earth, and activity is received
After rice grain is supported in this nanometer rods formation composite, can more fully play small interface
Complex effect, often shows more excellent catalytic performance.Traditional nanometer rare earth oxide rod is base
The preparation method of composite nano materials is usually the hydrothermal synthesis method using complex process, and finally give is
Composite nano-powder.But, these traditional handicrafts not only need substantial amounts of surfactant, growth inducing
The organic reagent such as agent and protective agent, and need strictly to control the concentration of hydrothermal temperature, time and solution
Deng.And the surface that nanometer powder is high when high temperature sintering can often result in the reunion of active phase, causes
The decline of catalytic performance, particularly in high-temperature catalytic field, makes due to reunion and the sintering of nanometer powder
The decline of catalytic performance is become to inactivate.And the active phase great majority added in this process are by chemistry
Effect is deposited on the surface of nanometer rare earth oxide rod, and force ratio is more weak, is in use easy to
Inactivation, therefore the preparation method of preparation at present is difficult to be formed in situ active specy, produces firm nanometer chi
Degree interface, and maintain the high activity of rare earth oxide based nano composite material.
Summary of the invention
The present invention is in order to overcome the deficiency of background technology, it is provided that a kind of three-dimensional nanometer rare earth oxide rod structure
Frame supported precious metal nano-particle preparation method, utilizes removal alloying and surface in situ load oxidation technology,
By aluminum, rare earth metal, noble metal is prepared as ternary forerunner's alloy by the method for melting, and alloy is by molten
Body fast quenching is prepared as alloy thin band, alloy thin band 20-80 DEG C, 5%-20% alkaline solution is carried out close
After aurification corrosion, after 100-800 DEG C of calcining 1 hour, so that it may obtain three-dimensional nanometer rare earth oxide rod former
The nanocomposite catalytic of position carried noble metal active specy, the present invention utilizes alloy melting and de-alloy
It is easy to the control by primitive component and controls active component, and by these active specy growth in situ
In the three-dimension-framework matrix of nanometer rare earth oxide bar construction, constitute composite and just can stop this group
Poly-tendency, can maintain its nano-sized state to give full play to nano effect so that it is catalytic performance carries significantly
High；During this most not by concentration, time, temperature and the alloy state of corrosive liquid to its composite wood
The forming process impact of material, is more beneficial for the preparation of this composite and large-scale application.
In order to achieve the above object, the present invention adopts the following technical scheme that and is achieved:
The preparation method of three-dimensional nanometer rare earth oxide rod framework supported precious metal nano-particle composite,
Comprise the steps:
(1) by mole, by the aluminum of 70-93.99%, the rare earth metal of 6-15%, 0.01-15%
The mixing of three kinds of raw materials of noble metal, and be heated to 600 DEG C-900 DEG C under vacuum or 0.1MPa ar gas environment
After being smelted into uniform ternary alloy three-partalloy, it is prepared as ingot casting with common casting method；
(2) gained ingot casting is heated to 600 DEG C-900 DEG C two under the conditions of vacuum or 0.1MPa protective atmosphere
Secondary fusing, is prepared as ternary alloy three-partalloy strip with melt-quenching method；
(3) by ternary alloy three-partalloy strip in strong alkali solution at 60-80 DEG C water-bath carry out removal alloying corrosion
After, repeatedly clean with deionized water and ethanol, be placed in the thermostatic drying chamber of 50 DEG C dry after cleaning up
Dry 2 hours；
(4) the ternary alloy three-partalloy strip roasting 1-3 in the air of 100-800 DEG C after removal alloying being corroded
Hour, i.e. can get the composite of nanometer rare earth oxide rod framework supported precious metal nano-particle.
Rare earth metal described in step (1) includes cerium oxide, lanthana, yittrium oxide or Disamarium trioxide.
Noble metal metal described in step (1) includes noble silver, gold, palladium or platinum.
Strong base solution described in step (3) is KOH or NaOH solution, and its mass fraction is 5%-20
%.
Removal alloying etching time described in step (3) is 8-13 hour.
Compared with the prior art, the invention have the benefit that
The composite catalyzing material prepared by said method shows high after 400 DEG C of heat treatments
Structural stability and catalysis activity.After calcining, noble metal nano particles is supported on nanometer rare earth oxide in situ
The surface of rod framework, forms interface clearly.The nanometer rare earth oxide rod formed when adding noble metal is born
Supported noble metal nano-particle, to NaBH4Catalysis oxidation performance goes out high activity.Such as, compared with fine silver,
Ag/CeO2The unit mass oxidate current of NaBH4 is improved nearly 2.5 times.Alloy is utilized to design
With the pure CeO going alloyage to prepare2, in air speed 60000h-1Time, the CO converting 1% reaches 50%
During conversion ratio, the temperature of needs is about 240 DEG C, and the pure CeO utilizing other method to prepare that document is reported2
The temperature that the CO of catalysis oxidation 1% reaches to need during the conversion of 50% is up to 300 DEG C.Work as CeO2Nanometer rods
During upper load Au nano-particle, the catalytic oxidation activity of CO is obviously enhanced, the CO of 1% under room temperature
I.e. can reach the conversion ratio of 20%, 50% temperature converted only needs 60 DEG C.The most this method prepare three
Its advantage of material of dimension compound rare earth nano rod base is that rare earth element and noble metal are added simultaneously to presoma
In alloy, final product can be controlled by corrosion and heat treatment process, technique is simple, it is controlled to facilitate,
Pollution-free, the composite finally given will not be made too high surface energy and cause noble metal nano particles and reunite,
Promote giving full play to of composite catalytic performance.This method makes full use of the character of addition element, alloy
Composition design and the structure of the regulation and control composite such as heat treatment temperature, reducing consumption same of rare precious metal
Time can also significantly increase composite catalysis activity, for preparing low precious metal content high catalytic activity
Composite catalyst provides a kind of new approaches.Use the oxide nano-rod base obtained by this method multiple
Closing catalysis material, the size of oxide diameter is not more than 15 nanometers, rod length between 50-200 nanometer,
After removal alloying, noble metal component is not lost, and after roasting, being smaller in size than of the nano-particle of addition element 20 is received
Rice, and be firmly supported on three-dimensional oxide nanometer rods.By adding the in precursor alloy
Three elements, removal alloying and oxidizing process can realize active specy nano-particle is supported on three-dimensional oxidation
In thing nanometer rods, this technique can be greatly saved the consumption of noble metal and noble metal is fully used
Given play to high-performance simultaneously.The oxygen that the performance of prepared composite is prepared apparently higher than traditional method
The composite of compound nanometer rods base.
Accompanying drawing explanation
Below in conjunction with the drawings and the specific embodiments, the present invention is described in further detail.
Fig. 1 is the three-dimensional CeO of the embodiment of the present invention 12The structure of nanometer rods loaded Ag nano-particle.Its
In, (a) and (b) figure are the stereoscan photograph of low power；C () figure is the stereoscan photograph of high power；(d)
Figure is the transmission electron microscope photo of high power.
Fig. 2 is the three-dimensional CeO of the embodiment of the present invention 22Nanometer rods load Ag nano particles and porous Ag
Catalysis oxidation NaBH4Volt-ampere cyclic curve figure.
Detailed description of the invention
Embodiment one
The step of the present embodiment includes: by mol ratio 79%Al, formulated former of 6%Ce and 15%Ag
Material under vacuo with electric arc be heated to 700 DEG C be smelted into uniform forerunner's alloy after, use common casting method
It is prepared as ingot casting；Alloy cast ingot secondary fusion adding in the fast melt-quenching stove of 0.1MPa protective atmosphere condition
Heat, to 750 DEG C, prepares strip with melt-quenching method；Strip is at the NaOH aqueous solution that mass fraction is 5%
In 60 DEG C of water-baths, removal alloying corrodes 12 hours, after not having obvious bubble, with deionized water and ethanol repeatedly
Clean, be placed on after cleaning up in the thermostatic drying chamber of 50 DEG C and be dried 2 hours, then at 400 DEG C of air
After atmosphere kiln roasting 1 hour, prepare cerium oxide loading nano silvery granule nanometer three-dimension-framework composite.
Obtained nano composite material goes out high activity to NaBH4 oxidation performance.The present embodiment is three-dimensional
CeO2The microstructure of the composite of nanometer rods loaded Ag nano-particle can be found in Fig. 1, can from Fig. 1
Finding out, CeO2 nanometer rods has substantially loaded a lot of Ag nano-particle, and the width of nanometer rods is averagely about
10nm, length is about 40-200nm.Figure it is seen that with the list of nanoporous Ag, NaBH4
Position quality oxide electric current density significantly improves.
Embodiment two
By mol ratio 89.7%Al, raw material formulated for 10%Ce and 0.3%Au is at argon shield gas
Under atmosphere with electric arc melting be heated to 750 DEG C be smelted into uniform forerunner's alloy after, prepare with common casting method
Become ingot casting；Alloy cast ingot secondary fusion being heated in the fast melt-quenching stove of 0.1MPa protective atmosphere condition
800 DEG C, prepare strip with melt-quenching method；Strip is in the NaOH aqueous solution that mass fraction is 10%
Alloying is corroded 12 hours, after not having obvious bubble, repeatedly cleans with deionized water and ethanol, cleans dry
It is placed on after Jing in the thermostatic drying chamber of 50 DEG C and is dried 2 hours；Then at 400 DEG C of air atmosphere kiln roastings
Cerium oxide loading nano silvery granule nanometer three-dimension-framework composite is i.e. prepared after 1 hour.
CO catalysis oxidation performance is gone out high activity, the most i.e. can reach the conversion ratio of 20%.
Embodiment three
By mol ratio 84%Al, raw material formulated for 6%Ce and 10%Ag adds with electric arc under vacuo
After heat is smelted into uniform forerunner's alloy to 600 DEG C, it is prepared as ingot casting with common casting method；Alloy cast ingot
Secondary fusion be heated to 650 DEG C in the fast melt-quenching stove of 0.1MPa protective atmosphere condition, fast with melt
The method of quenching prepares strip；Strip is removal alloying in 60 DEG C of water-baths of NaOH aqueous solution that mass fraction is 5%
Corrode 13 hours, after there is no obvious bubble, repeatedly clean with deionized water and ethanol, put after cleaning up
Put and be dried 2 hours in the thermostatic drying chamber of 50 DEG C, then at 400 DEG C of air atmosphere kiln roastings 1 hour
After, prepare cerium oxide loading nano silvery granule nanometer three-dimension-framework composite.
Embodiment four
By mol ratio 88.5%Al, raw material formulated for 10%Sm and 1.5%Ag electricity consumption under vacuo
Arc be heated to 700 DEG C be smelted into uniform forerunner's alloy after, be prepared as ingot casting with common casting method；Alloy
Ingot casting secondary fusion be heated to 750 DEG C in the fast melt-quenching stove of 0.1MPa protective atmosphere condition, with molten
Body quick quenching technique prepares strip；Strip goes to close in 60 DEG C of water-baths of NaOH aqueous solution that mass fraction is 5%
Aurification is corroded 12 hours, after not having obvious bubble, repeatedly cleans with deionized water and ethanol, cleans up
After be placed in the thermostatic drying chamber of 50 DEG C be dried 2 hours, then at 400 DEG C of air atmosphere kiln roastings 1
After hour, prepare Disamarium trioxide loading nano silvery granule nanometer three-dimension-framework composite.
Embodiment five
By mol ratio 93.99%Al, raw material formulated for 15%La and 0.01%Pt is at 0.1MPa argon
After being smelted into uniform forerunner's alloy by electric arc heated 750 DEG C under compression ring border, it is prepared as with common casting method
Ingot casting；Alloy cast ingot secondary fusion being heated in the fast melt-quenching stove of 0.1MPa protective atmosphere condition
800 DEG C, prepare strip with melt-quenching method；Strip is in the KOH aqueous solution that mass fraction is 20%
Alloying is corroded, and after not having obvious bubble, repeatedly cleans with deionized water and ethanol, puts after cleaning up
Put and be dried 4 hours in the thermostatic drying chamber of 40 DEG C, then at 500 DEG C of air atmosphere kiln roastings 2 hours
After, prepare lanthana load nano-platinum particle nanometer three-dimension-framework composite.This composite is in room temperature
Under show the CO catalytic oxidation performance of enhancing.
Embodiment six
By mol ratio 84.5%Al, raw material formulated for 15%Sm and 0.5%Pt is at 0.1MPa argon
After being smelted into uniform forerunner's alloy by electric arc heated 750 DEG C under environment, it is prepared as casting with common casting method
Ingot；Alloy cast ingot secondary fusion being heated in the fast melt-quenching stove of 0.1MPa protective atmosphere condition
800 DEG C, prepare strip with melt-quenching method；Strip is in the KOH aqueous solution that mass fraction is 10%
Alloying is corroded, and after not having obvious bubble, repeatedly cleans with deionized water and ethanol, puts after cleaning up
Put and be dried 4 hours in the thermostatic drying chamber of 40 DEG C, then at 500 DEG C of air atmosphere kiln roastings 2 hours
After, prepare Disamarium trioxide load nano-platinum particle nanometer three-dimension-framework composite.This composite is in room temperature
Under show the CO catalytic oxidation performance of enhancing.
Embodiment seven
By mol ratio 89%Al, raw material formulated for 10%La and 1%Au is under argon atmosphere
With electric arc melting be heated to 750 DEG C be smelted into uniform forerunner's alloy after, with common casting method be prepared as casting
Ingot；Alloy cast ingot secondary fusion being heated in the fast melt-quenching stove of 0.1MPa protective atmosphere condition
800 DEG C, prepare strip with melt-quenching method；Strip is in the NaOH aqueous solution that mass fraction is 10%
Alloying is corroded 12 hours, after not having obvious bubble, repeatedly cleans with deionized water and ethanol, cleans dry
It is placed on after Jing in the thermostatic drying chamber of 50 DEG C and is dried 2 hours；Then at 400 DEG C of air atmosphere kiln roastings
After 1 hour, i.e. prepare lanthana supported nano-gold granule nanometer three-dimension-framework composite.CO is catalyzed
Oxidation performance goes out high activity, and oxidation reaction at room temperature can occur.
Embodiment eight
By mol ratio 73%Al, raw material formulated for 12%Ce and 5%Pd is at 0.1MPa argon ring
Under border electric induction furnace be heated to 800 DEG C be smelted into uniform forerunner's alloy after, be prepared as with common casting method
Ingot casting；Alloy cast ingot secondary fusion being heated in the fast melt-quenching stove of 0.1MPa protective atmosphere condition
850 DEG C, prepare strip with melt-quenching method；Strip is in the NaOH aqueous solution that mass fraction is 15%
Alloying is corroded, and after not having obvious bubble, repeatedly cleans with deionized water and ethanol, puts after cleaning up
Put and be dried 2 hours in the thermostatic drying chamber of 50 DEG C, then at 400 DEG C of air atmosphere kiln roastings 1 hour
After, prepare the three-dimension-framework composite of cerium oxide load nanoparticle palladium.
Embodiment nine
By mol ratio 70%Al, raw material formulated for 15%Y and 15%Pd is at 0.1MPa argon ring
Under border electric induction furnace be heated to 850 DEG C be smelted into uniform forerunner's alloy after, be prepared as with common casting method
Ingot casting；Alloy cast ingot secondary fusion being heated in the fast melt-quenching stove of 0.1MPa protective atmosphere condition
900 DEG C, prepare strip with melt-quenching method；Strip is in the NaOH aqueous solution that mass fraction is 15%
Alloying is corroded, and after not having obvious bubble, repeatedly cleans with deionized water and ethanol, puts after cleaning up
Put and be dried 2 hours in the thermostatic drying chamber of 50 DEG C, then at 400 DEG C of air atmosphere kiln roastings 1 hour
The rear three-dimension-framework composite preparing yittrium oxide load nanoparticle palladium.
Claims (5)
1. the preparation side of three-dimensional nanometer rare earth oxide rod framework supported precious metal nano-particle composite
Method, it is characterised in that comprise the steps:
(1) by mole, by the aluminum of 70-93.99%, the rare earth metal of 6-15%, 0.01-15%
The mixing of three kinds of raw materials of noble metal, and be heated to 600 DEG C-900 DEG C under vacuum or 0.1MPa ar gas environment
After being smelted into uniform ternary alloy three-partalloy, it is prepared as ingot casting with common casting method；
(2) gained ingot casting is heated to 600 DEG C-900 DEG C two under the conditions of vacuum or 0.1MPa protective atmosphere
Secondary fusing, is prepared as ternary alloy three-partalloy strip with melt-quenching method；
(3) by ternary alloy three-partalloy strip in strong alkali solution at 60-80 DEG C water-bath carry out removal alloying corrosion
After, repeatedly clean with deionized water and ethanol, be placed in the thermostatic drying chamber of 50 DEG C dry after cleaning up
Dry 2 hours；
(4) the ternary alloy three-partalloy strip roasting 1-3 in the air of 100-800 DEG C after removal alloying being corroded
Hour, i.e. can get the composite of nanometer rare earth oxide rod framework supported precious metal nano-particle.
Three-dimensional nanometer rare earth oxide rod framework carried noble metal nanometer the most according to claim 1
The preparation method of particle composite material, it is characterised in that the rare earth metal described in step (1) includes oxidation
Cerium, lanthana, yittrium oxide or Disamarium trioxide.
Three-dimensional nanometer rare earth oxide rod framework carried noble metal nanometer the most according to claim 1
The preparation method of particle composite material, it is characterised in that the noble metal metal described in step (1) includes expensive
Argent, gold, palladium or platinum.
Three-dimensional nanometer rare earth oxide rod framework carried noble metal nanometer the most according to claim 1
The preparation method of particle composite material, it is characterised in that the strong base solution described in step (3) is KOH
Or NaOH solution, its mass fraction is 5%-20%.
Three-dimensional nanometer rare earth oxide rod framework carried noble metal nanoparticle the most according to claim 1
The preparation method of sub-composite, it is characterised in that the removal alloying etching time described in step (3) is
8-13 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610316365.4A CN106000400A (en) | 2016-05-12 | 2016-05-12 | Method for preparing three-dimensional rare earth oxide nanorod framework loaded noble metal nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610316365.4A CN106000400A (en) | 2016-05-12 | 2016-05-12 | Method for preparing three-dimensional rare earth oxide nanorod framework loaded noble metal nanoparticles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106000400A true CN106000400A (en) | 2016-10-12 |
Family
ID=57099485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610316365.4A Pending CN106000400A (en) | 2016-05-12 | 2016-05-12 | Method for preparing three-dimensional rare earth oxide nanorod framework loaded noble metal nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106000400A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108956745A (en) * | 2018-06-12 | 2018-12-07 | 齐鲁工业大学 | Preparation method and applications based on nanoporous platinum-cobalt oxide hybrid material modified electrode |
| CN109012668A (en) * | 2018-08-17 | 2018-12-18 | 西安交通大学 | CeO2The preparation method of skeleton adulteration transition metal oxide and noble metal composite-material |
| CN111826544A (en) * | 2020-06-18 | 2020-10-27 | 西安工程大学 | Preparation method of cellular nano-porous Ag-Ni conductive powder |
| US10987657B1 (en) * | 2020-09-23 | 2021-04-27 | King Abdulaziz University | Gold supported yttrium oxide nanorods and methods of use thereof |
| CN115491691A (en) * | 2022-10-24 | 2022-12-20 | 吉林大学 | Preparation method and application of self-supporting nano porous layer sheet FeCo/Ce-O-N composite electrode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974345A (en) * | 2012-11-13 | 2013-03-20 | 西安交通大学 | Preparation method of noble metal load cerium oxide nano-porous catalytic material |
| CN104624200A (en) * | 2014-12-30 | 2015-05-20 | 西安交通大学 | Preparation method of nano porous copper oxide loaded precious metal catalytic material |
-
2016
- 2016-05-12 CN CN201610316365.4A patent/CN106000400A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974345A (en) * | 2012-11-13 | 2013-03-20 | 西安交通大学 | Preparation method of noble metal load cerium oxide nano-porous catalytic material |
| CN104624200A (en) * | 2014-12-30 | 2015-05-20 | 西安交通大学 | Preparation method of nano porous copper oxide loaded precious metal catalytic material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108956745A (en) * | 2018-06-12 | 2018-12-07 | 齐鲁工业大学 | Preparation method and applications based on nanoporous platinum-cobalt oxide hybrid material modified electrode |
| CN109012668A (en) * | 2018-08-17 | 2018-12-18 | 西安交通大学 | CeO2The preparation method of skeleton adulteration transition metal oxide and noble metal composite-material |
| CN111826544A (en) * | 2020-06-18 | 2020-10-27 | 西安工程大学 | Preparation method of cellular nano-porous Ag-Ni conductive powder |
| US10987657B1 (en) * | 2020-09-23 | 2021-04-27 | King Abdulaziz University | Gold supported yttrium oxide nanorods and methods of use thereof |
| CN115491691A (en) * | 2022-10-24 | 2022-12-20 | 吉林大学 | Preparation method and application of self-supporting nano porous layer sheet FeCo/Ce-O-N composite electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106000400A (en) | Method for preparing three-dimensional rare earth oxide nanorod framework loaded noble metal nanoparticles | |
| CN104941674B (en) | Catalyst of phosphatization cobalt and its preparation method and application is loaded on a kind of activated carbon | |
| Jin et al. | Palladium nanocrystals enclosed by {100} and {111} facets in controlled proportions and their catalytic activities for formic acid oxidation | |
| Trinh et al. | Synthesis, characterization and environmental applications of bismuth vanadate | |
| CN102553582B (en) | Method for preparing carbon supported Au-Pt or Au-Pd catalyst | |
| CN102350346B (en) | Preparation method of visible light catalyst with surface plasmon effect and application thereof | |
| CN104624200A (en) | Preparation method of nano porous copper oxide loaded precious metal catalytic material | |
| KR101265075B1 (en) | Preparing method of alloy catalyst for fuel cell using silica coating | |
| CN104815651B (en) | Preparation method of precious metal/titanium dioxide nano composite | |
| CN104646025B (en) | A kind of preparation method of hollow Pt/Ni alloys and graphene aerogel composite | |
| CN108855173B (en) | Method for producing hydrogen by photoelectrocatalysis water decomposition, plasma catalyst used in method and preparation method | |
| CN105977502A (en) | Three-dimensional graphene/silver nanoparticle composite material employing nickel foam as matrix and preparation method of three-dimensional graphene/silver nanoparticle composite material | |
| Gebre et al. | Trimetallic nanostructures and their applications in electrocatalytic energy conversions | |
| CN110216282A (en) | The preparation method of acid bronze alloy contact | |
| CN107088415A (en) | A kind of preparation method of platinum alloy nanometer powder catalyst | |
| Zhang et al. | Recent progress in ultrafine 3D Pd-based nanocubes with multiple structures for advanced fuel cells electrocatalysis | |
| CN102974345B (en) | Preparation method of noble metal load cerium oxide nano-porous catalytic material | |
| CN109012668A (en) | CeO2The preparation method of skeleton adulteration transition metal oxide and noble metal composite-material | |
| Jiang et al. | Synergism of multicomponent catalysis: one-dimensional Pt-Rh-Pd nanochain catalysts for efficient methanol oxidation | |
| Li et al. | Concave structure of Cu 2 O truncated microcubes: PVP assisted {100} facet etching and improved facet-dependent photocatalytic properties | |
| CN109107573A (en) | A kind of co-modified Sn of Au/Ag3O4The preparation method of nano composite photocatalytic material | |
| Chen et al. | Advances in photochemical deposition for controllable synthesis of heterogeneous catalysts | |
| CN113145133B (en) | Photocatalytic material based on metal-semiconductor composite structure, preparation method and magnetic field auxiliary application thereof | |
| CN113206264A (en) | Platinum-based intermetallic nanocrystalline with ordered structure and medium and low temperature preparation and application thereof | |
| CN109174092A (en) | A kind of zinc oxide/platinum composite material microballoon and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161012 |
|
| RJ01 | Rejection of invention patent application after publication |