CN102489337A - SnO2 catalytic material loaded with nano precious metals and preparation method thereof - Google Patents

SnO2 catalytic material loaded with nano precious metals and preparation method thereof Download PDF

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Publication number
CN102489337A
CN102489337A CN2011103923429A CN201110392342A CN102489337A CN 102489337 A CN102489337 A CN 102489337A CN 2011103923429 A CN2011103923429 A CN 2011103923429A CN 201110392342 A CN201110392342 A CN 201110392342A CN 102489337 A CN102489337 A CN 102489337A
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noble metal
nano
sno
preparation
catalysis material
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CN2011103923429A
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周晓龙
曹建春
陈敬超
于杰
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The invention relates to a SnO2 catalytic material loaded with nano precious metals and a preparation method thereof. The technique is based on processing of supersaturated tin-based alloy, and combined with the heat treatment technique on the condition of an oxygen atmosphere to obtain the SnO2 catalytic material of a multi-layer cylindrical honeycomb structure, the SnO2 catalytic material has a large specific surface area, the nano precious metals are evenly distributed, the structure of the catalytic material is firm, and the catalytic effect is obvious. The preparation technique integrates preparation of precious metal nano particles, preparation of carriers and structural design into one, and has the advantages of being low in cost, short in process, environment-friendly and high in property. Products prepared by means of the technique can be used in the fields of automobiles, oil, the chemical industry and the like.

Description

A kind of SnO of loaded with nano noble metal 2Catalysis material and preparation method thereof
Technical field:
The present invention relates to a kind of multi-layer cylinder shape honeycomb SnO of loaded with nano noble metal 2Catalysis material and preparation method thereof belongs to the catalysis material technical field.
Background technology:
Nano-noble metal has unique photoelectron, chemical characteristic because of it; As catalyst, medical material, function solenoid material, absorbing material, sensor components and parts material and nano composite material etc., oneself demonstrates extremely important using value in research fields such as metallurgy, chemical industry, light industry, electronics, national defence, nuclear technology, Aero-Space.But we notice such fact in the application of noble metal nano particles; For consumption, the reduction material/product cost of practicing thrift noble metal; Usually noble metal nano particles is loaded on certain carrier/surface of solids, comprise vacuum moulding machine, inert gas evaporation, DIFFUSION CONTROLLED reunion, chemistry and the electrochemical deposition etc. of metal.Developed at present Ag, Pt, Au nanocrystal have been distributed to zeolite, TiO 2, Al 2O 3, SiO 2, surface such as graphite, CNT.On this application direction; Existing material preparation technology (physics, chemical method etc.) is fixedly remaining in some problems aspect the noble metal nano particles effectively; Material is not enough to the physics, the chemical property that keep high in application, this is a huge challenge that faces during noble metal nano particles uses.If noble metal nano particles because and can not form effective metallurgical binding between the carrier, in use might receive the huge surface of nano particle can influence and reunite, and then the performance of nano material character is brought negative effect.
SnO 2Belong to the n type semiconductor oxide, have being with of broad, it is as the carrier material of nano-noble metal, and the performance of nano-noble metal catalytic activity is had important function.In view of the above, SnO 2The structure of carrier material, particularly carrier material specific area size, determined the distribution of nano-noble metal, and the quantity of catalytic activity point.Therefore, the present invention passes through carrier S nO 2The structural design of material obtains multi-layer cylinder shape honeycomb SnO 2Carrier to be increasing its specific area, thereby improves the specific area of the nano-noble metal of load, improved the catalytic activity point of catalyst, finally improves the catalytic performance of such catalyst.
Summary of the invention
The SnO that the purpose of this invention is to provide a kind of loaded with nano noble metal 2Catalysis material and preparation method thereof obtains the SnO that the surface is combined with the nano-noble metal particle evenly, securely 2Catalysis material solves nano-noble metal and can not effectively combine with carrier, causes the physics of catalysis material, the problem of unstable chemcial property.
Technical scheme of the present invention is: the SnO of loaded with nano noble metal 2Catalysis material is to be that carrier, top layer are SnO with tin 2And load has the multi-layer cylinder shape honeycomb catalysis material of nano-noble metal particle.The nano-noble metal of load is one or more any mixture among Ag, Pd, the Pt, and grain graininess is a nanoscale, and its percentage by weight is 1%~3% (accounting for the percentage by weight of whole catalysis material).
The SnO of loaded with nano noble metal of the present invention 2The preparation method of catalysis material is: the kamash alloy that at first contains 1%~3% noble metal (percentage by weight) through the melting preparation; Then through plate rolling and honeycomb processing; Acquisition has the base alloy material of multi-layer cylinder shape honeycomb; At last this material is put into the heat-treatment furnace with certain flow oxygen atmosphere and heat-treat and the in-situ oxidation reaction, finally obtain the multi-layer cylinder shape honeycomb SnO that load has nano-noble metal 2The catalysis material product.Concrete preparation process is following:
(1) earlier by 1%~3% percentage by weight, get one or more any mixture among Ag, Pd, the Pt, prepare burden with metallic tin, put into smelting furnace then, adjustment vacuum<1 * 10 -3Pa carries out melting under 220~250 ℃ of temperature conditions, treat that raw material melted the back electromagnetic agitation 1~3 minute fully, pours into a mould ingot blank and cooling naturally then;
(2) under the normal temperature condition; With common metal board rolling method; < the kamash alloy strip of 1mm obtains honeycomb through the honeycomb milling method again, obtains multi-layer cylinder shape honeycomb then through curling being rolled into thickness down with the ingot blank that obtains in the middle of the step (1);
(3) the honeycomb kamash alloy that obtains is put into heat-treatment furnace; Be heated to 180~220 ℃; Flow by 5~15L/min feeds high purity oxygen gas then; Alloy is heat-treated and in-situ oxidation was handled 1~5 hour, come out of the stove after the cooling naturally then, obtain the multi-layer cylinder shape honeycomb SnO that the firm load in surface has the nano-noble metal particle 2Catalysis material.
The purity of said noble metal and metallic tin is equal>99.95%.
Said high purity oxygen gas is that purity is 99.999% oxygen.
The present invention processes alloy material with noble metal and carrier material earlier; Be reprocessed into multi-layer cylinder shape honeycomb; Under certain oxidizing atmosphere condition, alloy heat-treated with in-situ oxidation then and handle; In conjunction with processing characteristics and the deposition of noble metal in heat treatment process of supersaturation metal alloy separate out and form the method that nanophase and matrix oxidation form metal oxide; The preparation and the preparing carriers of noble metal nano particles are united two into one, finally prepare the cylindric multi-layer honeycomb structure SnO that is evenly distributed with nano-noble metal 2Catalysis material.
The present invention compared with prior art has the following advantages:
(1) can obtain that specific area is big, nano-noble metal is evenly distributed, catalysis material sound construction, the tangible new structure catalysis material of catalytic effect;
(2) can combine existing metal alloy compositions preparation, processing and Equipment for Heating Processing, have less investment, low cost and other advantages.
(3) development trend of Composite Preparation technology " efficient, low-cost, short flow process, environmental friendliness, high-performance ".
Description of drawings:
Fig. 1 is a process chart of the present invention;
Fig. 2 is the cylinder-shaped honeycomb structure SnO that area load of the present invention has the nano-noble metal particle 2The catalysis material sketch map.
Specific embodiments:
Below in conjunction with accompanying drawing and embodiment the present invention is done further elaboration, but protection content of the present invention is not limited to said scope.
Embodiment 1: (like Fig. 1)
(1) with Chun Du>99.95% precious metals ag is by the amount of gross weight 1%, with Chun Du>99.95% metallic tin is prepared burden, and puts into smelting furnace then, adjustment vacuum 1 * 10 -5Pa carries out melting under 220 ℃ of temperature conditions, treat that raw material melted the back electromagnetic agitation 1 minute fully, pours into a mould ingot blank and cooling naturally then;
(2) under the normal temperature condition; With common metal board rolling method; The ingot blank that obtains in the middle of the step (1) in the kamash alloy strip that is rolled into thickness 0.8mm down, is obtained honeycomb through the honeycomb milling method again, obtain multi-layer cylinder shape honeycomb then through curling;
(3) the honeycomb kamash alloy that obtains is put into heat-treatment furnace; Be heated to 200 ℃; The flow of pressing 10L/min then feeds high purity oxygen gas; Alloy is heat-treated and in-situ oxidation was handled 3 hours, come out of the stove after the cooling naturally then, obtain the multi-layer cylinder shape honeycomb SnO that the firm load in surface has the nano-noble metal particle 2Catalysis material is to be that carrier, top layer are SnO with tin 2And load has the multi-layer cylinder shape honeycomb SnO of nano-noble metal particle 2Catalysis material, the granularity of the nano-noble metal of tin carrier surface be less than 100nm, the purity purity > of noble metal and metallic tin; 99.95%, the nano-noble metal of load is Ag, and its percentage by weight is 1%.
(like Fig. 2)
Embodiment 2: (like Fig. 1)
(1) with Chun Du>99.95% precious metals pd is by the amount of gross weight 2%, with Chun Du>99.95% metallic tin is prepared burden, and puts into smelting furnace then, adjustment vacuum<1 * 10 -4Pa carries out melting under 230 ℃ of temperature conditions, treat that raw material melted the back electromagnetic agitation 3 minutes fully, pours into a mould ingot blank and cooling naturally then;
(2) under the normal temperature condition; With common metal board rolling method; The ingot blank that obtains in the middle of the step (1) in the kamash alloy strip that is rolled into thickness 0.5mm down, is obtained honeycomb through the honeycomb milling method again, obtain multi-layer cylinder shape honeycomb then through curling;
(3) the honeycomb kamash alloy that obtains is put into heat-treatment furnace; Be heated to 180 ℃; The flow of pressing 15L/min then feeds high purity oxygen gas; Alloy is heat-treated and in-situ oxidation was handled 1 hour, come out of the stove after the cooling naturally then, obtain the multi-layer cylinder shape honeycomb SnO that the firm load in surface has the nano-noble metal particle 2Catalysis material is to be that carrier, top layer are SnO with tin 2And load has the multi-layer cylinder shape honeycomb SnO of nano-noble metal particle 2Catalysis material, the granularity of the nano-noble metal of tin carrier surface be less than 100nm, the purity purity > of noble metal and metallic tin; 99.95%, the nano-noble metal of load is Pd, and its percentage by weight is 2%.(like Fig. 2)
Embodiment 3: (like Fig. 1)
(1) with the amount of precious metals pt, prepares burden, put into smelting furnace then, adjustment vacuum 1 * 10 with metallic tin by gross weight 3% -4Pa carries out melting under 250 ℃ of temperature conditions, treat that raw material melted the back electromagnetic agitation 2 minutes fully, pours into a mould ingot blank and cooling naturally then;
(2) under the normal temperature condition; With common metal board rolling method; The ingot blank that obtains in the middle of the step (1) in the kamash alloy strip that is rolled into thickness 0.7mm down, is obtained honeycomb through the honeycomb milling method again, obtain multi-layer cylinder shape honeycomb then through curling;
(3) the honeycomb kamash alloy that obtains is put into heat-treatment furnace; Be heated to 220 ℃; The flow of pressing 5L/min then feeds high purity oxygen gas; Alloy is heat-treated and in-situ oxidation was handled 5 hours, come out of the stove after the cooling naturally then, obtain the multi-layer cylinder shape honeycomb SnO that the firm load in surface has the nano-noble metal particle 2Catalysis material is to be that carrier, top layer are SnO with tin 2And load has the multi-layer cylinder shape honeycomb SnO of nano-noble metal particle 2Catalysis material, the granularity of the nano-noble metal of tin carrier surface be less than 100nm, the purity purity > of noble metal and metallic tin; 99.95%, the nano-noble metal Pt of load, its percentage by weight are 3%.(like Fig. 2)
Embodiment 4: (like Fig. 1)
(1) be 99.95% precious metals pd and Pt amount with purity by gross weight 2.5%, with purity be that 99.95% metallic tin is prepared burden, put into smelting furnace then, adjustment vacuum 1 * 10 -5Pa carries out melting under 245 ℃ of temperature conditions, treat that raw material melted the back electromagnetic agitation 1.5 minutes fully, pours into a mould ingot blank and cooling naturally then;
(2) under the normal temperature condition; With common metal board rolling method; The ingot blank that obtains in the middle of the step (1) in the kamash alloy strip that is rolled into thickness 0.6mm down, is obtained honeycomb through the honeycomb milling method again, obtain multi-layer cylinder shape honeycomb then through curling;
(3) the honeycomb kamash alloy that obtains is put into heat-treatment furnace; Be heated to 220 ℃; The flow of pressing 11L/min then feeds high purity oxygen gas; Alloy is heat-treated and in-situ oxidation was handled 4 hours, come out of the stove after the cooling naturally then, obtain the multi-layer cylinder shape honeycomb SnO that the firm load in surface has the nano-noble metal particle 2Catalysis material is to be that carrier, top layer are SnO with tin 2And load has the multi-layer cylinder shape honeycomb SnO of nano-noble metal particle 2Catalysis material, the granularity of the nano-noble metal of tin carrier surface be less than 100nm, the purity purity > of noble metal and metallic tin; The nano-noble metal of 99.95% load is any mixture of Pd and Pt, and its percentage by weight is 2.5%.(like Fig. 2)
Embodiment 5: (like Fig. 1)
(1) with any mixture of precious metals ag, Pd and Pt amount, prepares burden, put into smelting furnace then, adjustment vacuum 1 * 10 with metallic tin by gross weight 1.5% -5Pa carries out melting under 240 ℃ of temperature conditions, treat that raw material melted the back electromagnetic agitation 2.5 minutes fully, pours into a mould ingot blank and cooling naturally then;
(2) under the normal temperature condition; With common metal board rolling method; The ingot blank that obtains in the middle of the step (1) in the kamash alloy strip that is rolled into thickness 0.9mm down, is obtained honeycomb through the honeycomb milling method again, obtain multi-layer cylinder shape honeycomb then through curling;
(3) the honeycomb kamash alloy that obtains is put into heat-treatment furnace; Be heated to 190 ℃; The flow of pressing 12L/min then feeds high purity oxygen gas; Alloy is heat-treated and in-situ oxidation was handled 4 hours, come out of the stove after the cooling naturally then, obtain the multi-layer cylinder shape honeycomb SnO that the firm load in surface has the nano-noble metal particle 2Catalysis material is to be that carrier, top layer are SnO with tin 2And load has the multi-layer cylinder shape honeycomb SnO of nano-noble metal particle 2Catalysis material, the granularity of the nano-noble metal of tin carrier surface be less than 100nm, the purity purity > of noble metal and metallic tin; 99.95%, the nano-noble metal of load is any mixture of Ag, Pd and Pt, and its percentage by weight is 1.5%.(like Fig. 2).

Claims (7)

1. the SnO of a loaded with nano noble metal 2Catalysis material is characterized in that: be to be that carrier, top layer are SnO with tin 2And load has the multi-layer cylinder shape honeycomb SnO of nano-noble metal particle 2Catalysis material.
2. the SnO of loaded with nano noble metal according to claim 1 2Catalysis material is characterized in that: the granularity of the nano-noble metal of tin carrier surface is less than 100nm, the purity purity > of noble metal and metallic tin; 99.95%.
3. the SnO of loaded with nano noble metal according to claim 1 and 2 2Catalysis material is characterized in that: the nano-noble metal of load is one or more any mixture among Ag, Pd, the Pt, and its percentage by weight is 1%~3%.
4. the SnO of a loaded with nano noble metal 2The preparation method of catalysis material; It is characterized in that: the kamash alloy that at first contains 1%~3% noble metal through the melting preparation; Then through plate rolling and honeycomb processing; Acquisition has the kamash alloy material of multi-layer cylinder shape honeycomb, at last this material is put into the heat-treatment furnace with certain flow oxygen atmosphere and heat-treats and the in-situ oxidation reaction, finally obtains the multi-layer cylinder shape honeycomb SnO that load has nano-noble metal 2The catalysis material product.
5. the SnO of loaded with nano noble metal according to claim 4 2The preparation method of catalysis material is characterized in that: concrete preparation process is following:
(1) noble metal and metallic tin are prepared burden, put into smelting furnace then, adjustment vacuum<1 * 10 -3Pa carries out melting under 220 ℃~250 ℃ temperature conditions, treat that raw material melted the back electromagnetic agitation 1~3 minute fully, pours into a mould ingot blank and cooling naturally then;
(2) under the normal temperature condition,, the ingot blank that obtains in the middle of the step (1) is being rolled into thickness < the kamash alloy strip of 1mm, and then be processed into multi-layer cylinder shape honeycomb down with common metal board rolling method;
(3) the honeycomb kamash alloy that obtains is put into heat-treatment furnace; Be heated to 180~220 ℃; Flow by 5~15L/min feeds high purity oxygen gas then; Alloy is heat-treated and in-situ oxidation was handled 1~5 hour, come out of the stove after the cooling naturally then, obtain the multi-layer cylinder shape honeycomb SnO that the firm load in surface has the nano-noble metal particle 2Catalysis material.
6. according to the SnO of claim 4 or 5 described loaded with nano noble metals 2The preparation method of catalysis material is characterized in that: the granularity of the nano-noble metal of tin carrier surface is less than 100nm, the purity purity > of noble metal and metallic tin; 99.95%.
7. according to the SnO of claim 4 or 5 described loaded with nano noble metals 2The preparation method of catalysis material is characterized in that: noble metal is one or more any mixture among Ag, Pd, the Pt, and its percentage by weight is 1%~3% of a gross weight.
CN2011103923429A 2011-12-01 2011-12-01 SnO2 catalytic material loaded with nano precious metals and preparation method thereof Pending CN102489337A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010090051A1 (en) * 2009-02-03 2010-08-12 カルソニックカンセイ株式会社 Metallic catalyst support and process for producing same
CN102029153A (en) * 2010-12-20 2011-04-27 昆明理工大学 Method for preparing nano Ag-loaded honeycomb-structured SnO2 catalyst
CN102068985A (en) * 2010-12-20 2011-05-25 昆明理工大学 Method for preparing honeycomb-structured SnO2 catalyst loaded with nano Pt
CN102078812A (en) * 2010-12-20 2011-06-01 昆明理工大学 Method for preparing SnO2 catalyst loading nanometer Pd and having honeycomb structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010090051A1 (en) * 2009-02-03 2010-08-12 カルソニックカンセイ株式会社 Metallic catalyst support and process for producing same
CN102029153A (en) * 2010-12-20 2011-04-27 昆明理工大学 Method for preparing nano Ag-loaded honeycomb-structured SnO2 catalyst
CN102068985A (en) * 2010-12-20 2011-05-25 昆明理工大学 Method for preparing honeycomb-structured SnO2 catalyst loaded with nano Pt
CN102078812A (en) * 2010-12-20 2011-06-01 昆明理工大学 Method for preparing SnO2 catalyst loading nanometer Pd and having honeycomb structure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张昆华 等: "热挤压工艺对反应合成AgSnO2材料纤维组织的影响", 《贵金属》 *

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Application publication date: 20120613