CN101396661B - High aperture-ratio foam manganese dioxide catalyst material and preparation method and use thereof - Google Patents
High aperture-ratio foam manganese dioxide catalyst material and preparation method and use thereof Download PDFInfo
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- CN101396661B CN101396661B CN2007100129686A CN200710012968A CN101396661B CN 101396661 B CN101396661 B CN 101396661B CN 2007100129686 A CN2007100129686 A CN 2007100129686A CN 200710012968 A CN200710012968 A CN 200710012968A CN 101396661 B CN101396661 B CN 101396661B
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- 239000000463 material Substances 0.000 title claims abstract description 98
- 239000006260 foam Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title abstract description 14
- 239000003054 catalyst Substances 0.000 title description 9
- 239000010949 copper Substances 0.000 claims abstract description 82
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052802 copper Inorganic materials 0.000 claims abstract description 59
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 45
- 238000007747 plating Methods 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 206010070834 Sensitisation Diseases 0.000 claims description 8
- 238000009713 electroplating Methods 0.000 claims description 8
- 230000008313 sensitization Effects 0.000 claims description 8
- 230000001235 sensitizing effect Effects 0.000 claims description 7
- 238000005375 photometry Methods 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 5
- ATWGHWZRHOJITC-UHFFFAOYSA-N [S].C1=CC=NC=C1 Chemical compound [S].C1=CC=NC=C1 ATWGHWZRHOJITC-UHFFFAOYSA-N 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 29
- 239000011572 manganese Substances 0.000 abstract description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052748 manganese Inorganic materials 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000002798 spectrophotometry method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 238000005406 washing Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000013011 aqueous formulation Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Catalysts (AREA)
Abstract
The invention relates to a high porosity cystose MnO2 catalytic material and a preparation and the application thereof, solving problems of catalyzing highly efficiently, prolonging the service life of catalyzed matters, improving the purity of the catalyzed matters, improving the catalytic effect and the like while ozone flows through a carrier. The catalytic material can be applied to an ozone converter of an ultraviolet spectrophotometry ozone analyzer based on a microprocessor and used as a highly efficient catalytic active matter for alkaline manganese batteries. Foam sponge is used as base material. After the conductive treatment, the foam sponge is plated with copper on the surface firstly. When Cu plated film reaches the required thickness, the foam sponge is taken out to be dried. The heat treatment is implemented on the foam sponge in a vacuum furnace or a furnace which is protected with argon. A cystose copper mesh is molded. Then, an Mn plated layer is deposited on the surface of the cystose copper mesh. When the Mn plated layer reaches the required thickness, the mesh is taken out and dried. Under the common oxygen atmosphere of an atmospheric pressure, the oxidation treatment is implemented on the copper mesh to obtain the high porosity cystose MnO2 catalytic material. The porosity of the material is 85-95 percent, and the specific area is regulated in the scope of 12.6m<2>/m<3>-29.6m<2>/m<3> according to practical requirements.
Description
Technical field:
The present invention relates to the manufacturing process technology of porous foam-like material, be specially a kind of porous foam-like MnO
2Catalysis material system and preparation method and application may be used on based on the ozone catalytic material of the ultraviolet photometry ozone analyzer of microprocessor and the high-efficiency catalytic activity thing of alkaline Mn cell.
Background technology:
Owing to artificial reason has been destroyed atmospheric ozone layer, it is no longer safe that sunlight also becomes.International community thinks that ozone layer depletion, climate warming and bio-diversity fall sharply, and has become current three global environment problems the most serious that face.In order to protect the ozone peace to enjoy sunlight, each state has all strengthened the environmental monitoring dynamics and has put into effect some effective improvement measures in recent years.Tenth Five-Year Plan Period, State Environmental Protection Administration's plan will be equipped more than 400 national network monitoring station, more than 350 environmental information center, 100 urban air ground automatic monitoring systems, these all will be finished by instrument and meter, and the market share that wherein relates to just reaches 1,000,000,000 to tens billion of units.With regard to the environmental quality monitoring field, national environment friendly system and all departments, industry, enterprise have built more than 4000 of monitoring stations, and the practitioner is the people more than 60,000, also has several ten thousand environment scientific research institutions.Project comprises: PM
10, SO
2, NO
x, O
3, air pollutants and meteorological parametric measurements such as CO, wind direction, wind speed, temperature, humidity, in the period of following 5, the gross investment demand of environment supervision instrument equipment will reach about 2,000,000,000 yuan, exist extremely vast market development space.And present homemade environment supervision instrument aggregate level is low, lacks the core technology of oneself, and innovation ability is not strong, and the applicability of Yan Fa new and high technology instrument and equipment is relatively poor voluntarily, and product quality is not high, unstable properties, fault rate height.
Chinese invention patent (publication number CN1129672) discloses a kind of manufacture method that is used for the activated manganese dioxide catalyst of battery inserts, and it is to contain MnO
2The natural manganese ore powder of 70-72% and husk catalyst mix batching add MnSO during slurrying
4H
2O increases manganese slurrying, and the disproportionation oxidation reaction adopts gradation to carry out for reinforced 3-4 time, uses H during washing earlier
2SO
4Solution carries out pickling, and neutralization reaction adds NH
4HCO
3, adopting this method to have does not increase equipment, improves work efficiency, product MnO
2Stable content is greater than 75%, and apparent gravity reaches 1.8-2.1 gram/cm
3, discharge performance is good, and intermittent discharge and continuous discharge all meet or exceed the electrolytic manganese dioxide standard.Its weak point is: (1) catalyst is a powdery, and response area is little; (2) chemical purity is not high enough, and catalytic effect is undesirable.
The manganese dioxide-catalyst that uses on ozone analyzer at present is from the product of the U.S. or French import, this product load manganese dioxide on the copper mesh of two-dimensional network structure or stainless (steel) wire makes, gas can and make ozone obtain catalysis in the catalyst of flowing through by netted manganese dioxide free flow, the catalytic efficiency height.Its weak point is: (1) response area is little, once need pack into and could satisfy actual requirement more than 15; (2) manganese dioxide-catalyst film and substrate combinating strength are low, easily cause catalyst layer to peel off in the use, shorten its service life.
Summary of the invention:
The object of the present invention is to provide a kind of porous foam-like MnO that at room temperature can high efficiency catalysis
2Catalysis material and preparation method and application, it is little to solve existing two-dimensional network structure manganese dioxide-catalyst response area, and the sheet number of once packing into is many, and manganese dioxide catalytic membrane and substrate combinating strength are low, easily cause Catalytic Layer to be peeled off in the use, and MnO
2Problems such as catalytic materials purity is low, catalytic effect difference and service life are short.
Technical scheme of the present invention is:
A kind of porous foam-like MnO
2Catalysis material, this catalysis material are to be load MnO on the foam-like copper mesh surface that the plating copper film obtains on the base material at foam sponge
2The porous composite foam shape structure of oxide-film, the thickness of copper film are 15 microns-20 microns, MnO
2The thickness of oxide-film is the 8-12 micron, and the voidage of foam-like catalysis material is 85-95%, and specific area is at 12.6m
2/ m
3-29.6m
2/ m
3Can adjust according to the actual requirements in the scope.
Described porous foam-like MnO
2The preparation method of catalysis material is a base material with the foam sponge, carried metal Cu and MnO
2Oxide-film forms porous foam-like catalysis material, and concrete steps are as follows:
(1) the conduction processing of base material;
(2) plating copper film on base material;
(3) heat treatment, the material that plating is good are at 700-850 ℃ vacuum drying oven or have in the atmosphere of argon shield and heat-treated 1-4 hour, to remove the organic foam composition in the rack, form the foamed metal copper mesh;
(4) plating Mn film on the foamed metal copper mesh surface after the heat treatment;
(5) oxidation processes is carried out oxidation processes with being coated with in the general oxygen atmosphere of material under an atmospheric pressure of Mn film, and oxidizing temperature is 390-410 ℃, oxidization time 1-4 hour.Promptly obtain carried metal Cu and MnO with stove cooling back taking-up
2The porous foam-like catalysis material of oxide-film, the plated film of this porous foam-like catalysis material is by metal Cu and MnO
2Oxide-film is formed.
Described conduction treatment step is as follows:
(1) with the at first sensitization processing of foam sponge material, detailed process is handled in sensitization and process parameters range is: sensitizing solution is formulated by the hydrochloric acid 40-50ml/L and the distilled water surplus of stannous chloride 10-30g/L, mass concentration 37%, at room temperature sample is put into the sensitizing solution immersion and is got final product in 3-5 minute;
(2) immerse again after taking-up is washed and make matrix surface form active metal level in the solution that contains oxidant, the solution composition of oxidant is: silver nitrate 1.5-2.0g/L, ammoniacal liquor adds to the transparent and distilled water surplus of solution, at room temperature sample is put into the solution that contains above-mentioned oxidant and is soaked 10-20 minute.When beginning to add ammoniacal liquor, solution is because of the generation of AgOH and be decomposed into Ag
2O precipitates and is the muddy shape of brown, with the increase of ammoniacal liquor addition, and Ag
2O is dissolved, generate the silver ammonia complex of colourless solubility and become transparent gradually.Concrete reaction is as follows:
(Ag
2O+4NH
3+H
2O＝2[Ag(NH
3)
2]OH)。
(3) get chemical copper plating solution thin up to its weight then and account for 10-30%, material after the above-mentioned processing is soaked 10-30 after second therein, at room temperature directly into soaking 5-10 minute in the chemical copper plating solution, copper is got in plating makes the foam sponge material obtain electric conductivity without the water cleaning; Described chemical copper plating solution composition is: copper sulphate 15-22g/L, ATMP 40-60g/L, HEDP 5-10g/L, the formalin 10-30ml/L of mass concentration 37%, NaOH 45-65g/L, 2-sulfhydryl benzene a pair of horses going side by side sulphur pyridine 2-5ml/L and distilled water surplus.
Described plating copper film adopts conventional electro-plating method to carry out electro-coppering, perhaps adopts conventional electroless copper plating method to carry out plated film, and the Mn plated film adopts conventional galvanoplastic plated film.
Porous foam-like MnO of the present invention
2Catalysis material may be used on based on the ozone catalytic material of the ultraviolet photometry ozone analyzer of microprocessor and the high-efficiency catalytic activity thing of alkaline Mn cell.
Advantage of the present invention and beneficial effect are:
1, the present invention utilizes good plasticity of metal Cu and electric conductivity; it is carried on the foam sponge material; form the foam-like framework material of metal Cu; at high-temperature vacuum or have under the hot conditions of protective atmosphere and make the foam sponge material breakdown; thereby become and have resistant to elevated temperatures foamed metal copper mesh; on the foamed metal copper mesh surface after the heat treatment, deposit the Mn film then and carry out oxidation processes, thereby obtain carried metal Cu and MnO
2The porous foam-like catalysis material of oxide-film.
2, the present invention adopts Cu as framework material, then with MnO through serious analysis and checking repeatedly
2Oxide-film is compound on the foam-like copper mesh surface, and the porous foam-like catalysis material of acquisition may be used on not only can increasing substantially response area, but also can significantly improving MnO on the ultraviolet photometry ozone analyzer based on microprocessor
2The bond strength of oxide-film and Cu film, thus its service life prolonged; Be applied on the alkaline Mn cell, can improve catalytic materials purity, improve its catalytic effect and charge-discharge performance.
3, porous foam-like MnO of the present invention
2The catalysis material preparation method is simple, cost is lower.The present invention is base material with the foam sponge, carried metal Cu and MnO
2Oxide-film and obtain porous foam-like MnO
2Catalysis material; base material through the conductionization processing; electroplate Cu coating; when plated copper film reaches needed thickness; at vacuum drying oven or have in the stove of argon shield and heat-treat; form porous foamed metal copper mesh, carrying out oxidation processes, the carried metal Cu and the MnO that can obtain making in plating Mn film and the general oxygen atmosphere under an atmospheric pressure on the heat treated foamed metal copper mesh surface at last
2Oxide-film porous foam-like catalysis material.This foam-like MnO
2The plated film of catalysis material is by metallic copper and MnO
2Oxide-film is formed, final foam-like MnO
2Catalysis material only has metallic framework and MnO
2Oxide-film exists, and has made it fire prevention and resistance and high temperature resistance property.
4, adopt the porous foam-like catalysis material of the present invention's preparation, have the characteristics of porous, its porosity can reach 85-95%, and specific area is at 12.6m
2/ m
3-29.6m
2/ m
3Adjust according to the actual requirements in the scope, the advantage of this structure mainly contains: (1) specific area is big, can improve reaction efficiency dramatically; (2) aperture relatively evenly and mutually connects, and through hole is not easy to be stopped up by the field trash in air or the liquid; (3) light weight is when giving catalytic performance and the weight of equipment increase is very little; (4) excellent in durability through using the rear surface plated film not come off after a while, still can continue to use and keep good catalytic effect.
Description of drawings:
Fig. 1 is porous foam-like MnO
2The photomacrograph of catalysis material.
The specific embodiment:
Embodiment 1
With at first sensitization processing of foam sponge material (aperture is about 550 microns), detailed process is handled in sensitization and process parameters range is: at room temperature sample is put into sensitizing solution (stannous chloride 20g/L, the hydrochloric acid 40ml/L and the distilled water surplus of mass concentration 37%) in, soak and immerse solution (the silver nitrate 1.7g/L that at room temperature contains oxidant after 3 minutes after the taking-up washing again, ammoniacal liquor adds to the transparent and distilled water surplus of solution, the ammoniacal liquor addition is 10ml in the present embodiment) the middle metal level that made matrix surface form activity in 10 minutes that soaks, get 200ml chemical copper plating solution thin up then to 1L, material after the above-mentioned processing is soaked (bringing in the chemical plating fluid to prevent the activating solution that remains in specimen surface) after 20 seconds therein, clean at room temperature directly into soaking 5 minutes in the chemical copper plating solution without water, copper is got in plating makes the foam sponge material obtain electric conductivity, described chemical copper plating solution composition is: copper sulphate 22g/L, ATMP 50g/L, HEDP 6g/L, the formalin 20ml/L of mass concentration 37%, NaOH 50g/L, 2-sulfhydryl benzene a pair of horses going side by side sulphur pyridine 3ml/L and distilled water surplus.
Under composition proportion as shown in table 1 and technological parameter condition, foam sponge material after the conductive processing is carried out electroplating copper film, when the thickness of plated material is approximately 15 μ m, from electroplating solution, take out, dry after the washing, insert that (vacuum is about 10Pa) kept 2 hours in 800 ℃ the vacuum drying oven, take out after reducing to room temperature, remove the foam sponge in the rack, form the foamed metal copper mesh.
Table 1 is electroplated Cu aqueous formulation and technological parameter
| Component | Content (g/L) | Process conditions | Parameter |
| Cupric pyrophosphate (Cu 2P 2O 7) | 55-70 | The pH value | 8.3-8.8 |
| Potassium pyrophosphate (K 4P 2O 7.3H 2O) | 300-350 | Temperature/℃ | 40-50 |
| Ammonium citrate [(NH 4)HC 6H 5O 7] | 20-25 | Current density A.dm -2 | 1-1.5 |
Thereafter, under composition proportion as shown in table 2 and technological parameter condition, 8 microns Mn film is deposited on the foamed metal copper mesh surface for preparing, carry out oxidation processes with being coated with in general oxygen (tonnage oxygen) atmosphere of material under an atmospheric pressure of Mn film, oxidizing temperature is 390 ℃, oxidization time 4 hours.Promptly obtain carried metal Cu and MnO with stove cooling back taking-up
2The porous foam-like catalysis material of oxide-film, the plated film of this porous foam-like catalysis material is by metal Cu and MnO
2Oxide-film is formed, and the foamed porosity of present embodiment is 95%, and specific area is about 29.6m
2/ m
3
Table 2 is electroplated Mn aqueous formulation and technological parameter
| Component | Content (g/L) | Process conditions | Parameter |
| Manganese sulfate (MnSO 4·2H 2O) | 95-105 | The pH value | 4-5.5 |
| Ammonium sulfate [(NH 4) 2SO 4] | 70-80 | Temperature/℃ | 25 |
| Ammonium thiocyanate (NH 4CNS) | 55-65 | Current density A.dm -2 | 10-25 |
As shown in Figure 1, porous foam-like MnO
2The photomacrograph of catalysis material, the micropore of foam-like catalysis material relatively evenly and mutually connects as seen from the figure.
The present invention carries out the ozone catalytic performance test to the material for preparing, and concrete method of testing is as follows:
Testing equipment: US-built 1008-AH type ozone analyzer; MnO with the diameter millimeter
26 every group of catalysis sheets are put into equipment ozone catalytic converter, are connected to 1008AH type ultraviolet photometry O
3In the analyzer gas circuit, and the model machine that this instrument is tested in contrast.With 1008PC type ultraviolet photometry O
3Analyzer is the test standard instrument in contrast, and the gas circuit condition identical with model machine is provided.Standard machine and model machine are adjusted to steady operational status, feed zero controlled atmosphere to zero point, feed 800ppbO
3Gas, the O of reference standard machine
3The difference of value and model machine is as performance assessment criteria, and difference is qualified greater than 780ppb after 2 hours, and test result is listed in table 3.
Table 3 foam-like MnO
2The ozone catalytic The performance test results of catalysis material
| Time (my god) | 1 | 3 | 5 | 7 | 9 | 11 | 13 |
| Standard specimen difference (ppb) | 785 | 782 | 767 | 764 | 756 | 743 | 731 |
| Catalytic rate (%) | 98.125 | 97.75 | 95.875 | 95.5 | 94.5 | 92.875 | 91.375 |
By table 3 as can be seen, porous foam-like MnO
2Catalysis material at room temperature has superior catalytic effect to ozone, still can satisfy the criterion of acceptability requirement after 3 days, and its catalytic rate is still up to 91.375% after 13 days.
Embodiment 2
Difference from Example 1 is:
With at first sensitization processing of foam sponge material (aperture is about 550 microns), at room temperature sample is put into sensitizing solution (stannous chloride 10g/L, the hydrochloric acid 50ml/L and the distilled water surplus of mass concentration 37%) in, soak and immerse solution (the silver nitrate 2.0g/L that at room temperature contains oxidant after 5 minutes after the taking-up washing again, ammoniacal liquor adds to the transparent and distilled water surplus of solution, the ammoniacal liquor addition is 12ml in the present embodiment) the middle metal level that made matrix surface form activity in 15 minutes that soaks, get 200ml chemical copper plating solution thin up then to 1L, after short time soaks 30 seconds therein with the material after the above-mentioned processing, clean at room temperature directly into soaking 8 minutes in the chemical copper plating solution without water, copper is got in plating makes the foam sponge material obtain electric conductivity, described chemical copper plating solution composition is: copper sulphate 15g/L, ATMP 40g/L, HEDP 5g/L, the formalin 30ml/L of mass concentration 37%, NaOH 45g/L, 2-sulfhydryl benzene a pair of horses going side by side sulphur pyridine 2ml/L and distilled water surplus.
Under composition proportion as shown in table 1 and technological parameter condition, foam sponge material after the conductive processing is carried out electroplating copper film, when the thickness of plated material is approximately 20 μ m, from electroplating solution, take out, dry after the washing, insert in 700 ℃ the argon gas atmosphere and kept 4 hours, take out after reducing to room temperature, remove the fiber composition in the rack, form the foamed metal copper mesh.Thereafter, under composition proportion as shown in table 2 and technological parameter condition, 12 microns Mn film is deposited on the foamed metal copper mesh surface for preparing, and carries out oxidation processes with being coated with in the general oxygen atmosphere of material under an atmospheric pressure of Mn film, oxidizing temperature is 410 ℃, oxidization time 1 hour.Promptly obtain carried metal Cu and MnO with stove cooling back taking-up
2The porous foam-like catalysis material of oxide-film, the plated film of this porous foam-like catalysis material is by metal Cu and MnO
2Film is formed in the oxidation, and the foamed porosity of present embodiment is 85%, and specific area is about 12.6m
2/ m
3
Present embodiment carries out the ozone catalytic performance test to the material for preparing, and the result shows porous foam-like MnO
2Catalysis material at room temperature has superior catalytic effect to ozone.
Embodiment 3
Difference from Example 1 is:
With at first sensitization processing of foam sponge material (aperture is about 550 microns), at room temperature sample is put into sensitizing solution (stannous chloride 30g/L, the hydrochloric acid 40ml/L and the distilled water surplus of mass concentration 37%) in, soak to immerse again after the taking-up washing after 4 minutes and at room temperature contain oxidant (silver nitrate 1.5g/L, ammoniacal liquor adds to the transparent and distilled water surplus of solution, the ammoniacal liquor addition is 8ml in the present embodiment) solution in soak and to make matrix surface form active metal level in 20 minutes, get 200ml chemical copper plating solution thin up then to 1L, after material after the above-mentioned processing soaked 10 seconds therein, clean at room temperature directly into soaking 10 minutes in the chemical copper plating solution without water, copper is got in plating makes the foam sponge material obtain electric conductivity, described chemical copper plating solution composition is: copper sulphate 20g/L, ATMP 60g/L, HEDP 10g/L, the formalin 10ml/L of mass concentration 37%, NaOH 65g/L, 2-sulfhydryl benzene a pair of horses going side by side sulphur pyridine 5ml/L and distilled water surplus.
Under composition proportion as shown in table 1 and technological parameter condition, foam sponge material after the conductive processing is carried out electroplating copper film, when the thickness of plated material is approximately 10 μ m, from electroplating solution, take out, dry after the washing, insert in 850 ℃ the argon gas atmosphere and kept 1 hour, take out after reducing to room temperature, remove the fiber composition in the rack, form the foamed metal copper mesh.Thereafter, under composition proportion as shown in table 2 and technological parameter condition, 10 microns Mn film is deposited on the foamed metal copper mesh surface for preparing, and carries out oxidation processes with being coated with in the general oxygen atmosphere of material under an atmospheric pressure of Mn film, oxidizing temperature is 400 ℃, oxidization time 2 hours.Promptly obtain carried metal Cu and MnO with stove cooling back taking-up
2The porous foam-like catalysis material of oxide-film, the plated film of this porous foam-like catalysis material is by metal Cu and MnO
2Oxide-film is formed, and the foamed porosity of present embodiment is 90%, and specific area is about 20.8m
2/ m
3
Present embodiment carries out the ozone catalytic performance test to the material for preparing, and the result shows porous foam-like MnO
2Catalysis material at room temperature has superior catalytic effect to ozone.
Claims (6)
1. porous foam-like MnO
2Catalysis material is characterized in that: this catalysis material is to be load MnO on the foam-like copper mesh surface that the plating copper film obtains on the base material at foam sponge
2The porous composite foam shape structure of oxide-film, the thickness of copper film are 15 microns-20 microns, MnO
2The thickness of oxide-film is the 8-12 micron, and the porosity of foam-like catalysis material is 85-95%, and specific area is at 12.6m
2/ m
3-29.6m
2/ m
3Can adjust according to the actual requirements in the scope.
2. according to the described porous foam-like of claim 1 MnO
2The preparation method of catalysis material is characterized in that: be base material with the foam sponge, carried metal Cu at first forms the foamed metal copper mesh, and then at foam-like copper mesh area load MnO
2Coating, concrete steps are as follows:
(1) the conduction processing of base material;
(2) plating copper film on base material;
(3) heat treatment, the material that plating is good are at 700-850 ℃ vacuum drying oven or have in the atmosphere of argon shield and heat-treated 1-4 hour, to remove the organic foam composition in the rack, form the foam-like copper mesh;
(4) surface of the foam-like copper mesh after heat treatment plating Mn film;
(5) oxidation processes is carried out oxidation processes in the general oxygen atmosphere under an atmospheric pressure and is obtained loaded Cu and MnO
2Porous foam-like MnO
2Catalysis material, the plated film of this catalysis material is by compound MnO on the foam-like Cu net surface
2Oxidation film is formed.
3. according to the described porous foam-like of claim 2 MnO
2The preparation method of catalysis material is characterized in that described conduction treatment step is as follows:
(1) with the at first sensitization processing of foam sponge material, detailed process is handled in sensitization and process parameters range is: sensitizing solution is formulated by the hydrochloric acid 40-50ml/L and the distilled water surplus of stannous chloride 10-30g/L, mass concentration 37%, at room temperature sample is put into the sensitizing solution immersion and is got final product in 3-5 minute;
(2) immerse again after taking-up is washed and make matrix surface form active metal level in the solution that contains oxidant, the solution composition of oxidant is: silver nitrate 1.5-2.0g/L, ammoniacal liquor adds to the transparent and distilled water surplus of solution, at room temperature sample is put into the solution that contains above-mentioned oxidant and is soaked 10-20 minute;
(3) getting the chemical copper plating solution adding distil water then is diluted to its weight and accounts for 10-30%, material after the above-mentioned processing is soaked 10-30 after second therein, at room temperature directly into soaking 5-10 minute in the chemical copper plating solution, copper is got in plating makes the foam sponge material obtain electric conductivity without the water cleaning; Described chemical copper plating solution composition is: copper sulphate 15-22g/L, ATMP 40-60g/L, HEDP 5-10g/L, the formalin 10-30ml/L of mass concentration 37%, NaOH 45-65g/L, 2-sulfhydryl benzene a pair of horses going side by side sulphur pyridine 2-5ml/L and distilled water surplus.
4. according to the described porous foam-like of claim 2 MnO
2The preparation method of catalysis material is characterized in that: oxidation temperature is 390-410 ℃, and the time is 1-4 hour.
5. according to the described porous foam-like of claim 2 MnO
2The preparation method of catalysis material is characterized in that: described plating copper film adopts electro-plating method to carry out electro-coppering, perhaps adopts electroless copper plating method to carry out plated film, and the Mn plated film adopts the galvanoplastic plated film.
6. according to the described porous foam-like of claim 1 MnO
2The application of catalysis material is characterized in that: this porous foam-like MnO
2Catalysis material is applied to the ultraviolet photometry ozone analyzer based on microprocessor, perhaps is applied to alkaline Mn cell.
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| US9336958B2 (en) * | 2010-12-21 | 2016-05-10 | Tohuku University | Nanoporous ceramic composite metal |
| US9809468B1 (en) * | 2017-08-18 | 2017-11-07 | Ashli Iyer Jain | Water disinfection system using functional mixture, copper foam catalyst, continuous flow, UV radiation, optical pipe |
| CN108017151B (en) * | 2017-12-18 | 2020-05-08 | 西南石油大学 | Method for enhancing SBR excess sludge reduction through multistage increase-decompression and equipment for sludge reduction |
| CN109306502B (en) * | 2018-12-10 | 2020-11-24 | 桂林理工大学 | Manganese electrolyte additive and using method thereof |
| CN113355647B (en) * | 2021-06-07 | 2023-04-11 | 江苏中天科技股份有限公司 | Porous metal, and method and apparatus for producing same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109922A (en) * | 1995-03-11 | 1995-10-11 | 吉林大学 | Process for preparing spongy foam nickel |
| CN2263828Y (en) * | 1996-06-27 | 1997-10-01 | 郓城县鲁峰贸易有限公司 | Flow concentration pull net foam nickel (copper) |
| US20020061437A1 (en) * | 2000-11-17 | 2002-05-23 | Hong Gan | Double current collector cathode design using the same active material in varying formulations for alkali metal or ion electrochemical cells |
| CN1797826A (en) * | 2004-12-30 | 2006-07-05 | 比亚迪股份有限公司 | Foam nickel, and method for fabricating the foam nickel, and battery of using the foam nickel |
-
2007
- 2007-09-26 CN CN2007100129686A patent/CN101396661B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109922A (en) * | 1995-03-11 | 1995-10-11 | 吉林大学 | Process for preparing spongy foam nickel |
| CN2263828Y (en) * | 1996-06-27 | 1997-10-01 | 郓城县鲁峰贸易有限公司 | Flow concentration pull net foam nickel (copper) |
| US20020061437A1 (en) * | 2000-11-17 | 2002-05-23 | Hong Gan | Double current collector cathode design using the same active material in varying formulations for alkali metal or ion electrochemical cells |
| CN1797826A (en) * | 2004-12-30 | 2006-07-05 | 比亚迪股份有限公司 | Foam nickel, and method for fabricating the foam nickel, and battery of using the foam nickel |
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