CN103623842B - Granular supported nano gold catalyst for closed CO2 laser device - Google Patents
Granular supported nano gold catalyst for closed CO2 laser device Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 239000010931 gold Substances 0.000 title claims abstract description 69
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 52
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 238000005470 impregnation Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 14
- 238000009938 salting Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 239000011943 nanocatalyst Substances 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 8
- 241000370738 Chlorion Species 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 claims 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims 1
- 238000011056 performance test Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 230000008859 change Effects 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 12
- 230000004044 response Effects 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- B01J23/48—Silver or gold
- B01J23/52—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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
- B01J35/45—Nanoparticles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/02—Constructional details
- H01S3/03—Constructional details of gas laser discharge tubes
- H01S3/036—Means for obtaining or maintaining the desired gas pressure within the tube, e.g. by gettering, replenishing; Means for circulating the gas, e.g. for equalising the pressure within the tube
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/22—Gases
- H01S3/223—Gases the active gas being polyatomic, i.e. containing two or more atoms
- H01S3/2232—Carbon dioxide (CO2) or monoxide [CO]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a granular composite-oxide-modified alumina-supported nano gold catalyst for a closed CO2 laser device. An isometric impregnation method is utilized to prepare a series of alumina-supported gold catalysts modified by different metal oxide compositions in different proportions. The CO2 laser device is utilized to simulate an atmosphere to evaluate the catalytic activity and stability of the catalyst. When a better catalyst is packaged in a gas storage tube of the radio-frequency-excited CO2 laser device, the experimental result indicates that the catalyst can stabilize the output power of the laser device for a long time, thereby prolonging the service life of the closed CO2 laser device.
Description
Technical field
The present invention relates to for closed CO
2the particulate supported type nano catalyst of laser instrument.
Background technology
Since pneumatic CO in 1966
2since laser instrument is born, the laser technique of countries in the world has just had tremendous development.CO
2laser instrument is a class gas laser of current most study, and it is widely applied to the fields such as communication, materials processing, medical treatment, military affairs.It is large with power output, operating efficiency is high and famous, almost accounts for 45% of global laser market.
CO
2in laser instrument, main operation material by CO, nitrogen, helium three kinds of gas compositions.Wherein CO is the gas producing laser emission, and nitrogen and helium are complementary gas.The chief component of its machine comprises laser tube, optical resonator, power supply and pumping, and wherein laser tube is the part of most critical in laser instrument, is usually made up of discharge tube, water cooling tube, cylinder three part.
Following many chemical reactions can be there is in laser works process:
（1） CO
2→CO+ O；（2）N
2+ O→N
2O；（3）N
2+ 2O→2NO；（4）2O→O
2
Visible, lasing while, intrasystem CO
2concentration can reduce gradually, CO
2minimizing not only reduce laser output power, and affect the working life of laser instrument; CO has certain influence to impedance discharge and laser gain; Derivative NO
x(NO, N
2o etc.) also there is larger impact to glow discharge and power output.When these pernicious gases run up to a certain degree, laser instrument is cisco unity malfunction just.For addressing this problem, two kinds of modes can be taked: (1) periodic replacement gas; (2) catalysis compound CO
2, by CO
2decompose CO and the O produced
2catalysis is combined into CO again
2.Because He gas price lattice are more expensive, and substitution gas time consumption and energy consumption, make cost increase, be unfavorable for laser instrument extensive use industrially.Catalysis compound CO
2just become the effective means addressed this problem.This CO no longer needing regularly inflation
2laser instrument is called closed CO
2laser instrument.
Pt/SnO
2,pt/MnO
2, Pd/SnO
2,rh/SnO
2, Ru/MnO
2cO was applied to once Deng catalyst series
2laser instrument, (S. D. Gardener, G. B. Hoflund; " Alternative catalysts for low temperature CO oxidation, NASA conference publication 3076, October, 1989,123-135).What nearly more than ten years laboratory research was more is Au series catalysts (Hao Zhengping, " research of load type gold catalyst ", thesis for the doctorate, in June, 1996).
Laser works gas catalysis composite purification device can be divided into catalysis composite purification two kinds in laser chamber outer circulation and chamber.In chamber, the advantage of catalysis complex method is obvious, and namely equipment is simple, there is not the problems such as the additional mechanism providing additional operation of chamber outer circulation gas and leakage thereof, but higher to the requirement of catalyst, catalyst will under room temperature or operating temperature, high concentration CO
2, have good activity under low concentration CO and stoichiometric oxygen condition, and do not produce the pollution of solid particle.Catalyst also needs to have good heat endurance, mechanical stability and minimum air resistance.Most conventional CO oxidation catalyst, as: the palladium of support type, platinum, ruthenium, rhodium, the catalyst such as copper all can not meet above-mentioned requirements [J. A. Macken, IEEE J. Quant Electronic 25 (7) (1989) 1695; C. Willis, J. G. Purdon, J. Appl. Phys. 50 (4) (1979) 2539; Wang Wennan, Wang Shunhua, Cheng Zuhai, Chen Tao's applicable technology market, 8 (1996) 13].
From the Masatake Haruta discovery eighties in last century transition metal oxide Fe
2o
3, NiO, Co
3o
4upper loaded with nano gold particle can at low temperatures by CO complete oxidation [M. Haruta, N. Yamada, T. Kobayashi, S. Iijima, J. Catal., 115 (2) (1989) 301].Au catalyst is at CO
2trial on laser instrument also launches thereupon, particulate supported type nano catalyst (Zhengping. Hao, Lidun. An, Hongli. Wang, Chin. Chem. Lett., 6 (5) (1995) 447) and CO
2the coaxial electrode of laser instrument and the gold-plated film of laser tube inwall [A. K Tripthin, India J. Technol 30 (2) (1992) 107; I. Borisovitch, et.al, WO 00/21167; Dong little Gang and Qu Qianhua, vacuum science and technology, 21 (2) (2001) 150; Xu Haijun, carbon dioxide laser gas catalysis technique, CN101232144A] all in research and development.Compare and encapsulate particulate supported type nano catalyst in laser tube, extend CO by golden membrane coat
2the cost in service life of laser instrument is high, and physics manufacturing process set direction is poor, and preparation condition is harsh.
Oxidation of Carbon Monoxide particulate supported type nano catalyst that this laboratory development goes out [An Lidun, Qi Shixue, Zou Xuhua, Chinese invention patent, ZL 00 1 22829.3, international monopoly, publication number WO2006007774(A1) 01/25/2006.An Lidun, Qi Shixue, rope palm bosom, Weng Yonggen, Zou Xuhua, Chinese invention patent, ZL 03 1 38786.1.An Lidun; Qi Shixue; Zou Xuhua, Chinese invention patent ZL 2,004 1 0024509.6,2008] catalytic stability can be in leading in the world, being used successfully in Miniature mine protection CO filter type self-rescuer, is the Au catalyst that domestic the first drops into industrial applications.The preliminary experimental results that this catalyst loading carbon dioxide laser is good shows the great potential that load type gold catalyst is applied in this field.This laboratory was also once studied LaFeOx and was modified Al
2o
3gained complex carrier carries Au catalyst Au/LaFeOx/Al
2o
3through O
3the impact (woods clear spring An Lidun etc., " catalysis journal " 2008 year 6 phases) of process on catalyst heat endurance in CO oxidation reaction.
Summary of the invention
The present invention is on the basis of R&D work in the past, according to CO
2the structure of laser instrument, condition of work and gas compositing characteristic, provide a kind of for closed CO
2the low carrying capacity of stable graininess of laser instrument, the load type nano gold catalyst of high dispersive, by select different composite oxide modifying Al
2o
3carrier and reasonably preparation method, realize CO
2cO and O produced in laser works
2situ catalytic is combined into CO again
2, thus do not needing supplementary CO
2when unstripped gas, effective stable laser power output, and extend its service life.
The present invention is by the following technical solutions:
For a particulate supported type nano catalyst for closed CO2 laser instrument, it is characterized in that, active component is Au, and carrier is composite oxide modified aluminium oxide MFeLaOx/ Al2O3, and wherein M is blank, or Cu, or Zn, or Mn, or Ni.
It is 0.2 ~ 3% that gold element accounts for catalyst gross mass percentage, and in composite oxide modified aluminium oxide, FeLaOx is the atomic ratio 0 ~ 5 of 1 ~ 5%, M and Fe of AL2O3 weight.
Wherein the precursor of gold is HAuCl4H2O or AuCl3 or metallic gold; The precursor compound of described M component and Fe, La is its corresponding nitrate or hydrochloride or acetate respectively.
The preparation method of described load type nano gold catalyst, is characterized in that, adopts equi-volume impregnating preparation.
Its preparation technology is:
(1) Al2O3 carrier 1.94 ~ 1.96 weight portion is taken through 600 ~ 700 DEG C of roasting 4h, for subsequent use; Take 0.0356 ~ 0.1782 mass parts La (NO3) 36H2O, 0.0326 ~ 0.1638 mass parts Fe (NO3) 39H2O, 0 ~ 0.6112 mass parts M salt, be dissolved in 2.8 mass parts deionized waters, form M-Fe-La mixing salt solution; With the baked Al2O31.5h of described M-Fe-La salting liquid incipient impregnation, products therefrom through 80 DEG C ~ 120 DEG C drying 4 ~ 8h, then through 600 ~ 950 DEG C of roasting 4h, obtains MFeLaOx/Al2O3 complex carrier;
(2) get HAuCl4H2O and add the solution that deionized water makes 1.4 ~ 21.6gAu/L, use aqueous slkali to regulate above-mentioned pH value of solution to 6 ~ 10, obtain golden precursor solution; Use above-mentioned golden precursor solution incipient impregnation step (1) gained MFeLaOx/Al2O3 complex carrier 1.5h, products therefrom soaks 24h through ammoniacal liquor, be washed till without chlorion by deionized water again, then at 50 ~ 100 DEG C, 5 ~ 12h is dried, again through 300 DEG C ~ 450 DEG C hydrogen reducing 1h, obtained Au/MFLA finished catalyst;
In step (2), aqueous slkali used is the solution of Na2CO3 or NaOH or K2CO3 or KOH.
Its preparation technology is specially further:
(1) Al2O3 carrier 1.94 weight portion is taken through 650 DEG C of roasting 4h, for subsequent use; Take 0.0525 ~ 0.0712 mass parts La (NO3) 36H2O, 0.0482g ~ 0.0701 mass parts Fe (NO3) 39H2O, 0 ~ 0.0367 mass parts M salt is dissolved in 2.8 mass parts deionized waters, forms M-Fe-La mixing salt solution; With the baked Al2O31.5h of described M-Fe-La salting liquid incipient impregnation, products therefrom through 80 DEG C ~ 120 DEG C drying 4 ~ 8h, then through 850 DEG C of roasting 4h, obtains MFeLaOx/Al2O3 complex carrier;
(2) get HAuCl4H2O and add the solution that deionized water makes 7.14gAu/L, use aqueous slkali to regulate above-mentioned pH value of solution to 9 ~ 10, obtain golden precursor solution; Use above-mentioned golden precursor solution incipient impregnation step (1) gained MFeLaOx/Al2O3 complex carrier 1.5h, products therefrom soaks 24h through ammoniacal liquor, then is washed till without chlorion by deionized water, then at 60 DEG C, dries 12h, again through 300 DEG C of hydrogen reducing 1h, obtained Au/MFLA finished catalyst;
In step (2), aqueous slkali used is KOH solution.
The application process of described load type nano gold catalyst, is characterized in that, is contained in by 0.3 ~ 2.0g catalyst sealing in closed rf-excited co2 laser, in order to stable laser power output, and extends the service life of laser instrument.
The application process of described load type nano gold catalyst, is characterized in that, under the oxygen-enriched atmosphere condition containing 1%CO, the minimum full conversion temperature that described catalyst CO is oxidized is-20 DEG C ~ 100 DEG C.
The application process of described load type nano gold catalyst, it is characterized in that, be CO:O2:CO2:He:N2:H2O=1.0:0.5:60:10:28 in atmosphere: trace or 1%CO, 0.5%O2,60%CO2,0.5% steam, Balance Air is under the condition of inert gas N2, and the temperature that described catalyst CO is oxidized to CO2 is 30 ~ 400 DEG C.
beneficial effect of the present invention:
1, particulate supported type nano catalyst of the present invention is applied to closed CO
2in laser instrument, achieve the CO in high concentration
2atmosphere in efficient cryogenic catalytic oxidation to CO.
2, particulate supported type nano catalyst of the present invention is encapsulated in closed RF excited CO
2in laser instrument, the power output long-time stable of laser instrument can be made constant, thus extend the closed CO of radio frequency
2the Acceptable life of laser instrument.
Detailed description of the invention
Technical scheme of the present invention and beneficial effect is further illustrated below in conjunction with specific embodiment.
embodiment 1
Take Al
2o
3original vector 1.94g is through 650 DEG C of roasting 4h, for subsequent use; Take 0.0712g La (NO
3)
36H
2o, 0.0655g Fe (NO
3)
39H
2o is dissolved in 2.8ml deionized water, forms Fe-La salting liquid; With the above-mentioned Al through roasting of this Fe-La salting liquid incipient impregnation
2o
31.5h, then by products therefrom 80 DEG C of dry 8h, 850 DEG C of roasting 4h, obtain FeLaO
x/ Al
2o
3(being called for short FLA) complex carrier.
Take HAuCl
4h
2o adds deionized water preparation 7.14g
authe solution of/L, regulates described pH value of solution to 9 ~ 10 with KOH, obtains golden precursor solution; With this golden precursor solution incipient impregnation above-mentioned FLA complex carrier 1.5h, products therefrom is soaked 24h through ammoniacal liquor, then through deionized water washing removing chlorion, then at 60 DEG C, dry 12h, then through 300 DEG C of hydrogen reducing 1h, i.e. obtained 1%Au/FLA catalyst.
Consist of at unstripped gas: CO:1%; O
2: 21%; N
2: 78%(percent by volume), gas volume air speed is 6.0 × 10
4h
-1when, CO transforms completely, and (remaining CO concentration is lower than chromatographic detection limit 50ppm) is CO
2permission minimum response temperature (being called " minimum full conversion temperature ", as follows) be-15 DEG C.
embodiment 2
Adopt Au/FLA catalyst prepared by specific embodiment 1, adopt simulation CO
2gas composition (1%CO, 0.5%O of laser instrument
2, 60%CO
2, 0.5% steam, Balance Air is inert gas N
2), the catalyst at every turn getting fresh preparation is the catalytic capability that is oxidized CO of detecting catalyst at different temperature.Result is as table 1, and Au/FLA catalyst shows reasonable catalytic activity, and within the time period investigated at 120 DEG C the stability of catalysts better.
The catalytic activity of table 1 1%Au/FLA catalyst in analog laser atmosphere at differential responses temperature (conversion rate R: CO mol (g
au)
-1h
-1) with the change in reaction time (h)
embodiment 3
Take 0.0610g La (NO
3)
36H
2o, 0.0561g Fe (NO
3)
39H
2o, 0.0210g zinc nitrate is dissolved in 2.8ml deionized water and forms Zn-Fe-La salting liquid, takes the preparation procedure of embodiment 1, obtains ZnFeLaO
x/ Al
2o
3(ZFLA) carrier.According to the step in embodiment 1, only reduction temperature is adjusted to 450 DEG C, i.e. obtained 1%Au/ZFLA catalyst.
Adopt the appreciation condition of embodiment 1, CO is converted into CO completely
2minimum full conversion temperature be-10 DEG C.
Adopt the appreciation condition of embodiment 2,1%Au/ZFLA catalyst also shows reasonable catalytic performance in different temperatures section, and is also that stability compares better 120 DEG C time.Exemplary statistical data is as shown in table 2.
The catalytic activity of table 2 1%Au/ZFLA catalyst in analog laser atmosphere at differential responses temperature (R: CO mol (g
au)
-1h
-1) with the change in reaction time (h)
| Time (h) temperature (DEG C) | 0.5 | 1.5 | 2.5 | 3.5 | 4.5 | 5.5 | 6.5 | 7.5 | 8.5 | 9.5 | 10.5 |
| 30 | 0.58 | 0.48 | 0.48 | 0.42 | 0.50 | 0.38 | 0.35 | 0.32 | 0.29 | － | － |
| 70 | 0.95 | 0.92 | 0.77 | 0.73 | 0.70 | 0.63 | 0.54 | 0.48 | 0.42 | 0.39 | － |
| 120 | 2.14 | 2.15 | 2.07 | 1.92 | 2.04 | 1.84 | 1.96 | 1.90 | 1.85 | 1.76 | 1.69 |
| 200 | 3.82 | 3.83 | 3.49 | 3.39 | 2.91 | 2.80 | 2.70 | 2.81 | 2.63 | 2.20 | 2.18 |
| 400 | 8.82 | 7.79 | 7.38 | 6.92 | 6.78 | 6.35 | 6.24 | 6.24 | 5.65 | 5.59 | 5.62 |
embodiment 4
Change La (NO in embodiment 3
3)
36H
2o, Fe (NO
3)
39H
2the amount of O and zinc nitrate is respectively 0.0534g, 0.0491g and 0.0367g, and the catalyst of preparation adopts the appreciation condition of embodiment 1, and CO is converted into CO completely
2minimum full conversion temperature be 0 DEG C.
Adopt the appreciation condition of specific embodiment 2,1%Au/ZFLA catalyst also shows reasonable catalytic performance in different temperatures section.Exemplary statistical data is as shown in table 3.
The catalytic activity of table 3 1%Au/ZFLA catalyst in analog laser atmosphere at differential responses temperature (R: CO mol (g
au)
-1h
-1) along with the change in reaction time (h)
| Time (h) temperature (DEG C) | 0.5 | 1.5 | 2.5 | 3.5 | 4.5 | 5.5 | 6.5 | 7.5 | 8.5 | 9.5 | 10.5 |
| 70 | 0.78 | 0.57 | 0.49 | 0.42 | 0.33 | 0.29 | 0.25 | 0.17 | 0.17 | 0.12 | 0.09 |
| 120 | 1.60 | 1.28 | 1.13 | 0.94 | 0.90 | 0.84 | 0.70 | 0.77 | 0.71 | 0.62 | 0.60 |
embodiment 5
Take 0.0604g La (NO
3)
36H
2o, 0.0524g Fe (NO
3)
39H
2o, 0.0207g nickel nitrate is dissolved in 2.8ml deionized water and forms Ni-Fe-La salting liquid, takes the preparation flow of embodiment 1, obtains NiFeLaO
x/ Al
2o
3(NFLA) carrier.According to the step in embodiment 1, reduction temperature is adjusted to 450 DEG C, i.e. obtained 1%Au/NFLA catalyst.
Adopt the appreciation condition of specific embodiment 1, CO is converted into CO completely
2be minimumly entirely converted into-6 DEG C.
Adopt the appreciation condition of specific embodiment 2,1%Au/NFLA catalyst also shows reasonable catalytic performance in different temperatures section.Exemplary statistical data is as shown in table 4.
The catalytic activity of table 4 1%Au/NFLA catalyst in analog laser atmosphere at differential responses temperature (R: CO mol (g
au)
-1h
-1) with the change in reaction time (h)
embodiment 6
Take 0.0617g La (NO
3)
36H
2o, 0.0568g Fe (NO
3)
39H
2o, 0.0171g manganese acetate is dissolved in 2.8ml deionized water and forms Mn-Fe-La salting liquid, takes the preparation flow of embodiment 1, obtains MnFeLaO
x/ Al
2o
3(being called for short MFLA) carrier., according to the step in embodiment 1, only reduction temperature is adjusted to 450 DEG C, i.e. obtained 1%Au/MFLA catalyst.
Adopt the appreciation condition of embodiment 1, CO is converted into CO completely
2minimum full conversion temperature be 3 DEG C.
Adopt the appreciation condition of embodiment 2,1%Au/MFLA catalyst also shows reasonable catalytic performance in different temperatures section, and stability compares, good temperature is 400 DEG C.Exemplary statistical data is as shown in table 5.
The catalytic activity of table 5 1%Au/MFLA catalyst in analog laser atmosphere at differential responses temperature (R: CO mol (g
au)
-1h
-1) change with the reaction time (h)
embodiment 7
Change La (NO in embodiment 6
3)
36H
2o, Fe (NO
3)
39H
2the amount of O and manganese acetate is respectively 0.0525g, 0.0482g and 0.0297g, and obtained Au/MFLA catalyst adopts the appreciation condition of embodiment 1, and CO is converted into CO completely
2minimum full conversion temperature be 80 DEG C.
Adopt the appreciation condition of specific embodiment 2,1%Au/MFLA catalyst also shows reasonable catalytic performance in different temperatures section.Exemplary statistical data is as shown in table 6.
The catalytic activity of table 6 1%Au/MFLA catalyst in analog laser atmosphere at differential responses temperature (R: CO mol (g
au)
-1h
-1) with the change in reaction time (h)
| Time (h) temperature (DEG C) | 0.5 | 1.5 | 2.5 | 3.5 | 4.5 | 5.5 | 6.5 | 7.5 | 8.5 | 9.5 | 10.5 |
| 70 | 0.62 | 0.34 | 0.28 | 0.18 | 0.12 | 0.11 | 0.03 | 0.02 | 0 | 0 | 0 |
| 120 | 1.25 | 0.79 | 0.76 | 0.51 | 0.43 | 0.34 | 0.17 | 0.16 | 0.12 | 0.10 | 0.08 |
embodiment 8
Take 0.0612g La (NO
3)
36H
2o, 0.0563g Fe (NO
3)
39H
2o, 0.0171g copper nitrate is dissolved in 2.8ml deionized water and forms Cu-Fe-La salting liquid, takes the preparation procedure of embodiment 1, obtains CuFeLaO
x/ Al
2o
3(being called for short CFLA) carrier.According to the step in embodiment 1, i.e. obtained 1%Au/CFLA catalyst.
Adopt the appreciation condition of embodiment 1, CO is converted into CO completely
2minimum full conversion temperature be-10 DEG C.
Adopt the appreciation condition of embodiment 2,1%Au/CFLA catalyst also shows reasonable catalytic performance in different temperatures section, and stability compares, good temperature is 70 DEG C and 120 DEG C.Exemplary statistical data is as shown in table 7.
The catalytic activity of table 7 1%Au/CFLA catalyst in analog laser atmosphere at differential responses temperature (R: CO mol (g
au)
-1h
-1) change with the reaction time (h)
embodiment 9
Change La (NO in embodiment 8
3)
36H
2o, Fe (NO
3)
39H
2the amount of O and copper nitrate is respectively 0.0536g, 0.0493g and 0.0299g, and obtained 1%Au/CFLA-9 catalyst adopts the appreciation condition of embodiment 1, and CO is converted into CO completely
2minimum full conversion temperature be 2 DEG C.
Adopt the appreciation condition of specific embodiment 2,1%Au/CFLA-9 catalyst also shows the catalytic performance slightly poor compared with embodiment 8 in different temperatures section.Exemplary statistical data is as shown in table 8.
The catalytic activity of table 8 1%Au/CFLA-9 catalyst in analog laser atmosphere at differential responses temperature (R: CO mol (g
au)
-1h
-1) with the change in reaction time (h)
| Time (h) temperature (DEG C) | 0.5 | 1.5 | 2.5 | 3.5 | 4.5 | 5.5 | 6.5 | 7.5 | 8.5 | 9.5 | 10.5 |
| 70 | 0.42 | 0.31 | 0.25 | 0.18 | 0.12 | 0.09 | 0.05 | 0.03 | 0.02 | 0.005 | 0 |
| 120 | 1.83 | 1.32 | 0.96 | 0.80 | 0.73 | 0.59 | 0.42 | 0.34 | 0.25 | 0.29 | 0.19 |
embodiment 10
The catalyst adopting specific embodiment 1 to prepare and the unstripped gas of embodiment 1, by the catalyst after primary first-order equation again from low-temperature test its to the oxidability of CO, 1%CO still can transform at-10 DEG C by catalyst completely.Result shows that this catalyst can reuse, and activity stabilized.
embodiment 11
Take Al
2o
3original vector 1.96g, through 650 DEG C of roasting 4h, for subsequent use; Take 0.0712g La (NO
3)
3, 0.0701g Fe (NO
3)
39H
2o is dissolved in 2.8ml deionized water, forms Fe-La salting liquid; With the above-mentioned baked Al of described Fe-La salting liquid incipient impregnation
2o
31.5h, then by products therefrom 120 DEG C of dry 4h, 850 DEG C of roasting 4h, obtain FeLaO
x/ Al
2o
3carrier.
Take HAuCl
4h
2o adds deionized water preparation 1.4g
authe solution of/L, uses KOH to regulate described pH value of solution to 9 ~ 10, obtains golden precursor solution; With this golden precursor solution incipient impregnation above-mentioned FLA complex carrier 1.5h, products therefrom is soaked 24h through ammoniacal liquor, then through washing removing chlorion, then at 60 DEG C, dry 12h, then through 300 DEG C of hydrogen reducing 1h, i.e. obtained 0.2%Au/FLA catalyst.
Adopt the appreciation condition of embodiment 1, CO is converted into CO completely
2minimum full conversion temperature be 100 DEG C.
Adopt the appreciation condition of embodiment 2, the initial activity of catalyst is fair, but along with the prolongation in reaction time, its stability is not as 1%Au/FLA catalyst (embodiment 2).Exemplary statistical data is as shown in table 9.
The catalytic activity of table 9 0.2%Au/FLA catalyst in analog laser atmosphere at differential responses temperature (R: CO mol (g
au)
-1h
-1) change with the reaction time (h)
embodiment 12
Take Al
2o
3original vector 1.95g, through 650 DEG C of roasting 4h, for subsequent use; Take 0.0712g La (NO
3)
3, 0.0701g Fe (NO
3)
39H
2o is dissolved in 2.8ml deionized water, forms Fe-La salting liquid; With the above-mentioned baked Al of described Fe-La salting liquid incipient impregnation
2o
31.5h, by products therefrom 80 DEG C of dry 2h, dry 4h for 120 DEG C, 850 DEG C of roasting 4h, obtain FeLaO
x/ Al
2o
3(being called for short FLA) carrier.
Take HAuCl
4h
2o adds the solution of deionized water preparation 3.5gAu/L, uses KOH to regulate described pH value of solution to 9 ~ 10, obtains golden precursor solution; With this golden precursor solution incipient impregnation above-mentioned FLA complex carrier 1.5h, products therefrom is soaked 24h through ammoniacal liquor, then through washing removing chlorion, then at 60 DEG C, dry 12h, then through 300 DEG C of hydrogen reducing 1h, i.e. obtained 0.5%Au/FLA catalyst.
Adopt the appreciation condition of embodiment 1, CO is converted into CO completely
2minimum full conversion temperature be 50 DEG C.
Adopt the appreciation condition of embodiment 2, the initial activity of catalyst is fair, and along with the prolongation in reaction time, its stability is better than 0.2%Au/FLA catalyst (embodiment 11).Exemplary statistical data is as shown in table 10.
The catalytic activity of table 10 0.5%Au/FLA catalyst in analog laser atmosphere at differential responses temperature (R: CO mol (g
au)
-1h
-1) change with the reaction time (h)
embodiment 13
Adopt the Au/FLA catalyst that embodiment 1 is obtained, fresh 0.5g catalyst silk screen is encapsulated, is fixed on RF excited CO
2the gas storage tube chamber of laser instrument is inner, keep normal radio frequency laser production technology constant, optical tests is gone out for a long time with the radio frequency laser that catalyst is housed, and time recording data (dutycycle, power, current value), properties of product are mainly manifested in power stability: standard is that maximum duty cycle bright dipping (60%) power is not less than 160W at present, and fluctuation range is no more than the +/-10W of mean power.Exemplary statistical data is as shown in table 11.
Table 11 is equipped with the RF excited CO of 0.5g Au/FLA catalyst
2optical output power of laser over time
The RF excited CO of model of the same race
2laser device laser pipe, the blank tube not installing catalyst also carries out test experiments simultaneously, the results are shown in Table 12.
Table 12 is unkitted the blank RF excited CO of catalyst
2laser tube light power over time
Visible, the RF-laser pipe in position loading appropriate Au catalyst significantly can stablize light power within the longer testing time, thus extends RF excited CO
2the Acceptable life of laser instrument.
Claims (9)
1. one kind for closed CO
2the particulate supported type nano catalyst of laser instrument, is characterized in that, active component is Au, and carrier is composite oxide modified aluminium oxide MFeLaO
x/ Al
2o
3, wherein M is Cu, or Zn, or Mn, or Ni.
2. load type nano gold catalyst as claimed in claim 1, it is characterized in that, it is 0.2 ~ 3% that gold element accounts for catalyst gross mass percentage, FeLaO in composite oxide modified aluminium oxide
xfor AL
2o
3weight 1 ~ 5%, M and Fe atomic ratio 0 ~ 5.
3. load type nano gold catalyst as claimed in claim 1 or 2, is characterized in that, wherein the precursor of gold is HAuCl
4h
2o or AuCl
3or metallic gold; The precursor compound of described M component and Fe, La is its corresponding nitrate or hydrochloride or acetate respectively.
4. the preparation method of the load type nano gold catalyst as described in claim 1 or 2 or 3, is characterized in that, adopts equi-volume impregnating preparation.
5. the preparation method of load type nano gold catalyst as claimed in claim 4, it is characterized in that, its preparation technology is:
(1) Al is taken
2o
3carrier 1.94 ~ 1.96 weight portion is through 600 ~ 700 DEG C of roasting 4h, for subsequent use; Take 0.0356 ~ 0.1782 mass parts La (NO
3)
36H
2o, 0.0326 ~ 0.1638 mass parts Fe (NO
3)
39H
2o, 0 ~ 0.6112 mass parts M salt, is dissolved in 2.8 mass parts deionized waters, forms M-Fe-La mixing salt solution; With the baked Al of described M-Fe-La salting liquid incipient impregnation
2o
31.5h, products therefrom through 80 DEG C ~ 120 DEG C drying 4 ~ 8h, then through 600 ~ 950 DEG C of roasting 4h, obtains MFeLaO
x/ Al
2o
3complex carrier;
(2) HAuCl is got
4h
2o adds deionized water and makes 1.4 ~ 21.6g
authe solution of/L, uses aqueous slkali to regulate above-mentioned pH value of solution to 6 ~ 10, obtains golden precursor solution; Use above-mentioned golden precursor solution incipient impregnation step (1) gained MFeLaO
x/ Al
2o
3complex carrier 1.5h, products therefrom soaks 24h through ammoniacal liquor, then is washed till without chlorion by deionized water, then at 50 ~ 100 DEG C, dries 5 ~ 12h, then through 300 DEG C ~ 450 DEG C hydrogen reducing 1h, obtained Au/MFLA finished catalyst;
In step (2), aqueous slkali used is Na
2cO
3or NaOH or K
2cO
3or the solution of KOH.
6. the preparation method of load type nano gold catalyst as claimed in claim 5, it is characterized in that, its preparation technology is:
(1) Al is taken
2o
3carrier 1.94 weight portion is through 650 DEG C of roasting 4h, for subsequent use; Take 0.0525 ~ 0.0712 mass parts La (NO
3)
36H
2o, 0.0482g ~ 0.0701 mass parts Fe (NO
3)
39H
2o, 0 ~ 0.0367 mass parts M salt is dissolved in 2.8 mass parts deionized waters, forms M-Fe-La mixing salt solution; With the baked Al of described M-Fe-La salting liquid incipient impregnation
2o
31.5h, products therefrom through 80 DEG C ~ 120 DEG C drying 4 ~ 8h, then through 850 DEG C of roasting 4h, obtains MFeLaO
x/ Al
2o
3complex carrier;
(2) HAuCl is got
4h
2o adds deionized water and makes 7.14g
authe solution of/L, uses aqueous slkali to regulate above-mentioned pH value of solution to 9 ~ 10, obtains golden precursor solution; Use above-mentioned golden precursor solution incipient impregnation step (1) gained MFeLaO
x/ Al
2o
3complex carrier 1.5h, products therefrom soaks 24h through ammoniacal liquor, then is washed till without chlorion by deionized water, then at 60 DEG C, dries 12h, then through 300 ~ 450 DEG C of hydrogen reducing 1h, obtained Au/MFLA finished catalyst;
In step (2), aqueous slkali used is KOH solution.
7. the application process of the load type nano gold catalyst as described in claim 1 or 2 or 3, is characterized in that, 0.3 ~ 2.0g catalyst sealing is contained in closed RF excited CO
2in laser instrument, in order to stable laser power output, and extend the service life of laser instrument.
8. the application process of load type nano gold catalyst as claimed in claim 7, is characterized in that, is that each gas volume is than being CO:O in atmosphere
2: CO
2: He:N
2: H
2o=1.0:0.5:60:10:28: trace or percentage by volume are 1%CO, 0.5%O
2, 60%CO
2, 0.5% steam, Balance Air is inert gas N
2condition under, described catalyst CO is oxidized to CO
2temperature be 30 ~ 400 DEG C.
9. the catalytic performance test method of load type nano gold catalyst as claimed in claim 2, is characterized in that, under the air atmosphere condition containing 1%CO, the minimum full conversion temperature that described catalyst CO is oxidized is-20 DEG C ~ 100 DEG C.
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| PCT/CN2014/070759 WO2015089925A1 (en) | 2013-12-17 | 2014-01-17 | Granular supported nano-gold catalyst for closed co2 laser |
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| CN101698149B (en) * | 2009-10-14 | 2012-11-07 | 安立敦 | Supported gold-PGM alloy catalyst with stable storage property and preparation method thereof |
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| Title |
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| 林清泉等.LaFeO3修饰和O3处理对Au/A12O3催化剂在CO氧化反应中热稳定性的影响.《催化学报》.2008,第29卷(第6期), * |
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