CN116459844A - Supported nano palladium-gold catalyst and preparation method thereof - Google Patents
Supported nano palladium-gold catalyst and preparation method thereof Download PDFInfo
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- 239000010931 gold Substances 0.000 title claims abstract description 170
- 239000003054 catalyst Substances 0.000 title claims abstract description 134
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000012018 catalyst precursor Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 150000002505 iron Chemical class 0.000 claims description 6
- 150000002940 palladium Chemical class 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 238000004817 gas chromatography Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 22
- 238000011282 treatment Methods 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 150000003568 thioethers Chemical class 0.000 abstract description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 162
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 81
- 230000003647 oxidation Effects 0.000 description 11
- 238000011068 loading method Methods 0.000 description 9
- 239000011943 nanocatalyst Substances 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 239000000729 antidote Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000006540 mitochondrial respiration Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000007310 pathophysiology Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/8906—Iron and noble metals
-
- B01J35/393—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/106—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
-
- 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
Abstract
The invention provides a supported nano palladium-gold catalyst and a preparation method thereof, and nano Au particles and nano Pd particles on the supported nano Pd-Au catalyst prepared by the method are uniformly supported and have high dispersity, and the supported nano palladium-gold catalyst is easy to prepare on a large scale; the supported nano palladium-gold catalyst prepared by the method has good catalytic effect, can realize the complete conversion of CO at the temperature of minus 30 ℃, has good sulfur resistance and stability, and can be used in SO 2 Treatments 1H and H 2 S can still keep the relative airspeed of 1346h after 1h of treatment ‑1 CO with the concentration of 20000ppm is kept within 2 percent of the conversion rate reduction within 726 minutes; the supported nano Pd-Au catalyst prepared by the method can be widely applied to the environment in which sulfides exist, and can be kept stable for a long time.
Description
Technical Field
The invention belongs to the technical field of catalyst application, and particularly relates to a supported nano palladium-gold catalyst with good sulfur resistance and CO catalytic performance and a preparation method thereof.
Background
The insufficient combustion of fossil fuel in the chemical industry, the insufficient combustion of fire explosion and CO generation in a closed environment bring great potential safety hazard to the production and living safety of people. CO poisoning is the most common poisoning in the population, and there is no effective antidote treatment, and the pathophysiology of poisoning includes a reduction in overall oxygen delivery and inhibition of mitochondrial respiration. Therefore, it is important to use efficient CO catalytic oxidation materials to remove CO to ensure health and safety of humans.
Since gold nanoparticles were found to have excellent catalytic properties, they have been used in large amounts in catalytic oxidation reactions. The supported nano gold catalyst has stronger performance than other catalysts for low (normal) temperature catalytic oxidation of CO, and can realize full conversion of low-concentration CO at room temperature. Conditions affecting the performance of the supported nano-gold catalyst mainly include the particle size of the nano-gold particles, the interaction between the carrier and the nano-gold particles, and the like. The preparation method of the supported nano gold catalyst mainly comprises an impregnation method, a deposition precipitation method, a coprecipitation method, a chemical vapor precipitation method, a liquid phase reduction method and the like. Among them, the deposition precipitation method is widely used because of simple operation, and the catalyst with smaller particle size and uniform particle distribution can be prepared. The oxygen vacancy on the supported nano-gold catalyst carrier is the center of oxygen molecule activation, and the effective selection of the carrier is beneficial to obtaining a stronger supported nano-gold catalyst. alpha-Fe 2 O 3 Has rich oxygen vacancies, can provide rich active oxygen for the nano gold particles in the reaction process, and is an excellent carrier of the supported nano gold catalyst. When urea is used as a precipitant, urea slowly releases OH-with temperature changes, which is beneficial to Au (OH) 3 And studies have shown that urea-assisted deposition forms a variety of gold compounds that facilitate increasing the loading of the gold nanoparticles. When the supported nano gold catalyst is prepared by adopting chloroauric acid as an original solution through a deposition precipitation method, the residual chlorine is usedAu is agglomerated during the calcination process, and the ammonia washing catalyst can effectively prevent the Au from sintering by removing residual chlorine. Therefore, the supported nano gold catalyst prepared by adopting the urea-assisted deposition precipitation method and washed by ammonia water can be obtained, and the supported nano gold catalyst with small particle size and uniform distribution can be obtained.
The presence of sulfides in the environment can affect the activity of the supported nanogold catalyst, which severely limits the use of the nanogold catalyst for the treatment of pollutants in industrial flue gas. At SO 2 In the existing environment, the activity of the supported nano-gold catalyst for catalyzing CO is severely reduced, which is probably due to SO 2 The increase in adsorption strength between Au and CO after treatment results in the inhibition of the migration of CO adsorbed on the Au particles to the gold-carrier interface to form CO 2 . The poor sulfide poisoning resistance of the nano-gold catalyst is always one of the important reasons for restricting the application of the nano-gold catalyst. The supported nano Pd catalyst also has stronger CO catalytic oxidation performance, but has the defect of low activity under the low-temperature condition. The Pd-Au bimetallic supported catalyst can be efficiently used for various catalytic reactions. The method of Jinzhang simulates the addition of Au to Pd/TiO in the CO oxidation process by a theoretical calculation method 2 The results show that the addition of Au inhibits Pd/TiO during CO oxidation by forming "crown jewell" Pd-Au structure 2 Is a poisoning of (a). However, experimental studies have not been reported to investigate Pd-Au/FeO x /Al 2 O 3 Influence on the catalytic oxidation performance of CO. Wilburn et al have shown Pd-Pt alloys vs. SO using DRIFTS and TPD studies 2 The adsorption of (2) is related to the mole ratio of Pd to Pt, and the influence of sulfide on the catalyst performance can be reduced by regulating the proportion of the bimetal in the bimetal catalyst. Therefore, the influence of the proportion of Pd-Au active components on the catalytic activity and stability of CO and Pd-Au/FeO in the presence of sulfide are studied by further systematic and intensive experimental study x /Al 2 O 3 Influence of catalyst on CO catalytic activity and stability, and searching for optimal performance of CO catalytic oxidation Pd-Au/FeO x /Al 2 O 3 The catalyst system is a very interesting one.
Disclosure of Invention
First, the technical problem to be solved
The invention provides a supported nano palladium-gold catalyst and a preparation method thereof, which are used for realizing uniform palladium and gold loading, high dispersity and good catalytic effect of the prepared supported nano palladium-gold catalyst, and have good sulfur resistance, CO catalytic activity and stability.
(II) technical scheme
In order to solve the technical problems, the invention provides a preparation method of a supported nano palladium-gold catalyst, which comprises the following steps:
s1, preparing an iron salt solution with the concentration of 0.3-0.5 mol/L, wherein the iron salt solution is an iron nitrate solution, an iron sulfate solution or an iron chloride solution;
s2, activating the metal oxide, immersing the metal oxide in an iron salt solution, and drying to obtain a supported nano palladium-gold catalyst carrier; the metal oxide is aluminum oxide, zirconium oxide, magnesium hydroxide, manganese oxide, titanium oxide, copper oxide, calcium oxide, zinc oxide or cerium oxide; 1mL of ferric salt solution contains 1.5-2 g of metal oxide;
s3, activating the supported nano palladium-gold catalyst carrier, placing the activated carrier in a container, adding palladium salt solution and deionized water, soaking for 30min, performing ultrasonic auxiliary soaking for 30min, and performing constant-temperature water bath shaking table oscillation for 24h at room temperature to obtain a supported nano palladium catalyst precursor; the palladium salt solution is palladium nitrate solution, palladium chloride solution or palladium acetate solution; the mass ratio of the nano palladium-gold catalyst carrier to the palladium salt solution is 1 (0.01-0.03), and the volume of deionized water is 50-150 mL;
s4, taking out the precursor of the supported nano palladium catalyst, and then sequentially drying, roasting in oxygen atmosphere and roasting in hydrogen atmosphere to obtain the supported nano palladium catalyst;
s5, placing the supported nano palladium catalyst in a container, sequentially adding a precipitator, chloroauric acid and deionized water into the container, oscillating at a constant temperature water bath shaker at 75-85 ℃ until the pH value of the solution is 8-8.5, and standing for 4-6 h to obtain a supported nano gold catalyst precursor; the mass ratio of the supported nano palladium catalyst to the precipitator to the chloroauric acid to the deionized water is 1 (0.9-1.0) (0.02-0.065) (8.5-12); the precipitant is urea, sodium carbonate or sodium bicarbonate;
and S6, taking out the precursor of the supported nano-gold catalyst, and then sequentially washing, drying, roasting in oxygen atmosphere and roasting in hydrogen atmosphere to obtain the supported nano-palladium-gold catalyst.
Further, in step S2, the specific steps of activation are: heating the metal oxide to 550-650 ℃ at a speed of 5-15 ℃/min, preserving heat for 1.5-2.5 h, and then cooling to room temperature; the drying temperature is 120-140 ℃, and the drying time is 10-14 h.
Further, in step S2, the metal oxide is spherical, cubic, honeycomb, rod-like, or plate-like in shape.
Further, in step S3, the specific steps of activation are: heating the supported nano palladium-gold catalyst carrier to 450-550 ℃ at a speed of 5-15 ℃/min, preserving heat for 1.5-2.5 h, and then cooling to room temperature; the oscillating speed of the constant-temperature water bath shaking table is 80-150 rpm.
Further, in the step S4, the drying temperature is 120-140 ℃ and the drying time is 10-14 h; the roasting temperature in the oxygen atmosphere is 280-320 ℃ and the time is 1.5-2.5 h; the roasting temperature of the hydrogen atmosphere is 280-320 ℃ and the roasting time is 30-60 min.
Further, in the step S5, the mass percentage of gold in chloroauric acid is 48-50%; the rotation speed of the constant temperature water bath shaking table is 80-150 rpm.
Further, in the step S6, 100-150 mL/time deionized water washing is sequentially carried out for 3-5 times, and 50-80 mL/time ammonia water washing is carried out for 1-2 times after the supported nano gold catalyst precursor is taken out; the drying temperature is 120-140 ℃, and the drying time is 10-14 h; the roasting temperature in the oxygen atmosphere is 280-320 ℃ and the time is 1.5-2.5 h; the roasting temperature of the hydrogen atmosphere is 280-320 ℃ and the roasting time is 30-60 min.
Further, the step S2 and the step S3 are repeated for a plurality of times to obtain the supported nano-gold catalyst carrier meeting the thickness requirement.
In addition, the invention also provides a supported nano palladium-gold catalyst, which is prepared by adopting the method.
In addition, the invention also provides application of the supported nano palladium-gold catalyst, wherein the supported nano palladium-gold catalyst is subjected to sulfide pretreatment and then is subjected to CO catalytic oxidation reaction and gas chromatography for detection; wherein, the sulfide pretreatment is that SO with the concentration of 2ppm and the flow of 100mL/min is used before CO is catalyzed and oxidized by the catalyst 2 After purging for 1H, H was used at a concentration of 2ppm at a flow rate of 100mL/min 2 S, purging for 1h; when the conversion rate of CO along with the temperature change is detected, the concentration of CO is 2500ppm, and the flow is 50mL/min; when the stability of CO at room temperature is detected, the concentration of CO is 20000ppm, and the volume space velocity is 1346h -1 。
(III) beneficial effects
The invention provides a supported nano palladium-gold catalyst and a preparation method thereof, and nano Au particles and nano Pd particles on the supported nano Pd-Au catalyst prepared by the method are uniformly supported and have high dispersity, and the supported nano palladium-gold catalyst is easy to prepare on a large scale; the supported nano palladium-gold catalyst prepared by the method has good catalytic effect, can realize the complete conversion of CO at the temperature of minus 30 ℃, has good sulfur resistance and stability, and can be used in SO 2 Treatments 1H and H 2 S can still keep the relative airspeed of 1346h after 1h of treatment -1 CO with the concentration of 20000ppm is kept within 2 percent of the conversion rate reduction within 726 minutes; the supported nano Pd-Au catalyst prepared by the method can be widely applied to the environment in which sulfides exist, and can be kept stable for a long time.
Drawings
FIG. 1 is a schematic diagram of a supported nano palladium-gold catalyst Pd-Au/FeO prepared in example 1 x /Al 2 O 3 XRD test results of (a) are schematic; in the figure, t is alpha-Fe 2 O 3 Is used for the purpose of the peak of (2),is the peak of nano Au, and the diamond-solid is gamma-Al 2 O 3 Is a peak of (2); the abscissa is 2 theta, unit degree;
FIG. 2a shows Au/FeO at 50nm scale x /Al 2 O 3 TEM characterization of the catalyst; FIGS. 2b and 2c are, respectively, au/FeO x /Al 2 O 3 Mapping characterization graphs of Au and Fe elements on the catalyst; FIG. 2d is Au/FeO x /Al 2 O 3 Particle size distribution of the catalyst; FIG. 2e is a scale of 50nm Pd-Au/FeO x /Al 2 O 3 TEM characterization of the catalyst; FIGS. 2f, 2g, 2h are Pd-Au/FeO, respectively x /Al 2 O 3 An Au, pd and Fe element characterization diagram on the catalyst;
FIG. 3a is a schematic diagram of a supported nanocatalyst Pd-Au/FeO x /Al 2 O 3 XEDS characterization of sulfide adsorption, FIG. 3b is Au/FeO x /Al 2 O 3 XEDS characterization of sulfide adsorption;
FIG. 4 is a schematic diagram of a supported nanocatalyst Pd-Au/FeO x /Al 2 O 3 And Au/FeO x /Al 2 O 3 CO-TPR profile of (a);
FIG. 5 is a schematic diagram of a supported nanocatalyst Pd-Au/FeO x /Al 2 O 3 And Au/FeO x /Al 2 O 3 Schematic representation of CO conversion before and after sulfidation as a function of temperature;
FIG. 6 is a supported nanocatalyst Pd-Au/FeO x /Al 2 O 3 And Au/FeO x /Al 2 O 3 Schematic representation of CO conversion over time before and after sulfidation;
FIG. 7 is a graph of Pd-Au/FeO at different Au and Pd mass ratios x /Al 2 O 3 Catalyst and Au/FeO x /Al 2 O 3 A schematic of the conversion of CO by the catalyst as a function of temperature;
FIG. 8 is a Pd-Au/FeO with different Au and Pd mass ratios x /Al 2 O 3 Catalyst and Au/FeO x /Al 2 O 3 The catalyst is schematically shown for the conversion of CO with temperature change after sulfiding.
Detailed Description
To make the objects, contents and advantages of the present invention more apparent, the following detailed description of the present invention will be given with reference to the accompanying drawings and examples.
Example 1
Supported nano palladium-gold catalyst Pd-Au/FeO x /Al 2 O 3 Is prepared by the preparation method of (2)
S1, preparing ferric nitrate (FeN) with concentration of 0.4mol/L 3 O 9 ·9H 2 O) a solution;
s2, taking spherical aluminum oxide with the diameter of 2mm, placing the spherical aluminum oxide into a muffle furnace, heating to 600 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and then reducing to room temperature to obtain activated aluminum oxide; immersing activated aluminum oxide in ferric nitrate solution according to the volume ratio of 1:1, drying at 120 ℃ for 12 hours in an oven, taking out, then placing in a muffle furnace, heating to 500 ℃ at the heating rate of 10 ℃/min, preserving heat for 2 hours, and then cooling to room temperature to obtain the primary-immersed FeO x /Al 2 O 3 A carrier;
s3, repeating the step 2 for two times to obtain three impregnated FeO x /Al 2 O 3 A carrier;
s4, taking FeO x /Al 2 O 3 10g of carrier is put into a conical flask, palladium nitrate with the palladium content of 0.1g is added, the volume is fixed to 50mL, and the carrier is immersed for 30min under the assistance of ultrasound after standing for 30min; then the conical flask is put into a constant temperature water bath shaking table to perform shaking reaction for 24 hours at the rotating speed of 135rpm, so as to obtain a supported nano palladium catalyst precursor;
s5, taking out and drying for 12 hours after the reaction is completed; placing the dried sample into a tube furnace, roasting for 2 hours at 300 ℃ in an oxygen atmosphere, and roasting for 30 minutes at 300 ℃ in a hydrogen atmosphere to obtain Pd/FeO x /Al 2 O 3 A catalyst;
s6, pd/FeO is added according to the mass ratio of 1:1:0.042:10 x /Al 2 O 3 Sequentially adding a catalyst, urea, chloroauric acid with gold content of 48% and deionized water into a conical flask, placing the conical flask into a constant-temperature water bath shaking table oscillator, oscillating at a rotating speed of 130rpm and heating to 80 ℃, stopping oscillating and heating when the pH value of the solution is 8, and standing for 4 hours to obtain a supported nano palladium-gold catalyst precursor;
s7, taking out and washing the supported nano palladium-gold catalyst precursor, firstly using 1Washing with 20 mL/time deionized water for 4 times, and washing with 60 mL/time ammonia water for 2 times until no precipitate is generated by testing with 0.5mol/L silver nitrate solution; putting the washed catalyst into an oven to be dried for 12 hours at the temperature of 120 ℃; placing the dried sample into a tubular furnace, roasting for 2 hours at 300 ℃ in an oxygen atmosphere, and roasting for 30 minutes at 300 ℃ in a hydrogen atmosphere to obtain the supported nano palladium-gold catalyst Pd-Au/FeO x /Al 2 O 3 Wherein the mass ratio of Au to Pd is 2:1.
The supported nano palladium-gold catalyst Pd-Au/FeO prepared in the embodiment x /Al 2 O 3 The loading test results (ICP-OES) of the active components of Pd and Au show that the theoretical loading of Pd and Au is 1% and 2%, the actual loading is 0.7% and 1.7%, and the theoretical loading is relatively close to the actual loading, so that the catalyst prepared by the embodiment has good loading effect and high raw material utilization rate.
The supported nano palladium-gold catalyst Pd-Au/FeO prepared in the embodiment x /Al 2 O 3 With reference to FIG. 1, sharp peaks of aluminum oxide and iron oxide, as well as peaks of gold nanoparticles, appear, indicating successful loading of nanoparticles on FeO x /Al 2 O 3 The characteristic peaks of Pd on the support, but not shown, are due to the high dispersion of Pd on the catalyst support.
The supported nano catalyst Pd-Au/FeO prepared in the embodiment x /Al 2 O 3 And Au/FeO x /Al 2 O 3 The morphology, element distribution and particle size of (c) are shown in figure 2. Wherein, au is uniformly dispersed in FeO x /Al 2 O 3 On a carrier (fig. 2a and 2 b). The distribution of the Nano Au particles was counted by Nano Measurer particle size distribution software, and the average particle size was calculated to be 3.5nm (FIG. 2 d). Pd-Au/FeO x /Al 2 O 3 The catalyst has nano Pd particles with larger particle size and uniformly dispersed, nano Au particles with smaller particle size (shown in figures 2e, 2f and 2 g) are grown on the Pd particles, and the Au/FeO is shown in figures 2c and 2h respectively x /Al 2 O 3 Catalyst and Pd-Au/FeO x /Al 2 O 3 Fe element Mapping on catalystAnd (5) characterizing the graph.
The supported nano catalyst Pd-Au/FeO prepared in the embodiment x /Al 2 O 3 And Au/FeO x /Al 2 O 3 The elemental distribution after sulfidation is shown in figures 3a and 3b, respectively. Calculated out, pd-Au/FeO x /Al 2 O 3 The S element adsorbed by the catalyst was 7.8wt%, while Au/FeO x /Al 2 O 3 The S element adsorbed by the catalyst is 33.66wt percent and is Pd-Au/FeO x /Al 2 O 3 4.3 times of the catalyst proves that sulfide is not easy to be in Pd-Au/FeO x /Al 2 O 3 And (3) adsorbing on the catalyst.
The supported nano catalyst Pd-Au/FeO prepared in the embodiment x /Al 2 O 3 And Au/FeO x /Al 2 O 3 The oxidizing power for CO is shown in fig. 4. Pd-Au/FeO x /Al 2 O 3 The catalyst showed a peak of CO reduction and CO at 243.4 DEG C 2 Increased peak ascribed to oxidation of CO by supported nano Pd catalyst, au/FeO x /Al 2 O 3 The catalyst exhibited a peak of CO reduction and CO at 517 DEG C 2 The increased peak, which is attributed to the oxidation of CO by the supported nano Au catalyst. Pd-Au/FeO x /Al 2 O 3 The catalyst catalyzes the peak of CO and Au/FeO x /Al 2 O 3 The shift of the peak phase of the catalyst catalytic CO to low temperature also suggests Pd-Au/FeO x /Al 2 O 3 The catalyst has higher low-temperature catalytic CO activity.
The supported nano catalyst Pd-Au/FeO prepared in the embodiment x /Al 2 O 3 And Au/FeO x /Al 2 O 3 Complete conversion of 2500ppm CO at-30deg.C was achieved without sulfide pretreatment, as shown in FIG. 5. After being pretreated by sulfide, pd-Au/FeO x /Al 2 O 3 The catalyst had a CO conversion of 87.2% at a concentration of 2500ppm at-30 ℃. The conversion at 25 ℃ reached 100% and was maintained at 100% conversion as the temperature increased. Sulfide pretreated Au/FeO x /Al 2 O 3 The catalyst maintains 23 to 26 percent of conversion rate along with the temperature change, the conversion rate is obviously reduced compared with that before vulcanization, which shows that Pd-Au/FeO x /Al 2 O 3 The catalyst is less affected by sulfides.
The supported nano catalyst Pd-Au/FeO prepared in the embodiment x /Al 2 O 3 And Au/FeO x /Al 2 O 3 The stability of the catalyst to CO oxidation at 25 c before and after sulphide treatment is tested as shown in figure 6. Au/FeO without sulfide pretreatment x /Al 2 O 3 The conversion of the catalyst was reduced from 97.9% to 52.4% in 726 min; pd-Au/FeO x /Al 2 O 3 The conversion of the catalyst was reduced from 100% to 97.9% in 748 min. After being pretreated by sulfide, au/FeO x /Al 2 O 3 The conversion of the catalyst was reduced from 91.9% to 37% in 550 min; pd-Au/FeO x /Al 2 O 3 The conversion of the catalyst was reduced from 98.1% to 96.5% in 726 min. This means Pd-Au/FeO x /Al 2 O 3 The catalyst has very strong stability before and after sulphide treatment.
Example 2
This example is essentially the same as example 1, except Pd/FeO x /Al 2 O 3 Catalyst, urea, chloroauric acid with 48% gold content and deionized water with a mass ratio of 1:1:0.021:10, and Pd-Au/FeO with a mass ratio of 1:1 of Au to Pd are prepared x /Al 2 O 3 A catalyst.
Example 3
This example is essentially the same as example 1, except Pd/FeO x /Al 2 O 3 Catalyst, urea, chloroauric acid with 48% gold content and deionized water in a mass ratio of 1:1:0.063:10, and Pd-Au/FeO with 3:1 Au/Pd mass ratio is prepared x /Al 2 O 3 A catalyst.
Example 4
This example is essentially the same as example 1, except Pd/FeO x /Al 2 O 3 The mass ratio of the catalyst to urea to chloroauric acid with 48% of gold content to deionized water is 1:1:0.105:10, and the Pd-Au/FeOx/Al2O3 catalyst with 5:1 of Au to Pd mass ratio is prepared.
Example 5
This example is essentially the same as example 1, except Pd/FeO x /Al 2 O 3 The mass ratio of the catalyst to urea to chloroauric acid with 48% of gold content to deionized water is 1:1:0.21:10, and the Pd-Au/FeO with the mass ratio of Au to Pd of 10:1 is prepared x /Al 2 O 3 A catalyst.
The mass ratios of Au to Pd prepared in examples 2 to 5 are Pd-Au/FeO of 1:1,3:1,5:1 and 10:1 respectively x /Al 2 O 3 Catalyst and Au/FeO x /Al 2 O 3 The catalytic activity of the catalyst on CO results are shown in fig. 7. Wherein, at the temperature of minus 30 ℃, the mass ratio of Pd to Pd is 10:1 of Pd-Au/FeO x /Al 2 O 3 The catalytic conversion rate of the catalyst and other catalysts to CO reaches 100 percent. Pd-Au/FeO with mass ratio of Au to Pd of 10:1 x /Al 2 O 3 The catalyst also achieves complete catalytic conversion of CO at about-25 ℃. Pd-Au/FeO prepared by the above description x /Al 2 O 3 Catalyst and Au/FeO x /Al 2 O 3 The catalyst has very good activity of low-temperature catalytic oxidation of CO.
The mass ratios of Au to Pd prepared in examples 2 to 5 are Pd-Au/FeO of 1:1,3:1,5:1, 10:1, respectively x /Al 2 O 3 Catalyst and Au/FeO x /Al 2 O 3 The catalytic activity of the catalyst after sulfiding pretreatment on 2500ppm CO was as shown in FIG. 8. When the catalyst is successively passed through SO with concentration of 2ppm 2 And H at a concentration of 2ppm 2 S is pretreated for 1h, and Pd-Au/FeO with different proportions x /Al 2 O 3 The catalyst still achieves 100% CO catalytic conversion of 2500ppm at 20 ℃ and Au/FeO x /Al 2 O 3 The catalyst had a catalytic conversion of only 25% for 2500ppm CO, indicating Pd-Au/FeO x /Al 2 O 3 The catalyst has very good sulfide resistance stabilityAnd (5) qualitative property.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (10)
1. The preparation method of the supported nano palladium-gold catalyst is characterized by comprising the following steps of:
s1, preparing an iron salt solution with the concentration of 0.3-0.5 mol/L, wherein the iron salt solution is an iron nitrate solution, an iron sulfate solution or an iron chloride solution;
s2, activating the metal oxide, immersing the metal oxide in an iron salt solution, and drying to obtain a supported nano palladium-gold catalyst carrier; the metal oxide is aluminum oxide, zirconium oxide, magnesium hydroxide, manganese oxide, titanium oxide, copper oxide, calcium oxide, zinc oxide or cerium oxide; 1mL of ferric salt solution contains 1.5-2 g of metal oxide;
s3, activating the supported nano palladium-gold catalyst carrier, placing the activated carrier in a container, adding palladium salt solution and deionized water, soaking for 30min, performing ultrasonic auxiliary soaking for 30min, and performing constant-temperature water bath shaking table oscillation for 24h at room temperature to obtain a supported nano palladium catalyst precursor; the palladium salt solution is a palladium nitrate solution, a palladium chloride solution or a palladium acetate solution; the mass ratio of the nano palladium-gold catalyst carrier to the palladium salt solution is 1 (0.01-0.03), and the volume of deionized water is 50-150 mL;
s4, taking out the precursor of the supported nano palladium catalyst, and then sequentially drying, roasting in oxygen atmosphere and roasting in hydrogen atmosphere to obtain the supported nano palladium catalyst;
s5, placing the supported nano palladium catalyst in a container, sequentially adding a precipitator, chloroauric acid and deionized water into the container, oscillating at a constant temperature water bath shaker at 75-85 ℃ until the pH value of the solution is 8-8.5, and standing for 4-6 h to obtain a supported nano gold catalyst precursor; the mass ratio of the supported nano palladium catalyst to the precipitator to the chloroauric acid to the deionized water is 1 (0.9-1.0) (0.02-0.065) (8.5-12); the precipitant is urea, sodium carbonate or sodium bicarbonate;
and S6, taking out the precursor of the supported nano-gold catalyst, and then sequentially washing, drying, roasting in oxygen atmosphere and roasting in hydrogen atmosphere to obtain the supported nano-palladium-gold catalyst.
2. The preparation method according to claim 1, wherein in step S2, the specific steps of activation are: heating the metal oxide to 550-650 ℃ at a speed of 5-15 ℃/min, preserving heat for 1.5-2.5 h, and then cooling to room temperature; the drying temperature is 120-140 ℃, and the drying time is 10-14 h.
3. The method according to claim 1, wherein in step S2, the metal oxide is spherical, cubic, honeycomb, rod-like or plate-like in shape.
4. The preparation method according to claim 1, wherein in step S3, the specific steps of activation are: heating the supported nano palladium-gold catalyst carrier to 450-550 ℃ at a speed of 5-15 ℃/min, preserving heat for 1.5-2.5 h, and then cooling to room temperature; the oscillating speed of the constant-temperature water bath shaking table is 80-150 rpm.
5. The preparation method according to claim 1, wherein in the step S4, the drying temperature is 120-140 ℃ and the drying time is 10-14 h; the roasting temperature in the oxygen atmosphere is 280-320 ℃ and the time is 1.5-2.5 h; the roasting temperature of the hydrogen atmosphere is 280-320 ℃ and the roasting time is 30-60 min.
6. The preparation method of claim 1, wherein in the step S5, the mass percentage of gold in chloroauric acid is 48-50%; the rotation speed of the constant temperature water bath shaking table is 80-150 rpm.
7. The preparation method of claim 1, wherein in the step S6, 100-150 mL/time deionized water washing is sequentially performed for 3-5 times, and 50-80 mL/time ammonia washing is sequentially performed for 1-2 times after the supported nano-gold catalyst precursor is taken out; the drying temperature is 120-140 ℃, and the drying time is 10-14 h; the roasting temperature in the oxygen atmosphere is 280-320 ℃ and the time is 1.5-2.5 h; the roasting temperature of the hydrogen atmosphere is 280-320 ℃ and the roasting time is 30-60 min.
8. The preparation method of claim 1, wherein step S2 and step S3 are repeated a plurality of times to obtain a supported nano-gold catalyst support satisfying the thickness requirement.
9. A supported nano palladium-gold catalyst, characterized in that the supported nano palladium-gold catalyst is prepared by the method of any one of claims 1-8.
10. The application of the supported nano palladium-gold catalyst according to claim 9, wherein the supported nano palladium-gold catalyst is subjected to sulfide pretreatment and then is subjected to CO catalytic oxidation reaction and gas chromatography for detection; wherein the sulfide pretreatment is that SO with the concentration of 2ppm and the flow of 100mL/min is used before CO is catalyzed and oxidized by a catalyst 2 After purging for 1H, H was used at a concentration of 2ppm at a flow rate of 100mL/min 2 S, purging for 1h; when the conversion rate of CO along with the temperature change is detected, the concentration of CO is 2500ppm, and the flow is 50mL/min; when the stability of CO at room temperature is detected, the concentration of CO is 20000ppm, and the volume space velocity is 1346h -1 。
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