CN108212175A - A kind of porous C o3O4Mono-dispersion microballoon load Au-Pd alloy nano catalyst and preparation method thereof - Google Patents
A kind of porous C o3O4Mono-dispersion microballoon load Au-Pd alloy nano catalyst and preparation method thereof Download PDFInfo
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- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910002710 Au-Pd Inorganic materials 0.000 title claims description 30
- 229910045601 alloy Inorganic materials 0.000 title claims description 26
- 239000000956 alloy Substances 0.000 title claims description 26
- 239000006185 dispersion Substances 0.000 title abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004005 microsphere Substances 0.000 claims description 58
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 49
- 229910000510 noble metal Inorganic materials 0.000 claims description 41
- 239000010931 gold Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 33
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 229910052737 gold Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 229910052763 palladium Inorganic materials 0.000 claims description 21
- 239000012279 sodium borohydride Substances 0.000 claims description 20
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000004729 solvothermal method Methods 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000004581 coalescence Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 38
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 229910001252 Pd alloy Inorganic materials 0.000 abstract 4
- 241000549556 Nanos Species 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 69
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 9
- 239000012855 volatile organic compound Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000010718 Oxidation Activity Effects 0.000 description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910004042 HAuCl4 Inorganic materials 0.000 description 4
- 229910002666 PdCl2 Inorganic materials 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
- B01J23/8913—Cobalt and noble metals
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- 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
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- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a kind of porous C o3O4Mono-dispersion microballoon load Au Pd alloy nano catalyst and preparation method thereof, the porous C o3O4Mono-dispersion microballoon loads Au Pd alloy nano catalyst, including the Co of mono-dispersion microballoon shape pattern coalesced with porous cubic block3O4Carrier, on the hole wall of the carrier load have Au Pd alloys.It is provided by the invention that there is the porous C o for efficiently eliminating volatile organic matter3O4Mono-dispersion microballoon load Au Pd alloy nanos catalyst is porous nano catalyst, has better low-temperature catalytic activity, water resistant and heat resistance.
Description
Technical Field
The invention relates to the field of catalysts for eliminating volatile organic compounds, in particular to porous Co3O4A monodisperse microsphere loaded Au-Pd alloy nano-catalyst and a preparation method thereof.
Background
Volatile Organic Compounds (VOCs) discharged from the industry and the transportation industry pollute the atmospheric environment and harm the human health. Catalytic oxidation is one of the most effective ways to eliminate VOCs, and the development of high performance catalysts has been the focus of environmental catalysis. Catalysts for catalytic oxidative destruction of VOCs mainly include two main classes: transition metal oxides (including single and composite transition metal oxides) and supported noble metals or (and) transition metal catalysts, wherein the supported catalysts are widely applied. The function of the support is mainly to increase the effective surface of the catalyst, to provide a suitable pore structure and to guarantee sufficient mechanical strength and thermal stability.
For example, T ü ys ü z et al (H.T ü ys ü z, et al, chem. Commun.,2008, 4022-3O4Has high activity to CO low-temperature oxidation. Bruce et al (Y.ren, et al, Catal.Lett.,2009,131: 146-3O4、Cr2O3、Fe2O3、Mn2O3And Mn3O4The catalyst shows better catalytic CO oxidation performance. Dai et al (J.G.Deng, et al., J.Phys.chem.C., 2010,114:2694-n. 2010,11: 1171-. However, these porous materials are typically prepared using a nano-replication process, which is complicated by the use of a hard template and subsequent processing steps. Research shows that the catalytic performance of the nanocrystalline is extremely sensitive to the size, the morphology and the pore structure of the nanocrystalline. Preparing catalytic materials with controlled size, regular morphology and porous structure still faces major challenges.
Gold is generally considered to be catalytically inactive. Hutchings and co-workers (G.J. Hutchings, Catal.,1985,96: 292-. The research group of Haruta reported that ultrafine gold particles supported on a transition metal oxide (e.g., iron, cobalt, or nickel oxide) exhibited excellent CO oxidation catalytic performance (M.Haruta, et al, ChemLett,1987,16: 405-408). Compared with other noble metals (such as Pt, Rh or Pd, etc.), the gold is cheaper and more abundant. Since then, gold-loaded catalysis has become more and more widely used. Supported gold catalysts have received much attention in the area of VOCs elimination. For example, Ma et al (C.Y.Ma., et al., J.Am.chem.Soc.,2010,132:2608-3O4And the supported gold catalyst thereof shows high activity to ethylene oxidation reaction at 0 ℃. Xue et al (W.J.Xue, et al., Catal.Commun.,2011,12:1265-3O4Shows excellent catalytic activity (ethylene conversion of about 94% at 0 ℃). However, the Au catalyst has the defects of poor low-temperature catalytic performance, weak steam resistance and easy sintering at high temperature when used for catalyzing the oxidation of VOCs. For example, xAu/Co prepared by Dai et al (H.G.Yang, et al. ChemSusChem,2014,7:1745-3O4In microsphere (x is 1.6-7.4 wt%) series catalyst, 7.4Au/Co3O4Microsphere shows the best catalytic activity of toluene oxidation, but the space velocity is 20000mL/(g h)]The conversion rate of toluene reaches 90 percent90％Still up to 250 ℃; and at this temperature, when 3.0 vol% water vapor was introduced, the conversion of catalytic toluene dropped by 7%.
To increase the loadLow-temperature catalytic activity, high-temperature thermal stability and water resistance of the Au catalyst. Research shows that after Pd element is introduced into Au particles to form alloy, the Au-Pd supported nano catalyst shows excellent catalytic activity on methanol and toluene oxidation due to the synergistic effect between Au and Pd. Hutchings et al investigated Au-Pd/TiO2In the catalytic oxidation of methanol (D.I.Enache, et al., Science,2006,311(5759): 362-; the oxygen free radical bonded on the surface of the supported Au-Pd alloy catalyst is found to be the key of toluene activation. In addition, the mole ratio of Pd to Au in the Au-Pd bimetallic particles is also an important factor influencing the catalytic activity. Although studies of supported Au-Pd catalysts have been reported, controllable synthesis of Au-Pd bimetallic particle composition and size remains a significant challenge in bimetallic catalyst development. To our knowledge, no porous Co has been known so far3O4The preparation of the monodisperse microsphere-loaded Au-Pd alloy catalyst and the report of the application of the catalyst in the research of the toluene catalytic oxidation reaction.
Disclosure of Invention
One of the purposes of the invention is to provide porous Co with better low-temperature catalytic activity, water resistance and heat resistance and capable of efficiently eliminating volatile organic compounds3O4The monodisperse microsphere loads Au-Pd alloy nano-catalyst.
The second purpose of the invention is to provide a preparation method of the nano-catalyst.
In order to achieve the first object, the present invention provides the following technical solutions: porous Co3O4The monodisperse microsphere-supported Au-Pd alloy nano catalyst comprises Co with monodisperse microspherical morphology formed by agglomeration of porous cubes3O4The carrier is characterized in that Au-Pd alloy is loaded on the pore wall of the carrier.
Wherein the loading amount of the Au-Pd alloy is 1.0-2.0 wt%.
In order to achieve the second object, the present invention provides the following technical solutions: a porous Co as described above3O4A preparation method of a monodisperse microsphere loaded Au-Pd alloy nano catalyst, which uses CoCl2·6H2Preparing Co with porous cubic coalescence monodisperse microspherical morphology by taking O and urea as raw materials and adopting a glycerol-assisted solvothermal method3O4Carrier, then NaBH is adopted under the protection of PVA4Au-Pd alloy nano particles are loaded on the Co by a reduction method3O4On a carrier.
The glycerol-assisted solvothermal method specifically comprises the following steps:
step 1: adding CoCl2·6H2Dissolving O in a mixed solution of deionized water, glycerol and urea, and stirring for 1-3 h; wherein the CoCl2·6H2The mass ratio of the O to the urea is 1-3: 1-3;
step 2: transferring the solution obtained in the step 1 into a stainless steel self-pressing kettle with a polytetrafluoroethylene lining of 90-110 mL, carrying out hydrothermal treatment at 110-130 ℃ for 11-13 h, and then carrying out centrifugal separation on the solution to obtain a precipitate;
and step 3: washing the precipitate obtained after the hydrothermal treatment with absolute ethyl alcohol and deionized water for three times, and drying in an oven at 70-90 ℃ for 11-13 h to obtain magenta powder;
and 4, step 4: roasting the magenta powder obtained in the step 3 in a muffle furnace, raising the temperature from room temperature to 480-520 ℃ at the speed of 1-3 ℃/min, and keeping the temperature for 2-5 hours to obtain porous Co3O4A monodisperse microsphere carrier.
Preferably, the glycerol-assisted solvothermal method specifically comprises the following steps:
step 1: adding CoCl2·6H2Dissolving O in a mixed solution of deionized water, glycerol and urea, and stirring for 1 h; wherein,the CoCl2·6H2The mass ratio of O to urea is 1: 1;
step 2: transferring the solution obtained in the step 1 into a 100mL stainless steel self-pressure kettle with a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 120 ℃ for 12h, and then carrying out centrifugal separation on the solution to obtain a precipitate;
and step 3: washing the precipitate obtained after the hydrothermal treatment with absolute ethyl alcohol and deionized water for three times, and drying in an oven at 80 ℃ for 12 hours to obtain magenta powder;
and 4, step 4: roasting the magenta powder obtained in the step 3 in a muffle furnace, raising the temperature from room temperature to 500 ℃ at the speed of 1 ℃/min, and keeping the temperature for 3 hours to obtain porous Co3O4A monodisperse microsphere carrier.
Wherein, the PVA protected NaBH4The reduction method specifically comprises the following steps:
step S1: taking noble metals Au and Pd to prepare a noble metal M solution with Au and Pd concentrations of 0.01-0.03 mol/L respectively, wherein M is Au and Pd;
step S2: 0.01 to 0.03mol/L of noble metal solution is diluted to 2.0 to 2.2 x 10-4mixing PVA with the diluted noble metal solution in an ice water bath according to the mass ratio of M to PVA of 1.0-1.2: 1.0-1.5, and violently stirring for 10-15 min;
step S3: injecting 0.1-0.5 mol/L NaBH4Continuously stirring the aqueous solution for 20-30 min to obtain a noble metal sol; wherein the NaBH4According to M: NaBH4Adding the mixture according to the molar ratio of 1.0-1.2: 5.0-5.3;
step S4: the porous Co is added according to the proportion that the theoretical loading of the noble metal is 1.0-2.0 wt%3O4Adding the monodisperse microsphere carrier into the noble metal sol, carrying out ultrasonic treatment on the obtained suspension for 30-50 s, and stirring for 10-11 h until the colloidal gold is completely adsorbed; carrying out suction filtration to obtain a solid;
step S5: washing the solid with water, drying in an oven at 80-85 ℃ for 10-12 h, roasting in a muffle furnace, raising the temperature from room temperature to 450-460 ℃ at the speed of 1-3 ℃/min, and keeping the temperature for 4-4.2 h to obtain the porous Co3O4The monodisperse microsphere loads Au-Pd alloy nano-catalyst.
Preferably, the PVA-protected NaBH4The reduction method specifically comprises the following steps:
step S1: taking noble metals Au and Pd to prepare noble metal M solutions with Au and Pd concentrations of 0.01mol/L respectively, wherein M is Au and Pd;
step S2: 0.01mol/L noble metal solution is diluted to 2.0 multiplied by 10-4mixing PVA with the diluted noble metal solution in an ice water bath according to the mass ratio of M to PVA of 1.0:1.5, and violently stirring for 10 min;
step S3: injecting 0.1mol/L NaBH4Continuously stirring the aqueous solution for 20min to obtain noble metal sol; wherein the NaBH4According to M: NaBH4Adding the mixture according to the molar ratio of 1.0: 5.0;
step S4: the porous Co is added according to the proportion that the theoretical loading of the noble metal is 1.0wt percent3O4Adding the monodisperse microsphere carrier into the noble metal sol, carrying out ultrasonic treatment on the obtained suspension for 30s, and stirring for 10h until the colloidal gold is completely adsorbed; carrying out suction filtration to obtain a solid;
step S5: washing the solid with water, drying in an oven at 80 deg.C for 12h, calcining in a muffle furnace, heating from room temperature to 450 deg.C at 1 deg.C/min for 4h to obtain porous Co3O4The monodisperse microsphere loads Au-Pd alloy nano-catalyst.
Compared with the traditional method, the method has the following advantages:
the method has the characteristics of cheap and easily obtained raw materials, simple preparation process, controllable appearance and specific surface area of the obtained product and the like.
M/porous Co prepared by the invention3O4Monodisperse microspheres (M ═ Au, Pd, AuPd)2) Monodisperse microspherical Co agglomerated in porous cubic with specific morphology3O4The pore wall is loaded with M (Au, Pd, AuPd)2) The nano particles have good application prospect in the field of VOCs catalytic oxidation.
Drawings
FIG. 1 shows the porous Co obtained3O4Monodisperse microspheres and M/porous Co3O4Monodisperse microspheres (M ═ Au, Pd, AuPd)2) XRD spectrogram of the sample;
FIG. 2 shows the porous Co obtained3O4Monodisperse microspheres and M/porous Co3O4Monodisperse microspheres (M ═ Au, Pd, AuPd)2) SEM and HRTEM images of the samples;
FIG. 3 shows the porous Co obtained3O4Monodisperse microspheres and M/porous Co3O4Monodisperse microspheres (M ═ Au, Pd, AuPd)2) Toluene oxidation activity profile of the sample.
Detailed Description
The following claims are hereby incorporated into the detailed description of the invention, with the understanding that the present disclosure is to be considered as a full and non-limiting example, and any limited number of modifications that fall within the spirit and scope of the claims are intended to be included therein.
Example 1
Preparation of porous Co of example 13O4Monodisperse microspheres:
1.0g of CoCl2·6H2O dissolved in 20mL deionized water, 60mL glycerol and 1.0g ureaStirring the mixed solution for 1 hour; transferring the obtained red solution into a stainless steel self-pressure kettle with a 100mL polytetrafluoroethylene lining, and carrying out hydrothermal treatment at 120 ℃ for 12 h; carrying out centrifugal separation on the precipitate obtained after the hydrothermal treatment, washing the precipitate with absolute ethyl alcohol and deionized water for three times, and drying the precipitate in an oven at the temperature of 80 ℃ for 12 hours; finally, the obtained magenta powder was put in a muffle furnace and calcined in air atmosphere, raised from room temperature to 500 ℃ at a rate of 1 ℃/min and kept at this temperature for 3 hours to obtain porous Co3O4A monodisperse microsphere carrier.
Wherein, the XRD spectrum of the prepared sample is shown in the curve (a) in figure 1, and the prepared porous Co can be known by comparing with the standard XRD spectrum of the cobalt oxide sample3O4The monodisperse microspheres have cubic Co3O4A crystal structure; SEM pictures of the samples are detailed in the pictures (a, b, c) in FIG. 2, from which it is clear that porous Co3O4The monodisperse microspheres have the morphology of monodisperse microspheres with uniform size, and the particle size of the microspheres is about 10 mu m. Each microsphere is a whole formed by the coalescence and combination of porous cubic blocks, and each cubic block is formed by the disordered accumulation of nano particles with the diameter of 30-50 nm; the samples were tested at a toluene concentration of 1000ppm and a toluene to oxygen molar ratio of 1: the toluene oxidation activity at 400 and a space velocity of 20000mL/(gh) is shown in detail in FIG. 3 (a), and the reaction temperature at 90% toluene conversion is 280 ℃.
Preparation of AuPd2Porous Co3O4Monodisperse microsphere catalyst:
step S1: with PdCl2、HAuCl4And preparing noble metal M solutions with Au and Pd concentrations of 0.01mol/L respectively for the noble metal source, wherein M is Au and Pd.
Step S2: a certain stoichiometric amount of PdCl2And HAuCl4The solution is diluted to 2.0X 10 with deionized water-4mol/L concentration. Adding a certain amount of PVA into the noble metal solution in an ice-water bath, wherein AuPd2The PVA mass ratio is 1.0:1.5, and the mixture is stirred vigorously for 10 min.
Step S3: fast injection0.1mol/L NaBH4Aqueous solution of AuPd2/NaBH4The molar ratio is 1.0:5.0, and the noble metal sol is obtained after continuously stirring for 20 min.
Step S4: AuPd by theory2Loading of 1.0 wt.% of a certain amount of porous Co3O4Adding a monodisperse microsphere carrier into a noble metal sol, carrying out ultrasonic treatment on the obtained suspension for 30s at 60kHz, stirring the suspension for 10h by adopting magnetic stirring operation until the colloidal gold is completely adsorbed, fading the color of the suspension, carrying out suction filtration, and using the solid for next treatment;
step S5: washing the obtained solid with 2.0L deionized water, drying in 80 deg.C oven for 12h, roasting in muffle furnace, heating from room temperature to 450 deg.C at 1 deg.C/min rate, and maintaining at the temperature for 4h to obtain AuPd2Porous Co3O4Monodisperse microspherical catalyst.
Wherein, the XRD spectrum of the sample prepared in this example is shown in the curve (d) of FIG. 1, and the AuPd prepared by comparing with the standard XRD spectrum of cobalt oxide sample2Porous Co3O4The monodisperse microsphere catalyst has cubic Co3O4Crystal structure of supported AuPd2Does not cause Co3O4The crystal structure is obviously changed; HRTEM image of the sample is detailed in FIG. 2, panel (f), from AuPd2Porous Co3O4As can be seen from the high-resolution TEM photograph of the monodisperse microspherical catalyst, a plurality of AuPd with uniform size and 3-5nm particle size2Nanoparticles highly dispersed in Co3O4The surface of monodisperse microspheres; the toluene oxidation activity of the sample at a toluene concentration of 1000ppm, a toluene to oxygen molar ratio of 1/400 and a space velocity of 20000mL/(gh) is shown in detail in the graph (d) in FIG. 3, from which it can be seen that the toluene conversion increases with the increase of the reaction temperature, and AuPd2Porous Co3O4The monodisperse microsphere catalyst shows the highest catalytic activity, and the reaction temperature is 195 ℃ when the toluene conversion rate is 90 percent, which is obviously superior to that of Co3O4Monodisperse microspheres, Au/porous Co3O4Monodisperse microspheres and Pd/porous Co3O4Monodisperse microspherical catalyst.
Comparative example 1
Porous Co3O4Monodisperse microspheres were prepared as in example 1.
Preparation of Au/porous Co3O4Monodisperse microsphere catalyst:
step 1: with HAuCl4Preparing corresponding 0.01mol/L noble metal solution for the noble metal source.
Step 2: adding a stoichiometric amount of HAuCl4The solution is diluted to 2.0X 10 with deionized water-4And (3) adding a certain amount of PVA into the noble metal solution in an ice-water bath at the mol/L concentration, wherein the mass ratio of Au to PVA is 1.0:1.5, and vigorously stirring for 10 min.
And step 3: fast injection of 0.1mol/L NaBH4Aqueous solution, Au/NaBH4The molar ratio is 1.0:5.0, and the sol is obtained after continuously stirring for 20 min.
And 4, step 4: a certain amount of porous Co is added according to the theoretical Au loading of 1.0wt percent3O4Adding the monodisperse microsphere carrier into the sol, treating the obtained suspension liquid with ultrasonic waves for 30s at 60kHz, and stirring the suspension system for 10h by adopting the operation of magnetic stirring until the colloidal gold is completely adsorbed, namely the color of the solution is faded. And (5) carrying out suction filtration to obtain a solid.
And 5: washing the solid with 2.0L deionized water, drying in an oven at 80 deg.C for 12h, calcining in a muffle furnace at 1 deg.C/min from room temperature to 450 deg.C and holding at the temperature for 4h to obtain Au/porous Co3O4Monodisperse microspherical catalyst.
Wherein, the XRD spectrogram of the sample prepared in the comparative example is shown in the curve (b) in the figure 1, and the prepared Au/porous Co can be known by comparing with the standard XRD spectrogram of the cobalt oxide sample3O4The monodisperse microsphere catalyst has cubic Co3O4Crystal structure, Au loading does not result in Co3O4The crystal structure changed significantly from that of the sample AuPd 2/porous Co obtained in example 13O4The monodisperse microspherical catalyst is consistent; HRTEM image of sample prepared in this comparative example is detailed in FIG. 2, panel (d), from Au/porous Co3O4High resolution TEM image of the monodisperse microspherical catalyst was observed, which is similar to the AuPd sample prepared in example 12Porous Co3O4The same as the monodisperse microspherical catalyst, a plurality of Au nano particles with uniform size and 3-5nm of particle size are highly dispersed in Co3O4The surface of monodisperse microspheres; the toluene oxidation activity curve of the sample prepared in the comparative example under the conditions of the toluene concentration of 1000ppm, the toluene-oxygen molar ratio of 1/400 and the space velocity of 20000mL/(gh) is shown in the graph (b) in FIG. 3, the reaction temperature when the toluene conversion rate is 90% is 260 ℃, which is much higher than that of the sample AuPd prepared in the example2Porous Co3O4T90% (195 ℃) of monodisperse microspherical catalyst.
Comparative example 2
Porous Co3O4Monodisperse microspheres were prepared as in example 1.
Preparation of Pd/porous Co3O4Monodisperse microsphere catalyst:
step 1: with PdCl2Preparing a noble metal solution with Pd concentration of 0.01mol/L for a noble metal source;
step 2: a certain stoichiometric amount of PdCl2The solution is diluted to 2.0X 10 with deionized water-4Adding a certain amount of PVA into the noble metal solution in an ice-water bath at the mol/L concentration, wherein the mass ratio of Pd to PVA is 1.0:1.5, and stirring vigorously for 10 min;
step 3, quickly injecting 0.1mol/L NaBH4Aqueous solution of Pd/NaBH4The mol ratio is 1.0:5.0, and sol is obtained after continuously stirring for 20 min;
and 4, step 4: a certain amount of porous Co is added according to the theoretical Pd loading of 1.0 wt%3O4Adding monodisperse microsphere carrier into solAnd treating the obtained suspension by ultrasonic waves of 60kHz for 30s, and stirring the suspension for 10h by adopting magnetic stirring operation until the colloidal gold is completely adsorbed and the color of the suspension fades. And (5) carrying out suction filtration to obtain a solid.
And 5: washing the solid with 2.0L deionized water, drying in 80 deg.C oven for 12h, roasting in muffle furnace, heating from room temperature to 450 deg.C at 1 deg.C/min rate, and maintaining at the temperature for 4h to obtain Pd/porous Co3O4Monodisperse microspherical catalyst.
Wherein, the XRD spectrogram of the sample prepared in the comparative example is shown in the curve (c) in the figure 1, and the prepared Pd/porous Co can be known by comparing with the standard XRD spectrogram of the cobalt oxide sample3O4The monodisperse microsphere catalyst has cubic Co3O4Crystal structure, supported Pd does not result in Co3O4The crystal structure changed significantly, which is the same as that of AuPd of the sample prepared in example 12Porous Co3O4The monodisperse microspherical catalyst is consistent; HRTEM image of sample prepared in this comparative example is detailed in FIG. 2, panel (e), from Pd/porous Co3O4High resolution TEM image of the monodisperse microspherical catalyst was observed, which is similar to the AuPd sample prepared in example 12Porous Co3O4Like the monodisperse microspherical catalyst, a plurality of Pd nano-particles with uniform size and 3-5nm of particle diameter are highly dispersed in Co3O4The surface of monodisperse microspheres; the toluene oxidation activity of the sample prepared in this comparative example under the conditions of a toluene concentration of 1000ppm, a toluene/oxygen molar ratio of 1/400 and a space velocity of 20000mL/(gh) is shown in the graph (c) in FIG. 3, and the reaction temperature at 90% toluene conversion is 223 ℃ higher than that of the AuPd sample prepared in example 12Porous Co3O4T90% (195 ℃) of monodisperse microspherical catalyst.
The above description is only exemplary of the invention, and any modification, equivalent replacement, and improvement made within the spirit and scope of the present invention should be considered within the scope of the present invention.
Claims (7)
1. Porous Co3O4The Au-Pd alloy nano catalyst loaded on the monodisperse microspheres is characterized by comprising Co with the monodisperse microsphere morphology formed by the agglomeration of porous cubes3O4The carrier is characterized in that Au-Pd alloy is loaded on the pore wall of the carrier.
2. Porous Co according to claim 13O4The Au-Pd alloy nano-catalyst loaded by the monodisperse microspheres is characterized in that the loading of the Au-Pd alloy is 1.0 to E2.0wt％。
3. Porous Co as claimed in claim 13O4The preparation method of the Au-Pd alloy nano-catalyst loaded by the monodisperse microspheres is characterized in that CoCl is used2·6H2Preparing Co with porous cubic coalescence monodisperse microspherical morphology by taking O and urea as raw materials and adopting a glycerol-assisted solvothermal method3O4Carrier, then NaBH is adopted under the protection of PVA4Au-Pd alloy nano particles are loaded on the Co by a reduction method3O4On a carrier.
4. Porous Co according to claim 33O4The preparation method of the Au-Pd alloy nano catalyst loaded by the monodisperse microspheres is characterized by comprising the following steps of:
step 1: adding CoCl2·6H2Dissolving O in a mixed solution of deionized water, glycerol and urea, and stirring for 1-3 h; wherein the CoCl2·6H2The mass ratio of the O to the urea is 1-3: 1-3;
step 2: transferring the solution obtained in the step 1 into a stainless steel self-pressing kettle with a polytetrafluoroethylene lining of 90-110 mL, carrying out hydrothermal treatment at 110-130 ℃ for 11-13 h, and then carrying out centrifugal separation on the solution to obtain a precipitate;
and step 3: washing the precipitate obtained after the hydrothermal treatment with absolute ethyl alcohol and deionized water for three times, and drying in an oven at 70-90 ℃ for 11-13 h to obtain magenta powder;
and 4, step 4: roasting the magenta powder obtained in the step 3 in a muffle furnace, raising the temperature from room temperature to 480-520 ℃ at the speed of 1-3 ℃/min, and keeping the temperature for 2-5 hours to obtain porous Co3O4A monodisperse microsphere carrier.
5. Porous Co according to claim 43O4The preparation method of the monodisperse microsphere loaded Au-Pd alloy nano catalyst is characterized in thatThe glycerol-assisted solvothermal method specifically comprises the following steps:
step 1: adding CoCl2·6H2Dissolving O in a mixed solution of deionized water, glycerol and urea, and stirring for 1 h; wherein the CoCl2·6H2The mass ratio of O to urea is 1: 1;
step 2: transferring the solution obtained in the step 1 into a 100mL stainless steel self-pressure kettle with a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 120 ℃ for 12h, and then carrying out centrifugal separation on the solution to obtain a precipitate;
and step 3: washing the precipitate obtained after the hydrothermal treatment with absolute ethyl alcohol and deionized water for three times, and drying in an oven at 80 ℃ for 12 hours to obtain magenta powder;
and 4, step 4: roasting the magenta powder obtained in the step 3 in a muffle furnace, raising the temperature from room temperature to 500 ℃ at the speed of 1 ℃/min, and keeping the temperature for 3 hours to obtain porous Co3O4A monodisperse microsphere carrier.
6. Porous Co according to claim 33O4The preparation method of the Au-Pd alloy nano-catalyst loaded by the monodisperse microspheres is characterized in that the NaBH protected by the PVA is prepared4The reduction method specifically comprises the following steps:
step S1: taking noble metals Au and Pd to prepare a noble metal M solution with Au and Pd concentrations of 0.01-0.03 mol/L respectively, wherein M is Au and Pd;
step S2: 0.01 to 0.03mol/L of noble metal solution is diluted to 2.0 to 2.2 x 10-4mixing PVA with the diluted noble metal solution in an ice water bath according to the mass ratio of M to PVA of 1.0-1.2: 1.0-1.5, and violently stirring for 10-15 min;
step S3: injecting 0.1-0.5 mol/L NaBH4Continuously stirring the aqueous solution for 20-30 min to obtain a noble metal sol; wherein the NaBH4According to M: NaBH4Adding the mixture according to the molar ratio of 1.0-1.2: 5.0-5.3;
step S4: the porous Co is added according to the proportion that the theoretical loading of the noble metal is 1.0-2.0 wt%3O4Adding the monodisperse microsphere carrier into the noble metal sol, carrying out ultrasonic treatment on the obtained suspension for 30-50 s, and stirring for 10-11 h until the colloidal gold is completely adsorbed; carrying out suction filtration to obtain a solid;
step S5: washing the solid with water, drying in an oven at 80-85 ℃ for 10-12 h, roasting in a muffle furnace, raising the temperature from room temperature to 450-460 ℃ at the speed of 1-3 ℃/min, and keeping the temperature for 4-4.2 h to obtain the porous Co3O4The monodisperse microsphere loads Au-Pd alloy nano-catalyst.
7. Porous Co according to claim 63O4The preparation method of the Au-Pd alloy nano-catalyst loaded by the monodisperse microspheres is characterized in that the NaBH protected by the PVA is prepared4The reduction method specifically comprises the following steps:
step S1: taking noble metals Au and Pd to prepare noble metal M solutions with Au and Pd concentrations of 0.01mol/L respectively, wherein M is Au and Pd;
step S2: 0.01mol/L noble metal solution is diluted to 2.0 multiplied by 10-4mixing PVA with the diluted noble metal solution in an ice water bath according to the mass ratio of M to PVA of 1.0:1.5, and violently stirring for 10 min;
step S3: injecting 0.1mol/L NaBH4Continuously stirring the aqueous solution for 20min to obtain noble metal sol; wherein the NaBH4According to M: NaBH4Adding the mixture according to the molar ratio of 1.0: 5.0;
step S4: the porous Co is added according to the proportion that the theoretical loading of the noble metal is 1.0wt percent3O4Adding the monodisperse microsphere carrier into the noble metal sol, carrying out ultrasonic treatment on the obtained suspension for 30s, and stirring for 10h until the colloidal gold is completely adsorbed; carrying out suction filtration to obtain a solid;
step S5: washing the solid with water, drying in an oven at 80 deg.C for 12h, calcining in a muffle furnace, heating from room temperature to 450 deg.C at 1 deg.C/min for 4h to obtain porous Co3O4The monodisperse microsphere loads Au-Pd alloy nano-catalyst.
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| CN113546622A (en) * | 2021-06-03 | 2021-10-26 | 南京大学 | Catalyst for catalytic oxidation of toluene at low temperature and high activity, and preparation method and application thereof |
| CN117654547A (en) * | 2024-01-29 | 2024-03-08 | 上海大格生物科技有限公司 | Pd/Co 3 O 4 Nano enzyme material, preparation method and application thereof in immunohistochemistry |
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| CN110639548A (en) * | 2019-09-19 | 2020-01-03 | 北京工业大学 | Monoatomic palladium-cobalt bimetallic nano-catalyst for efficiently catalyzing benzene oxidation |
| CN110639548B (en) * | 2019-09-19 | 2022-06-14 | 北京工业大学 | Monoatomic palladium-cobalt bimetallic nano-catalyst for efficiently catalyzing benzene oxidation |
| CN111185166A (en) * | 2020-01-14 | 2020-05-22 | 北京工业大学 | Supported platinum-tungsten bimetallic nano catalyst for efficiently catalyzing and oxidizing benzene |
| CN113546622A (en) * | 2021-06-03 | 2021-10-26 | 南京大学 | Catalyst for catalytic oxidation of toluene at low temperature and high activity, and preparation method and application thereof |
| CN113546622B (en) * | 2021-06-03 | 2022-06-10 | 南京大学 | Catalyst for catalytic oxidation of toluene at low temperature and high activity, and preparation method and application thereof |
| CN113540480A (en) * | 2021-08-17 | 2021-10-22 | 北京化工大学 | Regularly coordinated cobalt or iron doped cobalt-based electrocatalyst and preparation and use thereof |
| CN117654547A (en) * | 2024-01-29 | 2024-03-08 | 上海大格生物科技有限公司 | Pd/Co 3 O 4 Nano enzyme material, preparation method and application thereof in immunohistochemistry |
| CN117654547B (en) * | 2024-01-29 | 2024-04-09 | 上海大格生物科技有限公司 | Pd/Co 3 O 4 Nano enzyme material, preparation method and application thereof in immunohistochemistry |
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