CN115414962A - Method for preparing molecular sieve loaded multi-element alloy nanoparticle material - Google Patents
Method for preparing molecular sieve loaded multi-element alloy nanoparticle material Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 160
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 87
- 229910001325 element alloy Inorganic materials 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 26
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000000889 atomisation Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
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- 238000001816 cooling Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
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- 239000011565 manganese chloride Substances 0.000 claims description 7
- 229940099607 manganese chloride Drugs 0.000 claims description 7
- 150000002484 inorganic compounds Chemical class 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 abstract description 73
- 229910045601 alloy Inorganic materials 0.000 abstract description 70
- 239000000126 substance Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000005204 segregation Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 229910002058 ternary alloy Inorganic materials 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 3
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- 239000000243 solution Substances 0.000 description 25
- 229910002059 quaternary alloy Inorganic materials 0.000 description 17
- 238000003917 TEM image Methods 0.000 description 14
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- 238000002360 preparation method Methods 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 5
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000007704 wet chemistry method Methods 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910002847 PtSn Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PPWHTZKZQNXVAE-UHFFFAOYSA-N Tetracaine hydrochloride Chemical compound Cl.CCCCNC1=CC=C(C(=O)OCCN(C)C)C=C1 PPWHTZKZQNXVAE-UHFFFAOYSA-N 0.000 description 1
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- -1 ion exchange methods Chemical compound 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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Abstract
The invention discloses a method for preparing a molecular sieve supported multi-element alloy nanoparticle material, which comprises the following steps: 1. preparing a precursor suspension containing a carrier; 2. atomizing and drying to obtain precursor-loaded molecular sieve powder; 3. calcining and reducing to obtain the molecular sieve loaded multi-element alloy nano-particle material. According to the invention, through atomization drying, each metal element forms precursor nano particles and is uniformly loaded on the surface of the molecular sieve carrier without time for diffusion and segregation, so that the uniform dispersibility of each alloy element is improved, the specific surface area of the multi-element alloy nano particles in a product is improved, more metal active sites are provided, the synergistic effect among components of the multi-element alloy is exerted, the catalytic performance of the molecular sieve loaded multi-element alloy nano particle material is improved, the limitation that the alloy components do not exceed ternary alloy when the molecular sieve loaded alloy nano particle material is prepared by a conventional wet chemical method is broken through, and the application potential of the multi-element alloy material in the field of catalysis is favorably expanded.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a method for preparing a molecular sieve loaded multi-element alloy nano particle material.
Background
The molecular sieve has a regular pore system, high specific surface area, good thermal stability and hydrothermal stability, and can load a plurality of active components to be applied to industrial catalytic reaction. The metal-loaded molecular sieves have good catalytic performance in oxidation, hydrogenation, dehydrogenation, hydroisomerization, selective catalytic reduction with ammonia, and the like, and thus have been studied intensively.
With the research and application of metal-supported molecular sieves, relevant researchers have realized that the preparation of more metals as alloys supported on molecular sieves can utilize the intermetallic synergy to obtain catalytic materials with higher performance than single-component metals. For example, jin equals the paper published in Science in 2020 that AuPd alloy loaded molecular sieve performs better than Au or Pd loaded molecular sieve alone in the catalytic oxidation of methane to methanol, and a series of works of Corma topic group confirm that PtSn alloy loaded molecular sieve can improve propylene selectivity when catalyzing propane dehydrogenation to propylene compared with molecular sieve loaded with Pt alone. Therefore, the search for supporting alloys with stronger composition synergy on molecular sieves is considered by some related researchers to be the direction of important attention for future metal-supported molecular sieve materials.
Multi-principal element alloys refer to alloys containing a plurality of principal elements in equal or substantially similar molar ratios. Compared with binary alloys, the alloy has more diversified compositions, can tailor components for specific reactions, and has more complex interaction among components. The active component serving as a substitute for single-component metal or binary alloy is loaded on a molecular sieve carrier, so that the performance of the metal-loaded molecular sieve catalyst is expected to be further improved.
At present, various methods are available for loading metals on molecular sieves, including ion exchange methods, impregnation methods, direct synthesis using metal organic complexes as raw materials, and the like. However, the above method relates to material synthesis and preparation under wet chemical method, and the article published in Science by Yao et al 2018 and the article published in Nature Communication by Gao et al 2021 both indicate that the conventional wet chemical method for preparing more than ternary alloy nanoparticles has difficulty in solving the problem of component segregation caused by the difference of energy required for the reduction of different metal components. Although the metal nanoparticle-supporting and binary alloy-supporting molecular sieves can be prepared by a solvent-free synthesis method using silicon oxide coating the metal nanoparticles or a small amount of seed crystals of the molecular sieve supporting the metal nanoparticles on the surface as the raw material, a liquid-phase chemical method is still required for preparing the raw material supporting the metal nanoparticles in these examples, and thus the above problems cannot be completely circumvented. Therefore, the existing method can not well meet the requirement of preparing the molecular sieve material loaded with the multi-element alloy nanoparticles, and a new method for preparing the multi-element alloy-loaded molecular sieve with high efficiency and low cost needs to be developed.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a molecular sieve supported multicomponent alloy nanoparticle material, aiming at the defects of the prior art. The method comprises the steps of dispersing a molecular sieve carrier in a multi-element alloy precursor solution to prepare a precursor suspension containing the carrier, atomizing and drying the precursor suspension, so that each metal element can form precursor nano particles and be uniformly loaded on the surface of the molecular sieve carrier in time of diffusion and segregation, the uniform dispersibility of each element alloy element is improved, more metal active sites are provided, the catalytic performance of the molecular sieve loaded multi-element alloy nano particle material is improved, and the problem of component segregation in the conventional wet chemistry method is solved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing a molecular sieve supported multi-element alloy nanoparticle material is characterized by comprising the following steps:
dispersing a molecular sieve carrier in a multi-element alloy precursor solution prepared from ultrapure water, ethanol and a metal inorganic compound, and continuously stirring to obtain a precursor suspension containing the carrier;
step two, atomizing and drying the precursor suspension containing the carrier obtained in the step one to obtain precursor-loaded molecular sieve powder;
and step three, calcining and reducing the precursor-loaded molecular sieve powder obtained in the step two to obtain the molecular sieve-loaded multi-element alloy nanoparticle material.
The invention disperses a molecular sieve carrier in a multi-element alloy precursor solution to prepare a precursor suspension containing the carrier, and the precursor suspension containing the carrier is atomized and dried, the precursor suspension is atomized and dispersed by high-pressure gas at an atomizing nozzle by utilizing atomization, converted into micro liquid drops with uniform components, and then quickly dried in high-temperature gas in a drying chamber, as the liquid drops are micro and the solvent volatilization speed is high, solutes, namely metal elements, in the micro liquid drops can not diffuse and segregate in time to form precursor nano particles and uniformly load the precursor nano particles on the surface of the molecular sieve carrier, and the molecular sieve loaded multi-element alloy nano particle material is obtained by calcining and reducing, so that the uniform dispersity of all element alloy elements in the molecular sieve loaded multi-element alloy nano particle material is improved, the problem of component segregation in the conventional wet chemical method is solved, and the limitation that the alloy components do not exceed ternary alloy when the molecular sieve loaded alloy nano particle material is prepared by the conventional wet chemical method is broken through; meanwhile, the small-size multi-element alloy nanoparticles highly dispersed and uniformly distributed on the molecular sieve carrier greatly improve the specific surface area of the multi-element alloy nanoparticles, provide more metal active sites for the molecular sieve loaded multi-element alloy nanoparticle material and improve the catalytic performance of the molecular sieve loaded multi-element alloy nanoparticle material.
The method for preparing the molecular sieve supported multi-element alloy nanoparticle material is characterized in that in the step one, the framework structure of the molecular sieve support is MFI, * BEA, FAU or MOR types. In fact, the framework structure of the molecular sieve carrier in the invention is not limited to the type commonly used in the industrial production, and molecular sieves with other topologies can also be used as the carrierAnd (3) a body. The invention can adopt molecular sieves with various framework structure types as carriers, meets the requirements of different types of catalytic reactions on the molecular sieve carrier structures, and is favorable for realizing customized production.
The method for preparing the molecular sieve supported multi-element alloy nanoparticle material is characterized in that in the first step, the metal inorganic compound is more than three of ammonium chloroplatinate, palladium chloride, copper chloride, cobalt chloride, manganese chloride, ferric chloride, ruthenium chloride, chloroauric acid, silver nitrate, ammonium tungstate and ammonium molybdate. According to different requirements of specific catalytic reactions, the specific combination of the metal inorganic compounds is selected as a precursor, so that the composition of the multi-element alloy in the product is changed, the synergistic effect among the components is enhanced, and the more efficient catalytic action can be exerted.
The method for preparing the molecular sieve supported multi-element alloy nanoparticle material is characterized in that the calcining reduction process in the third step is as follows: putting the molecular sieve powder loaded with the precursor in a reducing atmosphere, heating to 300 ℃ at a heating rate of 2-10 ℃/min, then preserving heat for 1-2 h, then heating to 600 ℃ at a heating rate of 2-10 ℃/min, then preserving heat for 1-2 h, and then cooling to room temperature. According to the invention, calcination reduction is carried out in a reducing atmosphere, so that the precursor is guaranteed to be decomposed, and each metal ion in the precursor is reduced to generate a simple alloy phase which is combined with a molecular sieve carrier to form a molecular sieve loaded multi-element alloy nanoparticle material; meanwhile, the molecular sieve powder loaded with the precursor is uniformly heated and reduced in a short time by controlling the heating speed, so that the structure of the product is not damaged, the problem of overlong preparation period caused by too low heating speed is avoided, and the problems of structural damage of the molecular sieve carrier and uneven heating of the sample caused by too high heating speed are avoided.
The method for preparing the molecular sieve supported multi-element alloy nanoparticle material is characterized in that the multi-element alloy in the molecular sieve supported multi-element alloy nanoparticle material in the third step is composed of more than three metal elements, and the size of the molecular sieve supported multi-element alloy nanoparticle material is 5 nm-20 nm. More preferably, the multicomponent alloy in the molecular sieve supported multicomponent alloy nanoparticle material is composed of more than five metal elements, and each metal element accounts for 5-35% of the high-entropy alloy nanoparticles in mole percentage of the alloy. The preparation method provided by the invention meets the preparation requirement of the molecular sieve carrier loaded multi-element alloy nanoparticles, forms simple solid solution phase alloy nanoparticles with stable structure and multi-element effect, breaks through the limitation that the alloy components do not exceed the ternary alloy when the molecular sieve loaded alloy nanoparticle material is prepared by the conventional wet chemistry method, provides a possibility for preparing a novel catalytic material, and is beneficial to expanding the application potential of the multi-element alloy material in the catalytic field.
Compared with the prior art, the invention has the following advantages:
1. the molecular sieve carrier is dispersed in the multi-element alloy precursor solution to prepare the precursor suspension containing the carrier, and the precursor suspension is atomized and dried, so that the metal elements can form precursor nano particles and can be uniformly loaded on the surface of the molecular sieve carrier in time of diffusion and segregation, the uniform dispersibility of the alloy elements is improved, the specific surface area of the multi-element alloy nano particles in the product is improved, more metal active sites are provided, the synergistic effect among the multi-element alloy components is exerted, the catalytic performance of the molecular sieve loaded multi-element alloy nano particle material is improved, and the problem of component segregation in the conventional wet chemical method is solved.
2. According to the invention, through an atomization drying method, the uniform dispersibility of each element alloy element on the surface of the molecular sieve carrier is improved, the limitation that the alloy components do not exceed ternary alloy when the molecular sieve loaded alloy nanoparticle material is prepared by a conventional wet chemical method is broken through, and even the molecular sieve loaded quinary or higher high-entropy alloy nanoparticle material can be prepared, thereby being beneficial to expanding the application potential of the multi-element alloy material in the field of catalysis.
3. According to the invention, ethanol with the volume fraction of more than 10% and ultrapure water are added into the precursor suspension containing the carrier to form an azeotrope, so that the drying speed of micro droplets in the atomization drying process is improved, the growth of multi-element nano alloy particles is effectively limited, the problem of overlarge size of the multi-element nano alloy particles caused by low drying speed is avoided, the specific surface area of the multi-element alloy nano particles in the product is increased, and the catalytic performance of the molecular sieve loaded multi-element alloy nano particle material is further improved.
4. Compared with the preparation method adopting the metal organic complex, the preparation method only adopts inorganic metal salt, ethanol, ultrapure water and a molecular sieve as raw materials, reduces the cost of the raw materials, only relates to two processes of spray drying and calcination reduction, is simple to operate, has no special requirement on equipment, and is suitable for large-scale industrial production.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a process diagram of preparing a molecular sieve supported multicomponent alloy nanoparticle material according to the present invention.
FIG. 2 is an XRD spectrum of a ZSM-5 molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in example 1 of the present invention.
FIG. 3a is a low-magnification TEM image of a ZSM-5 molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in example 1 of the present invention.
FIG. 3b is a high-magnification TEM image of a ZSM-5 molecular sieve loaded PtPdCuCoMn quinary alloy nanoparticle material prepared in example 1 of the present invention.
Fig. 4a is a STEM diagram of a ZSM-5 molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in example 1 of the present invention.
FIG. 4b is a distribution diagram of Pt elements in the ZSM-5 molecular sieve loaded PtPdCuCoMn quinary alloy nanoparticle material prepared in example 1 of the present invention.
Fig. 4c is a Pd element distribution diagram in a ZSM-5 molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in example 1 of the present invention.
FIG. 4d is a Cu element distribution diagram of a ZSM-5 molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in example 1 of the present invention.
Fig. 4e is a distribution diagram of Co element in the ZSM-5 molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in example 1 of the present invention.
FIG. 4f is a distribution diagram of Mn elements in the ZSM-5 molecular sieve loaded PtPdCuCoMn quinary alloy nanoparticle material prepared in example 1 of the invention.
FIG. 5 is a TEM image of a ZSM-5 molecular sieve loaded PtPdCuCoMn quinary alloy nanoparticle material prepared in comparative example 1 of the invention.
FIG. 6a is a low-power TEM image of a ZSM-5 molecular sieve loaded PtPdCuCo quaternary alloy nanoparticle material prepared in example 2 of the present invention.
FIG. 6b is a high-power TEM image of the quaternary alloy nanoparticle material PtPdCuCo loaded with ZSM-5 molecular sieve prepared in example 2 of the present invention.
Fig. 7 is an XRD spectrogram of the Beta molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in example 3 of the present invention.
Fig. 8a is a low-power TEM image of a Beta molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in example 3 of the present invention.
Fig. 8b is a high power TEM image of the Beta molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in example 3 of the present invention.
Detailed Description
Example 1
As shown in fig. 1, the present embodiment includes the following steps:
step one, dissolving ammonium chloroplatinate, palladium chloride, copper chloride, cobalt chloride and manganese chloride with the same amount of substances into 10% ethanol ultrapure water solution, enabling the total concentration of metal salts to be 4.2mmol/L, preparing to obtain a multi-element alloy precursor solution, adding a ZSM-5 molecular sieve for dispersion, continuously stirring and uniformly dispersing, wherein the mass ratio of the ZSM-5 molecular sieve to the multi-element alloy precursor solution is 1;
step two, atomizing and drying the precursor suspension containing the carrier obtained in the step one to obtain precursor-loaded molecular sieve powder; the atomization drying process comprises the following steps: keeping the flow of the precursor suspension containing the carrier pumped into the spray drying equipment at 2.0mL/min, the atomization air pressure at 0.2MPa, the inlet temperature at 180 ℃ and the flow of hot air at 3.0L/min, and carrying out spray drying;
step three, the loaded precursor obtained in the step two is processedCalcining and reducing the molecular sieve powder to obtain a ZSM-5 molecular sieve loaded PtPdCuCoMn quinary alloy nanoparticle material; the calcining reduction process comprises the following steps: putting the molecular sieve powder loaded with the precursor into H with the volume content of 8 percent 2 Under the mixed atmosphere of-Ar, firstly heating to 300 ℃ at the heating rate of 10 ℃/min, then preserving heat for 1h, then heating to 600 ℃ at the heating rate of 10 ℃/min, then preserving heat for 1h, and then cooling to room temperature.
Fig. 2 is an XRD spectrogram of the ZSM-5 molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in this example, and fig. 2 shows a characteristic peak of the ZSM-5 molecular sieve and a characteristic peak corresponding to the crystal face of the alloy (111), which illustrates that the nanoparticle material of the ZSM-5 molecular sieve supported PtPdCuCoMn quinary alloy prepared in the present invention is obtained.
Fig. 3a is a low-power TEM image of the ZSM-5 molecular sieve-supported PtPdCuCoMn quinary alloy nanoparticle material prepared in this embodiment, and fig. 3b is a high-power TEM image of the ZSM-5 molecular sieve-supported PtPdCuCoMn quinary alloy nanoparticle material prepared in this embodiment, and as can be seen from fig. 3a and fig. 3b, the particle size of the PtPdCuCoMn quinary alloy nanoparticles in the ZSM-5 molecular sieve-supported PtPdCuCoMn quinary alloy nanoparticle material is 5nm to 20nm, the average particle size is 7.5nm, and the PtPdCuCoMn quinary alloy nanoparticles are uniformly dispersed on the surface of the ZSM-5 molecular sieve carrier.
Fig. 4a is a STEM diagram of a ZSM-5 molecular sieve loaded PtPdCuCoMn quinary alloy nanoparticle material prepared in this embodiment, and fig. 4b to fig. 4f are distribution diagrams of Pd, pt, cu, co, and Mn elements in the ZSM-5 molecular sieve loaded PtPdCuCoMn quinary alloy nanoparticle material prepared in embodiment 1 of the present invention, and as can be seen from fig. 4a to fig. 4f, the PtPdCuCoMn quinary alloy nanoparticles in the ZSM-5 molecular sieve loaded PtPdCuCoMn quinary alloy nanoparticle material contain Pd, pt, cu, co, and Mn alloy elements, and there is no obvious uneven distribution.
The framework structure of the molecular sieve carrier in the first step of the embodiment can also be replaced by FAU or MOR type; in the step one, the metal inorganic compound may be more than three of ammonium chloroplatinate, palladium chloride, copper chloride, cobalt chloride, manganese chloride, ferric chloride, ruthenium chloride, chloroauric acid, silver nitrate, ammonium tungstate and ammonium molybdate except for the combination of ammonium chloroplatinate, palladium chloride, copper chloride, cobalt chloride and manganese chloride.
Comparative example 1
The comparative example differs from example 1 in that: in the first step, ammonium chloroplatinate, palladium chloride, copper chloride, cobalt chloride and manganese chloride with equal amount of substances are dissolved in ultrapure water, but ethanol is not added.
FIG. 5 is a TEM image of a ZSM-5 molecular sieve loaded PtPdCuCoMn quinary alloy nanoparticle material prepared in the comparative example, and as can be seen from FIG. 5, the particle size of the PtPdCuCoMn quinary alloy nanoparticle in the ZSM-5 molecular sieve loaded PtPdCuCoMn quinary alloy nanoparticle material cannot be controlled to be 5nm to 20nm, and more large-sized particles appear, wherein the diameter of the largest-sized particle reaches 50nm.
Comparing the embodiment 1 with the comparative example 1, it can be seen that when the multi-component alloy precursor solution does not contain ethanol, the evaporation speed of the micro droplets formed by the conversion of the precursor suspension containing the carrier in the atomization drying process is slower, so that the PtPdCuCoMn quinary alloy nanoparticles have more time to grow, the specific surface area and the number of exposed active sites of the PtPdCuCoMn quinary alloy nanoparticles are reduced, and the catalytic performance of the PtPdCuCoMn quinary alloy nanoparticle material loaded by the ZSM-5 molecular sieve is influenced.
Example 2
As shown in fig. 1, the present embodiment includes the following steps:
step one, dissolving ammonium chloroplatinate, palladium chloride, copper chloride and cobalt chloride with equal substance amount into ethanol ultrapure water solution with volume fraction of 10%, making the total concentration of metal salt be 4.2mmol/L, preparing to obtain a multi-element alloy precursor solution, then adding a ZSM-5 molecular sieve for dispersion, continuously stirring and uniformly dispersing, wherein the mass ratio of the ZSM-5 molecular sieve to the multi-element alloy precursor solution is 1;
step two, carrying out atomization drying on the precursor suspension containing the carrier obtained in the step one to obtain precursor-loaded molecular sieve powder; the atomization drying process comprises the following steps: keeping the flow of the precursor suspension containing the carrier pumped into the spray drying equipment at 2.0mL/min, the atomization air pressure at 0.2MPa, the inlet temperature at 180 ℃ and the flow of hot air at 3.0L/min, and carrying out spray drying;
thirdly, calcining and reducing the precursor-loaded molecular sieve powder obtained in the second step to obtain a ZSM-5 molecular sieve loaded PtPdCuCo quaternary alloy nanoparticle material; the calcining reduction process comprises the following steps: putting the molecular sieve powder loaded with the precursor into H with the volume content of 8 percent 2 Under the-Ar mixed atmosphere, heating to 300 ℃ at the heating rate of 10 ℃/min, then preserving heat for 1h, then heating to 600 ℃ at the heating rate of 10 ℃/min, preserving heat for 1h, and then cooling to room temperature.
Fig. 6a is a low-power TEM image of a ZSM-5 molecular sieve-supported PtPdCuCo quaternary alloy nanoparticle material prepared in embodiment 2 of the present invention, and fig. 6b is a high-power TEM image of the ZSM-5 molecular sieve-supported PtPdCuCo quaternary alloy nanoparticle material prepared in this embodiment, and as can be seen from fig. 6a and 6b, the diameter of the PtPdCuCo quaternary alloy nanoparticle in the ZSM-5 molecular sieve-supported PtPdCuCo quaternary alloy nanoparticle material is 5nm to 20nm, and the PtPdCuCo quaternary alloy nanoparticle is uniformly dispersed on the surface of the ZSM-5 molecular sieve.
Example 3
As shown in fig. 1, the present embodiment includes the following steps:
step one, dissolving ammonium chloroplatinate, palladium chloride, copper chloride, cobalt chloride and manganese chloride with the same substance amount into ethanol ultra-pure water solution with the volume fraction of 10%, enabling the total concentration of metal salt to be 4.2mmol/L, preparing to obtain a multi-element alloy precursor solution, then adding a Beta molecular sieve for dispersion, continuously stirring and uniformly dispersing, wherein the mass ratio of the Beta molecular sieve to the multi-element alloy precursor solution is 1;
step two, atomizing and drying the precursor suspension containing the carrier obtained in the step one to obtain precursor-loaded molecular sieve powder; the atomization drying process comprises the following steps: keeping the flow of the precursor suspension containing the carrier pumped into the spray drying equipment at 2.0mL/min, the atomization air pressure at 0.2MPa, the inlet temperature at 180 ℃ and the flow of hot air at 3.0L/min, and carrying out spray drying;
step three, dividing the load precursor obtained in the step twoCalcining and reducing the sub-sieve powder to obtain a ZSM-5 molecular sieve loaded PtPdCuCoMn quinary alloy nanoparticle material; the calcining reduction process comprises the following steps: putting the molecular sieve powder loaded with the precursor into H with the volume content of 8% 2 Under the-Ar mixed atmosphere, heating to 300 ℃ at the heating rate of 10 ℃/min, then preserving heat for 1h, then heating to 600 ℃ at the heating rate of 10 ℃/min, preserving heat for 1h, and then cooling to room temperature.
Fig. 7 is an XRD spectrogram of the Beta molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in this example, and fig. 7 shows characteristic peaks of the Beta molecular sieve and characteristic peaks corresponding to the crystal face of the alloy (111), which illustrates that the nanoparticle material prepared by the Beta molecular sieve supported PtPdCuCo quaternary alloy in the present invention.
Fig. 8a is a low-power TEM image of the Beta molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in this example, and fig. 8b is a high-power TEM image of the Beta molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material prepared in this example, and as can be seen from fig. 8a and 8b, the diameter of the PtPdCuCoMn quinary alloy nanoparticle in the Beta molecular sieve supported PtPdCuCoMn quinary alloy nanoparticle material is 5nm to 20nm, and the PtPdCuCoMn is uniformly dispersed on the surface of the Beta molecular sieve support.
Example 4
As shown in fig. 1, the present embodiment includes the following steps:
step one, dissolving ammonium chloroplatinate, palladium chloride, copper chloride and cobalt chloride with equal substance amount into ethanol ultrapure water solution with volume fraction of 10%, making the total concentration of metal salt be 4.2mmol/L, preparing to obtain a multi-element alloy precursor solution, then adding a ZSM-5 molecular sieve for dispersion, continuously stirring and uniformly dispersing, wherein the mass ratio of the ZSM-5 molecular sieve to the multi-element alloy precursor solution is 1;
step two, atomizing and drying the precursor suspension containing the carrier obtained in the step one to obtain precursor-loaded molecular sieve powder; the atomization drying process comprises the following steps: keeping the flow of the precursor suspension containing the carrier pumped into the spray drying equipment at 2.0mL/min, the atomization air pressure at 0.2MPa, the inlet temperature at 180 ℃, and the flow of hot air at 3.0L/min, and carrying out spray drying;
calcining and reducing the precursor-loaded molecular sieve powder obtained in the step two to obtain a ZSM-5 molecular sieve loaded PtPdCuCo quaternary alloy nanoparticle material; the calcining reduction process comprises the following steps: putting the molecular sieve powder loaded with the precursor into H with the volume content of 8% 2 Under the mixed atmosphere of-Ar, firstly heating to 300 ℃ at the heating rate of 2 ℃/min, then preserving heat for 1h, then heating to 600 ℃ at the heating rate of 2 ℃/min, preserving heat for 1h, and then cooling to room temperature.
Through detection, the diameter of the PtPdCuCo quaternary alloy nanoparticles in the ZSM-5 molecular sieve loaded PtPdCuCo quaternary alloy nanoparticle material prepared in the embodiment is 5 nm-20 nm, and the PtPdCuCo quaternary alloy nanoparticles are uniformly dispersed on the surface of the ZSM-5 molecular sieve.
Example 5
As shown in fig. 1, the present embodiment includes the following steps:
step one, dissolving ammonium chloroplatinate, palladium chloride, copper chloride and cobalt chloride with the same amount of substances into ethanol ultra-pure water solution with the volume fraction of 10%, enabling the total concentration of metal salt to be 4.2mmol/L, preparing to obtain a multi-element alloy precursor solution, then adding a ZSM-5 molecular sieve for dispersion, continuously stirring and uniformly dispersing, wherein the mass ratio of the ZSM-5 molecular sieve to the multi-element alloy precursor solution is 1;
step two, atomizing and drying the precursor suspension containing the carrier obtained in the step one to obtain precursor-loaded molecular sieve powder; the atomization drying process comprises the following steps: keeping the flow of the precursor suspension containing the carrier pumped into the spray drying equipment at 2.0mL/min, the atomization air pressure at 0.2MPa, the inlet temperature at 180 ℃, and the flow of hot air at 3.0L/min, and carrying out spray drying;
calcining and reducing the precursor-loaded molecular sieve powder obtained in the step two to obtain a ZSM-5 molecular sieve loaded PtPdCuCo quaternary alloy nanoparticle material; the calcining reduction process comprises the following steps: putting the molecular sieve powder loaded with the precursor in a H2-Ar mixed atmosphere with the volume content of 8%, heating to 300 ℃ at the heating rate of 10 ℃/min, then preserving heat for 2H, then heating to 600 ℃ at the heating rate of 10 ℃/min, preserving heat for 2H, and then cooling to room temperature.
Through detection, the diameter of the PtPdCuCo quaternary alloy nanoparticles in the ZSM-5 molecular sieve loaded PtPdCuCo quaternary alloy nanoparticle material prepared in the embodiment is 5 nm-20 nm, and the PtPdCuCo quaternary alloy nanoparticles are uniformly dispersed on the surface of the ZSM-5 molecular sieve.
Example 6
As shown in fig. 1, the present embodiment includes the following steps:
step one, dissolving chloroauric acid, ammonium chloroplatinate, iridium chloride, palladium chloride and ruthenium chloride with equal substance amount in 10% ethanol ultrapure water solution, enabling the total concentration of metal salts to be 4.2mmol/L, preparing to obtain a multi-element alloy precursor solution, then adding a ZSM-5 molecular sieve for dispersion, continuously stirring and uniformly dispersing, wherein the mass ratio of the ZSM-5 molecular sieve to the multi-element alloy precursor solution is 1;
step two, atomizing and drying the precursor suspension containing the carrier obtained in the step one to obtain precursor-loaded molecular sieve powder; the atomization drying process comprises the following steps: keeping the flow of the precursor suspension containing the carrier pumped into the spray drying equipment at 2.0mL/min, the atomization air pressure at 0.2MPa, the inlet temperature at 180 ℃ and the flow of hot air at 3.0L/min, and carrying out spray drying;
thirdly, calcining and reducing the precursor-loaded molecular sieve powder obtained in the second step to obtain a ZSM-5 molecular sieve loaded AuPtIrPdRu quinary alloy nanoparticle material; the calcining reduction process comprises the following steps: putting the molecular sieve powder loaded with the precursor into a H2-Ar mixed atmosphere with the volume content of 8%, heating to 300 ℃ at the heating rate of 10 ℃/min, then preserving heat for 1H, then heating to 600 ℃ at the heating rate of 10 ℃/min, preserving heat for 1H, and then cooling to room temperature to obtain the ZSM-5 molecular sieve loaded AuPtIrPdRu quinary alloy nanoparticle material.
Through detection, the ZSM-5 molecular sieve loaded AuPtIrPdRu quinary alloy nanoparticle material prepared in the embodiment contains an MFI framework structure of a ZSM-5 molecular sieve and AuPtIrPdRu quinary alloy nanoparticles, and the diameter of the AuPtIrPdRu quinary alloy nanoparticles is 5 nm-20 nm.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (5)
1. A method for preparing a molecular sieve supported multi-element alloy nanoparticle material is characterized by comprising the following steps:
dispersing a molecular sieve carrier in a multi-element alloy precursor solution prepared from ultrapure water, ethanol and a metal inorganic compound, and continuously stirring to obtain a precursor suspension containing the carrier;
step two, carrying out atomization drying on the precursor suspension containing the carrier obtained in the step one to obtain precursor-loaded molecular sieve powder;
and step three, calcining and reducing the precursor-loaded molecular sieve powder obtained in the step two to obtain the molecular sieve-loaded multi-element alloy nanoparticle material.
2. The method for preparing the molecular sieve supported multi-element alloy nanoparticle material as claimed in claim 1, wherein the framework structure of the molecular sieve support in the step one is MFI, * BEA, FAU or MOR types.
3. The method for preparing the molecular sieve supported multi-element alloy nanoparticle material as claimed in claim 1, wherein in the step one, the metal inorganic compound is at least three of ammonium chloroplatinate, palladium chloride, copper chloride, cobalt chloride, manganese chloride, ferric chloride, ruthenium chloride, chloroauric acid, silver nitrate, ammonium tungstate and ammonium molybdate.
4. The method for preparing the molecular sieve supported multi-element alloy nanoparticle material as claimed in claim 1, wherein the calcination reduction in the third step is as follows: putting the molecular sieve powder loaded with the precursor in a reducing atmosphere, heating to 300 ℃ at a heating rate of 2-10 ℃/min, then preserving heat for 1-2 h, then heating to 600 ℃ at a heating rate of 2-10 ℃/min, then preserving heat for 1-2 h, and then cooling to room temperature.
5. The method for preparing the molecular sieve supported multi-element alloy nanoparticle material as claimed in claim 1, wherein the multi-element alloy in the molecular sieve supported multi-element alloy nanoparticle material in the third step is composed of three or more metal elements, and the size of the molecular sieve supported multi-element alloy nanoparticle material is 5nm to 20nm.
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