CN113477936A - Method and device for preparing palladium and palladium alloy nanocrystals - Google Patents
Method and device for preparing palladium and palladium alloy nanocrystals Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 334
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 35
- 229910001252 Pd alloy Inorganic materials 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 140
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 76
- 239000002070 nanowire Substances 0.000 claims abstract description 64
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 49
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 49
- 239000011734 sodium Substances 0.000 claims abstract description 49
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 38
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 38
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 38
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 28
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 28
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 28
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims abstract description 27
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 235000009518 sodium iodide Nutrition 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 12
- 238000006073 displacement reaction Methods 0.000 claims description 11
- 239000010931 gold Substances 0.000 claims description 11
- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000002073 nanorod Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 86
- 229910000510 noble metal Inorganic materials 0.000 description 16
- 238000003917 TEM image Methods 0.000 description 10
- 229910001020 Au alloy Inorganic materials 0.000 description 9
- 239000003353 gold alloy Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 241000219122 Cucurbita Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- XEOCKQIQXJNTER-UHFFFAOYSA-N gold palladium platinum Chemical compound [Pd].[Pd].[Pd].[Pd].[Pd].[Pt].[Pt].[Pt].[Pt].[Pt].[Pt].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au].[Au] XEOCKQIQXJNTER-UHFFFAOYSA-N 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007130 inorganic reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0466—Alloys based on noble metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/04—Nanocrystalline
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Abstract
The invention discloses a method and a device for preparing palladium and palladium alloy nanocrystals, which comprise the following steps: adding deionized water, a preset solution and polyvinylpyrrolidone into a reaction kettle, and uniformly oscillating by ultrasonic to generate a reaction solution, wherein the preset solution comprises one of sodium iodide, sodium bromide, potassium iodide and potassium bromide; when sodium chloropalladate with a first mass is added into the reaction solution, generating an ultralong palladium nanowire under the reaction conditions of high temperature and high pressure; when ascorbic acid and a second mass of sodium chloropalladate are added into the reaction solution, palladium nano cubic blocks and palladium nano rods are generated; when ascorbic acid and a third mass of sodium chloropalladate are added to the reaction solution, palladium nano-cubes are generated. Compared with the synthetic method in the prior art, the synthetic method has the advantages of simple processing steps, simple operation and easy repetition.
Description
Technical Field
The invention relates to the technical field of multidisciplinary solution synthesis, in particular to a method and a device for preparing palladium and alloy nanocrystals thereof.
Background
Because the noble metal nano crystal has special adjustable property and has potential application value in the fields of catalysis, photonics, electronics, biosensing, biomedical research and the like, the controllability of the crystal face morphology of the noble metal nano crystal is widely concerned. The noble metal palladium nanocrystal has strong catalytic capability in organic or inorganic reactions of hydrogenation and dehydrogenation, but the use cost of the noble metal palladium nanocrystal is always a main obstacle limiting the industrialization of the noble metal palladium nanocrystal. The focus of the researchers is to reduce the preparation cost of the noble metal palladium nanocrystal and improve the catalytic efficiency.
In the past decades, the methods for synthesizing noble metal catalysts are various, and the solution synthesis method which is easy to operate is one of the important means for preparing palladium nanocrystals with various shapes. The method obtains palladium nanocrystals in various shapes including cubes, tetrahedrons, octahedrons, rods, wires and the like by easily adjusting experimental parameters.
In the aspect of noble metal morphology control synthesis, many excellent subjects at home and abroad, for example, professor charnaea of georgia academy of technology, usa, are known to synthesize noble metal nanocrystals in a liquid phase, and in particular, the methodology and methodology of cage-structured noble metal nanomaterials they have created [ chem.rev.,2020, DOI:10.1021/acs. chemrev.0c00454 ]. A series of high-quality palladium-based nanocrystals with different morphologies [ Sci.adv.,2020,6, eaba9731 ] are synthesized by Angew.chem.int.Ed.2011,50, 6315-. Compared with bulk phase materials, the palladium-based nanocrystals have the advantages of large specific surface area, high catalytic activity and the like.
Although the typical synthesis method gives great inspiration and encouragement to the industry, the method still has the defects of complicated steps, poor repeatability, harsh reaction conditions and the like in the synthesis process.
Disclosure of Invention
The invention provides a method and a device for preparing palladium and alloy nanocrystals thereof, which are used for overcoming at least one technical problem in the prior art.
According to a first aspect of embodiments of the present invention, there is provided a method for preparing palladium and alloy nanocrystals thereof, comprising: adding deionized water, a preset solution and polyvinylpyrrolidone into a reaction kettle, and uniformly oscillating by ultrasonic to generate a reaction solution, wherein the preset solution comprises one of sodium iodide, sodium bromide, potassium iodide and potassium bromide; when sodium chloropalladate with a first mass is added into the reaction solution, generating an ultralong palladium nanowire under the reaction conditions of high temperature and high pressure; when ascorbic acid and a second mass of sodium chloropalladate are added into the reaction solution, palladium nano cubic blocks and palladium nano rods are generated; when ascorbic acid and a third mass of sodium chloropalladate are added to the reaction solution, palladium nano-cubes are generated.
Optionally, the reaction solution is used as it is, and the mass ratio of the polyvinylpyrrolidone to the preset solution is 0.5-2: 1-5.
Optionally, after the step of generating the ultra-long palladium nanowire under the reaction condition of high temperature and high pressure when the first mass of sodium chloropalladate is added into the reaction solution, the method further includes: and (3) taking the ultra-long palladium nanowire as a substrate, and putting a high-potential chloroauric acid trihydrate raw material into the reaction solution to perform atomic potential displacement or etching to generate the gourd-shaped palladium nanowire.
Optionally, the reaction solution is ready for preparation, and the mass ratio of gold to palladium atoms is 0.5-1: 0.01-0.5.
Optionally, the reaction temperature for generating the calabash-shaped palladium nanowire, the palladium nano cubic block and the palladium nano rod and the palladium nano cubic block is 50-100 ℃, and the reaction time is 1-5 h.
Optionally, the reaction temperature for generating the ultra-long palladium nanowire is 160-200 ℃, and the reaction time is 1-24 h.
Optionally, the step of using the ultra-long palladium nanowire as a substrate, and adding a high-potential chloroauric acid trihydrate raw material into the reaction solution to perform atomic potential displacement or etching to generate the gourd-shaped palladium nanowire includes: taking the ultra-long palladium nanowire as a substrate, putting a high-potential chloroauric acid trihydrate raw material into the reaction solution for atomic potential replacement or etching, and generating the calabash-shaped palladium nanowire through oil bath reaction; the step of generating palladium nano-cubes and palladium nano-rods when ascorbic acid and a second mass of sodium chloropalladate are added into the reaction solution comprises the following steps: when ascorbic acid and a second mass of sodium chloropalladate are added into the reaction solution, palladium nano cubic blocks and palladium nano rods are generated through oil bath reaction; the step of generating palladium nano-cubes when ascorbic acid and a third mass of sodium chloropalladate are added to the reaction solution comprises: when ascorbic acid and a third mass of sodium chloropalladate are added into the reaction solution, palladium nano-cubic blocks are generated through an oil bath reaction.
According to a second aspect of embodiments of the present invention, there is provided a device for preparing palladium and alloy nanocrystals thereof, comprising: the first generation module is used for adding a first mass of deionized water, a third mass of preset solution and a fourth mass of polyvinylpyrrolidone into the reaction kettle with the first capacity, and uniformly generating a reaction solution through ultrasonic oscillation, wherein the preset solution comprises one of sodium iodide, sodium bromide, potassium iodide and potassium bromide; the second generation module is used for generating the ultralong palladium nanowire under the high-temperature and high-pressure reaction condition when the sodium chloropalladate with the first mass is added into the reaction solution; a third generation module, configured to generate palladium nano-cubes and palladium nano-rods when ascorbic acid and a second mass of sodium chloropalladate are added to the reaction solution; and the fourth generation module is used for generating palladium nano cubic blocks when ascorbic acid and third mass of sodium chloropalladate are added into the reaction solution.
Optionally, the reaction solution is used as it is, and the mass ratio of the polyvinylpyrrolidone to the preset solution is 0.5-2: 1-5.
Optionally, the apparatus further comprises: and the fifth generation module is used for taking the ultra-long palladium nanowire as a substrate, and putting a high-potential chloroauric acid raw material into the reaction solution to perform atomic potential displacement or etching to generate the gourd-shaped palladium nanowire.
Optionally, the reaction solution is ready for preparation, and the mass ratio of gold to palladium atoms is 0.5-1: 0.01-0.5.
Optionally, the reaction temperature of the fifth generation module, the reaction temperature of the fourth generation module and the reaction temperature of the third generation module are 50-100 ℃, and the reaction time is 1-5 hours.
Optionally, the reaction temperature of the second generation module is 160-200 ℃, and the reaction time is 1-24 hours.
Optionally, the fifth generating module is specifically configured to use the ultra-long palladium nanowire as a substrate, put a high-potential chloroauric acid raw material into the reaction solution to perform atomic potential displacement or etching, and generate a gourd-shaped palladium nanowire through an oil bath reaction; the third generating module 503 is specifically configured to generate palladium nano-cubes and palladium nano-rods through an oil bath reaction when ascorbic acid and a second mass of sodium chloropalladate are added to the reaction solution; the fourth generating module 504 is specifically configured to generate palladium nano-cubes through an oil bath reaction when ascorbic acid and a third mass of sodium chloropalladate are added to the reaction solution.
The innovation points of the embodiment of the invention comprise:
1. the method and the device for preparing the palladium and the palladium alloy nanocrystalline provided by the invention adopt chloroauric acid trihydrate and sodium chloropalladate as noble metal source precursors, and prepare and generate the ultra-long palladium nanowire, the ultra-long palladium gold nanowire and the palladium nano cubic block smaller than 30nm under the conditions of polyvinylpyrrolidone, a preset solution (one of sodium iodide, sodium bromide, potassium iodide and potassium bromide), ascorbic acid and a deionized water system. The method has the characteristics of simple and convenient operation, green solvent, high yield, easy repetition and the like, has potential application prospects in the fields of photocatalysis, electrocatalysis, biomedicine, electronic science and the like, and has simple treatment steps, simple operation and easy repetition compared with the synthetic method in the prior art. Is one of the innovative points of the embodiment of the invention.
2. The invention provides a preparation method and a device of palladium-gold alloy nanocrystalline, which are used for constructing novel noble metal nano building blocks on the basis of palladium nanowires and nano cubic blocks, and the advantages of noble metals are complemented to achieve the maximum synergistic effect. Is one of the innovative points of the embodiment of the invention.
3. The invention can prepare a series of high-quality palladium and alloy nanocrystals thereof, and provides various alternatives in systematicness and substrate diversity. Is one of the innovative points of the embodiment of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1a is a schematic process flow diagram of the preparation method of palladium and its alloy nanocrystals of the present invention;
FIG. 1b is an SEM image and an embedded TEM image of the ultra-long palladium nanowires generated in example 1;
FIG. 2 is a TEM image of the ultra-long Pd/Au nanowires generated in example 2;
FIG. 3 is a TEM image of palladium nanocubes of different morphologies generated in example 3;
FIG. 4 is a TEM image of 30nm palladium nanocubes of example 4;
FIG. 5 is a TEM image of 30nm palladium-gold nanocubes of example 5;
FIG. 6 is a schematic structural diagram of an apparatus for preparing palladium and palladium alloy nanocrystals of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
It is to be noted that the terms "comprises" and "comprising" and any variations thereof in the embodiments and drawings of the present invention are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
The embodiment of the invention discloses a method and a device for preparing palladium and palladium alloy nanocrystals. The following are detailed below.
The invention provides a preparation method of palladium and an alloy nanocrystal thereof, which can flexibly prepare gold nanoparticles, gold nanorods, gold nanowires and gold nanoplates by adjusting the concentration of chloroauric acid. Referring to fig. 1a, fig. 1a is a process flow diagram of the preparation method of palladium and alloy nanocrystals thereof according to the present invention. As shown in fig. 1a, the preparation method of palladium and its alloy nanocrystal comprises the following steps:
step 101, adding deionized water, a preset solution and polyvinylpyrrolidone into a reaction kettle, and uniformly oscillating by ultrasonic to generate a reaction solution.
Wherein the preset solution comprises one of sodium iodide, sodium bromide, potassium iodide and potassium bromide.
In one implementation, the volume of the reaction kettle may be 50mL, the mass of the deionized water may be 36g, the mass of the preset solution may be 1g, and the mass of the polyvinylpyrrolidone may be 0.8 g. That is, in a 50mL reaction vessel, 36g of deionized water, 1g of the predetermined solution and 0.8g of polyvinylpyrrolidone were added.
In another implementation, the volume of the reaction kettle may be 100mL, the mass of the deionized water may be 72g, the mass of the preset solution may be 2g, and the mass of the polyvinylpyrrolidone may be 1.6 g.
102, when a first mass of sodium chloropalladate is added into the reaction solution, generating an ultralong palladium nanowire under the reaction conditions of high temperature and high pressure, and executing step 104.
Wherein the first mass comprises 18-58 mg.
In the step, under the conditions that the first mass is 18-58 mg and the mass ratio of the polyvinylpyrrolidone to the preset solution is unchanged, the ultra-long palladium nanowire can be generated in the high-temperature high-pressure reaction kettle, and the method is simple in step, simple to operate and easy to repeat.
In general, water-dispersible palladium nanowires having a length of 50 μm or more can be produced.
In one implementation mode, the reaction solution is used as prepared, and the mass ratio of the polyvinylpyrrolidone to the preset solution is 0.5-2: 1-5.
It should be noted that the reaction temperature in step 102 is 160-200 ℃, and the reaction time is 1-24 h.
In a specific embodiment, reference is made to example 1 for specific details of the generation of ultra-long palladium nanowires.
In one implementation manner, on the basis of step 102, the ultra-long palladium nanowire is used as a substrate, and a high-potential chloroauric acid raw material is put into the reaction solution to perform atomic potential displacement or etching, so as to generate a gourd-shaped palladium nanowire.
Specifically, on the basis of the step 102, the ultralong palladium nanowire is used as a substrate, a high-potential chloroauric acid raw material is put into a reaction solution to perform atomic potential displacement or etching, and the calabash-shaped palladium nanowire is generated.
The reaction solution for producing the calabash-shaped palladium nanowires is ready for preparation, and the mass ratio of gold to palladium atoms is 0.5-1: 0.01-0.5.
The reaction temperature for generating the calabash-shaped palladium nanowire is 50-100 ℃, and the reaction time is 1-5 h.
In one embodiment, the ultra-long palladium nanowire is used as a substrate, a high-potential chloroauric acid trihydrate raw material is put into the reaction solution to perform atomic potential displacement or etching, and the palladium nanowire with a gourd shape is generated through an oil bath reaction.
In one embodiment, reference is made to example 2 for specific details of the generation of ultra-long palladium nanowires by the method of step 102.
103, when ascorbic acid and a second mass of sodium chloropalladate are added into the reaction solution, palladium nano cubic blocks and palladium nano rods are generated.
Wherein the second mass comprises 65-150 mg.
In the step, after ascorbic acid and a second mass of sodium chloropalladate are added into the reaction solution generated in the step 101, palladium nano cubic blocks and palladium nano rods can be generated, and the method is simple in steps, simple in operation and easy to repeat.
In general, palladium nanocubes with a diameter ratio of 20nm and palladium nanorods with a length of 100nm or more can be produced.
In one implementation, when ascorbic acid and a second mass of sodium chloropalladate are added to the reaction solution, palladium nano-cubes and palladium nano-rods are generated by an oil bath reaction.
The reaction temperature of step 103 is 50-100 ℃, and the reaction time is 1-5 h.
In a specific example, reference is made to example 3 for specific details of the generation of palladium nano-cubes, palladium nano-rods and polyhedrons by the method of step 103.
In another embodiment, the specific description of the generation of palladium nano-cubes by the method of step 103 can be found in example 4.
And 104, when ascorbic acid and a third mass of sodium chloropalladate are added into the reaction solution, generating palladium nano cubic blocks.
Wherein the third mass comprises 20-59 mg.
In the step, ascorbic acid and sodium chloropalladate of a third mass are added into the reaction solution generated in the step 101 to generate palladium nano cubic blocks, and the method is simple in step, simple in operation and easy to repeat.
In one implementation, when ascorbic acid and a third mass of sodium chloropalladate are added to the reaction solution, palladium nano-cubes are generated by an oil bath reaction.
The reaction temperature of step 104 is 50-100 ℃, and the reaction time is 1-5 h.
In specific implementation, all kinds of palladium nanocrystals can replace the gold nanocrystals on the surface of the palladium nanocrystals to form palladium-gold alloy; the palladium-gold alloy can also comprise palladium-gold, palladium-platinum, gold-palladium-platinum and the like.
The method for preparing the palladium and the palladium alloy nanocrystalline provided by the invention specifically comprises the steps of adding 18-58 mg of sodium chloropalladate into a reaction solution of deionized water, a preset solution and polyvinylpyrrolidone, and generating an ultralong palladium nanowire under the reaction conditions of high temperature and high pressure; adding ascorbic acid and 65-150 mg of sodium chloropalladate into the reaction solution to generate palladium nano cuboids and palladium nano rods; and adding ascorbic acid and 20-59 mg of sodium chloropalladate into the reaction solution to generate palladium nano cubic blocks. Compared with the synthetic method in the prior art, the synthetic method has the advantages of simple processing steps, simple operation and easy repetition.
The specific experimental conditions are as follows:
example 1
Preparing an ultra-long palladium nanowire: respectively dissolving 18-58 mg of sodium chloropalladate, 0.5-2 g of potassium iodide and 1-5 g of polyvinylpyrrolidone in 10-40 mL of deionized water, transferring the deionized water to a high-pressure stainless steel reaction kettle, placing the reaction kettle in a forced air drying box, setting the reaction temperature to be 160-200 ℃, setting the reaction time to be 1-24 h, and carrying out multiple centrifugal separation and acetone washing to generate the ultralong palladium nanowire.
The generated ultra-long palladium nanowire can be referred to fig. 1b, and fig. 1b is an SEM image and an embedded TEM image of the ultra-long palladium nanowire generated in example 1.
Example 2
Preparing an ultra-long palladium-gold alloy nanowire: dispersing 1-10 mL of the ultralong palladium nanowires in example 1 in 50-200 mg of a polyvinylpyrrolidone (55000) aqueous solution, adding 10-100 mu L of chloroauric acid trihydrate with the concentration of 0.01-1 mM, performing oil bath reaction at the reaction temperature of 50-100 ℃ for 1-5 h, and performing centrifugal separation and water and ethanol washing for multiple times to generate the ultralong palladium nanowires.
The generated ultra-long palladium-gold alloy nanowire can be referred to fig. 2, and fig. 2 is a TEM image of the ultra-long palladium-gold nanowire generated in example 2.
Example 3
Preparation of palladium nano cubes, rods and polyhedrons: firstly, dissolving 100-600 mg of potassium bromide, 10-60 mg of ascorbic acid and 10-120 mg of polyvinylpyrrolidone (55000) in 1-10 mL of aqueous solution, placing the solution in a 50mL vial with a cover, and preheating the vial in a water bath at 50-100 ℃ for 10 minutes under magnetic stirring; subsequently, 65-150 mg of sodium chloropalladate is dissolved in 1-10 mL of the aqueous solution and added to the solution by a pipette. The reaction temperature is 50-100 ℃, and the reaction time is 1-5 h. The product was collected by centrifugation at 10000 rpm for 30 minutes, washed 4 times with ultrapure water to remove excess polyvinylpyrrolidone and bromide, and redispersed to produce palladium nano-cubes, rods and polyhedra.
The palladium nano-cubes, rods and polyhedrons generated can be referred to in fig. 3, and fig. 3 is a TEM image of palladium nano-cubes with different morphologies generated in example 3.
Example 4
Preparation of palladium nano-cubes: firstly, dissolving 100-600 mg of potassium bromide, 10-60 mg of ascorbic acid and 10-120 mg of polyvinylpyrrolidone (55000) in 1-10 mL of aqueous solution, placing the solution in a 50mL vial with a cover, and preheating the vial in a water bath at 50-100 ℃ for 10 minutes under magnetic stirring; subsequently, 20-59 mg of sodium tetrachloropalladate is dissolved in 1-10 mL of an aqueous solution and added to the solution with a pipette. The reaction temperature is 50-100 ℃, and the reaction time is 1-5 h. The product was collected by centrifugation at 10000 rpm for 30 minutes, washed 4 times with ultrapure water to remove excess polyvinylpyrrolidone and bromide, and redispersed to yield palladium nano-cubes.
The palladium nano-cube generated can be referred to fig. 4, fig. 4 is a TEM image of a 30nm palladium nano-cube of example 4.
Example 5
Preparing palladium-gold alloy nano cubic blocks: dispersing 1-10 mL of palladium nano cubic block in example 4 in 50-200 mg of polyvinylpyrrolidone (55000) aqueous solution, adding 10-100 mu L of chloroauric acid trihydrate with the concentration of 0.01-1 mM, performing oil bath reaction at the reaction temperature of 60-80 ℃ for 1-5 h, and performing centrifugal separation and water and ethanol washing for multiple times to generate the palladium-gold nano cubic block.
The palladium-gold alloy nano-cube produced can be referred to fig. 5, fig. 5 is a TEM image (top right inset, high resolution TEM image) of the palladium-gold alloy nano-cube produced in example 5.
In summary, the present invention has the following advantages:
(1) the invention provides a preparation method of palladium and palladium alloy nanocrystals, relates to the technical field of multidisciplinary solution synthesis, and aims to provide a simple and green solution synthesis method for preparing high-quality palladium nanowires, palladium-gold nanowires, palladium nanorods and palladium nano cubes. Chloroauric acid trihydrate and sodium chloropalladate are used as noble metal source precursors, and the ultra-long palladium nanowires, the ultra-long palladium gold nanowires and palladium nano cubic blocks smaller than 30nm are prepared and generated under the conditions of a polyvinylpyrrolidone system, a preset solution (one of sodium iodide, sodium bromide, potassium iodide and potassium bromide), ascorbic acid and deionized water system. The method has the characteristics of simple and convenient operation, green solvent, high yield, easy repeatability and the like, and has potential application prospect in the fields of photocatalysis, electrocatalysis, biomedicine, electronic science and the like.
(2) The invention provides a preparation method of palladium-gold alloy nanocrystals, which is characterized in that novel noble metal nano building blocks are constructed on the basis of palladium nanowires and nano cubic blocks, and the advantages of noble metals are complemented to achieve the maximum synergistic effect.
(3) The invention prepares a series of high-quality palladium and alloy nanocrystals thereof, and provides various selectivity in systematicness and substrate diversity.
The invention provides a device for preparing palladium and palladium alloy nanocrystals, and referring to fig. 6, fig. 6 is a schematic structural diagram of the device for preparing palladium and palladium alloy nanocrystals of the invention. As shown in fig. 6, the apparatus 60 for preparing palladium and its alloy nanocrystals includes:
the first generation module 601 is configured to add deionized water, a preset solution and polyvinylpyrrolidone into a reaction kettle, and generate a reaction solution by uniformly performing ultrasonic oscillation, wherein the preset solution includes one of sodium iodide, sodium bromide, potassium iodide and potassium bromide;
a second generating module 602, configured to generate an ultra-long palladium nanowire under high-temperature and high-pressure reaction conditions when a first mass of sodium chloropalladate is added to the reaction solution;
a third generating module 603, configured to generate palladium nano-cubes and palladium nano-rods when ascorbic acid and a second mass of sodium chloropalladate are added to the reaction solution;
a fourth generating module 604 for generating palladium nano-cubes when ascorbic acid and a third mass of sodium chloropalladate are added to the reaction solution.
Optionally, the reaction solution is used as it is, and the mass ratio of the polyvinylpyrrolidone to the preset solution is 0.5-2: 1-5.
Optionally, the apparatus further comprises:
and the fifth generation module is used for taking the ultra-long palladium nanowire as a substrate, and putting a high-potential chloroauric acid raw material into the reaction solution to perform atomic potential displacement or etching to generate the gourd-shaped palladium nanowire.
Optionally, the reaction solution is ready for preparation, and the mass ratio of gold to palladium atoms is 0.5-1: 0.01-0.5.
Optionally, the reaction temperature of the fifth generation module, the reaction temperature of the fourth generation module and the reaction temperature of the third generation module are 50-100 ℃, and the reaction time is 1-5 hours.
Optionally, the reaction temperature of the second generation module is 160-200 ℃, and the reaction time is 1-24 hours.
Optionally, the fifth generating module is specifically configured to use the ultra-long palladium nanowire as a substrate, put a high-potential chloroauric acid raw material into the reaction solution to perform atomic potential displacement or etching, and generate a gourd-shaped palladium nanowire through an oil bath reaction;
the third generating module 603 is specifically configured to generate palladium nano-cubes and palladium nano-rods through an oil bath reaction when ascorbic acid and a second mass of sodium chloropalladate are added to the reaction solution;
the fourth generating module 604 is specifically configured to generate palladium nano-cubes through an oil bath reaction when ascorbic acid and a third mass of sodium chloropalladate are added to the reaction solution.
Therefore, the preparation device of the palladium and the palladium alloy nanocrystalline, provided by the invention, specifically comprises the steps of adding 18-58 mg of sodium chloropalladate into a reaction solution of deionized water, a preset solution and polyvinylpyrrolidone, and generating an ultralong palladium nanowire under the reaction conditions of high temperature and high pressure; adding ascorbic acid and 65-150 mg of sodium chloropalladate into the reaction solution to generate palladium nano cuboids and palladium nano rods; and adding ascorbic acid and 20-59 mg of sodium chloropalladate into the reaction solution to generate palladium nano cubic blocks. Compared with the synthetic method in the prior art, the synthetic method has the advantages of simple processing steps, simple operation and easy repetition.
Those of ordinary skill in the art will understand that: the figures are merely schematic representations of one embodiment, and the blocks or flow diagrams in the figures are not necessarily required to practice the present invention.
Those of ordinary skill in the art will understand that: modules in the devices in the embodiments may be distributed in the devices in the embodiments according to the description of the embodiments, or may be located in one or more devices different from the embodiments with corresponding changes. The modules of the above embodiments may be combined into one module, or further split into multiple sub-modules.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of palladium and alloy nanocrystals thereof is characterized by comprising the following steps:
adding deionized water, a preset solution and polyvinylpyrrolidone into a reaction kettle, and uniformly oscillating by ultrasonic to generate a reaction solution, wherein the preset solution comprises one of sodium iodide, sodium bromide, potassium iodide and potassium bromide;
when sodium chloropalladate with a first mass is added into the reaction solution, generating an ultralong palladium nanowire under the reaction conditions of high temperature and high pressure;
when ascorbic acid and a second mass of sodium chloropalladate are added into the reaction solution, palladium nano cubic blocks and palladium nano rods are generated;
when ascorbic acid and a third mass of sodium chloropalladate are added to the reaction solution, palladium nano-cubes are generated.
2. The method of claim 1,
the reaction solution is used as prepared, and the mass ratio of the polyvinylpyrrolidone to the preset solution is 0.5-2: 1-5.
3. The method of claim 1, wherein after the step of generating the ultra-long palladium nanowires under the reaction conditions of high temperature and high pressure when the first mass of sodium chloropalladate is added to the reaction solution, the method further comprises:
and (3) taking the ultra-long palladium nanowire as a substrate, and putting a high-potential chloroauric acid trihydrate raw material into the reaction solution to perform atomic potential displacement or etching to generate the gourd-shaped palladium nanowire.
4. The method of claim 3, wherein:
the reaction solution is ready for preparation, and the mass ratio of gold to palladium atoms is 0.5-1: 0.01-0.5.
5. The method of claim 3, wherein:
the reaction temperature of the generated calabash-shaped palladium nanowire, the generated palladium nano cubic block and the palladium nano rod and the generated palladium nano cubic block is 50-100 ℃, and the reaction time is 1-5 hours.
6. The method of claim 1, wherein:
the reaction temperature for generating the ultra-long palladium nanowire is 160-200 ℃, and the reaction time is 1-24 h.
7. The method according to claim 1 or 2, characterized in that:
the method comprises the following steps of taking the ultra-long palladium nanowire as a substrate, putting a high-potential chloroauric acid trihydrate raw material into the reaction solution for atomic potential replacement or etching to generate the calabash-shaped palladium nanowire, wherein the steps comprise:
taking the ultra-long palladium nanowire as a substrate, putting a high-potential chloroauric acid trihydrate raw material into the reaction solution for atomic potential replacement or etching, and generating the calabash-shaped palladium nanowire through oil bath reaction;
the step of generating palladium nano-cubes and palladium nano-rods when ascorbic acid and a second mass of sodium chloropalladate are added into the reaction solution comprises the following steps:
when ascorbic acid and a second mass of sodium chloropalladate are added into the reaction solution, palladium nano cubic blocks and palladium nano rods are generated through oil bath reaction;
the step of generating palladium nano-cubes when ascorbic acid and a third mass of sodium chloropalladate are added to the reaction solution comprises:
when ascorbic acid and a third mass of sodium chloropalladate are added into the reaction solution, palladium nano-cubic blocks are generated through an oil bath reaction.
8. A preparation device of palladium and alloy nanocrystalline thereof is characterized by comprising the following components:
the first generation module is used for adding a first mass of deionized water, a third mass of preset solution and a fourth mass of polyvinylpyrrolidone into the reaction kettle with the first capacity, and uniformly generating a reaction solution through ultrasonic oscillation, wherein the preset solution comprises one of sodium iodide, sodium bromide, potassium iodide and potassium bromide;
the second generation module is used for generating the ultralong palladium nanowire under the high-temperature and high-pressure reaction condition when the sodium chloropalladate with the first mass is added into the reaction solution;
a third generation module, configured to generate palladium nano-cubes and palladium nano-rods when ascorbic acid and a second mass of sodium chloropalladate are added to the reaction solution;
and the fourth generation module is used for generating palladium nano cubic blocks when ascorbic acid and third mass of sodium chloropalladate are added into the reaction solution.
9. The apparatus of claim 8, wherein:
the reaction solution is used as prepared, and the mass ratio of the polyvinylpyrrolidone to the preset solution is 0.5-2: 1-5.
10. The apparatus of claim 8, further comprising:
and the fifth generation module is used for taking the ultra-long palladium nanowire as a substrate, and putting a high-potential chloroauric acid raw material into the reaction solution to perform atomic potential displacement or etching to generate the gourd-shaped palladium nanowire.
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