CN101608341B - Dendritic silver palladium alloy single crystal nano-structure array and preparation method thereof - Google Patents
Dendritic silver palladium alloy single crystal nano-structure array and preparation method thereof Download PDFInfo
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- CN101608341B CN101608341B CN200910067341XA CN200910067341A CN101608341B CN 101608341 B CN101608341 B CN 101608341B CN 200910067341X A CN200910067341X A CN 200910067341XA CN 200910067341 A CN200910067341 A CN 200910067341A CN 101608341 B CN101608341 B CN 101608341B
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- palladium alloy
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 47
- 229910001252 Pd alloy Inorganic materials 0.000 title claims abstract description 27
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000013078 crystal Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 34
- 239000004332 silver Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 24
- 238000004381 surface treatment Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001069 Raman spectroscopy Methods 0.000 abstract description 5
- 235000019253 formic acid Nutrition 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract 1
- 239000000446 fuel Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 6
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000011260 aqueous acid Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 241000555268 Dendroides Species 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to a dendritic silver palladium alloy single crystal nano-structure array and a preparation method thereof. Filamentary silver or flaky silver which has cleanly treated surface is soaked into chloropalladite water solution to stand still for reaction; when in the reaction process, water bath is used for ensuring the temperature of the solution to be stable, so that the dendritic silver palladium alloy single crystal nano-structure array can be obtained. The nano-structure array is formed by dendritic nano-structures which have the length within the range of 10-20mum and are vertical to a substrate; every dendritic nano-structure is a hierarchical structure which is formed by a main framework and a plurality of branches that symmetrically grow on the main framework; smaller branches grow on every branch in the same way; the substrate is silver, and the dendritic nano-structures are formed by silver palladium alloy single crystal. The synthesized dendritic silver palladium alloy single crystal nano-structure array has stronger raman enhancement activity and electro-catalysis activity for formic acid oxidation, and application value in the fields such as analysis, catalysis, fuel cells, etc. The nano-structure array can be prepared on the surface of silver with different sizes and shapes.
Description
Technical field
The present invention relates to dendritic silver palladium alloy single crystal nano-structure array and preparation method.
Background technology
The development of nanosecond science and technology has proposed urgent and higher requirement to the preparation of nano material.The physics of nano material and chemical property and its crystallinity, pattern, components etc. are closely related.In addition, nano-structure array has the performance more excellent more than unordered nano material, for the exploitation significance of nano-device.Therefore, the controlled crystallinity of preparation pattern component nano material and it is built into orderly array is a great challenge preferably.Dendritic nano-structure is a kind of important, has the very hierarchy of high surface area.At present, the existing report of the dendritic nano-structure of metal (as gold, silver, palladium, copper), they are in catalysis, and aspects such as surface enhanced Raman scattering (SERS) and preparation biosensor and ultraphobic water surface have potential to use.(reference: 1.Qin, Y.; Song, Y.; Sun, N.; Zhao, N.; Li, M.; Qi, L.Chem.Mater.2008,20,3965.2.Lin, H.; Mock, J.; Smith, D.; Gao, T.; Sailor, M.J.J.Phys.Chem.B 2004,108,11654.3.Song, Y.J.; Kim, J.Y.; Park, K.W.Cryst.Growth Des.2009,9,505.4.Zhang, X.; Wang, G.; Liu, X.; Wu, H.; Fang, B.Cryst.Growth Des.2008,8,1430.) yet, also do not prepare dendritic silver palladium alloy single crystal nano-structure and construct the report of oldered array for basic construction unit with it.
Summary of the invention
The present invention adopts replacement(metathesis)reaction (galvanic replacement reaction) to prepare large-area dendritic silver palladium alloy single crystal nano-structure array at the bottom of the money base.
Dendritic silver palladium alloy nano-structure array provided by the invention is made of the dendritic nano-structure one by one perpendicular to substrate of length at 10～20 μ m; Each dendritic nano-structure all is a kind of hierarchies, by a trunk and some on trunk the branch of symmetric growth constitute; In each branch again with the same manner littler branch of growing; Described substrate is a silver, and described dendritic nano-structure is to be made of silver palladium alloy single crystal.
The preparation method's of dendritic silver palladium alloy single crystal nano-structure array provided by the invention step and condition are as follows: filamentary silver or silver strip that surface treatment is clean are immersed in 0.5 * 10
-3～2 * 10
-3Standing and reacting in the chlorine palladium aqueous acid of mol/l makes solution temperature be stabilized in 50～60 ℃ by water-bath in the reaction process, reacts 10 minutes～1 hour, and the filamentary silver surface becomes black, and water washes it, obtains dendritic silver palladium alloy single crystal nano-structure array.
Beneficial effect: the present invention has prepared dendritic silver palladium alloy single crystal nano-structure array first.The replacement(metathesis)reaction (galvanic replacement reaction) that the present invention adopts is a kind of non-electro-deposition technology, metal or the semi-conductor low with redox-potential provide electronics the metal ion reduction that the redox-potential in the solution is high as substrate, this method has easy and simple to handle, the advantage that cost is low.This method can prepare dendritic silver palladium alloy single crystal nano-structure array at the silver surface of various size and shape, and therefore good suitability is arranged.(referring to embodiment 1,8 and accompanying drawing 1,12) institute's synthetic dendritic silver palladium alloy single crystal nano-structure array has stronger surface enhanced Raman scattering (SERS) activity.The dendritic nano-structure of (referring to embodiment 9 and accompanying drawing 13) forming array has also shown electro catalytic activity to formic acid oxidation.(referring to embodiment 10 and accompanying drawing 14)
Description of drawings
Fig. 1 is the sem photograph of the clean diameter 0.25mm filamentary silver of surface treatment among the embodiment 1.
Fig. 2 is the sem photograph of the formed nano-array in filamentary silver surface that process method of the present invention obtains among the embodiment 1.
Fig. 3 is the sem photograph of the high-amplification-factor of the filamentary silver surface nano-array that forms that process method of the present invention obtains among the embodiment 1.Can observe nano-array is made of dendritic nano-structure.
Fig. 4 is the XRD figure of the dendritic nano-structure that process method of the present invention obtains among the embodiment 1.Five diffraction peaks are between two groups of diffraction peaks of simple substance silver and palladium and do not have peak division phenomenon, illustrate that this dendritic nano-structure is made of silver palladium alloy.
Fig. 5 is the transmission electron microscope of single dendritic nanostructure among the embodiment 1, electron diffraction (a) and high-resolution-ration transmission electric-lens figure (b).Illustrate that the silver palladium alloy dendritic nano-structure is a monocrystalline.
Fig. 6 is the sem photograph of the formed nano-array in filamentary silver surface that process method of the present invention obtains among the embodiment 2.
Fig. 7 is the sem photograph of the formed nano-array in filamentary silver surface that process method of the present invention obtains among the embodiment 3.
Fig. 8 is the sem photograph of the formed nano-array in filamentary silver surface that process method of the present invention obtains among the embodiment 4.
Fig. 9 is the sem photograph of the formed nano-array in filamentary silver surface that process method of the present invention obtains among the embodiment 5.
Figure 10 is the sem photograph of the formed nano-array in filamentary silver surface that process method of the present invention obtains among the embodiment 6.
Figure 11 is the sem photograph of the formed nano-array in filamentary silver surface that process method of the present invention obtains among the embodiment 7.
Figure 12 is the sem photograph of the formed nano-array in silver strip surface that process method of the present invention obtains among the embodiment 8.
Figure 13 is among the embodiment 9 10
-7M rhodamine 6G (R6G) is respectively at (a) nano-array and (b) Raman spectrogram of silver surface.Illustrate that the nano-array that obtains through method of the present invention has stronger surface enhanced Raman scattering (SERS) activity
Figure 14 be (a) dendroid silver palladium alloy nanostructure is modified among the embodiment 10 gold electrode and (b) gold electrode be cyclic voltammogram in the 0.2M formic acid and the 0.5M vitriolic aqueous solution at electrolyte solution, sweep fast 50mv/s.Illustrate that this nano-array has higher electro catalytic activity to formic acid oxidation.
Embodiment
Embodiment 1: the preparation method of dendritic silver palladium alloy single crystal nano-structure array is characterized in that step and condition are as follows: the filamentary silver that surface treatment is clean (diameter 0.25mm, purity is greater than 99%) is immersed in 1 * 10
-3Standing and reacting in the chlorine palladium aqueous acid of mol/l makes solution temperature be stabilized in 50 ℃ by water-bath in the reaction process, reacts 30 minutes, and the filamentary silver surface becomes black, and water washes it, obtains dendritic silver palladium alloy nano-structure array.Scanning electron microscope is carried out on the filamentary silver surface characterize, see accompanying drawing 2,3.Dendritic nanostructure is separated from filamentary silver by ultrasonic, carry out XRD respectively, transmission electron microscope characterizes, and sees accompanying drawing 4,5.
Embodiment 2: chlorine palladium aqueous acid concentration is become 0.5 * 10
-3Mol/l, other conditions are with embodiment 1, and the product that the present invention is obtained carries out the scanning electron microscope sign, sees accompanying drawing 6.
Embodiment 3: chlorine palladium aqueous acid concentration is become 2 * 10
-3Mol/l, other conditions are with embodiment 1, and the product that the present invention is obtained carries out the scanning electron microscope sign, sees accompanying drawing 7.
Embodiment 4: temperature of reaction is become 55 ℃, and other conditions are with embodiment 1, and the product that the present invention is obtained carries out the scanning electron microscope sign, sees accompanying drawing 8.
Embodiment 5: temperature of reaction is become 60 ℃, and other conditions are with embodiment 1, and the product that the present invention is obtained carries out the scanning electron microscope sign, sees accompanying drawing 9.
Embodiment 6: will become 10 minutes the reaction times, other conditions are with embodiment 1, and the product that the present invention is obtained carries out the scanning electron microscope sign, sees accompanying drawing 10.
Embodiment 7: will become 1 hour the reaction times, other conditions are with embodiment 1, and the product that the present invention is obtained carries out the scanning electron microscope sign, sees accompanying drawing 11.
Embodiment 8: filamentary silver is changed to the clean silver strip of surface treatment, and other conditions are with embodiment 1, and the black layer cross section on the silver strip surface that the present invention is obtained is carried out scanning electron microscope and characterized, and sees accompanying drawing 12.
Embodiment 9: rhodamine 6G (R6G) is used as the surface reinforced Raman active that tagged molecule is investigated prepared nano-array in the example 1.The filamentary silver that the present invention is obtained is immersed in 10
-7In the ethanolic soln of M R6G 10 minutes, seasoning in the air then characterized on Raman spectrometer (Renishaw 2000 confocal Raman spectrophotometer), and compares used excitation wavelength 514nm with the fine silver silk.The gained Raman spectrum is seen accompanying drawing 13.
Embodiment 10: the measurement of electro catalytic activity is to carry out on CHI 832 electrochemical workstations, adopts traditional three-electrode system.The gold electrode that dendroid silver palladium alloy nanostructure is modified is produced as follows: the filamentary silver that the present invention obtains is ultrasonic in water, obtain the suspension liquid of black, and then 1 μ l suspension liquid is dripped on the gold electrode of diameter 1mm seasoning in the air.The utmost point and reference electrode are respectively platinum electrode and silver/silver chloride reference electrode.Electrolyte solution is the 0.2M formic acid and the 0.5M vitriolic aqueous solution.Resultant cyclic voltammogram is seen accompanying drawing 14 curve a, and as a comparison, we have also detected the cyclic voltammogram of gold electrode under similarity condition, sees accompanying drawing 14 curve b.
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| CN103381364B (en) * | 2013-07-02 | 2015-10-14 | 湖南省吉安特技术有限公司 | A kind of preparation method of nano palladium oxide catalyst |
| CN110699646B (en) * | 2019-09-25 | 2021-03-30 | 清华大学 | Preparation and application of resonance wavelength adjustable silver nanorod array |
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Non-Patent Citations (2)
| Title |
|---|
| Jingyi Chen等.Optical Properties of Pd-Ag and Pt-Ag Nanoboxes Synthesized via Galvanic Replacement Reactions.《NANO LETTERS》.2005,第5卷(第10期),2058-2062. * |
| Jixiang Fang等.Dendritic Silver Nanostructure Growth and Evolution in Replacement Reaction.《CRYSTAL GROWTH & DESIGN》.2007,第7卷(第5期),864-867. * |
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Effective date of registration: 20131212 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |