CN1686782A - Nano tube made from noble metal, preparation method and application - Google Patents
Nano tube made from noble metal, preparation method and application Download PDFInfo
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- CN1686782A CN1686782A CN 200510013466 CN200510013466A CN1686782A CN 1686782 A CN1686782 A CN 1686782A CN 200510013466 CN200510013466 CN 200510013466 CN 200510013466 A CN200510013466 A CN 200510013466A CN 1686782 A CN1686782 A CN 1686782A
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Abstract
A nanotube of noble metal (Ag, Pd, Pt, Ru, or Pt-Pd) has open ends, 60 microns in length, 180-220 nm in external diameter, and 120-200 sq.m/g in specific surface area. It is prepared by aluminium oxide template method, and can be used for bearing oxygen, catalysis and fuel battery.
Description
Technical Field
The invention relates to the technical field of nanometer, in particular to a noble metal nanotube and a preparation method and application thereof. The noble metal M is Ag, Pd, Pt, Ru or Pt-Pd, and the nanotube is characterized in that: using oxygenThe noble metal nanotube prepared by the aluminum template method has an open tubular structure, the length of the noble metal nanotube can reach 60 mu m, the outer diameter is about 200nm, the thickness of the tube wall is 3-10 nm, and the specific surface area of the nanotube is 120-200m2(ii) in terms of/g. Due to the unique d electronic structure of the transition metal and the nanotube with large specific surface area and relatively low metal loading capacity, the transition metal has wide application prospect in the fields of hydrogen storage, catalysis, fuel cells and the like.
Technical Field
The nanotechnology is a major breakthrough in the ability of human beings to know the world and transform the world, and as a bridge of contact information communication technology and life science and a future starting technology, the nanotechnology can accelerate human life. Nanotechnology is to manipulate atoms and molecules in millionth of a millimeter range, process materials, and produce new products with specific functions. This necessitates research into nanomaterials and nanodevices. Among various types of nano materials, the nano tube has unique physical and chemical properties, and has wide application prospects in the fields of nano catalysis, advanced material preparation, energy storage and conversion and the like.
The uniquephysical and chemical properties of the noble metal elements enable the noble metal elements to be widely applied to the fields of multiple catalysis, information technology, laser technology, composite materials, medicines, aerospace materials and the like. The noble metal nano material has unique functions in optical, electrical and catalytic applications due to the unique size effect.
At present, the preparation method and application of noble metal nanoparticles and nanowires have been extensively studied at home and abroad (e.g., Sangwood Kim, Jongnam Park, Youngjin Jang, et al. Synthesis of Monodissperse Palladium nanoparticles. Nano particles. 2003, 3: 1289-. However, few reports have been made on the preparation and use of noble metal nanotubes (Brian Mayers, Xuchuan junction, David Sunderland, et al. hollow Nanostructures of Platinum with Controllable Dimensions Can synthesized by manipulating the organic solvent of gold. Soc.2003, 125: 13364 + 13365; Yugang Sun, Brian Mayer, Younan Xia. metal Nanostructures with noble metals Interiors. Adv. 2003, 15: 641 + 646). And the method for preparing the noble metal nano-tube reported at present mainly takes the silver nano-wire or the selenium nano-wire as a template, the reaction steps are complex, the energy consumption is higher, and the reaction process is not easy to control. It follows from this that: the exploration of a controllable preparation method of the high-purity noble metal nanotube is undoubtedly of great significance.
In addition, in the application of noble metal nanotubes, besides the subject group regarding the performance research of Pd nanotubes applied to Reversible hydrogen storage carriers (Yugang Sun, Zhangian Tao, Jun Chen, et al. Ag Nanowies Coated with Ag/Pd alloy sheathes and Their uses as Substrates for Reversible adsorption and Desorption of hydrogen.J.Am.chem.Soc.2004, 126: 5940-type 5941) and the application of Ru-Pt nanotubes to methanol fuel cell anode catalysts (Jun Chen, Zhangian Tao, solong Li.F.A.simulation of Ru and Ru-Based functional nanotubes J.Am.chem.Soc.2004, 126: 3060-type 3061), there are reports in the relevant fields, especially the application of Pd nanotubes as fuel electrodes in and abroad is not reported.
Disclosure of Invention
The invention aims to provide a noble metal nanotube, a preparation method and application thereof, and is characterized in that the noble metal nanotube with uniform size is prepared by taking porous alumina as a template, and the shape of the noble metal nanotube is effectively controlled. In particular to (1) realizing the low-temperature controllable preparation of the noble metal nanotube and the noble metal composite nanotube thereof; (2) the application of the nano-tube in hydrogen storage and fuel cell electrode catalyst is developed. The application of the noble metal nano-tube in hydrogen storage, catalysis and fuel cells is developed, which has high practical application value for developing novel hydrogen storage materials and fuel cell electrode catalysts.
The invention relates to a nanotube with regular openings, which is formed by noble metal M, wherein M is noble metal Ag, Pd, Pt, Ru or Pt-Pd; the length of the series of nanotubes is 50-60 μm, the outer diameter is 180-200nm, the thickness of the tube wall is 3-10 nm, and the specific surface area is 120-200m2/g。
The preparation method of the noble metal nanotube comprises the following steps:
1) mixing an aqueous solution containing a soluble salt of a noble metal M, including K2MCl6And M (NH)3)xOne or two of Cly, wherein x is 4 or 6, v is 2 or 3, is injected into the porous alumina template, and simultaneously 5-8 mol.L-1Introducing a mixed gas of hydrogen and argon in a volume ratio of 1: 19 at the flow rate, and heating at 150-380 ℃ for 1 hour.
2) Dissolving the template with alkali solution to remove, collecting the obtained solid, washing with anhydrous ethanol and deionized water for several times, and vacuum drying at 80 deg.C for 1 hr.
The invention provides a special device used in the preparation method of the noble metal nanotube. The device comprises an exhaust port, a liquid inlet, a cylindrical stainless steel reactor, an upper platinum net, an upper microporous filter, an alumina template, a lower platinum net, a liquid outlet, an air inlet and a lower microporous filter. The top end of the cylindrical stainless steel reactor is provided with an air outlet and a liquid inlet, and the lower end of the cylindrical stainless steel reactor is provided with an air inlet and a liquid outlet; an upper platinum net, an upper microporous filter, an alumina template, a lower microporous filter and a lower platinum net are sequentially arranged in the cylindrical stainless steel reactor.
The preparation method is characterized in that: the method for preparing the metal nano tube by using the porous alumina as the template and adopting the chemical deposition method is characterized in that metal particles obtained by reduction are firstly deposited on the hole wall of the template and gradually deposited to thicken. Therefore, the inner diameter of the nanotube can be controlled by controlling the deposition time, the heating temperature, the solution concentration and other reaction conditions, and the outer diameter is determined by the pore diameter of the template. For example, because the pore diameter of the template is very small, the solution is not easy to permeate into the template, and the mixed gas of hydrogen and argon with certain pressure is introduced, so that the difficulty can be effectively overcome. Hydrogen is used as a reducing agent, and a gas byproduct is finally obtained, so that the post-treatment is simple; at the same time, the hydrogen can be easily adjusted to the optimum concentration to obtain the product with the optimum morphology.
The characteristics in the aspect of application are as follows: the metal Pd has strong adsorption and cracking capacity to hydrogen, and the Pd nano-tube has large surface-to-mass ratio (large specific surface area and small mass) and quite a plurality of particle gaps, so the Pd nano-tube can be used as a carrier for hydrogen storage and has important application prospect in the fields of hydrogen storage and the like. In addition, since an intermediate product (like a carbon monoxide intermediate product) generated during the anodic oxidation of the fuel cell poisons platinum, a Pt-based catalyst having a certain resistance to carbon monoxide poisoning is often used. The Pt-Pd nanotube is used as an electrode material of the methanol fuel cell, has lower oxidation potential than Ru-Pt, and has high utilization value. The good performances of the two aspects promote the rapid development of the noble metal nanotube in hydrogen energy and fuel cells.
The reversible hydrogen storage of the Pd nano-tube is obtained by a gas/solid reaction hydrogen storage mode. Gas/solid reaction hydrogen storage is carried out in a pressure/composition/temperature (PCT, Advanced Materials Corp.) plant. The experimental device consists of a valve, a pressure gauge, a pressure sensor, a sample reactor, a heating furnace, temperature control and the like. The experimental temperature is 20, 70 and 120 ℃, the experimental air pressure is 0.002-40 atm, and the hydrogen absorption/hydrogen discharge curve is obtained by a step pressure reduction hydrogen discharge method.
The Pt-Pd nanotube used as anode catalyst of methanol fuel cell is analyzed by cyclic voltammetry, and a three-electrodesystem is adopted, namely the Pt-Pd nanotube is wrapped in a foamed nickel current collector to be used as a tested working electrode, Ag/AgCl/KCl (3M) is used as a reference electrode, Pt/C is used as a cathode, liquid methanol is used as fuel, and newly prepared 0.5M sulfuric acid is used as electrolyte. The cyclic voltammetry experiment is carried out under the control of a computer, and the sweep rate of the cyclic voltammetry is 20 mV/s.
The method has the advantages that the high-purity noble metal nanotube is prepared by adopting a template method, so that good controllability on materials is realized; the series of noble metal nanotubes have good performance when applied to reversible hydrogen storage carriers and methanol fuel cell electrode catalysts, have wide development prospect and application range in the aspects of hydrogen storage and fuel cells, and can greatly promote the development of hydrogen energy and fuel cells.
Drawings
FIG. 1 is a schematic structural diagram of an experimental apparatus for preparing noble metal nanotubes.
FIG. 2 is a schematic view of a process flow for preparing a noble metal nanotube by a template method.
FIG. 3 is an XRD pattern of Ru nanotubes.
FIG. 4 is an XRD pattern of Pd nanotubes.
Fig. 5 is an XRD pattern of Pt nanotubes.
Fig. 6 is an XRD pattern of Ag nanotubes.
FIG. 7 is a scanning electron microscopy analysis of Ru nanotubes: (a) is the wall of the nanotube; (b) are dispersed nanotubes.
FIG. 8 is a scanning electron microscopy analysis of Pd nanotubes.
FIG. 9 is a scanning electron microscopy analysis of Pt nanotubes.
FIG. 10 is a scanning electron microscopy analysis of Ag nanotubes.
FIG. 11 is a scanning electron microscopy analysis of Pt-Pd nanotubes.
FIG. 12 is a graph showing hydrogen absorption curves of Pd nanotubes.
FIG. 13 is transmission electron microscope analysis of Pd nanotubes after 50 cycles of hydrogen absorption/desorption.
FIG. 14 is a cyclic voltammogram of Pt-Pd nanotubes as anode catalyst for methanol fuel cells.
Detailed Description
Example 1:
and (3) preparing the Ru nanotube.
FIG. 1 is a schematic structural diagram of an experimental apparatus for preparing noble metal nanotubes. 1-exhaust port, 2-liquid inlet, 3-cylindrical stainless steel reactor, 4-upper platinum net, 5-upper microporous filter, 6-alumina template, 7-lower platinum net, 8-liquid outlet, 9-air inlet, 10-lower microporous filter. The top end of the cylindrical stainless steel reactor is provided with an air outlet and a liquid inlet, and the lower end of the cylindrical stainless steel reactor is provided with an air inlet and a liquid outlet; an upper platinum net, an upper microporous filter, an alumina template, a lower microporous filter and a lower platinum net are sequentially arranged in the cylindrical stainless steel reactor.
An aluminum oxide template: pore diameter: 200nm, thickness: 60 μm, diameter: 47mm (Whatman International Ltd, England); stainless steel microporous filter: pore diameter: 5 μm, thickness: 60 μm, diameter: 48 mm.
Using the above apparatus, 0.04M Ru (NH)3)6Cl3The solutionwas poured into a template, a mixed gas of hydrogen and argon was introduced at a volume ratio of 1: 19(V/V) at a flow rate of 8mL/min, heated at 150 ℃ for 1 hour, cooled to room temperature, and then the alumina template was dissolved and removed with 2M NaOH solution. The obtained black solid is washed by absolute ethyl alcohol and deionized water for several times to be cleaned. Finally the product was dried under vacuum at 80 ℃ for 1 hour. The reaction equation for the product formation is:
the XRD spectrogram of the Ru nanotube prepared by the method is shown in figure 3. The intensity and position of the diffraction peak were consistent with those of JCDPS standard card (No.06-0663), and no other impurity phase could be found in the figure, indicating that a higher purity crystal was obtained. The lattice constants a and c of the sample were calculated to be 0.2706nm and 0.4282nm according to XRD data, indicating that the product has a hexagonal structure (P6)3/mmc(194))。
The scanning electron microscope analysis (fig. 7) of the Ru nanotubes prepared by the method shows: a large number of products are regularly arranged together to form a bundle of aggregates, the length of the aggregates is 60 mu m, and the aggregates are matched with the thickness of a porous alumina template used in the preparation process; the diameter of the nanotube is uniform, the outer diameter is 200nm, the diameter of the nanotube is consistent with the aperture of the template, and the thickness of the tube wall is 6 nm. The specific surface area of the Ru nanotube prepared by the method is 120m measured by specific surface analysis (Japanese Shimadzu ASAP2010 type BET instrument)2/g。
Example 2:
preparation of Pd nanotubes
In the apparatus of FIG. 1, 0.06M Pd (NH)3)4Cl2Injecting the solution into a template, introducing mixed gas of hydrogen and argon in a volume ratio of 1: 19(V/V) at a flow rate of 6mL/min, heating at 180 ℃ for 1 hour, cooling to room temperature, and dissolving and removing the alumina template by using 2M NaOH solution. The resulting solid was washed several times with absolute ethanol and deionized water. Finally the product was dried under vacuum at 80 ℃ for 1 hour. The reaction equation for the product formation is:
the XRD spectrogram of the Pd nanotube prepared by the method is shown in figure 4: the intensity and position of the Pd specific peak are consistent with the data of JCDPS standard card (No.05-0681), and the Pd specific peak has a face-centered cubic structure.
The scanning electron microscope analysis (figure 8) of the Pd nanotubes prepared by the described method shows: a large number of products are regularly arranged together to form a bundle of aggregates with the length of 60 mu m, which is matched with the thickness of the porous alumina template used in the preparation process. The nanotube has smooth surface, uniform diameter, outer diameter of 200nm, aperture consistent with that of the template, and thickness of 3-4 nm. The Pd nano tube prepared by the method has the specific surface area of 150m2/g。
Example 3:
preparation of Pt nanotubes
The apparatus was as described above, 0.06M H2PtCl6Injecting the solution into a template, introducing mixed gas of hydrogen and argon in a volume ratio of 1: 19(V/V), heating at 180 ℃ for 1 hour at a flow rate of 6mL/min, cooling, dissolving out the template, and washing the obtained solid with absolute ethyl alcohol and deionized water for several times. Finally the product was dried under vacuum at 80 ℃ for 1 hour. The reaction equation for the product formation is:
the XRD spectrum (fig. 5) of the Pt nanotubes prepared by the method shows: the intensity and position of the diffraction peak are consistent with the data of JCDPS standard card (No.04-0802), which shows that the synthesized Pt nanotube has a face-centered cubic structure and the product purity is high. The broadening phenomenon of diffraction peak is caused by the nanometer level and fine crystal grain of the product.
The scanning electron microscope analysis of the Pt nanotubes prepared by the method is shown in fig. 9: the microscopic appearance of the product is fibrous, the length is about 60 mu m, and the length is matched with the thickness of the porous alumina template used in the preparation process; the product is a hollow tubular structure. The outer diameter of the nanotube is 200nm, which is consistent with the pore diameter of the template, and the thickness of the tube wall is 10 nm. The Pd nano tube prepared by the method has the specific surface area of 200m2/g。
Example 4:
preparation of Ag nanotubes
In the apparatus of FIG. 1, 0.06M AgNO was added3The solution was poured into a template, a mixed gas of hydrogen and argon was introduced at a volume ratio of 1: 19(V/V) at a flow rate of 6mL/min, heated at 180 ℃ for 1 hour, cooled to room temperature, and the alumina template was dissolved and removed with 2M NaOH solution. The resulting solid was washed several times with absolute ethanol and deionized water. Finally the product was dried under vacuum at 80 ℃ for 1 hour. The reaction equation for the product formation is:
the XRD spectrogram of the Ag nanotube prepared by the method is shown in figure 6: the intensity and position of the Ag diffraction peak were consistent with those of JCDPS standard card (No.04-0783), and had a face-centered cubic structure.
The scanning electron microscope analysis of the Ag nanotubes prepared by the method is shown in fig. 10: the microscopic appearance of the product is fibrous, the length is about 60 mu m, and the length is matched with the thickness of the porous alumina template used in the preparation process; the outer diameter of the nanotube is about 200nm, the diameter of the nanotube is consistent with that of the template, and the thickness of the tube wall is 5 nm. The Pd nano tube prepared by the method has the specific surface area of 130m2/g。
Example 5:
preparation of Pt-Pd nanotubes
In the apparatus of FIG. 1, K of 0.02M is applied2PtCl6Solution and 0.06M Pd (NH)3)4Cl2The solutions are respectively injected into a template, mixed gas of hydrogen and argon with the volume ratio of 1: 19(V/V) is introduced, the gas flow rate is 10mL/min,heating at 260 ℃ for 1 hour. After cooling to room temperature, the alumina template was dissolved away with 2M NaOH solution. The resulting solid was washed several times with absolute ethanol and deionized water. And finally, drying the product at 80 ℃ for 1 hour in vacuum to obtain the Pt-Pd nanotube. The reaction equation for the product formation is:
the scanning electron microscope analysis of the Pt-Pd nanotube prepared by the method is shown in fig. 11, and the overall appearance of the Pt-Pd nanotube is consistent with that of other noble metal nanotubes, and the thickness of the tube wall is 7 nm. The specific surface area of the Pt-Pd inner rice tube prepared by the method is 180m2/g。
Example 6:
the gas/solid hydrogen storage of the Pd nanotubes prepared according to example 1 is shown in fig. 12. The instrument was used as a pressure/composition/temperature (PCT) device from advanced materials corp. At 20 ℃, the hydrogen absorption amount of the Pd nano-tube before reaching the hydrogen absorption platform and the hydrogen absorption amount of the Pd nano-tube after reaching the hydrogen absorption platform are respectively 0.11 and 0.64 (atomic ratio H/Pd), and the hydrogen absorption amount is gradually increased along with the increase of the temperature; in contrast, the hydrogen absorption amounts of the Pd polycrystalline material at 20 ℃ were 0.008 and 0.61, respectively. Therefore, when the Pd nano tube is adopted for gas/solid hydrogen storage, the capacity is obviously increased compared with the corresponding polycrystalline material.
The Pd nanotubes also maintained the nanotube structure after 50 hydrogen absorption/desorption cycles (fig. 13). This indicates that the Pd nano-tube has good hydrogen absorption/desorption cycling stability.
Example 7:
the Pt-Pd nanotubes prepared according to example 1 were used as an anode electrocatalyst for a methanol fuel cell, and the catalytic performance thereof was analyzed using cyclic voltammetry. As shown in FIG. 14, methanol began to oxidize at 0.19V (vs. Ag/AgCl), and anoxidation peak appeared around 0.51V (vs. Ag/AgCl), which was much lower than the oxidation potential when Pt-Ru alloy or Pt-Ru nanoparticles were used as the catalyst, so that the oxidation reaction of methanol (equation below) proceeded more easily. In addition, no peaks appear during the flyback, indicating that the Nafion membrane protects Pt well so that it does not undergo oxidation. This catalytic performance of Pt-Pd nanotubes will greatly drive the Development of Methanol Fuel Cells (DMFC).
Claims (8)
1. A noble metal nanotube is characterized in that the noble metal nanotube is a tubular structure with regular openings and composed of noble metal M, the length of the nanotube is 50-60 mu M, the outer diameter is 180-200nm, the wall thickness is 3-10 nm, and the specific surface area is 120-200M-2/g。
2. The noble metal nanotube of claim 1, wherein said nanotube has an outer diameter of 200 nm.
3. The noble metal nanotube of claim 1, wherein said noble metal M is: ag. Pd, Pt, Ru or Pt-Pd.
4. A method for preparing the noble metal nanotubes of claim 1, comprising the steps of:
1) mixing soluble noble metal M salt water solution K2MCl6Or M (NH)3)xClyOr both, wherein x is 4 or 6, y is 2 or 3, and M is: ag. Pd, Pt, Ru or Pt-Pd, and injecting into the porous alumina template at 5-8 mol.L-1Introducing a mixed gas of hydrogen and argon in a volume ratio of 1: 19 at the flow rate of (1), and heating at 150-380 ℃for 1 hour;
2) dissolving an alumina template by using an alkali solution, collecting the obtained solid, washing the solid by using absolute ethyl alcohol and deionized water, and finally drying the solid for 1 hour in vacuum at the temperature of 80 ℃.
5. The method for preparing noble metal nanotubes of claim 4, wherein the alkali solution is 2M NaOH solution.
6. The special apparatus used in the method for preparing noble metal nanotubes of claim 4, which is characterized in that it comprises an exhaust port, a liquid inlet, a cylindrical stainless steel reactor, an upper platinum net, an upper microporous filter, an alumina template, a lower platinum net, a liquid outlet, a gas inlet and a lower microporous filter; the top end of the cylindrical stainless steel reactor is provided with an air outlet and a liquid inlet, and the lower end of the cylindrical stainless steel reactor is provided with an air inlet and a liquid outlet; an upper platinum net, an upper microporous filter, an alumina template, a lower microporous filter and a lower platinum net are sequentially arranged in the cylindrical stainless steel reactor.
7. The special apparatus according to claim 6, wherein the size of the alumina template is: pore diameter: 200nm, thickness: 60 μm, diameter: 47 mm; the stainless steel microporous filter has the following dimensions: pore diameter: 5 μm, thickness: 60 μm, diameter: 48 mm.
8. Use of the noble metal nanotubes of claim 1, characterized in that it is used as an electrode catalyst for hydrogen storage and methanol fuel cells.
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| CN101314182B (en) * | 2008-06-16 | 2011-05-04 | 南昌大学 | Method for preparing hollow metal nano-particle with gamma-aluminum oxide nano-particle as mould plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101314182B (en) * | 2008-06-16 | 2011-05-04 | 南昌大学 | Method for preparing hollow metal nano-particle with gamma-aluminum oxide nano-particle as mould plate |
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