CN114559028B - Large-size bismuth nanowire and preparation method thereof - Google Patents
Large-size bismuth nanowire and preparation method thereof Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 107
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000002070 nanowire Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910001152 Bi alloy Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 238000004146 energy storage Methods 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 3
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910016338 Bi—Sn Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910021069 Pd—Co Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
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- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
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- 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
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C25F3/00—Electrolytic etching or polishing
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Abstract
The invention discloses a large-size bismuth nanowire and a preparation method thereof, and relates to the technical field of nano materials. The preparation method of the bismuth nanowire comprises the following steps: carrying out electrochemical dealloying treatment on the lead-bismuth alloy to enable lead elements to be selectively desolventized, and obtaining large-size bismuth nanowires after cleaning and drying; the atomic percentage of bismuth in the lead-bismuth alloy is between 26% and 40%. The preparation method has the advantages of simple device, simple process, low cost, easy large-scale industrial production, and larger and flexible adjustable range, and the structure and the size of the bismuth nanowire can be conveniently regulated and controlled by controlling the proportion of alloy components and parameters of electrochemical dealloying conditions; the obtained bismuth nanowire has compact arrangement, orientation, large macroscopic size, high purity and no doped lead element, can be applied to the fields of catalysis, energy storage, sensing, energy conversion, superconducting and the like, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a large-size bismuth nanowire and a preparation method thereof.
Background
The semi-metal bismuth (Bi) has a series of unique physical and chemical properties such as high specific gravity, low melting point, volume expansion and thermal shrinkage during solidification, no toxicity, stable chemical property, and maximum diamagnetism (the magnetic susceptibility can reach-10) -4 ~ -10 -3 Magnitude), the lowest thermal conductivity among metals other than mercury (8W/(m ·)K) Low electron concentration (about 5 orders of magnitude lower than common metals), very high resistivity (1290 n Ω & m @20 ℃) and the like, and can be widely applied to the fields of metallurgy, chemical industry, electronics, aerospace, medicine and the like. Particularly, the one-dimensional bismuth nanostructure material has wide and important application in the fields of catalysis, energy storage, sensing detection, energy conversion, high-temperature superconductivity and the like. Along with the deep scientific research and the further development of industrial technology, the application field of the one-dimensional bismuth nanostructure material is still expanding continuously. Therefore, research and development of a synthesis and preparation method of bismuth nanowires, which has simple production process, low cost and easy scale, has been widely focused.
At present, common preparation methods of bismuth nanowires include a template method, a hydrothermal method, a solvothermal method, an electrodeposition method, a liquid phase reduction method, a vapor deposition method and the like, are rich and various, are rapidly developed, and can obtain a series of bismuth nanowires with different diameters and lengths. However, the existing preparation method still has a plurality of defects and shortcomings. For example, the template method has relatively complicated procedures and complex subsequent treatment processes; the hydrothermal method and the solvothermal method require high temperature and are harsh in conditions; although the electrodeposition method and the liquid phase reduction method have simple processes and are easy to realize large-scale industrial production, the controllability of the nanowire morphology structure is poor and the purity is not high; the vapor deposition method has high equipment requirement, high cost and low yield; in addition, the bismuth nanowires prepared by the method are difficult to form a macroscopic integral ordered structure, so that the application range of the bismuth nanowires is limited.
In recent years, dealloying (Dealloying) technology has received increasing attention for its advantages of low cost, scalable fabrication, and controllable structure, and has been widely used in a variety of fields. Dealloying refers to a technique of selectively dissolving or removing one or more components from an alloy precursor, and can be classified into chemical dealloying, electrochemical dealloying, gas phase dealloying, and the like (Nano Today 37 (2021) 101094). And the residual components spontaneously form unique micro-nano structures through migration and diffusion processes. Such as a typical bicontinuous nanoporous structure with ultra-high specific surface area and good electrical conductivity and rich and continuous mass transfer channels, can be widely used for transmissionSensing, energy storage, catalysis, photoelectricity and other fields. According to literature reports, various nanoporous metals can be obtained by dealloying of the corresponding alloys, such as nanoporous gold (Au-Ag, au-Al, au-Zn), nanoporous platinum (Pt-Ag, pt-Cu, pt-Si), nanoporous silver (Ag-Al, ag-Zn, ag-Mg), nanoporous palladium (Pd-Co, pd-Al), nanoporous copper (Cu-Al, cu-Zr, cu-Mn), nanoporous titanium (Ti-Mg), and the like. The professor j. Erlebacher, university of hopkins, john, believes (J Electrochem Soc, 2004, 151: C614-C626) that an alloy that is dealloyed to form a nanoporous structure generally has four basic common features: (i) One element is more inert than the other element and the dissolution potential difference Δ ϕ must reach several hundred millivolts; (ii) The alloy composition is typically rich in reactive components; (iii) The alloy must be homogeneous without phase separation prior to dissolution; (iv) The diffusion of the more inert atoms at the alloy/electrolyte interface must be sufficiently rapid. Alloys having these properties include alloys of gold with silver or copper, alloys of palladium with silver or copper, and many others.
Currently, there are relatively few studies on dealloying of bismuth alloys, and bismuth alloys reported in the literature include alloy systems such as Bi-Al, bi-Mg, and Bi-Sn. For example S. Liu et Al (J Mater Chem A, 2016, 4:10098-10104) for Al 30 Bi 70 The alloy strip is subjected to chemical dealloying to obtain a bismuth nano-rod bundle array structure with the diameter smaller than 200nm, and the structure is favorable for promoting diffusion of sodium ions and electrons and can be used as an advanced anode of a Sodium Ion Battery (SIBs). Al prepared by melt spinning 30 Bi 70 In the alloy strip, the pure Al phase and the pure Bi phase are respectively formed because the elements Al and Bi cannot be dissolved in a solid solution, and when the alloy strip is soaked in a 20 wt-percent NaOH solution with the temperature of 60 ℃ for chemical dealloying, the pure Al phase in the alloy strip is dissolved into the NaOH solution, and the pure Bi phase is reserved, so that the bismuth nano-rod bundles arranged in an array are finally formed.
Mg sintered powder with Tartaric Acid (TA) solution by the university of armed forces Jin Xianbo teaching team (Phys. Chem. Phys., 2021,23, 19195-19201) 3 Bi 2 Chemical dealloying of alloy to prepare nano-meterPorous bismuth and the size of the primary Bi nanoparticles was controlled by varying the concentration of TA, as the concentration of TA increased from 2 wt% to 20 wt%, the particle size of Bi increased from about 70 nm to 400 nm. Using the synthesized nano porous Bi sample as CO 2 The smaller the particle size, the higher the catalytic activity was found for the reduced electrocatalyst. However, nanoporous Bi comprising 70 nm particles suffers from mass transfer difficulties and sintering problems during the reaction, whereas 100 nm nanoporous Bi not only provides high formic acid current density and Faraday Efficiency (FE) (16 mA cm) -2 ，FE >90% at-0.88V vs. RHE) and also exhibits excellent durability.
Dealloying generally enables uniform or multi-level nanoporous structures to be obtained, while non-porous structures such as nanowires are rarely present. In the electrochemical dealloying study using the Sn-Bi alloy system, the subject group of Li Kangjin doctor et al (Electrochemistry Communications 81 (2017) 88-92) found that, as the Bi content in the Sn-Bi master alloy was reduced, the material obtained after complete dealloying was converted from a microporous structure composed of bismuth particles to an array-arranged bismuth nanowire-based three-dimensional composite material. And after selectively dissolving the Sn phase from the alloy with ultra-low Bi content, single crystal bismuth nanowires grown in the [110] direction can be obtained. A new strategy for directly preparing bismuth nanowires by electrochemical dealloying is presented for the first time.
The preparation method of the bismuth nanowire by using the electrochemical dealloying method has the special advantages of simplicity, strong reaction controllability, low cost, easiness in large-scale preparation and the like. Earlier, the subject group obtained chinese patent (patent publication No. CN102672162 a) for preparing bismuth nanofiber three-dimensional structure materials by electrochemical corrosion of tin-bismuth solid solution alloys. However, since the soluble bismuth content in tin bismuth solid solutions at room temperature is quite low (< 5 at%), the following problems are caused: the relative yield of the bismuth nanofiber is very low, the consumption of alloy and electric energy is huge, and the cost is relatively high; the bismuth nanowire is fluffy and easy to collapse; the adjustable range of the alloy component proportion is narrow, so that the regulation range of the bismuth nanowire is limited. In addition, tin ions have poor stability in aqueous solution, so that hydrolysis is easy to occur to cause turbidity of electrolyte, hydrolysis products are easy to adhere to the surface of the nanowire, the purity of the product is influenced, and even the smooth dealloying is prevented, and although a proper amount of stabilizers such as cresol sulfonic acid, phenol sulfonic acid and the like can be added to enhance the stability, the raw material cost and the cleaning post-treatment cost are certainly increased.
Disclosure of Invention
Aiming at overcoming the defects and shortcomings of the existing bismuth nanowire synthesis preparation technology, particularly the technical problem that the solid solution bismuth content of a tin-bismuth alloy system is extremely low and the stability of tin ions in aqueous solution is very poor, the invention provides a large-size bismuth nanowire and a preparation method thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a preparation method of large-size bismuth nanowires comprises the following steps: and (3) carrying out electrochemical dealloying treatment on the lead-bismuth alloy to enable lead elements to be selectively desolventized, and cleaning and drying to obtain the large-size bismuth nanowire.
Further, the content of bismuth in the lead bismuth alloy should not exceed a certain range; the lead and bismuth atoms in the alloy in said range being capable of forming a mesophase compound; the range of the lead bismuth alloy prepared by different methods is different; the preferred range of bismuth content in the alloy is between 26 and 40 atomic percent.
As is known from the Pb-Bi alloy phase diagram (N.A. Gokcen, 1992), the Pb-Bi alloy system has a compound intermediate phase (epsilon phase) belonging to the Hexagonal system (Hexagonal, PDF # 39-1087) and having a maximum Pb content of 59.8 to 73 wt%, and a typical composition of Pb 7 Bi 3 。
Compared with the prior art, the bismuth nanowire is obtained by dealloying lead-bismuth alloy containing epsilon phase, which is essentially different from the growth mechanism of preparing bismuth nanowire by dealloying Tetragonal tin-bismuth solid solution alloy (tetra-gonal, PDF#04-0673) in the prior art. In fact, for pure lead phase lead bismuth solid solution (cube, PDF#04-0686) alloys, typical bicontinuous nanoporous structure bismuth materials are formed after dealloying. When the bismuth content is less than 26 at%, the pure lead phase in the lead-bismuth alloy is excessively large in proportion, and a bismuth nano porous structure is formed after dealloying; when the bismuth content is more than 40 and at percent, the proportion of pure bismuth phase in the lead-bismuth alloy is too large, and the bismuth three-dimensional composite structure of the bismuth nanowire and other structures such as a bismuth micro-nano sheet and the like is formed after dealloying. Therefore, the bismuth content in the lead bismuth alloy is preferably in the range of 26 to 40 atomic percent at room temperature.
Compared with 0-5 at% Bi of the tin-bismuth alloy, the bismuth content in the lead-bismuth alloy is improved by more than 5 times, the adjustable range is enlarged by 2 times, and the series of problems caused by extremely low solid solution bismuth content of the tin-bismuth alloy system are overcome.
Further, the lead bismuth alloy can be prepared by smelting, vapor deposition, electrochemical deposition, liquid phase reduction and the like.
The lead bismuth alloy is a very common low-melting-point alloy, the industrialized preparation and application technology of the lead bismuth alloy are quite mature, the production cost is very low, and particularly, the lead bismuth alloy is prepared by adopting a smelting method, so that the alloy with large size and high purity can be conveniently and rapidly obtained.
Further, the electrochemical dealloying treatment is carried out by taking lead-bismuth alloy as a working electrode and carrying out constant potential or variable potential dealloying treatment, wherein the selected working potential is arranged between oxidation potentials of metallic lead and bismuth.
Standard electrode potentials of metallic lead and bismuth at 25 ℃ (p.van ý sek, 2000)E θ (Pb 2+ /Pb)、E θ (Bi 3+ /Bi)、E θ (PbO/Pb)E θ (Bi 2 O 3 Bi) are-0.1262, 0.308, -0.580 and-0.46V vs. SHE respectively, so that the standard oxidation potential difference of bismuth and lead under the acidic and alkaline conditions is 0.4342V and 0.120V respectively, thereby meeting the requirement of the dealloying method on the potential difference. Dealloying aims at allowing the more reactive lead to be oxidized and desolventized, while the relatively stable bismuth remains or rearranges; for this purpose, the working electrode potential must be positive to the oxidation potential of lead and negative to the oxidation potential of bismuth; the more positive the working electrode potential is to the oxidation potential of lead, the faster the dealloying rate of lead and the smaller the diameter of the bismuth nanowire.
Compared with the prior art, the preparation method of the large-size bismuth nanowire provided by the invention has the advantages that the lead element in the lead-bismuth alloy is selectively oxidized into the divalent lead ion (acid condition) or the plumbous acid ion (alkaline condition), the lead element is relatively stable in the corresponding electrolyte, the spontaneous hydrolysis is not easy, the stabilizer is not required to be added, and the problem caused by poor stability of tin ions in the aqueous solution when the tin-bismuth alloy is used for dealloying is avoided.
Further, the electrochemical dealloying treatment is carried out, wherein an acidic solution with pH of less than 5 or an alkaline solution with pH of more than 10 is adopted as electrolyte, the temperature of the electrolyte is 1-100 ℃, preferably 25 ℃, and the diameter of the obtained bismuth nanowire is larger as the temperature of the electrolyte is higher; the acid solution is one of nitric acid, acetic acid and hydrochloric acid solution, preferably nitric acid; the alkaline solution is one of potassium hydroxide and sodium hydroxide solution.
Further, after the cleaning and drying and dealloying treatment is finished, the working electrode is taken out from the electrolyte and put into deionized water for cleaning for a plurality of times, or the working electrode can be immersed into absolute ethyl alcohol for cleaning to reduce the influence of surface tension on the bismuth nanowire during drying, and then the bismuth nanowire is dried in vacuum in a vacuum drying oven to obtain the large-size bismuth nanowire.
Further, the preparation method of the large-size bismuth nanowire can conveniently regulate and control the structure and the size of the bismuth nanowire by controlling the alloy component proportion, the dealloying potential, the electrolyte composition and concentration, the temperature, the time or the electric quantity and other condition parameters.
The invention also provides a large-size bismuth nanowire which is prepared by the preparation method of the large-size bismuth nanowire.
Further, the diameter of the large-size bismuth nanowire is 5-1000 nm, and the longest length is larger than 1mm;
compared with the prior art, the large-size bismuth nanowire provided by the invention has a more compact structure, orientation on macroscopic arrangement, strong controllability of size, structure and morphology, high purity and no doped lead element, and the macroscopic size can reach the order of magnitude of centimeters or more.
The invention also provides application of the large-size bismuth nanowire.
Further, the large-size bismuth nanowire can be widely applied to the fields of catalysis, energy storage, sensing, energy conversion, high-temperature superconductivity and the like.
Drawings
Fig. 1 is a partial SEM image of large-sized bismuth nanowires in example 1 of the present invention.
Fig. 2 is an overall SEM image of large-sized bismuth nanowires in example 1 of the present invention.
Fig. 3 is an EDS face summary of a large-sized bismuth nanowire of example 1 of the present invention.
Fig. 4 is an overall SEM image of the bismuth nanoporous structure of comparative example 1 of the invention.
Fig. 5 is an overall SEM image of the bismuth three-dimensional composite structure in comparative example 2 of the present invention.
Detailed Description
The present invention will be further illustrated in detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
A large-size bismuth nanowire is prepared by the following steps:
(1) Preparing a lead-bismuth alloy: respectively weighing 1.010 g Bi grains (Alapine, 99.99% metals basic) and 2.341 g Pb grains (Shanghai test, 5N), mixing, smelting in a fume hood by using a small portable regulator Wen Xilu, firstly regulating to a heating block of 450 ℃, after the smelting is completed, regulating to a heating block of 300 ℃, continuously stirring and scraping off surface oxides during the process, pouring into a copper sheet after repeated smelting is uniform, and rapidly cooling and solidifying to form ingots; gradually cold pressing the alloy billets into alloy sheets with the thickness of about 0.17 mm by using a hand-operated tablet press (Cheng Long Wujin); finally, annealing in a tube furnace (GSL-1100X, a die of the family of fertilizer) for 30min, heating to 110 ℃, preserving heat for 24h, and slowly introducing protective N during the period 2 Cooling the gas with a furnace to obtain Pb 7 Bi 3 Master alloy sheet.
(2) Electrochemical dealloying: the lead-bismuth alloy is subjected to constant potential dealloying treatment by adopting a three-electrode system of a CHI660E electrochemical workstation, and a master alloy sheet is cut into rectangles of 0.50cm x 1.50cm so as to be clamped by an electrode clamp to be used as a working electrode, and saturated mercurous sulfate is usedThe electrode is a reference electrode, the platinum sheet electrode is a counter electrode, and the electrolyte is 250mL of 0.5M HNO 3 Placing the solution in a DC-1006 low temperature constant temperature tank (Nanjing Shunma instrument equipment Co., ltd.) at 25deg.C; the potential of the lead bismuth alloy working electrode is set to be-0.55V vs. MSE, and constant potential dealloying is started until the dealloying current density approaches zero.
(3) Cleaning and drying: after the dealloying treatment is finished, the working electrode is taken out from the electrolyte, put into deionized water for cleaning for 3-5 times, at least 3min each time, slowly stirred during the period so as to wash out the electrolyte in the material, and then vacuum-dried in a vacuum drying oven at 40 ℃ for 24 hours to obtain the large-size bismuth nanowire.
In this embodiment, pb 7 Bi 3 The X-ray diffraction analysis (XRD) characterization result of the master alloy is Pb 7 Bi 3 Hexagonal phase (Hexagonal, PDF#39-1087). The partial and whole Scanning Electron Microscope (SEM) morphology graphs of the large-size bismuth nanowires prepared after dealloying are respectively shown in fig. 1 and 2, and as shown in fig. 1-2, the bismuth nanowires are aligned along the dealloying direction, have the diameter of 150-200 nm and the length of about 100 mu m, and the unmatched interfaces appear in the middle due to the dealloying of the two sides at the same time. XRD characterization results of the large-size bismuth nanowire are Bi Hexagonal phase (Hexagonal, PDF#85-1329), an EDS surface total spectrum diagram of the bismuth nanowire is shown in figure 3, and the result shows that only Bi element peaks exist, and no doped lead or impurity is lower than the detection limit.
Example 2
A large-size bismuth nanowire is prepared by the following steps:
(1) Preparing a lead-bismuth alloy: weighing 0.998 g Bi grains (Allatin, 99.99% metals basic) and 2.313 g Pb grains (Shanghai test, 5N) respectively, uniformly mixing in a crucible, placing in a tubular furnace, vacuumizing for 3 times, filling protective argon of 0.05MPa, heating to 750 ℃ at 2 ℃/min, preserving heat for 1h, cooling with the furnace, taking out, turning over, remelting for 3-4 times repeatedly to obtain uniform and bright alloy billets, and gradually cold pressing into alloy sheets with the thickness of about 0.20 mm by using an electric roller press; finally placed in a tube furnace (GSL-1100X,the die of the family of the fertilizer) is annealed, vacuumized for 3 times, then filled with protective argon of 0.05MPa, heated to 110 ℃ for 30min, kept for 24h, and then cooled with a furnace to obtain Pb 7 Bi 3 Master alloy sheet.
(2) Electrochemical dealloying: adopting a three-electrode system of a CHI660E electrochemical workstation to perform constant potential dealloying treatment on lead-bismuth alloy, firstly cutting a master alloy sheet into squares with the length of 0.50cm and the length of 0.50cm, then bonding the squares on a copper-clad plate to prepare a working electrode, taking a saturated mercurous sulfate electrode as a reference electrode, a graphite electrode as a counter electrode and 250mL of 0.5M HNO electrolyte 3 Placing the solution in a DC-1006 low temperature constant temperature tank (Nanjing Shunma instrument equipment Co., ltd.) at 10deg.C; the potential of the lead bismuth alloy working electrode is set to be-0.55V vs. MSE, and constant potential dealloying is started until the dealloying current density approaches zero.
(3) Cleaning and drying: after the dealloying treatment is finished, the working electrode is taken out from the electrolyte, put into deionized water for cleaning for 3-5 times, at least 3min each time, and slowly stirred to wash out the electrolyte in the material, and as the obtained bismuth nanowire is thinner, the bismuth nanowire can be immersed into absolute ethyl alcohol for cleaning to reduce the influence of surface tension during drying, and then is dried in vacuum in a vacuum drying oven at 40 ℃ for 24 hours, so that the large-size bismuth nanowire is obtained.
In order to better illustrate the technical solutions of the present invention, the following is further contrasted by way of comparative examples and examples of the present invention.
Comparative example 1
The weight was changed to 1.058 g Bi grains and 3.149 g Pb grains based on example 1 to obtain Pb 75 Bi 25 The master alloy was obtained in the same manner as in example 1, to obtain a bismuth nanoporous structure material.
Comparative example 2
The weight was changed to 1.050 g Bi grains and 1.566 g Pb grains based on example 1 to obtain Pb 60 Bi 40 The master alloy was obtained in the same manner as in example 1, to obtain a bismuth three-dimensional composite structure material.
In comparison with example 1, comparative examples 1 and 2 onlyThe bismuth content of the lead-bismuth master alloy is changed, and the bismuth materials with different structures are obtained after dealloying. In comparative example 1, pb 75 Bi 25 XRD characterization of the master alloy resulted in Pb 7 Bi 3 The hexagonal phase (PDF#39-1087) and Pb Cubic phase (cube, PDF#04-0686) are dealloyed to obtain the bicontinuous bismuth nano porous structure material, the SEM appearance diagram of the bicontinuous bismuth nano porous structure material is shown in figure 4, and the XRD characterization result is Bi hexagonal phase (PDF#85-1329). In comparative example 2, pb 60 Bi 40 XRD characterization of the master alloy resulted in Pb 7 Bi 3 And the hexagonal phase (PDF#39-1087) and the Bi hexagonal phase (PDF#85-1329) are dealloyed to obtain the bismuth three-dimensional composite structural material of the bismuth nanowire and other structures such as the bismuth micro-nano plate and the like, the SEM (scanning electron microscope) topography is shown in figure 5, and the XRD characterization result is the Bi hexagonal phase (PDF#85-1329).
Claims (4)
1. A preparation method of large-size bismuth nanowires is characterized by comprising the following steps: the method comprises the following steps: carrying out electrochemical dealloying treatment on the lead-bismuth alloy to enable lead elements to be selectively desolventized, and obtaining large-size bismuth nanowires after cleaning and drying;
the atomic percentage of bismuth in the lead-bismuth alloy is between 30% and 40%;
the electrochemical dealloying treatment is to take lead bismuth alloy as a working electrode, perform variable-potential dealloying treatment, and set a selected working potential between oxidation potentials of metallic lead and bismuth;
the electrolyte for electrochemical dealloying treatment is alkaline solution with pH of more than 10, and the temperature of the electrolyte is 25 ℃;
the alkaline solution is one of potassium hydroxide and sodium hydroxide solution;
the cleaning and drying steps include taking the working electrode out of the electrolyte, putting the working electrode into deionized water for cleaning, and then carrying out vacuum drying to obtain the large-size bismuth nanowire;
the diameter of the bismuth nanowire is 5-1000 nm.
2. The method for preparing the large-size bismuth nanowire as claimed in claim 1, wherein: the lead bismuth alloy is prepared by smelting, vapor deposition, electrochemical deposition or liquid phase reduction.
3. A large-sized bismuth nanowire, characterized in that: is prepared by the preparation method of the large-size bismuth nanowire as claimed in any one of claims 1 to 2.
4. Use of the large-sized bismuth nanowire as claimed in claim 3 in the fields of catalysis, energy storage, sensing, energy conversion or high temperature superconductivity.
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| CN101603938A (en) * | 2008-06-11 | 2009-12-16 | 中山大学 | Be used for micro-nano structure bismuth pole of trace heavy metal detection and preparation method thereof |
| CN102672162A (en) * | 2012-06-04 | 2012-09-19 | 中山大学 | Bismuth nanofiber three-dimensional structural material and preparation method thereof |
| CN102706937A (en) * | 2012-06-04 | 2012-10-03 | 中山大学 | Micro-nano porous bismuth electrode and preparation method thereof |
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