CN115533090A - Hollow rhodium nano structure and preparation method thereof - Google Patents
Hollow rhodium nano structure and preparation method thereof Download PDFInfo
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- 239000010948 rhodium Substances 0.000 title claims abstract description 110
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 109
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 17
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 52
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical group O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000010931 gold Substances 0.000 claims abstract description 40
- 229910052737 gold Inorganic materials 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 102
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 61
- 239000011259 mixed solution Substances 0.000 claims description 47
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 32
- YDZWPBPSQHXITB-UHFFFAOYSA-N [Rh].[Au] Chemical compound [Rh].[Au] YDZWPBPSQHXITB-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 229960005070 ascorbic acid Drugs 0.000 claims description 18
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 17
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000002073 nanorod Substances 0.000 claims description 4
- 239000002070 nanowire Substances 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- 239000002244 precipitate Substances 0.000 description 22
- 239000006228 supernatant Substances 0.000 description 22
- 239000002211 L-ascorbic acid Substances 0.000 description 11
- 235000000069 L-ascorbic acid Nutrition 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002078 nanoshell Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241001233305 Xanthisma Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229960000278 theophylline Drugs 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0549—Hollow particles, including tubes and shells
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention relates to a hollow rhodium nano structure and a preparation method thereof, wherein the structure is formed by a discontinuous rhodium thin layer and discrete rhodium nanoclusters. The preparation method of the structure comprises the following steps: rhodium is deposited on the gold nanostructure, and then the hollow rhodium nanostructure is obtained after gold etching. The preparation method is mild in preparation conditions, the hollow rhodium nano structure is obtained by combining template growth with an etching process, and particularly the hollow rhodium nano xanthium structure can be prepared.
Description
Technical Field
The invention relates to a noble metal nano structure and a preparation method thereof, in particular to a hollow rhodium nano structure and a preparation method thereof.
Background
The noble metal nano material shows unique characteristics of optics, electric field, magnetic field and the like due to different compositions, sizes and appearances, and has attracted wide attention in the fields of catalysis, photonics, electronics, biomedicine and the like in recent years. As one of the noble metals, rhodium is used in various catalytic reactions because of its excellent catalytic performance. However, large-scale application of rhodium faces a great obstacle, limited by increasing prices and extremely low abundance in the crust. In recent years, researchers have developed many strategies to increase the utilization of rhodium and reduce its loading to achieve cost control. The hollow rhodium nano structure integrates the advantages of rich porous channels and large specific surface area, can greatly improve the utilization efficiency of rhodium, solves the problem of blockage of a nano catalyst, and is particularly excellent in various structures at present. In the existing rhodium nano catalyst, except for a thin film catalyst, a hollow rhodium nano cluster catalyst is not reported yet.
However, the hollow rhodium nanostructure developed at present is limited to one of isotropic structures such as nanospheres, which greatly limits the application range of the rhodium nanostructure in practical applications; in addition, the strategy for synthesizing the hollow rhodium nanostructure is mostly obtained by etching a template, and the conditions of aqua regia, iodide and the like used in the etching process are too harsh, so that the synthesis cost of the hollow rhodium nanostructure is greatly increased.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a hollow rhodium nano structure with anisotropy and large specific surface area;
the second purpose of the invention is to provide a preparation method of the hollow rhodium nano structure with large specific surface area.
The technical scheme is as follows: the hollow rhodium nano structure is formed by a discontinuous rhodium thin layer and discrete rhodium nanoclusters.
Wherein the diameter of the rhodium nanoclusters is 6-10nm.
The hollow rhodium nano structure is a hollow rhodium nano xanthium structure, a hollow rhodium nano rod structure, a hollow rhodium nano cube, a hollow rhodium nano wire or a hollow rhodium nano star.
According to the preparation method of the hollow rhodium nanostructure, rhodium is deposited on the gold nanostructure, and then gold is etched to obtain the hollow rhodium nanostructure.
The method specifically comprises the following steps:
(1) Adding the gold nanostructure solution into a hexadecyl trimethyl ammonium bromide solution, adding a rhodium trichloride aqueous solution and an ascorbic acid solution, and putting the obtained mixed solution into a drying oven to obtain a solid gold-rhodium nanostructure;
(2) Adding the solid gold-rhodium nano structure into a cetyl trimethyl ammonium bromide solution after centrifugal treatment, adding an acid solution at room temperature, and drying the obtained mixed solution;
(3) And (3) centrifuging the sample obtained in the step (2), placing the sample into a cetyl trimethyl ammonium bromide solution, and dispersing to obtain the hollow rhodium nano structure.
The preparation method of the hollow rhodium nanostructure has universality, and the hollow rhodium nanostructure with the target shape can be obtained only by using the gold nano metal structure with the corresponding shape. Preferably, the gold nanostructure in the step (1) is a gold nanopyramid, and the prepared hollow rhodium nanostructure is a hollow rhodium nano xanthium structure.
Preferably, the gold nanostructure in the step (1) is a gold nanorod, and the prepared hollow rhodium nanostructure is a hollow rhodium nanorod structure.
Wherein, the concentration of the hexadecyl trimethyl ammonium bromide solution in the step (1) is 0.01-0.1 mol/L, the concentration of the rhodium trichloride aqueous solution is 0.001-0.01 mol/L, and the concentration of the ascorbic acid solution is 0.01-0.1 mol/L; the volume ratio of the gold nanostructure to the cetyl trimethyl ammonium bromide to the rhodium chloride to the ascorbic acid is 10-40: 6 to 9:4 to 8:4 to 8. When the concentration of the reaction reagent is lower than the range, the consequences of over-slow reaction rate, incomplete rhodium deposition and the like are brought; when the concentration of the reaction reagent is higher than the above range, the reaction rate is too high, the morphology is not controllable, and in addition, too much rhodium deposition is possibly caused to be unfavorable for the subsequent gold core removal.
Wherein the reaction temperature in the step (1) is 40-80 ℃, and the reaction time is 1-8 h. The problems of incomplete rhodium deposition, too low reaction rate and the like are caused by too low reaction temperature or too short reaction time; the reaction temperature is too high or the reaction time is too long, so that the diffusion effect of the rhodium nanoshell layer on the surface of the gold core is remarkably improved, the appearance is not controllable, and the subsequent removal of the gold core is not facilitated.
Wherein, in the step (2), the concentration of the hexadecyl trimethyl ammonium bromide is 0.01-2 mol/L, the concentration of the acid solution is 1-5 mol/L, and the volume ratio of the solid gold-rhodium nano-structured solution to the hexadecyl trimethyl ammonium bromide solution to the acid solution is 1. When the concentration of the reaction reagent is lower than the range, a series of problems of poor dispersion of the solid gold-rhodium nano structure, uneven and incomplete gold core etching and the like can be caused; when the concentration of the reaction reagent is higher than the range, the problems of too fast etching rate, uncontrollable appearance, too large consumption of the reaction reagent, cost increase and the like are caused.
Wherein the reaction temperature in the step (2) is 60-80 ℃, and the reaction time is 4-8 h. If the reaction temperature is too low or the reaction time is too short, the rate of removing the gold nuclei becomes significantly slow or the gold nuclei cannot be completely removed.
Wherein, the acid solution in the step (2) is preferably hydrochloric acid.
Wherein, the concentration of the hexadecyl trimethyl ammonium bromide solution in the step (3) is 0.001-0.01 mol/L. The cetyl trimethyl ammonium bromide has the functions of serving as a surfactant and stabilizing the surface of the hollow rhodium structure, the concentration is lower than the range, the nano structure cannot be well dispersed, the agglomeration phenomenon is generated, and the performance is not favorable for subsequent application, and when the concentration is higher than the range, the concentration of bromide ions on the surface of the hollow rhodium nano structure is too high, so that the surface catalysis sites are not favorable for exposing, and the performance is reduced.
Wherein, the heating conditions in the steps (2) and (3) are as follows: heating in an oven, heating under water bath conditions, or heating under oil bath conditions.
In the step (3), the dispersing process is as follows: the dispersion was carried out after shaking in a shaker at room temperature.
The reaction principle is as follows: the rhodium metal precursor is subjected to a reduction reaction on the surface of the gold nanostructure under the action of ascorbic acid, and a rhodium nanoshell layer is formed on the surface of the gold nanostructure, so that a solid gold-rhodium nanometer bimetallic structure is formed; in the presence of hexadecyl trimethyl ammonium bromide, the core structure of the gold nanostructure can be etched away by the acidic solution, so that the hollow rhodium nanostructure is obtained. Further, based on a route of template growth and etching, the method takes a gold nanometer double cone as a template, and utilizes hydrochloric acid to etch after a rhodium nanometer cluster shell layer grows to obtain an anisotropic hollow rhodium nanometer xanthium structure. The preparation method can also be popularized to the preparation of hollow rhodium nanostructures in other shapes, and only the gold nanometer bipyramids are replaced by corresponding gold nanostructures, such as gold nanorods, nanocubes, nanowires, nanostars and the like.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: (1) Under the condition of the existence of ascorbic acid and hexadecyl trimethyl ammonium bromide, the gold nanostructure is used as a template agent, and the hollow rhodium nanostructure is prepared by utilizing the process of template growth and re-etching, and has anisotropy and large specific surface area; (2) The etching agent can be low-concentration hydrochloric acid, the preparation condition is mild and simple, and the operability is strong; (3) The obtained hollow rhodium nano xanthium structure is anisotropic and is not available in the prior art; (4) The obtained hollow rhodium nano xanthium structure has uniform appearance and good dispersibility, and has potential application in the fields of photocatalysis, electrocatalysis, ternary catalysis and the like.
Drawings
FIG. 1 is a schematic diagram of the preparation of the present invention;
FIG. 2 is a transmission electron micrograph of a hollow rhodium nano-xanthium structure of example 1;
FIG. 3 is an energy spectrum of the hollow rhodium nano xanthium structure of example 1;
FIG. 4 is a graph of the UV-VIS absorption spectrum of the hollow rhodium nano xanthium structure of example 1;
FIG. 5 is a transmission electron micrograph of solid and hollow Au-Rh nanostructures grown on the basis of Au nanorods according to example 12;
FIG. 6 is a transmission electron micrograph of the structures obtained in comparative examples 1 and 2.
Detailed Description
The present invention is described in further detail below.
Example 1
Step 1, adding 1mL of gold nanometer bipyramid solution into 9mL of 0.001mol/L hexadecyl trimethyl ammonium bromide solution, then adding 400 mu L of 0.01mol/L rhodium trichloride aqueous solution and 400 mu L of 0.1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into an oven with the temperature of 80 ℃ for reaction for 8 hours to obtain a solid gold-rhodium nanometer xanthium structure;
step 2, centrifuging the solid gold-rhodium nano xanthium structure at 8000rpm for 15min, discarding the supernatant, dispersing the lower precipitate into 5mL of 0.01mol/L hexadecyl trimethyl ammonium bromide solution, then respectively adding 5mL of 2mol/L hexadecyl trimethyl ammonium bromide solution and 5mL of 1mol/L hydrochloric acid solution, shaking the obtained mixed solution uniformly, and putting the mixed solution into an 80 ℃ oven for reacting for 8 hours;
and 3, centrifuging the sample obtained in the step 2 at 8000rpm for 10min, discarding the supernatant, dispersing the lower-layer precipitate in 5mL of 0.001mol/L hexadecyl trimethyl ammonium bromide solution, and oscillating for 1h at the rotation speed of 100rpm in an oscillator at room temperature to obtain the hollow rhodium nano xanthium structure.
The prepared hollow rhodium nano xanthium structure is subjected to shape analysis, and as seen in figures 1-3, a transmission electron microscope image, a high-resolution transmission electron microscope image and an energy spectrum image of the hollow rhodium nano xanthium structure are respectively shown, the structure only consists of rhodium elements, the surface of the structure is provided with rich porous channels, a rhodium nano structure layer consists of a discontinuous thin layer and discrete rhodium nanoclusters, the diameter of each cluster is 6-10nm, and the shape endows the hollow rhodium nano xanthium structure with a larger specific surface area.
Fig. 4 is an ultraviolet-visible light absorption spectrum corresponding to the synthesized hollow rhodium nano xanthium structure and the solid gold-rhodium nano xanthium structure, and it can be clearly seen that the SPR resonance peak attributed to the gold nano bipyramid almost disappears after the etching treatment, confirming the successful preparation of the hollow rhodium nano xanthium structure.
Example 2
Step 1, adding 1mL of gold nanometer bipyramid solution into 9mL of 0.001mol/L hexadecyl trimethyl ammonium bromide solution, then adding 500 mu L of 0.01mol/L rhodium trichloride aqueous solution and 500 mu L of 0.1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into an oven with the temperature of 80 ℃ for reaction for 8 hours to obtain a solid gold-rhodium nanometer xanthium structure;
step 2, centrifuging the solid gold-rhodium nano xanthium structure at 8000rpm for 15min, discarding the supernatant, dispersing the lower precipitate into 5mL of 0.01mol/L hexadecyl trimethyl ammonium bromide solution, then respectively adding 5mL of 2mol/L hexadecyl trimethyl ammonium bromide solution and 5mL of 2mol/L hydrochloric acid solution, shaking the obtained mixed solution uniformly, and putting the mixed solution into an 80 ℃ oven for reacting for 8 hours;
and 3, centrifuging the sample obtained in the step 2 at 8000rpm for 10min, discarding the supernatant, dispersing the lower-layer precipitate in 5mL of 0.001mol/L cetyl trimethyl ammonium bromide solution, and oscillating for 1h at the rotation speed of 100rpm in an oscillator at room temperature to obtain the hollow rhodium nano xanthium structure.
Example 3
Step 1, adding 1mL of gold nanometer bipyramid solution into 9mL of 0.001mol/L hexadecyl trimethyl ammonium bromide solution, then adding 600 mu L of 0.01mol/L rhodium trichloride aqueous solution and 600 mu L of 0.1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into an oven with the temperature of 80 ℃ for reaction for 8 hours to obtain a solid gold-rhodium nanometer xanthium structure;
step 2, centrifuging the solid gold-rhodium nano xanthium structure at 8000rpm for 15min, discarding the supernatant, dispersing the lower precipitate into 5mL of 0.01mol/L hexadecyl trimethyl ammonium bromide solution, then respectively adding 5mL of 2mol/L hexadecyl trimethyl ammonium bromide solution and 5mL of 3mol/L hydrochloric acid solution, shaking the obtained mixed solution uniformly, and putting the mixed solution into an 80 ℃ oven for reacting for 8 hours;
and 3, centrifuging the sample obtained in the step 2 at 8000rpm for 10min, discarding the supernatant, dispersing the lower-layer precipitate in 5mL of 0.001mol/L cetyl trimethyl ammonium bromide solution, and oscillating for 1h at the rotation speed of 100rpm in an oscillator at room temperature to obtain the hollow rhodium nano xanthium structure.
Example 4
Step 1, adding 1mL of gold nanometer bipyramid solution into 9mL of 0.001mol/L hexadecyl trimethyl ammonium bromide solution, then adding 700 mu L of 0.01mol/L rhodium trichloride aqueous solution and 700 mu L of 0.1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into an oven with the temperature of 80 ℃ for reaction for 8 hours to obtain a solid gold-rhodium nanometer xanthium structure;
step 2, centrifuging the solid gold-rhodium nano xanthium structure at 8000rpm for 15min, discarding the supernatant, dispersing the lower precipitate into 5mL of 0.01mol/L hexadecyl trimethyl ammonium bromide solution, then respectively adding 5mL of 2mol/L hexadecyl trimethyl ammonium bromide solution and 5mL of 4mol/L hydrochloric acid solution, shaking the obtained mixed solution uniformly, and putting the mixed solution into an 80 ℃ oven for reacting for 8 hours;
and 3, centrifuging the sample obtained in the step 2 at 8000rpm for 10min, discarding the supernatant, dispersing the lower-layer precipitate in 5mL of 0.001mol/L cetyl trimethyl ammonium bromide solution, and oscillating for 1h at the rotation speed of 100rpm in an oscillator at room temperature to obtain the hollow rhodium nano xanthium structure.
Example 5
Step 1, adding 1mL of gold nanometer bipyramid solution into 9mL of 0.001mol/L hexadecyl trimethyl ammonium bromide solution, then adding 800 mu L of 0.01mol/L rhodium trichloride aqueous solution and 800 mu L of 0.1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into an oven with the temperature of 80 ℃ for reaction for 8 hours to obtain a solid gold-rhodium nanometer xanthium structure;
step 2, centrifuging the solid gold-rhodium nano xanthium structure at 8000rpm for 15min, discarding the supernatant, dispersing the lower precipitate into 5mL of 0.01mol/L hexadecyl trimethyl ammonium bromide solution, then respectively adding 5mL of 2mol/L hexadecyl trimethyl ammonium bromide solution and 5mL of 5mol/L hydrochloric acid solution, shaking the obtained mixed solution uniformly, and putting the mixed solution into an 80 ℃ oven for reacting for 8 hours;
and 3, centrifuging the sample obtained in the step 2 at 8000rpm for 10min, discarding the supernatant, dispersing the lower-layer precipitate in 5mL of 0.001mol/L cetyl trimethyl ammonium bromide solution, and oscillating for 1h at the rotation speed of 100rpm in an oscillator at room temperature to obtain the hollow rhodium nano xanthium structure.
Example 6
Step 1, adding 2mL of gold nanometer bipyramid solution into 8mL of 0.001mol/L hexadecyl trimethyl ammonium bromide solution, then adding 400 mu L of 0.01mol/L rhodium trichloride aqueous solution and 400 mu L of 0.1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into an oven with the temperature of 80 ℃ for reaction for 8 hours to obtain a solid gold-rhodium nanometer xanthium structure;
step 2, centrifuging a solid gold-rhodium nano xanthium structure at 8000rpm for 15min, removing a supernatant, dispersing a lower-layer precipitate into 5mL of 0.10mol/L hexadecyl trimethyl ammonium bromide solution, then respectively adding 5mL of 2mol/L hexadecyl trimethyl ammonium bromide solution and 5mL of 3mol/L hydrochloric acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into an oven at 80 ℃ for reacting for 8 hours;
and 3, centrifuging the sample obtained in the step 2 at 8000rpm for 10min, discarding the supernatant, dispersing the lower-layer precipitate in 5mL of 0.001mol/L cetyl trimethyl ammonium bromide solution, and oscillating for 1h at the room temperature at the rotation speed of 200rpm in an oscillator to obtain the hollow rhodium nano xanthium structure.
Example 7
Step 1, adding 3mL of gold nanoparticle bipyramid solution into 7mL of 0.001mol/L hexadecyl trimethyl ammonium bromide solution, then adding 400 mu L of 0.01mol/L rhodium trichloride aqueous solution and 400 mu L of 0.1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into an oven with the temperature of 80 ℃ for reaction for 8 hours to obtain a solid gold-rhodium nano xanthium structure;
step 2, centrifuging the solid gold-rhodium nano xanthium structure at 8000rpm for 15min, discarding the supernatant, dispersing the lower precipitate into 5mL of 0.10mol/L hexadecyl trimethyl ammonium bromide solution, then respectively adding 5mL of 2mol/L hexadecyl trimethyl ammonium bromide solution and 5mL of 4mol/L hydrochloric acid solution, shaking the obtained mixed solution uniformly, and putting the mixed solution into an 80 ℃ oven for reacting for 8 hours;
and 3, centrifuging the sample obtained in the step 2 at 8000rpm for 10min, discarding the supernatant, dispersing the lower-layer precipitate in 5mL of 0.001mol/L cetyl trimethyl ammonium bromide solution, and oscillating for 1h at the room temperature at the rotation speed of 200rpm in an oscillator to obtain the hollow rhodium nano xanthium structure.
Example 8
Step 1, adding 4mL of gold nanoparticle bipyramid solution into 6mL of 0.001mol/L hexadecyl trimethyl ammonium bromide solution, then adding 400 mu L of 0.01mol/L rhodium trichloride aqueous solution and 400 mu L of 0.1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and putting the mixed solution into an oven at 80 ℃ for reaction for 8 hours to obtain a solid gold-rhodium nano xanthium structure;
step 2, centrifuging the solid gold-rhodium nano xanthium structure at 8000rpm for 15min, discarding the supernatant, dispersing the lower precipitate into 5mL of 0.10mol/L hexadecyl trimethyl ammonium bromide solution, then respectively adding 5mL of 2mol/L hexadecyl trimethyl ammonium bromide solution and 5mL of 5mol/L hydrochloric acid solution, shaking the obtained mixed solution uniformly, and putting the mixed solution into an 80 ℃ oven for reacting for 8 hours;
and 3, centrifuging the sample obtained in the step 2 at 8000rpm for 10min, discarding the supernatant, dispersing the lower-layer precipitate in 5mL of 0.001mol/L cetyl trimethyl ammonium bromide solution, and oscillating for 1h at the room temperature at the rotation speed of 200rpm in an oscillator to obtain the hollow rhodium nano xanthium structure.
Example 9
Step 1, adding 1mL of gold nanometer bipyramid solution into 9mL of 0.001mol/L hexadecyl trimethyl ammonium bromide solution, then adding 400 mu L of 0.01mol/L rhodium trichloride aqueous solution and 400 mu L of 0.1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into an oven with the temperature of 80 ℃ for reaction for 8 hours to obtain a solid gold-rhodium nanometer xanthium structure;
step 2, centrifuging a solid gold-rhodium nano xanthium structure at 12000rpm for 15min, removing a supernatant, dispersing a lower-layer precipitate into 5mL of 0.1mol/L hexadecyl trimethyl ammonium bromide solution, adding 5mL of 2mol/L hexadecyl trimethyl ammonium bromide solution and 5mL of 1mol/L hydrochloric acid solution respectively, shaking uniformly, and putting the obtained mixed solution into an oven at 80 ℃ for reacting for 8 hours;
and 3, centrifuging the sample obtained in the step 2 at 12000rpm for 10min, discarding the supernatant, dispersing the lower precipitate in 5mL of 0.01mol/L hexadecyl trimethyl ammonium bromide solution, and oscillating for 1h at room temperature in an oscillator at the rotating speed of 200rpm to obtain the hollow rhodium nano xanthium structure.
Example 10
Step 1, adding 1mL of gold nanometer bipyramid solution into 9mL of 0.001mol/L hexadecyl trimethyl ammonium bromide solution, then adding 400 mu L of 0.001mol/L rhodium trichloride aqueous solution and 400 mu L of 0.1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into a 40 ℃ oven for reaction for 1h to obtain a solid gold-rhodium nanometer xanthium structure;
step 2, centrifuging the solid gold-rhodium nano xanthium structure at 8000rpm for 10min, discarding the supernatant, dispersing the lower-layer precipitate into 5mL of 0.001mol/L hexadecyl trimethyl ammonium bromide solution, then respectively adding 5mL of 2mol/L hexadecyl trimethyl ammonium bromide solution and 5mL of 1mol/L hydrochloric acid solution, shaking the obtained mixed solution uniformly, and putting the mixed solution into a 60 ℃ drying oven for reacting for 4 hours;
and 3, centrifuging the sample obtained in the step 2 at 8000rpm for 10min, discarding the supernatant, dispersing the lower-layer precipitate in 5mL of 0.001mol/L cetyl trimethyl ammonium bromide solution, and oscillating for 1h at the rotation speed of 100rpm in an oscillator at room temperature to obtain the hollow rhodium nano xanthium structure.
Example 11
Step 1, adding 1mL of gold nano bipyramid solution into 9mL of 0.1mol/L hexadecyl trimethyl ammonium bromide solution, then adding 400 mu L of 0.01mol/L rhodium trichloride aqueous solution and 400 mu L of 1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into an oven at 80 ℃ for reaction for 8 hours to obtain a solid gold-rhodium nano xanthium structure;
step 2, centrifuging a solid gold-rhodium nano xanthium structure at 12000rpm for 15min, removing a supernatant, dispersing a lower-layer precipitate into 5mL of 0.01mol/L hexadecyl trimethyl ammonium bromide solution, then respectively adding 5mL of 2mol/L hexadecyl trimethyl ammonium bromide solution and 5mL of 5mol/L hydrochloric acid solution, shaking the obtained mixed solution uniformly, and putting the mixed solution into an oven at 80 ℃ for reacting for 8 hours;
and 3, centrifuging the sample obtained in the step 2 at 12000rpm for 15min, discarding the supernatant, dispersing the lower precipitate in 5mL of 0.01mol/L hexadecyl trimethyl ammonium bromide solution, and oscillating for 3h at the room temperature in an oscillator at the rotating speed of 200rpm to obtain the hollow rhodium nano xanthium structure.
Example 12
On the basis of example 1, the gold nanopyramids were replaced with a gold nanorod solution, unlike example 1.
As can be seen from FIG. 5, the gold nanorod sample with low purity is used as the template of the gold hollow rhodium nanostructure, wherein the gold nanorod sample, the gold nanosphere and the gold nanocube are included, and the corresponding shapes are marked in the figure. The solid gold-rhodium nanometer structure and the hollow rhodium nanometer structure are faithfully copied with the shape of the corresponding gold nanometer structure inner core, and the obtained hollow rhodium nanometer structure has the structures of a hollow rhodium nanometer rod structure, a hollow rhodium nanometer cube, a hollow rhodium nanometer sphere and the like. This example illustrates the general applicability of the preparation method of the present invention.
Comparative example 1
On the basis of example 1, the difference from example 1 is that the concentration of the rhodium trichloride solution in step 1 is 0.0008mol/L.
Comparative example 2
On the basis of example 1, the temperature in step 2 was 50 ℃ unlike example 1.
As can be seen from fig. 6, the synthesis of the hollow xanthium rhodium nanostructure is significantly influenced by the temperature and concentration of the reaction reagents. The problems of incomplete rhodium deposition, incomplete gold core etching and the like can occur when the concentration of the reaction reagent is too low or the reaction temperature is too low.
Claims (10)
1. A hollow rhodium nanostructure, formed from a discontinuous thin layer of rhodium and discrete rhodium nanoclusters.
2. The hollow rhodium nanostructure of claim 1, wherein the diameter of the rhodium nanoclusters is 6-10nm.
3. The hollow rhodium nanomaterial of claim 1, wherein the hollow rhodium nanostructure is a hollow rhodium nano xanthium structure, a hollow rhodium nanorod structure, a hollow rhodium nanocube, a hollow rhodium nanowire, or a hollow rhodium nanostar.
4. A method of making the hollow rhodium nanostructure of claim 1, wherein rhodium is deposited on the gold nanostructure and then the gold is etched to obtain the hollow rhodium nanostructure.
5. The method for preparing a hollow rhodium nanostructure according to claim 4, characterized by comprising the following steps:
(1) Adding the gold nanostructure solution into a hexadecyl trimethyl ammonium bromide solution, adding a rhodium trichloride aqueous solution and an ascorbic acid solution, and reacting the obtained mixed solution under a heating condition to obtain a solid gold-rhodium nanostructure;
(2) Adding a solid gold-rhodium nano structure into a hexadecyl trimethyl ammonium bromide solution after centrifugal treatment, adding an acid solution at room temperature, and reacting the obtained mixed solution under a heating condition;
(3) And (3) centrifuging the sample obtained in the step (2), placing the sample into a cetyl trimethyl ammonium bromide solution, and dispersing to obtain the hollow rhodium nano structure.
6. The method for preparing a hollow rhodium nanostructure according to claim 5, wherein the concentration of the cetyltrimethylammonium bromide solution in the step (1) is 0.01-0.1 mol/L, the concentration of the rhodium trichloride aqueous solution is 0.001-0.01 mol/L, and the concentration of the ascorbic acid solution is 0.01-0.1 mol/L.
7. The method for preparing the hollow rhodium nanostructure according to claim 5, wherein the reaction temperature in the step (1) is 40-80 ℃ and the reaction time is 1-8 h.
8. The method for preparing a hollow rhodium nanostructure according to claim 5, wherein the concentration of cetyl trimethyl ammonium bromide in the step (2) is 0.01-2 mol/L, and the concentration of the acidic solution is 1-5 mol/L.
9. The method for preparing the hollow rhodium nanostructure according to claim 5, wherein the reaction temperature in the step (2) is 60-80 ℃ and the reaction time is 4-8 h.
10. The method for preparing a hollow rhodium nanostructure according to claim 5, wherein the concentration of the cetyltrimethylammonium bromide solution in the step (3) is 0.001-0.01 mol/L.
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