KR101828388B1 - Site-selectively grown metal/semiconductor hybrid nanoparticle and method for manufacturing the same - Google Patents
Site-selectively grown metal/semiconductor hybrid nanoparticle and method for manufacturing the same Download PDFInfo
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- KR101828388B1 KR101828388B1 KR1020150120089A KR20150120089A KR101828388B1 KR 101828388 B1 KR101828388 B1 KR 101828388B1 KR 1020150120089 A KR1020150120089 A KR 1020150120089A KR 20150120089 A KR20150120089 A KR 20150120089A KR 101828388 B1 KR101828388 B1 KR 101828388B1
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 58
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000011941 photocatalyst Substances 0.000 claims abstract description 8
- 239000002923 metal particle Substances 0.000 claims description 17
- 239000010931 gold Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000011133 lead Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- -1 copper cyclohexane nebutyrate Chemical compound 0.000 description 2
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KFAUEMJQYWBXEL-UHFFFAOYSA-J C(C)(=O)[O-].[Cu+2].[Cu+2].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[Cu+2].[Cu+2].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] KFAUEMJQYWBXEL-UHFFFAOYSA-J 0.000 description 1
- YCBDFPZMZNMUTD-UHFFFAOYSA-K C(C)(=O)[O-].[Cu+2].[Cu]Br.C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[Cu+2].[Cu]Br.C(C)(=O)[O-] YCBDFPZMZNMUTD-UHFFFAOYSA-K 0.000 description 1
- KIMWXNAELBXZOQ-UHFFFAOYSA-N ClCCl.[N+](=O)([O-])[O-].[Cu+2].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.[N+](=O)([O-])[O-] Chemical compound ClCCl.[N+](=O)([O-])[O-].[Cu+2].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.[N+](=O)([O-])[O-] KIMWXNAELBXZOQ-UHFFFAOYSA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- 229910017912 NH2OH Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- PAGUDSGSKQZGHS-UHFFFAOYSA-N [Cu].C(C)P(CC)CC.[Cu] Chemical compound [Cu].C(C)P(CC)CC.[Cu] PAGUDSGSKQZGHS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940108925 copper gluconate Drugs 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- JIDMEYQIXXJQCC-UHFFFAOYSA-L copper;2,2,2-trifluoroacetate Chemical compound [Cu+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F JIDMEYQIXXJQCC-UHFFFAOYSA-L 0.000 description 1
- SEKCXMNFUDONGJ-UHFFFAOYSA-L copper;2-ethylhexanoate Chemical compound [Cu+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O SEKCXMNFUDONGJ-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- WFIPUECTLSDQKU-UHFFFAOYSA-N copper;ethyl 3-oxobutanoate Chemical compound [Cu].CCOC(=O)CC(C)=O WFIPUECTLSDQKU-UHFFFAOYSA-N 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J35/004—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
-
- B01J35/026—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The positionally grown grown metal-semiconductor hybrid nanoparticles include a metal core in a polyhedral shape and a semiconductor protrusion which is three-dimensionally grown around the vertex of the metal core. The nanoparticles can improve the performance as a photocatalyst.
Description
TECHNICAL FIELD The present invention relates to a catalyst, and more particularly, to metal-semiconductor hybrid nanoparticles usable as a catalyst and a method for producing the same.
Solar photocatalysts are being extensively studied in response to the demand for solar energy conversion for green technology. However, most known semiconductor photocatalysts are not only less efficient, but they can also cause water pollution problems. In addition, the semiconductor photocatalyst has a narrow optical absorption wavelength range and is rapidly recombined with electrons and holes, and its utilization is limited.
In order to solve these problems, studies have been conducted to combine with the plasmon metal domain, together with development for controlling the shape and structure of the semiconductor / metal hybrid nano structure.
Particularly, it is known that the surface plasmon resonance (SPR) effect due to bonding with the plasmon metal domain improves the interaction with the resonant photons and improves the light scattering property and light absorption property of the semiconductor / metal hybrid nanostructure as a photocatalyst have.
SUMMARY OF THE INVENTION The present invention provides a metal-semiconductor hybrid nanoparticle grown selectively in position.
The present invention also provides a method for producing the metal-semiconductor hybrid nanoparticles.
The positionally grown metal-semiconductor hybrid nanoparticles according to an embodiment of the present invention include a polyhedral metal core and a semiconductor protrusion which is three-dimensionally grown around the vertex of the metal core .
In one embodiment, the metal core comprises gold, platinum or lead.
In one embodiment, the semiconductor protrusion comprises an oxide of copper, nickel, iron or cobalt.
In one embodiment, the metal core has a tetrahedron, an octahedron, a tetrahexahedron, a hexoctahedron, or a cube.
In one embodiment, some of the vertices of the metal core are exposed without being covered by the semiconductor protrusions.
The method for producing metal-semiconductor hybrid nanoparticles according to the embodiment for realizing the object of the present invention includes the steps of preparing a first solution containing polyhedral metal particles and a dispersant, And a second solution containing a metal precursor and polyvinylpyrrolidone to selectively grow semiconductor protrusions on the surface of the metal particles.
In one embodiment, the dispersant comprises sodium citrate dihydrate.
In one embodiment, the first solution further comprises a hydroxyamine hydrochloride (NH2OH < RTI ID = 0.0 > HCI). ≪ / RTI >
In one embodiment, the first solution further comprises a base for increasing the pH.
In one embodiment, the weight average molecular weight of the polyvinylpyrrolidone is from 29,000 to 55,000.
In one embodiment, the growth of the semiconductor protrusions occurs at 50 캜 to 60 캜.
According to the present invention, metal-semiconductor hybrid nanoparticles having increased surface plasmon resonance effect can be obtained, and the nanoparticles can have greatly improved photocatalytic performance.
1 is a perspective view schematically showing metal-semiconductor hybrid nanoparticles produced according to an embodiment of the present invention.
FIG. 2A is a TEM photograph and a model perspective view of the nanoparticles obtained through Example 1. FIG.
FIG. 2B is a TEM photograph and a model perspective view of the nanoparticles obtained in Comparative Example 1. FIG.
2C is a TEM photograph and a model perspective view of the nanoparticles obtained through Comparative Example 2. FIG.
FIG. 3 is a graph showing photocatalytic performance of the nanoparticles of Example 1, Comparative Example 1, and Comparative Example 2. FIG.
Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the drawings. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component. The singular expressions include plural expressions unless the context clearly dictates otherwise.
In this application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a part or a combination thereof is described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.
According to an embodiment of the present invention, in order to prepare positionally grown metal-semiconductor hybrid nanoparticles, metal particles in the form of a polyhedron are prepared.
The metal particles have a polyhedral shape. Therefore, it has a plurality of vertexes. The polyhedral metal particles are covered with facets of a high index such as {321}, {310}, and {730}, and by including portions of large curvature, i.e., sharp apexes, Lt; RTI ID = 0.0 > semiconductor < / RTI > Preferably, each side of the polyhedron may have a triangular shape. For example, the metal particles may have a shape such as a tetrahedron, an octahedron, a tetrahexahedron, a hexoctahedron, a cube, or the like. Considering the curvature and number of vertices, it may be desirable to have a large number of faces. For example, in one embodiment, metal particles of hexahedrons can be preferably used.
The metal particles may include a metal having high catalytic activity such as lead (Pb), gold (Au), silver (Ag), platinum (Pt) .
For example, a first solution containing the polyhedral metal particles, the dispersant, and the reducing agent may be prepared. As the dispersing agent, sodium citrate dihydrate can be preferably used. In addition, the reducing agent may include hydroxyamine hydrochloride (NH 2 OH? HCl). In order to increase the pH of the solution, a base such as sodium hydroxide (NaOH) may be added. When the pH of the solution is increased, the growth kinetics of the semiconductor at the surface of the metal particle is increased, thereby promoting the selective growth of the semiconductor.
A second solution containing a metal precursor and the first solution are mixed to grow a semiconductor on the surface of the polyhedral metal particles.
The second solution comprises a metal precursor and a stabilizer. The metal precursor may include copper (Cu), nickel (Ni), iron (Fe), cobalt (Co), and the like. Examples of the copper precursor include bis (N, N'-di-sec-butylacetamidinate) diglycidyl (Cu), bis (6,6,7,7,8,8,8-heptafluoro (2,2,6,6-tetramethyl-3,5-heptanedionato) copper, bis (triphenylphosphine) copper Copper (II) acetate, copper (II) acetylacetonate, copper (I) bromide copper (II) acetate, Copper (II) chloride, copper cyanide, copper cyclohexane nebutyrate, copper ethyl acetoacetate, copper 2-ethylhexanoate, copper (II) chloride, copper Fluoride, copper formate, copper gluconate, copper hexafluoroacetylacetonate, copper hexafluoroacetylacetonate, copper iodide, (I) thiocyanate, copper (II) trifluoroacetate, copper (II) thiocyanate, copper (II) thiocyanate, copper (Triethylphosphine) copper, (1,10-penanthroline) bis (triphenylphosphine) copper nitrate dichloromethane, copper (II) trifluoromethanesulfonate, cyclopentadienyl Copper (I) chloride, copper (II) chloride, copper (II) chloride and the like can be used. And the like can be used.
As the stabilizer, polyvinyl pyrrolidone is used. The polyvinylpyrrolidone can stabilize the surface of the metal particles and make it possible for the semiconductor to positionally grow on the surface of the polyhedral metal particles in accordance with the difference in chemical potential .
For example, the weight average molecular weight of the polyvinyl pyrrolidone may be from about 29,000 to about 55,000.
The mixture of the first solution and the second solution may be heated at an appropriate temperature for crystal growth, for example, 50 ° C to 60 ° C.
The metal-semiconductor hybrid nanoparticles obtained through the reaction include a polyhedral metal core and a semiconductor portion selectively grown on some of the vertices of the metal core. The semiconductor portion may include a metal oxide formed from the metal precursor. For example, an oxide of copper, nickel, iron or cobalt, and in one embodiment, the semiconductor portion may comprise copper oxide (Cu 2 O).
1 is a perspective view schematically showing metal-semiconductor hybrid nanoparticles produced according to an embodiment of the present invention.
Referring to FIG. 1, the
The metal-semiconductor hybrid nanoparticles having such a structure can have high performance as a photocatalyst by the surface plasmon resonance effect and the charge equilibrium.
Hereinafter, effects of the present invention will be described with reference to Examples and Experimental Examples.
Example 1
An aqueous solution of 0.04 ml of CuCl 2 (50 mM) and 1.0 ml of polyvinylpyrrolidone (weight average molecular weight 55,000, 100 mg / ml) was mixed with 7.21 ml of purified water and shaken for several seconds. Next, 0.5 ml of sodium citrate dihydrate (100 mM), 0.5 ml of hexagonal octahedral gold particles (9.08 mM Au ), 0.25 ml of sodium hydroxide (1.0 M) and 0.5 ml of an aqueous solution of hydroxyamine hydrochloride The mixed solution was then heated at 55 [deg.] C for 2 hours.
Comparative Example 1
An aqueous solution of 0.1 ml of CuCl 2 (10 mM) and 0.1 ml of sodium dodecyl sulfate (300 mM) was mixed with 5.9 ml of purified water and shaken for several seconds. Subsequently, 1.0 ml of sodium citrate dihydrate (100 mM), 0.6 ml of cetyltrimethylammonium bromide (CTAB, 100 mM), 0.5 ml of hexagonal gold particles (4.54 mM Au ), 0.25 ml of sodium hydroxide After mixing with 0.65 ml of an aqueous solution of hydroxyamine (200 mM), the mixed solution was maintained in a bath at 25 DEG C for 1 hour.
Comparative Example 2
An aqueous solution of 0.1 ml of CuCl 2 (10 mM), 0.1 ml of sodium dodecyl sulfate (300 mM) and 1.0 ml of sodium citrate dihydrate (100 mM) was mixed with 6.65 ml of purified water and shaken for several seconds. Subsequently, 1.0 ml of sodium citrate dihydrate (100 mM), 0.6 ml of cetyltrimethylammonium bromide (CTAB, 100 mM), 0.5 ml of hexahedral gold particles (4.54 mM Au ), 0.125 ml of sodium hydroxide After mixing with 0.2 ml of an aqueous solution of hydroxyamine (200 mM), the mixed solution was maintained in a bath at 25 DEG C for 2 hours.
FIG. 2A is a TEM photograph and a model perspective view of the nanoparticles obtained through Example 1. FIG. FIG. 2B is a TEM photograph and a model perspective view of the nanoparticles obtained in Comparative Example 1. FIG. 2C is a TEM photograph and a model perspective view of the nanoparticles obtained through Comparative Example 2. FIG.
Referring to FIG. 2A, it can be seen that nanoparticles having protrusions in which copper oxide semiconductors are three-dimensionally grown centered on the vertexes of gold octahedral gold particles are obtained. In the nanoparticles, some vertices are exposed without projections. Referring to FIG. 2B, it can be seen that nanoparticles in which some vertexes of the hexagonal octahedral gold particles are exposed while the others are covered with copper oxide semiconductors are obtained. Referring to FIG. 2C, It can be confirmed that the nanoparticles covered by the copper oxide semiconductor as a whole are obtained.
When the experimental conditions of Example 1 and Comparative Example 1 are compared, it can be confirmed that the use of polyvinylpyrrolidone is an important factor for the selective growth of semiconductor protrusions.
The photocatalytic performance of the nanoparticles of Example 1, the nanoparticles of Comparative Example 1, and the nanoparticles of Comparative Example 2 was tested and shown graphically in FIG. Photocatalytic performance was evaluated by quantitatively measuring the hydrogen generated by using a xenon lamp (300 W, power density 90 mW cm -2 ) by gas chromatography.
Referring to FIG. 3, the nanoparticles of Comparative Example 1 in which some of the corners were exposed were superior to Comparative Example 2 in which the entire surface of the gold particles was covered with the copper oxide semiconductor. The copper oxide semiconductor was not formed as a layer, It can be confirmed that the nanoparticles of Example 1 having superior hydrogen generation performance are superior to those of Comparative Example 1 and Comparative Example 2.
The present invention can be used in various fields using a photocatalyst such as a pollutant removing device or the like.
Claims (14)
And a semiconductor protrusion which is three-dimensionally grown around a vertex of the metal core,
Wherein a part of the vertexes of the metal core is exposed without being covered by the semiconductor protrusions and the angle of the vertex of the semiconductor protrusion is smaller than the angle of the exposed vertex. .
Mixing the first solution with a second solution comprising a metal precursor and polyvinylpyrrolidone to grow the semiconductor protrusions in three dimensions around the vertex of the metal particles,
Wherein a part of the vertexes of the metal core is exposed without being covered by the semiconductor protrusions and the angle of the vertex of the semiconductor protrusion is smaller than the angle of the exposed vertex. Way.
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| H. Zhou et al., Progress in Natural Science: Materials International, 2013, 23, 273-285.* |
| N. Meir et al., Journal of Materials Chemistry A, 2013, 1, 1763-1769.* |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020028450A1 (en) * | 2018-07-31 | 2020-02-06 | Northwestern University | Tetrahexahedra nanoparticles |
| CN112672974A (en) * | 2018-07-31 | 2021-04-16 | 西北大学 | Tetragon nanoparticles |
| US11673197B2 (en) | 2018-07-31 | 2023-06-13 | Northwestern University | Tetrahexahedra nanoparticles |
| CN112672974B (en) * | 2018-07-31 | 2024-01-26 | 西北大学 | Tetrahedral nanoparticle |
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