CN107138157A - A kind of core shell structure Au@SiO2The preparation method of supporting Pt nanosphere - Google Patents
A kind of core shell structure Au@SiO2The preparation method of supporting Pt nanosphere Download PDFInfo
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- CN107138157A CN107138157A CN201710300468.6A CN201710300468A CN107138157A CN 107138157 A CN107138157 A CN 107138157A CN 201710300468 A CN201710300468 A CN 201710300468A CN 107138157 A CN107138157 A CN 107138157A
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- 239000002077 nanosphere Substances 0.000 title claims abstract description 33
- 239000011258 core-shell material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 21
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 21
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 21
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims abstract description 10
- 229910004042 HAuCl4 Inorganic materials 0.000 claims abstract description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000010931 gold Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 15
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 8
- 239000002114 nanocomposite Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- -1 stirred Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- 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
- B01J23/52—Gold
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a kind of core shell structure Au@SiO2The preparation method of supporting Pt nanosphere, this method one pot reaction prepares product, using cetyl trimethylammonium bromide as structure directing agent, by the orientated deposition of silicon source tetraethyl orthosilicate outside Au cores, and formaldehyde is as reducing agent, by Au sources HAuCl4·4H2O is reduced to kernel, Pt sources H2PtCl6·6H2O is reduced to SiO2The nano particle loaded on shell, product is core shell structure Au@SiO2Supporting Pt nanosphere.Compared to traditional preparation methods, preparation method of the present invention is simple, and operation is easily controllable, and reaction time is short, and environmental protection, cost is relatively low；Products therefrom nanosphere size tunable, kernel size tunable, the nano particle diameter loaded on shell are controllable, and the stability of product is high, catalytic performance is good, is adapted to electrochemical catalysis etc. and requires higher field to catalytic performance.
Description
Technical field
The invention belongs to the preparing technical field of nuclear-shell structured nano-composite material, and in particular to a kind of core shell structure Au@
SiO2The preparation method of supporting Pt nanosphere.
Background technology
All either there is core status, the nano combined material of hollow-core construction in chemical research or the catalysis of chemical industry association area
Material as catalyst can according to its type catalyst unit different with design feature configuration, most hollow-core constructions be it is spherical,
Such Hollow spheres material is exactly the predecessor of Core-shell structure material, because can fill difference in functionality in spherical shell according to reactant
Kernel.In addition, the particle size of kernel is also an important index.
In the preparation process of tiny balloon, the hollow usual method using sacrifice template is realized, such as with macromolecule material
Material, SiO2Or C is template, constructs the support system of tiny balloon, wherein SiO2Template, which prepares hollow material, to be needed to remove with HF,
High polymer material and C templates then need to remove by sintering.Either which kind of method operating process is all more complicated, it is impossible to one
Product is directly prepared in individual container；And remove template all can a certain degree of damage spheroid.
Hollow-core construction gradually forms core shell structure by the differentiation in several stages：It is individual layer hollow casing structure first, by
Gradually develop into onion shape multilayer nest shell mechanism；This multilayer nest sheathing material continues to develop, different spaces point in spherical shell
Not Bao Han different nano particles, now have evolved to the stage of ripeness of nuclear-shell structured nano-composite material.In addition, there is one kind
Core-shell structure material, shell is directly coated on outside kernel, does not have space between nucleocapsid.Such Core-shell structure material or with Au,
The noble metals such as Pt are kernel, or with Fe3O4It is kernel Deng magnetic material；Casing part can be made of a variety of materials such as SiO2、
TiO2Deng inorganic matter or high-molecular organic material.
The synthetic method of nuclear-shell structured nano-composite material includes soft template method, hard template method, template-free method and spraying
Method, nuclear-shell structured nano-composite material prepared by which kind of method, which all rarely has, is related to shell carried metal especially xenogenesis gold
Category.
The content of the invention
The technical problems to be solved by the invention are that the shortcoming for overcoming above-mentioned preparation method to exist operates letter there is provided one kind
Single, one pot reaction prepares core shell structure Au@SiO2The method of supporting Pt nanosphere.
Solving the technical scheme that is used of above-mentioned technical problem is：By the cetyl that mass fraction is 0.1%~0.3%
Trimethylammonium bromide (CTAB) aqueous solution is heated to 70~90 DEG C, adds the NaOH aqueous solution that mass fraction is 1%~3%, permanent
Temperature stirring 10~20 minutes, it is 0.5%~3% to sequentially add formalin, mass fraction that mass fraction is 3.7%
HAuCl4·4H2The O aqueous solution, mass fraction are 0.5%~3% H2PtCl6·6H2The O aqueous solution, 70~90 DEG C are continued to stir 10
~30 minutes, it was 1 that tetraethyl orthosilicate (TEOS) and absolute ethyl alcohol mass ratio are then added dropwise into reaction solution:1~2 mixed liquor,
Drip rear 70~90 DEG C of stirring reactions 1~3 hour, centrifuge, wash, dry after the completion of reaction, obtain core shell structure Au@SiO2
Supporting Pt nanosphere.
The above-mentioned CTAB aqueous solution and the NaOH aqueous solution, formalin, HAuCl4·4H2The O aqueous solution, H2PtCl6·6H2O
The volume ratio of the aqueous solution is 30:0.75:(2.50~6.25):1:2, the preferably CTAB aqueous solution and the NaOH aqueous solution, formaldehyde is water-soluble
Liquid, HAuCl4·4H2The O aqueous solution, H2PtCl6·6H2The volume ratio of the O aqueous solution is 30:0.75:(4~5):1:2；
Above-mentioned CTAB and TEOS mass ratio are 1:4~6, preferably CTAB and TEOS mass ratio are 1:5.
Preferred NaOH mass fraction is 2% in the above-mentioned NaOH aqueous solution.
Above-mentioned HAuCl4·4H2Preferred HAuCl in the O aqueous solution4·4H2O mass fraction is 1%.
Above-mentioned H2PtCl6·6H2Preferred H in the O aqueous solution2PtCl6·6H2O mass fraction is 1%.
The present invention prepares core shell structure Au@SiO using soft template method one pot reaction2Supporting Pt nanosphere, compared to other
The method for preparing core-shell structured nanomaterials has the following advantages that：
1st, simple to operate, one pot reaction, reaction time is short, and course of reaction is easily controllable, there is great business potential.
2nd, environmental protection, prior synthesizing method needs high-temperature calcination or HF removes template, and this reaction is used as knot using CTAB
Structure directed agents, outside TEOS hydrolysate orientated deposition to kernel, even if the later stage needs to remove CTAB, are extracted using ethanol
Method or vapor high-pressure process can be completed.Minimal amount of low concentration NaOH is only needed in product preparation process, reduces and synthesized
Pollution and potential safety hazard in journey.
3rd, synthesized core shell structure Au@SiO2The core A u of supporting Pt nanosphere size tunable, the Pt nanometers of load
Grain size tunable, SiO2Outer casing thickness is controllable, does not result in Au sources, the waste in Pt sources, saves medicine, and cost is relatively low.
4th, product stability height, excellent catalytic effect, with important industrial application value.
Brief description of the drawings
Fig. 1 is Au@SiO prepared by embodiment 12The transmission electron microscope photo of supporting Pt nanosphere.
Fig. 2 is Au@SiO prepared by embodiment 12The X-ray diffractogram of supporting Pt nanosphere.
Fig. 3 is Au@SiO prepared by embodiment 12The infrared spectrogram of supporting Pt nanosphere.
Fig. 4 is Au@SiO prepared by embodiment 22The transmission electron microscope photo of supporting Pt nanosphere.
Fig. 5 is Au@SiO prepared by embodiment 32The transmission electron microscope photo of supporting Pt nanosphere.
Fig. 6 is Au@SiO prepared by embodiment 42The transmission electron microscope photo of supporting Pt nanosphere.
Fig. 7 is Au@SiO prepared by embodiment 52The transmission electron microscope photo of supporting Pt nanosphere.
Fig. 8 is Au@SiO prepared by embodiment 62The transmission electron microscope photo of supporting Pt nanosphere.
Fig. 9 is Au@SiO prepared by embodiment 72The transmission electron microscope photo of supporting Pt nanosphere.
Embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
0.05g CTAB are added in 24mL deionized waters, stirred, heating water bath adds 0.6mL matter to after 80 DEG C
The NaOH aqueous solution that fraction is 2% is measured, 80 DEG C are stirred 15 minutes, sequentially add the formalin that 3.5mL mass fractions are 3.7%
Solution, 0.8mL mass fractions are 1% HAuCl4·4H2The O aqueous solution, 1.6mL mass fractions are 1% H2PtCl6·6H2O water
Solution, 80 DEG C are continued to stir 10 minutes, the mixed liquor of 0.25g TEOS and 0.5g ethanol are then added dropwise into reaction solution, 80 DEG C are stirred
Reaction 1 hour is mixed, centrifuges, wash after the completion of reaction, 60 DEG C of dryings 12 hours obtain core shell structure Au@SiO2Supporting Pt nanometer
Ball.
As seen from Figure 1, prepared Au@SiO2Supporting Pt nanosphere pattern is preferable.From Figure 2 it can be seen that the nucleocapsid knot prepared
The diffraction maximum of structure nano composite material is consistent with standard card, and thing compare it is pure, 5 diffraction maximums respectively correspond to face-centered cubic
(fcc) (111), (200), (220), (311), the crystal face of (222) of structure Au crystal.Because product is bimetal Au and Pt cores
Shell structure, Au lattice can be shunk, and its diffraction peak is moved to wide-angle.Can by Flied emission transmission electron microscope characterization result
See, the kernel of product is Au, SiO2What is loaded on shell is Pt nano particles.As seen from Figure 3,2.918 and 2.849cm-1Correspondence
The stretching vibration of c h bond in template CTAB, main peak is in 1.066cm-1Near, the stretching vibration of correspondence Si-O keys.
Embodiment 2
In the present embodiment, the mixed liquor of 0.2g TEOS and 0.4g ethanol is added dropwise, other steps are same as Example 1, obtain
Core shell structure Au@SiO2Supporting Pt nanosphere (see Fig. 4).
Embodiment 3
In the present embodiment, the mixed liquor of 0.3g TEOS and 0.6g ethanol is added dropwise, other steps are same as Example 1, obtain
Core shell structure Au@SiO2Supporting Pt nanosphere (see Fig. 5).
Embodiment 4
In the present embodiment, the formalin that 2mL mass fractions are 3.7% is added, other steps are same as Example 1,
Obtain core shell structure Au@SiO2Supporting Pt nanosphere (see Fig. 6).
Embodiment 5
In the present embodiment, the formalin that 2.5mL mass fractions are 3.7%, other steps and the phase of embodiment 1 are added
Together, core shell structure Au@SiO are obtained2Supporting Pt nanosphere (see Fig. 7).
Embodiment 6
In the present embodiment, the formalin that 3mL mass fractions are 3.7% is added, other steps are same as Example 1,
Obtain core shell structure Au@SiO2Supporting Pt nanosphere (see Fig. 8).
Embodiment 7
In the present embodiment, the formalin that 4mL mass fractions are 3.7% is added, other steps are same as Example 1,
Obtain core shell structure Au@SiO2Supporting Pt nanosphere (see Fig. 9).
Claims (6)
1. a kind of core shell structure Au@SiO2The preparation method of supporting Pt nanosphere, it is characterised in that：By mass fraction be 0.1%~
The 0.3% cetyl trimethylammonium bromide aqueous solution is heated to 70~90 DEG C, adds the NaOH that mass fraction is 1%~3%
The aqueous solution, constant temperature is stirred 10~20 minutes, and sequentially adding formalin, mass fraction that mass fraction is 3.7% is
0.5%~3% HAuCl4·4H2The O aqueous solution, mass fraction are 0.5%~3% H2PtCl6·6H2The O aqueous solution, 70~90
DEG C continue to stir 10~30 minutes, it is 1 that tetraethyl orthosilicate and absolute ethyl alcohol mass ratio are then added dropwise into reaction solution:1~2 it is mixed
Liquid is closed, rear 70~90 DEG C of stirring reactions are dripped 1~3 hour, centrifuges, wash, dry after the completion of reaction, obtain core shell structure
Au@SiO2Supporting Pt nanosphere；
The above-mentioned cetyl trimethylammonium bromide aqueous solution and the NaOH aqueous solution, formalin, HAuCl4·4H2The O aqueous solution,
H2PtCl6·6H2The volume ratio of the O aqueous solution is 30:0.75:(2.50~6.25):1:2, cetyl trimethylammonium bromide with just
The mass ratio of silester is 1:4~6.
2. core shell structure Au@SiO according to claim 12The preparation method of supporting Pt nanosphere, it is characterised in that：It is described
The cetyl trimethylammonium bromide aqueous solution and the NaOH aqueous solution, formalin, HAuCl4·4H2The O aqueous solution,
H2PtCl6·6H2The volume ratio of the O aqueous solution is 30:0.75:(4~5):1:2.
3. core shell structure Au@SiO according to claim 1 or 22The preparation method of supporting Pt nanosphere, it is characterised in that：
Described cetyl trimethylammonium bromide and the mass ratio of tetraethyl orthosilicate are 1:5.
4. core shell structure Au@SiO according to claim 1 or 22The preparation method of supporting Pt nanosphere, it is characterised in that：
NaOH mass fraction is 2% in the described NaOH aqueous solution.
5. core shell structure Au@SiO according to claim 1 or 22The preparation method of supporting Pt nanosphere, it is characterised in that：
Described HAuCl4·4H2HAuCl in the O aqueous solution4·4H2O mass fraction is 1%.
6. core shell structure Au@SiO according to claim 1 or 22The preparation method of supporting Pt nanosphere, it is characterised in that：
Described H2PtCl6·6H2H in the O aqueous solution2PtCl6·6H2O mass fraction is 1%.
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-
2017
- 2017-05-02 CN CN201710300468.6A patent/CN107138157B/en active Active
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| CN101670286A (en) * | 2008-09-12 | 2010-03-17 | 北京大学 | Supported transition metal or transition metal alloy nanocluster catalyst and preparation method and application thereof |
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| CN104707597A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Metal nanowire network/mesoporous silica core-shell structure catalyst preparation method |
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|---|
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