CN105879867A - Preparation method of semiconductor oxide in-situ supported noble metal cluster - Google Patents
Preparation method of semiconductor oxide in-situ supported noble metal cluster Download PDFInfo
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- CN105879867A CN105879867A CN201610309763.3A CN201610309763A CN105879867A CN 105879867 A CN105879867 A CN 105879867A CN 201610309763 A CN201610309763 A CN 201610309763A CN 105879867 A CN105879867 A CN 105879867A
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- noble metal
- cluster
- conductor oxidate
- metal ion
- precious metal
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 76
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000004065 semiconductor Substances 0.000 title claims abstract description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 64
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 53
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 34
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 239000010931 gold Substances 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010948 rhodium Substances 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 239000004332 silver Substances 0.000 claims abstract description 4
- 239000004020 conductor Substances 0.000 claims description 71
- 239000010970 precious metal Substances 0.000 claims description 55
- 229910021645 metal ion Inorganic materials 0.000 claims description 51
- 239000000084 colloidal system Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 13
- 230000007547 defect Effects 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 14
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 208000034809 Product contamination Diseases 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 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
- 239000002808 molecular sieve Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a semiconductor oxide in-situ supported noble metal cluster. A semiconductor oxide nanocrystalline colloidal solution and a solution containing noble metal ions are mixed according to a mole ratio of semiconductor oxides to the noble metal ions being (1 to 25):1; the semiconductor oxide nanocrystalline colloidal solution and the solution containing noble metal ions are mixed and are irradiated under the laser, and the irradiation time is 10 to 90 minutes, so that the semiconductor oxide in-situ supported noble metal cluster is prepared, wherein the wavelength of exciting light is smaller than or equal to 1239.5/ semiconductor oxide forbidden bandwidth; the semiconductor oxides are one or a plurality of materials from Fe2O3, SnO2, CuO or WO3; the solution containing noble metal ions is a solution containing one or a plurality of ions from gold, silver, ruthenium, rhodium, palladium, osmium, iridium and platinum. The preparation method has the advantages that surfactants and traditional reducing agents are not needed; the defect that by-product pollution can be easily generated when the traditional reducing agents are used for reducing the noble metal ions is overcome; the defect of catalytic activity reduction due to active agent adsorption on the surface of the noble metal cluster is avoided.
Description
Technical field
The present invention relates to loaded noble metal catalyst field, particularly relate to a kind of conductor oxidate carried noble metal group in situ
Bunch preparation method.
Background technology
Loaded noble metal catalyst is a very important industrial catalyst of class, it the energy (such as: the reformation of crude oil and
Isomery, electrode catalyst of fuel cell), environmental protection (such as: the removal of oxynitride in vehicle exhaust), chemicals add
The fields such as work (such as: the synthesis of fine chemicals) have broad application prospects.Commonly using of loaded noble metal catalyst
The materials such as the main active charcoal of carrier, Graphene, CNT, molecular sieve, conductor oxidate, quasiconductor oxygen therein
Compound has rich reserves, with low cost, stability is high and between the noble metal loaded Presence of an interface cooperative effect etc. excellent
Point, therefore suffers from the favor of numerous researcher.
At present, the main method at oxide surface supported precious metal catalyst is by reducing agent (such as: this reducing agent can
To use sodium borohydride, hydrazine hydrate etc.) make precious metal ion reduce and be carried on the surface of oxide, but use these to reduce
Agent inevitably results from the by-product with pollution.As well known to those skilled in the artly, the chi of noble metal catalyst is reduced
Very little, not only contribute to improve the catalytic performance of catalyst, and the atom utilization of noble metal can be effectively improved, it is thus possible to
Enough reduce the manufacturing cost of catalyst.In order to obtain size uniformity and ultra-fine noble metal catalyst, prior art generally exists
Surfactant is added (such as: polyvinylpyrrolidone, cetyl trimethyl bromine during synthesis noble metal catalyst
Change ammonium etc.), but these activating agents easily adsorb the surface at noble metal catalyst, occupy the avtive spot of catalyst, thus
The catalytic performance of catalyst can be reduced.
Summary of the invention
In order to solve above-mentioned technical problem of the prior art, the invention provides your gold a kind of conductor oxidate loads in situ
Belong to the preparation method of cluster, it is not necessary to use surfactant and tradition reducing agent, not only overcome employing tradition reducing agent reduction
The shortcoming being easily generated by-product contamination during precious metal ion, and avoid noble metal cluster surface and cause because of adsorption activity agent
The defect that catalysis activity reduces.
It is an object of the invention to be achieved through the following technical solutions:
The preparation method of a kind of conductor oxidate carried noble metal cluster in situ, according to conductor oxidate: precious metal ion
The mol ratio of=1～25:1, mixes conductor oxidate nanocrystalline colloid solution with the solution containing precious metal ion, is placed in
Carrying out irradiation under exciting light, exposure time is 10～90 minutes, thus prepares conductor oxidate carried noble metal cluster in situ；
Wherein, the energy gap of wavelength≤1239.5/ conductor oxidate of described exciting light；Described conductor oxidate is Fe2O3、
SnO2, CuO or WO3In one or more, the solution containing precious metal ion refer to containing gold, silver, ruthenium, rhodium, palladium, osmium,
The solution of one or more ions in iridium, platinum.
Preferably, at conductor oxidate: in the molar ratio range of precious metal ion=1～25:1, if semiconductor oxide species
Class is constant, conductor oxidate consumption is constant, precious metal ion kind is constant, then in the case of reaction condition is constant,
Along with the increase of precious metal ion consumption, the noble metal cluster quantity of conductor oxidate area load can increase, and finally prepares
The size of conductor oxidate in situ carried noble metal cluster can increase.
Preferably, described conductor oxidate is Fe2O3；According to Fe2O3: precious metal ion=8～the mol ratio of 25:1,
By Fe2O3Nanocrystalline colloid solution mixes with the solution containing precious metal ion, is placed in the visible ray that wavelength is 420～560nm
Lower irradiation 30～90 minutes, thus prepare Fe2O3Carried noble metal cluster in situ.
Preferably, described conductor oxidate is SnO2；According to SnO2: precious metal ion=1～the mol ratio of 5:1, by SnO2
Nanocrystalline colloid solution mixes with the solution containing precious metal ion, is placed under ultraviolet light irradiation 30～90 minutes, thus prepares
SnO2Carried noble metal cluster in situ.
Preferably, described conductor oxidate is CuO；According to CuO: precious metal ion=5～the mol ratio of 20:1, by CuO
Nanocrystalline colloid solution mixes with the solution containing precious metal ion, is placed in irradiation under the visible ray that wavelength is 420～730nm
10～30 minutes, thus prepare CuO carried noble metal cluster in situ.
Preferably, described conductor oxidate is WO3；According to WO3: precious metal ion=5～the mol ratio of 15:1, will
WO3Nanocrystalline colloid solution mixes with the solution containing precious metal ion, is placed in spoke under the visible ray that wavelength is 420～500nm
According to 30～90 minutes, thus prepare WO3Carried noble metal cluster in situ.
As seen from the above technical solution provided by the invention, the conductor oxidate that the embodiment of the present invention is provided is the most negative
The preparation method of supported noble metal cluster uses the light induced electron of photo-excited semiconductor oxide generation as reducing agent, successfully will
The absorption precious metal ion in-situ reducing on conductor oxidate surface is precious metal simple substance atom, and final gathering is formed the most negative
It is loaded in the noble metal cluster on conductor oxidate surface.And the present invention is by changing conductor oxidate in precursors
Kind or consumption, the kind of precious metal ion or consumption, the wavelength of exposure light or the technological parameter such as power, response time, can
Effectively to regulate the final conductor oxidate the prepared component of carried noble metal cluster, particle diameter and load capacity in situ.Thus
Visible, the present invention, without using surfactant, stabilizer and tradition reducing agent, not only overcomes employing tradition reducing agent also
The shortcoming being easily generated by-product contamination during former precious metal ion, it is to avoid noble metal cluster surface causes urging because of adsorption activity agent
The defect that change activity reduces, and the conductor oxidate that preparation technology is simple, production efficiency is high, universality is strong, obtained
Carried noble metal cluster has the advantages such as surface " clean ", ultra-fine grain diameter, size uniformity in situ, therefore in fuel cell and essence
The fields such as refinement work have a wide range of applications.
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, in describing embodiment below, required use is attached
Figure is briefly described, it should be apparent that, the accompanying drawing in describing below is only some embodiments of the present invention, for ability
From the point of view of the those of ordinary skill in territory, on the premise of not paying creative work, it is also possible to obtain other according to these accompanying drawings attached
Figure.
Fig. 1 is the Fe that the embodiment of the present invention 1 prepares2O3The transmission electron microscope photo of supporting Pt cluster in situ.
Fig. 2 is the Fe that the embodiment of the present invention 2 prepares2O3Supporting Pt cluster, Fe in situ2O3Load P d cluster and Fe in situ2O3
Supporting Pt, the transmission electron microscope photo of Pd bis-constituent element cluster in situ.
Fig. 3 is the SnO that the embodiment of the present invention 3 prepares2The transmission electron microscope photo of supporting Pt cluster and corresponding Pt in situ
The particle diameter distribution histogram of cluster.
Fig. 4 is the preparation principle schematic diagram of conductor oxidate carried noble metal cluster provided by the present invention.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely retouched
State, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on this
Bright embodiment, the every other enforcement that those of ordinary skill in the art are obtained under not paying creative work premise
Example, broadly falls into protection scope of the present invention.
The preparation method of the conductor oxidate provided the present invention below carried noble metal cluster in situ is described in detail.
The preparation method of a kind of conductor oxidate carried noble metal cluster in situ, according to conductor oxidate: precious metal ion
The mol ratio of=1～25:1, mixes conductor oxidate nanocrystalline colloid solution with the solution containing precious metal ion, is placed in
Carrying out irradiation under exciting light (such as: described exciting light is visible ray or ultraviolet light), exposure time is 10～90 minutes,
Thus obtain the noble metal cluster of conductor oxidate load in situ.
Wherein, the energy gap (i.e. λ≤1239.5/Eg) of wavelength≤1239.5/ conductor oxidate of described exciting light.Partly lead
Oxide body is Fe2O3、SnO2, CuO or WO3In one or more, say, that described conductor oxidate is received
The brilliant colloid solution of rice is Fe2O3Nanocrystalline colloid solution, SnO2Nanocrystalline colloid solution, CuO nanocrystalline colloid solution or WO3
One or more in nanocrystalline colloid solution, the solution containing precious metal ion refer to containing gold, silver, ruthenium, rhodium, palladium, osmium,
The solution of one or more ions in iridium, platinum.
Specifically, it is respectively Fe when conductor oxidate2O3、SnO2, CuO or WO3Time, provided by the present invention partly lead
The preparation method preferred embodiment of oxide body carried noble metal cluster in situ is as follows:
(1) it is Fe when conductor oxidate2O3Time, according to Fe2O3: precious metal ion=8～the mol ratio of 25:1, by Fe2O3
Nanocrystalline colloid solution mixes with the solution containing precious metal ion, is placed in irradiation under the visible ray that wavelength is 420～560nm
30～90 minutes, thus prepare Fe2O3Carried noble metal cluster in situ.
(2) it is SnO when conductor oxidate2Time, according to SnO2: precious metal ion=1～the mol ratio of 5:1, by SnO2Receive
The brilliant colloid solution of rice mixes with the solution containing precious metal ion, is placed in irradiation 30～90 under the ultraviolet light that dominant wavelength is 254nm
Minute, thus prepare SnO2Carried noble metal cluster in situ.
(3) when conductor oxidate is CuO, according to CuO: precious metal ion=5～the mol ratio of 20:1, CuO is received
The brilliant colloid solution of rice mixes with the solution containing precious metal ion, be placed under the visible ray that wavelength is 420～730nm irradiation 10～
30 minutes, thus prepare CuO carried noble metal cluster in situ.
(4) it is WO when conductor oxidate3Time, according to WO3: precious metal ion=5～the mol ratio of 15:1, by WO3
Nanocrystalline colloid solution mixes with the solution containing precious metal ion, is placed in irradiation under the visible ray that wavelength is 420～500nm
30～90 minutes, thus prepare WO3Carried noble metal cluster in situ.
Further, the preparation method of conductor oxidate provided by the present invention carried noble metal cluster in situ, its principle is such as
Under: as shown in Figure 4, when conductor oxidate is irradiated by light, the electrons of valence band obtains the energy of photon and transition
To conduction band, form light induced electron (e-)；And these light induced electrons can by the absorption noble metal on conductor oxidate surface from
Son is (such as: PtCl6 2-、PdCl4 2-、AuCl4 -、Ag+、Ir3+Deng) in-situ reducing is precious metal simple substance atom；Along with this
That plants precious metal simple substance atom is on the increase gathering, may eventually form the uniform load noble metal group on conductor oxidate surface
Bunch (such as: preparation method provided by the present invention can prepare Pt/Fe2O3、Pd/Fe2O3、PtPd/Fe2O3、Ir/Fe2O3、
Pt/SnO2、Pt/CuO、Ag/CuO、Pt/WO3Deng material).By changing your gold in the described solution containing precious metal ion
Belong to the kind of ion, the group of the noble metal cluster of conductor oxidate surface in situ load in the final product prepared can be controlled
Point.By changing the kind of conductor oxidate in described conductor oxidate nanocrystalline colloid solution, can control finally to make
It the product obtained is the noble metal cluster in which kind of conductor oxidate surface in situ load.At conductor oxidate: noble metal from
In the molar ratio range of son=1～25:1, if semiconductor oxide species is constant, conductor oxidate consumption is constant, your gold
Belong to ionic species constant, then in the case of reaction condition is constant, along with the increase of precious metal ion consumption, quasiconductor oxygen
The noble metal cluster quantity of compound area load can increase, the final conductor oxidate prepared carried noble metal cluster in situ
Size can increase.In the case of reactant is identical with other conditions, the power of exposure light in 20～500W, exposure light
Power is the biggest, and the noble metal cluster quantity of conductor oxidate area load can increase, and the final conductor oxidate prepared is former
The size of position carried noble metal cluster can increase.In the case of reactant is identical with other conditions, exposure time is 10～90
In minute, exposure time is the longest, and the noble metal cluster quantity of conductor oxidate area load can increase, half finally prepared
The size of conducting oxide carried noble metal cluster in situ can increase.
As can be seen here, the present invention uses light induced electron that photo-excited semiconductor oxide produces as reducing agent, it is not necessary to use table
Face activating agent, stabilizer and tradition reducing agent, be easily generated pair when not only overcoming employing tradition reducing agent reduction precious metal ion
The shortcoming of product pollution, it is to avoid noble metal cluster surface causes the defect being catalyzed activity reduction because of adsorption activity agent, and
Preparation technology is simple, production efficiency is high, universality is strong, and obtained conductor oxidate carried noble metal cluster in situ has
The advantages such as surface " clean ", ultra-fine grain diameter, size uniformity, therefore have widely in the field such as fuel cell and fine chemistry industry
Application prospect.
In order to more clearly from show technical scheme provided by the present invention and produced technique effect, below with concrete real
Execute example the preparation method of conductor oxidate provided by the present invention carried noble metal cluster in situ is described in detail.
Embodiment 1
By Fe2O3Nanocrystalline join in deionized water, thus prepare Fe2O3Nanocrystalline colloid solution；According to Fe2O3: your gold
Belong to the mol ratio of ion=25:1, by Fe2O3Nanocrystalline colloid solution mixes with the solution containing precious metal ion, uses 500W
Xenon lamp and use 420nm filter plate (this be equivalent to power be 500W, wavelength be 420～560nm visible ray) to mixed
Closing liquid and carry out irradiation, exposure time is 90 minutes, thus prepares Fe2O3Carried noble metal cluster in situ.
Specifically, Fe2O3Being a kind of important N-type semiconductor material, its energy gap is about 2.2eV.Described noble metal from
Son uses PtCl6 2-, and prepare Fe according to the embodiment of the present invention 12O3Supporting Pt cluster in situ.The embodiment of the present invention 1 is made
The Fe obtained2O3Supporting Pt cluster characterizes in situ, thus it is micro-to obtain high angle scattering dark field transmission electron as shown in Figure 1
Mirror photo (i.e. HAADF-STEM image)；Wherein, Fig. 1 a is the Fe that the embodiment of the present invention 1 prepares2O3Supporting Pt in situ
The HAADF-STEM image one of cluster, Fig. 1 b is the Fe that the embodiment of the present invention 1 prepares2O3Supporting Pt cluster in situ
HAADF-STEM image two.By Fig. 1 a and Fig. 1 b it can be seen that the Pt cluster that the embodiment of the present invention 1 is formed uniformly is divided
Cloth is at Fe2O3Surface, its size is about at about 1nm, and the most also the monatomic Pt of part exists.
Embodiment 2
By Fe2O3Nanocrystalline join in deionized water, thus prepare Fe2O3Nanocrystalline colloid solution；According to Fe2O3: your gold
Belong to the mol ratio of ion=8:1, by Fe2O3Nanocrystalline colloid solution mixes with the solution containing precious metal ion, uses 500W xenon
Lamp and use 420nm filter plate (this be equivalent to power be 500W, wavelength be 420～560nm visible ray) to mixing
Liquid carries out irradiation, and exposure time is 90 minutes, thus prepares Fe2O3Carried noble metal cluster in situ.
Specifically, Fe2O3Being a kind of important N-type semiconductor material, its energy gap is about 2.2eV.Described noble metal from
Son is respectively adopted PtCl6 2-、PdCl4 2-And PtCl6 2-And PdCl4 2-, and prepare Fe respectively according to the embodiment of the present invention 22O3In situ
Supporting Pt cluster, Fe2O3Load P d cluster and Fe in situ2O3Supporting Pt, Pd bis-constituent element cluster in situ.Real to the present invention respectively
Execute the Fe that example 2 prepares2O3Supporting Pt cluster, Fe in situ2O3Load P d cluster and Fe in situ2O3Supporting Pt, Pd bis-groups in situ
Unit's cluster characterizes, thus obtains transmission electron microscope photo (i.e. TEM image) as shown in Figure 2；Wherein, figure
2a is the Fe that the embodiment of the present invention 2 prepares2O3The TEM image of supporting Pt cluster in situ, Fig. 2 b is that the embodiment of the present invention 2 is made
The Fe obtained2O3The TEM image of load P d cluster in situ, Fig. 2 c is the Fe that the embodiment of the present invention 2 prepares2O3In situ supporting Pt,
The TEM image of Pd bis-constituent element cluster.By Fig. 2 a, Fig. 2 b and Fig. 2 c it can be seen that work as and change noble metal in precursors
During the kind of ion, the component of the noble metal cluster of conductor oxidate area load changes the most therewith, say, that this
Bright can be extended to constructing of conductor oxidate surface noble metal cluster.
Embodiment 3
By SnO2Nanocrystalline join in deionized water, thus prepare SnO2Nanocrystalline colloid solution；Respectively according to SnO2:
PtCl6 2-=5:3, the mol ratio of 5:4,1:1, by SnO2Nanocrystalline colloid solution with containing PtCl6 2-Solution mixing, and use
These three mixed liquor is carried out by 250W mercury lamp (this is equivalent to power is 250W, and dominant wavelength is the ultraviolet light of 254nm) respectively
Irradiation, exposure time is 90 minutes, thus prepares Pt0.60/SnO2、Pt0.69/SnO2、Pt0.93/SnO2These three SnO2
Supporting Pt cluster in situ.
Specifically, SnO2Energy gap be about 3.6eV.The SnO that the embodiment of the present invention 3 is prepared2Supporting Pt cluster in situ
Characterize, thus obtain high angle scattering dark field transmission electron microphotograph (i.e. HAADF-STEM as shown in Figure 3
Image) and the particle diameter distribution histogram of corresponding Pt cluster；Wherein, Fig. 3 a is the Pt that the embodiment of the present invention 3 prepares0.60/SnO2
HAADF-STEM image one, Fig. 3 b is the Pt that the embodiment of the present invention 3 prepares0.60/SnO2HAADF-STEM image
Two, Fig. 3 c is that the embodiment of the present invention 3 prepares Pt0.60/SnO2The particle diameter distribution histogram of middle Pt cluster, Fig. 3 d is that the present invention is real
Execute the Pt that example 3 prepares0.69/SnO2HAADF-STEM image one, Fig. 3 e is the Pt that the embodiment of the present invention 3 prepares0.69/SnO2
HAADF-STEM image two, Fig. 3 f is that the embodiment of the present invention 3 prepares Pt0.69/SnO2The particle diameter distribution Nogata of middle Pt cluster
Figure, Fig. 3 g is the Pt that the embodiment of the present invention 3 prepares0.93/SnO2HAADF-STEM image one, Fig. 3 h is that the present invention is real
Execute the Pt that example 3 prepares0.93/SnO2HAADF-STEM image two, Fig. 3 i is that the embodiment of the present invention 3 prepares Pt0.93/SnO2
The particle diameter distribution histogram of middle Pt cluster.By Fig. 3 a, Fig. 3 b, Fig. 3 c, Fig. 3 d, Fig. 3 e, Fig. 3 f, Fig. 3 g, Fig. 3 h
With Fig. 3 i it can be seen that the Pt prepared in the embodiment of the present invention 30.60/SnO2、Pt0.69/SnO2、Pt0.93/SnO2These three SnO2
In situ in supporting Pt cluster, Pt cluster is all evenly distributed in SnO2Surface, and along with PtCl in precursors6 2-Concentration
Increase, SnO2Load capacity and the size of surface Pt cluster are all gradually increased；As can be seen here, at conductor oxidate: noble metal from
In the molar ratio range of son=1～25:1, if semiconductor oxide species is constant, conductor oxidate consumption is constant, your gold
Belong to ionic species constant, then in the case of reaction condition is constant, along with the increase of precious metal ion consumption, quasiconductor oxygen
The noble metal cluster quantity of compound area load can increase, the final conductor oxidate prepared carried noble metal cluster in situ
Size can increase.
As fully visible, the embodiment of the present invention, without using surfactant and tradition reducing agent, not only overcomes employing tradition also
The shortcoming being easily generated by-product contamination during former dose of reduction precious metal ion, and avoid noble metal cluster surface because of adsorption activity
Agent molecule and causing is catalyzed the defect of activity reduction.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, and appoints
How those familiar with the art is in the technical scope that the invention discloses, the change that can readily occur in or replacement, all
Should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection domain of claims
It is as the criterion.
Claims (6)
1. the preparation method of a conductor oxidate carried noble metal cluster in situ, it is characterised in that according to quasiconductor oxygen
Compound: precious metal ion=1～the mol ratio of 25:1, by molten with containing precious metal ion of conductor oxidate nanocrystalline colloid solution
Liquid mixes, and is placed under exciting light carrying out irradiation, and exposure time is 10～90 minutes, thus prepares conductor oxidate in situ
Carried noble metal cluster；
Wherein, the energy gap of wavelength≤1239.5/ conductor oxidate of described exciting light；Described conductor oxidate is
Fe2O3、SnO2, CuO or WO3In one or more, the solution containing precious metal ion refer to containing gold, silver, ruthenium, rhodium,
The solution of one or more ions in palladium, osmium, iridium, platinum.
Preparation method the most according to claim 1, it is characterised in that at conductor oxidate: precious metal ion=1～
In the molar ratio range of 25:1, if semiconductor oxide species is constant, conductor oxidate consumption is constant, precious metal ion
Kind is constant, then in the case of reaction condition is constant, along with the increase of precious metal ion consumption, conductor oxidate table
The noble metal cluster quantity of face load can increase, the size meeting of the final conductor oxidate prepared carried noble metal cluster in situ
Increase.
Preparation method the most according to claim 1 and 2, it is characterised in that described conductor oxidate is Fe2O3；
According to Fe2O3: precious metal ion=8～the mol ratio of 25:1, by Fe2O3Nanocrystalline colloid solution and the solution containing precious metal ion
Mixing, is placed under the visible ray that wavelength is 420～560nm irradiation 30～90 minutes, thus prepares Fe2O3Load expensive in situ
Metal cluster.
Preparation method the most according to claim 1 and 2, it is characterised in that described conductor oxidate is SnO2；
According to SnO2: precious metal ion=1～the mol ratio of 5:1, by SnO2Nanocrystalline colloid solution mixes with the solution containing precious metal ion
Close, be placed under ultraviolet light irradiation 30～90 minutes, thus prepare SnO2Carried noble metal cluster in situ.
Preparation method the most according to claim 1 and 2, it is characterised in that described conductor oxidate is CuO；
According to CuO: precious metal ion=5～the mol ratio of 20:1, CuO nanocrystalline colloid solution is mixed with the solution containing precious metal ion
Close, be placed under the visible ray that wavelength is 420～730nm irradiation 10～30 minutes, thus prepare CuO carried noble metal in situ
Cluster.
Preparation method the most according to claim 1 and 2, it is characterised in that described conductor oxidate is WO3；
According to WO3: precious metal ion=5～the mol ratio of 15:1, by WO3Nanocrystalline colloid solution mixes with the solution containing precious metal ion
Close, be placed under the visible ray that wavelength is 420～500nm irradiation 30～90 minutes, thus prepare WO3Carried noble metal in situ
Cluster.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109759057A (en) * | 2019-01-23 | 2019-05-17 | 常州市龙星工业自动化系统有限公司 | A kind of preparation method and its catalyst of noble metal-oxide composite catalyst |
| CN110891680A (en) * | 2017-07-19 | 2020-03-17 | 乐金华奥斯有限公司 | Catalyst particle for treating automobile exhaust gas, method for producing same, and method for treating automobile exhaust gas using same |
| CN114042451A (en) * | 2021-11-09 | 2022-02-15 | 上海理工大学 | Method for loading metal clusters on photocatalyst |
| CN114734051A (en) * | 2022-04-21 | 2022-07-12 | 中国科学院合肥物质科学研究院 | Method for in-situ preparation of ultra-small precious metal and non-precious metal alloy on carbon carrier |
| CN115672320A (en) * | 2022-11-04 | 2023-02-03 | 上海交通大学 | In WO 3 Method for loading noble metal catalyst nanoparticles on film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008104996A (en) * | 2006-10-27 | 2008-05-08 | Central Japan Railway Co | Photocatalyst, coating liquid for forming photocatalyst and method for manufacturing photocatalyst |
| CN101773827A (en) * | 2009-05-27 | 2010-07-14 | 南京理工大学 | Preparation method of high-activity platinum-loaded TiO2 nanotube photocatalyst |
| CN102784638A (en) * | 2011-05-20 | 2012-11-21 | 北京化工大学 | New process for preparing Pt-M (Mo, au, ce)/C/TiO2fuel cell anode electrocatalyst by in-situ reduction with illumination |
| CN104084193A (en) * | 2014-07-04 | 2014-10-08 | 中国科学院长春应用化学研究所 | Method for preparing Pt catalyst |
-
2016
- 2016-05-10 CN CN201610309763.3A patent/CN105879867A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008104996A (en) * | 2006-10-27 | 2008-05-08 | Central Japan Railway Co | Photocatalyst, coating liquid for forming photocatalyst and method for manufacturing photocatalyst |
| CN101773827A (en) * | 2009-05-27 | 2010-07-14 | 南京理工大学 | Preparation method of high-activity platinum-loaded TiO2 nanotube photocatalyst |
| CN102784638A (en) * | 2011-05-20 | 2012-11-21 | 北京化工大学 | New process for preparing Pt-M (Mo, au, ce)/C/TiO2fuel cell anode electrocatalyst by in-situ reduction with illumination |
| CN104084193A (en) * | 2014-07-04 | 2014-10-08 | 中国科学院长春应用化学研究所 | Method for preparing Pt catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 王其武: "Energy Gaps and Catalytic Properties of Oxides", 《中国科学技术大学学报》 * |
| 王进贤等: "《静电纺丝技术与无机纳米材料合成》", 31 August 2012, 国防工业出版社 * |
| 肖正华等: "光还原法制备Ag/SnO2及其光催化脱色性能研究", 《四川理工学院学报（自然科学版）》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110891680A (en) * | 2017-07-19 | 2020-03-17 | 乐金华奥斯有限公司 | Catalyst particle for treating automobile exhaust gas, method for producing same, and method for treating automobile exhaust gas using same |
| US20200222880A1 (en) * | 2017-07-19 | 2020-07-16 | Lg Hausys, Ltd. | Catalyst particles for treating vehicle exhaust gas, preparation method therefor, and method for treating vehicle exhaust gas by using same |
| US11697109B2 (en) * | 2017-07-19 | 2023-07-11 | Lg Hausys, Ltd. | Catalyst particles for treating vehicle exhaust gas, preparation method therefor, and method for treating vehicle exhaust gas by using same |
| CN109759057A (en) * | 2019-01-23 | 2019-05-17 | 常州市龙星工业自动化系统有限公司 | A kind of preparation method and its catalyst of noble metal-oxide composite catalyst |
| CN114042451A (en) * | 2021-11-09 | 2022-02-15 | 上海理工大学 | Method for loading metal clusters on photocatalyst |
| CN114734051A (en) * | 2022-04-21 | 2022-07-12 | 中国科学院合肥物质科学研究院 | Method for in-situ preparation of ultra-small precious metal and non-precious metal alloy on carbon carrier |
| CN114734051B (en) * | 2022-04-21 | 2024-04-26 | 中国科学院合肥物质科学研究院 | Method for in-situ preparation of ultra-small-size noble metal non-noble metal alloy on carbon carrier |
| CN115672320A (en) * | 2022-11-04 | 2023-02-03 | 上海交通大学 | In WO 3 Method for loading noble metal catalyst nanoparticles on film |
| CN115672320B (en) * | 2022-11-04 | 2024-05-31 | 上海交通大学 | In WO3Method for loading noble metal catalyst nano particles on film |
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