CN106040234A - Platinum and gallium composite nano-catalyst and preparation method thereof - Google Patents
Platinum and gallium composite nano-catalyst and preparation method thereof Download PDFInfo
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- CN106040234A CN106040234A CN201610397753.XA CN201610397753A CN106040234A CN 106040234 A CN106040234 A CN 106040234A CN 201610397753 A CN201610397753 A CN 201610397753A CN 106040234 A CN106040234 A CN 106040234A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 301
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 150
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 144
- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000002347 injection Methods 0.000 claims abstract description 7
- 239000007924 injection Substances 0.000 claims abstract description 7
- 238000005119 centrifugation Methods 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 104
- 239000002105 nanoparticle Substances 0.000 claims description 36
- 150000001298 alcohols Chemical class 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000376 reactant Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052756 noble gas Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 abstract 1
- IMMRYVXLCAMRNK-UHFFFAOYSA-N gallium;pentane-2,4-dione Chemical compound [Ga+3].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O IMMRYVXLCAMRNK-UHFFFAOYSA-N 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 77
- 239000002245 particle Substances 0.000 description 37
- 239000000843 powder Substances 0.000 description 16
- 238000006555 catalytic reaction Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- 101100335921 Mus musculus Gapt gene Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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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
- B01J23/38—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
-
- 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
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a platinum and gallium composite nano-catalyst. The preparation method comprises the following steps: S1, platinum bis(acetylacetonate) and gallium(III) 2,4-pentanedionate are dissolved in an alcohol solvent and mixed uniformly, and a mixed solution is prepared; S2, the alcohol solvent is added to a reactor and heated under inert gas shielding; S3, a catalyst carrier is added to the reactor in advance, the mixed solution is added to the reactor with a thermal injection method, and a reaction liquid is obtained through a reaction; S4, the reaction liquid is reacted for a period of time at a higher temperature in advance and then is heated and stirred in water bath, centrifugation, drying and roasting are performed sequentially after stirring, and the platinum and gallium composite nano-catalyst is prepared. Correspondingly, the invention further discloses the platinum and gallium composite nano-catalyst. The preparation method adopts the thermal injection method, the alcohol solvent is taken as a solvent and a reducing agent, and common reduction, nucleation and growth of platinum and gallium are promoted under the reduction action of the alcohol solvent at a high temperature in the nitrogen environment.
Description
Technical field
The present invention relates to field of nanometer material technology, particularly relate to a kind of platinum gallium composite nano-catalyst and preparation method thereof.
Background technology
Compared with body phase material, noble metal nanometer material shows many distinct physicochemical properties, space flight,
The energy, medicine, environmental protection, chemical industry and photoelectric field have showed the prospect of being widely applied.Research shows, the property of noble metal nanometer material
Matter is closely related with its pattern and size, and people can be come by the appearance structure and size that control noble metal nanometer material
Realize the regulation and control to its performance, but the controlledly synthesis how realizing noble metal nanometer material is the key realizing its application.
Platinum, as a kind of common precious metal material, physicochemical properties based on its excellence, has ten at catalytic field
Divide and be widely applied.Platinum based catalyst shows the catalysis of excellence in the reactions such as hydrocarbons hydrogenation, coupling, dehydrogenation and aromatization
Activity, but to still suffer from some problems, such as catalyst life in use the highest for platinum catalyst；At high temperature it is easily generated long-pending
Carbon, these carbon distributions are attached to catalyst surface, plug reaction channel, thus cause rapid catalyst deactivation.Develop new urging
Change system, the high-temperature stability improving platinum based catalyst is the key solving current problem.Research shows, prepares composite catalyst
It is favorably improved stability and the reactivity of platinum catalyst, such as when adding gallium element as auxiliary agent in platinum catalyst, no
It is only capable of the reactivity significantly improving catalyst, and the stability of catalyst can be improved, by gallium in regulation catalyst
Content, it is possible to make catalyst present preferable aromatisation, isomerization or hydrocracking reaction selectivity.Existing preparation
The method of composite catalyst include physical mixed, active nanoparticles be carried on carrier, the decomposition of metal-carbonyl, slaine also
Former and bimetallic common reduction etc..But the composite catalyst composition prepared of physical mixing processes and particle diameter skewness
Even；It is relatively low that load method preparation method obtains catalyst nano Compound Degree ratio, poor repeatability, although can be increased by post processing
Compound Degree, but the catalytic performance of catalyst can be reduced to a certain extent and increase process costs；Electronation and heat point
The methods such as solution exist that synthesis mechanism is unclear, productivity is relatively low, poor repeatability, cannot problems such as synthesis on a large scale；In order to more
The good pattern controlling composite nanometer particle and size, conventional synthesis all in oil-based system (such as oleyl amine) carry out, these are molten
Agent is attached to the surface of nano-particle and is difficult to be removed by conventional method (centrifugal or roasting), can form carbon distribution under the high temperature conditions
It is attached to catalyst surface, thus blocking catalyst surface activity site.Therefore a kind of efficiently prepared composition of exploitation be evenly distributed,
The actual application tool of platinum based catalyst is of great significance by the method for the composite catalyst that scale topography is controlled.
Summary of the invention
For solving above-mentioned technical problem, it is desirable to provide the preparation method of a kind of platinum gallium composite nano-catalyst, bag
Include following steps:
S1, acetylacetone,2,4-pentanedione platinum and acetylacetone,2,4-pentanedione gallium are dissolved in alcohols solvent and mix homogeneously, prepare mixed solution；
S2, alcohols solvent is added in reactor, and described alcohols solvent is heated under inert gas shielding；
S3, in advance catalyst carrier is added in reactor, more described mixed solution is added reaction by hot injection method
In device, reaction obtains reactant liquor；
S4, reactant liquor react a period of time the most at relatively high temperatures, subsequently described reactant liquor are carried out heating in water bath also
Stirring, is centrifuged separation, dry, roasting successively, prepares platinum gallium composite nano-catalyst after stirring.
Further, in described step S2, the temperature of heating is 160-245 DEG C；
In described step S3, reaction condition is: pressure be 0.1MPa, temperature be 160-245 DEG C under conditions of react 5-
30min。
Further, in described step S2, noble gas is nitrogen or argon.
Further, the straight chain that alcohols solvent is C4-C10 in described step S1 or the branched chain dihydric alcohol or many of C4-C10
Unit's alcohol.
Further, reactant liquor described in described step S4 carries out the temperature of heating in water bath and is 60-80 DEG C, and mixing time is
5-8h。
Further, being roasted in Muffle furnace in described step S4 is carried out, and roasting condition is the temperature at 600-800 DEG C
The lower roasting 1-3h of degree.
Further, in the centrifugation of described step S4, using ethanol as good solvent, acetone is as bad molten
Agent.
Further, in described step S1, mixed solution is to prepare in glove box.
Correspondingly, present invention also offers a kind of platinum gallium composite nano-catalyst, described catalyst is by above-mentioned method
Preparing, described catalyst includes that platinum gallium nano-particle and catalyst carrier, described platinum gallium nano-particle are supported on catalysis
On agent carrier.
Further, the load capacity of described platinum gallium nano-particle is 2-4%, a size of 10-15nm, described platinum gallium nanometer
In Li, the ratio of gallium is 13%-82%.
Present invention also offers a kind of method preparing platinum gallium nano-particle, comprise the following steps:
S1, in glove box, acetylacetone,2,4-pentanedione platinum and acetylacetone,2,4-pentanedione gallium are dissolved in alcohols solvent and mix homogeneously, prepare mixed
Close solution；
S2, pipette alcohols solvent in reactor, and described alcohols solvent is heated under inert atmosphere protection；
S3, being added in reactor by hot injection method by described mixed solution, reaction obtains reactant liquor；
S4, by described reactant liquor centrifugation and be dried, prepare platinum gallium composite nanometer particle.
Further, the straight chain that alcohols solvent is C4-C10 in described step S1 or the branched chain dihydric alcohol or many of C4-C10
Unit's alcohol；
In described step S2, the temperature of heating is 160-245 DEG C, and described noble gas is nitrogen or argon；
In described step S3, reaction condition is: pressure be 0.1MPa, temperature be 160-245 DEG C under conditions of react 5-
30min；
Centrifugation in described step S4, uses ethanol as good solvent, and acetone is as poor solvent.
The platinum gallium composite nanometer particle a size of 4-6nm prepared by said method, in aqueous phase system, by regulation
Acetylacetone,2,4-pentanedione gallium and the consumption of acetylacetone,2,4-pentanedione platinum, the component ratio of the platinum gallium in control platinum gallium composite particles, obtained answers
In conjunction granule, the proportional components of gallium is from 13% to 82% continuously adjustabe.
Platinum gallium composite nano-catalyst of the present invention and preparation method thereof, has the advantages that
1, the method using heat to inject, uses alcohols solvent to serve not only as solvent, also as reducing agent, protects at noble gas
Protect down, utilize common reduction, nucleation and the growth promoting the two under the reduction high temperature of alcohols solvent.
2, the present invention synthesizes the method for platinum gallium nano-particle and can complete at short notice, and hot injection method can more effectively control
The particle diameter distribution of nano-particle, obtained platinum gallium composite nanometer particle dimensional homogeneity is good, and platinum gallium component ratio continuously may be used
Adjusting, obtained material is at nano-catalytic, magnetics application, information storage, nanosecond medical science, bio-sensing and photothermal technique etc.
Field has shown huge application potential.
3, the inventive method is to carry out in aqueous phase system, and prepared platinum gallium nano-particle dispersibles in ethanol, because of
After this load, the solvent of nano grain surface can be by being dried and roasting removal, and therefore the present invention is effectively by nanometer synthetic technology
Combine with Industrial Catalysis, start with from process for synthetic catalyst, by the catalysis of nano-particle controlledly synthesis regulation and control catalyst
Performance, has important actual application value.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to
Other accompanying drawing is obtained according to these accompanying drawings.
Fig. 1 is the method flow diagram of platinum gallium composite nano-catalyst in the embodiment of the present invention one；
Fig. 2 be the transmission electron micrograph of platinum gallium composite nanometer particle in the embodiment of the present invention one, high-resolution and
Element mapping graph；
Fig. 3 is that the transmission electron microscope element of platinum gallium composite nanometer particle in the embodiment of the present invention one maps spectrogram；
Fig. 4 is the x-ray photoelectron energy spectrogram of platinum gallium composite nanometer particle in the embodiment of the present invention one to six；
Fig. 5 is the transmission electron microscope figure of platinum gallium composite nanometer particle in the embodiment of the present invention one to six；
Fig. 6 is catalysis activity and the selectivity schematic diagram of platinum gallium composite nanometer particle in the embodiment of the present invention nine.
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 carried out clear, complete
Describe, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments wholely.Based on
Embodiment in the present invention, it is all that those of ordinary skill in the art are obtained on the premise of not making creative work
Other embodiments, broadly fall into the scope of protection of the invention.
Embodiment one:
As it is shown in figure 1, embodiments provide the preparation method of a kind of platinum gallium composite nano-catalyst, including following
Step:
S1, in glove box, weigh 0.0073g acetylacetone,2,4-pentanedione gallium pressed powder and 0.0079g acetylacetone,2,4-pentanedione platinum pressed powder
In the vial equipped with 3mL diethylene glycol, stirring makes its mix homogeneously, makes mixed solution, pipettes 17mL diethylene glycol simultaneously
In reactor, reactor can be selected for three-neck flask；
In above-mentioned system, alcohols solvent plays the dual function of solvent and reducing agent, utilize alcohols reproducibility and
Acetylacetone,2,4-pentanedione presoma (i.e. mixed solution) thermal decomposition at high temperature prepares even size distribution, composition adjustable platinum gallium again
Closing nano-particle, alcohols solvent can select multiple, according to carbon chain lengths and the difference of hydroxy radical content, optional C4-C10's
Straight or branched dihydroxylic alcohols or polyhydric alcohol.Due to the change in terms of solvent, reducing agent of the chemical property of dihydroxylic alcohols and polyhydric alcohol
Character is more consistent, and the embodiment of the present invention only provides one of which technical scheme, i.e. selects diethylene glycol as in course of reaction
The alcohols solvent used.
Diethylene glycol is also known as diethylene glycol, and molecular formula is HO-CH2-CH2-O-CH2-CH2-OH, and for dihydroxylic alcohols, outward appearance is nothing
Color is transparent, the liquid of mechanical impurity, and acrid in the mouth is peppery and micro-sweet, has a hygroscopicity, colourless to weak yellow liquid or crystallization, zest gas
Taste, is corrosive, fusing point 18-26 DEG C, boiling point 242-245 DEG C, density 1.1164 (20 DEG C), insoluble in benzene and carbon tetrachloride, molten
In ethanol, ether, water.
Acetylacetone,2,4-pentanedione platinum pressed powder is yellow solid powder, stable under normal temperature and pressure, melts at 249-252 DEG C and divides
Solve；Acetylacetone,2,4-pentanedione gallium pressed powder is white solid powder, melts at 196-198 DEG C and decomposes.
S2, it is connected to be connected in the path of nitrogen by the reactor filling diethylene glycol configured described in step S1, makes
It is allowed to warm to 160 DEG C by heating mantle；
S3, when temperature reaches 160 DEG C, the acetylacetone,2,4-pentanedione precursor solution of mix homogeneously in vial is injected into
In reactor, and it is 0 at pressure, under 1MPa, reacts 30min；
S4, question response terminate, and are cooled to room temperature, are then centrifuged for washing, use ethanol as good solvent, and acetone is as bad
Solvent, obtains platinum gallium composite nanometer particle after drying.
Such as Fig. 2 a, it is the transmission electron microscope figure of (100nm, 20nm) under different amplification respectively.From figure permissible
Find out that the particle diameter of synthesis granule is about 5.72nm, the platinum gallium that the preparation method of the platinum gallium composite nanometer particle of the present invention obtains is described
Composite nanometer particle, narrow diameter distribution, dimensional homogeneity is good.
As shown in Figure 2 c, by the high-resolution picture under 2nm rank amplification, can obtain being formed compound lattice
Spacing is 0.225nm, and this spacing of lattice compound with GaPt in document has good correspondence；In 5nm rank amplification
Under transmission electron microscope element map spectrogram as shown in Fig. 2 d-2g, in figure, 2d represents that the angle of elevation annular of platinum gallium composite nanometer particle is dark
Field picture-scanning transmission charge pattern；2e-2g represents the element Surface scan figure of element Surface scan figure (2e) the platinum element of gallium element respectively
(2f) and the superposition spectrogram (2g) of both signals.This it appears that the distribution of platinum and gallium is visibly homogeneous from figure, and do not have
The situation having simple substance to be independently distributed occurs.
As a example by the platinum gallium composite nanometer particle prepared in embodiment one, determined multiple by X-ray photoelectron spectroscopic analysis
The metal state of metallic atom and the state of oxidation in conjunction, the Ga 2p track from Fig. 3 a it can be seen that under the different state of oxidation
The binding energy of electronics is respectively 1116.7eV (Ga 2p3/2), 1143.5eV (Ga 2p1/2), 1117.8eV (Ga (III) 2p3/
2), 1144.6eV (Ga (III) 2p1/2), show that aoxidizing the Ga in front sample is presented in Ga0 and Ga3+, through peroxide
After change processes, Ga is all oxidized to three valence states；Fig. 3 b be in sample Pt before oxidation after different conditions, permissible from figure
Finding out, the platinum during platinum gallium is compound before oxidation is mainly presented in Pt0 and Pt2+, is changed into Pt2+ and Pt4+ after oxidation.
It is a kind of compound structure rather than two kinds of metals that these results all demonstrate the existence form of obtained platinum gallium composite catalyst
Simple physical bond.
The platinum gallium composite nanometer particle that the present embodiment preparation method obtains, its size is about 5.72nm, each component in being combined
Content be Pt:Ga=57:43.
Or step S3 and S4 are changed to following S3 ' and S4 ', prepare platinum gallium composite nano-catalyst in situ:
S3 ', it is previously added catalyst carrier, when temperature reaches 160 DEG C, by the acetyl of mix homogeneously in vial
Acetone precursor solution is injected in reactor, and maintains the response time at 30min, obtains reactant liquor；
S4 ', described reactant liquor is stirred 7 hours under the water-bath of 70 DEG C so that platinum gallium nano-particle is well into carrier
Hole, carries out centrifugation, is dried, obtain dried object, by obtained dried object 700 DEG C of high temperature in Muffle furnace after stirring
2 hours prepared platinum gallium composite nano-catalysts of roasting.
Wherein, catalyst carrier is commercial vector (Sasol, SIRAL 40).
Correspondingly, present invention also offers a kind of platinum gallium composite nano-catalyst, described catalyst is by above-mentioned method
Preparing, described catalyst includes that platinum gallium nano-particle and catalyst carrier, described platinum gallium nano-particle are supported on catalysis
On agent carrier.The load capacity of described platinum gallium nano-particle is 2%, a size of 10.5nm, the ratio of gallium in described platinum gallium nano-particle
Example is 43%.
Embodiment two:
A preferred embodiment of the present invention provides the preparation method of a kind of platinum gallium composite nanometer particle and platinum gallium composite Nano to urge
The preparation method of agent, it is essentially identical with the preparation method described in embodiment one, does not repeats them here.
It is in place of difference: the acetylacetone,2,4-pentanedione gallium pressed powder and the acetylacetone,2,4-pentanedione platinum pressed powder that weigh in glove box divide
Not Wei 0.0157g and 0.0025g, the diethylene glycol total amount simultaneously pipetted is 20mL.
Wherein in step S2, the temperature of heating is 170 DEG C, and noble gas is nitrogen；In described step S3, reaction condition is:
Pressure be 0.1MPa, temperature be 170 DEG C under conditions of react 15min.
Described step S3 ' in reaction condition be: pressure be 100Pa, temperature be 170 DEG C under conditions of react 15min；Institute
State step S4 ' described in reactant liquor to carry out the temperature of heating in water bath be 60 DEG C, mixing time is 7h, and described roasting condition is horse
Not roasting 1h at a temperature of 750 DEG C in stove.
The platinum gallium composite nanometer particle that the present embodiment preparation method obtains, its a size of 4.54nm, each component in being combined
Content is Pt:Ga=34:66.
The platinum gallium composite nano-catalyst that the present embodiment preparation method obtains, catalyst carrier be commercial vector (Sasol,
SIRAL 40), the load capacity of described platinum gallium nano-particle is 2%, a size of 11nm, the ratio of gallium in described platinum gallium nano-particle
It is 66%.
Embodiment three:
A preferred embodiment of the present invention provides the preparation method of a kind of platinum gallium composite nanometer particle and platinum gallium composite Nano to urge
The preparation method of agent, it is essentially identical with the preparation method described in embodiment one, does not repeats them here.
It is in place of difference: the acetylacetone,2,4-pentanedione gallium pressed powder and the acetylacetone,2,4-pentanedione platinum pressed powder that weigh in glove box divide
Not Wei 0.0629g and 0.0049g, the diethylene glycol total amount simultaneously pipetted is 20mL.
Wherein in step S2, the temperature of heating is 180 DEG C, and noble gas is nitrogen；In described step S3, reaction condition is:
Pressure be 1000Pa, temperature be 180 DEG C under conditions of react 5min.
Described step S3 ' in reaction condition be: pressure be 1000Pa, temperature be 180 DEG C under conditions of react 5min；Institute
State step S4 ' described in reactant liquor to carry out the temperature of heating in water bath be 80 DEG C, mixing time is 8h, and described roasting condition is horse
Not roasting 0.5h at a temperature of 800 DEG C in stove.
The platinum gallium composite nanometer particle that the present embodiment preparation method obtains, its a size of 5.66nm, each component in being combined
Content is Pt:Ga=26:74.
The platinum gallium composite nano-catalyst that the present embodiment preparation method obtains, catalyst carrier be commercial vector (Sasol,
SIRAL 40), the load capacity of described platinum gallium nano-particle is 3%, a size of 13nm, the ratio of gallium in described platinum gallium nano-particle
It is 74%.
Embodiment four:
A preferred embodiment of the present invention provides the preparation method of a kind of platinum gallium composite nanometer particle and platinum gallium composite Nano to urge
The preparation method of agent, it is essentially identical with the preparation method described in embodiment one, does not repeats them here.
It is in place of difference: the acetylacetone,2,4-pentanedione gallium pressed powder and the acetylacetone,2,4-pentanedione platinum pressed powder that weigh in glove box divide
Not Wei 0.0944g and 0.0049g, the diethylene glycol total amount simultaneously pipetted is 20mL.
Wherein in step S2, the temperature of heating is 200 DEG C, and noble gas is argon；In described step S3, reaction condition is:
Pressure be 1000Pa, temperature be 200 DEG C under conditions of react 20min.
Described step S3 ' in reaction condition be: pressure be 1000Pa, temperature be 200 DEG C under conditions of react 20min；
Described step S4 ' described in reactant liquor to carry out the temperature of heating in water bath be 60 DEG C, mixing time is 7h, described roasting condition be
Roasting 1h at a temperature of 750 DEG C in Muffle furnace.
The platinum gallium composite nanometer particle that the present embodiment preparation method obtains, its a size of 4.85nm, each component in being combined
Content is Pt:Ga=18:82.
The platinum gallium composite nano-catalyst that the present embodiment preparation method obtains, catalyst carrier be commercial vector (Sasol,
SIRAL 40), the load capacity of described platinum gallium nano-particle is 2.5%, a size of 15nm, the ratio of gallium in described platinum gallium nano-particle
Example is 82%.
Embodiment five:
A preferred embodiment of the present invention provides the preparation method of a kind of platinum gallium composite nanometer particle and platinum gallium composite Nano to urge
The preparation method of agent, it is essentially identical with the preparation method described in embodiment one, does not repeats them here.
It is in place of difference: the acetylacetone,2,4-pentanedione gallium pressed powder and the acetylacetone,2,4-pentanedione platinum pressed powder that weigh in glove box divide
Not Wei 0.0147g and 0.0472g, the diethylene glycol total amount simultaneously pipetted is 20mL.
Wherein in step S2, the temperature of heating is 220 DEG C, and noble gas is nitrogen；In described step S3, reaction condition is:
Pressure be 100Pa, temperature be 220 DEG C under conditions of react 15min.
Described step S3 ' in reaction condition be: pressure be 100Pa, temperature be 220 DEG C under conditions of react 15min；Institute
State step S4 ' described in reactant liquor to carry out the temperature of heating in water bath be 70 DEG C, mixing time is 7h, and described roasting condition is horse
Not roasting 1.5h at a temperature of 800 DEG C in stove.
The platinum gallium composite nanometer particle that the present embodiment preparation method obtains, its a size of 5.98nm, each component in being combined
Content is Pt:Ga=76:24.
The platinum gallium composite nano-catalyst that the present embodiment preparation method obtains, catalyst carrier be commercial vector (Sasol,
SIRAL 40), the load capacity of described platinum gallium nano-particle is 3%, a size of 14nm, the ratio of gallium in described platinum gallium nano-particle
It is 24%.
Embodiment six:
A preferred embodiment of the present invention provides the preparation method of a kind of platinum gallium composite nanometer particle and platinum gallium composite Nano to urge
The preparation method of agent, it is essentially identical with the preparation method described in embodiment one, does not repeats them here.
It is in place of difference: the acetylacetone,2,4-pentanedione gallium pressed powder and the acetylacetone,2,4-pentanedione platinum pressed powder that weigh in glove box divide
Not Wei 0.0037g and 0.0236g, the diethylene glycol total amount simultaneously pipetted is 20mL.
Wherein in step S2, the temperature of heating is 240 DEG C, and noble gas is nitrogen；In described step S3, reaction condition is:
Pressure be 1000Pa, temperature be 240 DEG C under conditions of react 5min.
Described step S3 ' in reaction condition be: pressure be 100Pa, temperature be 240 DEG C under conditions of react 5min；Institute
State step S4 ' described in reactant liquor to carry out the temperature of heating in water bath be 80 DEG C, mixing time is 6h, and described roasting condition is horse
Not roasting 1h at a temperature of 750 DEG C in stove.
The platinum gallium composite nanometer particle that the present embodiment preparation method obtains, its a size of 4.86nm, each component in being combined
Content is Pt:Ga=87:13.
The platinum gallium composite nano-catalyst that the present embodiment preparation method obtains, catalyst carrier be commercial vector (Sasol,
SIRAL 40), the load capacity of described platinum gallium nano-particle is 3%, a size of 15nm, the ratio of gallium in described platinum gallium nano-particle
It is 13%.
The preparation method of employing platinum gallium composite nanometer particle described in above-described embodiment one to six, the platinum gallium of preparation is combined
Nano-particle, uses X-ray powder diffraction analysis, and result is more consistent: in product system, the knot of platinum gallium composite nanometer particle
Crystalline substance is good, by comparison standard x RD spectrogram, there is not a large amount of platinum, gallium simple substance, but jointly reduce and formed in product
Composite construction；Wherein, as shown in Figure 4, the X-ray powder diffraction of the platinum gallium composite nanometer particle for preparing in above-described embodiment
Spectrogram, in figure, the most corresponding platinum, gallium component ratio are respectively 87:13；76:24；57:43；34:66；26:74；18:
82；From diffracting spectrum it can be seen that the platinum gallium composite nanometer particle characteristic absorption peak of different size and heterogeneity ratio is strong
Degree difference, represents the crystal property difference of product, and result is as aforementioned, in product system, and platinum gallium composite Nano
The crystallinity of grain is good, by comparison standard x RD spectrogram, there is not platinum simple substance, along with the increase of gallium precursor, meeting in product
More weak gallium simple substance peak occur, on the whole, whole system is the most jointly reduced and defines composite construction.
By the different proportion of regulation acetylacetone,2,4-pentanedione platinum with acetylacetone,2,4-pentanedione gallium, regulation and control obtain size uniformity and have heterogeneity
The platinum gallium composite nanometer particle of ratio.By six kinds of typical samples of analysis of ICP, obtain platinum, gallium component ratio is respectively 87:
13；76:24；57:43；34:66；26:74；18:82, the platinum gallium in these ratio correspondence embodiment one to embodiments six is compound to be received
The preparation method of rice grain.
Fig. 5 is the transmission electron microscope figure of the platinum gallium composite nanometer particle in above-described embodiment one to embodiment six, this
A little pictures show that the granule using this programme to obtain is respectively provided with good dispersibility, the advantages such as particle size distribution is narrower, granule
Size is respectively less than 10nm, this good basis provided for catalysis afterwards.In figure, a) corresponding platinum, gallium component ratio are Pt:Ga
=87:13；B) corresponding platinum, gallium component ratio are Pt:Ga=76:24；C) corresponding platinum, gallium component ratio are Pt:Ga=57:43；
D) corresponding platinum, gallium component ratio are Pt:Ga=34:66；E) corresponding platinum, gallium component ratio are Pt:Ga=26:74；F) corresponding platinum,
Gallium component ratio is Pt:Ga=18:82.
In embodiment two to embodiment four, difference platinum gallium nano-particle is supported on (Sasol, SIRAL on commercial vector
40) so that the load capacity of platinum gallium granule is 2-3%, concrete loading process is carried out under nitrogen atmosphere, by certain mass carrier
Add reactor reaction certain time, stir 6-8 hour under the water bath condition of 60-80 DEG C so that granule is well into carrier
Hole, is then placed in oven overnight and is dried, by obtained dried object 700-800 DEG C of high-temperature roasting 0.5-1.5 in Muffle furnace
Hour obtain platinum gallium supported catalyst.Obtained supported catalyst is catalyzed propane direct dehydrogenation (institute in fixed bed reactors
Experiment condition is: T=600 DEG C, P=0.1MPa, GHSV=6000h-1)。
Fig. 6 a-6b show gained catalyst for dehydrogenating propane catalysis activity and selectivity.From figure, we can
To find out, selectivity of catalyst and catalysis activity are gradually increased, when the content of gallium reaches 74% along with the increase of gallium content
Time, the selectivity of sample, catalysis activity all reach optimum state, along with gallium content increases further, the efficiency of catalyst again in
Existing downward trend, therefore we draw in this system, and Ga74Pt26 is a best proportion of catalyst.Fig. 6 c-6e institute
Being shown as the transmission electron microscope image of platinum gallium supported catalyst, ratio is respectively Ga66Pt34/SIRAL40 (c),
Ga74Pt26/SIRAL40 (d) and Ga82Pt18/SIRAL40 (e), as can be seen from the figure the platinum gallium alloy granule after load
Distribution of sizes is at 10nm to 15nm.
Platinum gallium composite nano-catalyst of the present invention and preparation method thereof, has the advantages that
1, the method using heat to inject, uses alcohols solvent to serve not only as solvent, also as reducing agent, at nitrogen environment
In, utilize common reduction, nucleation and the growth promoting the two under the reduction high temperature of alcohols solvent.
2, the present invention synthesizes the method for platinum gallium nano-particle and can complete at short notice, and hot injection method can more effectively control
The particle diameter distribution of nano-particle, obtained platinum gallium composite nanometer particle dimensional homogeneity is good, and platinum gallium component ratio continuously may be used
Adjusting, obtained material is at nano-catalytic, magnetics application, information storage, nanosecond medical science, bio-sensing and photothermal technique etc.
Field has shown huge application potential.
3, the inventive method is to carry out in aqueous phase system, and prepared platinum gallium nano-particle dispersibles in ethanol, because of
After this load, the solvent of nano grain surface can be by being dried and roasting removal, and therefore the present invention is effectively by nanometer synthetic technology
Combine with Industrial Catalysis, start with from process for synthetic catalyst, by the catalysis of nano-particle controlledly synthesis regulation and control catalyst
Performance, has important actual application value.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (10)
1. the preparation method of a platinum gallium composite nano-catalyst, it is characterised in that comprise the following steps:
S1, acetylacetone,2,4-pentanedione platinum and acetylacetone,2,4-pentanedione gallium are dissolved in alcohols solvent and mix homogeneously, prepare mixed solution；
S2, alcohols solvent is added in reactor, and described alcohols solvent is heated under inert gas shielding；
S3, in advance catalyst carrier is added in reactor, more described mixed solution is added in reactor by hot injection method,
Reaction obtains reactant liquor；
S4, reactant liquor react a period of time the most at a certain temperature, subsequently described reactant liquor are carried out heating in water bath and stir,
It is centrifuged separation, dry, roasting after stirring successively, prepares platinum gallium composite nano-catalyst.
The preparation method of platinum gallium composite nano-catalyst the most according to claim 1, it is characterised in that in described step S2
The temperature of heating is 160-245 DEG C；
In described step S3, reaction condition is: pressure be 0.1MPa, temperature be 160-245 DEG C under conditions of react 5-30min.
The preparation method of platinum gallium composite nano-catalyst the most according to claim 2, it is characterised in that in described step S2
Noble gas is nitrogen or argon.
4. according to the preparation method of the platinum gallium composite nano-catalyst described in claim 1-3 any one, it is characterised in that institute
State straight chain or the branched chain dihydric alcohol of C4-C10 or polyhydric alcohol that the alcohols solvent in step S1 is C4-C10.
The preparation method of platinum gallium composite nano-catalyst the most according to claim 4, it is characterised in that in described step S4
Described reactant liquor carries out the temperature of heating in water bath and is 60-80 DEG C, and mixing time is 5-8h.
The preparation method of platinum gallium composite nano-catalyst the most according to claim 5, it is characterised in that in described step S4
Roasting carry out in Muffle furnace, roasting condition is roasting 1-3h at a temperature of 600-800 DEG C.
The preparation method of platinum gallium composite nano-catalyst the most according to claim 6, it is characterised in that in described step S4
Centrifugation in, use ethanol as good solvent, acetone is as poor solvent.
8. according to the preparation method of the platinum gallium composite nano-catalyst described in claim 5-7 any one, it is characterised in that institute
Stating mixed solution in step S1 is to prepare in glove box.
9. a platinum gallium composite nano-catalyst, it is characterised in that described catalyst is by described in claim 1-8 any one
Method prepare, described catalyst includes platinum gallium nano-particle and catalyst carrier, and described platinum gallium nano-particle loads
On a catalyst support.
Platinum gallium composite nano-catalyst the most according to claim 9, it is characterised in that bearing of described platinum gallium nano-particle
Carrying capacity is 2-4%, a size of 10-15nm, and in described platinum gallium nano-particle, the ratio of gallium is 13%-82%.
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