CN105537624B - A kind of three square ring Pd sills and its preparation method and application - Google Patents
A kind of three square ring Pd sills and its preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000002086 nanomaterial Substances 0.000 claims abstract description 41
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 238000005859 coupling reaction Methods 0.000 claims abstract description 25
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 20
- 150000002739 metals Chemical class 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 16
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 238000006722 reduction reaction Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 17
- 239000010953 base metal Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006479 redox reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 238000011105 stabilization Methods 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 38
- 239000000463 material Substances 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 18
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 14
- 239000000243 solution Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 9
- 230000004224 protection Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229910002668 Pd-Cu Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910021069 Pd—Co Inorganic materials 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 235000013495 cobalt Nutrition 0.000 description 3
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical class [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229940070765 laurate Drugs 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910021065 Pd—Fe Inorganic materials 0.000 description 2
- XVIYCJDWYLJQBG-UHFFFAOYSA-N acetic acid;adamantane Chemical class CC(O)=O.C1C(C2)CC3CC1CC2C3 XVIYCJDWYLJQBG-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F9/26—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions using gaseous reductors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/8913—Cobalt and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/892—Nickel and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/8926—Copper and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/391—Physical properties of the active metal ingredient
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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Abstract
The invention discloses a kind of three square ring Pd based nano-materials and its preparation method and application, the three square rings Pd based nano-materials include zeroth order Pd metals and another zero-valent metal, and the molar ratio of zeroth order Pd metals and another zero-valent metal is 3:1~1:4, the shape of the Pd based nano-materials is three square rings, reduces the usage amount of noble metal, considerably increases the contact area for participating in reaction, and the conversion ratio for carbon carbon coupling reaction is up to 100%；Using two kinds of metal organic salts, oleyl amine is solvent for preceding object, adds surfactant, under the atmosphere of reducing gas, oxidized reduction reaction obtains, and the preparation method is easy to operate, and reaction product morphology controllable and stabilization, have a good application prospect.
Description
Technical field
The invention belongs to the preparation field of nano-noble metal-(non-) precious metal material morphology controllable, is related to a kind of three square rings
Pd sills and its preparation method and application.
Background technology
Nano-catalytic is a field quickly grown, has been related to total rudder homogeneous catalysis and heterogeneous catalysis application.Wherein,
Heterogeneous catalysis is ancient and relative maturity a nano science application field, including a variety of nanoparticles such as metal, semiconductor
Son is widely used in chemical catalysis reaction process.Here what is mainly discussed is noble metal catalyst, precious metal catalyst nanometer material
The hot spot of material always catalytic field research, the Pd noble metal catalysts mainly studied here.Pd base precious metals are a kind of use
Universal catalyst very extensive on the way, of good performance, can be used for hydrocarbon compound to convert, additionally may be used in petrochemical industry
For in coupling reaction, having the characteristics that high activity, high selectivity, using intersect Ou Lian reaction, many pharmaceutical intermediates with
And some natural products can be synthesized more easily, a simple and direct efficient approach is opened for synthesis chemistry.
But the reserves of noble metal are few, resource is limited, expensive, and common Pd base nano-particles are solid constructions,
In catalytic reaction, the only outermost layer to work can be contacted with reactant.
The content of the invention
The defects of it is an object of the invention to overcome the above in the prior art, there is provided a kind of three square ring Pd sills and its system
Preparation Method and application, the three square rings Pd based nano-materials include zeroth order Pd metals and another zero-valent metal, zeroth order Pd metals
Molar ratio with another zero-valent metal is 3:1~1:4, the shape of the Pd based nano-materials is three square rings, reduces your gold
The usage amount of category, considerably increases the contact area for participating in reaction, and the conversion ratio for carbon carbon coupling reaction is up to 100%；Using
Two kinds of metal organic salts are preceding object, and oleyl amine is solvent, add surfactant, are heat-treated by high temperature oil bath, in also Primordial Qi
Under the atmosphere of body, oxidized reduction reaction obtains, and the preparation method is easy to operate, and reaction product morphology controllable and stabilization, have
Good application prospect.
The present invention is achieved by the following technical solutions：
First aspect present invention provides a kind of three square ring Pd based nano-materials, including zeroth order Pd metals and another zeroth order gold
Belong to, the molar ratio of zeroth order Pd metals and another zero-valent metal is 3:1~1:4, the shape of the Pd based nano-materials is triangle
Ring.
Preferably, the molar ratio of zeroth order Pd metals and another zero-valent metal is 2:1~1:4, such as 2:1~1:1、1:1~
1:1.8 or 1:1.8~1:4.
Preferably, another zero-valent metal is zeroth order Pt metals, zeroth order Fe metals, zeroth order Ni metals, zeroth order Cu gold
Category or zeroth order Co metals.
Preferably, the outer ring length of the Pd based nano-materials is 65~75nm, and outer ring length refers to Pd based nano-materials
The outermost length of side of three square rings.
Second aspect of the present invention provides the preparation method of above-mentioned three square rings Pd based nano-materials, includes the following steps：By two
Kind metal organic salt is dissolved in oleyl amine, adds surfactant, under reducing gas atmosphere, oxidized reduction reaction obtains institute
Three square ring Pd based nano-materials are stated, described two metal organic salt one of which are Pd Base Metal organic salts.
Preferably, the preparation method includes the following steps：
(1) two kinds of metal organic salts are dissolved in oleyl amine, add surfactant, obtain suspending liquid A；
(2) suspending liquid A is heated, obtains solution B；
(3) by the solution B, redox reaction obtains solution C under reducing gas atmosphere；
(4) by solution C centrifugation, drying, the three square rings Pd based nano-materials are obtained.
Preferably, the Pd Base Metals organic salt and another molar ratio in described two metal organic salts are 3:1
~1:4.
Preferably, the molar ratio of oleyl amine and Pd Base Metal organic salts is 41.5:0.0125~41.5:0.05, such as 41.5:
0.0125~41.5:0.028 or 41.5:0.028~41.5:0.05, the molar ratio of surfactant and Pd Base Metal organic salts
For 0.319:0.0125~0.319:0.05, such as 0.319:0.0125~0.319:0.03 or 0.319:0.0125~0.319:
0.05。
It is furthermore preferred that the Pd Base Metals organic salt is 2 with another molar ratio in described two metal organic salts:
1~1：4, such as 2:1~1:1、1:1~1:1.8 or 1:1.8~1:4.
Preferably, the surfactant is organic carboxyl acid.It is furthermore preferred that the surfactant is selected from adamantane second
One or more in acid, stearic acid, laurate and benzoic acid.
Preferably, in step (2), the temperature of heating is 110~140 DEG C, and the time of heating is 3~5min.
Preferably, the temperature of redox reaction is 190~230 DEG C, such as 190~210 DEG C or 210~230 DEG C, and oxidation is also
The time of original reaction is 30~40min.
Preferably, redox reaction carries out in oil bath pan.
Preferably, the redox reaction is liquid phase oxidation reduction reaction.Liquid phase oxidation reduction reaction refers in liquid phase
The changed reaction of chemical valence between middle reactant.
Preferably, in step (4), dry temperature is 60 DEG C~80 DEG C, when drying time is 8~10 small.
Preferably, in step (4), it is dried under vacuum.
Preferably, in step (4), the solvent of centrifugation is absolute ethyl alcohol.
Third aspect present invention provides the purposes of above-mentioned three square rings Pd based nano-materials, for carbon carbon coupling reaction.
Preferably, the purposes is used for carbon carbon coupling reaction, and reaction condition is：Under Ar protective conditions, ethanol/water is molten
Agent, reaction temperature are 60~90 DEG C, and the reaction time is 2~6h.
The present invention one of at least has the advantages that：
(1) three square ring Pd based nano-materials of the invention have triangular ring structure, reduce the usage amount of noble metal, significantly
The contact area for participating in reaction is added, improves the service efficiency of catalyst, the conversion ratio for carbon carbon coupling reaction reaches
100%；
(2) preferably, particle size is homogeneous, stable structure for three square ring Pd based nano-materials of the invention dispersiveness；
(3) preparation method of the invention is used in oleyl amine system, adds surfactant as structure directing agent, and one
The three square rings Pd based nano-materials can be made in step, and easy to operate, reaction product morphology controllable and stabilization, have well
Application prospect.
Brief description of the drawings
Fig. 1 is the TEM collection of illustrative plates of the three square ring Pd based nano-materials prepared in embodiment 1~9；
Fig. 2 is the XRD spectrum of three square ring Pd based nano-materials of the preparation in embodiment 5.
Embodiment
Illustrate technical scheme below by way of specific instantiation.It is to be understood that the present invention mention one or
Multiple method and steps do not repel before and after the combination step that also there are other methods step or the step specifically mentioned at these
Other methods step can also be inserted between rapid；It should also be understood that these embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Moreover, unless otherwise indicated, the numbering of various method steps is only to differentiate the convenient tool of various method steps,
Rather than ordering or the enforceable scope of the restriction present invention, the change of its relativeness or tune for limitation various method steps
It is whole, in the case where changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Embodiment 1
Weigh 0.0125mmol palladium acetylacetonates and 0.05mmol acetylacetone cobalts are put into three-necked flask, and add 9ml
Oleyl amine and 3mmol adamantane acetic acids, obtain suspending liquid A.3~5min is dissolved by heating under the conditions of 130 DEG C, obtains mixed solution
B.Solution B is quickly transferred in 210 DEG C of oil bath pan, reacts 40min under reducing gas atmosphere, obtain mixed solution C.It is cold
But centrifuged three times with absolute ethyl alcohol to after room temperature, obtain three wet square ring Pd-Co nano materials D.By D at 60 DEG C vacuum
It is dry 10 it is small when, obtain three square ring bimetallic material of Pd-Co bases, TEM figures are shown in Fig. 1, can be obtained through TEM, outer ring length for 65~
75nm.Bimetallic nano material obtained above can be used in carbon carbon coupling reaction, and coupling reaction carries out in reaction tube, reaction
Condition is：T (temperature)=80 DEG C, Ar are protected, reaction time 4h, and ethanol/water is solvent, conversion ratio 100%.
Embodiment 2
Weigh 0.0125mmol palladium acetylacetonates and 0.05mmol acetylacetone cobalts are put into three-necked flask, and add 9ml
Oleyl amine and 3mmol stearic acid, obtain suspending liquid A.3~5min is dissolved by heating under the conditions of 130 DEG C, obtains mixed solution B.Will
Solution B is quickly transferred in 210 DEG C of oil bath pan, is reacted 40min under reducing gas atmosphere, is obtained mixed solution C.It is cooled to
Centrifuged three times with absolute ethyl alcohol after room temperature, obtain three wet square ring Pd-Co nano materials D.D is dried in vacuo at 60 DEG C
10 it is small when, obtain three square ring bimetallic material of Pd-Co bases, TEM figures are shown in Fig. 1, and outer ring length is 65~75nm.It is obtained above to receive
Rice bimetallic material can be used in carbon carbon coupling reaction, and coupling reaction carries out in reaction tube, and reaction condition is：T (temperature)=
80 DEG C, Ar protections, reaction time 4h, ethanol/water is solvent, conversion ratio 100%.
Embodiment 3
Weigh 0.0125mmol palladium acetylacetonates and 0.05mmol acetylacetone,2,4-pentanedione ferrous irons are put into three-necked flask, and add
The oleyl amine and 3mmol stearic acid of 9ml, obtains suspending liquid A.3~5min is dissolved by heating under the conditions of 130 DEG C, obtains mixed solution
B.Solution B is quickly transferred in 210 DEG C of oil bath pan, reacts 40min under reducing gas atmosphere, obtain mixed solution C.It is cold
But centrifuged three times with absolute ethyl alcohol to after room temperature, obtain three wet square ring Pd-Fe nano materials D.By D at 60 DEG C vacuum
When drying 10 is small, three square ring bimetallic material of Pd-Fe bases is obtained, TEM figures are shown in Fig. 1, and outer ring length is 65~75nm.It is above-mentioned to be made
Bimetallic nano material can be used for carbon carbon coupling reaction in, coupling reaction carries out in reaction tube, and reaction condition is：T (temperature
Degree)=80 DEG C, Ar protections, reaction time 4h, ethanol/water is solvent, conversion ratio 100%.
Embodiment 4
Weigh 0.0125mmol palladium acetylacetonates and 0.05mmol nickel acetylacetonates are put into three-necked flask, and add 9ml
Oleyl amine and 3mmol stearic acid, obtain suspending liquid A.3~5min is dissolved by heating under the conditions of 130 DEG C, obtains mixed solution B.Will
Solution B is quickly transferred in 210 DEG C of oil bath pan, is reacted 40min under reducing gas atmosphere, is obtained mixed solution C.It is cooled to
Centrifuged three times with absolute ethyl alcohol after room temperature, obtain three wet square ring Pd-Ni nano materials D.D is dried in vacuo at 60 DEG C
10 it is small when, obtain three square ring bimetallic material of Pd-Ni bases, TEM figures are shown in Fig. 1, and outer ring length is 65~75nm.It is obtained above to receive
Rice bimetallic material can be used in carbon carbon coupling reaction, and coupling reaction carries out in reaction tube, and reaction condition is：T (temperature)=
80 DEG C, Ar protections, reaction time 4h, ethanol/water is solvent, conversion ratio 100%.
Embodiment 5
Weigh 0.0125mmol palladium acetylacetonates and 0.05mmol acetylacetone coppers are put into three-necked flask, and add 9ml
Oleyl amine and 3mmol adamantane acetic acids, obtain suspending liquid A.3~5min is dissolved by heating under the conditions of 130 DEG C, obtains mixed solution
B.Solution B is quickly transferred in 210 DEG C of oil bath pan, reacts 40min under reducing gas atmosphere, obtain mixed solution C.It is cold
But centrifuged three times with absolute ethyl alcohol to after room temperature, obtain three wet square ring Pd-Cu nano materials D.By D at 60 DEG C vacuum
When drying 10 is small, three square ring bimetallic material of Pd-Cu bases is obtained, TEM figures are shown in Fig. 1, and outer ring length is 65~75nm, and XRD diagram is shown in
Fig. 2.Bimetallic nano material obtained above can be used in carbon carbon coupling reaction, and coupling reaction carries out in reaction tube, reaction
Condition is：T (temperature)=80 DEG C, Ar are protected, reaction time 4h, and ethanol/water is solvent, conversion ratio 100%.
Embodiment 6
Weigh 0.05mmol palladium acetylacetonates and 0.05mmol acetylacetone coppers are put into three-necked flask, and add 9ml's
Oleyl amine and 3mmol stearic acid, obtain suspending liquid A.3~5min is dissolved by heating under the conditions of 130 DEG C, obtains mixed solution B.Will be molten
Liquid B is quickly transferred in 210 DEG C of oil bath pan, is reacted 30min under reducing gas atmosphere, is obtained mixed solution C.It is cooled to room
Wen Houyong absolute ethyl alcohols centrifuge three times, obtain three wet square ring Pd-Cu nano materials D.D is dried in vacuo 10 at 60 DEG C
Hour, three square ring bimetallic material of Pd-Cu bases is obtained, TEM figures are shown in Fig. 1, and outer ring length is 65~75nm.Nanometer obtained above
Bimetallic material can be used in carbon carbon coupling reaction, and coupling reaction carries out in reaction tube, and reaction condition is：T (temperature)=80
DEG C, Ar protections, reaction time 4h, ethanol/water is solvent, conversion ratio 100%.
Embodiment 7
Weigh 0.05mmol palladium acetylacetonates and 0.025mmol acetylacetone coppers are put into three-necked flask, and add 9ml's
Oleyl amine and 3mmol laurate, obtain suspending liquid A.3~5min is dissolved by heating under the conditions of 130 DEG C, obtains mixed solution B.Will be molten
Liquid B is quickly transferred in 210 DEG C of oil bath pan, is reacted 30min under reducing gas atmosphere, is obtained mixed solution C.It is cooled to room
Wen Houyong absolute ethyl alcohols centrifuge three times, obtain three wet square ring Pd-Cu nano materials D.D is dried in vacuo 10 at 60 DEG C
Hour, three square ring bimetallic material of Pd-Cu bases is obtained, TEM figures are shown in Fig. 1, and outer ring length is 65~75nm.Nanometer obtained above
Bimetallic material can be used in carbon carbon coupling reaction, and coupling reaction carries out in reaction tube, and reaction condition is：T (temperature)=80
DEG C, Ar protections, reaction time 4h, ethanol/water is solvent, conversion ratio 100%.
Embodiment 8
Weigh 0.028mmol palladium acetylacetonates and 0.05mmol acetylacetone,2,4-pentanedione platinum is put into three-necked flask, and add 9ml's
Oleyl amine and 3mmol benzoic acid, obtain suspending liquid A.3~5min is dissolved by heating under the conditions of 130 DEG C, obtains mixed solution B.Will be molten
Liquid B is quickly transferred in 210 DEG C of oil bath pan, is reacted 30min under reducing gas atmosphere, is obtained mixed solution C.It is cooled to room
Wen Houyong absolute ethyl alcohols centrifuge three times, obtain three wet square ring Pd-Pt nano materials D.D is dried in vacuo 10 at 60 DEG C
Hour, three square ring bimetallic material of Pd-Pt bases is obtained, TEM figures are shown in Fig. 1, and outer ring length is 65~75nm.Nanometer obtained above
Bimetallic material can be used in carbon carbon coupling reaction, and coupling reaction carries out in reaction tube, and reaction condition is：T (temperature)=80
DEG C, Ar protections, reaction time 4h, ethanol/water is solvent, conversion ratio 100%.
Embodiment 9
Weigh 0.05mmol palladium acetylacetonates and 0.025mmol acetylacetone cobalts are put into three-necked flask, and add 9ml's
Oleyl amine and 3mmol laurate, obtain suspending liquid A.3~5min is dissolved by heating under the conditions of 130 DEG C, obtains mixed solution B.Will be molten
Liquid B is quickly transferred in 210 DEG C of oil bath pan, is reacted 30min under reducing gas atmosphere, is obtained mixed solution C.It is cooled to room
Wen Houyong absolute ethyl alcohols centrifuge three times, obtain three wet square ring Pd-Co nano materials D.D is dried in vacuo 10 at 60 DEG C
Hour, three square ring bimetallic material of Pd-Pt bases is obtained, TEM figures are shown in Fig. 1, and outer ring length is 65~75nm.Nanometer obtained above
Bimetallic material can be used in carbon carbon coupling reaction, and coupling reaction carries out in reaction tube, and reaction condition is：T (temperature)=80
DEG C, Ar protections, reaction time 4h, ethanol/water is solvent, conversion ratio 100%.
The above, be only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, on the premise of the method for the present invention is not departed from, can also make
Some improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are the equivalent embodiment of the present invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution for any equivalent variations that above-described embodiment is made, still fall within the scope of technical scheme
It is interior.
Claims (11)
1. a kind of three square ring Pd based nano-materials, it is characterised in that including zeroth order Pd metals and another zero-valent metal, zeroth order Pd
The molar ratio of metal and another zero-valent metal is 3：1~1：4, the shapes of the Pd based nano-materials is three square rings, the Pd
Based nano-material is obtained by the preparation method included the following steps：Two kinds of metal organic salts are dissolved in oleyl amine, add surface
Activating agent, under reducing gas atmosphere, oxidized reduction reaction obtains the three square rings Pd based nano-materials, described two metals
Organic salt one of which is Pd Base Metal organic salts, the Pd Base Metals organic salt with it is another in described two metal organic salts
The molar ratio of kind is 3:1~1:4, the molar ratio of oleyl amine and Pd Base Metal organic salts is 41.5:0.0125~41.5:0.05, table
The molar ratio of face activating agent and Pd Base Metal organic salts is 0.319:0.0125~0.319:0.05.
2. three square rings Pd based nano-materials according to claim 1, it is characterised in that the another kind zero-valent metal is zero
Valency Pt metals, zeroth order Fe metals, zeroth order Ni metals, zeroth order Cu metals or zeroth order Co metals.
3. three square rings Pd based nano-materials according to claim 1, it is characterised in that the outer shroud of the Pd based nano-materials
Length is 65~75nm.
4. the preparation method of three square rings Pd based nano-materials according to any one of claims 1 to 3, it is characterised in that including
Following steps：Two kinds of metal organic salts are dissolved in oleyl amine, add surfactant, it is oxidized under reducing gas atmosphere
Reduction reaction obtains the three square rings Pd based nano-materials, and described two metal organic salt one of which are organic for Pd Base Metals
Salt, the Pd Base Metals organic salt are 3 with another molar ratio in described two metal organic salts:1~1:4, oleyl amine with
The molar ratio of Pd Base Metal organic salts is 41.5:0.0125~41.5:0.05, surfactant rubs with Pd Base Metal organic salts
You are than being 0.319:0.0125~0.319:0.05.
5. preparation method according to claim 4, it is characterised in that include the following steps：
(1) two kinds of metal organic salts are dissolved in oleyl amine, add surfactant, obtain suspending liquid A；
(2) suspending liquid A is heated, obtains solution B；
(3) by the solution B, redox reaction obtains solution C under reducing gas atmosphere；
(4) by solution C centrifugation, drying, the three square rings Pd based nano-materials are obtained.
6. preparation method according to claim 4 or 5, it is characterised in that the surfactant is organic carboxyl acid.
7. preparation method according to claim 5, it is characterised in that in step (2), the temperature of heating is 110~140
DEG C, the time of heating is 3~5min.
8. preparation method according to claim 4 or 5, it is characterised in that the temperature of redox reaction is 190~230
DEG C, the time of redox reaction is 30~40min.
9. preparation method according to claim 5, it is characterised in that in step (4), dry temperature is 60 DEG C~80
DEG C, when drying time is 8~10 small.
10. three square rings Pd based nano-materials according to any one of claims 1 to 3 are used for carbon carbon coupling reaction.
11. purposes according to claim 10, it is characterised in that reaction condition is：Under Ar protective conditions, ethanol/water is
Solvent, reaction temperature are 60~90 DEG C, and the reaction time is 2~6h.
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