CN105413709A - Platinum-cobalt nano bimetallic catalyst adopting multi-cubic branched structure as well as preparation method and application of catalyst - Google Patents
Platinum-cobalt nano bimetallic catalyst adopting multi-cubic branched structure as well as preparation method and application of catalyst Download PDFInfo
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- CN105413709A CN105413709A CN201510925661.XA CN201510925661A CN105413709A CN 105413709 A CN105413709 A CN 105413709A CN 201510925661 A CN201510925661 A CN 201510925661A CN 105413709 A CN105413709 A CN 105413709A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 239000002184 metal Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 38
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims abstract description 15
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940117916 cinnamic aldehyde Drugs 0.000 claims abstract description 15
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 104
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 56
- 229910052697 platinum Inorganic materials 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 17
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 16
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 16
- 229930016911 cinnamic acid Natural products 0.000 claims description 16
- 235000013985 cinnamic acid Nutrition 0.000 claims description 16
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 16
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 claims description 14
- 239000002086 nanomaterial Substances 0.000 claims description 13
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 10
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 150000003973 alkyl amines Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000000265 homogenisation Methods 0.000 claims description 8
- 238000011282 treatment Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 5
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 5
- 229940070765 laurate Drugs 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- 229910052786 argon Inorganic materials 0.000 description 14
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 8
- 241000143437 Aciculosporium take Species 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000006641 stabilisation Effects 0.000 description 7
- 238000011105 stabilization Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
-
- B01J35/23—
-
- B01J35/40—
-
- B01J35/50—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
Abstract
The invention discloses a platinum-cobalt nano bimetallic catalyst adopting a multi-cubic branched structure as well as a preparation method and an application of the catalyst. The catalyst adopts the branched platinum-cobalt nano bimetallic structure and has eight branches, each branch is a separate cube, and the catalyst is good in dispersibility, controllable in component, magnetic and easy to collect. The catalyst is prepared with a liquid phase reduction method at two stages, products are controlled by controlling the proportion of metal precursors, the reaction time and the reaction temperature, platinum-cobalt nanoparticles with different components are obtained, used reagents are non-toxic, the method is simple, and operation is easy. The catalyst is used for cinnamaldehyde hydrogenation, has higher catalytic activity and has high selectivity to C=O.
Description
Technical field
The present invention relates to technology of preparing and the application of nano material, platinum cobalt nanometer bi-metal catalyst being specifically related to a kind of many cubes of dendritic morphologies and its preparation method and application.
Background technology
Platinum based nano-material all has wide practical use in a lot of field such as catalysis due to the physicochemical properties of its uniqueness.But the reserves of noble metal are rare, expensive, people transfer to sight in their service efficiency of raising, such as the noble metals such as platinum are combined with base metal and are prepared into bimetallic, not only significantly decrease noble metal dosage, and utilize the electro transfer effect between bimetallic to produce cooperative effect.
For metallic nano crystal body catalyst, atomic steps on high miller index surface, rib and angle, the atom in these regions has lower ligancy, thus there is higher catalytic activity, therefore, in order to improve the activity of nanocrystal catalyst, how to increase the atomic steps of plane of crystal and rib and angle, become the emphasis of research gradually.
For the nano particle of platinum cobalt binary system, reported major part is cube, octahedra grade for pattern, and these patterns are formed by low index crystal plane, and corner angle are less, catalytic activity is limited in the past.Therefore, preparation has the nanostructured in more how low ligancy site, will improve the catalytic activity of platinum-cobalt dual-metal nanocrystal further.The platinum cobalt single crystal nanoparticles be made up of multiple cube, has more rib and angle, and gap location exposes high-index surface, is conducive to the catalytic activity improving platinum-cobalt dual-metal nano particle.At present about the preparation of the platinum-cobalt dual-metal nano particle of this pattern, there is no report both at home and abroad.
Summary of the invention
The object of the invention is to overcome defect of the prior art, platinum cobalt nanometer bi-metal catalyst proposing a kind of many cubes of dendritic morphologies and its preparation method and application, described catalyst is dendritic platinum cobalt bimetallic nano structure, have eight branches, each branch is an independent cube, good dispersion, and composition is controlled, be magnetic, be easy to collect.Described catalyst adopts liquid phase reduction to obtain, and points two sections carry out, and regulate and control product by regulating and controlling the ratio of metal precursor, reaction time and reaction temperature, obtain the platinum cobalt nanometer particle that component is different, agents useful for same is nontoxic, and method is simple, is easy to operation.Described catalyst is used for hydrogenation on cinnamic aldehyde and has higher catalytic activity, and has higher selective to C=O.
The present invention is achieved by the following technical solutions:
First aspect present invention provides a kind of platinum cobalt nanometer bi-metal catalyst, and be dendritic platinum cobalt bimetallic nano structure, have eight branches, each branch is an independent cube.
Preferably, the particle diameter of described catalyst is 20nm ~ 40nm.
Second aspect present invention provides a kind of preparation method of above-mentioned platinum cobalt nanometer bi-metal catalyst, adopts liquid phase reduction preparation, comprises the following steps:
(1) under the protection of inert gas, acetylacetone,2,4-pentanedione platinum, acetylacetone cobalt, alkylamine and alkyl acid are carried out Homogenization Treatments, obtain the first mixed solution;
(2) described first mixed liquor that step (1) obtains is passed into reducing gas to react, obtain the first black suspension, Magneto separate, obtain black solid;
(3) under the protection of inert gas, the described black solid, acetylacetone,2,4-pentanedione platinum, alkylamine and the alkyl acid that step (2) are obtained carry out Homogenization Treatments, obtain the second mixed solution;
(4) described second mixed liquor that step (3) obtains is passed into reducing gas to react, obtain the second black suspension;
(5) described second black suspension that step (4) obtains is carried out clean, Magneto separate and drying, namely obtain described catalyst.
Preferably, in step (1), the mol ratio of described acetylacetone,2,4-pentanedione platinum and acetylacetone cobalt is 1:4 ~ 1:2, as 1:4 ~ 1:3 or 1:3 ~ 1:2, the mol ratio of described alkylamine and acetylacetone,2,4-pentanedione platinum is 1459:1 ~ 1094:1, as 1459:1 ~ 1276:1 or 1276:1 ~ 1094:1, the mol ratio of described alkyl acid and acetylacetone,2,4-pentanedione platinum is 482:1 ~ 365:1, as 482:1 ~ 429:1,429:1 ~ 371:1 or 371:1 ~ 365:1.
Preferably, in step (1) and step (3), the temperature of described Homogenization Treatments is 100 ~ 150 DEG C, and as 100 ~ 130 DEG C or 130 ~ 150 DEG C, the time of described Homogenization Treatments is 5 ~ 30min, as 5 ~ 10min or 10 ~ 30min.
Preferably, in step (1) and step (3), described alkylamine be selected from oleyl amine, lauryl amine and cetylamine one or more; Described alkyl acid be selected from oleic acid, stearic acid and laurate one or more.
Preferably, in step (2), reaction temperature is 220 DEG C ~ 235 DEG C, as 220 DEG C ~ 225 DEG C or 220 DEG C ~ 235 DEG C.
Step (2) can be carried out in high temperature oil bath, and the insulation scheduled time is 2min ~ 8min, as 2min ~ 5min or 5min ~ 8min, and then passes into reducing gas.
Preferably, in step (2), described reducing gas is carbon monoxide, and flow velocity is 100 ~ 300mL/min, as 100 ~ 190mL/min or 190 ~ 300mL/min.
Preferably, in step (2), the described reaction time is 10min ~ 1h, as 10min ~ 30min or 30min ~ 1h.
Preferably, in step (3), the mass ratio of the described black solid that step (2) obtains and acetylacetone,2,4-pentanedione platinum is 1:8 ~ 1:2, as 1:8 ~ 1:4,1:4 ~ 1:3.35 or 1:3.35 ~ 1:2, the mass ratio of described alkylamine and black solid is 5200:1 ~ 2300:1, as 5200:1 ~ 3750:1,3750:1 ~ 3400:1 or 3400:1 ~ 2300:1, the mass ratio of described alkyl acid and black solid is 996:1 ~ 311:1, as 996:1 ~ 650:1,650:1 ~ 452:1 or 452:1 ~ 311:1.
Preferably, in step (4), reaction temperature is 200 ~ 215 DEG C, as 200 ~ 210 DEG C or 210 ~ 215 DEG C.
Step (4) can be carried out in high temperature oil bath.
Preferably, in step (4), described reducing gas is carbon monoxide, and flow velocity is 100 ~ 300mL/min, as 100 ~ 190mL/min, 190 ~ 200mL/min or 200 ~ 300mL/min.
Preferably, in step (4), the described reaction time is 10min ~ 1h, as 10min ~ 15min, 15min ~ 30min or 30min ~ 1h.
Preferably, in step (5), clean with organic solvent, described organic solvent be selected from ethanol, chloroform, n-hexane and acetone one or more.
Third aspect present invention provides a kind of purposes of above-mentioned platinum cobalt nanometer bi-metal catalyst, reacts for hydrogenation on cinnamic aldehyde.
Preferably, the condition of hydrogenation reaction is: reaction pressure is 1.5 ~ 3MPa, as 1.5 ~ 2MPa or 2 ~ 3MPa, reaction temperature is 20 ~ 80 DEG C, as 20 ~ 50 DEG C, 50 ~ 60 DEG C or 60 ~ 80 DEG C, the reaction time is 8 ~ 24h, as 8 ~ 15h or 15 ~ 24h, described cinnamic acid and catalyst amount mass ratio are 10:1 ~ 100:1, as 10:1 ~ 20:1,20:1 ~ 50:1 or 50:1 ~ 100:1.
Beneficial effect of the present invention: platinum cobalt nanometer bi-metal catalyst of the present invention is dendritic platinum cobalt bimetallic nano structure, and have eight branches, each branch is an independent cube, good dispersion, and composition is controlled, is magnetic, is easy to collect.Described catalyst adopts liquid phase reduction to obtain, and points two sections carry out, and regulate and control product by regulating and controlling the ratio of metal precursor, reaction time and reaction temperature, obtain the platinum cobalt nanometer particle that component is different, agents useful for same is nontoxic, and method is simple, is easy to operation.Described catalyst is used for hydrogenation on cinnamic aldehyde and has higher catalytic activity, and has higher selective to C=O.
Accompanying drawing explanation
Fig. 1 is the low power TEM figure of the platinum cobalt nanometer bi-metal catalyst of preparation in embodiment 1 ~ 7;
Fig. 2 is that the high-resolution TEM of the platinum cobalt nanometer bi-metal catalyst of preparation in embodiment 1 ~ 7 schemes;
Fig. 3 is the evaluation result of platinum cobalt nanometer bi-metal catalyst for hydrogenation on cinnamic aldehyde of preparation in embodiment 1.
Detailed description of the invention
Below by way of specific instantiation, technical scheme of the present invention is described.Should be understood that one or more method steps that the present invention mentions do not repel and before and after described combination step, also to there is additive method step or can also insert additive method step between these steps clearly mentioned; Should also be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Embodiment 1
Take 0.017mmol acetylacetone,2,4-pentanedione platinum and 0.05mmol acetylacetone cobalt puts into there-necked flask, add oleyl amine and the 6.3mmol oleic acid of 24.8mmol, under argon shield, be uniformly mixed 5min in 130 DEG C of heating, obtain mixed liquor A.Mixed liquor A transferred to rapidly in the oil bath pan of 225 DEG C, after temperature stabilization 5min, pass into carbon monoxide, flow velocity is 190mL/min, and reaction 30min, obtains black suspension B.Magneto separate after cool to room temperature, obtains black solid A.Take 2mg black solid and 6.7mg acetylacetone,2,4-pentanedione platinum puts into there-necked flask, add oleyl amine and the 903.9mg oleic acid of 7.5g, under argon shield, be uniformly mixed 5min in 130 DEG C of heating, obtain mixed liquor C.Transferred to rapidly by mixed liquor C in the oil bath pan of 210 DEG C, pass into carbon monoxide simultaneously, flow velocity is 190mL/min, and reaction 15min, obtains black suspension D.Magneto separate after cool to room temperature, cleans three times with chloroform, dried in vacuo overnight at 60 DEG C, obtains the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube.
This catalyst is used for hydrogenation on cinnamic aldehyde reaction, reaction condition is as follows, 100mg cinnamic acid, 2mg catalyst, 100mg internal standard compound dodecane are scattered in 40mL ethanol, hydrogen is passed into 2MPa in batch reactor, be warming up to 60 DEG C, stop after reaction 24h, with GC-MS, the product under the differential responses time is monitored.
Fig. 1 is the TEM figure of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation, Fig. 2 is that the high-resolution TEM of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation schemes, from Fig. 1 and Fig. 2, the described platinum cobalt nanometer bi-metal catalyst particle size be made up of multiple cube obtained is at 20 ~ 40nm, for dendritic platinum cobalt bimetallic nano structure, have eight branches, each branch is all independent cubes, good dispersion, composition is controlled, be magnetic, be easy to collect.
Fig. 3 is the evaluation result that the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation reacts for hydrogenation on cinnamic aldehyde, result shows, the conversion ratio of cinnamic acid reaches 100% in 12h, now the selective of C=O hydrogenation is 51.3%, the selective of C=C hydrogenation is 20.6%, the selective of complete hydrogenation is 28.1%, and described catalyst is used for hydrogenation on cinnamic aldehyde and has higher catalytic activity, and has higher selective to C=O.
Embodiment 2
Take 0.017mmol acetylacetone,2,4-pentanedione platinum and 0.068mmol acetylacetone cobalt puts into there-necked flask, add 21.7mmol cetylamine and 8.2mmol laurate, under argon shield, be uniformly mixed 30min in 150 DEG C of heating, obtain mixed liquor A.Mixed liquor A transferred to rapidly in the oil bath pan of 235 DEG C, after temperature stabilization 8min, pass into carbon monoxide, flow velocity is 300mL/min, and reaction 10min, obtains black suspension B.Magneto separate after cool to room temperature, obtains black solid A.Take 2mg black solid and 6.7mg acetylacetone,2,4-pentanedione platinum puts into there-necked flask, add oleyl amine and the 1.3g oleic acid of 7.5g, under argon shield, be uniformly mixed 5min in 130 DEG C of heating, obtain mixed liquor C.Transferred to rapidly by mixed liquor C in the oil bath pan of 210 DEG C, pass into carbon monoxide simultaneously, flow velocity is 190mL/min, and reaction 15min, obtains black suspension D.Magneto separate after cool to room temperature, cleans three times with chloroform, dried in vacuo overnight at 60 DEG C, obtains the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube.
Fig. 1 is the TEM figure of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation, Fig. 2 is that the high-resolution TEM of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation schemes, from Fig. 1 and Fig. 2, the described platinum cobalt nanometer bi-metal catalyst particle size be made up of multiple cube obtained is at 20 ~ 40nm, for dendritic platinum cobalt bimetallic nano structure, have eight branches, each branch is all independent cubes, good dispersion, composition is controlled, be magnetic, be easy to collect.
This catalyst is used for hydrogenation on cinnamic aldehyde reaction, reaction condition is as follows, 100mg cinnamic acid, 1mg catalyst, 100mg internal standard compound dodecane are scattered in 40mL ethanol, hydrogen is passed into 1.5MPa in batch reactor, be warming up to 80 DEG C, stop after reaction 15h, with GC-MS, the product under the differential responses time is monitored.Result shows, and the conversion ratio of cinnamic acid reaches 100% in 15h, and now the selective of selective 40.7%, the C=C of being hydrogenation of C=O hydrogenation is 23.5%, and the selective of complete hydrogenation is 35.8%.
Embodiment 3
Take 0.017mmol acetylacetone,2,4-pentanedione platinum and 0.034mmol acetylacetone cobalt puts into there-necked flask, add 18.6mmol lauryl amine and 6.2mmol stearic acid, under argon shield, be uniformly mixed 10min in 100 DEG C of heating, obtain mixed liquor A.Mixed liquor A transferred to rapidly in the oil bath pan of 220 DEG C, after temperature stabilization 2min, pass into carbon monoxide, flow velocity is 100mL/min, and reaction 1h, obtains black suspension B.Magneto separate after cool to room temperature, obtains black solid A.Take 2mg black solid and 6.7mg acetylacetone,2,4-pentanedione platinum puts into there-necked flask, add oleyl amine and the 903.9mg oleic acid of 7.5g, under argon shield, be uniformly mixed 5min in 130 DEG C of heating, obtain mixed liquor C.Transferred to rapidly by mixed liquor C in the oil bath pan of 210 DEG C, pass into carbon monoxide simultaneously, flow velocity is 190mL/min, and reaction 15min, obtains black suspension D.Magneto separate after cool to room temperature, with ethanol purge three times, dried in vacuo overnight at 60 DEG C, obtains the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube.
Fig. 1 is the TEM figure of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation, Fig. 2 is that the high-resolution TEM of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation schemes, from Fig. 1 and Fig. 2, the described platinum cobalt nanometer bi-metal catalyst particle size be made up of multiple cube obtained is at 20 ~ 40nm, for dendritic platinum cobalt bimetallic nano structure, have eight branches, each branch is all independent cubes, good dispersion, composition is controlled, be magnetic, be easy to collect.
This catalyst is used for hydrogenation on cinnamic aldehyde reaction, reaction condition is as follows, 100mg cinnamic acid, 10mg catalyst, 100mg internal standard compound dodecane are scattered in 40mL ethanol, hydrogen is passed into 3MPa in batch reactor, be warming up to 20 DEG C, stop after reaction 8h, with GC-MS, the product under the differential responses time is monitored.Result shows, and the conversion ratio of cinnamic acid reaches 100% in 8h, and now the selective of selective 61.2%, the C=C of being hydrogenation of C=O hydrogenation is 30.5%, and the selective of complete hydrogenation is 8.3%.
Embodiment 4
Take 0.017mmol acetylacetone,2,4-pentanedione platinum and 0.05mmol acetylacetone cobalt puts into there-necked flask, add 24.8mmol oleyl amine and 6.3mmol oleic acid, under argon shield, be uniformly mixed 5min in 130 DEG C of heating, obtain mixed liquor A.Mixed liquor A transferred to rapidly in the oil bath pan of 225 DEG C, after temperature stabilization 5min, pass into carbon monoxide, flow velocity is 190mL/min, and reaction 30min, obtains black suspension B.Magneto separate after cool to room temperature, obtains black solid A.Take 2mg black solid and 4.0mg acetylacetone,2,4-pentanedione platinum puts into there-necked flask, add 7.5g oleyl amine and 903.9mgmmol oleic acid, under argon shield, be uniformly mixed 8min in 100 DEG C of heating, obtain mixed liquor C.Transferred to rapidly by mixed liquor C in the oil bath pan of 215 DEG C, pass into carbon monoxide simultaneously, flow velocity is 300mL/min, and reaction 10min, obtains black suspension D.Magneto separate after cool to room temperature, with ethanol purge three times, dried in vacuo overnight at 60 DEG C, obtains the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube.
Fig. 1 is the TEM figure of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation, Fig. 2 is that the high-resolution TEM of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation schemes, from Fig. 1 and Fig. 2, the described platinum cobalt nanometer bi-metal catalyst particle size be made up of multiple cube obtained is at 20 ~ 40nm, for dendritic platinum cobalt bimetallic nano structure, have eight branches, each branch is all independent cubes, good dispersion, composition is controlled, be magnetic, be easy to collect.
This catalyst is used for hydrogenation on cinnamic aldehyde reaction, reaction condition is as follows, 100mg cinnamic acid, 5mg catalyst, 100mg internal standard compound dodecane are scattered in 40mL ethanol, hydrogen is passed into 2MPa in batch reactor, be warming up to 50 DEG C, stop after reaction 8h, with GC-MS, the product under the differential responses time is monitored.Result shows, and the conversion ratio of cinnamic acid reaches 100% in 8h, and now the selective of selective 55.8%, the C=C of being hydrogenation of C=O hydrogenation is 23.1%, and the selective of complete hydrogenation is 21.1%.
Embodiment 5
Take 0.017mmol acetylacetone,2,4-pentanedione platinum and 0.05mmol acetylacetone cobalt puts into there-necked flask, add 24.8mmol oleyl amine and 7.3mmol oleic acid, under argon shield, be uniformly mixed 5min in 130 DEG C of heating, obtain mixed liquor A.Mixed liquor A transferred to rapidly in the oil bath pan of 225 DEG C, after temperature stabilization 5min, pass into carbon monoxide, flow velocity is 190mL/min, and reaction 30min, obtains black suspension B.Magneto separate after cool to room temperature, obtains black solid A.Take 1mg black solid and 8mg acetylacetone,2,4-pentanedione platinum puts into there-necked flask, add 5.2g lauryl amine and 995.8mgmmol stearic acid, under argon shield, be uniformly mixed 5min in 150 DEG C of heating, obtain mixed liquor C.Transferred to rapidly by mixed liquor C in the oil bath pan of 200 DEG C, pass into carbon monoxide simultaneously, flow velocity is 100mL/min, and reaction 1h, obtains black suspension D.Magneto separate after cool to room temperature, cleans three times with n-hexane, dried in vacuo overnight at 60 DEG C, obtains the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube.
Fig. 1 is the TEM figure of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation, Fig. 2 is that the high-resolution TEM of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation schemes, from Fig. 1 and Fig. 2, the described platinum cobalt nanometer bi-metal catalyst particle size be made up of multiple cube obtained is at 20 ~ 40nm, for dendritic platinum cobalt bimetallic nano structure, have eight branches, each branch is all independent cubes, good dispersion, composition is controlled, be magnetic, be easy to collect.
This catalyst is used for hydrogenation on cinnamic aldehyde reaction, reaction condition is as follows, 100mg cinnamic acid, 2mg catalyst, 100mg internal standard compound dodecane are scattered in 40mL ethanol, hydrogen is passed into 2MPa in batch reactor, be warming up to 60 DEG C, stop after reaction 8h, with GC-MS, the product under the differential responses time is monitored.Result shows, and the conversion ratio of cinnamic acid reaches 100% in 8h, and now the selective of selective 50.6%, the C=C of being hydrogenation of C=O hydrogenation is 21.7%, and the selective of complete hydrogenation is 27.7%.
Embodiment 6
Take 0.017mmol acetylacetone,2,4-pentanedione platinum and 0.05mmol acetylacetone cobalt puts into there-necked flask, add 24.8mmol oleyl amine and 6.3mmol oleic acid, under argon shield, be uniformly mixed 5min in 130 DEG C of heating, obtain mixed liquor A.Mixed liquor A transferred to rapidly in the oil bath pan of 225 DEG C, after temperature stabilization 5min, pass into carbon monoxide, flow velocity is 190mL/min, and reaction 30min, obtains black suspension B.Magneto separate after cool to room temperature, obtains black solid A.Take 2mg black solid and 8mg acetylacetone,2,4-pentanedione platinum puts into there-necked flask, add 4.6g cetylamine and 621.0mg laurate, under argon shield, be uniformly mixed 5min in 130 DEG C of heating, obtain mixed liquor C.Transferred to rapidly by mixed liquor C in the oil bath pan of 200 DEG C, pass into carbon monoxide simultaneously, flow velocity is 200mL/min, and reaction 30min, obtains black suspension D.Magneto separate after cool to room temperature, cleans three times with acetone, dried in vacuo overnight at 60 DEG C, obtains the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube.
Fig. 1 is the TEM figure of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation, Fig. 2 is that the high-resolution TEM of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation schemes, from Fig. 1 and Fig. 2, the described platinum cobalt nanometer bi-metal catalyst particle size be made up of multiple cube obtained is at 20 ~ 40nm, for dendritic platinum cobalt bimetallic nano structure, have eight branches, each branch is all independent cubes, good dispersion, composition is controlled, be magnetic, be easy to collect.
This catalyst is used for hydrogenation on cinnamic aldehyde reaction, reaction condition is as follows, 100mg cinnamic acid, 1mg catalyst, 100mg internal standard compound dodecane are scattered in 40mL ethanol, hydrogen is passed into 2MPa in batch reactor, be warming up to 60 DEG C, stop after reaction 24h, with GC-MS, the product under the differential responses time is monitored.Result shows, and the conversion ratio of cinnamic acid reaches 100% in 24h, and now the selective of selective 49.4%, the C=C of being hydrogenation of C=O hydrogenation is 23.5%, and the selective of complete hydrogenation is 27.1%.
Embodiment 7
Take 0.017mmol acetylacetone,2,4-pentanedione platinum 0.034mmol acetylacetone cobalt and put into there-necked flask, add 24.8mmol lauryl amine and 6.2mmol stearic acid, under argon shield, be uniformly mixed 10min in 100 DEG C of heating, obtain mixed liquor A.Mixed liquor A transferred to rapidly in the oil bath pan of 220 DEG C, after temperature stabilization 2min, pass into carbon monoxide, flow velocity is 100mL/min, and reaction 30min, obtains black suspension B.Magneto separate after cool to room temperature, obtains black solid A.Take 2mg black solid and 8mg acetylacetone,2,4-pentanedione platinum puts into there-necked flask, add 6.8g cetylamine and 621.0mg laurate, under argon shield, be uniformly mixed 5min in 130 DEG C of heating, obtain mixed liquor C.Transferred to rapidly by mixed liquor C in the oil bath pan of 200 DEG C, pass into carbon monoxide simultaneously, flow velocity is 200mL/min, and reaction 30min, obtains black suspension D.Magneto separate after cool to room temperature, cleans three times with acetone, dried in vacuo overnight at 60 DEG C, obtains the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube.
Fig. 1 is the TEM figure of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation, Fig. 2 is that the high-resolution TEM of the platinum cobalt nanometer bi-metal catalyst be made up of multiple cube of preparation schemes, from Fig. 1 and Fig. 2, the described platinum cobalt nanometer bi-metal catalyst particle size be made up of multiple cube obtained is at 20 ~ 40nm, for dendritic platinum cobalt bimetallic nano structure, have eight branches, each branch is all independent cubes, good dispersion, composition is controlled, be magnetic, be easy to collect.
This catalyst is used for hydrogenation on cinnamic aldehyde reaction, reaction condition is as follows, 100mg cinnamic acid, 2mg catalyst, 100mg internal standard compound dodecane are scattered in 40mL ethanol, hydrogen is passed into 2MPa in batch reactor, be warming up to 60 DEG C, stop after reaction 10h, with GC-MS, the product under the differential responses time is monitored.Result shows, and the conversion ratio of cinnamic acid reaches 100% in 10h, and now the selective of selective 48.5%, the C=C of being hydrogenation of C=O hydrogenation is 24.5%, and the selective of complete hydrogenation is 27.0%.
Claims (14)
1. a platinum cobalt nanometer bi-metal catalyst, is characterized in that, described catalyst is dendritic platinum cobalt bimetallic nano structure, and have eight branches, each branch is an independent cube.
2. platinum cobalt nanometer bi-metal catalyst as claimed in claim 1, it is characterized in that, the particle diameter of described catalyst is 20nm ~ 40nm.
3. the preparation method of platinum cobalt nanometer bi-metal catalyst as claimed in claim 1 or 2, is characterized in that, adopts liquid phase reduction preparation, comprises the following steps:
(1) under the protection of inert gas, acetylacetone,2,4-pentanedione platinum, acetylacetone cobalt, alkylamine and alkyl acid are carried out Homogenization Treatments, obtain the first mixed solution;
(2) described first mixed liquor that step (1) obtains is passed into reducing gas to react, obtain the first black suspension, Magneto separate, obtain black solid;
(3) under the protection of inert gas, the described black solid, acetylacetone,2,4-pentanedione platinum, alkylamine and the alkyl acid that step (2) are obtained carry out Homogenization Treatments, obtain the second mixed solution;
(4) described second mixed liquor that step (3) obtains is passed into reducing gas to react, obtain the second black suspension;
(5) described second black suspension that step (4) obtains is carried out clean, Magneto separate and drying, namely obtain described catalyst.
4. the preparation method of platinum cobalt nanometer bi-metal catalyst as claimed in claim 3, it is characterized in that, in step (1), the mol ratio of described acetylacetone,2,4-pentanedione platinum and acetylacetone cobalt is 1:4 ~ 1:2, the mol ratio of described alkylamine and acetylacetone,2,4-pentanedione platinum is 1459:1 ~ 1094:1, and the mol ratio of described alkyl acid and acetylacetone,2,4-pentanedione platinum is 482:1 ~ 365:1.
5. the preparation method of platinum cobalt nanometer bi-metal catalyst as claimed in claim 3, it is characterized in that, in step (1) and step (3), the temperature of described Homogenization Treatments is 100 ~ 150 DEG C, and the time of described Homogenization Treatments is 5 ~ 30min.
6. the preparation method of platinum cobalt nanometer bi-metal catalyst as claimed in claim 3, is characterized in that, in step (1) and step (3), described alkylamine be selected from oleyl amine, lauryl amine and cetylamine one or more; Described alkyl acid be selected from oleic acid, stearic acid and laurate one or more.
7. the preparation method of platinum cobalt nanometer bi-metal catalyst as claimed in claim 3, it is characterized in that, in step (2), reaction temperature is 220 DEG C ~ 235 DEG C.
8. the preparation method of platinum cobalt nanometer bi-metal catalyst as claimed in claim 3, it is characterized in that, in step (3), the mass ratio of the described black solid that step (2) obtains and acetylacetone,2,4-pentanedione platinum is 1:8 ~ 1:2, the mass ratio of described alkylamine and black solid is 5200:1 ~ 2300:1, and the mass ratio of described alkyl acid and black solid is 996:1 ~ 311:1.
9. the preparation method of platinum cobalt nanometer bi-metal catalyst as claimed in claim 3, it is characterized in that, in step (4), reaction temperature is 200 ~ 215 DEG C.
10. the preparation method of platinum cobalt nanometer bi-metal catalyst as claimed in claim 3 described, is characterized in that, in step (2) and step (4), described reducing gas is carbon monoxide, and flow velocity is 100 ~ 300mL/min.
The preparation method of 11. platinum cobalt nanometer bi-metal catalysts as claimed in claim 3, is characterized in that, in step (2) and step (4), the described reaction time is 10min ~ 1h.
The preparation method of 12. platinum cobalt nanometer bi-metal catalysts as claimed in claim 3, is characterized in that, in step (5), clean with organic solvent, described organic solvent be selected from ethanol, chloroform, n-hexane and acetone one or more.
13. platinum cobalt nanometer bi-metal catalysts as claimed in claim 1 or 2 are used for hydrogenation on cinnamic aldehyde reaction.
The purposes of 14. platinum cobalt nanometer bi-metal catalysts as claimed in claim 13, it is characterized in that, the condition of hydrogenation reaction is: reaction pressure is 1.5 ~ 3MPa, and reaction temperature is 20 ~ 80 DEG C, reaction time is 8 ~ 24h, and the mass ratio of described cinnamic acid and catalyst is 10:1 ~ 100:1.
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