CN110433797A - A kind of monatomic Pd base catalyst and its preparation method and application - Google Patents
A kind of monatomic Pd base catalyst and its preparation method and application Download PDFInfo
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- CN110433797A CN110433797A CN201910693668.1A CN201910693668A CN110433797A CN 110433797 A CN110433797 A CN 110433797A CN 201910693668 A CN201910693668 A CN 201910693668A CN 110433797 A CN110433797 A CN 110433797A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- RINOYHWVBUKAQE-UHFFFAOYSA-N 1-iodo-2-methylbenzene Chemical compound CC1=CC=CC=C1I RINOYHWVBUKAQE-UHFFFAOYSA-N 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- -1 halogenated aryl hydrocarbon Chemical class 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000012696 Pd precursors Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 235000011181 potassium carbonates Nutrition 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 108010053481 Antifreeze Proteins Proteins 0.000 claims description 3
- 230000002528 anti-freeze Effects 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000007341 Heck reaction Methods 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 230000000694 effects Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000011941 Heck reaction process Methods 0.000 description 1
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- 229910000364 palladium(II) sulfate Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—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
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Abstract
Present invention relates particularly to a kind of monatomic Pd base catalyst and its preparation method and application, the carrier of the catalyst is MgAl-LDO, and active component Pd is dispersed in the surface MgAl-LDO in the form of atom level.The preparation method of the catalyst, comprising the following steps: MgAl-LDH is prepared by coprecipitation, MgAl-LDO then is made by calcination process in MgAl-LDH；MgAl-LDO is impregnated in Pd presoma, then monatomic Pd base catalyst is made through low temperature ultrasonic reduction treatment.Preparation method of the invention is simple, environmentally protective, at low cost, has industrial application value, for showing excellent catalytic activity and reusable feature in Heck reaction.
Description
Technical field
The invention belongs to catalyst synthesis technology fields, and in particular to a kind of monatomic Pd base catalyst and preparation method thereof
With the application in Heck coupling reaction.
Background technique
The halogenated aryl hydrocarbon of palladium (Pd) catalysis and the Heck coupling reaction of alkene, which have become, synthesizes unsaturated carbon-carbon double bond
One of important methodology of organic synthesis is widely used in the important intermediate of synthetic drug molecule, natural products and new material.So
And homogeneous Pd base catalyst there are difficult separation and recycling, be easy inactivation, expensive and environmental pollution the problems such as, limit significantly
Its extensive use industrially.Therefore, generally by by Pd nanometer particle load on carrier to solve the above problems, often
It is active carbon with carrier, since physical bond is insecure between active component Pd and active carbon, active component Pd is be easy to cause to flow
Lose phenomenon.
Hydrotalcite (LDH) is also referred to as layered double hydroxide, is a kind of anion type laminated porous structural material, changes
Learning general formula is [M2+ 1-xM3+ x(OH)2]x+(An-)x/n·yH2O, wherein M2+And M3+Respectively divalent and trivalent metal cation, position
In in main layer board；An-For interlayer anion；X is M2+/(M2++M3+) molar ratio；Y is the number of interlayer hydrone.In
There is the minimum effect of lattice energy and lattice orientation effect in LDH crystal structure, metal ion is on laminate with certain side
Formula is uniformly distributed, and forms specific the Nomenclature Composition and Structure of Complexes.LDH by roasting after slough intermediary water, anion and form metal composite
Oxide (LDO), LDO have higher specific surface area, absorption property and strong basicity, are the excellent carriers of basic catalyst.
Monatomic catalyst is a kind of new catalyst, and the metal active constituent based on atomic level is maximizing activity
Bit number of points, enhancing show huge to the selectivity of target product, the intrinsic catalytic activity of raising and in terms of reducing noble metal dosage
Big advantage.
Also Heck idol is not applied to it about the monatomic Pd base catalyst of support type using MgAl-LDO as carrier at present
Join the relevant report of reaction.
Therefore, using MgAl-LDO as carrier, then by dip loading Pd presoma, low temperature ultrasonic restores the present invention, so that
Active component Pd is dispersed in MgAl-LDO carrier in the form of atom level.The catalyst shows excellent in Heck reaction
Catalytic effect and reusability.
Summary of the invention
The purpose of the present invention is to provide a kind of monatomic Pd base catalyst and preparation method thereof, the active groups of the catalyst
Divide between Pd and MgAl-LDO carrier and be firmly combined, active component Pd is dispersed in MgAl-LDO carrier in the form of atom level
On, for showing excellent catalytic activity and reusable feature in Heck reaction, and preparation process is simple.
To achieve the goals above, technical scheme is as follows:
A kind of monatomic Pd base catalyst, is made of active component Pd and carrier, which is characterized in that the carrier is
MgAl-LDO, the active component Pd are dispersed in the surface MgAl-LDO in the form of atom level.
In above-mentioned monatomic Pd base catalyst, MgAl-LDO partial size is 40-60 mesh, and Mg element and the molar ratio of Al element are
(2-4):1。
In above-mentioned monatomic Pd base catalyst, Pd load capacity is 0.01%-0.5%, partial size 0.01-1nm.
The preparation method of above-mentioned monatomic Pd base catalyst, comprising the following steps: MgAl-LDH is prepared by coprecipitation,
Then MgAl-LDO is made by calcination process in MgAl-LDH；MgAl-LDO is impregnated in Pd presoma, then super through low temperature
Sound reduction treatment makes active component Pd be dispersed in the surface MgAl-LDO in the form of atom level, and monatomic Pd base catalysis is made
Agent.
The preparation method of above-mentioned monatomic Pd base catalyst, specifically includes the following steps:
1, under conditions of room temperature and mechanical stirring, precipitant solution the preparation of MgAl-LDO presoma: is added drop-wise to Mg
(NO3) in the mixed solution of 26H2O and Al (NO3) 39H2O, pH value is controlled in 10-11, after being added dropwise, continues to stir
Reaction solution is centrifuged after 10-30min, 100-120 DEG C of crystallization 12-24h, washing to neutrality, MgAl- is made in 40-80 DEG C of drying
LDH；MgAl-LDH is roasted into 1-2h in 200-500 DEG C of air atmosphere, the product after roasting through tabletting, be ground up, sieved, take
MgAl-LDO is made in 40-60 powder material；
2, the preparation of monatomic Pd base catalyst: MgAl-LDO is stirred to dipping 5-10h in Pd precursor solution, then
In -50 to 0 DEG C of ultrasonic reduction treatment 1-2h, filters, wash after reaction, 60-100 DEG C of dry 12-24h is made monatomic
Pd base catalyst.
In above-mentioned steps 1, the total ion concentration of mixed solution is 0.5-1mol/L；Mg2+With Al3+Molar ratio be (2-
4):1。
In above-mentioned steps 1, the concentration of precipitant solution is 0.5-1mol/L, precipitating reagent and metal ion (Mg2++Al3+)
Molar ratio is (1-3): 1；Precipitating reagent is any one or more in NaOH, Na2CO3, KOH, K2CO3.
In above-mentioned steps 1, dropwise addition carries out under stiring, and revolving speed is 300-1000 revs/min, drop rate 1-3mL/
min。
In above-mentioned steps 1, the heating rate of roasting is 2-10 DEG C/min.
In above-mentioned steps 2, the concentration of Pd precursor solution is 0.0004-0.0005mol/L；Pd presoma is the solvable of Pd
Property salt；The solvent for dissolving Pd presoma is noncondensing anti-freeze solvent under low temperature environment.
In above-mentioned steps 2, the rate of stirring is 400-1000r/min.
In above-mentioned steps 2, ultrasonic power is 500-2000W.
Monatomic Pd base catalyst of the invention can be used in the Heck coupling reaction of halogenated aryl hydrocarbon and alkene, preferably react
Condition: 0.5mmol is to iodotoluene, 0.6mmol n-butyl acrylate, 1mmol potassium carbonate, solvent DMF 5mL, catalyst 30mg, nitrogen
Gas shielded, 90 DEG C of reaction 6h.Target product yield reaches 93%-99%, after circular response 5 times, target product yield after reacting 6h
Up to 90-96%, catalytic activity is without being decreased obviously.
Compared with prior art, preparation method of the invention is simple, environmentally protective, at low cost, has industrial application value,
It is firmly combined between active component Pd and the MgAl-LDO carrier of the catalyst, active component Pd is evenly dispersed in the form of atom level
On MgAl-LDO carrier, active component Pd load capacity is 0.01%-0.5%, for showing excellent urge in Heck reaction
Change activity and reusable feature.
1, metal ion is changed into corresponding oxide M gAl-LDO after MgAl-LDH roasting, and MgAl-LDO has higher ratio
Surface area, absorption property and strong basicity are the good carriers of basic catalyst.
2, the memory effect of MgAl-LDH makes MgAl-LDO load active component Pd in the process along with layer structure portion
Divide the laminate confinement effect for restoring and generating effectively to prevent the agglomeration of active component Pd, mildly restores ring in conjunction with low temperature
Border, so that Pd is dispersed in the surface MgAl-LDO in the form of atom level.
3, the Pd of atomic level have efficient atom utilization, in conjunction with the high surface area of MgAl-LDO, high adsorption and
Strong basicity so that active component Pd load capacity is low, and shows in Heck reaction excellent catalytic activity and repeatable makes
The characteristics of using.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of monatomic Pd base catalyst of the invention.
Specific embodiment
The present invention is described in detail With reference to embodiment.
Monatomic Pd base catalyst of the invention, active component Pd are dispersed in MgAl-LDO table in the form of atom level
Face.
In above-mentioned monatomic Pd base catalyst, the molar ratio of Mg element and Al element is (2-4): 1, partial size is 40-60 mesh.
In above-mentioned monatomic Pd base catalyst, Pd load capacity is 0.01%-0.5%, partial size 0.01-1nm.
The preparation method of above-mentioned monatomic Pd base catalyst, comprising the following steps: MgAl-LDH is prepared by coprecipitation,
Then MgAl-LDO is made by calcination process in MgAl-LDH；MgAl-LDO is impregnated in Pd presoma, then super through low temperature
Sound reduction treatment makes active component Pd be dispersed in the surface MgAl-LDO in the form of atom level, and monatomic Pd base catalysis is made
Agent.
The preparation method of above-mentioned monatomic Pd base catalyst, specifically includes the following steps:
1, under conditions of room temperature and mechanical stirring, precipitant solution the preparation of MgAl-LDO presoma: is added drop-wise to Mg
(NO3) in the mixed solution of 26H2O and Al (NO3) 39H2O, pH value is controlled in 10-11, after being added dropwise, continues to stir
Reaction solution is centrifuged after 10-30min, 100-120 DEG C of crystallization 12-24h, washing to neutrality, MgAl- is made in 40-80 DEG C of drying
LDH；MgAl-LDH is roasted into 1-2h in 200-500 DEG C of air atmosphere, the product after roasting through tabletting, be ground up, sieved, take
MgAl-LDO is made in 40-60 powder material；
2, the preparation of monatomic Pd base catalyst: MgAl-LDO is stirred to dipping 5-10h in Pd precursor solution, then
In -50 to 0 DEG C of ultrasonic reduction treatment 1-2h, filters, wash after reaction, 60-100 DEG C of dry 12-24h is made monatomic
Pd base catalyst.
In above-mentioned steps 1, the total ion concentration of mixed solution is 0.5-1mol/L；Mg2+With Al3+Molar ratio be (2-
4):1；The solvent of mixed solution is the conventional selection of those skilled in the art, appointing preferably in deionized water or C1-5 alcohols
It anticipates one or more, more preferably deionized water.
In above-mentioned steps 1, the concentration of precipitant solution is 0.5-1mol/L, precipitating reagent and metal ion (Mg2+And Al3+)
Molar ratio be (1-3): 1；Precipitating reagent is any one or more in NaOH, Na2CO3, KOH, K2CO3, dissolves precipitating reagent
Solvent be those skilled in the art conventional selection, preferably any one or more in deionized water or C1-5 alcohols,
More preferably deionized water.
In above-mentioned steps 1, dropwise addition carries out under stiring, and revolving speed is 300-1000 revs/min, drop rate 1-3mL/
min。
In above-mentioned steps 1, the heating rate of roasting is 2-10 DEG C/min.
In above-mentioned steps 2, the concentration of Pd precursor solution is 0.0001-0.0006mol/L；Pd presoma is the solvable of Pd
Property salt, for example, one of PdCl2, Pd (NO3) 2, PdSO4 or Na2PdCl4 or a variety of；Dissolution Pd presoma solvent be
Noncondensing anti-freeze solvent under low temperature environment, preferably deionized water or C1-5 alcohols, more preferably deionized water.
In above-mentioned steps 2, the rate of stirring is 400-1000r/min.
In above-mentioned steps 2, ultrasonic power is 500-2000W.
Monatomic Pd base catalyst of the invention can be used in the Heck coupling reaction of halogenated aryl hydrocarbon and alkene, preferably react
Condition: 0.5mmol is to iodotoluene, 0.6mmol n-butyl acrylate, 1mmol potassium carbonate, solvent DMF 5mL, catalyst 30mg, nitrogen
Gas shielded, 90 DEG C of reaction 6h, product is extracted with ethyl acetate after reaction, extracts organic phase and uses gas chromatograph GC-2010
Detect yield.
A specific embodiment of the invention is further described below with reference to embodiment, is not therefore limited the present invention
System is among the embodiment described range.
Embodiment 1
It is mixed by being made into 20mmolMg (NO3) 26H2O and 10mmolAl (NO3) 39H2O addition 40mL deionized water
Close solution；Using NaOH as precipitating reagent, 50mmolNaOH is added in 100mL deionized water and is made into precipitant solution；In room temperature and
Under the stirring condition of 300r/min, precipitant solution is added drop-wise in mixed solution with the speed of 1mL/min, until in system
PH value reaches 10；After being added dropwise, continuing to stir 10min, reaction solution is centrifuged by 100 DEG C of crystallization afterwards for 24 hours, washing to neutrality, and 40
MgAl-LDH is made in DEG C drying；MgAl-LDH is put into muffle furnace, roasts 1h in 200 DEG C of air atmospheres, heating rate is
2℃/min；Product after roasting through tabletting, be ground up, sieved, take 40-60 powder material, MgAl-LDO be made；MgAl-LDO is existed
In 10mL 0.0001mol/L PdCl2 aqueous solution, 400rpm impregnates 5h, and then in -50 DEG C of ultrasonic treatment 1h, ultrasonic power is
500W；It filters after reaction, deionized water washing, the monatomic Pd base that Pd load capacity is 0.01% is made in 60 DEG C of dry 12h
Catalyst.
The monatomic Pd base catalyst of embodiment 1 is used in the Heck coupling reaction of halogenated aryl hydrocarbon and alkene, item is reacted
Part: 0.5mmol is to iodotoluene, 0.6mmol n-butyl acrylate, 1mmol potassium carbonate, solvent DMF 5mL, catalyst 30mg, nitrogen
Protection, after 90 DEG C of reaction 6h, target product yield is up to 93%；After circular response 5 times, target product yield is up to 90%；Repetition makes
After 10 times, target product yield is up to 76%.
Embodiment 2
It is mixed by being made into 40mmolMg (NO3) 26H2O and 10mmolAl (NO3) 39H2O addition 50mL deionized water
Close solution；Using Na2CO3 as precipitating reagent, 100mmolNa2CO3 is added in 100mL deionized water and is made into precipitant solution；In room
Under the stirring condition of mild 1000r/min, precipitant solution is added drop-wise in mixed solution with the speed of 3mL/min, Zhi Daoti
PH value in system reaches 11；After being added dropwise, continues to stir 30min, reaction solution is centrifuged after 120 DEG C of crystallization 12h, is washed into
Property, MgAl-LDH is made in 80 DEG C of dryings；MgAl-LDH is put into muffle furnace, roasts 2h in 500 DEG C of air atmospheres, is heated up
Speed is 10 DEG C/min；Product after roasting through tabletting, be ground up, sieved, take 40-60 powder material, MgAl-LDO be made；It will
For MgAl-LDO in 20mL 0.0001mol/L Pd (NO3) 2 aqueous solution, 1000rpm impregnates 10h, is then ultrasonically treated at 0 DEG C
2h, ultrasonic power 2000W；It filters after reaction, deionized water washing, for 24 hours, Pd load capacity, which is made, is for 100 DEG C of dryings
0.5% monatomic Pd base catalyst.
The monatomic Pd base catalyst of embodiment 2 is used in the Heck coupling reaction of halogenated aryl hydrocarbon and alkene, item is reacted
Part: 0.5mmol is to iodotoluene, 0.6mmol n-butyl acrylate, 1mmol potassium carbonate, solvent DMF 5mL, catalyst 30mg, nitrogen
Protection, after 90 DEG C of reaction 6h, target product yield is up to 99%；After circular response 5 times, target product yield is up to 95%；Repetition makes
After 10 times, target product yield is up to 80%.
Embodiment 3
It is mixed by being made into 30mmolMg (NO3) 26H2O and 10mmolAl (NO3) 39H2O addition 40mL deionized water
Close solution；Using Na2CO3 as precipitating reagent, 90mmolNa2CO3 is added in 100mL deionized water and is made into precipitant solution；In room
Under the stirring condition of mild 500r/min, precipitant solution is added drop-wise in mixed solution with the speed of 2mL/min, until system
In pH value reach 11；After being added dropwise, continue to stir 10min, reaction solution is centrifuged by 120 DEG C of crystallization afterwards for 24 hours, is washed into
Property, MgAl-LDH is made in 80 DEG C of dryings；MgAl-LDH is put into muffle furnace, roasts 1h in 300 DEG C of air atmospheres, is heated up
Speed is 2 DEG C/min；Product after roasting through tabletting, be ground up, sieved, take 40-60 powder material, MgAl-LDO be made；By MgAl-
LDO is in 20mL 0.0006mol/LNa2PdCl4In aqueous solution, 500rpm impregnates 5h, then in -40 DEG C of ultrasonic treatment 2h, ultrasound
Power is 1000W；It filters after reaction, deionized water washing, 80 DEG C of dry 12h, single original that Pd load capacity is 0.1% is made
Sub- Pd base catalyst.
The monatomic Pd base catalyst of embodiment 3 is used in the Heck coupling reaction of halogenated aryl hydrocarbon and alkene, item is reacted
Part: 0.5mmol is to iodotoluene, 0.6mmol n-butyl acrylate, 1mmol potassium carbonate, solvent DMF 5mL, catalyst 30mg, nitrogen
Protection, after 90 DEG C of reaction 6h, target product yield is up to 98%；After circular response 5 times, target product yield is up to 96%；Repetition makes
After 10 times, target product yield is up to 84%.
Comparative example 1
For other steps with embodiment 3, difference, which is only that, is substituted for MgAl-LDH for carrier MgAl-LDO, and Pd is prepared and contains
The nano Pd particle base catalyst that amount is 0.1%.Catalyst 6h in the Heck coupling reaction to iodotoluene and n-butyl acrylate
Yield is 75%, and after circular response 5 times, target product yield is up to 60%；After reusing 10 times, target product yield reaches
50%.
Monatomic Pd base catalyst of the invention makes for showing excellent catalytic activity in Heck reaction with repeatable
The characteristics of using.
Technical solution of the present invention is described in detail in above-described embodiment.It is apparent that the present invention is not limited being retouched
The embodiment stated.Based on the embodiments of the present invention, those skilled in the art can also make a variety of variations accordingly, but appoint
What is equal with the present invention or similar variation shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of monatomic Pd base catalyst, is made of active component Pd and carrier, which is characterized in that the carrier is MgAl-
LDO, the active component Pd are dispersed in the surface MgAl-LDO in the form of atom level.
2. monatomic Pd base catalyst according to claim 1, which is characterized in that the partial size of the MgAl-LDO is 40-
The molar ratio of 60 mesh, Mg element and Al element is (2-4): 1.
3. monatomic Pd base catalyst according to claim 1 or 2, which is characterized in that the load of the active component Pd
Amount is 0.01%-0.5%, partial size 0.01-1nm.
4. the preparation method of monatomic Pd base catalyst according to claim 1 to 3, comprising the following steps: logical
Coprecipitation preparation MgAl-LDH is crossed, MgAl-LDO then is made by calcination process in the MgAl-LDH；By the MgAl-
LDO impregnates in Pd presoma, then through low temperature ultrasonic reduction treatment active component Pd is dispersed in the form of atom level
Monatomic Pd base catalyst is made in the surface MgAl-LDO.
5. the preparation method according to claim 4, specifically includes the following steps:
(1) under conditions of room temperature and mechanical stirring, precipitant solution the preparation of MgAl-LDO presoma: is added drop-wise to Mg
(NO3) in the mixed solution of 26H2O and Al (NO3) 39H2O, pH value is controlled in 10-11, after being added dropwise, continues to stir
Reaction solution is centrifuged after 10-30min, 100-120 DEG C of crystallization 12-24h, washing to neutrality, MgAl- is made in 40-80 DEG C of drying
LDH；The MgAl-LDH is roasted into 1-2h in 200-500 DEG C of air atmosphere, the product after roasting is through tabletting, grinding, mistake
Sieve, takes 40-60 powder material, and MgAl-LDO is made；
(2) preparation of monatomic Pd base catalyst: the MgAl-LDO is stirred to dipping 5-10h in Pd precursor solution, so
It afterwards in -50 to 0 DEG C of ultrasonic reduction treatment 1-2h, filters, washs, 60-100 DEG C of dry 12-24h after reaction, be made single former
Sub- Pd base catalyst.
6. preparation method according to claim 5, which is characterized in that the total ion concentration of mixed solution described in step 1
For 0.5-1mol/L；Mg2+With Al3+Molar ratio be (2-4): 1.
7. preparation method according to claim 5, which is characterized in that the concentration of precipitant solution described in step 1 is
The molar ratio of 0.5-1mol/L, precipitating reagent and metal ion is (1-3): 1；Precipitating reagent is in NaOH, Na2CO3, KOH, K2CO3
Any one or more.
8. preparation method according to claim 5, which is characterized in that the concentration of Pd precursor solution described in step 2 is
0.0004-0.0005mol/L；Pd presoma is the soluble-salt of Pd；The solvent of dissolution Pd presoma is not coagulate under low temperature environment
Solid anti-freeze solvent.
9. according to answering for monatomic Pd base catalyst made from preparation method described in claims requirement 4-8 any one
With, which is characterized in that the monatomic Pd base catalyst can be used in the Heck coupling reaction of halogenated aryl hydrocarbon and alkene.
10. according to application described in claims requirement 9, which is characterized in that Heck coupling reaction condition are as follows: 0.5mmol
To iodotoluene, 0.6mmol n-butyl acrylate, 1mmol potassium carbonate, solvent DMF 5mL, catalyst 30mg, nitrogen protection, 90 DEG C
React 6h.
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