CN104801316B - High dispersive small-size magnetic load type gold palladium alloy catalysts and preparation method thereof - Google Patents
High dispersive small-size magnetic load type gold palladium alloy catalysts and preparation method thereof Download PDFInfo
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 63
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001252 Pd alloy Inorganic materials 0.000 title claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 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 claims abstract description 31
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 31
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000011258 core-shell material Substances 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000010931 gold Substances 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 230000005415 magnetization Effects 0.000 claims abstract description 6
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- 238000011068 loading method Methods 0.000 claims abstract description 3
- 239000006249 magnetic particle Substances 0.000 claims abstract description 3
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
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- 239000012266 salt solution Substances 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 239000000969 carrier Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 238000000975 co-precipitation Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 6
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- HDWLUGYOLUHEMN-UHFFFAOYSA-N Dinobuton Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1OC(=O)OC(C)C HDWLUGYOLUHEMN-UHFFFAOYSA-N 0.000 claims description 3
- 241000425573 Talanes Species 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
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- 229910001020 Au alloy Inorganic materials 0.000 claims description 2
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- 239000010970 precious metal Substances 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 239000003643 water by type Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- -1 aryl alkene derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
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- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
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- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical class [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
A kind of high dispersive small-size magnetic load type gold palladium alloy catalysts and preparation method thereof, belong to magnetic loading type precious metal catalytic material field.Catalyst is that rhotanium nanoparticle made from reduction of ethylene glycol method is carried in magnetic multistage core shell structure hydrotalcite supports, obtain the magnetic multistage core shell structure load type gold palladium alloy catalysts of high dispersive small size, the mass percent of each element is respectively Pd in its active component rhotanium:1% 3%, Au:1% 3%, particle size distribution scope is<4nm；Honeycomb pattern is presented in the catalyst, and saturation magnetization Ms is 28 42emu/g；The core of magnetic multistage core shell structure hydrotalcite supports is Fe 3 O 4 magnetic particle, and shell is hydrotalcite (M2+‑M3+)‑LDH.Advantage is that for the rhotanium nano-particle high dispersive of the catalyst on the shell hydrotalcite of magnetic carrier, preparation technology is simple, can be reused after the completion of reaction by the rapid enriching and recovering of the externally-applied magnetic fields such as magnet.
Description
Technical field
The invention belongs to carried noble metal catalysis material technical field, in particular, provides a kind of high dispersive small size magnetic
Property load type gold palladium alloy catalysts and preparation method thereof.
Background technology
Heck reactions are that virtueization alkene is generated in the presence of highly basic and palladium catalyst by unsaturated halogenated hydrocarbons and alkene
One kind reaction.Since Heck in 1971 et al. has found the reaction, because the type reaction can be efficiently synthesized with important valency
Series of aryl alkene derivatives, cinnamate analog derivative and diphenyl ethylene derivatives of value etc. and gradually develop into a kind of application
Increasingly extensive modern organic synthesis method, is widely used in dyestuff, agricultural chemicals, medicine, luminescent material, daily chemicals and height
It is the key object that catalytic chemistry man and organic chemists study in the commercial synthesis field of polymers.Monometallic Pd is urged at present
Agent obtains system in-depth study because activity is higher, is developing progressively the dominant catalyst for Heck reactions.However, contain
Organic phosphine, the homogeneous palladium-based catalyst of nitrogen ligand is difficult because prepared by its part, cost is high, pollution environment, and such catalyst pair
The problem of water, heat, air etc. are more sensitive, and maximum is that homogeneous catalyst is difficult to separate with reaction solution, and recovery difficulty can not
Recycling so that its practical application is greatly limited.Although the increasing loaded catalyst one of Recent study
Determine to maintain good catalytic activity in degree, and recycling can be separated and recovered, but the separation of traditional filtering and centrifugation
Process there is it is numerous and diverse laborious, tediously long time-consuming the problem of.
Magnetic/functionalized catalysis material recycles and reuses because it can be rapidly separated by external magnetic field and turns into and solve in recent years
The available strategy that certainly separation and recovery of catalyst recycles.2011, this seminar was with hydrotalcite coated ferroferric oxide carrier
Upper load gold nano particle, a kind of multilevel core-shell structure magnetic nano gold catalyst (Chinese invention patent ZL 2,011 1 is made
0344754.5), it is applied to alcohol oxidation reaction, not only with good catalytic activity feature, and also it is stronger super using it
Paramagnetic performance can be reused by the convenient enriching and recovering of externally-applied magnetic field.In recent years, the stable bimetallic gold-palladium catalysis of part
Agent is widely used in alcohol because its special composition, structure and size, cloud density etc. have attracted increasing research interest
In the reaction systems such as oxidation, the preparation of hydrogen peroxide, nitro halogen benzene selective hydrogenation, but exist catalyst separation and environment ask
Topic.Hutchings etc. (Jennifer K.Edwards, Graham J.Hutchings.Journal of Catalysis,
2005,236,69-79) titania oxide supported rhotanium catalyst, the grain of gold-palladium nanoparticle are made using traditional immersion reduction method
Footpath distribution is wide, and two kinds of particle diameter distributions are presented, and small particle is 1-8nm, and big particle diameter is 40-70nm.(the Sarina such as Zhu
Sarina,Huaiyong Zhu.Journal of the American Chemical Society,2013,135,5793–
5801) zirconium oxide gold-supported palladium alloy catalysts are made using traditional immersion reduction method, the particle diameter of rhotanium nanoparticle is less than
8nm.So far, the preparation not yet about hydrotalcite coated ferroferric oxide magnetic carrier load gold-palladium nanometer alloy catalyst
And its report applied to Heck coupling reactions.
Thus, the present invention intends preparing rhotanium nano-particle using reduction of ethylene glycol method and is carried on multistage nucleocapsid
So as to obtained multistage core-shell structure magnetic load type gold palladium alloy catalysts, the work of the catalyst in structure magnetic hydrotalcite supports
Property component rhotanium nanoparticle particle diameter is less than 4nm, can be as a kind of green C-C coupling reaction catalyst of high activity.
The content of the invention
It is an object of the invention to provide a kind of high dispersive small-size magnetic load type gold palladium alloy catalysts and its preparation
Method.Size is small, is catalyzed on the shell hydrotalcite of magnetic carrier, presenting for the rhotanium nano-particle high dispersive of the catalyst
The characteristics of activity is high, preparation technology is simple, can repeat profit by the rapid enriching and recovering of the externally-applied magnetic fields such as magnet after the completion of reaction
With.
The catalyst of the present invention is that rhotanium nanoparticle made from reduction of ethylene glycol method is carried on into magnetic multistage nucleocapsid
In structure hydrotalcite supports, the magnetic multistage core shell structure load type gold palladium alloy catalysts of high dispersive small size are obtained, it is lived
The mass percent of each element is respectively Pd in property component rhotanium:1%-3%, Au:1%-3%, particle size distribution model
Enclose for<4nm；Honeycomb pattern is presented in the catalyst, and saturation magnetization Ms is 28-42emu/g；Magnetic multistage core shell structure water
The core of steatite support is Fe 3 O 4 magnetic particle, and its size is 500-600nm, accounts for total catalyst mass percent and is
44%-58%, shell are hydrotalcite (M2+-M3+)-LDH, M2+For Mg2+、Ni2+、Co2+、Cu2+It is any one in bivalent metal ion
Kind or two kinds, M3+For trivalent metal ion Al3+, shell thickness 30-120nm, mass percent 39%-53%.
Described catalyst has high catalytic activity and selectivity in Heck coupling reaction systems, with iodobenzene and styrene
It is coupled as probe reaction, catalyst (Fe3O4@NiAl-LDH@Pd-Au-3%-3%) input amount is 50mg, potassium carbonate is alkali addition
Agent, solvent is the mixed liquor of 12mL DMFs (DMF) and 4mL water, after 120 DEG C are reacted 3h, the conversion of iodobenzene
Rate is up to 100%, and target product is trans-yield of talan is up to 93%.Can be reclaimed rapidly using the magnetic characteristic of catalyst and
Reuse, reusing 5 activity does not substantially reduce.
Present invention process step is as follows：
(1) preparation of magnetic core
Using the solvent-thermal method of surfactant-free, specific preparation process：Weigh 3.24g (0.012mol) FeCl3·
6H2O, 8.64g (0.064mol) NaAc3H2O is dissolved in 80mL ethylene glycol；Ultrasound or stirring and dissolving is extremely at 20 DEG C -40 DEG C
Finely dispersed brown yellow solution；Resulting solution is transferred in 100mL reactor, 200 DEG C of reaction 8h.Reaction terminates
Afterwards, room temperature is originally water-cooled to, resulting black suspension ethanol and deionized water are alternately washed common 4-6 times,
Black solid is isolated using permanent magnet in washing process, gained sample is put into 60-80 DEG C of drying of drying box after washing
24-12h.It is designated as Fe3O4
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
1. the preparation of mixing salt solution weighs M2+(NO3)2·nH2O (0.009mol), M3+(NO3)3·9H2O
(0.003mol), 100mL methanol aqueous solutions (volume ratio VMethanol:VWater=0,1) stirred in 250mL beakers to being completely dissolved.
2. the preparation of mixed ammonium/alkali solutions weighs NaOH (0.02mol, 0.8g), Na2CO3(0.006mol, 0.64g), 100mL
Methanol aqueous solution (volume ratio VMethanol:VWater=0,1) in 250mL beakers, stirring is to being completely dissolved.
3. prepare Fe using double drop coprecipitations3O4@MA-LDH carriers.Weigh Fe3O4Nanoparticle (1.042g) in
In 500mL four-hole boiling flasks, 100mL methanol aqueous solution (methanol is added:Water=0,1), 10-20min of ultrasound and then beginning are slow
Alkali lye is added dropwise in the Fe3O4Mixed liquor is 10 to pH, after stable 5min, starts that mixing is added dropwise with 0.8~1.7mL/min drop speed
Salting liquid, it is 10 that pH is remained during this, until mixing salt solution is added dropwise；After stable 5min, the crystallization at 60 DEG C
Terminate reaction after 0-24h, it is neutrality to be washed with deionized to supernatant, and obtained solid product then is placed on into 60-70
24-18h is dried at a temperature of DEG C.It is designated as Fe3O4@(M2+-M3+)-LDH(M2+For Mg2+、Ni2+、Co2+、Cu2+In bivalent metal ion
Any one or two kinds, M3+For trivalent metal ion Al3+)
(3) preparation of magnetic multistage nucleocapsid loading type Pd-Au alloy catalysts
Down payment weight/mass percentage composition 1%-3% measures corresponding liquor capacity k to palladium weight/mass percentage composition 1%-3%2PdCl4
(10g/L) and HAuCl4·4H2O (10g/L) carries out the aqueous solution that mixed dissolution forms 100-175mL, is charged with 0.87g-
2.61g PVP and 25-100mL ethylene glycol, gained mixture 135 DEG C -145 DEG C backflow 1.5h -2.5h, it is then cold in atmosphere
But 0.5h -2h, 1g Fe are subsequently added into3O4@M2+M3+- LDH carriers, stirring 2h-4h, stand 12-48h；Separated with magnet, with third
Ketone and water alternately washing 3-5 times, dry 24-12h by gained solid sample at 60 DEG C -80 DEG C, obtain high dispersive small size magnetic
Property load type gold palladium alloy catalysts；The catalyst is designated as Fe3O4@M2+M3+-LDH@Pd-Au-n1-n2；Wherein, M2+For Mg2+、
Ni2+、Co2+、Cu2+Any one in bivalent metal ion or two kinds, M3+For trivalent metal ion Al3+, n1Represent Pd mass hundred
Divide ratio, n2Represent Au mass percents.
It is an advantage of the invention that：
(1) a kind of new high dispersive small-size magnetic load type gold palladium alloy catalysts and preparation method thereof are provided.It is special
It is not by based on rhotanium nanometer made from reducing agent ethylene glycol cheap and easy to get and stabilizer polyvinylpyrrolidone (PVP)
Particle is carried in magnetic multistage core shell structure hydrotalcite supports, obtains magnetic rhotanium catalyst Fe3O4@M2+M3+-LDH@
Pd-Au-n1-n2(M2+For Mg2+、Ni2+、Co2+、Cu2+Any one in bivalent metal ion or two kinds, M3+For trivalent metal from
Sub- Al3+, n1Represent Pd mass percents, n2Represent Au mass percents), its active component rhotanium particle diameter narrowly distributing
(<4nm), average grain diameter (~2nm) is significantly less than the particle diameter of load type gold palladium catalyst made from traditional immersion reduction method.
(2) catalyst being prepared has intrinsic alkaline and strong superparamagnetism, can be made up of modulation carrier element into
And the catalytic activity that regulating catalyst is reacted Heck, can effective enriching and recovering reaction solution rapidly by the response of external magnetic field
In catalyst.Using iodobenzene and styrene coupling reaction as probe reaction, with one of gained catalyst Fe3O4@NiAl-LDH@Pd-
Exemplified by Au-3%-3%, catalyst input amount 50mg, potassium carbonate is alkali, solvent be 12mL DMFs (DMF) with
4mL water, after 120 DEG C are reacted 3h, the conversion ratio of iodobenzene is up to 100%, and target product is trans-yield of talan is up to 93%.
Brief description of the drawings
Fig. 1 is sample F e in embodiment 13O4SEM spectrograms under 100K multiplication factors
Fig. 2 is sample F e in embodiment 13O4@NiAl-LDH@Pd-Au-3%-3% TEM spectrograms
Fig. 3 is sample F e in embodiment 13O4@NiAl-LDH@Pd-Au-3%-3% HR-TEM spectrograms
Fig. 4 is sample F e in embodiment 13O4@NiAl-LDH@Pd-Au-3%-3% rhotanium particle size distribution figure
Fig. 5 is sample F e in embodiment 13O4@NiAl-LDH@Pd-Au-3%-3% magnetic property figure
Fig. 6 is sample F e in embodiment 23O4SEM spectrograms of the@MgAl-LDH under 100K multiplication factors
Fig. 7 is sample F e in embodiment 23O4@MgAl-LDH@Pd-Au-3%-3% HR-TEM spectrograms
Fig. 8 is sample F e in embodiment 23O4@MgAl-LDH@Pd-Au-3%-3% rhotanium particle size distribution figure
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
(1) preparation of magnetic core
Fe is prepared using the solvent-thermal method of surfactant-free3O4Magnetic core (Chinese invention patent ZL 2011
10344754.5).Specific preparation process：Weigh 3.24g (0.012mol) FeCl3·6H2O, 8.64g (0.064mol) NaAc
3H2O is dissolved in 80mL ethylene glycol；Ultrasonic agitation 10min is dissolved to finely dispersed brown yellow solution；By resulting solution
It is transferred in 100mL reactor, reacts 8h at 200 DEG C.After reaction terminates, room temperature is originally water-cooled to, by gained
The black suspension ethanol and deionized water arrived alternately washing totally 4 times, isolate black using permanent magnet in washing process and consolidate
Body, gained sample is put into the dry 24h of 60 DEG C of drying box after washing, is designated as Fe3O4.Through measuring Fe3O4The average grain of particle
Footpath is about 500nm, and magnetism testing shows that the material has strong superparamagnetism, and its saturation magnetization is 76.5emu/g.
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
1. the preparation of mixing salt solution weighs Ni (NO3)2·6H2O (2.6172g), Al (NO3)3·9H2O (1.1264g),
100mL deionized waters are stirred in 250mL beakers to being completely dissolved.
2. the preparation of mixed ammonium/alkali solutions weighs NaOH (0.8g), Na2CO3(0.64g), 100mL deionized waters are burnt in 250mL
In cup, stirring is to being completely dissolved.
3. prepare the hud typed hydrotalcite supports of magnetic multilevel hierarchy using double drop coprecipitations.Weigh Fe3O4Nanoparticle
(1.042g) adds 100mL deionized waters, ultrasonic 10min, then, mixed alkali liquor is slowly added dropwise in 500mL four-hole boiling flasks
In Fe3O4To pH it is 10 in suspension, after stable 5min, then mixing salt solution is added dropwise with 0.8mL/min drop speed, during this
It is 10 to remain pH, until mixing salt solution is added dropwise；Terminate reaction after stable 5min, then separated with magnet, go from
Sub- water washing is for several times 7 to supernatant liquor pH, by gained sample in 60 DEG C of dry 24h, is designated as Fe3O4@NiAl-LDH.Through measurement
The hydrotalcite shell thickness of the hud typed carrier of the multilevel hierarchy is 30-70nm.
(3) preparation of magnetic multistage core shell structure load type gold palladium alloy catalysts
By 5.3mL k2PdCl4(10g/L) and 6.2mL HAuCl4·4H2O (10g/L) is mixed to form the water-soluble of 100mL
Liquid, is charged with 2.61g PVP (k-30) and 100mL ethylene glycol, and gained mixture flows back 2h at 140 DEG C, then in air
Then middle cooling 1.5h adds 1g carriers Fe to room temperature3O4@NiAl-LDH, 1h is stirred at room temperature, then stands 20h；Carried out with magnet
Alternately washing 3 times of solid-liquor separation, acetone and water, dry 24h by gained solid sample at 60 DEG C, obtain high dispersive small size magnetic
Property load type gold palladium alloy catalysts.The catalyst is designated as Fe3O4@M2+M3+-LDH@Pd-Au-n1-n2(M2+For Ni2+, M3+For three
Valence metal ion Al3+, n1Represent Pd mass percents, n2Au mass percents are represented, herein n1=3%, n2=3%) it is, and right
The magnetism testing of the catalyst understands that its saturation magnetization (Ms) is 28.5emu/g.The magnetic core mass percent of catalyst
About 44%, the mass percent of shell hydrotalcite is about 53%.
Embodiment 2
(1) preparation of magnetic core
Fe is prepared using the solvent-thermal method of surfactant-free3O4Magnetic core (Chinese invention patent ZL 2011
10344754.5).Specific preparation process：Weigh 3.24g (0.012mol) FeCl3·6H2O, 8.64g (0.064mol) NaAc
3H2O is dissolved in 80mL ethylene glycol；15min is stirred at 40 DEG C and is dissolved to finely dispersed brown yellow solution；Will be resulting
Solution is transferred in 100mL reactor, reacts 8h at 200 DEG C.After reaction terminates, room temperature is originally water-cooled to, will
Alternately washing totally 5 times of resulting black suspension ethanol and deionized water, isolated in washing process using permanent magnet black
Color solid, gained sample is put into the dry 18h of 70 DEG C of drying box after washing, is designated as Fe3O4.Through measuring Fe3O4Particle is put down
Equal particle diameter is about 600nm, and magnetism testing shows that the material has strong superparamagnetism.
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
1. the preparation of mixing salt solution weighs Mg (NO3)2·6H2O (2.3128g), Al (NO3)3·9H2O (1.1264g),
100mL methanol aqueous solutions (volume ratio VMethanol:VWater=1:1) stirred in 250mL beakers to being completely dissolved.
2. the preparation of mixed ammonium/alkali solutions weighs NaOH (0.8g), Na2CO3(0.64g), 100mL methanol aqueous solution (volume ratios
For VMethanol:VWater=1:1) in 250mL beakers, stirring is to being completely dissolved.
3. prepare the hud typed hydrotalcite supports of magnetic multilevel hierarchy using double drop coprecipitations.Weigh Fe3O4Nanoparticle
(1.042g) adds 100mL methanol aqueous solutions (volume ratio V in 500ml four-hole boiling flasksMethanol:VWater=1:1) it is, ultrasonic
15min, then, mixed alkali liquor is slowly added dropwise in Fe3O4To pH it is 10 in suspension, after stable 5min, then with 1.2mL/min's
Mixing salt solution is added dropwise in drop speed, and it is 10 that pH is remained during this, until mixing salt solution is added dropwise；After stable 5min,
Be placed on crystallization 24h in 60 DEG C of water-baths, then separated with magnet, deionized water wash for several times to supernatant liquor pH be 7, will
Gained sample is designated as Fe in 70 DEG C of dry 18h3O4@MgAl-LDH.Through the hydrotalcite shell for measuring the hud typed carrier of the multilevel hierarchy
Thickness degree is 80-120nm.
(3) preparation of magnetic multistage core shell structure load type gold palladium alloy catalysts
By 5.3mL k2PdCl4(10g/L) and 6.2mL HAuCl4·4H2O (10g/L) is mixed to form the water-soluble of 100mL
Liquid, is charged with 2.61g PVP and 100mL ethylene glycol, and gained mixture flows back 3h at 135 DEG C, then cools down in atmosphere
Then 0.5h adds 1g carriers Fe to room temperature3O4@MgAl-LDH, 3h is stirred at room temperature, then stands 48h；Solid-liquid point is carried out with magnet
From with alternately washing 4 time of acetone and water, gained solid sample being dried into 18h at 70 DEG C, high dispersive small-size magnetic is obtained and bears
Load type rhotanium catalyst.The catalyst is designated as Fe3O4@MgAl-LDH@Pd-Au-3%-3%, and to the magnetic of the catalyst
It can test and understand that its saturation magnetization (Ms) is 41.8emu/g.The magnetic core mass percent of catalyst is about 58%, shell water
The mass percent of talcum is about 39%.
Embodiment 3
(1) preparation of magnetic core
Fe is prepared using the solvent-thermal method of surfactant-free3O4Magnetic core (Chinese invention patent ZL 2011
10344754.5).Specific preparation process：Weigh 3.24g (0.012mol) FeCl3·6H2O, 8.64g (0.064mol) NaAc
3H2O is dissolved in 80mL ethylene glycol；20min is stirred at room temperature and is dissolved to finely dispersed brown yellow solution；Will be resulting
Solution is transferred in 100mL reactor, reacts 8h at 200 DEG C.After reaction terminates, room temperature is originally water-cooled to, will
Alternately washing totally 6 times of resulting black suspension ethanol and deionized water, isolated in washing process using permanent magnet black
Color solid, gained sample is put into the dry 12h of 80 DEG C of drying box after washing, is designated as Fe3O4。
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
1. the preparation of mixing salt solution weighs Ni (NO3)2·6H2O (2.6172g), Al (NO3)3·9H2O (1.1264g),
100mL deionized waters are stirred in 250mL beakers to being completely dissolved.
2. the preparation of mixed ammonium/alkali solutions weighs NaOH (0.8g), Na2CO3(0.64g), 100mL deionized waters are burnt in 250mL
In cup, stirring is to being completely dissolved.
3. prepare the hud typed hydrotalcite supports of magnetic multilevel hierarchy using double drop coprecipitations.Weigh Fe3O4Nanoparticle
(1.042g) adds 100mL deionized waters, ultrasonic 20min, then, mixed alkali liquor is slowly added dropwise in 500mL four-hole boiling flasks
In Fe3O4To pH it is 10 in suspension, after stable 5min, then mixing salt solution is added dropwise with 1.7mL/min drop speed, during this
It is 10 to remain pH, until mixing salt solution is added dropwise；Terminate reaction after stable 5min, then separated with magnet, go from
Sub- water washing is for several times 7 to supernatant liquor pH, by gained sample in 80 DEG C of dry 12h, is designated as Fe3O4@NiAl-LDH。
(3) preparation of magnetic multistage core shell structure load type gold palladium alloy catalysts
By 2.5mL k2PdCl4(10g/L) and 3.1mL HAuCl4·4H2O (10g/L) is mixed to form the water-soluble of 150mL
Liquid, is charged with 1.30g PVP and 50mL ethylene glycol, and gained mixture flows back 1.5h at 145 DEG C, then cools down in atmosphere
Then 2h adds 1g carriers Fe to room temperature3O4@NiAl-LDH, 4h is stirred at room temperature, then stands 12h；Solid-liquor separation is carried out with magnet,
Acetone and water alternately washing 5 times, dry 12h by gained solid sample at 80 DEG C, obtain high dispersive small-size magnetic support type
Rhotanium catalyst.The catalyst is designated as Fe3O4@[email protected]%-1.5%.
Embodiment 4
(1) preparation of magnetic core
Preparation process is the same as embodiment 1.
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
Preparation process is the same as embodiment 1.
(3) preparation of magnetic multistage core shell structure load type gold palladium alloy catalysts
By 2.5mL k2PdCl4(10g/L) and 3.1mL HAuCl4·4H2O (10g/L) is mixed to form the water-soluble of 150mL
Liquid, is charged with 1.3g PVP and 50mL ethylene glycol, and gained mixture flows back 2h at 140 DEG C, cools down 2h in atmosphere afterwards
To room temperature, 1g carriers Fe is then added3O4@MgAl-LDH, 1h is stirred at room temperature, then stands 24h；Then solid-liquid point is carried out with magnet
From acetone and water alternately washing 4 times, gained solid sample dry 24h at 70 DEG C, obtain high dispersive small-size magnetic support type
Rhotanium catalyst, is designated as Fe3O4@[email protected]%-1.5%.
Embodiment 5
(1) preparation of magnetic core
Preparation process is the same as embodiment 1.
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
Preparation process is the same as embodiment 1.
(3) preparation of magnetic multistage core shell structure load type gold palladium alloy catalysts
By 1.7mL K2PdCl4(10g/L) and 2.1mL HAuCl4·4H2O (10g/L) is mixed to form the water-soluble of 175mL
Liquid, is charged with 0.87g PVP and 25mL ethylene glycol, and gained mixture flows back 2h at 140 DEG C, cools down in atmosphere afterwards
Then 1.5h adds 1g carriers Fe to room temperature3O4@MgAl-LDH, 1h is stirred at room temperature, then stands 12h；Then consolidated with magnet
Liquid separates, and acetone and water alternately washing 3 times, gained solid sample dry 24h at 60 DEG C, obtain high dispersive small-size magnetic and bear
Load type rhotanium catalyst, is designated as Fe3O4@MgAl-LDH@Pd-Au-1%-1%.
Embodiment 6
(1) preparation of magnetic core
Preparation process is the same as embodiment 1.
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
1. the preparation of mixing salt solution weighs Co (NO3)2·6H2O (2.6193g), Al (NO3)3·9H2O (1.1264g),
100mL methanol aqueous solutions (volume ratio VMethanol:VWater=1:1) stirred in 250mL beakers to being completely dissolved.
2. the preparation of mixed ammonium/alkali solutions weighs NaOH (0.8g), Na2CO3(0.64g), 100mL methanol aqueous solution (volume ratios
For VMethanol:VWater=1:1) in 250mL beakers, stirring is to being completely dissolved.
3. prepare the hud typed hydrotalcite supports of magnetic multilevel hierarchy using double drop coprecipitations.Weigh Fe3O4Nanoparticle
(1.042g) adds 100mL methanol-water solutions (volume ratio V in 500mL four-hole boiling flasksMethanol:VWater=1:1) it is, ultrasonic
10min, then, mixed alkali liquor is slowly added dropwise in Fe3O4To pH it is 10 in suspension, after stable 5min, then with 0.8mL/min's
Mixing salt solution is added dropwise in drop speed, and it is 10 that pH is remained during this, until mixing salt solution is added dropwise；Tied after stable 5min
Shu Fanying, then separated with magnet, deionized water wash for several times to supernatant liquor pH be 7, by gained sample in 60 DEG C of dryings
24h, it is designated as Fe3O4@CoAl-LDH。
(3) preparation of magnetic multistage core shell structure load type gold palladium alloy catalysts
By 2.5mL k2PdCl4(10g/L) and 3.1mL HAuCl4·4H2O (10g/L) is mixed to form the water-soluble of 150mL
Liquid, is charged with 1.30g PVP and 50mL ethylene glycol, and gained mixture flows back 2h at 140 DEG C, cools down in atmosphere afterwards
Then 0.5h adds 1g carriers Fe to room temperature3O4@CoAl-LDH, 1h is stirred at room temperature, then stands 24h；Then consolidated with magnet
Liquid separates, and acetone and water alternately washing 3 times, gained solid sample is dried into 12h at 80 DEG C, obtains high dispersive small-size magnetic
Load type gold palladium alloy catalysts.The catalyst is designated as Fe3O4@[email protected]%-1.5%.
Embodiment 7
(1) preparation of magnetic core
Preparation process is the same as embodiment 1.
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
1. the preparation of mixing salt solution weighs Mg (NO3)2·6H2O (1.9231g), Cu (NO3)2·3H2O (0.3624g),
Al(NO3)3·9H2O (1.1264g), i.e. nMg:n Cu=5:1,100mL methanol aqueous solution (volume ratio VMethanol:VWater=1:1) in
Stirred in 250mL beakers to being completely dissolved.
2. the preparation of mixed ammonium/alkali solutions weighs NaOH (0.8g), Na2CO3(0.64g), 100mL methanol aqueous solution (volume ratios
For VMethanol:VWater=1:1) in 250mL beakers, stirring is to being completely dissolved.
3. prepare the hud typed hydrotalcite supports of magnetic multilevel hierarchy using double drop coprecipitations.Weigh Fe3O4Nanoparticle
(1.042g) adds 100mL methanol-water solutions (volume ratio V in 500mL four-hole boiling flasksMethanol:VWater=1:1) it is, ultrasonic
Then 20min starts to be slowly added dropwise mixed alkali liquor in Fe3O4Mixed liquor is 10 to pH, after stable 5min, is started with 1.2mL/min
Drop speed mixing salt solution is added dropwise, it is 10 that pH is remained during this, until mixing salt solution is added dropwise；It is placed on 60
Crystallization 24h in DEG C water-bath, is then separated, deionized water is washed to supernatant pH is 7 with magnet, by gained sample in 70 DEG C
18h is dried, is designated as Fe3O4@CuMgAl-LDH。
(3) preparation of magnetic multistage core shell structure load type gold palladium alloy catalysts.
By 5.3mL k2PdCl4(10g/L) and 6.2mL HAuCl4·4H2O (10g/L) is mixed to form the water-soluble of 100mL
Liquid, is charged with 2.61g PVP and 100mL ethylene glycol, and gained mixture flows back 2h at 140 DEG C, then cools down in atmosphere
Then 2h adds 1g carriers Fe to room temperature3O4@MgCuAl-LDH, 2h is stirred at room temperature, then stands 12h；Solid-liquid point is carried out with magnet
From acetone and water are alternately washed 4 times, and gained solid sample is dried into 24h at 60 DEG C, obtain the load of high dispersive small-size magnetic
Type rhotanium catalyst.The catalyst is designated as Fe3O4@MgCuAl-LDH@Pd-Au-3%-3%.
Claims (2)
1. a kind of high dispersive small-size magnetic load type gold palladium alloy catalysts, it is characterised in that reduction of ethylene glycol method is made
Rhotanium nanoparticle be carried in magnetic multistage core shell structure hydrotalcite supports, the magnetic for obtaining high dispersive small size is multistage
Core shell structure load type gold palladium alloy catalysts, the mass percent of each element is respectively Pd in its active component rhotanium:
1%-3%, Au:1%-3%, particle size distribution scope are<4nm；Honeycomb pattern, saturation magnetization is presented in the catalyst
Ms is 28-42emu/g；The core of magnetic multistage core shell structure hydrotalcite supports is Fe 3 O 4 magnetic particle, and its size is
500-600nm, it is 44%-58% to account for total catalyst mass percent, and shell is hydrotalcite (M2+-M3+)-LDH, M2+For Mg2+、
Ni2+、Co2+、Cu2+Any one in bivalent metal ion or two kinds, M3+For trivalent metal ion Al3+, shell thickness 30-
120nm, mass percent 39%-53%；
There is high catalytic activity and selectivity in Heck coupling reaction systems, be coupled with iodobenzene and styrene as probe reaction,
Use catalyst Fe3O4@NiAl-LDH@Pd-Au-3%-3% input amount is 50mg, and potassium carbonate is alkali additive, and solvent is
The mixed liquor of 12mL DMFs DMF and 4mL water, after 120 DEG C are reacted 3h, the conversion ratio of iodobenzene up to 100%,
Target product is trans-and the yield of talan is up to 93%；Using the magnetic characteristic recovery and reuse of catalyst, reuse
5 times activity does not substantially reduce.
2. a kind of preparation method of the high dispersive small-size magnetic load type gold palladium alloy catalysts described in claim 1, it is special
Sign is that processing step is as follows：
(1) preparation of magnetic core
Using the solvent-thermal method of surfactant-free, specific preparation process：Weigh 3.24g i.e. 0.012molFeCl3·6H2O,
8.64g i.e. 0.064molNaAc3H2O is dissolved in 80mL ethylene glycol；Ultrasound or at 20 DEG C -40 DEG C stirring and dissolving to scattered
Uniform brown yellow solution；Resulting solution is transferred in 100mL reactor, reacts 8h at 200 DEG C；Reaction terminates
Afterwards, room temperature is originally water-cooled to, resulting black suspension ethanol and deionized water are alternately washed common 4-6 times,
Black solid is isolated using permanent magnet in washing process, gained sample is put into 60-80 DEG C of drying of drying box after washing
24-12h；It is designated as Fe3O4
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
The preparation of mixing salt solution：Weigh M2+(NO3)2·nH2O0.009mol, M3+(NO3)3·9H2O 0.003mol, 100mL first
Alcohol solution, volume ratio VMethanol:VWater=0,1, stirred in 250mL beakers to being completely dissolved；
The preparation of mixed ammonium/alkali solutions：Weigh NaOH0.02mol i.e. 0.8g, Na2CO30.006mol is 0.64g, and 100mL methanol is water-soluble
Liquid, volume ratio VMethanol:VWater=0,1, in 250mL beakers, stirring is to being completely dissolved；
Fe is prepared using double drop coprecipitations3O4@MA-LDH carriers：Weigh Fe3O4Nanoparticle 1.042g is in 500mL four-hole boiling flasks
In, add 100mL methanol aqueous solutions, methanol:Then water=0,1,10-20min of ultrasound start to be slowly added dropwise alkali lye in this
Fe3O4Mixed liquor is 10 to pH, after stable 5min, starts that mixing salt solution, this process is added dropwise with 0.8~1.7mL/min drop speed
In remain that pH is 10, until mixing salt solution is added dropwise；After stable 5min, tied in 60 DEG C of water-baths after the -24h of crystallization 0
Shu Fanying, it is neutrality to be washed with deionized to supernatant, is done at a temperature of obtained solid product then is placed on into 60-70 DEG C
Dry 24-18h；It is designated as Fe3O4@(M2+-M3+)-LDH, M2+For Mg2+、Ni2+、Co2+、Cu2+Any one in bivalent metal ion
Or two kinds, M3+For trivalent metal ion Al3+；
(3) preparation of magnetic multistage nucleocapsid loading type Pd-Au alloy catalysts
Down payment weight/mass percentage composition 1%-3% measures corresponding liquor capacity 10g/L's to palladium weight/mass percentage composition 1%-3%
k2PdCl4With 10g/L HAuCl4·4H2O carries out the aqueous solution that mixed dissolution forms 100-175mL, is charged with 0.87g-
2.61g PVP and 25-100mL ethylene glycol, gained mixture 135 DEG C -145 DEG C backflow 1.5h -2.5h, it is then cold in atmosphere
But 0.5h -2h, 1g Fe are subsequently added into3O4@M2+M3+- LDH carriers, stirring 2h-4h, stand 12-48h；Separated with magnet, with third
Ketone and water alternately washing 3-5 times, dry 24-12h by gained solid sample at 60 DEG C -80 DEG C, obtain high dispersive small size magnetic
Property load type gold palladium alloy catalysts；The catalyst is designated as Fe3O4@M2+M3+-LDH@Pd-Au-n1-n2；Wherein, M2+For Mg2+、
Ni2+、Co2+、Cu2+Any one in bivalent metal ion or two kinds, M3+For trivalent metal ion Al3+, n1Represent Pd mass hundred
Divide ratio, n2Represent Au mass percents.
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| CN107335454B (en) * | 2017-08-28 | 2020-07-24 | 安徽大学 | Load type Pd3Preparation and application of Cl cluster catalyst |
| CN108187743B (en) * | 2018-01-17 | 2021-06-25 | 南京工程学院 | Ion exchange resin supported nano gold-palladium alloy catalyst and preparation method thereof |
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| CN111054333B (en) * | 2020-02-14 | 2022-11-01 | 郑州轻工业大学 | Hydrotalcite supported palladium catalyst for preparing styrene by selective hydrogenation of phenylacetylene, and preparation method and application thereof |
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