CN104801316A - High-dispersion small-sized magnetic load type gold-palladium alloy catalyst and preparation method thereof - Google Patents
High-dispersion small-sized magnetic load type gold-palladium alloy catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN104801316A CN104801316A CN201510145564.9A CN201510145564A CN104801316A CN 104801316 A CN104801316 A CN 104801316A CN 201510145564 A CN201510145564 A CN 201510145564A CN 104801316 A CN104801316 A CN 104801316A
- Authority
- CN
- China
- Prior art keywords
- magnetic
- preparation
- catalyst
- palladium alloy
- load type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001252 Pd alloy Inorganic materials 0.000 title claims abstract description 34
- 239000006185 dispersion Substances 0.000 title abstract 5
- 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 33
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 33
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 230000005415 magnetization Effects 0.000 claims abstract description 6
- 239000006249 magnetic particle Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000000523 sample Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 239000012266 salt solution Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 17
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 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
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 230000008569 process Effects 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
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 230000000694 effects Effects 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 241000425573 Talanes Species 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229940072033 potash Drugs 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910001020 Au alloy Inorganic materials 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 239000007788 liquid Substances 0.000 description 5
- 230000005389 magnetism Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- -1 aryl alkene derivatives Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000011084 recovery Methods 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical class [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
Abstract
The invention belongs to a high-dispersion small-sized magnetic load type gold-palladium alloy catalyst and a preparation method thereof, and belongs to the field of magnetic load type noble metal catalytic materials. Gold-palladium alloy nanoparticles are loaded on a magnetic hydrotalcite carrier with a multistage core-shell structure by an ethylene glycol reduction method to obtain the high-dispersion small-size magnetic load type gold-palladium alloy catalyst with the multistage core-shell structure. The mass percent of elements in active component gold-palladium alloy is 1%-3% of Pd and 1%-3% of Au; the particle size distribution range is smaller than 4 nm. The high-dispersion small-size magnetic load type gold-palladium alloy catalyst takes the shape of a honeycomb, the saturation magnetization Ms is equal to 28-42 emu/g; the magnetic hydrotalcite carrier with the multistage core-shell structure adopts ferroferric oxide magnetic particles as a core, and the shell adopts hydrotalcite (M<2+>-M<3->)-LDH. The high-dispersion small-size magnetic load type gold-palladium alloy catalyst and the preparation method have the advantages that the gold-palladium alloy nanoparticles of the catalyst are highly dispersed on the hydrotalcite shell of the magnetic carrier, the preparation process is simple, and the catalyst can be quickly enriched, recovered and repeatedly used through external magnetic fields such as a magnet after the reaction is completed.
Description
Technical field
The invention belongs to carried noble metal catalysis material technical field, in particular, provide a kind of high dispersive small-size magnetic load type gold palladium alloy catalysts and preparation method thereof.
Background technology
Heck reaction is the class reaction being generated virtueization alkene by unsaturated halogenated hydrocarbons and alkene under the effect of highly basic and palladium catalyst.Since the people such as Heck in 1971 find this reaction, series of aryl alkene derivatives, cinnamate analog derivative and diphenyl ethylene derivatives etc. with important value can be synthesized efficiently due to the type reaction and develop into a kind of increasingly extensive modern organic synthesis method of applying gradually, being widely used in the commercial synthesis field of dyestuff, agricultural chemicals, medicine, luminescent material, daily chemicals and high polymer, is the key object that catalytic chemistry man and organic chemists study.Current monometallic Pd catalyst obtains the deep research of system because activity is higher, develop into the dominant catalyst of Heck reaction gradually.But, homogeneous palladium containing organic phosphine, nitrogen ligand is catalyst based because the preparation of its part is difficult, cost is high, contaminated environment, and such catalyst is comparatively responsive to water, heat, air etc., and maximum problem is that homogeneous catalyst is difficult to be separated with reactant liquor, reclaim difficulty cannot reuse, its practical application is greatly limited.Although the increasing loaded catalyst of Recent study maintains good catalytic activity to a certain extent, and can separation and recovery reuse, traditional filtration and centrifugal separation process also exist numerous and diverse effort, tediously long problem consuming time.
Magnetic/functionalized catalysis material can become by the rapid separation and recovery recycling of external magnetic field the available strategy solving separation and recovery of catalyst recycling in recent years because of it.2011, this seminar is with hydrotalcite coated ferroferric oxide supported on carriers golden nanometer particle, obtained a kind of multilevel core-shell structure magnetic nano gold catalyst (Chinese invention patent ZL2011 1 0344754.5), be applied to alcohol oxidation reaction, not only there is good catalytic activity feature, and the superparamagnetic performance utilizing it stronger is by externally-applied magnetic field enriching and recovering recycling easily.In recent years, the bimetallic gold palladium catalyst of ligands stabilize has attracted increasing research interest because of its special composition, structure, size, cloud density etc., and be widely used in the reaction system such as preparation, nitro halobenzene selec-tive hydrogenation of alcohol oxidation, hydrogen peroxide, but there is catalyst separation and environmental problem.(the Jennifer K.Edwards such as Hutchings, Graham J.Hutchings.Journal of Catalysis, 2005,236,69 – 79) adopt traditional immersion reduction method to obtain titania oxide supported rhotanium catalyst, the domain size distribution of golden palladium nanoparticle is wide, presents two kinds of domain size distribution, small particle diameter is 1 – 8nm, and Large stone is 40-70nm.(the Sarina Sarina such as Zhu, Huaiyong Zhu.Journal of the American ChemicalSociety, 2013,135,5793 – 5801) adopt traditional immersion reduction method to obtain zirconia gold-supported palladium alloy catalysts, the particle diameter of rhotanium nanoparticle is less than 8nm.Up to now, not yet about hydrotalcite coated ferroferric oxide magnetic carrier gold-supported palladium nanometer alloy catalyst preparation and be applied to the report of Heck coupling reaction.
Thus, the present invention intends adopting reduction of ethylene glycol legal system for rhotanium nano particle and to be carried in multistage core-shell structure magnetic hydrotalcite supports thus obtained multistage core-shell structure magnetic load type gold palladium alloy catalysts, the active component rhotanium nanoparticle particle diameter of this catalyst is less than 4nm, can be used as a kind of highly active green C-C coupling reaction catalyst.
Summary of the invention
The object of the present invention is to provide a kind of high dispersive small-size magnetic load type gold palladium alloy catalysts and preparation method thereof.The rhotanium nano particle high dispersive of this catalyst, on the shell hydrotalcite of magnetic carrier, presents the feature that size is little, catalytic activity is high, and preparation technology is simple, after the completion of reaction by the rapid enriching and recovering recycling of the externally-applied magnetic fields such as magnet.
Catalyst of the present invention is carried in the multistage nucleocapsid structure hydrotalcite supports of magnetic by the rhotanium nanoparticle that reduction of ethylene glycol method is obtained, obtain the undersized magnetic of high dispersive multistage nucleocapsid structure load type gold palladium alloy catalysts, in its active component rhotanium, the mass percent of each element is respectively Pd:1%-3%, Au:1%-3%, particle size distribution scope is <4nm; This catalyst presents honeycomb pattern, and saturation magnetization Ms is 28-42emu/g; The core of the multistage nucleocapsid structure hydrotalcite supports of magnetic is Fe 3 O 4 magnetic particle, and it is of a size of 500-600nm, and accounting for total catalyst mass percent is 44%-58%, and shell is hydrotalcite (M
2+-M
3+)-LDH, M
2+for Mg
2+, Ni
2+, Co
2+, Cu
2+any one or two kinds in bivalent metal ion, M
3+for trivalent metal ion Al
3+, shell thickness is 30-120nm, and mass percent is 39%-53%.
Described catalyst has high catalytic activity and selective in Heck coupling reaction system, with iodobenzene and styrene coupling for probe reaction, and catalyst (Fe
3o
4niAl-LDHPd-Au-3%-3%) input amount is 50mg, potash is alkali additive, solvent is 12mL N, the mixed liquor of dinethylformamide (DMF) and 4mL water, after 120 DEG C of reaction 3h, the conversion ratio of iodobenzene reaches 100%, and target product is trans-and the productive rate of talan reaches 93%.Utilize the magnetic characteristic of catalyst to reclaim rapidly and to reuse, reuse 5 activity and obviously do not reduce.
Present invention process step is as follows:
(1) preparation of magnetic core
Adopt the solvent-thermal method of surfactant-free, concrete preparation process: take 3.24g (0.012mol) FeCl
36H
2o, 8.64g (0.064mol) NaAc3H
2o is dissolved in 80mL ethylene glycol; Ultrasonic or at 20 DEG C-40 DEG C stirring and dissolving to finely dispersed brown yellow solution; Obtained solution is transferred in the reactor of 100mL, 200 DEG C of reaction 8h.After reaction terminates, carry out running water and be cooled to room temperature, obtained black suspension ethanol and deionized water are alternately washed 4-6 time altogether, adopts permanent magnet to isolate black solid in washing process, after washing, gained sample is put into drying box 60-80 DEG C of dry 24-12h.Be designated as Fe
3o
4
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
1. the preparation of mixing salt solution takes M
2+(NO
3)
2nH
2o (0.009mol), M
3+(NO
3)
39H
2o (0.003mol), (volume ratio is V to 100mL methanol aqueous solution
methyl alcohol: V
water=0,1) be stirred in 250mL beaker and dissolve completely.
2. the preparation of mixed ammonium/alkali solutions takes NaOH (0.02mol, 0.8g), Na
2cO
3(0.006mol, 0.64g), (volume ratio is V to 100mL methanol aqueous solution
methyl alcohol: V
water=0,1) in 250mL beaker, be stirred to and dissolve completely.
3. two coprecipitation of dripping is adopted to prepare Fe
3o
4mA-LDH carrier.Take Fe
3o
4nanoparticle (1.042g) in 500mL four-hole boiling flask, then adds 100mL methanol aqueous solution (methyl alcohol: water=0,1), and then ultrasonic 10 – 20min start slowly to drip alkali lye in this Fe
3o
4mixed liquor is 10, after stablizing 5min to pH, starts to drip mixing salt solution with the speed of dripping of 0.8 ~ 1.7mL/min, remains that pH is 10, until mixing salt solution dropwises in this process; After stablizing 5min, at 60 DEG C, terminate reaction after crystallization 0 – 24h, spend deionized water to supernatant for neutral, then the solid product obtained is placed on dry 24-18h at 60-70 DEG C of temperature.Be designated as Fe
3o
4(M
2+-M
3+)-LDH (M
2+for Mg
2+, Ni
2+, Co
2+, Cu
2+any one or two kinds in bivalent metal ion, M
3+for trivalent metal ion Al
3+)
(3) preparation of the multistage nucleocapsid loading type Pd of magnetic-Au alloy catalyst
Down payment mass percentage 1%-3% measures corresponding liquor capacity k to palladium mass percentage 1%-3%
2pdCl
4(10g/L) and HAuCl
44H
2o (10g/L) carries out the aqueous solution that mixed dissolution forms 100 – 175mL, toward wherein adding 0.87g-2.61g PVP and 25-100mL ethylene glycol, gained mixture, at 135 DEG C-145 DEG C backflow 1.5h – 2.5h, then cools 0.5h – 2h in atmosphere, then adds 1g Fe
3o
4m
2+m
3+-LDH carrier, stirs 2h-4h, leaves standstill 12-48h; Be separated with magnet, with acetone and water alternately washing 3-5 time, by gained solid sample dry 24-12h at 60 DEG C-80 DEG C, obtain high dispersive small-size magnetic load type gold palladium alloy catalysts; This catalyst is designated as Fe
3o
4m
2+m
3+-LDHPd-Au-n
1-n
2; Wherein, M
2+for Mg
2+, Ni
2+, Co
2+, Cu
2+any one or two kinds in bivalent metal ion, M
3+for trivalent metal ion Al
3+, n
1represent Pd mass percent, n
2represent Au mass percent.
Advantage of the present invention is:
(1) a kind of novel high dispersive small-size magnetic load type gold palladium alloy catalysts and preparation method thereof is provided.Particularly by based on reducing agent ethylene glycol cheap and easy to get and the obtained rhotanium nanometer particle load of stabilizing agent polyvinylpyrrolidone (PVP) in the multistage nucleocapsid structure hydrotalcite supports of magnetic, obtain magnetic rhotanium catalyst Fe
3o
4m
2+m
3+-LDHPd-Au-n
1-n
2(M
2+for Mg
2+, Ni
2+, Co
2+, Cu
2+any one or two kinds in bivalent metal ion, M
3+for trivalent metal ion Al
3+, n
1represent Pd mass percent, n
2represent Au mass percent), its active component rhotanium particle diameter narrowly distributing (<4nm), average grain diameter (~ 2nm) is significantly less than the particle diameter of the load type gold palladium catalyst that traditional immersion reduction method obtains.
(2) catalyst prepared has intrinsic alkalescence and strong superparamagnetism, by modulation carrier element composition and then the regulating catalyst catalytic activity of react Heck, can catalyst rapidly effectively in enriching and recovering reactant liquor by the response of external magnetic field.With iodobenzene and styrene coupling reaction for probe reaction, with one of gained catalyst Fe
3o
4niAl-LDHPd-Au-3%-3% is example, catalyst input amount 50mg, and potash is alkali, solvent is 12mL DMF (DMF) and 4mL water, after 120 DEG C of reaction 3h, the conversion ratio of iodobenzene reaches 100%, and target product is trans-and the productive rate of talan reaches 93%.
Accompanying drawing explanation
Fig. 1 is sample F e in embodiment 1
3o
4sEM spectrogram under 100K multiplication factor
Fig. 2 is sample F e in embodiment 1
3o
4the TEM spectrogram of NiAl-LDHPd-Au-3%-3%
Fig. 3 is sample F e in embodiment 1
3o
4the HR-TEM spectrogram of NiAl-LDHPd-Au-3%-3%
Fig. 4 is sample F e in embodiment 1
3o
4the rhotanium particle size distribution figure of NiAl-LDHPd-Au-3%-3%
Fig. 5 is sample F e in embodiment 1
3o
4the magnetic property figure of NiAl-LDHPd-Au-3%-3%
Fig. 6 is sample F e in embodiment 2
3o
4the SEM spectrogram of MgAl-LDH under 100K multiplication factor
Fig. 7 is sample F e in embodiment 2
3o
4the HR-TEM spectrogram of MgAl-LDHPd-Au-3%-3%
Fig. 8 is sample F e in embodiment 2
3o
4the rhotanium particle size distribution figure of MgAl-LDHPd-Au-3%-3%
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
(1) preparation of magnetic core
The solvent-thermal method of surfactant-free is adopted to prepare Fe
3o
4magnetic core (Chinese invention patent ZL 2,011 10344754.5).Concrete preparation process: take 3.24g (0.012mol) FeCl
36H
2o, 8.64g (0.064mol) NaAc3H
2o is dissolved in 80mL ethylene glycol; Ultrasonic agitation 10min is dissolved to finely dispersed brown yellow solution; Obtained solution is transferred in the reactor of 100mL, at 200 DEG C, reacts 8h.After reaction terminates, carry out running water and be cooled to room temperature, obtained black suspension ethanol and deionized water are alternately washed totally 4 times, in washing process, adopts permanent magnet to isolate black solid, gained sample is put into drying box 60 DEG C of dry 24h after washing, be designated as Fe
3o
4.Through measuring Fe
3o
4the average grain diameter of particle is about 500nm, and magnetism testing shows this material and 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 takes Ni (NO
3)
26H
2o (2.6172g), Al (NO
3)
39H
2o (1.1264g), 100mL deionized water is stirred in 250mL beaker dissolves completely.
2. the preparation of mixed ammonium/alkali solutions takes NaOH (0.8g), Na
2cO
3(0.64g), 100mL deionized water, in 250mL beaker, is stirred to and dissolves completely.
3. two coprecipitation of dripping is adopted to prepare the hud typed hydrotalcite supports of magnetic multilevel hierarchy.Take Fe
3o
4nanoparticle (1.042g) in 500mL four-hole boiling flask, then adds 100mL deionized water, ultrasonic 10min, then, slowly drips mixed alkali liquor in Fe
3o
4in suspension to pH be 10, after stablizing 5min, then with 0.8mL/min drip speed drip mixing salt solution, remain in this process that pH is 10, until mixing salt solution dropwises; Terminate reaction after stablizing 5min, then washing several to supernatant liquor pH by magnet separation, deionized water is 7, by gained sample in 60 DEG C of dry 24h, is designated as Fe
3o
4niAl-LDH.Be 30-70nm through measuring the hydrotalcite shell thickness of the hud typed carrier of this multilevel hierarchy.
(3) preparation of magnetic multistage nucleocapsid structure load type gold palladium alloy catalysts
By 5.3mL k
2pdCl
4(10g/L) with 6.2mL HAuCl
44H
2o (10g/L) is mixed to form the aqueous solution of 100mL, and toward wherein adding 2.61g PVP (k-30) and 100mL ethylene glycol, gained mixture, at 140 DEG C of backflow 2h, then cools 1.5h in atmosphere to room temperature, then adds 1g carrier Fe
3o
4niAl-LDH, stirring at room temperature 1h, then leave standstill 20h; Carry out solid-liquor separation with magnet, acetone and water replace washing 3 times, by gained solid sample dry 24h at 60 DEG C, obtain high dispersive small-size magnetic load type gold palladium alloy catalysts.This catalyst is designated as Fe
3o
4m
2+m
3+-LDHPd-Au-n
1-n
2(M
2+for Ni
2+, M
3+for trivalent metal ion Al
3+, n
1represent Pd mass percent, n
2represent Au mass percent, n herein
1=3%, n
2, and be 28.5emu/g to known its saturation magnetization (Ms) of the magnetism testing of this catalyst=3%).The magnetic nuclear mass percentage of catalyst is about 44%, and the mass percent of shell hydrotalcite is about 53%.
Embodiment 2
(1) preparation of magnetic core
The solvent-thermal method of surfactant-free is adopted to prepare Fe
3o
4magnetic core (Chinese invention patent ZL 2,011 10344754.5).Concrete preparation process: take 3.24g (0.012mol) FeCl
36H
2o, 8.64g (0.064mol) NaAc3H
2o is dissolved in 80mL ethylene glycol; At 40 DEG C, stir 15min be dissolved to finely dispersed brown yellow solution; Obtained solution is transferred in the reactor of 100mL, at 200 DEG C, reacts 8h.After reaction terminates, carry out running water and be cooled to room temperature, obtained black suspension ethanol and deionized water are alternately washed totally 5 times, in washing process, adopts permanent magnet to isolate black solid, gained sample is put into drying box 70 DEG C of dry 18h after washing, be designated as Fe
3o
4.Through measuring Fe
3o
4the average grain diameter of particle is about 600nm, and magnetism testing shows this material and has strong superparamagnetism.
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
1. the preparation of mixing salt solution takes Mg (NO
3)
26H
2o (2.3128g), Al (NO
3)
39H
2o (1.1264g), (volume ratio is V to 100mL methanol aqueous solution
methyl alcohol: V
water=1:1) be stirred in 250mL beaker and dissolve completely.
2. the preparation of mixed ammonium/alkali solutions takes NaOH (0.8g), Na
2cO
3(0.64g), (volume ratio is V to 100mL methanol aqueous solution
methyl alcohol: V
water=1:1) in 250mL beaker, be stirred to and dissolve completely.
3. two coprecipitation of dripping is adopted to prepare the hud typed hydrotalcite supports of magnetic multilevel hierarchy.Take Fe
3o
4nanoparticle (1.042g) is in 500ml four-hole boiling flask, then (volume ratio is V to add 100mL methanol aqueous solution
methyl alcohol: V
water=1:1), ultrasonic 15min, then, slowly drips mixed alkali liquor in Fe
3o
4in suspension to pH be 10, after stablizing 5min, then with 1.2mL/min drip speed drip mixing salt solution, remain in this process that pH is 10, until mixing salt solution dropwises; After stablizing 5min, be placed on crystallization 24h in 60 DEG C of water-baths, then washing several to supernatant liquor pH by magnet separation, deionized water is 7, by gained sample in 70 DEG C of dry 18h, is designated as Fe
3o
4mgAl-LDH.Be 80 – 120nm through measuring the hydrotalcite shell thickness of the hud typed carrier of this multilevel hierarchy.
(3) preparation of magnetic multistage nucleocapsid structure load type gold palladium alloy catalysts
By 5.3mL k
2pdCl
4(10g/L) with 6.2mL HAuCl
44H
2o (10g/L) is mixed to form the aqueous solution of 100mL, and toward wherein adding 2.61g PVP and 100mL ethylene glycol, gained mixture, at 135 DEG C of backflow 3h, then cools 0.5h in atmosphere to room temperature, then adds 1g carrier Fe
3o
4mgAl-LDH, stirring at room temperature 3h, then leave standstill 48h; Carry out Separation of Solid and Liquid with magnet, replace washing 4 times with acetone and water, by gained solid sample dry 18h at 70 DEG C, obtain high dispersive small-size magnetic load type gold palladium alloy catalysts.This catalyst is designated as Fe
3o
4mgAl-LDHPd-Au-3%-3%, and be 41.8emu/g to known its saturation magnetization (Ms) of the magnetism testing of this catalyst.The magnetic nuclear mass percentage of catalyst is about 58%, and the mass percent of shell hydrotalcite is about 39%.
Embodiment 3
(1) preparation of magnetic core
The solvent-thermal method of surfactant-free is adopted to prepare Fe
3o
4magnetic core (Chinese invention patent ZL 2,011 10344754.5).Concrete preparation process: take 3.24g (0.012mol) FeCl
36H
2o, 8.64g (0.064mol) NaAc3H
2o is dissolved in 80mL ethylene glycol; At room temperature stir 20min and be dissolved to finely dispersed brown yellow solution; Obtained solution is transferred in the reactor of 100mL, at 200 DEG C, reacts 8h.After reaction terminates, carry out running water and be cooled to room temperature, obtained black suspension ethanol and deionized water are alternately washed totally 6 times, in washing process, adopts permanent magnet to isolate black solid, gained sample is put into drying box 80 DEG C of dry 12h after washing, be designated as Fe
3o
4.
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
1. the preparation of mixing salt solution takes Ni (NO
3)
26H
2o (2.6172g), Al (NO
3)
39H
2o (1.1264g), 100mL deionized water is stirred in 250mL beaker dissolves completely.
2. the preparation of mixed ammonium/alkali solutions takes NaOH (0.8g), Na
2cO
3(0.64g), 100mL deionized water, in 250mL beaker, is stirred to and dissolves completely.
3. two coprecipitation of dripping is adopted to prepare the hud typed hydrotalcite supports of magnetic multilevel hierarchy.Take Fe
3o
4nanoparticle (1.042g) in 500mL four-hole boiling flask, then adds 100mL deionized water, ultrasonic 20min, then, slowly drips mixed alkali liquor in Fe
3o
4in suspension to pH be 10, after stablizing 5min, then with 1.7mL/min drip speed drip mixing salt solution, remain in this process that pH is 10, until mixing salt solution dropwises; Terminate reaction after stablizing 5min, then washing several to supernatant liquor pH by magnet separation, deionized water is 7, by gained sample in 80 DEG C of dry 12h, is designated as Fe
3o
4niAl-LDH.
(3) preparation of magnetic multistage nucleocapsid structure load type gold palladium alloy catalysts
By 2.5mL k
2pdCl
4(10g/L) with 3.1mL HAuCl
44H
2o (10g/L) is mixed to form the aqueous solution of 150mL, and toward wherein adding 1.30g PVP and 50mL ethylene glycol, gained mixture, at 145 DEG C of backflow 1.5h, then cools 2h in atmosphere to room temperature, then adds 1g carrier Fe
3o
4niAl-LDH, stirring at room temperature 4h, then leave standstill 12h; Carry out solid-liquor separation with magnet, acetone and water replace washing 5 times, by gained solid sample dry 12h at 80 DEG C, obtain high dispersive small-size magnetic load type gold palladium alloy catalysts.This catalyst is designated as Fe
3o
4niAl-LDHPd-Au-1.5%-1.5%.
Embodiment 4
(1) preparation of magnetic core
Preparation process is with embodiment 1.
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
Preparation process is with embodiment 1.
(3) preparation of magnetic multistage nucleocapsid structure load type gold palladium alloy catalysts
By 2.5mL k
2pdCl
4(10g/L) with 3.1mL HAuCl
44H
2o (10g/L) is mixed to form the aqueous solution of 150mL, and toward wherein adding 1.3g PVP and 50mL ethylene glycol, gained mixture, at 140 DEG C of backflow 2h, cools 2h afterwards in atmosphere to room temperature, then adds 1g carrier Fe
3o
4mgAl-LDH, stirring at room temperature 1h, then leave standstill 24h; Then carry out Separation of Solid and Liquid with magnet, acetone and water replace washing 4 times, and gained solid sample is dry 24h at 70 DEG C, obtain high dispersive small-size magnetic load type gold palladium alloy catalysts, are designated as Fe
3o
4mgAl-LDHPd-Au-1.5%-1.5%.
Embodiment 5
(1) preparation of magnetic core
Preparation process is with embodiment 1.
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
Preparation process is with embodiment 1.
(3) preparation of magnetic multistage nucleocapsid structure load type gold palladium alloy catalysts
By 1.7mL K
2pdCl
4(10g/L) with 2.1mL HAuCl
44H
2o (10g/L) is mixed to form the aqueous solution of 175mL, and toward wherein adding 0.87g PVP and 25mL ethylene glycol, gained mixture, at 140 DEG C of backflow 2h, cools 1.5h afterwards in atmosphere to room temperature, then adds 1g carrier Fe
3o
4mgAl-LDH, stirring at room temperature 1h, then leave standstill 12h; Then carry out Separation of Solid and Liquid with magnet, acetone and water replace washing 3 times, and gained solid sample is dry 24h at 60 DEG C, obtain high dispersive small-size magnetic load type gold palladium alloy catalysts, are designated as Fe
3o
4mgAl-LDHPd-Au-1%-1%.
Embodiment 6
(1) preparation of magnetic core
Preparation process is with embodiment 1.
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
1. the preparation of mixing salt solution takes Co (NO
3)
26H
2o (2.6193g), Al (NO
3)
39H
2o (1.1264g), (volume ratio is V to 100mL methanol aqueous solution
methyl alcohol: V
water=1:1) be stirred in 250mL beaker and dissolve completely.
2. the preparation of mixed ammonium/alkali solutions takes NaOH (0.8g), Na
2cO
3(0.64g), (volume ratio is V to 100mL methanol aqueous solution
methyl alcohol: V
water=1:1) in 250mL beaker, be stirred to and dissolve completely.
3. two coprecipitation of dripping is adopted to prepare the hud typed hydrotalcite supports of magnetic multilevel hierarchy.Take Fe
3o
4nanoparticle (1.042g) is in 500mL four-hole boiling flask, then (volume ratio is V to add 100mL methanol-water solution
methyl alcohol: V
water=1:1), ultrasonic 10min, then, slowly drips mixed alkali liquor in Fe
3o
4in suspension to pH be 10, after stablizing 5min, then with 0.8mL/min drip speed drip mixing salt solution, remain in this process that pH is 10, until mixing salt solution dropwises; Terminate reaction after stablizing 5min, then washing several to supernatant liquor pH by magnet separation, deionized water is 7, by gained sample in 60 DEG C of dry 24h, is designated as Fe
3o
4coAl-LDH.
(3) preparation of magnetic multistage nucleocapsid structure load type gold palladium alloy catalysts
By 2.5mL k
2pdCl
4(10g/L) with 3.1mL HAuCl
44H
2o (10g/L) is mixed to form the aqueous solution of 150mL, and toward wherein adding 1.30g PVP and 50mL ethylene glycol, gained mixture, at 140 DEG C of backflow 2h, cools 0.5h afterwards in atmosphere to room temperature, then adds 1g carrier Fe
3o
4coAl-LDH, stirring at room temperature 1h, then leave standstill 24h; Then carry out Separation of Solid and Liquid with magnet, acetone and water replace washing 3 times, by gained solid sample dry 12h at 80 DEG C, obtain high dispersive small-size magnetic load type gold palladium alloy catalysts.This catalyst is designated as Fe
3o
4coAl-LDHPd-Au-1.5%-1.5%.
Embodiment 7
(1) preparation of magnetic core
Preparation process is with embodiment 1.
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
1. the preparation of mixing salt solution takes Mg (NO
3)
26H
2o (1.9231g), Cu (NO
3)
23H
2o (0.3624g), Al (NO
3)
39H
2o (1.1264g), i.e. n
mg: n
cu(volume ratio is V to=5:1,100mL methanol aqueous solution
methyl alcohol: V
water=1:1) be stirred in 250mL beaker and dissolve completely.
2. the preparation of mixed ammonium/alkali solutions takes NaOH (0.8g), Na
2cO
3(0.64g), (volume ratio is V to 100mL methanol aqueous solution
methyl alcohol: V
water=1:1) in 250mL beaker, be stirred to and dissolve completely.
3. two coprecipitation of dripping is adopted to prepare the hud typed hydrotalcite supports of magnetic multilevel hierarchy.Take Fe
3o
4nanoparticle (1.042g) is in 500mL four-hole boiling flask, then (volume ratio is V to add 100mL methanol-water solution
methyl alcohol: V
water=1:1), then ultrasonic 20min starts slowly to drip mixed alkali liquor in Fe
3o
4mixed liquor is 10, after stablizing 5min to pH, starts to drip mixing salt solution with the speed of dripping of 1.2mL/min, remains that pH is 10, until mixing salt solution dropwises in this process; Be placed on crystallization 24h in 60 DEG C of water-baths, then with magnet be separated, deionized water washing is 7 to supernatant pH, by gained sample in 70 DEG C of dry 18h, is designated as Fe
3o
4cuMgAl-LDH.
(3) preparation of magnetic multistage nucleocapsid structure load type gold palladium alloy catalysts.
By 5.3mL k
2pdCl
4(10g/L) with 6.2mL HAuCl
44H
2o (10g/L) is mixed to form the aqueous solution of 100mL, and toward wherein adding 2.61g PVP and 100mL ethylene glycol, gained mixture, at 140 DEG C of backflow 2h, then cools 2h in atmosphere to room temperature, then adds 1g carrier Fe
3o
4mgCuAl-LDH, stirring at room temperature 2h, then leave standstill 12h; Carry out Separation of Solid and Liquid with magnet, acetone and water replace washing 4 times, by gained solid sample dry 24h at 60 DEG C, obtain high dispersive small-size magnetic load type gold palladium alloy catalysts.This catalyst is designated as Fe
3o
4mgCuAl-LDHPd-Au-3%-3%.
Claims (3)
1. a high dispersive small-size magnetic load type gold palladium alloy catalysts, it is characterized in that, the rhotanium nanoparticle that reduction of ethylene glycol method is obtained is carried in the multistage nucleocapsid structure hydrotalcite supports of magnetic, obtain the undersized magnetic of high dispersive multistage nucleocapsid structure load type gold palladium alloy catalysts, in its active component rhotanium, the mass percent of each element is respectively Pd:1%-3%, Au:1%-3%, particle size distribution scope is <4nm; This catalyst presents honeycomb pattern, and saturation magnetization Ms is 28-42emu/g; The core of the multistage nucleocapsid structure hydrotalcite supports of magnetic is Fe 3 O 4 magnetic particle, and it is of a size of 500-600nm, and accounting for total catalyst mass percent is 44%-58%, and shell is hydrotalcite (M
2+-M
3+)-LDH, M
2+for Mg
2+, Ni
2+, Co
2+, Cu
2+any one or two kinds in bivalent metal ion, M
3+for trivalent metal ion Al
3+, shell thickness is 30-120nm, and mass percent is 39%-53%.
2. catalyst according to claim 1, is characterized in that, has high catalytic activity and selective in Heck coupling reaction system, with iodobenzene and styrene coupling for probe reaction, uses catalyst (Fe
3o
4niAl-LDHPd-Au-3%-3%) input amount is 50mg, and potash is alkali additive, and solvent is 12mL N, the mixed liquor of dinethylformamide DMF and 4mL water, after 120 DEG C of reaction 3h, the conversion ratio of iodobenzene reaches 100%, and target product is trans-and the productive rate of talan reaches 93%; Utilize the magnetic characteristic of catalyst reclaim and reuse, reuse 5 activity and obviously do not reduce.
3. a preparation method for high dispersive small-size magnetic load type gold palladium alloy catalysts according to claim 1, it is characterized in that, processing step is as follows:
(1) preparation of magnetic core
Adopt the solvent-thermal method of surfactant-free, concrete preparation process: take 3.24g (0.012mol) FeCl
36H
2o, 8.64g (0.064mol) NaAc3H
2o is dissolved in 80mL ethylene glycol; Ultrasonic or at 20 DEG C-40 DEG C stirring and dissolving to finely dispersed brown yellow solution; Obtained solution is transferred in the reactor of 100mL, at 200 DEG C of reaction 8h; After reaction terminates, carry out running water and be cooled to room temperature, obtained black suspension ethanol and deionized water are alternately washed 4-6 time altogether, adopts permanent magnet to isolate black solid in washing process, after washing, gained sample is put into drying box 60-80 DEG C of dry 24-12h.Be designated as Fe
3o
4
(2) preparation of the hud typed hydrotalcite supports of magnetic multilevel hierarchy
The preparation of mixing salt solution: take M
2+(NO
3)
2nH
2o (0.009mol), M
3+(NO
3)
39H
2o (0.003mol), 100mL methanol aqueous solution, volume ratio is V
methyl alcohol: V
water=0,1, be stirred in 250mL beaker and dissolve completely;
The preparation of mixed ammonium/alkali solutions: take NaOH (0.02mol, 0.8g), Na
2cO
3(0.006mol, 0.64g), 100mL methanol aqueous solution, volume ratio is V
methyl alcohol: V
water=0,1, in 250mL beaker, be stirred to and dissolve completely;
Two coprecipitation of dripping is adopted to prepare Fe
3o
4mA-LDH carrier: take Fe
3o
4nanoparticle 1.042g in 500mL four-hole boiling flask, then adds 100mL methanol aqueous solution, methyl alcohol: water=0, and 1, then ultrasonic 10 – 20min start slowly to drip alkali lye in this Fe
3o
4mixed liquor is 10, after stablizing 5min to pH, starts to drip mixing salt solution with the speed of dripping of 0.8 ~ 1.7mL/min, remains that pH is 10, until mixing salt solution dropwises in this process; After stablizing 5min, in 60 DEG C of water-baths, terminate reaction after crystallization 0 – 24h, spend deionized water to supernatant for neutral, then the solid product obtained is placed on dry 24-18h at 60-70 DEG C of temperature.Be designated as Fe
3o
4(M
2+-M
3+)-LDH, M
2+for Mg
2+, Ni
2+, Co
2+, Cu
2+any one or two kinds in bivalent metal ion, M
3+for trivalent metal ion Al
3+;
(3) preparation of the multistage nucleocapsid loading type Pd of magnetic-Au alloy catalyst
Down payment mass percentage 1%-3% measures corresponding liquor capacity k to palladium mass percentage 1%-3%
2pdCl
4(10g/L) and HAuCl
44H
2o (10g/L) carries out the aqueous solution that mixed dissolution forms 100 – 175mL, toward wherein adding 0.87g-2.61g PVP and 25-100mL ethylene glycol, gained mixture, at 135 DEG C-145 DEG C backflow 1.5h – 2.5h, then cools 0.5h – 2h in atmosphere, then adds 1g Fe
3o
4m
2+m
3+-LDH carrier, stirs 2h-4h, leaves standstill 12-48h; Be separated with magnet, with acetone and water alternately washing 3-5 time, by gained solid sample dry 24-12h at 60 DEG C-80 DEG C, obtain high dispersive small-size magnetic load type gold palladium alloy catalysts; This catalyst is designated as Fe
3o
4m
2+m
3+-LDHPd-Au-n
1-n
2; Wherein, M
2+for Mg
2+, Ni
2+, Co
2+, Cu
2+any one or two kinds in bivalent metal ion, M
3+for trivalent metal ion Al
3+, n
1represent Pd mass percent, n
2represent Au mass percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510145564.9A CN104801316B (en) | 2015-03-30 | 2015-03-30 | High dispersive small-size magnetic load type gold palladium alloy catalysts and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510145564.9A CN104801316B (en) | 2015-03-30 | 2015-03-30 | High dispersive small-size magnetic load type gold palladium alloy catalysts and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104801316A true CN104801316A (en) | 2015-07-29 |
| CN104801316B CN104801316B (en) | 2017-12-29 |
Family
ID=53686760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510145564.9A Expired - Fee Related CN104801316B (en) | 2015-03-30 | 2015-03-30 | High dispersive small-size magnetic load type gold palladium alloy catalysts and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104801316B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879881A (en) * | 2016-04-29 | 2016-08-24 | 盐城师范学院 | Preparation method of PtPd/Fe3O4 (platinum-palladium/ferroferric oxide) nanocatalyst and application thereof in HECK reaction |
| CN107335454A (en) * | 2017-08-28 | 2017-11-10 | 安徽大学 | A kind of loading type Pd3The preparation and its application of Cl cluster catalyst |
| CN108187743A (en) * | 2018-01-17 | 2018-06-22 | 南京工程学院 | A kind of ion exchange resin supports nanogold palladium alloy catalysts and preparation method thereof |
| CN108246311A (en) * | 2018-01-24 | 2018-07-06 | 济南大学 | A kind of metal simple-substance is inserted into the preparation method of layered double-hydroxide interlayer porous material |
| WO2019213995A1 (en) * | 2018-05-09 | 2019-11-14 | 南通龙翔新材料科技股份有限公司 | Palladium-platinum alloy nanosol catalyst and preparation method therefor |
| CN110882702A (en) * | 2019-12-16 | 2020-03-17 | 生态环境部环境规划院 | Preparation method and application of catalytic material based on magnetic layered double hydroxide |
| CN111054333A (en) * | 2020-02-14 | 2020-04-24 | 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 |
| WO2020175142A1 (en) * | 2019-02-28 | 2020-09-03 | 株式会社キャタラー | Supported catalyst particles |
| JP2022039147A (en) * | 2020-08-28 | 2022-03-10 | トヨタ自動車株式会社 | Exhaust gas purification unit |
| CN115212872A (en) * | 2022-08-03 | 2022-10-21 | 中山大学 | Monoatomic alloy catalyst for directly synthesizing high-concentration hydrogen peroxide from hydrogen and oxygen and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030039860A1 (en) * | 2001-08-16 | 2003-02-27 | Cheon Jin Woo | Method for synthesis of core-shell type and solid solution alloy type metallic nanoparticles via transmetalation reactions and applications of same |
| CN101683619A (en) * | 2008-09-28 | 2010-03-31 | 复旦大学 | Load type nano gold catalyst for preparing lactone by catalyzing air oxidation alpha, omega-diol and preparation method thereof |
| CN102088091A (en) * | 2010-12-17 | 2011-06-08 | 北京化工大学 | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof |
| CN102513126A (en) * | 2011-11-04 | 2012-06-27 | 北京化工大学 | Multilevel core-shell structure magnetic nano gold catalyst and preparation method thereof |
| CN103285880A (en) * | 2013-05-28 | 2013-09-11 | 浙江科技学院 | Preparation method of proton exchange membrane fuel battery catalyst |
-
2015
- 2015-03-30 CN CN201510145564.9A patent/CN104801316B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030039860A1 (en) * | 2001-08-16 | 2003-02-27 | Cheon Jin Woo | Method for synthesis of core-shell type and solid solution alloy type metallic nanoparticles via transmetalation reactions and applications of same |
| CN101683619A (en) * | 2008-09-28 | 2010-03-31 | 复旦大学 | Load type nano gold catalyst for preparing lactone by catalyzing air oxidation alpha, omega-diol and preparation method thereof |
| CN102088091A (en) * | 2010-12-17 | 2011-06-08 | 北京化工大学 | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof |
| CN102513126A (en) * | 2011-11-04 | 2012-06-27 | 北京化工大学 | Multilevel core-shell structure magnetic nano gold catalyst and preparation method thereof |
| CN103285880A (en) * | 2013-05-28 | 2013-09-11 | 浙江科技学院 | Preparation method of proton exchange membrane fuel battery catalyst |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879881A (en) * | 2016-04-29 | 2016-08-24 | 盐城师范学院 | Preparation method of PtPd/Fe3O4 (platinum-palladium/ferroferric oxide) nanocatalyst and application thereof in HECK reaction |
| CN107335454B (en) * | 2017-08-28 | 2020-07-24 | 安徽大学 | Load type Pd3Preparation and application of Cl cluster catalyst |
| CN107335454A (en) * | 2017-08-28 | 2017-11-10 | 安徽大学 | A kind of loading type Pd3The preparation and its application of Cl cluster catalyst |
| CN108187743A (en) * | 2018-01-17 | 2018-06-22 | 南京工程学院 | A kind of ion exchange resin supports nanogold palladium alloy catalysts and preparation method thereof |
| CN108246311A (en) * | 2018-01-24 | 2018-07-06 | 济南大学 | A kind of metal simple-substance is inserted into the preparation method of layered double-hydroxide interlayer porous material |
| CN108246311B (en) * | 2018-01-24 | 2020-08-14 | 济南大学 | Preparation method of metal simple substance inserted layered double hydroxide interlayer porous material |
| WO2019213995A1 (en) * | 2018-05-09 | 2019-11-14 | 南通龙翔新材料科技股份有限公司 | Palladium-platinum alloy nanosol catalyst and preparation method therefor |
| WO2020175142A1 (en) * | 2019-02-28 | 2020-09-03 | 株式会社キャタラー | Supported catalyst particles |
| CN113423501A (en) * | 2019-02-28 | 2021-09-21 | 株式会社科特拉 | Supported catalyst particles |
| JPWO2020175142A1 (en) * | 2019-02-28 | 2021-11-25 | 株式会社キャタラー | Supported catalyst particles |
| JP7093885B2 (en) | 2019-02-28 | 2022-06-30 | 株式会社キャタラー | Supported catalyst particles |
| CN113423501B (en) * | 2019-02-28 | 2023-11-03 | 株式会社科特拉 | Supported catalyst particles |
| CN110882702A (en) * | 2019-12-16 | 2020-03-17 | 生态环境部环境规划院 | Preparation method and application of catalytic material based on magnetic layered double hydroxide |
| CN111054333A (en) * | 2020-02-14 | 2020-04-24 | 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 |
| 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 |
| JP2022039147A (en) * | 2020-08-28 | 2022-03-10 | トヨタ自動車株式会社 | Exhaust gas purification unit |
| JP7235417B2 (en) | 2020-08-28 | 2023-03-08 | トヨタ自動車株式会社 | Exhaust gas purifier |
| CN115212872A (en) * | 2022-08-03 | 2022-10-21 | 中山大学 | Monoatomic alloy catalyst for directly synthesizing high-concentration hydrogen peroxide from hydrogen and oxygen and preparation method thereof |
| CN115212872B (en) * | 2022-08-03 | 2023-08-15 | 中山大学 | Monoatomic alloy catalyst for directly synthesizing high-concentration hydrogen peroxide by using hydrogen and oxygen and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104801316B (en) | 2017-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104801316A (en) | High-dispersion small-sized magnetic load type gold-palladium alloy catalyst and preparation method thereof | |
| Zhang et al. | Pulsed laser ablation based synthesis of colloidal metal nanoparticles for catalytic applications | |
| Jiang et al. | Facile synthesis of Ag@ Pd satellites–Fe 3 O 4 core nanocomposites as efficient and reusable hydrogenation catalysts | |
| Zhang et al. | Hierarchical architectures of monodisperse porous Cu microspheres: synthesis, growth mechanism, high-efficiency and recyclable catalytic performance | |
| CN104028269B (en) | Graphene loaded metal nano composite material, and preparation method and application thereof | |
| CN111330639B (en) | Hybrid material of porous cobalt-zinc core-shell metal organic framework compound confinement precious metal nanoparticles and preparation method and application thereof | |
| CN101758243B (en) | Preparation method of hollow gold nanometer cage | |
| CN103586048B (en) | A kind of nano Pd particle magnetic catalyst, preparation and react for liquid-phase catalysis | |
| CN107376996A (en) | A kind of ammonia borane hydrolysis releases hydrogen ruthenium cobalt dual-metal manometer load-type catalyst and preparation method thereof | |
| JP2008516882A (en) | Transition metal-magnetic iron oxide nanocomposite, production method and application thereof | |
| CN101007281A (en) | Novel preparation method of amorphous alloy catalyst | |
| CN108906058B (en) | Non-noble metal catalyst and preparation method thereof | |
| CN102806105B (en) | Loaded aurum palladium catalyst and preparation method and application thereof | |
| CN109894149B (en) | Composite nano-structure catalyst and preparation and application thereof | |
| Marandi et al. | Fe3O4@ TEA core-shell nanoparticles decorated palladium: A highly active and magnetically separable nanocatalyst for the Heck coupling reaction | |
| CN105170161B (en) | Hydrotalcite loads Au25‑xPdxCluster catalyst and preparation method thereof | |
| Murugan et al. | Efficient amphiphilic poly (propyleneimine) dendrimer stabilized gold nanoparticle catalysts for aqueous phase reduction of nitrobenzene | |
| CN100522824C (en) | Method for preparing Nano particles of monodisperse, ultra paramagnetic ferroferric oxide | |
| CN110433825A (en) | A kind of monatomic palladium-based catalyst and its preparation method and application | |
| CN109126820A (en) | Core-shell structure Au@PtCu is nanocrystalline and its preparation method and application | |
| CN108212175A (en) | A kind of porous C o3O4Mono-dispersion microballoon load Au-Pd alloy nano catalyst and preparation method thereof | |
| CN104624175B (en) | Nano-magnetic adsorbent and preparation method thereof | |
| CN102515984B (en) | Core-shell nano-composite material and its preparation method | |
| CN105562106B (en) | A kind of magnetic oxygenated graphene-supported phosphine schiff bases palladium catalyst and its preparation method and application | |
| Safari et al. | Dendritic macromolecules supported Ag nanoparticles as efficient catalyst for the reduction of 4-nitrophenol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171229 |