CN107824186A - A kind of praseodymium oxide load nanotube-palladium composite material and preparation method thereof - Google Patents
A kind of praseodymium oxide load nanotube-palladium composite material and preparation method thereof Download PDFInfo
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- CN107824186A CN107824186A CN201711144815.7A CN201711144815A CN107824186A CN 107824186 A CN107824186 A CN 107824186A CN 201711144815 A CN201711144815 A CN 201711144815A CN 107824186 A CN107824186 A CN 107824186A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 229910003447 praseodymium oxide Inorganic materials 0.000 title claims abstract description 59
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910002637 Pr6O11 Inorganic materials 0.000 claims abstract description 27
- 239000002086 nanomaterial Substances 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 51
- 238000001354 calcination Methods 0.000 claims description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- ZLGIGTLMMBTXIY-UHFFFAOYSA-K praseodymium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Pr+3] ZLGIGTLMMBTXIY-UHFFFAOYSA-K 0.000 claims description 8
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 3
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 3
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 13
- 239000002105 nanoparticle Substances 0.000 abstract description 10
- 238000011161 development Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002073 nanorod Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000001362 electron spin resonance spectrum Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/073—Ethylbenzene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of preparation method of praseodymium oxide load nanotube-palladium composite material, including：S1) by Pr6O11Nano material is distributed to the solution of containing palladium compound, stirring and adsorbing, the solid after being adsorbed；S2) solid after the absorption is calcined in reducing atmosphere high temperature, obtains praseodymium oxide load nanotube-palladium composite material.Compared with prior art, using the Pr with oxygen defect6O11Nanometer rods are carrier, it is reducing loaded after palladium nano-particles size it is very small, and the Lacking oxygen in carrier can provide more avtive spots, improve the activity and cyclical stability of catalyst in hydrogenation reaction；And the composite material and preparation method thereof is simple, it is easy to prepare on a large scale, there is provided a kind of method for preparing high performance and nano structure catalyst, be advantageous to the sustainable development of environment.
Description
Technical field
The invention belongs to technical field of nano material, more particularly to a kind of praseodymium oxide load nanotube-palladium composite material and its system
Preparation Method.
Background technology
Metal catalytic hydrogenation reaction plays very in the batch production process of the products such as medicine, polymer, fine chemistry industry
Important effect.Palladium nano-particles are a kind of very high noble metals of activity, there is boundless application in hydrogenation reaction
Prospect.However, the application of palladium-based catalyst has many restrictive conditions, for example, cost it is high, particle can be caused to hold due to high-ratio surface
Easy reunion, poor circulation etc..These problems can be improved by the way that palladium nano-particles are supported on various carriers at present, than
Such as metal oxide, organic polymer, carbon material and biomaterial.On the one hand, noble metal granule is supported on and lacked with oxygen
Dispersiveness can be not only improved on sunken metal oxide, additionally it is possible to activated reactant, the progress for accelerating reaction；On the other hand,
Strong interaction (SMSI) between noble metal and carrier can also influence reactivity and selectivity in catalytic process.Therefore carry
The reasonable selection of body has highly important influence to efficiency, the stability of catalytic reaction.
The content of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of praseodymium oxide load nanotube-palladium composite material and
Its preparation method, the composite have preferable catalytic performance and cyclical stability.
The invention provides a kind of preparation method of praseodymium oxide load nanotube-palladium composite material, including：
S1) by Pr6O11Nano material is distributed to the solution of containing palladium compound, stirring and adsorbing, the solid after being adsorbed；
S2) solid after the absorption is calcined in reducing atmosphere high temperature, obtains praseodymium oxide load Technique of Nano Pd composite wood
Material.
Preferably, the Pr6O11Nano material is prepared according to following steps：
A1 after) praseodymium nitrate is mixed in aqueous with weak base, hydro-thermal reaction is carried out, obtains praseodymium hydroxide；
A2) praseodymium hydroxide is calcined in atmosphere, obtains Pr6O11Nano material.
Preferably, the step A1) in mix after system pH value be 8~10.
Preferably, the step A1) in hydro-thermal reaction temperature be 110 DEG C~130 DEG C；The time of the hydro-thermal reaction is
6~10h；The step A2) in calcining temperature be 400 DEG C~800 DEG C；The time of the calcining is 1~5h.
Preferably, the containing palladium compound is selected from Na2PdCl4、H2PdCl4With K2PdCl4In one or more.
Preferably, the quality of element palladium is Pr in the solution of the containing palladium compound6O11The 1% of nano material quality~
2%.
Preferably, the concentration of element palladium is 0.4~1mmol/L in the solution of the containing palladium compound.
Preferably, the time of the stirring and adsorbing is 10~14h；The time of the high-temperature calcination is 300 DEG C~500 DEG C；
The time of the high-temperature calcination is 1~4h.
Present invention also offers praseodymium oxide prepared by the above method to load nanotube-palladium composite material.
The styrene catalyzed hydrogenation of praseodymium oxide load nanotube-palladium composite material prepared present invention also offers the above method is anti-
The purposes answered.
The invention provides a kind of preparation method of praseodymium oxide load nanotube-palladium composite material, including：S1) by Pr6O11Receive
Rice material is distributed to the solution of containing palladium compound, stirring and adsorbing, the solid after being adsorbed；S2) by the solid after the absorption
Calcined in reducing atmosphere high temperature, obtain praseodymium oxide load nanotube-palladium composite material.Compared with prior art, lacked using with oxygen
Sunken Pr6O11Nanometer rods are carrier, it is reducing loaded after palladium nano-particles size it is very small, and the Lacking oxygen in carrier can
More avtive spots are provided, improve the activity and cyclical stability of catalyst in hydrogenation reaction；And the composite system
Preparation Method is simple, is easy to prepare on a large scale, there is provided a kind of method for preparing high performance and nano structure catalyst, is advantageous to environment
Sustainable development.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo that praseodymium oxide prepared by the embodiment of the present invention 1 loads nanotube-palladium composite material；
Fig. 2 is the stereoscan photograph that praseodymium oxide prepared by the embodiment of the present invention 2 loads nanotube-palladium composite material；
Fig. 3 is the transmission electron microscope photo that praseodymium oxide prepared by the embodiment of the present invention 2 loads nanotube-palladium composite material；
Fig. 4 is the XRD that praseodymium oxide prepared by the embodiment of the present invention 2 loads nanotube-palladium composite material；
Fig. 5 is the electron paramagnetic resonance spectrum (EPR) that praseodymium oxide prepared by the embodiment of the present invention 2 loads nanotube-palladium composite material
(EPR) figure；
Fig. 6 is the transmission electron microscope photo that praseodymium oxide prepared by the embodiment of the present invention 3 loads nanotube-palladium composite material；
Fig. 7 is the praseodymium oxide (Pr with oxygen defect prepared by comparative example 1 of the present invention6O11) nanometer rods transmission electron microscope shine
Piece；
Fig. 8 is the styrene catalytic hydrogenation reaction that praseodymium oxide prepared by the embodiment of the present invention 2 loads nanotube-palladium composite material
Performance chart；
Fig. 9 is the styrene catalytic hydrogenation reaction that praseodymium oxide prepared by the embodiment of the present invention 2 loads nanotube-palladium composite material
Cycle performance curve map；
Figure 10 is praseodymium oxide (Pr6O11) the styrene catalyzed hydrogenation reaction of supported palladium nano particle composite material flow signal
Figure；
Figure 11 is the transmission electron microscope photo that praseodymium oxide prepared by the embodiment of the present invention 4 loads nanotube-palladium composite material；
Figure 12 is the styrene catalytic hydrogenation reaction that praseodymium oxide prepared by the embodiment of the present invention 4 loads nanotube-palladium composite material
Performance chart；
Figure 13 is the transmission electron microscope photo that praseodymium oxide prepared by the embodiment of the present invention 5 loads nanotube-palladium composite material；
Figure 14 is the styrene catalytic hydrogenation reaction that praseodymium oxide prepared by the embodiment of the present invention 5 loads nanotube-palladium composite material
Performance chart；
Figure 15 is the performance chart of the styrene catalytic hydrogenation reaction of praseodymium oxide prepared by comparative example 2 of the present invention.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
The invention provides a kind of preparation method of praseodymium oxide load nanotube-palladium composite material, including：S1) by Pr6O11Receive
Rice material is distributed to the solution of containing palladium compound, stirring and adsorbing, the solid after being adsorbed；S2) by the solid after the absorption
Calcined in reducing atmosphere high temperature, obtain praseodymium oxide load nanotube-palladium composite material.
The present invention is using the Pr with oxygen defect6O11Nanometer rods are carrier, it is reducing loaded after palladium nano-particles size it is non-
It is often small, and the Lacking oxygen in carrier can provide more avtive spots, improve in hydrogenation reaction the activity of catalyst and
Cyclical stability；And the composite material and preparation method thereof is simple, it is easy to prepare on a large scale, there is provided one kind prepares high-performance nano
The method of structure catalyst, be advantageous to the sustainable development of environment
Wherein, the present invention is not particularly limited to the source of all raw materials, for commercially available or self-control.
The Pr6O11Nano material is Pr well known to those skilled in the art6O11Nano material, have no special limit
System, it is preferably Pr in of the invention6O11Nanometer rods；The Pr6O11Nano material preferably obtains through calcining praseodymium hydroxide；The calcining
It is preferred that carry out in atmosphere；The temperature of the calcining is preferably 400 DEG C~800 DEG C, more preferably 500 DEG C~700 DEG C, further preferably
For 550 DEG C~650 DEG C, most preferably 600 DEG C；The time of the calcining is preferably 1~5h, more preferably 2~4h, further preferably for
3h；The praseodymium hydroxide is preferably prepared by following methods：After praseodymium nitrate is mixed in aqueous with weak base, it is anti-to carry out hydro-thermal
Should, obtain praseodymium hydroxide；The weak base is weak base well known to those skilled in the art, has no special limitation, the present invention
In be preferably ammoniacal liquor；The pH value of system is preferably 8~10 after the mixing, and more preferably 8~9, it is further preferably 8；The mixing
The concentration of praseodymium nitrate is preferably 10~20mg/ml in system afterwards, more preferably 13~18mg/ml, is further preferably 15~17mg/
Ml, most preferably 16mg/ml；Preferred stirring 10~50min, more preferably 10~40min after mixing, further preferably for 10~
Hydro-thermal reaction is carried out after 30min, most preferably 20min again；The temperature of the hydro-thermal reaction is preferably 110 DEG C~130 DEG C, more excellent
Elect 115 DEG C~125 DEG C as, be further preferably 120 DEG C；The time of the hydro-thermal reaction is preferably 6~10h, more preferably 7~9h,
It is further preferably 8h；Preferably centrifuge, wash after hydro-thermal reaction, praseodymium hydroxide is obtained after drying；The mode of the drying is preferably true
Sky is dried；The temperature of the drying is preferably 60 DEG C~80 DEG C；The time of the drying is preferably 10~20h, and more preferably 10
~16h, it is further preferably 12~14h.
Rare earth oxide has special electricity, optics, magnetics and chemical property, therefore is filled in high-performance fluorescence
Put, have in catalyst etc. and widely apply.Praseodymium oxide is a kind of critically important rare earth oxide, and current research application has
For the adsorbent of dyestuff removal, the oxidation of carbon monoxide, the synthetic catalyst of ethane and ethene, ceramic dyestuff etc..Praseodymium oxide
There are a variety of non-stoichiometric oxides, such as Pr2O3、PrO2、Pr4O7Deng.Wherein, Pr6O11It is a kind of n-type semiconductor, electricity
Conductance is high, and stable under air at room temperature, and the noble metal that this characteristic is allowed it to and loaded forms SMSI effects, therefore
Be advantageous to absorption and activated reactant and be eventually converted into end-product.
By Pr6O11Nano material is distributed to the solution of containing palladium compound, stirring and adsorbing, the solid after being adsorbed；It is described
The quality of element palladium is Pr in the solution of containing palladium compound6O11The 1%~2% of nano material quality, more preferably 1%~
1.5%, it is further preferably 1.5%；The concentration of element palladium is 0.4~1mmol/L in the solution of the containing palladium compound, more preferably
0.47~0.94mmol/L, it is further preferably 0.47~0.7mmol/L；The containing palladium compound is well known to those skilled in the art
Water miscible containing palladium compound, special limitation is had no, be preferably Na in the present invention2PdCl4、H2PdCl4With K2PdCl4In
One or more；The time of the stirring and adsorbing is preferably 10~14h, more preferably 11~13h；After stirring and adsorbing preferably from
The heart is dried, the solid after being adsorbed；The method of the drying is method well known to those skilled in the art, has no spy
Different limitation, it is preferably to be dried in vacuo in of the invention；The temperature of the drying is preferably 60 DEG C~80 DEG C；The time of the drying
Preferably 10~20h, more preferably 10~16h, it is further preferably 12~14h.
Solid after the absorption is calcined in reducing atmosphere high temperature, obtains praseodymium oxide load nanotube-palladium composite material；
The reducing atmosphere is reducing atmosphere well known to those skilled in the art, has no special limitation, is preferably in the present invention
The mixed atmosphere of hydrogen and argon gas；The volume fraction of hydrogen is preferably 5%~10% in the mixed atmosphere, and more preferably 5%
~8%；The temperature of the high-temperature calcination is preferably 300 DEG C~500 DEG C, and more preferably 350 DEG C~450 DEG C, be further preferably 350 DEG C
~400 DEG C；The time of the high-temperature calcination is preferably 1~4h, more preferably 1~3h.
Pr6O11For n-type semiconductor, conductance is high, and during hydrogen argon calcining reduction, due to palladium presence and
With the collective effect of its hydrogen so that the surfaces of carrier materials after reduction becomes coarse, in summary 2 points, it was demonstrated that carrier and
SMSI effects between noble metal be present, i.e. strong metal interacts, and according to having document report at present, this effect can influence
The selectivity and activity of catalytic reaction；During hydrogen argon calcining reduction, due to the presence of palladium and common with its hydrogen
Effect, can also form oxygen defect in oxide carrier, and the oxygen defect in carrier plays very important work to hydrogenation reaction
With oxygen defect can be used as electron donor so that the electron density increase that palladium particle goes out, therefore C=C activation is promoted, carry
High styrene catalytic reaction efficiency；Using Pr6O11As carrier, additionally it is possible to the dispersiveness and uniformity of palladium particle are improved,
And then improve reactivity.
Method and step provided by the invention is simple, and operation is simple, and the characteristics of having easily and fast, preparation lacks with oxygen
Sunken praseodymium oxide (Pr6O11) supported palladium nano particle composite material possess optimization Pd cloud densities and high active of hydrogenation catalysis it is high
The advantages of.
Present invention also offers praseodymium oxide prepared by a kind of above method to load nanotube-palladium composite material.
Present invention also offers a kind of above method prepare praseodymium oxide load nanotube-palladium composite material it is styrene catalyzed plus
The purposes of hydrogen reaction.
The present invention using TOF values weigh the catalytic efficiency of catalyst in styrene hydrogenation reaction, and TOF is turn
Over frequency, and conversion frequency, its calculation formula are TOF=styrene (mol)/Pd (mol) * time (h).
In order to further illustrate the present invention, Technique of Nano Pd is loaded to a kind of praseodymium oxide provided by the invention with reference to embodiments
Composite and preparation method thereof is described in detail.
Reagent used is commercially available in following examples.
Embodiment 1
1.1Pr6O11The preparation of nano-bar material：By 800mg Pr (NO3)2·6H2O is added in 50ml deionized waters, magnetic
Power stirs 10 minutes, forms homogeneous solution；Ammoniacal liquor is added dropwise into the solution, adjustment pH value of solution is 8.0, is stirred 20 minutes；Should
Solution is transferred in 50ml reactors, is put into 120 DEG C of baking ovens, reacts 8h；Reactor is taken out, centrifugation is then with distillation water washing
Twice, washed one time with ethanol, be placed in 60 DEG C of vacuum drying chambers and dry 12h；Obtained powder is transferred in tube furnace,
600 DEG C are heated to, calcines 3h in atmosphere.
1.2 Na by 1.41ml concentration for 10mmol/L2PdCl4Mother liquor, it is added in the 20ml aqueous solution, is uniformly dispersed,
Form clear transparent solutions and obtain Na2PdCl4Solution, then add 100mg Pr6O11Nanometer rods, make contained element Pd in solution
Quality be Pr6O11The 1.0% of the quality of nanometer rods, ultrasound 10 minutes, reaction 12h is stirred at room temperature；By centrifugation and clearly
After washing, 12h is dried in 60 DEG C of vacuum drying chambers.
1.3 by above-mentioned powder in 5%H2Calcining obtains the praseodymium oxide (Pr with oxygen defect in/Ar mixed gas6O11) negative
Nanotube-palladium composite material is carried, calcining heat is 350 DEG C, calcination time 2h.
The praseodymium oxide load nanotube-palladium composite material obtained in embodiment 1 is analyzed using transmission electron microscope,
Its transmission electron microscope photo is obtained, as shown in Figure 1.
Embodiment 2
Embodiment 1 is repeated, there is following difference：In absorption of the palladium ion in nanorod surfaces, contained element in solution
Pd quality is Pr6O11The 1.5% of nanometer rods quality.
Measured through inductively coupled plasma technology (ICP), the actual negative carrying capacity of palladium is 1.42%.
Analyzed using ESEM obtaining praseodymium oxide load nanotube-palladium composite material in embodiment 2, obtain it and sweep
Electromicroscopic photograph is retouched, as shown in Figure 2.Figure it is seen that there is the praseodymium oxide (Pr of oxygen defect after calcining6O11) load Technique of Nano Pd
Composite maintains one-dimensional rod-like pattern.
The praseodymium oxide load nanotube-palladium composite material obtained in embodiment 2 is analyzed using transmission electron microscope,
Its transmission electron microscope photo is obtained, as shown in Figure 3.Find out the composite after the calcining of hydrogen argon from the transmission electron microscope photo shown in Fig. 3,
With the praseodymium oxide (Pr prepared by embodiment 16O11) supported palladium nano particle composite material compares (see Fig. 1), it is seen that Pr6O11Receive
Rice rod surface becomes more coarse.
The praseodymium oxide load nanotube-palladium composite material obtained in embodiment 2 is analyzed using X-ray diffraction, obtains it
XRD curves, as shown in Figure 4.The thing of made composite is mutually Pr as can be seen from Figure 46O11。
Fig. 5 is according to the praseodymium oxide (Pr manufactured in the present embodiment with oxygen defect6O11) load nanotube-palladium composite material
Electron paramagnetic resonance collection of illustrative plates, from made Pd/Pr as can be seen from Figure 56O11Composite compares Pr6O11Material is in g=2.002 positions
Obvious peak intensity is equipped with, illustrates Pd/Pr6O11There is Lacking oxygen in composite, and simple Pr6O11Do not have then.
Praseodymium oxide (the Pr obtained using embodiment 26O11) nanotube-palladium composite material is loaded as catalyst, styrene is urged
The catalytic performance for changing hydrogenation reaction is measured, and for wherein ethanol as solvent, reaction environment is the H of an atmospheric pressure2, as a result
The circulation of styrene catalytic hydrogenation reaction shown in the performance test curve and Fig. 9 of styrene catalytic hydrogenation shown in Figure 8
Performance curve.From figure 8, it is seen that when the actual negative carrying capacity of palladium, (data are to use inductively coupled plasma skill for 1.42%
What art was measured) when, at 40 minutes or so, styrene was fully converted into ethylbenzene, and its corresponding conversion frequency (TOF) is up to
8957.7h-1.It is worth noting that, single Pr6O11Carrier does not have the activity of styrene catalyzed hydrogenation reaction.Moreover, from figure
9 as can be seen that after the circulation catalytic reaction of continuous ten times, and the activity of only styrene catalytic hydrogenation reaction only reduces 4%.
Therefore, the praseodymium oxide (Pr with oxygen defect that prepared by the present invention6O11) supported palladium nano particle composite material has excellent urge
Change the performance and stability of styrene hydrogenation reaction.
Figure 10 is praseodymium oxide (Pr6O11) the styrene catalyzed hydrogenation reaction of supported palladium nano particle composite material flow signal
Figure.
Embodiment 3
Embodiment 1 is repeated, there is following difference：In absorption of the palladium ion in nanorod surfaces, contained element in solution
Pd quality is Pr6O11The 2.0% of nanometer rods quality.
The praseodymium oxide load nanotube-palladium composite material obtained in embodiment 3 is analyzed using transmission electron microscope,
Its transmission electron microscope photo is obtained, as shown in Figure 6.From fig. 6, it can be seen that quality and Pr with contained element Pd in solution6O11
The increase of the mass ratio of nanometer rods, surface roughness increase.Measured through inductively coupled plasma technology (ICP), the reality of palladium
Load capacity is 1.91%.
Embodiment 4
Embodiment 1 is repeated, difference is that the temperature of hydrogen argon gas calcining is 500 DEG C, calcination time 2h.
The praseodymium oxide load nanotube-palladium composite material obtained in embodiment 4 is analyzed using transmission electron microscope,
Its transmission electron microscope photo is obtained, as shown in figure 11.
Praseodymium oxide (the Pr obtained using embodiment 46O11) nanotube-palladium composite material is loaded as catalyst, styrene is urged
The catalytic performance for changing hydrogenation reaction is measured, and method of testing obtains the performance test of styrene catalytic hydrogenation with embodiment 2
Curve, as shown in figure 12.
Embodiment 5
Embodiment 1 is repeated, difference is that the temperature of hydrogen argon gas calcining is 350 DEG C, calcination time 4h.
The praseodymium oxide load nanotube-palladium composite material obtained in embodiment 5 is analyzed using transmission electron microscope,
Its transmission electron microscope photo is obtained, as shown in figure 13.
Praseodymium oxide (the Pr obtained using embodiment 56O11) nanotube-palladium composite material is loaded as catalyst, styrene is urged
The catalytic performance for changing hydrogenation reaction is measured, and method of testing obtains the performance test of styrene catalytic hydrogenation with embodiment 2
Curve, as shown in figure 14.
Comparative example 1
Embodiment 1 is repeated, there is following difference：Without palladium ion nanorod surfaces absorption, directly in 5%H2/
Pr is calcined under Ar atmospheric conditions6O11Nanometer rods.
Fig. 7 is the Pr after the calcining obtained by this comparative example6O11Nanometer rods transmission electron microscope photo, from figure 7 it can be seen that
Pr6O11Nanorod surfaces are smooth, hence it is evident that different from the Pr after absorption palladium ion6O11Nanometer rods results for calcination.
Using the Pr after the calcining obtained by comparative example 16O11Nanometer rods are catalyst, to styrene catalytic hydrogenation reaction
Catalytic performance is measured, and method of testing obtains the performance test curve of styrene catalytic hydrogenation, such as Figure 15 with embodiment 2
It is shown.
Claims (10)
- A kind of 1. preparation method of praseodymium oxide load nanotube-palladium composite material, it is characterised in that including：S1) by Pr6O11Nano material is distributed to the solution of containing palladium compound, stirring and adsorbing, the solid after being adsorbed；S2) solid after the absorption is calcined in reducing atmosphere high temperature, obtains praseodymium oxide load nanotube-palladium composite material.
- 2. preparation method according to claim 1, it is characterised in that the Pr6O11Nano material is according to following steps system It is standby：A1 after) praseodymium nitrate is mixed in aqueous with weak base, hydro-thermal reaction is carried out, obtains praseodymium hydroxide；A2) praseodymium hydroxide is calcined in atmosphere, obtains Pr6O11Nano material.
- 3. preparation method according to claim 2, it is characterised in that the step A1) in mix after system pH value be 8 ~10.
- 4. preparation method according to claim 2, it is characterised in that the step A1) in hydro-thermal reaction temperature be 110 DEG C~130 DEG C；The time of the hydro-thermal reaction is 6~10h；The step A2) in calcining temperature be 400 DEG C~800 DEG C；Institute The time for stating calcining is 1~5h.
- 5. preparation method according to claim 1, it is characterised in that the containing palladium compound is selected from Na2PdCl4、H2PdCl4 With K2PdCl4In one or more.
- 6. preparation method according to claim 1, it is characterised in that the matter of element palladium in the solution of the containing palladium compound Measure as Pr6O11The 1%~2% of nano material quality.
- 7. preparation method according to claim 1, it is characterised in that element palladium is dense in the solution of the containing palladium compound Spend for 0.4~1mmol/L.
- 8. preparation method according to claim 1, it is characterised in that the time of the stirring and adsorbing is 10~14h；It is described The time of high-temperature calcination is 300 DEG C~500 DEG C；The time of the high-temperature calcination is 1~4h.
- 9. the praseodymium oxide load nanotube-palladium composite material prepared by claim 1~8 any one.
- 10. the praseodymium oxide load styrene catalyzed hydrogenation reaction of nanotube-palladium composite material prepared by claim 1~8 any one Purposes.
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