CN105728039A - Fullerene derivative/palladium nanoparticle film and preparation method and application thereof - Google Patents
Fullerene derivative/palladium nanoparticle film and preparation method and application thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 129
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 83
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 66
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 238000004062 sedimentation Methods 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005030 aluminium foil Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 108010077895 Sarcosine Proteins 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229940043230 sarcosine Drugs 0.000 claims description 5
- 125000003184 C60 fullerene group Chemical group 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 4
- 230000002085 persistent effect Effects 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 208000012839 conversion disease Diseases 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000000151 deposition Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000009713 electroplating Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- VCSZKSHWUBFOOE-UHFFFAOYSA-N dioxidanium;sulfate Chemical compound O.O.OS(O)(=O)=O VCSZKSHWUBFOOE-UHFFFAOYSA-N 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 2
- 241000238370 Sepia Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 0 *c1ccc(C=O)cc1 Chemical compound *c1ccc(C=O)cc1 0.000 description 1
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001652 electrophoretic deposition Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/646—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of aromatic or heteroaromatic rings
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Metallurgy (AREA)
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Abstract
The invention discloses a method for preparing a fullerene derivative/palladium nanoparticle film, which comprises the following steps: 1) synthesizing a fullerene derivative; 2) preparing nano particles of the fullerene derivative by a solvent method; 3) preparing a film of fullerene derivative nanoparticles by a deposition method; 4) and preparing the fullerene derivative/palladium nano-particle film by an electroplating method. In addition, the invention also discloses the fullerene derivative/palladium nanoparticle film prepared by the preparation method and application of the fullerene derivative/palladium nanoparticle film as a catalyst in catalytic hydrogenation reaction. The surface active centers of the nano-particle film are all in nano-scale and have uniform particle size distribution; meanwhile, a nanoparticle film formed by the fullerene derivative not only forms a direct carrier of the palladium nanoparticles, but also has good surface properties to generate good promotion effect on palladium active centers. Finally, when the nano-particle film is used as a catalyst for catalytic hydrogenation, the problems of low catalytic activity, low reaction conversion rate and low product selectivity of the existing carrier palladium catalyst are greatly improved.
Description
Technical field
The invention belongs to field of nanometer technology, relate to a kind of composite film material, especially relate to nanometer particle film of a kind of fullerene derivate/palladium and its preparation method and application.
Background technology
In organic catalysis hydrogenation, the hydrogenation catalyst with higher catalytic activity is the key of reaction.Current industrial conventional hydrogenation catalyst includes low-pressure hydrogenation catalyst and high-pressure hydrogenation catalyst, and mostly these catalyst are heterogeneous catalysis, especially supported heterogeneous catalysis.Such as, in the catalytic hydrogenation that nitrobenzene reduction is aniline, conventional catalyst is carrier palladium.These catalyst have some superiority in catalysis activity, reaction conversion ratio and selectivity of product etc., have building-up process simple simultaneously, and the features such as cost of material is low, are the Main way of present stage heterogeneous catalysis research.
For supported palladium catalyst, the carrier material such as activated carbon, coconut husk, ature of coal carbon, staple fibre carbon is all relatively common carrier.In catalytic reaction, the palladium on surface is only active center, and carrier plays very big effect, and palladium high-area carbon is for promoting reactant most important with contacting of active center.Additionally, the interaction between the dispersion of palladium and grain size and palladium and carrier is also the key factor affecting catalytic hydrogenation.But, existing supported palladium catalyst yet suffers from all deficiencies of catalysis activity, reaction conversion ratio and selectivity of product, and meanwhile, the structure of this kind of catalyst and catalytic mechanism are also relatively fuzzyyer.
In recent years, nanometer carbon material supported metal catalyst is subject to everybody extensive concern.These carbon nanomaterials include fullerene, CNT and Graphene etc..They have strong delocalizedπelectron, significant conjugation and have good heat conductivility and mechanical property etc., be of value to and put forward high catalytic activity, reaction conversion ratio and selectivity of product in catalytic process.But, the nanometer carbon material supported performance using routine is not ideal enough, still can not fully meet industry needs, it is necessary to structure and composition and preparation technology to material are improved further.One of research direction is namely based on composite film material, especially the heterogeneous carried catalyst of nanometer particle film.
For the preparation technology of nanometer particle film, presently, there are compound electric plating method, composite chemical plating method and Composite Brush plating etc..These methods have with having different in preparation technology, are respectively arranged with quality.Composite plating method is prepared composite film material and is obtained very big progress, but still there are some problems, the difficult point of research essentially consists in deposit in aqueous due to carbon nanomaterial in composite plating very easily reunites, and cause coating surface coarse and uneven, limit its potentiation in the composite.Composite chemical plating method is affected relatively big by solution state, and technology stability and concordance are unsatisfactory.Electrophoretic deposition is a kind of novel film coating preparation method, and sedimentary condition is gentle, generally can carry out at normal temperatures；Equipment needed thereby is simple, and cost is low.It is by regulating voltage or electric current, it is easy to the microstructure of sedimentation rate and coating is controlled；Deposition process is a non-rectilinear process, is suitable to complex-shaped, the multiple base material of porous surface.For nanometer particle film, selecting which kind of preparation technology, direct relation the catalytic performance quality of carried catalyst, also directly affects reaction conversion ratio and selectivity of product.
Therefore, in the urgent need to finding the preparation method of a kind of new nanometer particle film and by the obtained nanometer particle film of the method.
Summary of the invention
It is an object of the present invention to provide the preparation method of a kind of new nanometer particle film and by the obtained nanometer particle film of the method, to solve the problem that catalysis activity is not high, reaction conversion ratio is not high and selectivity of product is not high that existing supported palladium catalyst exists.
For achieving the above object, on the one hand, the present invention by the following technical solutions: a kind of method of nanometer particle film preparing fullerene derivate/palladium, comprise the steps:
1) following fullerene derivate is synthesized；
2) solvent method prepares the nano-particle of fullerene derivate；
3) sedimentation prepares the thin film of fullerene derivate nano-particle；
4) galvanoplastic prepare the nanometer particle film of fullerene derivate/palladium.
According to aforesaid preparation method, wherein, described step 1) fullerene derivate by C60, P-methoxybenzal-dehyde and sarcosine be obtained by reacting.
C60, P-methoxybenzal-dehyde and sarcosine amount of substance than for 1:(2-8): (1-6), it is preferred to 1:(3-7): (2-5), it is most preferred that for 1:(4-6): (3-4).Three reacts 1-24h at 100-150 DEG C.Cool down after reaction, filter, concentrate and column chromatography for separation.During column chromatography for separation, successively with (60-90 DEG C), VToluene:VPetroleum etherThe mixed solvent of=1:4 and VToluene:VPetroleum etherThe mixed solvent of=1:1 is as eluent.Finally use methanol washing and vacuum drying.
According to aforesaid preparation method, wherein, described step 2) solvent method be that fullerene derivate is dissolved in good solvent, then mix than with pessimum solvent with certain volume, obtain nano suspending liquid；It is centrifuged subsequently, washing, obtains the nano-particle of fullerene derivate.
Described good solvent is selected from chloroform, toluene, Carbon bisulfide, normal hexane, o-dichlorohenzene.Described pessimum solvent selected from methanol, ethanol, propanol, isopropanol, butanol, Hexalin, water.The volume ratio of good solvent and pessimum solvent is 1:3 to 1:10, it is preferred to 1:4 to 1: 8, it is most preferred that for 1:5 to 1:7.
In a specific embodiment, described good solvent is selected from chloroform and toluene, and it is 1:5 to 1:10 that described pessimum solvent is selected from the volume ratio of propanol and isopropanol, good solvent and pessimum solvent.
According to aforesaid preparation method, wherein, described step 3) sedimentation as follows: aluminium foil sand papering, cleaning, drying；Prepare the nano suspending liquid of fullerene derivate；Stainless steel anode is placed in nano suspending liquid, aluminium foil above is placed in nano suspending liquid as negative electrode, be deposited under the DC source effect under constant voltage mode.
The voltage of described DC source constant voltage mode is 50V, constant voltage mode persistent period 100-500s, it is preferred to 200-450s, it is most preferred that for 250-400s.
According to aforesaid preparation method, wherein, described step 4) galvanoplastic as follows: preparation 1-10g/L palladium sulfate solution；By step 3) electrode runs parallel put in palladium sulfate solution by the thin film of gained fullerene derivate nano-particle, platinum, and electro-deposition obtains the nanometer particle film of fullerene derivate/palladium.
The process conditions of described electro-deposition are as follows: spacing 1-4cm；Electric current density is 0.5-5mA/cm2, sedimentation time 200-400s.Preferably, spacing 2-3cm；Electric current density is 1-4mA/cm2, sedimentation time 240-360s.
On the other hand, present invention also offers a kind of nanometer particle film by the fullerene derivate/palladium prepared by aforesaid preparation method.
Another aspect, the invention provides the nanometer particle film of a kind of aforesaid fullerene derivate/palladium as catalyst application in catalytic hydrogenation.In a specific embodiment, described catalytic hydrogenation is nitrobenzene reduction is the catalytic hydrogenation of aniline.Advantageously, when catalytic reaction starts, the nanometer particle film of fullerene derivate and palladium is ground into the granule of 80-120 order.
Compared with prior art, the nanometer particle film Active sites being prepared the obtained fullerene derivate/palladium of the method for the nanometer particle film of fullerene derivate/palladium by the present invention is in nanoscale and even particle size distribution；Meanwhile, the nanometer particle film that fullerene derivate is formed not only constitutes the direct carrier of palladium nano-particles, and palladium active center is also created good facilitation by the surface nature that fullerene derivate is good.When finally making the catalyst that this type of nanometer particle film is used as catalytic hydrogenation, substantially improve the problem that catalysis activity is not high, reaction conversion ratio is not high and selectivity of product is not high that existing supported palladium catalyst exists.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention will be further described
In the present invention, if not refering in particular to, all percentage ratios are unit of weight, all devices and raw material and all can buy from market or the industry is conventional, the method in following embodiment, if no special instructions, are this area conventional method.
Embodiment 1 fullerene synthesis derivant
Take 720mgC60Being dissolved in 80mL newly to steam in toluene, under argon shield, magnetic agitation is about 1.5h and makes it be completely dissolved, and adds 400mg sarcosine and 408mg P-methoxybenzal-dehyde (before using re-distillation), wherein C60, P-methoxybenzal-dehyde and sarcosine amount of substance than for 1:5:3,100min is fully reacted at 120 DEG C, solution is become sepia from purple, continue to pass into argon in reaction mixture, allow to cool to room temperature, it being filtered, concentrates and column chromatography for separation, rotary evaporation removes solvent, does not first participate in the C of reaction with petroleum ether (60-90 DEG C) for eluant drip washing60, then with VToluene:VPetroleum ether=1:4 is the C of eluent drip washing residual60, then with VToluene:VPetroleum ether=1:1 is eluent drip washing sepia product band, products therefrom solution carries out concentration in Rotary Evaporators be spin-dried for, then dark-brown powder can be obtained 2-3 time with HPLC methanol wash column, vacuum drying 12h, namely brown-black powder shape product is obtained, its productivity is 27.5%, and this product is dissolved in chloroform, toluene, Carbon bisulfide, normal hexane, o-dichlorohenzene equal solvent, and synthetic route is as follows.
Infrared absorption spectroscopy (KBr tabletting), wherein: 526cm-1, 572cm-1, 1170cm-1, 1427cm-1The absworption peak at place is attributed to C60Characteristic absorption peak, 1460cm-1, 1512cm-1, 1610cm-1Place is the skeleton stretching vibration absworption peak of phenyl ring, additionally at 2777cm-1, 2827cm-1, 2908cm-1, 2962cm-1It is attributed to hydrocarbon stretching vibration peak.
In ultraviolet-ray visible absorbing, 289nm, 333nm, 344nm are C60, there is the little spike of 1 feature in characteristic peak, this peak is the C of [6,6] closed-loop structure near 431nm60The characteristic absorption peak of single additive derivative, has a weak parcel peak, relative to C near 700nm60It is moved to long wave direction.
1In H nuclear magnetic resoance spectrum, wherein 2.81 (3H s) is attributed to-N-CH3, 3.82 (3H s) is attributed to-O-CH3, 4.26 (1H, d) He 4.97 (1H d) is attributed to pyrrole ring C60-CH2The hydrogen of-N, 4.89 (1H s) is attributed to pyrrole ring C60The hydrogen of-CH-N, 7.69 (2H, d), 6.94 (2H d) is attributed to the hydrogen of phenyl ring.
Embodiment 2A solvent method prepares the nano-particle of fullerene derivate
The fullerene derivate of embodiment 1 is dissolved in toluene, prepare the toluene solution of 1g/L fullerene derivate, then according to after toluene solution mixes with propanol by the ratio of volume ratio 1:10, stir 2h under room temperature, obtain the nano suspending liquid of fullerene derivate.When rotating speed 5000r/min, above-mentioned nano suspending liquid being centrifuged, centrifugation time is 10min；Use ethanol water to be carried out separating the solid obtained subsequently, obtain the nano-particle of fullerene derivate, and at room temperature dry.
By SEM and TEM electronic microscope photos, it is possible to find that the nano-particle of prepared fullerene derivate is substantially spherical in shape.Additionally, use laser particle size analyzer to measure the D of fullerene derivate nano-particle90Diameter is 94nm.
Embodiment 2B solvent method prepares the nano-particle of fullerene derivate
The fullerene derivate of embodiment 1 is dissolved in chloroform, prepare the toluene solution of 10g/L fullerene derivate, then according to after chloroform soln mixes with isopropanol by the ratio of volume ratio 1: 5, stir 6h under room temperature, obtain the nano suspending liquid of fullerene derivate.When rotating speed 5000r/min, above-mentioned nano suspending liquid being centrifuged, centrifugation time is 15min；Use ethanol water to be carried out separating the solid obtained subsequently, obtain the nano-particle of fullerene derivate, and at room temperature dry.
By SEM and TEM electronic microscope photos, it is possible to find that the nano-particle of prepared fullerene derivate is substantially spherical in shape.Additionally, use laser particle size analyzer to measure the D of fullerene derivate nano-particle90Diameter is 105nm.
Embodiment 2C solvent method prepares the nano-particle of fullerene derivate
The fullerene derivate of embodiment 1 is dissolved in normal hexane, prepare the toluene solution of 5g/L fullerene derivate, then according to after chloroform soln mixes with isopropanol by the ratio of volume ratio 1:3, stir 4h under room temperature, obtain the nano suspending liquid of fullerene derivate.When rotating speed 5000r/min, above-mentioned nano suspending liquid being centrifuged, centrifugation time is 20min；Use ethanol water to be carried out separating the solid obtained subsequently, obtain the nano-particle of fullerene derivate, and at room temperature dry.
By SEM and TEM electronic microscope photos, it is possible to find that the nano-particle of prepared fullerene derivate is substantially spherical in shape.Additionally, use laser particle size analyzer to measure the D of fullerene derivate nano-particle90Diameter is 112nm.
Embodiment 3A-3C sedimentation prepares the thin film of fullerene derivate nano-particle
First the aluminium foil that thickness is 80 μm is polishing to surface through abrasive paper for metallograph uniformly bright.Then it is placed in distilled water, ultrasonic cleaning 10min；It is placed in acetone post processing 10min again, cleans with distilled water subsequently, dry.Weigh the fullerene derivate nano-particle of 50mg embodiment 2A-2C respectively, add in the beaker filling 100mL distilled water and appropriate amount of PEG 200, sonic oscillation 2h, obtain fullerene derivate nano suspending liquid.Stainless steel anode is placed in nano suspending liquid, aluminium foil above is placed in nano suspending liquid as negative electrode, direct current power source voltage is adjusted to 50V, electric current is adjusted to zero place, opening power, rapid high current, power supply output is made to be changed into rapidly constant voltage mode, persistent period 360s.After having deposited, respectively obtain the thin film of the fullerene derivate nano-particle of embodiment 3A-3C, dry.
Embodiment 4A-4C galvanoplastic prepare the nanometer particle film of fullerene derivate/palladium
Weighing 0.3g sulfate dihydrate palladium and be placed in beaker, add deionized water to 100mL, after stirring 10min, ultrasonic 10min clarifies to solution.Electrode runs parallel is put in electric depositing solution by the thin film of embodiment 3A-3C gained fullerene derivate nano-particle, platinum, adjusts its spacing and be about 2cm.Adopting potentiostat to electroplate, control electric current density is 1mA/cm2, sedimentation time 300s, electroplates complete, cleans film surface with deionized water, after drying, respectively obtain the nanometer particle film of the fullerene derivate/palladium of embodiment 4A-4C.
By SEM electron microscopic observation, the nanometer particle film surface of fullerene derivate/palladium that embodiment 4A-4C is obtained is equally distributed palladium nano-particles, particle diameter 20～60nm.By EDS elementary analysis, the nanometer particle film of fullerene derivate/palladium is mainly C, Al, Pd peak.
Comparative example 1 galvanoplastic prepare the nanometer particle film of palladium
Weighing 0.3g sulfate dihydrate palladium and be placed in beaker, add deionized water to 100mL, after stirring 10min, ultrasonic 10min clarifies to solution.Electrode runs parallel is put in electric depositing solution by the blank aluminium foil, the platinum that are used by embodiment 3A-3C, adjusts its spacing and is about 2cm.Adopting potentiostat to electroplate, control electric current density is 1mA/cm2, sedimentation time 300s, electroplates complete, cleans film surface with deionized water, after drying, obtain the palladium nano-particles thin film of comparative example 1.
By SEM electron microscopic observation, the obtained palladium nano-particles film surface of comparative example 1 is equally distributed palladium nano-particles, particle diameter 30～100nm.By EDS elementary analysis, palladium nano-particles thin film is mainly Al, Pd peak.
Comparative example 2 galvanoplastic prepare the nanometer particle film of fullerene and palladium
First the aluminium foil that thickness is 80 μm is polishing to surface through abrasive paper for metallograph uniformly bright.Then it is placed in distilled water, ultrasonic cleaning 10min；It is placed in acetone post processing 10min again, cleans with distilled water subsequently, dry.What weigh 50mg is purchased fullerene C60, add in the beaker filling 100mL distilled water and appropriate amount of PEG 200, sonic oscillation 2h, obtain fullerene suspension.Stainless steel anode is placed in nano suspending liquid, aluminium foil above is placed in suspension as negative electrode, direct current power source voltage is adjusted to 50V, electric current is adjusted to zero place, opening power, rapid high current, power supply output is made to be changed into rapidly constant voltage mode, persistent period 360s.After having deposited, the fullerene thin film obtained, dry.Weighing 0.3g sulfate dihydrate palladium and be placed in beaker, add deionized water to 100mL, after stirring 10min, ultrasonic 10min clarifies to solution.Electrode runs parallel is put in electric depositing solution by gained fullerene thin film, platinum, adjusts its spacing and be about 2cm.Adopting potentiostat to electroplate, control electric current density is 1mA/cm2, sedimentation time 300s, electroplates complete, cleans film surface with deionized water, after drying, obtain the fullerene of comparative example 2 and the nanometer particle film of palladium.
By SEM electron microscopic observation, fullerene and the nanometer particle film surface of palladium that comparative example 2 is obtained are equally distributed palladium nano-particles, particle diameter 20～150nm.It is mainly C, Al, Pd peak by the nanometer particle film of EDS elementary analysis, fullerene and palladium.
Application Example 1A-1C and Application comparison example 1-2
The nanometer particle film of the palladium nano-particles thin film obtained first by the pulverizer nanometer particle film by fullerene derivate/palladium obtained for embodiment of the present invention 4A-4C and comparative example 1 and the obtained fullerene derivate of comparative example 2 and palladium is ground into the granule of 80-120 order.Carry out, on conventional addition cure bed bioreactor, the catalytic hydrogenation that nitrobenzene reduction is aniline subsequently.The embodiment of the present invention 4A-4C used and the granule of comparative example 1 make consumption be Nitrobenzol 10%, process conditions are temperature 250 DEG C, pressure 1.5MPa.After calculating 24h, the reaction that the catalyst granules of embodiment of the present invention 4A-4C and comparative example 1-2 participates in is respectively as Application Example 1A-1C and Application comparison example 1-2.The conversion ratio of Nitrobenzol and the selectivity of aniline are as shown in table 1 below.
Table 1
| Conversion ratio | Selectivity | |
| Application Example 1A | 94.27% | 86.06% |
| Application Example 1B | 91.68% | 84.77% |
| Application Example 1C | 93.52% | 85.23% |
| Application comparison example 1 | 62.27% | 49.22% |
| Application comparison example 2 | 82.45% | 71.47% |
As can be seen from Table 1, the catalyst prepared by nanometer particle film of the fullerene derivate/palladium of Application Example 1A-1C of the present invention is compared with Application comparison example 1-2, the Active sites of the nanometer particle film of the fullerene derivate/palladium of the present invention is in nanoscale and even particle size distribution；Meanwhile, the nanometer particle film that fullerene derivate is formed not only constitutes the direct carrier of palladium nano-particles, and palladium active center is also created good facilitation by the surface nature that fullerene derivate is good.Meanwhile, compared with prior art, the conversion ratio of Nitrobenzol and the selectivity of aniline are all remarkably higher than the catalyst of Application comparison example 1-2.
The present invention also can have other various embodiments, and when without departing substantially from the present invention and essence thereof, those skilled in the art makes corresponding change and deformation according to invention, but these changes accordingly and deformation all should belong to the protection domain of the claims in the present invention.
Claims (10)
1. the method preparing the nanometer particle film of fullerene derivate/palladium, comprises the steps:
1) following fullerene derivate is synthesized；
2) solvent method prepares the nano-particle of fullerene derivate；
3) sedimentation prepares the thin film of fullerene derivate nano-particle；
4) galvanoplastic prepare the nanometer particle film of fullerene derivate/palladium.
2. preparation method according to claim 1, wherein, described step 1) fullerene derivate by C60, P-methoxybenzal-dehyde and sarcosine be obtained by reacting.
3. preparation method according to claim 1, wherein, described step 2) solvent method be that fullerene derivate is dissolved in good solvent, then mix than with pessimum solvent with certain volume, obtain nano suspending liquid；It is centrifuged subsequently, washing, obtains the nano-particle of fullerene derivate.
4. preparation method according to claim 3, wherein, described good solvent is selected from chloroform and toluene, and it is 1:5 to 1:10 that described pessimum solvent is selected from the volume ratio of propanol and isopropanol, good solvent and pessimum solvent.
5. preparation method according to claim 1, wherein, described step 3) sedimentation as follows: aluminium foil sand papering, cleaning, drying；Prepare the nano suspending liquid of fullerene derivate；Stainless steel anode is placed in nano suspending liquid, aluminium foil above is placed in nano suspending liquid as negative electrode, be deposited under the DC source effect under constant voltage mode.
6. preparation method according to claim 5, wherein, the voltage of described DC source constant voltage mode is 50V, constant voltage mode persistent period 100-500s.
7. preparation method according to claim 1, wherein, described step 4) galvanoplastic as follows: the palladium sulfate solution of preparation 1-10g/L；By step 3) electrode runs parallel put in palladium sulfate solution by the thin film of gained fullerene derivate nano-particle, platinum, and electro-deposition obtains the nanometer particle film of fullerene derivate/palladium.
8. preparation method according to claim 7, wherein, the process conditions of described electro-deposition are as follows: spacing 1-4cm；Electric current density is 0.5-5mA/cm2, sedimentation time 200-400s.
9. the nanometer particle film of fullerene derivate/palladium, it is characterised in that obtained by the preparation method described in any one of claim 1-8.
10. the nanometer particle film of the fullerene derivate/palladium described in claim 9 is as catalyst application in catalytic hydrogenation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245051A (en) * | 2017-07-04 | 2017-10-13 | 黄山学院 | A kind of preparation method of 3,4 fullerene chemistries of N methyl 2 (4 nitrobenzophenone) |
| CN109627203A (en) * | 2018-12-13 | 2019-04-16 | 黄山学院 | One kind containing 2- (2- bigcatkin willow aldehyde radical) ethyoxyl-phenyl fullerene chemistry preparation method and application |
| CN113926487A (en) * | 2021-09-14 | 2022-01-14 | 杭州师范大学 | Fullerol/palladium nano composite photocatalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002747A (en) * | 2009-09-01 | 2011-04-06 | 宝山钢铁股份有限公司 | Method for preparing metal surface fullerene film by electrophoresis |
| CN102041543A (en) * | 2009-10-20 | 2011-05-04 | 宝山钢铁股份有限公司 | Preparation method of fullerene/metal composite film on metal surface |
| CN103936660A (en) * | 2014-05-07 | 2014-07-23 | 黄山学院 | Preparation method and application of micron acicular-structure N-methyl-2-phenyl-3,4-fullerenylpyrrolidine |
| CN103965570A (en) * | 2014-05-05 | 2014-08-06 | 北京吉安信科技有限公司 | Preparation method for composite material of hydrophilic fullerene derivative and metallic oxide |
| CN104785247A (en) * | 2015-04-17 | 2015-07-22 | 东华大学 | Preparation method of fullerene loaded flower-shaped platinum catalyst |
-
2016
- 2016-03-15 CN CN201610151440.6A patent/CN105728039B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002747A (en) * | 2009-09-01 | 2011-04-06 | 宝山钢铁股份有限公司 | Method for preparing metal surface fullerene film by electrophoresis |
| CN102041543A (en) * | 2009-10-20 | 2011-05-04 | 宝山钢铁股份有限公司 | Preparation method of fullerene/metal composite film on metal surface |
| CN103965570A (en) * | 2014-05-05 | 2014-08-06 | 北京吉安信科技有限公司 | Preparation method for composite material of hydrophilic fullerene derivative and metallic oxide |
| CN103936660A (en) * | 2014-05-07 | 2014-07-23 | 黄山学院 | Preparation method and application of micron acicular-structure N-methyl-2-phenyl-3,4-fullerenylpyrrolidine |
| CN104785247A (en) * | 2015-04-17 | 2015-07-22 | 东华大学 | Preparation method of fullerene loaded flower-shaped platinum catalyst |
Non-Patent Citations (2)
| Title |
|---|
| BO JIN ET AL.: ""Reactions of [62]Fullerene with Halides and Amino Acids to Synthesize Fulleropyrrolidines"", 《EUR. J. ORG. CHEM.》 * |
| 黄飞等: ""富勒烯C60及其衍生物材料的应用研究进展"", 《黄山学院学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245051A (en) * | 2017-07-04 | 2017-10-13 | 黄山学院 | A kind of preparation method of 3,4 fullerene chemistries of N methyl 2 (4 nitrobenzophenone) |
| CN109627203A (en) * | 2018-12-13 | 2019-04-16 | 黄山学院 | One kind containing 2- (2- bigcatkin willow aldehyde radical) ethyoxyl-phenyl fullerene chemistry preparation method and application |
| CN113926487A (en) * | 2021-09-14 | 2022-01-14 | 杭州师范大学 | Fullerol/palladium nano composite photocatalyst and preparation method and application thereof |
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