CN108144631A - The preparation method of transition metal sulfide catalyst, preparation method and aromatic amine compound - Google Patents
The preparation method of transition metal sulfide catalyst, preparation method and aromatic amine compound Download PDFInfo
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- CN108144631A CN108144631A CN201711419312.6A CN201711419312A CN108144631A CN 108144631 A CN108144631 A CN 108144631A CN 201711419312 A CN201711419312 A CN 201711419312A CN 108144631 A CN108144631 A CN 108144631A
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- transition metal
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- metal sulfide
- sulfide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- -1 transition metal sulfide Chemical class 0.000 title claims abstract description 80
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 64
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 19
- 230000001052 transient effect Effects 0.000 claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 238000006555 catalytic reaction Methods 0.000 claims description 21
- 239000003638 chemical reducing agent Substances 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 17
- 150000003624 transition metals Chemical class 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000002604 ultrasonography Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 31
- 230000009467 reduction Effects 0.000 description 19
- 230000000694 effects Effects 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 239000004809 Teflon Substances 0.000 description 13
- 229920006362 Teflon® Polymers 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000002274 desiccant Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/33—
-
- B01J35/393—
-
- B01J35/394—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The present invention provides a kind of transition metal sulfide catalysts, are made of redox graphene and the transient metal sulfide for being carried on the redox graphene surface.Present invention also provides a kind of preparation methods of transition metal sulfide catalyst.Present invention also provides the methods that aromatic amine compound is prepared using transition metal sulfide catalyst.The transition metal sulfide catalyst that the application provides using transient metal sulfide as main active, redox graphene as carrier while also with certain catalytic activity, make catalyst have the characteristics that high conversion with it is highly selective.
Description
Technical field
The present invention relates to catalyst synthesis technology field more particularly to a kind of transition metal sulfide catalyst, its preparations
The preparation method of method and aromatic amine compound.
Background technology
Aromatic amine compound is particularly important organic synthesis intermediate, is widely used in dyestuff, pesticide and medicine
Synthesis.Aromatic amine is generally obtained by reducing aromatic nitro compound, and common restoring method includes metal/acid reduction method and catalysis
Hydrogenation method, but the generation of a large amount of metal mud can be caused using metal/acid catalyst, catalytic hydrogenation method generally requires under high pressure
It carries out, thus higher requirement is proposed to the security performance of equipment.Hydration in above-mentioned restoring method as liquid-phase reduction agent
Hydrazine has certain toxicity, and in comparison, sodium borohydride has the features such as cheap, nontoxicity, reaction condition is mild, therefore
Sodium borohydride is a kind of good reducing agent.It is traditionally used for the catalyst of sodium borohydride catalyzing Reduction of Aromatic Nitro Compounds
There are Pd/C, Pt, Au and Ag, but they are noble metal, it is expensive, therefore develop a kind of cheap new catalyst and particularly compel
It cuts.
In recent years, iron catalyst such as Fe (III) compound, FeO (OH) etc. use more, such catalyst price is low
It is honest and clean, but FeO (OH) catalyst can be converted into α-Fe when temperature is higher than 70 DEG C2O3, lead to rapid catalyst deactivation.Therefore, it grinds
Send out efficient and cheap catalyst seems extremely urgent to be catalyzed Reduction of Aromatic Nitro Compounds.
Graphene assigns the ratio table of its super large as a kind of new carbon, the two-dimensional structure of unique monoatomic layer thickness
Area, theoretical specific surface area are up to 2600m2/ g far above existing other materials, while has fabulous mechanical performance, heat
Performance and electric property are learned, is held out broad prospects in terms of catalytic applications.Grapheme material by graphite, graphite oxide and its can spread out
Prepared by biology, can realize mass production.The conjugated structure of graphene makes it have stronger adsorption capacity to reaction raw materials,
Fabulous electronic transmission performance can promote the electron transfer in catalysis reaction, and so as to improve catalytic activity, thus graphene both may be used
Active component as catalyst can also be used as carrier.Traditional hydrogenation catalyst is generally support type, and carrier material is used as
Supporting medium, some carriers do not provide activated centre, only provide larger surface with load active component, make its keep high dispersive,
High activity；Some carriers can also coordinate active component to play synergistic effect, regulate and control the activity or selectivity of catalyst.Graphene is special
Different structure feature cause its can with high dispersive, the load active component of high stable, the microscopic property of regulation activity component, and
There is higher adsorptivity to hydrogen molecule, be ideal catalyst carrier for hydrgenating.Therefore, the load of transition metal can be used as
Body prepares the catalyst of high efficiency low cost, for being catalyzed Reduction of Aromatic Nitro Compounds.
Invention content
Present invention solves the technical problem that it is to provide a kind of transition metal sulfide catalyst, the transition that the application provides
Metal sulfide catalyst as the catalyst for preparing aromatic amine compound there is high conversion, highly selective and high circulation to stablize
The characteristics of property.
In view of this, this application provides a kind of transition metal sulfide catalyst, by redox graphene and load
Transient metal sulfide in the redox graphene surface forms.
Preferably, the transition metal in the transient metal sulfide is in VIII group, IB races and Group IIB transition metal
One or more metallic elements, and not include Ru, Rh, Pt and Ir.
Preferably, the transient metal sulfide is selected from FeS, CoS or NiS.
Present invention also provides a kind of preparation method of transition metal sulfide catalyst, including：
Transition metal salt, sulfide, reducing agent, dispersant, water and graphene oxide are mixed, the water in autoclave
Thermal response obtains transition metal sulfide catalyst.
Preferably, the reducing agent is one or more in ethylene glycol, glycerine, acetaldehyde and propionic aldehyde；The dispersion
Agent is PVP (K-30)；The transition metal salt is transition metal nitrate；Transition metal in the transition metal salt is selected from
One or more metallic elements in VIII group, IB races and Group IIB transition metal, and do not include Ru, Rh, Pt and Ir；The sulphur
Compound is inorganic sulphide, selected from Na2S、K2S、(NH4)2SO4In it is one or more.
Preferably, the molar ratio of the transition metal salt and the sulfide is (0.5~2)：1.
Preferably, it is further included before mixing：
Graphene oxide powder is dispersed to ultrasound stripping in aqueous solution, obtains graphene oxide dispersion.
Preferably, the temperature of the hydro-thermal reaction is 150~200 DEG C, and the time is 24~36h.
Present invention also provides a kind of preparation method of aromatic amine compound, including：
Aromatic nitro compound, reducing agent, catalyst and water are subjected to water-bath, obtain aromatic amine compound；It is described
Catalyst is the transition metal sulfide catalyst prepared by the preparation method described in described in said program or said program.
Preferably, the reducing agent is sodium borohydride or potassium borohydride.
This application provides a kind of transition metal sulfide catalysts, by redox graphene and are carried on described go back
The transient metal sulfide composition of former surface of graphene oxide.The application is fragrant as preparing using transition metal sulfide catalyst
The catalyst of amine compounds, due to also having certain catalytic activity while redox graphene is as carrier；Mistake simultaneously
The transition metal crossed in metal sulfide has special 3d valence electron shell structurres, and special electronic structure imparts transition
The good chemical property of metal sulfide, the catalyst so as to make can quickly obtain aromatic amine compound at normal temperatures,
Make catalyst that there is high conversion, highly selective and high circulation stability.Further, the catalysis that the application provides
Agent is heterogeneous catalysis, can quick separating after the completion of reaction, realize recycling.
Description of the drawings
Fig. 1 is the principle schematic that the present invention prepares aromatic amine compound；
Fig. 2 is FeS@rGO stereoscan photographs prepared by the embodiment of the present invention 1；
Fig. 3 is FeS@rGO XRD spectras prepared by the embodiment of the present invention 1；
Fig. 4 is FeS@rGO catalysis 4-NP reduction effect figures prepared by the embodiment of the present invention 1；
Fig. 5 is CoS@rGO stereoscan photographs prepared by the embodiment of the present invention 2；
Fig. 6 is CoS@rGO XRD spectras prepared by the embodiment of the present invention 2；
Fig. 7 is CoS@rGO catalysis 4-NP reduction effect figures prepared by the embodiment of the present invention 2；
Fig. 8 is NiS@rGO stereoscan photographs prepared by the embodiment of the present invention 3；
Fig. 9 is NiS@rGO XRD spectras prepared by the embodiment of the present invention 3；
Figure 10 is NiS@rGO catalysis 4-NP reduction effect figures prepared by the embodiment of the present invention 3.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are only for the feature and advantage that further illustrate the present invention rather than to the claims in the present invention
Limitation.
For the catalyst for preparing aromatic amine compound in the prior art it is on the high side the problem of, the embodiment of the present invention discloses
A kind of transition metal sulfide catalyst, the catalyst are cheap and efficiently；Specifically, this application provides a kind of transition metal
Sulfide catalyst, by redox graphene and the transient metal sulfide group for being carried on the redox graphene surface
Into.
In this application, the transition metal sulfide catalyst is by redox graphene and transient metal sulfide group
Into wherein transient metal sulfide is carried on the redox graphene surface.Graphene is as a kind of New Two Dimensional carbon materials
Material, huge specific surface area cause it can be with high dispersive, the load active component of high stable, and conjugated structure makes it to reaction
Raw material has stronger adsorption capacity, and fabulous electronic transmission performance can promote the electron transfer in catalysis reaction, so as to change
Kind catalytic activity, thus it can not only be used for the active component of catalyst can also be used as carrier, and then play collaboration to catalysis reaction
Effect regulates and controls the activity or selectivity of catalyst；And redox graphene has better electric conductivity；The Transition Metal Sulfur
Compound has special 3d valence electron shell structurres, and special electronic structure assigns its good chemical property, born
Redox graphene surface is loaded in, can further improve its activity.
Transition metal in the application in most transient metal sulfides is selected from VIII group, IB races and Group IIB transition metal
In one or more metallic elements, and not include Ru, Rh, Pt and Ir；Specifically, the transition metal may be selected from Fe, Co,
Cu, Zn or Ni；In a particular embodiment, the transition metal is selected from Fe, Co or Ni.Herein described transient metal sulfide choosing
From FeS, CoS or NiS.
The present invention also provides a kind of preparation method of transition metal sulfide catalyst, including：
Transition metal salt, sulfide, reducing agent, dispersant, water and graphene oxide are mixed, the water in autoclave
Thermal response obtains transition metal sulfide catalyst.
It is above-mentioned prepare transition metal sulfide catalyst during, using water as solvent, graphene oxide as carry
Body, suitable transition metal salt and sulfide carry out hydro-thermal reaction, and reducing agent controls metal to redox graphene
Valence state, can obtain the better redox graphene of electric conductivity, dispersant is conducive to metal sulfide being dispersed in evenly
On carrier.
In this application, the reducing agent is one or more in ethylene glycol, glycerine, acetaldehyde and propionic aldehyde, is having
In body embodiment, the reducing agent is selected from ethylene glycol or glycerine；The dispersant is PVP (K-30)；The transition metal salt
For transition metal nitrate；Transition metal in the transition metal salt is selected from selected from VIII group, IB races and Group IIB transition metal
In one or more metallic elements, and not include Ru, Rh, Pt and Ir；The sulfide is inorganic sulfide compound, is selected from
Na2S、K2S、(NH4)2SO4In it is one or more.
The molar ratio of the transition metal salt and the sulfide is (0.5~2)：1.
It is above-mentioned prepare transition metal sulfide catalyst during have occurred single step reaction, specific reaction process is M2+
+S2+→ MS, the transient metal sulfide of generation are deposited on graphene film, then growth in situ, and PVP can be protected as dispersant
The homodisperse of nano-particle is demonstrate,proved, the week reduction of reducing agent can ensure transition metal ions as positive divalent, and then ensured
Metal principal mode is crossed as divalent, is existed in the form of MS.
Above-mentioned reaction process is that a step carries out, but the order of addition of raw material can carry out ensureing as follows
Raw material is sufficiently mixed：
Graphene oxide powder is distributed to ultrasound stripping in aqueous solution, obtains uniform graphene oxide dispersion；
Transition metal salt and dispersant, ultrasonic disperse are added in into graphene oxide dispersion, obtains the first solution；
Sulfide is added in reducing agent and is dissolved, obtains the second solution；
Second solution is added in the first solution, is stirred under room temperature；Above-mentioned solution is transferred to Teflon hydro-thermals
Hydro-thermal reaction in reaction kettle, cooled to room temperature can obtain the transition gold that redox graphene loads after filtering drying
Belong to sulfide catalyst.
According to the present invention, in above-mentioned hydrothermal reaction process, the temperature of the hydro-thermal reaction is 150~200 DEG C, and the time is
24~36h.
In transition metal sulfide catalyst preparation process, the molar ratio of transition metal salt and sulfide for (0.5~
2)：1, sulfide and graphene ratio are 1mmol:100mg, H2O and reducing agent volume ratio are 3:1, dispersant it is a concentration of
0.5mg/ml。
This application provides the method that aromatic amine compound is prepared using above-mentioned transition metal sulfide catalyst, including：
Aromatic nitro compound, reducing agent, catalyst and water are subjected to water-bath, obtain aromatic amine compound；It is described
Catalyst is the transition metal sulfide catalyst prepared by the preparation method described in described in said program or said program.
It is above-mentioned prepare aromatic amine compound during, the aromatic nitro compound is known to those skilled in the art
Aromatic nitro compound, this application is not particularly limited, in a particular embodiment, aromatic nitro compound choosing
Artoregistration nitro compound, more specifically, the aromatic nitro compound are selected from p-nitrophenol, then corresponding life after its reduction
Into para-aminophenol.The reducing agent is selected from sodium borohydride or potassium borohydride.As shown in FIG. 1, FIG. 1 is the application to prepare aromatic amine
The reaction schematic diagram of compound.In this application, aromatic nitro compound reacted under the action of reducing agent and catalyst to get
Aromatic amine compound is arrived.
In aromatic amine compound preparation process, catalyst concn 0.33mg/mL, aromatic nitro compound is a concentration of
1mmol/L, a concentration of 10mmol/L of reducing agent, the temperature of reaction is 20~70 DEG C, in a particular embodiment, the temperature of reaction
It is 30 DEG C.
Transition metal sulfide catalyst provided by the invention can quickly obtain corresponding amine chemical combination at normal temperatures and pressures
Object has the characteristics that high conversion, highly selective, high circulation stability.In addition, the catalyst that the application provides is urged to be heterogeneous
Agent can be recycled in quick separating, realization after the completion of reaction.The experimental results showed that the catalyst that the application provides
The conversion ratio and selectivity that can make raw material are connected on more than 99%.The present invention also provides a kind of synthetic method of aromatic amine,
Under above-mentioned catalyst action, using sodium borohydride as reducing agent, after reaction raw materials, solvent, sodium borohydride and catalyst are mixed,
It is stirred under normal temperature and pressure, you can quick to obtain corresponding aminated compounds.Synthetic method provided by the invention is easy to operate, without height
Temperature without pressurization, reduces the requirement to consersion unit, saves cost of equipment；And this method is quick, efficient, conversion ratio
It is very high with selectivity, it can be very good the large-scale production applied to aminated compounds.
For a further understanding of the present invention, with reference to embodiment to transition metal sulfide catalyst provided by the invention
And its application is described in detail, protection scope of the present invention is not limited by the following examples.
Embodiment 1
0.1g graphene oxide powders are distributed to ultrasound stripping in 60ml aqueous solutions, obtain uniform graphene oxide point
Dispersion liquid, then 404mg Fe (NO are added into solution3)3·9H2After O and 40mg PVP (K-30), ultrasonic disperse 30min with 20ml
Na of the ethylene glycol as solvent2S (1mmol, 78mg) solution mixes, and continues to stir at ambient temperature, is transferred to after 60min
In Teflon hydrothermal reaction kettles, for 24 hours, cooled to room temperature can obtain FeS rGO catalysis to 180 DEG C of hydro-thermals after filtering drying
Agent.Fig. 2 is the electron scanning micrograph of FeS@rGO catalyst manufactured in the present embodiment, as seen from the figure, the reduction after hydro-thermal
Graphene oxide sheet becomes drape, and which greatly enhances the specific surface areas of carrier, are more advantageous to adsorption reaction object, are conducive to pass
Matter, shinny part are FeS, it can be seen that FeS is uniformly dispersed on redox graphene.Fig. 3 is prepared for the present embodiment
FeS@rGO catalyst XRD spectrum, main peak position coincide with the general picture library of FeS standards (JCPDS65-9124) in figure, can be true
Products therefrom is recognized for FeS/rGO composite materials.
Embodiment 2
0.1g graphene oxide powders are distributed to ultrasound stripping in 60ml aqueous solutions, obtain uniform graphene oxide point
Dispersion liquid, then 291mg Co (NO are added into solution3)2·6H2After O and 40mg PVP (K-30), ultrasonic disperse 30min with 20ml
Na of the ethylene glycol as solvent2S (1mmol, 78mg) solution mixes, and continues to be transferred to after stirring 60min under room temperature
In Teflon hydrothermal reaction kettles, for 24 hours, cooled to room temperature can obtain CoS rGO catalysis to 180 DEG C of hydro-thermals after filtering drying
Agent.Fig. 5 is the electron scanning micrograph of CoS@rGO catalyst manufactured in the present embodiment, as seen from the figure, the reduction after hydro-thermal
Graphene oxide sheet becomes drape, and which greatly enhances the specific surface areas of carrier, are more advantageous to adsorption reaction object, are conducive to pass
Matter, shinny part are CoS, it can be seen that CoS is uniformly dispersed on redox graphene.Fig. 6 is prepared for the present embodiment
CoS@rGO catalyst XRD spectrum, main peak position coincide with the general picture library of CoS standards (PDF65-3418) in figure, can confirm
Products therefrom is CoS/rGO composite materials.
Embodiment 3
0.1g graphene oxide powders are distributed to ultrasound stripping in 60ml aqueous solutions, obtain uniform graphene oxide point
Dispersion liquid, then 291mg Ni (NO are added into solution3)2·6H2After O and 40mg PVP (K-30), ultrasonic disperse 30min with 20ml
Na of the ethylene glycol as solvent2S (1mmol, 78mg) solution mixes, and continues to be transferred to after stirring 60min under room temperature
In Teflon hydrothermal reaction kettles, for 24 hours, cooled to room temperature can obtain NiS rGO catalysis to 180 DEG C of hydro-thermals after filtering drying
Agent.Fig. 8 is the electron scanning micrograph of NiS@rGO catalyst manufactured in the present embodiment, as seen from the figure, the reduction after hydro-thermal
Graphene oxide sheet becomes drape, and which greatly enhances the specific surface areas of carrier, are more advantageous to adsorption reaction object, are conducive to pass
Matter, shinny part are NiS, it can be seen that NiS is uniformly dispersed on redox graphene.Fig. 9 is prepared for the present embodiment
NiS@rGO catalyst XRD spectrum, main peak position coincide with the general picture library of NiS standards (PDF 65-3419) in figure, can be true
Products therefrom is recognized for NiS/rGO composite materials.
Catalyst prepared by Examples 1 to 3 carries out as follows for the Performance Evaluation of catalyzing and synthesizing amine：
1mmol p-nitrophenols (4-NP), 20mg catalyst are added in the beaker of 100mL, adds the pure of 60mL
Water, 22.6mg NaBH4, reacted in 30 DEG C of water-baths, under stirring condition, per sub-sampling 2ml, cross after 0.22 μm of film make catalyst with
Reaction solution detaches, reaction solution measurement of ultraviolet-visible spectrophotometer, p-nitrophenyl at wave-length coverage 200-500nm, 400nm
Phenol (4-NP) characteristic absorption peak, 290nm are nearby para-aminophenol (4-AP) characteristic absorption peak.
Fig. 4 is the reduction effect figure of FeS@rGO catalysts 4-NP prepared by embodiment 1, as shown in Figure 4, FeS@rGO
Catalyst is fine to the reduction effect of 4-NP, and 4-NP can be fully converted to 4-AP in 2min, and selectivity is 100%；
Fig. 7 is the reduction effect figure of CoS@rGO catalysts 4-NP prepared by embodiment 2, as shown in Figure 7, CoS@rGO
Catalyst is fine to the reduction effect of 4-NP, and 4-NP can be fully converted to 4-AP in 2min, and selectivity is 100%；
Figure 10 is the reduction effect figure of NiS@rGO catalysts 4-NP prepared by embodiment 3, as shown in Figure 10, NiS@
RGO catalyst is fine to the reduction effect of 4-NP, and 4-NP can be fully converted to 4-AP in 1.5min, and selectivity is 100%.
Embodiment 4
0.1g graphene oxide powders are distributed to ultrasound stripping in 60ml aqueous solutions, obtain uniform graphene oxide point
Dispersion liquid, then 404mg Fe (NO are added into solution3)3·9H2After O and 40mg PVP (K-30), ultrasonic disperse 30min with 20ml
K of the ethylene glycol as solvent2S (1mmol, 110mg) solution mixes, and continues to be transferred to after stirring 60min under room temperature
In Teflon hydrothermal reaction kettles, for 24 hours, cooled to room temperature can obtain FeS rGO catalysis to 180 DEG C of hydro-thermals after filtering drying
Agent.
Embodiment 5
0.1g graphene oxide powders are distributed to ultrasound stripping in 60ml aqueous solutions, obtain uniform graphene oxide point
Dispersion liquid, then 291mg Co (NO are added into solution3)2·6H2After O and 40mg PVP (K-30), ultrasonic disperse 30min with 20ml
K of the ethylene glycol as solvent2S (1mmol, 110mg) solution mixes, and continues to be transferred to after stirring 60min under room temperature
In Teflon hydrothermal reaction kettles, for 24 hours, cooled to room temperature can obtain CoS rGO catalysis to 180 DEG C of hydro-thermals after filtering drying
Agent.
Embodiment 6
0.1g graphene oxide powders are distributed to ultrasound stripping in 60ml aqueous solutions, obtain uniform graphene oxide point
Dispersion liquid, then 291mg Ni (NO are added into solution3)2·6H2After O and 40mg PVP (K-30), ultrasonic disperse 30min with 20ml
K of the ethylene glycol as solvent2S (1mmol, 110mg) solution mixes, and continues to be transferred to after stirring 60min under room temperature
In Teflon hydrothermal reaction kettles, for 24 hours, cooled to room temperature can obtain NiS rGO catalysis to 180 DEG C of hydro-thermals after filtering drying
Agent.
Embodiment 7
0.1g graphene oxide powders are distributed to ultrasound stripping in 60ml aqueous solutions, obtain uniform graphene oxide point
Dispersion liquid, then 404mg Fe (NO are added into solution3)3·9H2After O and 40mg PVP (K-30), ultrasonic disperse 30min with 20ml
Na of the glycerine as solvent2S (1mmol, 78mg) solution mixes, and continues to stir at ambient temperature, is transferred to after 60min
In Teflon hydrothermal reaction kettles, for 24 hours, cooled to room temperature can obtain FeS rGO catalysis to 180 DEG C of hydro-thermals after filtering drying
Agent.
Embodiment 8
0.1g graphene oxide powders are distributed to ultrasound stripping in 60ml aqueous solutions, obtain uniform graphene oxide point
Dispersion liquid, then 291mg Co (NO are added into solution3)2·6H2After O and 40mg PVP (K-30), ultrasonic disperse 30min with 20ml
Na of the glycerine as solvent2S (1mmol, 78mg) solution mixes, and continues to be transferred to after stirring 60min under room temperature
In Teflon hydrothermal reaction kettles, 180 DEG C of hydro-thermal 24H, cooled to room temperature can obtain CoS rGO catalysis after filtering drying
Agent.
Embodiment 9
0.1g graphene oxide powders are distributed to ultrasound stripping in 60ml aqueous solutions, obtain uniform graphene oxide dispersion
Liquid, then 291mg Ni (NO are added into solution3)2·6H2After O and 40mg PVP (K-30), ultrasonic disperse 30min with 20ml third
Na of the triol as solvent2S (1mmol, 78mg) solution mixes, and continues to be transferred to after stirring 60min under room temperature
In Teflon hydrothermal reaction kettles, for 24 hours, cooled to room temperature can obtain NiS rGO catalysis to 180 DEG C of hydro-thermals after filtering drying
Agent.
Embodiment 10
0.1g graphene oxide powders are distributed to ultrasound stripping in 60ml aqueous solutions, obtain uniform graphene oxide point
Dispersion liquid, then 404mg Fe (NO are added into solution3)3·9H2After O and 40mg PVP (K-30), ultrasonic disperse 30min with 20ml
K of the glycerine as solvent2S (1mmol, 110mg) solution mixes, and continues to be transferred to after stirring 60min under room temperature
In Teflon hydrothermal reaction kettles, for 24 hours, cooled to room temperature can obtain FeS rGO catalysis to 180 DEG C of hydro-thermals after filtering drying
Agent.
Embodiment 11
0.1g graphene oxide powders are distributed to ultrasound stripping in 60ml aqueous solutions, obtain uniform graphene oxide point
Dispersion liquid, then 291mg Co (NO are added into solution3)2·6H2After O and 40mg PVP (K-30), ultrasonic disperse 30min with 20ml
K of the glycerine as solvent2S (1mmol, 110mg) solution mixes, and continues to be transferred to after stirring 60min under room temperature
In Teflon hydrothermal reaction kettles, for 24 hours, cooled to room temperature can obtain CoS rGO catalysis to 180 DEG C of hydro-thermals after filtering drying
Agent.
Embodiment 12
0.1g graphene oxide powders are distributed to ultrasound stripping in 60ml aqueous solutions, obtain uniform graphene oxide point
Dispersion liquid, then 291mg Ni (NO are added into solution3)2·6H2After O and 40mg PVP (K-30), ultrasonic disperse 30min with 20ml
K of the glycerine as solvent2S (1mmol, 110mg) solution mixes, and continues to be transferred to after stirring 60min under room temperature
In Teflon hydrothermal reaction kettles, for 24 hours, cooled to room temperature can obtain NiS rGO catalysis to 180 DEG C of hydro-thermals after filtering drying
Agent.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
The foregoing description of the disclosed embodiments enables professional and technical personnel in the field to realize or use the present invention.
A variety of modifications of these embodiments will be apparent for those skilled in the art, it is as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and the principles and novel features disclosed herein phase one
The most wide range caused.
Claims (10)
1. a kind of transition metal sulfide catalyst by redox graphene and is carried on the redox graphene surface
Transient metal sulfide composition.
2. transition metal sulfide catalyst according to claim 1, which is characterized in that in the transient metal sulfide
One or more metallic elements of the transition metal in VIII group, IB races and Group IIB transition metal, and do not include Ru, Rh,
Pt and Ir.
3. transition metal sulfide catalyst according to claim 1, which is characterized in that the transient metal sulfide choosing
From FeS, CoS or NiS.
4. a kind of preparation method of transition metal sulfide catalyst, including：
Transition metal salt, sulfide, reducing agent, dispersant, water and graphene oxide are mixed, hydro-thermal is anti-in autoclave
Should, obtain transition metal sulfide catalyst.
5. preparation method according to claim 4, which is characterized in that the reducing agent is selected from ethylene glycol, glycerine, acetaldehyde
With it is one or more in propionic aldehyde；The dispersant is PVP (K-30)；The transition metal salt is transition metal nitrate；Institute
One or more metallic elements of the transition metal in VIII group, IB races and Group IIB transition metal in transition metal salt are stated,
And do not include Ru, Rh, Pt and Ir；The sulfide is inorganic sulphide, selected from Na2S、K2S、(NH4)2SO4In one kind or more
Kind.
6. preparation method according to claim 4, which is characterized in that mole of the transition metal salt and the sulfide
Than for (0.5~2)：1.
7. preparation method according to claim 4, which is characterized in that further included before mixing：
Graphene oxide powder is dispersed to ultrasound stripping in aqueous solution, obtains graphene oxide dispersion.
8. preparation method according to claim 4, which is characterized in that the temperature of the hydro-thermal reaction is 150~200 DEG C,
Time is 24~36h.
9. a kind of preparation method of aromatic amine compound, including：
Aromatic nitro compound, reducing agent, catalyst and water are subjected to water-bath, obtain aromatic amine compound；The catalysis
Agent is the transition gold prepared by claims 1 to 3 any one of them or claim 4~8 any one of them preparation method
Belong to sulfide catalyst.
10. preparation method according to claim 9, which is characterized in that the reducing agent is sodium borohydride or potassium borohydride.
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