CN106378147B - A kind of magnetism Au/Fe3O4 catalyst and the preparation method and application thereof - Google Patents
A kind of magnetism Au/Fe3O4 catalyst and the preparation method and application thereof Download PDFInfo
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- CN106378147B CN106378147B CN201610714684.0A CN201610714684A CN106378147B CN 106378147 B CN106378147 B CN 106378147B CN 201610714684 A CN201610714684 A CN 201610714684A CN 106378147 B CN106378147 B CN 106378147B
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 230000005389 magnetism Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 11
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims 1
- -1 Aromatic Nitro Compounds Chemical class 0.000 abstract description 22
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 230000009467 reduction Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000908 ammonium hydroxide Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000010931 gold Substances 0.000 abstract 2
- 238000007598 dipping method Methods 0.000 abstract 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 41
- 229910052742 iron Inorganic materials 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 229910019931 (NH4)2Fe(SO4)2 Inorganic materials 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 230000005291 magnetic effect Effects 0.000 description 7
- 239000000696 magnetic material Substances 0.000 description 7
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000003938 benzyl alcohols Chemical class 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 1
- 229940075931 sodium dithionate Drugs 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- 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
- B01J35/33—Electric or magnetic 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- C07C209/325—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 reduction by other means than indicated in C07C209/34 or C07C209/36
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of magnetism Au/Fe3O4Catalyst and the preparation method and application thereof is that the magnetism Au/Fe is made through precipitation, dipping and calcining using molysite, ferrous salt, ammonium hydroxide and gold chloride as raw material3O4Catalyst.The method of the present invention manufacturing cost is low, and simple production process can be mass-produced, and gained catalyst has higher catalytic activity and selectivity, can be used for catalysis oxidation benzyl alcohol and catalysis Reduction of Aromatic Nitro Compounds, is conducive to the sustainable development of environment and the energy.
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to a kind of magnetism Au/Fe3O4Catalyst and its preparation side
Method is with it in catalysis oxidation benzyl alcohol and the application in catalysis Reduction of Aromatic Nitro Compounds.
Background technology
Magnetic material, i.e. ferromagnetic substance are functional materials ancient and that purposes is very extensive, before 3000 just
Recognized and applied by people, such as uses native magnet as compass.Various components, which are made, in magnetic material has conversion, passes
It passs, handle the functions such as information, storage energy, energy saving, be widely used in the energy, telecommunications, automatically control, communicate, household
The fields such as electric appliance, biology, health care, light industry, ore dressing, physics mine locating, military project, especially being had become in information technology field can not
The component part lacked.Since the 1950s, the output value and yield of global magnetic material almost just turned over one every 10 years
Kind, magnetic material market in the world's becomes the foundation stone of modern society and industrial development more than 20,000,000,000 dollars at present.Generally, it is considered that
Magnetic material refers to that magnetic substance can be directly or indirectly generated by transition element iron, cobalt, nickel and its alloy etc..In recent years,
Due to magnetic material have can guidance quality, quick separating, good selective, magnetic material is also widely used in life
The fields such as object medicine, catalysis, sewage disposal, the removal of heavy metal.
As industrialization degree is increasingly promoted, environmental pollution and energy crisis are that current mankind faces most severe problem,
Seriously threaten the sustainable development of human society.Seek efficient, environmentally friendly pollutant process technology and cleaning is reproducible
The energy becomes the focus of world attention in recent years.With the development of catalysis technique, the choosing of low temperature or room temperature catalysis organic compound
The redox of selecting property is increasingly approved by everybody, and has carried out pilot study to it.
In numerous selective oxidation reactions, the selective oxidation of aromatic series alcohol compound is among Fine Chemical Industry
It is a series of important can to obtain aldehydes, ketone and acids etc. by selective oxidation reaction for one important reaction of body synthesis
The intermediate of chemical products can be widely applied to the industrial circles such as medicine, dyestuff, fragrance, pesticide and material.But traditional is organic
Not only complex steps are synthesized, also relate to security risk caused by high temperature and pressure, and used oxidant is typically one
There is toxicity or corrosive strong oxidizer a bit.
In addition, aromatic nitro compound is discharge common in a kind of important dyestuff intermediate and industrial wastewater
Object, toxicity is big, stability is good, improvement is difficult.Traditional physical-chemical process processing cost is high, efficiency is low；Biochemical method is deposited
The deficiencies of bacterial isolation is difficult, processing capacity is poor.How effectively to degrade or convert aromatic nitro compound and has become mesh
The hot spot of preceding research.Meanwhile aromatic nitro compound passes through the amine compound that reduction obtains, and is also important organic centre
Body and fine chemical product are widely used in the fields such as synthetic rubber, dyestuff, pigment, medicine, pesticide, the huge market demand.But
Commercially produce the production of aromatic amine compounds at present all and be using the reducing agent measured, as sodium dithionate, sodium borohydride,
Iron, tin, zinc in hydrazine hydrate and ammonium hydroxide etc., and high temperature, high pressure and catalyst iron powder are related generally to during it, make its technique
That there are industrial wastewaters is more, generates the problems such as a large amount of iron cements, and not only energy consumption is high but also seriously pollutes environment.
Research synthesizes regulatable catalyst, is selectively oxidized to aromatic series alcohols and to aromatic nitro compound
Catalysis reduction is carried out, can be turned waste into wealth and the sustainable development of human society.Therefore, exploitation is cheap, is easy to get, easily
Separation, simple production process, the catalyst that can be prepared on a large scale, the selective oxidation reduction for aromatic organic compounds are non-
Often it is necessary to.
Invention content
The purpose of the present invention is to provide a kind of magnetism Au/Fe3O4Catalyst and the preparation method and application thereof, gained are urged
Agent catalytic activity is good, high selectivity, long lifespan, separation is convenient for withdraw, is environmentally friendly, can be used for aromatic organic compounds
Selective oxidation reduction, and its manufacturing cost is low, simple production process, can be mass-produced.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of magnetism Au/Fe3O4Catalyst, in butterfly-like, surface tool fold；Preparation method includes the following steps：
1）Molysite and ferrous salt are dissolved in deionized water together, are heated to 65 DEG C under agitation；
2）Keep step 1）Acquired solution temperature is 65 DEG C, and ammonia spirit is then slowly added dropwise while stirring, adjusts reaction
Liquid pH value is 10-11, continues to be stirred to react 1 h then at 65 DEG C；
3）After obtained solid is separated by filtration, it is neutrality to be washed with deionized to pH, is drying to obtain Fe3O4Solid；
4）By gained Fe3O4Solid is placed in container, using equi-volume impregnating, slowly in Fe3O4The surface of solids uniformly drips
Add chlorauric acid solution；
5）By step 4）It is impregnated with HAuCl4Fe3O4After being completely dried, 400 DEG C of 2 h of calcining are placed in, the magnetism is obtained
Au/Fe3O4Catalyst；
Wherein, molysite used is ferric trichloride（FeCl3）, ferrous salt used is six ferrous sulfate hydrate ammoniums（(NH4)2Fe
(SO4)2·6H2O）；The two molar ratio is 2:1.
Gained magnetism Au/Fe3O4Catalyst cannot be only used for solvent-free generation benzaldehyde, it may also be used for catalysis aromatic series nitre
Based compound reduction generates corresponding amine compound.
The remarkable advantage of the present invention is：
（1）Magnetism Au/Fe of the invention3O4Catalyst is in butterfly-like, and surface has fold, can be provided in catalytic process more
Active site, and its manufacturing cost is low, and simple production process can be mass-produced, and can expand gained catalyst in catalysis oxygen
Change the application in terms of reduction organic matter.
（2）Conventionally employed solution form prepares noble metal carrier catalyst, often requires to use surfactant, polymerization
Object and polyelectrolyte are to ensure the formation of noble metal, but the surfactant, polymer and the polyelectrolyte later stage that are added are difficult
To completely remove, the catalytic activity of gained catalyst can be generated and be seriously affected.In order to make catalyst play maximum catalytic
Can, pure phase Fe is first prepared in the present invention3O4, then equi-volume impregnating carried noble metal Au is used, it can avoid using organic molten
Agent, surfactant, polymer and polyelectrolyte etc., and the method is simple and environmentally-friendly, easy.
（3）Au/Fe of the present invention3O4Catalyst can be used for catalysis oxidation benzyl alcohol and catalysis Reduction of Aromatic Nitro Compounds,
And with high catalytic efficiency and highly selective, in the catalyzed oxidation test of benzyl alcohol, the conversion ratio for reacting 8h is 91%, choosing
Selecting property is 89%；In aromatic nitro compound CATALYTIC REDUCTION RUNS, conversion ratio is 91% or more, and selectivity is 98% or more.
（4）Gained Au/Fe of the invention3O4Catalyst has magnetic, easily separated recycling, the rate of recovery reachable
99.3%, be conducive to the sustainable development of environment and the energy, and react through 4 repetition catalysis, catalytic activity still keeps stable.
Description of the drawings
Fig. 1 is Au/Fe prepared by the present invention3O4SEM figure.
Fig. 2 is with FeCl2·4H2O（a）(NH4)2Fe(SO4)2·6H2O（b）For Fe obtained by predecessor3O4XRD
Figure.
Fig. 3 is with (NH4)2Fe(SO4)2·6H2O is Au/Fe made from predecessor3O4XRD diagram.
Fig. 4 is with FeCl2·4H2O is Au/Fe made from predecessor2O3XRD diagram.
Specific implementation mode
A kind of magnetism Au/Fe3O4The preparation method of catalyst includes the following steps：
1）By 2.70 g ferric trichlorides（FeCl3）With 1.96 g, six ferrous sulfate hydrate ammoniums（(NH4)2Fe(SO4)2·6H2O）
It is dissolved in together in 100mL deionized waters, is heated to 65 DEG C under agitation；
2）Keep step 1）Acquired solution temperature is 65 DEG C, and ammonia spirit is then slowly added dropwise while stirring（1:1, v/v）,
Adjusting reacting liquid pH value is 10-11, continues to be stirred to react 1 h then at 65 DEG C；
3）After obtained solid is separated by filtration, it is neutrality to be washed with deionized to pH, is drying to obtain Fe3O4Solid；
4）By 0.19 g Fe of gained3O4Solid is placed in container, using equi-volume impregnating, slowly in Fe3O4Solid table
Face drops evenly the chlorauric acid solution of a concentration of 0.5-1mol/L of 0.5-1 mL；
5）By step 4）It is impregnated with HAuCl4Fe3O4After being completely dried, 400 DEG C of 2 h of calcining are placed in, the magnetism is obtained
Au/Fe3O4Catalyst.
The experimental method of catalytic oxidation of benzyl alcohol is as follows：
（1）A certain amount of catalyst and a certain amount of benzyl alcohol are added in heat catalysis kettle and are stirred evenly；
（2）Temperature, rotating speed and pressure that reaction needs are adjusted, reaction after a certain period of time, separates and recovers catalyst, and take one
Quantitative product is diluted with ethyl alcohol, obtains reaction mixture；
（3）By reaction mixture into gas chromatographic analysis, pass through retention time and peak area qualitative.
The experimental method of aromatic nitro compound catalysis reduction is as follows：
（1）A certain amount of aromatic nitro compound solution is placed in reaction vessel, a certain amount of NaBH is added4；
（2）After stirring evenly, catalyst is added, reaction after a certain period of time, recycles catalyst；
（3）Products therefrom solution passes through retention time and peak area qualitative into liquid-phase chromatographic analysis.
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment
1）By 2.70 g ferric trichlorides（FeCl3）, 1.96 g, six ferrous sulfate hydrate ammoniums（(NH4)2Fe(SO4)2·6H2O）
It is dissolved in together in 100 mL deionized waters, is heated to 65 DEG C under agitation；Then ammonia spirit is slowly added dropwise while stirring
（1:1, v/v）, adjusting reacting liquid pH value is 10-11, continues to be stirred to react 1 h then at 65 DEG C；After obtained solid is separated by filtration, use
It is neutrality that deionized water, which is washed to pH, is drying to obtain Fe3O4Solid；
2）The 0.19 g Fe that will be prepared3O4Solid is placed in container, using equi-volume impregnating, slowly in Fe3O4
The surface of solids drops evenly the HAuCl of a concentration of 0.5mol/L of 1 mL4Solution；Then HAuCl will be impregnated with4Fe3O4It is completely dry
It is dry, then 400 DEG C of 2 h of calcining are placed in, obtain Au/Fe3O4Composite material, the load capacity of noble metal Au is in gained composite material
5wt%。
Fig. 1 is prepared Au/Fe3O4SEM figure.It can be seen from the figure that gained Au/Fe3O4Catalyst in butterfly-like,
There are many gauffers on surface, and more active sites can be provided in catalytic process.
Comparative example
1）By 2.70 g ferric trichlorides（FeCl3）, 0.994 g tetra- be hydrated iron（FeCl2·4H2O）It is dissolved in together
In 100 mL deionized waters, it is heated to 65 DEG C under agitation；Then ammonia spirit is slowly added dropwise while stirring（1:1, v/
v）, adjusting reacting liquid pH value is 10-11, continues to be stirred to react 1 h then at 65 DEG C；After obtained solid is separated by filtration, deionization is used
Water washing is neutrality to pH, is drying to obtain Fe3O4Solid；
2）The 0.19 g Fe that will be prepared3O4Solid is placed in container, using equi-volume impregnating, slowly in Fe3O4
The surface of solids drops evenly the HAuCl of a concentration of 0.5mol/L of 1 mL4Solution；Then HAuCl will be impregnated with4Fe3O4It is completely dry
It is dry, then 400 DEG C of 2 h of calcining are placed in, obtain Au/Fe2O3Composite material, the load capacity of noble metal Au is in gained composite material
5wt%。
Fig. 2 is with FeCl2·4H2O（a）(NH4)2Fe(SO4)2·6H2O（b）For Fe obtained by predecessor3O4XRD
Figure.From the figure, it can be seen that two samples have magnetic iron ore Fe3O4Diffraction maximum, 2 θ values of corresponding diffraction maximum 30.1 °,
35.5 °, 43.1 °, 53.5 °, 57.0 °, 62.6 ° and 74.0 °, magnetic iron ore Fe is corresponded to respectively3O4(220), (311), (400),
(422), (511), (440) and (533) crystal face, and there is no other diffraction maximums in XRD spectra.Illustrate to use the precipitation method
That prepare gained is pure phase Fe3O4.In addition, also illustrating to prepare Fe by predecessor of different divalent ferrous irons3O4, to Fe3O4Crystalline substance
Type will not have an impact.
Fig. 3 is with (NH4)2Fe(SO4)2·6H2O is Au/Fe obtained by predecessor3O4XRD diagram.It can from figure
It arrives, the sample after calcining has magnetic iron ore Fe3O4Diffraction maximum, 2 θ values of corresponding diffraction maximum 30.1 °, 35.5 °, 43.1 °,
53.5 °, 57.0 °, 62.6 ° and 74.0 °, magnetic iron ore Fe is corresponded to respectively3O4(220), (311), (400), (422), (511),
(440) and (533) crystal face, while there is also four apparent characteristic peaks, 2 θ values are at 38.2 °, 44.4 °, 64.6 ° and 77.6 °,
(111), (200), (220) and (311) crystal face of corresponding A u respectively.It is possible thereby to prove, with (NH4)2Fe(SO4)2·6H2O is
That predecessor is prepared is Au/Fe3O4。
Fig. 4 is with FeCl2·4H2O is Au/Fe obtained by predecessor2O3XRD diagram.From the figure, it can be seen that after calcining
Sample have bloodstone Fe2O3Diffraction maximum, 2 θ values of corresponding diffraction maximum 24.1 °, 33.1 °, 35.6 °, 40.8 °, 49.4 °,
54.0 °, 57.5 °, 62.4 °, 64.0 °, 71.8 ° and 75.4 °, bloodstone Fe is corresponded to respectively2O3(012), (104), (110),
(113), (024), (116), (018), (214), (300), (1010) and (220) crystal face, at the same it is apparent special there is also four
Peak is levied, 2 θ values are at 38.2 °, 44.4 °, 64.6 ° and 77.6 °, and (111), (200), (220) and (311) of corresponding A u are brilliant respectively
Magnetic iron ore Fe is not present in face3O4Diffraction maximum.It can be seen that with FeCl2·4H2That O is that predecessor is prepared is Au/
Fe2O3。
1. catalytic oxidation of benzyl alcohol performance test
In 100 mL catalytic reaction kettles, 0.1 g composite materials and 40 mL benzyl alcohols are added and are uniformly mixed, if
It sets that catalytic reaction temperature is 100 DEG C, stir speed (S.S.) is 1000 revs/min, pressure is 5 atmospheres oxygens, is carried out after reacting 8h
Detection, related data are as shown in table 1.
1 Au/Fe of table3O4And Au/Fe2O3The activity data of catalysis oxidation benzyl alcohol
By 1 result of table as it can be seen that Au/Fe3O4Conversion ratio and selectivity be apparently higher than Au/Fe2O3。
2. aromatic nitro compound catalytic reduction performance is tested
By 60 mg NaBH4It is uniformly mixed, adds with the aromatic nitro compound solution of a concentration of 10 ppm of 60 mL
6 mg composite materials, catalysis are detected after reacting 8 min, and related data is as shown in table 2.
2 Au/Fe of table3O4And Au/Fe2O3The activity data of catalyst Reduction of Aromatic Nitro Compounds
By 2 result of table as it can be seen that Au/Fe3O4Conversion ratio for paranitroanilinum is 98%, selectivity is 99%；For to nitre
The conversion ratio of base phenol is 99%, selectivity is 99%；For the conversion ratio to Nitrobromobenzene be 99%, selectivity is 99%, Au/
Fe3O4Conversion ratio for paranitrochlorobenzene is 94%, selectivity is 98%, Au/Fe3O4Conversion ratio for para-nitrotoluene is
98%, selectivity is 99%, Au/Fe3O4Conversion ratio for paranitroanisole is 91%, selectivity is 98%, obviously higher than
Au/Fe2O3。
By above-mentioned it is demonstrated experimentally that gained Au/Fe of the present invention3O4It can be used for catalysis oxidation benzyl alcohol and catalysis reduction aromatic series
Nitro compound, and with high catalytic efficiency and highly selective.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (1)
1. a kind of magnetism Au/Fe3O4Application of the catalyst in solvent-free catalysis oxidation benzyl alcohol generates benzaldehyde, feature exist
In：The Au/Fe3O4The preparation method of catalyst includes the following steps：
1）Molysite and ferrous salt are dissolved in deionized water together, are heated to 65 DEG C under agitation；
2）Keep step 1）Acquired solution temperature is 65 DEG C, and ammonia spirit is then slowly added dropwise while stirring, adjusts reaction solution pH
Value is 10-11, continues to be stirred to react 1 h at 65 DEG C；
3）After obtained solid is separated by filtration, it is neutrality to be washed with deionized to pH, is drying to obtain Fe3O4Solid；
4）By gained Fe3O4Solid is placed in container, using equi-volume impregnating, slowly in Fe3O4The surface of solids drops evenly chlorine
Auric acid solution；
5）By step 4）It is impregnated with HAuCl4Fe3O4After being completely dried, 400 DEG C of 2 h of calcining are placed in, the magnetism Au/ is obtained
Fe3O4Catalyst；
Molysite used is ferric trichloride, and ferrous salt used is six ferrous sulfate hydrate ammoniums；The two molar ratio is 2:1.
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| CN103819295A (en) * | 2012-11-19 | 2014-05-28 | 中国科学院大连化学物理研究所 | Application of catalyst to selective hydrogenation reaction of aromatic nitro compound |
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| Magnetite-Silica-Gold Nanocomposite: One-Pot Single-Step Synthesis and Its Application for Solvent-Free Oxidation of Benzyl Alcohol;Mangesh Kokate et al.;《J. Phys. Chem. C》;20150602;第119卷;第14214？14223页 * |
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