CN106378147A - Magnetic Au/Fe3O4 catalyst, preparation method and application thereof - Google Patents
Magnetic Au/Fe3O4 catalyst, preparation method and application thereof Download PDFInfo
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- CN106378147A CN106378147A CN201610714684.0A CN201610714684A CN106378147A CN 106378147 A CN106378147 A CN 106378147A CN 201610714684 A CN201610714684 A CN 201610714684A CN 106378147 A CN106378147 A CN 106378147A
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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 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 30
- -1 aromatic nitro compounds Chemical class 0.000 claims abstract description 23
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 150000002505 iron Chemical class 0.000 claims abstract description 5
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000006555 catalytic reaction Methods 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000011161 development Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 229910019931 (NH4)2Fe(SO4)2 Inorganic materials 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 239000000696 magnetic material Substances 0.000 description 7
- 238000000034 method Methods 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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 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
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 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
- 238000011056 performance test Methods 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
- 230000008569 process Effects 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
- 238000003786 synthesis reaction Methods 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 group [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
- 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 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
- 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
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000007613 environmental effect Effects 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
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 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
- 239000004615 ingredient Substances 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
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000032696 parturition Effects 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
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation 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
- 235000013599 spices Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage 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
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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 magnetic Au/Fe3O4 catalyst, a preparation method and application thereof. The magnetic Au/Fe3O4 catalyst is prepared by taking an iron salt, ferrous salt, ammonia water and chloroauric acid as the raw material, and carrying out precipitation, impregnation and calcinations. The preparation method provided by the invention has the advantages of low cost and simple production process, and can realize large-scale production. The obtained catalyst has high catalytic activity and selectivity, can be used for catalytic oxidation of benzyl alcohol and catalytic reduction of aromatic nitro compounds, and is conducive to the sustainable development of environment and energy sources.
Description
Technical field
The invention belongs to catalyst preparation technical field is and in particular to a kind of magnetic Au/Fe3O4Catalyst and its preparation side
Method application in catalysis oxidation benzyl alcohol with catalysis Reduction of Aromatic Nitro Compounds with it.
Background technology
Magnetic material, i.e. ferromagnetic substance, is ancient and the quite varied functional material of purposes, early in 3000 in the past
Recognized and applied by people, such as with native magnet as compass.Magnetic material is made various components and parts there is conversion, pass
Pass, the function such as processing information, storage energy, energy saving, be widely used in the energy, telecommunications, automatically control, communicate, domestic
The fields such as electrical equipment, biology, health care, light industry, ore dressing, physics mine locating, military project, especially becoming in areas of information technology can not
The ingredient lacking.Since the 1950's, the output value of global magnetic material and yield almost just turned over one every 10 years
Kind, current world magnetic material market, more than 20,000,000,000 dollars, becomes the foundation stone of modern society and industrial development.Generally, it is considered that
Magnetic material refers to can directly or indirectly be produced the material of magnetic by transition element ferrum, cobalt, nickel and its alloy etc..In recent years,
Due to magnetic material have can guidance quality, sharp separation, good selective, magnetic material is also widely used is giving birth to
The fields such as thing medicine, catalysis, sewage disposal, the removal of heavy metal.
Increasingly lifted with industrialization degree, environmental pollution and energy crisis are that current mankind faces problem the severeest,
Seriously threaten the sustainable development of human society.Seek efficient, the Pollutant Treatment technology of environmental protection 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
Selecting property oxidoreduction is increasingly approved by everybody, and has carried out exploratory study to it.
In numerous selective oxidation reactions, the selective oxidation of aromatic series alcohol compound is in the middle of Fine Chemical Industry
One important reaction of body synthesis, by selective oxidation reaction, can obtain aldehydes, ketone and acids etc. a series of important
The intermediate of chemical products, can be widely applied to the industrial circles such as medicine, dyestuff, spice, pesticide and material.But traditional is organic
Synthesis not only complex steps, also relate to the potential safety hazard that High Temperature High Pressure is brought, and the oxidant being used are typically one
There is toxicity or corrosive strong oxidizer.
In addition, aromatic nitro compound is a kind of important dyestuff intermediate, it is also common discharge in industrial wastewater
Thing, its toxicity is big, good stability, improvement difficulty.Traditional physical-chemical process processing cost is high, efficiency is low；Biochemical method is deposited
In deficiencies such as bacterial isolation difficulty, disposal ability differences.How effectively to degrade or convert aromatic nitro compound has become mesh
The focus of front research.Meanwhile, the amine compound that aromatic nitro compound obtains through reduction, 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 reducing agent that the production of aromatic amine compounds is all using metering at present, such as sodium dithionate, sodium borohydride,
Ferrum in hydrazine hydrate and ammonia, stannum, zinc etc., and relate generally to high temperature, high pressure and catalyst iron powder during it so as to technique
Have such problems as that industrial wastewater is many, produce a large amount of iron cements, not only consume energy high but also serious environment pollution.
Research synthesizes regulatable catalyst, and aromatic series alcohols is selectively oxidized and to aromatic nitro compound
Carry out catalysis reduction, can turn waste into wealth, be conducive to the sustainable development of human society again.Therefore, develop cheap, be easy to get, easily
Separation, simple production process, the catalyst that can prepare on a large scale, the selective oxidation reduction for aromatic organic compounds is non-
Often it is necessary.
Content of the invention
It is an object of the invention to provide a kind of magnetic Au/Fe3O4Catalyst and preparation method and application, its gained is urged
Agent catalysis activity is good, selectivity is high, life-span length, be easy to separate withdraw, environmentally friendly, can be used for aromatic organic compounds
Selective oxidation reduction, and its preparation cost is low, simple production process, can be mass-produced.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of magnetic Au/Fe3O4Catalyst, it is in butterfly-like, and surface has fold；Its preparation method comprises the following steps：
1）Iron salt and ferrous salt are together dissolved in deionized water, are heated to 65 DEG C under agitation；
2）Keep step 1）Resulting solution temperature is 65 DEG C, is then slowly added dropwise ammonia spirit while stirring, adjusts reactant liquor pH
It is worth for 10-11, then at 65 DEG C of continuation stirring reaction 1 h；
3）After gained solid filtration separation, being washed with deionized to pH is neutrality, is drying to obtain Fe3O4Solid；
4）By gained Fe3O4Solid is placed in container, using equi-volume impregnating, slowly in Fe3O4The surface of solids uniform Deca chlorine
Auric acid solution；
5）By step 4）It is impregnated with HAuCl4Fe3O4After being completely dried, it is placed in 400 DEG C of calcining 2 h, obtains described magnetic Au/
Fe3O4Catalyst；
Wherein, iron salt used is ferric chloride（FeCl3）, ferrous salt used is six ferrous sulfate hydrate ammoniums（(NH4)2Fe
(SO4)2·6H2O）；Both mol ratios are 2:1.
Gained magnetic 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）Magnetic Au/Fe of the present invention3O4Catalyst is in butterfly-like, and surface has fold, is provided that and more lives in catalytic process
Property site, and its preparation cost is low, simple production process, can be mass-produced, and can expand gained catalyst in catalysis oxidation also
The application in original machine object space face.
（2）Conventionally employed solution form prepares noble metal carrier catalyst, generally requires using surfactant, polymerization
Thing and polyelectrolyte are to guarantee the formation of noble metal, but the surfactant adding, polymer and polyelectrolyte later stage are difficult
To remove completely, the catalysis activity of gained catalyst can be produced and have a strong impact on.In order that catalyst plays maximum catalytic
Can, the present invention first prepares pure phase Fe3O4, then adopt equi-volume impregnating carried noble metal Au, 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 there is high catalytic efficiency and high selectivity,, in the catalyzed oxidation test of benzyl alcohol, the conversion ratio of reaction 8h is 91%, choosing for it
Selecting property is 89%；In aromatic nitro compound CATALYTIC REDUCTION RUNS, more than 91%, selectivity is more than 98% for conversion ratio.
（4）Gained Au/Fe of the present invention3O4Catalyst has magnetic, easily separated recycling use, its response rate up to
99.3%, be conducive to the sustainable development of environment and the energy, and through 4 repetition catalytic reactions, its catalysis activity still keeps stable.
Brief description
Fig. 1 is Au/Fe prepared by the present invention3O4SEM figure.
Fig. 2 is with FeCl2·4H2O（a）(NH4)2Fe(SO4)2·6H2O（b）Fe obtained by predecessor3O4XRD
Figure.
Fig. 3 is with (NH4)2Fe(SO4)2·6H2The Au/Fe that O is obtained for predecessor3O4XRD figure.
Fig. 4 is with FeCl2·4H2The Au/Fe that O is obtained for predecessor2O3XRD figure.
Specific embodiment
A kind of magnetic Au/Fe3O4The preparation method of catalyst comprises the following steps：
1）By 2.70 g ferric chlorides（FeCl3）With 1.96 g six ferrous sulfate hydrate ammonium（(NH4)2Fe(SO4)2·6H2O）Together
It is dissolved in 100mL deionized water, be heated to 65 DEG C under agitation；
2）Keep step 1）Resulting solution temperature is 65 DEG C, is then slowly added dropwise ammonia spirit while stirring（1:1, v/v）, adjust
Reacting liquid pH value is 10-11, then at 65 DEG C of continuation stirring reaction 1 h；
3）After gained solid filtration separation, being washed with deionized to pH is neutrality, is drying to obtain Fe3O4Solid；
4）By gained 0.19 g Fe3O4Solid is placed in container, using equi-volume impregnating, slowly in Fe3O4The surface of solids is equal
Even Deca 0.5-1 mL concentration is the chlorauric acid solution of 0.5-1mol/L；
5）By step 4）It is impregnated with HAuCl4Fe3O4After being completely dried, it is placed in 400 DEG C of calcining 2 h, obtains described magnetic Au/
Fe3O4Catalyst.
The experimental technique 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 stir；
（2）Adjust temperature, rotating speed and the pressure that reaction needs, after reaction certain time, separate and recover catalyst, and take a certain amount of
Product ethanol dilution, obtain reaction mixture；
（3）Reaction mixture is entered gas chromatographic analysiss, by retention time and peak area qualitative.
The experimental technique of aromatic nitro compound catalysis reduction is as follows：
（1）A certain amount of aromatic nitro compound solution is placed in reaction vessel, adds a certain amount of NaBH4；
（2）After stirring, add catalyst, after reaction certain time, reclaim catalyst；
（3）Products therefrom solution enters liquid-phase chromatographic analysis, by retention time and peak area qualitative.
In order that content of the present invention easily facilitates understanding, with reference to specific embodiment to of the present invention
Technical scheme is described further, but the present invention is not limited only to this.
Embodiment
1）By 2.70 g ferric chlorides（FeCl3）, 1.96 g six ferrous sulfate hydrate ammonium（(NH4)2Fe(SO4)2·6H2O）
Together it is dissolved in 100 mL deionized waters, be heated to 65 DEG C under agitation；Then it is slowly added dropwise ammonia spirit while stirring
（1:1, v/v）, regulation reacting liquid pH value is 10-11, then at 65 DEG C of continuation stirring reaction 1 h；After gained solid filtration separation, use
Deionized water wash is neutrality to pH, is drying to obtain Fe3O4Solid；
2）By prepare 0.19 g Fe3O4Solid is placed in container, using equi-volume impregnating, slowly in Fe3O4Solid
The uniform Deca in surface 1 mL concentration is the HAuCl of 0.5mol/L4Solution；Then HAuCl will be impregnated with4Fe3O4It is completely dried,
It is placed in 400 DEG C of calcining 2 h again, obtain Au/Fe3O4Composite, in gained composite, the load capacity of noble metal Au is 5wt%.
Fig. 1 is prepared Au/Fe3O4SEM figure.It can be seen that gained Au/Fe3O4Catalyst is in butterfly-like,
There are a lot of gauffers on surface, and it can provide more avtive spots in catalytic process.
Comparative example
1）By 2.70 g ferric chlorides（FeCl3）, 0.994 g tetra- hydration iron（FeCl2·4H2O）Together it is dissolved in 100
In mL deionized water, it is heated to 65 DEG C under agitation；Then it is slowly added dropwise ammonia spirit while stirring（1:1, v/v）, adjust
Section reacting liquid pH value is 10-11, then at 65 DEG C of continuation stirring reaction 1 h；After gained solid filtration separation, it is washed with deionized
It is neutrality to pH, be drying to obtain Fe3O4Solid；
2）By prepare 0.19 g Fe3O4Solid is placed in container, using equi-volume impregnating, slowly in Fe3O4Solid
The uniform Deca in surface 1 mL concentration is the HAuCl of 0.5mol/L4Solution；Then HAuCl will be impregnated with4Fe3O4It is completely dried,
It is placed in 400 DEG C of calcining 2 h again, obtain Au/Fe2O3Composite, in gained composite, the load capacity of noble metal Au is 5wt%.
Fig. 2 is with FeCl2·4H2O（a）(NH4)2Fe(SO4)2·6H2O（b）Fe obtained by predecessor3O4XRD
Figure.From the figure, it can be seen that two samples have magnetic iron ore Fe3O4Diffraction maximum, corresponding diffraction maximum 2 θ value 30.1 °,
35.5 °, 43.1 °, 53.5 °, 57.0 °, 62.6 ° and 74.0 °, correspond to magnetic iron ore Fe respectively3O4(220), (311), (400),
(422), (511), (440) and (533) crystal face, and do not have other diffraction maximums to exist in XRD spectra.Illustrate to adopt the sedimentation method
Prepare gained is pure phase Fe3O4.In addition, also illustrating to prepare Fe so that different bivalence is ferrous for predecessor3O4, to Fe3O4Crystalline substance
Type will not have an impact.
Fig. 3 is with (NH4)2Fe(SO4)2·6H2O is Au/Fe obtained by predecessor3O4XRD figure.Can from figure
Arrive, the sample after calcining has magnetic iron ore Fe3O4Diffraction maximum, corresponding diffraction maximum 2 θ value 30.1 °, 35.5 °, 43.1 °,
53.5 °, 57.0 °, 62.6 ° and 74.0 °, correspond to magnetic iron ore Fe respectively3O4(220), (311), (400), (422), (511),
(440) and (533) crystal face, also there are four obvious characteristic peaks simultaneously, its 2 θ value in 38.2 °, 44.4 °, 64.6 ° and 77.6 °,
(111), (200), (220) and (311) crystal face of corresponding A u respectively.Thus may certify that, with (NH4)2Fe(SO4)2·6H2O is
That predecessor prepares is Au/Fe3O4.
Fig. 4 is with FeCl2·4H2O is Au/Fe obtained by predecessor2O3XRD figure.From the figure, it can be seen that after calcining
Sample have bloodstone Fe2O3Diffraction maximum, corresponding diffraction maximum 2 θ value 24.1 °, 33.1 °, 35.6 °, 40.8 °, 49.4 °,
54.0 °, 57.5 °, 62.4 °, 64.0 °, 71.8 ° and 75.4 °, correspond to bloodstone Fe respectively2O3(012), (104), (110),
(113), also there are four significantly spies in, (024), (116), (018), (214), (300), (1010) and (220) crystal face simultaneously
Levy peak, in 38.2 °, 44.4 °, 64.6 ° and 77.6 °, (111), (200), (220) and (311) of corresponding A u are brilliant respectively for its 2 θ value
, there is not magnetic iron ore Fe in face3O4Diffraction maximum.As can be seen here, with FeCl2·4H2That O prepares for predecessor is Au/
Fe2O3.
1. catalytic oxidation of benzyl alcohol performance test
In 100 mL catalytic reaction kettle, add 0.1 g composite and 40 mL benzyl alcohol and be uniformly mixed, setting is urged
Change reaction temperature is 100 DEG C, stir speed (S.S.) is 1000 revs/min, pressure is 5 atmospheres oxygen, is detected after reaction 8h,
Related data is as shown in table 1.
Table 1 Au/Fe3O4And Au/Fe2O3The activity data of catalysis oxidation benzyl alcohol
From table 1 result, Au/Fe3O4Conversion ratio and selectivity apparently higher than Au/Fe2O3.
2. aromatic nitro compound catalytic reduction performance test
By 60 mg NaBH4The aromatic nitro compound solution mix homogeneously being 10 ppm with 60 mL concentration, adds 6 mg
Composite, is detected after catalytic reaction 8 min, related data is as shown in table 2.
Table 2 Au/Fe3O4And Au/Fe2O3The activity data of catalyst Reduction of Aromatic Nitro Compounds
From table 2 result, Au/Fe3O4For paranitroanilinum conversion ratio be 98%, selectivity be 99%；For to nitro
The conversion ratio of phenol is 99%, selectivity is 99%；For to the conversion ratio of Nitrobromobenzene be 99%, selectivity be 99%, Au/Fe3O4
For paranitrochlorobenzene conversion ratio be 94%, selectivity be 98%, Au/Fe3O4Conversion ratio for para-nitrotoluene is 98%, selects
Selecting property is 99%, Au/Fe3O4For paranitroanisole conversion ratio be 91%, selectivity be 98%, obviously higher than Au/
Fe2O3.
By above-mentioned it is demonstrated experimentally that gained Au/Fe of the present invention3O4Can be used for catalysis oxidation benzyl alcohol and catalysis reduction aromatic series
Nitro compound, and there is high catalytic efficiency and high selectivity.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (5)
1. a kind of magnetic Au/Fe3O4Catalyst it is characterised in that：Described catalyst is in butterfly-like, and surface has fold.
2. a kind of magnetic Au/Fe as claimed in claim 13O4The preparation method of catalyst it is characterised in that：Comprise the following steps：
1）Iron salt and ferrous salt are together dissolved in deionized water, are heated to 65 DEG C under agitation；
2）Keep step 1）Resulting solution temperature is 65 DEG C, is then slowly added dropwise ammonia spirit while stirring, adjusts reactant liquor pH
It is worth for 10-11, continuation stirring reaction 1 h at 65 DEG C；
3）After gained solid filtration separation, being washed with deionized to pH is neutrality, is drying to obtain Fe3O4Solid；
4）By gained Fe3O4Solid is placed in container, using equi-volume impregnating, slowly in Fe3O4The surface of solids uniform Deca chlorine
Auric acid solution；
5）By step 4）It is impregnated with HAuCl4Fe3O4After being completely dried, it is placed in 400 DEG C of calcining 2 h, obtains described magnetic Au/
Fe3O4Catalyst.
3. magnetic Au/Fe according to claim 23O4The preparation method of catalyst it is characterised in that：Iron salt used is trichlorine
Change ferrum, ferrous salt used is six ferrous sulfate hydrate ammoniums；Both mol ratios are 2:1.
4. a kind of magnetic Au/Fe as claimed in claim 13O4The application of catalyst it is characterised in that：For solvent-free catalysis oxygen
Change benzyl alcohol and generate benzaldehyde.
5. a kind of magnetic Au/Fe as claimed in claim 13O4The application of catalyst it is characterised in that：For being catalyzed aromatic series nitre
Based compound reduction generates corresponding amine compound.
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| CN109265326A (en) * | 2018-09-29 | 2019-01-25 | 武汉工程大学 | A kind of low-carbon alcohols promotion Fe3O4Method of the catalytic phenylmethanol oxidation preparation without chlorobenzaldehyde |
| CN111790449A (en) * | 2020-07-30 | 2020-10-20 | 泉州师范学院 | Iridium nanoparticle catalyst, preparation method thereof and application of iridium nanoparticle catalyst in catalytic reduction of nitro compound to amino compound |
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| WO2012158847A2 (en) * | 2011-05-16 | 2012-11-22 | The University Of Chicago | Materials and methods for the preparation of nanocomposites |
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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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| WO2012158847A2 (en) * | 2011-05-16 | 2012-11-22 | The University Of Chicago | Materials and methods for the preparation of nanocomposites |
| 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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| CN109265326A (en) * | 2018-09-29 | 2019-01-25 | 武汉工程大学 | A kind of low-carbon alcohols promotion Fe3O4Method of the catalytic phenylmethanol oxidation preparation without chlorobenzaldehyde |
| CN111790449A (en) * | 2020-07-30 | 2020-10-20 | 泉州师范学院 | Iridium nanoparticle catalyst, preparation method thereof and application of iridium nanoparticle catalyst in catalytic reduction of nitro compound to amino compound |
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