CN115155614A - Preparation method and application of flower-shaped magnetic nano gold catalyst - Google Patents
Preparation method and application of flower-shaped magnetic nano gold catalyst Download PDFInfo
- Publication number
- CN115155614A CN115155614A CN202210948376.XA CN202210948376A CN115155614A CN 115155614 A CN115155614 A CN 115155614A CN 202210948376 A CN202210948376 A CN 202210948376A CN 115155614 A CN115155614 A CN 115155614A
- Authority
- CN
- China
- Prior art keywords
- solution
- flower
- reaction
- preparing
- magnetic nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 239000010931 gold Substances 0.000 title claims abstract description 41
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 41
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 19
- 229910006636 γ-AlOOH Inorganic materials 0.000 claims abstract description 15
- 238000006722 reduction reaction Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 76
- 238000006243 chemical reaction Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000007885 magnetic separation Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000009210 therapy by ultrasound Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 11
- -1 gold ion Chemical class 0.000 claims description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 11
- 239000012279 sodium borohydride Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010981 drying operation Methods 0.000 claims description 5
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- POZPMIFKBAEGSS-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;trihydrate Chemical compound O.O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O POZPMIFKBAEGSS-UHFFFAOYSA-K 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001282 organosilanes Chemical class 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- CNODSORTHKVDEM-UHFFFAOYSA-N 4-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)C1=CC=C(N)C=C1 CNODSORTHKVDEM-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 description 16
- 238000011068 loading method Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
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
- 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
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a flower-shaped magnetic nano gold catalyst, belonging to the technical field of catalysts. The preparation method of the flower-shaped magnetic nano gold catalyst comprises the following steps: s1, preparing hollow Fe 3 O 4 Nanoparticles; s2, preparing modified magnetic nanoparticles; s3, preparing magnetic nanoparticles coated by the gamma-AlOOH carrier; s4, preparing a nano gold solution; s5, preparing the flower-shaped magnetic nano gold catalyst. The invention also disclosesThe application of the flower-shaped magnetic nano gold catalyst in the reduction reaction of p-nitrophenol.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method and application of a flower-shaped magnetic nano-gold catalyst.
Background
The noble metal nanoparticles have the characteristics of large specific surface area, rich active sites, easy surface modification, good dispersion consistency and the like, and attract the attention and research of broad scholars in the fields of targeted drugs, biological carriers, nuclear magnetic imaging, catalysts and the like. The catalyst of the noble metal nano particles has good adaptability to different reaction conditions and high catalytic efficiency, and is applied to the aspects of heavy metal ion catalysis, organic matter oxidation reduction and the likePlays a great role. The nano-catalyst needs to be fixed on a carrier to improve the stability and the catalytic efficiency due to the fact that particles are easy to gather and the recycling rate is low in the reaction process. The carrier material reported in the research is SiO 2 ，TiO 2 ZnO, etc., and magnetic Fe 3 O 4 Because of its high availability, low cost, large surface area, easy preparation and other characteristics, it is a very popular catalyst carrier. The magnetic nano-particles are non-toxic, easy to prepare, recyclable and have great application prospects in clean and sustainable green processes.
The core-shell magnetic nanoparticles have good stability, dispersibility, catalytic efficiency and recycling performance due to unique structural properties, such as functional shell layers, independently movable cores, mesoporous structures of the core-shell layers and the like, and are paid attention and researched by broad students. Chinese patent CN108993534B discloses a magnetic nano-catalyst, which is made of cubic Fe 3 O 4 The particles are used as cores, and meanwhile, the traditional nano gold particle loading process is optimized. However, in this invention, the specific surface area of the cubic crystal structure is relatively small compared to that of the spherical structure, and the catalyst loading is relatively low, which limits the efficiency of the catalytic reaction, and needs to be further studied.
In order to further improve the loading capacity of the nano particles and improve the catalytic efficiency, researchers begin with the aspects of introducing high specific surface area, increasing active sites, adjusting the structure of the nano particles and the like, and carry out a great deal of research on self-assembly layer-level nano structures.
In recent years, the concept of green chemistry is keen, and the conversion of toxic waste into low-toxicity or recyclable substances has become a research hotspot. Phenol and compounds thereof are listed as one of the pollutants needing to be preferentially controlled in water bodies in China. Wherein, the p-nitrophenol is a compound with high toxicity, difficult degradation and difficult treatment, and the treatment of the waste water containing the phenol and aromatic hydrocarbon compounds is still a technical problem in China and even the world. The reduction product of p-nitrophenol has relatively low toxicity to p-aminophenol, is an important chemical and medical intermediate, and is widely applied to the pesticide and dye industries. At present, common p-nitrophenol treatment methods comprise an adsorption method, a microbial degradation method, a photocatalytic degradation method, an electrochemical treatment method and the like, have a certain effect on removing p-nitrophenol, but have the limitations of ineffective degradation, slow degradation speed, secondary pollution and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a flower-shaped magnetic nano gold catalyst, and the catalyst prepared by the method has the advantages of large loading capacity, high catalytic efficiency, good magnetic separability and high recovery rate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a flower-shaped magnetic nano gold catalyst comprises the following steps:
s1, preparing hollow Fe 3 O 4 Nanoparticle:
dissolving ferric chloride hexahydrate in water, adding sodium citrate trihydrate and urea, stirring uniformly, transferring into a reaction kettle for hydrothermal reaction to generate Fe 3 O 4 Precipitating, fe 3 O 4 The precipitate is sequentially subjected to magnetic separation, water washing and drying to obtain hollow Fe 3 O 4 Nanoparticles;
s2, preparing modified magnetic nanoparticles:
subjecting said Fe to 3 O 4 Dissolving the nano particles in water, adding ammonia water and an organosilane solution, stirring uniformly, and then sequentially carrying out magnetic separation, water washing and drying operations to obtain modified magnetic nano particles;
s3, preparing the magnetic nano particles coated by the gamma-AlOOH carrier:
dissolving the modified magnetic nanoparticles in an aluminum solution to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution, then adding urea into the mixed solution, uniformly stirring, carrying out secondary ultrasonic treatment, transferring the mixed solution after the secondary ultrasonic treatment to a reaction kettle for heat seal reaction, cooling to room temperature after the heat seal reaction is finished, and carrying out magnetic separation, washing and drying on the reaction product of the heat seal reaction in sequence to obtain gamma-AlOOH carrier coated magnetic nanoparticles;
s4, preparing a nano gold solution:
adding a sodium citrate solution and a sodium borohydride solution into the gold ion solution to carry out reduction reaction to obtain a nano gold solution;
s5, preparing a flower-shaped magnetic nano gold catalyst:
dissolving the magnetic nano-particles coated by the gamma-AlOOH carrier in an ethanol solution, adding an aminosilane compound solution, sequentially stirring and ultrasonically treating to generate a precipitate, performing magnetic separation and water washing on the precipitate, dissolving the precipitate in a new ethanol solution to obtain a particle dispersion solution, adding an acetic acid solution and the nano-gold solution into the particle dispersion solution, uniformly mixing, and sequentially performing ultrasonic treatment, magnetic separation, water washing and drying to obtain the flower-shaped magnetic nano-gold catalyst.
Further, in the step S1, the reaction temperature of the hydrothermal reaction is 150-200 ℃, and the reaction time is 8-12h.
Further, in step S2, the organosilane solution is tetramethoxysilane, tetraethoxysilane, or trimethoxy silane.
Further, in step S3, the aluminum solution is one or more of aluminum isopropoxide, aluminum nitrate, aluminum sulfate and aluminum trichloride.
Further, in the step S3, the ultrasonic treatment time is 10-30min; the reaction temperature of the heat seal reaction is 150-200 ℃, and the reaction time is 12-48h.
Further, in step S4, the gold ion solution is chloroauric acid or gold chloride or potassium chloroaurate; the molar ratio of the sodium borohydride solution to the gold ion solution is 1:4-1:2.
further, in step S5, the aminosilane compound solution is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, or p-aminophenyltrimethoxysilane; the concentration of the ethanol solution is 0.1-2%.
Further, in step S5, the time of ultrasonic treatment is 10-30min.
Compared with the prior art, the invention has the following beneficial effects:
1. the catalyst prepared by the invention is hollow Fe 3 O 4 The magnetic nano-particles are taken as the core, the specific surface area of the core is increased by the porous structure of the magnetic nano-particles, and abundant active sites are provided, so that SiO 2 The coating layer has a more compact structure, and the resistance and the stability of the core are improved.
2. The surface-coated gamma-AlOOH carrier layer of the catalyst prepared by the method provides more active deposition sites, so that the loading capacity of the gold nanoparticles is greatly increased, and the catalyst and the gold nanoparticles form a firm power supply layer. Sodium borohydride negative ions are transferred to the gamma-AlOOH carrier layer through the gold nanoparticles, the substrate reduction reaction can be rapidly carried out, and the catalysis rate is greatly improved.
3. The catalyst prepared by the invention has the advantages that the silane compound is used for coating the magnetic core, the thermal stability of the catalyst is improved, the high-temperature tolerance is good, the magnetic field responsiveness of the catalyst is not influenced, and the repeated recycling performance is good.
Drawings
Fig. 1 is a catalytic efficiency curve diagram of the flower-like magnetic nanogold catalyst prepared in example 1 of the invention in a p-nitrophenol reduction reaction.
Fig. 2 is a catalytic efficiency curve diagram of the flower-like magnetic nano gold catalyst prepared in example 2 of the present invention in p-nitrophenol reduction reaction.
FIG. 3 is a graph showing the catalytic efficiency of the flower-like magnetic nanogold catalyst prepared in example 3 of the invention in p-nitrophenol reduction reaction.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
Example 1:
s1, dissolving 1.01g of ferric chloride hexahydrate in 25ml of water, adding 2.2g of sodium citrate trihydrate and 0.675g of urea, stirring uniformly at room temperature, and transferring to a reaction kettle for hydrothermal reaction. The reaction temperature of the hydrothermal reaction is 200 ℃, the reaction time is 12h, and Fe is generated by the reaction 3 O 4 Precipitating, fe 3 O 4 The precipitate is sequentially subjected to magnetic separation, water washing and drying to obtain hollow Fe 3 O 4 Nanoparticles;
s2, taking the Fe 3 O 4 Dissolving 150mg of nano particles in 15ml of water, adding 5ml of ammonia water and 15ml of tetraethoxysilane with the concentration of 2%, uniformly stirring, and then sequentially carrying out magnetic separation, water washing and drying operations to obtain modified magnetic nano particles;
s3, dissolving the modified magnetic nanoparticles in 200ml of aluminum nitrate to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution for 30min, then adding 10mg of urea into the mixed solution, uniformly stirring, carrying out secondary ultrasonic treatment for 30min, transferring the mixed solution after the secondary ultrasonic treatment into a reaction kettle for heat seal reaction, wherein the temperature of the heat seal reaction is 190 ℃, the reaction time is 36h, cooling to room temperature after the heat seal reaction is finished, and carrying out magnetic separation, water washing and drying on reaction products of the heat seal reaction in sequence to obtain gamma-AlOOH carrier-coated magnetic nanoparticles;
s4, adding a 20mL0.25mM sodium citrate solution into 0.6mL0.25mM chloroauric acid, then adding a 0.6mL0.1M sodium borohydride solution, and reacting to obtain a nanogold solution;
s5, dissolving 10mg of the gamma-AlOOH carrier-coated magnetic nanoparticles into 20mL of ethanol solution (with the concentration of 2%), adding 0.4mL of 3-aminopropyltriethoxysilane, sequentially stirring and ultrasonically treating for 30min to generate precipitates, performing magnetic separation and water washing on the precipitates, dissolving the precipitates into 1mL of new ethanol solution (with the concentration of 2%) to obtain particle dispersion, adding 0.1mL of acetic acid solution and the nanogold solution into the particle dispersion, uniformly mixing, and sequentially performing ultrasonic treatment for 30min, magnetic separation, water washing and drying to obtain the flower-shaped magnetic nanogold catalyst.
The catalytic efficiency of the flower-like magnetic nanogold catalyst prepared in the example was tested using p-nitrophenol reduction as a model. 1.25mL0.1mM p-nitrophenol is taken in a 3mL test tube, and 0.5mL0.1M sodium borohydride solution is added. The flower-like magnetic nanogold catalyst prepared in this example was dissolved in water to prepare a 0.1mg/mL catalyst solution, 0.4mL of the catalyst solution was injected into a test tube using a needle, and the absorption value at 400nm was recorded using a UV-VIS spectrophotometer, and the catalytic efficiency was as shown in fig. 1.
Example 2:
s1, dissolving 1.01g of ferric chloride hexahydrate in 25ml of water, adding 2.2g of sodium citrate trihydrate and 0.675g of urea, stirring uniformly at room temperature, and transferring to a reaction kettle for hydrothermal reaction. The reaction temperature of the hydrothermal reaction is 200 ℃, the reaction time is 12h, and Fe is generated by the reaction 3 O 4 Precipitating, adding Fe 3 O 4 The precipitate is sequentially subjected to magnetic separation, water washing and drying to obtain hollow Fe 3 O 4 Nanoparticles;
s2, taking the Fe 3 O 4 Dissolving 150mg of nano particles in 15ml of water, adding 5ml of ammonia water and 15ml of tetraethoxysilane with the concentration of 2%, uniformly stirring, and then sequentially carrying out magnetic separation, water washing and drying operations to obtain modified magnetic nano particles;
s3, dissolving the modified magnetic nanoparticles in 200ml of aluminum nitrate to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution for 30min, then adding 10mg of urea into the mixed solution, uniformly stirring, carrying out secondary ultrasonic treatment for 30min, transferring the mixed solution after the secondary ultrasonic treatment into a reaction kettle for heat seal reaction, wherein the temperature of the heat seal reaction is 190 ℃, the reaction time is 36h, cooling to room temperature after the heat seal reaction is finished, and carrying out magnetic separation, water washing and drying on reaction products of the heat seal reaction in sequence to obtain gamma-AlOOH carrier-coated magnetic nanoparticles;
s4, adding a 20mL0.25mM sodium citrate solution into 1.2mL0.25mM chloroauric acid, then adding a 0.6mL0.1M sodium borohydride solution, and reacting to obtain a nanogold solution;
s5, dissolving 10mg of the gamma-AlOOH carrier-coated magnetic nanoparticles into 20mL of ethanol solution (with the concentration of 2%), adding 0.4mL of 3-aminopropyltriethoxysilane, sequentially stirring and ultrasonically treating for 30min to generate precipitates, performing magnetic separation and water washing on the precipitates, dissolving the precipitates into 1mL of new ethanol solution (with the concentration of 2%) to obtain particle dispersion liquid, adding 0.1mL of acetic acid solution and the nanogold solution into the particle dispersion liquid, uniformly mixing, sequentially performing ultrasonic treatment for 30min, magnetic separation, water washing and drying to obtain the flower-shaped magnetic nanogold catalyst.
The catalytic efficiency of the flower-like magnetic nanogold catalyst prepared in the example was tested by using p-nitrophenol reduction as a model. 1.25mL0.1mM p-nitrophenol is put into a 3mL test tube, and 0.5mL0.1M sodium borohydride solution is added. The flower-like magnetic nanogold catalyst prepared in this example was dissolved in water to prepare a 0.1mg/mL catalyst solution, 0.4mL of the catalyst solution was injected into a test tube using a needle, and the absorbance at 400nm was recorded using a UV-VIS spectrophotometer, with the catalytic efficiency shown in fig. 2.
Example 3:
s1, dissolving 1.01g of ferric chloride hexahydrate in 25ml of water, adding 2.2g of sodium citrate trihydrate and 0.675g of urea, stirring uniformly at room temperature, and transferring to a reaction kettle for hydrothermal reaction. The reaction temperature of the hydrothermal reaction is 200 ℃, the reaction time is 12h, and Fe is generated by the reaction 3 O 4 Precipitating, fe 3 O 4 The precipitate is sequentially subjected to magnetic separation, water washing and drying to obtain hollow Fe 3 O 4 Nanoparticles;
s2, taking the Fe 3 O 4 Dissolving 150mg of nano particles in 15ml of water, adding 5ml of ammonia water and 15ml of tetraethoxysilane with the concentration of 2%, uniformly stirring, and then sequentially carrying out magnetic separation, water washing and drying operations to obtain modified magnetic nano particles;
s3, dissolving the modified magnetic nanoparticles in 200ml of aluminum nitrate to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution for 30min, then adding 10mg of urea into the mixed solution, uniformly stirring, carrying out secondary ultrasonic treatment for 30min, transferring the mixed solution after the secondary ultrasonic treatment into a reaction kettle for carrying out heat seal reaction, wherein the temperature of the heat seal reaction is 190 ℃, the reaction time is 36h, cooling to room temperature after the heat seal reaction is finished, and carrying out magnetic separation, water washing and drying on the reaction product of the heat seal reaction in sequence to obtain the gamma-AlOOH carrier-coated magnetic nanoparticles;
s4, adding a 20mL0.25mM sodium citrate solution into 1.8mL0.25mM chloroauric acid, then adding a 0.6mL0.1M sodium borohydride solution, and reacting to obtain a nanogold solution;
s5, dissolving 10mg of the gamma-AlOOH carrier-coated magnetic nanoparticles into 20mL of ethanol solution (with the concentration of 2%), adding 0.4mL of 3-aminopropyltriethoxysilane, sequentially stirring and ultrasonically treating for 30min to generate precipitates, performing magnetic separation and water washing on the precipitates, dissolving the precipitates into 1mL of new ethanol solution (with the concentration of 2%) to obtain particle dispersion liquid, adding 0.1mL of acetic acid solution and the nanogold solution into the particle dispersion liquid, uniformly mixing, sequentially performing ultrasonic treatment for 30min, magnetic separation, water washing and drying to obtain the flower-shaped magnetic nanogold catalyst.
The catalytic efficiency of the flower-like magnetic nanogold catalyst prepared in the example was tested by using p-nitrophenol reduction as a model. 1.25mL0.1mM p-nitrophenol is taken in a 3mL test tube, and 0.5mL0.1M sodium borohydride solution is added. The flower-like magnetic nanogold catalyst prepared in this example was dissolved in water to prepare a 0.1mg/mL catalyst solution, 0.4mL of the catalyst solution was injected into a test tube using a needle, and the absorbance at 400nm was recorded using a UV-VIS spectrophotometer, with the catalytic efficiency shown in fig. 3.
In connection with examples 1 to 3 and FIGS. 1 to 3, it can be concluded that: the flower-shaped magnetic nano gold catalyst prepared by the preparation method has a good effect on reduction of p-nitrophenol and has a good application prospect; with the increase of the loading capacity of the gold nanoparticles, the catalytic time is shortened, and the catalytic efficiency is improved; the loading performance of the catalyst carrier is stable.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The preparation method of the flower-shaped magnetic nano gold catalyst is characterized by comprising the following steps of:
s1, preparing hollow Fe 3 O 4 Nanoparticle:
dissolving ferric chloride hexahydrate in water, adding sodium citrate trihydrate and urea, uniformly stirring, transferring into a reaction kettle for hydrothermal reaction to generate Fe 3 O 4 Precipitating, adding Fe 3 O 4 The precipitate is sequentially subjected to magnetic separation, water washing and drying to obtain hollow Fe 3 O 4 Nanoparticles;
s2, preparing modified magnetic nanoparticles:
subjecting said Fe to 3 O 4 Dissolving the nano particles in water, adding ammonia water and an organosilane solution, stirring uniformly, and then sequentially carrying out magnetic separation, water washing and drying operations to obtain modified magnetic nano particles;
s3, preparing the magnetic nano particles coated by the gamma-AlOOH carrier:
dissolving the modified magnetic nanoparticles in an aluminum solution to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution, then adding urea into the mixed solution, uniformly stirring, carrying out secondary ultrasonic treatment, transferring the mixed solution after the secondary ultrasonic treatment to a reaction kettle for heat seal reaction, cooling to room temperature after the heat seal reaction is finished, and carrying out magnetic separation, washing and drying on the reaction product of the heat seal reaction in sequence to obtain gamma-AlOOH carrier coated magnetic nanoparticles;
s4, preparing a nano gold solution:
adding a sodium citrate solution and a sodium borohydride solution into the gold ion solution to carry out reduction reaction to obtain a nano gold solution;
s5, preparing a flower-shaped magnetic nano gold catalyst:
dissolving the magnetic nano-particles coated by the gamma-AlOOH carrier in an ethanol solution, adding an aminosilane compound solution, sequentially stirring and ultrasonically treating to generate a precipitate, performing magnetic separation and water washing on the precipitate, dissolving the precipitate in a new ethanol solution to obtain a particle dispersion solution, adding an acetic acid solution and the nano-gold solution into the particle dispersion solution, uniformly mixing, and sequentially performing ultrasonic treatment, magnetic separation, water washing and drying to obtain the flower-shaped magnetic nano-gold catalyst.
2. The method for preparing the flower-shaped magnetic nano gold catalyst according to claim 1, wherein the method comprises the following steps: in the step S1, the reaction temperature of the hydrothermal reaction is 150-200 ℃, and the reaction time is 8-12h.
3. The method for preparing the flower-shaped magnetic nano gold catalyst according to claim 1, wherein the method comprises the following steps: in step S2, the organosilane solution is tetramethoxysilane, tetraethoxysilane, or trimethoxysilane.
4. The method for preparing the flower-shaped magnetic nano gold catalyst according to claim 1, wherein the method comprises the following steps: in the step S3, the aluminum solution is one or more of aluminum isopropoxide, aluminum nitrate, aluminum sulfate and aluminum trichloride.
5. The method for preparing the flower-shaped magnetic nano gold catalyst according to claim 1, wherein the method comprises the following steps: in the step S3, the ultrasonic treatment time is 10-30min; the reaction temperature of the heat seal reaction is 150-200 ℃, and the reaction time is 12-48h.
6. The method for preparing the flower-shaped magnetic nano gold catalyst according to claim 1, wherein the method comprises the following steps: in the step S4, the gold ion solution is chloroauric acid or gold chloride or potassium chloroaurate; the molar ratio of the sodium borohydride solution to the gold ion solution is 1:4-1:2.
7. the method for preparing the flower-shaped magnetic nano gold catalyst according to claim 1, wherein the method comprises the following steps: in step S5, the aminosilane compound solution is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or p-aminophenyltrimethoxysilane; the concentration of the ethanol solution is 0.1-2%.
8. The method for preparing the flower-shaped magnetic nano gold catalyst according to claim 1, wherein the method comprises the following steps: in step S5, the ultrasonic treatment time is 10-30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210948376.XA CN115155614A (en) | 2022-08-09 | 2022-08-09 | Preparation method and application of flower-shaped magnetic nano gold catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210948376.XA CN115155614A (en) | 2022-08-09 | 2022-08-09 | Preparation method and application of flower-shaped magnetic nano gold catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115155614A true CN115155614A (en) | 2022-10-11 |
Family
ID=83479679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210948376.XA Pending CN115155614A (en) | 2022-08-09 | 2022-08-09 | Preparation method and application of flower-shaped magnetic nano gold catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115155614A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116747878A (en) * | 2023-08-16 | 2023-09-15 | 中国农业大学 | Magnetic nano microsphere and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974314A (en) * | 2012-12-04 | 2013-03-20 | 天津大学 | Magnetic gold nanoparticle composite material, and preparation method and application thereof |
| KR20130042363A (en) * | 2011-10-18 | 2013-04-26 | 숭실대학교산학협력단 | Novel fabrication of polyethyleneimine-capped au-ag alloy nanoparticles |
| CN103191784A (en) * | 2013-03-28 | 2013-07-10 | 北京化工大学 | Magnetic nickel aluminum hydrotalcite composite material loaded with gold nanoparticles and application thereof for catalyzing reduction reaction of p-nitrophenol |
| CN107824198A (en) * | 2017-11-09 | 2018-03-23 | 武汉工程大学 | A kind of preparation method and applications of the magnetic nano-catalyst of supported nano-gold |
| CN108212211A (en) * | 2017-12-30 | 2018-06-29 | 武汉工程大学 | A kind of preparation method of the magnetic nano-catalyst of supported nano-gold |
| CN112619666A (en) * | 2020-11-30 | 2021-04-09 | 深圳市人民医院 | Preparation method and application of central radial-diplopore nano composite material |
-
2022
- 2022-08-09 CN CN202210948376.XA patent/CN115155614A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130042363A (en) * | 2011-10-18 | 2013-04-26 | 숭실대학교산학협력단 | Novel fabrication of polyethyleneimine-capped au-ag alloy nanoparticles |
| CN102974314A (en) * | 2012-12-04 | 2013-03-20 | 天津大学 | Magnetic gold nanoparticle composite material, and preparation method and application thereof |
| CN103191784A (en) * | 2013-03-28 | 2013-07-10 | 北京化工大学 | Magnetic nickel aluminum hydrotalcite composite material loaded with gold nanoparticles and application thereof for catalyzing reduction reaction of p-nitrophenol |
| CN107824198A (en) * | 2017-11-09 | 2018-03-23 | 武汉工程大学 | A kind of preparation method and applications of the magnetic nano-catalyst of supported nano-gold |
| CN108212211A (en) * | 2017-12-30 | 2018-06-29 | 武汉工程大学 | A kind of preparation method of the magnetic nano-catalyst of supported nano-gold |
| CN112619666A (en) * | 2020-11-30 | 2021-04-09 | 深圳市人民医院 | Preparation method and application of central radial-diplopore nano composite material |
Non-Patent Citations (2)
| Title |
|---|
| LINFENG BAI ET AL.: "Spatially ensemble of polydopamine-protected-Au nanocrystals on Fe3O4@SiO2@γ-AlOOH microflower for improving catalytic performance", 《APPLIED SURFACE SCIENCE》, vol. 543, pages 1 - 9 * |
| SHOUHU XUAN ET AL.: "Hierarchical core/shell Fe3O4@SiO2@c-AlOOH@Au micro/nanoflowers for protein immobilization", 《CHEM. COMMUN.》, vol. 47, no. 9, pages 2514 - 2516 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116747878A (en) * | 2023-08-16 | 2023-09-15 | 中国农业大学 | Magnetic nano microsphere and preparation method and application thereof |
| CN116747878B (en) * | 2023-08-16 | 2023-12-05 | 中国农业大学 | Magnetic nano microsphere and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Recent advances in core–shell metal organic frame-based photocatalysts for solar energy conversion | |
| Yin et al. | Construction of NH2-MIL-125 (Ti)/Bi2WO6 composites with accelerated charge separation for degradation of organic contaminants under visible light irradiation | |
| CN107134587B (en) | A kind of solid electrolyte inorganic nano particle filler and preparation method thereof | |
| Xu et al. | MOFs-derived C-In2O3/g-C3N4 heterojunction for enhanced photoreduction CO2 | |
| CN107899592B (en) | Magnetic recyclable flaky NiFe2O4Preparation method and application of/BiOI composite nano material | |
| CN105921149B (en) | A kind of method of solvent hot preparation copper modified titanic oxide nanometer rods | |
| Huang et al. | Construction of a novel Z-scheme V2O5/NH2-MIL-101 (Fe) composite photocatalyst with enhanced photocatalytic degradation of tetracycline | |
| CN106881111A (en) | Composite bismuth vanadium photocatalyst of cuprous oxide and silver-colored mutual load and its preparation method and application | |
| CN101244383A (en) | Process for producing absorbent charcoal loading titanium dioxide photocatalyst | |
| CN103223322A (en) | Preparation method of nanosilver and sulfydryl jointly modified magnetic microspheres | |
| CN109675607A (en) | Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material | |
| CN103007931A (en) | Method for preparing nano silver and titanium dioxide thin films on surfaces of hollow glass beads | |
| CN110227453B (en) | Preparation method of AgCl/ZnO/GO composite visible light catalyst | |
| CN106830049A (en) | A kind of Cu of nanometer sheet composition9 S5The preparation method of hollow 26 face body | |
| CN113477220A (en) | Noble metal ion adsorption material based on magnetic metal organic framework and preparation method thereof | |
| CN103007957A (en) | Method for preparing modified hollow glass beads with magnetism and photocatalytic activity | |
| CN115155614A (en) | Preparation method and application of flower-shaped magnetic nano gold catalyst | |
| CN104923309A (en) | Preparation method for superparamagnetic nanoparticle photocatalyst with Fe3O4-PAMAM-TiO2 core-shell structure | |
| CN106984312A (en) | A kind of composite photocatalyst and preparation method thereof | |
| CN105536877A (en) | Preparation of superparamagnetic Fe3O4-PAMAM-ZnO / TiO2 nanoparticles with core-shell composite structure | |
| Shang et al. | Preparation of magnetic Fe3O4@ PDA/CuS core-shell nanocomposite as a green photocatalyst | |
| CN101786601B (en) | Preparation method of compound nano particle with Fe3O4/CoO core shell structure | |
| CN108295897B (en) | A kind of compounded visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And organic matter degradation application | |
| Li et al. | Three-dimensional monolithic TiO2/ZIF-8/AgCl/Ag-based photocatalytic microreactor for efficient degradation of organic pollutants | |
| CN101862627B (en) | Preparation method of titanium dioxide microcapsule coating noble metal nano particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221011 |