CN103157493A - Noble metal supported composite functional nano sphere catalyst having recoverability function and application thereof in catalyzing reduction of p-nitrophenol - Google Patents
Noble metal supported composite functional nano sphere catalyst having recoverability function and application thereof in catalyzing reduction of p-nitrophenol Download PDFInfo
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- CN103157493A CN103157493A CN2013100912525A CN201310091252A CN103157493A CN 103157493 A CN103157493 A CN 103157493A CN 2013100912525 A CN2013100912525 A CN 2013100912525A CN 201310091252 A CN201310091252 A CN 201310091252A CN 103157493 A CN103157493 A CN 103157493A
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Abstract
The invention belongs to the technical field of a preparation process of applied inorganic composite functional nano materials, and discloses a noble metal supported magnetic composite functional nano sphere catalyst and application thereof in catalyzing reduction of p-nitrophenol. The preparation process of the catalyst comprises the following steps: through an emulsion polymerization technology, coating noble metal nano particles and magnetic nano particles in a polymer; coating a silicon dioxide layer through a sol-gel technology; and calcining a catalyst precursor coated with the silicon material to remove high molecular polymers, surfactant and other organic supports, thus finally obtaining the noble metal supported composite functional nano sphere catalyst which has favorable dispersity in polar solvent and has a recoverability function. The obtained nano sphere catalyst is uniform in particle size distribution, has favorable dispersity in polar solvent, can be stable for a long time, is adjustable in magnetic and noble metal support amount and has economical efficiency of being recoverable. The catalyst shows favorable catalytic activity in catalyzing reduction of p-nitrophenol.
Description
Technical field
The invention belongs to the nano material preparing technical field, especially a kind of complex function nano-sphere catalyst with recyclable function of carried noble metal and the application in the reduction of catalysis p-nitrophenol thereof.
Technical background
Along with the development of nanoscale science and technology, nano-noble metal such as gold, silver, palladium etc. are widely used and study at the various chemical reactions of catalytic field catalysis.Especially the nano material of these noble metal nanometer materials and difference in functionality is combined and formed multi-functional integrated complex function nano material, have simultaneously the functions such as catalysis, electronics or magnetic characteristic, more and more receive publicity.This multi-functional integrated complex function nano material has very large application potential at aspects such as biomedicine, optical device and catalytic action.
In recent years, about synthetic quite a lot of (the Yuen Wu of report of the nanocatalyst of precious metal catalyst, Dingsheng Wang, Zhiqiang Niu, Pengcheng Chen, Gang Zhou, Yadong Li.A Strategy for Designing a Concave Pt – Ni Alloy through Controllable Chemical Etching [J], Angew.Chem.Int.Ed., 2012,51,12524 – 12528.), comprise various synthetic methods (as solvent heat and sol-gel etc.).Yet the noble metal nano catalyst that these obtain can not reclaim, and durability is not strong.Therefore, the complex function nano-sphere catalyst with recyclable function of the synthetic a kind of new carried noble metal of design, make the noble-metal-supported catalyst realize that catalysis simultaneously, has recyclable and durability, make the final realization of nano material utilization in practice have important directive significance.
Summary of the invention
What the purpose of this invention is to provide a kind of carried noble metal has complex function nano-sphere catalyst of recyclable function and preparation method thereof, and is applied to catalysis p-nitrophenol reduction reaction.
The present invention adopts emulsion polymerization technology, noble metal nano particles and magnetic nanoparticle are coated in polymer, then utilize sol-gel technique to coat layer of silicon dioxide, afterwards the catalyst precarsor of coated Si material is calcined, remove organic supports such as high molecular polymer and surfactant, obtained at last the complex function nano-sphere catalyst with recyclable function of good dispersion carried noble metal in polar solvent.
The preparation method of the complex function nano-sphere catalyst with recyclable function of carried noble metal of the present invention is as follows:
A. the noble metal nano particles of the magnetic nanoparticle of oil phase and oil phase is dispersed in the chloroform of 750-1000 μ l and obtains mixing nanoparticles solution, wherein magnetic nanoparticle is 2-3mmol, and noble metal nano particles is 0.03-0.8mmol; The dodecyl sodium sulfate of 0.05-0.55g is added in the 10-12ml deionized water dissolve, then join in above-mentioned mixing nanoparticles solution, under ice bath protection in the ultrasonic cell-break machine ultrasonic 3-5 minute, obtain the nano particle emulsion, then under vacuum condition 60-65 ℃ revolve and steamed 10-15 minute;
B. the 0.01-0.0125g dodecyl sodium sulfate is added in the 10-15ml deionized water and dissolve, then add 195-200 μ L styrene, 50-55 μ L GDMA and 95-100 μ L hydroxyethyl methacrylate, in the ultrasonic cell-break machine ultrasonic 3-5 minute;
C. the product that step a and b is obtained adds the 0.005-0.01g azo-bis-isobutyl cyanide after mixing, 75-80 ℃ of reaction 10-12h; Cooling rear centrifugal, the centrifugal 15-30 of 9000-10000r/min minute, the solid that obtains is dissolved in water, then centrifuge washing 2-3 time, at last with the product stable dispersion in the 5-10ml deionized water, the carried noble metal magnetic coupling function nano-ball of the sub-polymer overmold that namely secures satisfactory grades;
D. the 0.120-0.125g Tween-20 is dissolved in the 20-25mL deionized water, then add the product in step c, be put in supersonic wave cleaning machine ultrasonic, then add successively the 70-75mL isopropyl alcohol, 0.8-1mL ammoniacal liquor, 450-500 μ L ethyl orthosilicate, the mixed solution that obtains at room temperature stirs 10-12h, namely coats the layer of silicon dioxide shell on the surface of the carried noble metal magnetic coupling function nano-ball of original polymer overmold;
E. the centrifugal 15-30 of product 9000-10000r/min that steps d is obtained minute, the gained solid was placed in tube furnace 350-400 ℃ of calcining 5-10h at last at 60-65 ℃ of baking 5-10h.
The magnetic nanoparticle of described oil phase is the ferroferric oxide nano granules of coated with oleic acid, and particle diameter is at 5-10nm; The noble metal nano particles of oil phase is gold or the palladium nano-particles of coated with oleic acid, and particle diameter is at 2-5nm.
The particle diameter of the complex function nano-sphere catalyst with recyclable function of resulting carried noble metal is 50-100nm, and particle diameter is evenly distributed, and its structure is that noble metal and magnetic nanoparticle load on SiO
2In nanosphere, described noble metal is gold or palladium nano-particles, and magnetic nanoparticle is Fe
3O
4
The complex function nano-sphere catalyst with recyclable function of the carried noble metal of above-mentioned preparation is applied to the reduction reaction of catalysis p-nitrophenol.
The concrete operation step of above-mentioned catalysis p-nitrophenol reduction reaction is: the complex function nano-sphere catalyst with recyclable function of the carried noble metal of 2.5-25 μ g is joined the NaBH that 1mL concentration is 16mg/mL
4In solution, adding 1mL concentration after activation 30min is the p-nitrophenyl phenol solution of 0.4mg/mL again, and the volume water constant volume of end reaction test is 5mL; Then the test UV absorption changes on ultraviolet specrophotometer, and the spectrum test scope is 250-500nm.
Beneficial effect: the particle diameter of the nano-sphere catalyst of the complex function that the present invention obtains is evenly distributed, can be stable for a long time in polar solvent, and the load capacity of noble metal is adjustable, and has callable economy.After high-temperature calcination, the organic matters such as macromolecule and surfactant are burnt, and are conducive to improve the catalytic activity of noble metal.Due to the introducing of magnetic support material, not only make material have callable character, and stoped the reunion of hot conditions noble metal nano particles simultaneously.In addition, the complex function nano-sphere catalyst with recyclable function of the carried noble metal that synthesizes of the present invention has demonstrated good catalytic activity in the reduction of catalysis paranitrophenol.Synthesize the field in the catalyst preparation and have important application value, and synthetic cost is relatively cheap.
Description of drawings
The transmission electron microscope picture of the magnetic coupling function nano-ball of the carried noble metal gold that Fig. 1: embodiment 1 makes.
The transmission electron microscope picture of the magnetic coupling function nano-ball of the supported precious metal palladium that Fig. 2: embodiment 2 makes.
The transmission electron microscope picture of the magnetic coupling function nano-ball of the supported precious metal palladium that Fig. 3: embodiment 3 makes.
The particle diameter distribution map of the magnetic coupling function nano-ball of the supported precious metal palladium that Fig. 4: embodiment 3 makes.
The magnetic of the magnetic coupling function nano-ball of the supported precious metal palladium that Fig. 5: embodiment 3 makes separates photo in kind.
The fourier infrared conversion spectrum of the magnetic coupling function nano-ball of the supported precious metal palladium that Fig. 6: embodiment 3 makes.
The magnetic coupling function nano-ball X-ray diffractogram of the supported precious metal palladium that Fig. 7: embodiment 3 makes.
The magnetic coupling function nano-ball catalytic reduction p-nitrophenol uv-visible absorption spectra phenogram of the carried noble metal gold that Fig. 8: embodiment 1 makes.
The magnetic coupling function nano-ball catalytic reduction p-nitrophenol uv-visible absorption spectra phenogram of the supported precious metal palladium that Fig. 9: embodiment 2 makes.
The magnetic coupling function nano-ball catalytic reduction p-nitrophenol uv-visible absorption spectra phenogram of the supported precious metal palladium that Figure 10: embodiment 3 makes.
The specific embodiment
Embodiment 1
A. the gold nano grain of the ferroferric oxide nano granules of coated with oleic acid and coated with oleic acid is dispersed in the chloroform of 750 μ l and obtains mixing nanoparticles solution, wherein the ferroferric oxide nano granules of coated with oleic acid is 2mmol, particle diameter is at 5-10nm, the gold nano grain of coated with oleic acid is 0.03mmol, and particle diameter is at 2-5nm; The 0.05g dodecyl sodium sulfate is added in the 10ml deionized water dissolve, then join in above-mentioned mixing nanoparticles solution, under ice bath protection in the ultrasonic cell-break machine ultrasonic 3 minutes, obtain the nano particle emulsion, then lower 60 ℃ of vacuum condition revolves and steamed 10 minutes, obtains oil-in-water mixing nanoparticles solution;
B. the 0.01g dodecyl sodium sulfate is added in the 15ml deionized water and dissolve, then add 200 μ L styrene, 50 μ L GDMAs and 100 μ L hydroxyethyl methacrylates, in the ultrasonic cell-break machine ultrasonic 5 minutes;
C. the product that step a and b is obtained adds the 0.005g azo-bis-isobutyl cyanide after mixing, 78 ℃ of reaction 10h; Centrifugal 15 minutes of cooling rear 10000r/min is dissolved in water the solid that obtains, then centrifuge washing 2 times, at last with the product stable dispersion in the 5ml deionized water, the magnetic coupling function nano-ball of the carried noble metal gold of the sub-polymer overmold that namely secures satisfactory grades;
D. the 0.120g Tween-20 is dissolved in the 20mL deionized water, then add the product in step c, be put in supersonic wave cleaning machine ultrasonic, then add successively the 75mL isopropyl alcohol, 1mL concentration is the ammoniacal liquor of 25wt%, 500 μ L ethyl orthosilicates, the mixed solution that obtains at room temperature stirs 12h, namely coats the layer of silicon dioxide shell on the surface of the carried noble metal magnetic coupling function nano-ball of original polymer overmold;
E. centrifugal 15 minutes of the mixing material 10000r/min that steps d is obtained, gained solid are placed in 400 ℃ of calcining 5h of tube furnace at last at 60 ℃ of baking 5h.
The particle diameter of the complex function nano-sphere catalyst with recyclable function of the resulting carried noble metal of step e is 50-100nm, and particle diameter is evenly distributed, and its structure is that noble metal and magnetic nanoparticle load on SiO
2In nanosphere, described noble metal is gold nano grain, and magnetic nanoparticle is Fe
3O
4
The complex function nano-sphere catalyst with recyclable function of the carried noble metal of above-mentioned preparation is applied to the reduction reaction of catalysis p-nitrophenol, concrete operation step is: the complex function nano-sphere catalyst with recyclable function of the carried noble metal of 25 μ g is joined the NaBH that 1mL concentration is 16mg/mL
4In solution, adding 1mL concentration after activation 30min is the p-nitrophenyl phenol solution of 0.4mg/mL again, and the volume water constant volume of end reaction test is 5mL; Then test UV absorption every specified time interval and change on ultraviolet specrophotometer, the spectrum test scope is 250-500nm.
The test result of UV absorption can see in Fig. 8, and the kinetic constant that can calculate thus its catalysis is 0.00373S as calculated
-1, conversion ratio can reach more than 95%.
Embodiment 2
A. the palladium nano-particles of the ferroferric oxide nano granules of coated with oleic acid and coated with oleic acid is dispersed in the chloroform of 1000 μ l and obtains mixing nanoparticles solution, wherein the ferroferric oxide nano granules of coated with oleic acid is 3mmol, particle diameter is at 5-10nm, the palladium nano-particles of coated with oleic acid is 0.4mmol, and particle diameter is at 2-5nm; The 0.55g dodecyl sodium sulfate is added in the 12ml deionized water dissolve, then join in above-mentioned mixing nanoparticles solution, under ice bath protection in the ultrasonic cell-break machine ultrasonic 3 minutes, obtain the nano particle emulsion, then lower 65 ℃ of vacuum condition revolves and steamed 10 minutes, obtains oil-in-water mixing nanoparticles solution;
B. the 0.0125g dodecyl sodium sulfate is added in the 10ml deionized water and dissolve, then add 195 μ L styrene, 55 μ L GDMAs and 100 μ L hydroxyethyl methacrylates, in the ultrasonic cell-break machine ultrasonic 5 minutes;
C. the product that step a and b is obtained adds the 0.01g azo-bis-isobutyl cyanide after mixing, 80 ℃ of reaction 12h; Centrifugal 30 minutes of cooling rear 10000r/min is dissolved in water the solid that obtains, then centrifuge washing 3 times, at last with the product stable dispersion in the 10ml deionized water, the magnetic coupling function nano-ball of the supported precious metal palladium of the sub-polymer overmold that namely secures satisfactory grades;
D. the 0.125g Tween-20 is dissolved in the 25mL deionized water, then add the product in step c, be put in supersonic wave cleaning machine ultrasonic, then add successively the 70mL isopropyl alcohol, 0.8mL concentration is the ammoniacal liquor of 25wt%, 450 μ L ethyl orthosilicates, the mixed solution that obtains at room temperature stirs 10h, namely coats the layer of silicon dioxide shell on the surface of the carried noble metal magnetic coupling function nano-ball of original polymer overmold;
E. centrifugal 30 minutes of the mixing material 9000r/min that steps d is obtained, gained solid are placed in 400 ℃ of calcining 5h of tube furnace at last at 65 ℃ of baking 5h.
The particle diameter of the complex function nano-sphere catalyst with recyclable function of the resulting carried noble metal of step e is 50-100nm, and particle diameter is evenly distributed, and its structure is that noble metal and magnetic nanoparticle load on SiO
2In nanosphere, described noble metal is palladium nano-particles, and magnetic nanoparticle is Fe
3O
4
The complex function nano-sphere catalyst with recyclable function of the carried noble metal of above-mentioned preparation is applied to the reduction reaction of catalysis p-nitrophenol, concrete operation step is: the complex function nano-sphere catalyst with recyclable function of the carried noble metal of 2.5 μ g is joined the NaBH that 1mL concentration is 16mg/mL
4In solution, adding 1mL concentration after activation 30min is the p-nitrophenyl phenol solution of 0.4mg/mL again, and the volume water constant volume of end reaction test is 5mL; Then test UV absorption every specified time interval and change on ultraviolet specrophotometer, the spectrum test scope is 250-500nm.
The test result of UV absorption can see in Fig. 9, and the kinetic constant that can calculate thus its catalysis is 0.00459S as calculated
-1, conversion ratio can reach more than 95%.
A. the palladium nano-particles of the ferroferric oxide nano granules of coated with oleic acid and coated with oleic acid is dispersed in the chloroform of 800 μ l and obtains mixing nanoparticles solution, wherein the ferroferric oxide nano granules of coated with oleic acid is 2mmol, particle diameter is at 5-10nm, the palladium nano-particles of coated with oleic acid is 0.8mmol, and particle diameter is at 2-5nm; The 0.05g dodecyl sodium sulfate is added in the 10ml deionized water dissolve, then join in above-mentioned mixing nanoparticles solution, under ice bath protection in the ultrasonic cell-break machine ultrasonic 3 minutes, obtain the nano particle emulsion, then lower 60 ℃ of vacuum condition revolves and steamed 10 minutes, obtains oil-in-water mixing nanoparticles solution;
B. the 0.0125g dodecyl sodium sulfate is added in the 12ml deionized water and dissolve, then add 200 μ L styrene, 50 μ L GDMAs and 100 μ L hydroxyethyl methacrylates, in the ultrasonic cell-break machine ultrasonic 3 minutes;
C. the product that step a and b is obtained adds the 0.01g azo-bis-isobutyl cyanide after mixing, 75 ℃ of reaction 10h; Centrifugal 30 minutes of cooling rear 10000r/min is dissolved in water the solid that obtains, then centrifuge washing 2 times, at last with the product stable dispersion in the 5ml deionized water, the magnetic coupling function nano-ball of the supported precious metal palladium of the sub-polymer overmold that namely secures satisfactory grades;
D. the 0.120g Tween-20 is dissolved in the 25mL deionized water, then add the product in step c, be put in supersonic wave cleaning machine ultrasonic, then add successively the 70mL isopropyl alcohol, 1mL concentration is the ammoniacal liquor of 25wt%, 500 μ L ethyl orthosilicates, the mixed solution that obtains at room temperature stirs 10h, namely coats the layer of silicon dioxide shell on the surface of the carried noble metal magnetic coupling function nano-ball of original polymer overmold;
E. centrifugal 30 minutes of the mixing material 9000r/min that steps d is obtained, gained solid are placed in 350 ℃ of calcining 5h of tube furnace at last at 60 ℃ of baking 10h.
The particle diameter of the complex function nano-sphere catalyst with recyclable function of the resulting carried noble metal of step e is 50-100nm, and particle diameter is evenly distributed, and its structure is that noble metal and magnetic nanoparticle load on SiO
2In nanosphere, described noble metal is palladium nano-particles, and magnetic nanoparticle is Fe
3O
O
The complex function nano-sphere catalyst with recyclable function of the carried noble metal of above-mentioned preparation is applied to the reduction reaction of catalysis p-nitrophenol, concrete operation step is: the complex function nano-sphere catalyst with recyclable function of the carried noble metal of 2.5 μ g is joined the NaBH that 1mL concentration is 16mg/mL
4In solution, adding 1mL concentration after activation 30min is the p-nitrophenyl phenol solution of 0.4mg/mL again, and the volume water constant volume of end reaction test is 5mL; Then test UV absorption every specified time interval and change on ultraviolet specrophotometer, the spectrum test scope is 250-500nm.
The test result of UV absorption can see in Figure 10, and the kinetic constant that can calculate thus its catalysis is 0.013S as calculated
-1, conversion ratio can reach more than 95%.
Claims (4)
1. the preparation method of the complex function nano-sphere catalyst with recyclable function of a carried noble metal, is characterized in that, its concrete preparation process is as follows:
A. the noble metal nano particles of the magnetic nanoparticle of oil phase and oil phase is dispersed in the chloroform of 750-1000 μ l and obtains mixing nanoparticles solution, wherein magnetic nanoparticle is 2-3mmol, and noble metal nano particles is 0.03-0.8mmol; The dodecyl sodium sulfate of 0.05-0.55g is added in the 10-12ml deionized water dissolve, then join in above-mentioned mixing nanoparticles solution, under ice bath protection in the ultrasonic cell-break machine ultrasonic 3-5 minute, obtain the nano particle emulsion, then under vacuum condition 60-65 ℃ revolve and steamed 10-15 minute;
B. the 0.01-0.0125g dodecyl sodium sulfate is added in the 10-15ml deionized water and dissolve, then add 195-200 μ L styrene, 50-55 μ L GDMA and 95-100 μ L hydroxyethyl methacrylate, in the ultrasonic cell-break machine ultrasonic 3-5 minute;
C. the product that step a and b is obtained adds the 0.005-0.01g azo-bis-isobutyl cyanide after mixing, 75-80 ℃ of reaction 10-12h; Cooling rear centrifugal, the centrifugal 15-30 of 9000-10000r/min minute, the solid that obtains is dissolved in water, then centrifuge washing 2-3 time, at last with the product stable dispersion in the 5-10ml deionized water, the carried noble metal magnetic coupling function nano-ball of the sub-polymer overmold that namely secures satisfactory grades;
D. the 0.120-0.125g Tween-20 is dissolved in the 20-25mL deionized water, then add the product in step c, be put in supersonic wave cleaning machine ultrasonic, then add successively the 70-75mL isopropyl alcohol, 0.8-1mL ammoniacal liquor, 450-500 μ L ethyl orthosilicate, the mixed solution that obtains at room temperature stirs 10-12h, namely coats the layer of silicon dioxide shell on the surface of the carried noble metal magnetic coupling function nano-ball of original polymer overmold;
E. the centrifugal 15-30 of product 9000-10000r/min that steps d is obtained minute, the gained solid was placed in tube furnace 350-400 ℃ of calcining 5-10h at last at 60-65 ℃ of baking 5-10h.
2. preparation method according to claim 1, is characterized in that, the magnetic nanoparticle of described oil phase is the ferroferric oxide nano granules of coated with oleic acid, and particle diameter is at 5-10nm; The noble metal nano particles of oil phase is gold or the palladium nano-particles of coated with oleic acid, and particle diameter is at 2-5nm.
3. preparation method according to claim 1 and 2, it is characterized in that, the particle diameter of the complex function nano-sphere catalyst with recyclable function of resulting carried noble metal is 50-100nm, and particle diameter is evenly distributed, and its structure is that noble metal and magnetic nanoparticle load on SiO
2In nanosphere, described noble metal is gold or palladium nano-particles, and magnetic nanoparticle is Fe
3O
4
4. the application of the complex function nano-sphere catalyst catalysis p-nitrophenol reduction reaction with recyclable function of the carried noble metal for preparing of preparation method according to claim 1 and 2.
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| CN109847762A (en) * | 2019-01-18 | 2019-06-07 | 中国科学院宁波材料技术与工程研究所 | Catalyst, preparation method and application for the reaction of hydrogenation synthesis para-aminophenol |
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| CN101256864A (en) * | 2008-01-07 | 2008-09-03 | 吉林大学 | Superparamagnetism mesoporous silicon dioxide composite ball and preparing method thereof |
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| CN102527437A (en) * | 2010-12-16 | 2012-07-04 | 中国科学院福建物质结构研究所 | Magnetically-separable noble metal catalyst and preparation method thereof |
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| CN101256864A (en) * | 2008-01-07 | 2008-09-03 | 吉林大学 | Superparamagnetism mesoporous silicon dioxide composite ball and preparing method thereof |
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| CN109847762A (en) * | 2019-01-18 | 2019-06-07 | 中国科学院宁波材料技术与工程研究所 | Catalyst, preparation method and application for the reaction of hydrogenation synthesis para-aminophenol |
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