CN108311175A - A kind of hollow cu ferrite/Cellulose nanocrystal catalyst and preparation method thereof - Google Patents
A kind of hollow cu ferrite/Cellulose nanocrystal catalyst and preparation method thereof Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 90
- 239000001913 cellulose Substances 0.000 title claims abstract description 90
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 84
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 38
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 claims abstract description 16
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 27
- 238000013019 agitation Methods 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 13
- 235000019257 ammonium acetate Nutrition 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 239000005695 Ammonium acetate Substances 0.000 claims description 9
- 229940043376 ammonium acetate Drugs 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 229910016516 CuFe2O4 Inorganic materials 0.000 description 9
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- DXKGMXNZSJMWAF-UHFFFAOYSA-N copper;oxido(oxo)iron Chemical compound [Cu+2].[O-][Fe]=O.[O-][Fe]=O DXKGMXNZSJMWAF-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000002604 ultrasonography Methods 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
Hollow cu ferrite/Cellulose nanocrystal catalyst of dispersibility improvement and catalytic performance raising is made in a kind of hollow cu ferrite/Cellulose nanocrystal catalyst of present invention offer and preparation method thereof, the fabricated in situ cu ferrite in Cellulose nanocrystal.Preparation method includes the following steps, step 1, Cellulose nanocrystal, Hydrated copper chloride, iron chloride hexahydrate, ammonium class alkali source and surfactant is dissolved in organic solvent, mixed solution is obtained after being uniformly dispersed；Step 2, mixed solution is subjected to solvent thermal reaction, separates solid after the completion of reaction, washed, it is dry, obtain hollow cu ferrite/Cellulose nanocrystal catalyst.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of hollow cu ferrite/Cellulose nanocrystal catalysis
Agent and preparation method thereof.
Background technology
With the continuous development of industry and farming and animal husbandry, printing and dyeing, petrochemical industry, nitropheneol object caused by medicine and other fields
Matter steps into environment and is formed novel pollution, and since it is with certain bio-toxicity, paranitrophenol is by U.S.'s ring
It protects administration and Environmental Protection in China department is classified as " priority pollutants ", paranitrophenol has certain cumulative bad and holds in the environment
Long property will cause environment long-term harm, and the long-term exposure because of paranitrophenol in the environment, may lead to soil, earth's surface
Water, underground water are by different degrees of pollution.
Cu ferrite (CuFe2O4) have the characteristics that high conductivity, thermal stability and catalytic activity, in electronics, senses and urge
There is wider application in change, is the catalyst for paranitrophenol of degrading generally used.However, due to ferromagnetism and molecule
Between dipolar forces effect, cu ferrite there are problems that easily reunite, bad dispersibility, to limit its catalytic performance.To solve
This problem, a kind of method are that cu ferrite is supported on carrier.But the cu ferrite dispersibility loaded at present still compared with
Difference.
Invention content
It is an object of the invention to overcome current cu ferrite bad dispersibility, what catalytic performance needed to be further increased asks
Topic provides a kind of hollow cu ferrite/Cellulose nanocrystal catalyst and preparation method thereof, Cellulose nanocrystal (CNC,
NCC hollow cu ferrite/cellulose nanometer that dispersibility improves and catalytic performance improves is made in fabricated in situ cu ferrite on)
Crystalline substance (CuFe2O4/ CNC) catalyst.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of hollow cu ferrite/Cellulose nanocrystal catalyst, includes the following steps,
Step 1, Cellulose nanocrystal, Hydrated copper chloride, iron chloride hexahydrate, ammonium class alkali source and surfactant are dissolved in
In organic solvent, mixed solution is obtained after being uniformly dispersed；
Step 2, mixed solution is subjected to solvent thermal reaction, separates solid after the completion of reaction, washed, it is dry, it obtains
To cu ferrite/Cellulose nanocrystal catalyst.
Preferably, in step 1, the length of Cellulose nanocrystal is 150~250nm, a diameter of 10~20nm.
Preferably, in step 1, Cellulose nanocrystal, the ratio of Hydrated copper chloride and iron chloride hexahydrate in mixed solution
For：(0.06~0.2) g：0.1mmol：0.2mmol.
Preferably, in step 1, ammonium class alkali source is one or both of ammonium acetate, ammonium hydrogen carbonate.
Preferably, in step 1, surfactant is one or both of polyethylene glycol, polyvinylpyrrolidone.
Preferably, in step 1, organic solvent is ethylene glycol.
Preferably, in step 1, ammonium class alkali source be ammonium acetate, surfactant be polyethylene glycol and polyvinylpyrrolidone,
Cellulose nanocrystal, Hydrated copper chloride, iron chloride hexahydrate, ammonium acetate, polyethylene glycol and polyvinylpyrrolidine in mixed solution
The ratio of ketone is：(0.06~0.2) g：0.1mmol：0.2mmol：(2~7) g：(0.25~0.75) g：(0.1~0.2) g.
Preferably, step 1 is specially：First Cellulose nanocrystal is dissolved in organic solvent, ultrasonic disperse and mechanical agitation,
Cellulose nanocrystal solution is obtained, then Hydrated copper chloride, iron chloride hexahydrate, ammonium class alkali are added into Cellulose nanocrystal solution
After source, surfactant and organic solvent, ultrasonic disperse and mechanical agitation, mixed solution is obtained.
Preferably, in step 2, reaction temperature is 190~210 DEG C, and the reaction time is 9~11h.
It is a kind of to utilize hollow cu ferrite/Cellulose nanocrystal catalyst made from preparation method as described above.
Compared with prior art, the present invention has technique effect beneficial below：
The present invention prepares hollow cu ferrite/Cellulose nanocrystal catalyst using solvent-thermal method, in Cellulose nanocrystal
Upper fabricated in situ cu ferrite, to which cu ferrite is compound with Cellulose nanocrystal.Cellulose nanocrystal not only has fiber
The basic structure and performance of element, and the characteristic with nano particle, such as high length-diameter ratio, high-specific surface area and high-crystallinity are special
Point, and abundant hydroxyl is contained on surface, the fabricated in situ conducive to metal cation on its surface, thus be a kind of excellent nothing
The ferritic biological carrier materials of load hollow copper of malicious, renewable, degradable, high mechanical properties and good biocompatibility.This
It after cu ferrite is supported on Cellulose nanocrystal by invention, is dispersed on the surface of Cellulose nanocrystal, is not easy to reunite, disperse
Property improve, to improve the catalytic performance of catalyst.Simultaneously as Cellulose nanocrystal has suction-operated to paranitrophenol,
It can further improve the performance of catalyst degradation paranitrophenol.Ammonium class alkali source is added in the present invention, and ammonia is generated after heating, from
And cu ferrite obtained is made to be in hollow structure, a large amount of mesoporous holes are formed, in catalysis is reacted, paranitrophenol can be deep into
In cu ferrite hollow structure, therefore, catalytic site increases, and can further improve catalytic performance.
Further, the present invention by control different Cellulose nanocrystals dosage, prepare different degrees of scatter and
The cu ferrite catalyst of catalytic performance, to realize the controllable preparation of catalyst.
Hollow cu ferrite/Cellulose nanocrystal catalyst produced by the present invention, Kinetics Rate Constants By Using reach
0.56s-1, simple hollow cu ferrite Kinetics Rate Constants By Using is 0.09s-1。
Description of the drawings
Fig. 1 is the TEM figures of hollow cu ferrite/Cellulose nanocrystal catalyst prepared by embodiment 1.
Fig. 2 is the XRD diagram of hollow cu ferrite/Cellulose nanocrystal catalyst prepared by embodiment 1.
Fig. 3 is the FT-IR figures of hollow cu ferrite/Cellulose nanocrystal catalyst prepared by embodiment 1.
Specific implementation mode
The present invention is described in further details with reference to embodiment.
A kind of preparation method of hollow cu ferrite/Cellulose nanocrystal catalyst of the present invention, specifically includes following steps：
Step 1, first a certain amount of Cellulose nanocrystal is added in organic solvent, ultrasound and 25~35min of mechanical agitation,
Obtain Cellulose nanocrystal solution；150~250nm of length of Cellulose nanocrystal, 10~20nm of diameter；
Step 2, a certain amount of Hydrated copper chloride solid, hydration trichlorine are added into the Cellulose nanocrystal solution in step 1
Change iron solid, ammonium class alkali source, surfactant and organic solvent, ultrasonic disperse and 25~35min of mechanical agitation, obtains solution B.
Organic solvent is ethylene glycol (EG)；Ammonium class alkali source is one or both of ammonium acetate, ammonium hydrogen carbonate；Surfactant is poly- second
One or both of glycol (PEG), polyvinylpyrrolidone (PVP).Cellulose nanocrystal, Hydrated copper chloride and hydration trichlorine
Change iron ratio be：(0.06~0.2) g：0.1mmol：0.2mmol.
Step 3, solution B is sealed to using polytetrafluoroethylene (PTFE) as in the autoclave of liner, in 190~210 DEG C of horse
9~11h is not reacted in stove.
Step 4, black solid is detached by permanent magnet from mixture, uses deionized water and absolute ethyl alcohol each respectively
Wash black solid 3~5 times, after in 60 DEG C of vacuum drying chamber dry 2~4h, obtain a kind of hollow cu ferrite/fiber
Plain nanocrystalline catalyst.
In step 2, when ammonium class alkali source is ammonium acetate, surfactant is polyethylene glycol and polyvinylpyrrolidone, mix
Close Cellulose nanocrystal, Hydrated copper chloride, iron chloride hexahydrate, ammonium acetate, polyethylene glycol and polyvinylpyrrolidone in solution
Ratio be：(0.06~0.2) g：0.1mmol：0.2mmol：(2~7) g：(0.25~0.75) g：(0.1~0.2) g.
Wherein, Hydrated copper chloride uses Copper dichloride dihydrate (CuCl2·2H2O), iron chloride hexahydrate is using seven hydrations three
Iron chloride (FeCl3·7H2O)。
Specific embodiment is as follows.
Embodiment 1
The Cellulose nanocrystal of 0.1g is weighed in 40mL ethylene glycol, forms the cellulose nanometer that mass concentration is 0.23%
Brilliant solution, ultrasonic disperse and mechanical agitation 25min；Weigh 0.17g Copper dichloride dihydrates solid, seven iron chloride hexahydrates of 0.54g
Solid, 3.5g ammonium acetates solid, 0.5g polyethylene glycol solid, 0.15g polyvinylpyrrolidones solid and 20mL ethylene glycol are added
In Cellulose nanocrystal solution, ultrasonic disperse and mechanical agitation 25min；Solution after mixing is sealed to polytetrafluoroethyl-ne
Alkene is to react 9h in 200 DEG C of Muffle furnace in the autoclave of liner；By permanent magnet by black solid from mixture
Middle separation respectively washs black solid 3 times with deionized water and absolute ethyl alcohol respectively, after it is dry in 60 DEG C of vacuum drying chamber
2h is to get to hollow cu ferrite/Cellulose nanocrystal catalyst.
Embodiment 2
The Cellulose nanocrystal of 0.3g is weighed in 40mL ethylene glycol, forms the cellulose nanometer that mass concentration is 0.68%
Brilliant solution, ultrasonic disperse and mechanical agitation 35min；Weigh 0.43g Copper dichloride dihydrates solid, seven iron chloride hexahydrates of 1.35g
Solid, 13.9g ammonium acetates solid, 1.0g polyethylene glycol solid, 0.25g polyvinylpyrrolidones solid and 20mL ethylene glycol, add
Enter in Cellulose nanocrystal solution, ultrasonic disperse and mechanical agitation 35min；Solution after mixing is sealed to polytetrafluoro
Ethylene is to react 11h in 200 DEG C of Muffle furnace in the autoclave of liner；By permanent magnet by black solid from mixed
Close object in detach, respectively wash black solid 3 times with deionized water and absolute ethyl alcohol respectively, after in 60 DEG C of vacuum drying chamber do
Dry 4h is to get to hollow cu ferrite/Cellulose nanocrystal catalyst.
Embodiment 3
The Cellulose nanocrystal for weighing 0.2g is dissolved in 40mL ethylene glycol, forms Cellulose nanocrystal solution, ultrasonic disperse
And mechanical agitation 30min；Weigh 0.17g Copper dichloride dihydrates solid, seven iron chloride hexahydrate solids of 0.54g, 3.2g ammonium acetates
It is molten that Cellulose nanocrystal is added in solid, 0.75g polyethylene glycol solid, 0.2g polyvinylpyrrolidones solid and 20mL ethylene glycol
In liquid, ultrasonic disperse and mechanical agitation 35min；Solution after mixing is sealed to the high pressure using polytetrafluoroethylene (PTFE) as liner
In reaction kettle, 8h is reacted in 190 DEG C of Muffle furnace；Black solid is detached from mixture by permanent magnet, is used respectively
Deionized water and absolute ethyl alcohol respectively wash black solid 4 times, after at ambient temperature dry 9h to get to hollow cu ferrite/
Cellulose nanocrystal catalyst.
Embodiment 4
The Cellulose nanocrystal for weighing 0.12g is dissolved in 40mL ethylene glycol, forms Cellulose nanocrystal solution, ultrasonic disperse
And mechanical agitation 30min；Weigh 0.17g Copper dichloride dihydrates solid, seven iron chloride hexahydrate solids of 0.54g, 5g ammonium hydrogen carbonate,
0.6g polyvinylpyrrolidones and 20mL ethylene glycol are added in Cellulose nanocrystal solution, ultrasonic disperse and mechanical agitation
30min；Solution after mixing is sealed to using polytetrafluoroethylene (PTFE) as in the autoclave of liner, in 210 DEG C of Muffle
10h is reacted in stove；Black solid is detached from mixture by permanent magnet, is respectively washed with deionized water and absolute ethyl alcohol respectively
Wash black solid 5 times, after in 60 DEG C of vacuum drying chamber dry 10h urged to get to hollow cu ferrite/Cellulose nanocrystal
Agent.
Embodiment 5
The Cellulose nanocrystal of 0.1g is weighed in 40mL ethylene glycol, forms the cellulose nanometer that mass concentration is 0.23%
Brilliant solution, ultrasonic disperse and mechanical agitation 30min；Weigh 0.28g Copper dichloride dihydrates solid, seven iron chloride hexahydrates of 0.90g
Fiber is added in solid, 11.2g ammonium acetates solid, 0.4g polyethylene glycol solid, 0.32 polyvinylpyrrolidone and 20mL ethylene glycol
In plain nanocrystal solution, ultrasonic disperse and mechanical agitation 30min；Solution after mixing is sealed to and is with polytetrafluoroethylene (PTFE)
In the autoclave of liner, 11h is reacted in 210 DEG C of Muffle furnace；By permanent magnet by black solid from mixture
Separation, respectively wash black solid 5 times with deionized water and absolute ethyl alcohol respectively, after at ambient temperature dry 10h to get in
Empty cu ferrite/Cellulose nanocrystal catalyst.
Embodiment 6
Using the Cellulose nanocrystal of 0.2g, other conditions are same as Example 5.
Embodiment 7
Using the Cellulose nanocrystal of 0.3g, other conditions are same as Example 5.
Comparative example 1
Cellulose nanocrystal is not added, directly carries out solvent hot preparation in a kettle, other conditions are the same as embodiment 5.
It, can be with as shown in Figure 1, the TEM figures of the hollow cu ferrite/Cellulose nanocrystal catalyst obtained for embodiment 1
Find out hollow copper ferrite particle diameter about 300nm, hollow cavity 50~100nm of diameter, and is relatively uniformly dispersed throughout the network of CNC formation
In, illustrate that hollow cu ferrite is synthesized in CNC surface in situ, composite material is successfully prepared.The present invention is received by regulating and controlling cellulose
Meter Jing, the proportioning of cu ferrite and solvent heat preparation process, build the catalyst of different size and shapes.
It, can be with as shown in Fig. 2, the XRD diagram of the hollow cu ferrite/Cellulose nanocrystal catalyst obtained for embodiment 1
Find out hollow CuFe2O4/ CNC composite materials 2 θ=18.5 °, 30.2 °, 35.6 °, 43.2 °, 53.6 °, 57.1 °, 62.8 ° and
Single spinel structure CuFe in diffraction maximum at 74.5 °, with standard card (JCPDS77-0010)2O4Crystal face is consistent, right
The crystal face answered is respectively (111), (220), (311), (400), (422), (511), (440) and (533).Meanwhile 2 θ=
Characteristic peak at 22.5 ° corresponds to (002) crystal face of CNC, and the peak that the diffraction maximum at 50.4 ° is copper simple substance, because preparing
It is middle to use solvent ethylene glycol, due to its excess, part Cu2+It is reduced into Cu simple substance.Therefore, composite material is successfully prepared, and CNC
Addition does not cause CuFe2O4The variation of nanoparticle structure.
As shown in figure 3, the FT-IR figures of the hollow cu ferrite/Cellulose nanocrystal catalyst obtained for embodiment 1.
570cm-1The absorption peak at place corresponds to the vibration of Fe-O keys in cu ferrite；1645cm-1The absorption peak at place corresponds to-OH on CNC
Bending vibration；3400cm-1Place and 3523cm-1The absorption peak at place corresponds to the stretching vibration of N-H, and therefore, infrared spectrum can be with
Prove CuFe2O4/ CNC magnetic composites are successfully prepared.
The fibrous paper of 1 gained of embodiment 5-7 and comparative example is tested for the property, as shown in table 1 below.
Catalyst catalytic performance compares under the additive amount of the different Cellulose nanocrystals of table 1
The test condition of Kinetics Rate Constants By Using in the present invention：To addition 1mL deionizations in 25 μ L paranitrophenols (5mM)
Water, 1mL sodium borohydrides (500mM) and 75 μ L catalyst solutions, CuFe2O4CuFe in/CNC catalyst solutions2O4The concentration of/CNC
For 40mg/mL, in comparative example, CuFe2O4CuFe in catalyst solution2O4Mass concentration and CuFe2O4/ CNC catalyst solutions
Middle CuFe2O4Mass concentration it is identical.
As shown in Table 1, the present invention can be obviously improved the ferritic dispersion of hollow copper by adding Cellulose nanocrystal
Property, the catalyst of different degrees of scatter is built, hollow cu ferrite/Cellulose nanocrystal catalysis of different catalytic performances is obtained
The hollow cu ferrite of Cellulose nanocrystal is not added in agent relatively, adds the hollow cu ferrite of Cellulose nanocrystal, dynamics
Rate constant greatly improves, so as to significantly improve catalytic performance.It can also be seen that adding by adjusting Cellulose nanocrystal
The Kinetics Rate Constants By Using of dosage, gained catalyst changes therewith, i.e., catalytic performance changes therewith, can pass through cellulose nanometer
Brilliant additive amount regulates and controls the dispersibility and catalytic performance of catalyst.
Claims (10)
1. a kind of preparation method of hollow cu ferrite/Cellulose nanocrystal catalyst, which is characterized in that include the following steps,
Step 1, Cellulose nanocrystal, Hydrated copper chloride, iron chloride hexahydrate, ammonium class alkali source and surfactant are dissolved in organic
In solvent, mixed solution is obtained after being uniformly dispersed；
Step 2, mixed solution is subjected to solvent thermal reaction, separates solid after the completion of reaction, washed, it is dry, obtain copper
Ferrite/Cellulose nanocrystal catalyst.
2. the preparation method of hollow cu ferrite/Cellulose nanocrystal catalyst according to claim 1, feature exist
In in step 1, the length of Cellulose nanocrystal is 150~250nm, a diameter of 10~20nm.
3. the preparation method of hollow cu ferrite/Cellulose nanocrystal catalyst according to claim 1, feature exist
In in step 1, the ratio of Cellulose nanocrystal, Hydrated copper chloride and iron chloride hexahydrate is in mixed solution：(0.06~
0.2)g：0.1mmol：0.2mmol.
4. the preparation method of hollow cu ferrite/Cellulose nanocrystal catalyst according to claim 1, feature exist
In in step 1, ammonium class alkali source is one or both of ammonium acetate, ammonium hydrogen carbonate.
5. the preparation method of hollow cu ferrite/Cellulose nanocrystal catalyst according to claim 1, feature exist
In in step 1, surfactant is one or both of polyethylene glycol, polyvinylpyrrolidone.
6. the preparation method of hollow cu ferrite/Cellulose nanocrystal catalyst according to claim 1, feature exist
In in step 1, organic solvent is ethylene glycol.
7. the preparation method of hollow cu ferrite/Cellulose nanocrystal catalyst according to claim 1, feature exist
In in step 1, ammonium class alkali source is ammonium acetate, and surfactant is polyethylene glycol and polyvinylpyrrolidone, fine in mixed solution
The nanocrystalline, Hydrated copper chloride of dimension element, iron chloride hexahydrate, ammonium acetate, polyethylene glycol and polyvinylpyrrolidone ratio be：
(0.06~0.2) g：0.1mmol：0.2mmol：(2~7) g：(0.25~0.75) g：(0.1~0.2) g.
8. the preparation method of hollow cu ferrite/Cellulose nanocrystal catalyst according to claim 1, feature exist
In step 1 is specially：First Cellulose nanocrystal is dissolved in organic solvent, ultrasonic disperse and mechanical agitation obtain cellulose nanometer
Brilliant solution, then Hydrated copper chloride, iron chloride hexahydrate, ammonium class alkali source, surfactant are added into Cellulose nanocrystal solution
And organic solvent, ultrasonic disperse simultaneously after mechanical agitation, obtain mixed solution.
9. the preparation method of hollow cu ferrite/Cellulose nanocrystal catalyst according to claim 1, feature exist
In in step 2, reaction temperature is 190~210 DEG C, and the reaction time is 9~11h.
10. a kind of urged using hollow cu ferrite/Cellulose nanocrystal made from any one of the claim 1-9 preparation methods
Agent.
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| CN115679471A (en) * | 2022-12-09 | 2023-02-03 | 福州市福塑科学技术研究所有限公司 | Preparation method of rod-shaped hollow nano copper oxide antibacterial wear-resistant polyamide fiber |
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