CN108295904A - A kind of cu ferrite/Cellulose nanocrystal catalyst and preparation method thereof - Google Patents
A kind of cu ferrite/Cellulose nanocrystal catalyst and preparation method thereof Download PDFInfo
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- 239000001913 cellulose Substances 0.000 title claims abstract description 104
- 229920002678 cellulose Polymers 0.000 title claims abstract description 104
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 96
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 45
- 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 18
- 239000010949 copper Substances 0.000 claims abstract description 13
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 32
- 238000013019 agitation Methods 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000001632 sodium acetate Substances 0.000 claims description 9
- 235000017281 sodium acetate Nutrition 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 229910016516 CuFe2O4 Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- -1 polytetrafluoroethylene Polymers 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 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- DXKGMXNZSJMWAF-UHFFFAOYSA-N copper;oxido(oxo)iron Chemical compound [Cu+2].[O-][Fe]=O.[O-][Fe]=O DXKGMXNZSJMWAF-UHFFFAOYSA-N 0.000 description 4
- 235000011091 sodium acetates Nutrition 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 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
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910002480 Cu-O 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
- 241000872198 Serjania polyphylla Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 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
- 235000013339 cereals Nutrition 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
- 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
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 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
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 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
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Inorganic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Cu ferrite/Cellulose nanocrystal catalyst of dispersibility improvement and catalytic performance raising is made in a kind of 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, alkali source and surfactant are 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 cu ferrite/Cellulose nanocrystal catalyst.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of cu ferrite/Cellulose nanocrystal catalyst and
Preparation method.
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
It is widely used in change, is the catalyst for paranitrophenol of degrading generally used.However, due to ferromagnetism and intermolecular
The effect of dipolar forces so that the problem of easily reuniting, bad dispersibility occurs in cu ferrite, to limit its catalytic performance.For solution
Certainly this problem, a kind of method are that cu ferrite is supported on carrier.But the cu ferrite dispersibility loaded at present is still
It is poor.
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 cu ferrite/Cellulose nanocrystal catalyst and preparation method thereof, in Cellulose nanocrystal (CNC, NCC)
Cu ferrite/Cellulose nanocrystal (CuFe that dispersibility improves and catalytic performance improves is made in fabricated in situ cu ferrite2O4/
CNC) catalyst.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of cu ferrite/Cellulose nanocrystal catalyst, includes the following steps,
Step 1, Cellulose nanocrystal, Hydrated copper chloride, iron chloride hexahydrate, 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, 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, alkali source is one or more of sodium acetate, sodium hydroxide, ammonium hydroxide, urea and sodium carbonate.
Preferably, in step 1, surfactant is one or both of polyethylene glycol and polyvinylpyrrolidone.
Preferably, in step 1, organic solvent is ethylene glycol.
Preferably, in step 1, alkali source is sodium acetate, and surfactant is polyethylene glycol, cellulose nanometer in mixed solution
Crystalline substance, Hydrated copper chloride, iron chloride hexahydrate, the ratio of sodium acetate and polyethylene glycol are：(0.06~0.2) g：0.1mmol：
0.2mmol：(1~2) g：(0.25~0.75) 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, alkali source, table are added into Cellulose nanocrystal solution
After face activating agent 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 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 cu ferrite/Cellulose nanocrystal catalyst using solvent-thermal method, former in Cellulose nanocrystal
Position synthesis cu ferrite, to which cu ferrite is compound with Cellulose nanocrystal.Cellulose nanocrystal not only has cellulose
Basic structure and performance, and the characteristic with nano particle, such as the features such as high length-diameter ratio, high-specific surface area and high-crystallinity,
And abundant hydroxyl is contained on surface, be conducive to metal cation its surface fabricated in situ, thus be it is a kind of it is excellent it is nontoxic, can
It regenerates, the ferritic biological carrier materials of supported copper of degradable, high mechanical properties and good biocompatibility.Cu ferrite is born
It after being loaded in Cellulose nanocrystal, is dispersed on the surface of Cellulose nanocrystal, is not easy to reunite, dispersibility improves, to improve
The catalytic performance of catalyst.Simultaneously as Cellulose nanocrystal has suction-operated to paranitrophenol, catalysis can further improve
The performance of agent catalytic degradation paranitrophenol.
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.
Cu ferrite produced by the present invention/Cellulose nanocrystal catalyst, Kinetics Rate Constants By Using reach 0.19s-1, single
Fine copper ferrite Kinetics Rate Constants By Using is 0.11s-1, the cu ferrite obtained/more simple copper and iron of Cellulose nanocrystal catalyst
Oxysome catalyst improves 36~73%.
Description of the drawings
Fig. 1 is the SEM figures of cu ferrite/Cellulose nanocrystal catalyst prepared by embodiment 1.
Fig. 2 is the XRD diagram of cu ferrite/Cellulose nanocrystal catalyst prepared by embodiment 1.
Fig. 3 is the FT-IR figures of cu ferrite/Cellulose nanocrystal catalyst prepared by embodiment 1.
Specific implementation mode
The present invention is described in further details with reference to embodiment.
The preparation method of cu ferrite of the present invention/Cellulose nanocrystal catalyst, 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, alkali source, surfactant and organic solvent, ultrasonic disperse and 25~35min of mechanical agitation, obtains solution B；It is organic
Solvent is ethylene glycol (EG)；Alkali source is one or more of sodium acetate (NaAc), sodium hydroxide, ammonium hydroxide, urea and sodium carbonate；
Surfactant is one or both of polyethylene glycol (PEG) and polyvinylpyrrolidone.Cellulose nanocrystal, chloride hydrate
The ratio of copper and iron chloride hexahydrate is：(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
8~11h 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 dry 8~10h at ambient temperature, obtain cu ferrite/Cellulose nanocrystal catalyst.
In step 2, when alkali source is sodium acetate, surfactant is polyethylene glycol, Cellulose nanocrystal, water in solution B
Closing copper chloride, iron chloride hexahydrate, sodium acetate and polyethylene glycol ratio is：(0.06~0.2) g：0.1mmol：0.2mmol：(1
~2) g：(0.25~0.75) g：(20~100) mL.
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, 1.5g sodium acetates solid, 0.5g polyethylene glycol solid and 20mL ethylene glycol are added in Cellulose nanocrystal solution, ultrasound
Disperse simultaneously mechanical agitation 25min；Solution after mixing is sealed to using polytetrafluoroethylene (PTFE) as in the autoclave of liner,
11h is reacted in 200 DEG C of Muffle furnace；Black solid is detached from mixture by permanent magnet, uses deionized water respectively
Black solid is respectively washed with absolute ethyl alcohol 3 times, after at ambient temperature dry 8h received to get to a kind of cu ferrite/cellulose
The brilliant catalyst of rice.
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, 2.5g sodium acetates solid, 1.0g polyethylene glycol solid and 20mL ethylene glycol are added in Cellulose nanocrystal solution, ultrasound
Disperse simultaneously mechanical agitation 35min；Solution after mixing is sealed to using polytetrafluoroethylene (PTFE) as in the autoclave of liner,
11h is reacted in 200 DEG C of Muffle furnace；Black solid is detached from mixture by permanent magnet, uses deionized water respectively
Black solid is respectively washed with absolute ethyl alcohol 3 times, after dry 10h at ambient temperature to get to 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, 1.6g sodium acetates
Solid, 0.75g polyethylene glycol solid and 20mL ethylene glycol are added in Cellulose nanocrystal solution, ultrasonic disperse and mechanical agitation
35min；Solution after mixing is sealed to using polytetrafluoroethylene (PTFE) as in the autoclave of liner, in 190 DEG C of Muffle
8h 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 4 times, after dry 9h at ambient temperature to get to 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, 1.5g urea,
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 dry 10h at ambient temperature to get to cu ferrite/Cellulose nanocrystal catalyst.
Embodiment 5
The Cellulose nanocrystal for weighing 0.13g 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, 1.3g hydroxides
Sodium, 0.4g polyethylene glycol solid and 20mL ethylene glycol are added in Cellulose nanocrystal solution, ultrasonic disperse and mechanical agitation
25min；Solution after mixing is sealed to using polytetrafluoroethylene (PTFE) as in the autoclave of liner, in 200 DEG C of Muffle
9h 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 dry 9h at ambient temperature to get to cu ferrite/Cellulose nanocrystal catalyst.
Embodiment 6
The Cellulose nanocrystal for weighing 0.15g is dissolved in 40mL ethylene glycol, forms Cellulose nanocrystal solution, ultrasonic disperse
And mechanical agitation 35min；Weigh 0.17g Copper dichloride dihydrates solid, seven iron chloride hexahydrate solids of 0.54g, 2g sodium carbonate,
0.75g polyethylene glycol solid and 20mL ethylene glycol are added in Cellulose nanocrystal solution, ultrasonic disperse and mechanical agitation 35min；
Solution after mixing is sealed to using polytetrafluoroethylene (PTFE) as in the autoclave of liner, it is anti-in 200 DEG C of Muffle furnace
Answer 10h；Black solid is detached from mixture by permanent magnet, respectively washs black with deionized water and absolute ethyl alcohol respectively
Solid 5 times, after dry 10h at ambient temperature to get to a kind of cu ferrite/Cellulose nanocrystal catalyst.
Embodiment 7
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
Solid, 3.2g sodium acetates solid, 0.4g polyethylene glycol solid and 20mL ethylene glycol are added in Cellulose nanocrystal solution, ultrasound
Disperse simultaneously mechanical agitation 30min；Solution after mixing is sealed to using polytetrafluoroethylene (PTFE) as in the autoclave of liner,
11h is reacted in 210 DEG C of Muffle furnace；Black solid is detached from mixture by permanent magnet, uses deionized water respectively
Black solid is respectively washed with absolute ethyl alcohol 5 times, after at ambient temperature dry 10h received to get to a kind of cu ferrite/cellulose
The brilliant catalyst of rice.
Embodiment 8
Using the Cellulose nanocrystal of 0.2g, other conditions are same as Example 7.
Embodiment 9
Using the Cellulose nanocrystal of 0.3g, other conditions are same as Example 7.
Comparative example 1
Cellulose nanocrystal is not added, directly carries out solvent hot preparation in a kettle, other conditions are the same as embodiment 7.
As shown in Figure 1, the SEM figures of the cu ferrite/Cellulose nanocrystal catalyst obtained for embodiment 1, it can be seen that
CuFe2O4Cu ferrite grain size very little in/CNC composite materials, about 10nm, uniform particle sizes are more uniform to be distributed in CNC nets
In shape structure.The present invention builds different rulers by regulating and controlling Cellulose nanocrystal, the proportioning of cu ferrite and solvent heat preparation process
Very little and pattern catalyst.
As shown in Fig. 2, the XRD diagram of the cu ferrite/Cellulose nanocrystal catalyst obtained for embodiment 1, it can be seen that
CuFe2O4/ CNC composite materials are at 2 θ=18.5 °, 30.2 °, 35.6 °, 43.2 °, 53.6 °, 57.1 °, 62.8 ° and 74.5 °
Single spinel structure CuFe in diffraction maximum, with standard card (JCPDS77-0010)2O4Crystal face is consistent, corresponding crystal face
Respectively (111), (220), (311), (400), (422), (511), (440) and (533).Meanwhile the spy at 2 θ=22.5 °
(002) crystal face that peak corresponds to CNC is levied, and the peak that the diffraction maximum at 50.4 ° is copper simple substance, because using solvent second in preparation
Glycol, due to its excess, part Cu2+It is reduced into Cu simple substance.Therefore, composite material is successfully prepared, and the addition of CNC does not cause
CuFe2O4The variation of nanoparticle structure.
As shown in figure 3, the FT-IR figures of the cu ferrite/Cellulose nanocrystal catalyst obtained for embodiment 1, can see
Go out in Fig. 3 (a) is CuFe2O4、CuFe2O4The infrared spectrogram of/CNC.Known by curve (a), CuFe2O4588cm in curve-1It is
The Cu-O keys and Fe-O key absorption peaks of cu ferrite, 3437cm-1It is the absorption peak of O-H on the surface coated PEG of cu ferrite, table
The generation of spinel type ferrite is illustrated.Known by curve (b), 1624cm-1, 2929cm-1And 3437cm-1It corresponds on CNC respectively
The stretching vibration of C-O keys, methylene (- CH2) in c h bond stretching vibration absworption peak and O-H keys flexural vibrations peak,
1112cm-1And 1165cm-1The stretching vibration of the C-O stretching vibrations and C-C skeletons that correspond respectively to cellulosic molecule inner ether is inhaled
It receives, 1058cm-1Corresponding to the C-O stretching vibrations of cellulose alcohol.In addition, CuFe2O4Characteristic absorption peak in CuFe2O4On/CNC
Exist, further demonstrates CuFe2O4Good nucleation, growth on the surfaces CNC.
The fibrous paper of 1 gained of embodiment 7-9 and comparative example is tested for the property, as a result 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 boron in 100 μ L paranitrophenols solution (5mM)
Sodium hydride solution (100mM), 2mg CuFe2O4/ CNC catalyst and 1.9mL deionized waters, in comparative example catalyst amount with
CuFe2O4CuFe in/CNC catalyst2O4Amount it is identical, tested.
As shown in Table 1, the present invention can be obviously improved the dispersibility of cu ferrite, structure by adding Cellulose nanocrystal
The catalyst for building different degrees of scatter obtains cu ferrite/Cellulose nanocrystal catalyst of different catalytic performances, does not add relatively
The cu ferrite for adding Cellulose nanocrystal, adds the cu ferrite of Cellulose nanocrystal, and Kinetics Rate Constants By Using improves 36~
73%, so as to significantly improve catalytic performance.It can also be seen that by adjusting the additive amount of Cellulose nanocrystal, gained is urged
The Kinetics Rate Constants By Using of agent changes therewith, i.e., catalytic performance changes therewith, can pass through the additive amount of Cellulose nanocrystal
The dispersibility and catalytic performance of catalyst are regulated and controled.
Claims (10)
1. a kind of preparation method of cu ferrite/Cellulose nanocrystal catalyst, which is characterized in that include the following steps,
Step 1, Cellulose nanocrystal, Hydrated copper chloride, iron chloride hexahydrate, alkali source and surfactant are dissolved in organic solvent
In, obtain mixed solution 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 cu ferrite according to claim 1/Cellulose nanocrystal catalyst, which is characterized in that step
In rapid 1, the length of Cellulose nanocrystal is 150~250nm, a diameter of 10~20nm.
3. the preparation method of cu ferrite according to claim 1/Cellulose nanocrystal catalyst, which is characterized in that step
In rapid 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 cu ferrite according to claim 1/Cellulose nanocrystal catalyst, which is characterized in that step
In rapid 1, alkali source is one or more of sodium acetate, sodium hydroxide, ammonium hydroxide, urea and sodium carbonate.
5. the preparation method of cu ferrite according to claim 1/Cellulose nanocrystal catalyst, which is characterized in that step
In rapid 1, surfactant is one or both of polyethylene glycol and polyvinylpyrrolidone.
6. the preparation method of cu ferrite according to claim 1/Cellulose nanocrystal catalyst, which is characterized in that step
In rapid 1, organic solvent is ethylene glycol.
7. the preparation method of cu ferrite according to claim 1/Cellulose nanocrystal catalyst, which is characterized in that step
In rapid 1, alkali source is sodium acetate, and surfactant is polyethylene glycol, Cellulose nanocrystal, Hydrated copper chloride, water in mixed solution
Close ferric trichloride, the ratio of sodium acetate and polyethylene glycol is：(0.06~0.2) g：0.1mmol：0.2mmol：(1~2) g：
(0.25~0.75) g.
8. the preparation method of cu ferrite according to claim 1/Cellulose nanocrystal catalyst, which is characterized in that step
Rapid 1 is specially：First Cellulose nanocrystal is dissolved in organic solvent, it is molten to obtain Cellulose nanocrystal for ultrasonic disperse and mechanical agitation
Liquid, then Hydrated copper chloride, iron chloride hexahydrate, alkali source, surfactant and organic molten are added into Cellulose nanocrystal solution
After agent, ultrasonic disperse and mechanical agitation, mixed solution is obtained.
9. the preparation method of cu ferrite according to claim 1/Cellulose nanocrystal catalyst, which is characterized in that step
In rapid 2, reaction temperature is 190~210 DEG C, and the reaction time is 9~11h.
10. a kind of be catalyzed using cu ferrite/Cellulose nanocrystal made from any one of the claim 1-9 preparation methods
Agent.
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