CN107497498A - A kind of preparation method of three layers of spherical shell structure Biocomposite material and products thereof - Google Patents
A kind of preparation method of three layers of spherical shell structure Biocomposite material and products thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011173 biocomposite Substances 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 229910021389 graphene Inorganic materials 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 230000009514 concussion Effects 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000001963 growth medium Substances 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 8
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 2
- YTAHJIFKAKIKAV-XNMGPUDCSA-N [(1R)-3-morpholin-4-yl-1-phenylpropyl] N-[(3S)-2-oxo-5-phenyl-1,3-dihydro-1,4-benzodiazepin-3-yl]carbamate Chemical compound O=C1[C@H](N=C(C2=C(N1)C=CC=C2)C1=CC=CC=C1)NC(O[C@H](CCN1CCOCC1)C1=CC=CC=C1)=O YTAHJIFKAKIKAV-XNMGPUDCSA-N 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 66
- 239000004408 titanium dioxide Substances 0.000 abstract description 17
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000002860 competitive effect Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 21
- 241000233866 Fungi Species 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 210000004400 mucous membrane Anatomy 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical class [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 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
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical group [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/39—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of preparation method of three layers of spherical shell structure Biocomposite material and products thereof, purpose is that solving titanium dioxide is easily dispersed in water, when using it for water treatment field, it is difficult to be recycled, once it is discharged into natural environment, the problem of secondary pollution being caused to environment.This method comprises the following steps：Prepare nano ferriferrous oxide, prepare NTG composites, microculture preparation FMT composites.The present invention can not only be complicated effectively in wastewater by photocatalysis organic principle, and efficient absorption can be carried out to the organic pollution in waste water；Meanwhile the present invention can carry out light-catalyzed reaction, and can effectively recycle and reuse under the regulation and control in magnetic field in designated area.Meanwhile this Biocomposite material FMT prepared by the present invention can be suspended in the water surface, have the characteristics of magnetic recovery, it has the characteristics of cheap, green, is expected to turn into a kind of photochemical catalyst of pole competitive superiority.
Description
Technical field
The present invention relates to field of material preparation, especially catalysis material preparation field, is specially a kind of three layers of spherical shell knot
Preparation method of structure Biocomposite material and products thereof.The present invention passes through three layers of spherical shell structure of in situ synthesis self assembly
Biocomposite material（Referred to as：FMT）, Biocomposite material FMT can be suspended in the water surface, have it is cheap, green, can magnetic
The characteristics of recovery, it is expected to turn into a kind of photochemical catalyst of pole competitive superiority.
Background technology
Photocatalysis technology is substantially the strength that make use of luminous energy, belongs to green technological means, it is in water process
Field has obtained extensive research.The catalytic efficiency of photocatalysis technology depends primarily on the photocatalysis of used catalysis material
Activity；In common catalysis material, titanium dioxide is due to its good chemical stability, high cost performance, abnormal light
Electrical effect and nontoxicity, thus obtained extensive research.However, titanium dioxide is easily dispersed in water, it is difficult to recycling, one
Denier is discharged into natural environment, will be caused secondary pollution to environment, be caused the practice of titanium dioxide to be extremely limited.
Therefore, there is an urgent need to find a kind of method that can synthesize macro-scale composite, to realize titanium dioxide
Practice.
The content of the invention
The goal of the invention of the present invention is：Water is easily dispersed in for titanium dioxide, when using it for water treatment field, it is difficult to
It is recycled, once it is discharged into natural environment, the problem of secondary pollution being caused to environment, there is provided a kind of three layers of spherical shell structure
Preparation method of Biocomposite material and products thereof.The present invention overcomes the above-mentioned deficiency of prior art, there is provided a kind of growth in situ
A kind of Biocomposite material of three layers of spherical shell structure of method self assembly（FMT）Preparation method.This prepared by the present invention
Kind Biocomposite material FMT can be suspended in the water surface, have the characteristics of magnetic recovery, it has the characteristics of cheap, green, has
Prestige turns into a kind of photochemical catalyst of pole competitive superiority.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of preparation method of three layers of spherical shell structure Biocomposite material, comprises the following steps：
（1）Prepare nano ferriferrous oxide
A, by FeCl3•6H2O、FeCl2•4H2O and NaCl are dissolved in deionized water, obtain the first mixed solution, in the first mixing
Solution surface slowly covers one layer of oil film, is then slowly added to sodium hydroxide solution into the first mixed solution, and it is mixed to obtain second
Close solution；
B, the second mixed solution is subjected to magnetic agitation, nano particle therein separated after stirring, isolated
Grain is cleaned with deionized water, is centrifuged, is obtained sample, and obtained sample is freeze-dried successively, encapsulates guarantor
Deposit, obtain nano ferriferrous oxide；
（2）Prepare NTG composites
C, after mixing graphene oxide solution, ammoniacal liquor, deionized water and nine water sulfonic acid titaniums, while magnetic agitation, carry out
Ultrasonic disperse, obtain the 3rd mixed solution；
D, the 3rd mixed solution is transferred in reactor, and reactor is put into baking oven and reacted, be cooled to room afterwards
Temperature, obtain reaction product；
E, step d reaction product is centrifuged, washed, obtain washed product, and washed product ultrasonic disperse is existed
In water, NTG composites are obtained；
（3）Microculture prepares FMT composites
F, hypha,hyphae dispersion liquid, culture medium solution are respectively put into reactor, concussion and cultivate, obtain the 4th solution；
G, the nano ferriferrous oxide of preparation being added in the 4th solution prepared by step f, ultrasonic disperse is uniform, concussion and cultivate,
Obtain the second reaction product；
H, the second obtained reaction product is transferred in new culture medium, and adds excessive NTG composites, concussion and cultivate,
Obtain the 3rd reaction product；
I, the 3rd obtained reaction product is taken out, after salt acid soak, be washed with deionized to neutrality, then carry out freezing and do
Dry processing；
J, after being dried in the product reaction baking oven after freeze-drying process in step i, FMT composites are produced.
In the step a, FeCl3•6H2O、FeCl2•4H2O and NaCl mol ratio is 0.05-1：0.5：3.
In the step a, the concentration of sodium hydroxide is 0.5-2mol/L.
In the step b, cleaned 2-4 times using deionized water, centrifugation speed is 3000-6000 r/min, centrifugation
Time 5-10 min, obtains sample.
In the step c, the concentration of graphene oxide is 1-4 mg/L, ammoniacal liquor, graphene oxide and deionized water volume
Than for 0.5-1:10:12.
In the step c, the time of magnetic agitation and ultrasonic disperse is 0.5-2 h.
In the step d, the heating-up temperature of baking oven is 100-200 DEG C, and the isothermal reaction time is 10-30 h.
In the step e, the speed of centrifugation is 6000-12000 r/min, centrifugation time 5-10 min.
In the step e, step d reaction product is centrifuged, washed, repeated three to six times, washed
Product.
In the step c, with the total volume meter of reaction solution, the quality of the nine water sulfonic acid titaniums added in 1L reaction solutions for 3 ~
15g。
In the step f, hypha,hyphae dispersion liquid, the volume ratio of culture medium solution are 0.5-1:60.
In the step f, shaking table is put into, shaking table steady temperature is 18-26 DEG C, sets shaking speed as 80-160rmp, is returned
Rotation concussion 24-72h.
In the step f, it is put into shaking table, 30 ~ 70h of concussion and cultivate at 25 DEG C, obtains the 4th solution.
In the step g, the concussion and cultivate time is 24 ~ 72h.
In the step i, the concentration of hydrochloric acid is 0.05-0.4mol/L, and soak time is 3-9 h.
In the step j, oven temperature is 60-120 DEG C, and constant temperature time is 12-36 h.
The three layers of spherical shell structure Biocomposite material prepared using preceding method.
The application of the three layers of spherical shell structure Biocomposite material in water process.
For foregoing problems, the present invention provides a kind of preparation method of three layers of spherical shell structure Biocomposite material, this method
Comprise the following steps：Prepare nano ferriferrous oxide, prepare NTG composites, microculture preparation FMT composites.
In one instantiation, nano ferriferrous oxide is prepared first：First by FeCl3•6H2O、FeCl2•4H2O and NaCl are mixed in
In ionized water, then mixed solution surface slowly covering one layer of oil film, sodium hydroxide solution is added dropwise along chamber wall；Again
Obtained solution is separated using strong magnetic force to nano particle, cleaned using deionized water, is centrifuged finally by sample
Freeze-drying, encapsulation preservation obtain nano ferriferrous oxide.Then, NTG composites are prepared：By graphene oxide solution, ammonia
Water, deionized water and the mixing of nine water sulfonic acid titaniums, the additional ultrasonic disperse of magnetic agitation；The solution obtained again is transferred in reactor,
And reactor is put into baking oven and reacted, room temperature is cooled to afterwards；Then, reaction products therefrom is centrifuged and washed
In triplicate, then by product ultrasonic disperse NTG composites are obtained in water.Finally, microculture prepares FMT composite woods
Material：Hypha,hyphae dispersion liquid and culture medium solution are added in 250ml conical flasks, are put into concussion and cultivate in shaking table；Then, will
The iron oxide of nanometer four of preparation is added among culture medium, the uniform concussion and cultivate again of ultrasonic disperse；Obtained product will be reacted again
It is transferred in new culture medium, and adds excessive NTG, the concussion and cultivate in shaking table；Finally, obtained product is taken out, uses salt
After acid soak, it is washed with deionized water to neutrality, then carries out freeze-drying process, and the sample after freeze-drying process is put into baking
Case dries a period of time, obtains FMT composites.Wherein, graphene oxide concentration is 1-4 mg/L, ammoniacal liquor, graphene oxide
It is 0.5-1 with deionized water volume ratio:10:12, nine water sodium sulfonate quality are 0.5-2 g.
Hypha,hyphae（FH）As a kind of thread biological material, it possesses extremely strong vitality and power of regeneration.
Under suitable growing environment, hypha,hyphae can grow to the thread biomass of macro-size within these few days by individual cells,
This filamentous organisms matter is up to centimetre length, and diameter is below 10 microns.Therefore, hypha,hyphae can be obtained largely easily, and this has
Help the practice of fungi.In addition, the inexpensive of hypha,hyphae, green, the filament with uniqueness.Fungi bacterium
Silk often as load nano particle biomass template synthesizing new biomass nano material, microcosmic nano material with it is grand
See material between erected bridge, it is widely used in the fields such as battery, catalyst, water process, in addition, fungi template also by
It is widely used in synthesis nano-noble metal.In consideration of it, biomass template of the hypha,hyphae as carried titanium dioxide nano particle
It is possible to solve these realistic problems.And it is due to fungi that titanium dioxide, which can be easily attached on the cell membrane of hypha,hyphae,
Possess substantial amounts of functional group on the cell membrane of mycelia, such as：Phosphate group, oh group and amino group etc..In addition,
Because the functional group that hypha,hyphae cell wall enriches causes it to possess high adsorption capacity, it is anti-that this is beneficial to photocatalysis
Should, it means that FH（That is hypha,hyphae）With TiO2Collaboration may be played a part of by, which being combined, promotes.However, experimentation is found
Only a small amount of TiO2Nano particle can be attached to the surface of hypha,hyphae, it may be possible to because hypha,hyphae surface lacks activity
Site.
In order to load more TiO2Nano particle, we introduce new carbon graphene, because graphene
There is high specific surface area along with substantial amounts of avtive spot.Therefore, we are using graphene as load nano-TiO2's
Platform, and having loaded the graphene of titanium dioxide and hypha,hyphae can be connected with each other by the effect between functional group.More have
The meaning be titanium dioxide with graphene it is compound after, the absorption property of material can not only be lifted, and improve material pair can
See the susceptibility of light, promote the lifting of its photocatalysis performance.The doping of nitrogen can lift susceptibility of the titanium dioxide to visible ray,
And by hydro-thermal method to TiO2, also can be graphene-doped among/GO incorporations nitrogen can not only mix the lattice of titanium dioxide
Carbon skeleton among, its photocatalysis performance also show the nano composite material of this nitrogen-doped titanium dioxide and nitrogen-doped graphene
（NTG）Photocatalysis performance, and its photocatalysis performance is better than single N doping or only introduces graphene.
In addition, applicant is by introducing nano ferriferrous oxide granule so that the composite of the sandwich construction is circulating
During have can easily recycling advantage, realize product it is simple, efficiently separate, meet that water treatment applications are led
The demand in domain.
In the present invention, using the Biocomposite material of in situ synthesis self assembly three layers of spherical shell structure of kind（Referred to as：
FMT）.Wherein, FMT inside center is made up of hypha,hyphae；Material positioned at intermediate course is to aoxidize three by nanometer four
The nano composite material that iron is formed with hypha,hyphae；And FMT outermost Rotating fields be by N doping titanium dioxide/graphene with
What the composite of hypha,hyphae was formed.The present invention can not only be complicated effectively in wastewater by photocatalysis organic principle, and
And efficient absorption can be carried out to the organic pollution in waste water；Meanwhile it is of the invention under the regulation and control in magnetic field, can be in specified area
Domain carries out light-catalyzed reaction, and can effectively recycle and reuse.
In summary, preparation method of the present invention is gentle, easy to operate, and success rate is high, reproducible, can meet that high-volume is made
Standby and industrialized production demand.Meanwhile FMT can be suspended in the water surface, there is the characteristics of magnetic recovery, its is cheap, green
The characteristics of make it possible to turn into a kind of photochemical catalyst of pole competitive superiority.
Brief description of the drawings
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein：
Fig. 1 is NTG TEM image and TiO2/ GO and NTG XRD spectra.
Fig. 2 is TiO2/ GO and NTG Raman spectrogram.
Fig. 3 is FH and FMT digital pictures and the scanning electron microscope diagram of outer surface.
The cross-section structure analysis and research figure that Fig. 4 is FMT.
Embodiment
All features disclosed in this specification, or disclosed all methods or during the step of, except mutually exclusive
Feature and/or step beyond, can combine in any way.
Any feature disclosed in this specification, unless specifically stated otherwise, can be equivalent by other or with similar purpose
Alternative features are replaced.I.e., unless specifically stated otherwise, each feature is an example in a series of equivalent or similar characteristics
.
In the present embodiment, used six water glucose, absolute ethyl alcohol, solid sodium hydroxide, hydrochloric acid（36%）, dusty yeast
Powder, sodium chloride powder, tannin powder, Iron trichloride hexahydrate, four water frerrous chlorides, peptone powder, the concentrated sulfuric acid（98.3%）, nine
Water titanium sulfate, ammoniacal liquor, provided by Chengdu Ke Long chemical reagents factory, above medicine and reagent is that analysis is pure；And graphene oxide
Made by oneself with liquid fungal spawn useful by inventor.
The method of the present embodiment, comprises the following steps：
（1）It is 0.05-1 by mol ratio：0.5：3 FeCl3•6H2O、FeCl2•4H2O and NaCl be mixed in 200-500ml go from
In sub- water；
（2）One layer of oil film is slowly covered on mixed solution surface, by 50-100 ml 0.5-2 mol/L sodium hydroxide solutions edge
Chamber wall to be added dropwise, above procedure keeps magnetic agitation；
（3）By step（2）Obtained solution is separated using strong magnetic force to nano particle, is cleaned 2-4 times using deionized water,
Rotating speed 3000-6000 r/min are centrifuged, centrifugation time 5-10min, are finally freeze-dried sample, encapsulation preservation obtains
Nano ferriferrous oxide；
（4）It is 1-4 mg/L graphene oxide solutions by concentration, volume ratio 0.5-1:10:12 ammoniacal liquor, graphene oxide are molten
Liquid and deionized water, and 0.5-2 g nine water sulfonic acid titaniums mixing, the additional ultrasonic disperse 0.5-2h of magnetic agitation；
（5）By step（3）Obtained solution is transferred in reactor, and reactor is put into baking oven and carries out reacting baking oven heating
Temperature is 100-200 DEG C, and the isothermal reaction time is 10-30 h, is cooled to room temperature afterwards；
（6）By step（5）Obtained product, centrifuge（Centrifugation rate 6000-12000 r/min）With washing in triplicate,
Product ultrasonic disperse is finally obtained into NTG composites in water；
（7）Hypha,hyphae dispersion liquid and culture medium solution that volume ratio is 0.5-60 are added in 250ml conical flasks, is put into and shakes
Bed in concussion and cultivate for a period of time（Shaking table steady temperature is 18-26 DEG C, sets shaking speed and is circled round as 80-160rmp and shakes 24-
72h）；
（8）By step（3）The obtained iron oxide of nanometer four（0.05-0.4g）Add among culture medium, ultrasonic disperse is uniform, again
Concussion and cultivate is for a period of time（12-36h）；
（9）By step（8）Obtained product, which is transferred in new culture medium, adds excessive NTG, one section of concussion and cultivate in shaking table
Time（24-72h）；
（10）By step（9）Obtained sample uses hydrochloric acid after taking out（0.05-0.4mol/L）3-9 h are soaked, then use deionized water
After being washed till neutrality, freeze-drying process is carried out；
（11）Sample is put into baking oven（Oven temperature is 60-120 DEG C, and constant temperature time is 12-36 h）Dry, it is compound to obtain FMT
Material.
Embodiment 1
1st, FMT composites are prepared
（1）Nano ferriferrous oxide is prepared for using co-electrodeposition method
8g Iron trichloride hexahydrates, the water frerrous chlorides of 3g tetra- and 6g sodium chloride are taken, above solid is mixed with 300mL deionized water,
Wait stirs；One layer of oil film is slowly covered on the top layer of the mixed solution, by 80mL 0.8mol/L hydroxide
Sodium solution is added dropwise along chamber wall, and experimentation solution keeps magnetic agitation.Hereafter, nano particle is entered using strong magnetic force
Row separation, is cleaned three times with deionized water, and 3000r/min is centrifuged, and is finally freeze-dried sample, and encapsulation preserves.
（2）NTG composites are prepared using hydro-thermal method
The graphene oxide solution being already prepared to liquid-transfering gun absorption 20mL（4mg/L）, 2mL ammoniacal liquor add 100mL reaction
Among kettle inner bag, then 35mL deionized waters are measured, weigh in the balance and take the water titanium sulfates of 1g nine, above reagent chemicals is mixed, magnetic force
Stir additional 1 hour of ultrasonic disperse.Afterwards, reactor heated sealed is continued 20 hours to 150 DEG C, question response kettle is cooled to
Room temperature, take out reaction product.Reaction product is centrifuged and washed, in triplicate, finally by reactant ultrasonic disperse in water
In, obtain NTG composites.
（3）FMT composites are prepared using culture of microorganism
Drawn using liquid-transfering gun among the appropriate hypha,hyphae dispersion liquid prepared adds 250mL conical flask, then by 100mL
Culture medium solution is added thereto, and it is 20 DEG C to set shaking table steady temperature, sets shaking speed as 100rmp, and convolution concussion 36 is small
When.Then, 0.15g steps are taken（1）The magnetic ferroferric oxide nanometer particle of preparation is added among culture medium, and ultrasonic disperse is equal
It is even, concussion and cultivate 24 hours again.Then, the bead in culture medium is transferred among new culture medium, and adds excess
NTG, concussion and cultivate 36h.Finally, with after 0.15mol/L salt acid soak 5h after sample is taken out, after being washed to neutrality, enter
Row freeze-drying process, baking oven is placed into, 12h is dried under 80 degrees Celsius, obtains final products.
2nd, TEM and XRD signs and analytic explanation are carried out to sample prepared by embodiment 1
Fig. 1 is chooses FMT outer surfaces sample, with its microstructure of transmission electron microscope observing.According to Fig. 1 a, FMT outer surface is certain
The person of presence NTG, titanium dioxide granule can be clearly apparent and equably cover or be attached on graphene, because titanium dioxide
Titanium nano particle and graphene oxide during hydro-thermal reaction, make to form between them under HTHP Ti-C keys or
Ti-O-C keys.Fig. 1 b are the image K-M in the region, and image is made up of the discontinuous ring of light, and it is polycrystalline knot to illustrate the material
Structure.Tested by transmission electron microscope high-resolution（Fig. 1 c）, the sizes of titania nanoparticles is in 10nm or so, and titanium dioxide
Main interstitial void is 0.343nm, this and titanium dioxide rutile crystal type（101）It is consistent.In addition, we are surveyed using XRD
TiO is tried2/ GO and NTG（In Fig. 1 d, top lines represent TiO2/ Go, lower section lines represent N-TiO2/NG）, as a result such as Fig. 1 d
It is shown, it may be seen that TiO2/ GO and NTG collection of illustrative plates is extremely approximate, also without the peak occurred on nitrogen, by comparing, hair
Existing TiO2/ GO and NTG characteristic peak coincide with titanium dioxide rutile crest.It is worth noting that, 26o stone should be appeared in
Black alkene characteristic peak does not occur, and this is due to that the signal peak of titanium dioxide is extremely strong, is deposited on graphenic surface, masks graphite
The signal of alkene.
3rd, Raman test and analysis
Fig. 2 presents TiO2/ GO and NTG Raman spectrogram（In Fig. 2, top lines represent TiO2/ GO, lower section lines represent
NTG）, wave number 1000cm-1It is the characteristic peak on rutile crystal type below, its peak position is respectively 148（Eg）、198（Eg）、395
（B1g）、510（A1g）With 628（Eg）cm-1.In addition, in TiO2In/GO and NTG Raman spectrograms, wave number 1355cm-1With
1596cm-1Position there are two crests similar to graphene oxide characteristic peak, they represent D bands and G bands respectively.D
It is sp with what is represented3The degree of disorder of hydridization defect and structure；G is sp with what is represented2C=C of hydridization.By calculating D bands and G bands
Peak intensity ratio, find TiO2/GO（1.00）And NTG（1.12）The ratio of graphene oxide D/G in relevant report is above, this
Illustrate TiO2Graphene be present in/GO and NTG structures.In addition, Raman spectrogram medium wave number is more than 2500cm-1It is to belong to 2D
Band, 2D bands can illustrate the stacking situation of graphene, by that can analyze 2D bands the number of plies of graphene, and go out in Raman spectrogram
Two broad peaks are showed, then can illustrate that the material is multi-layer graphene structure, also demonstrated the graphene after hydro-thermal and do not have
It is stacked.
Embodiment 2
1st, FMT composites are prepared
（1）Nano ferriferrous oxide is prepared for using co-electrodeposition method
6g Iron trichloride hexahydrates, the water frerrous chlorides of 2g tetra- and 4g sodium chloride are taken, above solid is mixed with 200mL deionized water,
Wait stirs；One layer of oil film is slowly covered on the top layer of the mixed solution, by 60mL 1mol/L sodium hydroxide
Solution is added dropwise along chamber wall, and experimentation solution keeps magnetic agitation.Hereafter, nano particle is carried out using strong magnetic force
Separation, is cleaned three times with deionized water, and 5000r/min is centrifuged, and is finally freeze-dried sample, and encapsulation preserves.
（2）NTG composites are prepared using hydro-thermal method
The graphene oxide solution being already prepared to liquid-transfering gun absorption 30mL（3.5mg/L）, 2.5mL ammoniacal liquor add 100mL
Among reactor inner bag, then 35mL deionized waters are measured, weigh in the balance and take the water titanium sulfates of 0.8g nine, above reagent chemicals is mixed
Close, 1.5 hours of the additional ultrasonic disperse of magnetic agitation.Afterwards, reactor heated sealed is continued 24 hours to 160 DEG C, treated anti-
Answer kettle to be cooled to room temperature, take out reaction product.Reaction product is centrifuged and washed, repeated centrifugation separates and washed three times,
Finally by reactant ultrasonic disperse in water, NTG composites are obtained.
（3）FMT composites are prepared using culture of microorganism
Drawn using liquid-transfering gun among the hypha,hyphae dispersion liquids that have prepared of 2 mL add 250mL conical flask, then by 120mL
Culture medium solution is added thereto, and it is 20 DEG C to set shaking table steady temperature, sets shaking speed as 120rmp, and convolution concussion 48 is small
When.Then, the magnetic ferroferric oxide nanometer particle for taking 0.1g to prepare is added among culture medium, and ultrasonic disperse is uniform, shakes again
Swing culture 36 hours.Then, the bead in culture medium is transferred among new culture medium, and adds excessive NTG, shaken
Cultivate 48h.Finally, with after 0.2mol/L salt acid soak 6h after sample is taken out, after being washed to neutrality, carry out at freeze-drying
Reason, places into baking oven, dries 24h under 90 degrees Celsius, obtain final products.
2nd, determine
（1）Fig. 3 gives FH and FMT digital pictures and the scanning electron microscope diagram of outer surface.Wherein, Fig. 3 a are that blank is true
The digital pictures of bacterium mycelium pellet, Fig. 3 b are FMT digital pictures, and Fig. 3 c, Fig. 3 e are the scanning electron microscope diagram of hypha,hyphae
Picture, Fig. 3 d, Fig. 3 f are the scanning electron microscope image of FMT outer surfaces.
Fig. 3 a, Fig. 3 b present the macro geometry of FH and FMT hydrogels, and they are chondritic, diameter about 1cm.FMT
The color on surface and FH surface colors are entirely different, and FMT color is in black, it may be possible to because surface covers NTG composite woods
Material.Inventor observes the surface texture of hypha,hyphae by SEM, it is found that blank hypha,hyphae is by a large amount of
What the filamentous fungi of micron size and a small amount of biomass mucous membrane were formed, they are crisscross, have no rule in spatial distribution.Figure
3d presents the microstructure of FMT outer surfaces, it can be found that it is entirely different with the filament of blank hypha,hyphae, it is only a small amount of
Hypha,hyphae be exposed to outer surface, be largely to be made up of multilayer material, and this multilayer material is particularly likely that composite
NTG.In order to further recognize and analyze lamellar structure, inventor carries out the observation of bigger multiple to hypha,hyphae, found first
Hypha,hyphae surface is smooth, and diameter is only 2.5 microns of sizes, and as shown in Figure 3 e, and Fig. 3 f are on the contrary, surface covers greatly
The flakelet of amount, it is extremely approximate with the form of graphene.
（2）Fig. 4 gives FMT cross-section structure analysis and research figure.Wherein, Fig. 4 a be FMT section digital pictures, Fig. 4 b
For the scanning electron microscope image in FMT interlayers, Fig. 4 c are the outermost high-resolution SEM images of FMT, and Fig. 4 d are corresponding for Fig. 4 c
EDS test.
Fig. 4 a are the section digital photographing of FMT hydrogels, and it is the spheroid of a three-decker that can be clearly seen that FMT,
White innermost layer is blank hypha,hyphae；That middle layer is brown, it is believed that is nano ferriferrous oxide and fungi bacterium
The composite of silk（FH/Fe3O4）；Outermost layer shows black, can speculate be hypha,hyphae and NTG composite（FH/NTG）.
Fig. 4 b are the scanning electron microscope image of brown materials, it can be found that ferroferric oxide nano granules can be attached to fungi bacterium
The surface of silk and biomass mucous membrane.Fig. 4 c are the lamellar structure of FMT outer surfaces, it is notable that in the feelings of high-amplification-factor
Under condition, it is clear that on thin slice that uniform fold substantial amounts of little particle, this is particularly likely that nano titania
Grain, in order to confirm its actual constituent, we have carried out EDS tests to the material, and test shows that the group of this sheet surfaces will
Composition is Ti elements and O elements（Fig. 4 d）, this multilayer material surface just confirmed in SEM image is by substantial amounts of titanium dioxide
Nano particle forms.
The invention is not limited in foregoing embodiment.The present invention, which expands to, any in this manual to be disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (10)
1. a kind of preparation method of three layers of spherical shell structure Biocomposite material, it is characterised in that comprise the following steps：
（1）Prepare nano ferriferrous oxide
A, by FeCl3•6H2O、FeCl2•4H2O and NaCl are dissolved in deionized water, obtain the first mixed solution, molten in the first mixing
Liquid surface slowly covers one layer of oil film, is then slowly added to sodium hydroxide solution into the first mixed solution, obtains the second mixing
Solution；
B, the second mixed solution is subjected to magnetic agitation, nano particle therein separated after stirring, isolated
Grain is cleaned with deionized water, is centrifuged, is obtained sample, and obtained sample is freeze-dried successively, encapsulates guarantor
Deposit, obtain nano ferriferrous oxide；
（2）Prepare NTG composites
C, after mixing graphene oxide solution, ammoniacal liquor, deionized water and nine water sulfonic acid titaniums, while magnetic agitation, carry out
Ultrasonic disperse, obtain the 3rd mixed solution；
D, the 3rd mixed solution is transferred in reactor, and reactor is put into baking oven and reacted, be cooled to room afterwards
Temperature, obtain reaction product；
E, step d reaction product is centrifuged, washed, obtain washed product, and washed product ultrasonic disperse is existed
In water, NTG composites are obtained；
（3）Microculture prepares FMT composites
F, hypha,hyphae dispersion liquid, culture medium solution are respectively put into reactor, concussion and cultivate, obtain the 4th solution；
G, the nano ferriferrous oxide of preparation being added in the 4th solution prepared by step f, ultrasonic disperse is uniform, concussion and cultivate,
Obtain the second reaction product；
H, the second obtained reaction product is transferred in new culture medium, and adds excessive NTG composites, concussion and cultivate,
Obtain the 3rd reaction product；
I, the 3rd obtained reaction product is taken out, after salt acid soak, be washed with deionized to neutrality, then carry out freezing and do
Dry processing；
J, after being dried in the product reaction baking oven after freeze-drying process in step i, FMT composites are produced.
2. preparation method according to claim 1, it is characterised in that in the step a, FeCl3•6H2O、FeCl2•4H2O
Mol ratio with NaCl is 0.05-1：0.5：3.
3. preparation method according to claim 1, it is characterised in that in the step a, the concentration of sodium hydroxide is 0.5-
2mol/L。
4. according to the preparation method described in claim any one of 1-3, it is characterised in that in the step c, graphene oxide
Concentration is 1-4 mg/L, and ammoniacal liquor, graphene oxide and deionized water volume ratio are 0.5-1:10:12.
5. preparation method according to claim 1, it is characterised in that in the step d, the heating-up temperature of baking oven is 100-
200 DEG C, the isothermal reaction time is 10-30 h.
6. according to the preparation method described in claim any one of 1-5, it is characterised in that in the step f, hypha,hyphae disperses
Liquid, the volume ratio of culture medium solution are 0.5-1:60.
7. preparation method according to claim 1, it is characterised in that in the step f, be put into shaking table, shaking table constant temperature
Spend for 18-26 DEG C, set shaking speed as 80-160rmp, convolution concussion 24-72h.
8. preparation method according to claim 1, it is characterised in that in the step g, the concussion and cultivate time be 24 ~
72h。
9. according to the preparation method described in claim any one of 1-8, it is characterised in that in the step j, oven temperature is
60-120 DEG C, constant temperature time is 12-36 h.
10. the three layers of spherical shell structure Biocomposite material prepared using any one of preceding claims 1-9 methods described.
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| CN112758924A (en) * | 2021-03-17 | 2021-05-07 | 甘肃省科学院生物研究所 | Graphene material composite biomass activated carbon and preparation method thereof |
| CN114420957A (en) * | 2022-01-24 | 2022-04-29 | 福州大学 | Method for constructing porous iron nano composite carbon material based on saccharomycete carbon template |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110652968A (en) * | 2019-09-29 | 2020-01-07 | 中国农业科学院油料作物研究所 | Magnetic bacterium ball composite material loaded with reduced graphene oxide and preparation method thereof |
| CN110652968B (en) * | 2019-09-29 | 2023-08-18 | 中国农业科学院油料作物研究所 | Magnetic fungus ball composite material loaded with reduced graphene oxide and preparation method thereof |
| CN112758924A (en) * | 2021-03-17 | 2021-05-07 | 甘肃省科学院生物研究所 | Graphene material composite biomass activated carbon and preparation method thereof |
| CN114420957A (en) * | 2022-01-24 | 2022-04-29 | 福州大学 | Method for constructing porous iron nano composite carbon material based on saccharomycete carbon template |
| CN114420957B (en) * | 2022-01-24 | 2023-08-25 | 福州大学 | Method for constructing porous iron nanocomposite carbon material based on saccharomycete carbon template |
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