CN106348348A - Functionalized porous ferroferric oxide nano material for efficiently collecting oil-bearing algae and preparation method thereof - Google Patents
Functionalized porous ferroferric oxide nano material for efficiently collecting oil-bearing algae and preparation method thereof Download PDFInfo
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- CN106348348A CN106348348A CN201610604025.1A CN201610604025A CN106348348A CN 106348348 A CN106348348 A CN 106348348A CN 201610604025 A CN201610604025 A CN 201610604025A CN 106348348 A CN106348348 A CN 106348348A
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- ferroferric oxide
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 48
- 241000195493 Cryptophyta Species 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000724 poly(L-arginine) polymer Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000007306 functionalization reaction Methods 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 29
- 238000003306 harvesting Methods 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 14
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 4
- 238000011938 amidation process Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 238000005034 decoration Methods 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 1
- 108010011110 polyarginine Proteins 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- 238000003756 stirring Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000001509 sodium citrate Substances 0.000 description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000037452 priming Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000001154 acute effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical class CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001934 delay Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- -1 3- dimethylamino-propyl Chemical group 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The invention discloses a functionalized porous ferroferric oxide nano material for efficiently collecting oil-bearing algae and a preparation method thereof and belongs to nano materials and the technical field of their application. The functionalized porous ferroferric oxide nano material comprises porous ferroferric oxide and long-chain polyarginine that modifies the same; the functionalized porous ferroferric oxide nano material has bulk porous structure; when applied to efficiently collecting oil-bearing algae, 10-100 mg/L of the functionalized porous ferroferric oxide nano material can be added to provide collecting efficiency of 95% and above within 2-10 min, high collection can also be maintained in the pH range of 4.0-10.0, influence of external acid and base changes is effectively resisted, and 60-85% of the collecting efficiency can be maintained after 5 times of recycling; the process is simple, low in cost and safe and environment-friendly, and the obtained functionalized porous ferroferric oxide nano material is superparamagnetic, is easy to recycle and reusable, is high in collecting efficiency for oil-bearing algae, and has a promising application prospect.
Description
Technical field
Belong to nano material and its applied technical field, particularly to a kind of functionalization porous efficiently harvesting for oily algae
Ferriferrous oxide nanometer material and preparation method thereof.
Background technology
Bioenergy has that recyclability, amount of storage be big, storability and substituting good and Carbon budget balance, is considered
Be 21 century solve the most promising energy of energy crisis (Ji Zhanwu, Zheng Wenfan. with regard to development bioenergy dissolve the energy danger
The thinking [j] of machine. Northeastern University's journal (Social Science Edition), 2009,11 (6): 490-495).As biomass energy it
One, microalgae has photosynthetic efficiency height, and cell proliferation is fast, with short production cycle, lipid content height, the lubricant component being produced and vegetable oil
Similar, and the advantages of do not affect global energy and distribute, be prepare biodiesel desirable material (Jiang Xiaofei, Zhou Hongru,
Jin Qingzhe, etc. the progress [j] of microalgae grease preparation technique. Chinese oil, 2012,37 (10): 62-66).Microalgae
Biodiesel has a good application prospect as regenerative resource, on the premise of production technology feasibility has been found to, tool
There are huge productive potentialities and commercial value.Microalgae is because cell volume is little, density is low, water content is high so that difficult in harvesting
To be dehydrated.Additionally, each microalgae cell size, shape, density and Cell surface characteristics are all different, for
Plant-scale both culturing microalgae, a microalgae always bottleneck from algae solution.Traditional solid-liquid separation technique is all difficult to directly
For microalgae recovery: the Organic substance of individual excessively small microalgae and its secretion can lead to filter membrane blocking to make filtration inefficiencies；Surely
Fixed algae solution suspension system cannot natural subsidence；And the low concentration of algae solution then makes, and power centrifugal efficiency is low, cost is high.Conventional
Traditional microalgae harvesting method all exist economically with technical defect, application on have certain limitation.Using magnetic
Nano material Magnetic Isolation harvesting microalgae technology possess simple to operate, separate that rapid, operating cost is low and energy saving etc. is each
The advantage of kind.But exposed magnetic Nano material does not generally possess good water solublity, in the application due to the magnetic meeting of itself
Occur to reunite so as to performance drastically declines.In conjunction with frustule surface characteristic, suitable surface modification is carried out to magnetic Nano material
Make it surface-functionalized, its own agglomeration can be prevented effectively from and improve its adsorption capacity thus improving efficiency of crop simultaneously
Reduce absorption required dosage.Porous magnetic ferriferrous oxide nanometer material has larger specific surface area and loose structure, excellent
Magnetic property, the many poly arginines of the high electropositive long-chain of surface modification can be by the change of electrostatic adsorption and surface functional group
Learn bonding action and increase substantially the harvest efficiency to microalgae, can be returned by the separation that externally-applied magnetic field is realized from water body simultaneously
Receive, be a kind of efficient, safe, economic microalgae recovery method, there is huge application prospect and researching value, but at present not
Relevant report is had to be related to the functionalization porous ferroferric oxide nano material that oily algae efficiently harvests.
Content of the invention
It is an object of the invention to provide a kind of functionalization porous ferroferric oxide nano material.
Second object of the present invention is to provide a kind of functionalization porous ferroferric oxide efficiently harvesting for oily algae to receive
The preparation method of rice material.
Third object of the present invention is to provide arbitrary described functionalization porous ferroferric oxide nano material as oil
Algae efficiently harvests the application of material.
A kind of functionalization porous ferroferric oxide nano material, this material by porous ferroferric oxide and modifies described porous
Long-chain many poly arginines composition of ferroso-ferric oxide.
In the present invention, described functionalization porous ferroferric oxide nano material (hereinafter referred to as this material) possesses loose
Loose structure, specific surface area are big, absorption property is good.This material possesses preferable magnetic performance, and it is right to be improved by Magnetic Isolation
The efficiency of crop of oily algae, product is easy to extract and recycling, reduces cost.This material surface avtive spot is many, with a large amount of
Positive charged group, be effective against the impact to microalgae recovery for the extraneous soda acid change.
Heretofore described functionalization porous ferroferric oxide nano material particle diameter is 100-500nm, has 45-60mv's
Positive potential, poly arginic modification amount is 50-60%.
The preparation method of the functionalization porous ferroferric oxide nano material that the present invention provides, comprises the steps:
1) porous ferroferric oxide is prepared using hydro-thermal method；
2) described porous ferroferric oxide is carried out with the coupling of amino silane, obtains the porous ferroferric oxide (letter of apts modification
Claim p-fe3o4@apts)；
3) be there is amidation process with many poly arginines in the porous ferroferric oxide that described apts modifies, obtain functionalization porous
Ferriferrous oxide nanometer material (abbreviation p-fe3o4@pa).
In the solution of the present invention, step 1) is particularly as follows: weigh 1.35 g fecl3∙6h2O is dissolved in 60 ml ethylene glycol
In, stirring is to form the solution of homogeneous transparent.It is subsequently adding 2.0-3.0 g nh4Ac, after stirring 30 minutes, forms light brown
Suspension, is subsequently adding 1.0-1.8g sodium citrate na3Cit, is stirred vigorously this suspension and becomes uniformly solution until it.So
It is encapsulated afterwards in the stainless steel cauldron of 100 ml capacity, reactor is placed and is heated to 200 ° of c in an oven, and protect
Hold 10-18 hour, cool to room temperature afterwards.With Magnet, black precipitate is attracted out and cleaned for several times with ethanol and deionized water
To remove reaction dissolvent, finally in vacuum drying oven, 50 ° of c are dried 12 h.Wherein, described reactant nh4Ac and na3cit
Mass ratio be 2:1.08.
In the solution of the present invention, step 2) particularly as follows: 250 mg p-fe by step 1) gained3o4Be dispersed in equipped with
In 250 ml round-bottomed flasks of 150 ml ethanol, ultrasonic 30 min make its fully dispersed come, be subsequently adding 5 ml deionized waters
Mix homogeneously.It is subsequently adding 10 ml 3- TSL 8330 (apts) ultrasonic 10 min dispersions.Round bottom is burnt
Bottle connects condensing tube backflow, is placed in oil bath pan and is heated to 60 ° of c, quick stirring 7 h under the conditions of 60 ° of c.Then use ethanol
Cleaning 3 times, and nano-particle is disperseed in ethanol, to obtain p-fe3o4@apts.12 hs are dried with 50 ° of c of vacuum drying oven.
In the solution of the present invention, step 3) is particularly as follows: with step 2) p-fe of gained3o4@apts is sent out with many poly arginines
Raw amidation process.Weigh many poly arginines 50 mg of three kinds of different molecular weights respectively, and be completely dissolved in 1 ml pbs (phosphoric acid
Salt buffer, ph 7.2-7.4,0.01 m) in.By 100 mg edc, (1- (3- dimethylamino-propyl) -3- ethyl carbon two is sub-
Amine hydrochlorate) it is dissolved in 0.5 ml pbs, then its Deca is entered in poly arginine solution, then weigh 12 mg sulfo-
Nhs (n- hydroxy thiosuccinimide) simultaneously adds in above-mentioned mixed liquor, is completely dissolved.By above-mentioned mixed liquor mix homogeneously,
And reaction 15 minute is stirred at room temperature, there is priming reaction.
Further, weigh 50 mg steps 2) gained p-fe3o4@apts is dissolved in the pbs of 4 ml, and ultrasonic disperse is equal
Even；It is then added into the solution after above-mentioned activation, reaction is stirred at room temperature overnight.Last deionized water cleans 3 times to remove
Solvent, obtains functionalization porous ferroferric oxide nano material (abbreviation p-fe3o4@pa), it is dried with 50 ° of c of vacuum drying oven
12h.Wherein, described poly arginine molecule amount is 5000-15000,15000-70000, and > 70000.
Simple production process of the present invention, easy to operate, with low cost, product nonhazardouss, safety and environmental protection, possess good answering
Use prospect.
Brief description
Fig. 1 is the tem (a, b) of porous ferroferric oxide and sem (c, d) figure in embodiment 1.
Fig. 2 is the nitrogen Adsorption and desorption isotherms figure of porous ferroferric oxide in embodiment 1.
Fig. 3 is the pore size distribution curve of porous ferroferric oxide in embodiment 1.
Fig. 4 is tem the and sem figure of functionalization porous ferroferric oxide nano material in embodiment 1.
Fig. 5 is porous ferroferric oxide in embodiment 1-3, the porous ferroferric oxide that amino silane is modified, and functionalization is many
The ft-ir figure of hole ferriferrous oxide nanometer material.
Fig. 6 is porous ferroferric oxide in embodiment 1-3, the porous ferroferric oxide that amino silane is modified, and functionalization is many
The xps figure of hole ferriferrous oxide nanometer material.
Fig. 7 is (a) c 1s (b) n 1s (c) si of functionalization porous ferroferric oxide nano material in embodiment 1
The high-resolution collection of illustrative plates of 2p.
Fig. 8 is porous ferroferric oxide in embodiment 1-3, the porous ferroferric oxide that amino silane is modified, and functionalization is many
The thermogravimetric curve of hole ferriferrous oxide nanometer material.
Fig. 9 is porous ferroferric oxide in embodiment 1-3, the hydration power of functionalization porous ferroferric oxide nano material
Learn diameter Distribution (dls) figure.
Figure 10 is porous ferroferric oxide in embodiment 1-3, the porous ferroferric oxide that amino silane is modified, and functionalization is many
The zeta potential diagram of hole ferriferrous oxide nanometer material.
Figure 11 is to add the dosage functionalization porous four that many poly arginines are modified to different molecular weight oxidation three in embodiment 4
The impact figure of ferrum nano material harvesting microalgae efficiency.
Figure 12 is that in embodiment 5, the ph value functionalization porous ferroferric oxide that many poly arginines are modified to different molecular weight is received
The impact figure of rice material harvesting microalgae efficiency.
Figure 13 is functionalization porous four oxidation three of different molecular weight many poly arginines modification of circular regeneration in embodiment 6
The efficiency of crop variation diagram to microalgae for the ferrum nano material.
Specific embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with embodiments of the invention, to this
Technical scheme in inventive embodiments is clearly and completely described it is clear that described embodiment is that a present invention part is real
Apply example, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creation
Property work under the premise of the every other embodiment that obtained, broadly fall into the scope of protection of the invention.
Used in embodiment algae kind for early stage separation screening to high oil-producing chlorella hq(be preserved in China's commonly micro- life
Thing culture presevation administrative center, preserving number is no. cgmcc7601), carry out autotrophy and cultivate 20 days, initial algae solution concentration is
0.2g/l (in terms of frustule dry weight).Set up the standard curve of absorbance at frustule dry weight and wavelength 690nm, received by measurement
Obtain the light absorption value of before and after's supernatant to calculate algae solution concentration, thus measuring harvested biomass and efficiency of crop.
Embodiment 1.
Weigh 1.35 g fecl3∙6h2O is dissolved in 60 ml ethylene glycol, and stirring is to form the solution of homogeneous transparent.Then
Add 2.0g nh4Ac, after stirring 30 minutes, forms the suspension of light brown, is subsequently adding 1.08g sodium citrate na3Cit, acute
Strong this suspension of stirring becomes uniformly solution until it.Then it is encapsulated in the stainless steel cauldron of 100 ml capacity,
Reactor is placed and is heated to 200 ° of c in an oven, and keep 15 hours, cool to room temperature afterwards.With Magnet by black precipitate
Attract out and with ethanol and deionized water to clean for several times to remove reaction dissolvent, finally in vacuum drying oven, 50 ° of c are dried
12 h.
Weigh the above-mentioned p-fe of 250 mg3o4It is dispersed in equipped with 250 ml round-bottomed flasks of 150 ml ethanol, ultrasonic 30
Min make its fully dispersed come, be subsequently adding 5 ml deionized water mix homogeneously.It is subsequently adding 10 ml 3- aminopropyl front threes
TMOS (apts) ultrasonic 10 min dispersions.Round-bottomed flask is connected condensing tube backflow, is placed in oil bath pan and is heated to 60
° c, quick stirring 7 h under the conditions of 60 ° of c.Then use ethanol purge 3 times, and nano-particle is disperseed in ethanol, to obtain p-
fe3o4@apts.12 hs are dried with 50 ° of c of vacuum drying oven.
Weigh many poly arginines 50 mg that molecular weight is 15000-70000, and (phosphate delays to be completely dissolved in 1 ml pbs
Rush liquid, ph 7.2-7.4,0.01 m) in.By 100 mg edc (1- (3- dimethylamino-propyl) -3- ethyl carbodiimide salt
Hydrochlorate) it is dissolved in 0.5 ml pbs, then its Deca is entered in poly arginine solution, then weigh 12 mg sulfo-nhs
(n- hydroxy thiosuccinimide) simultaneously adds in above-mentioned mixed liquor, is completely dissolved.By above-mentioned mixed liquor mix homogeneously, and
, there is priming reaction in stirring reaction 15 minutes under room temperature.
Weigh described p-fe3o4@apts is dissolved in the pbs of 4 ml, and ultrasonic disperse is uniform；It is then added into above-mentioned activation
Solution afterwards, is stirred at room temperature reaction overnight.Last deionized water cleans 3 times to remove solvent, obtains functionalization porous four oxygen
Change three ferrum nano materials (abbreviation p-fe3o4@pa2), 12h is dried with 50 ° of c of vacuum drying oven.
As shown in figure 1, porous fe of above-mentioned preparation3o4Rounded, particle diameter distribution has thin on 100-300 nm, surface
The loose structure of pine.
As shown in Fig. 2 porous fe of above-mentioned preparation3o4Nitrogen Adsorption and desorption isotherms meet iv type feature isothermal line, show
This fe3o4Microsphere has pore structure (aperture < 2 nm).
As shown in figure 3, porous fe of above-mentioned preparation3o4In 20 a-2 nm, average pore size is 224.2 a to pore-size distribution, card
Bright hole is essentially from the fe of assembling microsphere3o4Hole between granule.
As shown in figure 4, the pattern modifying the functionalization porous ferroferric oxide nano material after many poly arginines does not have
Significantly change, still for loose and porous structure, microsphere size is about 200 nm.
Embodiment 2.
Weigh 1.35 g fecl3∙6h2O is dissolved in 60 ml ethylene glycol, and stirring is to form the solution of homogeneous transparent.Then
Add 2.0g nh4Ac, after stirring 30 minutes, forms the suspension of light brown, is subsequently adding 1.08g sodium citrate na3Cit, acute
Strong this suspension of stirring becomes uniformly solution until it.Then it is encapsulated in the stainless steel cauldron of 100 ml capacity,
Reactor is placed and is heated to 200 ° of c in an oven, and keep 15 hours, cool to room temperature afterwards.With Magnet by black precipitate
Attract out and with ethanol and deionized water to clean for several times to remove reaction dissolvent, finally in vacuum drying oven, 50 ° of c are dried
12 h.
Weigh the above-mentioned p-fe of 250 mg3o4It is dispersed in equipped with 250 ml round-bottomed flasks of 150 ml ethanol, ultrasonic 30
Min make its fully dispersed come, be subsequently adding 5 ml deionized water mix homogeneously.It is subsequently adding 10 ml 3- aminopropyl front threes
TMOS (apts) ultrasonic 10 min dispersions.Round-bottomed flask is connected condensing tube backflow, is placed in oil bath pan and is heated to 60
° c, quick stirring 7 h under the conditions of 60 ° of c.Then use ethanol purge 3 times, and nano-particle is disperseed in ethanol, to obtain p-
fe3o4@apts.12 hs are dried with 50 ° of c of vacuum drying oven.
Weigh many poly arginines 50 mg that molecular weight is 5000-15000, and (phosphate delays to be completely dissolved in 1 ml pbs
Rush liquid, ph 7.2-7.4,0.01 m) in.By 100 mg edc (1- (3- dimethylamino-propyl) -3- ethyl carbodiimide salt
Hydrochlorate) it is dissolved in 0.5 ml pbs, then its Deca is entered in poly arginine solution, then weigh 12 mg sulfo-nhs
(n- hydroxy thiosuccinimide) simultaneously adds in above-mentioned mixed liquor, is completely dissolved.By above-mentioned mixed liquor mix homogeneously, and
, there is priming reaction in stirring reaction 15 minutes under room temperature.
Weigh described p-fe3o4@apts is dissolved in the pbs of 4 ml, and ultrasonic disperse is uniform；It is then added into above-mentioned activation
Solution afterwards, is stirred at room temperature reaction overnight.Last deionized water cleans 3 times to remove solvent, obtains functionalization porous four oxygen
Change three ferrum nano materials (abbreviation p-fe3o4@pa1), 12h is dried with 50 ° of c of vacuum drying oven.
Embodiment 3.
Weigh 1.35 g fecl3∙6h2O is dissolved in 60 ml ethylene glycol, and stirring is to form the solution of homogeneous transparent.Then
Add 2.0g nh4Ac, after stirring 30 minutes, forms the suspension of light brown, is subsequently adding 1.08g sodium citrate na3Cit, acute
Strong this suspension of stirring becomes uniformly solution until it.Then it is encapsulated in the stainless steel cauldron of 100 ml capacity,
Reactor is placed and is heated to 200 ° of c in an oven, and keep 15 hours, cool to room temperature afterwards.With Magnet by black precipitate
Attract out and with ethanol and deionized water to clean for several times to remove reaction dissolvent, finally in vacuum drying oven, 50 ° of c are dried
12 h.
Weigh the above-mentioned p-fe of 250 mg3o4It is dispersed in equipped with 250 ml round-bottomed flasks of 150 ml ethanol, ultrasonic 30
Min make its fully dispersed come, be subsequently adding 5 ml deionized water mix homogeneously.It is subsequently adding 10 ml 3- aminopropyl front threes
TMOS (apts) ultrasonic 10 min dispersions.Round-bottomed flask is connected condensing tube backflow, is placed in oil bath pan and is heated to 60
° c, quick stirring 7 h under the conditions of 60 ° of c.Then use ethanol purge 3 times, and nano-particle is disperseed in ethanol, to obtain p-
fe3o4@apts.12 hs are dried with 50 ° of c of vacuum drying oven.
Weigh molecular weight > 70000 many poly arginines 50 mg, and be completely dissolved in 1 ml pbs (phosphate buffer,
Ph 7.2-7.4,0.01 m) in.By 100 mg edc (1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride)
It is dissolved in 0.5 ml pbs, then enters its Deca in poly arginine solution, then weigh 12 mg sulfo-nhs (n- hydroxyls
Base thiosuccimide) and add in above-mentioned mixed liquor, it is completely dissolved.By above-mentioned mixed liquor mix homogeneously, and at room temperature
, there is priming reaction in stirring reaction 15 minutes.
Weigh described p-fe3o4@apts is dissolved in the pbs of 4 ml, and ultrasonic disperse is uniform；It is then added into above-mentioned activation
Solution afterwards, is stirred at room temperature reaction overnight.Last deionized water cleans 3 times to remove solvent, obtains functionalization porous four oxygen
Change three ferrum nano materials (abbreviation p-fe3o4@pa3), 12h is dried with 50 ° of c of vacuum drying oven.
As shown in figure 5, common characteristic peak 574 cm before and after showing to modify of the ft-ir spectrum of material in embodiment 1-3-1It is
The stretching vibration of fe-o key, p-fe3o4@apts is in 1038 cm-1The new absworption peak at place is due to the stretching vibration of si-o key,
1654 cm-1(amide i), 1548 cm-1(amide ii) place is the characteristic absorption peak of co-nh key, 3326 cm-1With
3190 cm-1Place is-nh2Bending vibrations, show that amino silane and many poly arginines successfully modify porous ferroferric oxide table
Face.
As shown in fig. 6-7, in embodiment 1-3, the xps collection of illustrative plates of material shows p-fe3o4@apts and p-fe3o4@pa-1 ~ 3 are main
To contain the characteristic peaks such as si 2p, c 1s, n 1s, o 1s, and fe 2p.In porous ferroferric oxide collection of illustrative plates before modification not
There is si 2p and the characteristic peak of n 1s, but si 2p and n 1s occurs after modifying apts.C 1s characteristic peak can fit to two
Individual characteristic peak: 285.0 ev and 288.0 ev, the feature of the c-c key in expression poly arginine molecule and co-nh key respectively
Peak, shows the p-fe obtaining3o4@pa-1 ~ 3 surface has abundant co-nh active group, and this is consistent with the result of ft-ir.
As shown in figure 8, thermogravimetric curve there occurs before and after in embodiment 1-3, the thermogravimetric curve of material shows to modify amino silane
Significantly change, the modification mass fraction of porous ferroferric oxide surface sodium citrate is 44%, occurs in 540-800 DEG C of scope
In the new thermal loss stage, this is one of decomposition temperature scope of apts, show that apts substituted for porous ferroferric oxide table
The sodium citrate molecule in face.Functionalization porous ferroferric oxide nano material p-fe that many poly arginines are modified3o4@pa-1 ~ 3 table
The modification amount of face Organic substance (including polyamino acid and apts) is respectively 51.5%, 57.9% and 51.5%.
As shown in figure 9, the functionalization porous ferroferric oxide that in embodiment 1-3, the many poly arginines of different molecular weight are modified is received
Rice material p-fe3o4The hydration kinetics diameter of@pa-1 ~ 3 is respectively 100-300 nm, 100-400 nm, 200-500 nm.
As shown in Figure 10, in embodiment 1-3, the zeta current potential of the porous ferroferric oxide of preparation is negative value, modifies electropositive
Apts after, zeta current potential during ph 8.0 is increased on the occasion of (30.3 mv), modifies many poly arginines of three kinds of molecular weight
Afterwards, zeta current potential raises further, p-fe3o4The zeta current potential of@pa-1 ~ 3 respectively reaches 45.0 mv, 51.2 mv, 57.0
Mv, shows that the functionalization porous ferroferric oxide nano material of present invention preparation has high electropositive.
Embodiment 4.
Respectively take 10 ml algae solutions in conical flask, initial algae solution concentration is 0.2g/l, with 0.1 m hcl and 0.1 m naoh
Algae solution ph is all adjusted to 8.0, is separately added into the porous ferroferric oxide in 10-300 mg/l embodiment 1-3, amino silane is repaiied
The porous ferroferric oxide of decorations, the functionalization porous ferroferric oxide nano material that the many poly arginines of different molecular weight are modified, in
Shake 20min in 250 rpm shaking tables, form the complex of nano material and frustule.Then carry out magnetic outside bottle with permanent magnet
Property harvest, complex separates from suspending medium, now measures the absorbance in maximum absorption wave strong point for the supernatant, finally
Efficiency of crop is calculated according to Biomass-absorbance standard curve.
As shown in figure 11, with the increase of nano material consumption, the efficiency of crop of different materials improves, the optimal throwing of material
Dosage, by the 250mg/l of porous ferroferric oxide, is reduced to 200 mg/l of the porous ferroferric oxide of amino silane modification, and
It is further decreased to the 50/10/20 of the functionalization porous ferroferric oxide nano material that the many poly arginines of different molecular weight are modified
Mg/l, significantly reduces harvesting cost.
Embodiment 5.
Respectively take 10 ml algae solutions in conical flask, initial algae solution concentration is 0.2g/l, with 0.1 m hcl and 0.1 m
Algae solution ph is adjusted to 4.0-10.0 by naoh, is separately added into the porous ferroferric oxide in 20 mg/l embodiments 1-3, amino silicone
The porous ferroferric oxide that alkane is modified, the functionalization porous ferroferric oxide nanometer material that the many poly arginines of different molecular weight are modified
Material, shakes 20min in 250 rpm shaking tables, forms the complex of nano material and frustule.Then use permanent magnet outside bottle
Carry out magnetic results, complex is separated from suspending medium, now measure the extinction in maximum absorption wave strong point for the supernatant
Degree, calculates efficiency of crop finally according to Biomass-absorbance standard curve.
As shown in figure 12, under the conditions of different ph, for porous ferroferric oxide, porous four oxygen of amino silane modification
Change the functionalization porous ferroferric oxide nano material that three-iron and the many poly arginines of low-molecular-weight are modified, efficiency of crop is with ph value
Raise and reduce, and the functionalization porous ferroferric oxide nano material that many poly arginines are modified for higher molecular weight, surface
There is more abundant active group to combine microalgae cell, adsorption bridging flocculation and hydrogen bond action add in addition to electrostatic interaction
By force, higher efficiency of crop can all be kept in the range of wider soda acid.
Embodiment 6.
Respectively take 10 ml algae solutions in conical flask, initial algae solution concentration is 0.2g/l, with 0.1 m hcl and 0.1 m
Algae solution ph is adjusted to 8.0 by naoh, adds the functionalization porous ferroferric oxide nano material in 50 mg/l embodiments 1-2, in
Shake 20min in 250 rpm shaking tables, form the complex of nano material and frustule.Then carry out magnetic outside bottle with permanent magnet
Property harvest, complex separates from suspending medium, measures the absorbance in maximum absorption wave strong point for the supernatant, according to biology
Amount-absorbance standard curve calculates efficiency of crop.Adjust ph to 12 with highly basic after results, add 2ml in detached complex
The mixed solution (volume ratio 2:1) of chloroform and methanol, Magnetic Isolation after the ultrasonic 15min of 60w, add 500 l deionized waters to make back
Material redispersion after receipts, carries out results experiment next time, and circulation carries out 5 times.
As shown in figure 13, adding dosage is 50 mg/l, during ph 8.0, p-fe3o4Harvest after@pa-1 regeneration cycle five times
Efficiency is reduced to 61% from 95%, though there being certain range of decrease, efficiency of crop is still higher, by contrast p-fe3o4@pa-2 regeneration cycle five
Remain to after secondary reach up to 85% efficiency of crop.The functionalization porous ferroferric oxide nano material of present invention preparation possesses good
Good cyclical stability, it is possible to achieve regeneration.
Finally it is noted that various embodiments above, only in order to technical scheme to be described, is not intended to limit；To the greatest extent
Pipe has been described in detail to the present invention with reference to foregoing embodiments, it will be understood by those within the art that: its according to
So the technical scheme described in foregoing embodiments can be modified, or wherein some or all of technical characteristic is entered
Row equivalent；And these modifications or replacement, do not make the essence of appropriate technical solution depart from various embodiments of the present invention technology
The scope of scheme.
Claims (8)
1. a kind of functionalization porous ferroferric oxide nano material is it is characterised in that including porous ferroferric oxide and modifying institute
State the many poly arginines of long-chain of porous ferroferric oxide, described functionalization porous ferroferric oxide nano material has loose many
Pore structure.
2. functionalization porous ferroferric oxide nano material according to claim 1 is it is characterised in that described functionalization is many
The particle diameter of hole ferriferrous oxide nanometer material is 100-500nm.
3. functionalization porous ferroferric oxide nano material according to claim 1 is it is characterised in that described functionalization is many
Hole ferriferrous oxide nanometer material has the positive potential of 45-60mv.
4. functionalization porous ferroferric oxide nano material according to claim 1 is it is characterised in that described functionalization is many
In the ferriferrous oxide nanometer material of hole, poly arginic modification amount is 50-60%.
5. the preparation method of the arbitrary described functionalization porous ferroferric oxide nano material of Claims 1-4, its feature exists
In comprising the steps:
1) porous ferroferric oxide is prepared using hydro-thermal method；
2) described porous ferroferric oxide is carried out with the coupling of amino silane, obtains the porous ferroferric oxide (letter of apts modification
Claim p-fe3o4@apts)；
3) be there is amidation process with many poly arginines in the porous ferroferric oxide that described apts modifies, obtain functionalization porous
Ferriferrous oxide nanometer material (abbreviation p-fe3o4@pa).
6. preparation method according to claim 5 is it is characterised in that control the described hydro-thermal method response time to be 10-18h.
7. preparation method according to claim 5 is repaiied it is characterised in that carrying out described modification using the many poly arginines of long-chain
Decorations process, and control described modifier molecules amount to be 5000-15000,15000-70000, and > 70000.
8. the arbitrary described functionalization porous ferroferric oxide nano material of Claims 1-4 efficiently harvests material as oily algae
Application.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108333A (en) * | 2007-07-05 | 2008-01-23 | 复旦大学 | Amino- magnetic nano particle with metallic copper ion fixed on surface and method of preparing the same and application thereof |
| CN101559984A (en) * | 2009-05-27 | 2009-10-21 | 山东大学 | Preparation method of superparamagnetic Fe3O4 nano-particles |
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| CN101559984A (en) * | 2009-05-27 | 2009-10-21 | 山东大学 | Preparation method of superparamagnetic Fe3O4 nano-particles |
Non-Patent Citations (3)
| Title |
|---|
| BO-HUNG LAI ET AL.: ""Surface modification of iron oxide nanoparticles with polyarginine as a highly positively charged magnetic nano-adsorbent for fast and effective recovery of acid proteins"", 《PROCESS BIOCHEMISTRY》 * |
| FUPING DONG ET AL.: ""Highly Porous, Water-Soluble, Superparamagnetic, and Biocompatible Magnetite Nanocrystal Clusters for Targeted Drug Delivery"", 《CHEM. EUR. J.》 * |
| TING WANG ET AL.: ""Magnetic nanoparticles grafted with amino-riched dendrimer as magnetic flocculant for efficient harvesting of oleaginous microalgae"", 《CHEMICAL ENGINEERING JOURNAL》 * |
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|---|---|---|---|---|
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