CN111282600A - Mixed iron oxide nano material and biomimetic mineralization method and application thereof - Google Patents
Mixed iron oxide nano material and biomimetic mineralization method and application thereof Download PDFInfo
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- bacillus subtilis
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 98
- 230000033558 biomineral tissue development Effects 0.000 title claims abstract description 71
- 230000003592 biomimetic effect Effects 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 34
- 244000063299 Bacillus subtilis Species 0.000 claims abstract description 91
- 235000014469 Bacillus subtilis Nutrition 0.000 claims abstract description 91
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 35
- 238000005406 washing Methods 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 238000005070 sampling Methods 0.000 claims abstract description 17
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000012258 culturing Methods 0.000 claims abstract description 14
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 6
- 239000001963 growth medium Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 14
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 230000003321 amplification Effects 0.000 claims description 11
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 11
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 8
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 17
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 235000013980 iron oxide Nutrition 0.000 description 79
- 238000012360 testing method Methods 0.000 description 21
- 229910052500 inorganic mineral Inorganic materials 0.000 description 19
- 241000894006 Bacteria Species 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 18
- 239000011707 mineral Substances 0.000 description 18
- 230000001580 bacterial effect Effects 0.000 description 15
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- 241000193830 Bacillus <bacterium> Species 0.000 description 9
- 238000009630 liquid culture Methods 0.000 description 9
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- 150000002500 ions Chemical class 0.000 description 5
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- 239000005416 organic matter Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- -1 iron ion Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
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- 108010074122 Ferredoxins Proteins 0.000 description 1
- MSFSPUZXLOGKHJ-UHFFFAOYSA-N Muraminsaeure Natural products OC(=O)C(C)OC1C(N)C(O)OC(CO)C1O MSFSPUZXLOGKHJ-UHFFFAOYSA-N 0.000 description 1
- 108010013639 Peptidoglycan Proteins 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004173 biogeochemical cycle Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J35/33—
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- B01J35/39—
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- B01J35/394—
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- B01J35/40—
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- B01J35/61—
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- 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
- C02F2101/38—Organic compounds containing nitrogen
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a mixed iron oxide nano material and a biomimetic mineralization method and application thereof, wherein the biomimetic mineralization method comprises the following steps: 1) culturing Bacillus subtilis, collecting Bacillus subtilis, and washingObtaining bacillus subtilis wet cells; 2) suspending the wet bacillus subtilis thallus in Fe3+And carrying out biomimetic mineralization synthesis reaction in the solution, then sampling and centrifuging at different times, washing and drying to obtain the mixed iron oxide nano material. The invention can form a novel needle-like or strip-like mixed iron oxide nano material which is nano-scale, has the size of 50-300nm and large specific surface area, has better dispersibility and stability, thereby having higher and excellent stability, being used for the rapid degradation rate of organic pollutants and the electrocatalytic hydrogen evolution efficiency, and further being well applied to the fields of photocatalytic degradation of organic pollutants and electrocatalytic hydrogen evolution.
Description
Technical Field
The invention relates to the technical field of biomineralization materials, in particular to a mixed iron oxide nano material, a biomimetic mineralization method and application thereof.
Background
Since the eighties of the last century, the research on biomineralization has been continuously carried out abroad, and with the research on the forms, compositions, nanostructures and organic matter template effects of biomineralization calcium carbonate, calcium phosphate, calcium oxalate, pyrite, goethite, iron manganese nodule, intracellular magnetite and other biomineralization minerals, the mineralization of microorganisms and the interaction with environmental minerals are more and more emphasized.
Bacteria can live in any place in nature with liquid water, and under some extremely harsh conditions, bacteria are often the only life forms. Bacteria are said to be ubiquitous, numerous, and small in size, having relatively maximal surface area to volume ratios, capable of accumulating various metals on their surfaces and in their bodies. Bacteria are able to control many biogeochemical cycles in the environment.
Inorganic minerals in biomineralization are often formed in the presence of an organic matrix, nucleate on the organic matrix, and are regulated by the organic matrix and other vital activities throughout the crystallization process to have a high degree of uniformity and order in crystal morphology, size, and orientation, which in turn allows these inorganic materials to have specific functions. Inspired by this natural phenomenon, people began to study the basic principles of biomineralization and utilize these principles to simulate biomineralization processes, thereby exploring ideal inorganic materials and their preparation approaches.
Researchers explore the formation mechanism by simulating the mineral formation process in nature, and they find that the bacteria-mediated mineral formation on the surface is usually caused by the influence of some special groups on the surface of bacteria, such as hydroxyl, carboxyl, amine, halide and the like, which participate in the adsorption of heavy metal ions or chelate certain specific groups of ions, thereby causing the deposition and mineralization of the mineral on the surface, and the groups also regulate the appearance of the mineral in the mineralization process. Researchers inspire that materials with excellent performance are mineralized and synthesized by bacteria to carry out ecological restoration, sewage treatment, drug carriers and the like.
Iron oxides are of great significance in catalytic and magnetic systems, and these specific applications require explicit requirements for size and morphology, which is very difficult to achieve in the laboratory by chemical synthesis, not only requiring precise control of synthesis conditions, but also difficult maintenance of morphology after synthesis. Meanwhile, the biomineralization of the existing iron oxide can be realized only by the action of ferredoxin or other organic matrixes, but the biomineralization of the existing iron oxide can be realized only by obtaining a purer organic medium, so that the time and the money are consumed, and the stability of the material obtained by mineralization is poorer. Through search, the bacillus subtilis is found to be tolerant to a plurality of heavy metal ions in water and adsorb Ag+、Cu2+、Cd2+、Pb2+、Mn2+、Zn2+、Gd3 +And the like, has the effect of removing heavy metal ions in sewage, but the induction of mineral formation on the surface of the bacillus subtilis is not found so far.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a mixed iron oxide nano material, so as to solve the problems of poor stability and high mineralization cost of the existing iron oxide biomineralization material.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a biomimetic mineralization method of a mixed iron oxide nano material comprises the following steps:
1) culturing bacillus subtilis, collecting bacillus subtilis thallus, and washing to obtain bacillus subtilis wet thallus;
2) suspending the wet bacillus subtilis thallus in Fe3+And carrying out biomimetic mineralization synthesis reaction in the solution, then sampling and centrifuging at different times, washing and drying to obtain the mixed iron oxide nano material.
Optionally, the culturing bacillus subtilis thallus in the step 1), then collecting the bacillus subtilis thallus, and washing the bacillus subtilis thallus to obtain wet bacillus subtilis thallus comprises: streaking a preserved bacillus subtilis strain plate overnight for culture, selecting a single strain to be placed in a liquid LB culture medium for amplification culture, then inoculating the single strain into the liquid LB culture medium according to the proportion of 1: 50, carrying out overnight culture, then collecting bacillus subtilis thallus according to the conditions of 6000g, 4 ℃ and 10-20min, and washing the bacillus subtilis thallus to obtain the bacillus subtilis wet thallus.
Optionally, 1mL of said Fe in said step 2)3+2-20mg of the wet bacillus subtilis is suspended in the solution.
Optionally, the sampling centrifugation at different times in the step 2) comprises: sampling is carried out in sections within 1-96h, and then centrifugation is carried out at room temperature according to the conditions of 5000g and 3-10 min.
Optionally, said Fe in said step 2)3+The pH of the solution is acidic.
The second purpose of the invention is to provide a mixed iron oxide nano material, which is obtained by mineralization of the mixed iron oxide nano material by a biomimetic mineralization method.
The third purpose of the invention is to provide an application of the mixed iron oxide nano material in photocatalytic degradation of organic pollutants, which comprises the following steps: preparing methylene blue solution with the concentration of 0.2mM/L, adjusting the pH value to be acidic, then adding the mixed iron oxide nano material, stirring in a dark place, adding 0.2% (v/v) hydrogen peroxide solution, and degrading organic pollutants under natural light.
Optionally, 0.5g of mixed iron oxide nano-material is added into 1L of the methylene blue solution.
The fourth purpose of the invention is to provide an application of the mixed iron oxide nano material in electrocatalytic hydrogen evolution, which comprises the following steps: and (3) under the protection of inert gas, preserving the temperature of the mixed iron oxide nano material at 500 ℃ for 3h, and removing organisms to obtain the catalyst material for electrocatalytic hydrogen evolution.
The basic principle of the invention is as follows: the bacillus subtilis has thicker bacterial surface cell wall, chemical components of the bacillus subtilis generally only contain 90% of peptidoglycan and 10% of teichoic acid, the bacillus subtilis has simpler components and only contains a very small amount of protein, but a plurality of groups exist in the biological components, ferric ions can be adsorbed by virtue of electrostatic adsorption and are gathered on the bacterial surface, the ferric ions can be hydrolyzed to form colloid and precipitate on the bacterial surface when the pH is higher, and the biological components on the bacterial surface can regulate the appearance and the formation speed of the mineralized matters, so that the needle-shaped mixed iron oxide nano material with the appearance is formed on the surface of escherichia coli. In the process, processes such as iron ion adsorption, mineral deposition, organic matter regulation and the like exist. Due to the regulation of organic components on the surface of bacteria, the material forming process is regulated, a needle-shaped appearance with a large specific surface area is formed, the contact surface with organic matters is large, the electron transfer is rapid, and the high efficiency of the rapid degradation of the organic matters and the electrocatalytic hydrogen evolution can be realized.
Compared with the prior art, the biomimetic mineralization method of the mixed iron oxide nano material has the following advantages:
1. the invention adopts bacillus subtilis as a biomineralized organic medium, suspends the bacteria in a ferric ion solution, adsorbs iron ions and induces the iron ions to form a novel needle-like or belt-like mixed iron oxide nano material on the surface of the bacteria by utilizing the adsorption effect of the surface groups of the bacillus subtilis on the ions, the material is nano-scale, the size is 50-300nm, the specific surface area is large, and the material has better dispersibility and stability, so that the material has higher rapid degradation rate of organic pollutants and electrocatalytic hydrogen evolution efficiency, can be well applied to the fields of photocatalytic degradation of organic pollutants and electrocatalytic hydrogen evolution, can still keep the morphology after being calcined at high temperature, and has good temperature resistance.
2. The method has the advantages of cheap and easily-obtained raw materials, few synthesis steps, high reaction controllability, mild synthesis conditions, simple and feasible separation method and lower production and use costs.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is an SEM image of a mixed iron oxide nanomaterial of example 1 of the present invention;
fig. 2 is an SEM image of the mixed iron oxide nanomaterial of example 2 of the present invention;
fig. 3 is an SEM image of the mixed iron oxide nanomaterial of example 3 of the present invention;
fig. 4 is an SEM image of the mixed iron oxide nanomaterial of example 4 of the present invention;
FIG. 5 is an SEM image of mixed iron oxide nanomaterial of example 5 of the present invention;
fig. 6 is an SEM image of a mixed iron oxide nanomaterial of example 7 of the present invention;
fig. 7 is an SEM image of a mixed iron oxide nanomaterial of example 8 of the present invention;
fig. 8 is an SEM image of a mixed iron oxide nanomaterial of example 9 of the present invention;
FIG. 9 is the organic matter degradation curve of the mixed iron oxide nanomaterial of example 5 of the present invention;
FIG. 10 is a graph showing the effect of organic matter degradation of the mixed iron oxide nanomaterial of example 5 of the present invention;
FIG. 11 is a SEM image of calcined mixed iron oxide nanomaterial of example 5 of the present invention;
fig. 12 is a polarization curve diagram of electrocatalytic hydrogen evolution of the mixed iron oxide nanomaterial of example 5 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
A biomimetic mineralization method of a mixed iron oxide nano material specifically comprises the following steps:
1) culturing bacillus subtilis and obtaining the bacillus: streaking a preserved bacillus subtilis strain plate overnight for culture, selecting a single strain to be placed in a liquid LB culture medium for amplification culture, inoculating the single strain into the liquid culture medium according to the proportion of 1: 50, performing overnight culture, collecting bacillus subtilis strain according to the conditions of 6000g, 4 ℃ and 10-20min, and washing to obtain wet bacillus subtilis strain, wherein the obtained wet bacillus subtilis strain can be preserved at a low temperature for later use for convenience;
2) mineralization synthesis of nano materials: 0.4g of wet Bacillus subtilis cells were weighed and suspended in 80ml of acidic Fe3+And (2) evenly dividing the solution into 4 parts, subpackaging the 4 parts in an erlenmeyer flask, carrying out biomimetic mineralization synthesis reaction under a standing condition, then sampling within 1-6h of the biomimetic mineralization synthesis reaction, centrifuging according to the conditions of 5000g and 3-10min, washing the centrifuged bacterial precipitate, and drying to obtain the mixed iron oxide nano material.
The mixed iron oxide nano-material of the present example was subjected to SEM test, and the test results are shown in fig. 1.
As is clear from FIG. 1, in the mixed iron oxide nanomaterial of the present example, it can be seen that spherical mixed iron oxide is closely coated on the surface of Bacillus subtilis cells, and the diameter of the spherical mineral on the surface of the bacteria is approximately 100 nm.
Example 2
A biomimetic mineralization method of a mixed iron oxide nano material specifically comprises the following steps:
1) culturing bacillus subtilis and obtaining the bacillus: streaking a preserved bacillus subtilis strain plate overnight for culture, selecting a single strain to be placed in a liquid LB culture medium for amplification culture, inoculating the single strain into the liquid culture medium according to the proportion of 1: 50, performing overnight culture, collecting bacillus subtilis strain according to the conditions of 6000g, 4 ℃ and 10-20min, and washing to obtain bacillus subtilis wet strain, wherein the obtained escherichia coli wet strain can be preserved at low temperature for later use for convenience;
2) mineralization synthesis of nano materials: 0.4g of wet Bacillus subtilis cells were weighed and suspended in 80ml of acidic Fe3+And (2) evenly dividing the solution into 4 parts, subpackaging the 4 parts in an erlenmeyer flask, carrying out biomimetic mineralization synthesis reaction under a standing condition, then sampling within a period of 6-24h of the biomimetic mineralization synthesis reaction, centrifuging according to conditions of 5000g and 3-10min, washing a bacterial precipitate obtained by centrifuging, and drying to obtain the mixed iron oxide nano material.
The mixed iron oxide nano-material of the present example was subjected to SEM test, and the test results are shown in fig. 2.
As shown in FIG. 2, in the mixed iron oxide nanomaterial of the present embodiment, the minerals tightly coat the Bacillus subtilis cells, and the spherical minerals on the surface of the bacteria gradually grow into needle-like shapes with a size of about 100-200 nm.
Example 3
A biomimetic mineralization method of a mixed iron oxide nano material specifically comprises the following steps:
1) culturing bacillus subtilis and obtaining the bacillus: streaking a preserved bacillus subtilis strain plate overnight for culture, selecting a single strain to be placed in a liquid LB culture medium for amplification culture, inoculating the single strain into the liquid culture medium according to the proportion of 1: 50, performing overnight culture, collecting bacillus subtilis strain according to the conditions of 6000g, 4 ℃ and 10-20min, and washing to obtain wet bacillus subtilis strain, wherein the obtained wet bacillus subtilis strain can be preserved at a low temperature for later use for convenience;
2) mineralization synthesis of nano materials: 0.4g of wet Bacillus subtilis cells were weighed and suspended in 80ml of acidic Fe3+In the solution, dividing the solution into 4 parts on average, filling the parts into conical flasks, and performing simulation under the standing conditionPerforming a biomineralization synthesis reaction, then sampling within 24-48h of the biomimetic mineralization synthesis reaction, centrifuging according to the conditions of 5000g and 3-10min, washing the bacterial precipitate obtained by centrifuging, and then drying to obtain the mixed iron oxide nano material.
The mixed iron oxide nano-material of the present example was subjected to SEM test, and the test results are shown in fig. 3.
As can be seen from FIG. 3, in the mixed iron oxide nanomaterial of this embodiment, the needle-like minerals gradually grow more, some of which have been crosslinked into a net shape and tightly cover the Bacillus subtilis cells, and the mineral size on the surface of the bacteria is about 200-300 nm.
Example 4
A biomimetic mineralization method of a mixed iron oxide nano material specifically comprises the following steps:
1) culturing bacillus subtilis and obtaining the bacillus: streaking a preserved bacillus subtilis strain plate overnight for culture, selecting a single strain to be placed in a liquid LB culture medium for amplification culture, inoculating the single strain into the liquid culture medium according to the proportion of 1: 50, performing overnight culture, collecting bacillus subtilis strain according to the conditions of 6000g, 4 ℃ and 10-20min, and washing to obtain escherichia coli wet strain, wherein the obtained bacillus subtilis wet strain can be preserved at a low temperature for later use for convenience;
2) mineralization synthesis of nano materials: 0.4g of wet E.coli cells were weighed out and suspended in 80ml of acidic Fe3+And (2) evenly dividing the solution into 4 parts, subpackaging the 4 parts in an erlenmeyer flask, carrying out biomimetic mineralization synthesis reaction under the standing condition, then sampling within the period of 48-72h of the biomimetic mineralization synthesis reaction, centrifuging according to the conditions of 5000g and 3-10min, washing the centrifuged bacterial precipitate, and then drying to obtain the mixed iron oxide nano material.
The mixed iron oxide nano-material of the present example was subjected to SEM test, and the test results are shown in fig. 4.
As can be seen from FIG. 4, in the mixed iron oxide nanomaterial of the present embodiment, the mineral gradually grows more, and the needle-like mineral size on the surface of the bacteria is approximately 200-300 nm.
Example 5
A biomimetic mineralization method of a mixed iron oxide nano material specifically comprises the following steps:
1) culturing bacillus subtilis and obtaining the bacillus: streaking a preserved bacillus subtilis strain plate overnight for culture, selecting a single strain to be placed in a liquid LB culture medium for amplification culture, inoculating the single strain into the liquid culture medium according to the proportion of 1: 50, performing overnight culture, collecting bacillus subtilis strain according to the conditions of 6000g, 4 ℃ and 10-20min, and washing to obtain wet bacillus subtilis strain, wherein the obtained wet bacillus subtilis strain can be preserved at a low temperature for later use for convenience;
2) mineralization synthesis of nano materials: 0.4g of wet Bacillus subtilis cells were weighed and suspended in 80ml of acidic Fe3+And (2) evenly dividing the solution into 4 parts, subpackaging the 4 parts in an erlenmeyer flask, carrying out biomimetic mineralization synthesis reaction under a standing condition, then sampling within a period of 72-96h of the biomimetic mineralization synthesis reaction, centrifuging according to conditions of 5000g and 3-10min, washing a bacterial precipitate obtained by centrifuging, and drying to obtain the mixed iron oxide nano material.
The mixed iron oxide nano-material of the present example was subjected to SEM test, and the test results are shown in fig. 5.
As can be seen from fig. 5, in the mixed iron oxide nanomaterial of this embodiment, the belt-shaped and block-shaped mixed iron oxide is tightly coated on the bacillus subtilis cells, and the mineralization gradually agglomerates with the extension of the mineralization time, so that the needle-shaped morphology cannot be maintained.
Example 6
A biomimetic mineralization method of a mixed iron oxide nano material specifically comprises the following steps:
1) culturing bacillus subtilis and obtaining the bacillus: streaking a preserved bacillus subtilis strain plate overnight for culture, selecting a single strain to be placed in a liquid LB culture medium for amplification culture, inoculating the single strain into the liquid culture medium according to the proportion of 1: 50, performing overnight culture, collecting bacillus subtilis strain according to the conditions of 6000g, 4 ℃ and 10-20min, and washing to obtain wet bacillus subtilis strain, wherein the obtained wet bacillus subtilis strain can be preserved at a low temperature for later use for convenience;
2) mineralization synthesis of nano materials: weighing 0.4g of bacillus subtilis, carrying out biomimetic mineralization synthesis reaction under the oscillation condition, then sampling within 1-6h of the biomimetic mineralization synthesis reaction, centrifuging according to the conditions of 5000g and 3-10min, washing the centrifuged bacterial precipitate, and then drying to obtain the mixed iron oxide nano material.
Example 7
A biomimetic mineralization method of a mixed iron oxide nano material specifically comprises the following steps:
1) culturing bacillus subtilis and obtaining the bacillus: streaking a preserved bacillus subtilis strain plate overnight for culture, selecting a single strain to be placed in a liquid LB culture medium for amplification culture, inoculating the single strain into the liquid culture medium according to the proportion of 1: 50, performing overnight culture, collecting bacillus subtilis strain according to the conditions of 6000g, 4 ℃ and 10-20min, and washing to obtain wet bacillus subtilis strain, wherein the obtained wet bacillus subtilis strain can be preserved at a low temperature for later use for convenience;
2) mineralization synthesis of nano materials: 0.4g of wet Bacillus subtilis cells were weighed and suspended in 80ml of acidic Fe3+And (2) evenly dividing the solution into 4 parts, subpackaging the 4 parts in an erlenmeyer flask, carrying out biomimetic mineralization synthesis reaction under the oscillation condition, then sampling within a period of 6-24h of the biomimetic mineralization synthesis reaction, centrifuging according to the conditions of 5000g and 3-10min, washing the centrifuged bacterial precipitate, and then drying to obtain the mixed iron oxide nano material.
The mixed iron oxide nano-material of the present example was subjected to SEM test, and the test results are shown in fig. 6.
As can be seen from FIG. 6, the needle-like shape of the nano iron oxide formed on the surface of the bacteria under the oscillation condition is clearer and more complete, the stereoscopic impression is stronger, and the nano iron oxide is not easy to crosslink into a net shape, and the cross-linking in the mineral forming process is interrupted by the oscillation, so that the nano iron oxide is more stereoscopic, and the size is about 100nm and about 200 nm.
Example 8
A biomimetic mineralization method of a mixed iron oxide nano material specifically comprises the following steps:
1) culturing bacillus subtilis and obtaining the bacillus: streaking a preserved bacillus subtilis strain plate overnight for culture, selecting a single strain to be placed in a liquid LB culture medium for amplification culture, inoculating the single strain into the liquid culture medium according to the proportion of 1: 50, performing overnight culture, collecting bacillus subtilis strain according to the conditions of 6000g, 4 ℃ and 10-20min, and washing to obtain wet bacillus subtilis strain, wherein the obtained wet bacillus subtilis strain can be preserved at a low temperature for later use for convenience;
2) mineralization synthesis of nano materials: 0.4g of wet Bacillus subtilis cells were weighed and suspended in 80ml of acidic Fe3+And (2) evenly dividing the solution into 4 parts, subpackaging the 4 parts in an erlenmeyer flask, carrying out biomimetic mineralization synthesis reaction under the oscillation condition, then sampling within 24-48h of the biomimetic mineralization synthesis reaction, centrifuging according to the conditions of 5000g and 3-10min, washing the centrifuged bacterial precipitate, and drying to obtain the mixed iron oxide nano material.
The mixed iron oxide nano-material of the present example was subjected to SEM test, and the test results are shown in fig. 7.
As can be seen from fig. 7, the needle-like morphology of the nano iron oxide formed on the surface of the bacteria under the shaking condition is elongated with time, and a part of the needle-like morphology grows into a honeycomb shape and is cross-linked together.
Example 9
A biomimetic mineralization method of a mixed iron oxide nano material specifically comprises the following steps:
1) culturing bacillus subtilis and obtaining the bacillus: streaking a preserved bacillus subtilis strain plate overnight for culture, selecting a single strain to be placed in a liquid LB culture medium for amplification culture, inoculating the single strain into the liquid culture medium according to the proportion of 1: 50, performing overnight culture, collecting bacillus subtilis strain according to the conditions of 6000g, 4 ℃ and 10-20min, and washing to obtain wet bacillus subtilis strain, wherein the obtained wet bacillus subtilis strain can be preserved at a low temperature for later use for convenience;
2) mineralization synthesis of nano materials: 0.4g of wet Bacillus subtilis cells were weighed and suspended in 80ml of acidic Fe3+And (2) evenly dividing the solution into 4 parts, subpackaging the 4 parts in an erlenmeyer flask, carrying out biomimetic mineralization synthesis reaction under the oscillation condition, then sampling within the period of 48-96h of the biomimetic mineralization synthesis reaction, centrifuging according to the conditions of 5000g and 3-10min, washing the centrifuged bacterial precipitate, and then drying to obtain the mixed iron oxide nano material.
The mixed iron oxide nano-material of the present example was subjected to SEM test, and the test results are shown in fig. 8.
As can be seen from FIG. 8, the needle-like morphology of the nano-iron oxide formed on the surface of the bacteria under the shaking condition is almost only a small portion, and most of the minerals are gradually agglomerated and wrapped on the surface of the bacteria.
Example 10
The mixed iron oxide nano material of the embodiment 5 is used for photocatalytic degradation of organic pollutants, and specifically comprises the following steps: preparing 50mL of methylene blue solution with the concentration of 0.2mM/L, adjusting the pH value to be acidic, then adding 0.025g of mixed iron oxide nano material, stirring in a dark place, adding 0.2% (v/v) of hydrogen peroxide solution, and degrading organic pollutants under natural light.
The mixed iron oxide nanomaterial of example 5 was tested for the degradation rate of organic pollutants by the following specific test steps: in the degradation process, sampling and centrifuging are carried out every 5min, the absorbance of the sample is measured at 665nm, the degradation rate is calculated, and the degradation rate calculation formula is as follows: degradation rate ═ C0-Ct)/CO×100％
The degradation curve of methylene blue degradation is shown in FIG. 9, and the degradation effect is shown in FIG. 10.
As can be seen from fig. 9 and 10, in the methylene blue degradation experiment performed under natural illumination, the mixed iron oxide nanomaterial of example 1 has a degradation rate of 94.06% to methylene blue within 40min, and the color of the solution gradually becomes lighter during the degradation process. In example 5, the material can be recycled after degradation.
Example 11
The mixed iron oxide nano material of the embodiment 5 is used for electrocatalytic hydrogen evolution, and specifically comprises the following steps: under the protection of inert gas, the mixed iron oxide nano material is kept at 500 ℃ for 1-5h, organisms are removed, and the mixed iron oxide nano material is changed into elemental substances, so that the catalyst material for electrocatalytic hydrogen evolution is obtained.
SEM tests were performed on the catalyst material for electrocatalytic hydrogen evolution of the present example, and the test results are shown in fig. 11.
As can be seen from fig. 11, after the mixed iron oxide nanomaterial of example 5 is calcined, the bacterial morphology is substantially maintained, the bacterial surface material still maintains a hollow structure, the needle-like morphology is clear, and the honeycomb network formed by mineral cross-linking can be clearly seen.
The mixed iron oxide nanomaterial of example 5 was subjected to an electrocatalytic hydrogen evolution test, the specific test method being as follows: the electrochemical measurement is carried out by adopting a three-electrode battery, which comprises the following specific steps: platinum wire is used as a counter electrode, and a reversible hydrogen electrode is used as a reference electrode. Wherein the calcined mineralized sample, i.e., the catalyst material for electrocatalytic hydrogen evolution of the present example, had a platinum content of 1mg/cm on glassy carbon2. The electrocatalytic hydrogen evolution of the example was performed by collecting the polarization curve in KOH solution at a rotation speed of 5mV/s1. The test results are shown in fig. 12.
As can be seen from FIG. 12, when the current density was 10mA/cm2In the process, the overpotential of hydrogen evolution of the mixed iron oxide nano material in the embodiment 5 is 350mV, so that the mixed iron oxide nano material has better catalytic hydrogen evolution performance, and after the material is cycled for 1000 times, although the electrocatalytic hydrogen evolution performance is slightly reduced, the reduction trend is small, and the material has certain stability.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A biomimetic mineralization method of a mixed iron oxide nano material is characterized by comprising the following steps:
1) culturing bacillus subtilis, collecting bacillus subtilis thallus, and washing to obtain bacillus subtilis wet thallus;
2) suspending the wet bacillus subtilis thallus in Fe3+And carrying out biomimetic mineralization synthesis reaction in the solution, then sampling and centrifuging at different times, washing and drying to obtain the mixed iron oxide nano material.
2. The biomimetic mineralization method of mixed iron oxide nano-materials as claimed in claim 1, wherein the step 1) of culturing the bacillus subtilis thallus, then collecting the bacillus subtilis thallus and washing to obtain the wet bacillus subtilis thallus comprises: streaking a preserved bacillus subtilis strain plate overnight for culture, selecting a single strain to be placed in a liquid LB culture medium for amplification culture, then inoculating the single strain into the liquid LB culture medium according to the proportion of 1: 50, carrying out overnight culture, then collecting bacillus subtilis thallus according to the conditions of 6000g, 4 ℃ and 10-20min, and washing the bacillus subtilis thallus to obtain the bacillus subtilis wet thallus.
3. The biomimetic mineralization method of mixed iron oxide nanomaterials of claim 1, wherein 1mL of the Fe is used in step 2)3+2-20mg of the wet bacillus subtilis is suspended in the solution.
4. The biomimetic mineralization method of mixed iron oxide nanomaterials of claim 1, wherein the sampling centrifugation at different times in step 2) comprises: sampling is carried out in sections within 1-96h, and then centrifugation is carried out at room temperature according to the conditions of 5000g and 3-10 min.
5. The biomimetic mineralization method of mixed iron oxide nanomaterials of claim 1, wherein the Fe in step 2) is selected from the group consisting of3+P of solutionH is acidic.
6. A mixed iron oxide nanomaterial, characterized in that the mixed iron oxide nanomaterial is mineralized by the biomimetic mineralization method of the mixed iron oxide nanomaterial of any one of claims 1 to 5.
7. The use of the mixed iron oxide nanomaterial of claim 6 in photocatalytic degradation of organic pollutants, comprising the steps of: preparing methylene blue solution with the concentration of 0.2mM/L, adjusting the pH value to be acidic, then adding the mixed iron oxide nano material, stirring in a dark place, adding 0.2% (v/v) hydrogen peroxide solution, and degrading organic pollutants under natural light.
8. The use of the mixed iron oxide nanomaterial of claim 7 in photocatalytic degradation of organic pollutants, wherein 0.5g of the mixed iron oxide nanomaterial is added to 1L of the methylene blue solution.
9. The use of the mixed iron oxide nanomaterial of claim 6 in electrocatalytic hydrogen evolution, comprising the steps of: and under the protection of inert gas, preserving the temperature of the mixed iron oxide nano material at 500 ℃ for 1-5h, and removing organisms to obtain the catalyst material for electrocatalytic hydrogen evolution.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559664A (en) * | 2004-03-02 | 2005-01-05 | 武汉理工大学 | Preparation of bacteria mineralized nanometer needle iron ore and its application |
| DE102005031397A1 (en) * | 2005-07-05 | 2007-01-11 | Klose, Siegfried, Dipl.-Agr.-Ing. | Combined, granulated composition, useful as fertilizer for grass, comprises a basic calcium or magnesium compound mixed with microorganisms, biocatalysts, metal salts and biopolymers |
| CN103848459A (en) * | 2014-01-29 | 2014-06-11 | 浙江工业大学 | Method for preparing urchin-like alpha-Fe2O3 through biological mineralization |
-
2020
- 2020-01-14 CN CN202010036028.6A patent/CN111282600B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559664A (en) * | 2004-03-02 | 2005-01-05 | 武汉理工大学 | Preparation of bacteria mineralized nanometer needle iron ore and its application |
| DE102005031397A1 (en) * | 2005-07-05 | 2007-01-11 | Klose, Siegfried, Dipl.-Agr.-Ing. | Combined, granulated composition, useful as fertilizer for grass, comprises a basic calcium or magnesium compound mixed with microorganisms, biocatalysts, metal salts and biopolymers |
| CN103848459A (en) * | 2014-01-29 | 2014-06-11 | 浙江工业大学 | Method for preparing urchin-like alpha-Fe2O3 through biological mineralization |
Non-Patent Citations (3)
| Title |
|---|
| 孙振亚等: "铁( 氢) 氧化物矿物对有机污染物的光催化氧化作用", 《矿物学报》 * |
| 胡凯光等: "《核工业生物学》", 28 February 2015, 北京：北京理工大学出版社 * |
| 董济军等: "《浮动草床与微生态制剂调控养殖池塘水环境新技术》", 31 March 2017, 北京：海洋出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114317370A (en) * | 2022-01-11 | 2022-04-12 | 浙江大学 | Preparation method of bionic silicon mineralized bacteria and application of bionic silicon mineralized bacteria in treatment of phenol wastewater |
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