CN104450790B - It is a kind of to prepare the biological method that p ferrites modify n bloodstone heterojunction structures - Google Patents
It is a kind of to prepare the biological method that p ferrites modify n bloodstone heterojunction structures Download PDFInfo
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- CN104450790B CN104450790B CN201410805812.3A CN201410805812A CN104450790B CN 104450790 B CN104450790 B CN 104450790B CN 201410805812 A CN201410805812 A CN 201410805812A CN 104450790 B CN104450790 B CN 104450790B
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Abstract
The biological method that p ferrites modify n bloodstone heterojunction structures is prepared the present invention relates to a kind of utilization Shewanella putrefaciens MR 1, the method develops the p-type ferrite N-shaped bloodstone heterojunction structure of p n knots and ohm layer by biosynthesis technology, it is carried out in two steps, the first step：A Zn (A=Mg, Mn or Ni) the modification goethites of the nm of peptization technique of backflow prepared sizes about 50（FeOOH）Powder；Second step：Shewanella putrefaciens MR 1 is cultivated under room temperature anaerobic condition and reduces part ferric iron, obtain (A Zn) Fe2O4‑Fe2O3Hetero-junctions.The method is compared with prior art：Have the advantages that process is simple, pollute it is small, consume energy it is low, be easy to amplify, the rate of recovery it is high, by the method obtain (A Zn) Fe2O4‑Fe2O3Hetero-junctions surface defect is low, reunite less, epigranular, is provided simultaneously with preferable light thermo-magnetic characteristics.
Description
Technical field
P- ferrites modification n- bloodstone heterojunction structures are prepared the present invention relates to a kind of utilization Shewanella putrefaciens MR-1
Biological method, belongs to field of inorganic materials.
Background technology
N-type semiconductor bloodstone (Fe2O3；Band gap：2eV) it is an important semiconductor material in the field of catalyst
Material, it has been applied to photoelectric material, photocatalysis and magnetic storage medium.However, poor (the 0.2cm of carrier mobility2·V-1·s-1) and the defect such as ultrafast restructuring (~10ps) of photo-generated carrier limit its large-scale promotion.Research surface is designed and is made at present
Standby controllable Fe2O3Base heterojunction structure is remarkably improved the efficiency in light induced electron and hole, and stock blend physical mixed institute occurs not
The new attribute for possessing.For example, using Fe2O3With p-type ferrospinel (band gap： ) conjugation form p-n structure.
The incorporation of magnetic nano crystal can not only improve photocatalysis efficiency, and the catalyst that can be reclaimed in gentle magnetic field passes through
Magneto separate, this is that photocatalytic applications have a great attraction.2008, it is ferritic special that Pailhe' etc. reports zinc doping
Magnetic and photoluminescence property.Then, the seminar such as Lee, Sutka, Klimkiewicz is in succession using spray pyrolysis deposition, one
The step means such as chemical synthesis and liquid phase thermal synthesis are prepared for p-type ferrite-N-shaped bloodstone heterojunction structure, and report stock blend
The new parameters such as the magnetic, surface photovoltage, the hollow-core construction that are not had.Therefore, p-n junction ceramics are considered as to explore rich in iron
The advanced composite material (ACM) of the various nanostructureds of oxide, this is by the photoelectricity of various functions of the material for promoting application program integrated
Characteristic.
Traditional surface defect being either physically or chemically all difficult to avoid that because of high annealing, therefore, new research is concentrated
In preparation and the nano material described in biosynthesis.Recently, researcher uses different microbe researches nanoscale point brilliant
The synthetic work of stone, specific course of reaction is as follows：Lactic acid (Lactate-)+4Fe3++2H2O → 1,1- diethoxyethane
(acetal-)+HCO-+4Fe2++5H+；A2++2Fe(OH)3→AFe2O4+2H2O+2H+(A=Fe, Mg, Zn, Mn, Ni, Ca etc.).
The content of the invention
Present invention aim at, there is provided it is a kind of to prepare the biological method that p- ferrites modify n- bloodstone heterojunction structures, should
Method develops the p-type ferrite-N-shaped bloodstone heterojunction structure of p-n junction and ohm layer by biosynthesis technology, enters in two steps
OK, the first step：A-Zn (A=Mg, Mn or Ni) modification goethite (FeOOH) powder of peptization technique of backflow prepared sizes about 50nm
Body；Second step：Shewanella putrefaciens MR-1 reduction part ferric irons are cultivated under room temperature anaerobic condition, (A-Zn) Fe is obtained2O4-
Fe2O3Hetero-junctions.The method is compared with prior art：With process is simple, pollute it is small, consume energy it is low, be easy to amplify, the rate of recovery it is high
The advantages of.(A-Zn) Fe obtained by the method2O4-Fe2O3Hetero-junctions surface defect is low, reunite less, epigranular, while
Possess preferable light thermo-magnetic characteristics.
A kind of biological method for preparing p- ferrites modification n- bloodstone heterojunction structures of the present invention, the method is utilized
Shewanella putrefaciens MR-1 prepares p- ferrites modification n- bloodstone heterojunction structures, and concrete operations follow these steps to carry out：
A, by raw material MgCl2、MnCl2Or NiCl2With ZnCl2And FeCl3·6H2O Mg in molar ratio2+、Mn2+Or Ni2+∶Zn2+
∶Fe3+During=0.5: 0.5: 2 addition pH value are 2 aqueous solution of nitric acid, in temperature, 85 DEG C are flowed back 2 hours, are stood, true temp 50
DEG C drying 20 hours, obtains Mg2+、Mn2+Or Ni2+, and Zn2+The FeOOH powders of modification；
B, by 30gL-1Shewanella putrefaciens MR-1 obtains cell in liquid pancreas peptone soybean broth medium culture
Concentration is 2.3 × 108Cells/ml-1, Shewanella putrefaciens MR-1 strains are centrifuged out under 5 DEG C of freezing conditions of temperature, it is added to
In Mineralized Culture base, the FeOOH powders for being subsequently adding the modification for obtaining step a are configured to the Mg that concentration is 90mM2+、Mn2+Or
Ni2+, and Zn2+The FeOOH solution of modification, regulation solution ph is 6-8, and adds the ethyl sulfonic acid of Isosorbide-5-Nitrae-piperazine two and anthraquinone simultaneously
2,6- disulfonates, alleviate cell contact with FeOOH solution, accelerate Fe3+Reduction reaction；
C, the reaction solution aerobic sealing by step b, keep in dark place 45 days under the conditions of 30 DEG C of temperature, are centrifuged, true temp
70 DEG C of dryings 48 hours, obtain p- ferrites modification n- bloodstone heterojunction structures.
Mineralized Culture base component in step b is (NH4)2SO4 9.0mM,K2HPO4 5.7mM,KH2PO4 3.3mM,
NaHCO32.0mM,MgSO4·7H2O 1.01mM,CaCl2·2H2O0.485mM, 67.2 μM of Ferric Sodium Edetate,
H3BO356.6μM,NaCl 10.0μM,FeSO4·7H2O 5.4μM,CoSO4 5.0μM,Ni(NH4)2(SO4)2 5.0μM,
Na2MoO4 3.87μM,Na2SeO4 1.5μM,MnSO4 1.26μM,ZnSO4 1.04μM,CuSO40.2 μM, arginase 12 0mgL-1, glutamic acid 20mgL-1With serine 20mgL-1。
The biological method for preparing p- ferrites modification n- bloodstone heterojunction structures of the present invention, it is involved in the method
Shewanella putrefaciens MR-1 (Gram-negative, facultative anaerobic bacteria) for purchase product, by Midland, MI university, Chinese Geological
University, Dong's current chart seminar of Xinan Science and Technology Univ. provide, and Shewanella putrefaciens MR-1 genomes are 42c type cytochromes, cell
Cytochromes (tryptose pigment A-OmcA, tryptose pigment C-MtrC and tryptose pigment B-MtrB) and the iron hydrogenation of epimatrix
Enzyme is positioned in the diverse location of inner membrance and adventitia, forms " molecular line " configuration, there is provided insoluble electron acceptor and electronics are moved
Pass in and out the path of cell.These genome sequences provide a key step of bivalent metal ion reduction (and biological prosthetic)
And be Fe suddenly,2O3Surface divalent transition metal ion study on the modification provide a kind of new approach.
The biological method for preparing p- ferrites modification n- bloodstone heterojunction structures of the present invention, it is involved in the method
Liquid TSB culture mediums be pancreas peptone soybean broth culture medium.
Brief description of the drawings
Fig. 1 is the powder x-ray diffraction peak of the final product that the present invention was obtained by MR-1 microbial mineralizations treatment in 45 days
Shape, wherein- -represent Fe3O4Phase ,-▽-Fe2O3Phase, (1) is Fe3O4And Fe2O3XRD；(2) it is Zn-Mg codopes
Fe3O4-Fe2O3XRD；(3) it is Zn-Mn codopes Fe3O4-Fe2O3XRD；(4) it is Zn-Ni codopes Fe3O4-Fe2O3
XRD；
Fig. 2 is the powder Raman spectrum that the present invention processes the final product for obtaining by microbial mineralization, whereinGeneration
Table Fe3O4-Fe2O3Raman spectrum；Represent Zn-Mg codopes FeFe3O4-Fe2O3Raman spectrum；Represent
Zn-Mn codopes Fe3O4-Fe2O3Raman spectrum；Represent Zn-Ni codopes Fe3O4-Fe2O3Raman spectrum；Can from figure
To find out reactant as AZnFe2O4Compound Fe2O3Powder (Fe-O peak values：200~300cm-1), compared with former reactant, it is combined
Fe is included in phase2+-Fe3+Compound keys, this is the key reaction site of p-n junction.
Fig. 3 is (A-Zn) Fe that the present invention is obtained by microbiological treatment2O4-Fe2O3The ultraviolet-visible of hetero-junctions is unrestrained anti-
DRS figures are penetrated, whereinRepresent Zn-Mn codopes Fe3O4-Fe2O3UV-Vis DRS figure；Represent Zn-Mg
Codope Fe3O4-Fe2O3UV-Vis DRS figure；Represent Zn-Ni codopes Fe3O4-Fe2O3Ultraviolet-visible
Diffusing reflection figure；Represent Fe3O4-Fe2O3UV-Vis DRS figure；As can be seen from the figure product belongs to p-n junction
Heterojunction structure, p-type energy gap is 1.42~1.84eV, and N-shaped energy gap is 2.46~2.69eV.Particularly noteworthy is (Ni-
Zn)Fe2O4-Fe2O3Transition energy gap (2.76eV) is occurred in that in hetero-junctions, this can be used as effective electron and effective hole transport
Transfer area.Compared with traditional p-n junction, photoelectron is transported with capture rate faster.
Specific embodiment
Embodiment 1
A, in molar ratio be Mg2+∶Zn2+∶Fe3+Weigh raw material MgCl at=0.5: 0.5: 22、ZnCl2And FeCl3·6H2O, plus
Enter the aqueous solution of nitric acid that pH value is 2, flowed back 2 hours at 85 DEG C of temperature, reactant is that peptization back flow reaction occurs, and solution is by nothing
Color is transparent to be changed into khaki suspension, and reaction in 2 hours terminates, and solid-liquid layering, obtains khaki powder product, by powder after standing
After being washed to removal by-product ammonium chloride, the drying 20 hours of 50 DEG C of true temp obtains Mg2+And Zn2+Modification FeOOH powders；
B, by 30gL-1Shewanella putrefaciens MR-1 is cultivated in liquid pancreas peptone soybean broth culture medium, is obtained
To cell concentration 2.3 × 108Cells/ml-1, Shewanella putrefaciens MR-1 strains are centrifuged out under 5 DEG C of freezing conditions of temperature, will
Shewanella putrefaciens MR-1 strains are added to Mineralized Culture base for (NH4)2SO49.0mM,K2HPO45.7mM,KH2PO43.3mM,
NaHCO32.0mM,MgSO4·7H2O1.01mM,CaCl2·2H2O0.485mM, 67.2 μM of Ferric Sodium Edetate,
H3BO356.6μM,NaCl10.0μM,FeSO4·7H2O5.4μM,CoSO45.0μM,Ni(NH4)2(SO4)25.0μM,
Na2MoO43.87μM,Na2SeO41.5μM,MnSO41.26μM,ZnSO41.04μM,CuSO40.2 μM, arginase 12 0mgL-1, paddy
Propylhomoserin 20mgL-1With serine 20mgL-1In, be subsequently adding the modification for obtaining step a FeOOH powders be configured to it is dense
Spend the Mg for 90mM2+-Zn2+Modification FeOOH solution, regulation pH value is 8, and adds the ethyl sulfonic acid of Isosorbide-5-Nitrae-piperazine two (PIPES) simultaneously
With anthraquinone 2,6- disulfonates (AQDS), alleviation cell contact with FeOOH solution, acceleration Fe3+Reduction reaction；
C, the reaction solution aerobic sealing by step b, keep in dark place 45 days under the conditions of 30 DEG C of temperature, reactant be occur it is micro-
Biological Fe3+-Fe2+Reduction reaction, surface color is changed into yellowish-brown suspension from khaki powder, and reaction obtains dark brown after terminating
Color powder, centrifugation, 70 DEG C of true temp drying 48 hours obtains (Mg-Zn) Fe2O4-Fe2O3Hetero-junctions, the rate of recovery is
88.57%.
Embodiment 2
A, in molar ratio be Mn2+∶Zn2+∶Fe3+Weigh raw material MnCl at=0.5: 0.5: 22、ZnCl2And FeCl3·6H2O, plus
In entering the aqueous solution of nitric acid that pH value is 2, peptization flows back 2 hours at 85 DEG C of temperature, and solution is changed into light yellow outstanding from water white transparency
Turbid liquid, reaction in 2 hours terminates, and solid-liquid layering after standing, 50 DEG C of true temp drying 20 hours obtains isabelline Mn2+-Zn2+Repair
Decorations FeOOH powder；
B, by 30gL-1Shewanella putrefaciens MR-1 obtains cell in liquid pancreas peptone soybean broth medium culture
Concentration is 2.3 × 108Cells/ml-1, Shewanella putrefaciens MR-1 strains are centrifuged out under 5 DEG C of freezing conditions of temperature, by corruption
Shewanella MR-1 strains are added to Mineralized Culture base for (NH4)2SO4 9.0mM,K2HPO4 5.7mM,KH2PO4 3.3mM,
NaHCO3 2.0mM,MgSO4·7H2O 1.01mM,CaCl2·2H2O0.485mM, 67.2 μM of Ferric Sodium Edetate, H3BO3
56.6μM,NaCl 10.0μM,FeSO4·7H2O 5.4μM,CoSO4 5.0μM,Ni(NH4)2(SO4)2 5.0μM,Na2MoO4
3.87μM,Na2SeO4 1.5μM,MnSO4 1.26μM,ZnSO4 1.04μM,CuSO40.2 μM, arginase 12 0mgL-1, paddy ammonia
Sour 20mgL-1With serine 20mgL-1In, the FeOOH powders for being subsequently adding the modification for obtaining step a are configured to concentration
It is the Mn of 90mM2+-Zn2+Modification FeOOH solution, regulation pH value be 7, and simultaneously add the ethyl sulfonic acid of Isosorbide-5-Nitrae-piperazine two (PIPES) and
Anthraquinone 2,6- disulfonates (AQDS) alleviate cell contact with FeOOH solution, accelerate Fe3+Reduction reaction；
C, the reaction solution aerobic sealing by step b, keep in dark place 45 days under the conditions of 30 DEG C of temperature, reaction-ure surface color
Yellowish-brown suspension is changed into from khaki powder, reaction obtains Red-brown powder after terminating, and is centrifuged, 70 DEG C of dryings 48 of true temp
Hour, obtain (Mn-Zn) Fe2O4-Fe2O3Hetero-junctions, the rate of recovery is 94.28%.
Embodiment 3
A, in molar ratio be Ni2+∶Zn2+∶Fe3+Weigh raw material NiCl at=0.5: 0.5: 22、ZnCl2And FeCl3·6H2O, plus
Enter in the aqueous solution of nitric acid that pH value is 2, in temperature, 85 DEG C are flowed back 2 hours, and solution is changed into chartreuse suspension from water white transparency,
Solid-liquid layering after standing, 50 DEG C of true temp drying 20 hours obtains light yellow Ni2+-Zn2+Modification FeOOH powder；
By 30gL-1Shewanella putrefaciens MR-1 obtains cell dense in liquid pancreas peptone soybean broth medium culture
Spend is 2.3 × 108Cells/ml-1, Shewanella putrefaciens MR-1 strains are centrifuged out under 5 DEG C of freezing conditions of temperature, corruption is uncommon
Watt Salmonella MR-1 strains are added to Mineralized Culture base for (NH4)2SO4 9.0mM,K2HPO4 5.7mM,KH2PO4 3.3mM,NaHCO3
2.0mM,MgSO4·7H2O 1.01mM,CaCl2·2H2O0.485mM, 67.2 μM of Ferric Sodium Edetate, H3BO3 56.6μ
M,NaCl 10.0μM,FeSO4·7H2O 5.4μM,CoSO4 5.0μM,Ni(NH4)2(SO4)2 5.0μM,Na2MoO4 3.87μM,
Na2SeO4 1.5μM,MnSO4 1.26μM,ZnSO4 1.04μM,CuSO40.2 μM, arginase 12 0mgL-1, glutamic acid 20mg
L-1With serine 20mgL-1In, the FeOOH powders for being subsequently adding the modification for obtaining step a are configured to concentration for 90mM
Ni2+-Zn2+Modification FeOOH solution, regulation pH value is 6, and adds the ethyl sulfonic acid of Isosorbide-5-Nitrae-piperazine two (PIPES) and anthraquinone 2,6- simultaneously
Disulfonate (AQDS), alleviates cell contact with FeOOH solution, accelerates Fe3+Reduction reaction；
C, the reaction solution aerobic sealing by step b, keep in dark place 45 days under the conditions of 30 DEG C of temperature, reaction-ure surface color
Yellow green suspension is changed into from khaki powder, reaction obtains dark brown powder after terminating, and is centrifuged, 70 DEG C of dryings 48 of true temp
Hour, obtain (Ni-Zn) Fe2O4-Fe2O3Hetero-junctions, the rate of recovery is 87.14%.
Claims (2)
1. it is a kind of to prepare the biological method that p- ferrites modify n- bloodstone heterojunction structures, it is characterised in that the method is using corrupt
Shewanella MR-1 prepares p- ferrites modification n- bloodstone heterojunction structures, and concrete operations follow these steps to carry out：
A, by raw material MgCl2、MnCl2Or NiCl2With ZnCl2And FeCl3·6H2O Mg in molar ratio2+、Mn2+Or Ni2+∶Zn2+∶Fe3+
=0.5: 0.5: 2, in adding pH value to be 2 aqueous solution of nitric acid, in temperature, 85 DEG C are flowed back 2 hours, are stood, and 50 DEG C of true temp is done
Dry 20 hours, obtain Mg2+、Mn2+Or Ni2+, and Zn2+The FeOOH powders of modification；
B, by 30gL-1Shewanella putrefaciens MR-1 obtains cell concentration in liquid pancreas peptone soybean broth medium culture
It is 2.3 × 108Cells/ml-1, Shewanella putrefaciens MR-1 strains are centrifuged out under 5 DEG C of freezing conditions of temperature, then corruption is uncommon
Watt Salmonella MR-1 strains are added in Mineralized Culture base, be subsequently adding the modification for obtaining step a FeOOH powders be configured to it is dense
It is the Mg of 90 mM to spend2+、Mn2+Or Ni2+, and Zn2+The FeOOH solution of modification, regulation solution ph is 6-8, and adds 1 simultaneously,
The ethyl sulfonic acid of 4- piperazines two and anthraquinone 2,6- disulfonates alleviate cell contact with FeOOH solution, accelerate Fe3+Reduction reaction；
C, the reaction solution aerobic sealing by step b, keep in dark place 45 days under the conditions of 30 DEG C of temperature, are centrifuged, 70 DEG C of true temp
Dry 48 hours, obtain p- ferrites modification n- bloodstone heterojunction structures.
2. method according to claim 1, it is characterised in that the Mineralized Culture base component in step b is (NH4)2SO4 9.0
mM, K2HPO4 5.7 mM, KH2PO4 3.3 mM, NaHCO3 2.0 mM, MgSO4·7H2O 1.01 mM, CaCl2·
2H2The mM of O 0.485,67.2 μM of Ferric Sodium Edetate, H3BO3 56.6μM, NaCl 10.0μM, FeSO4·7H2O
5.4μM, CoSO4 5.0μM, Ni(NH4)2(SO4)2 5.0μM, Na2MoO4 3.87μM, Na2SeO4 1.5μM, MnSO4
1.26μM, ZnSO4 1.04μM, CuSO40.2 μM, the mgL of arginase 12 0−1, the mgL of glutamic acid 20−1And serine
20 mg·L−1。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062790A (en) * | 2007-04-20 | 2007-10-31 | 南京大学 | Simple preparation method of alpha-FeOOH and alpha-Fe2O3 nano stick |
| CN102583574A (en) * | 2012-03-09 | 2012-07-18 | 四川大学 | Cathode material, alpha-Fe2O3, of high-capacity lithium ion battery and preparation method for material |
| WO2012162817A1 (en) * | 2011-06-03 | 2012-12-06 | Orbite Aluminae Inc. | Methods for preparing hematite |
| CN103030181A (en) * | 2011-09-30 | 2013-04-10 | 朗盛德国有限责任公司 | Improved method for producing finely divided haematite and for producing iron oxide red pigments |
-
2014
- 2014-12-22 CN CN201410805812.3A patent/CN104450790B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062790A (en) * | 2007-04-20 | 2007-10-31 | 南京大学 | Simple preparation method of alpha-FeOOH and alpha-Fe2O3 nano stick |
| WO2012162817A1 (en) * | 2011-06-03 | 2012-12-06 | Orbite Aluminae Inc. | Methods for preparing hematite |
| CN103030181A (en) * | 2011-09-30 | 2013-04-10 | 朗盛德国有限责任公司 | Improved method for producing finely divided haematite and for producing iron oxide red pigments |
| CN102583574A (en) * | 2012-03-09 | 2012-07-18 | 四川大学 | Cathode material, alpha-Fe2O3, of high-capacity lithium ion battery and preparation method for material |
Non-Patent Citations (1)
| Title |
|---|
| "奥奈达希瓦氏菌MR-1的Fe(Ⅲ)还原特性及其影响因素";陈洁等;《安徽农业大学学报》;20110624;第38卷(第4期);第554-558页 * |
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