CN104450790A - Biological method of preparing p-ferrite-modified n-hematite heterostructure - Google Patents
Biological method of preparing p-ferrite-modified n-hematite heterostructure Download PDFInfo
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- CN104450790A CN104450790A CN201410805812.3A CN201410805812A CN104450790A CN 104450790 A CN104450790 A CN 104450790A CN 201410805812 A CN201410805812 A CN 201410805812A CN 104450790 A CN104450790 A CN 104450790A
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Abstract
The invention relates to a biological method of preparing a p-ferrite-modified n-hematite heterostructure by virtue of shewanella putrefaciens MR-1. According to the method, a p type ferrite-n type hematite heterostructure of a p-n junction and an ohmic layer is developed through a biosynthesis technology, and the method is carried out in two steps, step 1, preparing A-Zn (A is Mg, Mn or Ni)-modified goethite (FeOOH) powder with a particle size of about 50nm by virtue of a peptize reflux technology; and step 2, curing shewanella putrefaciens MR-1 under a room-temperature anaerobic condition and reducing a part of ferric iron to obtain a (A-Zn)Fe2O4-Fe2O3 heterojunction. Compared with the prior art, the method has the advantages of being simple in process, less in pollution, low in energy consumption, easy to enlarge, high in recovery rate and the like; the (A-Zn)Fe2O4-Fe2O3 heterojunction obtained through the method is low in surface defects, low in agglomeration, uniform in particle size, and good in optical, thermal and magnetic characteristics.
Description
Technical field
The present invention relates to a kind of biological method utilizing Shewanella putrefaciens MR-1 to prepare p-ferrite modification n-rhombohedral iron ore heterojunction structure, belong to field of inorganic materials.
Background technology
N-type semiconductor rhombohedral iron ore (Fe
2o
3; Band gap: 2eV) be the important semiconductor material of in the field of catalyzer one, it has been applied to photoelectric material, photochemical catalysis and magnetic storage medium.But, carrier mobility rate variance (0.2cm
2v
-1s
-1) and its large-scale promotion of the drawbacks limit such as ultrafast restructuring (~ 10ps) of photo-generated carrier.The Fe that current research surface design is controlled with preparation
2o
3base heterojunction structure can significantly improve the efficiency in light induced electron and hole, and occurs the new attribute not available for stock blend physical mixed.Such as, Fe is adopted
2o
3p-n junction structure is formed with p-type ferrospinel (band gap: 1.9 ~ 2.7eV) conjugation.Mixing of magnetic nano crystal not only can improve photocatalysis efficiency, and the catalyzer that can reclaim in the magnetic field of gentleness is by Magneto separate, and this is that photocatalytic applications haves a great attraction.2008, Pailhe' etc. reported the ferritic special magnetic of zinc doping and photoluminescence property.Then, the seminars such as Lee, Sutka, Klimkiewicz adopt the means such as spray pyrolysis deposits, a step chemosynthesis and liquid phase thermal synthesis to prepare p-type ferrite-N-shaped rhombohedral iron ore heterojunction structure in succession, and report the new argument such as magnetic, surface photovoltage, hollow structure that stock blend do not have.Therefore, p-n junction pottery is considered to explore the advanced composite material of the various nanostructures of the oxide compound being rich in iron, and this will promote the photoelectric characteristic of the several functions of the material that application program is integrated.
Traditional physics or chemical process are all difficult to avoid the surface imperfection because of high temperature annealing, and therefore, new research concentrates on preparation and the nano material described in biosynthesizing.Recently, researchist uses the different microbe researches synthetic work of nano-grade spinel, and concrete reaction process is as follows: lactic acid (Lactate
-)+4Fe
3++ 2H
2o → 1,1-diethoxyethane (acetat
-)+HCO
-+ 4Fe
2++ 5H
+; A
2++ 2Fe (OH)
3→ AFe
2o
4+ 2H
2o+2H
+(A=Fe, Mg, Zn, Mn, Ni, Ca etc.).
Summary of the invention
The object of the invention is, there is provided a kind of and prepare the biological method that p-ferrite modifies n-rhombohedral iron ore heterojunction structure, the method develops the p-type ferrite-N-shaped rhombohedral iron ore heterojunction structure of p-n junction and ohm layer by biosynthesis technology, carry out in two steps, the first step: the A-Zn (A=Mg, Mn or Ni) that peptization technique of backflow prepared sizes are about 50nm modifies pyrrhosiderite (FeOOH) powder; Second step: cultivate Shewanella putrefaciens MR-1 reduction part ferric iron under room temperature anaerobic condition, obtain (A-Zn) Fe
2o
4-Fe
2o
3heterojunction.The method is compared with prior art: have technique simple, pollute little, consume energy low, be easy to amplify, rate of recovery advantages of higher.(A-Zn) Fe obtained by the method
2o
4-Fe
2o
3heterojunction surface imperfection is low, reunite less, epigranular, possesses good photo-thermal magnetic properties simultaneously.
A kind of biological method preparing p-ferrite modification n-rhombohedral iron ore heterojunction structure of the present invention, the method utilizes Shewanella putrefaciens MR-1 to prepare p-ferrite and modifies n-rhombohedral iron ore heterojunction structure, and concrete operations follow these steps to carry out:
A, by raw material MgCl
2, MnCl
2or NiCl
2with ZnCl
2and FeCl
36H
2o is Mg in molar ratio
2+, Mn
2+or Ni
2+: Zn
2+: Fe
3+=0.5: 0.5: 2 to add pH value be in the aqueous nitric acid of 2, and temperature 85 DEG C backflow 2 hours, leave standstill, true temp 50 DEG C of dryings 20 hours, obtained Mg
2+, Mn
2+or Ni
2+, and Zn
2+the FeOOH powder modified;
B, by 30gL
-1shewanella putrefaciens MR-1 is in liquid pancreas peptone soybean broth culture medium culturing, and obtaining cell concn is 2.3 × 10
8cells/ml
-1, under temperature 5 DEG C of freezing conditions centrifugal go out Shewanella putrefaciens MR-1 bacterial classification, join in Mineralized Culture base, the FeOOH powder then adding the modification obtained by step a is mixed with the Mg that concentration is 90mM
2+, Mn
2+or Ni
2+, and Zn
2+the FeOOH solution modified, regulator solution pH value is 6-8, and adds Isosorbide-5-Nitrae-piperazine two ethyl sulfonic acid and anthraquinone 2,6-disulfonate simultaneously, alleviates the contact of cell and FeOOH solution, accelerates Fe
3+reduction reaction;
C, by reaction solution anaerobic sealing of step b, keep in Dark Place 45 days under temperature 30 DEG C of conditions, centrifugal, true temp 70 DEG C of dryings 48 hours, obtain p-ferrite and modify n-rhombohedral iron ore heterojunction structure.
Mineralized Culture base component in step b is (NH
4)
2sO
49.0mM, K
2hPO
45.7mM, KH
2pO
43.3mM, NaHCO
32.0mM, MgSO
47H
2o 1.01mM, CaCl
22H
2o0.485mM, Sytron 67.2 μMs, H
3bO
356.6 μMs, NaCl 10.0 μMs, FeSO
47H
2o 5.4 μMs, CoSO
45.0 μMs, Ni (NH
4)
2(SO
4)
25.0 μMs, Na
2moO
43.87 μMs, Na
2seO
41.5 μMs, MnSO
41.26 μMs, ZnSO
41.04 μMs, CuSO
40.2 μM, arginase 12 0mgL
-1, L-glutamic acid 20mgL
-1with Serine 20mgL
-1.
Preparation p-ferrite of the present invention modifies the biological method of n-rhombohedral iron ore heterojunction structure, Shewanella putrefaciens MR-1 (Gram-negative involved in the method, facultative anaerobe) for buying product, by Midland, MI university, China University of Geosciences, Dong's current chart seminar of Xinan Science and Technology Univ. provides, Shewanella putrefaciens MR-1 genome is 42c type cytopigment, cytopigment (the Trypsin pigment A-OmcA of extracellular matrix, Trypsin pigment C-MtrC and Trypsin pigment B-MtrB) and iron hydrogenase be positioned in the different positions of inner membrance and adventitia, form " molecular line " configuration, provide the path that insoluble electron acceptor(EA) and electronics move turnover cell.These genome sequences provide a committed step of divalent-metal ion reduction (and biological restoration), and are Fe
2o
3the study on the modification of surperficial divalent transition metal ion provide a kind of new approach.
Preparation p-ferrite of the present invention modifies the biological method of n-rhombohedral iron ore heterojunction structure, and liquid TSB substratum involved in the method is pancreas peptone soybean broth substratum.
Accompanying drawing explanation
The powder x-ray diffraction peak shape of Fig. 1 final product that to be the present invention obtain through the process of 45 days MR-1 microbial mineralizations, wherein--represent Fe
3o
4phase ,-▽-Fe
2o
3phase, (1) is Fe
3o
4and Fe
2o
3xRD figure; (2) be Zn-Mg codoped Fe
3o
4-Fe
2o
3xRD figure; (3) be Zn-Mn codoped Fe
3o
4-Fe
2o
3xRD figure; (4) be Zn-Ni codoped Fe
3o
4-Fe
2o
3xRD figure;
The powder Raman spectrum of Fig. 2 final product that to be the present invention obtain through microbial mineralization process, wherein
represent Fe
3o
4-Fe
2o
3raman spectrum;
represent Zn-Mg codoped FeFe
3o
4-Fe
2o
3raman spectrum;
represent Zn-Mn codoped Fe
3o
4-Fe
2o
3raman spectrum;
represent Zn-Ni codoped Fe
3o
4-Fe
2o
3raman spectrum; As can be seen from the figure reactant is AZnFe
2o
4compound Fe
2o
3powder (Fe-O peak value: 200 ~ 300cm
-1), compared with former reactant, in compound phase, comprise Fe
2+-Fe
3+compound keys, this is the principal reaction site of p-n junction.
Fig. 3 is (A-Zn) Fe that the present invention obtains through microbiological treatment
2o
4-Fe
2o
3the UV-Vis DRS DRS of heterojunction schemes, wherein
represent Zn-Mn codoped Fe
3o
4-Fe
2o
3uV-Vis DRS figure;
represent Zn-Mg codoped Fe
3o
4-Fe
2o
3uV-Vis DRS figure;
represent Zn-Ni codoped Fe
3o
4-Fe
2o
3uV-Vis DRS figure;
represent Fe
3o
4-Fe
2o
3uV-Vis DRS figure; As can be seen from the figure product belongs to p-n junction heterojunction structure, and p-type energy gap is 1.42 ~ 1.84eV, and N-shaped energy gap is 2.46 ~ 2.69eV.It should be noted that (Ni-Zn) Fe especially
2o
4-Fe
2o
3occurred transition energy gap (2.76eV) in heterojunction, this can be used as the transfer district of effective electron and effective hole transport.Compared with traditional p-n junction, photoelectron transports with capture rate faster.
Embodiment
Embodiment 1
A, be Mg in molar ratio
2+: Zn
2+: Fe
3+take raw material MgCl at=0.5: 0.5: 2
2, ZnCl
2and FeCl
36H
2o, add the aqueous nitric acid that pH value is 2, reflux 2 hours at temperature 85 DEG C, namely there is peptization back flow reaction in reactant, solution becomes khaki color suspension liquid from water white transparency, and reaction in 2 hours terminates, solid-liquid layering after leaving standstill, obtain khaki color powdered product, be washed to by powder after removing by-product ammonium chloride, true temp 50 DEG C of dryings obtain Mg in 20 hours
2+and Zn
2+modify FeOOH powder;
B, by 30gL
-1shewanella putrefaciens MR-1 cultivates in liquid pancreas peptone soybean broth substratum, obtains cell concn 2.3 × 10
8cells/ml
-1, under temperature 5 DEG C of freezing conditions centrifugal go out Shewanella putrefaciens MR-1 bacterial classification, it is (NH that Shewanella putrefaciens MR-1 bacterial classification is joined Mineralized Culture base
4)
2sO
49.0mM, K
2hPO
45.7mM, KH
2pO
43.3mM, NaHCO
32.0mM, MgSO
47H
2o 1.01mM, CaCl
22H
2o0.485mM, Sytron 67.2 μMs, H
3bO
356.6 μMs, NaCl 10.0 μMs, FeSO
47H
2o 5.4 μMs, CoSO
45.0 μMs, Ni (NH
4)
2(SO
4)
25.0 μMs, Na
2moO
43.87 μMs, Na
2seO
41.5 μMs, MnSO
41.26 μMs, ZnSO
41.04 μMs, CuSO
40.2 μM, arginase 12 0mgL
-1, L-glutamic acid 20mgL
-1with Serine 20mgL
-1in, the FeOOH powder then adding the modification obtained by step a is mixed with the Mg that concentration is 90mM
2+-Zn
2+modify FeOOH solution, adjust ph is 8, and adds Isosorbide-5-Nitrae-piperazine two ethyl sulfonic acid (PIPES) and anthraquinone 2,6-disulfonate (AQDS) simultaneously, alleviates the contact of cell and FeOOH solution, accelerates Fe
3+reduction reaction;
C, by reaction solution anaerobic sealing of step b, keeping in Dark Place 45 days under temperature 30 DEG C of conditions, namely there is microorganism Fe in reactant
3+-Fe
2+reduction reaction, surface color becomes tawny suspension liquid from khaki color powder, obtains chocolate powder after reaction terminates, centrifugal, and true temp 70 DEG C of dryings 48 hours obtain (Mg-Zn) Fe
2o
4-Fe
2o
3heterojunction, the rate of recovery is 88.57%.
Embodiment 2
A, be Mn in molar ratio
2+: Zn
2+: Fe
3+take raw material MnCl at=0.5: 0.5: 2
2, ZnCl
2and FeCl
36H
2o, adding pH value is in the aqueous nitric acid of 2, and at temperature 85 DEG C, peptization refluxes 2 hours, and solution becomes light yellow suspension liquid from water white transparency, and reaction in 2 hours terminates, and solid-liquid layering after leaving standstill, true temp 50 DEG C of dryings 20 hours, obtain isabelline Mn
2+-Zn
2+modify FeOOH powder;
B, by 30gL
-1shewanella putrefaciens MR-1 is in liquid pancreas peptone soybean broth culture medium culturing, and obtaining cell concn is 2.3 × 10
8cells/ml
-1, under temperature 5 DEG C of freezing conditions centrifugal go out Shewanella putrefaciens MR-1 bacterial classification, it is (NH that Shewanella putrefaciens MR-1 bacterial classification is joined Mineralized Culture base
4)
2sO
49.0mM, K
2hPO
45.7mM, KH
2pO
43.3mM, NaHCO
32.0mM, MgSO
47H
2o 1.01mM, CaCl
22H
2o0.485mM, Sytron 67.2 μMs, H
3bO
356.6 μMs, NaCl 10.0 μMs, FeSO
47H
2o 5.4 μMs, CoSO
45.0 μMs, Ni (NH
4)
2(SO
4)
25.0 μMs, Na
2moO
43.87 μMs, Na
2seO
41.5 μMs, MnSO
41.26 μMs, ZnSO
41.04 μMs, CuSO
40.2 μM, arginase 12 0mgL
-1, L-glutamic acid 20mgL
-1with Serine 20mgL
-1in, the FeOOH powder then adding the modification obtained by step a is mixed with the Mn that concentration is 90mM
2+-Zn
2+modify FeOOH solution, adjust ph is 7, and adds Isosorbide-5-Nitrae-piperazine two ethyl sulfonic acid (PIPES) and anthraquinone 2,6-disulfonate (AQDS) simultaneously, alleviates the contact of cell and FeOOH solution, accelerates Fe
3+reduction reaction;
C, by reaction solution anaerobic sealing of step b, keep in Dark Place 45 days under temperature 30 DEG C of conditions, reaction-ure surface color becomes tawny suspension liquid from khaki color powder, Red-brown powder is obtained after reaction terminates, centrifugal, true temp 70 DEG C of dryings 48 hours, obtain (Mn-Zn) Fe
2o
4-Fe
2o
3heterojunction, the rate of recovery is 94.28%.
Embodiment 3
A, be Ni in molar ratio
2+: Zn
2+: Fe
3+take raw material NiCl at=0.5: 0.5: 2
2, ZnCl
2and FeCl
36H
2o, adding pH value is in the aqueous nitric acid of 2, and temperature 85 DEG C backflow 2 hours, solution became oyster suspension liquid from water white transparency, and solid-liquid layering after leaving standstill, true temp 50 DEG C of dryings 20 hours, obtain light yellow Ni
2+-Zn
2+modify FeOOH powder;
By 30gL
-1shewanella putrefaciens MR-1 is in liquid pancreas peptone soybean broth culture medium culturing, and obtaining cell concn is 2.3 × 10
8cells/ml
-1, under temperature 5 DEG C of freezing conditions centrifugal go out Shewanella putrefaciens MR-1 bacterial classification, it is (NH that Shewanella putrefaciens MR-1 bacterial classification is joined Mineralized Culture base
4)
2sO
49.0mM, K
2hPO
45.7mM, KH
2pO
43.3mM, NaHCO
32.0mM, MgSO
47H
2o 1.01mM, CaCl
22H
2o0.485mM, Sytron 67.2 μMs, H
3bO
356.6 μMs, NaCl 10.0 μMs, FeSO
47H
2o 5.4 μMs, CoSO
45.0 μMs, Ni (NH
4)
2(SO
4)
25.0 μMs, Na
2moO
43.87 μMs, Na
2seO
41.5 μMs, MnSO
41.26 μMs, ZnSO
41.04 μMs, CuSO
40.2 μM, arginase 12 0mgL
-1, L-glutamic acid 20mgL
-1with Serine 20mgL
-1in, the FeOOH powder then adding the modification obtained by step a is mixed with the Ni that concentration is 90mM
2+-Zn
2+modify FeOOH solution, adjust ph is 6, and adds Isosorbide-5-Nitrae-piperazine two ethyl sulfonic acid (PIPES) and anthraquinone 2,6-disulfonate (AQDS) simultaneously, alleviates the contact of cell and FeOOH solution, accelerates Fe
3+reduction reaction;
C, by reaction solution anaerobic sealing of step b, keep in Dark Place 45 days under temperature 30 DEG C of conditions, reaction-ure surface color becomes yellow-green colour suspension liquid from khaki color powder, chocolate powder is obtained after reaction terminates, centrifugal, true temp 70 DEG C of dryings 48 hours, obtain (Ni-Zn) Fe
2o
4-Fe
2o
3heterojunction, the rate of recovery is 87.14%.
Claims (2)
1. prepare the biological method that p-ferrite modifies n-rhombohedral iron ore heterojunction structure, it is characterized in that the method utilizes Shewanella putrefaciens MR-1 to prepare p-ferrite and modifies n-rhombohedral iron ore heterojunction structure, concrete operations follow these steps to carry out:
A, by raw material MgCl
2, MnCl
2or NiCl
2with ZnCl
2and FeCl
36H
2o is Mg in molar ratio
2+, Mn
2+or Ni
2+: Zn
2+: Fe
3+=0.5: 0.5: 2, adding pH value is in the aqueous nitric acid of 2, and temperature 85 DEG C backflow 2 hours, leave standstill, true temp 50 DEG C of dryings 20 hours, obtained Mg
2+, Mn
2+or Ni
2+, and Zn
2+the FeOOH powder modified;
B, by 30gL
-1shewanella putrefaciens MR-1 is in liquid pancreas peptone soybean broth culture medium culturing, and obtaining cell concn is 2.3 × 10
8cells/ml
-1, under temperature 5 DEG C of freezing conditions centrifugal go out Shewanella putrefaciens MR-1 bacterial classification, then join in Mineralized Culture base by Shewanella putrefaciens MR-1 bacterial classification, the FeOOH powder then adding the modification obtained by step a is mixed with the Mg that concentration is 90 mM
2+, Mn
2+or Ni
2+, and Zn
2+the FeOOH solution modified, regulator solution pH value is 6-8, and adds Isosorbide-5-Nitrae-piperazine two ethyl sulfonic acid and anthraquinone 2,6-disulfonate simultaneously, alleviates the contact of cell and FeOOH solution, accelerates Fe
3+reduction reaction;
C, by reaction solution anaerobic sealing of step b, keep in Dark Place 45 days under temperature 30 DEG C of conditions, centrifugal, true temp 70 DEG C of dryings 48 hours, obtain p-ferrite and modify n-rhombohedral iron ore heterojunction structure.
2. method according to claim 1, is characterized in that the Mineralized Culture base component in step b is (NH
4)
2sO
49.0 mM, K
2hPO
45.7 mM, KH
2pO
43.3 mM, NaHCO
32.0 mM, MgSO
47H
2o 1.01 mM, CaCl
22H
2o 0.485 mM, Sytron 67.2 μMs, H
3bO
356.6 μMs, NaCl 10.0 μMs, FeSO
47H
2o 5.4 μMs, CoSO
45.0 μMs, Ni (NH
4)
2(SO
4)
25.0 μMs, Na
2moO
43.87 μMs, Na
2seO
41.5 μMs, MnSO
41.26 μMs, ZnSO
41.04 μMs, CuSO
40.2 μM, arginase 12 0 mgL
1, L-glutamic acid 20 mgL
1with Serine 20 mgL
1.
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CN201410805812.3A CN104450790B (en) | 2014-12-22 | 2014-12-22 | It is a kind of to prepare the biological method that p ferrites modify n bloodstone heterojunction structures |
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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 |
---|
陈洁等: ""奥奈达希瓦氏菌MR-1的Fe(Ⅲ)还原特性及其影响因素"", 《安徽农业大学学报》 * |
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