CN104450790A - Biological method of preparing p-ferrite-modified n-hematite heterostructure - Google Patents

Biological method of preparing p-ferrite-modified n-hematite heterostructure Download PDF

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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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ferrite
feooh
shewanella putrefaciens
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CN104450790B (en
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边亮
徐金宝
董海良
董发勤
宋绵新
侯文平
李海龙
王磊
常爱民
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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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

A kind of biological method preparing p-ferrite modification n-rhombohedral iron ore heterojunction structure
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.
CN201410805812.3A 2014-12-22 2014-12-22 It is a kind of to prepare the biological method that p ferrites modify n bloodstone heterojunction structures Expired - Fee Related CN104450790B (en)

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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
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