CN1687430A - Method for preparing nano metal sulfides - Google Patents

Method for preparing nano metal sulfides Download PDF

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Publication number
CN1687430A
CN1687430A CN 200510012417 CN200510012417A CN1687430A CN 1687430 A CN1687430 A CN 1687430A CN 200510012417 CN200510012417 CN 200510012417 CN 200510012417 A CN200510012417 A CN 200510012417A CN 1687430 A CN1687430 A CN 1687430A
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nano metal
preparation
rhodopseudomonas
metal sulphide
nano
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CN1298858C (en
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白红娟
张肇铭
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Shanxi University
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Shanxi University
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Abstract

A method of preparing nano-metal sulfide by microorganism, it comprises the steps of: it adapts the photosynthetic bacterium as the inoculants, which is fixed and activated; we put metal salts into substrate, then antisepticises, inoculates the bacterium, incubated at room temperature, illumination, culture condition for 12-72 hours; after ageing, we remove the supernatant, fluid, wash and dry the product, and then obtains the nano-metal sulfide. The products particulate is quite small, distributing is symmetrical, and has a high purity. It is prone to control the reaction with no pollution in the process, and low cost, and is prone to industrialization.

Description

The preparation method of nano metal sulphide
Technical field
The present invention relates to a kind of technology of preparing of nano metal sulphide, specifically belong to the method that adopts microbial method to prepare nano metal sulphide.
Background technology
The nano metal sulphide semiconductor particle has aspect performances such as excellent light, electricity, magnetic, catalysis because of it has quantum size effect and surface effects etc., has broad application prospects in civilian industries such as electronics, biology, coating.Wherein Nano lead sulfide, zinc sulphide are the main infrared acquisition materials that present military infrared electro system adopts, and infra-red material is the basis of infrared electro Detection Techniques, and the guidance of various guided missiles, infrared early warning, observation aiming etc. all be unable to do without infrared detection technique.Therefore, in environmental pollution serious day by day today, for the semi-conductive preparation of nano metal sulphide, to realize that technology is simple, the product particle diameter is less, be evenly distributed, productive rate is higher and cleaning procedure that can produce in enormous quantities is significant to the development of above-mentioned industry.
At present, in the semi-conductive preparation method of nano metal sulphide, synthetic substantially reaction scheme has: element direct reaction, permutoid reaction, pyrolytic reaction.(1) the element direct reaction prepares binary metal sulfide, takes the mode of high temperature gas phase/solid state reaction usually, and the product particle diameter that obtains is bigger.The sulfur vapor of preparation process generation simultaneously makes product be difficult to keep its chemical measurementization.(2) synthetic method of permutoid reaction is will contain metal ion and S in reaction medium 2-Different compounds mix, finish ion-exchange, but adopt the bigger H of toxicity in the reaction 2S gas or Na 2S, (NH 4) 2S makes sulphur source, Na 2S, (NH 4) 2S is very unstable, and is easily oxidized, and preparation must be carried out under oxygen free condition, and needs to use the Na of new system 2S, (NH 4) 2S, in case gluey elemental sulfur and other by product produce, the potential of hydrogen that need control solution simultaneously when synthetic corresponding sulfide stops the precursor generation hydrolysis of facile hydrolysis, or makes in the organic solvents such as being reflected at ethyl acetate, tetrahydrofuran (THF) and carry out.(3) synthetic method of pyrolytic reaction is to utilize the precursor compound that contains the M-S key to decompose under comparatively high temps, synthetic metallic sulfide, and reaction needed high temperature, and the product that obtains is impure.
Summary of the invention
The preparation method of the nano metal sulphide that the purpose of this invention is to provide that a kind of production process is pollution-free, reaction conditions is easy to control, production cost is low, product purity is high.
The present invention adopts microorganism to prepare nano metal sulphide, and promptly in the liquid nutrient medium that is added with a certain amount of metal-salt and vitriol, by the inducing action of metal ion, vitriol generates metallic sulfide through the immobilized microorganism assimilation.Microorganism constantly is discharged to the metallic sulfide that generates in the liquid nutrient medium by the micropore of immobilized spherule.By the bacterial micro-organism reactor, make reaction continue to go on, finish up to reaction.In the conversion process of microorganism to heavy metal, the particle diameter by active bio thalline and conversion incubation time control product makes the metallic sulfide of generation reach nano level.
Production method of the present invention specifically comprises the steps:
(1) photosynthetic bacterium of access 1/2-1/30 umber in the substratum of the sulfur-bearing hydrochlorate that is fit to photosynthetic bacterium growth under room temperature, illumination, anaerobic condition, was cultivated 3-30 days, as the inoculation bacterial classification;
(2) the inoculation bacterial classification is carried out immobilization, then at substratum activation 10-72h;
(3) metal-salt with sterilization adds in the substratum, and the inoculation immobilized bacteria is transferred pH to 5-9, under room temperature, illumination, anaerobic condition, cultivates 12-72h;
(4) above-mentioned culture solution is separated, abandoning supernatant is collected product, with deionized water wash, drying, obtains nano metal sulphide.
Described photosynthetic bacterium can be any strain bacterium or their arbitrary combination in the following photosynthetic bacterium: rhodospirillum Rhodospirillium, as Crimson rhodospirillum (Rhodospirillium rubrum); Rhodopseudomonas Rhodopseudomonas, as: Rhodopseudomonas palustris (Rhodopseudomonas palustris), Green color rhodopseudomonas (Rhodopseudomonas viridis), rhodopseudononas sulfovirdis (Rhodopseudomonas sulfoviridis), Pseudomonas sp. (Rhodopseudomonas marina); Red bacterium belongs to Rodobacter, as: Spherical red antibacterial (Rhodobacter sphaeroides) etc.
The source of above-mentioned bacterial classification document: Yao Zhuyun, Zhang Zhaoming. phenotypic characteristic of a few strain photosynthetic bacteriums and DNA-DNA homology analysis thereof. use and the environmental organism journal 1996,2 (1): 84-89; Zhang Zhaoming, Yang Suping, Zhao Chungui. the isolation identification research of Rhodopseudomonas palustris. University Of Shanxi's journal (natural science edition), 1992, (4): 379-385; Yang Suping, Zhang Zhaoming, Zhao Chungui. separating and evaluation of Green color rhodopseudomonas and rhodopseudononas sulfovirdis. microorganism journal, 1995,35 (2): 91-96; Zhang Zhaoming, Deng Songlu, Zhao Liangqi, etc. the research of separation, evaluation and the physiological property of the research A. Rhodopseudomonas spheroides of Purple Non-sulfur photosynthetic bacterium. University Of Shanxi's journal (natural science edition), 1984, (4): 54-59.
These bacterial classifications come from Life Science and Technology institute of Shanxi province Taiyuan city University Of Shanxi photosynthetic bacterium research department.
The substratum of described suitable photosynthetic bacterium growth can adopt photosynthetic bacteria culture medium of the prior art, the preferred following substratum of the present invention.Its composition and proportioning are:
Sodium acetate 1000-2000mg CaCl 2.2H 2O 50-100mg
MgSO 4.7?H 2O 100-300mg EDTA 10-30mg
Yeast extract paste 500-1500mg K 2HPO 4500-1500mg
(NH 4) 2SO 4 1000-2000mg KH 2PO 4 400-1000mg
FeSO 4.7H 2O 5-15mg trace element solution 1-5ml
Deionized water 1000-2000ml
Wherein trace element solution consists of:
H 3BO 3 200-300mg Na 2MoO 4.2H 2O 50-100mg
CuSO 4 2-10mg MnSO 4.4H 2O 150-250mg
ZnSO 4.7H 2O 20-30mg deionized water 100-200ml
Medium pH is 5-9.
Described immobilized bacteria can be made bead, bulk or membranaceous; The immobilized reagent that is adopted can be any one or an arbitrary combination by a certain percentage in sodium alginate, polyvinyl alcohol, Polyurethane, agarose, silica gel, the cellulose acetate.
The ratio of described inoculation immobilized bacteria is: bacterial classification: substratum=1: (2～30) (substratum is at 120-150 ℃ of sterilization 10-60min).Described illumination condition is 1000-5000lux.The metallic element of described metal-salt can be nickel, cobalt, zinc, cadmium, molybdenum, iron, tin or lead; Described vitriol can be sulfuric acid amine, sodium sulfate or vitriolate of tartar.
The present invention has following advantage:
1. because the present invention utilizes a kind of photosynthetic bacterium (being called for short PSB) microorganism.It can utilize low molecule organic matter as photosynthetic electron acceptor(EA) under the anaerobism illumination condition, carries out the photoheterotrophy growth; Under dark aerobic condition, can utilize organism to carry out aerobic or heterotrophic growth as respiratory substrate; Can not put the photosynthesis of oxygen.The cultivation raw material sources of photosynthetic bacterium are wide, low price, and growth conditions is controlled easily, and thalline can recycle, therefore makes the present invention can one go on foot synthesis of nano metal sulfide semiconductor efficiently, and it is easily simple more that whole process of preparation becomes.
Since the present invention in the immobilization photosynthetic bacterium just as the active bio reactor, product had the good control effect, can and control crystal particle diameter by the synthetic metallic sulfide of endobacillary biological respinse, micropore that again can be by immobilized spherule is discharged to nutrient solution with product and reaches with thalline and separate, and entire reaction course is very even.And the product particle diameter that makes less, be evenly distributed, have good dispersiveness, and a purity height.Productive rate generally can reach more than 85%.
3. technology of the present invention is simple, and whole preparation system makes up easily, and easy and simple to handle, condition is controlled easily, and is with low cost, operation at room temperature, and particle diameter is controlled easily, suitability for mass industrialized production.Simultaneously, whole process of production does not have any pollution, meets the Sustainable development requirement.
Description of drawings
Fig. 1 is the X diffraction analysis of nano metal lead sulfide of the present invention.
Fig. 2 is the TEM (transmission electron microscope) analysis of nano metal lead sulfide of the present invention.
Fig. 3 is the X diffraction analysis of nano metal Cadmium Sulfide of the present invention.
Fig. 4 is the TEM (transmission electron microscope) analysis of nano metal Cadmium Sulfide of the present invention.
Fig. 5 is the X diffraction analysis of nano metal zinc sulphide of the present invention.
Fig. 6 is the TEM (transmission electron microscope) analysis of nano metal zinc sulphide of the present invention.
Embodiment
Embodiment 1:
Dispose substratum by following component: sodium acetate 1500mg; CaCl 2.2H 2O 80mg; MgSO 4.7H 2O 150mg; EDTA 20mg; Yeast extract paste 1200mg; K 2HPO 41000mg; (NH 4) 2SO 41500mg; KH 2PO 4800mg; FeSO 4.7H 2O 10mg; Trace element solution 3ml; Deionized water 1500ml.Medium pH is 7.
Wherein trace element solution consists of: H 3BO 3240mg; Na 2MoO 4.2H 2O 70mg; CuSO 47mg; MnSO 4.4H 2O 200mg; ZnSO 4.7H 2O 24mg; Deionized water 1650ml.
The spherical red bacillus (Rhodobacter sphaeroides) of in the substratum of sterilization, inserting 1/20 umber, under illumination 2500lux, room temperature, anaerobic condition, cultivated 20 days, as the inoculation bacterial classification;
With the red bacillus of cultured sphere centrifugal 10min under 6000rpm, with physiological saline washing precipitation also centrifugal 2 times.Then 10% of gained being concentrated thalline mixes with the polyvinyl alcohol solution that is cooled to 35 ℃ 10%, this mixture is splashed in the saturated boric acid solution of pH7 with syringe, form the bead about 3mm, the bead that forms is positioned in 4 ℃ of refrigerators solidifies 18h, with physiological saline washing 3 times, activation 6h makes immobilized bacteria in substratum then, and is standby.
Get above-mentioned substratum 1000ml, transfer pH to 7,121 ℃ of sterilization 30min.Pb (the NO that adds 0.25mol/L 3) a10ml (121 ℃ of sterilization 30min) and immobilized bacteria (pressing 10% inoculation) under illumination 2500lux, room temperature, after anaerobism is cultivated 24h, take out immobilized spherule, carry out conventional centrifugation, and abandoning supernatant stays product, uses deionized water wash 3-5 time., at last the product that obtains is merged attached to the product on the immobilized spherule with deionized water rinsing, place 50 ℃ oven drying 2 hours, promptly obtain nano metal lead sulfide.
X X-ray analysis X result is a cubic structure, and collection of illustrative plates does not have assorted peak and occurs, its purity height, as shown in Figure 1.Transmission electron microscope results as shown in Figure 2, particle size distribution is even, median size is 20nm.Productive rate 91%.
Embodiment 2
Adopt Rhodopseudomonas palustris (Rhodopseudomonaspalustris), add the Pb (AC) of 0.20mol/L a10ml transforms incubation time 36h, and other condition is identical with embodiment 1 with step, the product Nano lead sulfide median size 25nm that obtains, and productive rate 90%, the black powder shape, x X-ray analysis X result is a cubic structure, the purity height.
Embodiment 3
Rhodopseudomonas palustris (Rhodopseudomonas palustris) is mixed and immobilization by 1: 1 with spherical red bacillus (Rhodobactersphaeroides), transform incubation time 40h, other condition is identical with embodiment 1 with step, the product nanometer sulfuration median size 23nm that obtains, productive rate 89%, black powder shape, x X-ray analysis X are cubic structure, the purity height.
Embodiment 4
Adopt Green color rhodopseudomonas (Rhodopseudomonas viridis), add the CdCl of 0.15mol/L 2Solution 10ml transforms incubation time 48h, and other condition is identical with embodiment 1 with step, and the product Nano cadmium sulphide that obtains is a yellow powder, and x X-ray analysis X result is a cubic structure, and collection of illustrative plates does not have assorted peak and occurs, its purity height, as shown in Figure 3.Transmission electron microscope results as shown in Figure 4, particle size distribution is even, median size 35nm, productive rate 85%.
Embodiment 5
Adopt rhodopseudononas sulfovirdis (Rhodopseudomonas sulfoviridis), add the Cd (NO of 0.12mol/L 3) 2Solution 10ml transforms incubation time 70h, and other condition and step and embodiment 1 are identical, the product Nano cadmium sulphide median size 40nm that obtains, and productive rate 86%, the yellow powder shape, x X-ray analysis X result is a cubic structure, the purity height.
Embodiment 6
Green color rhodopseudomonas (Rhodopseudomonas viridis), rhodopseudononas sulfovirdis (Rhodopseudomonassulfoviridis) and spherical red bacillus (Rhodobacter sphaeroides) were mixed and immobilization by 1: 2: 1, add the CdCl of 0.15mol/L 2Solution 10ml transforms incubation time 45h, and other condition is identical with embodiment 1 with step, the product Nano cadmium sulphide median size 33nm that obtains, and productive rate 87%, the yellow powder shape, x X-ray analysis X result is a cubic structure, the purity height.
Embodiment 7
With Crimson rhodospirillum (Rhodospirillum rubrum), add the Zn (AC) of 0.28mol/L 2Solution 10ml transforms incubation time 28h, and other condition is identical with embodiment 1 with step, and the product nano-zinc sulfide that obtains is a white powder, and x X-ray analysis X result is a hexagonal structure, and collection of illustrative plates does not have assorted peak and occurs, its purity height, as shown in Figure 5.Transmission electron microscope results as shown in Figure 6, particle size distribution is even, median size 12nm, productive rate 88%.
Embodiment 8
With Pseudomonas sp. (Rhodopseudomonas marina), add the Zn (NO of 0.25mol/L 3) 2Solution 10ml transforms incubation time 40h, and other condition is identical with embodiment 1 with step, the product nano-zinc sulfide median size 25nm that obtains, and productive rate 86%, white powder, x X-ray analysis X result is a hexagonal structure, the purity height.
Embodiment 9
Crimson rhodospirillum (Rhodospirillum rubrum) is mixed and immobilization by 3: 2 with Pseudomonas sp. (Rhodopseudomonasmarina), add the ZnCl of 0.28mol/L 2Solution 10ml transforms incubation time 50h, and other condition is identical with embodiment 1 with step, the product nano-zinc sulfide median size 30nm that obtains, and productive rate 88%, white powder, x X-ray analysis X result is a hexagonal structure, the purity height.

Claims (4)

1. the preparation method of a nano metal sulphide is characterized in that comprising the steps:
(1) will be fit to the medium sterilization of the sulfur-bearing hydrochlorate of photosynthetic bacterium growth, insert the photosynthetic bacterium of 1/2-1/30 umber, under room temperature, illumination, anaerobic condition, cultivate 3-30 days, as inoculating bacterial classification;
(2) the inoculation bacterial classification is carried out immobilization, at substratum activation 10-72h, make immobilized bacteria then;
(3) metal-salt with sterilization adds in the substratum, and the inoculation immobilized bacteria is transferred pH to 5-9, under room temperature, illumination, anaerobic condition, cultivates 12-72h;
(4) above-mentioned culture solution is separated, abandoning supernatant is collected product, with deionized water wash, drying, obtains nano metal sulphide.
2. the preparation method of a kind of nano metal sulphide according to claim 1, the metallic element of described metal-salt is nickel, cobalt, zinc, cadmium, molybdenum, iron, tin or lead.
3. the preparation method of a kind of nano metal sulphide according to claim 1, described vitriol is sulfuric acid amine, sodium sulfate or vitriolate of tartar.
4. the preparation method of a kind of nano metal sulphide according to claim 1, described photosynthetic bacterium is rhodospirillum (Rhodosprillium), Rhodopseudomonas (Rhodopseudomonas), the hybrid bacterial strain of any strain or arbitrary combination in the red bacterium genus (Rodobacter).
CNB2005100124170A 2005-03-22 2005-03-22 Method for preparing nano metal sulfides Expired - Fee Related CN1298858C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104520432A (en) * 2012-03-30 2015-04-15 智利圣地亚哥大学 Use of botrytis cinerea for obtaining gold nanoparticles
CN113667698A (en) * 2021-09-07 2021-11-19 中国科学技术大学 Microbial self-synthesis cadmium sulfide semiconductor, preparation method thereof and method for enhancing and fixing carbon dioxide

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6783963B2 (en) * 2002-03-29 2004-08-31 Council Of Scientific & Industrial Research Process for the preparation of metal sulfide nanoparticles

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104520432A (en) * 2012-03-30 2015-04-15 智利圣地亚哥大学 Use of botrytis cinerea for obtaining gold nanoparticles
CN113667698A (en) * 2021-09-07 2021-11-19 中国科学技术大学 Microbial self-synthesis cadmium sulfide semiconductor, preparation method thereof and method for enhancing and fixing carbon dioxide

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