CN104480019A - Preparation method of aspergillus niger-loaded gold nanometer granular composite material for dye degradation - Google Patents

Preparation method of aspergillus niger-loaded gold nanometer granular composite material for dye degradation Download PDF

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CN104480019A
CN104480019A CN201410587082.4A CN201410587082A CN104480019A CN 104480019 A CN104480019 A CN 104480019A CN 201410587082 A CN201410587082 A CN 201410587082A CN 104480019 A CN104480019 A CN 104480019A
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aspergillus niger
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CN104480019B (en
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李清彪
张金丽
孙道华
王海涛
何宁
王远鹏
郑艳梅
黄加乐
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Xiamen University
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used

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Abstract

The invention discloses a preparation method of an aspergillus niger-loaded gold nanometer granular composite material for dye degradation and relates to the thallus-loaded gold nanometer granular composite material. The aspergillus niger XM1 has a preservation center registration number of CGMCC No.9771. The preparation method comprises the following steps of 1, culturing aspergillus niger and preparing aspergillus niger powder, 2, preparing a chloroauric acid aqueous solution, and 3, mixing the aspergillus niger powder obtained by the step 1 and the chloroauric acid aqueous solution obtained by the step 2 for reaction, and then carrying out pumping filtration, washing and drying to obtain the aspergillus niger-loaded gold nanometer granular composite material for dye degradation. The aspergillus niger-loaded gold nanometer granular composite material for dye degradation contains an Au<0> simple substance and partly reduced and unreduced gold oxides, and has Au <delta +> oxide content more than 50%. The preparation method has simple and environmentally friendly processes and can be widely used for catalytic reduction degradation of organic waste water such as dye.

Description

For the preparation of the aspergillus niger load gold nano grain matrix material of dye degrades
Technical field
The present invention relates to a kind of thalline load gold nano grain matrix material, especially relate to and in-situ reducing can form the preparation of supported gold nanoparticles for the aspergillus niger load gold nano grain matrix material of dye degrades.
Background technology
Waste water from dyestuff comprises waste water in dye production and dyeing waste water.Waste water from dyestuff due to complicated component, toxicity is large, colourity is dark, organism and the feature such as inorganic salt concentration is high, biodegradability is poor, is the difficult point of wastewater treatment always.Research shows, chemical catalysis reduction pretreatment can not only significantly improve the biodegradability of waste water from dyestuff, and there is no sludge disposal problem, associating chemical reduction and bio-oxidation are a kind of cost-effective dye wastewater treatment novel method (Ghoreishi S M, et al.Chemical catalytic reactionand biological oxidation for treatment of non-biodegradable textile effluent [J] .ChemicalEngineering Journal, 2003,95 (1-3): 163-169).Metal nanoparticle, particularly gold nano grain have excellent dyestuff catalytic reduction performance, but due to colloidal gold nano particle instability, are easy to reunite and can not reclaim and recycle, and therefore supported gold nanoparticles causes people's great attention.At present, utilize gold nano grain (the 1.Chen L of mesoporous silicon material load, et al.Gold nanoparticles intercalated into the walls of mesoporous silica as a versatile redoxcatalyst [J] .Industrial & Engineering Chemistry Research, 2011,50 (24): 13642-13649.2.Azad U, et al.Catalytic reduction of organic dyes at gold nanoparticles impregnated silica materials:influence of functional groups and surfactants [J] .Journal of Nanoparticle Research, 2011,13 (9): 3951-3959) and the gold nano grain of macropore vinylbenzene and divinylbenzene copolymer load (Feral-Martin C, et al.Integrative chemistry toward the first spontaneous generation of gold nanoparticles withinmacrocellular polyHIPE supports (Au@polyHIPE) and their application to eosin reduction [J] .Reactive & Functional Polymers, 2007,67 (10): 1072-1082) report is seen in the catalytic reduction performance research of dyestuff.The gold nano grain of above-mentioned mesoporous silicon material load utilizes high-temperature roasting or additional reducing agent (NaBH 4) reduction is obtained, and lacks adsorption group due to silicon materials self, needs to introduce other organic groups as intermediate link silicon materials and gold nano grain, its preparation and modulation process complexity, do not meet the requirement of environmental protection; Although macroporous polymer carrier spontaneous reduction can form gold nano grain, the performance improving this Polymer-supported Au catalyst needs to adopt " comprehensive chemistry " means, and regulation process is very complicated, and universality is not strong.
In recent years, utilize microbiological process to obtain the catalytic reduction performance of thalline load gold nano grain to organic pollutant p-NP and be also seen in report.Narayanan etc. utilize broom to obstruct post spore bacterium (C.floridanum) viable bacteria body absorbing and reducing [AuCl 4] –the obtained gold nano grain be mainly distributed in born of the same parents, the gold nano grain of this broom stalk post spore bacterium load is converted in p-aminophenol at p-NP and demonstrates good catalytic activity (Narayanan K B et al.Synthesis and characterization ofnano-gold composite using Cylindrocladium floridanum and its heterogeneous catalysis in thedegradation of 4-nitrophenol [J] .Journal of Hazardous Materials, 2011, 189 (1 – 2): 519-525).Lin Liqin etc. utilize Pichia yeast (P.pastoris) dry mycelium absorbing and reducing [AuCl 4] –the obtained gold nano grain being distributed in phage surface, the reduction of gold nano grain to p-NP of this Pichia yeast load has higher catalytic activity, its reaction rate constant exceeds (Lin L more than 20 times than the gold nano grain of above-mentioned broom stalk post spore bacterium load, et al.Catalytic gold nanoparticlesimmobilized on yeast:From biosorption to bioreduction [J] .Chemical Engineering Journal, 2013,225,857-864).Research shows, in reducing dyes process, " still at the particle of growth " " the full-grown particle " more obtained than pre-reduction formed by metal ion in-situ reducing has higher catalytic activity (Pradhan N., Pal A., Pal T.Silvernanoparticle catalyzed reduction of aromatic nitro compounds [J] .Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2002,196 (2 – 3): 247-257).Therefore, if the in-situ reducing that can realize loading type (immobilization) gold nano grain is formed, will greatly improve the catalytic activity of gold nano grain, and provide a kind of new way to the preparation of dyestuff catalytic reduction gold nano grain.
Aspergillus niger (Aspergillus niger) is as a kind of fungal material of industrial widespread use, and the reduction of its viable bacteria body, viable bacteria body vat liquor and yeast culture supernatant liquor is prepared gold nano-material and has been seen in a small amount of report.(the Bhambure R such as Bhambure, et al.Extracellular biosynthesis of gold nanoparticles using Aspergillus niger-its Characterization andStability [J] .Chemical Engineering & Technology, 2009,32 (7): 1036-1041) utilize aspergillus strain culture supernatant to reduce and obtained the gold nano grain that mean particle size is 12.79nm, and find that this gold nano grain has high stability in the solution.(the Xie J such as Xie, et al.High-yield synthesis of complex gold nanostructures in a fungalsystem [J] .Journal of Physical Chemistry C, 2007, 111 (45): 16858-16865) aspergillus niger viable bacteria body is utilized respectively, gold nano grain has been prepared in yeast culture supernatant liquor and the reduction of thalline vat liquor, found that, aspergillus niger can synthesize the triangle sheet gold nano grain of spherical Sum fanction in born of the same parents, yeast culture supernatant liquor can synthesize the triangle of rule, truncation trigonometric sum hexagonal plate gold nano grain, and thalline vat liquor can synthesize the gold nano grain of the complex constructions such as sheet that spiral.But the research of noble metal nanometer material and application aspect thereof is prepared in the reduction of aspergillus niger dry mycelium, and there is not been reported so far.
Summary of the invention
The first object of the present invention aims to provide a kind of aspergillus niger (Aspergillus niger) XM1.
The second object of the present invention aims to provide and can form stable loading type (immobilization) gold nano grain in the reduction of reducing dyes process situ, thus has the preparation of the aspergillus niger load gold nano grain matrix material for dye degrades of very high catalytic activity and stability.
Described aspergillus niger (Aspergillus niger) XM1, be preserved in China Committee for Culture Collection of Microorganisms's common micro-organisms center on October 14th, 2014, preservation centre address: No. 3, Yard 1, BeiChen xi Road, Chaoyang District, Beijing City Institute of Microorganism, Academia Sinica, postcode 100101, registers on the books and is numbered CGMCC No.9771 in preservation center.
The preparation method of the described aspergillus niger load gold nano grain matrix material for dye degrades, comprises the following steps:
1) cultivation of aspergillus niger and the preparation of black-koji mould powder;
2) aqueous solution of chloraurate is prepared;
3) by step 1) the black-koji mould powder and the step 2 that obtain) aqueous solution of chloraurate prepared mixes, through suction filtration, washing, the dry aspergillus niger load gold nano grain matrix material that must be used for dye degrades after reaction.
In step 1) in, described aspergillus niger is aspergillus niger (Aspergillus niger) XM1, method prepared by the cultivation of aspergillus niger and bacterium powder can be: be transferred to by aspergillus niger strain on plate culture medium and cultivate, the flat board of spore is had to make monospore suspension with aseptic water washing is long again, and be inoculated in continuation cultivation in liquid nutrient medium, obtain seed liquor, get seed liquor and be inoculated in enlarged culturing in liquid nutrient medium, then filter, mycelium pellet washing post-drying, then grind the black-koji mould powder that sieves to obtain; Described plate culture medium can adopt PDA substratum, and the composition of plate culture medium can be: potato 200g/L, sucrose 20g/L, agar 15 ~ 20g/L, natural ph; Described being transferred on plate culture medium by aspergillus niger strain is cultivated, and the aspergillus niger strain that 4 DEG C are preserved can be transferred on plate culture medium and cultivate 4 ~ 7d in 30 DEG C; The spore concentration of described monospore suspension can be 10 6individual/mL; Described being inoculated in liquid nutrient medium continues to cultivate, and can continue to cultivate 24h under 30 DEG C of 170r/min; The composition of described liquid nutrient medium can be: sucrose 30.0g/L, SODIUMNITRATE 3.0g/L, dipotassium hydrogen phosphate 1.0g/L, Repone K 0.5g/L, magnesium sulfate 0.5g/L, ferrous sulfate 0.01g/L, natural ph; The inoculum size of described inoculation can be inoculated by liquid nutrient medium 5% by mass percentage; Described enlarged culturing can under 30 DEG C of 170r/min enlarged culturing 48h; The available deionized water washing by soaking of described washing 3 ~ 4 times; The condition of described oven dry can dry 48 ~ 60h in 50 ~ 60 DEG C; Described grinding is sieved and can be crossed 100 orders (150 μm) sieve.
In step 2) in, the volumetric molar concentration of described aqueous solution of chloraurate can be 0.06 ~ 1.44mmol/L, and the pH value of described aqueous solution of chloraurate can be 3 ~ 9.
In step 3) in, described black-koji mould powder mixes with aqueous solution of chloraurate, can adopt and add 0.1 ~ 0.6g black-koji mould powder in 100mL aqueous solution of chloraurate; The temperature of described reaction can be 20 ~ 60 DEG C, and the time of reaction can be 6 ~ 72h; Described washing, can adopt deionized water wash; Described drying can adopt 50 ~ 60 DEG C of vacuum-dryings.
Existing elemental Au in aspergillus niger load gold nano grain matrix material prepared by the present invention 0species, the oxidation state gold Au having again part to be reduced and not to be reduced δ+(Au +and Au 3+) species.By mass percentage, can be 0.6% ~ 11.9%, wherein Au for the content of gold in the aspergillus niger load gold nano grain matrix material of dye degrades δ+content account for more than 50% of total gold.
The present invention utilizes in aspergillus niger dry mycelium absorbing and reducing hydrochloro-auric acid process makes gold ion not be completely reduced due to the bonding stabilization of biomass, the overwhelming majority with oxidation state (Au +and Au 3+) characteristic that exists of form, obtained aspergillus niger load gold nano grain matrix material.In reducing dyes process, this oxidation state gold at phage surface secure bond can be formed loading type (immobilization) gold nano grain by strong reductant in-situ reducing such as sodium borohydrides and play katalysis, thus has very high catalytic activity.Its preparation technology of the present invention is simple, process environmental protection, can be widely used in the catalytic reduction degraded of the organic waste waters such as dyestuff.
Accompanying drawing explanation
The 4f XPS spectrum figure of Au element in the aspergillus strain load gold nano grain matrix material of Fig. 1 prepared by embodiment.In FIG, X-coordinate is electron binding energy B.E. (ev), and ordinate zou is the strong intensity in peak (a.u.).Au4f in Fig. 1 7/2spectrum peak divides electron binding energy and is respectively 83.9eV, 84.5eV, 85.3eV 3 peaks, corresponds respectively to Au 0, Au +and Au 3+species.Aspergillus strain existing elemental Au is on the surface described 0species, the oxidation state gold Au having again part to be reduced and not to be reduced δ+(Au +and Au 3+) species.According to the peak area of XPS spectrum figure, Au δ+(Au +and Au 3+) percentage composition that accounts for total gold is greater than 50%.
Fig. 2 be before and after reduction treatment aspergillus niger load gold nano grain matrix material to cationic red GTL catalytic reduction performance comparison diagram.In fig. 2, X-coordinate is time time (s), and ordinate zou is absorb light intensity A bs.
Embodiment
Following examples will the present invention will be further described by reference to the accompanying drawings.
Embodiment 1
The cultivation of aspergillus niger and the preparation of bacterium powder: the aspergillus niger strain that 4 DEG C are preserved is transferred on fresh PDA plate culture medium and cultivates 4d in 30 DEG C, afterwards, there is the flat board of spore to make the monospore suspension of certain turbidity with aseptic water washing is long, and be inoculated in liquid nutrient medium that (spore concentration reaches 10 6individual/mL) under 30 DEG C of 170r/min, cultivate 24h obtain seed liquor, get seed liquor, enlarged culturing 48h under 30 DEG C of 170r/min is inoculated in fresh liquid substratum by 5% inoculum size, then filter, in 60 DEG C of baking ovens, dry 48h after mycelium pellet ionized water washing by soaking 3 times, cross 100 orders (150 μm) after grinding and sieve to obtain black-koji mould powder.
The preparation of aspergillus niger load gold nano grain matrix material: preparation 100mL concentration is the aqueous solution of chloraurate of 0.48mM, and regulate its pH value to be 5.0 by the NaOH solution of 0.1mol/L, airtight, lucifuge vibration 10min under 30 DEG C of 150r/min, afterwards, adds 0.2g black-koji mould bacterium powder and continues airtight lucifuge vibration 72h, then suction filtration is carried out, filter cake, with after deionized water wash 3 times, moves to dry 48h in 50 DEG C of vacuum drying ovens, obtains aspergillus strain load gold nano grain matrix material.In aspergillus strain load gold nano grain matrix material, Au4f XPS spectrum figure is see Fig. 1.
Dyestuff catalytic reduction reaction carries out in a standard quartz cuvette (light path 1cm, capacity 3.5mL), adds deionized water, cationic red GTL solution and NaBH successively in cuvette 4solution, with the mixing of liquid-transfering gun pressure-vaccum, then add 0.3mL aspergillus niger load gold nano grain aqueous nancomposite scattered in advance and to fall apart liquid (m/V=10mg/30mL), controlling reaction solution cumulative volume is 3mL, and dye strength is 2 × 10 – 5mol/L, dyestuff and NaBH 4amount of substance ratio is 1: 100, with the rapid pressure-vaccum mixing of liquid-transfering gun, and with manual time-keeping, measures its absorbancy over time with ultraviolet spectrophotometer in dyestuff maximum absorption wave strong point, measures once every 20s.Catalyzed reaction result shows, cationic red GTL rapidly reduction reaction occurs and be completely reduced decolouring in 100s.
Embodiment 2
The preparation of aspergillus niger load gold nano grain matrix material is with embodiment 1.
Dyestuff is methylene blue, and dyestuff catalytic reduction reaction condition is with embodiment 1.Catalyzed reaction result shows, methylene blue rapidly reduction reaction occurs and be completely reduced decolouring in 120s.
Embodiment 3
The preparation of aspergillus niger load gold nano grain matrix material is with embodiment 1.
Dyestuff is eosin, and dyestuff catalytic reduction reaction condition is with embodiment 1.Catalyzed reaction result shows, eosin is carried out being swift in response after an inductive phase, and in 18min complete reaction.
Embodiment 4
The preparation of aspergillus niger load gold nano grain matrix material is with embodiment 1.
Dyestuff is tropeolin-D, and dyestuff catalytic reduction reaction condition is with embodiment 1.Catalyzed reaction result shows, tropeolin-D is carried out being swift in response after an inductive phase, and in 20min complete reaction.
Embodiment 5
The preparation of aspergillus niger load gold nano grain matrix material is with embodiment 1.
Dyestuff is Congo red, and dyestuff catalytic reduction reaction condition is with embodiment 1.Catalyzed reaction result shows, Congo redly carries out being swift in response after an inductive phase, and in 14min complete reaction.
Embodiment 6
The preparation of aspergillus niger load gold nano grain matrix material is with embodiment 1.
Dyestuff is azophloxine, and dyestuff catalytic reduction reaction condition is with embodiment 1.Catalyzed reaction result shows, azophloxine carries out being swift in response after an inductive phase, and in 14min complete reaction.
Embodiment 7
Preparation 100mL concentration is the aqueous solution of chloraurate of 0.48mM, regulates its pH value to be 3.0, then prepare aspergillus niger load gold nano grain matrix material according to the method identical with embodiment 1 with the HCl solution of 0.1mol/L.
Dyestuff is cationic red GTL, and dyestuff starting point concentration is 6 × 10 – 5mol/L, aspergillus niger load gold nano grain aqueous nancomposite scattered in advance falls apart, and to add volume be 0.5mL to liquid (m/V=10mg/30mL), other catalytic reaction conditions are with embodiment 1, and catalyzed reaction result shows, cationic red GTL is completely reduced decolouring in 300s.
Embodiment 8
Preparation 100mL concentration is the aqueous solution of chloraurate of 0.12mM, regulates its pH value to be 9.0, then prepare aspergillus niger load gold nano grain matrix material according to the method identical with embodiment 1 by the NaOH solution of 0.1mol/L.
Dyestuff is cationic red GTL, and its catalytic reaction condition is with embodiment 7, and catalyzed reaction result shows, cationic red GTL is completely reduced decolouring in 200s.
Embodiment 9
Preparation 100mL concentration is the aqueous solution of chloraurate of 0.12mM, regulates its pH value to be 5.0, at 20 DEG C, prepare aspergillus niger load gold nano grain matrix material according to the method identical with embodiment 9 by the NaOH solution of 0.1mol/L.
Dyestuff is cationic red GTL, and its catalytic reaction condition is with embodiment 7, and catalyzed reaction result shows, cationic red GTL is completely reduced decolouring in 220s.
Embodiment 10
Preparation 100mL concentration is the aqueous solution of chloraurate of 1.44mM, regulates its pH value to be 5.0, then prepare aspergillus niger load gold nano grain matrix material according to the method identical with embodiment 1 by the NaOH solution of 0.1mol/L.
Dyestuff is cationic red GTL, and its catalytic reaction condition is with embodiment 7, and catalyzed reaction result shows, cationic red GTL is completely reduced decolouring in 200s.
Embodiment 11
Preparation 100mL concentration is the aqueous solution of chloraurate of 0.06mM, regulates its pH value to be 5.0, then react 6h according to the method identical with embodiment 1 and obtain aspergillus niger load gold nano grain matrix material by the NaOH solution of 0.1mol/L.
Dyestuff is cationic red GTL, and its catalytic reaction condition is with embodiment 7, and catalyzed reaction result shows, cationic red GTL is completely reduced decolouring in 260s.
Embodiment 12
Preparation 100mL concentration is the aqueous solution of chloraurate of 0.50mM, regulates its pH value to be 5.0, then adds 0.6g black-koji mould powder, react 24h obtain aspergillus niger load gold nano grain matrix material according to the method identical with embodiment 1 by the NaOH solution of 0.1mol/L.
Dyestuff is cationic red GTL, and its catalytic reaction condition is with embodiment 7, and catalyzed reaction result shows, cationic red GTL is completely reduced decolouring in 160s.
Embodiment 13
Preparation 100mL concentration is the aqueous solution of chloraurate of 0.48mM, its pH value is regulated to be 5.0 by the NaOH solution of 0.1mol/L, lucifuge vibration 10min under 60 DEG C of 150r/min, afterwards, add 0.2g black-koji mould bacterium powder and continue airtight lucifuge vibration 24h, then carry out suction filtration, filter cake is with after deionized water wash 3 times, move to dry 48h in 50 DEG C of vacuum drying ovens, obtain aspergillus niger load gold nano grain matrix material.
Dyestuff is cationic red GTL, and its catalytic reaction condition is with embodiment 1, and catalyzed reaction result shows, cationic red GTL is completely reduced decolouring in 280s.
Comparative example 1
Adopt the NaBH of 5mmol/L (10 times to gold ion concentration) respectively 4obtain aspergillus niger load gold nano grain matrix material and carry out reduction treatment above-mentioned through reaction 24h with Vc, matrix material is after drying for catalyzed reaction, the catalytic activity of reducing to cationic red GTL with (see embodiment 13) matrix material before reduction treatment compares (see Fig. 2), result shows, through strong reductant NaBH 4after reduction treatment, the catalytic activity of matrix material obviously reduces, and the time lengthening of cationic red GTL complete reaction is to 600s, and the catalytic activity impact of weak reductant Vc on matrix material is little, and the time of cationic red GTL complete reaction is 300s.
The invention provides a kind of preparation method utilizing the combined adsorption and entrapment preparation energy in-situ reducing of black-koji mould to hydrochloro-auric acid to form the aspergillus niger load gold nano grain matrix material of stable loading type (immobilization) gold nano grain.Existing elemental Au in described aspergillus niger load gold nano grain matrix material 0species, the oxidation state gold Au having again part to be reduced and not to be reduced δ+(Au +and Au 3+) species, and oxidation state gold Au δ+account for more than 50% of total gold.During preparation, black-koji mould powder is mixed with aqueous solution of chloraurate, at 20 ~ 60 DEG C, react the gold nano grain matrix material through suction filtration, washing, dry aspergillus niger load after 6 ~ 72h.Aspergillus niger load gold nano grain matrix material of the present invention has high catalytic reduction performance to organic dye, and preparation technology is simple, process environmental protection, can be widely used in the catalytic reduction degraded of the organic waste waters such as dyestuff.

Claims (10)

1. aspergillus niger (Aspergillus niger) XM1, being preserved in China Committee for Culture Collection of Microorganisms's common micro-organisms center on October 14th, 2014, registers on the books and is numbered CGMCC No.9771 in preservation center.
2., for the preparation of the aspergillus niger load gold nano grain matrix material of dye degrades, it is characterized in that comprising the following steps:
1) cultivation of aspergillus niger and the preparation of black-koji mould powder;
2) aqueous solution of chloraurate is prepared;
3) by step 1) the black-koji mould powder and the step 2 that obtain) aqueous solution of chloraurate prepared mixes, through suction filtration, washing, the dry aspergillus niger load gold nano grain matrix material that must be used for dye degrades after reaction.
3., as claimed in claim 2 for the preparation of the aspergillus niger load gold nano grain matrix material of dye degrades, it is characterized in that in step 1) in, described aspergillus niger is aspergillus niger (Aspergillus niger) XM1; Method prepared by the cultivation of aspergillus niger and black-koji mould powder is: be transferred to by aspergillus niger strain on plate culture medium and cultivate, the flat board of spore is had to make monospore suspension with aseptic water washing is long again, and be inoculated in continuation cultivation in liquid nutrient medium, obtain seed liquor, get seed liquor and be inoculated in enlarged culturing in liquid nutrient medium, then filter, mycelium pellet washing post-drying, then grind the black-koji mould powder that sieves to obtain.
4. as claimed in claim 3 for the preparation of the aspergillus niger load gold nano grain matrix material of dye degrades, it is characterized in that described plate culture medium adopts PDA substratum, consisting of of plate culture medium: potato 200g/L, sucrose 20g/L, agar 15 ~ 20g/L, natural ph; Described being transferred on plate culture medium by aspergillus niger strain is cultivated, and the aspergillus niger strain that 4 DEG C are preserved can be transferred on plate culture medium and cultivate 4 ~ 7d in 30 DEG C.
5., as claimed in claim 3 for the preparation of the aspergillus niger load gold nano grain matrix material of dye degrades, it is characterized in that the spore concentration of described monospore suspension is 10 6individual/mL.
6. as claimed in claim 3 for the preparation of the aspergillus niger load gold nano grain matrix material of dye degrades, being inoculated in liquid nutrient medium and continuing to cultivate described in it is characterized in that, is continue to cultivate 24h under 30 DEG C of 170r/min; The composition of described liquid nutrient medium can be: sucrose 30.0g/L, SODIUMNITRATE 3.0g/L, dipotassium hydrogen phosphate 1.0g/L, Repone K 0.5g/L, magnesium sulfate 0.5g/L, ferrous sulfate 0.01g/L, natural ph; The inoculum size of described inoculation can be inoculated by liquid nutrient medium 5% by mass percentage.
7., as claimed in claim 3 for the preparation of the aspergillus niger load gold nano grain matrix material of dye degrades, it is characterized in that described enlarged culturing is enlarged culturing 48h under 30 DEG C of 170r/min; The available deionized water washing by soaking of described washing 3 ~ 4 times.
8., as claimed in claim 3 for the preparation of the aspergillus niger load gold nano grain matrix material of dye degrades, it is characterized in that the condition of described oven dry dries 48 ~ 60h in 50 ~ 60 DEG C; Described grinding is sieved and can be crossed 100 mesh sieves.
9. as claimed in claim 2 for the preparation of the aspergillus niger load gold nano grain matrix material of dye degrades, it is characterized in that in step 2) in, the volumetric molar concentration of described aqueous solution of chloraurate is 0.06 ~ 1.44mmol/L, and the pH value of described aqueous solution of chloraurate is 3 ~ 9.
10. as claimed in claim 2 for the preparation of the aspergillus niger load gold nano grain matrix material of dye degrades, it is characterized in that in step 3) in, described black-koji mould powder mixes with aqueous solution of chloraurate, is to adopt in 100mL aqueous solution of chloraurate, add 0.1 ~ 0.6g black-koji mould powder; The temperature of described reaction can be 20 ~ 60 DEG C, and the time of reaction can be 6 ~ 72h; Described washing, can adopt deionized water wash; Described drying can adopt 50 ~ 60 DEG C of vacuum-dryings.
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CN108499542A (en) * 2018-05-03 2018-09-07 石狮纳通新材料科技有限公司 A kind of composite material and preparation method based on egg shell of efficient process environmental wastewater

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