CN109019868A - A kind of application of load of microorganisms type platinum-nickel alloys nanocatalyst in p-nitrophenol or azo dyes catalytic degradation - Google Patents
A kind of application of load of microorganisms type platinum-nickel alloys nanocatalyst in p-nitrophenol or azo dyes catalytic degradation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
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Abstract
The invention discloses a kind of application of load of microorganisms type platinum-nickel alloys nanocatalyst in p-nitrophenol or azo dyes catalytic degradation, the method of the application includes the following steps: to mix containing the organic polluting water of p-nitrophenol or azo dyes with sodium borohydride solution, then load of microorganisms type platinum-nickel alloys nanocatalyst is added and carries out catalytic degradation reaction, the catalytic degradation of the organic polluting water is completed after fully reacting；The load of microorganisms type platinum-nickel alloys nanocatalyst has platinum-nickel alloys nano particle using microorganism as carrier, in the intracellular and/or extracellular load of microorganism.The catalyst activity that application of the invention uses is good, and thoroughly, degrading, the time used is short, and treatment effeciency is high for degradation.
Description
Technical field
The invention belongs to noble metal nano catalyst removal dyestuff contaminant field more particularly to a kind of load of microorganisms types
Application of the platinum-nickel alloys nanocatalyst in p-nitrophenol and azo dyes catalytic degradation.
Background technique
The waste water from dyestuff of the industries such as papermaking, leather, weaving, printing discharge has had resulted in serious environmental pollution, wherein
Azo dyes (azo dyes, azo group both ends connect a kind of organic compound of aryl) ratio shared in dyestuff is 50%
~70% or so, it is fabric clothing most widely used one kind synthetic dyestuffs in dyeing and printing process, for a variety of natural and conjunction
Dyeing and stamp at fiber, are also used for the coloring of paint, plastics, rubber etc..Under specific condition, it can decompose generation more than 20
Kind carcinogenic aromatic amine causes lesion by the DNA structure that activation changes human body and induces cancer.Azo dyes is current kind
A class most major class dyestuff contains azo group (- N=N-) in molecule, and chemical stability is high, has in water body anti-light anti-
Oxidability causes water ecosystem to be destroyed；In addition, azo dyes also has teratogenesis, carcinogenic, mutagenic " three cause "
Effect, seriously endangers the healthy and safe of human body.During production and application, there are about the dyestuff of 10%-15% is unprocessed
It is discharged into the health that goes and may seriously affect contactee in environment.Identical as azo dyes, p-nitrophenol is equally wide
It is general to be applied to dye industry, environment and human body are caused with serious harm similar therewith.Therefore, p-nitrophenol and azo dyes
Waste water must carry out harmless treatment before discharging.
Currently used physical absorption processing method only shifts pollutant, cannot achieve contaminant degradation, it is easy to
Cause secondary pollution；It is longer the time required to biodegradation method, it is unable to recycle, treatment effect is also undesirable.And utilizationization
Catalysis is short the time required to reacting degradation p-nitrophenol and azo dyes, degrades thoroughly, before increasingly having wide application
Scape and value.Therefore, the catalyst for seeking a kind of economy, efficient degradation p-nitrophenol and azo dyes, which becomes, prevents and treats its pollution
Problem can the road Xun Zhi.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Kind degradation time is short, degradation is efficiently thorough, the recyclable load of microorganisms type platinum-nickel alloys nanocatalyst reused is right
Application in nitrophenol or azo dyes catalytic degradation.
In order to solve the above technical problems, technical solution proposed by the present invention is to provide a kind of load of microorganisms type platinum-nickel alloys
Application of the nanocatalyst in azo dyes catalytic degradation, the method for the application includes the following steps: will be containing to nitro
The organic polluting water of phenol or azo dyes is mixed with sodium borohydride solution, and load of microorganisms type platinum-nickel alloys are then added and receive
Rice catalyst carries out catalytic degradation reaction, and the catalytic degradation of the organic polluting water is completed after fully reacting；The microorganism
Load type platinum palldium alloy nanocatalyst has platinum palladium using microorganism as carrier, in the intracellular and/or extracellular load of microorganism
Alloy nanoparticle.
Bimetallic composite nano materials are a kind of relatively dominant strategies for being effectively improved nanocatalyst performance, can integrate two
The excellent properties of kind metal have obviously to generate the strong effect of intercoupling, including three-dimensional effect and charge effect
The intrinsic performance of enhancing and many new kink characteristics.The platinum-nickel alloys duplex metal nano granule that the present invention uses, which can effectively enhance, to be received
The weak Lattice Contraction of the catalytic activity and stability of rice material, platinum and palladium can generate a small compression strain, while platinum and palladium
Between electric charge transfer occur form Pt-Pd key, to change the structure and activity between them, this strong work that intercouples
With make platinum-nickel alloys nano particle have more excellent catalytic performance.
Above-mentioned application, it is preferred that the microorganism that the load of microorganisms type platinum-nickel alloys nanocatalyst uses is uncommon
Waksmania (Shewanella), the partial size of the platinum-nickel alloys nano particle are 3~40nm, the load of microorganisms type platinum palladium
The mass ratio of microorganism, platinum and palladium is (10~100): (0.5~2): 1 in alloy nano catalyst.
The growth period is short, yield is high, is suitble to industrialization culture production, and is a kind of typical metal reduction
Bacterium has powerful electronics releasability, sulphur metabolic capability and the high tolerance to toxicity, and the bacterium is in Anaerobic respiration processes
In, a series of electron transmission that the reducing substances such as protein, polysaccharide of intraor extracellular can be participated in by cromocis is real
The reduction of existing external source metal ion, while the functional group of these protein and others can mention for the growth of nano particle
For nucleation site, and the aggregation for preventing nano particle is interacted therewith, plays reduction and stable effect.
Preferably, the preparation method of the load of microorganisms type platinum-nickel alloys nanocatalyst includes the following steps:
(1) genus Shewanella (Shewanella) is seeded to expand in LB culture medium and is cultivated, obtain wet thallus after centrifugation；
(2) mixed solution of platinum and palladium metal ion is prepared；
(3) wet thallus that the step (1) obtains is added in the mixed solution of the step (2) preparation, is inhaled
The attached mixing sample for obtaining microorganism and metal；
(4) electron donor is added in the mixing sample that the step (3) obtains, is filled in nitrogen removal mixing sample
Reduction reaction is carried out after oxygen, vacuum freeze drying obtains load of microorganisms type platinum-nickel alloys nanocatalyst.
Preferably, in the step (1), expand culture time be 12~48h, centrifugal rotational speed be 5000~
12000rpm, centrifugation time are 5~20min.
Preferably, in the step (2), the mass ratio of platinum and palladium metal ion is (0.5~2) in mixed solution: 1,
The pH control of mixed solution is 1~4.Platinum and palladium metal ion are easier to be adsorbed on cell surface, while pH high within the scope of the pH
When 4, platinum and palladium ion are easy to happen and hydrolyze to form precipitating, interfere the preparation of nano material.
Preferably, in the step (3), concentration of the wet thallus in mixed solution is 1~10g/L, adsorption temp 20
~50 DEG C, adsorption time is 10~30min.Within the scope of the cell concentration, bacterium can be preferably dispersed in solvent, to receive
The formation of rice grain provides sufficient nucleation site, and the properties such as size, shape for further influencing nano particle.
Preferably, in the step (4), electron donor is any one in sodium formate, sodium lactate, pyruvic acid and hydrogen
Kind, concentration is 10~50mM, and the temperature of reduction reaction is 20~50 DEG C, and the time of reduction reaction is 0.5~3h；It is filled with nitrogen
When a length of 5~20min, the time of vacuum freeze drying is 5~20h.Within the temperature range of the reduction reaction, cell has
Different growths and metabolic activity, can be with the nano material of reduction synthesis different sizes and shapes.
Preferably, the concentration of the sodium borohydride solution is 20~50mM；In the organic polluting water, p-nitrophenyl
The concentration of phenol or azo dyes is 0.1~0.5mM；The load of microorganisms type platinum-nickel alloys nanocatalyst and p-nitrophenol
Or the mass ratio of azo dyes is (1-50): 1.Concentrations above range is the best dense of sodium borohydride and organic dyestuff catalytic degradation
Degree, and the quality of sodium borohydride can be kept much higher than the matter of contained p-nitrophenol or azo dyes in organic polluting water
Amount, enables the deoxidization, degradation fully reacting of dyestuff；Mass ratio (1-50): 1 can provide sufficient active site, add
The generation of fast response ensures the complete of reaction.
Preferably, after catalytic degradation reaction is completed, the load of microorganisms type platinum-nickel alloys nanocatalyst is passed through
Centrifugation or membrane separation technique, the load of microorganisms type platinum-nickel alloys nanocatalyst is separated and recovered from reaction system, is followed
Ring uses.
It is furthermore preferred that the centrifugal rotational speed of the centrifugation is 1000~10000rpm, centrifugation time is 1~15min；The film
The filter sizes that isolation technics uses is 0.05~0.5 μm.
Application of the invention be based on the principle that using sodium borohydride as reducing agent, in the presence of no catalyst, hydroboration
Sodium can not achieve the reduction of p-nitrophenol or azo dyes, and load of microorganisms type platinum-nickel alloys nanocatalyst area load
Platinum-nickel alloys nano particle can adsorb sodium borohydride and dyestuff simultaneously to catalyst surface, reduce the object of two kinds of reactive materials
Distance is managed, while the reaction activity between sodium borohydride and dyestuff also can be effectively reduced in platinum-nickel alloys nano particle, promoted
Transmitting of the electronics from sodium borohydride to dyestuff, to realize the deoxidization, degradation of p-nitrophenol or azo dyes.
The present invention is anchored using microbial cells, reduction is received in microbial cell with extracellular synthesis platinum-nickel alloys
Rice grain, the size of the nano particle are 3-40nm, microbial cell using bioactive molecule in it is intracellular or it is extracellular also
Original prepares noble metal nano particles, while microbial cell functional group abundant can effectively adhere to the nano particle of synthesis,
The reunion for preventing nano particle is played the role of stablizing and be protected, so that evenly dispersed load of microorganisms type platinum be prepared
Palldium alloy nanocatalyst, and there is catalytic activity and stability better than monometallic nanocatalyst, and be applied to nitre
The processing of base phenol and azo dye wastewater.Compared to individual chemical catalyst, the present invention is closed using microorganism and platinum palladium
Synergistic effect between gold nano grain, antimicrobial surface functional group abundant can promote reaction substrate and be adsorbed on catalyst table
Face, meanwhile, electron stream can be generated between microorganism and platinum-nickel alloys nano particle, strengthen absorption of the reaction substrate to electronics,
To show the performance for being much better than individual chemical catalyst.
Compared with prior art, the invention has the benefit that
1, load of microorganisms type platinum-nickel alloys nanocatalyst of the invention is in p-nitrophenol or azo dyes catalysis drop
Application in solution, catalytic activity is good, and thoroughly, degrading, the time used is short, and treatment effeciency is high for degradation；Compared to individual chemical catalysis
Agent, the present invention are to utilize the synergistic effect between microorganism and platinum-nickel alloys nano particle, antimicrobial surface functional group abundant
It can promote reaction substrate and be adsorbed on catalyst surface, meanwhile, electron stream can be generated between microorganism and platinum-nickel alloys nano particle,
Absorption of the reaction substrate to electronics is strengthened, to show the performance for being much better than individual chemical catalyst.
2, of the invention using used load of microorganisms type platinum-nickel alloys nanocatalyst, using microorganism as also
Former agent and stabilizer, the nanoparticle size being prepared is smaller, is evenly distributed, and can meet higher catalytic activity simultaneously, can
A variety of requirements such as reusability and stability.
3, the load of microorganisms type platinum-nickel alloys nanocatalyst that the present invention uses only needs simple microorganism adsorption and goes back
Former two steps can rapid synthesis platinum-nickel alloys nanocatalyst, do not need high temperature and pressure and additional toxic reducing agent and stabilization
Agent, therefore the preparation process of the catalyst is simple, low in cost, environmental-friendly.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the transmission electron microscopy for the load of microorganisms type platinum-nickel alloys nanocatalyst being prepared in embodiment 1
Mirror figure.
Fig. 2 is the scanning electron microscopy for the load of microorganisms type platinum-nickel alloys nanocatalyst being prepared in embodiment 1
Mirror figure.
Fig. 3 is the X-ray diffractogram for the load of microorganisms type platinum-nickel alloys nanocatalyst being prepared in embodiment 1.
Fig. 4 be in embodiment 1 load of microorganisms type platinum-nickel alloys nanocatalyst catalysis methyl orange degradation during with
The ultraviolet-visible spectrogram in reaction time.
Fig. 5 is that load of microorganisms type platinum-nickel alloys nanocatalyst catalysis reduction methyl orange recycles six times in embodiment 1
Degradation rate variation.
Fig. 6 is that load of microorganisms type platinum-nickel alloys nanocatalyst is catalyzed methyl red Degradation of Azo Dyes mistake in embodiment 2
With the ultraviolet-visible spectrogram in reaction time in journey.
Fig. 7 is that load of microorganisms type platinum-nickel alloys nanocatalyst is catalyzed 4 Degradation of Azo Dyes of azogeramine in embodiment 3
In the process with the ultraviolet-visible spectrogram in reaction time.
Fig. 8 is that load of microorganisms type platinum-nickel alloys nanocatalyst is catalyzed in p-nitrophenol degradation process in embodiment 4
With the ultraviolet-visible spectrogram in reaction time.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is done below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of application of load of microorganisms type platinum-nickel alloys nanocatalyst of the invention in catalytic degradation methyl orange,
Using including the following steps:
1. preparing load of microorganisms type platinum-nickel alloys nanocatalyst:
(1) aseptically Shewanella (Shewanella oneidensis MR-1) bacterium solution is inoculated into and has been sterilized
100mL LB culture medium in, at 30 DEG C, 170r/min expand culture for 24 hours after, be centrifuged 10min under the conditions of 10000rpm,
It is collected into obtain the wet thallus after activation culture；
(2) prepare mixed solution that platinum and palladium metal ion concentration are 100mg/L (quality of platinum and palladium metal ion it
Than adjusting pH to 3.0, system 30mL for 1:1)；
(3) wet thallus for weighing 0.09g is added in the mixed solution of platinum and palladium, so that wet thallus concentration is 3.0g/L,
30min is adsorbed under the conditions of being placed in 30 DEG C；
(4) in the mixing sample of Xi Washi and two metal ion species, the sodium formate electron donor of 25mM is added, is filled with nitrogen
Gas 10min removes the oxygen in sample, under the conditions of most 30 DEG C of postposition, restores 1h, last vacuum freeze drying 10h obtains micro- life
Object load type platinum palldium alloy nanocatalyst.
Load of microorganisms type platinum-nickel alloys nanocatalyst, mass ratio (bacterium: platinum: palladium) are 30:1:1, are prepared average
Having a size of 13nm and evenly dispersed platinum-nickel alloys nanocatalyst, Fig. 1-3 are respectively that the transmitted electron of the nanocatalyst is aobvious
Micro mirror figure, scanning electron microscope diagram and X-ray diffractogram.
As shown in Figure 1, Shewanella can synthesize the evenly dispersed spherical platinum-nickel alloys nanometer of 5-20nm in the cell
Particle.
As shown in Figure 2, the platinum-nickel alloys nano particle that Shewanella can be evenly dispersed in extracellularly synthesis 9-25nm.
From the figure 3, it may be seen that the platinum-nickel alloys nano particle of Shewanella synthesis is face-centred cubic structure.
2. preparing methyl orange azo dyes and sodium borohydride mother liquor
The methyl orange of 10mM and the sodium borohydride mother liquor of 0.1M are prepared respectively, draw the methyl orange of 0.1ml and the boron hydrogen of 1mL
Change mother liquid of sodium into silica dish, the distilled water of 3.4mL is added, so that methyl orange and the ultimate density of sodium borohydride are respectively
0.3mM and 30mM.
3. catalysis reduction
The load of microorganisms type platinum-nickel alloys nanocatalyst being prepared for weighing 2mg is added to step 2 preparation and obtains
Methyl orange and sodium borohydride mixed solution in, make the mass ratio 5:1 of catalyst and methyl orange in mixed solution, occur immediately
Vigorous reaction utilizes the variation (such as Fig. 4) of reaction substrate and product in UV-Vis spectroscopic techniques detection reaction process.
4. being recycled
After complete reaction, reaction system is centrifuged 5min in 5000rpm, recycling obtains load of microorganisms type platinum-nickel alloys
Nanocatalyst is repeated 6 times according to step 2 and 3, verifies the stability (such as Fig. 5) of the catalyst.
As shown in Figure 4, which can realize urging for methyl orange in 2min
Change degradation, degradation rate reaches 96%, illustrates it with high catalytic performance.
As shown in Figure 5, after which is recycled 6 times, to the drop of methyl orange
Solution rate reaches 93% or more almost without decline, illustrates it with strong stability.
Embodiment 2:
The load of microorganisms type platinum-nickel alloys nanocatalyst that step 1 is prepared in above-described embodiment 1 is in catalytic degradation
Application in methyl red azo dyes, application include the following steps:
(1) it prepares the methyl red of 10mM and the sodium borohydride mother liquor of 0.1M respectively, draws the methyl red and 1mL of 0.1ml
Sodium borohydride mother liquor adds the distilled water of 3.4mL into silica dish, so that the ultimate density of methyl red and sodium borohydride is distinguished
For 0.3mM and 30mM；
(2) the load of microorganisms type platinum-nickel alloys nanocatalyst being prepared in the embodiment 1 of 2mg is weighed, is added to
In methyl red and sodium borohydride mixed solution in step 1, make the mass ratio 7:1 of catalyst and methyl red in mixed solution,
Vigorous reaction occurs immediately, using the variation of reaction substrate and product in UV-Vis spectroscopic techniques detection reaction process (as schemed
6)。
It will be appreciated from fig. 6 that the load of microorganisms type platinum-nickel alloys nanocatalyst can realize urging for methyl red in 6min
Change degradation, degradation rate reaches 92%, and catalytic activity is good, and thoroughly, degrading, the time used is short, and treatment effeciency is high for degradation.
Embodiment 3:
The load of microorganisms type platinum-nickel alloys nanocatalyst that step 1 is prepared in above-described embodiment 1 is in catalytic degradation
Application in 4 azo dyes of azogeramine, application include the following steps:
(1) azogeramine 4 of 10mM and the sodium borohydride mother liquor of 0.1M are prepared respectively, draw 4 He of azogeramine of 0.1ml
The sodium borohydride mother liquor of 1mL adds the distilled water of 3.4mL into silica dish, so that azogeramine 4 and sodium borohydride is final
Concentration is respectively 0.3mM and 30mM；
(2) the load of microorganisms type platinum-nickel alloys nanocatalyst being prepared in the embodiment 1 of 2mg is weighed, is added to
In azogeramine 4 and sodium borohydride mixed solution in step 1, make the mass ratio 4 of catalyst and acid red in mixed solution:
1, vigorous reaction occurs immediately, detects the variation of reaction substrate and product in reaction process (such as using UV-Vis spectroscopic techniques
Fig. 7).
As shown in Figure 7, which can realize azogeramine 4 in 11min
Catalytic degradation, degradation rate reach 94%, and catalytic activity is good, and thoroughly, degrading, the time used is short, and treatment effeciency is high for degradation.
Embodiment 4:
The load of microorganisms type platinum-nickel alloys nanocatalyst that step 1 is prepared in above-described embodiment 1 is in catalytic degradation
Application in p-nitrophenol, application include the following steps:
(1) p-nitrophenol of 10mM and the sodium borohydride mother liquor of 0.1M are prepared respectively, draw the p-nitrophenol of 0.1ml
Sodium borohydride mother liquor with 1mL adds the distilled water of 3.4mL into silica dish, so that p-nitrophenol and sodium borohydride
Ultimate density is respectively 0.3mM and 30mM；
(2) the load of microorganisms type platinum-nickel alloys nanocatalyst being prepared in the embodiment 1 of 2mg is weighed, is added to
In p-nitrophenol and sodium borohydride mixed solution in step 1, make the quality of catalyst and p-nitrophenol in mixed solution
Than vigorous reaction occurring immediately for 13:1, reaction substrate in UV-Vis spectroscopic techniques detection reaction process and product are utilized
Change (such as Fig. 8).
As shown in Figure 8, which can realize p-nitrophenol in 4min
Catalytic degradation, degradation rate reaches 97%, and catalytic activity is good, and thoroughly, degrading, the time used is short, and treatment effeciency is high for degradation.
Comparative example 1:
The load of microorganisms type platinum-nickel alloys nano-catalytic being prepared according to method same as step 1 in embodiment 1
Agent and load of microorganisms type platinum nano catalyst, load of microorganisms type palladium nanocatalyst, apply equally to methyl orange, methyl red
With the catalysis degeneration experiment of 4 azo dyes of azogeramine and p-nitrophenol pollutant, experiment condition is also the same as embodiment 1-4.Three
Kind load of microorganisms type nanocatalyst is as shown in table 1 to the time needed for four kinds of organic pollutant catalytic degradations.
1: three kind of load of microorganisms type nanocatalyst of table is to the time needed for four kinds of organic pollutant catalytic degradations
As shown in Table 1, in the catalytic degradation reaction of four kinds of organic pollutants, load of microorganisms type platinum palladium Nanoalloy is received
Time needed for rice catalyst is minimum, illustrates the catalytic activity of the alloy nano catalyst better than corresponding monometallic nano-catalytic
Agent.
Comparative example 2:
Compare load of microorganisms type platinum-nickel alloys nanocatalyst provided by the invention and business platinum carbon and palladium-carbon catalyst
The catalytic activity of azo dyes, using methyl orange as experimental subjects, experiment condition is the same as embodiment 1.Three kinds of catalyst are to methyl orange
Catalytic degradation the time required to as shown in table 2.
2: three kinds of catalyst of table are to the time needed for methyl orange catalytic degradation
As shown in Table 2, in the catalytic degradation of methyl orange, load of microorganisms type platinum-nickel alloys nanometer provided by the invention is urged
The catalytic activity of agent is much higher than the purifying chemical catalyst such as the platinum carbon of business and palladium carbon.
Claims (10)
1. a kind of load of microorganisms type platinum-nickel alloys nanocatalyst answering in p-nitrophenol or azo dyes catalytic degradation
With, which is characterized in that the method for the application includes the following steps: the organic contamination containing p-nitrophenol or azo dyes
Waste water is mixed with sodium borohydride solution, and it is anti-that load of microorganisms type platinum-nickel alloys nanocatalyst progress catalytic degradation is then added
It answers, the catalytic degradation of the organic polluting water is completed after fully reacting；The load of microorganisms type platinum-nickel alloys nano-catalytic
Agent has platinum-nickel alloys nano particle using microorganism as carrier, in the intracellular and/or extracellular load of microorganism.
2. application according to claim 1, which is characterized in that the load of microorganisms type platinum-nickel alloys nanocatalyst is adopted
Microorganism is genus Shewanella (Shewanella), and the partial size of the platinum-nickel alloys nano particle is 3~40nm, described micro-
The mass ratio of microorganism, platinum and palladium is (10~100): (0.5~2): 1 in biological load type platinum-nickel alloys nanocatalyst.
3. application according to claim 2, which is characterized in that the load of microorganisms type platinum-nickel alloys nanocatalyst
Preparation method includes the following steps:
(1) genus Shewanella (Shewanella) is seeded to expand in LB culture medium and is cultivated, obtain wet thallus after centrifugation；
(2) mixed solution of platinum and palladium metal ion is prepared；
(3) wet thallus that the step (1) obtains is added in the mixed solution of the step (2) preparation, adsorb
To the mixing sample of microorganism and metal；
(4) electron donor is added in the mixing sample that the step (3) obtains, the oxygen being filled in nitrogen removal mixing sample
After carry out reduction reaction, vacuum freeze drying obtains load of microorganisms type platinum-nickel alloys nanocatalyst.
4. application according to claim 3, which is characterized in that in the step (1), expand culture time be 12~
48h, centrifugal rotational speed are 5000~12000rpm, and centrifugation time is 5~20min.
5. application according to claim 3, which is characterized in that in the step (2), in mixed solution platinum and palladium metal from
The mass ratio of son is (0.5~2): 1, the pH control of mixed solution is 1~4.
6. application according to claim 3, which is characterized in that in the step (3), wet thallus is dense in mixed solution
Degree is 1~10g/L, and adsorption temp is 20~50 DEG C, and adsorption time is 10~30min.
7. application according to claim 3, which is characterized in that in the step (4), electron donor is sodium formate, lactic acid
Any one in sodium, pyruvic acid and hydrogen, concentration are 10~50mM, and the temperature of reduction reaction is 20~50 DEG C, and reduction is anti-
The time answered is 0.5~3h；It is filled with when a length of 5~20min of nitrogen, the time of vacuum freeze drying is 5~20h.
8. application described in any one of -7 according to claim 1, which is characterized in that the concentration of the sodium borohydride solution is 20
~50mM；In the organic polluting water, the concentration of p-nitrophenol or azo dyes is 0.1~0.5mM；The microorganism
The mass ratio of load type platinum palldium alloy nanocatalyst and p-nitrophenol or azo dyes is (1-50): 1.
9. application described in any one of -7 according to claim 1, which is characterized in that after catalytic degradation reaction is completed, by institute
Load of microorganisms type platinum-nickel alloys nanocatalyst is stated by centrifugation or membrane separation technique, the load of microorganisms type platinum palladium is closed
Gold nano catalyst is separated and recovered from reaction system, is recycled.
10. application according to claim 9, which is characterized in that the centrifugal rotational speed of the centrifugation is 1000~10000rpm,
Centrifugation time is 1~15min；The filter sizes that the membrane separation technique uses is 0.05~0.5 μm.
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Cited By (5)
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| CN110694636A (en) * | 2019-10-08 | 2020-01-17 | 中南大学 | Carbon-based-multi-metal composite nano catalytic material and preparation method and application thereof |
| CN111545226A (en) * | 2020-04-01 | 2020-08-18 | 中南大学 | Bifunctional carbon-based iron phosphide nano material based on microbial synthesis and preparation method and application thereof |
| CN111916772A (en) * | 2020-06-28 | 2020-11-10 | 中南大学 | Pd/HNC catalytic material, preparation method thereof and application of Pd/HNC catalytic material as fuel cell catalyst |
| CN113023906A (en) * | 2021-04-07 | 2021-06-25 | 杭州师范大学 | Method for degrading quinolone antibacterial drug wastewater by using bio-metal catalyst |
| CN113731168A (en) * | 2021-09-16 | 2021-12-03 | 中南大学 | Volatile organic waste gas purification system and method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110694636A (en) * | 2019-10-08 | 2020-01-17 | 中南大学 | Carbon-based-multi-metal composite nano catalytic material and preparation method and application thereof |
| CN110694636B (en) * | 2019-10-08 | 2021-05-07 | 中南大学 | Carbon-based-multi-metal composite nano catalytic material and preparation method and application thereof |
| CN111545226A (en) * | 2020-04-01 | 2020-08-18 | 中南大学 | Bifunctional carbon-based iron phosphide nano material based on microbial synthesis and preparation method and application thereof |
| CN111916772A (en) * | 2020-06-28 | 2020-11-10 | 中南大学 | Pd/HNC catalytic material, preparation method thereof and application of Pd/HNC catalytic material as fuel cell catalyst |
| CN113023906A (en) * | 2021-04-07 | 2021-06-25 | 杭州师范大学 | Method for degrading quinolone antibacterial drug wastewater by using bio-metal catalyst |
| CN113731168A (en) * | 2021-09-16 | 2021-12-03 | 中南大学 | Volatile organic waste gas purification system and method thereof |
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