CN107497422A - A kind of Pd/C catalyst and its biological preparation method applied to electric Fenton-like system negative electrode - Google Patents
A kind of Pd/C catalyst and its biological preparation method applied to electric Fenton-like system negative electrode Download PDFInfo
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Abstract
The invention discloses a kind of biological preparation method applied to electric Fenton-like system cathod catalyst, including following preparation process：Step 1, preparation of reagents；Step 2, S.oneidensis MR 1 culture；Step 3, S.oneidensis MR 1 cleaning and collection；Step 4, S.oneidensis MR 1OD600The measure of value；Step 5, biological reducing palladium and collection drying process；Step 6, the alkali activation process of material；The defects of present invention is directed to cathode material palladium metal catalyst in electric Fenton-like system and takes chemical synthesis mostly in commercial synthesis, and time-consuming, and cost is big, complex process, while environmental pollution is serious is improved.Present design avoids the addition of chemical reagent, and does not consume any energy, economical and convenient, reproducible, and low-carbon environment-friendly, is to promote O in electric Fenton-like system2Generate H2O2And a green syt approach further is provided as the cathode material of the efficient catalytic performance of OH catalytic degradation organic pollutions, while micro-reduction metal salt is also a kind of important method for reclaiming heavy metal.
Description
Technical field
The present invention relates to a kind of preparation method applied to electric Fenton-like system cathod catalyst, more particularly to a kind of use to give birth to
Catalyst applied to electric Fenton-like system negative electrode prepared by thing method and preparation method thereof.
Background technology
1894, Frenchman H.J.H Fenton had found to coexist in ferrous ion and hydrogen peroxide in a scientific research
Under conditions of, the tartaric acid in acidic aqueous solution can be aoxidized effectively.Descendant in order to souvenir he by ferrous salt and peroxidating
The combination of hydrogen is referred to as Fenton reagent, is referred to as Fenton reactions using the reaction of this reagent.It can the efficient oxidation removal tradition
The hardly degraded organic substance that can not be removed in wastewater processing technology, its essence is H2O2In Fe2+Catalytic action under generation have height
The hydroxyl free (OH) of reactivity, OH can act on most of organic matters makes its degraded.Electricity-Fenton methods combine electricity
Chemical process and Fenton oxidation process, Fe caused by electrochemical process2+And H2O2As the constant source of Fenton reagent,
Take full advantage of the oxidability of the two.The general principle of electricity-Fenton methods is：In an acidic solution, by way of electrolysis,
O2First H is generated in negative electrode by two electronic reduction reactions2O2, the H of generation2O2Rapidly with additional Fe in solution2+Reaction generation OH
And Fe3+, the purpose removed to hardly degraded organic substance, and Fe are reached using the Strong oxdiative ability of OH non-selectivities3+And can is in the moon
Pole is reduced into Fe2+, so that oxidation reaction circulation is carried out.
Electric Fenton (Electro-Fenton) is a kind of model electrochemical oxidation technology, because it can be produced in system
Pollutant in OH oxidative degradation water bodys, causes scholars' extensive concern.The technology has the advantages of notable：
(1) reaction condition is gentle, generally need to only be carried out under normal temperature, normal pressure；
(2) by there is the electrode of catalytic activity, hydroxyl radical free radical is directly or indirectly produced at the scene, being capable of non-selectivity
Degradable organic pollutant；
(3) without additional chemical oxidizing agent, so as to reduce the secondary pollution that may be brought by the addition of chemical reagent
Problem, it is a kind of green technique.
In recent years, increasing researcher combines Fenton reagent with other processing method, such as biological treatment
Method, supercritical ultrasonics technology, Coagulation Method, the precipitation method, activated carbon method etc..In a broad sense, Fenton methods are to utilize catalyst or light spoke
Penetrate or electrochemical action, pass through H2O2Produce the technology of OH processing organic pollutions.From the point of view of development course, Fenton method bases
Three routes are combined in sheet along photochemistry, electrochemistry and other methods to advance.
The yields of hydrogen peroxide of negative electrode is generally relatively low in Electro-Fenton systems at present, and current efficiency is not high.
The practical key of Electro-Fenton technological direction is developed to O2Generate H2O2Negative electrode material with efficient catalytic performance
Material, improving the current efficiency of electrode material and reducing energy consumption turns into current main direction.
This catalyst is the cathode material applied to electric Fenton-like system, the chemical synthesis with traditional business Pd/C catalyst
Method is different, and this method, as reducing agent, avoids chemical reagent using microorganism S.oneidensis MR-1 existing for environment
Addition, and do not consume any energy, be that reducing agent is former by using microorganism S.oneidensis MR-1 existing for environment
Position synthesis nano Pd particle forms nano composite material so as to a step, this method economical and convenient, reproducible, and low-carbon environment-friendly.
The content of the invention
It is an object of the invention to overcome cathode material palladium metal catalyst in electric Fenton-like system in the prior art to prepare consumption
The defects of duration, cost is big, complex process, and catalytic efficiency is not high, environmental pollution is serious, there is provided one kind applies electric Fenton-like system
Cathode material-Pd/C catalyst biological preparation method；
The present invention is achieved by the following technical solutions：The invention discloses a kind of electric Fenton-like system negative electrode of application
The biological preparation method of Pd/C catalyst, including following preparation process：
Step 1, preparation of reagents；
1) preparation of LB culture mediums
By sodium chloride, tryptone and dusty yeast in mass ratio 2:2:1 amount is weighed, and ultra-pure water constant volume is used after mixing, system
LB nutrient solutions just liquid, then liquid at the beginning of the LB nutrient solutions is sealed, sterilize and cooling treatment after save backup, obtain LB
Culture medium；
2) preparation of anaerobic culture medium
Three water dipotassium hydrogen phosphates, potassium dihydrogen phosphate, sodium chloride, ammonium sulfate, epsom salt, HEPES, lactic acid are weighed respectively
Sodium and micro- storing solution, ultra-pure water constant volume is used after mixing, then adjust pH value to 7.0 with sodium hydroxide, obtain anaerobism training
The first liquid of nutrient solution；Liquid at the beginning of the Anaerobic culturel liquid is added in serum bottle, saved backup after inflated with nitrogen, sealing and sterilization treatment,
Obtain anaerobic culture medium；
3) preparation of Pd (II) mother liquor
With the ultra-pure water after sterilizing under the conditions of lucifuge by chlorine palladium acid sodium grain dissolution, constant volume, then solution is poured into and gone out
In the brown bottle of complete bacterium, sealing, which is placed in refrigerator, to be saved backup；
Step 2, S.oneidensis MR-1 culture；
After S.oneidensis MR-1 are taken out from -80 DEG C of refrigerators and carry out LB plate streaking processing to it, it will cultivate
Ware back-off, which is put into constant incubator, to be cultivated, and marks date and bacterial strain；Then the LB flat boards after line is handled are put into refrigerator
It is sealed；S.oneidensis MR-1 monoclonals are selected on the LB flat boards to be put into the LB culture mediums and 30
DEG C, cultivated in 150rpm shaking table；
Step 3, S.oneidensis MR-1 cleaning and collection；
Centrifugal treating is carried out to cultured bacterium solution in step 2, supernatant is removed, retains bottom precipitation；Then with described
Anaerobic culture medium carries out repeated washing, centrifugal treating to bottom precipitation respectively, repeats 3 times, is trained after cleaning with the anaerobism
Support base to cultivate bottom precipitation bacterium solution, obtain S.oneidensis MR-1 collection liquids；
Step 4, S.oneidensis MR-1OD600The measure of value；
Measure S.oneidensis MR-1 collection liquids described in 100 μ L and be diluted with water to 10mL, mix；By spectrophotometric
Meter wavelength is adjusted to 600nm, determines 2 times, averages, calculate the concentration OD of collection liquid600；
Step 5, biological reducing palladium and collection drying process；
2) the S.oneidensis MR-1 collection liquids are scattered in in the serum bottle equipped with anaerobic culture medium, then
Standby chlorine palladium acid sodium solution in being injected 3) into the serum bottle, 3h is cultivated in 30 DEG C, 150rpm shaking table；Then will be mixed
Close liquid to be centrifuged, washed successively, be repeated 3 times, the bacterium palladium mixed liquor of collection is placed in -70 DEG C of refrigerator and freezes 1h, take out
After be put into freeze drier dry 72h, weigh；
Step 6, the alkali activation process of material；
By dried bacterium palladium mixture in step 5 and KOH in mass ratio 1:After 1 mixing, mixture is put into tube furnace
In heated；After room temperature cooling, cleaned respectively with the hydrochloric acid and deionized water that mass fraction is 5% to neutralize alkali and go
Removing chloride remains；Dry, grind and preservation of weighing after, obtain target product.
Further, in the quality and sterilization effect of nutrient solution in order to better improve, 1) LB nutrient solutions just liquid be by
28g sodium chloride, 28g tryptones and 14g dusty yeasts are settled to 2800mL with ultra-pure water and obtained；Sterilization treatment is will to state LB cultures
Liquid is just placed 20min under liquid is 0.13MPa in 121 DEG C, pressure and sterilized.
Further, just liquid is by the water phosphoric acid of 1.132g tri- to Anaerobic culturel liquid in order to reach optimal catalytic efficiency, 2)
Hydrogen dipotassium, 0.675g potassium dihydrogen phosphates, 1.380g sodium chloride, 0.765g ammonium sulfate, 0.072g epsom salts,
After 14.298gHEPES, 6.726g sodium lactate and the mixing of 15mL trace elements storing solution obtained by ultra-pure water is settled to 3000mL；
3) concentration of Pd (II) mother liquor is 15mmol/L in, solution is fitted into brown bottle seal and be placed on preserved in 4 DEG C of refrigerators it is standby
With.
Further, micro- storing solution is by 1.5g NTA (Nitrilotriacetic acid), is adopted
500mL is settled to ultra-pure water, potassium hydroxide adjusts pH value to 6.5, adds 3.0g magnesium sulfate (MgSO4), the water chlorinations of 1.0g bis-
Calcium (CaCl2.2H2O), 1.0g sodium chloride (NaCl), 0.5g manganese sulfate (MnSO4), 0.18g white vitriols (ZnSO4.7H2O),
0.1g ferrous sulfate heptahydrates (FeSO4.7H2O), 0.18g cobalt sulfates (CoSO4.7H2O), the water nickel chlorides of 0.025g six
(NiCl2.6H2O), the water of 0.02g 12 and alum (KAl (SO4)2.12H2O), 0.01g cupric sulfate pentahydrates
(CuSO4.5H2O), 0.01g boric acid (H3BO3), 0.01g Sodium Molybdate Dihydrates (Na2MoO4.2H2O), 0.3mg Sodium selenite (Na2SeO3) pentahydrates
(Na2SeO3.5H2O), 1000mL is dissolved to again after shaking up dissolving, is preserved in 4 DEG C of refrigerators.
Further, the cleanliness factor of catalyst in order to better improve, the centrifugal treating in step 3 and step 5, centrifugation
The rotating speed of machine is 7000-8000rpm, centrifugation time 15-20min.
Further, in order to accelerate the drying of catalyst, and can avoids catalyst high temperature deactivation simultaneously, is mixed in step 6
Thing is that 420 DEG C of heating is carried out in the tube furnace of vacuum atmosphere, and heating rate is 1 DEG C/min, a length of during heated at constant temperature
3h。
This method uses microorganism S.oneidensis MR-1 existing for environment for reducing agent, to avoid chemical reagent
Addition, and any energy is not consumed, it is that reducing agent is in situ by using microorganism S.oneidensis MR-1 existing for environment
Nano Pd particle is synthesized so as to which a step forms nano composite material.In addition, this method is electrochemistry and the technology in biological study field
Cooperation, prepares nano material for biology-electrochemical process low-carbon environment-friendly and nano composite material provides new approaches and new tool.
The present invention applies Pd/C catalyst made from bioanalysis in electric Fenton-like system, by the way that catalyst is supported on into gas
, can be with more efficient degradable organic pollutant compared with catalyst is directly added on diffusion electrode.And the business of contrast chemical industry synthesis
Product Pd/C, Pd/C catalyst made from this bioanalysis are more efficient electric Fenton-like system degradable organic pollutant.
Brief description of the drawings
Fig. 1 is to be schemed using the TEM of palladium carbon catalyst made from bioanalysis；
Fig. 2 is to be schemed using the EDS of palladium carbon catalyst made from bioanalysis.
Embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
Embodiment 1 discloses a kind of biological preparation method applied to electric Fenton-like system cathod catalyst, including following system
Standby step：
Step 1, preparation of reagents；
1) preparation of LB culture mediums
By sodium chloride, tryptone and dusty yeast in mass ratio 2:2:1 amount is weighed, and ultra-pure water constant volume is used after mixing, system
LB nutrient solutions just liquid, then liquid at the beginning of the LB nutrient solutions is sealed, sterilize and cooling treatment after save backup, obtain LB
Culture medium；Wherein just liquid is to be settled to by 28g sodium chloride, 28g tryptones and 14g dusty yeasts with ultra-pure water to LB nutrient solutions
2800mL is obtained；Sterilization treatment is that liquid at the beginning of LB nutrient solutions is placed into 20min in the case where 121 DEG C, pressure is 0.13MPa to be sterilized.
2) preparation of anaerobic culture medium
The water dipotassium hydrogen phosphates of 1.132g tri-, 0.675g potassium dihydrogen phosphates, 1.380g sodium chloride, 0.765g sulfuric acid are weighed respectively
Ammonium, 0.072g epsom salts, 14.298gHEPES, 6.726g sodium lactate and 15mL trace element storing solutions, with super after mixing
Pure water is settled to 3000mL, then adjusts pH value to 7.0 with sodium hydroxide, obtains Anaerobic culturel liquid just liquid；By Anaerobic culturel liquid
First liquid is added in serum bottle, is saved backup after inflated with nitrogen, sealing and sterilization treatment, is obtained anaerobic culture medium；Wherein, micro member
Plain storing solution is by 1.5g NTA, and 500mL is settled to using ultra-pure water, adjusts pH value to 6.5 with potassium hydroxide, so
3.0g magnesium sulfate, 1.0g calcium chloride dihydrates, 1.0g sodium chloride, 0.5g manganese sulfates, 0.18g white vitriols, 0.1g seven are added afterwards
Aqueous ferrous sulfate, 0.18g cobalt sulfates, the water nickel chlorides of 0.025g six, the water of 0.02g 12 and alum, the water sulphur of 0.01g five
Sour copper, 0.01g boric acid, 0.01g Sodium Molybdate Dihydrates, 0.3mg Sodium selenite (Na2SeO3) pentahydrates, it is dissolved to again with ultra-pure water after shaking up dissolving
Obtained by 1000mL, it is placed in 4 DEG C of refrigerators and preserves；
3) preparation of Pd (II) mother liquor
With the ultra-pure water after sterilizing under the conditions of lucifuge by chlorine palladium acid sodium grain dissolution, constant volume, then solution is poured into and gone out
In the brown bottle of complete bacterium, the concentration of Pd (II) mother liquor is 15mmol/L, and solution is fitted into brown bottle and seals and be placed on 4 DEG C of ice
Saved backup in case.
Step 2, S.oneidensis MR-1 culture；
After S.oneidensis MR-1 are taken out from -80 DEG C of refrigerators and carry out LB plate streaking processing to it, it will cultivate
Ware back-off, which is put into constant incubator, to be cultivated, and marks date and bacterial strain；Then the LB flat boards after line is handled are put into refrigerator
It is sealed；S.oneidensis MR-1 monoclonals are selected on the LB flat boards to be put into the LB culture mediums and 30
DEG C, cultivated in 150rpm shaking table；
Step 3, S.oneidensis MR-1 cleaning and collection；
Centrifugal treating is carried out to cultured bacterium solution in step 2, supernatant is removed, retains bottom precipitation；Then with described
Anaerobic culture medium carries out repeated washing, centrifugal treating to bottom precipitation respectively, repeats 3 times, and the rotating speed of centrifuge is
8000rpm, centrifugation time 20min.Bottom precipitation bacterium solution is cultivated with the anaerobic culture medium after cleaning, obtained
S.oneidensis MR-1 collection liquids；
Step 4, S.oneidensis MR-1OD600The measure of value；
Measure S.oneidensis MR-1 collection liquids described in 100 μ L and be diluted with water to 10mL, mix；By spectrophotometric
Meter wavelength is adjusted to 600nm, determines 2 times, averages, calculate the concentration OD of collection liquid600；
Step 5, biological reducing palladium and collection drying process；
2) the S.oneidensis MR-1 collection liquids are scattered in in the serum bottle equipped with anaerobic culture medium, then
Standby chlorine palladium acid sodium solution in being injected 3) into the serum bottle, 3h is cultivated in 30 DEG C, 150rpm shaking table；Then will be mixed
Close liquid to be centrifuged, washed successively, be repeated 3 times, the rotating speed of centrifuge is 8000rpm, centrifugation time 20min.It will collect
Bacterium palladium mixed liquor be placed in -70 DEG C of refrigerator and freeze 1h, be put into after taking-up in freeze drier and dry 72h, weighed；
Step 6, the alkali activation process of material；
By dried bacterium palladium mixture in step 5 and KOH in mass ratio 1:After 1 mixing, mixture is placed on vacuum gas
Carry out 420 DEG C of heating in the tube furnace of atmosphere, heating rate is 1 DEG C/min, a length of 3h during heated at constant temperature；Room temperature cools down
Afterwards, cleaned respectively with the hydrochloric acid and deionized water that mass fraction is 5% to neutralize alkali and remove Chloride residue；Dry,
Grind and weigh after preservation, obtain target product.
Fig. 1 is to scheme (projection Electronic Speculum) using the TEM of palladium carbon catalyst made from bioanalysis, as can be seen from the figure charcoal
A large amount of palladium particles are loaded in space, individual particles size is larger, reaches 30-40nm, and most particles are 10-15nm, this method
The size of obtained palladium particle more conforms to needs of production compared to palladium particle size made from other method；
Fig. 2 is to scheme (Energy Dispersive X-ray spectrum) using the EDS of palladium carbon catalyst made from this bioanalysis, passes through element point
Analysis determines Pd presence.(note：Because sample is placed on copper Web-based testing, there are Cu elements)
By palladium carbon catalyst made from bioanalysis electric Fenton-like system negative electrode application example-organic pollution methyl orange
Degradation experiment：
1) experiment material
Pd/C gas-diffusion electrodes：Weigh powdered carbon 9g and be put into large beaker, submerged with ethanol, be stirred continuously in the heater
The general temperature of 15-20min reaches 80 DEG C, adds 15mLPTFE, then constantly observation, with hand examination until can into viscous shape after 1-2h
Kneading to take out, and finally rolled repeatedly with tablet press machine, until surface is smooth, thickness is moderate, then is placed on stainless (steel) wire and presses
The thin slice integrally changed.The piece pressed is put into Muffle furnace, and heat up 100min, and stopping 20min at 340 DEG C fires, after cooling terminates
Take out standby.The electrode slice prepared is cut into diameter 2.5cm, area 4.9cm with scissors2Circular piece.Weigh equivalent
Palladium nano-particles are put into 2.0mL EP pipes, are then respectively adding 200 μ L Nafion and 200 μ L pure water, and ultrasound is allowed to mix
Uniformly.Finally palladium liquid is uniformly coated onto in circular piece with hairbrush, it is overnight air-dry after save backup.
Methyl orange：40mg/L
Na2SO4：0.05mol/L
FeSO4·7H2O：0.5mmol/L
Commodity Pd/C：No. CAS：7440-05-3；Molecular formula：Pd/C；Palladium content：5%；Granule strength：90-95%；Selection
Property：90-95%；Lot number：X88887；Producer：Shandong West Asia chemical industry Co., Ltd
2) experimental procedure
Methyl orange electrolyte (the methyl orange that will be prepared：40mg/L；Na2SO4：0.05mol/L；FeSO4·7H2O：
0.5mmol/L) pour into 500mL beakers, be put into Pd/C gas-diffusion electrodes, be passed through oxygen cylinder conduit, oxygen gas flow rate is
300mL/min, preaeration 20min.
Take out Pd/C gas-diffusion electrodes and assemble reaction tank, add 40mL methyl orange electrolyte, access oxygen cylinder is led
Pipe, loads onto platinum filament anode, connects the both positive and negative polarity of DC power supply, opens DC power supply switch, and regulation electric current is
100mA, timing 30min.
DC power supply switch is closed, takes out oxygen cylinder conduit, methyl orange electrolyte is loaded into 50mL centrifuge tubes protects
Deposit.Sample is surveyed to absorbance and TOC and COD respectively.(by ten groups of contrast experiments, averaging)
3) experimental result
Degradation rate：Biosynthesis Pd/C was 99.5% in 30 minutes, and the commodity Pd/C bought was 49.8% in 30 minutes,
So the Pd/C catalyst of biosynthesis is 2 times of commodity chemical industry synthesis Pd/C to the degradation rate of organic pollution methyl orange.
TOC：Biosynthesis Pd/C was 23.3% in 30 minutes, and the commodity Pd/C bought was 3.3% in 30 minutes, data
The Pd/C catalyst for showing biosynthesis is 7 times of commodity chemical industry synthesis Pd/C to the TOC clearances of organic pollution methyl orange.
(wherein, 45.6%) biosynthesis Pd/C TOC clearances are up to
COD：Biosynthesis Pd/C COD clearance average values are up to 70.4, and be far longer than commodity Pd/C 21.6 remove
Rate.
4) experiment conclusion
Experiment shows, using the Pd/C of biosynthesis than the Pd/C that in the market is bought, the methyl orange drop within the unit interval
Obvious degradation capability has been played in solution experiment, there is higher catalytic efficiency.
Embodiment 2
By palladium carbon catalyst made from bioanalysis electric Fenton-like system negative electrode application example-organic pollution methyl orange
Degradation experiment：
1) experiment material
Pd/C gas-diffusion electrodes：Weigh powdered carbon 9g and be put into large beaker, submerged with ethanol, be stirred continuously in the heater
The general temperature of 15-20min reaches 80 DEG C, adds 15mLPTFE, then constantly observation, with hand examination until can into viscous shape after 1-2h
Kneading to take out, and finally rolled repeatedly with tablet press machine, until surface is smooth, thickness is moderate, then is placed on stainless (steel) wire and presses
The thin slice integrally changed.The piece pressed is put into Muffle furnace, and heat up 100min, and stopping 20min at 340 DEG C fires, after cooling terminates
Take out standby.The electrode slice prepared is cut into diameter 2.5cm, area 4.9cm with scissors2Circular piece.Weigh equivalent
Palladium nano-particles are put into 2.0mL EP pipes, are then respectively adding 200 μ L Nafion and 200 μ L pure water, and ultrasound is allowed to mix
Uniformly.Finally palladium liquid is uniformly coated onto in circular piece with hairbrush, it is overnight air-dry after save backup.
Methyl orange：40mg/L
Na2SO4：0.05mol/L
FeSO4·7H2O：0.5mmol/L
Commodity Pd/C：No. CAS：7440-05-3；Molecular formula：Pd/C；Palladium content：5%；Granule strength：90-95%；Selection
Property：90-95%；Lot number：X88887；Producer：Shandong West Asia chemical industry Co., Ltd
2) experimental procedure
Methyl orange electrolyte (the methyl orange that will be prepared：40mg/L；Na2SO4：0.05mol/L；FeSO4·7H2O：
It is 1-2,3-4,5-6,13-14 0.5mmol/L) to adjust pH respectively, then pours into respectively in 500mL beakers, is put into Pd/C gases
Diffusion electrode, it is passed through oxygen cylinder conduit, oxygen gas flow rate 300mL/min, preaeration 20min.
Take out Pd/C gas-diffusion electrodes and assemble reaction tank, add 40mL methyl orange electrolyte, access oxygen cylinder is led
Pipe, loads onto platinum filament anode, connects the both positive and negative polarity of DC power supply, opens DC power supply switch, and regulation electric current is
100mA, timing 30min.
DC power supply switch is closed, takes out oxygen cylinder conduit, methyl orange electrolyte is loaded into 50mL centrifuge tubes protects
Deposit.Sample is surveyed to absorbance and TOC and COD respectively.(by ten groups of contrast experiments, averaging)
3) experimental result
| PH value | Degradation rate (%) | TOC clearances (%) |
| 1-2 | 99.1 | 16.65 |
| 3-4 | 99.5 | 42.95 |
| 5-6 | 96.4 | 12.5 |
| 13-14 | 12.4 | 20.8 |
4) experiment conclusion
Experiment shows, when solution ph is 3-4, the effect of the Pd/C catalyst degradation organic pollution methyl oranges of biosynthesis
Fruit is best, degradation rate 99.5%, and TOC clearances are 42.95%.
Embodiment 3
By palladium carbon catalyst made from bioanalysis electric Fenton-like system negative electrode application example-organic pollution methyl orange
Degradation experiment：
1) experiment material
Pd/C gas-diffusion electrodes：Weigh powdered carbon 9g and be put into large beaker, submerged with ethanol, be stirred continuously in the heater
The general temperature of 15-20min reaches 80 DEG C, adds 15mLPTFE, then constantly observation, with hand examination until can into viscous shape after 1-2h
Kneading to take out, and finally rolled repeatedly with tablet press machine, until surface is smooth, thickness is moderate, then is placed on stainless (steel) wire and presses
The thin slice integrally changed.The piece pressed is put into Muffle furnace, and heat up 100min, and stopping 20min at 340 DEG C fires, after cooling terminates
Take out standby.The electrode slice prepared is cut into diameter 2.5cm with scissors, area is 4.9cm2 circular piece.Weigh equivalent
Palladium nano-particles are put into 2.0mL EP pipes, are then respectively adding 200 μ L Nafion and 200 μ L pure water, and ultrasound is allowed to mix
Uniformly.Finally palladium liquid is uniformly coated onto in circular piece with hairbrush, Pd/C load capacity is respectively 2mg/cm2、4mg/cm2And 6mg/
cm2, it is overnight air-dry after save backup.
Methyl orange：40mg/L
Na2SO4：0.05mol/L
FeSO4·7H2O：0.5mmol/L
Commodity Pd/C：No. CAS：7440-05-3；Molecular formula：Pd/C；Palladium content：5%；Granule strength：90-95%；Selection
Property：90-95%；Lot number：X88887；Producer：Shandong West Asia chemical industry Co., Ltd
2) experimental procedure
Methyl orange electrolyte (the methyl orange that will be prepared：40mg/L；Na2SO4：0.05mol/L；FeSO4·7H2O：
0.5mmol/L) pour into 500mL beakers, be put into Pd/C gas-diffusion electrodes, be passed through oxygen cylinder conduit, oxygen gas flow rate is
300mL/min, preaeration 20min.
Take out Pd/C gas-diffusion electrodes and assemble reaction tank, add 40mL methyl orange electrolyte, access oxygen cylinder is led
Pipe, loads onto platinum filament anode, connects the both positive and negative polarity of DC power supply, opens DC power supply switch, and regulation electric current is
100mA, timing 30min.
DC power supply switch is closed, takes out oxygen cylinder conduit, methyl orange electrolyte is loaded into 50mL centrifuge tubes protects
Deposit.Sample is surveyed to absorbance and TOC and COD respectively.(by ten groups of contrast experiments, averaging)
3) experimental result
| Load capacity (mg/cm2) | Degradation rate (%) | TOC clearances (%) |
| 2 | 97.9 | 11.3 |
| 4 | 99.0 | 15.45 |
| 6 | 90.4 | 5.25 |
4) experiment conclusion
Experiment shows that Pd/C load capacity is 4mg/cm2When, the Pd/C catalyst degradation organic pollution methyl of biosynthesis
The effect of orange is best, degradation rate 99.0%, and TOC clearances are 15.45%.
Claims (8)
1. a kind of biological preparation method applied to electric Fenton-like system cathod catalyst, it is characterised in that prepare step including following
Suddenly：
Step 1, preparation of reagents；
1) preparation of LB culture mediums
By sodium chloride, tryptone and dusty yeast in mass ratio 2:2:1 amount is weighed, and ultra-pure water constant volume is used after mixing, and LB is made
Nutrient solution just liquid, then liquid at the beginning of the LB nutrient solutions is sealed, sterilize and cooling treatment after save backup, obtain LB culture
Base；
2) preparation of anaerobic culture medium
Weigh respectively three water dipotassium hydrogen phosphates, potassium dihydrogen phosphate, sodium chloride, ammonium sulfate, epsom salt, HEPES, sodium lactate and
Micro- storing solution, ultra-pure water constant volume is used after mixing, then adjust pH value to 7.0 with sodium hydroxide, obtain Anaerobic culturel liquid
First liquid；Liquid at the beginning of the Anaerobic culturel liquid is added in serum bottle, saves backup, obtains after inflated with nitrogen, sealing and sterilization treatment
Anaerobic culture medium；
3) preparation of Pd (II) mother liquor
With the ultra-pure water after sterilizing under the conditions of lucifuge by chlorine palladium acid sodium grain dissolution, constant volume, solution is then poured into bacterium of having gone out
Brown bottle in, sealing is placed in refrigerator and saved backup；
Step 2, S.oneidensis MR-1 culture；
After S.oneidensis MR-1 are taken out from -80 DEG C of refrigerators and carry out LB plate streaking processing to it, culture dish is fallen
Button, which is put into constant incubator, to be cultivated, and marks date and bacterial strain；Then the LB flat boards after line is handled, which are put into refrigerator, to be sealed
Preserve；Selected on the LB flat boards S.oneidensis MR-1 monoclonals be put into the LB culture mediums and 30 DEG C,
Cultivated in 150rpm shaking table；
Step 3, S.oneidensis MR-1 cleaning and collection；
Centrifugal treating is carried out to cultured bacterium solution in step 2, supernatant is removed, retains bottom precipitation；Then with the anaerobism
Culture medium carries out repeated washing, centrifugal treating to bottom precipitation respectively, repeats 3 times, with the anaerobic culture medium after cleaning
Bottom precipitation bacterium solution is cultivated, obtains S.oneidensis MR-1 collection liquids；
Step 4, S.oneidensis MR-1 OD600The measure of value；
Measure S.oneidensis MR-1 collection liquids described in 100 μ L and be diluted with water to 10mL, mix；By spectrophotometer ripple
It is long to be adjusted to 600nm, determine 2 times, average, calculate the concentration OD of collection liquid600；
Step 5, biological reducing palladium and collection drying process；
2) the S.oneidensis MR-1 collection liquids are scattered in in the serum bottle equipped with anaerobic culture medium, then to institute
Chlorine palladium acid sodium solution standby in being injected 3) in serum bottle is stated, 3h is cultivated in 30 DEG C, 150rpm shaking table；Then by mixed liquor
Centrifuged, washed successively, is repeated 3 times, the bacterium palladium mixed liquor of collection is placed in -70 DEG C of refrigerator and freezes 1h, is put after taking-up
Enter and 72h is dried in freeze drier, weigh；
Step 6, the alkali activation process of material；
By dried bacterium palladium mixture in step 5 and KOH in mass ratio 1:After 1 mixing, mixture is put into tube furnace
Row heating；After room temperature cooling, cleaned respectively with the hydrochloric acid and deionized water that mass fraction is 5% to neutralize alkali and go to dechlorinate
Ion residues；Dry, grind and preservation of weighing after, obtain target product.
2. it is applied to the biological preparation method of electric Fenton-like system cathod catalyst as claimed in claim 1, it is characterised in that 1)
Described in LB nutrient solutions just liquid be to be settled to 2800mL with ultra-pure water by 28g sodium chloride, 28g tryptones and 14g dusty yeasts to obtain
Arrive；The sterilization treatment is that liquid at the beginning of the LB nutrient solutions is placed into 20min in the case where 121 DEG C, pressure is 0.13MPa to be sterilized.
3. it is applied to the biological preparation method of electric Fenton-like system cathod catalyst as claimed in claim 1, it is characterised in that 2)
Described in Anaerobic culturel liquid just liquid be by the water dipotassium hydrogen phosphates of 1.132g tri-, 0.675g potassium dihydrogen phosphates, 1.380g sodium chloride,
0.765g ammonium sulfate, 0.072g epsom salts, 14.298gHEPES, 6.726g sodium lactate and 15mL trace element storing solutions mix
After conjunction obtained by ultra-pure water is settled to 3000mL；3) concentration of Pd described in (II) mother liquor is 15mmol/L, and solution is loaded into palm fibre
Seal and be placed in 4 DEG C of refrigerators in color bottle and saved backup.
4. it is applied to the biological preparation method of electric Fenton-like system cathod catalyst as claimed in claim 1, it is characterised in that step
Rapid three and step 5 in the centrifugal treating, the rotating speed of centrifuge is 7000-8000rpm, centrifugation time 15-20min.
5. it is applied to the biological preparation method of electric Fenton-like system cathod catalyst as claimed in claim 1, it is characterised in that step
Mixture described in rapid six is the heating of 420 DEG C of the progress in the tube furnace of vacuum atmosphere, and heating rate is 1 DEG C/min,
A length of 3h during heated at constant temperature.
6. the biological preparation method applied to electric Fenton-like system cathod catalyst as described in claim 1 or 3, its feature exist
In the micro- storing solution is by 1.5g NTA, is settled to 500mL using ultra-pure water, is adjusted with potassium hydroxide
PH value is saved to 6.5, then adds 3.0g magnesium sulfate, 1.0g calcium chloride dihydrates, 1.0g sodium chloride, 0.5g manganese sulfates, the water of 0.18g seven
Zinc sulfate, 0.1g ferrous sulfate heptahydrates, 0.18g cobalt sulfates, the water nickel chlorides of 0.025g six, the water of 0.02g 12 and aluminum sulfate
Potassium, 0.01g cupric sulfate pentahydrates, 0.01g boric acid, 0.01g Sodium Molybdate Dihydrates, 0.3mg Sodium selenite (Na2SeO3) pentahydrates, used again after shaking up dissolving
Ultra-pure water is dissolved to obtained by 1000mL.
7. a kind of Pd/C catalyst, it is characterised in that the Pd/C catalyst is used as any right will in claim 1-5
Ask made from the described biological preparation method applied to electric Fenton-like system cathod catalyst.
8. it is a kind of using Pd/C catalyst as claimed in claim 7 electric Fenton-like system negative electrode application.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710389A (en) * | 2013-11-25 | 2014-04-09 | 大连理工大学 | Biosynthesis method of magnetic Pd nanocomposite material |
| CN103936115A (en) * | 2014-05-14 | 2014-07-23 | 中国科学院新疆理化技术研究所 | Three-dimensional electro-fenton water treatment method |
-
2017
- 2017-09-13 CN CN201710820459.XA patent/CN107497422A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710389A (en) * | 2013-11-25 | 2014-04-09 | 大连理工大学 | Biosynthesis method of magnetic Pd nanocomposite material |
| CN103936115A (en) * | 2014-05-14 | 2014-07-23 | 中国科学院新疆理化技术研究所 | Three-dimensional electro-fenton water treatment method |
Non-Patent Citations (4)
| Title |
|---|
| HUI WANG等: ""Comparative study on electrochemical degradation of 2,4-dichlorophenol by different Pd/C gas-diffusion cathodes"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| SONGHU YUAN等: ""Pd-Catalytic In Situ Generation of H2O2 from H2 and O2 Produced by Water Electrolysis for the Efficient Electro-Fenton Degradation of Rhodamine B"", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》 * |
| WIM DE WINDT等: ""Bioreductive deposition of palladium (0) nanoparticles on reductive dechlorination of polychlorinated biphenyls"", 《ENVIRONMENTAL MICROBIOLOGY》 * |
| 孔宛芹: ""纳米钯协同Shewanella oneidensis MR-1还原转化氯硝基苯类化合物的研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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