CN111533244A - Co based on sheet-like flexible carbon cloth3O4Nano-structured microbial composite material and preparation method and application thereof - Google Patents

Co based on sheet-like flexible carbon cloth3O4Nano-structured microbial composite material and preparation method and application thereof Download PDF

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CN111533244A
CN111533244A CN202010394408.7A CN202010394408A CN111533244A CN 111533244 A CN111533244 A CN 111533244A CN 202010394408 A CN202010394408 A CN 202010394408A CN 111533244 A CN111533244 A CN 111533244A
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carbon cloth
sheet
nano
composite material
flexible carbon
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CN111533244B (en
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路建美
陈冬赟
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Suzhou University
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Suzhou University
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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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses Co based on sheet-shaped flexible carbon cloth3O4The preparation method comprises the following steps of sequentially carrying out sulfuric acid cleaning, solvent cleaning and nitric acid soaking on carbon cloth to obtain treated carbon cloth; mixing the treated carbon cloth with ammonia water, glycol, sodium carbonate and cobalt nitrate, carrying out hydrothermal reaction, and calcining to obtain Co3O4Nanosheets; loading of microorganisms to Co3O4Obtaining Co based on the sheet-shaped flexible carbon cloth on the nano sheet3O4A nanostructured microbial composite. The invention successfully prepares Co by a hydrothermal method3O4The composite material disclosed by the invention has better adsorption and degradation effects on azo dyes. In addition, the invention can effectively combine the adsorption method with the biological method and fully exert the adsorption method and the biological methodThe method has the advantages of good development potential and application prospect.

Description

Co based on sheet-like flexible carbon cloth3O4Nano-structured microbial composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of composite material preparation, and particularly relates to pretreatment of carbon cloth and Co3O4Preparation method of nanosheet composite material and application of nanosheet composite material in azo dye treatment。
Background
With the rapid development of the social economy and printing industry, the environmental problems are particularly prominent, and people are attracted strong attention. Dyes have become an important component of the textile, printing, cosmetic, pharmaceutical and food processing industries, and complex dye components can induce mutation in animals and humans and have teratogenic effects, wherein azo dyes account for the largest proportion of harmful dyes; in addition, the biological carcinogenic, teratogenic and mutagenic effects of the anilines produced by azo dyes are more severe. Therefore, the removal of dyes from dye waste water has become an important issue for water treatment. Therefore, finding an economic and sustainable method becomes a hot spot of domestic and foreign research. The biological method has the advantages of economy, environmental protection and sustainability, people pay attention to the method, if microorganisms are directly used for degrading the dye, the degradation time is long, and the high-concentration dye can also influence the microorganisms. Therefore, the mere utilization of microorganisms is limited in practical practice and further investigation is required.
Disclosure of Invention
The invention discloses Co on flexible carbon cloth with a sheet structure3O4A nano-structured microbial composite material prepared from Co, its preparing process and its application3O4The flaky nano structure is combined with the pretreated carbon cloth through a hydrothermal method and finally compounded with microorganisms, so that the effects of local enrichment and separation of the dye are realized, and the treatment effect on the azo dye is achieved.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
co based on flaky flexible carbon cloth3O4The preparation method of the nano-structured microbial composite material comprises the following steps:
(1) sequentially carrying out sulfuric acid cleaning, solvent cleaning and nitric acid soaking on the carbon cloth to obtain treated carbon cloth;
(2) mixing the treated carbon cloth with ammonia water, glycol, sodium carbonate and cobalt nitrate, carrying out hydrothermal reaction, and then calcining to obtain Co3O4Nanosheets;
(3) loading of microorganisms to Co3O4Obtaining Co based on the sheet-shaped flexible carbon cloth on the nano sheet3O4A nanostructured microbial composite.
The invention also discloses a treatment method of the azo dye, which comprises the following steps:
(1) sequentially carrying out sulfuric acid cleaning, solvent cleaning and nitric acid soaking on the carbon cloth to obtain treated carbon cloth;
(2) mixing the treated carbon cloth with ammonia water, glycol, sodium carbonate and cobalt nitrate, carrying out hydrothermal reaction, and then calcining to obtain Co3O4Nanosheets;
(3) loading microorganisms to the Co3O4Obtaining Co based on the sheet-shaped flexible carbon cloth on the nano sheet3O4A nanostructured microbial composite;
(4) co based on the sheet-shaped flexible carbon cloth3O4And adding the nano-structure microbial composite material into an azo dye solution to complete the treatment of the azo dye.
The invention discloses Co based on sheet-shaped flexible carbon cloth3O4The preparation method of the nano-structure microbial composite material can specifically comprise the following steps:
(1) first, the carbon cloth was cut into small pieces and H was used2SO4Cleaning is carried out, followed by H2SO4Sequentially carrying out ultrasonic treatment on the treated carbon cloth by using acetone, water and ethanol for further cleaning, and finally, carrying out ultrasonic treatment on the cleaned carbon cloth by using HNO3Soaking;
(2) adding concentrated NH3·H2Mixing O and EG under vigorous stirring; then adding Na2CO3Pouring into the mixture and further stirring; then adding Co (NO)3)2Adding the mixture into the mixture and further stirring; then transferring the solution into a stainless steel high-pressure reaction kettle, and inserting the pretreated carbon cloth into the reaction kettle to perform hydrothermal reaction; the carbon cloth-loaded Co was then removed from the autoclave3O4Washing the nanocrystals with water and ethanol in sequence, and oven dryingDrying in the middle; finally calcining the precursor in air to obtain Co3O4Nanosheet, noted CC/Co3O4；
(3) Loading of microorganisms to Co3O4Obtaining Co based on sheet-shaped flexible carbon cloth on the surface of the nanosheet3O4A nanostructured microbial composite.
In the above technical scheme, in the step (1), the sulfuric acid used is a sulfuric acid solution, wherein H is2SO4Has a concentration of 1mol/L, H2SO4The cleaning time is 2 hours; the ultrasonic treatment time of acetone, water and ethanol is 30 minutes; HNO3The soaking time was 12 hours.
In the technical scheme, in the step (2), the dosage ratio of ammonia water, glycol, sodium carbonate and cobalt nitrate is 12.5 mL: 15 mL: 3.5 mmol: 5mmol, preferably, the sodium carbonate is 1M Na2CO3Adding aqueous solution of cobalt nitrate in 1M Co (NO)3)2Adding the aqueous solution; the time and the temperature of the hydrothermal reaction are respectively 8 hours and 180 ℃; the drying temperature is 60 ℃; the calcination was at 300 ℃ for 5 hours.
In the above technical scheme, in the step (3), Co is added3O4The nano-sheet is activated by NHS, DCC and DMAP; then the microorganism and the activated Co3O4Dispersing the nano-sheets in PBS together, oscillating by a constant temperature shaking table to obtain Co loaded with microorganisms3O4The carbon cloth composite material with the nano structure is Co based on flaky flexible carbon cloth3O4A nanostructured microbial composite.
The invention also discloses Co based on the flaky flexible carbon cloth3O4Application of the nano-structured microbial composite material in azo dye treatment.
The scheme has the advantages that:
1. the invention discloses the prepared CC/Co3O4Namely, the preparation method of the carbon cloth composite material loaded with the cobaltosic oxide nanosheets is simple, the cost of the raw material carbon cloth is low, and the carbon cloth composite material is easy to obtain and treat. The test method and instrument in the experiment are more common。
2. The carbon cloth composite material loaded with cobaltosic oxide nanosheets prepared by the method disclosed by the invention can realize effective adsorption and biodegradation of azo dyes, and the used raw material carbon cloth is high in stability, free of pollution and good in application prospect in the aspect of environmental protection.
3. The carbon cloth composite material loaded with cobaltosic oxide nanosheets obtained by the invention has good adsorption efficiency on azo dyes, can completely remove pollutants, can effectively combine an adsorption method with a biological method, and exerts the advantages of the adsorption method and the biological method.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of a pretreated carbon cloth;
FIG. 2 shows Co3O4Scanning Electron Micrographs (SEM);
FIG. 3 is CC/Co3O4Scanning Electron Micrographs (SEM);
FIG. 4 shows a loadP.Putida CC/Co3O4Scanning Electron Micrographs (SEM);
FIG. 5 shows CC/Co3O4The adsorption effect graph on azo dyes (50 mg/L);
FIG. 6 shows CC/Co3O4Graph of adsorption effect on azo dye (100 mg/L)
FIG. 7 shows a loadP. putidaCC/Co of3O4A graph of the degradation effect on azo dyes (50 mg/L);
FIG. 8 shows a loadP. putidaCC/Co of3O4The degradation effect on azo dyes is shown (100 mg/L).
Detailed Description
The invention discloses Co based on sheet-shaped flexible carbon cloth3O4The preparation method of the nano-structure microbial composite material comprises the following steps:
(1) sequentially carrying out sulfuric acid cleaning, solvent cleaning and nitric acid soaking on the carbon cloth to obtain treated carbon cloth;
(2) mixing the treated carbon cloth with ammonia water, glycol, sodium carbonate and cobalt nitrateHydrothermal reaction and then calcination to obtain Co3O4Nanosheets;
(3) loading microorganisms to the Co3O4Obtaining Co based on the sheet-shaped flexible carbon cloth on the nano sheet3O4A nanostructured microbial composite.
(4) Co based on the sheet-shaped flexible carbon cloth3O4And adding the nano-structure microbial composite material into an azo dye solution to complete the treatment of the azo dye.
Specifically, the invention discloses a microorganism-loaded Co3O4The preparation method of the carbon cloth composite material with the nano structure can be expressed as follows:
(1) pretreatment of carbon cloth
First, the carbon cloth was cut into small pieces and H was used2SO4Cleaning is carried out, followed by H2SO4And (4) ultrasonically treating the treated carbon cloth by using acetone, water and ethanol in sequence to further clean. Finally, the treated carbon cloth is treated by HNO3And (5) soaking.
（2）CC/Co3O4Preparation of the Complex
Adding concentrated NH3·H2O is mixed with EG under vigorous stirring. Then, adding Na2CO3Poured into the above mixture and further stirred. Thereafter, Co (NO) is added3)2Adding into the mixture and stirring. Then, the solution was transferred to a stainless steel autoclave, and the pretreated carbon cloth was inserted into the autoclave. The hydrothermal reaction is carried out for 8 hours in a stainless steel high-pressure reaction kettle. Subsequently, the carbon cloth-supported Co was taken out of the autoclave3O4The nanocrystals were washed sequentially with water and ethanol and dried in an oven. Finally, the precursor is calcined in air to obtain Co3O4Nanosheet, noted CC/Co3O4。
(3) Load(s)P. putidaCC/Co of3O4Preparation of
Loading of microorganisms to CC/Co3O4Surface to thereby obtain nanogenerationA composite material.
All the raw materials are commercially available, and the specific preparation method and the test method are conventional technologies.
The embodiment I comprises the following specific steps of:
first, the carbon cloth was cut into small pieces (1 mm by 1 mm) and tested at 1M H2SO4Cleaning was carried out by continuous sonication in aqueous solution for 2 hours, followed by H2SO4The treated carbon cloth is further cleaned by ultrasonic treatment for 30 minutes respectively by acetone, water and ethanol. Finally, the treated carbon cloth is treated by HNO3(8M) soak treatment for 12 hours to give a treated carbon cloth, which was used in example two. FIG. 1 is a scanning electron microscope image of the pretreated carbon cloth, and the surface of the pretreated carbon cloth can be seen neatly.
Example II CC/Co3O4The preparation method of the compound comprises the following specific steps:
12.5mL of concentrated NH3·H2O (28 wt%) was mixed with 15mL EG (ethylene glycol) for 2 minutes with vigorous stirring. Then, 3.5mL (1M) of Na was added2CO3The aqueous solution was poured into the above mixture and stirred for 2 minutes. Thereafter, 5mL of 1M Co (NO)3)2The aqueous solution was added to the mixture and stirred for another 20 minutes. Then, the solution was transferred to a 50mL Teflon-lined stainless steel autoclave, and the above pretreated carbon cloth (0.5 g) was inserted into the autoclave, and the stainless steel autoclave was maintained at 180 ℃ for 8 hours and naturally cooled at room temperature. Subsequently, the carbon cloth-supported Co was taken out of the autoclave3O4The nanocrystals were washed thoroughly 3 times with water and ethanol in sequence and dried in an oven at 60 ℃ for 12 hours. Finally, Co was obtained by calcining the precursor at 300 ℃ in air for 5 hours3O4Nanosheet, noted CC/Co3O4For example three and dye treatment.
FIG. 2 and FIG. 3 are Co alone and Co alone, respectively3O4And CC/Co3O4Scanning electron micrographs of the composites, FIG. 2 showing Co alone3O4Is a sheet structure, and Co can be seen in FIG. 33O4The loading on the carbon cloth is successful, the loading is uniform, the loading amount is very dense, and the sheet structure is still kept.
Example three loadsP. putida(Pseudomonas putida) CC/Co3O4The preparation method comprises the following specific steps:
100mg of dried CC/Co3O4And 100mg of NHS (N-N-hydroxysuccinimide) were dispersed in a 100 mL round-bottomed flask containing 50mL of DMF, and 300 mg of DCC (N, N' -dicyclohexylcarbodiimide) and 178 mg of DMAP (4-dimethylaminopyridine) were added, stirred at room temperature for 24 hours for activation, and then centrifuged and washed 3 times with PBS. Culturing Pseudomonas putida in 50mL LB culture medium, centrifuging, washing with PBS for 3 times, and activating the thallus and CC/Co3O4Dispersed together in 50mL PBS at 30oC, placing the mixture in a constant temperature shaking table at 150 rpm for 24 hours to shake, connecting a large number of carboxyl functional groups on the surface with amino groups on the surface of the bacteria through chemical bonds, and firmly loading the bacteria on the CC/Co3O4Obtaining Co based on sheet-shaped flexible carbon cloth on the surface of the composite material3O4A nanostructured microbial composite.
FIG. 4 shows a loadP. putidaCC/Co of3O4Can be seen from the scanning electron microscope imageP. putidaHas been firmly loaded to CC/Co3O4As above, it was confirmed that the load had been successfully preparedP. putidaCC/Co of3O4A nano-composite material.
Example four CC/Co3O4The method for adsorbing the azo dye comprises the following specific steps:
in the adsorption experiment, 100mg of CC/Co is weighed respectively3O450mL of an aqueous solution of dye AO10 (50, 100 mg/L) at various initial concentrations were added, samples were taken at intervals, and the AO10 concentration in the solution was determined by UV-visible spectrophotometer at a wavelength of 478 nm until no further change in the equilibrium concentration of adsorption was achieved.
FIG. 5 and FIG. 6 are CC/Co, respectively3O4The adsorption effect of azo dye (50, 100 mg/L) is shown by pictures, and CC/Co can be seen in the initial stage3O4Rapid adsorption can be performed followed by a slowing to the adsorption equilibrium where the equilibration times are 30 minutes and 50 minutes respectively.
Example five loadsP. putidaCC/Co of3O4The method for degrading the azo dye comprises the following specific steps:
in the degradation experiment, 100mg of load was weighed out separatelyP. putidaCC/Co of3O450mL of different initial concentrations of aqueous dye AO10 (50, 100 mg/L) were added, samples were taken at intervals, and the AO10 concentration in the solution was determined by UV-visible spectrophotometer at a wavelength of 478 nm until no further change in the equilibrium concentration of adsorption was achieved.
FIG. 7 and FIG. 8 show a load, respectivelyP. putidaCC/Co of3O4The degradation effect of azo dye (50, 100 mg/L) is shown in the figure, the whole adsorption degradation can be completed by two processes, and CC/Co is used as an initial stage3O4Adsorbing azo dye, and loading when adsorption reaches balanceP. putidaCC/Co of3O4Degradation process of azo dyes. The adsorption degradation was completed in 13 hours and 27 hours for azo dyes at concentrations of 50mg/L and 100mg/L, and the degradation rate reached 100%.
According to the above method, AO10 aqueous solution (50 mg/L) was added aloneP. putida(Pseudomonas putida, using the culture method of example III), the degradation rate was 70% after 15 hours.
According to the method, the magnetic nanoparticle microbial composite material with the core-shell structure disclosed in the prior CN107583621A is added into an AO10 aqueous solution (50 mg/L) independently, and the degradation rate is 80% after 15 hours.
Directly replacing CC/Co of the third embodiment with the treated carbon cloth of the first embodiment3O4The prepared composite material is used for the dye treatment experiment, the effect is not good, and the degradation rate is 65 hours after 15 hours in AO10 aqueous solution (50 mg/L)%。
To summarize:
through the analysis, the CC/Co is successfully prepared by the hydrothermal method3O4Namely the carbon cloth composite material loaded with cobaltosic oxide nano-sheets, and the nano-composite material disclosed by the invention has good adsorption and degradation effects on azo dyes. In addition, the invention can effectively combine the adsorption and biological methods, integrate the adsorption and degradation, and fully utilize the advantages of the adsorption and degradation, and the novel adsorption and degradation method has great development potential and very wide application prospect.

Claims (10)

1. Co based on flaky flexible carbon cloth3O4Nanostructured microbial composites characterized by said Co based on sheet-like flexible carbon cloth3O4The preparation method of the nano-structure microbial composite material comprises the following steps:
(1) sequentially carrying out sulfuric acid cleaning, solvent cleaning and nitric acid soaking on the carbon cloth to obtain treated carbon cloth;
(2) mixing the treated carbon cloth with ammonia water, glycol, sodium carbonate and cobalt nitrate, carrying out hydrothermal reaction, and then calcining to obtain Co3O4Nanosheets;
(3) loading of microorganisms to Co3O4Obtaining Co based on the sheet-shaped flexible carbon cloth on the nano sheet3O4A nanostructured microbial composite.
2. Co based on sheet-like flexible carbon cloth according to claim 13O4The nano-structured microbial composite material is characterized in that in the step (1), the concentration of sulfuric acid is 1 mol/L.
3. Co based on sheet-like flexible carbon cloth according to claim 13O4The nano-structured microbial composite material is characterized in that in the step (2), the dosage ratio of ammonia water, glycol, sodium carbonate and cobalt nitrate is 12.5 mL: 15 mL: 3.5 mmol: 5 mmol.
4. Co based on sheet-like flexible carbon cloth according to claim 13O4The nano-structured microbial composite material is characterized in that in the step (2), the hydrothermal reaction time is 8 hours, and the temperature is 180 ℃; the calcination was at 300 ℃ for 5 hours.
5. Co based on sheet-like flexible carbon cloth according to claim 13O4The nanostructured microbial composite material is characterized in that, in the step (3), Co is added3O4The nano-sheet is activated by NHS, DCC and DMAP, and then the microorganism is loaded on Co3O4And (4) nano-chips.
6. Co based on sheet-like flexible carbon cloth according to claim 13O4Nanostructured microbial composites characterized by microbial loading on Co3O4The nano-scale reaction is carried out in a buffer solution under the shaking of a constant temperature shaking table.
7. A method for treating azo dyes, comprising the following steps:
(1) sequentially carrying out sulfuric acid cleaning, solvent cleaning and nitric acid soaking on the carbon cloth to obtain treated carbon cloth;
(2) mixing the treated carbon cloth with ammonia water, glycol, sodium carbonate and cobalt nitrate, carrying out hydrothermal reaction, and then calcining to obtain Co3O4Nanosheets;
(3) loading microorganisms to the Co3O4Obtaining Co based on the sheet-shaped flexible carbon cloth on the nano sheet3O4A nanostructured microbial composite;
(4) co based on the sheet-shaped flexible carbon cloth3O4And adding the nano-structure microbial composite material into an azo dye solution to complete the treatment of the azo dye.
8. The method for treating azo dyes according to claim 7, wherein the time for cleaning with sulfuric acid is 2 hours; the solvent cleaning is sequentially cleaning with acetone, water and ethanol; the time for the nitric acid soak was 12 hours.
9. The method for treating an azo dye according to claim 7, wherein the calcination is carried out in air in the step (2).
10. Co based on sheet-like flexible carbon cloth according to claim 13O4Application of the nano-structured microbial composite material in azo dye treatment.
CN202010394408.7A 2020-05-11 2020-05-11 Co based on sheet-like flexible carbon cloth 3 O 4 Nano-structure microbial composite material and preparation method and application thereof Active CN111533244B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108176403A (en) * 2018-01-24 2018-06-19 四川农业大学 A kind of activated carbon fiber-loaded Co3O4The preparation method of catalysis material
CN109569500A (en) * 2018-12-13 2019-04-05 苏州大学 Sour modified meerschaum Biological nanocomposite of loading microorganisms and the preparation method and application thereof
CN110124704A (en) * 2019-06-19 2019-08-16 哈尔滨工业大学 A kind of preparation method for the cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108176403A (en) * 2018-01-24 2018-06-19 四川农业大学 A kind of activated carbon fiber-loaded Co3O4The preparation method of catalysis material
CN109569500A (en) * 2018-12-13 2019-04-05 苏州大学 Sour modified meerschaum Biological nanocomposite of loading microorganisms and the preparation method and application thereof
CN110124704A (en) * 2019-06-19 2019-08-16 哈尔滨工业大学 A kind of preparation method for the cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate

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