专利摘要:
This invention proposes a method for the reduction of graphene oxide by the use of microorganisms comprising the following steps: reactivation and cultivation of the microbial biomass; preparation of a medium where the reduction process occurs, either on the solid graphene oxide or dispersed in an aqueous medium; and the contribution of a microbial element that produces the reduction of the oxide; where the aqueous medium occurs this reaction is tap water without any additional treatment, such as the additional contribution of nutrients or carbon sources, very common in other microbial cultures or a sheet of graphene oxide. Likewise, the temperature at which the reaction occurs is what could be considered "room temperature" and the process can be performed under aerobic conditions, but both characteristics must respect the limits and requirements of the microbial element to allow its growth. This process develops under simple conditions, because it is a passive microbial process that indirectly depends on the microbial metabolism. (Machine-translation by Google Translate, not legally binding)
公开号:ES2695310A1
申请号:ES201730850
申请日:2017-06-28
公开日:2019-01-03
发明作者:Delgado Raquel Simarro;Santa Cruz Luis Fernando Bautista;Fernandez Carolina Vargas;Benitez Natalia Gonzalez;Cobos Maria Del Carmen Molina;Pena Eva Maria Diaz;Peraltas Jose Alberto Reina
申请人:Universidad Rey Juan Carlos;
IPC主号:
专利说明:

[0001]
[0002]
[0003]
[0004] TECHNICAL SECTOR
[0005]
[0006] The present invention relative to the microbial reduction of graphene oxide belongs to the sector of the biological synthesis of nanomaterials, more specifically to the biological synthesis of reduced graphene oxide.
[0007]
[0008] The main object of the present invention is a biological process to reduce graphene oxide by producing graphene oxide reduced biologically by various microorganisms and microbial consortiums, which provides this field with an environmentally sustainable, fast and economical process for obtaining graphene of a certain purity. .
[0009]
[0010] BACKGROUND OF THE INVENTION
[0011]
[0012] Graphene is a carbon nanomaterial and main component of graphite, whose crystalline structure consists of one or more two-dimensional carbon atoms with hexagonal arrangement. The monolayer structure provides graphene with unusual properties: hardness, (similar to that of diamond and about 200 times greater than that of steel), high elasticity and flexibility (greater durability), high thermal conductivity (-4-103 Wm'1K'1 ) and electrical (~ 1-106 Q "1m" 1, higher than that of common conductive metals), transparent and very light (0.77 mg-m "2) and resistant to ionizing radiation.
[0013]
[0014] Its unique properties give it diverse applications in increasingly diverse fields of action, in which graphene is considered as a base material for devices and structures. Electronic technology is one of the most developed fields of application at present in which graphene is considered as the main component for the manufacture of optoelectronic devices (screens) that form part of mobile phones, glass screens ifquido (LCD) or fiber optic communications systems. The use of graphene as a battery is proposed as one of the alternatives with greater future projection. Other applications of graphene extend to fields related to environmental technologies focused on the sorption and photocatalysis of pollutant compounds and as a detector of atmospheric gases such as NO2 and CO. The applicability of graphene extends to fields as transcendental as biomedicine being used as a biosensor for detection in organisms of neurotransmitters or heavy metals.
[0015]
[0016] The most widespread processes for the synthesis of graphene, are based mainly on physical-chemical or chemical methods that directly use the graphite or other precursor as starting material, to obtain graphene oxide and later graphene, after a chemical process of reduction. The physical methods are based mainly on the repeated descaling of graphite by exfoliation and splitting [Novoselov et al 2004. Science, 306: 666-669], while the chemical methods involve the use of reducing agents whose main representative is hydrazine or N -methyl pyrrolidone [Hernandez et al. 2008. Nature Nanotechnology, 3: 563-568]. The latter are reproducible and highly productive processes, but the use of toxic and corrosive reducing agents such as hydrazine is a brake on their future industrial development. There is a second generation of processes based on electrochemical or thermal technologies that are proposed as scalable and reproducible, but also with a negative impact from the environmental point of view given the high level of energy consumption involved [Gurunathan et al 2013. Colloids and Surfaces , 102: 772 777], which implies a high economic cost [Wang et al 2013. Nature Materials, 12: 81 87].
[0017]
[0018] One of the most promising technologies are those based on biological processes to reduce graphene oxide and obtain reduced graphene oxide, whose properties are equal to the graphene obtained chemically proportional to the degree of reduction, in a fast, viable, reproducible and environmentally friendly process. respectful. The process can be developed in an active way, which implies the direct reduction of the oxide at the expense of the anaerobic metabolism of the microorganisms or through the use of certain cellular structures such as pylons. However, graphene oxide can be reduced passively and independently to microbial metabolism, as an indirect consequence of the movement of electrons and electron launchers that they are activated during microbial activity. The scientific studies that develop these processes involve the use of bacterial strains belonging to the genus Shewanella or the species Escherichia coli using aqueous or nutritious media [Akhavan and Ghaderi 2012. Carbon, 50: 1853-1860], under aerobic or anaerobic conditions given the condition facultative of the strains used. In this sense the following patents show biological processes of graphene production: Sun (CN103255177) presents a process of reduction of OG in aqueous medium under anaerobiosis using denitrifying bacteria; Sun (CN103395775) proposes the reduction of graphite oxide in aqueous medium by supplying Staphylococcus spp. in a fuel cell anode; Liu (CN103255177) patents the reduction of graphene oxide in aqueous medium and anaerobic conditions using as reducing agent reducing sulphate bacteria to obtain graphene simultaneously doped with sulfur and nitrogen.
[0019]
[0020] Contrary to these patents, this application proposes a novel method of graphene oxide reduction that, on the one hand, does not use chemical agents but microbial elements and, on the other hand, produces the chemical reaction in a simple aqueous medium, or on oxide. of solid graphene, under environmental conditions and without the need to use any additional additive or special nutrient medium.
[0021]
[0022] EXPLANATION OF THE INVENTION
[0023]
[0024] The biological process for obtaining reduced graphene oxide object of the invention comprises the use of strains and consortiums of microorganisms for the reduction of graphene oxide and its conversion into reduced graphene oxide, whose characteristics are more similar to graphene be its degree of reduction. The process is developed in a fast, environmentally sustainable and economically viable way by means of the microbial reduction of graphene oxide passively, which allows the process to be carried out in an aqueous, aerobic and at room temperature or on a solid structure of Graphene oxide.
[0025]
[0026] The main advantages of this process are:
[0027] • Simple environmental conditions: aerobic conditions, room temperature and aqueous reduction medium.
[0028] • Obtaining reduced graphene oxide quickly.
[0029] • Reduction agent: microbial biomass such as, for example, rapidly growing bacteria strains such as Escherichia coli, Shewanella baltica and Bacillus sp, facultative aerobes and mesophylls, or a microbial consortium from Rio Tinto, with reducing, facultative and mesophilic characteristics, although be any micro-organism, since it is a passive process.
[0030]
[0031] In general, the complete process of biological reduction is carried out following the following steps:
[0032] 1- Cultivation and growth of microbial strains and consortia. This is a standard process where the culture of microorganism, once grown, is washed and separated by a solid-liquid separation process such as, for example, sedimentation, centrifugation or filtration, for the removal of remains of the nutrient medium and collection of biomass.
[0033] 2- In the second step, object of this patent, the process of reducing a suspension of graphene oxide in water or on a sheet of graphene oxide, inoculating or extending respectively, the biomass collected in the first step is performed.
[0034] 3- In the third step the recovery of the product obtained after the reduction process, reduced graphene oxide, is carried out by sonication and centrifugation of the suspension, to eliminate the cells and the subsequent evaporation of the water by drying, to collect the reduced graphene oxide of the cell-free suspension. In case of working on sheets of graphene oxide, the sheets are cleaned to eliminate the cells by sonicating the sheet in an aqueous medium.
[0035]
[0036] This invention proposes a method for the reduction of graphene oxide by the use of microorganisms comprising the following steps: preparation of a medium where the reduction process takes place (graphene oxide sheet or an aqueous medium in which the dispersion is dispersed) graphene oxide) and the contribution of a microbial element to the reduction medium in the form of biomass, which passively produces the reduction of the oxide; where the aqueous medium in which the reaction occurs is simple water, without any type of additional treatment, such as the additional contribution of nutrients or carbon sources, very common in other biological processes. Likewise, the temperature at which the reaction occurs is the which is considered "ambient temperature", between 15 ° C and 30 ° C, but always depends on the range of action of the biological element that is used in the process.
[0037]
[0038] For a greater yield of the reduction reaction in aqueous media, the graphene oxide in the water can be dispersed by any of the conventional methods: manual agitation, vortex, etc., or with a low frequency ultrasound system, such as be, for example, at 20 Hz.
[0039]
[0040] Any concentration of the microbial element dissolved in the water reduces the graphene oxide, but the concentration between 30 mg / ml and 100 mg / ml produces especially good results, in the balance between reaction time and product obtained. It also occurs with the concentration of graphene oxide dispersed in water, although anyone is valid between 0.2 and 4 mg / ml obtain optimal yields.
[0041]
[0042] This reduction of graphene oxide can be made with all types of microorganisms. In this patent it is exemplified with the use of bacteria belonging to the genera Shawanella, Escherichia and Bacillus. As it happens between the different types of microorganisms (fungi, bacteria, microalgae) that can be used, specific species within each genre can show better results than others. Thus, in the examples of the present invention, despite the differences that may exist depending on the bacterial species used, any bacteria from each of the genera would be capable of adequately reducing the graphene oxide. To name a few, the species Escherichia coli produces excellent results in the reduction process. Microbial associations forming consortia, coming from certain habitats, are also capable of reducing graphene oxide. Microbial consortia are associations of microorganisms of various genera and associated species in a particular habitat in which they act cooperatively together. Specifically for the process that concerns us, the natural consortium of microorganisms from the Rio Tinto basin, has been especially active in the reduction of graphene oxide, possibly due to the natural processes of oxidation-microbial reduction of heavy metals and sulfides. that occur in a low pH environment.
[0043]
[0044] After the reduction process, the last step will be the recovery of the product, reduced graphene oxide, by a process that allows us to eliminate the microbial cells of the reduced product, either in solid phase or in sheet, based on the sonication and separation of the aqueous phase (when appropriate). The aqueous phase with the suspension cells or the graphene sheet immersed in water is sonicated in an ultrasonic bath for 20 minutes to allow the particles of the reduced graphene oxide that may be adsorbed on the cell surface to be released or release the cells from the surface of the sheet. Later, with the objective of eliminating the cells of the aqueous solution, the sample is centrifuged at a speed in a range of between 1,500 and 15,000 rpm, obtaining an optimum result at 13,000 rpm for 10 min. The supernatant contains the reduced graphene oxide dispersed in water, free of cells, which is then dried to obtain the reduced graphene oxide.
[0045]
[0046] BRIEF DESCRIPTION OF THE DRAWINGS
[0047]
[0048] To complement the description that is being made and in order to help a better understanding of the reproducibility and effectiveness of the process of microbial reduction of graphene oxide, a set of figures is included as an integral part of said description, with illustrative character and not limiting, the following has been represented:
[0049]
[0050] Figure 1: X-ray diffraction of an unreduced graphene oxide sample, in the lower part of the graficak, and after being subjected to a process of bacterial reduction by the strains Bacillus sp CECT40., Shewanella baltica CECT 323, Escherichia coli CECT 101 and the microbial consortium of Rio Tinto.
[0051]
[0052] Figure 2.- Thermogravimetry showing the loss of weight produced between 0 and 1000 ° C of a sample of graphene oxide (OG) without reducing compared to samples of graphene oxide biologically reduced by Bacillus sp CECT 40, Shewanella baltica CECT 323 ( S. baltica), Escherichia coli CECT 101 ( E. coli) and the microbial consortium of Rio Tinto.
[0053]
[0054] PREFERRED EMBODIMENT OF THE INVENTION
[0055]
[0056] The microorganisms used to exemplify the microbial process of reduction of graphene oxide comprising the present patent, are bacterial strains obtained from the Spanish Collection of Type Cultures (CECT) previously isolated from environmental samples from sediments and subsequently cultivated and identified. In addition, one of the proposed processes is carried out with a microbial consortium from the waters of the Rio Tinto. In any case, the bacterial biomass was cultivated and stored at -20 ° C until its use.
[0057]
[0058] First, the process of reactivation of microbial biomass for its cultivation and subsequent use as a microbial element that will reduce graphene oxide is shown by several examples. This is a process of reactivation and cultivation of biomass that can be applied in a general way for all microorganisms, although with certain specifications depending on the microorganism used, for the cultivation of biomass of any type of microorganism. The specifications will be determined by the type of culture medium or optimum temperature, or the incubation period required by each microorganism. Thus, the process of reactivation and cultivation of biomass in a generalized manner comprises the following phases: 1) reactivation of frozen or lyophilized microbial biomass in an optimum culture medium, at the optimum growth temperature of the microorganism; 2) incubation of the microorganisms until it reaches the appropriate cell density and it remains stable; 4) collection and washing of the biomass to separate the aqueous phase and remove remains of nutrients from the medium; 5) application of the biomass to the aqueous medium or to the solid element containing the graphene oxide so that the reduction process takes place.
[0059]
[0060] In the examples that follow, the reactivation and cultivation of biomass of the microbial strains used as an example in this patent is specified as a biological element to reduce graphene oxide. This process will be carried out in the same way for all strains: the microbial strains are cultured in solid nutritive culture media (bacto-tryptone 10 gl-1, extract of bacto-yeast 5 gl-1, NaCl 5 gl-1, agar ) at 30 ° C. From this biomass, liquid mother cultures of each strain and of the consortium without previous plate culture were prepared in nutritive medium (bacto-tryptone 10 gl-1, bacto-yeast extract 5 gl-1, NaCl 5 gl-1) , at 25 ° C, dark and constant stirring to provide oxygen. The cultures are kept in incubation until the cell density estimated from the measurement of the absorbance of the culture in a spectrophotometer at 600 nm, is constant (approximately 3 days). In this At this time, the biomass is harvested by centrifuging the culture twice for 15 minutes at 1500 rpm. Finally, and to eliminate any trace of medium, the biomass is washed with buffered saline and recentrifuged.
[0061]
[0062] Example 1: Graphene oxide reduction process with Bacillus sp CECT 40 Once biomass is obtained in the manner explained above, the culture is formed where the reduction process will be made up of 30 ml of aqueous solution with 0.4 mg / ml dispersed graphene oxide and 45 mg / ml biomass of Bacillus sp CECT 40. The process is carried out under aerobic conditions for which the cultures are maintained in agitation (150 rpm) and room temperature for 72 h.
[0063]
[0064] Once this time has elapsed, the last step consists in extracting the graphene oxide biologically reduced by Bacillus sp CECT 40 from the aqueous solution with cells. The culture is introduced in an ultrasonic bath and sonicated for 10 min and a double centrifugation at 1500 rpm 15 min. The supernatant containing the biologically reduced graphene oxide is dried in an oven at 65 ° C for 24 hours.
[0065]
[0066] The sample was analyzed by UV-vis, Raman and infrared spectroscopies (FT-IR), X-ray diffraction and thermogravimetry to determine the characteristics of the reduced graphene oxide.
[0067]
[0068] Bacillus sp CECT 40. is a bacterial strain effective in the reduction of graphene oxide as demonstrated by the characterization of the product obtained. After the process of reduction of graphene oxide by Bacillus sp CECT 40., the aqueous suspension of graphene oxide turns brown-brown to black which indicates the reduction thereof. The UV-vis spectroscopy shows that the final product has an absorption spectrum slightly displaced towards the visible range with a maximum absorption at 250 nm compared to the maxima that the graphene oxide has at 230 and 300 nm. The Raman spectroscopy shows that Bacillus displaces 5.74 cm-1 bands D and G with respect to its position in graphene oxide (1333 cm-1 and 1593 cm-1, respectively) and has a higher ID / IG intensity ratio. X-ray diffraction analysis (Figure 1) showed a consistent decrease in peak to 10.3 ° OG characteristic, which is attributed to the elimination of oxygen-containing functional groups during the reduction process. Finally, thermogravimetric analysis (Figure 2) indicates that Bacillus sp CECT 40 reduces the oxide of graphene forming a stable product with only a percentage of weight loss of 16.49% between 0-600 ° C compared to a 65.34% weight loss of graphene oxide. These results indicate a lower presence of oxygenated groups in the biologically reduced graphene oxide and a greater stability of the reduced product after 72 h of incubation.
[0069]
[0070] Example 2: process of reduction of graphene oxide with Shewanella baltica CECT 323
[0071] Once biomass is obtained, the culture is formed where the reduction process will be carried out, consisting of 30 ml of aqueous solution with 0.4 mg / ml dispersed graphene oxide and 45 mg / ml of biomass from Shewanella baltica CECT 323. The process is carried out under conditions aerobic for which crops are maintained in agitation (150 rpm) and room temperature for 72 h.
[0072]
[0073] Once this time has elapsed, the last step consists in extracting the graphene oxide biologically reduced by Shewanella baltica CECT 323 from the aqueous solution with cells. The culture is subjected to sonication in an ultrasonic bath for 10 min and a double centrifugation at 1500 rpm for 15 min. The supernatant containing the biologically reduced graphene oxide is dried in an oven at 65 ° C for 24 hours. The sample was analyzed by UV-vis, Raman and infrared spectroscopies (FT-IR), X-ray diffraction and thermogravimetry.
[0074]
[0075] Shewanella baltica CECT 323 is a bacterial strain effective in the reduction of graphene oxide as demonstrated by the characterization of the product obtained. After the process of reduction of graphene oxide by Shewanella baltica CECT 323, the aqueous suspension of graphene oxide turns brownish-brown to black, which indicates the reduction of it. The UV-vis spectroscopy shows that the final product has an absorption spectrum slightly displaced towards the visible range with a maximum absorption at 250 nm compared to the maxima that the graphene oxide has at 230 and 300 nm. The Raman spectroscopy shows that, after 48 hours of reduction, Shewanella baltica CECT 323 displaces 10.66 cm-1 and 5.48 cm-1, respectively, bands D and G in relation to their position in graphene oxide and presents a ratio of intensities ID / IG slightly higher. X-ray diffraction (Figure 1) showed a consistent decrease in peak at 10.3 °, characteristic of OG, which is attributed to the elimination of oxygen-containing functional groups during the reduction process. Finally, the thermogravimetric analysis between 0 and 600 ° C (Figure 2) indicates that Shewanella baltica CECT 323 reduces the graphene oxide and forms a stable product after 48 hours of reduction since this product has a percentage of weight loss of 5.88% between 0-600 ° C versus 65.34% weight loss of graphene oxide. These results indicate less presence of oxygenated groups in the biologically reduced product with respect to graphene oxide. These results indicate that Shewanella baltica CECT 323 is the one bacterial strain that effectively reduces graphene oxide under aerobic conditions and 48 h.
[0076]
[0077] Example 3: Graphene oxide reduction process with Escherichia coli CECT 101 Once the biomass is obtained, the culture is formed where the reduction process will be carried out with 30 ml of aqueous solution with 0.4 mg / ml graphene oxide and 45 mg / ml of biomass of E. coli CECT 101. The process is carried out under aerobic conditions for which the cultures are maintained in agitation (150 rpm) and room temperature for 72 h.
[0078]
[0079] Once this time has elapsed, the last step consists in extracting the graphene oxide biologically reduced by E. coli CECT 101, from the aqueous solution with cells. The culture is sonicated in an ultrasonic bath for 10 min and a double centrifugation at 1500 rpm for 15 min. The supernatant containing the biologically reduced graphene oxide is dried in an oven at 65 ° C for 24 hours. The sample was analyzed by UV-vis, Raman and infrared spectroscopy (FT-IR), X-ray diffraction and thermogravimetry.
[0080]
[0081] E. coli CECT 101 is a bacterial strain effective in the reduction of graphene oxide, as shown by the characterization of the product obtained. After the process of reducing graphene oxide by E. coli CECT 101, the aqueous suspension of graphene oxide turns brownish-brown to black, which indicates the reduction thereof. The UV-vis spectroscopy shows that the final product has an absorption spectrum slightly displaced to the visible range with a maximum absorption only at 250 nm compared to the maxima that the graphene oxide has at 230 and 300 nm. Raman spectroscopy shows that, after 72 h of reduction, E. coli CECT 101 displaces 4.96 cm-1 and 1.3 cm-1, respectively, bands D and G in relation to their position in graphene oxide and presents a ratio of intensities ID / IG slightly higher. The X-ray diffraction (Figure 1) showed a consistent decrease in peak at 10.3 °, characteristic of OG, which is attributed to the elimination of oxygen-containing functional groups during the reduction process. Finally, the thermogravimetric analysis between 0 and 600 ° C (Figure 2) indicates that E. coli CECT 101 reduces the graphene oxide and forms a stable product after 72 hours of reduction since this product has a weight loss percentage of 12.72. % between 0-600 ° C versus 65.34% weight loss of graphene oxide. These results indicate less presence of oxygenated groups in the biologically reduced product with respect to graphene oxide. These results indicate that E. coli CECT 101 is a bacterial strain that effectively reduces graphene oxide under aerobic conditions and 72 h.
[0082]
[0083] Example 4: graphene oxide reduction process with consortium from the Rio Tinto
[0084] From biomass of the Rio Tinto consortium, the medium is formed where the reduction process will be carried out with 30 ml of an aqueous solution with 0.4 mg / ml dispersed graphene oxide and 45 mg / ml of biomass from the Rio Tinto microbial consortium. The process is carried out under aerobic conditions for which the cultures are maintained in agitation (150 rpm) and room temperature for 72 h.
[0085]
[0086] Once this time has elapsed, the last step consists in the extraction of the graphene oxide reduced biologically by the bacterial consortium of the Rio Tinto, of the aqueous solution with cells. The culture is sonicated in an ultrasonic bath for 10 min and a double centrifugation at 1500 rpm for 15 min. The supernatant containing the biologically reduced graphene oxide is dried in an oven at 65 ° C for 24 hours. The sample was analyzed by UV-vis, Raman and infrared spectroscopies (FT-IR), X-ray diffraction and thermogravimetry.
[0087]
[0088] The isolated microbial consortium of Rio Tinto is effective in the reduction of graphene oxide as demonstrated by the characterization of the product obtained. After the graphene oxide reduction process by the Rio Tinto bacterial consortium, the aqueous suspension of graphene oxide turns brown-brown to black, which indicates its reduction. The infrared spectroscopy shows a progressive increase of the transmittance of the bands with maximums at 1630 cm-1 and 1100 cm-1, corresponding to the vibration of the C = C and CO bonds, which is much more accused after 72 hours of reduction. The UV-vis spectroscopy shows that the final product has an absorption spectrum slightly displaced to the visible range with a maximum absorption only at 250 nm compared to the maxima that the graphene oxide has at 230 and 300 nm. The Raman spectroscopy shows that the bacterial consortium generates a displacement of the D band of 1.31 cm-1 and 7.83 cm-1 after 48 and 72 h of reduction, respectively. The ratio of ID / IG intensities suffered an increase of 19.2% with respect to the value of graphene oxide after 48 h of the process. X-ray diffraction (Figure 1) showed a consistent decrease in peak at 10.3 °, characteristic of OG, which is attributed to the elimination of oxygen-containing functional groups during the reduction process. Finally, the thermogravimetric analysis between 0 and 600 ° C (Figure 2) indicates that the bacterial consortium reduces the graphene oxide and forms a stable product with hardly any difference between 48 and 72 h since this product presents a percentage of weight loss of the 7.02% and 8.69% respectively between 0-600 ° C versus 65.34% weight loss of graphene oxide. These results indicate less presence of oxygenated groups in the biologically reduced product with respect to graphene oxide. These results indicate that the Rio Tinto consortium is a bacterial strain that effectively reduces graphene oxide under aerobic conditions after 48 h and 72 h.
权利要求:
Claims (16)
[1]
1. Procedure for the reduction of graphene oxide by the use of microorganisms comprising the following steps:
to. reactivation of the microorganism and cultivation of biomass;
b. preparation of an aqueous medium or of the solid element containing the graphene oxide, where the reaction takes place;
c. contribution of microbial biomass to the medium containing the graphene oxide, where the reduction occurs, characterized in that the medium where the microbial element reduces the graphene oxide is at room temperature, without additional contribution of nutrients and / or carbon sources.
[2]
2. Process for the reduction of graphene oxide by the use of micro-organisms, according to claim 1, characterized in that the medium where the reaction takes place is an aqueous medium or a solid element, which contains the graphene oxide.
[3]
3. Process according to claim 1 or 2, characterized in that the graphene oxide can be supplied solidly, in the form of a film or film or dispersed in an aqueous medium.
[4]
4. Method, according to any of the preceding claims, characterized in that the medium where the reduction is carried out is water.
[5]
5. Process, according to any of the preceding claims, characterized in that the graphene oxide and the microbial element must be in contact.
[6]
6. Process, according to any of the preceding claims, characterized in that in an aqueous medium the graphene oxide and the microbial biomass are mixed to obtain a uniform mixture.
[7]
7. Process, according to any of the preceding claims, characterized in that in the aqueous medium, the dispersion of the graphene oxide is obtained by a solid-liquid mixing process as ultrasound.
[8]
8. Method, according to any of the preceding claims, characterized in that the microbial element forms an aqueous biofilm on the solid graphene oxide or is in the aqueous medium with the graphene oxide in dispersion.
[9]
9. Process, according to any of the preceding claims, characterized in that the microbial element in aqueous medium can be in a concentration between 30 and 100 mg / mL.
[10]
10. Method, according to any of the preceding claims, characterized in that the reducing element can be any type of unicellular microorganism whether fungus, bacteria or microalga.
[11]
11. Method according to any of the preceding claims, characterized in that the reducing element can be a bacterial strain selected from a group comprising the bacterial genera Shewanella, Escherichia and Bacillus.
[12]
12. Method according to any of the preceding claims, characterized in that the bacterial element is Escherichia coli CECT 101, Shewanella baltica CECT 323 or Bacillus sp. CECT 40
[13]
Method, according to any of the preceding claims, characterized in that the reducing element can be a microbial consortium formed by a compendium of associated microorganisms that come from the same environment or habitat.
[14]
14. Process, according to any of the preceding claims, characterized in that the reducing element is a microbial consortium from the waters of the Rio Tinto.
[15]
15. Recovery process of graphene oxide reduced microbiologically in an aqueous medium comprising the following steps:
to. the mixture is subjected to a sonication process, to release the reduced graphene oxide particles;
b. the microbial cells are separated from the aqueous phase by sedimentation or centrifugation;
c. and the supernatant is dried without bacterial cells to obtain the reduced graphene oxide.
[16]
16. Graphene oxide recovery process microbiologically reduced when this is a film or film comprising the following steps:
to. the film is subjected to a sonication process, to release the cells adhered to the reduced graphene oxide sheet; b. the sheet is washed with distilled water;
c. and dries to remove traces of water.
类似技术:
公开号 | 公开日 | 专利标题
Yang et al.2018|Algal biofilm-assisted microbial fuel cell to enhance domestic wastewater treatment: nutrient, organics removal and bioenergy production
Rashid et al.2013|Enhanced electricity generation by using algae biomass and activated sludge in microbial fuel cell
ElMekawy et al.2014|Techno-productive potential of photosynthetic microbial fuel cells through different configurations
Junfeng et al.2010|Biodegradation of microcystin-RR by a new isolated Sphingopyxis sp. USTB-05
Yan et al.2013|Carbon nanotubes promote Cr | reduction by alginate-immobilized Shewanella oneidensis MR-1
He et al.2014|Simultaneous wastewater treatment, electricity generation and biomass production by an immobilized photosynthetic algal microbial fuel cell
Kong et al.2014|Improved dechlorination and mineralization of 4-chlorophenol in a sequential biocathode–bioanode bioelectrochemical system with mixed photosynthetic bacteria
Wang et al.2019|Cost-effective domestic wastewater treatment and bioenergy recovery in an immobilized microalgal-based photoautotrophic microbial fuel cell |
Guo et al.2012|Reduction of Cr | by Escherichia coli BL21 in the presence of redox mediators
Parvanova-Mancheva et al.2009|Microbial denitrification by immobilized bacteria Pseudomonas denitrificans stimulated by constant electric field
Tomaszewski et al.2019|Short-term effects of reduced graphene oxide on the anammox biomass activity at low temperatures
Li et al.2009|Anaerobic biotransformation of azo dye using polypyrrole/anthraquinonedisulphonate modified active carbon felt as a novel immobilized redox mediator
Wang et al.2008|Autocatalysis in Reactive Black 5 biodecolorization by Rhodopseudomonas palustris W1
Qu et al.2015|Biodegradation of indole by a newly isolated Cupriavidus sp. SHE
Wang et al.2019|Growth enhancement of biodiesel-promising microalga Chlorella pyrenoidosa in municipal wastewater by polyphosphate-accumulating organisms
Chen et al.2020|Degradation and metabolic pathways of sulfamethazine and enrofloxacin in Chlorella vulgaris and Scenedesmus obliquus treatment systems
Li et al.2019|Enhancement of CO2 biofixation and bioenergy generation using a novel airlift type photosynthetic microbial fuel cell
Tang et al.2022|Calcium ions-effect on performance, growth and extracellular nature of microalgal-bacterial symbiosis system treating wastewater
Li et al.2021|Enhancing biomethane production and pyrene biodegradation by addition of bio-nano FeS or magnetic carbon during sludge anaerobic digestion
Liu et al.2021|Synergetic effects of biochars and denitrifier on nitrate removal
Liu et al.2020|Autotrophic induced heterotrophic bioreduction of bromate in use of elemental sulfur or zerovalent iron as electron donor
ES2695310B2|2019-05-27|BIOLOGICAL PROCESS FOR THE OBTAINING OF REDUCED GRAFEN OXIDE, THROUGH THE USE OF MICROORGANISMS
Li et al.2012|Biodegradation of 3, 4-dichloroaniline by a novel Myroides odoratimimus strain LWD09 with moderate salinity tolerance
Gabrielyan et al.2016|Comparative effects of Ni | and Cu | ions and their combinations on redox potential and hydrogen photoproduction by Rhodobacter sphaeroides
Luo et al.2021|Enhancing nitrate removal from wastewater by integrating heterotrophic and autotrophic denitrification coupled manganese oxidation process |: Internal carbon utilization performance
同族专利:
公开号 | 公开日
ES2695310B2|2019-05-27|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题
US20150336799A1|2014-05-23|2015-11-26|Mariam Al Ali Alamaadeed|Simple production method for graphene by microorganisms|
法律状态:
2019-01-03| BA2A| Patent application published|Ref document number: 2695310 Country of ref document: ES Kind code of ref document: A1 Effective date: 20190103 |
2019-05-27| FG2A| Definitive protection|Ref document number: 2695310 Country of ref document: ES Kind code of ref document: B2 Effective date: 20190527 |
优先权:
申请号 | 申请日 | 专利标题
ES201730850A|ES2695310B2|2017-06-28|2017-06-28|BIOLOGICAL PROCESS FOR THE OBTAINING OF REDUCED GRAFEN OXIDE, THROUGH THE USE OF MICROORGANISMS|ES201730850A| ES2695310B2|2017-06-28|2017-06-28|BIOLOGICAL PROCESS FOR THE OBTAINING OF REDUCED GRAFEN OXIDE, THROUGH THE USE OF MICROORGANISMS|
[返回顶部]