CN115888760A - Photocatalytic nanomaterial-microorganism heterozygote and preparation method and application thereof - Google Patents
Photocatalytic nanomaterial-microorganism heterozygote and preparation method and application thereof Download PDFInfo
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a photocatalytic nano material-microorganism heterozygote and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding graphene oxide into a mixed solution containing water-soluble divalent cadmium salt, thiourea and polyvinylpyrrolidone, carrying out hydrothermal reaction, washing, and drying in vacuum to obtain a CdX/RGO material; culturing Shewanella under aerobic condition to obtain bacterial liquid; dispersing the CdS/RGO material in an anaerobic buffer solution to obtain a buffer solution A; centrifuging the bacterial solution of the Shewanella, removing the supernatant, dispersing the centrifuged precipitate cells into a buffer solution A, mixing and stirring to obtain the CdS/RGO/MR-1 material. The invention prepares a novel hybrid of photocatalysis-biology synergy high-efficiency hydrogen production, which can realize the high-efficiency transmission of photo-generated electrons from outside to inside of cells for catalase so as to promote the light energy utilization efficiency and the hydrogen production efficiency.
Description
Technical Field
The invention belongs to the technical field of green hydrogen energy production, and particularly relates to a hybrid of a photocatalyst, a conductive carbon material and a microorganism, a preparation method of the hybrid and hydrogen production application of the hybrid.
Background
Solar hydrogen production is a clean energy production technology with great development potential, the technology usually utilizes photocatalyst to decompose water to produce hydrogen, but because of the limitation of light absorption range or photon-generated carrier recombination and other factors, the hydrogen production efficiency of the existing photocatalyst is generally not high. In addition, the hydrogen can be generated by utilizing the microorganism to anaerobically decompose the organic matters, and the technology can be coupled with a wastewater treatment process, thereby providing a new way for recycling wastewater. However, the existence of other competitive organic catabolic pathways results in insufficient electron donors to be effectively utilized for hydrogen production, thereby also limiting the hydrogen production efficiency and long-term operating stability.
In recent years, researchers have attempted to construct inorganic-biological hybrid systems (IBSs) to couple photocatalytic and bio-hydrogen production processes. The system can provide additional electrons for microbial metabolism by utilizing the excellent light absorption performance of inorganic semiconductor materials, and meanwhile, hydrogen is produced by catalyzing organic matter conversion by utilizing catalase in microbial cells, so that the hydrogen production process with continuity, stability and low cost is hopefully realized. However, the photocatalytic material is located outside the cell, and the microorganism catalase is located inside the cell, so that the photo-generated electrons are difficult to be effectively utilized by the microorganism, and the hydrogen production efficiency of the IBSs is severely limited. The key to breaking through this bottleneck is to increase the electron transfer rate at the interface between the material and the microbial cell. At present, researchers Lower, B.H. and the like (APPLIED AND ENVIRONMENTAL MICROBIOLOGY,2009.75 (9): p.2931-2935) try to utilize soluble electronic media such as dye molecules and the like to construct an electronic channel between a photocatalyst and intracellular catalase, but the diffusion mass transfer efficiency of the substances is low and the substances can be lost continuously, and part of the electronic media molecules also have cytotoxicity and are not beneficial to long-term efficient and stable operation. Therefore, there is an urgent need to develop inorganic-biological hybrids with stronger interfacial electron transfer capability to improve the solar hydrogen production conversion efficiency.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a hybrid of a photocatalyst, a conductive carbon material and a microorganism, a preparation method thereof and hydrogen production application, solves the problem of low interface electron transfer efficiency in a photocatalytic composite system constructed by an inorganic material and microbial cells at present, utilizes a microorganism (such as Shewanella) with excellent transmembrane electron transfer capability and hydrogen production capability, adds a two-dimensional nano material (such as graphene oxide) with better biocompatibility and conductivity between the inorganic photocatalytic material (such as cadmium sulfide and CdS) and the microbial cells as an electron transfer medium, enforces the combination of the inorganic material and the biological cells and improves the interface electron transfer efficiency, thereby realizing the high-efficiency transfer of photo-generated electrons from the outside of the cells to the inside of the cells to promote the light energy utilization efficiency and the hydrogen production efficiency.
The technical scheme of the invention is as follows:
the invention relates to a preparation method of a photocatalytic nano material-microorganism heterozygote, which comprises the following steps:
(1) Preparation of CdS/RGO
Adding Graphene Oxide (GO) into a mixed solution containing water-soluble divalent cadmium salt, thiourea and polyvinylpyrrolidone, carrying out hydrothermal reaction, washing, and drying in vacuum to obtain a CdX/RGO material;
(2) Culture of Shewanella
Culturing Shewanella under aerobic condition to obtain bacterial liquid;
(3) Preparation of CdS/RGO/MR-1
Dispersing the CdS/RGO material in an anaerobic buffer solution to obtain a buffer solution A; centrifuging the bacterial liquid obtained in the step (2) to remove the supernatant, dispersing the centrifuged precipitate cells into a buffer solution A, mixing and stirring to obtain the CdS/RGO/MR-1 material.
Preferably, the water-soluble divalent cadmium salt is cadmium chloride.
Preferably, the concentration of the divalent cadmium salt is 90-100mmol/L, the concentration of thiourea is 90-100mmol/L, and the concentration of polyvinylpyrrolidone is 10-12mg/mL;
in the step (1), the graphene oxide is added in the form of an ethylene glycol solution of the graphene oxide, the concentration of the ethylene glycol solution of the graphene oxide is 0.4-0.6mg/mL, and the mass of the graphene oxide accounts for 0.5-0.9% of the mass of the polyvinylpyrrolidone.
Preferably, in the step (1), the hydrothermal reaction temperature is 160-200 ℃ and the time is 12-20h; the vacuum drying temperature is 60-80 deg.C, and the drying time is 6-12h.
Preferably, in the step (2), the culture process of the bacterial liquid comprises the following steps: shewanella is inoculated in advance and primary aerobic culture is carried out under aerobic conditions, and then 10-20mL of aerobically cultured bacterial liquid is taken and transferred into 100-200mL of fresh culture solution to be aerobically cultured again under the same conditions.
Preferably, the culture solution used in step (2) is an LB (Luria-Bertani) medium, and further preferably, the LB medium contains the following components: 5g/L of yeast extract, 10g/L of tryptone and 10g/L of sodium chloride, wherein the pH value of an LB culture medium is 6.8-7.2;
the time of primary aerobic culture is 11-13h, and the time of secondary aerobic culture is 11-13h.
Preferably, in the step (3), the concentration of the CdS/RGO material in the buffer A is 0.025-0.1g/L; when the buffer solution A is prepared, the CdS/RGO material is dispersed in an anaerobic buffer solution by ultrasonic for 40-60min;
centrifuging to obtain precipitate, transferring to buffer solution A, and magnetically stirring for 30-40min with Shewanella bacteria OD600 value of 1-3 in anaerobic buffer solution.
Preferably, the anaerobic buffer solution used in the step (3) is subjected to aeration oxygen removal and sterilization treatment, wherein the aeration oxygen removal time is 30-40min, the sterilization temperature is 121 ℃, and the sterilization time is 20min;
the anaerobic buffer solution contains 50mmol/L hydroxyethyl piperazine ethanethiosulfonic acid, 50mmol/L sodium chloride, 20mmol/L sodium lactate and 1mmol/L ascorbic acid, and has a pH value of 6.8-7.2.
The invention also relates to a photocatalytic nano material-microorganism heterozygote prepared by the preparation method.
The invention also relates to the application of the photocatalytic nano material-microorganism heterozygote in solar hydrogen production.
The invention has the beneficial effects that:
1) According to the invention, microorganisms with excellent transmembrane electron transfer capacity and hydrogen production capacity are utilized, and a two-dimensional nanomaterial with better biocompatibility and conductivity is added between an inorganic photocatalytic material and microbial cells as an electron transfer medium, so that the inorganic material and the biological cells are combined, the interface electron transfer efficiency is improved, the efficient transfer of photoproduction electrons from the outside to the inside of cells and catalase is realized, and the light energy utilization efficiency and the hydrogen production efficiency are promoted;
2) Compared with the conventional IBSs, the novel IBSs constructed by the invention can realize the high-efficiency collection of photoelectrons and the rapid transfer between the photoelectrons and microbial cells; the CdS/RGO/MR-1 hybrid system constructed by the method has the advantages of high stability and high hydrogen production performance, the hydrogen production of the hybrid system in 12 hours is obviously far greater than that of a CdS/MR-1 system and an MR-1 system, the operation is simple, the preparation process is safe, and the cost is low;
3) The IBSs with high-efficiency electron transfer performance constructed by the invention have wide application prospects in the fields of solar hydrogen production and other photocatalysis.
Drawings
The invention is further described with reference to the following figures and examples:
FIG. 1 SEM topographic image of CdS/RGO in example 1;
FIG. 2: panel A is an SEM image of CdS/RGO/MR-1 in example 1; b is the EDS-mapping image of C, O, cd and the S element of the area framed by A;
FIG. 3 is an XRD pattern for CdS/RGO, cdS and RGO materials;
FIG. 4: the A picture is a C1s map of graphene oxide GO; B-D diagrams sequentially show the C1S, cd 3D and S2p maps of CdS/RGO in example 1;
FIG. 5 Effect of bacteria concentration and material concentration on hydrogen production performance in example 1;
FIG. 6 cumulative hydrogen production for different hybrid systems of example 1 and comparative examples 1-2;
FIG. 7 is a graph showing cumulative hydrogen production in the case of light and in the case of dark in the experimental group;
FIG. 8 XRD pattern of CdS/RGO-MR-1 after the end of the photocatalytic reaction in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It is to be understood that these descriptions are only illustrative and are not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
The invention provides a preparation method of a photocatalytic nano material-microorganism heterozygote, which comprises the following steps:
(1) Taking a proper amount of water-soluble divalent cadmium salt and thiourea) and polyvinylpyrrolidone (PVP) to dissolve in ethylene glycol to form a homogeneous mixed solution; wherein the water-soluble divalent cadmium salt is preferably cadmium chloride, the concentration of the divalent cadmium salt is 90-100mmol/L, the concentration of thiourea is 90-100mmol/L, and the concentration of polyvinylpyrrolidone is 10-12mg/mL;
(2) Adding a proper amount of graphene oxide into the mixed solution obtained in the step (1), carrying out hydrothermal reaction for a period of time (the reaction temperature is 160-200 ℃ and the time is 12-20 hours), repeatedly washing the graphene oxide with water and ethanol, and carrying out vacuum drying (the temperature is 60-80 ℃ and the time is 6-12 hours) to obtain the CdS/RGO material, wherein the graphene oxide is added in the form of a glycol solution of the graphene oxide, the concentration of the glycol solution of the graphene oxide is 0.4-0.6mg/mL, and the mass of the graphene oxide accounts for 0.5-0.9% of that of polyvinylpyrrolidone;
(3) Inoculating Shewanella with good activity in advance, performing primary aerobic culture for 11-13h under aerobic condition, transferring 10-20mL of aerobic culture solution to 100-200mL of fresh culture solution, and performing aerobic culture for 11-13h under the same condition; wherein the culture solution is LB (Luria-Bertani) culture medium, and more preferably, the LB culture medium comprises the following components: 5g/L of yeast extract, 10g/L of tryptone and 10g/L of sodium chloride, and the pH value of an LB culture medium is 6.8-7.2;
(4) Preparing an anaerobic reactor filled with an anaerobic buffer culture medium, removing oxygen by aerating inert gas (argon), and sterilizing after aeration; the culture medium contains the following components: 50mmol/L hydroxyethylpiperazine ethanethiosulfonic acid, 50mmol/L sodium chloride, 20mmol/L sodium lactate, and 1mmol/L ascorbic acid, wherein the pH range is 6.8-7.2; the aeration time is 30-40min, the sterilization temperature is 121 ℃, and the time is 20min;
(5) Adding a proper amount of the CdS/RGO material prepared in the step (2) into the anaerobic reactor in the step (4), and further uniformly dispersing by ultrasonic to obtain a buffer solution A, wherein the concentration of the CdS/RGO material in the buffer solution A is preferably 0.025-0.1g/L, and is further preferably 0.05g/L;
(6) Centrifuging a proper amount of the Shewanella bacteria liquid cultured in the step (3) to remove supernatant, then centrifuging to obtain precipitates, washing the precipitates for 2-3 times by using a buffer salt culture medium, then resuspending, transferring the precipitates into the buffer solution A in the step (5), wherein the OD600 value of Shewanella in an anaerobic buffer solution is 1-3, further placing an anaerobic reactor on a magnetic stirrer for mixing and stirring, and the magnetic stirring time is 30-40min to obtain a photocatalytic nano material-microorganism hybrid system (CdS/RGO/MR-1 material).
Example 1
(1) Preparation of CdS/RGO: 3.5mmol of cadmium chloride (CdCl) 2 . 2.5H 2 O) with 3.5mmol of thiourea (NH) 2 CSNH 2 ) And 389mg polyvinylpyrrolidone (PVP) is dissolved in 35mL of ethylene glycol, graphene oxide (5 mL,0.5mg/mL of ethylene glycol solution of graphene oxide) is added, a homogeneous solution is formed by ultrasonic treatment, and hydrothermal reaction is carried out for 12 hours at 160 ℃; centrifuging (10000rpm, 10min) to obtain yellow precipitate; then washing for six times by water and ethanol, and drying for 6 hours in vacuum at 80 ℃ to obtain a CdS/RGO material;
(2) Culture of Shewanella: selecting a strain of Shewanella oneidensis MR-1; inoculating Shewanella strain into 50mL LB medium (containing yeast extract 5g/L, tryptone 10g/L and sodium chloride 10g/L, pH = 7), and shaking at 30 deg.C (200 rpm) for 12h to obtain bacterial liquid; transferring 20mL of bacterial liquid into 200mL of fresh LB culture medium according to the volume ratio of 1;
(3) Preparation of CdS/RGO/MR-1: dispersing 1.5mg CdS/RGO photocatalyst in an anaerobic reactor filled with 30mL of anaerobic buffer solution by ultrasonic dispersion (the anaerobic buffer solution contains 50mmol/L of hydroxyethyl piperazine ethanesulfonic acid, 50mmol/L of sodium chloride, 20mmol/L of sodium lactate and 1mmol/L of ascorbic acid, the pH value is 7.0, the anaerobic buffer solution removes oxygen by exposing inert gas (argon), and the buffer solution A is obtained after aeration and sterilization, wherein the aeration time is 30-40min, the sterilization temperature is 121 ℃, and the sterilization time is 20 min); centrifugally collecting the bacterial liquid obtained in the step (2), washing for 2 times by using an anaerobic buffer solution, then carrying out heavy suspension, transferring the bacterial suspension into a buffer solution A, wherein the OD600 value of Shewanella in the anaerobic buffer solution is 1, and stirring an anaerobic reactor on a magnetic stirrer for 30min to obtain a photocatalytic nano material-microorganism hybrid system (CdS/RGO/MR-1 material);
(4) Photocatalytic hydrogen production: and (4) illuminating the CdS/RGO/MR-1 mixed solution obtained in the step (3), and detecting the accumulated hydrogen content in the gas phase every 4h by using a gas chromatograph (GC-9790).
Comparative example 1
This example also provides a method for synthesizing pure CdS
The procedure for preparing CdS/RGO in step (1) of example 1 was substantially the same, except that the addition amount of PVP was 0g and the addition amount of graphene oxide was 0mg, and the CdS material prepared in this comparative example 1 was subjected to XRD characterization.
Shewanella is cultured according to the step (2) in the example 1, then the CdS/RGO material in the step (3) in the example 1 is replaced by the CdS material in the comparative example 1 to prepare a CdS/MR-1 material, and the photocatalytic hydrogen production performance of the CdS/MR-1 mixed solution is tested.
Comparative example 2
This example also provides a method for synthesizing pure RGO
The preparation process of CdS/RGO in step (1) of example 1 is substantially the same, except that 40mg of graphene oxide is dissolved in 20mL of ethylene glycol, and then hydrothermal reaction is performed. Characterization by XRD was performed on the RGO material prepared in this comparative example 2.
Shewanella is cultured according to the step (2) in the example 1, then the CdS/RGO material in the step (3) in the example 1 is replaced by the RGO material in the comparative example 2 to prepare an RGO/MR-1 material, and the photocatalytic hydrogen production performance of the RGO/MR-1 mixed solution is tested.
Performance index testing was performed on the CdS/RGO/MR-1 inorganic biological hybrid system prepared in example 1
(1) Materials and bacteria SEM characterization sample preparation
Taking a proper amount of CdS/RGO material synthesized in the step (1) of the embodiment 1, adding 1mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 80-90 min, and dripping the CdS/RGO material on a silicon wafer for carrying out scanning electron microscope characterization.
1mL of the mixture solution in the anaerobic reactor in the step (3) of example 1 was centrifuged at 5000g for 5min, the supernatant was discarded, washed with PBS 2 times, and fixed with 1mL of 2.5% glutaraldehyde for 4 hours or more. The solution was characterized by dehydrating with a concentration gradient of ethanol (30%, 50%,70%,80%,95%, 100%), centrifuging, removing the supernatant, resuspending with 1mL of anhydrous ethanol, and dropping the resulting solution on a silicon wafer for characterization by scanning electron microscopy.
FIG. 1 is an SEM image of the CdS/RGO photocatalytic material synthesized in example 1, from which it can be seen that CdS is uniformly distributed on RGO and the CdS is wrapped by RGO. FIG. 2 shows SEM images of CdS/RGO/MR-1 synthesized in example 1 and EDS-mapping images of C, O, cd and S element, and it can be seen that RGO encapsulates CdS and thus covers bacteria.
(2) XRD characterization sample preparation
The CdS/RGO material synthesized in the step (1) of the example 1 and the material synthesized in the comparative examples 1 and 2 are taken to be subjected to X-ray diffraction analysis and characterization. FIG. 3 is an XRD pattern of each material, comparing standard cards (# 77-2306), illustrating that the phase of the nanomaterial synthesized in comparative example 1 is CdS; the reason why the peak of RGO does not appear on the CdS/RGO pattern is that the addition amount of RGO is small and the crystallinity is poor.
(3) XPS characterization sample preparation
An appropriate amount of CdS/RGO synthesized in step (1) of example 1 was taken for XPS characterization. FIG. 4 is an XPS spectrum of the material prepared in example 1, demonstrating the synthesis of RGO by analyzing the peak of the CdS/RGO composite carbon and finding a rapid decrease in the percentage of C-O to C = O in the composite; the XPS spectrum of Cd 3d shows two characteristic peaks at 403.9eV and 410.7eV, and the fact that Cd in CdS is represented by Cd 2+ ；S2p 1/2 And S2p 3/2 Orbitals were observed at 161.2eV and 162.8eV, respectively, indicating thatS 2- (ii) is present; in combination with SEM, XRD results, the synthesized material was identified as CdS/RGO.
(4) Determination of optimum hydrogen production conditions
With reference to the mixed solution obtained in step (3) of example 1, concentration gradients of different bacteria (OD 600=1,2,3) and materials (0.025, 0.05,0.1 g/L) were set, the mixed solution was subjected to light irradiation, and the accumulated hydrogen content in the gas phase was detected every 4h using a gas chromatograph (GC-9790). Fig. 5 is an evaluation of determination of the optimum hydrogen production conditions, and it is understood from the figure that the optimum hydrogen production conditions are bacteria concentration OD600=1 and material concentration is 0.05g/L.
(5) Evaluation of photocatalytic hydrogen production performance of inorganic biological mixture
The CdS/RGO/MR-1 mixed solution obtained in the step (3) obtained in the example 1, the CdS/MR-1 mixed solution obtained in the comparative example 1 and the RGO/MR-1 mixed solution obtained in the comparative example 2 were respectively subjected to a photocatalytic hydrogen production test, and FIG. 6 shows the accumulated hydrogen content of the three experimental groups in different time periods. As can be seen from the graph, the composite catalyst of the embodiment of the invention has higher hydrogen production efficiency, and the accumulated hydrogen content at 12h is 12 times of the sum of the accumulated hydrogen content of the CdS/MR-1 group and the accumulated hydrogen content of the RGO/MR-1 group.
(6) Hydrogen production performance test of experimental group and control group
The CdS/RGO material obtained in step (1) of example 1 (without adding bacteria), the bacteria obtained in step (2) (without adding materials) and the CdS/RGO/MR-1 mixed solution obtained in step (3) were taken and subjected to hydrogen production test in the environment with light (experimental group) and without light (control group), respectively.
FIG. 7 shows the accumulated hydrogen content of the 6 experimental groups and the control group in different time periods, and it can be seen from the graph that the accumulated hydrogen content of CdS/RGO/MR-1 in example 1 of the invention in 12h is 22 times of that of the pure bacteria group (MR-1) under the illumination condition.
(7) XRD characterization sample preparation after hydrogen production
Taking the CdS/RGO/MR-1 mixed solution subjected to photocatalytic hydrogen production (the accumulation time is 24 h) in the step (4) in the example 1, centrifuging at 7000rpm for 10min, removing supernatant liquid, and drying the collected precipitate in a vacuum drying oven at 80 ℃ for 6h; the dried solid was ground to a uniform powder using an agate mortar, and an appropriate amount of the powder was taken for characterization by X-ray diffraction analysis. As shown in FIG. 8, in which CdS/RGO represents the CdS/RGO material synthesized in step (1) of example 1, as can be seen from the XRD pattern, the CdS/RGO material peak was present in the CdS/RGO-MR-1 after the reaction, and the peak position was almost unchanged, as for the broader peak at 2 θ =20 °, the peak was a bacterial peak, and the peak intensity was decreased by the presence of bacteria.
(8) ICP-AES (inductively coupled plasma-atomic emission Spectrometry) test of Cd element concentration after hydrogen production
The solution before and after photocatalytic hydrogen production in the step (4) in the example 1 is centrifuged at 12000rpm for 5min, and the supernatant is left after the precipitate is discarded. Digesting the obtained supernatant, adding 4mL of nitric acid, boiling at high temperature, adding 1mL of perchloric acid, finishing digestion when dense white smoke is emitted from a digestion tube, fixing the volume of the solution to 5mL, and measuring the concentration of the Cd element in the solution by adopting ICP-AES. The dissolution concentration of Cd element after the photocatalytic reaction is 0.045mg/L and the dissolution rate is 0.09%, and the inorganic biological hybridization system has good stability during the photocatalytic reaction period by combining the XRD characterization result after the photocatalytic hydrogen production.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (10)
1. A preparation method of a photocatalytic nano material-microorganism heterozygote is characterized by comprising the following steps:
(1) Preparation of CdS/RGO
Adding graphene oxide into a mixed solution containing water-soluble divalent cadmium salt, thiourea and polyvinylpyrrolidone, carrying out hydrothermal reaction, washing, and drying in vacuum to obtain a CdX/RGO material;
(2) Culture of Shewanella
Culturing Shewanella under aerobic condition to obtain bacterial liquid;
(3) Preparation of CdS/RGO/MR-1
Dispersing the CdS/RGO material in an anaerobic buffer solution to obtain a buffer solution A; centrifuging the bacterial liquid obtained in the step (2) to remove the supernatant, dispersing the centrifuged precipitate cells into a buffer solution A, mixing and stirring to obtain the CdS/RGO/MR-1 material.
2. The method of claim 1, wherein the water-soluble divalent cadmium salt is cadmium chloride.
3. The preparation method according to claim 1, wherein the mixed solution containing the water-soluble divalent cadmium salt, thiourea and polyvinylpyrrolidone uses ethylene glycol as a solvent, the concentration of the divalent cadmium salt is 90-100mmol/L, the concentration of the thiourea is 90-100mmol/L, and the concentration of the polyvinylpyrrolidone is 10-12mg/mL; in the step (1), the graphene oxide is added in the form of a graphene oxide glycol solution, the concentration of the graphene oxide glycol solution is 0.4-0.6mg/mL, and the mass of the graphene oxide accounts for 0.5-0.9% of the mass of the polyvinylpyrrolidone.
4. The preparation method according to claim 1, wherein in the step (1), the hydrothermal reaction temperature is 160-200 ℃ and the time is 12-20h; the vacuum drying temperature is 60-80 deg.C, and the drying time is 6-12h.
5. The method according to claim 1, wherein the culture of the bacterial suspension in the step (2): inoculating Shewanella in advance, performing primary aerobic culture under aerobic condition, and then transferring 10-20mL of aerobic culture solution to 100-200mL of fresh culture solution for secondary aerobic culture under the same condition.
6. The production method according to claim 5, wherein the culture solution used in the step (2) is LB medium; the time of primary aerobic culture is 11-13h, and the time of secondary aerobic culture is 11-13h.
7. The method according to claim 1, wherein in the step (3), the concentration of the CdS/RGO material in the buffer A is 0.025-0.1g/L; centrifuging to obtain precipitate, transferring to buffer solution A, and magnetically stirring for 30-40min with Shewanella bacteria OD600 value of 1-3 in anaerobic buffer solution.
8. The method according to claim 1, wherein the anaerobic buffer used in step (3) is subjected to aeration for oxygen removal and sterilization.
9. A photocatalytic nanomaterial-microorganism hybrid obtained by the production method according to any one of claims 1 to 8.
10. Use of the photocatalytic nanomaterial-microorganism hybrid of claim 9 in solar hydrogen production.
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| CN104941665A (en) * | 2015-05-29 | 2015-09-30 | 江苏大学 | Hydrothermal synthesis preparation method of GO-CdS composite material with efficient photocatalysis performance |
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