CN115043425B - Preparation of oxygen-deficient titanium dioxide and escherichia coli biological composite system for hydrogen production - Google Patents
Preparation of oxygen-deficient titanium dioxide and escherichia coli biological composite system for hydrogen production Download PDFInfo
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- CN115043425B CN115043425B CN202210358072.8A CN202210358072A CN115043425B CN 115043425 B CN115043425 B CN 115043425B CN 202210358072 A CN202210358072 A CN 202210358072A CN 115043425 B CN115043425 B CN 115043425B
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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Abstract
The invention provides oxygen-deficient titanium dioxide-escherichia coli (TiO) 2‑x Preparation method of @ E.Coli) biological composite system mainly involves the following steps: oxygen deficient titanium dioxide (TiO) 2‑x ) Preparation and characterization of nanomaterials, tiO 2‑x Preparation and characterization of the Coli biological composite system and exploration of hydrogen production performance of the composite system. TiO (titanium dioxide) 2‑x The @ E.Coli biocomposite system utilizes not only TiO 2‑x The high photo-activity and photochemical stability and the high specific biocatalytic capability in E.Coli organisms are utilized, and TiO modified by Polyethyleneimine (PEI) 2‑x Positively charged, more favorable for combining with negatively charged bacteria E.Coli, and can be used for biological hydrogen production. The TiO 2‑x The @ E.Coli biocomposite system was sensitive to visible light (780 nm>λ>420 nm) can reach 1.25mmol of hydrogen production under the irradiation of three hours, is TiO 2 The hydrogen yield of the @ E.Coli biological composite system is 1.31 times that of pure escherichia coli and 3.13 times that of pure escherichia coli, so that the hydrogen production efficiency is remarkably improved.
Description
Technical Field
The invention belongs to the field of biological hydrogen production; oxygen-deficient titanium dioxide for hydrogen production and E.coli biocomposite systems (TiO 2-x Coli) mainly involves the following steps: oxygen deficient titanium dioxide (TiO) 2-x ) Preparation and characterization of nanomaterials, tiO 2-x Preparation and characterization of the Coli biological composite system and exploration of hydrogen production performance of the composite system.
Background
Due to the exhaustion of energy sources and environmental problems caused by the combustion of fossil fuels, it is desirable to utilize renewable, eco-friendly solar energy. Solar-driven generation of hydrogen energy provides an ideal strategy for solving the problem of limited fossil fuel shortages, and is therefore of great interest. In recent years, a biocomposite system composed of an inorganic semiconductor excellent in light absorption efficiency and a high hydrogen-producing microorganism has attracted great attention. Generally, photosynthetic organism complex systems (PBSS) include both enzyme-based (cell-free) and whole cell-based forms. The cell-free PBSS has high requirements on enzyme purification, and the purified enzyme has complex operation and high cost. The whole cell PBSS is a novel method for taking whole cells expressing hydrogenase as a biocatalyst, and has obvious advantages compared with a pure hydrogenase biological composite system due to simple preparation and high stability.
In the prototype of whole cell PBSS, several nanoparticle-cell biocomposites were designed to achieve electron transfer between inorganic materials and living cells. Wherein the non-photosynthetic, hot acetic acid bacteria are self-photosensitized by the biologically precipitated cadmium sulfide and promote the production of acetic acid under light. Cadmium is then integrated with different bacterial species, including E.coli, rhodopseudomonas palustris, and Thiobacillus denitrificans, for converting solar energy into chemicals. In addition, aglnS has also been successfully demonstrated 2 /In 2 S 3 Integration of InP and cds@zns with microorganisms. Despite these promising advances, PBSS is still in an early stage of development, with little knowledge of the electron transport mechanisms and interface effects at biological and non-biological interfaces. In this study, we achieved an improvement in visible light absorption and charge separation efficiency by introducing a defect band below the conduction band of titania. And oxygen-deficient TiO 2-x The nanoparticle is combined with facultative anaerobic bacteria E.coli (E.Coli) for biological hydrogen production.
Disclosure of Invention
The invention aims to solve the problems of TiO 2 Has larger forbidden bandwidth, can only absorb less than 5% of ultraviolet light in sunlight, and leads to TiO 2 The problem of low hydrogen production efficiency of the Coli biological compound system is solved. The method can be used for mass production of oxygen defect TiO 2-x Nanoparticles to achieve improved visible light absorption and charge separation efficiency. Next, the method modifies TiO with PEI 2-x Nanoparticles, tiO 2-x The nanoparticle changes from negative to positive so that it can bind to E.coli with a negatively charged surface via electrostatic interactions. Thus, the TiO can be remarkably improved 2-x Hydrogen production efficiency of the coli biocomposite system.
To solve the above problems, the present invention provides oxygen-deficient titania-E.coli (TiO 2-x @E.Coli) The preparation of a biological composite system mainly relates to: oxygen deficient titanium dioxide (TiO) 2-x ) Preparation and characterization of nanomaterials, tiO 2-x Preparation and characterization of the Coli biological composite system and exploration of hydrogen production performance of the composite system. The method specifically comprises the following steps:
step one, 1.0g of TiO 2 NPs with 1.0g NaBH 4 Grinding for 30min, heating to 300 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen in a tube furnace, and keeping for 90min;
step two, cooling the material to room temperature and then removing unreacted NaBH by using water and ethanol 4 Vacuum drying at 50deg.C to obtain oxygen-deficient TiO 2-x NPs；
Step three, modifying the oxygen defect TiO by Polyethyleneimine (PEI) 2-x NPs are uniformly mixed on a magnetic stirrer, centrifugally cleaned, and TiO is measured by using Zeta potential 2-x Electrical properties of NPs;
preparing LB culture solution required by the growth of escherichia coli, adjusting the pH to 7.3-7.4, and placing the prepared LB culture solution in a high-pressure steam sterilization pot for sterilization (20 min at 121 ℃);
step five, after the culture solution to be sterilized is kept stand at room temperature, bacteria are inoculated in an ultra-clean bench, and the inoculated bacterial culture solution is placed in a shaking table (100 rpm at 37 ℃) for culture;
step six, measuring the OD600 of the bacteria by using an ultraviolet-visible absorption spectrum, and adding 200ug/ml of PEI modified oxygen defect TiO when the OD600 value of the bacterial culture solution is 0.5 2-x NPs, cultured for 2-4 hours to cause oxygen defect TiO 2-x NPs bind to bacteria;
step seven, centrifuging the culture solution (3000 rmmin -1 10 min), transferring the precipitate into an anaerobic bottle, adding sterilized fresh culture solution (0.5 g yeast extract, 1g-1.5g peptone, 1g-1.2g sodium chloride, 100ml deionized water, glucose), and culturing overnight in a shaker to adapt bacteria to anaerobic environment;
step eight, centrifuging the bacteria after anaerobic culture (3000 r min -1 10 min), and adding into 100ml anaerobic reactor, and adding new sterilized culture solution (0.5 g yeastExtract, 1g-1.5g peptone, 1g-1.2g sodium chloride, 100ml deionized water, 12.1mg cysteine, glucose, methyl viologen);
step nine, starting to measure TiO 2-x Hydrogen production by the coli biocomposite system was measured from hour 0 for a total of 3 hours.
The invention synthesizes the oxygen defect TiO by a simple and environment-friendly method 2-x NPs, which have higher photo-activity, photochemical stability, can significantly improve visible light absorption and charge separation efficiency.
Oxygen deficient TiO of the present invention 2-x NPs are modified by PEI to show electropositivity and can be combined with E.coli with negatively charged surface through electrostatic interaction.
The invention optimizes the oxygen defect TiO 2-x The addition amount of NPs to obtain the optimal oxygen defect TiO 2-x NPs concentration was 200ug/ml.
The TiO of the invention 2-x The @ E.Coli biocomposite system was modified in visible light (780 nm>λ>420 nm) can reach 1.25mmol of hydrogen production under the irradiation of three hours, is TiO 2 The hydrogen yield of the @ E.Coli biological composite system is 1.31 times that of pure escherichia coli and 3.13 times that of pure escherichia coli, so that the hydrogen production efficiency is remarkably improved.
Drawings
FIG. 1 is TiO 2-x TEM images of NPs.
FIG. 2 is TiO 2 NPs and TiO 2-x UV-Vis profile of NPs.
FIG. 3 is TiO 2 NPs and TiO 2-x PL profile of NPs.
FIG. 4 is a graph showing the concentration of TiO at various concentrations 2-x OD600 values for different time periods after NPs were added to the bacterial broth.
FIG. 5 is TiO 2-x @E.Coli biocomposite system, tiO 2 Comparative plots of coli biocomposite system and pure bacterial hydrogen production.
Detailed Description
Embodiment 1:
step one, 1.0g of TiO 2 NPs with 1.0g NaBH 4 Grinding for 30min, and preserving nitrogen in a tube furnaceHeating to 300 ℃ at a heating rate of 10 ℃/min under protection, and keeping for 90min;
step two, cooling the material to room temperature and then removing unreacted NaBH by using water and ethanol 4 Vacuum drying at 50deg.C to obtain oxygen-deficient TiO 2-x NPs；
Step three, modifying the oxygen defect TiO by Polyethyleneimine (PEI) 2-x NPs are uniformly mixed on a magnetic stirrer, centrifugally cleaned, and TiO is measured by using Zeta potential 2-x Electrical properties of NPs;
preparing LB culture solution required by the growth of escherichia coli, adjusting the pH to 7.3-7.4, and placing the prepared LB culture solution in a high-pressure steam sterilization pot for sterilization (20 min at 121 ℃);
step five, after the culture solution to be sterilized is kept stand at room temperature, bacteria are inoculated in an ultra-clean bench, and the inoculated bacterial culture solution is placed in a shaking table (100 rpm at 37 ℃) for culture;
step six, measuring the OD600 of the bacteria by using an ultraviolet-visible absorption spectrum, and adding 200ug/ml of PEI modified oxygen defect TiO when the OD600 value of the bacterial culture solution is 0.5 2-x NPs, cultured for 2-4 hours to cause oxygen defect TiO 2-x NPs bind to bacteria;
step seven, centrifuging the culture solution (3000 rmmin -1 10 min), transferring the precipitate into an anaerobic bottle, adding sterilized fresh culture solution (0.5 g yeast extract, 1g-1.5g peptone, 1g-1.2g sodium chloride, 100ml deionized water, glucose), and culturing overnight in a shaker to adapt bacteria to anaerobic environment;
step eight, centrifuging the bacteria after anaerobic culture (3000 r min -1 10 min), placing into a 100ml anaerobic reactor, and adding new sterilized culture solution (0.5 g yeast extract, 1g-1.5g peptone, 1g-1.2g sodium chloride, 100ml deionized water, 12.1mg cysteine, glucose, methyl viologen);
step nine, starting to measure TiO 2-x Hydrogen production by the coli biocomposite system was measured from hour 0 for a total of 3 hours.
The following tests are adopted to verify the effects of the invention:
1. oxygen gasDefective titanium dioxide (TiO) 2-x ) Preparation and characterization of nanomaterials
As observed from TEM, the prepared oxygen-deficient TiO 2-x NPs had a uniform particle size and good dispersibility, and the particle size was about 23nm (fig. 1).
The UV-visible diffuse reflection absorption spectrum investigated the passage of NaBH 4 Light absorption properties of reduced oxygen-deficient titanium dioxide nanoparticles, with absorption band edges near 400nm, with TiO 2 The intrinsic absorption band edges of the nanoparticles are uniform. From (FIG. 2), it can be seen that TiO is obtained after hydrogenation 2-x NPs absorb visible-near infrared light with higher intensity than TiO 2 NPs are greatly enhanced.
The separation and transfer of photo-generated carriers of saturated and oxygen-deficient titania was studied using steady state fluorescence spectroscopy (PL). From the graph, the PL intensity of the oxygen-deficient titanium dioxide is obviously lower than that of a saturated titanium dioxide system, which indicates that the oxygen-deficient titanium dioxide nano-particles effectively improve the separation efficiency of photo-generated electrons and holes.
2.TiO 2-x Preparation and characterization of the @ E.Coli biocomposite System
Determination of different TiO by ultraviolet visible absorption Spectrometry 2-x NPs addition amount of TiO 2-x OD600 value of @ E.coli biocomposite System to determine TiO 2-x Optimal concentration of NPs. 200ug/ml, 400ug/ml and 1000ug/ml of PEI modified positively charged TiO are respectively added into the bacterial culture solution 2-x NPs, which measure the OD600 of the bacteria over different time periods, eventually give the best growth status of the bacteria when added at a concentration of 200ug/ml (FIG. 4), while the growth rate of the bacteria starts to slow down and the total growth decreases when the concentration is 400ug/ml or 1000 ug/ml. Thus, tiO 2-x The optimal addition concentration of NPs was 200ug/ml.
3. Exploration of hydrogen production performance of composite system
Investigation of TiO Using a gas chromatograph 2-x Hydrogen production performance of the @ E.Coli biocomposite system was measured in visible light (780 nm>λ>420 nm) was subjected to a hydrogen production test for three hours. (FIG. 5) results in TiO 2-x Three of the @ E.Coli biocomposite systemsThe total hydrogen yield per hour can reach 1.25mmol, which is TiO 2 The hydrogen yield of the @ E.Coli biological composite system is 1.31 times that of pure escherichia coli and 3.13 times that of pure escherichia coli, so that the hydrogen production efficiency is remarkably improved.
Coli is an excellent biocatalyst, and oxygen-deficient titania can promote the separation of photogenerated electrons and holes, thereby prolonging the life of the electrons and holes. Combining oxygen-deficient titanium dioxide with Escherichia coli to produce TiO 2-x The @ E.Coli biological composite system has high hydrogen production efficiency, simple operation, wide material source and low cost, and is a promising method for developing photocatalysis hydrogen production in future.
Claims (5)
1. The preparation method of the oxygen-deficient titanium dioxide nano particle and escherichia coli biological composite system for producing hydrogen is characterized by comprising the following steps of:
step one, 1.0g of TiO 2 NPs with 1.0g NaBH 4 Grinding for 30min, heating to 300 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen in a tube furnace, and keeping for 90min;
step two, cooling the material to room temperature and then removing unreacted NaBH by using water and ethanol 4 Vacuum drying at 50deg.C to obtain oxygen-deficient TiO 2-x NPs；
Step three, modifying oxygen defect TiO by polyethyleneimine PEI 2-x NPs are uniformly mixed on a magnetic stirrer, centrifugally cleaned, and TiO is measured by using Zeta potential 2-x Electrical properties of NPs;
preparing LB culture solution required by the growth of escherichia coli, adjusting the pH to 7.3-7.4, and placing the prepared LB culture solution in a high-pressure steam sterilization pot for sterilization at 121 ℃ for 20min;
step five, after the culture solution to be sterilized is kept stand at room temperature, bacteria are inoculated in an ultra-clean bench, and the inoculated bacteria culture solution is placed in a shaking table for culture at 37 ℃ and the rotating speed is 100rpm;
step six, measuring the OD600 of bacteria by using ultraviolet-visible absorption spectrum, when the OD600 value of a bacterial culture solution is 0.5, adding 200ug/ml oxygen-deficient titanium dioxide nano particles modified by polyethyleneimine, and culturing for 2-4 hours to combine the oxygen-deficient titanium dioxide nano particles with the bacteria;
step seven, the culture solution is processed for 3000r min -1 Centrifuging for 10min, transferring the precipitate into an anaerobic bottle, adding sterilized fresh culture solution, wherein the culture solution consists of 0.5g of yeast extract, 1g-1.5g of peptone, 1g-1.2g of sodium chloride, 100ml of deionized water and glucose, and placing into a shaking table for overnight culture to enable bacteria to adapt to anaerobic environment;
step eight, the bacteria after anaerobic culture are subjected to 3000r min -1 After centrifugation for 10min, putting the mixture into a 100ml anaerobic reactor, and adding the mixture into a new sterilized culture solution, wherein the culture solution consists of 0.5g of yeast extract, 1g-1.5g of peptone, 1g-1.2g of sodium chloride, 100ml of deionized water, 12.1mg of cysteine, glucose and methyl viologen;
step nine, starting to measure TiO 2-x The hydrogen production of the E.Coli biocomposite system was measured starting from hour 0 for a total of 3 hours.
2. The method for preparing hydrogen-producing oxygen-deficient titanium dioxide nanoparticles and E.coli biological composite system according to claim 1, wherein the oxygen-deficient titanium dioxide nanoparticles added in the step six are prepared by mixing saturated TiO 2 Nanoparticles and NaBH 4 Mixing the oxygen-deficient TiO obtained by high temperature treatment 2-x The light absorption of the nanoparticles in the visible and near infrared regions is greatly enhanced.
3. The method for preparing hydrogen-producing oxygen-deficient titanium dioxide nanoparticles and escherichia coli biological composite system as claimed in claim 1, wherein the oxygen-deficient titanium dioxide nanoparticles added in the step six are modified by polyethyleneimine, and are changed from negative to positive, so that bacteria with negative surface charge can be combined with TiO 2-x NPs bind by electrostatic interactions.
4. The method for preparing a hydrogen-producing oxygen-deficient titanium dioxide nanoparticle and escherichia coli biological composite system according to claim 1, wherein in the seventh step, bacteria combined with the oxygen-deficient titanium dioxide nanoparticle are centrifuged and replaced with a new culture solution, and the bacteria are cultured in an anaerobic bottle to adapt to anaerobic environment.
5. The method for preparing the oxygen-deficient titanium dioxide nanoparticle and escherichia coli biological composite system for generating hydrogen according to claim 1, wherein the step nine researches TiO 2-x Hydrogen production by E.Coli biocomposite systems, which system is at 780nm in visible light>λ>The hydrogen yield under 420nm irradiation for three hours can reach 1.25mmol, which is TiO 2 The hydrogen yield of the E.Coli biological composite system is 1.31 times that of pure escherichia coli and 3.13 times that of pure escherichia coli, so that the hydrogen production efficiency is remarkably improved.
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| CN1655869A (en) * | 2002-03-25 | 2005-08-17 | 住友钛株式会社 | Titanium oxide-based photocatalyst, manufacturing method therefor and its application |
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| US20090137013A1 (en) * | 2007-11-07 | 2009-05-28 | Sustainable Green Technologies, Inc. | Microorganisms and methods for increased hydrogen production using diverse carbonaceous feedstock and highly absorptive materials |
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| CN1655869A (en) * | 2002-03-25 | 2005-08-17 | 住友钛株式会社 | Titanium oxide-based photocatalyst, manufacturing method therefor and its application |
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