CN113862308B - Chemical-biological composite hydrogen production system based on quantum dot nano material and preparation method thereof - Google Patents
Chemical-biological composite hydrogen production system based on quantum dot nano material and preparation method thereof Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 76
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 68
- 239000001257 hydrogen Substances 0.000 title claims abstract description 68
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 56
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 230000000243 photosynthetic effect Effects 0.000 claims abstract description 26
- 241000894006 Bacteria Species 0.000 claims abstract description 19
- 230000000536 complexating effect Effects 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 241000190950 Rhodopseudomonas palustris Species 0.000 claims description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 13
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims description 8
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 6
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical class [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 6
- VQNPSCRXHSIJTH-UHFFFAOYSA-N cadmium(2+);carbanide Chemical compound [CH3-].[CH3-].[Cd+2] VQNPSCRXHSIJTH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 claims 5
- 230000001699 photocatalysis Effects 0.000 abstract description 29
- 238000007146 photocatalysis Methods 0.000 abstract description 23
- -1 methyl violet nitrile Chemical class 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 230000001360 synchronised effect Effects 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 7
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000029553 photosynthesis Effects 0.000 description 2
- 238000010672 photosynthesis Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000190932 Rhodopseudomonas Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- Bioinformatics & Cheminformatics (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention provides a chemical-biological composite hydrogen production system based on a quantum dot nanomaterial, which comprises a nanopore carrier, and a quantum dot composite layer, a methyl violet nitrile layer and a photosynthetic bacteria layer which are sequentially arranged on the surface of the nanopore carrier. The composite hydrogen production system utilizes unique luminescence characteristic and excellent biological compatibility characteristic of quantum dots, adopts quantum dot complexing technology, takes quantum dot nano particles as media, and combines chemical photocatalysis hydrogen production with biological photocatalysis hydrogen production, so as to ensure synchronous chemical photocatalysis and biological photocatalysis, overcome the defect of chemical photocatalysis hydrogen production and effectively improve biological photocatalysis hydrogen production efficiency. Meanwhile, the invention also provides a preparation method of the chemical-biological composite hydrogen production system based on the quantum dot nanomaterial.
Description
Technical Field
The invention relates to the field of photocatalytic hydrogen production, in particular to a chemical-biological composite hydrogen production system based on quantum dot nano materials and a preparation method thereof.
Background
The shortage of energy and environmental pollution are important problems to be solved in the development of human society, and the development of renewable energy supply systems which do not depend on fossil energy is a necessary way to realize sustainable development. Hydrogen is used as a clean and efficient renewable energy source, has rich reserves, high combustion heat value and no pollution of combustion products, and is an ideal alternative energy source. At present, the industrialized hydrogen production mainly comes from the catalytic reforming of fossil fuel and the electrolysis of water to produce hydrogen, and the sustainable development is difficult to realize. Solar energy is the most ideal hydrogen energy production and supply energy source, and has wide application prospect in developing a green solar hydrogen energy production system.
Solar hydrogen production mainly includes two types: one is to utilize the biological photocatalysis hydrogen production of hydrogen release characteristic under the illumination condition of the photosynthetic organisms in the nature, and the other is to produce hydrogen based on chemical photocatalysis of artificial inorganic semiconductor materials. The former is that photosynthetic microorganism uses self biological enzyme as catalyst through self light effect, under the drive of light energy, the photolyzed water or organic hydrogen is produced, which is the solar energy utilization and hydrogen energy conversion process commonly existing in nature. The latter is to simulate natural photosynthesis by utilizing the photocatalysis characteristic of inorganic semiconductor material and to design and manufacture artificial photocatalysis system to decompose water or organic hydrogen.
The biological photocatalysis hydrogen production is a process of converting solar energy obtained by photosynthesis into hydrogen energy by photosynthetic organisms, and the acquisition of the solar energy and the conversion of the light energy play a vital role in hydrogen production efficiency. The light energy conversion rate of the photosynthetic bacteria photocatalytic hydrogen production is 1-5%, which is far higher than the photosynthetic efficiency of the algae hydrogen production, but still is low. Because the light energy conversion rate is low, the light dependence is strong, the problems of high energy consumption, complex design of a photo-reactor and the like exist in the biological photo-catalytic hydrogen production, the large-scale production is difficult to realize, and the development of the photosynthetic biological photo-catalytic hydrogen production technology is restricted. The chemical photocatalysis hydrogen production has the outstanding advantage of being capable of specifically producing the photocatalyst, so that water or organic matters can be rapidly decomposed in a large scale to produce hydrogen, and the photocatalysis can be realized with higher efficiency and the large-scale production can be realized. However, there are still problems such as that the photocatalyst is stable and effective only in the ultraviolet region, the photocatalyst activity in the visible region is low, and the photo-etching phenomenon, low energy conversion efficiency and the like are almost all present.
In order to solve the above problems, an ideal technical solution is always sought.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art, and provides a chemical-biological composite hydrogen production system based on quantum dot nano materials and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a chemical-biological composite hydrogen production system based on quantum dot nano materials comprises a nano-pore carrier, and a quantum dot composite layer, a methyl violet nitrile layer and a photosynthetic bacteria layer which are sequentially arranged on the surface of the nano-pore carrier.
Based on the above, the photosynthetic bacteria are rhodopseudomonas palustris, and the composite quantum dots comprise 45% -55% of zinc sulfide quantum dots, 15% -25% of sulfur/copper oxide quantum dots and 25% -35% of sulfur/nickel oxide quantum dots.
Based on the above, the nano-pore carrier is SiO 2 A nanopore carrier.
Based on the above, the preparation method of the chemical-biological composite hydrogen production system based on the quantum dot nanomaterial comprises the following steps of firstly adopting a nanopore carrier to adsorb and fix composite quantum dots, and then using methyl violet nitrile as a complexing medium to complex photosynthetic bacteria.
Based on the above, siO 2 Pickling the nano-pore glass in 65-75% sulfuric acid for 36-58 h, and baking at 75-85 ℃ for 10-20 min to obtain the nano-pore carrier, thereby forming a first nano-pore glass carrier layer.
Based on the above, znSO is added 4 Dissolving in dimethyl cadmium solution to obtain dimethyl zinc, adding Na 2 S is dissolved in tri-n-octyl phosphine oxide, na is added at 250-350 DEG C 2 S reacts with dimethyl zinc to generate ZnS quantum dot solution, and then sulfur/copper oxide and sulfur/nickel oxide are added to be uniformly mixed to obtain the composite quantum dot solution.
Based on the above, the particle size of sulfur/copper oxide and sulfur/nickel oxide is 10 to 20. 20 nm.
Based on the above, spraying the composite quantum dot solution on the nano-pore carrier, and then baking at 180-220 ℃ for 10-20 min to form a second quantum dot composite layer.
Based on the above, under the condition of 60-70 ℃, continuing to adsorb the methyl violet nitrile 6-10 h on the nano-pore carrier after adsorbing the composite quantum dots to form a third methyl violet nitrile composite layer; then complexing rhodopseudomonas palustris 45-55 h at 32-37 ℃ to form a fourth photosynthetic bacteria layer.
Based on the above, the rhodopseudomonas palustris has a thallus concentration of 1.2-1.8 g/L and a methyl violet nitrile concentration of 8-12 g/L.
Compared with the prior art, the invention has outstanding substantive characteristics and remarkable progress, and in particular provides a chemical-biological composite hydrogen production system based on quantum dot nano materials.
Furthermore, the existing photosynthetic organism hydrogen production reactor has a complex structure due to the design of an illumination system. The hydrogen production system is directly modified by adopting the chemical photocatalytic hydrogen production photoreactor, the design of the photoreactor is simplified, the illumination is enhanced by the endogenous emission spectrum of the quantum dots, only illumination conditions are ensured, and a complex structure is not required to be designed.
Furthermore, the biological nontoxic chemical photocatalysis hydrogen production nano semiconductor is adopted, the biological activity and the hydrogen production activity of photosynthetic bacteria are compatible, the unique luminescence characteristic and the excellent biological compatibility characteristic of the quantum dots are utilized, the quantum dot complexing technology is adopted, the quantum dot nano particles are used as media, the chemical photocatalysis hydrogen production and the biological photocatalysis hydrogen production are connected, the synchronous performance of the chemical photocatalysis and the biological photocatalysis is ensured, the defect of chemical photocatalysis hydrogen production is overcome, and the biological photocatalysis hydrogen production efficiency is effectively promoted.
Further, the quantum dots are subjected to quantum dot loss in the reaction process due to unique quantum effects and chemical activities, and the quantum dots are subjected to immobilization treatment in order to keep the stability and the persistence of hydrogen production. Adopts a silicon-based nano-pore carrier immobilization technology and utilizes SiO 2 The unique nano-pore structure of the nano-pore glass adsorbs and fixes the quantum dots, and prevents the quantum dots from losing.
Furthermore, the invention adopts zinc sulfide, sulfur/copper oxide and sulfur/nickel oxide to carry out composite quantum dots, thereby ensuring better biocompatibility and further ensuring synchronous carrying out of chemical photocatalysis and biological photocatalysis; and the composite quantum dots with the endogenous emission spectrum energy coupled with the absorption spectrum of the biological photosynthetic system are adopted to promote the conversion of the light energy of the hydrogen production by the composite photocatalysis.
Drawings
FIG. 1 is a schematic view (one) of the structure of a reactor in the example.
FIG. 2 is a schematic diagram of the structure of the reactor (II) in the example.
In the figure: 1. an external xenon lamp; 2. a catalytic plate; 3. and (3) compounding a hydrogen-producing monomer.
Detailed Description
The technical scheme of the invention is further described in detail through the following specific embodiments.
Example 1
The embodiment provides a chemical-biological composite hydrogen production system based on quantum dot nano materials, which comprises a nano-pore carrier, and a quantum dot composite layer, a methyl violet nitrile layer and a photosynthetic bacteria layer which are sequentially arranged on the surface of the nano-pore carrier.
Specifically, the photosynthetic bacteria are rhodopseudomonas palustris, and the composite quantum dots comprise 50% of zinc sulfide quantum dots, 20% of copper oxide quantum dots and 30% of nickel oxide quantum dots. In other embodiments, the composite quantum dots may include 55% zinc sulfide quantum dots, 17% copper oxide quantum dots, and 28% nickel oxide quantum dots; the composite quantum dots include 45% zinc sulfide quantum dots, 22% sulfur/copper oxide quantum dots, and 33% sulfur/nickel oxide quantum dots or other values within the scope of the present invention. In addition, in other embodiments, copper sulfide and nickel sulfide may be used instead of copper oxide and nickel oxide.
In other embodiments, other types of photosynthetic bacteria may be used, such as: the composite quantum dots can also correspondingly adopt other quantum dots with good biocompatibility.
Specifically, the nano-pore carrier is SiO 2 A nanopore carrier.
The embodiment also provides a preparation method of the chemical-biological composite hydrogen production system based on the quantum dot nanomaterial, which comprises the following steps of firstly adopting a nanopore carrier to adsorb and fix composite quantum dots, and then using methyl violet nitrile as a complexing medium to complex photosynthetic bacteria.
Specifically, siO is prepared under the condition of 65 DEG C 2 The nano-pore glass is pickled in 70% sulfuric acid for 48 and h, and baked at 80 ℃ for 15 min to obtain the nano-pore carrier, so as to form a first nano-pore glass carrier layer.
ZnSO is added to 4 Dissolving in dimethyl cadmium solution to obtain dimethyl zinc, adding Na 2 S is dissolved in tri-n-octyl phosphine oxide, na is dissolved at 300 DEG C 2 S reacts with dimethyl zinc to generate ZnS quantum dot solution, and then copper sulfide and nickel sulfide are added and mixed uniformly to obtain composite quantum dot solution; wherein the average particle size of the copper sulfide and nickel sulfide is 20 nm.
Spraying a composite quantum dot solution on the nano-pore carrier, and then drying at 200 ℃ for 15 min to form a second quantum dot composite layer.
Continuing to adsorb the methyl violet nitrile 8 and h on the nano-pore carrier after adsorbing the composite quantum dots at 65 ℃ to form a third methyl violet nitrile composite layer, complexing rhodopseudomonas palustris 48 h at 35 ℃, and circularly refluxing for multiple times during the complexing process to form a fourth photosynthetic bacteria layer to obtain a composite photocatalytic hydrogen production monomer; wherein, the thallus concentration of rhodopseudomonas palustris is 1.5 g/L, and the concentration of methyl violet nitrile is 10 g/L.
Hydrogen production experiment
With working volume of 0.9L and effective cross-sectional area of fluid flow of 3500 mm 2 The transparent reactor takes straw powder as an organic substrate, the illumination intensity is 192W/m < 2 >, the hydrogen production temperature is 35 ℃, the substrate concentration is 30 g/L, the hydrogen production time is 144 h, and the hydrogen production amount of the rhodopseudomonas palustris culture solution is 147 mL/g. Wherein the rhodopseudomonas zeylanica culture solution is 1.5 g/L rhodopseudomonas palustris, 0.4 g/L ammonium chloride, 0.2 g/L magnesium chloride, 0.1 g/L yeast powder, 0.5 g/L dipotassium hydrogen phosphate, 2 g/L sodium chloride and 3.56 g/L glutamine.
With working volume of 0.9L and effective cross-sectional area of fluid flow of 3500 mm 2 Referring to fig. 1-2, catalytic plates 2 with the dimensions of 210 (L) ×50 (H) ×170 (W) mm are placed on two sides of the transparent reactor, 80 composite hydrogen-producing monomers 3 with the specifications of 10mm×10mm are uniformly arranged on each catalytic plate 2, the composite hydrogen-producing monomers 3 of the two catalytic plates 2 are staggered, an external xenon lamp 1 provides illumination, the illumination intensity is 192W/m 2, the hydrogen production temperature is 35 ℃, straw powder is used as an organic substrate, the substrate concentration is 30 g/L, the hydrogen production time is 144H, and the hydrogen production amount is 213 mL/g.
Example 2
The embodiment provides a preparation method of a chemical-biological composite hydrogen production system based on quantum dot nano materials, which comprises the following steps of firstly adopting a nano-pore carrier to adsorb and fix composite quantum dots, and then using methyl violet nitrile as a complexing medium to complex photosynthetic bacteria.
Specifically, siO is produced under 70 DEG C 2 Pickling the nano-pore glass in 65% sulfuric acid for 58 h, and baking at 85 ℃ for 10 min to obtain the nano-pore carrier, thereby forming a first nano-pore glass carrier layer.
Specifically, znSO is to 4 Dissolving in dimethyl cadmium solution to obtain dimethyl zinc, adding Na 2 S is dissolved in tri-n-octyl phosphine oxide, na is dissolved at 300 DEG C 2 S reacts with dimethyl zinc to generate ZnS quantum dot solution, and then copper oxide and nickel oxide are added and mixed uniformly to obtain composite quantum dot solution; wherein the particle size of the copper oxide and nickel oxide is 10 nm.
Spraying a composite quantum dot solution on the nano-pore carrier, and then drying at 180 ℃ for 20 min to form a second quantum dot composite layer.
And (3) continuing to adsorb the methyl violet nitrile 10 h on the nano-pore carrier after adsorbing the composite quantum dots at the temperature of 60 ℃ to form a third methyl violet nitrile layer, complexing rhodopseudomonas palustris 55 h at the temperature of 37 ℃ and performing repeated circulating reflux to form a fourth photosynthetic bacteria layer. Wherein, the thallus concentration of rhodopseudomonas palustris is 1.2 g/L, and the concentration of methyl violet nitrile is 8 g/L.
Example 3
The embodiment provides a preparation method of a chemical-biological composite hydrogen production system based on quantum dot nano materials, which comprises the following steps of firstly adopting a nano-pore carrier to adsorb and fix composite quantum dots, and then using methyl violet nitrile as a complexing medium to complex photosynthetic bacteria.
Specifically, siO is produced under 60 DEG C 2 Pickling the nano-pore glass in 65% sulfuric acid for 36 h, and baking at 75 ℃ for 20 min to obtain the nano-pore carrier, thereby forming a first nano-pore glass carrier layer.
ZnSO is added to 4 Dissolving in dimethyl cadmium solution to obtain dimethyl zinc, adding Na 2 S is dissolved in tri-n-octyl phosphine oxide, na is dissolved at 300 DEG C 2 S reacts with dimethyl zinc to generate ZnS quantum dot solution, and then copper sulfide and nickel oxide are added and mixed uniformly to obtain the composite quantum dot solution; wherein the particle size of the copper sulfide and nickel oxide is 15 nm.
Spraying a composite quantum dot solution on the nano-pore carrier, and then baking at 220 ℃ for 10 min to form a second quantum dot composite layer.
Continuing to adsorb the methyl violet nitrile 9 h on the nano-pore carrier after adsorbing the composite quantum dots at the temperature of 70 ℃ to form a third methyl violet nitrile layer; complexing rhodopseudomonas palustris 50 and h at the temperature of 33 ℃ to form a fourth photosynthetic bacteria layer; wherein, the thallus concentration of rhodopseudomonas palustris is 1.8 g/L, and the concentration of methyl violet nitrile is 12 g/L.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same; while the invention has been described in detail with reference to the preferred embodiments, those skilled in the art will appreciate that: modifications may be made to the specific embodiments of the present invention or equivalents may be substituted for part of the technical features thereof; without departing from the spirit of the invention, it is intended to cover the scope of the invention as claimed.
Claims (5)
1. A chemical-biological composite hydrogen production system based on quantum dot nano materials is characterized in that: the quantum dot composite layer, the methyl viologen layer and the photosynthetic bacteria layer are sequentially arranged on the surface of the nano-pore carrier;
spraying a composite quantum dot solution on a nano-pore carrier, adsorbing and fixing the composite quantum dots by adopting the nano-pore carrier, and then baking at 180-220 ℃ for 10-20 min to form a second quantum dot composite layer; then under the condition of 60-70 ℃, continuing to adsorb the methyl viologen 6-10 h on the nano-pore carrier after adsorbing the composite quantum dots to form a third methyl viologen composite layer; then, taking methyl viologen as a complexing medium, complexing rhodopseudomonas palustris 45-55 h at the temperature of 32-37 ℃ and complexing photosynthetic bacteria to form a fourth photosynthetic bacteria layer; the composite quantum dots comprise 45% -55% of zinc sulfide quantum dots, 15% -25% of sulfur/copper oxide quantum dots and 25% -35% of sulfur/nickel oxide quantum dots; the nano-pore carrier is SiO 2 A nanopore carrier.
2. According to claimThe chemical-biological composite hydrogen production system based on quantum dot nano material as set forth in claim 1, characterized in that SiO is produced at 60-70 DEG C 2 Pickling the nano-pore glass in 65-75% sulfuric acid for 36-58 h, and baking at 75-85 ℃ for 10-20 min to obtain the nano-pore carrier, thereby forming a first nano-pore glass carrier layer.
3. The chemical-biological composite hydrogen production system based on quantum dot nanomaterials as claimed in claim 2, wherein ZnSO is used to produce hydrogen 4 Dissolving in dimethyl cadmium solution to obtain dimethyl zinc, adding Na 2 S is dissolved in tri-n-octyl phosphine oxide, na is added at 250-350 DEG C 2 S reacts with dimethyl zinc to generate ZnS quantum dot solution, and then sulfur/copper oxide and sulfur/nickel oxide are added to be uniformly mixed to obtain the composite quantum dot solution.
4. A chemical-biological composite hydrogen production system based on quantum dot nanomaterials as claimed in claim 3, wherein: the particle size of the sulfur/copper oxide and sulfur/nickel oxide is 10-20 nm.
5. The chemical-biological composite hydrogen production system based on quantum dot nanomaterials of claim 1, wherein: the concentration of rhodopseudomonas palustris thallus is 1.2-1.8 g/L, and the concentration of methyl viologen is 8-12 g/L.
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| CN110330532A (en) * | 2019-07-24 | 2019-10-15 | 南京邮电大学 | A kind of novel phosphorescent iridium complex and the preparation method and application thereof |
| CN110643637A (en) * | 2019-09-05 | 2020-01-03 | 江苏大学 | Cu2Preparation method and application of O/RGO @ SW inorganic/biological hybrid photocatalyst |
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| CN102181485B (en) * | 2011-01-27 | 2014-04-02 | 同济大学 | Method for promoting hydrogen prepared from organic wastewater by photosynthetic bacteria |
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| CN110330532A (en) * | 2019-07-24 | 2019-10-15 | 南京邮电大学 | A kind of novel phosphorescent iridium complex and the preparation method and application thereof |
| CN110643637A (en) * | 2019-09-05 | 2020-01-03 | 江苏大学 | Cu2Preparation method and application of O/RGO @ SW inorganic/biological hybrid photocatalyst |
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| Quantum dot interactions with and toxicity to Shewanella oneidensis MR-1;Anna M Wroblewska-Wolna et al;《Nanotechnology》;第第31卷卷;第1-10页 * |
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