CN113832496B - Biological semiconductor nano material and preparation method and application thereof - Google Patents

Biological semiconductor nano material and preparation method and application thereof Download PDF

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CN113832496B
CN113832496B CN202111334065.6A CN202111334065A CN113832496B CN 113832496 B CN113832496 B CN 113832496B CN 202111334065 A CN202111334065 A CN 202111334065A CN 113832496 B CN113832496 B CN 113832496B
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cys
nano material
semiconductor nano
bacillus
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CN113832496A (en
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屈庆
李顺灵
李蕾
李晓虹
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Yunnan University YNU
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
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    • 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
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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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention provides a biological semiconductor nano material and a preparation method and application thereof, belonging to the technical field of semiconductor nano materials and microorganisms. According to the invention, bacillus is used as a semiconductor producer, the bacillus secretes a functional compound containing an L-Cys residue by adding L-cysteine (L-Cys) and controlling the incubation temperature, the functional compound can promote cations in soluble salt to be converted into a semiconductor nano material and can be doped into the semiconductor nano material, the sunlight absorption capability of the semiconductor nano material is enhanced, the rapid migration of carriers is facilitated, and finally the biological semiconductor material with excellent photoelectrocatalysis activity is obtained.

Description

Biological semiconductor nano material and preparation method and application thereof
Technical Field
The invention relates to the technical field of semiconductor nano materials and microorganisms, in particular to a biological semiconductor nano material and a preparation method and application thereof.
Background
In recent years, due to the increasing energy and environmental crisis, the enhancement of effective utilization and conversion of clean energy such as solar energy will become one of the important development directions for realizing sustainable development of human society. Photoelectrochemical (PEC) water splitting is an effective means of converting solar energy into clean energy storage. Although many high performance photoanode materials have been developed, the efficient transfer and utilization of photogenerated charge has been a bottleneck that limits their applications. Therefore, there is a continuing interest in the scientific community to develop photoanode semiconductor materials that promote the rapid migration of photogenerated electrons, improve interfacial charge transfer and surface charge recombination, and thus improve PEC performance.
In recent years, a semi-artificial photosynthesis system combines the high-efficiency capture capability of a semiconductor material on light energy and the high-selectivity catalytic capability of organisms, can effectively absorb solar energy to generate photo-generated electrons or reducing power and accelerate the effective migration of electrons to drive organisms to produce hydrogen (Ye, j.yu, j.zhang, y.et al.light-drive carbon dioxide reduction to methyl methane sodium bihybrid. Appl.c.c.b-environ, 257117916 (2019)), which provides a thought for preparing high-performance semiconductor materials, but the system is limited by the surface recombination of microorganisms and inorganic semiconductor materials (such as CdS), still has the problem of slow photo-induced charge dynamics of a photo-anode, and the photocatalytic activity needs to be improved.
Disclosure of Invention
The invention aims to provide a biological semiconductor nano material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a biological semiconductor nano material, which comprises the following steps:
mixing soluble salt, L-cysteine, bacillus and a solvent to obtain a mixed feed liquid; the metal element or metalloid element in the soluble salt is the metal element or metalloid element in the biological semiconductor nano material;
incubating the mixed feed liquid to obtain an incubation liquid; the incubation temperature is 25-40 ℃;
centrifuging the hatching fluid, and dialyzing the supernatant to obtain a colloidal material;
and drying the colloidal material to obtain the biological semiconductor nano material.
Preferably, the metal element in the soluble salt comprises one or more of Ni, bi, cd, au and Ag, and the metalloid element comprises Te.
Preferably, the bacillus comprises bacillus megaterium or brevibacillus marinus.
Preferably, the concentration of soluble salt in the mixed material liquid is 1-40 mg/L, the concentration of L-cysteine is less than or equal to 0.025mmol/L, and the effective viable count of bacillus is (0.5-2.5) multiplied by 10 7 CFU/mL。
Preferably, the incubation time is 1-7 days.
Preferably, the centrifugation is performed for 3-6 times, the temperature is 4-10 ℃, the rotating speed is 5000-12000 rpm, and the time of single centrifugation is 5-20 min.
Preferably, the molecular interception of the dialysis bag used for dialysis is 100-500 kDa, the dialysis time is 10-48 h, and the dialysis medium used for dialysis is water; the drying is freeze drying.
The invention provides the biological semiconductor nano material prepared by the preparation method in the technical scheme.
The invention provides application of the biological semiconductor nano material in the technical scheme in photoelectrocatalysis water decomposition hydrogen production.
Preferably, the biological semiconductor nano material is used as a photo-anode material.
The invention provides a preparation method of a biological semiconductor nano material. According to the invention, bacillus is used as a semiconductor producer, the bacillus secretes a functional compound containing an L-Cys residue by adding L-cysteine (L-Cys) and controlling the incubation temperature, the functional compound can promote cations in soluble salt to be converted into a semiconductor nano material and can be doped into the semiconductor nano material, the sunlight absorption capability of the semiconductor nano material is enhanced, the fast migration of carriers is facilitated, and finally the biological semiconductor material with excellent photoelectrocatalysis activity is obtained.
Drawings
FIG. 1 shows Ni prepared in example 1 x S x-1 /Ni 5 P 4 TEM image of Cys;
FIG. 2 shows Ni prepared in example 1 x S x-1 /Ni 5 P 4 -XRD pattern of Cys;
FIG. 3 shows Ni prepared in example 1 x S x-1 /Ni 5 P 4 -FTIR plot of Cys and L-Cys;
FIG. 4 shows Ni prepared in example 1 x S x-1 /Ni 5 P 4 -UV-Vis DRS map of Cys;
FIG. 5 shows Ni prepared in example 1 x S x-1 /Ni 5 P 4 -LSV profile of Cys versus the bio-semiconductor nanomaterial prepared in comparative example 1;
FIG. 6 shows P-dot/Bi prepared in example 2 2 O 3 TEM image of Cys;
FIG. 7 is a TEM image of P-doped/Te-Cys prepared in example 3;
FIG. 8 is a TEM image of P-coped/CdS-Cys prepared in example 4;
FIG. 9 is a TEM image of P-doped/AuAg-Cys prepared in example 5.
Detailed Description
The invention provides a preparation method of a biological semiconductor nano material, which comprises the following steps:
mixing soluble salt, L-cysteine, bacillus and a solvent to obtain a mixed feed liquid; the metal element or metalloid element in the soluble salt is the metal element or metalloid element in the biological semiconductor nano material;
incubating the mixed feed liquid to obtain an incubation liquid; the incubation temperature is 25-40 ℃;
centrifuging the hatching fluid, and dialyzing the supernatant to obtain a colloidal material;
and drying the colloidal material to obtain the biological semiconductor nano material.
Soluble salt, L-cysteine, bacillus and a solvent are mixed to obtain mixed feed liquid; the metal element or metalloid element in the soluble salt is the metal element or metalloid element in the biological semiconductor nano material. In the invention, the metal elements in the soluble salt preferably comprise one or more of Ni, bi, cd, au and Ag, the metalloid elements preferably comprise Te, and the soluble salt preferably comprises NiCl 2 、Bi(NO 3 ) 3 、TeCl 4 、CdCl 2 、AgNO 3 And HAuCl 4 One or more of them. In the present invention, the bacillus preferably includes bacillus megaterium or brevibacillus marinus;the sources of the Bacillus megaterium and Brevibacillus marinus are not particularly limited in the present invention, and in the examples of the present invention, the Bacillus megaterium is preferably B-16 T Strain (Bacillus nematocida sp. Nov., a novel bacterial strain with a biochemical activity isolated from soil in Yunnan, china; xiao-Wei Huang, qiu-HongNiu, wei Zhou, ke-Qin Zhang; systematic and applied microbiology 28 (2005) 323-327). In the invention, the bacillus megaterium and the brevibacillus laterosporus are beneficial bacteria, have the advantages of environmental friendliness, safety to grain crops, no harm to human and livestock and the like, and are widely distributed in various environments such as water, soil, plants, animals, air and the like. In the invention, the concentration of soluble salt in the mixed material liquid is preferably 1-40 mg/L, and more preferably 15-30 mg/L; the concentration of the L-cysteine is preferably less than or equal to 0.025mmol/L, and more preferably 0.005-0.015 mmol/L; the effective viable count of Bacillus is preferably (0.5-2.5). Times.10 7 CFU/mL, more preferably (0.5 to 1.5). Times.10 7 CFU/mL. In the present invention, the solvent preferably includes water, which is preferably sterile distilled water.
The invention preferentially cultures the bacillus to obtain bacillus fermentation liquor; dissolving soluble salt in water to obtain soluble salt water solution; dissolving L-cysteine in water to obtain an L-cysteine aqueous solution; and mixing the bacillus fermentation liquor, the soluble salt water solution and the L-cysteine water solution to obtain the mixed feed liquid. In the present invention, the effective viable count of the bacillus fermentation liquid is preferably (1.0 to 5.0) × 10 9 CFU/mL, more preferably (1.0 to 2.0). Times.10 9 CFU/mL; the concentration of the soluble salt water solution is preferably 1-40 mg/L, and more preferably 10-30 mg/L; the concentration of the aqueous solution of L-cysteine is preferably 5mmol/L or less, more preferably 1 to 2mmol/L. The method for culturing Bacillus in the present invention is not particularly limited, and any method known to those skilled in the art may be used. In an embodiment of the invention, the method of culturing comprises the steps of: inoculating bacillus into a culture medium for incubation to obtain bacillus megaterium fermentation liquor; the culture medium is preferably LB liquid culture medium; the temperature of the hatchingThe degree is preferably 25 to 40 ℃, and more preferably 27 to 35 ℃; the incubation time is preferably 15-30 h, more preferably 20-24 h; the incubation is preferably carried out in a constant temperature shaker. In the present invention, the soluble salt aqueous solution and the L-cysteine aqueous solution are preferably independently filtered before use to remove undesired bacteria therein; in the present invention, the soluble salt aqueous solution and the L-cysteine aqueous solution are preferably filtered by using a 0.22 μm filter head.
After the mixed feed liquid is obtained, the mixed feed liquid is incubated to obtain the incubation liquid. In the invention, the incubation temperature is 25-40 ℃, and preferably 27-35 ℃; the incubation time is preferably 1 to 7 days, more preferably 4 to 5 days. In the invention, in the hatching process, under the action of L-cysteine at the same time under a proper temperature condition, the bacillus can secrete a functional compound containing an L-Cys residue, the functional compound can promote cations in soluble salt to be converted into a semiconductor nano material and can be doped into the semiconductor nano material, the sunlight absorption capability of the semiconductor nano material is enhanced, the rapid migration of carriers is facilitated, and finally the biological semiconductor material with excellent photoelectrocatalysis activity is obtained. The biological semiconductor nano material can not be prepared successfully even if the temperature is too high or too low in the hatching process, and particularly, the activity of bacillus can be ensured in the hatching temperature range, cations in soluble salt can be converted into the semiconductor nano material, and the finally prepared biological semiconductor nano material is ensured to have excellent photoelectric catalytic activity; the secretion and the secretion amount of the functional compound containing the L-Cys residue are related to the hatching temperature and the content of the L-cysteine, the content of the L-cysteine is preferably controlled within the range, so that the finally obtained biological semiconductor nano material is ensured to have excellent photoelectrocatalysis activity, and the content of the L-cysteine is too little or too much, so that the photoelectrocatalysis activity of the biological semiconductor nano material is not effectively improved.
After obtaining the hatching fluid, the invention centrifuges the hatching fluid and dialyzes the supernatant fluid to obtain the colloidal material. In the present invention, the number of the centrifugation is preferably 3 to 6 times, more preferably 4 to 5 times; the temperature is preferably 4 to 10 ℃, and more preferably 4 to 6 ℃; the rotation speed is preferably 5000-12000 rpm, more preferably 10000-12000 rpm; the time for a single centrifugation is preferably 5 to 20min, more preferably 15 to 20min. In the invention, after each centrifugation, the supernatant is centrifuged for the next time, and the supernatant obtained from the last centrifugation is subjected to subsequent dialysis. In the invention, the molecular cut-off of the dialysis bag used for dialysis is preferably 100 to 500kDa, more preferably 300 to 500kDa; the dialysis time is preferably 10 to 48 hours, more preferably 24 to 36 hours; the dialysis medium used for dialysis is water, and the water is preferably ultrapure water.
After the colloid material is obtained, the invention dries the colloid material to obtain the biological semiconductor nano material. In the present invention, the drying is preferably freeze-drying.
The invention adopts a co-culture method to prepare the biological semiconductor nano material, has simple operation and mild reaction condition which is close to room temperature condition, and is beneficial to realizing large-scale production.
The invention provides the biological semiconductor nano material prepared by the preparation method of the technical scheme. In the present invention, the biological semiconductor nanomaterial has both ultraviolet and visible absorption bands. In an embodiment of the invention, the biological semiconductor nanomaterial comprises Ni x S x-1 /Ni 5 P 4 Cys (x ranges from 1 to 9) and P-coped/Bi 2 O 3 -Cys, P-coped/Te-Cys, P-coped/CdS-Cys or P-coped/AuAg-Cys. In the present invention, the size and morphology of the bio-semiconductor nanomaterial are related to the composition of the bio-semiconductor nanomaterial, specifically, the Ni x S x-1 /Ni 5 P 4 Cys, P-dots/CdS-Cys and P-dots/AuAg-Cys are quantum dots with the size less than 10nm, and the P-dots/Bi 2 O 3 -Cys and P-doped/Te-Cys are nano materials with lamellar structure, and a plurality of fine particles are distributed on the surface of the lamella of the P-doped/Te-CysAnd (3) nanoparticles.
The invention provides application of the biological semiconductor nano material in the technical scheme in photoelectrocatalysis water decomposition hydrogen production. In the invention, the biological semiconductor nano material is particularly used as a photo-anode material. The invention preferably uses the biological semiconductor nano material as a photo-anode material to prepare a photoelectrode, and the preparation method of the photoelectrode preferably comprises the following steps:
mixing the biological semiconductor nano material, nafion solution, isopropanol and water, coating the obtained mixed material on the surface of an electrode matrix, and drying to obtain the photoelectrode.
In the present invention, the concentration of the Nafion solution is preferably 0.5wt%; the dosage ratio of the biological semiconductor nano material, the Nafion solution, the isopropanol and the water is preferably (10-20) mg: (1-10) μ L: (50-500) μ L: μ L (50 to 500), more preferably (15 to 20) mg: (3-5) μ L: (50-55) μ L: (50-55) mu L. In the present invention, the biological semiconductor nanomaterial, nafion solution, isopropyl alcohol and water are mixed, preferably the biological semiconductor nanomaterial and Nafion solution are mixed and then subjected to ultrasonic treatment, and then the obtained material is mixed with isopropyl alcohol and water. In the present invention, the time of the ultrasonic treatment is preferably 1 to 2 hours. In the invention, the material of the electrode substrate is preferably FTO, and the coating amount of the mixed material on the surface of the electrode substrate is preferably 50-100 mu L/cm 2 More preferably 60 to 80. Mu.L/cm 2 . In the present invention, the temperature of the drying is preferably 30 to 40 ℃, and more preferably 35 ℃; the drying time is not particularly limited, and sufficient drying can be achieved.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Ni x S x-1 /Ni 5 P 4 -preparation of Cys, procedure as follows:
s1, culturing bacillus megaterium: bacillus megaterium (B-16) T Bacterial strain) is inoculated into an LB liquid culture medium and placed in a constant temperature oscillator at 27 ℃ for 24 hours to obtain a bacillus megatherium fermentation liquor;
s2, preparing 200mL NiCl with the concentration of 30mg/L 2 The aqueous solution was filtered through a 0.22 μm filter head to remove NiCl 2 Mixed bacteria in the water solution to obtain sterile NiCl 2 An aqueous solution; preparing 1mL of 1mM L-cysteine aqueous solution, and filtering with a 0.22 μm filter head to remove mixed bacteria in the L-cysteine aqueous solution to obtain sterile L-cysteine aqueous solution; to the sterile NiCl 2 Adding the sterile L-cysteine aqueous solution and 1mL of viable count of 1.0 multiplied by 10 into the aqueous solution 9 Placing the obtained mixed solution in a constant-temperature shaking table at 27 ℃ for incubation for 4d to obtain incubation liquid;
s3, centrifuging the hatching fluid in a centrifuge with the rpm of 12000 and the temperature of 4 ℃ for 20min, discarding solids, repeatedly centrifuging the supernatant for 4 times, placing the supernatant obtained by the last centrifugation in a dialysis bag with the molecular cut-off of 500kDa, and dialyzing in ultrapure water for 36h to obtain Ni x S x-1 /Ni 5 P 4 -a Cys colloid; subjecting the Ni to x S x-1 /Ni 5 P 4 -Cys colloid is freeze-dried to obtain Ni x S x-1 /Ni 5 P 4 -Cys powder.
Comparative example 1
A bio-semiconductor nanomaterial was prepared according to the method of example 1, except that L-cysteine was not added.
Ni prepared in example 1 x S x-1 /Ni 5 P 4 Cys, as follows:
FIG. 1 shows Ni prepared in example 1 x S x-1 /Ni 5 P 4 TEM image of-Cys, as can be seen from FIG. 1, ni x S x-1 /Ni 5 P 4 HR-TEM of-Cys shows clear lattice fringes, ni x S x-1 /Ni 5 P 4 -Cys has lattice spacings in the (022) and (042) crystal planes of 0.47nm and 0.32nm, respectively.
FIG. 2 shows Ni prepared in example 1 x S x-1 /Ni 5 P 4 XRD pattern of Cys, from FIG. 2, the sample has diffraction peaks at 30.59 ° and 46.06 °, which correspond to Ni 9 S 8 (PDF#22-1193)、Ni 7 S 6 (PDF # 24-1021) and Ni 5 P 4 Characteristic diffraction peaks of (PDF # 18-0883), indicating successful Ni production x S x-1 /Ni 5 P 4 -Cys。
FIG. 3 shows Ni prepared in example 1 x S x-1 /Ni 5 P 4 FTIR patterns of-Cys and L-Cys, as can be seen from FIG. 3, the product prepared in example 1 contained L-Cys, indicating that Ni was successfully prepared x S x-1 /Ni 5 P 4 -Cys。
FIG. 4 shows Ni prepared in example 1 x S x-1 /Ni 5 P 4 UV-Vis DRS map of-Cys, ni, as can be seen from FIG. 4 x S x-1 /Ni 5 P 4 Cys has two absorption bands, with the tangent line as a straight line portion intersecting the abscissa (intersecting the abscissa at 425nm and 668 nm) in FIG. 4, by the formula E g = 1240/lambda calculation to get Ni x S x-1 /Ni 5 P 4 Two band gap values for-Cys are 2.92eV and 1.86eV, respectively.
Ni prepared in example 1 x S x-1 /Ni 5 P 4 -Cys was tested for PEC performance and compared to the bio-semiconductor nanomaterial prepared in comparative example 1, as follows:
s1, assembling a PEC-2000 photoelectrochemical test system (Pofilly) by adopting a three-electrode system, and measuring the performance of photoanode photocatalytic water decomposition at room temperature (25 +/-1 ℃), wherein Ni is coated on the PEC-2000 photoelectrochemical test system x S x-1 /Ni 5 P 4 FTO (1 cm) of Cys 2 ) As a working electrode, pt wire as a counter electrode, ag/AgCl electrode as a reference electrode, 0.35M Na 2 SO 3 、0.25M Na 2 S and 0.5M Na 2 SO 4 The aqueous solution of (A) is an electrolyte(ii) a The preparation method of the working electrode comprises the following steps: 20mg of Ni x S x-1 /Ni 5 P 4 Mixing Cys powder with 5 mu L of Nafion solution with the concentration of 5wt%, performing ultrasonic treatment for 2 hours, dispersing in 50 mu L of isopropanol and 50 mu L of deionized water to obtain a mixed material, coating 60 mu L of the mixed material on the surface of FTO, and drying at 35 ℃ to obtain a working electrode;
s2, in the PEC-2000 photoelectrochemical test system (100 mW/cm) 2 300W xenon lamp, pofely) is added with an AM1.5 global optical filter, then the test is carried out, and OCP, EIS, LSV and i-t curves are collected, wherein the scanning range of the LSV test is-0.6-0.7V, and the scanning speed is 5 mV/s; the EIS is the change of alternating current signal voltage and current along with frequency measured under the conditions of constant potential (0.64V) and AM1.5G solar illumination.
FIG. 5 shows Ni prepared in example 1 x S x-1 /Ni 5 P 4 LSV graph of Cys vs. the nano-material of the bio-semiconductor prepared in comparative example 1, it can be seen from FIG. 5 that the initial potential of the nano-material of the bio-semiconductor prepared in comparative example 1 is 0.41V, and the current density J is 4.62mA cm at 1.23V vs. RHE 2 And Ni prepared in example 1 x S x-1 /Ni 5 P 4 Cys powder with an initial potential of 0.42V and a current density J of 5.97mAcm at 1.23V vs. RHE 2 。
Example 2
P-doped/Bi 2 O 3 -preparation of Cys powder, steps as follows:
s1, culturing bacillus megaterium: bacillus megaterium (B-16) T Bacterial strain) is inoculated into an LB liquid culture medium and placed in a constant temperature oscillator at 27 ℃ for 24 hours to obtain a bacillus megatherium fermentation liquor;
s2, preparing 200mL of Bi (NO) with the concentration of 30mg/L 3 ) 3 The aqueous solution was filtered through a 0.22 μm filter head to remove Bi (NO) 3 ) 3 Mixed bacteria in the water solution to obtain sterile Bi (NO) 3 ) 3 An aqueous solution; preparing 1mL of 1mM L-cysteine aqueous solution, and filtering with a 0.22 μm filter head to remove mixed bacteria in the L-cysteine aqueous solution to obtain sterile L-cysteine aqueous solution; to the sterilityBi(NO 3 ) 3 Adding the sterile L-cysteine aqueous solution and 1mL of viable count of 1.0 multiplied by 10 into the aqueous solution 9 Placing the obtained mixed solution in a constant-temperature shaking table at 27 ℃ for incubation for 5d to obtain incubation liquid, wherein the CFU/mL bacillus megaterium fermentation liquid is obtained;
s3, centrifuging the hatching fluid in a centrifuge with the rpm of 12000 and the temperature of 4 ℃ for 20min, discarding solids, repeatedly centrifuging the supernatant for 4 times, placing the supernatant obtained by the last centrifugation in a dialysis bag with the molecular cut-off of 500kDa, and dialyzing in ultrapure water for 36h to obtain P-coped/Bi 2 O 3 -a Cys colloid; mixing the P-coped/Bi 2 O 3 Freeze drying the-Cys colloid to obtain P-dots/Bi 2 O 3 -Cys powder.
FIG. 6 shows P-dots/Bi prepared in example 2 2 O 3 TEM image of Cys, as can be seen from FIG. 6, the P-coped/Bi 2 O 3 Cys is a two-dimensional sheet-like nanomaterial.
Example 3
The preparation method of the P-coped/Te-Cys powder comprises the following steps:
s1, culturing bacillus megaterium: bacillus megaterium (B-16) T Bacterial strain) is inoculated into an LB liquid culture medium and placed in a constant-temperature oscillator at 27 ℃ for incubation for 24 hours to obtain a bacillus megaterium fermentation liquid;
s2, preparing 200mL of TeCl with the concentration of 30mg/L 4 The aqueous solution was filtered through a 0.22 μm filter head to remove TeCl 4 Mixed bacteria in the aqueous solution to obtain sterile TeCl 4 An aqueous solution; preparing 1mL of 1mM L-cysteine aqueous solution, and filtering with a 0.22 μm filter head to remove mixed bacteria in the L-cysteine aqueous solution to obtain sterile L-cysteine aqueous solution; to the sterile TeCl 4 Adding the sterile L-cysteine aqueous solution and 1mL of viable count of 1.0 × 10 9 Placing the obtained mixed solution in a constant-temperature shaking table at 27 ℃ for incubation for 4d to obtain incubation liquid, wherein the CFU/mL bacillus megaterium fermentation liquid is obtained;
s3, centrifuging the hatching fluid in a centrifuge with the rpm of 12000 and the temperature of 4 ℃ for 20min, discarding solids, repeatedly centrifuging the supernatant for 4 times, placing the supernatant obtained by the last centrifugation in a dialysis bag with the molecular cut-off of 500kDa, and dialyzing in ultrapure water for 36h to obtain a P-coped/Te-Cys colloid; and (3) carrying out freeze drying on the P-dot/Te-Cys colloid to obtain P-dot/Te-Cys powder.
FIG. 7 is a TEM image of P-doped/Te-Cys prepared in example 3, and it can be seen from FIG. 7 that the P-doped/Te-Cys is a lamellar structured nano-material with many fine nanoparticles distributed on the surface of the lamella.
Example 4
The preparation method of the P-coped/CdS-Cys powder comprises the following steps:
s1, culturing bacillus megaterium: bacillus megaterium (B-16) T Bacterial strain) is inoculated into an LB liquid culture medium and placed in a constant temperature oscillator at 27 ℃ for 24 hours to obtain a bacillus megatherium fermentation liquor;
s2, preparing 200mL of CdCl with the concentration of 30mg/L 2 The aqueous solution was filtered through a 0.22 μm filter head to remove CdCl 2 Mixed bacteria in the water solution to obtain sterile CdCl 2 An aqueous solution; preparing 1mL of 1mM L-cysteine aqueous solution, and filtering with a 0.22 μm filter head to remove mixed bacteria in the L-cysteine aqueous solution to obtain sterile L-cysteine aqueous solution; to the sterile CdCl 2 Adding the sterile L-cysteine aqueous solution and 1mL of the effective viable count of 1.0 multiplied by 10 9 Placing the obtained mixed solution in a constant-temperature shaking table at 27 ℃ for incubation for 4d to obtain incubation liquid;
s3, centrifuging the hatching fluid in a centrifuge with the rpm of 12000 and the temperature of 4 ℃ for 20min, discarding solids, repeatedly centrifuging the supernatant for 4 times, placing the supernatant obtained by the last centrifugation in a dialysis bag with the molecular cut-off of 500kDa, and dialyzing in ultrapure water for 36h to obtain a P-coped/CdS-Cys colloid; and (4) carrying out freeze drying on the P-coped/CdS-Cys colloid to obtain P-coped/CdS-Cys powder.
FIG. 8 is a TEM image of P-dots/CdS-Cys prepared in example 4, and from FIG. 8, the P-dots/CdS-Cys are quantum dots with a size of about 5nm.
Example 5
The preparation method of the P-coped/AuAg-Cys comprises the following steps:
s1, cultivating the Brevibacillus laterosporus: inoculating the brevibacillus laterosporus into an LB liquid culture medium, and placing the culture medium in a constant temperature oscillator at 27 ℃ for incubation for 24 hours to obtain brevibacillus laterosporus fermentation liquor;
s2, respectively preparing 100mL of AgNO with the concentration of 30mg/L 3 Aqueous solution and HAuCl 4 Filtering the aqueous solution with 0.22 μm filter head to remove foreign bacteria to obtain sterile AgNO 3 Aqueous solution and sterile HAuCl 4 An aqueous solution; preparing 1mL of 1mM L-cysteine aqueous solution, and filtering with a 0.22 μm filter head to remove mixed bacteria in the L-cysteine aqueous solution to obtain sterile L-cysteine aqueous solution; subjecting the sterile AgNO to 3 Aqueous solution, sterile HAuCl 4 Aqueous solution, sterile L-cysteine aqueous solution and 1mL of the mixture with the effective viable count of 1.0 multiplied by 10 9 Mixing CFU/mL Brevibacillus marinus fermentation liquor, and placing the obtained mixed solution in a constant-temperature shaking table at 27 ℃ for incubation for 4d to obtain an incubation solution;
s3, centrifuging the hatching fluid in a centrifuge with the rpm of 12000 and the temperature of 4 ℃ for 20min, discarding solids, repeatedly centrifuging the supernatant for 4 times, placing the supernatant obtained by the last centrifugation in a dialysis bag with the molecular cut-off of 500kDa, and dialyzing in ultrapure water for 36h to obtain a P-coped/AuAg-Cys colloid; and (3) carrying out freeze drying on the P-dot/AuAg-Cys colloid to obtain P-dot/AuAg-Cys powder.
FIG. 9 is a TEM image of P-dots/AuAg-Cys prepared in example 5, and it can be seen from FIG. 9 that the P-dots/AuAg-Cys are quantum dots with a size of 1-5 nm.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A preparation method of a biological semiconductor nano material comprises the following steps:
mixing soluble salt, L-cysteine, bacillus and a solvent to obtain a mixed feed liquid; the soluble saltThe metal element or metalloid element in the biological semiconductor nano material is the metal element or metalloid element in the biological semiconductor nano material; the metal element in the soluble salt comprises one or more of Ni, bi, au and Ag, and the metalloid element is Te; the bacillus comprises bacillus megaterium or brevibacillus marinus; the concentration of the L-cysteine is less than or equal to 0.025mmol/L; the concentration of soluble salt in the mixed feed liquid is 1 to 40mg/L, and the effective viable count of bacillus is (0.5 to 2.5) multiplied by 10 7 CFU/mL；
Incubating the mixed feed liquid to obtain an incubation liquid; the incubation temperature is 25 to 40 ℃;
centrifuging the hatching fluid, and dialyzing the supernatant to obtain a colloidal material;
and drying the colloidal material to obtain the biological semiconductor nano material.
2. The method of claim 1, wherein the incubation time is 1 to 7d.
3. The preparation method according to claim 1, wherein the centrifugation is performed for 3 to 6 times, the temperature is 4 to 10 ℃, the rotation speed is 5000 to 12000rpm, and the time of single centrifugation is 5 to 20min.
4. The preparation method according to claim 1, wherein the molecular cut-off of a dialysis bag used for dialysis is 100 to 500kDa, the dialysis time is 10 to 48h, and a dialysis medium used for dialysis is water; the drying is freeze drying.
5. A biological semiconductor nanomaterial prepared by the preparation method of any one of claims 1 to 4.
6. The use of the biological semiconductor nanomaterial of claim 5 in photoelectrocatalytic water decomposition for hydrogen production.
7. The use according to claim 6, wherein the biological semiconductor nanomaterial is used as a photoanode material.
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