CN113457656B - Molybdenum selenide/porous carbon composite structure light-controlled nanoenzyme, preparation method and application - Google Patents
Molybdenum selenide/porous carbon composite structure light-controlled nanoenzyme, preparation method and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 116
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 78
- 239000011780 sodium chloride Substances 0.000 claims abstract description 39
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 31
- 239000008103 glucose Substances 0.000 claims abstract description 31
- 102000004190 Enzymes Human genes 0.000 claims abstract description 29
- 108090000790 Enzymes Proteins 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 8
- QKUSRAKPUWQSJS-UHFFFAOYSA-N diazanium 3-ethyl-2H-1,3-benzothiazole-6-sulfonate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)C1=CC=C2N(CC)CSC2=C1.[O-]S(=O)(=O)C1=CC=C2N(CC)CSC2=C1 QKUSRAKPUWQSJS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 238000007740 vapor deposition Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000012047 saturated solution Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 4
- 239000003642 reactive oxygen metabolite Substances 0.000 description 4
- 238000009818 secondary granulation Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
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Abstract
The invention discloses a molybdenum selenide/porous carbon composite structure light-controlled nanoenzyme, a preparation method and application, belonging to the technical field of inorganic nanomaterials and nanoenzyme photocatalysis. A molybdenum selenide/porous carbon composite structure light-controlled nano enzyme is prepared by reacting twice-granulated molybdenum trioxide with selenium powder by vapor deposition method and in-situ synthesizing on glucose-coated sodium chloride crystal powder, wherein the thickness of molybdenum selenide is 2-10 atomic layers, and the aperture of porous carbon is 2-20 nm. The molybdenum selenide/porous carbon composite structure light-controlled nano enzyme has higher photocatalytic activity, particularly has stronger performances of catalyzing substrates such as o-phenylenediamine, 3', 5' -tetramethyl benzidine, 2' -diazobis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt and the like, and has the advantages of simple preparation process, easy operation and low cost.
Description
Technical Field
The invention belongs to the technical field of inorganic nano materials and nano enzyme photocatalysis, and particularly relates to a molybdenum selenide/porous carbon composite structure light-controlled nano enzyme, a preparation method and application.
Background
Natural enzymes are widely applied to a plurality of fields due to the advantages of remarkable catalytic activity, extremely high specificity and the like, but as biological macromolecules, the problems of poor stability, high price, easy inactivation and the like of the natural enzymes limit practical application. The nano-enzyme has the advantages of stable structure, low cost, rich surface chemical properties and the like, and shows great application prospects in the fields of disease treatment, biochemical detection, environmental protection and the like, so that the nano-enzyme is expected to replace natural enzyme, but the relatively low catalytic activity of the nano-enzyme is a prominent problem to be solved urgently.
The light-regulated nanoenzyme is characterized in that under the action of light, a nanomaterial with unique physical and chemical properties is excited to generate Reactive Oxygen Species (ROS), and the ROS synergistically acts on a substrate to generate enzyme-like catalytic activity. The light-controlled nanoenzyme is an important means for regulating the catalytic activity of the nanoenzyme in recent years. Therefore, how to design a light-sensitive material system and improve the ability of the light-activated nano enzyme to generate ROS is a research method for improving the catalytic activity of the nano enzyme.
Semiconducting two-dimensional MX 2 (such as molybdenum selenide (MoSe) 2 ) And the like) as a two-dimensional structure layered material, has the advantages of large specific surface area, easy surface modification, low toxicity, strong light absorption capacity, high photo-thermal effect, more edge active points and the like, and is attracted by attention in the enzyme-like catalysis aspect. However, two-dimensional MX 2 The lack of active sites in the passivated basal plane and the photo-generated charge recombination phenomenon limit the photocatalytic capability.
Carbon-based materials (porous carbon, carbon quantum dots, graphene quantum dots, carbon nanotubes and the like) are chemically stable, low in cost, easy to modify, high in photoproduction charge separation transfer efficiency and dynamically adjustable in energy level structure, and become one of the hot materials of the multiphase photocatalyst.
In order to solve the defects in the prior art, the invention develops the two-dimensional MX 2 The carbon-based material is combined to construct a composite structure so as to obtain the light-controlled nano enzyme with higher enzyme catalysis-like capability.
Disclosure of Invention
The invention aims to provide the molybdenum selenide/porous carbon composite structure light-controlled nano enzyme which is easy to operate, low in cost and high in catalytic activity.
The invention also aims to provide a preparation method of the light-controlled nano enzyme.
The invention also aims to provide application of the light-controlled nano enzyme.
The technical scheme adopted by the invention is as follows:
a molybdenum selenide/porous carbon composite structure light-controlled nano enzyme is prepared by reacting twice-granulated molybdenum trioxide with selenium powder by vapor deposition method and in-situ synthesizing on glucose-coated sodium chloride crystal powder, wherein the thickness of molybdenum selenide is 2-10 atomic layers, and the aperture of porous carbon is 2-20 nm.
Further, the preparation method of the molybdenum selenide/porous carbon composite structure light-controlled nano-enzyme comprises the steps of adding glucose into a sodium chloride saturated solution, recrystallizing with absolute ethyl alcohol to obtain glucose-coated sodium chloride crystal powder, using the glucose-coated sodium chloride crystal powder as a composite substrate, reacting secondarily granulated molybdenum trioxide and selenium powder by using a vapor deposition method, synthesizing two-dimensional molybdenum diselenide in situ on the composite substrate, washing with water, drying and removing the sodium chloride composite substrate to obtain the molybdenum selenide/porous carbon composite structure light-controlled nano-enzyme.
Preferably, the preparation method comprises the following steps:
(1) Preparing a sodium chloride saturated solution, adding glucose, quickly pouring absolute ethyl alcohol to recrystallize white crystals, and obtaining sodium chloride crystal powder coated with glucose as a composite substrate after vacuum drying, grinding and crushing;
(2) Pressing molybdenum trioxide powder into a sheet under high pressure, crushing and screening into molybdenum trioxide particles with the particle size of 50-200 mu m;
(3) Putting enough 1g of selenium powder into an alumina boat, placing the alumina boat in a low-temperature region of a reaction system, weighing 200-600 mg of molybdenum trioxide particles with the particle size, placing the molybdenum trioxide particles in a high-temperature region of the reaction system, and placing sodium chloride crystal powder coated with glucose on one side of the molybdenum trioxide;
(4) Vacuumizing an alumina boat reaction chamber, regulating the vacuum to 50-300 Pa by using argon/hydrogen mixed carrier gas, starting heating at the heating rate of 5-10 ℃/min, controlling a low-temperature region to 250-350 ℃, controlling a high-temperature region to 550-650 ℃, reacting for 50-80 min after reaching a preset temperature, naturally cooling after finishing, and finally washing and drying to obtain the molybdenum selenide/porous carbon composite structure.
Preferably, in the step (1), 10 to 30 g of sodium chloride is prepared into a saturated solution, and then 10 to 30 g of glucose is added for recrystallization.
And (2) keeping the pressure of 2 g of molybdenum trioxide powder for 6 min at 25 MPa, and pressing the molybdenum trioxide powder into a sheet.
The step (2) is that the molybdenum trioxide pieces are crushed and sieved by a 75-325 mesh sieve to obtain 50-200 mu m molybdenum trioxide particles.
And (4) vacuumizing the reaction chamber to be below 5 Pa.
The argon flow in the step (4) is 45-65 sccm, and the hydrogen flow is 4-8 sccm.
Furthermore, the invention also discloses application of the molybdenum selenide/porous carbon composite structure light-controlled nano enzyme in catalyzing o-phenylenediamine, 3', 5' -tetramethylbenzidine and 2,2' -dinitrobis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt substrates.
The invention utilizes two-dimensional MX 2 The carbon-based material is combined to construct a composite structure, and the advantage complementation of the performance is realized through material compounding, so that the aim of enhancing the catalytic activity of the similar enzyme under the synergistic effect is fulfilled. In order to verify the activity of the light-controlled nanoenzyme with the molybdenum selenide/porous carbon composite structure, the dynamic steady-state curve diagram of the light-controlled nanoenzyme is shown in fig. 6 when the light-controlled nanoenzyme is used for catalyzing o-phenylenediamine mimic enzyme, and as can be seen from fig. 6, the composite structure has strong peroxidase-like enzyme catalytic activity.
Compared with the prior art, the invention has the beneficial effects that:
(1) The molybdenum selenide/porous carbon composite structure light-controlled nano enzyme prepared by the invention has higher photocatalytic activity, and especially has stronger performances of catalyzing substrates such as o-phenylenediamine, 3', 5' -tetramethyl benzidine, 2' -diazobis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt and the like;
(2) Wherein the sodium chloride template removed by washing and drying can be recycled;
(3) The preparation method has the advantages of simple preparation process, easy operation and low cost, and can generate the molybdenum selenide/porous carbon composite structure in one step.
Drawings
FIG. 1 is a schematic view of the growth process for a molybdenum selenide/porous carbon composite structure prepared in accordance with the present invention;
FIG. 2 is a scanning electron microscope map of a molybdenum selenide/porous carbon composite structure on unwashed sodium chloride prepared in accordance with the present invention;
FIG. 3 is a scanning electron microscope map of a molybdenum selenide/porous carbon composite structure prepared in accordance with the present invention;
FIG. 4 is a transmission electron microscope map of a molybdenum selenide/porous carbon composite structure prepared in accordance with the present invention;
FIG. 5 is an X-ray photoelectron spectrum of a molybdenum selenide/porous carbon composite structure prepared in accordance with the present invention;
FIG. 6 is a steady state graph of the catalytic o-phenylenediamine simulated enzyme kinetics of the molybdenum selenide/porous carbon composite structure prepared by the invention under illumination.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples, but the scope of the present invention is not limited thereto.
Example 1
A light-controlled nanometer enzyme with a molybdenum selenide/porous carbon composite structure comprises 200 mg of molybdenum trioxide particles subjected to secondary granulation, the particle size of the molybdenum trioxide particles is 100-150 mu m, 18g of glucose and 30 g of sodium chloride; and the thickness of the molybdenum selenide in the molybdenum selenide/porous carbon composite structure is 2-5 atomic layers, the aperture of the porous carbon is 7-12 nm, and the composite structure has strong nano-enzyme catalytic activity on o-phenylenediamine.
The preparation method of the molybdenum selenide/porous carbon composite structure light-controlled nano enzyme has the process flow as shown in figure 1, and comprises the following steps:
(1) Weighing 30 g of sodium chloride to prepare a saturated solution, adding 18g of glucose, quickly pouring absolute ethyl alcohol to recrystallize white crystals, and obtaining sodium chloride crystal powder coated with glucose after vacuum drying, grinding and crushing;
(2) Weighing 2 g of molybdenum trioxide powder, maintaining the pressure for 6 min at 25 MPa to form a sheet, crushing the molybdenum trioxide sheet, and sieving the molybdenum trioxide sheet with a sieve with 100-140 meshes to obtain molybdenum trioxide particles with the particle size of 100-150 mu m;
(3) Putting enough 1g of selenium powder into an alumina boat, placing the alumina boat in a low-temperature region of a reaction system, weighing 200 mg of molybdenum trioxide particles with the particle size of 100-150 mu m, placing the molybdenum trioxide particles in a high-temperature region of the reaction system, and placing the glucose-coated sodium chloride crystal powder prepared in the step (1) on one side of the molybdenum trioxide;
(4) Vacuumizing the reaction chamber to be below 5 Pa, regulating the vacuum to be 80 Pa by argon/hydrogen mixed carrier gas, wherein the flow of the argon is 50 sccm, and the flow of the hydrogen is 6 sccm;
(5) The heating temperature of the low-temperature region is 280 ℃, the heating temperature of the high-temperature region is 600 ℃, the heating rate is 10 ℃/min, the reaction is carried out for 60 min after the preset temperature is reached, the temperature is naturally reduced after the reaction is finished, and finally, the molybdenum selenide/porous carbon composite structure is obtained through washing and drying.
The prepared molybdenum selenide/porous carbon composite structure light-controlled nanoenzyme is characterized, fig. 2 is a scanning electron microscope map of the molybdenum selenide/porous carbon composite structure on unwashed sodium chloride prepared by the invention, and the map shows that the molybdenum selenide/porous carbon composite structure is coated with a NaCl crystal which is not completely covered, so that an obvious NaCl cubic structure can be seen; FIG. 3 is a scanning electron microscope chromatogram of a molybdenum selenide/porous carbon composite structure prepared in accordance with the present invention, showing that the porous carbon is a network-like three-dimensional structure, and the molybdenum selenide is not clearly visible; fig. 4 is a transmission electron microscope map of the molybdenum selenide/porous carbon composite structure prepared by the present invention, in which the molybdenum selenide is a two-dimensional layered structure, stacked on the surface of PCN to form a vertical heterostructure, it can be clearly seen that the lattice spacing at the cross section is 0.628 nm, and the number of judged layers is 2 to 5; fig. 5 is an X-ray photoelectron spectrum of the molybdenum selenide/porous carbon composite structure prepared by the present invention, in which the composite structure shown in the figure contains three elements of C, mo, yes and Se, and the content ratio of molybdenum to selenium is calculated to be close to the stoichiometric ratio 1 of molybdenum selenide according to the peak area and the sensitivity factor.
Example 2
In the embodiment, the light-controlled nanoenzyme with the molybdenum selenide/porous carbon composite structure comprises 250 mg of molybdenum trioxide particles subjected to secondary granulation, the particle size of the molybdenum trioxide particles is 100-150 mu m, 10 g of glucose and 20 g of sodium chloride; and the thickness of the molybdenum selenide in the molybdenum selenide/porous carbon composite structure is 3-6 atomic layers, the aperture of the porous carbon is 15-20 nm, and the composite structure has stronger nano enzyme catalytic activity to o-phenylenediamine.
The preparation method of the molybdenum selenide/porous carbon composite structure light-controlled nano enzyme comprises the following steps:
(1) Weighing 20 g of sodium chloride to prepare a saturated solution, adding 12 g of glucose, quickly pouring absolute ethyl alcohol to recrystallize white crystals, and obtaining sodium chloride crystal powder coated with glucose after vacuum drying, grinding and crushing;
(2) Weighing 2 g of molybdenum trioxide powder, maintaining the pressure for 6 min at 25 MPa to form a sheet, crushing the molybdenum trioxide sheet, and sieving the crushed molybdenum trioxide sheet into molybdenum trioxide particles of 100-150 mu m through a sieve of 100-140 meshes;
(3) Putting enough 1g of selenium powder into an aluminum oxide boat, placing the aluminum oxide boat in a low-temperature region of a reaction system, weighing 100 mg of molybdenum trioxide particles with the particle size of 100-150 mu m, placing the molybdenum trioxide particles in a high-temperature region of the reaction system, and placing the glucose-coated sodium chloride crystal powder prepared in the step (1) on one side of the molybdenum trioxide;
(4) Vacuumizing the reaction chamber to be below 5 Pa, regulating the vacuum to be 150 Pa by argon/hydrogen mixed carrier gas, wherein the flow of the argon is 45 sccm, and the flow of the hydrogen is 5 sccm;
(5) The heating temperature of the low-temperature region is 250 ℃, the heating temperature of the high-temperature region is 550 ℃, the heating rate is 10 ℃/min, the reaction is carried out for 50 min after the preset temperature is reached, the temperature is naturally reduced after the reaction is finished, and finally, the molybdenum selenide/porous carbon composite structure is obtained through washing and drying.
Example 3
In the embodiment, the light-controlled nanoenzyme with the molybdenum selenide/porous carbon composite structure comprises 400 mg of molybdenum trioxide particles subjected to secondary granulation, the particle size of the molybdenum trioxide particles is 50-100 mu m, 15 g of glucose and 30 g of sodium chloride; and the thickness of the molybdenum selenide in the molybdenum selenide/porous carbon composite structure is 4-8 atomic layers, the aperture of the porous carbon is 10-14 nm, and the composite structure has strong nano-enzyme catalytic activity on 3,3', 5' -tetramethyl benzidine.
The preparation method of the molybdenum selenide/porous carbon composite structure light-controlled nano enzyme comprises the following steps:
(1) Weighing 30 g of sodium chloride to prepare a saturated solution, adding 15 g of glucose, quickly pouring absolute ethyl alcohol to recrystallize white crystals, and obtaining sodium chloride crystal powder coated with glucose after vacuum drying, grinding and crushing;
(2) Weighing 2 g of molybdenum trioxide powder, maintaining the pressure for 6 min at 25 MPa to form a sheet, crushing the molybdenum trioxide sheet, and sieving the crushed molybdenum trioxide sheet into 50-100 mu m molybdenum trioxide particles through a sieve with the mesh number of 140-325;
(3) Putting enough 1g of selenium powder into an alumina boat, placing the alumina boat in a low-temperature region of a reaction system, weighing 400 mg of molybdenum trioxide particles with the particle size of 50-100 mu m, placing the molybdenum trioxide particles in a high-temperature region of the reaction system, and placing the glucose-coated sodium chloride crystal powder prepared in the step (1) on one side of the molybdenum trioxide;
(4) Vacuumizing the reaction chamber to be less than 5 Pa, regulating the vacuum to be 300 Pa by using argon/hydrogen mixed carrier gas, wherein the flow of the argon is 65 sccm, and the flow of the hydrogen is 8 sccm;
(5) The heating temperature of the low-temperature region is 350 ℃, the heating temperature of the high-temperature region is 650 ℃, the heating rate is 10 ℃/min, the reaction is carried out for 80 min after the preset temperature is reached, the temperature is naturally reduced after the reaction is finished, and finally, the molybdenum selenide/porous carbon composite structure is obtained through washing and drying.
Example 4
In the embodiment, the light-controlled nanoenzyme with the molybdenum selenide/porous carbon composite structure comprises 600 mg of molybdenum trioxide particles subjected to secondary granulation, the particle size of the molybdenum trioxide particles is 150-200 mu m, 30 g of glucose and 30 g of sodium chloride; in addition, the thickness of the molybdenum selenide in the molybdenum selenide/porous carbon composite structure is 7-10 atomic layers, the pore diameter of the porous carbon is 2-7 nm, and the composite structure has strong nano-enzyme catalytic activity on 2,2' -dinitrogen bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt.
The preparation method of the molybdenum selenide/porous carbon composite structure light-controlled nano enzyme comprises the following steps:
(1) Weighing 30 g of sodium chloride to prepare a saturated solution, adding 30 g of glucose, quickly pouring absolute ethyl alcohol to recrystallize white crystals, and obtaining sodium chloride crystal powder coated with glucose after vacuum drying, grinding and crushing;
(2) Weighing 2 g of molybdenum trioxide powder, maintaining the pressure for 6 min at 25 MPa to form a sheet, crushing the molybdenum trioxide sheet, and sieving the crushed molybdenum trioxide sheet into 150-200 mu m molybdenum trioxide particles through a sieve with 75-100 meshes;
(3) Putting enough 1g of selenium powder into an alumina boat, placing the alumina boat in a low-temperature region of a reaction system, weighing 600 mg of molybdenum trioxide particles with the particle size of 150-200 mu m, placing the molybdenum trioxide particles in a high-temperature region of the reaction system, and placing the glucose-coated sodium chloride crystal powder prepared in the step (1) on one side of the molybdenum trioxide;
(4) Vacuumizing the reaction chamber to be below 5 Pa, regulating the vacuum to be 50 Pa by argon/hydrogen mixed carrier gas, wherein the flow of the argon is 45 sccm, and the flow of the hydrogen is 4 sccm;
(5) The heating temperature of the low-temperature area is 320 ℃, the heating temperature of the high-temperature area is 630 ℃, the heating rate is 10 ℃/min, the reaction is carried out for 70 min after the preset temperature is reached, the temperature is naturally reduced after the reaction is finished, and finally, the molybdenum selenide/porous carbon composite structure is obtained through water washing and drying.
Claims (8)
1. A preparation method of molybdenum selenide/porous carbon composite structure light-modulation nano enzyme is characterized in that glucose is added into a sodium chloride saturated solution, glucose-coated sodium chloride crystal powder is prepared after recrystallization through absolute ethyl alcohol, the sodium chloride crystal powder is used as a composite substrate, molybdenum trioxide and selenium powder which are granulated twice are reacted through a vapor deposition method, two-dimensional molybdenum diselenide is synthesized in situ on the composite substrate, the sodium chloride composite substrate is removed through washing and drying, and the molybdenum selenide/porous carbon composite structure light-modulation nano enzyme is obtained, wherein the thickness of each atomic layer of molybdenum selenide is 2-10, and the aperture of porous carbon is 2-20 nm.
2. The method of claim 1, comprising the steps of:
(1) Preparing a sodium chloride saturated solution, adding glucose, quickly pouring absolute ethyl alcohol to recrystallize to obtain white crystals, and obtaining sodium chloride crystal powder coated with glucose as a composite substrate after vacuum drying, grinding and crushing;
(2) Pressing molybdenum trioxide powder into a sheet under high pressure, crushing and screening into molybdenum trioxide particles with the particle size of 50-200 mu m;
(3) Putting enough 1g of selenium powder into an aluminum oxide boat, placing the aluminum oxide boat in a low-temperature region of a reaction system, weighing 200-600 mg of molybdenum trioxide particles with the particle size, placing the molybdenum trioxide particles in a high-temperature region of the reaction system, and placing sodium chloride crystal powder coated with glucose on one side of the molybdenum trioxide;
(4) Vacuumizing an alumina boat reaction chamber, regulating the vacuum to 50-300 Pa by using argon/hydrogen mixed carrier gas, starting heating at the heating rate of 5-10 ℃/min, controlling a low-temperature region to 250-350 ℃, a high-temperature region to 550-650 ℃, reacting for 50-80 min after reaching a preset temperature, naturally cooling after finishing, and finally washing and drying to obtain the molybdenum selenide/porous carbon composite structure.
3. The method according to claim 2, wherein the step (1) is carried out by preparing a saturated solution of 10 to 30 g of sodium chloride and then adding 10 to 30 g of glucose to the saturated solution to carry out recrystallization.
4. The production method according to claim 2, wherein the step (2) is carried out by pressing 2 g of molybdenum trioxide powder into a sheet under a pressure of 25 MPa for 6 min.
5. The method according to claim 2, wherein the step (2) comprises crushing the molybdenum trioxide sheet and sieving the crushed molybdenum trioxide sheet with a 75-325 mesh sieve to obtain molybdenum trioxide particles of 50-200 μm.
6. The method of claim 2, wherein the step (4) is performed by evacuating the reaction chamber to a pressure below 5 Pa.
7. The production method according to claim 2, wherein the flow rate of argon in the step (4) is 45 to 65 sccm, and the flow rate of hydrogen is 4 to 8 sccm.
8. The application of the molybdenum selenide/porous carbon composite structure light-controlled nanoenzyme prepared by the preparation method according to any one of claims 1 to 7 in catalyzing o-phenylenediamine, 3', 5' -tetramethylbenzidine and 2,2' -dinitrobis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt substrates.
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