CN109225268B - Preparation method of honeycomb porous structure substrate-supported nano material - Google Patents
Preparation method of honeycomb porous structure substrate-supported nano material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 180
- 239000000758 substrate Substances 0.000 claims abstract description 117
- 239000000463 material Substances 0.000 claims abstract description 97
- 239000002243 precursor Substances 0.000 claims abstract description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 239000008367 deionised water Substances 0.000 claims abstract description 60
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002105 nanoparticle Substances 0.000 claims abstract description 51
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 238000007789 sealing Methods 0.000 claims abstract description 22
- 238000004140 cleaning Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 20
- 150000001661 cadmium Chemical class 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 53
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 53
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 53
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 53
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 33
- 239000010936 titanium Substances 0.000 claims description 33
- 229910052719 titanium Inorganic materials 0.000 claims description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 238000009832 plasma treatment Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- RMCKOIXJLDOSOT-UHFFFAOYSA-L cadmium(2+);oxalate Chemical compound [Cd+2].[O-]C(=O)C([O-])=O RMCKOIXJLDOSOT-UHFFFAOYSA-L 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 34
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- 230000001413 cellular effect Effects 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/04—Sulfides
-
- B01J35/56—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a preparation method of a honeycomb pore-shaped structure substrate-supported nano material, which comprises the following steps: pretreatment of the substrate: carrying out ultrasonic cleaning on the substrate by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 15-45 min each time; preparing a precursor solution: dissolving cadmium salt in deionized water, and stirring for 5-10 min to obtain 0.15-0.2 mol/L cadmium salt solution; dissolving a sulfur source in deionized water, and stirring for 3-5 min to obtain a sulfur source solution of 0.25-0.3 mol/L; mixing a cadmium salt solution and a sulfur source solution in a volume ratio of 1.2-2.5: 1, and adjusting the pH value of the mixed solution by using a NaOH solution of 3-5 mol/L to obtain a precursor solution; hydrothermal synthesis: putting the substrate and the precursor solution into an autoclave, sealing the autoclave, heating to 100-400 ℃, keeping for 0.5-6 h, and then naturally cooling to room temperature; and obtaining the substrate loaded CdS nano-particle material with the honeycomb duct-shaped structure. The method has the advantages of green and environment-friendly raw materials, simple one-step hydrothermal method, realization of mass production, adjustment of the size of the honeycomb pore channel through a simple pH value, and further optimization of catalytic performance.
Description
Technical Field
The invention relates to a preparation method of a CdS nano material, in particular to a preparation method of a substrate loaded nano material with a honeycomb duct-shaped structure.
Background
Cadmium sulfide is a typical IIB-VIA semiconductor material, has the forbidden band width of 2.42eV at room temperature, has strong photoelectric effect in the visible light range, and has important application prospects in the fields of photoelectrons and new energy resources, such as light emitting diodes, infrared detectors, photoconductive gas sensors, semiconductor lasers, solar cells, photocatalysis and photoelectrocatalysis.
Particularly in the field of catalysis, the nano-scale cadmium sulfide has higher surface area and richer active sites, and shows unique visible light catalytic activity. But also because the surface activation energy is improved, the nano-scale cadmium sulfide is easy to agglomerate, the specific surface area is reduced, the surface reaction active sites are reduced, and the stability and the catalytic activity of the nano-scale cadmium sulfide are further influenced. To solve this problem, CdS two-dimensional thin films are typically grown directly on the substrate to obtain good stability and catalytic activity.
Currently, sputtering methods (e.g. CN201510179496.8, CN201410537517.4), thermal evaporation methods (e.g. CN201410609550.3), atomic layer deposition methods (e.g. CN201510257498.4, CN201110107437.1), chemical vapor deposition methods (e.g. CN201510630858.0, CN201410564016.5), chemical bath deposition methods (e.g. CN201210012464.5, CN201210008821.0), microwave hydrothermal methods (e.g. CN201010182007.1, CN200910218822.6), atomized pyrolysis methods (e.g. CN201410152965.2) and the like are mainly used for preparing the cadmium sulfide thin film. However, these methods usually require expensive instruments, harsh experimental conditions, cumbersome preparation processes, and toxic raw materials. Therefore, an effective synthesis strategy is found, which can effectively avoid the agglomeration of CdS nanoparticles, and is extremely important and urgent in low cost, simple preparation process and environmental protection.
In order to realize the purpose, the CdS nano-particles prepared by a one-step hydrothermal method are directly loaded on cellular channel-shaped TiO2The structure of the material on the substrate can avoid the agglomeration of CdS nano particles, effectively ensure the large surface area and active sites of the nano particles, and simultaneously ensure the honeycomb porous TiO2The substrate is beneficial to charge transfer and gas adsorption and desorption in the catalysis process. The raw materials used in the preparation method are green and environment-friendly, the one-step hydrothermal method is simple, mass production can be realized, the size of the honeycomb pore channel can be adjusted through a simple pH value, and the catalytic performance is further optimized.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing a nanomaterial supported on a honeycomb cellular structure substrate, comprising the steps of:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 15-45 min each time;
step two, preparing a precursor solution: dissolving cadmium salt in deionized water, and stirring for 5-10 min to obtain 0.15-0.2 mol/L cadmium salt solution; dissolving a sulfur source in deionized water, and stirring for 3-5 min to obtain a sulfur source solution of 0.25-0.3 mol/L; mixing a cadmium salt solution and a sulfur source solution in a volume ratio of 1.2-2.5: 1, and adjusting the pH value of the mixed solution by using a NaOH solution of 3-5 mol/L to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the substrate and the precursor solution into an autoclave, sealing the autoclave, heating to 100-400 ℃, keeping for 0.5-6 h, and then naturally cooling to room temperature; and obtaining the substrate loaded CdS nano-particle material with the honeycomb duct-shaped structure.
Preferably, the substrate is any one of a titanium sheet, a copper sheet, a zinc sheet, an iron sheet, an aluminum sheet, a nickel sheet and a molybdenum sheet.
Preferably, the cadmium salt is any one of cadmium acetate, cadmium nitrate, cadmium sulfate, cadmium oxalate and cadmium chloride.
Preferably, the sulfur source is any one of potassium sulfide, sodium sulfide, thiocarbamide, thioacetamide, sodium thiosulfate and thiourea.
Preferably, in the second step, 0.01-0.2 mol/L of other element source solution is added into the precursor solution; the other element source solution is any one of ferrous sulfate solution, silver nitrate solution, cobalt nitrate solution and nickel nitrate solution; the volume ratio of the other element source solution to the cadmium salt solution is 1: 1-9.
Preferably, the pH value in the second step is 7-13.
Preferably, in the third step, the mixture is heated to 100-230 ℃ at the speed of 1-5 ℃/min and is kept for 3-4 hours.
Preferably, in the third step, the heating process is as follows: heating to 120 deg.C at a speed of 5 deg.C/min, maintaining for 30min, heating to 180 deg.C at a speed of 2 deg.C/min, maintaining for 1h, continuing heating to 250 deg.C at a speed of 2 deg.C/min, and maintaining for 30 min.
Preferably, the process in step three is replaced by: putting the substrate and the precursor solution into an autoclave, sealing the autoclave, heating the high-temperature high-pressure autoclave to 360-400 ℃, adjusting the pressure in the autoclave to 18-35 MPa, and reacting for 15-30 min; naturally cooling to room temperature; and obtaining the substrate loaded CdS nano-particle material with the honeycomb duct-shaped structure.
Preferably, in the third step, the CdS nanoparticle material loaded on the substrate with the honeycomb channel-shaped structure is reprocessed, and the process is as follows: placing the substrate with the honeycomb duct-shaped structure and loaded with the CdS nano-particle material in a low-temperature plasma treatment instrument for treatment for 10-20 min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon or nitrogen; the frequency of the low-temperature plasma treatment instrument is 30-50 KHz, the power is 30-50W, and the pressure of argon is 30-80 Pa.
The invention at least comprises the following beneficial effects: the invention utilizes a one-step hydrothermal method to prepare CdS nanoparticles directly loaded on honeycomb pore-shaped TiO2The structure of the material on the substrate can avoid the agglomeration of CdS nano particles, effectively ensure the large surface area and active sites of the nano particles, and simultaneously ensure the honeycomb porous TiO2The substrate is beneficial to charge transfer and gas adsorption and desorption in the catalysis process. The raw materials used in the preparation method are green and environment-friendly, the one-step hydrothermal method is simple, mass production can be realized, the size of the honeycomb pore channel can be adjusted through a simple pH value, and the catalytic performance is further optimized.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 shows cellular TiO prepared in example 1 of the present invention2SEM image of CdS nano-particle material loaded on the structure substrate;
FIG. 2 shows cellular TiO prepared in example 1 of the present invention2SEM image of CdS nano-particle material loaded on the structure substrate;
FIG. 3 is an SEM photograph of a substrate titanium plate used in example 1 of the present invention;
FIG. 4 shows cellular TiO prepared in example 1 of the present invention2The XRD pattern of the CdS nanoparticle material loaded on the structural substrate;
FIG. 5 shows cellular TiO prepared in examples 1 to 7 of the present invention2A specific surface area change diagram of the CdS nano-particle material loaded on the structural substrate;
FIG. 6 shows cellular TiO prepared in examples 1 to 7 of the present invention2The structural substrate supports a graph of the change in mean pore diameter of the CdS nanoparticle material.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 7 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, keeping for 4h, and then naturally cooling to room temperature; obtaining honeycomb porous TiO2The structural substrate supports a CdS nanoparticle material.
FIGS. 1-2 show SEM images of materials prepared in this example;
FIG. 3 shows an SEM image of an unreacted substrate titanium plate; as can be seen from comparison between FIGS. 1-2 and FIG. 3, the material prepared by the embodiment has a honeycomb channel-shaped structure, and CdS nanoparticles are loaded on the surface of the material.
The XRD pattern of the material prepared in this example is shown in FIG. 4, from which it can be seen that the diffraction pattern of the resulting product matches that of CdS in the cubic sphalerite structure, and better matches that of the powder diffraction file (PDF # 80-0019). The obvious diffraction peak shows the good crystallinity of the CdS nano material. All diffraction peaks at 2 θ values of 26.7 °, 44.0 ° and 51.7 ° are attributed to (111), (220) and (51) of cubic-phase CdS, respectively(311) A crystal plane. The rest diffraction peaks are derived from the characteristic diffraction peaks of the substrate titanium sheet, and are due to honeycomb porous TiO2The crystal phase content of the structure is low, so that TiO does not appear in a diffraction pattern2Characteristic peak of (2).
The specific surface of the material prepared in this example was tested to be 52m2G, average pore diameter 88 nm.
Example 2:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 8 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, keeping for 4h, and then naturally cooling to room temperature; obtaining honeycomb porous TiO2The structural substrate supports a CdS nanoparticle material.
The specific surface of the material prepared in this example was tested to be 67m2G, average pore diameter 95 nm.
Example 3:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 9 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, keeping for 4h, and then naturally cooling to room temperature; obtaining honeycomb porous TiO2The structural substrate supports a CdS nanoparticle material.
The specific surface of the material prepared in this example was tested to be 82m2G, average pore diameter 102 nm.
Example 4:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 10 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, keeping for 4h, and then naturally cooling to room temperature; obtaining honeycomb porous TiO2The structural substrate supports a CdS nanoparticle material.
The specific surface of the material prepared in this example was tested to be 90m2G, average pore diameter of 112 nm.
Example 5:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 11 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, keeping for 4h, and then naturally cooling to room temperature; obtaining honeycomb porous TiO2The structural substrate supports a CdS nanoparticle material.
The specific surface of the material prepared in this example was tested to be 102m2G, average pore diameter of 118 nm.
Example 6:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 12 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, keeping for 4h, and then naturally cooling to room temperature; obtaining honeycomb porous TiO2The structural substrate supports a CdS nanoparticle material.
The specific surface of the material prepared in this example was tested to be 125m2G, average pore diameter 123 nm.
Example 7:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 13 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, keeping for 4h, and then naturally cooling to room temperature; obtaining honeycomb porous TiO2The structural substrate supports a CdS nanoparticle material.
The specific surface of the material prepared in this example was tested to be 127m2G, average pore diameter 132 nm.
Example 8:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 7 by using a 5mol/L NaOH solution to obtain a precursor solution; adding 10mL of 0.1mol/L ferrous sulfate solution into the precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, keeping for 4h, and then naturally cooling to room temperature; obtaining honeycomb porous TiO2The structural substrate is loaded with a CdFeS nano-particle material.
The specific surface of the material prepared in this example was tested to be 62.8m2G, average pore diameter of 90 nm.
Example 9:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 7 by using a 5mol/L NaOH solution to obtain a precursor solution; adding 10mL of 0.1mol/L cobalt nitrate solution into the precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, keeping for 4h, and then naturally cooling to room temperature; obtaining honeycomb porous TiO2The structural substrate is loaded with CdCoS nano-particle materials.
The specific surface of the material prepared in this example was tested to be 63.3m2G, average pore diameter of 92 nm.
Example 10:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 7 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, preserving heat for 30min, then heating to 180 ℃ at the speed of 2 ℃/min, preserving heat for 1h, continuing heating to 250 ℃ at the speed of 2 ℃/min, preserving heat for 30min, and then naturally cooling to room temperature; the CdS nano-particle material loaded on the substrate with the honeycomb duct-shaped structure is obtained, the maximum benefit of each temperature section can be exerted by adopting temperature programming, the total energy loss is reduced, the integral energy utilization rate is improved, the reaction efficiency and effect can be further improved, and the specific surface area of the prepared material is increased;
the specific surface of the material prepared in this example was tested to be 85m2G, average pore diameter 95 nm.
Example 11:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 7 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into a high-pressure kettle, sealing the high-pressure kettle, heating the high-temperature high-pressure kettle to 380 ℃, adjusting the pressure in the high-pressure kettle to 25MPa, and reacting for 30 min; naturally cooling to room temperature; the CdS nano-particle material loaded on the honeycomb pore structure substrate is obtained, the supercritical hydrothermal reaction is adopted, the material with uniform particle size distribution can be prepared, the material can be quickly reacted and formed, the particles are prevented from growing up, the nano-scale material is obtained, the supercritical hydrothermal reaction is adopted, the reaction efficiency can be improved, and the specific surface of the material is further improved.
The specific surface of the material prepared in this example was tested to be 96m2G, average pore diameter of 98 nm.
Example 12:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 7 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into a high-pressure kettle, sealing the high-pressure kettle, heating the high-temperature high-pressure kettle to 395 ℃, adjusting the pressure in the high-pressure kettle to 24MPa, and reacting for 25 min; naturally cooling to room temperature; and obtaining the substrate loaded CdS nano-particle material with the honeycomb duct-shaped structure.
The specific surface of the material prepared in this example was tested to be 98m2G, average pore diameter of 96 nm.
Example 13:
in the third step, the obtained CdS nano-particle material loaded on the honeycomb pore channel structure substrate is reprocessed, and the process comprises the following steps: placing the substrate with the honeycomb duct-shaped structure loaded with the CdS nano-particle material in a low-temperature plasma treatment instrument for treatment for 20min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon or nitrogen; the frequency of the low-temperature plasma processor is 40KHz, the power is 40W, and the pressure of argon is 40 Pa. The specific surface area of the material can be further improved by processing the material through the low-temperature plasma processor.
The remaining process parameters and procedures were exactly the same as in example 1.
The specific surface of the material prepared in this example was tested to be 95m2G, average pore diameter 100 nm.
Example 14:
in the third step, the obtained CdS nano-particle material loaded on the honeycomb pore channel structure substrate is reprocessed, and the process comprises the following steps: placing the substrate with the honeycomb duct-shaped structure loaded with the CdS nano-particle material in a low-temperature plasma treatment instrument for treatment for 15min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon or nitrogen; the frequency of the low-temperature plasma processor is 35KHz, the power is 35W, and the pressure of argon is 35 Pa.
The remaining process parameters and procedures were exactly the same as in example 1.
The specific surface of the material prepared in this example was tested to be 96m2G, average pore diameter 102 nm.
Example 15:
in the third step, the obtained CdS nano-particle material loaded on the honeycomb pore channel structure substrate is reprocessed, and the process comprises the following steps: placing the substrate with the honeycomb duct-shaped structure loaded with the CdS nano-particle material in a low-temperature plasma treatment instrument for treatment for 20min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon or nitrogen; the frequency of the low-temperature plasma processor is 40KHz, the power is 40W, and the pressure of argon is 40 Pa.
The remaining process parameters and procedures were exactly the same as in example 10.
The specific surface of the material prepared in this example was tested to be 115m2G, average pore diameter of 106 nm.
Example 16:
in the third step, the obtained CdS nano-particle material loaded on the honeycomb pore channel structure substrate is reprocessed, and the process comprises the following steps: placing the substrate with the honeycomb duct-shaped structure loaded with the CdS nano-particle material in a low-temperature plasma treatment instrument for treatment for 20min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon or nitrogen; the frequency of the low-temperature plasma processor is 40KHz, the power is 40W, and the pressure of argon is 40 Pa.
The remaining process parameters and procedures were exactly the same as in example 11.
The specific surface of the material prepared in this example was tested to be 135m2G, average pore diameter 102 nm.
Example 17:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 7 by using a 5mol/L NaOH solution to obtain a precursor solution; adding 10mL of 0.1mol/L ferrous sulfate solution into the precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, preserving heat for 30min, then heating to 180 ℃ at the speed of 2 ℃/min, preserving heat for 1h, continuing heating to 250 ℃ at the speed of 2 ℃/min, preserving heat for 30min, and then naturally cooling to room temperature; obtaining honeycomb porous TiO2The structural substrate is loaded with a CdFeS nano-particle material.
The specific surface of the material prepared in this example was tested to be 82m2G, average pore diameter 93 nm.
Example 18:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate titanium sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 7 by using a 5mol/L NaOH solution to obtain a precursor solution; adding 10mL of 0.1mol/L ferrous sulfate solution into the precursor solution;
step three, hydro-thermal synthesis: putting the titanium sheet and the precursor solution into a high-pressure kettle, sealing the high-pressure kettle, heating the high-temperature high-pressure kettle to 395 ℃, adjusting the pressure in the high-pressure kettle to 24MPa, and reacting for 25 min; naturally cooling to room temperature; and obtaining the substrate loaded CdFeS nano-particle material with the honeycomb pore-shaped structure.
The specific surface of the material prepared in this example was tested to be 98m2G, average pore diameter 95 nm.
Example 19:
in the third step, the obtained CdFeS nano-particle material loaded on the honeycomb pore channel structure substrate is reprocessed, and the process comprises the following steps: placing the honeycomb pore-shaped structure substrate loaded with the CdFeS nano-particle material in a low-temperature plasma treatment instrument for treatment for 15min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon or nitrogen; the frequency of the low-temperature plasma processor is 35KHz, the power is 35W, and the pressure of argon is 35 Pa.
The remaining process parameters and procedures were exactly the same as in example 8.
The specific surface of the material prepared in this example was tested to be 108m2(ii)/g, mean pore diameter 103 nm.
Example 20:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: ultrasonic cleaning of a substrate nickel sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 7 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the nickel sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, keeping for 4h, and then naturally cooling to room temperature; and obtaining the CdS nano-particle material loaded on the substrate with the honeycomb porous nickel oxide structure.
The material prepared in this example was tested to have a specific surface of 58m2G, average pore diameter 85 nm.
Example 21:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: ultrasonic cleaning of a substrate nickel sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 7 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the nickel sheet and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at the speed of 5 ℃/min, preserving heat for 30min, then heating to 180 ℃ at the speed of 2 ℃/min, preserving heat for 1h, continuing heating to 250 ℃ at the speed of 2 ℃/min, preserving heat for 30min, and then naturally cooling to room temperature; and obtaining the substrate loaded CdS nano-particle material with the honeycomb duct-shaped structure.
The specific surface of the material prepared in this example was tested to be 88m2G, average pore diameter of 96 nm.
Example 22:
a preparation method of a honeycomb channel-shaped structure substrate loaded nanometer material comprises the following steps:
step one, pretreatment of a substrate: ultrasonic cleaning of a substrate nickel sheet by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 30min each time;
step two, preparing a precursor solution: dissolving 5mmol of cadmium sulfate in 30mL of deionized water, and stirring for 5min to obtain a cadmium sulfate solution; dissolving 5mmol of sodium sulfide in 20mL of deionized water, and stirring for 3min to obtain a sodium sulfide solution; mixing a cadmium sulfate solution and a sodium sulfide solution, and adjusting the pH value to 7 by using a 5mol/L NaOH solution to obtain a precursor solution;
step three, hydro-thermal synthesis: putting the nickel sheet and the precursor solution into a high-pressure kettle, sealing the high-pressure kettle, heating the high-temperature high-pressure kettle to 380 ℃, adjusting the pressure in the high-pressure kettle to 25MPa, and reacting for 30 min; naturally cooling to room temperature; obtaining a substrate loaded CdS nano-particle material with a honeycomb duct structure;
the specific surface of the material prepared in this example was tested to be 98m2G, average pore diameter 100 nm.
Example 23:
in the third step, the obtained CdS nano-particle material loaded on the honeycomb pore channel structure substrate is reprocessed, and the process comprises the following steps: placing the substrate with the honeycomb duct-shaped structure loaded with the CdS nano-particle material in a low-temperature plasma treatment instrument for treatment for 20min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon or nitrogen; the frequency of the low-temperature plasma processor is 40KHz, the power is 40W, and the pressure of argon is 40 Pa.
The remaining process parameters and procedures were exactly the same as in example 22.
The specific surface of the material prepared in this example was tested to be 132m2G, average pore diameter 108 nm.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (4)
1. A preparation method of a honeycomb pore-shaped structure substrate loaded nanometer material is characterized by comprising the following steps:
step one, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate by using acetone, ethanol and deionized water respectively, wherein the cleaning time is 15-45 min each time;
step two, preparing a precursor solution: dissolving cadmium salt in deionized water, and stirring for 5-10 min to obtain 0.15-0.2 mol/L cadmium salt solution; dissolving a sulfur source in deionized water, and stirring for 3-5 min to obtain a sulfur source solution of 0.25-0.3 mol/L; mixing a cadmium salt solution and a sulfur source solution in a volume ratio of 1.2-2.5: 1, and adjusting the pH value of the mixed solution by using a NaOH solution of 3-5 mol/L to obtain a precursor solution;
step three, hydro-thermal synthesis: placing the substrate and the precursor solution into an autoclave, sealing the autoclave, heating to 120 ℃ at a speed of 5 ℃/min, preserving heat for 30min, then heating to 180 ℃ at a speed of 2 ℃/min, preserving heat for 1h, continuing heating to 250 ℃ at a speed of 2 ℃/min, preserving heat for 30min, and then naturally cooling to room temperature; obtaining a substrate loaded CdS nano-particle material with a honeycomb duct structure;
the substrate is any one of a titanium sheet, a copper sheet, a zinc sheet, an iron sheet, an aluminum sheet, a nickel sheet and a molybdenum sheet;
the cadmium salt is any one of cadmium acetate, cadmium nitrate, cadmium sulfate, cadmium oxalate and cadmium chloride;
the sulfur source is any one of potassium sulfide, sodium sulfide, thiocarbamide, thioacetamide, sodium thiosulfate and thiourea;
in the second step, adding 0.01-0.2 mol/L of other element source solution into the precursor solution; the other element source solution is any one of ferrous sulfate solution, silver nitrate solution, cobalt nitrate solution and nickel nitrate solution; the volume ratio of the other element source solution to the cadmium salt solution is 1: 1-9.
2. The method for preparing the substrate-supported nanomaterial with the honeycomb channel-shaped structure according to claim 1, wherein the pH value in the second step is 7-13.
3. The method for preparing the substrate-supported nanomaterial with the honeycomb channel-shaped structure according to claim 1, wherein the process in the third step is replaced by: putting the substrate and the precursor solution into an autoclave, sealing the autoclave, heating the high-temperature high-pressure reaction kettle to 360-400 ℃, adjusting the pressure in the autoclave to 18-35 MPa, and reacting for 15-30 min; naturally cooling to room temperature; and obtaining the substrate loaded CdS nano-particle material with the honeycomb duct-shaped structure.
4. The method for preparing the substrate-supported nano material with the honeycomb channel-shaped structure according to claim 1, wherein in the third step, the obtained substrate-supported CdS nano particle material with the honeycomb channel-shaped structure is reprocessed, and the process comprises the following steps: placing the substrate with the honeycomb duct-shaped structure and loaded with the CdS nano-particle material in a low-temperature plasma treatment instrument for treatment for 10-20 min, wherein the atmosphere of the low-temperature plasma treatment instrument is argon or nitrogen; the frequency of the low-temperature plasma treatment instrument is 30-50 KHz, the power is 30-50W, and the pressure of argon is 30-80 Pa.
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