CN113415821B - Hollow Zn x Cd 1-x Preparation method and application of S solid solution nanosphere - Google Patents
Hollow Zn x Cd 1-x Preparation method and application of S solid solution nanosphere Download PDFInfo
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- 239000002077 nanosphere Substances 0.000 title claims abstract description 37
- 239000006104 solid solution Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000005530 etching Methods 0.000 claims abstract description 27
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 239000011701 zinc Substances 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 39
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 14
- 239000001509 sodium citrate Substances 0.000 claims description 13
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 10
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-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
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 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
- 230000035484 reaction time Effects 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
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- 239000001257 hydrogen Substances 0.000 abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000000377 silicon dioxide Substances 0.000 abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 24
- 229910021642 ultra pure water Inorganic materials 0.000 description 19
- 239000012498 ultrapure water Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002244 precipitate Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- -1 transition metal sulfides Chemical class 0.000 description 3
- 238000010923 batch production Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OWQUYBAASOSGNO-CDNKMLFNSA-N 2-[[(Z)-N-(2-hydroxy-5-sulfoanilino)-C-phenylcarbonimidoyl]diazenyl]benzoic acid Chemical compound C1=CC=C(C=C1)/C(=N/NC2=C(C=CC(=C2)S(=O)(=O)O)O)/N=NC3=CC=CC=C3C(=O)O OWQUYBAASOSGNO-CDNKMLFNSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229940043798 zincon Drugs 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G11/00—Compounds of cadmium
- C01G11/006—Compounds containing, besides cadmium, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a hollow Zn x Cd 1‑x The preparation method of S solid solution nanospheres and the application thereof are characterized in that silicon dioxide nanospheres are used as templates, added Zn and Cd ions are complexed with ammonia water and hydrolyzed under the alkalescent condition to generate hydroxyl complex, the hydroxyl complex reacts with thiourea, and Zn is firstly formed through continuous reaction etching x Cd 1‑x S shell layer grows on the surface of the silicon dioxide ball, strong alkali is added immediately to remove the silicon dioxide template, and hollow Zn is obtained x Cd 1‑x And (4) an S nanosphere. The method realizes hollow Zn by a continuous reaction etching method x Cd 1‑x And the S solid solution nanospheres are synthesized in one step, so that the loss of Zn element under the condition of multi-step alkaline etching is avoided. Zn prepared by the method x Cd 1‑x S has high activity of hydrolyzing water to produce hydrogen, and the maximum amount of S can be 2.52 mmoleg under the irradiation of visible light ‑1 h ‑1 And (4) hydrogen production efficiency. In addition, the preparation process has the advantages of simple synthesis, mild reaction conditions, rich and cheap raw materials and the like.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to hollow Zn x Cd 1-x A preparation method and application of S solid solution nanospheres.
Background
As an important photocatalytic hydrogen production material, transition metal sulfides are widely reported due to their characteristics of direct band gap, narrow forbidden band width, large exciton binding energy, and the like. Transition metal sulfides are generally lamellar structures, which are bonded by van der waals interactions between layers, and which give transition metal sulfides unique physical and chemical properties: such as high active specific surface, adjustable band gap, increased exciton binding energy, and the like.
Zn x Cd 1-x S is a CdS-based solid solution.
The main preparation methods at present comprise hydrothermal method, solvent thermal method and the like. Usually hydrothermal and solvothermal synthesis of Zn x Cd 1-x The S solid solution needs to be completed at high temperature and high pressure. Zn synthesized by the method x Cd 1-x S shape growth is difficult to control, synthesis conditions are harsh, cost is high, and yield is low, so that industrial batch production is difficult.
Disclosure of Invention
Aiming at the defects of the prior art, the first purpose of the invention is to provide the hollow Zn which has mild synthesis conditions, simple and controllable process and is suitable for industrial batch production x Cd 1-x A preparation method of S solid solution nanospheres.
The second purpose of the invention is to provide the hollow Zn prepared by the preparation method and having excellent natural light absorptivity and photocatalytic hydrogen production efficiency and uniform components x Cd 1-x S solid solution nanospheres.
The third purpose of the invention is to provide hollow Zn x Cd 1-x Application of S solid solution nanospheres.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention relates to a hollow Zn x Cd 1-x The preparation method of the S solid solution nanosphere comprises the following steps: dispersing silicon dioxide nanospheres in water to obtain a dispersion liquid, then adding a sodium citrate solution, a cadmium source, a zinc source, ammonia water and a sulfur source into the dispersion liquid to obtain a mixed liquid, reacting the mixed liquid at 60-90 ℃ for 150-240 min, then adding sodium hydroxide to obtain a reaction liquid, carrying out etching reaction, cooling, washing and drying the obtained product to obtain the hollow Zn x Cd 1-x And (4) an S nanosphere.
The preparation method of the invention takes the silicon dioxide nanosphere as a template, sodium citrate as a surface modifier, added Zn and Cd ions are complexed with ammonia water under the alkalescent condition to generate a hydroxyl complex, the hydroxyl complex reacts with thiourea, anions are replaced by sulfur to generate sulfide, and finally Zn is formed x Cd 1-x S shell layer grows on the surface of the silicon dioxide nanosphere, then sodium hydroxide is directly added in the final stage of growth to etch the silicon dioxide template, namely Zn grows on the silicon dioxide nanosphere through liquid phase continuous reaction etching x Cd 1-x S shell layer and removing the silicon dioxide template to obtain hollow Zn x Cd 1-x And (4) an S nanosphere. The method realizes hollow Zn by a continuous reaction etching method x Cd 1-x And the S solid solution nanospheres are synthesized in one step, so that the loss of Zn element under the alkaline etching condition is avoided.
In the invention, the time for adding the sodium hydroxide for etching is very important, the sodium hydroxide needs to be added in the later period of the reaction, and if the sodium hydroxide is added in the early period, Zn is added due to the early period x Cd 1-x The S shell layer is thin and fragile in the etching process, and if sodium hydroxide is used for separately etching step by step after the reaction is finished, the loss of the Zn element can be caused. In addition, in the present invention, it is also necessary to effectively control the reaction temperature, and if the reaction temperature is low, Zn is caused x Cd 1-x The S shell layer grows slowly and has poor crystallinity, if the reaction temperature is high, the local growth of the shell layer is too fast, and the appearance is difficult to maintain in the etching process.
Preferably, the concentration of the silicon dioxide nanospheres in the dispersion liquid is 0.35-0.55 mg/L.
Preferably, the concentration of the sodium citrate in the mixed solution is 2.5-9 mmol/L.
Preferably, the cadmium source is selected from one of a cadmium nitrate solution, a cadmium acetate solution and a cadmium chloride solution, and is preferably a cadmium nitrate solution.
Preferably, the concentration of cadmium ions in the mixed solution is 0.001-0.005 mol/L, preferably 0.002-0.004 mol/L.
In the invention, Zn with proper thickness can be smoothly grown by controlling the proportion relationship between the silicon dioxide nanospheres and the raw materials x Cd 1-x And (4) an S shell layer.
Preferably, the zinc source is selected from one of a zinc nitrate solution, a zinc acetate solution and a zinc chloride solution, and is preferably a zinc nitrate solution.
Preferably, in the mixed solution, the molar ratio of zinc ions to cadmium ions is 0-8: 1 to 7. Preferably 3-7: 3 to 7.
Preferably, the sulfur source is selected from one of thiourea, sodium sulfite, thioacetamide and sodium sulfide, and is preferably thiourea.
Preferably, in the mixed solution, in terms of molar ratio, (zinc ion + cadmium ion): elemental sulfur is 1: 1.5 to 5.
Preferably, NH is dissolved in the ammonia water 3 The mass fraction of the ammonia water is 20-25 wt%, and the volume ratio of the ammonia water to the water in the dispersion liquid is 1: 80-120, preferably 1: 100 to 110.
Preferably, the concentration of the sodium hydroxide in the reaction liquid is 0.5-2 mol/L.
In the actual operation process, firstly, sodium hydroxide is dissolved in water to obtain a sodium hydroxide solution with the concentration of 10mol/L, and then the sodium hydroxide solution is added into the mixed solution.
The inventor finds that the reaction effect is better when the sodium hydroxide is prepared into a solution and then added into the dispersion liquid, and the sodium hydroxide is dissolved and generates heat if the sodium hydroxide is directly added, so that the local concentration of the sodium hydroxide is too high to influence the product.
Preferably, the etching reaction time is 10-60min, and the product obtained after the etching reaction is cooled to room temperature through an ice bath.
In the actual operation process, after the etching reaction is finished, the product is cooled to room temperature through ice bath, ultrapure water and absolute ethyl alcohol are used for washing for multiple times, precipitates are collected centrifugally, and hollow Zn is obtained after drying x Cd 1-x And (4) an S nanosphere.
The invention also provides the hollow Zn prepared by the preparation method x Cd 1-x S solid solution nanospheres.
The invention also provides the hollow Zn prepared by the preparation method x Cd 1-x Application of S solid solution nanosphere to preparation of hollow Zn x Cd 1-x The S solid solution nanosphere is used for hydrogen production by photolysis of water. The catalytic hydrogen production efficiency can reach 2.52mmol at most under the visible light -1 h -1 。
Compared with the prior art, the invention has the advantages that:
1. the method prepares hollow Zn x Cd 1-x The S is thin in thickness and large in specific surface area, and is beneficial to improving the natural light absorption rate and the photocatalytic hydrogen production efficiency of the material.
2.Zn x Cd 1-x S is a material that is not acid-resistant nor alkali-resistant. The invention adopts a synthetic method of continuous reaction etching, thereby avoiding zincOn the premise of element loss in the etching process, the silicon dioxide template is well removed, so that hollow Zn is obtained x Cd 1-x And (4) an S nanosphere.
3. The synthesis method is simple, the reaction condition is mild, and the subsequent treatment is not needed. Can realize industrialized mass production.
Drawings
Fig. 1 is an SEM image of a monodisperse silica nanosphere template used in the present invention. Monodisperse SiO used in the invention 2 The SEM of the template is shown in FIG. 1, which exists as spheres with diameters below 500 nm.
FIG. 2 shows a hollow Zn obtained in example 2 of the present invention 0.3 Cd 0.7 SEM image of S solid solution nanospheres. From FIG. 2 it can be seen that Zn 0.3 Cd 0.7 S generally forms a spherical structure. Wherein the sphere is a hollow structure as seen from a broken sphere.
FIG. 3 shows a hollow Zn obtained in example 2 of the present invention 0.3 Cd 0.7 TEM images of S solid solution nanospheres. As can be seen from the TEM image of FIG. 3, the results are in agreement with SEM, Zn 0.3 Cd 0.7 S presents a distinct hollow spherical structure.
FIG. 4 shows the hollow Zn obtained in examples 1 to 4 of the present invention x Cd 1-x XRD pattern of S solid solution nanospheres.
FIG. 5 shows the hollow Zn obtained in examples 1 to 4 of the present invention x Cd 1-x And the UV-vis absorption spectrum of the S solid solution nanosphere.
FIG. 6 shows the hollow Zn obtained in examples 1 to 4 of the present invention x Cd 1-x And (3) a photocatalytic hydrogen production performance diagram of the S solid solution nanosphere.
FIG. 7 shows a hollow Zn film obtained in comparative example 1 of the present invention x Cd 1-x SEM image of S solid solution nanospheres.
FIG. 8 is an SEM image of comparative example 2 of the present invention.
FIG. 9 is an SEM photograph of comparative example 3 of the present invention.
Fig. 10 is an EDS plot of example 2 (top), comparative example 4 (middle) and comparative example 3 (bottom).
Detailed Description
The synthesis of the present invention is further described below by way of specific implementation. In particular, the embodiments described herein are only a part of the present invention, and not all embodiments, and all other embodiments that can be obtained by one of ordinary skill in the art without any inventive work based on the embodiments in the present invention are within the scope of the present invention.
The invention is further described with reference to the following figures and specific examples.
Example 1
Ultrasonically dispersing 55mg of monodisperse silicon dioxide nanospheres into 105mL of ultrapure water, and sequentially adding 5mL of 0.12mol/L sodium citrate solution; 5mL of 0.1mol/L cadmium nitrate solution; 1mL of 25wt% ammonia water; 0.5mol/L thiourea was added in an amount of 4mL and mixed well. After the mixture was stirred at 80 ℃ and reacted for 170min, 10mL of 10mol/L sodium hydroxide solution was added and etched for 20 min. And after etching is finished, rapidly cooling the product to room temperature through ice bath, washing the product for a plurality of times by using ultrapure water and absolute ethyl alcohol, centrifugally collecting precipitates, and drying in an oven to obtain the hollow CdS nanosphere-material 1.
Example 2
Ultrasonically dispersing 55mg of monodisperse silicon dioxide nanospheres into 105mL of ultrapure water, and sequentially adding 5mL of 0.12mol/L sodium citrate solution; 1.5mL of 0.1mol/L zinc nitrate and 3.5mL of 0.1mol/L cadmium nitrate solution; 1mL of 25wt% ammonia water; 0.5mol/L thiourea was added in an amount of 4mL and mixed well. After the mixture was stirred at 80 ℃ and reacted for 170min, 10mL of 10mol/L sodium hydroxide solution was added and etched for 20 min. After etching is finished, the product is rapidly cooled to room temperature through ice bath, ultrapure water and absolute ethyl alcohol are used for washing the product for a plurality of times, precipitates are centrifugally collected, and the precipitate is placed in an oven to be dried to obtain hollow Zn 0.3 Cd 0.7 S nanosphere-material 2.
FIG. 2 shows a hollow Zn obtained in example 2 of the present invention 0.3 Cd 0.7 SEM image of S solid solution nanospheres. From FIG. 2 it can be seen that Zn 0.3 Cd 0.7 S generally forms a spherical structure. Wherein the sphere is a hollow structure as seen from a broken sphere.
FIG. 3 shows a hollow Zn obtained in example 2 of the present invention 0.3 Cd 0.7 S solid solutionTEM image of nanospheres. As can be seen from the TEM image of FIG. 3, the results are in agreement with SEM, Zn 0.3 Cd 0.7 S presents a distinct hollow spherical structure.
FIG. 10 is an EDS chart of comparative example 3 (lower) of example 2 (upper) and comparative example 4 (middle), with specific element contents as shown in Table 1:
table 1 EDS element content of material 2 obtained in example 2
| Element | Weight％ | Atomic％ | Net Int. | Error％ | Kratio | Z | A | F |
| S K | 22.08 | 46.39 | 1844.40 | 2.75 | 0.2311 | 1.1518 | 0.8918 | 1.0189 |
| CdL | 61.90 | 37.10 | 1807.30 | 1.98 | 0.5181 | 0.8478 | 0.9877 | 0.9996 |
| ZnK | 16.02 | 16.51 | 111.00 | 6.03 | 0.1698 | 1.0189 | 0.9894 | 1.0510 |
Example 3
Ultrasonically dispersing 55mg of monodisperse silicon dioxide nanospheres into 105mL of ultrapure water, and sequentially adding 5mL of 0.12mol/L sodium citrate solution, 2.5mL of 0.1mol/L zinc nitrate and cadmium nitrate solution and 1mL of 25wt% ammonia water; 0.5mol/L thiourea was added in an amount of 4mL and mixed well. After the mixture was stirred at 80 ℃ and reacted for 170min, 10mL of 10mol/L sodium hydroxide solution was added and etched for 20 min. After etching is finished, the product is rapidly cooled to room temperature through ice bath, ultrapure water and absolute ethyl alcohol are used for washing the product for a plurality of times, precipitates are centrifugally collected, and the precipitate is placed in an oven to be dried to obtain hollow Zn 0.5 Cd 0.5 S nanosphere-material 3.
Example 4
Monodisperse 55mgUltrasonically dispersing the silicon dioxide nanospheres into 105mL of ultrapure water, and sequentially adding 5mL of 0.12mol/L sodium citrate solution; 3.5mL of 0.1mol/L zinc nitrate and 1.5mL of 0.1mol/L cadmium nitrate solution; 1mL of 25wt% ammonia water; 0.5mol/L thiourea was added in an amount of 4mL and mixed well. After the mixture was stirred at 80 ℃ and reacted for 170min, 10mL of 10mol/L sodium hydroxide solution was added and etched for 20 min. After etching is finished, the product is rapidly cooled to room temperature through ice bath, ultrapure water and absolute ethyl alcohol are used for washing the product for a plurality of times, precipitate is centrifugally collected, and the product is placed in an oven to be dried to obtain hollow Zn 0.7 Cd 0.3 S nanosphere-material 4.
Testing the photocatalytic hydrogen production performance of the materials 1 to 4:
10mg each of the materials 1 to 4 obtained in examples 1 to 4 was dispersed in a quartz reactor containing 100mL of ultrapure water, and 1.313g of sodium sulfite and 8.4g of sodium sulfide as sacrificial agents were added, and after 30 minutes of sonication, the reactor was put into a vacuum system to evacuate dissolved gases in the solution. The reactor is kept at a constant temperature of 5 ℃ and is continuously stirred, a 300W xenon lamp is adopted to test the hydrogen production rate of the photo-decomposed water of the sample, and a filter is used to filter incident light with the wavelength less than 420 nm. The hydrogen production was measured every 1 hour. The production of hydrogen was measured by a gas chromatograph equipped with a thermal conductivity detector. As a result, as shown in FIG. 6, it can be seen that excellent hydrogen generation performance was exhibited except that the hydrogen generation performance of the material 1 was slightly inferior, of which the most preferable was the material 4, H 2 The yield can reach 2.52 mmoleg at most -1 h -1 。
Comparative example 1
Ultrasonically dispersing 50mg of monodisperse silicon dioxide nanospheres into 105mL of ultrapure water, and sequentially adding 5mL of 0.12mol/L sodium citrate solution; 8mL of mixed solution of 0.07mol/L zinc nitrate and 0.03mol/L cadmium nitrate; 1mL of 25wt% ammonia water; 4mL of 0.5mol/L thiourea was mixed well. After the mixture was stirred at 80 ℃ and reacted for 170min, 10mL of 10mol/L sodium hydroxide solution was added and etched for 20 min. After etching is finished, the product is rapidly cooled to room temperature through ice bath, ultrapure water and absolute ethyl alcohol are used for washing the product for a plurality of times, precipitates are centrifugally collected, and the precipitate is placed in an oven to be dried to obtain hollow Zn 0.7 Cd 0.3 S nanosphere-comparative 1. FIG. 7 is an SEM image of comparative sample 1, and as a result, it was found that too much addition of the Zn/Cd source resulted in partial Zn x Cd 1-x S nucleate and grow separately.
Comparative example 2
Ultrasonically dispersing 50mg of monodisperse silicon dioxide nanospheres into 105mL of ultrapure water, and sequentially adding 5mL of 0.12mol/L sodium citrate solution; 2mL of a mixed solution of 0.07mol/L zinc nitrate and 0.03mol/L cadmium nitrate; 1mL of 25wt% ammonia water; 0.5mol/L thiourea was added in an amount of 4mL and mixed well. Stirring the mixed solution at 80 ℃ and reacting for 170min, rapidly cooling the product to room temperature by ice bath, washing the product with ultrapure water and absolute ethyl alcohol for several times, centrifuging, collecting precipitate, and drying in an oven to obtain hollow Zn 0.7 Cd 0.3 S nanosphere-control 2. FIG. 8 is an SEM image of comparative 2 where too little Zn/Cd source addition results in a too thin shell.
Comparative example 3
Ultrasonically dispersing 55mg of monodisperse silicon dioxide nanospheres into 105mL of ultrapure water, and sequentially adding 5mL of 0.12mol/L sodium citrate solution; 5mL of 0.1mol/L zinc nitrate; 1mL of 25wt% ammonia water; 0.5mol/L thiourea was added in an amount of 4mL and mixed well. After the mixture was stirred at 80 ℃ and reacted for 170min, 10mL of 10mol/L sodium hydroxide solution was added and etching was carried out for 20 min. And after etching, rapidly cooling the product to room temperature through ice bath, washing the product for several times by using ultrapure water and absolute ethyl alcohol, centrifugally collecting precipitates, and drying in an oven to obtain the hollow ZnO nanosphere-comparison sample 3. Fig. 9 is an SEM image of comparative example 3, and fig. 10 is an EDS image of comparative example 3 (upper) and comparative example 4 (middle) showing that the product is converted into zinc oxide due to an excessive Zn content ratio.
Comparative example 4
Ultrasonically dispersing 55mg of monodisperse silicon dioxide nanospheres into 105mL of ultrapure water, and sequentially adding 5mL of 0.12mol/L sodium citrate solution; 3.5mL of 0.1mol/L zinc nitrate and 1.5mL of 0.1mol/L cadmium nitrate solution; 1mL of 25wt% ammonia water; 0.5mol/L thiourea was added in an amount of 4mL and mixed well. Stirring the mixed solution at 80 ℃ and reacting for 170min, rapidly cooling the product to room temperature by ice bath, and using ultrapure water and anhydrous ethyl acetateWashing the product with alcohol for several times, centrifuging to collect precipitate, etching in 1mol/L NaOH for 20min, washing the etched product with ultrapure water and anhydrous ethanol for several times, centrifuging to collect precipitate, and drying in a drying oven to obtain hollow Zn 0.7 Cd 0.3 S nanosphere-control 4. FIG. 10 is an EDS chart of comparative example 3 (lower) of example 2 (upper) and comparative example 4 (middle), with specific element contents as shown in Table 2:
table 2 EDS elemental content of control 4
| Element | Weight％ | Atomic％ | Net Int. | Error％ | Kratio | Z | A | F |
| S K | 20.00 | 46.48 | 2423.99 | 3.33 | 0.2077 | 1.1613 | 0.8720 | 1.0258 |
| CdL | 79.00 | 52.38 | 3506.54 | 2.36 | 0.6794 | 0.8688 | 0.9904 | 0.9995 |
| ZnK | 1.00 | 1.14 | 16.85 | 42.88 | 0.0108 | 1.0272 | 0.9794 | 1.0686 |
It can be seen that the reacted product is separately etched to prepare Zn 0.7 Cd 0.3 S, EDS showed no Zn element.
Claims (6)
1. Hollow Zn x Cd 1-x The preparation method of the S solid solution nanosphere is characterized by comprising the following steps: the method comprises the following steps: dispersing the silicon dioxide nanospheres in water to obtain a dispersion liquid, then adding a sodium citrate solution, a cadmium source, a zinc source, ammonia water and a sulfur source into the dispersion liquid, and mixing to obtain a mixed liquid, wherein the molar ratio of zinc ions to cadmium ions in the mixed liquid is (3-7): 3-7, reacting the mixed solution at 60-90 ℃ for 150-240 min, and addingAdding sodium hydroxide to obtain reaction liquid, carrying out etching reaction, cooling, washing and drying the obtained product to obtain the hollow Zn x Cd 1-x And S nanospheres, wherein the concentration of sodium hydroxide in the reaction liquid is 0.5-2 mol/L, the etching reaction time is 10-60min, and the product obtained after the etching reaction is cooled to room temperature through ice bath.
2. A hollow Zn according to claim 1 x Cd 1-x The preparation method of the S solid solution nanosphere is characterized by comprising the following steps: in the dispersion liquid, the concentration of the silicon dioxide nanospheres is 0.35-0.55 mg/L, and the concentration of the sodium citrate in the mixed liquid is 2.5-9 mmol/L.
3. A hollow Zn according to claim 1 x Cd 1-x The preparation method of the S solid solution nanosphere is characterized by comprising the following steps: the cadmium source is selected from one of a cadmium nitrate solution, a cadmium acetate solution and a cadmium chloride solution, and the concentration of cadmium ions in the mixed solution is 0.001-0.005 mol/L.
4. A hollow Zn according to claim 1 x Cd 1-x The preparation method of the S solid solution nanosphere is characterized by comprising the following steps: the zinc source is selected from one of zinc nitrate solution, zinc acetate solution and zinc chloride solution.
5. A hollow Zn according to claim 1 x Cd 1-x The preparation method of the S solid solution nanosphere is characterized by comprising the following steps: the sulfur source is selected from one of thiourea, sodium sulfite, thioacetamide and sodium sulfide, and in the mixed solution, the molar ratio of (zinc ion + cadmium ion): elemental sulfur = 1: 1.5 to 5.
6. A hollow Zn according to claim 1 x Cd 1-x The preparation method of the S solid solution nanosphere is characterized by comprising the following steps: dissolving NH in the ammonia water 3 The mass fraction of the ammonia water is 20-25 wt%, and the volume ratio of the ammonia water to the water in the dispersion liquid is 1: 80-120 parts.
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