CN110975886A - Porous two-dimensional zinc cadmium sulfide nanosheet and preparation method and application thereof - Google Patents
Porous two-dimensional zinc cadmium sulfide nanosheet and preparation method and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 claims abstract description 24
- 238000004729 solvothermal method Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001661 cadmium Chemical class 0.000 claims abstract description 16
- 150000003751 zinc Chemical class 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- ZXMZHGJNBSYCEQ-UHFFFAOYSA-N C(CN)N.[S-2].[Zn+2] Chemical compound C(CN)N.[S-2].[Zn+2] ZXMZHGJNBSYCEQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- -1 zinc sulfide cadmium-ethylenediamine Chemical compound 0.000 claims abstract description 9
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 7
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 description 89
- 229910052984 zinc sulfide Inorganic materials 0.000 description 30
- 238000001035 drying Methods 0.000 description 15
- 239000002105 nanoparticle Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 6
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- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 238000009210 therapy by ultrasound Methods 0.000 description 2
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Classifications
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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
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/60—
-
- 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
-
- 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 provides a porous two-dimensional zinc cadmium sulfide nanosheet and a preparation method and application thereof, and belongs to the technical field of nano photocatalysts. The invention provides a preparation method of a porous two-dimensional cadmium zinc sulfide nanosheet, which comprises the following steps: mixing zinc salt, an ethylenediamine aqueous solution and a sulfur source, and carrying out a first solvothermal reaction to obtain a zinc sulfide-ethylenediamine precursor; mixing the zinc sulfide-ethylenediamine precursor, cadmium salt and an organic solvent, and carrying out a second solvothermal reaction to obtain a zinc sulfide cadmium-ethylenediamine precursor; and mixing the zinc cadmium sulfide-ethylenediamine precursor with water, and carrying out hydrothermal reaction to obtain the porous two-dimensional zinc cadmium sulfide nanosheet. The porous two-dimensional zinc cadmium sulfide nanosheet prepared by the method disclosed by the invention is uniform in surface pore channel distribution, multiple in reaction active sites, stable in performance and excellent in catalytic effect on photocatalytic water decomposition hydrogen production.
Description
Technical Field
The invention relates to the technical field of nano photocatalysts, in particular to a porous two-dimensional cadmium zinc sulfide nanosheet and a preparation method and application thereof.
Background
The hydrogen energy has the characteristics of high calorific value, environmental protection and the like, and is considered to be an ideal substitute of fossil fuel. The photocatalysis technology is a green new technology, has potential application prospect in the fields of light energy conversion and the like, can directly utilize solar energy to decompose water to prepare hydrogen, can convert solar energy which is difficult to directly utilize into chemical energy which can be directly utilized, and provides an ideal hydrogen production way. At present, the development of efficient and stable photocatalysts is still the key to the practical application of hydrogen production by water decomposition. Of the numerous photocatalytic materials, CdS acts as a visible light responsive photocatalyst as compared to other monomeric photocatalysts (e.g., TiO)2、g-C3N4Etc.) has good photocatalytic hydrogen production capacity, but photo-generated electrons and holes are easy to be combined, and photo-corrosion is easy to occur, the stability is poor, and in order to promote the rapid transfer of current carriers and prevent the photo-corrosion, people improve the stability and the photocatalytic performance of CdS by constructing a heterostructure. Wherein, the solid solution formed by CdS and ZnS has very excellent catalytic performance, and Cd is adjusted2+With Zn2 +Can realize CdxZn1-xThe continuous adjustment of the S energy band structure can make the material optical response range and the oxidation-reduction potential of a photon-generated carrier compatible, so that the positions of a conduction band and a valence band of the S energy band structure reach positions beneficial to a surface photocatalytic reaction. However, in the current report, CdxZn1-xS mainly exists in the form of nanoparticles (10-100 nm) or quantum dots (below 10 nm), and the S and the two-dimensional nano materials (graphene, g-C) which are widely researched at present3N4Etc.) are difficult to achieve good contact, and in addition, the nanoparticles and the ligand-modified quantum dot material are difficult to separate in aqueous solution, which is not favorable for recycling. To reserve CdxZn1-xOf S solid solutionHas the advantages of simultaneously realizing effective contact with a two-dimensional material and easier recycling, and preparing the two-dimensional nanostructure CdxZn1-xS is particularly important.
To reserve CdxZn1-xThe S solid solution has the advantages of realizing effective contact with a two-dimensional material and easier recycling, and making a lot of research by scientific workers. Chinese patent CN 109621978A provides a preparation method of ZnS nanosheet photocatalyst film, but the preparation method is complex, the equipment requirement is high, and the cost is high; the prepared ZnS nanosheet is thick and reaches 100 nm; in addition, the single ZnS has a low photocatalytic activity and is to be further improved. Chinese patent CN 106622289B discloses a nano material compounded by CdZnS quantum dots and carbon dots, a preparation method thereof and application thereof in hydrogen production by photolysis of water, but the prepared CdZnSQDs/C QDS compound is seriously agglomerated, so that the optimal hydrogen production activity is only 2063 mu mol g-1·h-1And the quantum dot system is extremely difficult to recycle in aqueous solution. Literature (J.Mater.chem.A., 2017,5,14682, Dramatic enhancement of the photocatalytic activity of Cd0.5Zn0.5Snanosheets via phosphorization calcination for visible-light-driven H2evolution) reported a ZnP-loaded Cd0.5Zn0.5The prepared sample is large in block, thick and nonuniform in size.
Disclosure of Invention
The invention aims to provide a porous two-dimensional zinc cadmium sulfide nanosheet and a preparation method and application thereof. The porous two-dimensional zinc cadmium sulfide nanosheet prepared by the preparation method provided by the invention has an ultrathin two-dimensional structure, uniform surface pore canal distribution, good stability and high activity of hydrogen production by photocatalytic decomposition of water.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a porous two-dimensional cadmium zinc sulfide nanosheet, which comprises the following steps:
mixing zinc salt, an ethylenediamine aqueous solution and a sulfur source, and carrying out a first solvothermal reaction to obtain a zinc sulfide-ethylenediamine precursor;
mixing the zinc sulfide-ethylenediamine precursor, cadmium salt and an organic solvent, and carrying out a second solvothermal reaction to obtain a zinc sulfide cadmium-ethylenediamine precursor;
and mixing the zinc cadmium sulfide-ethylenediamine precursor with water, and carrying out hydrothermal reaction to obtain the porous two-dimensional zinc cadmium sulfide nanosheet.
Preferably, the zinc salt comprises one or more of zinc chloride, zinc acetate and zinc nitrate;
the sulfur source comprises thiourea and/or thioacetamide.
Preferably, the molar ratio of the zinc salt to the sulfur source is 1 (1-6).
Preferably, the cadmium salt includes cadmium chloride and/or cadmium nitrate.
Preferably, the molar ratio of the cadmium salt to the zinc sulfide-ethylenediamine precursor is 1 (0.5-20).
Preferably, the temperature of the first solvothermal reaction is 140-180 ℃ and the time is 6-24 h.
Preferably, the temperature of the second solvent thermal reaction is 140-180 ℃ and the time is 0.5-16 h.
Preferably, the temperature of the hydrothermal reaction is 120-160 ℃, and the time is 3-6 h.
The invention provides a porous two-dimensional cadmium zinc sulfide nanosheet prepared by the preparation method in the technical scheme.
The invention also provides application of the porous two-dimensional cadmium zinc sulfide nanosheet in the technical scheme in hydrogen production through photocatalytic water decomposition.
The invention provides a preparation method of a porous two-dimensional cadmium zinc sulfide nanosheet, which comprises the following steps: mixing zinc salt, an ethylenediamine aqueous solution and a sulfur source, and carrying out a first solvothermal reaction to obtain a zinc sulfide-ethylenediamine precursor; mixing the zinc sulfide-ethylenediamine precursor, cadmium salt and an organic solvent, and carrying out a second solvothermal reaction to obtain a zinc sulfide cadmium-ethylenediamine precursor; and mixing the zinc cadmium sulfide-ethylenediamine precursor with water, and carrying out hydrothermal reaction to obtain the porous two-dimensional zinc cadmium sulfide nanosheet. The porous two-dimensional zinc cadmium sulfide nanosheet prepared by the method has an ultrathin two-dimensional structure, surface pore channels of the nanosheet are uniformly distributed, diffusion and mass transfer are facilitated, meanwhile, the nanosheet has a plurality of reaction active sites and stable performance, and has good application performance in the fields of photocatalytic water decomposition hydrogen production and the like; and the preparation method is simple to operate and suitable for industrial production.
Drawings
FIG. 1 shows Cd prepared in example 10.5Zn0.5An XRD pattern of the S nanosheet;
FIG. 2 shows Cd prepared in example 10.5Zn0.5SEM image of S nano sheet;
FIG. 3 shows Cd prepared in example 10.5Zn0.5A TEM image of S nanosheets;
FIG. 4 shows Cd prepared in example 20.22Zn0.78SEM image of S nano sheet;
FIG. 5 is a comparison of the XRD patterns of samples prepared in example 1 and example 2;
FIG. 6 shows Cd prepared by a one-step hydrothermal method0.5Zn0.5S nano-particles;
FIG. 7 shows Cd0.5Zn0.5S nanosheet and Cd0.5Zn0.5Hydrogen production curve diagram of S nano-particle photocatalysis 20 vol% triethanolamine solution;
FIG. 8 shows Cd0.22Zn0.78S nanosheet and Cd0.5Zn0.5Hydrogen production curve of S nano-particle photocatalysis 20 vol% triethanolamine solution.
Detailed Description
The invention provides porous two-dimensional CdxZn1-xThe preparation method of the S nanosheet comprises the following steps:
mixing zinc salt, ethylenediamine aqueous solution and sulfur source, and carrying out first solvothermal reaction to obtain zinc sulfide-ethylenediamine (ZnS (en) for short)0.5) A precursor;
converting said ZnS (en)0.5Mixing the precursor, cadmium salt and organic solvent, and carrying out a second solvothermal reaction to obtain cadmium zinc sulfide-ethylenediamine (abbreviated as Cd)xZn1-xS(en)y) A precursor;
will be described inCdxZn1-xS(en)yMixing the precursor with water, and carrying out hydrothermal reaction to obtain porous two-dimensional cadmium zinc sulfide (abbreviated as Cd)xZn1-xS, wherein x is more than 0 and less than 1).
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
Mixing zinc salt, ethylenediamine aqueous solution and sulfur source, and carrying out first solvothermal reaction to obtain ZnS (en)0.5And (3) precursor.
In the invention, the zinc salt preferably comprises one or more of zinc chloride, zinc acetate and zinc nitrate, and more preferably comprises zinc chloride, zinc acetate or zinc nitrate. In the present invention, the sulfur source preferably comprises thiourea and/or thioacetamide, more preferably comprises thiourea or thioacetamide. In the invention, the molar ratio of the zinc salt to the sulfur source is preferably 1 (1-6), more preferably 1 (1.5-5), and most preferably 1 (2-4).
In the invention, the volume fraction of ethylenediamine in the ethylenediamine aqueous solution is preferably 50-90%, and more preferably 60-80%. In the invention, the dosage ratio of the ethylenediamine aqueous solution to the zinc salt is preferably (40-80) mL:1mmol, more preferably (50-70) mL:1mmol, and most preferably 60mL:1 mmol.
In the present invention, the zinc salt, the ethylenediamine aqueous solution and the sulfur source are preferably mixed by stirring. The stirring speed in the present invention is not particularly limited, and a stirring speed well known in the art may be used. In the invention, the zinc salt, the ethylenediamine (en) aqueous solution and the sulfur source are preferably mixed in sequence by dissolving the zinc salt in the ethylenediamine aqueous solution, adding the sulfur source into the obtained mixed system and then stirring for 20-40 min.
In the invention, the temperature of the first solvothermal reaction is preferably 140-180 ℃, more preferably 150-170 ℃, and most preferably 160 ℃; the first solvent thermal reaction time is preferably 6-24 h, more preferably 10-20 h, and most preferably 16-18 h. In the present invention, during the first solvothermal reaction, the following reactions occur: zn2++NH2-SC-NH2+(NH2CH2)2→ZnS((NH2CH2)2)0.5. In the present invention, in the first solvothermal reaction process, ethylenediamine is used as a soft template and a structure-directing molecule, so that the generated ZnS (en)0.5Has a two-dimensional nanostructure.
After the first solvothermal reaction is completed, the method preferably further comprises washing and drying the obtained precursor in sequence. In the present invention, the solvent used for the washing is preferably ethanol; the number of washing is preferably 3 to 6. In the invention, the drying temperature is preferably 30-80 ℃, and more preferably 40-70 ℃; the drying time is preferably 1-48 h, and more preferably 5-20 h.
Obtaining ZnS (en)0.5After the precursor, the ZnS (en)0.5Mixing the precursor, cadmium salt and organic solvent, and carrying out a second solvothermal reaction to obtain CdxZn1-xS(en)yAnd (4) driving the body.
In the present invention, the cadmium salt preferably includes cadmium chloride and/or cadmium nitrate. In the present invention, the cadmium salt and ZnS (en)0.5The molar ratio of the precursors is preferably 1 (0.5-20), more preferably 1 (1-10), and most preferably 1 (1.5-5).
In the present invention, the organic solvent is preferably ethylene glycol or ethanol. The amount of the organic solvent used in the present invention is not particularly limited, and the cadmium salt can be dissolved therein.
In the present invention, the ZnS (en)0.5The precursor, the cadmium salt and the organic solvent are preferably mixed by dissolving the cadmium salt in the solvent, and mixing the obtained cadmium salt solution with the ZnS (en)0.5And (4) carrying out ultrasonic mixing on the precursor. In the invention, the ultrasonic mixing temperature is preferably 30-45 ℃, and the time is preferably 20-30 min.
In the invention, the temperature of the second solvent thermal reaction is 140-180 ℃, more preferably 150-170 ℃, and most preferably 160 ℃; the second solvent thermal reaction time is preferably 0.5-16 h, more preferably 2-10 h, and most preferably 4-8 h. In the present invention, the first solvothermal reaction processThe reaction that takes place is as follows: cd [ Cd ]2++ZnS(en)0.5→CdxZn1-xS(en)yWherein x is more than 0 and less than 1. In the present invention, during the second solvothermal reaction, cadmium ions enter ZnS (en)0.5By substituting Zn sites in the lattice and under the influence of the solvent heat, with a portion of ethylenediamine from ZnS (en)0.5Escape into solution, thereby producing structural changes. Specifically, the method comprises the following steps: 1) during the heat treatment ion exchange, en is from ZnS (en)0.5Partial dissolution of the crystal lattice into the solvent leads to lattice distortion with accompanying lattice shrinkage. 2) Due to Zn in the cation exchange process2+And Cd2+The in-out diffusion rate of (2) is different, and a large number of point defects such as S vacancies are formed. Migration and accumulation of point defects eventually produces some void volume defects, which are thermodynamically stable. 3) Zn2+And Cd2+There is a difference between the radii of (a) and (b). When a large amount of Cd2+Rapid entry into ZnS (en)0.5The resulting tensile stress can lead to lattice fracture. The three aspects described above collectively cause preliminary generation of pores and changes in the nanosheet structure.
After the second solvothermal reaction is completed, the method preferably further comprises washing and drying the obtained precursor in sequence. In the present invention, the solvent used for the washing is preferably ethanol; the number of washing is preferably 3 to 6. In the invention, the drying temperature is preferably 30-80 ℃, and more preferably 40-70 ℃; the drying time is preferably 1-48 h, and more preferably 5-20 h.
To obtain CdxZn1-xS(en)yAfter the precursor is prepared, the Cd is subjected to the preparation methodxZn1-xS(en)yMixing the precursor with water, and carrying out hydrothermal reaction to obtain porous two-dimensional CdxZn1-xS nanosheet; x is more than 0 and less than 1.
In the present invention, the water is preferably deionized water or distilled water. In the present invention, the CdxZn1-xS(en)yThe mass ratio of the precursor to water is preferably 1: (60-70), more preferably 1: (65-70).
In the present invention, the water is heatedThe reaction temperature is preferably 120-160 ℃, more preferably 130-150 ℃, and most preferably 140 ℃; the time of the hydrothermal reaction is preferably 3-6 h, and more preferably 4-5 h. In the present invention, the hydrothermal reaction occurs as follows: cd [ Cd ]xZn1-xS(en)y→CdxZn1-xAnd S. In the invention, in the hydrothermal reaction process, Cd is obtained0.5Zn0.5S(en)yWhen solvent-assisted heat treatment is carried out in pure water, the en molecules are completely hydrolyzed from Cd0.5Zn0.5S(en)yCd released from the crystal lattice to generate wurtzite structure0.5Zn0.5S, during the period, further escape of ethylenediamine molecules and orthorhombic and hexagonal wurtzite structure Cd0.5Zn0.5The mismatch of S further causes the unit cell to shrink to form the pore structure.
After the hydrothermal reaction is completed, the invention preferably further comprises washing and drying the obtained nanosheets in sequence. In the present invention, the washing is preferably water washing; the number of times of water washing is preferably 3 to 6. In the invention, the drying temperature is preferably 30-80 ℃, and more preferably 40-70 ℃; the drying time is preferably 1-48 h, and more preferably 5-20 h.
The invention provides porous two-dimensional CdxZn1-xThe S nanosheet preparation method comprises the steps of firstly preparing ZnS (en) by a solvothermal method0.5Precursor is then placed into reaction liquid containing cadmium ions for solvothermal reaction to obtain CdxZn1-xS(en)yPrecursor, and final reaction of obtained CdxZn1-xS(en)yPerforming hydrothermal treatment on the precursor to obtain the nano-porous two-dimensional CdxZn1-xAnd (3) S nanosheet. Cd prepared by the inventionxZn1-xThe S has an ultrathin two-dimensional structure, surface pore channels are uniformly distributed, diffusion mass transfer is facilitated, meanwhile, a plurality of reaction active sites are provided, and the performance stability is good and stable; and the operation is simple, and the method is suitable for industrial production.
The invention provides porous two-dimensional Cd prepared by the preparation method in the technical schemexZn1-xAnd (3) S nanosheet.
In the invention, the porous two-dimensional CdxZn1-xThe thickness of the S nano sheet is about 1.5-3 nm.
Compared with CdxZn1-xS (x is more than 0 and less than 1) nano-particles, quantum dots or CdxZn1-xS (x is more than 0 and less than 1) one-dimensional nano structure, Cd provided by the inventionxZn1-xThe S (x is more than 0 and less than 1) nanosheet has an ultrathin two-dimensional structure, and surface pore channels are uniformly distributed, so that the diffusion mass transfer is facilitated, and the separation is easy; and porous two-dimensional CdxZn1-xThe long-range order of the S (x is more than 0 and less than 1) nanosheet is also beneficial to the in-plane directional migration of photogenerated carriers, and compared with thick bulk CdxZn1-xS (x is more than 0 and less than 1) shortens the migration distance of the photo-generated electrons and the holes to the surface of the material; in addition, porous two-dimensional CdxZn1-xThe porous structure of the S (x is more than 0 and less than 1) nanosheet is beneficial to enlarging the specific surface area and the transmission channel of reactants, so that the surface reaction rate is accelerated, and the photocatalytic activity is obviously improved.
The invention also provides the porous two-dimensional Cd in the technical schemexZn1-xThe S nanosheet is applied to photocatalytic water splitting hydrogen production, photocatalytic carbon dioxide reduction, photocatalytic oxidation or photoelectrocatalysis.
In the invention, the porous two-dimensional CdxZn1-xThe application of the S nanosheet in hydrogen production by photocatalytic water decomposition is preferably hydrogen production by water in a photocatalytic triethanolamine solution. In the invention, the volume fraction of triethanolamine in the triethanolamine solution is preferably 15-25%, and more preferably 20%.
In the present invention, the method for producing hydrogen by photocatalytic catalysis of water in triethanolamine solution preferably comprises the following steps: an experiment of photocatalytic decomposition of water hydrogen was performed using a closed on-line detection system (Lab solarli-AG, Beijing Pofely Co.). First, 10mg of Cd was weighedxZn1-xThe S catalyst is placed in a centrifuge tube (volume 5mL) containing 3mL of water and is subjected to ultrasonic treatment for 15min for later use. Then the Cd dispersed by the ultrasonic wavexZn1-xS catalyst was added to a reactor containing 100mL of 20 vol% triethanolamine. Then, vacuum grease is coated on each interface part of the reactorTo ensure the container tightness. And finally, covering a quartz cover, vacuumizing the reactor, and placing a xenon lamp above the reactor for irradiation. Detecting H generated in the reaction process every 60min2Amount of the compound (A). The hydrogen yield was determined by gas chromatography (Tianmei GC-7900 gas chromatograph).
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Dissolving 2mmol of zinc acetate in 70mL of ethylenediamine aqueous solution (the volume ratio of ethylenediamine to water is 6:1), adding 3mmol of thiourea after the zinc acetate is completely dissolved, stirring for 30min, placing the mixed system in a hydrothermal reaction tank, reacting for 16h at 160 ℃, washing the obtained precursor with ethanol for 5 times, and drying for 6h at 60 ℃ to obtain ZnS (en)0.5Precursor (white powder).
(2) 160.6mg of cadmium chloride was dissolved in 70mL of ethylene glycol to obtain a cadmium chloride solution, and 180mg of ZnS (en) was added0.5Ultrasonically dispersing the precursor for 30min, placing the obtained mixed solution into a hydrothermal reaction tank, reacting for 8h at 160 ℃, washing the obtained precursor with ethanol for 5 times, and drying for 6h at 60 ℃ to obtain Cd0.5Zn0.5S(en)yPrecursor (yellow powder).
(3) Adding 100mg of Cd0.5Zn0.5S(en)yMixing the precursor with 70mL of deionized water, reacting for 3h at 140 ℃, centrifuging the product, and drying the obtained solid for 6h at 60 ℃ to obtain porous two-dimensional Cd0.5Zn0.5And (3) S nanosheet.
FIG. 1 shows a porous two-dimensional Cd prepared in this example0.5Zn0.5XRD pattern of S nanosheet. As can be seen from FIG. 1, ZnS (en)0.5For orthorhombic phase, after ion exchange, despite Cd0.5Zn0.5S(en)yDiffraction peak of (2)The intensity is diminished, but still comparable to ZnS (en)0.5The diffraction peaks of the two are matched, indicating that the Cd0.5Zn0.5S(en)yStill belongs to orthorhombic crystals, and after the last heat treatment, the diffraction peak of the sample shows a hexagonal wurtzite structure Cd0.5Zn0.5S, whose diffraction peaks are all shifted to a small angle compared to standard ZnS (PDF #01-0677), indicating an expansion of its lattice due to an enlargement of interplanar spacings, indicating a large ionic radius of Cd2+Has been successfully doped with the crystal lattice, Cd0.5Zn0.5S solid solution nanosheets have been successfully prepared.
Porous two-dimensional Cd prepared in this example0.5Zn0.5SEM images of the S nanosheets are shown in fig. 2, and TEM images are shown in fig. 3. As can be seen from FIGS. 2 to 3, Cd0.5Zn0.5S has a porous, ultrathin lamellar structure.
Example 2
(1) Dissolving 2mmol of zinc acetate in 70mL of ethylenediamine aqueous solution (the volume ratio of ethylenediamine to water is 6:1), adding 3mmol of thiourea after the zinc acetate is completely dissolved, stirring for 30min, placing the mixed system in a hydrothermal reaction tank, reacting for 16h at 160 ℃, washing the obtained precursor with ethanol for 5 times, and drying for 8h at 50 ℃ to obtain ZnS (en)0.5Precursor (white powder).
(2) 39.7mg of cadmium chloride was dissolved in 70mL of ethylene glycol to obtain a cadmium chloride solution, and 100mg of ZnS (en) was added0.5Ultrasonically dispersing the precursor for 30min, stirring for 10min, placing the obtained mixed solution into a hydrothermal reaction tank, reacting for 8h at 160 ℃, washing the obtained precursor with ethanol for 5 times, and drying for 8h at 50 ℃ to obtain Cd0.22Zn0.78S(en)yPrecursor (yellow powder).
(3) Adding 100mg of Cd0.22Zn0.78S(en)yMixing the precursor with 70mL of deionized water, reacting for 3h at 140 ℃, centrifuging the product, and drying the obtained solid for 8h at 50 ℃ to obtain porous two-dimensional Cd0.22Zn0.78S nanosheet (light yellow).
Porous two-dimensional Cd prepared in this example0.22Zn0.78The SEM image of the S nanosheets is shown in fig. 4. Therefore, the two-dimensional Cd with different Zn-Cd element ratios still can be obtained by changing the addition of the cadmium chloride0.22Zn0.78S。
Cd prepared in example 10.5Zn0.5S nanosheet and Cd prepared in example 20.22Zn0.78The XRD pattern of the S nanosheet is shown in FIG. 5, and as can be seen from FIG. 5, Cd0.22Zn0.78The diffraction peak of the S nanosheet is shifted to a large angle due to the slightly smaller interplanar spacing, demonstrating that Cd0.22Zn0.78S is successfully prepared.
Comparative example 1
Preparation of Cd by one-step hydrothermal method0.5Zn0.5S: 2.673g Cd (OAc)2·2H2O and 2.206g Zn (OAc)2·2H2O was dispersed in 50mL of deionized water and stirred for 5min, then 15mL of a 4mol/L NaOH solution and 1.90g of thiourea were added to the resulting mixture and stirred for 30min, then, kept at 180 ℃ for 24h, the obtained precipitate was collected by centrifugation and washed, and dried at 60 ℃ for 6h to obtain Cd0.5Zn0.5And (3) S nanoparticles.
Cd prepared in this control example0.5Zn0.5The SEM image of the S nanoparticles is shown in FIG. 6, and it can be seen from FIG. 6 that Cd0.5Zn0.5S is heavily agglomerated nanoparticles.
Application example 1
An experiment of photocatalytic decomposition of water hydrogen was performed using a closed on-line detection system (Lab solarli-AG, Beijing Pofely Co.). First, 10mg of Cd was weighedxZn1-xThe S catalyst is placed in a centrifuge tube (volume 5mL) containing 3mL of water and is subjected to ultrasonic treatment for 15min for later use. Then the Cd dispersed by the ultrasonic wavexZn1-xS catalyst was added to a reactor containing 100mL of 20 vol% triethanolamine. Vacuum grease was then applied to the reactor at each interface to ensure containment. And finally, covering a quartz cover, vacuumizing the reactor, and placing a xenon lamp above the reactor for irradiation. Detecting H generated in the reaction process every 60min2The amount and hydrogen yield were determined by gas chromatography (Tianmei GC-7900)。
Cd prepared in example 10.5Zn0.5S nanosheet and Cd prepared in comparative example 10.5Zn0.5The hydrogen production efficiency of the S nano-particles under the irradiation of a 300W xenon lamp (with the wavelength of 350-780 nm) is shown in figure 7. As can be seen from FIG. 7, Cd0.5Zn0.5The hydrogen production efficiency of the S nano-sheet is about 17 mmol-g-1·h-1One-step hydrothermal method for obtaining Cd0.5Zn0.5The hydrogen production efficiency of the S nano-particle activity is about 8.9 mmol/g-1·h-1Cd prepared by the invention0.5Zn0.5The activity of the S nanosheet is Cd0.5Zn0.5Nearly twice that of S nano-particles, which shows that Cd prepared by the method0.5Zn0.5The S nanosheet is high in activity and excellent in catalytic performance.
Cd prepared in example 20.22Zn0.78S nanosheet and Cd prepared in comparative example 10.5Zn0.5The hydrogen production efficiency of the S nano-particles under the irradiation of a 300W xenon lamp (with the wavelength of 350-780 nm) is shown in figure 8. As can be seen from FIG. 8, Cd0.22Zn0.78The hydrogen production efficiency of the S nano-sheet is about 17 mmol-g-1·h-1One-step hydrothermal method for obtaining Cd0.5Zn0.5The hydrogen production efficiency of the S nano-particle activity is about 12.3 mmol/g-1·h-1Cd prepared by the invention0.5Zn0.5The activity of the S nanosheet is Cd0.5Zn0.51.4 times of S nano-particles, which shows that the Cd prepared by the invention0.22Zn0.78The S nanosheet is high in activity and excellent in catalytic performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a porous two-dimensional cadmium zinc sulfide nanosheet is characterized by comprising the following steps:
mixing zinc salt, an ethylenediamine aqueous solution and a sulfur source, and carrying out a first solvothermal reaction to obtain a zinc sulfide-ethylenediamine precursor;
mixing the zinc sulfide-ethylenediamine precursor, cadmium salt and an organic solvent, and carrying out a second solvothermal reaction to obtain a zinc sulfide cadmium-ethylenediamine precursor;
and mixing the zinc cadmium sulfide-ethylenediamine precursor with water, and carrying out hydrothermal reaction to obtain the porous two-dimensional zinc cadmium sulfide nanosheet.
2. The preparation method according to claim 1, wherein the zinc salt comprises one or more of zinc chloride, zinc acetate and zinc nitrate;
the sulfur source comprises thiourea and/or thioacetamide.
3. The preparation method according to claim 1 or 2, wherein the molar ratio of the zinc salt to the sulfur source is 1 (1-6).
4. The method of claim 1, wherein the cadmium salt comprises cadmium chloride and/or cadmium nitrate.
5. The preparation method of claim 1 or 4, wherein the molar ratio of the cadmium salt to the zinc sulfide-ethylenediamine precursor is 1 (0.5-20).
6. The preparation method according to claim 1, wherein the temperature of the first solvothermal reaction is 140-180 ℃ and the time is 6-24 hours.
7. The preparation method according to claim 1, wherein the temperature of the second solvothermal reaction is 140-180 ℃ and the time is 0.5-16 h.
8. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 120-160 ℃ for 3-6 hours.
9. Porous two-dimensional cadmium zinc sulfide nanosheets prepared by the preparation method of any one of claims 1 to 8.
10. The porous two-dimensional cadmium zinc sulfide nanosheet of claim 9, for use in photocatalytic decomposition of water for hydrogen production, photocatalytic carbon dioxide reduction, photocatalytic oxidation or photoelectrocatalysis.
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