CN116273179A - Cd of Cd coordination sulfur matrix x Zn 1-x Preparation method and application of S nano crystal material - Google Patents
Cd of Cd coordination sulfur matrix x Zn 1-x Preparation method and application of S nano crystal material Download PDFInfo
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000011593 sulfur Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 30
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 22
- 239000011159 matrix material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 97
- 239000002707 nanocrystalline material Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 3
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004246 zinc acetate Substances 0.000 claims abstract description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 16
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 16
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 12
- 238000007146 photocatalysis Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000001257 hydrogen Substances 0.000 abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002608 ionic liquid Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910007609 Zn—S Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- -1 transition metal sulfides Chemical class 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 240000006829 Ficus sundaica Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical class [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000006104 solid solution Substances 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
- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
-
- 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—
-
- 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 discloses a Cd coordination sulfur interstitial Cd x Zn 1‑ x The preparation method and application of the S nano crystal material comprise the following steps: mixing zinc acetate, cadmium nitrate and ethylenediamine, adding thiourea to obtain a mixed solution, introducing acid gas into the mixed solution, performing constant pressure reaction, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain Cd of a Cd coordination sulfur matrix x Zn 1‑x S nanocrystalline material. The nano crystal material prepared by the invention has high-efficiency reaction activity and can be used as a high-efficiency photocatalytic hydrogen production photocatalyst. The invention adopts the method of introducing acid gas for the first time to selectively leadSulfur interstitial and Cd x Zn 1‑x And the preparation method is simple and controllable, low in cost and easy to obtain raw materials, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a Cd coordination sulfur interstitial Cd x Zn 1-x A preparation method and application of S nano crystal material.
Background
Doping sulfur into transition metal sulfides or oxides is a common practice and means for modifying semiconductors. When the doping element is the same as the non-metallic element of the semiconductor, an elemental interstitium is formed which, after coordination with the metallic element, forms an intrinsic defect in the semiconductor. The defects can change the energy band structure, the surface electron density, the hole-electron separation and other physical properties of the semiconductor, and have great development potential in the catalysis field. However, the currently developed sulfur matrix introduction mode cannot be selectively introduced around specific elements, and the industrial application is difficult to operate, so that the application of the sulfur matrix in mass production is seriously hindered. Therefore, in the transition metal sulfide, an effective method for selectively introducing sulfur interstitials is urgently required.
The introduction of sulfur interstitials plays an important role for photocatalytic applications. In the current photocatalytic application, the sulfur matrix is a randomly doped material, and in solid solutions with multiple metal elements, it is difficult to regulate the position of doped sulfur, thereby making the space for improving the photocatalytic performance limited. Thus, it is urgent and important to develop methods for selectively introducing sulfur interstitials into sulfide materials by studying effective ways of precisely controlling the coordination sites of sulfur incorporation.
The transition metal sulfide has obvious visible light response and low price, has impressive photocatalytic hydrogen production performance, and is a potential photocatalytic hydrogen production material in the future. Various cadmium sulfides represented by cadmium sulfide are photocatalytic materials with higher photocatalytic hydrogen production, but in the one-step regulation process, a method for accurately controlling the coordination ratio of a sulfur matrix around a Cd position and a Cd element is blank, and meanwhile, the realization of improvement of the performance of a photocatalyst through the sulfur matrix is one of photocatalysis research hot spots.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a Cd-coordinated sulfur interstitial Cd x Zn 1-x The preparation method and the application of the S nano crystal material can realize the precise control of the coordination proportion of the sulfur matrix and Cd element in the crystal material.
In order to achieve the technical purpose, the invention provides the following technical scheme:
the invention provides the Cd of the Cd coordination sulfur matrix x Zn 1-x S (wherein, x is more than 0 and less than 1) nano crystal material, which comprises the following steps: mixing zinc acetate, cadmium nitrate and ethylenediamine, adding thiourea to obtain a mixed solution, introducing acid gas into the mixed solution, performing constant pressure reaction, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain Cd of Cd coordination sulfur matrix x Zn 1-x S nanocrystalline material.
Preferably, the Cd (NO 3 ) 2 With Zn (CH) 3 COO) 2 The molar ratio of (1.0-10.0) to 1.0.
Preferably, the Zn (CH 3 COO) 2 The molar ratio of the catalyst to the ethylenediamine is (0.5-3): 1000.
preferably, the Cd (NO 3 ) 2 The molar ratio of the catalyst to thiourea is 1.0 (2.0-3.0).
Preferably, the reaction temperature of the constant pressure reaction is 90-200 ℃, the reaction time is 12-45 h, and the reaction pressure is 0.2-0.4 MPa.
Preferably, the acid gas is hydrogen sulfide or an acid mixed gas containing hydrogen sulfide.
Further preferably, the acid mixed gas containing hydrogen sulfide is a mixture of hydrogen sulfide and at least one of chlorine and sulfur dioxide.
Preferably, the molar ratio of the acid gas to thiourea is (0.01 to 0.1): 1.0.
Cd of the Cd coordination sulfur matrix prepared by the preparation method x Zn 1-x S nanocrystalline material.
Cd of the Cd coordination sulfur matrix x Zn 1-x The S nano crystal material is a rod-shaped nano crystal, the side length of the S nano crystal material is 50-200 nm, and the thickness of the S nano crystal material is 5-10 nm.
Cd of the Cd coordination sulfur matrix x Zn 1-x The S nano crystal material is used as a photocatalysis material in photocatalysis.
In the invention, acid gas is introduced for reverse reactionElemental sulfur, elemental sulfur and sulfide Cd should be generated x Zn 1-x S sulfur site acts to form metal and organic sulfur binding site. Under the reaction system, cadmium ions have stronger polarization effect than zinc ions, are easy to react with hydrogen sulfide and the like, and are easy to react with organic sulfur in the system to preferentially act on Cd sites, so that accumulation of sulfur interstitials is finally formed at the Cd sites.
The invention has the beneficial effects that:
1) The invention synthesizes Cd with different Zn/Cd ratios of Cd coordination sulfur matrix by adopting a one-step hydrothermal method x Zn 1-x S nanocrystalline material (I) S(Cd) -Cd x Zn 1-x S) due to coordination of the sulfur interstitium at the Cd site, I S(Cd) -Cd x Zn 1-x The hydrogen production performance of S in visible light photocatalysis hydrogen evolution is greatly improved, and the high-efficiency hydrogen production efficiency can be maintained under the action of visible light, a hole capturing agent and water.
2) The invention adopts the method of introducing acid gas for the first time to selectively lead the sulfur interstitial and Cd x Zn 1-x The coordination ratio of the sulfur interstitial and the Cd element can be precisely controlled by the coordination of the Cd in S, so that I S(Cd) -Cd x Zn 1-x S has ultrahigh hydrogen production performance and potential application prospect.
3) The preparation method is simple and controllable, low in cost and easy to obtain raw materials, and is suitable for large-scale production.
Drawings
FIG. 1 is the sample I in example 1 S(Cd) -Cd x Zn 1-x And an element Zn/Cd ratio analysis chart of the S nano crystal material.
FIG. 2 is the sample I in example 1 S(Cd) -Cd x Zn 1-x S element analysis diagram of S nanocrystalline material.
FIG. 3 is the sample I in example 1 S(Cd) -Cd 0.8 Zn 0.2 Zn-S coordination K-edge Fourier transform EXAFS diagram in S nano crystal material.
FIG. 4 is the sample I in example 1 S(Cd) -Cd 0.8 Zn 0.2 The Cd-S coordination K-edge Fourier transform EXAFS diagram in the S nano crystal material.
FIG. 5 is example 1Middle I S(Cd) -Cd x Zn 1-x XRD pattern of S nanocrystalline material.
FIG. 6 is the sample I in example 1 S(Cd) -Cd 0.8 Zn 0.2 SEM image of S nanocrystalline material.
FIG. 7 is a diagram of example 1I S(Cd) -Cd x Zn 1-x And (3) a photocatalytic hydrogen production performance diagram of the S nano crystal material.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
Example 1
Preparation of Cd-coordinated sulfur interstitials of Cd with different Zn/Cd ratios x Zn 1-x S nanocrystalline material (I) S(Cd) -Cd x Zn 1-x S)：
1) Taking x=0.9, preparation I S(Cd) -Cd 0.9 Zn 0.1 S nanocrystalline material:
60ml of ethylenediamine was placed in a beaker, and 0.625mmol of Zn (CH) 3 COO) 2 ，5.625mmol Cd(NO 3 ) 2 Stirring at 500r/min for 10min to obtain uniformly distributed ionic liquid. 12.5mmol CH 4 N 2 S, adding the solution into the solution, continuously stirring, and stirring for 30min at the rotating speed of 500r/min to obtain a mixed solution with uniformly distributed Zn ions, cd ions and organic ionic liquid. Transferring the mixed solution into a 300mL high-pressure constant-pressure reaction kettle, heating, continuously introducing 0.3mmol hydrogen sulfide at a constant flow rate, keeping the temperature at the constant pressure of 0.25MPa and the temperature of 150 ℃ for 24 hours, taking out, cooling and filtering after the reaction is finished, and repeatedly washing with ethanol and deionized water. Finally, drying the washed product in a vacuum drying oven at 80 ℃ for 24 hours to obtain I S(Cd) -Cd 0.9 Zn 0.1 S nanocrystalline material.
2) Taking x=0.8, preparation I S(Cd) -Cd 0.8 Zn 0.2 S nanocrystalline material
60ml of ethylenediamine was placed in a beaker, and 1.25mmol of Zn (CH) 3 COO) 2 ，5.0mmol Cd(NO 3 ) 2 Stirring at 500r/min for 10min to obtain uniformly distributed ionic liquid. 12.5mmol CH 4 N 2 S, adding the solution into the solution, continuously stirring, and stirring for 30min at the rotating speed of 500r/min to obtain a mixed solution with uniformly distributed Zn ions, cd ions and organic ionic liquid. Transferring the mixed solution into a 300mL high-pressure constant-pressure reaction kettle, heating, and continuously introducing 0.5mmol of sulfur dioxide and hydrogen sulfide mixed gas in total at a constant flow rate, wherein the molar ratio of the sulfur dioxide to the hydrogen sulfide is 2:1, preserving heat for 36h at the constant pressure of 0.3MPa and the temperature of 170 ℃, taking out, cooling and filtering after the reaction is finished, and repeatedly washing with ethanol and deionized water. Finally, drying the washed product in a vacuum drying oven at 80 ℃ for 24 hours to obtain I S(Cd) -Cd 0.8 Zn 0.2 S nanocrystalline material.
3) Taking x=0.7, preparation I S(Cd) -Cd 0.7 Zn 0.3 S nanocrystalline material:
60ml of ethylenediamine was placed in a beaker, and 1.875mmol of Zn (CH) 3 COO) 2 ，4.375mmol Cd(NO 3 ) 2 Stirring at 500r/min for 10min to obtain uniformly distributed ionic liquid. 11.8mmol CH was taken 4 N 2 S, adding the solution into the solution, continuously stirring, and stirring for 30min at the rotating speed of 500r/min to obtain a mixed solution with uniformly distributed Zn ions, cd ions and organic ionic liquid. Transferring the mixed solution into a 300mL high-pressure constant-pressure reaction kettle, heating, and continuously introducing mixed gas of 0.7mmol of hydrogen sulfide and chlorine gas at a constant flow rate, wherein the molar ratio of the hydrogen sulfide to the chlorine gas is 1:1, preserving the heat for 36 hours at the constant pressure of 0.35MPa and the temperature of 140 ℃, taking out, cooling and filtering after the reaction is finished, and repeatedly washing with ethanol and deionized water. Finally, drying the washed product in a vacuum drying oven at 80 ℃ for 24 hours to obtain I S(Cd) -Cd 0.7 Zn 0.3 S nanocrystalline material.
4) Taking x=0.6, preparation I S(Cd) -Cd 0.6 Zn 0.4 S nanocrystalline material:
60ml of ethylenediamine was placed in a beaker, and 2.50mmol of Zn (CH) 3 COO) 2 ，3.75mmol Cd(NO 3 ) 2 Stirring at 500r/min for 10min to obtain uniformityA distributed ionic liquid. 10.9mmol CH 4 N 2 S, adding the solution into the solution, continuously stirring, and stirring for 30min at the rotating speed of 500r/min to obtain a mixed solution with uniformly distributed Zn ions, cd ions and organic ionic liquid. Transferring the mixed solution into a 300mL high-pressure constant-pressure reaction kettle, heating, and continuously introducing acid mixed gas of sulfur dioxide, hydrogen sulfide and chlorine with the total amount of 0.85mmol at a constant flow rate, wherein the mole ratio of the sulfur dioxide to the hydrogen sulfide to the chlorine is 2:2:1, preserving the heat for 36 hours at the constant pressure of 0.4MPa and the temperature of 160 ℃, taking out, cooling and filtering after the reaction is finished, and repeatedly washing with ethanol and deionized water. Finally, drying the washed product in a vacuum drying oven at 80 ℃ for 24 hours to obtain I S(Cd) -Cd 0.6 Zn 0.4 S nanocrystalline material.
For I prepared in this example S(Cd) -Cd x Zn 1-x The S nano-crystalline material is subjected to element Zn/Cd ratio test, and the result is shown in figure 1. As can be seen from FIG. 1, I S(Cd) -Cd 0.9 Zn 0.1 S、I S(Cd) -Cd 0.8 Zn 0.2 S、I S(Cd) -Cd 0.7 Zn 0.3 S、I S(Cd) -Cd 0.6 Zn 0.4 The Zn/Cd ratio in S accords with the corresponding pure Cd x Zn 1-x Zn/Cd ratio in S.
For I prepared in this example S(Cd) -Cd x Zn 1-x The S element content in the S nanocrystalline material was tested and the results are shown in FIG. 2. As can be seen from FIG. 2, I S(Cd) -Cd 0.9 Zn 0.1 S、I S(Cd) -Cd 0.8 Zn 0.2 S、I S(Cd) -Cd 0.7 Zn 0.3 S、I S(Cd) -Cd 0.6 Zn 0.4 S/(Zn+Cd+S) ratio in S is greater than 0.5, indicating the presence of sulfur interstitials.
FIG. 3 shows the results of this example S(Cd) -Cd 0.8 Zn 0.2 Zn-S coordination K-edge Fourier transform EXAFS diagram in S nano crystal material. As can be seen from the graph, the coordination number of S around Zn has not been changed significantly, resulting in the strength of the first coordinated Zn-S shell of Zn and Cd 0.8 Zn 0.2 No difference in S. FIG. 4 shows the results of this example S(Cd) -Cd 0.8 Zn 0.2 The Cd-S coordination K-edge Fourier transform EXAFS diagram in the S nano crystal material. As can be seen from the figure, the intensity of the first coordinated Cd-S shell of Cd increases due to the increase of the S coordination number around Cd. It follows that the sulphur matrix coordinates successfully in the Cd position.
FIG. 5 shows the results of this example S(Cd) -Cd x Zn 1-x XRD pattern of S nanocrystalline material. As can be seen from the figure, I S(Cd) -Cd 0.8 Zn 0.2 S all peak-to-average and Cd 0.8 Zn 0.2 The S-standard PDF cards 49-1302 correspond and move to a low angle, indicating successful incorporation of the sulfur interstitials into the lattice.
FIG. 6 shows the results of this example S(Cd) -Cd 0.8 Zn 0.2 SEM image of S nanocrystalline material. As can be seen from the figure, I S(Cd) -Cd 0.8 Zn 0.2 The S crystal material is a rod-shaped nano crystal, and the grain size is 100-200 nm.
Example 2
For I prepared in example 1 S(Cd) -Cd x Zn 1-x The S nanocrystalline material was tested for photocatalytic activity in a photocatalytic reactor (Labsolar-6A, beijing Perfect technology Co., ltd.). For each test, 10.0mg of I was added to 100mL of deionized water S(Cd) -Cd x Zn 1-x S, 0.035mol of sodium sulfide and 0.025mol of sodium sulfite were sonicated in an ultrasonic bath for 30min, and the solution was stored at 5℃and irradiated with a 300W xenon lamp and a 420nm ultraviolet filter. The hydrogen production was measured by gas chromatography.
I S(Cd) -Cd x Zn 1-x The test results of hydrogen evolution performance of the S nano-crystalline material under visible light are shown in figure 7. As can be seen from FIG. 7, I S(Cd) -Cd 0.9 Zn 0.1 S、I S(Cd) -Cd 0.8 Zn 0.2 S、I S(Cd) -Cd 0.7 Zn 0.3 S and I S(Cd) -Cd 0.6 Zn 0.4 S leads the hydrogen production performance of the catalyst to be higher than that of pure Cd of Zn/Cd in corresponding proportion by introducing sulfur interstitials in Cd position x Zn 1-x S is greatly improved. As can be seen from the figure, I S(Cd) -Cd 0.9 Zn 0.1 S material is compared with Cd 0.9 Zn 0.1 The hydrogen production performance of S is improved by 5 times and is from 0.38 mmol.g -1 ·h -1 Lifting to 1.9 mmol.g -1 ·h -1 ；I S(Cd) -Cd 0.8 Zn 0.2 S is compared with Cd 0.8 Zn 0.2 The hydrogen production performance of S is improved by 4.8 times and is improved from 1.13 mmol.g -1 ·h -1 Lifting to 5.4 mmol.g -1 ·h -1 ；I S(Cd) -Cd 0.7 Zn 0.3 S is compared with Cd 0.7 Zn 0.3 The hydrogen production performance of S is improved by 4.8 times and is improved from 1.85 mmol.g -1 ·h -1 Lifting to 8.8 mmol.g -1 ·h -1 ；I S(Cd) -Cd 0.6 Zn 0.4 S is compared with Cd 0.6 Zn 0.4 The hydrogen production performance of S is improved by 4.4 times and is improved from 4.23 mmol.g -1 ·h -1 Lifting to 18.76 mmol.g -1 ·h -1 。
The invention synthesizes the nano crystal material I with adjustable element coordination by adopting an improved hydrothermal method S(Cd) -Cd x Zn 1-x S, S. I due to the change of coordination quantity of Cd-bit S element S(Cd) -Cd x Zn 1-x S has high-efficiency photocatalytic hydrogen evolution performance responding to visible light, and can be applied to photocatalytic decomposition of water.
Claims (10)
1. Cd of Cd coordination sulfur matrix x Zn 1-x The preparation method of the S nano crystal material comprises the following steps: mixing zinc acetate, cadmium nitrate and ethylenediamine, adding thiourea to obtain a mixed solution, introducing acid gas into the mixed solution, performing constant pressure reaction, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain Cd of Cd coordination sulfur matrix x Zn 1-x S nanocrystalline material.
2. The method of claim 1, wherein the Cd (NO 3 ) 2 With Zn (CH) 3 COO) 2 The molar ratio of (1.0-10.0) to 1.0.
3. The preparation method according to claim 1, which comprisesCharacterized in that the Zn (CH 3 COO) 2 The molar ratio of the catalyst to the ethylenediamine is (0.5-3): 1000.
4. the method of claim 1, wherein the Cd (NO 3 ) 2 The molar ratio of the catalyst to thiourea is 1.0 (2.0-3.0).
5. The preparation method according to claim 1, wherein the constant pressure reaction is carried out at a temperature of 90-200 ℃, for a reaction time of 12-45 h and at a pressure of 0.2-0.4 MPa.
6. The method of claim 1, wherein the molar ratio of acid gas to thiourea is (0.01-0.1): 1.0.
7. the method according to claim 1, wherein the acid gas is hydrogen sulfide or an acid mixed gas containing hydrogen sulfide.
8. The method according to claim 7, wherein the acidic mixed gas containing hydrogen sulfide is a mixture of hydrogen sulfide and at least one of chlorine and sulfur dioxide.
9. A Cd of a Cd coordination sulfur matrix produced by the production method according to any one of claims 1 to 8 x Zn 1-x S nanocrystalline material.
10. A Cd of the Cd coordination sulfur matrix of claim 9 x Zn 1-x The S nano crystal material is used as a photocatalysis material in photocatalysis.
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