CN116273179B - Preparation method and application of CdxZn1-xS nanocrystalline material with Cd-coordinated sulfur interstitial - Google Patents
Preparation method and application of CdxZn1-xS nanocrystalline material with Cd-coordinated sulfur interstitial Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 38
- 239000011593 sulfur Substances 0.000 title claims abstract description 37
- 239000002707 nanocrystalline material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 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 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 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
- 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
- 230000002378 acidificating effect Effects 0.000 claims abstract 3
- 239000000463 material Substances 0.000 claims description 23
- 239000011159 matrix material Substances 0.000 claims description 21
- 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
- 239000002253 acid Substances 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 238000007146 photocatalysis Methods 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 18
- 239000001257 hydrogen Substances 0.000 abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 18
- 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
- 239000002159 nanocrystal Substances 0.000 description 12
- 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
- 238000003756 stirring Methods 0.000 description 8
- 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
- 239000000243 solution Substances 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
- 239000007788 liquid Substances 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
- 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
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 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
- 238000012360 testing method Methods 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
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 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
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material 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
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 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
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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种Cd配位硫间质的CdxZn1‑ xS纳米晶体材料的制备方法与应用，包括如下步骤：将醋酸锌、硝酸镉和乙二胺混合，加入硫脲，得到混合液，再向混合液中通入酸性气体，进行恒压反应，反应结束后，冷却至室温，过滤、洗涤干燥，得到Cd配位硫间质的CdxZn1‑xS纳米晶体材料。本发明制得的纳米晶体材料具有高效的反应活性，能作为高效光催化产氢光催化剂。本发明首次采用通入酸性气体的方法选择性地将硫间质与CdxZn1‑xS中的Cd配位，制备方法简单可控、成本低廉、原料易得，适合于规模化生产。
The invention discloses a preparation method and application of a Cd-coordinated sulfur interstitial Cd x Zn 1- x S nanocrystalline material, comprising the following steps: mixing zinc acetate, cadmium nitrate and ethylenediamine, adding thiourea to obtain a mixed solution, then introducing an acidic gas into the mixed solution to perform a constant pressure reaction, and after the reaction is completed, cooling to room temperature, filtering, washing and drying to obtain a Cd-coordinated sulfur interstitial Cd x Zn 1-x S nanocrystalline material. The nanocrystalline material prepared by the invention has high reaction activity and can be used as a high-efficiency photocatalytic hydrogen production photocatalyst. The invention adopts the method of introducing an acidic gas for the first time to selectively coordinate the sulfur interstitial with Cd in Cd x Zn 1-x S, and the preparation method is simple and controllable, low in cost, and the raw materials are easily available, 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 preparation method and application of a Cd xZn1-x S nanocrystal material of a Cd coordination sulfur matrix.
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 problems in the prior art, the invention aims to provide a preparation method and application of a Cd xZn1-x S nano-crystalline material of a Cd coordination sulfur matrix, which can realize accurate control of the coordination ratio of the sulfur matrix and Cd element in the crystalline material.
In order to achieve the technical purpose, the invention provides the following technical scheme:
The preparation method of the Cd xZn1-x S (wherein, 0 is less than x is less than 1) nano crystal material of the Cd coordination sulfur matrix provided by the invention 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 xZn1-x S nano-crystalline material of Cd coordination sulfur matrix.
Preferably, the molar ratio of Cd (NO 3)2 to Zn (CH 3COO)2) is (1.0 to 10.0): 1.0.
Preferably, the molar ratio of Zn (CH 3COO)2) to ethylenediamine is (0.5-3): 1000.
Preferably, the molar ratio of Cd (NO 3)2 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.
The Cd xZn1-x S nano-crystalline material of the Cd coordination sulfur matrix prepared by the preparation method.
The Cd xZn1-x S nano crystal material of the Cd coordination sulfur matrix is a rod-shaped nano crystal, the side length of the nano crystal material is 50-200 nm, and the thickness of the nano crystal material is 5-10 nm.
The Cd xZn1-x S nanocrystalline material of the Cd coordination sulfur matrix is used as a photocatalysis material in photocatalysis.
In the invention, acid gas is introduced to react to generate elemental sulfur, and the elemental sulfur reacts with sulfur site of sulfide Cd xZn1-x S to form metal and organic sulfur binding sites. 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 the Cd xZn1-x S nano crystal material (I S(Cd)-CdxZn1-x S) with different Zn/Cd ratios by adopting a one-step hydrothermal method, and the hydrogen production performance of the I S(Cd)-CdxZn1-x S in visible light photocatalytic hydrogen evolution is greatly improved due to the coordination of the sulfur matrix at Cd sites, so that the high-efficiency hydrogen production efficiency can be maintained under the action of visible light, a hole capturing agent and water.
2) According to the invention, the method of introducing acid gas is adopted for the first time to selectively coordinate the sulfur interstitial with Cd in Cd xZn1-x S, so that the coordination ratio of the sulfur interstitial to Cd element can be accurately controlled, and the I S(Cd)-CdxZn1-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 a graph of elemental Zn/Cd ratios of the I S(Cd)-CdxZn1-x S nanocrystalline material in example 1.
FIG. 2 is an S-element analysis of the I S(Cd)-CdxZn1-x S nanocrystalline material of example 1.
FIG. 3 is a plot of the Zn-S coordination K-edge Fourier transform EXAFS of the I S(Cd)-Cd0.8Zn0.2 S nanocrystalline material of example 1.
FIG. 4 is a plot of the Cd-S coordination K-edge Fourier transform EXAFS of the I S(Cd)-Cd0.8Zn0.2 S nanocrystalline material of example 1.
Fig. 5 is an XRD pattern of the I S(Cd)-CdxZn1-x S nanocrystalline material in example 1.
Fig. 6 is an SEM image of the I S(Cd)-Cd0.8Zn0.2 S nanocrystalline material in example 1.
FIG. 7 is a graph showing the photocatalytic hydrogen production performance of the I S(Cd)-CdxZn1-x S nanocrystalline material in example 1.
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
Preparing Cd xZn1-x S nanocrystalline materials (I S(Cd)-CdxZn1-x S) of Cd coordination sulfur interstitials with different Zn/Cd ratios:
1) Taking x=0.9, preparing an I S(Cd)-Cd0.9Zn0.1 S nanocrystalline material:
Placing 60mL of ethylenediamine in a beaker, adding 0.625mmol of Zn (CH 3COO)2,5.625mmol Cd(NO3)2, stirring at a rotating speed of 500r/min for 10min to obtain uniformly distributed ionic liquid, taking 12.5mmol of CH 4N2 S, adding the solution, continuously stirring at a rotating speed of 500r/min for 30min to obtain uniformly distributed mixed solution of 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 of hydrogen sulfide at a constant flow rate, keeping the temperature at 150 for 24h at a constant pressure of 0.25MPa, taking out, cooling and filtering after the reaction is finished, repeatedly washing with ethanol and deionized water, and finally drying the washed product in a vacuum drying box at 80 for 24h to obtain the I S(Cd)-Cd0.9Zn0.1 S nanocrystalline material.
2) Taking x=0.8, preparing I S(Cd)-Cd0.8Zn0.2 S nano crystal material
Placing 60mL of ethylenediamine in a beaker, adding 1.25mmol of Zn (CH 3COO)2,5.0mmol Cd(NO3)2, stirring at a rotating speed of 500r/min for 10min to obtain uniformly distributed ionic liquid, taking 12.5mmol of CH 4N2 S, adding the solution, continuously stirring at the rotating speed of 500r/min for 30min to obtain uniformly distributed mixed liquid of Zn ions and Cd ions and organic ionic liquid, transferring the mixed liquid into a 300mL high-pressure constant-pressure reaction kettle, heating, continuously introducing 0.5mmol of sulfur dioxide and hydrogen sulfide mixed gas at a constant flow, wherein the molar ratio of the sulfur dioxide to the hydrogen sulfide is 2:1, keeping the temperature at a constant pressure of 0.3MPa and 170 for 36h, taking out, cooling and filtering after the reaction is finished, repeatedly washing the washed product with ethanol and deionized water, and drying the washed product at 80 for 24h in a vacuum drying box to obtain the I S(Cd)-Cd0.8Zn0.2 S nanocrystalline material.
3) Taking x=0.7, preparing an I S(Cd)-Cd0.7Zn0.3 S nanocrystalline material:
placing 60mL of ethylenediamine in a beaker, adding 1.875mmol of Zn (CH 3COO)2,4.375mmol Cd(NO3)2, stirring at a rotating speed of 500r/min for 10min to obtain uniformly distributed ionic liquid, taking 11.8mmol of CH 4N2 S, adding into the solution, continuously stirring at a rotating speed of 500r/min for 30min to obtain uniformly distributed mixed solution of Zn ions and Cd ions and organic ionic liquid, transferring the mixed solution into a 300mL high-pressure constant-pressure reaction kettle, heating, 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 temperature at a constant pressure of 0.35MPa and 140 for 36h, taking out, cooling and filtering after the reaction is finished, repeatedly washing the washed product with ethanol and deionized water, and finally drying the washed product in a vacuum drying box at 80 for 24h to obtain the I S(Cd)-Cd0.7Zn0.3 S nanocrystalline material.
4) Taking x=0.6, preparing an I S(Cd)-Cd0.6Zn0.4 S nanocrystalline material:
Placing 60mL of ethylenediamine in a beaker, adding 2.50mmol of Zn (CH 3COO)2,3.75mmol Cd(NO3)2, stirring at a rotating speed of 500r/min for 10min to obtain uniformly distributed ionic liquid, taking 10.9mmol of CH 4N2 S, adding the solution, continuously stirring at the rotating speed of 500r/min for 30min to obtain uniformly distributed mixed liquid of Zn ions and Cd ions and organic ionic liquid, transferring the mixed liquid into a 300mL high-pressure constant-pressure reaction kettle, heating, continuously introducing acid mixed gas of 0.85mmol of sulfur dioxide, hydrogen sulfide and chlorine at a constant flow rate, wherein the molar ratio of the sulfur dioxide to the hydrogen sulfide to the chlorine is 2:2:1, preserving the heat for 36h at a constant pressure of 0.4MPa and 160 , taking out, cooling and filtering, repeatedly washing with ethanol and deionized water, and finally drying the washed product in a vacuum drying box at 80 for 24h to obtain the I S(Cd)-Cd0.6Zn0.4 S nano crystal material.
The I S(Cd)-CdxZn1-x S nanocrystalline material prepared in this example was subjected to elemental Zn/Cd ratio testing, and the results are shown in FIG. 1. As can be seen from FIG. 1, the Zn/Cd ratio in ,IS(Cd)-Cd0.9Zn0.1SIS(Cd)-Cd0.8Zn0.2SIS(Cd)-Cd0.7Zn0.3SIS(Cd)-Cd0.6Zn0.4S corresponds to the Zn/Cd ratio in the corresponding pure Cd xZn1-x S.
The content of S element in the I S(Cd)-CdxZn1-x S nano crystal material prepared in the example is tested, and the result is shown in figure 2. As can be seen from FIG. 2, the S/(Zn+Cd+S) ratios in ,IS(Cd)-Cd0.9Zn0.1SIS(Cd)-Cd0.8Zn0.2SIS(Cd)-Cd0.7Zn0.3SIS(Cd)-Cd0.6Zn0.4S are all greater than 0.5, indicating the presence of sulfur interstitials.
FIG. 3 is a chart of the Zn-S coordination K-edge Fourier transform EXAFS of the I S(Cd)-Cd0.8Zn0.2 S nanocrystalline material produced in this example. As can be seen from the figure, there is no significant change in coordination number of S around Zn, resulting in no difference in the strength of the first coordinated Zn-S shell of Zn from that in Cd 0.8Zn0.2 S. FIG. 4 is a chart of the Cd-S coordination K-edge Fourier transform EXAFS of the I S(Cd)-Cd0.8Zn0.2 S nanocrystalline material produced in this example. 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 is an XRD pattern of the I S(Cd)-CdxZn1-x S nanocrystalline material produced in this example. As can be seen from the figure, all peaks of I S(Cd)-Cd0.8Zn0.2 S correspond to Cd 0.8Zn0.2 S standard PDF cards 49-1302 and move to low angles, indicating successful incorporation of the sulfur interstitials into the lattice.
FIG. 6 is an SEM image of an I S(Cd)-Cd0.8Zn0.2 S nanocrystalline material produced in this example. As can be seen from the figure, the I S(Cd)-Cd0.8Zn0.2 S crystal material is a rod-shaped nanocrystal, and the particle size is 100-200 nm.
Example 2
The I S(Cd)-CdxZn1-x S nanocrystalline material prepared in example 1 was tested for photocatalytic activity in a photocatalytic reactor (Labsolar-6A, beijing Perfect technologies Co., ltd.). For each test, 10.0mg of I S(Cd)-CdxZn1-x S, 0.035mol of sodium sulfide and 0.025mol of sodium sulfite were added to 100mL of deionized water, and the solution was sonicated in an ultrasonic bath for 30min, and then stored at 5and irradiated with a 300W xenon lamp and a 420nm ultraviolet filter. The hydrogen production was measured by gas chromatography.
The results of the hydrogen evolution performance test of the I S(Cd)-CdxZn1-x S nanocrystalline material under visible light are shown in FIG. 7. From FIG. 7, it can be seen that ,IS(Cd)-Cd0.9Zn0.1SIS(Cd)-Cd0.8Zn0.2SIS(Cd)-Cd0.7Zn0.3S and I S(Cd)-Cd0.6Zn0.4 S lead the hydrogen production performance to be greatly improved compared with the pure Cd xZn1-x S of the corresponding proportion Zn/Cd by introducing a sulfur matrix at the Cd position. As can be seen from the graph, the hydrogen production performance of the I S(Cd)-Cd0.9Zn0.1 S material is improved by 5 times compared with that of Cd 0.9Zn0.1 S, the hydrogen production performance of the I S(Cd)-Cd0.9Zn0.1 S material is improved by 4.8 times compared with that of Cd 0.8Zn0.2 S from 0.38 mmol.g -1h-1 to 1.9 mmol.g -1h-1;IS(Cd)-Cd0.8Zn0.2 S, the hydrogen production performance of the I S(Cd)-Cd0.9Zn0.1 S material is improved by 4.8 times compared with that of Cd 0.7Zn0.3 S from 1.13 mmol.g -1h-1 to 5.4 mmol.g -1h-1;IS(Cd)-Cd0.7Zn0.3 S, the hydrogen production performance of the I S(Cd)-Cd0.9Zn0.1 S material is improved by 4.4 times compared with that of Cd 0.6Zn0.4 S from 1.85 mmol.g -1h-1 to 8.8 mmol.g -1h-1;IS(Cd)-Cd0.6Zn0.4 S, and the hydrogen production performance of the I3834S material is improved by 4.4 times compared with that of Cd 0.6Zn0.4 S from 4.23 mmol.g -1h-1 to 18.76 mmol.g -1h-1.
The invention synthesizes the nano crystal material I S(Cd)-CdxZn1-x S with adjustable element coordination by adopting an improved hydrothermal method. As the coordination quantity of the Cd-site S element is changed, the I S(Cd)-CdxZn1-x S has high-efficiency photocatalytic hydrogen evolution performance responding to visible light, and can be applied to photocatalytic decomposition of water.
Claims (5)
1. A preparation method of a Cd xZn1-x S nanocrystalline material of a Cd coordination sulfur matrix 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 xZn1-x S nano-crystalline material of Cd coordination sulfur matrix;
The molar ratio of Cd (NO 3)2 to Zn (CH 3COO)2 is (1.0-10.0): 1.0;
The mol ratio of Zn (CH 3COO)2 to ethylenediamine is (0.5-3): 1000;
The molar ratio of the Cd (NO 3)2 to the thiourea is 1.0 (2.0-3.0);
The temperature of the constant pressure reaction is 90-200 , the reaction time is 12-45 h, and the pressure is 0.2-0.4 MPa;
The molar ratio of the acid gas to the thiourea is (0.01-0.1): 1.0.
2. The method according to claim 1, wherein the acid gas is hydrogen sulfide or an acid mixed gas containing hydrogen sulfide.
3. The method according to claim 2, wherein the acidic mixed gas containing hydrogen sulfide is a mixture of hydrogen sulfide and at least one of chlorine and sulfur dioxide.
4. A Cd xZn1-x S nanocrystalline material of a Cd-coordinated sulfur matrix produced according to the production process of any one of claims 1 to 3.
5. Use of a Cd xZn1-x S nanocrystalline material of a Cd-coordinated sulfur matrix according to claim 4 as photocatalytic material in photocatalysis.
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