CN115350714A - Cadmium lanthanum sulfide/nickel sulfide composite material, preparation method thereof and application thereof in photocatalytic hydrogen production - Google Patents
Cadmium lanthanum sulfide/nickel sulfide composite material, preparation method thereof and application thereof in photocatalytic hydrogen production Download PDFInfo
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- CN115350714A CN115350714A CN202211066693.5A CN202211066693A CN115350714A CN 115350714 A CN115350714 A CN 115350714A CN 202211066693 A CN202211066693 A CN 202211066693A CN 115350714 A CN115350714 A CN 115350714A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 80
- RAUBNOIKGSOZTM-UHFFFAOYSA-N cadmium(2+) lanthanum(3+) sulfide Chemical compound [S-2].[La+3].[Cd+2] RAUBNOIKGSOZTM-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 25
- 239000001257 hydrogen Substances 0.000 title claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 230000007547 defect Effects 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000000034 method Methods 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 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical group OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention provides a cadmium lanthanum sulfide/nickel sulfide composite material, a preparation method thereof and application thereof in photocatalytic hydrogen production. The preparation method of the cadmium lanthanum sulfide/nickel sulfide composite material comprises the following steps: s1: dissolving a lanthanum source, a cadmium source and an excessive sulfur source in a solvent, fully stirring, reacting, cleaning and drying a reaction product to obtain defect lanthanum cadmium sulfide; s2: mixing the defect cadmium lanthanum sulfide with a solvent to prepare a defect cadmium lanthanum sulfide suspension, adding a nickel source and a sulfur source into the defect cadmium lanthanum sulfide suspension, stirring, vacuumizing, irradiating by a xenon lamp, centrifuging, cleaning and drying to prepare the cadmium lanthanum sulfide/nickel sulfide composite material. The cadmium lanthanum sulfide/nickel sulfide composite material has good photocatalytic hydrogen production performance.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a cadmium lanthanum sulfide/nickel sulfide composite material, a preparation method thereof and application thereof in photocatalytic hydrogen production.
Background
Among the new energy sources, solar energy is considered as an abundant renewable energy source in addition to thermal energy, wind energy, tidal energy, and nuclear energy, and has characteristics of easy availability, environmental protection, and the like. The hydrogen energy is used as a clean energy source, has the characteristics of high fuel value, easy storage, cleanness and the like, and can be used for decomposing water to produce hydrogen by utilizing solar energy to replace the traditional fossil fuel to produce the hydrogen, thereby greatly relieving a series of environmental problems caused by over combustion of the fossil fuel, such as generation of greenhouse gases, such as carbon dioxide and the like. Therefore, photocatalytic decomposition of water to produce hydrogen is an environmentally friendly technology that can solve certain energy problems without causing environmental burdens.
Cadmium lanthanum sulfide (CdLa) 2 S 4 ) The ternary sulfide has a proper band gap (2.1 eV-2.5 eV), can respond to visible light, has strong light absorption capacity and certain photocatalytic activity, and can decompose organic matters and decompose water to produce hydrogen by utilizing the visible light. However, due to the pure CdLa 2 S 4 The problems of low carrier separation rate, slow transfer rate and the like caused by light excitation exist, so that the pure CdLa 2 S 4 The photocatalytic activity of (2) has yet to be improved.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a cadmium lanthanum sulfide/nickel sulfide composite material, a preparation method thereof and application thereof in photocatalytic hydrogen production.
The invention provides a preparation method of a cadmium lanthanum sulfide/nickel sulfide composite material, which comprises the following steps:
s1: dissolving a lanthanum source, a cadmium source and an excessive sulfur source in a solvent, fully stirring, reacting, and cleaning and drying a reaction product to obtain defective cadmium lanthanum sulfide;
s2: mixing the defect cadmium lanthanum sulfide with a solvent to prepare a defect cadmium lanthanum sulfide suspension, adding a nickel source and a sulfur source into the defect cadmium lanthanum sulfide suspension, stirring, vacuumizing, irradiating by a xenon lamp, centrifuging, cleaning and drying to prepare the cadmium lanthanum sulfide/nickel sulfide composite material.
Specifically, in the step S1, a lanthanum source is lanthanum nitrate, a cadmium source is cadmium nitrate, and a sulfur source is thiourea; the molar ratio of the lanthanum source to the cadmium source to the sulfur source is 1: (0.5-1): (4-8), for example 2.5:1.5:15.
in the step S1, the solvent is a mixed solvent of absolute ethyl alcohol and deionized water, and the volume ratio of the absolute ethyl alcohol to the deionized water is 1: (1.5-2.5), for example 1:2.
more specifically, 2.4mmol of La (NO) can be added 3 ) 3 ·6H 2 O、1.5mmol Cd(NO 3 ) 2 ·4H 2 O and 15mmol of thiourea were dissolved in a mixed solvent of 5mL of absolute ethanol and 10mL of water.
In step S1, the time for sufficient stirring is 1.5-2.5h, for example 2h; the reaction temperature is 150-170 ℃, for example 160 ℃; the reaction time is 68-76h, for example 72 h.
The preparation method can prepare the defect cadmium lanthanum sulfide (Vs-CdLa) 2 S 4 ) The construction of the cadmium lanthanum sulfide defect can regulate and control the electronic structure and the surface characteristics of the material, not only can increase the capture sites of free electrons, thereby achieving the purpose of reducing the high-speed recombination of photon-generated carriers, but also can influence the band gap and the Fermi level position of the material to form a new defect state level and be beneficial to the separation of electron hole pairs; in addition, the structure of the defect of the cadmium lanthanum sulfide relieves the photo-corrosion phenomenon, and the defect can reduce part of photon-generated carrier recombination, thereby realizing the purpose of carrier separation, and surface vacancy can also be used as a catalytic active site for hydrogen adsorption, so that the photocatalytic performance of the material is obviously improved.
In step S2, the solvent is an ethanol solution with a volume content of 20-30% (e.g. 25%), and the dosage ratio of the defect cadmium lanthanum sulfide to the solvent is 1mg: (1.5-1.7) mL, e.g., 1mg:1.6mL.
In step S2, a nickel nitrate solution with a nickel source of 0.08-0.12M (e.g., 0.1M) and a thiourea solution with a sulfur source of 0.8-1.2M (e.g., 1M); adding a nickel source and a sulfur source which are equal in volume into the suspension of the defect cadmium lanthanum sulfide, and controlling the mass ratio of nickel to the defect cadmium lanthanum sulfide to be (1-3): 100.
in the step S2, the stirring time is 40-80min, such as 1h; the xenon lamp irradiation time is 40-80min, such as 1h.
According to the preparation method, the defects are constructed and simultaneously the non-noble metal promoter is introduced, so that the transfer of photo-generated electrons can be promoted, and more active sites can be provided; in particular, deposition of the promoter by means of photo-deposition allows NiS to be obtained 1+x Under the induction of photo-generated electrons and holes, the cadmium sulfide is more adaptively and uniformly deposited on the surface of the defect cadmium lanthanum sulfide, so that the remarkable improvement of the performance can be realized when a small amount of non-noble metal promoter is introduced. The above-described constructive drawbacks enable a good synergy to be exerted with the introduction of the cocatalyst.
The invention also provides a lanthanum cadmium sulfide/nickel sulfide composite material which is prepared according to the preparation method.
The invention also provides application of the cadmium lanthanum sulfide/nickel sulfide composite material in photocatalytic hydrogen production.
The invention also provides a photocatalytic hydrogen production method, which comprises the following steps: adding a sacrificial agent and the cadmium lanthanum sulfide/nickel sulfide composite material into deionized water to carry out photocatalytic hydrogen production.
The implementation of the invention has at least the following advantages:
1. according to the preparation method, the photo-corrosion phenomenon of the cadmium lanthanum sulfide is relieved by constructing the defect, partial photon-generated carrier recombination can be reduced by the defect, and the photocatalytic performance of the material is remarkably improved;
2. the preparation method can realize the remarkable improvement of the performance only by adding a small amount of non-noble metal cocatalyst, thereby greatly reducing the manufacturing cost of the composite material;
3. the preparation method of the invention deposits the cocatalyst in a light deposition mode, so that NiS can be obtained 1+x Under the induction of photo-generated electrons and holes, the cadmium sulfide is more adaptively and uniformly deposited on the surface of the defect cadmium lanthanum sulfide;
4. the preparation method disclosed by the invention has the advantages that the reaction temperature is relatively low, the energy consumption is reduced, and the experimental process is safer; the reaction raw materials are simple and easy to obtain, the required energy consumption is low, and the operation is simple and convenient; the synthesized composite material has good photocatalytic hydrogen production performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows the results of X-ray diffraction measurements of composite materials prepared in examples 1 to 3 of the present invention;
FIG. 2 is a XPS test result of a composite material prepared in example 2 of the present invention;
FIG. 3 is a photo-catalytic hydrogen production performance test chart of the composite material prepared in examples 1-3 of the present invention under the irradiation of visible light (λ ≧ 420 nm);
FIG. 4 is a photo-catalytic hydrogen production stability test chart of the composite material prepared in example 2 of the present invention under the irradiation of visible light (λ ≧ 420 nm).
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an", and "the" include plural forms as well, unless the context clearly indicates otherwise, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be apparent that the described embodiments are some, but not all, embodiments of the present 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
The preparation method of the cadmium lanthanum sulfide/nickel sulfide composite material comprises the following steps:
1. preparation of defective cadmium lanthanum sulfide (Vs-CdLa) 2 S 4 )
2.4mmol of La (NO) 3 ) 3 ·6H 2 O、1.5mmol Cd(NO 3 ) 2 ·4H 2 Dissolving O and excessive thiourea (15 mmol) in a mixed solvent of 5mL of absolute ethyl alcohol and 10mL of LDI water, and fully stirring for 2 hours; then, the mixture is transferred to a polytetrafluoroethylene reaction kettle and reacted for 72 hours at 160 ℃; after the reaction is finished, cooling to room temperature, washing the material with pure water and ethanol for multiple times, and drying at 60 ℃ to obtain the defect cadmium lanthanum sulfide Vs-CdLa 2 S 4 。
2. Preparation of cadmium lanthanum sulfide/nickel sulfide composite material
50mg of Vs-CdLa prepared above was charged 2 S 4 Dissolving in 80mL of ethanol solution with the volume fraction of 25% to prepare suspension; equal volume of Ni (NO) 3 ) 2 Adding solution (0.1M) and thiourea solution (1M) into the suspension, and controlling Ni and Vs-CdLa 2 S 4 1:100, stirring for 1 hour, vacuumizing the stirred mixed solution, and irradiating for 1 hour by using a xenon lamp; centrifuging, cleaning, collecting product, and vacuum drying at 60 deg.C to obtain cadmium lanthanum sulfide/nickel sulfide composite material (designated as Vs-CdLa) 2 S 4 /NiS 1+x -1, abbreviated Vs-CLS/NiS (1+x) -1), the X-ray diffraction test results are shown in figure 1.
Example 2
The preparation method of the cadmium lanthanum sulfide/nickel sulfide composite material comprises the following steps:
1. preparation of defect cadmium lanthanum sulfide (Vs-Cdla) 2 S 4 )
2.4mmol of La (NO) 3 ) 3 ·6H 2 O、1.5mmol Cd(NO 3 ) 2 ·4H 2 A mixed solution of O and excess thiourea (15 mmol) in 5mL of absolute ethanol and 10mL of waterFully stirring for 2 hours in the agent; then, the mixture is transferred to a polytetrafluoroethylene reaction kettle and reacted for 72 hours at 160 ℃; after the reaction is finished, cooling to room temperature, washing the material with pure water and ethanol for multiple times, and drying at 60 ℃ to obtain the defect cadmium lanthanum sulfide Vs-CdLa 2 S 4 The results of the X-ray diffraction test are shown in FIG. 1.
2. Preparation of cadmium lanthanum sulfide/nickel sulfide composite material
50mg of Vs-CdLa prepared above was charged 2 S 4 Dissolving in 80mL of ethanol solution with the volume fraction of 25% to prepare suspension; equal volume of Ni (NO) 3 ) 2 Adding solution (0.1M) and thiourea solution (1M) into the suspension, and controlling Ni and Vs-CdLa 2 S 4 2:100, stirring for 1 hour, vacuumizing the stirred mixed solution, and irradiating for 1 hour by using a xenon lamp; centrifuging, cleaning, collecting product, and vacuum drying at 60 deg.C to obtain sulfur lanthanum cadmium/nickel sulfide composite material (designated as Vs-Cdla) 2 S 4 /NiS 1+x 2, abbreviated as Vs-CLS/NiS (1+x) -2), the results of the X-ray diffraction test are shown in FIG. 1.
The X-ray diffraction test results of FIG. 1 show that the XRD diffraction peak is analyzed by Jade software and is matched with the CdLa disclosed in the literature 2 S 4 The inosculation is good, and CdS and La are not found 2 S 3 Diffraction peaks of the like; and no NiS appears in XRD 1+x Possibly due to loading of NiS 1+x The amount of (c) is too low.
The XPS test results of FIG. 2 show that Vs-CdLa is measured in the S2 p spectrum curve 2 S 4 /NiS 1+x For-2, 161.9eV and 163eV are assigned to S2 p respectively 3/2 And S2 p 1/2 Compared with Vs-CdLa 2 S 4 Moving towards low binding energy by 0.1eV; in addition, cd 3d shifts to high binding energy by 0.1eV, and photogenerated electrons are strongly verified to grow from Vs-CdLa 2 S 4 Migration to NiS rich in sulfur 1+x The above. In the curve of the Ni 2p spectrum, 855.9eV (Ni 2 p) 3/2 ) And 873.8eV (Ni 2 p) 1/2 ) Two obvious characteristic peaks are present, satellite peaks of two characteristic peaks are present at 861.7eV and 879.3eV, and 852.2eV is present in a smaller characteristic peakCharacteristic peak, which represents NiS 1+x Characteristic peak of the medium Ni-S bond.
Example 3
1. Preparation of defective cadmium lanthanum sulfide (Vs-CdLa) 2 S 4 )
2.4mmol of La (NO) 3 ) 3 ·6H 2 O、1.5mmol Cd(NO 3 ) 2 ·4H 2 Dissolving O and excessive thiourea (15 mmol) in a mixed solvent of 5mL of absolute ethyl alcohol and 10mL of LDI water, and fully stirring for 2 hours; then, the mixture is transferred to a polytetrafluoroethylene reaction kettle and reacted for 72 hours at 160 ℃; after the reaction is finished, cooling to room temperature, washing the material with pure water and ethanol for multiple times, and drying at 60 ℃ to obtain the defect cadmium lanthanum sulfide Vs-CdLa 2 S 4 。
2. Preparation of cadmium lanthanum sulfide/nickel sulfide composite material
50mg of Vs-CdLa prepared above was charged 2 S 4 Dissolving in 80mL of ethanol solution with the volume fraction of 25% to prepare suspension; equal volume of Ni (NO) 3 ) 2 Adding solution (0.1M) and thiourea solution (1M) into the suspension, and controlling Ni and Vs-Cdla 2 S 4 3:100, stirring for 1 hour, vacuumizing the stirred mixed solution, and irradiating for 1 hour by using a xenon lamp; centrifuging, cleaning, collecting product, and vacuum drying at 60 deg.C to obtain sulfur lanthanum cadmium/nickel sulfide composite material (designated as Vs-CdLa) 2 S 4 /NiS 1+x -3, abbreviated Vs-CLS/NiS (1+x) -3), the results of the X-ray diffraction test are shown in FIG. 1.
Comparative example 1
This comparative example was prepared as in example 2 with the deficient lanthanum cadmium sulfide Vs CdLa 2 S 4 As a control.
Comparative example 2
This comparative example uses a common commercially available nickel sulfide as a control.
Comparative example 3
The comparative example uses cadmium lanthanum sulfide (CdLa) 2 S 4 ) As a control, cadmium lanthanum sulfide (CdLa) 2 S 4 ) The preparation method comprises the following steps:
2.4mmol of La (NO) 3 ) 3 ·6H 2 O、1.5mmol Cd(NO 3 ) 2 ·4H 2 Dissolving O and thiourea (5 mmol) in a mixed solvent of 5mL of absolute ethyl alcohol and 10mL of LDI water, and fully stirring for 2 hours; then, the mixture is transferred to a polytetrafluoroethylene reaction kettle and reacted for 72 hours at 160 ℃; after the reaction is finished, cooling to room temperature, washing the material with pure water and ethanol for multiple times, and drying at 60 ℃ to obtain the cadmium lanthanum sulfide CdLa 2 S 4 。
Comparative example 4
In the step of preparing cadmium lanthanum sulfide/nickel sulfide composite material, except that silver nitrate solution is used to replace Ni (NO) of example 2 3 ) 2 Solution, otherwise essentially the same as in example 2; control of Ag and Vs-Cdila 2 S 4 2:100, preparing the lanthanum cadmium sulfide/silver sulfide composite material (designated as Vs-CdLa) 2 S 4 /Ag 2 S-2, abbreviated as Vs-CLS/Ag 2 S-2)。
Test example 1
100mL of DI water was taken and 0.25M Na was added 2 SO 3 And 0.35M Na 2 S is used as a sacrificial agent, 10mg of materials of each example and each comparative example are used as catalysts to carry out a photocatalytic hydrogen production performance test, and the test time is 240min; the test results are shown in table 1 and fig. 3.
The photocatalytic hydrogen production stability test was performed on the composite material prepared in example 2 by the above method, and the result is shown in fig. 4.
TABLE 1 photocatalytic Hydrogen production Performance test results of each composite Material
Composite material | Hydrogen production rate (μmolg) -1 h -1 ) |
Example 1 | 6127.1 |
Example 2 | 8262.8 |
Example 3 | 5081.4 |
Comparative example 1 | 1026.9 |
Comparative example 2 | 547.6 |
Comparative example 3 | 142.3 |
Comparative example 4 | 1521.8 |
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a cadmium lanthanum sulfide/nickel sulfide composite material is characterized by comprising the following steps:
s1: dissolving a lanthanum source, a cadmium source and an excessive sulfur source in a solvent, fully stirring, reacting, cleaning and drying a reaction product to obtain defect lanthanum cadmium sulfide;
s2: mixing the defect cadmium lanthanum sulfide with a solvent to prepare a defect cadmium lanthanum sulfide suspension, adding a nickel source and a sulfur source into the defect cadmium lanthanum sulfide suspension, stirring, vacuumizing, irradiating by a xenon lamp, centrifuging, cleaning and drying to prepare the cadmium lanthanum sulfide/nickel sulfide composite material.
2. The preparation method according to claim 1, wherein in step S1, the lanthanum source is lanthanum nitrate, the cadmium source is cadmium nitrate, and the sulfur source is thiourea; the molar ratio of the lanthanum source to the cadmium source to the sulfur source is 1: (0.5-1): (4-8).
3. The preparation method according to claim 1, wherein in the step S1, the solvent is a mixed solvent of absolute ethyl alcohol and deionized water, and the volume ratio of absolute ethyl alcohol to deionized water is 1: (1.5-2.5).
4. The method according to claim 1, wherein in step S1, the time for sufficient stirring is 1.5 to 2.5 hours; the reaction temperature is 150-170 ℃, and the reaction time is 68-76h.
5. The preparation method according to claim 1, wherein in the step S2, the solvent is an ethanol solution with a volume content of 20-30%, and the dosage ratio of the defect cadmium lanthanum sulfide to the solvent is 1mg: (1.5-1.7) mL.
6. The production method according to claim 1, wherein in step S2, the nickel source is a 0.08 to 0.12M nickel nitrate solution, and the sulfur source is a 0.8 to 1.2M thiourea solution; adding a nickel source and a sulfur source which are equal in volume into the defect cadmium lanthanum sulfide suspension, and controlling the mass ratio of nickel to the defect cadmium lanthanum sulfide to be (1-3): 100.
7. the method according to claim 1, wherein in step S2, the stirring time is 40 to 80min; the xenon lamp irradiation time is 40-80min.
8. A cadmium lanthanum sulphide/nickel sulphide composite material, characterised in that it is obtained according to the preparation method described in any one of claims 1 to 7.
9. The use of the cadmium lanthanum sulfide/nickel sulfide composite material of claim 8 in photocatalytic hydrogen production.
10. A photocatalytic hydrogen production method is characterized by comprising the following steps: adding a sacrificial agent and the cadmium lanthanum sulfide/nickel sulfide composite material as claimed in claim 8 into deionized water to carry out photocatalytic hydrogen production.
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