CN108855141B - ReS2/CdS photocatalyst and preparation method and application thereof - Google Patents
ReS2/CdS photocatalyst and preparation method and application thereof Download PDFInfo
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- CN108855141B CN108855141B CN201810810565.4A CN201810810565A CN108855141B CN 108855141 B CN108855141 B CN 108855141B CN 201810810565 A CN201810810565 A CN 201810810565A CN 108855141 B CN108855141 B CN 108855141B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 146
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 119
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 81
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 230000001699 photocatalysis Effects 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 29
- 238000005303 weighing Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 24
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 15
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 12
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000007146 photocatalysis Methods 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- XFXWQRYJIJXOEZ-UHFFFAOYSA-N S(=O)(O)O.[Na+].[S-2].[Na+] Chemical compound S(=O)(O)O.[Na+].[S-2].[Na+] XFXWQRYJIJXOEZ-UHFFFAOYSA-N 0.000 claims description 7
- -1 cadmium ethylene diamine acetate Chemical compound 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- ABLUHSAGYBFGAI-UHFFFAOYSA-N ethane-1,2-diamine thiourea Chemical compound NC(=S)N.C(CN)N ABLUHSAGYBFGAI-UHFFFAOYSA-N 0.000 claims description 4
- ALYDDXONYRLFSU-UHFFFAOYSA-N ethene;thiourea Chemical group C=C.NC(N)=S ALYDDXONYRLFSU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- DGLFJZVTBSPHRT-UHFFFAOYSA-N C=C.[Cd] Chemical group C=C.[Cd] DGLFJZVTBSPHRT-UHFFFAOYSA-N 0.000 claims 1
- 150000004683 dihydrates Chemical class 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 239000004065 semiconductor Substances 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 150000003863 ammonium salts Chemical class 0.000 abstract 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 24
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 8
- AUIZLSZEDUYGDE-UHFFFAOYSA-L cadmium(2+);diacetate;dihydrate Chemical compound O.O.[Cd+2].CC([O-])=O.CC([O-])=O AUIZLSZEDUYGDE-UHFFFAOYSA-L 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- USWJSZNKYVUTIE-UHFFFAOYSA-N bis(sulfanylidene)rhenium Chemical compound S=[Re]=S USWJSZNKYVUTIE-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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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- 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
The invention discloses a ReS2/CdS photocatalyst, preparation method and application thereof, and ReS2The preparation method of the/CdS photocatalyst comprises the following steps: (1) weighing high rheniumDissolving ammonium salt, thioacetamide, hexamethylenetetramine and cadmium sulfide in distilled water to obtain a mixed solution B; (2) putting the mixed solution B obtained in the step (1) into a hydrothermal reaction kettle for hydrothermal reaction; (3) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, and adding dark green ReS in the hydrothermal reaction kettle2And performing alcohol washing, water washing and drying on the/CdS for later use. ReS obtained by the invention2The performance of the CdS photocatalyst on the photocatalytic hydrogen production of a CdS semiconductor is greatly improved, and the flexible ReS photocatalyst2The catalyst is loaded on the CdS surface as a cocatalyst, so that the scarcity and high cost of Pt are solved, the electron transfer of the CdS semiconductor photocatalytic material is accelerated, the carrier recombination probability of the CdS semiconductor photocatalytic material is inhibited, and a brand new way is provided for a CdS photocatalytic hydrogen production technology.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a ReS2A CdS photocatalyst, its preparation method and application are disclosed.
Background
In order to solve the global energy crisis and environmental pollution problems, the development and utilization of clean and renewable energy are the serious problems we face. The semiconductor photocatalyst is a promising technology based on renewable resources, which decomposes water into hydrogen, a clean energy source, by using solar energy. Classical photocatalysts, e.g. TiO2Because of its good stability, non-toxicity and low cost, it is widely studied as an excellent photocatalyst. TiO 22It has been shown to be excited under ultraviolet light, but ultraviolet light accounts for only 5% of sunlight, resulting in relatively low light use efficiency. Therefore, the development of efficient photocatalysts is a serious problem for all researchers. Currently, many different semiconductor materials, such as metal oxides, metal sulfides and metal nitrides, have proven to be successful in utilizing the sun for efficient hydrogen evolution studies.
Cadmium sulfide (CdS) photocatalyst is one of the most promising photocatalysts as a visible light driver. Due to its appropriate band gap (Eg ═ 2.42eV), visible light can be absorbed efficiently, with its valence and conduction band positions favoring thermal oxidation and reduction, respectively. However, because photo-generated electron and hole pairs cannot be effectively separated and transferred, the pure CdS photocatalyst is not favorable for Hydrogen Evolution Reaction (HER) due to low activity and high photo-etching speed. Loading a promoter on CdS to form a layered structure provides HER with a high activation potential and inhibits photo-corrosion of CdS. For example, platinum (Pt) as a promoter may improve the photocatalytic HER efficiency of CdS. However, Pt is limited due to its scarcity and high cost. Therefore, the search for effective non-noble metal promoters as alternatives to Pt is a direction of photocatalytic development.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a low-cost ReS aiming at the defects2A CdS photocatalyst, its preparation method and application are disclosed.
Inventive ReS2The technical scheme adopted by the preparation method and the application of the/CdS photocatalyst is as follows:
ReS2The preparation method of the/CdS photocatalyst comprises the following steps:
(1) weighing ammonium perrhenate, thioacetamide, hexamethylenetetramine and cadmium sulfide, dissolving in distilled water, and stirring for 10-20 min to obtain a mixed solution B;
(2) putting the mixed solution B obtained in the step (1) into a hydrothermal reaction kettle for hydrothermal reaction;
(3) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, and adding the ReS in the hydrothermal reaction kettle2and/CdS is subjected to alcohol washing and water washing for three times respectively, and dried for later use.
Preferably, in the step (1), the mass ratio of the cadmium sulfide to the ammonium perrhenate to the thioacetamide to the hexamethylenetetramine to the distilled water is 10: (0.025-2.505): (0.014-1.2655): (0.075-7.5): 1, the mass of the ammonium perrhenate loaded on the surface of the cadmium sulfide is 0.1-10%.
Preferably, the hydrothermal reaction conditions in step (2) are as follows: the reaction is carried out for 48h at the temperature of 100 ℃ and 250 ℃.
Preferably, the preparation method of the cadmium sulfide comprises the following steps:
(a) preparing a cadmium ethylene diamine acetate dihydrate solution and a thiourea ethylenediamine solution, and then dropwise adding the thiourea ethylenediamine solution into the cadmium ethylene diamine acetate dihydrate solution to obtain a mixed solution A;
(b) putting the mixed solution A obtained in the step (a) into a hydrothermal reaction kettle for hydrothermal reaction;
(c) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, washing cadmium sulfide in the hydrothermal reaction kettle with alcohol and water for three times respectively, and drying for later use.
Preferably, the mass concentration of the cadmium ethylene diamine acetate dihydrate solution in the step (a) is 0.14-0.15g/ml, the mass concentration of the thiourea ethylene diamine solution is 0.117-0.23g/ml, and the volume ratio of the cadmium ethylene diamine acetate dihydrate solution to the thiourea ethylene diamine solution is 1: 1.
Preferably, the hydrothermal reaction conditions in step (b) are as follows: reacting at 150 ℃ and 180 ℃ for 12-24 h.
The invention also provides the ReS prepared by the method2CdS photocatalyst with 1% ReS loaded on CdS surface2Of ReS2The band gap value of/CdS is 2.27eV, and the fluorescence lifetime is 1.56ns, which is longer than 1.51ns of pure CdS.
The invention also provides the ReS2The application of the CdS photocatalyst in photocatalytic hydrogen evolution.
Preferably, the method for photocatalytic hydrogen evolution comprises the following steps: weighing the obtained ReS2Adding a CdS photocatalyst into a sodium sulfide-sodium sulfite sacrificial reagent, and performing ultrasonic treatment to obtain a mixed solution; adding the obtained mixed solution into a reactor, accessing a hydrogen production photocatalysis system, and irradiating by using a xenon lamp source.
Preferably, the ReS2The mass ratio of the CdS photocatalyst to the sodium sulfide-sodium sulfite sacrificial reagent is 2: 5; ultrasonic processing for 3-5 min; the mass ratio of sodium sulfide to sodium sulfite to deionized water in the sodium sulfide-sodium sulfite sacrificial reagent is 1:0.381:23.81, when photocatalytic hydrogen evolution is carried out, the solution in the reactor is kept in a stirring state, and the temperature of the hydrogen production system is kept by circulating condensate water.
ReS prepared from cadmium sulfide obtained by the cadmium sulfide preparation method2The hydrothermal reaction condition can be controlled more easily in the case of the CdS photocatalyst.
The invention has the beneficial effects that:
(1) the invention prepares the ReS2When the catalyst is/CdS photocatalyst, deionized water is used as a solvent, CdS is used as a substrate, hexamethylenetetramine is used as a sulfur accelerator, and ammonium perrhenate is used asRhenium source and thioacetamide are used as sulfur source, and are kept in a hydrothermal reaction kettle for a certain temperature and time to obtain ReS2The preparation method of the/CdS photocatalyst is simple, easy to control and suitable for large-scale production, and the obtained ReS photocatalyst2The stability of the/CdS photocatalyst is good.
(2) ReS obtained by the invention2When the CdS photocatalyst is used for carrying out photocatalytic hydrogen evolution, the mixed solution of sodium sulfide and sodium sulfite is used as a sacrificial reagent to prepare the ReS2The catalyst is CdS, the xenon lamp is a catalytic light source, and the hydrogen evolution activity is detected in a photocatalytic system through gas chromatography, so that the catalytic efficiency is high.
(3) ReS obtained by the invention2The performance of the CdS photocatalyst for producing hydrogen by photocatalysis of CdS semiconductor is greatly improved, and the rhenium disulfide (ReS) is flexible2) The catalyst is loaded on the CdS surface as a cocatalyst, so that the scarcity and high cost of Pt are solved, the electron transfer of the CdS semiconductor photocatalytic material is accelerated, the carrier recombination probability of the CdS semiconductor photocatalytic material is inhibited, and a brand new way is provided for a CdS photocatalytic hydrogen production technology.
Drawings
FIG. 1 shows CdS and 1% ReS obtained in example 12Powder X-ray diffraction pattern of/CdS;
FIG. 2 shows CdS (left panel) and 1% ReS obtained in example 12Transmission electron microscopy of a powder of/CdS (right panel);
FIG. 3 shows CdS and 1% ReS obtained in example 12Photocatalytic performance of CdS;
FIG. 4 shows the ReS obtained in examples 1 to 62Photocatalytic Performance of/CdS photocatalyst (ReS)2Different load amount comparisons);
FIG. 5 shows the ReS obtained in example 1 and examples 7 to 112Photocatalytic Performance of/CdS photocatalyst (ReS)2Different thermal reaction conditions in the CdS preparation process).
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1
ReS2The preparation method of the/CdS photocatalyst comprises the following steps:
(1) weighing 4.317g of cadmium acetate dihydrate to dissolve in 30mL of ethylenediamine, weighing 3.699g of thiourea to dissolve in 30mL of ethylenediamine, and slowly dripping the thiourea into the ethylenediamine to obtain a mixed solution A;
(2) putting the mixed solution A obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 24 hours at 160 ℃;
(3) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, washing the yellow cadmium sulfide product in the hydrothermal reaction kettle with ethanol and deionized water for three times respectively, and drying for later use;
(4) weighing 400mg of the cadmium sulfide semiconductor material obtained in the step (3), 10.02mg of ammonium perrhenate and 5.617mg of thioacetamide, dissolving the ammonium perrhenate and the thioacetamide in 40ml of distilled water, and stirring for 10min until the materials are completely dissolved;
(5) putting the mixed solution B obtained in the step (4) into another hydrothermal reaction kettle, weighing 0.03g of hexamethylenetetramine, adding into the hydrothermal reaction kettle, and carrying out hydrothermal reaction at 200 ℃ for 48 hours;
(6) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, and then adding the dark green product ReS in the hydrothermal reaction kettle2The CdS is respectively washed three times by ethanol and deionized water and dried to obtain 1 percent ReS2/CdS。
Example 2
ReS2The preparation method of the/CdS photocatalyst comprises the following steps:
(1) weighing 4.317g of cadmium acetate dihydrate to dissolve in 30mL of ethylenediamine, weighing 3.699g of thiourea to dissolve in 30mL of ethylenediamine, and slowly dripping the thiourea into the ethylenediamine to obtain a mixed solution A;
(2) putting the mixed solution A obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 20h at 160 ℃;
(3) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, washing the yellow cadmium sulfide product in the hydrothermal reaction kettle with ethanol and deionized water for three times respectively, and drying for later use;
(4) weighing 400mg of the cadmium sulfide semiconductor material obtained in the step (3), 1.002mg of ammonium perrhenate and 0.561mg of thioacetamide, dissolving the ammonium perrhenate and the thioacetamide in 40ml of distilled water, and stirring for 20min until the materials are completely dissolved;
(5) putting the mixed solution B obtained in the step (4) into another hydrothermal reaction kettle, weighing 0.003g of hexamethylenetetramine, adding into the hydrothermal reaction kettle, and carrying out hydrothermal reaction at 200 ℃ for 48 hours;
(6) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, and then adding the dark green product ReS in the hydrothermal reaction kettle2The CdS is respectively washed three times by ethanol and deionized water and dried to obtain 0.1 percent ReS2/CdS。
Example 3
ReS2The preparation method of the/CdS photocatalyst comprises the following steps:
(1) weighing 4.317g of cadmium acetate dihydrate to dissolve in 30mL of ethylenediamine, weighing 3.699g of thiourea to dissolve in 30mL of ethylenediamine, and slowly dripping the thiourea into the ethylenediamine to obtain a mixed solution A;
(2) putting the mixed solution A obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 24 hours at the temperature of 150 ℃;
(3) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, washing the yellow cadmium sulfide product in the hydrothermal reaction kettle with ethanol and deionized water for three times respectively, and drying for later use;
(4) weighing 400mg of the cadmium sulfide semiconductor material obtained in the step (3), 5.01mg of ammonium perrhenate and 2.81mg of thioacetamide, dissolving the ammonium perrhenate and the thioacetamide in 40ml of distilled water, and stirring for 10min until the materials are completely dissolved;
(5) putting the mixed solution B obtained in the step (4) into another hydrothermal reaction kettle, weighing 0.015g of hexamethylenetetramine, adding into the hydrothermal reaction kettle, and carrying out hydrothermal reaction for 48 hours at 200 ℃;
(6) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, and then adding the dark green product ReS in the hydrothermal reaction kettle2The CdS is respectively washed three times by ethanol and deionized water and dried to obtain 0.5 percent ReS2/CdS。
Example 4
ReS2The preparation method of the/CdS photocatalyst comprises the following steps:
(1) weighing 4.317g of cadmium acetate dihydrate to dissolve in 30mL of ethylenediamine, weighing 3.699g of thiourea to dissolve in 30mL of ethylenediamine, and slowly dripping the thiourea into the ethylenediamine to obtain a mixed solution A;
(2) putting the mixed solution A obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 180 ℃;
(3) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, washing the yellow cadmium sulfide product in the hydrothermal reaction kettle with ethanol and deionized water for three times respectively, and drying for later use;
(4) weighing 400mg of the cadmium sulfide semiconductor material obtained in the step (3), 20.05mg of ammonium perrhenate and 11.234mg of thioacetamide, dissolving the ammonium perrhenate and the thioacetamide in 40ml of distilled water, and stirring for 15min until the materials are completely dissolved;
(5) putting the mixed solution B obtained in the step (4) into another hydrothermal reaction kettle, weighing 0.06g of hexamethylenetetramine, adding into the hydrothermal reaction kettle, and carrying out hydrothermal reaction at 200 ℃ for 48 hours;
(6) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, and then adding the dark green product ReS in the hydrothermal reaction kettle2The CdS is respectively washed three times by ethanol and deionized water and dried to obtain 2 percent ReS2/CdS。
Example 5
ReS2The preparation method of the/CdS photocatalyst comprises the following steps:
(1) weighing 4.317g of cadmium acetate dihydrate to dissolve in 30mL of ethylenediamine, weighing 3.699g of thiourea to dissolve in 30mL of ethylenediamine, and slowly dripping the thiourea into the ethylenediamine to obtain a mixed solution A;
(2) putting the mixed solution A obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 16h at 170 ℃;
(3) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, washing the yellow cadmium sulfide product in the hydrothermal reaction kettle with ethanol and deionized water for three times respectively, and drying for later use;
(4) weighing 400mg of the cadmium sulfide semiconductor material obtained in the step (3), 50.1mg of ammonium perrhenate and 28.05mg of thioacetamide, dissolving the ammonium perrhenate and the thioacetamide in 40ml of distilled water, and stirring for 20min until the materials are completely dissolved;
(5) putting the mixed solution B obtained in the step (4) into another hydrothermal reaction kettle, weighing 0.15g of hexamethylenetetramine, adding into the hydrothermal reaction kettle, and carrying out hydrothermal reaction for 48 hours at 200 ℃;
(6) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, and then adding the dark green product ReS in the hydrothermal reaction kettle2The CdS is respectively washed three times by ethanol and deionized water and dried to obtain 5 percent ReS2/CdS。
Example 6
ReS2The preparation method of the/CdS photocatalyst comprises the following steps:
(1) weighing 4.317g of cadmium acetate dihydrate to dissolve in 30mL of ethylenediamine, weighing 3.699g of thiourea to dissolve in 30mL of ethylenediamine, and slowly dripping the thiourea into the ethylenediamine to obtain a mixed solution A;
(2) putting the mixed solution A obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 20h at 150 ℃;
(3) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, washing the yellow cadmium sulfide product in the hydrothermal reaction kettle with ethanol and deionized water for three times respectively, and drying for later use;
(4) weighing 400mg of the cadmium sulfide semiconductor material obtained in the step (3), 100.2mg of ammonium perrhenate and 50.617mg of thioacetamide, dissolving the ammonium perrhenate and the thioacetamide in 40ml of distilled water, and stirring for 15min until the materials are completely dissolved;
(5) putting the mixed solution B obtained in the step (4) into another hydrothermal reaction kettle, weighing 0.3 parts of hexamethylenetetramine, adding into the hydrothermal reaction kettle, and carrying out hydrothermal reaction for 48 hours at the temperature of 200 ℃;
(6) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, and then adding the dark green product ReS in the hydrothermal reaction kettle2The CdS is respectively washed three times by ethanol and deionized water and dried to obtain 10 percent ReS2/CdS。
Example 7
ReS2The preparation method of the/CdS photocatalyst comprises the following steps:
only the reaction temperature of the step (5) was changed to 100 ℃ and the remaining steps and conditions were the same as those of example 1.
Example 8
ReS2The preparation method of the/CdS photocatalyst comprises the following steps:
only the reaction temperature of the step (5) was changed to 150 ℃ and the remaining steps and conditions were the same as those of example 1.
Example 9
ReS2The preparation method of the/CdS photocatalyst comprises the following steps:
only the reaction temperature in the step (5) was changed to 220 ℃ and the remaining steps and conditions were the same as in example 1.
Example 10
ReS2The preparation method of the/CdS photocatalyst comprises the following steps:
only the reaction temperature of the step (5) was changed to 250 ℃ and the remaining steps and conditions were the same as those of example 1.
EXAMPLE 11 catalytic characterisation determination to a clean beaker was added 50ml of a sacrificial reagent of sodium sulphide-sodium sulphite followed by 20mg of the ReS obtained in examples 1-102Performing ultrasonic treatment on the CdS photocatalyst for 3-5min, then pouring the solution into a quartz reactor, connecting the quartz reactor into a hydrogen production photocatalysis system, and keeping the circulating condensed water at 5 ℃. And vacuumizing the hydrogen production photocatalytic system connected with the quartz reactor. A xenon lamp light source is placed at the position 5cm above the quartz reactor, a sample is taken every half hour, enters the gas chromatograph through the hydrogen production photocatalytic system, the amount of hydrogen is detected through a TCD detector, and the results are shown in tables 1 and 2.
TABLE 1 comparison of the Hydrogen production of different photocatalysts
TABLE 2 comparison of hydrogen production at different thermal reaction temperatures
[ atlas analysis ]
FIG. 1 shows CdS (left graph) and 1% ReS obtained in example 1 of the present invention2Transmission electron microscopy of/CdS (right panel), from which ReS can be obtained2The nano-rod shape of the CdS is not changed by the load of the CdS, which shows that the surface of the CdS is loaded with the ReS2And ReS2The loading of CdS does not affect the structure of CdS itself.
FIG. 2 is CdS and 1% ReS prepared according to example 1 of the present invention2The XRD pattern of the/CdS photocatalyst at 2 theta of 5-80 degrees shows that the positions of photocatalyst peaks before and after loading do not shift, and no new peak appears. Description of the load ReS2The CdS structure is not changed, and the photocatalyst is well crystallized.
FIG. 3 shows CdS and 1% ReS obtained in example 1 of the present invention2The result of hydrogen production performance by photocatalytic reduction of CdS can be seen in the figure when 1% ReS is loaded with CdS2The post-hydrogen production performance is greatly improved, the hydrogen production per hour of CdS is 3.8umol, and 1 percent of ReS is loaded2The hydrogen production per hour is 487.2umol, which is improved by 128.21 times compared with CdS.
FIG. 4 shows 1% ReS obtained in example 1 of the present invention2PerCdS, 0.1% ReS from example 22PerCdS, 0.5% ReS from example 32PerCdS, 2% ReS from example 42PerCdS, 5% ReS from example 52CdS and 10% ReS from example 62The result of hydrogen production performance of water by photocatalytic reduction of CdS can be seen in the figure, and 0.1% ReS is loaded2The hydrogen production result of CdS photocatalysis is 1.5umol/h, and 0.5 percent of ReS is loaded2The hydrogen production result of CdS photocatalysis is 5.2umol/h, and 2 percent of ReS is loaded2The result of hydrogen production by CdS photocatalysis is 351.2umol/h, and 5 percent of ReS is loaded2The result of hydrogen production by CdS photocatalysis is 394.2umol/h, and the load is 10 percent of ReS2The result of hydrogen production by CdS photocatalysis is 318.4umol/h, and the load is 1 percent of ReS2The result of hydrogen production by CdS photocatalysis is 487.2umol/h, and the maximum performance is reached.
FIG. 5 shows 1% ReS of examples 1, 7 to 10 according to the invention21% ReS obtained at different hydrothermal reaction temperatures in CdS preparation2The results of hydrogen production performance by photocatalytic reduction of CdS/water show that the ReS obtained in example 12The hydrogen production result of the CdS photocatalysis is 487.2umol/h, and the ReS obtained in example 72The photocatalytic hydrogen production result of/CdS is 419.3 umol/h, as in example 8Get ReS2The hydrogen production result of the CdS photocatalysis is 431.5umol/h, and the ReS obtained in example 92The hydrogen production result of the CdS photocatalysis is 478.4umol/h, and the ReS obtained in the example 102The photocatalytic hydrogen production result of/CdS is 456.7 umol/h, and therefore, the ReS obtained under the thermal reaction condition of the example 1 is also obtained2The hydrogen production efficiency of CdS photocatalysis is maximum.
In other embodiments, ReS can also be prepared using cadmium sulfide purchased directly2A CdS photocatalyst.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by those of ordinary skill in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. ReS2The preparation method of the/CdS photocatalyst is characterized by comprising the following steps of:
(1) weighing ammonium perrhenate, thioacetamide, hexamethylenetetramine and cadmium sulfide, and dissolving in distilled water to obtain a mixed solution B;
(2) putting the mixed solution B obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 100 ℃ and 250 ℃;
(3) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, and adding dark green ReS in the hydrothermal reaction kettle2Performing alcohol washing, water washing and drying on the CdS for later use;
the mass ratio of cadmium sulfide, ammonium perrhenate, thioacetamide, hexamethylenetetramine and distilled water in the step (1) is 10: (0.2505-2.505): (0.014-1.2655): (0.075-7.5): 1, the mass of the ammonium perrhenate loaded on the surface of the cadmium sulfide is 1-10%.
2. The ReS of claim 12The preparation method of the/CdS photocatalyst is characterized in that the reaction time of the hydrothermal reaction in the step (2) is 48 hours.
3. The method of claim 1ReS2The preparation method of the/CdS photocatalyst is characterized in that the preparation method of the cadmium sulfide is as follows:
(a) preparing a cadmium ethylene diamine acetate dihydrate solution and a thiourea ethylenediamine solution, and then dropwise adding the thiourea ethylenediamine solution into the cadmium ethylene diamine acetate dihydrate solution to obtain a mixed solution A;
(b) putting the mixed solution A obtained in the step (a) into a hydrothermal reaction kettle for hydrothermal reaction;
(c) after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, and carrying out alcohol washing, water washing and drying on cadmium sulfide in the hydrothermal reaction kettle for later use.
4. The ReS of claim 32The preparation method of the/CdS photocatalyst is characterized in that the mass concentration of the cadmium ethylene diamine acetate dihydrate solution in the step (a) is 0.14-0.15g/ml, the mass concentration of the thiourea ethylene diamine solution is 0.117-0.23g/ml, and the volume ratio of the cadmium ethylene diamine dihydrate solution to the thiourea ethylene diamine solution is 1: 1.
5. The ReS of claim 42The preparation method of the/CdS photocatalyst is characterized in that the hydrothermal reaction conditions in the step (b) are as follows: reacting at 150 ℃ and 180 ℃ for 12-24 h.
6. ReS2/CdS photocatalyst, characterized in that the ReS2the/CdS photocatalyst is ReS prepared by the preparation method of any one of claims 1-52CdS photocatalyst with 1% ReS loaded on CdS surface2Of ReS2The band gap value of/CdS is 2.27eV, and the fluorescence lifetime is 1.56ns, which is longer than 1.51ns of pure CdS.
7. A ReS according to claim 62The application of the CdS photocatalyst in photocatalytic hydrogen evolution.
8. The ReS of claim 72The application of the CdS photocatalyst in photocatalytic hydrogen evolution is characterized in that the method for photocatalytic hydrogen evolution comprises the following steps: weighing the obtained ReS2Adding a CdS photocatalyst into a sodium sulfide-sodium sulfite sacrificial reagent, and performing ultrasonic treatment to obtain a mixed solution; adding the obtained mixed solution into a reactor, accessing a hydrogen production photocatalysis system, and irradiating by using a xenon lamp source.
9. The ReS of claim 82The application of the/CdS photocatalyst in photocatalytic hydrogen evolution is characterized in that the ReS is2The mass ratio of the CdS photocatalyst to the sodium sulfide-sodium sulfite sacrificial reagent is 2: 5; ultrasonic processing for 3-5 min; the mass ratio of sodium sulfide to sodium sulfite to deionized water in the sodium sulfide-sodium sulfite sacrificial reagent is 1:0.381: 23.81.
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