CN114632528A - Cadmium selenide/calcium molybdate photocatalyst and preparation method and application thereof - Google Patents
Cadmium selenide/calcium molybdate photocatalyst and preparation method and application thereof Download PDFInfo
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- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000011941 photocatalyst Substances 0.000 title abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 239000002159 nanocrystal Substances 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- NLZOGIZKBBJWPB-UHFFFAOYSA-N [Na].[SeH2] Chemical compound [Na].[SeH2] NLZOGIZKBBJWPB-UHFFFAOYSA-N 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 239000001201 calcium disodium ethylene diamine tetra-acetate Substances 0.000 claims description 2
- 235000011188 calcium disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 6
- 229910004647 CaMoO4 Inorganic materials 0.000 description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 6
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910020427 K2PtCl4 Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 108010024636 Glutathione Proteins 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229960003180 glutathione Drugs 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 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
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 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
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a cadmium selenide/calcium molybdate photocatalyst, a preparation method thereof and application of the photocatalyst in hydrogen production by water decomposition. The material is prepared by the following method: (1) synthesizing calcium molybdate by using an ultrasonic precipitation method; (2) synthesizing aqueous phase cadmium selenide nanocrystal; (3) and modifying the cadmium selenide nanocrystal on the surface of calcium molybdate to obtain the cadmium selenide/calcium molybdate photocatalyst. The cadmium selenide/calcium molybdate photocatalyst prepared by the invention has the advantages of simple synthesis method, low price of raw materials and the like. The cadmium selenide/calcium molybdate prepared by the invention is used for photocatalytic hydrogen production, compared with calcium molybdate, the hydrogen production efficiency is greatly improved, the photocatalytic hydrogen production amount in 6 hours can reach 48141.5 mu mol/g, and the material has good circulation stability in the hydrogen production process.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a cadmium selenide/calcium molybdate photocatalyst, a preparation method thereof and application of the photocatalyst in hydrogen production by water decomposition.
Background
In order to solve the problems of energy shortage, environmental pollution and the like, the photocatalytic water splitting is widely researched as a novel hydrogen production mode. The molybdate photocatalyst has the advantages of stable crystal structure, environmental friendliness, rich element resources, low cost, easiness in shape/size regulation and control and the like. However, the band gap is wide, the light absorption range is narrow, and the photogenerated electrons and holes are quickly compounded, so that the application of the material in the field of photocatalysis is limited. The II-VI group nanocrystalline is an important low-dimensional semiconductor material, and the energy band structure of the II-VI group nanocrystalline can be regulated and controlled by regulating the components, the size and other methods, so that the absorption and emission properties of the II-VI group nanocrystalline are further regulated and controlled. Cadmium selenide nanocrystals have appropriate energy band width and light absorption range, and are considered to be ideal photocatalytic materials.
Therefore, the composite photocatalyst is prepared by compounding the cadmium selenide nanocrystal with the calcium molybdate with a narrow band gap, the light absorption capacity of the calcium molybdate can be effectively improved, the separation and transfer of photoproduction electrons are accelerated, the recombination of the photoproduction electrons and holes is inhibited, and the hydrogen production efficiency by photolysis of water is improved.
In view of this, the invention is particularly proposed.
Disclosure of Invention
In order to improve the photocatalytic hydrogen production capability of calcium molybdate and solve the problems of narrow light absorption range, fast photoproduction electron-hole recombination and the like, the invention provides a cadmium selenide/calcium molybdate photocatalyst which takes calcium molybdate as a substrate and modifies cadmium selenide nanocrystals on the surface of the calcium molybdate. Meanwhile, the invention also provides a preparation method of the cadmium selenide/calcium molybdate photocatalyst and application of the cadmium selenide/calcium molybdate photocatalyst in the field of hydrogen production by decomposing water.
The invention aims to provide a preparation method of the cadmium selenide/calcium molybdate photocatalyst, which comprises the following steps:
(1) dissolving calcium chloride and disodium ethylene diamine tetraacetate in deionized water, fully stirring and dissolving, adding sodium molybdate, and continuously stirring for 10min to obtain a solution A;
(2) performing ultrasonic treatment on the solution A for 50min to obtain the calcium molybdate;
(3) adding Cd (NO) into a three-neck flask3)2·4H2Stirring and dissolving O and deionized water uniformly, adding a ligand as a stabilizer, and slowly dropwise adding a NaOH solution to adjust the pH of the solution to obtain a solution B;
(4) adding a sodium hydrogen selenide solution into the solution B, and heating and refluxing to prepare the cadmium selenide nanocrystal solution after the reaction is stable;
(5) adding a cadmium selenide nanocrystalline solution into the calcium molybdate, uniformly stirring, and heating and refluxing to obtain the cadmium selenide/calcium molybdate;
the steps (3) and (4) are all carried out in a nitrogen atmosphere.
Preferably, in the step (1), the molar ratio of the sodium molybdate, the calcium chloride and the disodium ethylenediamine tetraacetate is 1:1: (0.1-0.3).
Preferably, in the step (2), the precipitation reaction is performed in a beaker placed in an ultrasonic cleaner.
Preferably, Cd (NO) in the step (3)3)2The concentration of the solution is 0.0002-0.05 mol/L.
Preferably, the ligand in step (3) is one of mercaptopropionic acid, thioglycolic acid, cysteine, glutathione or the like.
Preferably, the molar ratio of Cd, Se and the ligand in the step (4) is 1 (0.15-0.25) to (2.0-3.0), the pH is adjusted to 9.00-11.00 by using 1M NaOH solution, and the heating reflux is carried out for 2-8h at 100 ℃.
Preferably, in the step (5), the mixed solution of the cadmium selenide nanocrystal solution and the calcium molybdate is heated and refluxed for 4 hours at 100 ℃.
The invention also aims to provide the application of the cadmium selenide/calcium molybdate in photocatalytic hydrogen production, and a specific photocatalytic hydrogen production decomposition test is carried out by using an all-glass automatic online trace gas analysis system (Labsolar-6A). Using Na2S·9H2O and Na2SO3An aqueous solution as a sacrificial agent. To the above aqueous solution was added 20mg of catalyst and 1 wt% K2PtCl4As a cocatalyst. In the photocatalytic hydrogen production test, a 300W xenon lamp is used as a simulated solar light source, a magnetic stirrer is started all the way to maintain the suspension and dispersion of the catalyst at a proper rotating speed, and a gas chromatograph (GC-2014) is used for measuring H2And (4) yield.
Compared with the prior art, the preparation method of cadmium selenide/calcium molybdate provided by the invention has the advantages of simple preparation method, cheap raw materials, convenience for large-scale production and the like. The cadmium selenide/calcium molybdate prepared by the method is used as a photocatalyst for hydrogen production, the hydrogen production effect is obviously improved compared with that of pure calcium molybdate, the hydrogen production amount in 6 hours can reach 48141.5 mu mol/g, and meanwhile, the material has good circulation stability.
Drawings
FIG. 1 is the CdSe/CaMoO prepared in example 34Scanning electron micrographs of the photocatalyst.
FIG. 2 is an X-ray diffraction pattern of the materials prepared in examples 1, 2 and 3.
FIG. 3 is a graph of the photocatalytic hydrogen production of the materials prepared in examples 1, 3, 4 and 5.
Detailed Description
The invention will be further described with reference to specific examples:
example 1
This example provides a CaMoO4The preparation method comprises the following steps:
(1) adding 1mmol of CaCl2And 0.2mmol of disodium ethylene diamine tetraacetate are added into 40mL of aqueous solution, after the solution is fully stirred and dissolved, 1mmol of H is added4MoNa2O6Continuously stirring for 10min to obtain solution A;
(2) subjecting the solution A to ultrasonic treatment in an ultrasonic cleaner for 50min to obtain the white precipitate CaMoO4。
Example 2
The embodiment provides a preparation method of a water-phase cadmium selenide nanocrystal, which comprises the following steps:
(1) 200mL of 0.001M Cd (NO) was added to a three-necked flask3)2Keeping the solution stirred, adding 42.18 mu L of 3-mercaptopropionic acid serving as a stabilizer, and slowly dropwise adding 1M NaOH solution to adjust the pH value to 10.00 to obtain a solution A;
(2) quickly injecting 0.06mL of sodium hydrogen selenide solution with the concentration of 0.6667M into the solution A by using an injector, and refluxing for 2h at 100 ℃ after the reaction is stable to prepare the cadmium selenide nanocrystal solution;
the steps (1) and (2) are all carried out in a nitrogen atmosphere.
Example 3
The embodiment provides a preparation method of cadmium selenide/calcium molybdate, which comprises the following steps:
(1) adding 1mmol of CaCl2And 0.2mmol disodium ethylenediaminetetraacetate were added to 40mL of the aqueous solution, sufficiently stirred and dissolved, and 1mmol H was added4MoNa2O6Continuously stirring for 10min to obtain solution A;
(2) subjecting the solution A to ultrasonic treatment in an ultrasonic cleaner for 50min to obtain the white precipitate CaMoO4。
(3) Into a three-necked flask was added 200mL of 0.001M Cd (NO)3)2Keeping the solution stirred, adding 42.18 mu L of 3-mercaptopropionic acid serving as a stabilizer, and slowly dropwise adding 1M NaOH solution to adjust the pH value to 10.00 to obtain a solution A;
(4) quickly injecting 0.06mL of sodium hydrogen selenide solution with the concentration of 0.6667M into the solution A by using an injector, and refluxing for 2h at 100 ℃ after the reaction is stable to prepare the cadmium selenide nanocrystal solution;
the steps (3) and (4) are all carried out in a nitrogen atmosphere.
(5) 100mg of the CaMoO was added to a single-neck flask4And uniformly stirring the powder and 50mL of the cadmium selenide nanocrystal solution, and heating and refluxing the mixture for 4 hours at the temperature of 100 ℃ to obtain the cadmium selenide/calcium molybdate.
The product obtained in example 3 was used as a photocatalyst to test the photocatalytic hydrogen production performance. The specific method comprises the following steps: 100mL of deionized water and 0.035mol of Na were added to the photochemical reactor2S·9H2O and 0.025mol of Na2SO3. To the above aqueous solution was added 20mg of catalyst and 1 wt% K2PtCl4As a cocatalyst. The closed test system was evacuated for 30min using a vacuum pump before the test began. In the photocatalytic hydrogen production test, a 300W xenon lamp is used as a simulated solar light source, a magnetic stirrer is started all the way to maintain the suspension and dispersion of the catalyst at a proper rotating speed, and a gas chromatograph (GC-2014) is used for measuring H2And (4) yield.
Example 4
The embodiment provides a preparation method of cadmium selenide/calcium molybdate, which comprises the following steps:
(1) adding 1mmol of CaCl2And 0.2mmol disodium ethylenediaminetetraacetate were added to 40mL of the aqueous solution, sufficiently stirred and dissolved, and 1mmol H was added4MoNa2O6Continuously stirring for 10min to obtain solution A;
(2) subjecting the solution A to ultrasonic treatment in an ultrasonic cleaner for 50min to obtain the white precipitate CaMoO4。
(3) Into a three-necked flask was added 200mL of 0.002M Cd (NO)3)2Keeping the solution stirred, adding 84.36 mu L of 3-mercaptopropionic acid serving as a stabilizer, and slowly dropwise adding 1M NaOH solution to adjust the pH value to 10.00 to obtain a solution A;
(4) quickly injecting 0.12mL of sodium hydrogen selenide solution with the concentration of 0.6667M into the solution A by using an injector, and refluxing for 2h at 100 ℃ after the reaction is stable to prepare the cadmium selenide nanocrystal solution;
the steps (3) and (4) are all carried out in a nitrogen atmosphere.
(5) 100mg of the CaMoO was added to a single-neck flask4And uniformly stirring the powder and 50mL of the cadmium selenide nanocrystal solution, and heating and refluxing the mixture for 4 hours at the temperature of 100 ℃ to obtain the cadmium selenide/calcium molybdate.
Example 5
The embodiment provides a preparation method of cadmium selenide/calcium molybdate, which comprises the following steps:
(1) adding 1mmol of CaCl2And 0.2mmol disodium ethylenediaminetetraacetate were added to 40mL of the aqueous solution, sufficiently stirred and dissolved, and 1mmol H was added4MoNa2O6Continuously stirring for 10min to obtain solution A;
(2) subjecting the solution A to ultrasonic treatment in an ultrasonic cleaner for 50min to obtain the white precipitate CaMoO4。
(3) Into a three-necked flask was placed 200mL of 0.0005M Cd (NO)3)2Keeping the solution stirred, adding 21.09 mu L of 3-mercaptopropionic acid serving as a stabilizer, and slowly dropwise adding 1M NaOH solution to adjust the pH value to 10.00 to obtain a solution A;
(4) quickly injecting 0.03mL of sodium hydrogen selenide solution with the concentration of 0.6667M into the solution A by using an injector, and refluxing for 2h at 100 ℃ after the reaction is stable to prepare the cadmium selenide nanocrystal solution;
the steps (3) and (4) are all carried out in a nitrogen atmosphere.
(5) 100mg of the CaMoO was added to a single-neck flask4And uniformly stirring the powder and 50mL of the cadmium selenide nanocrystal solution, and heating and refluxing the mixture for 4 hours at the temperature of 100 ℃ to obtain the cadmium selenide/calcium molybdate.
Example 6
The embodiment provides a preparation method of cadmium selenide/calcium molybdate, which comprises the following steps:
(1) adding 1mmol of CaCl2And 0.3mmol disodium ethylenediaminetetraacetate were added to 40mL of the aqueous solution, sufficiently stirred and dissolved, and 1mmol H was added4MoNa2O6Continuously stirring for 10min to obtain solution A;
(2) subjecting the solution A to ultrasonic treatment in an ultrasonic cleaner for 50min to obtain the white precipitate CaMoO4。
(3) Into a three-necked flask was added 200mL of 0.001M Cd (NO)3)2Keeping the solution stirred, adding 52.73 mu L of 3-mercaptopropionic acid serving as a stabilizer, and slowly dropwise adding 1M NaOH solution to adjust the pH value to 10.00 to obtain a solution A;
(4) quickly injecting 0.06mL of sodium hydrogen selenide solution with the concentration of 0.6667M into the solution A by using an injector, and refluxing for 2h at 100 ℃ after the reaction is stable to prepare the cadmium selenide nanocrystal solution;
the steps (3) and (4) are all carried out in a nitrogen atmosphere.
(5) 100mg of the CaMoO was added to a single-neck flask4And uniformly stirring the powder and 50mL of the cadmium selenide nanocrystal solution, and heating and refluxing the mixture for 4 hours at the temperature of 100 ℃ to obtain the cadmium selenide/calcium molybdate.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any person skilled in the art may modify or modify the technical details disclosed above into equivalent embodiments with equivalent variations. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are still covered in the protection scope of the technical solution of the present invention.
Claims (7)
1. The cadmium selenide/calcium molybdate is characterized in that calcium molybdate is synthesized by an ultrasonic precipitation method, and cadmium selenide nanocrystals are modified on the surface of the calcium molybdate to obtain the cadmium selenide/calcium molybdate.
2. The method of claim 1, comprising the steps of:
(1) dissolving calcium chloride and disodium ethylene diamine tetraacetate in deionized water, fully stirring and dissolving, adding sodium molybdate, and continuously stirring for 10min to obtain a solution A;
(2) performing ultrasonic treatment on the solution A for 50min to obtain the calcium molybdate;
(3) adding Cd (NO) into a three-neck flask3)2·4H2Stirring and dissolving O and deionized water uniformly, adding a ligand as a stabilizer, and slowly dropwise adding a NaOH solution to adjust the pH of the solution to obtain a solution B;
(4) adding a sodium hydrogen selenide solution into the solution B, and heating and refluxing to prepare the cadmium selenide nanocrystal solution after the reaction is stable;
(5) adding a cadmium selenide nanocrystalline solution into the calcium molybdate, uniformly stirring, and heating and refluxing to obtain the cadmium selenide/calcium molybdate;
the steps (3) and (4) are all carried out in a nitrogen atmosphere.
3. The method for preparing cadmium selenide/calcium molybdate according to claim 2, wherein in the step (1), the molar ratio of the sodium molybdate, the calcium chloride and the ethylene diamine tetraacetic acid disodium salt is 1:1 (0.1-0.3).
4. The method of claim 2, wherein the Cd (NO) in step (3) is Cd (NO)3)2The concentration of the solution is 0.0002-0.05 mol/L.
5. The method for preparing cadmium selenide/calcium molybdate according to claim 2, wherein the molar ratio of Cd, Se and the ligand in the step (4) is 1 (0.15-0.25) to (2.0-3.0), the pH is adjusted to 9.00-11.00 by using 1M NaOH solution, and the heating and refluxing are carried out at 100 ℃ for 2-8 h.
6. The method for preparing cadmium selenide/calcium molybdate according to claim 2, wherein in the step (5), the mixed solution of the cadmium selenide nanocrystal solution and the calcium molybdate is heated and refluxed at 100 ℃ for 4 hours.
7. The use of cadmium selenide/calcium molybdate according to claim 1 for photocatalytic hydrogen production.
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