CN114632528B - 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
- Publication number
- CN114632528B CN114632528B CN202210333188.6A CN202210333188A CN114632528B CN 114632528 B CN114632528 B CN 114632528B CN 202210333188 A CN202210333188 A CN 202210333188A CN 114632528 B CN114632528 B CN 114632528B
- Authority
- CN
- China
- Prior art keywords
- solution
- cadmium selenide
- calcium molybdate
- molybdate
- calcium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 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 51
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002159 nanocrystal Substances 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 19
- 230000001699 photocatalysis Effects 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 14
- 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 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 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 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- 108010024636 Glutathione Proteins 0.000 claims description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- 229960003180 glutathione Drugs 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims 3
- 239000001201 calcium disodium ethylene diamine tetra-acetate Substances 0.000 claims 1
- 235000011188 calcium disodium ethylene diamine tetraacetate Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 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 7
- 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
- 238000012360 testing method Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 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
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 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
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—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 an ultrasonic precipitation method; (2) synthesizing aqueous phase cadmium selenide nanocrystals; (3) And modifying the cadmium selenide nanocrystalline 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 raw material price and the like. Compared with calcium molybdate, the hydrogen production efficiency of the cadmium selenide/calcium molybdate prepared by the invention is greatly improved, the hydrogen production amount of the cadmium selenide/calcium molybdate 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 and 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, photocatalytic decomposition of water is a novel hydrogen production mode, and has led to extensive research. The molybdate photocatalyst has the advantages of stable crystal structure, environmental friendliness, rich element resources, low cost, easiness in shape/size regulation and the like. However, the band gap is wider, the light absorption range is narrow, and the photo-generated electron-hole recombination is fast, so that the application of the photo-generated electron-hole composite in the field of photocatalysis is limited. The II-VI family nanocrystalline is an important low-dimensional semiconductor material, and the energy band structure can be regulated and controlled by regulating the components, the size and the like of the material, so that the absorption and emission properties of the material are further regulated and controlled. Among them, cadmium selenide nanocrystals having a suitable energy band width and light absorption range are considered as an ideal photocatalytic material.
Therefore, the composite photocatalyst is prepared by compounding cadmium selenide nanocrystalline with narrower band gap with calcium molybdate, the light absorption capacity of the calcium molybdate can be effectively improved, the separation and transfer of photogenerated electrons are accelerated, the recombination of photogenerated electrons and holes is inhibited, and the hydrogen production efficiency by photolysis of water is further improved.
In view of this, the present invention has been made.
Disclosure of Invention
In order to improve the photocatalytic hydrogen production capability of calcium molybdate and solve the problems of narrow light absorption range, rapid photo-generated 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 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 water decomposition.
The invention aims to provide a preparation method of the cadmium selenide/calcium molybdate photocatalyst, which specifically comprises the following steps:
(1) Dissolving calcium chloride and ethylenediamine tetraacetic acid disodium salt in deionized water, fully stirring and dissolving, adding sodium molybdate, and continuously stirring for 10min to obtain a solution A;
(2) Ultrasonic treating the solution A for 50min to obtain the calcium molybdate;
(3) Cd (NO) was added to a three-necked flask 3 ) 2 ·4H 2 O and deionized water are stirred and dissolved uniformly, then a ligand is added as a stabilizer, and NaOH solution is slowly added dropwise to adjust the pH of the solution, so as to obtain solution B;
(4) Adding sodium selenide solution into the solution B, and heating and refluxing after the reaction is stable to prepare the cadmium selenide nanocrystalline solution;
(5) Adding the cadmium selenide nanocrystalline solution into the calcium molybdate, stirring uniformly, and heating and refluxing to obtain the cadmium selenide/calcium molybdate;
the steps (3) and (4) are all carried out under the 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, in the step (3), cd (NO 3 ) 2 The concentration of the solution is 0.0002-0.05 mol/L.
Preferably, the ligand in the step (3) is one of mercaptopropionic acid, mercaptoacetic acid, cysteine or glutathione, etc.
Preferably, in the step (4), the molar ratio of Cd, se and ligand is 1 (0.15-0.25): (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 at 100 ℃ for 2-8 hours.
Preferably, in the step (5), the mixed solution of the cadmium selenide nanocrystalline solution and the calcium molybdate is heated and refluxed for 4 hours at 100 ℃.
Another object of the invention is to provide the use of the above cadmium selenide/calcium molybdate in photocatalytic hydrogen production, in particular photocatalytic water splitting hydrogen production tests performed using a full glass automatic on-line trace gas analysis system (labsor-6A). Using Na 2 S·9H 2 O and Na 2 SO 3 The aqueous solution acts as a sacrificial agent. To the above aqueous solution 20mg of catalyst was added together with 1wt% K 2 PtCl 4 As 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 in the whole process to maintain the catalyst to be suspended and dispersed at a proper rotating speed, and a gas chromatograph (GC-2014) is used for measuring H 2 Yield.
Compared with the prior art, the preparation method of the cadmium selenide/calcium molybdate provided by the invention has the advantages of simplicity, low raw material price, convenience for mass 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 pure calcium molybdate, the photocatalytic 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 a CdSe/CaMoO as prepared in example 3 4 Scanning electron microscope photograph of the photocatalyst.
Fig. 2 is an X-ray diffraction pattern of the materials prepared in examples 1, 2 and 3.
FIG. 3 shows the photocatalytic hydrogen production of the materials prepared in examples 1, 3, 4 and 5.
Detailed Description
The invention is further described with reference to the following specific examples:
example 1
The present embodiment provides a CaMoO 4 The preparation method of (2) comprises the following steps:
(1) 1mmol CaCl 2 And 0.2mmol of disodium ethylenediamine tetraacetate are added into 40mL of aqueous solution, and after being fully stirred and dissolved, 1mmol of H is added 4 MoNa 2 O 6 Stirring for 10min to obtain solution A;
(2) Ultrasonic treating the solution A in an ultrasonic cleaner for 50min to obtain the white precipitate CaMoO 4 。
Example 2
The embodiment provides a preparation method of water phase cadmium selenide nanocrystals, which comprises the following steps:
(1) 200mL of 0.001M Cd (NO) was placed in a three-necked flask 3 ) 2 The solution is kept stirring, 42.18 mu L of 3-mercaptopropionic acid is added as a stabilizer, 1M NaOH solution is slowly added dropwise to adjust the pH to 10.00, and solution A is obtained;
(2) Rapidly injecting 0.06mL of sodium selenide solution with the concentration of 0.6667M into the solution A by using an injector, and refluxing for 2 hours at 100 ℃ after the reaction is stable to prepare the cadmium selenide nanocrystalline solution;
the steps (1) and (2) are carried out under the atmosphere of nitrogen.
Example 3
The embodiment provides a preparation method of cadmium selenide/calcium molybdate, which comprises the following steps:
(1) 1mmol CaCl 2 And 0.2mmol of disodium ethylenediamine tetraacetate are added into 40mL of water solution, and are fully stirred and dissolvedAfter that, 1mmol H was added 4 MoNa 2 O 6 Stirring for 10min to obtain solution A;
(2) Ultrasonic treating the solution A in an ultrasonic cleaner for 50min to obtain the white precipitate CaMoO 4 。
(3) 200mL of 0.001M Cd (NO) was placed in a three-necked flask 3 ) 2 The solution is kept stirring, 42.18 mu L of 3-mercaptopropionic acid is added as a stabilizer, 1M NaOH solution is slowly added dropwise to adjust the pH to 10.00, and solution A is obtained;
(4) Rapidly injecting 0.06mL of sodium selenide solution with the concentration of 0.6667M into the solution A by using an injector, and refluxing for 2 hours at 100 ℃ after the reaction is stable to prepare the cadmium selenide nanocrystalline solution;
the steps (3) and (4) are all carried out under the nitrogen atmosphere.
(5) 100mg of CaMoO was added to a one-necked flask 4 The powder and 50mL of the cadmium selenide nanocrystalline solution are stirred uniformly, and heated and refluxed for 4 hours at 100 ℃ to obtain the cadmium selenide/calcium molybdate.
The photocatalytic hydrogen production performance was tested using the product obtained in example 3 as a photocatalyst. The specific method comprises the following steps: 100mL of deionized water, 0.035mol of Na, was charged into a photochemical reactor 2 S·9H 2 O and 0.025mol Na 2 SO 3 . To the above aqueous solution 20mg of catalyst was added together with 1wt% K 2 PtCl 4 As 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 in the whole process to maintain the catalyst to be suspended and dispersed at a proper rotating speed, and a gas chromatograph (GC-2014) is used for measuring H 2 Yield.
Example 4
The embodiment provides a preparation method of cadmium selenide/calcium molybdate, which comprises the following steps:
(1) 1mmol CaCl 2 And 0.2mmol of disodium ethylenediamine tetraacetate are added into 40mL of aqueous solution, and after being fully stirred and dissolved, 1mmol of H is added 4 MoNa 2 O 6 Stirring for 10min to obtain solution A;
(2) Ultrasonic treating the solution A in an ultrasonic cleaner for 50min to obtain the white precipitate CaMoO 4 。
(3) 200mL of 0.002M Cd (NO) was added to a three-necked flask 3 ) 2 The solution is kept stirring, 84.36 mu L of 3-mercaptopropionic acid is added as a stabilizer, 1M NaOH solution is slowly added dropwise to adjust the pH to 10.00, and solution A is obtained;
(4) Rapidly injecting 0.12mL of sodium selenide solution with the concentration of 0.6667M into the solution A by using an injector, and refluxing for 2 hours at 100 ℃ after the reaction is stable to prepare the cadmium selenide nanocrystalline solution;
the steps (3) and (4) are all carried out under the nitrogen atmosphere.
(5) 100mg of CaMoO was added to a one-necked flask 4 The powder and 50mL of the cadmium selenide nanocrystalline solution are stirred uniformly, and heated and refluxed for 4 hours at 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) 1mmol CaCl 2 And 0.2mmol of disodium ethylenediamine tetraacetate are added into 40mL of aqueous solution, and after being fully stirred and dissolved, 1mmol of H is added 4 MoNa 2 O 6 Stirring for 10min to obtain solution A;
(2) Ultrasonic treating the solution A in an ultrasonic cleaner for 50min to obtain the white precipitate CaMoO 4 。
(3) 200mL of 0.0005M Cd (NO) was placed in a three-necked flask 3 ) 2 The solution is kept stirring, 21.09 mu L of 3-mercaptopropionic acid is added as a stabilizer, 1M NaOH solution is slowly added dropwise to adjust the pH to 10.00, and solution A is obtained;
(4) Rapidly injecting 0.03mL of sodium selenide solution with the concentration of 0.6667M into the solution A by using an injector, and refluxing for 2 hours at 100 ℃ after the reaction is stable to prepare the cadmium selenide nanocrystalline solution;
the steps (3) and (4) are all carried out under the nitrogen atmosphere.
(5) 100mg of CaMoO was added to a one-necked flask 4 Powder and 50mL of the cadmium selenideThe nanocrystalline solution is stirred uniformly and heated and reflowed 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) 1mmol CaCl 2 And 0.3mmol of disodium ethylenediamine tetraacetate are added into 40mL of aqueous solution, and after being fully stirred and dissolved, 1mmol of H is added 4 MoNa 2 O 6 Stirring for 10min to obtain solution A;
(2) Ultrasonic treating the solution A in an ultrasonic cleaner for 50min to obtain the white precipitate CaMoO 4 。
(3) 200mL of 0.001M Cd (NO) was placed in a three-necked flask 3 ) 2 The solution is kept stirring, 52.73 mu L of 3-mercaptopropionic acid is added as a stabilizer, 1M NaOH solution is slowly added dropwise to adjust the pH to 10.00, and solution A is obtained;
(4) Rapidly injecting 0.06mL of sodium selenide solution with the concentration of 0.6667M into the solution A by using an injector, and refluxing for 2 hours at 100 ℃ after the reaction is stable to prepare the cadmium selenide nanocrystalline solution;
the steps (3) and (4) are all carried out under the nitrogen atmosphere.
(5) 100mg of CaMoO was added to a one-necked flask 4 The powder and 50mL of the cadmium selenide nanocrystalline solution are stirred uniformly, and heated and refluxed for 4 hours at 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 invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention are still included in the protection scope of the technical solution of the present invention.
Claims (7)
1. The cadmium selenide/calcium molybdate composite photocatalyst for photocatalytic hydrogen production is characterized in that calcium molybdate is synthesized by an ultrasonic precipitation method, cadmium selenide nanocrystals are modified on the surface of the calcium molybdate to obtain the cadmium selenide/calcium molybdate, and the preparation method of the cadmium selenide/calcium molybdate composite photocatalyst comprises the following steps:
(1) Dissolving calcium chloride and ethylenediamine tetraacetic acid disodium salt in deionized water, fully stirring and dissolving, adding sodium molybdate, and continuously stirring for 10min to obtain a solution A;
(2) Ultrasonic treating the solution A for 50min to obtain calcium molybdate;
(3) Cd (NO) was added to a three-necked flask 3 ) 2 ·4H 2 O and deionized water are stirred and dissolved uniformly, then a ligand which is one of mercaptopropionic acid, thioglycollic acid, cysteine or glutathione is added as a stabilizer, and NaOH solution is slowly added dropwise to adjust the pH of the solution, so that a solution B is obtained;
(4) Adding sodium selenide solution into the solution B, and heating and refluxing after the reaction is stable to prepare cadmium selenide nanocrystalline solution;
(5) Adding the cadmium selenide nanocrystalline solution into the calcium molybdate, stirring uniformly, and heating and refluxing to obtain the cadmium selenide/calcium molybdate;
the steps (3) and (4) are all carried out under the nitrogen atmosphere.
2. The method for preparing the cadmium selenide/calcium molybdate composite photocatalyst for photocatalytic hydrogen production according to claim 1, comprising the steps of:
(1) Dissolving calcium chloride and ethylenediamine tetraacetic acid disodium salt in deionized water, fully stirring and dissolving, adding sodium molybdate, and continuously stirring for 10min to obtain a solution A;
(2) Ultrasonic treating the solution A for 50min to obtain calcium molybdate;
(3) Cd (NO) was added to a three-necked flask 3 ) 2 ·4H 2 O and deionized water are stirred and dissolved uniformly, then a ligand which is one of mercaptopropionic acid, thioglycollic acid, cysteine or glutathione is added as a stabilizer, and NaOH solution is slowly added dropwise to adjust the pH of the solution, so that a solution B is obtained;
(4) Adding sodium selenide solution into the solution B, and heating and refluxing after the reaction is stable to prepare cadmium selenide nanocrystalline solution;
(5) Adding the cadmium selenide nanocrystalline solution into the calcium molybdate, stirring uniformly, and heating and refluxing to obtain the cadmium selenide/calcium molybdate;
the steps (3) and (4) are all carried out under the nitrogen atmosphere.
3. The method according to claim 2, wherein the molar ratio of sodium molybdate, calcium chloride and disodium ethylenediamine tetraacetate in the step (1) is 1:1 (0.1-0.3).
4. The method according to claim 2, wherein the step (3) is performed by using Cd (NO 3 ) 2 The concentration of the solution is 0.0002-0.05 mol/L.
5. The method according to claim 2, wherein in the step (3), the pH is adjusted to 9.00 to 11.00 with a 1M NaOH solution; in the step (4), the molar ratio of Cd, se and ligand is 1 (0.15-0.25): 2.0-3.0, and heating reflux is carried out at 100 ℃ for 2-8h.
6. The method of claim 2, wherein in the step (5), the mixed solution of the cadmium selenide nanocrystalline solution and the calcium molybdate is heated to reflux 4h at 100 ℃.
7. Use of the cadmium selenide/calcium molybdate composite photocatalyst according to claim 1 in photocatalytic hydrogen production.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210333188.6A CN114632528B (en) | 2022-03-30 | 2022-03-30 | Cadmium selenide/calcium molybdate photocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210333188.6A CN114632528B (en) | 2022-03-30 | 2022-03-30 | Cadmium selenide/calcium molybdate photocatalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114632528A CN114632528A (en) | 2022-06-17 |
| CN114632528B true CN114632528B (en) | 2023-07-25 |
Family
ID=81951950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210333188.6A Active CN114632528B (en) | 2022-03-30 | 2022-03-30 | Cadmium selenide/calcium molybdate photocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114632528B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103623803A (en) * | 2012-08-30 | 2014-03-12 | 上海纳晶科技有限公司 | Visible light photocatalyst and preparation method therefor |
| CN106542579A (en) * | 2015-09-17 | 2017-03-29 | 天津工业大学 | A kind of preparation method of flower ball-shaped calcium molybdate |
| CN107519898A (en) * | 2016-06-22 | 2017-12-29 | 张家港市金港镇宏业海绵复合厂 | The preparation method of cadmium selenide-bismuth tungstate composite photocatalyst |
| CN111939944A (en) * | 2020-07-28 | 2020-11-17 | 西北师范大学 | Preparation and application of cadmium selenide quantum dot/molybdenum disulfide composite photocatalyst |
| CN113134371A (en) * | 2021-04-20 | 2021-07-20 | 青岛科技大学 | Cadmium indium selenide/zinc copper sulfide nano composite material and preparation method and application thereof |
-
2022
- 2022-03-30 CN CN202210333188.6A patent/CN114632528B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103623803A (en) * | 2012-08-30 | 2014-03-12 | 上海纳晶科技有限公司 | Visible light photocatalyst and preparation method therefor |
| CN106542579A (en) * | 2015-09-17 | 2017-03-29 | 天津工业大学 | A kind of preparation method of flower ball-shaped calcium molybdate |
| CN107519898A (en) * | 2016-06-22 | 2017-12-29 | 张家港市金港镇宏业海绵复合厂 | The preparation method of cadmium selenide-bismuth tungstate composite photocatalyst |
| CN111939944A (en) * | 2020-07-28 | 2020-11-17 | 西北师范大学 | Preparation and application of cadmium selenide quantum dot/molybdenum disulfide composite photocatalyst |
| CN113134371A (en) * | 2021-04-20 | 2021-07-20 | 青岛科技大学 | Cadmium indium selenide/zinc copper sulfide nano composite material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| A Z-scheme Bi2MoO6/CdSe-diethylenetriamine heterojunction for enhancing photocatalytic hydrogen production activity under visible light;Feifei Mei et al.;《Dalton Transactions》;第48卷;1067-1074 * |
| Fabrication of CdSe/CaTiO3 nanocomposties in aqueous solution for improved photocatalytic hydrogen production;Jishu Han et al.;《Applied Surface Science》;第459卷;520-526 * |
| Synthesis of AMoO4 (A = Ca, Sr, Ba) photocatalysts and their potential application for hydrogen evolution and the degradation of tetracycline in water;Ali M. Huerta-Flores et al.;《Journal of Photochemistry and Photobiology A: Chemistry》;第356卷;29-37 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114632528A (en) | 2022-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jin et al. | Ni, Co-based selenide anchored g-C3N4 for boosting photocatalytic hydrogen evolution | |
| CN113134371B (en) | Cadmium indium selenide/zinc copper sulfide nano composite material and preparation method and application thereof | |
| CN109806888B (en) | 1T-MoS2Modified ZnCoS solid solution hollow dodecahedron nanocomposite and preparation method and application thereof | |
| CN110385146B (en) | Ni0.85Se/PDA/g-C3N4Composite photocatalyst and application thereof | |
| CN109201102A (en) | A kind of Z-type hetero-junctions M-C3N4The preparation method of/CdS composite photo-catalyst | |
| CN110075875A (en) | It is a kind of using NiSe as efficient heterojunction photocatalyst of auxiliary agent and its preparation method and application | |
| CN113145138B (en) | Thermal response type composite photocatalyst and preparation method and application thereof | |
| CN108404960A (en) | A kind of preparation method of sulfur-indium-zinc gold carbonitride two-dimensional layer composite photo-catalyst | |
| CN105885847B (en) | A kind of cadmium sulfoselenide solid solution quantum dot and preparation method thereof and Photocatalyzed Hydrogen Production application | |
| CN110980795A (en) | Hydrothermal method for preparing Cu2-xMethod for preparing S nanoflower and application of S nanoflower to near-infrared photothermal material | |
| CN110813335A (en) | Preparation method of nickel phosphide cocatalyst by performing photo-deposition on cadmium sulfide | |
| CN113198493A (en) | Nanometer flower-like zinc cadmium sulfide solid solution photocatalyst and preparation method thereof | |
| CN109453818B (en) | Cadmium sulfur selenium/diethylenetriamine/diamine organic-inorganic hybrid high-efficiency hydrogen production material and preparation method thereof | |
| CN110026207B (en) | CaTiO3@ZnIn2S4Nano composite material and preparation method and application thereof | |
| CN114632528B (en) | Cadmium selenide/calcium molybdate photocatalyst and preparation method and application thereof | |
| CN108311163A (en) | A kind of bismuth oxybromide composite photo-catalyst and preparation method thereof for hydrogen manufacturing | |
| CN111632612B (en) | Indium phosphide-indium oxide p-n junction porous microsphere composite material and preparation method and application thereof | |
| CN109926070B (en) | Mn (manganese)0.5Cd0.5S/WO3Preparation method of Au supported photocatalyst | |
| CN109092330B (en) | CdSQDs@CdIn2S4/CdWO4Preparation of the Material | |
| CN103586051B (en) | Composite metal sulfide photocatalyst, and preparation method and application thereof | |
| CN113289645B (en) | One-dimensional self-assembly composite photocatalyst and preparation method and application thereof | |
| CN116726949A (en) | Cd (cadmium sulfide) 0.5 Zn 0.5 S preparation method and experimental method for fixing nitrogen under photocatalysis | |
| CN112978795B (en) | BaZrS3Preparation method and application of nanocrystalline | |
| CN107540012B (en) | A kind of green simple synthesis of cadmiumsulfide quantum dot | |
| CN114832835B (en) | Z-type heterojunction NiS/Co 3 S 4 ZnCdS nano material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |