CN115301257A - Manganese zinc selenide/molybdenum copper sulfide hollow cube, and preparation method and application thereof - Google Patents
Manganese zinc selenide/molybdenum copper sulfide hollow cube, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115301257A CN115301257A CN202210942709.8A CN202210942709A CN115301257A CN 115301257 A CN115301257 A CN 115301257A CN 202210942709 A CN202210942709 A CN 202210942709A CN 115301257 A CN115301257 A CN 115301257A
- Authority
- CN
- China
- Prior art keywords
- copper sulfide
- zinc selenide
- manganese zinc
- hollow cube
- molybdenum copper
- 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.)
- Withdrawn
Links
- VWHRUUYKIVGMSI-UHFFFAOYSA-N zinc manganese(2+) selenium(2-) Chemical compound [Se-2].[Mn+2].[Zn+2].[Se-2] VWHRUUYKIVGMSI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 40
- 239000011733 molybdenum Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 24
- OIGPMFVSGDDYHS-UHFFFAOYSA-N copper sulfanylidenemolybdenum Chemical compound [S].[Cu].[Mo] OIGPMFVSGDDYHS-UHFFFAOYSA-N 0.000 claims abstract description 23
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 22
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 12
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 12
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 12
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 12
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000002159 nanocrystal Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 26
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- RBRLCUAPGJEAOP-UHFFFAOYSA-M sodium selanide Chemical compound [Na+].[SeH-] RBRLCUAPGJEAOP-UHFFFAOYSA-M 0.000 claims description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 9
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000007146 photocatalysis Methods 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
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a manganese zinc selenide/molybdenum copper sulfide hollow cube, which comprises the following steps: (1) Dropwise adding sodium hydroxide and ascorbic acid into the copper chloride solution at 55 ℃ respectively, and standing to obtain cuprous oxide cubes; (2) Sequentially adding the cuprous oxide cube, polyvinylpyrrolidone, sodium molybdate and thioacetamide into ethylene glycol, and transferring the mixture into a reaction kettle to react for 24 hours at 200 ℃ to obtain a molybdenum copper sulfide hollow cube; (3) And compounding the molybdenum copper sulfide hollow cube with a manganese zinc selenide nanocrystal to obtain the manganese zinc selenide/molybdenum copper sulfide hollow cube. The invention also provides a manganese zinc selenide/molybdenum copper sulfide hollow cube prepared by the method, and the manganese zinc selenide/molybdenum copper sulfide hollow cube can obviously improve light by taking the manganese zinc selenide/molybdenum copper sulfide hollow cube as a photocatalystCatalytic hydrogen production amount. The photocatalytic hydrogen production amount in 4 hours can reach 13.26 mmol/g ‑1 And the material can keep good circulation stability in the process of photocatalytic hydrogen production.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a manganese zinc selenide/molybdenum copper sulfide hollow cube, a preparation method and application thereof.
Background
Due to the shortage of fossil energy and the increasing problem of environmental pollution, various renewable new energy sources are gradually explored and developed. Hydrogen energy is considered as an effective alternative to traditional fossil energy sources due to its advantages of high combustion energy, no environmental pollution and being renewable. Among many hydrogen production methods, photocatalytic water splitting hydrogen production is a convenient, low-consumption and pollution-free technical method, and is one of important means for solving the problems of environment and resources. Therefore, designing and developing high-efficiency photocatalysts become a research hotspot at present.
Among a plurality of nano materials with photocatalytic performance, the photocatalyst material based on a hollow structure has the advantages of high specific surface area, low density, fast charge transmission and the like, and is continuously researched and improved. At present, when a single-component hollow structure photocatalyst is used, the problems of low separation efficiency of photo-generated electrons, high electron-hole recombination rate and the like occur, and the photocatalytic activity is reduced.
The II-VI group nanocrystalline is used as a narrow-bandgap semiconductor material, has proper forbidden band width, has stronger absorption characteristic in a visible light region, has low toxicity, low preparation raw material cost and rich sources, and becomes a novel photocatalyst material. Therefore, the heterojunction structure is constructed by selecting the appropriate nanocrystalline material and the hollow structure photocatalyst, the visible light absorption efficiency of the heterojunction structure is effectively improved, the migration rate of carriers is accelerated, the recombination rate of photo-generated electrons and holes is reduced, and the hydrogen production efficiency of the composite material photocatalytic water is greatly improved finally.
In view of this, the invention is particularly proposed.
Disclosure of Invention
In order to solve the problem of poor photocatalytic performance of the photocatalyst in the prior art, the invention provides a manganese zinc selenide/molybdenum copper sulfide hollow cubic composite material obtained by using a molybdenum copper sulfide hollow cube as a substrate and coating a manganese zinc selenide nanocrystal on the outer layer, and also provides a preparation method of the manganese zinc selenide/molybdenum copper sulfide hollow cube and application of the manganese zinc selenide/molybdenum copper sulfide hollow cube in photocatalytic hydrogen production.
The invention aims to provide a preparation method of the manganese zinc selenide/molybdenum copper sulfide hollow cube, which comprises the following steps:
(1) Dissolving copper chloride dihydrate in 100mL of deionized water, heating to 55 ℃, stirring for 30 minutes, and slowly dropwise adding sodium hydroxide into the copper chloride solution to obtain brown suspension;
(2) Continuously stirring the brown suspension in the step (1) for 30 minutes at 55 ℃, slowly dropwise adding ascorbic acid, standing for 3 hours at 55 ℃, centrifuging, washing with deionized water, washing with ethanol, and drying to obtain the cuprous oxide cube;
(3) Sequentially adding the cuprous oxide cube, polyvinylpyrrolidone, sodium molybdate and thioacetamide in the step (2) into 60mL of ethylene glycol, uniformly stirring, transferring into a reaction kettle, reacting at 200 ℃ for 24 hours, centrifuging, washing and drying to obtain the molybdenum-copper sulfide hollow cube;
(4) Sequentially adding zinc nitrate hexahydrate and manganese chloride tetrahydrate into 200mL of deionized water, adding a ligand in a nitrogen atmosphere, fully stirring, and adjusting the pH value with a NaOH solution to obtain a solution A;
(5) Adding sodium hydroselenide into the solution A under the nitrogen atmosphere, fully stirring, and heating and refluxing at 100 ℃ to obtain the manganese zinc selenide nanocrystalline solution;
(6) And mixing the manganese zinc selenide nanocrystalline solution with the molybdenum copper sulfide, and heating and refluxing at 100 ℃ to obtain the manganese zinc selenide/molybdenum copper sulfide hollow cube.
Preferably, in the step (1), the concentration of the copper chloride solution is 0.01mol/L.
Preferably, in the step (1), the amount of sodium hydroxide used is 0.015 to 0.025mol.
Preferably, in the step (2), the dosage of the ascorbic acid is 4.8 to 7.2mmol.
Preferably, in the step (3), the mass ratio of the cuprous oxide cubes, the polyvinylpyrrolidone, the sodium molybdate and the thioacetamide is 1 (10-15) to 1.5 (2-4).
In a preferred embodiment of the method of the invention,in the step (4), the concentration of zinc nitrate is 0.001-0.1 mol/L, and Zn 2+ 、Mn 2+ The molar ratio of the ligand is 1 (0.01-0.1) to 2.
Preferably, in the step (5), the amount of the sodium hydroselenide is 0.04-4 mmol, and the reflux time is 8 hours.
Preferably, in the step (6), the manganese zinc selenide nanocrystalline solution and the molybdenum copper sulfide are mixed and then heated and refluxed for 3 hours.
The invention also aims to provide the application of the manganese zinc selenide/molybdenum copper sulfide hollow cube in photocatalytic water hydrogen production. The photocatalytic water hydrogen production test is carried out in an all-glass automatic on-line trace gas analysis system (Labsolar-6A), a hollow cube of manganese zinc selenide/molybdenum copper sulfide is used as a photocatalyst, and anhydrous Na 2 SO 3 And Na 2 S·9H 2 O as a sacrificial agent, a 300W xenon lamp (MICROCOLAR 300) was used as a light source, and the hydrogen content was measured by an on-line gas chromatography (GC-7806).
Compared with the prior art, the preparation method of the manganese zinc selenide/molybdenum copper sulfide hollow cube provided by the invention has the advantages that the raw materials are low in toxicity, low in cost and rich in sources, meanwhile, the preparation process is green and pollution-free, the reaction conditions are mild, the operation is simple, and low-cost large-scale production is expected. In addition, the manganese zinc selenide/molybdenum copper sulfide hollow cube prepared by the invention is used as a photocatalyst, and the photocatalytic hydrogen production amount in 4 hours can reach 13.26 mmol/g -1 And shows higher photocatalytic hydrogen production activity. And the material can keep good circulation stability in the process of photocatalytic hydrogen production.
Detailed Description
The invention will be further described with reference to specific examples:
example 1
The embodiment provides a preparation method of a molybdenum-copper sulfide hollow cube, which comprises the following steps:
(1) Dissolving 0.17g of copper chloride dihydrate in 100mL of deionized water, heating to 55 ℃, stirring for 30 minutes, and slowly dropwise adding 10mL of 2mol/L sodium hydroxide into the copper chloride solution to obtain a brown suspension;
(2) Continuously stirring the brown suspension obtained in the step (1) at 55 ℃ for 30 minutes, slowly dropwise adding 10mL of ascorbic acid with the concentration of 0.6mol/L, standing at 55 ℃ for 3 hours, and performing centrifugation, deionized water washing, ethanol washing and drying to obtain the cuprous oxide cube;
(3) And (3) sequentially adding 80mg of the cuprous oxide cube in the step (2), 1g of polyvinylpyrrolidone, 120mg of sodium molybdate and 240mg of thioacetamide into 60mL of ethylene glycol, uniformly stirring, transferring into a reaction kettle, reacting for 24 hours at 200 ℃, centrifuging, washing and drying to obtain the molybdenum copper sulfide hollow cube.
Example 2
The embodiment provides a preparation method of a manganese zinc selenide nanocrystal, which comprises the following steps:
(1) Sequentially adding 1.9mmol of zinc nitrate hexahydrate and 0.1mmol of manganese chloride tetrahydrate into 200mL of deionized water, adding 352.1 mu L of 3-mercaptopropionic acid under the nitrogen atmosphere, fully stirring, and adjusting the pH to 10.50 by using a 1M NaOH solution to obtain a solution A;
(2) And (3) rapidly adding 0.4mmol of sodium hydroselenide into the solution A in the nitrogen atmosphere, fully stirring, and heating and refluxing for 8 hours at 100 ℃ to obtain the manganese zinc selenide nanocrystalline solution.
Example 3
The embodiment provides a preparation method of a manganese zinc selenide/molybdenum copper sulfide hollow cube, which comprises the following steps:
(1) Dissolving 0.17g of copper chloride dihydrate in 100mL of deionized water, heating to 55 ℃, stirring for 30 minutes, and slowly dropwise adding 10mL of 2mol/L sodium hydroxide into the copper chloride solution to obtain a brown suspension;
(2) Continuously stirring the brown suspension obtained in the step (1) at 55 ℃ for 30 minutes, slowly dropwise adding 10mL of ascorbic acid with the concentration of 0.6mol/L, standing at 55 ℃ for 3 hours, and performing centrifugation, deionized water washing, ethanol washing and drying to obtain the cuprous oxide cube;
(3) And (3) sequentially adding 80mg of the cuprous oxide cube in the step (2), 1g of polyvinylpyrrolidone, 120mg of sodium molybdate and 240mg of thioacetamide into 60mL of ethylene glycol, uniformly stirring, transferring into a reaction kettle, reacting for 24 hours at 200 ℃, centrifuging, washing and drying to obtain the molybdenum copper sulfide hollow cube.
(4) Sequentially adding 1.9mmol of zinc nitrate hexahydrate and 0.1mmol of manganese chloride tetrahydrate into 200mL of deionized water, adding 352.1 mu L of 3-mercaptopropionic acid under the nitrogen atmosphere, fully stirring, and adjusting the pH to 10.50 by using a 1M NaOH solution to obtain a solution A;
(5) And (3) rapidly adding 0.4mmol of sodium hydroselenide into the solution A in the nitrogen atmosphere, fully stirring, and heating and refluxing for 8 hours at 100 ℃ to obtain the manganese zinc selenide nanocrystalline solution.
(6) And mixing 100mL of the manganese zinc selenide nanocrystalline solution and 50mg of the molybdenum copper sulfide hollow cube powder, fully stirring, and heating and refluxing for 3 hours at 100 ℃ to obtain the manganese zinc selenide/molybdenum copper sulfide hollow cube.
Example 4
The embodiment provides a preparation method of a manganese zinc selenide/molybdenum copper sulfide hollow cube, which comprises the following steps:
(1) Dissolving 0.17g of copper chloride dihydrate in 100mL of deionized water, heating to 55 ℃, stirring for 30 minutes, and slowly dropwise adding 10mL of 2mol/L sodium hydroxide into the copper chloride solution to obtain a brown suspension;
(2) Continuously stirring the brown suspension obtained in the step (1) at 55 ℃ for 30 minutes, slowly dropwise adding 12mL of ascorbic acid with the concentration of 0.6mol/L, standing at 55 ℃ for 3 hours, and performing centrifugation, deionized water washing, ethanol washing and drying to obtain the cuprous oxide cube;
(3) And (3) sequentially adding 80mg of the cuprous oxide cube in the step (2), 1g of polyvinylpyrrolidone, 120mg of sodium molybdate and 240mg of thioacetamide into 60mL of ethylene glycol, uniformly stirring, transferring into a reaction kettle, reacting for 24 hours at 200 ℃, centrifuging, washing and drying to obtain the molybdenum copper sulfide hollow cube.
(4) Sequentially adding 1.9mmol of zinc nitrate hexahydrate and 0.1mmol of manganese chloride tetrahydrate into 200mL of deionized water, adding 352.1 mu L of 3-mercaptopropionic acid under the nitrogen atmosphere, fully stirring, and adjusting the pH to 10.50 by using a 1M NaOH solution to obtain a solution A;
(5) And (3) rapidly adding 0.4mmol of sodium hydroselenide into the solution A in the nitrogen atmosphere, fully stirring, and heating and refluxing for 8 hours at 100 ℃ to obtain the manganese zinc selenide nanocrystalline solution.
(6) And mixing 100mL of the manganese zinc selenide nanocrystalline solution and 50mg of the molybdenum copper sulfide hollow cube powder, fully stirring, and heating and refluxing for 3 hours at 100 ℃ to obtain the manganese zinc selenide/molybdenum copper sulfide hollow cube.
Example 5
The embodiment provides a preparation method of a manganese zinc selenide/molybdenum copper sulfide hollow cube, which comprises the following steps:
(1) Dissolving 0.17g of copper chloride dihydrate in 100mL of deionized water, heating to 55 ℃, stirring for 30 minutes, and slowly dropwise adding 10mL of 2mol/L sodium hydroxide into the copper chloride solution to obtain a brown suspension;
(2) Continuously stirring the brown suspension obtained in the step (1) at 55 ℃ for 30 minutes, slowly dropwise adding 10mL of ascorbic acid with the concentration of 0.6mol/L, standing at 55 ℃ for 3 hours, and performing centrifugation, deionized water washing, ethanol washing and drying to obtain the cuprous oxide cube;
(3) And (3) sequentially adding 80mg of the cuprous oxide cube in the step (2), 1.2g of polyvinylpyrrolidone, 120mg of sodium molybdate and 240mg of thioacetamide into 60mL of ethylene glycol, uniformly stirring, transferring into a reaction kettle, reacting for 24 hours at 200 ℃, centrifuging, washing and drying to obtain the molybdenum copper sulfide hollow cube.
(4) Sequentially adding 1.9mmol of zinc nitrate hexahydrate and 0.1mmol of manganese chloride tetrahydrate into 200mL of deionized water, adding 352.1 mu L of 3-mercaptopropionic acid under the nitrogen atmosphere, fully stirring, and adjusting the pH to 10.50 by using a 1M NaOH solution to obtain a solution A;
(5) And (3) rapidly adding 0.4mmol of sodium hydroselenide into the solution A in the nitrogen atmosphere, fully stirring, and heating and refluxing for 8 hours at 100 ℃ to obtain the manganese zinc selenide nanocrystalline solution.
(6) And mixing 100mL of the manganese zinc selenide nanocrystalline solution and 50mg of the molybdenum copper sulfide hollow cube powder, fully stirring, and heating and refluxing for 3 hours at 100 ℃ to obtain the manganese zinc selenide/molybdenum copper sulfide hollow cube.
Example 6
The embodiment provides a preparation method of a manganese zinc selenide/molybdenum copper sulfide hollow cube, which comprises the following steps:
(1) Dissolving 0.17g of copper chloride dihydrate in 100mL of deionized water, heating to 55 ℃, stirring for 30 minutes, and slowly dropwise adding 10mL of 2mol/L sodium hydroxide into the copper chloride solution to obtain a brown suspension;
(2) Continuously stirring the brown suspension obtained in the step (1) at 55 ℃ for 30 minutes, slowly dropwise adding 10mL of ascorbic acid with the concentration of 0.6mol/L, standing at 55 ℃ for 3 hours, and performing centrifugation, deionized water washing, ethanol washing and drying to obtain the cuprous oxide cube;
(3) And (3) sequentially adding 80mg of the cuprous oxide cube in the step (2), 1g of polyvinylpyrrolidone, 120mg of sodium molybdate and 280mg of thioacetamide into 60mL of ethylene glycol, uniformly stirring, transferring into a reaction kettle, reacting for 24 hours at 200 ℃, centrifuging, washing and drying to obtain the molybdenum copper sulfide hollow cube.
(4) Sequentially adding 1.9mmol of zinc nitrate hexahydrate and 0.1mmol of manganese chloride tetrahydrate into 200mL of deionized water, adding 352.1 mu L of 3-mercaptopropionic acid under the nitrogen atmosphere, fully stirring, and adjusting the pH to 10.50 by using a 1M NaOH solution to obtain a solution A;
(5) And (3) rapidly adding 0.4mmol of sodium hydroselenide into the solution A in the nitrogen atmosphere, fully stirring, and heating and refluxing for 8 hours at 100 ℃ to obtain the manganese zinc selenide nanocrystalline solution.
(6) And mixing 100mL of the manganese zinc selenide nanocrystalline solution and 50mg of the molybdenum copper sulfide hollow cube powder, fully stirring, and heating and refluxing for 3 hours at 100 ℃ to obtain the manganese zinc selenide/molybdenum copper sulfide hollow cube.
Example 7
The embodiment provides a preparation method of a manganese zinc selenide/molybdenum copper sulfide hollow cube, which comprises the following steps:
(1) Dissolving 0.17g of copper chloride dihydrate in 100mL of deionized water, heating to 55 ℃, stirring for 30 minutes, and slowly dropwise adding 10mL of 2mol/L sodium hydroxide into the copper chloride solution to obtain a brown suspension;
(2) Continuously stirring the brown suspension obtained in the step (1) at 55 ℃ for 30 minutes, slowly dropwise adding 10mL of ascorbic acid with the concentration of 0.6mol/L, standing at 55 ℃ for 3 hours, and performing centrifugation, deionized water washing, ethanol washing and drying to obtain the cuprous oxide cube;
(3) And (3) sequentially adding 80mg of the cuprous oxide cube in the step (2), 1g of polyvinylpyrrolidone, 120mg of sodium molybdate and 240mg of thioacetamide into 60mL of ethylene glycol, uniformly stirring, transferring into a reaction kettle, reacting for 24 hours at 200 ℃, centrifuging, washing and drying to obtain the molybdenum copper sulfide hollow cube.
(4) Sequentially adding 1.96mmol of zinc nitrate hexahydrate and 0.04mmol of manganese chloride tetrahydrate into 200mL of deionized water, adding 352.1 mu L of 3-mercaptopropionic acid under the nitrogen atmosphere, fully stirring, and adjusting the pH to 10.50 by using a 1M NaOH solution to obtain a solution A;
(5) And (3) rapidly adding 0.4mmol of sodium hydroselenide into the solution A in the nitrogen atmosphere, fully stirring, and heating and refluxing for 8 hours at 100 ℃ to obtain the manganese zinc selenide nanocrystalline solution.
(6) And mixing 100mL of the manganese zinc selenide nanocrystalline solution and 50mg of the molybdenum copper sulfide hollow cube powder, fully stirring, and heating and refluxing for 3 hours at 100 ℃ to obtain the manganese zinc selenide/molybdenum copper sulfide hollow cube.
Example 8
The embodiment provides a preparation method of a manganese zinc selenide/molybdenum copper sulfide hollow cube, which comprises the following steps:
(1) Dissolving 0.17g of copper chloride dihydrate in 100mL of deionized water, heating to 55 ℃, stirring for 30 minutes, and slowly dropwise adding 10mL of 2mol/L sodium hydroxide into the copper chloride solution to obtain a brown suspension;
(2) Continuously stirring the brown suspension obtained in the step (1) at 55 ℃ for 30 minutes, slowly dropwise adding 10mL of ascorbic acid with the concentration of 0.6mol/L, standing at 55 ℃ for 3 hours, and performing centrifugation, deionized water washing, ethanol washing and drying to obtain the cuprous oxide cube;
(3) And (3) sequentially adding 80mg of the cuprous oxide cube in the step (2), 1g of polyvinylpyrrolidone, 120mg of sodium molybdate and 240mg of thioacetamide into 60mL of ethylene glycol, uniformly stirring, transferring into a reaction kettle, reacting for 24 hours at 200 ℃, centrifuging, washing and drying to obtain the molybdenum copper sulfide hollow cube.
(4) Sequentially adding 1.9mmol of zinc nitrate hexahydrate and 0.1mmol of manganese chloride tetrahydrate into 200mL of deionized water, adding 352.1 mu L of 3-mercaptopropionic acid under the nitrogen atmosphere, fully stirring, and adjusting the pH to 10.50 by using a 1M NaOH solution to obtain a solution A;
(5) And (3) rapidly adding 0.4mmol of sodium hydroselenide into the solution A in the nitrogen atmosphere, fully stirring, and heating and refluxing for 8 hours at 100 ℃ to obtain the manganese zinc selenide nanocrystalline solution.
(6) And mixing 100mL of the manganese zinc selenide nanocrystalline solution and 25mg of the molybdenum copper sulfide hollow cube powder, fully stirring, and heating and refluxing for 3 hours at 100 ℃ to obtain the manganese zinc selenide/molybdenum copper sulfide hollow cube.
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 (9)
1. A preparation method of a manganese zinc selenide/molybdenum copper sulfide hollow cube is characterized by comprising the following steps:
(1) Dissolving copper chloride dihydrate in 100mL of deionized water, heating to 55 ℃, stirring for 30 minutes, and slowly dropwise adding sodium hydroxide into the copper chloride solution to obtain brown suspension;
(2) Continuously stirring the brown suspension in the step (1) for 30 minutes at 55 ℃, slowly dropwise adding ascorbic acid, standing for 3 hours at 55 ℃, centrifuging, washing with deionized water, washing with ethanol, and drying to obtain the cuprous oxide cube;
(3) Sequentially adding the cuprous oxide cube, polyvinylpyrrolidone, sodium molybdate and thioacetamide in the step (2) into 60mL of ethylene glycol, uniformly stirring, transferring into a reaction kettle, reacting at 200 ℃ for 24 hours, centrifuging, washing and drying to obtain the molybdenum-copper sulfide hollow cube;
(4) Sequentially adding zinc nitrate hexahydrate and manganese chloride tetrahydrate into 200mL of deionized water, adding a ligand in a nitrogen atmosphere, fully stirring, and adjusting the pH value with a NaOH solution to obtain a solution A;
(5) Adding sodium hydroselenide into the solution A in the nitrogen atmosphere, fully stirring, and heating and refluxing at 100 ℃ to obtain the manganese zinc selenide nanocrystalline solution;
(6) And mixing the manganese zinc selenide nanocrystalline solution with the molybdenum copper sulfide, and heating and refluxing at 100 ℃ to obtain the manganese zinc selenide/molybdenum copper sulfide hollow cube.
2. The method for preparing a manganese zinc selenide/molybdenum copper sulfide hollow cube according to claim 1, wherein in the step (1), the concentration of the copper chloride solution is 0.01mol/L.
3. The method for preparing a manganese zinc selenide/molybdenum copper sulfide hollow cube according to claim 1, wherein in the step (1), the amount of sodium hydroxide is 0.015 to 0.025mol.
4. The method for preparing a manganese zinc selenide/molybdenum copper sulfide hollow cube according to claim 1, wherein in the step (2), the amount of the ascorbic acid is 4.8 to 7.2mmol.
5. The method for preparing the hollow cube of manganese zinc selenide/molybdenum copper sulfide as claimed in claim 1, wherein in the step (3), the mass ratio of cuprous oxide cube, polyvinylpyrrolidone, sodium molybdate and thioacetamide is 1 (10-15) to 1.5 (2-4).
6. The method for preparing a manganese zinc selenide/molybdenum copper sulfide hollow cube according to claim 1, wherein in the step (4), the concentration of zinc nitrate is 0.001-0.1 mol/L, zn 2+ 、Mn 2+ The molar ratio of the ligand is 1 (0.01-0.1) to 2.
7. The method for preparing a manganese zinc selenide/molybdenum copper sulfide hollow cube according to claim 1, wherein in the step (5), the amount of the sodium hydroselenide is 0.04-4 mmol, and the reflux time is 8 hours.
8. The method for preparing a manganese zinc selenide/molybdenum copper sulfide hollow cube according to claim 1, wherein in the step (6), the manganese zinc selenide nanocrystal solution and the molybdenum copper sulfide are mixed and then heated and refluxed for 3 hours.
9. The application of the manganese zinc selenide/molybdenum copper sulfide hollow cube in photocatalytic hydrogen production, wherein the manganese zinc selenide/molybdenum copper sulfide hollow cube is prepared by the preparation method of claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210942709.8A CN115301257A (en) | 2022-08-08 | 2022-08-08 | Manganese zinc selenide/molybdenum copper sulfide hollow cube, and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210942709.8A CN115301257A (en) | 2022-08-08 | 2022-08-08 | Manganese zinc selenide/molybdenum copper sulfide hollow cube, and preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115301257A true CN115301257A (en) | 2022-11-08 |
Family
ID=83861500
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210942709.8A Withdrawn CN115301257A (en) | 2022-08-08 | 2022-08-08 | Manganese zinc selenide/molybdenum copper sulfide hollow cube, and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115301257A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116651467A (en) * | 2023-06-02 | 2023-08-29 | 常州大学 | Hollow Cu 2-x S@ cadmium manganese sulfide composite photocatalyst and preparation method and application thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101468985B1 (en) * | 2013-07-12 | 2014-12-04 | 한양대학교 산학협력단 | Tunable emission wavelength of core/doped shell/shell quantum dots and method for preparing thereof |
CN104338547A (en) * | 2013-07-29 | 2015-02-11 | 中国科学院理化技术研究所 | Photocatalyst based on quantum dot/rod and molybdenum disulfide nanosheet, preparation method thereof, photocatalysis system and hydrogen production method by reforming biomass |
CN106830080A (en) * | 2016-12-13 | 2017-06-13 | 中国科学技术大学 | Cu2MoS4Nano material and preparation method thereof |
CN110327943A (en) * | 2019-07-16 | 2019-10-15 | 安徽师范大学 | A kind of Cu-Mo-S composite material and preparation method and application |
CN112838201A (en) * | 2021-04-06 | 2021-05-25 | 湖南镕锂新材料科技有限公司 | Cu2MoS4Composite negative electrode material, preparation method thereof and sodium ion battery |
CN114570395A (en) * | 2022-02-28 | 2022-06-03 | 青岛科技大学 | Hollow zinc copper selenide/zinc sulfide/zinc titanate nano composite material and preparation method and application thereof |
-
2022
- 2022-08-08 CN CN202210942709.8A patent/CN115301257A/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101468985B1 (en) * | 2013-07-12 | 2014-12-04 | 한양대학교 산학협력단 | Tunable emission wavelength of core/doped shell/shell quantum dots and method for preparing thereof |
CN104338547A (en) * | 2013-07-29 | 2015-02-11 | 中国科学院理化技术研究所 | Photocatalyst based on quantum dot/rod and molybdenum disulfide nanosheet, preparation method thereof, photocatalysis system and hydrogen production method by reforming biomass |
CN106830080A (en) * | 2016-12-13 | 2017-06-13 | 中国科学技术大学 | Cu2MoS4Nano material and preparation method thereof |
CN110327943A (en) * | 2019-07-16 | 2019-10-15 | 安徽师范大学 | A kind of Cu-Mo-S composite material and preparation method and application |
CN112838201A (en) * | 2021-04-06 | 2021-05-25 | 湖南镕锂新材料科技有限公司 | Cu2MoS4Composite negative electrode material, preparation method thereof and sodium ion battery |
CN114570395A (en) * | 2022-02-28 | 2022-06-03 | 青岛科技大学 | Hollow zinc copper selenide/zinc sulfide/zinc titanate nano composite material and preparation method and application thereof |
Non-Patent Citations (3)
Title |
---|
FENGYAN LI ET AL.: "Design and fabrication of hollow structured Cu2MoS4/ZnIn2S4 nanocubes with significant enhanced photocatalytic hydrogen evolution performance", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》, vol. 46, pages 37847 - 37859, XP086834397, DOI: 10.1016/j.ijhydene.2021.09.035 * |
SRIDEVI D.V ET AL.: "A facile synthesis of Mn-doped ZnSe nanoparticles for an enhanced photocatalytic activity and biological applications", 《CERAMICS INTERNATIONAL》, vol. 48, pages 29394 - 29402 * |
WEI WEI ET AL.: "Loading Rh single atoms onto hollow cubic Cu2MoS4 nanoparticles for decreased electron/hole recombination and increased photocatalytic performance", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 896, pages 162832 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116651467A (en) * | 2023-06-02 | 2023-08-29 | 常州大学 | Hollow Cu 2-x S@ cadmium manganese sulfide composite photocatalyst and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109589991B (en) | Zinc indium sulfide/copper indium sulfide two-dimensional heterojunction photocatalyst, and preparation method and application thereof | |
CN113134371B (en) | Cadmium indium selenide/zinc copper sulfide nano composite material and preparation method and application thereof | |
CN115301257A (en) | Manganese zinc selenide/molybdenum copper sulfide hollow cube, and preparation method and application thereof | |
CN110586135B (en) | Containing Mn0.5Cd0.5S and Cu2Preparation method of O-supported photocatalyst | |
CN109939744B (en) | Preparation method and application of ultrathin two-dimensional metal phthalocyanine/bismuth vanadate composite photocatalyst | |
CN113351226B (en) | Petal-shaped loaded ZnIn 2 S 4 Preparation method of bismuth oxide composite visible light catalytic material and product prepared by same | |
CN113600210A (en) | In-situ growth three-element composite photocatalyst and preparation method and application thereof | |
CN110586137B (en) | Containing Mn0.5Cd0.5Preparation method of S and Au supported photocatalyst | |
CN110743598B (en) | Porous carbon nitride/tin/stannous oxide photocatalytic material and preparation method thereof | |
CN112076742A (en) | Ternary heterojunction composite photocatalyst and preparation method and application thereof | |
CN114570395B (en) | Hollow zinc copper selenide/zinc sulfide/zinc titanate nanocomposite and preparation method and application thereof | |
CN115845925A (en) | Self-assembled SH-MOF composite hollow spherical C 3 N 4 Preparation method and application thereof in nitrogen fixation and ammonia synthesis | |
CN114984937B (en) | Spatially separated double-vacancy titanium dioxide homojunction catalyst and preparation method and application thereof | |
CN115475634A (en) | Preparation method of core-shell structure photocatalyst for reducing carbon dioxide emission in environment | |
CN113318758B (en) | Photocatalyst and preparation method and application thereof | |
CN114433132A (en) | Method for synthesizing Z-type heterojunction catalytic material by ultrasonic-assisted method | |
CN107626293A (en) | A kind of porous ZnO/TiO with photocatalysis hydrogen production function2The preparation method of hollow sub-microsphere | |
CN114887632B (en) | Cadmium indium selenide/zinc sulfide/iron-cobalt oxide photocatalyst and preparation method and application thereof | |
CN112808280A (en) | S-doped TiO2-CdS composite photocatalytic hydrogen production material and preparation method thereof | |
CN115007127B (en) | Preparation method of ternary composite photocatalytic material | |
CN114768871B (en) | PANI/NH 2 MIL-101 (Fe) composite material and preparation method and application thereof | |
CN114618534B (en) | Visible light responsive sulfur-doped bismuth telluride nanowire photocatalytic material and preparation method thereof | |
CN114950506B (en) | Ni (nickel) 2 P/ZnIn 2 S 4 Heterojunction photocatalyst preparation method and application thereof | |
CN109794270B (en) | V-shaped groove2O5Preparation method of/BiOI semiconductor composite photocatalyst | |
CN115025787B (en) | Preparation method and application of CdS nanoparticle-doped coated ZnO nanoflower powder |
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 | ||
WW01 | Invention patent application withdrawn after publication | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20221108 |