CN113477253A - Preparation method of hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nano-structure material - Google Patents
Preparation method of hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nano-structure material Download PDFInfo
- Publication number
- CN113477253A CN113477253A CN202110823751.3A CN202110823751A CN113477253A CN 113477253 A CN113477253 A CN 113477253A CN 202110823751 A CN202110823751 A CN 202110823751A CN 113477253 A CN113477253 A CN 113477253A
- Authority
- CN
- China
- Prior art keywords
- ethanol
- solution
- precipitate
- cobalt
- sulfur
- 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.)
- Granted
Links
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 236
- 239000002244 precipitate Substances 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 238000003756 stirring Methods 0.000 claims abstract description 55
- 239000000047 product Substances 0.000 claims abstract description 39
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 20
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 11
- -1 copper-cobalt-sulfur-iron oxide Chemical compound 0.000 claims abstract description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 235000019441 ethanol Nutrition 0.000 claims description 72
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 230000035484 reaction time Effects 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 19
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 12
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000000926 separation method Methods 0.000 abstract description 13
- 239000000969 carrier Substances 0.000 abstract description 11
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000002114 nanocomposite Substances 0.000 abstract description 3
- UATOFRZSCHRPBG-UHFFFAOYSA-N acetamide;hydrate Chemical compound O.CC(N)=O UATOFRZSCHRPBG-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229960003280 cupric chloride Drugs 0.000 abstract 1
- NHPHQYDQKATMFU-UHFFFAOYSA-N [Cu]=S.[Co] Chemical compound [Cu]=S.[Co] NHPHQYDQKATMFU-UHFFFAOYSA-N 0.000 description 15
- 239000004065 semiconductor Substances 0.000 description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 13
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical class [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a hollow copper-cobalt-sulfur-iron oxide composite three-dimensional nano-structure material, belongs to the field of nano-composite materials, and aims to solve the problems that the surface area expansion and heterojunction formation of the existing hollow rod-shaped structure cannot be realized simultaneously and cannot be separated out after use, and the preparation method comprises the following steps: taking ZIF-67 ethanol dispersion, adding ethanol and thioacetamide, stirring, transferring into a high-temperature reaction kettle, filtering a product, washing with absolute ethanol, and vacuum-drying the obtained clean precipitate to obtain a Co precursor; taking a product Co precursor, then taking ferric chloride, cupric chloride, water and thioacetamide, stirring into a solution, then transferring into a high-temperature reaction kettle, filtering, taking a precipitate, washing with ethanol, drying and grinding to obtain the product Co. The material is hollow and magnetic, has larger surface area, promotes the rapid separation of carriers, prolongs the service life of photocarriers, improves the photocatalysis performance, and can be separated after use.
Description
Technical Field
The invention discloses a preparation method of a hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nano-structured material, and belongs to the technical field of nano-composite materials.
Background
In recent years, sulfide nano materials have potential application values in the aspects of environmental protection, energy, national defense and the like due to special structures and excellent properties such as narrow band gaps, proper energy width positions and the like, and are photocatalysts with remarkable effects. The mechanism of photocatalysis is proposed according to the energy band structure of a semiconductor, the semiconductor consists of a valence band (VII) filled with electrons and an empty Conduction Band (CB), the highest energy level filled with electrons is called valence band top, the lowest empty energy level is called conduction band bottom, the energy level difference between the conduction band bottom and the valence band top is called energy band gap (Eg) of the semiconductor, the energy band gap determines the absorption range of the semiconductor to light, and the mechanism of photocatalysis of the semiconductor is divided into three main processes:
(1) generating photo-generated carriers by photo-excitation under illumination;
(2 migrate to the surface of the semiconductor material and the electrons and holes, which have not recombined, participate in the photocatalytic reaction.
(3) Electrons and holes on the surface of the semiconductor material may be captured by a capture agent or surface defects on the surface of the semiconductor, inhibit the recombination of the electron and the hole, and promote the redox reaction of the electrons and the holes on the surface of the semiconductor material.
In recent years, sulfide is considered to be a good photocatalyst because it has excellent properties such as a narrow band gap, a suitable energy width, and the like. For example, Ag2S exhibits good absorption of visible light due to its narrow band gap (0.92 eV). There are reports of Ag2S photocatalytic degradation of organic pollutants and catalytic cracking for preparing H2The nature of (c). Cobalt sulfides such as Co9S8、CoS、Co3S4The method is applied to capacitors,Dye solar cells and as catalysts, etc. Recently, CoS nanosheets as catalysts have been reported to be well-catalyzed to degrade the dye methylene blue. Semiconductor nanoplatelets of two-dimensional size, graphene or a wide variety of materials having graphene shape such as metal sulfide TiS2、VS2、MoS2MnO of metal oxide2、SnO2And the like draw great attention and interest due to the unique physicochemical properties thereof. Graphene oxide/Ag/TiO as reported in the literature2The compound shows good photocatalytic effect on the dye under visible light. Compared with the bulk material, the photocatalyst with the sheet structure has better photocatalytic performance, and the sheet structure is more favorable for forming a continuous electron flow system and promoting the separation and recombination of charges in a reaction system. The platelet structured catalyst also contributes to efficient absorption of visible light. With these advantages, the photocatalyst of a sheet structure is more potential and promising for large-scale application.
Metal sulfides (e.g. Co)3S4) The interest of the hydrolysis method is due to its unique electronic and optical properties. Due to the potential gradient of the heterojunction, the metal sulfide having a suitable energy band structure can accelerate the separation and migration of photoexcited carriers. Co3S4As a hollow structure material, the distance between a body and a surface can be shortened to accelerate the separation of photo-generated charges, and a large surface area and rich active sites can be provided to promote redox reaction. In addition, the hollow nanostructures may enhance light absorption by internal light scattering/reflection, and may facilitate reduced diffusion length of charge and enhanced exposure of catalytically active sites.
Research shows that the rapid separation and transfer of electrons and holes to the surface of a semiconductor are key steps for realizing photocatalytic reaction. The key to obtaining a high catalytic performance catalyst is therefore to optimize the charge separation process. Researchers have synthesized nanomaterials with a wide variety of structures to solve this problem. Of these, doping, the compounding together of two nanomaterials is considered to be a good approach. In a single nanometer semiconductor material, electrons are limited in a single nanometer material range, and the electrons and holes cannot be effectively separated, so that good catalytic performance cannot be shown.
The photocatalytic effect of the doped semiconductor metal oxide is greatly improved due to the large active surface area of the doped semiconductor metal oxide, for example, the doped semiconductor metal oxide such as Liu and the like adopts a simple hydrothermal method and an electrochemical replacement reaction to prepare Sn4+The doped cobalt sulfide nano material is modified on the surface of the glassy carbon electrode to construct the Sn-based nano material4+Doping with Co3S4The electrochemical sensor for detecting p-nitrophenol of GCE has good effect. When two kinds of nanometer materials with different band gaps are compounded, a certain energy level gradient can be formed on the surface of the nanometer materials, and the rapid separation of carriers can be promoted. Therefore, the service life of carriers excited by light is prolonged, the efficiency of charge separation is improved, and the photocatalytic activity is greatly improved. A Co as described in Chinese patent (CN 111729675A)3S4The @ ZnIn2S4 composite photocatalyst can be used for preparing hydrogen by photolyzing water. By optimizing hollow Co3S4In an amount of Co3S4And ZnIn2S4The hydrogen generation of the formed composite is higher than that of pure ZnIn2S4The nanosphere formed by the nanosheets is 5 times higher, so that the catalytic cost is not reduced, and the catalytic efficiency is improved; xu et al in oleylamine solution by thermal decomposition to obtain graphene-like Co3S4Carrying Ag2And (3) an S nano-composite. The synthesized compound has good photocatalytic effect on methylene blue and methyl orange under visible light and has good reusability.
Compared with the traditional single component, although the two nano materials with different band gaps are compounded, a certain energy level gradient can be formed on the surface of the nano materials, the carriers can be promoted to be rapidly separated, the service life of the photocarriers is prolonged, the heterostructure has higher photocatalysis performance, but cannot be separated out after reaction, and in addition, the problem that the surface area of the hollow rod-shaped structure cannot be enlarged any more if a heterojunction is formed exists.
Disclosure of Invention
The invention aims to: the method is used for manufacturing a magnetic structure which grows a flaky structure on the outer wall of a hollow rod-shaped structure and forms a heterojunction, and solves the problems that the surface area expansion and the heterojunction formation of the conventional hollow rod-shaped structure cannot be realized at the same time and cannot be separated after use.
The technical scheme adopted by the invention is as follows:
a preparation method of a hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nanostructure material comprises the following steps:
step 1, adding 0.01-100g of cobalt nitrate hexahydrate into 10-100ml of methanol and stirring to form a solution A; weighing 0.01-200g of 2-methylimidazole, adding into 10-100ml of methanol, and stirring to form a solution B; mixing the solution A and the solution B, stirring to form a uniform solution, standing, and washing with ethanol to obtain 10-60ml of ZIF-67 ethanol dispersion;
step 2, taking 1-10ml of ZIF-67 ethanol dispersion liquid obtained in the step 1, then taking 1-10ml of ethanol and 5-50mg of thioacetamide, adding the ethanol and the thioacetamide into the ZIF-67 ethanol dispersion liquid, fully stirring, then transferring the mixture into a high-temperature reaction kettle, centrifuging or filtering a product, washing the obtained precipitate with absolute ethanol, and carrying out vacuum drying on the obtained clean precipitate to obtain a product Co precursor;
and 3, taking the product Co precursor obtained in the step 2, then taking 0.01-1g of ferric chloride, 0.1-2mmol of copper chloride, 5-50ml of water and 5-80mg of thioacetamide, fully stirring to form a solution, then transferring the solution into a high-temperature reaction kettle, centrifuging or filtering the product after reaction, taking the precipitate, washing the precipitate with ethanol to obtain a clean precipitate, drying and grinding to obtain the hollow copper-cobalt-sulfur-iron oxide composite three-dimensional nano-structure material.
In the technical scheme, a methanol solution of cobalt nitrate hexahydrate and a methanol solution of 2-methylimidazole are mixed and stirred to form a uniform solution, the uniform solution is stood and washed by ethanol to obtain a ZIF-67 ethanol dispersion liquid, and unnecessary impurities are prevented from being introduced into the ZIF-67 due to drying when the uniform solution reacts with a reactant in the next step; the sulfur-doped ZIF is generated through the hydrothermal reaction of ZIF-67, thioacetamide and ethanol, and has a hollow rod-shaped structure and a large surface area; the product is hydrothermally reacted with ferric chloride, copper chloride, water and thioacetamide to generate copper cobalt sulfide wrapped by ferroferric oxide, namely, a plurality of sheet structures appear on an original hollow rod-shaped structure, and the sheet structures are favorable for forming a continuous electron flow system and promoting the separation and compounding of charges in the reaction system, and moreover, the structure of the final product has a larger surface area, rich pores and edges than the hollow rod-shaped structure, so that the light absorption can be enhanced through internal light scattering/reflection, sufficient space and exposed surfaces are provided for the deposition of electrochemical active substances, and the photocatalytic performance is greatly improved; copper cobalt sulfide and ferroferric oxide wrapped outside the copper cobalt sulfide form a heterojunction, and due to the potential gradient of the copper cobalt sulfide, the rapid separation of current carriers can be promoted, the service life of the photo-carriers is prolonged, and the photocatalytic performance is indirectly improved; the askew coated ferroferric oxide which is also a magnetic substance can attract the magnet, so that the structure can be effectively separated after photocatalysis.
In the present invention, by retaining hollow Co3S4On the basis of the structure, the copper, cobalt and sulfur and the iron oxide are combined into a three-dimensional structure, so that not only are rich pores and edges formed, but also the electrochemical active sites and the specific surface area are remarkably increased, and sufficient space and exposed surfaces are provided for the deposition of electrochemical active substances, and the remarkable photocatalytic property of the composite three-dimensional nano-structure material is realized; the prepared hollow copper-cobalt-sulfur-iron oxide composite three-dimensional nano-structure material is hollow and magnetic, has a larger surface area, promotes rapid separation of carriers, prolongs the service life of photocarriers, improves the photocatalytic performance, and can be separated after use.
Preferably, in the step 1, the solution A and the solution B are mixed and stirred for 1-30min and then are kept stand for 1-36 h.
More preferably, in step 1, the solution A and the solution B are mixed and stirred for 20min and then are kept stand for 24 h.
Preferably, in the step 2, the time period of the sufficient stirring is 5-60min, the temperature of the high-temperature reaction kettle is 150-210 ℃, the reaction time is 1-7h, the obtained precipitate is washed for 3-4 times by using absolute ethyl alcohol, and the clean precipitate is dried in a vacuum oven at the temperature of 20-100 ℃ for 1-24 h.
More preferably, in step 2, the time period of the full stirring is 30min, the temperature of the high-temperature reaction kettle is 200 ℃, the reaction time is 5h, the obtained precipitate is washed for 3 times by absolute ethyl alcohol, and the clean precipitate is dried for 12h in a vacuum oven at 60 ℃.
Preferably, in the step 3, the stirring time is 5-60min, the temperature of the high-temperature reaction kettle is 120-200 ℃, the reaction time is 1-7h, the mixture is washed by ethanol for 3-4 times, and the clean precipitate is dried in a vacuum oven at 20-100 ℃ for 1-24 h.
More preferably, in step 3, the stirring time is 30min, the temperature of the high-temperature reaction kettle is 180 ℃, the reaction time is 5h, the reaction kettle is washed by ethanol for 4 times, and the clean precipitate is dried in a vacuum oven at 60 ℃ for 12 h.
In the technical scheme of the application, ZIF-67 represents zeolite imidazolate framework-67.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the direct preparation of the ZIF-67 ethanol dispersion avoids the conventional method of drying in a constant temperature box to obtain the ZIF-67, and avoids the introduction of unnecessary impurities in the drying step;
2. the hollow structure is not reserved, a plurality of sheet structures grow on the hollow structure, and the sheet structures are favorable for forming a continuous electron flow system and promoting the separation and the combination of charges in a reaction system;
3. the structure of the final product has larger surface area, abundant pores and edges than that of a hollow rod-shaped structure, so that light absorption can be enhanced through internal light scattering/reflection, and sufficient space and exposed surface are provided for deposition of electrochemical active substances, so that the photocatalytic performance is greatly improved;
4. copper cobalt sulfide and ferroferric oxide wrapped outside the copper cobalt sulfide form a heterojunction, and due to the potential gradient of the copper cobalt sulfide, the rapid separation of current carriers can be promoted, the service life of the photo-carriers is prolonged, and the photocatalytic performance is indirectly improved;
5. the coated ferroferric oxide is a magnetic substance and can attract magnets, so that the structure can be effectively separated after photocatalysis.
Drawings
FIG. 1 is a scanning electron microscope photograph of a hollow copper cobalt sulfur @ iron oxide composite three-dimensional nanostructured material prepared in example 1 of the present invention;
fig. 2 is a photograph of a magnet adsorbed by the hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nanostructured material prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
As shown in fig. 1 and 2, a preparation method of a hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nanostructure material comprises the following steps:
step 1, adding 2g of cobalt nitrate hexahydrate into 65ml of methanol and stirring to form a solution A; weighing 2.5g of 2-methylimidazole, adding into 65ml of methanol and stirring to form a solution B; mixing the solution A and the solution B, stirring for 20min to form a uniform solution, standing for 24h, and washing with ethanol to obtain 20ml of ZIF-67 ethanol dispersion;
step 2, taking 10ml of ZIF-67 ethanol dispersion liquid obtained in the step 1, then taking 10ml of ethanol and 45mg of thioacetamide, adding the ethanol and 45mg of thioacetamide into the ZIF-67 ethanol dispersion liquid, fully stirring for 30min, then moving the mixture into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 200 ℃, the reaction time is 5 hours, centrifuging or filtering a product, washing the obtained precipitate for 3 times by using absolute ethanol, drying the obtained clean precipitate in a vacuum oven at 60 ℃ for 12 hours, and obtaining a product of sulfur-doped ZIF;
and 3, taking the sulfur-doped ZIF product obtained in the step 2, then taking 0.1g of ferric chloride, 1.3mmol of copper chloride, 15ml of water and 45mg of thioacetamide, fully stirring for 30min to form a solution, then transferring the solution into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 180 ℃, the reaction time is 5h, centrifuging or filtering the product after reaction, taking the precipitate, washing the precipitate with ethanol for 4 times to obtain a clean precipitate, drying the clean precipitate in a vacuum oven at 60 ℃ for 12h, and grinding to obtain the ferroferric oxide-coated copper cobalt sulfide, namely the hollow copper cobalt sulfur @ iron oxide composite three-dimensional nanostructure material.
In fig. 1, the outer coating layer is ferroferric oxide, and the coated layer is copper cobalt sulfide.
Figure 2 left shows the magnet and right shows the copper cobalt sulphur @ iron oxide in ethanol (demonstrating its magnetic properties).
Example 2
A preparation method of a hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nanostructure material comprises the following steps:
step 1, adding 0.1g of cobalt nitrate hexahydrate into 15ml of methanol and stirring to form a solution A; weighing 0.1g of 2-methylimidazole, adding into 14ml of methanol and stirring to form a solution B; mixing the solution A and the solution B, stirring for 5min to form a uniform solution, standing for 32h, and washing with ethanol to obtain 12ml of ZIF-67 ethanol dispersion;
step 2, taking 2ml of ZIF-67 ethanol dispersion liquid obtained in the step 1, then taking 2ml of ethanol and 4mg of thioacetamide, adding the ethanol and the 4mg of thioacetamide into the ZIF-67 ethanol dispersion liquid, fully stirring for 20min, then moving the mixture into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 210 ℃, the reaction time is 1h, centrifuging or filtering a product, washing the obtained precipitate for 4 times by using absolute ethanol, and drying the obtained clean precipitate in a vacuum oven at 20 ℃ for 24h to obtain a product of sulfur-doped ZIF;
and 3, taking the sulfur-doped ZIF product obtained in the step 2, then taking 0.02g of ferric chloride, 0.14mmol of copper chloride, 8ml of water and 10mg of thioacetamide, fully stirring for 20min to form a solution, then transferring the solution into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 200 ℃, the reaction time is 1h, centrifuging or filtering the product after reaction, taking the precipitate, washing the precipitate with ethanol for 4 times to obtain a clean precipitate, drying the clean precipitate in a vacuum oven at 20 ℃ for 24h, and grinding to obtain the ferroferric oxide-coated copper cobalt sulfide, namely the hollow copper cobalt sulfur @ iron oxide composite three-dimensional nanostructure material.
Example 3
A preparation method of a hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nanostructure material comprises the following steps:
step 1, adding 18g of cobalt nitrate hexahydrate into 75ml of methanol and stirring to form a solution A; weighing 15g of 2-methylimidazole, adding the 2-methylimidazole into 75ml of methanol, and stirring to form a solution B; mixing the solution A and the solution B, stirring for 10min to form a uniform solution, standing for 28h, and washing with ethanol to obtain 30ml of ZIF-67 ethanol dispersion;
step 2, taking 8ml of ZIF-67 ethanol dispersion liquid obtained in the step 1, then taking 5ml of ethanol and 15mg of thioacetamide, adding the ethanol and 15mg of thioacetamide into the ZIF-67 ethanol dispersion liquid, fully stirring for 15min, then moving the mixture into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 150 ℃, the reaction time is 7 hours, centrifuging or filtering a product, washing the obtained precipitate for 4 times by using absolute ethanol, and drying the obtained clean precipitate in a vacuum oven at 100 ℃ for 4 hours to obtain a sulfur-doped ZIF product;
and 3, taking the sulfur-doped ZIF product obtained in the step 2, then taking 0.08g of ferric chloride, 1.1mmol of copper chloride, 30ml of water and 65mg of thioacetamide, fully stirring for 15min to form a solution, then transferring the solution into a high-temperature reaction kettle, controlling the temperature of the high-temperature reaction kettle to be 120 ℃, controlling the reaction time to be 7h, centrifuging or filtering the product after the reaction, taking the precipitate, washing the precipitate with ethanol for 4 times to obtain a clean precipitate, drying the clean precipitate in a vacuum oven at 100 ℃ for 4h, and grinding to obtain the ferroferric oxide-coated copper cobalt sulfide, namely the hollow copper cobalt sulfur @ iron oxide composite three-dimensional nanostructure material.
Example 4
A preparation method of a hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nanostructure material comprises the following steps:
step 1, adding 36g of cobalt nitrate hexahydrate into 78ml of methanol and stirring to form a solution A; weighing 50g of 2-methylimidazole, adding into 80ml of methanol and stirring to form a solution B; mixing the solution A and the solution B, stirring for 15min to form a uniform solution, standing for 20h, and washing with ethanol to obtain 48ml of ZIF-67 ethanol dispersion;
step 2, taking 6ml of ZIF-67 ethanol dispersion liquid obtained in the step 1, then taking 8ml of ethanol and 35mg of thioacetamide, adding the ethanol and 35 ml of thioacetamide into the ZIF-67 ethanol dispersion liquid, fully stirring for 18min, then moving the mixture into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 180 ℃, the reaction time is 4 hours, centrifuging or filtering a product, washing the obtained precipitate for 3 times by using absolute ethanol, and drying the obtained clean precipitate in a vacuum oven at 70 ℃ for 10 hours to obtain a sulfur-doped ZIF product;
and 3, taking the sulfur-doped ZIF product obtained in the step 2, then taking 0.45g of ferric chloride, 1.5mmol of copper chloride, 40ml of water and 75mg of thioacetamide, fully stirring for 18min to form a solution, then transferring the solution into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 170 ℃, the reaction time is 4h, centrifuging or filtering the product after reaction, taking the precipitate, washing the precipitate for 3 times by using ethanol to obtain a clean precipitate, drying the clean precipitate in a vacuum oven at 70 ℃ for 10h, and grinding to obtain the ferroferric oxide-coated copper cobalt sulfide, namely the hollow copper cobalt sulfide @ iron oxide composite three-dimensional nanostructure material.
Example 5
A preparation method of a hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nanostructure material comprises the following steps:
step 1, adding 80g of cobalt nitrate hexahydrate into 90ml of methanol and stirring to form a solution A; weighing 150g of 2-methylimidazole, adding the 2-methylimidazole into 88ml of methanol, and stirring to form a solution B; mixing the solution A and the solution B, stirring for 30min to form a uniform solution, standing for 1h, and washing with ethanol to obtain 60ml of ZIF-67 ethanol dispersion;
step 2, taking 10ml of ZIF-67 ethanol dispersion liquid obtained in the step 1, then taking 8ml of ethanol and 48mg of thioacetamide, adding the ethanol and the thioacetamide into the ZIF-67 ethanol dispersion liquid, fully stirring for 30min, then moving the mixture into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 190 ℃, the reaction time is 6 hours, centrifuging or filtering a product, washing the obtained precipitate for 4 times by using absolute ethanol, and drying the obtained clean precipitate in a vacuum oven at 80 ℃ for 9 hours to obtain a sulfur-doped ZIF product;
and 3, taking the sulfur-doped ZIF product obtained in the step 2, then taking 0.88g of ferric chloride, 1.85mmol of copper chloride, 48ml of water and 78mg of thioacetamide, fully stirring for 30min to form a solution, then transferring the solution into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 160 ℃, the reaction time is 6h, centrifuging or filtering the product after reaction, taking the precipitate, washing the precipitate with ethanol for 4 times to obtain a clean precipitate, drying the clean precipitate in a vacuum oven at 80 ℃ for 9h, and grinding to obtain the ferroferric oxide-coated copper cobalt sulfide, namely the hollow copper cobalt sulfur @ iron oxide composite three-dimensional nanostructure material.
Example 6
A preparation method of a hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nanostructure material comprises the following steps:
step 1, adding 0.01g of cobalt nitrate hexahydrate into 12ml of methanol and stirring to form a solution A; weighing 0.01g of 2-methylimidazole, adding into 10ml of methanol and stirring to form a solution B; mixing the solution A and the solution B, stirring for 1min to form a uniform solution, standing for 36h, and washing with ethanol to obtain 4ml of ZIF-67 ethanol dispersion;
step 2, taking 1ml of ZIF-67 ethanol dispersion liquid obtained in the step 1, then taking 1.2ml of ethanol and 5mg of thioacetamide, adding the ethanol and the 5mg of thioacetamide into the ZIF-67 ethanol dispersion liquid, fully stirring for 5min, then moving the mixture into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 170 ℃, the reaction time is 2 hours, centrifuging or filtering a product, washing the obtained precipitate for 3 times by using absolute ethanol, and drying the obtained clean precipitate in a vacuum oven at 90 ℃ for 3.5 hours to obtain a sulfur-doped ZIF product;
and 3, taking the sulfur-doped ZIF product obtained in the step 2, then taking 0.01g of ferric chloride, 0.12mmol of copper chloride, 5ml of water and 8mg of thioacetamide, fully stirring for 5min to form a solution, then transferring the solution into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 150 ℃, the reaction time is 2h, centrifuging or filtering the product after reaction, taking the precipitate, washing the precipitate for 3 times by using ethanol to obtain a clean precipitate, drying the clean precipitate in a vacuum oven at 90 ℃ for 3.5h, and grinding to obtain the ferroferric oxide-coated copper cobalt sulfide, namely the hollow copper cobalt sulfur @ iron oxide composite three-dimensional nanostructure material.
Example 7
A preparation method of a hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nanostructure material comprises the following steps:
step 1, adding 100g of cobalt nitrate hexahydrate into 100ml of methanol and stirring to form a solution A; weighing 200g of 2-methylimidazole, adding into 98ml of methanol and stirring to form a solution B; mixing the solution A and the solution B, stirring for 25min to form a uniform solution, standing for 5h, and washing with ethanol to obtain 60ml of ZIF-67 ethanol dispersion;
step 2, taking 10ml of ZIF-67 ethanol dispersion liquid obtained in the step 1, then taking 10ml of ethanol and 50mg of thioacetamide, adding the ethanol and 50mg of thioacetamide into the ZIF-67 ethanol dispersion liquid, fully stirring for 25min, then moving the mixture into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 160 ℃, the reaction time is 3 hours, centrifuging or filtering a product, washing the obtained precipitate for 4 times by using absolute ethanol, and drying the obtained clean precipitate in a vacuum oven at 65 ℃ for 11 hours to obtain a sulfur-doped ZIF product;
and 3, taking the sulfur-doped ZIF product obtained in the step 2, then taking 1g of ferric chloride, 2mmol of copper chloride, 50ml of water and 80mg of thioacetamide, fully stirring for 25min to form a solution, then transferring the solution into a high-temperature reaction kettle, wherein the temperature of the high-temperature reaction kettle is 140 ℃, the reaction time is 3h, centrifuging or filtering the product after reaction, taking the precipitate, washing the precipitate with ethanol for 4 times to obtain a clean precipitate, drying the clean precipitate in a vacuum oven at 65 ℃ for 11h, and grinding to obtain the ferroferric oxide-coated copper cobalt sulfide, namely the hollow copper cobalt sulfide @ iron oxide composite three-dimensional nanostructure material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. A preparation method of a hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nanostructure material is characterized by comprising the following steps of:
step 1, adding 0.01-100g of cobalt nitrate hexahydrate into 10-100ml of methanol and stirring to form a solution A; weighing 0.01-200g of 2-methylimidazole, adding into 10-100ml of methanol, and stirring to form a solution B; mixing the solution A and the solution B, stirring to form a uniform solution, standing, and washing with ethanol to obtain 10-60ml of ZIF-67 ethanol dispersion;
step 2, taking 1-10ml of ZIF-67 ethanol dispersion liquid obtained in the step 1, then taking 1-10ml of ethanol and 5-50mg of thioacetamide, adding the ethanol and the thioacetamide into the ZIF-67 ethanol dispersion liquid, fully stirring, then transferring the mixture into a high-temperature reaction kettle, centrifuging or filtering a product, washing the obtained precipitate with absolute ethanol, and carrying out vacuum drying on the obtained clean precipitate to obtain a product Co precursor;
and 3, taking the product Co precursor obtained in the step 2, then taking 0.01-1g of ferric chloride, 0.1-2mmol of copper chloride, 5-50ml of water and 5-80mg of thioacetamide, fully stirring to form a solution, then transferring the solution into a high-temperature reaction kettle, centrifuging or filtering the product after reaction, taking the precipitate, washing the precipitate with ethanol to obtain a clean precipitate, drying and grinding to obtain the hollow copper-cobalt-sulfur-iron oxide composite three-dimensional nano-structure material.
2. The preparation method of the hollow copper-cobalt-sulfur-iron oxide composite three-dimensional nanostructured material according to claim 1, wherein in the step 1, the solution A and the solution B are mixed and stirred for 1-30min, and then are allowed to stand for 1-36 h.
3. The preparation method of the hollow copper-cobalt-sulfur-iron oxide composite three-dimensional nanostructured material according to claim 2, wherein in the step 1, the solution A and the solution B are mixed and stirred for 20min and then are allowed to stand for 24 h.
4. The method for preparing the hollow copper-cobalt-sulfur-iron oxide composite three-dimensional nanostructured material as claimed in claim 1, wherein in the step 2, the time period of the sufficient stirring is 5-60min, the temperature of the high-temperature reaction kettle is 150-210 ℃, the reaction time is 1-7h, the obtained precipitate is washed 3-4 times with absolute ethyl alcohol, and the clean precipitate is dried in a vacuum oven at 20-100 ℃ for 1-24 h.
5. The preparation method of the hollow copper-cobalt-sulfur-iron oxide composite three-dimensional nanostructured material according to claim 4, wherein in the step 2, the time period of the sufficient stirring is 30min, the temperature of the high-temperature reaction kettle is 200 ℃, the reaction time is 5h, the obtained precipitate is washed 3 times with absolute ethyl alcohol, and the clean precipitate is dried in a vacuum oven at 60 ℃ for 12 h.
6. The method for preparing the hollow copper-cobalt-sulfur-iron oxide composite three-dimensional nanostructured material as claimed in claim 1, wherein in the step 3, the stirring time is 5-60min, the temperature of the high-temperature reaction kettle is 120-200 ℃, the reaction time is 1-7h, the reaction kettle is washed with ethanol for 3-4 times, and the clean precipitate is dried in a vacuum oven at 20-100 ℃ for 1-24 h.
7. The preparation method of the hollow copper-cobalt-sulfur-iron oxide composite three-dimensional nanostructured material according to claim 6, wherein in the step 3, the stirring time is 30min, the temperature of the high-temperature reaction kettle is 180 ℃, the reaction time is 5h, the reaction kettle is washed with ethanol for 4 times, and the clean precipitate is dried in a vacuum oven at 60 ℃ for 12 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110823751.3A CN113477253B (en) | 2021-07-21 | 2021-07-21 | Preparation method of hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nano-structure material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110823751.3A CN113477253B (en) | 2021-07-21 | 2021-07-21 | Preparation method of hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nano-structure material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113477253A true CN113477253A (en) | 2021-10-08 |
| CN113477253B CN113477253B (en) | 2022-10-11 |
Family
ID=77942752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110823751.3A Active CN113477253B (en) | 2021-07-21 | 2021-07-21 | Preparation method of hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nano-structure material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113477253B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115672354A (en) * | 2022-10-17 | 2023-02-03 | 常州大学 | Preparation method and application of ZIF-67 derived hollow cobalt sulfide/cadmium manganese sulfide composite photocatalyst |
| CN115990493A (en) * | 2022-12-28 | 2023-04-21 | 电子科技大学 | Preparation method of cobalt-based multi-metal sulfide heterostructure nanomaterial |
| CN116013700A (en) * | 2022-09-27 | 2023-04-25 | 福州大学 | Copper cobalt sulfide/poly 3, 4-ethylenedioxythiophene composite electrode material and preparation method thereof |
| CN115990493B (en) * | 2022-12-28 | 2024-06-07 | 电子科技大学 | Preparation method of cobalt-based multi-metal sulfide heterostructure nanomaterial |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108359105A (en) * | 2018-02-11 | 2018-08-03 | 安徽工程大学 | Metal organic framework/iron oxide composite material of core-shell structure preparation method |
| CN109876809A (en) * | 2019-04-01 | 2019-06-14 | 中国科学院过程工程研究所 | A kind of hollow more Shell Materials of metal composite oxide and its preparation method and application |
| CN110961159A (en) * | 2019-12-31 | 2020-04-07 | 五邑大学 | Supported Fe-Co/ZIF-67 bimetallic catalyst and preparation method and application thereof |
| CN111729675A (en) * | 2020-05-28 | 2020-10-02 | 上海大学 | ZIF-67-DERIVED Co3S4And ZnIn2S4Preparation method and application of formed composite photocatalyst |
| CN111804313A (en) * | 2020-06-10 | 2020-10-23 | 上海大学 | Fe2O3@Co9S8Preparation method and application of double-hollow core-shell structure nano composite material |
| CN112108121A (en) * | 2020-09-28 | 2020-12-22 | 南京林业大学 | Magnetic Fe3O4Preparation method of @ MOF composite material, product and application thereof |
| AU2021100865A4 (en) * | 2021-02-12 | 2021-04-22 | Guangdong University Of Technology | Preparation and application of a series non-copper catalyst for preparing methane by electrocatalytic carbon dioxide |
-
2021
- 2021-07-21 CN CN202110823751.3A patent/CN113477253B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108359105A (en) * | 2018-02-11 | 2018-08-03 | 安徽工程大学 | Metal organic framework/iron oxide composite material of core-shell structure preparation method |
| CN109876809A (en) * | 2019-04-01 | 2019-06-14 | 中国科学院过程工程研究所 | A kind of hollow more Shell Materials of metal composite oxide and its preparation method and application |
| CN110961159A (en) * | 2019-12-31 | 2020-04-07 | 五邑大学 | Supported Fe-Co/ZIF-67 bimetallic catalyst and preparation method and application thereof |
| CN111729675A (en) * | 2020-05-28 | 2020-10-02 | 上海大学 | ZIF-67-DERIVED Co3S4And ZnIn2S4Preparation method and application of formed composite photocatalyst |
| CN111804313A (en) * | 2020-06-10 | 2020-10-23 | 上海大学 | Fe2O3@Co9S8Preparation method and application of double-hollow core-shell structure nano composite material |
| CN112108121A (en) * | 2020-09-28 | 2020-12-22 | 南京林业大学 | Magnetic Fe3O4Preparation method of @ MOF composite material, product and application thereof |
| AU2021100865A4 (en) * | 2021-02-12 | 2021-04-22 | Guangdong University Of Technology | Preparation and application of a series non-copper catalyst for preparing methane by electrocatalytic carbon dioxide |
Non-Patent Citations (5)
| Title |
|---|
| LANG GAN等: "Preparation of double-shell Co9S8/Fe3O4 embedded in S/N co-decorated", 《JOURNAL OF POWER SOURCES》 * |
| LIWEI CHEN等: "Rational design and synthesis of hollow Co3O4@Fe2O3 core-shell", 《CHEMICAL ENGINEERING JOURNAL》 * |
| ZHEN-FENG HUANG等: "Hollow Cobalt-Based Bimetallic Sulfide Polyhedra for Efficient All-pHValue Electrochemical and Photocatalytic Hydrogen Evolution", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 杨金曼等: "MOFs诱导中空Co3O4/CdIn2S4合成及光催化CO2还原性能研究", 《化工学报》 * |
| 邢锦娟等: "Co-MOFs材料在锂离子电池负极材料中的应用研究进展", 《化学研究》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116013700A (en) * | 2022-09-27 | 2023-04-25 | 福州大学 | Copper cobalt sulfide/poly 3, 4-ethylenedioxythiophene composite electrode material and preparation method thereof |
| CN115672354A (en) * | 2022-10-17 | 2023-02-03 | 常州大学 | Preparation method and application of ZIF-67 derived hollow cobalt sulfide/cadmium manganese sulfide composite photocatalyst |
| CN115672354B (en) * | 2022-10-17 | 2024-05-28 | 常州大学 | Preparation method and application of ZIF-67-derived hollow cobalt sulfide/manganese cadmium sulfide composite photocatalyst |
| CN115990493A (en) * | 2022-12-28 | 2023-04-21 | 电子科技大学 | Preparation method of cobalt-based multi-metal sulfide heterostructure nanomaterial |
| CN115990493B (en) * | 2022-12-28 | 2024-06-07 | 电子科技大学 | Preparation method of cobalt-based multi-metal sulfide heterostructure nanomaterial |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113477253B (en) | 2022-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ding et al. | Metal-organic framework derived Co3O4/TiO2 heterostructure nanoarrays for promote photoelectrochemical water splitting | |
| Tian et al. | Anchoring metal-organic framework nanoparticles on graphitic carbon nitrides for solar-driven photocatalytic hydrogen evolution | |
| Yang et al. | Graphdiyne (g-CnH2n-2) based Co3S4 anchoring and edge-covalently modification coupled with carbon-defects g-C3N4 for photocatalytic hydrogen production | |
| Wang et al. | Recent advances in bismuth vanadate-based photocatalysts for photoelectrochemical water splitting | |
| Yan et al. | 3D layered nano-flower MoSx anchored with CoP nanoparticles form double proton adsorption site for enhanced photocatalytic hydrogen evolution under visible light driven | |
| Li et al. | Rational design of a cobalt sulfide/bismuth sulfide S-scheme heterojunction for efficient photocatalytic hydrogen evolution | |
| Kadi et al. | Uniform dispersion of CuO nanoparticles on mesoporous TiO2 networks promotes visible light photocatalysis | |
| CN113477253B (en) | Preparation method of hollow copper-cobalt-sulfur @ iron oxide composite three-dimensional nano-structure material | |
| Wang et al. | Photocatalytic CO2 reduction with water vapor to CO and CH4 in a recirculation reactor by Ag-Cu2O/TiO2 Z-scheme heterostructures | |
| Yan et al. | Sustainable and efficient hydrogen evolution over a noble metal-free WP double modified Zn x Cd 1− x S photocatalyst driven by visible-light | |
| Li et al. | Trimetallic oxyhydroxide modified 3D coral-like BiVO4 photoanode for efficient solar water splitting | |
| Yang et al. | NiCo LDH in situ derived NiCoP 3D nanoflowers coupled with a Cu 3 P p–n heterojunction for efficient hydrogen evolution | |
| Wu et al. | Enhanced visible light activated hydrogen evolution activity over cadmium sulfide nanorods by the synergetic effect of a thin carbon layer and noble metal-free nickel phosphide cocatalyst | |
| Ji et al. | 3D ordered macroporous Pt/ZnS@ ZnO core-shell heterostructure for highly effective photocatalytic hydrogen evolution | |
| Li et al. | Prickly Ni3S2 nanowires modified CdS nanoparticles for highly enhanced visible-light photocatalytic H2 production | |
| Cheng et al. | Lollipop-shaped Co9S8/CdS nanocomposite derived from zeolitic imidazolate framework-67 for the photocatalytic hydrogen production | |
| Que et al. | The Ni2+-LaNiO3/CdS hollow core–shell heterojunction towards enhanced visible light overall water splitting H2 evolution via HER/OER synergism of Ni2+/Ov | |
| Zhang et al. | Effective electron–hole separation over controllable construction of CdS/Co-Ni-P core/shell nanophotocatalyst for improved photocatalytic hydrogen evolution under visible-light-driven | |
| Liu et al. | Marigold shaped mesoporous composites Bi2S3/Ni (OH) 2 with nn heterojunction for high efficiency photocatalytic hydrogen production from water decomposition | |
| Zhang et al. | Efficient photo-catalytic hydrogen production performance and stability of a three-dimensional porous CdS NPs-graphene hydrogel | |
| Selvaratnam et al. | TiO2-MgO mixed oxide nanomaterials for solar energy conversion | |
| Yu et al. | Construction of CoS/CeO2 heterostructure nanocages with enhanced photocatalytic performance under visible light | |
| Hu et al. | Red/black phosphorus Z-scheme heterogeneous junction modulated by co-MOF for enhanced photocatalytic hydrogen evolution | |
| Zhang et al. | Metal-organic framework-derived nitrogen-doped carbon-coated hollow tubular In2O3/CdZnS heterojunction for efficient photocatalytic hydrogen evolution | |
| Huang et al. | Increase and enrichment of active electrons by carbon dots induced to improve TiO2 photocatalytic hydrogen production activity |
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 |