CN106495204A - A kind of preparation method of single dispersing yolk shell structure C uO microballoons - Google Patents
A kind of preparation method of single dispersing yolk shell structure C uO microballoons Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 210000002969 egg yolk Anatomy 0.000 title description 3
- 239000004005 microsphere Substances 0.000 claims abstract description 62
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 22
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 12
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 7
- 229940043267 rhodamine b Drugs 0.000 claims description 7
- 238000012546 transfer Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 238000001816 cooling Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 72
- 239000000243 solution Substances 0.000 description 15
- 239000005751 Copper oxide Substances 0.000 description 9
- 229910000431 copper oxide Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 239000013084 copper-based metal-organic framework Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000013742 energy transducer activity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Organic Chemistry (AREA)
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- Manufacturing Of Micro-Capsules (AREA)
Abstract
本发明公开了一种单分散yolk‑shell结构CuO微球的制备方法，将乙酸铜或乙酸铜与PVP分散乙二醇中充分溶解，将溶液转移至高压反应釜中恒温加热反应，待反应结束过后自然冷却沉降，去除上层清液，抽滤后获得蓝色固体产物在真空干燥箱中，烘干至恒重得具有单分散特性yolk‑shell结构的CuO微球前驱物；利用可控升温速率的电阻炉，将所获得的前驱物在空气气氛中控温退火，冷却至室温即可获得。本发明巧妙的运用乙二醇同时作为有机溶剂和结构导向剂，实现对结构的可控设计；原料易得，成本低廉，对环境几乎无污染，产物易分离，纯度高，形貌好且均一，制备工艺简单，易操作，光化学性能显著高于其他结构。
The invention discloses a method for preparing CuO microspheres with a monodisperse yolk-shell structure. Copper acetate or copper acetate is fully dissolved in PVP-dispersed ethylene glycol, and the solution is transferred to a high-pressure reactor for constant temperature heating reaction until the reaction is completed. After natural cooling and sedimentation, the supernatant was removed, and the blue solid product was obtained after suction filtration in a vacuum drying oven, and dried to a constant weight to obtain a CuO microsphere precursor with a monodisperse yolk-shell structure; using a controllable heating rate The obtained precursor is annealed in an air atmosphere under temperature control and cooled to room temperature in a resistance furnace. The invention cleverly uses ethylene glycol as an organic solvent and a structure-directing agent at the same time to realize the controllable design of the structure; the raw materials are easy to obtain, the cost is low, the environment is almost non-polluting, the product is easy to separate, the purity is high, and the appearance is good and uniform , the preparation process is simple, easy to operate, and the photochemical performance is significantly higher than other structures.
Description
技术领域technical field
本发明涉及一种无机功能微纳米结构材料的制备方法，尤其涉及一种单分散yolk-shell结构CuO微球的制备方法。The invention relates to a method for preparing an inorganic functional micro-nano structure material, in particular to a method for preparing CuO microspheres with a monodisperse yolk-shell structure.
背景技术Background technique
CuO是p型窄带系半导体，禁带宽度约1.2 eV，在许多领域都有着潜在的应用，比如传感器、高性能电化学电容器、锂离子电池负极材料、催化和光催化剂、太阳能电池等。近几年，由于不同尺寸和形貌微/纳米CuO材料所具有的优异性能吸引了越来越多材料科学科研工作者的关注。CuO is a p-type narrow-band semiconductor with a band gap of about 1.2 eV. It has potential applications in many fields, such as sensors, high-performance electrochemical capacitors, anode materials for lithium-ion batteries, catalysis and photocatalysts, and solar cells. In recent years, due to the excellent properties of micro/nano CuO materials with different sizes and morphologies, more and more material science researchers have attracted attention.
目前，众多研究小组已开发许多方法来可控制备具有特定结构和形貌的CuO微/纳米材料应用于这些领域，并且取得了很好的效果。如使用表面活性剂在水热环境中制备具有手性结构的氧化铜纳米花；在水热溶剂热环境中，制备了由菱形纳米带通过自组装而成的蒲公英状CuO介孔晶体；在室温条件下，利用脱水干燥纳米线状氢氧化铜水溶液制备了胡桃状氧化铜纳米颗粒；在微波辅助水热环境中实现了叶片状和球状氧化铜纳米颗粒制备；在室温下通过液相化学的方法制备了超长晶体状氧化铜纳米线；通过快速湿化学方法制备了氧化铜纳米带和氧化铜纳米花；通过热处理铜基配位聚合物的方法制备了分级蝴蝶片状的氧化铜纳米材料以及空心氧化铜纳米管；通过热处理基于铜的金属-有机框架模板合成出多孔八面体的氧化铜空心框架。At present, many research groups have developed many methods to controllably prepare CuO micro/nanomaterials with specific structures and morphologies for these fields, and achieved good results. For example, using surfactants to prepare copper oxide nanoflowers with chiral structure in a hydrothermal environment; in a hydrothermal solvothermal environment, a dandelion-shaped CuO mesoporous crystal composed of rhomboid nanoribbons was prepared through self-assembly; at room temperature Under certain conditions, walnut-shaped copper oxide nanoparticles were prepared by dehydrating and drying nanowire-like copper hydroxide aqueous solution; leaf-shaped and spherical copper oxide nanoparticles were prepared in a microwave-assisted hydrothermal environment; at room temperature by liquid-phase chemical method Superlong crystal-like copper oxide nanowires were prepared; copper oxide nanobelts and copper oxide nanoflowers were prepared by a fast wet chemical method; hierarchical butterfly-shaped copper oxide nanomaterials were prepared by heat treatment of copper-based coordination polymers and Hollow copper oxide nanotubes; porous octahedral copper oxide hollow frameworks synthesized by heat-treating copper-based metal-organic framework templates.
发明人发现，一种具有单分散yolk-shell结构的CuO微球在光化学性能应用方面可充分利用光线的多次反射和散射来增强光子的捕获能力，进而提高光的利用效率，实现对具有yolk-shell结构CuO微球的可控制备具有十分重要的研究意义和实用价值。然而，到目前为止，未见相关技术的报道，而通过使用一种简单、绿色的溶剂进行溶剂热制备具单分散yolk-shell结构的CuO微球前驱物并结合简单的退火方法获得单分散yolk-shell结构的CuO微球更未曾报道过。The inventors found that a CuO microsphere with a monodisperse yolk-shell structure can make full use of multiple reflections and scattering of light to enhance the capture ability of photons in the application of photochemical properties, thereby improving the utilization efficiency of light and realizing the application of yolk The controllable preparation of CuO microspheres with -shell structure has very important research significance and practical value. However, so far, there has been no report on related technologies, and by using a simple, green solvent for solvothermal preparation of CuO microsphere precursors with a monodisperse yolk-shell structure combined with a simple annealing method to obtain monodisperse yolk CuO microspheres with -shell structure have never been reported.
发明内容Contents of the invention
为了解决现有技术中存在的不足，本发明的目的在于提供一种简单、绿色的溶剂热法制备具有单分散特性的yolk-shell结构的CuO微球前驱物，通过直接在空气环境中进行退火，实现具有单分散特性的yolk-shell结构的CuO微球的制备。In order to solve the deficiencies in the prior art, the object of the present invention is to provide a simple and green solvothermal method to prepare CuO microsphere precursors with monodisperse yolk-shell structure, by annealing directly in the air environment , to achieve the preparation of CuO microspheres with monodisperse yolk-shell structure.
为达到上述目的，本发明所采用的技术手段是：一种单分散yolk-shell结构CuO微球的制备方法，步骤包括：In order to achieve the above object, the technical means adopted in the present invention is: a kind of preparation method of monodisperse yolk-shell structure CuO microsphere, and step comprises:
一、取一定量的乙酸铜或乙酸铜和聚乙烯吡咯烷酮的混合物，分散在装有乙二醇的容器中，搅拌至充分溶解，形成清澈透明蓝色溶液；1. Take a certain amount of copper acetate or a mixture of copper acetate and polyvinylpyrrolidone, disperse it in a container filled with ethylene glycol, stir until fully dissolved, and form a clear and transparent blue solution;
二、将步骤一中得到的蓝色溶液转移至高压反应釜中，在140～200℃恒温加热反应1～3h；2. Transfer the blue solution obtained in step 1 to a high-pressure reactor, and heat the reaction at a constant temperature of 140-200°C for 1-3 hours;
三、将步骤二加热反应结束后的产物冷却至室温，经沉降，去除上层清液，抽滤后获得蓝色固体物；3. Cool the product after the heating reaction in step 2 to room temperature, remove the supernatant after settling, and obtain a blue solid after suction filtration;
四、将步骤三中得到的蓝色固体物在真空干燥箱中，40～60℃烘干至恒重，得到具有单分散特性yolk-shell结构的CuO微球前驱物；4. Dry the blue solid obtained in step 3 in a vacuum drying oven at 40-60° C. to constant weight to obtain a CuO microsphere precursor with monodisperse yolk-shell structure;
五、利用可控升温速率的电阻炉，将步骤四中获得的前驱物在空气气氛中和一定的温度条件下进行退火，获得具有单分散特性yolk-shell结构的CuO微球。5. Using a resistance furnace with a controllable heating rate, the precursor obtained in step 4 is annealed in an air atmosphere at a certain temperature to obtain CuO microspheres with a monodisperse yolk-shell structure.
进一步的，所述乙酸铜和聚乙烯吡咯烷酮的质量比1～3：1～4，所述乙酸铜和乙二醇的质量体积比为1～3：280～320 g/ml；或乙酸铜与聚乙烯吡咯烷酮的混合物与乙二醇的质量体积比为2～7：280～320 g/ml。Further, the mass ratio of copper acetate to polyvinylpyrrolidone is 1-3:1-4, and the mass-volume ratio of copper acetate to ethylene glycol is 1-3:280-320 g/ml; or copper acetate and The mass volume ratio of the mixture of polyvinylpyrrolidone and ethylene glycol is 2-7: 280-320 g/ml.
进一步的，所述步骤二中的高压反应釜为具有聚四氟乙烯内衬的高压反应釜。Further, the high-pressure reactor in the step 2 is a high-pressure reactor with a polytetrafluoroethylene lining.
进一步的，所述步骤四中，对抽滤后获得的蓝色固体物无须洗涤，直接放入真空干燥箱中，设置真空度0.08～0.09MPa，烘干至恒重。Further, in the step 4, the blue solid obtained after suction filtration is directly put into a vacuum drying oven without washing, and the vacuum degree is set at 0.08-0.09 MPa, and dried to a constant weight.
进一步的，所述步骤五中，可控升温速率的电阻炉升温速率为1～3℃/每分钟，从室温升温至350～400℃，在350～400℃维持1～2 h。Further, in the step five, the heating rate of the resistance furnace with a controllable heating rate is 1-3°C/min, the temperature is raised from room temperature to 350-400°C, and maintained at 350-400°C for 1-2 hours.
进一步的，所述单分散yolk-shell结构CuO微球是指，在光催化体系中加入浓度为25～28% H2O2，实现对罗丹明B在30min内达到92%以上的降解效果。Further, the monodisperse CuO microspheres with yolk-shell structure means that the concentration of 25-28% H 2 O 2 is added to the photocatalytic system to achieve a degradation effect of more than 92% on rhodamine B within 30 minutes.
本发明的有益效果是：采用简单、绿色的溶剂热法制备具有单分散特性的yolk-shell结构的CuO微球前驱物，通过直接在空气环境中退火，实现具有单分散特性的yolk-shell结构的CuO微球；该结构的CuO微球直径在1.7～2.1μm，表面壳层与内核之间的距离约200nm，成分检测结果表明不含其他杂质；本方法巧妙的运用了乙二醇，使其同时作为有机溶剂和结构导向剂，实现对yolk-shell结构可控设计；原料易得，成本低廉，对环境几乎无污染，产物易分离，纯度高，形貌好且均一，制备工艺简单，易于操作；所获得的单分散yolk-shell结构CuO微球具有优异的光化学性能，与其他结构的CuO相比，特别是与相同用量的具有实心结构的CuO微球相比，能显著提高材料的光催化性能。The beneficial effects of the present invention are: the simple and green solvothermal method is used to prepare the CuO microsphere precursor with monodisperse yolk-shell structure, and the yolk-shell structure with monodisperse property can be realized by directly annealing in the air environment CuO microspheres; the diameter of CuO microspheres with this structure is 1.7-2.1 μm, the distance between the surface shell and the inner core is about 200nm, and the composition test results show that there are no other impurities; this method cleverly uses ethylene glycol, so that It serves as an organic solvent and a structure-directing agent at the same time to realize the controllable design of the yolk-shell structure; the raw materials are easy to obtain, the cost is low, there is almost no pollution to the environment, the product is easy to separate, the purity is high, the shape is good and uniform, and the preparation process is simple. Easy to operate; the obtained monodisperse yolk-shell structure CuO microspheres have excellent photochemical properties, compared with CuO with other structures, especially compared with the same amount of CuO microspheres with solid structure, it can significantly improve the Photocatalytic performance.
附图说明Description of drawings
下面结合附图和实施例对本发明作进一步的阐述。The present invention will be further elaborated below in conjunction with the accompanying drawings and embodiments.
图1 本发明所得具有单分散特性yolk-shell结构的CuO微球前驱物的X射线衍射(XRD)图谱；Fig. 1 the X-ray diffraction (XRD) pattern of the CuO microsphere precursor with monodisperse characteristic yolk-shell structure obtained by the present invention;
图2本发明所得具有单分散特性yolk-shell结构的CuO微球前驱物的扫描电子显微电镜照片；图3本发明所得具有单分散特性yolk-shell结构的CuO微球前驱物的透射电子显微镜照片；Fig. 2 is the scanning electron micrograph of the CuO microsphere precursor with monodisperse characteristic yolk-shell structure obtained by the present invention; Fig. 3 is the transmission electron microscope of the CuO microsphere precursor with monodisperse characteristic yolk-shell structure obtained by the present invention photo;
图4本发明所得具有单分散特性yolk-shell结构的CuO微球的X射线衍射(XRD)图谱；The X-ray diffraction (XRD) spectrum of the CuO microsphere that Fig. 4 gained of the present invention has monodisperse characteristic yolk-shell structure;
图5本发明所得具有单分散特性yolk-shell结构的CuO微球的扫描电子显微电镜照片；Fig. 5 is a scanning electron microscopic photo of CuO microspheres with monodisperse characteristic yolk-shell structure obtained by the present invention;
图6本发明所得具有单分散特性yolk-shell结构的CuO微球的500nm透射电子显微镜照片；The 500nm transmission electron micrograph of the CuO microsphere with monodisperse characteristic yolk-shell structure obtained by Fig. 6 of the present invention;
图7本发明所得具有单分散特性yolk-shell结构的CuO微球的100nm透射电子显微镜照片；The 100nm transmission electron micrograph of the CuO microsphere with monodisperse characteristic yolk-shell structure obtained in Fig. 7 of the present invention;
图8本发明所得具有单分散特性yolk-shell结构的CuO微球与CuO其它相关结构材料的光化学性能在时间轴上的对比图；Fig. 8 is a comparison diagram of the photochemical properties of CuO microspheres with monodisperse yolk-shell structure and CuO other related structural materials on the time axis obtained by the present invention;
图9本发明所得具有单分散特性yolk-shell结构的CuO微球与CuO其它相关结构材料的光降解率对比图。Fig. 9 is a comparison chart of the photodegradation rate of CuO microspheres with monodisperse yolk-shell structure obtained in the present invention and other CuO related structural materials.
具体实施方式detailed description
实施例1Example 1
一种单分散yolk-shell结构CuO微球的制备方法，包括以下步骤：A preparation method of monodisperse yolk-shell structure CuO microspheres, comprising the following steps:
(1)准确称取0.242g的乙酸铜(Cu(CH3COO)2·H2O)，把其分散在装有乙二醇的容器中，在磁力搅拌的作用下充分溶解，形成清澈透明蓝色溶液；(1) Accurately weigh 0.242g of copper acetate (Cu(CH 3 COO) 2 ·H 2 O), disperse it in a container containing ethylene glycol, fully dissolve it under the action of magnetic stirring, and form a clear and transparent blue solution;
(2)将步骤(1)中得到的清澈透明蓝色溶液转移至高压反应釜中，在180℃恒温加热反应1h；(2) Transfer the clear and transparent blue solution obtained in step (1) to an autoclave, and heat and react at a constant temperature of 180° C. for 1 h;
(3)反应结束后冷却至室温，经沉降后，将上层清液去除，抽滤后获得蓝色固体产物；(3) After the reaction is finished, cool to room temperature, remove the supernatant after settling, and obtain a blue solid product after suction filtration;
(4)将步骤(3)中得到的蓝色固体产物在真空干燥箱中，40～60℃烘干至恒重得到具有单分散特性yolk-shell结构的CuO微球前驱物备用；(4) drying the blue solid product obtained in step (3) in a vacuum drying oven at 40-60° C. to constant weight to obtain a CuO microsphere precursor with a monodisperse yolk-shell structure for use;
(5) 利用可控升温速率的电阻炉，将步骤(4)获得的产物在空气气氛中，以升温速率为2℃每分钟把电阻炉升温至350℃，并在该温度下恒温加热1小时，冷却至室温即可获得具有单分散特性yolk-shell结构的CuO微球。(5) Using a resistance furnace with a controllable heating rate, heat the product obtained in step (4) to 350° C. per minute at a heating rate of 2° C. in an air atmosphere, and heat it at this temperature for 1 hour. , cooling to room temperature to obtain CuO microspheres with monodisperse yolk-shell structure.
实施例2Example 2
一种单分散yolk-shell结构CuO微球的制备方法，包括以下步骤：A preparation method of monodisperse yolk-shell structure CuO microspheres, comprising the following steps:
(1)准确称取0.242g的乙酸铜(Cu(CH3COO)2·H2O)和0.1g、0.2g、0.3g或者0.4g聚乙烯吡咯烷酮(PVP)，把其分散在装有乙二醇的容器中，在磁力搅拌的作用下充分溶解，形成清澈透明蓝色溶液；(1) Accurately weigh 0.242g of copper acetate (Cu(CH 3 COO) 2 ·H 2 O) and 0.1g, 0.2g, 0.3g or 0.4g of polyvinylpyrrolidone (PVP), and disperse them in a In the diol container, fully dissolve under the action of magnetic stirring to form a clear and transparent blue solution;
(2)将步骤(1)中得到的清澈透明蓝色溶液转移至高压反应釜中，在140℃恒温加热反应1h或者3h；(2) Transfer the clear and transparent blue solution obtained in step (1) to an autoclave, and heat the reaction at a constant temperature of 140° C. for 1 hour or 3 hours;
(3)反应结束后冷却至室温，经沉降后，将上层清液去除，抽滤后获得蓝色固体产物；(3) After the reaction is finished, cool to room temperature, remove the supernatant after settling, and obtain a blue solid product after suction filtration;
(4)将步骤(3)中得到的蓝色固体产物在真空干燥箱中，40～60℃烘干至恒重得到具有单分散特性yolk-shell结构的CuO微球前驱物备用；(4) drying the blue solid product obtained in step (3) in a vacuum drying oven at 40-60° C. to constant weight to obtain a CuO microsphere precursor with a monodisperse yolk-shell structure for use;
(5) 利用可控升温速率的电阻炉，将步骤(4)获得的产物在空气气氛中，以升温速率为2℃每分钟把电阻炉升温至350℃，并在该温度下恒温加热1小时，冷却至室温即可获得具有单分散特性yolk-shell结构的CuO微球。(5) Using a resistance furnace with a controllable heating rate, heat the product obtained in step (4) to 350° C. per minute at a heating rate of 2° C. in an air atmosphere, and heat it at this temperature for 1 hour. , cooling to room temperature to obtain CuO microspheres with monodisperse yolk-shell structure.
实施例3Example 3
一种单分散yolk-shell结构CuO微球的制备方法，包括以下步骤：A preparation method of monodisperse yolk-shell structure CuO microspheres, comprising the following steps:
(1)准确称取0.242g的乙酸铜(Cu(CH3COO)2·H2O)和0.1g、0.2g、0.3g或者0.4g聚乙烯吡咯烷酮(PVP)，把其分散在装有乙二醇的容器中，在磁力搅拌的作用下充分溶解，形成清澈透明蓝色溶液；(1) Accurately weigh 0.242g of copper acetate (Cu(CH 3 COO) 2 ·H 2 O) and 0.1g, 0.2g, 0.3g or 0.4g of polyvinylpyrrolidone (PVP), and disperse them in a In the diol container, fully dissolve under the action of magnetic stirring to form a clear and transparent blue solution;
(2)将步骤(1)中得到的清澈透明蓝色溶液转移至高压反应釜中，在160℃恒温加热反应1h或者3h；(2) Transfer the clear and transparent blue solution obtained in step (1) to an autoclave, and heat the reaction at a constant temperature of 160° C. for 1 hour or 3 hours;
(3)反应结束后冷却至室温，经沉降后，将上层清液去除，抽滤后获得蓝色固体产物；(3) After the reaction is finished, cool to room temperature, remove the supernatant after settling, and obtain a blue solid product after suction filtration;
(4)将步骤(3)中得到的蓝色固体产物在真空干燥箱中，40～60℃烘干至恒重得到具有单分散特性yolk-shell结构的CuO微球前驱物备用；(4) drying the blue solid product obtained in step (3) in a vacuum drying oven at 40-60° C. to constant weight to obtain a CuO microsphere precursor with a monodisperse yolk-shell structure for use;
(5) 利用可控升温速率的电阻炉，将步骤(4)获得的产物在空气气氛中，以升温速率为2℃每分钟把电阻炉升温至350℃，并在该温度下恒温加热1小时，冷却至室温即可获得具有单分散特性yolk-shell结构的CuO微球。(5) Using a resistance furnace with a controllable heating rate, heat the product obtained in step (4) to 350° C. per minute at a heating rate of 2° C. in an air atmosphere, and heat it at this temperature for 1 hour. , cooling to room temperature to obtain CuO microspheres with monodisperse yolk-shell structure.
实施例4Example 4
一种单分散yolk-shell结构CuO微球的制备方法，包括以下步骤：A preparation method of monodisperse yolk-shell structure CuO microspheres, comprising the following steps:
(1)准确称取0.242g的乙酸铜(Cu(CH3COO)2·H2O)和0.1g、0.2g或者0.3g聚乙烯吡咯烷酮(PVP)，把其分散在装有乙二醇的容器中，在磁力搅拌的作用下充分溶解，形成清澈透明蓝色溶液；(1) Accurately weigh 0.242g of copper acetate (Cu(CH 3 COO) 2 ·H 2 O) and 0.1g, 0.2g or 0.3g of polyvinylpyrrolidone (PVP), and disperse them in a In the container, it is fully dissolved under the action of magnetic stirring to form a clear and transparent blue solution;
(2)将步骤(1)中得到的清澈透明蓝色溶液转移至高压反应釜中，在180℃恒温加热反应1h或者3h；(2) Transfer the clear and transparent blue solution obtained in step (1) to a high-pressure reactor, and heat the reaction at a constant temperature of 180° C. for 1 hour or 3 hours;
(3)反应结束后冷却至室温，经沉降后，将上层清液去除，抽滤后获得蓝色固体产物；(3) After the reaction is finished, cool to room temperature, remove the supernatant after settling, and obtain a blue solid product after suction filtration;
(4)将步骤(3)中得到的蓝色固体产物在真空干燥箱中，40～60℃烘干至恒重得到具有单分散特性yolk-shell结构的CuO微球前驱物备用；(4) drying the blue solid product obtained in step (3) in a vacuum drying oven at 40-60° C. to constant weight to obtain a CuO microsphere precursor with a monodisperse yolk-shell structure for use;
(5) 利用可控升温速率的电阻炉，将步骤(4)获得的产物在空气气氛中，以升温速率为2℃每分钟把电阻炉升温至360℃，并在该温度下恒温加热1小时，冷却至室温即可获得具有单分散特性yolk-shell结构的CuO微球。(5) Using a resistance furnace with a controllable heating rate, heat the product obtained in step (4) to 360 ° C per minute at a heating rate of 2 ° C in an air atmosphere, and heat it at this temperature for 1 hour. , cooling to room temperature to obtain CuO microspheres with monodisperse yolk-shell structure.
实施例5Example 5
一种单分散yolk-shell结构CuO微球的制备方法，包括以下步骤：A preparation method of monodisperse yolk-shell structure CuO microspheres, comprising the following steps:
(1)准确称取0.242g的乙酸铜(Cu(CH3COO)2·H2O)和0.1g、0.2g或者0.3g聚乙烯吡咯烷酮(PVP)，把其分散在装有乙二醇的容器中，在磁力搅拌的作用下充分溶解，形成清澈透明蓝色溶液；(1) Accurately weigh 0.242g of copper acetate (Cu(CH 3 COO) 2 ·H 2 O) and 0.1g, 0.2g or 0.3g of polyvinylpyrrolidone (PVP), and disperse them in a In the container, it is fully dissolved under the action of magnetic stirring to form a clear and transparent blue solution;
(2)将步骤(1)中得到的清澈透明蓝色溶液转移至高压反应釜中，在200℃恒温加热反应1h或者3h；(2) Transfer the clear and transparent blue solution obtained in step (1) to a high-pressure reactor, and heat the reaction at a constant temperature of 200° C. for 1 hour or 3 hours;
(3)反应结束后冷却至室温，经沉降后，将上层清液去除，抽滤后获得蓝色固体产物；(3) After the reaction is finished, cool to room temperature, remove the supernatant after settling, and obtain a blue solid product after suction filtration;
(4)将步骤(3)中得到的蓝色固体产物在真空干燥箱中，40～60℃烘干至恒重得到具有单分散特性yolk-shell结构的CuO微球前驱物备用；(4) drying the blue solid product obtained in step (3) in a vacuum drying oven at 40-60° C. to constant weight to obtain a CuO microsphere precursor with a monodisperse yolk-shell structure for use;
(5) 利用可控升温速率的电阻炉，将步骤(4)获得的产物在空气气氛中，以升温速率为2℃每分钟把电阻炉升温至380℃，并在该温度下恒温加热1小时，冷却至室温即可获得具有单分散特性yolk-shell结构的CuO微球。(5) Using a resistance furnace with a controllable heating rate, heat the product obtained in step (4) to 380° C. per minute at a heating rate of 2° C. in an air atmosphere, and heat it at this temperature for 1 hour. , cooling to room temperature to obtain CuO microspheres with monodisperse yolk-shell structure.
实施例6Example 6
如图1-7所示，实施例1-5所得到的具有单分散特性yolk-shell结构的CuO微球前驱物和具有单分散特性yolk-shell结构的CuO微球的照片。As shown in Figures 1-7, the photos of the CuO microsphere precursor with monodisperse yolk-shell structure and CuO microspheres with monodisperse yolk-shell structure obtained in Examples 1-5.
将上述实施例子中获得的单分散yolk-shell结构CuO微球在可见光照射下，进行光化学实验，包括以下步骤：The monodisperse yolk-shell structure CuO microspheres obtained in the above examples were subjected to a photochemical experiment under visible light irradiation, including the following steps:
(1) 准确称量20mg具有yolk-shell结构的CuO微球，放入体积容量为100ml烧杯中，其中，该烧杯装有浓度为10-5 M的罗丹明B溶液50ml和浓度为25～28%的H2O2 5ml。(1) Accurately weigh 20 mg of CuO microspheres with a yolk-shell structure, and put them into a beaker with a volume capacity of 100 ml, wherein the beaker is filled with 50 ml of rhodamine B solution with a concentration of 10 -5 M and a concentration of 25 to 28 % H 2 O 2 5ml.
(2) 在暗室环境中，在磁力搅拌的作用下，使得具有yolk-shell结构的CuO微球对罗丹明B达到吸附平衡。(2) In a darkroom environment, under the action of magnetic stirring, the CuO microspheres with yolk-shell structure reached an adsorption equilibrium for rhodamine B.
(3) 在500W氙灯照射下，进行光化学性能测试实验，每间隔15min对罗丹明B浓度进行监测，45分钟后完成光化学性能测试实验。(3) Under the irradiation of 500W xenon lamp, the photochemical performance test experiment was carried out, the concentration of rhodamine B was monitored every 15 minutes, and the photochemical performance test experiment was completed after 45 minutes.
对比试验包括以下三个方面：The comparative test includes the following three aspects:
①无任何催化剂和H2O2的条件下，在500W氙灯照射下，对罗丹明B溶液进行光化学实验；②除在体系中未加H2O2外，商用CuO样品的光化学测试实验步骤同上；③商用CuO样品和具有实心结构的CuO样品的光化学测试实验步骤同上。光化学测试实验所测试曲线结果如图8、9。①In the absence of any catalyst and H 2 O 2 , under the irradiation of 500W xenon lamp, the photochemical experiment was carried out on Rhodamine B solution; ②Except that no H 2 O 2 was added to the system, the photochemical test procedure of commercial CuO samples was the same as above ; ③ The photochemical test procedure of commercial CuO samples and CuO samples with solid structure is the same as above. The test curve results of the photochemical test experiment are shown in Figures 8 and 9.
以上实施例只是我们列举的部分实施例，用于验证在不同实验条件下，可以得到相应的实验结果。The above examples are only some of the examples listed by us, and are used to verify that corresponding experimental results can be obtained under different experimental conditions.
从上述实施例中不难看出，本发明与现有技术比较具有以下优点：It is not difficult to find out from above-mentioned embodiment, the present invention has the following advantages compared with prior art:
1、采用简单、绿色的溶剂热法制备具有单分散特性的yolk-shell结构的CuO微球前驱物，经过X射线衍射仪(XRD；Philips X’pert Pro X-ray diffractometer with Cu-Kαradiation (1.5418 Å))分析，所制备的前驱物为Cu-乙二醇配合物(如图1)；1. A simple and green solvothermal method was used to prepare CuO microsphere precursors with monodisperse yolk-shell structure, and X-ray diffractometer (XRD; Philips X'pert Pro X-ray diffractometer with Cu-Kαradiation (1.5418 Å)) analysis, the prepared precursor is Cu-ethylene glycol complex (as shown in Figure 1);
通过对其进行扫描电子显微镜(日本电子扫描电子显微镜(JEOL-6610-LV)，加速电压10KV)和透射电子显微镜(日本电子透射电子显微镜(JEOL-JEM-2100)，加速电压200KV)分析，可以发现所得到的前驱物具有单分散特性的yolk-shell结构，其颗粒直径在1.7～2.1μm(如图2、3)。By carrying out scanning electron microscope (Japan Electron Scanning Electron Microscope (JEOL-6610-LV), accelerating voltage 10KV) and transmission electron microscope (Japan Electron Transmission Electron Microscope (JEOL-JEM-2100), accelerating voltage 200KV) analysis to it, it can It is found that the obtained precursor has a monodisperse yolk-shell structure, and its particle diameter is 1.7-2.1 μm (as shown in Figures 2 and 3).
利用可控升温速率的电阻炉，将所获得的Cu-乙二醇配合物在空气气氛中和一定的温度条件下进行退火，即可获得具有单分散特性yolk-shell结构的CuO微球。经过X射线衍射仪分析，所得到的产物为CuO，无其它杂质衍射峰出现(如图4)；Using a resistance furnace with a controllable heating rate, the obtained Cu-ethylene glycol complex is annealed in an air atmosphere at a certain temperature to obtain CuO microspheres with a monodisperse yolk-shell structure. After X-ray diffractometer analysis, the obtained product is CuO, and no other impurity diffraction peaks appear (as shown in Figure 4);
通过对其进行扫描电子显微镜和透射电子显微镜分析，可以发现其结构依然保持了前驱物Cu-乙二醇配合物所具有单分散特性的yolk-shell结构，这种yolk-shell结构的表面壳层与内核之间的距离大约200nm (如图5、6、7)。Through scanning electron microscopy and transmission electron microscopy analysis, it can be found that its structure still maintains the yolk-shell structure with the monodisperse characteristics of the precursor Cu-ethylene glycol complex. The surface shell of this yolk-shell structure The distance from the core is about 200nm (as shown in Figures 5, 6, and 7).
2、本发明巧妙的运用了乙二醇作为有机溶剂和结构导向剂，实现对yolk-shell结构的可控设计；2. The present invention cleverly uses ethylene glycol as an organic solvent and a structure-directing agent to realize the controllable design of the yolk-shell structure;
3、原料易得、价格成本低廉，环境几乎无污染，产物容易分离，所得产物纯度高，形貌好且均一，制备过程及工艺简单，易于操作；3. The raw materials are easy to obtain, the price is low, the environment is almost pollution-free, the product is easy to separate, the obtained product has high purity, good and uniform appearance, the preparation process and process are simple, and it is easy to operate;
4、所获得的单分散yolk-shell结构CuO微球具有优异的光化学性能，当在光反应体系中加入5mLH2O2(浓度为25～28%)，可以实现对罗丹明B在30min内达到92%以上的降解效果，与其他相关结构的CuO相比，特别是与相同用量的具有实心结构的CuO微球相比(如图8)，能显著提高该材料的光催化性能，其原因可归结于具有yolk-shell结构CuO微球可以充分利用光线的多次反射和散射而增强了光子的捕获能力(如图9中插图所示)，提高了其光催化降解效率，该结果也进一步充分体现了具有yolk-shell结构CuO微球材料的优异特性。4. The obtained CuO microspheres with monodisperse yolk-shell structure have excellent photochemical properties. When 5mLH 2 O 2 (concentration is 25-28%) is added to the photoreaction system, the rhodamine B can be achieved within 30min. The degradation effect of more than 92%, compared with CuO with other related structures, especially compared with CuO microspheres with a solid structure in the same amount (as shown in Figure 8), can significantly improve the photocatalytic performance of the material. The reason can be Due to the fact that the CuO microspheres with yolk-shell structure can make full use of the multiple reflection and scattering of light to enhance the photon capture ability (as shown in the inset in Figure 9), and improve its photocatalytic degradation efficiency, the result is further sufficient. It embodies the excellent characteristics of CuO microsphere material with yolk-shell structure.
本发明所公开的实施例只是对本发明的技术方案的解释，不能作为对本发明内容的限制，本领域技术人员在本发明基础上的简单变更，依然在本发明的保护范围内。The embodiments disclosed in the present invention are only explanations of the technical solutions of the present invention, and cannot be used as limitations on the content of the present invention. Simple changes made by those skilled in the art on the basis of the present invention are still within the protection scope of the present invention.
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| CN109110797A (en) * | 2018-09-20 | 2019-01-01 | 西安凯立新材料股份有限公司 | A kind of preparation method of sector multi-layer cupric oxide powder |
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