CN113351216A - Low-dimensional self-assembled flower-shaped Cu2Preparation method and application of O-ZnO catalyst - Google Patents
Low-dimensional self-assembled flower-shaped Cu2Preparation method and application of O-ZnO catalyst Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 99
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 75
- 239000000243 solution Substances 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 28
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004246 zinc acetate Substances 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 14
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 10
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 78
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 25
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 17
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 claims description 12
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004471 Glycine Substances 0.000 claims description 12
- 239000004220 glutamic acid Substances 0.000 claims description 12
- 235000013922 glutamic acid Nutrition 0.000 claims description 12
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 claims description 12
- 239000002096 quantum dot Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001338 self-assembly Methods 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 6
- 239000003344 environmental pollutant Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 239000002135 nanosheet Substances 0.000 description 17
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 9
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 6
- 238000005034 decoration Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229940112669 cuprous oxide Drugs 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000002211 L-ascorbic acid Substances 0.000 description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- NHNKWEHVEHQUDE-UHFFFAOYSA-M lithium ethanol hydroxide Chemical compound [Li+].[OH-].CCO NHNKWEHVEHQUDE-UHFFFAOYSA-M 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- XKKVXDJVQGBBFQ-UHFFFAOYSA-L zinc ethanol diacetate Chemical compound C(C)O.C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-] XKKVXDJVQGBBFQ-UHFFFAOYSA-L 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明公开了一种低维自组装花状Cu2O‑ZnO催化剂的制备方法及应用，属于光催化材料的制备领域，通过将花状Cu2O或花状ZnO超声分散于溶液后，依次加入乙酸锌醇溶液、氢氧化锂醇溶液或者依次加入氢氧化锂、氯化铜和抗坏血酸，待反应后，冷却至室温，取出经离心清洗、干燥，即得花状Cu2O‑ZnO催化剂。本发明的有益效果是：通过水热法合成花状Cu2O或花状ZnO，然后再利用湿化学法，获得低维自组装花状Cu2O‑ZnO催化剂，改进了单一催化剂的缺点，即降低单纯Cu2O光生电子‑空穴的复合，扩宽单纯ZnO的光响应范围，既能实现对太阳光全波段光进行吸收又能提高其光电转化效率，同时还能抑制载流子的复合，全方位提高光催化效率。
The invention discloses a preparation method and application of a low-dimensional self-assembled flower-like Cu 2 O - ZnO catalyst, and belongs to the field of preparation of photocatalytic materials. Zinc acetate alcohol solution, lithium hydroxide alcohol solution or lithium hydroxide, copper chloride and ascorbic acid are added in sequence, after reaction, cooled to room temperature, taken out, centrifugally cleaned and dried to obtain flower-shaped Cu 2 O-ZnO catalyst. The beneficial effects of the invention are as follows: the flower-like Cu 2 O or flower-like ZnO is synthesized by a hydrothermal method, and then a low-dimensional self-assembled flower-like Cu 2 O-ZnO catalyst is obtained by a wet chemical method, which improves the shortcomings of a single catalyst, That is, the recombination of photogenerated electron-holes of pure Cu 2 O is reduced, and the photoresponse range of pure ZnO is widened, which can not only absorb the full-band sunlight of sunlight, but also improve its photoelectric conversion efficiency, and at the same time, it can suppress the carrier's emission. composite to improve the photocatalytic efficiency in an all-round way.
Description
Technical Field
The invention belongs to the field of preparation of photocatalytic materials, and particularly relates to low-dimensional self-assembled flower-shaped Cu2A preparation method and application of an O-ZnO catalyst.
Background
In recent years, the environmental damage for economic development has attracted attention from all countries, so that the research on pollutant degradation is increasing, wherein the degradation of organic substances in sewage by photocatalysis becomes one of the current research hotspots. The cuprous oxide nano material is used as a typical p-type semiconductor, the band gap is 2.17eV, compared with some traditional photocatalytic materials, the cuprous oxide has the advantages of higher utilization rate of visible light, high photocatalytic degradation efficiency, low toxicity, low cost, unique physical and chemical properties and wide application in the aspects of gas sensors, photocatalysts, lithium ion batteries and the like. Researches show that the structure and the appearance of the cuprous oxide nano material have great influence on the physical and chemical properties of the cuprous oxide nano material, and people have unique properties on the prepared structure, such as nanospheres, nano cubes, nano cages, one-dimensional nanowires and the like, in order to improve the properties of the cuprous oxide nano material. Among these morphologies, the morphology in which a three-dimensional structure is assembled from low-dimensional nanostructures has the characteristics of low density and high specific surface area and is receiving wide attention. Which has a high specific surface area and an inner contact surface, helping to obtain a sufficient diffusion path and enhanced reaction sites.
A single catalytic material has more or less defects, such as wide ZnO band gap and narrow response interval to light, and Cu2O is susceptible to recombination of photogenerated electrons-holes, resulting in limited applications. Therefore, in order to overcome the disadvantages, the construction of a heterogeneous composite phase is an alternative approach.
Accordingly, the present inventors have made extensive studies to solve the above problems and have made the present invention.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a low-dimensional self-assembly flower-shaped Cu2Preparation method of O-ZnO catalyst, and flower-like Cu synthesis by hydrothermal method2O or flower-shaped ZnO, then using wet chemical method, centrifugal cleaning with deionized water and alcohol alternatively, drying to obtain low-dimensional self-assembly flower-shaped Cu2An O-ZnO catalyst. The specific scheme is as follows:
low-dimensional self-assembly flower-shaped Cu2Preparation method of O-ZnO catalyst, flower-like Cu2Ultrasonically dispersing O or flower-shaped ZnO in the solution, sequentially adding zinc acetate alcohol solution and lithium hydroxide alcohol solution or sequentially adding lithium hydroxide, copper chloride and ascorbic acid, reacting, cooling to room temperature, taking out, centrifugally cleaning and drying to obtain the low-dimensional self-assembled flower-shaped Cu2An O-ZnO catalyst.
Preferably, flower-like Cu2Dispersing O in the solution by ultrasonic, sequentially adding a zinc acetate alcohol solution and a lithium hydroxide alcohol solution, heating in a water bath for reaction, cooling to room temperature, taking out, alternately centrifuging and cleaning by using deionized water and ethanol, and drying in vacuum at 60 ℃ for 6 hours to obtain the low-dimensional self-assembled flower-shaped Cu2An O-ZnO catalyst.
Preferably, the mass percent of the ZnO quantum dots is 1-15wt%, the water bath temperature is 60-80 ℃, and the time is 15-20 min.
Preferably, the concentration of the zinc acetate is 12mg/ml, the concentration of the lithium hydroxide is 5mg/ml, and the volume ratio of the zinc acetate to the lithium hydroxide is 1: 1, the solution is ethanol or methanol.
Preferably, the flower-like Cu2The preparation process of O comprises the steps of dissolving copper nitrate, glutamic acid, glycine, sodium dihydrogen phosphate dihydrate and NaOH in deionized water, stirring to fully dissolve the copper nitrate, the glutamic acid, the glycine, the sodium dihydrogen phosphate dihydrate and the NaOH, then putting the mixture into a reaction kettle, carrying out hydrothermal reaction, cooling to room temperature, taking out the mixture, carrying out alternate centrifugal cleaning by the deionized water and ethanol, and carrying out vacuum drying at 60 ℃.
Preferably, the mass ratio of copper nitrate, glutamic acid, glycine, sodium dihydrogen phosphate dihydrate and NaOH is 4.2: 6: 6: 5: 19, the volume of the deionized water is 100-200 ml.
Preferably, the stirring speed is 100-200rpm, the stirring time is 10-30min, the hydrothermal reaction temperature is 140-160 ℃, and the reaction time is 2-4 h.
Preferably, after flower-shaped ZnO is ultrasonically dispersed in the solution, lithium hydroxide, copper chloride and ascorbic acid are sequentially added, magnetic stirring reaction is carried out for 30min at the temperature of 15-20 ℃ and the speed of 100-200rpm, the mixture is cooled to room temperature, and then the mixture is taken out, centrifugally cleaned by deionized water and ethanol alternately, and dried for 6h at the temperature of 60 ℃ in vacuum, thus obtaining the low-dimensional self-assemblyFilling flower shaped Cu2An O-ZnO catalyst.
Preferably, Cu2The mass percentage of the O quantum dots is 1-20wt%, and the concentrations of the lithium hydroxide, the copper chloride and the ascorbic acid are 0.1mol/l, 0.05mol/l and 0.025mol/l respectively.
Preferably, the flower-like ZnO is prepared by sequentially adding a zinc acetate solution and a sodium hydroxide solution into a citric acid solution, adding 20ml of ethanol, stirring for reaction, transferring the mixed solution into a reaction kettle for hydrothermal reaction, cooling to room temperature, taking out, centrifuging with deionized water and ethanol, and vacuum-drying at 80 ℃.
Preferably, the concentration of citric acid is 0.05g/ml, the concentration of zinc acetate is 0.15-0.02g/ml, the concentration of NaOH is 0.014-0.05g/ml, and the volume ratio is 1: (2-3): 2, the hydrothermal reaction temperature is 160-.
The low-dimensional self-assembly flower-shaped Cu prepared by the method2Application of O-ZnO catalyst in photocatalytic degradation of environmental pollutants and CO2Reduction and solar hydrogen production.
Has the advantages that:
the technical scheme of the invention has the following beneficial effects:
(1) synthesis of flower-like Cu by hydrothermal method2O or flower-shaped ZnO, and then obtaining the low-dimensional self-assembled flower-shaped Cu by a wet chemical method2O-ZnO catalyst, improves the defect of single catalyst, namely reduces pure Cu2The O photo-generated electron-hole recombination widens the photoresponse range of pure ZnO, can realize the absorption of sunlight full-wave band light and improve the photoelectric conversion efficiency, and can inhibit the recombination of carriers and improve the photocatalytic efficiency in all directions.
(2) By using flower-like Cu2O as core, ZnO quantum dot as decoration or flower-shaped ZnO as core, and Cu2The O nano-particles are decoration, have high specific surface area from the appearance of assembling into a three-dimensional structure, are beneficial to obtaining sufficient diffusion paths and enhanced reaction sites, and thus the catalytic efficiency of the composite catalyst is greatly improved.
(3) The flower-shaped Cu prepared by the invention2The O-ZnO catalyst can absorb the full-wave band light of sunlight and improve the photoelectric conversion efficiency, has large specific surface area, can provide more active points, and has high-efficiency photocatalytic efficiency, so that the obtained catalyst can degrade environmental pollutants and CO in photocatalysis2Has good application prospect in the fields of reduction, solar hydrogen production and the like.
(4) The invention synthesizes flower-shaped Cu by a hydrothermal method2O or flower-shaped ZnO, and then a wet chemical method is utilized to obtain the low-dimensional self-assembled flower-shaped Cu2The O-ZnO catalyst has simple preparation method and good repeatability, can be produced in large scale, and in addition, the obtained flower-shaped Cu2The O-ZnO catalyst has good chemical stability and is easy to store.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows Cu prepared according to the first embodiment of the present invention2O, scanning electron microscope photos with low magnification;
FIG. 2 shows Cu prepared by the first embodiment of the present invention2O high-power scanning electron microscope photo;
FIG. 3 is a scanning electron micrograph of ZnO prepared in example V of the present invention;
FIG. 4 is a scanning electron micrograph of ZnO prepared according to example seven of the present invention;
FIG. 5 shows Cu prepared according to example seven of the present invention2Scanning electron microscope photo of O-ZnO catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In this embodiment, flower-like Cu is synthesized by hydrothermal method2O or flower-shaped ZnO, then using wet chemical method, centrifugal cleaning with deionized water and alcohol alternatively, drying to obtain low-dimensional self-assembly flower-shaped Cu2An O-ZnO catalyst. The specific scheme is as follows:
low-dimensional self-assembly flower-shaped Cu2Preparation method of O-ZnO catalyst, flower-like Cu2Ultrasonically dispersing O or flower-shaped ZnO in the solution, sequentially adding zinc acetate alcohol solution and lithium hydroxide alcohol solution or sequentially adding lithium hydroxide, copper chloride and ascorbic acid, reacting, cooling to room temperature, taking out, centrifugally cleaning and drying to obtain the low-dimensional self-assembled flower-shaped Cu2An O-ZnO catalyst.
As a preferred embodiment, flower-shaped Cu is used2Dispersing O in the solution by ultrasonic, sequentially adding a zinc acetate alcohol solution and a lithium hydroxide alcohol solution, heating in a water bath for reaction, cooling to room temperature, taking out, alternately centrifuging and cleaning by using deionized water and ethanol, and drying in vacuum at 60 ℃ for 6 hours to obtain the low-dimensional self-assembled flower-shaped Cu2An O-ZnO catalyst.
As a preferred embodiment, the mass percent of the ZnO quantum dots is 1-15wt%, the water bath temperature is 60-80 ℃, and the time is 15-20 min.
In a preferred embodiment, the concentration of zinc acetate is 12mg/ml, the concentration of lithium hydroxide is 5mg/ml, and the volume ratio of the two is 1: 1, the solution is ethanol or methanol.
As a preferred embodiment, the flower-like Cu2O is prepared by mixing sodium sulfateDissolving copper acid, glutamic acid, glycine, sodium dihydrogen phosphate dihydrate and NaOH in deionized water, stirring to fully dissolve the copper acid, the glutamic acid, the glycine, the sodium dihydrogen phosphate dihydrate and the NaOH, then putting the mixture into a reaction kettle, carrying out hydrothermal reaction, cooling to room temperature, taking out the mixture, carrying out alternate centrifugal cleaning by the deionized water and ethanol, and carrying out vacuum drying at 60 ℃.
As a preferred embodiment, the mass ratio of copper nitrate, glutamic acid, glycine, sodium dihydrogen phosphate dihydrate and NaOH is 4.2: 6: 6: 5: 19, the volume of the deionized water is 100-200 ml.
As a preferred embodiment, the stirring speed is 100-200rpm, the stirring time is 10-30min, the hydrothermal reaction temperature is 140-160 ℃, and the reaction time is 2-4 h.
As a preferred embodiment, after flower-shaped ZnO is ultrasonically dispersed in the solution, lithium hydroxide, copper chloride and ascorbic acid are sequentially added, magnetic stirring reaction is carried out at the temperature of 15-20 ℃ and the speed of 100-200rpm for 30min, cooling is carried out to room temperature, the flower-shaped ZnO is taken out, alternately centrifugally cleaned by deionized water and ethanol, and vacuum drying is carried out at the temperature of 60 ℃ for 6h, thus obtaining the low-dimensional self-assembled flower-shaped Cu2An O-ZnO catalyst.
As a preferred embodiment, Cu2The mass percentage of the O quantum dots is 1-20wt%, and the concentrations of the lithium hydroxide, the copper chloride and the ascorbic acid are 0.1mol/l, 0.05mol/l and 0.025mol/l respectively.
In a preferred embodiment, the flower-like ZnO is prepared by sequentially adding a zinc acetate solution and a sodium hydroxide solution to a citric acid solution, adding 20ml of ethanol, stirring for reaction, transferring the mixed solution to a reaction kettle for hydrothermal reaction, cooling to room temperature, taking out, centrifuging with deionized water and ethanol, and vacuum drying at 80 ℃.
In a preferred embodiment, the citric acid concentration is 0.05g/ml, the zinc acetate concentration is 0.15-0.02g/ml, the NaOH concentration is 0.014-0.05g/ml, and the volume ratio is 1: (2-3): 2, the hydrothermal reaction temperature is 160-.
The low-dimensional self-assembly flower-shaped Cu prepared by the method2Application of O-ZnO catalyst in photocatalytic degradation of environmental pollutants and CO2Reduction and solar hydrogen production.
The flower-shaped Cu obtained by the technical scheme of the embodiment is obtained by the following groups of examples and comparative examples2The beneficial effects of the O-ZnO catalyst are further illustrated.
The first embodiment is as follows:
the embodiment is in the form of flower Cu2The synthesis method of the heterogeneous composite catalyst with O as a core and ZnO quantum dots for decoration comprises the following steps of:
step 1: flower-shaped Cu with self-assembled nanosheets2Preparation of O: dissolving 0.83g of copper nitrate trihydrate, 1.2g of glutamic acid, 1.2g of glycine, 1.0g of sodium dihydrogen phosphate dihydrate and 3.8g of NaOH in 150ml of deionized water, stirring at the rotating speed of 150rpm for 20min to dissolve the copper nitrate trihydrate, transferring the mixture into a reaction kettle to react at 160 ℃ for 2 hours, cooling to room temperature, taking out the mixture, cleaning the mixture with deionized water and ethanol, and drying the mixture in vacuum at 60 ℃ to obtain the flower-shaped Cu with the self-assembled nanosheets2O (as shown in fig. 1 and 2).
Step 2: taking the synthesized flower-shaped Cu2Dispersing O40 mg in 20ml ethanol by ultrasonic, sequentially adding 270ul of 0.012g/ml zinc acetate ethanol solution and 270ul of 0.005g/ml lithium hydroxide ethanol solution, reacting at the water bath temperature of 60 ℃ and 150rpm for 15min, cooling to room temperature, centrifugally cleaning by ethanol, and drying in vacuum at 60 ℃ for 6h to obtain the nanosheet self-assembled flower-shaped Cu2An O-ZnO catalyst.
Example two:
the embodiment is in the form of flower Cu2The synthesis method of the heterogeneous composite catalyst with O as a core and ZnO quantum dots for decoration comprises the following steps of:
step 1: flower-shaped Cu with self-assembled nanosheets2Preparation of O: dissolving 0.83g of copper nitrate trihydrate, 1.2g of glutamic acid, 1.2g of glycine, 1.0g of sodium dihydrogen phosphate dihydrate and 3.8g of NaOH in 150ml of deionized water, stirring at the rotating speed of 150rpm for 20min to dissolve the copper nitrate trihydrate, transferring the mixture into a reaction kettle to react at the temperature of 140 ℃ for 4 hours, cooling to room temperature, taking out the mixture, cleaning the mixture by using the deionized water and ethanol, and drying the mixture in vacuum at the temperature of 60 ℃ to obtain the flower-shaped Cu with the self-assembled nanosheets2O。
Step 2: taking the synthesized flower-shaped Cu2Dispersing O40 mg in 20ml ethanol by ultrasonic, then adding 450ul of 0.012g/ml zinc acetate ethanol solution and 450ul of 0.005g/ml lithium hydroxide ethanol solution in sequence, reacting for 15min at the water bath temperature of 60 ℃ at 150rpm, then cooling to room temperature, centrifugally cleaning by ethanol, and drying in vacuum for 6h at 60 ℃ to obtain the nanosheet self-assembled flower-shaped Cu2An O-ZnO catalyst.
Example three:
the embodiment is in the form of flower Cu2The synthesis method of the ZnO quantum dot decorated heterogeneous composite catalyst with O as a core comprises the following steps:
step 1: flower-shaped Cu with self-assembled nanosheets2Preparation of O: dissolving 0.83g of copper nitrate trihydrate, 1.2g of glutamic acid, 1.2g of glycine, 1.0g of sodium dihydrogen phosphate dihydrate and 3.8g of NaOH in 150ml of deionized water, stirring at the rotating speed of 150rpm for 20min to dissolve the copper nitrate trihydrate, transferring the mixture into a reaction kettle to react at the temperature of 140 ℃ for 4 hours, cooling to room temperature, taking out the mixture, cleaning the mixture by using the deionized water and ethanol, and drying the mixture in vacuum at the temperature of 60 ℃ to obtain the flower-shaped Cu with the self-assembled nanosheets2O。
Step 2: taking the synthesized flower-shaped Cu2Dispersing O40 mg in 20ml ethanol by ultrasonic, then sequentially adding 1.5ml of 0.012g/ml zinc acetate ethanol solution and 1.5ml of 0.005g/ml lithium hydroxide ethanol solution, reacting for 15min at the water bath temperature of 60 ℃ at 150rpm, then cooling to room temperature, centrifugally cleaning by ethanol, and drying in vacuum at 60 ℃ for 6h to obtain the nanosheet self-assembled flower-shaped Cu2An O-ZnO catalyst.
Example four:
in this example, Cu is grown with flower-like ZnO as a nucleus2Method for the synthesis of O nanoparticle decorated heterogeneous composite catalysts, in which Cu2The mass percent of the O quantum dots is 1wt%, and the method comprises the following steps:
step 1: dissolving 0.5g of citric acid in 10ml of deionized water, dissolving 0.58g of zinc acetate in 30ml of deionized water, dissolving 1.04g of NaOH in 20ml of water, then slowly and sequentially dripping the zinc acetate solution and the sodium hydroxide solution into the citric acid solution, then dripping 10ml of ethanol, reacting for 30min, transferring the solution into a reaction kettle, preserving heat at 180 ℃ for 6h, cooling to room temperature, taking out, centrifuging, and drying at 80 ℃ to obtain the nano-sheet self-assembled flower-shaped ZnO.
Step 2: 40mg of the flower-shaped ZnO prepared above is dissolved in 20ml of deionized water, after ultrasonic dispersion is carried out for 1h, 0.6ml of 0.1mol/l lithium hydroxide and 0.6ml of 0.05mol/l CuCl are sequentially added2And 0.6ml of 0.025mol/l ascorbic acid, magnetically stirring the mixture at 20 ℃ and 150rpm for reaction for 30 minutes, centrifuging the reaction product, and drying the reaction product in vacuum at 60 ℃ to obtain the nanosheet self-assembled flower-shaped Cu2An O-ZnO catalyst.
Example five:
in this example, Cu is grown with flower-like ZnO as a nucleus2Method for the synthesis of O nanoparticle decorated heterogeneous composite catalysts, in which Cu2The mass percent of the O quantum dots is 3wt%, and the method comprises the following steps:
step 1: dissolving 0.5g of citric acid in 10ml of deionized water, dissolving 0.58g of zinc acetate in 30ml of deionized water, dissolving 1.04g of NaOH in 20ml of deionized water, then slowly dripping the zinc acetate solution and the sodium hydroxide solution into the citric acid solution in sequence, then dripping 10ml of ethanol, reacting for 30min, transferring the solution into a reaction kettle, preserving the temperature for 8h at 160 ℃, cooling to room temperature, taking out, centrifuging, and drying at 80 ℃ to obtain the nano-sheet self-assembled flower-shaped ZnO (shown in figure 3).
Step 2: 40mg of the flower-shaped ZnO prepared above is dissolved in 20ml of deionized water, after 1 hour of ultrasonic dispersion, 1.7ml of 0.1mol/l lithium hydroxide and 1.7ml of 0.05mol/l CuCl are added in turn2And 1.7ml of 0.025mol/l ascorbic acid, magnetically stirring the mixture at 20 ℃ and 150rpm for reaction for 30 minutes, centrifuging the reaction product, and drying the reaction product in vacuum at 60 ℃ to obtain the nanosheet self-assembled flower-shaped Cu2An O-ZnO catalyst.
Example six:
in this example, Cu is grown with flower-like ZnO as a nucleus2Method for the synthesis of O nanoparticle decorated heterogeneous composite catalysts, in which Cu2The mass percent of the O quantum dots is 5wt%, and the method comprises the following steps:
step 1: dissolving 0.5g of citric acid in 10ml of deionized water, dissolving 0.58g of zinc acetate in 30ml of deionized water, dissolving 1.04g of NaOH in 20ml of water, then slowly and sequentially dripping the zinc acetate solution and the sodium hydroxide solution into the citric acid solution, then dripping 10ml of ethanol, reacting for 30min, transferring the solution into a reaction kettle, preserving heat at 180 ℃ for 6h, cooling to room temperature, taking out, centrifuging, and drying at 80 ℃ to obtain the nano-sheet self-assembled flower-shaped ZnO.
Step 2: dissolving 20mg of the flower-shaped ZnO prepared in the above into 20ml of deionized water, ultrasonically dispersing for 1h, and then sequentially adding 0.8ml of 0.1mol/l lithium hydroxide and 0.8ml of 0.05mol/l CuCl2And 0.8ml of 0.025mol/l ascorbic acid, magnetically stirring and reacting for 30 minutes at 20 ℃ and 150rpm, centrifuging, and drying in vacuum at 60 ℃ to obtain the nanosheet self-assembled flower-shaped Cu2An O-ZnO catalyst.
Example seven:
in this example, Cu is grown with flower-like ZnO as a nucleus2Method for the synthesis of O nanoparticle decorated heterogeneous composite catalysts, in which Cu2The mass percent of the O quantum dots is 20wt%, and the method comprises the following steps:
step 1: dissolving 0.5g of citric acid in 10ml of deionized water, dissolving 0.029g of zinc acetate in 20ml of ethanol, dissolving 0.27g of NaOH in 20ml of water, then slowly dripping the zinc acetate solution and the sodium hydroxide solution into the citric acid solution in sequence, reacting for 30min, transferring the solution into a reaction kettle, preserving the temperature at 180 ℃ for 6h, cooling to room temperature, taking out, centrifuging, and drying at 80 ℃ to obtain the nanorod self-assembled flower-shaped ZnO (shown in figure 4).
Step 2: dissolving 20mg of the flower-shaped ZnO prepared in the above into 20ml of deionized water, ultrasonically dispersing for 1h, and then sequentially adding 6ml of 0.1mol/l lithium hydroxide and 6ml of 0.05mol/l CuCl2And 6ml of 0.025mol/l ascorbic acid, magnetically stirring the mixture at 20 ℃ and 150rpm for reaction for 30 minutes, centrifuging the reaction product, and drying the reaction product in vacuum at 60 ℃ to obtain the nanorod self-assembled flower-shaped Cu2An O-ZnO catalyst (as shown in figure 5).
FIGS. 1 and 2 show Cu prepared in example one2O low power scanning electron microscope photo and high power scanning electron microscope photo, showing that the Cu is prepared2The shape of O is the flower shape of a nano sheet, the size is uniform, and the dispersity is good; FIG. 3 is a scanning electron microscope photograph of ZnO prepared in example V, which shows that the prepared ZnO is in the form of a nanosheet and has good dispersibility; FIGS. 4 and 5 show ZnO and Cu, respectively, prepared in EXAMPLE VII2Scanning electron microscope photographs of the O-ZnO catalyst show that the prepared ZnO and Cu2The shapes of the O-ZnO catalysts are all flower shapes of nanorods.
The invention synthesizes flower-shaped Cu by a hydrothermal method2O or flower-shaped ZnO, and then obtaining the low-dimensional self-assembled flower-shaped Cu by a wet chemical method2O-ZnO catalyst, improves the defect of single catalyst, namely reduces pure Cu2The O photo-generated electrons and holes are compounded, the photoresponse range of pure ZnO is widened, the full-wave-band light of sunlight can be absorbed, the photoelectric conversion efficiency of the pure ZnO photo-generated electrons and holes can be improved, the compounding of carriers can be inhibited, and the photocatalytic efficiency is improved in all directions; furthermore, by using flower-like Cu2O as core, ZnO quantum dot as decoration or flower-shaped ZnO as core, and Cu2The O nano-particles are decoration, have high specific surface area from the appearance of assembling into a three-dimensional structure, are beneficial to obtaining sufficient diffusion paths and enhanced reaction sites, and thus the catalytic efficiency of the composite catalyst is greatly improved. The flower-shaped Cu prepared by the invention2The O-ZnO catalyst can absorb the full-wave band light of sunlight and improve the photoelectric conversion efficiency, has large specific surface area, can provide more active points, and has high-efficiency photocatalytic efficiency, so that the obtained catalyst can degrade environmental pollutants and CO in photocatalysis2Has good application prospect in the fields of reduction, solar hydrogen production and the like. Finally, the invention synthesizes flower-shaped Cu by a hydrothermal method2O or flower-shaped ZnO, and then a wet chemical method is utilized to obtain the low-dimensional self-assembled flower-shaped Cu2The O-ZnO catalyst has simple preparation method and good repeatability, can be produced in large scale, and the obtained flower-shaped Cu2The O-ZnO catalyst has good chemical stability and is easy to store.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Low-dimensional self-assembly flower-shaped Cu2O-ZnOA process for the preparation of a catalyst, characterized in that,
flower-shaped Cu2Ultrasonically dispersing O or flower-shaped ZnO in the solution, sequentially adding zinc acetate alcohol solution and lithium hydroxide alcohol solution or sequentially adding lithium hydroxide, copper chloride and ascorbic acid, reacting, cooling to room temperature, taking out, centrifugally cleaning, and drying to obtain flower-shaped Cu2An O-ZnO catalyst.
2. The low dimensional self-assembled flower-like Cu of claim 12The preparation method of the O-ZnO catalyst is characterized in that flower-shaped Cu is added2Dispersing O in the solution by ultrasonic, sequentially adding zinc acetate alcohol solution and lithium hydroxide alcohol solution, heating in water bath for reaction, cooling to room temperature, taking out, alternately centrifuging and cleaning with deionized water and ethanol, and vacuum drying at 60 deg.C for 6h to obtain flower-like Cu2An O-ZnO catalyst.
3. The low dimensional self-assembled flower-like Cu of claim 22The preparation method of the O-ZnO catalyst is characterized in that the mass percent of ZnO quantum dots is 1-15wt%, the concentration of zinc acetate is 12mg/ml, the concentration of lithium hydroxide is 5mg/ml, and the volume ratio of the ZnO quantum dots to the zinc acetate is 1: 1, the solution is ethanol or methanol.
4. A low dimensional self-assembled flower-like Cu according to claim 1 or 22The preparation method of the O-ZnO catalyst is characterized in that the flower-shaped Cu2The preparation process of O comprises the steps of dissolving copper nitrate, glutamic acid, glycine, sodium dihydrogen phosphate dihydrate and NaOH in deionized water, stirring to fully dissolve the copper nitrate, the glutamic acid, the glycine, the sodium dihydrogen phosphate dihydrate and the NaOH, then putting the mixture into a reaction kettle, carrying out hydrothermal reaction, cooling to room temperature, taking out the mixture, carrying out alternate centrifugal cleaning by the deionized water and ethanol, and carrying out vacuum drying at 60 ℃.
5. The low dimensional self-assembled flower-like Cu of claim 42The preparation method of the O-ZnO catalyst is characterized in that the mass ratio of copper nitrate, glutamic acid, glycine, sodium dihydrogen phosphate dihydrate and NaOH is 4.2: 6: 6: 5: 19, toThe volume of the ionized water is 100-200 ml; the stirring speed is 100-200rpm, the stirring time is 10-30min, the hydrothermal reaction temperature is 140-160 ℃, and the reaction time is 2-4 h.
6. The low dimensional self-assembled flower-like Cu of claim 12The preparation method of the O-ZnO catalyst is characterized in that after flower-shaped ZnO is dispersed in solution by ultrasonic, lithium hydroxide, copper chloride and ascorbic acid are added in sequence, the mixture is magnetically stirred and reacted for 30min at the temperature of 15-20 ℃ and the speed of 100 plus 200rpm, the mixture is cooled to room temperature, taken out and is alternately centrifugally cleaned by deionized water and ethanol, and dried for 6h in vacuum at the temperature of 60 ℃ to obtain the flower-shaped Cu2An O-ZnO catalyst.
7. The low dimensional self-assembled flower-like Cu of claim 62The preparation method of the O-ZnO catalyst is characterized in that Cu2The mass percentage of the O quantum dots is 1-20wt%, and the concentrations of the lithium hydroxide, the copper chloride and the ascorbic acid are 0.1mol/l, 0.05mol/l and 0.025mol/l respectively.
8. A low dimensional self-assembled flower Cu according to claim 1 or 62The preparation method of the O-ZnO catalyst is characterized in that the flower-shaped ZnO catalyst is prepared by sequentially adding a zinc acetate solution and a sodium hydroxide solution into a citric acid solution, then adding 20ml of ethanol, stirring for reaction, transferring the mixed solution into a reaction kettle for hydrothermal reaction, cooling to room temperature, taking out the mixed solution, centrifuging with deionized water and ethanol, and drying in vacuum at 80 ℃.
9. The low dimensional self-assembled flower-like Cu of claim 82The preparation method of the O-ZnO catalyst is characterized in that the concentration of citric acid is 0.05g/ml, the concentration of zinc acetate is 0.15-0.02g/ml, the concentration of NaOH is 0.014-0.05g/ml, and the volume ratio is 1: (2-3): 2, the hydrothermal reaction temperature is 160-.
10. Low dimensional self-assembled flower-like Cu prepared by the method according to any one of claims 1 to 92Use of an O-ZnO catalyst, characterized in that the flower-like Cu2Application of O-ZnO catalyst in photocatalytic degradation of environmental pollutants and CO2Reduction and solar hydrogen production.
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