CN111545220A - CuS/CuO/Cu nanowire heterojunction array material and preparation and application thereof - Google Patents
CuS/CuO/Cu nanowire heterojunction array material and preparation and application thereof Download PDFInfo
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- 239000002070 nanowire Substances 0.000 title claims abstract description 58
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- 239000010949 copper Substances 0.000 claims abstract description 115
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 claims abstract description 43
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
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- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
Abstract
The invention relates to a CuS/CuO/Cu nanowire heterojunction array material and a preparation method and application thereof, wherein the preparation method specifically comprises the following steps: (a) soaking the pretreated copper material in NaOH and (NH)4)2S2O8In the mixed solution, Cu (OH) grows on the copper material2A nanowire array; (b) subjecting step (a) to obtainHas Cu (OH) grown2Copper material of nanowire array is soaked in Na2And vulcanizing the S solution, taking out, washing, drying and carrying out heat treatment to obtain the CuS/CuO/Cu heterojunction array material. The nanowire heterojunction array material takes copper as a substrate material, and CuO and CuS grow on the copper in sequence from bottom to top. Compared with the prior art, the method realizes the preparation of the CuS/CuO nanowire heterojunction array on the metal Cu net, and quantitatively and controllably prepares Cu (OH)2The obtained CuS/CuO/Cu nanowire heterojunction array material has excellent photocatalytic activity and can be applied to the fields of photocatalytic degradation process, environmental pollution treatment and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to a CuS/CuO/Cu nanowire heterojunction array material and preparation and application thereof.
Background
The development of the synthesis technology of the nanometer functional material promotes the design of the nanometer functional material to develop towards the shape and components of nanometer scale. Among them, nano-scale heterostructures are in the central position in the fields of chemistry and material science. In particular, inorganic nanostructural materials with precise dimensions, shapes and dimensions are rapidly changing the understanding of material properties and material structure. In nano heterostructure materials with different morphologies, the nanowire has attracted great research interest due to its unique structural factors, such as the possibility of assembling diverse structures, the benefit of charge directional migration, and the like.
CuO is a semiconductor material with narrow band gap, good conductivity, no toxicity, low price and environmental friendliness, and is also a frequently used photocatalytic material. However, the further application of CuO in the field of photocatalysis is limited by the disadvantages of general visible light utilization rate, low charge separation efficiency, easy recombination of photogenerated electrons and holes, and the like. To overcome this disadvantage, attempts have been made to use materials such as Cu2O、TiO2、WO3、BiVO4Metal organic frame structure, carbon material and polymer, etc. are compounded or doped with CuO nano structure to prepare CuO-base composite nano material. Meanwhile, Kao et al (Synthesis and Photocalatic Properties of CuO-CuS Core-Shell Nanowings, materials,2019,12(7),1106) reported that CuS/CuO nanowire composite material was prepared by high-temperature gas-phase oxidation method, but the high-temperature gas-phase oxidation method has high Synthesis temperature, relatively complex preparation conditions and unsatisfactory performance of the obtained material. Meanwhile, the research on the preparation of the CuS/CuO nanowire heterojunction composite material by using the liquid phase reaction under the relatively mild condition has not been reported.
Disclosure of Invention
The invention aims to solve the problems and provide a CuS/CuO/Cu nanowire heterojunction array material and a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a CuS/CuO/Cu nanowire heterojunction array material specifically comprises the following steps:
(a) soaking the pretreated copper material in NaOH and (NH)4)2S2O8In the mixed solution, Cu (OH) grows on the copper material2A nanowire array;
(b) growing Cu (OH) on the substrate obtained in step (a)2Copper material of nanowire array is soaked in Na2And vulcanizing the S solution, taking out, washing, drying and carrying out heat treatment to obtain the CuS/CuO/Cu nanowire heterojunction array material.
Preferably, in step (a), NaOH and (NH) are added to the mixture4)2S2O8The molar ratio of (20-50) to (1-5).
Preferably, in step (a), the mixture is prepared from NaOH solution and (NH)4)2S2O8The solution is obtained by magnetically stirring and mixing until the solution is transparent, the stirring speed is 100-300 r/min, and the stirring time is 10-30 min.
Preferably, in the step (a), the copper material is sequentially and respectively washed and pretreated by dilute hydrochloric acid, deionized water and ethanol, and the copper material is a 3cm × 4cm copper net.
Preferably, in the step (a), the soaking temperature is 10-35 ℃, and the soaking time is 5-30 min.
Preferably, in the step (b), the vulcanization temperature is 20-50 ℃, and the vulcanization time is 1-240 min.
Preferably, in step (b), the Na2The concentration of the S solution is 5-30 mM.
Preferably, in the step (b), the washing is performed three times by using deionized water and absolute ethyl alcohol respectively.
Preferably, in the step (b), the drying temperature is 90-150 ℃, the drying time is 0.5-1.5 h, and the drying is carried out under the protection of a nitrogen atmosphere.
Preferably, in the step (b), the heat treatment temperature is 160-220 ℃, and the heat treatment time is 1-3 h.
The CuS/CuO/Cu nanowire heterojunction array material prepared by the preparation method takes a copper material as a base material, CuO and CuS grow on the copper material from bottom to top in sequence, the thickness of the CuS is 5-50 nm, the length of the CuS is 1-10 mu m, the thickness of the CuO is 5-50 nm, and the length of the CuO is 1-10 mu m. The mass ratio of CuS to CuO depends on the amount of conversion of the Cu salt to CuS and can be determined by the Cu2+The amount of conversion of the ions to CuS, i.e. Cu, is controlled2+The greater the amount of ion conversion to CuS, the greater the mass of CuS, and the less mass of CuO.
An application of a CuS/CuO/Cu nanowire heterojunction array material in the field of photocatalysis.
The method utilizes one-step solution reaction and drying heat treatment with mild conditions at room temperature, takes common inorganic matters as raw materials, realizes the preparation of the CuS/CuO nanowire heterojunction array on the metal Cu net, quantitatively and controllably prepares Cu (OH) through regulating and controlling experimental parameters such as the concentration of reactants, reaction time, reaction temperature and the like in the reaction process2The obtained CuS/CuO/Cu nanowire heterojunction array material has excellent photocatalytic activity, for example, visible light irradiation is 40min, the catalytic degradation rate to methylene blue is 98.6%, and good photocatalysis is shownThe performance is that the material can be applied to the fields of photocatalytic degradation process, environmental pollution treatment and the like.
Drawings
FIG. 1 is a graph comparing X-ray diffraction patterns of materials obtained in examples 1 to 4 and comparative examples 1 and 2;
FIG. 2 is a scanning electron micrograph of the material of example 2 before vulcanization;
FIG. 3 is a scanning electron micrograph of the cured material of example 2.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A CuS/CuO/Cu nanowire heterojunction array material takes copper as a substrate material, CuO and CuS grow on the copper from bottom to top in sequence, the thickness of the CuS is about 5nm, the length of the CuS is 1-10 mu m, the thickness of the CuO is 45-50 nm, the length of the CuO is 1-10 mu m, and the mass ratio of the CuS to the CuO is about 1:19(Cu is the Cu/CuO/Cu nanowire heterojunction array material)2+The conversion of the ions to CuS is about 5%), and the preparation method comprises the following steps:
25mL of 2M NaOH and 25mL of 0.1M (NH) were added at room temperature4)2S2O8Mixing, magnetically stirring at 100r/min for 0.5 hr to transparent, soaking copper net (3cm × 4cm) cleaned with diluted hydrochloric acid, distilled water and ethanol respectively into the above mixture at 20 deg.C for 5min to obtain Cu (OH)2And (4) nanowire arrays. Copper screen Cu (OH)2The nanowire array was immersed in 50mL of 5mM Na2And (3) vulcanizing in the S solution, wherein the vulcanizing temperature is 20 ℃, the vulcanizing reaction time is controlled to be 1min, and the copper mesh is taken out and washed with deionized water and absolute ethyl alcohol for three times. Then, drying for 1 hour at 90 ℃ under the protection of nitrogen; subsequently, the sample of the CuS/CuO/Cu nanowire heterojunction array material with the CuS content of about 5 wt% is obtained by heat treatment for 2 hours at 160 ℃, and the X-ray diffraction pattern of the material is specifically shown in FIG. 1, and the diffraction peak intensity is low, namely CuS is loaded on the surface of CuO.
The CuS/CuO/Cu heterojunction array material is used for a photocatalysis experiment, visible light irradiates for 40min, the catalytic degradation rate of methylene blue is 98.6%, and good photocatalysis performance is shown.
Example 2
A CuS/CuO/Cu nanowire heterojunction array material takes a copper material as a base material, CuO and CuS grow on the copper material from bottom to top in sequence, the thickness of the CuS is 5-10 nm, the length of the CuS is 1-10 mu m, the thickness of the CuO is 40-45 nm, the length of the CuO is 1-10 mu m, and the mass ratio of the CuS to the CuO is about 1:9 (Cu/CuO/Cu nanowire heterojunction array material is Cu2+The conversion of the ions to CuS is about 10%), and is prepared by the following steps:
25mL of 3M NaOH and 25mL of 0.2M (NH) were added at room temperature4)2S2O8Mixing, magnetically stirring at 200r/min for 0.5 hr to transparent, soaking copper net (3cm × 4cm) cleaned with dilute hydrochloric acid, distilled water and ethanol respectively into the above mixture at 30 deg.C for 10min to obtain Cu (OH)2The scanning electron microscope image of the nanowire array is shown in fig. 2, and the small image at the upper right corner of the image is a macroscopic image, so that the prepared material is actually in linear distribution and has a smooth and flat surface. Copper screen Cu (OH)2The nanowire array was immersed in 50mL of 10mM Na2And (3) vulcanizing in the S solution, wherein the vulcanizing temperature is 30 ℃, the vulcanizing reaction time is controlled to be 10min, and the copper mesh is taken out and washed with deionized water and absolute ethyl alcohol for three times. Then, drying for 1 hour at 110 ℃ under the protection of nitrogen; and then, carrying out heat treatment at 180 ℃ for 2 hours to obtain a CuS/CuO/Cu nanowire heterojunction array material sample with the CuS content of about 10 wt%, which is marked as CuS/CuO/Cu-10, wherein an X-ray diffraction pattern of the material is shown as a figure 1, a remarkable CuS diffraction peak appears, and a scanning electron microscope image is shown as a figure 3, and the vulcanized material has more concave-convex surfaces and is still in linear distribution. The CuS/CuO/Cu nanowire heterojunction array material has good photocatalytic performance.
Example 3
A Cu/CuO/Cu nanowire heterojunction array material takes a copper material as a substrate material, and CuO are sequentially grown on the copper material from bottom to topCuS, the thickness of the CuS is 10-20 nm, the length of the CuS is 1-10 mu m, the thickness of the CuO is 30-40 nm, the length of the CuO is 1-10 mu m, and the mass ratio of the CuS to the CuO is about 1:4 (Cu)2+The conversion of the ions to CuS is about 20%), and the preparation method comprises the following steps:
25mL of 4M NaOH and 25mL of 0.3M (NH) were added at room temperature4)2S2O8Mixing, magnetically stirring at 200r/min for 0.5 hr to transparent, soaking copper net (3cm × 4cm) cleaned with dilute hydrochloric acid, distilled water and ethanol respectively into the above mixture at 25 deg.C for 15min to obtain Cu (OH)2And (4) nanowire arrays. Copper screen Cu (OH)2The nanowire array was immersed in 50mL of 15mM Na2And (3) vulcanizing in the S solution, wherein the vulcanizing temperature is 30 ℃, the vulcanizing reaction time is controlled to be 60min, and the copper mesh is taken out and washed with deionized water and absolute ethyl alcohol for three times. Then, drying for 1 hour at 130 ℃ under the protection of nitrogen; subsequently, the sample of the CuS/CuO/Cu nanowire heterojunction array material with the CuS content of about 20 wt% can be obtained by heat treatment for 2 hours at 200 ℃, and the X-ray diffraction pattern of the material is specifically shown in figure 1, and the CuS diffraction peak is stronger, which is marked as CuS/CuO/Cu-60. The CuS/CuO/Cu nanowire heterojunction array material has good photocatalytic performance.
Example 4
A CuS/CuO/Cu nanowire heterojunction array material takes a copper material as a base material, CuO and CuS grow on the copper material from bottom to top in sequence, the thickness of the CuS is 20-50 nm, the length of the CuS is 1-10 mu m, the thickness of the CuO is 10-30 nm, the length of the CuO is 1-10 mu m, and the mass ratio of the CuS to the CuO is about 4:1 (Cu/CuO/Cu nanowire heterojunction array material is characterized in that2+About 80% or more conversion of ions to CuS) prepared by the following steps:
25mL of 5M NaOH and 25mL of 0.5M (NH) were added at room temperature4)2S2O8Mixing, magnetically stirring at 300r/min for 1 hr to obtain transparent solution, soaking copper net (3cm × 4cm) cleaned with dilute hydrochloric acid, distilled water and ethanol respectively into the above mixture at 30 deg.C for 30min to obtain Cu (OH)2And (4) nanowire arrays. Copper screen Cu (OH)2The nanowire array was immersed in 50mL of Na at a concentration of 30mM2And (3) vulcanizing in the S solution, wherein the vulcanizing temperature is 40 ℃, the vulcanizing reaction time is controlled to be 240min, and the copper mesh is taken out and washed with deionized water and absolute ethyl alcohol for three times. Then, drying for 1 hour at 150 ℃ under the protection of nitrogen; and then, carrying out heat treatment at 220 ℃ for 2 hours to obtain a CuS/CuO/Cu nanowire heterojunction array material sample with the CuS content of 80 wt%, wherein the sample is marked as CuS/CuO/Cu-240, and the X-ray diffraction pattern of the material is shown in figure 1. The CuS/CuO/Cu nanowire heterojunction array material has good photocatalytic performance.
Comparative example 1
Cu(OH)2The Cu is prepared by the following steps: 25mL of 2M NaOH and 25mL of 0.1M (NH) were added at room temperature4)2S2O8Mixing, magnetically stirring at 100r/min for 0.5 hr to transparent, soaking copper net (3cm × 4cm) cleaned with diluted hydrochloric acid, distilled water and ethanol respectively into the above mixture at 20 deg.C for 10min to obtain Cu (OH)2And (4) nanowire arrays. The copper net is taken out and washed three times by deionized water and absolute ethyl alcohol. Then, drying for 1 hour at 90 ℃ under the protection of nitrogen; thus obtaining Cu (OH)2The X-ray diffraction pattern of the material is shown in FIG. 1, and Cu (OH) with good crystallization can be seen2Diffraction peak, i.e. Cu (OH) is prepared2The Cu sample.
Comparative example 2
The CuO/Cu is prepared by the following steps: 25mL of 2M NaOH and 25mL of 0.1M (NH) were added at room temperature4)2S2O8Mixing, magnetically stirring at 100r/min for 0.5 hr to transparent, soaking copper net (3cm × 4cm) cleaned with diluted hydrochloric acid, distilled water and ethanol respectively into the above mixture at 20 deg.C for 10min to obtain Cu (OH)2And (4) nanowire arrays. The copper net is taken out and washed three times by deionized water and absolute ethyl alcohol. Then, drying for 1 hour at 90 ℃ under the protection of nitrogen; subsequently, at 160 deg.CThen, the sample is heat treated for 2 hours to obtain a CuO/Cu sample, the X-ray diffraction pattern of the material is specifically shown in FIG. 1, and a CuO diffraction peak with good crystallization can be seen, namely, the CuO/Cu sample is prepared.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a CuS/CuO/Cu nanowire heterojunction array material is characterized by comprising the following steps:
(a) soaking the pretreated copper material in NaOH and (NH)4)2S2O8In the mixed solution, Cu (OH) grows on the copper material2A nanowire array;
(b) growing Cu (OH) on the substrate obtained in step (a)2Copper material of nanowire array is soaked in Na2And vulcanizing the S solution, taking out, washing, drying and carrying out heat treatment to obtain the CuS/CuO/Cu nanowire heterojunction array material.
2. The method of claim 1, wherein in the step (a), NaOH and (NH) are added to the mixed solution4)2S2O8The molar ratio of (20-50) to (1-5).
3. The method for preparing CuS/CuO/Cu nanowire heterojunction array material as claimed in claim 1, wherein in the step (a), the copper material is respectively cleaned and pretreated by dilute hydrochloric acid, deionized water and ethanol.
4. The method for preparing a CuS/CuO/Cu nanowire heterojunction array material as claimed in claim 1, wherein in the step (a), the soaking temperature is 10-30 ℃ and the soaking time is 5-30 min.
5. The method for preparing a CuS/CuO/Cu nanowire heterojunction array material as claimed in claim 1, wherein in the step (b), the temperature for sulfurization is 20-50 ℃ and the time for sulfurization is 1-240 min.
6. The method for preparing a CuS/CuO/Cu nanowire heterojunction array material as claimed in claim 1, wherein in the step (b), the washing is performed for a plurality of times by using deionized water and absolute ethyl alcohol respectively.
7. The method for preparing a CuS/CuO/Cu nanowire heterojunction array material as claimed in claim 1, wherein in the step (b), the drying temperature is 90-150 ℃, the drying time is 0.5-1.5 h, and the drying is performed under the protection of a nitrogen atmosphere.
8. The method for preparing a CuS/CuO/Cu nanowire heterojunction array material as claimed in claim 1, wherein in the step (b), the heat treatment temperature is 160-220 ℃ and the heat treatment time is 1-3 h.
9. The CuS/CuO/Cu nanowire heterojunction array material prepared by the preparation method according to any one of claims 1 to 8, wherein the nanowire heterojunction array material takes copper as a base material, CuO and CuS grow on the copper in sequence from bottom to top, the thickness of the CuS is 5-50 nm, the length of the CuO is 1-10 μm, and the thickness of the CuO is 5-50 nm, and the length of the CuO is 1-10 μm.
10. The use of a CuS/CuO/Cu nanowire heterojunction array material according to claim 9 in the field of photocatalysis.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112951623A (en) * | 2021-01-28 | 2021-06-11 | 天津工业大学 | Copper-cobalt-zinc composite self-supporting nano array electrode material and preparation method and application thereof |
| CN113955794A (en) * | 2021-11-30 | 2022-01-21 | 西安建筑科技大学 | CuO nanowire loaded copper mesh and preparation method and application thereof |
| CN114367671A (en) * | 2021-12-13 | 2022-04-19 | 山东黄海科技创新研究院有限责任公司 | Method for growing nano-wire on foam copper |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011063087A1 (en) * | 2009-11-20 | 2011-05-26 | The Trustees Of Boston College | Ionic vacancy diffusion driven growth of aligned nanostructures |
| CN106082303A (en) * | 2016-06-07 | 2016-11-09 | 上海工程技术大学 | A kind of CuS material of flower-like structure and its preparation method and application |
| CN106902844A (en) * | 2017-02-15 | 2017-06-30 | 辽宁科技大学 | Zinc oxide zinc sulfide heterojunction nano-wire array and its preparation method and application |
| CN110237564A (en) * | 2019-05-24 | 2019-09-17 | 安徽大学 | A kind of preparation method of self-heating nano linear array foam |
| CN110849813A (en) * | 2019-11-07 | 2020-02-28 | 曲阜师范大学 | CuO-Cu2Preparation method and application of O/CM nanowire array heterostructure |
-
2020
- 2020-04-03 CN CN202010257931.5A patent/CN111545220A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011063087A1 (en) * | 2009-11-20 | 2011-05-26 | The Trustees Of Boston College | Ionic vacancy diffusion driven growth of aligned nanostructures |
| CN106082303A (en) * | 2016-06-07 | 2016-11-09 | 上海工程技术大学 | A kind of CuS material of flower-like structure and its preparation method and application |
| CN106902844A (en) * | 2017-02-15 | 2017-06-30 | 辽宁科技大学 | Zinc oxide zinc sulfide heterojunction nano-wire array and its preparation method and application |
| CN110237564A (en) * | 2019-05-24 | 2019-09-17 | 安徽大学 | A kind of preparation method of self-heating nano linear array foam |
| CN110849813A (en) * | 2019-11-07 | 2020-02-28 | 曲阜师范大学 | CuO-Cu2Preparation method and application of O/CM nanowire array heterostructure |
Non-Patent Citations (5)
| Title |
|---|
| WEI CHENHUINAN ET AL: "A highly sensitive non-enzymatic glucose sensor based on CuS nanosheets modified Cu2O/CuO nanowire arrays", 《ELECTROCHIMICA ACTA》 * |
| WU CHONGCHONG ET AL: "Fabrication of CuS/CuO nanowire heterostructures on copper mesh with improved visible light photocatalytic properties", 《JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS》 * |
| 孙和云等: "纳米 CuO 的表面硫化", 《济南大学学报(自然科学版)》 * |
| 谭亮等: "Cu_7S_4/CuO微纳米异质结构的同步合成及光催化性能研究", 《化工新型材料》 * |
| 赵金祥等: "Cu_2O/CuS复合光催化膜的制备及其性能研究", 《河南工程学院学报(自然科学版)》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112951623A (en) * | 2021-01-28 | 2021-06-11 | 天津工业大学 | Copper-cobalt-zinc composite self-supporting nano array electrode material and preparation method and application thereof |
| CN113955794A (en) * | 2021-11-30 | 2022-01-21 | 西安建筑科技大学 | CuO nanowire loaded copper mesh and preparation method and application thereof |
| CN114367671A (en) * | 2021-12-13 | 2022-04-19 | 山东黄海科技创新研究院有限责任公司 | Method for growing nano-wire on foam copper |
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