CN112473667B - Cu of different morphology and surface + Preparation method of CuO catalyst - Google Patents
Cu of different morphology and surface + Preparation method of CuO catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000010949 copper Substances 0.000 claims abstract description 41
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 13
- 239000012498 ultrapure water Substances 0.000 claims abstract description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical group O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 27
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000010301 surface-oxidation reaction Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 13
- 239000008103 glucose Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- 229960003280 cupric chloride Drugs 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
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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
-
- B01J35/23—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- 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
Abstract
The invention discloses Cu with different shapes and surfaces + The preparation method of the CuO catalyst comprises the following steps: step 1, weighing a divalent copper source and ultrapure water, uniformly stirring, and then dropwise adding sodium hydroxide to form copper hydroxide to adjust the pH value to 9-10; and 2, adding the product obtained in the step 1 into cyclohexane to form an azeotrope, then transferring the azeotrope into an oil bath pot, reacting for 0.5 to 6 hours respectively to obtain CuO precipitate solutions, and drying the obtained precipitates after centrifugal treatment to obtain the CuO catalyst. According to the preparation method, the CuO nano-materials with different shapes and surface oxidation state contents are prepared by controlling different reaction times through simple one-pot thermal reaction, and the correlation between the shapes and the oxidation states and the reaction times is researched.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to Cu with different shapes and surfaces + A preparation method of the CuO catalyst.
Background
In recent years, it has been reported that the morphology and surface valence of CuO nanostructured catalysts are critical to the catalytic performance. For controlling the morphology of the catalyst, the electrostatic stabilization and steric hindrance of a surfactant and the domain limitation of a soft template are generally utilized, but the removal of an added substance in subsequent treatment is difficult, so that the research on the morphology of the material is limited. Furthermore, the control of the oxidation state is generally achieved by electrochemical reduction or addition of a reducing agent, which makes the degree of reduction of the catalyst difficult to control, and the residual reducing agent may affect the catalytic performance. This greatly limits the study of the oxidation state. Therefore, the invention provides a simple preparation scheme, and CuO with different shapes and surface oxidation state contents can be prepared by controlling the reaction time.
Disclosure of Invention
The invention aims to provide Cu with different shapes and surfaces + The preparation method of the CuO catalyst can effectively improve the sensitivity of the glucose sensor.
The technical scheme adopted by the invention is as follows: cu of different morphology and surface + The preparation method of the CuO catalyst comprises the following steps:
and 2, adding the product obtained in the step 1 into cyclohexane to form an azeotrope, then transferring the azeotrope into an oil bath pot, reacting for 0.5 to 6 hours respectively to obtain CuO precipitate solutions, and drying the obtained precipitates after centrifugal treatment to obtain the CuO catalyst.
The technical solution adopted by the invention is also characterized in that,
in the step 1, the cupric source is cupric chloride dihydrate, the mass ratio of the cupric chloride dihydrate to the ultrapure water is 2.5-3.5, and the mass ratio of the cupric chloride dihydrate to the sodium hydroxide is 1-1.5.
The amount of sodium hydroxide in step 1 is 0.4-0.6M.
The mass ratio of the product of the step 1 to cyclohexane in the step 2 is 6-8.
In the step 2, the reaction temperature in an oil bath kettle is 80-85 ℃.
The drying temperature in the step 2 is 60 ℃, and the drying time is 6-8 h.
The beneficial effects of the invention are: through simple one-pot thermal reaction, different reaction times are controlled, cuO nano-materials with different shapes and surface oxidation state contents are prepared, and the correlation between the shapes and the oxidation states and the reaction times is researched. As a design scheme of non-noble metal catalysts with different shapes and mixed valence states, the method has the characteristics of simple manufacturing process, simple regulation and control mode, high performance and the like, and has very important significance for material preparation and development of glucose sensors.
Drawings
FIG. 1 shows Cu of different shapes and surfaces according to the present invention + Preparation method of CuO catalyst of content the morphology of CuO catalyst prepared in example 1 is shown in the figure;
FIG. 2 shows Cu of different shapes and surfaces according to the present invention + Preparation method of CuO catalyst of content the morphology of CuO catalyst prepared in example 2 is shown in the figure;
FIG. 3 shows Cu of different shapes and surfaces according to the present invention + Preparation method of CuO catalyst of content the morphology of the CuO catalyst prepared in example 3 is shown in the figure;
FIG. 4 shows Cu of different shapes and surfaces according to the present invention + Method for preparing CuO catalyst with high content the CuO catalyst prepared in example 1 was Cu 2p with high resolution 3/2 XPS spectra;
FIG. 5 shows Cu of different shapes and surfaces according to the present invention + Method for preparing CuO catalyst with high content the CuO catalyst prepared in example 2 was Cu 2p with high resolution 3/2 XPS spectra;
FIG. 6 shows Cu of different shapes and surfaces according to the present invention + Method for preparing CuO catalyst with high content the CuO catalyst prepared in example 3 was Cu 2p with high resolution 3/2 XPS spectra;
FIG. 7 shows Cu of different shapes and surfaces according to the present invention + Preparation method of CuO catalyst content test chart for glucose sensitivity of example 1;
FIG. 8 shows Cu of different shapes and surfaces according to the present invention + Preparation method of CuO catalyst content test pattern for glucose sensitivity of example 2;
FIG. 9 shows Cu of different shapes and surfaces according to the present invention + Preparation of CuO catalyst content method test chart for glucose sensitivity of example 1.
Detailed Description
The invention is further elucidated on the basis of the figures and the detailed description.
Cu with different shapes and surfaces + The preparation method of the CuO catalyst comprises the following steps:
In the above step, the cupric chloride dihydrate is used as the cupric chloride source, the mass ratio of the cupric chloride dihydrate to the ultrapure water is (2.5-3.5): 1, and the mass ratio of the cupric chloride dihydrate to the sodium hydroxide is (1-1.5): 1.
And 2, adding the product obtained in the step 1 into cyclohexane to form an azeotrope, wherein the mass ratio of the product to the cyclohexane is (6-8): 1, then moving the product into an oil bath pan, respectively reacting for 0.5-6 h at 80-85 ℃ to obtain a CuO precipitate solution, centrifuging the CuO precipitate solution, and placing the precipitate in a 60 ℃ oven for 6-8 h to obtain the CuO catalyst.
Example 1
Example 2
Respectively and sequentially adding copper chloride dihydrate and ultrapure water with the mass ratio of 3.
Example 3
Respectively and sequentially adding copper chloride dihydrate and ultrapure water with the mass ratio of 3.5 to 1 into a round-bottom flask, uniformly stirring by utilizing magnetons, then dropwise adding 0.5M sodium hydroxide solution to adjust the pH to 9, wherein the mass ratio of the copper chloride dihydrate to the sodium hydroxide is 1.
Example 4
Respectively and sequentially adding copper chloride dihydrate and ultrapure water with the mass ratio of 2.5 into a round-bottom flask, uniformly stirring by utilizing magnetons, then dropwise adding 0.5M sodium hydroxide solution to adjust the pH to 10, wherein the mass ratio of the copper chloride dihydrate to the sodium hydroxide is 1.3.
Example 5
Respectively and sequentially adding copper chloride dihydrate and ultrapure water in a mass ratio of 3.
Example 6
Respectively and sequentially adding copper chloride dihydrate and ultrapure water with the mass ratio of 3.5 into a round-bottom flask, uniformly stirring by utilizing magnetons, then dropwise adding 0.5M sodium hydroxide solution to adjust the pH to 9, wherein the mass ratio of the copper chloride dihydrate to the sodium hydroxide is 1.5.
As shown in fig. 1, 2 and 3, the appearance characterization diagrams of the CuO catalysts prepared in examples 1, 2 and 3 of the present invention are sequentially shown, and it can be seen from fig. 1 to 3 that all CuO catalysts prepared in the present invention by using different reaction times have nanosheet structures, and the surface exhibits a variation rule of rough-smooth-rough with the increase of the reaction time, wherein the CuO catalyst prepared in example 1 with a reaction time of 0.5 hour has the roughest surface and a size range of 420 to 680nm, and the CuO catalyst prepared in example 2 with a reaction time of 2 hours has the smoothest surface and a size range of 200 to 260nm. The surface of the CuO catalyst prepared in example 3 with the reaction time of 6 hours is rough again with the increase of the reaction time, and the size range is 80-300 nm. This variation in morphology and size may be due to the following: the solution concentration increases with increasing reaction time due to the azeotrope formation of water and cyclohexane, resulting in water evaporation. In addition, as reaction time and agitation increased, the interplanar spacing of the larger nanoparticles broke to form small pieces of CuO nanoplatelets, while Cu 2+ An increase in concentration will increase the nucleation rate and form smaller nanoplates. The ostwald ripening cannot be stopped, and the nanoparticles with rough surface disappear with the lapse of reaction time, and the nano-flake of CuO becomes larger with the concentration being unchanged. Eventually exhibiting a phenomenon in which the surface changes to rough-smooth-rough with increasing reaction time.
In addition, the CuO catalyst prepared by the invention has Cu on the surface + The content shows a certain change rule along with the increase of the reaction time, as shown in fig. 4, 5 and 6, which are high-resolution Cu 2p of the CuO catalyst prepared in example 1, example 2 and example 3 of the present invention respectively 3/2 XPS spectra of Cu on the surface of CuO catalyst prepared in example 1 with a reaction time of 0.5 hour + And Cu 2+ The ratio of (A) to (B) is 0.440, and the reaction time of example 2 is 2 hoursCu + And Cu 2+ In a ratio of 0.726, 6 hours Cu on the surface of the CuO catalyst prepared in example 3 + And Cu 2+ The ratio of (2) is 0.498. By comparing different reaction times surface Cu + And Cu 2+ The ratio of (A) to (B) can be found to be surface Cu + And Cu 2+ The proportion of (A) shows a certain change rule along with time. This is probably due to the fact that as the reaction time increases, solutions of different concentrations may form as the solvent evaporates, thereby affecting the oxidation state of the catalyst surface.
The CuO nano-sheets with different reaction times prepared by the method are used for testing the glucose sensitivity in a two-chamber three-electrode reaction device. CuO prepared at different reaction times was coated on a carbon cloth as a working electrode, CV test was performed in NaOH, which was an electrolyte, and then a comparative experiment of CV test was performed by adding 1mM glucose solution to the previous NaOH solution. As shown in fig. 7, 8 and 9, the current response results of the CuO catalysts prepared in example 1, example 2 and example 3 according to the present invention are compared in order. As can be seen from the figure, after glucose is added, the current becomes larger to indicate that the glucose is oxidized, namely the CuO nanosheet prepared by the invention can detect the glucose, and the CuO catalyst prepared in example 2 with the reaction time of 2 hours has a much higher change of current response after the glucose is added than the CuO catalyst prepared in example 1 with the reaction time of 0.5 hours and the CuO catalyst prepared in example 3 with the reaction time of 6 hours, which indicate that the CuO catalyst has a smaller size, a smoother surface and a Cu surface + And Cu 2+ A higher proportion of CuO has better glucose oxidation properties.
The invention provides Cu with different shapes and surfaces + The preparation method of the CuO catalyst with the content mainly comprises the addition of a template and a surfactant in the aspect of controlling the morphology of the nano material, and the morphology of the prepared material is well controlled due to the specific domain limiting effect of the template and the special electrostatic stabilization effect and steric hindrance effect of the surfactant. However, post-processing of the template and surfactant is difficult. Furthermore, the surface oxidation state is generally controlled by electrochemical reduction or by addition of a reducing agent, which makes the reduction less difficultOn the other hand, residual reducing agent may affect catalytic performance. Therefore, the CuO materials with different shapes and surface oxidation states can be simultaneously prepared by utilizing a simple one-pot heating method and only controlling different reaction times. In the process of preparing the CuO catalyst, the cyclohexane is added to form an azeotrope, so that Cu with different shapes and surfaces is realized by controlling the reaction time + Content of CuO catalyst.
As a design scheme of non-noble metal catalysts with different shapes and mixed valence states, the method has the characteristics of simple manufacturing process, simple regulation and control mode, high performance and the like, and has very important significance for material preparation and development of glucose sensors.
Claims (3)
1. Cu of different morphology and surface + The preparation method of the CuO catalyst is characterized by comprising the following steps:
step 1, weighing a divalent copper source and ultrapure water, uniformly stirring, and then dropwise adding sodium hydroxide to form copper hydroxide to adjust the pH to 9-10; the divalent copper source is copper chloride dihydrate, the mass ratio of the copper chloride dihydrate to the ultrapure water is (2.5) - (3.5);
and 2, adding the product obtained in the step 1 into cyclohexane to form an azeotrope, wherein the mass ratio of the product obtained in the step 1 to the cyclohexane is 6-8, then transferring the mixture into an oil bath pot, reacting at the temperature of 80-85 ℃ in the oil bath pot for 0.5-6 h to obtain a CuO precipitate solution, and drying the obtained precipitate after centrifugal treatment to obtain the CuO catalyst.
2. The differential morphology and surface Cu of claim 1 + The preparation method of the CuO catalyst with the content is characterized in that the mass of the sodium hydroxide in the step 1 is 0.4 to 0.6M.
3. The differential morphology and surface Cu of claim 1 + The preparation method of the CuO catalyst is characterized in that the drying temperature in the step 2 is 60 ℃, and the drying time is 6 to 8h.
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| CN100443414C (en) * | 2005-09-30 | 2008-12-17 | 南京理工大学 | Production of nanometer copper oxide with controllable microstructure |
| WO2007136488A2 (en) * | 2006-04-20 | 2007-11-29 | The Trustees Of Columbia University In The City Of New York | Copper oxide nanoparticle system |
| CN101652176B (en) * | 2007-04-10 | 2012-07-04 | 出光兴产株式会社 | Catalyst precursor and catalyst using the same |
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| Title |
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| 一维CuO纳米棒的微乳-均匀沉淀耦合法制备与结构表征;尹贻东等;《无机化学学报》;20100210(第02期);第122-128页 * |
| 不同形貌CuO的制备与表征;朱刚等;《硅酸盐通报》;20150915(第09期);第292-295页 * |
| 乙醇/水混合溶剂热法制备不同形貌的CuO晶体;鞠剑峰等;《人工晶体学报》;20100615(第03期);第224-227页 * |
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