CN112047372B - CuO porous nanosheet, preparation method thereof and application thereof in thermal catalysis and photo-thermal catalysis - Google Patents
CuO porous nanosheet, preparation method thereof and application thereof in thermal catalysis and photo-thermal catalysis Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 56
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical group [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 48
- 229940116318 copper carbonate Drugs 0.000 claims description 34
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 34
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000004202 carbamide Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 18
- 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 17
- 239000000463 material Substances 0.000 claims description 17
- 235000009518 sodium iodide Nutrition 0.000 claims description 16
- 239000000376 reactant Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 241000446313 Lamella Species 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims 1
- 150000002496 iodine Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 26
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 2
- 230000010718 Oxidation Activity Effects 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 69
- 239000000047 product Substances 0.000 description 20
- 230000003647 oxidation Effects 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000005751 Copper oxide Substances 0.000 description 8
- 229910000431 copper oxide Inorganic materials 0.000 description 8
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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Abstract
本发明公开了一种CuO多孔纳米片、其制备方法及其在热催化和光热催化方面的应用。本发明采用I离子辅助水热法制备前驱体，最终得到的CuO多孔纳米片具有较多的氧空位有利于提高催化剂的一氧化碳催化氧化活性。该CuO多孔纳米片在太阳光谱都有较强的吸收，具有高效的光热催化氧化一氧化碳的活性。本发明方法设备简单，易于操作，多孔纳米材料结晶质量好，尺寸均一，分布均匀，有利于大规模推广应用。利用光热催化，可实现无外加热源下高效的一氧化碳催化氧化反应。
The invention discloses a CuO porous nanosheet, a preparation method thereof and its application in thermal catalysis and photothermal catalysis. The present invention adopts the I ion-assisted hydrothermal method to prepare the precursor, and the finally obtained CuO porous nanosheet has more oxygen vacancies, which is beneficial to improve the carbon monoxide catalytic oxidation activity of the catalyst. The CuO porous nanosheets have strong absorption in the solar spectrum and have efficient photothermal catalytic oxidation activity of carbon monoxide. The method of the invention has the advantages of simple equipment, easy operation, good crystal quality, uniform size and uniform distribution of the porous nanomaterial, which is favorable for large-scale popularization and application. Using photothermal catalysis, efficient carbon monoxide catalytic oxidation reaction can be realized without external heating source.
Description
Technical Field
The invention belongs to the field of photo-thermal catalysis, and particularly relates to a CuO porous nanosheet, a preparation method thereof and application thereof in the aspects of thermal catalysis and photo-thermal catalysis.
Background
The energy crisis hastens the growth of the solar catalytic conversion industry. Solar energy can be converted into electric energy or chemical energy by methods such as solar cells, photocatalysis, photoelectrochemical cells, noble metal plasma catalysis and the like. Photothermolysis is one important class of conversion forms: the catalyst, which has strong absorption in the solar spectral range, absorbs solar energy, and its surface temperature is raised by photothermal conversion, and when the temperature exceeds the temperature of the thermocatalytic reaction on the catalyst, the catalytic reaction takes place on the catalyst surface. Photothermal catalysis has been used for a variety of catalytic reactions, including the catalytic oxidation of carbon monoxide.
Because the noble metal-based catalyst has high cost and low storage capacity, a green and environment-friendly substitute with low price has a very large market. Among them, nano CuO has attracted researchers' interest as a p-type semiconductor in a narrow bandgap photocatalyst due to its high abundance, low cost, and narrow bandgap (-1.2 eV). CuO in CO oxidation, VOC treatment, NOxThe catalyst has high activity in a plurality of catalytic fields such as removal and the like, and has good performance under the traditional thermal catalytic condition and the solar photothermal catalytic condition. The activity of the nano CuO is mainly related to the morphology, the particle size, the crystallinity, the surface state and the like of the nano CuO.
At present, the synthesis method of nano CuO mainly comprises a solid-phase reaction method, an electrochemical method, a coprecipitation method, a sol-gel method, a hydrothermal method and the like. The hydrothermal method (or the solvothermal method) is relatively simple in steps, high in product purity, rich and controllable in appearance and high in crystallinity, so that the method is widely applied, and the hydrothermal preparation methods of the copper oxide with the appearances of the nanoflower, the nanosheet, the nanosphere and the like are also reported. However, in the preparation process of the copper oxide nanosheet, strong base, surfactant or organic additive and the like are often required to be added, the process steps are complicated, large-scale application is not facilitated, and research on the copper oxide nanosheet with the porous structure is relatively less.
Disclosure of Invention
The invention aims to provide a preparation method of a CuO porous nanosheet material, which is low in cost, short in preparation period and excellent in (photo) thermocatalytic property.
The invention adopts the following technical scheme:
a CuO porous nano-sheet has a porous and flaky micro-morphology, wherein the length of the sheet layer is 1-20um, the width is 0.1-2.5um, and the thickness is 0.1-0.5 um.
The invention also provides a preparation method of the CuO porous nanosheet, which comprises the steps of solution preparation, preparation of the basic copper carbonate and copper iodide nanosheet precursor and preparation of the CuO porous nanosheet.
The preparation method comprises the following specific steps:
1) solution preparation: preparing water or ethanol solution containing copper salt, iodized salt and alkaline reactant;
2) preparing a precursor of basic copper carbonate and copper iodide nanosheets: putting the solution obtained in the step 1) into a hydrothermal kettle with a polytetrafluoroethylene inner container, carrying out hydrothermal reaction, and after the reaction is finished, carrying out centrifugal separation and drying on a reaction product to obtain a precursor of basic copper carbonate and copper iodide nanosheets.
3) Preparing a CuO porous nanosheet: and (3) carrying out heat treatment on the precursor in the step 2) in air or other oxygen-containing atmosphere to obtain the CuO porous nanosheet.
In the above technical solution, further, the copper salt in step 1) is copper nitrate, copper chloride, copper sulfate; the iodized salt is sodium iodide or potassium iodide; the alkaline reactant is urea; the relative molar ratio of the three is 1 (0.5-2) to 1-5, and the concentration of copper salt is 0.05-0.5M.
Further, the hydrothermal reaction temperature in the step 2) is 100-140 ℃, and the time is 1-48 hours.
Further, the reaction temperature of the heat treatment in the step 3) is 300-.
The CuO porous nanosheet is used as a photo-thermal catalysis material and a photo-catalysis material.
The invention provides a simpler, more efficient and more environment-friendly hydrothermal method for preparing porous sheet layered copper oxide, enriches the morphology and variety of the copper oxide reported at present, and the I ion-assisted hydrothermal process can indirectly regulate and control the oxygen vacancy of an annealing final product, so that the catalytic activity of the copper oxide porous nanosheet is improved, and the copper oxide porous nanosheet has higher application value in the aspects of thermal catalysis and photo-thermal catalysis.
The invention has the beneficial effects that:
1) the invention utilizes urea hydrolysis to release OH, creates alkaline environment, and prepares regular flaky basic carbon with good crystal qualityAnd (3) acid copper precursor. Decomposition of carbonates during annealing releasing CO2So that the final product CuO not only maintains the structure of the nano-sheet, but also obtains a large amount of pores. The prepared CuO has increased specific surface area and increased active sites; the light incident path is lengthened, the light absorption capacity is enhanced, and the photo-thermal catalytic oxidation performance is improved.
2) According to the invention, the precursor is synthesized in an I ion auxiliary mode, CuO with more surface oxygen vacancies is obtained after heat treatment, and the CuO catalytic performance is improved because the oxygen vacancies are beneficial to the oxidation process of reducing gases such as CO and the like and organic matters such as rhodamine B and the like.
3) The CuO crystal obtained by combining the I ion-assisted hydrothermal method and the heat treatment has high quality, few defect recombination centers, reduced carrier recombination probability, and is beneficial to photo-thermal catalysis and photo-catalytic oxidation, and the method is simple and convenient, low in cost and high in yield.
4) The CuO porous nanosheet provided by the invention can be directly used as a photo-thermal catalysis and photocatalytic material, can realize complete thermal catalysis at 170 ℃ and photo-thermal catalytic oxidation under the irradiation of a 300W Xe lamp for CO catalytic oxidation reaction, and has more excellent performance than commercial nano CuO.
Drawings
Fig. 1 is a scanning electron microscope SEM picture of the surface topography of the basic copper carbonate and copper iodide nanosheet precursor prepared in example 5 of the present invention.
Fig. 2 is a scanning electron microscope SEM picture of the surface morphology of the CuO porous nanosheet prepared in example 5 of the present invention.
Fig. 3 is an X-ray diffraction XRD spectrum of the basic copper carbonate and copper iodide nanosheet precursor and CuO porous nanosheet prepared in example 5 of the present invention;
FIG. 4 is a UV-Vis UV-visible absorption spectrum of CuO porous nanosheets prepared in example 5 of the present invention;
fig. 5 is a thermal catalytic oxidation CO performance curve of CuO porous nanosheets in example 10 of the present invention.
Detailed Description
The invention will be further described by way of example with reference to the accompanying drawings. It is to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art in light of the foregoing description are intended to be included within the scope of the invention. The specific process parameters and the like in the following examples are also only an example of suitable ranges, and those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values in the following examples.
Example 1
Preparation of CuO porous nano-sheet (photo) thermocatalytic material
1) Preparing 50mL of 0.1M copper nitrate aqueous solution, adding a certain amount of sodium iodide and urea, wherein the molar ratio of copper nitrate to sodium iodide to urea is 1: 2: 1; stirring for 10min to dissolve.
2) Preparing a precursor of basic copper carbonate and copper iodide nanosheets: placing the reactant in the step 1) in a hydrothermal kettle containing 100ml of polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 6h at 120 ℃, repeatedly washing and centrifugally separating the reaction product with deionized water and ethanol after the reaction is finished to obtain a precursor product, and placing the precursor product in a 60 ℃ drying oven for 2h for drying to obtain the precursor of the basic copper carbonate and the copper iodide nanosheet.
3) Preparing a CuO porous nanosheet: putting the basic copper carbonate and copper iodide nanosheet precursor into an air atmosphere tube furnace, heating to 350 ℃ at a speed of 5 ℃/min, preserving heat for 1.5h, and carrying out heat treatment to obtain the CuO porous nanosheet, wherein the length of a lamella is 2-20um, the width is 0.2-3um, and the thickness is 0.1-0.8 um.
Example 2
Preparation of CuO porous nano-sheet (photo) thermocatalytic material
1) Preparing 50mL of 0.5M copper nitrate aqueous solution, adding a certain amount of sodium iodide and urea, wherein the molar ratio of copper sulfate to sodium iodide to urea is 1: 0.5: 1; stirring for 10min to dissolve the solute completely.
2) Preparing a precursor of basic copper carbonate and copper iodide nanosheets: placing the reactant in the step 1) in a hydrothermal kettle containing 100ml of polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 9h at 120 ℃, repeatedly washing and centrifugally separating the reaction product with deionized water and ethanol after the reaction is finished to obtain a precursor product, and placing the precursor product in a 60 ℃ drying oven for 2h for drying to obtain the precursor of the basic copper carbonate and the copper iodide nanosheet.
3) Preparing a CuO porous nanosheet: putting the basic copper carbonate and copper iodide nanosheet precursor into an air atmosphere tube furnace, heating to 350 ℃ at a speed of 5 ℃/min, preserving heat for 1.5h, and carrying out heat treatment to obtain the CuO porous nanosheet, wherein the length of a lamella is 1-16um, the width is 0.2-2um, and the thickness is 0.1-0.6 um.
Example 3
Preparation of CuO porous nano-sheet (photo) thermocatalytic material
1) Preparing 50mL of 0.05M copper nitrate aqueous solution, adding a certain amount of potassium iodide and urea, wherein the molar ratio of copper nitrate to potassium iodide to urea is 1: 2: 5; stirring for 10min to dissolve the solute completely.
2) Preparing a precursor of basic copper carbonate and copper iodide nanosheets: placing the reactant in the step 1) in a hydrothermal kettle containing 100ml of polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 9h at 120 ℃, repeatedly washing and centrifugally separating the reaction product with deionized water and ethanol after the reaction is finished to obtain a precursor product, and placing the precursor product in a 60 ℃ drying oven for 2h for drying to obtain the precursor of the basic copper carbonate and the copper iodide nanosheet.
3) Preparing a CuO porous nanosheet: putting the basic copper carbonate and copper iodide nanosheet precursor into an air atmosphere tube furnace, heating to 350 ℃ at a speed of 5 ℃/min, preserving heat for 1.5h, and carrying out heat treatment to obtain the CuO porous nanosheet, wherein the length of a lamella is 1-16um, the width is 0.2-2um, and the thickness is 0.1-0.6 um.
Example 4
Preparation of CuO porous nano-sheet (photo) thermocatalytic material
1) Preparing 50mL of copper chloride aqueous solution with the concentration of 0.1M, adding a certain amount of potassium iodide and urea, wherein the molar ratio of copper chloride to potassium iodide to urea is 1: 0.5: 5; stirring for 10min to dissolve the solute completely.
2) Preparing a precursor of basic copper carbonate and copper iodide nanosheets: placing the reactant in the step 1) in a hydrothermal kettle containing 100ml of polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 9h at 120 ℃, repeatedly washing and centrifugally separating the reaction product with deionized water and ethanol after the reaction is finished to obtain a precursor product, and placing the precursor product in a 60 ℃ drying oven for 2h for drying to obtain the precursor of the basic copper carbonate and the copper iodide nanosheet.
3) Preparing a CuO porous nanosheet: placing the basic copper carbonate and copper iodide nanosheet precursor in an air atmosphere tube furnace, heating to 350 ℃ at a speed of 5 ℃/min, preserving heat for 1.5h, and carrying out heat treatment to obtain the CuO porous nanosheet, wherein the length of a lamella is 1-10um, the width is 0.2-1.5um, and the thickness is 0.1-0.4 um.
Example 5
Preparation of CuO porous nano-sheet (photo) thermocatalytic material
1) Preparing 50mL of 0.1M copper nitrate aqueous solution, adding a certain amount of sodium iodide and urea, wherein the molar ratio of copper nitrate to sodium iodide to urea is 1: 1: 2; stirring for 10min to dissolve.
2) Preparing a precursor of basic copper carbonate and copper iodide nanosheets: placing the reactant in the step 1) in a hydrothermal kettle containing 100ml of polytetrafluoroethylene liner, carrying out hydrothermal reaction for 12h at 120 ℃, repeatedly cleaning and centrifugally separating a reaction product by using deionized water and ethanol after the reaction is finished to obtain a precursor product, and placing the precursor product in a drying oven at 60 ℃ for 2h for drying to obtain a precursor of basic copper carbonate and copper iodide nanosheets, wherein the SEM surface appearance is shown in figure 1, the solid nanosheets with smooth surfaces are obtained, and the XRD diffraction pattern is shown in figure 3.
3) Preparing a CuO porous nanosheet: placing the basic copper carbonate and copper iodide nanosheet precursor in an air atmosphere tube furnace, heating to 350 ℃ at a speed of 5 ℃/min, preserving heat for 1.5h, and performing heat treatment to obtain the porous nanosheet. As shown in FIG. 2, the sheet has a length of 3-10um, a width of 0.4-1.5um, and a thickness of 0.1-0.3 um. The obtained nanosheet XRD diffraction pattern is as shown in figure 3, each peak corresponds to a standard diffraction peak of CuO, no other impurity diffraction peaks appear, and the peak intensity is high, which indicates that the annealed product is CuO and the crystallization quality is high. The ultraviolet-visible light absorption spectrum of the copper oxide nanosheet is shown in fig. 4, and the ultraviolet-visible light absorption spectrum shows that the nanosheet has strong absorption in the whole ultraviolet and visible light range (400-700 nm).
Example 6
Preparation of CuO porous nano-sheet (photo) thermocatalytic material
1) Solution: preparing 50mL of 0.1M copper nitrate aqueous solution, adding a certain amount of sodium iodide and urea, wherein the molar ratio of copper nitrate to sodium iodide to urea is 1: 1: 2; stirring for 10min to dissolve the solute completely.
2) Preparing a precursor of basic copper carbonate and copper iodide nanosheets: placing the reactant in the step 1) in a hydrothermal kettle containing 100ml of a polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 1h at 140 ℃, repeatedly washing and centrifugally separating a reaction product by using deionized water and ethanol after the reaction is finished to obtain a precursor product, and placing the precursor product in a 60 ℃ drying oven for 2h for drying to obtain the precursor of the basic copper carbonate and the copper iodide nanosheet.
3) Preparing a CuO porous nanosheet: placing the basic copper carbonate and copper iodide nanosheet precursor in an air atmosphere tube furnace, heating to 350 ℃ at a speed of 5 ℃/min, preserving heat for 1.5h, and carrying out heat treatment to obtain the CuO porous nanosheet, wherein the length of a lamella is 2-10um, the width is 0.4-1.8um, and the thickness is 0.1-0.3 um.
Example 7
Preparation of CuO porous nano-sheet (photo) thermocatalytic material
1) Solution: preparing 50mL of 0.1M copper nitrate aqueous solution, adding a certain amount of sodium iodide and urea, wherein the molar ratio of copper nitrate to sodium iodide to urea is 1: 1: 2; stirring for 10min to dissolve the solute completely.
2) Preparing a precursor of basic copper carbonate and copper iodide nanosheets: and (2) placing the reactant in the step 1) in a hydrothermal kettle containing 100ml of a polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 48h at 100 ℃, repeatedly washing and centrifugally separating a reaction product by using deionized water and ethanol after the reaction is finished to obtain a precursor product, and placing the precursor product in a 60 ℃ drying oven for 2h for drying to obtain the precursor of the basic copper carbonate and the copper iodide nanosheet.
3) Preparing a CuO porous nanosheet: placing the basic copper carbonate and copper iodide nanosheet precursor in an air atmosphere tube furnace, heating to 350 ℃ at a speed of 5 ℃/min, preserving heat for 1.5h, and carrying out heat treatment to obtain the CuO porous nanosheet, wherein the length of a lamella is 1-8um, the width is 0.1-1.8um, and the thickness is 0.1-0.3 um.
Example 8
Preparation of CuO porous nano-sheet (photo) thermocatalytic material
1) Solution: preparing 50mL of 0.1M copper nitrate aqueous solution, adding a certain amount of sodium iodide and urea, wherein the molar ratio of copper nitrate to sodium iodide to urea is 1: 1: 2; stirring for 10min to dissolve the solute completely.
2) Preparing a precursor of basic copper carbonate and copper iodide nanosheets: placing the reactant in the step 1) in a hydrothermal kettle containing 100ml of polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 12h at 120 ℃, repeatedly washing and centrifugally separating the reaction product with deionized water and ethanol after the reaction is finished to obtain a precursor product, and placing the precursor product in a 60 ℃ drying oven for 2h for drying to obtain the precursor of the basic copper carbonate and the copper iodide nanosheet.
3) Preparing a CuO porous nanosheet: placing the basic copper carbonate and copper iodide nanosheet precursor in an air atmosphere tube furnace, heating to 300 ℃ at a speed of 5 ℃/min, preserving heat for 5h, and carrying out heat treatment to obtain the CuO porous nanosheet, wherein the length of a lamella layer is 1-10um, the width is 0.5-2.0um, and the thickness is 0.1-0.5 um.
Example 9
Preparing a CuO porous nanosheet (photo) thermocatalytic material.
1) Solution: preparing 50mL of 0.1M copper nitrate aqueous solution, adding a certain amount of sodium iodide and urea, wherein the molar ratio of copper nitrate to sodium iodide to urea is 1: 1: 2; stirring for 10min to dissolve the solute completely.
2) Preparing a precursor of basic copper carbonate and copper iodide nanosheets: placing the reactant in the step 1) in a hydrothermal kettle containing 100ml of polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 12h at 120 ℃, repeatedly washing and centrifugally separating the reaction product with deionized water and ethanol after the reaction is finished to obtain a precursor product, and placing the precursor product in a 60 ℃ drying oven for 2h for drying to obtain the precursor of the basic copper carbonate and the copper iodide nanosheet.
3) Preparing a CuO porous nanosheet: placing the basic copper carbonate and copper iodide nanosheet precursor in an air atmosphere tube furnace, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 0.5h, and carrying out heat treatment to obtain the CuO porous nanosheet, wherein the length of a lamella is 1-8um, the width is 0.2-1.3um, and the thickness is 0.1-0.3 um.
Example 10
And testing the thermocatalysis performance of the CuO porous nanosheet.
1) 50mg of the CuO porous nanosheet (photo) thermal catalytic material obtained in example 5 is placed in a quartz tube reactor; the mixed gas containing 1% CO, 7% O2 and 92% Ar enters from one end of the quartz tube, and is discharged to the gas washing bottle from the other end.
2) Testing the thermal catalysis performance: the quartz tube was placed in a tube furnace and the tube furnace started to heat up at 1 deg.C/min after the CO concentration in the reactor remained stable. CO, CO in catalytic reaction processes2The concentration is detected on line by a gas chromatograph. The CO catalytic oxidation conversion was greater than 95% at 170 ℃ in a tube furnace as shown in fig. 5.
Example 11
And testing the photo-thermal catalytic performance of the CuO porous nanosheet.
1) 50mg of the CuO porous nanosheet (photo) thermal catalytic material obtained in example 5 is placed in a quartz tube reactor; the mixed gas containing 1% CO, 7% O2 and 92% Ar enters from one end of the quartz tube, and is discharged to the gas washing bottle from the other end.
2) Testing the photo-thermal catalysis performance: the quartz tube was placed under a 300W Xe lamp while the CO concentration in the reactor remained stable. The Xe lamp was turned on at 300W to ensure uniform spot irradiation on the catalyst surface. Different light power irradiation conditions are obtained by adjusting the Xe lamp current and the relative distance of the light source and the catalyst. CO, CO in catalytic reaction processes2The concentration is detected on line by a gas chromatograph. At the luminous power of 5kW m-2Under the irradiation condition, the conversion rate of CO catalytic oxidation is more than 75%.
Comparative example 1
The specific implementation steps are basically the same as those of the example 10, except that the catalysts are respectively commercial nano CuO 50mg and P25 commercial TiO250mg, and the CO catalytic oxidation conversion rate is 1 percent and 3 percent respectively under the condition of 170 ℃ in the tubular furnace.
Comparative example 2
The specific implementation steps are basically the same as those of the example 11, except that the catalysts are respectively 50mg of commercial nano CuO and 50mg of P25 commercial TiO250mg, at an optical power of 5kW m in a 300W Xe lamp-2Under the irradiation condition, the conversion rate of CO catalytic oxidation is respectivelyIs 5% and 4%.
According to the analysis of the examples and the comparative examples, the thermal catalytic activity and the photothermal catalytic activity of the CuO porous nanosheet are much higher than those of the commercial nano CuO and the commercial P25 in the same mixed gas of 50mg of catalytic material, namely, the thermal catalytic activity and the photothermal catalytic activity of the mixed gas of 1% CO.
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| CN103058257A (en) * | 2013-01-04 | 2013-04-24 | 南京大学 | CuO ball, preparation method and use thereof, as well as visible light catalyst |
| CN106207148A (en) * | 2016-08-31 | 2016-12-07 | 青海中兴新能源有限公司 | A kind of preparation method of lithium ion battery negative material micro nano structure CuO |
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| CN106207148A (en) * | 2016-08-31 | 2016-12-07 | 青海中兴新能源有限公司 | A kind of preparation method of lithium ion battery negative material micro nano structure CuO |
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