CN113713815B - Copper oxide nanotube containing oxygen vacancy and preparation method and application thereof - Google Patents

Copper oxide nanotube containing oxygen vacancy and preparation method and application thereof Download PDF

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CN113713815B
CN113713815B CN202110772888.0A CN202110772888A CN113713815B CN 113713815 B CN113713815 B CN 113713815B CN 202110772888 A CN202110772888 A CN 202110772888A CN 113713815 B CN113713815 B CN 113713815B
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copper oxide
nanotubes
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copper
cuo
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CN113713815A (en
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高山
王强
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Anhui University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • 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—
    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/802—Photocatalytic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention discloses a copper oxide nanotube containing oxygen vacancies. The invention discloses a preparation method of the copper oxide nano tube containing oxygen vacancy, which comprises the following steps: putting copper hydroxide nanotube powder into a quartz boat, and placing the quartz boat into a tube furnace for calcination in air or argon atmosphere at 200-300 ℃. Cu (OH) is obtained by simple hydrolysis reaction 2 And (3) calcining the nanotube precursor to obtain the CuO nanotube catalyst, and regulating and controlling the oxygen vacancy content under different calcining conditions. The invention discloses application of the copper oxide nanotube containing oxygen vacancies as a catalyst in photocatalytic carbon monoxide oxidation. The copper oxide nanotube obtained by the method has the advantages of high catalytic rate, high catalytic efficiency, good stability and higher practical application value.

Description

Copper oxide nanotube containing oxygen vacancy and preparation method and application thereof
Technical Field
The invention relates to the technical field of photocatalysis nano materials, in particular to a copper oxide nanotube containing oxygen vacancies, a preparation method and application thereof.
Background
Carbon monoxide (CO) is one of the important components of atmospheric pollutants. The CO in the atmosphere is mainly generated by incomplete combustion of carbon-containing fuel or under the high-temperature and high-pressure combustion condition of an internal combustion engine, and the CO in the atmospheric pollutants can influence human health, the vision of people is impaired and headache can occur due to long-time inhalation at low concentration, and the consciousness disturbance and central nervous system pathological changes can even occur due to the disposable inhalation of high-concentration CO. In practical life, the catalytic oxidation of CO is also widely applied, such as purification of CO in automobile exhaust, elimination of trace CO in a laser, and the like. Therefore, the catalytic oxidation of CO has important significance in environmental protection, life and industrial production.
The light energy is inexhaustible clean energy which is enough to meet the global requirement, so that the CO is oxidized by photocatalysis
Is considered as a very potential solution; in addition, compared with other methods, the photocatalytic oxidation of CO is usually carried out at normal temperature and normal pressure, solar energy is directly utilized, other auxiliary energy sources are not needed to be consumed, and compared with the thermal catalytic oxidation of CO, the method is more environment-friendly, and a large amount of heat energy and facility cost are saved. To date, many photocatalytic materials have been used in photocatalytic oxidation of CO, however very low catalytic rates and catalyst stability have severely hampered their practical use.
CO oxidation catalysts can be broadly divided into two broad categories, noble metal catalysts and non-noble metal catalysts. Noble metal catalysts generally have good catalytic activity, and most of the current commercial use is noble metal catalysts, such as gold catalysts, but the high cost and low stability of noble metal catalysts greatly limit the large-scale application thereof.
Although the catalytic performance of the non-noble metal catalyst is still to be improved, the content of the non-noble metal in the environment is rich, and the non-noble metal catalyst has good commercial use value. The Cu and the derivative thereof have abundant reserves in the earth, low price, no toxicity and environmental protection, and particularly the Cu and the derivative thereof have better stability, so the search of a copper-based photocatalytic CO oxidation catalyst with high selectivity, high efficiency, stability and cheapness is of great significance.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a copper oxide nanotube containing oxygen vacancies, and a preparation method and application thereof. The copper oxide nanotube catalyst prepared by the invention carries out photocatalytic oxidation on CO under the irradiation condition of visible light, and has more excellent catalytic activity and stability than a commercial CuO catalyst.
A method for preparing copper oxide nanotubes containing oxygen vacancies, comprising the steps of: and loading the copper hydroxide nanotubes into a quartz boat, and placing the quartz boat into a tube furnace for calcination in an air or argon atmosphere at 200-300 ℃.
And obtaining the black copper oxide nanotubes with different defect contents by regulating and controlling the calcination atmosphere and the calcination time. The longer the calcination time in the same atmosphere, the more defects the copper oxide nanotubes have.
Preferably, the calcination temperature is 245-255 ℃, and temperatures exceeding 300 ℃ may destroy certain tubular structures.
Preferably, the copper hydroxide nanotubes are prepared by the steps of: after copper nitrate trihydrate is dissolved in water, sodium hydroxide solution is added dropwise into the copper nitrate trihydrate, the dropping speed is 1-5 drops/second, the copper nitrate trihydrate is stirred, centrifuged, washed and dried to obtain the copper hydroxide nanotube.
Preferably, the molar ratio of copper nitrate trihydrate to sodium hydroxide is 1:1-3
Preferably, the sodium hydroxide solution is stirred for 2-10 hours after the dropwise addition is completed.
Preferably, the product after centrifugation is washed with deionized water and absolute ethanol in sequence.
Preferably, the drying temperature is 30-100deg.C and the drying time is 10-20h.
The method obtains a precursor (namely copper hydroxide) through simple hydrolysis reaction, and then obtains the copper oxide nanotubes with different oxygen vacancy contents through regulating and controlling the calcination atmosphere and the calcination time.
The obtained precursor and the copper oxide nanotubes have uniform tube length, and the tube shape of the precursor can be maintained in the calcination process; the adjustment and control of the oxygen vacancy content are realized by adjusting and controlling the calcination conditions, and the optimal calcination temperature and time are obtained.
The copper oxide nanotube containing oxygen vacancy is prepared by adopting the preparation method of the copper oxide nanotube containing oxygen vacancy.
Preferably, the copper oxide nanotubes containing oxygen vacancies have a tube length of 0.2-1 μm.
The copper oxide nanotube containing oxygen vacancies is used as a catalyst in photocatalytic carbon monoxide oxidation.
The copper oxide nanotube containing oxygen vacancy is applied to 90Kpa CO+O 2 In +Ar mixed gas (volume contents are respectively CO:1%, O) 2 :20%, ar: 79%) tested for CO oxidation performance.
Specifically, the copper oxide nanotubes containing oxygen vacancies are dispersed in absolute ethyl alcohol, then the dispersion is dripped on the surface of a glass sheet, and the glass sheet is dried and then put into a photocatalysis system, and a xenon lamp (an optical filter with the wavelength of 420nm is added) is adopted as a light source for testing. The specific operation is as follows:
opening a vacuum pump to pump redundant gas in the system, and introducing 90Kpa CO+O after reaching vacuum 2 In +Ar mixed gas (volume contents are respectively CO:1%, O) 2 :20%, ar:79 percent), opening a stirrer to circulate gas in the system, opening condensed water to maintain the temperature in the system at normal temperature (20 ℃), opening a xenon lamp for a certain time, detecting a gas product by a gas chromatograph connected with a photocatalysis system, and detecting CO according to the detected gas product 2 The amount is used to judge the degree of catalytic oxidation of CO. After the complete conversion time was determined, the cyclic operation was started to determine catalyst stability and compared to commercial CuO.
The above operation can remove the influence of ultraviolet light by adding a filter with a wavelength of 420 nm.
Compared with the prior art, the invention has the following beneficial effects:
1. the method for synthesizing the CuO nanotube catalyst by simple hydrolysis reaction and calcination technology provided by the invention can realize a large amount of synthesis and has a relatively wide application prospect in actual large-scale industrial application.
2. The invention utilizes different calcining atmospheres and different calcining times to regulate and control the oxygen vacancy content, thereby affecting the catalytic performance, and providing a method for regulating and controlling the oxygen vacancy for future work.
3. The invention provides a simple method for testing the photocatalytic CO oxidation performance of a catalyst material, and compared with other methods in documents, the adopted testing method is simple to operate and has low requirements on equipment.
4. The CuO nanotube catalyst prepared by the invention shows excellent catalytic activity and stability when used for photocatalytic CO oxidation, and completely oxidizes 90Kpa CO+O 2 +Ar mixed gas (volume contents are CO:1%, O) 2 :20%, ar: 79%) of CO, the fastest catalytic rate only requires 9min (calcination conditions: the temperature under argon atmosphere is 250 ℃, and the calcination time is 10min)；
Through illumination for 10min, the conversion rate of commercial CuO is only 25.69%, the CO conversion rate of the CuO nano tube calcined in the air atmosphere is 70-90% (different conversion rates according to the calcining time), the CO conversion rate of the CuO nano tube calcined in the argon atmosphere can reach 95-100%, and the catalytic efficiency of the CuO nano tube is superior to that of commercial CuO;
the CuO calcined for 10min at 250 ℃ in the argon atmosphere has high catalytic rate and better stability, and the catalytic activity begins to be reduced after 409 times of circulation are catalyzed. The catalyst which is simple in preparation, high in catalytic activity and good in stability has high practical application value.
Drawings
Fig. 1 is a representation of the copper hydroxide precursor obtained in examples 4-5, wherein fig. 1a is a Transmission Electron Microscope (TEM) photograph of the obtained copper hydroxide precursor and fig. 1b is an X-ray diffraction (XRD) pattern of the obtained copper hydroxide precursor.
Fig. 2 is a photograph and characterization of the obtained copper hydroxide precursor after 80-fold scaling up of the amounts of each raw material used in the original scheme of example 4, wherein fig. 2a is a photograph of the product quality and fig. 2b is a photograph of a Transmission Electron Microscope (TEM) of the obtained copper hydroxide precursor.
Fig. 3 is a Transmission Electron Microscope (TEM) photograph of CuO nanotubes obtained in examples 4 to 5, wherein fig. 3a is a TEM photograph of CuO nanotubes obtained in example 4, and fig. 3b is a TEM photograph of CuO nanotubes obtained in example 5.
FIG. 4 is an X-ray diffraction (XRD) pattern of the CuO nanotubes obtained in examples 4 to 5, wherein air was used at-250℃for 10min for the CuO nanotubes obtained in example 4, and argon was used at-250℃for 10min for the CuO nanotubes obtained in example 5.
FIG. 5 is an ultraviolet-visible absorption spectrum of the CuO nanotube obtained in examples 4-5, wherein air is at-250℃for 10min, the CuO nanotube obtained in example 4, and argon is at-250℃for 10min, the CuO nanotube obtained in example 5.
FIG. 6 is an XPS spectrum of O1s of the CuO nanotubes obtained in examples 4-5, wherein air was used at-250℃for 10min for the CuO nanotubes obtained in example 4 and argon was used at-250℃for 10min for the CuO nanotubes obtained in example 5.
FIG. 7 is a graph showing the photocatalytic CO oxidation performance (the amount of time required for a single complete conversion of CO) of the CuO nanotubes obtained in examples 4-5 versus that of commercial CuO, wherein air was used at-250℃for 10min for the CuO nanotubes obtained in example 4 and argon was used at-250℃for 10min for the CuO nanotubes obtained in example 5.
FIG. 8 is a schematic comparison of the results of the photocatalytic CO oxidation stability of the CuO nanotubes obtained in examples 4-5, wherein air is at-250deg.C for 10min for the CuO nanotubes obtained in example 4 and argon is at-250deg.C for 10min for the CuO nanotubes obtained in example 5.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
Example 1
A method for preparing copper oxide nanotubes containing oxygen vacancies, comprising the steps of:
after copper nitrate trihydrate was dissolved in water, a sodium hydroxide solution was added dropwise thereto, and the molar ratio of copper nitrate trihydrate to sodium hydroxide was 1:1, dropwise adding at a rate of 5 drops/second, stirring for 2 hours, centrifuging, washing with deionized water and absolute ethyl alcohol in sequence, and drying at 100 ℃ for 10 hours to obtain copper hydroxide nanotubes;
copper hydroxide nanotubes are placed into a quartz boat and placed into a tube furnace, and calcined in an air atmosphere at 300 ℃ for 3min.
Example 2
A method for preparing copper oxide nanotubes containing oxygen vacancies, comprising the steps of:
after copper nitrate trihydrate was dissolved in water, a sodium hydroxide solution was added dropwise thereto, and the molar ratio of copper nitrate trihydrate to sodium hydroxide was 1:3, stirring for 10 hours at the dropping rate of 1 drop/second, centrifuging, washing by adopting deionized water and absolute ethyl alcohol in sequence, and drying at 30 ℃ for 20 hours to obtain copper hydroxide nanotubes;
copper hydroxide nanotubes are placed into a quartz boat and placed into a tube furnace, and calcined in an air atmosphere at 200 ℃ for 15min.
Example 3
Step 1, 35mL of H was added to a beaker 2 O, 1.5mmol of copper nitrate trihydrate is weighed and added into the beaker, and stirred until the copper nitrate trihydrate is completely dissolved for later use. Weighing 3.75mmol sodium hydroxide solidBody was dissolved in 5mL H 2 In O, the ultrasound causes it to dissolve completely. Slowly adding the sodium hydroxide solution into the prepared copper nitrate solution at the adding rate of 1 drop/second, stirring for 4 hours, centrifuging, washing the product by deionized water for three times, and washing by absolute ethyl alcohol for three times. And (5) collecting a blue product, and drying the blue product in a constant-temperature drying oven at 60 ℃ for 12 hours to obtain a copper hydroxide precursor.
And 2, placing the blue powder obtained after the drying in the step 1 in a quartz boat, placing in a tube furnace, calcining in air at the calcining temperature of 250 ℃ for 5min at constant temperature to obtain the black CuO nanotube containing oxygen vacancies.
Example 4
The procedure is as in example 3, except that: and 2, calcining at constant temperature for 10min, and keeping other conditions unchanged.
Example 5
The procedure is as in example 4, except that: in the step 2, the calcination atmosphere is argon, and other conditions are kept unchanged.
The blue copper hydroxide precursor and the black oxygen-vacancy-containing CuO nanotubes obtained in examples 4 to 5 were characterized as follows:
(1) The result of subjecting the precursor to X-ray diffraction and electron microscope transmission is shown in FIG. 1. As can be seen from fig. 1 a: the obtained precursor is tubular; as shown in FIG. 1b, the XRD diffraction peaks of the resulting precursor can be compared with those of Cu (OH) with the card number PDF #13-0420 2 Correspondingly, the precursor is proved to be tubular Cu (OH) 2 。
The amount of each raw material used in the original scheme of example 4 was 80 times as large as the same ratio, and the obtained precursor was subjected to X-ray diffraction and electron microscopic transmission again, and the results are shown in FIG. 2. From fig. 2b, it can be seen that the tubular structure can be maintained, and it is proved that the nano-catalyst obtained by the present invention can be synthesized in a large amount, and has commercial value.
(2) The CuO nanotubes containing oxygen vacancies obtained in examples 4-5 were subjected to electron microscopy for transmission as shown in FIG. 3. As can be seen from fig. 3: the tubular structure of the CuO nanotubes obtained by calcining for 10min in air at 250 ℃ and argon atmosphere can be well maintained, and meanwhile, by exploring other calcining temperatures, the calcination at 250 ℃ is the best temperature for maintaining the tubular structure of the catalyst.
(3) The oxygen vacancy-containing CuO nanotubes obtained in examples 4 to 5 were subjected to phase analysis by XRD, as shown in fig. 4. The CuO nanotubes obtained by calcining for 10min in the air or argon atmosphere at the temperature of 250 ℃ can correspond to the CuO with the card number of PDF#48-1548, which indicates that the CuO nanotubes are obtained under different calcining atmosphere conditions.
(4) The oxygen vacancy-containing CuO nanotubes obtained in examples 4 to 5 were subjected to uv-vis absorption spectroscopy as shown in fig. 5. As can be seen from fig. 5: the difference in the absorption intensity of the CuO nanotubes obtained under different calcination atmospheres at the same calcination time for ultraviolet and visible light is small, and only affects the absorption intensity of the CuO nanotubes for infrared light with lower energy, so that the difference in the performance of the catalysts obtained in examples 4 to 5 is not due to the variation in the light absorption intensity of the catalysts, but due to the difference in the defect amount contained therein. Meanwhile, according to the related literature, it is reported that the difference in oxygen vacancy content affects the difference in infrared light absorption intensity of the oxide material, so that FIG. 5 also indirectly illustrates that the CuO nanotubes obtained in examples 4 to 5 also have different oxygen vacancy contents.
(5) The XPS spectra of O1s of the CuO nanotubes containing oxygen vacancies obtained in examples 4-5 (FIG. 6) are shown as follows: the obtained CuO nanotube contains three oxygen species, namely lattice oxygen, chemisorbed oxygen and surface hydroxyl oxygen, wherein the larger the peak area ratio of the chemisorbed oxygen is, the more oxygen vacancies the material contains. The ratio of the area of the chemisorbed oxygen peak of the CuO nanotube obtained in example 4 was 38.48% and the ratio of the area of the chemisorbed oxygen peak of the CuO nanotube obtained in example 5 was 43.33%, which indicates that the method of the present invention is feasible by controlling different calcining atmospheres to obtain CuO having different oxygen vacancies; moreover, the performance of the catalytic oxidation of CO increases with the increase of oxygen vacancies within a certain oxygen vacancy range.
By combining all the characterization results, the Cu (OH) is obtained by a simple hydrolysis reaction 2 And (3) the precursor is calcined to obtain the CuO nanotube catalyst, and the oxygen vacancy content is regulated and controlled under different calcining conditions. The Cu (OH) obtained 2 Nanotube precursorThe bulk and CuO nanotube catalyst tubes are uniform in length and the tubular shape of the precursor can be maintained during calcination.
Example 6
The procedure is as in example 4, except that: the calcination temperature in step 2 was 280℃and the other conditions were kept unchanged, and the result was close to example 3.
Example 7
The procedure is as in example 4, except that: in step 1, 4.0mmol of sodium hydroxide was added, and the other conditions were kept unchanged, and the result was close to example 3.
Example 8
The procedure is as in example 4, except that: the sodium hydroxide solution was added at a drop rate of 2 drops/sec in step 1, and the other conditions were kept unchanged, resulting in a result close to example 3.
Example 9
The procedure is as in example 4, except that: the stirring time in step 1 was 6h, the other conditions remained unchanged, and the result was close to example 3.
Example 10
12mg of the CuO nanotubes containing oxygen vacancies obtained in examples 4 to 5 above were weighed and dispersed in 500. Mu.L of absolute ethyl alcohol, respectively. 100 mu L of the uniformly dispersed mixed solution is taken by a pipetting gun with the measuring range of 20 mu L and is dripped on the surface of pi multiplied by 4cm for five times 2 After drying, the glass sheet was put into a photocatalytic system, and a xenon lamp (filter with a wavelength of 420 nm) was used as a light source for testing. The test operation procedure was as follows: opening a vacuum pump to pump redundant gas in the system, and introducing 90Kpa CO/O after reaching vacuum 2 In Ar mixed gas (volume contents are respectively CO:1%, O) 2 :20%, ar:79 percent), opening a stirrer to circulate gas in the system, opening condensed water to maintain the temperature in the system at normal temperature (20 ℃), opening a xenon lamp, detecting a gas product after a certain time by a gas chromatograph connected with a photocatalysis system, and detecting CO according to the detected gas product 2 The amount was used to determine the degree of CO oxidation.
After the complete conversion time is determined, the cyclic operation can be started to determine the catalyst stability and compare it with the catalyst performance of commercially available CuO.
Comparative tests were performed on the oxygen vacancy-containing CuO nanotubes obtained in examples 4 to 5 and commercial CuO under the same photocatalytic conditions. The conversion rate of commercial CuO is only 25.69% after illumination for 10min, the CO conversion rate of the CuO nano tube calcined in the air atmosphere is 70-90% (different conversion rates according to the calcining time), and the CO conversion rate of the CuO nano tube calcined in the argon atmosphere can reach 90-100%.
The time for one cycle of complete CO conversion of CuO nanotubes containing oxygen vacancies obtained in examples 4 and 5 was 11min and 9min, respectively, while the time required for single complete CO conversion of commercial CuO was 48min (as shown in fig. 7), i.e., the catalytic efficiency of CuO nanotubes was greatly superior to commercial CuO.
The CuO nanotubes obtained in examples 4 to 5 were subjected to a photocatalytic CO oxidation stabilization test, and the results are shown in fig. 8. The CuO nanotubes obtained in example 4 started to weaken after 328 cycles of catalysis, whereas the CuO nanotubes obtained in example 5 started to decrease in catalytic activity after 409 cycles of catalysis, not only at a fast catalytic rate, but also with better stability.
The results of the above photocatalytic test demonstrate that: the CuO nanotube obtained by the invention can be well applied to CO photocatalytic oxidation at normal temperature, has higher catalytic activity than commercial CuO, and has higher practical application value.
Example 11
The procedure is as in example 10, except that: the dispersion was carried out with 300. Mu.L of absolute ethanol, the other conditions remained unchanged, and the results obtained were close to those obtained in example 10.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (6)

1. A method for preparing a copper oxide nanotube containing oxygen vacancies, which is characterized by comprising the following steps: placing copper hydroxide nanotubes into a quartz boat and placing the quartz boat into a tube furnace for calcination in air or argon atmosphere at 200-300 ℃;
the copper hydroxide nanotubes were prepared by the following steps: dissolving copper nitrate trihydrate in water, dropwise adding sodium hydroxide solution into the solution at the dropwise adding rate of 1-5 drops/second, stirring, centrifuging, washing and drying to obtain copper hydroxide nanotubes;
the molar ratio of copper nitrate trihydrate to sodium hydroxide is 1:1-3;
stirring for 2-10h after the sodium hydroxide solution is completely dripped;
the drying temperature is 30-60 ℃ and the drying time is 10-20h.
2. The method for preparing the copper oxide nano tube containing oxygen vacancies according to claim 1, wherein the product after centrifugation is washed with deionized water and absolute ethyl alcohol in sequence.
3. Copper oxide nanotubes containing oxygen vacancies, characterized in that they are produced by a process for the preparation of copper oxide nanotubes containing oxygen vacancies according to any one of claims 1 to 2.
4. The oxygen vacancy-containing copper oxide nanotube according to claim 3, wherein the tube length of the oxygen vacancy-containing copper oxide nanotube is 0.2 to 1 μm.
5. Use of copper oxide nanotubes containing oxygen vacancies according to claim 3 or 4 as a catalyst for photocatalytic carbon monoxide oxidation.
6. A method of photocatalytic oxidation of carbon monoxide using oxygen vacancy containing copper oxide nanotubes as claimed in claim 3 or 4, comprising the steps of: dispersing the copper oxide nanotubes containing oxygen vacancies according to claim 3 or 4 in a solvent, then dripping the dispersion on the surface of a transparent carrier, drying, placing in a photocatalytic system, extracting the excess gas in the system to a vacuum state, and then introducing CO and O 2 And Ar to the system pressure of 90kPa, turning on a xenon lamp to perform photocatalysis。
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Synthesis of Cu(OH)2 and CuO nanotubes arrays on a silicon wafer;Laurent Schlur;RSC Advances(第5期);6061–6070 *
Synthesis of Different Cu(OH)2 and CuO (Nanowires, Rectangles, Seed-, Belt-, and Sheetlike) Nanostructures by Simple Wet Chemical Route;Dinesh Pratap Singh等;J. Phys. Chem. C(第113期);实验部分 *

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