CN113083277B - Preparation method and application of nano ZnO rich in oxygen vacancy for photocatalytic reduction of hexavalent uranium - Google Patents
Preparation method and application of nano ZnO rich in oxygen vacancy for photocatalytic reduction of hexavalent uranium Download PDFInfo
- Publication number
- CN113083277B CN113083277B CN202110341978.4A CN202110341978A CN113083277B CN 113083277 B CN113083277 B CN 113083277B CN 202110341978 A CN202110341978 A CN 202110341978A CN 113083277 B CN113083277 B CN 113083277B
- Authority
- CN
- China
- Prior art keywords
- zno
- solution
- hour
- rich
- uranium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 47
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000001301 oxygen Substances 0.000 title claims abstract description 39
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 37
- 230000009467 reduction Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 132
- 239000000243 solution Substances 0.000 claims abstract description 83
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 37
- 239000011701 zinc Substances 0.000 claims abstract description 33
- 239000011259 mixed solution Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 12
- 239000006228 supernatant Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 18
- 239000012498 ultrapure water Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000012159 carrier gas Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000889 atomisation Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000009832 plasma treatment Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 230000007480 spreading Effects 0.000 claims description 6
- 238000003892 spreading Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000013032 photocatalytic reaction Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- VBWSWBQVYDBVGA-NAHFVJFTSA-N uranium-234;uranium-235;uranium-238 Chemical compound [234U].[235U].[238U] VBWSWBQVYDBVGA-NAHFVJFTSA-N 0.000 claims 3
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 92
- 239000011787 zinc oxide Substances 0.000 description 61
- 238000006722 reduction reaction Methods 0.000 description 18
- 239000012459 cleaning agent Substances 0.000 description 7
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000007853 buffer solution Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002354 radioactive wastewater Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- AAORDHMTTHGXCV-UHFFFAOYSA-N uranium(6+) Chemical compound [U+6] AAORDHMTTHGXCV-UHFFFAOYSA-N 0.000 description 1
- 125000005289 uranyl group Chemical group 0.000 description 1
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium, which comprises the following steps: dropwise adding sodium hydroxide solution into zinc nitrate solution at a certain speed, stirring, ultrasonic treating, standing, pouring out supernatant, and centrifuging to obtain Zn (OH)2Precipitating; reduction of Zn (OH)2Adding the precipitate to a certain concentration of H2O2Stirring and ultrasonically treating the solution to obtain a mixed solution, transferring the mixed solution into a polytetrafluoroethylene autoclave, preserving the temperature for a certain time, naturally cooling to room temperature, washing and drying to obtain ZnO2A solid; adding ZnO2And heating the solid in air to 400-800 ℃, preserving the heat, and calcining to obtain the nano ZnO rich in oxygen vacancies. The nano ZnO prepared by the method can better treat uranium-containing wastewater; ZnO rich in oxygen vacancies is prepared by a method combining hydrothermal treatment and calcination, and has higher photocatalytic reduction capability on hexavalent uranium.
Description
Technical Field
The invention belongs to the technical field of organic and inorganic nano materials and preparation thereof, and particularly relates to a preparation method and application of nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium.
Background
Nuclear energy is considered as a new energy source capable of thoroughly solving energy problems due to its characteristics of cleanliness, economy and sustainability, and will occupy a large proportion in future energy demands.
The rapid development of nuclear power on the one hand alleviates the crisis of energy shortage and the problem of global warming, and on the other hand nuclear power is potentially dangerous in practical applications. The occurrence of nuclear accidents not only destroys the local ecological environment but also threatens the life safety of human beings. At present, the domestic and foreign needle treatment method of uranium-containing wastewater mainly comprises methods such as an adsorption method, a chemical precipitation method, a biological treatment method and the like for treating uranium-containing wastewater. The conversion of soluble U (VI) into insoluble U (IV) is an ideal strategy for treating uranium-containing wastewater. The traditional method for treating the uranium-containing wastewater has the defects of high cost, low efficiency, easy generation of secondary pollution and the like. In recent years, photocatalytic technology has been applied to the treatment of wastewater containing organic pollutants and metal ions. Compared with the traditional method for treating the uranium-containing wastewater, the method for treating the uranium-containing wastewater by using the photocatalysis technology has the advantages of environmental protection, simple operation, low cost, good reduction effect and the like. The method for treating uranium (VI) containing wastewater by using the photocatalytic technology has theoretical significance and application value, but the method for constructing the photocatalyst with high efficiency and high solar utilization rate is a challenge at present.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium, comprising the steps of:
step one, Zn (NO)3)2·6H2Adding of OAdding the zinc nitrate into deionized water, stirring for 0.5-1 hour, and carrying out ultrasonic treatment for 0.5-1 hour to obtain a zinc nitrate solution with the concentration of 0.08-0.11 mol/L;
step two, according to Zn (NO)3)2·6H2Weighing a certain amount of NaOH into ultrapure water according to the molar ratio of O to NaOH of 1:2, stirring for 0.5-1 hour, and carrying out ultrasonic treatment for 0.5-1 hour to obtain a sodium hydroxide solution;
thirdly, dropwise adding the sodium hydroxide solution into the zinc nitrate solution at a certain speed, stirring for 0.5-1 hour, carrying out ultrasonic treatment for 0.5-1 hour, standing for 2 hours, pouring out the supernatant, and centrifuging by using a centrifuge to obtain Zn (OH)2Precipitating;
step four, Zn (OH)2Adding the precipitate into 1-3 mol/L H2O2Stirring the solution for 0.5 to 1 hour, performing ultrasonic treatment for 0.5 to 1 hour to obtain a mixed solution, transferring the mixed solution into a polytetrafluoroethylene autoclave, preserving the heat for 1 to 3 hours at the temperature of between 60 and 80 ℃, naturally cooling the mixed solution to room temperature, washing the mixed solution for 3 times by using absolute ethyl alcohol and ultrapure water respectively, and finally drying the washed solution for 24 hours in a vacuum drying oven at the temperature of between 60 and 80 ℃ to obtain ZnO2A solid; taking ZnO2Uniformly spreading the solid on a magnetic boat, and treating for 50-60 seconds by using hydrogen plasma;
step five, treating the ZnO subjected to the hydrogen plasma treatment2And (3) heating the solid in the air to 400-800 ℃ at a heating rate of 3-7 ℃/min, preserving the heat for 1-3 hours, and calcining to obtain the nano ZnO rich in oxygen vacancies.
Preferably, the concentration of the sodium hydroxide solution is 0.19-0.21 mol/L.
Preferably, in the third step, a double-channel injection pump is utilized to dropwise add a sodium hydroxide solution into the zinc nitrate solution at the speed of 100 mL/h; the centrifugal speed of the centrifugal machine is 8000r/min, and the centrifugal time is 4-8 min.
Preferably, in the fourth step, the process parameters of the hydrogen plasma treatment are as follows: the pressure is 10 to 100Pa and the power is 50 to 300W.
Preferably, the process of the third step is replaced by: passing the sodium hydroxide solution through an ultrasonic atomizer to be ultrasonicAtomizing sodium hydroxide atomized substance, introducing the sodium hydroxide atomized substance into zinc nitrate solution through carrier gas, stirring for 0.5-1 hour, carrying out ultrasonic treatment for 0.5-1 hour, standing for 2 hours, pouring out supernatant, and centrifuging by using a centrifugal machine to obtain Zn (OH)2And (4) precipitating.
Preferably, the frequency of ultrasonic atomization is 1.6-1.8 MHz, and the atomization rate is 0.5-1.5 mL/min; the carrier gas is inert gas, and the flow rate of the carrier gas is 400-600 mL/min.
Preferably, said H2O2The preparation method of the solution comprises the following steps: mixing 30% of H2O2Adding deionized water to obtain H2O2And (3) solution.
Preferably, in the fifth step, ZnO is added2Uniformly placing the mixture in a rectangular boat, placing the rectangular boat in a quartz tube, heating to 300-600 ℃ at a heating rate of 3-7 ℃/min, preserving heat for 1-3 hours, and calcining to obtain the oxygen vacancy-rich nano ZnO.
Preferably, in the fourth step, before the mixed solution is transferred into a polytetrafluoroethylene autoclave, an Nd-YAG pulse laser is used for carrying out ultraviolet pulse laser irradiation on the mixed solution for 15-20 min; the wavelength of the ultraviolet pulse laser irradiation is 355nm, the pulse width is 10-20 ns, and the pulse frequency is 10-30 Hz; the single pulse energy is 20-100 mJ.
The invention also provides application of the nano ZnO rich in the oxygen vacancy in photocatalytic reduction of hexavalent uranium, which is characterized in that the nano ZnO rich in the oxygen vacancy is added into radioactive wastewater containing uranium, the radioactive wastewater containing hexavalent uranium is stirred for 120min under a dark condition, and then photocatalytic reaction is carried out under a condition that a xenon lamp simulates sunlight, so that the photocatalytic reduction of hexavalent uranium in the radioactive wastewater containing uranium is realized.
The invention at least comprises the following beneficial effects: the nano ZnO prepared by the method can better treat uranium-containing wastewater; ZnO rich in oxygen vacancies is prepared by a method combining hydrothermal treatment and calcination, and has higher photocatalytic reduction capability on hexavalent uranium.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is an SEM image of ZnO-400 after photocatalysis in accordance with the present invention;
FIG. 2 is an EDS diagram of ZnO-400 after photocatalysis in accordance with the present invention;
FIG. 3 is an SEM image of ZnO-400 prepared by the present invention;
FIG. 4 is an EDS diagram of ZnO-400 prepared in accordance with the present invention;
FIG. 5 is an XRD pattern of nano ZnO prepared by the present invention;
FIG. 6 is a standard curve of a uranium solution used in the present invention;
FIG. 7 is a photo-catalytic reduction curve of hexavalent uranium with nano ZnO prepared by the present invention;
FIG. 8 is a photo-catalytic reduction curve of hexavalent uranium with nano ZnO prepared in examples 1,4 and 5 of the present invention;
fig. 9 is a photo-catalytic reduction curve of hexavalent uranium with nano ZnO prepared in examples 4, 6, and 7 of the present invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a preparation method of nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium comprises the following steps:
step one, 2.97445g Zn (NO)3)2·6H2Adding O into 100mL of deionized water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a zinc nitrate solution;
step two, adding 0.8g of NaOH into 100mL of ultrapure water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a sodium hydroxide solution;
step three, using a double-channel injection pump to feed zinc nitrate at the speed of 100mL/hDropwise adding a sodium hydroxide solution into the solution; stirring for 1 hr, ultrasonic treating for 1 hr, standing for 2 hr, pouring out supernatant, centrifuging at 8000r/min for 5min to obtain Zn (OH)2Precipitating;
step four, Zn (OH)2The precipitate is added to 2mol/L of H2O2Stirring the solution for 1 hour, performing ultrasonic treatment for 1 hour to obtain a mixed solution, transferring the mixed solution into a polytetrafluoroethylene autoclave, preserving the heat at 75 ℃ for 2 hours, naturally cooling to room temperature, washing with absolute ethyl alcohol and ultrapure water for 3 times, and finally drying in a vacuum drying oven at 75 ℃ for 24 hours to obtain ZnO2A solid; wherein, 2mol/L of H2O2The preparation method of the solution comprises the following steps: 25.5mL of H with the mass fraction of 30 percent2O2Mixing with 99.5mL of deionized water to obtain the water-based cleaning agent;
step five, ZnO is added2Heating the solid in air to 400 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and calcining to obtain the oxygen vacancy-rich nano ZnO, namely ZnO-400.
Example 2:
a preparation method of nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium comprises the following steps:
step one, 2.97445g Zn (NO)3)2·6H2Adding O into 100mL of deionized water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a zinc nitrate solution;
step two, adding 0.8g of NaOH into 100mL of ultrapure water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a sodium hydroxide solution;
thirdly, dropwise adding a sodium hydroxide solution into the zinc nitrate solution at the speed of 100mL/h by using a double-channel injection pump; stirring for 1 hr, ultrasonic treating for 1 hr, standing for 2 hr, pouring out supernatant, centrifuging at 8000r/min for 5min to obtain Zn (OH)2Precipitating;
step four, Zn (OH)2The precipitate is added to 2mol/L of H2O2Stirring for 1 hr, ultrasonic treating for 1 hr to obtain mixed solution, transferring the mixed solution to polytetrafluoroethylene autoclave, and reacting at 7 deg.CKeeping the temperature at 5 deg.C for 2 hr, naturally cooling to room temperature, washing with anhydrous ethanol and ultrapure water for 3 times, and drying in 75 deg.C vacuum drying oven for 24 hr to obtain ZnO2A solid; wherein, 2mol/L of H2O2The preparation method of the solution comprises the following steps: 25.5mL of H with the mass fraction of 30 percent2O2Mixing with 99.5mL of deionized water to obtain the water-based cleaning agent;
step five, ZnO is added2Heating the solid in air to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and calcining to obtain the oxygen vacancy-rich nano ZnO, namely ZnO-600.
Example 3:
a preparation method of nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium comprises the following steps:
step one, 2.97445g Zn (NO)3)2·6H2Adding O into 100mL of deionized water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a zinc nitrate solution;
step two, adding 0.8g of NaOH into 100mL of ultrapure water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a sodium hydroxide solution;
thirdly, dropwise adding a sodium hydroxide solution into the zinc nitrate solution at the speed of 100mL/h by using a double-channel injection pump; stirring for 1 hr, ultrasonic treating for 1 hr, standing for 2 hr, pouring out supernatant, centrifuging at 8000r/min for 5min to obtain Zn (OH)2Precipitating;
step four, Zn (OH)2The precipitate is added to 2mol/L of H2O2Stirring the solution for 1 hour, performing ultrasonic treatment for 1 hour to obtain a mixed solution, transferring the mixed solution into a polytetrafluoroethylene autoclave, preserving the heat at 75 ℃ for 2 hours, naturally cooling to room temperature, washing with absolute ethyl alcohol and ultrapure water for 3 times, and finally drying in a vacuum drying oven at 75 ℃ for 24 hours to obtain ZnO2A solid; wherein, 2mol/L of H2O2The preparation method of the solution comprises the following steps: 25.5mL of H with the mass fraction of 30 percent2O2Mixing with 99.5mL of deionized water to obtain the water-based cleaning agent;
step five, ZnO is added2The solid is in the air, and the solid is in the air,heating to 800 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and calcining to obtain the oxygen vacancy-rich nano ZnO, namely ZnO-800.
Example 4:
a preparation method of nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium comprises the following steps:
step one, 2.97445g Zn (NO)3)2·6H2Adding O into 100mL of deionized water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a zinc nitrate solution;
step two, adding 0.8g of NaOH into 100mL of ultrapure water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a sodium hydroxide solution;
thirdly, dropwise adding a sodium hydroxide solution into the zinc nitrate solution at the speed of 100mL/h by using a double-channel injection pump; stirring for 1 hr, ultrasonic treating for 1 hr, standing for 2 hr, pouring out supernatant, centrifuging at 8000r/min for 5min to obtain Zn (OH)2Precipitating;
step four, Zn (OH)2The precipitate is added to 2mol/L of H2O2Stirring the solution for 1 hour, performing ultrasonic treatment for 1 hour to obtain a mixed solution, transferring the mixed solution into a polytetrafluoroethylene autoclave, preserving the heat at 75 ℃ for 2 hours, naturally cooling to room temperature, washing with absolute ethyl alcohol and ultrapure water for 3 times, and finally drying in a vacuum drying oven at 75 ℃ for 24 hours to obtain ZnO2A solid; taking ZnO2Uniformly spreading the solid on a magnetic boat, and treating for 50-60 seconds by using hydrogen plasma; wherein, 2mol/L of H2O2The preparation method of the solution comprises the following steps: 25.5mL of H with the mass fraction of 30 percent2O2Mixing with 99.5mL of deionized water to obtain the water-based cleaning agent; the process parameters of the hydrogen plasma treatment are as follows: the air pressure is 60Pa, and the power is 300W;
step five, ZnO is added2Heating the solid in air to 400 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and calcining to obtain the oxygen vacancy-rich nano ZnO, namely ZnO-400-1.
Example 5:
a preparation method of nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium comprises the following steps:
step one, 2.97445g Zn (NO)3)2·6H2Adding O into 100mL of deionized water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a zinc nitrate solution;
step two, adding 0.8g of NaOH into 100mL of ultrapure water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a sodium hydroxide solution;
thirdly, dropwise adding a sodium hydroxide solution into the zinc nitrate solution at the speed of 100mL/h by using a double-channel injection pump; stirring for 1 hr, ultrasonic treating for 1 hr, standing for 2 hr, pouring out supernatant, centrifuging at 8000r/min for 5min to obtain Zn (OH)2Precipitating;
step four, Zn (OH)2The precipitate is added to 2mol/L of H2O2Stirring the solution for 1 hour, performing ultrasonic treatment for 1 hour to obtain a mixed solution, and performing ultraviolet pulse laser irradiation on the mixed solution for 20min by using an Nd (yttrium aluminum garnet) YAG (yttrium aluminum garnet) pulse laser; the wavelength of the ultraviolet pulse laser irradiation is 355nm, the pulse width is 15ns, and the pulse frequency is 20 Hz; the single pulse energy is 80 mJ; transferring the irradiated mixed solution into a polytetrafluoroethylene autoclave, preserving the heat for 2 hours at 75 ℃, naturally cooling to room temperature, washing with absolute ethyl alcohol and ultrapure water for 3 times respectively, and finally drying in a vacuum drying oven at 75 ℃ for 24 hours to obtain ZnO2A solid; taking ZnO2Uniformly spreading the solid on a magnetic boat, and treating for 50-60 seconds by using hydrogen plasma; wherein, 2mol/L of H2O2The preparation method of the solution comprises the following steps: 25.5mL of H with the mass fraction of 30 percent2O2Mixing with 99.5mL of deionized water to obtain the water-based cleaning agent; the process parameters of the hydrogen plasma treatment are as follows: the air pressure is 60Pa, and the power is 300W;
step five, ZnO is added2Heating the solid in air to 400 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and calcining to obtain the oxygen vacancy-rich nano ZnO, namely ZnO-400-2.
Example 6:
a preparation method of nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium comprises the following steps:
step one, 2.97445g Zn (NO)3)2·6H2Adding O into 100mL of deionized water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a zinc nitrate solution;
step two, adding 0.8g of NaOH into 100mL of ultrapure water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a sodium hydroxide solution;
step three, the sodium hydroxide solution is ultrasonically atomized into sodium hydroxide atomized substance through an ultrasonic atomizer, the sodium hydroxide atomized substance is introduced into the zinc nitrate solution through carrier gas, the mixture is stirred for 1 hour, the mixture is ultrasonically treated for 1 hour, the mixture is kept still for 2 hours, supernatant is poured out, a centrifugal machine is used for centrifuging for 5 minutes, and the centrifuging speed is 8000r/min, so that Zn (OH) is obtained2Precipitating; the frequency of the ultrasonic atomization is 1.7MHz, and the atomization rate is 1 mL/min; the carrier gas is inert gas, and the flow rate of the carrier gas is 500 mL/min;
step four, Zn (OH)2The precipitate is added to 2mol/L of H2O2Stirring the solution for 1 hour, performing ultrasonic treatment for 1 hour to obtain a mixed solution, transferring the mixed solution into a polytetrafluoroethylene autoclave, preserving the heat at 75 ℃ for 2 hours, naturally cooling to room temperature, washing with absolute ethyl alcohol and ultrapure water for 3 times, and finally drying in a vacuum drying oven at 75 ℃ for 24 hours to obtain ZnO2A solid; taking ZnO2Uniformly spreading the solid on a magnetic boat, and treating for 50-60 seconds by using hydrogen plasma; wherein, 2mol/L of H2O2The preparation method of the solution comprises the following steps: 25.5mL of H with the mass fraction of 30 percent2O2Mixing with 99.5mL of deionized water to obtain the water-based cleaning agent; the process parameters of the hydrogen plasma treatment are as follows: the air pressure is 60Pa, and the power is 300W;
step five, ZnO is added2Heating the solid in air to 400 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and calcining to obtain the oxygen vacancy-rich nano ZnO, namely ZnO-400-3.
Example 7:
a preparation method of nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium comprises the following steps:
step one, 2.97445g Zn (NO)3)2·6H2O is added toStirring the mixture for 1 hour in 100mL of deionized water, and performing ultrasonic treatment for 1 hour to obtain a zinc nitrate solution;
step two, adding 0.8g of NaOH into 100mL of ultrapure water, stirring for 1 hour, and performing ultrasonic treatment for 1 hour to obtain a sodium hydroxide solution;
step three, the sodium hydroxide solution is ultrasonically atomized into sodium hydroxide atomized substance through an ultrasonic atomizer, the sodium hydroxide atomized substance is introduced into the zinc nitrate solution through carrier gas, the mixture is stirred for 1 hour, the mixture is ultrasonically treated for 1 hour, the mixture is kept still for 2 hours, supernatant is poured out, a centrifugal machine is used for centrifuging for 5 minutes, and the centrifuging speed is 8000r/min, so that Zn (OH) is obtained2Precipitating; the frequency of the ultrasonic atomization is 1.7MHz, and the atomization rate is 1 mL/min; the carrier gas is inert gas, and the flow rate of the carrier gas is 500 mL/min;
step four, Zn (OH)2The precipitate is added to 2mol/L of H2O2Stirring the solution for 1 hour, performing ultrasonic treatment for 1 hour to obtain a mixed solution, and performing ultraviolet pulse laser irradiation on the mixed solution for 20min by using an Nd (yttrium aluminum garnet) YAG (yttrium aluminum garnet) pulse laser; the wavelength of the ultraviolet pulse laser irradiation is 355nm, the pulse width is 15ns, and the pulse frequency is 20 Hz; the single pulse energy is 80 mJ; transferring the irradiated mixed solution into a polytetrafluoroethylene autoclave, preserving the heat for 2 hours at 75 ℃, naturally cooling to room temperature, washing with absolute ethyl alcohol and ultrapure water for 3 times respectively, and finally drying in a vacuum drying oven at 75 ℃ for 24 hours to obtain ZnO2A solid; taking ZnO2Uniformly spreading the solid on a magnetic boat, and treating for 50-60 seconds by using hydrogen plasma; wherein, 2mol/L of H2O2The preparation method of the solution comprises the following steps: 25.5mL of H with the mass fraction of 30 percent2O2Mixing with 99.5mL of deionized water to obtain the water-based cleaning agent; the process parameters of the hydrogen plasma treatment are as follows: the air pressure is 60Pa, and the power is 300W;
step five, ZnO is added2Heating the solid in air to 400 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and calcining to obtain the oxygen vacancy-rich nano ZnO, namely ZnO-400-4.
Carrying out a photocatalysis reduction hexavalent uranium experiment on the nano ZnO rich in oxygen vacancies prepared in the embodiment 1-3;
preparing a buffer solution and an azoarsine III solution:
buffer solution: respectively weighing 20g of chloroacetic acid and 7.5g of sodium acetate, dissolving the chloroacetic acid and the sodium acetate in 2.5L of deionized water, and shaking up to obtain a buffer solution;
azoarsine III solution: 0.6g of azoarsine III particles are dissolved in 600mL of deionized water to obtain 1g/L azoarsine III solution, and the azoarsine III solution can be developed with U (VI) so as to be convenient for detecting the concentration of an unknown U (VI) solution by using an ultraviolet spectrophotometer;
preparation of uranium solution and establishment of standard curve:
uranium solution: weighing 843.910mg of uranyl nitrate, dissolving in 2L of deionized water, and shaking up to obtain a uranium solution of 200 mg/L;
adding 2mL of buffer solution, 0.35mL of azoarsine III solution, 7.55mL of deionized water and 0.1mL of uranium solution with different concentrations (200mg/L, 180mg/L, 160mg/L, 140mg/L, 120mg/L, 100mg/L, 80mg/L, 60mg/L, 40mg/L, 20mg/L and 0mg/L) into a 10mL test tube; the standard curve is shown in FIG. 6; the correlation coefficient of the curve reaches 0.999; the unknown u (vi) concentration tested was confirmed to be authentic.
In the photocatalytic process, 5mg of photocatalyst (oxygen vacancy-rich nano ZnO prepared in examples 1 to 7 and commercial ZnO) was added to 25mL of 200ppm UO2 2+The solution was placed in a 30mL glass bottle and the pH was adjusted by adding negligible volumes of hydrochloric acid or sodium hydroxide solution; a 500W xenon lamp is adopted and is matched with a cut-off filter for simulating sunlight (the radiation intensity is 100 mW/cm)2) Stirring in dark for 120min to make the solution reach adsorption-desorption equilibrium, turning on the light source, removing 0.3mL suspension every 5 or 10 min, and rapidly filtering with cellulose acetate syringe membrane (pore size 0.22 μm); measuring the concentration of U (VI) in the filtrate at 651.8nm by using an ultraviolet-visible spectrophotometry by using azoarsine III as a color developing agent, and calculating the removal rate; the results are shown in FIG. 8; when the pH of the solution is 5.6, the photocatalytic activity of the ZnO obtained at different calcination temperatures and commercial ZnO on U (VI) is shown in figure 7, and the strongest adsorption capacity of ZnO-400 and certain reduction effect can be observed; commercial ZnO has poor adsorption effect but certain reduction capability; from ZnO-400 toThe photoreductivity of ZnO-800 uranium was in turn diminished, and the photoreductivity of ZnO-400 was more effective than commercial ZnO, probably due to the smaller grain size of ZnO-400, which is rich in oxygen vacancies.
SEM and EDS of ZnO-400 after photocatalytic reaction are tested; as shown in FIGS. 1-4; from the EDS chart, it is known that Zn, O and U are uniformly distributed in ZnO-400. The EDS image further estimates the content of elements, and the comparison of the EDS image of ZnO-400 before and after photocatalysis shows that the ZnO-400 after photocatalytic reduction is rich in U elements, and the result shows that uranium is successfully trapped by the catalyst.
Prepared ZnO is subjected to XRD2And the crystal structures of the samples annealed at different temperatures were studied. As can be seen from FIG. 5, the cubic ZnO2Peaks of (PDF 76-1364) at 2 θ ═ 32 °, 37 °, 53 °, and 63 ° correspond to lattice planes (111), (200), (220), and (311), respectively, and broad peaks indicate ZnO2The crystallinity of the sample is not very good, and the particle size is smaller as calculated by the Sherre formula; the samples annealed at different temperatures are found by analysis to be wurtzite (hexagonal) structure (PDF 99-0111), and the peaks of the structure at 2 theta of 32 degrees, 34 degrees, 36 degrees, 48 degrees, 57 degrees, 63 degrees, 66 degrees, 68 degrees and 69 degrees correspond to crystal planes of (100), (002), (101), (102), (110), (103), (200), (112) and (201), respectively. ZnO (zinc oxide)2And ZnO-400 have smaller crystal sizes. In addition, the crystallinity of the sample is obviously improved along with the increase of the annealing temperature, the grain sizes of different annealing temperatures are calculated through the Scherrer formula, and the grain sizes are known to be larger along with the increase of the annealing temperature.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (7)
1. A preparation method of nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium is characterized by comprising the following steps:
step one, Zn (NO)3)2•6H2Adding O into deionized water, stirring for 0.5-1 hour, and performing ultrasonic treatment for 0.5-1 hour to obtain a zinc nitrate solution with the concentration of 0.08-0.11 mol/L;
step two, according to Zn (NO)3)2•6H2Weighing a certain amount of NaOH into ultrapure water according to the molar ratio of O to NaOH of 1:2, stirring for 0.5-1 hour, and carrying out ultrasonic treatment for 0.5-1 hour to obtain a sodium hydroxide solution;
step three, carrying out ultrasonic atomization on the sodium hydroxide solution through an ultrasonic atomizer to obtain a sodium hydroxide atomized substance, introducing the sodium hydroxide atomized substance into a zinc nitrate solution through a carrier gas, stirring for 0.5-1 hour, carrying out ultrasonic treatment for 0.5-1 hour, standing for 2 hours, pouring out a supernatant, and centrifuging by using a centrifugal machine to obtain Zn (OH)2Precipitating; the frequency of ultrasonic atomization is 1.6-1.8 MHz, and the atomization rate is 0.5-1.5 mL/min; the carrier gas is inert gas, and the flow rate of the carrier gas is 400-600 mL/min;
step four, Zn (OH)2Adding the precipitate into 1-3 mol/L H2O2Stirring the solution for 0.5 to 1 hour, performing ultrasonic treatment for 0.5 to 1 hour to obtain a mixed solution, transferring the mixed solution into a polytetrafluoroethylene autoclave, preserving the heat for 1 to 3 hours at the temperature of between 60 and 80 ℃, naturally cooling the mixed solution to room temperature, washing the mixed solution for 3 times by using absolute ethyl alcohol and ultrapure water respectively, and finally drying the washed solution for 24 hours in a vacuum drying oven at the temperature of between 60 and 80 ℃ to obtain ZnO2A solid; taking ZnO2Uniformly spreading the solid on a magnetic boat, and treating for 50-60 seconds by using hydrogen plasma;
step five, treating the ZnO subjected to the hydrogen plasma treatment2Heating the solid in air to 400-800 ℃ at a heating rate of 3-7 ℃/min, preserving the heat for 1-3 hours, and calcining to obtain the nano ZnO rich in oxygen vacancies;
in the fourth step, before the mixed solution is transferred into a polytetrafluoroethylene high-pressure kettle, performing ultraviolet pulse laser irradiation on the mixed solution for 15-20 min by using an Nd-YAG pulse laser; the wavelength of the ultraviolet pulse laser irradiation is 355nm, the pulse width is 10-20 ns, and the pulse frequency is 10-30 Hz; the single pulse energy is 20-100 mJ.
2. The method for preparing nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium according to claim 1, wherein the concentration of the sodium hydroxide solution is 0.19 to 0.21 mol/L.
3. The method for preparing nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium according to claim 1, wherein in the third step, a sodium hydroxide solution is added dropwise to a zinc nitrate solution at a rate of 100mL/h by using a two-channel syringe pump; the centrifugal speed of the centrifugal machine is 8000r/min, and the centrifugal time is 4-8 min.
4. The method for preparing nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium according to claim 1, wherein in the fourth step, the process parameters of the hydrogen plasma treatment are as follows: the pressure is 10 to 100Pa and the power is 50 to 300W.
5. The process for the preparation of oxygen vacancy rich nano ZnO for the photocatalytic reduction of hexavalent uranium of claim 1, wherein the H is2O2The preparation method of the solution comprises the following steps: mixing 30% of H2O2The solution was added to deionized water.
6. The method of preparing nano ZnO rich in oxygen vacancies for photocatalytic reduction of hexavalent uranium according to claim 1, wherein in the fifth step, ZnO is added2Uniformly placing the mixture in a long square boat, placing the long square boat in a quartz tube, heating to 400-600 ℃ at the heating rate of 3-7 ℃/min, preserving the heat for 1-3 hours, and calcining to obtain the nano ZnO rich in oxygen vacancies.
7. The application of the nano ZnO rich in oxygen vacancy prepared by the preparation method of any one of claims 1 to 6 in the photocatalytic reduction of hexavalent uranium is characterized in that the nano ZnO rich in oxygen vacancy is added into radioactive uranium-containing wastewater, the radioactive uranium-containing wastewater is stirred for 120min under dark conditions, and then photocatalytic reaction is carried out under the condition that a xenon lamp simulates sunlight, so that the photocatalytic reduction of hexavalent uranium in the radioactive uranium-containing wastewater is realized.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110341978.4A CN113083277B (en) | 2021-03-30 | 2021-03-30 | Preparation method and application of nano ZnO rich in oxygen vacancy for photocatalytic reduction of hexavalent uranium |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110341978.4A CN113083277B (en) | 2021-03-30 | 2021-03-30 | Preparation method and application of nano ZnO rich in oxygen vacancy for photocatalytic reduction of hexavalent uranium |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113083277A CN113083277A (en) | 2021-07-09 |
CN113083277B true CN113083277B (en) | 2022-04-22 |
Family
ID=76670980
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110341978.4A Active CN113083277B (en) | 2021-03-30 | 2021-03-30 | Preparation method and application of nano ZnO rich in oxygen vacancy for photocatalytic reduction of hexavalent uranium |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113083277B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114917877B (en) * | 2022-03-11 | 2023-08-18 | 西南科技大学 | Preparation and application of metal organic framework composite material for radionuclide treatment |
CN115106077B (en) * | 2022-06-24 | 2023-05-23 | 西南科技大学 | Preparation and application of erbium-doped zinc oxide nano-sheet based on photocatalytic reduction uranium |
CN116078415A (en) * | 2022-10-24 | 2023-05-09 | 西南科技大学 | Preparation and application of mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102531039A (en) * | 2012-03-13 | 2012-07-04 | 浙江理工大学 | Method for preparing zinc oxide (ZnO) nanoparticles |
CN102872850A (en) * | 2012-09-27 | 2013-01-16 | 清华大学 | Oxygen-defect ZnO photocatalyst and preparation method |
CN103641155A (en) * | 2013-12-16 | 2014-03-19 | 江苏大学 | Pulse laser-induced preparation method of zinc oxide nano-structure |
CN103721698A (en) * | 2014-01-10 | 2014-04-16 | 中国天辰工程有限公司 | Zinc oxide catalyst of ordered layered structure and preparation method thereof |
CN105132981A (en) * | 2015-09-18 | 2015-12-09 | 盐城工学院 | Preparation method of disorder photon zinc oxide nanowire-embedded plasma nanogold photoanode material |
CN108543530A (en) * | 2018-03-15 | 2018-09-18 | 中国科学技术大学先进技术研究院 | A kind of Zinc oxide nano sheet in oxygen-enriched vacancy, preparation method and applications |
CN109970135A (en) * | 2019-04-09 | 2019-07-05 | 中南大学 | The application of the TOC of calcium sulfate and/or calcium phosphate in removal hydrometallurgy raffinate |
CN110496612A (en) * | 2019-07-22 | 2019-11-26 | 陕西师范大学 | A kind of method of methylene chloride anaerobic catalysis burning building metal oxide Lacking oxygen |
FR3081710A1 (en) * | 2018-05-31 | 2019-12-06 | Bionuclei | ENZYMATIC MOLECULE MIMING ANTIOXIDANT ACTIVITY |
CN111018041A (en) * | 2019-12-19 | 2020-04-17 | 南华大学 | Preparation method and application of polypyrrole graphite phase carbon nitride composite material for treating uranium-containing wastewater through photocatalytic reduction |
CN111359600A (en) * | 2020-05-26 | 2020-07-03 | 北京锦绣新技术发展有限公司 | Load composite modified nano TiO2Waste water and waste gas pollutant treating ball |
CN112169804A (en) * | 2020-09-28 | 2021-01-05 | 中南大学 | Zinc oxide loaded copper-based multi-metal alloy catalyst and preparation method and application thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7867636B2 (en) * | 2006-01-11 | 2011-01-11 | Murata Manufacturing Co., Ltd. | Transparent conductive film and method for manufacturing the same |
-
2021
- 2021-03-30 CN CN202110341978.4A patent/CN113083277B/en active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102531039A (en) * | 2012-03-13 | 2012-07-04 | 浙江理工大学 | Method for preparing zinc oxide (ZnO) nanoparticles |
CN102872850A (en) * | 2012-09-27 | 2013-01-16 | 清华大学 | Oxygen-defect ZnO photocatalyst and preparation method |
CN103641155A (en) * | 2013-12-16 | 2014-03-19 | 江苏大学 | Pulse laser-induced preparation method of zinc oxide nano-structure |
CN103721698A (en) * | 2014-01-10 | 2014-04-16 | 中国天辰工程有限公司 | Zinc oxide catalyst of ordered layered structure and preparation method thereof |
CN105132981A (en) * | 2015-09-18 | 2015-12-09 | 盐城工学院 | Preparation method of disorder photon zinc oxide nanowire-embedded plasma nanogold photoanode material |
CN108543530A (en) * | 2018-03-15 | 2018-09-18 | 中国科学技术大学先进技术研究院 | A kind of Zinc oxide nano sheet in oxygen-enriched vacancy, preparation method and applications |
FR3081710A1 (en) * | 2018-05-31 | 2019-12-06 | Bionuclei | ENZYMATIC MOLECULE MIMING ANTIOXIDANT ACTIVITY |
CN109970135A (en) * | 2019-04-09 | 2019-07-05 | 中南大学 | The application of the TOC of calcium sulfate and/or calcium phosphate in removal hydrometallurgy raffinate |
CN110496612A (en) * | 2019-07-22 | 2019-11-26 | 陕西师范大学 | A kind of method of methylene chloride anaerobic catalysis burning building metal oxide Lacking oxygen |
CN111018041A (en) * | 2019-12-19 | 2020-04-17 | 南华大学 | Preparation method and application of polypyrrole graphite phase carbon nitride composite material for treating uranium-containing wastewater through photocatalytic reduction |
CN111359600A (en) * | 2020-05-26 | 2020-07-03 | 北京锦绣新技术发展有限公司 | Load composite modified nano TiO2Waste water and waste gas pollutant treating ball |
CN112169804A (en) * | 2020-09-28 | 2021-01-05 | 中南大学 | Zinc oxide loaded copper-based multi-metal alloy catalyst and preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
"Influence of crystalline phase and defects in the ZrO2 nanoparticles synthesized by thermal plasma route on its photocatalytic properties";Ashok B. Nawale et al;《Materials Research Bulletin》;20120727;第47卷;第3432-3439页 * |
"半导体材料的能带调控及其光催化性能的研究";王俊鹏;《中国优秀博硕士学位论文全文数据库(博士) 基础科学辑》;20131015(第10期);第63页3.2.2.1节,第69页3.3.2.1节,第72页第1段,第83页第4节 * |
Also Published As
Publication number | Publication date |
---|---|
CN113083277A (en) | 2021-07-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113083277B (en) | Preparation method and application of nano ZnO rich in oxygen vacancy for photocatalytic reduction of hexavalent uranium | |
CN107298477B (en) | Method for degrading organic pollutants in wastewater by catalyzing persulfate | |
CN106944074B (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
CN105964250B (en) | It is a kind of with visible light-responded Ag10Si4O13Photochemical catalyst and its preparation method and application | |
CN103230802B (en) | Preparation method of composite photocatalyst with visible light response and arsenic removing method | |
WO2022047813A1 (en) | Organic wastewater treatment method based on multi-element co-doped tio2 nano photocatalytic material | |
CN106881111A (en) | Composite bismuth vanadium photocatalyst of cuprous oxide and silver-colored mutual load and its preparation method and application | |
CN103357395B (en) | Lanthanide-doped nanotube TiO 2the preparation method of composite photo-catalyst and the application in VOCs administers thereof | |
CN101773831A (en) | Micro-pore cuprous oxide visible light catalyst and preparation method and application thereof | |
CN107162051A (en) | The preparation method of flower-shaped BiOCl photochemical catalysts and obtained BiOCl photochemical catalysts and application | |
CN106975509B (en) | Preparation method and application of nitrogen and iron co-doped bismuth vanadate visible-light-driven photocatalyst | |
CN105536765A (en) | Shell-based boron-doped titanium dioxide composite photocatalyst and preparation method thereof | |
CN112495400B (en) | SnS with S vacancy2Preparation of nanosheet and application thereof in photodegradation of Cr (VI) | |
CN104096555A (en) | Preparation method for rare earth doped silicon dioxide-titanium dioxide photocatalytic material | |
CN107597093A (en) | A kind of nano-particles self assemble Chinese herbaceous peony shape La3+Adulterate ZnO and its preparation method and application | |
CN103506104A (en) | Carbon-doped TiO2 visible light-responding catalytic film on glass carrier and preparation method thereof | |
CN111701612A (en) | Magnetic nano composite material and preparation method thereof | |
CN105561969A (en) | Preparation and application of porous TixSn1-xO2 solid solution microspheres | |
CN107673441B (en) | Method for degrading rhodamine B under irradiation of ultraviolet lamp light source | |
CN115301225A (en) | Preparation method and application of bismuth/titanium dioxide photocatalytic degradation material with hollow microsphere structure | |
CN112246256B (en) | Piezoelectric catalytic degradation and ammonia synthesis catalyst, and preparation method and application thereof | |
CN112221481A (en) | Catalyst for converting Cr (VI) in water by Z-shaped structure and preparation method and application thereof | |
CN107570161A (en) | A kind of preparation method of the ZnO photocatalyst of Co doping | |
Hao et al. | Photocatalytic degradation of tetracycline over Ce-doped TiO 2@ SiO 2@ Fe 3 O 4 magnetic material | |
CN111841605A (en) | Gas etching type carbon-nitrogen polymer photocatalyst, preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |