CN114558606B - Catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application of catalyst - Google Patents
Catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application of catalyst Download PDFInfo
- Publication number
- CN114558606B CN114558606B CN202210191719.2A CN202210191719A CN114558606B CN 114558606 B CN114558606 B CN 114558606B CN 202210191719 A CN202210191719 A CN 202210191719A CN 114558606 B CN114558606 B CN 114558606B
- Authority
- CN
- China
- Prior art keywords
- uranium
- catalyst
- seawater
- containing wastewater
- catalyst precursor
- 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 128
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 239000013535 sea water Substances 0.000 title claims abstract description 37
- 239000002351 wastewater Substances 0.000 title claims abstract description 33
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 10
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229940116357 potassium thiocyanate Drugs 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052724 xenon Inorganic materials 0.000 claims description 11
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000005289 uranyl group Chemical group 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 14
- 238000005286 illumination Methods 0.000 description 11
- OOAWCECZEHPMBX-UHFFFAOYSA-N oxygen(2-);uranium(4+) Chemical compound [O-2].[O-2].[U+4] OOAWCECZEHPMBX-UHFFFAOYSA-N 0.000 description 11
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 9
- 230000005587 bubbling Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- -1 azo arsine Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
-
- B01J35/19—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/0278—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of new energy development, and discloses a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application thereof, wherein the catalyst is prepared by the following steps: grinding and mixing carbon nitride, potassium chloride and potassium thiocyanate uniformly, and then preserving heat for 3-5 hours at the temperature of 500-600 ℃ to obtain a catalyst precursor; washing the catalyst precursor with clear water and an alcohol solution in sequence to wash salt and impurities on the surface of the catalyst precursor and obtain a washed catalyst precursor; and (3) freeze-drying the catalyst precursor to obtain the catalyst. The catalyst has good circulation performance, and the uranium can be continuously separated from the water body by using the separation method, and the whole process only needs sunlight, so that the method is environment-friendly, sustainable and pollution-free.
Description
Technical Field
The invention relates to the technical field of new energy development, in particular to a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application thereof.
Background
The development and utilization of uranium resources are of great significance for sustainable development of nuclear energy. However, land uranium resources have been found to be limited. The global sea water contains about 45 million tons of uranium, which is thousands of times the known land uranium resources. The method for extracting uranium from seawater which is widely studied at present mainly comprises an adsorption method, but the method has the advantages of poor selectivity, low extraction efficiency, difficult elution and high cost. The photocatalysis method provided in recent years provides a new idea for separating and extracting uranium in the water body. The photocatalysis method has the advantages of green, high efficiency, high selectivity, large extraction capacity and the like, and has wide application prospect. However, in practical application, the photocatalytic method can only occur under illumination, and the photocatalytic reduction of uranium can not be performed when no illumination exists at night, and reoxidation and dissolution of uranium reduction products are easily caused, so that the photocatalytic reduction efficiency is affected.
In summary, the existing photocatalysis uranium extraction technology has the following problems: the existing uranium photocatalytic reduction technology can only occur under the drive of illumination, and the uranium catalytic reduction cannot be continuously carried out in the dark and is easy to cause oxidation and resolubilization of extracted uranium. In summary, the existing technology still has difficulty in realizing continuous photocatalytic reduction of uranium under illumination and darkness, and achieves the purpose of extracting uranium from seawater in both day and night.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application thereof.
The invention relates to a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application thereof, which are realized by the following technical scheme:
the first object of the invention is to provide a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater, which is prepared by the following steps:
grinding and mixing carbon nitride, potassium chloride and potassium thiocyanate uniformly, and then preserving heat for 3-5 hours at the temperature of 500-600 ℃ to obtain a catalyst precursor;
washing the catalyst precursor with water and alcohol solution in sequence to wash salt and impurities on the surface of the catalyst precursor and obtain the washed catalyst precursor;
and (3) freeze-drying the washed catalyst precursor to obtain the catalyst.
Further, the mass ratio of the carbon nitride to the potassium chloride to the potassium thiocyanate is 1:1-3:4-6.
Further, the vacuum degree of the freeze drying treatment is below 10Pa, the treatment temperature is-15 to-5 ℃, and the treatment time is 8 to 16 hours.
Further, the temperature is raised from room temperature to 500-600 ℃ at a rate of 5-10 ℃/min.
Further, washing the catalyst precursor with water until no potassium ions are detected in the washing liquid; the catalyst precursor is then washed with absolute ethanol to remove alcohol soluble impurities from the catalyst precursor.
The second object of the invention is to provide an application of the catalyst based on any of the above in extracting and separating uranium from uranium-containing wastewater or seawater.
Further, uranium in uranium-bearing wastewater or seawater is separated by the following steps:
step 1, catalytic reduction:
uniformly dispersing the catalyst in an aqueous solvent, then adding uranium-containing wastewater or uranium-containing seawater, uniformly mixing, adjusting the pH to 5.5-6.5, adding a sacrificial agent, uniformly mixing to obtain a first mixed solution, irradiating the first mixed solution under a nitrogen atmosphere for 8-60 min under a xenon lamp, performing suction filtration to separate a solid phase and a liquid phase, and collecting solids to obtain a uranium-containing extract;
or uniformly dispersing the catalyst material in a water solvent, regulating the pH to 5.5-6.5, adding a sacrificial agent, uniformly mixing to obtain a second mixed solution, irradiating the second mixed solution to change the color of the second mixed solution from yellow to blue under natural light or under a xenon lamp, forming stable reducing free radicals on the surface of the material, removing a light source, adding uranium-containing wastewater or uranium-containing seawater, uniformly mixing, reacting for 40 minutes, carrying out suction filtration, separating a solid-liquid phase, and collecting solids to obtain a uranium-containing extract;
step 2, separating and extracting uranium:
oxidizing the uranium-containing extract in air for 8-16 h, adding a dilute nitric acid solution, uniformly stirring to elute uranium, filtering, and collecting filtrate to obtain a uranyl-enriched solution.
Further, the dosage ratio of the total volume of the water solvent and uranium-containing wastewater or uranium-containing seawater to the catalyst is 1 mL:0.5-1.5 mg.
Further, the sacrificial agent is any one of methanol, ethanol, isopropanol and formic acid.
Further, the dosage ratio of the sacrificial agent to the catalyst is 1 mL:4-8 mg.
Further, the nitrogen bubbling rate is 120mL/min, and the bubbling time is 1-3 h.
Further, the dosage ratio of the dilute nitric acid solution to the catalyst is 1 mL:5-10 mg;
the concentration of the dilute nitric acid solution is 0.05-0.15 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the catalyst precursor is obtained by uniformly mixing and sintering carbon nitride powder, potassium chloride and potassium thiocyanate, and is sequentially washed by water and alcohol solution, so that excessive salt and alcohol-soluble impurities in the catalyst precursor are washed away, and the influence of the salt and the alcohol-soluble impurities on the performance of the catalyst is avoided. The catalyst is obtained by freeze-drying the washed catalyst precursor.
The catalyst can effectively reduce hexavalent uranium in uranium-containing wastewater or uranium-containing seawater by photocatalysis under illumination; the catalyst of the invention generates charge separation on the surface of the catalyst under the irradiation of light so as to form stable and long-acting reductive free radical, N 2 Under the protection, the free radical can exist stably for more than 48 hours; in the absence of illumination, the catalyst can continuously reduce hexavalent uranium in the solution through the free radicals, and can prevent tetravalent uranium generated by reduction on the surface of the catalyst from being oxidized and dissolved, so that the catalyst can realize the effect of extracting uranium from seawater in all day and night.
According to the invention, the uranium-containing wastewater or the uranium-containing seawater is treated by using the catalyst, so that hexavalent uranium in the uranium-containing wastewater or the uranium-containing seawater can be reduced on the surface of the catalyst rapidly, then the uranium reduced on the surface of the catalyst is separated into a dilute nitric acid solution by dilute nitric acid treatment, and the catalyst is filtered out, so that the uranium in the uranium-containing wastewater or the uranium-containing seawater is extracted into the dilute nitric acid solution, and the uranium in the uranium-containing wastewater or the uranium-containing seawater is extracted and separated.
The catalyst has good circulation performance, and the uranium can be continuously separated from the water body by using the separation method, and the whole process only needs sunlight, so that the method is environment-friendly, sustainable and pollution-free.
Drawings
FIG. 1 is a schematic diagram of a uranium separation route according to the present invention;
FIG. 2 is an XPS spectrum of the catalyst of example 1 of the present invention;
FIG. 3 is an infrared spectrum of the catalyst in example 1 of the present invention;
FIG. 4 is an X-ray diffraction pattern of the catalyst of example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of the catalyst in example 1 of the present invention;
FIG. 6 is a transmission electron microscope image of the catalyst in example 1 of the present invention;
FIG. 7 is an ultraviolet-visible diffuse reflectance graph of the catalyst of example 1 of the present invention;
FIG. 8 is a photocurrent response of the catalyst of example 1 of the present invention;
FIG. 9 shows that the catalyst of example 2 of the present invention remains stable for 48 hours at the surface free radical signal;
FIG. 10 shows XPS spectra of uranium reduction after various times of exposure of the catalyst in example 2 of the present invention;
FIG. 11 shows the photocatalytic effect on uranium of the catalyst under illumination in example 1 of the present invention;
FIG. 12 shows the uranium dark catalytic effect of the post-illumination catalyst of example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The concentration of the present invention was 4.0X10 -3 UO of mol/L 2 (NO 3 ) 2 The following example operations were performed as uranium-containing wastewater or uranium-containing seawater.
Example 1
The embodiment provides a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater, which is prepared by the following steps:
respectively weighing carbon nitride, potassium thiocyanate and potassium chloride with corresponding mass according to the mass ratio of 1:2:6, grinding and uniformly mixing, placing the mixture into a quartz boat, placing the quartz boat into a tube furnace, heating to 550 ℃ at the speed of 8 ℃/min, and preserving heat for 4 hours to obtain a light yellow solid catalyst precursor;
grinding the catalyst precursor into powder, and washing the ground catalyst precursor with ultrapure water for several times until K is undetectable in the washing liquid after washing + Washing the ground catalyst precursor for several times by using absolute ethyl alcohol to wash alcohol-soluble impurities in the catalyst precursor, so that the influence of other substances on the catalytic performance of the catalyst is reduced, and the catalytic performance of the catalyst is improved; subsequently, the catalyst powder was freeze-dried at-15℃under 10Pa for 12 hours to remove water, thereby obtaining a catalyst.
Example 2
The embodiment provides a catalyst for extracting and separating uranium from uranium-containing wastewater or seawater, which is prepared by the following steps:
respectively weighing carbon nitride, potassium thiocyanate and potassium chloride with corresponding mass according to the mass ratio of 1:3:5, grinding and uniformly mixing, placing into a quartz boat, placing into a tube furnace, heating to 550 ℃ at the speed of 8 ℃/min, and preserving heat for 4 hours to obtain a light yellow solid catalyst precursor;
grinding the catalyst precursor into powder, and washing the ground catalyst precursor with ultrapure water for several times until K is undetectable in the washing liquid after washing + Washing the ground catalyst precursor for several times by using absolute ethyl alcohol to wash alcohol-soluble impurities in the catalyst precursor, so that the influence of other substances on the catalytic performance of the catalyst is reduced, and the catalytic performance of the catalyst is improved; subsequently, the catalyst powder was freeze-dried at-10℃under 8Pa for 10 hours, and the water was removed, thereby obtaining a catalyst.
Example 3
This embodiment differs from embodiment 1 in that:
in this example, the mass ratio of carbon nitride, potassium chloride and potassium thiocyanate was 1:1:4.
In this example, the holding temperature was 500 ℃, the holding time was 5 hours, and the heating rate was 5 ℃/min.
In this example, the degree of vacuum in the freeze-drying treatment was 10Pa or less, the treatment temperature was-15 to-5℃and the treatment time was 8 to 16 hours.
Example 4
This embodiment differs from embodiment 1 in that:
in this example, the mass ratio of carbon nitride, potassium chloride and potassium thiocyanate was 1:3:6.
In this example, the holding temperature was 600 ℃, the holding time was 3 hours, and the heating rate was 10 ℃/min.
In this example, the degree of vacuum in the freeze-drying treatment was 10Pa or less, the treatment temperature was-15 to-5℃and the treatment time was 8 to 16 hours.
Example 5
This example provides a separation method for extracting and separating uranium from uranium-containing wastewater or seawater, and uses the catalyst of example 1 to perform a separation process for uranium having a concentration of 4.0X10 -3 UO of mol/L 2 (NO 3 ) 2 Uranium in the solution is separated and extracted, and the specific steps are as follows:
15mg of the catalyst material was weighed into a quartz tube and dispersed uniformly in 14.625mL of distilled water by sonication, followed by the addition of 0.375mL of 4.0X10 -3 mol/L UO 2 (NO 3 ) 2 Mixing the solution, adjusting pH to 6.0, adding 2.5mL of methanol as sacrificial agent, and bubbling N with 120m under dark condition 2 For 2 hours to remove dissolved oxygen, then irradiated under a 500W xenon lamp (with a 420nm filter) for 40min, and filtered to obtain uranium-containing extract. Oxidizing the obtained uranium-containing extract in air for 12 hr, adding 2mL of 0.1mol/L dilute nitric acid solution, stirring for 10min, and filtering to obtain UO 2 (NO 3 ) 2 Uranium in the solution is transferred to the filtrate, and separation of uranium is realized.
Example 6
This example provides a separation method for extracting and separating uranium from uranium-containing wastewater or seawater, and uses the catalyst of example 2 to perform a separation process for uranium having a concentration of 4.0X10 -3 UO of mol/L 2 (NO 3 ) 2 Uranium in the solution is separated and extracted, and the specific steps are as follows:
15mg of catalyst material was weighed and placedDispersing in 14.625mL distilled water by ultrasonic in a quartz tube, adjusting pH to 6.0, adding 2.5mL methanol as sacrificial agent, and bubbling N at 120mL/min 2 Bubbling for 2 hr to remove dissolved oxygen, then placing under 500W xenon lamp (with 420nm filter) and irradiating for 1min, adding 0.375mL of 4.0X10 after the solution color changes from pale yellow to blue -3 mol/L UO 2 (NO 3 ) 2 The solution is mixed evenly, and is filtered after the reaction is carried out for 40min, thus obtaining the uranium-containing extract. Oxidizing the obtained uranium-containing extract in air for 12 hr, adding 2mL of 0.1mol/L dilute nitric acid solution, stirring for 10min, and filtering to obtain UO 2 (NO 3 ) 2 Uranium in the solution is transferred to the filtrate, and separation of uranium is realized.
Example 7
This example differs from example 5 in that, in performing the performance test on the catalyst:
adjusting the pH to 5.5;
the irradiation time of the xenon lamp is 8min;
the oxidation time of the uranium-containing extract is 8 hours;
the ratio of the total volume of the water solvent to uranium-containing wastewater or uranium-containing seawater to the catalyst was 1 mL/0.5 mg.
The sacrificial agent was ethanol and the ratio of sacrificial agent to catalyst was 1mL:4mg.
The nitrogen bubbling time was 1h.
The ratio of the amount of the dilute nitric acid solution to the catalyst was 1 mL/5 mg, and the concentration of the dilute nitric acid solution was 0.05mol/L.
Example 8
This example differs from example 5 in that, in performing the performance test on the catalyst:
adjusting the pH to 6.5;
the irradiation time of the xenon lamp is 60min;
the oxidation time of the uranium-containing extract is 16h;
the ratio of the total volume of the water solvent to uranium-containing wastewater or uranium-containing seawater to the catalyst was 1 mL/1.5 mg.
The sacrificial agent was isopropanol and the ratio of sacrificial agent to catalyst was 1mL:8mg.
The bubbling time of nitrogen was 3 hours.
The dosage ratio of the dilute nitric acid solution to the catalyst was 1 mL/10 mg, and the concentration of the dilute nitric acid solution was 0.15mol/L.
Example 9
This example differs from example 6 in that, in performing the performance test on the catalyst:
adjusting the pH to 6.5;
adding UO 2 (NO 3 ) 2 The reaction time after the solution is 30min;
the sacrificial agent is formic acid.
Test section
In order to verify the performance of the catalyst prepared according to the invention, the following tests were carried out:
XPS test (one)
The invention takes the catalyst of example 1 as an example, and XPS test is carried out on the catalyst, and the result is shown in figure 2, and it can be seen that the catalyst material prepared by the method of the invention has more obvious potassium element (K + ) And XPS characteristic peaks of cyano groups (-C.ident.N), indicating successful doping of potassium ions and cyano groups into the catalyst.
(II) Infrared Spectrometry test
The catalyst of example 1 was used as an example of the present invention, and the results of the infrared spectrum test are shown in FIG. 3, it can be seen that the catalyst material prepared by the method of the present invention has an infrared vibration peak similar to that of graphite-phase carbon nitride, wherein the infrared vibration peak is located at 3000 to 3300cm -1 The characteristic peak between the two corresponds to the stretching vibration of N-H and O-H bonds; is positioned at 1000-1800cm -1 The characteristic peak corresponds to the stretching vibration of the aromatic C-N heterocyclic skeleton in the heptazine ring; 810cm -1 The characteristic peak at which corresponds to the stretching vibration of the triazinyl ring. In addition, at 2170cm -1 A strong infrared vibration peak appears at the position corresponding to the asymmetric stretching vibration peak of the cyano group, and the result further confirms the successful doping of the cyano group.
(III) X-ray diffraction test
Taking the catalyst of example 1 as an example, and carrying out X-ray diffraction test on the catalyst, and the result is shown in figure 4, it can be seen that the catalyst material prepared by the method has obvious signal peak at the position of the diffraction angle of 27.9 degrees, and the signal peak corresponds to the (002) crystal face of graphite phase carbon nitride which is stacked in an interlayer; the diffraction angle is slightly shifted to a high angle compared with the diffraction angle (27.5 ℃) of the (002) crystal face of the classical graphite phase carbon nitride, which shows that the prepared catalyst material has smaller interlayer stacking distance than the classical graphite phase carbon nitride material. In addition, diffraction peaks occurring at 8.0 and 9.9 ° can be attributed to the (110) and (010) crystal planes of the polyimide structure.
(IV) topography testing
The catalyst of example 1 was taken as an example, and a scanning electron microscope test and a transmission electron microscope test were performed on the catalyst, and the results are shown in fig. 5 and 6, respectively. As can be seen from fig. 5, the catalyst material prepared by the method of the present invention exhibits an irregular chip and lamellar stacking structure; and as can be seen from fig. 6, the catalyst material prepared by the method of the present invention exhibits irregular layered nano-sheet packing, and the nano-sheets are small in size.
(V) UV-visible diffuse reflection
Taking the catalyst of example 1 as an example, the ultraviolet-visible diffuse reflection test is carried out on the catalyst, and the result is shown in fig. 7, and it can be seen that the catalyst material prepared by the method of the invention has higher light absorption in ultraviolet and visible light regions.
(six) photocurrent response
The photo-current response test is carried out on the catalyst of the embodiment 1 by taking the catalyst as an example, and the result is shown in fig. 8, so that when the catalyst is irradiated by light, the photo-current signal of the catalyst material is rapidly increased, which proves that the catalyst material prepared by the method has obvious photo-electric response, and the catalyst material has high-efficiency photo-generated carrier separation capability.
(seventh) radical stability test
In order to ensure that the catalyst prepared by the method can be used as a catalyst in the process of extracting and separating uranium from uranium-containing wastewater or seawater, the catalyst of the invention is taken as an example of the catalyst of the embodiment 2, and the free radical stability is tested, and the result is shown in fig. 9, and the catalyst of the embodiment 2 can be still stable within 48 hours in surface free radical signals, so that the catalyst prepared by the method of the invention has good stability and can be used as a catalyst in the process of extracting and separating uranium from uranium-containing wastewater or seawater.
In order to further verify the separation effect of the catalyst prepared by the method in the process of extracting and separating uranium from uranium-containing wastewater or seawater, the following tests are carried out:
the method comprises the steps of irradiating the catalyst in the embodiment 2 with a 500W xenon lamp for 10 minutes, placing the catalyst in the dark for different times, adding uranyl solution, analyzing the uranium valence change by XPS, and reducing to mainly generate non-metering uranium dioxide (UO) 2+x ) As shown in FIG. 10, it can be seen that the radicals formed after illumination can maintain good reactivity within 24 hours, and uranium in the solution is treated as UO 2+x The form is deposited completely on the catalyst surface. After the catalyst is placed for 48 hours after illumination, part of uranium is adsorbed in a uranyl form, but part of uranium is reduced to tetravalent, which indicates that free radicals formed on the surface of the catalyst after illumination can exist stably for a long time, and uranium in the solution can be completely reduced and deposited within at least 24 hours.
The concentration of the supernatant was measured by the azo arsine III spectrophotometry by taking 1mL of the suspensions of the different reaction stages of example 5 and example 6 and filtering, and the results are shown in FIG. 11 and FIG. 12.
As can be seen from fig. 11, after the catalyst of example 1 was mixed with the uranium-containing solution, the reaction was carried out in the dark for 2 hours to reach adsorption equilibrium, at which time about 75% of uranium in the solution was adsorbed on the catalyst, at which time the catalyst system was irradiated with a 500W xenon lamp, and all the uranium was completely reduced and deposited on the catalyst surface to be extracted in 5 minutes by the photocatalytic reaction.
As can be seen from fig. 12, after the catalyst of example 2 was irradiated with a 500W xenon lamp for 10 minutes, the uranium in the solution was completely reduced and deposited on the catalyst surface to be extracted within 5 minutes under the protection of nitrogen after being mixed with the uranium-containing solution, and the extraction rate was 100%.
It should be apparent that the embodiments described above are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (9)
1. The catalyst for extracting and separating uranium from uranium-containing wastewater or seawater is characterized by being prepared by the following steps:
grinding and mixing carbon nitride, potassium chloride and potassium thiocyanate uniformly, and then preserving heat for 3-5 hours at the temperature of 500-600 ℃ to obtain a catalyst precursor;
washing the catalyst precursor with water and alcohol solution in sequence to obtain a washed catalyst precursor;
the catalyst is obtained after the washed catalyst precursor is subjected to freeze drying treatment;
the mass ratio of the carbon nitride to the potassium chloride to the potassium thiocyanate is 1:1-3:4-6.
2. The catalyst according to claim 1, wherein the degree of vacuum of the freeze-drying treatment is 10Pa or less, the treatment temperature is-15 to-5 ℃, and the treatment time is 8 to 16 hours.
3. The catalyst of claim 1, wherein the temperature is raised from room temperature to 500 to 600 ℃ at a rate of 5 to 10 ℃/min.
4. Use of a catalyst according to any one of claims 1 to 3 for the extraction and separation of uranium from uranium-containing wastewater or seawater.
5. Use according to claim 4, characterized in that uranium is separated from uranium-containing wastewater or seawater by:
step 1, catalytic reduction:
uniformly dispersing the catalyst in a water solvent, then adding uranium-containing wastewater or uranium-containing seawater, uniformly mixing, adjusting the pH to 5.5-6.5, adding a sacrificial agent, uniformly mixing to obtain a first mixed solution, irradiating the first mixed solution under a nitrogen atmosphere for 8-60 min under a xenon lamp, carrying out solid-liquid separation, and collecting separated solids to obtain a uranium-containing extract;
or uniformly dispersing the catalyst material in a water solvent, regulating the pH to 5.5-6.5, adding a sacrificial agent, uniformly mixing to obtain a second mixed solution, irradiating the second mixed solution to change the color of the second mixed solution from yellow to blue under natural light or under a xenon lamp, at this time, forming stable reducing free radicals on the surface of the material, removing a light source, adding uranium-containing wastewater or uranium-containing seawater, uniformly mixing, reacting for 30-60 min, carrying out solid-liquid separation, and collecting separated solids to obtain a uranium-containing extract;
step 2, separating and extracting uranium:
oxidizing the uranium-containing extract in air for 8-16 h, adding a dilute nitric acid solution, uniformly stirring to elute uranium, filtering, and collecting filtrate to obtain a uranyl-enriched solution.
6. The use according to claim 5, wherein the sacrificial agent is any one of methanol, ethanol, isopropanol, formic acid.
7. The use according to claim 5, wherein the ratio of the total volume of the aqueous solvent to uranium-containing wastewater or uranium-containing seawater to the catalyst is 1ml to 0.5-1.5 mg;
the dosage ratio of the sacrificial agent to the catalyst is 1 mL:4-8 mg.
8. The method according to claim 5, wherein the nitrogen is bubbled at a rate of 120mL/min for a period of 1 to 3 hours.
9. The use according to claim 5, wherein the ratio of the dilute nitric acid solution to the catalyst is 1ml to 5-10 mg;
the concentration of the dilute nitric acid solution is 0.05-0.15 mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210191719.2A CN114558606B (en) | 2022-02-28 | 2022-02-28 | Catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application of catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210191719.2A CN114558606B (en) | 2022-02-28 | 2022-02-28 | Catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application of catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114558606A CN114558606A (en) | 2022-05-31 |
| CN114558606B true CN114558606B (en) | 2023-07-25 |
Family
ID=81715341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210191719.2A Active CN114558606B (en) | 2022-02-28 | 2022-02-28 | Catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application of catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114558606B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115148389B (en) * | 2022-07-01 | 2023-06-16 | 华北电力大学 | Photocatalysis uranium removal method without catalyst |
| CN115821080A (en) * | 2022-10-17 | 2023-03-21 | 西北工业大学 | Process for extracting uranium from uranium-containing wastewater and preparing yellow cake |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940338A (en) * | 2018-07-09 | 2018-12-07 | 湖南大学 | Potassium element adulterates nitride porous carbon photochemical catalyst and its preparation method and application |
| CN113499790A (en) * | 2021-07-08 | 2021-10-15 | 西南科技大学 | Preparation and application of Ag-doped CdSe nanosheet photocatalytic material separated by uranium reduction |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2634731A1 (en) * | 1975-08-04 | 1977-02-17 | Ciba Geigy Ag | Metal carbide-nitride powder prodn. - using triazine or pyrimidine cpd. as carbon and nitrogen source |
| FR2948126B1 (en) * | 2009-07-17 | 2011-09-16 | Commissariat Energie Atomique | PROCESS FOR EXTRACTING AT LEAST ONE CHEMICAL ELEMENT FROM A MELT SALT MEDIUM |
| CN107486231B (en) * | 2017-08-24 | 2019-07-09 | 福州大学 | A kind of preparation method of graphite phase carbon nitride colloid photochemical catalyst |
| CN108584892A (en) * | 2018-04-26 | 2018-09-28 | 福州大学 | A kind of preparation method and applications of crystalline phase azotized carbon nano particle |
| CN108906102A (en) * | 2018-06-11 | 2018-11-30 | 中国科学院地质与地球物理研究所兰州油气资源研究中心 | A method of uranium extraction is carried out using photocatalysis technology under visible light |
| 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 |
| CN111627588B (en) * | 2020-06-15 | 2021-08-10 | 华北电力大学 | Application of graphene aerogel in removing uranium through photocatalysis |
| CN111792628B (en) * | 2020-07-07 | 2022-09-30 | 清华大学 | Double-function carbon nitride material synthesized by molten salt method and preparation method and application thereof |
| CN113171766B (en) * | 2021-04-29 | 2023-08-22 | 常州大学 | Preparation method and application of ternary magnetic nano graphite phase carbon nitride material integrating oil absorption/adsorption of metal ions/photocatalysis |
-
2022
- 2022-02-28 CN CN202210191719.2A patent/CN114558606B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940338A (en) * | 2018-07-09 | 2018-12-07 | 湖南大学 | Potassium element adulterates nitride porous carbon photochemical catalyst and its preparation method and application |
| CN113499790A (en) * | 2021-07-08 | 2021-10-15 | 西南科技大学 | Preparation and application of Ag-doped CdSe nanosheet photocatalytic material separated by uranium reduction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114558606A (en) | 2022-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114558606B (en) | Catalyst for extracting and separating uranium from uranium-containing wastewater or seawater and application of catalyst | |
| CN113045723B (en) | Preparation method of porous covalent organic framework and application of porous covalent organic framework in capture of uranyl ions | |
| CN112958150B (en) | Preparation of ethylenediamine-coated cadmium telluride nano-belt photocatalyst and separation method of uranium in radioactive wastewater | |
| CN113289647B (en) | Biochar doped BiOBr x Cl 1-x Photocatalyst, preparation method and application | |
| CN111018041A (en) | Preparation method and application of polypyrrole graphite phase carbon nitride composite material for treating uranium-containing wastewater through photocatalytic reduction | |
| Xiong et al. | Engineering a phase transition induced g-C3N5/poly (triazine imide) heterojunction for boosted photocatalytic H2 evolution | |
| CN105642275A (en) | CeO2/Bi2WO6/MgAl-LDH composite photo-catalyst and preparation method and application thereof | |
| CN113499790A (en) | Preparation and application of Ag-doped CdSe nanosheet photocatalytic material separated by uranium reduction | |
| CN113976148B (en) | Z-shaped C 60 Bi/BiOBr composite photocatalyst and preparation method and application thereof | |
| CN114177928B (en) | Composite photocatalyst Bi@H-TiO with visible light response 2 /B-C 3 N 4 Preparation method and application thereof | |
| CN113976147B (en) | Bi/Bi 4 O 5 Br 2 Photocatalyst, preparation method and application thereof | |
| CN114572960A (en) | Preparation method of graphite oxide alkyne membrane material for adsorbing and separating uranium | |
| CN111939958B (en) | g-C3N4/Bi2WO6/CuS ternary composite photocatalyst and preparation method thereof | |
| CN111905817B (en) | Reduction of CO 2 Preparation method and application of efficient photocatalytic material PCN-222-Zn serving as formic acid | |
| CN111234295B (en) | Molecularly imprinted photocatalytic material and preparation method and application thereof | |
| CN110182808B (en) | Preparation method of silicon-carbon alkene and method for preparing hydrogen by photolysis of water vapor | |
| CN116803527A (en) | Transition metal sulfide-covalent organic framework composite material and application thereof | |
| CN111215116A (en) | 3D defect carbon nitride photocatalytic material and preparation method and application thereof | |
| CN111841605B (en) | Gas etching type carbon-nitrogen polymer photocatalyst, preparation method and application thereof | |
| CN115010101A (en) | Preparation method and application of carbon nitride nanosheet with wide spectral response and high crystallinity | |
| CN114917877B (en) | Preparation and application of metal organic framework composite material for radionuclide treatment | |
| CN115138354B (en) | Core-shell structure Cs 0.32 WO 3 /BiVO 4 Heterojunction, preparation method and application thereof | |
| CN114931936B (en) | Preparation and application of MoS2/TiO2/rGO composite photocatalytic material | |
| CN115672362B (en) | Preparation and application of red phosphorus oxide for photocatalytic reduction of uranium | |
| He et al. | The photocatalytic extraction of U (VI) by CdS/g-C3N4 cellulose film |
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 |