WO2021121167A1 - 利用含有氧空位的金属氧化物电化学海水提铀的方法 - Google Patents

利用含有氧空位的金属氧化物电化学海水提铀的方法 Download PDF

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WO2021121167A1
WO2021121167A1 PCT/CN2020/135832 CN2020135832W WO2021121167A1 WO 2021121167 A1 WO2021121167 A1 WO 2021121167A1 CN 2020135832 W CN2020135832 W CN 2020135832W WO 2021121167 A1 WO2021121167 A1 WO 2021121167A1
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seawater
solution
electrode
oxygen vacancies
hour
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竹文坤
何嵘
李怡
段涛
雷佳
陈涛
杨帆
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西南科技大学
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

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  • the invention relates to a method for extracting uranium from seawater, in particular to a method for extracting uranium from electrochemical seawater using metal oxides containing oxygen vacancies.
  • Uranium is a raw material for nuclear power, and there are very few uranium reserves in natural ore. At present, the world's exploitable uranium resources are limited. The world's total ocean water is about 1.37 ⁇ 10 12 m 3 , and the total reserves of uranium in the seawater reach 4.29 billion tons, which is nearly 1,000 times the land reserves. With the development of nuclear power and low-carbon economy, the demand for uranium resources has become increasingly urgent. Based on the scarcity of uranium and the limited uranium mineral resources, it is of great significance to extract uranium from seawater as a supplement or substitute for traditional ore-type uranium resources.
  • the current methods of extracting uranium mainly include chemical precipitation, ion exchange, membrane separation, and adsorption.
  • the chemical precipitation method has simple equipment, low cost and high efficiency, but the polymer produced by the reaction needs to be further concentrated, dehydrated and solidified; the ion exchange method has high extraction efficiency and good purification effect, but it is expensive, poor selectivity, and limited exchange capacity; membrane
  • the separation method has simple operation, low energy consumption and strong adaptability, but it has high requirements for the water quality of raw water and often needs to be combined with other water treatment technologies; while the adsorption method requires large processing capacity and strong adsorbent selectivity for adsorbents , Strong corrosion resistance, high mechanical strength and other characteristics, and the existing adsorption materials in practical applications also have the defects of low adsorption efficiency, high production cost, difficulty in recycling and reuse.
  • Compounds with oxygen vacancies can capture oxygen ions, while uranium in seawater is uranyl ions, which are uranium-oxygen complexes, such as UO 2 2+ .
  • Oxygen vacancies capture oxygen, which can achieve the effect of indirect capture of uranium.
  • Compounds are easier to capture uranyl ions.
  • the compound with oxygen vacancies is coated on carbon paper as the working electrode, platinum wire is used as the counter electrode, calomel electrode is used as the reference electrode, and the uranium in the seawater is fixed on the electrode by electrifying the electrode. On the working electrode, the extraction of uranium in seawater is realized.
  • An object of the present invention is to solve at least the above-mentioned problems and/or disadvantages and to provide at least the advantages described later.
  • a method for extracting uranium from electrochemical seawater using metal oxides containing oxygen vacancies includes the following steps:
  • Step 1 Prepare an indium nitrate isopropanol solution with a concentration of 0.024 ⁇ 0.028mol/L; add glycerin to the indium nitrate isopropanol solution, stir for 0.5-1 hour, and ultrasonic for 0.5-1 hour to obtain a mixed solution;
  • Step 2 Transfer the mixed solution to a polytetrafluoroethylene high-temperature and high-pressure reactor, heat up to 160 ⁇ 200°C, keep it for 1 ⁇ 3 hours, cool to room temperature naturally, separate the solid and liquid, and wash the solid with deionized water and ethanol. , And then dried in a vacuum drying oven at 60-80°C for 10-14 hours to obtain spherical indium hydroxide solid;
  • Step 3 Dissolve the spherical indium hydroxide solid in deionized water, sonicate it for 0.5-1 hour, then transfer the sonicated solution to a polytetrafluoroethylene high-temperature and high-pressure reactor, heat up to 40 ⁇ 60°C, and keep it warm for 1 ⁇ 3 After hours, it is naturally cooled to room temperature, washed with ethanol, and then dried in an oven at 60-80°C for 10-14 hours to obtain flake indium hydroxide solid;
  • Step 4 Heating the flake indium hydroxide solid to 350-450°C in an atmosphere with a hydrogen content of less than 5%, and calcining for 1 to 3 hours to obtain a calcined In 2 O 3-x sample with oxygen vacancies;
  • Step 5 Add the In 2 O 3-x sample to ethanol and sonicate for 0.5 to 1 hour, then add the membrane solution, and continue to sonicate for 0.5 to 1 hour; spread the ultrasonic solution evenly on the carbon paper, and let the carbon paper be natural After drying, clamp the dried carbon paper with a gold electrode and use it as the working electrode in the three-electrode system.
  • the counter electrode in the three-electrode system is a platinum wire and the reference electrode is a calomel electrode;
  • Step 6 Add simulated seawater to the electrolytic cell, place the three-electrode system in the simulated seawater of the electrolytic cell, stir the simulated seawater for electrolysis to extract uranium from seawater, set the electrolytic cell voltage to -0.3 ⁇ -0.5V, and electrolyze for 10 ⁇ 100min , In the process of electrolysis, every 1 ⁇ 2min when the power is turned on, the power will be cut off for 30 ⁇ 60s.
  • the method for preparing the indium nitrate isopropanol solution is: dissolving In(NO 3 ) 3 ⁇ 4.5H 2 O in isopropanol, stirring for 0.5 to 1 hour, and ultrasonicating for 0.5 to 1 hour to obtain nitric acid Indium isopropanol solution; the mass ratio of In(NO 3 ) 3 ⁇ 4.5H 2 O to glycerol is 3:80-120;
  • the mass-volume ratio of the spherical indium hydroxide solid to the deionized water is 1 g:120-160 mL.
  • the mass-volume ratio of the In 2 O 3-x sample to ethanol is 1 mg:0.2-0.6 mL; the mass-volume ratio of the In 2 O 3-x sample to the membrane solution is 1 mg: 10uL.
  • the membrane solution is a nafion membrane solution.
  • the method for preparing the simulated seawater is: dissolving uranyl nitrate and sodium chloride in deionized water and ultrasonicating for 0.5 to 1 hour to obtain simulated seawater; the concentration of U 6+ in the simulated seawater is 50 to 150 ug /L, the concentration of sodium chloride is 0.1 to 1 mol/L.
  • the sixth step after the electrolysis is completed, place the three-electrode system in an electrolytic cell containing 0.1-1 mol/L sodium chloride solution and stir for electrolysis; set the electrolytic cell voltage to +0.3 ⁇ +0.5V , Power on for 1 to 3 minutes, power off for 0.5 to 1 minute, repeat the power on and power off process 15 to 30 times; let U 4+ on the working electrode be oxidized in a sodium chloride solution with a concentration of 0.1 to 1 mol/L U 6+ .
  • the ultrasonic power used in step 1, step 3, and step 5 is 600 to 1200 W, and the frequency is 28 to 40 KHz.
  • the rate of temperature rise is 3-6°C/min; in the third step, the rate of temperature rise is 3-6°C/min; in the fourth step, the rate of temperature rise is 8 ⁇ 12°C/min.
  • the process of the second step is replaced by: adding the mixed solution to a high-pressure reactor, injecting high-pressure carbon dioxide into the reactor, and stirring and reacting at a temperature of 150-180°C and a pressure of 18-28 MPa for 1 to 1.5 hours, After being naturally cooled to room temperature, the pressure is relieved, the solid is separated, the solid is washed with deionized water and ethanol, and then dried in a vacuum drying oven at 60-80° C. for 10-14 hours to obtain a spherical indium hydroxide solid.
  • compounds with oxygen vacancies can capture oxygen ions, while uranium in seawater is uranyl ions, which are uranium-oxygen complexes, such as UO 2 2+ .
  • Oxygen vacancies capture oxygen, which can achieve indirect capture of uranium. The effect of this makes it easier for oxygen vacancy compounds to capture uranyl ions.
  • the vacancies of compounds with oxygen vacancies capture oxygen, it is equivalent to grabbing a UO 2 2+ , and we have to negatively charge it to reduce it to UO 2 crystals. It can be fixed. Once reduced UO 2 crystals appear, the subsequent reduction process is similar to the crystal crystallization process. The longer it grows and the larger it is, the extraction of uranium in seawater is realized.
  • the present invention includes at least the following beneficial effects: the present invention prepares the metal oxide In 2 O 3-x containing oxygen vacancies, mixes the oxide with the film solution and uniformly coats it on the carbon paper, and waits for the carbon paper to dry naturally. Afterwards, the dried carbon paper was clamped with gold electrodes and used as the working electrode in the three-electrode system.
  • the three-electrode system was used to electrolyze uranium-containing simulated seawater to achieve the extraction of uranium. The extraction method is simple and easy to implement.
  • Fig. 1 is an XRD pattern of In 2 O 3-x samples with oxygen vacancies and pure In 2 O 3 prepared in Examples 1 and 4 of the present invention
  • Example 2 is an HRTEM image of an In 2 O 3-x sample with oxygen vacancies prepared in Example 1 of the present invention
  • Example 3 is a TEM image of an In 2 O 3-x sample with oxygen vacancies prepared in Example 1 of the present invention
  • a method for extracting uranium from electrochemical seawater using metal oxides containing oxygen vacancies including the following steps:
  • Step 1 Dissolve 3g In(NO 3 ) 3 ⁇ 4.5H 2 O in 300 mL of isopropanol, stir for 0.5 hours, and ultrasonic for 1 hour to obtain indium nitrate isopropanol solution; add 100g to indium nitrate isopropanol solution Glycerol, stirring for 0.5 hours, sonicating for 0.5 hours to obtain a mixed solution; the ultrasonic power is 800W, and the frequency is 35KHz;
  • Step 2 Transfer the mixed solution to a polytetrafluoroethylene high-temperature and high-pressure reactor, heat up to 180°C at a rate of 5°C/min, keep it for 1 hour, and cool to room temperature naturally, separate the solid and liquid, and use deionized water for the solids. Wash with ethanol, and then dry in a vacuum drying oven at 60°C for 12 hours to obtain spherical indium hydroxide solid;
  • Step 3 Dissolve 0.2g of spherical indium hydroxide solid in 30mL of deionized water, sonicate for 0.5 hours, then transfer the sonicated solution to a polytetrafluoroethylene high-temperature and high-pressure reactor, and heat up to 50°C at 5°C/min. Keep it warm for 1 hour, cool to room temperature naturally, wash with ethanol, and then dry in an oven at 60°C for 12 hours to obtain flake indium hydroxide solid; the ultrasonic power is 800W, and the frequency is 35KHz;
  • Step 4 The flake indium hydroxide solid is heated to 400°C at 10°C/min under an atmosphere with a hydrogen content of 5% or less, and calcined for 2 hours to obtain a calcined In 2 O 3-x sample with oxygen vacancies ; ( X in In 2 O 3-x represents oxygen vacancy content);
  • Step 5 Add 50mg In 2 O 3-x sample to 20mL ethanol and sonicate for 1 hour, then add 500uL nafion membrane solution and continue sonication for 1 hour; spread the ultrasonic solution evenly on the 1x2cm carbon paper and wait for the carbon paper After natural drying, the dried carbon paper is clamped with a gold electrode and used as the working electrode in the three-electrode system, and the counter electrode in the three-electrode system is a platinum wire, and the reference electrode is a calomel electrode; The power is 800W and the frequency is 35KHz;
  • Step 6 Add 166.38ug of uranyl nitrate and 29.2g of sodium chloride to 1L of deionized water, and sonicate to obtain simulated seawater with a U 6+ concentration of 100 ug/L and a sodium chloride concentration of 0.5 mol/L; the ultrasound
  • the power is 800W, the frequency is 35KHz; the simulated seawater is added to the electrolytic cell, the three-electrode system is placed in the simulated seawater of the electrolytic cell, and the simulated seawater is stirred for electrolysis.
  • the electrolytic cell voltage is set to -4V, and the electrolysis is 10min.
  • the power is cut off for 30 seconds every 1 minute; the extraction of uranium in simulated seawater is completed; the U 6+ concentration after uranium extraction in simulated seawater is tested by ICP-MS to be 10ug/L;
  • Step 7 After the electrolysis is completed, place the three-electrode system in an electrolytic cell containing 0.5mol/L sodium chloride solution and stir for electrolysis; set the electrolytic cell voltage to +0.4V, power on for 2 minutes, power off for 0.5 minutes, and repeat The power-on and power-off processes are 20 times; U 4+ on the working electrode is oxidized to U 6+ in a sodium chloride solution with a concentration of 0.5 mol/L; ICP-MS is used to test a 0.5 mol/L sodium chloride solution The concentration of U 6+ in is 87ug/L.
  • a method for extracting uranium from electrochemical seawater using metal oxides containing oxygen vacancies including the following steps:
  • Step 1 Dissolve 3g of In(NO 3 ) 3 ⁇ 4.5H 2 O in 300 mL of isopropanol, stir for 1 hour, and ultrasound for 0.5 hours to obtain an indium nitrate isopropanol solution; add 100g to the indium nitrate isopropanol solution Glycerol, stirring for 1 hour, sonicating for 0.5 hour to obtain a mixed solution; the ultrasonic power is 800W, and the frequency is 40KHz;
  • Step 2 Transfer the mixed solution to a polytetrafluoroethylene high-temperature and high-pressure reactor, heat up to 185°C at a rate of 5°C/min, keep it for 2 hours, and cool to room temperature naturally, separate the solid and liquid, and use deionized water for the solids. Wash with ethanol, and then dry in a vacuum drying oven at 60°C for 12 hours to obtain spherical indium hydroxide solid;
  • Step 3 Dissolve 1g of spherical indium hydroxide solid in 150mL deionized water, sonicate for 1 hour, then transfer the sonicated solution to a polytetrafluoroethylene high-temperature and high-pressure reactor, heat up to 60°C at 5°C/min, and keep it warm. 2 hours, naturally cooled to room temperature, washed with ethanol, and then dried in an oven at 60°C for 12 hours to obtain flake indium hydroxide solid; the ultrasonic power is 800W, and the frequency is 40KHz;
  • Step 4 The flake indium hydroxide solid is heated to 385°C at 10°C/min under an atmosphere with a hydrogen content of 5% or less, and calcined for 3 hours to obtain a calcined In 2 O 3-x sample with oxygen vacancies ;
  • Step 5 Add 50mg In 2 O 3-x sample to 20mL ethanol and sonicate for 1 hour, then add 500uL nafion membrane solution and continue sonication for 1 hour; spread the ultrasonic solution evenly on the 1x2cm carbon paper and wait for the carbon paper After natural drying, the dried carbon paper is clamped with a gold electrode and used as the working electrode in the three-electrode system, and the counter electrode in the three-electrode system is a platinum wire, and the reference electrode is a calomel electrode; The power is 800W and the frequency is 40KHz;
  • Step 6 Add 166.38ug of uranyl nitrate and 29.2g of sodium chloride to 1L of deionized water, and sonicate to obtain simulated seawater with a U 6+ concentration of 100 ug/L and a sodium chloride concentration of 0.5 mol/L; the ultrasound
  • the power is 800W, the frequency is 35KHz;
  • the simulated seawater is added to the electrolytic cell, the three-electrode system is placed in the simulated seawater of the electrolytic cell, and the simulated seawater is stirred for electrolysis.
  • the electrolytic cell voltage is set to -5V, and the electrolysis is 10min.
  • the power is turned off for 30 seconds every 1 minute when the power is turned on; the extraction of uranium in the simulated seawater is completed; through the process of power on, power off, and stirring, the concentration of U 6+ near the working electrode can be increased, and the extraction efficiency can be improved; ICP is adopted -MS test simulated the U 6+ concentration after extracting uranium from seawater is 9ug/L;
  • Step 7 After the electrolysis is completed, place the three-electrode system in an electrolytic cell containing 0.5 mol/L sodium chloride solution and stir for electrolysis; set the electrolytic cell voltage to +0.5V, power on for 2 minutes, power off for 0.5 minutes, and repeat The power-on and power-off process is 20 times; U 4+ on the working electrode is oxidized to U 6+ in a sodium chloride solution with a concentration of 0.8 mol/L; ICP-MS is used to test a 0.5 mol/L sodium chloride solution The concentration of U 6+ in is 87ug/L.
  • a method for extracting uranium from electrochemical seawater using metal oxides containing oxygen vacancies including the following steps:
  • Step 1 Dissolve 3g In(NO 3 ) 3 ⁇ 4.5H 2 O in 300 mL of isopropanol, stir for 1 hour, and ultrasonic for 1 hour to obtain indium nitrate isopropanol solution; add 100g to indium nitrate isopropanol solution Glycerol, stirring for 1 hour, sonicating for 1 hour to obtain a mixed solution; the ultrasonic power is 800W, and the frequency is 40KHz;
  • Step 2 Transfer the mixed solution to a polytetrafluoroethylene high-temperature and high-pressure reactor, heat up to 200°C at a rate of 5°C/min, keep it for 1 hour, and cool to room temperature naturally, separate the solid and liquid, and use deionized water for the solids. Wash with ethanol, and then dry in a vacuum drying oven at 60°C for 12 hours to obtain spherical indium hydroxide solid;
  • Step 3 Dissolve 1g of spherical indium hydroxide solid in 150mL deionized water, sonicate for 1 hour, then transfer the sonicated solution to a polytetrafluoroethylene high-temperature and high-pressure reactor, heat up to 60°C at 5°C/min, and keep it warm. 2 hours, naturally cooled to room temperature, washed with ethanol, and then dried in an oven at 60°C for 12 hours to obtain flake indium hydroxide solid; the ultrasonic power is 800W, and the frequency is 40KHz;
  • Step 4 The flake indium hydroxide solid is heated to 400°C at 10°C/min under an atmosphere with a hydrogen content of 5% or less, and calcined for 2 hours to obtain a calcined In 2 O 3-x sample with oxygen vacancies ;
  • Step 5 Add 50mg In 2 O 3-x sample to 20mL ethanol and sonicate for 1 hour, then add 500uL nafion membrane solution and continue sonication for 1 hour; spread the ultrasonic solution evenly on the 1x2cm carbon paper and wait for the carbon paper After natural drying, the dried carbon paper is clamped with a gold electrode and used as the working electrode in the three-electrode system, and the counter electrode in the three-electrode system is a platinum wire, and the reference electrode is a calomel electrode; The power is 800W and the frequency is 40KHz;
  • Step 6 Add 166.38ug of uranyl nitrate and 29.2g of sodium chloride to 1L of deionized water, and sonicate to obtain simulated seawater with a U 6+ concentration of 100 ug/L and a sodium chloride concentration of 0.5 mol/L; the ultrasound
  • the power is 800W, the frequency is 35KHz; the simulated seawater is added to the electrolytic cell, the three-electrode system is placed in the simulated seawater of the electrolytic cell, and the simulated seawater is stirred for electrolysis.
  • the electrolytic cell voltage is set to -3V, and the electrolysis is 10min.
  • the power is cut off for 30 seconds every 1 minute; the extraction of uranium in simulated seawater is completed; the U 6+ concentration after uranium extraction in simulated seawater is tested by ICP-MS to be 8ug/L;
  • Step 7 After electrolysis is completed, place the three-electrode system in an electrolytic cell containing 0.5 mol/L sodium chloride solution and stir for electrolysis; set the electrolytic cell voltage to +0.3V, power on for 2 minutes, power off for 0.5 minutes, and repeat The power-on and power-off process is 20 times; the U 4+ on the working electrode is oxidized to U 6+ in a sodium chloride solution with a concentration of 0.5 mol/L. The concentration of U 6+ in the 0.5mol/L sodium chloride solution tested by ICP-MS was 88ug/L.
  • a method for extracting uranium from electrochemical seawater using metal oxides containing oxygen vacancies including the following steps:
  • Step 1 Dissolve 3g In(NO 3 ) 3 ⁇ 4.5H 2 O in 300 mL of isopropanol, stir for 0.5 hours, and ultrasonic for 1 hour to obtain indium nitrate isopropanol solution; add 100g to indium nitrate isopropanol solution Glycerol, stirring for 0.5 hours, sonicating for 0.5 hours to obtain a mixed solution; the ultrasonic power is 800W, and the frequency is 35KHz;
  • Step 2 Add the mixed solution to the high-pressure reactor, inject high-pressure carbon dioxide into the reactor, stir and react for 1 hour at a temperature of 180°C and a pressure of 20 MPa, cool to room temperature and release the pressure, separate the solid and liquid, and use the solid separately Wash with ionized water and ethanol, and then dry in a vacuum drying cabinet at 60°C for 12 hours to obtain spherical indium hydroxide solids.
  • the reaction is carried out in the supercritical carbon dioxide reaction system, and the reaction is more uniform under the action of supercritical carbon dioxide. Increase the oxygen vacancy content of the In 2 O 3-x sample prepared subsequently;
  • Step 3 Dissolve 0.2g of spherical indium hydroxide solid in 30mL of deionized water, sonicate for 0.5 hours, then transfer the sonicated solution to a polytetrafluoroethylene high temperature and high pressure reactor, and heat up to 50°C at 5°C/min. Insulate for 1 hour, cool to room temperature naturally, wash with ethanol, and then dry in an oven at 60°C for 12 hours to obtain flake indium hydroxide solid;
  • Step 4 The flake indium hydroxide solid is heated to 400°C at 10°C/min under an atmosphere with a hydrogen content of less than 5%, and calcined for 2 hours to obtain a calcined In 2 O 3-x sample with oxygen vacancies ;
  • Step 5 Add 50mg In 2 O 3-x sample to 20mL ethanol and sonicate for 1 hour, then add 500uL nafion membrane solution and continue sonication for 1 hour; spread the ultrasonic solution evenly on the 1x2cm carbon paper and wait for the carbon paper After natural drying, the dried carbon paper is clamped with a gold electrode and used as the working electrode in the three-electrode system, and the counter electrode in the three-electrode system is a platinum wire, and the reference electrode is a calomel electrode; The power is 800W and the frequency is 35KHz;
  • Step 6 Add 166.38ug of uranyl nitrate and 29.2g of sodium chloride to 1L of deionized water, and sonicate to obtain simulated seawater with a U 6+ concentration of 100 ug/L and a sodium chloride concentration of 0.5 mol/L; the ultrasound
  • the power is 800W, the frequency is 35KHz; the simulated seawater is added to the electrolytic cell, the three-electrode system is placed in the simulated seawater of the electrolytic cell, and the simulated seawater is stirred for electrolysis.
  • the electrolytic cell voltage is set to -4V, and the electrolysis is 10min.
  • the power is turned off for 30 seconds every 1 minute; the extraction of uranium in simulated seawater is completed; the U 6+ concentration after uranium extraction in simulated seawater is tested by ICP-MS to be 6ug/L;
  • Step 7 After the electrolysis is completed, place the three-electrode system in an electrolytic cell containing 0.5mol/L sodium chloride solution and stir for electrolysis; set the electrolytic cell voltage to +0.4V, power on for 2 minutes, power off for 0.5 minutes, and repeat The power-on and power-off processes are 20 times; the U 4+ on the working electrode is oxidized to U 6+ in a sodium chloride solution with a concentration of 0.3-0.8 mol/L. The concentration of U 6+ in the 0.5mol/L sodium chloride solution is 90ug/L by ICP-MS.
  • Figure 1 the In 2 O 3-x samples with oxygen vacancies prepared in Example 1 and Example 4 are consistent with the crystal phase of pure In 2 O 3 and are cubic crystal phases;
  • Figure 2 is Example 1 The prepared In 2 O 3-x sample with oxygen vacancies can also be characterized as a cubic crystal phase;
  • Figure 3 is the TEM image of the In 2 O 3-x sample with oxygen vacancies prepared in Example 1. It can be seen that In The 2 O 3-x sample has a sheet-like appearance;
  • Figure 4 is the ESR spectrum of the In 2 O 3-x sample with oxygen vacancies and pure In 2 O 3 prepared in Examples 1 and 4 of the present invention; it shows around 3400Gs The signal of is due to the capture of electrons by oxygen vacancies.
  • Figure 5 shows the In 2 with oxygen vacancies prepared in Examples 1 and 4 of the present invention PL spectra of O 3-x sample and pure In 2 O 3 ; the PL emission peak at 435nm is mainly due to the recombination of oxygen vacancies caused by the capture of electrons by photo-generated holes.
  • the stronger the signal the better the prepared In 2 O
  • the oxygen vacancy content of the 3-x sample is higher;
  • Figure 6 is the XPS spectra (O1s) of the In 2 O 3-x sample with oxygen vacancies and pure In 2 O 3 prepared in Examples 1 to 4 of the present invention, O1s core Two peaks can also be clearly identified in the layer spectrum.
  • the In-O-In bond at 529.8 is the In-O-In bond, and the other at 531.4eV is the oxygen atom near the oxygen vacancy.
  • a method for extracting uranium from electrochemical seawater using metal oxides containing oxygen vacancies including the following steps:
  • Step 1 Dissolve 3g of In(NO 3 ) 3 ⁇ 4.5H 2 O in 300 mL of isopropanol, stir for 1 hour, and ultrasound for 0.5 hours to obtain an indium nitrate isopropanol solution; add 100g to the indium nitrate isopropanol solution Glycerol, stirring for 1 hour, sonicating for 0.5 hour to obtain a mixed solution; the ultrasonic power is 800W, and the frequency is 40KHz;
  • Step 2 Add the mixed solution to the high-pressure reactor, inject high-pressure carbon dioxide into the reactor, stir and react for 2 hours at a temperature of 185°C and a pressure of 22MPa, cool to room temperature and release the pressure, separate the solid and liquid, and use the solid separately Wash with ionized water and ethanol, and then dry in a vacuum drying oven at 60°C for 12 hours to obtain spherical indium hydroxide solid;
  • Step 3 Dissolve 1g of spherical indium hydroxide solid in 150mL deionized water, sonicate for 1 hour, then transfer the sonicated solution to a polytetrafluoroethylene high-temperature and high-pressure reactor, heat up to 60°C at 5°C/min, and keep it warm. 2 hours, naturally cool to room temperature, wash with ethanol, and then dry in an oven at 60°C for 12 hours to obtain flake indium hydroxide solid;
  • Step 4 The flake indium hydroxide solid is heated to 385°C at 10°C/min under an atmosphere with a hydrogen content of 5% or less, and calcined for 3 hours to obtain a calcined In 2 O 3-x sample with oxygen vacancies ;
  • Step 5 Add 50mg In 2 O 3-x sample to 20mL ethanol and sonicate for 1 hour, then add 500uL nafion membrane solution and continue sonication for 1 hour; spread the ultrasonic solution evenly on the 1x2cm carbon paper and wait for the carbon paper After natural drying, the dried carbon paper is clamped with a gold electrode and used as the working electrode in the three-electrode system, and the counter electrode in the three-electrode system is a platinum wire, and the reference electrode is a calomel electrode; The power is 800W and the frequency is 40KHz;
  • Step 6 Add 166.38ug of uranyl nitrate and 29.2g of sodium chloride to 1L of deionized water, and sonicate to obtain simulated seawater with a U 6+ concentration of 100 ug/L and a sodium chloride concentration of 0.5 mol/L; the ultrasound
  • the power is 800W, the frequency is 35KHz; the simulated seawater is added to the electrolytic cell, the three-electrode system is placed in the simulated seawater of the electrolytic cell, and the simulated seawater is stirred for electrolysis.
  • the electrolytic cell voltage is set to -5V, and the electrolysis is 10min.
  • the power is cut off for 30 seconds every 1 minute; the extraction of uranium in simulated seawater is completed; the U 6+ concentration after uranium extraction in simulated seawater is tested by ICP-MS to be 5ug/L;
  • Step 7 After the electrolysis is completed, place the three-electrode system in an electrolytic cell containing 0.5 mol/L sodium chloride solution and stir for electrolysis; set the electrolytic cell voltage to +0.5V, power on for 2 minutes, power off for 0.5 minutes, and repeat The power-on and power-off processes are 20 times; the U 4+ on the working electrode is oxidized to U 6+ in a sodium chloride solution with a concentration of 0.5 mol/L. The concentration of U 6+ in the 0.5mol/L sodium chloride solution tested by ICP-MS was 91ug/L.
  • a method for extracting uranium from electrochemical seawater using metal oxides containing oxygen vacancies including the following steps:
  • Step 1 Dissolve 3g In(NO 3 ) 3 ⁇ 4.5H 2 O in 300 mL of isopropanol, stir for 1 hour, and ultrasonic for 1 hour to obtain indium nitrate isopropanol solution; add 100g to indium nitrate isopropanol solution Glycerol, stirring for 1 hour, sonicating for 1 hour to obtain a mixed solution; the ultrasonic power is 800W, and the frequency is 40KHz;
  • Step 2 Add the mixed solution to the high-pressure reactor, inject high-pressure carbon dioxide into the reactor, stir and react for 1 hour at a temperature of 200°C and a pressure of 25MPa, cool to room temperature and release the pressure, separate the solid and liquid, and use the solid separately Wash with ionized water and ethanol, and then dry in a vacuum drying oven at 60°C for 12 hours to obtain spherical indium hydroxide solid;
  • Step 3 Dissolve 1g of spherical indium hydroxide solid in 150mL deionized water, sonicate for 1 hour, then transfer the sonicated solution to a polytetrafluoroethylene high-temperature and high-pressure reactor, heat up to 60°C at 5°C/min, and keep it warm. 2 hours, naturally cool to room temperature, wash with ethanol, and then dry in an oven at 60°C for 12 hours to obtain flake indium hydroxide solid;
  • Step 4 The flake indium hydroxide solid is heated to 400°C at 10°C/min under an atmosphere with a hydrogen content of 5% or less, and calcined for 2 hours to obtain a calcined In 2 O 3-x sample with oxygen vacancies ;
  • Step 5 Add 50mg In 2 O 3-x sample to 20mL ethanol and sonicate for 1 hour, then add 500uL nafion membrane solution and continue sonication for 1 hour; spread the ultrasonic solution evenly on the 1x2cm carbon paper and wait for the carbon paper After natural drying, the dried carbon paper is clamped with a gold electrode and used as the working electrode in the three-electrode system, and the counter electrode in the three-electrode system is a platinum wire, and the reference electrode is a calomel electrode; The power is 800W and the frequency is 40KHz;
  • Step 6 Add 166.38ug of uranyl nitrate and 29.2g of sodium chloride to 1L of deionized water, and sonicate to obtain simulated seawater with a U 6+ concentration of 100 ug/L and a sodium chloride concentration of 0.5 mol/L; the ultrasound
  • the power is 800W, the frequency is 35KHz; the simulated seawater is added to the electrolytic cell, the three-electrode system is placed in the simulated seawater of the electrolytic cell, and the simulated seawater is stirred for electrolysis.
  • the electrolytic cell voltage is set to -3V, and the electrolysis is 10min.
  • the power is cut off for 30 seconds every 1 minute; the extraction of uranium in simulated seawater is completed; the U 6+ concentration after uranium extraction in simulated seawater is tested by ICP-MS to be 5ug/L;
  • Step 7 After electrolysis is completed, place the three-electrode system in an electrolytic cell containing 0.5 mol/L sodium chloride solution and stir for electrolysis; set the electrolytic cell voltage to +0.3V, power on for 2 minutes, power off for 0.5 minutes, and repeat The power-on and power-off process is 20 times; the U 4+ on the working electrode is oxidized to U 6+ in a sodium chloride solution with a concentration of 0.5 mol/L. The concentration of U 6+ in the 0.5mol/L sodium chloride solution tested by ICP-MS was 92ug/L.

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Abstract

一种利用含有氧空位的金属氧化物电化学海水提铀的方法，包括：在硝酸铟异丙醇溶液中加入丙三醇，然后转移到高温高压反应釜中反应，得到球形氢氧化铟固体；将球形氢氧化铟固体溶于去离子水中，然后转移到高温高压反应釜中反应，即得到片状氢氧化铟固体；将片状氢氧化铟固体煅烧得到煅烧后的具有氧空位的In 2O 3-x；将In 2O 3-x加入乙醇，然后再加入膜溶液；将溶液均匀的涂在碳纸上，自然干燥后，用金电极夹住干燥后的碳纸，并被用作三电极体系中的工作电极，且三电极体系中的对电极为铂丝，参比电极为甘汞电极；将模拟海水加入电解池中，将三电极体系放置在电解池的模拟海水中，搅拌模拟海水进行电解，实现铀的提取。

Description

利用含有氧空位的金属氧化物电化学海水提铀的方法 技术领域
本发明涉及一种海水提铀的方法，具体涉及一种利用含有氧空位的金属氧化物电化学海水提铀的方法。
背景技术
铀是核电原料，天然矿石中的铀矿储量很少。目前，全球可开发性矿石铀资源有限，世界海洋总水量约为1.37×10 12m 3，海水中铀元素总储备量达42.9亿吨，是陆地储量的近1000倍。随着核电以及低碳经济的发展，铀资源的需求日益迫切，基于铀的稀缺性以及铀矿产资源的有限性，从海水中提取铀作为传统矿石类铀资源的补充或替代，具有重要意义。
目前提取的铀方法主要有化学沉淀法、离子交换法、膜分离法和吸附法等。化学沉淀法设备简单、费用低、效率高，但反应所产生的聚合物需进一步浓缩、脱水和固化；离子交换法提取效率高，净化效果好，但价格昂贵，选择性差，交换容量有限；膜分离法操作简单、能耗低、适应性强，但对原水的水质要求较高，常需与其他水处理技术联用；而吸附法对于吸附剂要求需要有处理量大、吸附剂选择性强、耐腐性强、机械强度大等特性，并且现有的吸附材料在实际应用中还存在吸附效率低、生产成本高、回收再利用困难等缺陷。
具有氧空位的化合物能够对氧离子进行捕捉，而海水里面铀是铀酰离子，就是铀氧络合物，比如UO 2 2+，氧空位是捕捉氧，可以达到间接捕捉铀的效果使氧空位化合物更容易捕捉铀酰离子。同时采用电化学电解方法，将具有氧空位的化合物涂在碳纸上作为工作电极，并采用铂丝为对电极，甘汞电极为参比电极，通过给电极通电，将海水中的铀固定在工作电极上，实现对海水中的铀的提取。
发明内容
本发明的一个目的是解决至少上述问题和/或缺陷，并提供至少后面将说明的优点。
为了实现根据本发明的这些目的和其它优点，提供了一种利用含有氧空位的金属氧化物电化学海水提铀的方法，包括以下步骤：
步骤一、配制浓度为0.024～0.028mol/L的硝酸铟异丙醇溶液；在硝酸铟异丙醇溶液中加入丙三醇，搅拌0.5～1小时，超声0.5～1小时，得到混合溶液；
步骤二、将混合溶液转移到聚四氟乙烯高温高压反应釜中，升温至160～200℃，保温1～3小时，自然冷却至室温后，固液分离，固体分别用去离子水和乙醇洗涤，然后在真空干燥箱中60～80℃干燥10～14小时，得到球形氢氧化铟固体；
步骤三、将球形氢氧化铟固体溶于去离子水中，超声0.5～1小时，然后将超声后的溶液转移到聚四氟乙烯高温高压反应釜中，升温至40～60℃，保温1～3小时，自然冷却至室温，用乙醇洗涤，然后在烘箱中60～80℃干燥10～14小时，即得到片状氢氧化铟固体；
步骤四、将片状氢氧化铟固体在氢气含量为5％以下的气氛下，升温至350～450℃，煅烧1～3小时，得到煅烧后的具有氧空位的In 2O 3-x样品；
步骤五、将In 2O 3-x样品加入乙醇中超声0.5～1小时，然后再加入膜溶液，继续超声0.5～1小时；将超声后的溶液均匀的涂在碳纸上，待碳纸自然干燥后，用金电极夹住干燥后的碳纸，并被用作三电极体系中的工作电极，且三电极体系中的对电极为铂丝，参比电极为甘汞电极；
步骤六、将模拟海水加入电解池中，将三电极体系放置在电解池的模拟海水中，搅拌模拟海水进行电解实现海水提铀，设置电解池电压为-0.3～-0.5V，电解10～100min，在电解的过程中，每通电1～2min，断电30～60s。
优选的是，所述硝酸铟异丙醇溶液的配制方法为：将In(NO 3) 3·4.5H 2O溶于异丙醇中，搅拌0.5～1小时，超声0.5～1小时，得到硝酸铟异丙醇溶液；所述In(NO 3) 3·4.5H 2O与丙三醇的质量比为3:80～120；
优选的是，所述步骤三中，球形氢氧化铟固体与去离子水中的质量体积比为1g:120～160mL。
优选的是，所述步骤五中，In 2O 3-x样品与乙醇的质量体积比为 1mg:0.2～0.6mL；所述In 2O 3-x样品与膜溶液的质量体积比为1mg:10uL。
优选的是，所述步骤五中，膜溶液为nafion膜溶液。
优选的是，所述模拟海水制备方法为：将硝酸铀酰和氯化钠溶于去离子水中，超声0.5～1小时，得到模拟海水；所述模拟海水中U 6+的浓度为50～150ug/L、氯化钠浓度为0.1～1mol/L。
优选的是，所述步骤六中，电解完成后，将三电极体系放置在含有0.1～1mol/L氯化钠溶液的电解池中，搅拌进行电解；设置电解池电压为+0.3～+0.5V，通电1～3分钟，断电0.5～1分钟，重复该通电、断电过程15～30次；让工作电极上的U 4+在浓度为0.1～1mol/L的氯化钠溶液中氧化成为U 6+。
优选的是，所述步骤一、步骤三、步骤五中采用的超声的功率为600～1200W，频率为28～40KHz。
优选的是，所述步骤二中，升温的速率为3～6℃/min；所述步骤三中，升温的速率为3～6℃/min；所述步骤四中，升温的速率为8～12℃/min。
优选的是，所述步骤二的过程替换为：将混合溶液加入到高压反应器中，向反应器内注入高压二氧化碳，在温度150～180℃、压力18～28MPa下搅拌反应1～1.5小时，自然冷却至室温后泄压，固液分离，固体分别用去离子水和乙醇洗涤，然后在真空干燥箱中60～80℃干燥10～14小时，得到球形氢氧化铟固体。
在本发明中，具有氧空位的化合物能够对氧离子进行捕捉，而海水里面铀是铀酰离子，就是铀氧络合物，比如UO 2 2+，氧空位是捕捉氧，可以达到间接捕捉铀的效果，使氧空位化合物更容易捕捉铀酰离子，具有氧空位的化合物的空位捕捉到氧后，相当于抓了一个UO 2 2+，我们得给它通负电让它还原成UO 2晶体，才能固定下来，一旦有还原的UO 2晶体出现，后面的还原过程就类似于晶体结晶过程，在上面越长越大，实现海水中铀的提取。
本发明至少包括以下有益效果：本发明通过制备含有氧空位的金属氧化物In 2O 3-x，并将该氧化物与膜溶液进行混合后均匀的涂在碳纸上，待碳纸自然干燥后，用金电极夹住干燥后的碳纸，并被用作三电极体系中的工作电极，采用该三电极体系对含铀模拟海水进行电解，实现对铀的提取，该提取方法简单易行，且将电解后的三电极体系放置在含有氯化钠溶液的电解池中，反 向设置电压进行电解，可以将工作电极上的U 4+在氯化钠溶液中氧化成为U 6+；实现铀的回收。
本发明的其它优点、目标和特征将部分通过下面的说明体现，部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。
附图说明：
图1为本发明实施例1和4制备的具有氧空位的In 2O 3-x样品和纯In 2O 3的XRD图；
图2为本发明实施例1制备的具有氧空位的In 2O 3-x样品的HRTEM图；
图3为本发明实施例1制备的具有氧空位的In 2O 3-x样品的TEM图；
图4为本发明实施例1和4制备的具有氧空位的In 2O 3-x样品和纯In 2O 3的ESR谱图；
图5为本发明实施例1和4制备的具有氧空位的In 2O 3-x样品和纯In 2O 3的PL谱图；
图6为本发明实施例1和4制备的具有氧空位的In 2O 3-x样品和纯In 2O 3的XPS谱图(O1s)。
具体实施方式：
下面结合附图对本发明做进一步的详细说明，以令本领域技术人员参照说明书文字能够据以实施。
应当理解，本文所使用的诸如“具有”、“包含”以及“包括”术语并不配出一个或多个其它元件或其组合的存在或添加。
实施例1：
一种利用含有氧空位的金属氧化物电化学海水提铀的方法，包括以下步骤：
步骤一、将3g In(NO 3) 3·4.5H 2O溶于300mL异丙醇中，搅拌0.5小时，超声1小时，得到硝酸铟异丙醇溶液；在硝酸铟异丙醇溶液中加入100g丙三醇，搅拌0.5小时，超声0.5小时，得到混合溶液；所述超声的功率为800W，频率为35KHz；
步骤二、将混合溶液转移到聚四氟乙烯高温高压反应釜中，以5℃/min的速度升温至180℃，保温1小时，自然冷却至室温后，固液分离，固体分别用去离子水和乙醇洗涤，然后在真空干燥箱中60℃干燥12小时，得到球形氢氧化铟固体；
步骤三、将0.2g球形氢氧化铟固体溶于30mL去离子水中，超声0.5小时，然后将超声后的溶液转移到聚四氟乙烯高温高压反应釜中，以5℃/min升温至50℃，保温1小时，自然冷却至室温，用乙醇洗涤，然后在烘箱中60℃干燥12小时，即得到片状氢氧化铟固体；所述超声的功率为800W，频率为35KHz；
步骤四、将片状氢氧化铟固体在氢气含量为5％以下的气氛下，以10℃/min升温至400℃，煅烧2小时，得到煅烧后的具有氧空位的In 2O 3-x样品；(In 2O 3-x中的X代表氧空位含量)；
步骤五、将50mg In 2O 3-x样品加入20mL乙醇中超声1小时，然后再加入500uL nafion膜溶液，继续超声1小时；将超声后的溶液均匀的涂在1x2cm碳纸上，待碳纸自然干燥后，用金电极夹住干燥后的碳纸，并被用作三电极体系中的工作电极，且三电极体系中的对电极为铂丝，参比电极为甘汞电极；所述超声的功率为800W，频率为35KHz；
步骤六、将166.38ug硝酸铀酰和29.2g氯化钠加入1L去离子水，超声，得到U 6+的浓度为100ug/L、氯化钠浓度为0.5mol/L的模拟海水；所述超声的功率为800W，频率为35KHz；将模拟海水加入电解池中，将三电极体系放置在电解池的模拟海水中，搅拌模拟海水进行电解，设置电解池电压为-4V，电解10min，在电解的过程中，每通电1min，断电30s；完成对模拟海水中铀的提取；采用ICP-MS测试模拟海水提铀后的U 6+浓度为10ug/L；
步骤七、电解完成后，将三电极体系放置在含有0.5mol/L氯化钠溶液的电解池中，搅拌进行电解；设置电解池电压为+0.4V，通电2分钟，断电0.5分钟，重复该通电、断电过程20次；让工作电极上的U 4+在浓度为0.5mol/L的氯化钠溶液中氧化成为U 6+；采用ICP-MS测试0.5mol/L的氯化钠溶液中的U 6+浓度为87ug/L。
实施例2：
一种利用含有氧空位的金属氧化物电化学海水提铀的方法，包括以下步骤：
步骤一、将3g In(NO 3) 3·4.5H 2O溶于300mL异丙醇中，搅拌1小时，超声0.5小时，得到硝酸铟异丙醇溶液；在硝酸铟异丙醇溶液中加入100g丙三醇，搅拌1小时，超声0.5小时，得到混合溶液；所述超声的功率为800W，频率为40KHz；
步骤二、将混合溶液转移到聚四氟乙烯高温高压反应釜中，以5℃/min的速度升温至185℃，保温2小时，自然冷却至室温后，固液分离，固体分别用去离子水和乙醇洗涤，然后在真空干燥箱中60℃干燥12小时，得到球形氢氧化铟固体；
步骤三、将1g球形氢氧化铟固体溶于150mL去离子水中，超声1小时，然后将超声后的溶液转移到聚四氟乙烯高温高压反应釜中，以5℃/min升温至60℃，保温2小时，自然冷却至室温，用乙醇洗涤，然后在烘箱中60℃干燥12小时，即得到片状氢氧化铟固体；所述超声的功率为800W，频率为40KHz；
步骤四、将片状氢氧化铟固体在氢气含量为5％以下的气氛下，以10℃/min升温至385℃，煅烧3小时，得到煅烧后的具有氧空位的In 2O 3-x样品；
步骤五、将50mg In 2O 3-x样品加入20mL乙醇中超声1小时，然后再加入500uL nafion膜溶液，继续超声1小时；将超声后的溶液均匀的涂在1x2cm碳纸上，待碳纸自然干燥后，用金电极夹住干燥后的碳纸，并被用作三电极体系中的工作电极，且三电极体系中的对电极为铂丝，参比电极为甘汞电极；所述超声的功率为800W，频率为40KHz；
步骤六、将166.38ug硝酸铀酰和29.2g氯化钠加入1L去离子水，超声，得到U 6+的浓度为100ug/L、氯化钠浓度为0.5mol/L的模拟海水；所述超声的功率为800W，频率为35KHz；将模拟海水加入电解池中，将三电极体系放置在电解池的模拟海水中，搅拌模拟海水进行电解，设置电解池电压为-5V，电解10min，在电解的过程中，每通电1min，断电30s；完成对模拟海水中铀的提取；通过通电、断电，以及搅拌的过程，可以提高U 6+在工作电极附近的浓度，提高提取的效率；采用ICP-MS测试模拟海水提铀后的U 6+浓度为 9ug/L；
步骤七、电解完成后，将三电极体系放置在含有0.5mol/L氯化钠溶液的电解池中，搅拌进行电解；设置电解池电压为+0.5V，通电2分钟，断电0.5分钟，重复该通电、断电过程20次；让工作电极上的U 4+在浓度为0.8mol/L的氯化钠溶液中氧化成为U 6+；采用ICP-MS测试0.5mol/L的氯化钠溶液中的U 6+浓度为87ug/L。
实施例3：
一种利用含有氧空位的金属氧化物电化学海水提铀的方法，包括以下步骤：
步骤一、将3g In(NO 3) 3·4.5H 2O溶于300mL异丙醇中，搅拌1小时，超声1小时，得到硝酸铟异丙醇溶液；在硝酸铟异丙醇溶液中加入100g丙三醇，搅拌1小时，超声1小时，得到混合溶液；所述超声的功率为800W，频率为40KHz；
步骤二、将混合溶液转移到聚四氟乙烯高温高压反应釜中，以5℃/min的速度升温至200℃，保温1小时，自然冷却至室温后，固液分离，固体分别用去离子水和乙醇洗涤，然后在真空干燥箱中60℃干燥12小时，得到球形氢氧化铟固体；
步骤三、将1g球形氢氧化铟固体溶于150mL去离子水中，超声1小时，然后将超声后的溶液转移到聚四氟乙烯高温高压反应釜中，以5℃/min升温至60℃，保温2小时，自然冷却至室温，用乙醇洗涤，然后在烘箱中60℃干燥12小时，即得到片状氢氧化铟固体；所述超声的功率为800W，频率为40KHz；
步骤四、将片状氢氧化铟固体在氢气含量为5％以下的气氛下，以10℃/min升温至400℃，煅烧2小时，得到煅烧后的具有氧空位的In 2O 3-x样品；
步骤五、将50mg In 2O 3-x样品加入20mL乙醇中超声1小时，然后再加入500uL nafion膜溶液，继续超声1小时；将超声后的溶液均匀的涂在1x2cm碳纸上，待碳纸自然干燥后，用金电极夹住干燥后的碳纸，并被用作三电极体系中的工作电极，且三电极体系中的对电极为铂丝，参比电极为甘汞电极；所述超声的功率为800W，频率为40KHz；
步骤六、将166.38ug硝酸铀酰和29.2g氯化钠加入1L去离子水，超声，得到U 6+的浓度为100ug/L、氯化钠浓度为0.5mol/L的模拟海水；所述超声的功率为800W，频率为35KHz；将模拟海水加入电解池中，将三电极体系放置在电解池的模拟海水中，搅拌模拟海水进行电解，设置电解池电压为-3V，电解10min，在电解的过程中，每通电1min，断电30s；完成对模拟海水中铀的提取；采用ICP-MS测试模拟海水提铀后的U 6+浓度为8ug/L；
步骤七、电解完成后，将三电极体系放置在含有0.5mol/L氯化钠溶液的电解池中，搅拌进行电解；设置电解池电压为+0.3V，通电2分钟，断电0.5分钟，重复该通电、断电过程20次；让工作电极上的U 4+在浓度为0.5mol/L的氯化钠溶液中氧化成为U 6+。采用ICP-MS测试0.5mol/L的氯化钠溶液中的U 6+浓度为88ug/L。
实施例4：
一种利用含有氧空位的金属氧化物电化学海水提铀的方法，包括以下步骤：
步骤一、将3g In(NO 3) 3·4.5H 2O溶于300mL异丙醇中，搅拌0.5小时，超声1小时，得到硝酸铟异丙醇溶液；在硝酸铟异丙醇溶液中加入100g丙三醇，搅拌0.5小时，超声0.5小时，得到混合溶液；所述超声的功率为800W，频率为35KHz；
步骤二、将混合溶液加入到高压反应器中，向反应器内注入高压二氧化碳，在温度180℃、压力20MPa下搅拌反应1小时，自然冷却至室温后泄压，固液分离，固体分别用去离子水和乙醇洗涤，然后在真空干燥箱中60℃干燥12小时，得到球形氢氧化铟固体；在超临界二氧化碳反应体系中进行反应，在超临界二氧化碳的作用下，使反应更加均匀，并进一步增加了后续制备的In 2O 3-x样品的氧空位含量；
步骤三、将0.2g球形氢氧化铟固体溶于30mL去离子水中，超声0.5小时，然后将超声后的溶液转移到聚四氟乙烯高温高压反应釜中，以5℃/min升温至50℃，保温1小时，自然冷却至室温，用乙醇洗涤，然后在烘箱中60℃干燥12小时，即得到片状氢氧化铟固体；
步骤四、将片状氢氧化铟固体在氢气含量为5％以下的气氛下，以10℃ /min升温至400℃，煅烧2小时，得到煅烧后的具有氧空位的In 2O 3-x样品；
步骤五、将50mg In 2O 3-x样品加入20mL乙醇中超声1小时，然后再加入500uL nafion膜溶液，继续超声1小时；将超声后的溶液均匀的涂在1x2cm碳纸上，待碳纸自然干燥后，用金电极夹住干燥后的碳纸，并被用作三电极体系中的工作电极，且三电极体系中的对电极为铂丝，参比电极为甘汞电极；所述超声的功率为800W，频率为35KHz；
步骤六、将166.38ug硝酸铀酰和29.2g氯化钠加入1L去离子水，超声，得到U 6+的浓度为100ug/L、氯化钠浓度为0.5mol/L的模拟海水；所述超声的功率为800W，频率为35KHz；将模拟海水加入电解池中，将三电极体系放置在电解池的模拟海水中，搅拌模拟海水进行电解，设置电解池电压为-4V，电解10min，在电解的过程中，每通电1min，断电30s；完成对模拟海水中铀的提取；采用ICP-MS测试模拟海水提铀后的U 6+浓度为6ug/L；
步骤七、电解完成后，将三电极体系放置在含有0.5mol/L氯化钠溶液的电解池中，搅拌进行电解；设置电解池电压为+0.4V，通电2分钟，断电0.5分钟，重复该通电、断电过程20次；让工作电极上的U 4+在浓度为0.3～0.8mol/L的氯化钠溶液中氧化成为U 6+。采用ICP-MS测试0.5mol/L的氯化钠溶液中的U 6+浓度为90ug/L。
从图1中可以看出，实施例1和实施例4制备的具有氧空位的In 2O 3-x样品与纯In 2O 3的晶相一致，为立方晶相；图2为实施例1制备的具有氧空位的In 2O 3-x样品，也可以表征其为立方晶相；图3为实施例1制备的具有氧空位的In 2O 3-x样品的TEM图，可以看出In 2O 3-x样品为片状相貌；图4为本发明实施例1和4制备的具有氧空位的In 2O 3-x样品和纯In 2O 3的ESR谱图；在3400Gs左右表现出的信号是由于氧空位对电子的捕获，信号越强，说明制备的In 2O 3-x样品的氧空位含量越高；图5为本发明实施例1和4制备的具有氧空位的In 2O 3-x样品和纯In 2O 3的PL谱图；在435nm处的PL发射峰主要归因于光生空穴对电子的捕获导致氧空位的复合，信号越强，说明制备的In 2O 3-x样品的氧空位含量越高；图6为本发明实施例1～4制备的具有氧空位的In 2O 3-x样品和纯In 2O 3的XPS谱图(O1s)，O1s核心层光谱中也可以清楚地识别出两个峰，位于529.8是属于In-O-In键，而另一个位于531.4eV的则是氧空 位附近的氧原子，这部分峰面积越大，说明氧空位旁边的氧原子就越多，说明氧空位越多。
实施例5：
一种利用含有氧空位的金属氧化物电化学海水提铀的方法，包括以下步骤：
步骤一、将3g In(NO 3) 3·4.5H 2O溶于300mL异丙醇中，搅拌1小时，超声0.5小时，得到硝酸铟异丙醇溶液；在硝酸铟异丙醇溶液中加入100g丙三醇，搅拌1小时，超声0.5小时，得到混合溶液；所述超声的功率为800W，频率为40KHz；
步骤二、将混合溶液加入到高压反应器中，向反应器内注入高压二氧化碳，在温度185℃、压力22MPa下搅拌反应2小时，自然冷却至室温后泄压，固液分离，固体分别用去离子水和乙醇洗涤，然后在真空干燥箱中60℃干燥12小时，得到球形氢氧化铟固体；
步骤三、将1g球形氢氧化铟固体溶于150mL去离子水中，超声1小时，然后将超声后的溶液转移到聚四氟乙烯高温高压反应釜中，以5℃/min升温至60℃，保温2小时，自然冷却至室温，用乙醇洗涤，然后在烘箱中60℃干燥12小时，即得到片状氢氧化铟固体；
步骤四、将片状氢氧化铟固体在氢气含量为5％以下的气氛下，以10℃/min升温至385℃，煅烧3小时，得到煅烧后的具有氧空位的In 2O 3-x样品；
步骤五、将50mg In 2O 3-x样品加入20mL乙醇中超声1小时，然后再加入500uL nafion膜溶液，继续超声1小时；将超声后的溶液均匀的涂在1x2cm碳纸上，待碳纸自然干燥后，用金电极夹住干燥后的碳纸，并被用作三电极体系中的工作电极，且三电极体系中的对电极为铂丝，参比电极为甘汞电极；所述超声的功率为800W，频率为40KHz；
步骤六、将166.38ug硝酸铀酰和29.2g氯化钠加入1L去离子水，超声，得到U 6+的浓度为100ug/L、氯化钠浓度为0.5mol/L的模拟海水；所述超声的功率为800W，频率为35KHz；将模拟海水加入电解池中，将三电极体系放置在电解池的模拟海水中，搅拌模拟海水进行电解，设置电解池电压为-5V，电解10min，在电解的过程中，每通电1min，断电30s；完成对模拟海水中 铀的提取；采用ICP-MS测试模拟海水提铀后的U 6+浓度为5ug/L；
步骤七、电解完成后，将三电极体系放置在含有0.5mol/L氯化钠溶液的电解池中，搅拌进行电解；设置电解池电压为+0.5V，通电2分钟，断电0.5分钟，重复该通电、断电过程20次；让工作电极上的U 4+在浓度为0.5mol/L的氯化钠溶液中氧化成为U 6+。采用ICP-MS测试0.5mol/L的氯化钠溶液中的U 6+浓度为91ug/L。
实施例6：
一种利用含有氧空位的金属氧化物电化学海水提铀的方法，包括以下步骤：
步骤一、将3g In(NO 3) 3·4.5H 2O溶于300mL异丙醇中，搅拌1小时，超声1小时，得到硝酸铟异丙醇溶液；在硝酸铟异丙醇溶液中加入100g丙三醇，搅拌1小时，超声1小时，得到混合溶液；所述超声的功率为800W，频率为40KHz；
步骤二、将混合溶液加入到高压反应器中，向反应器内注入高压二氧化碳，在温度200℃、压力25MPa下搅拌反应1小时，自然冷却至室温后泄压，固液分离，固体分别用去离子水和乙醇洗涤，然后在真空干燥箱中60℃干燥12小时，得到球形氢氧化铟固体；
步骤三、将1g球形氢氧化铟固体溶于150mL去离子水中，超声1小时，然后将超声后的溶液转移到聚四氟乙烯高温高压反应釜中，以5℃/min升温至60℃，保温2小时，自然冷却至室温，用乙醇洗涤，然后在烘箱中60℃干燥12小时，即得到片状氢氧化铟固体；
步骤四、将片状氢氧化铟固体在氢气含量为5％以下的气氛下，以10℃/min升温至400℃，煅烧2小时，得到煅烧后的具有氧空位的In 2O 3-x样品；
步骤五、将50mg In 2O 3-x样品加入20mL乙醇中超声1小时，然后再加入500uL nafion膜溶液，继续超声1小时；将超声后的溶液均匀的涂在1x2cm碳纸上，待碳纸自然干燥后，用金电极夹住干燥后的碳纸，并被用作三电极体系中的工作电极，且三电极体系中的对电极为铂丝，参比电极为甘汞电极；所述超声的功率为800W，频率为40KHz；
步骤六、将166.38ug硝酸铀酰和29.2g氯化钠加入1L去离子水，超声， 得到U 6+的浓度为100ug/L、氯化钠浓度为0.5mol/L的模拟海水；所述超声的功率为800W，频率为35KHz；将模拟海水加入电解池中，将三电极体系放置在电解池的模拟海水中，搅拌模拟海水进行电解，设置电解池电压为-3V，电解10min，在电解的过程中，每通电1min，断电30s；完成对模拟海水中铀的提取；采用ICP-MS测试模拟海水提铀后的U 6+浓度为5ug/L；
步骤七、电解完成后，将三电极体系放置在含有0.5mol/L氯化钠溶液的电解池中，搅拌进行电解；设置电解池电压为+0.3V，通电2分钟，断电0.5分钟，重复该通电、断电过程20次；让工作电极上的U 4+在浓度为0.5mol/L的氯化钠溶液中氧化成为U 6+。采用ICP-MS测试0.5mol/L的氯化钠溶液中的U 6+浓度为92ug/L。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节和这里示出与描述的图例。

Claims (10)

  1. 一种利用含有氧空位的金属氧化物电化学海水提铀的方法，其特征在于，包括以下步骤：
    步骤一、配制浓度为0.024～0.028mol/L的硝酸铟异丙醇溶液；在硝酸铟异丙醇溶液中加入丙三醇，搅拌0.5～1小时，超声0.5～1小时，得到混合溶液；
    步骤二、将混合溶液转移到聚四氟乙烯高温高压反应釜中，升温至160～200℃，保温1～3小时，自然冷却至室温后，固液分离，固体分别用去离子水和乙醇洗涤，然后在真空干燥箱中60～80℃干燥10～14小时，得到球形氢氧化铟固体；
    步骤三、将球形氢氧化铟固体溶于去离子水中，超声0.5～1小时，然后将超声后的溶液转移到聚四氟乙烯高温高压反应釜中，升温至40～60℃，保温1～3小时，自然冷却至室温，用乙醇洗涤，然后在烘箱中60～80℃干燥10～14小时，即得到片状氢氧化铟固体；
    步骤四、将片状氢氧化铟固体在氢气含量为5％以下的气氛下，升温至350～450℃，煅烧1～3小时，得到煅烧后的具有氧空位的In 2O 3-x样品；
    步骤五、将In 2O 3-x样品加入乙醇中超声0.5～1小时，然后再加入膜溶液，继续超声0.5～1小时；将超声后的溶液均匀的涂在碳纸上，待碳纸自然干燥后，用金电极夹住干燥后的碳纸，并被用作三电极体系中的工作电极，且三电极体系中的对电极为铂丝，参比电极为甘汞电极；
    步骤六、将模拟海水加入电解池中，将三电极体系放置在电解池的模拟海水中，搅拌模拟海水进行电解实现海水提铀，设置电解池电压为-0.3～-0.5V，电解10～100min，在电解的过程中，每通电1～2min，断电30～60s。
  2. 如权利要求1所述的利用含有氧空位的金属氧化物电化学海水提铀的方法，其特征在于，所述硝酸铟异丙醇溶液的配制方法为：将In(NO 3) 3·4.5H 2O溶于异丙醇中，搅拌0.5～1小时，超声0.5～1小时，得到硝酸铟异丙醇溶液；所述In(NO 3) 3·4.5H 2O与丙三醇的质量比为3:80～120；
  3. 如权利要求1所述的利用含有氧空位的金属氧化物电化学海水提铀的方法，其特征在于，所述步骤三中，球形氢氧化铟固体与去离子水中的质量 体积比为1g:120～160mL。
  4. 如权利要求1所述的利用含有氧空位的金属氧化物电化学海水提铀的方法，其特征在于，所述步骤五中，In 2O 3-x样品与乙醇的质量体积比为1mg:0.2～0.6mL；所述In 2O 3-x样品与膜溶液的质量体积比为1mg:10uL。
  5. 如权利要求1所述的利用含有氧空位的金属氧化物电化学海水提铀的方法，其特征在于，所述步骤五中，膜溶液为nafion膜溶液。
  6. 如权利要求1所述的利用含有氧空位的金属氧化物电化学海水提铀的方法，其特征在于，所述模拟海水制备方法为：将硝酸铀酰和氯化钠溶于去离子水中，超声0.5～1小时，得到模拟海水；所述模拟海水中U 6+的浓度为50～150ug/L、氯化钠浓度为0.1～1mol/L。
  7. 如权利要求1所述的利用含有氧空位的金属氧化物电化学海水提铀的方法，其特征在于，所述步骤六中，电解完成后，将三电极体系放置在含有0.3～0.8mol/L氯化钠溶液的电解池中，搅拌进行电解；设置电解池电压为+0.3～+0.5V，通电1～3分钟，断电0.5～1分钟，重复该通电、断电过程15～30次；让工作电极上的U 4+在浓度为0.1～1mol/L的氯化钠溶液中氧化成为U 6+。
  8. 如权利要求1所述的利用含有氧空位的金属氧化物电化学海水提铀的方法，其特征在于，所述步骤一、步骤三、步骤五中采用的超声的功率为600～1200W，频率为28～40KHz。
  9. 如权利要求1所述的利用含有氧空位的金属氧化物电化学海水提铀的方法，其特征在于，所述步骤二中，升温的速率为3～6℃/min；所述步骤三中，升温的速率为3～6℃/min；所述步骤四中，升温的速率为8～12℃/min。
  10. 如权利要求1所述的利用含有氧空位的金属氧化物电化学海水提铀的方法，其特征在于，所述步骤二的过程替换为：将混合溶液加入到高压反应器中，向反应器内注入高压二氧化碳，在温度150～180℃、压力18～28MPa下搅拌反应1～1.5小时，自然冷却至室温后泄压，固液分离，固体分别用去离子水和乙醇洗涤，然后在真空干燥箱中60～80℃干燥10～14小时，得到球形氢氧化铟固体。
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