CN116078415A - Preparation and application of mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium - Google Patents

Preparation and application of mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium Download PDF

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CN116078415A
CN116078415A CN202211301548.0A CN202211301548A CN116078415A CN 116078415 A CN116078415 A CN 116078415A CN 202211301548 A CN202211301548 A CN 202211301548A CN 116078415 A CN116078415 A CN 116078415A
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tio
uranium
titanium dioxide
photocatalytic
dioxide photocatalyst
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陈涛
竹文坤
李明哲
何嵘
杨帆
李�瑞
王瑞祥
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Southwest University of Science and Technology
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention discloses a preparation and application of a mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium, which comprises the following steps: adding deaerated water and manganese acetate into a sealed tank, stirring for dissolving, adding tetrabutyl titanate into the sealed tank, sealing, standing for aging, filtering, and repeatedly washing precipitate to obtain Mn-TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Mn-TiO 2 Soaking in phosphoric acid solution, heating, stirring, filtering, washing, drying, and baking at 450-550deg.C to obtain Mn-TiO 2 @PO 4 Namely, the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium. Mn-TiO prepared by the invention 2 @PO 4 Has high charge separation and abundanceThe enriched uranium restriction sites have remarkably improved removal efficiency for U (VI) and excellent durability and anti-interference capability under the condition of interfering ions and acid and alkali.

Description

Preparation and application of mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium
Technical Field
The invention relates to the technical field of photocatalyst preparation, in particular to preparation and application of a mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium.
Background
Concentrating and recovering uranium from radioactive wastewater systems is critical to protecting the environment and alleviating the growing demand for nuclear fuels. Light-assisted uranium extraction is a green technology with high selectivity for non-reduced ions, and enrichment and separation of uranium from uranium-containing wastewater can be achieved by reducing soluble hexavalent uranium (U (VI)) to insoluble tetravalent uranium (U (IV)). However, the conventional photocatalyst has low catalytic efficiency. Therefore, there is an urgent need to explore photocatalysts with high catalytic efficiency to achieve efficient uranium extraction.
TiO 2 As an environment-friendly material, the material is widely used as a starting material for photocatalytic reduction of uranium due to low cost, innocuity and high chemical stability. However, as with most conventional photocatalysts, tiO 2 Is large, has a narrow visible response range, and lacks uranium confinement sites on the surface. Various strategies have been proposed in the prior art to modulate photocatalysts to enhance uranium extraction, mainly including adjusting the band structure or introducing restriction sites with high uranium selectivity. An efficient way to adjust the energy band structure results from introducing a hetero-energy state into the bandgap of the photocatalyst, which can be achieved by introducing hetero-atoms, since the entry of doping atoms results in energy level hybridization between the original catalyst and the dopant. Previous studies have demonstrated that heteroatom doping alters the energy band structure, charge distribution and valence state of the active site, thereby improving photocatalytic activity; in addition, the functional groups with high selectivity on uranium on the surface of the catalyst can be modified, so that effective uranium extraction can be realized. Thus, the elementThe combination of prime doping and surface function modification is a very promising strategy for increasing the visible light utilization range and the selectivity to U (VI), thereby realizing the efficient extraction of uranium from radioactive wastewater, but the prior art does not have the related selectivity to TiO 2 And simultaneously carrying out element doping and surface function modification to realize the scheme of reducing uranium by photocatalysis.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a method for preparing a mesoporous titania photocatalyst for photocatalytic reduction of uranium, comprising the steps of:
adding deaerated water and manganese acetate into a sealing tank, stirring and dissolving, adding tetrabutyl titanate into the sealing tank, sealing, standing and aging, filtering, and repeatedly washing precipitate to obtain Mn-TiO 2 ；
Step two, mn-TiO is processed 2 Soaking in phosphoric acid solution, heating, stirring, filtering, washing, drying, and baking at 450-550deg.C to obtain Mn-TiO 2 @PO 4 Namely, the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium.
Preferably, in the first step, the Mn-TiO is obtained 2 And treating with hydrogen plasma for 30-60 seconds.
Preferably, the process parameters of the hydrogen plasma treatment are as follows: the air pressure is 10-100 Pa, and the power is 50-300W.
Preferably, in the first step, the mass ratio of the deaerated water to the manganese acetate is 30-60:1; the mass volume ratio of the manganese acetate to the tetrabutyl titanate is 1 g:2-5 mL; the stirring and dissolving time is 15-45 min; the aging time is 12-36 hours; the precipitate is repeatedly washed with distilled water.
Preferably, in the second step, mn-TiO 2 And the mass volume ratio of the phosphoric acid solution is 4-6 mg to 1mL; the concentration of the phosphoric acid solution is 0.2-0.3 mol/L; heating and stirring at 75-85 DEG CStirring for 8-15 h; washing with ethanol and deionized water for three times respectively, and drying at 50-70 ℃ for 8-15 h; the baking time is 0.5-1.5 h.
The invention also provides an experimental method for photocatalytic reduction of uranium in simulated radioactive wastewater by using the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium, which is prepared by the preparation method, and the mesoporous titanium dioxide photocatalyst is dispersed into U (VI) solutions with different concentrations; then adjusting the pH of the U (VI) solution with 0.1mol/L NaOH and HCl solution; before the photocatalytic reaction, stirring the U (VI) solution dispersed with the mesoporous titanium dioxide photocatalyst for 60min under the light-shielding condition; then, a 300W xenon lamp with an AM1.5G filter is used as a light source, the photocatalytic reaction is carried out under stirring, the U (VI) concentration is measured at 651.8nm by an ultraviolet spectrophotometer at different times of the photocatalytic reaction, and the removal efficiency of the U (VI) after photocatalysis is calculated:
removal efficiency= (C 0 -C t )/C 0 ×100％；
Wherein C is 0 Is the initial concentration of U (VI), C t Is the concentration of U (VI) after a certain period of time.
Preferably, the mass volume ratio of the mesoporous titanium dioxide photocatalyst to the U (VI) solution with different concentrations is 1 mg/4 mL; the concentrations of the U (VI) solutions with different concentrations are respectively as follows: 8mg/L,20mg/L,50mg/L,100mg/L, and 200mg/L; the pH is regulated to 4-9; the different time for the photocatalytic reaction is 10-200 min.
Preferably, the mesoporous titanium dioxide photocatalyst is dispersed into a U (VI) solution containing interfering ions; then adjusting the pH of the U (VI) solution to 4 with 0.1mol/L NaOH and HCl solution; before the photocatalytic reaction, stirring the U (VI) solution dispersed with the mesoporous titanium dioxide photocatalyst for 60min under the light-shielding condition; then, a 300W xenon lamp with an AM1.5G filter is used as a light source, the mixture is stirred for carrying out photocatalytic reaction for 120min, the concentration of U (VI) is measured at 651.8nm by an ultraviolet spectrophotometer, and the removal efficiency of the U (VI) after photocatalysis is calculated:
removal efficiency= (C 0 -C t )/C 0 ×100％；
Wherein C is 0 Is the initial concentration of U (VI) of 8mg/L, C t Is the concentration of U (VI) after a certain time;
when the interfering ion is K + ，Na + ，Ca 2+ ，Mg 2+ ，Sr 2+ ，Cu 2+ At any one of the cations, the concentration of the interfering ions in the U (VI) solution is 80mg/L;
when the interfering ion is F - 、NO 3 - In the case of any one of the anions, the molar ratio of U (VI) to the anion is 1:2-8.
The invention also provides an application of the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium in radioactive wastewater, which is prepared by the preparation method, wherein the mesoporous titanium dioxide photocatalyst is added into uranium-containing radioactive wastewater, stirred for 60min under a dark condition, and then stirred for photocatalytic reaction under sunlight irradiation, so that the photocatalytic reduction of hexavalent uranium in the uranium-containing radioactive wastewater is realized.
Preferably, the mass volume ratio of the mesoporous titanium dioxide photocatalyst to uranium-containing radioactive wastewater is 1 mg:3-6 mL; the time for stirring to perform the photocatalytic reaction is 60-180 min.
The invention at least comprises the following beneficial effects: mn-TiO prepared by the invention 2 @PO 4 Has high-efficiency charge separation and abundant uranium restriction sites, remarkably improves the removal efficiency of U (VI), and has excellent durability and anti-interference capability under the conditions of interfering ions and acid and alkali.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIGS. 1a and b are Mn-TiO 2 @PO 4 A TEM image of (a);
FIG. 2 is Mn-TiO 2 @PO 4 HRTEM images of (a);
FIG. 3 is Mn-TiO 2 @PO 4 SEM images of (2);
FIG. 4 is a diagram of TiO 2 ，TiO 2 @PO 4 、Mn-TiO 2 And Mn-TiO 2 @PO 4 FTIR spectra of (c);
FIG. 5 is a diagram of TiO 2 ，TiO 2 @PO 4 、Mn-TiO 2 And Mn-TiO 2 @PO 4 An XRD pattern of (b);
FIG. 6 is a diagram of the prepared TiO 2 ，TiO 2 @PO 4 、Mn-TiO 2 And Mn-TiO 2 @PO 4 Photoluminescence spectrum (PL) of (a);
FIG. 7 is a diagram of the prepared TiO 2 ，TiO 2 @PO 4 、Mn-TiO 2 And Mn-TiO 2 @PO 4 Electrochemical Impedance Spectroscopy (EIS);
FIG. 8 is a diagram of the prepared TiO 2 ，TiO 2 @PO 4 、Mn-TiO 2 And Mn-TiO 2 @PO 4 Is a transient photocurrent response of (a);
FIG. 9 is a diagram of the prepared TiO 2 ，TiO 2 @PO 4 、Mn-TiO 2 And Mn-TiO 2 @PO 4 Tauc/Davis-Mott;
FIG. 10 is a diagram of the prepared TiO 2 ，TiO 2 @PO 4 、Mn-TiO 2 And Mn-TiO 2 @PO 4 A valence band edge (VB) spectral plot of (B);
FIG. 11 is a diagram of the prepared TiO 2 ，TiO 2 @PO 4 、Mn-TiO 2 And Mn-TiO 2 @PO 4 Is a band structure diagram of (a);
FIG. 12 is a diagram of TiO 2 、Mn-TiO 2 、TiO 2 @PO 4 And Mn-TiO 2 @PO 4 Photocatalytic reaction time profile in darkness and light;
FIG. 13 is Mn-TiO 2 、1-Mn-TiO 2 、Mn-TiO 2 @PO 4 And 1-Mn-TiO 2 @PO 4 Photocatalytic reaction time profile in darkness and light;
FIG. 14 is Mn-TiO 2 @PO 4 The extraction efficiency of uranium subjected to photocatalytic reaction in U (VI) solutions of different pH;
FIG. 15 is Mn-TiO 2 @PO 4 The extraction efficiency of uranium subjected to photocatalytic reaction under U (VI) solutions with different catalyst addition amounts (different solid-to-liquid ratios);
FIG. 16 is Mn-TiO 2 @PO 4 The extraction efficiency of uranium subjected to photocatalytic reaction in U (VI) solutions of different initial concentrations;
FIG. 17 shows the interfering ion K + ，Na + ，Ca 2+ ，Mg 2+ ，Sr 2+ ，Cu 2+ The extraction efficiency of uranium in the photocatalysis reaction of the photocatalyst in the cation;
FIG. 18 shows the interfering ion F - And NO 3 - The extraction efficiency of uranium in the photocatalysis reaction of the photocatalyst in the anions;
FIG. 19 is Mn-TiO 2 @PO 4 Infrared spectrum FT-IR after photocatalytic reaction;
FIG. 20 is Mn-TiO 2 @PO 4 XRD pattern after photocatalytic reaction;
FIG. 21 is a diagram of TiO 2 、Mn-TiO 2 、TiO 2 @PO 4 And Mn-TiO 2 @PO 4 A Linear Sweep Voltammetric (LSV) curve of U (VI) reduction.
The specific embodiment is as follows:
the present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
the preparation method of the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium comprises the following steps:
adding 50mL of deaerated water and 1.3g of manganese acetate into a sealed tank, stirring for 0.5h until the mixture is dissolved, adding 4mL of tetrabutyl titanate into the sealed tank under the condition of no stirring, sealing, standing and aging for 24 hours, filtering, and repeatedly washing a precipitate with distilled water to obtain Mn-TiO 2 ；
Step two, 100mg Mn-TiO 2 Soaking in 20mL phosphoric acid solution with concentration of 0.25mol/L, heating to 80deg.C, stirring for 12 hr, filtering, washing with ethanol and deionized water respectively for 3 times, drying at 60deg.C for 12 hr, and baking at 500deg.C for 1 hr to obtain Mn-TiO 2 @PO 4 Namely, the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium.
Example 2:
the preparation method of the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium comprises the following steps:
adding 50mL of deaerated water and 1.3g of manganese acetate into a sealed tank, stirring for 0.5h until the mixture is dissolved, adding 4mL of tetrabutyl titanate into the sealed tank under the condition of no stirring, sealing, standing and aging for 24 hours, filtering, and repeatedly washing a precipitate with distilled water to obtain Mn-TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The obtained Mn-TiO 2 Treating with hydrogen plasma for 60 seconds; obtaining 1-Mn-TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The technological parameters of the hydrogen plasma treatment are as follows: the air pressure is 30Pa, and the power is 100W;
step two, 100mg Mn-TiO 2 Soaking in 20mL of 0.25mol/L phosphoric acid solution, heating to 80deg.C, stirring for 12 hr, filtering, washing with ethanol and deionized water respectively for 3 times, drying at 60deg.C for 12 hr, and baking at 500deg.C for 1 hr to obtain 1-Mn-TiO 2 @PO 4 Namely, the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium.
Comparative example 1:
adding 50mL of deaerated water into a sealed tank, adding 4mL of tetrabutyl titanate into the sealed tank under the condition of no stirring, sealing, standing and aging for 24 hours, filtering, repeatedly washing precipitate with distilled water, washing with absolute ethyl alcohol for 2 times, vacuum drying at 60 ℃ for 12 hours, and calcining at 500 ℃ for 1 hour to obtain TiO 2 。
Comparative example 2:
100mg of TiO 2 Immersing in 20mL of 0.25mol/L phosphoric acid solution, heating to 80deg.C, stirring for 12 hr, filtering, washing with ethanol and deionized water respectively for 3 times, drying at 60deg.C for 12 hr, baking at 500deg.C for 1 hr,obtaining TiO 2 @PO 4 。
As shown in FIGS. 1a and 1b, mn-TiO 2 @PO 4 TEM image of (A), FIG. 2 is Mn-TiO 2 @PO 4 HRTEM images of (a); FIG. 3 is Mn-TiO 2 @PO 4 SEM images of (2); as can be seen from FIGS. 1 to 3, all the samples exhibited microsphere morphology with a size of about 1-2. Mu.m, consisting of uniform nanocrystalline grains with a size of 7-9 nm, mn-TiO 2 @PO 4 Has a hierarchical pore structure accumulated by uniform mesoporous microspheres; to further visualize mesoporous Mn-TiO 2 @PO 4 The crystal structure of the microspheres, figure 2 provides an HRTEM image; mn-TiO 2 @PO 4 The HRTEM image of (2) clearly shows lattice fringes with a interplanar spacing of 0.35nm, corresponding to anatase-TiO 2 The (101) plane of (PDF- # 73-1764) (FIG. 5).
FIG. 4 is a diagram of TiO 2 ，TiO 2 @PO 4 、Mn-TiO 2 And Mn-TiO 2 @PO 4 FTIR spectra of (c); FIG. 5 is a diagram of TiO 2 ，TiO 2 @PO 4 、Mn-TiO 2 And Mn-TiO 2 @PO 4 An XRD pattern of (b); FIG. 5 shows mesoporous TiO 2 The microspheres have several broad peaks at 25.6 °, 38.1 °, 48.1 °, 54.2 °, 55.4 °, 63.0 ° and 75 °, corresponding to (101), (004), (200), (105), (211), (204) and (215) anatase TiO, respectively 2 (PDF- # 73-1764) crystal plane. As can be seen from fig. 4, tiO 2 And Mn-TiO 2 Is 581cm in FTIR -1 The typical absorption band is shown here, corresponding to Ti-O bonds, 3402cm -1 And 1651cm -1 The absorption band at this point is related to the vibration peak of the water molecules. After modification of phosphoric acid function, tiO 2 Po4 and Mn-TiO 2 @PO 4 Is 1184cm in FTIR -1 A new P-O telescopic vibration absorption band appears at the position, which indicates that the phosphate group is positioned in the TiO 2 The surface was successfully modified.
To explore the energy band structural changes caused by Mn doping, and the role of surface phosphate groups in promoting electron transfer, tiO was characterized by optical and electrochemical methods 2 ，TiO 2 @PO 4 、Mn-TiO 2 And Mn-TiO 2 @PO 4 . FIG. 6 showsShowing the TiO produced 2 ，TiO 2 @PO 4 、Mn-TiO 2 And Mn-TiO 2 @PO 4 Photoluminescence (PL) spectrum of (a). With TiO 2 Compared to Mn doping and surface phosphate functional modification, respectively, significantly reduced PL intensity. Meanwhile, the synergistic effect of the two factors further reduces the PL intensity, which shows that Mn doping induced defect engineering and surface phosphate functional modification jointly promote the electron-hole separation process. As can be seen from Electrochemical Impedance Spectroscopy (EIS) (FIG. 7), with TiO 2 (2.0Ω) compared with TiO 2 After the lattice is replaced by Mn, tiO 2 Exhibits a significant decrease in the charge transfer resistance (Rct), indicating Mn-TiO 2 The charge transfer kinetics are faster. In addition, with Mn-TiO 2 And TiO 2 @PO 4 In comparison with Mn-TiO 2 @PO 4 Exhibits a low impedance (1.5 Ω), indicating that the surface function modification promotes the charge transport process. The transient photocurrent response sequence for all samples in fig. 8 is as follows: mn-TiO 2 @PO 4 >TiO 2 @PO 4 >Mn-TiO 2 >TiO 2 . For Mn-TiO 2 @PO 4 The photocurrent density recorded was about 1.2 muA, much higher than that of TiO 2 (0.7. Mu.A). Based on the above results, it can be derived that the photo-generated carrier separation efficiency is improved due to the generation of oxygen vacancy Ov caused by the doping of the element, and the surface function modification accelerates the electron transfer rate, thereby making Mn-TiO 2 @PO 4 Hole and electron separation efficiency with higher quality is constructed.
FIG. 9 shows Mn-TiO 2 And Mn-TiO 2 @PO 4 The band gap of (2) is 1.8eV, which is far lower than that of TiO 2 @PO 4 And TiO 2 (3.1 eV). The above results not only demonstrate that elemental doping (Mn) is a viable way to tailor the band structure, but also verify that surface phosphate modification only promotes electron transfer without altering the band structure. Fig. 10 shows the valence band edge (VB) spectrum. Mn-TiO relative to standard hydrogen energy level 2 And Mn-TiO 2 @PO 4 VB position of 1.5eV, far less than TiO 2 And TiO 2 @PO 4 VB position (2.4 eV). Considering the band gap value, tiO 2 And TiO 2 @PO 4 The Conduction Band (CB) edge positions of (C) are calculated as-0.3 eV and-0.7 eV, respectively. Based on the above data, tiO 2 、Mn-TiO 2 、TiO 2 @PO 4 And Mn-TiO 2 @PO 4 The band structure of (a) is shown in fig. 11. Clearly, mn doping effectively adjusts TiO by lowering VB position and raising CB position 2 Is a band structure of (a).
Photocatalytic uranium reduction experiments:
5mg of mesoporous titania photocatalyst was dispersed into U (VI) solutions (C U(VI) =8 mg/L,20mg/L,50mg/L,100mg/L,200 mg/L); then adjusting the pH value of the U (VI) solution to 4-9 by using 0.1mol/L NaOH and HCl solution; before the photocatalytic reaction, stirring the U (VI) solution dispersed with the mesoporous titanium dioxide photocatalyst for 60min under the light-shielding condition; then, a 300W xenon lamp with an AM1.5G filter is used as a light source, the photocatalytic reaction is carried out under stirring, the U (VI) concentration is measured at 651.8nm by an ultraviolet spectrophotometer at different times (10-120 min) of the photocatalytic reaction, and the removal efficiency of the U (VI) after photocatalysis is calculated:
removal efficiency= (C 0 -C t )/C 0 ×100％；
Wherein C is 0 Is the initial concentration of U (VI), C t Is the concentration of U (VI) after a certain period of time.
FIG. 12 is a diagram of TiO 2 、Mn-TiO 2 、TiO 2 @PO 4 And Mn-TiO 2 @PO 4 Photocatalytic reaction time profile under darkness and light (5 mg mesoporous titania photocatalyst, 20mL U (VI) solution (C U(VI) =200 mg/L; the pH is 4, and the mixture is stirred for 60min under the dark condition and 120min under the illumination condition). Mn-TiO under dark conditions 2 、TiO 2 @PO 4 And Mn-TiO 2 @PO 4 All show a specific ratio to TiO 2 Better adsorption performance due to surface defects caused by Mn doping and rich phosphate groups as restriction sites to trap U (VI). However, the adsorption property exhibited by the above materials is not worth mentioning in comparison with the photocatalytic property. After the simulated sunlight is introduced into the reaction system, photocatalysis is carried out for 120min, mn-TiO is carried out 2 And TiO 2 @PO 4 The photocatalytic properties for U (VI) are 57% and 34%, respectively, which are much higher than those of TiO 2 (14%) photocatalytic properties. The Mn doping and the surface phosphate group modification can effectively improve the extraction rate of U (VI). Notably, mn-TiO2@PO4 showed significant U (VI) extraction capacity with a removal of 93%. The above results confirm that Mn doping and surface phosphoric acid modification are performed on mesoporous TiO 2 Integration on the microspheres simultaneously achieves the improvement of the utilization rate of visible light and the construction of the U (VI) restriction sites, synergistically promotes the reaction kinetics and improves the U (VI) extraction promotion capability.
FIG. 13 is Mn-TiO 2 、1-Mn-TiO 2 、Mn-TiO 2 @PO 4 And 1-Mn-TiO 2 @PO 4 Photocatalytic reaction time profile under darkness and light (5 mg mesoporous titania photocatalyst, 20mL U (VI) solution (C U(VI) =200 mg/L; the pH is 4, and the mixture is stirred for 60min under the dark condition and 120min under the illumination condition). Under dark conditions, 1-Mn-TiO 2 Exhibits a specific Mn-TiO ratio 2 Better adsorption performance, also Mn-TiO 2 @PO 4 Exhibit a specific 1-Mn-TiO ratio 2 @PO 4 Better adsorption performance; under the illumination condition, 1-Mn-TiO 2 Also shows a specific Mn-TiO ratio 2 Better adsorption performance, mn-TiO 2 @PO 4 Also shows a specific 1-Mn-TiO 2 @PO 4 Better adsorption performance, which indicates Mn-TiO treatment by hydrogen plasma 2 The ability of the prepared mesoporous titanium dioxide photocatalyst to reduce uranium by photocatalysis can be obviously improved.
FIG. 14 is Mn-TiO 2 @PO 4 Extraction efficiency of uranium (5 mg mesoporous titania photocatalyst, 20mL U (VI) solution (C) U(VI) =8mg/L; stirring for 60min under the condition of light shielding at the pH of 4-9 and stirring for 120min under the condition of illumination); as can be seen from the figure, mn-TiO2@PO 4 The extraction capacity for U (VI) is maintained within a relatively wide pH range>High level of 90%.
FIG. 15 is Mn-TiO 2 @PO 4 Uranium extraction efficiency by photocatalytic reaction under U (VI) solutions with different catalyst addition amounts (solid-to-liquid ratios)Rate (different solid to liquid ratios, 20mL U (VI) solution (C) U(VI) =8mg/L; stirring under light shielding condition for 60min at pH 4, and stirring under light irradiation for 120 min); when the solid-to-liquid ratio was increased from 0.17g/L to 0.25g/L, the U (VI) extraction increased from 82% to 95%, indicating an optimum solid-to-liquid ratio of 0.25g/L.
FIG. 16 is Mn-TiO 2 @PO 4 Extraction efficiency of uranium (5 mg mesoporous titania photocatalyst, 20mL U (VI) solution (C) U(VI) =8mg/L, 20mg/L,50mg/L,100mg/L,200 mg/L); stirring under light shielding condition for 60min at pH 4, and stirring under light irradiation for 120 min); mn-TiO 2 @PO 4 Still significant U (VI) extractability was exhibited at initial U (VI) concentrations of 8ppm to 200 ppm. Calculated Mn-TiO at an initial concentration of 200mg/L of U (VI) 2 @PO 4 The U (VI) extraction amount reaches 680mg/g and is unsaturated.
Photocatalytic reduction uranium experiments in the presence of interfering ions:
5mg of mesoporous titania photocatalyst was dispersed into a U (VI) solution containing interfering ions (C U(VI) =8 mg/L); then adjusting the pH of the U (VI) solution to 4 with 0.1mol/L NaOH and HCl solution; before the photocatalytic reaction, stirring the U (VI) solution dispersed with the mesoporous titanium dioxide photocatalyst for 60min under the light-shielding condition; then, a 300W xenon lamp with an AM1.5G filter is used as a light source, the photocatalytic reaction is stirred, the concentration of U (VI) is measured at 651.8nm by an ultraviolet spectrophotometer at different times (120 min) of the photocatalytic reaction, and the removal efficiency of the U (VI) after photocatalysis is calculated:
removal efficiency= (C 0 -C t )/C 0 ×100％；
Wherein C is 0 Is the initial concentration of U (VI), C t Is the concentration of U (VI) after a certain time;
when the interfering ion is K + ，Na + ，Ca 2+ ，Mg 2+ ，Sr 2+ ，Cu 2+ At any one of the cations, the concentration of the interfering ions in the U (VI) solution is 80mg/L;
when the interfering ion is F - 、NO 3 - In the case of any one of anions, the molar ratio of U (VI) to the anions is 1:2-8;
FIG. 17 shows the interfering ion K + ，Na + ，Ca 2+ ，Mg 2+ ，Sr 2+ ，Cu 2+ The extraction efficiency of uranium in the photocatalysis reaction of the photocatalyst in the cation; mn-TiO in the presence of interfering metal ions 2 @PO 4 The photocatalytic performance of (a) can be maintained above 90% (fig. 5 b) due to the transfer of electrons on the semiconductor to phosphate groups to limit the capture of uranium and subsequent reduction of U (VI). Considering the presence of a large amount of F in uranium-containing waste streams produced by nuclear production plants - And NO 3 - The extraction capacity of the catalyst is greatly affected. For this purpose, uranium-containing wastewater was simulated using uranium solutions of different molar ratios (molar ratio of anions to uranyl ions). As shown in FIG. 18, mn-TiO 2 @PO 4 The removal rate of U (VI) can be kept at about 93%, which shows Mn-TiO 2 @PO 4 Has excellent anti-interference capability.
FIG. 19 is Mn-TiO 2 @PO 4 Infrared spectrum FT-IR after photocatalytic reaction, mn-TiO as the reaction proceeds 2 @PO 4 At 919cm -1 A typical o=u=o antisymmetric vibration peak appears, indicating Mn-TiO 2 The surface generates new uranium-containing species.
FIG. 20 is Mn-TiO 2 @PO 4 XRD pattern after photocatalytic reaction; mn-TiO 2 @PO 4 XRD spectra after photocatalytic reaction showed that uranium was mainly as uranium oxide hydrate ((UO) 2 )O 2 ·2H 2 O)) exist in the form of a compound.
FIG. 21 is Mn-TiO 2 @PO 4 A U (VI) reduced Linear Sweep Voltammetry (LSV) curve; as shown in FIG. 21, the peak between-0.34 eV and-0.44 eV is the characteristic peak of U (VI) reduced to U (V), while the peak between-1.08 eV and-1.29 eV is the characteristic peak of U (VI). U (V) is reduced to U (IV). With TiO 2 And single strategy modified TiO 2 In comparison with Mn-TiO 2 @PO 4 Has the maximum positive reduction potential. The results indicate that by parallel strategySlightly modified TiO 2 Has a lower reduction activation energy and overpotential due to doping and low band gap with phosphate groups on the surface as U (VI) surface restriction sites.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.

Claims (10)

1. The preparation method of the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium is characterized by comprising the following steps of:
adding deaerated water and manganese acetate into a sealing tank, stirring and dissolving, adding tetrabutyl titanate into the sealing tank, sealing, standing and aging, filtering, and repeatedly washing precipitate to obtain Mn-TiO 2 ；
Step two, mn-TiO is processed 2 Soaking in phosphoric acid solution, heating, stirring, filtering, washing, drying, and baking at 450-550deg.C to obtain Mn-TiO 2 @PO 4 Namely, the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium.
2. The method for preparing a mesoporous titania photocatalyst for photocatalytic reduction of uranium according to claim 1, wherein in the first step, the obtained mn—tio 2 And treating with hydrogen plasma for 30-60 seconds.
3. The method for preparing the mesoporous titania photocatalyst for photocatalytic reduction of uranium according to claim 2, wherein the technological parameters of the hydrogen plasma treatment are as follows: the air pressure is 10-100 Pa, and the power is 50-300W.
4. The method for preparing a mesoporous titania photocatalyst for photocatalytic reduction of uranium according to claim 1, wherein in the first step, a mass ratio of deaerated water to manganese acetate is 30-60:1; the mass volume ratio of the manganese acetate to the tetrabutyl titanate is 1 g:2-5 mL; the stirring and dissolving time is 15-45 min; the aging time is 12-36 hours; the precipitate is repeatedly washed with distilled water.
5. The method for preparing a mesoporous titania photocatalyst for photocatalytic reduction of uranium according to claim 1, wherein in the second step, mn—tio 2 And the mass volume ratio of the phosphoric acid solution is 4-6 mg to 1mL; the concentration of the phosphoric acid solution is 0.2-0.3 mol/L; heating and stirring at 75-85 ℃ for 8-15 h; washing with ethanol and deionized water for three times respectively, and drying at 50-70 ℃ for 8-15 h; the baking time is 0.5-1.5 h.
6. An experimental method for photocatalytic reduction of uranium in simulated radioactive wastewater by using the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium prepared by the preparation method according to any one of claims 1 to 5, wherein the mesoporous titanium dioxide photocatalyst is dispersed into U (VI) solutions with different concentrations; then adjusting the pH of the U (VI) solution with 0.1mol/L NaOH and HCl solution; before the photocatalytic reaction, stirring the U (VI) solution dispersed with the mesoporous titanium dioxide photocatalyst for 60min under the light-shielding condition; then, a 300W xenon lamp with an AM1.5G filter is used as a light source, the photocatalytic reaction is carried out under stirring, the U (VI) concentration is measured at 651.8nm by an ultraviolet spectrophotometer at different times of the photocatalytic reaction, and the removal efficiency of the U (VI) after photocatalysis is calculated:
removal efficiency= (C 0 -C t )/C 0 ×100％；
Wherein C is 0 Is the initial concentration of U (VI), C t Is the concentration of U (VI) after a certain period of time.
7. The experimental method for photocatalytic reduction of uranium in simulated radioactive wastewater by using the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium, prepared by the preparation method of claim 6, wherein the mass-to-volume ratio of the mesoporous titanium dioxide photocatalyst to U (VI) solutions with different concentrations is 1 mg/4 mL; the concentrations of the U (VI) solutions with different concentrations are respectively as follows: 8mg/L,20mg/L,50mg/L,100mg/L, and 200mg/L; the pH is regulated to 4-9; the different time for the photocatalytic reaction is 10-200 min.
8. The experimental method for photocatalytic reduction of uranium in simulated radioactive wastewater by using the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium prepared by the preparation method of claim 6, wherein the mesoporous titanium dioxide photocatalyst is dispersed into a U (VI) solution containing interfering ions; then adjusting the pH of the U (VI) solution to 4 with 0.1mol/L NaOH and HCl solution; before the photocatalytic reaction, stirring the U (VI) solution dispersed with the mesoporous titanium dioxide photocatalyst for 60min under the light-shielding condition; then, a 300W xenon lamp with an AM1.5G filter is used as a light source, the mixture is stirred for carrying out photocatalytic reaction for 120min, the concentration of U (VI) is measured at 651.8nm by an ultraviolet spectrophotometer, and the removal efficiency of the U (VI) after photocatalysis is calculated:
removal efficiency= (C 0 -C t )/C 0 ×100％；
Wherein C is 0 Is the initial concentration of U (VI) of 8mg/L, C t Is the concentration of U (VI) after a certain time;
when the interfering ion is K + ，Na + ，Ca 2+ ，Mg 2+ ，Sr 2+ ，Cu 2+ At any one of the cations, the concentration of the interfering ions in the U (VI) solution is 80mg/L;
when the interfering ion is F - 、NO 3 - In the case of any one of the anions, the molar ratio of U (VI) to the anion is 1:2-8.
9. The application of the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium prepared by the preparation method according to any one of claims 1 to 5 in radioactive wastewater, wherein the mesoporous titanium dioxide photocatalyst is added into uranium-containing radioactive wastewater, stirred for 60 minutes under a dark condition, and then subjected to photocatalytic reaction under sunlight irradiation, so as to realize photocatalytic reduction of hexavalent uranium in the uranium-containing radioactive wastewater.
10. The application of the mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium in radioactive wastewater, which is prepared by the preparation method of claim 9, and is characterized in that the mass-volume ratio of the mesoporous titanium dioxide photocatalyst to uranium-containing radioactive wastewater is 1 mg/3-6 mL; the time for stirring to perform the photocatalytic reaction is 60-180 min.
CN202211301548.0A 2022-10-24 2022-10-24 Preparation and application of mesoporous titanium dioxide photocatalyst for photocatalytic reduction of uranium Pending CN116078415A (en)

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