CN114133928B - Cerium oxide-doped photosensitizer suitable for photosensitive glass-ceramic and preparation method and application thereof - Google Patents

Cerium oxide-doped photosensitizer suitable for photosensitive glass-ceramic and preparation method and application thereof Download PDF

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CN114133928B
CN114133928B CN202111516201.3A CN202111516201A CN114133928B CN 114133928 B CN114133928 B CN 114133928B CN 202111516201 A CN202111516201 A CN 202111516201A CN 114133928 B CN114133928 B CN 114133928B
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霍伟荣
樊睿
于天来
罗汝佳
王万彬
胡斌
林彬
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University of Electronic Science and Technology of China
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Abstract

The invention discloses a doped cerium oxide photosensitizer suitable for photosensitive glass ceramics and a preparation method and application thereof 1‑x W x O 2 The general formula is shown in the specification, wherein x is as follows: x = 0.05-0.25. The fuel is prepared by taking cerium nitrate, ammonium metatungstate hydrate and organic fuel as raw materials and adopting a sol-gel self-propagating combustion method. The cerium oxide doped photosensitizer provided by the invention is a conventional photosensitizer CeO 2 And (3) carrying out W ion doping, improving the light absorption performance of the glass, and enabling the absorption peak to move so as to enable the absorption peak to be matched with the existing light source, thereby improving the nucleation efficiency and the exposure quality of the photosensitive microcrystalline glass.

Description

Cerium oxide doped photosensitizer suitable for photosensitive microcrystalline glass and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photosensitive glass ceramics, relates to a photosensitizer, and particularly relates to a cerium oxide doped photosensitizer suitable for photosensitive glass ceramics, and a preparation method and application thereof.
Background
With the rapid development of the electronic industry, a novel material-Li 2 O-Al 2 O 3 -SiO 2 The photosensitive glass-ceramics gradually enter the visual field of people. The photosensitive glass ceramics has the advantages of high strength, good dielectric property and the like, can be processed into sheets in various shapes, and has great application potential in the electronic industry due to excellent mechanical and electrical properties. The relatively low dielectric constant and dielectric loss and the low cost make the photosensitive glass ceramics hopeful to replace silicon materials and be widely appliedThe method is applied to the fields of integrated circuits, biomedicine, aerospace and the like.
Cerium oxide is Li 2 O-Al 2 O 3 -SiO 2 The photosensitive microcrystalline glass is an important component and can be used as a photosensitizer for capturing photons. In which CeO is present 2 Is a valence-variable substance capable of releasing free electrons under ultraviolet irradiation and containing Ag as a nucleating agent 2 O captures free electrons to form silver atoms. The relevant equation is shown below:
Ce 3+ +hv→Ce 4+ +e -
Ag + +e - →Ag
Li 2 O-Al 2 O 3 -SiO 2 the photosensitive glass ceramics is processed by the exposure process and then is processed by heat treatment, silver atoms in the exposed glass are converged into silver colloid particles, and the silver colloid particles can be used as crystal nucleus to induce Li 2 O·SiO 2 The crystallization of (4). Due to Li 2 O·SiO 2 The crystalline phase dissolves in the HF solution faster than the unexposed area of the glass matrix, so that the microstructure on the surface or inside of the photosensitive glass-ceramic can be processed by the above steps.
Although CeO is currently available 2 As a photosensitizer for photosensitive glass ceramics, ceO is widely used 2 The absorption peak of (A) is about 320nm, and the current common exposure light source in industry is a 0.35um photoetching machine. CeO (CeO) 2 The mismatch of the absorption peak and the industrial exposure light source band leads to the reduction of the exposure efficiency and quality of the photosensitive glass ceramics. At present, no special photoetching machine with the wavelength of 320nm is available for producing the photosensitive microcrystalline glass, and if the special photoetching machine with the wavelength of 320nm is manufactured for improving the exposure efficiency and the quality, the production cost is greatly improved.
Disclosure of Invention
Photosensitizer CeO aiming at existing photosensitive glass ceramics 2 The invention aims to provide a cerium oxide doped photosensitizer suitable for photosensitive glass ceramics and a preparation method and application thereof, and solves the problems of low exposure efficiency and low quality of the photosensitive glass ceramics caused by mismatching of an absorption peak and an industrial exposure light source wave bandSelf-propagating combustion method for photosensitizer CeO 2 Doping modification is carried out, the light absorption performance of the microcrystalline glass is improved, and the absorption peak of the microcrystalline glass is moved so as to be matched with the existing light source, so that the nucleation efficiency and the exposure quality of the photosensitive microcrystalline glass are improved.
In order to achieve the purpose, the invention provides a doped cerium oxide photosensitizer suitable for photosensitive microcrystalline glass, which is prepared by the general formula Ce 1-x W x O 2 The general formula is shown in the specification, wherein x is as follows: x =0.05 to 0.25.
When the W doping amount of the doped cerium oxide photosensitizer suitable for photosensitive microcrystalline glass is too large, ceO can be reduced 2 The crystallinity, x, is preferably selected from the following values: x =0.1 to 0.2, and more preferably x =0.1.
The preparation method of the doped cerium oxide photosensitizer applicable to the photosensitive glass ceramics comprises the following steps:
(1) Preparing materials: with cerium nitrate, ammonium metatungstate hydrate ((NH) 4 ) 6 H 2 W 12 O 40 ·xH 2 O) and organic fuel as raw materials according to the general formula Ce 1-x W x O 2 Weighing and proportioning according to a chemical formula determined by a set value of x, wherein the molar ratio of metal ions to the organic fuel is 1:1.5 to 2;
(2) Dissolving: dissolving cerium nitrate in deionized water, dissolving ammonium metatungstate hydrate in nitric acid, and mixing the two solutions to form a mixed solution;
(3) Preparing a precursor solution: adding organic fuel into the mixed solution, stirring until the organic fuel is dissolved, adding ammonia water under the stirring condition to adjust the pH value of the mixed solution to 7-8, and obtaining a precursor solution;
(4) Preparing precursor powder: heating the precursor solution to boiling and continuously stirring until dry gel is formed, igniting the dry gel powder, and performing self-propagating combustion to obtain loose precursor powder;
(5) And (3) sintering: sintering the obtained precursor powder at 950-1100 ℃ for 3-4 h, and naturally cooling to obtain sintered powder;
(6) Ball with ball-shaped sectionGrinding: carrying out wet ball milling on the cooled sintering powder, and drying the ball-milled slurry to obtain the material with the chemical formula of Ce 1-x W x O 2 Doped ceria photosensitizers of (a).
In the preparation method of the doped cerium oxide photosensitizer suitable for photosensitive glass ceramics, in the step (1), the metal ions refer to cerium ions and tungsten ions.
According to the preparation method of the cerium oxide doped photosensitizer suitable for the photosensitive microcrystalline glass, the ammonium metatungstate hydrate is dissolved in nitric acid, the dosage and the concentration of the nitric acid are not specially required, the ammonium metatungstate hydrate is completely dissolved, and the concentration of the nitric acid is the concentration of a conventional commercially available nitric acid solution or the concentration of a conventional laboratory. Further, the ratio of the molar amount of metal ions in the ammonium metatungstate hydrate to the nitric acid may be: when the molar weight of the metal ions in the ammonium metatungstate hydrate is 0.01mol, the metal ions can be dissolved in a nitric acid solution with the concentration of 14.4-15.2mol/L and the volume of 15 ml. In the examples of the present invention, the nitric acid solution was commercially available at a concentration of 14.4 to 15.2mol/L.
In the preparation method of the doped cerium oxide photosensitizer suitable for the photosensitive microcrystalline glass, the organic fuel has the function of generating a strong oxidation-reduction exothermic reaction with nitrate during heating so as to maintain the reaction process and cause self-propagating combustion, so that the organic fuel can be selected from conventional organic fuels in the field such as citric acid, aminoacetic acid, oxalic acid or polyacrylic acid, and the like, and is preferably citric acid which is a ternary weak acid, is ionized in a water solution in multiple stages, and then is subjected to a complexing reaction with metal ions. The nitrate/citric acid ratio affects the stability and self-combustion of the gel.
In the preparation method of holmium-doped copper ferrite multiferroic ceramic, the pH value of the system can influence the multistage ionization of citric acid, and further influences the distribution of components in the sol. When the pH value of the reaction system is lower, the multi-stage ionization of the citric acid is inhibited, part of metal ions in the sol system is complexed with citrate, and part of metal ions still exist in the form of nitrate, so that the components of the sol are unevenly distributed; when the pH value is higher, the ionization of the citric acid is more complete, but the alkaline condition can lead metal ions to form precipitates which cannot be fully complexed, and the uniformity of gel components is also influenced, thereby further influencing the self-combustion characteristic of the xerogel. In the invention, the pH value is controlled to be 7-8, and the full complexation of the citrate and the metal ions and the complete combustion of the subsequent xerogel can be realized in the range.
In the preparation method of the doped cerium oxide photosensitizer suitable for photosensitive glass ceramics, in the step (5), the sintering temperature rise rate is a conventional rate, and is preferably 3-4 ℃/min.
In the above preparation method of the doped cerium oxide photosensitizer suitable for photosensitive glass-ceramic, in the step (6), the wet ball milling may adopt a ball milling medium and a dispersing agent which are conventional in the art, and conventional ball milling parameters, which are not particularly limited. In the present invention, it is preferable to perform wet ball milling on the sintered powder using ethanol as a medium and triethanolamine as a dispersant.
The invention provides a doped cerium oxide photosensitizer suitable for photosensitive glass ceramics and a preparation method thereof, wherein the doping principle is as follows: ceO (CeO) 2 Has a band gap of about 3.2eV, resulting from the transition of the electron on oxygen 2p to Ce 4f, doped CeO 2 The doped CeO of the nano-particles is characterized in that the doped metal W provides a lower unoccupied orbital than 4f (Ce), and the energy required for electrons to jump from a 2p (O) orbital to the unoccupied orbital is lower 2 Nanoparticle to undoped CeO 2 Can absorb more light with longer wavelength, and causes the absorption to move to the long-wave direction, thereby generating the red shift phenomenon.
The invention also provides application of the doped cerium oxide photosensitizer suitable for the photosensitive glass ceramics as a photosensitizer in photosensitive glass ceramics.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) The cerium oxide doped photosensitizer suitable for photosensitive glass ceramics provided by the invention is used for the existing photosensitizer CeO 2 Carrying out W ion doping to obtain CeO 2 Nanoparticles, electrons jump from the 2p (O) orbital to an unoccupied orbital due to the doping of the metal W providing a lower unoccupied orbital than 4f (Ce)The required energy is lower, so that the doped CeO 2 Nanoparticles than undoped CeO 2 The light absorption peak can be matched with the existing light source by improving the light absorption performance of the light absorption peak, and the light absorption peak can be applied to photosensitive glass ceramics as a photosensitizer, so that the nucleation efficiency and the exposure quality of the photosensitive glass ceramics can be effectively improved.
(2) According to the preparation method of the doped cerium oxide photosensitizer suitable for the photosensitive glass ceramics, the doped cerium oxide photosensitizer is synthesized by a self-propagating combustion method, pre-sintering is not needed, the sintering phase forming temperature is low, the sintering time is short, and a good energy-saving effect is achieved; and the preparation process is simple, the equipment used for preparation is low in price, the cost is low, the preparation process period is short, and the preparation method has a good application prospect and is worthy of popularization and application in the field.
Drawings
FIG. 1 is an XRD pattern of cerium oxide photosensitizer samples doped with different concentrations W prepared in examples 1-4;
FIG. 2 is a sample of W-doped cerium oxide photosensitizer prepared in example 2 and pure CeO 2 Ultraviolet-visible absorption spectrum of photosensitizer sample, wherein, the graph (a) is absorption spectrum of 200 nm-650 nm wave band, and the graph (b) is partial graph of the graph (a), namely absorption spectrum of 300 nm-400 nm wave band;
FIG. 3 shows Ag in an application example 2 CO 3 And CeO 2 Ag 3d and Ce 3d XPS spectra of the sample, wherein plots (a 1) and (a 2) are unexposed Ag 3d and Ce 3d XPS spectra, respectively, plots (b 1) and (b 2) are Ag 3d and Ce 3d XPS spectra exposed to a 320nm ultraviolet light source, respectively, and plots (c 1) and (c 2) are Ag 3d and Ce 3d XPS spectra exposed to a 350nm ultraviolet light source, respectively;
FIG. 4 shows Ag in the application example 2 CO 3 And Ce 0.9 W 0.1 O 2 Ag 3d and Ce 3d XPS spectra of the sample, wherein the graphs (a 1) and (a 2) are unexposed Ag 3d and Ce 3d XPS spectra, respectively, the graphs (b 1) and (b 2) are Ag 3d and Ce 3d XPS spectra exposed by a 320nm ultraviolet light source, respectively, and the graphs (c 1) and (c 2) are 350nm ultraviolet light source, respectivelyExposed Ag 3d and Ce 3d XPS spectra.
Detailed Description
So that the technical solutions of the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings, it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, belong to the present invention.
Example 1
This example prepared the chemical formula Ce by using a citric acid-nitrate self-propagating combustion method 0.95 W 0.05 O 2 (i.e., x = 0.05) a doped ceria photosensitizer suitable for use in photosensitive glass ceramics, comprising in particular the steps of:
(1) Preparing materials: with Ce (NO) 3 ) 3 ·6H 2 O、(NH 4 ) 6 H 2 W 12 O 40 ·xH 2 O and citric acid as raw materials according to a chemical formula Ce 0.95 W 0.05 O 2 Weighing and proportioning the components according to the determined chemical formula, wherein the molar ratio of the metal ions to the organic fuel is 1:1.5;
(2) Dissolving: 0.0285mol of Ce (NO) 3 ) 3 ·6H 2 O was dissolved in deionized water and 0.000125mol (NH) was added 4 ) 6 H 2 W 12 O 40 ·xH 2 Dissolving O in 15ml of nitric acid with the concentration of 14.4-15.2mol/L, and mixing the two solutions to form a mixed solution;
(3) Preparing a precursor solution: adding 0.045mol of citric acid into the mixed solution, stirring until the citric acid is completely dissolved, slowly adding 30ml of ammonia water under the stirring condition, observing that flocculent precipitate appears, then disappearing, finally clarifying the solution, and adjusting the pH value to 7-8 to obtain a precursor solution;
(4) Preparing precursor powder: transferring the precursor solution into a crucible, heating the crucible on an electric furnace to boiling and continuously stirring until dry gel is formed, igniting the dry gel powder, and performing self-propagating combustion to obtain loose precursor powder;
(5) And (3) sintering: collecting the obtained precursor powder in a small crucible, putting the crucible into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the sintering time is 3 hours, and naturally cooling to obtain sintered powder;
(6) Ball milling: collecting the cooled sintering powder, performing wet ball milling by using ethanol as a medium and triethanolamine as a dispersing agent, and drying the ball-milled slurry in an oven at 50 ℃ to obtain a chemical formula Ce 0.95 W 0.05 O 2 Doped ceria photosensitizers of (a).
Example 2
This example uses citric acid-nitrate self-propagating combustion method to prepare the chemical formula Ce 0.9 W 0.1 O 2 (i.e., x = 0.1) a doped ceria photosensitizer suitable for use in photosensitive glass ceramics, comprising in particular the steps of:
(1) Preparing materials: with Ce (NO) 3 ) 3 ·6H 2 O、(NH 4 ) 6 H 2 W 12 O 40 ·xH 2 O and citric acid as raw materials according to the chemical formula Ce 0.9 W 0.1 O 2 Weighing and proportioning the components according to the determined chemical formula, wherein the molar ratio of the metal ions to the organic fuel is 1:1.5;
(2) Dissolving: 0.027mol of Ce (NO) 3 ) 3 ·6H 2 O was dissolved in deionized water, 0.00025mol (NH) 4 ) 6 H 2 W 12 O 40 ·xH 2 Dissolving O in 15ml of nitric acid with the concentration of 14.4-15.2mol/L, and mixing the two solutions to form a mixed solution;
(3) Preparing a precursor solution: adding 0.045mol of citric acid into the mixed solution, stirring until the citric acid is completely dissolved, slowly adding 30ml of ammonia water under the stirring condition, observing that flocculent precipitates appear, then eliminating the flocculent precipitates, finally clarifying the solution, and adjusting the pH value to 7-8 to obtain a precursor solution;
(4) Preparing precursor powder: transferring the precursor solution into a crucible, heating the crucible to boiling on an electric furnace and continuously stirring until dry gel is formed, igniting the dry gel powder to perform self-propagating combustion to obtain loose precursor powder;
(5) And (3) sintering: collecting the obtained precursor powder in a small crucible, putting the crucible into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the sintering time is 3 hours, and naturally cooling to obtain sintered powder;
(6) Ball milling: collecting the cooled sintering powder, performing wet ball milling by using ethanol as a medium and triethanolamine as a dispersing agent, and drying the ball-milled slurry in an oven at 50 ℃ to obtain a chemical formula Ce 0.9 W 0.1 O 2 Doped ceria photosensitizers of (a).
Example 3
This example prepared the chemical formula Ce by using a citric acid-nitrate self-propagating combustion method 0.85 W 0.15 O 2 The doped cerium oxide photosensitizer suitable for photosensitive glass ceramics (namely x = 0.15) specifically comprises the following steps:
(1) Preparing materials: with Ce (NO) 3 ) 3 ·6H 2 O、(NH 4 ) 6 H 2 W 12 O 40 ·xH 2 O and citric acid as raw materials according to the chemical formula Ce 0.85 W 0.15 O 2 Weighing and proportioning the components according to the determined chemical formula, wherein the molar ratio of the metal ions to the organic fuel is 1:1.5;
(2) Dissolving: 0.0255mol of Ce (NO) 3 ) 3 ·6H 2 O was dissolved in deionized water and 0.000375mol (NH) was added 4 ) 6 H 2 W 12 O 40 ·xH 2 Dissolving O in 15ml of nitric acid with the concentration of 14.4-15.2mol/L, and mixing the two solutions to form a mixed solution;
(3) Preparing a precursor solution: adding 0.045mol of citric acid into the mixed solution, stirring until the citric acid is completely dissolved, slowly adding 30ml of ammonia water under the stirring condition, observing that flocculent precipitate appears, then disappearing, finally clarifying the solution, and adjusting the pH value to 7-8 to obtain a precursor solution;
(4) Preparing precursor powder: transferring the precursor solution into a crucible, heating the crucible on an electric furnace to boiling and continuously stirring until dry gel is formed, igniting the dry gel powder, and performing self-propagating combustion to obtain loose precursor powder;
(5) And (3) sintering: collecting the obtained precursor powder in a small crucible, putting the crucible into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the sintering time is 3 hours, and naturally cooling to obtain sintered powder;
(6) Ball milling: collecting the cooled sintering powder, carrying out wet ball milling by using ethanol as a medium and triethanolamine as a dispersing agent, and drying the ball-milled slurry in an oven at 50 ℃ to obtain a chemical formula Ce 0.85 W 0.15 O 2 Doped ceria photosensitizer of (a).
Example 4
This example uses citric acid-nitrate self-propagating combustion method to prepare the chemical formula Ce 0.8 W 0.2 O 2 The doped cerium oxide photosensitizer suitable for photosensitive glass ceramics (namely x = 0.2) specifically comprises the following steps:
(1) Preparing materials: with Ce (NO) 3 ) 3 ·6H 2 O、(NH 4 ) 6 H 2 W 12 O 40 ·xH 2 O and citric acid as raw materials according to the chemical formula Ce 0.8 W 0.2 O 2 Weighing and proportioning the components according to the determined chemical formula, wherein the molar ratio of the metal ions to the organic fuel is 1:1.5;
(2) Dissolving: 0.024mol of Ce (NO) 3 ) 3 ·6H 2 O was dissolved in deionized water and 0.0005mol (NH) was added 4 ) 6 H 2 W 12 O 40 ·xH 2 Dissolving O in 15ml of nitric acid with the concentration of 14.4-15.2mol/L, and mixing the two solutions to form a mixed solution;
(3) Preparing a precursor solution: adding 0.045mol of citric acid into the mixed solution, stirring until the citric acid is completely dissolved, slowly adding 30ml of ammonia water under the stirring condition, observing that flocculent precipitates appear, then eliminating the flocculent precipitates, finally clarifying the solution, and adjusting the pH value to 7-8 to obtain a precursor solution;
(4) Preparing precursor powder: transferring the precursor solution into a crucible, heating the crucible to boiling on an electric furnace and continuously stirring until dry gel is formed, igniting the dry gel powder to perform self-propagating combustion to obtain loose precursor powder;
(5) And (3) sintering: collecting the obtained precursor powder in a small crucible, putting the crucible into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the sintering time is 3 hours, and naturally cooling to obtain sintered powder;
(6) Ball milling: collecting the cooled sintering powder, performing wet ball milling by using ethanol as a medium and triethanolamine as a dispersing agent, and drying the ball-milled slurry in an oven at 50 ℃ to obtain a chemical formula Ce 0.8 W 0.2 O 2 Doped ceria photosensitizers of (a).
Example 5
This example prepared the chemical formula Ce by using a citric acid-nitrate self-propagating combustion method 0.75 W 0.25 O 2 (i.e., x = 0.25) indicates a doped ceria photosensitizer suitable for use in photosensitive glass ceramics, comprising in particular the steps of:
(1) Preparing materials: with Ce (NO) 3 ) 3 ·6H 2 O、(NH 4 ) 6 H 2 W 12 O 40 ·xH 2 O and citric acid as raw materials according to the chemical formula Ce 0.75 W 0.25 O 2 Weighing and proportioning the components according to the determined chemical formula, wherein the molar ratio of the metal ions to the organic fuel is 1:1.5;
(2) Dissolving: 0.0225mol of Ce (NO) 3 ) 3 ·6H 2 O was dissolved in deionized water and 0.000625mol (NH) 4 ) 6 H 2 W 12 O 40 ·xH 2 Dissolving O in 15ml of nitric acid with the concentration of 14.4-15.2mol/L, and mixing the two solutions to form a mixed solution;
(3) Preparing a precursor solution: adding 0.045mol of citric acid into the mixed solution, stirring until the citric acid is completely dissolved, slowly adding 30ml of ammonia water under the stirring condition, observing that flocculent precipitates appear, then eliminating the flocculent precipitates, finally clarifying the solution, and adjusting the pH value to 7-8 to obtain a precursor solution;
(4) Preparing precursor powder: transferring the precursor solution into a crucible, heating the crucible on an electric furnace to boiling and continuously stirring until dry gel is formed, igniting the dry gel powder, and performing self-propagating combustion to obtain loose precursor powder;
(5) And (3) sintering: collecting the obtained precursor powder in a small crucible, putting the crucible into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the sintering time is 3 hours, and naturally cooling to obtain sintered powder;
(6) Ball milling: collecting the cooled sintering powder, carrying out wet ball milling by using ethanol as a medium and triethanolamine as a dispersing agent, and drying the ball-milled slurry in an oven at 50 ℃ to obtain a chemical formula Ce 0.75 W 0.25 O 2 Doped ceria photosensitizers of (a).
Example 6
This example uses citric acid-nitrate self-propagating combustion method to prepare the chemical formula Ce 0.9 W 0.1 O 2 (i.e., x = 0.1) a doped ceria photosensitizer suitable for use in photosensitive glass ceramics, comprising in particular the steps of:
(1) Preparing materials: with Ce (NO) 3 ) 3 ·6H 2 O、(NH 4 ) 6 H 2 W 12 O 40 ·xH 2 O and citric acid as raw materials according to a chemical formula Ce 0.9 W 0.1 O 2 Weighing and proportioning the components according to the determined chemical formula, wherein the molar ratio of the metal ions to the organic fuel is 1:2;
(2) Dissolving: 0.027mol of Ce (NO) 3 ) 3 ·6H 2 O was dissolved in deionized water and 0.00025mol (NH) was added 4 ) 6 H 2 W 12 O 40 ·xH 2 Dissolving O in 15ml of nitric acid with the concentration of 14.4-15.2mol/L, and mixing the two solutions to form a mixed solution;
(3) Preparing a precursor solution: adding 0.06mol of citric acid into the mixed solution, stirring until the citric acid is completely dissolved, slowly adding 30ml of ammonia water under the stirring condition, observing that flocculent precipitates appear, then eliminating the phenomenon that the solution is finally clear, and adjusting the pH value to 7-8 to obtain a precursor solution;
(4) Preparing precursor powder: transferring the precursor solution into a crucible, heating the crucible to boiling on an electric furnace and continuously stirring until dry gel is formed, igniting the dry gel powder to perform self-propagating combustion to obtain loose precursor powder;
(5) And (3) sintering: collecting the obtained precursor powder in a small crucible, putting the crucible into a muffle furnace for sintering, wherein the sintering temperature is 950 ℃, the sintering time is 3 hours, and naturally cooling to obtain sintered powder;
(6) Ball milling: collecting the cooled sintering powder, carrying out wet ball milling by using ethanol as a medium and triethanolamine as a dispersing agent, and drying the ball-milled slurry in an oven at 50 ℃ to obtain a chemical formula Ce 0.9 W 0.1 O 2 Doped ceria photosensitizers of (a).
Example 7
This example uses citric acid-nitrate self-propagating combustion method to prepare the chemical formula Ce 0.9 W 0.1 O 2 (i.e., x = 0.1) a doped ceria photosensitizer suitable for use in photosensitive glass ceramics, comprising in particular the steps of:
(1) Preparing materials: with Ce (NO) 3 ) 3 ·6H 2 O、(NH 4 ) 6 H 2 W 12 O 40 ·xH 2 O and citric acid as raw materials according to the chemical formula Ce 0.9 W 0.1 O 2 Weighing and proportioning the components according to the determined chemical formula, wherein the molar ratio of the metal ions to the organic fuel is 1:2;
(2) Dissolving: 0.027mol of Ce (NO) 3 ) 3 ·6H 2 O was dissolved in deionized water and 0.00025mol (NH) was added 4 ) 6 H 2 W 12 O 40 ·xH 2 Dissolving O in 15ml of nitric acid with the concentration of 14.4-15.2mol/L, and mixing the two solutions to form a mixed solution;
(3) Preparing a precursor solution: adding 0.06mol of citric acid into the mixed solution, stirring until the citric acid is completely dissolved, slowly adding 30ml of ammonia water under the stirring condition, observing that flocculent precipitates appear, then eliminating the phenomenon that the solution is finally clear, and adjusting the pH value to 7-8 to obtain a precursor solution;
(4) Preparing precursor powder: transferring the precursor solution into a crucible, heating the crucible on an electric furnace to boiling and continuously stirring until dry gel is formed, igniting the dry gel powder, and performing self-propagating combustion to obtain loose precursor powder;
(5) And (3) sintering: collecting the obtained precursor powder in a small crucible, putting the crucible into a muffle furnace for sintering, wherein the sintering temperature is 1100 ℃, the sintering time is 3 hours, and naturally cooling to obtain sintered powder;
(6) Ball milling: collecting the cooled sintering powder, carrying out wet ball milling by using ethanol as a medium and triethanolamine as a dispersing agent, and drying the ball-milled slurry in an oven at 50 ℃ to obtain a chemical formula Ce 0.9 W 0.1 O 2 Doped ceria photosensitizer of (a).
Comparative example
The comparative example utilizes a citric acid-nitrate self-propagating combustion method to prepare the conventional photosensitizer CeO of the photosensitive microcrystalline glass 2 The method specifically comprises the following steps:
(1) Preparing materials: with Ce (NO) 3 ) 3 ·6H 2 And O and citric acid are used as raw materials, and the raw materials are weighed and proportioned, wherein the molar ratio of the metal ions to the organic fuel is 1:1.5;
(2) Dissolving: 0.03mol of Ce (NO) 3 ) 3 ·6H 2 Dissolving O in deionized water to form a cerium nitrate solution;
(3) Preparing a precursor solution: adding 0.045mol of citric acid into a cerium nitrate solution, stirring until the citric acid is completely dissolved, slowly adding 30ml of ammonia water under the stirring condition, observing that flocculent precipitates appear, then eliminating the flocculent precipitates, finally clarifying the solution, and adjusting the pH value to 7-8 to obtain a precursor solution;
(4) Preparing precursor powder: transferring the precursor solution into a crucible, heating the crucible on an electric furnace to boiling and continuously stirring until dry gel is formed, igniting the dry gel powder, and performing self-propagating combustion to obtain loose precursor powder;
(5) And (3) sintering: collecting the obtained precursor powder in a small crucible, putting the crucible into a muffle furnace for sintering, wherein the sintering temperature is 1000 ℃, the sintering time is 3 hours, and naturally cooling to obtain sintered powder;
(6) Ball milling: collecting the cooled sintering powder, performing wet ball milling by using ethanol as a medium and triethanolamine as a dispersing agent,drying the ball-milled slurry in an oven at 50 ℃ to obtain CeO 2 A photosensitizer.
The following doped cerium oxide photosensitizer samples prepared in examples 1 to 5 and CeO prepared in comparative example 2 Photosensitizer samples were subjected to performance analysis.
(I) structural analysis
In order to investigate the phase structure of the doped cerium oxide photosensitizer samples prepared by the method of the present invention, phase analysis was performed on the doped cerium oxide photosensitizer samples prepared in examples 1 to 4 using an X-ray diffractometer (XRD), and the results are shown in fig. 1. As can be seen from FIG. 1, all samples exhibited the cubic fluorite structure of CeO 2 The JCPDS card has no diffraction peak of raw materials and other impurities, which indicates that all samples have single-phase structures, and the structure of a matrix is not changed by doping ions.
(II) ultraviolet absorption analysis
In order to investigate the UV-visible light absorption properties of the doped ceria photosensitizer samples prepared by the method of the present invention, the doped ceria photosensitizer sample prepared in example 2 and CeO prepared in comparative example 2 The photosensitizer samples were subjected to uv absorption analysis and the results are shown in figure 2. As can be seen from FIG. 2, ceO is present in the wavelength range of 250nm to 320nm 2 The highest absorption strength of (a); ce 0.9 W 0.1 O 2 The absorption intensity of the sample is highest near and after the 350nm band.
Application example
Ce prepared in example 2 0.9 W 0.1 O 2 And Ag 2 CO 3 Weighing 60g of powder according to the mass ratio of 0.09, and mixing the CeO prepared by the comparative example 2 And Ag 2 CO 3 Weighing 60g of powder according to the mass ratio of 0.08, grinding the powder in a mortar with moderate force for 1 hour, weighing 20 g of uniformly mixed powder, exposing the powder for 30 minutes under a light source of 320nm, weighing 20 g of uniformly mixed powder, exposing the powder for 30 minutes under a light source of 350nm, and leaving 20 g of powder unexposed. XPS tests were performed on both exposed and unexposed samples, and the results are shown in fig. 3 and 4.
As can be seen from FIG. 3, ag 2 CO 3 And CeO 2 XPS spectra of samples with Ag alone before unexposed + Indicates that no elemental Ag is present. After exposure to 320nm or 350nm ultraviolet light source, ag appears 0 The peak value of (2) indicates that the simple substance Ag is separated out. Meanwhile, the Ce is exposed after being exposed by 320nm or 350nm ultraviolet light source 3+ All of the peak areas of (a) are smaller than those of the unexposed ones, indicating that part of Ce is present 3+ Conversion to Ce by exposure 4+ . At the same time, ag can be seen 2 CO 3 And CeO 2 Ag of sample after exposure under 320nm ultraviolet light source 0 Peak area of (1) is largest, ce 3+ The peak area of (A) is minimal, indicating that CeO 2 The exposure performance is best under the condition of 320 nm.
As can be seen from FIG. 4, ag 2 CO 3 And Ce 0.9 W 0.1 O 2 XPS spectra of (A) with Ag before Exposure + Peak, almost no Ag 0 Peak(s). After 320nm or 350nm ultraviolet light exposure, ag appears obviously 0 The peak (b) indicates the precipitation of the simple substance Ag. Ce of samples after exposure to 320nm UV light source compared to unexposed samples 3+ The peak area is slightly reduced, while the Ce of the sample after the 350nm ultraviolet light source exposure 3+ The peak area is obviously reduced, indicating that Ag 2 CO 3 And Ce 0.9 W 0.1 O 2 The sample of (2) has more Ce under the condition of 350nm 3+ Conversion to Ce 4+ . Ag of the sample after exposure to 350nm ultraviolet light source 0 Peak area of (1) is largest, ce 3+ The peak area of (B) is the smallest, indicating that the sample Ce is 0.9 W 0.1 O 2 The exposure performance at 350nm is best.
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art, having the benefit of this disclosure, may effect numerous modifications thereto and changes may be made without departing from the scope of the invention in its aspects.

Claims (6)

1. The doped cerium oxide photosensitizer suitable for photosensitive microcrystalline glass is used as a photosensitizer in the photosensitive microcrystalline glass, and the doped cerium oxide photosensitizer is represented by a general formula Ce 1-x W x O 2 In the general formula, x takes the value as follows: x =0.05 to 0.25.
2. The use of the doped ceria photosensitizer suitable for use in a photosensitive glass-ceramic as claimed in claim 1 as a photosensitizer in a photosensitive glass-ceramic, wherein: the value of x is: x =0.1 to 0.2.
3. The use of the doped ceria photosensitizer for photosensitive glass ceramics according to claim 1 as photosensitizer in photosensitive glass ceramics, characterized in that: the value of x is: x =0.1.
4. The use of the doped ceria photosensitizer suitable for use in a photosensitive glass-ceramic as claimed in claim 1 as a photosensitizer in a photosensitive glass-ceramic, wherein: the preparation method of the doped cerium oxide photosensitizer comprises the following steps:
(1) Preparing materials: cerium nitrate, ammonium metatungstate hydrate and organic fuel are used as raw materials, and the general formula is Ce 1-x W x O 2 Weighing and proportioning according to a chemical formula determined by a set value of x, wherein the molar ratio of metal ions to the organic fuel is 1:1.5 to 2;
(2) Dissolving: dissolving cerium nitrate in deionized water, dissolving ammonium metatungstate hydrate in nitric acid, and mixing the two solutions to form a mixed solution;
(3) Preparing a precursor solution: adding the organic fuel into the mixed solution, stirring until the organic fuel is dissolved, adding ammonia water under the stirring condition to adjust the pH value of the mixed solution to 7-8, and obtaining a precursor solution;
(4) Preparing precursor powder: heating the precursor solution to boiling and continuously stirring until dry gel is formed, igniting the dry gel powder, and performing self-propagating combustion to obtain loose precursor powder;
(5) And (3) sintering: sintering the obtained precursor powder at the sintering temperature of 950-1100 ℃ for 3-4 h, and naturally cooling to obtain sintered powder;
(6) Ball milling: carrying out wet ball milling on the cooled sintering powder, and drying the ball-milled slurry to obtain the slurry with the chemical formula of Ce 1-x W x O 2 Doped ceria photosensitizers of (a).
5. The use of the doped ceria photosensitizer suitable for use in a photosensitive glass ceramic as claimed in claim 4, as a photosensitizer in a photosensitive glass ceramic, wherein: the organic fuel is one of citric acid, glycine, oxalic acid or polyacrylic acid.
6. The use of the doped cerium oxide photosensitizer suitable for photosensitive glass ceramics according to claim 4 or 5, as a photosensitizer in photosensitive glass ceramics, characterized in that: and (6) performing wet ball milling on the sintered powder by using ethanol as a medium and triethanolamine as a dispersing agent.
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