Nanoscale Ti2O3, preparation method and application of nanoscale Ti2O3 as catalyst carrier
Nanoscale Ti2O3 powder was prepared by solid-state synthesis and inert atmosphere calcination, and then loaded with noble metals. This solved the problems of large particles, severe agglomeration and uneven particle size in the preparation process of existing technologies, and realized efficient and rapid preparation of nanoscale Ti2O3 and its application as a catalyst.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-26
- Publication Date
- 2026-03-27
AI Technical Summary
In existing technologies, the preparation methods of nano-scale Ti2O3 have problems such as high reaction temperature and long reaction time, resulting in large powder particles, severe agglomeration and uneven particle size distribution. At the same time, hydrogen reduction poses an explosion hazard, and carbon powder residue affects the purity of the product.
A solid-state synthesis method was adopted, using nano-titanium powder and nano-titanium dioxide as raw materials to control the synthesis of nano-scale Ti2O3 powder. The catalyst was prepared by calcining under an inert atmosphere and adjusting the reaction conditions, followed by loading noble metals.
Rapid synthesis of nano-sized Ti2O3 with uniform particle size was achieved. The preparation method is simple and efficient, and the product has high purity, making it suitable for electrochemical catalysis and energy conversion.
Smart Images
Figure CN121735302A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of nanomaterial preparation technology, specifically relating to a nano-scale Ti2O3, its preparation method, and its application as a catalyst support. Background Technology
[0002] Ti₂O₃ is a sub-titanium oxide with a hexagonal corundum crystal structure. Its unique electronic structure and strong electronic correlation effect give it an ultra-narrow band gap (0.1 eV), making it an excellent photothermal material with a wide range of applications in the photothermal field. At the same time, Ti₂O₃ possesses good electrical conductivity, high chemical stability (acid and alkali resistance), and a wide electrochemical window, thus it is believed to have great potential as a support in the electrochemical field.
[0003] Currently, the main method for solid-phase preparation of Ti₂O₃ is the titanium dioxide reduction method, which uses hydrogen or carbon powder as a reducing agent to reduce titanium dioxide at 1200℃ for more than 10 hours under vacuum or inert atmosphere. Due to the high reaction temperature and long reaction time, the prepared powder has problems such as large particles, severe agglomeration, and uneven particle size distribution. At the same time, hydrogen reduction poses an explosion hazard, while carbon powder residue easily affects product purity. Therefore, preparing nanoscale Ti₂O₃ with uniform particle size distribution is a promising but challenging endeavor. Summary of the Invention
[0004] The purpose of this invention is to provide a nano-sized Ti2O3, its preparation method, and its application as a catalyst support.
[0005] This invention utilizes a solid-phase synthesis method, using nano-titanium powder and nano-titanium dioxide as raw materials, to controllably synthesize nano-sized, uniformly distributed brownish-black Ti₂O₃ powder. Simultaneously, this invention uses it as a catalyst support to synthesize a series of noble metal-supported catalysts.
[0006] The first objective of this invention is to provide a simple and efficient method for preparing nano-sized Ti2O3, the steps of which are as follows: (1) Mix titanium powder and titanium dioxide and grind them into a uniform powder; The molar ratio of titanium powder to titanium dioxide is 1:3~5; Titanium powder is nano-sized titanium powder with a particle size of 50~200nm; Titanium dioxide is rutile or anatase phase titanium dioxide with a particle size of 5~100nm; (2) Place the powder obtained in step (1) in an inert atmosphere and calcine at 900~1100℃ for 1~5h (heating rate is 5~10℃ / min), cool to room temperature and take it out to obtain the nano-scale Ti2O3 powder of the present invention.
[0007] The inert atmosphere is either argon or helium.
[0008] The second objective of this invention is to provide a nanoscale Ti2O3 prepared by the above method.
[0009] The third objective of this invention is to provide the application of the aforementioned nano-sized Ti₂O₃ as a catalyst support. This involves dispersing nano-sized Ti₂O₃ in deionized water, adding a noble metal source (iridium trichloride, ruthenium trichloride, chloroplatinic acid, chloroauric acid, rhodium chloride, palladium chloride, etc.), and adjusting the pH of the reaction system to 9-11 with ammonia. The reaction is then reduced at 70-90°C for 4-6 hours, cooled to room temperature, and repeatedly centrifuged and washed with water. The dried powder is then calcined in air at 200-400°C for 1-3 hours to obtain a noble metal-supported catalyst, namely Ti₂O₃@MO. x The catalyst material contains M = Ru, Rh, Pd, Ir, Pt, or Au; the mass fraction of the noble metal in the catalyst is 10%~50%.
[0010] The fourth objective of this invention is to provide the application of the aforementioned nano-sized Ti2O3 as a catalyst support. This involves using nano-sized Ti2O3 as a support, dispersing it in an alcohol solution (ethanol, ethylene glycol, glycerol, etc.), then adding a noble metal source (iridium chlorochloride, ruthenium trichloride, chloroplatinic acid, chloroauric acid, rhodium chloride, or palladium chloride, etc.), stirring for 1-3 hours, and then isothermally reducing it at 150-200°C for 5-8 hours. After drying, a noble metal-supported catalyst, namely Ti2O3@M catalyst material, is prepared by alcohol reduction, where M = Ru, Rh, Pd, Ir, Pt, or Au; the mass fraction of the noble metal in the catalyst is 10%-50%.
[0011] Beneficial effects This invention enables the rapid synthesis of nano-sized Ti₂O₃, producing samples with uniform particle sizes around 300 nm. The preparation method is characterized by high efficiency and speed, low equipment requirements, simplicity and reproducibility, high product purity, and the ability to synthesize in large quantities. Furthermore, the small and uniform size of the nano-sized Ti₂O₃ obtained by this invention results in catalysts prepared using it as a support exhibiting good dispersibility and excellent electrocatalytic activity. It can also produce highly uniform catalyst slurries, suitable for electrochemical catalysis and energy conversion fields (such as...). Figure 7 (As shown). Attached Figure Description
[0012] Figure 1 The XRD pattern of nano-sized Ti2O3 prepared in Example 1 of this invention; Figure 2 A scanning electron microscope (SEM) image of nanoscale Ti2O3 prepared in Example 1 of this invention; Figure 3 The XRD pattern of Ti2O3@IrO2 prepared in Example 1 of this invention; Figure 4 Transmission electron microscope (TEM) image of Ti2O3@IrO2 prepared in Example 1 of this invention; Figure 5 The XRD pattern of Ti2O3@Ir prepared in Example 1 of this invention; Figure 6 Transmission electron microscope (TEM) image of Ti2O3@Ir prepared in Example 1 of this invention; Figure 7 The OER LSV curves of Ti2O3@IrO2 and Ti2O3@Ir prepared in Example 1 of this invention in 0.1M HClO4 electrolyte solution; Figure 8 The XRD pattern of nano-sized Ti2O3 prepared in Example 2; Figure 9 The XRD pattern of nano-sized Ti2O3 prepared in Example 3; Figure 10 The XRD pattern of nano-sized Ti2O3 prepared in Example 4; Figure 11 The XRD pattern of nano-sized Ti2O3 prepared in Example 5; Figure 12 The XRD pattern of nano-sized Ti2O3 prepared in Example 6; Figure 13 The XRD pattern of nano-sized Ti2O3 prepared in Example 7; Figure 14 The XRD pattern of nanoscale Ti2O3 prepared in Example 8. Detailed Implementation
[0013] The present invention will be further described in conjunction with the embodiments and accompanying drawings. However, the scope of protection of the present invention includes, but is not limited to, the following embodiments. Any changes and adjustments made without departing from the spirit and scope of the present invention will also be included within the scope of protection of the present invention.
[0014] The present invention will now be described with reference to specific embodiments. The process condition values used in the following embodiments are exemplary, and their possible value ranges are as shown in the foregoing description of the invention. For process parameters not specifically noted, conventional techniques can be referred to.
[0015] Example 1 Preparation of nano-sized Ti2O3 powder: 120 mg of titanium powder with a particle size of 100 nm and 584 mg of anatase phase titanium dioxide powder with a particle size of 20 nm were placed in an agate mortar and mixed evenly, and then ground into a fine and uniform powder; then the fine powder was placed in a corundum crucible and calcined at 950 °C for 2 hours in an argon atmosphere (heating rate of 10 °C / min), and after cooling to room temperature, 650 mg of nano-sized Ti2O3 powder was obtained.
[0016] Preparation of Ti2O3@MO x (M = Ru, Rh, Pd, Ir, Pt, Au) Materials: 200 mg of nano-sized Ti₂O₃ powder was ultrasonically dispersed in 30 mL of deionized water. The appropriate noble metal source (iridium trichloride, ruthenium trichloride, chloroplatinic acid, chloroauric acid, rhodium chloride, or palladium chloride) was added according to the catalyst loading ratio of 30 wt% noble metal. To synthesize Ti₂O₃@IrO₂, since the mass fraction of Ir is 30%, 86 mg of Ir needs to be added, i.e., 86 / 286 = 30%. The mass fraction of iridium in iridium trichloride is 54%, so 159 mg of iridium trichloride is needed, i.e., 86 / 54% = 30%. 159 mg of Ti2O3@IrO2 catalyst material was obtained by stirring for 2 hours and then adding ammonia (28% by mass) to adjust the pH to 10. The mixture was stirred at 80℃ for 5 hours and then cooled to room temperature. After repeated centrifugation and washing with water, the dried powder was placed in a corundum crucible and calcined at 300℃ in air for 1 hour to obtain 280 mg of Ti2O3@IrO2 catalyst material.
[0017] Preparation of Ti2O3@M (M = Ru, Rh, Pd, Ir, Pt, Au) material: 200 mg of nano-sized Ti2O3 powder was ultrasonically dispersed in 30 mL of ethylene glycol. The appropriate noble metal source (chloroiridic acid, ruthenium trichloride, chloroplatinic acid, chloroauric acid, rhodium chloride, or palladium chloride) was added according to the catalyst loading of 30 wt% noble metal. For example, to synthesize Ti2O3@Ir, since the mass fraction of Ir is 30%, 86 mg of Ir is needed, i.e., 86 / 286 = 30%. Since the mass fraction of iridium in chloroiridic acid is 35%, 246 mg of chloroiridic acid is needed, i.e., 86 / 35% = 246 mg. After stirring for 2 h, the mixture was stirred at a constant temperature of 180 °C for 6 h. After cooling to room temperature, it was centrifuged and washed with water multiple times, and finally dried to obtain 260 mg of Ti2O3@Ir catalyst material.
[0018] Characterization of Oxygen Evolution Catalytic Performance of Ti2O3@IrO2 and Ti2O3@Ir Catalysts: The electrocatalytic OER performance of the two prepared catalysts was evaluated in a three-electrode system using 0.1M HClO4 electrolyte. 8 mg of catalyst was ultrasonically dispersed in 400 μL of isopropanol and 400 μL of naphthol solution (0.5 wt%) to prepare a homogeneous slurry. 2.0 μL of the slurry was dropped onto a glassy carbon electrode (3 mm in diameter). Using the glassy carbon electrode with the catalyst as the working electrode, a platinum wire as the counter electrode, and a saturated calomel electrode as the reference electrode, the oxygen evolution catalytic performance was evaluated using a Chenhua electrochemical workstation.
[0019] The nanoscale Ti2O3 powder prepared by the above method, as well as the Ti2O3@IrO2 catalyst material and Ti2O3@Ir catalyst material prepared with it as a support, were characterized.
[0020] Figure 1 The XRD pattern of the prepared Ti2O3 shows that the diffraction peak positions are consistent with those of the standard PDF card for Ti2O3, indicating that pure phase Ti2O3 was synthesized.
[0021] Figure 2 The SEM image of the prepared Ti2O3 shows that the sample is composed of uniform particles of about 300 nm.
[0022] Figure 3 The XRD pattern of the prepared Ti2O3@IrO2 shows that the diffraction peaks of Ti2O3 are well preserved, while the diffraction peaks of IrO2 are broadened, proving the successful loading of IrO2.
[0023] Figure 4 The TEM image of the prepared Ti2O3@IrO2 shows that IrO2 is uniformly loaded on Ti2O3 to form a complete shell.
[0024] Figure 5 The XRD pattern of the prepared Ti2O3@Ir shows that the diffraction peaks of Ti2O3 are well preserved, while the diffraction peaks of Ir elemental are broadened, proving the successful loading of Ir particles.
[0025] Figure 6 TEM images of the prepared Ti2O3@Ir show that Ir elemental particles are uniformly loaded onto Ti2O3 to form a complete shell.
[0026] Figure 7 The OER LSV curves of Ti2O3@IrO2 and Ti2O3@Ir catalyst materials in 0.1M HClO4 electrolyte solution are shown, at a current density of 10 mA / cm². -2At these times, their overpotentials were 312 mV and 273 mV, respectively, indicating that both catalysts have good oxygen evolution catalytic activity.
[0027] By increasing the amount of raw materials tenfold, under the same conditions, gram-scale preparation of nano-sized Ti2O3 can be achieved. The gram-scale prepared Ti2O3 nanoparticles have uniform size and retain their excellent properties.
[0028] Example 2 This embodiment is the same as Example 1, except that the calcination temperature is changed from 950℃ to 900℃ and the calcination time is changed from 2 hours to 4 hours. All other synthesis conditions remain unchanged, and nano-sized Ti2O3 powder can still be obtained. Figure 8 The XRD pattern of the prepared Ti2O3 showed that the diffraction peak positions were consistent with those of the standard PDF card for Ti2O3, indicating that phase-pure Ti2O3 was synthesized. The XRD characterization results also showed that appropriately adjusting the calcination temperature and calcination time would not affect the preparation of nano-sized Ti2O3.
[0029] Example 3 This embodiment is the same as Example 1, except that the calcination temperature is changed from 950℃ to 1000℃ and the calcination time is changed from 2 hours to 3 hours. Other synthesis conditions remain unchanged, and nano-sized Ti2O3 powder can still be obtained. Figure 9 The XRD pattern of the prepared Ti2O3 showed that the diffraction peak positions were consistent with those of the standard PDF card for Ti2O3, indicating that phase-pure Ti2O3 was synthesized. The XRD characterization results also showed that appropriately adjusting the calcination temperature and calcination time would not affect the preparation of nano-sized Ti2O3.
[0030] Example 4 This embodiment is the same as Example 1, except that the calcination temperature is changed from 950℃ to 1100℃ and the calcination time is changed from 2 hours to 1 hour. Other synthesis conditions remain unchanged, and nano-sized Ti2O3 powder can still be obtained. Figure 10 The XRD pattern of the prepared Ti2O3 showed that the diffraction peak positions were consistent with those of the standard PDF card for Ti2O3, indicating that phase-pure Ti2O3 was synthesized. The XRD characterization results also showed that appropriately adjusting the calcination temperature and calcination time would not affect the preparation of nano-sized Ti2O3.
[0031] Example 5 This embodiment is the same as Example 1, except that the calcination temperature is changed from 950℃ to 1050℃ and the calcination time is changed from 2 hours to 5 hours. Other synthesis conditions remain unchanged, and nano-sized Ti2O3 powder can still be obtained. Figure 11The XRD pattern of the prepared Ti2O3 showed that the diffraction peak positions were consistent with those of the standard PDF card for Ti2O3, indicating that phase-pure Ti2O3 was synthesized. The XRD characterization results also showed that appropriately adjusting the calcination temperature and calcination time would not affect the preparation of nano-sized Ti2O3.
[0032] Example 6 This embodiment is the same as Example 1, except that the titanium powder with a particle size of 100 nm is replaced with titanium powder with a particle size of 50 nm, and the anatase phase titanium dioxide powder with a particle size of 20 nm is replaced with anatase phase titanium dioxide powder with a particle size of 100 nm. Other synthesis conditions remain unchanged, and nano-sized Ti2O3 powder can still be obtained. Figure 12 The XRD pattern of the prepared Ti2O3 showed that the diffraction peak positions were consistent with those of the standard PDF card for Ti2O3, indicating that phase-pure Ti2O3 was synthesized. The XRD characterization results show that appropriately adjusting the particle size of the raw materials does not affect the preparation of nano-sized Ti2O3.
[0033] Example 7 This embodiment is the same as Example 1, except that the anatase phase titanium dioxide powder with a particle size of 20 nm is replaced with rutile phase titanium dioxide powder with a particle size of 20 nm. Other synthesis conditions remain unchanged, and nano-sized Ti2O3 powder can still be obtained. Figure 13 The XRD pattern of the prepared Ti2O3 showed that the diffraction peak positions were consistent with those of the standard PDF card for Ti2O3, indicating that phase-pure Ti2O3 was synthesized. The XRD characterization results show that appropriate modulation of the crystal phase of titanium dioxide does not affect the preparation of nano-scale Ti2O3.
[0034] Example 8 This embodiment is the same as Example 1, except that the calcination atmosphere is changed from argon to helium. All other synthesis conditions remain unchanged, and nano-sized Ti2O3 powder can still be obtained. Figure 14 The XRD pattern of the prepared Ti2O3 showed that the diffraction peak positions were consistent with those of the standard PDF card for Ti2O3, indicating that phase-pure Ti2O3 was synthesized. The XRD characterization results also showed that appropriate modulation of the calcination atmosphere would not affect the preparation of nano-sized Ti2O3.
Claims
1. A method for preparing nano-sized Ti2O3, comprising the following steps: (1) Mix titanium powder and titanium dioxide and grind them into a uniform powder; in, The molar ratio of titanium powder to titanium dioxide is 1:3~5; Titanium powder is nano-sized titanium powder with a particle size of 50~200nm; Titanium dioxide is rutile or anatase phase titanium dioxide with a particle size of 5~100nm; (2) Place the powder obtained in step (1) in an inert atmosphere and calcine at 900~1100℃ for 1~5h, cool to room temperature and take it out to obtain nano-sized Ti2O3 powder.
2. The method for preparing nano-sized Ti2O3 as described in claim 1, characterized in that: The inert atmosphere in step (2) is argon or helium, and the heating rate during calcination is 5~10℃ / min.
3. A nano-scale Ti2O3, characterized in that: It is prepared by the preparation method described in claim 1 or 2.
4. The application of the nano-sized Ti2O3 as a catalyst support as described in claim 3.
5. The application of nano-sized Ti2O3 as a catalyst support as described in claim 4, characterized in that: Nanoscale Ti₂O₃ was dispersed in deionized water, and a noble metal source was added. The pH of the reaction system was adjusted to 9–11 with ammonia. The mixture was then reduced at 70–90 °C for 4–6 h. After cooling to room temperature, it was centrifuged and washed repeatedly. The dried powder was calcined in air at 200–400 °C for 1–3 h to obtain the noble metal-supported catalyst, Ti₂O₃@MO. x The catalyst material contains M = Ru, Rh, Pd, Ir, Pt, or Au; the mass fraction of the noble metal in the catalyst is 10%~50%.
6. The application of nano-sized Ti2O3 as a catalyst support as described in claim 4, characterized in that: Using nano-sized Ti2O3 as a support, it is dispersed in an alcohol solution, and then a noble metal source is added. After stirring for 1-3 hours, it is reduced at a constant temperature of 150-200℃ for 5-8 hours. After drying, the noble metal supported catalyst, namely Ti2O3@M catalyst material, is prepared by alcohol reduction method, where M = Ru, Rh, Pd, Ir, Pt or Au; the mass fraction of noble metal in the catalyst is 10%-50%.
7. The application of nanoscale Ti2O3 as a catalyst support as described in claim 5 or 6, characterized in that: The precious metal sources are iridium trichloride, ruthenium trichloride, chloroplatinic acid, chloroauric acid, rhodium chloride, or palladium chloride.
8. The application of nano-sized Ti2O3 as a catalyst support as described in claim 6, characterized in that: The alcohol solution is ethanol, ethylene glycol, or glycerol, etc.