Preparation method of catalyst of carbon-loaded titanium dioxide and platinum nanoparticles
Carbon-supported titanium dioxide and platinum nanoparticle catalysts were prepared by an improved sol-gel method and polyol reduction method, which solved the problems of transition metal precipitation and insufficient conductivity of the support, and improved catalytic activity and stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-03-03
- Publication Date
- 2026-04-03
AI Technical Summary
In existing technologies, alloying with transition metal elements carries the risk of precipitation, which can contaminate the proton exchange membrane. Furthermore, the metal oxide support has insufficient conductivity, which affects catalytic performance.
An improved sol-gel method was used to support amorphous TiO2, and carbon-supported anatase TiO2 nanoparticles were formed by annealing in an inert atmosphere. Platinum nanoparticles were then supported by a polyol reduction method to form a Pt-TiO2/C catalyst.
It improves catalytic activity, avoids insufficient conductivity of the support and corrosion of carbon support, and enhances the stability and performance of the catalyst.
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Figure CN121775835A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing a catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles. Background Technology
[0002] On the one hand, in the past, Pt was alloyed with transition metal elements (Fe, Ni, Co, etc.) to utilize the size difference between transition metal atoms and Pt atoms to induce lattice distortion, thereby adjusting the d-band center of Pt to improve its activity. However, transition metal elements pose a risk of precipitation, which can contaminate the proton exchange membrane and ionomers of PEMWE, reduce the proton conduction rate, and affect the increase of overpotential under high current.
[0003] On the other hand, some metal oxides (TiO2, SnO2, etc.) have also been reported to exhibit strong metal-support interaction (SMSI) when used as supports for Pt nanoparticles, which may help improve catalytic performance. However, the poor conductivity of these metal oxides hinders their application in electrocatalysts.
[0004] Therefore, it is necessary to design a method for preparing a catalyst supported on carbon-coated titanium dioxide and platinum nanoparticles. Summary of the Invention
[0005] The purpose of this invention is to provide a method for preparing a catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles, so as to solve the problems in the prior art.
[0006] The objective of this invention can be achieved through the following technical solutions: A method for preparing a catalyst supported on carbon-based titanium dioxide and platinum nanoparticles, the method comprising the following steps: S1: Amorphous TiO2 was loaded using a modified sol-gel method, washed and dried for later use; S2: The sample obtained in S1 was annealed under an inert atmosphere to obtain carbon-supported anatase TiO2 nanoparticles. S3: The sample obtained in S2 was dispersed in a polyol, and the loaded platinum nanoparticles were reduced by heating. After washing and drying, Pt-TiO2 / C was obtained.
[0007] Furthermore, in step S1, the titanium alkoxide used in the improved sol-gel method is one or more of tetrabutyl titanate, tetraisopropyl titanate, or tetraethyl titanate.
[0008] Furthermore, in step S1, the carbon support used is one or more of Cabot XC-72R, Cabot BP2000, KetjenBlack EC300J, Ketjen Black EC600JD, acetylene black, and carbon nanotubes.
[0009] Furthermore, in step S1, the improved sol-gel method involves using sodium dodecylbenzenesulfonate as an aid to achieve a more uniform loading of amorphous titanium dioxide.
[0010] Furthermore, in step S1, the improved sol-gel method used involves using a weak alkali such as ammonia to promote the hydrolysis of titanium alkoxides.
[0011] Furthermore, in step S2, the inert atmosphere used is one or more of Ar, N2, and H2 / Ar mixture.
[0012] Furthermore, in step S2, annealing is performed in an inert atmosphere for 60-120 minutes at a temperature of 300-500°C.
[0013] Furthermore, in step S3, the polyol reduction method requires the addition of sodium hydroxide to the selected organic solvent, with a molar ratio of noble metal salt to sodium hydroxide of 1:6~20.
[0014] Furthermore, in step S3, the reduction temperature range of the polyol reduction method is 60~160 ℃, and the time is 30 min~180 min.
[0015] Furthermore, in step S3, before washing using the polyol reduction method, 1M hydrochloric acid is added to deposit platinum nanoparticles at a certain volume ratio of 1:0.4~1, and the mixture is stirred for 30 minutes before washing and drying.
[0016] The beneficial effects of this invention are: 1. This invention utilizes the strong metal-support interaction between titanium dioxide and Pt nanoparticles to improve catalytic activity.
[0017] 2. This invention utilizes carbon-supported titanium dioxide nanoparticles followed by Pt nanoparticles, thus avoiding the problem of insufficient conductivity of the carrier.
[0018] 3. This invention utilizes the presence of titanium dioxide on the carbon surface to protect the carbon support and reduce the possibility of carbon support corrosion. Attached Figure Description
[0019] The invention will now be further described with reference to the accompanying drawings.
[0020] Figure 1This is a TEM image of an embodiment of the technical solution of this invention; Figure 2 This is a diagram illustrating an implementation example of the technical solution of this invention. Detailed Implementation
[0021] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Example
[0022] A method for preparing a catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles, comprising the following steps: S1: Amorphous TiO2 was loaded using a modified sol-gel method, washed and dried for later use; In step S1, the titanium alkoxide used in the improved sol-gel method is one or more of tetrabutyl titanate, tetraisopropyl titanate, or tetraethyl titanate.
[0023] In step S1, the carbon support used is one or more of Cabot XC-72R, Cabot BP2000, Ketjen Black EC300J, Ketjen Black EC600JD, acetylene black, and carbon nanotubes.
[0024] In step S1, the improved sol-gel method uses sodium dodecylbenzenesulfonate as an aid to achieve a more uniform loading of amorphous titanium dioxide.
[0025] In step S1, the improved sol-gel method used involves using a weak alkali such as ammonia to promote the hydrolysis of titanium alkoxides.
[0026] S2: The sample obtained in S1 was annealed under an inert atmosphere to obtain carbon-supported anatase TiO2 nanoparticles. In step S2, the inert atmosphere used is one or more of Ar, N2, and H2 / Ar mixture.
[0027] In step S2, annealing is performed in an inert atmosphere for 60 minutes at a temperature of 300°C.
[0028] S3: The sample obtained in S2 was dispersed in a polyol, and the loaded platinum nanoparticles were reduced by heating. After washing and drying, Pt-TiO2 / C was obtained.
[0029] In step S3, the polyol reduction method used requires the addition of sodium hydroxide to the selected organic solvent, with a molar ratio of noble metal salt to sodium hydroxide of 1:6.
[0030] In step S3, the reduction temperature range using the polyol reduction method is 80 °C, and the time is 30 min.
[0031] In step S3, before washing using the polyol reduction method, 1M hydrochloric acid is added in a certain volume ratio to deposit platinum nanoparticles, with a volume ratio of 1:0.4. The mixture is stirred for 30 minutes before washing and drying. Example
[0032] A method for preparing a catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles, comprising the following steps: S1: Amorphous TiO2 was loaded using a modified sol-gel method, washed and dried for later use; In step S1, the titanium alkoxide used in the improved sol-gel method is one or more of tetrabutyl titanate, tetraisopropyl titanate, or tetraethyl titanate.
[0033] In step S1, the carbon support used is one or more of Cabot XC-72R, Cabot BP2000, Ketjen Black EC300J, Ketjen Black EC600JD, acetylene black, and carbon nanotubes.
[0034] In step S1, the improved sol-gel method uses sodium dodecylbenzenesulfonate as an aid to achieve a more uniform loading of amorphous titanium dioxide.
[0035] In step S1, the improved sol-gel method used involves using a weak alkali such as ammonia to promote the hydrolysis of titanium alkoxides.
[0036] S2: The sample obtained in S1 was annealed under an inert atmosphere to obtain carbon-supported anatase TiO2 nanoparticles. In step S2, the inert atmosphere used is one or more of Ar, N2, and H2 / Ar mixture.
[0037] In step S2, annealing is performed in an inert atmosphere for 80 minutes at a temperature of 400°C.
[0038] S3: The sample obtained in S2 was dispersed in a polyol, and the loaded platinum nanoparticles were reduced by heating. After washing and drying, Pt-TiO2 / C was obtained.
[0039] In step S3, the polyol reduction method used requires the addition of sodium hydroxide to the selected organic solvent, with a molar ratio of noble metal salt to sodium hydroxide of 1:12.
[0040] In step S3, the reduction temperature range using the polyol reduction method is 120 °C, and the time is 100 min.
[0041] In step S3, before washing using the polyol reduction method, 1M hydrochloric acid is added to deposit platinum nanoparticles at a volume ratio of 1:0.8. The mixture is stirred for 30 minutes before washing and drying. Example
[0042] A method for preparing a catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles, comprising the following steps: S1: Amorphous TiO2 was loaded using a modified sol-gel method, washed and dried for later use; In step S1, the titanium alkoxide used in the improved sol-gel method is one or more of tetrabutyl titanate, tetraisopropyl titanate, or tetraethyl titanate.
[0043] In step S1, the carbon support used is one or more of Cabot XC-72R, Cabot BP2000, Ketjen Black EC300J, Ketjen Black EC600JD, acetylene black, and carbon nanotubes.
[0044] In step S1, the improved sol-gel method uses sodium dodecylbenzenesulfonate as an aid to achieve a more uniform loading of amorphous titanium dioxide.
[0045] In step S1, the improved sol-gel method used involves using a weak alkali such as ammonia to promote the hydrolysis of titanium alkoxides.
[0046] S2: The sample obtained in S1 was annealed under an inert atmosphere to obtain carbon-supported anatase TiO2 nanoparticles. In step S2, the inert atmosphere used is one or more of Ar, N2, and H2 / Ar mixture.
[0047] In step S2, annealing is performed in an inert atmosphere for 120 minutes at a temperature of 500°C.
[0048] S3: The sample obtained in S2 was dispersed in a polyol, and the loaded platinum nanoparticles were reduced by heating. After washing and drying, Pt-TiO2 / C was obtained.
[0049] In step S3, the polyol reduction method used requires the addition of sodium hydroxide to the selected organic solvent, with a molar ratio of noble metal salt to sodium hydroxide of 1:20.
[0050] In step S3, the reduction temperature range using the polyol reduction method is 80~160 ℃, and the time is 180 min.
[0051] In step S3, before washing using the polyol reduction method, 1M hydrochloric acid is added in a certain volume ratio to deposit platinum nanoparticles (volume ratio 1:1), and the mixture is stirred for 30 minutes before washing and drying.
[0052] This invention provides a catalyst for preparing carbon-supported titanium dioxide and platinum nanoparticles using the above method.
[0053] In the following specific embodiments, all operations without specified conditions are carried out under conventional conditions or manufacturer's recommendations, and all raw materials without specified manufacturers and specifications are conventional products that can be obtained commercially.
[0054] The obtained carbon-supported titanium dioxide and platinum nanoparticle catalyst was tested using an electrochemical cyclic voltammetry method.
[0055] The electrochemical cyclic voltammetry (CV) test instrument consisted of a rotating disk electrode system from Ivy (Netherlands) connected to a Chi 760E electrochemical workstation from Shanghai Chenhua Instrument Co., Ltd. The test conditions were as follows: the catalyst ink formulation was 750 μL ultrapure water, 250 μL isopropanol, and 4 μL Nafion solution. The catalyst was dispersed in the solvent using an ultrasonic bath for 30 min to form a uniformly dispersed ink. A glassy carbon electrode was used as the test electrode, and the electrolyte was a 0.1 M perchloric acid solution. Nitrogen gas was purged for 30 min before the test. The test scan range was 0.05 ~ 1.1 V vs. RHE, and the scan rate was 50 mV s. -1 Hydrogen evolution reaction (HER) was also performed using a rotating disk electrode system from Ivy & Mather (Netherlands) connected to a Chi 760E electrochemical workstation. The electrolyte was a 0.1 M perchloric acid solution. Nitrogen gas was bubbled through the system for 30 min. The test rotation speed was 1600 rpm, the test scan range was -0.2 V to 0.05 V vs. HER, and the scan rate was 10 mV / s. -1 .
[0056] The proton exchange membrane electrolysis (PEMWE) membrane electrode was prepared by ultrasonic spraying. A catalyst slurry was prepared by mixing the catalyst with water, alcohol, and ionomer in a specific ratio. This slurry was then ultrasonically sprayed onto a proton exchange membrane (DuPont Nafion N115), and finally assembled with a gas diffusion layer to form the membrane electrode. The effective area of the membrane electrode was 25 cm². 2 The anode uniformly uses commercially available iridium oxide (IrO). x Catalysts, cathodes, and catalysts prepared using implementation and comparative examples.
[0057] Implementation Case 1: like Figure 1 As shown, 2 g of Cabot XC-72R was placed in a flask, and 100 ml of 5 wt.% sodium dodecylbenzenesulfonate solution was added. The mixture was ultrasonically dispersed for 2 h, followed by the addition of 1 L of anhydrous ethanol and stirring for 30 min. This solution was designated as solution A and was kept for later use. 8.3 mL of tetrabutyl titanate was added to 300 mL of anhydrous ethanol, followed by the addition of 7.2 mL of acetic acid and stirring until homogeneous. This solution was designated as solution B and was kept for later use.
[0058] While stirring continuously, solution B was added dropwise to solution A, followed by stirring at a constant temperature of 30°C for 2 hours. The pH of the reaction solution was adjusted to 9 by adding ammonia water diluted with anhydrous ethanol, then 300 mL of anhydrous ethanol was added, and the mixture was stirred for an additional 30 minutes. The solution was then filtered, washed first with anhydrous ethanol, then with ultrapure water, and dried for later use.
[0059] The dried powder was ground and then annealed at 450°C under an Ar atmosphere for 2 hours.
[0060] Annealed C-TiO2 was dispersed in a certain amount of ethylene glycol, and a chloroplatinic acid ethylene glycol solution was added to achieve a Pt loading of 20 wt.%. Simultaneously, a sodium hydroxide ethylene glycol solution was added to achieve a chloroplatinic acid:sodium hydroxide molar ratio of 1:7. After stirring for a certain period of time, the mixture was heated to 160℃, and after cooling, a 1M HCl solution was added at a volume ratio of 1:1 with the reaction solution. The mixture was stirred for 30 minutes, then filtered, washed, and subsequently dried.
[0061] Implementation Case 2: Unlike Implementation Case 1, the amount of tetrabutyl titanate was increased from 8.3 mL to 12.5 mL.
[0062] Implementation Case 3: Unlike Implementation Case 1, the Cabot XC-72R was replaced with a Ketjen Black EC600JD.
[0063] Implementation Case 4: Unlike Implementation Case 1, tetrabutyl titanate was replaced with tetraisopropyl titanate.
[0064] Comparative Cases: Pt / C was prepared using a reduction method essentially the same as in Implementation Case 1, with Cabot XC-72R used as the carbon support. The difference was that these carbon supports were not loaded with nano-titanium dioxide.
[0065] like Figure 2As shown, under the same current conditions, the comparative case requires a larger voltage, while the implementation cases 1 to 4 require a smaller current. Furthermore, the voltage of the implementation cases tends to be concentrated, stable, and consistent, showing a better improvement compared to the comparative case.
[0066] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.
Claims
1. A method for preparing a catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles, characterized in that, The catalyst preparation method includes the following steps: S1: Amorphous TiO2 was loaded using a modified sol-gel method, washed and dried for later use; S2: The sample obtained in S1 was annealed under an inert atmosphere to obtain carbon-supported anatase TiO2 nanoparticles. S3: The sample obtained in S2 was dispersed in a polyol, and the loaded platinum nanoparticles were reduced by heating. After washing and drying, Pt-TiO2 / C was obtained.
2. The method for preparing the catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles according to claim 1, characterized in that, In step S1, the titanium alkoxide used in the improved sol-gel method is one or more of tetrabutyl titanate, tetraisopropyl titanate, or tetraethyl titanate.
3. The method for preparing the catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles according to claim 2, characterized in that, In step S1, the carbon support used is one or more of Cabot XC-72R, Cabot BP2000, Ketjen Black EC300J, Ketjen Black EC600JD, acetylene black, and carbon nanotubes.
4. The method for preparing the catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles according to claim 3, characterized in that, In step S1, the improved sol-gel method uses sodium dodecylbenzenesulfonate as an aid to achieve a more uniform loading of amorphous titanium dioxide.
5. The method for preparing the catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles according to claim 4, characterized in that, In step S1, the improved sol-gel method used involves using a weak alkali such as ammonia to promote the hydrolysis of titanium alkoxides.
6. The method for preparing the catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles according to claim 1, characterized in that, In step S2, the inert atmosphere used is one or more of Ar, N2, and H2 / Ar mixture.
7. The method for preparing the catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles according to claim 6, characterized in that, In step S2, annealing is performed in an inert atmosphere for 60-120 minutes at a temperature of 300-500°C.
8. The method for preparing the catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles according to claim 1, characterized in that, In step S3, the polyol reduction method used requires the addition of sodium hydroxide to the selected organic solvent, with a molar ratio of noble metal salt to sodium hydroxide of 1:6~20.
9. The method for preparing the catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles according to claim 8, characterized in that, In step S3, the reduction temperature range of the polyol reduction method is 60~160 ℃, and the time is 30 min~180 min.
10. The method for preparing the catalyst supported on carbon-supported titanium dioxide and platinum nanoparticles according to claim 9, characterized in that, In step S3, before washing using the polyol reduction method, 1M hydrochloric acid is added to deposit platinum nanoparticles at a certain volume ratio of 1:0.4~1. The mixture is stirred for 30 minutes before washing and drying.