Preparation method of tungsten oxide loaded platinum nanocluster catalyst containing oxygen vacancy
The preparation of tungsten oxide support and loading platinum nanoclusters by hydrothermal method solves the resource scarcity and stability of precious metal catalysts, and realizes the efficient preparation of electrolytic hydrogen analysis catalysts, which is suitable for the electrolytic hydrogen production process.
Patent Information
- Application Number
- CN202510679661.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-23
- Publication Date
- 2025-08-29
AI Technical Summary
The existing precious metal catalysts are scarce, cost-effective and unstable in the process of electrolyzing hydrogen production, and are difficult to apply on a large scale. The controllable preparation of nanocluster catalysts is still a challenge.
The tungsten oxide support containing oxygen defects was prepared by hydrothermal method, and the platinum nanoclusters were loaded by impregnation method to form a Pt nanocluster catalyst supported by tungsten oxide, and the size of the nanoclusters was adjusted by controlling the concentration of the metal precursor solution of the platinum.
The preparation of an efficient and stable electrolytic hydrogen evolution catalyst is achieved. The catalyst exhibits excellent electrocatalytic properties in electrolytic water, which are suitable for large-scale production and application.
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Figure CN120556073A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of catalyst preparation, and in particular to a method for preparing a tungsten oxide-supported platinum nanocluster catalyst containing oxygen defects. Background Art
[0002] The continued consumption of traditional fossil fuels has triggered a series of energy and environmental challenges, necessitating an urgent need to improve the supply chain for alternative energy sources, from acquisition to utilization. Hydrogen, as a clean, green, high-energy-density, and pollution-free renewable energy source, is an ideal alternative and considered one of the most promising new energy sources. Currently, hydrogen can be produced through a variety of methods, including traditional industrial methods such as petroleum cracking and methane cracking, as well as emerging approaches such as photocatalytic water splitting and electrolysis. However, traditional hydrogen production methods, such as petroleum cracking and coal gasification, are often accompanied by significant toxic gas emissions, making them difficult to meet current environmental sustainability requirements. Photocatalytic water splitting, on the other hand, is limited by low photoelectric conversion efficiency. In contrast, electrolysis has attracted widespread attention due to its advantages such as ease of operation, high product purity, and environmental friendliness. Furthermore, alternative energy sources such as wind, tidal, and solar energy exhibit significant regional, seasonal, and unstable characteristics, making them difficult to directly connect to the power grid and utilize. Therefore, utilizing these energy sources to produce hydrogen through electrolysis offers an effective solution to energy utilization challenges.
[0003] Therefore, driven by the global energy transition, water electrolysis has become a major route for producing "green hydrogen" and has been strongly supported by policies in various countries. As the hydrogen energy application market matures, water electrolysis will become the mainstream direction of the future low-carbon economy. Water electrolysis has attracted widespread attention due to its simple operation, high purity, and environmentally friendly properties. Currently, in the actual application of water electrolysis for hydrogen production, commercial water electrolysis catalysts are mainly precious metal catalysts, such as Pt / C and IrO2. However, the scarcity of resources, high cost, and poor stability of precious metal catalysts under acidic conditions are the main reasons hindering their large-scale application. Therefore, the development of stable and efficient low-precious metal catalysts has become a major problem that needs to be solved urgently. Nanocluster-level catalysts have extremely high atomic utilization because more metal active sites can participate in the catalytic reaction, which enables the catalyst to exert the maximum catalytic effect during the catalytic process. However, their controllable preparation remains a major challenge. Summary of the Invention
[0004] The first technical problem to be solved by the present invention is to provide a method for preparing a tungsten oxide-supported platinum nanocluster catalyst containing oxygen defects. The preparation method achieves the preparation of an efficient and stable catalyst for hydrogen evolution by electrolysis of water by anchoring platinum nanoclusters on a defective tungsten oxide carrier. The catalyst obtained by the present invention is a tungsten oxide-supported Pt nanocluster electrocatalyst.
[0005] In order to solve the above-mentioned first technical problem, the technical solution adopted by the present invention is as follows:
[0006] A method for preparing a tungsten oxide-supported platinum nanocluster catalyst containing oxygen defects comprises the following steps:
[0007] 1) Disperse tungsten chloride in anhydrous ethanol, stir ultrasonically to fully dissolve it, transfer it to a hydrothermal reactor, increase the temperature and react;
[0008] 2) After the reaction is completed, the supernatant is removed, and the remaining reaction product is centrifuged and washed with a mixed solution of deionized water and anhydrous ethanol, and then placed in a drying oven to dry to obtain tungsten oxide;
[0009] 3) Disperse tungsten oxide in deionized water, dissolve it uniformly under ultrasonication, and stir to form solution A;
[0010] 4) Disperse the platinum precursor salt in deionized water, dissolve it by ultrasonication, and slowly add it dropwise to solution A, stirring to react;
[0011] 5) After the reaction is completed, the reaction solution is centrifuged to obtain a solid, and the solid is placed in a vacuum drying oven to dry to obtain a solid product;
[0012] 6) calcining the solid product under an inert atmosphere to obtain a tungsten oxide-supported platinum nanocluster catalyst.
[0013] As a further improvement of the technical solution, in step 1), the mass concentration of the tungsten chloride is 3-10 mg / mL, and the ultrasonic dispersion conditions are: 40%-80% of 400 W power, and ultrasonication for 1-5 min.
[0014] Preferably, in step 1), the elevated temperature refers to the temperature being elevated to 100-170° C., and the reaction time is 9-12 hours.
[0015] As a further improvement of the technical solution, in step 2), the volume ratio of the mixed solution of deionized water and anhydrous ethanol is 1:5-1:1, and the washing centrifugation refers to adding deionized water and anhydrous ethanol to the centrifuged product, ultrasonically dispersing it and centrifuging it again to collect the solid product, and repeating the above process 2-3 times; the centrifugation conditions are 5000-10000 rpm and the time is 5-8 min.
[0016] Preferably, in step 2), the temperature in the vacuum drying oven is 35-60° C., and the vacuum degree is 0.08-0.1 MPa.
[0017] As a further improvement of the technical solution, in step 3), the mass concentration of the tungsten oxide in deionized water is 1-4 mg / mL.
[0018] Preferably, in step 3), the stirring temperature is 40-80° C., and the stirring time is 30-90 minutes.
[0019] As a further improvement of the technical solution, in step 4), the precursor salt of platinum is selected from one of chloroplatinic acid and potassium tetrachloroplatinate.
[0020] Preferably, in step 4), the mass concentration of the platinum precursor salt solution is 1-26 mg / mL; and the ultrasonic conditions are: 40%-80% of 400 W power, and ultrasonication for 1-5 min.
[0021] Preferably, in step 4), the stirring reaction time is 4-8 hours.
[0022] As a further improvement of the technical solution, in step 5), the centrifugation condition is 5000-10000 rpm and the time is 5-8 min.
[0023] Preferably, in step 5), the temperature in the vacuum drying oven is 40-80° C., and the vacuum degree is 0.08-0.1 MPa.
[0024] As a further improvement of the technical solution, in step 6), the calcination treatment needs to first purge the system with inert gas for 60-150 minutes.
[0025] Preferably, in step 6), the inert gas is nitrogen or argon.
[0026] Preferably, in step 6), the heating rate after purging is 3-10° C. / min, the calcination temperature is 300-500° C., and is maintained for 60-150 min.
[0027] Any range described in the present invention includes the end value and any numerical value between the end values and any sub-range formed by the end value or any numerical value between the end values.
[0028] Unless otherwise specified, all raw materials in the present invention can be purchased commercially, and the equipment used in the present invention can adopt conventional equipment in the relevant field or refer to the existing technology in the relevant field.
[0029] Compared with the prior art, the present invention has the following beneficial effects:
[0030] The preparation method of the present invention uses a hydrothermal method to prepare a tungsten oxide carrier containing oxygen defects, and then loads uniformly dispersed platinum nanoclusters on the tungsten oxide through a simple impregnation method. The size of the platinum nanoclusters can be precisely controlled by varying the concentration of the platinum metal precursor solution. Characterization results such as X-ray diffraction spectra, transmission electron microscopy, and elemental distribution maps confirm the uniform loading of the Pt nanoclusters on the tungsten oxide containing oxygen defects. This simple preparation method facilitates the scale-up production of the catalyst. In addition, the prepared catalyst exhibits excellent electrocatalytic performance in hydrogen evolution by water electrolysis, and has a very broad application prospect. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.
[0032] Figure 1 shows the X-ray diffraction pattern of the sample prepared in Example 1;
[0033] Figure 2 Shows the EPR results of the sample prepared in Example 1;
[0034] Figure 3 shows a transmission electron microscope image of the sample prepared in Example 1;
[0035] Figure 4 shows the element distribution diagram of the sample prepared in Example 1;
[0036] Figure 5 This is the X-ray diffraction pattern of the sample obtained in Example 2;
[0037] Figure 6 The EPR results of the sample obtained in Example 2 are as follows;
[0038] Figure 7 This is a transmission electron microscope image of the sample obtained in Example 2;
[0039] Figure 8 This is the X-ray diffraction pattern of the sample obtained in Example 3;
[0040] Figure 9 This is the EPR result of the sample obtained in Example 3;
[0041] Figure 10 This is a transmission electron microscope image of the sample obtained in Example 3;
[0042] Figure 11 This is the X-ray diffraction pattern of the sample obtained in Comparative Example 1;
[0043] Figure 12 The EPR results of the sample obtained in Comparative Example 1 are as follows;
[0044] Figure 13 The performance comparison chart of the samples prepared in comparative example 2 and example 1 is shown. DETAILED DESCRIPTION
[0045] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the following detailed description is illustrative rather than restrictive and should not be used to limit the scope of protection of the present invention.
[0046] For ease of description, if the descriptions in the present invention involve "first", "second", etc., they are only set for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" or "second" may explicitly or implicitly include at least one of such features. In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the fact that they can be implemented by ordinary technicians in this field. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by the present invention.
[0047] As one aspect of the present invention, a method for preparing a tungsten oxide-supported platinum nanocluster catalyst containing oxygen defects comprises the following steps:
[0048] 1) Disperse tungsten chloride in anhydrous ethanol, stir ultrasonically to fully dissolve it, transfer it to a hydrothermal reactor, increase the temperature and react;
[0049] 2) After the reaction is completed, the supernatant is removed, and the remaining reaction product is washed by centrifugation with a mixed solution of deionized water and anhydrous ethanol, and then placed in a drying oven to dry to obtain tungsten oxide;
[0050] 3) Disperse tungsten oxide in deionized water, dissolve it uniformly under ultrasonication, and stir to form solution A;
[0051] 4) Disperse the platinum precursor salt in deionized water, dissolve it by ultrasonication, and slowly add it dropwise to solution A, stirring to react;
[0052] 5) After the reaction is completed, the reaction solution is centrifuged to obtain a solid, and the solid is placed in a vacuum drying oven to dry to obtain a solid product;
[0053] 6) calcining the solid product under an inert atmosphere to obtain a tungsten oxide-supported platinum nanocluster catalyst.
[0054] In certain embodiments of the present invention, in step 1), the mass concentration of the tungsten chloride is 3-10 mg / mL, and the ultrasonic dispersion conditions are: 40%-80% of 400 W power, and ultrasonication for 1-5 min.
[0055] In certain embodiments of the present invention, in step 1), raising the temperature means raising the temperature to 100-170° C., and the reaction time is 9-12 hours.
[0056] In certain embodiments of the present invention, in step 2), the volume ratio of the mixed solution of deionized water and anhydrous ethanol is 1:5 to 1:1, and the washing centrifugation refers to adding deionized water and anhydrous ethanol to the centrifuged product, ultrasonically dispersing it and centrifuging it again to collect the solid product, and repeating the above process 2-3 times; the centrifugation conditions are 5000-10000 rpm and the time is 5-8 min.
[0057] In certain embodiments of the present invention, in step 2), the temperature in the vacuum drying oven is 35-60° C., and the vacuum degree is 0.08-0.1 MPa.
[0058] In certain embodiments of the present invention, in step 3), the mass concentration of the tungsten oxide in deionized water is 1-4 mg / mL.
[0059] In certain embodiments of the present invention, in step 3), the stirring temperature is 40-80° C., and the stirring time is 30-90 minutes.
[0060] In certain embodiments of the present invention, in step 4), the precursor salt of platinum is selected from one of chloroplatinic acid and potassium tetrachloroplatinate.
[0061] In certain embodiments of the present invention, in step 4), the mass concentration of the platinum precursor salt solution is 1-26 mg / mL; and the ultrasonic conditions are: 40%-80% of 400 W power for 1-5 min.
[0062] In certain embodiments of the present invention, in step 4), the stirring reaction time is 4-8 hours.
[0063] In certain embodiments of the present invention, in step 5), the centrifugation condition is 5000-10000 rpm and the time is 5-8 min.
[0064] In certain embodiments of the present invention, in step 5), the temperature in the vacuum drying oven is 40-80° C., and the vacuum degree is 0.08-0.1 MPa.
[0065] In certain embodiments of the present invention, in step 6), the calcination treatment requires first purging the system with an inert gas for a purging time of 60-150 minutes.
[0066] In certain embodiments of the present invention, in step 6), the inert gas is nitrogen or argon.
[0067] In certain embodiments of the present invention, in step 6), the heating rate after purging is 3-10° C. / min, the calcination temperature is 300-500° C., and the temperature is maintained for 60-150 min.
[0068] Example 1
[0069] A method for preparing a tungsten oxide-supported platinum nanocluster catalyst containing oxygen defects comprises the following steps:
[0070] 1) Disperse tungsten oxide in anhydrous ethanol at a concentration of 8 mg / mL, stir ultrasonically to fully dissolve it, transfer it to a hydrothermal reactor, and react at 160°C for 10 hours;
[0071] 2) After the reaction is completed, the supernatant is discarded, and the reaction product is washed 2 to 3 times with a mixed solution of deionized water and anhydrous ethanol in a volume ratio of 1:1, and then placed in a drying oven to dry to obtain tungsten oxide;
[0072] 3) Disperse tungsten oxide in deionized water to a concentration of 1 mg / mL, dissolve it uniformly under ultrasound, and continue stirring at 60°C for 40 minutes to form solution A;
[0073] 4) Potassium tetrachloroplatinate was selected as the platinum metal precursor salt and dispersed in deionized water at a concentration of 4 mg / mL. After ultrasonic dissolution, it was slowly added dropwise to the above solution A and the reaction was continued for 6 hours;
[0074] 5) After stirring, the solution was centrifuged and the obtained solid was placed in a vacuum drying oven to dry to obtain a solid product.
[0075] 6) The solid product was calcined at 300° C. for 1 hour under an argon atmosphere, and the temperature was naturally lowered to obtain a final product, a tungsten oxide-supported platinum nanocluster catalyst containing oxygen defects.
[0076] Figure 1 The X-ray diffraction pattern of the sample prepared in Example 1 is shown, indicating that Pt exists in the form of nanoclusters;
[0077] Figure 2 The EPR results of the sample prepared in Example 1 are shown, confirming the presence of oxygen vacancies;
[0078] Figure 3 The transmission electron microscope image of the sample prepared in Example 1 is shown;
[0079] Figure 4 The element distribution diagram of the sample prepared in Example 1 is shown.
[0080] Example 2
[0081] Example 1 was repeated, except that in step 4), the concentration of the platinum metal precursor salt solution was 9 mg / mL, and nanocluster catalysts of different sizes were prepared.
[0082] Figure 5 This is the X-ray diffraction pattern of the sample prepared in Example 2, indicating that Pt exists in the form of nanoclusters;
[0083] Figure 6 The EPR results of the sample prepared in Example 2 confirm the presence of oxygen vacancies;
[0084] Figure 7 This is a transmission electron microscope image of the sample obtained in Example 2.
[0085] Example 3
[0086] Example 1 was repeated, except that in step 4), the concentration of the platinum metal precursor salt solution was 1 mg / mL, and nanocluster catalysts of different sizes were prepared.
[0087] Figure 8 This is the X-ray diffraction pattern of the sample prepared in Example 3, indicating that Pt exists in the form of nanoclusters;
[0088] Figure 9 The EPR results of the sample prepared in Example 3 confirm the presence of oxygen vacancies;
[0089] Figure 10 This is a transmission electron microscope image of the sample prepared in Example 3.
[0090] Comparative Example 1
[0091] Example 1 was repeated except that steps 3), 4) and 5) were not performed to prepare a tungsten oxide carrier containing oxygen vacancies and without metal loading.
[0092] Figure 11 This is the X-ray diffraction pattern of the sample obtained in Comparative Example 1;
[0093] Figure 12 The EPR result of the sample prepared in this comparative example 1 confirmed the existence of oxygen defects.
[0094] Comparative Example 2
[0095] Example 1 was repeated, with the only difference being that in step 3), stirring was performed at room temperature (25°C). The performance of the obtained sample was compared with that of the catalyst sample prepared in Example 1, and it was found that the performance of the sample under room temperature stirring was significantly reduced.
[0096] Figure 13The performance comparison between the sample prepared in this comparative example 2 and that in Example 1 is shown.
[0097] In summary, the present invention provides a method for preparing a tungsten oxide-supported platinum nanocluster catalyst containing oxygen defects, in which the temperature, reaction time, solution concentration, calcination conditions, etc. are coordinated and cooperated with each other to form a complete technical solution, so that the supported nanocluster catalyst required by the present invention can be better prepared.
[0098] Obviously, the above embodiments of the present invention are merely examples for the purpose of clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that other variations or modifications based on the above description are possible. It is not possible to enumerate all embodiments here. Any obvious variations or modifications arising from the technical solution of the present invention remain within the scope of protection of the present invention.
Claims
1. A method for preparing a tungsten oxide-supported platinum nanocluster catalyst containing oxygen defects, characterized in that: The steps include: 1) Disperse tungsten chloride in anhydrous ethanol, stir ultrasonically to fully dissolve it, transfer it to a hydrothermal reactor, increase the temperature and react; 2) After the reaction is completed, the supernatant is removed, and the remaining reaction product is centrifuged and washed with a mixed solution of deionized water and anhydrous ethanol, and then placed in a drying oven to dry to obtain tungsten oxide; 3) Disperse tungsten oxide in deionized water, dissolve it uniformly under ultrasonication, and stir to form solution A; 4) Disperse the platinum precursor salt in deionized water, dissolve it by ultrasonication, and slowly add it dropwise to solution A, stirring to react; 5) After the reaction is completed, the reaction solution is centrifuged to obtain a solid, and the solid is placed in a vacuum drying oven to dry to obtain a solid product; 6) calcining the solid product under an inert atmosphere to obtain a tungsten oxide-supported platinum nanocluster catalyst.
2. The method for preparing the tungsten oxide-supported platinum nanocluster catalyst according to claim 1, wherein: In step 1), the mass concentration of the tungsten chloride is 3-10 mg / mL, and the ultrasonic dispersion conditions are: 40%-80% of 400 W power, and ultrasonication for 1-5 minutes.
3. The method for preparing the tungsten oxide-supported platinum nanocluster catalyst according to claim 1, wherein: In step 1), the elevated temperature refers to a temperature raised to 100-170° C., and the reaction time is 9-12 hours.
4. The method for preparing the tungsten oxide-supported platinum nanocluster catalyst according to claim 1, wherein: In step 2), the volume ratio of the mixed solution of deionized water and anhydrous ethanol is 1:5-1:1, and the washing centrifugation refers to adding deionized water and anhydrous ethanol to the centrifuged product, ultrasonically dispersing it and centrifuging it again to collect the solid product, and repeating the above process 2-3 times; the centrifugation conditions are 5000-10000 rpm and the time is 5-8 min.
5. The method for preparing the tungsten oxide-supported platinum nanocluster catalyst according to claim 1, wherein: In step 2), the temperature in the vacuum drying oven is 35-60° C., and the vacuum degree is 0.08-0.1 MPa.
6. The method for preparing the tungsten oxide-supported platinum nanocluster catalyst according to claim 1, characterized in that: In step 3), the mass concentration of the tungsten oxide in deionized water is 1-4 mg / mL.
7. The method for preparing the tungsten oxide-supported platinum nanocluster catalyst according to claim 1, wherein: In step 3), the stirring temperature is 40-80° C. and the stirring time is 30-90 minutes.
8. The method for preparing the tungsten oxide-supported platinum nanocluster catalyst according to claim 1, characterized in that: In step 4), the platinum precursor salt is selected from one of chloroplatinic acid and potassium tetrachloroplatinate; Preferably, in step 4), the mass concentration of the platinum precursor salt solution is 1-26 mg / mL; the ultrasonic conditions are: 40%-80% of 400W power, ultrasonication for 1-5 minutes; Preferably, in step 4), the stirring reaction time is 4-8 hours.
9. The method for preparing the tungsten oxide-supported platinum nanocluster catalyst according to claim 1, characterized in that: In step 5), the centrifugation condition is 5000-10000 rpm and the time is 5-8 min; Preferably, in step 5), the temperature in the vacuum drying oven is 40-80° C., and the vacuum degree is 0.08-0.1 MPa.
10. The method for preparing the tungsten oxide-supported platinum nanocluster catalyst according to claim 1, characterized in that: In step 6), the calcination treatment requires first purging the system with inert gas for 60-150 minutes; Preferably, in step 6), the inert gas is nitrogen or argon; Preferably, in step 6), the heating rate after purging is 3-10° C. / min, the calcination temperature is 300-500° C., and is maintained for 60-150 min.