PtSn-based ternary intermetallic compound electrode coating material and preparation method and application thereof
By using PtSn-based ternary intermetallic compounds as electrode coating materials, the problem of low sensitivity and accuracy of existing electrochemical formaldehyde sensor electrode materials is solved, and the effect of high formaldehyde sensitivity and low detection limit is achieved, which is suitable for large-scale commercial applications.
Patent Information
- Application Number
- CN202510296039.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-13
- Publication Date
- 2025-06-06
AI Technical Summary
The sensitivity and accuracy of existing electrochemical formaldehyde sensor electrode materials are low and the detection limit is high.
PtSn-based ternary intermetallic compound is used as the electrode coating material. By placing the Pt metal precursor, the Sn metal precursor and the third component metal precursor in a solvent, ultrasonic until it is completely dissolved, then drop by drop into the carbon carrier, ultrasonic uniformly, then dry and grind, and finally calcined at high temperature under a reducing atmosphere, PtSn-based ternary intermetallic compound electrode coating material with high formaldehyde sensitivity was prepared.
It achieves the effects of high formaldehyde sensitivity, low detection limit and high accuracy, and the preparation process is simple and the products are uniform, making it easy to promote and apply on a large scale.
Smart Images
Figure CN120098493A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the field of formaldehyde-sensitive coating materials for electrochemical sensors, and in particular to a PtSn-based ternary intermetallic compound and a preparation method and application thereof. Background Art
[0002] Formaldehyde is an important organic raw material, widely used in building materials, furniture, textile industry, cleaning products and food preservation. Since formaldehyde is highly volatile and easily released from liquid or solid materials, it has become one of the main sources of indoor air pollution. After entering the human body, formaldehyde will be enriched and converted into methyl derivatives, destroying RNA in cells, causing sudden canceration and necrosis of cells, thereby causing serious damage to organ tissues and the nervous system. In 2004, it was included in the first category of carcinogens by the World Health Organization's International Agency for Research on Cancer (IARC). In addition, the release period of formaldehyde in indoor home building materials is as long as 3 to 15 years, which will continue to affect human health.
[0003] Since indoor formaldehyde is toxic, volatile, and widely distributed, it needs to be detected frequently. The main detection methods for formaldehyde currently include spectrophotometry, chromatography, mass spectrometry, and electrochemical sensors. The first three traditional detection methods are expensive and have long test cycles. In the absence of regular calibration and traceability, the accuracy of the test data is poor. In addition, there are high professional requirements for operators, making it difficult to apply them to daily life. The emerging electrochemical sensors are not only sensitive, accurate, simple, fast, and low-cost, but also have significant advantages in detection range and anti-interference ability (Chen P., et al., Analytical Biochemistry 2019, 574, 23-30), and are ideal portable household formaldehyde sensing devices. The ability of the sensitive material coated on the electrode to recognize formaldehyde determines the selectivity and sensitivity of the sensor. Therefore, the development of new and efficient formaldehyde-sensitive electrode materials with good selectivity, high accuracy and long life is the key to realizing the large-scale commercial application of electrochemical formaldehyde sensing technology (Yang Q., et al., Bioelectrochemistry 2021, 138, 107713). In recent years, it has been found that some precious metal nanoparticles have a strong ability to oxidize formaldehyde molecules, which can be further used as new sensing materials for detecting formaldehyde through modification and assembly. Theoretical calculations indicate that the relatively strong electronegativity of Pt in single metal electrode materials is conducive to the formaldehyde sensor to generate recordable electrical signals, and the specific sensitivity of the sensor can be adjusted by doping atoms with different electronegativity (Li Y., Sensors and Actuators: A. Physical, 2022, 338, 113460). Among them, the oxophilic metal Sn with less electronegativity than Pt as a doping metal can effectively improve the oxidation ability of Pt-based materials for C1 compounds (Lu Y., et al., ACS Applied Materials & Interfaces 2024, 16, 35134). On this basis, the introduction of a transition metal M with smaller electronegativity and atomic radius than Pt and Sn as the third metal to weaken the adsorption of intermediate products can further improve the formaldehyde sensitivity. Summary of the invention
[0004] The purpose of the present invention is to design and provide a method for synthesizing a PtSn-based ternary intermetallic compound formaldehyde sensitive material and formaldehyde sensing application in view of the problems of low sensitivity and accuracy and high detection limit of the existing electrochemical formaldehyde sensor electrode materials. The PtSn-based ternary intermetallic compound has the advantages of high formaldehyde sensitivity, low detection limit and high accuracy, and the preparation process is simple, the product is uniform, and it is easy to promote and apply on a large scale.
[0005] In order to achieve the above object, the technical solution adopted by the present invention is:
[0006] A preparation method of a PtSn-based ternary intermetallic compound electrode coating material and its formaldehyde sensing application, comprising the following steps:
[0007] (1) adding a Pt metal precursor, a Sn metal precursor and a third component metal precursor to a solvent in sequence to prepare a precursor impregnation solution, and ultrasonicating until the metal precursor is completely dissolved to obtain a metal precursor impregnation solution;
[0008] (2) dripping the metal precursor impregnation liquid obtained in step (1) dropwise into the pretreated carbon support, and drying and grinding the mixture after ultrasonic homogenization to obtain a powder impregnated with the metal precursor;
[0009] (3) The powder impregnated with the metal precursor obtained in step (2) is calcined at high temperature under a reducing atmosphere to obtain a PtSn-based ternary intermetallic compound electrode coating material.
[0010] Preferably, in step (1), the Pt metal precursor is chloroplatinic acid or platinum acetylacetonate; the Sn metal precursor is tin tetrachloride or tin acetylacetonate; the third component metal precursor is an inorganic metal salt of Mn, Cr, Fe, Co, Ni or one of the acetylacetonate salts of Mn, Cr, Fe, Co, Ni.
[0011] Preferably, in step (1), the concentration of the Pt precursor is 1.5 to 4 times the sum of the concentrations of Sn and the third metal precursor, and the solvent is ethanol or DMF.
[0012] Preferably, in step (2), the carbon carrier is mesoporous carbon; the pretreatment is acid washing, water washing, drying, roasting and grinding; the roasting temperature is 800-1100° C., and the roasting time is 0.5-2.5 h.
[0013] Preferably, in step (2), the temperature of the ultrasound is 0-30°C, and the drying is vacuum drying at a temperature of 20-30°C.
[0014] Preferably, in step (3), the reducing atmosphere is H 2 / Ar mixed gas or ammonia, the high temperature calcination temperature is 600-950°C, and the calcination time is 1.5-6h.
[0015] The second aspect of the present invention provides a formaldehyde sensitizing electrode modified with a PtSn-based ternary intermetallic compound coating material prepared by the above method.
[0016] Preferably, the PtSn-based ternary intermetallic compound electrode coating material is dissolved in a solution containing Nafion, wherein the solution is an aqueous solution, an ethanol solution, an isopropanol solution or a mixture thereof of Nafion, and the volume percentage concentration of Nafion is 0.1-5%. After being evenly dispersed by ultrasonic, the material is coated on the surface of the working electrode, and after low-temperature drying with an infrared lamp or natural drying, the material becomes the formaldehyde-sensitizing electrode of the electrochemical sensor.
[0017] A PtSn-based ternary intermetallic compound electrode coating material prepared by any of the preparation methods described above.
[0018] Application of the PtSn-based ternary intermetallic compound electrode coating material prepared by any of the preparation methods described above in the field of formaldehyde sensing sensitization.
[0019] The present invention adopts a simple synthesis method of mesoporous carbon confined in-situ reduction to form a PtSn-based ternary intermetallic compound material with small particle size and highly ordered structure. The obtained material exhibits excellent catalytic activity and stability to formaldehyde and can be used as an electrode coating material for an electrochemical formaldehyde sensor. The material preparation process is simple and efficient and easy to industrialize.
[0020] Compared with the prior art, the present invention has the following advantages and beneficial effects:
[0021] The present invention provides a PtSn-based ternary intermetallic compound electrode coating material, which has high formaldehyde sensitivity and is simple to operate and low in cost when applied to an electrochemical formaldehyde sensor, and has practical application significance for the detection of toxic and harmful gas formaldehyde. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 The Pt prepared in Example 1 3 Sn 0.5 Mn 0.5 TEM image of / FDU intermetallic compound.
[0023] Figure 2 Pt prepared in Example 2 3 Sn 0.7 Cr 0.3 TEM image of / DMC intermetallic compound.
[0024] Figure 3 Pt prepared in Example 2 3 Sn 0.7 Cr 0.3 / DMC intermetallic compound XRD pattern.
[0025] Figure 4 The Pt prepared in Example 3 3 Sn 0.5 Mn 0.5Formaldehyde electrochemical sensing response curve of / DMC intermetallic compound coated electrode.
[0026] Figure 5 The Pt prepared in Example 3 3 Sn 0.5 Mn 0.5 Formaldehyde electrochemical sensing selectivity response diagram of / DMC intermetallic compound coated electrode.
[0027] Figure 6 Pt prepared in Example 4 3 Sn 0.6 Co 0.4 Electrochemical sensing response curve of DMC intermetallic compound coated electrode at ultra-low formaldehyde concentration (<1ppb). DETAILED DESCRIPTION
[0028] The present invention is further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.
[0029] Example 1
[0030] FDU-15 was placed in 0.5MH 2 SO 4 After acid washing in the solution for 8 h, the mixture was washed with water until the pH value was neutral, and then vacuum dried and heated in NH 3 Calcinate at 800℃ for 40min in an ambient environment, cool down, take out and grind for later use.
[0031] 0.15mmol chloroplatinic acid, 0.025mmol stannous chloride, and 0.025mmol manganese chloride were dissolved in 1mL ethanol to a concentration of 0.15mol / L, 0.025mol / L, and 0.025mol / L, respectively, and ultrasonically mixed until the metal precursor solution was completely uniform.
[0032] 180 μL of the metal precursor solution was slowly dripped into 20 mg of pretreated mesoporous carbon FDU-15 evenly spread, ultrasonicated in a 0°C ice-water mixture for 60 min, and then vacuum dried at 25°C. The dried product was ground and heated in H 2 The volume fraction of H is 10%. 2 / Ar atmosphere at 750℃ for 4h to obtain the formaldehyde sensitive electrode material Pt 3 Sn 0.5 Mn 0.5 / FDU. Figure 1 It is a transmission electron microscope image, and it can be seen that Pt 3 Sn 0.5 Mn 0.5 The particle size of the ternary intermetallic compounds is uniform and evenly dispersed on the FDU-15 mesoporous carbon.
[0033] Pt 3 Sn 0.5 Mn 0.5 / FDU is dissolved in 0.25% Nafion / ethanol solution, evenly dispersed by ultrasonication, and coated on the surface of the working electrode. After natural drying at room temperature, it can be used for formaldehyde sensing electrode sensitization.
[0034] Example 2
[0035] The ZIF-8 derived carbon DMC was placed in 0.5 MH 2 SO 4 After acid washing in the solution for 10 h, the mixture was washed with water until the pH value was neutral, and then vacuum dried and heated in NH 3 Calcinate at 800℃ for 40min in an ambient environment, cool down, take out and grind for later use.
[0036] 0.15mmol chloroplatinic acid, 0.035mmol stannous chloride, and 0.015mmol chromium chloride were dissolved in 1mL ethanol to a concentration of 0.15mol / L, 0.035mol / L, and 0.015mol / L, respectively, and ultrasonically mixed until the metal precursor solution was completely uniform.
[0037] Take 200 μL of the metal precursor solution and slowly drip it into 20 mg of pre-treated DMC evenly spread, ultrasonicate it in a 0°C ice-water mixture for 90 min, and then vacuum dry it at 20°C. 2 The volume fraction of H is 10%. 2 / Ar atmosphere at 800℃ for 3.5h to obtain the formaldehyde sensitive electrode material Pt 3 Sn 0.7 Cr 0.3 / DMC. Figure 2 It is a transmission electron microscope image, and it can be seen that Pt 3 Sn 0.7 Cr 0.3 The particle size of the ternary metal compounds is uniform and evenly dispersed on the DMC mesoporous carbon. Figure 3 Its XRD spectrum is compared with the ordered Pt 3 Sn and Pt 3 Comparison of Cr intermetallic compound XRD standard cards shows that Pt 3 Sn 0.7 Cr 0.3 A highly ordered ternary intermetallic compound structure has been formed.
[0038] Pt 3 Sn 0.7 Cr 0.3 / DMC is dissolved in 0.5% Nafion / isopropanol solution, evenly dispersed by ultrasonication, and coated on the surface of the working electrode. After natural drying at room temperature, it can be used for formaldehyde sensing electrode sensitization.
[0039] Example 3
[0040] The ZIF-8 derived carbon DMC was placed in 0.5 MH 2 SO 4 After acid washing in the solution for 10 h, the mixture was washed with water until the pH value was neutral, and then vacuum dried and heated in NH 3 Calcinate at 800℃ for 40min in an ambient environment, cool down, take out and grind for later use.
[0041] 0.15mmol chloroplatinic acid, 0.025mmol stannous chloride, and 0.025mmol manganese chloride were dissolved in 1mL ethanol to a concentration of 0.15mol / L, 0.025mol / L, and 0.025mol / L, respectively, and ultrasonically mixed until the metal precursor solution was completely uniform.
[0042] Take 200 μL of the metal precursor solution and slowly drip it into 20 mg of pre-treated DMC evenly spread, ultrasonicate it in a 0°C ice-water mixture for 90 min, and then vacuum dry it at 20°C. 2 The volume fraction of H is 10%. 2 / Ar atmosphere at 750℃ for 4h to obtain the formaldehyde sensitive electrode material Pt 3 Sn 0.5 Mn 0.5 / DMC.
[0043] Pt 3 Sn 0.5 Mn 0.5 / DMC is dissolved in a 0.25% Nafion / (isopropanol+water) mixed solution, evenly dispersed by ultrasonication, and coated on the surface of the working electrode. After natural drying at room temperature, it can be used for formaldehyde sensing electrode sensitization. Figure 4 The formaldehyde electrochemical sensing response curve of the electrode coated with it shows that Pt 3 Sn 0.5 Mn 0.5 The electrode modified with / DMC is very sensitive to formaldehyde and shows obvious response when the formaldehyde concentration is 1 ppb. Figure 5 Pt 3 Sn 0.5 Mn 0.5 The formaldehyde electrochemical sensing selectivity response diagram of the / DMC intermetallic compound coated electrode shows that when many similar interferents exist at the same time, the electrode modified by the coating material still shows high selectivity for formaldehyde.
[0044] Example 4
[0045] The ZIF-8 derived carbon DMC was placed in 0.5 MH 2 SO4 After acid washing in the solution for 10 h, the mixture was washed with water until the pH value was neutral, and then vacuum dried and heated in NH 3 Calcinate at 800℃ for 40min in an ambient environment, cool down, take out and grind for later use.
[0046] 0.15mmol platinum acetylacetonate, 0.03mmol tin acetylacetonate, and 0.02mmol cobalt acetylacetonate were dissolved in 1mL DMF with concentrations of 0.15mol / L, 0.03mol / L, and 0.02mol / L, respectively, and ultrasonically mixed until the metal precursor solution was completely uniform.
[0047] Take 200 μL of the metal precursor solution and slowly drip it into 20 mg of pre-treated DMC evenly spread, ultrasonicate it at 20 °C for 90 min, and then vacuum dry it at 20 °C. 2 NH with a volume fraction of 10% 3 Calcinate at 650℃ for 2h in atmosphere to obtain the formaldehyde sensitive electrode material Pt 3 Sn 0.6 Co 0.4 / DMC.
[0048] Pt 3 Sn 0.6 Co 0.4 / DMC is dissolved in a 0.5% Nafion / isopropanol mixed solution, evenly dispersed by ultrasonication, and coated on the surface of the working electrode. After low-temperature drying with an infrared lamp, it can be used for formaldehyde sensing electrode sensitization. Figure 6 The electrochemical sensing response curve of the coated electrode at ultra-low formaldehyde concentration (<1ppb) shows that Pt 3 Sn 0.6 Co 0.4 The electrode modified with / DMC is extremely sensitive to formaldehyde, with a detection limit of 0.1ppb.
[0049] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.
Claims
1. A method for preparing a PtSn-based ternary intermetallic compound electrode coating material, characterized in that: The following steps are involved: (1) adding a Pt metal precursor, a Sn metal precursor and a third component metal precursor to a solvent in sequence to prepare a precursor impregnation solution, and ultrasonicating until the metal precursor is completely dissolved to obtain a metal precursor impregnation solution; (2) dripping the metal precursor impregnation liquid obtained in step (1) dropwise into the pretreated carbon support, and drying and grinding the mixture after ultrasonic homogenization to obtain a powder impregnated with the metal precursor; (3) The powder impregnated with the metal precursor obtained in step (2) is calcined at high temperature under a reducing atmosphere to obtain a PtSn-based ternary intermetallic compound electrode coating material.
2. The method for preparing a PtSn-based ternary intermetallic compound electrode coating material according to claim 1, characterized in that: In step (1), the Pt metal precursor is chloroplatinic acid or platinum acetylacetonate; the Sn metal precursor is tin tetrachloride or tin acetylacetonate; the third component metal precursor is an inorganic metal salt of Mn, Cr, Fe, Co, Ni or one of the acetylacetonate salts of Mn, Cr, Fe, Co, Ni.
3. The method for preparing a PtSn-based ternary intermetallic compound electrode coating material according to claim 1, characterized in that: In step (1), the concentration of the Pt precursor is 1.5 to 4 times the sum of the concentrations of Sn and the third metal precursor, and the solvent is ethanol or DMF.
4. The method for preparing a PtSn-based ternary intermetallic compound electrode coating material according to claim 1, characterized in that: In step (2), the carbon carrier is mesoporous carbon; the pretreatment is acid washing, water washing, drying, roasting and grinding; the roasting temperature is 800-1100° C., and the roasting time is 0.5-2.5 h.
5. The method for preparing a PtSn-based ternary intermetallic compound electrode coating material according to claim 1, characterized in that: In step (2), the temperature of the ultrasound is 0-30°C, and the drying is vacuum drying at a temperature of 20-30°C.
6. The method for preparing a PtSn-based ternary intermetallic compound electrode coating material according to claim 1, characterized in that: In step (3), the reducing atmosphere is H2 / Ar mixed gas or ammonia, the high temperature calcination temperature is 600-950°C, and the calcination time is 1.5-6h.
7. A PtSn-based ternary intermetallic compound electrode coating material prepared by the preparation method according to any one of claims 1 to 6.
8. The PtSn-based ternary intermetallic compound electrode coating material according to claim 7 is used in the field of formaldehyde sensing sensitization.
9. The use according to claim 8, characterized in that: The PtSn-based ternary intermetallic compound electrode coating material is dissolved in a Nafion solution, uniformly dispersed by ultrasonication, and then coated on the surface of the working electrode. After drying, it becomes the formaldehyde sensitization electrode of the electrochemical sensor.
10. The use according to claim 8, characterized in that: The solution is a Nafion aqueous solution, an ethanol solution, an isopropanol solution or a mixture thereof, and the volume percentage concentration of the Nafion is 0.1-5%. The drying is low-temperature drying with an infrared lamp or natural drying.