Cystamine modified electrolytic hydrogen sulfide catalytic material as well as preparation method and application thereof
By modifying electrolytic hydrogen sulfide catalytic materials by cysteamine, the problems of high catalyst costs and unenvironmental protection in the prior art are solved, and more efficient and low-cost catalytic performance and environmental protection are achieved.
Patent Information
- Application Number
- CN202510175655.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-18
- Publication Date
- 2025-06-06
AI Technical Summary
In the prior art, the catalyst for electrocatalytic decomposition of hydrogen sulfide is expensive and difficult to achieve large-scale application. The traditional method of treating hydrogen sulfide is high in energy consumption, has a large carbon emissions and is not environmentally friendly.
A cysteamine-modified electrolytic hydrogen sulfide catalytic material is prepared by modifying the cysteamine-modified electrolytic hydrogen sulfide catalytic material.
The catalyst/molecular layer interface is constructed, the active surface area and catalytic performance of the catalytic material are improved, the preparation cost is reduced, and it is environmentally friendly and pollution-free.
Smart Images
Figure CN120099557A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of hydrogen sulfide electrolysis catalytic materials, and in particular to a cysteamine-modified hydrogen sulfide electrolysis catalytic material and a preparation method and application thereof. Background Art
[0002] Under the dual pressures of global energy transformation and environmental protection, finding an efficient, clean and sustainable way of energy utilization has become a common goal of countries around the world. Hydrogen energy, as a high-energy-density, pollution-free, renewable clean energy, is crucial to achieving deep decarbonization in high-carbon fields. The development of the hydrogen energy industry is of great strategic significance for promoting a cleaner, more efficient and sustainable global energy structure. Hydrogen can be divided into gray hydrogen, blue hydrogen and green hydrogen due to its different production paths. The formation process of green hydrogen does not produce carbon dioxide. Green hydrogen is the only way to convert electricity into chemical energy and the key to achieving carbon neutrality.
[0003] Green hydrogen can be produced by electrocatalytic decomposition of hydrogen sulfide, which is a highly toxic and smelly harmful substance and an important sulfur and hydrogen resource. Long-term exposure will endanger human health. Hydrogen sulfide in fossil fuels will corrode oil and natural gas pipelines, causing serious economic losses. The traditional method of treating hydrogen sulfide is the Claus process, which has high energy consumption, large carbon emissions and is not environmentally friendly. Compared with this method, the electrocatalytic decomposition of hydrogen sulfide technology has the advantages of low reaction energy consumption, mild conditions and controllable rate. In the electrocatalytic decomposition of hydrogen sulfide technology, precious metals such as platinum are catalysts with better catalytic performance, but their cost is too high to be suitable for large-scale application, so many studies are devoted to the development of cheap non-precious metal catalysts. Summary of the invention
[0004] In view of the above problems, the present invention aims to provide a cysteamine-modified hydrogen sulfide electrolysis catalytic material and a preparation method and application thereof.
[0005] The technical solution of the present invention is as follows:
[0006] In one aspect, a method for preparing a cysteamine-modified hydrogen sulfide electrolysis catalytic material is provided, comprising the following steps:
[0007] S1: preparing a cysteamine solution and obtaining a nanomaterial to be modified, wherein the nanomaterial to be modified is a catalytic material for electrolysis of hydrogen sulfide;
[0008] S2: soaking the nanomaterial to be modified in the cysteamine solution until the cysteamine is modified onto the surface of the nanomaterial to be modified;
[0009] S3: taking out the modified nanomaterial, and drying it to obtain the cysteamine-modified hydrogen sulfide electrolysis catalytic material.
[0010] Preferably, in step S1, when preparing the cysteamine solution, the solvent of the cysteamine solution is deionized water or ethanol, and the concentration is 1M-10 -2 M.
[0011] Preferably, in step S1, the nanomaterial to be modified has unsaturated sites, and the thiol sulfur atom of cysteamine in the cysteamine solution can form a coordination bond with the unsaturated sites through a lone pair of electrons, thereby modifying the nanomaterial to be modified with cysteamine.
[0012] Preferably, the nanomaterial to be modified is Ni 3 S 2 Any one of nanomaterials, NiSe nanomaterials, and CoP nanomaterials.
[0013] Preferably, the nanomaterial to be modified is produced by in-situ growing the nanomaterial on a substrate.
[0014] Preferably, when the nanomaterial to be modified is Ni 3 S 2 When using nanomaterials, the Ni 3 S 2 Nanomaterials are made through the following steps:
[0015] Preparing a substrate and pre-treating the substrate;
[0016] preparing a thiourea solution, and immersing the pretreated substrate in the thiourea solution;
[0017] The Ni 3 S 2 Nanomaterials.
[0018] Preferably, the substrate is any one of foamed iron, foamed nickel, foamed copper, and foamed nickel-iron; when preparing the thiourea solution, the solvent used is deionized water or ethanol, the mass of the solute is 0.05g-0.15g, and the volume of the solvent is 30mL-50mL.
[0019] Preferably, when the heating reaction is carried out, the heating temperature is 140°C-160°C, and the heating time is 5h-13h; when the drying is carried out, the drying temperature is 40°C-80°C, and the drying time is 4h-6h.
[0020] On the other hand, a cysteamine-modified hydrogen sulfide electrolysis catalytic material prepared by any of the above-mentioned methods for preparing a cysteamine-modified hydrogen sulfide electrolysis catalytic material and its application in hydrogen sulfide electrolysis desulfurization are also provided.
[0021] The beneficial effects of the present invention are:
[0022] The present invention can anchor cysteamine on the surface of the electrolytic hydrogen sulfide catalytic material by a simple soaking method to construct a catalyst / molecular layer modification interface. The preparation method is simple to operate, low in cost, and environmentally friendly and pollution-free. The modified material has a larger active surface area than the raw material. When used, the amino group of cysteamine can also interact with the electrolyte. The combined effect of the two makes the present invention have better catalytic performance; the present invention has important application value in the field of efficient and low-cost hydrogen production. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.
[0024] Figure 1 Ni before cysteamine modification prepared in Comparative Example 1 3 S 2 SEM images of nanomaterials;
[0025] Figure 2 Ni modified with cysteamine prepared in Example 1 3 S 2 SEM images of nanomaterials;
[0026] Figure 3 Ni before and after cysteamine modification of Example 1 and Comparative Example 1 3 S 2 Infrared spectra of nanomaterials;
[0027] Figure 4 Ni before and after cysteamine modification of Example 1 and Comparative Example 1 3 S 2 Schematic diagram of the SOR performance test results of nanomaterials under the conditions of electrolysis of hydrogen sulfide in an electrolytic cell;
[0028] Figure 5 It is a schematic diagram of the SOR performance test results of the CoP nanomaterials before and after cysteamine modification of Example 2 and Comparative Example 2 under the condition of electrolysis of hydrogen sulfide in an electrolytic cell;
[0029] Figure 6 It is a schematic diagram of the SOR performance test results of NiSe nanomaterials before and after cysteamine modification in Example 3 and Comparative Example 3 under the condition of electrolysis of hydrogen sulfide in an electrolytic cell;
[0030] Figure 7 Ni of Example 1 and Comparative Example 4 3 S 2Schematic diagram of the SOR performance test results of nanomaterials under the conditions of hydrogen sulfide electrolysis in an electrolytic cell. DETAILED DESCRIPTION
[0031] The present invention is further described below in conjunction with the accompanying drawings and embodiments. It should be noted that, in the absence of conflict, the embodiments in this application and the technical features in the embodiments can be combined with each other. It should be noted that, unless otherwise specified, all technical and scientific terms used in this application have the same meanings as those generally understood by those of ordinary skill in the art to which this application belongs. The words "including" or "comprising" and the like used in the disclosure of the present invention mean that the elements or objects appearing before the word cover the elements or objects listed after the word and their equivalents, without excluding other elements or objects.
[0032] In one aspect, the present invention provides a method for preparing a cysteamine-modified hydrogen sulfide electrolysis catalytic material, comprising the following steps:
[0033] S1: preparing a cysteamine solution and obtaining a nanomaterial to be modified, wherein the nanomaterial to be modified is a catalytic material for electrolysis of hydrogen sulfide.
[0034] In a specific embodiment, when preparing the cysteamine solution, the solvent of the cysteamine solution is deionized water or ethanol, and the concentration is 1M-10 -2 M.
[0035] In a specific embodiment, the nanomaterial to be modified has unsaturated sites, and the thiol sulfur atom of cysteamine in the cysteamine solution can form a coordination bond with the unsaturated sites through a lone pair of electrons, thereby modifying the nanomaterial to be modified with cysteamine.
[0036] In a specific embodiment, the nanomaterial to be modified is Ni 3 S 2 Any one of nanomaterials, NiSe nanomaterials, and CoP nanomaterials.
[0037] In a specific embodiment, the nanomaterial to be modified is prepared by in-situ growth of the nanomaterial on the substrate. 3 S 2 When using nanomaterials, the Ni 3 S 2 Nanomaterials are made through the following steps:
[0038] Prepare a substrate and pre-treat the substrate; prepare a thiourea solution and immerse the pre-treated substrate in the thiourea solution; perform a heating reaction, cool to room temperature after the reaction is completed, wash and dry to obtain the Ni 3 S 2 Nanomaterials.
[0039] In a specific embodiment, the substrate is any one of foamed iron, foamed nickel, foamed copper, and foamed nickel-iron; when preparing the thiourea solution, the solvent used is deionized water or ethanol, the mass of the solute is 0.05g-0.15g, and the volume of the solvent is 30mL-50mL.
[0040] In a specific embodiment, when the heating reaction is performed, the heating temperature is 140°C-160°C, and the heating time is 5h-13h; when the drying is performed, the drying temperature is 40°C-80°C, and the drying time is 4h-6h.
[0041] S2: Soaking the nanomaterial to be modified in the cysteamine solution until the cysteamine is modified onto the surface of the nanomaterial to be modified.
[0042] The invention soaks the nano material to be modified in a cysteamine solution, and utilizes the thiol sulfur atoms of the cysteamine molecules in the cysteamine solution to form coordination bonds with unsaturated sites on the electrolytic hydrogen sulfide catalytic material, thereby modifying the electrolytic hydrogen sulfide catalytic material with cysteamine to form a catalyst / molecular layer interface with excellent interface mass transfer performance.
[0043] In a specific embodiment, when the concentration of the cysteamine solution is 1M-10 -2 M, the soaking time is 1h-2h. It should be noted that the soaking conditions such as the soaking concentration and soaking time can be adjusted according to the actual catalytic performance requirements. As long as the cysteamine molecules can evenly cover the electrolytic hydrogen sulfide catalytic material, and the performance of the modified catalyst is improved, it is the cysteamine-modified electrolytic hydrogen sulfide catalytic material claimed in the present invention.
[0044] S3: taking out the modified nanomaterial, and drying it to obtain the cysteamine-modified hydrogen sulfide electrolysis catalytic material.
[0045] On the other hand, the present invention also provides a cysteamine-modified hydrogen sulfide electrolysis catalytic material prepared by any of the above-mentioned methods for preparing a cysteamine-modified hydrogen sulfide electrolysis catalytic material and its application in hydrogen sulfide electrolysis desulfurization.
[0046] When used, the cysteamine-modified hydrogen sulfide electrolysis catalytic material of the present invention can utilize its catalyst / molecular layer interface to combine with the amino group of cysteamine to interact with the electrolyte, so that the present invention has better catalytic performance.
[0047] Example 1
[0048] A cysteamine-modified hydrogen sulfide electrolysis catalytic material is prepared by the following steps:
[0049] (1) preparing a 2 cm×3 cm nickel foam substrate as a substrate, and washing the substrate multiple times with deionized water, ethanol, and 3M hydrochloric acid;
[0050] (2) dissolving 0.1 g of thiourea in 40 mL of ultrapure water, stirring until fully dissolved to obtain a thiourea solution, and transferring the solution to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave;
[0051] (3) immersing the pretreated substrate in the thiourea solution, and then placing the stainless steel autoclave in an oven to react at 150° C. for 11 hours;
[0052] (4) After the stainless steel autoclave is cooled to room temperature, it is taken out, the sample is rinsed with deionized water, and placed in a drying oven at 60°C for 4 hours to obtain the in-situ grown Ni 3 S 2 Nanomaterials;
[0053] (5) Weigh 0.031 g of cysteamine and dissolve it in 4 mL of water to prepare a cysteamine solution. 3 S 2 The nanomaterial was cut into a size of 0.5 cm×1.5 cm and placed in the cysteamine solution for 1 hour. After the immersion, the nanomaterial was taken out and dried in a drying oven at 60° C. for 1 hour to obtain the cysteamine-modified hydrogen sulfide electrolysis catalytic material.
[0054] Example 2
[0055] A cysteamine-modified hydrogen sulfide electrolysis catalytic material is prepared by the following steps:
[0056] (1) preparing a 2 cm×3 cm nickel foam substrate as a substrate, and washing the substrate multiple times with deionized water, ethanol, and 3M hydrochloric acid;
[0057] (2) 0.873 g of cobalt nitrate hexahydrate, 0.9 g of urea and 0.222 g of ammonium fluoride were dissolved in 30 mL of water and transferred to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave. The pretreated substrate was also placed in the stainless steel autoclave and reacted at 150 ° C for 11 h. After cooling, the substrate was taken out and dried to obtain Co(OH) 2 Material;
[0058] (3) Take 1g of sodium hypophosphite and place it in a porcelain boat, place it upstream of the tube furnace, and mix the Co(OH) 2 The material was placed in another porcelain boat, which was placed downstream of the tube furnace. The temperature was raised at a rate of 5°C / min and maintained at 300°C for 2h, with argon flowing throughout the process.
[0059] (4) After the tube furnace is cooled to room temperature, the sample is taken out, rinsed with deionized water, and placed in a drying oven at 60° C. for 4 h to obtain in-situ grown CoP nanomaterials;
[0060] (5) Weigh 0.031 g of cysteamine and dissolve it in 4 mL of water to prepare a cysteamine solution. Cut the in situ grown CoP nanomaterial obtained in step (4) into pieces of 0.5 cm × 1.5 cm in size and soak it in the cysteamine solution for 1 hour. After soaking, take it out and dry it in a drying oven at 60° C. for 1 hour to obtain the cysteamine-modified electrolytic hydrogen sulfide catalytic material.
[0061] Example 3
[0062] A cysteamine-modified hydrogen sulfide electrolysis catalytic material is prepared by the following steps:
[0063] (1) preparing a 2 cm×3 cm nickel foam substrate as a substrate, and washing the substrate multiple times with deionized water, ethanol, and 3M hydrochloric acid;
[0064] (2) 5 mmol of nickel nitrate hexahydrate and 10 mmol of HMT were dissolved in 30 mL of water, transferred to a reactor and reacted at 100° C. for 10 h, then centrifuged at 8000 r / min for 5 min, and dried at 60° C. for 4 h to obtain nickel hydroxide powder;
[0065] (3) Dissolve 0.218 g of sodium borohydride in 5 mL of water, add 0.197 g of selenium powder, shake well, and add to the reactor. Then, mix 30 mL of ethanol and 0.0025 mol of the nickel hydroxide powder and add to the reactor, immerse the pretreated substrate in the solution, and then put the stainless steel autoclave into an oven and react at 140° C. for 12 hours;
[0066] (4) After the stainless steel autoclave is cooled to room temperature, it is taken out, the sample is rinsed with deionized water, and placed in a drying oven at 60° C. for 4 h to obtain in-situ grown NiSe nanomaterials;
[0067] (5) Weigh 0.031 g of cysteamine and dissolve it in 4 mL of water to prepare a cysteamine solution. Scrape the in situ grown NiSe nanomaterial obtained in step (4) into powder and soak it in the cysteamine solution for 1 hour. After soaking, take it out and dry it in a drying oven at 60° C. for 1 hour to obtain the cysteamine-modified electrolytic hydrogen sulfide catalytic material.
[0068] Comparative Example 1
[0069] The Ni prepared by steps (1) to (4) of Example 1 3 S 2Nanomaterials are used as catalytic materials for electrolysis of hydrogen sulfide. That is, in this comparative example, step (5) is not performed, and Ni before cysteamine modification is used. 3 S 2 Nanomaterials as catalytic materials for electrolysis of hydrogen sulfide.
[0070] Comparative Example 2
[0071] The CoP nanomaterial prepared in steps (1) to (4) of Example 2 was used as the catalytic material for electrolysis of hydrogen sulfide, that is, step (5) was not performed in this comparative example, and the CoP nanomaterial before cysteamine modification was used as the catalytic material for electrolysis of hydrogen sulfide.
[0072] Comparative Example 3
[0073] The NiSe nanomaterial prepared in steps (1) to (4) of Example 3 was used as the catalytic material for electrolysis of hydrogen sulfide. That is, step (5) was not performed in this comparative example, and the NiSe nanomaterial before cysteamine modification was used as the catalytic material for electrolysis of hydrogen sulfide.
[0074] Comparative Example 4
[0075] Different from Example 1, the step (5) of this comparative example does not use a cysteamine solution but an L-cysteine solution.
[0076] Test Example 1
[0077] The Ni before and after cysteamine modification prepared in Example 1 and Comparative Example 1 3 S 2 The nanomaterials were observed using a scanning electron microscope. Figure 1 and Figure 2 As shown. Figure 1 and Figure 2 It can be seen that the Ni modified by cysteamine of the present invention 3 S 2 The surface of nanomaterials is covered with uniform particles.
[0078] Test Example 2
[0079] The materials obtained in Examples 1-3 and Comparative Examples 1-3 were analyzed by infrared spectroscopy. The infrared spectroscopy analysis results of Example 1 and Comparative Example 1 are as follows: Figure 3 As shown. Figure 3 It can be seen that cysteamine was successfully modified to Ni 3 S 2 On nanomaterials.
[0080] Test Example 3
[0081] The SOR activity of the materials of Examples 1-3 and Comparative Examples 1-4 in the electrolysis of hydrogen sulfide in an electrolytic cell was tested. Preparation of the model electrolyte for hydrogen sulfide electrolysis: 50 mL of 1 M NaOH solution was added with 12 g of Na 2 S was stirred and dissolved as an electrolyte to prepare a model electrolyte for hydrogen production by electrolysis of hydrogen sulfide and put it into the electrolytic cell. A three-electrode system was used, with a mercury / mercuric oxide electrode as the reference electrode and a graphite rod as the counter electrode. The electrochemical parameters selected for the SOR test were -0.8V to 0V. The test conditions were: temperature 25°C, electrolyte 1mol / L NaOH + 1mol / L Na 2 S, test results such as Figure 4-7 shown.
[0082] from Figure 4 It can be seen that at the same voltage, the Ni 3 S 2 Nanomaterials are better than Ni before cysteamine modification 3 S 2 The nanomaterial has a higher current density. This is due to the cysteamine loaded on the Ni 3 S 2 The surface of the nanomaterial can form a catalyst / molecular layer interface with excellent interfacial mass transfer performance, and the amino group of cysteamine can interact with the electrolyte to further accelerate the mass transfer rate. 3 S 2 Nanomaterials exhibit better catalytic performance in the electrolysis of hydrogen sulfide.
[0083] from Figure 5 It can be seen that at the same voltage, the CoP nanomaterials modified with cysteamine also have a higher current density than the CoP nanomaterials before cysteamine modification.
[0084] from Figure 6 It can be seen that at the same voltage, the NiSe nanomaterial modified with cysteamine also has a higher current density than the NiSe nanomaterial before cysteamine modification.
[0085] from Figure 7 It can be seen that at the same voltage, L-cysteine, which also has sulfhydryl and amino groups, is used to modify Ni 3 S 2 The current density of the nanomaterials before and after modification was not much different, indicating that the modification of Ni with L-cysteine 3 S 2 Nanomaterials cannot improve Ni 3 S 2 Catalytic properties of nanomaterials.
[0086] In summary, the present invention can utilize cysteamine to improve the catalytic performance of the electrolytic hydrogen sulfide catalytic material. Compared with the prior art, the present invention has significant progress.
[0087] The above description is only a representative embodiment of the present invention and does not limit the present invention in any form. Any technician familiar with the profession, without departing from the scope of the technical solution of the present invention, uses the above-disclosed technical contents to make some changes or modifications to the embodiments are equivalent embodiments of the present invention. However, any simple modification, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.
Claims
1. A method for preparing a cysteamine-modified electrolytic hydrogen sulfide catalytic material, characterized in that: The following steps are involved: S1: preparing a cysteamine solution and obtaining a nanomaterial to be modified, wherein the nanomaterial to be modified is a catalytic material for electrolysis of hydrogen sulfide; S2: soaking the nanomaterial to be modified in the cysteamine solution until the cysteamine is modified onto the surface of the nanomaterial to be modified; S3: taking out the modified nanomaterial, and drying it to obtain the cysteamine-modified hydrogen sulfide electrolysis catalytic material.
2. The method for preparing the cysteamine-modified electrolytic hydrogen sulfide catalytic material according to claim 1, characterized in that: In step S1, when preparing the cysteamine solution, the solvent of the cysteamine solution is deionized water or ethanol, and the concentration is 1M-10 -2 M.
3. The method for preparing the cysteamine-modified electrolytic hydrogen sulfide catalytic material according to claim 1, characterized in that: In step S1, the nanomaterial to be modified has unsaturated sites, and the thiol sulfur atom of cysteamine in the cysteamine solution can form a coordination bond with the unsaturated sites through a lone pair of electrons, thereby modifying the nanomaterial to be modified with cysteamine.
4. The method for preparing the cysteamine-modified electrolytic hydrogen sulfide catalytic material according to claim 3, characterized in that: The nanomaterial to be modified is any one of Ni3S2 nanomaterial, NiSe nanomaterial and CoP nanomaterial.
5. The method for preparing the cysteamine-modified electrolytic hydrogen sulfide catalytic material according to claim 4, characterized in that: The nanomaterial to be modified is prepared by in-situ growing the nanomaterial on a substrate.
6. The method for preparing the cysteamine-modified electrolytic hydrogen sulfide catalytic material according to claim 5, characterized in that: When the nano material to be modified is a Ni3S2 nano material, the Ni3S2 nano material is prepared by the following steps: Preparing a substrate and pre-treating the substrate; preparing a thiourea solution, and immersing the pretreated substrate in the thiourea solution; The heating reaction is carried out, and after the reaction is completed, the reaction is cooled to room temperature, and the Ni3S2 nanomaterial is obtained after washing and drying.
7. The method for preparing the cysteamine-modified electrolytic hydrogen sulfide catalytic material according to claim 6, characterized in that: The substrate is any one of foamed iron, foamed nickel, foamed copper and foamed nickel-iron; when preparing the thiourea solution, the solvent used is deionized water or ethanol, the mass of the solute is 0.05g-0.15g, and the volume of the solvent is 30mL-50mL.
8. The method for preparing the cysteamine-modified electrolytic hydrogen sulfide catalytic material according to claim 6, characterized in that: When the heating reaction is carried out, the heating temperature is 140°C-160°C, and the heating time is 5h-13h; when the drying is carried out, the drying temperature is 40°C-80°C, and the drying time is 4h-6h.
9. A cysteamine-modified hydrogen sulfide electrolysis catalytic material, characterized in that: The catalyst is prepared by the method for preparing a cysteamine-modified electrolytic hydrogen sulfide catalytic material according to any one of claims 1 to 8.
10. Use of the cysteamine-modified electrolytic hydrogen sulfide catalytic material according to claim 9 in the desulfurization of electrolytic hydrogen sulfide.