Method for preparing catalyst by preparing layered porous metal oxide to adsorb hydrogen phosphide
By preparing a layered porous metal oxide for phosphine adsorption, the problem of synthesizing Co3O4 and NiO materials was solved, achieving efficient phosphine adsorption and electrocatalytic water splitting, thus promoting the development of green energy.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- YUNNAN MINZU UNIV
- Filing Date
- 2026-01-22
- Publication Date
- 2026-05-05
AI Technical Summary
Existing technologies make it difficult to synthesize layered porous Co3O4 and NiO materials using simple and low-cost methods. Furthermore, the treatment and conversion of phosphine gas pose safety and environmental threats in industrial emissions. Meanwhile, traditional precious metal catalysts limit the efficiency and cost of electrocatalytic water splitting.
By preparing layered porous metal oxides to adsorb phosphine, Nix1Py1 or Cox2Py2 electrocatalysts are prepared by reacting nickel or cobalt source precursors with phosphine. The micro- and nanoporous structures are used to increase the specific surface area and active sites, simplify the process, and reduce costs.
It achieves efficient adsorption of phosphine, reduces the risk of industrial exhaust emissions, and provides a cheap and efficient electrocatalyst for electrocatalytic water splitting to produce hydrogen, promoting the production of green energy.
Smart Images
Figure CN121972191A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of electrocatalytic materials engineering technology, specifically to a method for preparing a catalyst by adsorbing phosphine using a layered porous metal oxide. Background Technology
[0002] Gas sensors have wide applications in environmental quality monitoring, industrial production, and indoor gas detection, playing an increasingly important role in both production activities and daily life. Among them, metal oxide gas sensors have advantages such as fast response speed, low cost, high sensitivity, and long service life. Currently, most research on improving the gas-sensing performance of metal oxide materials mainly focuses on three aspects: nanostructures, layered porous structures, and noble metal surface modification. These three measures can increase the surface area of the material, thereby providing more gas channels and improving the material utilization rate. In addition, layered porous structures can provide more surface active sites, allowing the material to directly contact the target gas, which not only increases physical and chemical adsorption but also significantly shortens the response and recovery time. Among many semiconductor metal oxides, Co3O4 and NiO have become important gas-sensing materials due to their high sensitivity, low cost, and high strength. To date, many porous structures of these two metal oxides have been synthesized; however, there are few reports on synthesizing their layered porous structures using a simple and universal method.
[0003] Phosphine is a flammable, explosive, and highly toxic gas. If released into the atmosphere without treatment, it will seriously threaten human health and the ecological environment, and will also indirectly contribute to the greenhouse effect. The exhaust gas emitted by the phosphorus chemical industry is one of the main sources of phosphine in the atmosphere. The concentration of phosphine in the exhaust gas emitted by yellow phosphorus production plants is about 1000 ppm. Therefore, in order to protect human health and the environment, PH3 in the exhaust gas must be effectively treated.
[0004] The efficient production of high-purity hydrogen is of great significance in energy technology; for example, the economical production of hydrogen fuel could make carbon dioxide-free aviation possible, provided that hydrogen is produced using carbon-free technologies. Compared to methane reforming and coal gasification, electrocatalytic water splitting offers an environmentally friendly method for hydrogen production; it can also effectively convert and store intermittent renewable energy sources such as wind and solar power. Water electrolysis consists of two main half-reactions, particularly the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), requiring highly efficient and stable catalysts to lower the activation energy and thus accelerate the kinetics. Traditionally, precious metal catalysts have been used because… The industrial electrocatalytic water splitting process is severely limited by the low availability and high cost of these catalysts. Therefore, it is crucial to develop inexpensive and efficient non-precious metal catalysts for these reactions. Transition metal phosphide electrocatalytic materials have proven to be ideal alternatives to scarce precious metals such as platinum and platinum-based catalysts for hydrogen production through electrocatalytic water splitting due to their excellent conductivity, abundant active sites, and low cost. Currently, the preparation of metal phosphides is mainly achieved through phosphine gas generated by heating phosphorus-containing chemicals such as sodium hypophosphite and red phosphorus at a certain temperature. This preparation process is relatively complex and costly.
[0005] Therefore, providing a method for preparing a catalyst by adsorbing phosphine using layered porous metal oxides to avoid secondary pollution and achieve efficient PH3 adsorption is a technical problem that urgently needs to be solved in this field. Summary of the Invention
[0006] The purpose of this invention is to propose a method for preparing a catalyst by adsorbing phosphine using a layered porous metal oxide. This invention produces a layered porous metal oxide material that achieves efficient removal of phosphine from exhaust gas while simultaneously synthesizing an electrocatalyst that is beneficial for the generation of green energy.
[0007] To achieve the above objectives, the present invention adopts the following technical solution:
[0008] A method for preparing an electrocatalyst by adsorbing phosphine using a layered porous metal oxide comprises the following steps:
[0009] S1: Prepare a nickel source precursor or a cobalt source precursor by using a nickel source or a cobalt source;
[0010] S2: The nickel or cobalt source precursor is placed in a quartz tube, placed in a tube furnace, and phosphine is introduced to prepare a product containing Ni. x1 P y1 or Co x2 P y2 Electrocatalyst.
[0011] Preferably, X1=2 or 5, y1=1 or 4, X2=1 or 2, and y2=1.
[0012] Preferably, the method for preparing the cobalt source precursor includes the following steps:
[0013] S1.1: Co(CH3CO2)2·4H2O was added to H2NCONH2 solution and stirred to obtain a purple solution;
[0014] S1.2: The purple solution is subjected to hydrothermal treatment, followed by washing and drying to obtain purple powder;
[0015] S1.3: The purple powder is calcined and sieved to obtain a cobalt source precursor.
[0016] Preferably, the method for preparing the nickel source precursor includes the following steps:
[0017] S1.4: Dissolve Ni(CH3CO2)2·4H2O and HOCH2CH2NH2 in H2O to obtain a green solution;
[0018] S1.5: The green solution is subjected to hydrothermal treatment, followed by washing and drying to obtain green powder;
[0019] S1.6: The green powder is roasted, crushed, and sieved to obtain a nickel source precursor.
[0020] Preferably, the concentration of Co(CH3CO2)2·4H2O is 0.4 mol / L. -1 The concentration of H2NCONH2 is 0.8 mol / L. -1 The mass ratio of Co(CH3CO2)2·4H2O to H2NCONH2 is 1:2; the stirring time is 30-60 minutes; the hydrothermal conditions are: hydrothermal at 100℃ for 10-15 hours; washing with deionized water; the drying conditions are: temperature 60℃-80℃ for 5-12 hours; the calcination conditions are: temperature 400℃-500℃ for 80-120 minutes; and sieving is performed using a 40-60 mesh sieve.
[0021] Preferably, in step S2, the concentration of phosphine is 1000 ppm to 1050 ppm; the phosphating temperature is 300 to 340°C; the phosphine flow rate is 100 mL / min; and the phosphating time is 300 min to 360 min, to obtain a product containing Co. x2 P y2 Electrocatalyst.
[0022] Preferably, the concentration of Ni(CH3CO2)2·4H2O is 0.4 mol / L. -1The mass ratio of Ni(CH3CO2)2·4H2O to H2NCONH2 and H2O is 5:5:17; the stirring time is 30-60 minutes; the hydrothermal conditions are: hydrothermal at 120℃ for 24-64 hours; washing with deionized water; the drying conditions are: temperature 60℃-80℃ for 5-12 hours; the calcination conditions are: temperature 400℃-500℃ for 80-120 minutes; and sieving is performed using a 40-60 mesh sieve.
[0023] Preferably, in step S2, the concentration of phosphine is 1000 ppm to 1050 ppm; the phosphating temperature is 340 to 380°C; the phosphine flow rate is 100 mL / min; and the phosphating time is 300 min to 360 min, to obtain a product containing Ni. x1 P y1 Electrocatalyst.
[0024] Compared with the prior art, the present invention has the following beneficial effects:
[0025] This invention proposes a method for preparing a catalyst by adsorbing phosphine using a layered porous metal oxide. This method employs a simple and universal approach to fabricate layered porous metal oxide materials. The layered porous structure, with its micro- and nano-scale channels including micropores, mesopores, and macropores, significantly increases the specific surface area of the material, providing more interfaces for catalytic reactions. The pore structure also facilitates contact between the active sites of the metal phosphide, such as phosphorus atoms, metal atoms, or defect sites, and the electrolyte, improving atom utilization. The catalyst obtained by reacting the layered porous metal oxide material with phosphine contains Ni. x1 P y1 or Co x2 P y2 The electrocatalytic material has low preparation cost, short preparation time, and simple process, which effectively solves the problem of yellow phosphorus tail gas emission and promotes the production of green energy; moreover, the electrocatalyst has good application prospects in the field of electrocatalytic water splitting to produce hydrogen. Attached Figure Description
[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. The drawings in this description are merely embodiments of the present invention.
[0027] Figure 1 The images show SEM images of layered porous metal oxides, with NiO on the left and Co3O4 on the right.
[0028] Figure 2The graphs show the adsorption performance of the layered porous metal oxides prepared in Examples 1 and 2 on phosphine at different temperatures. The left graph shows the adsorption performance of NiO on phosphine at different temperatures, and the right graph shows the adsorption performance of Co3O4 on phosphine at different temperatures.
[0029] Figure 3 The images show the electrochemical performance of the layered porous metal oxides after phosphating in Examples 1 and 2. The left image shows the electrochemical performance of NiO after phosphating, and the right image shows the electrochemical performance of Co3O4 after phosphating. Detailed Implementation
[0030] Embodiments of the present invention are described below, examples of which are shown in the accompanying drawings. The embodiments described with reference to the drawings are exemplary and intended to explain the present invention, but are not to be construed as limiting the present invention.
[0031] Example 1
[0032] Preparation method of cobalt source precursor (layered porous cobalt oxide):
[0033] Add 25 mL of 0.4 mol / L -1 Co(CH3CO2)2·4H2O was added to 50 mL of 0.8 mol / L solution. -1 Stirring the H2NCONH2 solution for 30 minutes yields a purple solution.
[0034] The purple solution was hydrothermally heated at a constant temperature of 100℃ for 10 hours, then washed with deionized water and dried at 60℃ for 5 to 12 hours to obtain purple powder.
[0035] The purple powder was placed in a tube furnace and calcined at 400℃ for 80 minutes. After crushing and sieving, a precursor Co3O4 with a mesh size of 40-60 was obtained.
[0036] 0.05 g of the precursor obtained in Example 1 was placed in a quartz tube. The phosphating temperature of the precursor Co3O4 was controlled at 300~340℃ using a tube furnace. Phosphine at a concentration of 1000 ppm was introduced into the quartz tube at a flow rate of 100 mL / min. After phosphating for 600 min, CoP electrocatalytic material was prepared. The phosphated material in Example 1 was subjected to electrochemical testing.
[0037] Example 2
[0038] Preparation method of nickel source precursor (layered porous nickel oxide):
[0039] 10 mL of 0.4 mol / L -1 Ni(CH3CO2)2·4H2O and 10 mL of HOCH2CH2NH2 were dissolved in 34 mL of H2O to obtain a green solution;
[0040] The green solution was hydrothermally heated at a constant temperature of 120°C for 64 hours, then washed with deionized water and dried to obtain green powder.
[0041] The green powder was calcined at 400℃ for 80 minutes, crushed, and sieved to obtain a 40-60 mesh precursor NiO.
[0042] 0.05 g of the precursor obtained in Example 1 was placed in a quartz tube. The phosphating temperature of the precursor NiO was controlled at 340~380℃ by a tube furnace. Phosphine with a concentration of 1000 ppm was introduced into the quartz tube at a flow rate of 100 mL / min. After phosphating for 600 min, Ni2P electrocatalytic material was prepared. The phosphated material in Example 2 was subjected to electrochemical testing.
[0043] Based on the above embodiments and Figure 1-3 It is known that the Ni2P and CoP-containing electrocatalytic materials provided by this invention have a relatively short preparation time, the raw materials are inexpensive and readily available, are not limited by time and location, and do not produce side reactions; they have good application prospects in fields such as photoelectrocatalytic water splitting to produce hydrogen and photocatalytic degradation of organic pollutants.
[0044] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for preparing an electrocatalyst by adsorbing phosphine using a layered porous metal oxide, characterized in that, Includes the following steps: S1: Prepare a nickel source precursor or a cobalt source precursor by using a nickel source or a cobalt source; S2: The nickel or cobalt source precursor is placed in a quartz tube, placed in a tube furnace, and phosphine is introduced to prepare a product containing Ni. x1 P y1 or Co x2 P y2 Electrocatalyst.
2. The method for preparing an electrocatalyst by adsorbing phosphine using a layered porous metal oxide according to claim 1, characterized in that, X1=2 or 5, y1=1 or 4, X2=1 or 2, y2=1.
3. The method for preparing an electrocatalyst by adsorbing phosphine using a layered porous metal oxide according to claim 2, characterized in that, The method for preparing the cobalt source precursor includes the following steps: S1.1: Co(CH3CO2)2·4H2O was added to H2NCONH2 solution and stirred to obtain a purple solution; S1.2: The purple solution is subjected to hydrothermal treatment, followed by washing and drying to obtain purple powder; S1.3: The purple powder is roasted, crushed, and sieved to obtain a cobalt source precursor.
4. The method for preparing an electrocatalyst by adsorbing phosphine using a layered porous metal oxide according to claim 2, characterized in that, The method for preparing the nickel source precursor includes the following steps: S1.4: Dissolve Ni(CH3CO2)2·4H2O and HOCH2CH2NH2 in H2O to obtain a green solution; S1.5: The green solution is subjected to hydrothermal treatment, followed by washing and drying to obtain green powder; S1.6: The green powder is roasted, crushed, and sieved to obtain a nickel source precursor.
5. The method for preparing an electrocatalyst by adsorbing phosphine using a layered porous metal oxide according to claim 3, characterized in that, The concentration of Co(CH3CO2)2·4H2O is 0.4 mol / L. -1 The concentration of H2NCONH2 is 0.8 mol / L. -1 The mass ratio of Co(CH3CO2)2·4H2O to H2NCONH2 is 1:2; the stirring time is 30-60 minutes; the hydrothermal conditions are: hydrothermal at 100℃ for 10-15 hours; washing with deionized water; the drying conditions are: temperature 60℃-80℃ for 5-12 hours; the calcination conditions are: temperature 400℃-500℃ for 80-120 minutes; and sieving is performed using a 40-60 mesh sieve.
6. The method for preparing an electrocatalyst by adsorbing phosphine using a layered porous metal oxide according to claim 3, characterized in that, In step S2, the concentration of phosphine is 1000 ppm to 1050 ppm; the phosphating temperature is 300 to 340°C; the phosphine flow rate is 100 mL / min; and the phosphating time is 300 to 360 min, yielding a product containing Co. x2 P y2 Electrocatalyst.
7. The method for preparing an electrocatalyst by adsorbing phosphine using a layered porous metal oxide according to claim 4, characterized in that, The concentration of Ni(CH3CO2)2·4H2O is 0.4 mol / L. -1 The mass ratio of Ni(CH3CO2)2·4H2O to H2NCONH2 and H2O is 5:5:17; the stirring time is 30-60 minutes; the hydrothermal conditions are: hydrothermal at 120℃ for 24-64 hours; washing with deionized water; the drying conditions are: temperature 60℃-80℃ for 5-12 hours; the calcination conditions are: temperature 400℃-500℃ for 80-120 minutes; and sieving is performed using a 40-60 mesh sieve.
8. The method for preparing an electrocatalyst by adsorbing phosphine using a layered porous metal oxide according to claim 7, characterized in that, In step S2, the concentration of phosphine is 1000 ppm to 1050 ppm; the phosphating temperature is 340 to 380 °C; the phosphine flow rate is 100 mL / min; and the phosphating time is 300 min to 360 min, yielding a product containing Ni. x1 P y1 Electrocatalyst.