High-entropy transition metal phosphide catalyst and preparation and application thereof
By using a high entropy transition metal phosphide catalyst, the problems of high overpotential and poor stability in the electrolytic oxygen evolution reaction are solved, and high OER activity and long-term stable electrocatalytic performance are achieved.
Patent Information
- Application Number
- CN202411535190.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-31
- Publication Date
- 2025-02-11
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
In the prior art, the overpotential of the electrolytic oxygen-excited reaction is high and the stability is poor, which limits the widespread use of non-precious metal catalysts in practical applications.
Using a high-entropy transition metal phosphide catalyst, the OER activity and stability of the catalyst are improved through specific composition and structural design. The catalyst consists of Co, Ni, Cu, Zn, Fe and P, with a cube particle structure and high phase purity.
Low overpotentials (204 mV) and high current density (100 mA cm-2) were achieved while exhibiting excellent stability for up to 300 hours.
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Figure CN119411162A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of electrochemical catalysis, and in particular relates to a high entropy transition metal phosphide catalyst and its preparation and application. Background Art
[0002] Among various hydrogen production technologies, electrochemical water splitting technology stands out for its cleanliness and environmental friendliness. This technology produces hydrogen by electrically driven water decomposition, making it an ideal green hydrogen production strategy due to its sustainability and mild reaction conditions. However, the rate of cathode HER is limited by the sluggish nature of OER, as the anode oxygen evolution reaction requires a large overpotential, which greatly reduces the efficiency of the entire energy conversion process. Although noble metal catalysts such as IrO2, RuO2 and Pt / C can effectively minimize the required overpotential, their limited reserves and high costs hinder their widespread use in practical applications. Therefore, there is an urgent need to develop highly active water electrolysis electrocatalysts based on non-noble metals.
[0003] In the field of non-precious metal catalysts, transition metal oxides, nitrides, phosphides and sulfides are considered to be viable alternatives to precious metal catalysts due to their abundant reserves, low cost and good catalytic activity. In addition, the introduction of different transition metal elements and the use of the synergistic effect between metals to promote the electron transfer process are effective ways to further improve the OER activity. However, compared with precious metal-based materials, their performance in electrocatalytic OER is still mediocre, which to some extent limits their widespread application in practical environments. Therefore, the further development of advanced electrocatalysts with high activity and stability based on transition metal materials is still the biggest challenge at present. Summary of the invention
[0004] In order to overcome the shortcomings of the above-mentioned prior art, the purpose of the present invention is to provide a high entropy transition metal phosphide catalyst and its preparation and application, which is used to develop a controllable preparation technology of high entropy transition metal phosphide catalyst and solve the technical problems of high overpotential and poor stability of oxygen evolution reaction in water electrolysis.
[0005] In order to achieve the above object, the present invention adopts the following technical solutions: A high entropy transition metal phosphide catalyst, the catalyst structure is orthorhombic cobalt phosphide, the space group is Pnma, a=5.077Å, b=3.281Å, c=5.587Å; the catalyst components are as follows: x(Co) is 9%~11%, x(Ni) is 9%~11%, x(Cu) is 9%~11%, x(Zn) is 9%~11%, x(Fe) is 9%~11%, x(P) is 48%~52%, and the sum of all components is 100%; the catalyst has the morphology of cubic particles with a particle size of 110~120 nm.
[0006] A method for preparing a high entropy transition metal phosphide catalyst comprises the following steps: S1: adding a surfactant and a transition metal salt into water to obtain a mixed solution A; S2: Add metallic iron salt to water to obtain a clear solution B; S3: mixing the mixed solution A and the clear solution B, stirring and standing to obtain a precipitate, washing and drying the precipitate to obtain a high entropy transition metal framework compound; S4: The high entropy transition metal framework compound is phosphated to obtain a high entropy transition metal phosphide catalyst.
[0007] Preferably, the transition metal salt in step S1 is a mixture of chlorides, nitrates or sulfates of different elements of cobalt (Co), nickel (Ni), copper (Cu) and zinc (Zn); the concentration of the transition metal salt in the aqueous solution is 0.01-0.1 mmol / mL.
[0008] Preferably, in step S1, the mass ratio of the transition metal salt to the surfactant is 1:30 to 30:1.
[0009] Preferably, the surfactant in step S1 is polyvinyl pyrrolidone or trisodium citrate.
[0010] Preferably, in step S2, the concentration of the metal iron salt in the aqueous solution is 0.01-0.1 mmol / mL.
[0011] Preferably, the standing time in step S3 is 12 to 48 hours; and the volume ratio of the mixed solution A to the clear solution B is 1:2 to 2:1.
[0012] Preferably, the reagent for phosphating the high entropy transition metal framework compound in step S4 is NaH2PO2⋅H2O, and the mass ratio of the reagent to the high entropy transition metal framework compound is 1:10 to 10:1.
[0013] Preferably, in step S4, the atmosphere for phosphating the high entropy transition metal framework compound is N2 or H2 / Ar mixed gas, and the phosphating time is 1-6 hours.
[0014] High entropy transition metal phosphide catalysts are used for electrocatalytic oxygen evolution reaction.
[0015] When the cubic nanoparticle-shaped high entropy transition metal phosphide catalyst is used for electrocatalytic oxygen evolution reaction, the high entropy transition metal phosphide catalyst exhibits high OER activity at 1.43 V. vs. At RHE potential, it reaches 100 mAcm -2The overpotential required for the current density is 204 mV, and at 1.45 V vs. High entropy transition metal phosphides exhibit 300 mA cm-2 under RHE potential. -2 The large anodic OER current density and Tafel slope are 45.4 mV dec -1 ; At a constant potential of 1.44 V vs. After 300 h of continuous OER catalysis under RHE, the initial 100 mA cm -2 The high current density can still be maintained at 91.8%.
[0016] Compared with the prior art, the present invention has the following beneficial effects: The present invention discloses an application of a high entropy transition metal phosphide in electrocatalytic oxygen evolution reaction. Since the catalyst has adjustable components and a large number of active sites, the prepared catalyst material exhibits significant OER activity. The catalyst only needs an overpotential of 204 mV to reach 100 mA cm- 2 The current density was 1.45 V and the stability was excellent for 300 hours. vs. The potential of RHE can reach 300 mA cm -2 of current density.
[0017] The present invention also discloses a preparation method of the high entropy transition metal phosphide catalyst, which selects metal cobalt salt, metal nickel salt, metal copper salt, metal zinc salt, polyvinyl pyrrolidone, trisodium citrate and potassium ferrocyanide as raw materials, and can realize the controllable preparation of binary to pentacyclic transition metal phosphide catalysts of specific composition; the method has simple process, low production cost and is suitable for industrial production.
[0018] The present invention also discloses a transition metal phosphide catalyst prepared by the method. The generated catalyst has high purity and good OER catalytic activity and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 The X-ray diffraction pattern of the five-element transition metal CoNiCuZnFe phosphide catalyst prepared in Example 1; Figure 2 This is a SEM image of the five-element transition metal CoNiCuZnFe phosphide catalyst prepared in Example 1; Figure 3 TEM image of the five-element transition metal CoNiCuZnFe phosphide catalyst prepared in Example 1; Figure 4 HRTEM image of the five-element transition metal CoNiCuZnFe phosphide catalyst prepared in Example 1; Figure 5 The linear sweep voltammetric curve of the electrocatalytic OER of the five-element transition metal CoNiCuZnFe phosphide catalyst prepared in Example 1; Figure 6 The Tafel curve of the electrocatalytic OER of the five-element transition metal CoNiCuZnFe phosphide catalyst prepared in Example 1; Figure 7 This is the stability curve of the electrocatalytic OER of the five-element transition metal CoNiCuZnFe phosphide catalyst prepared in Example 1.
[0020] Figure 8 The Gibbs free energy curves of the five-element transition metal CoNiCuZnFe phosphide catalyst and the transition metal Co phosphide catalyst prepared in Example 1.
[0021] Fig. 9 This is an LSV curve diagram of the five-membered transition metal CoNiCuZnFe phosphide catalyst prepared in Example 1 and other transition metal phosphide catalysts.
[0022] Fig.10 Tafel curves of OER of the five-membered transition metal CoNiCuZnFe phosphide catalyst prepared in Example 1 and other transition metal phosphide catalysts. DETAILED DESCRIPTION
[0023] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.
[0024] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.
[0025] In this article, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values within the range (including integers and fractions).
[0026] In this document, unless otherwise specified, “includes,” “including,” “contains,” “has,” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”
[0027] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.
[0028] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.
[0029] The following examples use conventional instruments and equipment in the art. The experimental methods in the following examples where specific conditions are not specified are usually carried out under conventional conditions or under conditions recommended by the manufacturer. The various raw materials used in the following examples are conventional commercial products unless otherwise specified, and their specifications are conventional specifications in the art. In the specification of the present invention and the following examples, unless otherwise specified, "%" means weight percentage, "part" means weight part, and ratio means weight ratio. Example
[0030] A method for preparing a five-element transition metal CoNiCuZnFe phosphide comprises the following steps: S1: Add 0.5 mmol Co(NO3)2∙6H2O (0.1455 g), 0.5 mmol Ni(NO3)2∙6H2O (0.1454 g), 0.5 mmol Cu(NO3)2∙6H2O (0.1208 g), 0.5 mmol Zn(NO3)2∙6H2O (0.1487 g) and 2.25 mmol Na3C6H5O7∙2H2O into 50 mL of water and stir to dissolve them to obtain a mixed solution A; the concentration of transition metal ions in the solution is 0.04 mmol / mL; S2: Add 2 mmol potassium ferrocyanide (K3Fe(CN)6, 0.659 g) to 50 mL of water and stir to dissolve them to obtain a clear solution B; the concentration of K3Fe(CN)6 in the solution is 0.04 mmol / mL; S3: The mixed solution A and the clarified solution B are mixed, stirred for thirty minutes, and then allowed to stand for 24 hours. The precipitate is collected by centrifugation, washed three times with water and ethanol, and vacuum dried to obtain a five-membered high entropy transition metal framework compound.
[0031] S4: The high entropy transition metal framework compound catalyst was phosphated with NaH2PO2 at a mass ratio of 1:5 under N2 atmosphere for 6 hours to further obtain a high entropy transition metal phosphide catalyst.
[0032] The electrocatalytic OER was tested using the following method.
[0033] When testing the catalytic performance of the electrode, a three-electrode system was used, with a high entropy transition metal phosphide catalyst as the working electrode, a Pt sheet as the counter electrode, and Hg / HgO (1 M KOH) as the reference electrode. A 1 M KOH saturated O2 aqueous solution was used as the electrolyte.
[0034] Electrochemical tests: All electrochemical experiments were performed using a three-electrode electrochemical workstation (CHI660E).
[0035] Figure 1 The figure shows the X-ray diffraction pattern of the catalyst prepared in Example 1. From the X-ray diffraction pattern of the product, it can be seen that the synthesized product is CoP with high phase purity, which is highly consistent with the standard card JCPDF No. 29-497 of CoP, and the structure corresponding to the product is cubic CoP.
[0036] Figure 2 The figure shows a scanning electron microscope image of the catalyst prepared in Example 1. The scanning electron microscope image shows that the catalyst is a cubic particle, and the size of the particle is about 120 nm.
[0037] Figure 5 The linear sweep voltammetric curve of the electrocatalytic OER of the catalyst prepared in Example 1 is shown. The catalyst exhibits high OER activity with an initial potential of 1.43 V. vs. RHE, up to 100 mA cm -2 The overpotential required for the current density is 204 mV, and at 1.45 V vs. Under RHE potential, the catalyst exhibited a conductivity of 300 mA cm -2 The large anodic OER current density.
[0038] Figure 6 The Tafel curve of the electrocatalytic OER of the catalyst prepared in Example 1 is shown; the Tafel slope of the catalyst nanocube is 45.4 mV dec -1 , which is beneficial to the OER catalytic reaction kinetics.
[0039] Figure 7 The stability curve of the electrocatalytic OER of the catalyst prepared in Example 1 is shown at a constant potential of 1.44 V. vs. After 300 h of continuous OER catalysis under RHE, the initial 100 mA cm -2 The high current density can still be maintained at 91.8%.
[0040] Figure 8 Curves 1 and 2 in the figure are the Gibbs free energy curves of CoP and CoNiCuZnFeP, respectively. As can be seen from the figure, the ∆G value required for the rate-determining step of curve CoNiCuZnFeP is (1.70 eV), which is significantly smaller than the ∆G value required for the rate-determining step of curve CoP (2.98 eV), which indicates that the high entropy effect accelerates the OER kinetics to a great extent.
[0041] Fig. 9 Curves 1, 2, 3, and 4 in the figure are LSV curves of CoFeP, CoNiFeP, CoNiZnFeP, and CoNiCuZnFeP, respectively. By comparison, it can be found that at a current density of 100mA cm-2, the voltage required for CoNiCuZnFeP is significantly lower than that of other materials. At the same time, it can be found that with the transition to high entropy materials, the electrocatalytic performance gradually improves, which indicates that high entropy materials have potential application value in the field of electrocatalysis.
[0042] Fig.10 Curves 1, 2, 3, and 4 in the figure are the Tafel curves of CoFeP, CoNiFeP, CoNiZnFeP, and CoNiCuZnFeP, respectively. Compared with CoNiZnFeP (58.9 mV dec-1), CoNiFeP (57.1 mV dec-1), and CoFeP (67.3 mV dec-1), the Tafel slope of CoNiZnCuFeP (45.4 mV dec-1) is the smallest, corresponding to the LSV curve, further confirming the potential of CoNiCuZnFeP, a high entropy material, as an efficient electrocatalyst. Example
[0043] According to the method of Example 1, except that the metal cobalt salt used in step (1) is cobalt chloride, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained. Example
[0044] According to the method of Example 1, except that the metal cobalt salt used in step (1) is cobalt sulfate, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained. Example
[0045] According to the method of Example 1, except that the metal nickel salt used in step (1) is nickel chloride, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained. Example
[0046] According to the method of Example 1, except that the metal nickel salt used in step (1) is nickel sulfate, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained. Example
[0047] According to the method of Example 1, except that the metal copper salt used in step (1) is copper sulfate, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained. Example
[0048] According to the method of Example 1, except that the metal copper salt used in step (1) is copper chloride, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained. Example
[0049] According to the method of Example 1, except that the metal zinc salt used in step (1) is zinc sulfate, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained. Example
[0050] According to the method of Example 1, except that the metal zinc salt used in step (1) is zinc chloride, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0051] Embodiment 10: According to the method of Example 1, except that the trisodium citrate used in step (1) is polyvinyl pyrrolidone, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0052] Embodiment 11: According to the method of Example 1, except that the trisodium citrate used in step (1) is polyvinyl pyrrolidone, the metal cobalt salt is cobalt chloride, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0053] Embodiment 12: According to the method of Example 1, except that the trisodium citrate used in step (1) is polyvinyl pyrrolidone, the metal cobalt salt is cobalt sulfate, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0054] Embodiment 13: According to the method of Example 1, except that the trisodium citrate used in step (1) is polyvinyl pyrrolidone, the metal nickel salt is nickel chloride, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0055] Embodiment 14: According to the method of Example 1, except that the trisodium citrate used in step (1) is polyvinyl pyrrolidone, the metal nickel salt is nickel sulfate, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0056] Embodiment 15: According to the method of Example 1, except that the trisodium citrate used in step (1) is polyvinyl pyrrolidone, the metal copper salt is copper chloride, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0057] Embodiment 16: According to the method of Example 1, except that the trisodium citrate used in step (1) is polyvinyl pyrrolidone, the metal copper salt is copper sulfate, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0058] Embodiment 17: According to the method of Example 1, except that the trisodium citrate used in step (1) is polyvinyl pyrrolidone, the metal zinc salt is zinc chloride, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0059] Embodiment 18: According to the method of Example 1, except that the trisodium citrate used in step (1) is polyvinyl pyrrolidone, the metal zinc salt is zinc sulfate, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0060] Embodiment 19: According to the method of Example 1, except that the concentration of the metal cobalt salt in step (1) is 0.1 mmol / mL, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0061] Embodiment 20: According to the method of Example 1, except that the concentration of the metal cobalt salt in step (1) is 0.05 mmol / mL, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0062] Embodiment 21: According to the method of Example 1, except that the concentration of the metal cobalt salt in step (1) is 0.01 mmol / mL, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0063] Embodiment 22: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt sulfate, the concentration of the cobalt salt is 0.1 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0064] Embodiment 23: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt sulfate, the concentration of the cobalt salt is 0.05 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0065] Embodiment 24: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt sulfate, the concentration of the cobalt salt is 0.01 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0066] Embodiment 25: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt chloride, the concentration of the cobalt salt is 0.1 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0067] Embodiment 26: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt chloride, the concentration of the cobalt salt is 0.05 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0068] Embodiment 27: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt chloride, the concentration of the cobalt salt is 0.01 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0069] Embodiment 28: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel chloride, the concentration of the nickel salt is 0.1 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0070] Embodiment 29: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel chloride, the concentration of the nickel salt is 0.05 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0071] Embodiment 30: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel chloride, the concentration of the nickel salt is 0.01 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0072] Embodiment 31: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel sulfate, the concentration of the nickel salt is 0.1 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0073] Embodiment 32: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel sulfate, the concentration of the nickel salt is 0.05 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0074] Embodiment 33: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel sulfate, the concentration of the nickel salt is 0.01 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0075] Embodiment 34: According to the method of Example 1, except that the metal copper salt in step (1) is copper chloride, the concentration of the copper salt is 0.1 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0076] Embodiment 35: According to the method of Example 1, except that the metal copper salt in step (1) is copper chloride, the concentration of the copper salt is 0.05 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0077] Embodiment 36: According to the method of Example 1, except that the metal copper salt in step (1) is copper chloride, the concentration of the copper salt is 0.01 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0078] Embodiment 37: According to the method of Example 1, except that the metal copper salt in step (1) is copper sulfate, the concentration of the copper salt is 0.1 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0079] Embodiment 38: According to the method of Example 1, except that the metal copper salt in step (1) is copper sulfate, the concentration of the copper salt is 0.05 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0080] Embodiment 39: According to the method of Example 1, except that the metal copper salt in step (1) is copper sulfate, the concentration of the copper salt is 0.01 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0081] Embodiment 40: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc chloride, the concentration of the zinc salt is 0.1 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0082] Embodiment 41: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc chloride, the concentration of the zinc salt is 0.05 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0083] Embodiment 42: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc chloride, the concentration of the zinc salt is 0.01 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0084] Embodiment 43: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc sulfate, the concentration of the zinc salt is 0.1 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0085] Embodiment 44: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc sulfate, the concentration of the zinc salt is 0.05 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0086] Embodiment 45: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc sulfate, the concentration of the zinc salt is 0.01 mmol / mL, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0087] Embodiment 46: According to the method of Example 1, except that the mass ratio of the metal salt to trisodium citrate in step (1) is 0.033, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0088] Embodiment 47: According to the method of Example 1, except that the mass ratio of the metal salt to trisodium citrate in step (1) is 1, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0089] Embodiment 48: According to the method of Example 1, except that the mass ratio of the metal salt to trisodium citrate in step (1) is 5, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0090] Embodiment 49: According to the method of Example 1, except that the mass ratio of the metal salt to trisodium citrate in step (1) is 10, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0091] Embodiment 50: According to the method of Example 1, except that the mass ratio of the metal salt to trisodium citrate in step (1) is 20, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0092] Embodiment 51: According to the method of Example 1, except that the mass ratio of the metal salt to trisodium citrate in step (1) is 30, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0093] Embodiment 52: According to the method of Example 1, except that the mass ratio of metal salt to polyvinyl pyrrolidone in step (1) is 0.033, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0094] Embodiment 53: According to the method of Example 1, except that the mass ratio of the metal salt to polyvinyl pyrrolidone in step (1) is 1, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0095] Embodiment 54: According to the method of Example 1, except that the mass ratio of metal salt to polyvinyl pyrrolidone in step (1) is 5, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0096] Embodiment 55: According to the method of Example 1, except that the mass ratio of metal salt to polyvinyl pyrrolidone in step (1) is 10, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0097] Embodiment 56: According to the method of Example 1, except that the mass ratio of metal salt to polyvinyl pyrrolidone in step (1) is 20, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0098] Embodiment 57: According to the method of Example 1, except that the mass ratio of metal salt to polyvinyl pyrrolidone in step (1) is 30, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0099] Embodiment 58: According to the method of Example 1, except that the concentration of the metal iron salt in step (2) is 0.01 mmol / mL, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0100] Embodiment 59: According to the method of Example 1, except that the concentration of the metal iron salt in step (2) is 0.02 mmol / mL, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0101] Embodiment 60: According to the method of Example 1, except that the concentration of the metal iron salt in step (2) is 0.03 mmol / mL, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0102] Example 61: According to the method of Example 1, except that the concentration of the metal iron salt in step (2) is 0.04 mmol / mL, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0103] Embodiment 62: According to the method of Example 1, except that the concentration of the metal iron salt in step (2) is 0.05 mmol / mL, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0104] Embodiment 63: According to the method of Example 1, except that the concentration of the metal iron salt in step (2) is 0.1 mmol / mL, and the rest is the same as Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0105] Embodiment 64: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt chloride, the concentration of the metal iron salt in step (2) is 0.01 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0106] Embodiment 65: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt chloride, the concentration of the metal iron salt in step (2) is 0.02 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0107] Embodiment 66: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt chloride, the concentration of the metal iron salt in step (2) is 0.03 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0108] Embodiment 67: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt chloride, the concentration of the metal iron salt in step (2) is 0.04 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0109] Embodiment 68: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt chloride, the concentration of the metal iron salt in step (2) is 0.05 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0110] Embodiment 69: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt chloride, the concentration of the metal iron salt in step (2) is 0.1 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0111] Embodiment 70: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt sulfate, the concentration of the metal iron salt in step (2) is 0.01 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0112] Embodiment 71: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt sulfate, the concentration of the metal iron salt in step (2) is 0.02 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0113] Embodiment 72: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt sulfate, the concentration of the metal iron salt in step (2) is 0.03 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0114] Embodiment 73: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt sulfate, the concentration of the metal iron salt in step (2) is 0.04 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0115] Embodiment 74: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt sulfate, the concentration of the metal iron salt in step (2) is 0.05 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0116] Embodiment 75: According to the method of Example 1, except that the metal cobalt salt in step (1) is cobalt sulfate, and the concentration of the metal iron salt in step (2) is 0.1 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0117] Embodiment 76: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel sulfate, the concentration of the metal iron salt in step (2) is 0.01 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0118] Embodiment 77: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel sulfate, the concentration of the metal iron salt in step (2) is 0.02 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0119] Embodiment 78: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel sulfate, the concentration of the metal iron salt in step (2) is 0.03 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0120] Embodiment 79: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel sulfate, the concentration of the metal iron salt in step (2) is 0.04 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0121] Embodiment 80: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel sulfate, the concentration of the metal iron salt in step (2) is 0.05 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0122] Embodiment 81: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel sulfate, the concentration of the metal iron salt in step (2) is 0.1 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0123] Embodiment 82: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel chloride, the concentration of the metal iron salt in step (2) is 0.01 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0124] Embodiment 83: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel chloride, the concentration of the metal iron salt in step (2) is 0.02 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0125] Embodiment 84: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel chloride, the concentration of the metal iron salt in step (2) is 0.03 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0126] Embodiment 85: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel chloride, the concentration of the metal iron salt in step (2) is 0.04 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0127] Embodiment 86: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel chloride, the concentration of the metal iron salt in step (2) is 0.05 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0128] Embodiment 87: According to the method of Example 1, except that the metal nickel salt in step (1) is nickel chloride, the concentration of the metal iron salt in step (2) is 0.1 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0129] Embodiment 88: According to the method of Example 1, except that the metal copper salt in step (1) is copper chloride, the concentration of the metal iron salt in step (2) is 0.01 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0130] Embodiment 89: According to the method of Example 1, except that the metal copper salt in step (1) is copper chloride, the concentration of the metal iron salt in step (2) is 0.02 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0131] Embodiment 90: According to the method of Example 1, except that the metal copper salt in step (1) is copper chloride, the concentration of the metal iron salt in step (2) is 0.03 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0132] Embodiment 91: According to the method of Example 1, except that the metal copper salt in step (1) is copper chloride, the concentration of the metal iron salt in step (2) is 0.04 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0133] Embodiment 92: According to the method of Example 1, except that the metal copper salt in step (1) is copper chloride, the concentration of the metal iron salt in step (2) is 0.05 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0134] Embodiment 93: According to the method of Example 1, except that the metal copper salt in step (1) is copper chloride, the concentration of the metal iron salt in step (2) is 0.1 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0135] Embodiment 94: According to the method of Example 1, except that the metal copper salt in step (1) is copper sulfate, the concentration of the metal iron salt in step (2) is 0.01 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0136] Embodiment 95: According to the method of Example 1, except that the metal copper salt in step (1) is copper sulfate, the concentration of the metal iron salt in step (2) is 0.02 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0137] Embodiment 96: According to the method of Example 1, except that the metal copper salt in step (1) is copper sulfate, the concentration of the metal iron salt in step (2) is 0.03 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0138] Embodiment 97: According to the method of Example 1, except that the metal copper salt in step (1) is copper sulfate, the concentration of the metal iron salt in step (2) is 0.04 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0139] Embodiment 98: According to the method of Example 1, except that the metal copper salt in step (1) is copper sulfate, the concentration of the metal iron salt in step (2) is 0.05 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0140] Embodiment 99: According to the method of Example 1, except that the metal copper salt in step (1) is copper sulfate, the concentration of the metal iron salt in step (2) is 0.1 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0141] Embodiment 100: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc sulfate, the concentration of the metal iron salt in step (2) is 0.01 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0142] Embodiment 101: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc sulfate, the concentration of the metal iron salt in step (2) is 0.02 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0143] Embodiment 102: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc sulfate, the concentration of the metal iron salt in step (2) is 0.03 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0144] Embodiment 103: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc sulfate, the concentration of the metal iron salt in step (2) is 0.04 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0145] Embodiment 104: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc sulfate, the concentration of the metal iron salt in step (2) is 0.05 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0146] Embodiment 105: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc sulfate, the concentration of the metal iron salt in step (2) is 0.1 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0147] Embodiment 106: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc chloride, the concentration of the metal iron salt in step (2) is 0.01 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0148] Embodiment 107: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc chloride, the concentration of the metal iron salt in step (2) is 0.02 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0149] Embodiment 108: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc chloride, the concentration of the metal iron salt in step (2) is 0.03 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0150] Embodiment 109: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc chloride, the concentration of the metal iron salt in step (2) is 0.04 mmol / mL, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0151] Embodiment 110: According to the method of Example 1, except that the metal zinc salt in step (1) is zinc chloride, the standing time in step (3) is 48 h, and the rest is the same as in Example 1, a high entropy transition metal phosphide catalyst is obtained.
[0152] Embodiment 111: The method of Example 1 is followed, except that in step (4), the mass ratio of NaH2PO2⋅H2O to the high entropy transition metal framework compound is 1:1, and the rest is the same as Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0153] Embodiment 112: The method of Example 1 is followed, except that in step (4), the mass ratio of NaH2PO2⋅H2O to the high entropy transition metal framework compound is 1:10, and the rest is the same as in Example 1, to obtain a high entropy transition metal phosphide catalyst.
[0154] Embodiment 113: The method of Example 1 is followed, except that the atmosphere for phosphating the high entropy transition metal framework compound in step (4) is a H2 / Ar mixed gas.
[0155] Embodiment 114: The method of Example 1 is followed, except that the metal cobalt salt in step (1) is cobalt sulfate, and the atmosphere for phosphating the high entropy transition metal framework compound in step (4) is a H2 / Ar mixed gas.
[0156] Embodiment 115: The method of Example 1 is followed, except that in step (4), the time for phosphating the high entropy transition metal framework compound is 1 hour.
[0157] Embodiment 116: The method of Example 1 is followed, except that in step (4), the time for phosphating the high entropy transition metal framework compound is 4 hours.
[0158] Embodiment 117: The method of Example 1 is followed, except that the metal cobalt salt in step (1) is cobalt sulfate, and the time for phosphating the high entropy transition metal framework compound in step (4) is 2 hours.
[0159] The above contents are only for explaining the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.
Claims
1. A high entropy transition metal phosphide catalyst, characterized in that The catalyst structure is orthorhombic cobalt phosphide, the space group is Pnma, a=5.077Å, b=3.281Å, c=5.587Å; the catalyst components are as follows: x(Co) is 9%~11%, x(Ni) is 9%~11%, x(Cu) is 9%~11%, x(Zn) is 9%~11%, x(Fe) is 9%~11%, x(P) is 48%~52%, and the sum of all components is 100%; the morphology of the catalyst is cubic particles, and the particle size is 110~120 nm.
2. A method for preparing a high entropy transition metal phosphide catalyst according to claim 1, characterized in that: The following steps are involved: S1: adding a surfactant and a transition metal salt into water to obtain a mixed solution A; S2: Add metallic iron salt to water to obtain a clear solution B; S3: mixing the mixed solution A and the clear solution B, stirring and standing to obtain a precipitate, washing and drying the precipitate to obtain a high entropy transition metal framework compound; S4: Phosphating the high entropy transition metal framework compound to obtain a high entropy transition metal phosphide catalyst.
3. The method according to claim 2, characterized in that The transition metal salt in step S1 is a mixture of chlorides, nitrates or sulfates of different elements of cobalt (Co), nickel (Ni), copper (Cu) and zinc (Zn); the concentration of the transition metal salt in the aqueous solution is 0.01-0.1 mmol / mL.
4. The method according to claim 2, characterized in that: The mass ratio of the transition metal salt to the surfactant in step S1 is 1:30 to 30:
1.
5. The method according to claim 2, characterized in that: The surfactant in step S1 is polyvinyl pyrrolidone or trisodium citrate.
6. The method according to claim 2, characterized in that The concentration of the metal iron salt in the aqueous solution in step S2 is 0.01-0.1 mmol / mL.
7. The method according to claim 2, characterized in that The standing time in step S3 is 12 to 48 hours; the volume ratio of the mixed solution A to the clear solution B is 1:2 to 2:
1.
8. The method according to claim 2, characterized in that: The reagent for phosphating the high entropy transition metal framework compound in step S4 is NaH2PO2⋅H2O, and the mass ratio of the reagent to the high entropy transition metal framework compound is 1:10~10:
1.
9. The method according to claim 2, characterized in that: The atmosphere for phosphating the high entropy transition metal framework compound in step S4 is N2 or H2 / Ar mixed gas, and the phosphating time is 1 to 6 hours.
10. The use of a high entropy transition metal phosphide catalyst according to claim 1, characterized in that: The high entropy transition metal phosphide catalyst is used for electrocatalytic oxygen evolution reaction.