Preparation and performance research of Pt cluster doped multi-metal nickel-based phosphide
By introducing Pt clusters on a multi-metal phosphide substrate, the problems of low atomic utilization and high cost of traditional Pt-based catalysts are solved, and efficient electrocatalytic water splitting performance is achieved, showing excellent HER and OER activity and long-term stability.
Patent Information
- Application Number
- CN202510961877.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-14
- Publication Date
- 2025-09-23
AI Technical Summary
The low atomic utilization rate and high cost of traditional Pt-based catalysts restrict their large-scale application. Precious metal clusters are prone to migration and aggregation during the electrolysis process, resulting in the loss of active sites.
Pt clusters are introduced on a multi-metal phosphide substrate by photodeposition to form multi-level composite particles. The cluster size and distribution are adjusted to achieve efficient anchoring of precious metals. The electronic synergistic effect between the clusters and the phosphide substrate is combined to optimize the charge transfer dynamics.
The catalytic performance was significantly improved, with the HER and OER overpotentials reduced to 19mV and 242mV, respectively. The long-term operation stability was good, and the water electrolysis voltage at the current density was lower than that of commercial Pt/C, showing excellent catalytic activity and stability.
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Abstract
Description
Technical Field
[0001] The present invention relates to the field of electrocatalytic water splitting, and in particular to the preparation of a Pt cluster-doped multi-metal nickel-based phosphide. Background Art
[0002] As one of the core technologies for achieving the "dual carbon" goals, hydrogen production through water electrolysis relies heavily on the development of high-performance catalytic materials for both catalytic efficiency and cost control. While traditional Pt-based catalysts possess excellent electrocatalytic activity, their low atomic utilization and high cost severely restrict their large-scale application. The construction of precious metal clusters can effectively improve precious metal utilization, breaking through the performance bottleneck of single materials.
[0003] Clusters are microscopic aggregates of several to thousands of metal atoms formed through chemical bonds or physical interactions, occupying a transitional state between single atoms and nanoparticles. Each metal atom in a cluster participates in the catalytic reaction, increasing atomic utilization to nearly 100% compared to traditional nanoparticles. Low-coordinate atoms at the edges and corners of clusters have stronger adsorption capacity, accelerating water dissociation (Volmer step) and H2 desorption (Tafel step). Clusters, due to their discontinuous electronic energy levels and ultra-high surface area, fully expose active sites. However, their ultra-small size leads to high surface activity, making them susceptible to migration and aggregation during electrolysis. This is especially true at high temperatures or high current densities, where they form large particles through the Ostwald ripening mechanism, leading to loss of active sites. The metal-like conductivity and three-dimensional hierarchical pore structure of the phosphide substrate reduce interfacial resistance and promote rapid electron transfer to the cluster. In catalysis, the high activity of metal clusters is often accompanied by decreased stability, and excessive pursuit of stability can compromise activity. Therefore, we further introduced precious metal clusters and activated the transition metal substrate with a small amount of Pt, maintaining high catalytic activity while significantly reducing costs. Based on this, we prepared two Pt cluster-doped multimetal phosphide catalysts. Summary of the Invention
[0004] To overcome the low atomic utilization and high cost constraints of traditional Pt-based catalysts, which hinder their large-scale application, and achieve deep synergy between "multi-metal active sites" and "carrier electronic regulation," this invention provides a preparation method and performance study of Pt cluster-doped multi-metal nickel-based phosphides.
[0005] The preparation of a Pt cluster-doped multimetal nickel-based phosphide comprises the following steps:
[0006] 1. Weigh nickel hexahydrate molybdenum polyoxide (0.10 g, 0.070 mmol) and cobalt nitrate (0.043 g, 0.18 mmol) in 10 mL of deionized water and place a 1*1.5 cm 2Foamed iron (IF) was stirred at room temperature for 30 min. The sample was placed in a 180°C forced air drying oven for 18 h, cooled to room temperature, washed three times with ethanol and deionized water, and then dried at 60°C for 12 h to obtain the product Mo4O 11 / NiCoFe-LDH@IF.
[0007] 2. The material obtained in step 1 was placed downstream and sodium hypophosphite was placed upstream, and placed in a tube furnace. The mixture was heated to 450°C at 5°C / min, maintained for 2 hours, and cooled to room temperature at the same rate. The mixture was washed and dried in the same manner to obtain the products CoP2 / Fe2P / MoNiP@IF.
[0008] 3. The electrode material obtained in step 2 was immersed in a solution containing 10 mL of chloroplatinic acid and illuminated for 30 minutes. It was also washed and dried to obtain the product CoPt3-CoP2 / Fe2P / MoNiP@IF.
[0009] The application of the above-mentioned Pt cluster-doped multi-metal nickel-based phosphide electrode material is mainly in the electrocatalytic complete water splitting aspect.
[0010] The above application method is as follows: the test was carried out in 1.0M KOH and alkaline seawater, using a three-electrode system with a saturated calomel electrode as the reference electrode, a carbon rod as the counter electrode, and a modified iron foam as the working electrode. -2 At the current density, the HER overpotential of CoPt3-CoP2 / Fe2P / MoNiP@IF is 19mV, the OER overpotential is 242mV, and it can remain stable for up to 48 hours.
[0011] Compared with the prior art, the present invention has the following characteristics:
[0012] By effectively regulating the size and distribution of clusters through photodeposition, the Pt-Mo clusters were uniformly anchored on the phosphide substrate, and a catalyst with a multi-level composite particle morphology was prepared as an alkaline HER and OER bifunctional water electrolysis catalyst with both stability and catalytic activity. The composition, morphology and electronic structure of the catalyst were systematically characterized, and it was found that the introduction of precious metal clusters not only increased the density of active sites, but also optimized the charge transfer kinetics and reduced the reaction energy barrier through the electronic synergistic effect between the clusters and the phosphide substrate, thereby significantly improving the catalytic performance. Electrochemical tests confirmed that it has a 10mAcm -2 The HER overpotential and OER overpotential of CoPt3-CoP2 / Fe2P / MoNiP@IF are 19mV and 242mV respectively. Under this current density, there is no HER voltage decay for 48 hours of continuous operation and no OER voltage decay for 24 hours of continuous operation, which is comparable to commercial Pt / C. -2The electrolyzer assembled with CoPt3-CoP2 / Fe2P / MoNiP@IF catalyst can still show a low overpotential at a high current density, which is better than Pt / C. The overall water splitting voltage of the electrolyzer assembled with CoPt3-CoP2 / Fe2P / MoNiP@IF catalyst is 10 mA cm -2 It reaches 1.638V. BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Figure 1 This is the XPS spectrum of a Pt cluster-doped multi-metal nickel-based phosphide prepared by anchoring the Pt-Mo cluster on the phosphide substrate in Example 1 of the present invention.
[0014] Figure 2 This is the XRD spectrum of a Pt cluster-doped multi-metal nickel-based phosphide prepared by anchoring the Pt-Mo cluster on the phosphide substrate in Example 1 of the present invention.
[0015] Figure 3 HER polarization curves of a Pt cluster-doped multimetallic nickel-based phosphide and its intermediates prepared in Example 1 of the present invention in a 1.0 M KOH medium.
[0016] Figure 4 This is the OER polarization curve of a Pt cluster-doped multimetallic nickel-based phosphide and its intermediates prepared in Example 1 of the present invention in a 1.0 M KOH medium.
[0017] Figure 5 This is the chronoamperometric response diagram of CoPt3-CoP2 / Fe2P / MoNiP@IF catalyst.
[0018] Figure 6 This is the polarization curve of the complete water splitting of a Pt cluster-doped multi-metal nickel-based phosphide prepared in Example 1 of the present invention (the inset is a photo of the dual-electrode system electrolytic cell). DETAILED DESCRIPTION
[0019] The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
[0020] Example 1, a Pt cluster-doped multimetal nickel-based phosphide, comprising the following preparation steps:
[0021] (1) Weigh nickel molybdenum hexahydrate (0.10 g, 0.070 mmol) and cobalt nitrate (0.043 g, 0.18 mmol) in 10 mL of deionized water and place a piece of foamed iron (1*1.5 cm 2 ), stirred at room temperature for 30 minutes. The sample was placed in a 180°C forced air drying oven for 18 hours, cooled to room temperature, washed three times with ethanol and deionized water, and then dried at 60°C for 12 hours to obtain the product Mo4O 11 / NiCoFe-LDH@IF.
[0022] (2) The material obtained in step 1 was placed downstream, and sodium hypophosphite was placed upstream, and placed in a tube furnace, heated to 450°C at 5°C / min, maintained for 2 h, and cooled to room temperature at the same rate. The product was also washed and dried to obtain the product CoP2 / Fe2P / MoNiP@IF.
[0023] (3) The electrode material obtained in step 2 was immersed in a solution containing 10 mL of chloroplatinic acid and irradiated with light for 30 min to obtain the product CoPt3-CoP2 / Fe2P / MoNiP@IF.
[0024] like Figure 1 Based on XPS valence state analysis, the valence states and chemical environment of the CoP2 / Fe2P / MoNiP@IF composite were thoroughly investigated, confirming the successful preparation of the composite. The introduction of Pt and the resulting valence state changes enhanced the composite's electrocatalytic performance by modulating its electronic properties.
[0025] like Figure 2 Shown is the XRD pattern of a Pt cluster-doped multimetal phosphide fabricated by anchoring Pt-Mo clusters to a phosphide substrate. The material exhibits a clustered structure with numerous pores between the particles, facilitating fluid or ion transport.
[0026] like Figure 3 The following are the HER polarization curves of Pt cluster-doped multimetallic phosphides and their intermediates in 1.0 M KOH medium. The CoPt3-CoP2 / Fe2P / MoNiP@IF catalyst exhibits extraordinary activity in HER: reaching 10 mA cm -2 Only 19mV overpotential is required at the current density, which is 58.7% lower than that of commercial Pt / C (46mV). The overpotential of Pt3Mo-FeP / CoP / MoO3@IF is 26mV, which is 43.5% lower than that of commercial Pt / C (46mV).
[0027] like Figure 4 The OER polarization curves of Pt cluster-doped multimetallic phosphides and their intermediates in 1.0 M KOH are shown. In the LSV test of OER performance, the overpotential of the CoPt3-CoP2 / Fe2P / MoNiP@IF catalyst was 242 mV, narrowing the gap to 10.7% and 29.4% compared with commercial Pt / C (187 mV), respectively.
[0028] like Figure 5This is the chronoamperometric response of the CoPt3-CoP2 / Fe2P / MoNiP@IF catalyst. In continuous electrolysis tests simulating industrial operating conditions, the CoPt3-CoP2 / Fe2P / MoNiP@IF catalyst exhibited excellent potential stability: the potential fluctuation during the HER process over 48 hours under alkaline conditions was <1.0%, and the current density decay rate during the 24-hour OER test was only 2.4%, with no drift due to active site deactivation. These test data demonstrate the excellent structural stability and durability of the CoPt3-CoP2 / Fe2P / MoNiP@IF composite catalyst during long-term electrocatalytic operation.
[0029] like Figure 6 The following is a comparison of the polarization curves of the complete water splitting of Pt clusters doped with multi-metal phosphides (the inset is a photo of the electrolytic cell of the two-electrode system). -2 When the cell voltage of CoPt3-CoP2 / Fe2P / MoNiP@IF‖CoPt3-CoP2 / Fe2P / MoNiP@IF was 1.638V, close to Pt / C‖RuO2 (1.580V); this result shows that a Pt cluster-doped multi-metal nickel-based phosphide composite catalyst performs well in reducing the overall water splitting voltage and improving the electrochemical performance.
Claims
1. A Pt cluster doped multi-metal nickel-based phosphide material is a spherical unit nanomaterial, characterized in that Its morphology shows that the spherical units are compactly distributed and the shape is approximately full sphere. The surface of the spherical units has an orderly concave-convex texture structure and a rough granular surface. The morphological characteristics of the spherical unit accumulation and the granular surface are conducive to enhancing the adsorption capacity and catalytic activity.
2. Preparation and performance study of a Pt cluster-doped multimetallic nickel-based phosphide, the preparation method comprising the following steps: (1) Weigh nickel molybdenum hexapolyacid (0.10 g, 0.070 mmol) and cobalt nitrate (0.043 g, 0.18 mmol) in 10 mL of deionized water and place a piece of foam iron (1*1.5 cm 2 ), stirred at room temperature for 30 min, placed the sample in a 180°C forced air drying oven for 18 h, cooled to room temperature, washed three times with ethanol and deionized water, and then dried at 60°C for 12 h to obtain the product; (2) placing the above product downstream and sodium hypophosphite upstream, respectively, in a tube furnace, heating to 450°C at 5°C / min, maintaining for 2 hours, cooling to room temperature at the same rate, washing and drying to obtain a phosphide material; (3) The prepared phosphide material was immersed in 10 mL of chloroplatinic acid solution, stirred for 30 min under light conditions, washed and dried to obtain CoPt3-CoP2 / Fe2P / MoNiP@IF.
3. The preparation of a Pt cluster-doped multi-metal nickel-based phosphide as described in patent claim 2 is applied in the field of electrocatalytic water splitting.
4. The use according to claim 3, characterized in that The application method is as follows: a three-electrode system is used, with a saturated calomel electrode as the reference electrode, a carbon rod as the counter electrode, and a modified iron foam (IF) as the working electrode. The test is carried out in 1.0 M KOH and alkaline seawater at 10 mA cm -2 At the current density, the HER overpotential and OER overpotential of CoPt3-CoP2 / Fe2P / MoNiP@IF are 19 mV and 242 mV, respectively, which shows that the Pt cluster-doped multi-metal nickel-based phosphide material of the present invention is an electrocatalyst with high efficiency and significantly improved electrocatalytic water decomposition performance.
5. The use according to claim 3, characterized in that: Under alkaline conditions, after 1000 CV cycles, the -2 Under the current density, the overpotential of the LSV curve of CoPt3-CoP2 / Fe2P / MoNiP@IF only had a slight shift of 1mV (the decay rate was less than 1.1%); in the continuous electrolysis test simulating industrial operating conditions, the CoPt3-CoP2 / Fe2P / MoNiP@IF catalyst showed good potential stability: the potential fluctuation amplitude of the HER process for 48 hours under alkaline conditions was 1.0%, and the current density decay rate of the 24-hour OER test was only 2.4%. There was no drift phenomenon caused by deactivation of active sites, which proved that a Pt cluster-doped multi-metal nickel-based phosphide catalyst material has good structural stability and durability in long-term electrocatalytic operation, thereby concluding that a Pt cluster-doped multi-metal nickel-based phosphide material of the present invention is a very stable catalyst for electrocatalytic complete water splitting.