WO2024002126A1 - 一维Ni12P5/Ni2P多晶异质结构高效水氧化催化剂的制备方法 - Google Patents

一维Ni12P5/Ni2P多晶异质结构高效水氧化催化剂的制备方法 Download PDF

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WO2024002126A1
WO2024002126A1 PCT/CN2023/103043 CN2023103043W WO2024002126A1 WO 2024002126 A1 WO2024002126 A1 WO 2024002126A1 CN 2023103043 W CN2023103043 W CN 2023103043W WO 2024002126 A1 WO2024002126 A1 WO 2024002126A1
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catalyst
preparation
nickel foam
hours
polycrystalline
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章福祥
马哈茂德兰希德
郭向阳
范文俊
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中国科学院大连化学物理研究所
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to the technical field of catalytic materials, specifically, to a method for preparing a one-dimensional Ni 12 P 5 /Ni 2 P polycrystalline heterostructure high-efficiency water oxidation catalyst.
  • transition metal phosphides are considered to be one of the most promising electrocatalysts due to their high conductivity and easily tunable electronic structure.
  • M electropositive metal
  • one-dimensional nanomaterials have high electrochemical activity specific surface area, fast charging and efficient transport of reactive species, and have broad application prospects in reducing overpotential.
  • the nanorod structure can not only promote interfacial electron transfer by improving electron transfer on the substrate surface, but also its structural characteristics are beneficial to the release of bubbles on the electrode/electrolyte surface.
  • strategies such as element doping, oxygen or phosphorus vacancies, crystal face engineering, and interface engineering have been widely used to prepare high-performance one-dimensional electrocatalytic materials.
  • interface engineering has become one of the most effective strategies to improve the activity and stability of water splitting electrocatalysis.
  • one-dimensional materials not only have good catalytic properties, but also can serve as effective support materials for electrocatalysis. It can be seen that the preparation of transition metal phosphide materials with one-dimensional unique polycrystalline heterostructure on nickel foam carriers is the best way to obtain good activity and high stability. An efficient approach to OER electrocatalysts.
  • the present invention provides a method for preparing a one-dimensional Ni 12 P 5 /Ni 2 P polycrystalline heterostructure high-efficiency water oxidation catalyst.
  • the present invention mainly uses low-priced commercial nickel foam (NF) as a conductive carrier and nickel source, and obtains a one-dimensional Ni 12 P 5 /Ni 2 P/NF polycrystalline heterostructure through a two-step hydrothermal-phosphating method.
  • the two-step hydrothermal method increases the roughness and defect level of the nickel foam surface.
  • the heterostructure and interface in the Ni 12 P 5 /Ni 2 P/NF catalyst skillfully adjust the electronic structure of Ni and P ions in the electrocatalyst, which is beneficial to reducing the energy barrier of the rate-limiting step.
  • the one-dimensional polycrystalline heterostructure facilitates the adsorption of water molecules at the catalytic sites and the desorption of oxygen from the catalyst surface.
  • the tight connection between the polycrystalline heterojunction electrocatalyst and the nickel foam carrier effectively prevents the catalyst from peeling off during the reaction, thereby achieving long-term stability in alkaline electrolytes.
  • the technical means adopted in the present invention are as follows: a method for preparing a one-dimensional Ni 12 P 5 /Ni 2 P polycrystalline heterostructure efficient water oxidation catalyst, using low-cost commercial nickel foam (NF) as a conductive carrier and nickel source. Using phosphite as the phosphorus source, a one-dimensional Ni 12 P 5 /Ni 2 P/NF polycrystalline heterostructure was obtained through a two-step hydrothermal-phosphating method.
  • NF nickel foam
  • the phosphite is NaH 2 PO 2 ⁇ H 2 O.
  • the preparation method specifically includes the following steps:
  • step 3 Mix NaH 2 PO 2 ⁇ H 2 O and r-NF obtained in step 2 according to different weight ratios and place them in a ceramic boat, then put them together into a quartz tube, and use a tube furnace under a nitrogen atmosphere at 270 to 380 Heating at °C for 2-4 hours, naturally cooling to room temperature, washing and drying, the target material Ni 12 P 5 /Ni 2 P/NF catalyst was obtained.
  • the size of the nickel foam is 3 ⁇ 3 ⁇ 6 ⁇ 6cm 2 .
  • the concentration of the (NH 4 ) 2 HPO 4 aqueous solution is 1-2mM, and the concentration of the NaOH aqueous solution is 100-200mM.
  • step three the weight ratio of NaH 2 PO 2 ⁇ H 2 O to r-NF obtained in step two is 9 to 11:1.
  • the nitrogen flow rate is 100-150 sccm
  • the heating rate is 5-8°C/min
  • the heating temperature is controlled at 270-380°C
  • the material Ni 12 P 5 /Ni 2 P/NF is obtained -T
  • T is the heating temperature value, which can be 275°C, 300°C, 325°C, 350°C, 375°C respectively.
  • the nitrogen flow rate is 150 sccm
  • the heating rate is 5°C/min
  • the heating temperature is controlled at 400°C
  • natural cooling, washing and drying are performed to obtain the material Ni 12 P 5 /NF.
  • the nitrogen flow rate is 150 sccm
  • the heating rate is 5°C/min
  • the heating temperature is controlled at 250°C
  • natural cooling, washing, and drying are performed to obtain the material Ni 2 P/NF.
  • step three NaH 2 PO 2 ⁇ H 2 O is placed upstream of the ceramic boat, and the r-NF obtained in step 2 is placed downstream of the ceramic boat.
  • NaH 2 PO 2 ⁇ H 2 O and r The -NF weight ratio is 9 to 11:1, the nitrogen flow rate is 150 sccm, the heating rate is 5°C/min, the heating temperature is controlled at 250°C, natural cooling, washing and drying are performed to prepare the material Ni 2 P/NF.
  • the drying conditions are: vacuum drying at room temperature for 12-24 hours.
  • the ethanol/water solution of potassium hexachloroiridate and the above potassium hexachloroiridate solution are drop-coated onto the obtained Ni 12 P 5 /Ni 2 P/NF catalyst, then heated at 60-90°C, and naturally cooled to room temperature to prepare the Ir-Ni 12 P 5 /Ni 2 P/NF-275 catalyst;
  • the concentration of potassium hexachloroiridate solution is 0.02-0.04mM
  • the solvent is mixed with ethanol/water volume ratio 1/(1-2) to prepare Ir x -Ni 12 P 5 /Ni 2 P/
  • the present invention provides an application of the above catalyst in electrocatalytic moisture desorption of oxygen.
  • the specific reaction conditions are: the obtained Ni 12 P 5 /Ni 2 P/NF-T, Ni 12 P 5 /NF, Ni 2 P/NF or Ir-Ni 12 P 5 /Ni 2 P/NF catalyst is directly used as an oxygen evolution catalyst.
  • Electrode, a two-electrode system performs electrocatalytic water splitting reaction.
  • the electrolyte used in the electrocatalytic water splitting reaction is an alkaline electrolyte
  • the base is one of KOH, NaOH, LiOH, and CsOH, preferably KOH
  • the concentration of the alkaline electrolyte It is 0.5 ⁇ 10M, preferably 1M.
  • the raw materials used in the one-dimensional Ni 12 P 5 /Ni 2 P polycrystalline heterostructure high-efficiency water oxidation catalyst involved in the present invention are low in price, the synthesis method is simple and convenient, the chemical properties are stable, and the electrode structure is robust. It has superior OER activity and stability and is easy to promote and apply.
  • a one-dimensional polycrystalline heterostructure catalyst is synthesized through a two-step hydrothermal-phosphating method, which can effectively solve the problem of large overpotential, poor internal charge transfer, and catalyst instability in TMPs catalysts in the existing technology. and problems such as easy peeling.
  • the one-dimensional heterostructure is closely combined with the conductive carrier nickel foam, which is beneficial to charge transport and the release of bubbles on the electrode/electrolyte surface.
  • the prepared Ni 12 P 5 /Ni 2 P/NF catalyst performs electrocatalytic water oxidation reaction in alkaline solution and has low electrocatalytic water oxidation reaction.
  • the overpotential at 10mA/ cm2 current density is 254mV, its performance is better than the current best RuO2 catalyst (overpotential is 295mV), the corresponding Ni2P /NF (overpotential potential of 278mV) and Ni 12 P 5 /NF (overpotential of 288mV); 200 hours stability at a current density of 50mA/cm.
  • the overpotential for water oxidation can be further reduced.
  • the overpotential can be further reduced to 196mV while maintaining Stability over 100 hours at 50mA/ cm2 current density.
  • This two-step hydrothermal and phosphating method using commercial nickel foam as the precursor shows broad application prospects in the synthesis of alkaline OER electrocatalysts.
  • the present invention can be widely promoted in fields such as water splitting electrocatalytic materials.
  • Figure 1 is a transmission electron microscope (TEM) image of the target material Ni 12 P 5 /Ni 2 P/NF-275.
  • Figure 2 is a high-resolution transmission electron microscope (HRTEM) image of the target material Ni 12 P 5 /Ni 2 P/NF-275.
  • Figure 3 shows the LSV polarization curves of the target materials Ni 12 P 5 /Ni 2 P/NF-275, Ni 12 P 5 /NF, Ni 2 P/NF and RuO 2 /NF.
  • Figure 4 shows the stability test chart of the target material Ni 12 P 5 /Ni 2 P/NF-275 at a current density of 50mA/cm -2 (test time 200h).
  • Figure 5 is a spherical aberration transmission electron microscope (HAADF-STEM) image of the target material 3% Ir-Ni 12 P 5 /Ni 2 P/NF-275.
  • HAADF-STEM spherical aberration transmission electron microscope
  • Figure 6 is the LSV polarization curve of the target material x%Ir-Ni 12 P 5 /Ni 2 P/NF-275.
  • Figure 7 is a stability test chart of the target material 3% Ir-Ni 12 P 5 /Ni 2 P/NF-275 at a current density of 50mA/cm -2 (test time 120h).
  • step 2 Mix NaH 2 PO 2 ⁇ H 2 O and r-NF obtained in step 2 at a weight ratio of 10:1 and place them in a ceramic boat. Then put them together into a quartz tube and heat them in a tube furnace at 275°C for 2 hours under a nitrogen atmosphere. (Nitrogen flow rate is 150 sccm, heating rate is 5°C/min), naturally cooled to room temperature, washed with deionized water, and then placed in a vacuum drying oven to dry at room temperature overnight to obtain the target material Ni 12 P 5 /Ni 2 P/NF. -275.
  • the transmission electron microscope image ( Figure 1) and the high-resolution transmission electron microscope image ( Figure 2) show that the target material is a polycrystalline heterostructure, with a lattice stripe spacing of 0.192nm corresponding to the (210) crystal of Ni 2 P plane, 0.195nm and 0.22nm respectively correspond to the (420) and (202) crystal planes of Ni 12 P 5 .
  • the electrochemical double layer capacitance was measured by cyclic voltammetry (CV) at different scan rates in the potential range of 0.9V ⁇ 1.02V (vs. Hg/HgO).
  • the EIS test records data in the range of 0.1Hz to 100KHz at a potential of 1.53V (vs.RHE).
  • the obtained polarization curve, electric double layer capacitance diagram, EIS and stability test are shown in Figures 3 to 4.
  • the r-NF preparation process is the same as in Example 1.
  • step 2 Mix NaH 2 PO 2 ⁇ H 2 O and r-NF obtained in step 2 at a weight ratio of 10:1 and place them in a ceramic boat. Then put them together into a quartz tube and heat them in a tube furnace at 300°C for 2 hours under a nitrogen atmosphere. (Nitrogen flow rate is 150cc, heating rate is 5°C/min), naturally cooled, washed with deionized water, and then placed in a vacuum drying box to dry at room temperature overnight to obtain the target material Ni 12 P 5 /Ni 2 P/NF-300 .
  • the electrochemical test conditions are the same as in Example 1.
  • the electrochemical test performance is shown in Figure 3.
  • the corresponding overpotential is 324mV under the current density condition of 50mA/ cm2 .
  • the r-NF preparation process is the same as in Example 1.
  • step 2 Mix NaH 2 PO 2 ⁇ H 2 O and r-NF obtained in step 2 at a weight ratio of 10:1 and place it in a ceramic boat. Put them together into a quartz tube, use a tube furnace to heat at 325°C for 2 hours under a nitrogen atmosphere (nitrogen flow rate is 150cc, heating rate is 5°C/min), cool naturally, wash with deionized water, and then put it into a vacuum drying box at room temperature. After drying overnight, the target material Ni 12 P 5 /Ni 2 P/NF-325 was obtained.
  • the electrochemical test conditions are the same as in Example 1.
  • the electrochemical test performance is shown in Figure 3.
  • the corresponding overpotential is 330mV under the current density condition of 50mA/ cm2 .
  • the r-NF preparation process is the same as in Example 1.
  • step 2 Mix NaH 2 PO 2 ⁇ H 2 O and r-NF obtained in step 2 at a weight ratio of 10:1 and place them in a ceramic boat. Then put them together into a quartz tube and heat them in a tube furnace at 350°C for 2 hours under a nitrogen atmosphere. (Nitrogen flow rate is 150 sccm, heating rate is 5°C/min), naturally cooled, washed with deionized water, and then placed in a vacuum drying box and dried at room temperature overnight to obtain the target material Ni 12 P 5 /Ni 2 P/NF-350 .
  • the electrochemical test conditions are the same as in Example 1.
  • the electrochemical test performance is shown in Figure 3.
  • the corresponding overpotential is 340mV under the current density condition of 50mA/ cm2 .
  • the r-NF preparation process is the same as in Example 1.
  • step 2 Mix NaH 2 PO 2 ⁇ H 2 O and r-NF obtained in step 2 at a weight ratio of 10:1 and place them in a ceramic boat. Then put them together into a quartz tube and heat them in a tube furnace at 375°C for 2 hours under a nitrogen atmosphere. (Nitrogen flow rate is 150cc, heating rate is 5°C/min), naturally cooled to room temperature, washed with deionized water, and then placed in a vacuum drying box to dry at room temperature overnight to obtain the target material Ni 12 P 5 /Ni 2 P/NF. -375.
  • the electrochemical test conditions are the same as in Example 1.
  • the electrochemical test performance is shown in Figure 3.
  • the corresponding overpotential under the current density condition of 50mA/ cm2 is 351mV.
  • the electrochemical test conditions are the same as in Example 1.
  • the electrochemical test performance is shown in Figure 6.
  • the corresponding overpotential under the current density condition of 10mA/ cm2 is 230mV; the corresponding overpotential under the current density condition of 50mA/ cm2 is 274mV.
  • the electrochemical test conditions are the same as in Example 1.
  • the electrochemical test performance is shown in Figure 6.
  • the corresponding overpotential under the current density condition of 10mA/ cm2 is 210mV; the corresponding overpotential under the current density condition of 50mA/ cm2 is 258mV.
  • the target material 3% Ir-Ni 12 P 5 /Ni 2 P/NF-275 has a one-dimensional polycrystalline heterostructure.
  • the spherical aberration electron microscope ( Figure 5) shows that Ir is in Ni 12 P 5 /Ni 2 P/NF-275. Dispersed for single atoms.
  • the electrochemical test conditions are the same as in Example 1.
  • the electrochemical test performance is shown in Figure 6.
  • the corresponding overpotential under the current density condition of 10mA/ cm2 is 199mV; the corresponding overpotential under the current density condition of 50mA/ cm2 is 239mV.
  • Stability test results show that the catalyst is stable during the 120h test period at a current density of 50mA/ cm2 ( Figure 7).
  • the electrochemical test conditions are the same as in Example 1.
  • the electrochemical test performance is shown in Figure 6.
  • the corresponding overpotential under the current density condition of 10mA/ cm2 is 200mV; the corresponding overpotential under the current density condition of 50mA/ cm2 is 240mV.
  • the r-NF preparation process is the same as in Example 1.
  • step 2 Mix NaH 2 PO 2 ⁇ H 2 O and r-NF obtained in step 2 at a weight ratio of 10:1 and place them in a ceramic boat. Then put them together into a quartz tube and heat them in a tube furnace at 400°C for 2 hours under a nitrogen atmosphere. (Nitrogen flow rate is 150 sccm, heating rate is 5°C/min), natural cooling, washing, and drying to obtain the target material Ni 12 P 5 /NF.
  • the electrochemical test conditions are the same as in Example 1.
  • the electrochemical test performance is shown in Figure 3.
  • the corresponding overpotential under the current density condition of 10mA/ cm2 is 288mV; the corresponding overpotential under the current density condition of 50mA/ cm2 is 358mV.
  • the r-NF preparation process is the same as in Example 1.
  • the weight ratio of NaH 2 PO 2 ⁇ H 2 O to r-NF is 10:1, and the nitrogen flow rate is 150 sccm.
  • the heating rate is 5°C/min, the heating temperature is controlled at 250°C, natural cooling, washing and drying are performed to obtain the material Ni 2 P/NF.
  • the electrochemical test conditions are the same as in Example 1.
  • the electrochemical test performance is shown in Figure 3.
  • the corresponding overpotential under the current density condition of 10mA/ cm2 is 278mV; the corresponding overpotential under the current density condition of 50mA/ cm2 is 320mV.
  • the electrochemical test conditions are the same as in Example 1.
  • the electrochemical test performance is shown in Figure 3.
  • the corresponding overpotential under the current density condition of 10mA/ cm2 is 294mV; the corresponding overpotential under the current density condition of 50mA/ cm2 is 373mV.

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Abstract

本发明公开了一种一维Ni12P5/Ni2P多晶异质结构高效水氧化催化剂的制备方法，其以泡沫镍为导电载体和镍源，以亚磷酸钠盐作为磷源，通过两步水热-磷化方法合成一维多晶异质结构催化剂Ni12P5/Ni2P/NF。多晶异质结构和界面有效解决了过渡金属磷化物(TMPs)催化剂过电势大、内部电荷传递差、催化剂不稳定和易剥落等问题；一维异质结构与泡沫镍导电载体的紧密结合有利于电荷传输和电极/电解质表面气泡的释放。所制备Ni12P5/Ni2P/NF催化剂在碱性溶液中具有较低的电催化水氧化过电势和长时间的稳定性。在Ni12P5/Ni2P/NF上负载单原子Ir后可进一步将水氧化过电势降低，具有广阔的应用前景。

Description

一维Ni12P5/Ni2P多晶异质结构高效水氧化催化剂的制备方法 技术领域
本发明涉及催化材料技术领域，具体而言，尤其涉及一维Ni12P5/Ni2P多晶异质结构高效水氧化催化剂的制备方法。
背景技术
全球经济和人类社会的巨大发展高度依赖于化石燃料，势必导致日益严重的能源危机和环境问题。为了解决这些问题，人们在电解液、可充电金属-空气电池、燃料电池、水电解等电化学体系生产可再生氢能研究领域进行了大量的研究。然而，上述体系生产可再生氢的电化学性能极大地受制于析氧反应(OER)。这是由于在OER过程中，多反应中间体产生缓慢的OER动力学，导致过电位大、能量效率损失显著。因此，人们进行了大量研究来制备高活性、高稳定性和低成本的OER催化剂。虽然，基于贵金属的电催化剂的电解水性能优异，但是其含量稀缺，且在碱性电解水体系中稳定性低，并非理想的商业催化剂。
近年来，开发活性高、稳定性好和低成本的无金属、单原子分散、过渡金属基硫属化物、硼化物、碳化物、氮化物和磷化物等OER电催化剂成为科学家们的研究重点。但是，目前此类非贵金属OER催化剂的电催化性能还远远无法满足工业应用的要求。同时，其导电性差、比表面积小，大大阻碍了催化剂材料内部的电荷传输、电解质与催化剂表面活性位点的接触。在上述众多材料中，过渡金属磷化物(TMPs)由于其高的导电性和易于调节的电子结构而被认为是最有前途的电催化剂之一。然而，TMPs中正电性金属(M＝Co、Ni、Fe等)原子和高电负性非金属P原子的高离子特性削弱了电子离域能力，导致其电催化活性低、稳定性差。众所周知，一维纳米材料具有高的电化学活性比表面积、快速充电和反应物种的高效传输特性，在降低过电位方面具有广泛的应用前景。此外，已有研究表明纳米棒结构不仅可以通过改善基底表面的电子传递来促进界面电子转移，而且其结构特性有利于电极/电解质表面气泡的释放。最近，元素掺杂、氧或磷空位、晶面工程和界面工程等策略广泛用于高性能一维电催化材料的制备。其中，界面工程已成为提高水分解电催化活性和稳定性的最有效策略之一。尽管过渡金属磷化物类水分解电催化剂研究取得了一些进展，但仍然缺乏低过电势、高稳定性和长寿命的TMPs基电催化体系。应当指出的是，一维材料不仅具有良好的催化性能，而且可以作为电催化的有效载体材料。由此可见，在泡沫镍载体上制备具有一维独特多晶异质结构的过渡金属磷化物材料是获得良好活性和高稳定性 OER电催化剂的有效途径。
发明内容
为解决上述技术问题，本发明提供一种一维Ni12P5/Ni2P多晶异质结构高效水氧化催化剂的制备方法。本发明主要利用价格低的商业泡沫镍(NF)作为导电载体和镍源，通过两步水热-磷化方法获得一维Ni12P5/Ni2P/NF多晶异质结构。两步水热方法增大了泡沫镍表面的粗糙度和缺陷程度。Ni12P5/Ni2P/NF催化剂中的异质结构和界面巧妙地调节了电催化剂中Ni和P离子的电子结构，有利于降低限速步骤的能垒。另外，一维多晶异质结构有利于水分子在催化位点的吸附和氧气从催化剂表面的脱附。此外，多晶异质结电催化剂与泡沫镍载体的紧密连接有效阻止了反应过程中催化剂的剥离，从而起到碱性电解液中长时间稳定的效果。
本发明采用的技术手段如下：一种一维Ni12P5/Ni2P多晶异质结构高效水氧化催化剂的制备方法，以成本低的商业泡沫镍(NF)作为导电载体和镍源，以亚磷酸盐作为磷源，通过两步水热-磷化方法获得一维Ni12P5/Ni2P/NF多晶异质结构。
所述亚磷酸盐为NaH2PO2·H2O。
所述制备方法具体包括以下步骤：
一、泡沫镍(NF)裁剪为特定尺寸、轻压使其变薄，放入1.0-4.0M HCl溶液中超声处理20-60min，之后依次在去离子水、乙醇、丙酮中超声处理20-40min，将洗涤后的泡沫镍放入真空干燥箱中50-70℃真空干燥24-36h，得到干净的NF片，备用；
二、配置(NH4)2HPO4水溶液，将步骤一得到的NF片放入其中，进行溶剂热反应，反应温度控制在170-190℃，时间控制在10-16h，自然冷却至室温，去离子水洗涤，真空干燥箱中50-70℃真空干燥10-16h，将干燥后的NF片放入NaOH水溶液中100-130℃下溶剂热反应4-6h，洗涤、干燥，得到表面粗糙有缺陷的泡沫镍片r-NF，备用；
三、将NaH2PO2·H2O与步骤二所得r-NF按不同重量比混合后置于陶瓷舟中，之后一起放入石英管中，于氮气氛围下使用管式炉在270～380℃下加热2-4h，自然冷却至室温，洗涤、干燥，制得目标材料Ni12P5/Ni2P/NF催化剂。
基于上述方案，优选地，步骤一中，泡沫镍尺寸为3×3～6×6cm2。
基于上述方案，优选地，步骤二中，(NH4)2HPO4水溶液浓度为1-2mM，NaOH水溶液浓度为100-200mM。
基于上述方案，优选地，步骤三中，NaH2PO2·H2O与步骤二所得r-NF重量比为9～11：1。
基于上述方案，优选地，步骤三中，氮气流量为100～150sccm，升温速率为5-8℃/min，加热温度控制在270～380℃，制得材料Ni12P5/Ni2P/NF-T，T为加热温度数值，可以分别为275℃、300℃、325℃、350℃、375℃。
基于上述方案，优选地，步骤三中，氮气流量为150sccm，升温速率为5℃/min，加热温度控制在400℃，自然冷却，洗涤、干燥，制得材料Ni12P5/NF。
基于上述方案，优选地，氮气流量为150sccm，升温速率为5℃/min，加热温度控制在250℃，自然冷却，洗涤、干燥，制得材料Ni2P/NF。
基于上述方案，优选地，步骤三中，将NaH2PO2·H2O置于陶瓷舟的上游处，步骤二所得r-NF置于陶瓷舟下游，NaH2PO2·H2O与r-NF重量比为9～11：1，氮气流量为150sccm，升温速率为5℃/min，加热温度控制在250℃，自然冷却，洗涤、干燥，制得材料Ni2P/NF。
基于上述方案，优选地，步骤三中，干燥的条件为：室温真空干燥12-24h。
基于上述方案，优选地，根据上述方案所制备的Ni12P5/Ni2P/NF催化剂，将六氯铱酸钾的乙醇/水溶液，将上述六氯铱酸钾溶液滴涂到所得Ni12P5/Ni2P/NF催化剂上，之后60-90℃加热，自然冷却至室温后制得的Ir-Ni12P5/Ni2P/NF-275催化剂；
基于上述方案，优选地，六氯铱酸钾溶液浓度为0.02-0.04mM，溶剂为乙醇/水体积比1/(1-2)混合，制得Irx-Ni12P5/Ni2P/NF-T材料中Ir与Ni12P5/Ni2P/NF催化剂的质量比为0.01～0.04：1，x＝1-4，例如1、2、3或4。
另一方面，本发明提供了一种上述催化剂在电催化水分解析氧中的应用。具体反应条件为：得到的Ni12P5/Ni2P/NF-T、Ni12P5/NF、Ni2P/NF或Ir-Ni12P5/Ni2P/NF催化剂直接作为析氧电极，以两电极体系进行电催化水分解反应。
基于上述方案，优选地，所述电催化水分解的反应所用的电解液为碱性电解液，碱为KOH、NaOH、LiOH、CsOH的中的一种，优选为KOH；碱性电解液的浓度为0.5～10M，优选为1M。
本发明的有益效果：本发明涉及的一维Ni12P5/Ni2P多晶异质结构高效水氧化催化剂所用原料价格低廉，合成方法简单方便，化学性质稳定，所构成的电极结构稳健，具有优越的OER活性和稳定性，易于推广和应用。以泡沫镍为导电载体和镍源，通过两步水热-磷化方法合成一维多晶异质结构催化剂，能够有效解决现有技术中TMPs催化剂过电势大、内部电荷传递差、催化剂不稳定和易剥落等问题。另外，一维异质结构与导电载体泡沫镍紧密结合，有利于电荷传输和电极/电解质表面气泡的释放。所制备Ni12P5/Ni2P/NF催化剂在碱性溶液中进行电催化水氧化反应，具有较低的电催化水 氧化过电势和长时间的稳定性，10mA/cm2电流密度下的过电势为254mV，其性能优于目前最好的RuO2催化剂(过电势为295mV)、相应的Ni2P/NF(过电势为278mV)和Ni12P5/NF(过电势为288mV)；在50mA/cm2电流密度下具有200小时的稳定性。Ir单原子负载在Ni12P5/Ni2P/NF多晶异质结构上时，可进一步将水氧化过电势降低，10mA/cm2电流密度下，过电位可进一步降低至196mV，同时保持50mA/cm2电流密度下100小时以上的稳定性。这种以商业泡沫镍为前驱体的两步水热、磷化的方法在合成碱性OER电催化剂方面显示了广阔的应用前景。
基于上述理由本发明可在水分解电催化材料等领域广泛推广。
附图说明
图1为目标材料Ni12P5/Ni2P/NF-275的透射电镜(TEM)图。
图2为目标材料Ni12P5/Ni2P/NF-275高分辨透射电镜(HRTEM)图。
图3为目标材料Ni12P5/Ni2P/NF-275、Ni12P5/NF、Ni2P/NF和RuO2/NF的LSV极化曲线。
图4为目标材料Ni12P5/Ni2P/NF-275在50mA/cm-2电流密度下的稳定性测试图(测试时间200h)。
图5为目标材料3％Ir-Ni12P5/Ni2P/NF-275的球差透射电镜(HAADF-STEM)图。
图6为目标材料x％Ir-Ni12P5/Ni2P/NF-275的LSV极化曲线。
图7为目标材料3％Ir-Ni12P5/Ni2P/NF-275在50mA/cm-2电流密度下的稳定性测试图(测试时间120h)。
具体实施方式
为了进一步说明本发明，列举以下实施实例并结合附图对本发明进行详细说明，但它并不限制各附加权利要求所定义的发明范围。
实施例1
把泡沫镍(NF)裁剪为3×3cm2、轻压使其变薄，放入3.0M HCl溶液中超声处理30min，之后依次在去离子水、乙醇、丙酮中超声处理30min，将洗涤后的泡沫镍放入真空干燥箱中60℃真空干燥24h，得到干净的NF片，备用。
配置1mM(NH4)2HPO4水溶液，将步骤一得到的NF片放入其中，进行溶剂热反应，控制反应温度为160℃，时间控制在12h，自然冷却至室温，去离子水洗涤，真空干燥箱中60℃真空干燥12h，将干燥后的NF片放入100mM NaOH水溶液中120℃下溶剂热反应5h，去离子水洗涤，之后放入真空干燥箱中室温干燥过夜，得到表面粗 糙有缺陷的泡沫镍片r-NF，备用。
将NaH2PO2·H2O与步骤二所得r-NF按10：1重量比混合后置于陶瓷舟中，之后一起放入石英管中，于氮气氛围下使用管式炉275℃加热2h(氮气流量为150sccm，升温速率为5℃/min)，自然冷却至室温，去离子水洗涤，之后放入真空干燥箱中室温干燥过夜，制得目标材料Ni12P5/Ni2P/NF-275。
目标材料的结构表征：透射电镜图(图1)和高分辨透射电镜图(图2)可以看出目标材料为多晶异质结构，晶格条纹间距0.192nm对应Ni2P的(210)晶面，0.195nm和0.22nm分别对应Ni12P5的(420)和(202)晶面。
Ni12P5/Ni2P/NF-275催化剂的电化学测试：在电化学工作站上测试目标材料的电化学性能，使用石墨棒用作为对电极，Hg/HgO电极(KOH，1M)作为参比电极。根据能斯特方程，将本文测得的所有电位均校准为可逆氢电极(RHE)，E(RHE)＝0.098+E(Hg/HgO)+0.0592×pH。在O2饱和的1M KOH电解质中以1mV/s的扫描速率记录极化曲线。极化曲线和塔菲尔斜率均进行90％的iR补偿。通过循环伏安法(CV)在不同的扫描速率下，在0.9V～1.02V(vs.Hg/HgO)的电位范围内测量电化学双层电容。EIS测试在1.53V(vs.RHE)电位下记录0.1Hz至100KHz范围内数据。稳定性测试条件：计时电流法，I＝50mA/cm2。所得的极化曲线、双电层电容图，EIS和稳定性测试如图3～4所示。极化曲线(图3)可以看出，在10mA/cm2电流密度下对应的过电位为254mV，优于同类材料Ni12P5/NF、Ni2P/NF和商业RuO2/NF；在50mA/cm2电流密度下对应的过电位为295mV。稳定性测试结果表明，该催化剂在50mA/cm2电流密度下200h测试期内表现稳定(图4)。
实施例2
r-NF制备处理同实施例1。
将NaH2PO2·H2O与步骤二所得r-NF按10：1重量比混合后置于陶瓷舟中，之后一起放入石英管中，于氮气氛围下使用管式炉300℃加热2h(氮气流量为150cc，升温速率为5℃/min)，自然冷却，去离子水洗涤，之后放入真空干燥箱中室温干燥过夜，制得目标材料Ni12P5/Ni2P/NF-300。
电化学测试条件同实施例1，电化学测试性能见图3，在50mA/cm2电流密度条件下对应的过电位为324mV。
实施例3
r-NF制备处理同实施例1。
将NaH2PO2·H2O与步骤二所得r-NF按10：1重量比混合后置于陶瓷舟中，之后 一起放入石英管中，于氮气氛围下使用管式炉325℃加热2h(氮气流量为150cc，升温速率为5℃/min)，自然冷却，去离子水洗涤，之后放入真空干燥箱中室温干燥过夜，制得目标材料Ni12P5/Ni2P/NF-325。
电化学测试条件同实施例1，电化学测试性能见图3，在50mA/cm2电流密度条件下对应的过电位为330mV。
实施例4
r-NF制备处理同实施例1。
将NaH2PO2·H2O与步骤二所得r-NF按10：1重量比混合后置于陶瓷舟中，之后一起放入石英管中，于氮气氛围下使用管式炉350℃加热2h(氮气流量为150sccm，升温速率为5℃/min)，自然冷却，去离子水洗涤，之后放入真空干燥箱中室温干燥过夜，制得目标材料Ni12P5/Ni2P/NF-350。
电化学测试条件同实施例1，电化学测试性能见图3，在50mA/cm2电流密度条件下对应的过电位为340mV。
实施例5
r-NF制备处理同实施例1。
将NaH2PO2·H2O与步骤二所得r-NF按10：1重量比混合后置于陶瓷舟中，之后一起放入石英管中，于氮气氛围下使用管式炉375℃加热2h(氮气流量为150cc，升温速率为5℃/min)，自然冷却至室温，去离子水洗涤，之后放入真空干燥箱中室温干燥过夜，制得目标材料Ni12P5/Ni2P/NF-375。
电化学测试条件同实施例1，电化学测试性能见图3，在50mA/cm2电流密度条件下对应的过电位为351mV。
实施例6
配置浓度为0.02mM的六氯铱酸钾的乙醇/水溶液(体积比1/1)，将100μL上述六氯铱酸钾溶液滴涂到实施例1所制备的Ni12P5/Ni2P/NF-275催化剂上，之后70℃加热2h，自然冷却至室温后制得的目标1％Ir-Ni12P5/Ni2P/NF-275催化剂。
电化学测试条件同实施例1，电化学测试性能见图6，在10mA/cm2电流密度条件下对应的过电位为230mV；50mA/cm2电流密度条件下对应的过电位为274mV。
实施例7
配置浓度为0.02mM的六氯铱酸钾的乙醇/水溶液(体积比1/1)，将200μL上述六氯铱酸钾溶液滴涂到实施例1所制备的Ni12P5/Ni2P/NF-275催化剂上，之后70℃加热2h，自然冷却至室温后制得的目标2％Ir-Ni12P5/Ni2P/NF-275催化剂。
电化学测试条件同实施例1，电化学测试性能见图6，在10mA/cm2电流密度条件下对应的过电位为210mV；50mA/cm2电流密度条件下对应的过电位为258mV。
实施例8
配置浓度为0.02mM的六氯铱酸钾的乙醇/水溶液(体积比1/1)，将300μL上述六氯铱酸钾溶液滴涂到实施例1所制备的Ni12P5/Ni2P/NF-275催化剂上，之后70℃加热2h，自然冷却至室温后制得的目标3％Ir-Ni12P5/Ni2P/NF-275催化剂。
目标材料3％Ir-Ni12P5/Ni2P/NF-275为一维多晶异质结构，球差电镜(图5)可知，Ir在Ni12P5/Ni2P/NF-275为单原子分散。
电化学测试条件同实施例1，电化学测试性能见图6，在10mA/cm2电流密度条件下对应的过电位为199mV；50mA/cm2电流密度条件下对应的过电位为239mV。稳定性测试结果表明，该催化剂在50mA/cm2电流密度下120h测试期内表现稳定(图7)。
实施例9
配置浓度为0.02mM的六氯铱酸钾的乙醇/水溶液(体积比1/1)，将400μL上述六氯铱酸钾溶液滴涂到实施例1所制备的Ni12P5/Ni2P/NF-275催化剂上，之后70℃加热2h，自然冷却至室温后制得的目标4％Ir-Ni12P5/Ni2P/NF-275催化剂。
电化学测试条件同实施例1，电化学测试性能见图6，在10mA/cm2电流密度条件下对应的过电位为200mV；50mA/cm2电流密度条件下对应的过电位为240mV。
对比例1
非异质结构Ni12P5/NF催化剂电化学水氧化对照实验。
r-NF制备处理同实施例1。
将NaH2PO2·H2O与步骤二所得r-NF按10：1重量比混合后置于陶瓷舟中，之后一起放入石英管中，于氮气氛围下使用管式炉400℃加热2h(氮气流量为150sccm，升温速率为5℃/min)，自然冷却，洗涤、干燥，制得目标材料Ni12P5/NF。
电化学测试条件同实施例1，电化学测试性能见图3，在10mA/cm2电流密度条件下对应的过电位为288mV；50mA/cm2电流密度条件下对应的过电位为358mV。
对比例2
非异质结构Ni2P/NF催化剂电化学水氧化对照实验。
r-NF制备处理同实施例1。
将NaH2PO2·H2O置于陶瓷舟的上游处，r-NF置于陶瓷舟下游，NaH2PO2·H2O与r-NF重量比为10：1，氮气流量为150sccm，升温速率为5℃/min，加热温度控制在250℃，自然冷却，洗涤、干燥，制得材料Ni2P/NF。
电化学测试条件同实施例1，电化学测试性能见图3，在10mA/cm2电流密度条件下对应的过电位为278mV；50mA/cm2电流密度条件下对应的过电位为320mV。
对比例3
商业RuO2负载在泡沫镍上的电化学水氧化对照实验。
将5mg商业RuO2催化剂分散在450μL体积比为1：3.5的水/乙醇混合溶剂中，并向其中加入50μL质量分数为5％的Nafion水溶液，持续超声30min形成均匀的墨水状混合液。然后，将制备好的催化剂墨水状混合液滴在0.5×0.5cm2的泡沫镍上(含量约为1.0mg/cm2)作为工作电极。
电化学测试条件同实施例1，电化学测试性能见图3，在10mA/cm2电流密度条件下对应的过电位为294mV；50mA/cm2电流密度条件下对应的过电位为373mV。

Claims (10)

  1. 一种一维Ni12P5/Ni2P多晶异质结构高效水氧化催化剂的制备方法，其特征在于，所述制备方法包括以下步骤：
    一、泡沫镍放入1.0-4.0M HCl溶液中超声处理20-60min，之后依次在去离子水、乙醇、丙酮中超声处理20-40min，将洗涤后的泡沫镍进行干燥，得到干净的泡沫镍片，备用；
    二、将步骤一得到的泡沫镍片放入(NH4)2HPO4水溶液中，进行溶剂热反应，反应温度控制在170-190℃，时间控制在10-16h，自然冷却至室温，洗涤，干燥12h，将干燥后的泡沫镍片放入NaOH水溶液中100-130℃下溶剂热反应4-6h，洗涤、干燥，得到表面粗糙有缺陷的泡沫镍片，备用；
    三、将NaH2PO2·H2O与步骤二所得表面粗糙有缺陷的泡沫镍片混合后于氮气氛围下使用管式炉在270～380℃下加热2-3h，自然冷却，洗涤、干燥，制得Ni12P5/Ni2P/NF催化剂。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤一中，泡沫镍尺寸为3×3～6×6cm2；干燥的条件为：50-70℃真空干燥24-36h。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤二中，(NH4)2HPO4水溶液浓度为1-2mM，NaOH水溶液浓度为100-200mM；干燥的条件为：50-70℃真空干燥10-16h。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤三中，NaH2PO2·H2O与步骤二所得r-NF重量比为9～11：1。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤三中，氮气流量为100～150sccm，升温速率控制在5-8℃/min；干燥的条件为：室温真空干燥12-24h。
  6. 根据权利要求1～5中任意一项所述的制备方法，其特征在于，将六氯铱酸钾溶于体积比为1：1-2的乙醇/水混合溶剂中配置六氯铱酸钾的乙醇/水溶液，将上述六氯铱酸钾溶液滴涂到所得Ni12P5/Ni2P/NF催化剂上，之后60-90℃加热2-4h，自然冷却后制得Ir-Ni12P5/Ni2P/NF催化剂，x＝1-4。
  7. 根据权利要求6所述的制备方法，其特征在于，六氯铱酸钾溶液浓度为0.02-0.04mM，制得Ir-Ni12P5/Ni2P/NF催化剂中Ir与Ni12P5/Ni2P/NF催化剂的质量比为0.01～0.04：1。
  8. 一种权利要求1-5中任意一项所述的制备方法制备Ni12P5/Ni2P/NF催化剂在电催化产氧方面的应用。
  9. 一种权利要求6-7中任意一项所述的制备方法制备Ir-Ni12P5/Ni2P/NF-T催化剂在 电催化产氧方面的应用。
  10. 根据权利要求8-9中任意一项所述的应用，其特征在于：所述电催化水分解的反应所用的电解液为碱性电解液，碱为KOH、NaOH、LiOH、CsOH中的一种，优选为KOH；碱性电解液的浓度为0.5～10M，优选为1M。
PCT/CN2023/103043 2022-07-01 2023-06-28 一维Ni12P5/Ni2P多晶异质结构高效水氧化催化剂的制备方法 WO2024002126A1 (zh)

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