WO2023082449A1 - 多相纳米异质结材料及其制备方法与应用 - Google Patents

多相纳米异质结材料及其制备方法与应用 Download PDF

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WO2023082449A1
WO2023082449A1 PCT/CN2021/143125 CN2021143125W WO2023082449A1 WO 2023082449 A1 WO2023082449 A1 WO 2023082449A1 CN 2021143125 W CN2021143125 W CN 2021143125W WO 2023082449 A1 WO2023082449 A1 WO 2023082449A1
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phase
nano
nise
heterojunction material
mose
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郎建平
薛江燕
倪春燕
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苏州大学
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • 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
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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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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 invention relates to the technical field of nanomaterial preparation, in particular to a multiphase nanometer heterojunction material and its preparation method and application.
  • Hydrogen energy generated by electrolysis of water is considered to be one of the most promising clean energy carriers due to its high energy density, no carbon emissions, and practicality in transportation and distribution.
  • Commercial noble metal catalysts exhibit low overpotential, low Tafel slope, and high current density in the hydrogen production reaction of electrolyzed water, but they face low natural abundance, high price, Serious bottleneck problems such as poor electrochemical stability. Therefore, the development of efficient, low-cost, and abundant raw materials for hydrogen evolution electrocatalysts is the focus of future research.
  • Transition metal chalcogenides have become potential alternatives to noble metal catalysts due to their high activity, low cost, and environmental friendliness.
  • MoSe 2 molybdenum diselenide
  • the technical problem to be solved by the present invention is to provide a preparation method of multi-phase nano-heterojunction materials, successfully preparing four-phase 1T/2H-MoSe 2 -H/R-NiSe and three-phase 1T/2H-MoSe 2 -H-NiSe nano-heterojunction material.
  • This multiphase nano-heterojunction material has a simple synthesis method, and has a large double-layer capacitance, a large electrochemical active area, and a small impedance, which greatly improves the activity and stability of electrocatalytic hydrogen production.
  • the present invention provides a method for preparing a multiphase nano-heterojunction material, comprising the following steps:
  • NiMoO 4 precursor Provide a substrate loaded with NiMoO 4 precursor; dissolve selenium powder in hydrazine hydrate, add water or sodium molybdate aqueous solution, then add the substrate loaded with NiMoO 4 precursor, and react at 180-200°C; After the reaction is finished, the multi-phase nano-heterojunction material is obtained.
  • the obtained heterogeneous nano-heterojunction material is a four-phase 1T/2H-MoSe 2 -H/R-NiSe nano-heterojunction material.
  • the obtained multi-phase nano-heterojunction material is a three-phase 1T/2H-MoSe 2 -H-NiSe nano-heterojunction material.
  • MoSe 2 represents molybdenum diselenide
  • NiSe nickel selenide
  • 1T represents the Trigonal phase of MoSe 2
  • 2H represents the Hexagonal phase of MoSe 2
  • H represents the Hexagonal phase of NiSe
  • R represents the Rhombohedral phase of NiSe.
  • NiMoO 4 -NF is used as a sacrificial template to obtain different multi-phase nano-hybrid materials through surface and interface regulation.
  • element doping and structure optimization are realized, the operation is simple, and rare three-phase products and four-phase products can be obtained. phase product.
  • the preparation process there is no need to introduce surfactants for shape regulation, and the surface of the product is clean and easy to clean; the prepared product can be directly used as a self-supporting electrode material for catalytic hydrogen production, which is convenient and quick.
  • NiMoO 4 can be obtained by growing NiMoO 4 nanorods on a substrate by a hydrothermal method, wherein the substrate is preferably nickel foam (NF).
  • the synthesis method of NiMoO 4 is as follows: nickel nitrate and sodium molybdate are dissolved in deionized water, added to the substrate, and reacted at 150° C. for 6 h to obtain NiMoO 4 nanorods.
  • volume ratio of the hydrazine hydrate to water is 1-2:8-9, preferably 1.6:8.4.
  • the molar ratio of the selenium powder to sodium molybdate is 2:0.5-1, preferably 2:1.
  • reaction temperature is 200°C.
  • reaction time is 2-6 hours.
  • the step of washing and drying the obtained product is also included.
  • the solvent used in the washing is deionized water and absolute ethanol.
  • the washed product is dried using a blast drying oven.
  • the drying temperature is 40-60° C., and the drying time is 2-12 hours. More preferably, the drying temperature is 60° C., and the drying time is 12 hours.
  • Another aspect of the present invention provides a four-phase 1T/2H-MoSe2-H/R-NiSe nano-heterojunction material and a three-phase 1T/2H- MoSe2 -H-NiSe nano-heterojunction prepared by the method Material.
  • the present invention also provides the four-phase 1T/2H-MoSe 2 -H/R-NiSe nano-heterojunction material and the three-phase 1T/2H-MoSe 2 -H-NiSe nano-heterojunction material as electrocatalysts in alkaline Application of catalytic hydrogen evolution reaction under mild conditions.
  • the present invention first adopts the hydrothermal method to generate NiMoO 4 nanorods on the substrate, and then uses them as sacrificial templates to obtain three-phase heterojunction 1T/2H-MoSe 2 -H-NiSe nanosheets and four-phase The heterojunction 1T/2H-MoSe 2 -H/R-NiSe nanorods, the synthesis method is simple, and at the same time, the construction and structure optimization of complex heterojunctions are realized, which is easy to operate.
  • the three-phase heterojunction 1T/2H-MoSe 2 -H-NiSe nanosheets and the four-phase heterojunction 1T/2H-MoSe 2 -H/R-NiSe nanorods prepared by the present invention have larger Double-layer capacitance, larger electrochemically active area, and lower impedance greatly enhance the activity and stability of electrocatalytic hydrogen production.
  • the present invention introduces conductive substrate nickel foam in the preparation process, which can be directly used as a self-supporting electrode material and is easy to operate.
  • the material prepared by the present invention belongs to non-precious metal catalyst, and the price is low.
  • the overpotential value of HER is only 87.6mV, and the Tafel slope is also as low as 139.5mV ⁇ dec -1 at low density.
  • the HER overpotential is only 30.6mV, and the Tafel slope is as low as 132.2mV ⁇ dec -1 .
  • the catalytic activity of 1T/2H-MoSe 2 -H-NiSe nanosheets did not decrease significantly.
  • Fig. 1 is the scanning electron microscope (SEM) figure of precursor NiMoO 4 ;
  • Figure 2 is a scanning electron microscope (SEM) image (a) and a transmission electron microscope (TEM) image (b) of 1T/2H-MoSe 2 -H/R-NiSe, the scale bar is (a) 1 ⁇ m; (b) 500nm;
  • Figure 3 is a high-resolution transmission electron microscope (TEM) image (a, b), energy distribution surface scanning (EDX-Mapping) image (c) and powder X-ray diffraction image (c) of 1T/2H-MoSe 2 -H/R-NiSe d);
  • TEM transmission electron microscope
  • EDX-Mapping energy distribution surface scanning
  • c powder X-ray diffraction image
  • Fig. 4 is an energy dispersive X-ray spectrum (EDX) diagram of 1T/2H-MoSe 2 -H/R-NiSe;
  • Fig. 5 is an X-ray photoelectron spectrum (XPS) diagram of 1T/2H-MoSe 2 -H/R-NiSe;
  • Figure 6 is a scanning electron microscope (SEM) image (a) and a transmission electron microscope (TEM) image (b) of 1T/2H-MoSe 2 -H-NiSe, and the scale bar is (a) 2 ⁇ m; (b) 50nm;
  • Figure 7 is a high-resolution transmission electron microscope (TEM) image (a, b), an energy distribution surface scanning (EDX-Mapping) image (c) and a powder X-ray diffraction image (d) of 1T/2H-MoSe 2 -H-NiSe ;
  • TEM transmission electron microscope
  • EDX-Mapping energy distribution surface scanning
  • d powder X-ray diffraction image
  • Fig. 8 is an energy dispersive X-ray spectrum (EDX) diagram of 1T/2H-MoSe 2 -H-NiSe;
  • Fig. 9 is an X-ray photoelectron spectrum (XPS) diagram of 1T/2H-MoSe 2 -H-NiSe;
  • Figure 10 is the HER of 1T/2H-MoSe 2 -NF, H/R-NiSe-NF, 1T/2H-MoSe 2 -H/R-NiSe and 1T/2H-MoSe 2 -H-NiSe in 1.0M KOH Polarization curve diagram (a), Tafel slope diagram (b), double layer capacitance diagram (c) and Nyquist diagram (d);
  • Fig. 11 is a chronopotentometric titration diagram of 1T/2H-MoSe 2 -H-NiSe.
  • NiMoO 4 -NF where NF stands for nickel foam.
  • the dried NiMoO 4 -NF was calcined at 450° C.
  • the scanning electron microscope image of NiMoO 4 -NF shows that the precursor is a uniform nanorod morphology.
  • 1T/2H-MoSe 2 -H/R-NiSe maintains the morphology of nanorods, but the surface of the rods is composed of nanosheets.
  • 1T/2H-MoSe 2 -H/R-NiSe is composed of 1T phase MoSe 2 , 2H phase MoSe 2 , H phase NiSe and R phase NiSe, and Ni, Se, Mo The three elements are evenly distributed.
  • 1T/2H-MoSe 2 -H-NiSe is composed of 1T phase MoSe 2 , 2H phase MoSe 2 and H phase NiSe, and Ni, Se, and Mo are evenly distributed.
  • 1T/2H-MoSe 2 -H-NiSe photoelectron spectroscopy shows that Ni is +2 valence, Mo is +4 valence, Se is -2 valence, and XPS also shows that MoSe 2 is composed of 1T and 2H phase mixed composition.
  • Embodiment 3 HER performance test in alkaline electrolyte
  • the entire electrocatalytic test is carried out under the standard three-electrode system, in which the working electrode is 1T/2H-MoSe 2 -H/R-NiSe-NF or 1T/2H-MoSe 2 -H-NiSe-NF (the effective area is 0.5cm 2 ), the reference electrode is an Ag/AgCl (saturated chlorine KCl solution) electrode, and the auxiliary electrode is a platinum wire electrode.
  • the electrolyte solution used for the linear sweep voltammetry (LSV) test is 1M KOH solution, the potential scan range is -1.6 ⁇ -1V, and the scan speed is 5mV/s. The test data has not been compensated by iR.
  • both 1T/2H-MoSe 2 -H/R-NiSe-NF and 1T/2H-MoSe 2 -H-NiSe-NF exhibit excellent electrocatalytic performance for HER
  • 1T/2H-MoSe 2 -H-NiSe-NF is even better, at a current density of 10mA cm -2 , the overpotential values are 87.6mV and 30.6mV, and the Tafel slopes are 139.5mV dec -1 and 132.2mV ⁇ dec -1 .
  • the three-phase and four-phase nano-heterojunction materials of the present invention exhibit more excellent electrocatalytic properties.
  • Figure 10(c) and (d) show that the excellent performance of 1T/2H-MoSe 2 -H/R-NiSe-NF and 1T/2H-MoSe 2 -H-NiSe-NF can be attributed to the larger electrochemical active area and less impedance.
  • the performance of 1T/2H-MoSe 2 -H-NiSe-NF did not decrease significantly after 40 hours of stability testing (Fig. 11).
  • the four-phase 1T/2H-MoSe 2 -H/R-NiSe and three-phase 1T/2H-MoSe 2 -H-NiSe nano-heterojunction materials prepared by the present invention have larger double-layer capacitance, electrical
  • the chemically active area and small impedance greatly improve the activity and stability of electrocatalytic hydrogen production, and can be used as a non-noble metal electrocatalyst to catalyze hydrogen evolution reaction under alkaline conditions.

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Abstract

本发明涉及纳米材料技术领域，具体公开了一种多相纳米异质结材料的制备方法，包括以下步骤：提供一负载有NiMoO4前驱物的基底；将硒粉溶于水合肼中，加入水或钼酸钠水溶液，再加入所述负载有NiMoO4前驱物的基底，于180～200℃下进行反应；反应结束后，得到所述多相纳米异质结材料。本发明还提供了由所述方法制备得到的四相1T/2H-MoSe2-H/R-NiSe纳米异质结材料、三相1T/2H-MoSe2-H-NiSe纳米异质结材料以及作为电催化剂在碱性条件下催化氢气析出反应的应用。本发明制备的多相纳米异质结材料，具有较大的双层电容值、较大的电化学活性面积和较小的阻抗，大幅提升了电催化产氢的活性和稳定性。

Description

多相纳米异质结材料及其制备方法与应用 技术领域
本发明涉及纳米材料制备技术领域，具体涉及多相纳米异质结材料及其制备方法与应用。
背景技术
电解水所产生的氢能由于高能量密度，无碳排放和运输配送的实用性被认为是最具发展前景的清洁能源载体之一。(F.Podjaski,D.Weber,S.Zhang,L.Diehl,R.Eger,V.Duppel,E.Alarcón-Lladó,G.Richter,F.Haase,A.Morral,C.Scheu and B.V.Lotsch,Nat.Catal.,2020,3,55–63.)商用贵金属催化剂在电解水产氢反应中表现出低过电位、低Tafel斜率、高电流密度的特性，但是面临着天然丰度低、价格高、电化学稳定性差等严重瓶颈问题。因此，开发高效、低成本、原料丰富的析氢电催化剂是未来研究的重点。
过渡金属硫属化合物具有活性高、成本低、环境友好等优点，已成为潜在的贵金属催化剂替代品。作为典型的具有HER活性的二维层状催化剂，二硒化钼(MoSe 2)因其可调的晶体结构和电子结构、显著的活性和稳定性而受到广泛研究。研究表明，MoSe 2的HER性能受其物相(1T/2H)的影响很大。1T相具有更高的活性，但是热力学不稳定，易转化为导电率和催化活性较低的2H相。此外，单组分的物相电子传输能力较差，催化性能容易触及天花板。构建多相纳米异质结材料可以有效解决这些问题，产生的异质结可以互相弥补缺点，形成一个有协同效应的整体，从而优化电催化剂的固有活性物种、活性位点和导电性，促进催化表面发生的HER反应。(R.Subbaraman,D.Tripkovic,D.Strmcnik,K.-C.Chang,M.Uchimura,A.P.Paulikas,V.Stamenkovic and N.M.Markovic, Science,2011,334,1256.)。Hu等人在金属NiSe纳米线上成功制备了1T-MoSe 2纳米片阵列，将高效产氢和水解离的协同效应耦合到析氢反应中。更重要的是，从NiSe到MoSe 2的电子转移促进了MoSe 2从2H相到1T相的转变，并且50mA cm -2电流密度的过电位为200mV，具有较好的电催化活性。(X.Zhang,Y.Y.Zhang,Y.Zhang,W.J.Jiang,Q.H.Zhang,Y.G.Yang,L.Gu,J.S.Hu and L.J.Wan,Small Methods,2019,3,1800317.)
目前大多数的纳米异质结材料的研究都局限于两种物相，对于更复杂的多相异质结材料的研究很少，并且一些潜在的问题仍然困扰着我们，是否异质结材料的物相越多，性能越好？因此，通过相位调制协同界面工程来调整材料结构，构建高活性高稳定性的MoSe 2基异质结催化剂(>二相)，在电催化领域有重要意义，为大于两相的异质结材料的合理设计和利用开拓新的思路。
发明内容
本发明要解决的技术问题是提供一种多相纳米异质结材料的制备方法，成功地制备得到了四相1T/2H-MoSe 2-H/R-NiSe和三相1T/2H-MoSe 2-H-NiSe纳米异质结材料。这种多相纳米异质结材料合成方法简单，且具有较大的双层电容值、较大的电化学活性面积和较小的阻抗，大幅提升了电催化产氢的活性和稳定性。
为了解决上述技术问题，本发明提供了一种多相纳米异质结材料的制备方法，包括以下步骤：
提供一负载有NiMoO 4前驱物的基底；将硒粉溶于水合肼中，加入水或钼酸钠水溶液，再加入所述负载有NiMoO 4前驱物的基底，于180～200℃下进行反应；反应结束后，得到所述多相纳米异质结材料。
当向水合肼中加入水时，得到的多相纳米异质结材料为四相1T/2H-MoSe 2-H/R-NiSe纳米异质结材料。当向水合肼中加入钼酸钠水溶液时，得到的多相纳米异质结材料为三相1T/2H-MoSe 2-H-NiSe纳米异质结材料。其 中，MoSe 2代表二硒化钼，NiSe代表硒化镍，1T代表MoSe 2的Trigonal相，2H代表MoSe 2的Hexagonal相，H代表NiSe的Hexagonal相，R代表NiSe的Rhombohedral相。
本发明中，以NiMoO 4-NF为牺牲模板，通过表界面调控得到不同的多相纳米杂化材料，同时实现了元素掺杂和结构优化，操作简单，且能得到罕见的三相产物和四相产物。在制备过程中无须引入表面活性剂进行形貌调控，产物表面洁净易清洗；制备得到的产物可以直接用作催化产氢的自支撑电极材料，方便快捷。
本发明中，NiMoO 4可采用水热法在基底生长NiMoO 4纳米棒而得到，其中基底优选为泡沫镍(NF)。优选地，NiMoO 4的合成方法为：将硝酸镍与钼酸钠溶于去离子水中，加入基底，于150℃下反应6h，得到NiMoO 4纳米棒。
进一步地，所述水合肼和水的体积比为1～2:8～9，优选为1.6:8.4。
进一步地，所述硒粉与钼酸钠的摩尔比为2:0.5～1，优选为2:1。
进一步地，所述反应的温度为200℃。
进一步地，反应的时间为2～6h。
进一步地，还包括对得到的产物进行洗涤和干燥的步骤。更进一步地，所述洗涤采用的溶剂为去离子水和无水乙醇。
进一步地，采用鼓风干燥箱对洗涤后的产物进行干燥。优选地，所述干燥温度为40～60℃，干燥时间为2～12h。更优选地，所述干燥温度为60℃，干燥时间为12h。
本发明另一方面提供了由所述的方法制备得到的四相1T/2H-MoSe2-H/R-NiSe纳米异质结材料和三相1T/2H-MoSe 2-H-NiSe纳米异质结材料。
本发明还提供了所述的四相1T/2H-MoSe 2-H/R-NiSe纳米异质结材料和三相1T/2H-MoSe 2-H-NiSe纳米异质结材料作为电催化剂在碱性条件下催化氢气 析出反应的应用。
本发明的有益效果在于：
1.本发明首先采用水热法在基底上生成NiMoO 4纳米棒，然后以其为牺牲模板，水热反应得到三相的异质结1T/2H-MoSe 2-H-NiSe纳米片和四相的异质结1T/2H-MoSe 2-H/R-NiSe纳米棒，合成方法简单，同时实现了复杂异质结的构建和结构优化，便于操作。
2.本发明制备的三相的异质结1T/2H-MoSe 2-H-NiSe纳米片和四相的异质结1T/2H-MoSe 2-H/R-NiSe纳米棒，具有较大的双层电容值，较大的电化学活性面积，和较小的阻抗，大幅提升了电催化产氢的活性和稳定性。
3.本发明在制备过程中引入了导电基底泡沫镍，可直接用作自支撑的电极材料，便于操作。
4.本发明制备的材料属于非贵金属催化剂，价格低廉。
5.本发明制备的1T/2H-MoSe 2-H/R-NiSe纳米棒在碱性电解质(pH＝14)中催化HER反应，表现出了优异的催化性能，在10mA·cm -2的电流密度下，HER过电势的值仅为87.6mV，塔菲尔斜率也低至139.5mV·dec -1。
6.本发明制备的1T/2H-MoSe 2-H-NiSe纳米片在碱性电解质(pH＝14)中催化HER反应，表现出了更优异的催化性能，在10mA·cm -2的电流密度下，HER过电势的值仅为30.6mV，塔菲尔斜率也低至132.2mV·dec -1。经过40小时的稳定性测试，1T/2H-MoSe 2-H-NiSe纳米片的催化活性没有明显的降低。
附图说明
图1是前驱物NiMoO 4的扫描电镜(SEM)图；
图2是1T/2H-MoSe 2-H/R-NiSe的扫描电镜(SEM)图(a)，透射电镜(TEM)图(b)，标尺为(a)1μm；(b)500nm；
图3是1T/2H-MoSe 2-H/R-NiSe的高分辨透射电镜(TEM)图(a，b)，能 量分布面扫描(EDX-Mapping)图(c)和粉末X射线衍射图(d)；
图4是1T/2H-MoSe 2-H/R-NiSe的能量色散X射线光谱(EDX)图；
图5是1T/2H-MoSe 2-H/R-NiSe的X射线光电子能谱(XPS)图；
图6是1T/2H-MoSe 2-H-NiSe的扫描电镜(SEM)图(a)，透射电镜(TEM)图(b)，标尺为(a)2μm；(b)50nm；
图7是1T/2H-MoSe 2-H-NiSe的高分辨透射电镜(TEM)图(a，b)，能量分布面扫描(EDX-Mapping)图(c)和粉末X射线衍射图(d)；
图8是1T/2H-MoSe 2-H-NiSe的能量色散X射线光谱(EDX)图；
图9是1T/2H-MoSe 2-H-NiSe的X射线光电子能谱(XPS)图；
图10是1T/2H-MoSe 2-NF、H/R-NiSe-NF、1T/2H-MoSe 2-H/R-NiSe和1T/2H-MoSe 2-H-NiSe在1.0M KOH中的HER极化曲线图(a)，塔菲尔斜率图(b)，双层电容图(c)和尼奎斯特图(d)；
图11是1T/2H-MoSe 2-H-NiSe的计时电位滴定图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
实施例1：1T/2H-MoSe 2-H/R-NiSe的制备
首先称取0.5mmol的硝酸镍和0.5mmol的钼酸钠溶于15mL去离子水中，然后转移到含有聚四氟乙烯内衬的不锈钢反应釜中，浸入一片泡沫镍 (2cm*2cm)，密封后置于烘箱中，在150℃下反应6h。反应结束后自然冷却至室温，经去离子水和乙醇洗涤，于鼓风干燥箱中60℃干燥后得到前驱物NiMoO 4-NF，其中NF代表泡沫镍(nickle foam)。干燥后的NiMoO 4-NF在氩气气氛中450℃煅烧2小时即得到晶态的NiMoO 4。将2/3mmol的硒粉溶于1.6mL的水合肼溶液中，再加入8.4mL的去离子水，浸入一片煅烧过的NiMoO 4-NF(2cm*2cm)，密封后置于烘箱中，在200℃下反应2h。反应结束后自然冷却至室温，经去离子水和乙醇洗涤，于鼓风干燥箱中60℃干燥后得到1T/2H-MoSe 2-H/R-NiSe。
如图1所示，NiMoO 4-NF的扫描电镜图显示前驱物是均一的纳米棒形貌。
如图2所示，1T/2H-MoSe 2-H/R-NiSe保持了纳米棒的形貌，但是棒的表面是由纳米片组成的。
如图3所示，1T/2H-MoSe 2-H/R-NiSe是由1T相的MoSe 2，2H相的MoSe 2，H相的NiSe和R相的NiSe组成的，且Ni，Se，Mo三种元素均匀分布。
如图4所示，Ni，Se，Mo三种元素的含量与结构大体一致。
如图5所示，1T/2H-MoSe 2-H/R-NiSe光电子能谱(XPS)显示Ni是+2价，Mo是+4价，Se是-2价，且XPS也显示了MoSe 2是由1T和2H相混合组成的。
实施例2：1T/2H-MoSe 2-H-NiSe的制备
将2/3mmol的硒粉溶于1.6mL的水合肼溶液中，将1/3mmol钼酸钠溶于8.4mL的去离子水中并与水合肼溶液混合均匀，浸入一片煅烧过的NiMoO 4-NF(2cm*2cm)，密封后置于烘箱中，在200℃下反应2h。反应结束后自然冷却至室温，经去离子水和乙醇洗涤，于鼓风干燥箱中60℃干燥后得到1T/2H-MoSe 2-H-NiSe。
如图6所示，1T/2H-MoSe 2-H-NiSe的形貌不再是纳米棒，而是彻底演化成了纳米片。
如图7所示，1T/2H-MoSe 2-H-NiSe是由1T相的MoSe 2，2H相的MoSe 2 和H相的NiSe组成的，且Ni，Se，Mo三种元素均匀分布。
如图8所示，Ni，Se，Mo三种元素的含量与结构大体一致。
如图9所示，1T/2H-MoSe 2-H-NiSe光电子能谱(XPS)显示Ni是+2价，Mo是+4价，Se是-2价，且XPS也显示了MoSe 2是由1T和2H相混合组成的。
实施例3：碱性电解质中HER性能测试
整个电催化测试都是在标准的三电极体系下进行，其中工作电极为1T/2H-MoSe 2-H/R-NiSe-NF或1T/2H-MoSe 2-H-NiSe-NF(有效面积为0.5cm 2)，参比电极为Ag/AgCl(饱和氯KCl溶液)电极，辅助电极为铂丝电极。用于线性扫描伏安法(LSV)测试的电解质溶液为1M KOH溶液，电势的扫描范围为-1.6～-1V，扫描速度为5mV/s，测试的数据没有经过iR的补偿。
如图10(a)、(b)所示，1T/2H-MoSe 2-H/R-NiSe-NF和1T/2H-MoSe 2-H-NiSe-NF都表现出优异的HER电催化性能，但是1T/2H-MoSe 2-H-NiSe-NF更胜一筹，在10mA·cm -2的电流密度下，过电势的值分别为87.6mV和30.6mV，塔菲尔斜率分别为139.5mV·dec -1和132.2mV·dec -1。与1T/2H-MoSe 2-NF和H/R-NiSe-NF相比，本发明的三相和四相纳米异质结材料都展现了更优异的电催化性能。
图10(c)和(d)表明，1T/2H-MoSe 2-H/R-NiSe-NF和1T/2H-MoSe 2-H-NiSe-NF的优异性能可归因于较大的电化学活性面积和较小的阻抗。1T/2H-MoSe 2-H-NiSe-NF在经过40小时的稳定性测试后，性能没有明显降低(图11)。
综上，本发明制备的四相1T/2H-MoSe 2-H/R-NiSe和三相1T/2H-MoSe 2-H-NiSe纳米异质结材料，具有较大的双层电容值、电化学活性面积和较小的阻抗，大幅提升了电催化产氢的活性和稳定性，可作为在碱性条件下催化氢气析出反应的非贵金属电催化剂。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或 变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。

Claims (10)

  1. 一种多相纳米异质结材料的制备方法，其特征在于，包括以下步骤：
    提供一负载有NiMoO 4前驱物的基底；
    将硒粉溶于水合肼中，加入水或钼酸钠水溶液，再加入所述负载有NiMoO 4前驱物的基底，于180～200℃下进行反应；反应结束后，得到所述多相纳米异质结材料。
  2. 根据权利要求1所述的多相纳米异质结材料的制备方法，其特征在于，当向水合肼中加入水时，得到的多相纳米异质结材料为四相1T/2H-MoSe 2-H/R-NiSe纳米异质结材料；
    当向水合肼中加入钼酸钠水溶液时，得到的多相纳米异质结材料为三相1T/2H-MoSe 2-H-NiSe纳米异质结材料。
  3. 根据权利要求1所述的多相纳米异质结材料的制备方法，其特征在于，所述基底为泡沫镍。
  4. 根据权利要求1所述的多相纳米异质结材料的制备方法，其特征在于，所述水合肼和水的体积比为1～2:8～9。
  5. 根据权利要求1所述的多相纳米异质结材料的制备方法，其特征在于，所述硒粉与钼酸钠的摩尔比为2:0.5～1。
  6. 根据权利要求1所述的多相纳米异质结材料的制备方法，其特征在于，反应的时间为2～6h。
  7. 根据权利要求1所述的多相纳米异质结材料的制备方法，其特征在于，还包括对得到的产物进行洗涤和干燥的步骤，所述洗涤采用的溶剂为去离子水和无水乙醇。
  8. 根据权利要求7所述的多相纳米异质结材料的制备方法，其特征在于，所述干燥温度为40～60℃，干燥时间为2～12h。
  9. 根据权利要求1～8任一项所述的方法制备得到的四相1T/2H-MoSe 2-H/R-NiSe纳米异质结材料和三相1T/2H-MoSe 2-H-NiSe纳米异质结材料。
  10. 权利要求9所述的四相1T/2H-MoSe 2-H/R-NiSe纳米异质结材料和三相1T/2H-MoSe 2-H-NiSe纳米异质结材料作为电催化剂在碱性条件下催化氢气析出反应的应用。
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