CN111871427A - Precious metal/molybdenum-nickel composite material and preparation method and application thereof - Google Patents

Precious metal/molybdenum-nickel composite material and preparation method and application thereof Download PDF

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CN111871427A
CN111871427A CN202010687438.7A CN202010687438A CN111871427A CN 111871427 A CN111871427 A CN 111871427A CN 202010687438 A CN202010687438 A CN 202010687438A CN 111871427 A CN111871427 A CN 111871427A
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molybdenum
nickel
inorganic
noble metal
composite material
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CN111871427B (en
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刘碧录
杨丰宁
罗雨婷
余强敏
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Tsinghua-Berkeley Shenzhen Institute Preparation Office
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • B01J35/23—
    • B01J35/33—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention discloses a noble metal/molybdenum-nickel composite material and a preparation method and application thereof, wherein the noble metal/molybdenum-nickel composite material comprises a molybdenum-nickel material with a three-dimensional structure and a noble metal loaded on the molybdenum-nickel material; the molybdenum-nickel material comprises ABO4A core of a type compound, and an ABO dispersed in said ABO4Around the core of the type compoundsAB alloy and B oxide, wherein A is any one of iron, cobalt, nickel, copper and zinc, and B is VIB group element. The noble metal/molybdenum-nickel composite material has the advantages of adjustable noble metal loading capacity and high noble metal dispersion, has excellent catalytic performance, and has good application prospect in the fields of hydrogen production by water electrolysis and the like.

Description

Precious metal/molybdenum-nickel composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a noble metal/molybdenum-nickel composite material and a preparation method and application thereof.
Background
Environmental pressure and energy shortages worldwide place new demands on the upgrading of energy systems. As a renewable energy source, hydrogen energy has a good application prospect because the hydrogen energy is clean and pollution-free in the using process and has energy density twice higher than that of fossil energy (gasoline). Hydrogen production by water electrolysis is one of the current environmentally friendly and sustainable hydrogen production methods, which can be driven by external voltage to decompose water into hydrogen and oxygen without producing any other by-products. The water electrolysis hydrogen production technology can be effectively combined with other new energy technologies, especially the electric energy generated by wind energy and solar energy is converted into chemical energy to be stored in hydrogen, so that the energy utilization rate can be improved, the energy waste is avoided, and the use and sustainable development of clean energy are realized.
However, compared with hydrogen production by methane reforming and hydrogen production by coal gasification, hydrogen production by water electrolysis has no economic advantage at present, and the cost is about one to two times of that of other methods. Therefore, how to further improve the efficiency of hydrogen production by water electrolysis so as to reduce the cost is an important technical problem in the field. To date, much research has focused on low hydrogen production rates (low current densities, e.g., 10mA cm)-2) Has excellent catalytic performance and high hydrogen production rate (high current density, for example)>1000mA cm-2) The problem of deterioration of the lower catalytic performance is difficult to overcome, and the requirement of improving the hydrogen evolution efficiency in practical application cannot be met. Therefore, the search for the water electrolysis catalyst with high catalytic activity and high stability under high current density is the key point and difficulty of the current electrocatalysis research.
CN109225257A discloses a supported monatomic catalyst and a preparation method thereof. The catalyst is formed by uniformly loading monodisperse metal atoms on the surface of a nano substrate material. The preparation method comprises the following steps: in an electrolyte solution containing metal salt, performing electrochemical deposition by adopting a three-electrode system, taking a glassy carbon electrode loaded with a nano substrate material as a working electrode, taking a graphite rod as a counter electrode, taking a silver/silver chloride electrode as a reference electrode, and performing linear voltammetry scanning to ensure that metal atoms are monodispersed and uniformly deposited on the nano substrate material to obtain the supported monatomic catalyst. The supported monatomic catalyst has a single structure, is developed into a catalyst with rich nano-structure, high performance and high stability, and has important significance for the field. Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a noble metal/molybdenum-nickel composite material, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, a noble metal/molybdenum-nickel composite material is provided, which is characterized by comprising a molybdenum-nickel material having a three-dimensional structure and a noble metal supported on the molybdenum-nickel material; the molybdenum-nickel material comprises ABO4A core of a type compound, and an ABO dispersed in said ABO4AB alloy around the core of the type compound and B oxide, wherein A is any one of Fe, Co, Ni, Cu and Zn, and B is VIB group element.
AB alloy means an alloy containing A and B, e.g. MoNi4、MoNi3。
According to some embodiments of the invention, B is molybdenum or tungsten.
According to some embodiments of the invention, the three-dimensional structure comprises a rod, flower, or tube.
According to some embodiments of the invention, the ABO4The core of the type compound is a nickel molybdate core, the AB alloy is a molybdenum-nickel alloy, and the oxide of the B is an oxide of molybdenum.
According to some embodiments of the invention, the oxide of molybdenum comprises at least one of molybdenum dioxide, molybdenum trioxide; the molybdenum-nickel alloy bagIncluding MoNi4、MoNi3At least one of (1).
According to some embodiments of the invention, the noble metal comprises at least one of gold, silver, platinum group metals. The platinum group metals include ruthenium (Ru), iridium (Ir), rhodium (Rh), osmium (Os), palladium (Pd), and platinum (Pt).
In a second aspect of the present invention, there is provided a method for preparing the above noble metal/molybdenum-nickel composite material, comprising the following steps:
carrying out hydrothermal reaction on a precursor mixed solution or a precursor mixed solution added into a substrate in a closed container, wherein the precursor mixed solution comprises a precious metal precursor, an inorganic B source precursor and an inorganic A source precursor;
and introducing inert gas and reducing gas, and carrying out reduction reaction to obtain the noble metal/molybdenum-nickel composite material.
In the process of synthesizing by a hydrothermal method, a high valence oxide of VIB group elements with relatively large atomic radius is taken as a basic crystal form structure, iron, cobalt, nickel, copper, zinc and other elements with relatively small atomic radius replace part of VIB group element atoms, and the structure of the original oxide is still kept, so that the ABO is similar to that of the VIB group elements4The structures of the substances all show similar crystal forms, and the prepared composite materials can form ABO4Core structure of the compound.
The mode of adopting the closed container ensures that the hydrothermal reaction is carried out in a certain pressure intensity, and has the following advantages: 1. the possibility of preparing the composite material is ensured. If the reaction is carried out at normal pressure (in an open container) at the temperature of the hydrothermal reaction, the solvent aqueous solution will evaporate, thereby affecting the concentration of the precursor, and the crystalline phase structure of the intermediate specified in the present application, and the three-dimensional structure specified in the present application, cannot be formed under the pressure condition and the solvent condition of the reaction. 2. The effectiveness of the reaction is ensured. In a closed container, the saturated vapor pressure of a solvent, such as an aqueous solution, increases with increasing temperature, resulting in a change in pressure throughout the container. If the hydrothermal reaction temperature is 60-200 ℃, the saturated vapor pressure is changed from-15 kPa to-1500 kPa, so different morphological structures are generated, including three-dimensional structures such as rod-shaped, flower-shaped, tubular and the like, and therefore, the pressure belongs to an important index, and the three-dimensional structures cannot be generated if the hydrothermal reaction is not carried out in a closed container.
The process of carrying out the reduction reaction using a reducing gas has the following advantages: 1. improving the conductivity of the composite material, and obtaining an intermediate containing noble metal oxide and ABO through the hydrothermal reaction treatment of the previous step4The conductivity of the core of the type compound (such as nickel molybdate) is difficult to meet the performance of subsequent application, and after reduction reaction treatment, the molybdenum-nickel alloy and noble metal nanoparticles can be formed on the surface, so that the conductivity of the composite material is greatly improved, and the performance of subsequent application is further improved. 2. By utilizing the advantage that the reduction potential of the noble metal at the active site is lower than that of the transition metal, the noble metal mixed in the composite material is separated out on the surface, so that the noble metal is enriched on the surface of the composite material. For example, the enthalpy of formation Δ H ° (298.15K) — 167(± 42) kJ · mol-1 of platinum oxide, the enthalpy of formation Δ H ° (298.15K) — 130(± 20) of ruthenium oxide is Δ H ° (298.15K) — 1335.0(± 0.9) of molybdenum trioxide, and the enthalpy of formation Δ H ° (298.15K) — 239.8(± 0.05) kJ · mol-1 of nickel oxide. Therefore, in the reducing atmosphere, the noble metal platinum ruthenium is more easily reduced and deposited on the surface. Therefore, after the reduction reaction treatment, the concentration gradient dispersion structure with the enriched precious metal on the surface is obtained.
According to some embodiments of the invention, the reducing gas comprises at least one of hydrogen, natural gas.
According to some embodiments of the invention, the inert gas comprises argon and/or nitrogen. The argon and/or nitrogen may be argon, nitrogen or a combination of argon and nitrogen.
Preferably, the inert gas is introduced at a rate of 50 to 95 sccm. Preferably, the reducing gas is introduced at a rate of 1 to 20 sccm.
According to some embodiments of the invention, the inorganic a source precursor comprises any one of an inorganic iron source precursor, an inorganic cobalt source precursor, an inorganic nickel source precursor, an inorganic copper source precursor, and an inorganic zinc source precursor, and the inorganic B source precursor comprises an inorganic molybdenum source precursor, an inorganic tungsten sourceAny one of the precursors; preferably, the inorganic iron source precursor comprises any one of ferric chloride, ferric nitrate and ferric sulfate, the inorganic cobalt source precursor comprises any one of cobalt nitrate, cobalt chloride and cobalt sulfate, the inorganic nickel source precursor comprises any one of nickel nitrate, nickel chloride and nickel sulfate, the inorganic copper source precursor comprises any one of copper chloride, copper nitrate and copper sulfate, and the inorganic zinc source precursor comprises any one of zinc chloride, zinc nitrate and zinc sulfate; the inorganic molybdenum source precursor comprises any one of molybdic acid, ammonium molybdate, sodium molybdate and potassium molybdate, and the inorganic tungsten source precursor comprises any one of tungstic acid, ammonium tungstate, potassium tungstate and sodium tungstate. The organic precursor can volatilize at high temperature and can not form ABO4The core structure of the compound (such as nickel molybdate) generally needs to be added with a carrier with high specific surface area to provide a growth site during the preparation process so as to grow and catalyze, and the noble metal particles which play a catalytic role grow on the carrier. Whereas the present application utilizes ABO that inorganic precursors are capable of forming4The core of the type compound (such as nickel molybdate) is used as a carrier for improving the specific surface area, noble metal and molybdenum-nickel alloy particles with active sites are provided, the special addition of the carrier with high specific surface area is not needed, an inorganic precursor can form a three-dimensional structure through spontaneous nucleation in a hydrothermal reaction, and the noble metal can be embedded into the crystal lattice of the carrier in the nucleation process, so that the integrity and the mechanical stability of the composite material can be greatly improved. In addition, the noble metal is more easily reduced during the reduction reaction than A, B element in the inorganic precursor, and thus a stable crystalline phase structure can still be maintained.
According to some embodiments of the invention, the temperature of the hydrothermal reaction is 60 to 200 ℃; preferably, the time of the hydrothermal reaction is 2-10 h.
According to some embodiments of the invention, the temperature of the reduction reaction is 100 to 1000 ℃; preferably, the temperature of the reduction reaction is 450-550 ℃. Preferably, the time of the reduction reaction is 1-360 min.
According to some embodiments of the invention, the reduction reaction is carried out by heating at an elevated temperatureThe heating rate is 1-50 deg.C min-1(ii) a Preferably, the substrate is any one of metal foam, doped metal foam, porous metal, porous carbon. The size of the substrate used may depend on the size of the containment vessel.
According to some embodiments of the invention, the noble metal precursor: inorganic molybdenum source precursor: the molar ratio of the inorganic nickel source precursor is (0.2-2): (10-40): 80. different three-dimensional structures can be obtained by changing the proportion of the added precursor in the preparation process.
In a third aspect of the invention, the application of the precious metal/molybdenum-nickel composite material in hydrogen production by water electrolysis, fuel cells, methanol oxidation reaction, ethanol oxidation reaction, supercapacitors and ion batteries is provided.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a noble metal/molybdenum-nickel composite material with a three-dimensional structure, which can provide enough electrochemical active area through the abundant three-dimensional structure, so that the noble metal is highly dispersed, and the consumption of the noble metal is reduced.
The embodiment of the invention also provides a preparation method of the noble metal/molybdenum-nickel composite material, wherein an inorganic precursor is selected as a reaction raw material, an intermediate with a specific crystal phase is firstly synthesized in a closed container through hydrothermal reaction, then the surface of the composite material is alloyed through reduction treatment, and meanwhile, the noble metal mixed in the composite material is separated out on the surface of the composite material and is enriched on the surface by utilizing the advantage of low reduction potential of the active site of the noble metal, so that AB alloy and noble metal nano particles are formed on the surface of the composite material, the conductivity of the composite material is greatly improved, and the performance of subsequent application is further improved. In addition, when a substrate is added to prepare a film composite material sample, the hydrothermal treatment and the reduction treatment of the embodiment of the invention can improve the binding force between the noble metal/molybdenum-nickel composite material and the substrate, thereby achieving the purpose of greatly improving the overall reaction performance and stability.
Drawings
FIG. 1 is an X-ray diffraction spectrum of an intermediate platinum/molybdenum nickel compound in example 1;
FIG. 2 shows the Pt/MoNi composite material finally obtained in example 14@NiMoO4The scanning electron microscope picture of (a);
FIG. 3 shows the Pt/MoNi composite material obtained in example 14@NiMoO4Transmission electron microscopy images of;
FIG. 4 shows the Pt/MoNi composite material finally obtained in example 14@NiMoO4Low power transmission electron microscope-energy spectrum picture;
FIG. 5 shows the Pt/MoNi composite material finally obtained in example 14@NiMoO4X-ray diffraction spectrum of (a);
FIG. 6 shows the Pt/MoNi composite material finally obtained in example 14@NiMoO4High power transmission electron microscope pictures and lattice fringe pictures of different components;
FIG. 7 shows a Mo-Ni alloy composite MoNi of comparative example 14@NiMoO4X-ray diffraction spectrum of (a);
FIG. 8 is a plot of current density versus voltage for the materials of example 1 and comparative examples 1-3;
FIG. 9 is a plot of current density versus voltage for the materials of example 2, comparative example 1, and comparative example 4;
FIG. 10 is a graph of current density versus voltage for the noble metal/molybdenum-nickel based composites of examples 3-5;
FIG. 11 shows the Pt/MoNi composite material of noble metal/Mo-Ni prepared in example 54@NiMoO4Scanning electron microscope images of;
FIG. 12 is a graph of current density versus voltage for the noble metal/molybdenum-nickel based composites of examples 5, 6 and 7;
FIG. 13 is a SEM picture of a noble metal/Mo-Ni based composite material prepared in example 5;
FIG. 14 is a scanning electron microscope photograph of the noble metal/molybdenum-nickel based composite material prepared in example 6;
FIG. 15 is a SEM picture of a noble metal/Mo-Ni based composite material prepared in example 7;
FIG. 16 is a graph showing the size distribution of surface particles of three noble metal/molybdenum-nickel based composite materials prepared in examples 5 to 7;
FIG. 17 is a graph of current density versus voltage for the noble metal/molybdenum-nickel based composites of examples 1, 8-12.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4The preparation method comprises the following steps:
(1) according to a molar ratio of 1: 20: 80 respectively taking a noble metal precursor (chloroplatinic acid), an inorganic molybdenum source precursor (ammonium molybdate) and an inorganic nickel source precursor (nickel nitrate), adding the noble metal precursor (chloroplatinic acid), the inorganic molybdenum source precursor (ammonium molybdate) and the inorganic nickel source precursor (nickel nitrate) into 30mL of deionized water, mixing to form a precursor mixed solution, placing the precursor mixed solution into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ so that platinum-containing molybdenum-nickel oxide uniformly grows on foamed nickel (an electrode current collector) to obtain an intermediate platinum/molybdenum-nickel compound electrode;
(2) placing the platinum/molybdenum-nickel compound electrode prepared in the step (1) in a heating central area of a horizontal tubular furnace, introducing 300sccm inert gas (argon and/or nitrogen) to remove air, continuously introducing 95sccm inert gas into the horizontal tubular furnace, heating the reaction furnace to 500 ℃, and keeping the condition of introducing 95sccm inert gasUnder the condition of reducing reaction, introducing reducing gas (hydrogen) at the rate of 5sccm, and preserving heat for 15 min; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reducing the temperature of the reaction system to 25 ℃ to obtain the noble metal/molybdenum-nickel composite material Pt/MoNi with the three-dimensional structure4@NiMoO4。
The intermediate platinum/molybdenum nickel compound prepared in the step (1) is subjected to X-ray diffraction spectrum characterization, and the result is shown in fig. 1, which indicates that the intermediate comprises nickel molybdate without crystal water and nickel molybdate with crystal water in the crystal phase structure.
FIG. 2 shows the Pt/MoNi composite material finally obtained in this example4@NiMoO4Fig. 3 is a drawing of a scanning electron microscope showing the precious metal/molybdenum-nickel composite material Pt/MoNi finally obtained in this example4@NiMoO4The three-dimensional structure of the material shows a rod-like structure.
FIG. 4 shows the Pt/MoNi composite material finally obtained in this example4@NiMoO4The low power transmission electron microscope-energy spectrum picture of (2) again proves that the substance is composed of MO, Ni and Pt elements and is distributed more uniformly. FIG. 5 shows the Pt/MoNi composite material finally obtained in this example4@NiMoO4The result shows that the composite material contains simple substance nickel and molybdenum-nickel-four (molybdenum-nickel alloy MoNi)4) Molybdenum dioxide and nickel molybdate.
FIG. 6 shows the Pt/MoNi composite material finally obtained in this example4@NiMoO4The high-power transmission electron microscope picture and the lattice stripe picture of different components show that, in the composite material structure, the inside is nickel molybdate (marked as e in the figure), molybdenum dioxide particles (marked as d in the figure) and molybdenum-nickel-four (marked as c in the figure) are dispersed outside, and noble metal Pt particles (marked as b in the figure) are separated out and enriched on the surface of the composite material.
Effect example 1
Comparative example 1: comparative example 1 provides a molybdenum-nickel alloy composite MoNi without noble metals4@NiMoO4The preparation process is the same as that of example 1, except that no noble metal precursor is added in the step (1), and the specific preparation process is as follows:
(1) according to a molar ratio of 20: 80, respectively taking an inorganic molybdenum source precursor (ammonium molybdate) and an inorganic nickel source precursor (nickel nitrate), adding the inorganic molybdenum source precursor and the inorganic nickel source precursor (nickel nitrate) into 30mL of deionized water, mixing, placing the mixture into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ to enable molybdenum-nickel oxide to uniformly grow on the electrode current collector foamed nickel;
(2) placing the molybdenum-nickel oxide electrode prepared in the step (1) in a horizontal tubular furnace to obtain a heating central area, introducing 300sccm inert gas (argon and/or nitrogen) to remove air, continuously introducing 95sccm inert gas into the horizontal tubular furnace, heating the reaction furnace to 500 ℃, introducing reaction gas (hydrogen) at a rate of 5sccm under the condition of keeping the introduction of 95sccm inert gas, and keeping the temperature for 15min to perform heating reaction; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reducing the temperature of the reaction system to 25 ℃ to obtain the noble metal-free molybdenum-nickel alloy composite MoNi4@NiMoO4。
Comparative example 2: comparative example 2 provides a blank nickel foam electrode.
Comparative example 3: comparative example 2 provides a glassy carbon electrode, and a platinum carbon electrode is a catalyst for hydrogen production by electrolysis of water, which is commercially available at present, and has good catalytic activity. Compared with the electrocatalytic performance of a platinum-carbon electrode, the electrocatalytic hydrogen production activity of the noble metal/molybdenum-nickel composite material prepared in example 1 can be intuitively felt. The specific preparation process of the platinum-carbon electrode comprises the following steps:
(1) 3mg of 20% Pt/C solid powder was dispersed in 5mL of a 30: 29: 1 ethanol/deionized water/5 wt% Nafion solution, and ultrasonically oscillating to form a mixed solution;
(2) cutting the foamed nickel into 1 × 1.5cm rectangles, and ultrasonically cleaning the rectangles by using ethanol;
(3) and (3) absorbing the mixed solution under the baking of an infrared lamp, uniformly dripping the mixed solution on the front side and the back side of the cleaned foamed nickel, and dripping the mixed solution again after the mixed solution is baked until all the liquid is dripped, thus obtaining the glassy carbon electrode.
FIG. 7 shows a Mo-Ni alloy composite MoNi of comparative example 14@NiMoO4The composite material comprises elementary nickel, molybdenum-nickel alloy and molybdenum dioxide crystal phase species, and the reason why the nickel molybdate core is not formed is that the nickel molybdate synthesized in the hydrothermal method is completely reduced in the thermal reduction step. In example 1, the noble metal is preferentially reduced due to the addition of the noble metal, and the internal nickel molybdate core is reduced later. The inner core nickel molybdate was not completely reduced due to the short annealing time. However, in comparative example 1, nickel molybdate was directly reduced without addition of a noble metal, resulting in complete reduction of all nickel molybdate, and thus no nickel molybdate species was present.
The noble metal/molybdenum-nickel composite material Pt/MoNi finally prepared in the example 1 is taken4@NiMoO4Molybdenum-nickel alloy composite material MoNi in comparative example 14@NiMoO4The blank nickel foam electrolysis in the comparative example 2 and the glassy carbon electrode in the comparative example 3 are used as electrode samples to carry out electrochemical performance tests, and the test method comprises the following steps: linear sweep voltammetry. The obtained current density-voltage curve is shown in FIG. 8, from which it can be seen that the Mo-Ni alloy composite material MoNi without noble metal prepared in comparative example 14@NiMoO4In the hydrogen production half-reaction of (2), at 2000mA cm-2The overpotential under the large current density is 202mV, the main reason is that no noble metal precursor is added in the comparative example 1, so that the noble metal cluster precipitated on the surface is provided for improving the main performance in the noble metal/molybdenum-nickel composite material of the embodiment of the invention. The open potential of the nickel foam electrode in comparative example 2 had reached 205mV at 2000mA cm-2The overpotential under the heavy current density is 605mV, and the electrocatalytic hydrogen production performance is seriously deteriorated, which indicates that the copper foam is an inert substance and has low contribution to the electrocatalytic hydrogen production. Comparative example 3 in which the glassy carbon electrode was at 2000mA cm-2The overpotential already exceeds 750mV under large current density. The noble metal/molybdenum-nickel composite material Pt/MoNi prepared in the example 14@NiMoO4Has a low initial overpotential of 2000mA cm-2The overpotential under the large current density is only 109mV, which shows thatThe noble metal/molybdenum-nickel composite material provided by the embodiment of the invention has better electrocatalytic hydrogen production performance.
Example 2
The embodiment provides a noble metal/molybdenum-nickel composite material Ru/MoNi with a three-dimensional structure4@NiMoO4The preparation method comprises the following steps:
(1) according to a molar ratio of 1: 20: 80 respectively taking a noble metal precursor (ruthenium chloride), an inorganic molybdenum source precursor (ammonium molybdate), an inorganic nickel source precursor (nickel chloride) and foam nickel with the size of 1 x 3cm, adding the noble metal precursor (ruthenium chloride), the inorganic molybdenum source precursor (ammonium molybdate) and the inorganic nickel source precursor (nickel chloride) into 30mL of deionized water, mixing to form a precursor mixed solution, placing the precursor mixed solution into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ to uniformly grow ruthenium-containing molybdenum nickel oxide on an electrode current collector to obtain an intermediate ruthenium-molybdenum nickel oxide electrode;
(2) placing the ruthenium-molybdenum-nickel oxide electrode prepared in the step (1) in a horizontal tubular furnace to obtain a heating central area, introducing 300sccm inert gas (argon and/or nitrogen) to remove air, continuously introducing 95sccm inert gas into the horizontal tubular furnace, heating the reaction furnace to 500 ℃, introducing 5sccm reaction gas (hydrogen) under the condition of keeping the introduction of 95sccm inert gas, and keeping the temperature for 15min to perform heating reaction; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reducing the temperature of the reaction system to 25 ℃ to obtain the noble metal/molybdenum-nickel composite material Ru/MoNi with the three-dimensional structure4@NiMoO4。
Effect example 2
Comparative example 4: comparative example 4 provides an iridium oxide electrode, which is an electrolytic aqueous oxygen catalyst that has been commercialized so far, having good catalytic activity. Compared with the electrocatalytic performance of an iridium oxide electrode, the electrocatalytic oxygen generation activity of the noble metal/molybdenum-nickel composite material prepared in example 2 can be intuitively felt. The specific preparation process of the iridium oxide electrode comprises the following steps:
(1) 4.5mg of iridium oxide solid powder was dispersed in 50mL of a solid dispersion having a volume ratio of 48: 1: 1 ethanol/deionized water/5 wt% Nafion solution, and ultrasonically oscillating to form a mixed solution;
(2) cutting the foamed nickel into 1 × 1.5cm rectangles, and ultrasonically cleaning the rectangles by using ethanol;
(3) and (3) absorbing the mixed solution under the baking of an infrared lamp, uniformly dripping the mixed solution on the front side and the back side of the cleaned foamed nickel, and dripping the mixed solution again after the mixed solution is baked until all the liquid is dripped, thus obtaining the iridium oxide electrode.
The precious metal/molybdenum-nickel composite material Ru/MoNi finally prepared in the example 2 is taken4@NiMoO4Molybdenum-nickel alloy composite material MoNi in comparative example 14@NiMoO4And the iridium oxide electrode in the comparative example 4 is used as an electrode sample to carry out electrochemical performance test, and the test method comprises the following steps: linear sweep voltammetry. The current density curve with voltage was obtained as shown in FIG. 9, from which it can be seen that the iridium oxide electrode in comparative example 4 was 2000mA cm-2The working potential reaches 2300mV under large current density, and the noble metal/molybdenum-nickel composite material Ru/MoNi prepared in the example 24@NiMoO4Has low initial overpotential at 2000mAcm-2The overpotential under the large current density is only 420mV, which shows that the noble metal/molybdenum-nickel composite material provided by the embodiment of the invention has better electrocatalytic oxygen generation performance.
Example 3
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4The preparation method comprises the following steps:
(1) according to a molar ratio of 0.2: 20: 80 respectively taking a noble metal precursor (chloroplatinic acid), an inorganic molybdenum source precursor (ammonium molybdate) and an inorganic nickel source precursor (nickel nitrate), adding the noble metal precursor (chloroplatinic acid), the inorganic molybdenum source precursor (ammonium molybdate) and the inorganic nickel source precursor (nickel nitrate) into 30mL of deionized water, mixing to form a precursor mixed solution, placing the precursor mixed solution into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ so that platinum-containing molybdenum-nickel oxide uniformly grows on foamed nickel (an electrode current collector) to obtain an intermediate platinum/molybdenum-nickel compound electrode;
(2) placing the platinum/molybdenum-nickel compound electrode prepared in the step (1) in a heating central area of a horizontal tubular furnace, introducing 300sccm inert gas (argon and/or nitrogen) to remove air, and continuously introducing the inert gas into the horizontal tubular furnaceAdding inert gas with the flow rate of 95sccm, heating the reaction furnace to 600 ℃, introducing reducing gas (hydrogen) at the flow rate of 5sccm under the condition of keeping introducing the inert gas of 95sccm, and preserving the temperature for 120min to perform a reduction reaction; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reducing the temperature of the reaction system to 25 ℃ to obtain the noble metal/molybdenum-nickel composite material Pt/MoNi with the three-dimensional structure4@NiMoO4。
The noble metal/molybdenum-nickel composite material of the embodiment is taken as an electrode sample to carry out electrochemical performance test, and the test method comprises the following steps: linear sweep voltammetry. The resulting current density versus voltage curve is shown in FIG. 10, from which it can be seen that the noble metal/molybdenum-nickel composite of example 3 has a lower initial overpotential at 500mA cm-2The overpotential under the large current density is only 270mV, which shows that the noble metal/molybdenum-nickel composite material provided by the embodiment of the invention has better electrocatalytic hydrogen production performance.
Example 4
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4The difference from example 3 is that the Pt precursor was prepared according to the following procedure, in terms of the amount of Pt precursor added:
(1) according to a molar ratio of 1: 20: 80 respectively taking a noble metal precursor (chloroplatinic acid), an inorganic molybdenum source precursor (ammonium molybdate) and an inorganic nickel source precursor (nickel nitrate), adding the noble metal precursor (chloroplatinic acid), the inorganic molybdenum source precursor (ammonium molybdate) and the inorganic nickel source precursor (nickel nitrate) into 30mL of deionized water, mixing to form a precursor mixed solution, placing the precursor mixed solution into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ so that platinum-containing molybdenum-nickel oxide uniformly grows on foamed nickel (an electrode current collector) to obtain an intermediate platinum/molybdenum-nickel compound electrode;
(2) placing the platinum/molybdenum-nickel compound electrode prepared in the step (1) in a heating central area of a horizontal tubular furnace, introducing 300sccm inert gas (argon and/or nitrogen) to remove air, continuously introducing 95sccm inert gas into the horizontal tubular furnace, heating the reaction furnace to 600 ℃, and introducing reducing gas at a rate of 5sccm under the condition of keeping introducing 95sccm inert gas(hydrogen) and preserving the temperature for 120min for reduction reaction; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reducing the temperature of the reaction system to 25 ℃ to obtain the noble metal/molybdenum-nickel composite material Pt/MoNi with the three-dimensional structure4@NiMoO4。
The noble metal/molybdenum-nickel composite material of the embodiment is taken as an electrode sample to carry out electrochemical performance test, and the test method comprises the following steps: linear sweep voltammetry. The resulting current density versus voltage curve is shown in FIG. 10, from which it can be seen that the noble metal/molybdenum-nickel composite of example 4 has a lower initial overpotential at 500mA cm-2The overpotential under the large current density is only 140 mV.
Example 5
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4The difference from example 3 is that the Pt precursor was prepared according to the following procedure, in terms of the amount of Pt precursor added:
(1) according to a molar ratio of 2: 20: 80 respectively taking a noble metal precursor (platinum chlorate), an inorganic molybdenum source precursor (nickel molybdate) and an inorganic nickel source precursor (nickel nitrate), adding the noble metal precursor (platinum chlorate), the inorganic molybdenum source precursor (nickel molybdate) and the inorganic nickel source precursor (nickel nitrate) into 30mL of deionized water, mixing to form a precursor mixed solution, placing the precursor mixed solution into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ so that platinum-containing molybdenum-nickel oxide uniformly grows on foamed nickel (an electrode current collector) to obtain an intermediate platinum/molybdenum-nickel compound electrode;
(2) placing the platinum/molybdenum-nickel compound electrode prepared in the step (1) in a heating central area of a horizontal tubular furnace, introducing 300sccm inert gas (argon and/or nitrogen) to remove air, continuously introducing the inert gas with the flow rate of 95sccm into the horizontal tubular furnace, heating the reaction furnace to 600 ℃, introducing reducing gas (hydrogen) at the flow rate of 5sccm under the condition of keeping introducing the inert gas of 95sccm, and preserving heat for 120min to perform a reduction reaction; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reducing the temperature of the reaction system to 25 ℃ to obtain the noble metal/molybdenum-nickel composite material Pt/MoNi with the three-dimensional structure4@NiMoO4。
FIG. 11 shows the Pt/MoNi composite material of the present embodiment4@NiMoO4The composite material obtained in this example has a flower-like structure.
The noble metal/molybdenum-nickel composite material of the embodiment is taken as an electrode sample to carry out electrochemical performance test, and the test method comprises the following steps: linear sweep voltammetry. The resulting current density versus voltage curve is shown in FIG. 10, from which it can be seen that the noble metal/molybdenum-nickel composite of example 5 has a lower initial overpotential at 500mA cm-2The overpotential under the large current density is only 220 mV. By comparing examples 3 to 5, when other conditions are consistent, the platinum precursor, the inorganic molybdenum source precursor, and the inorganic nickel source precursor are mixed in a molar ratio of 1: 20: at 80 deg.C, the hydrogen evolution reaction performance is best.
Example 6
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4The difference from example 4 is that the thermal reduction temperature is different, and the preparation method comprises the following steps:
(1) according to a molar ratio of 2: 20: 80 respectively taking a noble metal precursor (platinum chlorate), an inorganic molybdenum source precursor (nickel molybdate) and an inorganic nickel source precursor (nickel nitrate), adding the noble metal precursor (platinum chlorate), the inorganic molybdenum source precursor (nickel molybdate) and the inorganic nickel source precursor (nickel nitrate) into 30mL of deionized water, mixing to form a precursor mixed solution, placing the precursor mixed solution into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ so that platinum-containing molybdenum-nickel oxide uniformly grows on foamed nickel (an electrode current collector) to obtain an intermediate platinum/molybdenum-nickel compound electrode;
2) placing the platinum/molybdenum-nickel compound electrode prepared in the step (1) in a heating central area of a horizontal tubular furnace, introducing 300sccm inert gas (argon and/or nitrogen) to remove air, continuing introducing the inert gas with the flow rate of 95sccm into the horizontal tubular furnace, heating the reaction furnace to 400 ℃, introducing reducing gas (hydrogen) at the flow rate of 5sccm under the condition of keeping introducing the inert gas of 95sccm, and preserving heat for 120min to perform a reduction reaction; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reactingThe temperature of the system is reduced to 25 ℃, and the noble metal/molybdenum-nickel composite material Pt/MoNi with the three-dimensional structure is obtained4@NiMoO4。
The noble metal/molybdenum-nickel composite material of example 6 was used as an electrode sample for electrochemical performance testing, and the test method was: linear sweep voltammetry. The resulting current density versus voltage curve is shown in FIG. 12, from which it can be seen that the noble metal/molybdenum-nickel composite of example 6 has a lower initial overpotential at 500mA cm-2The overpotential at high current density is only 175 mV.
Example 7
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4The difference from example 4 is that the thermal reduction temperature is different, and the preparation method comprises the following steps:
(1) according to a molar ratio of 2: 20: 80 respectively taking a noble metal precursor (platinum chlorate), an inorganic molybdenum source precursor (ammonium molybdate) and an inorganic nickel source precursor (nickel nitrate), adding the noble metal precursor (platinum chlorate), the inorganic molybdenum source precursor (ammonium molybdate) and the inorganic nickel source precursor (nickel nitrate) into 30mL of deionized water, mixing to form a precursor mixed solution, placing the precursor mixed solution into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ so that platinum-containing molybdenum-nickel oxide uniformly grows on foamed nickel (an electrode current collector) to obtain an intermediate platinum/molybdenum-nickel compound electrode;
2) placing the platinum/molybdenum-nickel compound electrode prepared in the step (1) in a heating central area of a horizontal tubular furnace, introducing 300sccm inert gas (argon and/or nitrogen) to remove air, continuously introducing the inert gas with the flow rate of 95sccm into the horizontal tubular furnace, heating the reaction furnace to 500 ℃, introducing reducing gas (hydrogen) at the flow rate of 5sccm under the condition of keeping introducing the inert gas of 95sccm, and preserving heat for 120min to perform a reduction reaction; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reducing the temperature of the reaction system to 25 ℃ to obtain the noble metal/molybdenum-nickel composite material Pt/MoNi with the three-dimensional structure4@NiMoO4。
Fig. 13 to 15 are scanning electron micrographs of the noble metal/moly-nickel composite materials prepared in examples 5 to 7, respectively, and fig. 16 is a size distribution diagram of surface particles of the noble metal/moly-nickel composite materials of examples 5 to 7, and it is understood that the particle size of the surface of the material increases with the temperature of the thermal reduction, resulting in a change in the surface roughness of the material.
The noble metal/molybdenum-nickel composite material of example 7 was used as an electrode sample for electrochemical performance testing, and the test method was: linear sweep voltammetry. The resulting current density versus voltage curve is shown in FIG. 12, from which it can be seen that the noble metal/molybdenum-nickel composite of example 7 has a lower initial overpotential at 500mA cm-2The overpotential under the large current density is only 100 mV. By comparing examples 5, 6 and 7, when other conditions are consistent, the thermal reduction temperature is 500 ℃, the hydrogen evolution reaction performance is the best, the performance of the noble metal/molybdenum nickel composite material prepared at the thermal reduction temperature of 500 ℃ is better than that of the noble metal/molybdenum nickel composite material prepared at the low thermal reduction temperature, the main reason is that the molybdate often has two phases of alpha and beta, the transformation process of the molybdate from the alpha phase to the beta phase often occurs in the thermal reduction temperature range of the invention, the transformation temperature of the molybdate is about 500-. The phase transition during the thermal reduction treatment was confirmed by comparing the X-ray diffraction spectrum before the thermal reduction treatment in fig. 1 with the X-ray diffraction spectrum after the thermal reduction treatment in fig. 5. In addition, although the crystal phase is changed at 600 ℃, the temperature of 600 ℃ is higher, active material (noble metal) particles precipitated by reduction are agglomerated and sintered, and the number of exposed atoms is reduced, so that the catalytic activity is not favorable, and the thermal reduction temperature is preferably 450 to 550 ℃.
Example 8
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4The difference from example 1 is that the thermal reduction treatment time is different, and the preparation is carried out according to the following steps:
(1) according to a molar ratio of 1: 20: 80 respectively taking a noble metal precursor (platinum chlorate), an inorganic molybdenum source precursor (ammonium molybdate) and an inorganic nickel source precursor (nickel nitrate), adding the noble metal precursor (platinum chlorate), the inorganic molybdenum source precursor (ammonium molybdate) and the inorganic nickel source precursor (nickel nitrate) into 30mL of deionized water, mixing to form a precursor mixed solution, placing the precursor mixed solution into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ so that platinum-containing molybdenum-nickel oxide uniformly grows on foamed nickel (an electrode current collector) to obtain an intermediate platinum/molybdenum-nickel compound electrode;
placing the platinum/molybdenum-nickel compound electrode prepared in the step (1) in a heating central area of a horizontal tubular furnace, introducing 300sccm inert gas (argon and/or nitrogen) to remove air, continuously introducing the inert gas with the flow rate of 95sccm into the horizontal tubular furnace, heating the reaction furnace to 500 ℃, introducing reducing gas (hydrogen) at the flow rate of 5sccm under the condition of keeping introducing the inert gas of 95sccm, and preserving heat for 5min to perform a reduction reaction; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reducing the temperature of the reaction system to 25 ℃ to obtain the noble metal/molybdenum-nickel composite material Pt/MoNi with the three-dimensional structure4@NiMoO4。
The noble metal/molybdenum-nickel composite material of example 8 was used as an electrode sample for electrochemical performance testing, and the test method was: linear sweep voltammetry. The resulting current density versus voltage curve is shown in FIG. 17, from which it can be seen that the noble metal/molybdenum-nickel composite of example 8 has a lower initial overpotential at 500mA cm-2The overpotential under the heavy current density is only 90mV, which shows that the hydrogen production performance by electrocatalysis is better.
Example 9
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4The difference from example 1 is that the thermal reduction treatment time is different, and the preparation is carried out according to the following steps:
(1) according to a molar ratio of 1: 20: 80 respectively taking a noble metal precursor (platinum chlorate), an inorganic molybdenum source precursor (ammonium molybdate) and an inorganic nickel source precursor (nickel nitrate), adding the noble metal precursor (platinum chlorate), the inorganic molybdenum source precursor (ammonium molybdate) and the inorganic nickel source precursor (nickel nitrate) into 30mL of deionized water, mixing to form a precursor mixed solution, placing the precursor mixed solution into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ so that platinum-containing molybdenum-nickel oxide uniformly grows on foamed nickel (an electrode current collector) to obtain an intermediate platinum/molybdenum-nickel compound electrode;
placing the platinum/molybdenum-nickel compound electrode prepared in the step (1) in a heating central area of a horizontal tubular furnace, introducing 300sccm inert gas (argon and/or nitrogen) to remove air, continuously introducing the inert gas with the flow rate of 95sccm into the horizontal tubular furnace, heating the reaction furnace to 500 ℃, introducing reducing gas (hydrogen) at the flow rate of 5sccm under the condition of keeping introducing the inert gas of 95sccm, and preserving heat for 30min to perform a reduction reaction; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reducing the temperature of the reaction system to 25 ℃ to obtain the noble metal/molybdenum-nickel composite material Pt/MoNi with the three-dimensional structure4@NiMoO4。
The noble metal/molybdenum-nickel composite material of example 9 was used as an electrode sample for electrochemical performance testing, and the test method was: linear sweep voltammetry. The resulting current density versus voltage curve is shown in FIG. 17, from which it can be seen that the noble metal/molybdenum-nickel composite of example 9 has a lower initial overpotential at 500mA cm-2The overpotential under the heavy current density is only 55mV, which shows that the hydrogen production performance by electrocatalysis is better.
Example 10
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4The difference from example 1 is that the thermal reduction treatment time is different, and the preparation is carried out according to the following steps:
(1) according to a molar ratio of 1: 20: 80 respectively taking a noble metal precursor (platinum chlorate), an inorganic molybdenum source precursor (ammonium molybdate) and an inorganic nickel source precursor (nickel nitrate), adding the noble metal precursor (platinum chlorate), the inorganic molybdenum source precursor (ammonium molybdate) and the inorganic nickel source precursor (nickel nitrate) into 30mL of deionized water, mixing to form a precursor mixed solution, placing the precursor mixed solution into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ so that platinum-containing molybdenum-nickel oxide uniformly grows on foamed nickel (an electrode current collector) to obtain an intermediate platinum/molybdenum-nickel compound electrode;
placing the platinum/molybdenum-nickel compound electrode prepared in the step (1) in a heating central area of a horizontal tubular furnace, introducing 300sccm inert gas (argon and/or nitrogen) to remove air, continuously introducing the inert gas with the flow rate of 95sccm into the horizontal tubular furnace, heating the reaction furnace to 500 ℃, introducing reducing gas (hydrogen) at the flow rate of 5sccm under the condition of keeping introducing the inert gas of 95sccm, and preserving heat for 60min to perform a reduction reaction; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reducing the temperature of the reaction system to 25 ℃ to obtain the noble metal/molybdenum-nickel composite material Pt/MoNi with the three-dimensional structure4@NiMoO4。
The noble metal/molybdenum-nickel composite material of example 10 was used as an electrode sample for electrochemical performance testing, and the test method was: linear sweep voltammetry. The resulting current density versus voltage curve is shown in FIG. 17, from which it can be seen that the noble metal/molybdenum-nickel composite of example 10 has a lower initial overpotential at 500mA cm-2The overpotential under the heavy current density is only 90mV, which shows that the hydrogen production performance by electrocatalysis is better.
Example 11
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4The preparation process is the same as that of the example 1, and the difference from the example 1 is that the thermal reduction treatment time is different, and the preparation method comprises the following steps:
(1) according to a molar ratio of 1: 20: 80 respectively taking a noble metal precursor (platinum chlorate), an inorganic molybdenum source precursor (ammonium molybdate) and an inorganic nickel source precursor (nickel nitrate), adding the noble metal precursor (platinum chlorate), the inorganic molybdenum source precursor (ammonium molybdate) and the inorganic nickel source precursor (nickel nitrate) into 30mL of deionized water, mixing to form a precursor mixed solution, placing the precursor mixed solution into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ so that platinum-containing molybdenum-nickel oxide uniformly grows on foamed nickel (an electrode current collector) to obtain an intermediate platinum/molybdenum-nickel compound electrode;
placing the platinum/molybdenum-nickel compound electrode prepared in the step (1) in the heating central area of a horizontal tube furnace, and introducing 30After 0sccm inert gas (argon and/or nitrogen) is exhausted, continuously introducing the inert gas with the flow rate of 95sccm into the horizontal tubular furnace, heating the reaction furnace to 500 ℃, introducing reducing gas (hydrogen) at the rate of 5sccm under the condition of keeping introducing the inert gas of 95sccm, and preserving heat for 120min for reduction reaction; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reducing the temperature of the reaction system to 25 ℃ to obtain the noble metal/molybdenum-nickel composite material Pt/MoNi with the three-dimensional structure4@NiMoO4。
The noble metal/molybdenum-nickel composite material of example 11 was used as an electrode sample for electrochemical performance testing, and the test method was: linear sweep voltammetry. The resulting current density versus voltage curve is shown in FIG. 17, from which it can be seen that the noble metal/molybdenum-nickel composite of example 11 has a lower initial overpotential at 500mA cm-2The overpotential under the heavy current density is only 130mV, which shows that the hydrogen production performance by electrocatalysis is better.
Example 12
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4The difference from example 1 is that the thermal reduction treatment time is different, and the preparation is carried out according to the following steps:
(1) according to a molar ratio of 1: 20: 80 respectively taking a noble metal precursor (platinum chlorate), an inorganic molybdenum source precursor (ammonium molybdate) and an inorganic nickel source precursor (nickel nitrate), adding the noble metal precursor (platinum chlorate), the inorganic molybdenum source precursor (ammonium molybdate) and the inorganic nickel source precursor (nickel nitrate) into 30mL of deionized water, mixing to form a precursor mixed solution, placing the precursor mixed solution into a reaction kettle, and carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at the temperature of 150 ℃ so that platinum-containing molybdenum-nickel oxide uniformly grows on foamed nickel (an electrode current collector) to obtain an intermediate platinum/molybdenum-nickel compound electrode;
placing the platinum/molybdenum-nickel compound electrode prepared in the step (1) in a heating central area of a horizontal tubular furnace, introducing 300sccm inert gas (argon and/or nitrogen) to remove air, continuously introducing 95sccm inert gas into the horizontal tubular furnace, heating the reaction furnace to 500 ℃, and introducing 5sccm inert gasIntroducing reducing gas (hydrogen) at the sccm rate, and preserving the temperature for 180min to perform a reduction reaction; stopping introducing hydrogen after the reaction, keeping introducing 95sccm inert gas, naturally cooling, and reducing the temperature of the reaction system to 25 ℃ to obtain the noble metal/molybdenum-nickel composite material Pt/MoNi with the three-dimensional structure4@NiMoO4。
The noble metal/molybdenum-nickel composite material of example 12 was used as an electrode sample for electrochemical performance testing, and the test method was: linear sweep voltammetry. The resulting current density versus voltage curve is shown in FIG. 17, from which it can be seen that the noble metal/molybdenum-nickel composite of example 12 has a lower initial overpotential at 500mA cm-2The overpotential under the heavy current density is only 150mV, which shows that the hydrogen production performance by electrocatalysis is better. By comparing example 1 and examples 8 to 12, the hydrogen evolution reaction performance was better when the thermal reduction treatment time was 15 to 30min under the other conditions.
Example 13
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4In this example, the nickel foam was replaced with 1 × 3cm carbon paper in step (1), and the reduction reaction was performed by keeping the temperature for 180min in step (2), unlike example 1, which differs only in the substrate added and the time for the reduction reaction.
Example 14
This example provides a noble metal/molybdenum-nickel composite Pt/MoNi with three-dimensional structure4@NiMoO4The difference from example 1 is that no substrate is added and the composite material finally obtained is present in the form of a powder.

Claims (10)

1. A noble metal/molybdenum-nickel composite material is characterized by comprising a molybdenum-nickel material with a three-dimensional structure and a noble metal loaded on the molybdenum-nickel material; the molybdenum-nickel material comprises ABO4A core of a type compound, and an ABO dispersed in said ABO4AB alloy around the core of the type compound and B oxide, wherein A is any one of Fe, Co, Ni, Cu and Zn, and B is VIB group elementAnd (4) element.
2. The precious metal/molybdenum-nickel based composite material according to claim 1, wherein the three-dimensional structure comprises a rod, flower or tube shape.
3. The precious metal/molybdenum-nickel-based composite material according to claim 1, wherein the ABO is selected from the group consisting of4The core of the type compound is a nickel molybdate core, the AB alloy is a molybdenum-nickel alloy, and the oxide of the B is an oxide of molybdenum; preferably, the molybdenum oxide comprises at least one of molybdenum dioxide and molybdenum trioxide, and the molybdenum-nickel alloy comprises MoNi4、MoNi3At least one of (1).
4. The precious metal/molybdenum-nickel composite of any one of claims 1 to 3, wherein the precious metal comprises at least one of gold, silver, platinum group metals.
5. The method for preparing a noble metal/molybdenum-nickel composite material according to any one of claims 1 to 4, comprising the steps of:
carrying out hydrothermal reaction on a precursor mixed solution or a precursor mixed solution added into a substrate in a closed container, wherein the precursor mixed solution comprises a precious metal precursor, an inorganic B source precursor and an inorganic A source precursor;
and introducing inert gas and reducing gas, and carrying out reduction reaction to obtain the noble metal/molybdenum-nickel composite material.
6. The method for preparing a noble metal/molybdenum-nickel composite material according to claim 5, wherein the inorganic A source precursor includes any one of an inorganic iron source precursor, an inorganic cobalt source precursor, an inorganic nickel source precursor, an inorganic copper source precursor, and an inorganic zinc source precursor, and the inorganic B source precursor includes any one of an inorganic molybdenum source precursor and an inorganic tungsten source precursor; preferably, the inorganic iron source precursor comprises any one of ferric chloride, ferric nitrate and ferric sulfate, the inorganic cobalt source precursor comprises any one of cobalt nitrate, cobalt chloride and cobalt sulfate, the inorganic nickel source precursor comprises any one of nickel nitrate, nickel chloride and nickel sulfate, the inorganic copper source precursor comprises any one of copper chloride, copper nitrate and copper sulfate, and the inorganic zinc source precursor comprises any one of zinc chloride, zinc nitrate and zinc sulfate; the inorganic molybdenum source precursor comprises any one of molybdic acid, ammonium molybdate, sodium molybdate and potassium molybdate, and the inorganic tungsten source precursor comprises any one of tungstic acid, ammonium tungstate, potassium tungstate and sodium tungstate.
7. The method for preparing a noble metal/molybdenum-nickel composite material according to claim 5, wherein the temperature of the hydrothermal reaction is 60 to 200 ℃; preferably, the time of the hydrothermal reaction is 2-10 h.
8. The method for preparing a noble metal/molybdenum-nickel composite material according to any one of claims 5 to 7, wherein the temperature of the reduction reaction is 100 to 1000 ℃; preferably, the temperature of the reduction reaction is 450-550 ℃.
9. The method for producing a noble metal/molybdenum-nickel composite material according to any one of claims 5 to 7, wherein the noble metal precursor: inorganic molybdenum source precursor: the molar ratio of the inorganic nickel source precursor is (0.2-2): (10-40): 80.
10. use of the noble metal/molybdenum-nickel composite material according to any one of claims 1 to 4 in hydrogen production by electrolysis of water, fuel cells, methanol oxidation, ethanol oxidation, supercapacitors and ion batteries.
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