阅读说明：本技术 一种三元过渡金属电解水析氢催化剂复合材料及制备方法 (Ternary transition metal electrolysis water hydrogen evolution catalyst composite material and preparation method thereof ) 是由 戴凌杰 王国勇 孙贵训 王瑜喆 于 2021-09-15 设计创作，主要内容包括：本发明提供一种三元过渡金属电解水析氢催化剂复合材料及制备方法,包括如下步骤：按照一定摩尔比,将C-(6)H-(17)FeO-(10)、C-(4)H-(6)NiO-(4)·4H-(2)O、C-(4)H-(6)CoO-(4)·4H-(2)O加入到C-(3)H-(8)O-(2)中再加入C-(3)H-(8)O到混合溶液中,共同放入反应釜中,得到FeCoNiOH/NF前驱体；将所得FeCoNiOH/NF前驱体与NaH-(2)PO-(2)分别放在两个瓷舟中,将装有NaH-(2)PO-(2)的瓷舟放在管式炉的上风口,将装有FeCoNiOH/NF前驱体的瓷舟放在管式炉的下风口；在氩气氛围内以一定的升温速率升温至350℃并保温一定时间,得到FeCoNiP/NF复合材料。以泡沫镍为导电基底的生长FeCoNiP三元过渡金属磷化物,泡沫镍的三维骨架结构可以增加电解水催化剂的比表面积,提供更多的电催化活性位点,而且,泡沫镍具有良好的机械性能,保证了活性电极在催化过程中结构的稳定性。(The invention provides a ternary transition metal electrolysis water hydrogen evolution catalyst composite material and a preparation method thereof, wherein the preparation method comprises the following steps: according to a certain mole ratio, adding C 6 H 17 FeO 10 、C 4 H 6 NiO 4 ·4H 2 O、C 4 H 6 CoO 4 ·4H 2 Addition of O to C 3 H 8 O 2 Adding C 3 H 8 Adding O into the mixed solution, and putting into a reaction kettle together to obtain a FeCoNiOH/NF precursor; the FeCoNiOH/NF precursor and NaH are obtained 2 PO 2 Respectively placing in two porcelain boats, and filling NaH 2 PO 2 The porcelain boat is placed on the tube furnaceA tuyere, wherein the porcelain boat filled with FeCoNiOH/NF precursor is placed at the lower tuyere of the tube furnace; heating to 350 ℃ at a certain heating rate in an argon atmosphere, and preserving the heat for a certain time to obtain the FeCoNiP/NF composite material. The three-dimensional skeleton structure of the foam nickel can increase the specific surface area of the water electrolysis catalyst and provide more electrocatalytic active sites, and the foam nickel has good mechanical property, thereby ensuring the structural stability of the active electrode in the catalysis process.)

1. A ternary transition metal electrolysis water hydrogen evolution catalyst composite material and a preparation method thereof are characterized in that: the method comprises the following steps:

step one, preparing FeCoNiOH/NF precursor:

according to a certain mole ratio, preparing C₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂O、C₃H₈O₂、C₃H₈O, mixing C with₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂Addition of O to C₃H₈O₂Mixing with medium ultrasonic wave for a certain time, adding C₃H₈Performing ultrasonic treatment on the O in the mixed solution for a certain time; putting the mixed solution obtained by the ultrasonic treatment and the foamed nickel into a reaction kettle together, and preserving the heat for a certain time at a certain temperature to obtain a FeCoNiOH/NF precursor;

step two, preparing FeCoNiP/NF composite material:

FeCoNiOH/NF precursor obtained in the step one and NaH₂PO₂Respectively placing the two porcelain boats with NaH in a certain mass ratio₂PO₂The porcelain boat is placed at the upper air inlet of the tube furnace, and the porcelain boat filled with FeCoNiOH/NF precursor is placed at the lower air inlet of the tube furnace; heating to 350 ℃ at a certain heating rate in an argon atmosphere, and preserving the heat for a certain time to obtain the FeCoNiP/NF composite material.

2. The three-way transition metal electrolysis hydrogen evolution catalyst composite material and the preparation method thereof according to claim 1, wherein C in the first step₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂O、C₃H₈O₂、C₃H₈The molar ratio of O is 0.5mmol to 0.5mmmol to 1.5mmmol to 525mmol to 135mmol, and the ultrasonic treatment time is 30 min.

3. The ternary transition metal electrolysis hydrogen evolution catalyst composite material and the preparation method thereof as claimed in claim 1, wherein in the first step, the temperature in a reaction kettle is kept at 160 ℃ for 12 h.

4. The ternary transition metal electrolysis hydrogen evolution catalyst composite material and the preparation method thereof as claimed in claim 1, wherein in the first step, the foamed nickel is sequentially cleaned by 5% HCL, absolute ethyl alcohol and deionized water for 15-30 min by ultrasonic cleaning before use.

5. The three-way transition metal electrolysis hydrogen evolution catalyst composite material and the preparation method thereof as claimed in claim 1, wherein the FeCoNiOH/NF precursor obtained in the first step is firstly dried in vacuum at 60 ℃ for 12h, and then the FeCoNiOH/NF precursor and NaH are dried according to the second step₂PO₂Are respectively put into two porcelain boats according to the mass ratio of 1: 5.

6. The ternary transition metal electrolysis hydrogen evolution catalyst composite material and the preparation method thereof as claimed in claim 1, wherein the flow rate of argon in the argon atmosphere in the second step is 80-100 scm, the heating rate is 5 ℃/min, and the time of heat preservation at 350 ℃ is 2 h.

Technical Field

The invention belongs to the technical field of water electrolysis, and particularly relates to a ternary transition metal electrolysis water hydrogen evolution catalyst composite material and a preparation method thereof.

Background

Due to the increasing severity of the energy crisis and the development of a series of environmental problems caused by excessive dependence on fossil energy to maintain social activities such as industrial production, a brand new alternative energy and energy storage system which are sustainable, renewable and environmentally friendly to some extent are urgently explored. It is known that hydrogen combustion can release huge energy, and the combustion only generates water without releasing greenhouse gases or other harmful substances, so that the hydrogen can be used as a new energy source with high efficiency and no pollution.

Currently, the most efficient electrolytic water hydrogen evolution catalyst is a platinum group catalyst, but the practical application of the platinum group catalyst is limited by the expensive price and limited resources. Transition metal phosphide, a non-noble metal catalyst, is a very potential electrolytic water catalyst material due to its good electronic structure effect, high conductivity and better durability, as well as its unique electrocatalytic properties over a wide range of pH.

In recent years, three-component catalysts with complex three-dimensional structures and high catalytic activity have been developed, but the catalysts have poor stability, complex preparation method and poor repeatability, and are not beneficial to realizing industrial scale production; therefore, the ternary transition metal electrolysis water hydrogen evolution catalyst FeCoNiP/NF composite material is high in catalytic activity, simple in preparation method and good in repeatability.

Disclosure of Invention

In order to solve the technical problems, the invention provides a ternary transition metal electrolysis water evolution hydrogen catalyst composite material and a preparation method thereof, and aims to solve the problems that the catalyst is poor in stability, complex in preparation method, poor in repeatability and not beneficial to industrial scale production.

The purpose and the efficacy of the ternary transition metal electrolysis water evolution hydrogen catalyst composite material and the preparation method thereof are achieved by the following specific technical means:

a ternary transition metal electrolysis water hydrogen evolution catalyst composite material and a preparation method thereof comprise the following steps:

step one, preparing FeCoNiOH/NF precursor:

according to a certain mole ratio, preparing C₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂O、C₃H₈O₂、C₃H₈O, mixing C with₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂Addition of O to C₃H₈O₂Mixing with medium ultrasonic wave for a certain time, adding C₃H₈Performing ultrasonic treatment on the O in the mixed solution for a certain time; putting the mixed solution obtained by the ultrasonic treatment and the foamed nickel into a reaction kettle together, and preserving the heat for a certain time at a certain temperature to obtain a FeCoNiOH/NF precursor;

step two, preparing FeCoNiP/NF composite material:

FeCoNiOH/NF precursor obtained in the step one and NaH₂PO₂Respectively placing the two porcelain boats with NaH in a certain mass ratio₂PO₂The porcelain boat is placed at the upper air inlet of the tube furnace, and the porcelain boat filled with FeCoNiOH/NF precursor is placed at the lower air inlet of the tube furnace; heating to 350 ℃ at a certain heating rate in an argon atmosphere, and preserving the heat for a certain time to obtain the FeCoNiP/NF composite material.

Further, C in the first step₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂O、C₃H₈O₂、C₃H₈The molar ratio of O is 0.5mmol to 0.5mmmol to 1.5mmmol to 525mmol to 135mmol, and the ultrasonic treatment time is 30 min.

Further, in the first step, the temperature in the reaction kettle is kept at 160 ℃ for 12 hours.

Further, before the use of the foamed nickel in the step one, 5% HCL, absolute ethyl alcohol and deionized water are respectively used for ultrasonic cleaning for 15-30 min in sequence.

Further, the FeCoNiOH/NF precursor obtained in the first step is dried in vacuum at 60 ℃ for 12h, and then the FeCoNiOH/NF precursor and NaH are added according to the second step₂PO₂Are respectively put into two porcelain boats according to the mass ratio of 1: 5.

Further, in the second step, the flow of argon in the argon atmosphere is 80-100 scm, the heating rate is 5 ℃/min, and the heat preservation time at 350 ℃ is 2 h.

The invention at least comprises the following beneficial effects:

the electrolytic water hydrogen evolution catalyst FeCoNiP/NF composite material provided by the invention is a grown FeCoNiP ternary transition metal phosphide taking foamed nickel as a conductive substrate; the composite material has a current density of 10mA/cm²The overpotential is only 83.6mV, and has small Tafel slope and good stability, and the excellent electrochemical performance is mainly due to the existence of Nickel Foam (NF) and a unique ternary transition metal heterostructure; the ternary transition metal heterostructure has unique electronic structure characteristics, so that the electronic transmission is accelerated, and the conductivity of the material is improved; meanwhile, the three-dimensional skeleton structure of the foamed nickel can increase the specific surface area of the electrolytic water catalyst and provide more electrocatalytic active sites, and the foamed nickel has good mechanical properties, so that the structural stability of the active electrode in the catalysis process is ensured, and the excellent electrochemical properties of the active electrode can be still maintained in the long-time circulation process.

Drawings

FIG. 1 is an X-ray diffraction pattern of a ternary transition metal electrohydronium catalyst precursor FeCoNiOH prepared in the first example of the present invention.

FIG. 2 is an X-ray diffraction pattern of a ternary transition metal electrohydrolization hydrogen evolution catalyst FeCoNiP prepared in the first embodiment of the invention.

FIG. 3 is a scanning electron microscope image of the field emission of a ternary transition metal electrogenerated hydrogen evolution catalyst precursor FeCoNiOH/NF composite material prepared in the first embodiment of the present invention.

FIG. 4 is a scanning electron microscope image of the field emission of the ternary transition metal electrolysis hydrogen evolution catalyst FeCoNiP/NF composite material prepared in the first embodiment of the present invention.

FIG. 5 is a mapping distribution diagram of iron element of the ternary transition metal electrolysis hydro-evolution hydrogen catalyst FeCoNiP/NF composite material prepared in the first embodiment of the invention.

FIG. 6 is a cobalt mapping distribution diagram of a ternary transition metal electrolysis hydro-evolution catalyst FeCoNiP/NF composite material prepared in the first embodiment of the present invention.

FIG. 7 is a mapping distribution diagram of nickel element of a ternary transition metal electrolysis water evolution hydrogen catalyst FeCoNiP/NF composite material prepared in the first embodiment of the invention.

FIG. 8 is a phosphorus mapping distribution diagram of a ternary transition metal electrolysis water evolution hydrogen catalyst FeCoNiP/NF composite material prepared in the first embodiment of the invention.

FIG. 9 is a performance diagram of the catalytic electrolyzed water of the ternary transition metal electrolytic water evolution hydrogen catalyst FeCoNiP/NF composite material prepared in the first embodiment of the invention.

FIG. 10 is a Tafel slope curve of a ternary transition metal electrolysis water evolution hydrogen catalyst FeCoNiP/NF composite material prepared in the first embodiment of the present invention.

Detailed Description

The embodiments of the present invention will be described in further detail with reference to the drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

In the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "coaxial," "bottom," "one end," "top," "middle," "other end," "upper," "side," "top," "inner," "front," "center," "two ends," and the like are used in an orientation or positional relationship indicated in the drawings for convenience in describing and simplifying the description, and are not intended to indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the invention. Furthermore, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

In the description of the present invention, it should be noted that, unless explicitly stated or limited otherwise, the terms "mounted," "disposed," "connected," "fixed," "screwed" and the like are to be understood broadly, and for example, they may be fixedly connected, detachably connected, or integrated; can be mechanically or electrically connected; the terms may be directly connected or indirectly connected through an intermediate, and may be communication between two elements or interaction relationship between two elements, unless otherwise specifically limited, and the specific meaning of the terms in the present invention will be understood by those skilled in the art according to specific situations.

The first embodiment is as follows:

as shown in figures 1 to 10:

the embodiment provides a ternary transition metal electrolysis water hydrogen evolution catalyst composite material and a preparation method thereof, and the preparation method comprises the following steps:

s1: c was prepared in a molar ratio of 0.5mmol:0.5mmmol:1.5mmmol:525mmol:135mmol₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂O、C₃H₈O₂、C₃H₈O, mixing C with₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂Addition of O to C₃H₈O₂Mixing with ultrasonic wave for 30min, and adding C₃H₈Performing ultrasonic treatment on the mixed solution for 30 min; putting the mixed solution obtained by the ultrasonic treatment and the foamed nickel into a reaction kettle, and keeping the temperature at 160 ℃ for 12 hours to obtain a FeCoNiOH/NF precursor;

s2: FeCoNiOH/NF precursor obtained from S1 and NaH₂PO₂Respectively placing the two porcelain boats in a mass ratio of 1:5, and filling NaH₂PO₂The porcelain boat is placed at the upper air inlet of the tube furnace, and the porcelain boat filled with FeCoNiOH/NF precursor is placed at the lower air inlet of the tube furnace; heating to 350 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, and keeping the temperature for a certain time to obtain a FeCoNiP/NF composite material;

example two:

the embodiment provides a ternary transition metal electrolysis water hydrogen evolution catalyst composite material and a preparation method thereof, and the preparation method comprises the following steps:

s1: c was prepared in a molar ratio of 0.5mmol:0.5mmmol:1.5mmmol:525mmol:135mmol₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂O、C₃H₈O₂、C₃H₈O, mixing C with₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂Addition of O to C₃H₈O₂Mixing with ultrasonic wave for 30min, and adding C₃H₈Performing ultrasonic treatment on the mixed solution for 30 min; putting the mixed solution obtained by the ultrasonic treatment and the foamed nickel into a reaction kettle, and keeping the temperature at 120 ℃ for 12 hours to obtain a FeCoNiOH/NF precursor;

s2: FeCoNiOH/NF precursor obtained from S1 and NaH₂PO₂Respectively placing the two porcelain boats in a mass ratio of 1:5, and filling NaH₂PO₂The porcelain boat is placed at the upper air inlet of the tube furnace, and the porcelain boat filled with FeCoNiOH/NF precursor is placed at the lower air inlet of the tube furnace; heating to 350 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, and keeping the temperature for a certain time to obtain a FeCoNiP/NF composite material;

example three:

the embodiment provides a ternary transition metal electrolysis water hydrogen evolution catalyst composite material and a preparation method thereof, and the preparation method comprises the following steps:

s1: according to 0.5molar ratio of mmol 0.5mmmol 1.5mmmol 525mmol 135mmol C was prepared₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂O、C₃H₈O₂、C₃H₈O, mixing C with₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂Addition of O to C₃H₈O₂Mixing with ultrasonic wave for 30min, and adding C₃H₈Performing ultrasonic treatment on the mixed solution for 30 min; putting the mixed solution obtained by the ultrasonic treatment and the foamed nickel into a reaction kettle, and keeping the temperature at 140 ℃ for 12 hours to obtain a FeCoNiOH/NF precursor;

s2: FeCoNiOH/NF precursor obtained from S1 and NaH₂PO₂Respectively placing the two porcelain boats in a mass ratio of 1:5, and filling NaH₂PO₂The porcelain boat is placed at the upper air inlet of the tube furnace, and the porcelain boat filled with FeCoNiOH/NF precursor is placed at the lower air inlet of the tube furnace; heating to 350 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, and keeping the temperature for a certain time to obtain a FeCoNiP/NF composite material;

example four:

the embodiment provides a ternary transition metal electrolysis water hydrogen evolution catalyst composite material and a preparation method thereof, and the preparation method comprises the following steps:

s1: c was prepared in a molar ratio of 0.5mmol:0.5mmmol:1.5mmmol:525mmol:135mmol₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂O、C₃H₈O₂、C₃H₈O, mixing C with₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂Addition of O to C₃H₈O₂Mixing with ultrasonic wave for 30min, and adding C₃H₈Performing ultrasonic treatment on the mixed solution for 30 min; putting the mixed solution obtained by ultrasonic treatment and foamed nickel into reaction togetherIn the kettle, keeping the temperature at 160 ℃ for 12h to obtain FeCoNiOH/NF precursor;

s2: FeCoNiOH/NF precursor obtained from S1 and NaH₂PO₂Respectively placing the two porcelain boats in a mass ratio of 1:10, and filling NaH₂PO₂The porcelain boat is placed at the upper air inlet of the tube furnace, and the porcelain boat filled with FeCoNiOH/NF precursor is placed at the lower air inlet of the tube furnace; heating to 350 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, and keeping the temperature for a certain time to obtain a FeCoNiP/NF composite material;

example five:

the embodiment provides a ternary transition metal electrolysis water hydrogen evolution catalyst composite material and a preparation method thereof, and the preparation method comprises the following steps:

s1: c was prepared in a molar ratio of 0.5mmol:0.5mmmol:1.5mmmol:525mmol:135mmol₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂O、C₃H₈O₂、C₃H₈O, mixing C with₆H₁₇FeO₁₀、C₄H₆NiO₄·4H₂O、C₄H₆CoO₄·4H₂Addition of O to C₃H₈O₂Mixing with ultrasonic wave for 30min, and adding C₃H₈Performing ultrasonic treatment on the mixed solution for 30 min; putting the mixed solution obtained by the ultrasonic treatment and the foamed nickel into a reaction kettle, and keeping the temperature at 160 ℃ for 12 hours to obtain a FeCoNiOH/NF precursor;

s2: FeCoNiOH/NF precursor obtained from S1 and NaH₂PO₂Respectively placing the two porcelain boats in a mass ratio of 1:5, and filling NaH₂PO₂The porcelain boat is placed at the upper air inlet of the tube furnace, and the porcelain boat filled with FeCoNiOH/NF precursor is placed at the lower air inlet of the tube furnace; heating to 350 ℃ at a heating rate of 3 ℃/min in an argon atmosphere and preserving heat for a certain time to obtain a FeCoNiP/NF composite material;

experimental example:

1. in a three-electrode test system, the FeCoNiP/NF composite material prepared by the embodiment of the invention has the current density of 10mA/cm²The overpotential is 83.6-103.4 mV, and the electrochemical performance is excellent;

2. carrying out various characterizations and tests on the composite electrode material prepared in the first embodiment; specifically, as shown in fig. 1, which is an X-ray diffraction (XRD) pattern of a ternary transition metal electrohydrolization hydrogen evolution catalyst precursor FeCoNiOH prepared in example one, it can be seen that the precursor is made of Fe₃O₄、Ni(OH)₂And Co (OH)₂Forming; FIG. 2 is an X-ray diffraction (XRD) pattern of a ternary transition metal electrohydrolization hydrogen evolution catalyst FeCoNiP prepared in example one, and it can be seen from the pattern that the ternary transition metal catalyst is formed by FeP₂、Ni₂P and CoP;

3. FIG. 3 is a scanning electron microscope image of the field emission of a ternary transition metal electrogenerated hydrogen evolution catalyst precursor FeCoNiOH prepared in the first embodiment, from which it can be seen that the precursor has a petal-shaped morphology; FIG. 4 is a scanning electron microscope image of the field emission of the ternary transition metal electrolytic water evolution hydrogen catalyst FeCoNiP prepared in the first example, because the foamed nickel substrate causes stronger electrostatic offset, the image is less clear, but it can be seen that the surface of the ternary transition metal catalyst has a rougher surface;

4. FIGS. 5, 6, 7 and 8 are mapping distribution diagrams of iron element, cobalt element, nickel element and phosphorus element of the ternary transition metal electrohydroevolution hydrogen catalyst FeCoNiP/NF composite material prepared in the first embodiment; the figure shows that Fe, Co, Ni and P are uniformly distributed in the ternary transition metal electrolysis water evolution hydrogen catalyst FeCoNiP/NF composite material;

5. the composite electrode material prepared in the second embodiment is tested in a three-electrode system, wherein FIG. 9 shows that the concentration of the ternary transition metal electrolysis hydrogen evolution catalyst FeCoNiP/NF composite material is 0.5 mol.L^-1H of (A) to (B)₂SO₄Polarization curve in electrolyte, we can see from FIG. 9 that at current density 10mA/cm²The overpotential is only 83.6mV, and the catalyst has quite excellent catalytic performance; FIG. 10 is a Tafel slope curve of a ternary transition metal electrolysis hydro-evolution catalyst FeCoNiP/NF composite material; the tafel slope curve represents the hydrogen evolution process of the electrolyzed waterThe rate in the equation is that the lower the slope represents the better the catalytic performance, and from FIG. 10, it can be seen that the Tafel slope of the composite material is 60mV/dec, which has quite excellent catalytic performance.

The invention is not described in detail, but is well known to those skilled in the art.

The embodiments of the present invention have been presented for purposes of illustration and description, and are not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.