CN113668011A - Electrode material with crystalline-state amorphous-state synergetic catalytic interface and preparation method thereof - Google Patents

Electrode material with crystalline-state amorphous-state synergetic catalytic interface and preparation method thereof Download PDF

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CN113668011A
CN113668011A CN202110839910.9A CN202110839910A CN113668011A CN 113668011 A CN113668011 A CN 113668011A CN 202110839910 A CN202110839910 A CN 202110839910A CN 113668011 A CN113668011 A CN 113668011A
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amorphous
nimos
electrode material
reaction kettle
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CN113668011B (en
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杨春明
周立海
胡玉娟
卞玉洁
任宇飞
张瑞娜
王传涛
闫挺
甄延忠
付峰
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Yanan University
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Abstract

The invention discloses an electrode material with a crystalline-amorphous concerted catalysis interface, which comprises crystalline Ni (OH)2And amorphous NiMoS, wherein amorphous NiMoS is composed of Ni (OH)2Conversion to crystalline Ni (OH)2And the amorphous NiMoS form a cooperative catalytic interface. The invention also discloses a preparation method of the electrode material with the crystalline-state and amorphous-state synergetic catalytic interface, which is implemented according to the following steps: step 1, preparing in-situ grown crystalline Ni (OH) on a titanium mesh2A nanosheet precursor; step 2, crystal obtained in step 1State Ni (OH)2Molybdenum sulfurization treatment is carried out on the nanosheet precursor to prepare crystalline Ni (OH)2Amorphous NiMoS has an electrode material with a co-catalytic interface.

Description

Electrode material with crystalline-state amorphous-state synergetic catalytic interface and preparation method thereof
Technical Field
The invention belongs to the technical field of electrode materials and industrial catalysis, and particularly relates to an electrode material with a crystalline-state and amorphous-state cooperative catalysis interface, and a preparation method of the electrode material with the crystalline-state and amorphous-state cooperative catalysis interface.
Background
The consumption of fossil fuels poses a serious energy and environmental crisis. In order to solve this problem, a great deal of research has been put into the utilization of clean energy such as wind energy, geothermal energy, solar energy, and hydrogen energy. Among them, hydrogen energy is receiving more and more attention due to its abundance and higher energy density. The electrochemical water decomposition is considered to be a hydrogen production method with development prospect due to the advantages of safe equipment, environmental protection, rich raw materials and the like.
The development of efficient electrocatalysts is a core problem of water electrolysis technology, and most of the electrocatalysts reported at present show excellent performance in terms of reducing the thermodynamic overpotential and accelerating the kinetics, but the performance of the electrocatalysts is usually limited to a very narrow pH range or under acidic/alkaline conditions with strong corrosiveness. And few catalysts having excellent catalytic performance in natural seawater. The seawater accounts for about 97 percent of the total amount of water resources of the earth, and has great attraction for large-scale industrial hydrogen production to replace fresh water. However, the development of seawater electrolysis is hindered by problems such as chloride release, formation of insoluble deposits, susceptibility of electrodes to corrosion, and the like. Therefore, the development of a durable non-noble metal-based electrocatalyst with wide application is the primary problem in the large-scale production of hydrogen by using seawater.
NiMo-based chalcogenides have higher intrinsic activity and better conductivity than other materials, and thus exhibit excellent HER activity. Interface engineering is an effective strategy to reconfigure the catalyst electronic structure and optimize the surface microenvironment. Are commonly used to accelerate the catalytic kinetics of Ni-Mo-S systems, thereby increasing activity. The catalytic activity of the bimetallic compound strongly depends on the number of active sites and the conductivity of the electrocatalyst and can be improved by adjusting the crystal form of the catalyst. Amorphous materials with randomly oriented bonds can expose more surface defect sites to increase catalytic activity compared to the corresponding crystalline compound. Furthermore, due to the slow kinetics of the water dissociation process, the HER performance of the catalyst in non-acidic electrolytes is much lower than required for industrial applications. Due to its good affinity for water, Ni (OH)2Are considered to be effective water-splitting "promoters". Ni (OH)2Are widely used to modify catalysts and improve their ability to dissociate water. In recent years, the use of interface engineering to design amorphous/crystalline heterostructures has proven to be an effective technique to improve hydrogen evolution efficiency. It is important and challenging to verify the synergistic mechanism between crystalline and amorphous species in the composite, helping us to understand the catalytic mechanism and design a more efficient hydrogen evolution catalyst.
Disclosure of Invention
The first purpose of the invention is to provide an electrode material with a crystalline-amorphous concerted catalysis interface, which solves the problem that an electrocatalyst used in the preparation of hydrogen by using seawater is limited to a very narrow pH range or under acidic/alkaline conditions with strong corrosiveness or can show higher activity by using a large voltage.
In order to achieve the purpose, the invention adopts the technical scheme that: an electrode material with a crystalline-amorphous concerted catalytic interface is prepared from crystalline Ni (OH)2And amorphous NiMoS, wherein amorphous NiMoS is composed of Ni (OH)2Conversion to crystalline Ni (OH)2And amorphous NiMoSA co-catalytic interface is formed therebetween.
The second purpose of the invention is to provide a preparation method of the electrode material with the crystalline-amorphous concerted catalysis interface, which is used for preparing the electrode material with the crystalline-amorphous concerted catalysis interface.
In order to achieve the purpose, the invention adopts the technical scheme that: an electrode material with a crystalline-amorphous concerted catalysis interface is implemented according to the following steps:
step 1, preparing in-situ grown crystalline Ni (OH) on a titanium mesh2A nanosheet precursor;
step 2, the crystalline state Ni (OH) obtained in the step 12Molybdenum sulfurization treatment is carried out on the nanosheet precursor to prepare crystalline Ni (OH)2Amorphous NiMoS has an electrode material with a co-catalytic interface.
The technical scheme of the invention also has the following characteristics:
as a further improvement of the technical scheme of the invention, in the step 1, crystalline Ni (OH) growing in situ is prepared on a titanium net2The nanosheet precursor specifically comprises the following components:
step 1.1, shearing two titanium nets, putting the titanium nets into a hydrochloric acid solution for ultrasonic treatment, washing the titanium nets for several times by using absolute ethyl alcohol and ultrapure water, and drying the titanium nets for later use;
step 1.2, according to 1: 5-10: the molar ratio of 5-10 is measured as Ni (NO)3)2·6H2O、CO(NH2)2And NH4F, dissolving the three components in ultrapure water, and carrying out constant-temperature magnetic stirring to obtain a light green transparent solution;
step 1.3, transferring the light green transparent solution obtained in the step 1.2 into a reaction kettle, then putting the titanium net obtained in the step 1.1 at a certain angle against the inner wall of the reaction kettle for sealing, then putting the reaction kettle into an electric heating constant temperature blast drying box for reaction, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the titanium net for a plurality of times by ultrapure water and absolute ethyl alcohol, and carrying out vacuum drying treatment to obtain crystalline Ni (OH)2And (3) a nanosheet precursor.
As a further improvement of the technical scheme of the invention, in the step 1, in the step 1.1, the concentration of the used hydrochloric acid is 1-5 mol/L, and the time of ultrasonic treatment is 15-30 min.
As a further improvement of the technical solution of the present invention, in step 1.3: the temperature for reaction in the electric heating constant temperature blast drying oven is 120-180 ℃ and the time is 4-10 h.
As a further improvement of the technical solution of the present invention, in step 1.3: the temperature of the vacuum drying treatment is 60-80 ℃, and the time is 6-12 h.
As a further improvement of the technical scheme of the invention, in the step 2, the crystalline state Ni (OH) obtained in the step 1 is treated2The molybdenum vulcanization treatment of the nanosheet precursor is as follows:
step 2.1, measure (NH)4)2MoS4Dissolving in ultrapure water, carrying out constant-temperature magnetic stirring until the ultrapure water is dissolved, and then transferring to a reaction kettle; wherein Ni (NO)3)2·6H2O and (NH)4)2MoS4In a molar ratio of 1: 0.2 to 0.7;
step 2.2, the crystalline state Ni (OH) obtained in the step 12Sealing a nanosheet precursor after leaning against the inner wall of the reaction kettle at a certain angle, then placing the reaction kettle into an electric heating constant-temperature blast drying box for reaction, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the reaction kettle for a plurality of times by using ultrapure water and absolute ethyl alcohol, and finally carrying out vacuum drying treatment to obtain crystalline Ni (OH)2And amorphous NiMoS electrode materials with a co-catalytic interface.
As a further improvement of the technical scheme of the invention, in the step 2.1, the time of magnetic stirring is 15min-30 min.
As a further improvement of the technical scheme of the invention, in the step 2.2, the reaction is carried out in an electrothermal constant-temperature air-blast drying oven at the temperature of 140-160 ℃ for 4-10 h.
As a further improvement of the technical scheme of the invention, in the step 2.2, the temperature of the vacuum drying treatment is 60-80 ℃, and the time is 6-12 h.
Advantageous effects of the inventionThe fruit is as follows: the crystalline Ni (OH) is obtained by the preparation method of the electrode material with the crystalline amorphous concerted catalysis interface2The amorphous NiMoS electrode material with a synergetic catalytic interface has more electrochemical active sites, small electron transmission impedance and electrocatalytic activity compared with crystalline Ni (OH)2Amorphous NiMoS and crystalline Ni (OH)2With crystalline NiMoS (MoS)2And NiS), has good electrocatalytic stability, simple preparation process, mild condition and convenient operation.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows crystalline Ni (OH) obtained by the preparation method of the present invention2Nanosheet precursor, crystalline ni (oh)2SEM, TEM, and EDX elemental mapping images of the electrode material with a co-catalytic interface for amorphous NiMoS;
FIG. 2 shows crystalline Ni (OH) obtained by the preparation method of the present invention2Nanosheet precursor, crystalline ni (oh)2X-ray powder diffraction patterns of electrode materials with a co-catalytic interface for amorphous NiMoS;
FIG. 3 shows crystalline Ni (OH) obtained by the preparation method of the present invention2The amorphous NiMoS has an X-ray photoelectron energy spectrum of an electrode material of a cooperative catalytic interface;
FIG. 4 shows crystalline Ni (OH) obtained by the preparation method of the present invention2A raman spectrum of an electrode material with a co-catalytic interface in amorphous NiMoS;
FIG. 5 shows crystalline Ni (OH) obtained by the preparation method of the present invention2Amorphous NiMoS electrode material with a concerted catalytic interface and crystalline Ni (OH) obtained in comparative example 12X-ray powder diffraction and HRTEM of crystalline NiMoS electrocatalytic material;
FIG. 6 shows crystalline Ni (OH) obtained by the preparation method of the present invention2Electrode material with a co-catalytic interface for amorphous NiMoS and obtained in comparative example 2The X-ray powder diffraction pattern of the amorphous NiMoS electro-catalytic material and the EDX element distribution pattern of the amorphous NiMoS electro-catalytic material;
FIG. 7 is crystalline Ni (OH)2Nanosheet precursor, crystalline Ni (OH) obtained by the preparation method of the invention2An electrocatalysis performance comparison graph and a stability test graph of the electrode material with the amorphous NiMoS synergistic catalysis interface in 1M KOH, 1M PBS and natural seawater;
FIG. 8 is crystalline Ni (OH)2Nanosheet precursor, crystalline Ni (OH) obtained by the preparation method of the invention2Pressure impedance plot of electrode material with co-catalytic interface in 1M KOH, 1M PBS and natural seawater for amorphous NiMoS;
FIG. 9 shows crystalline Ni (OH) obtained by the preparation method of the present invention2Amorphous NiMoS electrode material with a concerted catalytic interface, crystalline Ni (OH) obtained in comparative example 12Electrocatalytic performance plots for the crystalline NiMoS electrocatalytic material and the amorphous NiMoS electrocatalytic material obtained in comparative example 2;
FIG. 10 shows crystalline Ni (OH) obtained by the preparation method of the present invention2Amorphous NiMoS electrode material with a concerted catalytic interface, crystalline Ni (OH) obtained in comparative example 12An electrochemically active area contrast plot of a crystalline NiMoS electrocatalytic material;
FIG. 11 shows crystalline Ni (OH) obtained by the preparation method of the present invention2Amorphous NiMoS electrode materials with a co-catalytic interface at 0.5M H2SO4Electrochemical performance test pattern in solution.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
The invention relates to an electrode material with a crystalline-amorphous concerted catalysis interface, which comprises crystalline Ni (OH)2And amorphous NiMoS, whichThe medium amorphous NiMoS is prepared from Ni (OH)2Conversion to crystalline Ni (OH)2And the amorphous NiMoS form a cooperative catalytic interface.
The invention relates to a preparation method of an electrode material with a crystalline-state and amorphous-state synergetic catalytic interface, which is implemented according to the following steps:
step 1, preparing in-situ grown crystalline Ni (OH) on a titanium mesh2A nanosheet precursor; preparation of in-situ grown crystalline Ni (OH) on titanium mesh2The nanosheet precursor specifically comprises the following components:
step 1.1, shearing two titanium nets, putting the titanium nets into a hydrochloric acid solution with the concentration of 1-5 mol/L for ultrasonic treatment for 15-30 min, cleaning the titanium nets for several times by using absolute ethyl alcohol and ultrapure water, and drying the titanium nets for later use;
step 1.2, according to 1: 5-10: the molar ratio of 5-10 is measured as Ni (NO)3)2·6H2O、CO(NH2)2And NH4F, dissolving the three components in ultrapure water, and carrying out constant-temperature magnetic stirring to obtain a light green transparent solution;
step 1.3, transferring the light green transparent solution obtained in the step 1.2 into a reaction kettle, then putting the titanium net obtained in the step 1.1 at a certain angle against the inner wall of the reaction kettle for sealing, putting the reaction kettle into an electric heating constant temperature blast drying oven for reaction at the temperature of 120-180 ℃ for 4-10 h, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the titanium net for a plurality of times by using ultrapure water and absolute ethyl alcohol, and performing vacuum drying treatment to obtain crystalline Ni (OH)2The temperature of the nano sheet precursor is 60-80 ℃ and the time is 6-12 h after vacuum drying treatment;
step 2, the crystalline state Ni (OH) obtained in the step 12Molybdenum sulfurization treatment is carried out on the nanosheet precursor to prepare crystalline Ni (OH)2An electrode material with a concerted catalytic interface of amorphous NiMoS; for crystalline Ni (OH) obtained in step 12The molybdenum vulcanization treatment of the nanosheet precursor is as follows:
step 2.1, measure (NH)4)2MoS4Dissolving in ultrapure water, magnetically stirring at constant temperature for 15-30 min to dissolve, and transferring to reverse reactionReaction in a kettle; wherein Ni (NO)3)2·6H2O and (NH)4)2MoS4In a molar ratio of 1: 0.2-0.7.
Step 2.2, the crystalline state Ni (OH) obtained in the step 12Sealing a nanosheet precursor after leaning against the inner wall of a reaction kettle at a certain angle, then placing the reaction kettle into an electric heating constant-temperature air-blowing drying oven for reaction, wherein the temperature for reaction in the electric heating constant-temperature air-blowing drying oven is 140-160 ℃, the time is 4-10 h, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the reaction kettle for a plurality of times by using ultrapure water and absolute ethyl alcohol, and finally carrying out vacuum drying treatment to obtain crystalline Ni (OH)2The temperature of vacuum drying treatment is 60-80 ℃, and the time is 6-12 h.
Example 1
The invention relates to a preparation method of an electrode material with a crystalline-state and amorphous-state synergetic catalytic interface, which is implemented according to the following steps:
step 1, preparing in-situ grown crystalline Ni (OH) on a titanium mesh2A nanosheet precursor; preparation of in-situ grown crystalline Ni (OH) on titanium mesh2The nanosheet precursor specifically comprises the following components:
step 1.1, shearing two titanium nets, placing the titanium nets into a hydrochloric acid solution with the concentration of 1mol/L for ultrasonic treatment for 15min, washing the titanium nets for several times by using absolute ethyl alcohol and ultrapure water, and drying the titanium nets for later use;
step 1.2, according to 1: 5: 5 molar ratio of Ni (NO)3)2·6H2O、CO(NH2)2And NH4F, dissolving the three components in ultrapure water, and carrying out constant-temperature magnetic stirring to obtain a light green transparent solution;
step 1.3, transferring the light green transparent solution obtained in the step 1.2 into a reaction kettle, then putting the titanium mesh obtained in the step 1.1 at a certain angle against the inner wall of the reaction kettle for sealing, putting the reaction kettle into an electric heating constant temperature blast drying box for reaction, wherein the reaction temperature is 120 ℃, the reaction time is 4 hours, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the titanium mesh for a plurality of times by ultrapure water and absolute ethyl alcohol, and drying the titanium mesh in vacuumCrystalline Ni (OH) is obtained after treatment2The temperature of the nano sheet precursor is 60 ℃ and the time of the vacuum drying treatment is 6 h;
step 2, the crystalline state Ni (OH) obtained in the step 12Molybdenum sulfurization treatment is carried out on the nanosheet precursor to prepare crystalline Ni (OH)2An electrode material with a concerted catalytic interface of amorphous NiMoS; for crystalline Ni (OH) obtained in step 12The molybdenum vulcanization treatment of the nanosheet precursor is as follows:
step 2.1, measure (NH)4)2MoS4Dissolving in ultrapure water, carrying out constant-temperature magnetic stirring for 15min until the ultrapure water is dissolved, and then transferring to a reaction kettle; wherein Ni (NO)3)2·6H2O and (NH)4)2MoS4In a molar ratio of 1: 0.2.
step 2.2, the crystalline state Ni (OH) obtained in the step 12Sealing a nanosheet precursor after leaning against the inner wall of a reaction kettle at a certain angle, then placing the reaction kettle into an electric heating constant-temperature air-blowing drying oven for reaction, wherein the temperature for reaction in the electric heating constant-temperature air-blowing drying oven is 140 ℃, the time is 4 hours, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the reaction kettle for a plurality of times by using ultrapure water and absolute ethyl alcohol, and finally carrying out vacuum drying treatment to obtain a crystalline state Ni (OH)2And the temperature of the vacuum drying treatment is 60 ℃, and the time is 6 hours.
Example 2
The invention relates to a preparation method of an electrode material with a crystalline-state and amorphous-state synergetic catalytic interface, which is implemented according to the following steps:
step 1, preparing in-situ grown crystalline Ni (OH) on a titanium mesh2A nanosheet precursor; preparation of in-situ grown crystalline Ni (OH) on titanium mesh2The nanosheet precursor specifically comprises the following components:
step 1.1, shearing two titanium nets, placing the titanium nets into a hydrochloric acid solution with the concentration of 3mol/L for ultrasonic treatment for 15min-30min, cleaning the titanium nets with absolute ethyl alcohol and ultrapure water for a plurality of times, and drying the titanium nets for later use;
step 1.2, according to 1: 7: 8 molar ratio of Ni (NO)3)2·6H2O、CO(NH2)2And NH4F, dissolving the three components in ultrapure water, and carrying out constant-temperature magnetic stirring to obtain a light green transparent solution;
step 1.3, transferring the light green transparent solution obtained in the step 1.2 into a reaction kettle, then putting the titanium net obtained in the step 1.1 at a certain angle against the inner wall of the reaction kettle for sealing, putting the reaction kettle into an electric heating constant temperature blast drying oven for reaction at the temperature of 150 ℃ for 7 hours, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the titanium net for a plurality of times by ultrapure water and absolute ethyl alcohol, and performing vacuum drying treatment to obtain crystalline Ni (OH)2The temperature of the nano sheet precursor is 70 ℃ and the time of the vacuum drying treatment is 9 h;
step 2, the crystalline state Ni (OH) obtained in the step 12Molybdenum sulfurization treatment is carried out on the nanosheet precursor to prepare crystalline Ni (OH)2An electrode material with a concerted catalytic interface of amorphous NiMoS; for crystalline Ni (OH) obtained in step 12The molybdenum vulcanization treatment of the nanosheet precursor is as follows:
step 2.1, measure (NH)4)2MoS4Dissolving in ultrapure water, performing constant-temperature magnetic stirring for 27min until the ultrapure water is dissolved, and then transferring to a reaction kettle; wherein Ni (NO)3)2·6H2O and (NH)4)2MoS4In a molar ratio of 1: 0.5.
step 2.2, the crystalline state Ni (OH) obtained in the step 12Sealing a nanosheet precursor after leaning against the inner wall of the reaction kettle at a certain angle, then placing the reaction kettle into an electric heating constant-temperature air-blowing drying oven for reaction, wherein the temperature for reaction in the electric heating constant-temperature air-blowing drying oven is 150 ℃, the time is 7 hours, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the reaction kettle for a plurality of times by using ultrapure water and absolute ethyl alcohol, and finally carrying out vacuum drying treatment to obtain a crystalline state Ni (OH)2And the temperature of the vacuum drying treatment is 70 ℃, and the time is 9 hours.
Example 3
The invention relates to a preparation method of an electrode material with a crystalline-state and amorphous-state synergetic catalytic interface, which is implemented according to the following steps:
step 1, preparing in-situ grown crystalline Ni (OH) on a titanium mesh2A nanosheet precursor; preparation of in-situ grown crystalline Ni (OH) on titanium mesh2The nanosheet precursor specifically comprises the following components:
step 1.1, shearing two titanium nets, putting the titanium nets into a hydrochloric acid solution with the concentration of 1-5 mol/L for ultrasonic treatment for 15-30 min, cleaning the titanium nets for several times by using absolute ethyl alcohol and ultrapure water, and drying the titanium nets for later use;
step 1.2, according to 1: 10: the molar ratio of 10 is taken as Ni (NO)3)2·6H2O、CO(NH2)2And NH4F, dissolving the three components in ultrapure water, and carrying out constant-temperature magnetic stirring to obtain a light green transparent solution;
step 1.3, transferring the light green transparent solution obtained in the step 1.2 into a reaction kettle, then putting the titanium net obtained in the step 1.1 at a certain angle against the inner wall of the reaction kettle for sealing, putting the reaction kettle into an electric heating constant temperature blast drying oven for reaction at the temperature of 180 ℃ for 10 hours, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the titanium net for a plurality of times by ultrapure water and absolute ethyl alcohol, and performing vacuum drying treatment to obtain crystalline Ni (OH)2The temperature of the nano sheet precursor is 80 ℃ and the time of the nano sheet precursor is 12 h;
step 2, the crystalline state Ni (OH) obtained in the step 12Molybdenum sulfurization treatment is carried out on the nanosheet precursor to prepare crystalline Ni (OH)2An electrode material with a concerted catalytic interface of amorphous NiMoS; for crystalline Ni (OH) obtained in step 12The molybdenum vulcanization treatment of the nanosheet precursor is as follows:
step 2.1, measure (NH)4)2MoS4Dissolving in ultrapure water, performing constant-temperature magnetic stirring for 30min until the ultrapure water is dissolved, and then transferring to a reaction kettle; wherein Ni (NO)3)2·6H2O and (NH)4)2MoS4In a molar ratio of 1: 0.7.
step 2.2, the crystalline state Ni (OH) obtained in the step 12Nanosheet precursorLeaning against the inner wall of the reaction kettle at a certain angle, sealing, then putting the reaction kettle into an electric heating constant temperature air blast drying oven for reaction, wherein the temperature for reaction in the electric heating constant temperature air blast drying oven is 160 ℃, the time is 10 hours, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the reaction kettle for a plurality of times by using ultrapure water and absolute ethyl alcohol, and finally carrying out vacuum drying treatment to obtain crystalline Ni (OH)2And the temperature of the vacuum drying treatment is 80 ℃, and the time is 12 hours.
Comparative example 1
For comparison, we also prepared crystalline Ni (OH)2The amorphous NiMoS electrocatalytic material is prepared by the following specific steps:
step 1.1, shearing two titanium nets, putting the titanium nets into a 3M hydrochloric acid solution for ultrasonic treatment for about 15min, washing the titanium nets with absolute ethyl alcohol and ultrapure water for several times, and drying the titanium nets for later use;
step 1.2, measure 1.4mmol of Ni (NO)3)2·6H2O, 7mmol of CO (NH)2)2And 7mmol of NH4F, dissolving in 35mL of ultrapure water, and carrying out constant-temperature magnetic stirring for 30min to obtain a green transparent solution;
step 1.3, transferring the transparent solution obtained in the step 1.2 into a reaction kettle, then putting the titanium mesh obtained in the step 1.1 at a certain angle against the inner wall of the reaction kettle for sealing, putting the reaction kettle into an electric heating constant-temperature blast drying box, carrying out reaction for 6h at 120 ℃, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the reaction kettle for a plurality of times by using ultrapure water and absolute ethyl alcohol, and carrying out vacuum drying treatment for 6h at 60 ℃ to obtain crystalline Ni (OH)2And (3) a nanosheet precursor.
Step 2.1, measure 0.1g of (NH)4)2MoS4Dissolving in 35mL of ultrapure water, carrying out constant-temperature magnetic stirring for 30min until the ultrapure water is dissolved, and then transferring to a reaction kettle;
step 2.2, the crystalline state Ni (OH) obtained in the step 1.32The nanosheet precursor leans against the inner wall of the reaction kettle to be sealed, then the reaction kettle is placed into an electric heating constant-temperature air-blast drying oven to be reacted for 6 hours at the temperature of 140 ℃, and the reaction is finishedThen naturally cooling the reaction kettle to room temperature, washing the reaction kettle for a plurality of times by ultrapure water and absolute ethyl alcohol, and carrying out vacuum drying treatment for 6h at the constant temperature of 60 ℃ to obtain crystalline Ni (OH)2Amorphous NiMoS has an electrode material with a co-catalytic interface.
Step 2.3, the crystalline state Ni (OH) obtained in the step 2.2 is treated in Ar atmosphere at the constant temperature of 500 DEG C2Calcining the electrode material with the amorphous NiMoS and the concerted catalytic interface for 1h to finally obtain crystalline Ni (OH)2Crystalline NiMoS electrocatalytic material.
Comparative example 2
In addition, we also prepared the amorphous NiMoS electrocatalytic material for comparison, and the specific preparation method is as follows:
step 1.1, shearing two titanium nets, putting the titanium nets into a 3M hydrochloric acid solution for ultrasonic treatment for about 15min, washing the titanium nets with absolute ethyl alcohol and ultrapure water for several times, and drying the titanium nets for later use;
step 1.2, measure 1.4mmol of Ni (NO)3)2·6H2O, 7mmol of CO (NH)2)2And 7mmol of NH4F, dissolving in 35mL of ultrapure water, and carrying out constant-temperature magnetic stirring for 30min to obtain a green transparent solution;
step 1.3, transferring the transparent solution obtained in the step 1.2 into a reaction kettle, then putting the titanium mesh obtained in the step 1.1 at a certain angle against the inner wall of the reaction kettle for sealing, putting the reaction kettle into an electric heating constant-temperature blast drying box, carrying out reaction for 6h at 120 ℃, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the reaction kettle for a plurality of times by using ultrapure water and absolute ethyl alcohol, and carrying out vacuum drying treatment for 6h at 60 ℃ to obtain crystalline Ni (OH)2And (3) a nanosheet precursor.
Step 2.1, measure 0.1g of (NH)4)2MoS4Dissolving in 35mL of ultrapure water, carrying out constant-temperature magnetic stirring for 30min until the ultrapure water is dissolved, and then transferring to a reaction kettle;
step 2.2, the crystalline state Ni (OH) obtained in the step 1.32The nanosheet precursor leans against the inner wall of the reaction kettle to be sealed, then the reaction kettle is placed into an electric heating constant-temperature air-blowing drying oven to be reacted for 6 hours at the temperature of 140 ℃, and the reaction kettle is placed into the reaction kettle after the reaction is finishedThen cooling to room temperature, washing with ultrapure water and absolute ethyl alcohol for several times, and vacuum drying at constant temperature of 60 ℃ for 6h to obtain crystalline Ni (OH)2Amorphous NiMoS has an electrode material with a co-catalytic interface.
Step 2.3, Ti @ Ni (OH) obtained in step 2.22Acid etching of NiMoS under acidic conditions, using a three-electrode system of an electrochemical workstation at-50 mA cm-2The stability test was carried out for 12h at constant current density, and then the electrocatalytic material of amorphous NiMoS (labeled as Ti @ NiMoS) was obtained by 6h vacuum drying at constant temperature of 60 ℃.
For convenience of description in conjunction with FIGS. 1-11, crystalline Ni (OH) will be described herein2The nanosheet precursor is noted as Ti @ Ni (OH)2Crystalline Ni (OH)2The amorphous NiMoS electrode material with a concerted catalytic interface is marked as Ti @ Ni (OH)2NiMoS, the electrocatalytic material of amorphous crystalline NiMoS is denoted as Ti @ NiMoS.
In FIG. 1, the symbol (a) represents Ti @ Ni (OH)2SEM image of (b) is Ti @ Ni (OH)2SEM images of NiMoS; the nanosheets are clearly visible in figures (a) and (b) and as the molybdenum sulphides, the nanosheets undergo some change, becoming coarser, with the nanosheets having a thickness of about 86.67nm, and in figure (c) being Ti @ ni (oh)2TEM image of NiMoS, image (d) is a high-resolution TEM image of the yellow zone of image (c), from which it is clear that the crystalline and amorphous regions are distinct, the crystalline regions showing lattice fringes corresponding to Ni (OH)2And (012) crystal planes, and no other lattice fringes about NiMoS are found, indicating that the amorphous region corresponds to NiMoS. FIG. (e) is Ti @ Ni (OH)2EDX spectral images of NiMoS, from which it can be seen that the Ni, Mo and S elements are present and uniformly distributed in Ti @ Ni (OH)2-the surface of NiMoS.
FIG. 2 shows Ti @ Ni (OH)2And Ti @ Ni (OH)2-XRD pattern of NiMoS; from the figure, it appears that Ni (OH)2The characteristic diffraction peak of the compound is not found after molybdenum vulcanization, and the NiMoS is proved to be in an amorphous form and crystalline Ni (OH)2Coexisting, indicating part of the crystalline state Ni (OH)2Partial conversion to amorphous NiMoS occurred.
FIG. 3 shows Ti @ Ni (OH)2XPS plot of NiMoS, able to analyze Ti @ Ni (OH)2-surface composition and chemical valence of NiMoS; the Ni 2p spectrum (FIG. a) clearly shows characteristic peaks for Ni 2p3/2 at 853.6eV and 856.3eV and 2p1/2 at 871.0eV and 874.3eV, respectively. In the spectrum of Mo3d (FIG. b), the peak at 226.1eV corresponds to the Mo-S bond. In addition, the characteristic peaks at 228.6eV and 232.1eV in the Mo3d spectrum correspond to Mo3d 5/2 and Mo3d 3/2, respectively, while the characteristic peak at 235.5eV belongs to the hexavalent peak of molybdenum. In S2 p (FIG. c), the characteristic peak at 161.8eV corresponds to a Mo-S bond. The formation of NiMoS was verified by the peaks at the binding energies of 161.2eV and 168.2eV, respectively, pointing to the Ni — S bond.
FIG. 4 shows Ti @ Ni (OH)2Raman map of NiMoS. 374.5 and 404.9cm can be seen in the figure-1The characteristic peak of (A) is represented by MoS2E of (A)1 2g(in-plane) A1gCaused by (out-of-plane) vibration, 943.4cm-1The characteristic peak belongs to the Mo-S symmetrical stretching state. 196.7, 245.1, 304 and 333.5cm-1The characteristic peak of (a) is related to the vibration of the Ni-S bond. These results further show that a portion of Ni (OH)2The precursor is transformed into amorphous NiMoS by molybdenum sulfide.
Ti@Ni(OH)2-NiMoS-500 is represented in Ti @ Ni (OH)2Calcination was carried out on the basis of NiMoS, the calcination temperature being 500 ℃. FIG. 5 is a graph (a) showing Ti @ Ni (OH)2-NiMoS and Ti @ Ni (OH)2-X-ray diffraction pattern of NiMoS-500; FIGS. (b) and (c) are Ti @ Ni (OH)2-high resolution TEM images of NiMoS-500; as can be seen from FIG. (a), Ti @ Ni (OH)2After calcination in an argon atmosphere, NiMoS shows many new diffraction peaks corresponding to MoS2And the characteristic peak of NiS, which shows that the amorphous NiMoS is successfully converted into MoS2And NiS, Ni (OH)2Still present. FIGS. (b) and (c) clearly show Ti @ Ni (OH)2Morphology of NiMoS-500 and lattice fringes of different crystal forms, visible in graph (c) at Ti @ Ni (OH)2NiMoS-500 Ni (OH)2、MoS2Crystal face different from NiSAlso, this demonstrates the successful conversion of amorphous NiMoS to crystalline NiMoS (MoS)2And NiS), NiMoS is calcined into MoS after being analyzed after calcination2And NiS, essentially in the form of these two crystalline materials).
FIG. 6 is a graph (a) showing Ti @ Ni (OH)2-X-ray diffraction patterns of NiMoS and Ti @ NiMoS; FIG. (b) is the EDX elemental profile of Ti @ NiMoS; as can be seen from FIG. (a), Ti @ Ni (OH)2After acid etching, the XRD pattern of NiMoS only has a characteristic peak of Ti mesh, and no other diffraction peaks are found, which indicates that Ti @ Ni (OH)2Ni (OH) in NiMoS2Is completely etched in an acidic solution. Graph (b) is the EDX distribution plot of Ti @ NiMoS after test etching, from which it can still be seen that the Ni, Mo and S elements are present and uniformly distributed.
Crystalline Ni (OH) prepared according to the invention2The amorphous NiMoS electrode material with the synergetic catalytic interface can be used for high-efficiency electro-catalytic hydrogen evolution in the full pH value range and natural seawater. The hydrogen energy has the advantages of high heat value, wide source, various utilization forms, no pollution of reactants and the like, and is clean and stable sustainable energy. The electrolyzed water is called as one of the cleanest and economic hydrogen production modes due to the characteristics of high efficiency, environmental protection, no carbon emission and the like. Most of the reported electrocatalysts are limited to a very narrow pH range or a highly corrosive acidic/alkaline solution, and the number of the catalysts with excellent electrocatalysis performance in natural seawater is much less. The seawater accounts for about 97 percent of the total amount of water resources of the earth, and has great attraction for replacing fresh water by large-scale industrial electrolytic water hydrogen production. However, the development of hydrogen production by seawater electrolysis is hindered by problems such as the release of chloride, the formation of insoluble deposits, and the easy corrosion of electrodes. Therefore, the non-noble metal-based electrocatalyst which is durable and widely applied is found to have important significance for large-scale hydrogen production by using seawater.
The experimental conditions were as follows: ti @ Ni (OH) prepared using a typical three-electrode system2NiMoS as working electrode, graphite rod electrode as counter electrode, mercury/mercuric oxide electrode (i.e. KOH and natural seawater) and saturated calomel electrode (i.e. H)2SO4And PBS) as referenceAn electrode; all voltages relative to RHE were scaled by the following equation: eRHE＝EHg/HgO+0.059pH +0.098V (KOH and Natural seawater) and ERHE＝ESCE+0.059pH+0.242V(H2SO4And PBS). The scanning speed of the linear voltammetry scanning test is 2 mV/s.
FIG. 7 is Ti @ Ni (OH)2Nano precursor material and Ti @ Ni (OH)2Comparing electrocatalysis performance of NiMoS in 1M KOH, 1M PBS and natural seawater and testing stability, wherein 1M KOH represents 1mol/L KOH, and 1M PBS represents 1mol/L phosphoric acid buffer solution; for Ti mesh, Ti @ Ni (OH)2、Ti@Ni(OH)2NiMoS and commercial Pt/C in 1M KOH, 1M PBS and natural seawater electrochemical test. As can be seen from (a), (d) and (g) in FIG. 7, Ti @ Ni (OH)2NiMoS also showed a comparison with Ti @ Ni (OH)2Has better HER performance than Ti mesh, and can reach 10mA cm at the over-potential of 180mV-2Furthermore, Ti @ Ni (OH)2NiMoS up to 10mA cm in 1M PBS (pH 7) and natural seawater-2The overpotential of (1) is 198 and 371mV, which is much lower than that of Ni (OH)2And Ti mesh. From the graphs (b), (e) and (h), Ti @ Ni (OH)2NiMoS has the smallest Tafel slope except Pt/C in 1M KOH, 1M PBS and natural seawater, indicating that it has faster reaction kinetics. Stability is also an important parameter for evaluating the quality of the catalyst, as can be seen from the stability tests in FIGS. (c), (f) and (i), Ti @ Ni (OH)2NiMoS also showed no decay in performance after one thousand cycles at different pH and essentially zero change in current after 12 hours of continuous electrolysis, indicating excellent stability and durability.
FIG. 8 shows Ti mesh (titanium mesh), Ti @ Ni (OH)2And Ti @ Ni (OH)2NiMoS in 1M KOH, 1M PBS and natural sea water in the pressure resistance test, 1M KOH for 1mol/L KOH, 1M PBS for 1mol/L phosphoric acid buffer solution; as can be seen from (a), (b) and (c), Ti @ Ni (OH)2The minimum arc radius of NiMoS in different electrolytes indicates Ti @ Ni (OH)2NiMoS has the smallest electrochemical impedance and the strongest electron transfer capability.
FIG. 9 is Ti @ Ni (OH)2-NiMoS、Ti@Ni(OH)2-plot of electrochemical performance of NiMoS-500 and Ti @ NiMoS in 1M KOH, 1M PBS and natural seawater; as can be seen from FIGS. (a), (b) and (c), Ti @ Ni (OH)2NiMoS can show the highest hydrogen evolution performance in alkaline, neutral and natural seawater, and is 10mA cm-2Shows minimal overvoltage at the current density of (a).
FIG. 10 is Ti @ Ni (OH)2-NiMoS、Ti@Ni(OH)2-the electrochemically active area of NiMoS-500 in 1M KOH, 1M PBS and natural seawater; from the figure, in different electrolytes, Ti @ Ni (OH)2NiMoS vs Ti @ Ni (OH)2NiMoS-500 has the largest electrochemically active area and thus more active sites, all due to crystalline Ni (OH)2And a co-catalytic interface of amorphous NiMoS.
FIG. 11 is a drawing (a) showing Ti mesh, Ti @ Ni (OH)2And Ti @ Ni (OH)2NiMoS and Pt/C at 0.5M H2SO4The electrochemical performance test in (1), wherein the plot (b) is the Tafel slope corresponding to the plot (a); FIG. (c) is Ti @ Ni (OH)2NiMoS at 0.5M H2SO4Testing medium stability; graph (d) is Ti @ Ni (OH) before and after etching in an acidic solution2-NiMoS electrochemical performance test; panel (e) is Ti mesh, Ti @ Ni (OH)2And electrochemical active area analysis of Ti @ NiMoS; panel (f) is Ti mesh, Ti @ Ni (OH)2And electrochemical impedance testing of Ti @ NiMoS.
As can be seen from the above, in FIG. (a), Ti @ Ni (OH)2NiMoS at a current density of 10mA cm-2The overpotential at this time was 138 mV. Ti @ Ni (OH)2Tafel slope of 81mV dec for NiMoS-1(FIG. b), both lower than Ti @ Ni (OH)2And Ti mesh, which shows excellent hydrogen evolution performance in an acidic solution. FIG. c is Ti @ Ni (OH)2NiMoS at 0.5M H2SO4At 12h, there was a slight float in current and a slight decrease in performance after 1000 LSV tests due to Ni (OH)2Caused by dissolution under acidic conditions. After 12h electrolysis, it was found from testing XRD and EDX element distribution that nickel hydroxide was completely dissolved, leaving only amorphous NiMoS, whereas Ti @ NiMoS showed similar excellence as seen in graph (d)Indicating that the active sites are mainly from amorphous NiMoS under acidic conditions. Ti @ NiMoS can also be seen to have the largest active area and the smallest electron transfer resistance by electrochemical active area and resistance testing.
While the foregoing description shows and describes several preferred embodiments of the invention, it is to be understood, as noted above, that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. An electrode material with a crystalline-amorphous concerted catalytic interface is characterized by comprising crystalline Ni (OH)2And amorphous NiMoS, wherein amorphous NiMoS is composed of Ni (OH)2Conversion to crystalline Ni (OH)2And the amorphous NiMoS form a cooperative catalytic interface.
2. A preparation method of an electrode material with a crystalline-state amorphous-state synergetic catalytic interface is characterized by comprising the following steps:
step 1, preparing in-situ grown crystalline Ni (OH) on a titanium mesh2A nanosheet precursor;
step 2, the crystalline state Ni (OH) obtained in the step 12Molybdenum sulfurization treatment is carried out on the nanosheet precursor to prepare crystalline Ni (OH)2Amorphous NiMoS has an electrode material with a co-catalytic interface.
3. The method for preparing electrode material with crystalline and amorphous concerted catalytic interface as claimed in claim 2, wherein in step 1, in-situ grown crystalline Ni (OH) is prepared on titanium mesh2The nanosheet precursor specifically comprises the following components:
step 1.1, shearing two titanium nets, putting the titanium nets into a hydrochloric acid solution for ultrasonic treatment, washing the titanium nets for several times by using absolute ethyl alcohol and ultrapure water, and drying the titanium nets for later use;
step 1.2, according to 1: 5-10: the molar ratio of 5-10 is measured as Ni (NO)3)2·6H2O、CO(NH2)2And NH4F, dissolving the three components in ultrapure water, and carrying out constant-temperature magnetic stirring to obtain a light green transparent solution;
step 1.3, transferring the light green transparent solution obtained in the step 1.2 into a reaction kettle, then putting the titanium net obtained in the step 1.1 at a certain angle against the inner wall of the reaction kettle for sealing, then putting the reaction kettle into an electric heating constant temperature blast drying box for reaction, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the titanium net for a plurality of times by ultrapure water and absolute ethyl alcohol, and carrying out vacuum drying treatment to obtain crystalline Ni (OH)2And (3) a nanosheet precursor.
4. The method for preparing an electrode material with a crystalline and amorphous concerted catalysis interface according to the claim 3, characterized in that in the step 1.1, the concentration of the hydrochloric acid is 1-5 mol/L, and the time of ultrasonic treatment is 15-30 min.
5. The method for preparing an electrode material with a crystalline amorphous concerted catalytic interface as claimed in claim 4, wherein in step 1.3: the temperature for reaction in the electric heating constant temperature blast drying oven is 120-180 ℃ and the time is 4-10 h.
6. The method for preparing an electrode material with a crystalline amorphous concerted catalytic interface as claimed in claim 5, wherein in step 1.3: the temperature of the vacuum drying treatment is 60-80 ℃, and the time is 6-12 h.
7. The method for preparing an electrode material with a crystalline and amorphous concerted catalytic interface as claimed in claim 6, wherein in the step 2, the crystalline Ni (OH) obtained in the step 1 is treated2Molybdenum is carried out on nanosheet precursorThe vulcanization treatment is specifically as follows:
step 2.1, measure (NH)4)2MoS4Dissolving in ultrapure water, carrying out constant-temperature magnetic stirring until the ultrapure water is dissolved, and then transferring to a reaction kettle; wherein Ni (NO)3)2·6H2O and (NH)4)2MoS4In a molar ratio of 1: 0.2-0.7.
Step 2.2, the crystalline state Ni (OH) obtained in the step 12Sealing a nanosheet precursor after leaning against the inner wall of the reaction kettle at a certain angle, then placing the reaction kettle into an electric heating constant-temperature blast drying box for reaction, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the reaction kettle for a plurality of times by using ultrapure water and absolute ethyl alcohol, and finally carrying out vacuum drying treatment to obtain crystalline Ni (OH)2And amorphous NiMoS electrode materials with a co-catalytic interface.
8. The method for preparing an electrode material with a crystalline and amorphous concerted catalytic interface as claimed in claim 7, wherein in the step 2.1, the time of magnetic stirring is 15min-30 min.
9. The method for preparing the electrode material with the crystalline amorphous concerted catalytic interface as claimed in claim 8, wherein in the step 2.2, the reaction is carried out in an electrothermal constant-temperature air-blast drying oven at the temperature of 140-160 ℃ for 4-10 h.
10. The method for preparing an electrode material with a crystalline and amorphous concerted catalytic interface according to claim 9, wherein in the step 2.2, the temperature of the vacuum drying treatment is 60-80 ℃ and the time is 6-12 h.
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