CN113930800A - Heterostructure electrocatalytic hydrogen evolution material and preparation method and application thereof - Google Patents

Heterostructure electrocatalytic hydrogen evolution material and preparation method and application thereof Download PDF

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CN113930800A
CN113930800A CN202111257235.5A CN202111257235A CN113930800A CN 113930800 A CN113930800 A CN 113930800A CN 202111257235 A CN202111257235 A CN 202111257235A CN 113930800 A CN113930800 A CN 113930800A
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hydrogen evolution
heterostructure
electrocatalytic hydrogen
coo
electrocatalytic
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崔亮
冯中汉
刘敬权
田相鑫
刘伟
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Linyi University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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    • C25B11/063—Valve metal, e.g. titanium
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • 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
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    • 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

Abstract

The invention discloses a heterostructure electrocatalytic hydrogen evolution material and a preparation method and application thereof, belonging to the technical field of preparation of inorganic nano catalytic materials. The molecular structural formula of the electrocatalytic hydrogen evolution material is CoO/Co3O4. The catalyst is loaded on a metal Ti substrate, and an active substance layer and an active component are formed on the surface of the Ti substrateThe layer is compact and has no crack, and is formed by arranging nanowire arrays containing a large number of oxygen vacancies, so that the contact area of the nanowire arrays and an electrolyte solution is increased, more active sites are exposed, and the hydrogen evolution reaction can be better carried out at room temperature. By reaction at H2Reduction of Co in the atmosphere3O4Nanowire array formation CoO/Co3O4Increase CoO/Co3O4Electrochemical performance of hydrogen evolution reaction. The preparation method of the material is simple to operate, is suitable for large-scale production, can be widely applied to electrochemical energy storage and conversion technology, and has high application value.

Description

Heterostructure electrocatalytic hydrogen evolution material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of inorganic nano catalytic materials, relates to a preparation method of a heterostructure electrocatalytic hydrogen evolution material, and particularly discloses a hydrogen evolution reaction electrocatalyst of a metal cobalt oxide, a preparation method of the electrocatalyst and application of the electrocatalyst in electrolyzed water.
Background
Environmental issues arising from increasing fossil fuel consumption are receiving increasing attention and it is therefore necessary to establish a clean and sustainable energy system on a global scale. The hydrogen production by water electrolysis is a promising method, and the obtained hydrogen has high purity and can be directly used as a fuel cell. A typical electrochemical water electrolysis system consists essentially of a cathode, an anode and an electrolyte, the cathode producing H by a Hydrogen Evolution Reaction (HER)2. However, the generation of external potentials due to the slow response under alkaline conditions is becoming a bottleneck for its scale-up. To solve this problem, noble metal-based electrocatalysts (e.g., Pt/C) are commonly used for high iron, but their scarcity and high cost severely limit their commercialization. Therefore, the development of an efficient, inexpensive and earth-resource-rich electrocatalyst is urgently needed.
Disclosure of Invention
In view of the above, the present invention provides a heterostructure electrocatalytic hydrogen evolution material, and a preparation method and an application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a heterostructure electrocatalytic hydrogen evolution material comprises a titanium mesh substrate and a carrier loaded on the titanium mesh substrateAn active component having a heterostructure on the mesh substrate; the active components are Co/CoO and CoO/Co3O4Or Co3O4。
It should be noted that in recent years, the abundant non-noble metal cobalt has been studied and applied in a great deal due to its unique electronic structure and better synergistic effect. Although the hydrogen evolution performance of cobalt-based phosphide, sulfide, hydroxide, boride, nitride and other electric catalysts prepared by various strategies is improved, the preparation process of the catalysts is complex, time-consuming and energy-consuming, so that the wide application of the catalysts is limited. Cobalt-based oxide catalysts have attracted much attention because of their inexpensive raw materials, simple preparation method, and good stability in alkaline media. In the cobalt-based oxide nano material catalyst, the HER performance can be obviously improved by adjusting the internal structure of the material and constructing a strategy of a heterostructure on rich interfaces among different components. The existence of the heterostructure in the material can expose more active sites, valence electrons can be transferred through an interface, the electron transmission capability is enhanced, different components can be complemented in a coordinated mode to generate an electron coupling reaction, and the HER catalytic activity can be obviously improved.
Preferably, the active component is CoO/Co3O4。
And the aperture of the titanium mesh substrate is 0.1-10 mm, the porosity is 90-99%, and the pore density is 50-200 PPI.
Further preferably, the pore diameter of the titanium mesh substrate is 0.1 mm-1 mm, the porosity is 96% -99%, and the pore density is 100 PPI-150 PPI.
It should be noted that the PPI is generally referred to as Pores Per Linear inc, which is a unit of pore density.
In addition, the thickness of the titanium mesh substrate is 0.1 mm-1 mm, preferably 0.1 mm-0.5 mm; and all commercial titanium mesh (Ti mesh) on the market can be used as the titanium mesh substrate of the invention, and the commercial titanium mesh with the pore diameter and porosity within the limited range of the invention is preferred; and the size of the titanium mesh substrate is 1cm2～ 10cm2Preferably 4cm2～8cm2。
The invention also aims to provide a preparation method of the heterostructure electrocatalytic hydrogen evolution material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a heterostructure electrocatalytic hydrogen evolution material comprises the following specific steps:
(1) carrying out hydrothermal treatment, heat treatment and hydrogen reduction treatment on a reaction system containing cobalt ions, a titanium mesh substrate and a solvent to obtain a precursor material;
and the precursor material comprises a titanium mesh substrate and composite metal oxides containing different cobalt oxides loaded on the titanium mesh substrate.
(2) And taking the precursor material as a working electrode to participate in the electrocatalytic hydrogen evolution reaction, thereby carrying out electrochemical activation on the precursor material to finally obtain the heterostructure electrocatalytic hydrogen evolution material.
By adopting the technical scheme, the invention has the following beneficial effects:
the preparation method disclosed by the invention is simple and convenient to operate, and the prepared electro-catalytic hydrogen evolution material has high catalytic activity and wide application prospect in the field of new energy.
Preferably, in the step (1), the cobalt ions are derived from soluble cobalt salt, and the aperture of the titanium mesh substrate is 0.1 mm-10 mm, preferably 0.1 mm-1 mm; the porosity is 90-99%, preferably 96-99%; the solvent is water, and the mass volume ratio of the soluble cobalt salt to the solvent is (0.1-10): 100g/mL, preferably (0.5-5): 100 g/mL.
And the quantity ratio of the soluble cobalt salt, the urea, the ammonium fluoride and the solvent is 1: 15: 8: 2778.
wherein the water may be one or more of deionized water, distilled water, pure water, high purity water and ultra pure water.
Further, the conditions of the hydrothermal treatment include: the temperature of the hydrothermal treatment is 120 ℃; the hydrothermal treatment time is 8 h; the conditions of the hydrogen reduction treatment include: the reduction temperature is 250-450 ℃, preferably 300-400 ℃; the reduction time was 2 h.
According to the present invention, the inventors of the present application found in their studies that the temperature of the treatment for hydrogen reduction can significantly affect the effect of electrochemical activation. When the temperature of the hydrogen reduction treatment is 300-400 ℃, the optimal electrochemical activation effect can be obtained.
According to the present invention, the temperature of the hydrogen reduction treatment can be enumerated as 250 ℃, 300 ℃, 350 ℃, 400 ℃ and any value therebetween.
According to the present invention, the hydrothermal treatment may be carried out in a reaction vessel.
According to the invention, after the hydrothermal treatment is completed, the precursor material is cooled to room temperature and then is subjected to heat treatment and hydrogen reduction treatment.
According to the present invention, the heat treatment and the hydrogen reduction treatment can be performed in a tube furnace.
According to the present invention, after the hydrogen reduction treatment, the precursor material may be subjected to step (2) after being cooled to room temperature.
Preferably, in the step (2), the potential of the working electrode is-0.1V to-0.5V, preferably-0.16V to-0.20V, and the reference electrode is a reversible hydrogen electrode.
The electrocatalytic hydrogen evolution reaction time in the step (2) is 10-30 h, the electrocatalytic hydrogen evolution reaction temperature is 20-40 ℃, and the preferred temperature is 25-35 ℃; and the electrolyte of the electrocatalytic hydrogen evolution reaction is a KOH solution with the concentration of 0.1-10 mol/L.
Exemplarily, the preparation method specifically comprises the following steps:
1) hydrothermal reaction:
1mmol Co(NO3)2·6H2O(0.873g)、8mmol NH4f (0.296g) and 15mmol (NH)2)2CO (0.901g) was dissolved in 50ml of deionized water and stirred for 25 minutes. Then the mixed solution was poured into a 50ml hydrothermal kettle, and a titanium mesh substrate (2X 3 cm)2) Obliquely placing and sealing, and placing the reaction kettle in an oven at 120 ℃ for reaction for 6 hours. Placing the reacted titanium net in a stripping deviceAnd ultrasonically washing the titanium substrate in water for 45 seconds, and then washing and drying the titanium substrate by using absolute ethyl alcohol to obtain a Co-precursor nanorod array (Co-precusor NA/Ti) loaded on a titanium net.
2) And (3) calcining reaction:
placing Co-precorsorrNA/Ti obliquely in a porcelain boat, heating to 250 ℃ at the temperature rising speed of 5 ℃/min in a tubular furnace under the air atmosphere, then keeping the temperature for 1 hour, and naturally cooling to obtain Co loaded on a titanium net3O4Nanoarrays (Co)3O4 NA/Ti)。
3) Reduction reaction:
mixing Co3O4NA/Ti is placed in a porcelain boat in an inclined manner in H2In an/Ar atmosphere, the temperature was raised to 350 ℃ at a rate of 5 ℃/min and then maintained at this temperature for 2 hours. Naturally cooling to room temperature to obtain the CoO/Co loaded on the titanium mesh3O4Nanowire arrays (CoO/Co)3O4 NA/Ti)。
And, the reaction principle in the above preparation process is as follows:
cobalt nitrate: providing a cobalt source;
ammonium fluoride (NH)4F) The method comprises the following steps Not only has the function of improving the reaction rate, but also can adjust the stability of the reaction. Generally, fluorine ions may be selectively adsorbed on each crystal face, so as to change the crystallization kinetic behavior of each crystal face, and finally, the difference in crystal morphology is caused. And NH4 +Relatively difficult to adsorb, but can change the polarity of the solution and influence mass transfer;
urea: as a reaction precipitant.
It is a further object of the present invention to provide the use of heterostructure electrocatalytic hydrogen evolution materials in the field of electrolysis of water.
In some application scenarios, the application of the heterostructure electrocatalytic hydrogen evolution material in the field of perhydrolysis is also included, and the electrocatalytic hydrogen evolution material is used as a cathode when the perhydrolysis is performed.
According to the technical scheme, compared with the prior art, the invention provides the heterostructure electrocatalytic hydrogen evolution material and the preparation method and application thereof, and the heterostructure electrocatalytic hydrogen evolution material has the following excellent effects:
the molecular structural formula of the electrocatalytic hydrogen evolution material is CoO/Co3O4. The catalyst is loaded on a metal Ti substrate, an active substance layer is formed on the surface of the Ti substrate, the active substance layer is compact and has no crack, the catalyst is formed by arranging nanowire arrays containing a large number of oxygen vacancies, the contact area of the catalyst and an electrolyte solution is increased, more active sites are exposed, and the hydrogen evolution reaction can be better carried out at room temperature. By reaction at H2Reduction of Co in the atmosphere3O4Nanowire array formation CoO/Co3O4Increase CoO/Co3O4Electrochemical performance of hydrogen evolution reaction.
Furthermore, CoO/Co3O4The material has excellent Hydrogen Evolution Reverse (HER) catalytic performance and long-term stability in electric conductivity in alkaline electrolyte solution, and is compared with Co3O410mA · cm thereof-2The corresponding overpotential, Tafel slope and exchange current density are obviously improved, and more importantly, the activity and the stability of the catalyst are superior to those of a commercial noble metal oxide Pt/C catalyst.
In addition, the preparation method of the material is simple to operate, is easy for large-scale production, can be widely applied to electrochemical energy storage and conversion technology, and has high application value.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a diagram of CoO/Co3O4A preparation process schematic diagram of the NA/Ti heterostructure catalytic hydrogen evolution material.
In FIG. 2, (a) is a exfoliated CoO/Co3O4XRD spectrogram of the nanowire; (b-d) are eachPrecursors NA/Ti, Co3O4NA/Ti and CoO/Co3O4SEM image of NA/Ti.
In FIG. 3, (a-b) is CoO/Co3O4TEM images of the nanowires; (c) is CoO/Co3O4HRTEM images of nanowires; (d) is CoO/Co3O4Nanowire SAED image, in which CoO/Co3O4Stem segment images of nanowires and corresponding EDX element mapping; (e-g) is CoO/Co3O4Transmission electron microscope photograph and element energy spectrogram of the nano wire.
FIG. 4 is a diagram of CoO/Co3O4XPS spectra of the composite, wherein (a) is Co 2 p; (b) is O1 s.
In FIG. 5, (a) is the LSV curve of-48 mv versus RHE at 1.0M KOH for different samples and (b) the corresponding overpotential contrast plot and (c) the Tafel plot; (d) is CoO/Co3O4NA/Ti Multi-Current Process: the current density is from 2.5mA cm-2At first, 17.5mA cm-2At the end, every 1000s, 2.5mA cm-2No iR correction is required; (e) is CoO/Co3O4NA/Ti at constant current density of 10mA cm-2Next, time potential curve without iR correction; (f) is infrared corrected CoO/Co3O4Polarization curves of NA/Ti before and after 1000CV cycles.
In FIG. 6, (a) is a sample XRD spectrum at a reduction temperature of 250 ℃, (b) is a sample XRD spectrum at a reduction temperature of 300 ℃, and (c) is a sample XRD spectrum at a reduction temperature of 400 ℃.
In FIG. 7, (a) is the LSV curve of-48 mv vs. RHE at 1.0M KOH for samples of different reduction temperatures and (b) the corresponding Tafel plot.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a preparation method of a heterostructure electrocatalytic hydrogen evolution material.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1:
a preparation method of a heterostructure electrocatalytic hydrogen evolution material comprises the following steps:
1) cutting a commercial titanium net into small blocks of 2cm x 3cm, firstly soaking the titanium net in concentrated hydrochloric acid for 5 minutes, then respectively ultrasonically cleaning the titanium net for 5 minutes by deionized water and ethanol/acetone, and drying the titanium net for later use.
2) 1mmol of Co (NO)3)2·6H2O(0.873g)、8mmol NH4F(0.296g)、15mmol (NH2)2Dissolving CO (0.901g) in 50ml of deionized water, and stirring for 25 minutes to prepare a Co-containing solution; the Co-containing solution thus obtained was transferred to a 50ml hydrothermal reactor lined with polytetrafluoroethylene, and a pretreated titanium mesh substrate (2X 3 cm) was placed in the Co-containing solution in an inclined manner2) And to allow it to soak thoroughly.
3) And sealing the reaction kettle, and then putting the reaction kettle into an oven to perform hydrothermal reaction at the reaction temperature of 120 ℃ for 6 hours. After the reaction is finished, the reaction kettle is naturally cooled to room temperature, a sample (namely a precursor material) is taken out, is fully cleaned by deionized water and ethanol/acetone, and is naturally dried for later use.
4) Suspending the bottom of the sample obtained in the step 3) and obliquely placing the sample in a porcelain boat, placing the porcelain boat in a tubular furnace, heating the porcelain boat to 250 ℃ at a heating speed of 5 ℃/min in the air atmosphere, then keeping the porcelain boat at the temperature for 1 hour, and finally electro-catalyzing a hydrogen evolution material intermediate.
5) Co of the prepared sample obtained in the step 4)3O4NA/Ti bottom suspensionEmpty and inclined in a porcelain boat at H2Heating to 350 deg.C at a heating rate of 5 deg.C/min under Ar atmosphere, and maintaining at the temperature for 2 h. And finally, cooling to room temperature to obtain the heterostructure electrocatalytic hydrogen evolution material.
The flow chart of the electrocatalytic preparation is shown in figure 1.
And the obtained electrocatalytic hydrogen evolution material is subjected to XRD test, and the obtained XRD pattern is shown as figure 2 (a).
As can be seen from FIG. 2(a), the five peaks located in the 36.6 °, 42.6 °, 61.8 °, 74.4 ° and 77.5 ° crystal planes are ascribed to the X-ray characteristic diffraction peaks of the (111), (200), (220), (311) and (222) crystal planes of CoO (PDF # 01-1227). Twelve peaks located in the 31.3 °, 42.6 °, 38.5 °, 44.8 °, 49.1 °, 55.6 °, 59.3 °, 65.2 °, 74.4 °, 77.5 °, 78.4 ° and 82.6 ° crystallographic planes are assigned to Co3O4(PDF #78-1970) X-ray characteristic diffraction peaks for (220), (311), (222), (400), (331), (422), (511), (440), (620), (533), (622), and (444) crystal planes. From the matching result, it can be preliminarily determined that CoO and Co loaded on the titanium mesh can be obtained by adopting hydrothermal and controllable reduction calcination treatment3O4Grains, indicating the successful formation of CoO/Co3O4A heterostructure.
And, for the prepared cobalt precursor, Co3O4Nanoarrays and CoO/Co3O4SEM analysis of the nano-array material was performed, and the obtained SEM pictures are shown in FIGS. 2 (b-d). And as can be seen from fig. 2b, the exposed titanium mesh surface after the hydrothermal treatment is completely covered by the nanowire array, indicating that the precursor is successfully prepared. In addition, it can be seen that during calcination, with untreated Co3O4Compared with the nano-wires, the nano-wires have rough surfaces after reduction process and are Co3O4The results of the reductive decomposition (FIGS. 2 b-d). And as can be seen from fig. 2b, the surface of the nanowires is rough, and a large number of oxygen vacancies are present, and the vacancies can increase the contact area of the material and the electrolyte, thereby facilitating the electrochemical action.
Further, TEM analysis was performed on the produced electrocatalytic hydrogen evolution material, and a TEM picture was obtained as shown in fig. 3.
As can be seen from FIG. 3, the nanowires on the surface of the titanium mesh substrate are stacked by a plurality of nanospheres with the same size, the nanospheres have the size of about a few nanometers, and contain abundant heterostructures, and clear lattice fringes and heterojunctions can be seen in the high-resolution TEM photograph, wherein the (200) crystal face of CoO (PDF #01-1227) and Co3O4(PDF #78-1970) the (311) lattice plane constitutes CoO/Co3O4The interface of the heterostructure further proves that CoO/Co3O4The successful preparation.
And performing selective electron diffraction on the prepared electro-catalytic hydrogen evolution material, wherein the result is shown in figure 3(d), and the selective electron diffraction graph shows the multiphase characteristics of the sample, which shows that CoO and Co3O4Presence of and CoO/Co3O4Successful fabrication of heterostructures.
Meanwhile, EDS test is carried out on the prepared electro-catalytic hydrogen evolution material, the graph is shown in figure 3(e-g), and Co and O elements are in CoO/Co according to figure 3(e-g)3O4Medium and uniform distribution while CoO/Co3O4The ratio of Co to O elements in the sample was about 46:54, from which the CoO/Co ratio was calculated3O4CoO and Co in heterostructures3O4In a molar ratio of 11: 4.
Furthermore, the obtained electrocatalytic hydrogen evolution material was subjected to XPS test, and the results are shown in fig. 4. FIG. 4a is a nuclear XPS spectrum of Co 2p, the Co element in CoO generates two typical main peaks, Co 2p1/2 (796.1eV) and Co 2p3/2(780.3eV), indicating that CoO/Co3O4Surface of Co2+Species of the species. O1s XPS spectrum as shown in FIG. 4b, the peak at 529.5eV can be assigned to the O of CoO2-The small shoulder around 531eV is ascribed to the hydroxyl group of the CoO surface layer.
Finally, the linear voltammograms and other electrochemical test curves of the produced electrocatalytic hydrogen evolution material are shown in fig. 5, and the results are analyzed as follows.
The results of the linear voltammetric scan are shown in FIG. 5a, indicating that the prepared CoO/Co3O4Has better electrocatalytic hydrogen evolution performance, and compared with a precursor material, the reduced hydrogen evolutionThe HER activity of the material was significantly enhanced. Reduced hydrogen evolution material 10mA cm-2The hydrogen evolution current density corresponds to the over-potential of only 108 mV. Even at 100mA cm-2The overpotential required for the reduced hydrogen evolution material electrode is only 151.8mV at the high current density of (2). This result demonstrates that the precursor material can be reduced in an alkaline medium to a highly active HER electrocatalyst.
The test result of the multi-step current method shows that the potential immediately generates response along with the change of the current density, which indicates that CoO/Co3O4The electron transfer rate between is very high. The test data graph is shown in fig. 5 (d). CoO/Co3O4At 1.0M KOH and 10mA cm-2Under the conditions, the test result of the timing potential is shown in fig. 5(e), which shows a parallel trend with the time axis, and no obvious potential drop shows that the timing potential has good sustainability and stability. In a 1.0M KOH solution, at a scan rate of 5mV s-1The results of 1000 cyclic voltammetry tests under the conditions (A) are shown in FIG. 5(f), and the linear voltammograms before and after the cycle almost coincide with each other, indicating that CoO/Co3O4Long term stability of (c).
Example 2:
steps 1) -5) in example 2 were the same as in example 1, and step 6) was substantially the same as in example 1 except that the reaction time (i.e., the temperature of the reduction treatment) was adjusted to 250 ℃.
Example 3:
steps 1) -5) in example 3 were the same as in example 1, and step 6) was substantially the same as in example 1 except that the reaction time (i.e., the temperature of the reduction treatment) was adjusted to 300 ℃.
Example 4:
steps 1) -5) in example 4 were the same as in example 1, and step 6) was substantially the same as in example 1 except that the reaction time (i.e., the temperature of the reduction treatment) was adjusted to 400 ℃.
The structural composition characterization results of the materials of examples 2-4 are shown in FIG. 6, and it can be found by comparison that the compositions of the materials are different at different reduction temperatures, and the main component of the material is Co under the reduction conditions of 250 ℃ and 300 ℃3O4The main composition at 400 ℃ is Co/Co3O4(ii) a The corresponding electrochemical test results are shown in fig. 7, and it can be seen from fig. 5(a),
the previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A heterostructure electrocatalytic hydrogen evolution material, comprising a titanium mesh substrate and an active component having a heterostructure supported on the titanium mesh substrate; the active components are Co/CoO and CoO/Co3O4Or Co3O4。
2. A heterostructure electrocatalytic hydrogen evolution material as set forth in claim 1, wherein the active component is CoO/Co3O4And the aperture of the titanium mesh substrate is 0.1 mm-10 mm, the porosity is 90% -99%, and the pore density is 50 PPI-200 PPI.
3. A method for preparing a heterostructure electrocatalytic hydrogen evolution material as set forth in claim 1, comprising the steps of:
(1) carrying out hydrothermal treatment and hydrogen reduction treatment on a reaction system containing cobalt ions, ammonium fluoride, urea, a titanium mesh substrate and a solvent to obtain a precursor material;
(2) and taking the precursor material as a working electrode to participate in the electrocatalytic hydrogen evolution reaction, thereby carrying out electrochemical activation on the precursor material to finally obtain the heterostructure electrocatalytic hydrogen evolution material.
4. The method for preparing a heterostructure electrocatalytic hydrogen evolution material according to claim 3, wherein in the step (1), the cobalt ions are derived from soluble cobalt salt, the pore diameter of the titanium mesh substrate is 0.1 mm-10 mm, the porosity is 90% -99%, and the solvent is water.
5. The method for preparing the heterostructure electrocatalytic hydrogen evolution material according to claim 4, wherein the mass-to-volume ratio of the soluble cobalt salt to the solvent is (0.1-10): 100g/mL, and the mass ratio of the soluble cobalt salt, urea, ammonium fluoride and solvent is 1: 15: 8: 2778.
6. a method for preparing a heterostructure electrocatalytic hydrogen evolution material according to claim 3 or 5, characterized in that the conditions of the hydrothermal treatment comprise: the temperature of the hydrothermal treatment is 120 ℃, and the time of the hydrothermal treatment is 6 h; the conditions of the hydrogen reduction treatment include: the reduction temperature is 250-450 ℃, and the reduction time is 2 h.
7. The method for preparing a heterostructure electrocatalytic hydrogen evolution material of claim 3, wherein in the step (2), the potential of the working electrode is-0.1V to-0.5V, and the reference electrode is a reversible hydrogen electrode.
8. The preparation method of the heterostructure electrocatalytic hydrogen evolution material as set forth in claim 3, wherein the electrochemical activation time in the step (2) is 10-30 h, and the electrocatalytic hydrogen evolution reaction temperature is 20-40 ℃; and the electrolyte of the electrocatalytic hydrogen evolution reaction is a KOH solution with the concentration of 0.1-10 mol/L.
9. Use of the heterostructure electrocatalytic hydrogen evolution material as defined in claim 1 or prepared by the method as defined in claim 3 in the field of electrolysis of water.
10. Use according to claim 9, characterised in that it comprises the use of an electrocatalytic hydrogen evolution material in the field of perhydrolysis and in that said electrocatalytic hydrogen evolution material is used as cathode in the case of perhydrolysis.
CN202111257235.5A 2021-10-27 2021-10-27 Heterostructure electrocatalytic hydrogen evolution material and preparation method and application thereof Withdrawn CN113930800A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114540833A (en) * 2022-02-22 2022-05-27 临沂大学 CeO (CeO)2@Co3S4Heterogeneous multi-level nano-structure catalytic material and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114540833A (en) * 2022-02-22 2022-05-27 临沂大学 CeO (CeO)2@Co3S4Heterogeneous multi-level nano-structure catalytic material and preparation method and application thereof

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