CN112023926A - Electro-catalytic hydrogen evolution material and preparation method and application thereof - Google Patents
Electro-catalytic hydrogen evolution material and preparation method and application thereof Download PDFInfo
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J35/33—
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- B01J35/56—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides an electrocatalytic hydrogen evolution material, which comprises: the composite material comprises a foamed nickel substrate and an active component loaded on the foamed nickel substrate, wherein the active component comprises simple substance Co, a first composite metal oxide shown in a formula (I) and a second composite metal oxide shown in a formula (II), and Co3‑xNixO4Formula (I); co1‑yNiyO formula (II), wherein x is more than 0 and less than 3, and y is more than 0 and less than 1. The electrocatalytic hydrogen evolution material has excellent catalytic activity and stability.
Description
Technical Field
The invention relates to the field of inorganic nano materials, in particular to an electro-catalytic hydrogen evolution material and a preparation method and application thereof.
Background
The hydrogen is used as a secondary energy and clean energy carrier, has the advantages of wide source, high combustion heat value, cleanness, low carbon and the like, has important significance for guaranteeing national energy safety, coping with climate change, preventing and treating atmospheric pollution and the like, and is one of the clean energy with the most development potential in the 21 st century.
Among a plurality of hydrogen production processes, the hydrogen production by electrolyzing water is favored by researchers due to the advantages of simple and convenient operation, environmental protection and the like, and has wide application prospect. The core of the water electrolysis technology is the electrocatalytic water decomposition process, which occurs on the surface of an electrocatalyst. Therefore, the development of an electrocatalyst with high activity and high stability, the reduction of the reaction overpotential and the improvement of the reaction kinetics are important research subjects for realizing high-efficiency hydrogen production.
At present, noble metal platinum (Pt) is considered as the optimal hydrogen evolution catalyst for water electrolysis, however, Pt has the problems of high price, poor reserves and the like, which seriously limits the large-scale application of Pt in Hydrogen Evolution Reaction (HER). Therefore, finding an inexpensive and efficient electrocatalyst is a major challenge in the current field of hydrogen production from electrolyzed water.
Transition metal compounds, particularly nickel-cobalt bimetallic oxides, are of great interest because of their low cost, excellent electronic properties, good chemical stability and redox activity. It is worth noting that, although much work has been done by scientists, the synthesis of nickel-cobalt bimetallic oxides at present often involves complex multi-step reactions or high temperature calcination reactions, and the hydrogen evolution properties of the materials are not very desirable. These problems cannot meet the design requirements of electrocatalysts, and are not conducive to industrial mass production.
Disclosure of Invention
In view of the problems in the prior art, it is an object of the present invention to provide a power supplyThe catalytic hydrogen evolution material takes foam nickel as a matrix and simple substances of Co and Co3-xNixO4And Co1-yNiyO is used as an active component and has excellent catalytic activity and stability.
The second purpose of the present invention is to provide a method for preparing an electrocatalytic hydrogen evolution material corresponding to the first purpose.
The invention also aims to provide an application of the electrocatalytic hydrogen evolution material corresponding to the aim in the field of water electrolysis.
The fourth purpose of the invention is to provide an application of the electrocatalytic hydrogen evolution material corresponding to the purpose in the field of total moisture decomposition.
In order to achieve one of the purposes, the technical scheme adopted by the invention is as follows:
an electrocatalytic hydrogen evolution material comprising: a foamed nickel matrix and an active component loaded on the foamed nickel matrix, wherein the active component comprises simple substance Co, a first composite metal oxide shown in a formula (I) and a second composite metal oxide shown in a formula (II),
Co3-xNixO4formula (I)
Co1-yNiyO formula (II)
In the formula (I), the value range of x is more than 0 and less than 3, and in the formula (II), the value range of y is more than 0 and less than 1.
The inventors of the present application have found, through research, that an active component system composed of elemental Co, the first composite metal oxide represented by formula (I), and the second composite metal oxide represented by formula (II) has higher catalytic activity.
According to the invention, Co3-xNixO4Co representing Ni doping3O4And (4) crystal grains.
According to the invention, Co1-yNiyO represents a composite crystal grain composed of Ni-doped CoO and Co-doped NiO.
According to the invention, Co1-yNiyO is the main active species in the hydrogen evolution reaction.
In some preferred embodiments of the present invention, x is in the range of 0.2. ltoreq. x.ltoreq.1.0, preferably 0.4. ltoreq. x.ltoreq.0.8.
According to the invention, x can be any value between 0.2 and 1.0, preferably between 0.4 and 0.8.
According to the invention, the value range of x is 0.7-0.8.
In some preferred embodiments of the present invention, y is in the range of 0.1. ltoreq. y.ltoreq.0.9, and more preferably 0.2. ltoreq. y.ltoreq.0.8.
According to the invention, y can be any value between 0.1 and 0.9, preferably between 0.2 and 0.8.
According to the invention, the value range of y is 0.45-0.55.
In some preferred embodiments of the invention, the molar ratio of the Co element to the Ni element in the active component is (1-10): 1, preferably (3-5): 1.
According to the present invention, in the active component, the Co element means a Co atom in the simple substance Co, the first composite metal oxide, and the second composite metal oxide.
In some preferred embodiments of the present invention, the pore size of the foamed nickel matrix is 0.1mm to 10mm, preferably 0.1mm to 1 mm.
In some preferred embodiments of the invention, the foamed nickel matrix has a porosity of 90% to 99%, preferably 95% to 98%.
In some preferred embodiments of the present invention, the foamed nickel matrix has a pore density of from 50PPI to 200PPI, preferably from 100PPI to 150 PPI.
According to the present invention, the PPI is collectively referred to as Pores Per Linear inc, which is a unit of pore density.
According to the invention, the thickness of the nickel foam matrix is 0.5mm to 5mm, preferably 1mm to 2 mm.
According to the invention, all commercial Nickel Foams (NF) are available on the market as the nickel foam matrix of the invention, and commercial nickel foams with the pore size and porosity within the limited range of the invention are preferred.
The size of the nickel foam matrix according to the present invention is not particularly limited and may be conventionally selected by those skilled in the art according to actual needs.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of an electrocatalytic hydrogen evolution material comprises the following steps:
s1, providing a precursor material, wherein the precursor material comprises a foamed nickel matrix and a composite metal oxide containing cobalt and nickel loaded on the foamed nickel matrix;
s2, enabling the precursor material to be used as a working electrode to participate in an electrocatalytic hydrogen evolution reaction, and thus carrying out electrochemical activation on the precursor material to obtain the electrocatalytic hydrogen evolution material.
According to the present invention, in step S1, the composite metal oxide containing cobalt and nickel may be a composite metal oxide represented by formula (I) above.
In some preferred embodiments of the present invention, in step S1, the precursor material is prepared by performing hydrothermal treatment on a reaction system containing cobalt ions, a nickel foam matrix and a solvent.
In some preferred embodiments of the present invention, in step S2, the potential of the working electrode is-0.1V to-0.5V, preferably-0.16V to-0.20V, relative to the reference electrode.
In some preferred embodiments of the present invention, in step S2, the electrolyte of the electrocatalytic hydrogen evolution reaction is an alkaline solution, preferably a KOH solution, more preferably a KOH solution with a concentration of 0.1mol/L to 10mol/L, and even more preferably a KOH solution with a concentration of 0.5mol/L to 2 mol/L.
In some preferred embodiments of the present invention, in step S2, the time of the electrocatalytic hydrogen evolution reaction is 10 to 30 hours, preferably 15 to 25 hours.
In some preferred embodiments of the present invention, in step S2, the temperature of the electrocatalytic hydrogen evolution reaction is 20 ℃ to 40 ℃, preferably 25 ℃ to 35 ℃.
In some preferred embodiments of the present invention, in step S1, the cobalt ion is derived from a soluble cobalt salt, preferably, the soluble cobalt salt is Co (NO)3)2·6H2O。
In some preferred embodiments of the present invention, the pore size of the foamed nickel matrix is 0.1mm to 10mm, preferably 0.1mm to 1 mm; the porosity is 90-99%, preferably 95-98%.
According to the invention, the nickel foam matrix is preferably pretreated in order to remove impurities from the nickel foam matrix. The pretreatment step comprises the steps of respectively carrying out ultrasonic cleaning on the foam nickel matrix by using deionized water and ethanol, and drying the foam nickel matrix after cleaning.
In some preferred embodiments of the invention, the solvent is water.
According to the present invention, the water may be one or more of deionized water, distilled water, pure water, high purity water, and ultrapure water.
In some preferred embodiments of the present invention, the mass-to-volume ratio of the soluble cobalt salt to the solvent is (0.1-10): 100g/mL, preferably (0.5-5): 100 g/mL.
According to the invention, the mass to volume ratio refers to the ratio of the mass of the soluble cobalt salt to the volume of the solvent.
In some preferred embodiments of the present invention, in step S1, the conditions of the hydrothermal treatment include: the temperature of the hydrothermal treatment is 180 ℃ to 250 ℃, preferably 190 ℃ to 220 ℃.
In some preferred embodiments of the present invention, in step S1, the hydrothermal treatment time is 10 to 25 hours, preferably 15 to 20 hours.
According to the present invention, the inventors of the present application found in their studies that the time of the hydrothermal treatment can significantly affect the effect of the electrochemical activation. When the time of the hydrothermal treatment is 15-20 h, the optimal electrochemical activation effect can be obtained.
According to the present invention, the time of the hydrothermal treatment may be set to 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h, 19.5h, 20h, and any value therebetween.
According to the present invention, the hydrothermal treatment may be performed in a reaction tank.
According to the present invention, after the hydrothermal treatment is completed, the precursor material may be cooled to room temperature and then subjected to step S2.
In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:
the application of the electrocatalytic hydrogen evolution material or the electrocatalytic hydrogen evolution material prepared by the preparation method in water electrolysis hydrogen evolution is provided.
According to the present invention, the electrocatalytic hydrogen evolution material is used as a working electrode when the water electrolysis is performed.
According to the invention, the electrocatalytic hydrogen evolution material or the electrocatalytic hydrogen evolution material prepared according to the preparation method can be applied to a conventional alkaline environment and can also be applied to a neutral environment.
In order to achieve the fourth purpose, the technical scheme adopted by the invention is as follows:
the application of the electrocatalytic hydrogen evolution material or the electrocatalytic hydrogen evolution material prepared by the preparation method in the field of total moisture decomposition is disclosed.
In some preferred embodiments of the present invention, the electrocatalytic hydrogen evolution material is used as a cathode in performing the total water splitting.
According to the invention, when the full water decomposition is carried out, the type of the anode material is not limited, and the anode material commonly used in the field can be matched with the electrocatalytic hydrogen evolution material of the invention to realize the full water decomposition, and the anode material can be conventionally selected by a person skilled in the art according to the needs. Preferably, NiFe LDH/NF can be used as the anode for total water splitting.
According to the invention, NiFe LDH/NF refers to NiFe layered double hydroxides supported on foamed nickel. The layered double hydroxide of NiFe, abbreviated as NiFe LDH. The material is a typical electrocatalytic oxygen evolution material with higher activity, takes NiFe LDH/NF as an anode, and is assembled with the hydrogen evolution material of the invention into a full-water decomposition electrolytic tank of a two-electrode system, and has higher full-water decomposition capability.
According to the present invention, NiFe LDH can be prepared by the preparation methods provided in the prior art references. The method comprises the following specific steps: weighing 2mmolFeCl2·4H2O，1mmol Ni(NO3)2·6H2O, 25mmol of urea, these three were dissolved in 35mL of deionized water and the solution was transferred to a 50mL kettle and stirred vigorously for 30 minutes. A piece of 2cm by 2cm of nickel foam was then placed in the above solution and thoroughly wetted. Sealing the reaction kettle, putting the reaction kettle into an oven, and reacting for 6 hours at 90 ℃. And after the reaction is finished, naturally cooling the reaction kettle to room temperature, taking out the sample, fully cleaning the sample by using deionized water and absolute ethyl alcohol, and finally fully drying the sample in a 60 ℃ drying oven.
The invention has the advantages that the process is simple, the operation is convenient, and the prepared electro-catalytic hydrogen evolution material has higher catalytic activity and wide application prospect in the field of new energy.
Drawings
Figure 1 is an XRD pattern of the precursor material prepared in example 1.
Fig. 2 is an SEM picture of the precursor material prepared in example 1.
Fig. 3 is a TEM picture of the precursor material prepared in example 1.
Figure 4 is an EDS spectrum of the precursor material prepared in example 1.
Figure 5 is an EDS elemental profile of the precursor material prepared in example 1.
FIG. 6 is a graph showing the results of the test of the hydrogen evolution reaction in example 1 (i.e., chronoamperometric graph).
Fig. 7 is an XRD pattern of the electrocatalytic hydrogen evolution material prepared in example 1.
Fig. 8 is an SEM picture of the electrocatalytic hydrogen evolution material prepared in example 1.
Fig. 9 is a TEM picture of the electrocatalytic hydrogen evolution material prepared in example 1.
FIG. 10 is the EDS elemental distribution diagram of the electrocatalytic hydrogen evolution material prepared in example 1.
FIG. 11 is an EELS elemental profile of the active component of the electrocatalytic hydrogen evolution material prepared in example 1.
FIG. 12 is a linear voltammogram of example 1 and comparative examples 1 to 3.
FIG. 13 is a graph showing the results of test example 1.
FIG. 14 is a graph showing the results of test example 2.
FIG. 15 is a graph showing the results of test example 3.
FIG. 16 is a graph showing the results of test example 4.
Fig. 17 is a graph of the chronoamperometry in example 2.
Fig. 18 is a graph of the chronoamperometry of example 3.
Fig. 19 is a graph of the chronoamperometry of example 4.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the following embodiments, unless otherwise specified, commercial nickel foam is available from Hunan Korea New energy resources, Inc. with a thickness of 1.6mm and a pore density of 110 PPI.
In the embodiments described below, NiFe LDH/NF may be prepared by reference, for example, to which reference may be madehttps:// doi.org/10.1039/C5NR06802AThe references shown (Hierarchical 3-dimensional scientific-iron nanoshell arrays on carbon fiber paper as a novel electrode for non-enzymatic glucose sensing, Pananisam Kannan et al, Nanoscale, 2016, 2) were prepared. Specifically, 2mmol of FeCl is weighed2·4H2O，1mmol Ni(NO3)2·6H2O, 25mmol of urea, these three were dissolved in 35mL of deionized water and the solution was transferred to a 50mL kettle and stirred vigorously for 30 minutes. A piece of 2cm by 2cm of nickel foam was then placed in the above solution and thoroughly wetted. Sealing the reaction kettle, putting the reaction kettle into an oven, and reacting for 6 hours at 90 ℃. And after the reaction is finished, naturally cooling the reaction kettle to room temperature, taking out the sample, fully cleaning the sample by using deionized water and absolute ethyl alcohol, and finally fully drying the sample in a 60 ℃ drying oven.
In the embodiment described below, it is preferred that,the linear voltammograms were measured on an electrochemical workstation model CHI 760E, manufactured by chenhua instruments ltd. The test was performed at room temperature using a three-electrode test system, i.e. nickel foam (or precursor material, 1cm x 1cm platinum sheet) as the working electrode, where the geometric area of the working electrode was 1cm2(ii) a Graphite rod (purchased from Tianjin Elder Heng Cheng scientific and technological development Limited) as counter electrode; the Hg/HgO electrode (purchased from Tianjin Elata Heng Cheng scientific and technological development Co., Ltd.) was used as a reference electrode, and the electrolyte was 1M KOH. The sweep rate in the linear voltammetry test was 5mV/s, with a potential range of-0.85V to-1.4V (relative to the Hg/HgO reference electrode).
Example 1
1) Cutting commercial foam nickel into small pieces of 2cm x 2cm, then respectively ultrasonically cleaning the small pieces for 15min by using deionized water and ethanol, and drying the small pieces for later use.
2) Weighing 0.2910g Co (NO)3)2·6H2O, dissolving the O in 30mL of deionized water to prepare a Co-containing solution; the resulting Co-containing solution was then transferred to a teflon lined 50mL reactor while a piece of pre-treated nickel foam (2cm x 2cm) was placed in the Co-containing solution and allowed to soak thoroughly.
3) And sealing the reaction kettle, and then putting the reaction kettle into an oven for hydrothermal reaction at the reaction temperature of 200 ℃ for 18 h. After the reaction is finished, the reaction kettle is naturally cooled to room temperature, a sample (namely a precursor material) is taken out, fully washed by deionized water and ethanol, and then put into a 60 ℃ oven for drying for later use.
4) The precursor material is used as a working electrode, the graphite rod is used as a counter electrode, Hg/HgO is used as a reference electrode, 1M KOH is used as electrolyte, and electrocatalytic hydrogen evolution reaction is carried out in a three-electrode system. In the reaction process, the potential of the fixed working electrode is-0.18V (relative to RHE), and the reaction time is controlled to be 20 h. After the reaction is finished, the electrocatalytic hydrogen evolution material is obtained.
The obtained precursor material was subjected to XRD test, and the obtained XRD pattern was shown in fig. 1.
As can be seen from FIG. 1, the diffraction peaks, except for the characteristic diffraction peaks of nickel foam, are at 19.5 °, 31.6 °, 37.2 °, 38.7 °, 55.8 °, 59.6 ° and 65.2 °Seven peaks ascribed to Co3O4(JCPDS #42-1467) has X-ray characteristic diffraction peaks for the (111), (220), (311), (222), (422), (511) and (440) crystal planes. From the matching result, the Co growing on the foam nickel matrix in situ can be obtained by adopting a one-step hydrothermal method3O4And (4) crystal grains. The characteristic diffraction peak shape of the sample in the figure is sharp, which shows that the Co synthesized by the method is3O4The grain size is large and the crystallinity is high.
SEM analysis was performed on the obtained precursor material, and the obtained SEM picture is shown in fig. 2.
As can be seen from fig. 2, the three-dimensional skeleton surface of the nickel foam is densely covered with a layer of irregular particles, and the surface of the particles is smooth and takes on the shape of a polyhedron. A large number of gaps are reserved among the particles, and the gaps can increase the contact area of the material and the electrolyte, so that the electrolyte can fully soak the material, and the electrochemical action is facilitated.
TEM analysis was performed on the obtained precursor material, and the obtained TEM picture is shown in fig. 3.
As can be seen from fig. 3, the size of these polyhedral grains on the surface of the nickel foam is about several micrometers, and the edges and corners are well defined. Clear lattice fringes can be seen in high resolution TEM photographs, in which
And
the fringe spacing of (A) can be respectively attributed to Co3O4The (311) and (400) crystallographic planes of (JCPDS #42-1467) further confirmed that Co3O4The successful preparation.
The EDS test was performed on the obtained precursor crystal grains, and the pattern results are shown in FIGS. 4 and 5, and the data results are shown in Table 1 below.
TABLE 1
As is clear from fig. 4 and table 1, the atomic ratio of Ni, Co, and O in the obtained precursor crystal grains was 10.01:39.62: 50.37. This result suggests that these grains of the NF surface should be Ni-doped Co3O4Recorded as Co3- xNixO4. Scaled, x is about 0.79.
FIG. 5 is a diagram of an element distribution. As can be seen from FIG. 5, the three elements Ni, Co and O are in Co3-xNixO4The particles are uniformly distributed.
The test results of the hydrogen evolution reaction in step 4) are shown in fig. 6.
As can be seen from fig. 6, the hydrogen evolution current density of the working electrode became higher with the increase of the test time and became stable up to 20 hours. The hydrogen evolution current density is from 23mA cm at the beginning-2Increase to 51mA cm at steady-2. This particular phenomenon indicates that there is an electrochemical activation process for HER reactions of precursor materials in alkaline media. The material subjected to electrochemical activation was named EA-Co3-xNixO4。
For the prepared electro-catalytic hydrogen evolution material (namely EA-Co)3-xNixO4) XRD testing was performed and the XRD pattern obtained is shown in FIG. 7.
As can be seen from FIG. 7, Co3-xNixO4The characteristic diffraction peak of (a) was significantly weakened, and at the same time, a diffraction peak of metal Co newly appeared, corresponding to standard card Co (JCPDS # 1-1254). This phenomenon illustrates bulk Co during electrochemical activation3-xNixO4Is reduced to metallic Co.
SEM analysis is carried out on the prepared electro-catalytic hydrogen evolution material, and an obtained SEM picture is shown in figure 8.
As can be seen from fig. 8, the overall morphology of the material after electrochemical activation did not change much compared to the material before activation. The active particles are still densely distributed on the three-dimensional skeleton surface of the foam nickel, and the polyhedron shape before activation is maintained. No significant exfoliation was observed on the surface of the nickel foam indicating that these active particles were strongly bonded to the nickel foam matrix.
The obtained electrocatalytic hydrogen evolution material was subjected to TEM analysis, and the obtained TEM picture is shown in fig. 9.
As can be seen from fig. 9, the surface structure of the electrochemically activated material has changed significantly. Unlike the sharp edges of the active particles prior to electrochemical activation, the edges of the activated active particles have become rough, forming a large number of interwoven nanoparticles of about 20nm in size. High resolution TEM tests on these nanoparticles can reveal clear lattice fringes, demonstrating that these particles are well crystalline. The measurement of these lattice fringes can find out
And
the stripe pitches of (a) and (b) correspond to the (200) and (111) crystal planes of NiO or CoO, respectively. In addition to ordered lattice fringes, distinct misalignments of some regions of the lattice fringes were observed, indicating that a large number of lattice defects were present in these nanoparticles. These nanoparticles, and the structural defects abundant therein, are capable of providing sufficient active sites for the electrocatalytic hydrogen evolution process.
EDS analysis was performed on the obtained electrocatalytic hydrogen evolution material, and the obtained EDS element distribution diagram is shown in FIG. 10.
As can be seen from fig. 10, Ni and O are uniformly distributed in the activated active particles, while Co is concentrated in the interior of the particles, and the signal at the edges of the particles is relatively weak. This result indicates that the activated active particles exhibit a heterogeneous structure. The combination of XRD and TEM analysis shows that the metal Co is concentrated in the bulk structure of the activated active particles, and the surface structure of the activated active particles is mainly NiO or CoO.
EELS analysis was performed on the active components in the obtained electrocatalytic hydrogen evolution material, and the obtained EELS element distribution diagram is shown in FIG. 11.
As can be seen from FIG. 11, as shown in the graph a in FIG. 11, based on the distribution of Ni, Co, and O obtained by integrating the element signals, it can be qualitatively seen that the semaphores of Ni and Co are different at different positions, while that of OThe amount of signal is not much related to the position. The pictures b-d in fig. 11 are elemental distribution plots based on elemental composition (atomic percent). It can be quantitatively seen from the pictures b-d that the distribution and composition of Ni and Co show complementary situation, while the content of oxygen element is more stable (maintained at about 50%). The EELS results further prove that the surface structure of the activated active particles is a composite structure formed by Ni-doped CoO and Co-doped NiO, and the surface structure is represented as Co1-yNiyO (according to FIG. 11, it is calculated that the value of y varies within the range of 0.2 to 0.8).
The linear voltammogram of the prepared electrocatalytic hydrogen evolution material is shown in fig. 12.
Example 2
Steps 1) -2) in example 2 are the same as in example 1. Step 3) was substantially the same as in example 1 except that the reaction time (i.e., the time of hydrothermal treatment) was adjusted to 6 hours. Step 4) is also essentially the same as in example 1, except that the activation time is extended to 23 h. The results are shown in FIG. 17. As can be seen from FIG. 17, the hydrogen evolution current density started at 21mA cm-2Reduced to 18mA cm-2。
Example 3
Steps 1) -2) in example 3 are the same as in example 1. Step 3) was substantially the same as in example 1 except that the reaction time was adjusted to 12 hours. Step 4) is also essentially the same as in example 1, except that the activation time is extended to 27 h. The results are shown in FIG. 18. As can be seen from FIG. 18, the hydrogen evolution current density started at 25mA cm-2Increase to 33mA cm at steady-2。
Example 4
Steps 1) -2) in example 4 are the same as in example 1. Step 3) was substantially the same as in example 1 except that the reaction time was adjusted to 24 hours. Step 4) is also essentially the same as in example 1, except that the activation time is extended to 37 h. The results are shown in FIG. 19. As can be seen from FIG. 19, the hydrogen evolution current density started at 23mA cm-2Increase to 33mA cm at steady-2。
Test example 1
This test example serves to illustrate the stability of the electrocatalytic hydrogen evolution material provided by the present invention.
After the electrocatalytic hydrogen evolution material prepared in example 1 was tested for 300 hours under a constant overpotential of 120mV, the hydrogen evolution current density decayed only 6.2%. In addition, from the results of the chronopotentiometry test, it can be seen that: at 20mA/cm2After the constant hydrogen evolution current density of the hydrogen sensor is tested for 300 hours, the overpotential is increased by only 12 mV. The test data graph is shown in fig. 13.
Test example 2
The test example is used for illustrating the industrial application value of the electrocatalytic hydrogen evolution material provided by the invention.
Since alkaline industrial electrolysis of water is usually carried out in a 30% by weight KOH solution, we further evaluated the hydrogen evolution performance of the electrocatalytic hydrogen evolution material prepared in example 1 in a 30% KOH electrolyte. As shown in FIG. 14, at 200mA · cm-2After the hydrogen evolution current density of (1) is continuously operated for 354 hours, the overpotential is increased from the initial 364mV to 407mV, and the overpotential is increased by only 11.8 percent. This further demonstrates that the electrocatalytic hydrogen evolution material provided by the present invention also has excellent stability under industrial alkaline electrolyzed water operating conditions.
Test example 3
In order to further simulate the alkaline industrial electrolyzed water, a two-electrode system was assembled by using a NiFe layered double hydroxide (NiFe LDH/NF) supported on foamed nickel as an anode and the electrocatalytic hydrogen evolution material prepared in example 1 as a cathode, and the full-water decomposition performance of the electrolytic cell was tested in a KOH solution with a mass fraction of 30%. As shown in FIG. 15, 10mA · cm was obtained-2The required groove pressure of the current density is 1.50V; obtain 200mA cm-2The required cell voltage for current density of (1.85V).
Test example 4
In view of the severe corrosion of materials and equipment by alkaline electrolytes in practical applications, it is urgently required to develop a hydrogen evolution electrocatalyst having excellent activity also in neutral electrolytes. In view of this, the present inventors also evaluated the hydrogen evolution performance of the electrocatalytic hydrogen evolution material prepared in example 1 in 1M phosphate buffered saline (PBS, pH 7.0). Three-electrode system for testingThe electrocatalytic hydrogen evolution material prepared in example 1 was used as a working electrode, a graphite rod was used as a counter electrode (purchased from tianjin aida hengshen technologies development limited), and Ag/AgCl (a filling liquid was saturated potassium chloride) was used as a reference electrode (purchased from tianjin aida hengshen technologies development limited), and a linear voltammetry test was performed in a potential interval of-0.55V to-1.09V (relative to the Ag/AgCl reference electrode). As shown in FIG. 16, 10mA · cm was obtained-2The overpotential required by the hydrogen evolution current density is 87 mV; when the hydrogen evolution current density is more than 30mA cm-2The hydrogen evolution activity of the electrocatalytic material prepared in example 1 exceeded that of the platinum sheet.
Comparative example 1
A linear voltammogram was obtained using nickel foam, one of the raw materials in example 1, as a working electrode. The voltammogram is shown in FIG. 12.
Comparative example 2
The precursor material in example 1 was used as a working electrode to obtain a linear voltammogram. The voltammogram is shown in FIG. 12.
Comparative example 3
And taking a platinum sheet as a working electrode to obtain a linear voltammogram. The voltammogram is shown in FIG. 12.
As can be seen from fig. 12, the HER activity of the hydrogen evolution material after activation was significantly improved compared to the precursor material. Activated hydrogen evolution material 10mA cm-2The hydrogen evolution current density corresponds to an overpotential of only 57mV, which is superior to 67mV of a platinum sheet. Even at 200mA · cm-2Under the high current density of (2), the overpotential required by the activated hydrogen evolution material electrode is only 219mV, which is close to 214mV of a platinum sheet. The result shows that the precursor material can become a high-activity HER electrocatalyst through electrochemical activation in an alkaline medium, and is expected to replace a noble metal platinum-based material.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. An electrocatalytic hydrogen evolution material comprising: a foamed nickel matrix and an active component loaded on the foamed nickel matrix, wherein the active component comprises simple substance Co, a first composite metal oxide shown in a formula (I) and a second composite metal oxide shown in a formula (II),
Co3-xNixO4formula (I)
Co1-yNiyO formula (II)
In the formula (I), x is more than 0 and less than 3, preferably more than 0.2 and less than or equal to 1.0, and more preferably more than or equal to 0.4 and less than or equal to 0.8, and in the formula (II), y is more than 0 and less than 1, preferably more than or equal to 0.1 and less than or equal to 0.9, and more preferably more than or equal to 0.2 and less than or equal to 0.8.
2. The electrocatalytic hydrogen evolution material as set forth in claim 1, wherein the molar ratio of the Co element to the Ni element in the active component is (1-10): 1, preferably (3-5): 1.
3. The electrocatalytic hydrogen evolution material according to claim 1 or 2, wherein the pore size of the foamed nickel matrix is between 0.1mm and 10mm, preferably between 0.1mm and 1 mm; the porosity is 90-99%, preferably 95-98%; the pore density is 50PPI to 200PPI, preferably 100PPI to 150 PPI.
4. A preparation method of an electrocatalytic hydrogen evolution material comprises the following steps:
s1, providing a precursor material, wherein the precursor material comprises a foamed nickel matrix and a composite metal oxide containing cobalt and nickel loaded on the foamed nickel matrix;
s2, enabling the precursor material to be used as a working electrode to participate in an electrocatalytic hydrogen evolution reaction so as to carry out electrochemical activation on the precursor material to obtain the electrocatalytic hydrogen evolution material,
preferably, in step S1, the precursor material is prepared by performing hydrothermal treatment on a reaction system containing cobalt ions, a nickel foam matrix and a solvent.
5. The method according to claim 4, wherein in step S2, the potential of the working electrode is-0.1V to-0.5V, preferably-0.16V to-0.20V, relative to the reference electrode; more preferably, the reference electrode is a reversible hydrogen electrode; and/or
In step S2, the time of the electrocatalytic hydrogen evolution reaction is 10 to 30 hours, preferably 15 to 25 hours; and/or the temperature of the electrocatalytic hydrogen evolution reaction is 20-40 ℃, preferably 25-35 ℃.
6. The method according to claim 4 or 5, wherein in step S2, the electrolyte of the electrocatalytic hydrogen evolution reaction is an alkaline solution, preferably a KOH solution, more preferably a KOH solution with a concentration of 0.1mol/L to 10mol/L, and still more preferably a KOH solution with a concentration of 0.5mol/L to 2 mol/L.
7. The method according to any one of claims 4 to 6, wherein in step S1, the cobalt ion is derived from a soluble cobalt salt, preferably the soluble cobalt salt is Co (NO)3)2·6H2O; and/or the aperture of the foam nickel matrix is 0.1 mm-10 mm, preferably 0.1 mm-1 mm; the porosity is 90-99%, preferably 95-98%; and/or the solvent is water,
preferably, the mass-to-volume ratio of the soluble cobalt salt to the solvent is (0.1-10): 100g/mL, preferably (0.5-5): 100 g/mL.
8. The method according to any one of claims 4 to 7, wherein in step S1, the conditions of the hydrothermal treatment include: the temperature of the hydrothermal treatment is 180-250 ℃, and preferably 190-220 ℃; the time of the hydrothermal treatment is 10 to 25 hours, preferably 15 to 20 hours.
9. Use of the electrocatalytic hydrogen evolution material according to any one of claims 1 to 3 or prepared according to the preparation method of any one of claims 4 to 8 in the field of electrolysis of water.
10. Use of the electrocatalytic hydrogen evolution material according to any one of claims 1-3 or prepared according to the preparation method of any one of claims 4-8 in the field of total water decomposition, preferably with the electrocatalytic hydrogen evolution material as cathode when carrying out the total water decomposition.
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