CN109183058B - Construction method of catalytic hydrogen evolution electrode capable of fully exposing molybdenum disulfide active site - Google Patents
Construction method of catalytic hydrogen evolution electrode capable of fully exposing molybdenum disulfide active site Download PDFInfo
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Abstract
The invention belongs to the technical field of two-dimensional material preparation and catalytic hydrogen evolution, and particularly relates to a construction method of a catalytic hydrogen evolution electrode capable of fully exposing molybdenum disulfide active sites. Aiming at the problem of low abundance of the hydrogen evolution active sites catalyzed by the existing molybdenum disulfide nanosheets, the technical core of the invention comprises the following points: [1] utilizing a printing method to fixedly carry molybdenum disulfide to construct a three-dimensional catalytic hydrogen evolution electrode; [2] the surfactant polyvinylpyrrolidone is doped to assist in stripping the molybdenum disulfide and prevent the molybdenum disulfide nano-sheets from re-agglomerating; [3] reduced graphene oxide is doped to provide anchor points for the dispersion of the molybdenum disulfide nano flakes, so that the molybdenum disulfide nano flakes are further prevented from being stacked; [4] a carrier with high surface roughness is selected as an electrode substrate. The invention is suitable for the catalytic hydrogen evolution reaction in acidic solution at normal temperature.
Description
Technical Field
The invention belongs to the technical field of two-dimensional material preparation and electro-catalysis hydrogen evolution, and particularly relates to a construction method of a catalytic hydrogen evolution electrode capable of fully exposing molybdenum disulfide active sites.
Background
Conventional fossil fuels are gradually being replaced by new sustainable energy sources due to serious environmental pollution problems and non-renewable nature of the fuels. Hydrogen energy is used as an efficient and clean energy carrier and is taken as an ideal substitute for the traditional fossil fuel. However, the development of hydrogen energy is limited by the inefficiency of hydrogen production and the complexity of the production process.
The hydrogen production by water electrolysis is considered as an important way for continuously obtaining hydrogen, and the design of the high-efficiency electro-catalysis hydrogen evolution material is a key for realizing the technology. At present, the core task in the field of hydrogen production by water electrolysis is to solve the contradiction between high hydrogen production efficiency and low catalytic cost, so as to develop a high-efficiency, economic and green hydrogen production catalyst and related processes, so as to replace a metal platinum catalyst with limited resources and high cost and realize low-cost conversion of energy.
As a graphene-like two-dimensional material, molybdenum disulfide has hydrogen adsorption free energy similar to that of metal platinum, can stably exist in a strong acid solution, is rich in resources, and is expected to replace a traditional noble metal hydrogen evolution material. Research (Anders B L, Soren K, Soren D, et al, molybdenum resins for electric and photonic hydrogen evolution, Energy&Environmentalcience, 2012,5:5577) showed that the catalytically active site of molybdenum disulfide was located
The edge of the crystal face, therefore, the edge exposed area of the molybdenum disulfide is increased to become an important way for improving the catalytic hydrogen evolution performance of the molybdenum disulfide. At present, the exposure of the catalytic active sites of the catalyst has a plurality of problems, which are mainly shown in the following steps: (1) the graphene-like sheet layer of the molybdenum disulfide has larger size, which is extremely not beneficial to the exposure of the active sites at the edge of the graphene-like sheet layer; (2) the molybdenum disulfide nanosheets are easy to re-accumulate due to van der waals force action, so that the abundance of hydrogen evolution active sites is reduced; (3) the immobilization mode of the molybdenum disulfide is single, and the spatial structure design means capable of exposing more active sites is deficient.
Disclosure of Invention
Aiming at the problems that the existing molybdenum disulfide sheets have large size, are easy to accumulate among the sheets and lack the space structure design means capable of exposing more active sites, the invention provides a construction method of a catalytic hydrogen evolution electrode capable of fully exposing the molybdenum disulfide active sites. The purpose is as follows: the stripping of molybdenum disulfide of a body material is effectively promoted by adding a surfactant polyvinylpyrrolidone, the radial size of a sheet layer is reduced, and the stacking of molybdenum disulfide nanosheets is prevented; reduced graphene oxide is added to provide a dispersion anchor point of the molybdenum disulfide lamella, so that the accumulation of the molybdenum disulfide nanosheet layer is further prevented; the electrode substrate with high surface roughness is adopted, so that the specific surface area of the electrode is effectively increased, and the number of catalytic active sites is increased; the advantage that patterning can be conveniently carried out by utilizing a digital printing technology is utilized, a three-dimensional graphical structure of the catalytic hydrogen evolution active substance is formed, and the exposure quantity of active sites is further improved.
The technical scheme adopted by the invention is as follows:
a construction method of a catalytic hydrogen evolution electrode capable of fully exposing molybdenum disulfide active sites is characterized by comprising the following steps:
[1] preparing a dispersion liquid containing molybdenum disulfide nanosheets;
[2] and (3) taking the dispersion liquid containing the molybdenum disulfide nano flakes prepared in the step (1) as printing ink, and forming a three-dimensional patterned molybdenum disulfide-based catalytic hydrogen evolution electrode on the electrode substrate by adopting an ink-jet printing method.
The printed electronic technology takes an additive method as a micro-patterning process route to realize the direct deposition of functional materials, and compared with the traditional etching subtractive method in the field of microelectronics, the printed electronic technology has the advantages of simple and convenient production process, small raw material loss, less equipment investment, and realization of large-area, low-cost and batch production. Inkjet printing is one of the non-contact, plate-making-free digital printing techniques. The technical scheme transfers the ink jet printing technology to the preparation of the catalytic hydrogen evolution electrode, so that the molybdenum disulfide nano sheet used as the electrocatalyst forms a three-dimensional pattern on the electrode substrate. The exposed number of the catalytic hydrogen evolution active sites is effectively increased, so that the catalytic hydrogen evolution electrode prepared by the method has better catalytic activity.
Preferably, the preparation method of the dispersion liquid containing the molybdenum disulfide nanosheets comprises the following steps:
[1-1] adopting a liquid phase ultrasonic stripping method to obtain a suspension containing molybdenum disulfide nano flakes, wherein a surfactant and a heavy accumulation inhibitor are added into a stripping solvent in the liquid phase ultrasonic stripping method;
(1-2) carrying out centrifugal separation on the suspension containing the molybdenum disulfide nano flakes obtained in the step (1-1), and taking two thirds of supernatant to obtain molybdenum disulfide-based nano flake dispersion liquid;
further preferably, the surfactant is polyvinylpyrrolidone.
The polyvinylpyrrolidone is added, so that the stripping of the molybdenum disulfide of the body can be effectively promoted, the radial size of the sheet layer is reduced, and the re-stacking of the molybdenum disulfide nano sheet layer is prevented, thereby improving the number of catalytic hydrogen evolution active sites of the finally prepared electrode.
Further preferably, in the liquid phase ultrasonic stripping process in the step [1-1], the mass ratio of polyvinylpyrrolidone and molybdenum disulfide added into the stripping solvent is 0.15-0.25: 1.
More preferably, the redeposition inhibitor is reduced graphene oxide.
The addition of the reduced graphene oxide can provide a dispersion anchor point for the molybdenum disulfide in the lamellar layer, and further prevent the accumulation of the molybdenum disulfide nanosheet layer, so that the exposure quantity of active sites of the catalytic hydrogen evolution electrode made of the molybdenum disulfide nanosheet is increased.
Further preferably, in the liquid phase ultrasonic stripping process in the step [1-1], the mass ratio of the reduced graphene oxide and the molybdenum disulfide added into the stripping solvent is 0.05-0.15: 1.
Preferably, the electrode substrate in the step [2] is a rigid or flexible substrate with a conductive film covered on the surface and large surface roughness.
Preferably, the process of forming the three-dimensional patterned molybdenum disulfide-based catalytic hydrogen evolution electrode in the step [2] is as follows: the printing is carried out for many times by spraying and printing for many times by using a plane figure and then by using a square convolution pattern or a concentric circle pattern.
Preferably, the process of forming the three-dimensional patterned molybdenum disulfide-based catalytic hydrogen evolution electrode in the step [2] is as follows: the printing is performed 10 times in a plane pattern, and then 10-20 times in a square spiral pattern or a concentric circle pattern.
Compared with the prior art, the invention has the beneficial effects that:
(1) the advantage that patterning can be conveniently carried out by utilizing a digital printing technology is utilized, a three-dimensional graphical structure of the catalytic hydrogen evolution active substance is formed, and the exposure quantity of the catalytic hydrogen evolution active sites is further improved; (2) the surfactant polyvinylpyrrolidone is added, so that the stripping of molybdenum disulfide of a body can be effectively promoted, the radial size of a sheet layer is reduced, and the re-stacking of molybdenum disulfide nano sheet layers is prevented, so that the number of catalytic hydrogen evolution active sites is increased; (3) adding a heavy stacking inhibitor to reduce graphene oxide, providing a dispersion anchor point of the lamellar molybdenum disulfide, further preventing the stacking of the molybdenum disulfide nanosheets, and improving the exposure quantity of catalytic hydrogen evolution active sites; (4) the electrode substrate with high surface roughness can effectively increase the specific surface area, thereby improving the exposure quantity of catalytic hydrogen evolution active sites; (5) the catalytic hydrogen evolution electrode prepared by the invention has very high catalytic hydrogen evolution activity; (6) the technical scheme of the invention is very easy to implement, has low preparation cost and can realize mass preparation.
Drawings
The invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is an optical microscope photograph of a three-dimensional catalytic hydrogen evolution electrode on Teslin paper base obtained in example 1 of the present invention;
FIG. 2 is a linear sweep voltammogram graph and a Tafel graph of a three-dimensional catalytic hydrogen evolution electrode on a Teslin paper base obtained in example 1 of the present invention;
FIG. 3 is a linear sweep voltammogram and Tafel plot of a planar catalytic hydrogen evolution electrode on Teslin paper base obtained in example 2 of the present invention;
FIG. 4 is a linear sweep voltammogram and Tafel plot of a planar catalytic hydrogen evolution electrode on a Teslin paper base obtained in comparative example 1 of the present invention;
FIG. 5 is a linear sweep voltammogram and Tafel plot of a three-dimensional catalytic hydrogen evolution electrode on Teslin paper base obtained in comparative example 2 of the present invention;
FIG. 6 is a linear sweep voltammogram and Tafel plot of a three-dimensional catalytic hydrogen evolution electrode on Teslin paper base obtained in comparative example 3 of the present invention;
FIG. 7 is an SEM image of molybdenum disulfide (a) in comparative example 2, molybdenum disulfide/polyvinylpyrrolidone (b) in comparative example 3, and molybdenum disulfide/polyvinylpyrrolidone/reduced graphene oxide (c) in example 1 according to the present invention;
FIG. 8 is a graph of UV-VIS absorption spectra of molybdenum disulfide of comparative example 2, molybdenum disulfide/polyvinylpyrrolidone of comparative example 3, and molybdenum disulfide/polyvinylpyrrolidone/reduced graphene oxide of example 1 in accordance with the present invention;
FIG. 9 is a linear sweep voltammogram and Tafel plot of a three-dimensional catalytic hydrogen evolution electrode on a polyimide substrate obtained in comparative example 4 of the present invention.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
A construction method of a catalytic hydrogen evolution electrode capable of fully exposing molybdenum disulfide active sites comprises the following steps:
[1] preparing a dispersion liquid containing molybdenum disulfide nanosheets;
[2] and (3) taking the dispersion liquid containing the molybdenum disulfide nano flakes prepared in the step (1) as printing ink, and forming a three-dimensional patterned molybdenum disulfide-based catalytic hydrogen evolution electrode on the electrode substrate by adopting an ink-jet printing method.
Preferably, the preparation method of the dispersion liquid containing the molybdenum disulfide nanosheets comprises the following steps:
[1-1] adopting a liquid phase ultrasonic stripping method to obtain a suspension containing molybdenum disulfide nano flakes, and adding a surfactant and a heavy accumulation inhibitor into a stripping solvent in the liquid phase ultrasonic stripping method;
(1-2) carrying out centrifugal separation on the suspension containing the molybdenum disulfide nano flakes obtained in the step (1-1), and taking two thirds of supernatant to obtain molybdenum disulfide-based nano flake dispersion liquid;
further preferably, the surfactant is polyvinylpyrrolidone.
Further preferably, in the liquid phase ultrasonic stripping process in the step [1-1], the mass ratio of polyvinylpyrrolidone and molybdenum disulfide added into the stripping solvent is 0.15-0.25: 1.
More preferably, the redeposition inhibitor is reduced graphene oxide.
Further preferably, in the liquid phase ultrasonic stripping process in the step [1-1], the mass ratio of the reduced graphene oxide and the molybdenum disulfide added into the stripping solvent is 0.05-0.15: 1.
Preferably, the electrode substrate in the step [2] is a rigid or flexible substrate with a conductive film covered on the surface and large surface roughness.
Preferably, the process of forming the three-dimensional patterned molybdenum disulfide-based catalytic hydrogen evolution electrode in the step [2] is as follows: the printing is carried out for many times by spraying and printing the plane figure and then the square convolution pattern for many times.
Preferably, the process of forming the three-dimensional patterned molybdenum disulfide-based catalytic hydrogen evolution electrode in the step [2] is as follows: the printing is carried out 10 times by the plane figure, and then 10-20 times by the square convolution pattern or the concentric circle pattern.
The technical solution of the present invention is further illustrated with reference to the accompanying drawings and examples.
Example 1
Mixing 10mL of ethanol and 10mL of deionized water in a beaker, adding 40mg of polyvinylpyrrolidone, weighing 200mg of molybdenum disulfide powder raw material and 20mg of reduced graphene oxide powder raw material, dispersing in a mixed solution, and preparing a molybdenum disulfide suspension. And transferring the molybdenum disulfide suspension into an ultrasonic pool for liquid phase stripping, centrifuging the molybdenum disulfide suspension subjected to liquid phase ultrasonic treatment, and taking supernatant liquid at two thirds of a centrifugal tube to obtain molybdenum disulfide/polyvinylpyrrolidone/reduced graphene oxide dispersion liquid (namely molybdenum disulfide nano-flake dispersion liquid), namely the catalytic hydrogen evolution active material.
And spraying and printing the molybdenum disulfide/polyvinylpyrrolidone/reduced graphene oxide on a Teslin paper base with the surface covered with a copper conductive film by using an ink jet printing method. The patterning configuration is as follows: first, a plane pattern (area 0.5 x 0.5 cm)2) And (4) carrying out spray printing for 10 times, and then carrying out spray printing for 10 times by using a square convolution pattern to obtain the catalytic hydrogen evolution working electrode with a three-dimensional configuration. To the working electricityThe electrode is subjected to linear scanning volt-ampere characteristic characterization by adopting a three-electrode system, the electrolyte is 0.5M sulfuric acid solution, the reference electrode is a silver/silver chloride electrode, and the counter electrode is a platinum sheet electrode.
FIG. 1 is an optical micrograph of a three-dimensional catalytic hydrogen evolution electrode on Teslin paper substrate obtained in an example of the present invention. The three-dimensional configuration of the catalytically active material, which configuration facilitates the exposure of more catalytically active sites, is clearly visible in fig. 1.
FIG. 2 is a linear sweep voltammogram graph and a Tafel graph of a three-dimensional catalytic hydrogen evolution electrode on a Teslin paper base obtained in an embodiment of the invention. As can be seen from FIG. 2, in the example, the molybdenum disulfide-based catalytic hydrogen evolution electrode has a current density of 10mA/cm2The overpotential of hydrogen evolution is 51mV, and the Tafel slope is 55mV/dec, which shows that the three-dimensional catalytic hydrogen evolution electrode on the Teslin paper base has excellent catalytic hydrogen evolution performance.
Example 2
Mixing 10mL of ethanol and 10mL of deionized water in a beaker, adding 40mg of polyvinylpyrrolidone, weighing 200mg of molybdenum disulfide powder raw material and 20mg of reduced graphene oxide powder raw material, dispersing in a mixed solution, and preparing a molybdenum disulfide suspension. And transferring the molybdenum disulfide suspension into an ultrasonic pool for liquid phase stripping, centrifuging the molybdenum disulfide suspension subjected to liquid phase ultrasonic treatment, and taking supernatant liquid at two thirds of a centrifugal tube to obtain molybdenum disulfide/polyvinylpyrrolidone/reduced graphene oxide dispersion liquid (namely molybdenum disulfide nano-flake dispersion liquid), namely the catalytic hydrogen evolution active material.
And spraying and printing the molybdenum disulfide/polyvinylpyrrolidone/reduced graphene oxide on a Teslin paper base with the surface covered with a copper conductive film by using an ink jet printing method. The patterning configuration is as follows: first, a plane pattern (area 0.5 x 0.5 cm)2) And (3) carrying out jet printing for 10 times, and then carrying out jet printing for 10 times by using concentric circle patterns to obtain the catalytic hydrogen evolution working electrode with a three-dimensional configuration. The working electrode is characterized by linear sweep voltammetry characteristics, a three-electrode system is adopted for characterization, the electrolyte is 0.5M sulfuric acid solution, the reference electrode is a silver/silver chloride electrode, and the counter electrode is a platinum sheet electrodeAnd (4) a pole.
FIG. 3 is a linear sweep voltammogram graph and a Tafel graph of a three-dimensional catalytic hydrogen evolution electrode on Teslin paper base obtained in the example of the present invention. As can be seen from FIG. 3, in the example, the molybdenum disulfide-based catalytic hydrogen evolution electrode has a current density of 10mA/cm2The overpotential for hydrogen evolution was 54mV and the Tafel slope was 56 mV/dec.
Comparative example 1
Mixing 10mL of ethanol and 10mL of deionized water in a beaker, adding 40mg of polyvinylpyrrolidone, weighing 200mg of molybdenum disulfide powder raw material and 20mg of reduced graphene oxide powder raw material, dispersing in a mixed solution, and preparing a molybdenum disulfide suspension. And transferring the molybdenum disulfide suspension into an ultrasonic pool for liquid phase stripping, centrifuging the molybdenum disulfide suspension subjected to liquid phase ultrasonic treatment, and taking supernatant liquid at two thirds of a centrifugal tube to obtain molybdenum disulfide/polyvinylpyrrolidone/reduced graphene oxide dispersion liquid, namely the catalytic hydrogen evolution active material.
And spraying and printing the molybdenum disulfide/polyvinylpyrrolidone/reduced graphene oxide composite material on a Teslin paper base with the surface covered with a copper conductive film by using an ink jet printing method. When jet printing, the ink is printed in a plane pattern (0.5 x 0.5cm in area)2) And repeating the spray printing for 20 times to obtain the catalytic hydrogen evolution planar working electrode. The working electrode is characterized by linear sweep voltammetry characteristics, a three-electrode system is adopted for characterization, the electrolyte is 0.5M sulfuric acid solution, the reference electrode is a silver/silver chloride electrode, and the counter electrode is a platinum sheet electrode.
FIG. 4 is a linear sweep voltammogram and Tafel plot of a catalytic hydrogen evolution planar electrode on Teslin paper substrate obtained in comparative example 1 of the present invention. As can be seen from FIG. 4, the Teslin paper-based catalytic hydrogen evolution planar electrode in comparative example 1 has a current density of 10mA/cm2The overpotential for hydrogen evolution was 56mV and the Tafel slope was 57 mV/dec.
As can be seen from examples 1 and 2 and comparative example 1, the catalytic hydrogen evolution material is subjected to a three-dimensional configuration by using an inkjet printing method, so that more catalytic hydrogen evolution active sites can be effectively exposed in a unit area, and the catalytic hydrogen evolution performance of the electrode is improved.
Comparative example 2
Mixing 10mL of ethanol and 10mL of deionized water in a beaker, and then weighing 200mg of molybdenum disulfide powder raw material and dispersing the raw material in the mixed solution to prepare a molybdenum disulfide suspension. And transferring the molybdenum disulfide suspension into an ultrasonic pool for liquid phase stripping, centrifuging the molybdenum disulfide suspension subjected to liquid phase ultrasonic treatment, and taking supernatant liquid at two thirds of a centrifugal tube to obtain molybdenum disulfide dispersion liquid, namely the catalytic hydrogen evolution active material.
And spraying and printing the molybdenum disulfide catalytic hydrogen evolution material on a Teslin paper base with the surface covered with a copper conductive film by using an ink jet printing method. The patterning configuration is as follows: first, a plane pattern (area 0.5 x 0.5 cm)2) And (4) carrying out spray printing for 10 times, and then carrying out spray printing for 10 times by using a square convolution pattern to obtain the catalytic hydrogen evolution working electrode with a three-dimensional configuration. The working electrode is characterized by linear sweep voltammetry characteristics, a three-electrode system is adopted for characterization, the electrolyte is 0.5M sulfuric acid solution, the reference electrode is a silver/silver chloride electrode, and the counter electrode is a platinum sheet electrode.
FIG. 5 is a linear sweep voltammogram and Tafel plot of a three-dimensional catalytic hydrogen evolution electrode on Teslin paper substrate obtained in comparative example 2 of the present invention. As can be seen from FIG. 5, the Teslin paper-based three-dimensional catalytic hydrogen evolution electrode in comparative example 2 has a current density of 10mA/cm2The overpotential for hydrogen evolution was 93mV, and the Tafel slope was 77 mV/dec.
Comparative example 3
Mixing 10mL of ethanol and 10mL of deionized water in a beaker, then weighing 200mg of molybdenum disulfide powder raw material and 40mg of polyvinylpyrrolidone powder, and dispersing in a mixed solution to prepare a molybdenum disulfide suspension. And transferring the molybdenum disulfide suspension into an ultrasonic pool for liquid phase stripping, centrifuging the molybdenum disulfide suspension subjected to liquid phase ultrasonic treatment, and taking supernatant liquid at two thirds of a centrifugal tube to obtain molybdenum disulfide/polyvinylpyrrolidone dispersion liquid, namely the catalytic hydrogen evolution active material.
And (3) spraying and printing the molybdenum disulfide/polyvinylpyrrolidone composite material on a Teslin paper base with the surface covered with a copper conductive film by using an ink jet printing method. Patterning thereofThe configuration is as follows: first, a plane pattern (area 0.5 x 0.5 cm)2) And (4) carrying out spray printing for 10 times, and then carrying out spray printing for 10 times by using a square convolution pattern to obtain the catalytic hydrogen evolution working electrode with a three-dimensional configuration. The working electrode is characterized by linear sweep voltammetry characteristics, a three-electrode system is adopted for characterization, the electrolyte is 0.5M sulfuric acid solution, the reference electrode is a silver/silver chloride electrode, and the counter electrode is a platinum sheet electrode.
FIG. 6 is a linear sweep voltammogram and Tafel plot of a three-dimensional catalytic hydrogen evolution electrode on Teslin paper substrate obtained in comparative example 3 of the present invention. As can be seen from FIG. 6, the Teslin paper-based catalytic hydrogen evolution three-dimensional electrode in comparative example 3 has a current density of 10mA/cm2The overpotential for hydrogen evolution was 63mV and the Tafel slope was 56 mV/dec.
Fig. 7 is SEM images of molybdenum disulfide (a) in comparative example 2, molybdenum disulfide/polyvinylpyrrolidone (b) in comparative example 3, and molybdenum disulfide/polyvinylpyrrolidone/reduced graphene oxide (c) in example 1. As can be seen from the figure, the radial dimension of the molybdenum disulfide is greatly reduced after the polyvinylpyrrolidone is added; after the reduced graphene oxide is added, the reduced graphene oxide is three-dimensionally dispersed in the molybdenum disulfide, so that the accumulation of the thin molybdenum disulfide layer can be prevented.
Fig. 8 is a graph showing ultraviolet-visible absorption spectra of molybdenum disulfide in comparative example 2, molybdenum disulfide/polyvinylpyrrolidone in comparative example 3, and molybdenum disulfide/polyvinylpyrrolidone/reduced graphene oxide in example 1, and it can be seen from the graph that the concentrations of molybdenum disulfide increase in the order of addition of polyvinylpyrrolidone and reduced graphene oxide, and the concentrations of molybdenum disulfide in comparative example 2, comparative example 3, and example 1 are calculated to be 0.15, 0.41, 0.71mg/mL in the order of addition. This further demonstrates the assisted exfoliation of polyvinylpyrrolidone and the inhibition of re-stacking of reduced graphene oxide.
As can be seen from comparative examples 2 and 3, the incorporation of polyvinylpyrrolidone effectively improves the catalytic hydrogen evolution performance of molybdenum disulfide; from example 1 and comparative example 3, it can be known that the doping of the reduced graphene oxide further improves the catalytic hydrogen evolution performance of the molybdenum disulfide.
Comparative example 4
Mixing 10mL of ethanol and 10mL of deionized water in a beaker, adding 40mg of polyvinylpyrrolidone, weighing 200mg of molybdenum disulfide powder raw material and 20mg of reduced graphene oxide powder raw material, dispersing in a mixed solution, and preparing a molybdenum disulfide suspension. And transferring the molybdenum disulfide suspension into an ultrasonic pool for liquid phase stripping, centrifuging the molybdenum disulfide suspension subjected to liquid phase ultrasonic treatment, and taking supernatant liquid at two thirds of a centrifugal tube to obtain molybdenum disulfide/polyvinylpyrrolidone/reduced graphene oxide dispersion liquid (namely molybdenum disulfide nano-flake dispersion liquid), namely the catalytic hydrogen evolution active material.
And (3) spraying and printing the molybdenum disulfide/polyvinylpyrrolidone/reduced graphene oxide composite material on the polyimide substrate with the surface covered with the copper conductive film by using an ink jet printing method. The patterning configuration is as follows: first, a plane pattern (area 0.5 x 0.5 cm)2) And (4) carrying out spray printing for 10 times, and then carrying out spray printing for 10 times by using a square convolution pattern to obtain the catalytic hydrogen evolution working electrode with a three-dimensional configuration. The working electrode is characterized by linear sweep voltammetry characteristics, a three-electrode system is adopted for characterization, the electrolyte is 0.5M sulfuric acid solution, the reference electrode is a silver/silver chloride electrode, and the counter electrode is a platinum sheet electrode.
FIG. 9 is a linear sweep voltammogram and Tafel plot of a polyimide-based three-dimensional catalytic hydrogen evolution electrode obtained in comparative example 4 of the present invention. As can be seen from FIG. 9, the polyimide-based three-dimensional catalytic hydrogen evolution electrode in comparative example 4 had a current density of 10mA/cm2The overpotential for hydrogen evolution was 67mV and the Tafel slope was 62 mV/dec.
From example 1 and comparative example 4, compared with the polyimide film substrate, the Teslin paper substrate has the advantage that the number of catalytic active sites in a unit area is increased due to the large surface roughness, so that the catalytic hydrogen evolution performance of the electrode is improved.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (5)
1. A construction method of a catalytic hydrogen evolution electrode capable of fully exposing molybdenum disulfide active sites is characterized by comprising the following steps: [1] preparing a dispersion liquid containing molybdenum disulfide nanosheets; [2] taking the dispersion liquid containing the molybdenum disulfide nano flakes prepared in the step (1) as printing ink, and forming a three-dimensional patterned molybdenum disulfide-based catalytic hydrogen evolution electrode on an electrode substrate by adopting an ink-jet printing method; the electrode substrate is a rigid or flexible base material with the surface covered with a conductive film and large surface roughness;
the preparation method of the dispersion liquid containing the molybdenum disulfide nanosheet comprises the following steps:
[1-1] obtaining a suspension containing molybdenum disulfide nanosheets by adopting a liquid-phase ultrasonic stripping method, adding a surfactant and a heavy accumulation inhibitor into a stripping solvent in the liquid-phase ultrasonic stripping method, wherein the heavy accumulation inhibitor is reduced graphene oxide, and the mass ratio of the reduced graphene oxide to the molybdenum disulfide added into the stripping solvent in the liquid-phase ultrasonic stripping process in the step [1-1] is 0.05-0.15: 1;
and (1-2) carrying out centrifugal separation on the suspension containing the molybdenum disulfide nano flakes obtained in the step (1-1), and taking two thirds of supernatant to obtain a molybdenum disulfide-based nano flake dispersion liquid.
2. The method of claim 1 for constructing a catalytic hydrogen evolution electrode with substantially exposed molybdenum disulfide active sites, comprising: the surfactant is polyvinylpyrrolidone.
3. The method of claim 2 wherein the method of constructing a catalytic hydrogen evolution electrode substantially exposing active sites of molybdenum disulfide comprises: in the liquid phase ultrasonic stripping process in the step (1-1), the mass ratio of polyvinylpyrrolidone and molybdenum disulfide added into the stripping solvent is 0.15-0.25: 1.
4. The method for constructing a catalytic hydrogen evolution electrode with substantially exposed molybdenum disulfide active sites as claimed in claim 1, wherein the step [2] of forming the three-dimensionally patterned molybdenum disulfide-based catalytic hydrogen evolution electrode comprises: the printing is carried out for many times by spraying and printing for many times by using a plane figure and then by using a square convolution pattern or a concentric circle pattern.
5. The method of claim 4 wherein the molybdenum disulfide electrode is printed 10 times in a flat pattern and 10-20 times in a square spiral or concentric pattern.
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