CN111270264A - Preparation method and application of monatomic platinum-nitrogen-doped graphite foil self-supporting hydrogen evolution electrode - Google Patents
Preparation method and application of monatomic platinum-nitrogen-doped graphite foil self-supporting hydrogen evolution electrode Download PDFInfo
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- 239000010439 graphite Substances 0.000 title claims abstract description 80
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 54
- 239000001257 hydrogen Substances 0.000 title claims abstract description 54
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 70
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Abstract
The invention discloses a preparation method and application of a monatomic platinum-aza graphite foil self-supporting hydrogen evolution electrode, which solve the problem that monatomic platinum catalyst in the prior art is difficult to keep high activity and stability under high current density because the monatomic platinum catalyst is usually powder and needs to be loaded on a working electrode by using a binder. The invention comprises the following steps: (S1) ultrasonically cleaning and drying the graphite foil; (S2) bombarding the dried graphite foil with nitrogen plasma to obtain a nitrogen-doped graphite foil; (S3) using a photoreduction method to load the monatomic platinum on the aza-graphite foil, thereby obtaining the monatomic platinum-aza-graphite foil self-supporting hydrogen evolution electrode. The invention obtains the platinum monoatomic-aza-graphite foil self-supporting hydrogen evolution electrode in a simple and environment-friendly way, realizes the regulation and control of the surface appearance and the doping elements of the substrate in one step, obtains the self-supporting hydrogen evolution electrode suitable for high current density, provides a good preposed foundation for the research of obtaining hydrogen energy by electrolyzing water, and is suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to a preparation method and application of a monatomic platinum-aza graphite foil self-supporting hydrogen evolution electrode.
Background
The hydrogen preparation by water electrolysis is an effective way for obtaining clean hydrogen energy, and the hydrogen evolution reaction is used as a half reaction in the water electrolysis process, so that the catalytic promotion of the dynamic process is of great significance. Compared with the noble metal-based catalyst, the transition metal compound catalyst and the nonmetal catalyst, the catalytic activity and the stability of the platinum-based catalyst are still far higher than those of other various hydrogen evolution reaction catalysts. However, the large-scale practical application of the noble metal platinum is severely restricted due to the low reserves and high price of the noble metal platinum. On the premise of not remarkably reducing the catalytic activity of the catalyst, the reduction of the loading amount of the metal platinum in the hydrogen evolution reaction catalyst has important significance. Strategies for reducing platinum particle size, preparing core-shell structures, preparing alloys, and the like have been developed to reduce platinum usage.
Compared with the strategy, the preparation of the monatomic platinum catalyst not only can further greatly reduce the loading of platinum, but also can realize catalytic activity and stability superior to those of a catalyst based on platinum nanoparticles, and has important application prospect. At present, atomic layer deposition, pyrolysis, photo-reduction, chemical reduction and other methods have been developed to prepare platinum monatomic catalysts. However, the monatomic platinum catalyst prepared at present is usually a powder material, and when the monatomic platinum catalyst is applied to an electrocatalytic reaction, a chemical binder needs to be mixed and then loaded on a working electrode for use. The structure not only reduces the electrochemical active area of the electrode, thereby reducing the specific activity of the catalyst, but also is difficult to promote the transportation of electrolyte and eliminate the influence of the release of bubbles in the hydrogen evolution reaction on the surface structure of the electrode, and can obviously reduce the activity and the stability of the electrode under high current density. And the use of binders further covers portions of the active sites, slowing charge and species transport.
Disclosure of Invention
The invention aims to provide a preparation method and application of a monatomic platinum-aza graphite foil self-supporting hydrogen evolution electrode, and mainly solves the problem that a monatomic platinum catalyst in the prior art is difficult to keep high activity and stability under high current density because the monatomic platinum catalyst is usually powder and needs to be loaded on a working electrode by using a binder.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a monatomic platinum-nitrogen-doped graphite foil self-supporting hydrogen evolution electrode comprises the following steps:
(S1) ultrasonically cleaning and drying the graphite foil;
(S2) bombarding the dried graphite foil with nitrogen plasma to obtain a nitrogen-doped graphite foil;
(S3) the monatomic platinum is supported on the aza-graphite foil by using a photoreduction method, and a monatomic platinum-monohybrid graphite foil self-supporting hydrogen evolution electrode is obtained.
Specifically, the specific process of the step (S1) is as follows: and (3) placing the graphite foil in ethanol, acetone and water in sequence for ultrasonic cleaning.
Specifically, the specific process of the step (S2) is as follows: placing the dried graphite foil in beamline ion injection equipment based on a Koffman ion source, and treating in a nitrogen atmosphere to obtain the single-doped graphite foil, wherein: the plasma voltage is 10-60kV, and the treatment time is 10-60 min.
Specifically, the specific process of the step (S3) is as follows: and (3) dripping a pure solution of chloroplatinic acid on the surface of the aza-graphite foil, naturally airing, placing under a mercury lamp for irradiating for 15-60min, wherein the power of the mercury lamp is 200W, and rinsing with deionized water to obtain the monatomic platinum-aza-graphite foil self-supporting hydrogen evolution electrode.
Preferably, the concentration of the chloroplatinic acid solution is 0.1-5mmol/L, and the dropping volume is 5-50 mu L/cm2。
Compared with the prior art, the invention has the following beneficial effects:
compared with other monatomic platinum hydrogen evolution reaction catalysts, the monatomic platinum-nitrogen-doped graphite foil self-supporting hydrogen evolution electrode prepared by the method can be used for preparing a platinum-loaded self-supporting electrode, and the surface of the electrode is rich in nitrogen heteroatoms, so that the platinum monatomic can be efficiently anchored, and the dispersibility and stability of the platinum monatomic are ensured; the surface of the electrode is provided with a nano array structure which is uniformly distributed, so that the surface area of the electrode is greatly increased, the transport of electrolyte and the desorption of bubbles can be promoted in the hydrogen evolution reaction, and the catalytic activity and the stability of the hydrogen evolution reaction under high current density are ensured; the electrode matrix keeps a graphite structure, has high conductivity and mechanical stability, and can enhance the catalytic performance of the composite electrode; the reduction process does not involve the processes of pyrolysis, ball milling and the like, a self-supporting electrode can be prepared, a chemical binder is not needed for the electrode, and catalytic active sites can be fully exposed.
The invention mainly uses two methods of plasma treatment and photoreduction, does not relate to common toxic nitrogen sources such as ammonia gas and nitric acid, and has the characteristics of environmental protection and easy preparation expansion. The monatomic platinum-aza graphite foil self-supporting hydrogen evolution electrode prepared by the method has a proper surface appearance and a proper chemical structure, provides a good preposed foundation for obtaining hydrogen energy by using an electrolytic water method, and is suitable for popularization and application.
Drawings
FIG. 1 is a schematic flow chart of the preparation of the monatomic platinum-aza graphite foil self-supporting hydrogen evolution electrode of the present invention.
Fig. 2 is a schematic electron microscope of a monoatomic platinum-azagraphite foil self-supporting hydrogen evolution electrode in example 1 of the present invention, wherein (a, b) is a schematic scanning electron microscope, (c) is a schematic transmission electron microscope, and (d) is a transmission electron microscope photograph for spherical aberration correction.
Fig. 3 is (a) X-ray diffraction pattern of the monoatomic platinum-azagraphite foil self-supporting hydrogen evolution electrode according to the present invention, in example 1, wherein (b) is a schematic diagram of N1s X photoelectron spectroscopy result, (c) is a schematic diagram of X-ray absorption near-edge structure of platinum element, and (d) is a schematic diagram of extended X-ray absorption fine structure of platinum element.
Fig. 4 is a schematic diagram of a monatomic platinum-aza graphite foil self-supporting hydrogen evolution electrode catalyzing hydrogen evolution reaction in example 1 of the present invention, wherein (a) is a polarization curve, (b) is a mass specific activity diagram at an overpotential of 0.05V, (c) is a constant potential test diagram, and (d) is an accelerated degradation test diagram.
Detailed Description
The present invention will be further described with reference to the following description and examples, which include but are not limited to the following examples.
The invention provides a preparation method of a monatomic platinum-aza graphite foil self-supporting hydrogen evolution electrode, which has the advantages of simple preparation method and no pollution in the process, and the obtained monatomic platinum-aza graphite foil self-supporting hydrogen evolution electrode has proper surface appearance and chemical structure in the aspect of realizing hydrogen energy preparation by electrocatalysis reaction, and provides a good prepositive basis for obtaining hydrogen energy by using an electrolytic water method. The main design idea of the invention is to prepare a graphite substrate with proper surface appearance and abundant heteroatoms in one step and then carry platinum monoatomic atoms with higher density by photoreduction. The main flow is shown in fig. 1, and comprises: firstly, preparing a nitrogen-doped graphite foil substrate; and secondly, preparing the monatomic platinum-nitrogen-doped graphite foil self-supporting hydrogen evolution electrode.
These two main processes are described in turn below.
Firstly, preparing nitrogen-doped graphite foil substrate
Firstly, placing a graphite foil in ethanol, acetone and water in sequence for ultrasonic cleaning, and then bombarding a commercial graphite foil by using nitrogen plasma to obtain an aza-graphite foil substrate, wherein the method specifically comprises the following steps: and (3) placing the dried graphite foil in beam line ion injection equipment based on a Kaufman ion source, and treating for a period of time in a nitrogen atmosphere to obtain the nitrogen-doped graphite foil. The method does not relate to harmful nitrogen sources such as ammonia gas, nitric acid and the like, has high preparation speed, can realize the regulation and control of the surface nano structure and the doping of surface nitrogen elements in one step, and simultaneously keeps the high conductivity and the high mechanical stability of the graphite foil.
Secondly, preparing the monoatomic platinum-nitrogen-doped graphite foil self-supporting hydrogen evolution electrode
In the invention, the monatomic platinum is loaded on the aza-graphite foil by using a photoreduction method, and the method specifically comprises the following steps: and (3) dripping an ethanol solution of chloroplatinic acid on the surface of the prepared aza-graphite foil, naturally airing, irradiating under a mercury lamp, and rinsing with deionized water to obtain the monatomic platinum-aza-graphite foil self-supporting hydrogen evolution electrode. The ethanol can assist the chloroplatinic acid to realize uniform dispersion, the reduction process is simple to operate and pollution-free, the utilization rate of the chloroplatinic acid precursor is high, the mechanical property of the substrate material is not influenced, the self-supporting electrode can be prepared, and the size of the substrate can be adjusted to realize mass production.
The following description will be made by taking a few practical cases as a technical solution of the present invention.
Example 1
Sequentially placing the graphite foil in ethanol, acetone and water for ultrasonic cleaning, drying, placing in beamline ion injection equipment based on a Koffman ion source, controlling the voltage to be 60kV, and treating for 30min in a nitrogen atmosphere to obtain the nitrogen-doped graphite foil; 10 μ L of 0.3mmol/L chloroplatinic acid ethanol solution was applied dropwise to 1cm2And naturally airing the surface of the aza-graphite foil, placing the aza-graphite foil under a mercury lamp for irradiating for 30min, wherein the power of the mercury lamp is 200W, and rinsing the surface with deionized water to obtain the monatomic platinum-aza-graphite foil self-supporting hydrogen evolution electrode.
As can be seen from (a, b) in fig. 2, the surface of the monatomic platinum-azagraphite foil self-supporting hydrogen evolution electrode is in a uniform nano-array structure which is favorable for electrocatalytic reactions involving gas generation, and moreover, the existence of platinum nanoparticles is not observed by scanning electron microscopy. The presence of platinum particles was also not observed on the transmission electron microscope (FIG. 2 c). Observed by using a transmission electron microscope with spherical aberration correction, the platinum monoatomic atoms are uniformly distributed on the surface of the aza-graphite foil (fig. 2 d). X-ray diffraction results also indicated the absence of platinum particles in the system (figure 3 a). X photoelectron spectroscopy the surface monoatomic platinum-azagraphite foil showed abundant nitrogen heteroatoms and was present mainly as pyridine nitrogen, pyrrole nitrogen and graphite nitrogen (fig. 3 b). As can be seen in FIG. 3c, platinumThe monoatomic atom has a higher valence than the metal platinum, which is caused by coordination with a heteroatom such as nitrogen. As can be seen from FIG. 3d, the monatomic platinum-aza graphite foil self-supporting hydrogen evolution electrode is mainly platinum-nitrogen bonds and does not contain platinum-platinum bonds, and the fitting result shows that the platinum monatomic is Pt-N4And (5) structure. As can be seen from FIG. 4a, the current density of the composite electrode is 10mA cm-2The overpotential is 0.023V; its mass ratio catalytic activity is 16.6 times that of platinum carbon catalyst at 0.05V overpotential (fig. 4 b); the current density thereof remained 98% after the 100000s test (fig. 4 c); after 1000 cycles of accelerated degradation experiments, the polarization curve remained substantially unchanged (fig. 4d), showing good activity and stability.
Example 2
Sequentially placing the graphite foil in ethanol, acetone and water for ultrasonic cleaning, drying, placing in a beam line ion injection device based on a Koffman ion source, controlling the voltage to be 50kV, and treating for 30min in a nitrogen atmosphere to obtain the nitrogen-doped graphite foil; 10 μ L of an ethanol solution of chloroplatinic acid at a concentration of 2mmol/L was applied dropwise to 0.5cm2And naturally airing the surface of the aza-graphite foil, placing the aza-graphite foil under a mercury lamp for irradiating for 30min, wherein the power of the mercury lamp is 200W, and rinsing the surface with deionized water to obtain the monatomic platinum-aza-graphite foil self-supporting hydrogen evolution electrode.
Example 3
Sequentially placing the graphite foil in ethanol, acetone and water for ultrasonic cleaning, drying, placing in a beamline ion injection device based on a Koffman ion source, controlling the voltage to be 30kV, and treating for 60min in a nitrogen atmosphere to obtain the nitrogen-doped graphite foil; 100 μ L of ethanol solution of chloroplatinic acid with concentration of 0.5mmol/L was applied dropwise to 10cm2And naturally airing the surface of the aza-graphite foil, irradiating the surface of the aza-graphite foil for 20min under a mercury lamp with the power of 200W, and rinsing the surface of the aza-graphite foil by deionized water to obtain the monatomic platinum-aza-graphite foil self-supporting hydrogen evolution electrode.
Example 4
Sequentially placing the graphite foil in ethanol, acetone and water for ultrasonic cleaning, drying, placing in a beam line ion injection device based on a Koffman ion source, controlling the voltage to be 60kV, and treating for 60min in a nitrogen atmosphere to obtain the nitrogen-doped graphite foil; the concentration of 300 mu L is 1mmoThe ethanol solution of the chloroplatinic acid is dripped on 30cm2And naturally airing the surface of the aza-graphite foil, placing the aza-graphite foil under a mercury lamp for irradiating for 60min, wherein the power of the mercury lamp is 200W, and rinsing the surface with deionized water to obtain the monatomic platinum-aza-graphite foil self-supporting hydrogen evolution electrode.
The invention obtains the platinum monoatomic-aza-graphite foil self-supporting hydrogen evolution electrode in a simple and environment-friendly manner, realizes the regulation and control of the surface appearance and doping elements of the substrate in one step, obtains the self-supporting hydrogen evolution electrode suitable for high current density, and provides a good prepositive basis for the research of obtaining hydrogen energy by electrolyzing water. Therefore, compared with the prior art, the invention has obvious technical advantages, outstanding substantive features and obvious progress.
The above examples are only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the technical problems solved by the present invention should be consistent with the present invention, and should be included in the scope of the present invention, unless there is any meaningful change or retouching in the spirit and concept of the subject invention.
Claims (6)
1. A preparation method of a monatomic platinum-nitrogen-doped graphite foil self-supporting hydrogen evolution electrode is characterized by comprising the following steps:
(S1) ultrasonically cleaning and drying the graphite foil;
(S2) bombarding the dried graphite foil with nitrogen plasma to obtain a nitrogen-doped graphite foil;
(S3) the monatomic platinum is supported on the aza-graphite foil by using a photoreduction method, and a monatomic platinum-monohybrid graphite foil self-supporting hydrogen evolution electrode is obtained.
2. The method for preparing the monatomic platinum-azagraphite foil self-supporting hydrogen evolution electrode according to claim 1, wherein the specific process of the step (S1) is as follows: and (3) placing the graphite foil in ethanol, acetone and water in sequence for ultrasonic cleaning.
3. The method for preparing the monatomic platinum-azagraphite foil self-supporting hydrogen evolution electrode according to claim 1 or 2, wherein the specific process of the step (S2) is as follows: placing the dried graphite foil in beamline ion injection equipment based on a Koffman ion source, and treating in a nitrogen atmosphere to obtain the single-doped graphite foil, wherein: the plasma voltage is 10-60kV, and the treatment time is 10-60 min.
4. The method for preparing the monatomic platinum-azagraphite foil self-supporting hydrogen evolution electrode according to claim 3, wherein the specific process of the step (S3) is as follows: and (3) dripping a pure solution of chloroplatinic acid on the surface of the aza-graphite foil, naturally airing, placing under a mercury lamp for irradiating for 15-60min, wherein the power of the mercury lamp is 200W, and rinsing with deionized water to obtain the monatomic platinum-aza-graphite foil self-supporting hydrogen evolution electrode.
5. The method for preparing the monatomic platinum-aza graphite foil self-supporting hydrogen evolution electrode as claimed in claim 4, wherein the chloroplatinic acid solution has a concentration of 0.1 to 5mmol/L and a drop-coating volume of 5 to 50 μ L/cm2。
6. The use of the monatomic platinum-aza-graphite foil self-supporting hydrogen evolution electrode obtained by the preparation method according to any one of claims 1 to 5 in the aspect of hydrogen energy preparation through electrocatalytic reaction.
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