CN112680745B

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Publication number: CN112680745B
Application number: CN202011424235.5A
Authority: CN
Inventors: 范修军; 刘静; 张献明
Original assignee: Shanxi University
Current assignee: Shanxi University
Priority date: 2020-12-08
Filing date: 2020-12-08
Publication date: 2021-12-31
Anticipated expiration: 2040-12-08
Also published as: CN112680745A

Abstract

Translated fromChinese

本发明涉及一种限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极及其制备方法和应用。本发明的制备方法为：先合成氧化钨纳米多孔薄膜，然后将其作为载体，通过水热法将钌纳米团簇限域负载在氧化钨纳米多孔孔道及镂空孔壁内，再通过化学气相沉积法一步合成限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极，且具有稳定的结构形貌。本发明以金属钨箔作为模板和钨源，在不额外加入钨盐的情况下，首次采用三步法(阳极氧化—水热限域负载—化学气相氮化)直接在钨箔上生长氮化钨，制备的限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极可作为酸性和碱性条件下的析氢催化剂电极，且具有高催化性能、长循环寿命、高容量和高循环稳定性的优势。

The invention relates to a tungsten nitride nano-porous thin film integrated electrode with confined ruthenium nano-clusters and a preparation method and application thereof. The preparation method of the invention is as follows: firstly synthesizing a tungsten oxide nanoporous film, then using it as a carrier, confining and loading the ruthenium nanocluster in the tungsten oxide nanoporous channel and the hollow hole wall by a hydrothermal method, and then by chemical vapor deposition One-step synthesis of tungsten nitride nanoporous thin film integrated electrodes loaded with ruthenium nanoclusters confinement, and has stable structure and morphology. In the present invention, metal tungsten foil is used as template and tungsten source, and the three-step method (anodic oxidation-hydrothermal confinement loading-chemical vapor nitridation) is used for the first time to directly grow nitridation on tungsten foil without adding tungsten salt. Tungsten, the prepared tungsten nitride nanoporous thin film integrated electrode with confined ruthenium nanoclusters can be used as hydrogen evolution catalyst electrode under acidic and alkaline conditions, and has high catalytic performance, long cycle life, high capacity and high cycle stability sexual advantage.

Description

Tungsten nitride nano porous film integrated electrode with ruthenium nanocluster loaded in limited domain and preparation method and application thereof

Technical Field

The invention belongs to the technical field of new material preparation and electrochemistry, and particularly relates to a tungsten nitride nano porous film integrated electrode with ruthenium nanoclusters loaded in a limited domain, and a preparation method and application thereof.

Background

Depletion of traditional fossil fuels and gradual environmental degradation worldwide have forced development of promising clean renewable energy sources. Clean, pollution-free solar, wind, water and nuclear energy and the electric energy generated by the energy will be the main force of future energy.

Hydrogen is a promising alternative to traditional fossil fuels because of its high energy density (120mJ/kg) and renewability, and zero greenhouse gas emissions. Electrocatalytic water splitting, a mature and commercially available technology, is considered an environmentally friendly method for large-scale production of hydrogen. Platinum (Pt) -based materials are one of the most advanced catalysts for Hydrogen Evolution (HER) reactions in acidic media. However, Pt severely hinders its large-scale application in energy conversion systems due to its high cost and low abundance, and moreover, it is necessary to develop a potent HER catalyst over a wide pH range. There is still a need for low cost catalysts for industrial hydrogen production. With the rapid development of scientific technology, new higher requirements on materials have been put forward in the aspects of high efficiency, device miniaturization, high integration, intellectualization, portability and the like of energy storage and conversion technology. Therefore, it is urgent to develop efficient and cheap electrode materials suitable for different energy storage and conversion systems.

The transition metal nitride has a 3 d-valence electron shell structure, and has the characteristics of metal property, wide d band, excellent electronic property and the like, so that the transition metal nitride is distinguished from other materials as an electrochemical active material. The prepared tungsten nitride material expands metal crystal lattices due to the insertion of element N, and the density of metal surface states is increased. Most transition metal nitrides have high affinity for hydrogen and oxygen, especially in the aspect of electrocatalytic hydrogen production and oxygen production as electrocatalysts. Notably, their superior stability advantages make them good carriers for stable formation of small metal nanoclusters. Furthermore, synergy between nanoclusters and substrate may lead to unique catalytic properties.

The metal-H binding energy directly determines the intrinsic activity of the catalyst on HER. Pt shows the optimal metal-H binding energy, located in the center of the volcano plot. Density Functional Theory (DFT) calculations show that the binding energies of Ru-H and Pt-H are 0.54 and 0.53eV, respectively, indicating that the electronic structures of Ru and Pt are similar. Meanwhile, the price of Ru is much lower than that of Pt, which makes the use of Ru on HER interesting, stimulating researchers to optimize Ru-based catalysts by adjusting the adsorption/desorption energy of reactive species on the catalyst surface.

Throughout the literature and the patent, the traditional tungsten nitride is mostly a powder material prepared by a hydrothermal method, and due to the requirements of subsequent electrochemical tests, a binder (such as Nafion) is usually required to be added, and the use of a non-conductive binder inevitably limits the electron transmission rate and blocks the active center of the catalyst. Meanwhile, the release of continuous gas during electrolysis makes the catalyst coating on the electrode easily peel off, thereby affecting the long-term stability of the catalyst. The in situ synthesis of catalysts directly on a conductive support may be a particularly promising strategy to achieve extraordinary electrocatalytic activity.

Disclosure of Invention

The invention aims to provide a tungsten nitride nano porous film integrated electrode with ruthenium nanoclusters loaded in a limited domain, and a preparation method and application thereof.

According to the invention, a metal tungsten foil is used as a template and a tungsten source, tungsten nitride is directly grown on the tungsten foil by adopting a three-step method (anodic oxidation, hydrothermal limited-area loading and chemical vapor phase nitridation) for the first time under the condition of not additionally adding tungsten salt, so that the tungsten nitride nano porous film integrated electrode with the ruthenium nanocluster loaded in the limited area is prepared, and the obtained tungsten nitride nano porous film electrode can be used as a hydrogen evolution catalyst electrode under acidic and alkaline conditions. The anodized tungsten foil can not only provide a tungsten source for tungsten nitride, but also serve as a conductive substrate to stabilize the material, thereby improving its capacity, catalytic activity and cycling stability.

The technical scheme adopted by the invention is as follows:

a preparation method of a tungsten nitride nano porous film integrated electrode with ruthenium nanoclusters loaded in a limited domain comprises the steps of firstly synthesizing a tungsten oxide nano porous film, then taking the tungsten oxide nano porous film as a carrier, loading the ruthenium nanoclusters in the tungsten oxide nano porous pore channels and the hollow pore walls in a limited domain mode through a hydrothermal method, and then synthesizing the tungsten nitride nano porous film integrated electrode with ruthenium nanoclusters loaded in a limited domain mode in one step through a chemical vapor deposition method, wherein the tungsten nitride nano porous film integrated electrode has a stable structural morphology.

Further, the preparation method of the tungsten nitride nano-porous film integrated electrode with the ruthenium nanocluster loaded in a limited domain specifically comprises the following steps:

(1) and (3) anode treatment: ultrasonically cleaning 20-320 square mm tungsten foil with acetone, anhydrous ethanol and deionized water respectively to remove organic matters on the surface, and drying with nitrogen; the cleaned tungsten foil is used as an anode, a platinum sheet is used as a cathode, the surface area ratio of the cathode to the anode is controlled to be 1:1-6:1, and a 10-70V direct current constant voltage power supply is adopted to dissolve 0.15-0.3mol/L oxalic acid and 0.1-0.3mol/L Na₂SO₄Anodizing in 0.01-0.03mol/L NaF electrolyte for 10-100 minutes, cleaning with flowing deionized water, and blow-drying with nitrogen to obtain anode nano porous tungsten oxide;

(2) carrying out limited loading of ruthenium nanoclusters in tungsten oxide nanopores: 0.4-2mg of RuCl₃·3H₂Dissolving O in a deionized water solvent, settling a magnetic stirrer at the bottom of the solvent, placing the nano porous tungsten oxide obtained in the step (1) in a cubic copper cage and suspending on the middle upper part of the solvent, stirring for 1-6h and uniformly mixing on the magnetic stirrer at the air atmosphere and room temperature, transferring the solution and the nano porous tungsten oxide into a reaction kettle, packaging, heating in an oven at 100-200 ℃ for 5-20h, and then cooling to room temperature in the oven; taking out the nano porous tungsten oxide, washing with absolute ethyl alcohol and deionized water, and drying;

(3) CVD nitridation reaction: and (3) placing the nano porous tungsten oxide obtained in the step (2) in the center of a quartz tube of a CVD tube furnace, setting the furnace temperature at 500-900 ℃, introducing argon and ammonia gas, keeping the total pressure at 0.25-0.4KPa, carrying out nitridation reaction for 0.5-3h, and then naturally cooling to room temperature under the argon atmosphere to obtain the tungsten nitride nano porous film integrated electrode loaded with ruthenium nanoclusters in a limited area.

Further, the reaction kettle is a reaction kettle with a polytetrafluoroethylene substrate.

Further, in the CVD nitridation reaction process, ammonia is used as a reaction gas, and the furnace temperature is increased to 500-900 ℃ at a constant speed in the presence of argon and ammonia.

Furthermore, in the CVD nitridation reaction process, the flow rate of the argon gas is 50-200sccm, and the flow rate of the ammonia gas is 10-100 sccm.

Further, during the CVD nitridation reaction, the reaction time was 3 h.

Further, RuCl in the step (2)₃·3H₂The mass volume ratio of the O to the deionized water is 1:6-30 mg/ml.

The invention also provides a tungsten nitride nano porous film integrated electrode of the limited-domain loaded ruthenium nanocluster prepared by the preparation method.

The invention also provides application of the tungsten nitride nano porous film integrated electrode with the limited-domain loaded ruthenium nanocluster in catalytic hydrogen evolution in acidic electrolyzed water and catalytic hydrogen evolution in alkaline electrolyzed water.

Further, the application process comprises the following steps: performing electrochemical measurement on an electrochemical workstation by using a three-electrode system; the integrated electrode is encapsulated by using a sealing film and a lead and directly used as a working electrode.

Compared with the prior art, the invention has the following advantages:

(1) in the composite electrode prepared by the invention, the tungsten foil is used as a conductive substrate, and meanwhile, a tungsten source is provided, so that the cost is low, the used elements are rich in reserves, the preparation process is simple, tungsten nitride directly and uniformly grows on the tungsten foil, and the mechanical stability of the electrode structure is effectively improved;

(2) compared with the traditional process, the integrated electrode prepared by the invention does not need to add auxiliary materials such as conductive agents, binders and the like in the electrode preparation process. The process is simple and easy, the cost is low, and the period is short. The obtained electrode material can be directly applied to electrolytic water catalysis, when the electrode material is used as an electrolytic water catalysis electrode, the operation processes of grinding, slurry preparation, drying and the like are not needed, an additional conductive substrate is not needed, and the electrode material has the advantages of high catalysis performance, long cycle life, high capacity and high cycle stability;

(3) the carrier of the tungsten nitride nano porous film with the ruthenium nanoclusters loaded in the limited domain prepared by the process is a hollow porous tungsten nitride nano porous film different from the traditional pore channel, is favorable for high dispersion of the ruthenium nanoclusters, improves the exposure of active sites, increases the active specific surface area of tungsten nitride, is easy for permeation of electrolyte, and is favorable for conduction of electrons;

(4) the tungsten nitride nano porous film material with the limited-area supported ruthenium nanoclusters prepared by the process has electro-catalytic hydrogen evolution performance in acidic and alkaline electrolytes, namely high activity, low initial potential, high current density, small Tafel slope, stable performance and the like.

Drawings

FIG. 1 is an XRD pattern of the product obtained in example 1 of the present invention;

FIG. 2 is an SEM photograph of a product obtained in example 2 of the present invention;

FIG. 3 is a TEM image of the product obtained in example 3 of the present invention;

FIG. 4 is an XPS plot of the product of example 4 of the present invention;

FIG. 5 is a graph showing a polarization curve and b Tafel curve of the product obtained in example 7 in the case of electrochemical acidic hydrogen evolution, with a scan rate of 50mV/s and an electrolyte of 0.5M H₂SO₄；

FIG. 6 is a graph of a polarization curve and a graph of b Tafel curve of the product obtained in example 7 in the electrochemical alkaline hydrogen evolution reaction, with a scan rate of 50mV/s and 1.0M KOH as electrolyte;

FIG. 7 shows the hydrogen saturation of the product obtained in example 7 of the invention at 0.5M H₂SO₄Cathodic current density of 10mA cm for hydrogen evolution reaction in solution and 1.0M KOH solution^-2Constant current stability test chart.

Detailed Description

The invention is further illustrated with reference to the following figures and examples.

Example 1:

(1) and (3) anode treatment: ultrasonically cleaning a 1 square centimeter tungsten foil by using acetone, absolute ethyl alcohol and deionized water respectively, removing organic matters on the surface, and drying by using nitrogen; using a circular tungsten foil with an exposed surface diameter of 0.5 square centimeter and an area of 0.19625 square centimeters as an anode, 0.15mol/L oxalic acid and 0.1mol/L Na₂SO₄And 0.01mol/L NaF electrolyte, a platinum sheet as a cathode, and anodizing at 60V for 60 minutes. After the reaction is finished, washing a sample by using flowing deionized water, and drying by using nitrogen to obtain the anode nano-porous tungsten oxide;

(2) carrying out limited loading of ruthenium nanoclusters in tungsten oxide nanopores: 1mg of RuCl₃·3H₂Dissolving O in 6ml of deionized water solvent, putting in a magneton, precipitating at the bottom of the solvent, putting the nano-porous tungsten oxide obtained in the step (1) in a cubic copper cage and suspending on the middle-upper part of the solvent, stirring for 3 hours at room temperature in an air atmosphere on a magnetic stirrer, transferring the solution and the nano-porous tungsten oxide to a reaction kettle with a polytetrafluoroethylene substrate, packaging, putting in a 100 ℃ drying oven, heating for 10 hours, and then cooling to room temperature in the drying oven; then taking out the nano-porous tungsten oxide, washing with absolute ethyl alcohol and deionized water, and drying.

(3) CVD nitridation reaction: and (3) placing the nano porous tungsten oxide obtained in the step (2) in the center of a quartz tube of a CVD tube furnace, setting the furnace temperature to be 800 ℃, the argon gas flow to be 100sccm, the ammonia gas flow to be 50sccm and the total gas pressure to be 0.3KPa, carrying out nitridation reaction for 1h, and then naturally cooling to room temperature under the argon atmosphere to obtain the tungsten nitride nano porous film integrated electrode with the ruthenium nanoclusters loaded in a limited area.

As shown in fig. 1, which is an XRD pattern of the product obtained in this example 1, the XRD pattern of the material corresponds to the (111), (200), (220) and (311) crystal planes of tungsten nitride (JCPDS No.75-1012) and the (110), (200) and (211) crystal planes of simple substance tungsten (JCPDS No.04-0806) in the standard card library, which illustrates the successful synthesis of the prepared tungsten nitride nano-porous film material with domain-limited supported ruthenium nanoclusters integrated electrode, and the metal is amorphous and does not contain any crystalline metal phase.

Example 2

(1) And (3) anode treatment: ultrasonically cleaning a 1 square centimeter tungsten foil by using acetone, absolute ethyl alcohol and deionized water respectively, removing organic matters on the surface, and drying by using nitrogen; 0.15mo of a circular tungsten foil having an exposed surface diameter of 0.5 cm square and an area of 0.19625 cm square as an anodeL/L oxalic acid, 0.1mol/L Na₂SO₄And 0.01mol/L NaF electrolyte, a platinum sheet as a cathode, and anodizing at 60V for 60 minutes. After the reaction is finished, washing a sample by using flowing deionized water, and drying by using nitrogen to obtain the anode nano-porous tungsten oxide;

(2) carrying out limited loading of ruthenium nanoclusters in tungsten oxide nanopores: 1mg of RuCl₃·3H₂Dissolving O in 30ml of deionized water solvent, putting in a magneton, precipitating at the bottom of the solvent, putting the nano-porous tungsten oxide obtained in the step (1) in a cubic copper cage and suspending on the middle-upper part of the solvent, stirring for 3 hours at room temperature in an air atmosphere on a magnetic stirrer, transferring the solution and the nano-porous tungsten oxide to a reaction kettle with a polytetrafluoroethylene substrate, packaging, putting in a 100 ℃ drying oven, heating for 12 hours, and then cooling to room temperature in the drying oven; then taking out the nano-porous tungsten oxide, washing with absolute ethyl alcohol and deionized water, and drying.

As shown in fig. 2, which is an SEM image of the product obtained in this example, it can be seen that the morphology of the product is Ru nanocluster confinement loading and is uniformly dispersed in the porous tungsten nitride nanopores and hollow hole walls.

Example 3

(1) And (3) anode treatment: ultrasonically cleaning a 1 square centimeter tungsten foil by using acetone, absolute ethyl alcohol and deionized water respectively, removing organic matters on the surface, and drying by using nitrogen; using a circular tungsten foil with an exposed surface diameter of 0.5 square centimeter and an area of 0.19625 square centimeters as an anode, 0.15mol/L oxalic acid and 0.1mol/L Na₂SO₄And 0.01mol/L NaF electrolyte, a platinum sheet as a cathode, and anodizing at 60V for 60 minutes. After the reaction is finished, the sample is washed clean by flowing deionized water and is usedDrying the anode nano porous tungsten oxide by nitrogen to obtain anode nano porous tungsten oxide;

(2) carrying out limited loading of ruthenium nanoclusters in tungsten oxide nanopores: 1mg of RuCl₃·3H₂Dissolving O in 12ml of deionized water solvent, putting in a magneton, precipitating at the bottom of the solvent, putting the nano-porous tungsten oxide obtained in the step (1) in a cubic copper cage and suspending on the middle-upper part of the solvent, stirring for 3 hours at room temperature in an air atmosphere on a magnetic stirrer, transferring the solution and the nano-porous tungsten oxide to a reaction kettle with a polytetrafluoroethylene substrate, packaging, putting in a 100 ℃ drying oven, heating for 10 hours, and then cooling to room temperature in the drying oven; then taking out the nano-porous tungsten oxide, washing with absolute ethyl alcohol and deionized water, and drying.

(3) CVD nitridation reaction: and (3) placing the nano porous tungsten oxide obtained in the step (2) in the center of a quartz tube of a CVD tube furnace, setting the furnace temperature at 700 ℃, the argon gas flow at 100sccm, the ammonia gas flow at 50sccm and the total gas pressure at 0.3KPa to perform nitridation reaction for 1h, and then naturally cooling to room temperature under the argon atmosphere to obtain the tungsten nitride nano porous film integrated electrode with the ruthenium nanoclusters loaded in a limited area.

As shown in fig. 3, which is a TEM topography of the tungsten nitride nanoporous thin film integrated electrode with ruthenium nanoclusters loaded in a limited domain prepared in this example, a graph shows a nanoporous structure of tungsten nitride in a sample, and a pore size is about 100nm, and a graph b shows the uniform dispersion and hollow holes of ruthenium nanoclusters.

Example 4

(1) And (3) anode treatment: ultrasonically cleaning a 1 square centimeter tungsten foil by using acetone, absolute ethyl alcohol and deionized water respectively, removing organic matters on the surface, and drying by using nitrogen; using a circular tungsten foil with an exposed surface diameter of 0.5 square centimeter and an area of 0.19625 square centimeters as an anode, 0.15mol/L oxalic acid, 0.01mol/L NaF and 0.1mol/L Na₂SO₄The electrolyte solution (2) was anodized at a voltage of 60V for 60 minutes with a platinum sheet as a cathode. After the reaction is finished, washing a sample by using flowing deionized water, and drying by using nitrogen to obtain the anode nano-porous tungsten oxide;

(2) carrying out limited loading of ruthenium nanoclusters in tungsten oxide nanopores: 1mg of RuCl₃·3H₂Dissolving O in 12ml of deionized water solvent, putting in a magneton, precipitating at the bottom of the solvent, putting the nano-porous tungsten oxide obtained in the step (1) in a cubic copper cage and suspending on the middle-upper part of the solvent, stirring for 3 hours at room temperature in an air atmosphere on a magnetic stirrer, transferring the solution and the nano-porous tungsten oxide to a reaction kettle with a polytetrafluoroethylene substrate, packaging, putting in a 100 ℃ drying oven, heating for 15 hours, and then cooling to room temperature in the drying oven; then taking out the nano-porous tungsten oxide, washing with absolute ethyl alcohol and deionized water, and drying.

As shown in fig. 4, an XPS spectrum of the tungsten nitride nanoporous film integrated electrode with ruthenium nanoclusters loaded in the limited domain prepared in this example is shown in fig. 4a, which is an XPS full spectrum scan of the tungsten nitride nanoporous film with ruthenium nanoclusters loaded in the limited domain, which shows that the tungsten nitride nanoporous film with ruthenium nanoclusters loaded in the limited domain contains Ru, W, N, C, and O elements, fig. 4b is a scan of Ru elements, which proves that ruthenium exists in a metal valence state, fig. 4C is a scan of W elements, fig. 4d is a scan of N elements, and W and N both are derived from tungsten nitride.

Example 5

(1) And (3) anode treatment: ultrasonically cleaning a 1 square centimeter tungsten foil by using acetone, absolute ethyl alcohol and deionized water respectively, removing organic matters on the surface, and drying by using nitrogen; using a circular tungsten foil with an exposed surface diameter of 0.5 square centimeter and an area of 0.19625 square centimeters as an anode, 0.2mol/L oxalic acid, 0.02mol/L NaF and 0.2mol/L Na₂SO₄The electrolyte solution (2) was anodized at a voltage of 10V for 100 minutes with a platinum sheet as a cathode. After the reaction, the sample was rinsed with flowing deionized water and nitrogen was addedAir drying to obtain anode nano porous tungsten oxide;

(2) carrying out limited loading of ruthenium nanoclusters in tungsten oxide nanopores: 2mg of RuCl₃·3H₂Dissolving O in 30ml of deionized water solvent, putting in a magneton, precipitating at the bottom of the solvent, putting the nano-porous tungsten oxide obtained in the step (1) in a cubic copper cage and suspending on the middle-upper part of the solvent, stirring for 6 hours at room temperature in an air atmosphere on a magnetic stirrer, transferring the solution and the nano-porous tungsten oxide to a reaction kettle with a polytetrafluoroethylene substrate, packaging, heating for 5 hours in a 200 ℃ drying oven, and then cooling to room temperature in the drying oven; then taking out the nano-porous tungsten oxide, washing with absolute ethyl alcohol and deionized water, and drying.

(3) CVD nitridation reaction: and (3) placing the nano porous tungsten oxide obtained in the step (2) in the center of a quartz tube of a CVD tube furnace, setting the furnace temperature at 500 ℃, the argon gas flow at 50sccm, the ammonia gas flow at 10sccm and the total gas pressure at 0.25KPa to perform nitridation reaction for 0.5h, and then naturally cooling to room temperature under the argon atmosphere to obtain the tungsten nitride nano porous film integrated electrode with the ruthenium nanoclusters loaded in a limited domain.

Example 6

(1) And (3) anode treatment: ultrasonically cleaning a 1 square centimeter tungsten foil by using acetone, absolute ethyl alcohol and deionized water respectively, removing organic matters on the surface, and drying by using nitrogen; using a circular tungsten foil with an exposed surface diameter of 0.5 square centimeter and an area of 0.19625 square centimeters as an anode, 0.3mol/L oxalic acid, 0.03mol/L NaF and 0.3mol/L Na₂SO₄The electrolyte solution (2) was anodized at a voltage of 70V for 10 minutes with a platinum sheet as a cathode. After the reaction is finished, washing a sample by using flowing deionized water, and drying by using nitrogen to obtain the anode nano-porous tungsten oxide;

(2) carrying out limited loading of ruthenium nanoclusters in tungsten oxide nanopores: 0.4mg of RuCl₃·3H₂Dissolving O in 8ml of deionized water solvent, putting in a magneton, precipitating at the bottom of the solvent, putting the nano-porous tungsten oxide obtained in the step (1) in a cubic copper cage and suspending on the middle-upper part of the solvent, stirring for 1h in an air atmosphere at room temperature on a magnetic stirrer, and then dissolving the obtained nano-porous tungsten oxide in the solventTransferring the solution and the nano-porous tungsten oxide into a reaction kettle with a polytetrafluoroethylene substrate, packaging, heating in a drying oven at 150 ℃ for 10h, and then, cooling to room temperature in the drying oven; then taking out the nano-porous tungsten oxide, washing with absolute ethyl alcohol and deionized water, and drying.

(3) CVD nitridation reaction: and (3) placing the nano porous tungsten oxide obtained in the step (2) in the center of a quartz tube of a CVD tube furnace, setting the furnace temperature at 900 ℃, the argon gas flow rate at 200sccm, the ammonia gas flow rate at 100sccm and the total gas pressure at 0.4KPa to perform nitridation reaction for 3 hours, and then naturally cooling to room temperature under the argon atmosphere to obtain the tungsten nitride nano porous film integrated electrode with the ruthenium nanoclusters loaded in a limited area.

Example 7

The application of the material obtained in example 7 in the electrochemical field is verified experimentally as follows:

testing the performance of acidic electrocatalysis hydrogen evolution:

to study the hydrogen evolution catalytic performance of the material, a three-electrode system was used for testing on an electrochemical workstation of type CHI-660E, Chen Hua, Shanghai. At 0.5M H₂SO₄The aqueous solution is used as electrolyte, a high-purity platinum sheet is used as a counter electrode, and Hg/Hg of the KCl solution is saturated₂Cl₂The electrode was used as a reference electrode, the tungsten nitride nanoporous membrane with limited loading of ruthenium nanoclusters was used as a working electrode (exposed effective area of 0.19625 square centimeters), hydrogen was bubbled for 30 minutes to remove dissolved oxygen, polarization curve measurement was performed at 50mV/s sweep rate, and all potentials were changed to standard hydrogen electrode (RHE): e_(RHE)＝E_(SCE)+ (0.242+0.059 pH). As shown in FIG. 5a, the initial hydrogen evolution potential of the tungsten nitride nanoporous thin film integrated electrode with ruthenium nanoclusters loaded in a limited domain is about 30mV, and when the current reaches 10mA/cm²The overpotential was 65mV, as shown in FIG. 5b, which is a Tafel plot, and it can be seen that this material has a lower Tafel slope, about 48 mV/dec.

And (3) testing the performance of alkaline electrocatalysis hydrogen evolution:

to study the hydrogen evolution catalytic performance of the material, a three-electrode system was used for testing on an electrochemical workstation of type CHI-660E, Chen Hua, Shanghai. Taking 1.0M KOH aqueous solution as electrolyte, taking a high-purity platinum sheet as a counter electrode, and saturating Hg/Hg of KCl solution₂Cl₂The electrode was used as a reference electrode, the tungsten nitride nanoporous membrane with limited loading of ruthenium nanoclusters as a working electrode (exposed effective area of 0.19625 square centimeters), bubbled with hydrogen for 30 minutes to remove dissolved oxygen, polarization curve measurements were performed at a sweep rate of 50mV/s, and all potentials were exchanged for a standard hydrogen electrode (RHE): e_(RHE)＝E_(SCE)+ (0.242+0.059 pH). As shown in FIG. 6a, the initial hydrogen evolution potential of the tungsten nitride nano-porous film integrated electrode with ruthenium nanoclusters supported in a limited area is about 30mV, and when the current reaches 10mA/cm²The overpotential for this time was 70mV, as shown in FIG. 6b, which is 62mV/dec compared to the material with a lower Tafel slope.

And (3) stability testing: as shown in fig. 7, the tungsten nitride nanoporous film integrated electrode with ruthenium nanoclusters loaded in a limited domain prepared in example 7 of the invention is 0.5M H saturated in hydrogen₂SO₄Galvanostatic stability test curves in solution and in 1M KOH solution. From fig. 7, it can be seen that the tungsten nitride nanoporous film integrated electrode with ruthenium nanoclusters supported in a limited domain prepared by the invention has almost no attenuation compared with the initial value and shows good stability after being tested for 30h and 20h under the acidic and alkaline conditions respectively under constant potential.

Claims

Translated fromChinese

1.一种限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极的制备方法，其特征在于：先合成氧化钨纳米多孔薄膜，然后将其作为载体，通过水热法将钌纳米团簇限域负载在氧化钨纳米多孔孔道及镂空孔壁内，再通过化学气相沉积法一步合成限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极，且具有稳定的结构形貌；1. a preparation method of the tungsten nitride nanoporous thin film integrated electrode of confined load ruthenium nanocluster, it is characterized in that: first synthesize tungsten oxide nanoporous thin film, then as carrier, by hydrothermal method, ruthenium nanometer Clusters are confined and loaded in tungsten oxide nanoporous channels and hollow pore walls, and then a tungsten nitride nanoporous film integrated electrode with confined ruthenium nanoclusters is synthesized by one-step chemical vapor deposition method, and has a stable structure and morphology ;

具体包括以下步骤：Specifically include the following steps:

(1)阳极处理：将20-320平方毫米的钨箔分别用丙酮、无水乙醇和去离子水超声清洗，除去表面的有机物，氮气吹干；将清洗后的钨箔作为阳极，铂片作为阴极，阴阳极表面积比例控制在1:1-6:1之间，采用10-70V直流恒压电源在溶有0.15-0.3mol/L 草酸、0.1-0.3mol/L Na₂SO₄和0.01-0.03mol/L NaF的电解液中阳极氧化10-100分钟，用流动去离子水清洗后用氮气吹干，得到阳极纳米多孔氧化钨；(1) Anode treatment: ultrasonically clean 20-320 square millimeters of tungsten foil with acetone, anhydrous ethanol and deionized water, respectively, to remove organic matter on the surface, and blow dry with nitrogen; the cleaned tungsten foil is used as the anode, and the platinum sheet is used as the anode. Cathode, the ratio of cathode to anode surface area is controlled between 1:1-6:1, using 10-70V DC constant voltage power supply to dissolve 0.15-0.3mol/L oxalic acid, 0.1-0.3mol/L Na₂ SO₄ and 0.01- Anodize in the electrolyte of 0.03mol/L NaF for 10-100 minutes, rinse with flowing deionized water, and dry with nitrogen to obtain anode nanoporous tungsten oxide;

(2)于氧化钨纳米多孔中限域负载钌纳米团簇：将0.4-2mg RuCl₃·3H₂O溶于去离子水溶剂中，将磁力搅拌子沉于溶剂底部，将步骤(1)中得到的纳米多孔氧化钨放于立方铜笼中且悬浮于溶剂中上部，在磁力搅拌器上于空气气氛及室温下搅拌1-6h混合均匀，接着将溶液及纳米多孔氧化钨转移到反应釜中封装好，放入100-200℃的烘箱中加热5-20h，然后在烘箱中程序降温至室温；取出纳米多孔氧化钨并用无水乙醇、去离子水洗涤，干燥；(2) Confinement loading of ruthenium nanoclusters in the tungsten oxide nanoporous medium: Dissolve 0.4-2 mg RuCl₃ ·3H₂ O in deionized water solvent, place a magnetic stirrer at the bottom of the solvent, and place in step (1) The obtained nanoporous tungsten oxide is placed in a cubic copper cage and suspended in the upper part of the solvent, stirred for 1-6 hours on a magnetic stirrer in an air atmosphere and at room temperature, and then the solution and nanoporous tungsten oxide are transferred to the reaction kettle. After packaging, put it into an oven at 100-200°C for 5-20 hours, and then cool it down to room temperature in the oven; take out the nanoporous tungsten oxide, wash it with absolute ethanol and deionized water, and dry it;

(3)CVD氮化反应：将步骤(2)中得到的纳米多孔氧化钨放在CVD管式炉的石英管中央，设置炉温为500-900℃，通入氩气和氨气，总气压为0.25-0.4KPa进行氮化反应，反应时间0.5-3h，然后在保持氩气气氛下，自然冷却到室温，得到限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极。(3) CVD nitridation reaction: place the nano-porous tungsten oxide obtained in step (2) in the center of the quartz tube of the CVD tube furnace, set the furnace temperature to 500-900 ° C, feed argon and ammonia, and the total pressure The nitridation reaction is carried out for 0.25-0.4KPa, the reaction time is 0.5-3h, and then naturally cooled to room temperature in an argon atmosphere to obtain a tungsten nitride nanoporous film integrated electrode with confined ruthenium nanoclusters.

2.根据权利要求1所述的一种限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极的制备方法，其特征在于：所述反应釜为具有聚四氟乙烯材质衬底的反应釜。2. the preparation method of the tungsten nitride nanoporous film integrated electrode of a kind of confined load ruthenium nanoclusters according to claim 1, it is characterized in that: described reaction kettle is a kind of substrate with polytetrafluoroethylene material Reactor.

3.根据权利要求1所述的一种限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极的制备方法，其特征在于：在CVD氮化反应过程中，氨气为反应气，炉温在氩气、氨气存在下匀速升温至500-900℃。3. the preparation method of the tungsten nitride nanoporous thin film integrated electrode of a kind of confined load ruthenium nanocluster according to claim 1, is characterized in that: in CVD nitridation reaction process, ammonia gas is reactant gas, The furnace temperature is heated to 500-900°C at a constant rate in the presence of argon and ammonia.

4.根据权利要求1所述的一种限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极的制备方法，其特征在于：在CVD氮化反应过程中，氩气气体流量为50-200sccm，氨气气体流量10-100sccm。4. the preparation method of the tungsten nitride nanoporous thin film integrated electrode of a kind of confined load ruthenium nanocluster according to claim 1, is characterized in that: in CVD nitridation reaction process, argon gas flow rate is 50 -200sccm, ammonia gas flow 10-100sccm.

5.根据权利要求1所述的一种限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极的制备方法，其特征在于：在CVD氮化反应过程中，所述反应时间为3h。5. The preparation method of a tungsten nitride nanoporous thin film integrated electrode with a confined load of ruthenium nanoclusters according to claim 1, characterized in that: in the CVD nitridation reaction process, the reaction time is 3h .

6.根据权利要求1所述的一种限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极的制备方法，其特征在于：所述步骤(2)中RuCl₃·3H₂O与去离子水的质量体积比为1:6-30mg/ml。6 . The method for preparing a tungsten nitride nanoporous thin film integrated electrode with confined ruthenium nanoclusters according to claim 1 , wherein in the step (2), RuCl₃ ·3H₂ O and The mass to volume ratio of deionized water is 1:6-30 mg/ml.

7.一种权利要求1～6任一项所述的制备方法制得的限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极。7 . A tungsten nitride nanoporous thin film integrated electrode with confined support of ruthenium nanoclusters prepared by the preparation method according to any one of claims 1 to 6 .

8.一种权利要求7所述的限域负载钌纳米团簇的氮化钨纳米多孔薄膜一体化电极在酸性电解水中催化析氢以及碱性电解水中催化析氢的应用。8 . The application of the tungsten nitride nanoporous thin film integrated electrode of confined load ruthenium nanoclusters as claimed in claim 7 in catalyzing hydrogen evolution in acidic electrolyzed water and catalyzing hydrogen evolution in alkaline electrolyzed water. 9 .

9.根据权利要求8所述的应用，其特征在于，包括以下步骤：使用三电极体系在电化学工作站上进行电化学测量；使用封口膜和导线将一体化电极封装，直接用作工作电极。9 . The application according to claim 8 , comprising the following steps: using a three-electrode system to perform electrochemical measurement on an electrochemical workstation; packaging the integrated electrode with a sealing film and a wire, and directly using it as a working electrode. 10 .