阅读说明：本技术 一种棒状钌颗粒/硒化物复合催化剂及其制备方法与应用 (Rod-shaped ruthenium particle/selenide composite catalyst and preparation method and application thereof ) 是由 王春栋 琚君 李林峰 于 2021-10-09 设计创作，主要内容包括：本发明公开了一种棒状钌颗粒/硒化物复合催化剂及其制备方法与应用,属于新能源材料与电化学储能技术领域。本发明通过硒粉、NaBH-(4)、去离子水混合,在室温下搅拌得NaHSe溶液；随后将NaHSe溶液、乙醇、泡沫镍转移到反应釜中,水热法合成NiSe/NF材料；将NiSe/NF材料、RuCl-(3)通过刻蚀法得到所述棒状钌颗粒/硒化物复合催化剂Ru@NiSe。本发明设计了一种简便化学水浴、刻蚀法制备出棒状钌纳米颗粒/硒化物复合材料,该材料在析氢、析氧反应中表现了较低的过电位和良好的稳定性,适于推广与应用。(The invention discloses a rod-shaped ruthenium particle/selenide composite catalyst and a preparation method and application thereof, belonging to the technical field of new energy materials and electrochemical energy storage. The invention uses selenium powder and NaBH 4 Mixing with deionized water, and stirring at room temperature to obtain NaHSe solution; then transferring the NaHSe solution, ethanol and foamed nickel into a reaction kettle, and synthesizing a NiSe/NF material by a hydrothermal method; mixing NiSe/NF material and RuCl 3 And obtaining the rod-shaped ruthenium particle/selenide composite catalyst Ru @ NiSe by an etching method. The invention designs a simple chemical water bath and etching method for preparing rod-like rutheniumThe nano-particle/selenide composite material shows lower overpotential and good stability in hydrogen evolution and oxygen evolution reactions, and is suitable for popularization and application.)

1. A preparation method of a rod-shaped ruthenium particle/selenide composite catalyst is characterized by comprising the following steps:

(1) repeatedly washing the foamed nickel by using dilute hydrochloric acid and deionized water to remove an oxide layer on the surface;

(2) adding NaBH into deionized water₄Mixing the solution and selenium powder for reaction to obtain NaHSe solution;

(3) putting the pretreated nickel foam into a mixed solution of NaHSe solution, ethanol and deionized water, and carrying out hydrothermal reaction to obtain a NiSe/NF precursor;

(4) soaking the NiSe/NF precursor in RuCl₃And taking out the solution, washing the solution with deionized water, and drying the solution in air to obtain the rod-shaped ruthenium particle/selenide composite catalyst.

2. The method for preparing a ruthenium particle/selenide complex catalyst in rod form according to claim 1, wherein the dilute hydrochloric acid concentration in the step (1) is 3mol/L to 5mol/L, and the foamed nickel size is 3 x 2cm²Or 4X 2cm²The pore diameter is 0.1mm, and the porosity is 97.2%.

3. The method for preparing a ruthenium particle/selenide complex catalyst in rod form according to claim 1, wherein, in the step (2),NaBH₄and the selenium powder is 0.039-0.078 g: 0.043-0.086 g.

4. The method for preparing a ruthenium/selenide rod composite catalyst as claimed in claim 1, wherein the volume ratio of ethanol to deionized water in the step (3) is (13-18): (7-2).

5. The method for preparing the rod-shaped ruthenium particle/selenide composite catalyst according to claim 1, wherein the soaking temperature in the step (4) is room temperature, and the soaking time is 12-36 h.

6. The method for preparing a rod-shaped ruthenium particle/selenide composite catalyst according to claim 5, wherein the drying temperature in the air is 60-70 ℃, and the drying time is 8-10 h.

7. The method for preparing a ruthenium/selenide rod composite catalyst as claimed in claim 1 or 6, wherein the NiSe/NF precursor is mixed with RuCl₃The ratio of the solution is 3 x 2cm²～4×2cm²：20～40mL。

8. A ruthenium particle/selenide complex catalyst in rod form prepared by the process of claim 1, wherein the catalyst comprises a foamed nickel support and Ru @ nisi supported on the surface of the foamed nickel support; the Ru @ NiSe vertically grows in a three-dimensional stereoscopic manner on the surface of the foamed nickel, is closely arranged, has a nanorod structure, and is loaded with granular Ru.

9. Use of a rod-shaped ruthenium particle/selenide composite catalyst prepared by the method of claim 1 or the rod-shaped ruthenium particle/selenide composite catalyst of claim 8 in the field of electrocatalysis.

Technical Field

The invention belongs to the technical field of new energy materials and electrochemical energy storage, relates to a preparation method of an inorganic nano catalytic material, and particularly discloses a preparation method of a rod-shaped ruthenium particle/selenide composite catalyst.

Background

With the increasing energy crisis and the drastic change of climate in the world, the earth is facing a growing environmental problem, and the exploration of clean renewable energy sources capable of being applied in large scale becomes a problem to be solved urgently, most renewable energy sources, such as solar energy, wind energy and the like, are intermittent, but hydrogen production by water electrolysis is considered as an effective strategy for developing clean and sustainable new energy sources, and is receiving more and more attention all over the world in the hydrogen production field, and the development of catalysts with low overpotential, high activity and long-term stability becomes more important.

Transition metal oxides, sulfides, phosphides and combinations thereof show good hydrogen evolution reaction and oxygen evolution reaction performances, but compared with noble metal materials, the overpotentials of the transition metal oxides, the sulfides, the phosphides and the combinations thereof are still higher, and in the reaction process of electrocatalytic water decomposition and hydrogen release, the transition metal compounds are generally easy to dissolve in electrolyte, so that the instability of catalytic reaction is more prominent, and the steady operation of water decomposition and hydrogen production cannot be continuously and efficiently promoted. Therefore, in order to ensure the high-efficiency catalytic performance, the utilization rate of the noble metal can be improved through reasonable design, and the aim of reducing the cost is fulfilled.

During the past decade, considerable effort has been devoted to the study of promising noble metal electrode alternatives. Generally, there are two design directions for reducing the consumption of precious metals: (1) synthesis of noble metal-based alloys or non-platinum noble metals, e.g. Pt-WC/W₂C，Au/Ti，Au-MoS₂And NiAu/Au; (2) synthesis of non-noble metal catalysts, e.g. Cu₇S₄@MoS₂，MoS₂And Mo₂C. Although they exhibit good catalytic properties, the high consumption of non-platinum metals and the low specific surface area are not satisfactory. Ru is a catalyst material with excellent performance, and compared with Pt, the Ru has more abundant content on the earth, and the selling price of the Ru is only 1/15 of Pt. Yamauchi et al use organic polymers to constrain Ru and uniformly disperse Ru nanoclusters in carbon nitride compounds with three-dimensional structures by a heat treatment methodThe resultant Ru/NCs catalyst exhibits excellent HER performance at low pH, when the current density reaches 10mA cm^-2At this time, the overpotential is only 30mV, which is comparable to 20 wt% commercial Pt-C. Although the design shows good catalytic activity, the metal Ru coated by the carbon-nitrogen compound enables only the metal on the surface to participate in the reaction, but the metal inside the metal Ru cannot directly participate in the reaction, so that the utilization rate of Ru is reduced, and the quality activity is reduced.

Therefore, in order to fully exert the advantages of the catalytic performance of various metals in the composite structure material, reasonably construct the interface structure between the carrier and the metals, optimize the electronic structure of the catalyst, load metal nanoparticles with high density and small size on the surface as far as possible on the premise of keeping good morphology, realize the purpose of exposing more active sites, and improve the catalytic performance through the synergistic effect between the metal nanoparticles and the metal nanoparticles.

Disclosure of Invention

In view of the above, the present invention provides a rod-like ruthenium particle/selenide composite catalyst, a preparation method thereof and an application thereof, aiming at the problems existing in the prior art.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a preparation method of a rod-shaped ruthenium particle/selenide composite catalyst specifically comprises the following steps:

(1) repeatedly washing the foamed nickel by using dilute hydrochloric acid and deionized water to remove an oxide layer on the surface;

(2) adding NaBH into deionized water₄Adding selenium powder into the solution to react to obtain NaHSe solution;

(3) putting the pretreated nickel foam into a mixed solution of NaHSe solution, ethanol and deionized water, and carrying out hydrothermal reaction to obtain a NiSe/NF precursor;

(4) soaking the NiSe/NF precursor in RuCl₃And taking out the solution, washing the solution with deionized water, and drying the solution in air to obtain the rod-shaped ruthenium particle/selenide composite catalyst.

It is noted that the invention discloses a simple chemical bath deposition method and a wet chemical etching method, and NiSe/NF rods are usedThe nano structure and Ru noble metal nano particles are polymerized together, and Ni is RuCl with low pH value₃Partial oxidation in solution will lose electrons and transfer them to NiSe to make Ru³⁺The obtained electrons are reduced to Ru on the NiSe surface, the mechanism similar to that of the copper-zinc primary battery is used for finally obtaining the NiSe composite structure catalyst loaded with Ru clusters, and the formed heterojunction interface improves the electronic structure of the material and promotes the improvement of catalytic activity.

Preferably, the concentration of the dilute hydrochloric acid in the step (1) is 3 mol/L-5 mol/L, and the size of the foamed nickel is 3 multiplied by 2cm²Or 4X 2cm²The pore diameter is 0.1mm, and the porosity is 97.2%.

Preferably, in the step (2), NaBH₄And the selenium powder is 0.039-0.078 g: 0.043-0.086 g.

Preferably, in the step (3), the volume ratio of the ethanol to the deionized water is (13-18) to (7-2).

Preferably, the soaking temperature in the step (4) is room temperature, and the soaking time is 12-36 h.

And the drying temperature in the air is 60-70 ℃, and the drying time is 8-10 h. The ruthenium etch selenide duration is preferably 12h, 24h, 36h, most preferably 12 h.

And, the NiSe/NF precursor and RuCl₃The ratio of the solution is 3 x 2 (cm)²)～4×2(cm²)：20(mL)～40(mL)。

In addition, the invention also claims a rod-shaped ruthenium particle/selenide composite catalyst prepared by the method, wherein the catalyst comprises a foamed nickel carrier and Ru @ NiSe loaded on the surface of the foamed nickel carrier; the Ru @ NiSe grows vertically in a three-dimensional solid mode on the surface of the foamed nickel, is closely arranged, and has a nanorod structure.

And, it is still another object of the present invention to provide a use of the rod-shaped ruthenium particle/selenide composite catalyst in the field of electrolysis of water.

According to the technical scheme, compared with the prior art, the rod-shaped ruthenium particle/selenide composite catalyst and the preparation method and application thereof provided by the invention have the following excellent effects:

(1) the invention adopts the chemical water bath method to prepare the nickel-based selenide so as to improve the HER and OER performances, and the method for preparing the selenide precursor has simple and convenient operation, environmental protection and low cost, and is suitable for industrial production;

(2) the hydrogen evolution and oxygen evolution performance of the composite material obtained by modifying noble metal ruthenium are effectively improved, and the selenide precursor is synthesized by a water bath method and then NiSe is loaded with a small amount of Ru and Ru by a wet chemical etching method³⁺Electrons are obtained and reduced to Ru on the surface of NiSe, so that the ruthenium particles/selenide have larger specific surface area, more active sites are exposed, and the electrocatalytic performance is improved; the preparation method of the ruthenium particle/selenide disclosed by the invention is simple and easy to understand, the content of noble metal is reduced, and the cost is low;

(3) according to the invention, HER and OER performances are preferably discussed through the short etching time, the short etching time is not beneficial to loading of ruthenium, the long etching time is severe to damage the morphology, and negative effects are caused on the improvement of the catalytic performance; the etching time of the ruthenium particles/selenide prepared by the method is preferably 12 hours, and the obtained catalyst has good catalytic performance and best appearance; and because of low ruthenium load, the cost is greatly reduced, and the commercialization requirement is met;

in addition, the overpotential of the NiSe nanorod modified by Ru is obviously reduced, the kinetics speed of hydrogen evolution and oxygen evolution reactions is improved, and the interaction of electrons in the Ru and Ni composite structure promotes the improvement of Ru @ NiSe catalytic performance;

(4) the preparation method of the rod-shaped ruthenium particle/selenide composite catalyst provided by the invention is simple and convenient to operate, mild in reaction condition and suitable for large-scale production; the prepared product has the characteristics of stability and high catalytic activity of electrolyzed water, can be widely applied to electrochemical energy storage and conversion technology, and has high application value.

The analysis is combined to know that the invention provides a method for preparing the electrode material on a large scale, which is simple and easy to operate, short in preparation period and environment-friendly, and can reduce the consumption of noble metal; the nickel-based selenide high-efficiency catalyst modified by noble metal ruthenium is obtained, and when the etching time of Ru is 12 hours, the catalytic performance and the morphology are better.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.

Fig. 1 is a schematic diagram of the preparation of the ruthenium particle/selenide catalyst material of the invention.

Fig. 2 is an XRD pattern of the ruthenium particle/selenide catalyst material prepared in example 1 of the present invention.

Fig. 3 is SEM and EDS spectra of the ruthenium particle/selenide catalyst material prepared in example 1 of the invention.

Fig. 4 is a TEM image of the ruthenium particle/selenide catalyst material prepared in example 1 of the present invention.

Fig. 5 is a HER performance graph of the ruthenium particle/selenide catalyst material prepared in the inventive example 1.

Fig. 6 is a graph of OER performance of the ruthenium particle/selenide catalyst material prepared in example 1 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The embodiment of the invention discloses a method for synthesizing a rod-shaped ruthenium particle/selenide composite catalyst by a one-step method.

The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.

The technical solution of the present invention will be further described with reference to the following specific examples.

Example 1:

a preparation method of a rod-shaped ruthenium particle/selenide composite catalyst is realized according to the following steps:

(1) preparing a foamed nickel material: the foamed nickel (3X 2cm) was repeatedly rinsed with 3.0M/L dilute hydrochloric acid and deionized water²) To remove the oxide layer on the surface of the foam nickel;

(2) preparation of selenide on foam nickel material: se powder (0.078g) is added to a solution containing NaBH₄(0.086g) in deionized water (2.0 mL); slightly stirring for several minutes to obtain a reddish brown transparent solution, adding ethanol (18mL) into the solution, transferring the solution into a polytetrafluoroethylene-lined stainless steel high-pressure kettle containing a piece of pretreated foamed nickel, then putting the high-pressure kettle into an electric furnace, heating for 12 hours at 140 ℃ to obtain NiSe/NF, finally collecting a sample, washing for multiple times by using water and ethanol, and drying for 8 hours at 60 ℃;

(3) preparing a Ru @ NiSe heterojunction composite electrode material: a rod-shaped NiSe precursor was immersed in 4mg mL^-1RuCl₃Soaking in the solution for 12 h; and then taking out the sample from the solution, washing the sample by using deionized water, and drying the sample in the air to obtain the Ru @ NiSe heterojunction composite material.

Example 2:

this example differs from example 1 in the step (3) of immersion of RuCl₃The solution concentration was 2mg mL^-1Other parameters and the specific implementation steps are the same as those in embodiment 1.

Example 3:

this example differs from example 1 in the step (3) of immersion of RuCl₃The solution concentration was 6mg mL^-1Other parameters and the specific implementation steps are the same as those in embodiment 1.

Example 4:

this exampleThe difference from example 1 is RuCl immersed in step (3)₃The solution concentration was 8mg mL^-1Other parameters and the specific implementation steps are the same as those in embodiment 1.

Example 6:

the difference between this example and example 1 is that the soaking time in step (3) is 24h, and other parameters and specific implementation steps are the same as those in example 1.

Example 7:

the difference between this example and example 1 is that the soaking time in step (3) is 36h, and other parameters and specific implementation steps are the same as those in example 1.

FIG. 1 is a flow diagram for the preparation of Ru @ NiSe.

A rod-shaped NiSe precursor (1 cm. times.2 cm each) was immersed in 4mg mL of the precursor^-1RuCl₃Soaking in the solution for a period of time; and then taking out the sample from the solution, washing the sample with deionized water, and drying the sample in the air to obtain the Ru @ NiSe composite catalyst.

FIG. 2 is an XRD pattern of NiSe, Ru @ NiSe-12h, Ru @ NiSe-24h and Ru @ NiSe-36h prepared in example 1, in which the content of metallic Ru is very small and is difficult to detect, so that the diffraction peak of Ru is difficult to observe.

FIG. 3 is a SEM and EDS spectra of Ru @ NiSe-12h prepared in example 1, from which it can be seen that the prepared material contains Ru element in addition to C, O, Ni, Se element, which demonstrates the successful anchoring of ruthenium to nickel-based selenide by etching.

FIG. 4 is a TEM image prepared in example 1, from which it can be seen that the rough nanorod structure is formed, and a plurality of Ru nanoclusters are formed on the surface and uniformly distributed to cling to the NiSe nanorods; and the side surface reacts with Ru loaded on the surface of NiSe.

Fig. 5 and 6 are HER and OER performance graphs of Ru @ NiSe prepared at different etching times in the embodiment of the present invention, and it can be seen from the graphs that the catalytic performance of hydrogen evolution and oxygen evolution after etching is significantly improved, and the performance of etching for 12h is better than 24h but inferior to 36h, because of the overlong etching time, a large amount of ruthenium is loaded on the surface of the NiSe, the morphology of the original rod-like structure is damaged, and most of the reasons for the good performance are the effect of a large amount of ruthenium.

However, it should be noted that although the etching performance is better for 36h, the profile is destroyed and the cost is greatly increased.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.