CN109364963B - Ruthenium-phosphorus co-modified nickel composite catalyst and preparation method thereof - Google Patents

Ruthenium-phosphorus co-modified nickel composite catalyst and preparation method thereof Download PDF

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CN109364963B
CN109364963B CN201811400658.6A CN201811400658A CN109364963B CN 109364963 B CN109364963 B CN 109364963B CN 201811400658 A CN201811400658 A CN 201811400658A CN 109364963 B CN109364963 B CN 109364963B
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熊昆
黄丽萍
龙川
张海东
陈佳
沈慧珍
卓越
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Chongqing Technology and Business University
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Abstract

The invention belongs to the technical field of electrolytic hydrogen production, and particularly discloses a ruthenium-phosphorus co-modified nickel composite catalyst, which comprises a ruthenium element and nickel phosphide, wherein the ruthenium element is embedded into the nickel phosphide. The invention also discloses a preparation method of the ruthenium-phosphorus co-modified nickel composite catalyst, which comprises the following steps: (1) oxidizing the foamed nickel to prepare foamed nickel with rough surface and containing nickel oxide; (2) and (2) taking the nickel-containing oxide foamed nickel prepared in the step (1) as a cathode, taking a carbon rod as an anode, preparing a mixed solution of a pH electrolyte regulating solution, a ruthenium source and a phosphorus source as an electrolyte, and performing cathodic polarization at the same potential to obtain the ruthenium-phosphorus co-modified nickel composite catalyst. The hydrogen evolution activity of the catalyst prepared by the technical scheme of the invention can be compared favorably with that of a Pt noble metal catalyst.

Description

Ruthenium-phosphorus co-modified nickel composite catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of electrolytic hydrogen production, and particularly discloses a ruthenium-phosphorus co-modified nickel composite catalyst and a preparation method thereof.
Background
In the face of the continuous reduction of global fossil energy and the environmental problems caused by corresponding pollutants, hydrogen energy has been widely concerned by global researchers as a renewable secondary clean energy source.
The most effective catalyst for hydrogen electrolysis is Pt-based noble metal, but the Pt-based noble metal has high cost and scarce resources and cannot be applied in large scale, so at present, researchers change the chemical composition and the electronic structure of the non-noble metal catalyst through measures such as alloying, surface modification, hybridization and the like, and design and synthesize a series of non-noble metal catalysts capable of replacing the Pt-based noble metal. Among them, the transition metal phosphide catalyst has attracted attention because of its electronic structural properties similar to those of hydrogenases and noble metals Pt, good electrical conductivity and corrosion resistance. However, the hydrogen evolution activity of the existing phosphide catalyst still cannot be compared with that of the Pt noble metal catalyst.
Disclosure of Invention
The invention aims to provide a ruthenium-phosphorus co-modified nickel composite catalyst and a preparation method thereof, and aims to improve the hydrogen evolution activity of a phosphide catalyst and enable the hydrogen evolution activity of the phosphide catalyst to be comparable with that of a Pt noble metal.
In order to achieve the purpose, the invention provides the following technical scheme:
a ruthenium-phosphorus co-modified nickel composite catalyst comprises ruthenium element and nickel phosphide, wherein the ruthenium element is embedded into the nickel phosphide by an electrochemical method.
The working principle and the beneficial effects of the basic scheme are as follows:
the hydrogen evolution activity of the ruthenium-phosphorus co-modified nickel composite catalyst can be compared favorably with that of a Pt noble metal catalyst.
The invention also provides a preparation method of the ruthenium-phosphorus co-modified nickel composite catalyst, which comprises the following steps:
(1) oxidizing the foamed nickel to prepare foamed nickel with rough surface and containing nickel oxide;
(2) and (2) taking the nickel-containing oxide foamed nickel prepared in the step (1) as a cathode, taking a carbon rod as an anode, preparing a mixed solution of a pH electrolyte regulating solution, a ruthenium source and a phosphorus source as an electrolyte, and performing cathodic polarization at the same potential to obtain the ruthenium-phosphorus co-modified nickel composite catalyst.
The working principle and the beneficial effects of the basic scheme are as follows:
the preparation method comprises the following steps (1): the surface of the foamed nickel is rough, which is beneficial to increasing the active specific surface area, the catalytic hydrogen evolution activity and the active potential of the foamed nickel, promotes the transmission of electrolyte and the timely diffusion of the generated gas product in the reaction process, and provides possibility for the catalytic electrode to have better hydrogen evolution catalytic activity.
In the step (2): under the same potential, the phosphorus source and the foam nickel with rough surface and containing nickel oxide generate nickel phosphide, and the ruthenium source is reduced to obtain metal ruthenium, thereby forming a phosphide catalyst structure with ruthenium element embedded in the nickel phosphide.
Because the hydrogen evolution catalytic performance of ruthenium is equivalent to that of Pt, but the price is only 1/20 of Pt, and ruthenium also shows excellent corrosion resistance and heavy metal poisoning resistance in practical application, currently, ruthenium is used singly as an example of a catalyst in industry, and the existing ruthenium catalyst is prepared by coating solution type ruthenium ions on the surface of a support, heating at high temperature to enable the ruthenium ions to generate metal ruthenium or ruthenium oxide, and then carrying out practical industrial application.
In addition, the applicant consults the literature and learns that most of the existing enterprises adopt high-temperature solid-phase phosphating reaction to prepare nickel phosphide, and the adoption of the method can inevitably cause a phosphorus source to generate PH at high temperature3And the like. The applicant has therefore considered that if the existing preparation method (using high temperature conditions) is used only, the ruthenium metal or ruthenium oxide is coated on the surface of the nickel phosphide, which not only produces pH3And the like, and the preparation process of the ruthenium-phosphorus co-modified nickel composite catalyst is complex and is not suitable for large-scale application.
The key point of the invention is that the nickel phosphide is prepared by adopting a normal-temperature and normal-pressure electrochemical reduction method instead of a high-temperature and harsh solid-phase phosphating method. Meanwhile, the method is different from the conventional electrochemical deposition method that the electrolyte containing a nickel source and a phosphorus source is directly subjected to reduction deposition to prepare the Ni-P electrode, but the electrochemical phosphating is carried out on the foam nickel with rough surface and containing nickel oxide, so that the purposes of adjusting the surface phosphating degree, crystalline state, oxygen content and the like of the nickel phosphide and further improving the hydrogen evolution activity of the nickel phosphide are realized. On the basis of ensuring electrochemical phosphorization, the ruthenium source is subjected to in-situ reduction and is deposited on the nickel phosphide under the condition of a phosphorization potential, so that the ruthenium source and the phosphorus are paired to form the ruthenium-phosphorus co-modified nickel composite catalyst, and the hydrogen evolution activity of the nickel phosphide is further improved.
In conclusion, the invention avoids using high-temperature solid-phase phosphorization reaction to prepare phosphide catalyst, and simultaneously introduces ruthenium in the electrochemical phosphorization process to form the ruthenium-phosphorus co-modified nickel composite catalyst in one step, thereby realizing co-modification of the ruthenium catalyst and the nickel phosphide at the same potential, further improving the hydrogen evolution activity of the phosphide catalyst, leading the hydrogen evolution performance of the phosphide catalyst to be comparable with Pt noble metal, and greatly reducing the production cost. The preparation method is simple and easy to implement, safe to operate, low in cost, suitable for the fields of chlor-alkali electrolysis and water electrolysis hydrogen production, and has a wide industrial application prospect.
Further, the ruthenium-phosphorus co-modified nickel composite catalyst comprises a flower spherical structure integrated by nanosheet stacks. The specific surface area of the catalytic electrode is obviously increased, which is beneficial to increasing the active potential of the catalytic electrode, promoting the transmission of electrolyte and the timely diffusion of generated gas products in the reaction process, and providing possibility for the catalytic electrode to have better hydrogen evolution activity.
Further, the step (1) is to put the cleaned foam nickel into hydrogen peroxide for soaking, and to seal and heat the soaking solution of the hydrogen peroxide. The hydrogen peroxide has strong oxidizing property, the surface of the foamed nickel forms nickel oxide under the action of the hydrogen peroxide, and the hydrogen peroxide is adopted to soak the foamed nickel under the room temperature condition, so that the reaction speed is slow, and the oxidation degree of the surface of the foamed nickel is low. Therefore, the soaking liquid is subjected to sealed heating, hydrogen peroxide is gasified, and the air pressure in the sealed environment is increased, so that the sealed environment is high in temperature and pressure, and has stronger corrosion capability. The reaction product of the foamed nickel and the hydrogen peroxide is nickel oxide and water, and the nickel oxide is soluble in the water, so that pits can be formed on the part of the foamed nickel corroded by the hydrogen peroxide. By controlling the concentration of hydrogen peroxide, the oxidation temperature and the oxidation time in the sealed environment, the foamed nickel can form a rough surface containing nickel oxide.
Further, the mass concentration of hydrogen peroxide in the step (1) is 0.5-30%, and the prepared nickel phosphide has good surface phosphorization degree, crystalline state, oxygen content and hydrogen evolution activity under the mass concentration of hydrogen peroxide.
Further, the oxidation temperature in the step (1) is 60-200 ℃, and the oxidation time is 2-24 hours. Under the oxidation condition, the prepared nickel phosphide has better surface phosphorization degree, crystalline state, oxygen content and hydrogen evolution activity.
Further, the pH electrolyte adjusting solution in the step (2) comprises sodium citrate and ammonium sulfate. Because the ammonium is alkaline and the sulfate ions are stable, the ammonium sulfate plays a role in regulating and controlling the acidity and alkalinity of the electrolyte. And (2) generating a complex by ruthenium trichloride and citrate ions, and slowly removing ruthenium ions from the complex when a phosphorus source and the foamed nickel with the rough surface and containing the nickel oxide prepared in the step (1) generate nickel phosphide to obtain electron-precipitated metal ruthenium, and combining the metal ruthenium with the nickel phosphide.
The applicant considers that if ruthenium ions rapidly obtain electrons to precipitate a large amount of metal ruthenium, the metal ruthenium can be deposited into blocks, the shape of the ruthenium-phosphorus co-modified nickel composite catalyst is not controllable, and the metal ruthenium cannot be uniformly combined on nickel phosphide, so that the hydrogen evolution activity of the nickel phosphide cannot be effectively improved. Therefore, the applicant adds citrate ions into the electrolyte, so that the ruthenium trichloride firstly generates a complex with the citrate ions.
Further, the pH electrolyte regulating solution in the step (2) further comprises hydrochloric acid; the ruthenium source is ruthenium trichloride; the phosphorus source is sodium hypophosphite.
The hydrochloric acid is added to inhibit the hydrolysis reaction of the ruthenium trichloride, and in addition, the hydrochloric acid can also be used for adjusting the acidity and alkalinity of the electrolyte. Although the prior literature reports that sodium hypophosphite is also used as a phosphorus source, toxic gas is formed in the high-temperature solid-phase phosphorization process, the inorganic salt sodium hypophosphite is selected as the phosphorus source, any toxic gas is not generated through electrochemical phosphorization, and the preparation condition is milder.
Further, the concentration of the sodium citrate in the step (2) is 5-100 mmol/L, the concentration of the hydrochloric acid is 5-20 mmol/L, the concentration of the ammonium sulfate is 5-100 mmol/L, the concentration of the ruthenium trichloride is 5-50 mmol/L, and the concentration of the sodium hypophosphite is 10-500 mmol/L. Under the conditions, the prepared ruthenium-phosphorus co-modified nickel composite catalyst has better hydrogen evolution activity.
Further, the cathode polarization potential in the step (2) is-0.8 to-1.2V, and the cathode polarization time is 0.5 to 2 hours. Under the conditions, the prepared ruthenium-phosphorus co-modified nickel composite catalyst has better hydrogen evolution activity.
Drawings
FIG. 1 is a scanning electron microscope image of a ruthenium-phosphorus co-modified nickel composite catalyst (Ru-Ni-NF) according to example 1 of the present invention;
FIG. 2 is an XRD pattern of NF and Ru-Ni-NF formed by electrochemical phosphorization after hydrogen peroxide oxidation etching in example 1 of the present invention;
FIG. 3 is a hydrogen evolution linear sweep voltammogram of NF, Ru-Ni-NF and commercial Pt/C catalysts after oxidation etching of NF and hydrogen peroxide in example 1 of the present invention.
Detailed Description
The following is further detailed by way of specific embodiments:
a ruthenium-phosphorus co-modified nickel composite catalyst and a method for preparing the same will be described in detail below by taking example 1 as an example, and examples 2 to 5 are shown in Table 1, and the portions not shown are the same as example 1.
Example 1
A ruthenium-phosphorus co-modified nickel composite catalyst comprises ruthenium element and nickel phosphide, wherein the ruthenium element is embedded into the nickel phosphide by an electrochemical method.
A preparation method of a ruthenium-phosphorus co-modified nickel composite catalyst specifically comprises the following steps:
(1) putting the cleaned nickel foam into a reaction kettle containing 15% hydrogen peroxide by mass concentration, oxidizing at 150 ℃ for 16h, and carrying out hydrothermal oxidation etching to obtain nickel oxide-containing nickel foam;
(2) and (2) taking the foamed nickel with the rough surface and containing the nickel oxide obtained in the step (1) as a cathode and a carbon rod as an anode, preparing a mixed solution of 50mmol/L sodium citrate, 10mmol/L hydrochloric acid, 50mmol/L ammonium sulfate, 10mmol/L ruthenium trichloride and 100mmol/L sodium hypophosphite as an electrolyte, reacting for 2 hours under the constant potential condition of-1.2V, and obtaining the ruthenium-phosphorus co-modified nickel composite catalyst through cathode polarization.
TABLE 1
Figure BDA0001876240900000051
Comparative example
A commercial Pt/C catalyst having a loading of 20 wt% Pt, model Johnson Matthey, was used.
A three-electrode system is adopted, a 1mol/L KOH aqueous solution is used as an electrolyte solution, the ruthenium-phosphorus co-modified nickel composite catalyst prepared in examples 1-5 and a commercial Pt/C catalyst of a comparative example are used as working electrodes, a mercury/mercury oxide electrode is used as a reference electrode, a carbon rod is used as an auxiliary electrode, and the hydrogen evolution linear sweep voltammetry curve is tested on an electrochemical workstation.
Conclusion
(1) As can be observed from fig. 1, the surface of the foamed nickel is oxidized and etched by hydrogen peroxide and then electrochemically phosphated to form the ruthenium-phosphorus co-modified nickel composite catalyst, the catalyst mainly comprises a flower-ball structure integrated by a nanosheet stack, the specific surface area of the catalytic electrode is obviously increased, the increase of the active potential of the catalytic electrode is facilitated, the transmission of electrolyte and the timely diffusion of a gas product generated in the reaction process are promoted, and the possibility of better hydrogen evolution activity of the catalytic electrode is provided.
(2) As can be observed from fig. 2, the characteristics of the metal NF are still maintained after the Nickel Foam (NF) is oxidized and etched by the hydrogen peroxide, no obvious oxide is detected by XRD, which indicates that the NF is oxidized by the hydrogen peroxide and only stays on the surface, however, after the ruthenium-phosphorus co-modified nickel composite catalyst is formed by the subsequent electrochemical phosphorization, the diffraction peak presents a broadening and a new characteristic diffraction peak appears, and the nickel phosphide is confirmed by comparing with a standard spectrogram, but a small amount of nickel oxide still exists, so the crystal diffraction peak of the nickel phosphide is small; the figure does not show any diffraction peaks for ruthenium-containing species, probably due to very low ruthenium content, good dispersion and poor crystal formation of the electrochemical reduction deposit.
(3) As can be observed from FIG. 3, the curveThe line a is a linear sweep voltammetry curve of NF, the curve b is a linear sweep voltammetry curve of NF after hydrogen peroxide oxidation etching, the curve C is a linear sweep voltammetry curve of the ruthenium-phosphorus co-modified nickel composite catalyst, and the curve d is a linear sweep voltammetry curve of the commercial Pt/C catalyst; at a current density of 10mA/cm2During the process, the overpotentials of the NF, the ruthenium-phosphorus co-modified nickel composite catalyst and the commercial Pt/C catalyst after oxidation etching of NF and hydrogen peroxide are 172mV, 137mV, 45mV and 38mV respectively, and the data show that the hydrogen evolution activity of the ruthenium-phosphorus co-modified nickel composite catalyst formed by performing electrochemical phosphorization after oxidation etching of hydrogen peroxide on the surface of the foamed nickel is obviously improved and is very close to the potential of the commercial Pt/C catalyst electrode.
The foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent.

Claims (7)

1. The preparation method of the ruthenium-phosphorus co-modified nickel composite catalyst is characterized by comprising the following steps of:
(1) oxidizing the foamed nickel to prepare foamed nickel with rough surface and containing nickel oxide;
(2) preparing a pH electrolyte regulating solution by using the nickel-containing oxide foamed nickel prepared in the step (1) as a cathode and a carbon rod as an anode, wherein the pH electrolyte regulating solution comprises sodium citrate, ammonium sulfate and hydrochloric acid, and a mixed solution of a ruthenium source, a phosphorus source and the regulating solution is used as an electrolyte to obtain a ruthenium-phosphorus co-modified nickel composite catalyst through same-potential cathodic polarization;
the ruthenium-phosphorus co-modified nickel composite catalyst comprises a flower spherical structure integrated by nanosheet stacks, and comprises a ruthenium element and nickel phosphide, wherein the ruthenium element is embedded into the nickel phosphide.
2. The preparation method of the ruthenium-phosphorus co-modified nickel composite catalyst according to claim 1, wherein the step (1) comprises soaking the cleaned foamed nickel in hydrogen peroxide, and hermetically heating the soaking solution of the hydrogen peroxide.
3. The preparation method of the ruthenium-phosphorus co-modified nickel composite catalyst according to claim 2, wherein the mass concentration of hydrogen peroxide in the step (1) is 0.5-30%.
4. The preparation method of the ruthenium-phosphorus co-modified nickel composite catalyst according to claim 3, wherein the oxidation temperature in the step (1) is 60-200 ℃ and the oxidation time is 2-24 h.
5. The method for preparing the ruthenium-phosphorus co-modified nickel composite catalyst according to claim 4, wherein the ruthenium source is ruthenium trichloride; the phosphorus source is sodium hypophosphite.
6. The preparation method of the ruthenium-phosphorus co-modified nickel composite catalyst according to claim 5, wherein the concentration of the sodium citrate in the step (2) is 5-100 mmol/L, the concentration of the hydrochloric acid is 5-20 mmol/L, the concentration of the ammonium sulfate is 5-100 mmol/L, the concentration of the ruthenium trichloride is 5-50 mmol/L, and the concentration of the sodium hypophosphite is 10-500 mmol/L.
7. The method for preparing the ruthenium-phosphorus co-modified nickel composite catalyst according to claim 3, wherein the cathodic polarization potential in the step (2) is-0.8V to-1.2V, and the cathodic polarization time is 0.5 h to 2 h.
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