CN113604832B - (Ru-P) @ Pt monatomic alloy material and preparation method and application thereof - Google Patents
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Abstract
The invention relates to the technical field of electrochemistry, in particular to a (Ru-P) @ Pt monatomic alloy material and a preparation method and application thereof. The invention discloses a (Ru-P) @ Pt monatomic alloy material which has platinum and ruthenium double active sites and has a synergistic effect, so that the (Ru-P) @ Pt monatomic alloy material has high-efficiency performance of hydrogen evolution from electrolyzed water and durability and stability, and has a wide application prospect in the field of electrocatalysis.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a (Ru-P) @ Pt monatomic alloy material and a preparation method and application thereof.
Background
Over the past decade, hydrogen fuel cells have been overlooked due to the explosion of lithium battery technology and industry. In recent years, the lithium battery industry has met with some bottlenecks, and the hydrogen fuel battery has attracted attention of the host factory again. In addition to the high range of operation achievable with small volumes of liquid hydrogen if the hydrogen storage system is at a sufficiently high pressure, hydrogen is the cleanest energy source and the reaction product of hydrogen fuel cells is water alone. Hydrogen can store electric energy in large quantities and for a long time, and is also an energy carrier which can be transported for a long distance. In addition, the fuel in the fuel cell can be used for generating power and driving the automobile. In the future, it is expected to utilize hydrogen derived from renewable energy sources to establish carbon dioxide (CO) free from production to use 2 ) The hydrogen supply system of (1). The hydrogen generated by electrochemical water decomposition can realize energy conversion between electric energy and hydrogen, and provides greater possibility for sustainable hydrogen economy. While electrochemical Hydrogen Evolution (HER) plays an important role in clean, sustainable hydrogen energyAnd (4) color. In general, HER occurs in either acidic or basic media. However, the use of acidic HER catalysts is limited by expensive proton exchange membranes and slow acidic oxygen evolution reactions at the electrodes, and basic HER can avoid these obstacles. Unlike acidic conditions, alkaline solutions lack the H required for HER reactions + The ions, and therefore the need to add an additional water dissociation step, lead to a reduction in the reaction kinetics, which is two orders of magnitude lower than in the acid, even with the platinum catalyst, which has been considered the most active. Thus, obtaining highly efficient basic HER catalysts remains a great challenge.
Disclosure of Invention
In view of the above, the invention provides a (Ru-P) @ Pt monatomic alloy material and a preparation method and application thereof, the material has platinum and ruthenium double active sites, and the double active sites have a synergistic effect, so that the (Ru-P) @ Pt monatomic alloy material has high-efficiency electrolyzed water hydrogen evolution performance and durable stability.
The invention provides a (Ru-P) @ Pt monatomic alloy material, comprising: the carbon nano tube and (Ru-P) @ Pt monatomic alloy loaded on the surface of the carbon nano tube;
the (Ru-P) @ Pt monatomic alloy includes: ruthenium atoms, phosphorus atoms, and platinum nanoparticles;
phosphorus atoms and platinum atoms are loaded on the surface of the platinum nanoparticles.
In the invention, different atoms in the (Ru-P) @ Pt monatomic alloy material are mutually cooperated, so that the catalytic activity is improved. In the present invention, the mass ratio of ruthenium atoms, phosphorus atoms and platinum atoms in the (Ru-P) @ Pt monatomic alloy material is (3 to 12): (1-5): (1-4), preferably 3.
The invention also provides a preparation method of the (Ru-P) @ Pt monatomic alloy material, which comprises the following steps:
step 1: adding the carbon nano tube solution into the ruthenium source solution, heating and refluxing, then adding a reducing agent solution, and carrying out reduction reaction to obtain the carbon nano tube loaded with the amorphous ruthenium nano particles;
step 2: grinding the carbon nano tube loaded with the amorphous ruthenium nano particles, and carrying out heat treatment to obtain the carbon nano tube loaded with the shaped ruthenium nano particles;
and 3, step 3: carrying out heat treatment on the carbon nano tube loaded with the shaped ruthenium nano particles in the presence of a phosphorus source to obtain the carbon nano tube loaded with the ruthenium nano particles and the phosphorus nano particles;
and 4, step 4: and mixing the solution of the carbon nano tube loaded with the ruthenium nano particles and the phosphorus nano particles with a platinum source, and adding a reducing agent to react to obtain the (Ru-P) @ Pt monatomic alloy material.
The P atom and the Pt monoatomic atom are doped on the Ru nano particles to modify the nano particles, so that the dispersity of Ru is good, and the TEM result shows that the Ru nano particles are uniformly dispersed on the carbon nano tubes. Meanwhile, the catalytic activity can be improved by the synergistic effect of different atoms.
The invention utilizes the synergistic catalytic action of Ru nano particles and Pt single atoms loaded on the carbon nano tube to construct double active sites, and in addition, the electronegativity of P is very large, so that the P is easy to form bonds with metals and generate charge transfer. Meanwhile, the radius of the P atom is very small, and the P atom is doped in the crystal lattice without changing the original crystal lattice configuration.
In the invention, in an alkaline environment, ru nano particles are reduced and loaded on the carbon nano tubes to provide H 2 The adsorption and dissociation sites of O are phosphated to regulate the electronic structure orbit of Ru and reduce H on Ru 2 The adsorption energy of O enables H to be efficiently carried out at Ru sites 2 Adsorption and dissociation of O. And then, loading the monoatomic Pt, and performing H absorption and desorption on Pt sites, thereby achieving the purpose of efficiently electrolyzing water to generate hydrogen.
In the step 1 of the invention, the ruthenium source solution needs to be heated and refluxed to form a uniform solution, and then the uniform solution is mixed with the carbon nano tube solution; the heating reflux temperature is 100-120 deg.C, preferably 110 deg.C, and the time is 40-80 min, preferably 1h.
In step 1 of the invention, the heating reflux temperature is 100-120 ℃, preferably 110 ℃, and the time is 40-80 min, preferably 1h;
the temperature of the reduction reaction is 100-120 ℃, the preferable temperature is 110 ℃, and the time is 1.5-2.5 h, and the preferable time is 2h;
the reducing agent is sodium hydroxide; the solvent of the reducing agent solution is ethanol and/or water; the reducing agent is used to reduce ruthenium ions. In the present invention, it is preferable to add additional reducing agent after a part of the reducing agent is added to ensure complete reduction of trivalent ruthenium ions.
In step 2 of the present invention, the heat treatment specifically comprises: at H 2 Heating to 450-500 ℃ at the heating rate of 3-5 ℃/min in the/Ar mixed atmosphere, and keeping the temperature for 1-2 h, preferably heating to 450 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 1h.
In step 3 of the present invention, the heat treatment specifically comprises: heating to 350-400 ℃ at the heating rate of 2-3 ℃/min, and keeping the temperature for 3-4 h, preferably heating to 400 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 3h.
In step 3 of the invention, after adding the reducing agent, preferably transferring the reaction solution to an ice bath, and then adding the reducing agent in a dropwise manner under the ice bath condition;
the reducing agent is one or more than two of sodium borohydride, ethylenediamine, hydrazine hydrate and ascorbic acid;
in the invention, the ruthenium source is one or more than two of ruthenium trichloride, ruthenium triiodide, ruthenium oxide and ruthenium acetate;
the platinum source is one or more than two of chloroplatinic acid hexahydrate, potassium chloroplatinate and ammonium chloroplatinate;
the phosphorus source is one or more than two of sodium hypophosphite, sodium dihydrogen hypophosphite and triphenyl phosphorus.
In the invention, the mass ratio of the ruthenium source to the carbon nano tube is 1;
the mass ratio of the ruthenium source to the phosphorus source to the platinum source is (10-30): (0.5-1.5): (50 to 150), preferably 20:1:100.
the invention also provides application of the (Ru-P) @ Pt monatomic alloy material in hydrogen evolution reaction.
According to the technical scheme, the invention has the following advantages:
the invention provides a (Ru-P) @ Pt monatomic alloy material which has platinum and ruthenium double active sites and has synergistic effect, so that the (Ru-P) @ Pt monatomic alloy material has high-efficiency performance of hydrogen evolution from electrolyzed water and durable stability, and has wide application prospect in the field of electrocatalysis.
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, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is an X-ray diffraction (XRD) pattern of a (Ru-P) @ Pt monatomic alloy provided in example 2 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of (Ru-P) @ Pt monatomic alloy material provided in example 2 of the present invention;
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) survey of the (Ru-P) @ Pt monatomic alloy material provided in example 2 of the present invention;
FIG. 4 is a graph of linear scan polarization curve (LSV) performance of the (Ru-P) @ Pt monatomic alloy material and Ru/C and commercial Pt/C provided in example 2 of the present invention;
FIG. 5 is a Linear Sweep Voltammetry (LSV) graph of (Ru-P) @ Pt monoatomic alloy material provided in examples 2 to 4 of the present invention;
FIG. 6 is a Tafel slope (Tafel) plot of (Ru-P) @ Pt monatomic alloy material and Ru/C and commercial Pt/C provided in example 2 of the present invention;
FIG. 7 is an impedance (ESI) plot of the @ Pt monatomic alloy material and Ru/C and commercial Pt/C provided in example 2 of the present invention;
FIG. 8 is a graph of LSV after 1000 cycles of the (Ru-P) @ Pt monatomic alloy material provided in example 2 of the present invention.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the embodiments described below 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.
Example 1
Preparing P-doped Ru nano particles;
83mg of RuCl are first weighed 3 Ultrasonically dispersing in 100mL of ethanol, placing in an oil bath pan after 30min, heating to 110 ℃, and refluxing for 1h; secondly, injecting 200mg of Carbon Nanotubes (CNTs) dispersed in an ethanol solution into the solution; then 48mg of NaOH (in ethanol or water) was injected rapidly when the solution temperature was stable at 110 ℃. After 2 hours, an additional 8mg of NaOH was injected to ensure Ru 3+ And (4) completely reducing. After refluxing the solution for another 30min, the composite was centrifuged, washed 3 times with ethanol and dried overnight under vacuum. At this time, the Ru nanoparticles supported on CNTs belong to an amorphous Ru metal core, and are denoted as Ru (N).
To obtain shaped Ru nanoparticles loaded on carbon nanotubes, ru (N) was ground for 10min and then filled with H 2 Ar (5% of the total H) 2 ) And (3) heating to 450 ℃ in a tube furnace with mixed atmosphere, keeping for 1h at the heating rate of 3 ℃/min, then naturally cooling to room temperature, and collecting a sample and recording as Ru/C.
Placing 30mg Ru/C in a porcelain boat, placing the porcelain boat at the upper end of a quartz tube, and placing 1g NaH 2 PO 4 Putting the quartz tube into a porcelain boat, placing the quartz tube into a tube furnace at the lower end of the quartz tube, heating to 400 ℃, keeping the temperature for 3 hours at the heating rate of 2 ℃/min, then naturally cooling to room temperature, and collecting a sample and recording the sample as P-Ru/C.
Example 2
The preparation method of the (Ru-P) @ Pt monatomic alloy material comprises the following specific preparation steps:
20mg of the P-Ru/C obtained in example 1 was dispersed in 40mL of a solution (ethanol: water = 1), ultrasonically dispersed for 30min, and placed in a 0 ℃ ice bath and stirred for 1h. Then 25ul 50mM H was taken 2 PtCl 6 ·6H 2 O was added to the above solution, stirred for 1.5h, then 3mg of 5ml sodium borohydride (NaBH) 4 ) Ice water solution, complete reduction of Pt 4+ . Taking out after 1h, centrifuging, washing for 3 times by ethanol, and drying overnight in vacuum to obtain a sample (Ru-P) @ Pt monatomic alloy material.
FIG. 1 is an X-ray diffraction (XRD) pattern of (Ru-P) @ Pt monatomic alloy material produced in example 2, from which diffraction peaks of Ru and the base carbon nanotube can be seen, and no diffraction peak of Pt is observed, indicating that Pt atoms may be monodispersed supported on Ru nanoparticles or Pt nanoparticles are too small.
FIG. 2 is a Transmission Electron Microscope (TEM) image of the (Ru-P) @ Pt monoatomic alloy material prepared in example 2, in which ruthenium Nanoparticles (NPs) having a diameter of about 8nm are uniformly distributed on the carbon nanotube, as shown. Inset is a high resolution TEM image with lattice spacings of 2.34, 2.14 and
corresponding to the (100), (001) and (101) faces of the hexagonal Ru, respectively. Also, no Pt nanoparticles were seen, and Pt was presumed to be a monoatomic form, consistent with the XRD measurements.
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) survey of the monoatomic alloy material (Ru-P) @ Pt prepared in example 2, and it can be seen that the catalyst contains five elements of Ru, pt, C, O and P, indicating that P atoms and Pt atoms are successfully incorporated into Ru nanoparticles, and the mass ratio of the ruthenium source, the phosphorus source and the platinum source is 3:1:1.
the loading of Pt in the (Ru-P) @ Pt monatomic alloy material in this example was about 1wt%.
Example 3
20mg of P-Ru/C prepared in example 1 was dispersed in 40mL of a solution (ethanol: water = 1. 40ul 50mM H was then taken 2 PtCl 6 .6H 2 O was added to the above solution, stirred for 1.5h, and then 3mg of 5ml sodium borohydride (NaBH) was added dropwise 4 ) Ice water solution, complete reduction of Pt 4+ . Taking out after 1h, centrifuging, and extracting with ethanolWashing 3 times, vacuum drying overnight, get sample (Ru-P) @ Pt monatomic alloy material.
The loading of Pt in the (Ru-P) @ Pt monatomic alloy material in this example was about 2wt%.
Example 4
20mg of P-Ru/C prepared in example 1 was dispersed in 40mL of a solution (ethanol: water = 1), ultrasonically dispersed for 30min and then placed in a 0 ℃ ice bath and stirred for 1h. Then 60ul 50mM H 2 PtCl 6 .6H 2 O was added to the above solution, stirred for 1.5h, and then 3mg of 5ml sodium borohydride (NaBH) was added dropwise 4 ) Ice water solution, complete reduction of Pt 4+ . Taking out after 1h, centrifuging, washing for 3 times by ethanol, and drying overnight in vacuum to obtain a sample (Ru-P) @ Pt monatomic alloy material.
The loading of Pt in the (Ru-P) @ Pt monatomic alloy material of this example was about 4wt%.
Test examples
HER performance test:
all HER catalytic measurements were carried out in a standard three-electrode system using CHI760E electrochemical workstation (CH instruments, shanghai), with (Ru-P) @ Pt monoatomic alloy material as the working electrode, a carbon rod as the counter electrode, an Ag/AgCl electrode as the reference electrode, and 1.0M KOH solution as the electrolyte, with the purpose of removing dissolved oxygen, before the test N was used 2 The electrolyte was bubble purified for 30min. Typically, 5mg of (Ru-P) @ Pt monatomic alloy material was weighed and ultrasonically dispersed in 1mL of a mixed solution (730. Mu.L of isopropanol + 250. Mu.L of deionized water + 20. Mu.L of Nafion) for 30 minutes to form a uniform catalyst ink. Then, 12. Mu.L of the catalyst ink was loaded on a glassy carbon Rotating Disk Electrode (RDE) (diameter: 5mm, area: 0.196 cm) 2 ) After natural drying, the catalytic activity was measured by Linear Sweep Voltammetry (LSV) at a sweep rate of 1mV s -1 The RDE rotation rate was 1600rpm. Wherein all potentials are calibrated to Reversible Hydrogen Electrode (RHE) with E (RHE) = E (Ag/AgCl) +0.197V +0.05pH and the current is normalized to the geometric area to obtain the current density. And obtaining the Tafel slope according to the LSV graph.
The charge passed during the hydrogen desorption was integrated by Cyclic Voltammetry (CV), under nitrogenSaturated 0.5MH 2 SO 4 In solution, the scanning rate is 50mV s at room temperature -1 The electrochemically active specific surface area (ECSA) was determined. Electrochemical Impedance Spectroscopy (EIS) measurements were performed on RHE at 50mV over a frequency range of 10kHz to 0.01 Hz.
Durability tests were performed in 1.0MKOH solutions using the chronopotentiometry method.
FIG. 4 is a graph of Linear Sweep Voltammetry (LSV) of (Ru-P) @ Pt monoatomic alloy material and Ru/C and commercial Pt/C prepared in example 2, from which it can be seen that the composite material prepared was at 10mAcm -2 The overpotential of (c) is only 17mV, which is already significantly better than that of the commercial platinum-carbon catalyst (35 mV).
FIG. 5 is a plot of Linear Sweep Voltammetry (LSV) for the resulting (Ru-P) @ Pt monatomic alloy materials of examples 2-4 at various Pt loadings, as seen at 10mAcm when the Pt loading was about 1% or so -2 The overpotential at this time was minimal, only 17mV.
FIG. 6 is a graph of the produced (Ru-P) @ Pt monoatomic alloy material of example 2, ru/C and commercial Pt/C Tafel (Tafel), from which it can be seen that the Tafel value of the prepared composite material is 27mV dec -1 Has obviously better performance than commercial platinum-carbon catalyst (53 mV dec) -1 )。
FIG. 7 is a diagram of Electrochemical Impedance Spectroscopy (EIS) of Ru-P @ Pt monatomic alloy material and Ru/C and commercial Pt/C obtained in example 2, and it can be seen that the charge transfer resistance (Rct) of the prepared composite material is 3.2 Ω, which is significantly better than that of the commercial platinum-carbon catalyst (5.5 Ω).
FIG. 8 is the LSV of the (Ru-P) @ Pt monatomic alloy material obtained in example 2 after 1000 cycles, and it can be seen from the LSV graphs that the LSV curves before and after the cycle of the composite material obtained substantially coincide, indicating that the obtained (Ru-P) @ Pt monatomic alloy has excellent cycle stability.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (3)
1. A preparation method of (Ru-P) @ Pt monatomic alloy material is characterized by comprising the following steps:
step 1: 83mg of RuCl was weighed 3 Ultrasonically dispersing in 100mL of ethanol, placing in an oil bath pan after 30min, heating to 110 ℃, and refluxing for 1h; injecting 200mg of carbon nanotubes dispersed in an ethanol solution into the solution; then when the temperature of the solution is stabilized at 110 ℃, injecting 48mg of NaOH, after 2 hours, injecting 8mg of NaOH, after the solution reflows for 30min, centrifuging the composite material, washing with ethanol, and drying in vacuum overnight to obtain the carbon nano tube loaded with the amorphous ruthenium nano particles;
step 2: grinding the carbon nano-tube loaded with the amorphous ruthenium nano-particles until the carbon nano-tube is filled with H 2 Heating to 450 ℃ in a tubular furnace with a/Ar mixed atmosphere, keeping for 1h, and then naturally cooling to room temperature to obtain the carbon nano tube loaded with the shaped ruthenium nano particles;
and 3, step 3: placing 30mg of carbon nano tube loaded with shaped ruthenium nano particles into a porcelain boat, placing the porcelain boat at the upper end of a quartz tube, and placing 1g of NaH 2 PO 4 Putting the carbon nano tube into a porcelain boat, placing the porcelain boat in a tube furnace at the lower end of a quartz tube, heating to 400 ℃, keeping for 3 hours, and naturally cooling to room temperature to obtain the carbon nano tube loaded with the ruthenium nano particles and the phosphorus nano particles;
and 4, step 4: and (2) dispersing 20mg of carbon nanotubes loaded with ruthenium nanoparticles and phosphorus nanoparticles in 40mL of ethanol: to a solution of water =1 2 PtCl 6 ·6H 2 Adding O into the solution, stirring, dropwise adding sodium borohydride ice water solution, and completely reducing Pt 4+ And taking out after 1h, centrifuging, washing with ethanol, and drying in vacuum overnight to obtain the (Ru-P) @ Pt monoatomic alloy material.
2. The preparation method of claim 1 is used for preparing the (Ru-P) @ Pt monatomic alloy material, and the preparation method comprises the following steps:
the carbon nano tube and (Ru-P) @ Pt monatomic alloy loaded on the surface of the carbon nano tube;
the (Ru-P) @ Pt monatomic alloy includes: ruthenium atoms, phosphorus atoms and platinum nanoparticles, wherein the phosphorus atoms and the platinum atoms are doped and loaded on the surfaces of the ruthenium nanoparticles.
3. The use of the (Ru-P) @ Pt monoatomic alloy material of claim 2 in a hydrogen evolution reaction.
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