CN116139894A - Preparation of palladium-based high-entropy compound nano material and application of palladium-based high-entropy compound nano material in electrocatalytic and photocatalytic fields - Google Patents

Preparation of palladium-based high-entropy compound nano material and application of palladium-based high-entropy compound nano material in electrocatalytic and photocatalytic fields Download PDF

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CN116139894A
CN116139894A CN202310109528.1A CN202310109528A CN116139894A CN 116139894 A CN116139894 A CN 116139894A CN 202310109528 A CN202310109528 A CN 202310109528A CN 116139894 A CN116139894 A CN 116139894A
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palladium
entropy
magnetic field
laser
sulfur
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刘璞
付国帅
杨国伟
于鹏
谢康帆
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Sun Yat Sen University
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/097—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds comprising two or more noble metals or noble metal alloys
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Abstract

The invention belongs to the technical field of catalytic materials, and particularly relates to a preparation method of a palladium-based high-entropy compound nano material and application of the palladium-based high-entropy compound nano material in the fields of electrocatalysis and photocatalysis. In order to develop a palladium catalytic material with excellent performance, the invention takes a palladium phosphorus sulfur and/or tantalum palladium sulfur two-dimensional compound crystal material as a parent material, mixes the palladium phosphorus sulfur and/or tantalum palladium sulfur two-dimensional compound crystal material with magnetic transition metal powder and noble metal powder, and then adopts a method of magnetic field induction and laser liquid phase melting corrosion in cooperation with the laser liquid phase melting corrosion to carry out laser melting corrosion treatment under the magnetic field induction on the mixed raw material powder, so that the mixed powder forms nano particles under the dual action of a magnetic field and laser, and further the palladium high-entropy compound nano material is prepared. The prepared palladium-based high-entropy compound nano material belongs to a multifunctional catalyst, has good overpotential and catalytic activity under alkaline, neutral or acidic conditions, has catalytic performance comparable to that of a platinum-based catalyst, and can be applied to the field of electrocatalysis or photocatalysis.

Description

Preparation of palladium-based high-entropy compound nano material and application of palladium-based high-entropy compound nano material in electrocatalytic and photocatalytic fields
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a preparation method of a palladium-based high-entropy compound nano material and application of the palladium-based high-entropy compound nano material in the fields of electrocatalysis and photocatalysis.
Background
In the catalytic field, the catalytic materials that are currently best and commercially available are noble metal platinum or platinum-based materials. The use of platinum metal or platinum-based catalytic materials can greatly reduce the overpotential of various catalytic reactions and increase the energy conversion efficiency in the catalytic process. However, the problems of relatively scarce platinum resources, high price of platinum materials, low total reserves of the mineral world related to platinum and the like have been limited for a long time, and it is generally required to increase the specific surface area of the platinum-based material or disperse the platinum-based noble metal on a carrier of a non-noble metal material (such as a carbon-based material), so as to increase the use efficiency of the catalytic site of the platinum-based catalytic material and reduce the use amount of the platinum noble metal in the catalytic material.
Meanwhile, some researchers have been working to find non-platinum metal-based catalysts with excellent performance or to alloy platinum metal with other transition metals or metal compounds to make them inexpensive alternatives to platinum-based materials. Among them, a high-entropy material is a catalytic material that has been proved to have very high catalytic activity, and is currently becoming a very important exploration direction in the field of catalytic research. In addition, the palladium metal is located very close to the platinum metal in the volcanic plot, and in theory the palladium-based material may have catalytic properties comparable to those of the platinum-based material. However, there are few reports on palladium-based high-entropy compound nano catalytic materials. Therefore, the development of the palladium high-entropy compound nano catalytic material with excellent performance has good application prospect.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of a palladium high-entropy compound nano material, and the prepared palladium high-entropy compound nano material is a catalytic material with excellent performance, has good electrocatalytic performance under alkaline and acidic conditions, has excellent photocatalytic hydrogen evolution performance, and is expected to be applied to the electrochemical field and the photoelectrocatalysis field.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention discloses a preparation method of a palladium high-entropy compound nano material, which comprises the following steps: with palladium phosphorus sulfur (PdPS) and/or tantalum palladium sulfur (Ta) 2 PdS 6 ) The two-dimensional compound crystal material is used as a parent material, the two-dimensional compound crystal material is mixed with magnetic transition metal powder and noble metal powder, then laser ablation treatment is carried out on the mixed raw material powder under the induction action of a magnetic field, and the mixed raw material powder forms nano particles under the laser ablation action of magnetic field synergy, so that the palladium series high-entropy compound nano material is prepared.
As a preferred embodiment of the present invention, the method for preparing the palladium-based high-entropy compound nanomaterial includes the steps of:
s1, palladium phosphosulfide (PdPS) and/or tantalum Palladium sulfide (Ta 2 PdS 6 ) Adding magnetic transition metal powder and noble metal powder into a mixed solution of an organic solvent and water, and uniformly dispersing;
s2, placing the dispersed mixed powder dispersion liquid in a uniform magnetic field, and carrying out laser ablation treatment by using high-energy pulse laser under the induction action of the magnetic field, so that the mixed powder forms nano particles under the laser ablation action of the magnetic field synergy, and the palladium series high-entropy compound nano material is prepared.
Preferably, the magnetic transition metal is at least one of iron, cobalt and nickel; the noble metal is at least one of platinum, ruthenium, iridium and silver.
The high entropy compound nanoparticle contains four or more elements, and a solid solution structure is formed by uniformly mixing the elements. Gao ShangnaThe composition of the rice particles has flexibility, so that the catalytic activity of the rice particles is adjustable, and the synergistic effect of multiple elements in the high-entropy nano particles can provide a series of different adsorption sites, so that the rice particles become ideal choices for multifunctional catalytic reactions. In addition, the high entropy mixing can form a stable structure under severe operating conditions, so that the high entropy mixing has excellent stability in the catalytic reaction process. Palladium has a hydrogen atom adsorption gibbs free energy similar to that of platinum, making palladium-based materials an ideal alternative to platinum-based catalysts in the field of electrocatalysis. For this purpose, the invention uses palladium phosphorus sulfur (PdPS) or tantalum palladium sulfur (Ta 2 PdS 6 ) Magnetic transition metals (iron, cobalt and nickel) and noble metals (silver, platinum, ruthenium and iridium) are used as precursors, and the magnetic field induction synergistic laser ablation technology is adopted to carry out laser treatment in a liquid phase so as to form the high-entropy nano particles. The prepared high-entropy nano particles provide excellent catalytic activity due to the synergistic effect of multiple elements, have excellent catalytic activity in the fields of HER and ORR catalysis, have photocatalytic and electrocatalytic properties comparable to those of platinum-based catalysts, and are expected to be applied to the fields of electrochemistry and photoelectrocatalysis.
In the invention, palladium two-dimensional compound crystal material [ Pd P S (PdPS) or Ta2Pd S (Ta 6) ] is used as a parent material, and is mixed with magnetic transition metals (iron, cobalt and nickel) and noble metals (platinum, ruthenium, iridium and silver), and then laser irradiation treatment is carried out on the mixed powder in a liquid phase under the synergistic effect of magnetic field induction, so as to prepare the high-entropy nano particles. The laser liquid phase erosion under the induction of the magnetic field is essentially different from the common laser liquid phase erosion because the plasma generated by the laser liquid phase erosion can generate a magnetic pinch effect under the action of the strong magnetic field, so that ionized substances eroded by the high-energy laser generate a local aggregation behavior, and the process is favorable for generating a high entropy state. In addition, the strong laser action breaks the weaker chemical bonds in the palladium two-dimensional compound parent material, and simultaneously metal atoms in a molten state under the laser action are uniformly embedded into the two-dimensional compound parent material with the broken chemical bonds due to the 'magnetic pinch' effect of the magnetic field. Because the two-dimensional matrix material is based and the synergistic effect of magnetic fields is assisted, the high-intensity magnetic field energy can be transferred to the molecular and atomic systems of the acted material through the laser ablation effect, so that the microstructure and the performance of the material are affected, the free energy of the material is changed, and finally the high-entropy nano compound is prepared. In addition, the 'entropy state' of the palladium series high entropy compound nano material can be effectively adjusted by regulating and controlling the magnetic field induction effect (different magnetic field sizes, different magnetic field loading modes and the like), and the mass transfer of the catalyst can be obviously improved by regulating and controlling the magnetic field, the conductivity of the electrode is improved, and the charge transfer efficiency of the catalytic process is obviously improved, so that the product obtains the optimal catalytic activity. Therefore, the magnetic field induction synergistic laser liquid phase erosion technology is a new strategy for effectively generating the high-entropy compound nano structure and enhancing the catalytic activity of the high-entropy compound nano structure.
Preferably, the strength of the magnetic field is 1-9T.
Preferably, the energy of pulse laser adopted in the laser ablation treatment is 50-500mJ, the frequency is 1-50Hz, and the action time is 1-10h.
Preferably, the laser ablation process employs a 532nm YAG laser and a 532nm total reflection mirror, or a 355nm YAG laser and a 355nm total reflection mirror.
Preferably, the palladium phosphorus sulfur (PdPS) and/or tantalum palladium sulfur (Ta 2 PdS 6 ) The molar ratio of the palladium content to the magnetic transition metal content and the noble metal content is 1:1:1.
Preferably, the organic solvent is isopropanol or ethanol, and the volume ratio of the organic solvent to water is (1-4): 1. More preferably, the volume ratio of the organic solvent to water is 3:1.
Preferably, the uniform dispersion in the step S1 is uniform dispersion by adopting ultrasonic, the frequency of the ultrasonic is 30-50kHz, and the ultrasonic time is 10-20min.
Preferably, in step S1, palladium phosphorus sulfur (PdPS) and/or tantalum palladium sulfur (Ta 2 PdS 6 ) The feed liquid ratio between the mixed powder of the magnetic transition metal and the noble metal and the mixed solution of the organic solvent and water is 10mg/40-60mL.
The second aspect of the invention discloses a palladium high-entropy compound nanomaterial prepared by the preparation method of the first aspect.
The palladium high-entropy compound nano material prepared by the invention is a multifunctional photo-electric catalyst, has better electrochemical performance under acidic, neutral and alkaline conditions, has catalytic performance comparable to that of a platinum catalyst, and has excellent photo-catalytic performance.
The third aspect of the invention discloses application of the palladium high-entropy compound nanomaterial in the photocatalytic field and/or the electrocatalytic field. In the aspect of electrocatalytic application, when the electrocatalytic is electrochemical hydrogen evolution, the palladium high-entropy compound nano material comprises nano particles formed by combining palladium phosphorus sulfur, cobalt, nickel and platinum, nano particles formed by combining palladium phosphorus sulfur, nickel, silver and ruthenium, nano particles formed by combining tantalum palladium sulfur and nickel, ruthenium and iridium, and nano particles formed by combining tantalum palladium sulfur and cobalt, iridium and silver. When the electrocatalytic is electrochemical oxygen reduction, the palladium high-entropy compound nano material is nano particles formed by combining palladium phosphorus sulfur with iron, ruthenium and platinum. In the aspect of photocatalysis application, the photocatalysis is photocatalytic hydrogen evolution, and the palladium high-entropy compound nanomaterial is a nanoparticle formed by combining palladium phosphorus sulfur, cobalt, nickel and platinum.
The palladium high-entropy compound nano material prepared by the method is a multifunctional electrocatalyst, has better overpotential under acidic and alkaline conditions, has photo-catalytic performance and electrocatalytic performance comparable with those of platinum-based catalysts, can be applied to preparing materials with catalytic effects, and has wide application value in the electrocatalytic field or the photocatalysis field. Meanwhile, the problem of high cost of the platinum-based catalyst is solved.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of palladium high-entropy compound nano material, which uses palladium phosphorus sulfur (PdPS) and/or tantalum palladium sulfur (Ta) 2 PdS 6 ) The two-dimensional compound crystal material is used as a parent material, and is mixed with magnetic transition metal powder and noble metal powder, and then is collectedAnd performing laser ablation treatment on the mixed raw material powder under the induction of a magnetic field by using a method of combining magnetic field induction and laser liquid phase ablation, so that the mixed powder forms nano particles under the dual action of the magnetic field and laser, and further preparing the palladium high-entropy compound nano material. The prepared palladium-based high-entropy compound nano material belongs to a multifunctional catalyst, has good overpotential and catalytic activity under acidic and alkaline conditions, has excellent electrochemical hydrogen evolution or electrochemical oxygen reduction performance under acidic and alkaline conditions, has catalytic performance comparable to that of a platinum-based catalyst, and has excellent photocatalytic hydrogen evolution performance. Therefore, the palladium-based high-entropy compound nano material prepared by the method has good electrocatalytic activity and photocatalytic activity, can be applied to the electrocatalytic field or the photocatalytic field, and has great potential application value.
Drawings
FIG. 1 is a TEM image of spherical-like nanoparticles obtained by combining palladium phosphorus sulfur (PdPS) with nickel, cobalt and platinum under the action of a magnetic field induced synergistic laser;
FIG. 2 is a TEM image of a spherical-like nanoparticle obtained by combining palladium phosphorus sulfur (PdPS) with nickel, silver and ruthenium under the action of a magnetic field induced synergistic laser;
FIG. 3 is a TEM image of a dendrite-like nanomaterial obtained by combining palladium phosphorus sulfur (PdPS) with iron, ruthenium, and platinum under the magnetic field induced synergistic laser;
FIG. 4 shows Ta-Pd-S (Ta) under magnetic field induced synergistic laser 2 PdS 6 ) TEM image of nanostructure obtained by combining with nickel, ruthenium, iridium;
FIG. 5 shows Ta-Pd-S (Ta) under magnetic field induced synergistic laser 2 PdS 6 ) TEM images of nanoparticles combined with cobalt, iridium, silver;
FIG. 6 is an EDS element distribution diagram (Pd, ni, co, pt) of spherical-like nanoparticles obtained by combining palladium phosphorus sulfur (PdPS) with nickel, cobalt and platinum under the action of a magnetic field induced synergistic laser;
FIG. 7 is a graph showing electrochemical hydrogen evolution performance of spherical-like nanoparticles obtained by combining palladium phosphorus sulfur (PdPS) with nickel, cobalt and platinum under the action of a magnetic field-induced synergistic laser under an acidic condition;
FIG. 8 shows Ta-Pd-S (Ta) under magnetic field induced synergistic laser 2 PdS 6 ) Electrochemical hydrogen evolution performance diagram of nano-particles combined with cobalt, iridium and silver under an acidic condition;
FIG. 9 is a graph showing electrochemical hydrogen evolution performance of spherical-like nanoparticles obtained by combining palladium phosphorus sulfur (PdPS) with nickel, cobalt and platinum under the action of magnetic field-induced synergistic laser under alkaline conditions;
FIG. 10 is a graph showing electrochemical hydrogen evolution performance of spherical-like nanoparticles obtained by combining palladium phosphorus sulfur (PdPS) with nickel, silver and ruthenium under the action of a magnetic field-induced synergistic laser under alkaline conditions;
FIG. 11 shows Ta-Pd-S (Ta) under magnetic field induced synergistic laser action 2 PdS 6 ) Electrochemical hydrogen evolution performance diagram of the nanostructure obtained by combining the nano-structure with nickel, ruthenium and iridium under alkaline condition;
FIG. 12 is a graph showing electrochemical oxygen reduction performance of dendritic nano-materials obtained by combining palladium phosphorus sulfur (PdPS) with iron, ruthenium and platinum under the action of magnetic field induction synergistic laser under alkaline conditions;
FIG. 13 is a graph showing photocatalytic hydrogen evolution performance of spheroidal nanoparticles obtained by combining palladium phosphorus sulfur (PdPS) with nickel, cobalt and platinum under the action of a magnetic field induced synergistic laser;
FIG. 14 is a process flow and apparatus diagram of the present invention;
in fig. 14, 1 is a YAG laser (Nd: YAG pulse laser, laser wavelength 532 or 355 nm), 21 is a total reflection mirror (adjusting laser light path), 22 is a focusing mirror, 3 is a laser liquid phase melting reaction zone, 41 is a superconducting magnet device, 42 is a computer for controlling magnetic field, and 5 is a nanostructure generated in the laser liquid phase melting reaction under the induction of magnetic field.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
Example 1 preparation of Palladium-based high entropy Compound nanomaterial
As shown in fig. 14, palladium phosphorus sulfur (PdPS) and nickel, cobalt, and platinum were mixed in a molar ratio of 1:1:1:1, then 10mg of powder was added to a mixed solution of isopropyl alcohol and water (volume ratio of 3:1), the total volume of the solution was 50mL, the mixed solution was placed in an open glass bottle (the container depicted as an open glass bottle for the inner fixed black frame of the magnet in fig. 14), and ultrasonic was uniformly dispersed at room temperature for 10min (ultrasonic frequency was 40 kHz), and then the glass bottle was fixed in a magnet device (a 9T compact type liquid-free helium superconducting magnet system manufactured by uk Cryogenic Limited and having a model number m-CFM-9T-51-H3, comprising a superconducting magnet device 41 and a computer 42 for manipulating a magnetic field, the magnetic field strength was 8T, and the magnetic field was able to penetrate the glass bottle to act in the mixed solution because the glass bottle was not shielded from the magnetic field. After the stabilization of the magnetic field, a YAG laser (model LAB-170-50 YAG laser manufactured by U.S. Newport Corporation) was turned on, and a 355nm YAG laser 1, a 355nm total reflection mirror 21 and a focusing mirror 22 were used to irradiate the mixed solution with pulsed laser having an energy of 100mJ, a frequency of 50Hz and an irradiation time of 1h at the bottle mouth. After 8T strong magnetic field assisted laser liquid phase ablation, the palladium high entropy compound nano material 5 (M-LAL-PdPS/Ni/Co/Pt) is obtained in the laser liquid phase ablation reaction zone 3.
Example 2 preparation of Palladium-based high entropy Compound nanomaterial
As shown in fig. 14, palladium phosphorus sulfur (PdPS) was mixed with nickel, silver, ruthenium in a molar ratio of 1:1:1:1, then 10mg of powder was added to a mixed solution of absolute ethanol and water (volume ratio of 3:1), the total volume of the solution was 50mL, the mixed solution was placed in a glass bottle, and sonicated at room temperature for 10min (ultrasonic frequency was 40 kHz) to uniformly disperse, and then the glass bottle was fixed in a magnet device (9T compact type liquid-free helium superconducting magnet system manufactured by uk Cryogenic Limited and having model number m-CFM-9T-51-H3, comprising superconducting magnet device 41 and computer 42 for manipulating magnetic field) with a magnetic field strength of 7T, and the magnetic field was able to penetrate the glass bottle to act in the mixed solution because the glass bottle has no shielding effect on the magnetic field. After the stabilization of the magnetic field, a YAG laser (model LAB-170-50 YAG laser manufactured by U.S. Newport Corporation) was turned on, and a 355nm YAG laser 1, a 355nm total reflection mirror 21 and a focusing mirror 22 were used to irradiate the mixed solution with pulsed laser having an energy of 200mJ, a frequency of 25Hz and an irradiation time of 1h at the bottle mouth. After 7T strong magnetic field assisted laser liquid phase ablation, the palladium high entropy compound nano material 5 (M-LAL-PdPS/Ni/Ag/Ru) is obtained in the laser liquid phase ablation reaction zone 3.
Example 3 preparation of Palladium-based high entropy Compound nanomaterial
As shown in fig. 14, palladium phosphorus sulfur (PdPS) was mixed with iron, ruthenium, and platinum in a molar ratio of 1:1:1:1, then 10mg of powder was added to a mixed solution of absolute ethanol and water (volume ratio of 3:1), the total volume of the solution was 50mL, the mixed solution was placed in a glass bottle, and sonicated at room temperature for 10min (ultrasonic frequency was 40 kHz) to uniformly disperse, and then the glass bottle was fixed in a magnet device (9T compact type liquid-free helium superconducting magnet system manufactured by uk Cryogenic Limited and having model number m-CFM-9T-51-H3, including superconducting magnet device 41 and computer 42 for manipulating magnetic field) with magnetic field strength of 7T, and the magnetic field was able to penetrate the glass bottle to act in the mixed solution because the glass bottle has no shielding effect on the magnetic field. After the stabilization of the magnetic field, a YAG laser (model PRO-250-10E manufactured by us Newport Corporation) was turned on, and a 532nm YAG laser 1, a 532nm total reflection mirror 21, and a focusing mirror 22 were used to irradiate a pulsed laser with an energy of 300mJ, a frequency of 10Hz, and an irradiation time of 3 hours to the mixed solution at the bottle mouth. After the 5T strong magnetic field assisted laser liquid phase melting and etching, the palladium high entropy compound nano material 5 (M-LAL-PdPS/Fe/Ru/Pt) is obtained in the laser liquid phase melting and etching reaction zone 3.
Example 4 preparation of Palladium-based high entropy Compound nanomaterial
As shown in fig. 14, tantalum palladium sulfur (Ta 2 PdS 6 ) With nickel, ruthenium,Iridium is mixed according to a molar ratio of 1:1:1:1, then 10mg of powder is added into a mixed solution of absolute ethyl alcohol and water (volume ratio is 3:1), the total volume of the solution is 50mL, the mixed solution is placed in a glass bottle, ultrasound is conducted for 10min (ultrasonic frequency is 40 kHz) at room temperature to uniformly disperse the mixed solution, then the glass bottle is fixed in a magnet device (9T compact type liquid-free superconducting magnet system manufactured by UK Cryogenic Limited and having the model number of m-CFM-9T-51-H3, the superconducting magnet device 41 and a computer 42 for controlling a magnetic field are included), the magnetic field strength is 9T, and the glass bottle has no shielding effect on the magnetic field, so that the magnetic field can penetrate the glass bottle to act in the mixed solution. After the stabilization of the magnetic field, a YAG laser (model PRO-250-10E manufactured by us Newport Corporation) was turned on, and a 532nm YAG laser 1, a 532nm total reflection mirror 21, and a focusing mirror 22 were used to irradiate the mixed solution with pulsed laser light having an energy of 400mJ, a frequency of 10Hz, and an irradiation time of 3 hours at the bottle mouth. After the laser liquid phase melting and etching action assisted by a 9T strong magnetic field, the palladium high-entropy compound nano material 5 (M-LAL-TaPdS/Ni/Ru/lr) is obtained in the laser liquid phase melting and etching reaction zone 3.
Example 5 preparation of Palladium-based high entropy Compound nanomaterial
As shown in fig. 14, tantalum palladium sulfur (Ta 2 PdS 6 ) Mixing with cobalt, iridium and silver according to a molar ratio of 1:1:1:1, adding 10mg of powder into a mixed solution of absolute ethyl alcohol and water (volume ratio is 3:1), placing the mixed solution into a glass bottle, performing ultrasonic treatment at room temperature for 10min (ultrasonic frequency is 40 kHz) to uniformly disperse, fixing the glass bottle into a magnet device (9T compact type liquid-free helium superconducting magnet system manufactured by UK Cryogenic Limited and having the model of m-CFM-9T-51-H3), wherein the magnetic field strength is 3T, and the glass bottle has no shielding effect on the magnetic field, so that the magnetic field can penetrate the glass bottle to act in the mixed solution. After the magnetic field stabilization, a YAG laser (model PRO-250-10E, manufactured by U.S. Newport Corporation) was turned on, and a 532nm YAG laser 1, a 532nm total reflection mirror 21 and a focusing mirror 22 were used to irradiate a mixed solution with pulsed laser having an energy of 500mJ and a frequency of 10H at the bottle mouthAnd z, the irradiation time is 3h. After the laser liquid phase melting and etching action assisted by a 3T strong magnetic field, the palladium high-entropy compound nano material 5 (M-LAL-TaPdS/Co/lr/Ag) is obtained in the laser liquid phase melting and etching reaction zone 3.
Comparative example 1 preparation of Palladium-based high entropy Compound nanomaterial
Mixing palladium phosphorus sulfur (PdPS) with nickel, cobalt and platinum according to a molar ratio of 1:1:1, adding 10mg of powder into a mixed solution of isopropanol and water (volume ratio of 3:1), placing the mixed solution into a glass bottle, performing ultrasonic treatment at room temperature for 10min (ultrasonic frequency is 40 kHz) to uniformly disperse, starting a YAG laser (model PRO-250-10E manufactured by U.S. Newport Corporation) under the condition of no magnetic field application, and performing laser irradiation on the mixed solution at a bottle mouth by using a 532nm YAG laser, a 532nm total reflection mirror and a focusing mirror, wherein the energy of the pulse laser is 300mJ, the frequency is 10Hz, and the irradiation time is 1h to obtain the palladium high-entropy compound nanomaterial (LAL-pdP S/Ni/Co/Pt).
Comparative example 2 preparation of Palladium-based high entropy Compound nanomaterial
Mixing palladium phosphorus sulfur (PdPS) with nickel, cobalt and platinum according to a molar ratio of 1:1:1:1, adding 10mg of powder into a mixed solution of isopropanol and water (volume ratio of 3:1), placing the mixed solution into a glass bottle, performing ultrasonic treatment at room temperature for 10min (ultrasonic frequency is 40 kHz) to uniformly disperse, fixing the glass bottle into a magnet device (a 9T compact type liquid-free helium superconducting magnet system manufactured by uk Cryogenic Limited and having the model number of M-CFM-9T-51-H3, comprising a superconducting magnet device 41 and a computer 42 for controlling a magnetic field), and performing action for 1H under the magnetic field with the magnetic field strength of 8T without applying laser irradiation to obtain the palladium high-entropy compound nanomaterial (M-PdPS/Ni/Co/Pt) in which nickel, cobalt and platinum nano particles are simply mixed.
Experimental example 1 Property and Performance analysis of Palladium-based high entropy Compound nanomaterial
(1) Transmission Electron Microscope (TEM) analysis
The palladium-based high-entropy compound nano-materials prepared in examples 1 to 5 are used as test samples, and are subjected to TEM analysis by using a 300kV transmission electron microscope (FEI Tecnai G2F 30, FEI company of America), and TEM images obtained are shown in figures 1 to 5, and as can be seen from the TEM images, the prepared palladium-based high-entropy compound nano-particles are spherical micro-nano-particles or dendrite nano-materials with uniform size distribution.
(2) EDS (energy spectrometer) element distribution analysis
EDS elemental distribution analysis was performed using a spectrometer equipped with a transmission electron microscope (FEI Tecnai G2F 30). Fig. 6 is an EDS element distribution diagram of a palladium-based high-entropy compound nanomaterial, and it can be clearly seen from the figure that palladium, nickel, cobalt and platinum in the spheroidal nanoparticles are uniformly mixed to form a solid solution structure, and the palladium, nickel, cobalt and platinum elements are uniformly distributed on the spheroidal nanoparticles, so that the palladium-nickel cobalt-platinum composite nanomaterial has the basic characteristics of the high-entropy compound. The reason is presumed to be that the strong laser action breaks weaker chemical bonds in the palladium phosphorus sulfur parent material, and simultaneously metal atoms in a molten state under the laser action are uniformly embedded into the palladium phosphorus sulfur parent compound material with the chemical bonds broken based on the 'magnetic pinch' effect of a magnetic field, so that the high-entropy compound nano material is formed.
(3) Chemical property test
A. Electrocatalytic performance test
All electrocatalytic performance tests were carried out using a three-electrode system, the working electrode in the test being a glassy carbon electrode loaded with palladium-based high entropy compound nanomaterial, the counter electrode being a graphite rod electrode, the reference electrode being a silver/silver chloride electrode under acidic conditions, and a mercury/mercury oxide electrode under alkaline conditions, the electrolyte being either a 0.5M sulfuric acid solution (examples 1, 5, comparative examples 1, 2), or a 0.1M potassium hydroxide solution (example 3), or a 1M potassium hydroxide solution (examples 1, 2,4, comparative examples 1, 2). The preparation method of the working electrode comprises the following steps:
weighing 5mg of palladium high-entropy compound nano particles, adding 780 mu L of deionized water and 200 mu L of isopropanol, adding 20 mu L of 5wt% Nafion dispersion liquid, uniformly dispersing by ultrasonic, and taking 5 mu L of prepared ink drops on the surface of a polished glassy carbon electrode, and naturally drying at room temperature to obtain the working electrode.
The electrocatalytic hydrogen evolution performance under acidic conditions was carried out in 0.5M sulfuric acid and the test results are shown in FIGS. 7-8, wherein the scanning rate of the linear sweep voltammetry was 5mV/s. The electrocatalytic hydrogen evolution performance at alkaline was carried out in 1M potassium hydroxide and the test results are shown in fig. 9-11. Wherein the scanning rate of the linear sweep voltammetry is 5mV/s.
As can be seen from the electrochemical performance diagram of FIG. 7, under acidic conditions, the original palladium phosphorus sulfur (PdPS) was measured at 10mA cm -2 The corresponding overpotential under the current density is-448 mV, the electrocatalytic hydrogen evolution activity is far lower than that of the high entropy compound nano particles obtained by magnetic field induced synergistic laser action, while the spherical high entropy nano particles obtained by combining palladium phosphorus sulfur (PdPS) with nickel, cobalt and platinum by magnetic field induced synergistic laser liquid phase ablation show the optimal electrochemical hydrogen evolution activity at 10mAcm -2 The corresponding overpotential at current density of-62 mV, shows HER catalytic activity comparable to that of commercial Pt/C (Shan A, teng X, zhang Y, et al Interfacial electronic structure modulation of Pt-MoS 2 heterostructure for enhancing electrocatalytic hydrogen evolution reaction. Nano Energy,2022, 94:106913.) the catalytic activity of the catalyst obtained by laser action only or magnetic field action only was poor or very poor, at 10mAcm -2 The corresponding overpotential at the current density is-172 mV and-200 mV, respectively. As can be seen from the electrochemical performance diagram of fig. 8, under acidic conditions, the magnetic field induces tantalum palladium sulfur (Ta 2 PdS 6 ) The nano particles obtained by combining with cobalt, iridium and silver also show better catalytic activity at 10mAcm -2 The corresponding overpotential at the current density is-150 mV.
As can be seen from the electrochemical performance diagram of FIG. 9, under alkaline conditions, the original palladium phosphorus sulfur (PdPS) was 10mAcm -2 The corresponding overpotential under the current density is-490 mV, the electrochemical hydrogen evolution activity is far lower than that of the high-entropy nano particles obtained by magnetic field induced synergistic laser action, and the spherical high-entropy nano particles obtained by combining palladium phosphorus sulfur (PdPS) with nickel, cobalt and platinum under the magnetic field induced synergistic laser action show the optimal electrochemical hydrogen evolution activity at 10mAcm -2 Corresponding overpotential at current density of-100 mV, while only lasing andthe nano particles obtained by only performing the magnetic field effect are-261 mV and-294 mV respectively, and the catalytic activity is far lower than that of the high-entropy nano particles obtained by the magnetic field synergistic laser effect. As can be seen from the electrochemical performance diagram of FIG. 10, the spherical nanoparticles obtained by combining palladium phosphorus sulfur (PdPS) with nickel, silver and ruthenium were formed at 10mAcm -2 Corresponding overpotential at current density of-103 mV, whereas in the electrochemical performance diagram of fig. 11, tantalum palladium sulfur (Ta 2 PdS 6 ) The nanostructure obtained by combining the nano-particles with nickel, ruthenium and iridium is 10mA cm -2 The corresponding overpotential at the current density of-132 mV, all showed excellent catalytic activity. The high-entropy compound with uniform distribution is formed after the magnetic field induction synergistic laser action, more catalytic active sites are provided by the synergistic action of multiple elements, the mass transfer of the catalyst is improved by the synergistic action of the magnetic field, the charge transfer efficiency is higher, and excellent electrochemical hydrogen evolution performance is further shown.
The electrocatalytic oxygen reduction performance at alkaline was carried out in 0.1M potassium hydroxide and the test results are shown in fig. 12. Wherein the scanning rate of the linear sweep voltammetry is 10mV/s.
FIG. 12 is a graph showing electrochemical oxygen reduction properties of dendrite-like nanomaterial obtained by combining Pd-P-S (PdPS) with iron, ruthenium, and platinum, where the half-wave potential of dendrite-like nanomaterial obtained by combining Pd-P-S (PdPS) with iron, ruthenium, and platinum is 0.83V, and the limiting current density is-5.5 mA cm -2 This electrocatalytic performance is comparable to that of the existing commercial Pt/C catalysts (Zhang M, xu Y, zhang H, et al Synergistic coupling of P-supported Pd 4 S nanoparticles with P/S-co-doped reduced graphene oxide for enhanced alkaline oxygen reduction. Chemical Engineering Journal,2022, 429:132194.) have reached the level of commercial catalysts.
B. Photocatalytic Performance test
The photocatalytic hydrogen production activity was evaluated on a CEL-SPH2N-D9 test system using the palladium-based high-entropy compound nanomaterial of example 1 as a test material. The light source was a 300W xenon lamp equipped with a CUT400 filter. Using detectors with TCD
Figure BDA0004076307490000101
The amount of hydrogen was measured by gas chromatography on a molecular sieve column. Argon was selected as carrier gas and the test results are shown in fig. 13.
FIG. 13 shows the loading of C with spheroidal nanoparticles of palladium phosphorus sulfur (PdPS) combined with nickel, cobalt, and platinum 3 N 4 The obtained photocatalytic performance map C 3 N 4 The photocatalytic performance of the carrier material (CN for short) is 19 mu mol/h/g, however, the performance of the spherical nano particles obtained by combining supported palladium phosphorus sulfur (PdPS) with nickel, cobalt and platinum is improved to 665 mu mol/h/g, and the spherical nano particles have the photocatalytic performance (Pan J, wang P, wang P, et al The photocatalytic overall water splitting hydrogen production of g-C) which is comparable with that of a platinum-based catalyst 3 N 4 /CdS hollow core-shell heterojunction via the HER/OER matching of Pt/MnO x .Chemical Engineering Journal,2021,405:126622.)。
In conclusion, the palladium-based high-entropy compound nano material prepared by the method is a multifunctional catalyst, has excellent electrochemical hydrogen evolution or electrochemical oxygen reduction performance under acidic and alkaline conditions, has excellent photocatalytic hydrogen evolution performance, and has important potential application values in the electrochemical field and the photoelectrocatalysis field.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.

Claims (10)

1. The preparation method of the palladium high-entropy compound nano material is characterized in that a palladium phosphorus sulfur and/or tantalum palladium sulfur two-dimensional compound crystal material is used as a parent material, the parent material is mixed with magnetic transition metal powder and noble metal powder, and then laser ablation treatment is carried out on the mixed raw material powder under the induction action of a magnetic field, so that the mixed raw material powder forms nano particles under the laser ablation action of magnetic field synergy, and the palladium high-entropy compound nano material is prepared.
2. The method for preparing the palladium-based high-entropy compound nanomaterial according to claim 1, comprising the steps of:
s1, adding palladium phosphorus sulfur and/or tantalum palladium sulfur, magnetic transition metal powder and noble metal powder into a mixed solution of an organic solvent and water, and uniformly dispersing;
s2, placing the dispersed mixed powder dispersion liquid in a uniform magnetic field, and carrying out laser ablation treatment by using high-energy pulse laser under the induction action of the magnetic field, so that the mixed powder forms nano particles under the laser ablation action of the magnetic field synergy, and the palladium series high-entropy compound nano material is prepared.
3. The method for preparing a palladium-based high-entropy compound nanomaterial according to claim 2, wherein the magnetic transition metal is at least one of iron, cobalt, and nickel; the noble metal is at least one of platinum, ruthenium, iridium and silver.
4. The method for preparing a palladium-based high-entropy compound nanomaterial according to claim 2, wherein the strength of the magnetic field is 1 to 9T.
5. The method for preparing the palladium high-entropy compound nanomaterial according to claim 2, wherein the laser ablation treatment adopts a 532nm YAG laser and a 532nm laser adjusting light path, or a 355nm YAG laser and a 355nm laser adjusting light path; the energy of pulse laser adopted in the laser ablation treatment is 50-500mJ, the frequency is 1-50Hz, and the action time is 1-10h.
6. The method for preparing the palladium high-entropy compound nanomaterial according to claim 2, wherein the molar ratio of palladium content in palladium phosphorus sulfur and/or tantalum palladium sulfur to the magnetic transition metal content and the noble metal content is 1:1:1.
7. The palladium-based high-entropy compound nanomaterial prepared by the preparation method of any one of claims 1 to 6.
8. The use of the palladium-based high-entropy compound nanomaterial in the field of electrocatalysis, wherein the electrocatalysis is electrochemical hydrogen evolution, and the palladium-based high-entropy compound nanomaterial comprises nanoparticles formed by combining palladium phosphorus sulfur, cobalt, nickel and platinum, nanoparticles formed by combining palladium phosphorus sulfur, nickel, silver and ruthenium, nanoparticles formed by combining tantalum palladium sulfur with nickel, ruthenium and iridium, and nanoparticles formed by combining tantalum palladium sulfur with cobalt, iridium and silver.
9. The use of the palladium-based high-entropy compound nanomaterial in the field of electrocatalysis, wherein the electrocatalysis is electrochemical oxygen reduction, and the palladium-based high-entropy compound nanomaterial is a nanoparticle formed by combining palladium phosphorus sulfur with iron, ruthenium and platinum.
10. The application of the palladium high-entropy compound nano material in the field of photocatalysis as claimed in claim 7, wherein the photocatalysis is photocatalytic hydrogen evolution, and the palladium high-entropy compound nano material is nano particles formed by palladium phosphorus sulfur, cobalt, nickel and platinum.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190039913A1 (en) * 2017-08-01 2019-02-07 Iowa State University Research Foundation, Inc. Preparation of metal chalcogenides
CN112643040A (en) * 2020-10-14 2021-04-13 南京大学 Method for preparing micro-nano medium-entropy and high-entropy material by laser ablation
CN114160165A (en) * 2021-12-13 2022-03-11 中国矿业大学 High-entropy alloy/NiIn2S4Preparation method of composite photocatalyst
CN114939654A (en) * 2022-05-27 2022-08-26 中机新材料研究院(郑州)有限公司 High-entropy alloy powder for laser additive manufacturing and preparation method and application thereof
CN115449836A (en) * 2022-08-24 2022-12-09 中山大学 Preparation of phosphorus-sulfur alloy-state micro-nano particles and application of phosphorus-sulfur alloy-state micro-nano particles in electrocatalysis field

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190039913A1 (en) * 2017-08-01 2019-02-07 Iowa State University Research Foundation, Inc. Preparation of metal chalcogenides
CN112643040A (en) * 2020-10-14 2021-04-13 南京大学 Method for preparing micro-nano medium-entropy and high-entropy material by laser ablation
CN114160165A (en) * 2021-12-13 2022-03-11 中国矿业大学 High-entropy alloy/NiIn2S4Preparation method of composite photocatalyst
CN114939654A (en) * 2022-05-27 2022-08-26 中机新材料研究院(郑州)有限公司 High-entropy alloy powder for laser additive manufacturing and preparation method and application thereof
CN115449836A (en) * 2022-08-24 2022-12-09 中山大学 Preparation of phosphorus-sulfur alloy-state micro-nano particles and application of phosphorus-sulfur alloy-state micro-nano particles in electrocatalysis field

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