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CN-119320176-B - High-entropy metal phosphorus sulfur compound nano-sheet and preparation method and application thereof

CN119320176BCN 119320176 BCN119320176 BCN 119320176BCN-119320176-B

Abstract

The invention provides a high-entropy metal phosphorus sulfur compound nano-sheet, a preparation method and application thereof. The preparation method of the high-entropy metal phosphorus sulfur compound nanosheets comprises the steps of mixing manganese, cobalt, nickel, copper, silver, phosphorus and sulfur element powders according to a preset mass ratio, tabletting after grinding uniformly to obtain a tabletting sample, vacuumizing the tabletting sample, packaging, heating the packaged tabletting sample to 590-710 ℃, preserving heat for 150-200 hours, cooling to obtain a block sample, grinding the block sample, dispersing the block sample in a polar solvent, performing ultrasonic cleaning to obtain a cleaning mixed solution, taking supernatant of the cleaning mixed solution, performing ultrasonic crushing treatment, centrifuging to obtain a nanosheet crude product, cleaning the nanosheet crude product, and performing vacuum freeze drying to obtain the nanosheet product. The invention aims to solve the problem of poor catalytic performance of metal phosphorus sulfide.

Inventors

  • WANG RAN
  • LI XIAOFENG
  • ZHANG XINGHONG
  • HAN JIECAI

Assignees

  • 哈尔滨工业大学

Dates

Publication Date
20260512
Application Date
20241016

Claims (8)

  1. 1. The preparation method of the high-entropy metal phosphorus sulfur compound nano sheet is characterized by comprising the following steps of: mixing manganese, cobalt, nickel, copper, silver, phosphorus and sulfur element powders according to a preset mass ratio, grinding uniformly, tabletting to obtain a tabletting sample, wherein the element powders are mixed according to the following mass parts of 0.03-0.035 part of manganese, 0.15-0.2 part of cobalt, 0.025-0.035 part of nickel, 0.01-0.025 part of copper, 0.02-0.035 part of silver, 0.17-0.19 part of phosphorus and 0.45-0.55 part of sulfur; vacuumizing the tabletting sample and packaging; heating the packaged tabletting sample to 590-710 ℃, preserving heat for 150-200h, and cooling to obtain a block sample; after grinding the block sample, dispersing the block sample in a polar solvent for ultrasonic cleaning to obtain a cleaning mixed solution; Taking the supernatant of the cleaning mixed solution, carrying out ultrasonic crushing treatment, and centrifuging to obtain a crude nano-sheet product; and cleaning the nano sheet crude product, and then performing vacuum freeze drying to obtain the nano sheet product.
  2. 2. The method for preparing high-entropy metal phosphorus sulfur compound nano-sheets according to claim 1, wherein the temperature rising rate of the packaged tabletting sample is 1-5 ℃ per minute when the tabletting sample is heated.
  3. 3. The method for preparing high-entropy metal phosphorus sulfur compound nanoplatelets according to claim 1, wherein the centrifugation comprises: centrifuging the supernatant of the cleaning mixed solution at a rotating speed of 3000-4000r/min, and centrifuging the centrifuged supernatant at a rotating speed of 9000-10000 r/min.
  4. 4. The method for preparing high-entropy metal phosphorus sulfur compound nano-sheet according to claim 1, wherein the vacuum-pumping pressure of the pressed sheet sample is 7 x 10 "4-9 x 10" 4Pa.
  5. 5. A high-entropy metal phosphorus sulfur compound nano-sheet prepared based on the preparation method of any one of claims 1 to 4, wherein the high-entropy metal phosphorus sulfur compound nano-sheet comprises the following elements of manganese, cobalt, nickel, copper, silver, phosphorus and sulfur; Wherein the molar ratio of manganese, cobalt, nickel, copper, silver, phosphorus and sulfur is (0.1-0.2): (0.1-0.2): (0.1-0.2): (0.1-0.2): (0.1-0.2): (1:3).
  6. 6. The high entropy metal phosphorus sulfur compound nanoplatelets of claim 5, wherein the high entropy metal phosphorus sulfur compound nanoplatelets have a thickness in the range of 1.5-4.5nm.
  7. 7. The high entropy metal phosphorus sulfur compound nanoplatelets of claim 5, wherein the number of layers of the high entropy metal phosphorus sulfur compound nanoplatelets ranges from 1 to 4.
  8. 8. Use of the high entropy metal phosphorus sulfur compound nanoplatelets of any of claims 5-7 in electrocatalytic hydrogen evolution reactions and electrocatalytic oxygen evolution reactions.

Description

High-entropy metal phosphorus sulfur compound nano-sheet and preparation method and application thereof Technical Field The invention relates to the technical field of nano catalyst materials, in particular to a high-entropy metal phosphorus sulfur compound nano sheet and a preparation method and application thereof. Background The two-dimensional metal phosphosulfide (MPCh 3) is a catalytic platform with application potential due to the high specific surface area and the unique electronic structure. However, the single MPCh 3 base has poor activity and fails to provide sufficient active sites for the reaction, thereby limiting further improvement of the catalytic performance. Currently, doping of MPCh 3 materials with mono-or di-elements is a common material design and preparation strategy for modulating the basal plane site activity of MPCh 3. For example, in the related art, the activation of NiPS 3 in-plane active sites is achieved by converting the semiconductor NiPS 3 to a metallic state using B and C doping. However, the activation performance of a single or simple combination of elements is limited, which is disadvantageous for further improvement of the catalyst performance. Disclosure of Invention The invention aims to solve the problem of poor catalytic performance of metal phosphorus sulfide. In order to solve the problems, the invention provides a high-entropy metal phosphorus sulfur compound nano-sheet, and a preparation method and application thereof. In a first aspect, the present invention provides a method for preparing a high entropy metal phosphorus sulfur compound nanosheet, comprising: mixing manganese, cobalt, nickel, copper, silver, phosphorus and sulfur element powders according to a preset mass ratio, grinding uniformly, and tabletting to obtain a tabletting sample; vacuumizing the tabletting sample and packaging; heating the packaged tabletting sample to 590-710 ℃, preserving heat for 150-200h, and cooling to obtain a block sample; after grinding the block sample, dispersing the block sample in a polar solvent for ultrasonic cleaning to obtain a cleaning mixed solution; Taking the supernatant of the cleaning mixed solution, carrying out ultrasonic crushing treatment, and centrifuging to obtain a crude nano-sheet product; and cleaning the nano sheet crude product, and then performing vacuum freeze drying to obtain the nano sheet product. Optionally, the elemental powders are mixed in parts by mass of 0.03-0.035 parts manganese, 0.15-0.2 parts cobalt, 0.025-0.035 parts nickel, 0.01-0.025 parts copper, 0.02-0.035 parts silver, 0.17-0.19 parts phosphorus, and 0.45-0.55 parts sulfur. Optionally, the temperature rising rate of the encapsulated tabletting sample is 1-5 ℃ per minute when the encapsulated tabletting sample is heated. Optionally, the centrifuging comprises: Centrifuging the supernatant at a rotating speed of 3000-4000r/min, and centrifuging the centrifuged supernatant at a rotating speed of 9000-10000 r/min. Alternatively, the vacuum of the pellet sample is applied at a pressure in the range of 7X 10 -4-9×10-4 Pa. In a second aspect, the invention also provides the high-entropy metal phosphorus sulfur compound nano-sheet prepared based on the preparation method. Optionally, the high entropy metal phosphorus sulfur compound nanoplatelets comprise elements of manganese, cobalt, nickel, copper, silver, phosphorus, and sulfur; Wherein the molar ratio of manganese, cobalt, nickel, copper, silver, phosphorus and sulfur is (0.1-0.2): (0.1-0.2): (0.1-0.2): (0.1-0.2): (0.1-0.2): (1:3). Optionally, the high-entropy metal phosphorus sulfur compound nano-sheet has a thickness ranging from 1.5 to 4.5nm. Optionally, the number of layers of the high-entropy metal phosphorus sulfur compound nano-sheet ranges from 1 layer to 4 layers. In a third aspect, the invention also provides an application of the high-entropy metal phosphorus sulfur compound nanosheets in electrocatalytic hydrogen evolution reaction and electrocatalytic oxygen evolution reaction. Compared with the prior art, the invention has the following beneficial effects: The invention carries out solid phase synthesis on a plurality of high-entropy metal elements, phosphorus and sulfur elements at 590-710 ℃, and then adopts a polar solvent to primarily strip the synthesized block sample into a single-layer or less-layer sample. The polar solvent can help the bulk sample overcome the van der waals forces between the layers, thereby initially exfoliating the bulk sample. Finally, the sample after preliminary stripping is further stripped by adopting an ultrasonic breaking mode, so that the block sample is completely stripped. The completely stripped nano-sheet has larger specific surface area and rich active sites, and promotes the exertion of catalytic performance. The ultrasonic stripping can reduce the number of layers of the nano-sheets and simultaneously lead the nano-sheets to be broken, so that the transverse dimension of th