阅读说明：本技术 一种钯铜磷化物异质二聚体材料的制备方法 (Preparation method of palladium-copper phosphide heterodimer material ) 是由 吕燕飞 彭雪 蔡庆锋 赵士超 于 2021-01-29 设计创作，主要内容包括：本发明公开了一种钯铜磷化物异质二聚体材料的制备方法,本发明采用红磷、氯化钯作为磷化钯、磷化亚铜异质二聚体的前驱物,在硅基底上通过气固反应,制备磷化钯-磷化亚铜异质二聚体材料。制备的材料可用于光催化领域。本发明将双金属高温下磷化在硅基片表面制备成双金属磷化物纳米晶体,该材料存在磷化钯和磷化亚铜的晶界,能够增强磷化物的光催化性能。(The invention discloses a preparation method of a palladium-copper phosphide heterodimer material. The prepared material can be used in the field of photocatalysis. The invention prepares the bimetallic phosphide nanocrystal by phosphorizing the bimetal on the surface of the silicon substrate at high temperature, and the material has a grain boundary of palladium phosphide and cuprous phosphide, so that the photocatalysis performance of phosphide can be enhanced.)

1. A preparation method of a palladium-copper phosphide heterodimer material is characterized by comprising the following steps:

cleaning a substrate with deionized water, and drying the substrate with nitrogen for later use; dripping 0.05-0.2mol/l palladium chloride hydrochloric acid solution onto the surface of the substrate by a pipette; then, placing the substrate in a quartz tube, wherein the position is 20-25 cm away from the quartz boat in the downstream direction of carrier gas flow, and placing the quartz tube in a tube furnace;

step (2), heating the quartz tube in the tube furnace to 600-900 ℃, wherein the heating rate is 20-30 ℃/min; after the temperature is raised to 600-900 ℃, the temperature is preserved for 60-100 min;

stopping heating the quartz tube, cooling the tube furnace to room temperature in a room temperature environment, starting the tube furnace, cooling the quartz tube to room temperature at room temperature, taking out the substrate, and obtaining palladium particles on the substrate;

a substrate with metal palladium particles growing on the surface is immersed into a reagent containing an aqueous solution, wherein the aqueous solution contains hexadecylamine, glucose water and copper chloride; then standing at room temperature for 24-72h, and then heating to 100 ℃ in an oil bath for 5-10 h; finally, taking out the substrate, and respectively washing the substrate with ethanol and deionized water; obtaining metal palladium-copper bimetallic nano-crystals; the mass ratio of the hexadecylamine to the glucose to the copper chloride is 45:25: 1;

step (5), putting the product obtained in the step (4) into the middle part of a quartz tube of a tube furnace, and then putting a quartz boat filled with red phosphorus solid powder into the quartz tube in the tube furnace; the quartz boat is arranged at the upstream end of the carrier gas of the quartz tube;

starting a mechanical pump to vacuumize, and simultaneously inputting a carrier gas argon-hydrogen mixed gas into the quartz tube, wherein the volume content of hydrogen is 5%, stopping inputting the carrier gas when the vacuum degree in the tube is 300-500 Pa, and sealing the carrier gas inlet and outlet at two ends of the quartz tube;

step (7), heating the tube furnace to 400-650 ℃, wherein the heating rate is 20-30 ℃/min; keeping the temperature after the temperature is raised to 400-650 ℃, wherein the heat preservation time is 60-100 min;

step (5), stopping heating the quartz tube, cooling the tube furnace to room temperature in a room temperature environment, dredging an air inlet and an air outlet at two ends of the quartz tube, inputting argon-hydrogen mixed gas, wherein the volume content of hydrogen is 5%, opening the tube furnace after 10 minutes, taking out the substrate, and obtaining the palladium phosphide-cuprous phosphide heterodimer nanoparticles on the substrate; the particle size is 30-100 nm.

2. The method of claim 1, wherein the palladium copper phosphide heterodimer material comprises: the size of the substrate is 2.5-3.5 cm multiplied by 1.5-2.0 cm.

3. The method of claim 1, wherein the palladium copper phosphide heterodimer material comprises: the dropping amount of the palladium chloride in the step (1) is 0.1-0.5 ml.

4. The method of claim 1, wherein the palladium copper phosphide heterodimer material comprises: the quartz tube is replaced by a corundum tube.

5. The method of claim 1, wherein the palladium copper phosphide heterodimer material comprises: the substrate is a silicon wafer with an oxide layer growing on the surface.

Technical Field

The invention belongs to the technical field of materials, and particularly relates to a preparation method of cuprous phosphide-palladium phosphide heterodimer nanoparticles.

Background

Cuprous phosphide is a semiconductor material with rich performance, and researches show that the cuprous phosphide can be used for electrocatalytic decomposition of water. Palladium phosphide is also used in the study of photolysis of water as a photocatalytic material. The single material is limited by the combination of photon-generated carriers, the photocatalysis efficiency is lower, and the existence of a heterojunction space electric field is beneficial to the separation of the photon-generated carriers, so that the heterojunction material generally has good photocatalysis performance.

The metal phosphide preparation method can be divided into a solid (gas) phase method and a liquid phase method. The solid (gas) phase method is represented by: high-energy mechanical ball milling, phosphate reduction, metal or metal oxide phosphating. The liquid phase auxiliary method is mainly a water (solvent) thermal method, and usually takes metal halide, sulfate and red phosphorus as reaction sources, and water, ethylene glycol and ethanol as solvents. The above process produces a single cuprous or palladium phosphide product.

Disclosure of Invention

The invention provides a preparation method of a palladium-copper phosphide heterodimer material aiming at the defects of the prior art. The prepared material can be used in the field of photocatalysis.

The preparation method of the palladium phosphide-cuprous phosphide heterodimer nanomaterial comprises the steps of firstly growing a metal palladium (Pd) nanomaterial on the surface of a silicon substrate, then precipitating a copper (Cu) nanocrystal on the surface of the Pd by a reduction method in solution to form a Pd-Cu bimetallic nanocrystal, and then carrying out metal phosphating treatment to form the palladium phosphide-cuprous phosphide heterodimer nanomaterial.

The preparation method of the palladium phosphide-cuprous phosphide heterodimer nanomaterial comprises the following specific steps:

and (1) cleaning a substrate (with the size of 2.5-3.5 cm multiplied by 1.5-2.0 cm) by using deionized water, and drying the substrate by using nitrogen for later use. 0.05-0.2mol/l of palladium chloride (PdCl)₂) And (3) dropwise adding 0.1-0.5ml of hydrochloric acid solution to the surface of the substrate by using a pipette. Then, placing the substrate in a quartz tube, wherein the position is 20-25 cm away from the quartz boat in the downstream direction of the carrier gas flow; putting the quartz tube into a tube furnace;

and (2) heating the quartz tube in the tube furnace to 600-900 ℃, wherein the heating rate is 20-30 ℃/min. And (3) keeping the temperature after the temperature is raised to 600-900 ℃, wherein the heat preservation time is 60-100 min.

And (3) stopping heating the quartz tube, cooling the tube furnace to room temperature in a room temperature environment, starting the tube furnace, cooling the quartz tube to room temperature at room temperature, taking out the substrate, and obtaining palladium particles on the substrate.

And (4) immersing the silicon wafer with the metal palladium particles growing on the surface in a reagent containing 10ml of aqueous solution, wherein the aqueous solution contains 90mg of hexadecylamine, 50mg of glucose water and 2mg of copper chloride. Then the mixture is placed at room temperature for 24-72h, and then is heated to 100 ℃ in an oil bath for 5-10 h. And finally, taking out the substrate, and washing the substrate by using ethanol and deionized water respectively. Metallic palladium (Pd) -copper (Cu) bimetallic nanocrystals were obtained.

And (5) putting the product obtained in the step (4) into the middle of a quartz tube of a tube furnace, and then putting a quartz boat filled with the red green solid powder into the quartz tube (with the diameter of 1 inch) in the tube furnace. The quartz boat is placed at the carrier gas upstream end of the quartz tube.

And (3) starting a mechanical pump to pump vacuum, and simultaneously inputting carrier gas argon-hydrogen mixed gas (5% H) into the quartz tube₂) And stopping inputting the carrier gas when the vacuum degree in the tube is 300-500 Pa, and sealing the inlet and outlet of the two ends of the quartz tube.

And (4) heating the tube furnace to 400-650 ℃, wherein the heating rate is 20-30 ℃/min. And (3) keeping the temperature after the temperature is raised to 400-650 ℃, wherein the heat preservation time is 60-100 min.

And (5) stopping heating the quartz tube, cooling the tubular furnace to room temperature in a room temperature environment, dredging the inlet and outlet carrier gas ports at two ends of the quartz tube, inputting carrier gas, opening the tubular furnace after 10 minutes, taking out the substrate, and obtaining the palladium phosphide-cuprous phosphide heterodimer nanoparticles on the substrate. The particle size is 30-100 nm.

The quartz tube in the step (1) is a quartz tube or a corundum tube.

In the step (1), the carrier gas is argon-hydrogen mixed gas, and the volume ratio of the hydrogen is 5%.

And (3) the substrate in the step (2) is a silicon wafer with an oxide layer growing on the surface.

Has the advantages that: the invention prepares the bimetallic phosphide nanocrystal by phosphorizing the bimetal on the surface of the silicon substrate at high temperature, and the material has a grain boundary of palladium phosphide and cuprous phosphide, so that the photocatalysis performance of phosphide can be enhanced.

Detailed Description

The first embodiment is as follows: a preparation method of a palladium-copper phosphide heterodimer material specifically comprises the following steps:

cleaning a substrate with the size of 2.5 multiplied by 1.5cm by deionized water, and then drying the substrate by nitrogen for later use, wherein the substrate is a silicon wafer with an oxide layer growing on the surface; dropwise adding 0.05mol/l palladium chloride hydrochloric acid solution to the surface of the substrate by a pipette, wherein the dropwise adding amount of the palladium chloride is 0.1 ml; then, the substrate is placed in a corundum tube, the position of the corundum tube is 20cm away from the quartz boat in the downstream direction of the carrier gas flow, and the corundum tube is placed in a tube furnace;

step (2), heating the corundum tube in the tube furnace to 600 ℃, wherein the heating rate is 20 ℃/min; keeping the temperature for 60min after the temperature is raised to 600 ℃;

stopping heating the corundum tube, cooling the tubular furnace to room temperature in a room temperature environment, starting the tubular furnace, cooling the corundum tube to room temperature at room temperature, taking out the substrate, and obtaining palladium particles on the substrate;

a substrate with metal palladium particles growing on the surface is immersed into a reagent containing an aqueous solution, wherein the aqueous solution contains hexadecylamine, glucose water and copper chloride; then standing at room temperature for 24h, then heating to 100 ℃ in an oil bath for 5 h; finally, taking out the substrate, and respectively washing the substrate with ethanol and deionized water; obtaining metallic palladium (Pd) -copper (Cu) bimetallic nanocrystals; the mass ratio of the hexadecylamine to the glucose to the copper chloride is 45:25: 1;

step (5), putting the product obtained in the step (4) into the middle of a corundum tube of a tube furnace, and then putting a quartz boat filled with red phosphorus solid powder into the corundum tube in the tube furnace; the quartz boat is arranged at the upstream end of the carrier gas of the corundum tube;

starting a mechanical pump to pump vacuum, and simultaneously inputting carrier gas argon-hydrogen mixed gas into the corundum tube, wherein the volume content of hydrogen is 5%, stopping inputting carrier gas when the vacuum degree in the corundum tube is 300Pa, and sealing the carrier gas inlet and outlet at two ends of the corundum tube;

step (7), heating the tube furnace to 400 ℃, wherein the heating rate is 20 ℃/min; keeping the temperature for 60min after the temperature is raised to 400 ℃;

step (8), stopping heating the corundum tube, cooling the tubular furnace to room temperature in a room temperature environment, dredging the gas carrying ports at two ends of the corundum tube, inputting argon-hydrogen mixed gas, wherein the volume content of hydrogen is 5%, opening the tubular furnace after 10 minutes, taking out the substrate, and obtaining the palladium phosphide-cuprous phosphide heterodimer nano particles on the substrate; the particle size was 30 nm.

Example two: a preparation method of a palladium-copper phosphide heterodimer material specifically comprises the following steps:

step (1), cleaning a substrate with the size of 3.5cm multiplied by 2.0cm by deionized water, and drying the substrate by nitrogen for later use; 0.2mol/l of palladium chloride (PdCl)₂) Hydrochloric acid solution, the dropping amount of palladium chloride is 0.5ml, and the solution is dropped to the surface of the substrate by a pipette; then, the substrate is placed in a quartz tube, the position is 25cm away from a quartz boat in the downstream direction of carrier gas flow, and the quartz tube is placed in a tube furnace;

step (2), heating a quartz tube in the tube furnace to 900 ℃, wherein the heating rate is 30 ℃/min; keeping the temperature for 100min after the temperature is increased to 900 ℃;

stopping heating the quartz tube, cooling the tube furnace to room temperature in a room temperature environment, starting the tube furnace, cooling the quartz tube to room temperature at room temperature, taking out the substrate, and obtaining palladium particles on the substrate;

a substrate with metal palladium particles growing on the surface is immersed into a reagent containing an aqueous solution, wherein the aqueous solution contains hexadecylamine, glucose water and copper chloride; then standing at room temperature for 72h, and then heating to 100 ℃ in an oil bath for 10 h; finally, taking out the substrate, and respectively washing the substrate with ethanol and deionized water; obtaining metallic palladium (Pd) -copper (Cu) bimetallic nanocrystals; (ii) a The mass ratio of the hexadecylamine to the glucose to the copper chloride is 45:25: 1;

step (5), putting the product obtained in the step (4) into the middle part of a quartz tube of a tube furnace, and then putting a quartz boat filled with red phosphorus solid powder into the quartz tube in the tube furnace; the quartz boat is arranged at the upstream end of the carrier gas of the quartz tube;

starting a mechanical pump to pump vacuum, and simultaneously inputting a carrier gas argon-hydrogen mixed gas into the quartz tube, wherein the volume content of hydrogen is 5%, stopping inputting the carrier gas when the vacuum degree in the tube is 500Pa, and sealing the carrier gas inlet and outlet at two ends of the quartz tube;

step (7), heating the tube furnace to 650 ℃, wherein the heating rate is 30 ℃/min; keeping the temperature for 100min after the temperature is raised to 650 ℃;

step (5), stopping heating the quartz tube, cooling the tube furnace to room temperature in a room temperature environment, dredging an air inlet and an air outlet at two ends of the quartz tube, inputting argon-hydrogen mixed gas, wherein the volume content of hydrogen is 5%, opening the tube furnace after 10 minutes, taking out the substrate, and obtaining the palladium phosphide-cuprous phosphide heterodimer nanoparticles on the substrate; the particle size was 100 nm.

Example three: a preparation method of a palladium-copper phosphide heterodimer material specifically comprises the following steps:

step (1), cleaning a substrate with the size of 2cm multiplied by 1.8cm by deionized water, and then blowing nitrogen for later use; 0.1mol/l of palladium chloride (PdCl)₂) Dripping hydrochloric acid solution to the surface of the substrate by a pipette, wherein the dripping amount of palladium chloride is 0.3 ml; then, the substrate is placed in a quartz tube, the position is 22cm away from the quartz boat in the downstream direction of the carrier gas flow, and the quartz tube is placed in a tube furnace;

step (2), heating a quartz tube in the tube furnace to 800 ℃, wherein the heating rate is 25 ℃/min; keeping the temperature for 80min after the temperature is raised to 800 ℃;

stopping heating the quartz tube, cooling the tube furnace to room temperature in a room temperature environment, starting the tube furnace, cooling the quartz tube to room temperature at room temperature, taking out the substrate, and obtaining palladium particles on the substrate;

a substrate with metal palladium particles growing on the surface is immersed into a reagent containing an aqueous solution, wherein the aqueous solution contains hexadecylamine, glucose water and copper chloride; then standing at room temperature for 60h, then heating to 100 ℃ in an oil bath for 7 h; finally, taking out the substrate, and respectively washing the substrate with ethanol and deionized water; obtaining metallic palladium (Pd) -copper (Cu) bimetallic nanocrystals; the mass ratio of the hexadecylamine to the glucose to the copper chloride is 45:25: 1;

step (5), putting the product obtained in the step (4) into the middle part of a quartz tube of a tube furnace, and then putting a quartz boat filled with red phosphorus solid powder into the quartz tube in the tube furnace; the quartz boat is arranged at the upstream end of the carrier gas of the quartz tube;

starting a mechanical pump to pump vacuum, and simultaneously inputting carrier gas argon-hydrogen mixed gas into the quartz tube, wherein the volume content of hydrogen is 5%, stopping inputting carrier gas when the vacuum degree in the tube is 400Pa, and sealing the carrier gas inlet and outlet at two ends of the quartz tube;

step (7), heating the tube furnace to 550 ℃, wherein the heating rate is 25 ℃/min; keeping the temperature for 80min after the temperature is increased to 550 ℃;

step (5), stopping heating the quartz tube, cooling the tube furnace to room temperature in a room temperature environment, dredging an air inlet and an air outlet at two ends of the quartz tube, inputting argon-hydrogen mixed gas, wherein the volume content of hydrogen is 5%, opening the tube furnace after 10 minutes, taking out the substrate, and obtaining the palladium phosphide-cuprous phosphide heterodimer nanoparticles on the substrate; the particle size was 70 nm.