CN113755875B - Carbon-coated tungsten phosphide nanowire self-supporting structure composite material and preparation method thereof - Google Patents

Carbon-coated tungsten phosphide nanowire self-supporting structure composite material and preparation method thereof Download PDF

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CN113755875B
CN113755875B CN202111056308.4A CN202111056308A CN113755875B CN 113755875 B CN113755875 B CN 113755875B CN 202111056308 A CN202111056308 A CN 202111056308A CN 113755875 B CN113755875 B CN 113755875B
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吕存财
娄萍萍
王淑芳
李亚光
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Hebei University
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Abstract

The invention provides a carbon-coated tungsten phosphide nanowire self-supporting structure composite material and a preparation method thereof. In the carbon-coated tungsten phosphide nanowire self-supporting structure composite material, a thin-layer carbon shell is uniformly coated on the surface of a tungsten phosphide nanowire, a hydrated tungsten oxide nanowire precursor is loaded on a substrate, and the composite material is annealed at a high temperature in an argon atmosphere and simultaneously acetonitrile is injected to obtain a thin-layer carbon-coated tungsten oxide nanowire/substrate composite structure, and the thin-layer carbon-coated tungsten oxide nanowire/substrate composite structure is prepared by phosphating with sodium hypophosphite. The preparation process is simple, the operation is easy, the cost is low, the chemical stability of the obtained composite material is high, the oxidation resistance is high, the electrocatalytic performance is improved, and the preparation process has potential for large-scale application to the development of industrial electrolyzed water catalysts.

Description

Carbon-coated tungsten phosphide nanowire self-supporting structure composite material and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a carbon-coated tungsten phosphide nanowire self-supporting structure composite material and a preparation method thereof.
Background
Transition metal phosphides have similar physicochemical properties as carbides, borides and nitrides, such as: stable structure, ceramic and metal characteristics, good heat and electricity conducting performance, thermodynamic stability and the like. The transition metal phosphide has wide application in hydrofining, hydrodesulfurization, hydrodenitrogenation, hydrodechlorination, electronic materials, biomedical environmental protection, lithium ion batteries and the like.
Tungsten phosphide is used as a member of transition metal phosphide, has metalloid characteristics, and can ensure rapid electron transfer. Meanwhile, the phosphorus element in the tungsten phosphide can adjust the electron concentration around the metal atoms, so that the adsorption and desorption of the metal atoms to the reaction intermediate are optimized, and the tungsten phosphide has good electrocatalytic hydrogen evolution activity. The modification of the metal phosphide electrocatalyst is mainly developed around the aspects of regulating and controlling the shape, size and electronic structure of the metal phosphide electrocatalyst, such as preparing metal phosphide nano-particle/nano-wire/nano-rod structures and the like, and doping elements or compounding various catalysts. Recently, the research reports that the carbon layer coating is carried out on the surface of the metal phosphide, which is beneficial to improving the electronic structure of the surface of the phosphide, optimizing the hydrogen adsorption capacity of the surface of the phosphide and further improving the electrocatalytic hydrogen evolution activity of the phosphide. Meanwhile, the surface carbon of the phosphide is coated, so that the oxidation resistance of the surface of the phosphide is improved, and the chemical stability of the catalyst is improved. Therefore, the surface carbon modification of the metal phosphide is an important way for improving the electrocatalytic hydrogen evolution activity of the metal phosphide.
However, at present, for carbon coating of metal phosphide, the metal phosphide is mainly spread around powder, when an electrode is constructed, the metal phosphide needs to be prepared into suspension liquid to be coated on a current collector such as glassy carbon, and a high-cost binder needs to be added to improve stability, and the electrochemical performance of a catalyst is reduced due to the doping of a polymer binder.
Disclosure of Invention
The invention aims to provide a carbon-coated tungsten phosphide nanowire self-supporting structure composite material and a preparation method thereof, which are used for solving the problems of low conductivity, poor oxidation resistance and low electrocatalytic hydrogen evolution activity of the existing electrolyzed water catalyst.
The invention is realized in the following way:
a carbon-coated tungsten phosphide nanowire self-supporting structure composite material specifically comprises: and uniformly growing tungsten phosphide nanowires on the surface of the substrate to form a self-supporting electrode structure, wherein the thin carbon layer is uniformly coated on the surface of the tungsten phosphide nanowires, and the thickness of the thin carbon layer is about 2nm. The substrate can be selected from common substrate materials in the art, such as carbon fiber paper, foam nickel, foam copper, titanium sheet, etc., preferably carbon fiber paper with a size of 2×5cm 2 。
When the carbon-coated tungsten phosphide nanowire self-supporting structure composite material is used as an acidic electrolyzed water catalyst, the current density is 20mAcm -2 In this case, the overpotential is 125 to 156mV, preferably 125mV.
The preparation method of the carbon-coated tungsten phosphide nanowire self-supporting structure composite material comprises the following steps:
(a) Loading a hydrated tungsten oxide nanowire precursor on a substrate;
(b) Carrying out high-temperature annealing on the substrate loaded hydrated tungsten oxide nanowire precursor obtained in the step (a) in a tubular furnace under argon atmosphere, and injecting acetonitrile in the process to obtain a thin-layer carbon-coated tungsten oxide nanowire self-supporting composite structure;
(c) And (c) phosphating the surface of the thin-layer carbon-coated tungsten oxide nanowire self-supporting composite structure obtained in the step (b) to obtain the thin-layer carbon-coated tungsten phosphide nanowire self-supporting structure composite material.
In the step (a), a solvothermal method, specifically a solvothermal synthesis method, is adopted to load a hydrated tungsten oxide nanowire precursor on a substrate, wherein the solvothermal method can adopt a reaction temperature and a reaction time which are known to a person skilled in the art, preferably, the reaction temperature is 150-200 ℃, and the reaction time is 12-20 h; more preferably, the reaction temperature is 180 ℃ and the reaction time is 16h.
The hydrated tungsten oxide nanowire precursor can be synthesized by using known raw materials and solvents, preferably, an acidic solution containing tungsten ions is mixed with oxalic acid to obtain a transparent solution, and then ammonium sulfate is dissolved in the solution to obtain a final reaction solution.
Optionally, the acidic solution containing tungsten ions is a solution obtained by dissolving inorganic tungstate in deionized water and then adjusting the pH of the solution to 1.2, wherein the inorganic tungstate is sodium tungstate or ammonium tungstate.
Specifically, sodium tungstate dihydrate is taken as a raw material, deionized water is taken as a solvent, and the ratio of the sodium tungstate dihydrate to the deionized water is 2.5mmol:20mL of a solution was prepared, and then hydrochloric acid was added dropwise to adjust the pH of the solution to 1.2, then 7mmol of oxalic acid dihydrate was dissolved in the above solution, and the solution was diluted to 50mL, and finally 2.5g of ammonium sulfate was added to obtain a colorless transparent solution.
When the hydrated tungsten oxide nanowire precursor is loaded on the substrate, transferring the obtained reaction liquid into a reaction container, and simultaneously placing the substrate obliquely by the wall, and performing hydrothermal synthesis reaction at a set temperature.
In the step (b), the sample obtained in the step (a) is placed in a tube furnace, and the temperature is increased to 600 ℃ (heating rate: 5 ℃ for min) under the argon atmosphere -1 ) And acetonitrile was injected. The reaction temperature for acetonitrile injection is preferably 600 ℃, and the injection rate is 5mLh -1 Pouring intoThe shot time was 2h.
In the step (c), the sample obtained in the step (b) is phosphated by adopting a high-temperature phosphating method, specifically, 2g of sodium hypophosphite is placed in a ceramic boat at the upstream side of a tube furnace, and the sample obtained in the step (b) is placed in the ceramic boat at the middle of the tube furnace. High temperature phosphating is carried out under argon atmosphere. The temperature of the sodium phosphite is 350 ℃, the phosphating temperature of the sample is 700-900 ℃ and the phosphating time is 60-180 min.
The invention combines the hydrothermal reaction, the organic matter pyrolysis reaction and the phosphating reaction to prepare the thin-layer carbon-coated tungsten phosphide nanowire composite structure in one step. The introduction of the surface thin-layer carbon can improve the surface oxidation resistance of the material, thereby improving the chemical stability of the material. Meanwhile, the coating effect of the thin-layer carbon on the surface of the tungsten phosphide can improve the electronic structure of the composite system, so that the electrocatalytic hydrogen evolution activity of the composite system is enhanced. The composite material has obvious advantages in the aspects of chemical stability and electrocatalytic activity, and has considerable application prospect, which does not appear in the previous report.
The preparation process of the composite material is simple, the operation is easy, the cost is low, the mass production is easy to carry out, and the composite material has the potential of large-scale application for the development of industrial electrolyzed water catalysts.
Drawings
FIG. 1 is an XRD spectrum of the sample prepared in example 1, and a standard sample of carbon fiber paper and tungsten phosphide.
Fig. 2 is an SEM image of the sample prepared in example 1.
Fig. 3 is a TEM image of the sample prepared in example 1.
FIG. 4 is a Raman spectrum of the sample prepared in example 2.
FIG. 5 is a graph showing the polarization curves of the samples prepared in examples 1, 3 to 8 and comparative example 1 in an acidic electrolyte.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
The procedures and methods not described in detail in the examples below are conventional methods well known in the art, and the reagents used in the examples are all analytically or chemically pure and are either commercially available or prepared by methods well known to those of ordinary skill in the art. The following examples all achieve the object of the invention.
Example 1
2.5mmol of sodium tungstate dihydrate was dissolved in 20mL of deionized water to obtain a colorless transparent solution, the pH value of the solution was adjusted to 1.2 by dropwise addition of hydrochloric acid to obtain a pale yellow solution, then 7mmol of oxalic acid dihydrate was added to the solution, the solution was diluted to 50mL, and 2.5g of ammonium sulfate was added to obtain a colorless transparent solution. The mixed solution was transferred to a reaction vessel while carbon fiber paper (2X 5cm 2 ) And (3) placing the carbon fiber paper obliquely by using the wall, heating to 180 ℃, reacting for 16 hours, naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and vacuum drying at 60 ℃ for 12 hours. The sample was placed in a tube furnace at 5℃for a min under argon (flow rate 60 sccm) -1 Heating to 600deg.C, and then injecting acetonitrile at 600deg.C with 5mLh by syringe pump -1 The constant feeding rate injection equipment is subjected to heat preservation for 120min, and then naturally cooled to room temperature, so that the thin-layer carbon-coated carbon fiber paper-loaded tungsten oxide nanowire self-supporting structure composite material is obtained.
The sample obtained above and 2g of sodium hypophosphite were placed in a double-temperature zone tube furnace, with sodium hypophosphite placed on the upstream side of the tube furnace. The tube furnace was then warmed up under argon atmosphere with a sample position at 5℃min -1 The temperature was raised to 800℃and the sodium hypophosphite position was raised to 350℃over the same time and held at this temperature for 120min. Finally, the tubular furnace is automatically cooled to room temperature, and the thin-layer carbon-coated tungsten phosphide nanowire/carbon fiber paper self-supporting structure composite material is obtained.
The prepared material was characterized, and the results are shown in fig. 1 to 3. As can be seen from FIG. 1, the tungsten phosphide phase in the prepared thin-layer carbon-coated tungsten phosphide nanowire/carbon fiber paper self-supporting structure composite material is matched with the WP29-1364 of the JCPDS card. As can be seen from fig. 2, the obtained composite material is uniformly supported on carbon fiber paper, and the composite material has a nanowire-like structure. As can be seen from fig. 3, the surface of the tungsten phosphide nanowire was uniformly coated with a thin carbon shell, and the thickness of the thin carbon shell was about 2nm.
Comparative example 1
2.5mmol of sodium tungstate dihydrate was dissolved in 20mL of deionized water to obtain a colorless transparent solution, the pH value of the solution was adjusted to 1.2 by dropwise addition of hydrochloric acid to obtain a pale yellow solution, then 7mmol of oxalic acid dihydrate was added to the solution, the solution was diluted to 50mL, and 2.5g of ammonium sulfate was added to obtain a colorless transparent solution. The mixed solution was transferred to a reaction vessel while carbon fiber paper (2X 5cm 2 ) And (3) placing the carbon fiber paper obliquely by using the wall, heating to 180 ℃, reacting for 16 hours, naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and vacuum drying at 60 ℃ for 12 hours. The sample was placed in a tube furnace at 5℃for a min under argon (flow rate 60 sccm) -1 Heating to 600 ℃, keeping the temperature for 120min, and naturally cooling to room temperature to obtain the carbon fiber paper-loaded tungsten oxide nanowire self-supporting structure composite material.
The sample obtained above and 2g of sodium hypophosphite were placed in a double-temperature zone tube furnace, with sodium hypophosphite placed on the upstream side of the tube furnace. The tube furnace was then warmed up under argon atmosphere with a sample position at 5℃min -1 The temperature was raised to 800℃and the sodium hypophosphite position was raised to 350℃over the same time and held at this temperature for 120min. Finally, the tube furnace is automatically cooled to room temperature, and the tungsten phosphide nanowire/carbon fiber paper self-supporting structure composite material is obtained.
Example 2
2.5mmol of sodium tungstate dihydrate was dissolved in 20mL of deionized water to obtain a colorless transparent solution, the pH value of the solution was adjusted to 1.2 by dropwise addition of hydrochloric acid to obtain a pale yellow solution, then 7mmol of oxalic acid dihydrate was added to the solution, the solution was diluted to 50mL, and 2.5g of ammonium sulfate was added to obtain a colorless transparent solution. The mixed solution was transferred to a reaction vessel while titanium flakes (2X 5 cm) 2 ) And (3) placing the titanium sheet obliquely by using the wall, heating to 180 ℃, reacting for 16 hours, naturally cooling, taking out the titanium sheet, washing the titanium sheet with deionized water, and vacuum drying at 60 ℃ for 12 hours. The sample was placed in a tube furnace at 5℃for a min under argon (flow rate 60 sccm) -1 Heating to 600 ℃, then at 600℃, causingAcetonitrile was pumped with syringe at 5mLh -1 The constant feeding rate injection equipment is subjected to heat preservation for 120min, and then naturally cooled to room temperature, so that the thin-layer carbon-coated titanium sheet loaded tungsten oxide nanowire self-supporting structure composite material is obtained.
The sample obtained above and 2g of sodium hypophosphite were placed in a double-temperature zone tube furnace, with sodium hypophosphite placed on the upstream side of the tube furnace. The tube furnace was then warmed up under argon atmosphere with a sample position at 5℃min -1 The temperature was raised to 800℃and the sodium hypophosphite position was raised to 350℃over the same time and held at this temperature for 120min. Finally, the tubular furnace is automatically cooled to room temperature, and the thin-layer carbon-coated tungsten phosphide nanowire/titanium sheet self-supporting structure composite material is obtained. The resulting samples were subjected to Raman testing and the results are shown in fig. 4.
Example 3
2.5mmol of sodium tungstate dihydrate was dissolved in 20mL of deionized water to obtain a colorless transparent solution, the pH value of the solution was adjusted to 1.2 by dropwise addition of hydrochloric acid to obtain a pale yellow solution, then 7mmol of oxalic acid dihydrate was added to the solution, the solution was diluted to 50mL, and 2.5g of ammonium sulfate was added to obtain a colorless transparent solution. The mixed solution was transferred to a reaction vessel while carbon fiber paper (2X 5cm 2 ) And (3) placing the carbon fiber paper obliquely by using the wall, heating to 180 ℃, reacting for 16 hours, naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and vacuum drying at 60 ℃ for 12 hours. The sample was placed in a tube furnace at 5℃for a min under argon (flow rate 60 sccm) -1 Heating to 600deg.C, and then injecting acetonitrile at 600deg.C with 5mLh by syringe pump -1 The constant feeding rate injection equipment is subjected to heat preservation for 120min, and then naturally cooled to room temperature, so that the thin-layer carbon-coated carbon fiber paper-loaded tungsten oxide nanowire self-supporting structure composite material is obtained.
The sample obtained above and 2g of sodium hypophosphite were placed in a double-temperature zone tube furnace, with sodium hypophosphite placed on the upstream side of the tube furnace. The tube furnace was then warmed up under argon atmosphere with a sample position at 5℃min -1 The temperature was raised to 700℃and the sodium hypophosphite position was raised to 350℃over the same time and held at this temperature for 120min. Finally, the tube furnace is automatically cooled toAnd (3) obtaining the thin-layer carbon-coated tungsten phosphide nanowire/carbon fiber paper self-supporting structure composite material at room temperature.
Example 4
2.5mmol of sodium tungstate dihydrate was dissolved in 20mL of deionized water to obtain a colorless transparent solution, the pH value of the solution was adjusted to 1.2 by dropwise addition of hydrochloric acid to obtain a pale yellow solution, then 7mmol of oxalic acid dihydrate was added to the solution, the solution was diluted to 50mL, and 2.5g of ammonium sulfate was added to obtain a colorless transparent solution. The mixed solution was transferred to a reaction vessel while carbon fiber paper (2X 5cm 2 ) And (3) placing the carbon fiber paper obliquely by using the wall, heating to 180 ℃, reacting for 16 hours, naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and vacuum drying at 60 ℃ for 12 hours. The sample was placed in a tube furnace at 5℃for a min under argon (flow rate 60 sccm) -1 Heating to 600deg.C, and then injecting acetonitrile at 600deg.C with 5mLh by syringe pump -1 The constant feeding rate injection equipment is subjected to heat preservation for 120min, and then naturally cooled to room temperature, so that the thin-layer carbon-coated carbon fiber paper-loaded tungsten oxide nanowire self-supporting structure composite material is obtained.
The sample obtained above and 2g of sodium hypophosphite were placed in a double-temperature zone tube furnace, with sodium hypophosphite placed on the upstream side of the tube furnace. The tube furnace was then warmed up under argon atmosphere with a sample position at 5℃min -1 The temperature was raised to 900 ℃, the sodium hypophosphite position was raised to 350 ℃ over the same time and held at this temperature for 120min. Finally, the tubular furnace is automatically cooled to room temperature, and the thin-layer carbon-coated tungsten phosphide nanowire/carbon fiber paper self-supporting structure composite material is obtained.
Example 5
2.5mmol of sodium tungstate dihydrate was dissolved in 20mL of deionized water to obtain a colorless transparent solution, the pH value of the solution was adjusted to 1.2 by dropwise addition of hydrochloric acid to obtain a pale yellow solution, then 7mmol of oxalic acid dihydrate was added to the solution, the solution was diluted to 50mL, and 2.5g of ammonium sulfate was added to obtain a colorless transparent solution. The mixed solution was transferred to a reaction vessel while carbon fiber paper (2X 5cm 2 ) The carbon fiber paper is placed obliquely by the wall, heated to 180 ℃ and reacted for 12 hours, then naturally cooled, taken out and washed clean by deionized water at 60 DEG CAnd vacuum drying for 12h. The sample was placed in a tube furnace at 5℃for a min under argon (flow rate 60 sccm) -1 Heating to 600deg.C, and then injecting acetonitrile at 600deg.C with 5mLh by syringe pump -1 The constant feeding rate injection equipment is subjected to heat preservation for 120min, and then naturally cooled to room temperature, so that the thin-layer carbon-coated carbon fiber paper-loaded tungsten oxide nanowire self-supporting structure composite material is obtained.
The sample obtained above and 2g of sodium hypophosphite were placed in a double-temperature zone tube furnace, with sodium hypophosphite placed on the upstream side of the tube furnace. The tube furnace was then warmed up under argon atmosphere with a sample position at 5℃min -1 The temperature was raised to 800℃and the sodium hypophosphite position was raised to 350℃over the same time and held at this temperature for 120min. Finally, the tubular furnace is automatically cooled to room temperature, and the thin-layer carbon-coated tungsten phosphide nanowire/carbon fiber paper self-supporting structure composite material is obtained.
Example 6
2.5mmol of sodium tungstate dihydrate was dissolved in 20mL of deionized water to obtain a colorless transparent solution, the pH value of the solution was adjusted to 1.2 by dropwise addition of hydrochloric acid to obtain a pale yellow solution, then 7mmol of oxalic acid dihydrate was added to the solution, the solution was diluted to 50mL, and 2.5g of ammonium sulfate was added to obtain a colorless transparent solution. The mixed solution was transferred to a reaction vessel while carbon fiber paper (2X 5cm 2 ) And (3) placing the carbon fiber paper obliquely by using the wall, heating to 180 ℃, reacting for 20 hours, naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and vacuum drying at 60 ℃ for 12 hours. The sample was placed in a tube furnace at 5℃for a min under argon (flow rate 60 sccm) -1 Heating to 600deg.C, and then injecting acetonitrile at 600deg.C with 5mLh by syringe pump -1 The constant feeding rate injection equipment is subjected to heat preservation for 120min, and then naturally cooled to room temperature, so that the thin-layer carbon-coated carbon fiber paper-loaded tungsten oxide nanowire self-supporting structure composite material is obtained.
The sample obtained above and 2g of sodium hypophosphite were placed in a double-temperature zone tube furnace, with sodium hypophosphite placed on the upstream side of the tube furnace. The tube furnace was then warmed up under argon atmosphere with a sample position at 5℃min -1 Heating to 800 deg.C, and positioning sodium hypophosphiteThe temperature was increased to 350℃over the same time period and maintained at this temperature for 120min. Finally, the tubular furnace is automatically cooled to room temperature, and the thin-layer carbon-coated tungsten phosphide nanowire/carbon fiber paper self-supporting structure composite material is obtained.
Example 7
2.5mmol of sodium tungstate dihydrate was dissolved in 20mL of deionized water to obtain a colorless transparent solution, the pH value of the solution was adjusted to 1.2 by dropwise addition of hydrochloric acid to obtain a pale yellow solution, then 7mmol of oxalic acid dihydrate was added to the solution, the solution was diluted to 50mL, and 2.5g of ammonium sulfate was added to obtain a colorless transparent solution. The mixed solution was transferred to a reaction vessel while carbon fiber paper (2X 5cm 2 ) And (3) placing the carbon fiber paper obliquely by using the wall, heating to 180 ℃, reacting for 16 hours, naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and vacuum drying at 60 ℃ for 12 hours. The sample was placed in a tube furnace at 5℃for a min under argon (flow rate 60 sccm) -1 Heating to 600deg.C, and then injecting acetonitrile at 600deg.C with 5mLh by syringe pump -1 The constant feeding rate injection equipment is subjected to heat preservation for 120min, and then naturally cooled to room temperature, so that the thin-layer carbon-coated carbon fiber paper-loaded tungsten oxide nanowire self-supporting structure composite material is obtained.
The sample obtained above and 2g of sodium hypophosphite were placed in a double-temperature zone tube furnace, with sodium hypophosphite placed on the upstream side of the tube furnace. The tube furnace was then warmed up under argon atmosphere with a sample position at 5℃min -1 The temperature was raised to 800℃and the sodium hypophosphite position was raised to 350℃over the same time and held at this temperature for 60min. Finally, the tubular furnace is automatically cooled to room temperature, and the thin-layer carbon-coated tungsten phosphide nanowire/carbon fiber paper self-supporting structure composite material is obtained.
Example 8
2.5mmol of sodium tungstate dihydrate was dissolved in 20mL of deionized water to obtain a colorless transparent solution, the pH value of the solution was adjusted to 1.2 by dropwise addition of hydrochloric acid to obtain a pale yellow solution, then 7mmol of oxalic acid dihydrate was added to the solution, the solution was diluted to 50mL, and 2.5g of ammonium sulfate was added to obtain a colorless transparent solution. The mixed solution was transferred to a reaction vessel while carbon fiber paper (2X 5cm 2 ) By inclined arrangement of the walls, heatingAnd (3) reacting for 16 hours at 180 ℃, naturally cooling, taking out the carbon fiber paper, washing with deionized water, and vacuum drying for 12 hours at 60 ℃. The sample was placed in a tube furnace at 5℃for a min under argon (flow rate 60 sccm) -1 Heating to 600 ℃, then injecting acetonitrile into equipment at a constant feeding rate of 5mLh-1 by using an injection pump at 600 ℃, preserving heat for 120min, and naturally cooling to room temperature to obtain the thin-layer carbon-coated carbon fiber paper-loaded tungsten oxide nanowire self-supporting structure composite material.
The sample obtained above and 2g of sodium hypophosphite were placed in a double-temperature zone tube furnace, with sodium hypophosphite placed on the upstream side of the tube furnace. The tube furnace was then warmed up under argon atmosphere with a sample position at 5℃min -1 The temperature was raised to 800℃and the sodium hypophosphite position was raised to 350℃over the same time and held at this temperature for 180min. Finally, the tubular furnace is automatically cooled to room temperature, and the thin-layer carbon-coated tungsten phosphide nanowire/carbon fiber paper self-supporting structure composite material is obtained.
Example 9
The thin-layer carbon-coated tungsten phosphide nanowire composites prepared in examples 1 and 3-8 and the carbon fiber paper-supported tungsten phosphide nanowire material prepared in comparative example 1 were used for acid electrocatalytic hydrogen evolution. The samples were electrochemically characterized using an electrochemical workstation and measured using a three electrode system. Wherein, a mercury/mercurous sulfate electrode is used as a reference electrode, a carbon fiber paper loaded thin layer carbon coated tungsten phosphide nanowire composite material or a carbon fiber paper loaded tungsten phosphide nanowire material is used as a working electrode, and the electrode is 0.5MH 2 SO 4 As an electrolyte. The electrochemical properties were characterized by scanning the polarization curves of the materials prepared in examples 1, 3 to 8 and comparative example 1, at a scanning speed of 5mVs -1 The test potential was converted to a standard hydrogen electrode potential.
The results are shown in FIG. 5, and it can be seen from the graph that the carbon fiber paper supported thin layer carbon coated tungsten phosphide nanowire composite materials obtained in examples 1 and 3-8 have excellent electrocatalytic hydrogen production performance, particularly when the current density is 20mA/cm, compared with the carbon fiber paper supported tungsten phosphide nanowire material prepared in comparative example 1 2 At the minimum, the overpotential is 125mV. Therefore, the method can directly prepare the carbon fiber paper-loaded thin-layer carbon-coated tungsten phosphide nanowire composite material with excellent electrocatalytic performance.

Claims (4)

1. The self-supporting structure composite material of the carbon-coated tungsten phosphide nanowire is characterized in that the carbon-coated tungsten phosphide nanowire is uniformly grown on a substrate, namely: uniformly coating the surface of the tungsten phosphide nanowire with thin-layer carbon, wherein the thickness of the thin-layer carbon is about 2 nm;
the thin-layer carbon-coated tungsten phosphide nanowire self-supporting structure composite material is prepared by the following method: firstly, loading a hydrated tungsten oxide nanowire precursor on a substrate; then, the precursor is annealed at high temperature in argon atmosphere, and acetonitrile is injected at the same time, so that a thin-layer carbon-coated tungsten oxide nanowire/substrate composite structure is obtained; finally, phosphating is carried out through sodium hypophosphite to obtain the thin-layer carbon-coated tungsten phosphide nanowire self-supporting structure composite material;
the thin-layer carbon-coated tungsten phosphide nanowire self-supporting structure composite material is used for acid electrocatalytic hydrogen evolution, and the substrate-supported thin-layer carbon-coated tungsten phosphide nanowire self-supporting structure composite material is directly used as a working electrode;
the substrate is carbon fiber paper, foam nickel, foam copper or titanium sheet.
2. The preparation method of the carbon-coated tungsten phosphide nanowire self-supporting structure composite material is characterized by comprising the following steps of:
(a) Loading a hydrated tungsten oxide nanowire precursor on a substrate; loading a hydrated tungsten oxide nanowire precursor on a substrate by adopting a solvothermal method; the solvent in the solvothermal method is water, the reaction temperature is 150-200 ℃, and the reaction time is 6-24 hours;
(b) Injecting acetonitrile into the substrate loaded hydrated tungsten oxide nanowire precursor obtained in the step (a) in an argon atmosphere to obtain a thin-layer carbon-coated tungsten oxide nanowire; the method specifically comprises the following steps: under argon atmosphere at 5 deg.C for min -1 The heating rate of (2) was increased to 600℃and the temperature at the time of acetonitrile injection was 600℃and the injection rate was 5mL h -1 Injection time was 2 h;
(c) Carrying out high-temperature phosphating on the surface of the thin-layer carbon-coated tungsten oxide nanowire obtained in the step (b) by utilizing sodium hypophosphite, wherein the phosphating temperature is 700-900 ℃, and the phosphating time is 60-180 min; the thin-layer carbon-coated tungsten phosphide nanowire self-supporting structure composite material can be obtained;
when acid electrocatalytic hydrogen evolution is carried out, the substrate-supported thin-layer carbon-coated tungsten phosphide nanowire self-supporting structure composite material is directly used as a working electrode.
3. The use of the carbon-coated tungsten phosphide nanowire self-supporting structure composite material of claim 1 in the field of industrial electrolytic water catalysts.
4. Use of a carbon-coated tungsten phosphide nanowire self-supporting structure composite material according to claim 3 in the field of industrial electrolytic water catalysts, characterized in that in the presence of an acidic electrolyte, when the current density is 20mA cm -2 The overpotential is 125-156 mV.
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