CN113106490B - Lily-shaped tungsten nitride/tungsten oxycarbide composite material and preparation method and application thereof - Google Patents
Lily-shaped tungsten nitride/tungsten oxycarbide composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a lily-shaped tungsten nitride/tungsten oxycarbide composite material and a preparation method and application thereof, wherein the method comprises the following steps: uniformly mixing pyrrole, absolute ethyl alcohol, a tungsten source and ultrapure water, and centrifuging to obtain a precipitate; and drying the precipitate, and nitriding at 800-1000 ℃ under protective gas to obtain the lily-shaped tungsten nitride/tungsten oxycarbide composite material. WN/W2The (C, O) composite material has uniform chemical composition, high purity and high crystallinity, particularly a lily-shaped self-assembly body, increases the conductivity and the specific surface area of the material, can provide more active sites to participate in electrochemical reaction, finally reduces the reaction barrier in the electrochemical reaction process, has excellent performance of hydrogen evolution by electrolyzing water, improves the hydrogen production efficiency, effectively improves the performance of the electrolyzed water, and has wide application prospect.
Description
The technical field is as follows:
the invention belongs to the technical field of electrochemistry, and particularly relates to a lily-shaped tungsten nitride/tungsten oxycarbide composite material as well as a preparation method and application thereof.
Background art:
currently, it is urgent to find new generation of sustainable development, green, environment-friendly, economic and efficient new energy. Water decomposition is one of the ways of generating clean energy, and the decomposition product is only O2And H2The method has no emission of pollution gas and zero pollution to the environment, so that the hydrogen gas is prepared by decomposing water. Although there are many techniques for producing hydrogen, the production of hydrogen by the splitting of electrolytic water is considered to be the most importantOne potential, because it is minimally affected by the external environment. Therefore, the preparation of hydrogen by electrocatalysis water cracking as a clean sustainable energy conversion and storage technology is one of effective ways for preparing hydrogen energy.
Transition metal nitrides have received much attention in the electrochemical field due to their excellent catalytic activity, high mechanical strength and excellent electrical conductivity. Due to its importance, various transition metal nitride nanostructures, such as mesoporous VN, CoN nanowires, Ni, have been synthesized3N nanowires and mesoporous WN, and the like. Among them, Tungsten nitride (WN) is a promising substitute for Pt, which is a kind of Transition Metal Nitride (TMN) and has excellent properties such as high conductivity, thermal stability, corrosion resistance and excellent hardness, and is referred to in the literature [ ZHao Y, Lv C, Huang Q, et al].Rsc Advances,2016,6(92).]. In addition, tungsten nitride is very similar to tungsten carbide, having a Pt-like electronic structure.
Therefore, the tungsten nitride is very necessary to be used as a substitute carrier material of Pt, and has important value for preparing hydrogen through electrolytic water cracking, but in the process of preparing the tungsten nitride, the synthesis temperature of the tungsten nitride is high, the surface appearance is uncontrollable, so that the tungsten nitride composite material with high efficiency, durability and low cost is difficult to obtain at present, and the catalytic efficiency of electrolytic water is difficult to improve.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the lily-shaped tungsten nitride/tungsten oxycarbide composite material and the preparation method and the application thereof, and the composite material has excellent performance of hydrogen evolution in electrolyzed water, effectively improves the performance of the electrolyzed water and has wide application prospect.
The invention is realized by the following technical scheme:
the preparation method of the lily-shaped tungsten nitride/tungsten oxycarbide composite material comprises the following steps:
uniformly mixing pyrrole, absolute ethyl alcohol, a tungsten source and ultrapure water, and centrifuging to obtain a precipitate;
and drying the precipitate, and nitriding at 800-1000 ℃ under protective gas to obtain the lily-shaped tungsten nitride/tungsten oxycarbide composite material.
Preferably, the tungsten source is tungsten phosphate.
Further, the proportion of the pyrrole, the absolute ethyl alcohol, the tungsten phosphate and the ultrapure water is 1 mL: (40-60) mL: (4.8-8) g: (320-400) mL.
Preferably, the pyrrole, the absolute ethyl alcohol, the tungsten source and the ultrapure water are stirred for 12-18 h and then centrifuged to obtain a precipitate.
Preferably, the precipitate is nitrided at the temperature for 1-3 h.
Preferably, the temperature of the precipitate is increased from room temperature to the temperature, and the temperature increasing rate is 5-10 ℃/min.
Preferably, the obtained lily-shaped tungsten nitride/tungsten oxycarbide composite material is ground into powder.
Preferably, the diameter of the lily-shaped tungsten nitride/tungsten oxycarbide composite material is 0.5-1 μm.
The lily-shaped tungsten nitride/tungsten oxycarbide composite material is prepared by the preparation method of any one of the lily-shaped tungsten nitride/tungsten oxycarbide composite materials.
Application of lily-shaped tungsten nitride/tungsten oxycarbide composite material in electrocatalytic hydrogen production.
Compared with the prior art, the invention has the following beneficial technical effects:
the preparation method of the lily-shaped tungsten nitride/tungsten oxycarbide composite material comprises the steps of uniformly mixing pyrrole, absolute ethyl alcohol, a tungsten source and ultrapure water, centrifuging, inducing pyrrole polymerization by using tungsten phosphate to form a polypyrrole-tungsten phosphate composite, carrying out carbothermic reduction on the composite to generate WN, and simultaneously generating W by using a part of tungsten ions which are not reduced to generate W2(C, O) forming a tungsten nitride and tungsten oxycarbide composite electrocatalyst; the invention adopts a high-temperature solid phase method to overcome the defects of the traditional one-step calcining method, forms a uniform-dispersion lily-shaped appearance, has a simple synthesis process, does not need harsh reaction conditions, and has high product yield. In addition, because the addition of inducer, template and dispersion are not requiredThe reagent and the like, so that the whole reaction process is simple, the purity and the crystallinity of the product are high, the cost of raw materials is low, and the method is environment-friendly and suitable for industrial production; because complex pyrrole and organic absolute ethyl alcohol are introduced in the reaction process, the mixing process can ensure that the tungsten source in the whole mixed solution is in a uniform state, so that the product prepared by the whole reaction is relatively uniform in crystal structure and appearance, and has higher purity and crystallinity; WN/W2The (C, O) powder has a unique radial structure, shows a lily-shaped appearance, and can effectively overcome the agglomeration phenomenon which is easy to occur in the electrocatalysis process by the structure, so that the circulation stability of the material can be further improved. WN/W prepared by the invention2The (C, O) powder is formed by self-assembling a large number of lilies, and the material shows a large specific surface area due to the ultra-small self-assembly, and the large specific surface area can increase the electrolyte and WN/W2Contact between (C, O) electrode materials, thereby increasing the number of reactions at the active site. WN/W2The (C, O) has uniform chemical composition, high purity and high crystallinity, and particularly, the lily-shaped self-assembly body increases the conductivity and the specific surface area of the material, so that more active sites can be provided to participate in electrochemical reaction, the reaction barrier in the electrochemical reaction process is finally reduced, and the hydrogen production efficiency is improved.
Drawings
FIG. 1 shows the lily-shaped WN/W prepared in example 1 of the present invention2XRD pattern of (C, O).
FIG. 2 shows the nano WN/W prepared in example 2 of the present invention2And (C, O) hydrogen production performance diagram.
FIG. 3a, FIG. 3b and FIG. 3c are all lily-shaped WN/W prepared in example 3 of the present invention2SEM image of (C, O).
FIG. 4 is W prepared in comparative example 12XRD pattern of (C, O).
FIG. 5 is W prepared in comparative example 12And (C, O) hydrogen production performance diagram.
The specific implementation mode is as follows:
the present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to lily-shaped WN/W2The preparation method of the (C, O) composite material comprises the following steps:
step 1, uniformly mixing pyrrole and absolute ethyl alcohol, wherein the volume ratio of pyrrole to absolute ethyl alcohol is 1: (40-60) to obtain a solution A;
step 3, mixing the raw materials in a volume ratio of 1: 4 mixing the solution A and the solution B, stirring for 12-18 h, inducing pyrrole polymerization by tungsten phosphate to form polypyrrole PPy, centrifuging, drying the precipitate at the drying temperature of 60-80 ℃, and collecting the obtained product and marking as PPy-PW12(ii) a Since the molecular formula of the tungsten phosphate is H3O40PW12.xH2O, abbreviated herein as PW12；
Step 4, putting the collected sample into a porcelain boat, placing the porcelain boat in a high-temperature tube furnace, vacuumizing, filling argon, repeating for 3-5 times, removing air in the tube, heating to 800-1000 ℃ under the protection of argon atmosphere, and nitriding for 1-3 hours, wherein the precursor PPy-PW is12WN is generated by carbothermal reduction, and W is generated by a part of tungsten ions which are not reduced2(C, O), heating at the rate of 5-10 ℃/min, and taking out the porcelain boat when the porcelain boat is cooled to room temperature;
step 5, pouring the samples in the porcelain boat into a mortar, and grinding the samples into powder without granular sensation to obtain lily-shaped WN/W2(C,O)；
WN/W2The (C, O) nano powder is a lily-shaped structure with the diameter of 0.5-1 mu m, is a catalyst for preparing hydrogen by water electrolysis cracking, and can be applied to lithium ion batteries, fuel cells and electro-catalysis hydrogen production.
Example 1:
(1) uniformly mixing pyrrole and absolute ethyl alcohol, wherein the volume ratio of the pyrrole to the absolute ethyl alcohol is 1: 40, obtaining a solution A;
(2) adding 1.2g of tungsten phosphate into 80mL of ultrapure water to obtain a solution B;
(3) mixing 20mL of the solution A and the solution B, stirring for 12h, centrifuging, drying at 60 ℃ in a vacuum drying oven, and collecting the obtained product and marking the product as PPy-PW12；
(4) Placing the collected sample into a porcelain boat, placing the porcelain boat in a high-temperature tube furnace, vacuumizing, filling argon, repeatedly removing air in the tube for three times, heating to 800 ℃ at a speed of 5 ℃/min under the protection of argon atmosphere, nitriding for 2 hours, and taking out the porcelain boat when the porcelain boat is cooled to room temperature;
(5) pouring the sample in the porcelain boat into a mortar to be ground into powder without granular sensation, and obtaining lily-shaped WN/W2(C,O)。
Example 2:
(1) uniformly mixing pyrrole and absolute ethyl alcohol, wherein the volume ratio of the pyrrole to the absolute ethyl alcohol is 1: 50 to obtain a solution A;
(2) adding 1.4g of tungsten phosphate into 90mL of ultrapure water to obtain a solution B;
(3) mixing 22.5mL of solution A and solution B, stirring for 14h, centrifuging, drying at 70 ℃ in a vacuum drying oven, and collecting the obtained product labeled as PPy-PW12；
(4) Placing the collected sample into a porcelain boat, placing the porcelain boat in a high-temperature tube furnace, vacuumizing, filling argon, repeatedly removing air in the tube for three times, heating to 900 ℃ at a speed of 10 ℃/min under the protection of argon atmosphere, nitriding for 3 hours, and taking out the porcelain boat when the porcelain boat is cooled to room temperature;
(5) pouring the sample in the porcelain boat into a mortar to be ground into powder without granular sensation, and obtaining lily-shaped WN/W2(C,O)。
Example 3:
(1) uniformly mixing pyrrole and absolute ethyl alcohol, wherein the volume ratio of the pyrrole to the absolute ethyl alcohol is 1: 60 to obtain a solution A;
(2) adding 1.6g of tungsten phosphate into 100mL of ultrapure water to obtain a solution B;
(3) mixing 25mL of solution A and solution B, stirring for 16h, centrifuging, and addingDrying in vacuum drying oven at 80 deg.C, collecting the product and labeling as PPy-PW12；
(4) Putting the collected sample into a porcelain boat, placing the porcelain boat in a high-temperature tube furnace, vacuumizing, filling argon, repeatedly removing air in the tube for five times, heating to 1000 ℃ at a speed of 5 ℃/min under the protection of argon atmosphere, nitriding for 2 hours, and taking out the porcelain boat when the porcelain boat is cooled to room temperature;
(5) pouring the sample in the porcelain boat into a mortar to be ground into powder without granular sensation, and obtaining lily-shaped WN/W2(C,O)。
Example 4:
(1) uniformly mixing pyrrole and absolute ethyl alcohol, wherein the volume ratio of the pyrrole to the absolute ethyl alcohol is 1: 50 to obtain a solution A;
(2) adding 2g of tungsten phosphate into 90mL of ultrapure water to obtain a solution B;
(3) mixing 22.5mL of solution A and solution B, stirring for 18h, centrifuging, drying at 60 ℃ in a vacuum drying oven, and collecting the obtained product labeled as PPy-PW12；
(4) Putting the collected sample into a porcelain boat, placing the porcelain boat in a high-temperature tube furnace, vacuumizing, filling argon, repeatedly removing air in the tube for four times, heating to 900 ℃ at a speed of 7 ℃/min under the protection of argon atmosphere, nitriding for 1h, and taking out the porcelain boat when the porcelain boat is cooled to room temperature;
(5) pouring the sample in the porcelain boat into a mortar to be ground into powder without granular sensation, and obtaining lily-shaped WN/W2(C,O)。
Comparative example 1:
(1) uniformly mixing pyrrole and absolute ethyl alcohol, wherein the volume ratio of the pyrrole to the absolute ethyl alcohol is 1: 70, obtaining a solution A;
(2) adding 1g of tungsten phosphate into 80mL of ultrapure water to obtain a solution B;
(3) mixing 20mL of the solution A and the solution B, stirring for 14h, centrifuging, drying at 80 ℃ in a vacuum drying oven, and collecting to obtain a product;
(4) placing the collected sample into a porcelain boat, placing the porcelain boat in a high-temperature tube furnace, vacuumizing, filling argon, repeatedly removing air in the tube for three times, heating to 800 ℃ at a temperature of 10 ℃/min under the protection of argon atmosphere, nitriding for 3 hours, and taking out the porcelain boat when the porcelain boat is cooled to room temperature;
(5) pouring the sample in the porcelain boat into a mortar to be ground into powder without granular sensation, and obtaining lily-shaped W2(C, O), when the volume ratio of the pyrrole to the absolute ethyl alcohol is reduced, the concentration content of a nitrogen source in the solution is reduced, and WN cannot be generated in the subsequent high-temperature nitridation process.
It can be seen from FIG. 1 that the diffraction peak of the sample is well matched with the standard card, the intensity is high, and the diffraction peak is sharp, which shows WN/W obtained by the embodiment2The (C, O) has high crystallinity and high purity.
Figure 2 shows a graph of hydrogen production performance measured at an electrochemical workstation using a typical three-electrode system using a Saturated Calomel Electrode (SCE) and a carbon rod as reference and counter electrodes, respectively. The working electrode was treated as follows: (i) dispersing 10mg of the catalyst obtained in the step 2 in 300. mu.L of isopropanol, and carrying out ultrasonic treatment to obtain a mixed solution; (ii) dropping 2 μ L of the mixed solution onto the working electrode with a loading of about 0.9mg cm-2(ii) a (iii) After the catalyst is naturally dried, 2 muL of Nafion with the mass fraction of 1% needs to be dripped on the surface of the catalyst to prevent the catalyst from falling off in the test process. Under the test condition of pH 14(1MKOH), the current density is-10 mA/cm2When the scanning speed is 3mV/s, the overpotential of the sample is 108mV, which shows that the catalyst has extremely excellent catalytic performance.
Fig. 3a, 3b and 3c are only different in resolution, and it can be seen from fig. 3a, 3b and 3c that the sample morphology is a three-dimensional lily-shaped structure, the sample dispersibility is good, and the specific surface area is large.
From FIG. 4, it can be seen that the diffraction peak of the sample corresponds to the standard card, and the diffraction peak is sharp, indicating that W is successfully prepared2(C,O)。
FIG. 5 shows the current density at-10 mA/cm at a scan rate of 3mV/s under test conditions of pH 14(1M KOH)2The overpotential required to be overcome by the sample is 257mV which is more than WN/W2The overpotential required for (C, O) is 108mV, which indicates the composite phase WN/W2The hydrogen production performance of (C, O) is better than that of W2(C,O)。
Claims (5)
1. The preparation method of the lily-shaped tungsten nitride/tungsten oxycarbide composite material is characterized by comprising the following steps of:
stirring pyrrole, absolute ethyl alcohol, tungsten phosphate and ultrapure water for 12-18 h, and centrifuging, wherein the proportion of pyrrole, absolute ethyl alcohol, tungsten phosphate and ultrapure water is 1 mL: (40-60) mL: (4.8-8) g: (320-400) mL to obtain a precipitate;
and drying the precipitate, and nitriding the dried precipitate at 800-1000 ℃ for 1-3 h under protective gas, heating the precipitate from room temperature to the temperature at the heating rate of 5-10 ℃/min, so as to obtain the lily-shaped tungsten nitride/tungsten oxycarbide composite material.
2. The method for preparing a lily-shaped tungsten nitride/tungsten oxycarbide composite material according to claim 1, wherein the obtained lily-shaped tungsten nitride/tungsten oxycarbide composite material is ground into powder.
3. The method for preparing the lily-shaped tungsten nitride/tungsten oxycarbide composite material according to claim 1, wherein the diameter of the lily-shaped tungsten nitride/tungsten oxycarbide composite material is 0.5 to 1 μm.
4. The lily-shaped tungsten nitride/tungsten oxycarbide composite material obtained by the preparation method of the lily-shaped tungsten nitride/tungsten oxycarbide composite material according to any one of claims 1 to 3.
5. The use of the lilium brownie tungsten nitride/tungsten oxycarbide composite material of claim 4 in the electrocatalytic hydrogen production.
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