CN114635154A - Vanadium nitride/vanadium trioxide composite electro-catalytic material, preparation method and application thereof in aspect of hydrogen production by water cracking - Google Patents
Vanadium nitride/vanadium trioxide composite electro-catalytic material, preparation method and application thereof in aspect of hydrogen production by water cracking Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
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Abstract
The invention discloses a vanadium nitride/vanadium trioxide composite electrocatalytic material, a preparation method and application thereof in hydrogen production by water cracking. The VN/V2O3The composite electro-catalytic material comprises mutually interwoven VN nano sheets and V inlaid on the surfaces of the VN nano sheets2O3Granules in which VN and V2O3The mass ratio of (A) to (B) is 2:1-10: 1. the composite electro-catalytic material has good two-phase dispersibility, and excellent catalytic performance is obtained by the synergistic effect of the two phases.
Description
Technical Field
The invention belongs to the field of electrocatalysts, and particularly relates to VN/V2O3A composite electro-catalytic material, a preparation method and application thereof in hydrogen production by water cracking.
Background
The lack of traditional energy sources and the increasingly prominent problem of environmental pollution have attracted extensive attention by researchers and scholars. Hydrogen, as a clean, green, abundant energy source with potential renewability and cleanliness for the environment, is considered as a new generation energy source to replace Pt-based materials. More than 96% of hydrogen energy is derived from fossil fuels due to production cost problems, but the use of fossil fuels to produce hydrogen gas is contrary to the gist of sustainable development and causes damage to the environment. In order to reduce the production cost of hydrogen energy, more work is being done to develop new technologies for producing hydrogen, wherein research on processes and materials for producing hydrogen by water cracking is the focus of research.
The vanadium nitride material is used as a transition metal nitride, has good electric conduction and heat conduction catalytic performance, and has wide application in the fields of physics, chemistry and materials. ZHEN et al prepared by reacting aminovanadium (IV), ammonium bicarbonate and (NH)4)2[(VO)6(CO3)4(OH)9]·10H2O is reduced and pyrolyzed in hydrogen to obtain spherical V2O3Nano powder ([ Pinna N, Antonietti M, Niederberger M.A novel non-aqueous route to V)2O3 and Nb2O5 nanocrystals[J].Colloids&Surfaces A Physicochemical&Engineering Aspects,2004,250:211-213.])。
Disclosure of Invention
The technical purpose of the invention is to develop a VN/V2O3The composite electro-catalytic material has good two-phase dispersibility, and excellent catalysis is obtained by two-phase synergistic effectAnd (4) performance.
In a first aspect, the present invention provides a VN/V2O3A composite electrocatalytic material. The VN/V2O3The composite electro-catalytic material comprises mutually interwoven VN nano sheets and V inlaid on the surfaces of the VN nano sheets2O3Granules in which VN and V2O3The mass ratio of (A) to (B) is 2:1-10: 1. VN, as a transition metal nitride, has a Pt-like electronic structure, excellent electron conductivity, a low tafel slope, and good stability. The invention controls VN and V2O3According to the mass ratio of (A) to (B), synthesizing V2O3The composite electro-catalytic material for modifying VN has satisfactory electro-catalytic performance.
Preferably, the VN nanosheet has a thickness of 5-20nm, and V2O3The particle size of the particles is 20-100 nm.
Preferably, the VN/V2O3The electrochemical area of the composite electro-catalytic material is 20-30mF cm-2. The electrochemically active area is the area of the portion of the region where the catalyst is able to exert a catalytic effect.
In a second aspect, the present invention also provides a VN/V according to any preceding claim2O3A preparation method of a composite electro-catalytic material. The preparation method comprises the following steps: raw materials containing a nitrogen source and a vanadium source are mixed according to the mass ratio of (2-6): (1-3) uniformly mixing to form a mixture, and performing thermal pyrolysis on the mixture at the temperature of 700-900 ℃ for 120-180min in an inert atmosphere to obtain the VN/V2O3A composite electrocatalytic material.
Preferably, the nitrogen source generates reducing gas in the thermal pyrolysis process so that the components of the composite electro-catalytic material are uniformly dispersed. The reducing gas includes, but is not limited to, ammonia gas and the like.
Agglomeration easily occurs during the sintering process of the solid phase method, so that the prepared sample particles are generally large in size, which is not favorable for improving the catalytic performance. According to the invention, the nitrogen source which generates the reducing gas in the solid-phase reaction process is introduced into the raw materials, so that the morphology can be regulated, and the mass ratio of the nitrogen source to the vanadium source is strictly controlled to generate the VN nanosheetTime promotion of V2O3Nanoparticle generation, induction of VN/V formation2O3A composite electrocatalytic material.
Preferably, the nitrogen source comprises at least one of urea, dicyandiamide, melamine.
Preferably, the vanadium source comprises at least one of ammonium metavanadate, sodium metavanadate and vanadium acetylacetonate.
Preferably, the inert atmosphere is argon.
In a third aspect, the present invention also provides a VN/V according to any preceding claim2O3The application of the composite electro-catalytic material in the aspect of hydrogen production by water cracking.
The invention has the following beneficial effects:
1. VN/V of the invention2O3The material has high purity and crystallinity, VN nano sheets are mutually interwoven, and V2O3Nanoparticles are embedded on VN nano-sheets to expose more active sites, so that the electrochemical area is larger, and VN/V is promoted2O3And the electrocatalysis performance is improved.
2. The electrocatalyst has the characteristics of good conductivity, small overpotential and the like, and has great advantages in the aspect of hydrogen production by water electrolysis.
3. The preparation method provides a novel synthesis strategy for the design of the synthesis method of the nitride electrocatalyst, and the one-step solid phase method is simple, easy to operate and easy to control, and meets the requirement of industrial production.
Drawings
FIG. 1 is VN/V prepared in example 12O3An XRD spectrum of the composite electrocatalytic material;
FIG. 2 is VN/V prepared in example 22O3SEM image of the composite electrocatalytic material;
FIG. 3 is VN/V prepared in example 32O3A TEM image of the composite electrocatalytic material;
FIG. 4 is VN/V prepared in example 62O3Hydrogen production performance diagram of the composite electro-catalytic material under the condition of pH 14;
FIG. 5 is VN/V prepared in example 62O3Hydrogen production performance diagram of the composite electro-catalytic material under the condition of pH 0;
FIG. 6 shows a single phase V of comparative example 22O3An XRD pattern of (a);
FIG. 7 shows a single phase V of comparative example 22O3Hydrogen production performance under the condition of pH 14;
FIG. 8 shows a single phase V of comparative example 22O3Hydrogen production performance diagram under the condition of pH 0;
figure 9 is an XRD pattern of single phase VN of comparative example 1;
FIG. 10 is a graph of hydrogen production performance of single-phase VN of comparative example 1 at pH 14;
fig. 11 is an SEM image of single phase VN of comparative example 1;
FIG. 12 shows a single phase V of comparative example 22O3SEM image of (d).
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. Unless otherwise specified, each percentage means a mass percentage.
The following exemplary description describes the VN/V of the invention2O3A preparation method of a composite electro-catalytic material.
And weighing the nitrogen source and the vanadium source according to a certain mass ratio. The mass ratio of the nitrogen source to the vanadium source can be (2-6): (1-3). When the mass ratio of the nitrogen source to the vanadium source exceeds the range, the reduction gas generated by pyrolysis is too little to reduce vanadium in vanadate radical to generate VN, and only V is contained in the product2O3Or too much reducing gas is generated by pyrolysis, so that all vanadium in the vanadate radical is reduced to VN, which is not beneficial to the catalytic performance of the composite electro-catalytic material.
In the preparation method of the invention, the nitrogen source is pyrolyzed in the subsequent reaction process to generate reducing gas (such as ammonia gas), so that the nitrogen source not only plays the role of a reducing agent, but also can realize VN particles and V in a composite structure2O3The particles are uniformly dispersed, and no additional reducing agent or dispersing agent is needed, so that the use of dangerous reducing gas is avoided. In addition, the nitrogen source is low in price, suitable for industrial production and safe in reaction.
Preferably, the mass percent of nitrogen in the nitrogen source is more than 30%. When the mass percentage of nitrogen element in the nitrogen source is high, the yield of the generated product is high and the catalytic performance is excellent. In some embodiments, the mass percent of nitrogen in the nitrogen source is between 40 and 70%. In particular embodiments, the nitrogen source includes, but is not limited to, one of ammonium dicyandiamide, melamine, and urea.
And weighing the nitrogen source and the vanadium source to obtain a mixture. Preferably dry mixing. For example, the mixing may be performed by stirring, ball milling, or the like. The mixing time is not limited, so that all the raw materials are uniformly mixed. Preparing a target product VN/V from the mixture in a solid phase synthesis manner2O3A composite electrocatalytic material. The solid phase synthesis is carried out under an inert protective atmosphere. The inert protective atmosphere may be argon. Preferably, the flow rate of the inert protective atmosphere is 20-40 mL/min.
For example, the mixture is put into an agate mortar, ground until the raw material is uniformly fine, and then put into a porcelain boat. The grinding time can be 20-30 min. The porcelain boat is placed in a tubular atmosphere furnace, and two furnace plugs are respectively placed at two ends of the tube. The furnace plug spacing may be 5 cm. And (3) introducing inert atmosphere into the tubular atmosphere furnace, then exhausting and supplementing air for 4-6 times, exhausting air in the tubular atmosphere furnace, and not exhausting air after the last air supplement. The inert atmosphere may be argon or nitrogen. The temperature of the solid phase synthesis may be 700-900 ℃. The incubation time for solid phase synthesis can be 120-180 min. In some embodiments, the temperature is raised to 700-900 ℃ at a rate of 5-10 ℃/min. After the heat preservation is finished, cooling to room temperature along with the furnace, grinding the sample to obtain VN/V2O3A composite electrocatalytic material.
In some embodiments, the nitrogen source is preferably urea. The urea is pyrolyzed in the solid-phase reaction process to generate reducing gas, and the reducing gas plays a role in dispersing to promote the sample to be dispersed more uniformly, so that the appearance of the sample is regulated and controlled, and the phenomenon that the urea is easy to agglomerate in the solid-phase sintering process is avoided; and secondly, reducing the vanadium to form VN by the generated reducing gas.
VN/V of the invention2O3A synergistic relationship exists between the two. Good VN conductivity and releaseThe low reaction potential barrier of hydrogen gas, and V-O can be effectively combined with H by theoretical calculation+。VN/V2O3Balances the hydrogen production reaction kinetics, and is more than single-phase VN and V2O3Has more excellent catalytic performance. For example, VN/V according to the invention2O3The current density of the composite electro-catalytic material is 10mA/cm2The overpotential in alkaline solution and acidic solution can reach 98mV and 136mV respectively.
In some embodiments, the invention can additionally add a dispersant such as ammonium bicarbonate to further perform morphology control on the compound so as to improve the hydrogen catalysis performance of the cracked water.
The electrochemical area of the composite electrocatalytic material was calculated by CV. And (3) testing CV curves of different sweep speeds, taking the current density difference of the intermediate value of the voltage as a vertical coordinate, taking the sweep speed as a horizontal coordinate, fitting a straight line, and taking half of the slope of the straight line as the double-layer capacitor Cdl. Cdl represents the size of the electrochemically active area.
Electrochemical testing was performed by a typical three-electrode system using an electrochemical workstation (CHI660E B17060, shanghai CH instruments, china). Saturated Calomel Electrode (SCE) and carbon rod were used as reference and counter electrodes, respectively. Processing the working electrode: (i) dispersing 10mg of catalyst in 300 mu L of isopropanol, and carrying out ultrasonic homogenization on the catalyst; (ii) dropping 2 μ L of the mixture solution onto a glassy carbon electrode with a loading of about 0.9mg cm-2(ii) a (iii) After the catalyst is naturally dried, 2 mu L 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. The prepared sample was acidified (0.5M H)2SO4) And respectively carrying out electro-catalytic hydrogen production test under the alkaline (1M KOH) condition by using 3mV s-1Is tested.
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
(1) Urea and acetylacetone vanadium are mixed according to the mass ratio CH4N2O：C15H21O6V is 2:1, burdening;
(2) mixing and fully grinding the urea and the vanadium acetylacetonate in the mass ratio, loading the mixture into a porcelain boat, placing the porcelain boat into a high-temperature tube type atmosphere furnace, and placing two furnace plugs at two ends of the tube respectively;
(3) introducing argon gas atmosphere into the tube, then performing air extraction and air supplement for 6 times, exhausting the air in the tube, and not performing air extraction after the last air supplement. Introducing atmosphere at the rate of 20mL/min, heating to 700 ℃ at the rate of 5 ℃/min, and preserving the heat at 700 ℃ for 120 min; (4) cooling to room temperature, and fully grinding the black sample in the porcelain boat in a mortar to obtain VN/V2O3A composite electrocatalytic material.
FIG. 1 is VN/V prepared in example 12O3XRD pattern of the composite electrocatalytic material can show that VN and V are samples2O3The diffraction peak of (A) well matched the standard card, indicating that VN/V obtained in this example2O3The crystallinity is good.
Example 2
(1) Urea and acetylacetone vanadium raw materials are mixed according to the mass ratio CH4N2O：C15H21O6And V is 3: 2, burdening;
(2) mixing urea and vanadium acetylacetonate, fully grinding, placing the mixture into a porcelain boat, placing the porcelain boat into a high-temperature tube type atmosphere furnace, and respectively placing two furnace plugs at two ends of the tube;
(3) introducing argon gas atmosphere into the tube, then performing air extraction and air supplement for 6 times, exhausting the air in the tube, and not performing air extraction after the last air supplement. Introducing atmosphere at the rate of 30mL/min, heating to 800 ℃ at the rate of 10 ℃/min, and preserving the temperature at 800 ℃ for 180 min;
(4) cooling to room temperature, and fully grinding the black sample in the porcelain boat in a mortar to obtain VN/V2O3Composite electrocatalysisA material.
FIG. 2 is VN/V prepared in example 22O3SEM image of the composite electro-catalytic material shows that VN nano sheets are mutually interwoven, V2O3Nanoparticles are embedded on VN nano-sheets, and show larger specific surface area, and more active sites are exposed.
Example 3
(1) Urea and acetylacetone vanadium raw materials are mixed according to the mass ratio CH4N2O：C15H21O6V ═ 4: 3, burdening;
(2) mixing urea and vanadium acetylacetonate, fully grinding, placing the mixture into a porcelain boat, placing the porcelain boat into a high-temperature tube type atmosphere furnace, and respectively placing two furnace plugs at two ends of the tube;
(3) introducing argon gas atmosphere into the tube, then performing air extraction and air supplement for 6 times, exhausting the air in the tube, and not performing air extraction after the last air supplement. Introducing atmosphere at the rate of 40mL/min, heating to 900 ℃ at the rate of 5 ℃/min, and preserving heat at 900 ℃ for 120 min;
(4) cooling to room temperature, and fully grinding the black sample in the porcelain boat in a mortar to obtain VN/V2O3A composite electrocatalytic material.
FIG. 3 is VN/V prepared in example 32O3TEM image of the composite electrocatalytic material, it can be seen that VN is in the form of nano-platelets, V2O3The VN/V obtained in this example was further demonstrated by the distinct corresponding lattice fringes for the nanoparticles embedded in the VN nanoplates2O3The crystallinity is good.
Example 4
(1) Urea and acetylacetone vanadium raw materials are mixed according to the mass ratio CH4N2O：C15H21O6And V is 5: 2, proportioning;
(2) mixing urea and vanadium acetylacetonate, fully grinding, placing the mixture into a porcelain boat, placing the porcelain boat into a high-temperature tube type atmosphere furnace, and respectively placing two furnace plugs at two ends of the tube;
(3) introducing argon gas atmosphere into the tube, then performing air extraction and air supplement for 6 times, exhausting the air in the tube, and not performing air extraction after the last air supplement. Introducing atmosphere at the rate of 20mL/min, heating to 700 ℃ at the rate of 10 ℃/min, and preserving the temperature at 700 ℃ for 180 min;
(4) cooling to room temperature, and fully grinding the black sample in the porcelain boat in a mortar to obtain VN/V2O3A composite electrocatalytic material.
Example 5
(1) Urea and acetylacetone vanadium raw materials are mixed according to the mass ratio CH4N2O：C15H21O6V ═ 6: 1, burdening;
(2) mixing urea and vanadium acetylacetonate, fully grinding, placing the mixture into a porcelain boat, placing the porcelain boat into a high-temperature tube type atmosphere furnace, and respectively placing two furnace plugs at two ends of the tube;
(3) introducing argon gas atmosphere into the tube, then performing air extraction and air supplement for 6 times, exhausting the air in the tube, and not performing air extraction after the last air supplement. Introducing atmosphere at the rate of 30mL/min, heating to 800 ℃ at the rate of 5 ℃/min, and preserving the temperature at 800 ℃ for 120 min;
(4) cooling to room temperature, and fully grinding the black sample in the porcelain boat in a mortar to obtain VN/V2O3A composite electrocatalytic material.
Example 6
(1) Urea and acetylacetone vanadium raw materials are mixed according to the mass ratio CH4N2O：C15H21O6V-4: 1, burdening;
(2) mixing urea and vanadium acetylacetonate, fully grinding, placing the mixture into a porcelain boat, placing the porcelain boat into a high-temperature tube type atmosphere furnace, and respectively placing two furnace plugs at two ends of the tube;
(3) introducing argon atmosphere into the tube, performing air extraction and air supplementation for 6 times, exhausting the air in the tube, introducing the atmosphere at the speed of 40mL/min without air extraction after the last air supplementation, heating to 800 ℃ at the speed of 10 ℃/min, and preserving the temperature for 180min at 800 ℃;
(4) cooling to room temperature, and fully grinding the black sample in the porcelain boat in a mortar to obtain VN/V2O3A composite electrocatalytic material.
FIG. 4 is VN/V prepared in example 62O3The hydrogen production performance of the composite electro-catalytic material is shown in the figure, which shows that under the alkaline test condition, the current density is 10mA/cm2When the scanning rate is 3mV/s, the overpotential of the sample is 98mV, which shows that the catalyst has excellent catalytic activity.
FIG. 5 is VN/V prepared in example 62O3The hydrogen production performance diagram of the composite electro-catalytic material shows that under the acidic test condition, the current density is 10mA/cm2When the scanning rate is 3mV/s, the overpotential of the sample is 136mV, which shows that the sample has excellent catalytic activity.
Comparative example 1
Essentially the same as example 1, except that: the mass ratio of urea to vanadium acetylacetonate is 7: 1. only a single phase VN is generated at this time.
Fig. 9 is an XRD pattern of single phase VN of comparative example 1 and it can be seen that the diffraction peaks of sample and VN match well with the standard card indicating that the sample is better crystalline. FIG. 10 is a graph of hydrogen production performance of single-phase VN of comparative example 1, which shows that the current density is 10mA/cm under the alkaline test condition2At a scan rate of 3mV/s, the overpotential for this sample was 420mV, indicating that the performance was very modest and very poor under acidic test conditions. Fig. 11 is an SEM image of single-phase VN of comparative example 1, and only single-phase VN nanoplates and VN nanoparticles were observed. This is because too high a urea content leads to the generation of reducing gases NH during pyrolysis at high temperatures3Fully reduces all vanadium in the vanadate radical to generate VN, so that only VN is generated in the product phase.
Comparative example 2
Essentially the same as example 5, except that: the mass ratio of urea to vanadium acetylacetonate is 1: 1. all generate V at this time2O3And (3) nanoparticles.
FIG. 6 shows a single phase V of comparative example 22O3XRD pattern of (A), it can be seen that sample and V2O3The diffraction peak of (A) is well matched with the standard card, indicating that V2O3The crystallinity is good. FIG. 7 shows a single phase V of comparative example 22O3A hydrogen production performance chart which shows that under the alkaline test condition, the current density is 10mA/cm2When the scanning speed is 3mV/s, the overpotential of the sample is 255mV, which is inferior to VN/V2O3The alkaline condition hydrogen production performance of the composite electro-catalytic material. FIG. 8 is a comparisonEXAMPLE 2 Single-phase V2O3The hydrogen production performance is shown in the figure, which shows that under the acid test condition, the current density is 10mA/cm2The overpotential of this sample was 173mV, lower than VN/V, at a scan rate of 3mV/s2O3The hydrogen production performance of the composite electro-catalytic material under acidic conditions. FIG. 12 shows a single phase V of comparative example 22O3SEM image of (1), V can be clearly seen2O3Is in the form of nanometer particles. This is because the urea content is low, resulting in the reducing gas NH generated during pyrolysis3Too little vanadium in the vanadate radical can not be reduced to generate VN, so that only V is in the product phase2O3And (3) nanoparticles.
Claims (9)
1. VN/V2O3Composite electrocatalytic material, characterized in that said VN/V2O3The composite electro-catalytic material comprises mutually interwoven VN nano sheets and V embedded on the surfaces of the VN nano sheets2O3Granules in which VN and V2O3The mass ratio of (A) to (B) is 2:1-10: 1.
2. a VN/V according to claim 12O3The composite electro-catalytic material is characterized in that the VN nanosheet is 5-20nm in thickness and V2O3The particle size of the particles is 20-100 nm.
3. A VN/V according to claim 1 or 22O3Composite electrocatalytic material, characterized in that said VN/V2O3The electrochemical area of the composite electro-catalytic material is 20-30mF cm-2。
4. A VN/V according to any one of claims 1 to 32O3The preparation method of the composite electro-catalytic material is characterized by comprising the following steps: raw materials containing a nitrogen source and a vanadium source are mixed according to the mass ratio of (2-6): (1-3) uniformly mixing to form a mixture, and performing thermal pyrolysis on the mixture at the temperature of 700-900 ℃ for 120-180min in an inert atmosphere to obtain the VN/V2O3A composite electrocatalytic material.
5. The preparation method according to claim 4, wherein the nitrogen source is used for generating reducing gas during the thermal pyrolysis process so as to uniformly disperse the components of the composite electrocatalytic material.
6. The method according to claim 4 or 5, wherein the nitrogen source comprises at least one of urea, dicyandiamide, and melamine.
7. The method according to any one of claims 4 to 6, wherein the vanadium source comprises at least one of ammonium metavanadate, sodium metavanadate, and vanadium acetylacetonate.
8. The method according to any one of claims 4 to 7, wherein the inert atmosphere is argon or nitrogen.
9. VN/V according to any one of claims 1 to 32O3The application of the composite electro-catalytic material in the aspect of hydrogen production by water cracking.
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| CN109280934A (en) * | 2018-09-28 | 2019-01-29 | 陕西科技大学 | A kind of carbon-coated vanadium nitride elctro-catalyst, preparation method and application |
| CN110560141A (en) * | 2019-09-30 | 2019-12-13 | 陕西科技大学 | Preparation method and application of VN @ WN nanoparticles with electrocatalytic function |
| CN110581284A (en) * | 2019-09-30 | 2019-12-17 | 陕西科技大学 | Electrocatalysis function V2O3Preparation method and application of @ Co |
| CN111701594A (en) * | 2020-06-09 | 2020-09-25 | 电子科技大学 | Three-dimensional porous V modified by supported monodisperse Ni nanoparticles2O3Preparation method of micro-flower rice |
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| CN109280934A (en) * | 2018-09-28 | 2019-01-29 | 陕西科技大学 | A kind of carbon-coated vanadium nitride elctro-catalyst, preparation method and application |
| CN110560141A (en) * | 2019-09-30 | 2019-12-13 | 陕西科技大学 | Preparation method and application of VN @ WN nanoparticles with electrocatalytic function |
| CN110581284A (en) * | 2019-09-30 | 2019-12-17 | 陕西科技大学 | Electrocatalysis function V2O3Preparation method and application of @ Co |
| CN111701594A (en) * | 2020-06-09 | 2020-09-25 | 电子科技大学 | Three-dimensional porous V modified by supported monodisperse Ni nanoparticles2O3Preparation method of micro-flower rice |
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