CN108823600A - A kind of nickel-molybdenum carbide nanoparticle/carbon fiber composite nano materials, preparation method and applications - Google Patents
A kind of nickel-molybdenum carbide nanoparticle/carbon fiber composite nano materials, preparation method and applications Download PDFInfo
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Abstract
A kind of nickel-molybdenum carbide nanoparticle/carbon fiber composite nano materials, preparation method and its application in electrocatalytic hydrogen evolution or analysis oxygen, belong to base metal base carbon fibre composite nano materials controllable preparation technical field.The present invention utilizes three electrostatic spinning technique, air atmosphere low temperature calcination and argon atmosphere high-temperature calcination steps, is prepared for nickel-molybdenum carbide nanoparticle/carbon fiber composite nano materials.Composite material integrally exists with fiber morphology, and nickel nano particle and molybdenum carbide nanoparticle are evenly distributed on the inside and outside of carbon fiber.This method heavy industrialization application low in cost, simple and easy, achievable.Nickel prepared by the present invention-molybdenum carbide nanoparticle/carbon fiber composite nano materials are as electro-catalysis water decomposition bifunctional electrocatalyst, excellent catalytic activity is shown, it realizes and efficiently prepares free of contamination hydrogen energy source, new strategy is proposed to cope with the environmental problem got worse, there is important practical application value.
Description
Technical field
The invention belongs to base metal base carbon fibre composite nano materials controllable preparation technical fields, and in particular to a kind of
Nickel-molybdenum carbide nanoparticle/carbon fiber composite nano materials, preparation method and its application in electrocatalytic hydrogen evolution or analysis oxygen.
Background technique
The dominant direction that sustainable development has become future source of energy environment and economic strategy develops, and fossil energy since tradition
The energy output technology of source conversion faces the dual test of shortage of resources and environmental pollution.Hydrogen has clear as renewable alternative energy source
Clean, efficient, free of contamination advantage.Electro-chemical water decomposition can produce high-purity hydrogen, be divided into liberation of hydrogen (HER) and analysis oxygen (OER) two
A half-reaction, however most of oxygen evolution reaction all carries out under alkaline environment, therefore alkaline Electrocatalytic Activity for Hydrogen Evolution Reaction agent is developed to closing weight
It wants.Platinum (Pt) noble metal catalyst is the generally acknowledged highest liberation of hydrogen catalyst of activity, however its reserves it is rare, it is expensive,
Easily by OH-Poison, hinders its extensive use.Therefore, exploitation base metal alkalinity liberation of hydrogen catalyst is needed.
W metal is typical alkaline liberation of hydrogen catalyst, cheap and have optimal OH-Ni2+δ(0≤δ≤
1.5), be conducive to adsorb intermediate product, reduce overpotential.However Ni nanoparticle easily corroded in strong acid and strong base environment with it is blunt
Change, stability is poor.Recently, transition metal carbide (TMCs) is used as liberation of hydrogen catalyst, high mechanical strong because of its strong corrosion resistance
The advantages that degree and good stability, has attracted the extensive concern of people.Wherein molybdenum carbide (Mo2C) because its preparation process is nontoxic,
Wide pH value adaptability and there is d identical with Pt race metal to charge the characteristics such as minor structure and become is a kind of potential analysis
Hydrogen catalyst.But its electric conductivity is poor, interface reaction kinetics are slow, independent Mo2The catalytic property of C is still far away from Pt base
Material.Known hydrogen evolution activity and metal-hydrogen bond strength are closely related, and the hydrogen of Ni combines energy (HBE) weaker, and Mo2The HBE of C compared with
By force.Therefore by Ni and Mo2HBE can be adjusted to moderate value by C chemical Coupling, to balance the heat between hydrogen absorption and parsing
Mechanics improves catalytic activity for hydrogen evolution.Furthermore has document report Mo2C not only has good hydrogen evolution activity while also having
Oxygen evolution activity.2015, Kwak et al. successfully prepared molybdenum carbide/carbon mano-tube composite as bifunctional catalyst and is catalyzed oxygen also
Former (ORR) and analysis oxygen OER reaction, and be published in《ACS Nano》On.2017, Gao et al. existed《ChemSusChem》Report
Molybdenum carbide/carbon nanosheet of the successful preparation in road can be used for being catalyzed overall moisture solution.In addition to the selection of catalyst, the shape of catalyst
Looks and size equally will affect catalytic activity.Carbon fiber (CNFs) as typical monodimension nanometer material have large specific surface area,
The advantages that electric conductivity is strong, flexible structure is a kind of bracket for being preferably used to support catalytically-active materials.Nanoparticle is encapsulated
It can effectively avoid corrosion caused by the reunion and external environment of particle in CNFs and aoxidize, to improve the stabilization of catalyst
Property.In addition, hetero atom (such as nitrogen-atoms), which is doped in carbon fiber, can activate neighbouring carbon atom to improve electric conductivity and urge
Change activity.
Summary of the invention
The object of the present invention is to provide a kind of base metal elctro-catalyst nickel-molybdenum carbide difunctional with efficient water decomposition
Nanoparticle/carbon fiber composite nano materials, preparation method and its application in electrocatalytic hydrogen evolution analysis oxygen, to solve noble metal
Catalyst is expensive, stability it is poor can not large-scale use the problem of.
The present invention is prepared using electrostatic spinning technique combination air atmosphere low temperature calcination and inert atmosphere high-temperature calcination technology
Nickel-molybdenum carbide nanoparticle/carbon fiber composite nano materials catalyst, composite material integrally exist with fiber morphology, nickel nanometer
Particle and molybdenum carbide nanoparticle are evenly distributed on the inside and outside of carbon fiber.Pass through the optimization to preparation process, it is determined that suitable
Reaction condition, prepared catalyst has excellent catalytic activity, in 1mol/L KOH electrolyte, when current density reaches
10mA.cm-2The overpotential of Shi Suoxu evolving hydrogen reaction and oxygen evolution reaction is respectively -143mV and 288mV.
A kind of nickel of the present invention-molybdenum carbide nanoparticle/carbon fiber composite nano materials preparation method, step
It is as follows：
(1) composite nano-fiber membrane is prepared by method of electrostatic spinning：Firstly, 0.1~0.3g polyacrylonitrile (PAN) is dissolved in
In 1.0~4.0g n,N-Dimethylformamide (DMF), magnetic agitation at 80~100 DEG C, after PAN all dissolution, by 0.033
~0.133g nickel acetate (Ni (Ac)2.4H2) and 0.067~0.267g acetyl acetone (MoO O2(acac)2) it is dissolved in above-mentioned solution
In be stirred overnight, obtain uniform thick shape spinning solution presoma；Spinning solution is injected in the glass spin duct of electrostatic spinning apparatus
Presoma, spinning under conditions of 15~30cm of spinning distance, 10~30kV of spinning voltage, to be obtained on aluminium foil receiver board
PAN/Ni(Ac)2·4H2O/MoO2(acac)2Composite nano-fiber membrane；
(2) PAN/Ni (Ac) for obtaining step (1)2·4H2O/MoO2(acac)2Composite nano-fiber membrane is in air
1~3h is calcined under the conditions of 200~350 DEG C, 1~3h is then calcined under the conditions of argon atmosphere, 700~900 DEG C, to obtain this
Invention nickel-molybdenum carbide nanoparticle/carbon fiber (the Ni/Mo2C-CNFs) composite nano materials, product are in black thin film
Shape.
Nickel acetate in step (1) is also possible to other nickel salts such as nickel nitrate, nickel acetylacetonate, nickel chloride, nickel sulfate；Second
Acyl acetone molybdenum is also possible to other molybdenum salt such as hexacarbonylmolybdenum；The molecular weight of PAN is 100000~300000.
Nickel of the present invention-molybdenum carbide nanoparticle/carbon fiber composite nano materials can be used as bifunctional electrocatalyst
Catalytic hydrogen evolution and oxygen evolution reaction.Specifically nickel prepared by the present invention-molybdenum carbide nanoparticle/carbon fiber composite nano materials are surpassed
Sound is distributed to the dispersion liquid for being configured to that concentration is 2.0~6.0mg/mL in ethyl alcohol；Then 13.7~82.5 μ L dispersant liquid drops are existed
Diameter is to drip 1~5 μ L Nafion (0.5w.t.%) on its surface again after being completely dried on the rotating circular disk glass-carbon electrode of 5mm
Solution spontaneously dries in air, obtains catalyst-loaded glass-carbon electrode；The glass-carbon electrode prepared is carried out in electrolytic cell
Test, test system be three-electrode system (catalyst-loaded glass-carbon electrode be working electrode, carbon-point (being used for liberation of hydrogen test),
Platinum filament or platinized platinum (for analysing oxygen test) are to electrode, mercuric oxide electrode (Hg/HgO), saturated calomel electrode (SCE) or silver chlorate
Electrode (Ag/AgCl) is reference electrode), electrolyte is the KOH solution of 0.1~2.0mol/L.Before test, into electrolytic cell
Logical N2Or O2To saturation, N is remained in test process2Or O2Atmosphere.Liberation of hydrogen and oxygen evolution activity are evaluated, polarization curve survey is carried out
It tries (LSV), scanning speed is 5mV s-1, rotation speed 1600rpm.Nickel-molybdenum carbide nanoparticle/carbon fiber composite Nano material
Expect that liberation of hydrogen or oxygen evolution activity are better than many transition metal bifunctional electrocatalysts reported in the literature.
This method heavy industrialization application low in cost, simple and easy, achievable.Nickel-molybdenum carbide prepared by the present invention
Nanoparticle/carbon fiber composite nano materials have shown excellent catalysis as electro-catalysis water decomposition bifunctional electrocatalyst
Activity, overpotential needed for can greatly reducing water decomposition reaction, realizes and efficiently prepares free of contamination hydrogen energy source, to cope with increasingly
Serious environmental problem proposes new strategy, has important practical application value.
Detailed description of the invention
Fig. 1：The Ni/Mo prepared at 800 DEG C in embodiment 72The stereoscan photograph of C-CNFs-800 composite nano materials；
Fig. 2：The Ni/Mo prepared at 800 DEG C in embodiment 72The transmission electron microscope photo of C-CNFs-800 composite nano materials；
Fig. 3：The Ni/Mo prepared at 800 DEG C in embodiment 72The Raman spectrum of C-CNFs-800 composite nano materials；
Fig. 4：The Ni/Mo prepared at 800 DEG C in embodiment 72The X-ray diffraction spectrum of C-CNFs-800 composite nano materials
Figure；
Fig. 5：The Ni/Mo prepared at 800 DEG C in embodiment 72C-CNFs-800 composite nano materials catalyst is to liberation of hydrogen mistake
Polarization curve (j vs V) phenogram of journey.
Fig. 6：The Ni/Mo prepared at 800 DEG C in embodiment 72C-CNFs-800 composite nano materials catalyst is to analysis oxygen mistake
Polarization curve (j vs V) phenogram of journey.
As shown in Figure 1, the Ni/Mo prepared at 800 DEG C in embodiment 72The scanning electricity of C-CNFs-800 composite nano materials
Mirror photo, it can be seen that composite material generally fiber morphology, fibre diameter are about 100~310nm, and fiber surface is coarse,
There is the particle of protrusion.
As shown in Fig. 2, the Ni/Mo prepared at 800 DEG C in embodiment 72The transmission electricity of C-CNFs-800 composite nano materials
Mirror photo, it can be seen that fiber surface has small hole, nanoparticle is distributed in inside and outside carbon fiber, wherein biggish grain
Son is nickel nano particle, and lesser particle is molybdenum carbide nanoparticle.
As shown in figure 3, the Ni/Mo prepared at 800 DEG C in embodiment 72The Raman light of C-CNFs-800 composite nano materials
Spectrum.352cm-1、825cm-1、892cm-1And 945cm-1The characteristic peak at place corresponds to Mo-O-Ni extension vibration mode, shows Ni
And Mo2Interaction between C nano particle.1324cm-1And 1586cm-1The characteristic peak at place corresponds to D the and G band of carbon fiber
Characteristic peak.2655cm-1The characteristic peak at place corresponds to the characteristic peak of the 2D band of carbon fiber, 2901cm-1The characteristic peak at place corresponds to carbon
The peak D+G of fiber.
As shown in figure 4, the Ni/Mo prepared at 800 DEG C in embodiment 72The X-ray of C-CNFs-800 composite nano materials is spread out
Penetrate spectrogram, it can be seen that nickel prepared by the present invention-molybdenum carbide nanoparticle/carbon fiber respectively 34.6 °, 38.1 °, 39.6 °,
52.3 °, 61.9 °, 69.7 °, 74.9 ° and 75.7 ° there is Mo2(100) of C, (002), (101), (102), (110),
(103), the characteristic peak in (112) and (201) face occurs (111), (200) and (220) of Ni at 44.2 °, 51.4 ° and 75.8 °
The characteristic peak in face occurs the characteristic peak in (002) face of C at 26.0 °, it was demonstrated that the present invention is successfully prepared nickel-molybdenum carbide nanometer
Particle/carbon fiber composite nano materials.
As shown in figure 5, being the Ni/Mo prepared at 800 DEG C in embodiment 72C(1：2)-CNFs-800 composite nano materials
Alkaline liberation of hydrogen HER polarization curve (j vs V) phenogram.It can clearly be seen that Ni/Mo from figure2C-CNFs-800 is in electric current
Density reaches 10mA cm-2Shi Suoxu overpotential is -143mV, reaches 100mA cm in current density-2Shi Suoxu overpotential is only
For -195mV, this is the alkaline liberation of hydrogen catalyst in non-precious metal catalyst with lower overpotential, illustrates institute of the present invention
The nickel of preparation-molybdenum carbide nanoparticle/carbon fiber composite nano materials have excellent electrocatalytic hydrogen evolution activity.
As shown in fig. 6, being the Ni/Mo prepared at 800 DEG C in embodiment 72The alkalinity of C-CNFs-800 composite nano materials
Analyse oxygen OER polarization curve (j vs V) phenogram.It can clearly be seen that Ni/Mo from figure2C-CNFs-800 is in current density
Reach 10,100 and 200mA cm-2When, required overpotential is respectively 288,432 and 561mV, this is in non-precious metal catalyst
Alkaline oxygen-separating catalyst with lower overpotential illustrates that nickel prepared by the present invention-molybdenum carbide nanoparticle/carbon fiber is multiple
Closing nano material has excellent electro-catalysis oxygen evolution activity.
Specific embodiment
1, method of electrostatic spinning preparation PAN/Ni (Ac)2·4H2O/MoO2(acac)2Composite nano-fiber membrane
Embodiment 1：
0.2g PAN is dissolved in 2.3g DMF, magnetic agitation at 90 DEG C, after PAN all dissolution, by 0.067g Ni
(Ac)2·4H2O and 0.133g MoO2(acac)2It is dissolved in above-mentioned solution and being stirred overnight, obtain uniform thick shape spinning solution forerunner
Body.The injection spinning solution presoma in the glass spin duct of electrostatic spinning apparatus, spinning distance 20cm, spinning voltage 18kV, most
PAN/Ni (Ac) is obtained eventually2·4H2O/MoO2(acac)2Composite nano-fiber membrane.
Embodiment 2：
0.2g PAN is dissolved in 2.3g DMF, magnetic agitation at 90 DEG C, after PAN all dissolution, by 0.1g Ni
(Ac)2·4H2O and 0.1g MoO2(acac)2It is dissolved in above-mentioned solution and being stirred overnight, obtain uniform thick shape spinning solution forerunner
Body.The injection spinning solution presoma in the glass spin duct of electrostatic spinning apparatus, spinning distance 20cm, spinning voltage 18kV, most
PAN/Ni (Ac) is obtained eventually2·4H2O/MoO2(acac)2Composite nano-fiber membrane.
Embodiment 3：
0.2g PAN is dissolved in 2.3g DMF, magnetic agitation at 90 DEG C, after PAN all dissolution, by 0.133g Ni
(Ac)2·4H2O and 0.067g MoO2(acac)2It is dissolved in above-mentioned solution and being stirred overnight, obtain uniform thick shape spinning solution forerunner
Body.The injection spinning solution presoma in the glass spin duct of electrostatic spinning apparatus, spinning distance 20cm, spinning voltage 18kV, most
PAN/Ni (Ac) is obtained eventually2·4H2O/MoO2(acac)2Composite nano-fiber membrane.
Embodiment 4：
0.2g PAN is dissolved in 2.3g DMF, magnetic agitation at 90 DEG C, after PAN all dissolution, by 0.033g Ni
(Ac)2·4H2O and 0.067g MoO2(acac)2It is dissolved in above-mentioned solution and being stirred overnight, obtain uniform thick shape spinning solution forerunner
Body.The injection spinning solution presoma in the glass spin duct of electrostatic spinning apparatus, spinning distance 20cm, spinning voltage 18kV, most
PAN/Ni (Ac) is obtained eventually2·4H2O/MoO2(acac)2Composite nano-fiber membrane.
Embodiment 5：
0.2g PAN is dissolved in 2.3g DMF, magnetic agitation at 90 DEG C, after PAN all dissolution, by 0.133g Ni
(Ac)2·4H2O and 0.267g MoO2(acac)2It is dissolved in above-mentioned solution and being stirred overnight, obtain uniform thick shape spinning solution forerunner
Body.The injection spinning solution presoma in the glass spin duct of electrostatic spinning apparatus, spinning distance 20cm, spinning voltage 18kV, most
PAN/Ni (Ac) is obtained eventually2·4H2O/MoO2(acac)2Composite nano-fiber membrane.
2, air atmosphere calcining, inert atmosphere high-temperature calcination prepare Ni/Mo2C-CNFs composite nano materials
Embodiment 6：
The PAN/Ni (Ac) that embodiment 1 is obtained2·4H2O/MoO2(acac)2Composite nano-fiber membrane is by specifically forging
Burning process (first calcining 2h at 280 DEG C in air, then calcine 2h at 700 DEG C of argon atmosphere) is converted into Ni/Mo2C-
CNFs-700 composite nano materials, product are in black film-form.
Embodiment 7：
The PAN/Ni (Ac) that embodiment 1 is obtained2·4H2O/MoO2(acac)2Composite nano-fiber membrane is by specifically forging
Burning process (first calcining 2h at 280 DEG C in air, then calcine 2h at 800 DEG C of argon atmosphere) is converted into Ni/Mo2C-
CNFs-800 composite nano materials, product are in black film-form.
Embodiment 8：
The PAN/Ni (Ac) that embodiment 1 is obtained2·4H2O/MoO2(acac)2Composite nano-fiber membrane is by specifically forging
Burning process (first calcining 2h at 280 DEG C in air, then calcine 2h at 900 DEG C of argon atmosphere) is converted into Ni/Mo2C-
CNFs-900 composite nano materials, product are in black film-form.
Embodiment 9：
The PAN/Ni (Ac) that embodiment 2 is obtained2·4H2O/MoO2(acac)2Composite nano-fiber membrane is by specifically forging
Burning process (first calcining 2h at 280 DEG C in air, then calcine 2h at 800 DEG C of argon atmosphere) is converted into Ni/Mo2C-
CNFs-800 composite nano materials.Product is in black film-form.
Embodiment 10：
The PAN/Ni (Ac) that embodiment 3 is obtained2·4H2O/MoO2(acac)2Composite nano-fiber membrane is by specifically forging
Burning process (first calcining 2h at 280 DEG C in air, then calcine 2h at 800 DEG C of argon atmosphere) is converted into Ni/Mo2C-
CNFs-800 composite nano materials, product are in black film-form.
Embodiment 11：
The PAN/Ni (Ac) that embodiment 4 is obtained2·4H2O/MoO2(acac)2Composite nano-fiber membrane is by specifically forging
Burning process (first calcining 2h at 280 DEG C in air, then calcine 2h at 800 DEG C of argon atmosphere) is converted into Ni/Mo2C-
CNFs-800 composite nano materials, product are in black film-form.
Embodiment 12：
The PAN/Ni (Ac) that embodiment 5 is obtained2·4H2O/MoO2(acac)2Composite nano-fiber membrane is by specifically forging
Burning process (first calcining 2h at 280 DEG C in air, then calcine 2h at 800 DEG C of argon atmosphere) is converted into Ni/Mo2C-
CNFs-800 composite nano materials composite nano materials, product are in black film-form.
3、Ni/Mo2C-CNFs composite nano materials electrocatalytic hydrogen evolution property
Embodiment 13：
Product ultrasonic disperse calcined in embodiment 7 800 DEG C is configured to point that concentration is 4mg/mL into ethyl alcohol
Dispersion liquid；Then by 68.5 μ L dispersant liquid drops on the rotating circular disk glass-carbon electrode that diameter is 5mm, again on its surface after being completely dried
2.5 μ L Nafion (0.5w.t.%) solution are dripped, is spontaneously dried in air, obtains catalyst-loaded glass-carbon electrode.It will preparation
Good catalyst-loaded glass-carbon electrode is tested in electrolytic cell, and test system is that three-electrode system is (catalyst-loaded
Glass-carbon electrode is working electrode, and carbon-point is to electrode, and mercuric oxide electrode (Hg/HgO) is reference electrode), electrolyte 1mol/L
KOH solution.Before test, N is led into electrolytic cell2To saturation, N is remained in test process2Atmosphere.It is living to evaluate liberation of hydrogen
Property, it carries out polarization curve test (LSV), voltage scan range is -0.924~-1.124V, and scanning speed is 5mV s-1, rotation
Speed is 1600rpm.
4、Ni/Mo2Oxygen property is analysed in C-CNFs composite nano materials electro-catalysis
Embodiment 14：
Analysis oxygen test equally is carried out to calcined product at 800 DEG C in embodiment 7.Electrochemical test method and embodiment
13 is identical, and it is platinum electrode to electrode that difference, which is to change, and voltage scan range is 0.076~0.876V.
Claims (6)
1. a kind of nickel-molybdenum carbide nanoparticle/carbon fiber composite nano materials preparation method, its step are as follows：
(1) composite nano-fiber membrane is prepared by method of electrostatic spinning：Firstly, 0.1~0.3g polyacrylonitrile is dissolved in 1.0~4.0g
In n,N-Dimethylformamide, magnetic agitation at 80~100 DEG C, after polyacrylonitrile all dissolution, by 0.033~0.133g nickel
Salt and 0.067~0.267g molybdenum salt are dissolved in above-mentioned solution and being stirred overnight, and obtain uniform thick shape spinning solution presoma；In electrostatic
Spinning solution presoma is injected in the glass spin duct of device for spinning, in spinning distance 15~30cm, 10~30kV of spinning voltage
Under the conditions of spinning, to obtain composite nano-fiber membrane on aluminium foil receiver board；
(2) composite nano-fiber membrane for obtaining step (1) calcines 1~3h under the conditions of 200~350 DEG C in air, then exists
Argon atmosphere calcines 1~3h under the conditions of 700~900 DEG C, to obtain nickel-molybdenum carbide nanoparticle/carbon fiber Ni/Mo2C-
CNFs composite nano materials, product are in black film-form.
2. a kind of nickel-molybdenum carbide nanoparticle/carbon fiber composite nano materials preparation method as described in claim 1,
It is characterized in that：Nickel salt is nickel acetate, nickel nitrate, nickel acetylacetonate, nickel chloride or nickel sulfate.
3. a kind of nickel-molybdenum carbide nanoparticle/carbon fiber composite nano materials preparation method as described in claim 1,
It is characterized in that：Molybdenum salt is acetyl acetone or hexacarbonylmolybdenum.
4. a kind of nickel-molybdenum carbide nanoparticle/carbon fiber composite nano materials preparation method as described in claim 1,
It is characterized in that：The molecular weight of polyacrylonitrile is 100000~300000.
5. a kind of nickel-molybdenum carbide nanoparticle/carbon fiber composite nano materials, it is characterised in that：It is to be appointed by Claims 1 to 4
What the method is prepared.
6. nickel described in claim 5-molybdenum carbide nanoparticle/carbon fiber composite nano materials are in electrocatalytic hydrogen evolution or analysis oxygen
Application.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621969A (en) * | 2018-12-25 | 2019-04-16 | 江南大学 | A kind of self-supporting bimetallic nickel tungsten carbide complete solution water material and preparation method thereof |
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| WO2020134740A1 (en) * | 2018-12-24 | 2020-07-02 | 江南大学 | Electrolysed water catalytic material of platinum-doped carbide and preparation method thereof |
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| CN113652709A (en) * | 2021-07-07 | 2021-11-16 | 暨南大学 | Nitrogen-doped carbon nanotube-coated nickel iron/molybdenum carbide and preparation method and application thereof |
| CN113652709B (en) * | 2021-07-07 | 2023-01-17 | 暨南大学 | Nitrogen-doped carbon nanotube-coated nickel iron/molybdenum carbide and preparation method and application thereof |
| CN114031079A (en) * | 2021-11-03 | 2022-02-11 | 北京化工大学 | Molybdenum carbide carbon nanofiber composite material and preparation method and application thereof |
| CN114031079B (en) * | 2021-11-03 | 2023-10-27 | 北京化工大学 | Molybdenum carbide carbon nanofiber composite material and preparation method and application thereof |
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| CN116240577A (en) * | 2023-01-06 | 2023-06-09 | 成都大学 | Spherical mixed crystal nano-particles for electrocatalytic oxygen evolution and preparation method and application thereof |
| CN116240577B (en) * | 2023-01-06 | 2023-10-13 | 成都大学 | Spherical mixed crystal nano-particles for electrocatalytic oxygen evolution and preparation method and application thereof |
| CN116603561A (en) * | 2023-06-28 | 2023-08-18 | 湖南理工学院 | High-performance molybdenum-based electrolyzed water catalyst and preparation method and application thereof |
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