CN109967116A - A kind of preparation method of the Mo-VC nano-powder of carbon atomic layer cladding - Google Patents

A kind of preparation method of the Mo-VC nano-powder of carbon atomic layer cladding Download PDF

Info

Publication number
CN109967116A
CN109967116A CN201910322553.1A CN201910322553A CN109967116A CN 109967116 A CN109967116 A CN 109967116A CN 201910322553 A CN201910322553 A CN 201910322553A CN 109967116 A CN109967116 A CN 109967116A
Authority
CN
China
Prior art keywords
powder
nano
atomic layer
carbon atomic
layer cladding
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910322553.1A
Other languages
Chinese (zh)
Inventor
曹丽云
张宁
李晓艺
冯亮亮
黄剑锋
李嘉胤
冯永强
赵亚娟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201910322553.1A priority Critical patent/CN109967116A/en
Publication of CN109967116A publication Critical patent/CN109967116A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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

Abstract

A kind of preparation method of the Mo-VC nano-powder of carbon atomic layer cladding, is uniformly mixed to obtain reactant feed for dicyandiamide, ammonium metavanadate, ammonium molybdate and ammonium oxalate；Reactant feed is placed in porcelain boat, porcelain boat is put into high temperature process furnances, black powder is calcined to obtain under protective atmosphere；Black powder is moved into H2SO4Centrifuge separation；After the solid product vacuum drying after separation, grinding obtains the Mo-VC nano-powder of carbon atomic layer cladding.The present invention produces hydrogen elctro-catalyst as water-splitting using the Mo-VC nano-powder material that dicyandiamide, ammonium metavanadate, ammonium molybdate and ammonium oxalate prepare carbon atomic layer cladding as starting material, one-step calcination method.Since the intrinsic activity of catalyst is by Δ EH*(hydrogen combines energy) and Δ GH*(Gibbs free energy of H absorption) control, Mo element doping can change electronic structure and optimize Δ EH*With Δ GH*, so that electrocatalysis characteristic is excellent.

Description

A kind of preparation method of the Mo-VC nano-powder of carbon atomic layer cladding
Technical field
The present invention relates to nano-powder preparation fields, and in particular to a kind of Mo-VC nano-powder of carbon atomic layer cladding Preparation method.
Background technique
Hydrogen Energy is that have the renewable energy of bright prospects.Water-splitting hydrogen manufacturing is a kind of efficient production hydrogen means, and exploitation is high The production hydrogen catalyst of effect is the key that the technology.There is superior electric catalytic activity, but its by the noble metal catalyst of representative of Pt At high cost, stability is poor, it is difficult to investment large-scale production.And with transition metal base elctro-catalyst (with transition metal element, Carbon, sulphur, hydrogen, oxygen are essential element) it is that the effective exploitation of non-precious metal catalyst of representative can avoid the above problem well. In transition metal carbide (TMCs), relatively inexpensive VC has excellent hydrogen absorption property, with Mo2C is compared with WC, is had more Small density, makes it be more suitable for catalyst.However, due to its high synthesis temperature and uncontrollable pattern, VC sill Research as catalyst is less, especially produces the application in terms of hydrogen produces oxygen in water-splitting.Therefore exploitation VC base water-splitting produces hydrogen Elctro-catalyst, which is one, has challenge and the work of meaning.
Transition metal carbide catalytic activity with higher in HER, especially molybdenum carbide (MoxC), due to having with platinum There is similar d electronic structure, there is the catalysis behavior similar to noble metal.For example, Liu et al. is reported through ammonium molybdate and double cyanogen One step of the ammoxidation pyrolysis of amine can obtain the ultra-fine Mo of insertion enriched carbon layer2C nano particle [Liu, Y.；Yu,G.；Li,G.-D.； Sun,Y.；Asefa,T.；Chen,W.；Zou,X.Coupling Mo2C with Nitrogen-Rich Nanocarbon Leads to Efficient Hydrogen-Evolution Electrocatalytic Sites.Angew.Chem., Int.Ed.2015,54,10752-10757.].And MoxThe electric conductivity of C is poor, will affect the electron transport rate on electrode, from And its electro catalytic activity is limited, if both can reveal that and more urged by designing unique nanostructure, synthesis VC sill etc. Change active site, can also effectively solve the problems such as its electric conductivity is weak.
Summary of the invention
It is prepared the purpose of the present invention is to provide a kind of preparation method of the Mo-VC nano-powder of carbon atomic layer cladding Material chemical constituent it is uniform, form equally distributed nanoscale VC particle, stable structure, good conductivity.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
1) by dicyandiamide, ammonium metavanadate, ammonium molybdate and ammonium oxalate with (5~25): (2~10): (1~7): the matter of (1~2) Amount is than being uniformly mixed to obtain reactant feed；
2) reactant feed is placed in porcelain boat, porcelain boat is put into high temperature process furnances, under protective atmosphere, with 3 DEG C/min Heating rate be warming up to 500~1000 DEG C from room temperature to 50 DEG C, then with the heating rate of 5~10 DEG C/min, heat preservation 1~ 2h, cooling black powder；
3) black powder is moved into the H of 0.5mol/L2SO4In, immersion 12~be centrifugated afterwards for 24 hours；
4) by after the solid product vacuum drying after separation, grinding obtains the Mo-VC nano-powder of carbon atomic layer cladding.
The reactant feed of the step 1) is through being fully ground to obtain.
The protective atmosphere of the step 2) is H2Or Ar.
The present invention prepares carbon by starting material, one-step calcination method of dicyandiamide, ammonium metavanadate, ammonium molybdate and ammonium oxalate The Mo-VC nano-powder material of atomic layer cladding produces hydrogen elctro-catalyst as water-splitting.Since the intrinsic activity of catalyst is by Δ EH*(hydrogen combines energy) and Δ GH*(Gibbs free energy of H absorption) control, Mo element doping can change electronic structure and optimize ΔEH*With Δ GH*, so that electrocatalysis characteristic is excellent.Materials chemistry is obtained using calcination method and forms uniform, equally distributed nanometer Grade VC particle, stable structure, good conductivity have certain electrocatalysis, can be used for Electrocatalytic Activity for Hydrogen Evolution Reaction field.
Compared with prior art, the invention has the following beneficial technical effects:
1) introducing of molybdenum atom is the key that the structural generation in raw material, and Mo element doping can change electronic structure and excellent Change Δ EH*With Δ GH*, further improve HER electrocatalysis characteristic；
2) dicyandiamide is rich in nitrogen, so that the N doping content of the Mo-VC of the carbon atomic layer cladding of preparation is high, is conducive to The activity of catalyst improves.
Detailed description of the invention
Fig. 1 is the XRD diagram of VC@CL prepared by the embodiment of the present invention 1；
The TEM figure that Fig. 2 is VC@CL prepared by the embodiment of the present invention 3；
The LSV figure that Fig. 3 is VC@CL prepared by the embodiment of the present invention 4.
Specific embodiment
With reference to the accompanying drawing and embodiment invention is further described in detail.
Embodiment 1:
1) dicyandiamide, ammonium metavanadate, ammonium molybdate and ammonium oxalate are mixed with the mass ratio of 5:2:1:1 and is fully ground to obtain reaction Raw material；
2) reactant feed is placed in porcelain boat, porcelain boat is put into high temperature process furnances, in H2Under protective atmosphere, with 3 DEG C/ The heating rate of min is warming up to 500 DEG C from room temperature to 50 DEG C, then with the heating rate of 5 DEG C/min, keeps the temperature 2h, cooling Black powder；
3) black powder is moved into the H of 0.5mol/L2SO4In, it is centrifugated after impregnating 12h；
4) by after the solid product vacuum drying after separation, grinding obtains the Mo-VC nano-powder of carbon atomic layer cladding.
The corresponding VC of Mo-VC nano-powder material of the cladding of carbon atomic layer prepared by the present embodiment as seen from Figure 1 Standard PDF card number is 73-0476, and five diffraction maximums respectively correspond crystal face (111), (200), (220), (311) and (222), Diffraction maximum is sharp, and intensity is high, and the VC crystallinity for illustrating that the embodiment obtains is fine, and position shows graphite in 26 ° of diffraction maximum Change the presence of carbon.
Embodiment 2:
1) mixing dicyandiamide, ammonium metavanadate, ammonium molybdate and ammonium oxalate with the mass ratio of 15:5:3:1 is fully ground instead Answer raw material；
2) reactant feed is placed in porcelain boat, porcelain boat is put into high temperature process furnances, in H2Under protective atmosphere, with 3 DEG C/ The heating rate of min is warming up to 700 DEG C from room temperature to 50 DEG C, then with the heating rate of 5 DEG C/min, keeps the temperature 2h, cooling Black powder；
3) black powder is moved into the H of 0.5mol/L2SO4In, it is centrifugated after impregnating 16h；
4) by after the solid product vacuum drying after separation, grinding obtains the Mo-VC nano-powder of carbon atomic layer cladding.
Embodiment 3:
1) mixing dicyandiamide, ammonium metavanadate, ammonium molybdate and ammonium oxalate with the mass ratio of 20:8:5:2 is fully ground instead Answer raw material；
2) reactant feed is placed in porcelain boat, porcelain boat is put into high temperature process furnances, in H2Under protective atmosphere, with 3 DEG C/ The heating rate of min is warming up to 900 DEG C from room temperature to 50 DEG C, then with the heating rate of 10 DEG C/min, keeps the temperature 1h, cooling Black powder；
3) black powder is moved into the H of 0.5mol/L2SO4In, it is centrifugated after impregnating 20h；
4) by after the solid product vacuum drying after separation, grinding obtains the Mo-VC nano-powder of carbon atomic layer cladding.
The Mo-VC nano-powder material microstructure of prepared prepared carbon atomic layer cladding as seen from Figure 2 For the vanadium carbide of carbon atomic layer cladding, vanadium carbide partial size is small, and lattice fringe is obvious, illustrates for graphitic carbon, consistent with XRD result.
Embodiment 4:
1) mixing dicyandiamide, ammonium metavanadate, ammonium molybdate and ammonium oxalate with the mass ratio of 25:10:7:2 is fully ground instead Answer raw material；
2) reactant feed is placed in porcelain boat, porcelain boat is put into high temperature process furnances, under Ar protective atmosphere, with 3 DEG C/ The heating rate of min is warming up to 1000 DEG C from room temperature to 50 DEG C, then with the heating rate of 10 DEG C/min, keeps the temperature 1h, cooling Obtain black powder；
3) black powder is moved into the H of 0.5mol/L2SO4In, immersion is centrifugated afterwards for 24 hours；
4) by after the solid product vacuum drying after separation, grinding obtains the Mo-VC nano-powder of carbon atomic layer cladding.
Fig. 3 is that the Mo-VC of the cladding of carbon atomic layer prepared by the present embodiment produces the LSV figure of hydrogen elctro-catalyst, indicates pH 14 Under test condition, when current density is 10mA/cm2, when sweep speed is 3mV/s, which is 177mV, illustrates sample It is excellent that the catalysis of product produces hydrogen activity.
Embodiment 5:
1) dicyandiamide, ammonium metavanadate, ammonium molybdate and ammonium oxalate are mixed with the mass ratio of 10:3:2:1.5 and is fully ground Reactant feed；
2) reactant feed is placed in porcelain boat, porcelain boat is put into high temperature process furnances, in H2Under protective atmosphere, with 3 DEG C/ The heating rate of min is warming up to 800 DEG C from room temperature to 50 DEG C, then with the heating rate of 8 DEG C/min, keeps the temperature 1.5h, cooling Obtain black powder；
3) black powder is moved into the H of 0.5mol/L2SO4In, it is centrifugated after impregnating 20h；
4) by after the solid product vacuum drying after separation, grinding obtains the Mo-VC nano-powder of carbon atomic layer cladding.

Claims (3)

1. a kind of preparation method of the Mo-VC nano-powder of carbon atomic layer cladding, it is characterised in that the following steps are included:
1) by dicyandiamide, ammonium metavanadate, ammonium molybdate and ammonium oxalate with (5~25): (2~10): (1~7): the mass ratio of (1~2) It is uniformly mixed to obtain reactant feed；
2) reactant feed is placed in porcelain boat, porcelain boat is put into high temperature process furnances, under protective atmosphere, with the liter of 3 DEG C/min Warm rate is warming up to 500~1000 DEG C from room temperature to 50 DEG C, then with the heating rate of 5~10 DEG C/min, keeps the temperature 1~2h, Cooling black powder；
3) black powder is moved into the H of 0.5mol/L2SO4In, immersion 12~be centrifugated afterwards for 24 hours；
4) by after the solid product vacuum drying after separation, grinding obtains the Mo-VC nano-powder of carbon atomic layer cladding.
2. the preparation method of the Mo-VC nano-powder of carbon atomic layer cladding according to claim 1, it is characterised in that: institute The reactant feed of step 1) is stated through being fully ground to obtain.
3. the preparation method of the Mo-VC nano-powder of carbon atomic layer cladding according to claim 1, it is characterised in that: institute The protective atmosphere for stating step 2) is H2Or Ar.
CN201910322553.1A 2019-04-22 2019-04-22 A kind of preparation method of the Mo-VC nano-powder of carbon atomic layer cladding Pending CN109967116A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910322553.1A CN109967116A (en) 2019-04-22 2019-04-22 A kind of preparation method of the Mo-VC nano-powder of carbon atomic layer cladding

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910322553.1A CN109967116A (en) 2019-04-22 2019-04-22 A kind of preparation method of the Mo-VC nano-powder of carbon atomic layer cladding

Publications (1)

Publication Number Publication Date
CN109967116A true CN109967116A (en) 2019-07-05

Family

ID=67085535

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910322553.1A Pending CN109967116A (en) 2019-04-22 2019-04-22 A kind of preparation method of the Mo-VC nano-powder of carbon atomic layer cladding

Country Status (1)

Country Link
CN (1) CN109967116A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114645284A (en) * 2020-12-15 2022-06-21 陕西科技大学 Three-phase system vanadium trioxide/vanadium nitride/molybdenum carbide nano electrode material and preparation method and application thereof
CN114645283A (en) * 2020-12-15 2022-06-21 陕西科技大学 High-efficiency vanadium nitride/molybdenum carbide heterojunction hydrogen production electrocatalyst and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109592683A (en) * 2019-01-24 2019-04-09 陕西科技大学 A kind of extra small vanadium carbide insertion carbon atomic layer material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109592683A (en) * 2019-01-24 2019-04-09 陕西科技大学 A kind of extra small vanadium carbide insertion carbon atomic layer material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ELISA NAVARRO-FLORES ET AL.: ""Characterization of Ni, NiMo, NiW and NiFe electroactive coatings as electrocatalysts for hydrogen evolution in an acidic medium"", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL 226》 *
YIQIANG SUN ET AL.: ""Mo doped Ni2P nanowire arrays: an efficient electrocatalyst for the hydrogen evolution reaction with enhanced activity at all pH values"", 《NANOSCALE》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114645284A (en) * 2020-12-15 2022-06-21 陕西科技大学 Three-phase system vanadium trioxide/vanadium nitride/molybdenum carbide nano electrode material and preparation method and application thereof
CN114645283A (en) * 2020-12-15 2022-06-21 陕西科技大学 High-efficiency vanadium nitride/molybdenum carbide heterojunction hydrogen production electrocatalyst and preparation method and application thereof
CN114645284B (en) * 2020-12-15 2023-11-24 陕西科技大学 Three-phase system vanadium trioxide/vanadium nitride/molybdenum carbide nano electrode material and preparation method and application thereof
CN114645283B (en) * 2020-12-15 2024-02-09 陕西科技大学 High-efficiency vanadium nitride/molybdenum carbide heterojunction hydrogen-producing electrocatalyst and preparation method and application thereof

Similar Documents

Publication Publication Date Title
Li et al. Spinel LiMn2O4 nanofiber: an efficient electrocatalyst for N2 reduction to NH3 under ambient conditions
CN109841854B (en) Nitrogen-doped carbon-supported monatomic oxygen reduction catalyst and preparation method thereof
Li et al. Fe-doped CoSe2 nanoparticles encapsulated in N-doped bamboo-like carbon nanotubes as an efficient electrocatalyst for oxygen evolution reaction
CN109524678B (en) Oxygen evolution iron-cobalt alloy-cobalt ferrite/nitrogen doped carbon nanotube composite catalyst and preparation method and application thereof
CN105107540B (en) Nitrogen-doped carbon nanotube nickel-iron coated oxygen evolution catalytic material for water electrolysis and application
CN106229521B (en) A kind of FeCx@NC catalyst with core-casing structure and preparation method thereof
CN109248703B (en) Loaded Ni3Preparation method of Fe nitrogen-doped carbon nanocomposite material, and obtained material and application thereof
CN111346640B (en) Transition metal monoatomic-supported electrolyzed water catalyst and preparation method thereof
CN107681166B (en) Method for preparing carbon catalyst by inducing Fe-N growth through carbon template and carbon catalyst
CN109701545A (en) A kind of electrocatalysis material and preparation method thereof loading vanadium cobalt alloy nanoparticles
Zhang et al. Engineering electrocatalytic fiber architectures
CN108611658A (en) A kind of one-dimensional porous nano composite material and preparation method and the application in electrolysis water
Huang et al. Ni activated Mo2C nanoparticles supported on stereotaxically-constructed graphene for efficient overall water splitting
Yesudoss et al. Accelerated N2 reduction kinetics in hybrid interfaces of nbtio4 and nitrogen-doped carbon nanorod via synergistic electronic coupling effect
CN106450354A (en) Hydrothermal synthesis method for nitrogen-doping graphene-loaded cobalt oxygen reduction reaction electrocatalyst
CN108550471B (en) A kind of carbon fiber flexible electrode material and preparation method thereof
CN111068717B (en) Ruthenium simple substance modified sulfur-doped graphene two-dimensional material and preparation and application thereof
Xu et al. Semi‐metal 1T′ phase MoS2 nanosheets for promoted electrocatalytic nitrogen reduction
CN112725819A (en) Tungsten-molybdenum-based nitrogen carbide nano material and preparation method and application thereof
CN109967116A (en) A kind of preparation method of the Mo-VC nano-powder of carbon atomic layer cladding
Amarnath et al. Phase-Pure High-Entropy Spinel Oxide (Ni, Fe, Mn, Cu, Zn) 3O4 via Thermal Plasma: A Promising Electrocatalyst for Oxygen Evolution Reaction
Yang et al. Achieving enhanced electrocatalytic performance towards hydrogen evolution of molybdenum carbide via morphological control
CN114164445A (en) V-Ni constructed based on doping and heterojunction strategies3FeN/Ni @ N-GTs full-electrolysis water-electric catalyst
CN111013619B (en) Molybdenum carbide nanorod for catalyst and preparation method and application thereof
CN105833871B (en) A kind of cobalt of richness defect inlays carbon nanotube, preparation method and applications

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20190705