CN109926082A - A kind of carbon coating nickel oxide molybdenum composite material and preparation method thereof - Google Patents
A kind of carbon coating nickel oxide molybdenum composite material and preparation method thereof Download PDFInfo
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- CN109926082A CN109926082A CN201910223899.6A CN201910223899A CN109926082A CN 109926082 A CN109926082 A CN 109926082A CN 201910223899 A CN201910223899 A CN 201910223899A CN 109926082 A CN109926082 A CN 109926082A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention provides a kind of carbon coating nickel oxide molybdenum composite material and preparation method thereof.For the material to nitrogenize nickel-molybdenum alloy as kernel, carbon-coating of the thickness less than 10 nanometers is the composite material of shell.The specific preparation step of the material includes: to prepare NiMoO by hydro-thermal method4Solid, by NiMoO4Solid is uniformly mixed with the organic solid of nitrogenous carbon, is heated to 500 ~ 1000 DEG C under protection of argon gas, and Temperature fall after 20 ~ 300 min of constant temperature obtains carbon coating nickel oxide molybdenum composite material.Preparation method is simple by the present invention, and in high-temperature heat treatment process, carbon containing nitrogen organic decomposes the carbon species generated and restores NiMoO4, while the nitrogen for decomposing generation penetrates into and generates NiMoN alloy phase, the Carbon deposition cladding being then decomposed.Carbon-coating densification is covered in nitridation nickel-molybdenum alloy phase in gained composite material, realizes the protective value excellent to its, and ultra-thin carbon-coating does not limit the performance of NiMoN catalytic performance, provides a kind of anti-corrosion composite functional material.
Description
Technical field
The invention belongs to advanced composite material (ACM) field more particularly to a kind of carbon coating nickel oxide molybdenum composite material and its preparations
Method.
Background technique
Nickel oxide molybdenum (nickel molybdenum nitride) has been widely used in electrochemistry, petrochemical industry and magnetic fields tool.Such as
NiMoN can be used for being catalyzed oil product heavy aromatics saturated hydrogenation, can be used for the cathode for hydrogen evolution electrode material of water electrolysis hydrogen production.Chen Zheng
(cobalt-base catalyst, the preparation of nickel molybdenum nitrogen electrocatalysis material and its research of the aqueous energy of electrocatalytic decomposition, academic dissertation, Nanjing are big
Learn) report it is a kind of using NH3High temperature reduction nitrogenizes NiMoO4The method for obtaining NiMoN compound, has simultaneously in alkaline solution
Standby preferable hydrogen evolution activity and oxygen evolution activity.But the NH that this method uses3Have inflammable and explosive and toxicity higher at high temperature
The shortcomings that, it is unfavorable for industrialization promotion use, in addition, NiMoN compound still cannot effectively avoid surface oxidation bring negative
Face is rung, thus is mainly used under alkaline condition.Document (Highly efficient and durable MoNiNC
Catalyst for hydrogen evolution reaction. Nano Energy 2017,37,1-6.) report one
Kind pyrocarbon heat-ammonia reduction prepares molybdenum nickel bimetal carboritride (MoNiNC) catalyst, reaches 10 in liberation of hydrogen electric current
When mAcm-2, overpotential is only 110 mV, presents the electrocatalysis characteristic close to business Pt.But it is also used in this method
NH3Presoma as nitridation.
At present it has been reported that method in, largely need using NH3As the raw material for realizing NiMo nitridation, and can not be real
Now to the anti-oxidant and thorough protection of NiMoN.Not yet have been reported that a kind of thin layer carbon coating nickel oxide molybdenum composite material and its preparation
Method.
Summary of the invention
In view of problem above, the purpose of the present invention is to provide a kind of carbon coating nickel oxide molybdenum composite material and its preparation sides
Method, this method have non precious metal element, use without ammonia, feature simple and easy to do, at low cost.
The core technical features that the present invention is different from existing nickel oxide molybdenum material are: to nitrogenize nickel-molybdenum alloy as kernel,
Carbon-coating using thickness less than 10 nanometers realizes the protective value excellent to nickel oxide molybdenum as the composite material of shell, and ultra-thin
Carbon-coating do not limit the performance of NiMoN catalytic performance again.Carbon coating nickel oxide molybdenum composite material of the present invention is by following technology
Scheme is realized:
(1) using sodium molybdate or ammonium molybdate as molybdenum salt, with one of nickel chloride, nickel nitrate, nickel sulfate or nickel acetate for nickel salt, lead to
90 ~ 180 DEG C of hydro-thermal process 3-24 h are crossed, NiMoO is prepared4Deposit.
(2) by NiMoO4After deposit filtration washing, in 60 ~ 150 DEG C of 1 ~ 12 h of drying, after obtain NiMoO4Solid.
(3) by one of melamine, dicyandiamide, urea, polypyrrole, polyaniline or a variety of itrogenous organic substance solids,
With NiMoO4After solid mixed grinding is uniform, be heated under hydrogen and argon gas mixed gas or the protection of simple argon gas 500 DEG C ~
1000 DEG C, Temperature fall after 20 ~ 300 min of constant temperature obtains carbon coating nickel oxide molybdenum composite material.
Various specific chemical names in above-mentioned bracket are to provide specific example, and but not limited to this.
The advantages of technical solution of the present invention, is, using melamine, dicyandiamide, urea, polypyrrole or polyaniline conduct
Itrogenous organic substance solid and NiMoO4Pyroreaction is carried out, nitrogenous carbon organic solid compound decomposes the carburetted hydrogen gas for generating reproducibility
Body is by NiMoO4When reduction, while the nitrogen for decomposing generation penetrates into NiMo intermediate product, and generates NiMoN alloy phase, then by
Decompose protective effect of the carbon-coating cladding realization of deposition to NiMoN.
Good effect of the present invention is as follows:
(1) carbon coating nickel oxide molybdenum composite material being prepared using easy hydro-thermal reaction and high temperature pyrolysis process, method is simple,
It is convenient to operate, convenient for amplification.
(2) using melamine, dicyandiamide, urea, polypyrrole or the polyaniline of solid as nitrogen, carbon source, a step high temperature
Process realizes the heavy carbon of reduction-nitriding-, not only avoids NH in nickel molybdenum nitridation process3Use, improve safety, also simplify
Preparation flow.
(3) using prepared carbon coating nickel oxide molybdenum composite material as hydrogen evolution electrode material, in sulfuric acid solution and hydrogen
Excellent electrocatalytic hydrogen evolution performance is presented in sodium hydroxide solution, liberation of hydrogen current density reaches 10 mA cm-2Overpotential is small
In 50 mV.Even if after high potential oxidation, similar Hydrogen Evolution Performance before still having and aoxidizing presents excellent resist
Oxidation susceptibility is also expected to as other function material.
Detailed description of the invention
Fig. 1 is the high-resolution transmission plot of carbon coating nickel oxide molybdenum composite material prepared by the present invention.
Specific embodiment
Technical characteristic in order to better illustrate the present invention is illustrated below by specific embodiment
Embodiment 1
Configure 0.04 M Ni(NO3)2·6H2O and 0.01M (NH4)6Mo7O24·4H2The mixed solution of O measures 200 mL and is placed in
In reaction kettle, cooled to room temperature after constant temperature 6 hours is warming up at 150 DEG C.Three times by the solid filtration washing in reaction kettle
Afterwards, it is transferred in baking oven, is warming up to 6 h of freeze-day with constant temperature at 180 DEG C.2 g NiMoO4 solids and the bis- cyanogen of 5 g after weighing drying
Amine solid, ground and mixed are uniform.NiMoO4- dicyandiamide hybrid solid is placed in crucible, and is put into tube furnace, is passed through argon gas,
700 DEG C are warming up to 10 DEG C/min, starts Temperature fall after keeping constant temperature 2h.After dropping to room temperature, taking-up obtains carbon coating nitridation
Nickel molybdenum composite material.Using this composite material as cathode for hydrogen evolution catalyst, when electric current reaches 10mAcm-2 in 1 M KOH, mistake
Current potential is only 42 mV;After the positive 1.5V high potential oxidation of reference reversible hydrogen electrode, re-test Hydrogen Evolution Performance, overpotential is also only
43 mV.When electric current reaches 10mAcm-2 in 0.5 M H2SO4, overpotential is 38 mV;Show good electrocatalytic hydrogen evolution
Activity and antioxygenic property.
Attached drawing 1 is the high resolution electron microscopy figure of carbon coating nickel oxide molybdenum composite material prepared by the present embodiment 1.It is respectively in figure
(1,0, the 1) crystal face of NiMoN and (0,0,2) crystal face of carbon, and NiMoN outer layer is coated by very thin carbon-coating.
Embodiment 2
Configure 0.05M Ni(NO3)2·6H2O and 0.01M (NH4)6Mo7O24·4H2The mixed solution of O measures 200 mL and is placed in
In reaction kettle, cooled to room temperature after constant temperature 3 hours is warming up at 180 DEG C.Three times by the solid filtration washing in reaction kettle
Afterwards, it is transferred in baking oven, is warming up to 6 h of freeze-day with constant temperature at 180 DEG C.2 g NiMoO4 solids and 3g melamine after weighing drying
Amine solid, ground and mixed are uniform.NiMoO4- dicyandiamide hybrid solid is placed in crucible, and is put into tube furnace, is passed through argon gas,
700 DEG C are warming up to 10 DEG C/min, starts Temperature fall after keeping constant temperature 1h.After dropping to room temperature, taking-up obtains carbon coating nitridation
Nickel molybdenum composite material.Using this composite material as cathode for hydrogen evolution catalyst, when electric current reaches 10mAcm-2 in 1 M KOH, mistake
Current potential is only 38 mV;After the positive 1.5V high potential oxidation of reference reversible hydrogen electrode, re-test Hydrogen Evolution Performance, overpotential is also only
40 mV.When electric current reaches 10mAcm-2 in 0.5 M H2SO4, overpotential 36mV;It is living to show good electrocatalytic hydrogen evolution
Property and antioxygenic property.
Embodiment 3
Configure 0.06M Ni(NO3)2·6H2O and 0.01M (NH4)6Mo7O24·4H2The mixed solution of O measures 400 mL and is placed in
In reaction kettle, cooled to room temperature after constant temperature 4 hours is warming up at 160 DEG C.By the solid filtration washing three in reaction kettle
It after secondary, is transferred in baking oven, is warming up to 6 h of freeze-day with constant temperature at 180 DEG C.3 g NiMoO4 solids and 10 g after weighing drying
Polyaniline solids, ground and mixed are uniform.NiMoO4- dicyandiamide hybrid solid is placed in crucible, and is put into tube furnace, is passed through argon
Gas is warming up to 800 DEG C with 10 DEG C/min, starts Temperature fall after keeping constant temperature 1h.After dropping to room temperature, taking-up obtains carbon coating nitrogen
Change nickel molybdenum composite material.Using this composite material as cathode for hydrogen evolution catalyst, when electric current reaches 10mAcm-2 in 1 M KOH,
Overpotential is only 46 mV;After the positive 1.5V high potential oxidation of reference reversible hydrogen electrode, re-test Hydrogen Evolution Performance, overpotential 45
mV.When electric current reaches 10 mAcm-2 in 0.5 M H2SO4, overpotential is 41 mV;It is living to show good electrocatalytic hydrogen evolution
Property and antioxygenic property.
Claims (3)
1. a kind of carbon coating nickel oxide molybdenum composite material, it is characterised in that: to nitrogenize nickel-molybdenum alloy as kernel, with thickness less than 10
The carbon-coating of nanometer is the composite material of core-shell structure of shell building;The specific preparation step of the material includes:
(1) using sodium molybdate or ammonium molybdate as molybdenum salt, with one of nickel chloride, nickel nitrate, nickel sulfate or nickel acetate for nickel salt, lead to
90 ~ 180 DEG C of hydro-thermal process 3-24 h are crossed, NiMoO is prepared4Deposit;
(2) by NiMoO4After deposit filtration washing, in 60 ~ 150 DEG C of 1 ~ 12 h of drying, after obtain NiMoO4Solid;
(3) by one of melamine, dicyandiamide, urea, polypyrrole, polyaniline or a variety of itrogenous organic substance solids, with
NiMoO4After solid mixed grinding is uniform, 500 DEG C ~ 1000 are heated under hydrogen and argon gas mixed gas or the protection of simple argon gas
DEG C, Temperature fall after 20 ~ 300 min of constant temperature obtains carbon coating nickel oxide molybdenum composite material.
2. carbon coating nickel oxide molybdenum composite material as described in claim 1, which is characterized in that in step (1) the nickel salt with
Nickel molybdenum element content molar ratio range is 0.25 to 4 in molybdenum salt.
3. carbon coating nickel oxide molybdenum composite material as described in claim 1, which is characterized in that the carbon containing nitrogen described in step (2)
Organic matter accounts for NiMoO4Quality is 0.2 ~ 10 than range.
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Cited By (3)
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CN110391428A (en) * | 2019-08-07 | 2019-10-29 | 吉林大学 | Self-supporting nanoporous Mo/Mo2N@Ni3Mo3N composite material and preparation method and application |
CN113912009A (en) * | 2021-11-24 | 2022-01-11 | 北京化工大学 | Electrochemical method for controlling on-off of hydrogen production by hydrolysis reaction |
CN115044920A (en) * | 2022-08-16 | 2022-09-13 | 河南师范大学 | Preparation method of self-supporting ultralow-crystallinity nano-array electrocatalyst for hydrogen production by water electrolysis |
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CN109300703A (en) * | 2018-12-04 | 2019-02-01 | 浙江理工大学 | Cobalt nickel bimetal hydroxide nano piece/nitridation carbon coating N doping hollow graphite alkene ball composite material and preparation method and application |
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A. GOMATHI: "Ternary metal nitrides by the urea route", 《MATERIALS RESEARCH BULLETIN》 * |
ZHE LV ET AL: "Well-dispersed molybdenum nitrides on a nitrogen-doped carbon matrix for highly efficient hydrogen evolution in alkaline media", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110391428A (en) * | 2019-08-07 | 2019-10-29 | 吉林大学 | Self-supporting nanoporous Mo/Mo2N@Ni3Mo3N composite material and preparation method and application |
CN110391428B (en) * | 2019-08-07 | 2022-05-10 | 吉林大学 | Self-supporting nanoporous Mo/Mo2N@Ni3Mo3N composite material and preparation method and application thereof |
CN113912009A (en) * | 2021-11-24 | 2022-01-11 | 北京化工大学 | Electrochemical method for controlling on-off of hydrogen production by hydrolysis reaction |
CN113912009B (en) * | 2021-11-24 | 2023-11-21 | 北京化工大学 | Electrochemical method for controlling hydrogen production on and off by hydrolysis reaction |
CN115044920A (en) * | 2022-08-16 | 2022-09-13 | 河南师范大学 | Preparation method of self-supporting ultralow-crystallinity nano-array electrocatalyst for hydrogen production by water electrolysis |
CN115044920B (en) * | 2022-08-16 | 2022-11-01 | 河南师范大学 | Preparation method of self-supporting ultralow-crystallinity nano-array electrocatalyst for hydrogen production by water electrolysis |
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