CN109759103A - A kind of preparation method of the molybdenum carbide nanometer sheet of nickel doping - Google Patents
A kind of preparation method of the molybdenum carbide nanometer sheet of nickel doping Download PDFInfo
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- CN109759103A CN109759103A CN201910088084.1A CN201910088084A CN109759103A CN 109759103 A CN109759103 A CN 109759103A CN 201910088084 A CN201910088084 A CN 201910088084A CN 109759103 A CN109759103 A CN 109759103A
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- 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
The preparation method of the molybdenum carbide nanometer sheet of a kind of nickel doping, it is characterised in that: specifically include following steps, it is dissolved in deionized water respectively, is respectively labeled as solution A and B by S1, firstly, weighing suitable ammonium molybdate and nickel nitrate；Again in the case of stirring, solution B is slowly added into solution A；Sodium hydroxide solution is slowly added dropwise in S2, the mixed solution into step S1, carries out pH adjusting, is adjusted between 9-10 to pH, the mixed solution is transferred in hydrothermal reaction kettle later, carries out hydro-thermal process；After S3, hydro-thermal reaction, centrifuge washing and drying are carried out to product, obtain lurid powdery product；The powdery product is made after being grinded with a mortar again, uniformly paving is dispersed in corundum boat, is put into tube furnace and carries out carburizing sintering；S4, by the product cooled to room temperature after carburizing sintering in step S3, again centrifuge washing and drying, so that it may obtain the molybdenum carbide nanometer sheet of nickel doping.
Description
Technical field
The present invention relates to electrolysis waters to prepare hydrogen field, especially electrolysis water evolving hydrogen reaction, is particularly used for electrolysis water
The preparation of elctro-catalyst in evolving hydrogen reaction.
Background technique
It is for the demand of clean energy resource also more more and more urgent as environment, energy problem get worse.Numerous clear
In the clean energy, hydrogen is due to becoming a kind of very popular research object with very high energy density and widest distribution.
Unfortunately, hydrogen is not to exist with molecular state in nature, this means that need people to convert it after
It can use.
Currently, the method for more efficiently preparing hydrogen is electrolysis aquatic products hydrogen, hydrogen can be prepared by this method simultaneously
HER reaction can occur in electrolytic cell for gas and oxygen.For HER reaction, due to having the reality much higher than theoretical overpotential
Border overpotential, for this purpose, indispensable in HER reaction using efficient elctro-catalyst.Common effective catalyst is noble metal
Base catalyst, such as Pt, Rh and Pd, they have lower overpotential and low Tafel slope, but these noble metal catalysts,
It is limited to its factor such as content and cost in the earth's crust, it is difficult to be widely popularized in practical applications.In order to solve this problem, section
It grinds personnel to develop with reference to the catalyst of other systems, and develops the electrocatalysis material of other matrix, such as transition metal phosphatization
Object (MoP, CoNiP etc.), transient metal sulfide (MoS2、Ni3S2Deng), transition metal hydroxide (LDHs) etc..In addition to opening
The catalyst material of different systems is issued, in order to further increase the comprehensive performance of electrocatalyst materials, researcher is also in electricity
Other hetero atoms are introduced in catalyst preparation process, to realize to the part substitution of meta-element or impurity, by this
The electrocatalyst materials that method is prepared show more preferably electrocatalysis characteristic.For this purpose, in existing a variety of doped sources,
Select suitable doped source and basis material, by reasonable method to obtain efficient elctro-catalyst be still one very
Important research topic.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of the molybdenum carbide nanometer sheet of nickel doping, and the present invention is for the first time in carbon
Change in molybdenum nanometer sheet and introduce hetero atom nickel, nickle atom combination molybdenum carbide nanometer sheet shows efficient electrocatalysis characteristic.
Specifically, the present invention is to achieve the object of the present invention by the following technical solutions.
A kind of preparation method of the molybdenum carbide nanometer sheet of nickel doping, specifically includes the following steps:
S1, firstly, weighing suitable ammonium molybdate and nickel nitrate, it is dissolved in deionized water respectively, is respectively labeled as solution A
And B；Again in the case of stirring, solution B is slowly added into solution A；
Be slowly added dropwise sodium hydroxide solution in S2, the mixed solution into step S1, carry out pH adjusting, to pH be adjusted to 9-10 it
Between, the mixed solution is transferred in hydrothermal reaction kettle later, carries out hydro-thermal process；
After S3, hydro-thermal reaction, centrifuge washing and drying are carried out to product, obtain lurid powdery product；Again should
Powdery product makes after being grinded with a mortar, and uniformly paving is dispersed in corundum boat, is put into tube furnace and carries out carburizing sintering；
S4, by the product cooled to room temperature after carburizing sintering in step S3, centrifuge washing and drying again, so that it may obtain
The molybdenum carbide nanometer sheet of nickel doping.
Preferably, in step S1, the mass ratio of ammonium molybdate and nickel nitrate is 1:1-2.
Preferably, in step S1, the volume ratio of ammonium molybdate and nickel nitrate solvent for use is 1-5:1.
Preferably, in step S2, the concentration of sodium hydroxide is 0.1-0.5M.
Preferably, in step S2, hydrothermal reaction condition is that reaction temperature is 160-180 DEG C, reaction time 5-10h.
Preferably, in step S3, light yellow product corundum boat paving dissipate it is thinner, carbonization effect it is better, thickness is preferred
0.05-1mm, can be used scraper or spray gun carries out powder dispersion.
Preferably, in step S3, the temperature program in tube furnace are as follows: first using hydrogen-argon-mixed, with the heating of 2 DEG C/min
Rate is warming up to 500 DEG C of progress reduction reaction 2-4h, and then closes hydrogen-argon-mixed entrance, after with the heating speed of 5 DEG C/min
Tube furnace is warming up to 800 DEG C by rate, then opens methane and hydrogen inlet, carries out carburizing reagent, reaction time 1-3h.
The principle of the invention lies in the molybdenum oxides for mixing nickel for preparing nano-sheet under hydrothermal conditions first, then exist again
Under high temperature, first molybdenum oxide is restored, later using methane as carbon source, is carbonized to the nanometer sheet after reduction, in this way
Continuous two step, available performance is uniform, efficient HER electrocatalyst materials.
The present invention achieves following beneficial technical effect:
Firstly, having prepared the molybdenum carbide nanometer sheet of nickel doping by two-step method；Secondly, introducing prepares the carbon source methane of graphene
Mixed gas carries out carbonization treatment to product as carbon source；Finally, obtain nickel doping molybdenum carbide nanometer sheet show it is higher
Electro catalytic activity, current density is in 10mA/cm2In the case where, overpotential 110mV, Tafel slope also down to
50.1mV/dec and show excellent cyclical stability.
Detailed description of the invention
The transmitted electron photo of product prepared by Fig. 1 embodiment of the present invention 1；
The transmitted electron photo of product prepared by Fig. 2 embodiment of the present invention 2.
Specific embodiment
Embodiment 1
2.1g ammonium molybdate is first weighed, is dissolved in the deionized water of 30mL, solution A is denoted as；Then the nitre of 3.3g is weighed again
Sour nickel, is dissolved in the deionized water of 10ml, is denoted as solution B；Again in the case of stirring, by solution B slowly to drip
Acceleration is added in solution A；Be added dropwise reuse after mixing evenly 0.3M sodium hydroxide solution it is molten to above-mentioned mixing
The pH value of liquid is adjusted, adjust to pH=8.5 or so, then the mixed solution is transferred in the hydrothermal reaction kettle of 60mL,
5h is reacted at 180 DEG C.After reaction, hydrothermal reaction kettle is taken out, and is rapidly cooled using tap water.Later to product
Conventional centrifuge washing and drying are carried out, pale yellow powder is obtained.After hand lapping, which is uniformly put down using scraper
It is layered in corundum boat, is then placed in tube furnace, carry out heating treatment, the formula of heating is hydrogen-argon-mixed first to use, with 2
DEG C/heating rate of min is warming up to 500 DEG C of progress reduction reaction 2h, and then closes hydrogen-argon-mixed entrance, after with 5 DEG C/
Tube furnace is warming up to 800 DEG C by the heating rate of min, then opens methane and hydrogen inlet, carries out carburizing reagent, reaction time
For 3h.After reaction, after naturally cool to room temperature, again centrifuge washing and drying, so that it may obtain the molybdenum carbide of nickel doping
Nanometer sheet.
Embodiment 2
2.1g ammonium molybdate is first weighed, is dissolved in the deionized water of 30mL, solution A is denoted as；Then the nitre of 3.3g is weighed again
Sour nickel, is dissolved in the deionized water of 10ml, is denoted as solution B；Again in the case of stirring, by solution B slowly to drip
Acceleration is added in solution A；Be added dropwise reuse after mixing evenly 0.3M sodium hydroxide solution it is molten to above-mentioned mixing
The pH value of liquid is adjusted, adjust to pH=10.0 or so, then the mixed solution is transferred in the hydrothermal reaction kettle of 60mL,
5h is reacted at 170 DEG C.After reaction, hydrothermal reaction kettle is taken out, and is rapidly cooled using tap water.Later to production
Object carries out conventional centrifuge washing and drying, obtains pale yellow powder.It is after hand lapping, the powder is uniform using scraper
It is laid in corundum boat, is then placed in tube furnace, carry out heating treatment, the formula of heating is hydrogen-argon-mixed first to use, with 2
DEG C/heating rate of min is warming up to 500 DEG C of progress reduction reaction 2h, and then closes hydrogen-argon-mixed entrance, after with 5 DEG C/
Tube furnace is warming up to 800 DEG C by the heating rate of min, then opens methane and hydrogen inlet, carries out carburizing reagent, reaction time
For 3h.After reaction, after naturally cool to room temperature, again centrifuge washing and drying, so that it may obtain the molybdenum carbide of nickel doping
Nanometer sheet.
Embodiment 3
2.1g ammonium molybdate is first weighed, is dissolved in the deionized water of 30mL, solution A is denoted as；Then the nitre of 4.0g is weighed again
Sour nickel, is dissolved in the deionized water of 10ml, is denoted as solution B；Again in the case of stirring, by solution B slowly to drip
Acceleration is added in solution A；Be added dropwise reuse after mixing evenly 0.3M sodium hydroxide solution it is molten to above-mentioned mixing
The pH value of liquid is adjusted, adjust to pH=8.5 or so, then the mixed solution is transferred in the hydrothermal reaction kettle of 60mL,
5h is reacted at 180 DEG C.After reaction, hydrothermal reaction kettle is taken out, and is rapidly cooled using tap water.Later to product
Conventional centrifuge washing and drying are carried out, pale yellow powder is obtained.After hand lapping, which is uniformly put down using scraper
It is layered in corundum boat, is then placed in tube furnace, carry out heating treatment, the formula of heating is hydrogen-argon-mixed first to use, with 2
DEG C/heating rate of min is warming up to 500 DEG C of progress reduction reaction 2h, and then closes hydrogen-argon-mixed entrance, after with 5 DEG C/
Tube furnace is warming up to 800 DEG C by the heating rate of min, then opens methane and hydrogen inlet, carries out carburizing reagent, reaction time
For 3h.After reaction, after naturally cool to room temperature, again centrifuge washing and drying, so that it may obtain the molybdenum carbide of nickel doping
Nanometer sheet.
Embodiment 4
2.1g ammonium molybdate is first weighed, is dissolved in the deionized water of 30mL, solution A is denoted as；Then the nitre of 2.1g is weighed again
Sour nickel, is dissolved in the deionized water of 10ml, is denoted as solution B；Again in the case of stirring, by solution B slowly to drip
Acceleration is added in solution A；Be added dropwise reuse after mixing evenly 0.3M sodium hydroxide solution it is molten to above-mentioned mixing
The pH value of liquid is adjusted, adjust to pH=9.0 or so, then the mixed solution is transferred in the hydrothermal reaction kettle of 60mL,
8h is reacted at 160 DEG C.After reaction, hydrothermal reaction kettle is taken out, and is rapidly cooled using tap water.Later to product
Conventional centrifuge washing and drying are carried out, pale yellow powder is obtained.After hand lapping, which is uniformly put down using scraper
It is layered in corundum boat, is then placed in tube furnace, carry out heating treatment, the formula of heating is hydrogen-argon-mixed first to use, with 2
DEG C/heating rate of min is warming up to 500 DEG C of progress reduction reaction 2h, and then closes hydrogen-argon-mixed entrance, after with 5 DEG C/
Tube furnace is warming up to 800 DEG C by the heating rate of min, then opens methane and hydrogen inlet, carries out carburizing reagent, reaction time
For 3h.After reaction, after naturally cool to room temperature, again centrifuge washing and drying, so that it may obtain the molybdenum carbide of nickel doping
Nanometer sheet.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art
It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention
Design or beyond the scope defined by this claim, be within the scope of protection of the invention.
Claims (8)
1. a kind of preparation method of the molybdenum carbide nanometer sheet of nickel doping, it is characterised in that: following steps are specifically included,
S1, firstly, weighing suitable ammonium molybdate and nickel nitrate, it is dissolved in deionized water respectively, is respectively labeled as solution A
And B；Again in the case of stirring, solution B is slowly added into solution A；
Be slowly added dropwise sodium hydroxide solution in S2, the mixed solution into step S1, carry out pH adjusting, to pH be adjusted to 9-10 it
Between, the mixed solution is transferred in hydrothermal reaction kettle later, carries out hydro-thermal process；
After S3, hydro-thermal reaction, centrifuge washing and drying are carried out to product, obtain lurid powdery product；Again should
Powdery product makes after being grinded with a mortar, and uniformly paving is dispersed in corundum boat, is put into tube furnace and carries out carburizing sintering；
S4, by the product cooled to room temperature after carburizing sintering in step S3, centrifuge washing and drying again, so that it may obtain
The molybdenum carbide nanometer sheet of nickel doping.
2. a kind of preparation method of the molybdenum carbide nanometer sheet of nickel doping according to claim 1, it is characterised in that: the step
In rapid S1, the mass ratio of ammonium molybdate and nickel nitrate is 1:1-2.
3. a kind of preparation method of the molybdenum carbide nanometer sheet of nickel doping according to claim 1, it is characterised in that: the step
In rapid S1, the volume ratio of ammonium molybdate and nickel nitrate solvent for use is 1-5:1.
4. a kind of preparation method of the molybdenum carbide nanometer sheet of nickel doping according to claim 1, it is characterised in that: the step
In rapid S2, the concentration of sodium hydroxide is 0.1-0.5M.
5. a kind of preparation method of the molybdenum carbide nanometer sheet of nickel doping according to claim 1, it is characterised in that: the step
In rapid S2, hydrothermal reaction condition is that reaction temperature is 160-180 DEG C, reaction time 5-10h.
6. a kind of preparation method of the molybdenum carbide nanometer sheet of nickel doping according to claim 1, it is characterised in that: the step
In rapid S3, light yellow product the paving of corundum boat dissipate with a thickness of 0.05-1mm, scraper can be used or spray gun carries out powder point
It dissipates.
7. a kind of preparation method of the molybdenum carbide nanometer sheet of nickel doping according to claim 1, it is characterised in that: the step
In rapid S3, the temperature program in tube furnace are as follows: first using hydrogen-argon-mixed, with the heating rate of 2 DEG C/min be warming up to 500 DEG C into
Row reduction reaction 2-4h, and then close hydrogen-argon-mixed entrance；Tube furnace is warming up to the heating rate of 5 DEG C/min afterwards
800 DEG C, methane and hydrogen inlet are then opened, carries out carburizing reagent, reaction time 1-3h.
8. the molybdenum carbide nanometer sheet of the nickel doping of any one of -7 the methods preparation is reacted for HER according to claim 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110180569A (en) * | 2019-05-23 | 2019-08-30 | 武汉科技大学 | Sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material and its preparation method |
| CN110368969A (en) * | 2019-08-20 | 2019-10-25 | 南昌航空大学 | A kind of preparation method and applications loading Heteroatom doping molybdenum carbide liberation of hydrogen catalyst on carbon paper or carbon cloth |
| CN110614105A (en) * | 2019-09-25 | 2019-12-27 | 上海应用技术大学 | Mo for hydrogen evolution2C/NiCoSex heterojunction electrocatalytic material and preparation method thereof |
| CN112808286A (en) * | 2021-01-27 | 2021-05-18 | 常州工学院 | Cobalt/molybdenum carbide nano catalyst and preparation method and application thereof |
-
2019
- 2019-01-29 CN CN201910088084.1A patent/CN109759103A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110180569A (en) * | 2019-05-23 | 2019-08-30 | 武汉科技大学 | Sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material and its preparation method |
| CN110368969A (en) * | 2019-08-20 | 2019-10-25 | 南昌航空大学 | A kind of preparation method and applications loading Heteroatom doping molybdenum carbide liberation of hydrogen catalyst on carbon paper or carbon cloth |
| CN110368969B (en) * | 2019-08-20 | 2022-04-01 | 南昌航空大学 | Preparation method and application of heteroatom-doped molybdenum carbide hydrogen evolution catalyst loaded on carbon paper or carbon cloth |
| CN110614105A (en) * | 2019-09-25 | 2019-12-27 | 上海应用技术大学 | Mo for hydrogen evolution2C/NiCoSex heterojunction electrocatalytic material and preparation method thereof |
| CN110614105B (en) * | 2019-09-25 | 2022-05-31 | 上海应用技术大学 | Mo for hydrogen evolution2C/NiCoSex heterojunction electrocatalytic material and preparation method thereof |
| CN112808286A (en) * | 2021-01-27 | 2021-05-18 | 常州工学院 | Cobalt/molybdenum carbide nano catalyst and preparation method and application thereof |
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Application publication date: 20190517 |