CN105529474B - The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen and preparation method thereof of graphene package - Google Patents
The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen and preparation method thereof of graphene package Download PDFInfo
- Publication number
- CN105529474B CN105529474B CN201610043820.8A CN201610043820A CN105529474B CN 105529474 B CN105529474 B CN 105529474B CN 201610043820 A CN201610043820 A CN 201610043820A CN 105529474 B CN105529474 B CN 105529474B
- Authority
- CN
- China
- Prior art keywords
- super
- electro
- graphene
- catalyst
- dispersed nano
- 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.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic 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
- Y02E60/50—Fuel cells
Abstract
The invention belongs to electro-catalysis hydrogen producing technology fields, and in particular to a kind of super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen and preparation method thereof of graphene package.Super-dispersed nano MoC(1 ~ 20 nanometer that the catalyst is wrapped up by 1 ~ 10 layer of graphene) it forms, and there are very big specific surface area (100 ~ 300 m2/ g) and double-pore structure abundant (3 ~ 4 and 20 ~ 500 nanometers).Preparation method include the following: use Mo3(BTC)2As hydridization presoma; it can be prepared by a kind of super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of above-mentioned graphene package by 500 ~ 1000 DEG C of carbonizations under protection of argon gas; in 1 ~ 80 DEG C/min, carbonization time is 0.5 ~ 24 hour for the heating rate control of the carbonisation.The catalyst shows high electro-catalysis hydrogen production activity and stability under acid and alkaline condition, and cost of material is cheap, technical maturity is stable, easy to operate, controllability is strong needed for preparation process, is suitable for large-scale production and the hydrogen manufacturing of industrial electrolysis water.
Description
Technical field
The invention belongs to electro-catalysis hydrogen producing technology fields, and in particular to a kind of super-dispersed nano molybdenum carbide of graphene package
Electro-catalysis catalyst for preparing hydrogen and preparation method thereof.
Background technique
As continuing to increase for world population is constantly progressive with the development of society, demand of the mankind to the energy is growing day by day.
Nowadays, traditional " to change with the worsening of the traditional fossil energies such as petroleum, coal petered out with environmental problem
Energy resource structure system based on the stone energy " is faced with unprecedented challenge and crisis.The highest energy that hydrogen has is close
Degree, it is excellent have good burning performance, cleanliness without any pollution the advantages that made the best alternative green of traditional fossil energy
The energy.However, the utilization of Hydrogen Energy is heavily dependent on the development of hydrogen producing technology technique, industrial hydrogen production technique is mainly at present
Effect of Catalysis In Petrochemistry cracking and natural gas steam reformation hydrogen production, the technique from the viewpoint of environment and total energy approach not
Meet the energy development strategy of now current " Green Sustainable ".In recent years, as new-generation technology (such as send out by solar energy
Electricity, wind-power electricity generation, nuclear energy power generation, hydroelectric generation, geothermal power generation etc.) continuous development and network system continuing to optimize and rise
Grade, the advantage of water electrolysis hydrogen production technology are constantly amplified, or even are described as " optimal industry by many scientists and enterprisers
Hydrogen production process ", and the most crucial problem of the technology is the exploitation of efficient, stable, honest hydrogen manufacturing elctro-catalyst.
Currently, the most effective elctro-catalyst of electro-catalysis process for making hydrogen is platinum based catalyst, because such catalyst is being electrolysed
There is minimum overpotential and very high stability in water hydrogen production process.But the fancy price of platinum and low amount of storage are serious
Constrain the tremendous development of extensive use and the process for making hydrogen of such catalyst in water electrolysis hydrogen production.Therefore, it looks for honest and clean
Valence, replaceable high activity electro-catalysis catalyst for preparing hydrogen are the key problems for developing the process for making hydrogen.It recent studies have shown that, preceding mistake
It crosses metal carbides and shows higher catalytic activity and stability in electro-catalysis hydrogen production reaction.Wherein, molybdenum carbide (MoCx)
It is one of the optimal alternative catalyst being widely studied in recent years.However, a variety of synthetic methods reported at this stage have
There are certain limitation, molybdenum carbide (MoCx) synthesis process inevitably use high temperature (~ 900 DEG C), will cause synthesis
Molybdenum carbide (MoC in the processx) particle sintering and reunion, be difficult to realize high uniformity dispersion Superfine powder structure；In addition,
High synthesis temperature can cause collapsing for the pore structure of catalyst, so that the catalyst generally possesses lesser specific surface area (< 50
m2/ g).Above-mentioned technical bottleneck seriously constrains molybdenum carbide (MoCx) catalyst in electro-catalysis hydrogen production process the exposure of active sites and
The diffusion of reaction product and reactant largely affects activation plays and the extensive use of such elctro-catalyst.
Summary of the invention
An object of the present invention is to provide a kind of super-dispersed nano molybdenum carbide electro-catalysis producing hydrogen, catalyzing of graphene package
Agent.The catalyst raw material is from a wealth of sources, low in cost, and shows high electro-catalysis hydrogen manufacturing under acid and alkaline condition
Activity and stability can replace and uses most wide platinum based catalyst at this stage.
The second object of the present invention is to provide the super-dispersed nano molybdenum carbide electro-catalysis producing hydrogen, catalyzing of above-mentioned graphene package
The preparation method of agent.This method mentality of designing is clearly novel, and mature preparation process is stable, easy to operate, controllability is strong, is suitable for
Large-scale production.
The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package provided by the invention, by Mo3(BTC)2
(Mo-MOFs) the super-dispersed nano carbon that hydridization presoma is wrapped up by 1 ~ 10 layer of graphene generated in place during high temperature cabonization
Change molybdenum (MoC) (its partial size is 1 ~ 20 nm) composition, and there are very big specific surface area (100 ~ 300 m2/ g) and diplopore abundant
Structure (respectively 3 ~ 4 nm and 20 ~ 500 nm)；It is prepared by following preparation methods.
The preparation method of above-mentioned electro-catalysis catalyst for preparing hydrogen provided by the invention, specific steps are as follows:
Using Mo3(BTC)2It (Mo-MOFs) is hydridization presoma；Under protection of argon gas, above-mentioned hydridization presoma is warming up to
500 ~ 1000 DEG C, heating rate control is 1 ~ 80 DEG C/min；It is carbonized 0.5 ~ 24 hour at this temperature, obtains the graphite
The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of alkene package.
Wherein, carburizing temperature is preferably 700 DEG C ~ 900 DEG C, and heating rate is preferably 5 ~ 10 DEG C/min, and carbonization time is preferred
It is 3 ~ 5 hours.
The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of prepared graphene package, can be used for acid and alkalinity
Under the conditions of water electrolysis hydrogen production reaction, but be not intended to limit the catalyst for being catalyzed other catalytic hydrogenations and hydrogenolysis.
Technical principle of the invention are as follows: utilize Mo3(BTC)2(Mo-MOFs) Mo atom and equal benzene front three in hydridization presoma
Organic ligand abundant and porosity, overcome high―temperature nuclei in " atomic level contact " and Mo-MOFs presoma between sour ligand
The reunion in the activated centre MoC and pore structure collapse in the process, so that the super-dispersed nano that prepared above-mentioned graphene wraps up
The electro-catalysis catalyst for preparing hydrogen of molybdenum carbide has very distinct structure feature and advantage: being wrapped up by 1 ~ 10 layer of graphene ultra-dispersed
Nanometer MoC(1 ~ 20 nanometer) composition, and there are very big specific surface area (100 ~ 300 m simultaneously2/ g) and double-pore structure abundant
(3 ~ 4 and 20 ~ 500 nanometers).Ultra-dispersed nanometer MoC in catalyst composition can sufficiently expose its catalytic active site；Graphite
Alkene shell can effectively improve the electric conductivity of elctro-catalyst, accelerate charge transfer rate in electrochemical process；Bigger serface and rich
Rich porosity is conducive to the diffusion of the hydrogen generated and electrolyte, reduces the resistance to mass tranfer during electro-catalysis.The above structure
Characteristic makes the catalyst show high electro-catalysis hydrogen production activity and stability under acid and alkaline condition.
Compared with the prior art, the invention has the following beneficial effects:
1, the present invention makes full use of Mo3(BTC)2(Mo-MOFs) in hydridization presoma between Mo atom and trimesic acid ligand
" atomic level contact " and Mo-MOFs presoma in organic ligand abundant and porosity, overcome MoC during high―temperature nuclei
The reunion in activated centre and collapsing for pore structure, so that the electricity for the super-dispersed nano molybdenum carbide that prepared above-mentioned graphene wraps up
The nm of super-dispersed nano MoC(1 ~ 20 that catalyzing manufacturing of hydrogen catalyst is wrapped up by 1 ~ 10 layer of graphene) it forms, and have simultaneously very big
Specific surface area (100 ~ 300 m2/ g) and double-pore structure abundant (3 ~ 4 nm and 20 ~ 500 nm).The MoC that this method is prepared
No matter elctro-catalyst all compares from the partial size and dispersibility in catalyst self structure and porosity and the activated centre MoC obtained
Previous preparation method has apparent advantage；
2, the super-dispersed nano molybdenum carbide particles of graphene package prepared by the present invention assemble the electro-catalysis hydrogen manufacturing of formation again
Catalyst substantially reduces the catalysis using the synergistic effect of its super-dispersed nano structure, graphene shell and abundant porosity
Overpotential of the agent in water electrolysis hydrogen production reaction, greatly improves electro-catalysis hydrogen production activity and stability；
3, the present invention passes through " Mo3(BTC)2(Mo-MOFs) above-mentioned graphene package can be prepared in high temperature cabonization method "
The electro-catalysis catalyst for preparing hydrogen of super-dispersed nano molybdenum carbide.The raw material sources of the preparation method are abundant, cheap, and technique
It is mature and stable, easy to operate, controllability is strong, be suitable for large-scale production.
Detailed description of the invention
Fig. 1 is the composition figure of the electro-catalysis catalyst for preparing hydrogen of the super-dispersed nano molybdenum carbide of graphene package.Wherein, (a)
For scanning electron microscope (SEM) photograph, it is (b) particle diameter distribution of transmission electron microscope picture and MoC, (c) is transmission electron microscope picture, (d) is transmitted for high-resolution
Electron microscope.
Fig. 2 is the character figure of the electro-catalysis catalyst for preparing hydrogen of the super-dispersed nano molybdenum carbide of graphene package.Wherein, left
Figure is nitrogen adsorption desorption curve, and right figure is pore size distribution curve.
Fig. 3 is the polarization curve of the electro-catalysis catalyst for preparing hydrogen of the super-dispersed nano molybdenum carbide of graphene package.Its
In, left figure is in 0.5 mol/L H2SO4Polarization curve in electrolyte (acidity), right figure are to be electrolysed in 1.0 mol/L KOH
Polarization curve in liquid (alkalinity).
Fig. 4 is the electro-catalysis catalyst for preparing hydrogen for the super-dispersed nano molybdenum carbide that the graphene wraps up in 0.5 mol/L
H2SO4The polarization curve of 3000 front and backs of circulation in electrolyte.
Specific embodiment
The present invention is further described below by specific embodiment, but is not intended to limit the present invention.
Embodiment 1, by Mo3(BTC)2(Mo-MOFs) as in tube furnace, under argon gas protection, temperature programming to 700 DEG C of carbon
Change 5 hours, the super-dispersed nano molybdenum carbide electro-catalysis system of the graphene package is made in 5 DEG C/min in heating rate control
Hydrogen catalyst.Prepared electro-catalysis catalyst for preparing hydrogen is by the super-dispersed nano MoC that is wrapped up by 1 ~ 3 layer of graphene as shown in Figure 1:
(~ 3 nm) composition；As shown in Figure 2: the catalyst has very big specific surface area (187 m2/ g) and double-pore structure abundant (3 ~
4 nm and 20 ~ 300 nm).
The super-dispersed nano molybdenum carbide electricity of graphene package obtained urges the electro-chemical test of catalyst for preparing hydrogen by following step
It is rapid to carry out:
(a) the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen for weighing the package of graphene described in 15 mg is dispersed in
Include in the mixed solution of the Nafion solution (5%) of the deionized water of 750 μ L, the dehydrated alcohol of 250 μ L and 80 μ L,
Ultrasound 1 hour to form uniform suspension.Then the 4 above-mentioned hanging drops of μ L is taken to be coated onto the glass-carbon electrode that diameter is 3 mm
(GC) on, working electrode can be prepared in natural drying；
(b) the electrochemistry hydrogen manufacturing performance test for the working electrode being prepared is all made of three-electrode system, electrolyte difference
For the sulfuric acid solution (acidity) of 0.5 mol/L and the potassium hydroxide solution (alkalinity) of 1 mol/L.It is graphite rod to electrode,
Reference electrode is saturated calomel electrode (Saturated calomel electrode, SCE), and linear sweep voltammetry curve is in electricity
It being carried out on chem workstation (CHI660E, Shanghai Hua Chen instrument company), test temperature is room temperature, and sweep speed is 5 mV/s,
Scanning range is 0.1 to -0.6 V, and experimental data carries out iR correction.Electrode potential is obtained by comparison saturated calomel electrode
It arrives, and is converted into the electrode potential relative to reversible hydrogen electrode (Reversible hydrogen electrode, RHE), change
It is as follows to calculate equation: ERHE=ESCE + 0.059 pH + 0.241。
As shown in figure 3, the elctro-catalyst shows high hydrogen evolution activity, current density under acid and alkaline condition
For -10 mA/cm2Under conditions of overpotential be respectively 132 and 77 mV；As shown in figure 4, the elctro-catalyst is shown in acidity
High liberation of hydrogen stability does not observe apparent activity decline after 3000 circulations.
Embodiment 2, by Mo3(BTC)2(Mo-MOFs) as in tube furnace, under argon gas protection, temperature programming to 800 DEG C of carbon
Change 5 hours, the super-dispersed nano molybdenum carbide electro-catalysis system of the graphene package is made in 5 DEG C/min in heating rate control
Hydrogen catalyst.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package obtained is the same as implementation
The step of case 1 (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is 159 mV.
Embodiment 3, by Mo3(BTC)2(Mo-MOFs) as in tube furnace, under argon gas protection, temperature programming to 900 DEG C of carbon
Change 5 hours, the super-dispersed nano molybdenum carbide electro-catalysis system of the graphene package is made in 5 DEG C/min in heating rate control
Hydrogen catalyst.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package obtained is the same as implementation
The step of case 1 (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is 185 mV.
Embodiment 4, by Mo3(BTC)2(Mo-MOFs) as in tube furnace, under argon gas protection, temperature programming to 700 DEG C of carbon
Change 3 hours, the super-dispersed nano molybdenum carbide electro-catalysis system of the graphene package is made in 10 DEG C/min in heating rate control
Hydrogen catalyst.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package obtained is the same as implementation
The step of case 1 (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is 144 mV.
Embodiment 5, by Mo3(BTC)2(Mo-MOFs) as in tube furnace, under argon gas protection, temperature programming to 800 DEG C of carbon
Change 3 hours, the super-dispersed nano molybdenum carbide electro-catalysis system of the graphene package is made in 10 DEG C/min in heating rate control
Hydrogen catalyst.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package obtained is the same as implementation
The step of case 1 (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is 164 mV.
Embodiment 6, by Mo3(BTC)2(Mo-MOFs) as in tube furnace, under argon gas protection, temperature programming to 900 DEG C of carbon
Change 3 hours, the super-dispersed nano molybdenum carbide electro-catalysis system of the graphene package is made in 10 DEG C/min in heating rate control
Hydrogen catalyst.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package obtained is the same as implementation
The step of case 1 (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is 200 mV.
Embodiment 7, by Mo3(BTC)2(Mo-MOFs) as in tube furnace, under argon gas protection, temperature programming to 600 DEG C of carbon
Change 5 hours, the super-dispersed nano molybdenum carbide electro-catalysis system of the graphene package is made in 5 DEG C/min in heating rate control
Hydrogen catalyst.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package obtained is the same as implementation
The step of case 1 (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is 117 mV.
Embodiment 8, by Mo3(BTC)2(Mo-MOFs) as in tube furnace, under argon gas protection, temperature programming is to 1000 DEG C
The super-dispersed nano molybdenum carbide electro-catalysis of the graphene package is made in 5 DEG C/min in carbonization 5 hours, heating rate control
Catalyst for preparing hydrogen.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package obtained is the same as implementation
The step of case 1 (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is 250 mV.
Embodiment 9, by Mo3(BTC)2(Mo-MOFs) as in tube furnace, under argon gas protection, temperature programming to 600 DEG C of carbon
Change 5 hours, the super-dispersed nano molybdenum carbide electro-catalysis system of the graphene package is made in 20 DEG C/min in heating rate control
Hydrogen catalyst.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package obtained is the same as implementation
The step of case 1 (a) and (b).
The elctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is -10 mA/cm2Under conditions of mistake
Potential is 168 mV.
In conclusion the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package prepared by the present invention uses
Mo3(BTC)2(Mo-MOFs) it is used as hydridization presoma, protects lower high temperature cabonization can be prepared by by argon gas.Preparation method utilizes
Mo3(BTC)2(Mo-MOFs) " atomic level contact " and Mo-MOFs in hydridization presoma between Mo atom and trimesic acid ligand
Organic ligand abundant and porosity, overcome the reunion and pore structure in the activated centre MoC during high―temperature nuclei in presoma
Collapse so that the electro-catalysis catalyst for preparing hydrogen being prepared have very distinct structure feature and advantage: by 1 ~ 10 layer of graphite
The nm of super-dispersed nano MoC(1 ~ 20 of alkene package) composition, and there are very big specific surface area (100 ~ 300 m simultaneously2/ g) and it is rich
Rich double-pore structure (3 ~ 4 nm and 20 ~ 500 nm).The catalyst can preferably expose catalytic active site, improve elctro-catalyst
Electric conductivity accelerates the diffusion of the hydrogen generated and electrolyte to reduce electro-catalysis to accelerate charge transfer rate in electrochemical process
Resistance to mass tranfer in the process shows high electro-catalysis hydrogen production activity and stability under acid and alkaline condition.The system
Cost of material needed for Preparation Method is cheap, and technical maturity is stable, easy to operate, controllability is strong, is suitable for large-scale production.
Above content is only the basic explanation under present inventive concept, and any etc. made by technical solution according to the present invention
Effect transformation, is within the scope of protection of the invention.
Claims (6)
1. a kind of super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package, it is characterised in that:
The graphene is Mo3(BTC)2Hydridization presoma passes through high temperature cabonization, 1 ~ 10 layer of graphene generated in place；
The particle diameter distribution of the super-dispersed nano molybdenum carbide is 1 ~ 20 nanometer, and is wrapped in by above-mentioned graphene shell；
Its specific surface area is 100 ~ 300 m2/ g, have double-pore structure abundant, respectively 3 ~ 4 nanometers and 20 ~ 500 nanometers.
2. the preparation side of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package as described in claim 1
Method, it is characterised in that specific steps are as follows:
Using Mo3(BTC)2For hydridization presoma；Under protection of argon gas, by above-mentioned hydridization presoma be warming up to carburizing temperature 500 ~
1000 DEG C, heating rate control is 1 ~ 80 DEG C/min；It is carbonized 0.5 ~ 24 hour at this temperature, obtains the graphene packet
The nano silicon carbide molybdenum electro-catalysis catalyst for preparing hydrogen wrapped up in.
3. the preparation side for the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen that the graphene as described in claim 2 wraps up
Method, it is characterised in that the carburizing temperature is 700 DEG C ~ 900 DEG C.
4. the preparation side for the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen that the graphene as described in claim 3 wraps up
Method, it is characterised in that the heating rate is 5 ~ 10 DEG C/min.
5. the preparation side for the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen that the graphene as described in claim 4 wraps up
Method, it is characterised in that the carbonization time is 3 ~ 5 hours.
6. the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of graphene package as described in claim 1 is in acid or alkali
Property under the conditions of water electrolysis hydrogen production reaction in application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610043820.8A CN105529474B (en) | 2016-01-22 | 2016-01-22 | The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen and preparation method thereof of graphene package |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610043820.8A CN105529474B (en) | 2016-01-22 | 2016-01-22 | The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen and preparation method thereof of graphene package |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105529474A CN105529474A (en) | 2016-04-27 |
| CN105529474B true CN105529474B (en) | 2019-01-15 |
Family
ID=55771565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610043820.8A Expired - Fee Related CN105529474B (en) | 2016-01-22 | 2016-01-22 | The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen and preparation method thereof of graphene package |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105529474B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058193A (en) * | 2016-07-20 | 2016-10-26 | 华南理工大学 | Novel negative electrode material of sodium-ion battery as well as preparation method and application thereof |
| CN106637288B (en) * | 2016-12-27 | 2019-01-15 | 复旦大学 | A kind of nitrogen mixes phosphorus doping molybdenum carbide nano wire electro-catalysis catalyst for preparing hydrogen of mineral carbon load and preparation method thereof |
| CN108940328B (en) * | 2018-06-28 | 2020-02-18 | 大连理工大学 | Nano sheet-nano rod coupled three-dimensional composite material Ni-Co modified molybdenum carbide electro-catalysis hydrogen production catalyst and preparation method thereof |
| CN109136973B (en) * | 2018-08-28 | 2020-07-14 | 南京工业大学 | Non-noble metal doped molybdenum carbide hydrogen evolution electrode and preparation method and application thereof |
| CN111359647B (en) * | 2020-03-17 | 2021-02-23 | 中国石油大学(北京) | Ultrathin carbon layer coated nitrogen-doped cross-linked hierarchical pore molybdenum carbide material and preparation thereof |
| CN111905783B (en) * | 2020-06-29 | 2021-10-26 | 复旦大学 | Molybdenum carbide/carbon nano hydrogen production catalyst synthesized by using ink |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367521A (en) * | 2008-10-13 | 2009-02-18 | 复旦大学 | Synthesis of stephanoporate molybdenum carbide nano-wire |
-
2016
- 2016-01-22 CN CN201610043820.8A patent/CN105529474B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367521A (en) * | 2008-10-13 | 2009-02-18 | 复旦大学 | Synthesis of stephanoporate molybdenum carbide nano-wire |
Non-Patent Citations (3)
| Title |
|---|
| Highly active and durable nanostructured molybdenum carbide electrocatalysts for hydrogen production;W.-F. Chen等;《Energy & Environmental Science》;20130131;第6卷;943-951页 |
| Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production;Hao Bin Wu等;《Nature Communications》;20150311;第6卷;6512-6519页 |
| Synthesis and properties of the metal-organic framework Mo3(BTC)2 (TUDMOF-1);Markus Kramer等;《Journal of Materails Chemistry》;20060412;第16卷(第23期);2245-2248页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105529474A (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105529474B (en) | The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen and preparation method thereof of graphene package | |
| Jiang et al. | Promoting vanadium redox flow battery performance by ultra-uniform ZrO2@ C from metal-organic framework | |
| Du et al. | Nitrogen-doped carbon nanotubes/reduced graphene oxide nanosheet hybrids towards enhanced cathodic oxygen reduction and power generation of microbial fuel cells | |
| Chen et al. | Waste-derived catalysts for water electrolysis: circular economy-driven sustainable green hydrogen energy | |
| CN110295375B (en) | Electro-reduction of CO2Preparation of catalyst, catalyst and application | |
| CN109046408B (en) | Composite hydrogen evolution electro-catalytic material and preparation method and application thereof | |
| CN106180747B (en) | A kind of palladium copper binary alloy nano material, preparation method and its CO is restored as catalyst electro-catalysis2Application | |
| CN109569651B (en) | Dual-function catalyst RuCo @ HCSs and preparation method and application thereof | |
| CN109628951B (en) | Nickel sulfide hydrogen evolution electrocatalyst and preparation method and application thereof | |
| Chen et al. | N-doped 3D porous carbon catalyst derived from biowaste Triarrhena sacchariflora panicle for oxygen reduction reaction | |
| CN114293200B (en) | Porous carbon supported amorphous/crystalline ruthenium-based high-efficiency hydrogen evolution catalyst and preparation and application thereof | |
| CN106345501A (en) | Method for preparing iron phosphide based on magnetic ionic liquid modified carbon nanotube composite, and products and application thereof | |
| Lv et al. | Carbon-quantum-dots-involved Fe/Co/Ni phosphide open nanotubes for high effective seawater electrocatalytic decomposition | |
| CN109112563B (en) | Ruthenium phosphide/carbon nanotube composite material and preparation method and application thereof | |
| CN108179433A (en) | Ordered mesopore carbon loads nanometer iridium base electrocatalytic hydrogen evolution electrode and its preparation and application | |
| CN111939981A (en) | CoFeMOF-P/b-CNF composite material electrocatalyst and preparation method thereof | |
| CN115133045A (en) | Preparation method of iron and nitrogen co-doped gamma-graphite single alkyne carbon material | |
| CN107570166B (en) | Preparation method and application of composite carbon and transition element oxide nano-catalyst | |
| CN113668008B (en) | Molybdenum disulfide/cobalt carbon nanotube electrocatalyst and preparation method and application thereof | |
| Zhang et al. | Three-dimension in-situ nitrogen doping porous cellulosic biomass-based carbon aerogel for electrocatalytic CO2 reduction | |
| CN113026053B (en) | Preparation of graphene/silicon carbide three-dimensional composite aerogel and molybdenum disulfide-loaded electrocatalyst prepared from graphene/silicon carbide three-dimensional composite aerogel | |
| CN111905783B (en) | Molybdenum carbide/carbon nano hydrogen production catalyst synthesized by using ink | |
| Han et al. | Design yolk-shelled FeCo layered double hydroxide via a “one-stone-two-birds” strategy for oxygen evolution reaction | |
| CN112246261A (en) | Cobalt phosphide graded porous nanowire material and preparation and application thereof | |
| CN109097788B (en) | Double-carbon coupling transition metal nickel-based quantum dot electrocatalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190115 Termination date: 20220122 |