CN107694586A - A kind of graphene winding molybdenum carbide/carbosphere elctro-catalyst and preparation method thereof and apply in acid condition in water electrolysis hydrogen production - Google Patents
A kind of graphene winding molybdenum carbide/carbosphere elctro-catalyst and preparation method thereof and apply in acid condition in water electrolysis hydrogen production Download PDFInfo
- Publication number
- CN107694586A CN107694586A CN201710785956.0A CN201710785956A CN107694586A CN 107694586 A CN107694586 A CN 107694586A CN 201710785956 A CN201710785956 A CN 201710785956A CN 107694586 A CN107694586 A CN 107694586A
- Authority
- CN
- China
- Prior art keywords
- carbosphere
- catalyst
- elctro
- molybdenum carbide
- preparation
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 33
- 238000004804 winding Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000001257 hydrogen Substances 0.000 title claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 9
- 239000002253 acid Substances 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001694 spray drying Methods 0.000 claims abstract description 20
- 229920001661 Chitosan Polymers 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000000137 annealing Methods 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 235000007686 potassium Nutrition 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract 1
- 239000003643 water by type Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910003178 Mo2C Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to catalysis material field, it is related to a kind of graphene winding molybdenum carbide/carbosphere elctro-catalyst and preparation method thereof and applies in acid condition in water electrolysis hydrogen production, comprise the following steps：Step 1：Molybdate and graphene oxide is soluble in water, chitosan is dissolved in the in the mixed solvent of acetic acid and water, then mixed two kinds of solution, is stirred under certain speed；Step 2：By step 1 mixed solution by spray drying, solid powder is then collected, the high temperature anneal under atmosphere of inert gases, obtains graphene winding molybdenum carbide/carbosphere elctro-catalyst.Graphene winding molybdenum carbide/carbosphere size uniform prepared by the present invention, molybdenum carbide nano-particle is uniformly dispersed, and its preparation process is simple, and easy to operate, controllability is strong, and excellent chemical property is shown in electrolysis water liberation of hydrogen.
Description
Technical field
The invention belongs to catalysis material field, is related to a kind of graphene winding molybdenum carbide/carbosphere elctro-catalyst and its system
Applied in Preparation Method and in acid condition water electrolysis hydrogen production.
Background technology
With the fast development of modern society, global environmental pollution is serious, and energy resource consumption is rapid, scarcity of resources, compels to be essential
Want a kind of clean reproducible energy.Therefore, the development of effective cleaning and sustainable Hydrogen Energy source technology has attracted more next
More concerns, in the past few years, hydrogen are described as a promising energy, for reduction we to fossil fuel according to
Rely, reduce greenhouse gases and the discharge of other toxic gases, benefit environment.In the past few years, increasing notice collection
In by sustainable electrochemical process produce hydrogen, in order to realize the water decomposition of high-energy, liberation of hydrogen is reduced with catalyst
Reaction（HER）Driving energy be very important.
Pt/C is that H2-producing capacity is best in the market, a kind of most stable of catalyst.But because its resource is less, into
This is higher, it is impossible to large-scale application.Increasing research concentrates on pursuit has similar activity and stability with Pt
Inexpensive substitute.In the past decade, transient metal sulfide, nitride, phosphide, carbide are as before having
The elctro-catalyst on way is reported, particularly transition metal carbide, for example, molybdenum carbide (J. Mater. Chem. A, 2017,
5,4879) there is significant catalytic activity, be attributed to its unique electricity and catalytic performance similar to noble metal and (pass through induction
Carbon is to metal lattice).But after high-temperature process carbide polymerism occurs so that become large-sized, specific surface area
Reduce；CN106925312 discloses a kind of carbonization grapheme modified composite of molybdenum doping linear polymer and preparation method thereof,
Molybdenum carbide nano-particle is dispersed in polymer and graphene, but its preparation method is more complicated, is unfavorable for actual answer
With.
The content of the invention
The present invention is in view of the above-mentioned problems, provide a kind of graphene winding molybdenum carbide/carbosphere elctro-catalyst and its preparation side
Applied in method and in acid condition water electrolysis hydrogen production.
The technical solution used in the present invention is as follows：A kind of preparation of graphene winding molybdenum carbide/carbosphere elctro-catalyst
Method, comprise the following steps：
Step 1：Molybdate and graphene oxide is soluble in water, chitosan is dissolved in the in the mixed solvent of acetic acid and water, then
Two kinds of solution are mixed, stirred under certain speed；
Step 2：By step 1 mixed solution by spray drying, solid powder is then collected, the high temperature under atmosphere of inert gases
Annealing, obtain graphene winding molybdenum carbide/carbosphere elctro-catalyst.
In step 1, the mass ratio of the chitosan and molybdate is 0.5：1~2:1.
In step 1, the mass ratio of the molybdate and graphene oxide is 1：10-5：10.
In step 1, molybdate can be the one or more in ammonium molybdate, sodium molybdate, potassium molybdate.
In step 1, the mass volume ratio of chitosan and acetic acid is 1:1-1:4 g/ml.
In step 1, it is 500-1600 r/min that two kinds of solution, which mix speed,.
It is 100 ~ 130 DEG C that temperature is set during spray drying, and sample introduction speed is 4 ~ 6mL/min.
In annealing, annealing temperature is 600 DEG C ~ 900 DEG C, 1 ~ 5 DEG C/min of heating rate, is incubated 2 ~ 5h.
A kind of graphene winding molybdenum carbide/carbosphere elctro-catalyst obtained by above-mentioned preparation method
Above-mentioned graphene winding molybdenum carbide/carbosphere elctro-catalyst is applied in water electrolysis hydrogen production in acid condition.
Beneficial effects of the present invention are as follows：
1. the present invention by different quality than chitosan solution and ammonium molybdate solution with spray-on process mix high-speed stirred, mixed
Uniform solution is closed, is advantageous to make the dispersed full and uniform mixing for realizing raw material of molybdenum carbide nanoparticle in product.Particularly
Combined using the amino in chitosan with molybdenum acid ion so that Mo2C nano-particles are evenly distributed in carbosphere, are avoided
Because of the agglomeration that high temperature occurs, so as to the more avtive spots of exposure.
2. graphene oxide can effectively improve the electric conductivity of elctro-catalyst in the present invention, accelerate electricity in electrochemical process
Lotus transfer rate, microballoon made from spray drying process have the property of bigger serface and concrete dynamic modulus rate, be advantageous to electrolyte with
The diffusion of hydrogen, reduce the resistance to mass tranfer during electro-catalysis.
3. containing abundant nitrogen employed in the present invention in the chitosan of raw material, nitrogen-atoms is realized after high annealing
Doped and compounded material, so as to reduce energy of adsorption of the hydrogen in material surface, be advantageous to the precipitation of electrolysis water process hydrogen.
4. preparation process of the present invention is simple, easy to operate, controllability is strong, available for mass producing and be used for industrial electro
Solve elutriation hydrogen.
Brief description of the drawings
Fig. 1 is to wind molybdenum carbide/carbosphere electricity according to synthesized graphene in embodiment 2 by the method for the invention to urge
The XRD of agent；
Fig. 2 is the ESEM and high-resolution picture that graphene winds molybdenum carbide/carbosphere elctro-catalyst；
Fig. 3 and Fig. 4 is that graphene winds molybdenum carbide/carbosphere elctro-catalyst catalytic hydrogen evolution performance map.Wherein, Mo2C/NC is pair
The sample of ratio 1, S-Mo2C/NC0.3GO750 is the sample of embodiment 2.
Embodiment
The present invention is specifically described or further illustrated by the following examples, its object is to be better understood from this
The technical connotation of invention, but it is not intended to limit the present invention.
Embodiment 1：
Sample preparation：1g molybdates and 14mL7.2mg/mL graphene oxides are dissolved in 28mL deionized waters, by 1g chitosans
The in the mixed solvent of 2 mL acetic acid and 186mL deionized waters is dissolved in, is then mixed two kinds of solution, 500-1600 r/min's
Stirred under speed.By mixed solution by spray drying, it is 100 ~ 130 DEG C that temperature is set during spray drying, sample introduction speed is 4 ~
6mL/min, solid powder is then collected, the high temperature anneal under argon atmosphere, 750 DEG C are warming up to through 6h, be incubated after 3h certainly
So cooling, obtain graphene winding molybdenum carbide/carbosphere elctro-catalyst.
Electro-catalysis application：2mg sample and 1mg conductive carbon are dissolved in 500 μ L alcohol-water mixtures, and ultrasound makes its mixing equal
It is even, black suspension is formed, it is 0.5% to pipette 10 μ L suspensions in 5 μ L mass fractions are added dropwise on glass-carbon electrode, after naturally dry
Nafion.In three-electrode system（Glass-carbon electrode is as working electrode, and saturation Ag/AgCl electrodes are as reference electrode, platinum filament electricity
Pole is used as to electrode）In, with 0.5M H2SO4Solution is the linear sweep voltammetry curve that electrolyte solution measures catalyst.The sample
Product current density is 10mA/cm2When, overpotential 76mV.
Embodiment 2：
Sample preparation：1g molybdates and 42mL7.2mg/mL graphene oxides are dissolved in 28mL deionized waters, by 1g chitosans
The in the mixed solvent of 2 mL acetic acid and 158mL deionized waters is dissolved in, is then mixed two kinds of solution, 500-1600 r/min's
Stirred under speed.By mixed solution by spray drying, it is 100 ~ 130 DEG C that temperature is set during spray drying, sample introduction speed is 4 ~
6mL/min, solid powder is then collected, the high temperature anneal under argon atmosphere, 750 DEG C are warming up to through 6h, be incubated after 3h certainly
So cooling, obtain graphene winding molybdenum carbide/carbosphere elctro-catalyst.
Electro-catalysis application：Electrode and test are prepared with example 1.The sample current density is 10mA/cm2When, overpotential is
70mV.This sample electrocatalysis characteristic is optimal.
Embodiment 3：
Sample preparation：1g molybdates and 70mL7.2mg/mL graphene oxides are dissolved in 28mL deionized waters, by 1g chitosans
The in the mixed solvent of 2 mL acetic acid and 130mL deionized waters is dissolved in, is then mixed two kinds of solution, 500-1600 r/min's
Stirred under speed.By mixed solution by spray drying, it is 100 ~ 130 DEG C that temperature is set during spray drying, sample introduction speed is 4 ~
6mL/min, solid powder is then collected, the high temperature anneal under argon atmosphere, 750 DEG C are warming up to through 6h, be incubated after 3h certainly
So cooling, obtain graphene winding molybdenum carbide/carbosphere elctro-catalyst.
Electro-catalysis application：Electrode and test are prepared with example 1.The sample current density is 10mA/cm2When, overpotential is
96mV。
Embodiment 4：
Sample preparation：1g molybdates and 42mL7.2mg/mL graphene oxides are dissolved in 28mL deionized waters, by 1g chitosans
The in the mixed solvent of 2 mL acetic acid and 158mL deionized waters is dissolved in, is then mixed two kinds of solution, 500-1600 r/min's
Stirred under speed.By mixed solution by spray drying, it is 100 ~ 130 DEG C that temperature is set during spray drying, sample introduction speed is 4 ~
6mL/min, solid powder is then collected, the high temperature anneal under argon atmosphere, be warming up to 850 DEG C through 6h 50min, insulation
Natural cooling after 3h, obtain graphene winding molybdenum carbide/carbosphere elctro-catalyst.
Electro-catalysis application：Electrode and test are prepared with example 1.The sample current density is 10mA/cm2When, overpotential is
88mV。
Comparative example 1：
Sample preparation：1g molybdates are dissolved in 28mL deionized waters, by 1g chitosans be dissolved in 2 mL acetic acid and 200 mL go from
The in the mixed solvent of sub- water, then two kinds of solution are mixed, stirred under 500-1600 r/min speed.Mixed solution is led to
Cross spray drying, it is 100 ~ 130 DEG C to set temperature during spray drying, and sample introduction speed be 4 ~ 6mL/min, then collection solid powder
End, the high temperature anneal under argon atmosphere, 750 DEG C are warming up to through 6h, is incubated natural cooling after 3h, obtain graphene winding carbon
Change molybdenum/carbosphere elctro-catalyst.
Electro-catalysis application：Electrode and test are prepared with example 1.The sample current density is 10mA/cm2When, overpotential is
97mV。
Comparative example 2：
Sample preparation：1g molybdates are dissolved in 28mL deionized waters, by 0.5g chitosans be dissolved in 2 mL acetic acid and 200mL go from
The in the mixed solvent of sub- water, then two kinds of solution are mixed, stirred under 500-1600 r/min speed.Mixed solution is led to
Cross spray drying, it is 100 ~ 130 DEG C to set temperature during spray drying, and sample introduction speed be 4 ~ 6mL/min, then collection solid powder
End, the high temperature anneal under argon atmosphere, 750 DEG C are warming up to through 6h, is incubated natural cooling after 3h, obtain graphene winding carbon
Change molybdenum/carbosphere elctro-catalyst.
Electro-catalysis application：Electrode and test are prepared with example 1.When the sample current density is 10mA/cm2, overpotential is
114mV。
Comparative example 3：
Sample preparation：1g molybdates are dissolved in 28mL deionized waters, 2g chitosans are dissolved in 2 mL acetic acid and 200mL deionizations
The in the mixed solvent of water, then two kinds of solution are mixed, stirred under 500-1600 r/min speed.Mixed solution is passed through
Spray drying, it is 100 ~ 130 DEG C that temperature is set during spray drying, and sample introduction speed is 4 ~ 6mL/min, then collects solid powder,
The high temperature anneal under argon atmosphere, 750 DEG C are warming up to through 6h, is incubated natural cooling after 3h, obtain graphene winding carbonization
Molybdenum/carbosphere elctro-catalyst.
Electro-catalysis application：Electrode and test are prepared with example 1.The sample current density is 10mA/cm2When, overpotential is
148mV。
Claims (10)
1. a kind of preparation method of graphene winding molybdenum carbide/carbosphere elctro-catalyst, it is characterised in that comprise the following steps：
Step 1：Molybdate and graphene oxide is soluble in water, chitosan is dissolved in the in the mixed solvent of acetic acid and water, then
Two kinds of solution are mixed, stirred under certain speed；
Step 2：By step 1 mixed solution by spray drying, solid powder is then collected, the high temperature under atmosphere of inert gases
Annealing, obtain graphene winding molybdenum carbide/carbosphere elctro-catalyst.
2. a kind of preparation method of graphene winding molybdenum carbide/carbosphere elctro-catalyst as claimed in claim 1, its feature exist
In：In step 1, the mass ratio of the chitosan and molybdate is 0.5：1~2:1.
3. a kind of preparation method of graphene winding molybdenum carbide/carbosphere elctro-catalyst as claimed in claim 1 or 2, it is special
Sign is：In step 1, the mass ratio of the molybdate and graphene oxide is 1：10-5：10.
4. a kind of preparation method of graphene winding molybdenum carbide/carbosphere elctro-catalyst as claimed in claim 1, its feature exist
In：In step 1, molybdate can be the one or more in ammonium molybdate, sodium molybdate, potassium molybdate.
5. a kind of preparation method of graphene winding molybdenum carbide/carbosphere elctro-catalyst as claimed in claim 1, its feature exist
In：In step 1, the mass volume ratio of chitosan and acetic acid is 1:1-1:4 g/ml.
6. a kind of preparation method of graphene winding molybdenum carbide/carbosphere elctro-catalyst as claimed in claim 1, its feature exist
In：In step 1, it is 500-1600 r/min that two kinds of solution, which mix speed,.
7. a kind of preparation method of graphene winding molybdenum carbide/carbosphere elctro-catalyst as claimed in claim 1, its feature exist
In：It is 100 ~ 130 DEG C that temperature is set during spray drying, and sample introduction speed is 4 ~ 6mL/min.
8. a kind of preparation method of graphene winding molybdenum carbide/carbosphere elctro-catalyst as claimed in claim 1, its feature exist
In：In annealing, annealing temperature is 600 DEG C ~ 900 DEG C, 1 ~ 5 DEG C/min of heating rate, is incubated 2 ~ 5h.
9. graphene winding molybdenum carbide/carbosphere electricity that a kind of preparation method as described in claim any one of 1-8 obtains is urged
Agent.
10. graphene winding molybdenum carbide/carbosphere elctro-catalyst described in claim 9 is in acid condition in water electrolysis hydrogen production
Using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710785956.0A CN107694586B (en) | 2017-09-04 | 2017-09-04 | It a kind of graphene winding molybdenum carbide/carbosphere elctro-catalyst and preparation method thereof and applies in water electrolysis hydrogen production in acid condition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710785956.0A CN107694586B (en) | 2017-09-04 | 2017-09-04 | It a kind of graphene winding molybdenum carbide/carbosphere elctro-catalyst and preparation method thereof and applies in water electrolysis hydrogen production in acid condition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107694586A true CN107694586A (en) | 2018-02-16 |
| CN107694586B CN107694586B (en) | 2019-03-05 |
Family
ID=61171937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710785956.0A Active CN107694586B (en) | 2017-09-04 | 2017-09-04 | It a kind of graphene winding molybdenum carbide/carbosphere elctro-catalyst and preparation method thereof and applies in water electrolysis hydrogen production in acid condition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107694586B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109081347A (en) * | 2018-07-16 | 2018-12-25 | 湖南大学 | A method of based on mutually separation synthesis porous carbon microsphere |
| CN110433835A (en) * | 2019-07-02 | 2019-11-12 | 常州大学 | A kind of efficient liberation of hydrogen catalyst and preparation method thereof |
| WO2022222430A1 (en) * | 2021-04-20 | 2022-10-27 | 广东石油化工学院 | Tin-based bimetallic carbide@carbon nano chain core-shell structure, preparation method therefor and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513139A (en) * | 2011-12-02 | 2012-06-27 | 浙江工业大学 | Pt-WC (Wolfram Carbide)/ graphene composite electric catalyst and preparation method thereof |
| CN103357408A (en) * | 2012-03-31 | 2013-10-23 | 浙江工业大学 | WC/CNT (wolfram carbide/carbon nano-tube), WC/CNT/Pt (wolfram carbide/carbon nano-tube/platinum) composite materials and preparation method and application thereof |
-
2017
- 2017-09-04 CN CN201710785956.0A patent/CN107694586B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513139A (en) * | 2011-12-02 | 2012-06-27 | 浙江工业大学 | Pt-WC (Wolfram Carbide)/ graphene composite electric catalyst and preparation method thereof |
| CN103357408A (en) * | 2012-03-31 | 2013-10-23 | 浙江工业大学 | WC/CNT (wolfram carbide/carbon nano-tube), WC/CNT/Pt (wolfram carbide/carbon nano-tube/platinum) composite materials and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ZONGHUA PU ET AL.: "Mo2C quantum dot embedded chitosan-derived nitrogen-doped carbon for efficient hydrogen evolution in a broad pH range", 《CHEM. COMMUN.》 * |
| 王平: "氮掺杂石墨烯和碳化钼/石墨烯复合纳米材料的电催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109081347A (en) * | 2018-07-16 | 2018-12-25 | 湖南大学 | A method of based on mutually separation synthesis porous carbon microsphere |
| CN110433835A (en) * | 2019-07-02 | 2019-11-12 | 常州大学 | A kind of efficient liberation of hydrogen catalyst and preparation method thereof |
| WO2022222430A1 (en) * | 2021-04-20 | 2022-10-27 | 广东石油化工学院 | Tin-based bimetallic carbide@carbon nano chain core-shell structure, preparation method therefor and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107694586B (en) | 2019-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108385124B (en) | Preparation method of transition metal/carbon tube/graphene electrocatalyst for hydrogen evolution reaction | |
| CN109046408B (en) | Composite hydrogen evolution electro-catalytic material and preparation method and application thereof | |
| CN107904620B (en) | Three-dimensional graphene/carbon nanotube-based molybdenum disulfide/cobalt sulfide composite material electrocatalyst and preparation method and application thereof | |
| Xiong et al. | An oxygen reduction catalyst derived from a robust Pd-reducing bacterium | |
| CN105688958A (en) | Polyhedron cobalt phosphide/graphite carbon hybrid material and preparing method and application thereof | |
| CN112495408B (en) | Preparation method of electrocatalytic hydrogen evolution nano material | |
| CN105170169A (en) | Nitrogen-doped graphene-iron-based nanoparticle composite catalyst and preparation method thereof | |
| CN103413951A (en) | Nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and preparation method thereof | |
| CN112517011B (en) | Carbon-based nickel-iron bimetal oxygen evolution catalyst and preparation method thereof | |
| CN105070924B (en) | A kind of DMFC molybdenum sulfide functionalized carbon nano-tube carries Pt catalyst and preparation method thereof | |
| CN106025244A (en) | Nickel selenide/graphene/carbon nanotube composite material and preparation method thereof | |
| Wei et al. | Economical, green and rapid synthesis of CDs-Cu2O/CuO nanotube from the biomass waste reed as sensitive sensing platform for the electrochemical detection of hydrazine | |
| CN107335451A (en) | The preparation method of platinum/molybdenum disulfide nano sheet/graphene three-dimensional combination electrode catalyst | |
| CN110787823B (en) | Three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nano particle as well as preparation method and application thereof | |
| CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN112103520A (en) | Anode catalyst of alcohol fuel cell | |
| CN107694586B (en) | It a kind of graphene winding molybdenum carbide/carbosphere elctro-catalyst and preparation method thereof and applies in water electrolysis hydrogen production in acid condition | |
| CN111659394A (en) | Copper-based catalyst and preparation method and application thereof | |
| CN105778088B (en) | A kind of graphene/polyaniline nanometer stick array composite and preparation method and application | |
| CN112657523A (en) | Preparation method of molybdenum disulfide nanosheet/carbon nitride nanosheet/graphene three-dimensional composite electrode catalyst | |
| CN108273524B (en) | Carbon composite material modified by chalcogenide and transition metal and preparation method and application thereof | |
| CN104525218B (en) | A kind of Pt-CoSi2the preparation method of/Graphene composite electrocatalyst | |
| CN114232012A (en) | Ionic liquid modified nano carbon material catalyst and preparation method and application thereof | |
| CN115094440B (en) | Preparation method of cobalt/ferroferric oxide/carbon nano tube/C porous microsphere hydrogen production catalyst | |
| CN114990628B (en) | Double-function electrocatalyst for quick synthesis of Joule heat and its application in high-efficiency water decomposition |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20180216 Assignee: WENZHOU JIUYUAN LITHIUM BATTERY TECHNOLOGY DEVELOPMENT Co.,Ltd. Assignor: Wenzhou University Contract record no.: X2020330000100 Denomination of invention: A graphene wound molybdenum carbide / carbon microsphere electrocatalyst and its preparation method and application in hydrogen production by electrolyzing water under acidic conditions Granted publication date: 20190305 License type: Common License Record date: 20201115 |
|
| EE01 | Entry into force of recordation of patent licensing contract |