CN105126876B - A kind of flower-shaped carbon load MoS2Composite of nano particle and preparation method thereof - Google Patents
A kind of flower-shaped carbon load MoS2Composite of nano particle and preparation method thereof Download PDFInfo
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- CN105126876B CN105126876B CN201510559685.8A CN201510559685A CN105126876B CN 105126876 B CN105126876 B CN 105126876B CN 201510559685 A CN201510559685 A CN 201510559685A CN 105126876 B CN105126876 B CN 105126876B
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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 invention belongs to catalysis material field, specially a kind of flower-shaped carbon load MoS2Composite of nano particle and preparation method thereof.The present invention obtains flower-shaped carbon by presoma of biomass first with flower-shaped ZnO as template by simple hydro-thermal method and subsequent high-temperature heat treatment and acid etch;Then the flower-shaped carbon that will be obtained obtains MoS with four thio ammonium molybdate by solvent heat2Composite of the nano particle uniform load on flower-shaped carbon.The test of liberation of hydrogen catalysis shows that the material has relatively low liberation of hydrogen take-off potential(~110 mV), less Tafel slope(65 mV/dec)And good long-time stability.The present invention is simple to operate using hydro-thermal and solvent heat two-step method using extensive biomass as the presoma of flower-shaped carbon of originating; production cost is relatively low; environmental pollution is small, it is easy to mass, large-scale production, with the basic and wide application prospect of good industrialized production.
Description
Technical field
The invention belongs to catalysis material technical field, and in particular to a kind of liberation of hydrogen catalysis material and preparation method thereof and should
With.
Background technology
In world's today, the population of rapid growth and industry are to the bigger demand of the energy and the environmental crisis for thus causing
The more effective more environmentally friendly energy of exploitation is set to become more and more urgent.Wherein Hydrogen Energy as a kind of most potential energy, due to height
Combustion heat value and reusable edible the characteristics of be considered as being likely to replace fossil energy in future.At present, electrochemistry hydrogen manufacturing is still
It is so a kind of method for preparing hydrogen being widely used.In order to improve the efficiency of electrochemistry hydrogen manufacturing, generally requiring to use can be with
Reduce the catalyst of overpotential of hydrogen evolution, the catalyst of platinum base is considered as most effective of which catalyst, because its liberation of hydrogen mistake
Current potential is no better than zero.But platinum is few in earth content, and expensive, so as to greatly limit them in business
Large-scale application.Therefore, the base metal liberation of hydrogen catalyst for developing low cost, high efficiency and high stability just becomes very must
Will.To current, existing various non-platinum based catalysts are proved to catalytic activity for hydrogen evolution high, such as《Germany should change》
(Angew. Chem. 2015, 127, 1)The iron of report is nanocrystalline,《JACS》(J. Am. Chem. Soc.
2013, 135, 17881)The molybdenum bisuphide of report,《Germany should change》(Angew. Chem. Int. Ed. 2014, 53,
12855)The phosphatization cobalt of report and and《Energy and environment science》(Energy Environ. Sci., 2013, 6, 943)
Molybdenum carbide of report etc..
Molybdenum bisuphide(MoS2)It is a kind of typical two-dimensional layer material, liberation of hydrogen catalysis material is prepared based on it and is received
Extensive concern is arrived.In the past few years, substantial amounts of theoretical and experimental study discloses the catalytic activity of hydrogen evolution of molybdenum bisuphide
Mostly come from the unsaturated sulphur atom positioned at edge.But its intrinsic low conductivity and serious agglomeration traits are inhibited
The conduction of electronics and catalysis activity edge it is exposed, cause poor catalytic activity of hydrogen evolution.It is substantial amounts of to grind in order to solve these problems
Study carefully and be devoted to nano level MoS2It is supported on electrically-conductive backing plate to form molybdenum bisuphide-carbon hybrid material, such as Graphene, carbon
Nanotube and some other carbon material.Such as, Dai Hongjie etc. exists《JACS》(J. Am. Chem. Soc.
2011,133,7296) report MoS at first2Nano particle in situ is grown on graphene film preparing liberation of hydrogen catalysis high
The composite of activity.Then, by MoS2Nano particle is supported on《Application material and interface》(ACS Appl. Mater.
Interfaces, 2014, 6 (23), 21534)The graphene aerogel of report,《Advanced function material》(Adv. Funct.
Mater. 2013, 23, 5326)The mesoporous grapheme foam of report,《Nanoscale》(Nanoscale, 2013, 5,
7768; Nanoscale, 2014, 6, 5624)The CNT and graphene paper of report and《Materials chemistry will A》(J.
Mater. Chem. A, 2015,3, 5041)Carbon fiber foam of report etc. prepares the work quilt of liberation of hydrogen catalytic composite materials
Report in succession.These work show the material electronicses conducting power for improving and increase exposed MoS2Active number of edges is shadow
Ring two key factors of catalysis activity.
Although the Graphene and CNT of various structures are often used to load MoS2Nano particle, but these conductive bases
The preparation process of body is often relatively costly, and environmental pollution is larger.And biomass are just wide due to its source and recyclability
It is used for preparing conductive carbon material generally.Hydrothermal carbonization method is a kind of extensive adopted method of conversion of biomass, because this
It is method low cost, environment-friendly and easily operated.The biomass enough to hydrothermal carbonization further carry out high-temperature heat treatment can be with
Significantly improve the electric conductivity of material.Additionally, studies have reported that during the hydrothermal carbonization of biomass, adding some template materials
Material, such as graphene oxide sheet or MoS2Piece, can make the hydro-thermal carbon coating of generation on these mould material surfaces.
In the present invention, we realize the hydro-thermal carbon coating of biomass on flower-shaped ZnO surfaces by hydro-thermal method first, through subsequent
High temperature cabonization and acid etch after, obtained flower-shaped carbon material.Then with conductive flower-shaped carbon it is again substrate and tetrathio molybdenum
Sour ammonium solvent heat finally gives MoS2Nano particle is supported on the nano composite material on flower-shaped carbon.As liberation of hydrogen catalysis material,
Flower-shaped carbon can not only provide material good electronic conduction ability, additionally due to it and MoS2Between strong interaction may be used also
Significantly to suppress MoS2Reunion so that exposed more active MoS2Edge.In addition flower-shaped carbon three-dimensional porous knot in itself
Structure, can also increase the contact area with electrolyte, and promote hydrionic diffusion.Therefore this material shows relatively low analysis
Hydrogen take-off potential, less Tafel slope and good long-time stability.
The content of the invention
It is an object of the invention to provide the flower-shaped carbon load that a kind of inexpensive, environment-friendly and catalytic activity of hydrogen evolution is excellent
MoS2Nano composite material of nano particle and its preparation method and application.
The MoS that the present invention is provided2Nano particle is supported on the nano composite material on graphite, is in flower by solvent-thermal method
Shape carbon surface growth in situ MoS2Nano particle.The introducing of conductive flower-shaped carbon, can not only improve the electron transmission energy of material
Power, can also suppress MoS2Reunion, so as to expose more active sites, obtain good liberation of hydrogen catalytic effect.
The flower-shaped carbon load MoS that the present invention is provided2The nano composite material preparation method of nano particle, concretely comprises the following steps:
(1)The flower-shaped ZnO that 50 ~ 500 mg synthesize is dispersed in 5 ~ 20 ml deionized waters, 5 ~ 20 min of ultrasound, then
Add 50 ~ 500 mg biomass, 5 ~ 15 min of ultrasound;Then mixed liquor is transferred in autoclave pressure, is placed in 120 ~ 250 DEG C of bakings
8 ~ 24 h are reacted in case;After room temperature is naturally cooled to, product taking-up absolute ethyl alcohol is centrifuged repeatedly washing 3 ~ 8 times;Then
Product is placed in 2-24 h drying in 50 ~ 150 DEG C of baking ovens, it is powdered;
(2)The powder for taking 0.1 ~ 1.0 g drying is placed in tube furnace, under nitrogen protection with the intensification of 2 ~ 10 DEG C/min
Speed is heated to 400 ~ 1000 DEG C, is incubated 1 ~ 5 h;Then it is cooled to room temperature under gas shield;Then by the material after heat treatment
Material processes 0.5-6 h with 0.5 ~ 5 M HCl, then with deionized water and ethanol eccentric cleaning repeatedly, in 50 ~ 150 DEG C of baking ovens
Drying, obtains flower-shaped carbon;
(3)Weigh 5 ~ 50mg four thio ammonium molybdates to be added in 10 ml solvents, 5 ~ 60 min of ultrasound make four thio ammonium molybdate
Fully dissolving;The flower-shaped carbon of 2 ~ 20 mg is subsequently adding, 10 ~ 120 min of ultrasound help dispersion;The hydrazine hydrates of 0.1 ~ 1.0 ml mono- are added,
Then mixed liquor is transferred in autoclave pressure, 6 ~ 24 h of reaction in 100 ~ 250 DEG C of baking ovens are placed in;After room temperature is naturally cooled to,
By feed liquid taking-up deionized water centrifuge washing 3 ~ 10 times;Then reactant is placed in into 2 ~ 24 h in 30 ~ 120 DEG C of vacuum drying ovens to dry
It is dry, obtain final flower-shaped carbon load MoS2The composite of nano particle.
In the present invention, step(1)In biomass used be, one kind in cellulose, glucose, shitosan, or wherein
Several mixtures.
In the present invention, step(3)In solvent used be the one kind in DMF, acetone, tetrahydrofuran,
Or wherein several mixed solvent.
MoS prepared by the present invention2Nano particle is supported on the nano composite material on flower-shaped carbon, is by simple hydro-thermal
Realized with solvent heat two-step method.First with biomass as carbon matrix precursor, with flower-shaped ZnO as template, by hydro-thermal method and then
High annealing and acid etch obtain final three-dimensional porous flower-shaped carbon.Then again with flower-shaped carbon as substrate, by with four sulphur
MoS is loaded for ammonium molybdate solvent heat treatment obtaining shape carbon2The composite of nano particle.This material can be used as evolving hydrogen reaction
Catalyst, show good catalytic activity of hydrogen evolution, it has relatively low liberation of hydrogen take-off potential(~110 mV), less tower it is luxuriant and rich with fragrance
That slope(65 mV/dec)With excellent long-time stability.This is because the introducing of flower-shaped carbon not only can be with the electronics of reinforcing material
Conducting power, while MoS can also effectively be suppressed2Reunion, so as to expose more active sites.In addition cosmetic carbon with
MoS2Between strong electron interaction can also promote MoS2On electronics be rapidly transmitted to cosmetic carbon surface.
The present invention is easy to operate, and preparation condition is simple, and low production cost is more environmentally friendly, it is easy to mass, large-scale production,
With the basic and wide application prospect of good industrialized production.
Brief description of the drawings
The scanning electron microscope (SEM) photograph of the flower-shaped carbon of Fig. 1(a)With transmission electron microscope picture(b).
Fig. 2 add the flower-shaped carbon load MoS that 22 mg four thio ammonium molybdates are obtained2The scanning of nano particle composite material
Electron microscope.
Fig. 3 add the flower-shaped carbon load MoS that 22 mg four thio ammonium molybdates are obtained2The transmission of nano particle composite material
Electron microscope.
The flower-shaped carbon load MoS that Fig. 4 different ratios are obtained2The linear sweep voltammetry curve of nano particle composite material
(a)With Tafel slope figure(b).
The pure MoS that Fig. 5 four thio ammonium molybdate solvent heats are obtained2Scanning electron microscopy(a)And transmission electron microscopy
Figure(b).
Fig. 6 add the flower-shaped carbon load MoS that 10 mg four thio ammonium molybdates are obtained2The scanning of nano particle composite material
Electron microscope(a)And transmission electron microscope picture(b).
Fig. 7 add the flower-shaped carbon load MoS that 40 mg four thio ammonium molybdates are obtained2The scanning of nano particle composite material
Electron microscope(a)And transmission electron microscope picture(b).
Specific embodiment
Flower-shaped carbon load MoS of the invention is further described by the following examples2The system of nano particle composite material
Preparation Method and its catalytic activity of hydrogen evolution, the embodiment are merely possible to provide explanation rather than the restriction present invention.
Embodiment 1
(1)The flower-shaped ZnO that 100 mg synthesize is dispersed in 10 ml deionized waters, ultrasonic 20 min is subsequently adding 100
Mg glucose, ultrasonic 10 min;Then mixed liquor is transferred in pressure good fortune kettle, is placed in 180 DEG C of baking ovens and reacts 24 h;Treat
After naturally cooling to room temperature, product taking-up absolute ethyl alcohol is centrifuged repeatedly washing 5 times;Then product is placed in 60 DEG C of baking ovens
6 h are dried;
(2)The powder for taking 1.0 g drying is placed in tube furnace, is heated with the heating rate of 5 DEG C/min under nitrogen protection
2 h are incubated to 800 DEG C;Finally room temperature is cooled under gas shield.Then by the material after heat treatment with 2 M HCl treatment
1 h, then with deionized water and ethanol eccentric cleaning repeatedly, dries in 60 DEG C of baking ovens, obtains flower-shaped carbon;
(3)Weigh 22 mg four thio ammonium molybdates to be added in 10 ml DMF, ultrasonic 10 min fills four thio ammonium molybdate
Divide dissolving;The flower-shaped carbon of 10 mg is subsequently adding, ultrasonic 30 min helps dispersion;The hydrazine hydrates of 0.1 ml mono- are added, then by mixed liquor
It is transferred in autoclave pressure, is placed in 200 DEG C of baking ovens and reacts 18 h;After room temperature is naturally cooled to, by feed liquid taking-up deionization
Water centrifuge washing 6 times;Then reactant is placed in 12 h drying in 30 DEG C of vacuum drying ovens, obtains final MoS2Nano particle with
The liberation of hydrogen catalysis material of flower-shaped carbon.
Flower-shaped carbon is presented three-dimensional structure as can see from Figure 1, and contains some big holes.Through with 22 mg tetrathio molybdenums
Can see the certain uniform load of flower-shaped carbon surface by the scanning electron microscopy in Fig. 2 after sour ammonium solvent heat treatment has substantial amounts of
MoS2Nano particle.Transmission electron microscope figure in Fig. 3 further demonstrates flower-shaped carbon surface MoS2The load of nano particle,
And have high-resolution transmission plot it can be seen that MoS2Crystal it is small-sized(Less than 10 nm), with many defects, these defects
Introducing be conducive to increase active site.Addition is can see from the linear sweep voltammetry figure and Tafel slope figure of Fig. 4
Preferably, it has relatively low liberation of hydrogen take-off potential to the catalysis activity of the composite of 22 mg four thio ammonium molybdates(~110 mV/
dec)With less Tafel slope.Adding the catalytic performance of the composite of flower-shaped carbon will be significantly higher than pure MoS2Nanometer
Grain, illustrates flower-shaped carbon and MoS2Between there is cooperative effect.
Embodiment 2
Weigh 40 mg four thio ammonium molybdates to be added in 10 ml DMF, ultrasonic 10 min makes four thio ammonium molybdate fully molten
Solution;The hydrazine hydrates of 0.1 ml mono- are added, then mixed liquor is transferred in autoclave pressure, be placed in 200 DEG C of baking ovens and react 18 h;Treat certainly
After being so cooled to room temperature, by feed liquid taking-up deionized water centrifuge washing 6 times;Then reactant is placed in 30 DEG C of vacuum drying ovens
12 h are dried, and obtain final MoS2Nano particle liberation of hydrogen catalysis material.
It is seen from fig 5 that four thio ammonium molybdate itself solvent heat obtains nano flower-like structure.Its catalytic activity of hydrogen evolution is very
Difference.
Embodiment 3
(1)The flower-shaped ZnO that 100 mg synthesize is dispersed in 10 ml deionized waters, ultrasonic 20 min is subsequently adding 100
Mg glucose, ultrasonic 10 min;Then mixed liquor is transferred in pressure good fortune kettle, is placed in 180 DEG C of baking ovens and reacts 24 h;Treat
After naturally cooling to room temperature, product taking-up absolute ethyl alcohol is centrifuged repeatedly washing 5 times;Then product is placed in 60 DEG C of baking ovens
6 h are dried;
(2)The powder for taking 1.0 g drying is placed in tube furnace, is heated with the heating rate of 5 DEG C/min under nitrogen protection
2 h are incubated to 800 DEG C;Finally room temperature is cooled under gas shield.Then by the material after heat treatment with 2 M HCl treatment
1 h, then with deionized water and ethanol eccentric cleaning repeatedly, dries in 60 DEG C of baking ovens, obtains flower-shaped carbon;
(3)Weigh 10 mg four thio ammonium molybdates to be added in 10 ml DMF, ultrasonic 10 min fills four thio ammonium molybdate
Divide dissolving;The flower-shaped carbon of 10 mg is subsequently adding, ultrasonic 30 min helps dispersion;The hydrazine hydrates of 0.1 ml mono- are added, then by mixed liquor
It is transferred in autoclave pressure, is placed in 200 DEG C of baking ovens and reacts 18 h;After room temperature is naturally cooled to, by feed liquid taking-up deionization
Water centrifuge washing 6 times;Then reactant is placed in 12 h drying in 30 DEG C of vacuum drying ovens, obtains final MoS2Nano particle with
The liberation of hydrogen catalysis material of flower-shaped carbon.
As seen from Figure 6, the composite that 10 mg four thio ammonium molybdates are obtained is added it can be seen that MoS2Nano particle
Flower-shaped carbon surface is distributed in sparsely.Due to MoS2Content is less, therefore its catalysis activity is nor very well.
Embodiment 4
(1)The flower-shaped ZnO that 100 mg synthesize is dispersed in 10 ml deionized waters, ultrasonic 20 min is subsequently adding 100
Mg glucose, ultrasonic 10 min;Then mixed liquor is transferred in pressure good fortune kettle, is placed in 180 DEG C of baking ovens and reacts 24 h;Treat
After naturally cooling to room temperature, product taking-up absolute ethyl alcohol is centrifuged repeatedly washing 5 times;Then product is placed in 60 DEG C of baking ovens
6 h are dried;
(2)The powder for taking 1.0 g drying is placed in tube furnace, is heated with the heating rate of 5 DEG C/min under nitrogen protection
2 h are incubated to 800 DEG C;Finally room temperature is cooled under gas shield.Then by the material after heat treatment with 2 M HCl treatment
1 h, then with deionized water and ethanol eccentric cleaning repeatedly, dries in 60 DEG C of baking ovens, obtains flower-shaped carbon;
(3)Weigh 40 mg four thio ammonium molybdates to be added in 10 ml DMF, ultrasonic 10 min fills four thio ammonium molybdate
Divide dissolving;The flower-shaped carbon of 10 mg is subsequently adding, ultrasonic 30 min helps dispersion;The hydrazine hydrates of 0.1 ml mono- are added, then by mixed liquor
It is transferred in autoclave pressure, is placed in 200 DEG C of baking ovens and reacts 18 h;After room temperature is naturally cooled to, by feed liquid taking-up deionization
Water centrifuge washing 6 times;Then reactant is placed in 12 h drying in 30 DEG C of vacuum drying ovens, obtains final MoS2Nano particle with
The liberation of hydrogen catalysis material of flower-shaped carbon.
It will be seen in fig. 7 that the composite for adding 40 mg four thio ammonium molybdates to obtain can see in the presence of a large amount of free
MoS2Nano flower-like structure, and MoS2In the presence of serious agglomeration, serious reunion suppresses the performance of catalysis activity.
Claims (4)
1. a kind of flower-shaped carbon is in situ loads MoS2The preparation method of nano particle composite material, it is characterised in that concretely comprise the following steps:
(1)The flower-shaped ZnO that 50 ~ 500 mg synthesize is dispersed in 5 ~ 20 mL deionized waters, 5 ~ 20 min of ultrasound are subsequently adding
50 ~ 500 mg biomass, 5 ~ 15 min of ultrasound;Then mixed liquor is transferred in autoclave pressure, is placed in 120 ~ 250 DEG C of baking ovens
8 ~ 24 h of reaction;After room temperature is naturally cooled to, product is taken out, washing 3 ~ 8 times is centrifuged repeatedly with absolute ethyl alcohol;To then produce
Thing is placed in 2-24 h drying in 50 ~ 150 DEG C of baking ovens;
(2)The powder for taking 0.1 ~ 1.0 g drying is placed in tube furnace, under nitrogen protection with the heating rate of 2 ~ 10 DEG C/min
400 ~ 1000 DEG C are heated to, 1 ~ 5 h is incubated;Then it is cooled to room temperature under gas shield;Then the material after heat treatment is used
0.5 ~ 5 M HCl process 0.5-6 h, then with deionized water and ethanol eccentric cleaning repeatedly, are dried in 50 ~ 150 DEG C of baking ovens,
Obtain flower-shaped carbon;
(3)Weigh 22mg four thio ammonium molybdates to be added in 10 mL solvents, 5 ~ 60 min of ultrasound make four thio ammonium molybdate fully molten
Solution;The flower-shaped carbon of 2 ~ 20 mg is subsequently adding, 10 ~ 120 min of ultrasound help dispersion;The hydrazine hydrates of 0.1 ~ 1.0 mL mono- are added, then will
Mixed liquor is transferred in autoclave pressure, is placed in 6 ~ 24 h of reaction in 100 ~ 250 DEG C of baking ovens;After room temperature is naturally cooled to, by feed liquid
Take out, with deionized water centrifuge washing 3 ~ 10 times;Then reactant is placed in 2 ~ 24 h drying in 30 ~ 120 DEG C of vacuum drying ovens, is obtained
MoS is loaded to final flower-shaped carbon2Nano particle composite material;
Step(1)In biomass used be the one kind in cellulose, glucose, shitosan, or wherein several mixture.
2. preparation method according to claim 1, it is characterised in that step(3)In solvent used be N, N- dimethyl methyls
One kind in acid amides, acetone, tetrahydrofuran, or wherein several mixed solvents.
3. a kind of flower-shaped carbon original position prepared by the preparation method of claim 1 or 2 loads MoS2Nano particle composite material.
4. flower-shaped carbon as claimed in claim 3 loads MoS2The composite of nano particle as liberation of hydrogen catalyst application.
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