CN105126876A - Flowerlike carbon-loaded MoS<2> nano-particle composite and preparation method thereof - Google Patents
Flowerlike carbon-loaded MoS<2> nano-particle composite and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of catalytic materials and particularly provides a flowerlike carbon-loaded MoS<2> nano-particle composite and a preparation method thereof. The preparation method comprises the steps that firstly, flowerlike ZnO serves as a template and biomass serves as a precursor, and flowerlike carbon is obtained through a simple hydrothermal method and subsequent high-temperature heat treatment and acid etching; then the obtained flowerlike carbon and ammonium tetrathiomolybdate are subjected to solvothermal processing, and the composite in which MoS<2> nano-particles are evenly loaded on the flowerlike carbon is obtained. Hydrogen evolution catalysis tests indicate that the composite is low in hydrogen evolution take-off potential and Tafele slope and good in long-term stability, wherein the hydrogen evolution take-off potential is approximately 110 mV, and the Tafele slope is 65 mV/dec. According to the flowerlike carbon-loaded MoS<2> nano-particle composite and the preparation method thereof, the biomass which is wide in source serves as the precursor of the flowerlike carbon, a two-step method, namely the hydrothermal processing and the solvothermal processing, is adopted, the operation is simple, the production cost is low, little pollution is caused to the environment, the serial production and large-scale production are easy to achieve, and the flowerlike carbon-loaded MoS<2> nano-particle composite has a good industrial production basis and a wide application prospect.
Description
Technical field
The invention belongs to catalysis material technical field, be specifically related to a kind of liberation of hydrogen catalysis material and its preparation method and application.
Background technology
In world's today, the population increased fast and industry make the energy of the more effective more environmental protection of exploitation become more and more urgent to the larger demand of the energy and the environmental crisis that causes thus.Wherein Hydrogen Energy is as the most potential energy of one, because the feature of high combustion heat value and reusable edible is considered to probably replace fossil energy in future.At present, electrochemistry hydrogen manufacturing remains a kind of method preparing hydrogen be widely used.In order to improve the efficiency of electrochemistry hydrogen manufacturing, often need to adopt the catalyst that can reduce overpotential of hydrogen evolution, the catalyst of platinum base is considered to wherein the most effective catalyst, because its overpotential of hydrogen evolution is no better than zero.But platinum is few at earth content, and expensive, thus greatly limit their large-scale application in business.Therefore, the base metal liberation of hydrogen catalyst developing low cost, high efficiency and high stability just becomes very necessary.Up till now, existing multiple non-platinum based catalyst is proved to be has high catalytic activity for hydrogen evolution, such as " Germany should change " (Angew.Chem.2015,127,1) iron reported is nanocrystalline, " JACS " (J.Am.Chem.Soc.2013,135,17881) molybdenum bisuphide reported, " Germany should change " (Angew.Chem.Int.Ed.2014,53,12855) the phosphatization cobalt reported and and " energy and environment science " (EnergyEnviron.Sci., 2013,6,943) molybdenum carbide etc. reported.
Molybdenum bisuphide (MoS
2) be a kind of typical two-dimensional layer material, based on it, prepare liberation of hydrogen catalysis material receive and pay close attention to widely.In the past few years, the catalytic activity of hydrogen evolution that a large amount of theories and experimental study disclose molybdenum bisuphide mainly comes from the unsaturated sulphur atom being positioned at edge.But the low conductivity that it is intrinsic and serious agglomeration traits inhibit the exposed of the conduction of electronics and catalytic activity edge, cause the catalytic activity of hydrogen evolution of difference.In order to address these problems, large quantifier elimination is devoted to nano level MoS
2load forms molybdenum bisuphide-carbon hybrid material on electrically-conductive backing plate, such as Graphene, CNT and some other material with carbon element.Such as, Dai Hongjie etc. report MoS at first in " JACS " (J.Am.Chem.Soc.2011,133,7296)
2the composite of high catalytic activity for hydrogen evolution is prepared in nano particle in situ growth on graphene film.Subsequently, by MoS
2nano particle load is at " application material and interface " (ACSAppl.Mater.Interfaces; 2014; 6 (23); 21534) graphene aerogel reported, " advanced function material " (Adv.Funct.Mater.2013; 23,5326) the mesoporous grapheme foam reported, " nanoscale " (Nanoscale, 2013; 5,7768; Nanoscale, 2014,6,5624) CNT reported and graphene paper and " materials chemistry will A " (J.Mater.Chem.A
,2015
,3
,5041) work that the carbon fiber foam etc. reported prepares liberation of hydrogen catalytic composite materials is reported in succession.These work show the material electronics conducting power of raising and increase exposed MoS
2active number of edges is two key factors affecting catalytic activity.
Although the Graphene of various structure and CNT are often used to load MoS
2nano particle, but often cost is higher for the preparation process of these conducting bases, and also environmental pollution is larger.And living beings are used for preparing conductive carbon material due to its source and recyclability just widely.Hydrothermal carbonization method is a kind of extensive adopted method of conversion of biomass because this method cost is low, environmental friendliness and be easy to operation.The living beings enough to hydrothermal carbonization carry out the electric conductivity that high-temperature heat treatment can significantly improve material further.In addition, studies have reported that in the hydrothermal carbonization process of living beings, add some mould materials, as graphene oxide sheet or MoS
2sheet, can make the hydro-thermal carbon of generation be coated on these mould material surfaces.
In the present invention, the hydro-thermal carbon that first we realize living beings by hydro-thermal method is coated on flower-shaped ZnO surface, after high temperature cabonization subsequently and acid etch, obtains flower-shaped material with carbon element.And then with the flower-shaped carbon of conduction for substrate and four thio ammonium molybdate solvent heat finally obtain MoS
2the nano composite material of nano particle load on flower-shaped carbon.As liberation of hydrogen catalysis material, flower-shaped carbon not only can provide the electronic conduction ability that material is good, in addition due to it and MoS
2between strong interaction can also suppress MoS significantly
2reunion, thus exposed more active MoS
2edge.In addition the three-dimensional porous structure of flower-shaped carbon itself, can also increase the contact area with electrolyte, and promote hydrionic diffusion.Therefore this material performance is lower liberation of hydrogen take-off potential, less Tafel slope and good long-time stability.
Summary of the invention
The object of the present invention is to provide a kind of low cost, environmental friendliness and the flower-shaped carbon load MoS of catalytic activity of hydrogen evolution excellence
2nano composite material of nano particle and its preparation method and application.
MoS provided by the invention
2the nano composite material of nano particle load on graphite is at flower-shaped carbon surface growth in situ MoS by solvent-thermal method
2nano particle.The introducing of the flower-shaped carbon of conduction, not only can improve the electron transmission ability of material, can also suppress MoS
2reunion, thus expose more active site, obtain good liberation of hydrogen catalytic effect.
Flower-shaped carbon load MoS provided by the invention
2the Nano-composite materials method of nano particle, concrete steps are:
(1) be dispersed in 5 ~ 20ml deionized water by the flower-shaped ZnO that 50 ~ 500mg synthesizes, ultrasonic 5 ~ 20min, then adds 50 ~ 500mg living beings, ultrasonic 5 ~ 15min; Then mixed liquor is transferred in autoclave pressure, be placed in 120 ~ 250 DEG C of baking oven reaction 8 ~ 24h; After naturally cooling to room temperature, by product taking-up absolute ethyl alcohol centrifuge washing 3 ~ 8 times repeatedly; Subsequently product is placed in 50 ~ 150 DEG C of baking oven 2-24h to dry, powdered;
(2) powder getting 0.1 ~ 1.0g oven dry is placed in tube furnace, is heated to 400 ~ 1000 DEG C under nitrogen protection with the heating rate of 2 ~ 10 DEG C/min, insulation 1 ~ 5h; Then cool to room temperature under gas shield; Then by the 0.5 ~ 5MHCl process 0.5-6h of the material after heat treatment, then use deionized water and ethanol eccentric cleaning repeatedly, dry in 50 ~ 150 DEG C of baking ovens, obtain flower-shaped carbon;
(3) taking 5 ~ 50mg four thio ammonium molybdate joins in 10ml solvent, and ultrasonic 5 ~ 60min makes four thio ammonium molybdate fully dissolve; Then add the flower-shaped carbon of 2 ~ 20mg, ultrasonic 10 ~ 120min helps dispersion; Add 0.1 ~ 1.0ml mono-hydrazine hydrate, subsequently mixed liquor is transferred in autoclave pressure, be placed in 100 ~ 250 DEG C of baking oven reaction 6 ~ 24h; After naturally cooling to room temperature, by feed liquid taking-up deionized water centrifuge washing 3 ~ 10 times; Then reactant is placed in 30 ~ 120 DEG C of vacuum drying oven 2 ~ 24h to dry, obtains final flower-shaped carbon load MoS
2the composite of nano particle.
In the present invention, living beings used in step (1) are, the one in cellulose, glucose, shitosan, or wherein several mixtures.
In the present invention, solvent used in step (3) is the one in DMF, acetone, oxolane, or wherein several mixed solvents.
MoS prepared by the present invention
2the nano composite material of nano particle load on flower-shaped carbon is realized by simple hydro-thermal and solvent heat two-step method.First take living beings as carbon matrix precursor, with flower-shaped ZnO for template, obtain final three-dimensional porous flower-shaped carbon by hydro-thermal method and high annealing subsequently and acid etch.And then with flower-shaped carbon for substrate, by with obtaining of four thio ammonium molybdate solvent heat treatment shape carbon load MoS
2the composite of nano particle.This material can be used as the catalyst of evolving hydrogen reaction, shows good catalytic activity of hydrogen evolution, and it has lower liberation of hydrogen take-off potential (~ 110mV), less Tafel slope (65mV/dec) and excellent long-time stability.This is because the introducing of flower-shaped carbon not only can the electronic conduction ability of reinforcing material, effectively can also suppress MoS simultaneously
2reunion, thus expose more active site.In addition cosmetic carbon and MoS
2between strong electron interaction also can promote MoS
2on electronics be transmitted to cosmetic carbon surface rapidly.
The present invention is easy to operate, and preparation condition is simple, and production cost is low, comparatively environmental protection, is easy to mass, large-scale production, has good suitability for industrialized production basis and wide application prospect.
Accompanying drawing explanation
Fig. 1. scanning electron microscope (SEM) photograph (a) and the transmission electron microscope picture (b) of flower-shaped carbon.
Fig. 2. add the flower-shaped carbon load MoS that 22mg four thio ammonium molybdate obtains
2the scanning electron microscope (SEM) photograph of nano particle composite material.
Fig. 3. add the flower-shaped carbon load MoS that 22mg four thio ammonium molybdate obtains
2the transmission electron microscope picture of nano particle composite material.
Fig. 4. the flower-shaped carbon load MoS that different ratio obtains
2linear sweep voltammetry curve (a) of nano particle composite material and Tafel slope figure (b).
Fig. 5. the pure MoS that four thio ammonium molybdate solvent heat obtains
2scanning electron microscopy (a) and transmission electron microscopy figure (b).
Fig. 6. add the flower-shaped carbon load MoS that 10mg four thio ammonium molybdate obtains
2the scanning electron microscope (SEM) photograph (a) of nano particle composite material and transmission electron microscope picture (b).
Fig. 7. add the flower-shaped carbon load MoS that 40mg four thio ammonium molybdate obtains
2the scanning electron microscope (SEM) photograph (a) of nano particle composite material and transmission electron microscope picture (b).
Detailed description of the invention
Further describe the present invention's flower-shaped carbon load MoS by the following examples
2the preparation method of nano particle composite material and catalytic activity of hydrogen evolution thereof, this embodiment is only illustrate as providing instead of limit the present invention.
embodiment 1
(1) be dispersed in 10ml deionized water by the flower-shaped ZnO that 100mg synthesizes, ultrasonic 20min, then adds 100mg glucose, ultrasonic 10min; Then mixed liquor is transferred in pressure good fortune still, be placed in 180 DEG C of baking ovens and react 24h; After naturally cooling to room temperature, by product taking-up absolute ethyl alcohol centrifuge washing 5 times repeatedly; Subsequently product is placed in 60 DEG C of baking oven 6h to dry;
(2) powder getting 1.0g oven dry is placed in tube furnace, is incubated 2h at being heated to 800 DEG C under nitrogen protection with the heating rate of 5 DEG C/min; Finally cool to room temperature under gas shield.Then by the material 2MHCl process 1h after heat treatment, then use deionized water and ethanol eccentric cleaning repeatedly, dry in 60 DEG C of baking ovens, obtain flower-shaped carbon;
(3) taking 22mg four thio ammonium molybdate joins in 10mlDMF, and ultrasonic 10min makes four thio ammonium molybdate fully dissolve; Then add the flower-shaped carbon of 10mg, ultrasonic 30min helps dispersion; Add 0.1ml mono-hydrazine hydrate, subsequently mixed liquor is transferred in autoclave pressure, be placed in 200 DEG C of baking ovens and react 18h; After naturally cooling 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 oven 12h to dry, obtains final MoS
2the liberation of hydrogen catalysis material of nano particle and flower-shaped carbon.
Flower-shaped carbon presents three-dimensional structure as can see from Figure 1, and containing some large holes.Through with 22mg four thio ammonium molybdate solvent heat treatment after can see that the certain uniform load of flower-shaped carbon surface has a large amount of MoS by the scanning electron microscopy in Fig. 2
2nano particle.Transmission electron microscope figure in Fig. 3 further demonstrates flower-shaped carbon surface MoS
2the load of nano particle, and have high-resolution transmission plot to see MoS
2small-sized (being less than 10nm) of crystal, have a lot of defect, the introducing of these defects is conducive to increasing active site.Can see that the catalytic activity of the composite adding 22mg four thio ammonium molybdate is best from the linear sweep voltammetry figure of Fig. 4 and Tafel slope figure, it has lower liberation of hydrogen take-off potential (~ 110mV/dec) and less Tafel slope.The catalytic performance adding the composite of flower-shaped carbon will be significantly higher than pure MoS
2nano particle, illustrates flower-shaped carbon and MoS
2between there is cooperative effect.
embodiment 2
Taking 40mg four thio ammonium molybdate joins in 10mlDMF, and ultrasonic 10min makes four thio ammonium molybdate fully dissolve; Add 0.1ml mono-hydrazine hydrate, subsequently mixed liquor is transferred in autoclave pressure, be placed in 200 DEG C of baking ovens and react 18h; After naturally cooling 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 oven 12h to dry, obtains final MoS
2nano particle liberation of hydrogen catalysis material.
As seen from Figure 5, four thio ammonium molybdate self solvent heat obtains nano flower-like structure.Its catalytic activity of hydrogen evolution is very poor.
embodiment 3
(1) be dispersed in 10ml deionized water by the flower-shaped ZnO that 100mg synthesizes, ultrasonic 20min, then adds 100mg glucose, ultrasonic 10min; Then mixed liquor is transferred in pressure good fortune still, be placed in 180 DEG C of baking ovens and react 24h; After naturally cooling to room temperature, by product taking-up absolute ethyl alcohol centrifuge washing 5 times repeatedly; Subsequently product is placed in 60 DEG C of baking oven 6h to dry;
(2) powder getting 1.0g oven dry is placed in tube furnace, is incubated 2h at being heated to 800 DEG C under nitrogen protection with the heating rate of 5 DEG C/min; Finally cool to room temperature under gas shield.Then by the material 2MHCl process 1h after heat treatment, then use deionized water and ethanol eccentric cleaning repeatedly, dry in 60 DEG C of baking ovens, obtain flower-shaped carbon;
(3) taking 10mg four thio ammonium molybdate joins in 10mlDMF, and ultrasonic 10min makes four thio ammonium molybdate fully dissolve; Then add the flower-shaped carbon of 10mg, ultrasonic 30min helps dispersion; Add 0.1ml mono-hydrazine hydrate, subsequently mixed liquor is transferred in autoclave pressure, be placed in 200 DEG C of baking ovens and react 18h; After naturally cooling 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 oven 12h to dry, obtains final MoS
2the liberation of hydrogen catalysis material of nano particle and flower-shaped carbon.
As seen from Figure 6, add the composite that 10mg four thio ammonium molybdate obtains and can see MoS
2nano particle is more sparsely distributed in flower-shaped carbon surface.Due to MoS
2content is less, and therefore its catalytic activity neither be fine.
embodiment 4
(1) be dispersed in 10ml deionized water by the flower-shaped ZnO that 100mg synthesizes, ultrasonic 20min, then adds 100mg glucose, ultrasonic 10min; Then mixed liquor is transferred in pressure good fortune still, be placed in 180 DEG C of baking ovens and react 24h; After naturally cooling to room temperature, by product taking-up absolute ethyl alcohol centrifuge washing 5 times repeatedly; Subsequently product is placed in 60 DEG C of baking oven 6h to dry;
(2) powder getting 1.0g oven dry is placed in tube furnace, is incubated 2h at being heated to 800 DEG C under nitrogen protection with the heating rate of 5 DEG C/min; Finally cool to room temperature under gas shield.Then by the material 2MHCl process 1h after heat treatment, then use deionized water and ethanol eccentric cleaning repeatedly, dry in 60 DEG C of baking ovens, obtain flower-shaped carbon;
(3) taking 40mg four thio ammonium molybdate joins in 10mlDMF, and ultrasonic 10min makes four thio ammonium molybdate fully dissolve; Then add the flower-shaped carbon of 10mg, ultrasonic 30min helps dispersion; Add 0.1ml mono-hydrazine hydrate, subsequently mixed liquor is transferred in autoclave pressure, be placed in 200 DEG C of baking ovens and react 18h; After naturally cooling 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 oven 12h to dry, obtains final MoS
2the liberation of hydrogen catalysis material of nano particle and flower-shaped carbon.
As seen from Figure 7, add the composite that 40mg four thio ammonium molybdate obtains and can see there is a large amount of free MoS
2nano flower-like structure, and MoS
2there is serious agglomeration, serious reunion suppresses the performance of catalytic activity.
Claims (5)
1. a flower-shaped carbon original position load MoS
2the preparation method of nano particle composite material, is characterized in that concrete steps are:
(1) be dispersed in 5 ~ 20ml deionized water by the flower-shaped ZnO that 50 ~ 500mg synthesizes, ultrasonic 5 ~ 20min, then adds 50 ~ 500mg living beings, ultrasonic 5 ~ 15min; Then mixed liquor is transferred in pressure good fortune still, be placed in 120 ~ 250 DEG C of baking oven reaction 8 ~ 24h; After naturally cooling to room temperature, product is taken out, with absolute ethyl alcohol centrifuge washing 3 ~ 8 times repeatedly; Subsequently product is placed in 50 ~ 150 DEG C of baking oven 2-24h to dry;
(2) powder getting 0.1 ~ 1.0g oven dry is placed in tube furnace, is heated to 400 ~ 1000 DEG C under nitrogen protection with the heating rate of 2 ~ 10 DEG C/min, insulation 1 ~ 5h; Then cool to room temperature under gas shield; Then by the 0.5 ~ 5MHCl process 0.5-6h of the material after heat treatment, then use deionized water and ethanol eccentric cleaning repeatedly, dry in 50 ~ 150 DEG C of baking ovens, obtain flower-shaped carbon;
(3) taking 5 ~ 50mg four thio ammonium molybdate joins in 10ml solvent, and ultrasonic 5 ~ 60min makes four thio ammonium molybdate fully dissolve; Then add the flower-shaped carbon of 2 ~ 20mg, ultrasonic 10 ~ 120min helps dispersion; Add 0.1 ~ 1.0ml mono-hydrazine hydrate, subsequently mixed liquor is transferred in autoclave pressure, be placed in 100 ~ 250 DEG C of baking oven reaction 6 ~ 24h; After naturally cooling to room temperature, feed liquid is taken out, with deionized water centrifuge washing 3 ~ 10 times; Then reactant is placed in 30 ~ 120 DEG C of vacuum drying oven 2 ~ 24h to dry, obtains final flower-shaped carbon load MoS
2nano particle composite material.
2. preparation method according to claim 1, is characterized in that living beings used in step (1) are the one in cellulose, glucose, shitosan, or wherein several mixtures.
3. preparation method according to claim 1, is characterized in that solvent used in step (3) is the one in DMF, acetone, oxolane, or wherein several mixed solvents.
4. the flower-shaped carbon original position load MoS prepared by one of claim 1-3 preparation method
2nano particle composite material.
5. flower-shaped carbon load MoS as claimed in claim 4
2the composite of nano particle is as the application of liberation of hydrogen catalysis.
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| CN110787823A (en) * | 2019-09-30 | 2020-02-14 | 温州大学 | Three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nano particle, and preparation method and application thereof |
| CN110787823B (en) * | 2019-09-30 | 2022-08-12 | 温州大学 | Three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nano particle as well as preparation method and application thereof |
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