CN105080577B - Two cobaltous selenide nanobelts assembling ball, its preparation method and its application - Google Patents

Two cobaltous selenide nanobelts assembling ball, its preparation method and its application Download PDF

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CN105080577B
CN105080577B CN201510578454.1A CN201510578454A CN105080577B CN 105080577 B CN105080577 B CN 105080577B CN 201510578454 A CN201510578454 A CN 201510578454A CN 105080577 B CN105080577 B CN 105080577B
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nanobelts
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cobaltous
cose
nanobelt
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CN105080577A (en
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俞书宏
郑亚荣
高敏锐
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention provides the preparation method that a kind of two cobaltous selenides nanobelt assembles ball, comprise the following steps:Water, organic amine, cobalt source, selenium source are mixed with carbon quantum dot, then obtained mixture is reacted, two cobaltous selenide nanobelts assembling ball is obtained.During two cobaltous selenide nanobelts assembling ball is prepared, the addition of carbon quantum dot can participate in the nucleating growth of two cobaltous selenide nanobelts, and induce nanobelt assembling balling-up, and the two cobaltous selenide nanobelts assembling ball of carbon quantum dot modification is obtained, it can be used as electro-catalysis hydrolysis liberation of hydrogen, the bifunctional catalyst of oxygen uptake reaction.The low production cost of the present invention, synthetic method is simple, achievable large-scale production, when the two cobaltous selenide nanobelts assembling ball of prepared carbon quantum dot modification is used as electro-catalysis hydrolysis liberation of hydrogen, the catalyst of oxygen uptake reaction, with high activity and good stability.

Description

Two cobaltous selenide nanobelts assembling ball, its preparation method and its application
Technical field
The present invention relates to catalyst technical field, more particularly to two cobaltous selenide nanobelts assembling ball, its preparation method and its Using.
Background technology
At present, the energy turns into the key issue of restriction human development.Water-and as current maximum potential energy source, it is how high Water decomposition is at low cost that hydrogen and oxygen obtain the renewable sources of energy by effect, is gradually paid attention to by everybody.Usual hydrolytic process meeting It is related to evolving hydrogen reaction and oxygen evolution reaction, due to the slow dynamics and high cost catalyst of above-mentioned reaction, largely makes The about development of Hydrolysis Industry, therefore it is developing industry to find with high activity, low cost, the catalyst for being easy to prepare on a large scale Change the most important thing in hydrolysis field.In recent years, study hotspot both domestic and external is focused primarily upon efficiently analyses under research acidic electrolyte bath Oxygen-separating catalyst in hydrogen catalyst or alkaline electrolyte, preparing, there is dual or multi-catalytic activity inexpensive catalyst to be One important directions in current catalyst research field.
Cobalt-based chalcogenide is increasingly closed due to aboundresources and in the potential application of catalytic field by everybody Note.Applicant is prepared for the Transition-metal dichalcogenide of a series of new, such as iron sulfide, nickelous selenide, two in research process Cobaltous selenide etc., and find that there is Transition-metal dichalcogenide certain electricity to urge liberation of hydrogen and oxygen evolution activity, especially two cobaltous selenides Nanobelt and its composite hybridization material show excellent electrocatalytic hydrogen evolution and oxygen evolution activity.Research finds two cobaltous selenide nanobelts Hybrid material generally has an excellent catalytic activity in one aspect, but two cobaltous selenides are a kind of to have multi-functional catalysis in itself The material of potentiality, and its preparation method is simple, and how easily extension production, rich reserves select suitable functional material pair It is modified, so as to obtain the Research Challenges that the catalyst with high activity and good stability is such material.
The content of the invention
Present invention solves the technical problem that being to provide a kind of two cobaltous selenides nanobelt assembling ball and preparation method thereof, this Shen The two cobaltous selenide nanobelts that please be prepared, which assemble ball as catalyst for water electrolysis, has high activity and good stability.
In view of this, this application provides the preparation method that a kind of two cobaltous selenides nanobelt assembles ball, comprise the following steps:
Water, organic amine, cobalt source, selenium source are mixed with carbon quantum dot, then obtained mixture is reacted, two are obtained Cobaltous selenide nanobelt assembles ball.
It is preferred that, the cobalt source is that cobalt acetate, the selenium source are sodium selenite.
It is preferred that, the organic amine is diethylenetriamine, triethylene tetramine or TEPA.
It is preferred that, the reaction is specially:
Obtained mixture is placed in hydrothermal reaction kettle and sealed, 12~24h is then reacted at 140~200 DEG C.
It is preferred that, the volume ratio of the water and organic amine is 1:2, the mol ratio of the cobalt source and selenium source is 1:1.
It is preferred that, the proportionate relationship of the cumulative volume of the cobalt source, the water and organic amine and the carbon quantum dot is (0.5 ~2) mmol:(35~40) ml:(0.02~0.1) g.
Ball is assembled present invention also provides two cobaltous selenide nanobelts prepared by the preparation method described in such scheme.
It is preferred that, carbon quantum dot is distributed with two cobaltous selenide nanobelts of the two cobaltous selenides nanobelt assembling ball.
Present invention also provides two cobaltous selenides described in prepared by the preparation method described in such scheme or such scheme Nanobelt assembles application of the ball in catalyst for water electrolysis.
This application provides the preparation method that a kind of two cobaltous selenides nanobelt assembles ball.Preparing two cobaltous selenide nanobelts During, water, organic amine, cobalt source, selenium source are mixed with carbon quantum dot, then obtained mixture is reacted, two are obtained Cobaltous selenide nanobelt assembles ball.The application two cobaltous selenide nanobelts assembling ball be two cobaltous selenide nanobelts in growth course by Formed in the participation induction nanobelt of carbon quantum dot, on the one hand the two cobaltous selenide nanobelts modified by carbon quantum dot can change The electronic structure of kind active site cobalt, the nanobelt of one side carbon quantum dot induction assembles the three-dimensional structure of ball, is conducive to It is as the transmission of catalyst electrolyte and generation gas in catalytic process, and therefore, two cobaltous selenides prepared by the application are received Rice has high activity and good stability with assembling ball as catalyst for water electrolysis.
Brief description of the drawings
Fig. 1 is pure CoSe prepared by the embodiment of the present invention 12SEM (SEM) image of nanobelt, illustration is The enlarged drawing of transmission electron microscope (TEM);
Fig. 2 is CDs-CoSe prepared by the embodiment of the present invention 22The TEM figures of composite, illustration is schemed for partial enlargement TEM;
Fig. 3 is the high-resolution TEM figures of CDs composites prepared by the embodiment of the present invention 2, and right part of flg is partial enlargement carbon amounts Son point high-resolution TEM figures;
Fig. 4 is pure CoSe prepared by the embodiment of the present invention 12CDs-CoSe prepared by nanobelt and the embodiment of the present invention 22It is multiple The X-ray electronic diffraction collection of illustrative plates of condensation material;
Fig. 5 is CDs-CoSe prepared by the embodiment of the present invention 22The STEM-mapping figures of composite;
Fig. 6 is glass-carbon electrode, 20wt% commercializations platinum carbon, the pure CoSe of the preparation of the embodiment of the present invention 12Nanobelt and Ben Fa CDs-CoSe prepared by bright embodiment 22The electrocatalytic hydrogen evolution catalytic activity test curve figure of composite;
Fig. 7 is pure CoSe prepared by the embodiment of the present invention 12CDs-CoSe prepared by nanobelt and the embodiment of the present invention 22It is multiple The electrocatalytic hydrogen evolution stability test curve map of condensation material;
Fig. 8 is CDs-CoSe prepared by the embodiment of the present invention 22Composite, commercial oxidation ruthenium and the embodiment of the present invention 1 are made Standby pure CoSe2The electro-catalysis analysis oxygen catalytic activity test curve figure of nanobelt;
Fig. 9 is CDs-CoSe prepared by the embodiment of the present invention 22The electro-catalysis analysis oxygen catalytic stability test of composite is bent Line chart;
Figure 10 is CDs-CoSe prepared by the embodiment of the present invention 32The TEM figures of composite, illustration is partial enlargement TEM Figure;
Figure 11 is CDs-CoSe prepared by the embodiment of the present invention 42The TEM figures of composite, illustration is partial enlargement TEM Figure;
Figure 12 is the CDs-CoSe for preparing under different predecessor input amounts2Assemble the electrocatalytic hydrogen evolution active testing curve of ball Figure;
Figure 13 is that herein described two cobaltous selenides nanobelt assembles TEM figure of the ball under the differential responses time.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention Limitation.
The embodiment of the invention discloses the preparation method that a kind of two cobaltous selenides nanobelt assembles ball, comprise the following steps:
Water, organic amine, cobalt source, selenium source are mixed with carbon quantum dot, then obtained mixture is reacted, two are obtained Cobaltous selenide nanobelt assembles ball.
During two cobaltous selenide nanobelts assembling ball is prepared, the addition of carbon quantum dot can participate in two cobaltous selenide nanobelts Nucleating growth, and induce nanobelt assembling balling-up, that is, obtain the two cobaltous selenide nanobelts assembling ball of carbon quantum dot modification, it can The bifunctional catalyst of liberation of hydrogen, oxygen evolution reaction is hydrolyzed as electro-catalysis.
During two cobaltous selenide nanobelts assembling ball is prepared, the application is first mixed raw material.The application institute State carbon quantum dot similar with various metal quantum points, carbon quantum dot can emit a brilliant light under light conditions.The application institute State what carbon quantum dot was directly prepared for the applicant using pollen, specifically refer to Adv.Sci.2015,2,1500002.
During mixing, the volume ratio of the water and organic amine is preferably 1:2, the cobalt source is rubbed with the selenium source That ratio preferably 1:1, the cumulative volume of the mole of herein described cobalt source, the water and the organic amine mixed solution with it is described The ratio of the quality of carbon quantum dot is preferably (0.5~2) mmol:(35~40) mL:(0.02~0.1) g.Herein described cobalt source Preferably cobalt acetate, the selenium source is preferably sodium selenite;The organic amine is preferably diethylenetriamine, triethylene tetramine or four The amine of ethene five, more preferably diethylenetriamine.
According to the present invention, mixture is preferably reacted in the environment of HTHP after raw material mixing.The application institute State mixture and reacted in the environment of HTHP and specifically referred to:
The mixture is placed in hydrothermal reaction kettle and sealed, 12~24h is then reacted at 140 DEG C~200 DEG C.
In above-mentioned course of reaction, organic amine molecule is protonated under high-temperature solvent heat condition with water reaction, so that shape Into the amine molecule of positively charged, the amine molecule of protonation with selenium coordination by being connected to close in two selenizing cobalt layers, with linear junction The amine of structure serves template molecule effect, and results in layered nano-structure, and the growth that carbon quantum dot can participate in nanobelt is born It is loaded among nanobelt.The specific forming process of two cobaltous selenide nanobelts assembling ball is as shown in figure 13, as seen from the figure, in carbon quantum Under the participation put, two cobaltous selenide nanobelts can reunite forms aggregate together, and initial reaction stage aggregate flocks together around It is scattered many short-term structures, as reaction proceeds to 8h, a large amount of laminated structures of aggregate superficial growth continue to react 18h, obtained To the assembling ball of a large amount of banded structures of many internal consolidation superficial growths, continue reaction assembling spheroid and continue to grow up, band onto surface Structure tails off.
Present invention also provides two cobaltous selenide nanobelts assembling ball (CDs- prepared by the preparation method described in such scheme CoSe2).The two cobaltous selenides nanobelt assembling ball (CDs-CoSe2) surface distributed has carbon quantum dot.
Present invention also provides the CDs-CoSe described in prepared by such scheme or such scheme2Ball is assembled in water electrolysis Application in catalyst, it can be used for electro-catalysis to hydrolyze evolving hydrogen reaction and analyses the catalyst of oxygen.
Herein described CDs-CoSe2Assemble ball includes following step for the preparation that electro-catalysis hydrolyzes liberation of hydrogen test electrode Suddenly:
(1) three-electrode system is used, with the CDs-CoSe of the present invention2Assembling ball is used as working electrode, saturated calomel electrode As reference electrode, platinized platinum is as to electrode;
(2) electrolyte is 0.5M sulfuric acid solution, and test electro-catalysis hydrolysis liberation of hydrogen is lived under logical hydrogen, room temperature condition before test Property.
CDs-CoSe of the present invention2Assemble ball includes following step for the preparation that electro-catalysis hydrolyzes analysis oxygen test electrode Suddenly:
(1) three-electrode system is used, with the CDs-CoSe of the present invention2Assembling ball is used as working electrode, silver/silver chloride electrode As reference electrode, platinized platinum is as to electrode;
(2) electrolyte is 0.1M potassium hydroxide solution, logical oxygen before test;Electro-catalysis hydrolysis analysis is tested under room temperature condition Oxygen activity;
(3) stability test is in 0.1M potassium hydroxide solution, under constant voltage, to test its curent change.
This application provides a kind of two cobaltous selenides nanobelt assembling ball, its preparation method and its application.Herein described two Cobaltous selenide nanobelt assembling ball is that a kind of carbon quantum dot induces two cobaltous selenide nanobelts assembling ball, and the addition of carbon quantum dot can be participated in The nucleating growth of two cobaltous selenide nanobelts, and induce nanobelt assembling balling-up;Detailed process is:By cobalt source, selenium source and carbon quantum Point is dissolved in the in the mixed solvent that organic amine and water are constituted, then is reacted under high temperature and high pressure environment, produces carbon quantum dot modification Two cobaltous selenide nanobelts assemble ball, and it can be used as electro-catalysis hydrolyst.
The present invention induces two cobaltous selenide nanobelt CoSe using carbon quantum dot2The synthetic method for assembling ball is simple, is produced into This is cheap, and large-scale production can be achieved, the two cobaltous selenide nanobelt CoSe prepared using the present invention2Assembling ball has good pair Function electrocatalytic hydrogen evolution, oxygen evolution activity and stability, and still there is preferable electrocatalytic hydrogen evolution activity in neutral conditions, can Applied to electrolysis water and wastewater industry and electrochemistry hydrogen manufacturing system etc..
For a further understanding of the present invention, the two cobaltous selenide nanobelts that the present invention is provided are assembled with reference to embodiment Ball, its preparation method and its application are described in detail, and protection scope of the present invention is not limited by the following examples.
What the carbon quantum dot employed in following embodiments was directly prepared for applicant using pollen, it is specific to prepare Process has been published in Adv.Sci.2015,2,1500002.
Embodiment 1
It is 2 that the sodium selenite of 1mmol cobalt acetate and 1mmol is dissolved in into volume ratio:1 diethylenetriamine and water mixing In solution, 40min is stirred;Said mixture is transferred in the 50mL reactors of polytetrafluoroethyllining lining and sealed, in temperature control 18h is reacted in baking oven at 180 DEG C, completes to take out after reaction and is cooled to room temperature;Products therefrom is cleaned with ethanol, and at 60 DEG C Vacuum environment in dry 8 hours, produce pure CoSe2Nanobelt.
CoSe prepared by the present embodiment2The SEM figures of nanobelt are as shown in figure 1, illustration is TEM pictures.Can from SEM figures To see, simple CoSe2Nanobelt soilless sticking body is present, and TEM pictures display width is 200nm~500nm CoSe2Nanometer It is uniformly distributed with random.
Embodiment 2
It is 2 that 1mmol cobalt acetate, 1mmol sodium selenite and 0.1g carbon quantum dots are dissolved in into volume ratio:1 diethyl In alkene triamine and water mixed solution, stir 40 minutes;Said mixture is transferred to the 50mL reactors of polytetrafluoroethyllining lining In and seal, reacted 18 hours at 180 DEG C in temperature control oven, take out after completing reaction and be cooled to room temperature;Products therefrom Cleaned, and dried 8 hours in 60 DEG C of vacuum environment with ethanol, produce CDs-CoSe2Composite.
CDs-CoSe prepared by the present embodiment2The TEM figures of composite are as shown in Fig. 2 illustration is schemed for partial enlargement TEM Piece.From the figure, it can be seen that CoSe2No longer exist with scattered nanometer band forms, and be wound around being assembled into about 500nm sizes Ball, the TEM figures from partial enlargement are as can be seen that CoSe2Spherical assembly still has layer structure, shows preparing pure CoSe2 During nanobelt, the introducing of carbon quantum dot can induce CoSe2Growth, make its assembling balling-up.
Fig. 3 is CDs-CoSe manufactured in the present embodiment2Composite high-resolution picture, it can be seen that carbon quantum dot is uniformly divided Cloth is in CoSe2Surface, right side is carbon quantum dot amplification picture, shows that carbon quantum dot is successfully introduced into the composite of preparation; Fig. 4 is CDs-CoSe manufactured in the present embodiment2Pure CoSe prepared by composite and embodiment 12The XRD spectrum of nanobelt, curve The pure CoSe of A2The XRD spectrum of nanobelt, curve B is CDs-CoSe2The XRD spectrum of composite, shows to introduce institute after carbon quantum dot It is CoSe to obtain product2;Fig. 5 is the CDs-CoSe prepared by the present embodiment2The STEM-mapping figures of composite, it can be seen that Co, Se and C element are evenly distributed on CDs-CoSe2Assemble on ball, show to be successfully prepared CDs-CoSe2Composite.
Fig. 6 is glass-carbon electrode, 20wt% commercializations platinum carbon, the pure CoSe of the preparation of embodiment 12Nanobelt and this implementation are made Standby CDs-CoSe2The electrocatalytic hydrogen evolution catalytic activity test curve figure of composite, wherein curve A urges for the electricity of glass-carbon electrode Change the catalytic activity curve of liberation of hydrogen, curve B is the catalytic activity curve for the electrocatalytic hydrogen evolution that 20wt% is commercialized platinum carbon, curve C The pure CoSe prepared for embodiment 12The catalytic activity curve of the electrocatalytic hydrogen evolution of nanobelt, curve D is that this implementation is prepared CDs-CoSe2The catalytic activity curve of composite;From the figure, it can be seen that pure glass-carbon electrode is almost in 0.5M sulfuric acid solutions There is no electrocatalytic hydrogen evolution activity, the overpotential of 20wt% commercialization platinum carbons is about 0V, pure CoSe2Nanobelt shows higher rise Beginning overpotential is about 95mV, in 10mAcm-2The overpotential of current density be about 212mV, and prepared by the present embodiment CDs-CoSe2Composite starting overvoltage can be reduced to 37mV, and as overvoltage increase current density is quickly raised, in mistake Potential 128mV is that can reach 10mA cm-2Current density, compared to better than other transition metal sulfur family catalyst (molybdenum sulfide, Cobalt sulfide, cobaltous selenide etc.), show that the introducing of carbon quantum is conducive to the raising of composite electrocatalytic hydrogen evolution catalytic activity;
Fig. 7 is pure CoSe prepared by embodiment 12CDs-CoSe prepared by nanobelt and the embodiment of the present invention 22Composite wood Curve A is pure CoSe in the electrocatalytic hydrogen evolution stability test curve map of material, figure2The electrocatalytic hydrogen evolution of nanobelt original state is bent Line, curve B is pure CoSe2Electrocatalytic hydrogen evolution curve after the circle of nanobelt circulation 1000, curve C is CDs-CoSe2Nanobelt is initial The electrocatalytic hydrogen evolution curve of state, curve D is CDs-CoSe2Electrocatalytic hydrogen evolution curve after the circle of nanobelt circulation 1000.From figure In as can be seen that by 1000 circle cyclic voltammetry scans after, pure CoSe2Nanobelt activity is greatly reduced, 10mA·cm-2Current density when, the pure CoSe after stability test2Its overpotential rise about 34mV, and CDs-CoSe2 The catalytic activity of assembling ball has almost no change, and shows the introducing induction CoSe of carbon quantum dot2After assembling balling-up, because it is more excellent Architectural feature, can be well in catalytic process keep its three-dimensional chondritic, be greatly improved CoSe2The electricity of material Catalytic hydrogen evolution stability.
Fig. 8 is the CDs-CoSe prepared by the present embodiment2Prepared by composite, commercial oxidation ruthenium and embodiment 1 pure CoSe2Curve A is current density-electricity of commercial oxidation ruthenium in the electro-catalysis analysis oxygen catalytic activity test curve figure of nanobelt, figure Buckle line, curve B is CDs-CoSe2The current density voltage curve of composite, curve C is pure CoSe prepared by embodiment 12 The current density voltage curve of nanobelt.As in figure it can be found that CDs-CoSe prepared by the present embodiment2Composite Onset potential (about 273mV) is close with commercial oxidation ruthenium (about 250mV), compared to pure CoSe2Nanometer is carried and is obviously improved, and 10mA·cm-2Current density when, CDs-CoSe2Composite and pure CoSe2Nanobelt reduces about 370mV, and higher than report Other non-precious metal catalysts (manganese oxide, cobalt oxide, cobalt sulfide, cobaltous selenide etc.) in road.
Fig. 9 is the CDs-CoSe prepared by the embodiment of the present invention 12The electro-catalysis analysis oxygen catalytic stability test of composite Curve map.As can be seen from the figure under constant overpotential, current density does not almost occur bright after 10000s test Aobvious decay, therefore, is also demonstrated that CDs-CoSe prepared by present example2Composite is used as electro-catalysis oxygen-separating catalyst With good stability.
Embodiment 3
It is 2 that 0.5mmol cobalt acetate, 0.5mmol sodium selenite and 0.1g carbon quantum dots are dissolved in into volume ratio:1 In diethylenetriamine and water mixed solution, stir 40 minutes;The 50mL that said mixture is transferred into polytetrafluoroethyllining lining is anti- Answer in kettle and seal, reacted 18 hours at 180 DEG C in temperature control oven, complete to take out after reaction and be cooled to room temperature;Gained Product is cleaned with ethanol, and is dried 8 hours in 60 DEG C of vacuum environment, produces CDs-CoSe2Composite.The present embodiment system Standby CDs-CoSe2The SEM figures and TEM figures of composite are as indicated by 10.
Embodiment 4
It is 2 that 2mmol cobalt acetate, 2mmol sodium selenite and 0.1g carbon quantum dots are dissolved in into volume ratio:1 diethyl In alkene triamine and water mixed solution, stir 40 minutes;Said mixture is transferred to the 50mL reactors of polytetrafluoroethyllining lining In and seal, reacted 18 hours at 180 DEG C in temperature control oven, take out after completing reaction and be cooled to room temperature;Products therefrom Cleaned, and dried 8 hours in 60 DEG C of vacuum environment with ethanol, produce CDs-CoSe2Composite.It is manufactured in the present embodiment CDs-CoSe2Assemble ball SEM figures and TEM figures are as shown in figure 11.Figure 12 is the CDs-CoSe for preparing under different predecessor input amounts2 It is that 0.05mmol predecessors put into the lower CDs- prepared to assemble A curves in the electrocatalytic hydrogen evolution active testing curve map of ball, figure CoSe2The electrocatalytic hydrogen evolution activity curve of ball is assembled, curve B is that 2mmol predecessors put into the lower CDs-CoSe prepared2Assemble ball Electrocatalytic hydrogen evolution activity curve, curve C is that 1mmol predecessors put into the lower CDs-CoSe prepared2Assemble the electro-catalysis analysis of ball Hydrogen activity curve, as seen from Figure 12, the assembling ball prepared in 1mmol input amount have relatively low take-off potential, show Go out preferably electrocatalytic hydrogen evolution activity.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair , under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention. A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one The most wide scope caused.

Claims (9)

1. a kind of two cobaltous selenides nanobelt assembles the preparation method of ball, comprise the following steps:
Water, organic amine, cobalt source, selenium source are mixed with carbon quantum dot, are then placed in obtained mixture close in hydrothermal reaction kettle Envelope, then reacted at 140~200 DEG C, obtain two cobaltous selenide nanobelts assembling ball.
2. preparation method according to claim 1, it is characterised in that the cobalt source is that cobalt acetate, the selenium source are sub- selenium Sour sodium.
3. preparation method according to claim 1, it is characterised in that the organic amine is diethylenetriamine, triethylene four Amine or TEPA.
4. preparation method according to claim 1, it is characterised in that the time of the reaction is 12~24h.
5. preparation method according to claim 1, it is characterised in that the volume ratio of the water and organic amine is 1:2, it is described Cobalt source and the mol ratio of selenium source are 1:1.
6. preparation method according to claim 5, it is characterised in that the cumulative volume of the cobalt source, the water and organic amine Proportionate relationship with the carbon quantum dot is (0.5~2) mmol:(35~40) ml:(0.02~0.1) g.
7. the two cobaltous selenide nanobelts assembling ball prepared by the preparation method described in any one of claim 1~6.
8. two cobaltous selenides nanobelt according to claim 7 assembles ball, it is characterised in that the two cobaltous selenides nanobelt group Carbon quantum dot is distributed with the two cobaltous selenide nanobelts for filling ball.
9. application of the two cobaltous selenide nanobelts assembling ball in catalyst for water electrolysis described in any one of claim 7~8.
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