阅读说明：本技术 一种量子点材料及其制备方法与应用 (Quantum dot material and preparation method and application thereof ) 是由 杨波 吴长征 谢毅 于 2019-09-23 设计创作，主要内容包括：本发明公开一种量子点材料及其制备方法与应用,其中,所述量子点材料的制备方法,包括以下步骤：将钼源、表面活性剂、第一溶剂混合,得到第一溶液；将诱发剂和第二溶剂混合,得到第二溶液；混合所述第一溶液和所述第二溶液,得到前驱物胶体；干燥所述前驱物胶体,得到粉末状的量子点材料。可以理解的,本发明的技术方案能够简化工艺流程,有利于实现量子点材料的宏量制备。(The invention discloses a quantum dot material and a preparation method and application thereof, wherein the preparation method of the quantum dot material comprises the following steps: mixing a molybdenum source, a surfactant and a first solvent to obtain a first solution; mixing an inducer and a second solvent to obtain a second solution; mixing the first solution and the second solution to obtain a precursor colloid; and drying the precursor colloid to obtain the powdery quantum dot material. The technical scheme of the invention can simplify the process flow and is beneficial to realizing the macro preparation of the quantum dot material.)

1. a kind of preparation method of quanta point material, which comprises the following steps:

Molybdenum source, surfactant, the first solvent are mixed, the first solution is obtained；

Inducing agent and the second solvent are mixed, the second solution is obtained；

First solution and second solution are mixed, predecessor colloid is obtained；

The dry predecessor colloid, obtains powdered quanta point material.

2. the preparation method of quanta point material as described in claim 1, which is characterized in that the molybdenum source is selected from molybdenum powder, brightness molybdenum Mine, molybdenum nitride, acetic acid molybdenum, molybdenum pentachloride, selenizing molybdenum, hexacarbonylmolybdenum, bicyclopentyl chlorine molybdenum, three carbonyl cycloheptatriene base molybdenums, molybdenum Acid, ammonium molybdate, phosphomolybdic acid, sodium molybdate, phosphating sludge, 12 molybdophosphate sodium of hydration, in three molybdenum carbonyl of molybdenyl trichloride and three amminos It is one or more.

3. the preparation method of quanta point material as described in claim 1, which is characterized in that the surfactant is selected from straight chain Sodium alkyl benzene sulfonate, lignosulfonates, sodium sulfate of polyethenoxy ether of fatty alcohol, heavy alkylbenzene sulfonate, alkylsulfonate, two Glycollic amide, cetyl trimethylammonium bromide, polyvinylpyrrolidone, polyvinyl alcohol, disodium ethylene diamine tetraacetate, lauroyl One of base glutamic acid and sodium stearyl sulfate are a variety of.

4. the preparation method of quanta point material as described in claim 1, which is characterized in that first solvent is selected from C1-C6 Alkylol, water, hexamethylene, oily one of ammonia and oleic acid or a variety of；

And/or second solvent is selected from C1-C6 alkylol, water, hexamethylene, oily one of ammonia and oleic acid or a variety of.

5. the preparation method of quanta point material as described in claim 1, which is characterized in that the inducing agent be selected from hydrogen peroxide, One of ammonium hydroxide, ascorbic acid, sodium borohydride, potassium borohydride, oxalic acid, acetic acid, citric acid, ethyl alcohol and sodium sulfite are more Kind.

6. the preparation method of quanta point material as described in claim 1, which is characterized in that the molybdenum source and the inducing agent Mass ratio is (3000~0.01): 1.

7. such as the preparation method of quanta point material described in any one of claims 1 to 6, which is characterized in that " the mixing institute State the first solution and second solution, obtain predecessor colloid " the step of include:

Second solution is added drop-wise in first solution, the temperature of first solution is adjusted, obtains predecessor colloid.

8. such as the preparation method of quanta point material described in any one of claims 1 to 6, which is characterized in that " the dry institute State predecessor colloid, obtain powdered quanta point material " the step of include:

The dry predecessor colloid obtains powdered quantum dot after 1 hour to 72 hours dry at -50 DEG C~200 DEG C Material.

9. a kind of quanta point material, which is characterized in that the quanta point material is by amount described in any item of the claim 1 to 8 The preparation method of son point material is prepared, and the quanta point material includes molybdenum oxide.

10. a kind of application of quanta point material as claimed in claim 9, which is characterized in that the quanta point material is for making Standby pigment, coating, electrode and supercapacitor.

Technical field

The present invention relates to technology of quantum dots field, in particular to a kind of quanta point material and the preparation method and application thereof.

Background technique

Quanta point material is widely used in the neck such as luminescent device, solar battery, catalysis, biomarker and biomedicine The basic research and application and development in domain.The practical value of quanta point material is widely excavated, preparation and application by More and more concerns.However, the technology of preparing of quanta point material nevertheless suffers from limitation at present, quanta point material is mostly used greatly The operations such as prepared by solvent-thermal method, solvent-thermal method will be separated by solid-liquid separation, be washed when preparing, in this way, process flow is undoubtedly increased, It is unfavorable for the magnanimity preparation of quantum dot.

Summary of the invention

The main object of the present invention is to provide a kind of preparation method of quanta point material, it is intended to simplification of flowsheet, to have It is prepared conducive to the magnanimity of quanta point material.

To achieve the above object, the preparation method of quanta point material proposed by the present invention, comprising the following steps:

Molybdenum source, surfactant, the first solvent are mixed, the first solution is obtained；

Inducing agent and the second solvent are mixed, the second solution is obtained；

First solution and second solution are mixed, predecessor colloid is obtained；

The dry predecessor colloid, obtains powdered quanta point material.

Optionally, the molybdenum source is selected from molybdenum powder, molybdenite, molybdenum nitride, acetic acid molybdenum, molybdenum pentachloride, selenizing molybdenum, six carbonyls Molybdenum, bicyclopentyl chlorine molybdenum, three carbonyl cycloheptatriene base molybdenums, molybdic acid, ammonium molybdate, phosphomolybdic acid, sodium molybdate, phosphating sludge, hydration 12 One of three molybdenum carbonyl of molybdophosphate sodium, molybdenyl trichloride and three amminos is a variety of.

Optionally, the surfactant is selected from sodium n-alkylbenzenesulfonate, lignosulfonates, aliphatic alcohol polyethenoxy Ether sodium sulfate, heavy alkylbenzene sulfonate, alkylsulfonate, diglycollic amide, cetyl trimethylammonium bromide, polyvinyl pyrrole One of alkanone, polyvinyl alcohol, disodium ethylene diamine tetraacetate, lauroyl glutamate and sodium stearyl sulfate are a variety of.

Optionally, first solvent is selected from C1-C6 alkylol, water, hexamethylene, oily one of ammonia and oleic acid or more Kind；And/or second solvent is selected from C1-C6 alkylol, water, hexamethylene, oily one of ammonia and oleic acid or a variety of.

Optionally, the inducing agent is selected from hydrogen peroxide, ammonium hydroxide, ascorbic acid, sodium borohydride, potassium borohydride, oxalic acid, second One of acid, citric acid, ethyl alcohol and sodium sulfite are a variety of.

Optionally, the mass ratio of the molybdenum source and the inducing agent is (3000~0.01): 1.

Optionally, the step of described " mixing first solution and second solution, obtain predecessor colloid " includes:

Second solution is added drop-wise in first solution, the temperature of first solution is adjusted, obtains predecessor Colloid.

Optionally, the step of described " dry the predecessor colloid, obtain powdered quanta point material " includes:

The dry predecessor colloid obtains powdered amount after 1 hour to 72 hours dry at -50 DEG C~200 DEG C Son point material.

The present invention also proposes a kind of quanta point material, the quanta point material by above-mentioned quanta point material preparation method It is prepared, the quanta point material includes molybdenum oxide.

The present invention also proposes a kind of application of quanta point material, and the quanta point material is used to prepare pigment, coating, electrode And supercapacitor.

In technical solution of the present invention, the preparation method of quanta point material mixes molybdenum source, surfactant, the first solvent It closes, obtains the first solution；Inducing agent and the second solvent are mixed, the second solution is obtained；Mix first solution and described Two solution obtain predecessor colloid；The dry predecessor colloid, obtains powdered quanta point material.The present invention passes through mixed The first solution and the second solution are closed, predecessor colloid is prepared into, predecessor colloid is effectively gone by being dried to obtain quanta point material In addition to liquid component, in this way, dry predecessor colloid, it will be able to directly obtain powdered quanta point material, thus avoid The generation of liquid product, without operations such as separation of solid and liquid, washings.It should be understood that technical solution of the present invention can simplify work Skill process is advantageously implemented the magnanimity preparation of quantum dot.

Detailed description of the invention

Fig. 1 is the transmission electron microscope picture of sample prepared by the embodiment of the present invention 1；

Fig. 2 is the photoelectron spectroscopy figure of sample prepared by the embodiment of the present invention 1；

Fig. 3 is the photo figure in kind of sample prepared by the embodiment of the present invention 1~4；

Fig. 4 is ultraviolet-visible-near infrared absorption degree spectrogram of sample prepared by the embodiment of the present invention 1~4；

Specific embodiment

It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase Product.

The present invention proposes a kind of preparation method of quanta point material.

In embodiments of the present invention, the preparation method of quanta point material, comprising the following steps:

Molybdenum source, surfactant, the first solvent are mixed, the first solution is obtained；

Inducing agent and the second solvent are mixed, the second solution is obtained；

First solution and second solution are mixed, predecessor colloid is obtained；

The dry predecessor colloid, obtains powdered quanta point material.

In technical solution of the present invention, the preparation method of quanta point material mixes molybdenum source, surfactant, the first solvent It closes, obtains the first solution；Inducing agent and the second solvent are mixed, the second solution is obtained；Mix first solution and described Two solution obtain predecessor colloid；The dry predecessor colloid, obtains powdered quanta point material.The present invention passes through mixed The first solution and the second solution are closed, predecessor colloid is prepared into, predecessor colloid is effectively gone by being dried to obtain quanta point material In addition to liquid component, in this way, dry predecessor colloid, it will be able to directly obtain powdered quanta point material, thus avoid The generation of liquid product, without operations such as separation of solid and liquid, washings.It should be understood that technical solution of the present invention can simplify work Skill process is advantageously implemented the magnanimity preparation of quantum dot.

Meanwhile in the inventive solutions, the present invention mixes the first solution and the second solution, prepares predecessor glue Body, dry predecessor colloid, can be prepared powdered quanta point material.This preparation method is without behaviour such as washing, separation Make, simplifies operating procedure.Meanwhile the solvent to be volatilized in drying process can recycle.Therefore, amount provided by the invention Son point preparation method it is not only simple, it is low in cost, the secondary pollutions such as waste liquid will not be generated, but also can realize magnanimity prepare, tool There are good economic benefit and environmental benefit, can be used for the fields such as pigment, coating, electrode material and super capacitor.

It should be noted that molybdenum source described in the embodiment of the present invention can be dissolved in the first solvent, while in the first solution Surfactant is also introduced, surfactant is dissolved in the first solvent, and when heating predecessor colloid, the first solvent is with heating The progress of process is constantly volatilized, at this point, molybdenum source is dispersed in surfactant, the embodiment of the present invention is by introducing surface-active Agent avoids the reunion of molybdenum source with this, ensure that the effecting reaction of molybdenum source and inducing agent.Meanwhile the surfactant of introducing again energy Clad is enough formed, makes predecessor colloid obtain powdered quanta point material by drying process with this, to prevent Obtained quanta point material water suction is reunited.Certainly, the inducing agent can be dissolved in the second solvent, when heating predecessor colloid When, the second solvent volatilization, inducing agent is reacted with molybdenum source, guarantees the generation of quanta point material with this.In addition, institute of the embodiment of the present invention The first solvent and the second solvent are stated, can not only use same solvent, but also can be using kind of a solvent is not had to, as long as can be molten respectively Solve molybdenum source and inducing agent.

In an embodiment of the present invention, the molybdenum source is selected from molybdenum powder, molybdenite, molybdenum nitride, acetic acid molybdenum, molybdenum pentachloride, selenium Change molybdenum, hexacarbonylmolybdenum, bicyclopentyl chlorine molybdenum, three carbonyl cycloheptatriene base molybdenums, molybdic acid, ammonium molybdate, phosphomolybdic acid, sodium molybdate, phosphatization One of molybdenum, 12 molybdophosphate sodium of hydration, three molybdenum carbonyl of molybdenyl trichloride and three amminos are a variety of.Preferably, the molybdenum source Selected from molybdenum powder, molybdenite, molybdenum nitride, acetic acid molybdenum, molybdenum pentachloride, selenizing molybdenum, hexacarbonylmolybdenum, molybdic acid, ammonium molybdate, phosphomolybdic acid, molybdenum One of sour sodium, phosphating sludge, 12 molybdophosphate sodium of hydration, three molybdenum carbonyl of molybdenyl trichloride and three amminos are a variety of.More preferably, The molybdenum source is selected from molybdenum powder, molybdenite, acetic acid molybdenum, molybdenum pentachloride, hexacarbonylmolybdenum, molybdic acid, ammonium molybdate, phosphomolybdic acid, sodium molybdate, water It puts the palms together before one one of three molybdenum carbonyl of two molybdophosphate sodium, molybdenyl trichloride and three amminos or a variety of.Molybdenum in molybdenum source of the embodiment of the present invention Element can be molybdenum simple substance, can be the molybdenum element of+1 valence ,+divalent ,+trivalent ,+4 valences ,+5 valences or+6 valences, certainly, molybdenum source both may be used Think ionic compound, and can be covalent compound, the embodiment of the present invention is not only restricted to this.It, can when molybdenum source is lower valency The quanta point material containing molybdenum oxide is prepared using the inducing agent with oxidisability；It, can when molybdenum source is high-valence state The quanta point material containing molybdenum oxide is prepared using the inducing agent with reproducibility.The present invention can be according to molybdenum source Difference select different inducing agents, the preparation containing molybdenum oxide quanta point material is realized with this.

In an embodiment of the present invention, the surfactant is selected from sodium n-alkylbenzenesulfonate, lignosulfonates, rouge Fat alcohol polyethenoxy ether sodium sulfate, heavy alkylbenzene sulfonate, alkylsulfonate, diglycollic amide, cetyl trimethyl bromination In ammonium, polyvinylpyrrolidone, polyvinyl alcohol, disodium ethylene diamine tetraacetate, lauroyl glutamate and sodium stearyl sulfate It is one or more.Preferably, the surfactant is selected from sodium n-alkylbenzenesulfonate, fatty alcohol polyoxyethylene ether sulfuric acid Sodium, heavy alkylbenzene sulfonate, alkylsulfonate, diglycollic amide, cetyl trimethylammonium bromide, polyvinylpyrrolidone, One of polyvinyl alcohol, disodium ethylene diamine tetraacetate and sodium stearyl sulfate are a variety of.More preferably, the surfactant Selected from sodium n-alkylbenzenesulfonate, sodium sulfate of polyethenoxy ether of fatty alcohol, diglycollic amide, cetyl trimethylammonium bromide, One of polyvinylpyrrolidone, polyvinyl alcohol, disodium ethylene diamine tetraacetate and sodium stearyl sulfate are a variety of.It needs Bright, the sodium n-alkylbenzenesulfonate includes neopelex.It lives in order to enable molybdenum source is dispersed in surface Property agent, the embodiment of the present invention selects different surfactants so that molybdenum source and surfactant have good compatibility, with Just molybdenum source can be dispersed in surfactant, to guarantee the effecting reaction of molybdenum source and inducing agent.

In an embodiment of the present invention, first solvent is in C1-C6 alkylol, water, hexamethylene, oily ammonia and oleic acid It is one or more；Preferably, first solvent is selected from one of C1-C6 alkylol, water, hexamethylene and oleic acid or more Kind；More preferably, first solvent is selected from one of C1-C6 alkylol, water and hexamethylene or a variety of.It should be noted that C1-C6 alkylol described in the embodiment of the present invention refers to the alkylol containing 1~6 carbon atom, including methanol, ethyl alcohol, propyl alcohol Deng.In order to reduce impurity, the water can be deionized water.Molybdenum source of the embodiment of the present invention selects the first different solvents, with this Guarantee that molybdenum source is dissolved in the first solvent.Certainly, the embodiment of the present invention can also be using can dissolve molybdenum source and inducing agent simultaneously First solvent, the embodiment of the present invention is unrestricted with this, within the scope of the present invention with upper type.

In an embodiment of the present invention, the mass volume ratio of the molybdenum source and first solvent is (0.01~6) g: 20mL, and the mass volume ratio of the surfactant and first solvent is no more than 3g:20mL.Preferably, the molybdenum source Be (0.1~6) g:20mL with the mass ratio of first solvent, and or, the surfactant and first solvent matter It measures volume ratio and is no more than 1g:10mL.The embodiment of the present invention by adjusting molybdenum source, surfactant and the first solvent mixing dosage Than, on the one hand make molybdenum source and surfactant be dissolved completely in the first solvent, on the other hand when the first solvent volatilizees, molybdenum source It can be dispersed in surfactant, molybdenum source reunion is avoided, ensure that the effecting reaction of molybdenum source and inducing agent with this.

In an embodiment of the present invention, the inducing agent is selected from hydrogen peroxide, ammonium hydroxide, ascorbic acid, sodium borohydride, boron hydrogen Change one of potassium, oxalic acid, acetic acid, citric acid, ethyl alcohol and sodium sulfite or a variety of.Preferably, the inducing agent is selected from peroxide Change one of hydrogen, ammonium hydroxide, ascorbic acid, sodium borohydride, potassium borohydride, oxalic acid, acetic acid, citric acid and sodium sulfite or more Kind.More preferably, the inducing agent be selected from hydrogen peroxide, ammonium hydroxide, ascorbic acid, sodium borohydride, potassium borohydride, oxalic acid, acetic acid and One of citric acid is a variety of.The embodiment of the present invention is selected from different inducing agents according to different molybdenum sources, to realize different molybdenums The preparation of oxide quantum dots material.

In an embodiment of the present invention, the mass volume ratio of the inducing agent and second solvent is (0.01~5) g: 10mL.Preferably, mass volume ratio (0.01~1) g:2mL of the inducing agent and second solvent.More preferably, described to lure Send out mass volume ratio (0.01~0.5) g:2mL of agent and second solvent.The embodiment of the present invention is by adjusting inducing agent and The mixing amount ratio of two solvents guarantees inducing agent and molybdenum source effecting reaction so that inducing agent is dissolved completely in the second solvent with this.

In an embodiment of the present invention, the mass ratio of the molybdenum source and the inducing agent is (3000~0.01): 1.It is preferred that , the mass ratio (600~0.01) of the molybdenum source and the inducing agent: 1.More preferably, the matter of the molybdenum source and the inducing agent Amount is (400~0.01): 1.The embodiment of the present invention ensure that the molybdenum source by the mass ratio of control molybdenum source and inducing agent with this With sufficiently reacting for the inducing agent, so that the quanta point material containing molybdenum oxide be prepared.

In an embodiment of the present invention, described " to mix first solution and second solution, obtain predecessor glue The step of body " includes: that second solution is added drop-wise in first solution, adjusts the temperature of first solution, obtains Predecessor colloid.In order to guarantee the preparation of quanta point material, the embodiment of the present invention is by being added drop-wise to described first for the second solution In solution, with this make include inducing agent the second solution sufficiently with the first solvent reaction, to realize quanta point material Preparation.Preferably, it is 1 drop/sec~30 drops/sec that second solution, which is added drop-wise to the rate of addition in first solution,.It is more excellent , rate of addition is 1 drop/sec~20 drops/sec.Optimal, rate of addition is 1 drop/sec~10 drops/sec.Also, by the second solution While being added drop-wise to the first solution, the temperature for adjusting first solution is 5 DEG C to 100 DEG C, so that the first solvent volatilizees, is obtained Predecessor colloid.Certainly, not only the first solvent and the second solvent can be made to volatilize by high-temperature heating, but also the can be made with cryogenic vacuum One solvent and the volatilization of the second solvent, the embodiment of the present invention is not only restricted to this, within the scope of the present invention with upper type. Preferably, the temperature for adjusting first solution is 25 DEG C~100 DEG C.More preferably, the temperature for adjusting first solution is 35 DEG C~95 DEG C, the present invention can use different temperature according to solvent is not had to, and predecessor colloid is prepared.

In an embodiment of the present invention, described " the dry predecessor colloid, obtain powdered quanta point material " Step includes: that the drying predecessor colloid at -50 DEG C~200 DEG C obtains powdered after drying 1 hour to 72 hours Quanta point material.Preferably, the drying mode is selected from constant pressure and dry, is dried under reduced pressure, is spray-dried, being freeze-dried, boiling and do One of dry, infrared drying, microwave drying and hygroscopic desiccation.More preferably, the drying mode is selected from constant pressure and dry, decompression One of drying, spray drying, freeze-drying, infrared drying, microwave drying and hygroscopic desiccation.Optimal, the drying Mode is selected from constant pressure and dry, is dried under reduced pressure, is spray-dried, being freeze-dried, one of infrared drying and microwave drying.It is preferred that , the drying temperature is -25 DEG C~200 DEG C, optimal, -5 DEG C of drying temperature temperature~180 DEG C.The embodiment of the present invention By adjusting drying temperature, guarantee removing the first solvent and while the second solvent with this, molybdenum source and inducing agent it is effective anti- It answers, to realize the preparation comprising molybdenum oxide quanta point material.Preferably, 1 hour to the 48 hours drying time.It is more excellent , drying time is 1 hour to 24 hours.The embodiment of the present invention adjusts drying temperature and drying time, so that molybdenum source and induction Agent effecting reaction realizes the preparation of molybdenum oxide quanta point material.

The present invention also proposes a kind of quanta point material, the quanta point material by above-mentioned quanta point material preparation method It is prepared.Since quanta point material uses whole technical solutions of above-mentioned all embodiments, at least there is above-mentioned reality All beneficial effects brought by the technical solution of example are applied, this is no longer going to repeat them.Quantum dot material described in the embodiment of the present invention Material, the quanta point material includes molybdenum oxide.Quantum dot size prepared by the embodiment of the present invention is uniform, and quantum dot is averaged Partial size is 3nm~5nm, and the quantum dot prepared has different degrees of absorption to visible light and infrared light, is realized pair with this The adjustment effect of light.

The present invention also proposes a kind of application of quanta point material, and the quanta point material is used to prepare pigment, coating, electrode And supercapacitor.The embodiment of the present invention is prepared with this to visible light and infrared light by selecting unused molybdenum source and inducing agent With the quantum dot absorbed in various degree, so that the regulatory function to light is realized, in this way, prepared quantum dot can be applied to The fields such as pigment, coating, electrode and supercapacitor.

To further illustrate the technical scheme of the present invention combined with specific embodiments below.It should be understood that this place is retouched It states that the specific embodiments are only for explaining the present invention, is not intended to limit the scope of the present invention..