阅读说明：本技术 纳米材料及纳米材料修饰的玻碳电极的制备方法 (The preparation method of nano material and nanometer-material-modified glass-carbon electrode ) 是由 吴静 王宇飞 于 2019-08-16 设计创作，主要内容包括：本说明书实施例提供了一种纳米材料的制备方法,所述纳米材料为CsPbX<Sub>3</Sub>型无机钙钛矿量子点材料,其中X为Cl、Br或I中的一种或多种。该方法包括以下步骤：首先,称取0.3mmolPbX<Sub>2</Sub>、0.1mmolCsCO<Sub>3</Sub>、1.5mL油酸、1.5mL油胺和10mL 1-十八碳烯,放入容器中混合均匀,作为反应原料；然后,将容器放入微波炉中,并以预设加热功率加热预设加热时长,以使反应原料发生反应得到反应产物,其中包括所述纳米材料；接着,将反应产物冷却至预设温度,以预设离心转速离心预设离心时长,以从中分离出纳米材料；再去除上清液,并利用环己烷和乙醇对分离出的纳米材料进行清洗。如此可以实现简单、快速、高通量合成多种不同的无机钙钛矿量子点。所得无机钙钛矿量子点可应用于电化学发光传感器。(This specification embodiment provides a kind of preparation method of nano material, and the nano material is CsPbX 3 The inorganic perovskite quanta point material of type, wherein X is one of Cl, Br or I or a variety of.Method includes the following steps: firstly, weighing 0.3mmolPbX 2 、0.1mmolCsCO 3 , 1.5mL oleic acid, 1.5mL oleyl amine and 10mL 1- octadecene, be put into container and be uniformly mixed, as reaction raw materials；Then, container is put into micro-wave oven, and with the default default heating duration of heating power heating, so that reaction raw materials react to obtain reaction product, including the nano material；Then, reaction product is cooled to preset temperature, with the default default centrifugation duration of centrifugal rotational speed centrifugation, therefrom to isolate nano material；Supernatant is removed again, and the nano material isolated is cleaned using hexamethylene and ethyl alcohol.Simple, quick, a variety of different inorganic perovskite quantum dots of high throughput synthesis so may be implemented.The inorganic perovskite quantum dot of gained can be applied to electrochemical luminescence sensor.)

1. a kind of preparation method of nano material, the nano material is CsPbX₃The inorganic perovskite quanta point material of type, wherein X For one of Cl, Br or I or a variety of, which is characterized in that the described method comprises the following steps:

Weigh 0.3mmolPbX₂、0.1mmolCsCO₃, 1.5mL oleic acid, 1.5mL oleyl amine and 10mL1- octadecene, be put into container In be uniformly mixed, as reaction raw materials；

The container is put into micro-wave oven, and with the default default heating duration of heating power heating, so that reaction raw materials occur Reaction obtains reaction product, includes the nano material in the reaction product；

The reaction product is cooled to preset temperature, with the default default centrifugation duration of centrifugal rotational speed centrifugation, therefrom to isolate Nano material；

Supernatant is removed, and the nano material isolated is cleaned using hexamethylene and ethyl alcohol.

2. the method according to claim 1, wherein the default heating power is 640 W, the default heating Shi Changwei 16min.

3. described preset turns the method according to claim 1, wherein the preset temperature is 15 DEG C to 40 DEG C Speed is 9000rpm, when default centrifugation a length of 10min.

4. the method according to claim 1, wherein in the removal supernatant, and utilizing hexamethylene and ethyl alcohol After being cleaned to the nano material isolated, the method also includes:

Nano material after cleaning is dissolved in the hexamethylene of predetermined volume, nanomaterial solution is obtained.

5. according to the method described in claim 4, wherein, the predetermined volume is 4mL.

6. a kind of preparation method of nanometer-material-modified glass-carbon electrode, which is characterized in that the described method comprises the following steps:

Utilize 0.3 μm of α-Al₂O₃Glass-carbon electrode is polished to mirror surface by powder；

To the glass-carbon electrode after polishing, its surface is rinsed with deionized water, and with being dried with nitrogen；

Take 10 μ L nanomaterial solution drop as claimed in claim 4 on the surface of glass-carbon electrode, naturally dry is obtained such as right It is required that glass-carbon electrode nanometer-material-modified described in 4.

7. a kind of H₂O₂Detection method, which is characterized in that the described method includes:

Using nanometer-material-modified glass-carbon electrode as claimed in claim 6 as anode, H in detection substance is treated₂O₂It is dense Degree is detected.

8. the method according to the description of claim 7 is characterized in that described treat H in detection substance₂O₂Concentration detected In include determining H using following formula₂O₂Concentration:

Y=100509x+8883,

Wherein, x indicates H₂O₂Concentration, y indicate be added H₂O₂The intensity of the electrochemical luminescence generated afterwards in anode, also, it is related Coefficient is 0.9907.

9. a kind of detection method of dopamine, which is characterized in that the described method includes:

Using nanometer-material-modified glass-carbon electrode as claimed in claim 6 as anode, dopamine in detection substance is treated Concentration detected.

10. according to the method described in claim 6, it is characterized in that, the concentration for treating dopamine in detection substance carries out Include that the concentration of dopamine is determined using following formula in detection:

Y=23.00x+0.9984,

Wherein, x indicates the concentration of dopamine, and y indicates that the electrochemical luminescence intensity rate before and after dopamine is added, also, related Coefficient is 0.9917.

Technical field

This specification one or more embodiment is related to field of nanometer material technology more particularly to a kind of prepares inorganic perovskite amount The method of son point material, and the method being applied in electrochemical luminescence sensor.

Background technique

Semiconductor nano is also referred to as quantum dot, it has been studied extensively as a kind of potential photoelectric material.This amount Son point material has both dimensional effect, surface is easy to be modified and with free colloidal state exist etc. advantageous properties so that it Show superior optical property relative to forming identical macroscopic material.They can be dispersed in multi-solvents and difference In matrix, so as to for making a variety of photoelectric devices.

Currently, the most mature photoelectric nano crystalline substance material of development is that divalent and polyvalent metal oxides are nanocrystalline, and metal Halide nano material is then opposite to be studied less.Inorganic perovskite quantum dot (CsPbX₃, X=Cl, one of Br or I or It is a variety of) be a kind of emerging high-quantum efficiency nano luminescent material.It is received by this trivalent of regulation of composition, morphology and size The transmitting light of meter Jing can cover entire visible light region.However, being now widely used in the inorganic perovskite quanta point material of synthesis Method is hot injection method, and this method is needed in very short time (5s) interior quenching reaction, this is easy to generate temperature and dense in the solution Gradient is spent, causes synthesized quantum dot size inhomogenous.Moreover, hot injection method needs prepare precursors in advance, operate It is cumbersome；Pyroreaction under the conditions of anhydrous and oxygen-free is needed, condition is harsh；Resulting product amount is few, low yield.

Inorganic perovskite quantum dot not only has excellent photoluminescent property but also shows good electroluminescent properties.Electricity Chemiluminescence be one kind since electrochemical reaction makes ionized material be excited, release energy during returning to ground state and In the phenomenon that electrode surface shines.The connection that the process discloses electrochemistry and shines between the two.Related Si, CdTe, CdSe It is nanocrystalline repeatedly to be reported with nano-cluster electrochemical luminescence, and to the electrochemical luminescence property of inorganic perovskite quanta point material But rarely has research.

It can be seen that current urgent need develops, one kind is simple, be easily manipulated and high-throughput novel synthesis is inorganic to prepare Perovskite quantum dot, and its electrochemical luminescence property is studied, exploration is carried out related application.

Summary of the invention

In view of the above problems, it is an object of the invention to microwaves to synthesize a kind of nanometer that can be used for electrochemical luminescence sensor Material.Simple using microwave process for synthesizing, easily operated, high-throughput, once-through operation can synthesize a variety of different inorganic perovskites Quantum dot, and can realize a large amount of synthesis.Resulting inorganic perovskite quantum dot can generate very strong electrochemical luminescence.

To achieve the above object, in a first aspect, the present invention provides a kind of preparation method of nano material, the nanometer material Material is CsPbX₃The inorganic perovskite quanta point material of type, wherein X is one of Cl, Br or I or a variety of.The method includes with Lower step:

Weigh 0.3mmolPbX₂、0.1mmolCsCO₃, 1.5mL oleic acid, 1.5mL oleyl amine and 10mL1- octadecene, be put into It is uniformly mixed in container, as reaction raw materials；The container is put into micro-wave oven, and is added so that default heating power heating is default Hot duration, so that reaction raw materials react to obtain reaction product, it include the nano material in the reaction product；It will be described Reaction product is cooled to preset temperature, with the default default centrifugation duration of centrifugal rotational speed centrifugation, therefrom to isolate nano material；It goes The nano material isolated is cleaned except supernatant, and using hexamethylene and ethyl alcohol.

Preferably, the default heating power is 640W, when default heating a length of 16min.

Preferably, the preset temperature is 15 DEG C to 40 DEG C, and the preset rotation speed is 9000rpm, when the default centrifugation A length of 10min.

Preferably, in the removal supernatant, and the nano material isolated is cleaned using hexamethylene and ethyl alcohol Later, the method also includes: the nano material after cleaning is dissolved in the hexamethylene of predetermined volume, it is molten to obtain nano material Liquid.

Preferably, the predetermined volume is 4mL.

Second aspect, the present invention provides a kind of preparation methods of nanometer-material-modified glass-carbon electrode.The method packet Include following steps:

Utilize 0.3 μm of α-Al₂O₃Glass-carbon electrode is polished to mirror surface by powder；To the glass-carbon electrode after polishing, deionization is used Water rinses its surface, and with being dried with nitrogen；Take 10 μ L nanomaterial solution drop as claimed in claim 4 in the table of glass-carbon electrode Face, naturally dry obtain nanometer-material-modified glass-carbon electrode as claimed in claim 4.

The third aspect, the present invention provides a kind of H₂O₂Detection method.The described method includes: using such as claim 6 institute The nanometer-material-modified glass-carbon electrode stated treats H in detection substance as anode₂O₂Concentration detected.

Preferably, described to treat H in detection substance₂O₂Concentration detected in include determining H using following formula₂O₂ Concentration: y=100509x+8883, wherein x indicate H₂O₂Concentration, y indicate be added H₂O₂The electrochemistry generated afterwards in anode Luminous intensity, also, related coefficient is 0.9907.

Fourth aspect, the present invention provides a kind of detection methods of dopamine.The described method includes: using such as claim As anode, the concentration for treating dopamine in detection substance is detected nanometer-material-modified glass-carbon electrode described in 6.

Preferably, it is described treat detection substance in dopamine concentration detected in include, utilize following formula determine The concentration of dopamine: y=23.00x+0.9984, wherein x indicates the concentration of dopamine, and y indicates that the electricity before and after dopamine is added Chemiluminescence intensity ratio, also, related coefficient is 0.9917.

Detailed description of the invention

In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this For the those of ordinary skill of field, without creative efforts, it can also be obtained according to these attached drawings others Attached drawing.

Fig. 1 is the experiment schematic diagram of microwave process for synthesizing provided by the invention；

Fig. 2 is transmission electron microscope (TEM) photo that microwave provided by the invention synthesizes different heating power products therefrom；

Fig. 3 is the luminous intensity figure that microwave provided by the invention synthesizes different heating power products therefrom；

Fig. 4 is transmission electron microscope (TEM) photo that microwave provided by the invention synthesizes different heating time products therefrom；

Fig. 5 is the luminous intensity figure that microwave provided by the invention synthesizes different heating time products therefrom；

Fig. 6 is transmission electron microscope (TEM) photo of inorganic perovskite quantum dot provided by the invention；

Fig. 7 is X-ray diffraction (XRD) figure of inorganic perovskite quantum dot provided by the invention；

Fig. 8 is the absorption spectrum of inorganic perovskite quantum dot provided by the invention；

Fig. 9 is the fluorescence emission spectrum of inorganic perovskite quantum dot provided by the invention；

Figure 10 is the resulting inorganic perovskite quantum dot light emitting stability diagram of microwave process for synthesizing provided by the invention；

Figure 11 is the title that microwave process for synthesizing provided by the invention largely synthesizes inorganic perovskite quantum dot Weight schematic diagram；

Figure 12 is the cathode circulation volt-ampere curve schematic diagram of the electrode of inorganic perovskite quantum dot preparation provided by the invention；

Figure 13 is the anode circulation volt-ampere curve schematic diagram of the electrode of inorganic perovskite quantum dot preparation provided by the invention；

(voltage is certainly for the electrochemical luminescence of inorganic perovskite quantum dot caused by Figure 14 injects for hole provided by the invention 1.04V is scanned to -1.34V) schematic diagram；

Figure 15 be electron injection provided by the invention caused by inorganic perovskite quantum dot electrochemical luminescence (voltage from- 1.34V is scanned to 1.04V) schematic diagram；

Figure 16 is that electrochemical luminescence sensor provided by the invention is used for H₂O₂The schematic diagram of detection；

Figure 17 is the schematic diagram that electrochemical luminescence sensor provided by the invention is used for dopamine detection.

Specific embodiment

It should be understood that protection scope of the present invention is not limited to following specific specific embodiments；It is also understood that this hair Term used in bright embodiment is the protection model that is not intended to be limiting of the invention in order to describe specific specific embodiment It encloses；In description of the invention and claims, unless in addition explicitly pointed out in text, singular "one", " one " and " this It is a " it include plural form.

When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, the present invention used in all technologies and Scientific term is identical as the normally understood meaning of those skilled in the art of the present technique.Except specific method, equipment used in embodiment, Outside material, grasp and record of the invention according to those skilled in the art to the prior art can also be used and this Any method, equipment and the material of the similar or equivalent prior art of method described in inventive embodiments, equipment, material come real The existing present invention.

It is passed as previously mentioned, synthesizing a kind of nano material it is an object of the invention to microwave and being applied to electrochemical luminescence Sensor.Simple using microwave process for synthesizing, easily operated, high-throughput, once-through operation can synthesize a variety of different inorganic perovskites Quantum dot, and can realize a large amount of synthesis.Resulting inorganic perovskite quantum dot can generate very strong electrochemical luminescence.In the following, In conjunction with the embodiments, scheme provided by the invention is specifically described.