CN114853051A - Cuprous oxide @ copper oxide-graphene nanocomposite and preparation and application thereof - Google Patents

Cuprous oxide @ copper oxide-graphene nanocomposite and preparation and application thereof Download PDF

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CN114853051A
CN114853051A CN202210311193.7A CN202210311193A CN114853051A CN 114853051 A CN114853051 A CN 114853051A CN 202210311193 A CN202210311193 A CN 202210311193A CN 114853051 A CN114853051 A CN 114853051A
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rgo
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胡敬
李金娟
刘波
徐守西
魏涛
程淼
刘倩倩
李宛飞
凌云
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Suzhou University of Science and Technology
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
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    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C—CHEMISTRY; METALLURGY
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    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention relates to a cuprous oxide @ copper oxide-graphene nanocomposite and preparation and application thereof, and relates to the technical field of nanocomposites. The preparation method comprises the following steps of adding graphene oxide into cuprous oxide dispersion liquid under an alkaline condition to obtain a mixed liquid; the mass concentration of the cuprous oxide dispersion liquid is 1-5 mg/mL; the pH of the alkaline condition is 9-14; stirring and reacting the mixed solution to obtain the Cu 2 O @ CuO-RGO nanocomposite. The method has simple process, safety and reliability, and the obtained product has high purity, low cost and easy large-scale preparation; preparation of the obtained Cu 2 The O @ CuO-RGO multi-stage nano composite material has outstanding advantages in the application of detecting nitrogen dioxide gas.

Description

Cuprous oxide @ copper oxide-graphene nanocomposite and preparation and application thereof
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a cuprous oxide @ copper oxide-graphene nano composite material and preparation and application thereof.
Background
At present, in the field of research of new materials, nanomaterials are the most active objects of research, which have important influence on the development of human society. The transition metal nano oxide semiconductor material is suitable for being applied to the aspects of electrode materials, catalysts, sensor sensitive materials and the like due to the advantages of large specific surface area, unique structure, easy preparation and the like. In recent years, researchers at home and abroad research and develop a series of semiconductor materials with sensing characteristics, and the semiconductor materials are applied to the fields of safety early warning, environmental monitoring and the like.
Copper oxide is a very important p-type semiconductor material in transition metal oxide materials, and has the properties of narrow band gap (1.2eV), low cost, good thermal stability and the like. Compared with the traditional sensitive materials of the n-type semiconductor sensor, such as tin dioxide, zinc oxide and the like which are researched earlier, the nano copper oxide has obvious advantages and different sensing mechanisms in the aspects of selectivity, sensitivity and the like because the nano copper oxide belongs to hole conduction.
Chinese patent application publication No. CN102156156A discloses preparation of a three-dimensional copper oxide nano flower-sheet type enzyme-free glucose sensor electrode. The method is simple, is easy and convenient to operate, has good catalytic activity, stability and glucose sensing response characteristics, and the obtained product is attached to the surface of the copper foil and can be used for directly monitoring the blood glucose concentration in a catalytic manner. However, the product obtained by the method has a narrow application range because the copper foil is required to be used as a matrix. Chinese patent application publication No. CN104897726A discloses a method for preparing a nano copper oxide gas-sensitive material by a sol-gel method. The obtained nano copper oxide product is uniform, and the sensitivity to low-concentration gas can be obviously improved, but the method needs high-temperature treatment. Chinese patent application publication No. CN103420408A discloses a method for preparing nano copper oxide in solid phase. The method uses lignosulfonate as a template, utilizes the solid-phase reaction of copper salt and sodium hydroxide/potassium hydroxide, and removes the template through calcination at different temperatures to obtain the nano copper oxide, thereby realizing the controllable technology of the nano material. However, this method is a calcination method, and the reaction temperature is high, so that only uniform particles can be prepared.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the problems of harsh reaction conditions and uniform product of the nano composite material in the prior art.
In order to solve the technical problems, the invention provides a cuprous oxide @ copper oxide-graphene nanocomposite and preparation and application thereof. The method has the advantages of simple process, safety, reliability, high purity of the obtained product, low cost and easy large-scale preparation; preparation of the obtained Cu 2 The O @ CuO-RGO multi-stage nano composite material has outstanding advantages in the application of detecting nitrogen dioxide gas; by changing the concentration, reaction time and the like of each component in the reaction reagent, different Cu with different shapes and different shapes can be obtained 2 Cu of GO composition with O/CuO ratio and different reduction degrees 2 O @ CuO-RGO multi-stage nanocomposite.
It is a first object of the present invention to provide Cu 2 The preparation method of the O @ CuO-RGO nano composite material comprises the following steps,
s1, adding graphene oxide into the cuprous oxide dispersion liquid under an alkaline condition to obtain a mixed liquid; the mass concentration of the cuprous oxide dispersion liquid is 1-5 mg/mL; the pH of the alkaline condition is 9-14;
s2, stirring and reacting the mixed solution in the step S1 to obtain the Cu 2 O @ CuO-RGO nanocomposite.
In one embodiment of the present invention, in the step S1, the pH regulator is sodium hydroxide and/or potassium hydroxide.
In one embodiment of the present invention, in the step of S1, the molar concentration of the regulator is 0.01-1 mol/L.
In one embodiment of the present invention, in the step S1, the mass concentration of the graphene oxide in the mixed solution is 0.05-5 mg/mL.
In one embodiment of the present invention, in the step of S2, the temperature of the reaction is 0 to 39 ℃; the reaction time is 5min-24 h.
In one embodiment of the invention, in the step of S2, the rotation speed of the stirring is 50-1500 r/min.
In one embodiment of the invention, the method further comprises separating the Cu from the reaction liquid 2 The O @ CuO-RGO nano composite material comprises the steps of suction filtration, washing and drying treatment; the washing is performed by using deionized water and ethanol.
In one embodiment of the present invention, the washing is washing with deionized water and ethanol.
The second purpose of the invention is to provide Cu prepared by the method 2 O @ CuO-RGO nanocomposite.
It is a third object of the present invention to provide the Cu 2 The application of the O @ CuO-RGO nano composite material in the detection of nitrogen dioxide.
The principle of the invention is as follows: cuprous oxide (Cu) 2 O) is oxidized into copper hydroxide in an alkaline aqueous solution of Graphene Oxide (GO), the lost electrons simultaneously reduce the Graphene Oxide (GO) into Reduced Graphene Oxide (RGO) in situ, and then Cu (OH) 2 Further dehydrating to form CuO nanocrystalline, assembling the CuO nanocrystalline with the reaction to form CuO nanosheets, and carrying out RGO in-situ compounding to obtain Cu 2 O @ CuO-RGO multi-stage nanosheet flower structure.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the preparation method adopts a liquid phase synthesis method to stir and react at normal temperature to obtain the Cu 2 O @ CuO-RGO multi-stage nano composite gas-sensitive material prepared by Cu 2 The etching self-assembly process of O in alkaline solution is converted into CuO with a multi-stage structure, and GO is reduced in situ to form Cu supported by the multi-stage structure 2 The O @ CuO-RGO multi-stage nano flake composite material has the advantages of simple process, simple raw materials, higher product purity, higher yield and low cost, and can meet the requirement of large-scale production.
(2) The preparation method can obtain Cu with different shapes, different component proportions and different RGO reduction degrees by adjusting the concentration, the reaction temperature, the reaction time and the like of each component of the precursor liquid 2 O @ CuO-RGO multi-stage nano composite material, so that the requirements of various purposes are met.
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In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which:
FIG. 1 shows Cu in example 1 of the present invention 2 SEM picture of O @ CuO-RGO multi-stage nano-sheet flower composite material;
FIG. 2 shows Cu in example 1 of the present invention 2 XRD pattern of O @ CuO-RGO multi-stage nano-flake composite material;
FIG. 3 shows Cu in example 2 of the present invention 2 SEM image of O @ CuO-RGO multi-stage nano-flake composite material;
FIG. 4 shows Cu in example 3 of the present invention 2 SEM picture of O @ CuO-RGO multi-stage nano-sheet flower composite material;
FIG. 5 shows Cu in test example 1 of the present invention 2 O @ CuO-RGO multi-stage nano-flake composite material pair NO 2 Transient response recovery curve of gas;
FIG. 6 shows Cu in test example 2 of the present invention 2 O @ CuO-RGO multi-stage nano-flake composite material pair NO 2 Transient response recovery curve of gas.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
Cu 2 The preparation method of the O @ CuO-RGO nano composite material specifically comprises the following steps:
(1) 0.3g of cuprous oxide was dispersed in 100mL of ultrapure water by magnetic stirring;
(2) adding 17.5mL (1mol/L) of sodium hydroxide/potassium hydroxide into the dispersion liquid obtained in the step (1), and uniformly mixing by magnetic stirring, wherein the pH value is 12.83;
(3) then adding 5mL (10mg/mL) of graphene oxide, and continuously stirring to obtain a mixed solution;
(4) placing the reaction vessel containing the precursor liquid at normal temperature, stirring and reacting at the rotating speed of 700r/min for 5h, and repeatedly washing and drying the obtained product by suction filtration, deionized water and ethanol to obtain Cu 2 O @ CuO-RGO multi-stage nano-flake composite material.
Cu obtained in example 2 The shape of the O @ CuO-RGO multi-level nano-flake composite material is shown in figure 1, XRD of a test product is shown in figure 2, the obtained material is a compound of cuprous oxide and copper oxide, the cuprous oxide is formed into a cuprous oxide @ copper oxide multi-level nano-flake structure by etching and self-assembling original granular cuprous oxide, and a graphene oxide nanosheet is supported to form a fluffy structure, so that the comparative area is increased, and the gas-sensitive performance is improved by gas adsorption.
Example 2
Cu 2 The preparation method of the O @ CuO-RGO nano composite material specifically comprises the following steps:
(1) 0.5g of cuprous oxide was dispersed in 100mL of ultrapure water by magnetic stirring;
(2) adding 17.5mL (1mol/L) of sodium hydroxide/potassium hydroxide into the dispersion liquid obtained in the step (1), and uniformly mixing by magnetic stirring, wherein the pH value is 12.83;
(3) then adding 5mL (10mg/mL) of graphene oxide, and continuously stirring to obtain a mixed solution;
(4) placing the reaction vessel containing the precursor liquid at normal temperature, stirring and reacting at the rotating speed of 700r/min for 5h, and repeatedly washing and drying the obtained product by suction filtration, deionized water and ethanol to obtain Cu 2 O @ CuO-RGO multi-stage nano-flake composite material.
Cu obtained in example 2 The shape of the O @ CuO-RGO multi-stage nanosheet composite material is shown in figure 3, cuprous oxide is etched from the original granular surface part and self-assembled to form a cuprous oxide @ copper oxide multi-stage nanosheet structure, graphene oxide nanosheets are supported to form a coating structure, the nanosheet structure is obvious, but the cuprous oxide is added in a large amount, and the etched self-assembly degree of the surface of the cuprous oxide multi-stage nanosheet composite material is small.
Example 3
Cu 2 The preparation method of the O @ CuO-RGO nano composite material specifically comprises the following steps:
(1) 0.2g of cuprous oxide was dispersed in 100mL of ultrapure water by magnetic stirring;
(2) adding 17.5mL (1mol/L) of sodium hydroxide/potassium hydroxide into the dispersion liquid obtained in the step (1), and uniformly mixing by magnetic stirring, wherein the pH value is 12.83;
(3) then adding 5mL (10mg/mL) of graphene oxide, and continuously stirring to obtain a mixed solution;
(4) placing the reaction vessel containing the precursor liquid at normal temperature, stirring and reacting at the rotating speed of 700r/min for 5h, and repeatedly washing and drying the obtained product by suction filtration, deionized water and ethanol to obtain Cu 2 O @ CuO-RGO multi-stage nano-flake composite material.
Cu obtained in example 2 The O @ CuO-RGO multi-level nanosheet composite material is characterized in that the shape is shown in figure 4, cuprous oxide is in a cuprous oxide @ copper oxide multi-level nanosheet structure formed by etching and self-assembling original granular cuprous oxide, and graphene oxide nanosheets are supported to form a coating structure.
Example 4
Cu 2 The preparation method of the O @ CuO-RGO nano composite material specifically comprises the following steps:
(1) 0.4g of cuprous chloride was dispersed in 100mL of ultrapure water by magnetic stirring;
(2) adding 20mL (1mol/L) of sodium hydroxide/potassium hydroxide into the dispersion liquid obtained in the step (1), and uniformly mixing by magnetic stirring, wherein the pH value is 13.78;
(3) then adding 5mL (10mg/mL) of graphene oxide, and continuously stirring to obtain a mixed solution;
(4) placing the reaction vessel containing the precursor liquid at normal temperature, stirring at a rotating speed of 700r/min for reaction for 5 hours, and performing suction filtration, repeated washing with deionized water and ethanol and drying on the obtained product to obtain Cu 2 O @ CuO-RGO multi-stage nano-flake composite material. Cu obtained in example 2 The O @ CuO-RGO multi-level nano-flake composite material forms an RGO-coated cuprous oxide @ copper oxide multi-level nano-flake structure.
Comparative example 1
(1) 0.1g of cuprous oxide powder was dispersed in 100mL of ultrapure water by magnetic stirring;
(2) adding 1mL (1mol/L) of sodium hydroxide/potassium hydroxide into the ultrapure water obtained in the step (1), and dissolving the ultrapure water by magnetic stirring, wherein the pH value is 8.15;
(3) then adding 5mL (10mg/mL) of graphene oxide, and continuously stirring to obtain a mixed solution;
(4) and (3) placing the reaction container filled with the precursor liquid at normal temperature, stirring and reacting for 20 hours at the rotating speed of 700r/min, and performing suction filtration, repeated washing by deionized water and ethanol and drying on the obtained product to obtain the product material.
Since the amount of sodium hydroxide/potassium hydroxide added was small, the Cu obtained in this comparative example was obtained in spite of the prolonged reaction time 2 The multi-stage nanosheet flower structure is difficult to observe by the O @ CuO-RGO composite material.
Comparative example 2
(1) 0.05g of cuprous oxide powder was dispersed in 100mL of ultrapure water by magnetic stirring;
(2) adding 17.5mL (1mol/L) of sodium hydroxide/potassium hydroxide into the ultrapure water obtained in the step (1), and dissolving the ultrapure water by magnetic stirring, wherein the pH is 12.83;
(3) then adding 5mL (10mg/mL) of graphene oxide, and continuously stirring to obtain a mixed solution;
(4) and (3) placing the reaction container filled with the precursor liquid at normal temperature, stirring and reacting for 5 hours at the rotating speed of 700r/min, and performing suction filtration, repeated washing by deionized water and ethanol and drying on the obtained product to obtain the product material.
The RGO-coated copper oxide nanosheet material obtained by the comparative example has a low addition of cuprous oxide, so that the RGO reduction degree is insufficient.
Comparative example 3
(1) 0.7g commercial cuprous oxide powder was dispersed in 100mL ultrapure water by magnetic stirring;
(2) adding 17.5mL (1mol/L) of sodium hydroxide/potassium hydroxide into the ultrapure water obtained in the step (1), and dissolving the ultrapure water by magnetic stirring, wherein the pH is 12.83;
(3) then adding 5mL (10mg/mL) of graphene oxide, and continuously stirring to obtain a mixed solution;
(4) and (3) placing the reaction container filled with the precursor liquid at normal temperature, stirring and reacting for 5 hours at the rotating speed of 700r/min, and performing suction filtration, repeated washing by deionized water and ethanol and drying on the obtained product to obtain the product material.
Due to the fact that the addition amount of cuprous oxide is large, the amount of sodium hydroxide is insufficient, the reaction is not completely carried out, and the obtained product is obtained by only observing a small amount of copper oxide nanosheets and a large amount of cuprous oxide powder mixed with RGO.
Comparative example 4
(1) 0.1mM copper chloride was dispersed in 100mL of ultrapure water by magnetic stirring;
(2) adding 17.5mL (1mol/L) of sodium hydroxide/potassium hydroxide into the ultrapure water obtained in the step (1), and dissolving the ultrapure water by magnetic stirring, wherein the pH is 12.80;
(3) then adding 5mL (10mg/mL) of graphene oxide, and continuously stirring to obtain a mixed solution;
(4) and (3) placing the reaction vessel filled with the precursor liquid at normal temperature, stirring and reacting at the rotating speed of 700r/min for 8 hours, and repeatedly washing and drying the obtained product by suction filtration, deionized water and ethanol to obtain the GO-coated copper oxide material.
The GO coated copper oxide material obtained by the embodiment has the advantages that copper oxide presents various shapes such as nanowires and nanosheets, and GO is not reduced or is reduced too weakly and has extremely poor conductivity, so that the GO coated copper oxide material is not suitable for being used as a gas sensing material.
Test example 1
Cu obtained in example 1 2 O @ CuO-RGO multi-stage nanometer flake composite material is dripped on the surface of a finger inserting electrode to be dried, then a dynamic gas-sensitive test system is connected to test the gas-sensitive performance of the finger inserting electrode at room temperature, the test voltage is set to be 1V, dry air is used as background gas and diluent gas, and target gas (NO) is introduced 2 ) The device was previously purged with dry air while the current-time curve was recorded for continued testing until the baseline leveled off and NO was added at a concentration of 5ppm 2 The process was repeated 6 times with the gas passing into the test chamber for 60S and purging with dry air for 600S, with the response equation S ═ I (I) t -I 0 )/I 0 Calculating its response, where S is the response value, I t The current value of the device in the target gas, I 0 For the current values of the devices in dry air, a response-time curve as shown in FIG. 5 was obtained, which is for NO 2 The response sensitivity of (2) is high and reaches 140.
Test example 2
Cu obtained in example 2 2 O @ CuO-RGO multi-stage nanometer flake composite material is dripped on the surface of a finger inserting electrode to be dried, then a dynamic gas-sensitive test system is connected to test the gas-sensitive performance of the finger inserting electrode at room temperature, the test voltage is set to be 1V, dry air is used as background gas and diluent gas, and target gas (NO) is introduced 2 ) Blowing the device with dry air, continuously testing and recording the current-time change curve until the baseline is leveled, and adding NO with concentration of 5ppm 2 The process was repeated 6 times with gas passing into the test chamber for 60S and purging with dry air for 600S, with the response formula S ═ I t -I 0 )/I 0 Calculating its response, where S is the response value, I t The current value of the device in the target gas, I 0 For the current values of the devices in dry air, a response-time curve as shown in FIG. 6 was obtained, which is for NO 2 The response sensitivity of (a) is high, about 22.
Test example 3
Cu obtained in comparative example 2 2 O @ CuO-RGO composite material is coated on the surface of a finger inserting electrode in a dripping way and dried, then a dynamic gas-sensitive test system is connected to test the gas-sensitive performance of the finger inserting electrode at room temperature, the test voltage is set to be 1V, dry air is used as background gas and diluent gas, and target gas (NO) is introduced 2 ) Blowing the device with dry air, continuously testing and recording the current-time change curve until the baseline is leveled, and adding NO with concentration of 5ppm 2 The process was repeated 6 times with gas passing into the test chamber for 60S and purging with dry air for 600S, with the response formula S ═ I t -I 0 )/I 0 Calculating its response, where S is the response value, I t The current value of the device in the target gas, I 0 Response-time curve obtained for drying current values of devices in air to NO 2 The gas response is very weak.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. Cu 2 The preparation method of the O @ CuO-RGO nano composite material is characterized by comprising the following steps of,
s1, adding graphene oxide into the cuprous oxide dispersion liquid under an alkaline condition to obtain a mixed liquid; the mass concentration of the cuprous oxide dispersion liquid is 1-5 mg/mL; the pH of the alkaline condition is 9-14;
s2, stirring and reacting the mixed solution in the step S1 to obtain the Cu 2 O @ CuO-RGO nanocomposite.
2. Cu according to claim 1 2 A method for preparing O @ CuO-RGO nanocomposite, characterized in that, in the step S1, the method comprisesThe pH regulator is sodium hydroxide and/or potassium hydroxide.
3. Cu according to claim 2 2 The preparation method of the O @ CuO-RGO nano composite material is characterized in that in the step S1, the molar concentration of the regulator is 0.01-1 mol/L.
4. The Cu of claim 1 2 The preparation method of the O @ CuO-RGO nano composite material is characterized in that in the step of S1, the mass concentration of graphene oxide in the mixed solution is 0.05-5 mg/mL.
5. Cu according to claim 1 2 The preparation method of the O @ CuO-RGO nano composite material is characterized in that in the step of S2, the reaction temperature is 0-39 ℃; the reaction time is 5min-24 h.
6. The Cu of claim 1 2 The preparation method of the O @ CuO-RGO nano composite material is characterized in that in the step S2, the stirring speed is 50-1500 r/min.
7. Cu according to claim 1 2 The preparation method of the O @ CuO-RGO nano composite material is characterized by also comprising the step of separating the Cu from the reaction liquid 2 The O @ CuO-RGO nano composite material comprises the steps of suction filtration, washing and drying treatment; the washing is performed by using deionized water and ethanol.
8. Cu according to claim 1 2 The preparation method of the O @ CuO-RGO nano composite material is characterized in that the washing is carried out by adopting deionized water and ethanol.
9. Cu prepared by the process of any of claims 1 to 8 2 O @ CuO-RGO nanocomposite.
10. Cu as claimed in claim 9 2 O@CuThe application of the O-RGO nano composite material in detecting nitrogen dioxide.
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