CN108508070A - Au/Cu/Cu2O nanofibers ball, preparation method and application - Google Patents

Au/Cu/Cu2O nanofibers ball, preparation method and application Download PDF

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CN108508070A
CN108508070A CN201710108950.XA CN201710108950A CN108508070A CN 108508070 A CN108508070 A CN 108508070A CN 201710108950 A CN201710108950 A CN 201710108950A CN 108508070 A CN108508070 A CN 108508070A
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nano particles
nanofiber
electrode
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CN108508070B (en
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程喜庆
封心建
聂富强
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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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Abstract

The invention discloses a kind of Au/Cu/Cu2O nanofibers ball, preparation method and application.The preparation method includes：Clean substrate is provided；Cu/Cu is formed using electrical oscillation deposition technique on the substrate2O nano particles；By the Cu/Cu2O nano particles, which are placed in the aqueous solution of gold chloride and/or chloroaurate, carries out reduction treatment, obtains Au/Cu/Cu2O nanofiber balls.The Au/Cu/Cu2O nanofiber balls include comprising Cu/Cu2The core of O nano particles, and, the shell of the core is coated, the shell includes Au nanofibers.Sedimentation and chemical reduction method are combined by the present invention, greatly strengthen the synergistic effect of compound, and device therefor is simple, and easily operated, the reaction time is short, reduces production cost；The Au/Cu/Cu of acquisition2A diameter of 150~450 nanometers of O nanofiber balls, morphology and size is easy to regulate and control, and is had potential application in terms of glucose sensor, will generate good Social benefit and economic benefit.

Description

Au/Cu/Cu2O nanofibers ball, preparation method and application
Technical field
The present invention relates to a kind of Au/Cu/Cu2A kind of O nanofiber balls, and in particular to Au/Cu/Cu2O nanofibers ball, its Preparation method and application.
Background technology
Au/Cu/Cu2O nanofiber balls have unique semiconductor property, photoelectric property and biocompatibility, are urged in light Change, photoelectric device and biosensor etc. have significant application value.Industry scholar has worked out a variety of preparations at present Cu2The method of O compounds, such as sedimentation, spray coating method, metal assistant chemical reduction method etc., but these methods are difficult to realize Compound it is uniform compound, the synergistic effect of compound can be substantially reduced so that the application of material is restricted.
Moreover, industry not yet occurs about can both keep original Cu at present2O compounds are uniformly compound, and can be compound expensive The report of the method for metal.
Invention content
The main purpose of the present invention is to provide a kind of Au/Cu/Cu2O nanofibers ball, preparation method and application, with Overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes：
An embodiment of the present invention provides a kind of Au/Cu/Cu2The preparation method of O nanofiber balls comprising：
Clean substrate is provided；
Cu/Cu is formed using electrical oscillation deposition technique on the substrate2O nano particles；
By the Cu/Cu2O nano particles, which are placed in the aqueous solution of gold chloride and/or chloroaurate, carries out reduction treatment, obtains To Au/Cu/Cu2O nanofiber balls.
As one of preferred embodiment, the preparation method includes：Using the substrate as working electrode with to electrode and Reference electrode forms three-electrode system, or forms bipolar electrode system with to electrode using the substrate as working electrode, will be described Three-electrode system or bipolar electrode system are placed in comprising Cu2+With in the mixed solution of lactic acid and/or sodium citrate, and -0.3 ~-0.8mA/cm2Constant current density under carry out oscillating deposition, to form uniformly compound Cu/Cu on the substrate2O receives Rice grain.
Preferably, the time of the oscillating deposition is 300~1200s.
As one of preferred embodiment, the mixed solution includes the Cu of a concentration of 0.1~0.6mol/L2+And concentration For the lactic acid of 1~6mol/L.
Preferably, the pH value of the mixed solution is 8.5~10.5.
It is especially preferred, the Cu in the mixed solution2+From soluble copper salt, the soluble copper salt includes sulfuric acid Copper or copper sulfate hydrate.
As one of preferred embodiment, the preparation method includes：Load there is into the Cu/Cu2The base of O nano particles Bottom is placed in the gold chloride of a concentration of 0.6~2.4mM/L and/or the aqueous solution of chloroaurate, and is restored in 25~45 DEG C Processing, obtains the Au/Cu/Cu2O nanofiber balls.
Preferably, the time of the reduction treatment is 20~60s.
As one of preferred embodiment, the preparation method includes：Load there is into the Cu/Cu2The base of O nano particles Bottom is placed in the aqueous solution of gold chloride and/or chloroaurate, and carries out reduction treatment under conditions of accompanying by supersound process, is obtained The Au/Cu/Cu2O nanofiber balls.
Preferably, the power of the supersound process is 500~1000W.
As one of preferred embodiment, the preparation method includes：Load there is into the Cu/Cu2The base of O nano particles After bottom is fully cleaned with water, then it is placed in the aqueous solution of gold chloride and/or chloroaurate and carries out reduction treatment.
As one of preferred embodiment, the preparation method includes：The substrate is sequentially placed into deionized water, anhydrous It is 5~30 minutes ultrasonic respectively in the mixed liquor of ethyl alcohol and acetone, deionized water, it is dried up later with nitrogen stream, obtains clean base Bottom.
Preferably, it is 1 that the mixed liquor of the absolute ethyl alcohol and acetone, which includes volume ratio,:3~3:1 absolute ethyl alcohol and third Ketone.
Preferably, the time of the ultrasound is 5~20 minutes, especially preferably 10~15 minutes.
As one of preferred embodiment, the substrate includes FTO electro-conductive glass.
The embodiment of the present invention additionally provides the Au/Cu/Cu prepared by preceding method2O nanofiber balls comprising：Including Cu/Cu2The core of O nano particles, and, the shell of the core is coated, the shell includes Au nanofibers.
Preferably, the Au/Cu/Cu2A diameter of 150~450nm of O nanofiber balls, especially preferably 200~ 420nm。
Preferably, the grain size of the core is 150~475nm.
The embodiment of the present invention additionally provides aforementioned Au/Cu/Cu2O nanofibers ball is in preparing the use in glucose sensor On the way.
The embodiment of the present invention additionally provides aforementioned Au/Cu/Cu2O nanofibers ball is in preparing the purposes in electrocatalysis material.
Compared with prior art, advantages of the present invention at least that：
1. Au/Cu/Cu provided by the invention2The preparation method of O nanofiber balls is to be based on metal assistant chemical reduction method The improvement of nanocomposite method is prepared, i.e. electrical oscillation prepares metal/metal oxide, then metal and metal oxide The compound nanofiber ball of three is prepared in common reduction, specifically, uniformly compound Cu/ is prepared by electrical oscillation method Cu2O nano particles, copper and cuprous oxide standard electrode potential, that is, Cu/Cu2+(+0.337V, vs.SHE) and Cu2O/Cu2+(+ 0.203V, vs.SHE) it is below the standard electrode potential AuCl of gold4 -/ Au (+0.99V, vs.SHE), therefore copper and cuprous oxide Au can be restored3+Au is generated, thus Au/Cu/Cu may be implemented2The preparation of O nanofiber balls；
2. Au/Cu/Cu provided by the invention2The preparation method of O nanofiber balls mutually ties sedimentation with chemical reduction method It closes, greatly strengthens the synergistic effect of compound, and device therefor is simple, easily operated, the reaction time is short, reduces Nanowire The production cost of ball material is tieed up, prepare with scale and practical application are conducive to；
3. the Au/Cu/Cu that the present invention obtains2A diameter of 150~450 nanometers of O nanofiber balls, this nanofiber ball can To obtain super excellent synergistic effect, electrocatalysis material is may be used as, for the detection to glucose, in terms of glucose sensor It has potential application, good Social benefit and economic benefit will be generated；
4. the Au/Cu/Cu that the present invention obtains2The morphology and size of O nanofiber balls is easy to regulate and control, and can pass through regulation and control Cu/Cu2The conditions such as the size of O nano particles regulate and control Au/Cu/Cu2The size of O nanofiber balls.
Description of the drawings
Fig. 1 a, Fig. 1 b are the Au/Cu/Cu prepared in the embodiment of the present invention 1 respectively2The X-ray diffraction pattern of O nanofiber balls Spectrum and stereoscan photograph；
Fig. 2 a are the Au/Cu/Cu prepared in the embodiment of the present invention 12The energy spectrum analysis figure of O nanofiber balls；
Fig. 2 b- Fig. 2 d are each element distribution situation figure in Fig. 1 b respectively；
Fig. 3 is the Au/Cu/Cu prepared in the embodiment of the present invention 22The stereoscan photograph of O nanofiber balls；
Fig. 4 is the Au/Cu/Cu prepared in the embodiment of the present invention 32The stereoscan photograph of O nanofiber balls；
Fig. 5 is the Au/Cu/Cu prepared in the embodiment of the present invention 42The stereoscan photograph of O nanofiber balls；
Fig. 6 is the Au/Cu/Cu prepared in the embodiment of the present invention 52The stereoscan photograph of O nanofiber balls.
Specific implementation mode
For many defects of the prior art, inventor proposes the skill of the present invention through studying for a long period of time and largely putting into practice Art scheme as follows will be further explained the technical solution, its implementation process and principle etc..It is understood, however, that Within the scope of the present invention, above-mentioned each technical characteristic of the invention and each technical characteristic for specifically describing in (embodiment) below it Between can be combined with each other, to constitute new or preferred technical side's scheme.Due to space limitations, I will not repeat them here.
The one side of the embodiment of the present invention provides a kind of Au/Cu/Cu2The preparation method of O nanofiber balls, packet It includes：
Clean substrate is provided；
Cu/Cu is formed using electrical oscillation deposition technique on the substrate2O nano particles；
By the Cu/Cu2O nano particles, which are placed in the aqueous solution of gold chloride and/or chloroaurate, carries out reduction treatment, obtains To Au/Cu/Cu2O nanofiber balls.
As one of preferred embodiment, the preparation method includes：Using the substrate as working electrode with to electrode and Reference electrode forms three-electrode system, or forms bipolar electrode system with to electrode using the substrate as working electrode, will be described Three-electrode system or bipolar electrode system are placed in comprising Cu2+With in the mixed solution of lactic acid and/or sodium citrate, and -0.3 ~-0.8mA/cm2Constant current density under carry out oscillating deposition, to form uniformly compound Cu/Cu on the substrate2O receives Rice grain.Wherein, Cu and Cu may be implemented in electrical oscillation deposition2The moment alternating deposit of O, therefore can obtain uniformly compound Cu/Cu2O nano particles.
Preferably, the constant current density is -0.3~-0.8mA/cm2, especially preferably -0.5~-0.8mA/cm2。
Preferably, the time of the oscillating deposition is 300~1200s, especially preferably 600s.
As one of preferred embodiment, the mixed solution includes the Cu of a concentration of 0.1~0.6mol/L2+And concentration For the lactic acid of 1~6mol/L.
It is furthermore preferred that in the mixed solution lactic acid a concentration of 3M/L.
Preferably, the pH value of the mixed solution is 8.5~10.5, especially preferably 9.
It is especially preferred, the Cu in the mixed solution2+From soluble copper salt, the soluble copper salt includes sulfuric acid Copper or copper sulfate hydrate, such as cupric sulfate pentahydrate.
As one of preferred embodiment, the preparation method includes：Load there is into the Cu/Cu2The base of O nano particles Bottom is placed in the gold chloride of a concentration of 0.6~2.4mM/L and/or the aqueous solution of chloroaurate, and is restored in 25~45 DEG C Processing, obtains the Au/Cu/Cu2O nanofiber balls.
Preferably, the time of the reduction treatment is 20~60s.
Further, a concentration of 1.2mM/L of the aqueous solution of the gold chloride and/or chloroaurate.
Preferably, the temperature of the reduction treatment is 35 DEG C, and the time is 40~60s.
As one of preferred embodiment, the preparation method includes：Load there is into the Cu/Cu2The base of O nano particles Bottom is placed in the aqueous solution of gold chloride and/or chloroaurate, and carries out reduction treatment under conditions of accompanying by supersound process, is obtained The Au/Cu/Cu2O nanofiber balls.Preferably, the power of the supersound process is 500~1000W, especially preferably 600W, the too big fiber of ultrasonic power are easy to fall off, and the too small then fibrous nodules of ultrasonic power are uneven.
As one of preferred embodiment, the preparation method includes：Load there is into the Cu/Cu2The base of O nano particles After bottom is fully cleaned with water, then it is placed in the aqueous solution of gold chloride and/or chloroaurate and carries out reduction treatment.
As one of preferred embodiment, the preparation method includes：The substrate is sequentially placed into deionized water, anhydrous It is 5~30 minutes ultrasonic respectively in the mixed liquor of ethyl alcohol and acetone, deionized water, it is dried up later with nitrogen stream, obtains clean base Bottom.
Preferably, it is 1 that the mixed liquor of the absolute ethyl alcohol and acetone, which includes volume ratio,:3~3:1 absolute ethyl alcohol and third Ketone.
Preferably, the time of the ultrasound is 5~20 minutes, especially preferably 10~15 minutes.
As one of preferred embodiment, the substrate includes FTO electro-conductive glass, but not limited to this.Preferably, the base The size at bottom is 1cm x 2.5cm.
For example, in some more specific embodiment, the preparation method can also include the following steps：
(1) FTO electro-conductive glass substrate is immersed to the mixed liquor (1 of deionized water, absolute ethyl alcohol and acetone successively:1), go from It is 10~15 minutes ultrasonic respectively in sub- water, then dried up with nitrogen stream；
(2) using the above-mentioned FTO electro-conductive glass substrate cleaned up as working electrode, platinum filament is to be saturated calomel to electrode Electrode is reference electrode, three-electrode system in 0.3M/L copper sulphate and 3M/L lactic acid (pH=9) solution constant current density (- 0.5~-0.8mA/cm2) under oscillating deposition 600 seconds, you can obtain Cu/Cu in FTO electro-conductive glass substrates2O nano particles；
(3) by above-mentioned Cu/Cu2O/FTO is cleaned with a large amount of water；
(4) by above-mentioned Cu/Cu2O/FTO, which is put into 1.2mM/L aqueous solution of chloraurate, carries out reduction treatment, in 35 DEG C of low temperature Lower ultrasonic reaction 40~60 seconds, you can obtain a diameter of 200~420 nanometers of Au/Cu/Cu2O nanofibers ball is to get to mesh Mark product.
The embodiment of the present invention another aspect provides the Au/Cu/Cu prepared by preceding method2O nanofiber balls, Including：Including Cu/Cu2The core of O nano particles, and, the shell of the core is coated, the shell includes Au nanofibers.
Preferably, the Au/Cu/Cu2A diameter of 150~450nm of O nanofiber balls, especially preferably 200~ 420nm。
Preferably, the grain size of the core is 150~475nm.
The one side of the embodiment of the present invention additionally provides aforementioned Au/Cu/Cu2O nanofibers ball in prepare glucose pass Purposes in sensor.
The embodiment of the present invention additionally provides aforementioned Au/Cu/Cu2O nanofibers ball is in preparing the purposes in electrocatalysis material.
For example, a kind of electrocatalysis material comprising the Au/Cu/Cu2O nanofiber balls.
In conclusion the present invention is to prepare Au/Cu/Cu2The direct effective method of O nanofiber balls, uses current potential first Oscillating deposition method prepares uniformly compound Cu/Cu2O nano particles.Electrical oscillation sedimentation realize time and space from Assembly behavior is one of the technology that nano materials are concerned.Under the conditions of the present invention, electrical oscillation deposition may be implemented Cu and Cu2The moment alternating deposit of O, therefore uniformly compound Cu/Cu can be obtained2O nano particles.Finally, in chlorauric acid solution In, the Cu/Cu of outer layer2O nano particles restore Au3+Au is generated, center can be finally obtained and retain uniformly compound Cu/Cu2O receives Rice grain, the nanofiber ball of outer layer covers Au nanofibers.Furthermore, it is possible to by regulating and controlling Cu/Cu2The size of O nano particles Etc. conditions regulate and control Au/Cu/Cu2The size of O nanofiber balls.
Below by way of several embodiments and the technical solution that present invention be described in more detail in conjunction with attached drawing.However, selected Embodiment be merely to illustrate the present invention, and do not limit the scope of the invention.
Embodiment 1
FTO electro-conductive glass substrate is immersed to the mixed liquor (1 of deionized water, absolute ethyl alcohol and acetone successively:1), deionization It is 15 minutes ultrasonic respectively in water, it further takes out and is used as working electrode with nitrogen stream drying.It is to electrode, saturated calomel electrode with platinum filament For reference electrode, three-electrode system is in 0.3mol/L copper sulphate and 3mol/L lactic acid (pH value=9) solution in -0.5mA/cm2 It is deposited 600 seconds under current density, you can obtain Cu/Cu in FTO electro-conductive glass substrates2O nano particles.Then with a large amount of water Cleaning；Finally by above-mentioned Cu/Cu2O nano particles are put into 1.2mM/L aqueous solution of chloraurate and carry out reduction treatment, in 35 DEG C of low temperature Ultrasonic reaction 40 seconds, you can obtain the Au/Cu/Cu that diameter is about 200 nanometers2O nanofiber balls.
By Au/Cu/Cu manufactured in the present embodiment2The x-ray diffraction collection of illustrative plates (XRD) and scanning electron microscope of O nanofiber balls shine Piece (SEM) is referring to shown in Fig. 1 a and Fig. 1 b.By Au/Cu/Cu manufactured in the present embodiment2The energy spectrum analysis figure EDS of O nanofiber balls Shown in Fig. 2 a.Fig. 2 b- Fig. 2 d show the distribution situation of each element in Fig. 1 b.
Embodiment 2
FTO electro-conductive glass substrate is immersed to the mixed liquor (1 of deionized water, absolute ethyl alcohol and acetone successively:1), deionization It is 15 minutes ultrasonic respectively in water, it further takes out and is used as working electrode with nitrogen stream drying.It is to electrode, saturated calomel electrode with platinum filament For reference electrode, three-electrode system is in 0.3mol/L copper sulphate and 3mol/L lactic acid (pH value=9) solution in -0.5mA/cm2 It is deposited 600 seconds under current density, you can obtain Cu/Cu in FTO electro-conductive glass substrates2O nano particles.Then with a large amount of water Cleaning；Finally by above-mentioned Cu/Cu2O nano particles are put into 1.2mM/L aqueous solution of chloraurate and carry out reduction treatment, in 35 DEG C of low temperature Ultrasonic reaction 60 seconds, you can obtain the Au/Cu/Cu that diameter is about 170 nanometers2O nanofiber balls.
By Au/Cu/Cu manufactured in the present embodiment2The stereoscan photograph (SEM) of O nanofiber balls is shown in Figure 3.
Embodiment 3
FTO electro-conductive glass substrate is immersed to the mixed liquor (1 of deionized water, absolute ethyl alcohol and acetone successively:1), deionization It is 15 minutes ultrasonic respectively in water, it further takes out and is used as working electrode with nitrogen stream drying.It is to electrode, saturated calomel electrode with platinum filament For reference electrode, three-electrode system is in 0.3mol/L copper sulphate and 3mol/L lactic acid (pH value=9) solution in -0.8mA/cm2 It is deposited 600 seconds under current density, you can obtain Cu/Cu in FTO electro-conductive glass substrates2O nano particles.Then with a large amount of water Cleaning；Finally by above-mentioned Cu/Cu2O nano particles are put into 1.2mM/L aqueous solution of chloraurate and carry out reduction treatment, in 35 DEG C of low temperature Ultrasonic reaction 60 seconds, you can obtain the Au/Cu/Cu that diameter is about 420 nanometers2O nanofiber balls.
By Au/Cu/Cu manufactured in the present embodiment2The stereoscan photograph (SEM) of O nanofiber balls is shown in Figure 4.
Embodiment 4
FTO electro-conductive glass substrate is immersed to the mixed liquor (1 of deionized water, absolute ethyl alcohol and acetone successively:1), deionization It is 15 minutes ultrasonic respectively in water, it further takes out and is used as working electrode with nitrogen stream drying.It is to electrode, saturated calomel electrode with platinum filament For reference electrode, three-electrode system is in 0.6mol/L copper sulphate and 6mol/L lactic acid (pH value=9) solution in -0.3mA/cm2 It is deposited 1200 seconds under current density, you can obtain Cu/Cu in FTO electro-conductive glass substrates2O nano particles.Then it uses a large amount of Water cleans；Finally by above-mentioned Cu/Cu2O nano particles are put into 0.6mM/L aqueous solution of chloraurate and carry out reduction treatment, low at 35 DEG C Warm ultrasonic reaction 50 seconds, you can obtain the Au/Cu/Cu that diameter is about 150 nanometers2O nanofiber balls.
By Au/Cu/Cu manufactured in the present embodiment2The stereoscan photograph (SEM) of O nanofiber balls is shown in Figure 5.
Embodiment 5
FTO electro-conductive glass substrate is immersed to the mixed liquor (1 of deionized water, absolute ethyl alcohol and acetone successively:1), deionization It is 15 minutes ultrasonic respectively in water, it further takes out and is used as working electrode with nitrogen stream drying.It is to electrode, saturated calomel electrode with platinum filament For reference electrode, three-electrode system is in 0.1mol/L copper sulphate and 1mol/L lactic acid (pH value=9) solution in -0.8mA/cm2 It is deposited 900 seconds under current density, you can obtain Cu/Cu in FTO electro-conductive glass substrates2O nano particles.Then with a large amount of water Cleaning；Finally by above-mentioned Cu/Cu2O nano particles are put into 2.4mM/L aqueous solution of chloraurate and carry out reduction treatment, in 35 DEG C of low temperature Ultrasonic reaction 60 seconds, you can obtain the Au/Cu/Cu that diameter is about 450 nanometers2O nanofiber balls.
By Au/Cu/Cu manufactured in the present embodiment2The stereoscan photograph (SEM) of O nanofiber balls is shown in Figure 6.
Obviously, it can see Au/Cu/Cu according to Fig. 1-Fig. 62The morphology and size of O nanofiber balls, wherein Fig. 2 c- are schemed EDS figures in 2d are it can be seen that Au is distributed in the outside of nanofiber ball.
It should be understood that the technical concepts and features of above-described embodiment only to illustrate the invention, ripe its object is to allow The personage for knowing technique cans understand the content of the present invention and implement it accordingly, and the protection model of the present invention can not be limited with this It encloses.Any equivalent change or modification in accordance with the spirit of the invention should be covered by the protection scope of the present invention.

Claims (12)

1. a kind of Au/Cu/Cu2The preparation method of O nanofiber balls, it is characterised in that including：
Clean substrate is provided；
Cu/Cu is formed using electrical oscillation deposition technique on the substrate2O nano particles；
By the Cu/Cu2O nano particles, which are placed in the aqueous solution of gold chloride and/or chloroaurate, carries out reduction treatment, obtains Au/ Cu/Cu2O nanofiber balls.
2. preparation method according to claim 1, it is characterised in that including：Using the substrate as working electrode and to electrode Three-electrode system is formed with reference electrode, or bipolar electrode system is formed with to electrode using the substrate as working electrode, by institute It states three-electrode system or bipolar electrode system is placed in comprising Cu2+With in the mixed solution of lactic acid and/or sodium citrate, and -0.3 ~-0.8mA/cm2Constant current density under carry out oscillating deposition, to form uniformly compound Cu/Cu on the substrate2O receives Rice grain；Preferably, the time of the oscillating deposition is 300~1200s.
3. preparation method according to claim 2, it is characterised in that：The mixed solution include a concentration of 0.1~ The Cu of 0.6mol/L2+And the lactic acid of a concentration of 1~6mol/L；Preferably, the pH value of the mixed solution is 8.5~10.5.
4. preparation method according to claim 3, it is characterised in that：Cu in the mixed solution2+From solubility Mantoquita, the soluble copper salt include copper sulphate or copper sulfate hydrate.
5. preparation method according to claim 1 or 2, it is characterised in that including：Load there is into the Cu/Cu2O nanometers Grain substrate be placed in the gold chloride of a concentration of 0.6~2.4mM/L and/or the aqueous solution of chloroaurate, and in 25~45 DEG C into Row reduction treatment obtains the Au/Cu/Cu2O nanofiber balls；Preferably, the time of the reduction treatment is 20~60s.
6. preparation method according to claim 5, it is characterised in that including：Load there is into the Cu/Cu2O nano particles Substrate is placed in the aqueous solution of gold chloride and/or chloroaurate, and carries out reduction treatment under conditions of accompanying by supersound process, is obtained To the Au/Cu/Cu2O nanofiber balls；Preferably, the power of the supersound process is 500~1000W.
7. preparation method according to claim 5, it is characterised in that including：Load there is into the Cu/Cu2O nano particles After substrate is fully cleaned with water, then it is placed in the aqueous solution of gold chloride and/or chloroaurate and carries out reduction treatment.
8. preparation method according to claim 1, it is characterised in that including：By the substrate be sequentially placed into deionized water, It is 5~30 minutes ultrasonic respectively in the mixed liquor of absolute ethyl alcohol and acetone, deionized water, it is dried up, is obtained clean with nitrogen stream later Substrate；Preferably, it is 1 that the mixed liquor of the absolute ethyl alcohol and acetone, which includes volume ratio,:3~3:1 absolute ethyl alcohol and acetone； Preferably, the time of the ultrasound is 5~20 minutes, especially preferably 10~15 minutes.
9. preparation method according to claim 8, it is characterised in that：The substrate includes FTO electro-conductive glass.
10. the Au/Cu/Cu prepared by any one of claim 1-9 the methods2O nanofiber balls, it is characterised in that including： Including Cu/Cu2The core of O nano particles, and, the shell of the core is coated, the shell includes Au nanofibers；Preferably, described Au/Cu/Cu2A diameter of 150~450nm of O nanofiber balls, especially preferably 200~420nm；Preferably, the grain of the core Diameter is 150~475nm.
11. Au/Cu/Cu as claimed in claim 102O nanofibers ball is in preparing the purposes in glucose sensor.
12. Au/Cu/Cu as claimed in claim 102O nanofibers ball is in preparing the purposes in electrocatalysis material.
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