CN107732225A - Prepare controllable interface hetero-junctions or Cu2The method of O polyhedron nano-particles - Google Patents

Prepare controllable interface hetero-junctions or Cu2The method of O polyhedron nano-particles Download PDF

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Publication number
CN107732225A
CN107732225A CN201710941217.6A CN201710941217A CN107732225A CN 107732225 A CN107732225 A CN 107732225A CN 201710941217 A CN201710941217 A CN 201710941217A CN 107732225 A CN107732225 A CN 107732225A
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solution
minutes
junctions
hetero
agno
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CN107732225B (en
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隋永明
王光霞
邹勃
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Jilin University
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Jilin University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Crystallography & Structural Chemistry (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

The preparation controllable interface hetero-junctions or Cu of the present invention2The method of O polyhedron nano-particles belongs to the technical field of transition metal oxide semi-conducting material synthesis.Using Fehling Regent as precursor liquid, the Ag of denier is added+And gentle reducing agent glucose, 75 DEG C of reactions obtain less than 100 nanometers of Cu in 5 20 minutes2O polyhedrons or reaction obtain the hetero-junctions of controllable interface in 30 120 minutes.Preparation process of the present invention is simply green, and any pollution will not be brought to environment, and Product size is homogeneous, can be mass-produced, Stability Analysis of Structures, is widely used in catalysis, air-sensitive, Li ion battery negative poles etc..

Description

Prepare controllable interface hetero-junctions or Cu2The method of O polyhedron nano-particles
Technical field
The invention belongs to the technical field of transition metal oxide semi-conducting material synthesis, and in particular to a kind of simple green The Cu of less than 100 nanometers of synthesis2O and its method that hetero-junctions is formed with metal.
Background technology
Metal oxide is cheap due to its rich reserves, it is environment-friendly the features such as be widely used in being catalyzed, gas It is quick, energy storage etc..In numerous metal oxides, P-type semiconductor Cu2O, it is even more that chemical stability is good and draws because being easily-synthesized Play more concerns and research.So far, different-shape and the Cu of size2O has been reported that.It is well known that the shape of nano material Looks and size are an important factor for determining its chemical and physical features.However, Cu2Though O preparation is easy, polyhedron is being prepared Cu2In O report, most of dimension of particle is all between 100 nanometers to several microns.And smaller size of Cu2O particles, surface With abundant atom, have a great impact for physical property.By taking lithium battery applications as an example, except with larger ratio surface Outside product, the electrode material of nano-scale can also promote lithium ion deintercalation and electronics to shift, so as to improve circulating battery and multiplying power Performance, improve stock utilization.It is less than 100 nanometers of Cu in only synthesis2In O several reports, inevitably it is related to The use of complicated cumbersome experimental procedure and poisonous drugs, such as obtained in the presence of polyethylene glycol with r- radiation exposures Obtain less than 100 nanometers of Cu2O is octahedra；Harmful substance hydrazine hydrate makees strong reductant preparation and is less than 100 nanometers of Cu2O.Therefore, I Need to explore the Cu with the simple synthesis nano-scale of development green2O, so as to optimize relative catalysis, air-sensitive, battery etc. Property.Other metal-semiconductor or metal-metallic oxide hetero-junctions are because it is being catalyzed, the side such as energy storage, multi-functional detection The significant performance in face also receives researchers and widely paid close attention to.The rational design of metal-semiconductor interface has and can obtained The advantages such as higher active catalyst, and be selectively nucleated, be grown on a certain position to prepare the hydridization knot of controllable interface Structure provides a kind of effective method.
The content of the invention
The technical problem to be solved in the present invention is the problem of overcoming background technology to exist and defect, there is provided a kind of green ring Protect, technique is simple, can largely prepare Cu less than 100nm2O polyhedrons nano-particle and its with metal formed controllable interface it is different The method of matter knot.
The present invention adds the Ag of denier using Fehling Regent as precursor liquid+And gentle reducing agent glucose, 75 DEG C of conjunctions Cu into below 100 nanometers2The hetero-junctions of O polyhedrons and controllable interface.Concrete technical scheme is as follows：
A kind of method for preparing controllable interface hetero-junctions, take Fehling Regent to be diluted to 10 times of volumes with deionized water, instill AgNO3Solution or HAuCl4Solution, the by mol Cu and AgNO in Fehling Regent3In Ag or HAuCl4Au's in solution Ratio is 27~580:1, stirring 5 minutes adds glucose solution to uniform, in the copper and glucose solution in Fehling Regent The mol ratio of glucose is 14:25,70-80 DEG C of heating 30-120 minutes；10000 revs/min centrifuge 3 minutes, and 50 DEG C dry To Ag-Cu2O or Au-Cu2O hetero-junctions.
One kind prepares below 100nm Cu2The method of O polyhedron nano-particles, takes Fehling Regent to be diluted to deionized water 10 times of volumes, instill AgNO3Solution or HAuCl4Solution, the by mol Cu and AgNO in Fehling Regent3In Ag or HAuCl4 The ratio of Au in solution is 27~580:1, stirring 5 minutes adds glucose solution to uniform, copper and Portugal in Fehling Regent The mol ratio of glucose in grape sugar juice is 14:25,70-80 DEG C of heating 5-20 minutes；10000 revs/min centrifuge 3 minutes, 50 DEG C of drying obtain the Cu that particle diameter is less than 100nm2O polyhedron nano-particles.
Heretofore described Fehling Regent be specifically the cupric sulfate pentahydrate containing 28mM, 88.6mM sodium potassium tartrate tetrahydrate, The mixed aqueous solution of 57.2mM potassium hydroxide；Described AgNO3Solution and HAuCl4The preferred 0.01M of solution concentration.
Beneficial effect：
The present invention prepares less than 100 nanometers of Cu using simple solwution method2O, it only need to extend the reaction time and just can obtain It is formed at Cu2The hetero-junctions in O (100) face.Preparation process is extremely simple, and gained sample size is homogeneous, Stability Analysis of Structures, and increase is each in proportion Individual predecessor, sample topography is constant, is adapted to extensive prepare.
The present invention does not add any surfactant in experimentation, surface cleaning, virose adds without other yet Add agent, be all to use deionized water when washing sample, it is not necessary to organic solvent.Whole process is green, environment will not be brought and appointed What pollutes.
Ag-Cu prepared by the present invention2O hetero-junctions is used as cathode of lithium battery, is still obtained under conditions of high current density Excellent chemical property.
Brief description of the drawings
Fig. 1 is less than 100 nanometers of Cu prepared by embodiment 12O X ray diffracting spectrums.
Fig. 2 is the scanning electron microscopic picture of embodiment 1.
Fig. 3 is less than 100 nanometers of hetero-junctions Ag-Cu prepared by embodiment 22O X ray diffracting spectrums.
Fig. 4 is the scanning electron microscopic picture of the hetero-junctions of embodiment 2.
Fig. 5 is the transmission electron microscope picture of the hetero-junctions of embodiment 2.
Fig. 6 is the distribution diagram of element of the hetero-junctions of embodiment 2.
Fig. 7 is the transmission plot that embodiment 3 is reacted 5 minutes.
Fig. 8 is the scanning electron microscopic picture that embodiment 3 is reacted 10 minutes.
Fig. 9 is the transmission plot that embodiment 3 is reacted 15 minutes.
Figure 10 is the scanning figure that embodiment 4 adds that AgNO3 amounts are 5 microlitres.
Figure 11 is the scanning figure that embodiment 4 adds that AgNO3 amounts are 15 microlitres.
Figure 12 is the scanning figure that embodiment 4 adds that AgNO3 amounts are 30 microlitres.
Figure 13 is will to implement 2 Ag-Cu prepared2O is used for the performance map of lithium cell negative pole.
Embodiment
The present invention is more specifically described in conjunction with following embodiment, unless otherwise specified, agents useful for same is commercially available Obtainable product, purify not plus further and use.
Embodiment 1：Less than 100 nanometers Cu2The preparation of O polyhedron nano-particles
1ml Fehling Regents deionized water is taken to dilute 10 times to 10ml, the AgNO of 108 microlitre of 0.01 mol/L of instillation3, Stirring adds the glucose solution that 200 microlitres of concentration are 0.25 mol/L to uniform in 5 minutes, and 75 DEG C are heated 10 minutes；10000 Rev/min centrifugation 3 minutes, 50 DEG C drying, yield less than particle diameter be less than 100nm Cu2O polyhedron nano-particles.Gained sample X-ray diffraction as shown in figure 1, morphology characterization such as Fig. 2 of sample scanning figure.
Embodiment 2：Less than 100 nanometers controllable interface Ag-Cu2The preparation of O hetero-junctions
Take Fehling Regent to be diluted to 10 times of volumes with deionized water, instill the AgNO of 108 microlitre of 0.01 mol/L3, stirring To uniform, the glucose solution that 200 microlitres of concentration are 0.25 mol/L is added within 5 minutes, 75 DEG C are heated 60 minutes；10000 turns/ Minute centrifugation 3 minutes, 50 DEG C of drying obtain controllable interface Ag-Cu2O hetero-junctions.The X-ray diffraction of gained sample such as Fig. 3, scanning Characterize as Fig. 4, transmission test such as Fig. 5, Elemental redistribution are as shown in Figure 6.Sample prepared by the program is used for the electrode of lithium battery Resulting cycle performance figure is as shown in figure 13, as seen from Figure 13, the bar of sample prepared by the present invention in high current density Excellent chemical property is still achieved under part.
Embodiment 3：Mole Cu:Ag is 54 size adjustable Cu2The preparation of O polyhedron nano-particles
1ml Fehling Regents deionized water is taken to dilute 10 times to 10ml, the AgNO of 55 microlitre of 0.01 mol/L of instillation3, stir 5 minutes are mixed to uniform, adds the glucose solution that 200 microlitres of concentration are 0.25 mol/L, 75 DEG C are heated 5 minutes, 10 points respectively Clock, 15 minutes；10000 revs/min centrifuge 3 minutes, and 50 DEG C of drying respectively obtain various sizes of Cu2O polyhedron nano-particles. The transmission plot of 5 minutes gained samples of reaction is as shown in fig. 7, morphology characterization such as Fig. 8 of 10 minutes samples of reaction, reacts 15 minutes samples The transmission of product characterizes as shown in Figure 9.
Embodiment 4：Reaction time keeps constant, changes the mole Cu of addition:Ag prepares size adjustable Cu2O polyhedrons Nano-particle
Take 1ml Fehling Regents deionized water to dilute 10 times to 10ml, be respectively dropped into 5 microlitres, 15 microlitres, 30 microlitre 0.01 The AgNO of mol/L3, stirring 5 minutes adds the glucose solution that 200 microlitres of concentration are 0.25 mol/L to uniform, 75 DEG C Heating 10 minutes；10000 revs/min centrifuge 3 minutes, and 50 DEG C of drying respectively obtain various sizes of Cu2O polyhedron nanoparticles Son.AgNO3Measure as 5 microlitres of (Cu:Ag=580) scanning of reaction gained sample is as shown in Figure 10, AgNO3Measure as 15 microlitres of (Cu: Ag=193) scanning of sample is as shown in figure 11, AgNO3Measure as 30 microlitres of (Cu:Ag=97) scanning of reaction gained sample is as schemed Shown in 12.
In above-described embodiment, by AgNO3Solution changes HAuCl into4Solution, other conditions are constant, still can obtain 100 and receive Cu below rice2O or Au-Cu2O hetero-junctions, simply Au can be deposited on Cu2O any position.
Fehling Regent described in above-described embodiment be the cupric sulfate pentahydrate containing 28mM, 88.6mM sodium potassium tartrate tetrahydrate, The mixed aqueous solution of 57.2mM potassium hydroxide.

Claims (6)

1. a kind of method for preparing controllable interface hetero-junctions, taking Fehling Regent to be diluted to 10 times of volumes with deionized water, instill AgNO3Solution or HAuCl4Solution, the by mol Cu and AgNO in Fehling Regent3In Ag or HAuCl4Au's in solution Ratio is 27~580:1, stirring 5 minutes adds glucose solution to uniform, in the copper and glucose solution in Fehling Regent The mol ratio of glucose is 14:25,70~80 DEG C are heated 30~120 minutes；10000 revs/min centrifuge 3 minutes, 50 DEG C of drying Obtain Ag-Cu2O or Au-Cu2O hetero-junctions.
A kind of 2. method for preparing controllable interface hetero-junctions according to claim 1, it is characterised in that described film examination Agent be the cupric sulfate pentahydrate containing 28mM, 88.6mM sodium potassium tartrate tetrahydrate, 57.2mM potassium hydroxide mixed aqueous solution.
3. a kind of method for preparing controllable interface hetero-junctions according to claim 1 or 2, it is characterised in that described AgNO3Solution and HAuCl4Solution concentration 0.01M.
4. one kind prepares Cu2The method of O polyhedron nano-particles, take Fehling Regent to be diluted to 10 times of volumes with deionized water, instill AgNO3Solution or HAuCl4Solution, the by mol Cu and AgNO in Fehling Regent3Ag or HAuCl in solution4In solution Au ratio is 27~580:1, stirring 5 minutes adds glucose solution to uniform, copper and glucose solution in Fehling Regent In glucose mol ratio be 14:25,70~80 DEG C are heated 5~20 minutes；10000 revs/min centrifuge 3 minutes, 50 DEG C of bakings The dry Cu for obtaining particle diameter and being less than 100nm2O polyhedron nano-particles.
5. one kind according to claim 4 prepares Cu2The method of O polyhedron nano-particles, it is characterised in that described phenanthrene Woods reagent be the cupric sulfate pentahydrate containing 28mM, 88.6mM sodium potassium tartrate tetrahydrate, 57.2mM potassium hydroxide mixed aqueous solution.
6. one kind according to claim 4 or 5 prepares Cu2The method of O polyhedron nano-particles, it is characterised in that described AgNO3Solution and HAuCl4Solution concentration 0.01M.
CN201710941217.6A 2017-10-11 2017-10-11 Preparation of controlled interface heterojunction or Cu2Method for preparing O-polyhedral nanoparticles Expired - Fee Related CN107732225B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090113660A (en) * 2008-04-28 2009-11-02 울산대학교 산학협력단 One-step synthesis method for coating multi-walled carbon nanotubes with cuprous oxide nanoparticles
CN102515243A (en) * 2011-12-06 2012-06-27 青岛大学 Method for preparation of Cu2O and Au/Cu2O core-shell heterostructure nano cube through thermal oxidation
CN106629815A (en) * 2016-12-26 2017-05-10 北京理工大学 Semiconductor-based hetero-nanocrystal with hollow micro-reaction chamber structure, and preparation method thereof
CN106784775A (en) * 2017-01-19 2017-05-31 吉林大学 The Cu of hollow Nano basket structure2O‑CuO‑TiO2The preparation method of composite

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090113660A (en) * 2008-04-28 2009-11-02 울산대학교 산학협력단 One-step synthesis method for coating multi-walled carbon nanotubes with cuprous oxide nanoparticles
CN102515243A (en) * 2011-12-06 2012-06-27 青岛大学 Method for preparation of Cu2O and Au/Cu2O core-shell heterostructure nano cube through thermal oxidation
CN106629815A (en) * 2016-12-26 2017-05-10 北京理工大学 Semiconductor-based hetero-nanocrystal with hollow micro-reaction chamber structure, and preparation method thereof
CN106784775A (en) * 2017-01-19 2017-05-31 吉林大学 The Cu of hollow Nano basket structure2O‑CuO‑TiO2The preparation method of composite

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAN ZHU等: ""Selective growth of Au nanograins on specific positions(tips,edges and facets) of Cu2O octahedrons to form Cu2O-Au hierarchical heterostructures"", 《DALTON TRANSACTIONS》 *

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