CN106337275B - A kind of spherical Cu on activated carbon fibre surface2O crystal films and preparation method thereof - Google Patents
A kind of spherical Cu on activated carbon fibre surface2O crystal films and preparation method thereof Download PDFInfo
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- CN106337275B CN106337275B CN201610813500.6A CN201610813500A CN106337275B CN 106337275 B CN106337275 B CN 106337275B CN 201610813500 A CN201610813500 A CN 201610813500A CN 106337275 B CN106337275 B CN 106337275B
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Abstract
The invention discloses a kind of spherical Cu on activated carbon fibre surface2O crystal films and preparation method thereof.Soluble copper salt is dissolved in deionized water, adds in stabilizer, and controls the molal quantity of stabilizer and copper ion molal quantity in solution；Sodium hydrate regulator solution pH value is added dropwise；Electrolyte is made with the solution, using three-electrode method electrochemical deposition, wherein activated carbon fibre is working electrode；Adjust the V of voltage range 0.1 V~0.4（Vs Ag/AgCl reference electrodes）, control electrodeposition time and reaction temperature.By activated carbon fibre cleaning, the drying after electro-deposition, the spherical Cu for being deposited on activated carbon fibre surface is obtained2O crystal films.The spherical Cu on the activated carbon fibre surface that the present invention obtains2O crystal films combine the Cu with isotropism shape characteristic in conductive substrates2O crystal films, form a film even compact, has the surface property of stable uniform, is preferable catalysis material and sensor material.
Description
Technical field
The present invention relates to one kind to be based on conductive substrates material surface deposited crystal film and preparation method thereof, more particularly, to
A kind of spherical Cu on activated carbon fibre surface2O crystal films and preparation method thereof.
Background technology
Cu2O is a kind of new inorganic material, is P-type semiconductor, and about 2.1 eV of energy gap can directly utilize sunlight
Electron-hole pair is inspired, [promise semiconductor nano cuprous oxide photoelectrocatalysis is nitrogenous for effective nitrogenous pesticide of catalytic degradation
Application [D] Lanzhou in degradation of pesticide analysis:Chemistry ＆. Chemical Engineering College, Lanzhou Univ., 2010.] it is, organic in dyeing wastewater
Pollutant.However powder cuprous oxide is also not easy to recycling, limits its practical application there are loading problem.For this purpose,
Researchers begin one's study cuprous oxide and other materials is compound, film type material or composite material are made, so as to improve oxygen
Change cuprous practical application.
Activated carbon fibre（ACF）, as a kind of multifunctional ceiling enclosure material, mainly with viscose glue, phenolic fibre, polyacrylonitrile
（PAN）, pitch, based on the presomas such as polyimide fiber, be prepared through charing, activating process [Wang Qiaoyun, Zheng Yuying,
Huang Huimin, wait ACF preparation and its VOCs recycling in application progress [J] New Chemical Materials, 2009,37
(11): 34-36].Compared with general absorbent charcoal material, ACF is in addition to abundant and flourishing pore structure, also with non-individual body
The fine quality of material can be used as sorbing material, catalyst carrier and electrode base material etc., meet environmental protection, chemical industry, food
The application of the various fields such as product, electronics and electrochemistry needs.Therefore, in recent years, ACF materials and its surface-functionalized research and
Exploitation receives the very big concern of lot of domestic and international researcher.
Currently, Cu is made2O films be mostly with metal or electro-conductive glass etc. for substrate, using activated carbon fibre as substrate also
It has not been reported.Activated carbon has good electric conductivity, collector material that can be cuprous as electro deposition oxidation；Meanwhile activated carbon
The microcellular structure that fiber surface enriches is nucleated for cuprous oxide and crystallization provides advantage；Again, the company of activated carbon fibre
Continuous body material characteristics again can be as the basis material of load cuprous oxide.By Cu in a manner of electrochemical deposition2O is supported on netted
Cuprous oxide film is made in activated carbon fibre, solves the problems, such as powder body material loading problem and recycling.Cuprous oxide with
The composite material of carbon fiber is expected to pass without enzyme in glucose except applying in fields such as photocatalysis, sterilizing, organic contamination decomposition
Paid attention in sensor field.
The content of the invention
It is an object of the invention to provide a kind of spherical Cu on activated carbon fibre surface2O crystal films and preparation method thereof.
The preparation method makes full use of the pore structure that activated carbon surface enriches, and is Cu2O crystal is in activated carbon fibre surface heterogeneous nucleation knot
Crystalline substance provides substantial amounts of nuclearing centre, with reference to the adjusting of copper ion concentration, makes Cu2O crystal is preferentially tied on activated carbon fibre surface
Crystalline substance, then growth form the spherical morphology of isotropic.
Using the electric conductivity of activated carbon fibre, as the working electrode in three-electrode electro Chemical pond, sunk using electrochemistry
Product method deposits Cu on activated carbon fibre surface2O crystal films；Suitable voltage window is controlled, is made with reference to the complexing of stabilizer
With bivalent cupric ion being made to be reduced into univalent copper ion in electrodeposition process, so as to generate Cu2O crystal；Control electrochemical deposition
Reaction temperature is further ensured that the stability and adequacy of electrochemical deposition reaction.Based on above-mentioned electrochemical reaction mechanism and crystalline substance
The guidance of body growing principle and the comprehensive function of every response parameter, can establish a stable electrochemical reaction system,
On conductive activated carbon fibre surface to Cu2O crystal is precisely controlled into nuclear environment, the orientation of growth and crystalline rate, is facilitated each
The Cu of the spherical morphology of the item same sex2O crystal forms fine and close and uniform film layer on activated carbon fibre surface.
The step of the technical solution adopted by the present invention, is as follows：
First, a kind of spherical Cu on activated carbon fibre surface2O crystal films
A diameter of 3 microns~8 microns of active carbon fibre dimensional fabric, surface compact and equably coat spherical Cu2O crystal is thin
Film, spherical Cu2O crystal diameters are 200 nanometers~5 microns.
2nd, a kind of spherical Cu on activated carbon fibre surface2The step of preparation method of O crystal films, this method, is as follows：
1）Soluble copper salt is dissolved completely in deionized water, copper ion concentration is 0.1~0.4 mol/L；It stirs
To homogeneous solution；
2）It adds in stabilizer in above-mentioned solution, controls the ratio between molal quantity of stabilizer and copper ion molal quantity in solution to be
15:2~5, stirring makes stabilizer uniform dissolution；
3）In step 2）Sodium hydroxide is added dropwise in solution, it is 7~9 to adjust solution ph；
4）It is carried out using by working electrode, to the three-electrode electro Chemical pond that electrode and reference electrode form in activated carbon fibre
Thin film deposition, wherein activated carbon fibre is as working electrode, and platinized platinum is as auxiliary electrode, and Ag/AgCl electrodes are as reference electricity
Pole；By three electrode insertion steps 3）Solution in, keep 25 DEG C~60 DEG C of solution temperature, constant temperature stand 60 minutes；Adjust work
In the V of 0.1 V~0.4, sedimentation time is 10 minutes~30 minutes for voltage between electrode and reference electrode；
5）By activated carbon fibre cleaning, the drying after electro-deposition, obtain fine and close and be uniformly coated on active carbon fibre dimension table
The spherical Cu in face2O crystal films.
The soluble copper salt is the sulfate, nitrate or hydrochloride of copper.
The stabilizer is lactic acid, malic acid, tartaric acid or citric acid.
The invention has the advantages that：
The present invention is former based on electrochemical reaction by a kind of mild, low energy consumption, nontoxic, safe electrochemical deposition method
Reason and mechanism of crystal growth, start with from selection, a variety of synthetic technology parameters of comprehensive regulation, obtain activated carbon fibre surface compact and
The spherical Cu uniformly coated2O crystal films.The present invention utilizes the conduction of activated carbon fibre using principle of electrochemical reaction as guidance
Property, activated carbon fibre is introduced into three-electrode electro Chemical pond, has both working electrode and the base material of thin film deposition；With cupric from
The electrode potential difference of son and univalent copper ion is foundation, takes into full account thermodynamics of crystallization influence factor, sets suitable voltage
Window and reaction temperature, it is pure in activated carbon fibre Surface Creation using electro-reduction process with reference to the complexing of stabilizer
Net Cu2O crystal；For the present invention simultaneously also using mechanism of crystal growth as guidance, construction is conducive to activated carbon fibre surface C u2O crystal
Heterogeneous nucleation and to the crystalline environment of growth, provided using the porous structure on activated carbon fibre surface for crystallization a large amount of
Nuclearing centre forms the regulating and controlling effect of crystallization microenvironment using stabilizer, and reactive ion concentration and reaction temperature is controlled accurately to adjust
Crystal nucleation and growth rate is saved, obtains the Cu with spherical morphology uniformly coated in activated carbon fibre surface compact2O is brilliant
Body thin film.The spherical Cu on this activated carbon fibre surface2O crystal films assign activated carbon fiber material brand-new surface characteristic,
Such as catalytic performance, energy-storage property；Film layer has good bond strength with Basal Activity Carbon fibe, makes Cu2O crystal is answered
It is extended with performance by the body material forms of composite construction.In addition, fine and close and uniformly coat form and isotropism
Spherical morphology, be conducive to Cu2O crystal shows the performance of more stable uniform.
Description of the drawings
Fig. 1 is the XRD spectrum of 1 products therefrom of embodiment.
Fig. 2 is the electromicroscopic photograph of 1 products therefrom of embodiment.
Fig. 3 is the section electromicroscopic photograph of 1 products therefrom of embodiment.
Fig. 4 is the electromicroscopic photograph of 2 products therefrom of embodiment.
Fig. 5 is the electromicroscopic photograph of 3 products therefrom of embodiment.
Specific embodiment
The spherical Cu on the activated carbon fibre surface of the present invention2O crystal films, activated carbon fibre a diameter of 3 microns~8 are micro-
Rice, activated carbon fibre surface compact and equably coat spherical Cu2O crystal films, spherical Cu2O crystal diameters are 200 nanometers~5
Micron.
Embodiment 1：
By 9.9872 g cupric sulfate pentahydrates and 18.0160 g lactic acid（It analyzes pure）Deionized water is dissolved in jointly, is made into 100.0
The mixed solution of ml.Wherein 0.4 mol/L of copper ion concentration, lactic acid concn are 2.0 mol/Ls, stir to get homogeneous solution.
The ratio between the molal quantity of stabilizer lactic acid and copper ion molal quantity are 15 in solution:3.To the hydrogen of 4 mol/L of mixed solution and dripping
Sodium hydroxide solution, and constantly stir evenly, the pH for adjusting solution is 7.0.Solution temperature is controlled at 25.0 DEG C with water-bath, it will
Activated carbon fibre is impregnated 60 minutes in the solution.Electrolyte is made with the solution, electrochemical deposition, platinized platinum are carried out using three-electrode method
Make auxiliary electrode, Ag/AgCl electrodes make reference electrode, and soaking activated carbon fibre is working electrode.Electro-deposition current potential is 0.2
Lie prostrate；Electrodeposition time is 18 minutes.By activated carbon fibre cleaning, the drying after electro-deposition, acquisition is grown in active carbon fibre dimension table
The spherical Cu in face2O crystal films.
Fig. 1 is the XRD spectrum of 1 product of embodiment, the characteristic diffraction peak and Cu of crystalline material on the collection of illustrative plates2O standard x RD is composed
Figure（JCPDS No 34-1354）Match, illustrate the crystal structure and Cu of crystallized product2O is identical, is single pure phase.Fig. 2
It is the SEM photograph of 1 product of embodiment, there is the spherical Cu closely coated on the surface of activated carbon fibre2O crystal grain, a diameter of 300~
500 nanometers.Fig. 3 is 1 product section SEM photos of embodiment, spherical Cu2O crystal grain is complete and is closely coated on activated carbon fibre
Surface.
Embodiment 2：
By 2.4968 g cupric sulfate pentahydrates and 6.7045 g malic acid（It analyzes pure）Deionized water is dissolved in jointly, is made into 25.0
The mixed solution of ml.Wherein 0.4 mol/L of copper ion concentration, malic acid concentration are 2.0 mol/Ls, are stirred to get uniformly molten
Liquid.The ratio between the molal quantity of stabilizer malic acid and copper ion molal quantity are 15 in solution:3.To 4 moles of mixed solution and dripping/
The sodium hydroxide solution risen, and constantly stir evenly, the pH for adjusting whole solution is 9.0.Solution temperature is controlled with water-bath
At 40.0 DEG C, activated carbon fibre is impregnated 60 minutes in the solution.Electrolyte is made with the solution, electrification is carried out using three-electrode method
Deposition is learned, platinized platinum makees auxiliary electrode, and Ag/AgCl electrodes make reference electrode, and soaking activated carbon fibre makees working electrode.Electricity is heavy
Product current potential is 0.1 volt of；Electrodeposition time is 10 minutes.By activated carbon fibre cleaning, the drying after electro-deposition, it is grown in
The spherical Cu on activated carbon fibre surface2O crystal films.
Fig. 4 is the SEM photograph of 2 product of embodiment, there is the spherical Cu closely coated on the surface of activated carbon fibre2O crystal grain,
A diameter of 200~300 nanometers.
Embodiment 3：
By 0.6242 g cupric sulfate pentahydrates and 2.8142 g tartaric acid（It analyzes pure）Deionized water is dissolved in jointly, is made into 25.0
The mixed solution of ml.Wherein 0.1 mol/L of copper ion concentration, tartaric acid concentration are 0.75 mol/L, are stirred to get uniformly molten
Liquid.The ratio between the molal quantity of stabilizer tartaric acid and copper ion molal quantity are 15 in solution:2.To 4 moles of mixed solution and dripping/
The sodium hydroxide solution risen, and constantly stir evenly, the pH for adjusting whole solution is 8.5.Solution temperature is controlled with water-bath
At 60.0 DEG C, activated carbon fibre is impregnated 60 minutes in the solution.Electrolyte is made with the solution, electrification is carried out using three-electrode method
Deposition is learned, platinized platinum makees auxiliary electrode, and Ag/AgCl electrodes make reference electrode, and soaking activated carbon fibre makees working electrode.Electricity is heavy
Product current potential is 0.4 volt of；Electrodeposition time is 30 minutes.By activated carbon fibre cleaning, the drying after electro-deposition, it is grown in
The spherical Cu on activated carbon fibre surface2O crystal films.
Fig. 5 is the SEM photograph of 3 product of embodiment, there is the spherical Cu closely coated on the surface of activated carbon fibre2O crystal grain,
Diameter is about 2~5 microns.
Claims (3)
1. a kind of spherical Cu on activated carbon fibre surface2The preparation method of O crystal films, the activated carbon fibre of the crystal film
A diameter of 3 microns~8 microns of fabric, surface compact and equably coat spherical Cu2O crystal films, spherical Cu2O crystal diameters are
200 nanometers~5 microns；It is characterized in that, the step of preparation method of the crystal film, is as follows：
1）Soluble copper salt is dissolved completely in deionized water, copper ion concentration is 0.1~0.4 mol/L；It stirs to get
Even solution；
2）Stabilizer is added in above-mentioned solution, it is 15 to control the ratio between the molal quantity of stabilizer and copper ion molal quantity in solution:2
~5, stirring makes stabilizer uniform dissolution；
3）In step 2）Sodium hydroxide is added dropwise in solution, it is 7~9 to adjust solution ph；
4）Using by thin in working electrode, the three-electrode electro Chemical pond progress activated carbon fibre formed to electrode and reference electrode
Film deposits, and wherein activated carbon fibre is as working electrode, and platinized platinum is as auxiliary electrode, and Ag/AgCl electrodes are as reference electrode；It will
Three electrode insertion steps 3）Solution in, keep 25 DEG C~60 DEG C of solution temperature, constant temperature stand 60 minutes；Adjust working electrode with
In the V of 0.1 V~0.4, sedimentation time is 10 minutes~30 minutes for voltage between reference electrode；
5）By activated carbon fibre cleaning, the drying after electro-deposition, obtain fine and close and be uniformly coated on activated carbon fibre surface
Spherical Cu2O crystal films.
2. a kind of spherical Cu on activated carbon fibre surface according to claim 12The preparation method of O crystal films, feature
It is：The soluble copper salt is the sulfate, nitrate or hydrochloride of copper.
3. a kind of spherical Cu on activated carbon fibre surface according to claim 12The preparation method of O crystal films, feature
It is：The stabilizer is lactic acid, malic acid, tartaric acid or citric acid.
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| CN110327925A (en) * | 2019-07-29 | 2019-10-15 | 西安建筑科技大学 | Coal Quito pore catalyst and its preparation method and application of carbon monoxide in a kind of removing sintering flue gas |
| CN110302783A (en) * | 2019-08-07 | 2019-10-08 | 浙江理工大学 | A kind of flexible easily recycling carbon cloth@Cu2O optic catalytic composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732928A (en) * | 2012-07-18 | 2012-10-17 | 西北工业大学 | Preparation method of cuprous oxide semiconductor film material |
| CN104512878A (en) * | 2013-09-30 | 2015-04-15 | 上海交通大学 | Method for generating cubic nano cuprous oxide particles on surface of moulded porous carbon |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732928A (en) * | 2012-07-18 | 2012-10-17 | 西北工业大学 | Preparation method of cuprous oxide semiconductor film material |
| CN104512878A (en) * | 2013-09-30 | 2015-04-15 | 上海交通大学 | Method for generating cubic nano cuprous oxide particles on surface of moulded porous carbon |
Non-Patent Citations (1)
| Title |
|---|
| Preparation and photocatalytic activity of cuprous oxide/carbon nanofibres composite films;Yuanqian Wang et. al.;《Applied Surface Science》;20130123;第245-251页 * |
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