CN105908240A - Preparation method of copper oxide/titanium dioxide composite nanotube arrays - Google Patents
Preparation method of copper oxide/titanium dioxide composite nanotube arrays Download PDFInfo
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- CN105908240A CN105908240A CN201610278490.0A CN201610278490A CN105908240A CN 105908240 A CN105908240 A CN 105908240A CN 201610278490 A CN201610278490 A CN 201610278490A CN 105908240 A CN105908240 A CN 105908240A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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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
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
Abstract
The invention provides a preparation method of copper oxide/titanium dioxide composite nanotube arrays. The copper oxide/titanium dioxide composite nanotube arrays have the methyl orange decomposing capacity in the ultraviolet light. The preparation method of the copper oxide/titanium dioxide composite nanotube arrays includes the following steps that (1) anodizing is conducted, specifically, titanium dioxide nanotube arrays are prepared through an anodic oxidation method; (2) chemical precipitation is carried out, specifically, the nanotube arrays are soaked in copper salt and alkali liquor alternately, and copper oxides are doped; and (3) annealing is carried out, specifically, the nanotubes compounded with the copper oxides after the reaction are subjected to annealing, so that an anatase type titanium dioxide nanotube catalyst is obtained. The nanotube catalyst can be used repeatedly; the preparation method is simple, low in cost and free of pollution, and other preparation processes are better in energy saving; and a cathode of an electrolytic tank is low in cost and can be used repeatedly. According to the preparation method, anatase crystal type titanium dioxide is obtained after the nanotube arrays are subjected to annealing at the proper temperature, the catalytic efficiency is higher, the structure is firmer, and the situations that after long-term use, nanotube arrays adhering to a titanium sheet substrate fall down and the catalytic efficiency is greatly reduced are avoided.
Description
[technical field]
The present invention relates to nanotube preparing technical field, be specifically related to the system of a kind of Cu oxide/titanium dioxide composite nano tube array
Preparation Method.
[background technology]
Problem of environmental pollution is one of significant problem of facing of modern society, and Organic Pollution problem is the one of problem of environmental pollution
Individual very important part.Utilize the free radical of Strong oxdiative-reducing power that photocatalyst produces under light illumination, almost can be all
Organic matter degradation, so it is a kind of simple to operate for utilizing the present invention to process organic pollution, and be not likely to produce secondary pollution
The method solving Organic Pollution problem.
As far back as 1972, strong more than the basis of Tokyo Univ Japan deliver paper once teaching, teach titanium dioxide at ultraviolet lighting
Penetrate the lower phenomenon that can split water into oxygen and hydrogen.After this, photocatalyst is applied to field the most widely, uses
It is exactly one of its application in process organic pollution.But, titanium dioxide optical catalyst still has many shortcomings, such as: 1, normal
The powder catalyst recycling seen is cumbersome；2, catalytic efficiency is not high enough；3, it is catalyzed after long-lasting catalytic uses
Ability reduces.Publication No. CN102240550A Chinese invention patent discloses that " low concentration copper-doped titanium dioxide nanotube light is urged
Agent and preparation method thereof ", this invention obtains titanium dioxide nano tube catalyst by the method for anodization, electro-deposition and calcining,
But it uses electrodeposition process to add energy consumption, and additionally its calcining heat is more than 500 DEG C, and catalytic effect declines to a great extent.
[summary of the invention]
The goal of the invention of the present invention is: for the problem of above-mentioned existence, it is provided that a kind of Cu oxide/titanium dioxide composite nano tube
The preparation method of array, the method that present invention employs anodization, chemical deposition and annealing prepares Nano tube array of titanium dioxide,
The method electrolyte quota is simple, cost is relatively low, not do not pollute, and other preparation process are more energy efficient, cathode of electrolytic tank low cost and
Reusable.The nano-tube array of the present invention obtains the titanium dioxide of anatase crystal, catalytic efficiency after suitable temperature is annealed
Higher, structure is more firm, will not come off and catalytic efficiency because long-time use causes being attached to the suprabasil nano-tube array of titanium sheet
Decline to a great extent.
To achieve these goals, the technical solution used in the present invention is as follows:
The preparation method of a kind of Cu oxide/titanium dioxide composite nano tube array, comprises the following steps:
(1) anodization: clean surface, in the electrolytic solution anodic oxidation a period of time after titanium sheet is cut into small pieces, obtain titanium dioxide
Nano-tube array, wherein electrolyte is the solution that volume ratio is 5:1～8:1 of polyhydroxy organic solvent and water, simultaneously molten in electrolyte
Solved mass fraction be 0.5%～1.0% containing villiaumite；During anodization, clean titanium sheet, as anode, connects positive source；Stone
Electrode ink, as negative electrode, connects power cathode, and electrolyte temperature is 25 ± 5 DEG C, and electrolysis time is 4～8h, and decomposition voltage is 40～50V；
(2) chemical deposition: prepared nano-tube array immersed in soluble copper saline solution, time of repose is 40～60s, then
Taking out nanotube, immerse in aqueous slkali, time of repose is 40～60s, and twice submergence and the process of standing deposit as complete cycle
Process, whole cyclic deposition process repeats 3～7 times, and wherein the concentration of soluble copper saline solution is 0.03～0.06mol/L, and alkali is molten
The concentration of liquid is 2 times of mantoquita concentration；
(3) annealing: described annealing be by chemical deposition after nanotube in the air atmosphere of Muffle furnace, at the air of Muffle furnace
In atmosphere, it is heated to 400～450 DEG C with the firing rate of 2 DEG C/min, power-off after insulation 3～6h, allow Muffle furnace natural cooling,
I.e. can get the Nano tube array of titanium dioxide of the compound anatase crystal of the oxide of copper.
More preferably, described aqueous slkali is one or more mixing in ammonia, sodium hydroxide, potassium hydroxide, and aqueous slkali is mainly used
Deposit nanotube surface copper ion, increase the catalytic effect of nanotube.
More preferably, described polyhydroxy organic solvent is the mixing of one or more in glycerol, ethylene glycol and dihydroxy acetone,
For slowing down the formation on the barrier layer of nanotube surface in anode oxidation process.
More preferably, described is soluble-salt containing villiaumite, and is one or more mixing in ammonium fluoride, sodium fluoride, potassium fluoride,
For dissolving the oxide on titanium plate.
More preferably, described soluble copper salt is one or more mixing in copper sulfate, copper nitrate, copper chloride, is used for being doped into
Nanotube, improves the catalytic effect of nanotube.
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows:
(1) anodization of the present invention is prepared in Nano tube array of titanium dioxide, uses graphite electrode to do negative electrode, not only reduces cost,
And graphite electrode is more stable, the use longevity of cathode electrode in anodization repeatedly without being corroded, can be effectively increased
Life.
(2) present invention increases titanium sheet voltage in anode oxidation process, and decomposition voltage is the highest, and polyhydroxy organic solvent is to barrier layer shape
The impact of the speed become is the most obvious, and its changing value is the most linear with decomposition voltage, substantially conforms to Ohm's law, simultaneously electricity
Pressure is arranged on 40～50V, is more beneficial for nanotube molding；Improve the concentration of polyhydroxy organic solvent simultaneously, add polyhydroxy organic
Solvent makes anodised barrier layer form electric current density reduction, and it is elongated that barrier layer forms the time, i.e. reduces the shape on barrier layer
Become speed.
(3) present invention uses the method copper doped of chemical deposition to improve the catalytic effect of nanotube, not only reduces the cost of equipment, and
Power consumption has been reduced or avoided.
(4) present invention is in annealing process, is heated to 400～450 DEG C, can form Detitanium-ore-type, and Muffle furnace is with 2 DEG C/min
Firing rate heating, crystalline structure growth can be made more complete, improve the photocatalysis of nanotube to a greater degree, and
Anatase type nano tubular construction is firm, the nano-tube array being attached on titanium sheet substrate will be caused to come off because of long-time use,
Better assure that the catalytic effect of nanotube.
[accompanying drawing explanation]
Fig. 1 is the nanotube scanning electron microscope image of non-combined oxidation copper.
Fig. 2 is the nanotube scanning electron microscope image of non-combined oxidation copper.
Fig. 3 is that the nanotube EDS of combined oxidation copper can spectrogram.
Fig. 4 is the nanotube XRD x ray diffration pattern x of combined oxidation copper.
Fig. 5 is the nanotube uv-visible absorption spectroscopy of combined oxidation copper.
Fig. 6 be the nanotube of combined oxidation copper photocatalysis different time after the abosrption spectrogram of methyl orange solution.
Fig. 7 is that the nanotube of combined oxidation copper is to each solution degradation rate of methyl orange solution different time when 463 nanometers.
Fig. 8 is the absorbance curve figure of the nanotube repeatedly photocatalytic degradation of combined oxidation copper.
[detailed description of the invention]
Below against accompanying drawing with combine optimal detailed description of the invention the present invention is explained in detail.
One, preparation embodiment
Embodiment 1
The preparation method of a kind of Cu oxide/titanium dioxide composite nano tube array, comprises the following steps:
(1) anodization: clean surface, in the electrolytic solution anodic oxidation a period of time after titanium sheet is cut into small pieces, obtain titanium dioxide
Nano-tube array, wherein electrolyte is the solution that volume ratio is 5:1 of glycerol and water, has dissolved quality simultaneously and divide in electrolyte
Number be 0.5% containing ammonium fluoride；During anodization, clean titanium sheet, as anode, connects positive source；Graphite electrode as negative electrode,
Connecing power cathode, electrolyte temperature is 20 DEG C, and electrolysis time is 4h, and decomposition voltage is 40V；
(2) chemical deposition: being immersed in solubility copper-bath by prepared nano-tube array, time of repose is 40s, then
Taking out nanotube, immerse in ammonia spirit, time of repose is 40s, and twice submergence and standing process deposited as complete cycle
Journey, whole cyclic deposition process is repeated 3 times, and wherein the concentration of copper-bath is 0.03mol/L, and the concentration of ammonia spirit is sulfur
2 times of acid copper solution concentration；
(3) annealing: described annealing be by chemical deposition after nanotube in the air atmosphere of Muffle furnace, with adding of 2 DEG C/min
Thermal velocity is heated to 400 DEG C, power-off after insulation 3h, allows Muffle furnace natural cooling, i.e. can get the sharp titanium that the oxide of copper is compound
The Nano tube array of titanium dioxide of ore deposit crystal formation.
Embodiment 2
The preparation method of a kind of Cu oxide/titanium dioxide composite nano tube array, comprises the following steps:
(1) anodization: clean surface, in the electrolytic solution anodic oxidation a period of time after titanium sheet is cut into small pieces, obtain titanium dioxide
Nano-tube array, wherein electrolyte is the solution that volume ratio is 8:1 of ethylene glycol and water, has dissolved quality simultaneously and divide in electrolyte
Number is the containing sodium fluoride of 1.0%；During anodization, clean titanium sheet, as anode, connects positive source；Graphite electrode as negative electrode,
Connecing power cathode, electrolyte temperature is 30 DEG C, and electrolysis time is 8h, and decomposition voltage is 50V；
(2) chemical deposition: being immersed in copper chloride solution by prepared nano-tube array, time of repose is 60s, then takes out and receives
Mitron, immerses in sodium hydroxide solution, and time of repose is 60s, twice submergence and the process of standing as complete cycle deposition process,
Whole cyclic deposition process is repeated 7 times, and wherein the concentration of copper chloride solution is 0.06mol/L, and the concentration of sodium hydroxide solution is chlorine
Change copper solution concentration 2 times；
(3) annealing: described annealing be by chemical deposition after nanotube in the air atmosphere of Muffle furnace, with adding of 2 DEG C/min
Thermal velocity is heated to 450 DEG C, power-off after insulation 6h, allows Muffle furnace natural cooling, i.e. can get the sharp titanium that the oxide of copper is compound
The Nano tube array of titanium dioxide of ore deposit crystal formation.
Embodiment 3
The preparation method of a kind of Cu oxide/titanium dioxide composite nano tube array, comprises the following steps:
(1) anodization: clean surface, in the electrolytic solution anodic oxidation a period of time after titanium sheet is cut into small pieces, obtain titanium dioxide
Nano-tube array, wherein electrolyte is the solution that volume ratio is 6.5:1 of dihydroxy acetone and water, has dissolved matter in electrolyte simultaneously
Amount mark be 0.75% containing potassium fluoride；During anodization, clean titanium sheet, as anode, connects positive source；Graphite electrode does
For negative electrode, connecing power cathode, electrolyte temperature is 25 DEG C, and electrolysis time is 6h, and decomposition voltage is 45V；
(2) chemical deposition: being immersed in copper nitrate solution by prepared nano-tube array, time of repose is 50s, then takes out and receives
Mitron, immerses in potassium hydroxide solution, and time of repose is 50s, twice submergence and the process of standing as complete cycle deposition process,
Whole cyclic deposition process is repeated 5 times, and wherein the concentration of copper nitrate solution is 0.05mol/L, and the concentration of potassium hydroxide solution is nitre
2 times of acid copper solution concentration；
(3) annealing: described annealing be by chemical deposition after nanotube in the air atmosphere of Muffle furnace, with adding of 2 DEG C/min
Thermal velocity is heated to 425 DEG C, power-off after insulation 4.5h, allows Muffle furnace natural cooling, i.e. can get compound sharp of the oxide of copper
The Nano tube array of titanium dioxide of titanium ore crystal formation.
Two, checking embodiment
Embodiment 4
Fig. 1～Fig. 8 is correlation test installation drawing and the test datagram of checking embodiment.
The preparation method of a kind of Cu oxide/titanium dioxide composite nano tube array, comprises the following steps:
(1) anodization: clean surface, in the electrolytic solution anodic oxidation a period of time after titanium sheet is cut into small pieces, obtain titanium dioxide
Nano-tube array, wherein electrolyte is the solution that volume ratio is 5:1 of glycerol and water, has dissolved quality simultaneously and divide in electrolyte
Number be 0.75% containing potassium fluoride；During anodization, using clean titanium sheet as anode, connect positive source, graphite electrode as
Negative electrode, connects power cathode, and electrolyte temperature is 25 DEG C, and electrolysis time is 6h, and decomposition voltage is 45V；
(2) chemical deposition: being immersed in copper chloride solution by prepared nano-tube array, time of repose is 50s, then takes out and receives
Mitron, immerses in ammonia spirit, and time of repose is 50s, and twice submergence and the process of standing are as complete cycle deposition process, whole
Individual cyclic deposition process is repeated 5 times, and wherein the concentration of copper chloride solution is 0.05mol/L, and the concentration of ammonia spirit is that copper chloride is molten
2 times of liquid concentration；
(3) annealing: described annealing be by chemical deposition after nanotube in the air atmosphere of Muffle furnace, with adding of 2 DEG C/min
Thermal velocity is heated to 450 DEG C, power-off after insulation 6h, allows Muffle furnace natural cooling, i.e. can get the sharp titanium that the oxide of copper is compound
The Nano tube array of titanium dioxide of ore deposit crystal formation.
(4) to preparing nano-tube array, to carry out every test, design parameter and correlated results as follows:
1. as it is shown in figure 1, not compound titania nanotube amplifies 20,000 times of S-3400N scanning electron microscope images, can
To see the Nano tube array of titanium dioxide of the uniform diameter of pattern about 160 nanometer.
2. as in figure 2 it is shown, the titania nanotube of the oxide of complex copper amplifies 10,000 times of S-3400N scanning electron microscopies
Mirror image, it can be seen that be all attached to uniform heterojunction structure at the titania nanotube mouth of pipe and periphery.
3. as it is shown on figure 3, the element of titania nanotube surface attachment is analyzed by EDS power spectrum, it is determined that attachment
The oxide that heterojunction structure is copper.
The most as shown in Figure 4, it has been found that prepare product (CuO/TiO2NTs) XRD figure spectrum can be with Titanium standard card
And the titanium dioxide standard card (JCPDS:78-2468) of anatase crystal is the most identical (JCPDS:44-1294).This explanation
Our synthetic product titanium dioxide crystal form is Detitanium-ore-type；Product collection of illustrative plates does not occur the signal peak of copper oxide, is the oxygen of copper
The amount that compound is combined causes very little.
5. as it is shown in figure 5, by detection uv-visible absorption spectroscopy, it has been found that prepare the product suction to ultraviolet-visible light
Receipts are significantly better than that pure titinium dioxide nano-tube array.
The most as shown in Figure 6, photocatalytic degradation 10 milligrams per liter is carried out by the titania nanotube of the oxide by complex copper
Methyl orange is tested.Obtain the absorption spectrum of methyl orange solution after photocatalysis different time,；As it is shown in fig. 7, with each solution at light
Wavelength is the degradation rate of the absorbance sign methyl orange solution different time of 463 nanometers.
The most as shown in Figure 8, carry out repeatedly light degradation by the titania nanotube of the oxide by complex copper and test, find
After many experiments, within 3 hours, light-catalysed degradation rate still has about 55%, it is believed that the photocatalyst of the present invention has certain
Reusability.
Copper oxide/the titania nanotube of table 1 different temperatures annealing preparation is at ultraviolet light and sunlight
Photo-catalytic degradation of methyl-orange comparing result
By checking embodiment it can be seen that the anatase type titanium dioxide nano tube of the oxide of present invention complex copper is every
Effect in photocatalysis test is superior to the catalytic effect of the titania nanotube of the oxide of non-complex copper, table 1 data simultaneously
Relative analysis draws: 450 DEG C of corresponding anatase type titanium dioxide nano tube catalyst are best to Photocatalytic Degradation of Methyl Orange effect.
Claims (8)
1. the preparation method of Cu oxide/titanium dioxide composite nano tube array, it is characterised in that comprise the following steps:
(1) anodization: clean surface, in the electrolytic solution anodic oxidation after titanium sheet is cut into the size being actually needed, obtain titanium dioxide
Titanium nano-tube array；
(2) chemical deposition: prepared nano-tube array is immersed in soluble copper saline solution, stand, then take out nanotube, leaching
Entering in aqueous slkali, stand, twice submergence and standing process are considered a cyclic deposition process, are repeated several times cyclic deposition process；
(3) annealing: the nano-tube array after cyclic deposition is put in Muffle furnace, anneals at a certain temperature.
The preparation method of a kind of Cu oxide/titanium dioxide composite nano tube array, its feature exists
In: described electrolyte is the solution that volume ratio is 5:1～8:1 of polyhydroxy organic solvent and water, has wherein dissolved mass fraction and has been
0.5%～1.0% containing villiaumite；During anodization, clean titanium sheet, as anode, connects positive source；Graphite electrode as negative electrode,
Connect power cathode；Electrolyte temperature is 25 ± 5 DEG C, and electrolysis time is 4～8h；Decomposition voltage is 40～50V.
The preparation method of a kind of Cu oxide/titanium dioxide composite nano tube array, its feature exists
In: in described chemical deposition step, the concentration of soluble copper saline solution is 0.03～0.06mol/L, and the concentration of aqueous slkali is mantoquita
2 times of concentration, time of repose is 40～60s, and cyclic deposition number of times is 3～7 times.
The preparation method of a kind of Cu oxide/titanium dioxide composite nano tube array, its feature exists
Nanotube after: the annealing described in step (3) is by chemical deposition is in the air atmosphere of Muffle furnace, with adding of 2 DEG C/min
Thermal velocity is heated to 400～450 DEG C, power-off after insulation 3～6h, allows Muffle furnace natural cooling, the oxide that i.e. can get copper be combined
The Nano tube array of titanium dioxide of anatase crystal.
The preparation method of a kind of Cu oxide/titanium dioxide composite nano tube array, its feature exists
In: described aqueous slkali is one or more mixing in ammonia, sodium hydroxide solution, potassium hydroxide solution.
A kind of nano-tube array preparation method with photocatalytic degradation Organic substance ability, its feature
It is: described polyhydroxy organic solvent is the mixing of one or more in glycerol, ethylene glycol and dihydroxy acetone.
The preparation method of a kind of Cu oxide/titanium dioxide composite nano tube array, its feature exists
In: described is soluble-salt containing villiaumite, and is one or more mixing in ammonium fluoride, sodium fluoride, potassium fluoride.
The preparation method of a kind of Cu oxide/titanium dioxide composite nano tube array, its feature exists
In: the soluble copper salt in step (2) is one or more mixing in copper sulfate, copper nitrate, copper chloride.
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| CN106348383A (en) * | 2016-09-22 | 2017-01-25 | 浙江工商大学 | C3N4-Bi2O3-BiOI-TiO2NTs visible-light response photocatalysis electrode as well as preparation method and application thereof |
| CN108786811A (en) * | 2018-06-27 | 2018-11-13 | 刘青 | A kind of preparation method of titanium dichloride load copper and iron oxide composite catalyzing material |
| CN110913987A (en) * | 2017-05-12 | 2020-03-24 | 威廉马歇莱思大学 | Multi-component plasmonic photocatalyst consisting of plasmonic antenna and reactive catalytic surface: antenna-reactor effect |
| CN113502513A (en) * | 2021-08-12 | 2021-10-15 | 辽宁大学 | Method for directly depositing copper metal by utilizing solar energy |
| CN114602467A (en) * | 2022-04-02 | 2022-06-10 | 新疆油苗环保科技有限公司 | Copper oxide doped mixed crystal titanium dioxide nanotube photocatalytic composite material and preparation method and application thereof |
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