CN101162743A - Preparation method of microgrid structure a photocatalyst - Google Patents
Preparation method of microgrid structure a photocatalyst Download PDFInfo
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- CN101162743A CN101162743A CNA2007101783954A CN200710178395A CN101162743A CN 101162743 A CN101162743 A CN 101162743A CN A2007101783954 A CNA2007101783954 A CN A2007101783954A CN 200710178395 A CN200710178395 A CN 200710178395A CN 101162743 A CN101162743 A CN 101162743A
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Abstract
The invention provides a method for preparing photocatalyst with microgrid construction which is to combine an N type semiconductor with a P type semiconductor or combine metal with a semiconductor. The concrete procedure is as follows: an underlay layer is firstly prepared with a layer of N type or P type semiconductor film, and then the surface of the film is prepared with a layer of middle moulding board layer, finally, a layer of P type or N type semiconductor or metal is deposited on the uppermost layer; after the moulding board layer is eliminated, the underlay semiconductor film is compounded with the uppermost semiconductor or metal microgrid to obtain P-N hetero junction photocatalyst and semiconductor photocatalyst with decorated surface of metal microgrid. The invention solves the problem of uneven combination in the prior surface modification method, the grid structure with regular structure ensures that the surfaces of the two materials are orderly separated, which increases the contact area with organic matter, accelerates the process of transporting photo-induced carrier, lowers the combination probability of electron hole and raises the quantum efficiency of photocatalysis.
Description
Technical field
The present invention relates to a kind of new modified method of semiconductor light-catalyst, particularly a kind of microgrid structured light Preparation of catalysts method.
Background technology
Based on wide bandgap semiconductor (TiO
2Or ZnO) first generation photochemical catalyst utilizes ultraviolet light, has the almost defective of sharp have more than is needed visible light, and countries in the world are all competitively developed can not only efficiently utilize ultraviolet light, and can utilize the second generation photochemical catalyst of visible light.Also there be the science and the technical barrier of several keys in the photocatalysis technology of the first generation at present, its wide industrial is used be subjected to great restriction.Wherein distinct issues are: (1) quantum efficiency low (～4%) is difficult to handle a large amount of and high waste water and the waste gas of concentration; (2) solar energy utilization ratio is low.(Eg＞3.0eV) has determined to absorb the ultraviolet portion (radiation of sunlight medium ultraviolet only is～5%) in ultraviolet light or the sunlight because the band structure of wide bandgap semiconductor.From bibliographical information, utilize the study on the modification of visible light to concentrate on aspects such as doped transition metal ions, precious metal surface deposition, dye sensitization, semiconductor be compound mostly to first generation photochemical catalyst.
After semiconductor surface deposits an amount of noble metal, the charge carrier redistribution, electronics is transferred to the lower metal of Fermi level from the higher n N-type semiconductor N of Fermi level, and is identical until its Fermi level, thereby forms Schottky barrier.Schottky barrier becomes effective trap of capturing excitation electron, and photo-generated carrier is separated, thereby has suppressed the compound of electronics and hole.Noble metal commonly used is Pt, Ag, Au, Pd etc.
Along with nano material preparation technology and energy band engineering method obtain marked improvement, applying nano technology and heterojunction semiconductor method can prepare the catalyst that directly utilizes visible light.Two kinds of different energy level difference can strengthen separation of charge, suppress the compound of electronics and hole in the binary composite semiconductor, and expansion wavelength absorption scope improves the photon utilance, has better activity thereby demonstrate than single semiconductor.The TiO that is reported
2Compound system mainly contains CdS-TiO
2, SnO
2-TiO
2, WO
3-TiO
2, V
2O
5-TiO
2, Fe
3O
4-TiO
2Deng, these compound systems nearly all show and are higher than single semi-conductive photocatalysis performance.
Although the research of composite semiconductor heterojunction is more, mostly be n-n type composite semiconductor, two kinds of semiconductors are simple couplings, though certain promotion separation of charge effect is arranged, can not realize effective fast transferring of electric charge.Structure is with the composite semiconductor of ohmic contact form, charge migration with separate easilier, photocatalysis efficiency is also higher, so the agent of p-n heterojunction novel photocatalysis is the another focus of photochemical catalyst research.There are the part Study personnel to begin to attempt TiO
2With Cu
2The p-n junction photochemical catalyst that O is compound.That Fig. 1 represents is the photocatalysis principle figure of p-n junction heterojunction photocatalyst, by the semi-conductive compound separation of charge effect that improves system, expands its scope of spectral response.Its reason be attributable to different can level semiconductors between transporting of photo-generated carrier be easy to separate.When with the optical excitation of enough energy, the electronics band-to-band transition takes place in binary semiconductor simultaneously, because the difference of conduction band and valence-band level, light induced electron will accumulate on wherein a kind of conduction band, then assemble on the alternative valence band in the hole, and photo-generated carrier obtains separating, thereby has improved quantum efficiency.
There are some researches show, because the bulk effect of noble metal is modified TiO at Pt
2Improve in the research of photocatalysis performance, the use content of Pt generally is controlled within the 0.5-10wt%.Even yet the Pt of 10wt% modification, Pt is at TiO
2The area occupied percentage of particle surface only is about 6%.This that is to say that whole particle has 94% area can be used to provide the release of photohole, and only 6% area is provided and is used for adsorb oxygen and discharges electronics, and this obviously is unbalanced, thereby has noble metal decorated TiO
2Catalyst, surperficial situation likely be, the hole is consumed in a large number, and electronics is hoarded in a large number.The consequence that electronics is hoarded is the complex centre that becomes the hole, has reduced the quantum efficiency of material light catalysis.
In order to solve the accumulation problem of metal surface electronics, if can be with tiny plain conductor with TiO
2Particle is communicated with, and might can solve TiO
2Electronics on the particle is piled up problem, thereby increases substantially TiO
2Photocatalysis performance and quantum efficiency.That Fig. 2 represents is the several TiO that are in diverse location
2Particle is by the photoexcitation carrier transport process under the metal micro wiring connection situation.Suppose at a time TiO
2Particle A has absorbed a photon, has produced a pair of electronics and hole.The hole is diffused into particle surface and successfully reacts with the surface adsorption species and consume, and electronics is residual.Under common situation, excess electron will become the right composite object of next optical excitation electricity, cause quantum loss; If yet the metal connectivity structure of employing Fig. 2, so remaining free electron will be by metal separation, and be transported to the place that needs electronics by the metal that is communicated with: a kind of may be that an oxygen molecule has been adsorbed in a certain position on the metalolic network, and electron transfer reacts with it to this position and consumes; Another kind may be the some TiO in distant place
2Particle D is just also by photon excitation, its electronics just in time with the reactant of surface adsorption reaction has taken place and the hole is residual, this moment, the structure of metal conduction can transfer an electron to this particle, make it compound with it, though the photon utilization ratio (quantum efficiency) of this compound generation is 50%, yet the quantum efficiency low with respect to light-catalyzed reaction (＜5%) has been very big raising.And if this recombination process not, TiO
2The electric charge accumulation of particle surface will cause its quantum efficiency further loss.The purpose of little metal connectivity structure is the carrier flow usefulness mutually between enhanced granule, improves the photon utilization ratio.
P N-type semiconductor N Cu
2O (Eg=2.0eV) has visible light activity, and theoretical solar energy converting efficient can reach 13%, but because the composite action of photo-generated carrier makes efficient not high.Li etc. adopt the Cu of electrochemical process with nanoscale
2O is deposited on TiO
2Last preparation p-n compound is at the Cu of 3wt%
2Has the highest photocatalytic activity during O content.If TiO
2-Cu
2The compound inhomogeneous or too high levels of O semiconductor light-catalyst will cause the photo-generated carrier transport process to be obstructed, and the electronics of hoarding is very easily by Cu
2O catches, and causes the generation of composite photo-catalyst intoxicating phenomenon.
When illumination, produce electron hole pair in the semiconductor bulk, after these charge carriers are diffused into the surface, has catalytic effect, the form that these charge carriers arrive the surface is by diffusion, motion path is at random, and motion path is long, recombination probability height before arriving the surface, but present p-n heterojunction novel photocatalysis agent photochemical catalyst is undertaken compound by the form of doping and multilayer film, though the heterojunction that can be with two kinds of semiconductors of coupling to form helps the right separation in light induced electron hole, but the charge carrier of primer is diffused in the upper surface process, the charge carrier recombination probability height each other of two kinds of materials in the body, charge carrier diffusion after the separation is less than upper surface, can not be utilized by organic substance, photocatalysis efficiency is low, and composite material only could shorten the diffusion length that charge carrier arrives the surface below tens nanoscales, effectively improve the photocatalysis quantum efficiency.
Summary of the invention
Technology of the present invention is dealt with problems: overcome the deficiencies in the prior art, a kind of microgrid structured light Preparation of catalysts method is provided, adopt mould plate technique to obtain p-n heterojunction photocatalyst and metal microgrid modification photochemical catalyst, improved photocatalytic quantum.
Technical solution of the present invention: a kind of microgrid structured light Preparation of catalysts method, n N-type semiconductor N and P type semiconductor are combined with each other, or metal and semiconductor be combined with each other, specific as follows: as at first on substrate layer, to prepare one deck n type or p N-type semiconductor N film, subsequently at this layer film surface preparation one deck intermediate die flaggy, at last at the superiors' deposition one deck p type or n N-type semiconductor N or metal, after removing template layer, substrate layer semiconductive thin film and the superiors' semiconductor or metal microgrid are compound, obtain the semiconductor light-catalyst of p-n heterojunction photocatalyst and the finishing of metal microgrid.
Described substrate is glass or quartz substrate.
The semi-conducting material of the described substrate layer and the superiors is the special-shaped semi-conducting material of two kinds of different energy gaps, both can be with coupling, valence band and conduction band stagger mutually, and light induced electron accumulates on a kind of semi-conductive conduction band, and photohole then accumulates on the another kind of semi-conductive valence band.
Described metal is Ag, Au, Cu, Pt, Pd, Ru, Ir, Nb, thickness＜100nm.
Described template layer is the organic formwork with chondritic, microspherulite diameter 1～5 μ m, and processing mode is organic solvent dissolution or Low Temperature Heat Treatment.
Described n N-type semiconductor N material is TiO
2Or ZnO; Described p N-type semiconductor N is Cu
2O or Bi
2O
3
The preparation method of described n N-type semiconductor N film comprises: sol impregnation lifts 1～10 layer film, and the film heat treatment temperature is 450～750 ℃, is incubated 2～3 hours, film thickness 30～300nm; Magnetron sputtering method prepares film, adopts RF-reactively sputtered titanium, and film thickness is 35～305nm.
Described template layer prepares with the liquid level self-assembly method, and the metal microgrid prepares with direct current magnetron sputtering process.
The preparation method of described p N-type semiconductor N film comprises: the reaction magnetocontrol sputtering film, and film thickness is 55～305nm, electrochemical deposition method prepares film, film thickness＜50nm.
The present invention's advantage compared with prior art is: utilize rule uniformly network semiconductive thin film is carried out surface modification, avoided the compound problem of non-uniform that exists in the surface modifying method in the past, laminated film thickness can be in the sub-micrometer scale scope.The network of compound with regular structure causes the surface of two kinds of materials to be separated in order, has increased and organic contact area, accelerates the transport process of photo-generated carrier, has reduced the recombination probability of electron hole, has improved photocatalytic quantum.
Description of drawings
Fig. 1 is p-n junction heterojunction photocatalyst photocatalysis principle figure;
Fig. 2 is the photocatalysis principle figure of metal grill finishing photochemical catalyst;
Fig. 3 is the micro-structure diagram of microgrid structured light catalyst of the present invention.
Embodiment
The present invention is described in detail below in conjunction with embodiment and accompanying drawing, but protection scope of the present invention is not limited in the following example, should comprise the full content in claims.And those skilled in the art can realize full content the claim from following embodiment.
Embodiment 1
Get the 6.8ml butyl titanate, join the absolute ethyl alcohol of 50ml, with magnetic stirrer its dissolving is uniformly dispersed, the hydrochloric acid that in above mixed liquor, adds 50 μ l then, and add the 1ml acetylacetone,2,4-pentanedione, the water that the is added dropwise to 0.72ml at last TiO that ageing can obtain having certain viscosity in 24 hours that stirs
2Colloidal sol.Sol impregnation lifts the TiO that thickness is 33nm on glass substrate
2Film is warming up to 450～550 ℃ with 5 ℃/min in the air calcination stove, be incubated 2 hours, and at film surface liquid level self assembly one deck polystyrene microsphere, microspherulite diameter is 2 μ m, utilizes direct current reaction magnetron sputtering to deposit the Cu that a layer thickness is about 100nm then
2O, sputtering pressure 1Pa, power 80W, oxygen argon ratio is 1: 8, then composite sample be impregnated in the tetrahydrofuran solvent, PS microsphere template layer is removed in dissolving, finally obtains p type Cu
2The TiO that the O microgrid is modified
2Photocatalysis film.Radiation of visible light 3 hours, this photochemical catalyst can be degraded to 26% with methylene blue solution concentration.
Embodiment 2
Preparation thickness is the TiO of 33nm as described in the example 1 as implementing on quartz substrate
2Film and PS microsphere template layer adopt magnetically controlled DC sputtering depositing noble metal Ag, sputtering pressure 1.5Pa then, power 70W, sputtering time 1min impregnated in composite sample in the tetrahydrofuran solvent then, PS microsphere template layer is removed in dissolving, finally obtains the TiO that metal A g microgrid is modified
2Photocatalysis film.Fig. 3 is this sample microscopic appearance figure, and a, b are SEM figure, and c, d are AFM figure.Ultra violet lamp 1 hour, this photochemical catalyst can be degraded to 24.4% with methylene blue solution concentration.
Embodiment 3
On quartz substrate as implementing the TiO of preparation 33nm as described in the example 1
2Film and PS microsphere template layer adopt magnetically controlled DC sputtering plated metal Au then, sputtering pressure 1.5Pa, power 30W, sputtering time 1min.Then composite sample is put into 200 ℃ of heat treatments of muffle furnace, removed PS microsphere template layer, finally obtain the TiO that metal A u microgrid is modified
2Photocatalysis film.Ultra violet lamp 1 hour, this photochemical catalyst just methylene blue solution concentration are degraded to 36.7%.
Embodiment 4
At first RF-reactively sputtered titanium deposits the TiO that a layer thickness is about 100nm on glass substrate
2Film, sputtering pressure 0.5Pa, power 150W, oxygen argon ratio is 1: 10, at film surface liquid level self assembly one deck PS microsphere template, microspherulite diameter is 1 μ m, adopts dc reactive sputtering to deposit the Cu that a layer thickness is about 100nm then
2O, sputtering pressure 1Pa, power 80W, oxygen argon ratio is 1: 8, and composite sample be impregnated in the tetrahydrofuran solvent, PS microsphere template layer is removed in dissolving, finally obtains p type Cu
2The TiO that the O microgrid is modified
2Photocatalysis film.
Embodiment 5
On quartz substrate, prepare TiO as described in the example 4 as implementing
2Nano thin-film and PS microsphere template layer adopt magnetically controlled DC sputtering plated metal Ag, thickness＜100nm then, sputtering pressure 1.5Pa, power 70W impregnated in composite sample in the tetrahydrofuran solvent then, PS microsphere template layer is removed in dissolving, finally obtains the TiO that metal A g microgrid is modified
2Photocatalysis film.
Embodiment 6
On quartz substrate, prepare TiO as described in the example 4 as implementing
2Film and PS microsphere template layer adopt magnetically controlled DC sputtering plated metal Au, thickness＜100nm then, sputtering pressure 1.5Pa, power 30W puts into composite sample 200 ℃ of heat treatments of air calcination stove then, remove PS microsphere template layer, finally obtain the TiO that metal A u microgrid is modified
2Photocatalysis film.
Embodiment 7
At first on glass substrate, adopt dc reactive sputtering to deposit the Cu that a layer thickness is about 100nm
2The O film, sputtering pressure 1.5Pa, power 80W, oxygen argon ratio is 1: 9, at film surface liquid level self assembly one deck PS microsphere template, microspherulite diameter 1～3 μ m, RF-reactively sputtered titanium deposits the TiO that a layer thickness is about 100nm then
2Film, sputtering pressure 1Pa, power 120W, oxygen argon ratio is 1: 10, and composite sample be impregnated in the tetrahydrofuran solvent, PS microsphere template layer is removed in dissolving, finally obtains n type TiO
2The Cu that microgrid is modified
2The O photocatalysis film.
Embodiment 8
Prepare Cu as implementing as described in the example 7 in glass substrate
2O film and PS microsphere template layer, sol impregnation lifts 1～3 layer of TiO then
2Nano thin-film is warming up to 450～550 ℃ with 5 ℃/min in the tubular type atmosphere furnace, be incubated 2 hours, and protective gas is a nitrogen, finally obtains n type TiO
2The Cu that microgrid is modified
2The O photocatalysis film.
Embodiment 9
Can prepare Cu with method identical in the above example
2O or various metal microgrid are modified n type ZnO photocatalysis film.
Claims (10)
1. microgrid structured light Preparation of catalysts method, it is characterized in that: at first on substrate layer, prepare one deck n type or p N-type semiconductor N film, subsequently at this layer film surface preparation one deck intermediate die flaggy, at last at the superiors' deposition one deck p type or n N-type semiconductor N or metal, after removing template layer, substrate layer semiconductive thin film and the superiors' semiconductor or metal microgrid are compound, obtain the semiconductor light-catalyst of p-n heterojunction photocatalyst and the finishing of metal microgrid.
2. microgrid structured light Preparation of catalysts method according to claim 1, it is characterized in that: described substrate is glass or quartz substrate.
3. microgrid structured light Preparation of catalysts method according to claim 1, it is characterized in that: the semi-conducting material of the described substrate layer and the superiors is the special-shaped semi-conducting material of two kinds of different energy gaps, both can be with coupling, valence band and conduction band stagger mutually, light induced electron accumulates on a kind of semi-conductive conduction band, and photohole then accumulates on the another kind of semi-conductive valence band.
4. microgrid structured light Preparation of catalysts method according to claim 1 is characterized in that: metal is Ag or Au or Cu or Pt or Pd or Ru or Ir or Nb, thickness＜100nm.
5. microgrid structured light Preparation of catalysts method according to claim 1, it is characterized in that: described template layer is the organic formwork with chondritic, microspherulite diameter 1～5 μ m, processing mode is organic solvent dissolution or Low Temperature Heat Treatment.
6. microgrid structured light Preparation of catalysts method according to claim 1 is characterized in that: described n N-type semiconductor N material is TiO
2Or ZnO.
7. microgrid structured light Preparation of catalysts method according to claim 1, it is characterized in that: described p N-type semiconductor N is Cu
2O or Bi
2O
3
8. microgrid structured light Preparation of catalysts method according to claim 1, it is characterized in that: the preparation method of described n N-type semiconductor N film comprises: sol impregnation lifts 1～10 layer film, the film heat treatment temperature is 450～750 ℃, be incubated 2～3 hours, film thickness 30～300nm; Magnetron sputtering method prepares film, adopts RF-reactively sputtered titanium, and film thickness is 35～305nm.
9. microgrid structured light Preparation of catalysts method according to claim 1 is characterized in that: described template layer prepares with the liquid level self-assembly method, and the metal microgrid prepares with direct current magnetron sputtering process.
10. microgrid structured light Preparation of catalysts method according to claim 1, it is characterized in that: the preparation method of described p N-type semiconductor N film comprises: the reaction magnetocontrol sputtering film, film thickness is 55～305nm, and electrochemical deposition method prepares film, film thickness＜50nm.
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