A kind of novel photocatalysis material based on Cu and Ag and preparation method thereof
Technical field
The invention belongs to novel photocatalysis technical field of material, particularly relate to a kind of novel photocatalysis material C u based on Cu and Ag
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2and preparation method.
Background technology
Along with industrial expansion, the originally limited water resource of the mankind is subject to day by day serious pollution, removes the toxic and harmful substance in water body, as halogenated hydrocarbons, agricultural chemicals, surfactant etc. become an important process of field of Environment Protection.According to the variation characteristic of pollutant in processing procedure, wastewater treatment can be divided into 3 types, i.e. separating treatment, conversion processing and dilution process.Separating treatment just by pollutant from a kind of phase transfer to another phase, pollutant can not be made thoroughly to be decomposed or innoxious, some methods also also exist the problem of secondary pollution.Dilution process just alleviates the pollution of water body by dilution waste water, both not separated from contaminants, also can not change the chemical property of pollutant.Conversion processing is then the chemical nature being changed pollutant by the effect of chemistry or biochemistry, makes it be converted into harmless or separable material.Along with the development of green technology and the raising to Water quality requirement, conversion processing comes into one's own day by day.But current transformation processing method is the pollutant large for discharge capacity, concentration is higher mostly, purification that is lower for concentration in water body, that be difficult to the priority pollutant transformed is also helpless.And the solution that the Photocatalyst grown up gradually over nearly 20 years is this problem provides good approach.The people such as Matthews had once carried out systematic research to the photocatalysis Decomposition of 34 kinds of organic pollutions in water, result show photocatalytic oxidation can by the hydro carbons in water, halides, hydroxy acid, surfactant, dyestuff, itrogenous organic substance, organophosphorus insecticide etc. quickly complete oxidation be CO
2and H
2the innocuous substances such as O.Photocatalyst just can carry out under having normal temperature and pressure, thoroughly can destroy organic matter, does not have secondary pollution and expense not too advantages of higher.
But due to TiO
2can be with greater band gap (3.2eV), can only the shorter ultraviolet light of absorbing wavelength, cause it very low to the utilization rate of sunshine, and optical excitation TiO
2the electronics produced Deng semi-conducting material easily and hole-recombination, causes photo-quantum efficiency to reduce, therefore have impact on TiO
2deng the catalytic performance of semi-conducting material.Improve TiO
2deng the photolytic activity of semi-conducting material at visible region, the compound suppressing electronics and hole improves the committed step of catalyst efficiency.In recent years, people attempt by means such as metal-doped, nonmetal doping, metal and nonmetal codope, semiconductors coupling and dye photoactivations, the photoresponse scope of the semi-conducting materials such as expansion, suppress the compound in electronics and hole, thus improve TiO
2and the photocatalytic activity of compound.Therefore obtain that a kind of catalytic performance is excellent, the good catalysis material of visible light activity remains a challenge.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of Cu with good photocatalysis effect is provided
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2novel photocatalysis material and preparation method.
The object of the invention is to be achieved through the following technical solutions: a kind of novel photocatalysis material based on Cu and Ag, this material is Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2, wherein, 0<x, y≤1, this material is at TiO
2nano wire modifies Cu
xag
(1-x), (Cu
yag
(1-y))
2o nano particle and bulk Ag
3pO
4obtain, wherein, Cu
xag
(1-x)the diameter of particle is 10-50nm, (Cu
yag
(1-y))
2the diameter of O particle is 5-20nm, bulk Ag
3pO
4diameter be 50-200nm.
A kind of Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2the preparation method of novel photocatalysis material, comprises the following steps:
(1) TiO is prepared at titanium plate surface
2nano wire.
(2) TiO
2nanowire supported Cu
xag
(1-x)nano particle, is specially:
(2.1) 1g glucose and 0.5gPVP are dissolved in 25mL deionized water, the titanium sheet after then step 1 being processed is placed in solution, then in solution, add the Cu (NO of 0.1mol/L of 10mL
3)
2, continue to stir 0.5h; Then mixed solution and titanium sheet are transferred in reactor, 60-120 DEG C reaction 0.2-3h, take out reacted titanium sheet, after flushing in 60 DEG C of baking ovens dry 1h, obtain the TiO of surface ornament Cu nano particle
2nano wire;
(2.2) mixed with absolute ethyl alcohol equal-volume by silver ammino solution, the titanium sheet after then step 2.1 being processed is placed in the mixed solution by silver ammino solution and absolute ethyl alcohol, and 70 DEG C of temperature constant magnetic stirring 1h, obtain Cu
xag
(1-x)the TiO that nano particle is coated
2nano wire, i.e. Cu
xag
(1-x)/ TiO
2;
(3) Cu
xag
(1-x)the TiO that nano particle is coated
2nanowire supported (Cu
yag
(1-y))
2o nano particle, is specially:
(3.1) by the Cu (NO of the 0.1mol/L of 10mL
3)
2solution mixes with 80mL absolute ethyl alcohol, and the titanium sheet after then step 2 being processed is placed in Cu (NO
3)
2with in the mixed solution of absolute ethyl alcohol, react under agitation after 2 hours, take out titanium sheet, after calcining 2-3h after titanium sheet drying at 350 DEG C, be cooled to room temperature, obtain Cu
xag
(1-x)/ Cu
2o/TiO
2;
(3.2) NaOH solution of 0.5mol/L being instilled 30mL mass fraction is in the hydrogen peroxide of 30%, and make pH value reach 9 ~ 10, the titanium sheet after step 3.1 being processed is placed in one, and after 15min, takes out reactant, obtains Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/TiO
2;
(4) AgNO of 0.03mol/L is configured
3the NaH of solution and 0.03mol/L
2pO
4solution, the titanium sheet after step 3 being processed is successively at AgNO
3submergence 30min in solution, at NaH
2pO
4submergence 5min in solution, circulation submergence 3 times, obtains Cu
xag
(1-x)/ (Cu
yag
(1-y)) O/Ag
3pO
4/ TiO
2novel photocatalysis material.
The present invention has following technique effect:
(1) raw material is easy to get, and preparation process is simple, and repetitive rate is high, is applicable to industrial production.
(2) loaded Cu is passed through
xag
(1-x), (Cu
yag
(1-y))
2o, Ag
3pO
4etc. multiple particle, effectively can suppress the compound in electronics and hole, thus improve TiO
2and the photocatalysis performance of compound.
(3) at (Cu
yag
(1-y))
2o, Ag
3pO
4tiO is transferred to Deng the electronic energy that narrow gap semiconductor excites
2on, make photo-generated carrier be easy to be separated, thus significantly improve TiO
2visible light photocatalysis active.
Accompanying drawing explanation
In Fig. 1, A-D is that under different condition in Product scan electron microscope (SEM) figure, figure, A is TiO
2, B is Cu
xag
(1-x)/ TiO
2, C is Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/TiO
2, D is Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2;
In Fig. 2, A-D is that in transmission electron microscope (TEM) figure, the figure of product under different condition, A is TiO
2, B is Cu
xag
(1-x)/ TiO
2, C is Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/TiO
2, D is Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2;
Fig. 3 is the change in concentration (C/C of different catalysts along with the increase methylene blue in reaction time
0) figure: scheming A is TiO
2, figure B is Cu
xag
(1-x)/ TiO
2, figure C is Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/TiO
2, figure D is Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2.
Detailed description of the invention
A kind of Cu of the present invention
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2novel photocatalysis material, 0<x, y≤1, this material is at TiO
2nano wire modifies Cu
xag
(1-x), (Cu
yag
(1-y))
2o nano particle and bulk Ag
3pO
4obtain, wherein, Cu
xag
(1-x)the diameter of particle is 10-50nm, (Cu
yag
(1-y))
2the diameter of O particle is 5-20nm, bulk Ag
3pO
4diameter be 50-200nm.
A kind of Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2the preparation method of novel photocatalysis material, comprises the following steps:
(1) nano-TiO
2because it has the advantages such as stable chemical nature, nontoxic, absorption UV resistance is strong, be often used as catalysis material.First the present invention prepares TiO at titanium plate surface
2nano wire; This preparation method can be: the titanium sheet of 2.5cm × 2.5cm is put into acetone, ultrasonic process 15min, then uses the ultrasonic 5min of deionized water.The titanium sheet handled well is put into the hydrothermal reaction kettle of polytetrafluoroethylene (PTFE), the NaOH solution adding 2mol/L is about 10mL makes not have titanium sheet, and sealing hydrothermal reaction kettle is placed in baking oven, 240 DEG C of heated at constant temperature 12h.After completion of the reaction, naturally cool to room temperature, reactant is taken out, obtains TiO by washed with de-ionized water
2nano wire.The TiO prepared
2nano wire as shown in figs. la and 2.
(2) TiO
2nanowire supported Cu
xag
(1-x)nano particle, is specially:
(2.1) deionized water that 1g glucose and 0.5gPVP add 25mL is got, at room temperature magnetic agitation 3h, titanium sheet (the superficial growth TiO after step 1 being processed
2the titanium sheet of nano wire) be put in solution, and add the Cu (NO of the 0.1mol/L of 10mL
3)
20.5h is stirred in rear continuation, then by above-mentioned solution (glucose, PVP, Cu (NO
3)
2mixed solution) and titanium sheet transfer in reactor, reactor is placed in 60-120 DEG C and reacts 0.2-3h, after reaction, remove supernatant, adopt absolute ethyl alcohol and deionized water to rinse titanium sheet respectively three times, put into 60 DEG C of dry 1h of baking oven, obtain the TiO of surface ornament Cu nano particle
2nano wire;
(2.2) according to 0.1gAgNO
3adding 20mL deionized water configuration solution A, is the ammoniacal liquor of 25-28% and the deionized water configuration solution B of 50mL by 2mL concentration.In A, drip B solution, until without muddy (about adding 5mL), then add the absolute ethyl alcohol (about 25mL) equal with silver ammino solution volume, the titanium sheet (TiO of surface ornament Cu nano particle after step 2.1 being processed
2nano wire) be placed in one, 70 DEG C of temperature constant magnetic stirring 1h, obtain Cu
xag
(1-x)the TiO that nano particle is coated
2nano wire, as shown in figs. ib and 2b, as can be seen from Figure, Cu
xag
(1-x)the particle diameter of nano particle is between 10-50nm.The TiO of doped with Cu
2catalysis material can improve the response to visible light source, and the heavy metal nano particles such as Ag doped can suppress the compound in electronics and hole, thus improves TiO
2photocatalysis performance.
(3) Cu
xag
(1-x)the TiO that nano particle is coated
2nanowire supported (Cu
yag
(1-y))
2o nano particle:
(3.1) Cu (NO of the 0.1mol/L of 10mL
3)
2solution joins 80mL ethanol solution, and the titanium sheet after then step 2 being processed is placed in Cu (NO
3)
2with in the mixed solution of absolute ethyl alcohol, under room temperature, react 2 hours under magnetic agitation condition, then by reacted titanium sheet at 60 DEG C dry 6 hours, calcine 2-3h at 350 DEG C after, finally temperature is reduced to room temperature, makes Cu
2o loads to above-mentioned sample surfaces, obtains Cu
xag
(1-x)/ Cu
2o/TiO
2;
(3.2) NaOH solution of 0.5mol/L being instilled 30mL concentration is in the hydrogen peroxide of 30%, makes pH value reach 9 ~ 10, the titanium sheet (loaded Cu after step 3.1 being processed
xag
(1-x)/ Cu
2o/TiO
2titanium sheet) be placed in one, after 15min, take out reactant, obtain load (Cu
yag
(1-y))
2o nano particle and Surface coating Cu
xag
(1-x)the TiO of nano particle
2nano wire, as shown in Fig. 1 C and 2C, as can be seen from Figure, (Cu
yag
(1-y))
2the particle diameter of O nano particle is between 5-20nm.Under visible light illumination, from Cu
2o, Ag
2the electronic energy that the narrow gap semiconductors such as O excite transfers to TiO
2on, make photo-generated carrier be easy to be separated, thus significantly improve TiO
2visible light photocatalysis active.
(4) Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2the synthesis of novel photocatalysis material: the AgNO of configuration 0.03mol/L
3the NaH of mixed solution solution and 0.03mol/L
2pO
4solution, the nano wire (3) prepared alternately is immersed in two parts of solution, and the time of immersing is respectively 30min and 5min, and circulation immerses circulation 3 times according to the method described above, obtains Cu
xag
(1-x)/ (Cu
yag
(1-y)) O/Ag
3pO
4/ TiO
2novel photocatalysis material, as shown in Fig. 1 D and 2D, as can be seen from Figure, bulk Ag
3pO
4diameter be 50-200nm.Ag
3pO
4under visible light can fast degradation organic pollution, far above TiO
2activity, but Ag
3pO
4unstable chemcial property, at TiO
2area load Ag
3pO
4tiO can be significantly improved
2visible light activity and improve Ag
3pO
4stability in the reaction.
To Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2novel photocatalysis material carries out photocatalysis test: with the methylene blue solution of 9.2mg/L for target degradation product, get 100mL target degradation product and be placed in glass container, container skin uses condensed water constant temperature, using 500W visible lamp as light source, be placed in the center of glass container, illumination is after ten minutes under magnetic stirring, adds four each 10mg (TiO of sample
2, Cu
xag
(1-x)/ TiO
2, Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/TiO
2, Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2).Get a sample at interval of 30min, sample with 15min centrifugal under the condition of 1000r/min, gets supernatant liquor in centrifuges, adopts UV-8500 ultraviolet-visible spectrophotometer (UV-vis) to methylene blue change in concentration (C/C
0) change curve.As shown in Figure 3, Fig. 3 A is TiO to test result
2, Fig. 3 B is Cu
xag
(1-x)/ TiO
2, Fig. 3 C is Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/TiO
2, Fig. 3 D is Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2.Cu can be found out
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4/ TiO
2photocatalysis performance is good.By contrast TiO
2, with at TiO
2surface is loaded Cu respectively
xag
(1-x), Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o and Cu
xag
(1-x)/ (Cu
yag
(1-y))
2o/Ag
3pO
4four kinds of catalysis materials, to the absorbent properties of methylene blue, can be found out at TiO
2area load Cu
xag
(1-x), (Cu
yag
(1-y))
2o, Ag
3pO
4effectively TiO can be strengthened on particle
2photocatalysis performance.Existing to TiO
2in the technology that photocatalysis performance improves, the C/C of methylene blue after photocatalysis 2h
0be reduced near 0.6, and the nano composite photocatalytic material that the present invention obtains can by methylene blue C/C during 2h
0be reduced to less than 0.1, as shown in Figure 3, therefore this material light catalysis ability is better than prior art.