CN102698784B - Visible light response catalyst and preparation method thereof - Google Patents
Visible light response catalyst and preparation method thereof Download PDFInfo
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- CN102698784B CN102698784B CN201210199471.0A CN201210199471A CN102698784B CN 102698784 B CN102698784 B CN 102698784B CN 201210199471 A CN201210199471 A CN 201210199471A CN 102698784 B CN102698784 B CN 102698784B
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- vanadic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000004298 light response Effects 0.000 title claims abstract description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 27
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 7
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 3
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical group O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 6
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- OZNBFONAEYVYCP-UHFFFAOYSA-N [Dy].[V] Chemical compound [Dy].[V] OZNBFONAEYVYCP-UHFFFAOYSA-N 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 8
- 229940043267 rhodamine b Drugs 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 metals cation Chemical class 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- GEZAXHSNIQTPMM-UHFFFAOYSA-N dysprosium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Dy+3].[Dy+3] GEZAXHSNIQTPMM-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a visible light response catalyst and a preparation method thereof. The chemical composition general formula of the catalyst is xDyVO4/g-C3N4, wherein x is the mass fraction of dysprosium vanadate in the catalyst, the mass fraction of g-C3N4 is 1-x, and x is at least 0.1 and is at most 0.4. The preparation method of the catalyst comprises the following steps of preparing the dysprosium vanadate and graphite phase carbon nitride with a precipitation method and a direct roasting method; then according to the DyVO4/g-C3N4 mass ratio, mixing the dysprosium vanadate with the graphite phase carbon nitride to be ground for 10 minutes; and finally roasting for 2 hours at the temperature of 300-600 DEG C to obtain a catalyst finished product. The preparation method of the catalyst is simple and low in cost, and the visible light degradation performance to organic dyestuffs is good.
Description
Technical field
The present invention relates to a kind of visible light response catalyst and preparation method thereof.
Background technology
Environmental pollution is the significant challenge that current mankind faces, the drinking water source that it has caused people to live, and industry water source quality constantly declines, and atmosphere pollution constantly aggravates, and causes the continuous destruction of ecological environment, is having a strong impact on people's Health and Living quality.Therefore, how cost-effectively environment purification pollution is that we must tackle and the great key scientific challenges solving.With traditional physical absorption, the methods such as chemical catalysis are compared, and it is low that photocatalysis technology has cost, non-secondary pollution, and the advantage of applied range, is the green environment improvement technology of tool exploitation of 21 century future.
Find TiO from Fujishima in 1972 and Honda
2electrode can decomposition water under illumination since thereby this phenomenon opens photocatalysis research prelude, and existing numerous catalyst is in the news.Nano-TiO
2wherein to there is most one of photochemical catalyst of application potential, it has good chemical stability, abrasion resistance, fast light burn into low cost and the advantage such as nontoxic, thereby is widely used in preparation of photodissociation water, degradation of organic substances, sterilization and sensitization solar battery etc.But because the forbidden band (3.2ev) of titanium dioxide is wide, light abstraction width only limits to ultraviolet region, to the utilization rate of solar energy too low (approximately 4%), limit its large-scale application.Therefore, in order effectively to utilize solar energy, meet the indoor demand without UV environment light catalytic purifying simultaneously, find visible light-responded photochemical catalyst imperative.
The method of development of new visible light response catalyst mainly contains two approach at present, to TiO
2modify and make it have visible light-responded ability (as doping metals cation or metalloid anion, dye sensitization etc.) and directly develop the novel photocatalyst with visible light-responded ability.From current achievement in research, TiO
2the modified catalyst organic activity of degrading under solar light irradiation is not very high, and stability aspect also exists some problems.Therefore, people focus onto on rear a kind of development approach one after another, and large quantities of novel visible light catalysts are in the news, as the Ag of the exploitations such as Zou Zhigang
2zO
4type (Z represents Cr, Mo, W, Mn etc.) composite oxides (CN1799691A) and AgTO
2type (T represents Al, Ga, In, Cr, Fe, Co, Ni) composite oxides (CN1799690A), the disclosed BaBi of CN1905940A
xo
y(0.5<x<2,2<y<4) composite oxides etc.Because the 3d orbital electron of V can be by excited by visible light, thereby vanadate is also the semi-conducting material that a class has visible light-responded character, not only can be used as photoactivate semiconductor and modify other wide band gap semiconducters, itself also there is good photocatalysis performance, recently received more researcher's concern.Graphite mould carbonitride (g-C
3n
4) be a newfound class in polymer type catalysis material in 2009, because its cost performance is high, also there is higher heat endurance and chemical stability simultaneously, obtain rapidly researcher's attention.But it is shorter to be limited to search time, relevant research report is less.
Summary of the invention
The object of the present invention is to provide a kind of preparation method non-oxide titanium high-activity photocatalyst and preparation method simple, with low cost.
For implementing this goal of the invention, the technical scheme of employing is:
A kind of visible light response catalyst, is characterized in that: this catalyst is vanadic acid dysprosium composite graphite phase carbon nitride, and chemical composition general formula is xDyVO
4/ g-C
3n
4, x is the mass fraction of vanadic acid dysprosium in catalyst, graphite-phase carbonitride (g-C
3n
4) mass fraction be 1-x, 0.1≤x≤0.4.
Preferably x is 0.15.
G-C
3n
4be graphite-phase carbonitride (graphitic carbon nitride).
The preparation method of this catalyst, comprises the following steps:
(1) preparation of dysprosium nitrate:
In the situation that stirring, by vanadium dysprosium stoichiometric proportion (n
v/ n
dy=1:1?) ammonium metavanadate and dysprosium nitrate are dissolved in respectively in deionized water, again these two kinds of solution are mixed, generating after yellow mercury oxide toward the ammoniacal liquor that drips 30% in this solution regulates its pH value to equal 7, sediment filters after stirring ageing, clean, gained solid dry after 500 ° of C roasting temperatures 2 hours, obtain DyVO after cooling
4.
(2) preparation of graphite-phase carbonitride:
Melamine is put in Muffle furnace to 520 ° of C roastings 4 hours, obtains yellow g-C after cooling
3n
4.
(3) preparation of vanadic acid dysprosium composite graphite phase carbon nitride catalyst:
Press DyVO
4/ g-C
3n
4mass ratio, by vanadic acid dysprosium and graphite-phase carbonitride powder mixed grinding 10min, finally under 300-600 ° of C, roasting obtains this catalyst finished product for 2 hours.
The present invention adopts the compound method of semiconductor to carry out modification g-C
3n
4thinking, with g-C
3n
4for core component, by modifying DyVO
4to improve its photocatalysis performance, thereby develop a kind of highly active vanadic acid dysprosium composite graphite phase carbon nitride photochemical catalyst.
Photochemical catalyst for degradable organic pollutant prepared by the present invention has following two features: the high visible response that is first catalyst, this catalyst energy gap is 2.3eV left and right, can absorbing wavelength be less than the visible ray of 560nm, this makes catalyst prepared by the present invention have the ability of very high absorption visible ray; Secondly, also show in the light-catalyzed reaction activity of catalyst: this catalyst has engine dyeing thing all to have very high Visible Light Induced Photocatalytic activity to rhodamine B etc. is multiple.In addition, catalyst prepared by the present invention also has that preparation method is simple, applicable elements is not harsh, Photocatalytic Degradation Property is stable, the advantage such as can use for a long time, therefore, has higher commercial applications prospect.
Brief description of the drawings
Fig. 1 is the active figure of catalyst catalytic degradation rhodamine B under visible ray of embodiment 1 ~ 5 and comparative example 1 ~ 3 preparation.
Fig. 2 is the active figure of catalyst catalytic degradation rhodamine B under visible ray of embodiment 2,6 ~ 8 preparations.
Fig. 3 is the service life cycle figure of embodiment 3 rhodamine B degradation reaction under visible ray.
Fig. 4 is the X-ray powder diffraction (XRD) of the catalyst of embodiment 3 and comparative example 1 ~ 2 preparation.
Fig. 5 is that the UV, visible light of the catalyst of embodiment 3 and comparative example 1 ~ 2 preparation absorbs (UV-vis) spectrum.
Detailed description of the invention
Further illustrate the present invention with embodiment below, but the present invention is not limited to following examples.
Embodiment 1:
(1) take 1.254g ammonium metavanadate, add 50ml deionized water, 80 ° of C stirring in water bath are dissolved, and obtain ammonium metavanadate solution.Take 2.0g dysprosia, add 3ml red fuming nitric acid (RFNA) and 7ml deionized water, 80 ° of C stirring in water bath are dissolved, and obtain dysprosium nitrate solution.Then in the situation that stirring, dysprosium nitrate solution is slowly added drop-wise in ammonium metavanadate solution, generate yellow mercury oxide, stir ageing and filter after 2 hours, use washed with de-ionized water three times, gained solid is dried under 90 ° of C in baking oven, finally roasting 4 hours under 500 ° of C in muffle furnace.Naturally after cooling, obtain DyVO prepared by the precipitation method
4.
(2) take 5g melamine, put into the crucible of lid, then this crucible is put in Muffle furnace to 520 ° of C roastings 3 hours.Naturally after cooling, obtain yellow g-C
3n
4.
(3) take respectively the vanadic acid dysprosium of 0.10g and the graphite mould carbonitride of 0.90g, by its mixed grinding 10min, finally in 450 ° of C roasting temperatures 2 hours, the DyVO that the vanadic acid dysprosium mass fraction that obtains 450 ° of C roastings after naturally cooling is 0.1
4/ g-C
3n
4composite catalyst.
Embodiment 2:
(1) with the step of (1) in embodiment 1.
(2) with the step of (2) in embodiment 1.
(3) take respectively the vanadic acid dysprosium of 0.15g and the graphite mould carbonitride of 0.85g, by its mixed grinding 10min, finally in 450 ° of C roasting temperatures 2 hours, the DyVO that the vanadic acid dysprosium mass fraction that obtains 450 ° of C roastings after naturally cooling is 0.15
4/ g-C
3n
4composite catalyst.
Embodiment 3:
(1) with the step of (1) in embodiment 1.
(2) with the step of (2) in embodiment 1.
(3) take respectively the vanadic acid dysprosium of 0.20g and the graphite mould carbonitride of 0.80g, by its mixed grinding 10min, finally in 450 ° of C roasting temperatures 2 hours, the DyVO that the vanadic acid dysprosium mass fraction that obtains 450 ° of C roastings after naturally cooling is 0.2
4/ g-C
3n
4composite catalyst.
Embodiment 4:
(1) with the step of (1) in embodiment 1.
(2) with the step of (2) in embodiment 1.
(3) take respectively the vanadic acid dysprosium of 0.30g and the graphite mould carbonitride of 0.70g, by its mixed grinding 10min, finally in 450 ° of C roasting temperatures 2 hours, the DyVO that the vanadic acid dysprosium mass fraction that obtains 450 ° of C roastings after naturally cooling is 0.3
4/ g-C
3n
4composite catalyst.
Embodiment 5:
(1) with the step of (1) in embodiment 1.
(2) with the step of (2) in embodiment 1.
(3) take respectively the vanadic acid dysprosium of 0.40g and the graphite mould carbonitride of 0.60g, by its mixed grinding 10min, finally in 450 ° of C roasting temperatures 2 hours, the DyVO that the vanadic acid dysprosium mass fraction that obtains 450 ° of C roastings after naturally cooling is 0.4
4/ g-C
3n
4composite catalyst.
Embodiment 6:
(1) with the step of (1) in embodiment 1.
(2) with the step of (2) in embodiment 1.
(3) take respectively the vanadic acid dysprosium of 0.15g and the graphite mould carbonitride of 0.85g, by its mixed grinding 10min, finally in 300 ° of C roasting temperatures 2 hours, the DyVO that the vanadic acid dysprosium mass fraction that obtains 400 ° of C roastings after naturally cooling is 0.15
4/ g-C
3n
4composite catalyst.
Embodiment 7:
(1) with the step of (1) in embodiment 1.
(2) with the step of (2) in embodiment 1.
(3) take respectively the vanadic acid dysprosium of 0.15g and the graphite mould carbonitride of 0.85g, by its mixed grinding 10min, finally in 400 ° of C roasting temperatures 2 hours, the DyVO that the vanadic acid dysprosium mass fraction that obtains 500 ° of C roastings after naturally cooling is 0.15
4/ g-C
3n
4composite catalyst.
Comparative example 1:
Vanadic acid dysprosium, preparation method is with step (1) in embodiment 1.
Comparative example 2:
G-C
3n
4, preparation method is with step (2) in embodiment 1.
Comparative example 3:
N doped Ti O
2(N – TiO
2).The preparation method of this photochemical catalyst is as follows: get butyl titanate 10ml, add 5ml glacial acetic acid, keep solution temperature in 25 ° of C left and right, after magnetic agitation 10min, slowly drip 30% concentrated ammonia liquor, to reacting liquid pH value be 9.By deionized water rinsing 5 times for white depositions, under 85 ° of C, dry, porphyrize, finally 400 ° of C roasting temperatures 2 hours, obtain yellow N – TiO after cooling
2powder catalyst.
The evaluation of photocatalytic activity adopts self-control photocatalytic reaction device.Illuminator is 350W spherical xenon lamp, irradiation from top to bottom, and illuminator and liquid level spacing 15cm, side fan blowing cooling, light intensity is about 15mW/cm
2, when reaction, temperature is room temperature.Catalyst amount 200mg, liquor capacity 100mL, rhdamine B concentration is 1 × 10
-5mol/L.Before reaction, reactant liquor all stirs 1h under dark condition, to reach adsorption desorption balance.After reaction, extract the reactant liquor of 5ml left and right every 30min, by centrifugation, then measure the absorbance of supernatant liquor with ultraviolet-uisible spectrophotometer, then converse the concentration of rhodamine B according to Lambert-Beer's law, weigh the activity of catalyst with the percent of decolourization of dyestuff.
The activity of the photocatalytic degradation rhodamine B of the catalyst described in above embodiment 1 ~ 5 and comparative example 1,3 is shown in Fig. 1.Embodiment 2 and embodiment 6 ~ 7, the activity of the visible light photocatalytic degradation rhodamine B of the catalyst that comparative example 2 makes is shown in Fig. 2.The service life cycle of embodiment 2 rhodamine B degradation reaction under visible ray is shown in Fig. 3.A1 ~ a7 catalyst that corresponding embodiment 1 ~ 7 makes respectively, b1 ~ b3 catalyst that comparative example 1 ~ 3 makes respectively.From evaluation result, adopt the photochemical catalyst for degradation of dye waste water organic pollution under visible ray prepared by preparation method of the present invention to there is very high photocatalytic activity and service life.The degradation rate of the catalyst degradation rhdamine B that embodiment 2 makes under radiation of visible light is almost 100%.
X-ray powder diffraction (XRD) characterization result of the catalyst that embodiment 2 and comparative example 1 ~ 2 make is shown in Fig. 4, and the UV-vis DRS of the catalyst that embodiment 2 and comparative example 1 ~ 2 make absorbs (UV-vis) characterization result and sees Fig. 5.As can be seen from Figure 4, in catalyst, only there is DyVO
4and g-C
3n
4phase, due to the collaborative coupling effect between two semiconductors, make light induced electron-hole to this two alternate can directional migration, thereby effectively promoted the separation of electron hole pair, therefore greatly improved its photocatalytic activity.UV-vis DRS absorption spectrum characterization result shows that embodiment 2 has very strong absorbability being less than within the scope of 467nm visible region.This is consistent with above-mentioned catalytic performance test result, and the catalyst that embodiment 2 makes has very high Visible Light Induced Photocatalytic waste water dyestuff organic contamination physical performance.
Claims (2)
1. a preparation method for visible light response catalyst, this catalyst is vanadic acid dysprosium composite graphite phase carbon nitride, chemical composition general formula is xDyVO
4/ g-C
3n
4, x is the mass fraction of vanadic acid dysprosium in catalyst, g-C
3n
4mass fraction be 1-x, 0.1≤x≤0.4, is characterized in that this preparation method comprises the following steps:
(1) preparation of vanadic acid dysprosium:
In the situation that stirring, by vanadium dysprosium stoichiometric proportion, ammonium metavanadate and dysprosium nitrate are dissolved in respectively in deionized water, again these two kinds of solution are mixed, generating after yellow mercury oxide toward the ammoniacal liquor that drips 30% in this solution regulates its pH value to equal 7, sediment filters after stirring ageing, clean, gained solid dry after 500 DEG C of roasting temperatures 2 hours, obtain DyVO after cooling
4;
(2) preparation of graphite-phase carbonitride:
Melamine is put in Muffle furnace to 520 DEG C of roastings 4 hours, obtains yellow g-C after cooling
3n
4;
(3) press DyVO
4/ g-C
3n
4mass ratio, by vanadic acid dysprosium and graphite-phase carbonitride powder mixed grinding 10min, finally at 300-600 DEG C, roasting obtains this catalyst finished product for 2 hours.
2. preparation method according to claim 1, is characterized in that: x is 0.15.
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|---|---|---|---|
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| CN103272639B (en) * | 2013-06-09 | 2015-02-04 | 福州大学 | Copolymerization modified graphite-phase carbon nitride nanosheet visible-light-driven photocatalyst |
| CN103586064A (en) * | 2013-11-26 | 2014-02-19 | 中国科学院福建物质结构研究所 | Metal/graphite-like carbon nitride compound catalyst and preparing method thereof |
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