A kind of preparation method of support type silver orthophosphate/silver sulfide composite photo-catalyst
Technical field
The present invention relates to the preparation method of a kind of support type silver orthophosphate/silver sulfide composite photo-catalyst, belong to technical field of sewage in environmental protection.
Background technology
Traditional method for treating water efficiency is low, cost is high, there is secondary pollution problems, the solution that waste water control can not get always.Development and the application of nanometer technology probably thoroughly solve this difficult problem.1972 start to find TiO
2oxidation activity is higher, and chemical stability is good, and to human non-toxic's evil, cost is low, pollution-free, and thus applied range is paid attention to most, but TiO
2comparatively large (the such as anatase TiO of energy gap
2energy gap Eg=3.2eV), only can absorb the light of ultraviolet region (wavelength is less than 387nm), lower to the utilization ratio of solar energy.
China Sichuan has the svanbergite of rich reserves, and it is one of maximum in the world phosphoric acid aluminium profiles mineral deposit.This ore complicated, be the aluminate or phosphate of a kind of sulfur-bearing, strontium and rare earth etc., it had both been different from phosphate ore known in the world, was different from again calcium phosphate aluminium profiles mineral deposit.This ore deposit reserve is huge and ore bed directly overlays on phosphorite ore bed, since finding, has failed to obtain Appropriate application, and become in " slow-witted ore deposit " from 1958.This not only affects the exploitation of this resource, affects again the development deployment of the phosphorus block salt that it underlies.It develops for many years is an important research class body always, and for this reason, many researchers have successively carried out a large amount of research work.
In contaminant degradation and production of energy field, conductor photocatalysis is one of the most promising method.Will produce the separation of electron-hole pair when the photon irradiation that energy is more than or equal to semiconductor energy gap is in photocatalyst surface, this is the initial basic step of light-catalyzed reaction.In order to find efficient photochemical catalyst, a large amount of research work all concentrates in the influence factor of research photocatalytic activity.In June, 2010, material research institution researcher finds that silver orthophosphate has the effect of photochemical catalyst, and photooxidation effect is more than the decades of times of current known various photochemical catalyst.But because silver orthophosphate self is unstable, in photocatalysis, easy self-reversal, causes catalyst degradation performance to reduce rapidly.And to improve photocatalysis effect be an endless job.In addition, because nano particle is difficult to be separated from waste water after process waste water, therefore need nano particle load on some carriers.Svanbergite is a kind of material preferably, both can as the raw material of catalyst preparing, again can as catalyst carrier, but general Composite mechanism is by directly covering at carrier surface, and this contact is physical contact, being easy to come off causes catalyst loss.The material synthesized on its surface is a kind of composite, can have good photocatalysis effect.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, propose the preparation method of a kind of support type silver orthophosphate/silver sulfide composite photo-catalyst, the method forms catalyst at carrier surface, and catalyst and carrier are combined closely.
The technical solution used in the present invention adopts following steps:
1) cross the svanbergite 80 ~ 100g of 40 mesh sieves after taking grinding, be filled in and have in the glass tube of Valve controlling up and down;
2) compound concentration is the HNO of 0.02 ~ 0.2mol/L respectively
3solution 200mL, concentration are the NaNO of 0.01 ~ 0.1mol/L
3solution 400mL and concentration are the AgNO of 0.2 ~ 0.8mol/L
3solution 200mL;
3) by vertical for the glass tube being filled with svanbergite, open lower valve, in pipe, inject HNO by bottom
3solution, when after solution energy submergence svanbergite, discharges HNO
3solution, keeps bottom valve to open, injects NaNO by top
3solution, allows NaNO
3flow out from bottom after solution injects from top, then close bottom valve, inject AgNO from top
320 ~ 30min is soaked, by AgNO after solution
3solution is released from bottom, namely particle in glass tube obtains a kind of support type silver orthophosphate/silver sulfide composite photo-catalyst after deionization washing, drying, calcium phosphate elder generation in this process in hydroxyapatite and nitric acid reaction, part calcium ion dissolves, sodium nitrate is utilized to wash away, the hydrogen ion of hydroxyapatite surface is washed out, sodium phosphate is formed on svanbergite surface, finally the svanbergite obtained is soaked in liquor argenti nitratis ophthalmicus, forms a kind of support type silver orthophosphate/silver sulfide composite photo-catalyst.
The invention has the beneficial effects as follows: (1) silver orthophosphate can be combined in the surface of svanbergite, this combination is not common ground and mixed, neither simple surface deposition, but phosphate radical in carrier body and silver ion combine, and form silver orthophosphate crystal on surface.This combination is firm, makes silver orthophosphate difficult drop-off.
(2) silver orthophosphate and silver sulfide compound, synergy, silver sulfide can be made under the effect of visible ray also can to play catalytic action, and silver orthophosphate also because of the doping of other elements (as strontium etc.), and can obtain good catalytic effect.
Detailed description of the invention
Embodiment 1
Cross the svanbergite 100g of 40 mesh sieves after taking grinding, be filled in and have in the glass tube of Valve controlling up and down; Compound concentration is the HNO of 0.2mol/L respectively
3solution 200mL, concentration are the NaNO of 0.1mol/L
3solution 400mL and concentration are the AgNO of 0.8mol/L
3solution 200mL; By vertical for the glass tube being filled with svanbergite, open lower valve, in pipe, inject HNO by bottom
3solution, when after solution energy submergence svanbergite, discharges HNO
3solution, keeps bottom valve to open, injects NaNO by top
3solution, allows NaNO
3flow out from bottom after solution injects from top, then close bottom valve, inject AgNO from top
330min is soaked, by AgNO after solution
3solution is released from bottom, and namely the particle in glass tube obtains a kind of support type silver orthophosphate/silver sulfide composite photo-catalyst after deionization washing, drying.
It is in the acid red waste water of 50mg/L that the support type obtained silver orthophosphate/silver sulfide composite photo-catalyst 0.5g is joined 500mL concentration, and under 300w Metal halogen lamp irradiates, reaction 30min, percent of decolourization is 95.1%, can reuse after catalyst separation.
Embodiment 2
Cross the svanbergite 80g of 40 mesh sieves after taking grinding, be filled in and have in the glass tube of Valve controlling up and down; Compound concentration is the HNO of 0.02mol/L respectively
3solution 200mL, concentration are the NaNO of 0.01mol/L
3solution 400mL and concentration are the AgNO of 0.2mol/L
3solution 200mL; By vertical for the glass tube being filled with svanbergite, open lower valve, in pipe, inject HNO by bottom
3solution, when after solution energy submergence svanbergite, discharges HNO
3solution, keeps bottom valve to open, injects NaNO by top
3solution, allows NaNO
3flow out from bottom after solution injects from top, then close bottom valve, inject AgNO from top
320min is soaked, by AgNO after solution
3solution is released from bottom, and namely the particle in glass tube obtains a kind of support type silver orthophosphate/silver sulfide composite photo-catalyst after deionization washing, drying.
The support type obtained silver orthophosphate/silver sulfide composite photo-catalyst 0.5g being joined 500mL concentration is in gold orange 7 waste water of 50mg/L, and under 300w Metal halogen lamp irradiates, reaction 30min, percent of decolourization is 93.5%, can reuse after catalyst separation.For identical waste water at identical conditions, the degradation efficiency of pure phosphoric acid silver is 90.8%, but owing to being pure phosphoric acid silver, in catalyst, the consumption of silver is very large, is difficult to economically bear.
Embodiment 3
Cross the svanbergite 90g of 40 mesh sieves after taking grinding, be filled in and have in the glass tube of Valve controlling up and down; Compound concentration is the HNO of 0.1mol/L respectively
3solution 200mL, concentration are the NaNO of 0.1mol/L
3solution 400mL and concentration are the AgNO of 0.5mol/L
3solution 200mL; By vertical for the glass tube being filled with svanbergite, open lower valve, in pipe, inject HNO by bottom
3solution, when after solution energy submergence svanbergite, discharges HNO
3solution, keeps bottom valve to open, injects NaNO by top
3solution, allows NaNO
3flow out from bottom after solution injects from top, then close bottom valve, inject AgNO from top
325min is soaked, by AgNO after solution
3solution is released from bottom, and namely the particle in glass tube obtains a kind of support type silver orthophosphate/silver sulfide composite photo-catalyst after deionization washing, drying.
It is in the rose red b waste water of 50mg/L that the support type obtained silver orthophosphate/silver sulfide composite photo-catalyst 0.5g is joined 500mL concentration, and under 300w Metal halogen lamp irradiates, reaction 30min, percent of decolourization is 93.1%, can reuse after catalyst separation.