CN103285893B - Method for preparing coralline porous silver bromiodide/silver photocatalyst - Google Patents
Method for preparing coralline porous silver bromiodide/silver photocatalyst Download PDFInfo
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Abstract
The invention relates to a method for preparing a coralline porous silver bromiodide/silver photocatalyst. The content of silver iodide in the photocatalyst is 0 to 25 percent (mol/mol), and the surface of the photocatalyst consists of silver nano-particles. The method for preparing the porous photocatalyst comprises the following steps of: (1) in the presence of sodium hydroxide, preparing a porous silver simple substance through using a de-alloying method by using a silver aluminum alloy as a raw material; (2) in the presence of hydrogen peroxide and potassium bromide, converting porous silver into porous silver bromide; (3) converting part of silver bromide into silver bromiodide through using an ion exchange method; (4) performing photo-reduction treatment on the silver bromiodide through ultraviolet rays, and generating the silver nano-particles on the surface of the silver bromiodide to obtain the coralline porous silver bromiodide/silver photocatalyst. Compared with the existing method, the catalyst prepared by using the method has the advantages of high visible-light activity, recoverability and the like, and an organic pollutant such as dye can be efficiently degraded through visible light.
Description
Technical field
The present invention relates to a kind of coralliform porous silver bromiodide/silver photocatalyst and preparation method thereof that can be applicable to water pollutant degraded, belong to photocatalysis technology field.
Background technology
The fast development of modern industry and science and technology, on the one hand, greatly enrich the material and cultural life of people, promote the civilization and progress of human society, bring again generation and the discharge of a large amount of hazardous contaminant simultaneously, destroy air, water source and soil environment that the mankind depend on for existence, had a strong impact on normal life and the production of the mankind, even jeopardize the existence of the mankind.For the water pollution of China, the industrial wastewater discharge total amount of China in 2007 is 246.6 hundred million tons, and COD total emission volumn is 511.1 ten thousand tons, wherein 15.7 hundred million tons of waste water still below standard directly enter marine; City domestic sewage discharge capacity is 310.2 hundred million tons, and COD total emission volumn is 870.8 ten thousand tons, and is in reduction process rate state.This pollution situation is cumulative year after year state, and it makes the situation of natively water resource deficiency severeer, and the rivers and lakes of 70% receive pollution, and the 3.6 hundred million Chinese common people lack safe drinking water.Environmental pollution has become the bottleneck of serious restriction China strategy of sustainable development, and the Green Trade Barrier that it causes, national security and people's crisis of survival are increasingly serious.Conventional treatment method, as still undesirable in effects such as high temperature incineration, the absorption of active mud, anaerobic type absorptions, and there is secondary pollution; This type organic though biochemical treatment can thoroughly be degraded, investment is comparatively large, can biochemical ability the differing greatly of high, the different system of management expectancy, and particularly high toxicity organic matter can make its biochemical bacterial classification inactivation, makes it promote and is subject to certain restrictions.Therefore, the new material of exploitation and control environmental pollution, new technology and method are research topics of crucial importance and urgent.
Find at n-type semiconductor titanium dioxide (TiO from 20 century 70 Fujishima and Honda
2) on electrode since photolysis water hydrogen, Photocatalitic Technique of Semiconductor causes the very big concern of numerous researchers.In environmental contaminants improvement, conductor photocatalysis material can utilize sunshine to be nontoxic carbon dioxide and water by the most organic pollutant degradations in water body and air.Nano-TiO
2have that photochemical properties is stable, non-secondary pollution and the advantage such as cheap and easy to get, be considered to one of catalysis material of most application prospect.But, TiO
2energy gap (3.2eV) determine the ultraviolet light that it can only absorb below 400nm, and the solar spectrum medium ultraviolet light arriving earth surface only accounts for 3 ~ 5%, and it is extremely low to the utilization ratio of sunshine that this just causes titanium dioxide.In addition, due to nano-TiO
2undersized, process water pollution after be difficult to reclaim and recycling.The existence of these problems greatly hinders the application of photocatalysis technology in waste water control.
In order to improve TiO
2to the utilization ratio of sunshine, the modified measures such as researcher's applied metal doping on the one hand, nonmetal doping, dye sensitization, composite semiconductor expand TiO
2to the response range of visible ray; On the other hand, some research work are also had around non-TiO
2narrow band gap catalysis material launch; In recent years, utilized the plasma resonance effect of noble metal to expand the photoresponse of catalysis material to visible ray, became again new study hotspot.According to Angew.Chem.Int.Ed.2008,47,7931-7933 reports, a kind of silver chlorate/silver (Ag/AgCl) catalysis material based on Nano silver grain plasma resonance effect that utilized ion-exchange to prepare such as golden cypress mark, can efficiency utilization Visible Light Induced Photocatalytic organic matter, and there is good photostability.The structure of loose structure photochemical catalyst solves the repetition of catalyst on the one hand at Utilizing question, and on the other hand, loose structure can improve reactivity face, promotes mass-transfer efficiency, is also conducive to the raising of photocatalytic activity.Such as, according to people such as VijayT.John at Langmuir2009,25 (13), 7586-7593 reports, by anion surfactant and lecithin with 2: 1 ratio mixing, after adding TTIP, drying obtains dry glue, obtains porous TiO through calcining
2material, this catalyst has orderly macroporous structure, and its photocatalysis efficiency has greatly improved than business-like titanium dioxide P25 tool; Again according to J.Phys.Chem.C2007,111 (28), 10582-10589 reports, the people such as Yu Jiaguo, utilize hydrothermal synthesis method, and prepared the macroporous titanium dioxide of aperture 2-4 μm, its specific area can reach 200m
2/ g, realizes the raising of photocatalytic activity.But, the preparation of porous catalyst silver halide catalyst and photocatalysis research also rarely seen report.The present invention explores a kind of preparation method with the porous silver bromiodide/silver photocatalyst of coralliform structure.In institute's invention catalyst, Nano silver grain and bromo-iodide all can responding to visible light, and mutually through coralliform loose structure improves reactivity face, facilitates the turnover of reactant and product, is conducive to the raising of photocatalytic activity.Meanwhile, because monolith size is comparatively large, after degradation of contaminant waste water, catalyst, by the method removing of filtering or precipitate, is reused.
Summary of the invention
The present invention is directed to the shortcoming that current catalysis material visible light activity is low, be difficult to recycling, this invention exploits a kind of novel preparation method possessing coralliform loose structure AgBrI/Ag plasma resonance photochemical catalyst.In institute's invention catalyst, Nano silver grain and bromo-iodide all can responding to visible light, and coralliform loose structure improves reactivity face, facilitates the turnover of reactant and product, is conducive to the raising of photocatalytic activity.Meanwhile, because monolith size is comparatively large, after degradation of contaminant waste water, catalyst, by the method removing of filtering or precipitate, is reused.
The preparation method of porous AgBrI/Ag plasma resonance photochemical catalyst of the present invention comprises the following steps:
(1) adopting removal alloying legal system for porous silver simple substance: to take aerdentalloy as raw material, with NaOH corrosion dissolution aluminium wherein, by controlling the consumption of NaOH, the porous silver with coralliform structure can be obtained;
(2) oxidation-precipitation method are adopted to prepare porous silver bromide: to use hydrogen peroxide and KBr as oxidant and precipitating reagent respectively, by controlling their consumption, the porous silver bromide that can obtain having coralliform structure can be obtained;
(3) utilize ion-exchange to prepare porous bromo-iodide: be dispersed in by porous silver bromide in the appearance liquid of KI, stirring reaction can obtain porous bromo-iodide, regulated the molar ratio of bromine and iodine in final products by the consumption controlling KI;
(4) ultraviolet light reduction treatment obtains porous silver bromiodide/silver: be scattered in water by porous bromo-iodide, carries out photo-reduction process with ultraviolet light to suspension, makes catalyst surface original position form Nano silver grain.
In step (1), the molar ratio of NaOH and Aluminum in Alloy is 5: 1 ~ 25: 1; In step (2), the mol ratio of hydrogen peroxide and porous silver is 10: 1 ~ 220: 1; Control the consumption of KI in step (3), make silver iodide percentage composition in bromo-iodide be 0 ~ 25% (mol/mol).In step (3), adopt high-pressure sodium lamp or black light lamp as ultraviolet light source.
The method of removal alloying technology of preparing, oxidation-precipitation method, ion-exchange and ultraviolet light photo-reduction combines by the present invention, can under mild conditions, and preparation has the AgBrI/Ag catalyst of loose structure.Compared with prior art, the present invention has the advantages that technique is simple, reaction condition is gentle, and prepared catalyst has visible light activity height and is easy to the advantages such as recovery.
Photocatalytic Activity for Degradation methyl orange is reacted:
At room temperature, with the xenon lamp of 300W for visible light source (ultraviolet with optical filter below elimination 420nm), 25mL methyl orange solution (10mg/L) and 0.0250g catalyst is added in 50mL quartz glass reaction pipe, the distance of light source and glass reaction tube is 10cm, dark reaction adsorbs 30 minutes, make dyestuff after catalyst surface reaches adsorption-desorption balance, start to carry out light-catalyzed reaction, suspension in 1mL quartz ampoule is extracted every 3 minutes, after centrifugation, survey its absorbance with ultraviolet-visible spectrophotometer, and calculate the concentration of residual methyl orange.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram that embodiment 1 obtains porous Ag (a) and porous AgBrI/Ag (b).
Fig. 2 is the x-ray diffraction pattern that embodiment 1 obtains porous AgBrI/Ag.
The product that Fig. 3 is comparative example, embodiment 1 obtains and do not mix the comparison diagram of photo-catalytic degradation of methyl-orange efficiency of iodine porous AgBr/Ag.
Detailed description of the invention
Below in conjunction with example, the present invention is further described in detail.
Comparative example
Reference literature J.Phys.Chem.C, 2013, the report of 117 (1), 213-220, with KBr replacement sodium chloride wherein, adopts twin columns emulsion process to prepare the cubic silver bromide grain that particle diameter is 400 nanometers.Take the dry cube AgBr of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid in rear collected by centrifugation suspension, dry a few hours at 85 DEG C, the dry cube AgBr/Ag obtained.Take 25mgAgBr/Ag to be dispersed in in 25mL methyl orange aqueous solution, dark absorption 30 minutes, with 300W xenon lamp (band 420nm optical filter), for light source, its visible light photocatalytic degradation methyl orange is after 15 minutes after measured, and degradation rate reaches 72.57%.
Embodiment 1
In 500mL beaker, add 6.7g solid sodium hydroxide and 167.5mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 20: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 220: 1) of 20mL1mol/L, add the solution of 10mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0044g solid KI (molar ratio of KI and porous AgBr is 1: 10), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous Ag BrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Fig. 1 (a) and (b) are respectively SEM (SEM) photo of coralliform porous Ag and the AgBrI/Ag obtained according to embodiment 1.Can see from SEM figure, after removal alloying, the simple substance Ag with coralliform loose structure can be obtained; Further, after peroxidating-precipitation method conversion, halogen ion-exchange and photo-reduction, its coralloid loose structure still obtains intact reservation, is not subject to obvious destruction, illustrates that this scheme is practical.
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of the porous AgBrI/Ag that embodiment 1 obtains.In XRD figure, 26.72 °, 30.96 °, 44.35 °, 52.49 °, 55.04 °, 64.48 ° and 73.26 ° represent AgBr (111), (200), (220), (311), (222), (400) and (420) crystallographic plane diffraction peak respectively, and the peak at the places such as 23.76 °, 25.16 °, 30.46 °, 38.16 °, 39.24 °, 43.64 ° then represents the diffraction maximum of AgI.In addition, also there is the diffraction maximum of Ag simple substance at 38.10 °, due to Ag simple substance content seldom and dispersion is compared in distribution, exist again certain overlapping, therefore obvious not with the diffraction maximum of silver iodide.
The product that Fig. 3 is comparative example, embodiment 1 obtains and do not mix the comparison diagram of photo-catalytic degradation of methyl-orange efficiency of iodine porous AgBr/Ag three.Contrast cube AgBr/Ag and porous AgBr/Ag, after catalyst presents loose structure, the efficiency of its 15 minutes degraded methyl orange brings up to 93.62% from 72.57%, has obvious lifting.And contrast porous AgBr/Ag and porous AgBrI/Ag, after being mixed with part iodine, the efficiency of its 15 minutes degraded methyl orange brings up to 98.39% from 93.62%, and almost degraded is completely.
Embodiment 2
In 500mL beaker, add 3.3g solid sodium hydroxide and 82.5mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 5: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 220: 1) of 20mL1mol/L, add the solution of 10mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0044g solid KI (molar ratio of KI and porous AgBr is 1: 10), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous AgBrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Embodiment 3
In 500mL beaker, add 4.4g solid sodium hydroxide and 110mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 10: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 220: 1) of 20mL1mol/L, add the solution of 10mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0044g solid KI (molar ratio of KI and porous AgBr is 1: 10), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous AgBrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Embodiment 4
In 500mL beaker, add 5.6g solid sodium hydroxide and 140mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 15: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 220: 1) of 20mL1mol/L, add the solution of 10mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0044g solid KI (molar ratio of KI and porous AgBr is 1: 10), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous AgBrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Embodiment 5
In 500mL beaker, add 7.8g solid sodium hydroxide and 195mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 25: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 220: 1) of 20mL1mol/L, add the solution of 10mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0044g solid KI (molar ratio of KI and porous AgBr is 1: 10), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous AgBrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Embodiment 6
In 500mL beaker, add 6.7g solid sodium hydroxide and 167.5mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 20: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 10: 1) of 10mL0.1mol/L, add the solution of 20mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0044g solid KI (molar ratio of KI and porous AgBr is 1: 10), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous AgBrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Embodiment 7
In 500mL beaker, add 6.7g solid sodium hydroxide and 167.5mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 20: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 20: 1) of 20mL0.1mol/L, add the solution of 10mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0044g solid KI (molar ratio of KI and porous AgBr is 1: 10), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous AgBrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Embodiment 8
In 500mL beaker, add 6.7g solid sodium hydroxide and 167.5mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 20: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 50: 1) of 10mL0.5mol/L, add the solution of 20mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0044g solid KI (molar ratio of KI and porous AgBr is 1: 10), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous AgBrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Embodiment 9
In 500mL beaker, add 6.7g solid sodium hydroxide and 167.5mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 20: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 100: 1) of 20mL0.5mol/L, add the solution of 10mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0044g solid KI (molar ratio of KI and porous AgBr is 1: 10), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous AgBrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Embodiment 10
In 500mL beaker, add 6.7g solid sodium hydroxide and 167.5mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 20: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 100: 1) of 10mL1mol/L, add the solution of 20mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0044g solid KI (molar ratio of KI and porous AgBr is 1: 10), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous AgBrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Embodiment 11
In 500mL beaker, add 6.7g solid sodium hydroxide and 167.5mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 20: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 220: 1) of 20mL1.0mol/L, add the solution of 10mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0022g solid KI (molar ratio of KI and porous AgBr is 1: 20), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous AgBrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Embodiment 12
In 500mL beaker, add 6.7g solid sodium hydroxide and 167.5mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 20: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 220: 1) of 20mL1.0mol/L, add the solution of 10mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0088g solid KI (molar ratio of KI and porous AgBr is 1: 4), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous AgBrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, by lamp and high pressure mercury 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Embodiment 13
In 500mL beaker, add 6.7g solid sodium hydroxide and 167.5mL ultra-pure water, stirring and dissolving under 25 DEG C of water bath condition.With vigorous stirring, add 300mg aerdentalloy raw material (namely the molar ratio of NaOH and aluminium is 20: 1), and Keep agitation 72 hours.By solid milli-Q water remaining in suspension for several times, dry at 85 DEG C.The porous Ag material getting 10mg drying is placed in 50mL beaker, add the hydrogenperoxide steam generator (namely the molar ratio of hydrogen peroxide and porous Ag is 220: 1) of 20mL1.0mol/L, add the solution of 10mL containing 0.036g KBr simultaneously, stir 1 hour under dark condition, by gained porous AgBr milli-Q water several, dry at 85 DEG C.Get the dry porous AgBr of 10mg and be placed in 25mL beaker, add 5mL ultra-pure water, ultrasonic disperse, in beaker, add 0.0044g solid KI (molar ratio of KI and porous AgBr is 1: 10), stirring reaction 1 hour under dark condition.After reaction terminates, with the solid porous AgBrI several of milli-Q water, dry at 85 DEG C.Take the dry porous AgBrI of 50mg, be dispersed in 50mL ultra-pure water, under agitation, with black light lamp illumination 30 minutes, make its surface in situ generate Ag nano particle.Illumination terminates the solid porous AgBrI/Ag of rear collected by centrifugation, dry a few hours at 85 DEG C.The dry AgBrI/Ag obtained takes 25mg and is dispersed in 25mL methyl orange, dark absorption 30 minutes, and with 300W xenon lamp (band 420nm optical filter), for light source, the activity of its visible light photocatalytic degradation methyl orange is higher than the silver bromide/silver not mixing iodine after measured.
Claims (5)
1. a preparation method for coralliform porous silver bromiodide/silver photocatalyst, is characterized in that, described photochemical catalyst possesses similar coralloid loose structure, and its preparation method comprises the following steps:
(1) adopting removal alloying legal system for porous silver simple substance: to take aerdentalloy as raw material, with NaOH corrosion dissolution aluminium wherein, by controlling the consumption of NaOH, the porous silver with coralliform structure can be obtained;
(2) oxidation-precipitation method are adopted to prepare porous silver bromide: to use hydrogen peroxide and KBr as oxidant and precipitating reagent respectively, by controlling their consumption, the porous silver bromide with coralliform structure can be obtained;
(3) utilize ion-exchange to prepare porous bromo-iodide: to be dispersed in the solution of KI by porous silver bromide, stirring reaction can obtain porous bromo-iodide, is regulated the mol ratio of bromine and iodine in final products by the consumption controlling KI;
(4) ultraviolet reduction treatment obtains porous silver bromiodide/silver: be scattered in water by porous bromo-iodide, carries out photo-reduction process with ultraviolet to suspension, makes catalyst surface original position form Nano silver grain.
2. the preparation method of coralliform porous silver bromiodide/silver photocatalyst according to claim 1, is characterized in that, in step (1), the molar ratio of NaOH and Aluminum in Alloy is 5:1 ~ 25:1.
3. the preparation method of coralliform porous silver bromiodide/silver photocatalyst according to claim 1, is characterized in that, in step (2), the mol ratio of hydrogen peroxide and porous silver is 10:1 ~ 220:1.
4. the preparation method of coralliform porous silver bromiodide/silver photocatalyst according to claim 1, it is characterized in that, control the consumption of KI in step (3), make silver iodide percentage composition in bromo-iodide be 0 ~ 25% (mol/mol).
5. the preparation method of coralliform porous silver bromiodide/silver photocatalyst according to claim 1, is characterized in that, adopts high-pressure sodium lamp or black light lamp as ultraviolet light source.
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