CN109988451A - A kind of the photocatalysis construction technology and detection method of automatically cleaning prefabricated components - Google Patents

A kind of the photocatalysis construction technology and detection method of automatically cleaning prefabricated components Download PDF

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Publication number
CN109988451A
CN109988451A CN201910284748.1A CN201910284748A CN109988451A CN 109988451 A CN109988451 A CN 109988451A CN 201910284748 A CN201910284748 A CN 201910284748A CN 109988451 A CN109988451 A CN 109988451A
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photocatalysis
automatically cleaning
construction technology
prefabricated components
sample
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刘强
陈科
叶建雄
冯庆敏
陈松
余杰
李潇
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Chongqing University
Chongqing Construction Engineering Group Co Ltd
Chongqing Construction Residential Engineering Co Ltd
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Chongqing University
Chongqing Construction Engineering Group Co Ltd
Chongqing Construction Residential Engineering Co Ltd
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Abstract

The present invention proposes a kind of photocatalysis construction technology of automatically cleaning prefabricated components, it is quasi- to be combined by nano-photocatalyst with prefabricated component, it effectively will be in the function embodiment of the catalysis material indoors construction material of outer surface, it can be used as building structural materials also and can be used as functional material use, realizing in application aspect improves indoor and outdoor surroundings safety, comfort level and the effect for promoting building energy conservation, develops it to functionalization, ecology and innoxious direction.Meanwhile in its development process, using greening building energy saving measure, the use of the energy and resource is reduced, makes ecology, sustainable Green Development environment.

Description

A kind of the photocatalysis construction technology and detection method of automatically cleaning prefabricated components
Technical field
The present invention relates to photocatalysis field more particularly to the photocatalysis construction technologies and detection of a kind of automatically cleaning prefabricated components Method.
Background technique
In China, building inherently major power consumer, while also having significant impact to environment.China is in economical fast Fast developing period, people more also carry out the pursuit of high-caliber life stronger, and this consumption upgrades so that people are to building It is required that it is higher and higher, it consumes energy per capita also higher and higher, the building castoff of generation is more and more, also can not be small to the pollution of environment It looks.Meanwhile with the development of economy, urban atmospheric pollution situation is got worse, the nitrogen oxides and sulphur of automobile and industrial discharge Compound etc. steeply rises atmospheric pollution effect rate, the city NOx that China has oneself up to 50% or more.This protection advocated with the whole world The theory of environment is disagreed.In recent years, many studies have shown that, photocatalysis technology has good in terms of environmental contaminants improvement Application prospect, nano-photocatalyst is under ultraviolet light, using multiple building materials as carrier, is such as applied to paint, glass, porcelain On the basis materials such as brick, plastering and concrete, using it with good photochemical catalytic oxidation ability and surface super hydrophilic Can, it realizes oxygenolysis atmosphere pollution, organic pollutant can be resolved into CO2、H2The small-molecule substances such as O, are prevented bacteriostasis antibiosis A variety of purposes, windowpane and the ceramic tile such as mould, antifouling, anti-dew, antifog, as photocatalysis film, are made by addition nano-photocatalyst The self-cleaning function for obtaining them is modified, and the glass surface of China national theatre has been applied to.Nano-photocatalyst Also it is added in concrete or is used as coating application in ornamental concrete surfaces such as clear-water concretes, can both maintain to build Aesthetic appearance of material itself, and air quality can be improved, improve atmospheric environment, keep city cleaning, since it has certainly Clean-up performance can also save maintenance cost, to extend the service life of building itself.
Catalyst is the chemical substance for accelerating chemical reaction, itself is simultaneously not involved in reaction.Photochemical catalyst is exactly in photon Excitation under can play catalytic action chemical substance general designation.Photocatalysis technology is on the basis that the 1970s is born Nanotechnology, in China's Mainland, we this popular word can call photochemical catalyst with photocatalyst.Typical natural photochemical catalyst It is exactly our green elements of common juice, carbon dioxide and hydration in air is promoted to become oxygen and carbon in the photosynthesis of plant Hydrate.Generally speaking nano photo-catalytic technology is a kind of nano bionic technology, is used for the depollution of environment, and self-cleaning material is first Into new energy, treatment of cancer, multiple Disciplinary Frontiers such as high efficiency antibacterial.
In the world can as photocatalyst material it is numerous, including titanium dioxide (TiO2), zinc oxide (ZnO), tin oxide (SnO2), zirconium dioxide (ZrO2), many oxides sulfide semiconductor such as cadmium sulfide (CdS), titanium dioxide (TiO2), because of it Oxidability is strong, and chemical property is stablized nontoxic, and the nanometer for becoming most hot in the world permits catalyst material.Early stage, also once compared with Use zinc oxide (ZnO) and cadmium sulfide (CdS) as photocatalyst material more, but due to the unstable chemcial property of the two, Harmful metal ion can be dissolved out with certain bio-toxicity light-catalysed while light dissolution occurs, therefore developed country's mesh It is preceding seldom to regard its application as civilian catalysis material.
Summary of the invention
The present invention proposes the photocatalysis construction technology and detection method of a kind of automatically cleaning prefabricated components, develops a kind of be suitble to It in industrial nano-photocatalyst, is combined with prefabricated component, effectively by the function embodiment of catalysis material Indoors in the construction material of outer surface, it can be used as building structural materials also and can be used as functional material use.
The present invention is achieved through the following technical solutions:
Firstly, using metal salt as source metal, using hydro-thermal or water-bath synthetic method, by adjust its reaction condition (temperature, Time and concentration etc.), being made has metal oxide of different nature or more metal composites.Utilize XRD, XPS, UV- The means of testing such as vis, SEM (FESEM), TEM carry out table to component, appearance structure and optical property of prepared sample etc. Sign, and analyzed and researched the photocatalysis performance of different samples by photocatalysis performance test and comparison, study its mechanism of action.
Secondly, obtaining a certain amount of nano-photocatalyst, pass through physical blending, intercalation, in-situ polymerization and sol-gel method etc. Method is dispersed in traditional organic coating, forms modified Nano composite coating.By testing its ultraviolet-ray visible absorbing light Spectrogram judges the photocatalysis performance of modified coating.
Finally, will be configured to the modified coating slurries that a certain concentration contains nano-photocatalyst is sprayed at concrete prefabricated structure Nano coating is made in part surface layer.Nanometer is measured by the test of paint coatings stain resistance and the test of paint coatings resistance to ag(e)ing Influence of the photochemical catalyst to coating contaminated resistance and ageing-resistant performance.
The present invention is quasi- to be combined by nano-photocatalyst with prefabricated component, effectively by the function of catalysis material It is embodied in the construction material of indoor outer surface, can be used as building structural materials also and can be used as functional material use, answering Being realized with aspect improves indoor and outdoor surroundings safety, comfort level and the effect for promoting building energy conservation, makes it to functionalization, ecology Develop with innoxious direction.Meanwhile in its development process, using greening building energy saving measure, the energy and resource are reduced It uses, makes ecology, sustainable Green Development environment.SnO for other opposite photochemical catalysts, in the present invention2And BiOCl Nontoxic nonirritant, reaction condition is relatively mild, and low energy consumption, and light-catalyzed reaction speed is fast, and catalytic activity is high, and oxidability is strong, It is without secondary pollution, it is very promising green photochemical catalyst.
Detailed description of the invention
Fig. 1 is SnO in the present invention2Sample and commercialization SnO2Performance in terms of photocatalytic degradation colored dyes RhB and MB Comparison diagram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.
Semiconductor has the special band structure for being different from metal or megohmite insulant.Swash in the photon with certain energy It gives (photon excitation principle refer to photocatalyst reaction principle) electronics in molecular orbit can be made to leave valence band and transit to conduction band, from And photohole is formed in material valence band, light induced electron [e-] is formed in conduction band, due to titanium dioxide in body phase titanic oxide Particle is very big, light induced electron reach conduction band start to particle surface it is movable during be easy to it is compound with photohole, from And from macroscopically we can not observe the effect of photon excitation: but the titanium dioxide granule day of nanometer is in small-sized, institute It is easier to be diffused into plane of crystal with electronics, 2 different pieces of uncharged plane of crystal originally is caused polarity occur Opposite 2 microcells --- light induced electron and photohole.Since light induced electron and photohole have very strong energy, much It is higher by the intensity of the strand of general organic pollutant, it is possible to which organic pollutant is resolved into the state of most original easily. Photohole can also be formed with the hydrone in air and react simultaneously, generate hydroxyl free radical also decomposable organic pollutant and Kill bacterial virus.
In a semiconductor material, stannic oxide is a kind of wide N-type semiconductor of forbidden band (Eg=3.6ev, 300K), intrinsic Sn02 Material resistance is very big, can have Lacking oxygen in the synthesis process because of hypoxgia, and stannic oxide is tetragonal crystal system rutile structure, In P42/mnm space group, cell parameter is a=4.737, c=3.186, c/a=0.673 respectively, in each structure cell there are two Stannic oxide molecule, the non-polar conformations that stannic oxide has symmetry relatively good itself do not have anisotropic growth habit, complete The stannic oxide of beauty is insulator, and crystalline silica tin all contains interstitial atom and has Lacking oxygen, it is usually the case that two N-type semiconductor characteristic is presented in tin oxide.Each Sn atom is at the octahedra center that six O atoms form, and by three Sn originals The coordination structure of 6:3 is presented there are an O atom in molecular equilateral triangle center.The each not phase of the size of each surface energy Together, and comparison in difference is small, although crystal face energy highest, and c/a=0.673 makes it grow into the big wiener of draw ratio in c-axis Rice structure brings difficulty, and external environmental parameter largely changes the morphogenesis of stannic oxide crystal.
Tin dioxide nano-particle is prepared using alcohol heating method in the present invention.
By stannous chloride crystal ultrasonic dissolution in the tert-butyl alcohol, the solution that mass concentration is 100-120g/L is formed, institute is taken Solution 10mL is stated, 5.OOmL glycerol and 2.25mL hexamethylene are added thereto, stirring is transparent to Rong Ye Cheng Cheongju, fills kettle, is put into 200 DEG C baking oven reacts 8h.Cooled to room temperature is washed repeatedly with deionized water and second are liquor-saturated, centrifugation, 80 DEG C of vacuum dryings, and 500 DEG C 4h is roasted, sample 2 (Sample2) can be obtained.Other samples are made respectively with control variate method, are labeled as sample 1 (Sample1, alcohol agent are 1.OOmL glycerol) sample 3 (Sample3, alcohol agent are 5.OOmL ethylene glycol).
Heating rate is 2 DEG C of min when above-mentioned 500 DEG C of roastings-1。
Using the means of testing such as XPS, XRD, XPS, UV-vis, SEM (FESEM), TEM to prepared sample in the present invention Component, appearance structure and optical property etc. are characterized, and have been analyzed and researched difference by photocatalysis performance test and comparison The photocatalysis performance of sample studies its mechanism of action, show that sample 2 shows excellent catalytic performance.
Wherein,
XPS:X X-ray photoelectron spectroscopy X, the PHI 5000ESCA X-ray photoelectricity produced using Perkin Elmer company Sub- energy disperse spectroscopy, excitaton source are AlK α (1486.6eV) ray, high pressure 14.0kV, power 250W, X-ray and sample angle theta= 54 °, analysis chamber pressure is 10 when surveying virgin-9Torr can be corrected by the combination of Cls on the basis of (284.6eV)；
XRD:X ray powder diffraction carries out the object phase point of sample using 2000 type X-ray diffractometer of Rigacu company D Analysis is radiographic source (X=1.54A) using Cu K α radiation, and graphite monochromator, pipe presses 40KV, Guan Liu 20-30mA, and sweep speed is 1.2°/min；
UV-vis: UV-vis DRS carries out, scanning range 200- on Shimadzu UV-2450 type spectrophotometer 800nm, with high-purity BaS04For standard reagent；
FESEM: field emission scanning electron microscope scans electricity using the 4800 type cold field emission of S of Japanese HITACHI company production Sub- microscope, operating voltage 3.0KV；
TEM: transmission electron microscope, using Japanese 2010 type transmission electron microscope of JEM, sample is carefully ground before testing, and It is ultrasonically treated in ethanol.
Although prepared sample SnO2Partially absorbed in visible region, but be not it is very strong, light utilization efficiency be not still it is very high, Therefore here using 300W xenon lamp (λ > 200nm) the irradiation excitation composed entirely.In order to illustrate made SnO2Sample has in photocatalytic degradation Excellent properties in terms of color dyestuff RhB and MB, we have chosen commercialized SnO2As a comparison.As shown in Fig. 1 (a), in light When catalytic degradation RhB, compared to commercialization SnO2And make other samples by oneself, 2 activity of sample is best, through 4h light-catalyzed reaction, RhB Degradation rate is up to 60%.For similar rule as shown in Fig. 1 (b), sample 2 still shows optimum activity, anti-through 4h photocatalysis when degradation MB It answers, MB removal rate is up to 96%.Can be seen that from Fig. 1 (c), degrade RhB when, which is approximately-order reaction, and medium-rate is normal Following rule is calculated in number basis:
kRhB-Sample2(0.2168h-1)>kRhB-Sample3(0.1874h-1)>kRhB-Sample1(0.1342h-1)>kRhB-Commercial (0.07654h-1).Similarly, when degrading MB, similar rule is also obtained, as shown in Fig. 1 (d).According to calculating,
kMB-Sample2(0.8217h-1)>kMB-Sample3(0.5940h-1)>kMB-Sample1(0.4497h-1)>kMB-Commercial (0.3490h-1).The RhB or MB that no matter degrades is obtained by above data analysis, from the SnO of research and development2Activity and degradation rate are equal Higher than in commercialization Sn02, while other samples that compare, sample 2 show optimal catalytic effect.This is attributable to following Several points: 1) sample 2 with higher crystallinity: 2) there is biggish specific surface area, is conducive to the absorption to substrate: 3) biggish Hole holds aperture, is conducive to mass transfer；4) stronger light absorption, higher light utilization efficiency.
It follows that the present embodiment passes through the SnO that is prepared with alcohol heating method2Nanoparticle passes through the kind of modulation related solvents Class and amount, control generate SnO2Growth, it is basic to realize that size is controllable, be uniformly dispersed.Wherein closed under containing 5mL glycerol system At Sn02, due to its higher crystallinity, biggish specific surface area and higher light utilization efficiency, and then optimal light is presented Electro-catalysis and photocatalysis performance.Anodic polarization curves, which are tested, to be shown under equal conditions, the current density with higher of sample 2, And then preferably PhotoelectrocatalytiPerformance Performance is presented: photocatalysis test shows that optimal catalytic performance is presented in sample 2, through 4h photocatalysis Reaction, RhB and MB degradation rate is respectively up to 60%.SnO2 nanoparticle prepared by the method is in environmental catalysis purification and photoelectric conversion Aspect all has good application prospect.
The present invention also provides a kind of production methods of metal composite.
Under room temperature, five nitric hydrate bismuth of 240-250g is dissolved in 10L ethylene glycol, 110g chlorine is added while stirring Change stannous crystal, after solution clarification, 30L ethyl alcohol is added, continues to move into 50L reaction kettle after stirring 30min, in 160 DEG C of items For 24 hours, then via ethanol washing, 80 DEG C of drying, (heating rate is 2 DEG C of min to alcohol heat for 500 DEG C of roastings under part-1) be made after 4h SnO2/ BiOCl compound.
Since the unique electronic structure of Bi is conducive to the migration of photo-generated carrier, bismuth oxygen oxide (BiOX, X=Cl, Br, I) capable of serving as the role of co-catalyst well, (they are tetragonal phase structures, are (Bi between two X layers202)2+Layer, and it is every A [Bi2O2]X2It is made of 5 atoms, each 0, X, Bi is made to separately constitute an OBi4Tetrahedron, XBi4Quadrangular pyramid and Bi04X4 The anti-prism in positive quadrangle.Just because of this special construction, it has been found that, light reflects and at double between translucent BiOX piece Growth, the anisotropic of adhesion equally illustrate other than the edge of layer without others free radicals, and light excitation reflection not O-Bi-X can be destroyed, good photostability is shown.
Above-mentioned composite sample is utilized into transmission electron microscope observing, it is clear that compound is spherical substance, light and shade Variation shows that it is particularly likely that microcellular structure.The microstructure of sample is further observed with high resolution electron microscopy, SnO2 Clearly lattice fringe is shown with BiOCl, shows its crystallographic property.SiO2The spacing of lattice of nano particle is 0.25nm, the SnO with tetragonal phase2The spacing of lattice of certain one side is consistent；And 0.35nm is equivalent to the surface tetragonal phase BiOCl Spacing of lattice.Even if after ultrasound, SnO2 nanoparticle and BiOCl nanoparticle still being bonded together tightly, high-resolution Electron microscope, which clearly indicates, forms firm knot (hetero-junctions) in the different crystal contact face of two classes, makes SnO2With BiOCl is often firmly combined into hetero-junctions composite photocatalyst, while being formed by hetero-junctions also and make interface electron transmission more It is that smoothness is effective, greatly improves photocatalytic activity.
The raising of the catalytic activity of composite photo-catalyst is and two because compound so that effectively catalysis area improves The coupling effect of semiconductor also contributes to active increase.On the one hand, the specific surface area increase of compound helps to improve light and urges Change conversion zone.In addition, porous structure is conducive to transmitting of the photo-generated carrier from surface to organic molecule, and make its It is rapidly spread between reactants and products in reaction.On the other hand, it is known that photocatalytic process depends on current-carrying The generation and separation of son.The factor for influencing photocatalytic activity generally has electronics, hole, hydroxyl radical free radical and oxygen radical.In light According under the conditions of, photochemical catalyst is scattered in air or contaminated water, and the electronics on the hole and conduction band in valence band generates, these Electron-hole pair and substrate interaction, the hole of valence band and the water of catalyst surface or hydroxyl react to form carboxyl certainly By base, meanwhile, the hole of valence band can also aoxidize organic molecule, and the electronics of conduction band reduces oxygen molecule to form superoxide radical.It will Above-mentioned oxide or complex catalysts machine are compound with organic coating, are dispersed in sample in traditional organic coating, formation changes Property nano composite dope, judges the photocatalysis performance of modified coating by testing its UV-visible absorption spectrum；Sample with Organic coating complex method includes physical blending, intercalation, in-situ polymerization and sol-gel method, generally uses physical blending process, object Reason blending method is by nano-powder surface treated or to be prefabricated into the slurry of stable dispersion, is directly scattered in organic binder, It is to be introduced into nano structural material in multicomponent system coating, each component synergistic effect, to improve coating property.
Gained modified Nano composite coating is sprayed at concrete prefabricated element surface layer, forms nano coating；Pass through coating The test of coating stain resistance and paint coatings resistance to ag(e)ing test (international standard number: ASTM D3719:2000) to measure nanometer Influence of the photochemical catalyst to coating contaminated resistance and ageing-resistant performance.
Nano-photocatalyst is under ultraviolet light, using multiple building materials as carrier, is urged using it with good light Change oxidability and surface super hydrophilic performance, realize oxygenolysis atmosphere pollution, bacteriostasis antibiosis, is prevented mould proof, antifouling, anti-dew A variety of purposes such as mist.It is decorative mixed in clear-water concrete etc. that nano-photocatalyst is added in concrete or is used as coating application Solidifying soil surface, can not only maintain aesthetic appearance of construction material itself, but also can improve air quality, and improve atmospheric environment, protect City cleaning is held, maintenance cost can be saved, to extend the service life of building itself, reach good economy and society Benefit.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (6)

1. the photocatalysis construction technology and detection method of a kind of automatically cleaning prefabricated components, include the following steps:
(1) using metal salt as source metal, using hydro-thermal or water-bath synthetic method, by adjusting its reaction condition, being made has not Connatural metal oxide or more metal composite samples；
(2) component, appearance structure and the optical property aspect of sample prepared by step (1) are characterized, and passes through photocatalysis Performance test comparative analysis has studied the photocatalysis performance of different samples, studies its mechanism of action, and keep a record；
(3) sample prepared by step (1) is compound with organic coating respectively, it is dispersed in sample in traditional organic coating, Modified Nano composite coating is formed, judges the photocatalysis performance of modified coating by testing its UV-visible absorption spectrum；
(4) gained modified Nano composite coating in step (3) is sprayed at concrete prefabricated element surface layer, forms nano coating； Nano-photocatalyst is measured to coating stain resistant by the test of paint coatings stain resistance and the test of paint coatings resistance to ag(e)ing The influence of performance and ageing-resistant performance.
2. the photocatalysis construction technology and detection method of a kind of automatically cleaning prefabricated components according to claim 1, feature Be, one kind of metal oxide samples described in step (1) the preparation method is as follows:
By stannous chloride crystal ultrasonic dissolution in the tert-butyl alcohol, the solution that mass concentration is 100-120g/L is formed, is taken described molten 5L glycerol and 2.25L cyclohexane is added in liquid 10L thereto, and stirring to solution clear fills kettle, is put into 200 DEG C of baking ovens anti- Answer 18h；Cooled to room temperature is washed and is centrifuged repeatedly with deionized water and ethyl alcohol, then vacuum drying under the conditions of 80 DEG C, Drying gained is roasted into 4h at 500 DEG C, stannic oxide is made.
3. the photocatalysis construction technology and detection method of a kind of automatically cleaning prefabricated components according to claim 1, feature Be, one kind of metal composite sample described in step (1) the preparation method is as follows:
Under room temperature, five nitric hydrate bismuth of 240-250g is dissolved in 10L ethylene glycol, 110g protochloride is added while stirring 30L ethyl alcohol is added after solution clarification in tin crystal, continues to move into 50L reaction kettle after stirring 30min, under the conditions of 160 DEG C For 24 hours, then via ethanol washing, 80 DEG C dry alcohol heat, and SnO is made after 500 DEG C of roasting 4h2/ BiOCl compound.
4. the photocatalysis construction technology and detection method of a kind of automatically cleaning prefabricated components according to claim 2 or 3, special Sign is, heating rate is 2 DEG C of min-1 when 500 DEG C of roastings.
5. the photocatalysis construction technology and detection method of a kind of automatically cleaning prefabricated components according to claim 1, feature It is, sample and organic coating complex method include physical blending, intercalation, in-situ polymerization and sol-gel in the step (3) Method.
6. the photocatalysis construction technology and detection method of a kind of automatically cleaning prefabricated components according to claim 1, feature It is, using method when being characterized in the step (2) to component, appearance structure and the optical property aspect of prepared sample Including XPS, XRD, UV-vis, SEM, TEM.
CN201910284748.1A 2019-04-10 2019-04-10 A kind of the photocatalysis construction technology and detection method of automatically cleaning prefabricated components Pending CN109988451A (en)

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CN102847546A (en) * 2012-05-23 2013-01-02 上海师范大学 Preparation method of SnO2/BiOCl heterojunction photocatalyst
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US20060156941A1 (en) * 2000-06-26 2006-07-20 Fuji Photo Film Co., Ltd. Planographic printing method, original printing plate and printing press
CN101781482A (en) * 2009-12-04 2010-07-21 上海瓷龙化工有限公司 Photocatalytic self-cleaning nano ecology coating and preparation method thereof
CN102344721A (en) * 2010-08-04 2012-02-08 北新集团建材股份有限公司 Paint composition and preparation method thereof
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