CN107774241A - A kind of TiO2/ tourmaline composite photo-catalyst and TiO2/ tourmaline gauze - Google Patents
A kind of TiO2/ tourmaline composite photo-catalyst and TiO2/ tourmaline gauze Download PDFInfo
- Publication number
- CN107774241A CN107774241A CN201710218890.7A CN201710218890A CN107774241A CN 107774241 A CN107774241 A CN 107774241A CN 201710218890 A CN201710218890 A CN 201710218890A CN 107774241 A CN107774241 A CN 107774241A
- Authority
- CN
- China
- Prior art keywords
- tourmaline
- tio
- catalyst
- solution
- gauze
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052613 tourmaline Inorganic materials 0.000 title claims abstract description 92
- 229940070527 tourmaline Drugs 0.000 title claims abstract description 92
- 239000011032 tourmaline Substances 0.000 title claims abstract description 92
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229960000583 acetic acid Drugs 0.000 claims abstract description 11
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000002604 ultrasonography Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 47
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000004575 stone Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 7
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 235000013312 flour Nutrition 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 9
- 229930040373 Paraformaldehyde Natural products 0.000 description 8
- 125000005909 ethyl alcohol group Chemical group 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920002866 paraformaldehyde Polymers 0.000 description 8
- 230000008901 benefit Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 230000005684 electric field Effects 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000462 teratogen Toxicity 0.000 description 1
- 239000003439 teratogenic agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of TiO2/ tourmaline composite photo-catalyst and TiO2/ tourmaline gauze, the preparation of the photochemical catalyst comprise the following steps, and take glacial acetic acid to be added in absolute ethyl alcohol, stirring；Butyl titanate is slowly added to, stirs, obtains solution of tetrabutyl titanate；Tourmaline powder is added to ultrasound in another absolute ethyl alcohol, obtains tourmaline powder solution；Solution of tetrabutyl titanate is added drop-wise in tourmaline solution, stirred；Obtain mixed solution；Absolute ethyl alcohol, deionized water and concentrated hydrochloric acid are well mixed, are then added drop-wise in above-mentioned mixed solution, is stirred, forms grey colloidal sol, then stirring forms gel at a certain temperature；Gel drying, grinding, calcining form TiO2/ tourmaline catalyst powder.The present invention solves activity and fixes the bottleneck problem in two big photocatalyst applications；Environment additional function, service life with release negative aeroion are long, easy to operate, low using cost, can effectively improve air quality, have significant actual application prospect.
Description
Technical field
The invention belongs to field of material technology, more particularly, to a kind of TiO2/ tourmaline composite photo-catalyst and TiO2/ electricity
Gas stone gauze.
Background technology
As building and decoration industry develop rapidly, the extensive utilization of various new materials so that waved in room air
The content of hair property organic pollution greatly increases, and causes the pollution problem getting worse of room air.Wherein formaldehyde (HCHO) quilt
The World Health Organization is defined as carcinogenic and teratogen, huge to human health damage, more as treating indoor air pollution
Emphasis.Conventional method physisorphtion, chemical oxidization method and bioanalysis of air formaldehyde processing etc. are in the prevalence of removal ability
It is limited, be also easy to produce secondary pollution, the problems such as cost is high.And photocatalysis technology, because secondary pollution is few, catalytic reaction condition is gentle, can
Exhaustive oxidation decomposing organic matter is CO at normal temperatures and pressures2And H2O and more with prospects.
In numerous catalysis materials, TiO2With its non-selectivity, stable performance, it is safe and non-toxic, cost is low the advantages of
Extensive concern is caused in terms of the depollution of environment, has been supplied in dyestuff, agricultural chemicals, surfactant, organic resin, halo chemical combination
In the processing of the pollutants such as thing, oily waste water, particularly when organic pollution is dense or with conventional method be difficult degraded when,
This technology has more obvious advantage.Such conductor photocatalysis reaction mechanism is：When being more than energy gap by energy
During light irradiation, the electronics in valence band (VB) is excited on conduction band (CB), forms conduction band electron (e-), while leave sky in valence band
Cave (h+), hole can be the same as the OH adsorbed in catalyst surface-Or H2O, which has an effect, generates the OH of high activity, without selectively oxygen
Change gas chromatography, light induced electron also can be with O2Generation active oxygen radical of having an effect participates in redox reaction.But should
Technology has certain limitation in actual applications：Light induced electron and hole-recombination rate is higher causes light-catalyzed reaction efficiency not
It is high；Catalyst is not strong to volatile organic contaminant adsorption capacity；Powdered form catalyst is inconvenient for use.Therefore current research is more
With TiO2Based on, by metal ion, rare earth ion doped, semiconductors coupling, noble metal loading, outfield (thermal field, microwave,
Ultrasound, electric field) effect assists the technology such as photocatalysis the means such as to carry out reduces the recombination rate of photo-generated carrier, photocatalysis performance is improved,
Or by TiO2Immobilization (photochemical catalyst using glass, clay, hollow glass ball, Metal Substrate etc. as carrier is immobilized), but be catalyzed
Specific surface area reduces after agent is fixed, and the suction-operated of catalyst and extinction efficiency reduce, and catalyst activity can be caused to reduce again.
The content of the invention
In view of this, the present invention is directed to propose a kind of TiO2/ tourmaline composite photo-catalyst and TiO2/ tourmaline gauze, with
Overcome the deficiencies in the prior art, solves the problems, such as Formaldehyde Pollution of Indoor Air.
To reach above-mentioned purpose, the technical proposal of the invention is realized in this way：
A kind of TiO2/ tourmaline composite photo-catalyst, the preparation of the photochemical catalyst comprise the following steps,
1) take a certain amount of glacial acetic acid to be added in absolute ethyl alcohol, stir, make to be well mixed；It is slowly added to butyl titanate,
Stirring, obtains solution of tetrabutyl titanate；
2) take appropriate tourmaline powder to be added in another absolute ethyl alcohol ultrasonic, obtain tourmaline powder solution；
3) solution of tetrabutyl titanate obtained in step 1) is added drop-wise in the tourmaline solution that step 2) obtains, stirred；
Obtain mixed solution；
4) absolute ethyl alcohol, deionized water and concentrated hydrochloric acid are well mixed；
5) solution for obtaining step 4) is added drop-wise in the mixed solution that step 3) obtains, and stirring, forms grey colloidal sol, so
Gel is formed under stirring at a certain temperature afterwards；
6) gel drying, grinding, calcining are formed into TiO2/ tourmaline composite photo-catalyst powder.
Preferably, butyl titanate, the amount of glacial acetic acid corresponding to every 0.012~0.23g tourmaline powders be respectively 8~
12ml, 4~5ml.
Preferably, in step 1), the volume ratio of glacial acetic acid and absolute ethyl alcohol is：(4~5): (20~25)；Glacial acetic acid adds
To after absolute ethyl alcohol, 10~20min is stirred；20~30min is stirred after adding butyl titanate；Preferably, glacial acetic acid is added to
After absolute ethyl alcohol, 10min is stirred；30min is stirred after adding butyl titanate.
Preferably, in step 2), the amount that tourmaline powder is added in every 30mL absolute ethyl alcohols is 0.012~0.23g；Tourmaline
20~30min of ultrasound after powder is added in absolute ethyl alcohol；Preferably, 30min；Preferably, the tourmaline powder is by pre- place
Obtain, comprise the following steps after reason, tourmaline raw material adds distilled water 1~1.5h of ultrasonic disperse, then adds 1~2mol/L
Dilute hydrochloric acid solution 1~1.5h of ultrasonic disperse, stand 12~24h afterwards, finally washed repeatedly with distilled water until neutral, 80~
100 DEG C are dried for standby.
Preferably, in step 3), the solution of tetrabutyl titanate obtained in step 1) is added drop-wise to 8~10ml/min speed
In the tourmaline solution that step 2) obtains；After being added dropwise, 1~1.5h is stirred, mixing speed is 180~200r/min.
Preferably, in step 4), absolute ethyl alcohol, the volume ratio (20~25ml) of deionized water: (8~12ml)；After mixing,
The pH of solution is 1.7~2；
Preferably, in the step 5), solution that step 4) obtains is added drop-wise to step 3) with 3~5ml/min speed
The mixed solution arrived, keep being stirred with 180~200r/min mixing speed during dropwise addition；After dropwise addition 180~
Continue 1~2h of stirring under 200r/min mixing speed；Preferably, 2h；After forming grey colloidal sol, in 40~60 DEG C of temperature,
Under 30~40rpm mixing speed, 2~3h of gel；
In step 6), 80~100 DEG C of drying temperature, 10~12h of drying time；450~550 DEG C of calcining heat, during calcining
Between 2~4h.
Present invention also offers one kind to use TiO as described above2TiO prepared by/tourmaline composite photo-catalyst2/ electrically
Stone gauze, comprises the following steps,
1) under 70~90 DEG C of water bath conditions, ethyl cellulose is dissolved in absolute ethyl alcohol as binding agent；
2) gauze is impregnated in the binding agent of step 1) and taken out after 3~5min, the mesh of gauze is opened, then will
TiO2The powder even application of/tourmaline composite photo-catalyst on gauze, dry, that is, obtains TiO by room temperature2/ tourmaline gauze；
Preferably, by the gauze of dipping, the mesh of gauze is opened by the method for injection.
Preferably, in step 1), 1~2g ethyl cellulose is added in the absolute ethyl alcohol per 50mL.
Present invention provides TiO as described above2/ tourmaline composite photo-catalyst or TiO as described above2/ electrically
Application of the stone gauze in except formaldehyde.
Assist light-catalysed method that there is significant effect using extra electric field, its principle is by additional anodic bias
E- is flowed to negative electrode by external circuit, prevent the compound of photoinduced electron and hole, make there are more photohole h+ to deposit in system
So as to generate more OH, the efficiency of light quantum is being improved.But on the one hand the method needs additional power source, on the other hand
By TiO2Electrode is made, is difficult technically extensive raising space-time yield due to being limited by membrane electrode units activity area.
And natural mineral tourmaline uniquely has the mineral of pyroelectric effect and piezo-electric effect as nature, have unique heteropole symmetrical
Structure.Tourmaline shows as making in its micrometer range of surface thickness more than ten with spontaneous polarization, polarity effect in physical property
In the presence of 104-107V/m high electric field, when its surface or around with the presence of free electron when, it will by the anode of tourmaline
Ability that is rapid to attract and firmly capture, making free electron lose free movement, greatly reduces titanium dioxide photoproduction electronics
With the compound probability in hole, so as to improve the clearance of formaldehyde.In addition, the self power generation polarity of tourmaline also makes it have radiation far
Unique environmental functional properties such as infrared ray, release negative aeroion.
The present invention utilizes polyvinyl chloride from natural electric field cooperative reinforcing and indoor gaseous contamination processing feature, design
PVC nets (screen material) do substrate and prepare TiO2/ tourmaline composite photocatalyst net, Web materials are easy to the circulation of gas, in dirt
While contaminating thing efficient mass transfer, its pressure change can also strengthen the polarity of tourmaline, and enhancing electric microfield improves catalytic effect；As
Window screening is played degradation capability to directly be beneficial to sunshine, is made the product for rooms such as degradation of formaldehyde using more conducively light absorbs
Interior gaseous contaminant has higher economy and practicality.
Relative to prior art, a kind of TiO of the present invention2/ tourmaline composite photo-catalyst and TiO2/ tourmaline yarn
Net, have the advantage that：
1) green mineral are used as primary raw material, the defects of for traditional catalysis material, utilize electrical mineral tourmaline
Permanent spontaneous electric field promote the separation of photo-generate electron-hole, strengthen absorption mass transfer, obtained in a manner of being helped without impressed field
Safe and stable, efficient New Mineral base composite photocatalyst material, breach the limitation of the conventional mineral utilization of resources.
2) suitable application mode is developed for indoor vapor phase contaminants, it is material solid supported using window screening, both ensure to pollute
The contact surface of thing mass transfer directly receives light again, while strengthens electrical property, raising catalytic efficiency by the circulation of gas, is answered
For the improvement of volatile organic contaminant in surrounding air, while solve activity and fix in two big photocatalyst applications
Bottleneck problem；
3) the environment additional function, service life with release negative aeroion are long, easy to operate, low using cost, energy
Air quality is effectively improved, there is significant actual application prospect, the more of environmental benefit, economic benefit and social benefit can be realized
Win.
Brief description of the drawings
The accompanying drawing for forming the part of the invention is used for providing further understanding the invention, present invention wound
The schematic description and description made is used to explain the invention, does not form the improper restriction to the invention.
In accompanying drawing：
Fig. 1 is TiO2SEM pictures；
Fig. 2 is the SEM pictures of tourmaline；
Fig. 3 is the SEM pictures of Ti/T (1%) composite catalyst that the tourmaline mass fraction synthesized in embodiment 2 is 1%
The TiO of Fig. 4 difference tourmaline contents2/ tourmaline gauze and simple TiO2The contrast of gauze PARA FORMALDEHYDE PRILLS(91,95) degradation property
Figure.
Fig. 5 is TiO2The stability test figure of/tourmaline gauze
Fig. 6 is the TiO of different quality2The comparison diagram of/tourmaline gauze PARA FORMALDEHYDE PRILLS(91,95) degradation property.
Embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
Describe the present invention in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
1) preparation of photochemical catalyst powder
Using sol-gal process, take 4ml glacial acetic acids to be added in 30ml absolute ethyl alcohols, magnetic agitation 10min, make mixing equal
It is even, 10ml butyl titanates stirring 30min is then slowly added into, obtains solution of tetrabutyl titanate；
Meanwhile take appropriate tourmaline powder to be added to 20ml absolute ethyl alcohol ultrasound 30min, obtain tourmaline powder solution；Afterwards
Solution of tetrabutyl titanate is slowly dropped in tourmaline powder solution, strong stirring 1h, obtains mixed solution；
20ml absolute ethyl alcohols, 10ml deionized waters and concentrated hydrochloric acid is taken to make it well mixed, it is 1.7 or so to make pH value of solution, will
This solution is slowly dropped under strong stirring in the mixed solution of butyl titanate and tourmaline obtained above, strong stirring
2h forms grey colloidal sol, and then 40 DEG C of stirring in water bath 2h form gel.Gel is through 80 DEG C of drying 12h, grinding, 500 DEG C of calcining 2h
As TiO2Photochemical catalyst powder.
2) preparation of catalyst gauze
Take 1g ethyl celluloses to be added in 50ml absolute ethyl alcohols, be placed in 80 DEG C of water-baths and dissolve to obtain ethyl cellulose colloidal sol
As binding agent.Pretreated gauze is cut into 5cm × 5cm sheet, is impregnated in binding agent and is taken out after a few minutes, is utilized
The method of injection opens the mesh of gauze, is then equably sprayed on catalyst powder on gauze, room temperature is dried, and is produced negative
Carry firm TiO2Gauze, immobilized TiO2Quality is 0.168g.
Embodiment 1：
Added into 20ml absolute ethyl alcohols and account for TiO2The tourmaline of quality 0.5%, then ultrasonic 30min, obtains tourmaline
Powder solution.
Embodiment 2：
Added into 20ml absolute ethyl alcohols and account for TiO2The tourmaline of quality 1%, then ultrasonic 30min, obtains tourmaline powder
Solution.
TiO2, tourmaline, TiO2The SEM figures of/1% tourmaline, as shown in Figure 1, Figure 2, Fig. 3.
Embodiment 3：
Added into 20ml absolute ethyl alcohols and account for TiO2The tourmaline of quality 2%, then ultrasonic 30min, obtains tourmaline powder
Solution.
Embodiment 4：
Added into 20ml absolute ethyl alcohols and account for TiO2The tourmaline of quality 5%, then ultrasonic 30min, obtains tourmaline powder
Solution.
Embodiment 5：
Added into the countless ethanol of 20ml and account for TiO2The tourmaline of quality 10%, then ultrasonic 30min, obtains tourmaline powder
Solution.
TiO prepared by the measure present invention2Gauze and TiO2The degradation property of/tourmaline gauze PARA FORMALDEHYDE PRILLS(91,95) gas is as follows：
The test device that the present invention uses is cylindrical flange mouth glass reactor.Rotor is put into reactor first,
Then the 20 certain density formalins of μ l are taken in reactor, it is 100mg/m to make concentration of formaldehyde in reactor3, will be fixed with
The uviol lamp of catalyst gauze and cylindrical chamber assembling and good seal.Reactor is placed in into 2h in 40 DEG C of magnetic agitation water-baths to treat
It spreads uniformly, and rear sampling is once.Then uviol lamp is opened, every 10min samplings once, untill 60min, determines TiO2Yarn
Net and TiO2The degradation property of/tourmaline gauze PARA FORMALDEHYDE PRILLS(91,95) gas.Assay method of the present invention uses national standard GB/T18204.26-
2000 phenol reagent methods, 25 DEG C of constant temperature colour developings.
1) tourmaline is to TiO2The influence of Photo-Catalytic Degradation of Formaldehyde
Utilize the immobilized O.168g pure TiO of binder method2In on gauze, in addition, pressing equal quality TiO2, the electricity of different content
The composite photo-catalyst of the immobilized different quality of gas stone is on gauze, and measure different content tourmaline is to TiO2Formaldehyde degradation by photocatalytic oxidation process
The influence of gas, experimental result are as shown in Figure 4.As a result the TiO of load electrical stone is shown2The degradation rate of PARA FORMALDEHYDE PRILLS(91,95) almost reaches
100%, higher than simple TiO2The degradation rate of PARA FORMALDEHYDE PRILLS(91,95), show tourmaline to TiO2Photocatalysis there is facilitation.
2)TiO2Stability test of/tourmaline the gauze to degradation of formaldehyde gas
Tourmaline content is 1% TiO2/ tourmaline gauze is to 100mg/m3The degradation rate replication of formaldehyde four times, survey
It is as shown in Figure 5 to determine result.As a result TiO is shown2/ tourmaline gauze stability is preferable, reusable.
3) TiO of different quality2The influence of/tourmaline gauze PARA FORMALDEHYDE PRILLS(91,95) degradation property
Respectively on gauze immobilized quality be 0.048g, 0.128g, O.170g, 0.220g, 0.232g tourmaline content
1% TiO2/ tourmaline composite photo-catalyst, determine the TiO of different quality2The shadow of/tourmaline gauze PARA FORMALDEHYDE PRILLS(91,95) degradation property
Ring, experimental result is as shown in Figure 6.As a result show in certain limit, the degradation rate of formaldehyde gradually increases with the increase of catalyst, directly
It is about 0.232g to catalyst, now, the load of gauze surface catalyst is complete, and degradation rate is maximum, and up to 100%.
The preferred embodiment of the invention is the foregoing is only, is not intended to limit the invention creation, it is all at this
Within the spirit and principle of innovation and creation, any modification, equivalent substitution and improvements made etc., the invention should be included in
Protection domain within.
Claims (10)
- A kind of 1. TiO2/ tourmaline composite photo-catalyst, it is characterised in that：The preparation of the photochemical catalyst comprises the following steps,1) take a certain amount of glacial acetic acid to be added in absolute ethyl alcohol, stir, make to be well mixed；Butyl titanate is slowly added to, is stirred, Obtain solution of tetrabutyl titanate；2) appropriate tourmaline powder is added in another absolute ethyl alcohol ultrasonic, obtains tourmaline powder solution；3) solution of tetrabutyl titanate obtained in step 1) is added drop-wise in the tourmaline solution that step 2) obtains, stirred；Obtain Mixed solution；4) absolute ethyl alcohol, deionized water and concentrated hydrochloric acid are well mixed；5) solution for obtaining step 4) is added drop-wise in the mixed solution that step 3) obtains, and stirring, forms grey colloidal sol, Ran Hou Stirring forms gel under certain temperature；6) gel drying, grinding, calcining are formed into TiO2/ tourmaline composite photo-catalyst powder.
- 2. TiO according to claim 12/ tourmaline composite photo-catalyst, it is characterised in that：Every 0.012~0.23g is electric Butyl titanate, the amount of glacial acetic acid are respectively 8~12ml, 4~5ml corresponding to stone flour.
- 3. TiO according to claim 12/ tourmaline composite photo-catalyst, it is characterised in that：In step 1), glacial acetic acid with The volume ratio of absolute ethyl alcohol is：(4~5): (20~25)；After glacial acetic acid is added to absolute ethyl alcohol, 10~20min is stirred；Add 20~30min is stirred after butyl titanate；Preferably, after glacial acetic acid is added to absolute ethyl alcohol, 10min is stirred；Add metatitanic acid four 30min is stirred after butyl ester.
- 4. TiO according to claim 12/ tourmaline composite photo-catalyst, it is characterised in that：In step 2), per 30mL without The amount that tourmaline powder is added in water-ethanol is 0.012~0.23g；Tourmaline powder be added in absolute ethyl alcohol after ultrasound 20~ 30min；Preferably, 30min；Preferably, the tourmaline powder obtains after pretreatment, comprises the following steps, electrically Stone raw material adds distilled water 1~1.5h of ultrasonic disperse, then adds 1~2mol/L dilute hydrochloric acid solution 1~1.5h of ultrasonic disperse, 12~24h is stood afterwards, is finally washed repeatedly with distilled water until neutral, 80~100 DEG C are dried for standby.
- 5. TiO according to claim 12/ tourmaline composite photo-catalyst, it is characterised in that：In step 3), in step 1) Obtained solution of tetrabutyl titanate is added drop-wise to 8~10ml/min speed in the tourmaline solution that step 2) obtains；Drip Bi Hou, mixed solution is stirred into 1~1.5h, mixing speed is 180~200r/min.
- 6. TiO according to claim 12/ tourmaline composite photo-catalyst, it is characterised in that：In step 4), absolute ethyl alcohol, The volume ratio (20~25ml) of deionized water: (8~12ml)；After mixing, the pH of solution is 1.7~2.
- 7. TiO according to claim 12/ tourmaline composite photo-catalyst, it is characterised in that：In the step 5), step 4) solution obtained is added drop-wise to the mixed solution that step 3) obtains with 3~5ml/min speed, is kept during dropwise addition with 180 ~200r/min mixing speed is stirred；Continue 1~2h of stirring after dropwise addition under 180~200r/min mixing speed； Preferably, 2h；After forming grey colloidal sol, at 40~60 DEG C of temperature, 30~40rpm mixing speed, 2~3h of gel；In step 6), 80~100 DEG C of drying temperature, 10~12h of drying time；450~550 DEG C of calcining heat, calcination time 2~ 4h。
- A kind of 8. TiO using as described in any one of claim 1~72TiO prepared by/tourmaline composite photo-catalyst2/ electrically Stone gauze, it is characterised in that：Comprise the following steps,1) under 70~90 DEG C of water bath conditions, ethyl cellulose is dissolved in absolute ethyl alcohol as binding agent；2) gauze is impregnated in the binding agent of step 1) and taken out after 3~5min, the mesh of gauze opened, then by TiO2/ electricity The powder even application of gas stone composite photo-catalyst on gauze, dry, that is, obtains TiO by room temperature2/ tourmaline gauze；Preferably, By the gauze of dipping, the mesh of gauze is opened by the method for injection.
- 9. TiO according to claim 82/ tourmaline gauze, it is characterised in that：In step 1), the absolute ethyl alcohol per 50mL 1~2g of middle addition ethyl cellulose.
- 10. the TiO as described in any one of claim 1~72/ tourmaline composite photo-catalyst or such as the institute of claim 8 or 9 The TiO stated2Application of/tourmaline the gauze in except formaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710218890.7A CN107774241B (en) | 2017-04-01 | 2017-04-01 | TiO 22Tourmaline composite photocatalyst and TiO2Tourmaline gauze |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710218890.7A CN107774241B (en) | 2017-04-01 | 2017-04-01 | TiO 22Tourmaline composite photocatalyst and TiO2Tourmaline gauze |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107774241A true CN107774241A (en) | 2018-03-09 |
| CN107774241B CN107774241B (en) | 2020-12-01 |
Family
ID=61437513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710218890.7A Active CN107774241B (en) | 2017-04-01 | 2017-04-01 | TiO 22Tourmaline composite photocatalyst and TiO2Tourmaline gauze |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107774241B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993558A (en) * | 2018-08-13 | 2018-12-14 | 蒋黎婷 | A kind of preparation method of high-performance titanium dioxide optical catalyst |
| CN111604044A (en) * | 2020-06-30 | 2020-09-01 | 郑州大学 | Preparation and application of tourmaline/titanium dioxide composite photocatalyst sol |
| CN112010388A (en) * | 2020-08-18 | 2020-12-01 | 天津市职业大学 | Wastewater treatment device for photocatalytic degradation of organic pollutants for laboratory and use method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1420800A (en) * | 1999-10-15 | 2003-05-28 | Abb拉默斯环球有限公司 | Conversion of nitrogen oxides in presence of catalyst supported of mesh-like structure |
| CN1522954A (en) * | 2003-09-10 | 2004-08-25 | 河北工业大学 | Tourmaline/titanium dioxide composite collosol and preparing method and use thereof |
| CN102836729A (en) * | 2012-09-06 | 2012-12-26 | 中国地质大学（北京） | Preparation of TiO2/schorlite composite photo-catalytic material |
| KR20130004777A (en) * | 2011-07-04 | 2013-01-14 | 이상철 | Environment-friendly multi-functional natural paint and the manufacturing method thereof |
| CN102895972A (en) * | 2012-10-17 | 2013-01-30 | 陕西科技大学 | Method for preparing negative ion material used for organic pollutant and sewage treatment and having photo-catalysis performance |
| CN104492674A (en) * | 2014-11-20 | 2015-04-08 | 东南大学 | Method for preparing graphene-based air conditioner filter net by spraying method |
| CN104906970A (en) * | 2015-06-08 | 2015-09-16 | 上海洁晟环保科技有限公司 | Light-transmitting, breathable and static electricity repellent PM2.5 air filter membrane and preparation method thereof |
| CN205876146U (en) * | 2016-06-08 | 2017-01-11 | 中健一生（北京）国际医学科技有限公司 | Antifog haze window screening of static separation |
-
2017
- 2017-04-01 CN CN201710218890.7A patent/CN107774241B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1420800A (en) * | 1999-10-15 | 2003-05-28 | Abb拉默斯环球有限公司 | Conversion of nitrogen oxides in presence of catalyst supported of mesh-like structure |
| CN1522954A (en) * | 2003-09-10 | 2004-08-25 | 河北工业大学 | Tourmaline/titanium dioxide composite collosol and preparing method and use thereof |
| KR20130004777A (en) * | 2011-07-04 | 2013-01-14 | 이상철 | Environment-friendly multi-functional natural paint and the manufacturing method thereof |
| CN102836729A (en) * | 2012-09-06 | 2012-12-26 | 中国地质大学（北京） | Preparation of TiO2/schorlite composite photo-catalytic material |
| CN102895972A (en) * | 2012-10-17 | 2013-01-30 | 陕西科技大学 | Method for preparing negative ion material used for organic pollutant and sewage treatment and having photo-catalysis performance |
| CN104492674A (en) * | 2014-11-20 | 2015-04-08 | 东南大学 | Method for preparing graphene-based air conditioner filter net by spraying method |
| CN104906970A (en) * | 2015-06-08 | 2015-09-16 | 上海洁晟环保科技有限公司 | Light-transmitting, breathable and static electricity repellent PM2.5 air filter membrane and preparation method thereof |
| CN205876146U (en) * | 2016-06-08 | 2017-01-11 | 中健一生（北京）国际医学科技有限公司 | Antifog haze window screening of static separation |
Non-Patent Citations (4)
| Title |
|---|
| LI YU ET AL.: "Investigating the synergistic effects in tourmaline/TiO2-basedheterogeneous photocatalysis: Underlying mechanism insights", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 余力: "超声助电气石类芬顿及电气石负载TiO2光催化降解水中双酚A的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 方雪慧等: "气相中乙酸乙酯光解的光子效率: 波长和催化剂的影响", 《环境科学》 * |
| 高如琴等: "电气石对纳米二氧化钛结构及光催化性能的影响", 《硅酸盐学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993558A (en) * | 2018-08-13 | 2018-12-14 | 蒋黎婷 | A kind of preparation method of high-performance titanium dioxide optical catalyst |
| CN111604044A (en) * | 2020-06-30 | 2020-09-01 | 郑州大学 | Preparation and application of tourmaline/titanium dioxide composite photocatalyst sol |
| CN112010388A (en) * | 2020-08-18 | 2020-12-01 | 天津市职业大学 | Wastewater treatment device for photocatalytic degradation of organic pollutants for laboratory and use method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107774241B (en) | 2020-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11345616B2 (en) | Heterojunction composite material consisting of one-dimensional IN2O3 hollow nanotube and two-dimensional ZnFe2O4 nanosheet, and application thereof in water pollutant removal | |
| CN103433060B (en) | Core-shell TiO2/ZnIn2S4 composite photocatalyst and preparation method and application thereof | |
| CN102658130B (en) | Preparation method of Ru-Pd bimetal-supported TiO2 nanotube photocatalyst and application thereof | |
| CN107952464B (en) | Novel photocatalytic material and double-photocatalytic-electrode self-bias pollution control system | |
| WO2021212923A1 (en) | P-n heterojunction composite material supported on surface of nickel foam, preparation method therefor and use thereof | |
| CN106732738A (en) | A kind of Graphene/g C3N4Three-dimensional network laminated film and its preparation and application | |
| CN102861567B (en) | Floating type BiVO4/floating bead composite photocatalyst and preparation method and application thereof | |
| CN101966452B (en) | Method for preparing visible light-responded LaVO4 and TiO2 composite nanotube | |
| CN101780405A (en) | Preparation method of boron-doped titanium dioxide visible-light responsive photocatalyst | |
| CN107774241A (en) | A kind of TiO2/ tourmaline composite photo-catalyst and TiO2/ tourmaline gauze | |
| US20190308231A1 (en) | A novel method and a sand/water remediation system with a photocatalytic fuel cell | |
| CN109675607A (en) | Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material | |
| CN109453792B (en) | Preparation method of sulfide heterojunction material resistant to photo-corrosion in photo-Fenton reaction | |
| CN110252410A (en) | A kind of Three-element composite photocatalyst, preparation method and application | |
| CN105797762A (en) | Photocatalytic ceramsite as well as preparation method and application thereof | |
| CN105170115A (en) | Preparation method and applications of ternary polyaniline-titanium dioxide-hollow bead composite nano material | |
| Xu et al. | Synthesis and characterization of pyrochlore Bi2Sn2O7 doping with praseodymium by hydrothermal method and its photocatalytic activity study | |
| CN215996170U (en) | Device for enhancing formaldehyde removal efficiency and service life through catalytic oxidation of manganese oxide by electric field | |
| CN113181912B (en) | Cu (copper) alloy 2 O-TiO 2 Composite photocatalyst, preparation method and application thereof | |
| CN108998962A (en) | A method of the fabricated in situ titanium dioxide nano-particle directly on fabric fibre | |
| Zhou et al. | Efficient adsorption‐photocatalysis activity of ternary ZnO‐Sm2O3‐MgO co‐modified biochar for dye removal | |
| CN110585905B (en) | Fuel cell device for photocatalytic degradation of oil smoke and working method thereof | |
| CN103301825B (en) | Photocatalyst of titanium oxide nanosheet-coated flay ash microsphere | |
| Tada et al. | Visible light-responsive radial TiO 2 mesocrystal photocatalysts for the oxidation of organics | |
| CN104841416A (en) | Preparation method for novel square flaky bismuth borate oxide photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |