CN106277039B - A kind of cellular SnO2Semiconductor light-catalyst and preparation method thereof - Google Patents
A kind of cellular SnO2Semiconductor light-catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN106277039B CN106277039B CN201610574693.4A CN201610574693A CN106277039B CN 106277039 B CN106277039 B CN 106277039B CN 201610574693 A CN201610574693 A CN 201610574693A CN 106277039 B CN106277039 B CN 106277039B
- Authority
- CN
- China
- Prior art keywords
- sno
- catalyst
- crucible
- acetone
- absolute ethyl
- 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.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000001413 cellular effect Effects 0.000 title claims abstract description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000004065 semiconductor Substances 0.000 claims abstract description 12
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 235000014121 butter Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 235000015165 citric acid Nutrition 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 229910020923 Sn-O Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 241001466460 Alveolata Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000256844 Apis mellifera Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of cellular SnO2Semiconductor light-catalyst and preparation method thereof, photochemical catalyst reaction raw materials include stannic chloride pentahydrate, natrium carbonicum calcinatum, acetone, absolute ethyl alcohol, and the mol ratio control of stannic chloride pentahydrate and natrium carbonicum calcinatum is 1:When 6, using simple maneuverable solid-phase synthesis, heating 2h synthesizes to obtain a kind of cellular SnO at 540 DEG C2.Preparation technology of the present invention is simple, easy to operate, using SnO made from 0.3g2In 60W days with after ultraviolet light 120min, to 300ml 50mg/LCr (VI) percent reduction up to 87.8%, it is clear that the catalyst effect of honeycomb shape is preferable, can remove Cr VI in water removal with low energy consumption.
Description
Technical field
The present invention relates to photochemical catalyst preparing technical field, specially a kind of cellular SnO2Semiconductor light-catalyst and its
Preparation method.
Background technology
Photocatalitic Technique of Semiconductor can carry out catalyzing manufacturing of hydrogen, oxygen processed, processing water pollutant, gradually development using sunshine
As an emerging green technology, wherein light source and photochemical catalyst is two key elements of photocatalysis technology application.
Semiconductor light-catalyst more typical at present is metal oxide and sulfide (TiO2、ZnO、SnO2、WO3、Fe3O4, CdS etc.),
And by the activity improvement of semiconductor obtain it is compound, doping, dye-sensitized semiconductor photochemical catalyst.
SnO2Most common structure is tetragonal crystal system rutile, SnO2Structure cell is body-centered-orthorhomic parallelepiped, by two Sn
Formed with four O atoms, lattice constant a=b=0.4737nm, c=0.3186nm, c/a=0.637, body-centered and drift angle are
Sn ions, ligancy 6, the ligancy of O ions is 3.Taguchi has found the SnO of sintering within 19622Ceramics are in air
Trace active gas is more sensitive, and stability is very high, is a kind of excellent gas sensitive;SnO2As negative temperature coefficient heat
Quick material, also it is widely applied industrial and medical etc.;In addition improving material nonlinearity coefficient, improving material
The research of voltage-dependent characteristic also has very considerable application prospect.SnO2Nano material has good photocatalysis performance, photo electric
Energy and air-sensitive performance etc., can be as the ideal material of environment purification, production display, solar cell, gas sensor etc..
SnO2It is after TiO as the typical n-type wide bandgap semiconductor materials that a kind of energy gap is 3.5-4.0eV2Afterwards
Most one of photochemical catalyst of future.SnO2Except having and TiO2Outside similar rutile structure, TiO can also be covered2Light
Spectral limit, with reference to the various excellent properties possessed, become after TiO2Most one of photochemical catalyst of future afterwards.
Some research shows the porous SnO prepared using interfacial reaction2Material has larger specific surface area, uses it for photocatalysis drop
Solve the methyl orange in the aqueous solution test result indicates that, in experiment condition porous SnO under the same conditions2The photocatalysis performance of material
Than Degussa P25TiO2More preferably.Conventional SnO2The synthetic method of nano material has:The hot method of water (or solvent), synthesis in solid state
Method, sol-gel process, chemical vapour deposition technique, template etc., has related SnO at present2The report of photochemical catalyst, but honeybee
Nest shape SnO2Semiconductor light-catalyst is not developed also at present.
The content of the invention
It is an object of the invention to provide a kind of cellular SnO2Semiconductor light-catalyst and preparation method thereof, with solution
State the problem of being proposed in background technology.
To achieve the above object, the present invention provides following technical scheme:A kind of cellular SnO2Semiconductor light-catalyst and
Its preparation method, photochemical catalyst reaction raw materials include stannic chloride pentahydrate, natrium carbonicum calcinatum, acetone, absolute ethyl alcohol.
Preferably, its preparation method comprises the following steps:
A, first sodium carbonate is placed in vacuum drying chamber and dried, 100 DEG C of drying box temperature setting;
B, 30mmol natrium carbonicum calcinatums are weighed and are placed on agate mortar, 1ml acetone is added dropwise, grinding 10min is thin to powder
It is greasy uniform;
C, after acetone completely volatilization, 10mmol stannic chloride pentahydrates is added in the reactant that step B is obtained, are tentatively stirred
Mixing 5min is mixed, 2ml absolute ethyl alcohols are added dropwise;
D, after being persistently fully ground 15min, the obtained reactants of step C is transferred in crucible, crucible is placed in Muffle furnace
In calcine 2h at 540 DEG C;
E, room temperature is naturally cooled to after question response terminates, takes out crucible, and adds deionized water immersion thereto;
F, will be precipitated again in crucible respectively with ionized water and absolute ethyl alcohol washing, suction filtration;
G, the sample for finally obtaining step F dries 4h in vacuum drying chamber, and drying box temperature is 80 DEG C, and grinding is standby
With.
Compared with prior art, the beneficial effects of the invention are as follows:Preparation technology of the present invention is simple, easy to operate, uses
SnO made from 0.3g2It is reachable to 300ml 50mg/L Cr (VI) percent reduction in 60W days with after ultraviolet light 120min
87.8%, it is clear that the catalyst effect of honeycomb shape is preferable, can remove Cr VI in water removal with low energy consumption.
Figure of description
Fig. 1 is SnO produced by the present invention2XRD spectra;
Fig. 2 is SnO produced by the present invention2FESEM figure;
Fig. 3 is SnO produced by the present invention2FTIR spectrograms;
Fig. 4 is SnO produced by the present invention2UV-Vis spectrograms;
Fig. 5 is SnO produced by the present invention2EgCurve map;
Fig. 6 is the stannic chloride pentahydrate of the present invention, natrium carbonicum calcinatum mol ratio is 1:6 SnO prepared2Photocatalytic activity
Curve map.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
The present invention provides a kind of technical scheme:A kind of cellular SnO2Semiconductor light-catalyst and preparation method thereof, light are urged
Agent reaction raw materials include stannic chloride pentahydrate, natrium carbonicum calcinatum, acetone, absolute ethyl alcohol.
The preparation method of the present invention comprises the following steps:
A, first sodium carbonate is placed in vacuum drying chamber and dried, 100 DEG C of drying box temperature setting;
B, 30mmol natrium carbonicum calcinatums are weighed and are placed on agate mortar, 1ml acetone is added dropwise, grinding 10min is thin to powder
It is greasy uniform;
C, after acetone completely volatilization, 10mmol stannic chloride pentahydrates is added in the reactant that step B is obtained, are tentatively stirred
Mixing 5min is mixed, 2ml absolute ethyl alcohols are added dropwise;
D, after being persistently fully ground 15min, the obtained reactants of step C is transferred in crucible, crucible is placed in Muffle furnace
In calcine 2h at 540 DEG C;
E, room temperature is naturally cooled to after question response terminates, takes out crucible, and adds deionized water immersion thereto;
F, will be precipitated again in crucible respectively with ionized water and absolute ethyl alcohol washing, suction filtration;
G, 4h is finally dried in vacuum drying chamber by what step F was obtained, drying box temperature is 80 DEG C, and grinding is standby.
The experiment of Cr VI in treatment with ultraviolet light water is carried out to photochemical catalyst produced by the present invention:Experiment uses laboratory certainly
The ultraviolet catalytic reactor of system, is mainly made up of 60w uviol lamps and magnetic force heating stirrer.This experiment is with 50mg/L heavy chromium
Sour potassium solution is as simulating pollution waste water.Specifically experimentation is:By 0.3g SnO2It is put into 300ml above-mentioned simulated wastewater
In, lucifuge stirring 1h at room temperature is placed on magnetic stirring apparatus, afterwards during illumination reaction, at regular intervals from burning
About 4mL suspensions are taken out in cup, clear liquid is filtrated to get by filter, each group clear liquid is determined using the hydrazine method of diphenyl phosphinylidyne two
The content of middle Cr (VI), test its maximum absorption wavelength in the hydrazine of diphenyl phosphinylidyne two and Cr (VI) violet complex formed
(λmax=540nm) place absorbance, and record experimental data.In the range of experimental concentration, Cr (VI) concentration and its absorbance
It is directly proportional, thus using equation below:
Cr (VI) degradation rate=(A0-At)/A0× 100%
The absorbance surveyed is changed into Cr (VI) degradation rate, so as to learn degradation effect, wherein:A0For illumination 0min
When etching solution absorbance, AtFor illumination tmin when etching solution absorbance.
To product SnO produced by the present invention2Carry out XRD analysis:As shown in figure 1, all diffraction maximums and tetragonal crystal system gold
Red stone structure SnO2Standard diagram it is consistent, no miscellaneous peak occurs, and shows that the purity of product is high.Pass through formula:
D=K λ/Bcos θ
Estimate SnO2Particle size be 4nm, wherein, D is crystallite dimension, and λ is X-ray wavelength, and B is the half-peak of diffraction maximum
Width, θ are the angle of diffraction, and K is Scherrer constants, often takes 0.9.
FESEM analyses are carried out to product produced by the present invention:As shown in Figure 2.Small of a small amount of nanometer as we can see from the figure
The cake mass that grain reunion forms, what is more presented is the cellular pore space structure in agglomerate body, and the diameter of cellular cavity exists
50nm-100nm.And SnO2It is during common hydro-thermal and synthesis in solid state to form nanometer little particle or short grained aggregate more,
The alveolate texture formed in the method for the invention.The formation of said structure can be from SnO2Reaction of formation mechanism explain;
SnO2Reaction mechanism be SnCl first4It is dissolved in its crystallization water, and following chemical reaction occurs:
Sn4++4H2O→Sn(OH)4+4H+
Sn4++4CH3CH2OH→Sn(OH)4+4CH3CH2 +
Sn(OH)4→SnO2+2H2O
Due to SnCl4Generation hydrolyzes and alcoholysis reaction forms unbodied Sn (OH)4, then Sn (OH) at high temperature4Hair
Raw dehydrating condensation and crystallization, finally give SnO2.When system acidity is relatively low, be advantageous to SnCl4Hydrolysis, and work as acidity
When higher, hydrolysis is restricted, obtained SnO2Negligible amounts, SnO2Exist with nano particle.The carbon added in the method
Sour sodium is a kind of strong base-weak acid salt, has certain alkalescence, can effectively adjust the pH of reaction system, control hydrolysis and alcoholysis
Journey, form the alveolate texture that the present invention synthesizes.
It is as shown in Figure 3 that FTIR spectrum analysis are carried out to product produced by the present invention:SnO2Middle Sn-O vibration performance peak is
660cm-1.667cm in Fig. 3-1It is O-Sn-O Sn-O stretching vibrations corresponding to neighbouring absworption peak;530cm-1The peak at place is then
Sn-O-H Sn-O stretching vibrations, 3421cm-1、1634cm-1The peak occurred at left and right is that the flexible of O-H shakes in physical absorption water
It is dynamic, flexural vibrations characteristic peak.
The UV-Vis of product produced by the present invention is analyzed:Test product SnO2UV-Vis DRS spectrum, and make
Use formula:
F(R∞)=(1-R∞)2/2R∞=α/S=AC/S
R∞=Rsample/RBaSO4
Absorption spectrum is translated into, from fig. 4, it can be seen that product SnO2There is very high light absorbs energy in ultraviolet region
Power.Wherein F (R∞), S, α, R, C and A be respectively Kubelka-Munk functions, scattering coefficient, absorption coefficient, reflectivity, absorbent
The concentration and absorbance of kind.SnO2It is direct band-gap semicondictor material, so the band gap magnitude (E of productg) direct band gap half can be used
The light absorbs theoretical formula of conductor:
α h ν=B (h ν-Eg)1/2
Wherein α is absorption coefficient, and B is the relevant constant of material person's character, and h ν are the energy of single photon.So in summary
Theory, with (F (R ∞) h ν)2For ordinate, (h ν) maps for abscissa, and gained diagram is shown in Fig. 5, and its tangent line is extended into F (R
After ∞)=0, estimation product band gap magnitude is 3.2eV.
Cr VI in treatment with ultraviolet light water is carried out to product produced by the present invention to test:With 300ml 50mg/L's
K2Cr2O7Solution is simulating pollution thing, respectively with the made SnO of 0.3g2Photochemical catalyst is in 60W days with carrying out light under ultraviolet light source
Catalytic degradation, experimental result are as shown in Figure 6.SnO in figure2Added in the system of the photocatalytic degradation simulating pollution thing of product
2ml citric acids, and line 0ml is then not to addition citric acid in photocatalytic process.By Fig. 6 to find out, SnO is added2Photocatalysis
Agent is obvious to Cr (VI) degradation effect compared to photochemical catalyst is not added;After UV illumination penetrates 120min, SnO2Photocatalysis
Degraded Cr (VI) efficiency is 87.8%.In addition, as seen from Figure 6, divide in photocatalytic process into light-catalyzed reaction system
Not plus 0ml and 2ml citric acids are to SnO2Photocatalysis effect has significant difference, and catalytic effect can improve after citric acid is added,
Because citric acid plays a part of hole agent for capturing.
Preparation technology of the present invention is simple, easy to operate, using SnO made from 0.3g2In daily 60W days ultraviolet light
After 120min, to 300ml 50mg/L Cr (VI) percent reduction up to 87.8%, it is clear that the catalyst effect of honeycomb shape
Preferably, Cr VI in water removal can be gone with low energy consumption.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of changes, modification can be carried out to these embodiments, replace without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (1)
- A kind of 1. cellular SnO2The preparation method of semiconductor light-catalyst, it is characterised in that:Photochemical catalyst reaction raw materials include knot Brilliant butter of tin, natrium carbonicum calcinatum, acetone, absolute ethyl alcohol, comprise the following steps:A, first sodium carbonate is placed in vacuum drying chamber and dried, 100 DEG C of drying box temperature setting;B, 30mmol natrium carbonicum calcinatums are weighed and are placed on agate mortar, 1mL acetone is added dropwise, grinding 10min is fine and smooth to powder It is even;C, after acetone completely volatilization, 10mmol stannic chloride pentahydrates are added in the reactant that step B is obtained, preliminary stirring is mixed 5min is closed, 2mL absolute ethyl alcohols are added dropwise;D, after being persistently fully ground 15min, the obtained reactants of step C is transferred in crucible, crucible is placed in Muffle furnace 2h is calcined at 540 DEG C;E, room temperature is naturally cooled to after question response terminates, takes out crucible, and adds deionized water immersion thereto;F, will be precipitated again in crucible respectively with ionized water and absolute ethyl alcohol washing, suction filtration;G, the sample for finally obtaining step F dries 4h in vacuum drying chamber, and drying box temperature is 80 DEG C, and grinding is standby.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610574693.4A CN106277039B (en) | 2016-07-21 | 2016-07-21 | A kind of cellular SnO2Semiconductor light-catalyst and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610574693.4A CN106277039B (en) | 2016-07-21 | 2016-07-21 | A kind of cellular SnO2Semiconductor light-catalyst and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106277039A CN106277039A (en) | 2017-01-04 |
CN106277039B true CN106277039B (en) | 2018-01-12 |
Family
ID=57651619
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610574693.4A Expired - Fee Related CN106277039B (en) | 2016-07-21 | 2016-07-21 | A kind of cellular SnO2Semiconductor light-catalyst and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106277039B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110918007B (en) * | 2019-11-04 | 2022-04-22 | 江苏一夫新材料产业技术研究院有限公司 | PVP polymerized SnO2-graphene aerogels and method for the production thereof |
CN113663708A (en) * | 2021-08-16 | 2021-11-19 | 中化学朗正环保科技有限公司 | High-efficiency photocatalytic material and preparation method and application thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102153133B (en) * | 2011-03-17 | 2012-10-17 | 扬州大学 | Method for preparing controllable ordered porous tin dioxide nano structures |
CN103739007B (en) * | 2013-12-30 | 2016-01-20 | 扬州大学 | The porous SnO 2 nanostructure that template synthesis size is controlled |
CN105749902B (en) * | 2016-01-25 | 2018-08-10 | 扬州大学 | A kind of high-efficiency single-phase SnO2The preparation method of photochemical catalyst |
-
2016
- 2016-07-21 CN CN201610574693.4A patent/CN106277039B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN106277039A (en) | 2017-01-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Yu et al. | Novel rugby-ball-like Zn3 (PO4) 2@ C3N4 photocatalyst with highly enhanced visible-light photocatalytic performance | |
CN102380367B (en) | Control synthetic method of high-visible-light-activity mixed crystal type BiVO4 photocatalysts | |
CN102060330B (en) | Method for synthetizing bismuth molybdate octahedral nanoparticle by microwave radiation heating | |
CN101177296A (en) | Method for preparing sheet porous structural ZnO nano powder | |
Astuti et al. | Studying impact of different precipitating agents on crystal structure, morphology and photocatalytic activity of bismuth oxide | |
CN107138167B (en) | A kind of preparation method of the multiphase hetero-junctions Nano cadmium sulphide of special appearance | |
CN110813300B (en) | Cobalt-zinc-loaded bimetallic nano-carbon material, preparation method thereof and application thereof in catalytic oxidation of magnesium sulfite | |
CN111604053A (en) | Ternary hydrotalcite photocatalyst and preparation method and application thereof | |
CN102631919B (en) | Preparation method of copper-titanium-oxide mesomorphism material | |
CN103041795A (en) | Preparation method of titanium dioxide photocatalyst | |
CN108298591B (en) | synthesis method and application of hexagonal iron titanate nanosheet material | |
CN110449155A (en) | The preparation of copper ion modified nano-titanium dioxide and characterizing method | |
CN106277039B (en) | A kind of cellular SnO2Semiconductor light-catalyst and preparation method thereof | |
Chen et al. | Synthesis of halloysite nanotubes supported Bi-modified BaSnO3 photocatalysts for the enhanced degradation of methylene blue under visible light | |
CN112028119B (en) | Anatase TiO with co-exposed {101}, {100} and {111} -crystal faces 2 Nanocrystal | |
Zhang et al. | One step in situ synthesis of Bi2S3/Bi2O2CO3/Bi3O4Cl ternary heterostructures with enhanced photocatalytic performance | |
CN105727922B (en) | A kind of Li adulterates SrTiO3The preparation method and product of ten octahedron nanometer particles | |
CN110639521A (en) | Preparation method of iron oxide dodecahedral nanocrystal catalyst with exposed high-index surface | |
CN106582726A (en) | Bi4o5Br2 hollow sphere and preparation method using micro-emulsion as template | |
CN113426461A (en) | Preparation method of silver-doped polycrystalline zinc ferrite photocatalytic nano material | |
CN102079539B (en) | ZnO nano powder in sheet uniform porous structure as well as preparation method and applications thereof | |
CN108816267A (en) | A kind of loess load nitrogen-doped zinc oxide photochemical catalyst and preparation method thereof | |
CN110803710B (en) | Method for preparing zinc oxide material based on surfactant-free microemulsion | |
Ma et al. | Solar-driven WO3· H2O/TiO2 heterojunction films immobilized onto bamboo biotemplate: Relationship between physical color, crystal structure, crystal morphology, and energy storage ability | |
Tolan et al. | Effect of bismuth doping on the crystal structure and photocatalytic activity of titanium oxide |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180112 Termination date: 20180721 |
|
CF01 | Termination of patent right due to non-payment of annual fee |