CN107744825A - A kind of WO3/g‑C3N4B photochemical catalysts are constructed and its prepared and apply - Google Patents
A kind of WO3/g‑C3N4B photochemical catalysts are constructed and its prepared and apply Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 27
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- 230000015556 catabolic process Effects 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 22
- 229910052796 boron Inorganic materials 0.000 claims description 20
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- -1 sodium tetraphenylborate Chemical compound 0.000 claims description 11
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004807 desolvation Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000000103 photoluminescence spectrum Methods 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229960000789 guanidine hydrochloride Drugs 0.000 claims 1
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 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 abstract description 14
- 229940012189 methyl orange Drugs 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000002131 composite material Substances 0.000 description 18
- 230000001699 photocatalysis Effects 0.000 description 14
- 239000011941 photocatalyst Substances 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
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- 239000003708 ampul Substances 0.000 description 5
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- 238000010521 absorption reaction Methods 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 4
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- 238000002474 experimental method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
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- 230000000875 corresponding effect Effects 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 229910004333 CaFe2O4 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 230000002079 cooperative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical compound O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of WO3/g‑C3N4B photochemical catalysts are constructed and its prepared and apply, the WO3/g‑C3N4The method that B photochemical catalysts are calcined with water-bath is made, and it has preferable catalytic degradation effect to organic dyestuff, particularly azo organic dyestuff, such as methyl orange under visible light.
Description
Technical field
The invention belongs to field of photocatalytic material, is related to a kind of composite photo-catalyst and its system for administering waste water from dyestuff pollution
Preparation Method.
Background technology
g-C3N4With its photocatalytic activity is higher, stability is good, cost of material is cheap, especially without metal this protrusion
Advantage, a kind of new catalysis material is made it, however, single phase catalyst generally urges its light because quantum efficiency is low
It is not ideal enough to change performance.Because of g-C3N4Material photo-generate electron-hole recombination rate is higher, causes its catalytic efficiency relatively low, so as to
Limit its application in terms of photocatalysis.In order to improve g-C3N4Catalytic activity, recent years, people have studied a lot
Method of modifying.To g-C3N4The nonmetalloid being modified is including S, N, C, B, F, P etc., it is considered that these nonmetalloids
C, N in 3-s- triazine structural units, H element are instead of, so as to form g-C3N4Lattice defect causes photo-generate electron-hole pair
Efficiently separated, effectively improve its photocatalysis performance.Zhang etc. mixes dicyandiamide with BmimPF6 (ionic liquid), warp
P doping g-C is obtained after crossing high-temperature calcination3N4Catalyst, show that P element instead of C in construction unit through XPS analysis, a small amount of P mixes
Although miscellaneous can not change g-C3N4Structure, still, it substantially changes g-C3N4Electronic structure, photogenerated current is also obvious high
In not adulterating g-C3N4.Yan etc. is prepared for B doping g-C using the mixture of heat resolve melamine and boron oxide3N4, pass through
XPS spectrum analyses show that B instead of g-C3N4H in structure, photocatalytic degradation of dye research show B doping while improved to urge
Absorption of the agent to light, therefore, rhodamine B photocatalytic degradation efficiency is also improved.Liu etc. is by g-C3N4In H2In S atmosphere in
450 DEG C of calcinings are prepared for unique electronic structure S element dopings g-C3N4CNS catalyst, XPS analysis show S instead of
g-C3N4N in structure.As λ ＞ 300 and 420nm, S adulterates g-C3N4Photocatalysis Decomposition aquatic products hydrogen catalysis efficiency is respectively than single g-
C3N4Improve 7.2 and 8.0 times.Wang etc. reports B, F doping g-C3N4Research, they use NH4F is made as F sources and DCDA in F
Element doping g-C3N4Catalyst (CNF).Its result of study shows that F elements have mixed g-C3N4Skeleton in, form C-F keys,
Make a portion sp2C is converted into sp3C, so as to cause g-C3N4Planar structure is irregular.In addition, with F element doping quantity
Increase, absorption regions of the CNF in visible region also expands therewith, and its corresponding band-gap energy is dropped to by 2.69eV
2.63eV.Later, they used BH again3NH3The g-C of B element doping is prepared as boron source3N4Catalyst (CNB), hair is characterized to it
Existing B element incorporation instead of g-C3N4C element in construction unit.Lin etc., as B sources, is mixing the same of B using tetraphenylboron sodium
When, and because the effect of benzene leaving group causes g-C3N4Laminate structure is formed, the thickness of its layer is 2~5nm, reduces photoproduction electricity
Son reaches the energy of consumption required for catalyst surface, therefore improves photocatalysis efficiency.
Tungstic acid (WO3) there are many potential applications：Energy conversion device, virally inactivated and noxious pollutant drop
Solution.In recent years, the composite quilt of two kinds of semiconductors of different energy gaps is used for the combination for suppressing electronics and hole and understands photoproduction
The directionality transfer of carrier.Although some composite catalysts such as TiO2/WO3、CaFe2O4/WO3Add to a certain extent
WO3Catalytic activity, but the synthesis step of these composite catalysts is always too complicated and can not be extended and be applied in practice.
By simple infusion process by the Fe of zero dimension2O3WO of the Nanoparticle Modified in three-dimensional layered framework3Surface on, it is a kind of new
Composite photo-catalyst i.e. successfully synthesis.As expected, Fe2O3/WO3Composite photo-catalyst shows under visible light illumination
Show than pure WO3Higher catalytic activity.Result of study shows, improves the activity of photochemical catalyst, and maximally efficient method is
The semiconductors coupling of binary, after two kinds of different semiconductors progress are compound, photo-generated carrier can be allowed between different energy levels
Transmitted and separated, so as to extend the life-span of carrier, so as to improve light-catalyzed reaction activity.
However, above-mentioned preparation method not only complex operation, cost of material is high, moreover, its light of obtained modified catalyst is urged
Change efficiency increase limitation, it is impossible to meet industrial requirements.
Therefore, needing exploitation one kind badly has high catalytic efficiency, and preparation method is simple, photochemical catalyst easy to use.
The content of the invention
In order to solve the above problems, present inventor has performed studying with keen determination, as a result find：Utilize the method for water-bath-roasting
By urea, sodium tetraphenylborate and tungstic acid reaction the synthesis WO of different quality3/g-C3N4B photochemical catalysts, it shines in visible ray
Penetrate down, there is preferable catalytic degradation effect to methyl orange dye, degradation efficiency may be up to 87.8%, so as to complete this hair
It is bright.
It is an object of the invention to provide following aspect：
In a first aspect, the present invention provides a kind of obtained WO3/g-C3N4The method of B photochemical catalysts, it is characterised in that this method
Comprise the following steps：
(1) itrogenous organic substance is mixed in a solvent with boron-containing compound, stirred；
(2) Tungstenic compound is added, continues to stir, desolvation, obtains solid I；
(3) solid I is calcined, cooled down after roasting, optionally crushed after cooling.
Second aspect, the present invention also provide the WO according to made from above-mentioned first aspect methods described3/g-C3N4B photocatalysis
Agent, it is characterised in that
It is that 450nm or so has emission peak in wavelength according to its photoluminescence spectra.
The third aspect, the photochemical catalyst that the present invention also provides described in above-mentioned second aspect are administering dye wastewater, particularly
Containing organic dyestuff, the application in terms of sewage especially containing azo organic dyestuff, gained photochemical catalyst shines in visible ray
Penetrate the lower degradation efficiency to methyl orange and be up to 87.8%.
Brief description of the drawings
Fig. 1 shows the XRD of photochemical catalyst sample provided by the invention；
Fig. 2 shows the UV-Vis DRS spectrogram of sample；
Fig. 3 shows the energy gap figure of sample；
Fig. 4 shows the photoluminescence spectra figure of sample；
Fig. 5 shows the liquid phase UV-visible spectrum of sample；
Fig. 6 shows the visible light catalysis activity figure of sample degradation methyl orange.
Embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations
To be clear, clear and definite.
The present invention described below.
According to the first aspect of the invention, there is provided a kind of obtained WO3/g-C3N4The method of B photochemical catalysts, it is characterised in that
This method comprises the following steps：
Step 1, boron-containing compound is mixed with itrogenous organic substance, stirred.
In the present invention, the boron-containing compound is sodium tetraphenylborate, ammonia borine (BH3NH3), diboron trioxide etc., enter
One step is preferably sodium tetraphenylborate.
In the present invention, the itrogenous organic substance refers to the small organic molecule containing nitrogen and carbon simultaneously, special
Do not refer to the nitrogenous small organic molecule that can be decomposed in a heated condition, it is both used as nitrogen source in graphite phase carbon nitride is prepared
Material is used as carbon source material again.
The inventors discovered that the use of carbon-nitrogen ratio is 1:3~3:The itrogenous organic substance of 1 small-molecular-weight is as raw material, preferably
The use of carbon-nitrogen ratio is 1:2 small-molecular-weight itrogenous organic substance is as raw material, such as cyanamide, dicyandiamide, melamine, urea, salt
Sour guanidine etc., preferably urea.
In step 1 of the present invention, the weight of the boron-containing compound and itrogenous organic substance is than the weight for boron-containing compound:
The weight of itrogenous organic substance=(2.0000~10.0000mg):10g, it is preferably (4.0000~8.0000mg):10g, such as
6.0000mg:10g。
Mixed the inventors discovered that itrogenous organic substance and boron-containing compound are placed in liquid-phase system, above-mentioned two can be made
Kind material mixing is abundant, WO made from roasting3/g-C3N4B photochemical catalyst patterns are homogeneous.
In step 1 of the present invention, boron-containing compound and itrogenous organic substance mixture are stirred, the present invention is to stirring
Method is not specially limited, the method that can use any one stirring in the prior art, such as mechanical agitation, electromagnetic agitation.
The present invention is not specially limited to the solvent of liquid-phase system where itrogenous organic substance and boron-containing compound, is preferably used
Water, more preferably deionized water, distilled water, further, it is preferable to be distilled water.
In step 1 of the present invention, the amount of solvent for use is nitrogen-containing compound：Solvent=1:(1~5), preferably 1：(1.5
~3), such as 1:1.5.
Step 2, Tungstenic compound is added into step 1, continues to stir, desolvation, obtains solid I；
The Tungstenic compound is the oxygenatedchemicals of tungsten, and preferably tungstic acid, sodium tungstate, wolframic acid etc. are further excellent
Elect tungstic acid as.
The weight of the nitrogen-containing compound and tungstenic organic matter is than the weight for Tungstenic compound:The weight of itrogenous organic substance
=(0.005~0.25):10, be preferably (0.010~0.20):10, more preferably 0.015:10,0.075:10,0.180:
10。
In step 2, desolvation temperature is 30~95 DEG C, preferably 45~85 DEG C, such as 80 DEG C.
The inventors discovered that remove liquid phase where the mixture of itrogenous organic substance, boron-containing compound and Tungstenic compound
Solvent in system can significantly shorten roasting time, and therefore, present invention selection removes itrogenous organic substance before roasting and containing zinc
Solvent in liquid-phase system where compound mixture, the present invention are not specially limited to the mode for removing solvent, prior art
Middle any mode for removing solvent can be used, and such as normal temperature volatilization, normal heating, vacuum distillation, the present invention is to removing
Temperature during solvent is also not specially limited, not make itrogenous organic substance, boron-containing compound and Tungstenic compound be decomposed into preferably,
Desolvation temperature is 30~95 DEG C, preferably 45~85 DEG C, such as 80 DEG C.
Step 3, solid I is calcined, cooled down after roasting, optionally crushed after cooling.
In step 3 of the present invention, the temperature for selecting roasting is 400 DEG C~650 DEG C, preferably 450 DEG C~600 DEG C, such as 550
℃.1~6h of selection of time of roasting, preferably 2~4h.
In the present invention, the solid obtained to roasting cools down, and is cooled to room temperature, to facilitate subsequent treatment and use,
The present invention is not specially limited to the method for cooling, can use the side that any one is cooled down to solid in the prior art
Method, as natural cooling and it is artificial force cooling method, preferably using natural cooling.
Optionally, the solid after cooling is crushed, the present invention is not specially limited to the mode of crushing, can be used
Any one mode crushed to solid particle in the prior art, such as grind.
In step 3 of the present invention, obtained WO3/g-C3N4B photochemical catalysts, according to its photoluminescence spectra, it is in wavelength
Emission peak be present in 450nm or so.
According to the third aspect of the invention we, the photochemical catalyst described in above-mentioned second aspect is also provided and is administering dye wastewater,
Particularly contain organic dyestuff, the application in terms of sewage especially containing azo organic dyestuff.In visible ray existence condition
Under, 87.8% can be up to Photocatalytic Degradation of Methyl Orange rate.
In the present invention, it is not bound by any theory, inventors believe that the WO3/g-C3N4B photochemical catalysts sample it
So it is mainly due to WO with high activity3With g-C3N4B interface cooperative effect promotes the separative efficiency of photo-generated carrier,
The absorption region and intensity of visible ray are improved, and then improves WO3/g-C3N4The photocatalytic activity of B photochemical catalysts.
According to WO provided by the invention3/g-C3N4B photochemical catalysts are constructed and its prepared and apply, and are had below beneficial to effect
Fruit：
(1) WO3/g-C3N4The photocatalytic activity of B photochemical catalysts is high, such as under visible ray existence condition, to first
Base orange light catalysis degradation modulus can be up to 87.8%；
(2) WO3/g-C3N4B photochemical catalysts can carry out photocatalysis in visible wavelength range, and the scope of application is wider
It is general；
(3) WO3/g-C3N4B photochemical catalysts are to contaminant degradation efficiency high in waste water, especially waste water from dyestuff, degraded
Thoroughly and the used time is short；
(4) method provided by the invention is easy to operate, and reaction condition is gentle, workable；
(5) method provided by the invention was entirely prepared without using poisonous and harmful substances as raw material or precursor compound
Journey is green, so as to avoid secondary pollution.
Embodiment
Embodiment 1
(1) 10.0000g urea and 6.0000mg sodium tetraphenylborates are accurately weighed with electronic balance in 100mL beakers, is added
Enter 15.00mL distilled water, stir.
(2) tungstic acid (WO that 0.015g is added in beaker is stated then up3), continue to stir.Then again in constant temperature
Water-bath is gently mixed under conditions of being 80 DEG C, until solution volatilizees completely, obtains solid I；
(3) and then by above-mentioned solid I it is transferred in the porcelain crucible of the closing cleaned up, is placed in chamber type electric resistance furnace,
550 DEG C are heated to 10 DEG C/min speed, 2h is calcined at 550 DEG C, closes chamber type electric resistance furnace, be cooled to room temperature, then take out
Crucible, 20min is ground in agate mortar, obtain powdered samples, be then charged into hermetic bag and seal preservation；Production code member is
5%WO3/g-C3N4B。
Embodiment 2
Experimental procedure is same as Example 1, and difference is that tungstic acid dosage used is different, tungstic acid in the present embodiment
Dosage is 0.0750g；Production code member is 25%WO3/g-C3N4B。
Embodiment 3
Experimental procedure is same as Example 1, and difference is that tungstic acid dosage used is different, tungstic acid in the present embodiment
Dosage is 0.1800g；Production code member is 60%WO3/g-C3N4B。
Comparative example
Comparative example 1
(1) 10.0000g urea and 6.0000mg sodium tetraphenylborates are accurately weighed with electronic balance in 100mL beakers, is added
Enter 15.00mL distilled water, stir.
(2) it is gently mixed under conditions of being and then again 80 DEG C in thermostat water bath, until solution volatilizees completely, obtains solid
I；
(3) and then by above-mentioned solid I it is transferred in the porcelain crucible of the closing cleaned up, is placed in chamber type electric resistance furnace,
550 DEG C are heated to 10 DEG C/min speed, 2h is calcined at 550 DEG C, closes chamber type electric resistance furnace, be cooled to room temperature, then take out
Crucible, 20min is ground in agate mortar, obtain powdered samples, be then charged into hermetic bag and seal preservation；Production code member is
g-C3N4B。
Experimental example
The XRD of the photochemical catalyst sample of experimental example 1 is characterized
This experimental example specimen in use is by comparative example, embodiment and pure g-C3N4It is made.
X-ray diffraction spectra (XRD) is measured using Bruker D8Advance types X-ray diffractometers (XRD), and point
Analyse the crystal phase structure of each catalyst powder.As a result it is as shown in Figure 1.Instrument parameter：Copper target (Cu K α (λ=0.154nm)) ray,
Ni optical filters, operating voltage 40kV, electric current 40mA, 2 θ of scanning range=10-60 °.
A shows pure g-C3N4XRD curves；
B shows g-C3N4B XRD curves；
C shows that the XRD curves of sample are made in embodiment 1；
D shows that the XRD curves of sample are made in embodiment 2；
E shows that the XRD curves of sample are made in embodiment 3；
F shows WO3XRD curves；
It will be seen from figure 1 that WO3/g-C3N4B photochemical catalysts appear in 23.1 °, 23.6 °, 24.4 °, 26.7 °, 28.9 °,
27.3 °, 33.3 °, 34.2 °, 41.8 °, 49.9 °, 55.9 ° of diffraction maximum corresponds to (002) respectively, (020), (200), (120),
(002), (112), (022), (220), (222), (140), (420) crystal face.With WO3The increase of content, the intensity of diffraction maximum
Gradually increase, illustrates that diffraction peak intensity is stronger, WO3Content is higher.Simultaneously it can be seen that content is 60% WO3Diffraction maximum
Position is offset slightly, this explanation WO3And g-C3N4B interphase interaction is very strong.
Corresponding (002) crystal face of the diffraction maximum of 2 θ=26.7 °, is g-C3N4B diffraction maximum, illustrates WO3And g-C3N4B's answers
Merge without change g-C3N4B structure.
The UV-Vis DRS spectral characterization of the photochemical catalyst sample of experimental example 2
Take a small amount of above-mentioned comparative example, embodiment catalyst sample, WO3And pure g-C3N4Sample, overflow using ultraviolet-visible
Reflecting spectrograph characterizes to each photochemical catalyst sample, test wavelength 300-700nm, as a result as shown in Figure 2.
A shows WO3The UV-Vis DRS curve of spectrum of sample；
B shows pure g-C3N4The UV-Vis DRS curve of spectrum of sample；
C shows that the UV-Vis DRS curve of spectrum of sample is made in comparative example；
D shows that the UV-Vis DRS curve of spectrum of sample is made in embodiment 1；
E shows that the UV-Vis DRS curve of spectrum of sample is made in embodiment 2；
F shows that the UV-Vis DRS curve of spectrum of sample is made in embodiment 3.
Figure it is seen that boron doped g-C3N4The B and composite photo-catalyst WO of synthesis3/g-C3N4B absorption characteristic
It is similar, illustrate WO in the composite photo-catalyst of preparation3Do not destroy g-C3N4B structure.
The energy gap figure of the photochemical catalyst sample of experimental example 3
This experimental example specimen in use includes WO3, pure g-C3N4, sample made from comparative example and embodiment.
As a result as shown in figure 3,
Fig. 3 (a) and Fig. 3 (b) is shown in the semiconductor energy gap for the catalyst sample that Tauc curves are calculated.g-
C3N4、g-C3N4B, 5%WO3/g-C3N4B, 25%WO3/g-C3N4B, 60%WO3/g-C3N4B energy gap is respectively 2.70
EV, 2.64eV, 2.53eV, 2.42eV, 2.50eV.It can be seen that the formation of composite semiconductor makes the energy band of semiconductor
Narrow, improve absorbability of the catalyst to light, significantly more efficient can utilize solar energy.
The band-gap energy (energy gap) of semiconductor is calculated by following formula：
α h ν=A (h ν-Eg)n/2
α is absorptivity, and h is general Krona constant, and ν is light frequency, and Eg is band-gap energy, and A is the constant of semi-conducting material.
N is constant, and the n values of Direct-type bandwidth material generally take 1, and the n values of indirect-type take 4.
The photoluminescence spectra figure of the photochemical catalyst sample of experimental example 4
This experimental example specimen in use includes g-C3N4, g-C3N4B, 25%WO3/g-C3N4B。
Operating method：Take g-C3N4, g-C3N4B, 25%WO3/g-C3N4B catalyst fineses are placed in sample cell on a small quantity, real
Test middle use and characterize the similar method for making sample tabletting of detection with UV-Vis DRS, as far as possible sample should be pressed fine and close,
To keep the smooth of sample surfaces, the photoluminescence performance of various catalyst samples, test wavelength are detected using XRF
Scope 420-620nm, as a result as shown in Figure 4.
As seen from Figure 4, in 450nm or so there is emission peak in three kinds of catalyst.Content is 25% WO3Complex light is urged
The emissive porwer of agent is much smaller than pure g-C3N4And g-C3N4B emissive porwer, this shows 25%WO3/g-C3N4B complex lights are urged
Agent can improve catalytic activity, and this is due to that composite photo-catalyst has higher electronics-hole separative efficiency.Semiconductor
The catalytic activity of photochemical catalyst is relevant with the recombination probability of photo-generate electron-hole pair, it is, in general, that the intensity of PL spectrum is smaller,
The recombination probability in light induced electron-hole pair is lower, and the catalytic activity of semiconductor light-catalyst is just higher.Therefore catalyst activity
Sequentially it is：25%WO3/g-C3N4B>g-C3N4B>g-C3N4.This measures catalyst activity sequence consensus with experiment.
The liquid phase ultraviolet-visible spectrum of the photochemical catalyst sample of experimental example 5 characterizes
WO is accurately weighed with assay balance3、g-C3N4B, 25%WO3/g-C3N4Each 0.0500g of B samples in quartz ampoule,
Numbering is 1,2,3, and small magneton of the same size is then put into each quartz ampoule, and finally measuring 40mL concentration with graduated cylinder is
5.000mg·L-1Methyl orange solution pour into respectively in three quartz ampoules.Open light reaction instrument door and be sequentially placed into three quartz ampoules,
Timing 30min, after the time arrives, sampling carries out next step experiment, then carries out photo-irradiation treatment to surplus solution, is sampled after 30min,
Take sample three times altogether according to previous step, and liquid phase purple is done respectively by pertinent instruments (wavelength parameter is arranged into 300-700nm)
External spectrum, as a result as shown in Figure 5.
Figure (a) shows WO3The liquid phase UV-visible spectrum of sample；
Figure (b) shows that sample g-C is made in comparative example 13N4B liquid phase UV-visible spectrum；
Figure (c) shows that the liquid phase UV-visible spectrum of sample is made in embodiment 2.
Fig. 5 is shown in WO3、g-C3N4B and 25%WO3/g-C3N4In the presence of B, MO (methyl orange) is in light degradation process
In with the time differentiation.From Fig. 5 (a) and 5 (b) as can be seen that MO light degradation process is very slow.After 2h, in WO3And g-
C3N4In the presence of B, MO degradation rates are very low.But from 5 (c) as can be seen that with to 25% WO3/g-C3N4B irradiation times
Increase, the absworption peak at 500nm is decreased obviously in 2h, illustrates 25%WO3/g-C3N4B composite material exhibits go out higher light
Catalytic activity.Further illustrating catalyst activity order is：25%WO3/g-C3N4B>g-C3N4B>g-C3N4。
The visible light catalysis activity measure of the photochemical catalyst sample of experimental example 6
Operating method：Accurately weigh 0.2000g WO respectively with assay balance3、 g-C3N4、g-C3N4B, 5%WO3/g-
C3N4B, 25%WO3/g-C3N4B, 60%WO3/g-C3N4B is in quartz ampoule, numbering 0 (reference), 1,2,3,4,5.In quartz ampoule
In sequentially add 40ml (5mg/L) methyl orange solution, then quartz ampoule is put into photochemical reaction instrument, dark reaction time
For 30min, centrifugation 20min takes supernatant liquor to measure absorbance A after dark reaction terminates0.Xenon source is opened, the reaction time is
2h, a sample, centrifugation 20min measurement absorbance As are taken every 0.5ht；
Degradation rate is calculated according to the calculation formula of degradation rate：
W (%)=(A0- At)/A0× 100%,
The visible light activity figure of different catalysts sample is drawn out according to gained degradation rate, as a result as shown in fig. 6, wherein,
A shows WO3The visible light catalysis activity of sample；
B shows pure g-C3N4The visible light catalysis activity of sample；
C shows that the visible light catalysis activity of sample is made in comparative example；
D shows that the visible light catalysis activity of sample is made in embodiment 1；
E shows that the visible light catalysis activity of sample is made in embodiment 2；
F shows that the visible light catalysis activity of sample is made in embodiment 3.
Fig. 6 shows the photocatalytic activity of different catalysts, and WO is have rated by methyl orange of degrading under visible light3/g-
C3N4The photo-catalysis capability of B composite photo-catalysts.From Fig. 6 it can be seen that：Under the irradiation of visible ray, pure WO3、g-C3N4、g-
C3N4B has certain catalytic activity.And all WO3/g-C3N4B composite photo-catalyst is all shown under the irradiation of visible ray
Than pure WO3、g-C3N4、g-C3N4The high photocatalytic activity of B samples.Work as WO3Content when reaching 25%, the complex light of preparation
Obvious increase is presented in degraded of the catalyst for MO (methyl orange), and 87.8% drop can be reached by radiation of visible light 2h
Solution.However, by WO in composite photo-catalyst3Content increase to 60%, the effect for the MO that degrades under the same conditions is without 25%
WO3Good degrading effect.The result is due to WO3In pure g-C3N4Aggregation in B is excessive, may cause the nanometer of semiconductor surface
Particle have impact on photocatalytic activity, and this causes light induced electron-hole separating effect to reduce, therefore the WO of high level3It is compound
The photocatalytic activity of catalyst reduces.So it is not WO3The higher catalytic effect of content is better, the WO in composite photo-catalyst3
Proper ratio and decentralization for improving pure g-C3N4B catalytic activity is critically important.Composite photo-catalyst significantly improves
Catalytic activity, this explanation WO3And g-C3N4Interaction during composite catalyst is formed be present in B；And in visible ray
Irradiation under, WO3And g-C3N4Degraded of the composite photo-catalyst that B is formed to MO has synergy.
The present invention is described in detail above in association with embodiment and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
A variety of equivalencing, modification or improvement can be carried out to technical solution of the present invention and embodiments thereof, these each fall within the present invention
In the range of.Protection scope of the present invention is determined by the appended claims.
Claims (10)
1. one kind prepares WO3/g-C3N4The method of B photochemical catalysts, it is characterised in that this method comprises the following steps：
(1) itrogenous organic substance is mixed in a solvent with boron-containing compound, stirred；
(2) Tungstenic compound is added into step 1, continues to stir, desolvation, obtains solid I；
(3) solid I is calcined, cooled down after roasting, optionally crushed after cooling.
2. according to the method for claim 1, it is characterised in that in step 1, the itrogenous organic substance refers to contain nitrogen simultaneously
The small organic molecule of element and carbon, preferably carbon-nitrogen ratio are 1:3~3:The itrogenous organic substance of 1 small-molecular-weight, preferably
Carbon-nitrogen ratio is 1:2 small-molecular-weight itrogenous organic substance, such as cyanamide, dicyandiamide, melamine, urea, guanidine hydrochloride, it is preferably
Urea.
3. method according to claim 1 or 2, it is characterised in that in step 1, the boron-containing compound is tetraphenyl borate
Sodium, ammonia borine, diboron trioxide etc., more preferably sodium tetraphenylborate.
4. according to the method for claim 1, it is characterised in that in step 2, the Tungstenic compound is the oxygen-containing chemical combination of tungsten
Thing, preferably tungstic acid, sodium tungstate, wolframic acid etc., more preferably tungstic acid.
5. the method according to one of claims 1 to 3, it is characterised in that in step 1, the boron-containing compound with it is nitrogenous
The weight of organic matter is than the weight for boron-containing compound:The weight of itrogenous organic substance=(2.0000~10.0000mg):10g, it is excellent
Elect as (4.0000~8.0000mg):10g, such as 6.0000mg:10g.
6. the method according to claim 1 or 4, it is characterised in that in step 2, the nitrogen-containing compound and tungstenic are organic
The weight of thing is than the weight for Tungstenic compound:The weight of itrogenous organic substance=(0.005~0.25):10, it is preferably (0.010
~0.20):10, more preferably 0.015:10,0.075:10,0.180:10.
7. the method according to one of Claims 1 to 5, it is characterised in that in step 1, solvent for use is water, is preferably gone
Ionized water, distilled water, more preferably distilled water；The amount of solvent for use is nitrogen-containing compound：Solvent=1:(1~5), preferably 1：
(1.5~3), such as 1:1.5；
In step 2, desolvation temperature is 30~95 DEG C, preferably 45~85 DEG C, such as 80 DEG C.
8. according to the method for claim 1, it is characterised in that in step 3,
The temperature of roasting is 400 DEG C~650 DEG C, preferably 450 DEG C~600 DEG C, such as 550 DEG C；Heating rate is 5~15 during roasting
DEG C/min, preferably 10 DEG C/min；And/or
The time of roasting is 1~6h, preferably 2~4h.
9. the method according to one of claim 1~8, it is characterised in that in step 3, obtained photochemical catalyst WO3/g-
C3N4B,
It is that 450nm or so has emission peak in wavelength according to its photoluminescence spectra.
10. photochemical catalyst according to claim 9 is administering dye wastewater, particularly contain organic dyestuff, especially contain
There is the application in terms of the sewage of azo organic dyestuff；In light-catalyzed reaction 120min, obtained photochemical catalyst is for first
The degradation efficiency of base orange is up to 87.8%.
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