CN107715905A - A kind of photochemical catalyst CNU BA preparation and its application - Google Patents
A kind of photochemical catalyst CNU BA preparation and its application Download PDFInfo
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- CN107715905A CN107715905A CN201710978873.3A CN201710978873A CN107715905A CN 107715905 A CN107715905 A CN 107715905A CN 201710978873 A CN201710978873 A CN 201710978873A CN 107715905 A CN107715905 A CN 107715905A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 229940125717 barbiturate Drugs 0.000 claims abstract description 24
- 238000006731 degradation reaction Methods 0.000 claims abstract description 22
- 230000015556 catabolic process Effects 0.000 claims abstract description 21
- 239000000975 dye Substances 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002441 X-ray diffraction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 9
- 238000002329 infrared spectrum Methods 0.000 claims description 9
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004807 desolvation Methods 0.000 claims description 4
- -1 dicyanodiamine Chemical compound 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 238000010438 heat treatment Methods 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
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 2
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 29
- 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 12
- 229940012189 methyl orange Drugs 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000007598 dipping method Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000003921 particle size analysis Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 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
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 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
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease 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
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 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
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 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
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 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
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007811 spectroscopic assay Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/40—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
Abstract
The invention provides a kind of photochemical catalyst CNU BA preparation and its application, the photochemical catalyst CNU BA are made by the use of itrogenous organic substance with barbiturates as raw material and using dipping with the method being calcined, it is under visible light to organic dyestuff, particularly azo organic dyestuff, such as methyl orange have preferable catalytic degradation effect.
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 many method of modifying.To g-C3N4Enter
The modified nonmetalloid of row is including S, N, C, B, F, P etc., it is considered that these nonmetalloids instead of 3-s- triazine structures
C, N, H element in unit, so as to form g-C3N4Lattice defect causes photo-generate electron-hole to being efficiently separated, effectively to carry
Its high photocatalysis performance.
Zhang etc. mixes dicyandiamide with BmimPF6 (ionic liquid), and P doping g-C is obtained after high-temperature calcination3N4Urge
Agent, show that P element instead of C in construction unit through XPS analysis, although a small amount of P doping can not change g-C3N4Structure, but
It is that it substantially changes g-C3N4Electronic structure, photogenerated current is not also apparently higher than adulterating g-C3N4。
Yan etc. is prepared for B doping g-C using the mixture of heat resolve melamine and boron oxide3N4, by XPS spectrum
Analysis shows B instead of g-C3N4H in structure, photocatalytic degradation of dye research show B doping while improve catalyst to light
Absorption, therefore, rhodamine B photocatalytic degradation efficiency is also improved.
Liu etc. is by g-C3N4In H2It is prepared in S atmosphere in 450 DEG C of calcinings with 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-C3N4Light
Aquatic products hydrogen catalysis efficiency is catalytically decomposed respectively than single g-C3N4Improve 7.2 and 8.0 times.
Wang etc. reports B, F doping g-C3N4Research, they use NH4F element dopings g- is made as F sources and DCDA in F
C3N4Catalyst (CNF).Its result of study shows that F elements have mixed g-C3N4Skeleton in, form C-F keys, make wherein one
Divide sp2C is converted into sp3C, so as to cause g-C3N4Planar structure is irregular.In addition, with F element doping increasing numbers, CNF exists
Absorption region in visible region also expands therewith, and its corresponding band-gap energy drops to 2.63eV by 2.69eV.Later, they
BH is used again3NH3The g-C of B element doping is prepared as boron source3N4Catalyst (CNB), it is characterized and finds that B element incorporation instead of
g-C3N4C element in construction unit.
Lin etc. uses tetraphenylboron sodium as B sources, while B is mixed, and because the effect of benzene leaving group causes g-C3N4
Laminate structure is formed, the thickness of its layer is 2~5nm, reduces the energy that light induced electron reaches consumption required for catalyst surface,
Therefore photocatalysis efficiency is improved.
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 dipping and the method for roasting
By the organic monoacid of different quality and the photochemical catalyst CNU-BA of itrogenous organic substance reaction synthesis, it is right under visible light illumination
Methyl orange and methylene blue have preferable catalytic degradation effect, and degradation efficiency is respectively up to 81.06%, 89.02%, so as to complete
The present invention.
It is an object of the invention to provide following aspect：
In a first aspect, the present invention provides a kind of obtained photochemical catalyst CNU-BA method, it is characterised in that this method includes
Following steps：
(1) itrogenous organic substance and organic monoacid are mixed, stirred, dissolving, mixing is abundant, desolvation, crushes, obtains
To solid I；
(2) solid I is calcined, cooled down after roasting, optionally crushed after cooling.
Second aspect, the present invention also provide the photochemical catalyst CNU-BA according to made from above-mentioned first aspect methods described, its
In,
It is 810cm in wave number according to its infrared spectrum-1、1280cm-1、1375cm-1And 1649cm-1Nearby exist and absorb
Peak；And/or
It is obvious absorb in the range of 225nm~500nm be present in wavelength according to its UV-Vis DRS spectrogram
Peak.
In its XRD spectra, there is diffraction maximum in 2 θ=13.00 °, 27.40 °, and at 2 θ=27.40 ° peak intensity
Gradually die down and gradually broaden.
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 CNU-BA is can
See under light irradiation that there is preferable catalytic degradation effect to methyl orange and methylene blue, degradation efficiency respectively up to 81.06%,
89.02%.
Brief description of the drawings
Fig. 1 shows the XRD of photochemical catalyst sample provided by the invention；
Fig. 2 shows the Fourier transform infrared spectroscopy figure of sample；
Fig. 3 shows the UV-Vis DRS spectrogram of sample；
Fig. 4 .1 show the visible light catalysis activity block diagram of sample degradation methyl orange；
Fig. 4 .2 show the visible light catalysis activity block diagram of sample degradation methylene blue；
Fig. 5 .1 show the visible light catalysis activity figure of sample degradation methyl orange；
Fig. 5 .2 show the visible light catalysis activity figure of sample degradation methyl orange；
Fig. 6 shows the laser particle size analysis phenogram of sample.
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 photochemical catalyst CNU-BA method, it is characterised in that the party
Method comprises the following steps：
Step 1, itrogenous organic substance and organic monoacid are mixed, stirred, dissolving, mixing is abundant, desolvation, obtains
Solid I.
In the present invention, the organic monoacid is barbiturates.
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 as raw material, as cyanamide, dicyanodiamine, melamine, urea,
Guanidine hydrochloride etc., preferably urea.
In step 1 of the present invention, the weight of the organic monoacid and itrogenous organic substance is than the weight for organic monoacid:It is nitrogenous
The weight of organic matter=(0~0.5):10, be preferably (0.01~0.3):10, more preferably 0.01:10,0.03:10,0.05:
10,0.1:10 and 0.3:10.
The inventors discovered that when the weight of organic monoacid and itrogenous organic substance ratio is more than 0.3:When 10, organic monoacid content
Too high, the destruction to CNU molecular structures is excessive, its photocatalysis efficiency is reduced on the contrary；When organic monoacid with it is nitrogenous organic
The weight ratio of thing is less than 0.01:When 10, the modifying function of CNU molecules is failed to embody completely, the light of obtained photochemical catalyst is urged
Change efficiency to fail to be obviously improved, therefore, the weight ratio of present invention selection organic monoacid and itrogenous organic substance is preferably organic
The weight of weak acid:The weight of itrogenous organic substance=(0.01~0.3):10.
Mixed the inventors discovered that itrogenous organic substance and organic monoacid are placed in liquid-phase system, above two can be made
Material mixing is abundant, and CNU-BA photochemical catalysts pattern is homogeneous made from roasting.
In step 1 of the present invention, organic monoacid and itrogenous organic substance mixture are stirred, side of the present invention 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 organic monoacid, is preferably distilled
Water, deionized water, more preferably distilled water.The inventors discovered that remove liquid where itrogenous organic substance and organic monoacid mixture
Solvent in phase system can significantly shorten roasting time, and therefore, present invention selection removes itrogenous organic substance and had before roasting
Solvent in liquid-phase system where machine weak acid 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 and organic monoacid be decomposed into preferably, such as 30 DEG C~110
DEG C, more preferably 85 DEG C~100 DEG C, such as 95 DEG C.
In step 1 of the present invention, the mixture after desolvation is crushed, and the present invention is not specially limited to crushing, can
In a manner of using any one is crushed to solid particle in the prior art, such as grind.The inventors discovered that crushing makes
CNU-BA photochemical catalyst patterns are homogeneous made from obtaining, and catalytic efficiency is higher.
Step 2, the solid I that step 1 obtains is calcined, is cooled down after roasting, optionally crushed after cooling.
The inventors discovered that solid I is calcined, organic monoacid can decompose at high temperature with itrogenous organic substance.
In step 2 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
℃.The inventors discovered that under above-mentioned sintering temperature, organic monoacid can be decomposed sufficiently with nitrogen-containing compound, work as temperature
During more than 650 DEG C, the decomposition rate of organic monoacid and itrogenous organic substance is no longer obviously improved；It is organic when temperature is less than 400 DEG C
Weak acid decomposes insufficient with itrogenous organic substance, and organic weak acid or itrogenous organic substance residual is there may be in system, causes light to urge
The yield of agent reduces and the waste of raw material.
In step 2 of the present invention, heating rate is 5~15 DEG C/min, preferably 10 DEG C/min during roasting；The time of roasting
Select 2~5h, such as preferably 2~4h, 2h.The inventors discovered that under above-mentioned sintering temperature, solid I is calcined 2~5h, energy
Organic monoacid and itrogenous organic substance is fully decomposed, and make the material of generation sufficiently compound.When being more than 5 between upon firing,
Roasting time is long, and the photocatalysis efficiency of obtained photochemical catalyst reduces on the contrary；When being less than 2 hours between upon firing, during roasting
Between it is too short, the organic monoacid in solid I fails fully to decompose with itrogenous organic substance, makes the photocatalysis efficiency of obtained photochemical catalyst
It is not high.
In the present invention, the solid obtained to roasting cools down, and to facilitate subsequent treatment and use, the present invention is to cooling
Method be not specially limited, any one is cooled down to solid in the prior art method, such as natural cooling can be used
Method and artificial pressure 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.
According to the second aspect of the invention, there is provided obtained photochemical catalyst according to the method described above, it is above method step 2
In final obtained photochemical catalyst CNU-BA, be 810cm in wave number according to its infrared spectrum-1、1280cm-1、1375cm-1With
1649cm-1Nearby absworption peak be present.
It is 225nm~500nm in wavelength in the UV-Vis DRS spectrogram of gained photochemical catalyst according to the present invention
In the range of obvious absworption peak be present.
The inventors discovered that in gained photochemical catalyst CNU-BA, in BA insertion CNU graphite-phase Rotating fields, on the one hand, XRD
In, compound 2 θ=13.00 °, 27.40 ° appearance diffraction maximums, respectively with g-C3N4(100) and (002) crystal face it is corresponding, separately
On the one hand, the intensity at peak gradually dies down and gradually broadened at 2 θ=27.40 °, and display graphite-phase thickness of interlayer is obviously reduced, and says
Bright barbiturates (BA) content into graphite-phase interlayer increased.
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, photochemical catalyst respectively reaches 81.06%, 89.02% to the degradation efficiency of methyl orange and methylene blue.
According to photochemical catalyst CNU-BA provided by the invention and its preparation method and application, have the advantages that：
(1) photocatalytic activity of the photochemical catalyst CNU-BA is high, such as under visible ray existence condition, methyl orange and
The degradation efficiency of methylenum careuleum respectively reaches 81.06%, 89.02%；
(2) the photochemical catalyst CNU-BA can carry out photocatalysis in visible wavelength range, and the scope of application is more extensive；
(3) the photochemical catalyst CNU-BA is thorough to contaminant degradation efficiency high in waste water, especially waste water from dyestuff, degraded
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) 0.01g barbiturates is accurately weighed with electronic balance to be dissolved in the beaker equipped with 10mL distilled water, then is weighed
10g urea is added in above-mentioned beaker, and small magneton is put into beaker, and beaker is placed on into stirring on magnetic stirring apparatus accelerates mixing
Thing dissolves.Then beaker is placed on 100 DEG C of water bath methods in thermostat water bath, and is placed in agate mortar and pulverizes, obtained
Solid I；
(2) and then by above-mentioned solid I it is transferred in the porcelain crucible of dried and clean, is placed in Muffle furnace, with 10 DEG C/min's
Speed is heated to 550 DEG C, after being calcined 2h, is ground in agate mortar powdered, is then charged into hermetic bag and seals preservations, production
Product numbering is CNU-BA0.01。
Embodiment 2
Experimental procedure is same as Example 1, and difference is that barbiturates dosage used is different, barbiturates in the present embodiment
Dosage is 0.03g, production code member CNU-BA0.03。
Embodiment 3
Experimental procedure is same as Example 1, and difference is that barbiturates dosage used is different, barbiturates in the present embodiment
Dosage is 0.05g, production code member CNU-BA0.05。
Embodiment 4
Experimental procedure is same as Example 1, and difference is that barbiturates dosage used is different, barbiturates in the present embodiment
Dosage is 0.1g, production code member CNU-BA0.1。
Embodiment 5
Experimental procedure is same as Example 1, and difference is that barbiturates dosage used is different, barbiturates in the present embodiment
Dosage is 0.3g, production code member CNU-BA0.3。
Comparative example
Comparative example 1
(1) 0g barbiturates is accurately weighed with electronic balance it is dissolved in the beaker equipped with 10mL distilled water and stir, then weighs
10g urea is added in above-mentioned beaker, and small magneton is put into beaker, and beaker is placed on into stirring and dissolving on magnetic stirring apparatus.So
Beaker is placed on 100 DEG C of water bath methods in thermostat water bath afterwards, and is placed in agate mortar and pulverizes, obtains solid I；
(2) and then by above-mentioned solid I it is transferred in the porcelain crucible of dried and clean, is placed in Muffle furnace, with 10 DEG C/min's
Speed is heated to 550 DEG C, after being calcined 2h, is ground in agate mortar powdered, is then charged into hermetic bag and seals preservations, production
Product numbering is CNU.
Experimental example
The XRD of the photochemical catalyst sample of experimental example 1 is characterized
This experimental example specimen in use is made by comparative example and embodiment.
X-ray diffraction spectra (XRD) uses Bruker D8Advance types X-ray diffractometers (XRD), copper target (Cu K α (λ
=0.154nm)) ray, Ni optical filters, operating voltage 40kV, electric current 40mA, 2 θ of scanning range=10-80 °, sweep speed
8deg/min, analyze the crystal phase structure of sample.As a result it is as shown in Figure 1.
Curve a shows the X-ray diffraction spectra curve of embodiment 5；
Curve b shows the X-ray diffraction spectra curve of embodiment 4；
Curve c shows the X-ray diffraction spectra curve of embodiment 3；
Curve d shows the X-ray diffraction spectra curve of embodiment 2；
Curve e shows the X-ray diffraction spectra curve of embodiment 1；
Curve f shows the X-ray diffraction spectra curve of comparative example 1；
As seen from Figure 1, g-C3N4Highest peak in 2 θ=27.40 °, belong to g-C3N4(002) crystal face, its another spy
Peak is levied in 2 θ=13.00 °, corresponding g-C3N4(100) crystal face.We can also can be clearly seen that compound corresponds to peak from Fig. 1,
Its θ=13.00 ° of diffraction maximum 2,27.40 ° it is corresponding with (100) and (002) crystal face respectively, this just illustrate CNU-BA prepare very
Success.Also, Fig. 1 is shown with the increase of barbiturates (BA) content, at 2 θ=27.40 ° the intensity at peak gradually die down and
Gradually broaden, and its graphite-phase thickness of interlayer is obviously reduced.Its reason is probably derived from barbiturates insertion graphite-phase Rotating fields
In, destroy the original structure of graphite-phase.
The Fourier transform infrared spectroscopy of the photochemical catalyst sample of experimental example 2 characterizes
This experimental example specimen in use is made by comparative example and embodiment.
A small amount of above-mentioned photochemical catalyst sample is taken, is separately added into a small amount of potassium bromide powder, is ground to well mixed, is pressed into thin
Piece, infrared spectrum characterization is carried out to photochemical catalyst with FTIS, as a result as shown in Figure 2.
Curve a shows that the infrared spectrum curve of sample is made in comparative example 1；
Curve b shows that the infrared spectrum curve of sample is made in embodiment 1；
Curve c shows that the infrared spectrum curve of sample is made in embodiment 2；
Curve d shows that the infrared spectrum curve of sample is made in embodiment 3；
Curve e shows that the infrared spectrum curve of sample is made in embodiment 4；
Curve f shows that the infrared spectrum curve of sample is made in embodiment 5.
Fig. 2 shows the infrared spectrogram of different catalysts sample, and infrared spectrum is for measuring sample by continuous
During the Infrared irradiation of change frequency, the radiation of some frequencies of molecule absorption, and idol is caused by its oscillating movement or bending motion
The change of polar moment, cause transition of the energy level from ground state to excitation state, so as to form molecular absorption spectrum.
Analysis chart 2 is understood, in 810cm-1The absworption peak of vicinity belongs to the flexural vibrations of triazine ring skeleton.1280cm-1
And 1375cm-1Neighbouring absworption peak is graphite phase carbon nitride C-N characteristic absorption peak, 1649cm-1Neighbouring absworption peak is C
The stretching vibration peak of=N double bonds.
The UV-Vis DRS spectroscopic assay of the sample of experimental example 3
This experimental example specimen in use is made by comparative example and embodiment.
Each catalyst sample (powder) is characterized using UV-Vis DRS spectrometer, test wavelength 200-
700nm。
As a result as shown in figure 3, wherein,
Curve a shows that the UV-Vis DRS curve of spectrum of sample is made in embodiment 2；
Curve b shows that the UV-Vis DRS curve of spectrum of sample is made in embodiment 1；
Curve c shows that the UV-Vis DRS curve of spectrum of sample is made in embodiment 3；
Curve d shows that the UV-Vis DRS curve of spectrum of sample is made in embodiment 4；
Curve e shows that the UV-Vis DRS curve of spectrum of sample is made in embodiment 5；
Curve f shows that the UV-Vis DRS curve of spectrum of sample is made in comparative example 1.
From figure 3, it can be seen that UV-Vis DRS spectrogram shape before and after doping loads is almost similar, change
It is not it is obvious that not producing new collection of illustrative plates phenomenon；
It can also be seen that photochemical catalyst has an obvious absworption peak between wavelength 225-500nm from Fig. 3, and with
The trend gradually increased is presented in the growth of wavelength, light absorption value；
From Fig. 3 it can also be seen that compared with pure sample, CNU-BA types catalyst is in ultraviolet and utilization of the visibility region to light
Rate is all higher, and catalyst is to the strong and weak order of utilization rate of light：
(a)CNU-BA0.03>(b)CNU-BA0.01>(c)CNU-BA0.05>(d)CNU-BA0.1>(e)CNU-BA0.3>(f) CNU,
Generation red shift order：
(a)CNU-BA0.03>(b)CNU-BA0.01>(c)CNU-BA0.05>(d)CNU-BA0.1>(e)CNU-BA0.3>(f)CNU,
This is basically identical with catalyst activity.
The visible light catalysis activity measure of the sample of experimental example 4
This experimental example specimen in use is made by comparative example and embodiment.
Operating method：Accurately weigh respectively each 0.050g of photocatalyst powder made from above-mentioned comparative example and embodiment in
In quartz ampoule, numbering 1,2,3,4,5 and 6, it is 5mgL to be separately added into 40mL concentration successively-1Methyl orange solution (match somebody with somebody in advance
System), then a small magneton is put into each quartz ampoule respectively.Then quartz ampoule is put into photochemical reaction instrument, switch power supply,
Fan, stirring is opened, and ensure that each magneton fully rotates, lockup is write down while instrument door is shut.Holding
Under continuous stirring, dark treatment 30min, centrifuge tube of the 8mL solution after clean dried is taken respectively from the solution of each quartz ampoule
Middle centrifugation, then centrifuge tube is placed in high speed freezing centrifuge and centrifuges 20min, taken with ultraviolet-visible spectrophotometer measurement
Supernatant absorbance after sample centrifugation, and write down data A0.Dark treatment is completed and to open recirculated water after sampling, and opens visible ray
Light source, carry out illumination, a sample taken every 30min, repeat before the step of, sampled under light reaction three times, last result note
For At, degradation rate W is calculated according to following formula,
W (%)=(A0- At)/A0× 100%
The visible activity figure of 550 DEG C of catalyst samples is drawn out according to result of calculation, as a result such as Fig. 4 .1 and Fig. 4 .2, figure
Shown in 5.1 and Fig. 5 .2, wherein,
Fig. 4 .1 are the visible light catalysis activity block diagram of photocatalyst for degrading methyl orange, and Fig. 4 .2 are that photocatalyst for degrading is sub-
The visible light catalysis activity block diagram of methyl blue.
Fig. 5 .1 are the visible light catalysis activity figure of photocatalyst for degrading methyl orange, and Fig. 5 .2 are photocatalyst for degrading methylene
Blue visible light catalysis activity figure.
In Fig. 4 .1 and Fig. 4 .2,
Post 1 shows that the visible light catalysis activity of sample is made in comparative example 1；
Post 2 shows that the visible light catalysis activity of sample is made in embodiment 5；
Post 3 shows that the visible light catalysis activity of sample is made in embodiment 4；
Post 4 shows that the visible light catalysis activity of sample is made in embodiment 3；
Post 5 shows that the visible light catalysis activity of sample is made in embodiment 2；
Post 6 shows that the visible light catalysis activity of sample is made in embodiment 1.
In Fig. 5 .1 and Fig. 5 .2,
Curve a shows that the visible light catalysis activity of sample is made in comparative example 1；
Curve b shows that the visible light catalysis activity of sample is made in embodiment 5；
Curve c shows that the visible light catalysis activity of sample is made in embodiment 4；
Curve d shows that the visible light catalysis activity of sample is made in embodiment 3；
Curve e shows that the visible light catalysis activity of sample is made in embodiment 1；
Curve f shows that the visible light catalysis activity of sample is made in embodiment 2.
Dark treatment refers to closing lamp source；Illumination refers to opening lamp source.
From Fig. 4, Fig. 5 we can see that：Cloudy, turbid phase catalyst degradation rate is extremely low, and photoreaction stage is over time
Extension, the degree of catalyst degradation is from large to small.
It can also be seen that barbiturates, which is modified CNU, can effectively improve the degradation capability of its catalyst from Fig. 4, Fig. 5.Can be with
The degradation rate first increases and then decreases of the increase photochemical catalyst of barbiturates addition, synthesis ratio of the composite catalyst to presoma
Example has certain requirement, and when the addition of barbiturates is 0.03g, the degradation rate of photochemical catalyst reaches highest.
The diagram of CNU-BA degradation of methylene blue can also confirm the conclusion of CNU-BA degraded methyl oranges.It thereby it is assumed that,
Take the lead in increasing with the degraded for being continuously increased catalyst of barbiturates dosage reduces again, adds when barbiturates amount is 0.03g and drops
Solution rate highest, i.e. CNU-BA0.03Degradation rate is best, and compared with pure CNU, there is CNU-BA composite photo-catalysts higher light to urge
Change degraded methyl orange and methylene blue activity, wherein CNU-BA0.03The active highest of sample, under conditions of the experiment, CNU-
BA0.03Sample photo-catalytic degradation of methyl-orange and methylene blue degradation rate respectively reach 81.06% and 89.02%, and CNU-
BA0.03With good photocatalysis stability.
The laser particle size analysis of the sample of experimental example 5 characterizes
Prepare each catalyst sample, be then respectively adding injection port, be dissipating using light according to laser particle size analyzer
Principle is penetrated, to measure powder particles size.With CNU-BA0.03Exemplified by analyzed.As a result it is as shown in Figure 6.
Fig. 6 is catalyst sample laser particle size analysis phenogram.Scherrer formula：
Scherrer formula is the famous formula of XRD analysis crystallite dimension, and D=20.22um is calculated according to Scherrer formula, with
Gained laser particle size result is consistent, as shown in Figure 6.This illustrates that this experiment dipping obtains the granularity of sample particle group with roasting
It is smaller for particle diameter, so as to side confirmation dipping and the superiority of roasting.
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)
- A kind of 1. method for preparing photochemical catalyst CNU-BA, it is characterised in that this method comprises the following steps：(1) itrogenous organic substance and organic monoacid being mixed, stirred, dissolving, mixing is abundant, desolvation, crushes, consolidate Body I；(2) 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 organic monoacid is barbiturates.
- 3. method according to claim 1 or 2, it is characterised in that in step 1, the itrogenous organic substance refers to contain simultaneously There is the small organic molecule of nitrogen and carbon, preferably carbon-nitrogen ratio is 1:3~3:The itrogenous organic substance of 1 small-molecular-weight, It is preferred that carbon-nitrogen ratio is 1:2 small-molecular-weight itrogenous organic substance, such as cyanamide, dicyanodiamine, melamine, urea, guanidine hydrochloride, Preferably urea.
- 4. the method according to one of claims 1 to 3, it is characterised in that in step 1, the organic monoacid has with nitrogenous The weight of machine thing is than the weight for organic monoacid:The weight of itrogenous organic substance=(0~0.5):10, be preferably (0.01~0.3): 10, more preferably 0.01:10,0.03:10,0.05:10,0.1:10 and 0.3:10.
- 5. the method according to one of Claims 1 to 4, it is characterised in that in step 1, the solvent be distilled water, go from Sub- water, preferably distilled water.
- 6. the method according to one of Claims 1 to 5, it is characterised in that in step 2,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/orThe time of roasting is 2~5h, preferably 2~4h, more preferably 2h.
- 7. according to photochemical catalyst made from one of claim 1~6 methods described, it is characterised in that obtained photochemical catalyst It is 810cm in wave number according to its infrared spectrum for CNU-BA-1、1280cm-1、1375cm-1And 1649cm-1Nearby exist and absorb Peak.
- 8. photochemical catalyst according to claim 7, it is characterised in thatIt is to exist substantially in the range of 225nm~500nm in wavelength in the UV-Vis DRS spectrogram of the photochemical catalyst Absworption peak,In its XRD spectra, there is diffraction maximum in 2 θ=13.00 °, 27.40 °, and the intensity at peak is gradual at 2 θ=27.40 ° Die down and gradually broaden.
- 9. the application of the photochemical catalyst according to claim 7 or 8, for administering dye wastewater, particularly there is engine dyeing Material, the especially sewage containing azo organic dyestuff.
- 10. application according to claim 9, in light-catalyzed reaction 120min, obtained photochemical catalyst is for methyl The degradation efficiency of orange and methylene blue respectively reaches 81.06%, 89.02%.
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Application publication date: 20180223 |