CN107684922A - A kind of photochemical catalyst Zn g C3N4And its prepare and apply - Google Patents
A kind of photochemical catalyst Zn g C3N4And its prepare and apply Download PDFInfo
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- CN107684922A CN107684922A CN201710860281.1A CN201710860281A CN107684922A CN 107684922 A CN107684922 A CN 107684922A CN 201710860281 A CN201710860281 A CN 201710860281A CN 107684922 A CN107684922 A CN 107684922A
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- photochemical catalyst
- organic substance
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 239000000126 substance Substances 0.000 claims abstract description 31
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 230000015556 catabolic process Effects 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 15
- 239000000975 dye Substances 0.000 claims abstract description 15
- 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 claims abstract description 10
- 229940012189 methyl orange Drugs 0.000 claims abstract description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 24
- 238000006555 catalytic reaction Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000000103 photoluminescence spectrum Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 235000005074 zinc chloride Nutrition 0.000 claims description 12
- 239000011592 zinc chloride Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- -1 nitrogen-containing compound Chemical class 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000012153 distilled water Substances 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
- 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
- 239000005416 organic matter Substances 0.000 claims 1
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 239000011701 zinc Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 description 19
- 239000011941 photocatalyst Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000005215 recombination Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007791 liquid phase 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
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005284 excitation Effects 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
- 238000010348 incorporation Methods 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005424 photoluminescence Methods 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
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 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 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 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
- 229910021578 Iron(III) chloride Inorganic materials 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
- 238000000862 absorption spectrum Methods 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000356 contaminant 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
- 238000006471 dimerization reaction Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 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
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (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 photochemical catalyst Zn g C3N4And its prepare and apply, the photochemical catalyst Zn g C3N4By the use of itrogenous organic substance and zinc compound as raw material, it is made using the method for impregnation-calcination, 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 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 of benzene leaving group
Effect cause g-C3N4Laminate structure is formed, the thickness of its layer is 2~5nm, reduces light induced electron and reaches catalyst surface institute
The energy consumed is needed, therefore improves photocatalysis efficiency.
Metallic element doping and change g-C3N4The important means of electronic band structure.
Pan etc. predicts that metallic atom (Pd, Pt etc.) may be inserted into g-C by first-principles calculations3N4In nanotube, have
Effect improves g-C3N4Photo-generated carrier mobility, reduce its band gap and further expand g-C3N4Absorption to visible ray rings
Answer scope.Due to g-C3N4In electronegative N atoms can be interacted with cation, therefore g-C3N4With seizure cation
Ability, this contributes to metal ion to mix g-C3N4Skeleton in.
Wang etc. is with cyanamid dimerization and FeCl3For raw material, Fe has been synthesized by thermal polycondensation process3+The g-C of doping3N4。Fe3+Mix
It is miscellaneous to reduce g-C3N4Band gap, and expand g-C3N4To the absorption region of visible ray, the photochemical catalyst is used for visible ray
Activate H2O2The light-catalyzed reaction of mineralising rhodamine B, catalytic effect are notable.
On this basis, Ding seminars, which are also studied, confirms Fe3+、Mn3+、Co3+、Ni3+And Cu2+Mixed Deng transition metal ions
Enter g-C3N4Skeleton in can expand its absorption region to visible ray and effectively suppress photo-generate electron-hole it is compound.
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 dipping-roasting
By the zinc chloride and g-C of different quality3N4React the photochemical catalyst Zn-g-C of synthesis3N4, its under visible light illumination, to methyl
Orange dyestuff has preferable catalytic degradation effect, and degradation efficiency may be up to 84.2%, 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 Zn-g-C3N4Method, it is characterised in that this method bag
Include following steps：
(1) zinc compound is mixed in a solvent with itrogenous organic substance, stirred, dissolving, mixing is abundant, and removing is molten
Agent, dry, obtain solid I；
(2) the solid I that step 1 obtains is calcined, is cooled down after calcining, optionally crushed after cooling.
Second aspect, the present invention also provide the photochemical catalyst Zn-g-C according to made from above-mentioned first aspect methods described3N4,
Characterized in that,
It is 808cm in wave number according to its infrared spectrum-1、1300cm-1、1600cm-1And 2350cm-1Nearby exist and absorb
Peak；And/or
It is luminous signal be present in the range of 400nm~600nm 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 84.2%.
Brief description of the drawings
Fig. 1 shows the XRD of photochemical catalyst provided by the invention；
Fig. 2 shows the photoluminescence spectra figure of sample；
Fig. 3 shows the Fourier transform infrared spectroscopy figure of sample；
Fig. 4 shows the UV-Vis DRS spectrogram of sample；
Fig. 5 shows the visible light catalysis activity block diagram of sample degradation methyl orange；
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 photochemical catalyst Zn-g-C3N4Method, it is characterised in that should
Method comprises the following steps：
Step 1, zinc compound is mixed with itrogenous organic substance, stirred, dissolving, mixing is abundant, desolvation, does
It is dry, obtain solid I.
In the present invention, the zinc compound is zinc chloride, zinc sulfate etc., more preferably zinc chloride.
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 dicyandiamide.
In step 1 of the present invention, the weight of the zinc compound and itrogenous organic substance is than the weight for zinc compound:
The weight of itrogenous organic substance=(0.05~6.5):10, be preferably (1.0~6.5):10, more preferably 1.4:10,2.8:10,
4.2:10 and 5.6:10.
The inventors discovered that when the weight of zinc compound and itrogenous organic substance ratio is more than 6.5:When 10, zinc compound
Too high levels, Zn content is too high in obtained photochemical catalyst, and the destruction to CN molecular structures is excessive, makes its photocatalysis efficiency
Reduce on the contrary；When the weight of zinc compound and itrogenous organic substance ratio is less than 0.05:When 10, the content of zinc compound is too low,
Zn content is too low in obtained photochemical catalyst, the modifying function of CN molecules is failed to embody completely, the light of obtained photochemical catalyst
Catalytic efficiency fails to be obviously improved, and therefore, the weight ratio of present invention selection zinc compound and itrogenous organic substance is containing zinc
The weight of compound:The weight of itrogenous organic substance=(0.05~6.5):10.
Mixed the inventors discovered that itrogenous organic substance and zinc compound are placed in liquid-phase system, above-mentioned two can be made
Kind material mixing is abundant, Zn-g-C made from calcining3N4Photochemical catalyst pattern is homogeneous.
In step 1 of the present invention, zinc 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 zinc compound, is preferably used
Water, more preferably deionized water, distilled water, further, it is preferable to be deionized water.
In step 1 of the present invention, the amount of solvent for use is nitrogen-containing compound：Solvent=1:(4~10), preferably 1：(5~
8), such as 1:6.
The inventors discovered that the solvent in liquid-phase system where removing itrogenous organic substance and zinc compound mixture can
Significantly shorten calcination time, therefore, present invention selection removes where itrogenous organic substance and zinc compound mixture before calcination
Solvent in liquid-phase system, the present invention are not specially limited to the mode for removing solvent, and any removing is molten in the prior art
The mode of agent can be used, such as normal temperature volatilization, normal heating, vacuums distillation, and the temperature during solvent to removing of the invention is not yet
It is particularly limited to, not make itrogenous organic substance and zinc compound be decomposed into preferably, such as 30 DEG C~65 DEG C, more preferably 35 DEG C~
55 DEG C, such as 40 DEG C.In step 1, dried after desolvation, also for removing itrogenous organic substance and zinc compound before calcination
Solvent in mixture, to be advantageous to calcine, drying time is 3~28h, preferably 5~25h, such as 24h；Drying temperature is 60
~110 DEG C, preferably 70~85 DEG C.
Step 2, the solid I that step 1 obtains is calcined, is cooled down after calcining, optionally crushed after cooling.
In step 2 of the present invention, the temperature for selecting calcining is 400 DEG C~650 DEG C, preferably 450 DEG C~600 DEG C, such as 550
℃.The inventors discovered that under above-mentioned calcining heat, zinc compound can be decomposed sufficiently with nitrogen-containing compound, work as temperature
When degree is more than 650 DEG C, the decomposition rate of zinc compound and itrogenous organic substance is no longer obviously improved；When temperature is less than 400 DEG C,
Zinc compound decomposes insufficient with itrogenous organic substance, and zinc compound or itrogenous organic substance residual are there may be in system,
Causing the yield of photochemical catalyst reduces, and the waste of raw material.
In step 2 of the present invention, 2~6h of selection of time of calcining, such as preferably 3~5h, 4h.The inventors discovered that
Under above-mentioned calcining heat, solid I is calcined into 2~6h, zinc compound and itrogenous organic substance can be made fully to decompose, and generated multiple
The Zn-g-C of conjunction3N4.When being more than 6 between upon calcination, calcination time is long, and the photocatalysis efficiency of obtained photochemical catalyst drops on the contrary
It is low；When being less than 2 hours between upon calcination, calcination time is too short, and the zinc compound in solid I fails fully with itrogenous organic substance
Decompose, make the photocatalysis efficiency of obtained photochemical catalyst not high.
In the present invention, the solid obtained to calcining 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 2 of the present invention, obtained photochemical catalyst Zn-g-C3N4, it is 808cm in wave number according to its infrared spectrum-1、1300cm-1、1600cm-1And 2350cm-1Nearby absworption peak be present.
It is luminous signal be present in the range of 400nm~600nm in wavelength according to its photoluminescence spectra.
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, 84.2% 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 photochemical catalyst Zn-g-C3N4The institute of sample
To be mainly due to (1) zinc with high activity to g-C3N4It is compound constrained the compound of photo-generate electron-hole pair, so as to carry
The separative efficiency of electron-hole in its high composite photocatalyst, while its utilization ratio to light also has huge lifting,
And then improve Zn-g-C3N4The photocatalytic activity of catalyst；(2) zinc doping g-C3N4So that g-C3N4To visible absorption ability
(350-700nm) strengthens, and it absorbs band edge and moved to long wave direction.
According to novel photochemical catalyst Zn-g-C provided by the invention3N4And its prepare and apply, have the advantages that：
(1) the photochemical catalyst Zn-g-C3N4Photocatalytic activity it is high, such as under visible ray existence condition, to methyl
Orange light catalysis degradation modulus can be up to 84.2%；
(2) the photochemical catalyst Zn-g-C3N4Photocatalysis can be carried out in visible wavelength range, the scope of application is more extensive；
(3) the photochemical catalyst Zn-g-C3N4It is thorough to contaminant degradation efficiency high in waste water, especially waste water from dyestuff, degraded
The bottom and 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) 5.000g dicyandiamides are accurately weighed with electronic balance in 100mL beakers, add 30.00mL deionized water,
Then 0.7g zinc chloride (ZnCl is added2), add stirring magneton, stirring.Then again in the bar that thermostat water bath is 40 DEG C
Stirred under part, until solution volatilizees completely, obtain mixture, then put into air dry oven and dry, dry 24h, consolidate
Body I；
(2) and then by solid I it is transferred in the porcelain crucible cleaned up, covers crucible cover, be placed in chamber type electric resistance furnace,
550 DEG C are heated to 10 DEG C/min speed, 4h is calcined at 550 DEG C, closes chamber type electric resistance furnace, open the stove of chamber type electric resistance furnace
Mouthful, room temperature is naturally cooled to, then takes out crucible, is ground in agate mortar and obtains powdered samples, be then charged into hermetic bag
In seal preservation.
Embodiment 2
Experimental procedure is same as Example 1, and difference is that zinc chloride dosage used is different, zinc chloride dosage in the present embodiment
For 1.4g.
Embodiment 3
Experimental procedure is same as Example 1, and difference is that zinc chloride dosage used is different, zinc chloride dosage in the present embodiment
For 2.1g.
Embodiment 4
Experimental procedure is same as Example 1, and difference is that zinc chloride dosage used is different, zinc chloride dosage in the present embodiment
For 2.8g.
Comparative example
Comparative example 1
(1) 5.000g dicyandiamides are accurately weighed with electronic balance in 100mL beakers, add 30.00mL deionized water,
Add stirring magneton, stirring.Then stir under conditions of being again 40 DEG C in thermostat water bath, until solution volatilizees completely, obtain
Mixture, then put into air dry oven and dry, dry 24h, obtain solid I；
(2) and then by above-mentioned solid I it is transferred in the porcelain crucible cleaned up, covers crucible cover, be placed in box resistance
In stove, 550 DEG C are heated to 10 DEG C/min speed, 4h is calcined at 550 DEG C, closes chamber type electric resistance furnace, open chamber type electric resistance furnace
Fire door, naturally cool to room temperature, then take out crucible, in agate mortar grinding obtain powdered samples, be then charged into close
Preservation is sealed in envelope.
Experimental example
The XRD of the catalyst sample of experimental example 1 is characterized
The present embodiment specimen in use is made by comparative example and embodiment.
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：Cu-K α are radiated, tube voltage 36.00KV, pipe
Electric current is 20.00mA, and scanning range is 10-60 °, sweep speed 4deg/min.
Curve a shows that the XRD curves of sample are made in comparative example 1；
Curve b shows that the XRD curves of sample are made in embodiment 1；
Curve c shows that the XRD curves of sample are made in embodiment 2；
Curve d shows that the XRD curves of sample are made in embodiment 3；
Curve e shows that the XRD curves of sample are made in embodiment 4；
Fig. 1 respectively illustrate different quality than Zn-g-C3N4Composite catalyst and pure g-C3N4XRD.Analysis can
Know, a lines are g-C in Fig. 13N4Highest peak in 2 θ=27.40 °, belong to g-C3N4(002) crystal face, its another feature peak 2 θ=
12.7 °, corresponding g-C3N4(100) crystal face.After Zn load absorption, composite catalyst Zn-g-C3N4Due to graphite stack
Interference after load absorption, the characteristic peaks in 2 θ=27.40 ° are remarkably reinforced, and the characteristic peak in 2 θ=12.7 ° is widened.This
The Zn-g-C that explanation synthesis is obtained3N4Composite catalyst will not destroy raw catalyst g-C3N4Crystal structure.
The photoluminescence spectra measure of the sample of experimental example 2
This experimental example specimen in use is made by comparative example and embodiment.
A small amount of comparative example and embodiment catalyst sample (powder) is taken, various catalyst samples are tested using XRF
Photoluminescence performance.For the excitation wavelength used for 390nm, scanning range is 390-600nm.In experiment, glass should be used as far as possible
Sample is pressed fine and close by piece, and to keep the smooth of sample surfaces, and a sample at least twice, should ensure data by parallel testing
Validity.The photoluminescence performance of various catalyst samples is detected using XRF.
As a result as shown in Fig. 2 wherein,
Curve a shows that the photoluminescence spectra curve of sample is made in comparative example 1；
Curve b shows that the photoluminescence spectra curve of sample is made in embodiment 1；
Curve c shows that the photoluminescence spectra curve of sample is made in embodiment 2；
Curve d shows that the photoluminescence spectra curve of sample is made in embodiment 3；
Curve e shows that the photoluminescence spectra curve of sample is made in embodiment 4；
Photoluminescence spectra (PL) is to study semiconductor nano material electronic structure and the effective ways of optical property.Can
Disclose architectural characteristic and the photo-generated carriers (electron-hole pair) such as surface defect and the surface Lacking oxygen of semiconductor nano material
Separation and the information such as compound, so as to provide strong foundation with the high semiconductor functional material of utility to prepare.
Figure it is seen that there is emission peak, Zn-g-C in sample at 450 nm3N4Photochemical catalyst is much smaller than its pure phase
g-C3N4The emissive porwer of photochemical catalyst.In general theory, a conclusion can be obtained, be exactly its fluorescence signal it is stronger when,
The probability of recombination of electron-hole pair corresponding to it will become big, but corresponding photocatalytic activity will also diminish.With regard to this point
For analysis, Zn-g-C3N4Photochemical catalyst possesses higher electron-hole separative efficiency, so as to add its composite photo-catalyst
Catalytic efficiency.
It can further be seen from figure 2 that it is Zn-g-C in the range of 400-600nm in wavelength3N4Catalyst sample (powder) is shown
Strong and wide luminous signal.By photoluminescence spectrum intensity, we can know that the height of photo-generated carrier recombination rate.Can be with from Fig. 2
Find out, with pure g-C3N4Compare, Zn incorporation is compound so that Zn-g-C3N4The fluorescence spectrum of composite catalyst is in wavelength 450nm
The reduction of the intensity at the peak at place, illustrate that recombination probability of the compound rear light induced electron from Lacking oxygen to valence band reduces, and analysis chart 2 can
Know, (d) and (e) composite photocatalyst figure are very near, and its light induced electron and hole-recombination probability are minimum.It is it is generally believed that glimmering
Optical signal is stronger, and the recombination probability of photo-generated carrier (electron-hole pair) is higher, and photocatalytic activity is just corresponding lower.With regard to this
For point, Zn-g-C3N4Photochemical catalyst has higher electron-hole separative efficiency, improves the catalytic activity of catalyst, by
This infers that catalyst activity order is (a)<(b)<(c)<(d) ≈ (e), this catalyst activity order basic one with measuring
Cause.
The Fourier transform infrared spectroscopy measure of the catalyst sample of experimental example 3
This experimental example specimen in use is made by comparative example and embodiment.
Operating method：A small amount of above-mentioned comparative example and embodiment catalyst sample is taken, a small amount of potassium bromide powder is separately added into, grinds
It is milled to well mixed, is pressed into thin slice, infrared spectrum characterization is carried out to catalyst with FTIS, as a result as schemed
Shown in 3, wherein,
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；
Infrared spectrum is some frequencies of molecule absorption for measuring sample when by the Infrared irradiation of consecutive variations frequency
The radiation of rate, and cause by its oscillating movement or bending motion the change of dipole moment, cause jump of the energy level from ground state to excitation state
Move, so as to form molecular absorption spectrum.From Fig. 3, we can draw, Zn-g-C3N4The chemical constitution of composite photo-catalyst with it is pure
The g-C of phase3N4It is consistent, this shows that two samples should be identical or substantially similar in structure.Each catalyst is in 808cm-1
Stronger absworption peak is nearby respectively provided with, and the embodiment 3 represented in the absworption peak of these different photochemical catalysts with curve d is made
Photochemical catalyst to be most strong, this may have of a relatively high photocatalytic activity relevant with it.In addition in 808cm-1Absworption peak
The flexural vibrations of triazine ring are then belonged to, one can consider that triazine ring does not decompose.
The UV-Vis DRS spectral characterization of the photochemical catalyst sample of experimental example 4
A small amount of above-mentioned comparative example and embodiment catalyst sample is taken, each light is urged using UV-Vis DRS spectrometer
Agent sample is characterized, test wavelength 200-700nm, as a result as shown in Figure 4.
Curve a shows that the UV-Vis DRS curve of spectrum of sample is made in comparative example 1；
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 2；
Curve d shows that the UV-Vis DRS curve of spectrum of sample is made in embodiment 3；
Curve e shows that the UV-Vis DRS curve of spectrum of sample is made in embodiment 4.
As shown in Figure 4, UV-Vis DRS spectrogram shape before and after doping loads is almost similar, and change is not very
Substantially, new collection of illustrative plates phenomenon is not produced.The ultraviolet-visible that Fig. 4 illustrates corresponding to prepared different photochemical catalyst is inhaled
Receive spectrum.As seen from Figure 4, the absorption characteristic of composite photocatalyst and the g-C of pure phase are obtained after the zinc doping of synthesis3N4
The absorption characteristic formed is similar, and the composite photocatalyst that can obtain its formation does not destroy its g-C3N4Basic structure.
It can also be learnt by Fig. 4 simultaneously, Zn-g-C3N4Composite photocatalyst can increase photochemical catalyst to ultraviolet light and its is visible
The absorption efficiency of light, with the increase of zinc compound quantity, absorption of the composite photocatalyst to visible ray also can constantly strengthen.
It can also be seen that and pure g-C from Fig. 43N4Compare, Zn-g-C3N4Composite photocatalyst is in 350-600nm
Region has stronger absorbing properties, and at the same time ABSORPTION EDGE constantly moves to the direction of long wave.And with zinc compound quantity
It is constantly increasing, Zn-g-C3N4The absorption intensity of composite photocatalyst also can constantly be strengthened.This lives with the catalyst surveyed
Property is basically identical.
The visible light catalysis activity measure of the sample of experimental example 5
This experimental example specimen in use is made by comparative example and embodiment.
Operating method：Each 0.050g of photocatalyst powder made from above-mentioned comparative example and embodiment is accurately weighed respectively in five
In individual quartz ampoule, numbering 1,2,3,4,5, it is 5.00mgL to be separately added into 40mL concentration successively-1Methyl orange solution, and respectively
Add a small magneton.Quartz ampoule is put into photochemical reaction instrument, in the case where being stirred continuously, dark reaction 30min, sampling centrifugation,
Its absorbance A is determined respectively0；Visible lamp source, photo-irradiation treatment 30min are opened, sampling centrifugation twice, centrifuges 20min, surveyed every time
Obtain its absorbance At；
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 Figure 5 and Figure 6,
Wherein,
Fig. 5 is the visible light catalysis activity block diagram of photocatalyst for degrading methyl orange；
Fig. 6 is the visible light catalysis activity curve map of photocatalyst for degrading methyl orange.
A shows that the visible light catalysis activity of sample is made in comparative example 1；
B shows that the visible light catalysis activity of sample is made in embodiment 1；
C shows that the visible light catalysis activity of sample is made in embodiment 2；
D shows that the visible light catalysis activity of sample is made in embodiment 3；
E shows that the visible light catalysis activity of sample is made in embodiment 4.
From Fig. 5, Fig. 6 we can see that：The doping of zinc improves the degradation capability of catalyst.With regard to compound Zn-g-
C3N4For photochemical catalyst, the degradation rate of photochemical catalyst is with zinc and g-C3N4Quality ratio increase and first increases and then decreases.It is multiple
Closing synthesis ratio of the catalyst to presoma has certain requirement, and when the composite photocatalyst made from embodiment 3, its is right
The degradation rate answered reaches highest, i.e. photocatalytic activity representated by curve d.From Fig. 5, Fig. 6 can also be seen that it is compound after Zn-g-
C3N4Photochemical catalyst g-C of the catalytic activity than pure phase under visible light3N4Catalytic activity improve a lot because zinc
It is compound constrained photo-generate electron-hole it is compound, so as to improve the separation of electron-hole in its composite photocatalyst effect
Rate, while its utilization ratio to light also has huge lifting, this with before to being tied obtained by the sign of composite photocatalyst
Fruit is consistent, and embodies the superiority of composite photocatalyst.
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 photochemical catalyst Zn-g-C3N4Method, it is characterised in that this method comprises the following steps：
(1) zinc compound being mixed in a solvent with itrogenous organic substance, stirred, dissolving, mixing is abundant, desolvation,
Dry, obtain solid I；
(2) solid I is calcined, cooled down after calcining, optionally crushed after cooling.
2. according to the method for claim 1, it is characterised in that in step 1, the zinc compound is zinc chloride, sulfuric acid
Zinc etc., more preferably zinc chloride.
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, dicyandiamide, melamine, urea, guanidine hydrochloride, it is excellent
Elect dicyandiamide as.
4. the method according to one of claims 1 to 3, it is characterised in that in step 1, the zinc compound with it is nitrogenous
The weight of organic matter is than the weight for zinc compound:The weight of itrogenous organic substance=(0.05~6.5):10, it is preferably (1.0
~6.5):10, more preferably 1.4:10,2.8:10,4.2:10 and 5.6:10.
5. the method according to one of Claims 1 to 4, it is characterised in that in step 1, the solvent is water, is preferably gone
Ionized water, distilled water, more preferably deionized water；The amount of solvent for use is nitrogen-containing compound：Solvent=1:(4~10), preferably
For 1：(5~8), such as 1:6.
6. the method according to one of Claims 1 to 5, it is characterised in that in step 1, desolvation temperature is 30~65
DEG C, preferably 35~55 DEG C, such as 40 DEG C.
7. the method according to one of claim 1~6, it is characterised in that in step 1,
Drying time is 3~28h, preferably 5~25h, such as 24h；Drying temperature is 60~110 DEG C, preferably 70~85 DEG C.
8. the method according to one of claim 1~7, it is characterised in that in step 2,
The temperature of calcining 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 calcining
DEG C/min, preferably 10 DEG C/min；And/or
The time of calcining is 2~6h, preferably 3~5h, such as 4h.
9. the method according to one of claim 1~8, it is characterised in that in step 2, obtained photochemical catalyst Zn-g-
C3N4,
It is 808cm in wave number according to its infrared spectrum-1、1300cm-1、1600cm-1And 2350cm-1Nearby absworption peak be present；With/
Or
It is luminous signal be present in the range of 400nm~600nm in wavelength according to its photoluminescence spectra.
10. the application of photochemical catalyst made from the method according to one of claim 1 to 9, special for administering dye wastewater
It is not containing organic dyestuff, the especially sewage containing azo organic dyestuff；Preferably, in light-catalyzed reaction 90min, institute
Obtained photochemical catalyst is up to 84.2% for the degradation efficiency of methyl orange.
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