CN102247877B - Preparation method of visible light catalyst - Google Patents
Preparation method of visible light catalyst Download PDFInfo
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- CN102247877B CN102247877B CN 201110129397 CN201110129397A CN102247877B CN 102247877 B CN102247877 B CN 102247877B CN 201110129397 CN201110129397 CN 201110129397 CN 201110129397 A CN201110129397 A CN 201110129397A CN 102247877 B CN102247877 B CN 102247877B
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- source compound
- visible light
- preparation
- light catalyst
- modifier
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 238000001354 calcination Methods 0.000 claims abstract description 39
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- 239000003607 modifier Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 claims description 5
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 24
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000012986 modification Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000007654 immersion Methods 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 21
- 239000000843 powder Substances 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000003915 air pollution Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- BNWPUUZJGBXAFM-UHFFFAOYSA-N azane oxalonitrile Chemical compound N.N#CC#N BNWPUUZJGBXAFM-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 formaldehyde, benzene series Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
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Abstract
The invention discloses a preparation method of a visible light catalyst. Compared with the prior art, the invention adopts inexpensive, non-toxic and harmless urea as the raw material, with no need for highly toxic raw materials. By controlling the calcination temperature, C3N4 can be prepared, thus being in favor of environment protection. The invention also provides a preparation method of a visible light catalyst, comprising the steps of: preparing C3N4 according to the above process; mixing the obtained C3N4 with a modifier in a solvent for reaction, drying the reaction product, thus obtaining the visible light catalyst. The modifier can be an Fe source compound, a Cu source compound, a Zn source compound, a V source compound, a W source compound, a Pt source compound, an Au source compound or a Pd source compound. The method of the invention employs an immersion method for C3N4 metal ion modification, so that metal ions can adsorb the C3N4 surface, thus inhibiting photoinduced charge recombination. Therefore, the visible light catalyst prepared by the preparation method provided in the invention has a high photo catalytic performance.
Description
Technical field
The present invention relates to technical field of chemistry, more particularly, relate to a kind of preparation method of visible light catalyst.
Background technology
Along with Chinese economic development, the use amount of various chemical addition agents is also in continuous increase in construction material and the upholster coating, room air pollution is more and more serious, organic concentration increases greatly in the room air, because the sealing of modern architecture thing is good, cause the room air pollution problem to become increasingly conspicuous simultaneously.At present, formaldehyde, benzene series thing VOCs such as (benzene,toluene,xylenes) (being called for short VOCs) pollution are the main pollution factors of room air, become the main research object that solves room air pollution.
Traditional indoor VOCs purification techniques adopts the method for charcoal absorption, and still, active carbon can only be transferred to solid phase from gas phase with pollutant, therefore has problems such as post processing and regeneration.Compare anatase type nano TiO with active carbon
2Catalyst at room temperature deep oxidation VOCs, seldom produce secondary pollution, have advantages such as stable chemical performance, wear resistance be good, in room air VOCs administers, show good prospect.Yet, as catalysis material, TiO
2Forbidden band wideer (3.2eV), only can absorb the ultraviolet light less than 387nm, low to solar energy utilization ratio; And the recombination rate height of its carrier, quantum yield is low, photocatalysis efficiency and lower to the utilization rate of sunshine, thus restricted its application aspect room air improvement.In order to solve TiO
2The problem that catalyst utilizes visible light, the correlative study personnel adopt doping method to make TiO
2Possess visible light activity, principle is: doped chemical is incorporated into TiO
2Intracell is introduced new energy level or is formed defective in lattice.Doped chemical influences the moving situation in light induced electron and hole, has changed TiO
2Band structure, make the TiO after the doping
2Under radiation of visible light, possesses photocatalytic activity.Though this method has been improved TiO
2Activity under visible light, but TiO made
2Descend at the photocatalytic activity of ultra-violet (UV) band, the doping ion also makes TiO
2The chemical stability variation of itself, thus limited its practical application.
In recent years, the correlative study personnel have prepared the photochemical catalyst with low energy gap width, as composite metal oxide, nitrogen oxygen metallide etc.In above-mentioned photochemical catalyst, has the C of layer structure
3N
4Be a kind of polymer semiconductor, its energy gap is 2.7eV, can significantly absorb visible light, has good visible light catalytic performance, can utilize visible light photocatalytic degradation environmental contaminants and photolysis water hydrogen, has broad application prospects.Reported a kind of C in the prior art
3N
4The preparation method, this method adopts that cyanogen ammonia or the cynoguanidine of severe toxicity are arranged is that presoma prepares C
3N
4, be unfavorable for environmental protection.
The inventor considers, a kind of preparation method of visible light catalyst is provided, and this method need not hypertoxic feedstock production and obtains C
3N
4
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of visible light catalyst, and this method need not hypertoxic raw material, prepares C
3N
4
The invention provides a kind of preparation method of visible light catalyst, may further comprise the steps:
Urea 300～700 ℃ of calcinings down, is obtained C
3N
4
Preferably, described calcining heat is 400～600 ℃.
Preferably, described calcining heat is 550 ℃.
Preferably, described calcination time is 0.1～10h.
Preferably, described calcination time is 2h.
The present invention also provides a kind of preparation method of visible light catalyst, may further comprise the steps:
Prepare C according to any described method of claim 1～5
3N
4
With the C that obtains
3N
4Mix in solvent with modifier, reaction, drying obtains visible light catalyst, and described modifier is Fe source compound, Cu source compound, Zn source compound, V source compound, W source compound, Pt source compound, Au source compound or Pd source compound.
Preferably, obtain also comprising behind the visible light catalyst:
With described visible light catalyst at 50～400 ℃ of following heat treatment 0.1～5h.
Preferably, described Fe source compound is ferric nitrate, iron chloride or ferric sulfate; Described Cu source compound is copper nitrate, copper sulphate, Schweinfurt green or copper chloride; Described Zn source compound is zinc nitrate, zinc sulfate, zinc acetate or zinc chloride; Described V source compound is metavanadic acid ammonia or vanadium chloride; Described W source compound is wolframic acid, wolframic acid ammonia or metatungstic acid ammonia; Described Pt source compound is chloroplatinic acid; Described Au source compound is gold chloride; Described Pd source compound is palladium bichloride or palladium nitrate.
Preferably, described C
3N
4With the mol ratio of described modifier be 100: (0.001～10).
Preferably, described solvent is ethanol or water.
The invention provides a kind of preparation method of visible light catalyst, may further comprise the steps: urea 300～700 ℃ of calcinings down, is obtained C
3N
4Compared with prior art, the present invention is raw material with cheap, nontoxic urea, need not hypertoxic raw material, prepares C by the control calcining heat
3N
4, be conducive to environmental protection.Experimental result shows that the present invention prepares C
3N
4, this C
3N
4Has higher visible light catalytic performance.
The present invention also provides a kind of preparation method of visible light catalyst, may further comprise the steps: prepare C according to technique scheme
3N
4With the C that obtains
3N
4Mix in solvent with modifier, reaction, drying obtains visible light catalyst, and described modifier is Fe source compound, Cu source compound, Zn source compound, V source compound, W source compound, Pt source compound, Au source compound or Pd source compound.Compared with prior art, the present invention utilizes infusion process to C
3N
4Carry out metal ion-modifiedly, adsorption of metal ions is at C
3N
4The surface, suppressed the compound of photogenerated charge, therefore, this visible light catalyst of preparation has higher photocatalysis performance.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, to do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below, apparently, accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the SEM picture of the visible light catalyst of the embodiment of the invention 1 preparation;
Fig. 2 is the XRD collection of illustrative plates of the visible light catalyst of the embodiment of the invention 2 preparations;
Fig. 3 is the uv-visible absorption spectra of the visible light catalyst of the embodiment of the invention 3 preparations;
Fig. 4 is the XPS collection of illustrative plates of the visible light catalyst of the embodiment of the invention 4 preparations;
Fig. 5 is the XRD collection of illustrative plates of the visible light catalyst of the embodiment of the invention 7 preparations;
Fig. 6 is the SEM picture of the visible light catalyst of the embodiment of the invention 8 preparations.
The specific embodiment
Below the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
The invention discloses a kind of preparation method of visible light catalyst, may further comprise the steps:
Urea 300～700 ℃ of calcinings down, is obtained C
3N
4
Calcining described in the present invention can be carried out under aerobic or oxygen free condition, and wherein, calcining heat is that the present invention prepares C
3N
4Key, too high or too low for temperaturely all can not obtain C
3N
4, described calcining heat is preferably 400～600 ℃, more preferably 500～600 ℃, most preferably is 550 ℃.Simultaneously, calcination time also is at preparation C
3N
4Essential condition in the process, described calcination time is preferably 0.1～10h, and more preferably 1～5h most preferably is 2h.
The C of the present invention's preparation
3N
4Have layer structure, energy gap is 2.7eV, can significantly absorb visible light, and its absorbing wavelength red shift has the visible light catalytic performance to 600nm.And, C
3N
4Have abundant avtive spot and specific area, therefore, in humidity, under the identical condition of conditions such as oxygen concentration, C
3N
4The visible light catalytic effect is C doped Ti O
21.2～3.0 times of visible light catalytic effect.In addition, at the C to the present invention preparation of continuous 8～48h
3N
4Use in, C
3N
4The photocatalysis effect stability, no deactivation phenomenom.The C of the present invention's preparation
3N
4In the process of VOCs such as degraded toluene, the non-secondary pollution thing generates.
Compared with prior art, the present invention is raw material with cheap, nontoxic urea, need not hypertoxic raw material, prepares C
3N
4Simultaneously, this method technology is simple, and cost of material is cheap, has reduced production cost, is easy to realize industrial applications.
The present invention also provides a kind of preparation method of visible light catalyst, may further comprise the steps:
Prepare C according to the described method of technique scheme
3N
4
With the C that obtains
3N
4Mix in solvent with modifier, reaction, drying obtains visible light catalyst, and described modifier is Fe source compound, Cu source compound, Zn source compound, V source compound, W source compound, Pt source compound, Au source compound or Pd source compound.
The visible light catalyst of technique scheme preparation is the C of modification
3N
4, the scope of the visible absorption spectrum of this catalyst is 400～700nm.C in the preparation modification
3N
4Process in, described C
3N
4Can also be commercial C
3N
4
According to the present invention, described solvent is preferably ethanol or water, makes reaction system be convenient to disperse and stir.Because water and ethanol is middle can the volatilization in dry run, therefore, water and consumption of ethanol are little to the light-catalysed performance impact of final preparation.
Described Fe source compound is preferably ferric nitrate, iron chloride or ferric sulfate; Described Cu source compound is preferably copper nitrate, copper sulphate, Schweinfurt green or copper chloride; Described Zn source compound is preferably zinc nitrate, zinc sulfate, zinc acetate or zinc chloride; Described V source compound is preferably metavanadic acid ammonia or vanadium chloride; Described W source compound is preferably wolframic acid, wolframic acid ammonia or metatungstic acid ammonia; Described Pt source compound is preferably chloroplatinic acid; Described Au source compound is preferably gold chloride; Described Pd source compound is preferably palladium bichloride or palladium nitrate.
C described in the present invention
3N
4Be preferably 100 with the mol ratio of described modifier: (0.001～10), more preferably 100: (0.01～8) most preferably is 100: (1～5).
Obtain also preferably including behind the visible light catalyst: with described visible light catalyst at 50～400 ℃ of following heat treatment 0.1～5h.Described heat treatment temperature is preferably 50～400 ℃, more preferably 50～400 ℃, most preferably is 50～400 ℃; Described heat treatment time is preferably 0.5～5h, and more preferably 1～4h most preferably is 2～3h.
The C of the modification of the present invention's preparation
3N
4Have abundant avtive spot and specific area, be conducive to strengthen the reaction mass transfer process, accelerate pollutant to the mass transfer of catalysis material, thus the C of this modification
3N
4Has higher photocatalysis efficiency.In addition, at the C to this modification
3N
4In the use of continuous 8～48h, its photocatalysis effect stability, no deactivation phenomenom, therefore, with the C of this modification
3N
4Be applied to the improvement of indoor air pollutants, problem such as it is not long service life to have solved general photochemical catalyst, and visible light activity is not high.The C of the modification of the present invention's preparation
3N
4Generated water and carbon dioxide in the process of VOCs such as degraded toluene, the non-secondary pollution thing generates.
The visible light catalyst of the present invention's preparation not only can be used for treating indoor air pollution, and in aspects such as water pollution control, photolysis water hydrogen, solar cell and catalytic carrier very big application potential is arranged also.
Compared with prior art, the present invention utilizes infusion process to C
3N
4Carry out metal ion-modifiedly, adsorption of metal ions is at C
3N
4The surface, suppressed the compound of photogenerated charge, therefore, this visible light catalyst of preparation has higher photocatalysis efficiency, its photocatalysis effect is C
3N
41.2～10.0 times.
In order to further specify technical scheme of the present invention, be described below in conjunction with the preferred embodiment of the invention of embodiment, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The chemical reagent that adopts in the following embodiment of the invention is commercial.
Embodiment 1
Take by weighing 10.0g urea and place crucible, calcine under aerobic conditions, calcining heat is 550 ℃, and calcination time is 2h, and cooling obtains C
3N
4Catalyst.
As shown in Figure 1, the C for preparing for the invention process
3N
4The SEM picture.
Embodiment 2
Take by weighing 10.0g urea and place crucible, calcine under oxygen free condition, calcining heat is 450 ℃, calcination time 4h, and cooling obtains C
3N
4Catalyst.
As shown in Figure 2, the C for preparing for present embodiment
3N
4The XRD collection of illustrative plates.
Embodiment 3
Take by weighing 10.0g urea and place crucible, calcine under aerobic conditions, calcining heat is 650 ℃, calcination time 1h, and cooling obtains C
3N
4Catalyst.
As shown in Figure 3, the C for preparing for present embodiment
3N
4Uv-visible absorption spectra, as can be seen from the figure, C
3N
4Visible light there is stronger absorption.
Embodiment 4
Take by weighing 10.0g urea and place crucible, calcine under aerobic conditions then, calcining heat is 550 ℃, and calcination time is 2h, and cooling obtains C
3N
4
The configuration molar concentration is 1% iron nitrate solution 100ml;
C with preparation
3N
4Mix stirring with described iron nitrate solution, dry under reduced pressure, obtain powder;
Described powder is placed crucible, and at 150 ℃ of following heat treatment 2h, cooling obtains C
3N
4/ Fe
1.0%.
As shown in Figure 4, the C for preparing for present embodiment
3N
4/ Fe
1.0The XPS collection of illustrative plates of %, the as can be seen from the figure existence of Fe.
Take by weighing 10.0g urea and place crucible, under oxygen free condition, calcine then, 450 ℃ of calcining heats, calcination time 4h, cooling obtains C
3N
4
The configuration molar concentration is 2.0% copper nitrate solution 100ml;
C with preparation
3N
4Mix stirring with described copper nitrate solution, dry under condition of normal pressure, obtain powder;
Described powder is placed crucible, and at 300 ℃ of following heat treatment 0.5h, cooling obtains C
3N
4/ Cu
2.0%.
Embodiment 6
Take by weighing 10.0g urea and place crucible, calcine under aerobic conditions then, calcining heat is 650 ℃, and calcination time is 1h, and cooling obtains C
3N
4
The configuration molar concentration is 1.5% zinc nitrate solution 100ml;
C with preparation
3N
4Mix stirring with described zinc nitrate solution, dry under condition of normal pressure, obtain powder;
Described powder is placed crucible, and at 100 ℃ of following heat treatment 3h, cooling obtains C
3N
4/ Zn
1.5%.
Take by weighing 10.0g urea and place crucible, calcine under aerobic conditions then, calcining heat is 550 ℃, and calcination time is 2h, and cooling obtains C
3N
4
The configuration molar concentration is 0.8% wolframic acid ammonia solution 100ml;
C with preparation
3N
4Mix stirring with described wolframic acid ammonia solution, dry under reduced pressure, obtain powder;
Described powder is placed crucible, and at 200 ℃ of following heat treatment 3h, cooling obtains C
3N
4/ W
0.8%.
As shown in Figure 5, the C for preparing for present embodiment
3N
4/ W
0.8The XRD collection of illustrative plates of %.
Take by weighing 10.0g urea and place crucible, under oxygen free condition, calcine then, 450 ℃ of calcining heats, calcination time 4h, cooling obtains C
3N
4
The configuration molar concentration is 0.5% metavanadic acid ammonia solution 100ml;
C with preparation
3N
4Mix stirring with described metavanadic acid ammonia solution, dry under condition of normal pressure, obtain powder;
Described powder is placed crucible, and at 80 ℃ of following heat treatment 5h, cooling obtains C
3N
4/ V
0.5%.
As shown in Figure 5, the C for preparing for present embodiment
3N
4/ V
0.5The SEM picture of %, as can be seen from the figure, the C of present embodiment preparation
3N
4/ V
0.5% is layer structure.
Embodiment 9
Take by weighing 10.0g urea and place crucible, calcine under aerobic conditions then, calcining heat is 650 ℃, and calcination time is 1h, and cooling obtains C
3N
4
The configuration molar concentration is 0.1% platinum acid chloride solution 100ml;
C with preparation
3N
4Mix stirring with described platinum acid chloride solution, dry under condition of normal pressure, obtain powder;
Described powder is placed crucible, and at 400 ℃ of following heat treatment 1h, cooling obtains C
3N
4/ Pt
0.1%.
Take by weighing 10.0g urea and place crucible, calcine under aerobic conditions then, calcining heat is 550 ℃, and calcination time is 2h, and cooling obtains C
3N
4
The configuration molar concentration is 0.3% chlorauric acid solution 100ml;
C with preparation
3N
4Mix stirring with described chlorauric acid solution, dry under reduced pressure, obtain powder;
Described powder is placed crucible, and at 100 ℃ of following heat treatment 2h, cooling obtains C
3N
4/ Au
0.3%.
Embodiment 11
Take by weighing 10.0g urea and place crucible, calcine under oxygen free condition, calcining heat is 450 ℃, and calcination time is 4h, and cooling obtains C
3N
4
The configuration molar concentration is 0.05% palladium nitrate solution 100ml;
C with preparation
3N
4Mix stirring with described palladium nitrate solution, dry under condition of normal pressure, obtain powder;
Described powder is placed crucible, and at 300 ℃ of following heat treatment 1h, cooling obtains C
3N
4/ Pd
0.05%.
Take by weighing 10.0g urea and place crucible, under aerobic conditions, calcine then, 650 ℃ of calcining heats, calcination time 1h, cooling obtains C
3N
4
The configuration molar concentration is 5.0% ferric chloride solution 100ml;
C with preparation
3N
4Mix stirring with described ferric chloride solution, dry under condition of normal pressure, obtain powder;
Described powder is placed crucible, and at 300 ℃ of following heat treatment 2h, cooling obtains C
3N
4/ Fe
5.0%.
The visible light catalyst that embodiment 1～12 is prepared carries out the photocatalytic activity test respectively:
Continuous Flow is adopted in test, and experiment condition is: the initial concentration of toluene is 1mg/m
3, relative humidity is 60%, oxygen content is 21%, catalyst consumption is 0.1g, it is the xenon lamp of 150W that light source adopts power, is the evaluation index of photocatalytic activity with the ratio of the first order reaction apparent speed constant in the photochemical catalytic oxidation process, and visible light activity is with unmodified C
3N
4Be benchmark, test result is as shown in table 1.
The results of property of the visible light catalyst that table 1 embodiment 1～12 prepares
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments herein.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the wideest scope consistent with principle disclosed herein and features of novelty.
Claims (2)
1. the preparation method of a visible light catalyst may further comprise the steps:
Urea 300～700 ℃ of calcinings down, is obtained C
3N
4
With the C that obtains
3N
4Mix in solvent with modifier, reaction, drying obtains visible light catalyst, and described modifier is Fe source compound, Cu source compound, Zn source compound, V source compound or W source compound; Described C
3N
4With the mol ratio of described modifier be 100:(0.001～10);
Described Fe source compound is ferric nitrate or ferric sulfate; Described Cu source compound is copper nitrate, copper sulphate or Schweinfurt green; Described Zn source compound is zinc nitrate, zinc sulfate, zinc acetate or zinc chloride; Described V source compound is metavanadic acid ammonia or vanadium chloride; Described W source compound is wolframic acid, wolframic acid ammonia or metatungstic acid ammonia;
With described visible light catalyst at 50～400 ℃ of following heat treatment 0.1～5h.
2. preparation method according to claim 1 is characterized in that, described solvent is ethanol or water.
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