CN106179314B - A kind of multicomponent composite photo-catalyst and its preparation method and application - Google Patents
A kind of multicomponent composite photo-catalyst and its preparation method and application Download PDFInfo
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- CN106179314B CN106179314B CN201610529855.2A CN201610529855A CN106179314B CN 106179314 B CN106179314 B CN 106179314B CN 201610529855 A CN201610529855 A CN 201610529855A CN 106179314 B CN106179314 B CN 106179314B
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- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 11
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000012876 carrier material Substances 0.000 claims abstract description 6
- 239000003365 glass fiber Substances 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims description 3
- 239000003446 ligand Chemical group 0.000 claims description 3
- UBOOKRVGOBKDMM-UHFFFAOYSA-N 3h-imidazo[4,5-c]pyridine Chemical class C1=NC=C2NC=NC2=C1 UBOOKRVGOBKDMM-UHFFFAOYSA-N 0.000 claims description 2
- LJUQGASMPRMWIW-UHFFFAOYSA-N 5,6-dimethylbenzimidazole Chemical class C1=C(C)C(C)=CC2=C1NC=N2 LJUQGASMPRMWIW-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract 1
- 230000002153 concerted effect Effects 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
A kind of multicomponent composite photo-catalyst and its preparation method and application, includes the following steps：It takes organic ligand A and is dissolved in solution B, obtain clear solution, it is spare；Metallic compound C is added into clear solution, obtains mixed solution, it is spare；Carrier is put into mixed solution, MOFs/ carrier materials are obtained, it is spare；Metallic compound D is dissolved in organic solvent, then processed MOFs/ carrier materials are put into and are wherein loaded, it is spare；The material ageing for preparing gained is then dry, it calcines 3 ~ 5 hours, you can obtain composite photo-catalyst.The active component particles size of multicomponent composite photo-catalyst of the present invention is small, load capacity is high, be evenly distributed, photoresponse window is wide（Ultraviolet-visible）, the advantages that efficiency of light energy utilization is high, realize Multimetal oxide concerted catalysis, significantly improve the performance and application of photochemical catalyst, there is suitable industrialized production.
Description
Technical field
The present invention relates to photocatalysis to be used for environmental area, and in particular to a kind of multicomponent composite photo-catalyst and its preparation side
Method and application.
Background technology
In the 1990s, beginning attempt to photoactivation method removal organic exhaust gas in the world.Photocatalysis oxidation technique has
Quick and high efficient reaction, to pollutant complete decomposition and advantages of environment protection.But traditional loaded catalyst still has activity
Particle size poor controllability, active component easily reunite, photoresponse window narrows, the problems such as efficiency of light energy utilization is low.
Metal-organic framework (metal-organic frameworks, MOFs) material be by metal ion/cluster with it is organic
Ligand has the porous crystalline material of periodical multidimensional reticular structure by one kind that self assembling process hydridization generates, and has larger
Specific surface area, porosity and the microcosmic duct of abundant nanometer, as absorption, catalysis material show wide application prospect.
The unstability of MOFs multidimensional mesh skeletons structure under the high temperature conditions affects its application in terms of catalysis material preparation,
Therefore catalysis material of the exploitation based on MOFs technologies, which prepares new way, has important research significance and actual application value.
Invention content
The technical issues of solution：The present invention in order to promote the catalytic performance and photoresponse window of photochemical catalyst, with metal~
Organic backbone gives full play to the advantage of its three-dimensional porous structure as modified method so that photocatalytic activity component is uniformly spread
Into microcosmic duct.MOFs is organic framework structured in high-temperature calcination process simultaneously is carbonized, and ultimately forms with the original positions MOFs
The compound catalysis material of multicomponent that metal oxide and photocatalytic activity oxide are highly coupled.
Technical solution：A kind of preparation method of multicomponent composite photo-catalyst, includes the following steps：(1) organic ligand A is taken
And be dissolved in solution B, 10~30min is stirred at ambient temperature, obtains clear solution, it is spare；The organic ligand A is
Trimesic acid, terephthalic acid (TPA), trimellitic acid, 5- imidazole radicals -1,3- phthalic acid, 2,6-naphthalenedicarboxylic acid, 2- methyl miaows
At least one of azoles, 5,6- dimethylbenzimidazoles, 5- azabenzimidazoles；The solution B is ethyl alcohol, methanol or N, N- bis-
Methylformamide；Ligand and the amount ratio of organic solution are (0.5-1g):(25-30mL)；(2) clarification into step (1) is molten
Metallic compound C is added in liquid, stirs 10~30min under room temperature, obtains mixed solution, it is spare；The metallic compound C
For one kind in zinc nitrate hexahydrate, butyl titanate, copper nitrate, five nitric hydrate bismuths；Belong to the matter of compound C and organic ligand
Measure ratio 1:1~1:4；(3) carrier is put into the mixed solution described in step (2) and small in 50~200 DEG C of constant temperature dipping 2~8
When, MOFs/ carrier materials are obtained, it is spare；The carrier is one kind in glass fibre, diatomite or nickel foam；Carrier with it is organic
The mass ratio 1 of ligand:10；(4) metallic compound D is dissolved in organic solvent, 10~30min is stirred at room temperature, then will place
MOFs/ carrier materials obtained by the step of managing (3), which are put into, wherein to be loaded, spare；The metallic compound D is six hydrations
One kind in zinc nitrate, butyl titanate, copper nitrate, five nitric hydrate bismuths；The molar ratio of metallic compound D and organic solvent is
1:3；(5) material that gained will be prepared in step (4) is aged 12 hours, then 3~5 hours dry under the conditions of 60~100 DEG C,
It is calcined 3~5 hours in 300~500 DEG C of air, you can obtain composite photo-catalyst.
The mass ratio 1 of above-mentioned steps (2) metallic compound C and organic ligand:1.
Organic solvent in above-mentioned steps (4) is absolute ethyl alcohol.
The processing of above-mentioned steps (4) is to use distilled water again after being washed with ethyl alcohol, methanol or N,N-dimethylformamide
Or deionized water carries out washing and drying 3~5 hours under the conditions of 50~80 DEG C.
Multicomponent composite photo-catalyst obtained by above-mentioned preparation method.
Application of the above-mentioned multicomponent composite photo-catalyst in degradation benzene, toluene or formaldehyde.
Advantageous effect：The active component particles size of multicomponent composite photo-catalyst of the present invention is small, load capacity is high, distribution
Uniformly, photoresponse window wide (ultraviolet-visible light), the advantages that efficiency of light energy utilization is high, realize Multimetal oxide collaboration and urge
Change, significantly improves the performance and application of photochemical catalyst, there is suitable industrialized production.
Description of the drawings
Fig. 1 is Bi made from embodiment 12O3/TiO2Degradation rate of/glass fibre the photochemical catalyst to toluene.
Fig. 2 is ZnO/TiO made from embodiment 22Degradation rate of/glass fibre the photochemical catalyst to benzene.
Fig. 3 is ZnO/Bi made from embodiment 32O3The degradation rate of/glass fibre photochemical catalyst PARA FORMALDEHYDE PRILLS(91,95).
Specific implementation mode
It is further illustrated the present invention below by specific experiment scheme, but the present invention is not limited thereto.
Embodiment 1
A kind of preparation method and application of multicomponent composite photo-catalyst, includes the following steps：
(1) 1g terephthalic acid (TPA)s are dissolved in 40mL n,N-Dimethylformamide, are obtained after 10min is stirred at room temperature
Clear solution.
(2) 0.8g Bi (NO are added in the clear solution obtained to step (1)3)3·5H2O stirs 20min at room temperature, obtains
It is spare to mixed solution.
(3) 8g glass fibres are put into the mixed solution described in step (2) and are impregnated 2 hours in 100 DEG C of constant temperature, obtained
MOFs/ glass fibres, it is spare.
(4) 30mL butyl titanates are dissolved in 15mL absolute ethyl alcohols and stir 15min.Obtained by processed step (3)
MOFs/ glass fiber materials are put into solution of tetrabutyl titanate, are loaded, spare.Above-mentioned processing method is with ethyl alcohol, methanol
Or n,N-Dimethylformamide carry out washing MOFs/ glass fiber materials, then with distilled water or deionized water carry out washing and
It is 3~5 hours dry under the conditions of 50~80 DEG C.
(5) material for preparing step (4) is aged 12 hours.It is 4 hours dry under the conditions of 60 DEG C, it is then placed in Muffle furnace
In 500 DEG C calcine 3 hours, obtain Bi2O3/TiO2/ glass fibre photochemical catalyst, load capacity are as shown in table 1.
(6) above-mentioned photochemical catalyst 4g is weighed, is put into equipped with a concentration of 2.8g/m3Toluene is in glass box reaction chamber, in purple
Light-catalyzed reaction is carried out under external exposure, every 12h, is sampled in glass reactor, is analyzed and is produced with gas-chromatography (fid detector)
Residual toluene in object, and will be with TiO2/ glass fibre, Bi2O3/ glass fibre compares, and obtained data are as shown in Figure 1.
Table 1
| Catalyst | Weight before load | Weight after load | Load capacity |
| Bi2O3/TiO2/ glass fibre | 8.0g | 9.153g | 14.413% |
| TiO2/ glass fibre | 8.0g | 8.68g | 8.50% |
| Bi2O3/ glass fibre | 8.0g | 8.60g | 7.5% |
From the above data, in identical raw material dosage, its active component of the catalyst of this method preparation is negative
Carrying capacity is far above its traditional method.
Embodiment 2
A kind of preparation method and application of multicomponent composite photo-catalyst, includes the following steps：
(1) 0.5g terephthalic acid (TPA)s are dissolved in 25mL n,N-Dimethylformamide, are obtained after 15min is stirred at room temperature
Clear solution is obtained, it is spare.
(2) 0.35g Zn (NO are added into the obtained clear solution of step (1)3)2·6H2O is stirred at room temperature
It is spare to obtain mixed solution by 15min.
(3) 8g glass fibres are put into the mixed solution described in step (2) and are impregnated 2 hours in 120 DEG C of constant temperature, obtained
MOFs/ glass fibres, it is spare.
(4) 30mL butyl titanates are dissolved in 15mL absolute ethyl alcohols, stir 10min.Obtained by processed step (3)
MOFs/ glass fiber materials are put into butyl titanate and are loaded, spare.Above-mentioned processing method be with ethyl alcohol, methanol or N, N~
Dimethylformamide carries out washing MOFs/ glass fiber materials, then with distilled water or deionized water wash and 50~80
It is 3~5 hours dry under the conditions of DEG C.
(5) material for preparing step (4) is aged 12 hours.It is 4 hours dry under the conditions of 60 DEG C, it is then placed in Muffle furnace
In 500 DEG C calcine 3 hours, obtain ZnO/TiO2/ glass fibre photochemical catalyst.
(6) above-mentioned photochemical catalyst 4g is weighed, is put into equipped with a concentration of 2.8g/m3Benzene is in glass box reaction chamber, ultraviolet
The lower progress light-catalyzed reaction of irradiation is sampled every 12h in glass reactor, and product is analyzed with gas-chromatography (fid detector)
Middle residual toluene, and will be with TiO2/ glass fibre, ZnO/ glass fibres compare, and obtained data are as shown in Figure 2.
Embodiment 3
A kind of preparation method of multicomponent composite photo-catalyst, includes the following steps：
(1) 0.8g terephthalic acid (TPA)s are dissolved in 30mL n,N-Dimethylformamide, are obtained after 13min is stirred at room temperature
Clear solution is obtained, it is spare.
(2) 0.35g Zn (NO are added in the clear solution obtained to step (1)3)2·6H2O stirs 15min at room temperature,
It is spare to obtain mixed solution.
(3) 8g glass fibres are put into the mixed solution described in step (2) and are impregnated 2 hours in 120 DEG C of constant temperature, obtained
MOFs/ glass fibres, it is spare.
(4) by 35g Bi (NO3)3·5H2O is dissolved in 15mL absolute ethyl alcohols, stirs 13min.By processed step (3)
Gained MOFs/ glass fiber materials, which are put into bismuth nitrate solution, to be loaded, spare.Above-mentioned processing method is with ethyl alcohol, methanol
Or n,N-Dimethylformamide carry out washing MOFs/ glass fiber materials, then with distilled water or deionized water carry out washing and
It is 3~5 hours dry under the conditions of 50~80 DEG C.
(5) material for preparing step (4) is aged 12 hours.It is 4 hours dry under the conditions of 60 DEG C, it is then placed in Muffle furnace
In 500 DEG C calcine 3 hours, obtain ZnO/Bi2O3/ glass fibre.
(6) above-mentioned ZnO/Bi is weighed2O3/ glass fibre 4g, is put into equipped with a concentration of 2.8g/m3Formaldehyde reacts for glass box
In case, light-catalyzed reaction is carried out under visible light illumination, every 12h, is sampled in glass reactor, is measured with formaldehyde measurement instrument
Content of formaldehyde, and will be with Bi2O3/ glass fibre, ZnO/ glass fibres compare, and obtained data are as shown in Figure 3.
Claims (6)
1. a kind of preparation method of multicomponent composite photo-catalyst, it is characterised in that include the following steps：
(1) it takes organic ligand A and is dissolved in solution B, stir 10~30min at ambient temperature, obtain clear solution, it is standby
With；The organic ligand A is trimesic acid, terephthalic acid (TPA), trimellitic acid, 5- imidazole radicals -1,3- phthalic acid, 2,6-
At least one of naphthalenedicarboxylic acid, 2-methylimidazole, 5,6- dimethylbenzimidazoles, 5- azabenzimidazoles；The solution B is
Ethyl alcohol, methanol or N,N-dimethylformamide；Ligand and the amount ratio of organic solution are (0.5-1g):(25-30mL)；
(2) metallic compound C is added in the clear solution into step (1), stirs 10~30min under room temperature, is mixed
Solution is closed, it is spare；The metallic compound C is in zinc nitrate hexahydrate, butyl titanate, copper nitrate, five nitric hydrate bismuths
It is a kind of；Belong to the mass ratio 1 of compound C and organic ligand:1~1:4；
(3) carrier is put into the mixed solution described in step (2) and is impregnated 2~8 hours in 50~200 DEG C of constant temperature, obtain MOFs/
Carrier material, it is spare；The carrier is one kind in glass fibre, diatomite or nickel foam；The quality of carrier and organic ligand
Than 1:10；
(4) metallic compound D is dissolved in organic solvent, is stirred at room temperature 10~30min, then by processed step (3)
The MOFs/ carrier materials of gained, which are put into, wherein to be loaded, spare；The metallic compound D is zinc nitrate hexahydrate, metatitanic acid four
One kind in butyl ester, copper nitrate, five nitric hydrate bismuths；The molar ratio of metallic compound D and organic solvent is 1:3；
(5) material that gained will be prepared in step (4) is aged 12 hours, then 3~5 hours dry under the conditions of 60~100 DEG C,
It is calcined 3~5 hours in 300~500 DEG C of air, you can obtain composite photo-catalyst.
2. a kind of preparation method of multicomponent composite photo-catalyst according to claim 1, it is characterised in that the step (2)
The mass ratio 1 of metallic compound C and organic ligand:1.
3. a kind of preparation method of multicomponent composite photo-catalyst according to claim 1, it is characterised in that the step (4)
In organic solvent be absolute ethyl alcohol.
4. a kind of preparation method of multicomponent composite photo-catalyst according to claim 1, it is characterised in that the step (4)
Processing be to be washed simultaneously with distilled water or deionized water again after being washed with ethyl alcohol, methanol or N,N-dimethylformamide
It is 3~5 hours dry under the conditions of 50~80 DEG C.
5. multicomponent composite photo-catalyst obtained by any preparation method of Claims 1 to 4.
6. application of the multicomponent composite photo-catalyst described in claim 5 in degradation benzene, toluene or formaldehyde.
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