CN110876952A - Pt-loaded BMO @ g-C3N4Composite photocatalyst and preparation method and application thereof - Google Patents
Pt-loaded BMO @ g-C3N4Composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN110876952A CN110876952A CN201911107856.8A CN201911107856A CN110876952A CN 110876952 A CN110876952 A CN 110876952A CN 201911107856 A CN201911107856 A CN 201911107856A CN 110876952 A CN110876952 A CN 110876952A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000002131 composite material Substances 0.000 claims abstract description 118
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 31
- 239000006185 dispersion Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
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- 239000002904 solvent Substances 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000001103 potassium chloride Substances 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 150000001621 bismuth Chemical class 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 150000002751 molybdenum Chemical class 0.000 claims description 7
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 238000004299 exfoliation Methods 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 9
- 239000012279 sodium borohydride Substances 0.000 description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
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- 239000012153 distilled water Substances 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical group [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
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- 230000007547 defect Effects 0.000 description 2
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- 239000008098 formaldehyde solution Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- LLQPHQFNMLZJMP-UHFFFAOYSA-N Fentrazamide Chemical compound N1=NN(C=2C(=CC=CC=2)Cl)C(=O)N1C(=O)N(CC)C1CCCCC1 LLQPHQFNMLZJMP-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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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
- 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
-
- 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
Abstract
The invention discloses a Pt loaded BMO @ g-C3N4Composite photocatalyst, preparation method and application thereof, Pt-loaded BMO @ g-C3N4The carrier of the composite photocatalyst is BMO @ g-C3N4The active center of the composite material is platinum nano-particles; pt loaded BMO @ g-C3N4In the composite photocatalyst, the mass fraction of Pt is 0.01-0.2%, and g-C3N4The mass fraction of the BMO is 4-30%, and the mass fraction of the BMO is 69.8-95.8%. The composite photocatalyst provided by the invention has the advantages of ultralow noble metal content, low cost, wide raw material source, good compatibility with the environment, wide application range and capability of catalytically degrading formaldehyde under the irradiation of a fluorescent lamp at room temperature.
Description
Technical Field
The invention relates to the field of indoor air treatment and purification, in particular to Pt-loaded BMO @ g-C3N4A composite photocatalyst and a preparation method and application thereof.
Background
Modern buildings, especially those with high energy efficiency such as office buildings, hospitals, schools, etc., are often poor in ventilation efficiency due to the imperfect ventilation facilities, and thus have a large safety risk in terms of indoor air quality, which may seriously affect the health of the occupants in these buildings. Formaldehyde is a common indoor air pollutant, has great harm to human bodies, and can cause death when serious. Formaldehyde is available from a number of sources including wooden furniture, adhesives, and decorative materials. In the past decades, the treatment of benzene and radon, two carcinogenic indoor air pollutants, has been very effective, but formaldehyde is still the main harmful factor affecting indoor air quality. Therefore, in the modern society, the formaldehyde in the indoor air is purified, the indoor air quality is improved, and the formaldehyde purification device has extremely important significance for human life.
At present, there are many methods and approaches in treating and purifying indoor air, especially in removing formaldehyde in indoor air, and the more mature methods are: adsorption (including physical adsorption and chemical adsorption), biological absorption, thermal catalytic decomposition, and photocatalytic oxidative degradation. Formaldehyde in the indoor air is removed by adsorbing the formaldehyde through a physical or chemical way, so that additional equipment is required, and the cost is high; the formaldehyde in the indoor air is purified through a biological way, on one hand, a large number of plants with good absorption effect on the formaldehyde are needed to purify the air, the plants not only occupy the indoor space to place green plants, but also the maintenance cost is relatively high, and on the other hand, the biological way is relatively long in time effectiveness for purifying the indoor air; the aim of purifying indoor air is achieved by thermally catalyzing and decomposing formaldehyde, so that not only additional heating equipment needs to be provided, but also excessive energy needs to be consumed; the photocatalytic decomposition of formaldehyde in indoor air is a good choice and approach, and firstly, the formaldehyde in the indoor air treated by the photocatalyst can not only effectively utilize indoor light energy, but also achieve the purpose of purifying the indoor air without providing extra energy and special devices. Thus, it is possible to provideThe photocatalyst responding to visible light at room temperature is greatly concerned by the majority of researchers. The design, research, development and preparation of the catalyst which is efficient, stable, non-toxic, harmless, convenient to recycle and low in cost are key influencing factors for degrading formaldehyde under the irradiation of room-temperature visible light. The catalyst with better catalytic effect on formaldehyde at room temperature is a loaded noble metal type composite catalyst. Considerable research and scientific research results show that the structure and the micro-morphology of the catalyst and polar groups such as surface hydroxyl on the surface of the material are main influencing factors influencing the catalytic activity of the supported noble metal type catalyst. The catalyst can be roughly classified into metal oxides such as ZnO and Al2O3、CeO2、MnO2And partially complex oxides, non-metallic compounds, e.g. g-C3N4And composites thereof with metal oxides such as g-C3N4ZnO, etc. the catalyst can reach the effect of purifying formaldehyde in indoor air effectively only under specific conditions and additional energy supply. Therefore, the catalyst has the advantages of low design and preparation cost, simple preparation process, no toxicity, no harm, convenient recycling and environmental friendliness, and has great research significance.
Disclosure of Invention
The invention aims to overcome the technical defects and provides a Pt-loaded BMO @ g-C3N4The composite photocatalyst and the preparation method and the application thereof solve the technical problems that the existing catalyst in the prior art has complex preparation process and can only play a role under certain conditions.
To achieve the above technical object, the present invention provides a first solution: pt-loaded BMO @ g-C3N4The Pt-loaded BMO @ g-C composite photocatalyst3N4The carrier of the composite photocatalyst is BMO @ g-C3N4The active center of the composite material is platinum nano-particles; pt-loaded BMO @ g-C as described above3N4In the composite photocatalyst, the mass fraction of Pt is 0.01-0.2%, and g-C3N4The mass fraction of the BMO is 4-30%, and the mass fraction of the BMO is 69.8-95.8%.
The present invention provides a second solution: pt-loaded BMO @ g-C3N4The preparation method of the composite photocatalyst comprises the following steps:
preparation of ultrasonic peeling g-C3N4A material; preparation of BMO @ g-C3N4A composite material; preparation of Pt-Supported BMO @ g-C3N4A composite photocatalyst is provided.
Pt loaded BMO @ g-C as provided in the second solution of the invention3N4Preparation method of composite photocatalyst for preparing Pt-loaded BMO @ g-C provided in first solution of the invention3N4A composite photocatalyst is provided.
The present invention provides a third solution: pt-loaded BMO @ g-C3N4Application of composite photocatalyst, Pt-loaded BMO @ g-C3N4The composite photocatalyst is applied to catalytic degradation of formaldehyde, and Pt-loaded BMO @ g-C in the first solution of the invention is adopted3N4A composite photocatalyst is provided.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a Pt-loaded BMO @ g-C3N4The composite photocatalyst has the advantages of ultralow noble metal content, low cost, wide raw material source, good environmental compatibility and wide application range, and can be used for catalytically degrading formaldehyde under the irradiation of a fluorescent lamp at room temperature.
Drawings
FIG. 1 is an XRD pattern of the composite photocatalysts obtained in example 3, comparative example 1 and comparative example 2;
FIG. 2 is an SEM photograph of the composite photocatalyst obtained in example 3;
FIG. 3 is a diagram of a formaldehyde catalytic oxidation test unit;
FIG. 4 is a graph of room temperature formaldehyde removal rate versus time for the composite photocatalysts obtained in example 3, comparative example 3 and comparative example 4;
FIG. 5 is a graph of carbon dioxide production versus time for the composite catalysts obtained in example 3, comparative example 3, and comparative example 4;
in fig. 3: 1 infrared spectrum gas detector, 2 computer, 3 organic glass reactor, 31 air inlet, 32 formaldehyde solution injection hole, 33 surficial dish cover pull wire hole, 34 air outlet, 35 fluorescent tube, 36 front box door of box body, 37 surficial dish, 38 side box door of box body and 39 electric fan.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to embodiments and accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Aiming at the defects of the carrier in the prior art and graphite phase carbon nitride (g-C)3N4) And Bismuth Molybdate (BMO) have the characteristics of excellent physicochemical property, visible light response, simple preparation process, cheap and rich raw material sources, no toxicity, no harm, environmental friendliness and the like. The preparation method provided by the embodiment of the invention selects the carrier as a carrier of a composite catalyst for photocatalytic decomposition of formaldehyde at room temperature.
For the first solution of the present invention, the present invention provides a Pt loaded BMO @ g-C3N4The Pt-loaded BMO @ g-C composite photocatalyst3N4The carrier of the composite photocatalyst is BMO @ g-C3N4The active center of the composite material is platinum nano-particles; pt-loaded BMO @ g-C3N4In the composite photocatalyst, the mass fraction of Pt is 0.01-0.2%, and g-C3N4The mass fraction of the BMO is 4-30%, and the mass fraction of the BMO is 69.8-95.8%.
Preferably, the Pt-supported BMO @ g-C described above3N4In the composite photocatalyst, the mass fraction of Pt is 0.06-0.2%, and g-C3N4The mass fraction of the BMO is 4-28.8%, and the mass fraction of the BMO is 71-95.8%. In this range, the room temperature formaldehyde removal rate is higher. Wherein, the above-mentioned g-C3N4Is water-soluble g-C3N4。
For the second solution of the present invention, the present invention provides a Pt loaded BMO @ g-C3N4The preparation method of the composite photocatalyst comprises the following steps:
s1 preparation of ultrasonic peeled g-C3N4A material.
In step S1, dispersing the carbon-nitrogen-containing precursor, sodium salt, and potassium salt in water to obtain a dispersion liquid I; wherein, the carbon-nitrogen-containing precursor is one or more of dicyandiamide, melamine and thiourea; the sodium salt is one or more of sodium chloride, sodium carbonate and sodium bicarbonate, the potassium salt is one or more of potassium chloride, potassium carbonate and potassium bicarbonate, and the molar ratio of the carbon-nitrogen-containing precursor, the sodium salt and the potassium salt in the dispersion liquid I is (1-4) to 1: 1; preferably, in the dispersion liquid I, the carbon-nitrogen-containing precursor is dicyanodiamine, the sodium salt is sodium chloride, the potassium salt is potassium chloride, and the molar ratio of dicyanodiamine, sodium chloride and potassium chloride in the dispersion liquid I is 2:1: 1.
Subjecting the dispersion I to water bath treatment, evaporating to dryness and drying to obtain g-C3N4Precursor salt; wherein the temperature of the water bath is 70-90 ℃, and preferably 80 ℃; the water bath treatment process is carried out under the stirring condition; the drying temperature is 60-80 ℃, the drying time is 8-16 h, preferably, the drying temperature is 70 ℃, and the drying time is 12 h.
Mixing the above g-C3N4Calcining the precursor salt to obtain g-C3N4A crude product; wherein the calcining temperature is 550-650 ℃, the calcining time is 2-4 h, and the heating rate is 2 ℃/min in the calcining process.
Mixing the above g-C3N4Adding the crude product into water, performing ultrasonic dispersion, filtering, washing, concentrating and drying to obtain ultrasonic stripping g-C3N4(ii) a Wherein the ultrasonic dispersion time is 2-4 h, preferably 3 h; the filtering process comprises standing the suspension obtained after ultrasonic dispersion and filtering to obtain filtrate; concentrating the filtrate, diluting with ethanol water solution, and concentrating again to obtain concentrated solution; the washing process is to wash the concentrated solution, specifically, in the washing process, the used washing solvent is a mixed solution of ethanol and water, and the volume ratio of the ethanol to the water is 1: (1-5), preferably 1: 3; the washed filtrate needs to be concentrated before the drying process, so that the drying process can be smoothly carried out, the drying temperature is 60-80 ℃, the drying time is 8-16 h, preferably, the drying temperature is 70 ℃, and the drying time is 12 h.
S2 preparation of BMO @ g-C3N4A composite material.
In step S2, dispersing the bismuth salt and the molybdenum salt in the first solvent, respectively, and adding the mixture into the second solvent to obtain a solution I; wherein the dispersion time is 0.2-0.8 h; the dispersion process is carried out under the condition of stirring; the bismuth salt is one or more of bismuth nitrate, bismuth chloride and bismuth sulfate, the molybdenum salt is one or more of sodium molybdate, potassium molybdate and magnesium molybdate, and the first solvent is one or more of ethylene glycol, glycerol, water and ethanol; the concentration of bismuth salt in the solution I is 0.025-0.05 mol/L, and the concentration of molybdenum salt is 0.01-0.025 mol/L; preferably, the bismuth salt is bismuth nitrate, the molybdenum salt is sodium molybdate dihydrate, and the first solvent is ethylene glycol.
Ultrasonic stripping of g-C3N4Ultrasonically dispersing the solution I to obtain a solution II; wherein g-C is ultrasonically stripped3N4The mass concentration of the solution II is 0.5-4 g/L, and the ultrasonic dispersion time is 0.3-1.5 h.
Carrying out hydrothermal treatment on the solution II, centrifuging, washing and drying to obtain BMO @ g-C3N4A composite material; wherein the mixing process is carried out under the condition of stirring, the temperature of the hydrothermal treatment is 120-200 ℃, the time of the hydrothermal treatment is 8-12 h, preferably, the temperature of the hydrothermal treatment is 160-200 ℃, and the time of the hydrothermal treatment is 10-12 h.
S3 preparation of Pt Supported BMO @ g-C3N4A composite photocatalyst is provided.
In the step S3, the BMO @ g-C3N4Dispersing the composite material into water to obtain a dispersion liquid II; wherein, in the dispersion liquid II, BMO @ g-C3N4The mass concentration of the composite material is 10-40 g/L, the dispersion time is 0.15-0.3 h, and the dispersion is carried out under the condition of stirring.
Adding a platinum precursor solution into the dispersion liquid II, and uniformly mixing to obtain a mixed solution; the platinum precursor is one of chloroplatinic acid, potassium chloroplatinate and sodium chloroplatinate, and the mass fraction of the platinum precursor solution is 0.8-2%; the mixing time is 0.3 h-0.6 h, and the mixing is carried out under the condition of stirring. Dispersing a reducing agent and alkali into water to prepare an alkaline reducing solution; wherein the reducing agent is one or more of sodium borohydride and potassium borohydride, and the alkali is one or more of sodium hydroxide, potassium hydroxide and barium hydroxide; the concentration of the reducing agent in the alkaline reducing solution is 0.2-1 mol/L, the concentration of the alkali in the alkaline reducing solution is 0.1-0.5 mol/L, and the molar ratio of the reducing agent to the alkali is (2-5): 1.
Adding an alkaline reducing solution into the mixed solution, stirring, centrifuging, washing and drying to obtain Pt-loaded BMO @ g-C3N4A composite photocatalyst is provided.
Pt loaded BMO @ g-C as provided in the second solution of the invention3N4Preparation method of composite photocatalyst for preparing Pt-loaded BMO @ g-C provided in first solution of the invention3N4A composite photocatalyst is provided.
In a third solution of the invention, a Pt loaded BMO @ g-C is provided3N4Application of composite photocatalyst, and Pt-loaded BMO @ g-C3N4The composite photocatalyst is applied to catalytic degradation of formaldehyde, and Pt-loaded BMO @ g-C in the first solution of the invention is adopted3N4A composite photocatalyst is provided.
Examples 1 to 6
Examples 1 to 6 provide 6 differences, respectivelyPt loaded BMO @ g-C of3N4The composite photocatalyst is obtained through the following steps:
(1) preparation of ultrasonic peeling g-C3N4Materials:
dissolving 5.90g of dicyanodiamine, 2.05g of sodium chloride and 2.61g of potassium chloride (the molar ratio of the dicyanodiamine to the sodium chloride to the potassium chloride is 2:1:1) in 200mL of water to obtain a dispersion I; evaporating the solvent from the water bath treatment solution at 80 deg.C to obtain mixed salt solid, and drying the mixed salt solid at 70 deg.C overnight to obtain g-C3N4Precursor salt; g to C3N4Grinding precursor salt, adding a proper amount of the precursor salt into a clean crucible, and calcining at 600 ℃ for 2h (the heating rate is 2 ℃/min) to obtain g-C3N4The crude product of (2); g to C3N4Dissolving the crude product in water, performing ultrasonic treatment for 3h, filtering with a sand core funnel, taking filtrate, removing precipitate, concentrating the filtrate at 80 ℃ by using a rotary evaporator, adding 200ml of mixed solution of ethanol and water with the volume ratio of 1:3 into the concentrated solution, washing, continuing to concentrate at 80 ℃, drying the concentrated solution at 70 ℃ overnight to obtain the ultrasonic stripping g-C3N4A material.
(2) Preparation of BMO @ g-C3N4The composite material comprises the following components:
respectively dissolving 0.63g of bismuth nitrate pentahydrate and 0.16g of sodium molybdate dihydrate in 5mL of ethylene glycol, magnetically stirring for 0.5h, mixing the ethylene glycol solution of sodium molybdate with the ethylene glycol solution of bismuth nitrate, continuously stirring for 5min, then adding 30mL of absolute ethyl alcohol, and continuously stirring for 10min to obtain a solution I; ultrasonic stripping of g-C3N4Dissolving in the solution I, and performing ultrasonic dispersion for 0.3h to obtain a solution II; transferring the solution II into a reaction kettle, carrying out hydrothermal reaction for 10h at 180 ℃, centrifuging, washing and drying to obtain BMO @ g-C3N4A composite material.
(3) Preparation of Pt-Supported BMO @ g-C3N4The composite photocatalyst comprises:
take 0.4g BMO @ g-C3N4Dispersing the composite material into 20mL of distilled water, and magnetically stirring for 0.15-0.3 h to obtain a dispersion liquid II; into dispersion IIAdding a certain volume of chloroplatinic acid solution with the mass fraction of 1%, and continuously stirring for 0.5h to obtain a mixed solution; reacting NaBH4Dispersing NaOH and NaOH into 5mL of water to obtain an alkaline reduction solution; wherein, NaBH4And the concentration of NaOH is 0.5mol/L and 0.1mol/L respectively; adding the mixed solution into the alkaline reducing solution, continuously stirring for 0.5h, and then centrifuging, washing and drying to obtain Pt-loaded BMO @ g-C3N4A composite photocatalyst is provided.
Pt-loaded BMO @ g-C obtained in examples 1 to 63N4The contents of the components of the composite photocatalyst are shown in Table 1.
TABLE 1
Comparative example 1
This comparative example provides a Pt/g-C3N4The composite photocatalyst adopts the following steps:
(1) preparation of ultrasonic peeling g-C3N4Materials:
dissolving 5.90g of dicyanodiamine, 2.05g of sodium chloride and 2.61g of potassium chloride (the molar ratio of the dicyanodiamine to the sodium chloride to the potassium chloride is 2:1:1) in 200mL of water to obtain a dispersion I; evaporating the solvent from the water bath treatment solution at 80 deg.C to obtain mixed salt solid, and drying the mixed salt solid at 70 deg.C overnight to obtain g-C3N4Precursor salt; g to C3N4Grinding precursor salt, adding a proper amount of the precursor salt into a clean crucible, and calcining at 600 ℃ for 2h (the heating rate is 2 ℃/min) to obtain g-C3N4The crude product of (2); g to C3N4Dissolving the crude product in water, performing ultrasonic treatment for 3h, filtering with a sand core funnel, taking filtrate, discarding precipitate, concentrating the filtrate at 80 deg.C with a rotary evaporator, adding 200ml of mixed solution of ethanol and water at a volume ratio of 1:3 into the concentrated solution, washing, and continuing at 80 deg.CConcentrating, and drying the concentrate at 70 deg.C overnight to obtain ultrasonically-exfoliated g-C3N4A material.
(2) Preparation of Pt/g-C3N4The composite photocatalyst comprises:
taking 0.4g of ultrasonic stripping g-C3N4Dispersing the material into 20mL of distilled water, and magnetically stirring for 0.15-0.3 h to obtain a dispersion liquid II; adding 0.1ml of chloroplatinic acid solution with the mass fraction of 1% into the dispersion liquid II, and continuously stirring for 0.5h to obtain a mixed solution; wherein, the platinum element in the chloroplatinic acid accounts for 0.08 percent of the composite catalyst by mass; reacting NaBH4Dispersing NaOH and NaOH into 5mL of water to obtain an alkaline reduction solution; wherein, NaBH4And the concentration of NaOH is 0.5mol/L and 0.1mol/L respectively; adding the mixed solution into the alkaline reducing solution, continuously stirring for 0.5h, and then centrifuging, washing and drying to obtain Pt/g-C3N4A composite photocatalyst is provided.
Comparative example 2
The comparative example provides a Pt/BMO composite photocatalyst, which comprises the following steps:
(1) preparing BMO nano materials:
respectively dissolving 0.63g of bismuth nitrate pentahydrate and 0.16g of sodium molybdate dihydrate in 5mL of ethylene glycol, magnetically stirring for 0.5h, mixing the ethylene glycol solution of sodium molybdate with the ethylene glycol solution of bismuth nitrate, continuously stirring for 5min, then adding 30mL of absolute ethyl alcohol, and continuously stirring for 10min to obtain a solution I; and transferring the solution I into a reaction kettle, carrying out hydrothermal reaction for 10h at 180 ℃, and carrying out centrifugation, washing and drying to obtain the BMO nano material.
(2) Preparing a Pt/BMO composite photocatalyst:
dispersing 0.4g of BMO nano material into 20mL of distilled water, and magnetically stirring for 0.15-0.3 h to obtain a dispersion liquid II; adding 0.1ml of chloroplatinic acid solution with the mass fraction of 1% into the dispersion liquid II, and continuously stirring for 0.5h to obtain a mixed solution; wherein, the platinum element in the chloroplatinic acid accounts for 0.08 percent of the composite catalyst by mass; reacting NaBH4Dispersing NaOH and NaOH into 5mL of water to obtain an alkaline reduction solution; wherein, NaBH4And the concentration of NaOH is 0.5mol/L and 0.1mol/L respectively;and adding the mixed solution into the alkaline reducing solution, continuously stirring for 0.5h, and then centrifuging, washing and drying to obtain the Pt/BMO composite photocatalyst.
Comparative example 3
This comparative example provides a BMO @ g-C3N4The composite photocatalyst adopts the following steps:
(1) preparation of ultrasonic peeling g-C3N4Materials:
dissolving 5.90g of dicyanodiamine, 2.05g of sodium chloride and 2.61g of potassium chloride (the molar ratio of the dicyanodiamine to the sodium chloride to the potassium chloride is 2:1:1) in 200mL of water to obtain a dispersion I; evaporating the solvent from the water bath treatment solution at 80 deg.C to obtain mixed salt solid, and drying the mixed salt solid at 60 deg.C overnight to obtain g-C3N4Precursor salt; g to C3N4Grinding precursor salt, adding a proper amount of the precursor salt into a clean crucible, and calcining at 600 ℃ for 2h (the heating rate is 2 ℃/min) to obtain g-C3N4The crude product of (2); g to C3N4Dissolving the crude product in water, performing ultrasonic treatment for 3h, filtering with a sand core funnel, taking filtrate, removing precipitate, concentrating the filtrate at 80 ℃ by using a rotary evaporator, adding 200ml of mixed solution of ethanol and water with the volume ratio of 1:3 into the concentrated solution, washing, continuing to concentrate at 80 ℃, drying the concentrated solution at 70 ℃ overnight to obtain the ultrasonic stripping g-C3N4A material.
(2) Preparation of BMO @ g-C3N4The composite photocatalyst comprises:
respectively dissolving 0.63g of bismuth nitrate pentahydrate and 0.16g of sodium molybdate dihydrate in 5mL of ethylene glycol, magnetically stirring for 0.5h, mixing the ethylene glycol solution of sodium molybdate with the ethylene glycol solution of bismuth nitrate, continuously stirring for 5min, then adding 30mL of absolute ethyl alcohol, and continuously stirring for 10min to obtain a solution I; ultrasonic peeling 0.08g of g-C3N4Dissolving in the solution I, and performing ultrasonic dispersion for 1.5h to obtain a solution II; transferring the solution II into a reaction kettle, carrying out hydrothermal reaction for 10h at 180 ℃, centrifuging, washing and drying to obtain BMO @ g-C3N4A composite photocatalyst; wherein g-C3N4And BMThe mass ratio of O is 2: 10.
Comparative example 4
This comparative example provides a Pt/TiO alloy2The composite photocatalyst adopts the following steps:
0.4g of commercial P25 (TiO)2) Dispersing into 20mL of distilled water, and magnetically stirring for 0.15h to obtain a dispersion liquid; adding 0.1ml of chloroplatinic acid platinum solution with the mass fraction of 1% into the dispersion liquid, and continuously stirring for 0.5h to obtain a mixed liquid, wherein the Pt element in the chloroplatinic acid accounts for 0.08% of the mass of the composite catalyst; reacting NaBH4Dispersing NaOH and NaOH into 5mL of water to obtain an alkaline reduction solution; wherein, NaBH4And the concentration of NaOH is 0.5mol/L and 0.1mol/L respectively; adding the mixed solution into the alkaline reducing solution, continuously stirring for 0.5h, and then centrifuging, washing and drying to obtain Pt/TiO2A composite photocatalyst is provided.
The composite catalysts obtained in example 3, comparative example 1 and comparative example 2 were subjected to X-ray diffraction (XRD) and Scanning Electron Microscope (SEM) analysis, respectively, and the results thereof are shown in fig. 1 and 2, respectively.
As can be seen from FIG. 1, the composite catalysts obtained in example 3, comparative example 1 and comparative example 2 have typical graphite phase carbon nitride (g-C)3N4) A phase structure (JCPDS 87-1526) and a Bismuth Molybdate (BMO) phase structure (JCPDS-21-0102); FIG. 2 is a graphical representation of the composite photocatalyst obtained in example 3, further illustrating that the composite photocatalyst obtained in example 3 is Pt-loaded BMO @ g-C3N4A composite photocatalyst is provided.
The composite photocatalysts obtained in the examples 1-6 and the comparative examples 1-4 are respectively subjected to formaldehyde catalysis experiments at room temperature, and the test conditions are as follows:
as shown in fig. 3, 0.1g of the composite photocatalyst obtained in examples 1 to 6 and comparative examples 1 to 4 was uniformly spread and dispersed in a petri dish 37 having a diameter of 14cm, and the petri dish was placed in a 13L organic glass reactor containing a 5W fan and a 20W fluorescent lamp; injecting a formaldehyde solution with the mass fraction of 37% into the organic glass reactor, removing a glass cover of the watch glass and opening the fluorescent lamp for irradiation when the formaldehyde volatilizes until the concentration is balanced, so that the composite photocatalyst is contacted with the formaldehyde under the irradiation of the fluorescent lamp, and the concentration change of the formaldehyde is monitored on line by a multi-component gas analyzer (INNOVA air Tech Instruments Model 1412 i).
As can be seen from fig. 4 and 5, as the formaldehyde concentration decreases and the carbon dioxide concentration increases with the passage of time, formaldehyde is completely oxidized into carbon dioxide and water, which indicates that the composite photocatalysts obtained in example 3, comparative example 3 and comparative example 4 all have certain room-temperature formaldehyde removal performance; also, as can be seen in FIGS. 4 and 5, the Pt loaded BMO @ g-C obtained in example 33N4The formaldehyde removal rate of the composite photocatalyst under a light measurement test condition is obviously higher than that of the other two composite catalysts; in addition, as can be seen in FIGS. 4 and 5, the Pt loaded BMO @ g-C obtained in example 33N4The composite photocatalyst also has good room-temperature formaldehyde removal performance under dark conditions, so that the Pt-loaded BMO @ g-C in example 3 is further illustrated3N4The composite photocatalyst has excellent formaldehyde removal performance.
The activity data of the composite photocatalysts provided in the examples 1-6 and the comparative examples 1-4 for photocatalytic oxidation degradation of formaldehyde under the irradiation of a fluorescent lamp at room temperature (15 ℃) is shown in table 2.
TABLE 2
As can be seen from Table 2, under the irradiation of a fluorescent lamp at room temperature, the composite photocatalysts obtained in the examples 1-6 and the comparative examples 1-4 all show certain photocatalytic degradation activity on formaldehyde; meanwhile, under the irradiation of a room-temperature fluorescent lamp, comparing the data of the light test and the dark test of the sample obtained in the example 3, it can be seen that the photocatalytic activity of the composite photocatalyst obtained in the example 3 on formaldehyde under the irradiation of the room-temperature fluorescent lamp is obviously superior to that of formaldehyde under the dark test condition, and the composite photocatalyst obtained in the example 3 generates carbon dioxide under the irradiation of the room-temperature fluorescent lampThe rate is greater than 1, the root cause of which is: in a closed reaction system, along with the continuous progress of the photocatalytic reaction, formaldehyde adsorbed on the inner wall of the box body is continuously desorbed and released to enter the reaction system, carbon dioxide in the reaction system is from the degradation of the formaldehyde, and the reduction of the formaldehyde concentration and the increase of the carbon dioxide concentration are comprehensively compared, so that the high or low catalytic degradation activity of the photocatalyst on the formaldehyde can be obtained. Wherein Pt-loaded BMO @ g-C obtained in example 3 of the present invention3N4The composite photocatalyst has the highest visible light response activity (the conversion of formaldehyde to carbon dioxide is regarded as complete degradation of formaldehyde).
Pt-loaded BMO @ g-C obtained in example 33N4The composite catalyst catalyzes formaldehyde repeatedly for many times (the sample is stored in a sealed way after the test is finished), and the visible light response activity of the composite catalyst is shown in table 3.
TABLE 3
As can be seen from Table 3, Pt-loaded BMO @ g-C obtained in example 33N4After the composite material photocatalyst degrades formaldehyde by visible light at room temperature for many times, the catalytic degradation activity of the composite material photocatalyst on formaldehyde is still kept above 55%, which shows that the composite material has better physical and chemical stability.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a Pt-loaded BMO @ g-C3N4The composite photocatalyst has ultralow noble metal content, so that the cost of the prepared composite photocatalyst is greatly reduced, and the composite photocatalyst has good environmental compatibility and wide application range;
the invention provides a Pt-loaded BMO @ g-C3N4The preparation method of the composite photocatalyst has the advantages of simple preparation process, rich raw material sources, low cost, no toxicity, no harm and environmental friendliness;
the invention provides a Pt-loaded BMO @ g-C3N4Application of composite photocatalyst and composite obtained by applicationThe photocatalyst has extremely high catalytic activity to formaldehyde under the irradiation of a fluorescent lamp at room temperature, and can degrade the formaldehyde into nontoxic and harmless carbon dioxide and water.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. Pt-loaded BMO @ g-C3N4The composite photocatalyst is characterized in that the Pt-loaded BMO @ g-C3N4The carrier of the composite photocatalyst is BMO @ g-C3N4The active center of the composite material is platinum nano-particles; pt-loaded BMO @ g-C3N4In the composite photocatalyst, the mass fraction of Pt is 0.01-0.2%, and g-C3N4The mass fraction of the BMO is 4-30%, and the mass fraction of the BMO is 69.8-95.8%.
2. Pt-loaded BMO @ g-C3N4The preparation method of the composite photocatalyst is characterized by comprising the following steps:
preparation of ultrasonic peeling g-C3N4A material; preparation of BMO @ g-C3N4A composite material; preparation of Pt-Supported BMO @ g-C3N4A composite photocatalyst;
pt-loaded BMO @ g-C3N4Preparation method of composite photocatalyst for preparing Pt-loaded BMO @ g-C as claimed in claim 13N4A composite photocatalyst is provided.
3. Pt-loaded BMO @ g-C according to claim 23N4The preparation method of the composite photocatalyst is characterized in that the preparation method comprises the step of ultrasonically stripping g-C3N4The process of the material comprises:
dispersing a carbon-nitrogen-containing precursor, sodium salt and potassium salt in water to obtain a dispersion liquid I;
subjecting the dispersion I toWater bath treatment, followed by evaporation to dryness and drying to give g-C3N4Precursor salt;
subjecting said g-C to3N4Calcining the precursor salt to obtain g-C3N4A crude product;
subjecting said g-C to3N4Adding the crude product into water, performing ultrasonic dispersion, filtering, washing, concentrating and drying to obtain ultrasonic stripping g-C3N4。
4. Pt-loaded BMO @ g-C according to claim 33N4The preparation method of the composite photocatalyst is characterized in that the precursor containing carbon and nitrogen is one or more of dicyandiamide, melamine and thiourea;
the sodium salt is one or more of sodium chloride, sodium carbonate and sodium bicarbonate;
the potassium salt is one or more of potassium chloride, potassium carbonate and potassium bicarbonate;
the molar ratio of the carbon-nitrogen-containing precursor, the sodium salt and the potassium salt in the dispersion liquid I is (1-4) to 1: 1.
5. Pt-loaded BMO @ g-C according to claim 23N4The preparation method of the composite photocatalyst is characterized by preparing BMO @ g-C3N4The process of the composite material comprises the following steps:
respectively and uniformly dispersing bismuth salt and molybdenum salt in a first solvent, mixing, and adding a second solvent to obtain a solution I;
subjecting the ultrasonic exfoliation to g-C3N4Ultrasonically dispersing the solution I to obtain a solution II;
carrying out hydrothermal treatment on the solution II, centrifuging, washing and drying to obtain BMO @ g-C3N4A composite material.
6. Pt-loaded BMO @ g-C according to claim 53N4The preparation method of the composite photocatalyst is characterized in that the bismuth salt is bismuth nitrate, bismuth chloride and bismuth sulfateOne or more of;
the molybdenum salt is one or more of sodium molybdate, potassium molybdate and magnesium molybdate;
the first solvent is one or more of glycol, glycerol, water and ethanol;
the concentration of bismuth salt in the solution I is 0.025-0.05 mol/L, and the concentration of molybdenum salt is 0.01-0.025 mol/L.
7. Pt-loaded BMO @ g-C according to claim 53N4The preparation method of the composite photocatalyst is characterized in that the g-C is stripped by ultrasonic3N4The mass concentration of the solution II is 0.5-4 g/L.
8. Pt-loaded BMO @ g-C according to claim 23N4The preparation method of the composite photocatalyst is characterized in that the preparation method is used for preparing Pt-loaded BMO @ g-C3N4The process of the composite photocatalyst comprises the following steps:
subjecting said BMO @ g-C3N4Dispersing the composite material into water to obtain a dispersion liquid II;
adding a platinum precursor solution into the dispersion liquid II, and uniformly mixing to obtain a mixed solution;
dispersing a reducing agent and alkali into water to prepare an alkaline reducing solution;
adding the alkaline reducing solution into the mixed solution, stirring, centrifuging, washing and drying to obtain Pt-loaded BMO @ g-C3N4A composite photocatalyst is provided.
9. Pt-loaded BMO @ g-C according to claim 83N4The preparation method of the composite photocatalyst is characterized in that BMO @ g-C in the dispersion liquid II3N4The mass concentration of the composite material is 10-40 g/L.
10. Pt-loaded BMO @ g-C3N4Use of a composite photocatalyst, characterized in that it is Pt-supported as described in claim 1BMO@g-C3N4The composite photocatalyst is applied to catalytic degradation of formaldehyde.
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