CN116586081B - LaFeO 3 Base heterojunction composite photocatalysis nano material, preparation method and application - Google Patents
LaFeO 3 Base heterojunction composite photocatalysis nano material, preparation method and application Download PDFInfo
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- CN116586081B CN116586081B CN202310337150.0A CN202310337150A CN116586081B CN 116586081 B CN116586081 B CN 116586081B CN 202310337150 A CN202310337150 A CN 202310337150A CN 116586081 B CN116586081 B CN 116586081B
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 92
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910017771 LaFeO Inorganic materials 0.000 title claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 94
- 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 abstract description 31
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 12
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 10
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- 229960003280 cupric chloride Drugs 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 21
- 230000015556 catabolic process Effects 0.000 abstract description 19
- 238000006731 degradation reaction Methods 0.000 abstract description 19
- 230000031700 light absorption Effects 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 description 20
- 238000006722 reduction reaction Methods 0.000 description 19
- 238000005215 recombination Methods 0.000 description 12
- 230000006798 recombination Effects 0.000 description 12
- -1 bismuth halide Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 229940043267 rhodamine b Drugs 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 229960004106 citric acid Drugs 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- 229960002303 citric acid monohydrate Drugs 0.000 description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 230000005307 ferromagnetism Effects 0.000 description 5
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 5
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
The application provides a LaFeO 3 The preparation method and application of the base heterojunction composite photocatalytic nanomaterial comprise the following preparation steps: s1, lanthanum nitrate and ferric nitrate with a molar ratio of 1:1 are used as reaction raw materials, the temperature of the hydrothermal reaction is controlled to be 150-180 ℃ for 10-14h, a lanthanum nitrate-ferric nitrate complex is obtained, the target temperature of calcination is further controlled to be 650-850 ℃ for 4-6h, and the complex is calcined to obtain LaFeO 3 Particles; s2, laFeO 3 The particles, copper chloride and elemental sulfur react in an ethylenediamine solvent to generate a black precipitate, and the black precipitate is washed, centrifuged and dried to obtain the LaFeO 3 Base heterojunction composite photocatalytic nanomaterial LaFeO 3 /Cu 9 S 5 . The application uses Cu 9 S 5 With LaFeO 3 The composite material of the reduction photocatalysis heterojunction is constructed, which has higher efficiency, stronger carrier separation capability and wider light absorption range, and can be simultaneously applied to photocatalysis CO 2 Reduction and organic pollutant degradation, and can improve CO of catalytic nano material to a certain extent 2 Adsorption and activationIs provided).
Description
Technical Field
The application belongs to the field of nano materials, in particular to a LaFeO 3 A base heterojunction composite photocatalysis nano material, a preparation method and application thereof.
Background
In the rapid development of human society, the massive use of fossil energy has led to massive CO 2 Is discharged to the atmosphere in a short time, thereby causing a serious environmental problem such as greenhouse effect. CO is processed by 2 Is converted into high added value chemicals or fuels, and is an effective way capable of simultaneously solving environmental pollution and energy crisis. CO 2 Conversion techniques include electrocatalytic, thermocatalytic, biochemical conversion, and photocatalytic methods. Wherein the photocatalysis technology takes the input of light energy as driving force, and takes proper semiconductor material as photocatalyst to react, thus having the advantages of cleanness, safety, low energy consumption, low cost and the like, and being the most promising CO 2 One of the transformation methods.
Existing CO 2 The reduction catalytic material is concentrated on noble metal base, bismuth halide base and organic catalyst, and Cu base catalyst is commonly used for CO at present 2 Reduced photocatalytic material capable of reducing CO under photoexcitation or photoexcitation 2 Light carbon fuel is produced. Such as Cu 9 S 5 The nanoparticle is a relatively efficient semiconductor photoelectrocatalyst, and has a forbidden band width of about 1.5eV, in<The ultraviolet-visible light region of 500nm has strong absorption, the conduction band potential is about-0.4V (vs NHE, pH=7), and the CO can be well adapted 2 /CH 4 Reducing power of (-0.21V).
But Cu is 9 S 5 The defects of limited light absorption wavelength range, strong photo-generated carrier recombination and the like, which lead to poor selectivity and low conversion rate of the product, thus directly restricting Cu 9 S 5 Cu-like based catalyst for catalyzing CO 2 And (3) exerting reduction efficiency.Therefore, how to improve the carrier separation ability and widen the light absorption range becomes a problem to be solved urgently.
Disclosure of Invention
The present application provides a LaFeO for solving the above problems in the prior art 3 Base heterojunction composite photocatalysis nano material, preparation method and application thereof, cu is adopted 9 S 5 With LaFeO 3 The composite material of the reduction photocatalysis heterojunction is constructed, which has higher efficiency, stronger carrier separation capability and wider light absorption range, and the reduction photocatalysis heterojunction composite material is used for photocatalysis of CO 2 The method has good application effect in the aspects of reduction and organic pollutant degradation, and improves the photocatalytic reduction of CO by the nano material to a certain extent 2 And the ability to oxidize contaminants.
The specific application comprises the following steps:
in a first aspect, the present application provides a LaFeO 3 The preparation method of the base heterojunction composite photocatalytic nanomaterial comprises the following preparation steps:
s1, lanthanum nitrate and ferric nitrate with a molar ratio of 1:1 are used as reaction raw materials, the temperature of the hydrothermal reaction is controlled to be 150-180 ℃, the reaction time is controlled to be 10-14 hours, a lanthanum nitrate-ferric nitrate complex is obtained, the target temperature of calcination is further controlled to be 650-850 ℃, the calcination time is controlled to be 4-6 hours, and the complex is subjected to calcination treatment to obtain LaFeO 3 Particles;
s2, weighing LaFeO 3 Particles, copper chloride and elemental sulfur are used as reaction precursors, and react in ethylenediamine solvent to generate black precipitate, and the black precipitate is washed, centrifuged and dried to obtain the LaFeO 3 Base heterojunction composite photocatalytic nanomaterial LaFeO 3 /Cu 9 S 5 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the LaFeO 3 The mass of the particles accounts for 25-80% of the total mass of the reaction precursor, and the molar ratio of the cupric chloride to the elemental sulfur is 2:1.
optionally, in step S1, the hydrothermal method includes:
s11, stirring and dissolving lanthanum nitrate, ferric nitrate and citric acid with deionized water to obtain a mixed solution;
s12, transferring the mixed solution to a Teflon reaction kettle for hydrothermal reaction, and cooling, washing, centrifuging and drying a product to obtain a lanthanum nitrate-ferric nitrate complex;
s13, grinding the lanthanum nitrate-ferric nitrate complex, transferring to a crucible, placing the crucible into a tube furnace under the atmosphere of inert gas or nitrogen, heating to the target temperature at a heating rate of 5-10 ℃/min, and calcining to obtain black solid powder product LaFeO 3 And (3) particles.
Optionally, the temperature of the hydrothermal reaction is 180 ℃, and the reaction time is 12 hours.
Optionally, in step S12, the washing centrifugal detergent is deionized water, and the drying temperature is 60-90 ℃.
Optionally, in step S13, the heating rate is 10 ℃/min, the target temperature is 700 ℃, and the calcination time is 4 hours.
Optionally, in step S2, the washing centrifugation operation includes: washing with deionized water and ethanol for 3-4 times at intervals;
the temperature of the drying is 60-80 ℃.
Optionally, in step S2, the LaFeO 3 The mass of the particles was 47.76% of the total mass of the reaction precursor.
In a second aspect, the present application provides LaFeO obtained by the preparation method according to the first aspect 3 The base heterojunction composite photocatalysis nano material.
In a third aspect, the present application provides LaFeO obtained by the preparation method according to the first aspect 3 Application of base heterojunction composite photocatalysis nano material, laFeO 3 Base heterojunction composite photocatalytic nanomaterial for driving CO by visible light 2 Is reduced by (a).
In a fourth aspect, the present application provides LaFeO obtained by the preparation method according to the first aspect 3 Application of base heterojunction composite photocatalysis nano material, laFeO 3 The base heterojunction composite photocatalysis nano material is used for degrading organic pollutants driven by visible light.
Compared with the prior art, the application has the following advantages:
the LaFeO provided by the application 3 Preparation method of base heterojunction composite photocatalysis nano material by Cu 9 S 5 With LaFeO 3 The composite material of the reduction photocatalysis heterojunction-LaFeO with higher efficiency, stronger carrier separation capability and wider light absorption range is constructed 3 /Cu 9 S 5 . And due to LaFeO 3 Is introduced into successfully realize LaFeO 3 /Cu 9 S 5 The photo-generated electron-hole pairs of the composite photocatalytic nanomaterial are located at the hetero-interface (LaFeO 3 With Cu 9 S 5 ) Separation occurs, thereby avoiding single Cu 9 S 5 The rapid in-situ recombination of electrons and holes in the band gap of the catalytic nano material is beneficial to the separation of photo-generated carriers and the reduction of the band gap. Let LaFeO 3 /Cu 9 S 5 The composite photocatalytic nano material not only has excellent degradation effect on rhodamine b under the irradiation of visible light, but also can be used for preparing CO (carbon monoxide) 2 And the small molecular dye is generated by reduction, so that a new solution idea is provided for carbon neutralization.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows LaFeO provided by an embodiment of the present application 3 A flow chart of a preparation method of the base heterojunction composite photocatalytic nanomaterial;
FIG. 2 shows LaFeO provided by an embodiment of the present application 3 /Cu 9 S 5 SEM image of heterojunction composite photocatalytic nanomaterial;
FIG. 3 shows the ultraviolet diffuse reflectance spectrum of the photocatalytic nanomaterial provided in examples 1-3 of the present application;
FIG. 4 shows an embodiment of the applicationLaFeO supplied 3 /Cu 9 S 5 N of heterojunction composite photocatalytic nanomaterial 2 Adsorption-desorption isotherm plot;
FIG. 5 shows a Fourier infrared spectrum of the photocatalytic nanomaterial provided in examples 1-3 of the present application;
FIG. 6 shows a graph of performance contrast of visible light catalytic degradation rhodamine b for the photocatalytic nanomaterial provided in examples 1-3 of the present application;
FIG. 7 shows the visible light catalytic reduction of CO by the photocatalytic nanomaterial provided in examples 1-3 of the present application 2 Is a comparison of the performance of (3).
Detailed Description
The following examples are provided for a better understanding of the present application and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the application, any product which is the same or similar to the present application, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present application.
Specific experimental steps or conditions are not noted in the examples and may be performed in accordance with the operation or conditions of conventional experimental steps described in the prior art in the field. The reagents used, as well as other instruments, are conventional reagent products available commercially, without the manufacturer's knowledge.
Due to single Cu 9 S 5 There is a limited range of light absorption wavelengths, strong photo-generated carrier recombination and Cu 9 S 5 Insufficient stability and the like, wherein Cu + Is easily oxidized to Cu 2+ Thereby losing its reducing power. For this purpose, the inventors have utilized Cu 9 S 5 The method of constructing heterojunction with other materials by the crystal changes the forbidden band width, the energy band edge and the carrier separation capability of the photocatalyst. Specifically Cu 9 S 5 P-type semiconductor material LaFeO with wider mid-doping light absorption range and similar band gap 3 Construction of LaFeO 3 /Cu 9 S 5 Heterojunction composite photocatalytic nanomaterial to strengthen Cu 9 S 5 Photogenerated carriersImproving Cu 9 S 5 And the composite photocatalytic nano material is used for photocatalytic degradation of organic pollutants and CO 2 Is a photocatalytic reduction of (a). Based on the above, the application is embodied as follows:
the first object of the present application is to provide a LaFeO 3 Preparation method of base heterojunction composite photocatalytic nanomaterial, and FIG. 1 shows LaFeO provided by the embodiment of the application 3 The preparation method flow chart of the base heterojunction composite photocatalysis nano material is shown in fig. 1, and comprises the following preparation steps:
s1, lanthanum nitrate and ferric nitrate with a molar ratio of 1:1 are used as reaction raw materials, the temperature of the hydrothermal reaction is controlled to be 150-180 ℃, the reaction time is controlled to be 10-14 hours, a lanthanum nitrate-ferric nitrate complex is obtained, the target temperature of calcination is further controlled to be 650-850 ℃, the calcination time is controlled to be 4-6 hours, and the complex is subjected to calcination treatment to obtain LaFeO 3 And (3) particles.
In specific implementation, the hydrothermal method in the step specifically comprises the following steps:
s11, stirring and dissolving lanthanum nitrate, ferric nitrate and citric acid with deionized water to obtain a mixed solution; wherein, citric acid is used as complexing agent, has no special requirement on stirring speed, and can be selected from 200-600r/min;
s12, transferring the mixed solution to a Teflon reaction kettle for hydrothermal reaction, cooling, washing and centrifuging the product, and drying at 60-90 ℃ to obtain a lanthanum nitrate-ferric nitrate complex; the embodiment of the application selects to carry out hydrothermal reaction at 150-180 ℃ to fully complex lanthanum nitrate and ferric nitrate under the condition of being higher than the boiling point of water; the washing centrifugal detergent is deionized water, and the drying temperature is controlled to be 60-90 ℃.
S13, grinding the lanthanum nitrate-ferric nitrate complex, transferring to a crucible, placing the crucible into a tube furnace under the atmosphere of inert gas or nitrogen, and heating to a target temperature of 650-850 ℃ at a heating rate of 5-10 ℃/min for calcination to obtain black solid powder product LaFeO 3 And (3) particles.
In practice, due to the calcination processThe citric acid and nitrate radical can decompose to produce CO 2 And a small amount of gas, so that the calcination process cannot be performed in a vacuum-tight space, preventing high-pressure cracking.
In specific implementation, lanthanum nitrate-ferric nitrate complex generates LaFeO under the condition of high-temperature calcination 3 The choice of the calcination temperature should be such that the target calcination temperature is not too low, e.g., too low, the citric acid is not burned completely and a good LaFeO is formed 3 A crystal; the temperature is too high, the high temperature is equal to LaFeO 3 Has a large destructive effect on the crystallinity of LaFeO 3 Stability and activity are reduced. The calcination atmosphere is inert gas or nitrogen, so that CO generated by the burning of the citric acid 2 Can be continuously discharged. Therefore, the temperature rise rate is finally selected to be 5-10 ℃/min, the target temperature for calcination is 650-850 ℃, and the calcination time is controlled to be 4-6h.
In particular, the lanthanum nitrate in this step may be selected from La (NO 3 ) 3 、La(NO 3 ) 3 ·3H 2 O or La (NO) 3 ) 3 ·6H 2 O; the ferric nitrate is selected from Fe (NO) 3 ) 3 、Fe(NO 3 ) 3 ·3H 2 O or Fe (NO) 3 ) 3 ·6H 2 O. In specific implementation, the temperature rising rate of the application is preferably 10 ℃/min, the target temperature of calcination is preferably 700 ℃, and the calcination time is controlled to be 4h.
As an example, this step may be to add 4.3301g (0.01 mol) of lanthanum nitrate hexahydrate (La (NO) 3 ) 3 ·6H 2 O), 4.0400g (0.01 mol) of ferric nitrate nonahydrate (Fe (NO) 3 ) 3 ·9H 2 O) and 5.2535g (0.025 mol) citric acid monohydrate (C) 6 H 8 O 7 ·H 2 O) was dissolved in 180mL of deionized water and stirred at a stirring speed of 400r/min for 1h. The mixed solution was transferred to 200mL of stainless steel autoclave lined with polytetrafluoroethylene and transferred to an oven, reacted at 180 ℃ for 12 hours, and after natural cooling, washed with deionized water for 4 times and centrifuged to obtain a reddish brown precipitate. The reddish brown precipitate was transferred to an evaporation pan, dried at 60 ℃, and ground to give a yellowish brown powder. The tan powder was placed in a tube under nitrogen atmosphereCalcining in a furnace, heating to 700 ℃ at a heating rate of 10 ℃/min, keeping the temperature at 700 ℃ for 4 hours, and naturally cooling to obtain black LaFeO with strong ferromagnetism 3 Nanoparticle powder.
S2、LaFeO 3 The particles, copper chloride and elemental sulfur react in an ethylenediamine solvent to generate a red precipitate, and the red precipitate is washed, centrifuged and dried to obtain the LaFeO 3 Base heterojunction composite photocatalytic nanomaterial LaFeO 3 /Cu 9 S 5 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the LaFeO 3 The mass of the particles accounts for 25-80% of the total mass of the reaction precursor, and the molar ratio of the cupric chloride to the elemental sulfur is 2:1.
in particular, in step S2, the washing and centrifuging operation comprises: washing with deionized water and ethanol for 3-4 times at intervals; the temperature of the drying is 60-80 ℃.
In the specific implementation, in the step S2, laFeO 3 The preferred ratio of the mass of the particles to the total mass of the reaction precursor is 47.76%. As an example, this step (step S2) may be to add 1.066g LaFeO 3 The nano particles are dissolved in 28.8mL of ethylenediamine and magnetically stirred at a stirring speed of 300r/min, and then 1.066g of CuCl is added in sequence 2 ·2H 2 O,0.1g of elemental sulfur, magnetically stirring for 1h, centrifugally separating a sample, washing with deionized water and absolute ethyl alcohol for three times respectively, and drying in a vacuum constant-temperature drying oven at 80 ℃ for 8h to obtain black powder LaFeO 3 /Cu 9 S 5 。
In the preparation method provided by the application, lanthanum nitrate and ferric nitrate are selected as reaction raw materials, and LaFeO is obtained through hydrothermal reaction and calcination treatment 3 Granulating and then adding LaFeO 3 The particles, copper chloride and elemental sulfur are dissolved in ethylenediamine solvent to react to obtain LaFeO 3 Base heterojunction composite photocatalytic nanomaterial LaFeO 3 /Cu 9 S 5 . The method has mild preparation conditions and simple and effective operation. The obtained composite material has visible light absorption intensity capable of covering the full visible spectrum and has a larger absorption tail peak, which indicates that the composite material can utilize enough visible light. And due to LaFeO 3 Is introduced into successfully realize LaFeO 3 /Cu 9 S 5 The photo-generated electron-hole pairs of the composite photocatalytic nanomaterial are located at the hetero-interface (LaFeO 3 With Cu 9 S 5 ) Separation occurs, thereby avoiding single Cu 9 S 5 The rapid in-situ recombination of electrons and holes in the band gap of the catalytic nano material is beneficial to the separation of photo-generated carriers and the reduction of the band gap. Let LaFeO 3 /Cu 9 S 5 The composite photocatalytic nano material not only has excellent degradation effect on rhodamine b under the irradiation of visible light, but also can be used for preparing CO (carbon monoxide) 2 And the small molecular dye is generated by reduction, so that a new solution idea is provided for carbon neutralization.
A second object of the present application is to provide LaFeO obtained by the method of the first aspect 3 The base heterojunction composite photocatalysis nano material.
In specific implementation, the LaFeO provided by the application 3 The base heterojunction composite photocatalysis nano material is specifically LaFeO 3 /Cu 9 S 5 Composite photocatalytic nanomaterial. Wherein LaFeO 3 Is the mass of the reactant precursor (LaFeO) 3 Copper chloride and elemental sulfur). LaFeO 3 /Cu 9 S 5 Under the illumination condition, the composite photocatalysis nano material is in LaFeO 3 Electrons of the conduction band will pass through the Z-type charge transfer mechanism and Cu 9 S 5 Hole recombination in valence band, which effectively inhibits LaFeO by cross-interface recombination of photo-generated electron holes 3 And Cu 9 S 5 In-situ charge recombination, thereby enhancing the separation of photogenerated carriers and reducing carrier recombination. And LaFeO 3 Has strong ferromagnetism, is favorable for LaFeO 3 /Cu 9 S 5 And (3) recycling and reutilizing the heterojunction composite photocatalytic nanomaterial.
FIG. 2 shows LaFeO provided by an embodiment of the present application 3 /Cu 9 S 5 SEM image of heterojunction composite photocatalytic nanomaterial, as shown in FIG. 2, laFeO 3 /Cu 9 S 5 Is in a nano-sheet structure. By further adding LaFeO to 3 /Cu 9 S 5 Noble gold such as Pt, au, rh and the like is loaded on the composite photocatalysis nano materialThe catalyst can also be applied to the aspects of NO reduction and the like.
A third object of the present application is to provide LaFeO obtained by the above-mentioned preparation method of the first aspect 3 Application of base heterojunction composite photocatalysis nano material, laFeO 3 Base heterojunction composite photocatalytic nanomaterial for driving CO by visible light 2 Is reduced by (a).
The LaFeO provided by the application 3 Cu is used for the base heterojunction composite photocatalysis nano material 9 S 5 For CO 2 Unique reducing ability, can release CO in water body 2 Reduction to C 1 /C 2 Molecular fuel. At the same time in LaFeO 3 Electrons of the conduction band will pass through the Z-type charge transfer mechanism and Cu 9 S 5 Hole recombination in the valence band. The cross-interface recombination of the photo-generated electron holes effectively inhibits LaFeO 3 And Cu 9 S 5 Is in situ compounded, and the Z-type charge transfer mechanism can effectively retain Cu 9 S 5 Stronger reducing power than CO 2 /CH 4 More negative potential of LaFeO 3 /Cu 9 S 5 Compared with single Cu, the composite photocatalysis nano material 9 S 5 With stronger CO 2 Reducing power and a wider visible light response range.
In some embodiments, the present application provides LaFeO 3 /Cu 9 S 5 Organic contaminants that heterojunction composite photocatalytic nanomaterial can be used for photocatalytic degradation include, but are not limited to, CO 2 Formaldehyde, SO 2 Ammonia and NO X 。
In some embodiments, the present application provides LaFeO 3 /Cu 9 S 5 Heterojunction composite photocatalytic nanomaterial reduces CO within 5 hours 2 Is CH 4 The yield of (C) reaches 0.96546 mu mol/g/h, and the single LaFeO 3 And Cu 9 S 5 Reduction of CO within 5 hours of nanoparticles 2 Is CH 4 The yields of (2) were 0.13654. Mu. Mol/g/h and 0.05321. Mu. Mol/g/h, respectively.
A fourth object of the present application is to provide a system as defined in the first aspectLaFeO obtained by the preparation method 3 Application of base heterojunction composite photocatalysis nano material, laFeO 3 The base heterojunction composite photocatalysis nano material is used for visible light driving degradation of organic pollutants.
The LaFeO provided by the application 3 Under the irradiation of visible light, the base heterojunction composite photocatalysis nano material exists in Cu 9 S 5 Electrons of the conduction band can easily react with oxygen adsorbed on the surface of the catalyst to generate superoxide radical, and the superoxide radical free radical can rapidly reduce Jie Luodan Minb in a reaction environment; at the same time, is positioned at LaFeO 3 The photo-generated hole in the valence band has stronger oxidation-reduction capability and can directly act on the degradation of pollutants; and in LaFeO 3 Electrons of the conduction band will pass through the Z-type charge transfer mechanism and Cu 9 S 5 Hole recombination in valence band effectively avoids LaFeO 3 And Cu 9 S 5 Is in situ recombined with the charge of the (c). So that LaFeO 3 /Cu 9 S 5 Compared with single Cu, the composite photocatalysis nano material 9 S 5 Or LaFeO 3 Has stronger organic pollutant degradation capability.
In some embodiments, the present application provides LaFeO 3 /Cu 9 S 5 The heterojunction composite photocatalytic nanomaterial can be used for photocatalytic degradation of organic pollutants including, but not limited to, rhodamine b, methyl blue, methyl orange, bisphenol A and acetaminophen.
In some embodiments, in LaFeO 3 /Cu 9 S 5 Single LaFeO 3 And single Cu 9 S 5 Under the condition that the adding amount is the same and the determination targets are the same, 0.1g of LaFeO provided by the application is used 3 /Cu 9 S 5 The heterojunction composite photocatalysis nano material acts on 100mL of aqueous solution with rhodamine concentration of 5mg/L, the degradation efficiency of rhodamine reaches 100% within 120 minutes, and under the same addition amount condition, single LaFeO is adopted 3 And Cu 9 S 5 The degradation rate of the nano-particles to rhodamine b is only 38.42 percent and 64.16 percent respectively in 120 minutes.
To make geography more clear to those skilled in the artThe application is now described by the following examples of a LaFeO 3 The base heterojunction composite photocatalysis nano material, the preparation method and the application are described in detail.
Example 1
(1) Step 1: preparation of LaFeO 3 Nanoparticle powder
4.3301g (0.01 mol) of lanthanum nitrate hexahydrate (La (NO) 3 ) 3 ·6H 2 O), 4.0400g (0.01 mol) of ferric nitrate nonahydrate (Fe (NO) 3 ) 3 ·9H 2 O) and 5.2535g (0.025 mol) citric acid monohydrate (C) 6 H 8 O 7 ·H 2 O) was dissolved in 180mL of deionized water and stirred at a stirring speed of 400r/min for 1h. The mixed solution was transferred to 200mL of stainless steel autoclave lined with polytetrafluoroethylene and transferred to an oven, reacted at 180 ℃ for 12 hours, and after natural cooling, washed with deionized water for 4 times and centrifuged to obtain a reddish brown precipitate. The reddish brown precipitate was transferred to an evaporation pan, dried at 60 ℃, and ground to give a yellowish brown powder. Calcining brown powder in a tube furnace under nitrogen atmosphere, heating to 700deg.C at a heating rate of 10deg.C/min, maintaining the temperature at 700deg.C for 4 hr, and naturally cooling to obtain black LaFeO with strong ferromagnetism 3 Nanoparticle powder.
(2) Step 2: cu is added with 9 S 5 Nanoparticle composite in LaFeO 3 On the particle (LaFeO) 3 Is the mass of the reactant precursor (LaFeO) 3 47.76% of copper chloride and elemental sulphur)
1.066g LaFeO 3 The nano particles are dissolved in 28.8mL of ethylenediamine and magnetically stirred at a stirring speed of 300r/min, and then 1.066g of CuCl is added in sequence 2 ·2H 2 O,0.1g of elemental sulfur, magnetically stirring for 1h, centrifugally separating a sample, washing with deionized water and absolute ethyl alcohol for three times respectively, and drying in a vacuum constant-temperature drying oven at 80 ℃ for 8h to obtain black powder LaFeO 3 /Cu 9 S 5 。
Example 2
4.3301g (0.01 mol) of lanthanum nitrate hexahydrate (La (NO) 3 ) 3 ·6H 2 O), 4.0400g (0.01 mol) of ferric nitrate nonahydrate (F)e(NO 3 ) 3 ·9H 2 O) and 5.2535g (0.025 mol) citric acid monohydrate (C) 6 H 8 O 7 ·H 2 O) was dissolved in 180mL of deionized water and stirred at a stirring speed of 400r/min for 1h. The mixed solution was transferred to 200mL of stainless steel autoclave lined with polytetrafluoroethylene and transferred to an oven, reacted at 180 ℃ for 12 hours, and after natural cooling, washed with deionized water for 4 times and centrifuged to obtain a reddish brown precipitate. The reddish brown precipitate was transferred to an evaporation pan, dried at 60 ℃, and ground to give a yellowish brown powder. Calcining brown powder in a tube furnace under nitrogen atmosphere, heating to 700deg.C at a heating rate of 10deg.C/min, maintaining the temperature at 700deg.C for 4 hr, and naturally cooling to obtain black LaFeO with strong ferromagnetism 3 Nanoparticle powder.
Example 3
28.8mL of ethylenediamine is taken and magnetically stirred at the stirring speed of 300r/min, and 1.066g of CuCl is added in sequence 2 ·2H 2 O,0.1g of elemental sulfur, magnetically stirring for 1h, centrifugally separating a sample, washing with deionized water and absolute ethyl alcohol for three times respectively, and drying in a vacuum constant-temperature drying oven at 80 ℃ for 8h to obtain black powder Cu 9 S 5 。
FIG. 3 shows LaFeO provided in examples 1-3 of the present application 3 /Cu 9 S 5 Ultraviolet diffuse reflection spectrogram of the heterojunction composite photocatalysis nano material. As shown in FIG. 3, for Cu 9 S 5 The light absorption cut-off edge of the photocatalysis nano material is about 620nm, and the photocatalysis nano material has a certain absorption tail peak. And synthesized LaFeO 3 Has a wider and strong visible light range and has a Cu-like structure at 650nm 9 S 5 Is provided. LaFeO due to the complementary absorption 3 /Cu 9 S 5 The visible light absorption intensity of the heterojunction composite photocatalytic nanomaterial still covers the full visible spectrum, and a larger absorption tail peak appears, which indicates that the heterojunction composite photocatalytic nanomaterial can utilize enough visible light.
FIG. 4 shows LaFeO provided in example 1 of the present application 3 /Cu 9 S 5 N of heterojunction composite photocatalytic nanomaterial 2 Adsorption-desorption isotherm plot as shown in FIG. 4, laFeO 3 /Cu 9 S 5 The specific surface area of the heterojunction composite photocatalytic nanomaterial is 7.29m 2 And/g, the adsorption performance on pollutants is weaker, and the pollutants are reacted and degraded mainly due to the fact that persistent free radicals are generated through photocatalysis.
Fig. 5 shows fourier infrared spectra of photocatalytic nanomaterial provided in examples 1-3 of the present application. As shown in FIG. 5, to investigate the composition and structure of the composite material, FTIR analysis was employed for Cu provided in example 3 9 S 5 ，593cm -1 The stretching vibration peak corresponding to Cu-S shows that cubic crystal Cu 9 S 5 Is formed by the steps of (a). For LaFeO provided in example 2 3 ，LaFeO 3 Is in the range of 500cm -1 A sharp peak appears at the position, and the octahedral FeO 6 The Fe-O stretching vibration of the group corresponds to that of the group. For LaFeO provided in example 1 3 /Cu 9 S 5 ，LaFeO 3 And Cu 9 S 5 The main typical absorption peak of LaFeO exists 3 /Cu 9 S 5 In (C), further indicate LaFeO 3 /Cu 9 S 5 Successful synthesis of the composite catalyst.
Example 4
(1) Step 1: preparation of LaFeO 3 Nanoparticle powder
8.6602g (0.02 mol) of lanthanum nitrate hexahydrate (La (NO) 3 ) 3 ·6H 2 O), 8.0800g (0.02 mol) of ferric nitrate nonahydrate (Fe (NO) 3 ) 3 ·9H 2 O) and 5.2535g (0.025 mol) citric acid monohydrate (C) 6 H 8 O 7 ·H 2 O) was dissolved in 180mL of deionized water and stirred at a stirring speed of 400r/min for 1h. The mixed solution was transferred to 200mL of stainless steel autoclave lined with polytetrafluoroethylene and transferred to an oven, reacted at 150 ℃ for 14 hours, and after natural cooling, washed with deionized water for 4 times and centrifuged to obtain a reddish brown precipitate. The reddish brown precipitate was transferred to an evaporation pan, dried at 60 ℃, and ground to give a yellowish brown powder. Calcining brown powder in a tube furnace under nitrogen atmosphere, heating to 800 deg.C at a heating rate of 10deg.C/min, maintaining the temperature at 800 deg.C for 4.5 hr, and naturally cooling to obtain black powder with strong ferromagnetismLaFeO 3 Nanoparticle powder.
(2) Step 2: cu is added with 9 S 5 Nanoparticle composite in LaFeO 3 On the particle (LaFeO) 3 Is the mass of the reactant precursor (LaFeO) 3 Copper chloride and elemental sulfur) 25%)
0.3886g LaFeO 3 The nano particles are dissolved in 28.8mL of ethylenediamine and magnetically stirred at a stirring speed of 300r/min, and then 1.066g of CuCl is added in sequence 2 ·2H 2 O,0.1g of elemental sulfur, magnetically stirring for 1h, centrifugally separating a sample, washing with deionized water and absolute ethyl alcohol for three times respectively, and drying in a vacuum constant-temperature drying oven at 80 ℃ for 8h to obtain black powder LaFeO 3 /Cu 9 S 5 。
LaFeO prepared in example 4 3 /Cu 9 S 5 Ultraviolet diffuse reflection spectrogram and N of composite photocatalysis nano material 2 The adsorption-desorption isotherm plot and fourier infrared spectrum have the same trend as example 1 and are not repeated here.
Example 5
(1) Step 1: preparation of LaFeO 3 Nanoparticle powder
4.3301g (0.01 mol) of lanthanum nitrate hexahydrate (La (NO) 3 ) 3 ·6H 2 O), 4.0400g (0.01 mol) of ferric nitrate nonahydrate (Fe (NO) 3 ) 3 ·9H 2 O) and 5.2535g (0.025 mol) citric acid monohydrate (C) 6 H 8 O 7 ·H 2 O) was dissolved in 180mL of deionized water and stirred at a stirring speed of 400r/min for 1h. The mixed solution was transferred to 200mL of stainless steel autoclave lined with polytetrafluoroethylene and transferred to an oven, reacted at 180 ℃ for 12 hours, and after natural cooling, washed with deionized water for 4 times and centrifuged to obtain a reddish brown precipitate. The reddish brown precipitate was transferred to an evaporation pan, dried at 60 ℃, and ground to give a yellowish brown powder. Calcining brown powder in a tube furnace under nitrogen atmosphere, heating to 700deg.C at a heating rate of 10deg.C/min, maintaining the temperature at 700deg.C for 4 hr, and naturally cooling to obtain black LaFeO with strong ferromagnetism 3 Nanoparticle powder.
(2) Step 2: cu is added with 9 S 5 Nanoparticle composite in LaFeO 3 On the particle (LaFeO) 3 Is the mass of the reactant precursor (LaFeO) 3 80% of copper chloride and elemental sulfur)
4.664g LaFeO 3 The nano particles are dissolved in 28.8mL of ethylenediamine and magnetically stirred at a stirring speed of 300r/min, and then 1.066g of CuCl is added in sequence 2 ·2H 2 O,0.1g of elemental sulfur, magnetically stirring for 1h, centrifugally separating a sample, washing with deionized water and absolute ethyl alcohol for three times respectively, and drying in a vacuum constant-temperature drying oven at 80 ℃ for 8h to obtain black powder LaFeO 3 /Cu 9 S 5 。
LaFeO prepared in example 5 3 /Cu 9 S 5 Ultraviolet diffuse reflection spectrogram and N of composite photocatalysis nano material 2 The adsorption-desorption isotherm plot and fourier infrared spectrum have the same trend as example 1 and are not repeated here.
To further illustrate the LaFeO prepared by the present application 3 /Cu 9 S 5 The heterojunction composite photocatalytic nanomaterial has the advantages of high visible light utilization rate and high degradation rate of micro pollutants, and the application is specifically analyzed by combining the following experiments.
Experimental example 1
This experimental example was used to verify the LaFeO prepared in example 1, example 2 and example 3 3 /Cu 9 S 5 ，LaFeO 3 And Cu 9 S 5 Degradation performance of the photocatalytic nanomaterial on phenol.
(1) RhB degradation experiments of composite and Single Material:
5mg/L RhB aqueous solution is used as target pollutant for LaFeO 3 、Cu 9 S 5 And LaFeO with different doping ratios 3 /Cu 9 S 5 And carrying out photocatalytic degradation experiments on the composite material. First, 0.1g of the above photocatalyst and 100mL of RhB solution were charged into a photocatalytic reactor, and the mixed solution was placed in the dark and magnetically stirred for 30min to perform a dark adsorption experiment.
Then, under the simulated sunlight irradiation of a xenon lamp of 300W, the method comprises the following steps ofUltraviolet light was removed by an ultraviolet cut filter (420 nm), and a photodegradation experiment was performed on the RhB solution. 2.5mL of the reaction solution was extracted every 10min, centrifuged at 4000rpm for 10min, and the photocatalyst was removed from the reaction solution by filtration, and was purified by a UV-visible spectrophotometer (lambda) RhB =554 nm), the degradation rate η of RhB is calculated as:
η＝(C 0 /C t )/C 0 ×100％
wherein C is 0 And C t The initial concentration of RhB and the concentration after the light t time, respectively.
(2)Cu 9 S 5 And LaFeO 3 /Cu 9 S 5 Heterojunction composite photocatalytic nanomaterial photocatalytic CO 2 Reduction experiment:
CO was performed by irradiation under 300W xenon lamp using LabPLS-SXE300/300UV solar energy system (Perfect Light, china) 2 Is a photocatalytic reduction of (a). Ultraviolet rays were removed using an ultraviolet cut filter (420 nm). 0.02g of the catalyst was uniformly dispersed on a 2X 2cm glass plate and then placed in a quartz reactor. Evacuating the reactor with a vacuum pump, evacuating for about 30min, and subsequently saturating the high purity CO with water vapor 2 Filling the mixture into a reactor under a pressure of 1atm, sealing the reactor, and maintaining the whole reaction system at CO 2 In the atmosphere. The gas products were quantitatively identified on-line using a Flame Ionization Detector (FID) on a gas chromatograph (GC-2014C, shimadzu) using a 300W xenon lamp as a light source, sampled every 1h.
Fig. 6 shows a comparative graph of the performance of visible light catalytic degradation rhodamine b of the photocatalytic nanomaterial provided in examples 1-3 of the present application. As shown in FIG. 6, it can be seen that a single LaFeO 3 And single Cu 9 S 5 The degradation rate of the nano particles to rhodamine B in 120 minutes is 38.42 percent and 64.16 percent respectively, and the LaFeO is prepared by the following steps of 3 /Cu 9 S 5 The degradation efficiency of the photocatalytic nano material to rhodamine B is up to 100% within 120 minutes. The LaFeO provided by the application 3 Base heterojunction composite photocatalysis nano material (LaFeO) 3 /Cu 9 S 5 ) Under irradiation of visible light, exist in Cu 9 S 5 Electrons of the conduction band can easily react with oxygen adsorbed on the surface of the catalyst to generate superoxide radical, and the superoxide radical free radical can rapidly reduce Jie Luodan Minb in a reaction environment; at the same time, is positioned at LaFeO 3 The photo-generated hole in the valence band has stronger oxidation-reduction capability and can directly act on the degradation of pollutants; and in LaFeO 3 Electrons of the conduction band will pass through the Z-type charge transfer mechanism and Cu 9 S 5 Hole recombination in valence band effectively avoids LaFeO 3 And Cu 9 S 5 Is in situ recombined with the charge of the (c). So that LaFeO 3 /Cu 9 S 5 Compared with single Cu, the composite photocatalysis nano material 9 S 5 Or a single LaFeO 3 Has stronger organic pollutant degradation capability.
FIG. 7 shows LaFeO provided by an embodiment of the present application 3 /Cu 9 S 5 Heterojunction composite photocatalytic nanomaterial and single photocatalyst visible light catalytic reduction CO 2 Is a comparison of the performance of (3). As shown in FIG. 7, it can be seen that a single LaFeO 3 And single Cu 9 S 5 Reduction of CO within 5 hours of nanoparticles 2 Is CH 4 Yields of 0.13654. Mu. Mol/g/h and 0.05321. Mu. Mol/g/h, respectively, with LaFeO 3 /Cu 9 S 5 Reduction of CO 2 Is CH 4 The yield of (C) was 0.96546. Mu. Mol/g/h.
The LaFeO provided by the application 3 The basic heterojunction composite photocatalysis nano material, the preparation method and the application are described in detail, and specific examples are applied to illustrate the principle and the implementation mode of the application, and the description of the above examples is only used for helping to understand the method and the core idea of the application; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Claims (10)
1. LaFeO 3 The preparation method of the base heterojunction composite photocatalysis nano material is characterized by comprising the following preparation steps of：
S1, lanthanum nitrate and ferric nitrate with a molar ratio of 1:1 are used as reaction raw materials, the temperature of the hydrothermal reaction is controlled to be 150-180 ℃, the reaction time is controlled to be 10-14 hours, a lanthanum nitrate-ferric nitrate complex is obtained, the target temperature of calcination is further controlled to be 650-850 ℃, the calcination time is controlled to be 4-6 hours, and the complex is subjected to calcination treatment to obtain LaFeO 3 Particles;
s2, weighing LaFeO 3 Particles, copper chloride and elemental sulfur are used as reaction precursors, and react in ethylenediamine solvent to generate black precipitate, and the black precipitate is washed, centrifuged and dried to obtain the LaFeO 3 Base heterojunction composite photocatalytic nanomaterial LaFeO 3 /Cu 9 S 5 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the LaFeO 3 The mass of the particles accounts for 25-80% of the total mass of the reaction precursor, and the molar ratio of the cupric chloride to the elemental sulfur is 2:1.
2. the method according to claim 1, wherein in step S1, the hydrothermal method comprises:
s11, stirring and dissolving lanthanum nitrate, ferric nitrate and citric acid with deionized water to obtain a mixed solution;
s12, transferring the mixed solution to a Teflon reaction kettle for hydrothermal reaction, and cooling, washing, centrifuging and drying a product to obtain a lanthanum nitrate-ferric nitrate complex;
s13, grinding the lanthanum nitrate-ferric nitrate complex, transferring to a crucible, placing the crucible into a tube furnace under the atmosphere of inert gas or nitrogen, heating to the target temperature at a heating rate of 5-10 ℃/min, and calcining to obtain black solid powder product LaFeO 3 And (3) particles.
3. The process according to claim 1 or 2, wherein the hydrothermal reaction is carried out at a temperature of 180℃for a period of 12 hours.
4. The method according to claim 2, wherein in step S12, the washing centrifugal detergent is deionized water, and the drying temperature is 60-90 ℃.
5. The method according to claim 2, wherein in step S13, the temperature rise rate is 10 ℃/min, the target temperature is 700 ℃, and the calcination time is 4 hours.
6. The method according to claim 1, wherein in step S2, the washing and centrifuging operation comprises: washing with deionized water and ethanol for 3-4 times at intervals;
the temperature of the drying is 60-80 ℃.
7. The method according to claim 1, wherein in step S2, the LaFeO is prepared by 3 The mass of the particles was 47.76% of the total mass of the reaction precursor.
8. LaFeO obtained by the preparation method of any one of claims 1-7 3 The base heterojunction composite photocatalysis nano material.
9. LaFeO obtained by the preparation method of any one of claims 1-7 3 The application of the base heterojunction composite photocatalysis nano material is characterized in that the LaFeO 3 Base heterojunction composite photocatalytic nanomaterial for driving CO by visible light 2 Is reduced by (a).
10. LaFeO obtained by the preparation method of any one of claims 1-7 3 The application of the base heterojunction composite photocatalysis nano material is characterized in that the LaFeO 3 The base heterojunction composite photocatalysis nano material is used for degrading organic pollutants driven by visible light.
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| CN109019696A (en) * | 2018-08-01 | 2018-12-18 | 济南大学 | A kind of Au-LaFeO3The preparation method of nanocomposite |
| CN109759069A (en) * | 2019-03-18 | 2019-05-17 | 福州大学 | A kind of preparation and application of the perovskite material for photocatalytic reduction of carbon oxide |
| BR102019025561A2 (en) * | 2019-12-03 | 2021-06-15 | Fundação Universidade Federal De São Carlos | COMPOSITION FOR CERAMIC THIN FILMS, RESIN OBTAINING PROCESS FOR CERAMIC THIN FILMS ON GLASS/FTO SUBSTRATE AND CERAMIC THIN FILMS ON GLASS/FTO SUBSTRATE OBTAINED |
| CN113813967A (en) * | 2021-09-04 | 2021-12-21 | 江西理工大学 | LaFeO3/In2S3Preparation method and application of composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109019696A (en) * | 2018-08-01 | 2018-12-18 | 济南大学 | A kind of Au-LaFeO3The preparation method of nanocomposite |
| CN109759069A (en) * | 2019-03-18 | 2019-05-17 | 福州大学 | A kind of preparation and application of the perovskite material for photocatalytic reduction of carbon oxide |
| BR102019025561A2 (en) * | 2019-12-03 | 2021-06-15 | Fundação Universidade Federal De São Carlos | COMPOSITION FOR CERAMIC THIN FILMS, RESIN OBTAINING PROCESS FOR CERAMIC THIN FILMS ON GLASS/FTO SUBSTRATE AND CERAMIC THIN FILMS ON GLASS/FTO SUBSTRATE OBTAINED |
| CN113813967A (en) * | 2021-09-04 | 2021-12-21 | 江西理工大学 | LaFeO3/In2S3Preparation method and application of composite material |
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