CN115739195B - Double-site S-type heterojunction photo-Fenton catalyst and preparation method and application thereof - Google Patents
Double-site S-type heterojunction photo-Fenton catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN115739195B CN115739195B CN202211630440.6A CN202211630440A CN115739195B CN 115739195 B CN115739195 B CN 115739195B CN 202211630440 A CN202211630440 A CN 202211630440A CN 115739195 B CN115739195 B CN 115739195B
- Authority
- CN
- China
- Prior art keywords
- site
- tio
- catalyst
- double
- mpc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 14
- 231100000719 pollutant Toxicity 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 3
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- -1 phosphate radical Chemical class 0.000 claims description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 30
- 238000006731 degradation reaction Methods 0.000 abstract description 30
- 230000005684 electric field Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 230000001404 mediated effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 239000005447 environmental material Substances 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 229960001699 ofloxacin Drugs 0.000 description 30
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- 239000011941 photocatalyst Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229960003405 ciprofloxacin Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229960001180 norfloxacin Drugs 0.000 description 2
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000008863 intramolecular interaction Effects 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000003306 quinoline derived antiinfective agent Substances 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229960005404 sulfamethoxazole Drugs 0.000 description 1
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to the field of environmental materials, in particular to a double-site S-type heterojunction photo-Fenton catalyst, a preparation method and application thereof, and the double-site S-type heterojunction photo-Fenton catalyst (MPc-P-TiO) is prepared by phosphate-mediated sequential assembly 2 ) The catalyst reacts with H through hydrogen bond 2 O 2 Bind to make H 2 O 2 Loss of electron dissociation to form O 2 ‑ The method comprises the steps of carrying out a first treatment on the surface of the At the same time, electrons are transferred to FePc under the drive of built-in electric field and pass through O 2 The reduction reaction further produces O 2 ‑ Can realize synergistic effect, thereby greatly reducing H 2 O 2 Consumption, overcoming the defect that the pollutant degradation efficiency in the traditional photo Fenton process is limited by H 2 O 2 Limitations in the amount to be added. The invention develops the efficient photo Fenton technology based on the double-site structure design and the directional electron transfer strategy, and has the technical and economic comprehensive advantages of high pollutant removal rate, low oxidant consumption and the like.
Description
Technical Field
The invention relates to the field of environmental materials, in particular to a double-site S-type heterojunction photo-Fenton catalyst and a preparation method and application thereof.
Background
The photo Fenton is used as an advanced oxidation technology, can generate rich active oxygen species, and has higher removal efficiency on various pollutants in water. However, the reactive oxygen species of conventional photoFenton are mainly derived from H 2 O 2 Leading to H 2 O 2 Is high. H produced by industrial anthraquinone process 2 O 2 Relates generally to high pollution and high energy consumption, and H 2 O 2 Large-scale transport and storage of (c) is at great risk and is therefore high in H 2 O 2 The consumption limits the practical application of photo Fenton. By using dissolved oxygen (O) in water 2 ) Replacement or enhancement of H 2 O 2 The generation of active oxygen species is cheaper and safer. But from the thermodynamic point of view, H 2 O 2 Will be combined with O 2 Competing for electrons, and H 2 O 2 Is a reduction priority of (1) to O 2 Is difficult to be effectively utilized (E (H) 2 O 2 /·O 2 - )＝+1.14eV vs.E(O 2 /·O 2 - ) = -0.046 eV). Taking into account H 2 O 2 Can be used as both electron acceptor and electron donor, thus H can be generated by regulating the catalytic site 2 O 2 As electron donor only to eliminate its and O 2 Competing electrons.
Hydrogen bonding is a polar intermolecular or intramolecular interaction. Taking into account H 2 O 2 The molecule contains O-H groups, and the catalyst with Y groups on the surface can form hydrogen bonding action and further lose electrons. In this case H 2 O 2 As electron donor to eliminate its interaction with O 2 Competition for electrons. By constructing with H 2 O 2 Oxidation and O 2 Reducing double-site S-type heterojunction photocatalyst, on one hand, driving electrons from H by means of built-in electric field generated by balancing fermi energy level 2 O 2 Continuous transition to O 2 The method comprises the steps of carrying out a first treatment on the surface of the On the other hand, H is realized synchronously from strong oxidation-reduction capability 2 O 2 Oxidation and O 2 And (5) reduction. Thus by increasing O 2 Greatly reduces H 2 O 2 Consumption, the synergistic effect of the two can generate rich active oxygen species, thereby enhancing the removal of pollutants in water.
Ahmad et al (Applied Catalysis B: environmental,2020,264, 118534) employ an MIL-88B-Fe/Ti rich in unsaturated sites 3 C 2 The catalyst degrades the antibiotic sulfamethoxazole, and the concentration of the catalyst is 0.5g/L, H 2 O 2 Under the condition of the addition amount of 10mmol/L, the degradation rate constant is 0.035min -1 Its contaminationThe degradation rate is slower and the oxidant consumption is higher. The patent publication No. CN106238053A discloses a photo-Fenton catalyst Fe 3 O 4 /rGO/TiO 2 And its preparation method and application ", in catalyst concentration of 0.4g/L, H 2 O 2 Under the condition that the addition amount is 10mmol/L, the removal rate of the tetracycline hydrochloride of 25mg/L in 6 hours is about 95 percent, the reaction efficiency is low, and the dosages of the catalyst and the oxidant are relatively high.
Disclosure of Invention
The invention aims to overcome H faced by the existing optical Fenton technology 2 O 2 The defects of high dosage, low pollutant degradation rate and the like provide a double-site S-type heterojunction photo-Fenton catalyst, and a preparation method and application thereof, and can realize low H 2 O 2 High-efficiency degradation of pollutants in water under the conditions of low consumption and low catalyst addition.
The invention prepares the double-site S-type heterojunction photo-Fenton catalyst (MPc-P-TiO) through phosphate radical mediated sequential assembly 2 ). The catalyst reacts with H through hydrogen bond 2 O 2 Bind to make H 2 O 2 Loss of electron dissociation to form O 2 - The method comprises the steps of carrying out a first treatment on the surface of the At the same time, electrons are transferred to FePc under the drive of built-in electric field and pass through O 2 The reduction reaction further produces O 2 - Can realize synergistic effect, thereby greatly reducing H 2 O 2 Consumption, overcoming the defect that the pollutant degradation efficiency in the traditional photo Fenton process is limited by H 2 O 2 Limitations in the amount to be added. The invention develops the efficient photo Fenton technology based on the double-site structure design and the directional electron transfer strategy, and has the technical and economic comprehensive advantages of high pollutant removal rate, low oxidant consumption and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a double-site S-type heterojunction photo-Fenton catalyst is prepared from TiO 2 And MPc mediated by phosphate groups, the resulting complex being an S-type heterojunction, the catalyst having H 2 O 2 Electron-loss sites and O 2 And obtaining an electron site.
The invention provides a preparation method of the double-site S-type heterojunction photo-Fenton catalyst, which comprises the following steps:
(1) TiO is mixed with 2 Mixing with phosphoric acid or phosphate in water to obtain a mixture A. Drying to obtain phosphoric acid modified P-TiO 2 ；
(2) Dispersing MPc in organic solvent to obtain MPc suspension, and adding the above P-TiO 2 Stirring and self-assembling to obtain a mixture B; drying to obtain the double-site S-type heterojunction photo-Fenton catalyst MPc-P-TiO 2 。
Preferably, the TiO in the mixed solution A in the step (1) 2 The mass ratio of phosphoric acid or phosphate to water is as follows: 1:0.02-0.1:50-150. TiO (titanium dioxide) 2 The mass ratio of phosphoric acid or phosphate to water is as follows: any number within the range of 1:0.02-0.1:50-150, such as 1:0.02:50, 1:0.05:80, 1:0.1:150.
In any of the above schemes, preferably, the phosphate in the step (1) is any one or more of potassium phosphate, potassium phosphate monobasic, sodium phosphate monobasic and sodium phosphate monobasic.
In any of the above embodiments, preferably, the stirring time in the step (1) is 0.5 to 2 hours, and the stirring speed is 100 to 1000rpm; the drying temperature is 60-90 ℃ and the drying time is 10-30 h.
In any of the above embodiments, it is preferable that the P-TiO in the mixture B in the step (2) 2 The mass ratio of MPc to organic solvent is as follows: 1:0.01-0.09:100-1000.
P-TiO 2 The mass ratio of MPc to organic solvent is 1:0.01-0.09:100-1000, and may be 1:0.01:100, 1:0.04:500, or 1:0.09:1000.
Q-in any one of the above schemes, preferably, MPc in the step (2) comprises any one or more of iron phthalocyanine, copper phthalocyanine, manganese phthalocyanine and cobalt phthalocyanine; the organic solvent comprises any one or more of methanol, ethanol and N, N-dimethylformamide.
In any of the above schemes, preferably, the self-assembly temperature in the step (2) is 20-90 ℃, the stirring time is 0.2-5 h, and the stirring speed is 100-1000 rpm; the drying temperature is 60-90 ℃ and the drying time is 4-30 h.
The double-site S-type heterojunction photo-Fenton catalyst prepared by the method is applied to removal of pollutants in water.
When removing pollutants in water, the specific processing steps are as follows: MPc-P-TiO 2 Mixing with solution containing antibiotic, adding H 2 O 2 The light source is turned on to react.
Preferably, in the application, the contaminants, catalyst and H in the reaction 2 O 2 The mass ratio of the catalyst is 1:5-15:0.17-1.7, and the reaction time is 5-60 min. Catalyst and H 2 O 2 The mass ratio of (2) is 1:5-15:0.17-1.7, such as 1:5: 0.17,1:10:1, 1:15:1.7.
The technical effects are as follows:
compared with the prior art, the method has the following remarkable advantages:
(1) Compared with the traditional heterojunction catalyst, the double-site S-type heterojunction photo-Fenton catalyst prepared by the invention has H 2 O 2 Electron-loss sites and O 2 And obtaining an electron site.
(2) The invention mediates H through the built-in electric field of the S-type heterojunction 2 O 2 Migration of electrons to O 2 Compared with the conventional photo Fenton technology, H is eliminated 2 O 2 And O 2 To increase O 2 Thereby reducing the H to high 2 O 2 Dependence of the amount of addition.
(3) The double-site S-type heterojunction photo-Fenton catalyst prepared by the invention has H 2 O 2 And O 2 Combined double-site, synchronous realization of H 2 O 2 Oxidation and O 2 Reducing, enhancing the generation of active oxygen species, and can efficiently degrade various pollutants in water.
Drawings
FIG. 1 shows a double-site S-type heterojunction FePc-P-TiO in the invention 2 Is a transmission electron microscope image;
FIG. 2 shows a double-site S-type heterojunction FePc-P-TiO in the present invention 2 A work function map of (2);
FIG. 3 shows a double-site S-type heterojunction FePc-P-TiO in the present invention 2 Is a schematic diagram of charge transfer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. The various terms and phrases used herein have the ordinary meaning known to those skilled in the art. The materials used in the test and the test method are described generally or specifically. Although many materials and methods of operation are known in the art for accomplishing the objectives of the present invention, the present invention will be described in as much detail herein.
The instruments, reagents, materials, and the like in the following examples are conventional instruments, reagents, materials, and the like existing in the prior art unless otherwise specified, and are conventional experimental methods, detection methods, and the like existing in the prior art unless otherwise specified.
Example 1
Double-site S-type heterojunction FePc-P-TiO 2 The photocatalyst and the preparation method thereof specifically comprise the following steps in sequence:
a: 1g of TiO 2 With 20mg H 3 PO 4 Mixing and dissolving in 50ml of ultrapure water, fully stirring for 2 hours, and stirring at a speed of 100rpm;
b: evaporating in an oven at 60 ℃ for 30h. Finally, washing and drying to obtain phosphoric acid modified P-TiO 2 ；
c: dispersing 1mg FePc in 50g absolute ethanol, collecting the above obtained P-TiO 2 100mg of the mixture is added into FePc suspension, and stirred for 0.2h at 20 ℃ with the stirring speed of 500rpm;
d: evaporating the solvent at 90 ℃ for 4 hours to obtain FePc-P-TiO 2 And the number is A.
The double-site S-type heterojunction FePc-P-TiO obtained in this example 2 The projection electron microscope and work function of the photocatalyst are shown in fig. 1 and 2, and the charge transfer is shown in the schematic diagramAs shown in FIG. 3, it can be seen that the table FePc-P-TiO 2 The surface is rough and the length is 10-50nm. TiO (titanium dioxide) 2 And FePc work functions of 6.4eV and 4.7eV, electrons are transferred from FePc to TiO due to work function difference 2 Thereby forming a built-in electric field at the heterojunction interface. The density functional theory calculation shows that H 2 O 2 Tends to adsorb on TiO 2 The surface is on the phosphoric acid, and electrons are lost through the phosphoric acid; and O is 2 It is more likely to adsorb at the FePc end and get electrons reduced.
Ofloxacin is a typical fluoroquinolone antibiotic. The example was followed to obtain a double-site S-heterojunction FePc-P-TiO 2 The photocatalyst is used for degrading ofloxacin. The specific experimental conditions are as follows: 10mg of the catalyst was placed in 50mL of 20mg/L ofloxacin solution, and after 30min, the adsorption-desorption equilibrium was reached, followed by the addition of 0.4mM H 2 O 2 And starting 500W xenon lamp to initiate reaction, the degradation result of ofloxacin is shown in table 3, the degradation rate of ofloxacin in 30min reaches 99.8%, and the reaction kinetic constant reaches 0.275min -1 And H is 2 O 2 The addition amount of the catalyst is reduced by 5-250 times compared with the prior reported photo Fenton, and the catalyst is proved to be under ultra-low H 2 O 2 High efficiency under the condition of adding amount.
Example 2
A method for preparing a double-site S-type heterojunction photo-Fenton catalyst, which is similar to example 1, except that:
in step a, 1g of TiO is added 2 With 100mg KH 2 PO 4 Mixing and dissolving in 150ml of ultrapure water; in step b, the mixture was evaporated in an oven at 90℃for 20h. The catalyst obtained is numbered B. Under the same experimental conditions as in example 1, the degradation rate of ofloxacin within 30min was 99.3%.
Example 3
A method for preparing a double-site S-type heterojunction photo-Fenton catalyst, which is similar to example 1, except that:
in step a, the mixing mode is changed into: fully stirring for 0.5h at a stirring speed of 1000rpm; in step b, the drying conditions are changed to: evaporated in an oven at 70 ℃ for 15h. The catalyst obtained is numbered C. Under the same experimental conditions as in example 1, the degradation rate of ofloxacin within 30min was 98.6%.
Example 4
A method for preparing a double-site S-type heterojunction photo-Fenton catalyst, which is similar to example 1, except that:
in step c, 4.5mg of FePc is dispersed in 100ml of ethanol, and the obtained P-TiO is taken 2 50mg was added to the FePc suspension. In the step d, the drying mode is changed into: the solvent was evaporated at 60℃for 30h. The catalyst obtained is numbered D. Under the same experimental conditions as in example 1, the degradation rate of ofloxacin within 30min was 94.8%.
Example 5
A method for preparing a double-site S-type heterojunction photo-Fenton catalyst, which is similar to example 1, except that:
in step a, the mixing mode is changed into: fully stirring for 1h at a stirring speed of 500rpm; in step c, 2mg of CoPc is dispersed in 80ml of methanol, and the 8P-TiO obtained above is taken 2 100mg was added to the CoPc suspension. The catalyst obtained is numbered E. Under the same experimental conditions as in example 1, the degradation rate of ofloxacin within 30min was 96.9%.
Example 6
A method for preparing a double-site S-type heterojunction photo-Fenton catalyst, which is similar to example 1, except that:
in step c, the mixing mode is changed into: stirring for 5h at 30 ℃ with a stirring speed of 100rpm; in the step d, the drying mode is changed into: the solvent was evaporated at 80℃for 10h. The catalyst obtained is numbered F. Under the same experimental conditions as in example 1, the degradation rate of ofloxacin within 30min was 95.2%.
Example 7
A method for preparing a double-site S-type heterojunction photo-Fenton catalyst, which is similar to example 1, except that: in step c, the mixing mode is changed into: stirring for 1h at 30 ℃ with a stirring speed of 200rpm; the drying mode in the step d is changed into: drying temperature is 70 ℃ and 30 hours. The catalyst obtained is numbered G. Under the same experimental conditions as in example 1, the degradation rate of ofloxacin within 30min was 98.6%.
The degradation rate data of the double-site S-type heterojunction for ofloxacin prepared in examples 1-7 are shown in Table 1:
TABLE 1 degradation Rate of double-site S-heterojunction Parofloxacin prepared in examples 1-7
Example 8
To examine the degradation effect of the catalyst on different antibiotics, the same example 1 was repeated except that the pollutant was changed to any one of ciprofloxacin, tetracycline hydrochloride, norfloxacin, and the degradation rate of ciprofloxacin, tetracycline hydrochloride, norfloxacin, methylene blue, and bisphenol a was 95.8%,98.4%,98.0%,92.1%, and 90.5%, respectively, under the same experimental conditions as in example 1, indicating that the catalyst has broad spectrum for removing organic pollutants in water.
Example 9
To examine the effect of the catalyst on the degradation of ofloxacin in the presence of different inorganic salts, the same example 1 was repeated except that 10mM of Cl was added to the ofloxacin solution - 、SO 4 2- 、HCQ 3 - 、H 2 PQ 4 - NO and NO 3 - The degradation rate of ofloxacin is shown in table 2: the degradation rate of ofloxacin in 30min is 98.43%,99.56%,99.41%,98.87% and 97.99%, respectively, which shows that the catalyst can still remove ofloxacin in water with high efficiency under the existence of various inorganic salts.
TABLE 2 degradation Rate of ofloxacin in the Presence of different inorganic salts of double site S-type heterojunction
| Inorganic salt species | Cl - | SO 4 2- | HCO 3 - | H 2 PO 4 - | NO 3 - |
| Ofloxacin degradation rate (%) | 98.43 | 99.56 | 99.41 | 98.87 | 97.99 |
Example 10
To examine the effect of the catalyst on the degradation of ofloxacin under different pH conditions, the same as in example 1 was conducted except that the initial pH of the ofloxacin solution was adjusted to 4.03, 5.00, 6.02, 7.03 and 8.01, respectively, and the degradation rate of ofloxacin was as shown in Table 3: the degradation rate of ofloxacin in 30min is 98.33%,99.49%,99.39%,99.42% and 99.11%, respectively, which indicates that the catalyst can still remove ofloxacin in water with high efficiency under the condition of pH=3-8.
Table 3 degradation rate of ofloxacin at different pH conditions for double-site S-type heterojunction.
| pH | 4.03 | 5.00 | 6.02 | 7.03 | 8.01 |
| Ofloxacin degradation rate (%) | 98.33 | 99.49 | 99.39 | 99.42 | 99.11 |
Comparative example 1
To highlight the double-site S-type heterojunction FePc-P-TiO 2 Phosphoric acid in the photocatalyst plays an important role in the process of catalyzing and degrading ofloxacin, and a catalyst which is not modified by phosphoric acid is prepared, and the difference of the catalytic effect of the catalyst and the catalytic effect of the composite catalyst obtained in the example 1 is compared. The preparation process is the same as in example 1, except that 8P-TiO is used in step c 2 Change to TiO 2 The catalyst obtained had a degradation rate of ofloxacin of 71.8% in 30min under the same experimental conditions as in example 1.
Comparative example 2
To highlight the double-site S-type heterojunction FePc-P-TiO 2 The important role of FePc in the photocatalyst in the process of catalyzing and degrading ofloxacin is played, and the catalyst without compounding FePc is prepared, and the difference of the catalytic effect of the catalyst and the catalytic effect of the compound catalyst obtained in the example 1 is compared. The preparation method is the same as in example 1, except that the treatment of steps c and d is not carried out, the degradation rate of the obtained catalyst to ofloxacin in 30min is 98.9% under the same experimental conditions as in example 1, and the reaction is dynamicThe mechanical constant is reduced by 2.7 times.
The present invention is not limited to the above-mentioned embodiments, and any person skilled in the art, based on the technical solution of the present invention and the inventive concept thereof, can be replaced or changed within the scope of the present invention.
Claims (9)
1. A preparation method of a double-site S-type heterojunction photo-Fenton catalyst is characterized by comprising the following steps of 2 And metal phthalocyanine (MPc) through the mediation of phosphate radical, the obtained compound is S-shaped heterojunction, and the catalyst simultaneously has H 2 O 2 Electron-loss sites and O 2 Obtaining an electron site, comprising the following steps:
(1) TiO is mixed with 2 Mixing with phosphoric acid or phosphate in water, stirring to obtain mixture A, and drying to obtain phosphoric acid modified P-TiO 2 ；
(2) Dispersing MPc in an organic solvent to obtain MPc suspension, and adding the P-TiO prepared in the step (1) 2 Stirring and self-assembling to obtain a mixture B, and drying to obtain the double-site S-type heterojunction photo-Fenton catalyst MPc-P-TiO 2 。
2. The process according to claim 1, wherein TiO in mixture A in step (1) 2 The mass ratio of the water to the phosphoric acid or the phosphate is as follows: 1 (0.02-0.1) and 50-150).
3. The preparation method according to claim 1, wherein in the step (1), the stirring time is 0.5-2 hours, and the stirring speed is 100-1000 rpm; the drying temperature is 60-90 ℃ and the drying time is 10-30 h.
4. The method according to claim 1, wherein the phosphate in the step (1) is any one or more of potassium phosphate, potassium phosphate monobasic, sodium phosphate monobasic and sodium phosphate monobasic.
5. The process according to claim 1, wherein the P-TiO in the mixture B in the step (2) 2 The mass ratio of the organic solvent to MPc is as follows: 1 (0.01-0.09) and 100-1000.
6. The method according to claim 1, wherein the MPc in the step (2) comprises any one or more of iron phthalocyanine, copper phthalocyanine, manganese phthalocyanine and cobalt phthalocyanine; the organic solvent comprises any one or more of methanol, ethanol and N, N-dimethylformamide.
7. The preparation method according to claim 1, wherein the self-assembly temperature in the step (2) is 20-90 ℃, the stirring time is 0.2-5 h, and the stirring speed is 100-1000 rpm; the drying temperature is 60-90 ℃, and the drying time is 4-30 hours.
8. Use of a dual-site S-type heterojunction photo-fenton catalyst prepared according to the method of any one of claims 1-7 for removing contaminants from water.
9. The use according to claim 8, characterized in that the processing steps are as follows: MPc-P-TiO 2 Mixing with solution containing pollutant, adding H 2 O 2 Turning on light source to react, pollutant, catalyst and H 2 O 2 The mass ratio of (3) is as follows: 1 (5-15), 0.17-1.7, and the reaction time is 5-60 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211630440.6A CN115739195B (en) | 2022-12-15 | 2022-12-15 | Double-site S-type heterojunction photo-Fenton catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211630440.6A CN115739195B (en) | 2022-12-15 | 2022-12-15 | Double-site S-type heterojunction photo-Fenton catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115739195A CN115739195A (en) | 2023-03-07 |
| CN115739195B true CN115739195B (en) | 2024-02-23 |
Family
ID=85346538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211630440.6A Active CN115739195B (en) | 2022-12-15 | 2022-12-15 | Double-site S-type heterojunction photo-Fenton catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115739195B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102258992A (en) * | 2011-06-23 | 2011-11-30 | 浙江大学 | Surface iron modified titanium dioxide photocatalyst as well as preparation method and application thereof |
| CN106238053A (en) * | 2016-07-06 | 2016-12-21 | 华南理工大学 | A kind of light fenton catalyst Fe3o4/ rGO/TiO2and its preparation method and application |
| CN110665529A (en) * | 2019-10-12 | 2020-01-10 | 南京农业大学 | Method for catalytically degrading antibiotics by nitrogen-containing doped modified nano titanium dioxide and evaluation method |
| CN112791747A (en) * | 2021-01-05 | 2021-05-14 | 黑龙江大学 | Preparation method and application of ultrathin two-dimensional phosphoric acid regulated metal phthalocyanine/perylene bisimide composite photocatalyst |
| CN114082448A (en) * | 2021-12-09 | 2022-02-25 | 武汉大学(肇庆)资源与环境技术研究院 | Tb-MOF/P-TiO2Heterojunction photocatalyst and preparation and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7888502B2 (en) * | 2007-06-27 | 2011-02-15 | Xerox Corporation | Titanyl phthalocyanine processes and photoconductors thereof |
-
2022
- 2022-12-15 CN CN202211630440.6A patent/CN115739195B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102258992A (en) * | 2011-06-23 | 2011-11-30 | 浙江大学 | Surface iron modified titanium dioxide photocatalyst as well as preparation method and application thereof |
| CN106238053A (en) * | 2016-07-06 | 2016-12-21 | 华南理工大学 | A kind of light fenton catalyst Fe3o4/ rGO/TiO2and its preparation method and application |
| CN110665529A (en) * | 2019-10-12 | 2020-01-10 | 南京农业大学 | Method for catalytically degrading antibiotics by nitrogen-containing doped modified nano titanium dioxide and evaluation method |
| CN112791747A (en) * | 2021-01-05 | 2021-05-14 | 黑龙江大学 | Preparation method and application of ultrathin two-dimensional phosphoric acid regulated metal phthalocyanine/perylene bisimide composite photocatalyst |
| CN114082448A (en) * | 2021-12-09 | 2022-02-25 | 武汉大学(肇庆)资源与环境技术研究院 | Tb-MOF/P-TiO2Heterojunction photocatalyst and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115739195A (en) | 2023-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111889073B (en) | Preparation method of defect-rich molybdenum disulfide-bacterial cellulose heterojunction material for treating radioactive wastewater | |
| CN110776049B (en) | Method for treating organic wastewater by activating peroxymonosulfate with functionalized zirconium-based metal organic framework/protonated carbon nitride composite material | |
| CN108452820B (en) | Carbon nitride/alpha-type iron oxide catalyst, photoelectric auxiliary Fenton-like system and application of photoelectric auxiliary Fenton-like system in organic wastewater treatment | |
| CN113289647B (en) | Biochar doped BiOBr x Cl 1-x Photocatalyst, preparation method and application | |
| CN108479700A (en) | A kind of preparation method for Cr VI and the porous carbon composite material of methyl orange eutectoid content | |
| CN114345417B (en) | Polyvinylidene fluoride functional film loaded with copper-iron porphyrin composite nano-sheet and preparation and application thereof | |
| CN115739195B (en) | Double-site S-type heterojunction photo-Fenton catalyst and preparation method and application thereof | |
| CN105688929A (en) | Neutral advanced oxidation catalyst with pelelith as carrier and preparing method of neutral advanced oxidation catalyst | |
| CN108554458B (en) | Bismuth vanadate composite photocatalyst and preparation method thereof | |
| CN115090312A (en) | Preparation method and application of MOF-derived Co and Zn-doped porous carbon nitride catalyst | |
| CN113145158B (en) | Stripped tubular carbon nitride photocatalyst and preparation method and application thereof | |
| CN112169750B (en) | Application of basic potassium salt modified graphite phase carbon nitride in preparation of cationic dye adsorbent | |
| CN111203245B (en) | Composite photocatalyst for efficiently degrading ciprofloxacin and preparation method and application thereof | |
| CN111085174A (en) | Sn (tin)3O4-BiOCl heterojunction photocatalytic composite porous adsorption material and preparation method thereof | |
| CN111659468A (en) | MoS2Defective MIL-100(Fe) composite catalyst, preparation method and application | |
| CN108772081B (en) | FePO4 heterogeneous visible light Fenton catalyst and method for treating organic wastewater | |
| CN111013588A (en) | Fenton-like catalyst and preparation method and application thereof | |
| CN106268720A (en) | A kind of preparation method of the biological carbon composite adsorbing material removing surface water body molybdate | |
| CN116212931A (en) | Visible light driven seawater in-situ Fenton system and application thereof in rapid degradation of organic micro-pollutants in water | |
| CN113786849B (en) | FeOCl/GQDs composite transition metal catalyst and preparation method and application thereof | |
| CN114985006A (en) | Two-dimensional layered catalytic membrane material, preparation method and application | |
| CN114904534A (en) | Bismuth molybdate/ferric vanadate composite nanomaterial, preparation method thereof and application thereof in acousto-optic catalytic degradation of pollutants in water | |
| CN114807112A (en) | Method for immobilizing laccase by magnetic graphite-phase carbon nitride and application of laccase | |
| CN110624590B (en) | photo-Fenton heterogeneous composite catalyst and preparation method and application thereof | |
| CN113698058A (en) | Sludge pretreatment method based on sulfoporphyrin iron catalyst Fenton system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |