CN110694639A - Preparation method of multi-interface magnetic heterojunction - Google Patents
Preparation method of multi-interface magnetic heterojunction Download PDFInfo
- Publication number
- CN110694639A CN110694639A CN201910982465.4A CN201910982465A CN110694639A CN 110694639 A CN110694639 A CN 110694639A CN 201910982465 A CN201910982465 A CN 201910982465A CN 110694639 A CN110694639 A CN 110694639A
- Authority
- CN
- China
- Prior art keywords
- cavity
- precursor
- source precursor
- reaction
- tin
- 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.)
- Granted
Links
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 33
- 238000000151 deposition Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims description 92
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 229910052742 iron Inorganic materials 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 230000008021 deposition Effects 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 229960003405 ciprofloxacin Drugs 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 2
- 239000002800 charge carrier Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 18
- 239000010410 layer Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 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
- 230000008859 change Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 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 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a multi-interface magnetic heterojunction, in particular to a method for preparing a multi-interface magnetic heterojunction by utilizing an atomic layer deposition technology. The technical problem of easy recombination of photon-generated electron-hole pairs is solved by reasonably designing multiple interfaces in the heterojunction and increasing a charge carrier transfer way, and the problem of difficult recycling of the catalyst in the water treatment process is solved by depositing the magnetic shell photocatalyst. Subsequently, two catalysts, a and B, at least one of which has magnetic properties, are alternately deposited on the surface of the nano-core substrate using ALD technique and annealed. The prepared multi-interface magnetic heterojunction promotes the efficient separation and transfer of photon-generated carriers, is easy to recycle under the action of an external magnetic field, has remarkably enhanced photocatalytic activity, and has a ciprofloxacin pollutant solution (the initial concentration is 15mg/L) removal rate of more than 90% under the condition of 150W visible light for 30 min. After 5 times of cyclic catalytic degradation, the multi-interface heterojunction still shows higher catalytic stability.
Description
Technical Field
The invention relates to a method for preparing a multi-interface magnetic heterojunction by utilizing an atomic layer deposition technology. In particular to a preparation method of a multi-interface magnetic heterojunction.
Background
In recent years, some emerging micropollutants (such as antibiotics, pesticides and endocrine disruptors) are frequently detected in water, and cause great risks to human health. The photocatalytic oxidation technology is considered as a green, environment-friendly and efficient water treatment technology and is widely concerned by students.
The research and development of the high-activity photocatalyst are the premise and the key for improving the photocatalytic degradation efficiency, and the photocatalyst is developed from an initial single component to a double-component and multi-component doping body at present, so that the catalytic efficiency under visible light is obviously improved. The traditional catalyst preparation method mainly comprises a hydrothermal method, an impregnation method and a sintering method, and researches show that the composite catalyst prepared by the method has the problems of uneven component distribution, poor stability and uncontrollable preparation process, is easy to form an electron-hole recombination center, and becomes a main bottleneck for limiting the further improvement of the photocatalytic efficiency.
The Atomic Layer Deposition (ALD) technique can uniformly deposit an active functional layer on the surface of a substrate with a high aspect ratio through alternating pulse reaction between gas precursors, and can accurately control the thickness of the active functional layer on a nanometer scale, thereby being a high-precision catalyst preparation technique. At present, ALD has been used for assisting in the construction of single interface heterojunctions, and the catalytic activity under visible light is obviously improved. Kim et al in g-C by ALD3N4ZnS quantum dot deposited on surface and preparation of ZnS/g-C3N4The type II heterojunction has higher photocatalytic degradation efficiency on methylene blue than that of g-C3N4Increased by 1.6 times (appl. surf. Sci.,2017,419, 159-164). Wang et al on TiO by ALD2Pt nano particles and TiO are uniformly deposited on the surface of the nano wire2The degradation efficiency of a Pt single interface heterojunction on rhodamine B is improved to 2.12 times before deposition (Nanotechnology,2015,26, 254002). However, only a single interface present in the catalyst is facing the photo-generated electronsThe efficiency of hole pair separation is to be further improved, the transfer path of the charge carriers is relatively single, and this is not favorable for the rapid formation of active species and the improvement of photocatalytic efficiency. In addition, most of the reported ALD shell layer photocatalysts are not easy to recycle, and the recycling cost is high.
Disclosure of Invention
The invention uses ALD technology to alternatively deposit two components A and B on the surface of a nanometer core substrate, at least one of which has magnetism, and the magnetic multi-interface heterojunction is obtained through annealing treatment; the specific preparation steps are as follows:
1) dispersing the nano-core substrate material in an ethanol solution to prepare a suspension with the concentration range of 6-30g/L, uniformly dripping the suspension in a clean glass ware, and drying in a vacuum drying oven at the low temperature of less than or equal to 60 ℃;
2) placing the dried nano manganese oxide substrate material into an ALD (atomic layer deposition) cavity, wherein the pressure of the cavity is set to be 10-300Pa, the temperature of the cavity is set to be 150-400 ℃, the heating temperature of the precursor is set to be 30-150 ℃, and the temperature of a pipeline for transporting the precursor is set to be 100-300 ℃;
3) the iron source or the tin source precursor is pulsed to the reaction cavity, after the iron source or the tin source precursor and the substrate sample are subjected to chemical adsorption reaction fully, nitrogen or argon is introduced into the reaction cavity, and the unadsorbed iron source or tin source precursor is discharged out of the cavity; then, an oxygen source precursor is pulsed to the deposition cavity, after the oxygen source precursor and an iron source or tin source precursor are fully reacted, nitrogen or argon is introduced into the reaction cavity, and unreacted oxygen source precursor and reaction byproducts are discharged out of the cavity through cleaning;
4) repeating the step 3) for 1-10 times to obtain an iron oxide or tin oxide deposition layer;
5) after the tin source or the iron source precursor and the substrate sample are subjected to chemical adsorption reaction fully, introducing nitrogen or argon into the reaction cavity, and discharging the unadsorbed tin source or iron source precursor out of the cavity; the method comprises the steps of (1) pulsing an oxygen source precursor to a deposition cavity, introducing nitrogen or argon into the reaction cavity after the oxygen source precursor is fully reacted with a tin source or an iron source precursor, and discharging unreacted oxygen source precursor and reaction byproducts out of the cavity through cleaning;
6) repeating the step 5) for 1-10 times to obtain a tin oxide or iron oxide deposition layer;
7) and (3) sequentially completing the steps 4) and 6) for 1 deposition cycle calculation, and repeating the steps 4) and 6) for 10-1000 times to obtain the multi-interface heterojunction with the core-shell structure.
In the step 3), an iron source or tin source precursor is pulsed to the reaction cavity, and the pulse and the waiting time are respectively set to be 20-80ms and 10-20 s.
In the step 3), the oxygen source precursor is pulsed to the deposition cavity, and the pulse and the waiting time are respectively set to be 20-80ms and 10-20 s.
In the step 5), a precursor of the tin source or the iron source is pulsed to the reaction cavity, and the pulse time and the waiting time are respectively set to be 20-80ms and 10-20 s.
In the step 5), the oxygen source precursor is pulsed to the deposition cavity, and the pulse and the waiting time are respectively set to be 20-80ms and 10-20 s.
The time for introducing nitrogen or argon into the reaction cavity is preferably 10-20 s.
The nano-core substrate material is preferably manganese oxide.
The metal source precursor is preferably an iron source or a tin source.
The invention has the advantages that: according to the multi-interface magnetic heterojunction, the atomic layer deposition technology is utilized to accurately design the multi-interface formed by different components, and efficient separation and transfer of photon-generated carriers are promoted. Secondly, the prepared multi-interface heterojunction is easy to recycle under the action of an external magnetic field by depositing the heterojunction component with the adjustable magnetic effect. The photocatalytic activity of the multi-interface magnetic heterojunction prepared by the method is remarkably enhanced, and the removal rate of ciprofloxacin pollutant solution (the initial concentration is 15mg/L) reaches over 90 percent under the condition of 150W visible light for 30 min. After 5 times of cyclic catalytic degradation, the multi-interface heterojunction still shows higher catalytic stability.
Drawings
FIG. 1 is a schematic structural diagram of a multi-interface heterojunction;
FIG. 2 is an SEM picture of a multi-interface heterojunction of embodiment 1;
FIG. 3 is the concentration change of the multi-interface heterojunction in the process of photocatalytic degradation of ciprofloxacin in example 1;
FIG. 4 is the change of the removal rate of ciprofloxacin catalytically degraded by the multi-interface heterojunction cycle in example 1.
Detailed Description
Example 1: the preparation method of the multi-interface magnetic heterojunction of the embodiment is carried out by the following steps:
1) mn is added3O4Dispersing the nano particles in an ethanol solution to prepare a suspension with the concentration of 6g/L, uniformly dripping the suspension in a clean glass ware, and drying in a vacuum drying oven at 50 ℃ to obtain uniformly dispersed Mn3O4A nanoparticle;
2) and drying the Mn3O4Placing nanoparticles into an ALD (atomic layer deposition) cavity, setting the pressure of the cavity to be 60-300Pa, the temperature of the cavity to be 150 ℃, the temperature of an oxygen source precursor to be 30 ℃, the temperature of an iron source precursor to be 120 ℃, the temperature of a tin source precursor to be 100 ℃ and the temperature of a pipeline for transporting the precursor to be 100 ℃;
3) and the iron source precursor is pulsed for 20ms and enters the ALD reaction cavity, and the waiting time is set to 10s, so that the full chemical adsorption reaction between the precursor and the substrate sample is ensured. Then introducing nitrogen into the reaction cavity for cleaning for 10s, and discharging the residual iron source precursor out of the cavity; the ozone oxygen source precursor is pulsed for 20ms, enters an ALD reaction cavity, reacts with a sample which is saturated with the adsorbed iron source precursor for 10s, then nitrogen is introduced into the reaction cavity again for cleaning for 10s, and the residual ozone oxygen source precursor and reaction byproducts are discharged from the cavity, so that the first layer of Fe is finished2O3Depositing;
4) repeating the step 3) for 1 time to obtain Fe2O3Depositing a layer;
5) and the precursor of the tin source is pulsed for 20ms and enters an ALD reaction cavity, and the waiting time is set to 10s, so that the chemical adsorption reaction between the precursor and the substrate sample is fully generated. Followed byIntroducing nitrogen into the reaction cavity for cleaning for 10s, and discharging the residual tin source precursor out of the cavity; the method comprises the steps of enabling a deionized water oxygen source precursor to enter an ALD reaction cavity after 20ms of pulse, enabling the deionized water oxygen source precursor to react with a sample which adsorbs tin source precursor to be saturated for 10s, then introducing nitrogen into the reaction cavity again to clean for 10s, discharging the rest of the deionized water oxygen source precursor and reaction byproducts out of the cavity, and thus finishing the first layer of SnO2Depositing;
6) repeating the step 5) for 1 time to obtain SnO2Depositing a layer;
7) and (3) carrying out deposition cycle calculation for 1 time by sequentially finishing the steps 4) and 6), and repeating the steps 4) and 6) for 500 times to obtain the multi-interface heterojunction with the core-shell structure.
The embodiment has the following beneficial effects:
first, Mn obtained in the present embodiment3O4@Fe2O3/SnO2The schematic structure of the multi-interface heterojunction is shown in fig. 1, and can provide more transfer paths for electrons and holes, thereby facilitating the efficient separation of electron-hole pairs;
second, Mn obtained in the present embodiment3O4@Fe2O3/SnO2The SEM picture of the multi-interface heterojunction is shown in figure 2, and the catalyst nanoparticles have no obvious accumulation phenomenon due to Fe2O3The multi-interface heterojunction is easy to recycle under the action of a magnetic field due to the existence of the magnetic component;
third, Mn obtained in the present embodiment3O4@Fe2O3/SnO2The multi-interface heterojunction has stronger photocatalytic activity. As shown in figure 3, after 30min of visible light irradiation of a 150W xenon lamp, the removal rate of the ciprofloxacin pollutant solution with the initial concentration of 15mg/L reaches 92 percent;
fourth, Mn obtained in the present embodiment3O4@Fe2O3/SnO2The multi-interface heterojunction has stronger catalytic stability. As shown in fig. 4, after 5 cycles of degradation experiments (same conditions as three), the removal rate of ciprofloxacin by the multi-interface heterojunction is reduced by only 3.6%.
Example 2: the preparation method of the multi-interface magnetic heterojunction of the embodiment is carried out by the following steps:
1) MnO prepared by a hydrothermal method in advance2Dispersing the nano particles in an ethanol solution, preparing a suspension with the concentration range of 30g/L, uniformly dripping the suspension in a clean glass ware, and drying in a vacuum drying oven at 40 ℃;
2) putting the dried sample into an ALD (atomic layer deposition) cavity, setting the pressure of the cavity to be 10-200Pa, the temperature of the cavity to be 400 ℃, the temperature of an oxygen source precursor to be 50 ℃, the temperature of an iron source precursor to be 120 ℃, the temperature of a tin source precursor to be 150 ℃ and the temperature of a pipeline for transporting the precursor to be 300 ℃;
3) and the precursor of the tin source is pulsed for 80ms and enters the ALD reaction cavity, and the waiting time is set to be 20s, so that the chemical adsorption reaction between the precursor and the substrate sample is fully generated. Then introducing argon gas into the reaction cavity for cleaning for 20s, and discharging the residual tin source precursor out of the cavity; the ozone precursor is pulsed for 80ms, enters an ALD reaction cavity, reacts with a sample which is saturated by absorbing the tin source precursor for 20s, then argon is introduced into the reaction cavity again to clean for 20s, the residual ozone precursor and reaction byproducts are discharged from the cavity, and thus the first layer of SnO is finished2Depositing;
4) repeating the step 3) for 10 times to obtain SnO2Depositing a layer;
5) and the iron source precursor is pulsed for 80ms and enters the ALD reaction cavity, and the waiting time is set to be 20s, so that the chemical adsorption reaction between the precursor and the substrate sample is fully generated. Then introducing argon gas into the reaction cavity for cleaning for 20s, and discharging the residual iron source precursor out of the cavity; the method comprises the steps of enabling a deionized water oxygen source precursor to enter an ALD reaction cavity after 80ms of pulse, enabling the deionized water oxygen source precursor to react with a sample which is saturated with an adsorbed iron source precursor for 20s, then introducing argon into the reaction cavity again to clean the reaction cavity for 20s, discharging the rest deionized water oxygen source precursor and reaction byproducts out of the cavity, and thus finishing the first layer of Fe2O3Depositing;
6) repeating the step 5) for 10 times to obtain Fe2O3Depositing a layer;
7) and (3) carrying out deposition cycle calculation for 1 time by sequentially finishing the steps 4) and 6), and repeating the steps 4) and 6) for 1000 times to obtain the multi-interface heterojunction with the core-shell structure.
The embodiment has the following beneficial effects:
first, MnO obtained in the present embodiment2@SnO2/Fe2O3The multi-interface heterojunction can provide more transfer paths for electrons and holes, is favorable for promoting the high-efficiency separation of electron-hole pairs and improves the photocatalytic activity. After 30min of visible light illumination by a 150W xenon lamp, the removal rate of ciprofloxacin pollutant solution with the initial concentration of 15mg/L reaches 95 percent;
second, MnO obtained in the present embodiment2@SnO2/Fe2O3The multi-interface heterojunction nano particles have no obvious accumulation phenomenon due to Fe2O3The multi-interface heterojunction is easy to recycle under the action of a magnetic field due to the existence of the magnetic component;
MnO obtained in the present embodiment2@SnO2/Fe2O3The multi-interface heterojunction has stronger catalytic stability. After 5 times of cyclic degradation experiments (the same condition), the removal rate of ciprofloxacin by the multi-interface heterojunction is only reduced by 2.8%.
Example 3: the preparation method of the multi-interface magnetic heterojunction of the embodiment is carried out by the following steps:
1) mn prepared by hydrothermal method in advance3O4Dispersing the nano particles in an ethanol solution, preparing a suspension with the concentration range of 10g/L, uniformly dripping the suspension in a clean glass ware, and drying in a vacuum drying oven at 45 ℃;
2) putting the dried sample into an ALD (atomic layer deposition) cavity, setting the pressure of the cavity to be 60-300Pa, the temperature of the cavity to be 300 ℃, the temperature of an oxygen source precursor to be 60 ℃, the temperature of an iron source precursor to be 120 ℃, the temperature of a tin source precursor to be 130 ℃, and the temperature of a pipeline for transporting the precursor to be 200 ℃;
3) the precursor of the tin source is pulsed for 60ms and enters an ALD reaction cavity, the waiting time is set to 15s, and the sufficient chemical generation between the precursor and the substrate sample is ensuredAnd (5) carrying out adsorption reaction. Then introducing nitrogen into the reaction cavity for cleaning for 15s, and discharging the residual tin source precursor out of the cavity; the ozone oxygen source precursor is pulsed for 60ms, enters an ALD reaction cavity, reacts with a sample which adsorbs the tin source precursor to saturation for 15s, then nitrogen is introduced into the reaction cavity again to clean for 15s, the residual ozone oxygen source precursor and reaction byproducts are discharged from the cavity, and thus the first layer of SnO is finished2Depositing;
4) repeating the step 3) for 5 times to obtain SnO2Depositing a layer;
5) and the iron source precursor is pulsed for 60ms and enters the ALD reaction cavity, and the waiting time is set to 15s, so that the full chemisorption reaction between the precursor and the substrate sample is ensured. Then introducing nitrogen into the reaction cavity for cleaning for 15s, and discharging the residual iron source precursor out of the cavity; the method comprises the steps of enabling a deionized water oxygen source precursor to enter an ALD reaction cavity after 60ms of pulse, enabling the deionized water oxygen source precursor to react with a sample which is saturated with an iron source precursor for 15s, then introducing nitrogen into the reaction cavity again to clean the reaction cavity for 15s, discharging the rest deionized water oxygen source precursor and reaction byproducts out of the cavity, and thus finishing the first layer of Fe2O3Depositing;
6) repeating the step 5) for 5 times to obtain Fe2O3Depositing a layer;
7) and (3) carrying out deposition cycle calculation for 1 time by sequentially finishing the steps 4) and 6), and repeating the steps 4) and 6) for 10 times to obtain the multi-interface heterojunction with the core-shell structure.
The embodiment has the following beneficial effects:
first, Mn obtained in the present embodiment3O4@SnO2/Fe2O3The multi-interface heterojunction can provide more transfer paths for electrons and holes, is favorable for promoting the high-efficiency separation of electron-hole pairs and improves the photocatalytic activity. After 30min of visible light illumination by a 150W xenon lamp, the removal rate of the ciprofloxacin pollutant solution with the initial concentration of 15mg/L reaches 93 percent;
second, Mn obtained in the present embodiment3O4@SnO2/Fe2O3The multi-interface heterojunction nano particles have no obvious accumulation phenomenon due to Fe2O3The multi-interface heterojunction is easy to recycle under the action of a magnetic field due to the existence of the magnetic component;
third, Mn obtained in the present embodiment3O4@SnO2/Fe2O3The multi-interface heterojunction has stronger catalytic stability. After 5 times of cyclic degradation experiments (the same condition), the removal rate of ciprofloxacin by the multi-interface heterojunction is only reduced by 3.1%.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (8)
1. A preparation method of a multi-interface magnetic heterojunction is characterized by comprising the following steps:
1) dispersing the nano-core substrate material in an ethanol solution to prepare a suspension with the concentration range of 6-30g/L, uniformly dripping the suspension in a clean glass ware, and drying in a vacuum drying oven at the temperature of less than or equal to 60 ℃;
2) placing the dried nano manganese oxide substrate material into an ALD (atomic layer deposition) cavity, wherein the pressure of the cavity is set to be 10-300Pa, the temperature of the cavity is set to be 150-400 ℃, the heating temperature of the precursor is set to be 30-150 ℃, and the temperature of a pipeline for transporting the precursor is set to be 100-300 ℃;
3) the iron source or the tin source precursor is pulsed to the reaction cavity, after the iron source or the tin source precursor and the substrate sample are subjected to chemical adsorption reaction fully, nitrogen or argon is introduced into the reaction cavity, and the unadsorbed iron source or tin source precursor is discharged out of the cavity; then, an oxygen source precursor is pulsed to the deposition cavity, after the oxygen source precursor and an iron source or tin source precursor are fully reacted, nitrogen or argon is introduced into the reaction cavity, and unreacted oxygen source precursor and reaction byproducts are discharged out of the cavity through cleaning;
4) repeating the step 3) for 1-10 times to obtain an iron oxide or tin oxide deposition layer;
5) after the tin source or the iron source precursor and the substrate sample are subjected to chemical adsorption reaction fully, introducing nitrogen or argon into the reaction cavity, and discharging the unadsorbed tin source or iron source precursor out of the cavity; the method comprises the steps of (1) pulsing an oxygen source precursor to a deposition cavity, introducing nitrogen or argon into the reaction cavity after the oxygen source precursor is fully reacted with a tin source or an iron source precursor, and discharging unreacted oxygen source precursor and reaction byproducts out of the cavity through cleaning;
6) repeating the step 5) for 1-10 times to obtain a tin oxide or iron oxide deposition layer;
7) and (3) sequentially completing the steps 4) and 6) for 1 deposition cycle calculation, and repeating the steps 4) and 6) for 10-1000 times to obtain the multi-interface heterojunction with the core-shell structure.
2. The method as set forth in claim 1, wherein the iron source or tin source precursor is pulsed into the reaction chamber in the step 3), and the pulse and the waiting time are set to 20-80ms and 10-20s, respectively.
3. The method of claim 1, wherein in step 3) the oxygen source precursor is pulsed into the deposition chamber with pulse and wait times set to 20-80ms and 10-20s, respectively.
4. The method as set forth in claim 1, wherein the tin source or iron source precursor is pulsed into the reaction chamber in the step 5), and the pulse and the waiting time are set to 20-80ms and 10-20s, respectively.
5. The method according to claim 1, wherein the oxygen source precursor is pulsed into the deposition chamber in step 5), the pulse and the waiting time being set to 20-80ms and 10-20s, respectively.
6. The method of claim 1, wherein nitrogen or argon is introduced into the reaction chamber for 10-20 s.
7. The method of claim 1, wherein the nano-core substrate material is manganese oxide.
8. The method of claim 1, wherein the metal source precursor is an iron source or a tin source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910982465.4A CN110694639B (en) | 2019-10-16 | 2019-10-16 | Preparation method of multi-interface magnetic heterojunction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910982465.4A CN110694639B (en) | 2019-10-16 | 2019-10-16 | Preparation method of multi-interface magnetic heterojunction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110694639A true CN110694639A (en) | 2020-01-17 |
| CN110694639B CN110694639B (en) | 2022-07-29 |
Family
ID=69199786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910982465.4A Active CN110694639B (en) | 2019-10-16 | 2019-10-16 | Preparation method of multi-interface magnetic heterojunction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110694639B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101757926A (en) * | 2009-12-31 | 2010-06-30 | 南京大学 | Magnetic-particle photocatalyst with core-shell structure, preparation and application thereof |
| CN102151572A (en) * | 2011-02-23 | 2011-08-17 | 南京大学 | Iron-gadolinium-antimony based composite magnetic particle photo-catalyst in core-shell structure as well as preparation and application thereof |
| CN104888612A (en) * | 2015-05-25 | 2015-09-09 | 哈尔滨工业大学 | Method for carrying out compound photocatalyst modification on micro-filtration membrane by utilizing atomic layer deposition |
| US20160059228A1 (en) * | 2013-05-24 | 2016-03-03 | Council Of Scientific & Industrial Research | Semiconductor-oxides nanotubes-based composite particles useful for dye-removal and process thereof |
| CN107913667A (en) * | 2017-10-25 | 2018-04-17 | 浙江工商大学 | A kind of magnetic graphene/ferroso-ferric oxide/manganese dioxide nano-composite material and its preparation and application |
| CN109576680A (en) * | 2018-11-22 | 2019-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of composite material and products thereof and application |
| CN109876828A (en) * | 2019-01-29 | 2019-06-14 | 浙江大学 | A kind of TNT/CdS/TiO2/ Pt nuclear shell structure nano pipe and preparation method thereof |
| CN110038548A (en) * | 2019-05-10 | 2019-07-23 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of n-p-n type sandwich heterojunction nanometer material and products thereof and application |
| CN110302775A (en) * | 2019-06-28 | 2019-10-08 | 陕西科技大学 | A kind of preparation method of mangano-manganic oxide/tin dioxide nucleic shell structured catalysis material |
| CN110327917A (en) * | 2019-08-08 | 2019-10-15 | 华北电力大学（保定） | The metal-doped manganese dioxide photochemical catalyst preparation method of Treatment of Coking Effluent |
-
2019
- 2019-10-16 CN CN201910982465.4A patent/CN110694639B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101757926A (en) * | 2009-12-31 | 2010-06-30 | 南京大学 | Magnetic-particle photocatalyst with core-shell structure, preparation and application thereof |
| CN102151572A (en) * | 2011-02-23 | 2011-08-17 | 南京大学 | Iron-gadolinium-antimony based composite magnetic particle photo-catalyst in core-shell structure as well as preparation and application thereof |
| US20160059228A1 (en) * | 2013-05-24 | 2016-03-03 | Council Of Scientific & Industrial Research | Semiconductor-oxides nanotubes-based composite particles useful for dye-removal and process thereof |
| CN104888612A (en) * | 2015-05-25 | 2015-09-09 | 哈尔滨工业大学 | Method for carrying out compound photocatalyst modification on micro-filtration membrane by utilizing atomic layer deposition |
| CN107913667A (en) * | 2017-10-25 | 2018-04-17 | 浙江工商大学 | A kind of magnetic graphene/ferroso-ferric oxide/manganese dioxide nano-composite material and its preparation and application |
| CN109576680A (en) * | 2018-11-22 | 2019-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of composite material and products thereof and application |
| CN109876828A (en) * | 2019-01-29 | 2019-06-14 | 浙江大学 | A kind of TNT/CdS/TiO2/ Pt nuclear shell structure nano pipe and preparation method thereof |
| CN110038548A (en) * | 2019-05-10 | 2019-07-23 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of n-p-n type sandwich heterojunction nanometer material and products thereof and application |
| CN110302775A (en) * | 2019-06-28 | 2019-10-08 | 陕西科技大学 | A kind of preparation method of mangano-manganic oxide/tin dioxide nucleic shell structured catalysis material |
| CN110327917A (en) * | 2019-08-08 | 2019-10-15 | 华北电力大学（保定） | The metal-doped manganese dioxide photochemical catalyst preparation method of Treatment of Coking Effluent |
Non-Patent Citations (5)
| Title |
|---|
| RUI LI ET AL.: ""Aquatic environment remediation by atomic layer deposition-based multifunctional"", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| SHANNON C. RIHA ET AL.: ""Phase Discrimination through Oxidant Selection in Low-Temperature Atomic Layer Deposition of Crystalline Iron Oxides"", 《LANGMUIR》 * |
| 张涛等: ""Fe2O3-SnO2 纳米光催化剂模拟日光下降解酸性蓝废水"", 《化工进展》 * |
| 田华等: "氧化锰催化氧化甲醛的研究进展", 《化学通报》 * |
| 谷龙艳等: "一步法制备纳米SnO-SnO_2复合材料及其光催化性能增强机制的光生载流子动力学", 《复合材料学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110694639B (en) | 2022-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Momeni et al. | Preparation of TiO2 and WO3–TiO2 nanotubes decorated with PbO nanoparticles by chemical bath deposition process: a stable and efficient photo catalyst | |
| CN108840370B (en) | Transition metal oxide/nitrogen-doped ordered mesoporous carbon composite material and preparation method thereof | |
| WO2021120359A1 (en) | Wo3/tio2 nanotube having monoatomic noble metal anchored defects, and preparation and use thereof | |
| CN107892284A (en) | A kind of NiS/C3N4Binary complex and its methods for making and using same | |
| CN109126853A (en) | A kind of counter opal g-C with carbon defects3N4The preparation method of photochemical catalyst | |
| CN109692698B (en) | Bi/Ti for catalytic reduction of NOx3C2Nano-sheet photocatalyst and preparation method thereof | |
| CN112777565B (en) | Semiconductor photocatalytic water splitting method capable of inhibiting reverse reaction | |
| CN112058082A (en) | Method for removing zero-valent mercury and arsenic hydride by magnetic field in cooperation with photocatalytic oxidation | |
| CN110694639B (en) | Preparation method of multi-interface magnetic heterojunction | |
| CN106567102B (en) | A kind of TiO2The preparation method of/carbon nanotube/Ni photoelectric activity combination electrodes | |
| CN108579775B (en) | Silver phosphate/silver/titanium dioxide nanoflower composite material and preparation method and application thereof | |
| CN108554435B (en) | PdO loaded N, B co-doped titanium dioxide nanotube photocatalyst and preparation method thereof | |
| CN109675560A (en) | A kind of ceramsite catalyst and its preparation method and application that low-temperature plasma is modified | |
| CN108404926B (en) | Amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst and preparation method and application thereof | |
| CN113368872A (en) | Z-shaped composite photocatalyst based on selective modification and preparation method thereof | |
| CN112844384A (en) | Photocatalytic device based on titanium dioxide/copper composite film and preparation method and application thereof | |
| CN108117142B (en) | Flexible large-area TaON nanorod array composite BiOI carbon fiber cloth and preparation method thereof | |
| CN110801826A (en) | Photoelectrocatalysis graphite felt material and preparation method and application thereof | |
| CN111841597A (en) | Composite photocatalytic material of cobalt-loaded nitrogen-doped graphene oxide/mesoporous thin-layer carbon nitride and preparation method thereof | |
| CN112916000B (en) | Photocatalytic material for reducing nitrogen to produce ammonia and preparation method and application thereof | |
| CN110282703B (en) | Preparation of self-supporting MnOx/LSC three-dimensional composite electrode and application of self-supporting MnOx/LSC three-dimensional composite electrode in mineralization of refractory organic pollutants | |
| CN114797847A (en) | Metal-doped mesoporous carbon-based catalyst and preparation method and application thereof | |
| CN112359376A (en) | Preparation method of metal oxide-insulator-semiconductor structure photo-anode | |
| CN112138695B (en) | Z-type ZnO/Au/g-C 3 N 4 Preparation method and application of composite membrane photocatalytic material | |
| CN107456984A (en) | Iron carbon composite and preparation method with visible ray photolysis water hydrogen performance |
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 |