CN113912160A - Novel three-phase interface reactor and preparation method and application thereof - Google Patents
Novel three-phase interface reactor and preparation method and application thereof Download PDFInfo
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- CN113912160A CN113912160A CN202111220146.3A CN202111220146A CN113912160A CN 113912160 A CN113912160 A CN 113912160A CN 202111220146 A CN202111220146 A CN 202111220146A CN 113912160 A CN113912160 A CN 113912160A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- 238000000151 deposition Methods 0.000 claims abstract description 33
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 26
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 25
- 231100000719 pollutant Toxicity 0.000 claims abstract description 25
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 22
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 21
- 230000008021 deposition Effects 0.000 claims abstract description 19
- 238000004528 spin coating Methods 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 49
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 17
- 238000010926 purge Methods 0.000 claims description 16
- 239000002351 wastewater Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000000593 degrading effect Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- -1 mercaptan alkane Chemical class 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 13
- 238000006731 degradation reaction Methods 0.000 abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 37
- 239000010408 film Substances 0.000 description 31
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 11
- 239000007853 buffer solution Substances 0.000 description 9
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 102000003992 Peroxidases Human genes 0.000 description 6
- 108040007629 peroxidase activity proteins Proteins 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 108010029541 Laccase Proteins 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention discloses a novel three-phase interface reactor and a preparation method and application thereof.A metal oxide is deposited on an atomic layer on the surface of carbon paper and is subjected to hydrophobization treatment to obtain a hydrophobized atomic layer deposited porous breathable film; spin-coating metal sulfide on the surface of the porous breathable film subjected to atomic layer deposition to obtain a hydrophobic atomic deposition porous breathable film loaded with the metal sulfide; depositing the hydrophobic atoms loaded with the metal sulfide into a porous breathable film, and further loading biomolecules to obtain the metal sulfide-loaded porous breathable film. The three-phase interface reactor overcomes the defects of low dissolved oxygen concentration, short service life and poor repeatability in the traditional biological sewage degradation, and has better prospect in the degradation of benzene pollutants in the wastewater treatment.
Description
Technical Field
The invention relates to a three-phase interface reactor, in particular to a novel three-phase interface reactor and a preparation method and application thereof.
Background
With the increase of population and the development of modern society, people are generating more and more garbage and waste water. The serious water pollution problem caused by the waste water discharge directly or potentially threatens the survival and development of human beings, degrades and monitors pollutants in the waste water in real time, on line and in situ, improves the efficiency, stability and sensitivity of a treatment method, and becomes a target pursued by the current water pollution treatment and monitoring.
The traditional physical and chemical methods for treating wastewater can not completely remove pollutants and cause secondary pollution. The biological technology for degrading the wastewater has the advantages of low cost, quick response and the like, and is widely applied to wastewater treatment. However, the traditional biological technology directly puts free biological molecules into the water body and has the problems of low biological molecule activity, short service life and limited degradation effect by dissolved oxygen. Therefore, constructing a functionally stable and long-acting interface to improve the mass transfer rate and concentration of the reaction gas to the interface and obtaining high-efficiency detection precision or higher pollutant degradation rate is the core of research in the field. The novel three-phase interface reactor is constructed, and has wide application prospect in the fields of pollutant treatment, industrial synthesis and the like.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art and provides a method for constructing a novel three-phase interface reactor with stable performance by simple modification and application of the novel three-phase interface reactor constructed by the method in wastewater pollutant degradation.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a novel three-phase interface reactor comprises the following steps:
(1) depositing metal oxide on the surface of the carbon paper by using an atomic layer and performing hydrophobization treatment to obtain a hydrophobized atomic layer deposited porous breathable film;
(2) spin-coating metal sulfide on the surface of the porous breathable film subjected to atomic layer deposition in the step (1) to obtain a hydrophobic atomic deposition porous breathable film loaded with the metal sulfide;
(3) and (3) depositing the hydrophobic atoms loaded with the metal sulfide in the step (2) into a porous breathable film, and further loading biological molecules to obtain the metal sulfide-loaded porous breathable film.
Specifically, in the step (1), the carbon paper is used for depositing the metal oxide through an atomic layer deposition instrument, and the specific steps are as follows:
(a1) immersing carbon paper in an organic solvent, removing attachments on the surface of the carbon paper by ultrasonic, and drying by nitrogen;
(a2) placing the carbon paper treated in the step (a1) into a reaction chamber of an atomic layer deposition device with the temperature of 100-300 ℃, purging for 1-15 min by using high-purity nitrogen, and then using TiCl4Or titanium tetraisopropoxide is taken as a first precursor, and the first precursor is heated to 50-120 ℃ to form TiCl4Or titanium tetraisopropoxide steam, feeding the formed steam into the reaction chamber in a pulse mode, exposing for 5-20 s, purging for 10-30 s by using high-purity nitrogen, feeding deionized water of a second precursor into the reaction chamber in a pulse mode, exposing for 5-20 s, continuing purging for 10-30 s by using high-purity nitrogen, and completing one deposition cycle, namely depositing a layer of TiO on the surface of the carbon paper2A film; repeating the steps to deposit TiO with proper thickness on the surface of the carbon paper2A film.
Specifically, in the step (1), hydrophobization is performed on the carbon paper after the atomic layer deposition of the metal oxide in a reaction tank, and the specific steps are as follows:
(b1) and (2) immersing the carbon paper deposited with the metal oxide into a hydrophobic solvent mercaptan alkane or fluorine-containing reagent with the concentration of 0.5-2 mM, soaking for 3-12 h, taking out, drying by using nitrogen, and obtaining the hydrophobic atomic layer deposited porous breathable film according to the surface adsorption principle.
Specifically, in the step (2), the specific steps of spin coating the metal sulfide are as follows:
(c1) in order to construct a solid phase interface, a metal sulfide with the volume of 1 muL-1000 muL and the concentration of 0.001-100mM is coated on the surface of the hydrophobized atomic layer deposition porous breathable film in a spinning mode, and the hydrophobized atomic layer deposition porous breathable film loaded with the metal sulfide is obtained.
Specifically, in the step (3), the biomolecules are fixed on the surface of the metal sulfide-loaded hydrophobic atomic deposition porous breathable film through electrostatic adsorption, and the method specifically comprises the following steps:
(d1) biomolecules with the volume of 1 muL-1000 muL and the concentration of 0.001-100mM are fixed on the surface of the metal sulfide-loaded hydrophobic atom deposition porous breathable film.
The biological molecules can be selected for different pollutants, and can be enzymes, bacteria or polypeptides capable of green degradation of pollutants, for example, laccase draws electrons to reduce oxygen in the air into water, and target pollutants are oxidized into small molecules with economic benefits such as malonic acid and succinic acid.
Preferably, in the step (a1), the organic solvent is isopropanol, ethanol, chloroform or acetone, and the bath ratio of the carbon paper to the organic solvent is 1: 10-1000; and placing the container containing the carbon paper and the organic solvent in an ultrasonic cleaner for ultrasonic treatment for 0.5-6 h.
Preferably, in the step (a2), the purity of the high-purity nitrogen for purging is not lower than 99.999%; the purity of TiCl4 and titanium tetraisopropoxide is higher than 97%; the steam of the first precursor and the steam of the second precursor are respectively sent into the reaction chamber with the pulse time of 0.01 to 0.5 s; finally depositing TiO on the surface of the carbon paper2The thickness of the film is 5 to 30 nm.
Furthermore, the invention also claims a novel three-phase interface reactor prepared by the preparation method.
Furthermore, the invention also claims the application of the novel three-phase interface reactor in degrading pollutants in wastewater treatment.
Specifically, the novel three-phase interface reactor is immersed into the wastewater containing benzene pollutants to be used as a working electrode, and the working voltage is set to be-0.8V-0.8V.
Has the advantages that:
compared with the prior art, the invention overcomes the defects of low dissolved oxygen concentration, short service life and poor repeatability in the traditional biological sewage degradation. The novel three-phase interface reactor constructed by simple modification utilizes oxygen in natural air to directly degrade wastewater pollutants, and improves the reaction rate and efficiency. Meanwhile, after the wastewater pollutants are added into the novel three-phase interface reactor constructed by the method, the reaction rate and the degradation efficiency are obviously improved.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a graph showing the degradation capability of the novel three-phase interface reactor of the present invention and a conventional two-phase interface reactor for wastewater pollutants.
FIG. 2 is a graph comparing the capacity of a three-phase interfacial reactor of the present invention to degrade wastewater contaminants with a proportional two-phase interfacial reactor.
Detailed Description
The invention will be better understood from the following examples.
Example 1
The PBS buffer solution used in this example had a concentration of 0.01M and a pH of 7.4; the laccase (Lac) used was purchased from Sigma-alorich, USA; molybdenum disulfide (MoS)2) Solution, Lignin (LiG) from the national groups; carbon Paper (CP) was purchased from shanghai hesen electric limited.
(1) Modifying the surface of Carbon Paper (CP) by atomic layer deposition and carrying out hydrophobic treatment;
(a1) soaking the carbon paper in an organic solvent (ethanol) at a bath ratio of 1:30, placing the container containing the carbon paper and the organic solvent in an ultrasonic cleaner for ultrasonic treatment for 4h to remove attachments on the surface of the carbon paper, and drying the cleaned carbon paper by using nitrogen.
(a2) Placing the carbon paper treated in the step (a1) into a reaction chamber of an atomic layer deposition device with the temperature of 180 ℃, purging with nitrogen with the purity of 99.999% for 5min, and then using TiCl with the purity higher than 97%4Heating to 65 deg.C as the first precursor to form TiCl4Feeding the vapor into the reaction chamber in a pulse form for 0.05s, exposing for 8s, purging with high purity nitrogen gas for 20s, feeding the deionized water as the second precursor into the reaction chamber in a pulse form for 0.05s, exposing for 8s, and continuingAnd (3) blowing for 20s by adopting high-purity nitrogen to finish one deposition cycle, namely depositing a TiO2 film on the surface of the porous breathable film. The deposition cycle was repeated 200 times as described above, i.e., a thin film layer having a thickness of about 15nm was formed on the surface of the carbon paper.
(b1) Hydrophobically deposited carbon paper
Immersing the porous breathable film deposited with the metal oxide into polytetrafluoroethylene ethanol added with a hydrophobic solvent with the volume of 500 mu L and the concentration of 1mM, placing the reaction vessel containing the porous breathable film deposited with the atomic layer and the hydrophobic reagent for 10h, taking out nitrogen with tweezers, and drying by blowing to obtain the hydrophobic porous breathable film deposited with the atomic layer.
(2) Spin coating molybdenum disulfide (MoS)2) To hydrophobized atomic layer deposited porous breathable film surface:
spin-coating 1000 muL of a nano material with the concentration of 100mM into the hydrophobized atomic layer deposited porous breathable film to obtain the hydrophobized atomic layer deposited porous breathable film loaded with molybdenum disulfide;
(3) will be loaded with molybdenum disulfide (MoS)2) The hydrophobic atomic deposition porous ventilated membrane further fixes biomolecules to construct a novel three-phase interface reactor:
fixing laccase (Lac) molecules with volume of 10 μ L and concentration of 0.001mM in the surface of hydrophobic atomic deposition porous ventilated membrane loaded with molybdenum disulfide, and incubating in 4-degree refrigerator for 4h to obtain novel three-phase interface reactor Lac/MoS2/TiO2/CP。
The three-phase interface reactor prepared by the construction method is applied to degradation of wastewater pollutants:
the constructed novel three-phase interface reactor is immersed into an electrochemical reaction tank to be used as a working electrode, the voltage is set to be 0.6V below zero, the reactor is added into PBS buffer solution with the pH value of 7.0 and the concentration of 0.01M, and 20M lignin solution (degrading target pollutants) is added into the buffer solution to be used as an experimental group. Meanwhile, the sample was used as a blank control when no lignin solution (target pollutant degradation) was added. The results of electrochemical signals obtained from the two experimental groups are shown in FIG. 1. As can be seen from the figure: after the target pollutant is added, the oxidation current is increased, which indicates that the target pollutant is oxidized and degraded by the novel three-phase interface reactor.
Example 2
The PBS buffer solution used in this example had a concentration of 10mM and a pH of 7.4; peroxidase (HRP) used was purchased from Sigma-alorich, USA; molybdenum disulfide (WS)2) Solution, phenol (HP) from the national pharmaceutical group; carbon paper was purchased from shanghai hesen electrical limited.
(1) Modifying the surface of Carbon Paper (CP) by atomic layer deposition and carrying out hydrophobic treatment:
(a1) soaking the carbon paper in an organic solvent (ethanol) at a bath ratio of 1:30, placing the container containing the carbon paper and the organic solvent in an ultrasonic cleaner for ultrasonic treatment for 4h to remove attachments on the surface of the carbon paper, and drying the cleaned carbon paper by using nitrogen.
(a2) And (b) placing the carbon paper treated in the step (a1) into a reaction chamber of atomic layer deposition equipment with the temperature of 180 ℃, purging with nitrogen with the purity of 99.999% for 5min, heating titanium tetraisopropoxide with the purity higher than 97% as a first precursor to 65 ℃ to form titanium tetraisopropoxide vapor, sending the formed vapor into the reaction chamber in a pulse mode, setting the pulse time to be 0.05s, exposing for 8s, purging with high-purity nitrogen for 20s, sending a second precursor deionized water into the reaction chamber in a pulse mode, setting the pulse time to be 0.05s, exposing for 8s, purging with high-purity nitrogen for 20s at a continuous rate, and completing a deposition cycle, namely depositing a TiO2 thin film on the surface of the porous breathable film. The deposition cycle was repeated 200 times as described above, i.e., a thin film layer having a thickness of about 15nm was formed on the surface of the carbon paper.
(b1) Hydrophobically deposited carbon paper
Immersing the porous breathable film deposited with the metal oxide into polytetrafluoroethylene ethanol added with a hydrophobic solvent with the volume of 500 mu L and the concentration of 1mM, placing the reaction vessel containing the porous breathable film deposited with the atomic layer and the hydrophobic reagent for 10h, taking out nitrogen with tweezers, and drying by blowing to obtain the hydrophobic porous breathable film deposited with the atomic layer.
(2) Spin coating tungsten disulfide (WS)2) Atomic layer deposition after hydrophobizationThe surface of the porous breathable film of (a):
spin-coating tungsten disulfide with the volume of 80 mu L and the concentration of 50mM into the hydrophobized atomic layer deposited porous breathable film, and drying overnight to obtain the hydrophobized atomic layer deposited porous breathable film loaded with tungsten disulfide;
(3) will be loaded with tungsten disulfide (WS)2) The hydrophobic atomic deposition porous breathable film is further loaded with peroxidase (HRP) to construct a novel three-phase interface reactor:
immobilizing peroxidase molecules with the volume of 70 mu L and the concentration of 0.001mM in the surface of a hydrophobic atomic deposition porous breathable film loaded with tungsten disulfide, and placing the porous breathable film in a refrigerator with the temperature of 4 ℃ for incubation for 4 hours to obtain a novel three-phase interface reactor Lac/WS2/TiO2/CP。
The three-phase interface reactor prepared by the construction method is applied to degradation of wastewater pollutants:
the constructed novel three-phase interface reactor is immersed into an electrochemical reaction tank to be used as a working electrode, the voltage is set to be 0.4V below zero, the reactor is added into PBS buffer solution with the pH value of 7.0 and the concentration of 0.01M, and 10M phenol solution (degrading target pollutants) is added into the buffer solution.
Comparative example
The PBS buffer solution used had a concentration of 10mM and a pH of 7.4; peroxidase (HRP) used was purchased from Sigma-alorich, USA; molybdenum disulfide (WS)2) Solution, phenol (HP) from the national pharmaceutical group; ITO (GA, indium tin oxide electrode) is available from Kyork, Inc.
(1) Preparation of a two-phase interfacial reactor:
(a1) placing an ITO electrode into a reaction chamber of atomic layer deposition equipment with the temperature of 180 ℃, purging for 5min by using nitrogen with the purity of 99.999%, then using titanium tetraisopropoxide with the purity higher than 97% as a first precursor, heating the first precursor to 65 ℃ to form titanium tetraisopropoxide steam, sending the formed steam into the reaction chamber in a pulse form, setting the pulse time to be 0.05s, exposing for 8s, purging for 20s by using high-purity nitrogen, sending a second precursor deionized water into the reaction chamber in a pulse form, and purging for 0.05s, exposing for 8s by using high-purity nitrogen at a continuous rate, thereby completing one-time deposition cycle, namely depositing a layer of TiO2 thin film on the surface of the ITO electrode. The deposition cycle was repeated 200 times as described above, i.e., a thin film layer having a thickness of about 15nm was formed on the surface of the ITO electrode.
(a1) Spin coating tungsten disulfide (WS)2) To atomic layer deposition of TiO2Surface of ITO electrode (GA):
spin-coating tungsten disulfide with the volume of 80 mu L and the concentration of 50mM on the surface of the ITO electrode with atomic layer deposition, and drying overnight to obtain the ITO electrode carrying the tungsten disulfide atomic layer deposition;
(2) will be loaded with tungsten disulfide (WS)2) The ITO electrode for atomic layer deposition further loads peroxidase (HRP) to construct a two-phase interface reactor:
(b1) immobilizing peroxidase molecules with the volume of 70 mu L and the concentration of 0.001mM on the surface of an ITO electrode loaded with tungsten disulfide, and placing the ITO electrode in a 4-degree refrigerator for incubation for 4h to obtain a two-phase interface reactor Lac/MoS2/TiO2/GA。
The two-phase interface reactor prepared by the construction method is applied to the degradation of wastewater pollutants and is compared with a novel three-phase interface:
the constructed two-phase interface reactor is immersed into an electrochemical reaction pool as a working electrode, the voltage is set to be 0.4V below zero, PBS buffer solution with the pH value of 7.0 and the concentration of 0.01M is added, and 10M phenol solution (degrading target pollutants) is added into the buffer solution.
The Lac/MoS prepared in example 1 was used2the/TiO 2/CP three-phase interface reactor and the Lac/MoS prepared by the comparative example2The ability of the/TiO 2/GA two-phase interface reactor to degrade wastewater contaminants is shown in FIG. 2. As can be seen from the figure, the current of the three-phase interface reactor increased nearly four times more than that of the two-phase interface reactor, indicating that the three-phase interface reactor had a better current response.
The present invention provides a novel three-phase interface reactor, a method for preparing the same, and a method for applying the same, and a plurality of methods and ways for implementing the technical scheme, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. The preparation method of the novel three-phase interface reactor is characterized by comprising the following steps of:
(1) depositing metal oxide on the surface of the carbon paper by using an atomic layer and performing hydrophobization treatment to obtain a hydrophobized atomic layer deposited porous breathable film;
(2) spin-coating metal sulfide on the surface of the porous breathable film subjected to atomic layer deposition in the step (1) to obtain a hydrophobic atomic deposition porous breathable film loaded with the metal sulfide;
(3) and (3) depositing the hydrophobic atoms loaded with the metal sulfide in the step (2) into a porous breathable film, and further loading biomolecules to obtain the metal sulfide-loaded porous breathable film.
2. The method for preparing a novel three-phase interface reactor according to claim 1, wherein in the step (1), the carbon paper is used for depositing the metal oxide by an atomic layer deposition instrument, and the method comprises the following specific steps:
(a1) immersing carbon paper in an organic solvent, removing attachments on the surface of the carbon paper by ultrasonic, and drying by nitrogen;
(a2) placing the carbon paper treated in the step (a1) into a reaction chamber of an atomic layer deposition device with the temperature of 100-300 ℃, purging for 1-15 min by using high-purity nitrogen, and then using TiCl4Or titanium tetraisopropoxide is taken as a first precursor, and the first precursor is heated to 50-120 ℃ to form TiCl4Or titanium tetraisopropoxide steam, feeding the formed steam into the reaction chamber in a pulse mode, exposing for 5-20 s, purging for 10-30 s by using high-purity nitrogen, feeding the second precursor deionized water into the reaction chamber in a pulse mode, exposing for 5-20 s, continuing purging for 10-30 s by using high-purity nitrogen, and completing one deposition cycle, namely depositing a layer of TiO on the surface of the carbon paper2A film; repeating the steps to deposit TiO with proper thickness on the surface of the carbon paper2A film.
3. The method for preparing a novel three-phase interface reactor according to claim 1, wherein in the step (1), the carbon paper after the atomic layer deposition of the metal oxide is hydrophobized in the reaction tank, and the method comprises the following steps:
(b1) and (3) immersing the carbon paper deposited with the metal oxide into a hydrophobic solvent mercaptan alkane or fluorine-containing reagent with the concentration of 0.5-2 mM, soaking for 3-12 h, taking out, and drying by using nitrogen to obtain the hydrophobic porous breathable film deposited with the atomic layer.
4. The method for preparing a novel three-phase interface reactor as claimed in claim 1, wherein the step (2) of spin-coating the metal sulfide comprises the following steps:
(c1) and spin-coating metal sulfide with the volume of 1-1000 muL and the concentration of 0.001-100mM on the surface of the hydrophobized atomic layer deposited porous breathable film to obtain the hydrophobized atomic layer deposited porous breathable film loaded with the metal sulfide.
5. The method for preparing a novel three-phase interface reactor as claimed in claim 1, wherein in the step (3), the biomolecules are fixed on the surface of the metal sulfide-loaded hydrophobic atomic deposition porous breathable membrane through electrostatic adsorption, and the method comprises the following specific steps:
(d1) the biomolecules with the volume of 1-1000 mu L and the concentration of 0.001-100mM are fixed on the surface of the metal sulfide-loaded hydrophobic atom deposition porous breathable film.
6. The method for preparing a novel three-phase interface reactor according to claim 2, wherein in the step (a1), the organic solvent is isopropanol, ethanol, chloroform or acetone, and the bath ratio of the carbon paper to the organic solvent is 1: 10-1000; and placing the container containing the carbon paper and the organic solvent in an ultrasonic cleaner for ultrasonic treatment for 0.5-6 h.
7. The method for preparing a novel three-phase interfacial reactor according to claim 2,the method is characterized in that in the step (a2), the purity of the high-purity nitrogen for purging is not lower than 99.999%; the purity of TiCl4 and titanium tetraisopropoxide is higher than 97%; the steam of the first precursor and the steam of the second precursor are respectively sent into the reaction chamber with the pulse time of 0.01-0.5 s; finally depositing TiO on the surface of the carbon paper2The thickness of the film is 5 to 30 nm.
8. A novel three-phase interface reactor prepared by the preparation method of any one of claims 1 to 7.
9. Use of the novel three-phase interfacial reactor of claim 8 for degrading pollutants in wastewater treatment.
10. The use of claim 9, wherein the novel three-phase interface reactor is immersed in wastewater containing pollutants as a working electrode, and the working voltage is set to be-0.8V-0.8V.
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| CN108132285A (en) * | 2017-11-27 | 2018-06-08 | 西北工业大学 | A kind of preparation method for the thermal stimulus responsive enzyme anode for loading biological enzyme |
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| CN104862948A (en) * | 2015-04-28 | 2015-08-26 | 武汉纺织大学 | Production method of color carbon fibers |
| CN108132285A (en) * | 2017-11-27 | 2018-06-08 | 西北工业大学 | A kind of preparation method for the thermal stimulus responsive enzyme anode for loading biological enzyme |
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