AU2021106112A4 - Molecularly Imprinted Photocatalytic Material, Preparation Method Therefor and Application Thereof - Google Patents
Molecularly Imprinted Photocatalytic Material, Preparation Method Therefor and Application Thereof Download PDFInfo
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- AU2021106112A4 AU2021106112A4 AU2021106112A AU2021106112A AU2021106112A4 AU 2021106112 A4 AU2021106112 A4 AU 2021106112A4 AU 2021106112 A AU2021106112 A AU 2021106112A AU 2021106112 A AU2021106112 A AU 2021106112A AU 2021106112 A4 AU2021106112 A4 AU 2021106112A4
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- molecularly imprinted
- photocatalytic material
- photocatalytic
- imprinted
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- 239000000463 material Substances 0.000 title claims abstract description 100
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 123
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 28
- 231100000719 pollutant Toxicity 0.000 claims abstract description 23
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960005404 sulfamethoxazole Drugs 0.000 claims description 33
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical group O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims description 33
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 24
- 238000006731 degradation reaction Methods 0.000 claims description 18
- 230000015556 catabolic process Effects 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002135 nanosheet Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 19
- 238000001179 sorption measurement Methods 0.000 description 18
- 229960004306 sulfadiazine Drugs 0.000 description 14
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 102100039811 Mitochondrial folate transporter/carrier Human genes 0.000 description 8
- 101001034207 Homo sapiens Mitochondrial folate transporter/carrier Proteins 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 229940088710 antibiotic agent Drugs 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 229940090034 ibu Drugs 0.000 description 1
- 229960001680 ibuprofen Drugs 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- UCSUOYMTZRJAIH-UHFFFAOYSA-N iron(2+) oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Fe+2] UCSUOYMTZRJAIH-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229940125723 sedative agent Drugs 0.000 description 1
- 239000000932 sedative agent Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
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
- B01J35/39—Photocatalytic 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention belongs to the technical field of photocatalytic materials. Disclosed
are a molecularly imprinted photocatalytic material, a preparation method therefor and an
application thereof. The molecularly imprinted photocatalytic material of the present invention
consists of titanium dioxide, iron oxide and carbon nitride. According to the present invention,
molecularly imprinted titanium dioxide is compounded with iron oxide and carbon nitride, thus
reducing the band gap of titanium dioxide, and enabling the prepared molecularly imprinted
catalytic material to generate photogenerated electrons and holes in natural light; moreover, the
molecularly imprinted catalytic material prepared by the present invention is a ternary material,
and the exciton effect thereof may be utilized to improve the separation degree of
photogenerated electrons and holes of the photocatalytic material and the photocatalytic
efficiency, thereby improving the photocatalytic degradation performance of pollutants.
Therefore, the present invention has a good application prospect in the fields of complex water
purification.
Description
Molecularly Imprinted Photocatalytic Material, Preparation Method Therefor and
Application Thereof
The present invention relates to the technical field of photocatalytic materials, in
particular to a molecularly imprinted photocatalytic material, a preparation method therefor
and an application thereof.
With the rapid development of economy and people's attention to their own health,
pharmaceuticals and personal care products (PPCPs) are widely used. However, these
compounds are not fully absorbed by animals and human bodies, and are often excreted in
feces and urine, resulting in the existence of various micro-pollutants, e.g. antibiotics,
sedatives, steroids and endocrine disruptors in water. The abuse of antibiotics is a serious
problem, as antibiotics will produce drug-resistant bacteria, threatening the ecosystem and
human health. How to efficiently remove antibiotics from water bodies has become a
scientific hotspot in recent years. Currently, the main methods to remove antibiotics from
water bodies are biological methods, chemical oxidation, physical adsorption and advanced
oxidation. In view of the disadvantages of traditional biological, physical and chemical
methods, e.g. harsh reaction conditions, high cost and easy secondary pollution, the
advanced oxidation is still the most effective method to remove antibiotics from water
bodies.
In terms of advanced oxidation, photocatalytic technology can utilize solar energy,
which is a renewable energy source, to efficiently degrade pollutants by generating active
substances on the surface of photocatalytic materials, making it a cheap, environmentally
friendly and efficient technology to deal with environmental pollution. The practical
application of photocatalysis mainly depends on the properties of photocatalytic materials, and ideal photocatalytic materials are featured by low cost, no toxicity, abundant raw materials, high efficiency, strong stability, and easy separation and recovery. The widely studied photocatalytic materials are mainly metal-based semiconductors (TiO2, ZnO and
CdS), sulfides, precious metal-based plasma materials (Au, Ag) metal-organic complexes,
and the like. However, these photocatalytic materials are limited in application due to high
cost, or the defects of low quantum efficiency and insufficient utilization of solar energy.
Therefore, there is a need to find a low-cost and highly active photoactive material to further
improve the photocatalytic removal of different pollutants.
Because of good optical activity, low cost and stable chemical properties, titanium
dioxide (TiO2) can be used as a molecularly imprinted substrate to achieve photocatalytic
selectivity. However, it cannot produce free radicals under sunlight, which leads to the
catalytic degradation of pollutants only under ultraviolet light but not under visible light,
thereby limiting the application of titanium dioxide in practice. How to improve the activity
of molecularly imprinted titanium dioxide for degrading pollutants well under visible light is
a technical problem that those skilled in the art have been eager to solve.
The present invention intends to provide a molecularly imprinted photocatalytic
material, a preparation method therefor and an application thereof, so as to solve the
problems in the prior art, improve the activity of molecularly imprinted titanium dioxide, and
enable titanium dioxide to degrade pollutants well under visible light conditions.
To achieve the above purpose, the present invention provides the following technical
solutions:
One object of the present invention is to provide a molecularly imprinted photocatalytic
material, which consists of titanium dioxide, iron oxide and carbon nitride.
Furthermore, the molar ratio of titanium dioxide to iron oxide in the molecularly imprinted photocatalytic material is 100: (1-2.5).
Another object of the present invention is to provide a preparation method of the
molecularly imprinted photocatalytic material, wherein the method includes the following
steps:
dissolving n-butyl titanate, imprinted molecules and glacial acetic acid in absolute ethyl
alcohol, and stirring uniformly to obtain TiO2 sol;
adding an absolute ethyl alcohol solution of FeCl3-6H20 to distilled water gradually,
and stirring in a water bath to obtain Fe203 sol;
uniformly mixing the TiO2 sol and the Fe203 sol, aging to obtain xerogel, grinding and
calcining the xerogel to obtain a TiO2/Fe2O3 compound;
centrifuging an ethylene glycol dispersion liquid of g-C3N4 to obtain a g-C3N4
nanosheet solution; and
mixing the TiO2/Fe203 compound with the g-C3N4 nanosheet solution, standing and
centrifuging to obtain the molecularly imprinted photocatalytic material.
Furthermore, the mass-volume ratio of n-butyl titanate, the imprinted molecule, glacial
acetic acid and absolute ethyl alcohol is 10 ml: (1.15-1.73) g: (5-10 ml): (40-200 ml).
Furthermore, the mass-volume ratio of FeC3-6H20 to absolute ethyl alcohol in the
absolute ethyl alcohol solution of FeCl3-6H20 is 0.1588 g: (10-200) ml.
Furthermore, the concentration of g-C3N4 in the g-C3N4 nanosheet solution is 0.07
mg/L.
Furthermore, the mass-volume ratio of the TiO2/ Fe203 compound to the g-C3N4
nanosheet solution is (0.5-1.5) g:10 mL.
Furthermore, the molar ratio of titanium dioxide to iron oxide in the TiO2/ Fe203
compound is 100: (1-2.5).
Furthermore, the calcination temperature is 400-600°C and the calcination time is 2-5 h.
Furthermore, the imprinted molecule is sulfamethoxazole or other pollutant molecules
that can be vaporized at 400-600°C.
A third object of the present invention is to provide an application of the molecularly
imprinted photocatalytic material in catalytic degradation of micro-pollutants.
Furthermore, the molecularly imprinted photocatalytic material is applied to catalytic
degradation of sulfamethoxazole.
The present invention discloses the following technical effects:
(1) According to the present invention, the molecularly imprinted photocatalytic
material is synthesized into a porous molecularly imprinted titanium dioxide-iron
oxide-carbon nitride photocatalytic material by a simple self-assembly method. With simple
reaction conditions, the photocatalytic material is easy to recycle and reuse, and may be
conveniently produced and applied on a large scale.
(2) The molecularly imprinted photocatalytic material of the present invention has large
specific surface area and pore size to enrich micro-pollutants in water, and has fast electron
transfer rate and good sunlight absorption performance to improve the photocatalytic
degradation performance of pollutants.
(3) The molecularly imprinted photocatalytic material of the present invention has a
very good purification effect on micro-pollutants in complex water bodies, and can remove
up to 99% of sulfamethoxazole which is extremely difficult to degrade.
(4) According to the present invention, molecularly imprinted titanium dioxide is
compounded with iron oxide and carbon nitride, thus reducing the band gap of titanium
dioxide, and enabling the prepared molecularly imprinted catalytic material to generate
photogenerated electrons and holes in natural light; moreover, the molecularly imprinted
catalytic material prepared by the present invention is a ternary material, and the exciton effect thereof may be utilized to improve the separation degree of photogenerated electrons and holes of the photocatalytic material and the photocatalytic efficiency, thereby improving the photocatalytic degradation performance of pollutants. Therefore, the present invention has a good application prospect in the fields of complex water purification and the like.
In order to explain more clearly the embodiments in the present invention or the
technical solutions in the prior art, the following will briefly introduce the drawings needed
in the description of the embodiments. Obviously, drawings in the following description are
only some embodiments of the present invention, and for a person skilled in the art, other
drawings may also be obtained based on these drawings without paying any creative effort.
Fig. 1 is a surface scanning electron microscope image of the molecularly imprinted
photocatalytic material prepared in Example 1.
Fig. 2 is an X-ray diffraction pattern of the molecularly imprinted photocatalytic
material prepared in Example 1.
Fig. 3 is an ultraviolet-visible absorption spectrum of the molecularly imprinted
photocatalytic material prepared in Example 1.
Fig. 4 is a nitrogen adsorption and desorption diagram of the molecularly imprinted
photocatalytic material prepared in Example 1.
Fig. 5 is a pollutant degradation kinetic diagram of the molecularly imprinted
photocatalytic material prepared in Example 1.
Fig. 6 is an EDS diagram of the molecularly imprinted photocatalytic material prepared
in Example 1.
Various exemplary embodiments of the present invention will now be described in
detail, which should not be construed as being limited thereto, but should be understood as a more detailed description of certain aspects, features and embodiments thereof.
It should be understood that the terms described herein are only intended to describe
specific embodiments, and are not intended to limit the present invention. Furthermore, the
range of values in the present invention should be such understood that each intermediate
value between the upper and lower limits of the range is also specifically disclosed. Each
smaller range between any stated value or an intermediate value within a stated range and
any other stated value or an intermediate value within a stated range is also included in the
present invention. The upper and lower limits of these smaller ranges can be independently
included in or excluded from the scope.
Unless otherwise indicated, all technical and scientific terms used herein have the same
meaning as commonly understood to one of ordinary skill in the art to which the present
invention belongs. Although the present invention describes only preferred methods and
materials, any methods and materials similar or equivalent to those described herein can be
used in the practice or testing of the present invention. All literatures mentioned herein are
incorporated herein by reference for the purpose of disclosing and describing the methods
and/or materials associated with the literatures. In the event of a conflict with any
incorporated literature, the contents of this specification shall prevail.
It will be readily apparent to those skilled in the art that various modifications and
changes can be made to the specific embodiments of the specification of the present
invention without departing from the scope or spirit of the present invention. Upon reading
this disclosure, many alternative embodiments of the present invention will be apparent to
persons of ordinary skill in the art. The specification and examples of the present invention
are only exemplary.
As used herein, the terms "including", "comprising", "having" and "containing" are all
open terms, which means including but not limited to.
Example 1:
step 1. dissolving 10 ml of n-butyl titanate, 1.438 g of sulfamethoxazole (SMZ) and 10
ml of glacial acetic acid in 60 ml of absolute ethyl alcohol, and uniformly stirring to obtain
TiO2 sol;
step 2. dissolving 0.1588 g of FeC13-6H20 in 10 ml of absolute ethyl alcohol to obtain a
solution A, gradually adding the solution A into 50 ml of distilled water, and intensely
stirring in a water bath at 90°C for 3 h to form uniform and transparent Fe203 sol;
step 3. evenly mixing the TiO2 sol prepared in step 1 and the Fe203 sol prepared in step
2 to obtain TiO2/Fe23 composite sol, aging for 48 h to form xerogel, grinding the xerogel
into powder, and calcining a muffle furnace at 500°C for 4 h to obtain a TiO2/ Fe203
composite;
step 4. placing melamine in a crucible with a cover put on, calcining at 550°C for 3 h,
cooling to room temperature to obtain a blocky yellow solid g-C3N4, grinding the yellow
solid g-C3N4 into powder, ultrasonically dispersing 10 g of g-C3N4 powder in 100 mL of
ethylene glycol, centrifuging at 3000 rpm, and filtering to obtain a g-C3N4 nanosheet solution;
and
step 5. adding the TiO2/Fe2O3 composite prepared in step 3 to the g-C3N4 nanosheet
solution prepared in step 4, storing at room temperature for 24 h, and centrifuging at 3000
rpm to obtain a molecularly imprinted photocatalytic material TiO2@Fe23@g-C3N4 (MFTC
or MIP-FTC).
Results: the molar ratio of titanium dioxide molecules to iron oxide in the molecularly
imprinted photocatalytic material prepared in this embodiment was 99: 1.
The adsorption rate of the molecularly imprinted photocatalytic material for
sulfamethoxazole was 15.3%. When the amount of the molecularly imprinted photocatalytic
material was 100 mg, the concentration of the pollutant sulfamethoxazole was 10 mg/L and the volume was 100 ml, the molecularly imprinted photocatalytic material prepared in this embodiment could directionally degrade sulfamethoxazole in a complex system containing various pollutants within 120 min, and the degradation rate was 99%.
Fig. 1 is a surface scanning electron microscope image of the molecularly imprinted
photocatalytic material prepared in this embodiment. As seen from Fig. 1, the molecularly
imprinted photocatalytic material prepared in this embodiment has a porous structure with
pores distributed at micron level, indicating that a specific spatial structure is formed by
synthesizing molecularly imprinted dots in the process of synthesizing the molecularly
imprinted photocatalytic material.
Fig. 2 is an X-ray diffraction pattern of the molecularly imprinted photocatalytic
material prepared in this embodiment, where a represents a molecularly imprinted
photocatalytic material TiO2@Fe2O3@g-C3N4, b represents a non-molecularly imprinted
photocatalytic material TiO2@Fe2O3@g-C3N4, and c represents an uncalcined molecularly
imprinted photocatalytic material TiO2@Fe2O3@g-C3N4. As seen from Fig. 2, 20 values are
25.3, 37.8, 48.00, 53.9, 55.1, 62.7°, 68.8, 70.3° and 75.00 respectively, and comply with
the (101), (004), (200), (105), (211), (204), (116), (220) and (215) planes of anatase TiO2
(PDF#21-1272), confirming that the crystalline phase of the molecularly imprinted
photocatalytic material is anatase type; there is no obvious change in the crystal structure
before and after imprinting, indicating that the intrinsic properties of titanium dioxide matrix
are not changed during imprinting, but the photocatalytic performance of titanium dioxide
material is improved.
Fig. 3 is an ultraviolet-visible absorption spectrum of the molecularly imprinted
photocatalytic material prepared in this embodiment, wherein MT is molecularly imprinted
TiO2 (prepared on the basis of Example 1 without addition of Fe203 and C3N4), MTC is
molecularly imprinted TiO2@ g-C3N4 (prepared on the basis of Example 1 without addition of Fe203), MFT is molecularly imprinted TiO2@Fe23 (prepared on the basis of Example 1 without addition of C3N4), and MFTC is molecularly imprinted TiO2@Fe23@g-C3N4 photocatalytic material prepared in this embodiment. As seen from Fig. 3, the absorption edges of TiO2@Fe2O3@g-C3N4, TiO2@Fe2O3 and TiO2@ g-C3N4 move to higher wavelengths, and the absorption intensity increases in ultraviolet and visible light regions, indicating that Fe203 and C3N4 in the molecularly imprinted photocatalytic material improve the light absorption of TiO2. For TiO2@Fe2O3@g-C3N4, the red shift of the absorption edge is due to the lower forbidden band, which leads to a significant change in ultraviolet-visible absorption. The red shift of absorption edge indicates the lower energy band and the improvement of photocatalytic efficiency. TiO2@Fe23@g-C3N4 composite has lower energy band compared with TiO2@Fe23 and TiO2@ g-C3N4, and can generate more electron-hole pairs under visible light, which improves the photocatalytic performance of titanium dioxide.
Fig. 4 is a nitrogen adsorption and desorption diagram of the molecularly imprinted
photocatalytic material prepared in this embodiment, where NIP-FTC is a non-molecularly
imprinted photocatalytic material TiO2@Fe23@g-C3N4, and MIP-FTC is a molecularly
imprinted photocatalytic material TiO2@Fe2O3@g-C3N4 prepared in this embodiment. As
seen from Fig. 4, the specific surface area is positively correlated with the adsorption
capacity and photocatalytic activity, and the N2 adsorption-desorption isotherms of MIP-FTC
and NIP-FTC are iv curves, which further reflects the existence of mesopores. The pore size
distribution curve reveals a narrow pore size distribution, wherein the average pore size of
MIP-FTC is 17.915 nm, and that of NIP-FTC is 7.786 nm. The BET surface area of
MIP-FTC is 50.331 m2 . g-, and that of NIP-FTC is 46.690 m 2 .g- 1 , indicating that the
introduction of molecularly imprinted sites on MIP-FTC not only affects the morphology and
crystallinity of materials, but also increases the specific surface area of materials.
The molecularly imprinted photocatalytic material prepared in this embodiment is used
for oxidative degradation of sulfamethoxazole (SMZ), sulfadiazine (SDZ), ibuprofen (IBU)
and bisphenol A (BPA). To make a more reliable comparison, the SDZ with the same parent
nucleus as SMZ is selected in the present invention, and the degradation process complies
with the pseudo first-order kinetics. Fig. 5 is a pollutant degradation kinetic diagram of the
molecularly imprinted photocatalytic material (MIP-FTC) prepared in this embodiment. As
seen from Fig. 5, the PC oxidation rate constants of MIP-FTC for SMZ, SDZ, IBU and BPA
are 0.0333 min-1 , 0.0155 min-1 , 0.0043 min-' and 0.0057 min-' respectively. This shows that
the introduction of molecularly imprinted sites leads to strong supramolecular interaction
between SMZ and preformed functional groups around molecularly imprinted sites, thus
enhancing selectivity and adsorption of SMZ on MIP-FTC surface. On the contrary, the
adsorption of SDZ, IBU and BPA on MIP-FTC is much lower because they are not
recognized and adsorbed on molecular imprinting sites. Compared with IBU and BPA, SDZ
has a chemical structure similar to SMZ, which allows SDZ to be easily recognized and
adsorbed on MIP-FTC, and have a relatively high binding affinity. Thus, photocatalytic
materials are less selective to SMZ and SDZ, but the molecularly imprinted photocatalytic
material MIP-FTC prepared in the present invention has very strong selective recognition
ability to SMZ.
The main reactive oxygen in the oxidation process of PC is hydroxyl radical, which has
a short life (in the range of 10- s) and also short distribution distance on the catalyst surface
(in nanometer scale). Therefore, only pollutants near the surface, especially pollutants
adsorbed on the surface can be oxidized. In the oxidation process of PC, SMZ is easily
recognized and adsorbed on the catalyst surface, and activated by the supramolecular action
of MI sites; while SDZ, IBU and BPA are less effective in adsorption on the catalyst surface,
and the PC oxidation efficiency of SMZ is higher compared with SDZ, IBU and BPA. The enhanced kinetics of SMZ oxidation further lead to the preferential oxidation of SMZ over
SDZ, IBU and BPA, which contributes to the selective recognition ability of SMZ during PC
oxidation.
Fig. 6 is an EDS diagram of the molecularly imprinted photocatalytic material prepared
in this embodiment. As seen from Fig. 6, iron oxide and carbon nitride are uniformly
distributed on the surface of molecularly imprinted titanium dioxide.
Example 2
Different from Example 1, the imprinted molecule was BPA.
Results: When the amount of catalyst material was 100 mg, the concentration of
pollutants was 10 mg/L and the volume was 100 ml, the adsorption rate of BPA by the
molecularly imprinted photocatalytic material prepared in this embodiment was 12.8%, and
the degradation rate of BPA was 99% in 70 min.
Example 3
Different from Example 1, the imprinted molecule was SDZ, the addition amount of
FeC3-6H20was 0.158 g in step 2, and the calcination temperature was 600°C and the
calcination time was 2 h in step 3.
Results: The molar ratio of titanium dioxide molecules to iron oxide in the molecularly
imprinted photocatalytic materials prepared in this embodiment was 100: 1.
When the amount of catalyst material was 100 mg, the concentration of pollutants was
mg/L and the volume was 100 ml, the adsorption rate of SDZ by the molecularly
imprinted photocatalytic material prepared in this embodiment was 13.4%, and the
degradation rate of SDZ was 99% in 120 min.
Example 4
Different from Example 1, the imprinted molecule was IBU, the addition amount of
FeC3-6H20was 0.395 g in step 2, and the calcination temperature was 400°C and the calcination time was 5 h in step 3.
Results: The molar ratio of titanium dioxide molecules to iron oxide in the molecularly
imprinted photocatalytic materials prepared in this embodiment was 100: 2.5.
When the amount of catalyst material was 100 mg, the concentration of pollutants was
mg/L and the volume was 100 ml, the adsorption rate of IBU by the molecularly
imprinted photocatalytic material prepared in this embodiment was 14.1%, and the
degradation rate of IBU was 99% in 70 min.
Comparison example 1
Different from Example 1, the amount of imprinted molecules was 1.00 g in step 1.
Results: When the amount of catalyst material was 100 mg, the concentration of
pollutants was 10 mg/L and the volume was 100 ml, the adsorption rate of sulfamethoxazole
by the molecularly imprinted photocatalytic material prepared in this embodiment was 8.7%,
and the degradation rate of sulfamethoxazole was 89% in 120 min.
Comparison example 2
Different from Example 1, the amount of imprinted molecules was 2.00 g in step 1.
Results: When the amount of catalyst material was 100 mg, the concentration of
pollutants was 10 mg/L and the volume was 100 ml, the adsorption rate of sulfamethoxazole
by the molecularly imprinted photocatalytic material prepared in this embodiment was
10.9%, and the degradation rate of sulfamethoxazole was 87.2% in 120 min.
Comparison example 3
Different from Example 1, the addition amount of FeCl3-6H20 was 0.079 g in step 2.
Results: The molar ratio of titanium dioxide molecules to iron oxide in the molecularly
imprinted photocatalytic materials prepared in this comparison example was 100: 0.5.
Results: When the amount of catalyst material was 100 mg, the concentration of
pollutants was 10 mg/L and the volume was 100 ml, the adsorption rate of sulfamethoxazole by the molecularly imprinted photocatalytic material prepared in this comparison example was 9.2%, and the degradation rate of sulfamethoxazole was 72% in 120 min.
Comparison example 4
Different from Example 1, the addition amount of FeCl3-6H20 was 0.48 g in step 2.
Results: The molar ratio of titanium dioxide molecules to iron oxide in the molecularly
imprinted photocatalytic materials prepared in this comparison example was 100: 3.
Results: When the amount of catalyst material was 100 mg, the concentration of
pollutants was 10 mg/L and the volume was 100 ml, the adsorption rate of sulfamethoxazole
by the molecularly imprinted photocatalytic material prepared in this comparison example
was 7.2%, and the degradation rate of sulfamethoxazole was 63% in 120 min.
According to the present invention, an inorganic skeleton molecularly imprinted
TiO2@Fe23@g-C3N4 (MFTC) nanocomposite with molecular recognition photocatalytic
activity is successfully prepared by a one-step method. Template molecules may be
completely removed by high-temperature calcination, which avoids the time-consuming and
solvent-consuming problems of traditional extraction methods. Compared with
non-imprinted TiO2@Fe23@g-C3N4 (NFTC), MFTC has higher adsorption capacity and
selectivity for template molecules. The adsorption capacity and selectivity are improved
mainly due to the chemical interaction between target molecules and imprinted holes, and the
size matching between imprinted holes and target molecules. Since the MFTC has high
stability, the selective adsorption of MFTC on target molecules provides a way to form
intermediate products during SMZ degradation. As a result, the photocatalytic activity of
MFTC on target molecules is higher than that of NFTC,
The preferred embodiments described herein are only for illustration purpose, and are
not intended to limit the present invention. Various modifications and improvements on the
technical solution of the present invention made by those of ordinary skill in the art without departing from the design spirit of the present invention shall fall within the scope of protection as claimed in claims of the present invention.
Claims (10)
1. A molecularly imprinted photocatalytic material, characterized by consisting of
titanium dioxide, iron oxide and carbon nitride.
2. The molecularly imprinted photocatalytic material according to claim 1,
characterized in that the molar ratio of titanium dioxide molecules to iron oxide in the
molecularly imprinted photocatalytic material is 100: (1-2.5).
3. A preparation method of the molecularly imprinted photocatalytic material according
to claim 1, characterized by comprising the following steps:
dissolving n-butyl titanate, imprinted molecules and glacial acetic acid in absolute ethyl
alcohol, and stirring uniformly to obtain TiO2 sol;
adding an absolute ethyl alcohol solution of FeCl3-6H20 to distilled water, and stirring
in a water bath to obtain Fe203 sol;
uniformly mixing the TiO2 sol and the Fe203 sol, aging to obtain xerogel, grinding and
calcining the xerogel to obtain a TiO2/Fe2O3 compound;
centrifuging an ethylene glycol dispersion liquid of g-C3N4 to obtain a g-C3N4
nanosheet solution; and
mixing the TiO2/Fe23 compound with the g-C3N4 nanosheet solution, standing and
centrifuging to obtain the molecularly imprinted photocatalytic material.
4. The preparation method of the molecularly imprinted photocatalytic material
according to claim 3, characterized in that the mass-volume ratio of n-butyl titanate, the
imprinted molecule, glacial acetic acid and absolute ethyl alcohol is 10 ml: (1.15-1.73) g:
(5-10 ml): (40-200 ml).
5. The preparation method of the molecularly imprinted photocatalytic material
according to claim 3, characterized in that the mass-volume ratio of FeCl3-6H20 to absolute
ethyl alcohol in the absolute ethyl alcohol solution of FeCl3 -6H20 is 0.1588 g: (10-200) ml.
6. The preparation method of the molecularly imprinted photocatalytic material
according to claim 3, characterized in that the molar ratio of titanium dioxide to iron oxide in
the TiO2/ Fe203 compound is 100: (1-2.5).
7. The preparation method of the molecularly imprinted photocatalytic material
according to claim 3, characterized in that the calcination temperature is 400-600°C and the
calcination time is 2-5 h.
8. The preparation method of the molecularly imprinted photocatalytic material
according to claim 3, characterized in that the imprinted molecule is sulfamethoxazole or
other pollutant molecules that can be vaporized at 400-600°C.
9. An application of the molecularly imprinted photocatalytic material according to
claim 1 in catalytic degradation of micro-pollutants.
10. The application according to claim 9, characterized in that the molecularly
imprinted photocatalytic material is applied to catalytic degradation of sulfamethoxazole.
Intensity(a.u.)
10 20 (101)
30 (004)
40 FIGURES OF THE SPECIFICATION 1/3
(200)
50
FIG. 2 FIG. 1 (105) (211)
60 2 Theta(degree) (204) (116)
70 (220) (215)
80 c a
b
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