WO2022146032A1 - Nouveau composé organique et photocatalyseur au dioxyde de titane le comprenant - Google Patents

Nouveau composé organique et photocatalyseur au dioxyde de titane le comprenant Download PDF

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WO2022146032A1
WO2022146032A1 PCT/KR2021/020178 KR2021020178W WO2022146032A1 WO 2022146032 A1 WO2022146032 A1 WO 2022146032A1 KR 2021020178 W KR2021020178 W KR 2021020178W WO 2022146032 A1 WO2022146032 A1 WO 2022146032A1
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substituted
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carbon atoms
titanium dioxide
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손영아
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충남대학교산학협력단
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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring

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  • the present invention relates to a novel organic compound and a titanium dioxide photocatalyst comprising the same. More particularly, it relates to a novel organic compound capable of improving the photolysis activity of a titanium dioxide photocatalyst by using a novel porphyrin-squaraine-based organic compound sensitive to visible light region energy, and a titanium dioxide photocatalyst comprising the same.
  • VOCs volatile organic compounds
  • a photocatalyst is a substance that does not change before or after a reaction, but is defined as a substance that absorbs light to promote a reaction.
  • a photocatalyst is a material that has the advantage of being able to safely and easily decompose various chemicals just by using light energy and has characteristics such as antibacterial, sterilizing, and superhydrophilic properties.
  • the photocatalytic effect was carried out by Fugishima and Hyundai of Japan in the early 1970s.
  • the photocatalytic reaction was conducted using platinum as a cathode and titanium dioxide as an anode when irradiated with light to separate water into oxygen and hydrogen through photooxidation and photoreduction reactions. After the discovery, follow-up studies were conducted.
  • the photocatalytic reaction is when light of a wavelength having energy greater than or equal to the band gap of the photocatalytic material smokes electrons, electrons and holes inside react with the material adsorbed on the surface, resulting in a reaction by electrons (reduction reaction) and a reaction by holes ( Oxidation reaction) occurs at the same time to effectively decompose the adsorbed material.
  • titanium dioxide TiO 2 , anatase, rutile
  • ZnO ZnO
  • CdS ZrO 2
  • V 2 O 3 V 2 O 3
  • titanium dioxide (TiO 2 ) can be used semi-permanently because its properties as a photocatalyst do not change in the process of decomposing pollutants in contact with titanium dioxide (TiO 2 ) as the compound itself exhibits very good oxidation activity when irradiated with sunlight. do.
  • titanium dioxide (TiO 2 ) can be used semi-permanently because its properties as a photocatalyst do not change in the process of decomposing pollutants in contact with titanium dioxide (TiO 2 ) as the compound itself exhibits very good oxidation activity when irradiated with sunlight. do.
  • ZnO and CdS they absorb light and exhibit activity as a photocatalyst, but at the same time have the disadvantage of being slowly decomposed by exposure to light, so they are clearly distinguished from titanium dioxide (TiO 2 ) compounds.
  • the degree of activity for oxidation is TiO 2 (anatase) > TiO 2 (rutile) > ZnO > ZrO 2 >SnO 3 >V 2 O 3 Among them, TiO 2 is It shows the best activity.
  • titanium dioxide can absorb is ultraviolet light having a wavelength of about 380 nm or less. Therefore, the photocatalytic reaction of titanium dioxide occurs only when UV light is irradiated, and the reaction occurs as much as the amount of UV light, and only when UV light is irradiated, the effect of removing contaminants and harmful substances is exerted. There is a very limited problem with this.
  • the present applicant recognizes the limited light energy absorption capacity of titanium dioxide, the harmfulness of ultraviolet rays, and the insignificant optical resolution of ultraviolet energy itself, and to solve these problems, a novel organic compound capable of absorbing light in the visible region was combined with titanium dioxide to develop a titanium dioxide photocatalyst that can exhibit the effect of removing pollutants and harmful substances even in the indoor visible light wavelength condition.
  • Patent Document 1 KR 10-1400633 B1
  • Another object of the present invention is to absorb energy through a novel porphyrin-squaraine-based organic compound sensitive to visible light region energy, and transfer it to titanium dioxide, thereby exhibiting excellent photolytic activity, and a novel organic compound containing the same To provide a titanium dioxide photocatalyst.
  • a novel organic compound according to an embodiment of the present invention is a compound represented by the following formula (1):
  • n is an integer from 0 to 4,
  • M is selected from the group consisting of Zn, Cd, Hg, Sn, Cu, Co, Ni, Mn, Al, Fe and Ca,
  • X 1 and X 2 are the same as or different from each other, and are each independently a compound represented by Formula 2 or Formula 3,
  • L 1 and L 2 are the same as or different from each other, and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atom
  • Ar 1 and Ar 2 are the same as or different from each other, and each independently represents hydrogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to 30 alkenyl group, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted A heteroaryl group having 2 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon
  • R 1 to R 17 are the same as or different from each other, and each independently hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, A substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 alkynyl group , a substituted or unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C60 heteroaryl group, a substituted or unsubstitute
  • Titanium dioxide photocatalyst according to another embodiment of the present invention is titanium dioxide (TiO 2 ); and a compound represented by Formula 1, wherein the compound represented by Formula 1 is combined with the titanium dioxide (TiO 2 ).
  • hydrogen is hydrogen, light hydrogen, deuterium or tritium.
  • halogen group is fluorine, chlorine, bromine or iodine.
  • alkyl refers to a monovalent substituent derived from a saturated hydrocarbon having 1 to 40 carbon atoms in a straight or branched chain. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.
  • alkenyl refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.
  • alkynyl refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.
  • alkylthio refers to the above-described alkyl group bonded through a sulfur linkage (-S-).
  • aryl refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined.
  • two or more rings may be simply attached to each other (pendant) or condensed form may be included.
  • Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, dimethylfluorenyl, and the like.
  • heteroaryl refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms.
  • one or more carbons in the ring preferably 1 to 3 carbons, are substituted with a heteroatom such as N, O, S or Se.
  • a form in which two or more rings are simply attached to each other or condensed may be included, and further, a form condensed with an aryl group may be included.
  • heteroaryl examples include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl), purinyl, quinolyl, benzothiazole, and carbazolyl, and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but is not limited thereto.
  • 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl), purinyl, quinolyl, benzothiazole
  • aryloxy is a monovalent substituent represented by RO-, wherein R means aryl having 6 to 60 carbon atoms.
  • R means aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.
  • alkyloxy is a monovalent substituent represented by R'O-, wherein R' means an alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure.
  • R' means an alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure.
  • alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, and the like.
  • alkoxy may be a straight chain, branched chain or cyclic chain. Although the number of carbon atoms of alkoxy is not particularly limited, it is preferably from 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. may be, but is not limited thereto.
  • aralkyl refers to an aryl-alkyl group wherein aryl and alkyl are as described above. Preferred aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl and naphthalenylmethyl. Binding to the parent moiety is through an alkyl.
  • arylamino group refers to an amine substituted with an aryl group having 6 to 30 carbon atoms.
  • alkylamino group refers to an amine substituted with an alkyl group having 1 to 30 carbon atoms.
  • aralkylamino group refers to an amine substituted with an aryl-alkyl group having 6 to 30 carbon atoms.
  • heteroarylamino group refers to an amine group substituted with an aryl group having 6 to 30 carbon atoms and a heterocyclic group.
  • heteroarylkyl group refers to an aryl-alkyl group substituted with a heterocyclic group.
  • cycloalkyl refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms.
  • examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
  • heterocycloalkyl means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 carbon atoms, and at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S or Se substituted with a hetero atom such as Examples of such heterocycloalkyl include, but are not limited to, morpholine and piperazine.
  • alkylsilyl refers to silyl substituted with alkyl having 1 to 40 carbon atoms
  • arylsilyl refers to silyl substituted with aryl having 6 to 60 carbon atoms.
  • condensed ring refers to a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
  • “to form a ring by combining adjacent groups” means a substituted or unsubstituted aliphatic hydrocarbon ring by combining adjacent groups with each other; a substituted or unsubstituted aromatic hydrocarbon ring; substituted or unsubstituted aliphatic heterocycle; substituted or unsubstituted aromatic heterocycle; Or it means to form a condensed ring thereof.
  • substitution means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is not limited, and when two or more are substituted , two or more substituents may be the same as or different from each other.
  • the substituent is hydrogen, a cyano group, a nitro group, a halogen group, a hydroxyl group, a carboxy group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, A heteroalkyl group having 2 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, It may be substituted with one or more substituents selected from the group consisting of an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30
  • novel organic compound of the present invention absorbs energy through a novel porphyrin-squaraine-based organic compound that responds to visible light region energy, and transfers it to titanium dioxide, thereby exhibiting excellent photolytic activity.
  • FIG. 1 shows a photolysis mechanism of a titanium dioxide photocatalyst according to an embodiment of the present invention.
  • Figure 2 shows the photophysical properties of the porphyrin-squaraine-based compound (SP-TBU) and the titanium dioxide photocatalyst (SP-TBU-TiO 2 ) according to an embodiment of the present invention.
  • FIG 3 is a chemical composition and structural analysis result of a titanium dioxide photocatalyst (SP-TBU-TiO 2 ) according to an embodiment of the present invention.
  • SP-TBU porphyrin-squaraine-based compound
  • FIG. 6 is a diagram according to an embodiment of the present invention. Porphyrin-squaraine-based compound (SP-TBU) and titanium dioxide photocatalyst (SP-TBU-TiO 2 ) The photolysis activity of the experimental results.
  • SP-TBU Porphyrin-squaraine-based compound
  • SP-TBU-TiO 2 titanium dioxide photocatalyst
  • FIG. 7 is a diagram according to an embodiment of the present invention. Porphyrin-squaraine-based compound (SP-TBU) and titanium dioxide photocatalyst (SP-TBU-TiO 2 ) The photolysis activity of the experimental results.
  • SP-TBU Porphyrin-squaraine-based compound
  • SP-TBU-TiO 2 titanium dioxide photocatalyst
  • FIG. 8 is a fluorescence decay spectra analysis result of a titanium dioxide photocatalyst (SP-TBU-TiO 2 ) according to an embodiment of the present invention.
  • 9 is a stability evaluation result according to 10 times of reuse of a titanium dioxide photocatalyst (SP-TBU-TiO 2 ) according to an embodiment of the present invention.
  • DFT density functional theory
  • TDDFT Time-dependent density-functional theory
  • FIG. 11 is a diagram according to an embodiment of the present invention. The results of the transfer at the electronic level of the porphyrin-squaraine-based compound (SP-TBU) are shown.
  • SP-TBU porphyrin-squaraine-based compound
  • the present invention may be a compound represented by the following formula (1):
  • n is an integer from 0 to 4,
  • M is selected from the group consisting of Zn, Cd, Hg, Sn, Cu, Co, Ni, Mn, Al, Fe and Ca,
  • X 1 and X 2 are the same as or different from each other, and are each independently a compound represented by Formula 2 or Formula 3,
  • L 1 and L 2 are the same as or different from each other, and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atom
  • Ar 1 and Ar 2 are the same as or different from each other, and each independently represents hydrogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to 30 alkenyl group, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted A heteroaryl group having 2 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon
  • R 1 to R 17 are the same as or different from each other, and each independently hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, A substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 alkynyl group , a substituted or unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C60 heteroaryl group, a substituted or unsubstitute
  • Photocatalysts are polluted by decomposing organic materials adsorbed on the catalyst surface through oxidation and reduction reactions while generating electron (e-) and hole (h+) pairs inside when light with energy greater than the band gap is incident. It has the effect of decomposing substances.
  • titanium dioxide TiO 2
  • SiO 2 titanium dioxide
  • a novel porphyrin-squaraine-based organic compound that is sensitive to light in the visible light region was developed, and a photocatalyst was developed in which it was bound to the titanium dioxide (TiO 2 ).
  • the novel porphyrin-squaraine-based organic compound absorbs visible light energy and transfers the energy to titanium dioxide (TiO 2 ) to exhibit excellent photocatalytic decomposition activity.
  • the porphyrin-based compound has a strong absorption region at 400 to 450 nm in the 'soret band' and a weak absorption region in the 'Q-band' 550 to 600 nm, so unlike other materials, it has an absorption wavelength up to near IR, is used as
  • the squaraine-based compound is a type of organic dye that generally exhibits intense fluorescence in the red and near-infrared regions, and has a characteristic of exhibiting strong absorption in a wavelength range of 630 to 670 nm.
  • the titanium dioxide (TiO 2 ) in order to improve the visible light absorption coefficient of the titanium dioxide (TiO 2 )-based photocatalyst, is a novel porphyrin-square in which a porphyrin and a squaraine-based compound having a visible light sensitizing effect are combined.
  • a photocatalyst that can respond to energy in the visible light region with lower bandgap energy was developed.
  • the titanium dioxide photocatalyst of the present invention efficiently absorbs a wavelength range of 400 to 800 nm in the visible light region, and has a low bandgap energy. In addition, excellent stability can be exhibited, and excellent photocatalytic efficiency can be exhibited by inhibiting the recombination of holes and electrons.
  • the titanium dioxide photocatalyst of the present invention can rapidly decompose substances to be decomposed, such as pollutants, and thus has the advantage that it can be used in various industrial fields such as deodorants and antibacterial agents.
  • novel organic compound of the present invention is a compound represented by the following formula (1):
  • n is an integer from 0 to 4,
  • M is selected from the group consisting of Zn, Cd, Hg, Sn, Cu, Co, Ni, Mn, Al, Fe and Ca,
  • X 1 and X 2 are the same as or different from each other, and are each independently a compound represented by Formula 2 or Formula 3,
  • L 1 and L 2 are the same as or different from each other, and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atom
  • Ar 1 and Ar 2 are the same as or different from each other, and each independently represents hydrogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to 30 alkenyl group, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted A heteroaryl group having 2 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon
  • R 1 to R 17 are the same as or different from each other, and each independently hydrogen, a cyano group, a trifluoromethyl group, a nitro group, a halogen group, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, A substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 alkynyl group , a substituted or unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C60 heteroaryl group, a substituted or unsubstitute
  • the compound is a compound exhibiting a first absorption band in a range of 400 to 500 nm and a second absorption band in a range of 600 to 750 nm when measured by an ultraviolet-visible spectra.
  • the first absorption band appearing in the 400 to 500 nm range is a 'soret band' observed by the porphyrin ring, and in general, the soret band of the porphyrin monomer shows one absorption peak, but in the compound, 400 to 500 nm Two absorption peaks can be observed in the region of The splitting of these peaks is due to porphyrinic J-aggregation.
  • the second absorption band observed in the range of 600 to 750 nm is a Q-band, which is indicated by the merging of the Q-band of squarein and porphyrin.
  • the first absorption band and the second absorption band may exhibit maximum peaks at 428 nm and 701 nm, respectively.
  • the absorption of light in a wide wavelength band exhibited by the compound has the advantage of maximizing light-collecting ability and photocatalytic activity.
  • R 9 and R 10 are the same as or different from each other, and each independently represents hydrogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 7 to C 30 aralkyl group, a substituted or unsubstituted an aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, It may be selected from the group consisting of a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroarylamino group having 2 to 24
  • the compound represented by Formula 1 may be a novel porphyrin-squaraine-based organic compound, and may be a compound represented by Formula 4 below:
  • Titanium dioxide photocatalyst according to another embodiment of the present invention is titanium dioxide (TiO 2 ); and a compound represented by Formula 1, wherein the compound represented by Formula 1 is combined with the titanium dioxide (TiO 2 ).
  • the bond may be in the form of a chemical bond, a physical bond, or a bond containing them at the same time, specifically, may be in the form of a chemical bond, and more specifically may be bonded in the form of a covalent bond or an ionic bond, but limited thereto doesn't happen
  • the titanium dioxide photocatalyst may exhibit photocatalytic activity under visible light.
  • the titanium dioxide photocatalyst may be a catalyst for oxidation or a catalyst for decomposition, and more specifically, the titanium dioxide photocatalyst has high structural stability and low toxicity, excellent thermal and chemical stability, high visible light reactivity, smooth energy and With electron mobility, it has advantageous properties of generating reactive oxygen species and catalytic activity for oxidation not only in ultraviolet light but also in visible light region.
  • titanium dioxide photocatalyst responds to and transmits a wide absorption band for harmless visible light, thereby achieving significantly improved photolysis efficiency and decomposition efficiency of harmful compounds.
  • the titanium dioxide photocatalyst can respond to sunlight in daily life or indoor lighting (eg, incandescent lamp, LED, halogen, fluorescent lamp), thereby showing excellent practicality and usability.
  • indoor lighting eg, incandescent lamp, LED, halogen, fluorescent lamp
  • the titanium dioxide photocatalyst of the present invention is an effective visible light responsive photocatalyst, and has excellent effects of removing harmful substances, deodorizing, and sterilizing bacteria and viruses under visible light as well as ultraviolet light, It can be applied to all living spaces such as interior, windowless interior, and household items.
  • the household products specifically refer to masks, gloves, shoes, clothing, protective clothing, hats, etc., but all household products that require removal of harmful substances, deodorization and sterilization effect against bacteria, viruses, etc. can be used without limitation.
  • the application range of the titanium dioxide photocatalyst is not limited to the above example, and various applications are possible, such as clothing materials, paints, photocatalyst filters, and the like.
  • the titanium dioxide photocatalyst may be used as a wastewater treatment agent that adsorbs and removes contaminants in wastewater and oxidizes and decomposes organic matter, which is a harmful compound.
  • the organic material, which is the harmful compound may be selected from methylene blue, nitrobenzene, bisphenol A, methyl orange, etc., and the titanium dioxide photocatalyst generates reactive oxygen species under visible light, as well as decomposition of the above-mentioned harmful compound organic material. , can impart a sterilizing and disinfecting effect against bacteria and viruses.
  • the titanium dioxide photocatalyst of the present invention may exhibit photocatalytic activity under visible light, and the photocatalytic activity may be decomposition activity for methylene blue.
  • the titanium dioxide photocatalyst can be used as an adsorbent capable of adsorbing and removing volatile organic matter, greenhouse gases, odor substances, bacteria such as bacteria and viruses, etc. contained in the air and oxidatively decomposing them.
  • the adsorbent may be an adsorbent of greenhouse gases including CO or CH 4 .
  • the adsorption may be a phenomenon in which gas phase components are physically or chemically bonded to the surface of the titanium dioxide photocatalyst.
  • the titanium dioxide photocatalyst according to the present invention has an improved visible light absorption coefficient, and improves the separation efficiency of the electron (e ⁇ )-hole (h + ) pair (Electron-Hole Pair, EHP) of titanium dioxide for photoexcitation By lowering the activation energy required for , it is possible to effectively absorb light in the visible region as well as the ultraviolet region.
  • the visible light-sensitive decomposition method according to the present invention can activate the oxidation reaction using both ultraviolet and visible light, and thus a high photodegradation rate for harmful compounds and harmful gases (eg, greenhouse gases, etc.), bacteria and virus removal, etc. can be implemented.
  • harmful compounds and harmful gases eg, greenhouse gases, etc.
  • the titanium dioxide photocatalyst of the present invention When used, it shows high reactivity to visible light, which constitutes 46% of sunlight, and can realize a high photodegradation rate even under sunlight, and is irradiated with visible light indoors where sunlight cannot reach. As it can respond to artificial light, it is possible to realize a high photodegradation rate not only outdoors but also indoors.
  • a remarkably improved photodegradation rate that is, a high photodegradation rate for harmful compounds and harmful gases (eg, greenhouse gases, etc.), bacteria and viruses, etc.
  • harmful compounds and harmful gases eg, greenhouse gases, etc.
  • bacteria and viruses etc.
  • the titanium dioxide photocatalyst when irradiated with visible light, it generates reactive oxygen species such as hydroxyl radicals to effectively decompose and remove harmful compounds and harmful gases (eg, greenhouse gases, etc.), bacteria and viruses.
  • FIG. 1 shows the photolysis mechanism for methylene blue of the titanium dioxide photocatalyst of the present invention under visible light conditions.
  • TiO 2 anatase cannot directly absorb visible light, but the titanium dioxide photocatalyst (SP-TBU-TiO 2 ) of the present invention can effectively absorb visible light because it has a low bandgap energy. More specifically, the porphyrin-squaraine-based organic compound (SP-TBU) of the present invention absorbs visible light and transfers the excited electrons to titanium dioxide (TiO 2 ), [SP-TBU + -TiO 2 -] * can form. It then reacts with oxygen to form oxygen radicals, which react with H 2 O 2 to form hydroxyl radicals.
  • SP-TBU-TiO 2 titanium dioxide photocatalyst
  • the porphyrin-squaraine-based organic compound (SP-TBU) of the present invention absorbs visible light and transfers the excited electrons to titanium dioxide (TiO 2 ), [SP-TBU + -TiO 2 -] * can form. It then reacts with oxygen to form oxygen radicals, which react with H 2 O 2 to
  • the titanium dioxide photocatalyst (SP-TBU-TiO 2 ) of the present invention has an advantage in that the photocatalytic activity is maximized when visible light is irradiated in the presence of H 2 O 2 .
  • the titanium dioxide photocatalyst may have a rate constant k value of Equation 1 below in the range of 2.3 x 10 -2 to 3.3 x 10 -2 .
  • C 0 is the initial concentration of the substance to be decomposed
  • k is the rate constant.
  • the rate constant k may be in the range of 3.0 x 10 -2 to 3.3 x 10 -2 .
  • Relational Equation 1 shows the photolysis rate equation of the photocatalyst, and the titanium dioxide photocatalyst (SP-TBU-TiO 2 ) of the present invention has a large rate constant k value compared to TiO 2 anatase. have.
  • the present invention by using a titanium dioxide photocatalyst having excellent thermal and chemical stability and high visible light reactivity, it is possible to stably decompose substances to be decomposed such as methylene blue for a long period of time.
  • the titanium dioxide photocatalyst and visible light decomposition method using the same according to the present invention not only serves to decompose harmful compounds such as methylene blue, but also releases harmful substances regardless of location by using it for household goods, house interior materials, building materials, automobile interior materials, etc. It can contribute to fundamentally suppressing energy consumption, and furthermore, it can contribute to the development of new technology energy fields, such as improving the efficiency of solar energy use and reducing energy conversion costs.
  • the compound 3 (4.3 g, 0.01 mol) was mixed with the compound 6 (1.9 g, 0.011 mol) in 1.5 ml of triethylamine and 40 ml of ethanol and stirred for 2 hours to react.
  • IR(KBrpellet) v max /cm -1 865, 910, 1089, 1100, 1260, 1411, 1489, 1580, 1609, 1700, 3001.
  • the compound 8 (0.521 g, 1 mmol) and the compound 5 (0.345 mg, 1 mmol) were added to 40 ml of benzene and 30 ml of n-butanol, and refluxed for 24 hours. After evaporating the reaction solvent, the remaining material was purified by silica gel column chromatography (95:5 methanol/DCM) to obtain compound 9 as a bright orange solid (0.36 g, 71% yield).
  • SP-TBU porphyrin-squaraine-based compound
  • THF tetrabutyl ammonium fluoride
  • SP-TBU porphyrin-squaraine-based compound
  • Titanium tetrachloride (200 g, 1 mol) and sulfuric acid (3.0 M, 400 ml) were mixed and stored refrigerated, and a titanium dioxide (TiO 2 ) precipitate was obtained.
  • the titanium dioxide (TiO 2 ) precipitate was washed and neutralized with a 1.0 M sulfuric acid solution, and then filtered to obtain pure titanium dioxide (TiO 2 ) nanoparticles.
  • the titanium dioxide photocatalyst (SP-TBU-TiO 2 ) in which the porphyrin-squaraine-based compound (SP-TBU) and titanium dioxide (TiO 2 ) are combined was prepared as follows.
  • TiO 2 anatase titanium dioxide anatase
  • SP-TBU porphyrin-squaraine-based compound
  • FIG. 2( a ) The measurement results of the UV-visible spectra of the porphyrin-squaraine-based compound (SP-TBU) of the present invention are shown in FIG. 2( a ). Specifically, it is the result of an experiment in a concentration condition of THF 0.01M.
  • a first absorption band is exhibited in a range of 400 to 500 nm
  • a second absorption band is exhibited in a range of 600 to 750 nm.
  • the first absorption band refers to the B-band
  • the second absorption band refers to the Q-band.
  • the first absorption band appearing in the 400 to 500 nm range is a 'soret band' observed by the porphyrin ring, and in general, the soret band of the porphyrin monomer shows one absorption peak, but in the compound, 400 to 500 Two absorption peaks can be observed in the nm region. The splitting of these peaks is considered to be the effect of porphyrinic J-aggregation.
  • the second absorption band observed in the range of 600 to 750 nm is a Q-band, which is indicated by the merging of the Q-band of squarein and porphyrin.
  • the maximum peaks of the first absorption band and the second absorption band appear at 428 nm and 701 nm, respectively.
  • the absorption of light in a broad wavelength band including the visible light range of the compound has the advantage of maximizing the light collecting ability and the photocatalytic activity.
  • SP-TBU porphyrin-squaraine-based compound of the present invention
  • the emission maximum values under the excitation condition of 590 nm are 659 nm and 738 nm, 659 nm corresponds to the emission value of the porphyrin part, and 738 nm is the emission of the squaraine part means that it corresponds to the value.
  • Titanium dioxide photocatalyst of the present invention SP-TBU-TiO 2
  • Measurement of diffused reflectance spectrum UV-visible diffused reflectance spectra
  • the diffuse reflection spectrum of the titanium dioxide photocatalyst (SP-TBU-TiO 2 ) was compared with a general TiO 2 anatase (bare TiO 2 ) to which a porphyrin-squaraine-based compound (SP-TBU) is not bound, and the results are shown in FIG. 2 It is shown in (c).
  • the absorption peak does not appear at 400 nm or more, whereas in the case of the titanium dioxide photocatalyst of the present invention (SP-TBU-TiO 2 ), 350 to 500 nm
  • a characteristic peak of porphyrin can be confirmed in the range of
  • a characteristic peak of squaraine can be confirmed in a region of 600 to 800 nm.
  • the shift in the spectral value of the titanium dioxide photocatalyst (SP-TBU-TiO 2 ) compared to the spectral value of the porphyrin-squaraine-based compound (SP-TBU) of FIG. 2(a) is a titanium dioxide photocatalyst (SP-TBU- In the case of TiO 2 ), it can be confirmed that this is because the spectral value of the solid state was measured.
  • porphyrin-squaraine-based compound (SP-TBU) of the present invention is titanium dioxide anatase (TiO 2 anatase) without change in its molecular structure. It can be confirmed that it is successfully bonded to the surface.
  • (i) and (ii) show the results of SEM and TEM analysis of TiO 2 anatase (bare TiO 2 ), respectively, and (iii) and (iv) are titanium dioxide photocatalyst (SP-TBU-TiO) of the present invention. 2 ) shows the results of SEM and TEM analysis.
  • TiO 2 anatase bare TiO 2
  • titanium dioxide photocatalyst SP-TBU-TiO 2
  • the crystal structure was analyzed using X-ray diffraction analysis (XRD).
  • porphyrin-squaraine-based compound of the present invention interacts with the hydroxyl group (-OH) group of titanium dioxide.
  • TiO 2 anatase bare TiO 2
  • titanium dioxide photocatalyst SP-TBU-TiO 2
  • TiO 2 anatase (bare TiO 2 ) showed a value of 531.7 eV
  • titanium dioxide photocatalyst (SP-TBU-TiO 2 ) showed a value of 530.8 eV.
  • the change in the binding energy numerical value is due to the electron-donating property of the O atom of the porphyrin-squaraine-based compound.
  • the energy level of the HOMO state of the porphyrin-squaraine-based compound (SP-TBU) was determined to be -5.69 eV.
  • the difference between E 0-0 and HOMO energy level corresponds to LUMO, and according to FIG. 5 , the value of the energy level of LUMO identified in the porphyrin-squaraine-based compound (SP-TBU) corresponds to -3.37 eV.
  • the conduction band edge potential value of TiO 2 was -3.9 eV, which was lower than the energy value of LUMO found in the porphyrin-squaraine-based compound (SP-TBU).
  • the photolysis activity of the titanium dioxide photocatalyst (SP-TBU-TiO 2 ) for methylene blue (MB) of the present invention was tested under the conditions of irradiation with visible light ( ⁇ max > 400 nm).
  • TCPP-TiO 2 and TiO 2 anatase was set as a control, and compared with the photolysis activity of the titanium dioxide photocatalyst (SP-TBU-TiO 2 ), the results are shown in FIG. 6 .
  • TCPP-TiO 2 which is one of the photocatalysts used as the control, is as shown in Chemical Formula 5 below.
  • the photolytic activity of the TCPP and the porphyrin-squaraine-based compound (SP-TBU) was compared, and in this case, it was confirmed that the photolytic activity of the porphyrin-squaraine-based compound (SP-TBU) was superior.
  • TiO 2 anatase (bare TiO 2 ) had insignificant decomposition activity on methylene blue until about 80 minutes had elapsed, and it was confirmed that more than 80% of methylene blue remained.
  • titanium dioxide photocatalyst (SP-TBU-TiO 2 ) of the present invention it can be confirmed that about 60% of methylene blue is decomposed after 30 minutes, and about 75% of decomposition is made when 40 minutes have elapsed can check that
  • the excellent photolysis activity of the titanium dioxide photocatalyst is because the diaryl amine donor and squaraine-based compound region present in the porphyrin-based compound region effectively absorb energy in the visible light region. to be.
  • H 2 O 2 was added as much as a catalytic amount.
  • the photodegradation rate equation for the material to be decomposed (methylene blue) is as follows:
  • t is the reaction time (min)
  • C 0 is the initial concentration of the material to be decomposed
  • C is the concentration after the reaction time of the material to be decomposed
  • k is the rate constant (min -1 ).
  • the rate constant was calculated using the slope of the graph of FIG. 7 .
  • the rate constant value when no catalyst is added is 0.22 x 10 -2 .
  • the rate constant values of TiO 2 anatase, TCPP-TiO 2 and the titanium dioxide photocatalyst of the present invention are 0.34 x 10 -2 , 1.58 x 10 -2 and 3.17 x 10 -2 , respectively.
  • a high rate constant k means excellent photolysis activity, and it was found that the porphyrin-squaraine-based compound (SP-TBU) and titanium dioxide photocatalyst (SP-TBU-TiO 2 ) of the present invention exhibit the best activity.
  • SP-TBU porphyrin-squaraine-based compound
  • SP-TBU-TiO 2 titanium dioxide photocatalyst
  • the fluorescence lifetime of the photocatalyst was compared with TiO 2 anatase under LED conditions of 340 nm, and the results are shown in FIG. 8 .
  • the stability of the photocatalyst of the present invention was evaluated through the photolysis process for methylene blue. Reusability was evaluated 10 times using the same photocatalyst, and the activity of the photocatalyst was evaluated for 1 hour each time using TCPP-TiO 2 as a control group. The result is shown in FIG. 9 .
  • the titanium oxide photocatalyst (SP-TBU-TiO 2 ) of the present invention is stable under visible light conditions compared to the control group and can be reused repeatedly.
  • the density functional theory (DFT) calculation result of the porphyrin-squaraine-based compound (SP-TBU) of the present invention is shown in FIG. And it can be seen that the aromatic amine substituent is formed perpendicular to the porphyrin moiety.
  • the energy level of HOMO is -4.928 eV
  • that of LUMO is -3.004 eV
  • the optical band is 1.924 eV.
  • the energy level of the LUMO is higher than that of TiO 2 anatase.
  • the characteristic of the energy level of the porphyrin-squaraine-based compound (SP-TBU) of the present invention is that it absorbs the energy of the visible light wavelength more effectively and then transfers it to titanium dioxide (TiO 2 ), thereby maximizing the photocatalytic efficiency.
  • the present invention relates to a novel organic compound and a titanium dioxide photocatalyst comprising the same. More particularly, it relates to a novel organic compound capable of improving the photolysis activity of a titanium dioxide photocatalyst by using a novel porphyrin-squaraine-based organic compound sensitive to visible light region energy, and a titanium dioxide photocatalyst comprising the same.

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Abstract

La présente invention concerne un nouveau composé organique et un photocatalyseur au dioxyde de titane le comprenant. L'énergie est absorbée par un nouveau composé organique à base de porphyrine-squalène répondant à une énergie de lumière visible et est transférée au dioxyde de titane, ce qui permet d'obtenir une excellente activité photolytique.
PCT/KR2021/020178 2020-12-30 2021-12-29 Nouveau composé organique et photocatalyseur au dioxyde de titane le comprenant WO2022146032A1 (fr)

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Citations (2)

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CN102008980A (zh) * 2010-11-02 2011-04-13 浙江理工大学 金属卟啉敏化二氧化钛光催化剂及其制备方法
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CN102008980A (zh) * 2010-11-02 2011-04-13 浙江理工大学 金属卟啉敏化二氧化钛光催化剂及其制备方法
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