Water-soluble nickel (II) phthalocyanine with high photocatalytic activity

Abstract

The invention relates to the decomposition, removal from the environment, or conversion into an environmentally friendly form of NOX components, namely NO and NO2, which are malodorous and air-polluting gases formed from tube, stove, and chimney gases in indoor and outdoor environments, followed by the preparation of separate thin films of 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridin-4-methyl-propoxy- nickel(II) phthalocyanine iodide-based nano TiO2, blank binder, and pure TiO2 for use as traps or sensors in chimneys, detectors, aspirators, vacuum cleaners and all devices requiring filters, building facade coatings, air filters, concrete and asphalt coatings, and exhaust systems, realization of the coating process by spraying on glass surfaces in a certain proportion by weight, and comparison of the removal potential of pollutant gases NO, NO2 under solar (ultraviolet and visible region rays) (UV + Vis) light.

Description

[0001] DESCRIPTION WATER-SOLUBLE NICKEL (II) PHTHALOCYANINE WITH HIGH PHOTOCATALYTIC ACTIVITY

[0002] Technical Field of the Invention

[0003] The invention relates to the decomposition, removal from the environment, or conversion into an environmentally friendly form of NOx components, namely NO and NO2, which are malodorous and air-polluting gases formed from tube, stove, and chimney gases in indoor and outdoor environments, followed by the preparation of separate thin films of 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridin-4-methyl-propoxy- nickel(ll) phthalocyanine iodide-based nano TiO2, blank binder, and pure TiO2 for use as traps or sensors in chimneys, detectors, aspirators, vacuum cleaners and all devices requiring filters, building facade coatings, air filters, concrete and asphalt coatings, and exhaust systems, realization of the coating process by spraying on glass surfaces in a certain proportion by weight, and comparison of the removal potential of pollutant gases NO, NO2under solar (ultraviolet and visible region rays) (UV + Vis) light.

[0004] State of the Art

[0005] Nitrogen oxides (NOx) are a class of pollutants found both indoors and outdoors and have significant effects particularly on respiratory and cardiovascular diseases. Nitrogen dioxide (NO2) and nitrogen oxide (NO) are subclasses of NOx and are highly reactive gases which form during combustion. Indoor concentrations depend on both internal and external sources: pollutant levels are generally higher in enclosed spaces. The proximity of buildings to roads or the presence of garages connected to such buildings is considered the major factor affecting indoor concentrations.

[0006] The primary sources of NOx in indoor environments are building heating systems, fossil fuel use in stoves, and tobacco smoke. In houses, increased nitrogen oxide levels may occur when using gas stoves, kerosene heaters, and certain portable gas heaters with cylinders, as well as inadequately maintained central heating boilers or gas fireplaces. Therefore, the oxidation and conversion of the harmful components NO and NO2 accumulated in nature into NO3 is one of the most important steps taken to prevent the formation of air-polluting gases.

[0007] It is possible for the pollutant gases NO2 and NO, which are NOx components, to be decomposed photocatalytically. For this purpose, treatment with a substance that can be activated under sunlight (UV and Vis rays) and its oxidation and decomposition are required. Today, the most widely used substance with photocatalytic properties in this field is TiO2. However, according to studies, TiO2 can be active only under UV light. In photocatalytic systems, semiconductors such as TiO2generate electron and hole pairs under UV light. This process accelerates the conversion of NO gas into NO2and ultimately into NO3“ ions. Nitrate ions in anionic form are easily soluble in water, making them easy to clean and remove.

[0008] • TiO2 + hv — > e- + h+

[0009] • NO — > NO2— > NO3" reactions occur, resulting in the formation of harmless nitrate ions.

[0010] However, TiO2 can only adsorb the light it receives in the UV region. Therefore, in order for TiO2to have the ability to adsorb light also in the visible (Vis) region, it needs to be combined with a material that has photocatalytic activity in the visible region. Thus, under solar light (UV + Vis), it will be able to be activated and easily generate electronhole pairs, and through the OH" and O2* (superoxide) radicals formed, it will oxidize the pollutant gases (NO and NO2) present in the environment into environmentally harmless nitrate ions.

[0011] Phthalocyanines are macrocyclic compounds with an 18TT delocalized electron cloud, containing 8 N and 8 C atoms in their structure (16-membered ring). In addition, they have high thermal stability and a planar structure. Phthalocyanines (Pcs), due to their planar structure and TT-TT stackings arising from delocalized electrons in their structure, interlock on top of each other. This causes them to be resistant to dissolution in water or common organic solvents. However, thanks to their peripheral and non-peripheral positions that allow the attachment of various bulky substituent groups, their solubility can be improved. In photocatalytic applications field, through the formation of OH" radicals and superoxides (O2*), pollutants in water can be decomposed through radicalic reactions. Water molecules in the photocatalysis medium, immediately after the interaction of the semiconductor with ultraviolet rays, detach from the surface to form hydroxyl radicals, which act as oxidizing agents. Immediately after the formation of these radicals, a fragmentation reaction takes place in which the pollutant molecules adsorbed on the semiconductor surface undergo complete mineralization. In a reaction environment where there are no water molecules adsorbed and bound to the surface of the semiconductor, the formation of hydroxyl and / or peroxide radicals, which play an important role in the decomposition of contaminant molecules into harmless products, will not be possible. This causes the photocatalysis reaction to slow down significantly. In photocatalysis reactions, the hydrophilic properties of semiconductor surfaces play an important role in the use of the semiconductor either as a particle or as a thin film. Therefore, it is important that the phthalocyanine molecules to be used in this field have hydrophilic ends and are water soluble. Phthalocyanines, which are soluble in water and common organic solvents and do not show aggregation, have been the subject of study in many fields due to their increasing usability in scientific and technological fields. They are thus being incorporated into many fields such as dye pigments, catalysts, solar cells, nonlinear optical devices, semiconductors, photodynamic therapy (PDT), and photochromic materials.

[0012] In the patent application numbered CN102327231 in the state of the art, the method of preparation of 1 -3 generation poly(aryl ether) dendritic phthalocyanine complex loaded SiC>2 visible light photocatalyst, its photocatalytic performance, and its applicability in the photocatalytic treatment of organic pollutants in air, soil, and sewage are disclosed.

[0013] Another patent application numbered CN1861603 (A) discloses the use of silicon phthalocyanines substituted at axial positions as photosynthesizers in photodynamic therapy for the treatment of tumors.

[0014] In another patent application numbered US2011303617 (A1 ), it is disclosed that porphyrin, rose bengal, anthracene, pyrene, perylene, tetracene, rubrene, and naphthalene-substituted phthalocyanines are chromophore groups capable of absorbing visible and ultraviolet light, and also methods for synthesizing and applying photocatalysts for the photocatalytic degradation of water pollutants. Taking the patent studies above into consideration, a macro molecule containing water- soluble peripheral tetra-positioned 3-pyridin-4-yl-propan-1-ol functional groups and having Nickel metal bonded to the central cavity, namely 2(3), 9(10), 16(17), 23(24)- tetrakis-3-pyridin-4-methyl-propoxy-nickel(ll) phthalocyanine iodide, was obtained, and this compound was integrated into TiC>2 nanoparticles by the sol-gel method. The synthesized 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridin-4-methyl-propoxy-nickel(ll) phthalocyanine iodide / TiC>2 nanoparticles were sprayed onto a glass surface at a ratio of 50% by weight to form a thin film, and for comparison purposes, pure TiC>2 nanoparticles prepared under the same conditions and at the same ratios were also sprayed and coated onto glass surfaces. The obtained photocatalyst candidates were used under solar light (ultraviolet (UV) and visible (Vis) light) for the conversion of NOx components, NO and NO2, and the results were compared.

[0015] As a result of the conducted patent search, no invention step related to the synthesis of 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridin-4-methyl-propoxy-nickel(ll) phthalocyanine iodide and the preparation of nano TiO2 thin films from this molecule was found, and the thin films obtained in this study are original in terms of their application in the field for the removal of pollutant gases NO2 and NO, which are NOx components.

[0016] Problems to Be Solved bv the Invention

[0017] The object of the invention is to synthesize a water-soluble, non-aggregating, photocatalytically active, non-toxic, and easily producible 2(3), 9(10), 16(17), 23(24)- tetrakis-3-pyridin-4-methyl-propoxy-nickel(ll) phthalocyanine iodide molecule, which will be modified with TiO2nanoparticles in order to increase the potential of TiO2nanoparticles upon the adsorption and decomposition, or oxidation of harmful gases NO and NO2, which are NOx components accumulated in the air, into environmentally friendly substances, by enabling TiO2to be activated not only under UV light, where it is naturally active, but also under Vis light, thereby enhancing its efficiency.

[0018] Another object of the invention is to develop a new photocatalytic material to eliminate the adverse effects of NO and NO2gases, which are NOx components formed as intermediates of fuels used in indoor and outdoor environments, on human and animal cardiovascular and respiratory health as well as on plant photosynthesis. Another object of the invention is to produce a new, non-toxic, easily manufacturable sensor that can help detect and reduce the emission of NO and NO2 pollutant reactive gases, which are NOx components accumulated in air and water.

[0019] Another object of the invention is to enable the production and utilization of a promising, new, domestic, and national material by utilizing local resources, in order to reduce dependence on foreign sources and to detect and eliminate highly reactive, harmful, contaminant, and malodorous NO and NO2 gases, which are NOx components accumulated in the air.

[0020] Disclosure of the Invention

[0021] The invention relates to a water-soluble 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridin-4- methyl-propoxy-nickel(ll) phthalocyanine iodide compound, the synthesis method of this compound, and the process of producing a gas sensor candidate functioning as a photocatalyst, which is formed by being modified with TiC>2 nanoparticles in order to examine, for the first time, its photocatalytic activity against environmentally harmful NO and NO2 gases, which are NOx components, and by coating the obtained nanoparticles onto glass surfaces at an optimized rate of 50% by weight.

[0022] The synthesized water-soluble nickel phthalocyanine (6) compound containing 3- pyridin-4-yl-propoxy groups with the molecular name 2(3), 9(10), 16(17), 23(24)- tetrakis-3-pyridin-4-methyl-propoxy-nickel(ll) phthalocyanine iodide is shown in formula 1.

[0023]

[0024] Formula 1 .

[0025] In order to prove that the synthesized nickel phthalocyanine compound of the invention has 1 .25 times higher photocatalytic performance than commercial TiC>2 in the removal of NOx compounds under UV light and 18 times higher photocatalytic performance in the conversion of NO compound to NO2 under solar light (UV and Vis), UV-Vis spectrophotometer analysis of the synthesized water-soluble 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridine-4-methyl-propoxy-nickel(ll) phthalocyanine iodide compound, UV analysis proving the formation of nickel phthalocyanine / Ti02 nanoparticles, zetasizer (particle size) analysis showing that it is modified with nano TiO2, and photocatalytic degradation analysis proving that it shows highly effective properties under solar light (UV and Vis) against NO and NO2gases, which are components of NOx.

[0026] • UV-Vis Spectrophotometer Analysis of Compound (6)

[0027] According to the analysis carried out in the Chemistry Department of Karadeniz Technical University, Trabzon, using a Perkin Elmer Lambda 25 Spectrophotometer device, it was observed that the compound numbered (6), dissolved in the DMSO (dimethyl sulfoxide) solvent, exhibited strong absorption in the visible (Vis) region at the wavelength range of 550-750 nm1 / 6.

[0028] • UV-Vis Spectrophotometer Analysis of Compound (7)

[0029] This analysis was conducted in the Chemistry Department of Akdeniz University, Antalya. According to the analysis performed using a Varian 5000 UV-Vis-NIR Spectrophotometer device, it was observed that pure TiC>2 nanoparticles exhibited absorbance only in the UV region around approximately 230 nm, while the TiC>2- modified 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridin-4-methyl-propoxy-nickel(ll) phthalocyanine iodide compound (7) exhibited absorbance in both the UV and Vis (visible) regions. This result demonstrates that the doping process was successfully achieved2'6.

[0030] • Zeta-Sizer (Particle-size) Analysis

[0031] Nanomaterials expected to have good photocatalytic properties are expected to have a low particle size. This allows the incident light to bind more easily to the surface, facilitating the formation of radical OH’ and O2*. The particle size distributions of the unmodified TiO23 / 6and the compound numbered (7), which were synthesized as nanoparticles by combining with TiO2through the sol-gel method, were observed as 5.197 and 5.136 (d.nm), respectively, indicating that the pore structure did not expand and that the desired size reduction was achieved4'6.

[0032] • Analysis of the Removal of NOx Components NO and NO2 Air Pollutant Gases

[0033] This analysis was carried out at the Department of Materials Engineering, Politecnica delle Marche University, Ancona, Italy. Firstly, a glass surface coated with a reference material called blank binder, followed by a glass surface coated with pure TiC>2 at a ratio of 50% by weight, which served as the control group, and then a thin film of TiC>2 - modified 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridin-4-methyl-propoxy-nickel(ll) phthalocyanine iodide (7c) coated by spraying onto the glass surface at the same ratio by weight were placed separately in the device and a gas mixture containing NO and NO2 was introduced into the environment. The device environment was exposed to UV and solar light (UV-Vis) for 40 minutes under the determined optimum conditions. As a result of the analysis, it was observed that the TiO2-based nickel phthalocyanine nanoparticle (7c) coated on the glass surface at the ratio of 50% by weight showed 1 .25 times5'6higher removal efficiency of NOx components under UV light and 18 times higher activity (selectivity)6'6against NO gas under solar light (UV+Vis) compared to the pure TiO2 thin film (8c) coated at the ratio of 50%.

[0034] The preparation of the 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridin-4-methyl-propoxy- nickel(ll) phthalocyanine iodide-modified TiO2 nanoparticle (7) and the thin film (7c) thereof was carried out in 5 stages.

[0035] 1 . Stage: Synthesis of 4-(3-pyridin-4-ylpropoxy)phthalonitrile compound,

[0036] The synthesis of the molecule (4) referred to in Stage 1 is described in detail below.

[0037] 1. Stage: Synthesis of 4-(3-pyridin-4-ylpropoxy)phthalonitrile (4) compound comprises the process steps of:

[0038] • Dissolving 3-Pyridin-4-yl-propan-1 -ol in 10-50 mL DMF (dimethylformamide) in a single-neck flask,

[0039] • Adding 4-nitrophthalonitrile and K2CO3 into the dissolved mixture and deoxygenating the system in an inert gas nitrogen atmosphere,

[0040] • Stirring the mixture at 60 °C for 4 days,

[0041] • Evaporating the mixture at the end of the reaction to remove the solvent,

[0042] • Dissolving the crude product removed from the solvent in 40-60 mL of chloroform and extracting more than once with 30-50 mL of distilled water.

[0043] • After extraction, adding MgSC into the separated organic phase to remove the remaining water and evaporating chloroform by filtration.

[0044] • Purifying the crude product obtained by passing it through the column loaded with aluminum oxide with CHCI3 solvent and obtaining 4-(3-pyridin-4- ylpropoxy)phthalonitrile compound as a light yellow solid.

[0045] 2. Stage: Synthesis of 2(3), 9(10), 16(17), 23(24)-Tetrakis-3-pyridin-4-yl-propoxy- nickel(ll) phthalocyanine compound,

[0046] The synthesis of the molecule (5) referred to in Stage 2 is described in detail below.

[0047] 2. Stage: Synthesis of 32(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridin-4-yl-propoxy- nickel(ll) phthalocyanine (5) compound comprises the process steps of:

[0048] • Mixing 4-(3-pyridin-4-ylpropoxy)phthalonitrile (100 mg, 0.38 mmol) and NiCl2 (24.61 mg, 0.19 mmol) in 2 mL n-pentanol in the presence of 0.1 -0.4 mL DBU (1 ,8-Diazabicyclo(5.4.0)undec-7-ene) catalyst in a celite tube,

[0049] • Mixing the mixture in nitrogen atmosphere at 150-180 °C for 1 day,

[0050] • Precipitating by adding EtOH to the mixture brought to room temperature and filtering using a sintered crucible.

[0051] • Purifying the solid blue colored substance remaining in the crucible on a column loaded with aluminum oxide using CHCh and MeOH solutions to obtain the dark blue colored solid product, 3-pyridin-4-yl-propoxy phthalocyaninato nickel (II) compound.

[0052]

[0053] 3. Stage: Synthesis of water-soluble 2(3), 9(10), 16(17), 23(24)-tetrakis-3- pyridine-4-methyl-propoxy-nickel(ll) phthalocyanine iodide compound,

[0054] The synthesis of the molecule (6) referred to in Stage 3 is described in detail below. 3. Stage: Synthesis of water-soluble 2(3), 9(10), 16(17), 23(24)-tetrakis-3- Dyridine-4-methyl-DroDoxy-nickel(ll) phthalocyanine iodide (6) compound,

[0055] • Dissolving 32(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridin-4-yl-propoxy-nickel(ll) phthalocyanine compound in 4 mL CHCh solvent in a 50 mL flask,

[0056] • Adding 2-4 mL of CH3I (iodomethane) into the mixture and allow it to mix for 4 days in a dark environment with the container tightly closed,

[0057] • After washing the precipitated solid with CHCI3, acetone and finally diethylether and drying in a vacuum oven at the end of this period, obtaining the dark blue colored solid water-soluble 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridine-4- methyl-propoxy-nickel(ll) phthalocyanine iodide (6) compound.

[0058] Description of the Drawings

[0059] Fig. 1 : UV-Vis Spectrophotometer Analysis of Compound (6)

[0060] Industrial Use of the Invention

[0061] This invention provides a highly efficient material for the removal of environmental air pollution, emission control, and photocatalytic conversion of nitrogen oxide (NOx) components. The 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridine-4-methyl-propoxy- nickel(ll) phthalocyanine iodide / Ti02nanoparticles of the invention have a technology applicable in industrial and daily use areas such as flue gases, exhaust systems, air filters, building facade coatings, concrete and asphalt surfaces. The invention can be used in industrial plants, in reducing emissions from fossil fuel use, in indoor air filtration systems, and in the development of environmentally friendly coating materials. Furthermore, this photocatalytic material is also suitable for different industrial applications, such as controlling gases emitted from power generation plants, removing NO and NO2gases that cause respiratory diseases, and providing long-term protection against pollutants on building exteriors.

[0062] The applicability of the invention is increased by providing a low-cost production opportunity with materials obtained from domestic and national resources. Thanks to its easy production and widespread use, the product can be commercially deployed and used in different fields such as environmental engineering, construction industry, automotive industry, and air purification technologies.

Claims

CLAIMS1. The water-soluble 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridine-4-methyl- propoxy-nickel(ll) phthalocyanine iodide compound (6), characterized by being a nickel(ll) phthalocyanine compound containing 3-pyridin-4-yl-propoxy functional groups2. The 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridine-4-methyl-propoxy- nickel(ll)phthalocyanine iodide compound according to claim 1 , characterized in that it is a molecule that is soluble in water and other common organic solvents.

3. The 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridine-4-methyl-propoxy-nickel(ll) phthalocyanine iodide compound according to claim 1 , characterized in that it is a macromolecule with an effective photocatalytic effect under ultraviolet and visible region (UV-Vis) light.

4. The 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridine-4-methyl-propoxy- nickel(ll)phthalocyanine iodide compound according to claim 1 , characterized in that it is a compound that can be doped with commercially available products that are easy to produce, non-toxic, and possess photocatalytic effects, contributing to the production of more efficient photocatalysts.

5. The 2(3), 9(10), 16(17), 23(24)-tetrakis-3-pyridine-4-methyl-propoxy- nickel(ll)phthalocyanine iodide compound according to claim 1 , characterized in that it is mixed even in a dark environment and at temperatures up to 25°C.

6. The synthesizing step according to claim 5, characterized by mixing for at least 4 days.

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