AN ARTIFICIAL PHOTOSYNTHESIS SYSTEM TO PRODUCE SOLAR FUEL FROM CO2 AND CONVERSION OF DOPAMINE INTO INDOLE DERIVATIVE USING SUN ENERGY

Abstract

The effectiveness of light-harvesting polymeric materials as photocatalysts for industrial applications is often hindered by low crystallinity, which limits their activity and selectivity. This study introduces a novel approach using a soft-template induction technique to fabricate a metal-free heterojunction polymer—5,15-di-(4-aminophenyl)-10,20-diphenyl porphyrin (BP) integrated with perylene tetra-anhydride (PT), termed PTBP. The PTBP polymer exhibits enhanced crystallinity and a strong capacity for solar light absorption, leading to superior photocatalytic performance. The PTBP framework achieves high 1,4-NADH/NADPH regeneration efficiency (52.41/58.41%) and significant NADH utilization, yielding 119.25 µmol of solar fuel from CO2 within one hour. Additionally, it demonstrates excellent conversion efficiency (50.37%) of dopamine to indole derivatives, a marked improvement over PT (13.93%). The superior photocatalytic activity of PTBP is attributed to its bio-boosted photocatalytic cascade, thermal stability, reusability, and broad solar light responsiveness, presenting new avenues for optimizing polymeric frameworks in photocatalysis.

Specification

DESC:FIELD OF THE INVENTION
The present invention relates to an artificial photosynthesis system to produce solar fuel from CO2 and conversion of dopamine into indole derivative using sun energy.
BACKGROUND OF THE INVENTION
References which are cited in the present disclosure are not necessarily prior art and therefore their citation does not constitute an admission that such references are prior art in any jurisdiction. All publications, patents and patent applications herein are incorporated by reference to the same extent as if each individual or patent application was specifically and individually indicated to be incorporated by reference.
The fast expansion of human civilization needs a consistent energy supply and a healthy environment, therefore addressing the shortage of energy and environmental pollution issues that people face today is always a top concern. The photocatalysis process, which can convert sunlight to chemical energy in a variety of applications such as pollutant degradation, CO2 fixation, water splitting, selective clean energy production, and selective organic transformation, will be one of the most useful in the near future. (1-3) The photocatalysis method is based on photocatalysts that have been studied for the last few decades. However, the low efficiency of solar energy consumption and the weak photocatalytic activity of photocatalysts continue to limit their practical implementation. In nature, the most efficient gas-solid reaction system is found in leaves, where gaseous CO2 and H2O may be photocatalytically transformed into hydrocarbons and O2 (4, 5) The high photocatalytic performance of chloroplasts and the distinctive morphological feature of leaves, such as the electron transport path and vein configuration, which enable extremely effective proton/electron and mass transfer, are essentially the two main causes of an excellent conversion efficiency of CO2 in leaves. As a result, good artificial light-harvesting photocatalytic materials should be created to replicate the two elements indicated above, namely, merging the efficient/selective photocatalytic center and mass/charge transfer arrangement in a single system. However, a literature review indicates that recent studies on synthetic polymeric material are mostly focused on the photocatalytic center, with the framework structure/chain of the polymers being largely ignored.
Light harvesting covalent organic polymeric frameworks (COPFs) are crystalline polymers that exhibit great porosity and notable crystalline stability, among other benefits. They can be structurally designed. (6, 7) While the extended pi-conjugated light harvesting in-plane system and stacking direction of COPFs is similar to an electron migration chain, which may be accountable for proton/electron transfer, the unvarying mesoporous structures in covalent polymeric frameworks are similar to strains in leaves, which carry out the mass transfer mission. Artificial photosynthesis greatly benefits from these microstructural properties. COPFs have been tried to simulate photosynthesis from CO2 and H2O in recent years. In addition, photoactive centers in COPFs, such eosin dyes, perylene, acridine yellow G and porphyrin units, have been engineered to resemble catalytic centers, like those found in chloroplasts (8-10). The %Yield of oxidation product is extremely poor, nevertheless. The poor photocatalytic activity and uncomplimentary physical form of COPFs are the fundamental reasons for the very efficient conversion of CO2 by natural leaves, taking into account these two important factors. Using cleverly designed catalytic and photoactive centers in polymeric frameworks (PFs) to shorten the photo-electron transfer distance and increase electron-hole separation efficiency can increase the catalytic activity of COPFs. Regarding the COPFs physical shape, the COPFs catalysts utilized in these investigations are often made into a powder.(11, 12) This leads to two main issues that greatly reduce CO2 photoreduction efficiency: fewer exposed photoactive sites and irregular interfacial mass/charge transfer and diffusion procedures.(13) Creating homogeneous COPFs materials with complex chemical structures, as opposed to COPFs powders, could be a smart decision to address these issues and replicate an artificial leaf. Regretfully, as far as we are aware, no report has yet been published on this investigation on the use of COPFs materials mimic the natural photosynthesis for the CO2 fixation and organic transformation reaction. Herein, we designed and synthesized a metal-free heterojunction of perylene tetra-anhydride (PT)-based-5,15-di-(4-aminophenyl)-10,20-diphenyl porphyrin (BP), i.e., PTBP polymer with excellent crystallinity and solar light harvesting ability (Scheme S3 for PTBP structure). The PTBP polymeric framework was characterized and subsequently used for the first time as an artificial photocatalytic platform for solar-light-driven CO2 fixation and transformation of dopamine (D) into indole derivative like leucodopaminechrome (LDC). Surprisingly, the ideal PTBP polymeric framework has a record high formic acid (HCO2H) 119.25 µmol g-1 in a 1 h reaction, nearly selectivity 100%, and outstanding cyclic reusability (at 5 cycles) against CO2 photo-fixation under solid and gas conditions.
Mechanistic studies demonstrate that the chemical structure units of "PT" and "P" in the PTBP polymeric framework, as well as the rare physical form of the PTBP polymeric framework, as it is metal free, non-toxic, cost effective, easy handling which are significant causes for such an exceptional photocatalytic performance. "P" works as an amazing electron (e-) collector and functions as a photocatalytic center, and the polymeric framework functions as a surface.
Photocatalytic formic acid conversion from CO2, a greenhouse gas, results in environmentally friendly and sustainable chemical manufacturing relevant to industry. Formic acid is a useful chemical used in textiles, fuel cells, preservatives, coagulants, drug synthesis, antibacterial agents and agriculture. By utilizing renewable energy, this technique can lessen dependency on fossil fuels and encourage a circular carbon economy. As a result, it supports international initiatives for sustainable industrial practices and carbon neutrality. Dopamine to indole derivative leucodopaminechrome conversion is industrially relevant because of its potential to create and improve goods in the pharmaceutical and materials science industries. This approach can potentially improve not only the treatment of neurological diseases but also the development of high-performance, bioinspired materials.
The literature comparison table for the photocatalytic activity of different photocatalyst for 1,4-NADH/NADPH cofactor regeneration, formic acid production, and by comparing with the results from our work. Table 1 clearly indicated that our novel designed PTBP photocatalyst is superior to other reported materials. (14-21)
Several patents issued for photocatalysts but none of these are related to the present invention. Patent US11724253B2 concerns a method for the photocatalytic reduction of carbon dioxide carried out in the liquid phase and/or in the gas phase under irradiation using a photocatalyst comprising a support made from alumina or silica or silica-alumina and nanoparticles of molybdenum sulfide or tungsten sulfide having a band gap greater than 2.3 eV, said method comprising the following steps: a) bringing a feedstock containing carbon dioxide and at least one sacrificial compound into contact with said photocatalyst, b) irradiating the photocatalyst with at least one source of irradiation producing at least one wavelength smaller than the width of the band gap of said photocatalyst so as to reduce the carbon dioxide and oxidise the sacrificial compound in the presence of said photocatalyst activated by said source of irradiation, in such a way as to produce an effluent containing, at least in part, C1 or above carbon-containing molecules, different from CO2.
Another patent CN110152711B belongs to the field of nano material preparation and discloses CeO2@MoS2/g C3N4The composite photocatalytic material is prepared through (1) adding cerium oxide hexahydrate into the mixed solution of butylamine and toluene, hydrothermal treatment of the mixed solution, and calcining the reaction product to obtain CeO2A nanocrystal; (2) mixing sodium molybdate dihydrate with g-C3N4The nano-sheets are ultrasonically dispersed in a mixed solution of L-cysteine and dimethyl sulfoxide, and the obtained mixed solution is subjected to hydrothermal treatment to obtain MoS2/g C3N4Nanosheets; (3) adding CeO2Nanocrystalline and MoS2/g C3N4Ultrasonically dispersing in methanol solution, volatilizing methanol, and collecting the obtained product as CeO2 MoS2/g C3N4A composite material; (4) adding CeO2 MoS2/g C3N4The composite material is placed in a tube furnace and calcined in the nitrogen atmosphere to obtain CeO2@MoS2/g C3N4A ternary composite photocatalyst. The preparation method is simple and has strong controllability, and the obtained composite photocatalyst has excellent photocatalytic degradation performance.
Another patent US10105687B1 photocatalyst in the form of chloroplast-like heterostructures of Bi2S3-ZnS is disclosed. Additionally, methods for producing the chloroplast-like heterostructures of Bi2S3-ZnS with controlled morphology, as well as methods for the photocatalytic production of hydrogen gas under visible light irradiation employing the chloroplast-like heterostructures of Bi2S3-ZnS are disclosed.
Another patent US20220395821A1 describes a covalent organic framework. The covalent organic frameworks have unique structural and physical properties, which lends them to be versatile in a number of different applications and uses. In one aspect, the covalent organic frameworks are composed of a plurality of fused aromatic groups and electron-deficient chromophores. The covalent organic frameworks are useful as photocatalysts in a number of different applications.
Another patent US11628432B2 discloses a nitrogen-doped mesoporous carbon-coated Titanium dioxide composite photocatalyst, a preparation method and use thereof. The preparation method comprises the steps of: dissolving an organic ligand and Ti(OC3H7)4 in a mixture of methanol and DMF at a certain ratio, performing a hydrothermal reaction, centrifuging and drying to obtain a Titanium-based metal organic framework (Ti-MOF); pyrolyzing the obtained Ti-MOF under an inert atmosphere, and oxidizing the same for etching to obtain a nitrogen-doped mesoporous carbon-coated Titanium dioxide composite photocatalyst. The obtained composite photocatalyst not only facilitates the adsorption, enrichment and mass transfer of low concentration VOCs, but also efficiently degrades VOCs under sunlight. It has high degradation activity and stability when performing photocatalytic removal of VOCs in the presence of visible light, is simple in synthesis, low in preparation cost, and has strong potential for the use in environmental protection.
Another patent CN106076366B discloses a kind of short-bore road ordered mesopore carbon sulfur loaded indium cobalt and sulphur indium nickel Three-element composite photocatalyst and its preparation method and application. Short-bore Road ordered mesopore carbon sulfur loaded indium cobalt and sulphur the indium nickel Three-element composite photocatalyst is to mix pretreated short-bore road mesoporous carbon with cobalt salt, nickel salt, indium salts and reducing agent, is made through hydro-thermal reaction. Short-bore Road ordered mesopore carbon is that short-bore road ordered meso-porous silicon oxide and carbon source are calcined acquisition under nitrogen protection, and short-bore road ordered meso-porous silicon oxide is to be obtained by the mixture of surfactant, hydrochloric acid solution, ammonium fluoride and ethyl orthosilicate after the calcining of collosol and gel hydro-thermal is reacted successively. The photochemical catalyst has stronger adsorptivity and visible light catalysis activity to VOCs, just effectively can adsorb and degrade in catalyst surface original position be enriched with VOCs, the reaction rate and efficiency of photocatalysis degradation organic contaminant are greatly enhanced, adsorbent or photocatalyst applications can be used as in field of environment protection.
OBJECTS OF THE INVENTION
Main object of the present invention is an artificial photosynthesis system to produce solar fuel from CO2 and conversion of dopamine into indole derivative using sun energy.
Another object of the present invention is to develop an artificial photosynthesis system capable of efficiently converting CO2 into solar fuel using sunlight as an energy source.
Another object of the present invention is to create a metal-free heterojunction photocatalyst using a polymeric framework based on 5,15-di-(4-aminophenyl)-10,20-diphenyl porphyrin (BP) and perylene tetra-anhydride (PT).
Another object of the present invention is to achieve high selectivity and activity in the photocatalytic conversion of dopamine to valuable indole derivatives using solar energy.
Another object of the present invention is to achieve high selectivity and activity in the photocatalytic conversion of dopamine to valuable indole derivatives using solar energy.
Another object of the present invention is to demonstrate a scalable, eco-friendly photocatalytic approach that enables the regeneration of 1,4-NADH/NADPH and the efficient production of bioactive compounds and solar fuels directly from CO2 under ambient solar irradiation conditions.
SUMMARY OF THE INVENTION
This invention introduces a novel artificial photosynthesis system designed to produce solar fuel from CO2 and convert dopamine into indole derivatives using sunlight. The system employs a high-performance, metal-free PTBP polymeric framework photocatalyst, synthesized through a series of carefully controlled reactions. The process begins with the synthesis of 5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin, which involves refluxing pyrrole and benzaldehyde in propionic acid (PA) at elevated temperatures to form a brown reaction mixture. This intermediate is purified and dried, then converted into 5,15-di-(4-aminophenyl)-10,20-diphenyl porphyrin (P) by reduction with stannous chloride (SnCl2) in hydrochloric acid under aerobic conditions.
The PTBP photocatalyst is created by combining the P compound with perylene tetra-anhydride (PT) and imidazole in a high-temperature, inert atmosphere. Following this, the mixture undergoes a secondary reflux in ethanol to precipitate the PTBP polymer. This precipitate is purified through filtration, washed, and then oven-dried to yield a stable photocatalyst powder. The resulting PTBP polymeric framework demonstrates high crystallinity and superior solar light absorption, enabling efficient CO2-to-solar fuel conversion and selective chemical transformations, marking a significant advancement in sustainable photocatalysis.
Herein enclosed an artificial photosynthesis system (photocatalyst) to produce solar fuel from CO2 comprising of: (50 ml) PA, (2 mL) pyrrole, (0.675 mL) benzaldehyde, 500 mg 5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin, (Conc. 1 ml) HCl, (2 g) stannous chloride (SnCl2), ammonium hydroxide (NH4OH), perylene tetra-anhydride (PT), 2g imidazole crystal, and 30 ml ethanol.
The photosynthesis system as claimed in claim 1, wherein the system is comprising the steps of:
refluxing 50 ml of PA at 145ºC, a mixture of 2 mL of pyrrole and 0.675 mL of benzaldehyde were added to in boiling PA;
refluxing the reaction mixed for 1.5 hrs;
removing the flask from oil bath, it could get cooled at room temperature;
filtering the resultant brown colour reaction mixture through a filter paper and washed with DI water followed by methanol until it became clear;
getting the left purple residue (5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin) oven-dry overnight at 100°C;
dissolving 500 mg 5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin in to 1 ml concentrated HCl in a 50 ml round bottle flask;
adding 2 g stannous chloride (SnCl2) was added into this solution along with this;
allowing the solution to stir on a magnetic stirrer for 2 hours at the room temperature with aerobic condition and refluxed for 1.5 hours at 70?;
cooling the solution and neutralizing by adding ammonium hydroxide (NH4OH) dropwise to reached neutral pH;
adding water and chloroform into the solution, as a result of this, two layers were formed in the solution, one was chloroform and other was water;
separating the compound dissolved in chloroform by a separating funnel;
filtering the solution to remove impurities, the filtered solution was passed through sodium sulphate to trap the water;
drying the filtrate and stored the powder compound;
adding 100 mg PT, 216 mg of P and 2g imidazole crystal in a 0.100 L flask;
refluxing the mixture for 6 at 256 ? with inert atmosphere, added 30 ml ethanol in a melted solution and refluxed the solution at 78°C for 6 hours;
cooling this solution and precipitate was filtered out, cleaned the precipitate with water and ethanol;
drying at 100oC in oven, and (98 mg) newly synthesized PTBP polymeric framework photocatalyst obtained.
The PTBP polymeric framework photocatalyst is exposed to solar energy in the presence of CO2, facilitating the conversion of CO2 into solar fuel through a bio-boosted photocatalytic cascade that improves reaction yield and efficiency.
The exposing dopamine to the PTBP polymeric framework photocatalyst under sunlight, whereby the PTBP framework catalyzes the selective transformation of dopamine into indole derivatives with increased yield and efficiency relative to existing methods.
The framework facilitates the efficient regeneration of 1,4-NADH/NADPH under solar irradiation, enabling sustainable chemical transformations with high selectivity.
The PTBP polymeric framework's unique structural properties provide enhanced photocatalytic performance due to a bio-boosted photocatalytic cascade, a broad solar light response range, and resistance to thermal and structural degradation, allowing for effective photocatalytic fuel production and organic synthesis applications.
BRIEF DESCRIPTION OF THE DRAWINGS
The illustrated embodiments of the subject matter will be understood by reference to the drawings, wherein like parts are designated by like numerals throughout. The following description is intended only by way of example, and simply illustrates certain selected embodiments of devices, systems, and methods that are consistent with the subject matter as claimed herein, wherein:
Figure 1. Photocatalytic activities of PT (orange), and PTBP (blue) photocatalyst for (a, c) 1,4-NADH/NADPH cofactor regeneration, (b) Solar fuel HCO2H (formic acid) production , and (d) indole derivative LDC synthesis.
Figure 2. (a and b) UV- visible and the fourier transform infrared (FTIR) spectra of P, PT, and PTBP photocatalyst. (c) Thermogravimetric analysis (TGA) of PT, and PTBP photocatalyst.
Figure 3. Raman spectra of PT and PTBP photocatalyst.
Figure 4. DSC curves of (a) P and (b) PTBP polymeric framework photocatalyst.
Figure 5. Cyclic voltammetry of (a) PTBP photocatalyst with (b) rhodium complex (Rh) (0.2mM), PTBP (10 mM) with NAD+ (0.4 mM) solution.
Figure 6. Nitrogen adsorption-desorption isotherms with pore size distribution curves (inset) of PTBP photocatalyst.
Figure 7. Scanning electron microscopy (SEM) of (a) PT and (b) PTBP photocatalyst.
Figure 8. Energy-dispersive X-ray spectrum of (a) PT and (b) PTBP photocatalyst.
Figure 9. XRD data of PT (red) and PTBP (green) photocatalyst.
Figure 10. Possible 'enzymatically active/inactive' and intermediates 1,4-NADH/NADPH isomers generated during NAD+/NADP+ reduction and dopamine oxidation.
Figure 11. UV-visible spectra for a) photoregeneration 1,4-NADH, b) Photoregenerated 1,4-NADPH and c) conversion of dopamine into indole derivative LDC from PTBP photocatalyst.
DETAILED DESCRIPTION OF THE INVENTION
In some embodiments of the present invention, 5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin was synthesized by literature method. Firstly, 50 ml of PA was refluxed at 145ºC then a mixture of 2 mL of pyrrole and 0.675 mL of benzaldehyde were added to in boiling PA. The reaction mixed was reflux for 1.5 hrs.
In some embodiments of the present invention, then we removed the flask from oil bath so that bit could get cooled at room temperature. Now, the resultant brown colour reaction mixture was filtered through a filter paper and washed with DI water followed by methanol until it became clear. Later we left to purple residue to get oven-dry overnight at 100°C. After that, the residue was subsequently purified by column chromatography on silica gel (eluent: CHCl3)
In some embodiments of the present invention, for the reaction that was carried out, we dissolved 500 mg 5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin in to 1 ml concentrated HCl in a 50 ml round bottle flask. Along with this 2 g stannous chloride (SnCl2) was added into this solution.
In some embodiments of the present invention, the solution was then allowed to stir on a magnetic stirrer for 2 hours at the room temperature with aerobic condition and refluxed for 1.5 hours at 70?. Then the solution was cooled and neutralized by adding ammonium hydroxide (NH4OH) dropwise to reached neutral pH. Water and chloroform were then added into the solution.
In some embodiments of the present invention, as a result of this, two layers were formed in the solution, one was chloroform and other was water. We then separated the compound dissolved in chloroform by a separating funnel. The solution was later filtered to remove impurities. Further, the filtered solution was passed through sodium sulphate to trap the water. Finally, we dried the filtrate and stored the powder compound.
In some embodiments of the present invention, for the synthesis of PTBP polymeric framework photocatalyst, we initiated with adding 100 mg PT, 216 mg of P and 2g imidazole crystal in a 0.100 L flask. This mixture was refluxed for 6 at 256 ? with inert atmosphere. We then added 30 ml ethanol in in a melted solution and refluxed the solution at 78°C for 6 hours. This solution was then left to be cooled and precipitate was filtered out. This precipitate was cleaned with water and ethanol. Further we dried at 100oC in oven. Finally, 98 mg of newly synthesized PTBP polymeric framework photocatalyst obtained.
Herein enclosed an artificial photosynthesis system (photocatalyst) to produce solar fuel from CO2 comprising of: (50 ml) PA, (2 mL) pyrrole, (0.675 mL) benzaldehyde, 500 mg 5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin, (Conc. 1 ml) HCl, (2 g) stannous chloride (SnCl2), ammonium hydroxide (NH4OH), perylene tetra-anhydride (PT), 2g imidazole crystal, and 30 ml ethanol.
The photosynthesis system as claimed in claim 1, wherein the system is comprising the steps of:
refluxing 50 ml of PA at 145ºC, a mixture of 2 mL of pyrrole and 0.675 mL of benzaldehyde were added to in boiling PA;
refluxing the reaction mixed for 1.5 hrs;
removing the flask from oil bath, it could get cooled at room temperature;
filtering the resultant brown colour reaction mixture through a filter paper and washed with DI water followed by methanol until it became clear;
getting the left purple residue (5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin) oven-dry overnight at 100°C;
dissolving 500 mg 5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin in to 1 ml concentrated HCl in a 50 ml round bottle flask;
adding 2 g stannous chloride (SnCl2) was added into this solution along with this;
allowing the solution to stir on a magnetic stirrer for 2 hours at the room temperature with aerobic condition and refluxed for 1.5 hours at 70?;
cooling the solution and neutralizing by adding ammonium hydroxide (NH4OH) dropwise to reached neutral pH;
adding water and chloroform into the solution, as a result of this, two layers were formed in the solution, one was chloroform and other was water;
separating the compound dissolved in chloroform by a separating funnel;
filtering the solution to remove impurities, the filtered solution was passed through sodium sulphate to trap the water;
drying the filtrate and stored the powder compound;
adding 100 mg PT, 216 mg of P and 2g imidazole crystal in a 0.100 L flask;
refluxing the mixture for 6 at 256 ? with inert atmosphere, added 30 ml ethanol in a melted solution and refluxed the solution at 78°C for 6 hours;
cooling this solution and precipitate was filtered out, cleaned the precipitate with water and ethanol;
drying at 100oC in oven, and (98 mg) newly synthesized PTBP polymeric framework photocatalyst obtained.
The PTBP polymeric framework photocatalyst is exposed to solar energy in the presence of CO2, facilitating the conversion of CO2 into solar fuel through a bio-boosted photocatalytic cascade that improves reaction yield and efficiency.
The exposing dopamine to the PTBP polymeric framework photocatalyst under sunlight, whereby the PTBP framework catalyzes the selective transformation of dopamine into indole derivatives with increased yield and efficiency relative to existing methods.
The framework facilitates the efficient regeneration of 1,4-NADH/NADPH under solar irradiation, enabling sustainable chemical transformations with high selectivity.
The PTBP polymeric framework's unique structural properties provide enhanced photocatalytic performance due to a bio-boosted photocatalytic cascade, a broad solar light response range, and resistance to thermal and structural degradation, allowing for effective photocatalytic fuel production and organic synthesis applications.
EXAMPLE 1
EXPERIMENTAL SECTION
Synthesis of 5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin
5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin was synthesized by literature method. Firstly, 50 ml of PA was refluxed at 145ºC then a mixture of 2 mL of pyrrole and 0.675 mL of benzaldehyde were added to in boiling PA. The reaction mixed was reflux for 1.5 hrs. Then we removed the flask from oil bath so that bit could get cooled at room temperature. Now, the resultant brown colour reaction mixture was filtered through a filter paper and washed with DI water followed by methanol until it became clear. Later we left to purple residue to get oven-dry overnight at 100°C. After that, the residue was subsequently purified by column chromatography on silica gel (eluent: CHCl3).(22)
Synthesis of 5,15-di-(4-aminophenyl)-10,20-diphenyl porphyrin (P)
For the reaction that was carried out, we dissolved 500 mg 5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin in to 1 ml concentrated HCl in a 50 ml round bottle flask. Along with this 2 g stannous chloride (SnCl2) was added into this solution. The solution was then allowed to stir on a magnetic stirrer for 2 hours at the room temperature with aerobic condition and refluxed for 1.5 hours at 70?. Then the solution was cooled and neutralized by adding ammonium hydroxide (NH4OH) dropwise to reached neutral pH. Water and chloroform were then added into the solution. As a result of this, two layers were formed in the solution, one was chloroform and other was water. We then separated the compound dissolved in chloroform by a separating funnel. The solution was later filtered to remove impurities. Further, the filtered solution was passed through sodium sulphate to trap the water. Finally, we dried the filtrate and stored the powder compound.(23)
Synthesis of PTBP polymeric framework photocatalyst
For the synthesis of PTBP polymeric framework photocatalyst, we initiated with adding 100 mg PT, 216 mg of P and 2g imidazole crystal in a 0.100 L flask. This mixture was refluxed for 6 at 256 ? with inert atmosphere. We then added 30 ml ethanol in in a melted solution and refluxed the solution at 78°C for 6 hours. This solution was then left to be cooled and precipitate was filtered out. This precipitate was cleaned with water and ethanol. Further we dried at 100oC in oven. (24) Finally, 98 mg of newly synthesized PTBP polymeric framework photocatalyst obtained.
EXAMPLE 2
RESULTS
Unveiling the Power of Light: PTBP-Enhanced Photocatalysis for 1,4-NADH/NADPH Regeneration, indole derivative LDC conversion, and Solar Fuel Production
To investigate PT and PTBP photocatalysts for visible light-driven photo-regeneration of 1,4-NADH/NADPH cofactor and oxidation of dopamine into indole derivative LDC, a number of studies were conducted. UV-visible spectroscopy was used in each instance to determine the levels of dopamine oxidation and photo- regenerated 1,4-NADH/NADPH cofactor. As demonstrated in Figure 1a and Figure 1c, the PTBP polymeric framework was highly influential in 1,4-NADH/NADPH photo-regeneration and photo-oxidation of dopamine with steady accumulation up to 52.51/58.41% and 50.37% with temporal linearity. Additional tests were run to examine the photocatalytic performance of PT and PTBP for the CO2 to HCO2H conversion driven by solar light. With the help of high-performance liquid chromatography formic acid was measured. As can be seen in Figure 1b, when PTBP was utilized as a photocatalyst, the HCO2H production increased linearly with reaction time. Under solar light, the PTBP photocatalyst generated the most formic acid (119.25 µmol) than PT (13.09 µmol). (25, 26) The exclusive production of formic acid in a large volume clearly demonstrates PTBP's advantage over the other photocatalysts investigated. Figure 1d demonstrated the oxidation of dopamine with high yield 50.37% by PTBP photocatalyst than PT (13.93%). of as a result, PTBP is a good photocatalyst for light harvesting. A series of control studies were also performed in the absence of NAD+ and also in absence of Rh. However, no HCO2H was formed in these circumstances. These finding demonstrated the importance of Rh and NAD+ for proper functioning of this system. As a result, the PTBP polymeric framework photocatalyst is an outstanding photocatalyst for light harvesting. Overall, these findings motivated us to do more electrochemical research.
Characterization
The Ultraviolet-visible (UV-Visible) spectra of the P, PT, and PTBP photocatalysts are demonstrated in Figure 2. A soret band and weak Q-bands at 420 nm and range between 500 and 700 nm were visible in the P and PTBP. On the other hand, at the same concentration, the Q-bands of the PTBP polymer framework photocatalyst around 510 nm were wider and had a higher absorbance. The newly synthesized polymer framework photocatalysts' red-shifted absorbance maxima and broadened Q-band indicate the presence of robust intermolecular interactions caused by P and PT, in the newly designed PTBP photocatalyst. (27, 28) Additionally, the improvement in absorption in the domain of visible light confirms the connection between P and PT. At 420 nm, the PTBP polymer framework photocatalyst exhibits a strong absorption peak, and the broad spectrum at 530 nm amply demonstrates the covalent attachment of P and PT. In addition, we determined the 2.29 eV band gap by the Tauc plot method in Figure S1, which is extremely close to the calculated band gap (Eg = 2.36eV) by CV (Figure 5). Overall, the PTBP polymeric framework photocatalyst's estimated band gap is ideal for the conversion of dopamine into LDC and the photo regeneration of 1,4-NADH/NADPH cofactor. (29)
Additional support for the connection of P with PT in PTBP photocatalyst was supplied by the Fourier transform infrared (FTIR) spectroscopy. Characteristic bands were visible in the spectrum of the PTBP polymeric framework photocatalyst (Figure 2b) at 1692 cm-1 for the C-N stretching mode and 1350 cm-1 for the C-N-C stretching mode. Characteristic bands in the spectra of PT were seen at 1754 cm-1 (?C=O), 1729 cm-1 (?C-O), and 3119 cm-1 (?O-H). The spectra of P showed two prominent, recognizable bands at 3317 cm-1 (?N-H) and 2921 cm-1 (?C=C), respectively. The absence of a peak at 1729 cm-1 (?C-O) and a main amine peak in the range of 3000-3400 cm-1 in the spectrum of PTBP polymeric framework photocatalyst (Figure 2b) verified the creation of the PTBP polymer framework photocatalyst. (28) Spectroscopic analysis was also done on chemical composition of the PTBP. According to the Raman spectra of PTBP and PT (Figure 3), the C-O group vanished at a stretch of 1729 cm-1, and the appearance of C-N (1663 cm-1) and C-N-C (near) (1346 cm-1) chemical bonds confirmed the successful formation of the newly observed tertiary amine functional groups by a dehydration reaction between the two precursors. (27)
The DSC (Figure 4) and TGA (Figure 2c) were used to examine the thermal behavior of P, PT, and PTBP polymeric framework photocatalysts. The TGA and DSC were performed at a range of temperatures (25 to 700°C), and (25 to 600°C) with 5°C min-1 ramping rate. The DSC thermograms of P indicated a single exothermic peak at 331.4°C (H = -21820.35 J g-1) as the lone exothermic peak. The DSC thermogram in Figure 4b revealed double exothermic peaks at 355.8 °C (?H = -21820.35 J g-1) and 596.4 °C (?H = -30105.15 J g-1) following the attaching of P with PT. With a rise in temperature up to 700°C, the Thermogravimetric analysis (TGA) curve for PT showed a slight weight loss (29) while 3-step weight loss observed in PTBP polymeric framework. The first is that in the range of temperature (25°C to 350°C), the typical arrangement of sidewall polymerization is a a consistent decrease in weight up to 5.99%. In the temperature range of close to about 410 °C to close to 500 °C, it was followed by the second (12.03%) and third (17.46%) major weight losses (Figure 2c). At about 238.25-269.64 °C, an exothermic peak appeared in the DSC curve (Figure 4a), designating that the imine bonds (C-N) of the PTBP polymeric framework photocatalyst had broken.(30, 31)
To investigate the electrochemical characteristics of PTBP polymeric framework photocatalyst cyclic voltametry (CV) experiment was performed in an SPB (100 mM) at pH 7.0 using glassy a working electrode (carbon), reference electrode (calomel), and counter electrodes (platinum). The reduction potentials of Rh and PTBP were estimated to be around -0.71 eV (29) and -1.3 eV (Figure 5a). When the three components (PTBP,Rh and NAD+) were present in the solution, the CV voltammogram changed. The interaction between Rh and PTBP results in cathodic change or shift in Rh and an anodic change or shift in PTBP. The PTBP-Rh complex show the increased in reduction peak with NAD+, significantly indicating that system consist of PTBP and Rh had ability to catalyze the NAD+ reduction (Figure 5b). According to the published article, the catalytic action of Rh in the existence of NAD+ results in a significantly greater reduction of Rh.(32, 33) Since the excited electron of PTBP can be easily transported to Rh, the photoelectric behavior of PTBP can be considered for the photocatalytic activity of the PTBP-Rh complex. As per the reported article,(34) the photo-electrochemical beheavior of a conjugated solar light-absorbing molecule (PTBP photocatalyst) is triggerred by an excitation of electron from the V.B (E = -5.86 eV) to C.B (E = -3.5 eV), followed by the transfer of electrons into the Rh and cascades into Rh (E = -3.96 eV) without emitting solar light. The close contiguity and potential gradient between the highly efficient light absorbing PTBP polymer framework and the Rh core allow for efficient electron transport from one to the other. Following protonation by aqueous solution, the resulting electrically fixation of Rh, catalyzes the photoregeneration of 1, 4-NADH/NADPH (52.51/58.41% and 50.37%) which further consumed in CO2 conversion into formic acid on coupled with formate dehydrogenase enzyme.
Additionally, the movement of electron was shown by latimer diagram in PTBP photocatalyst (Scheme S4) derived from the cyclic voltammetry experiment using Ered = -1.3 V vs Hg/Hg2Cl2 and Eox = +1.06 V vs Hg/Hg2Cl2. In solar light, PTBP (PC) undergoes into excited state 1PC*(singlet state), which again converted into less energy more stable triplet state 3PC* through ISC along with SET and quenching process.(35-37)
Here, a condensation method-based high-crystalline PTBP polymeric framework photocatalyst with rich mesoporous was created (Figure 6). Small nanosheets stacking form porous aggregates that further assemble at random reveal that the PTBP has porous features SEM, Figure 7). (38, 39).
The EDX (electron dispersive x-ray spectroscopy) showed the different elements in the composition. The EDX spectrum(40) (Figure 8) of PT designated the existence of hetero (O) and non-hetero atom (C). The EDX spectrum of PTBP photocatalyst suggested the presence of hetero (O and N) and non-hetero atom (C). The EDX spectra of the PTBP photocatalyst clearly indicated the incorporation of PT with P.
The XRD study patterns provided additional evidence of the good crystallinity of PTBP. Diffraction peaks may be seen in the XRD patterns of PT and PTBP (Figure 9). Evidently, PTBP contains more peaks than PT, demonstrating a significant improvement in PTBP's integral crystallinity. With a larger FWHM than that of PT, the Peak of PTBP shifts near approximately 0.38° at 12.63° to the high 2?, indicating a reduction in interlayer distance and confirming the higher crystallinity (41-43) of PTBP framework photocatalyst.
Enzymatically active/inactive 1,4-NADH/NADPH isomers determination and dopamine coversion into indole derivative LDC by newly designed PTBP polymeric framework photocatalyst
As illustrated in Figure 10, however, a single electron-fixation of NAD+/NADP+ (NAD/NADP) in the form of a radical is generated, which can dimerize to form a physiologically inactive fixation product. Furthermore, throughout the regeneration of non-enzymatic NAD(P)H, and enzymatically inactive byproducts (1,2/1,6-1,4-NADH/NADPH ) have been seen to occur. (44-46) An electron facilitator, and catalyst are required components of a photo-redox system for cofactor regeneration of 1,4-NADH/NADPH. The development of a ferredoxin-NAD+ reductase (FNR)-based photo-redox system exemplifies the enzymatic reduction of NAD+. Using methyl-viologen (47) as a source of electron facilitator between the photosensitizer and FNR as a photocatalyst, a solar light-driven cofactor regeneration of the NADH system is constructed.(48) Even though this approach employs enzymes to obtain high selectivity, it has shortcomings in terms of corrosion ability, scalability, and durability. (34, 49, 50) We carried out the specific photo-fixation of NAD+/NADP+ to enzyme active 1,4-NADH/NADPH as well as the production of LDC using intermediate Rh complex (methyl viologen is replaced by Rh-complex) and PTBP polymeric framework in a photo-redox system in this study, which a prime focus on peculiar catalytic function of PTBP polymeric framework. In this subsequent reaction, we showed a straightforward and genuine method. Here, we describe a novel and simple procedure that utilizes the PTBP polymeric framework for the photoregeneration of 1,4-NADH/NADPH cofactor, formic acid production and oxidation of dopamine into indole derivative LDC as shown in Scheme 1b. An alteration in absorbance at 340 nm was used to assess the regeneration of 1,4-NADH/NADPH and indole derivative LDC from dopamine was also determined by UV-Visible spectroscopic technique with a distinctive absorption peak at 475 nm along with molar extinction coefficient was e_475 = 3600 M-1 cm-1.(51) (Figure 11)
Possible mechanistic pathway for the NADH/NADPH photoregeneration
Scheme 2 shows a schematic representation of the possible photocatalytic mechanistic process for NADH photo regeneration determined from a cyclic voltammetry experiment. The PTBP polymeric framework photocatalyst captures irradiated solar light resulting in HOMO and LUMO orbitals (Eg = 2.36 eV) electronic transition. After that, the photocatalyst PTBP transfers e- to the Rh-complex. It subsequently transfers the electron to NAD+/NADP+, turning it into NADH/NADPH to complete the photocatalytic cycle. In the final stage, NADH/NADPH incorporated with FDH, which converts CO2 to HCO2H. The reduced NAD+/NADP+ generated, behaves as a substrate for the successive photocatalytic cycle for continuous NADH/NADPH cofactor photo-regeneration.
The cyclic stability and reusability of PTBP photocatalyst up to five cycles without any significant change in 1,4-NADH/NADPH photoregeneration, HCO2H conversion and indole derivative LDC synthesis. The obtained result show that the excellent reusability and stability of newly designed PTBP photocatalyst.
Conclusion
To summarize, the current study provides a freshly synthesized robust PTBP polymeric framework photocatalyst for solar fuel generation and dopamine conversion into indole derivation under sun energy. Spectroscopy, thermal analysis, and microscopic examinations were used to characterize the photocatalyst. The credit for the most systematized solar light harvesting PT and P system goes to PTBP excellent photocatalytic activities, which resulted in a high 1,4-NADH/NADPH regeneration yield of 52.51/58.41/%, exclusive transformation of CO2 into HCO2H (119.25 mmol), and excellent dopamine coversion into indole derivative leucodopaminechrome (50.37%). The current studies clearly show that the PTBP outperforms the previously reported photocatalyst. This is a novel work reported on a light harnessing PTBP polymeric framework as photocatalyst, which has the ability to established a new standard in the field of artificial photosynthesis for production of solar fuel. Overall, the current research points to a promising new route for artificial photosynthesis. The results demonstrate the capability and adaptability of these PT and P-based materials, emphasizing their importance in solar light harnessing, photocatalysis, and solar fuels production.
Non Patent References
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,CLAIMS:1. An artificial photosynthesis system (photocatalyst) to produce solar fuel from CO2 comprising of:
(50 ml) PA, (2 mL) pyrrole, (0.675 mL) benzaldehyde, 500 mg 5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin, (Conc. 1 ml) HCl, (2 g) stannous chloride (SnCl2), ammonium hydroxide (NH4OH), perylene tetra-anhydride (PT), 2g imidazole crystal, and 30 ml ethanol.
2. The photosynthesis system as claimed in claim 1, wherein the system is comprising the steps of:
i. refluxing 50 ml of PA at 145ºC, a mixture of 2 mL of pyrrole and 0.675 mL of benzaldehyde were added to in boiling PA;
ii. refluxing the reaction mixed for 1.5 hrs;
iii. removing the flask from oil bath, it could get cooled at room temperature;
iv. filtering the resultant brown colour reaction mixture through a filter paper and washed with DI water followed by methanol until it became clear;
v. getting the left purple residue (5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin) oven-dry overnight at 100°C;
vi. dissolving 500 mg 5,15-di-(4-nitrophenyl)-10,20-diphenyl porphyrin in to 1 ml concentrated HCl in a 50 ml round bottle flask;
vii. adding 2 g stannous chloride (SnCl2) was added into this solution along with this;
viii. allowing the solution to stir on a magnetic stirrer for 2 hours at the room temperature with aerobic condition and refluxed for 1.5 hours at 70?;
ix. cooling the solution and neutralizing by adding ammonium hydroxide (NH4OH) dropwise to reached neutral pH;
x. adding water and chloroform into the solution, as a result of this, two layers were formed in the solution, one was chloroform and other was water;
xi. separating the compound dissolved in chloroform by a separating funnel;
xii. filtering the solution to remove impurities, the filtered solution was passed through sodium sulphate to trap the water;
xiii. drying the filtrate and stored the powder compound;
xiv. adding 100 mg PT, 216 mg of P and 2g imidazole crystal in a 0.100 L flask;
xv. refluxing the mixture for 6 at 256 ? with inert atmosphere, added 30 ml ethanol in a melted solution and refluxed the solution at 78°C for 6 hours;
xvi. cooling this solution and precipitate was filtered out, cleaned the precipitate with water and ethanol;
xvii. drying at 100oC in oven, and (98 mg) newly synthesized PTBP polymeric framework photocatalyst obtained.
3. The method as claimed in claim 2, wherein the PTBP polymeric framework photocatalyst is exposed to solar energy in the presence of CO2, facilitating the conversion of CO2 into solar fuel through a bio-boosted photocatalytic cascade that improves reaction yield and efficiency.
4. The method as claimed in claim 2, wherein exposing dopamine to the PTBP polymeric framework photocatalyst under sunlight, whereby the PTBP framework catalyzes the selective transformation of dopamine into indole derivatives with increased yield and efficiency relative to existing methods.
5. The method as claimed in claim 2, wherein the framework facilitates the efficient regeneration of 1,4-NADH/NADPH under solar irradiation, enabling sustainable chemical transformations with high selectivity.

6. The method as claimed in claim 2, wherein the PTBP polymeric framework's unique structural properties provide enhanced photocatalytic performance due to a bio-boosted photocatalytic cascade, a broad solar light response range, and resistance to thermal and structural degradation, allowing for effective photocatalytic fuel production and organic synthesis applications.

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