BODIPY-INFUSED PORPHYRIN NANOCOMPOSITE-ENZYMATIC PHOTOCATALYST BOOSTS SELECTIVE ALDEHYDES HYDROGENATION AND ORGANIC TRANSFORMATION UNDER SOLAR SPECTRUM

Abstract

The synthesis and development of the photocatalyst (NH2)4TPP@BODIPY, derived from 5,10,15,20-tetrakis(4-aminophenyl) porphyrin and BODIPY {5,5-difluoro-3,7-bis((E)-4-nitrobenzylidene)-10-(4-nitrophenyl)-5,7-dihydro-3H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine}, through a poly-condensation mechanism, shows promise in solar-driven organic chemical production. This composite exhibit excellent light-harvesting capabilities and photocatalytic activity, with a favorable band gap and efficient electron channels. It achieves an organic transformation efficiency of 98% and photo-regeneration of NADH at 66.92% within 60 minutes, facilitating aldehyde reduction to alcohol. The highly selective hydrogenation of aldehydes is mediated by alcohol dehydrogenase, which coordinates with the photocatalyst, regenerating NADH in the process. These findings establish a strong benchmark for NAD+ co-factor coupled solar-driven alcohol production using the (NH2)4TPP@BODIPY photocatalyst.

Specification

DESC:FIELD OF THE INVENTION
The present invention relates to BODIPY-infused Porphyrin Nanocomposite-Enzymatic Photocatalyst Boosts Selective Aldehydes Hydrogenation and Organic Transformation under Solar Spectrum. The synthesis and development of (NH2)4TPP@BODIPY photocatalyst, which was constructed from 5,10,15,20 tetrakis (4 amino phenyl) porphyrin and BODIPY {5,5-difluoro-3,7-bis((E)-4-nitrobenzylidene)-10-(4-nitrophenyl)-5,7-dihydro-3H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine} molecule through poly-condensation mechanism resulting in the composite formation which manifest excellent light harvesting properties and photocatalytic reactions with suitable satisfactory band gap and formation of huge electrons channels which bears the organic transformation (98%) and photo-regeneration of NADH (66.92%) in 60 minutes which further enhances reduction of aldehyde resulting alcohol production.
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.
Conversion of solar radiation into solar-driven organic chemicals in the process of photosynthesis is mainly associated with integrated photosystems consisting of an organized arrangement of metal clusters and chlorophyll pigments to ease the capture of light, separation and transfer of charge, production to an energy storage molecule such as reduced nicotinamide adenine dinucleotide phosphate (NADH) and adenosine triphosphate (ATP).[1] The emerging trans-membrane electrochemical potential is responsible for proton flow across the membrane.[2] This photoelectron's flow is stalked via thermal electron transfer resulting in the separation of charge which has been demonstrated to mimic the natural phenomenon of photosynthesis via covalently bonded electron donors and electron acceptors. Currently, inspired by the natural phenomenon of photosynthesis in green plants, the construction of an artificial track that mimics natural photosynthesis results in producing of solar organic chemicals is in demand.[3-5] Natural photosynthesis involves oxidation of water and reduction of CO2[6,7] therefore, involves 3 processes i.e. light-harvesting system, catalytic reaction, generation of electron carriers, and their separation.[8] Since artificial photosynthesis provides a single-step pathway for these processes will mimics the Z-scheme mechanism of natural photosynthesis.[9-12] The photocatalytic light-harvesting system mainly consists of semiconductors and dyes. With this perspective reduction of CO2 into chemicals takes place. [13-14] Under solar radiation photo generation of electrons occurs which further transfers to the electron medium. Co-enzyme NAD+ photo regenerates to NADH via receiving hydride anion from an electron medium.[15-16] While, NADH behaves as a hydrogen donor to CO2 reduction into organic chemical production also photo generated holes were consumed via sacrificial agents (i.e. ascorbic acid, TEOA, etc.) to overcome electron-hole recombination.[17-18] Based on this understanding, artificial photosynthesis manifests organic transformation and biotransformation of aldehyde to alcohol.[19] Therefore, the 4-Chlorobenzylamine has been effectively converted to respective benzylimines via photocatalyst and the transformation of aldehyde to alcohol via conventional microbial method can be replaced via solar-driven photocatalytic method in which the main enzyme that assistant the biotransformation is alcohol dehydrogenase (ADH) and the hetero-junction photocatalyst provide the energy level and accepts the charge carries to perform a particular catalytic transformation.[20-22] Alcohol is a promising chemical for hydrogen storage that can be fruitfully dehydrogenated by alcohol dehydrogenase (ADH) via the aid of coenzymes.[23-24] Typically, the biologically selective hydrogenation of alcohol production always assists via an enzyme called alcohol dehydrogenase (ADH) or also via some microorganism providing ADH like activity behaving as a whole-cell catalyst. To archive alcohol production some literature came up with biphasic Bacillus coagulans as a whole-cell catalyst in which alcohol production can be archived in situ, the productivity can also be enhanced when the in situ phase is separated from the cell-rich aqueous phase.[25-26] Despite that recent hydrogenative biotransformation of aldehyde can be archived via microbial activity and sugar as a carbon source for NADH regeneration to gain inner cellular energy to intake of aldehyde through the cell membrane.[22-27]
Currently, porphyrin is a hub for the huge conjugation which leads to efficient photocatalytic activity because of its unique properties and promising applications. [28-29] These properties induce a remarkable capacity to transport thermal and charge carriers.[30] Here keep in mind that excellent charge carrier's mobility and transportation not only show good physical and chemical properties of the compound but also shows excellent photocatalytic and photovoltaic behavior. Moreover, nitration and then amination of the porphyrin shows enhancement of the photocatalytic properties because of the amino group (-NH2) which increases the absorption of the native porphyrin macrostructure. [31-32] But this is also limited to some extent. Therefore, in addition, BODIPY also has a high molar extinction coefficient, photochemical efficiency, effective charge transfer, and huge conjugation which if covalently attached to amino porphyrin results in excellent photocatalytic efficiency.[33] Also, the chromophores attached i.e. -NO2 group of BODIPY and the -NH2 group of the amino porphyrin enhanced the electron density on the parent moiety (BODIPY, amino porphyrin) which increases the conjugation of the moieties.[34] On this account, these two moieties show excellent results when covalently attached. Among the various organic materials 5,10,15,20 tetrakis (4 amino phenyl) porphyrin [here called amino porphyrin] and BODIPY coupling show excellent photocatalytic activity.[35] Chemical properties which include photo-stability, capability to flow charge carriers, effective band gap, etc. [36-37] These are some principal keys of a desirable characteristic to perform photocatalytic reactions like organic transformations and bio-transformations of different aldehyde. This can be enhanced via coupling and resulting in azo (N=N) linkage which has proven to show high chemical as well as physical properties to perform photocatalytic reactions. [34-38] We therefore, speculated that the azo linkage (NH2)4TPP@BODIPY photocatalyst could be proven to be an optimistic contestant to perform organic transformation [39] and biotransformation coupled NADH regeneration activities owing to fulfilling all light harvesting photocatalytic conditions.[40]
Several patents issued for composites or photocatalysts but none of these are related to the present invention. Patent CN105597820B provides the preparation method of carbonitride/tetracarboxylic phenyl porphyrin nano composite of a species graphite-phase, is obtained using solid-phase ball milling method. The present invention also provides carbonitride/application of the tetracarboxylic phenyl porphyrin nano composite in photocatalysis of above-mentioned class graphite-phase. The preparation method of the present invention is simple, and cost is low, easy to operate, while can significantly save the reaction time. The nano composite material of the present invention has the sensitivity and stability that preferable Photoelectrochemical Properties Properties, stronger photocatalysis performance are become reconciled, and plays the role of in terms of organic pollutant degradation and photocatalytic degradation of dye important.
Another patent CN111514937B relates to a preparation method of a porphyrin-based metal organic framework material sensitized oxide type catalyst, which is used for treating organic pollutants in water through visible light catalytic degradation. A transmission channel of photo-generated charges is constructed by taking a porphyrin-based metal organic framework material as a sensitizing agent, silver and cerium double-doped zinc oxide and introducing a sensitizing auxiliary agent, so that the photocatalytic degradation performance under visible light conditions is enhanced. The degradation performance of the composite catalyst on methylene blue, a typical organic pollutant in water, is inspected under the condition of visible light, and the catalyst is proved to have better capability of degrading organic matters in water under the visible light.
Another patent CN110102342A discloses a kind of for producing hydrogen peroxide is sensitized nitridation carbon composite photocatalyst and preparation method thereof. This method step includes: to calcine carbon nitride precursor in Muffle furnace to obtain azotized carbon nano piece;Then p-bromobenzaldehyde and pyrroles are dissolved into organic solvent, and under the catalytic action of acid, reaction obtains porphyrin;Azotized carbon nano piece is scattered in ethyl alcohol, porphyrin solution is added, is reacted under room temperature and the porphyrin sensitization nitridation carbon composite photocatalyst for producing hydrogen peroxide is made. Preparation method provided by the invention has many advantages, such as that step is simple, at low cost and controllability is strong, and there is porphyrin sensitization nitridation carbon composite photocatalyst provided by the invention excellent photocatalysis to produce hydrogen peroxide performance.
Another patent KR101421572B1 includes a complex of TiO_2 and a porphyrin derivative, and relates to a photocatalyst electrodeposited with platinum particles and a method for preparing the same. Since the photocatalyst according to the present invention includes the TiO_2-porphyrin derivative complex, light in visible region can be absorbed among the sunlight. The photocatalyst has a wide absorption band and good efficiency as a photocatalyst, and thus, can be usefully applied in producing hydrogen by decomposing water.
Another patent CN114308084A discloses a preparation method of a titanium dioxide/lead-free halogen system perovskite composite photocatalytic material. Firstly, a ligand-assisted recrystallization method is used for preparing the lead-free halogen perovskite. Then, a certain amount of titanium dioxide is weighed and ultrasonically dispersed in a solvent to obtain a titanium dioxide solution. The lead-free halogen perovskite is added into a titanium dioxide solution according to a certain proportion and stirred for a period of time at a certain temperature. And finally, centrifuging and drying the mixed solution to obtain the titanium dioxide/lead-free halogen perovskite composite photocatalytic material. The invention will not contain leadThe halogen perovskite is loaded on the surface of the titanium dioxide, so that the specific surface area of the titanium dioxide is increased, and meanwhile, the photoresponse range is widened to a visible light region, so that the visible light catalytic performance of the titanium dioxide is effectively improved. The photocatalyst has wide application prospect, and can be used for water pollution treatment and CO2Reduction, hydrogen production and the like.
Another patent CN114247452A discloses a bismuth-bismuth sulfide-bismuth tungstate composite photocatalyst and a preparation method and application thereof. Respectively dissolving bismuth nitrate and sodium tungstate in ethylene glycol, and dissolving thiourea in an ethanol solution; mixing the three solutions to obtain a precursor solution; and carrying out solvothermal reaction on the precursor solution, washing and drying the black precipitate obtained by the reaction to obtain the bismuth-bismuth sulfide-bismuth tungstate composite photocatalyst. The invention synthesizes the bismuth-bismuth sulfide-bismuth tungstate composite photocatalyst by regulating and controlling the proportion of thiourea and sodium tungstate, simultaneously utilizing a reducing additive to generate metal bismuth and utilizing a solvothermal method in one pot. The invention has the advantages of simple preparation, easily obtained raw materials, low production cost and environmental protection. The bismuth-bismuth sulfide-bismuth tungstate composite photocatalyst has the advantages of wide visible light absorption range, low photo-generated carrier recombination rate, stable performance and high activity of photocatalytic degradation of plasticizer, and has wide application prospect in the aspects of visible light utilization and environmental protection.
OBJECTS OF THE INVENTION
Main object of the present invention is BODIPY-infused Porphyrin Nanocomposite-Enzymatic Photocatalyst Boosts Selective Aldehydes Hydrogenation and Organic Transformation under Solar Spectrum.
Another object of the present invention is to prepare BODIPY-infused Porphyrin Nanocomposite-Enzymatic Photocatalyst.
Another object of the present invention is to prepare photocatalyst boosts selective aldehydes hydrogenation and organic transformation under solar spectrum.
SUMMARY OF THE INVENTION
The present invention describes the synthesis of a BODIPY photocatalyst through a multi-step process. Initially, BODIPY {5,5-difluoro-3,7-bis((E)-4-nitrobenzylidene)-10-(4-nitrophenyl)-5,7-dihydro-3H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine} was synthesized by reacting 4-nitro benzaldehyde with pyrrole in a methanol/water mixture, catalyzed by HCl, and complexed with BF3.OEt2. This yielded dark brown crystals after purification. Separately, TNPP (tetrakis(4-aminophenyl) porphyrin) was reduced using hydrochloric acid and SnCl2, resulting in dark purple crystals.
In the final step, BODIPY and TAPP were combined in DMF under an inert atmosphere and refluxed at 150°C for 24 hours, forming the (NH2)4TPP@BODIPY photocatalyst. The resultant dark purple crystals were purified and characterized using various spectroscopic techniques, including nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS). The photocatalyst demonstrated stability and reusability, confirmed by cyclic experiments and FT-IR analysis.
Herein enclosed a photocatalyst composite, comprising:
a BODIPY derivative {5,5-difluoro-3,7-bis((E)-4-nitrobenzylidene)-10-(4-nitrophenyl)-5,7-dihydro-3H-4?4,5?4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine}; and
Tetrakis(4-aminophenyl) porphyrin (TAPP);
wherein the two components are combined through poly-condensation to form a nanocomposite.
A method for producing the photocatalyst composite as claimed in claim 1, wherein the method comprising the steps of:
synthesizing the BODIPY derivative by reacting 4-nitrobenzaldehyde and pyrrole in a methanol/water mixture (1:4) catalyzed by hydrochloric acid, followed by complexation with BF3·OEt2;
resulting a yellow-colored colloidal solution, after stirring overnight dark brown color of colloidal solution was formed;
doing workup of solution with chloroform and water to obtain dark brown crystals of BODIPY;
synthesizing TAPP by dissolving 500mg of TNPP in 20mL concentrated hydrochloric acid along with 2g of SnCl2 in a round bottom flask stirred at room temperature for 2 hours;
refluxing at 70oC the reaction mixture for 1.5 hours, and the reaction was then monitored using TLC;
after cooling, the mixture was quenched via ammonia solution, filtered and workup with chloroform and water;
obtaining the resultant dark purple crystals after crystallization;
combining the BODIPY derivative (68.20mg) and TAPP (100mg) dissolved in DMF in a round bottleneck flask in an inert atmosphere;
refluxing the reaction mixture at 150oC for 24hours;
after cooling the reaction mixture at room temperature, 21mL of distilled water was added to the reaction mixture and constant stir for 1hrs;
filtering the reaction mixture and workup was done via warm water and acetone followed by DMF; and
obtaining the dark purple crystal of (NH2)4TPP@BODIPY photocatalyst after crystallization.
The composite is capable of selective aldehyde hydrogenation under solar radiation.
The nanocomposite has a band gap and electron transport properties optimized for solar-driven organic transformations.
The reaction between the BODIPY derivative and TAPP takes place in dimethylformamide (DMF) under an inert atmosphere.
These and other aspects of the embodiments herein will be better appreciated and understood when considered in concurrence with the following explanation and the accompanying drawings. It should be understood, however, that the following descriptions, while indicating preferred embodiments and numerous specific details thereof, are given by way of illustration and not of limitation. Many changes and modifications may be made within the scope of the embodiments herein without departing from the spirit thereof, and the embodiments herein include all such modifications.
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: Diagrammatic representation of (i) natural photosynthesis viewing two light-harvesting systems (PSI and PSII) in the thylakoid and (ii) artificial photosynthesis viewing (NH2)4TPP@BODIPY photocatalyst along with Rh-complex and NAD+ co-factor.
Figure 2: Synthesis of BODIPY {(5,5-difluoro-3,7-bis((E)-4-nitrobenzylidene)-10-(4-nitrophenyl)-5,7-dihydro-3H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine)}
Figure 3: Synthesis of (NH2)4TPP via refluxing (NO2)4TPP
Figure 4: Schematic representation of synthesis of (NH2)4TPP@BODIPY photocatalyst
Figure 3: Synthesis of (NH2)4TPP@BODIPY photocatalyst via condensation mechanism of BODIPY and (NH2)4TPP
Figure 4: NADH regeneration % yield of (NH2)4TPP@BODIPY photocatalyst (66.92%) compared with (NH2)4TPP (6.10%) and BODIPY (7.61%)
Figure 5: Schematic representation of possibilities of NADH isomers formed during regeneration of NADH
Figure 6: Pictorial representation of electronic transmission for NADH regeneration comparing according to potential gradient
Figure 7: Oxidative Photo-catalytic coupling of 4-chloro Benzylamines in acetonitrile as a solvent for 8hrs
Figure 8: (i) UV-visible spectroscopy of (NH2)4TPP@BODIPY photocatalyst, (NH2)4TPP, and BODIPY (ii) Diffuse reflectance spectroscopy (DRS) spectra of (NH2)4TPP@BODIPY photocatalyst (iii) Tauc-plot derived by DRS of (NH2)4TPP@BODIPY photocatalyst (iv) FT-IR spectra of (NH2)4TPP@BODIPY photocatalyst, (NH2)4TPP and BODIPY
Figure 9: X-ray diffraction spectroscopy of (NH2)4TPP@BODIPY photocatalyst, BODIPY and (NH2)4TPP
Figure 10: (i) Scanning electron microscopy of BODIPY, (ii) Scanning electron microscopy of (NH2)4TPP@BODIPY photocatalyst, (iii) EDX of BODIPY and (iv) EDX of (NH2)4TPP@BODIPY photocatalyst
Figure 11: (i) Cyclic voltammetry of (NH2)4TPP@BODIPY photocatalyst and BODIPY (ii) Cyclic voltammetry of (NH2)4TPP@BODIPY photocatalyst compared with Rh-complex and NAD+ (iii) Cyclic voltammetry of Rh-complex and NAD+ (iv) Tafel plot of (NH2)4TPP@BODIPY photocatalyst and BODIPY
Figure 12: (i) Chronopotentiometry of (NH2)4TPP@BODIPY photocatalyst, (NH2)4TPP and BODIPY, (ii) EIS spectra of (NH2)4TPP@BODIPY photocatalyst, (NH2)4TPP and BODIPY
Figure 13: XPS spectra of (a) C1s, (b) N1s, (c) B1s and (d) F1s
The figures depict embodiments of the present subject matter for the purposes of illustration only. A person skilled in the art will easily recognize from the following description that alternative embodiments of the structures and methods illustrated herein may be employed without departing from the principles of the disclosure described herein.
DETAILED DESCRIPTION OF THE INVENTION
In some embodiments of the present invention, BODIPY was synthesized by using 4-nitro benzaldehyde (3eq.) with pyrrole (2eq.) in a mixture of MeOH/H2O (1:4) in the presence of catalytic HCl. After stirring BF3.OEt2 was added for complexation, and a yellow-colored colloidal solution was seen with the naked eye and checked via thin-layer chromatography (TLC).
In some embodiments of the present invention, after stirring overnight dark brown color of colloidal solution was formed. The solution was further workup with chloroform and water to obtain dark brown crystals of BODIPY {5,5-difluoro-3,7-bis((E)-4-nitrobenzylidene)-10-(4-nitrophenyl)-5,7-dihydro-3H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine}.
In some embodiments of the present invention, 500mg of TNPP was dissolved in 20mL concentrated hydrochloric acid along with 2g of SnCl2 in a round bottom flask stirred at room temperature for 2 hours. Further, at 70oC the reaction mixture was refluxed for 1.5 hours.
In some embodiments of the present invention, the reaction was then monitored using TLC. After cooling, the mixture was quenched via ammonia solution. The mixture then filtered and workup with chloroform and water. The resultant dark purple crystals were obtained after crystallization.
Herein enclosed a photocatalyst composite, comprising:
a BODIPY derivative {5,5-difluoro-3,7-bis((E)-4-nitrobenzylidene)-10-(4-nitrophenyl)-5,7-dihydro-3H-4?4,5?4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine}; and
Tetrakis(4-aminophenyl) porphyrin (TAPP);
wherein the two components are combined through poly-condensation to form a nanocomposite.
A method for producing the photocatalyst composite as claimed in claim 1, wherein the method comprising the steps of:
synthesizing the BODIPY derivative by reacting 4-nitrobenzaldehyde and pyrrole in a methanol/water mixture (1:4) catalyzed by hydrochloric acid, followed by complexation with BF3·OEt2;
resulting a yellow-colored colloidal solution, after stirring overnight dark brown color of colloidal solution was formed;
doing workup of solution with chloroform and water to obtain dark brown crystals of BODIPY;
synthesizing TAPP by dissolving 500mg of TNPP in 20mL concentrated hydrochloric acid along with 2g of SnCl2 in a round bottom flask stirred at room temperature for 2 hours;
refluxing at 70oC the reaction mixture for 1.5 hours, and the reaction was then monitored using TLC;
after cooling, the mixture was quenched via ammonia solution, filtered and workup with chloroform and water;
obtaining the resultant dark purple crystals after crystallization;
combining the BODIPY derivative (68.20mg) and TAPP (100mg) dissolved in DMF in a round bottleneck flask in an inert atmosphere;
refluxing the reaction mixture at 150oC for 24hours;
after cooling the reaction mixture at room temperature, 21mL of distilled water was added to the reaction mixture and constant stir for 1hrs;
filtering the reaction mixture and workup was done via warm water and acetone followed by DMF; and
obtaining the dark purple crystal of (NH2)4TPP@BODIPY photocatalyst after crystallization.
The composite is capable of selective aldehyde hydrogenation under solar radiation.
The nanocomposite has a band gap and electron transport properties optimized for solar-driven organic transformations.
The reaction between the BODIPY derivative and TAPP takes place in dimethylformamide (DMF) under an inert atmosphere.
EXAMPLE 1
BEST METHOD
Experimental
Material Required
The chemicals like Benzaldehyde, chloroform, conc. HNO3, ammonia solution, 4 nitro Benzaldehyde, pyrrole, methanol, BF3.OEt2, SnCl2, distilled water, 4-chloro benzylamine, acetonitrile, propionic acid, melamine, DMF, NaOH pellets, acetone, ADH (alcohol dehydrogenase), (Pentamethylcyclopentadienyl)- rhodium (III) Dichloride Dimer, acetonitrile, NAD+ co-factor, ascorbic acid and Mono/di-basic of sodium phosphate were purchased from Sigma Aldrich and used without purification.
Synthesis of BODIPY
BODIPY was synthesized by using 4-nitro benzaldehyde (3eq.) with pyrrole (2eq.) in a mixture of MeOH/H2O (1:4) in the presence of catalytic HCl (Fig. 02). After stirring BF3.OEt2 was added for complexation, and a yellow-colored colloidal solution was seen with the naked eye and checked via thin-layer chromatography (TLC). Therefore, after stirring overnight dark brown color of colloidal solution was formed. The solution was further workup with chloroform and water to obtain dark brown crystals of BODIPY {5,5-difluoro-3,7-bis((E)-4-nitrobenzylidene)-10-(4-nitrophenyl)-5,7-dihydro-3H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine}.[63-64]
Synthesis of 5,10,15,20 tetrakis (4-aminophenyl) porphyrin (TAPP)
Previously monomers were synthesized via reported papers. 500mg of TNPP was dissolved in 20mL concentrated hydrochloric acid along with 2g of SnCl2 in a round bottom flask stirred at room temperature for 2 hours. Further, at 70oC the reaction mixture was refluxed for 1.5 hours (Fig. 03). The reaction was then monitored using TLC. After cooling, the mixture was quenched via ammonia solution. The mixture then filtered and workup with chloroform and water. The resultant dark purple crystals were obtained after crystallization.[34]
Synthesis of (NH2)4TPP@BODIPY photocatalyst
The photocatalyst was synthesized via the reported method [34-40]. 68.20mg of BODIPY and 100mg of TAPP were dissolved in DMF in a round bottleneck flask in an inert atmosphere. The reaction mixture was then refluxed at 150oC for 24hours (Fig. 04-06). After cooling the reaction mixture at room temperature 21mL of distilled water was added to the reaction mixture and constant stir for 1hrs. Filtered the reaction mixture and workup was done via warm water and acetone followed by DMF. The dark purple crystal of (NH2)4TPP@BODIPY photocatalyst was obtained after crystallization. The crystallized photocatalyst was confirmed via nuclear magnetic hydrogen spectroscopy, nuclear magnetic carbon spectroscopy and X-ray photoelectron spectroscopy. Also, the reusability and stability of the synthesized photocatalyst was also confirmed via cyclic experiments and FT-IR. [34,40]
EXAMPLE 2
Synthetic Sunlight Symphony: Unveiling an Artificial Photosynthetic System Inspired by Nature's Own Mastery
In natural photosynthesis [Fig. 01(i)], the organelle involved in photosynthesis in plants is chloroplast which is a type of plastid having a sac-like structure consisting double membrane. This sac-like structure (chloroplast) serves as the site of photosynthesis.[41] In chloroplast, the reduction of CO2 and photo-excitation of NADH are compartmentalized via the thylakoid membrane. However, NADH behaves as a shuttle for the electron transfer to perform symbiotically reduction of CO2 and photo-excitation of NADH.[42] Therefore, in the thylakoid membrane the two photosystems are located (PSI and PSII). Nevertheless, when the radiation of the sun falls on the leaf surface (chloroplast), the photo-excited electron transfer via strongly integrated electron transport chain ferredoxin nicotinamide adenine dinucleotide phosphate reductase (FNR) located at the stroma of the thylakoid membrane. [43-44] Therefore, it converts the photo-excited electron to stable energy i.e. NADH which behaves as an electron and hydride carrier. The NADH further transfers that photo-excited electron to the stroma where the Calvin cycle performs by reducing the CO2.
This compartmentation prevents enzymatic damage and also improves the efficiency of electronic transport. Concerning the natural photosynthesis hypothesis, we constructed an artificial pathway [Fig. 01 (ii)] that mimics the natural process i.e. photocatalysis and biocatalysis.[14] In artificial photosynthesis, the passage of electron transfer between the photocatalyst and Rh-complex is just similar to PSI and PSII. The photocatalyst behaves as an electron donor to the cation form of the Rh-complex which reduces the Rh-complex.[45] The complex [Cp*Rh(bpy)(H2O)]2+ reacts with methanoate anion (HCOO-) to form CO2 by eliminating ß-hydride. Followed by reductive elimination and endo-orientation, NAD+ coordinated by the amide group and subsequently the transfer of hydride results in the formation of regioselective 1,4 NADH. [46-48]
Shining Light on Cellular Energy: A Breakthrough in NADH Photo-Regeneration with Cutting-Edge Photocatalysts
The photo-regeneration of NADH follows the line of action (scheme 4) which consists of NAD+ co-factor, a sacrificial agent (ascorbic acid), an electron mediator (rhodium complex; synthesized by reported method [70]), (NH2)4TPP@BODIPY photocatalyst solution configurated with buffer in a cylindrical glass Pyrex kept at room temperature under LED (artificial light source) having a cut-off filter at 340nm. Before the reaction medium was irradiated with light, firstly it was kept in the dark (absence of light) to achieve absorption-desorption equilibrium. Afterward, the reaction medium was allowed under light, and conversion to NADH from NAD+ was checked via absorbance using UV-visible spectroscopy at regular intervals of time which comes to be 66.92% in 60 minutes therefore, this outcome of regeneration of NADH via (NH2)4TPP@BODIPY photocatalyst shows better and said to be more efficient than both (NH2)4TPP (6.10%) and BODIPY (7.61%) as shown in Fig. 07.[49-50] However, the mechanism behind the regeneration and concentration of NADH with respect to NAD+ co-factor are depicted in ESI.
Twisting Tales in NADH Production: Unveiling the Dance of Conformational Isomers
The production of NADH from NAD+ co-factor results in the formation of different conformational isomers (Fig. 08), unwanted radical coupling, and non-selective protonation due to harsh conditions which are likely to introduced by stepwise reactions at high electrochemical conditions. Especially, the radical form (ii) can further go through two pathways (iii and iv) which leads to the formation of two monomers and dimers. Among various isomers (iva) is only enzymatically active while others are enzymatically inactive. Although, the enzymatically active form should be selectively produced during artificial photosynthesis associated by (NH2)4TPP@BODIPY photocatalyst. [46,50]
Solar Spirits: Harnessing the Sun's Glow to Craft Alcohol from Aromatic and Aliphatic Aldehydes with a Revolutionary Photocatalyst
The photo bio-catalytic alcohol production from its respective aldehyde was accompanied by photo-regeneration of NADH coupled with alcohol dehydrogenase enzyme (ADH) associated by (NH2)4TPP@BODIPY photocatalyst under LED light source. The reaction system was performed by the same protocol of photo-regeneration of NADH consisting of sacrificial agent, electron mediator, NAD+ co-factor, (NH2)4TPP@BODIPY photocatalyst solution configurated with buffer in a cylindrical glass pyrex at room temperature. The suspension was first kept in the dark before the reaction was carried out in light (same as in NADH regeneration protocol) and monitored via UV-visible spectroscopy. In the end, the hydrogenation of aldehydes like formaldehyde and benzaldehyde to respective alcohols like methanol and benzyl alcohol respectively was determined by HPLC, equipped with C18 column. The mobile phase consisted of CH3CN and H2O in a ratio of 55:45 (v/v) with 1mL/min flow rate. The accuracy of the samples was measured by compared with standard samples. [23,51]
Oxidative Coupling of 4-chloro Benzylamine via (NH2)4TPP@BODIPY Photocatalyst into respective imines
In a photocatalytic reaction medium, a 20W cold LED was taken as a light source. The reaction medium consisted of 4-chloro Benzylamine (25mg), (NH2)4TPP@BODIPY photocatalyst (10mg), 10ml of acetonitrile in a vial and irradiated for 8 hours along with stirring (Fig. 09). The organic transformation performed here is in the presence of oxygen (oxidative coupling). The reaction outcomes were monitored by using thin-layered chromatography (TLC). After the completion of the reaction, the photocatalyst was removed via filtration and the crude product was obtained after column chromatography (yield 98%) per reported literature.[39] For mechanism and optimization under different conditions see ESI.
EXAMPLE 3
Characterization
Spectrum Unveiled: Navigating the Invisible with UV-Visible Spectroscopy Insights
The UV-visible spectra of (NH2)4TPP, BODIPY, and (NH2)4TPP@BODIPY photocatalyst have been conducted in DMF [Fig. 10 (i)]. The absorption spectra range of 400-450 nm is allocated to p-p* TAPP moiety. Also, the broader redshift between 480-680nm arises due to intra-molecular charge transfer (ICT) in TAPP. [52-53] The (NH2)4TPP@BODIPY photocatalyst shows the strong Soret band at 410nm which explains the consistent with (NH2)4TPP and BODIPY and hence, concludes the charge transfer between the moieties. BODIPY shows low absorption at 418nm while (NH2)4TPP@BODIPY photocatalyst shows higher absorbance at the same concentration and wavelength range. The UV-visible diffuse reflectance spectrum (DRS) was performed to prove the presence of a porphyrin ring in the (NH2)4TPP@BODIPY photocatalyst. The DRS of (NH2)4TPP@BODIPY photocatalyst shows the soret band at 416nm and Q band between 310-340nm shows incorruption of porphyrin in the BODIPY which is also supported via UV-visible spectrum [Fig. 10(ii)].
Harmonizing Molecular Secrets: A Symphony of Discovery through Fourier Transform Infrared (FT-IR) Spectroscopy Studies
The characteristic structure of (NH2)4TPP@BODIPY photocatalyst which arises due to a poly-condensation reaction between the moieties can be investigated via Fourier transform infrared (FT-IR) spectrum. The FT-IR spectrum of BODIPY, (NH2)4TPP and (NH2)4TPP@BODIPY photocatalyst as shown in figure5(iv). The characteristic band -N=N- stretching was observed at 1703 cm-1 which shows the poly-condensation reaction along with different bands of aromatic rings originating shows successful coupling between the moieties. The covalent linking between the porphyrin and BODIPY monomers shows the reduced in -NH band promoting the coupling of the (-NH2) of TAPP and (-NO2) of BODIPY.[34]
Crystal Clear Insights: Decoding Materials with Powder X-ray Diffraction Spectroscopy (PXRD) Studies
The characteristic PXRD peaks of (NH2)4TPP@BODIPY photocatalyst, BODIPY and (NH2)4TPP have been shown in Fig. 11. The characteristic peak of (NH2)4TPP i.e. 2 ? value equal to 7o is due to the presence of amino group which enhanced the electrostatic interactions in the native porphyrin moiety which is shifted (diffracted) to 7.44o due to the coupling of amino group of porphyrin to the nitro group of BODIPY.[54] Interestingly, the broad peaks at 20o-30o are due to p-p stacking in the amino porphyrin moiety due to the corresponding porphyrin core having perpendicular tetra-pyrrole rings.[55] While, the characteristic peak of BODIPY having a nitro group is at 22.7o (strong) and 19.58o, 23.56o (weak), therefore shifted to 22.1o (strong) and 20.2o, 24.86o (weak). Concurrently, the shifting in the scattering peaks in the XRD pattern of (NH2)4TPP@BODIPY photocatalyst may be attributed to the coupling of amino and nitro group of (NH2)4TPP and BODIPY respectively.
Raman Resonance: Illuminating Molecular Mysteries through Vibrant Spectroscopy Studies
To investigate the structure of the (NH2)4TPP@BODIPY photocatalyst Raman spectroscopy has been performed which shows the bonding of the (NH2)4TPP and BODIPY resulting in the formation of azo linkage (N=N) at G-band at 1593.45cm-1 and D-band at 1546.53cm-1. The two bands found in spectra i.e. G-band and D-band imply the in-plane vibrations of sp2 atoms (tangential mode) and out-plane vibrations due to structural defects respectively (breathing mode).[56] Shift in the Raman spectra show the strong p-electron interaction in the hybrid material implies new compound formation. However, these shifts in the raman spectra also show a huge charge transfer phenomenon between the moieties [14,33].
Beyond the Surface: Exploring Morphological Marvels and Elemental Elegance
The morphology (NH2)4TPP@BODIPY photocatalyst and BODIPY were investigated via scanning electron microscopy (SEM). Due to p-p stacking between the moieties the irregular arrangement and disorderness have been exposed in the samples. According to some literatures, the morphology of the TPP is sphere-like with changes to angle type when coupled to the -NO2 group. Further, this morphology changes to rod-like after reducing to -NH2. This implies that due to the presence of -NH2 (i.e. electron donating group) p to p* and n to p* charge transition has been changed in the background which alters the morphology.[54] The morphology of BODIPY shows a non-uniform and massive arrangement [Fig. 12(i)].[57] However, after the poly-condensation mechanism results in (NH2)4TPP@BODIPY photocatalyst formation the morphology was seen as an aggregate of both somehow rod-like [(NH2)4TPP], massive texture like BODIPY and regular arrangement [Fig. 12(ii)]. Energy-dispersive x-ray spectroscopy (EDX) and elemental mapping has been performed which confirms the presence of nitrogen (N), boron (B), fluorine (F), and oxygen (O) in the BODIPY [Figure 11(iii)] while the presence of nitrogen (N), boron (B), and fluorine (F) in (NH2)4TPP@BODIPY photocatalyst [Figure 12(iv)].
Charged Perspectives: Illuminating Insights from Electrochemical and Photoelectrical Studies
The comprehension of the mechanism of process has been provided by cyclic voltammetry (CV) i.e. Fig. 13 (i&ii) Moreover, the electrochemical studies performed via (NH2)4TPP@BODIPY photocatalyst, Rh and NAD+ with CV using silver-silver chloride (reference), glassy carbon electrode (working) and platinum electrode (counter) in 0.01M TBHF (tetra-butylammonium-hexa- fluorate) solution. The reduction potential of (NH2)4TPP@BODIPY photocatalyst and Rhodium (Rh) are found to be -1.26 and -0.71 respectively. However, the CV voltammogram was observed to be changed when the solution contained both (NH2)4TPP@BODIPY and Rh [5(ii)]. Therefore, this can be attributed to the interaction of the Rh with the photocatalyst. Interestingly, the increase in the reduction potential of (NH2)4TPP@BODIPY photocatalyst-Rh along with NAD+ implies the (NH2)4TPP@BODIPY photocatalyst-Rh is capable to catalyzing the reduction of NAD+ [Fig. 13(ii)][58-59]. The photoelectrical studies revealed the mechanism of electronic and catalytic activity. According to many researchers, the excitation of electron takes place from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) of the hybrid light harvesting moiety (photocatalyst) when irradiated followed by transfer of that excited electron to Rh-complex.[60] In this case, the photo-excitation of an electron from the HOMO (E= -5.80) of (NH2)4TPP@BODIPY photocatalyst to its LUMO (E = -3.24) takes place which further descends into molecular orbital of Rh-complex due to lower potential energy of the Rh-complex (potential gradient). The resultant reduced Rh [Cp*Rh(bpy)] is being capable of further transfer of an electron to NAD+ co-factor which results in its reduction to NADH.[33] However, the band gap calculated via cyclic voltammetry studies comes to be 2.56eV which is suitable for this electronic energy flow pathway to reduce NAD+ into NADH and to perform other photocatalytic conversion. Additionally, the Tafel plot also explains the charge transfer phenomenon of the moiety. The (NH2)4TPP@BODIPY photocatalyst shows a lower tafel plot slope value implying better charge transfer than the BODIPY [Fig. 13(iv)] [61].
Innovative Illumination: Unraveling the Present and Future in Current Studies of a Newly Designed Photocatalyst
The photo generation of charge and its transfer when irradiated to solar light may also be attributed to the photocatalytic property of any moiety. This charge transfer mechanism is surely responsible for NADH regeneration and alcohol production (formed via the reduction of respective aldehyde). Fig. 14(i) shows that the current density of (NH2)4TPP@BODIPY photocatalyst is higher than that of BODIPY which shows comparatively better photocatalytic activities. However, this specified the electrons transferred came from the sacrificial agent (AsA) to the FTO (fluorine-doped tin oxide) glass through photocatalyst when irradiated by solar light. Accordingly, the photocatalyst here behaves as a photoactive moiety which is responsible for photo generation of charges and photocurrent.[33] Moreover, the photocurrent response of the photocatalyst was proven to increase the current density when irradiated and also recovered rapidly in the dark than (NH2)4TPP and BODIPY. Therefore, (NH2)4TPP@BODIPY photocatalyst shows better photocurrent than BODIPY.
Electrochemical impedance (EIS) shows the electrical properties of the photocatalyst. Nyquist EIS plot shows the arc radius of the moiety. The arc radius implies the capability to resist the charge transfer i.e. resistance. The smaller arc radius of the (NH2)4TPP@BODIPY photocatalyst than (NH2)4TPP and BODIPY shows to have a smaller resistance than BODIPY which implicated the high charge transfer ability or low recombination of the photocatalyst [Fig. 14(ii)].[62]
X-ray Photoelectron Spectroscopy (XPS) of (NH2)4TPP@BODIPY photocatalyst
X-ray photoelectron spectroscopy was suggested to appraise the chemical state and elemental composition of the structure of photocatalyst. The XPS spectra of (NH2)4TPP@BODIPY photocatalyst shows peak of C, N, B and F which confirms their presence in the photocatalyst. Fig. 15 (a) shows C1s spectrum having three peaks at 286.7eV, 284.3eV and 284.8eV attributes to C=C, sp2 C-C and C-N respectively. Fig. 15 (b) shows N1s spectrum having five peaks at 397.3eV, 398.8eV, 399.1eV, 399.8eV and 405.6eV attributes to N-B, C-N, N=N, N-H and N-N respectively. Similarly, Fig. 15(c) shows B1s spectrum at 191.45eV and 191.33eV allocated to B-N and B-F respectively. Uniformly, Fig. 15(d) shows spectrum of F1s having F-B peak at 683.98eV. Therefore, these results also demonstrate the bonding of -NO2 of BODIPY and -NH2 of (NH2)4TPP [65-69].
Conclusions
In summary, artificial photosynthesis was found to be an efficient pathway for the regeneration of NADH and hydrogenation of aldehyde in a bio-catalytic cascade. Herein reported (NH2)4TPP@BODIPY photocatalyst formed via poly-condensation mechanism of (NH2)4TPP and BODIPY was found to have a suitable band gap, low recombination, and effective separation of electrons and holes therefore, fulfilling all the demands of having a good photocatalyst. This (NH2)4TPP@BODIPY photocatalyst was characterized via UV-visible, FT-IR, CV, XRD, DRS, Tafel, SEM, 1H-NMR, 13C-NMR, XPS and EDX. This resultant photocatalyst reveals it's superiority over other moiety. The presence of highly efficient solar light harvesting BODIPY may responsible for excellent photocatalytic activity of (NH2)4TPP@BODIPY photocatalyst leading to high NADH regeneration (66.92%), capability of hydrogenation of aldehyde and oxidative coupling of Benzylamine (98%). The innovative molecular biomass transformation driven by solar radiation applies selective hydrogenation reactions in a board range for bio-based platform chemical production.
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[70] R. Shahin, R.K. Yadav, R. K. Verma, C. Singh, S. Singh, R. Singhal, N. K. Gupta, J. O. Baeg, G. A. El-Hiti, K. Yadav, Sein-EY marvels: effortless elegance in crafting flexible film photocatalysts for formic acid production from CO2 and cyclization of thioamides in the air's embrace, New J. Chem., 48, (2024), 12102-12111. https://doi.org/10.1039/D4NJ00531G. ,CLAIMS:1. A photocatalyst composite, comprising:
a BODIPY derivative {5,5-difluoro-3,7-bis((E)-4-nitrobenzylidene)-10-(4-nitrophenyl)-5,7-dihydro-3H-4?4,5?4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine}; and
Tetrakis(4-aminophenyl) porphyrin (TAPP);
wherein the two components are combined through poly-condensation to form a nanocomposite.
2. A method for producing the photocatalyst composite as claimed in claim 1, wherein the method comprising the steps of:
a) synthesizing the BODIPY derivative by reacting 4-nitrobenzaldehyde and pyrrole in a methanol/water mixture (1:4) catalyzed by hydrochloric acid, followed by complexation with BF3·OEt2;
b) resulting a yellow-colored colloidal solution, after stirring overnight dark brown color of colloidal solution was formed;
c) doing workup of solution with chloroform and water to obtain dark brown crystals of BODIPY;
d) synthesizing TAPP by dissolving 500mg of TNPP in 20mL concentrated hydrochloric acid along with 2g of SnCl2 in a round bottom flask stirred at room temperature for 2 hours;
e) refluxing at 70oC the reaction mixture for 1.5 hours, and the reaction was then monitored using TLC;
f) after cooling, the mixture was quenched via ammonia solution, filtered and workup with chloroform and water;
g) obtaining the resultant dark purple crystals after crystallization;
h) combining the BODIPY derivative (68.20mg) and TAPP (100mg) dissolved in DMF in a round bottleneck flask in an inert atmosphere;
i) refluxing the reaction mixture at 150oC for 24hours;
j) after cooling the reaction mixture at room temperature, 21mL of distilled water was added to the reaction mixture and constant stir for 1hrs;
k) filtering the reaction mixture and workup was done via warm water and acetone followed by DMF; and
l) obtaining the dark purple crystal of (NH2)4TPP@BODIPY photocatalyst after crystallization.
3. The method as claimed in claim 2, wherein the composite is capable of selective aldehyde hydrogenation under solar radiation.
4. The method as claimed in claim 2, wherein the nanocomposite has a band gap and electron transport properties optimized for solar-driven organic transformations.
5. The method as claimed in claim 2, wherein the reaction between the BODIPY derivative and TAPP takes place in dimethylformamide (DMF) under an inert atmosphere.

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