Transforming Pharmaceutical Synthesis with Sein-E-B Nanocomposite Photocatalyst through 1,4-NAD(P)H Cofactor Regeneration and C-N Bond Activation.

The need for sunlight chemical renewal and contemporary organic transformation has fostered the advancement of environmentally friendly photocatalytic techniques. For the first time, we report on the novel crafting of a bright future with selenium-infused Eosin-B (Sein-E-B) nanocomposite photocatalysts in this work. The Sein-E-B nanocomposite materials were created using a hydrothermal process for solar chemical regeneration and organic transformation under visible light. The synthesized samples were subjected to UV-DRS-visible spectroscopy, FT-IR, SEM, EDX, EIS and XRD analysis. The energy band gap of the Sein-E-B nanocomposite photocatalyst was measured using UV-DRS, and the result was around 2.06 eV. to investigate the generated Sein-E-B catalytic activity as a nanocomposite for 1,4-NADH/NADPH re-formation and C-N bond activation. This novel photocatalyst offers a promising alternative for the regeneration of solar chemicals and C-N bond creation between pyrrole and aryl halides.

Nature-inspired polymer photocatalysts for green NADH regeneration and nitroarene transformation.

Photocatalysis has emerged as a promising approach for generating solar chemical and organic transformations under the solar light spectrum, employing polymer photocatalysts. In this study, our aim is to achieve the regeneration of NADH and fixation of nitroarene compounds, which hold significant importance in various fields such as pharmaceuticals, biology, and chemistry. The development of an in-situ nature-inspired artificial photosynthetic pathway represents a challenging task, as it involves harnessing solar energy for efficient solar chemical production and organic transformation. In this work, we have successfully synthesized a novel artificial photosynthetic polymer, named TFc photocatalyst, through the Friedel-Crafts alkylation reaction between triptycene (T) and a ferrocene motif (Fc). The TFC photocatalyst is a promising material with excellent optical properties, an appropriate band gap, and the ability to facilitate the regeneration of NADH and the fixation of nitroarene compounds through photocatalysis. These characteristics are necessary for several applications, including organic synthesis and environmental remediation. Our research provides a significant step forward in establishing a reliable pathway for the regeneration and fixation of solar chemicals and organic compounds under the solar light spectrum.

Aloe vera-derived graphene-coupled phenosafranin photocatalyst for generation and regeneration of ammonia and NADH by mimicking natural photosynthetic route.

Aloe vera-derived graphene (ADG) coupled system photocatalyst, mimicking natural photosynthesis, is one of the most promising ways for converting solar energy into ammonia (NH3 ) and nicotinamide adenine dinucleotide (NADH) that have been widely used to make the numerous chemicals such as fertilizer and fuel. In this study, we report the synthesis of the aloe vera-derived graphene-coupled phenosafranin (ADGCP) acting as a highly efficient photocatalyst for the generation of NH3 and regeneration of NADH from nitrogen (N2 ) and oxidized form of nicotinamide adenine dinucleotide (NAD+ ). The results show a benchmark instance for mimicking natural photosynthesis activity as well as the practical applications for the solar-driven selective formation of NH3 and the regeneration of NADH by using the newly designed photocatalyst.

Photocatalytic fixation and oxygenation of NAD+ /NADP+ and sulfides using solar light: Exploring mechanistic investigations and their impact on synthetic applications.

Sulfur-doped Eosin-B (SDE-B) photocatalysts were synthesized for the first time utilizing sublimed sulfur (S8 ) as a dopant in an in situ thermal copolymerization technique. Sulfur doping not only increased Eosin-B (E-B) absorption range for solar radiation but also improved fixation and oxygenation capabilities. The doped sulfur bridges the S-S bond by substituting for the edge bromine of the E-B bond. The improved photocatalytic activity of SDE-B in the fixation and oxygenation of NAD+ /NADP+ and sulfides using solar light is attributed to the photo-induced hole of SDE-B's high fixation and oxygenation capacity, as well as an efficient suppression of electron and hole recombination. The powerful light-harvesting bridge system created using SDE-B as a photocatalyst works extremely well, resulting in high NADH/NADPH regeneration (79.58/76.36%) and good sulfoxide yields (98.9%) under solar light. This study focuses on the creation and implementation of a sulfur-doped photocatalyst for direct fine chemical regeneration and organic transformation.

Revolutionizing carbon chemistry: Solar-powered C(sp3 )-N bond activation and CO2 transformation via newly designed SBE-Y cutting-edge dynamic photocatalyst.

A solvent-free sulfur-bridge-eosin-Y (SBE-Y) polymeric framework photocatalyst was prepared for the first time through an in situ thermal polymerization route using elemental sulfur (S8 ) as a bridge. The addition of a sulfur bridge to the polymeric framework structure resulted in an allowance of the harvesting range of eosin-Y (E-Y) for solar light. This shows that a wider range of solar light can be used by the bridge material's photocatalytic reactions. In this context, supercharged solar spectrum: enhancing light absorption and hole oxidation with sulfur bridges. This suggests that the excited electrons and holes through solar light can contribute to oxidation-reduction reactions more potently. As a result, the photocatalyst-enzyme attached artificial photosynthesis system developed using SBE-Y as a photocatalyst performs exceptionally well, resulting in high 1,4-NADH regeneration (86.81%), followed by its utilization in the exclusive production of formic acid (210.01 µmol) from CO2 and synthesis of fine chemicals with 99.9% conversion yields. The creation of more effective photocatalytic materials for environmental clean-up and other applications that depend on the solar light-driven absorption spectrum of inorganic and organic molecules could be one of the practical ramifications of this research.

Photocatalytic oxygenation of sulfide using solar light and ingenious GQDs@AQ catalyst: Mechanistic and synthetic investigations.

The combination of excellent electronic properties and thermal stability positions orange-derived graphene quantum dots (GQDs) as promising materials for solar light-based applications. Researchers are actively exploring their potential in fields such as photovoltaics, photocatalysis, optoelectronics, and energy storage. Their abundance, cost-effectiveness, and eco-friendly nature further contribute to their growing relevance in cutting-edge scientific research. Furthermore, only GQDs are not much more effective in the UV-visible region, therefore, required band gap engineering in GQDs material. In this context, we designed GQDs-based light harvesting materials, which is active in UV-visible region. Herein we synthesized GQDs coupled with 2,6-diaminoanthrquninone (AQ), that is, GQDs@AQ light harvesting photocatalyst the first time for the oxidation of sulfide to sulfoxide under visible light. For the integrating reactions of sulfide in aerobic conditions under visible light by GQDs@AQ photocatalyst exhibit utmost higher photocatalytic activity than simple GQDs due to low molar extinction coefficient and slow recombination charges. The use of GQDs@AQ light harvesting photocatalyst, showed the excellent organic transformation efficiency of sulfide to sulfoxide with excellent yield (94%). The high efficiency and excellent yield of 94% indicate the effectiveness of GQDs@AQ as a photocatalyst for these specific organic transformations.

Selective aerobic coupling of amines to imines using solar spectrum-responsive flower-like Nen-graphene quantum dots (GQDs) decorated with 2, 4-dinitrophenylhydrazine (PH) as a photocatalyst.

Indeed, the development of ecologically benign molecular fabrication methods for highly efficient graphene quantum dots-based photocatalysts is of great significant. Graphene quantum dots-based photocatalysts have promising applications in various field, including environmental remediation, energy conversion, and splitting of water. However, ensuring resource reusability and minimizing the environmental impact are crucial considerations in the development. From this perspective, attention has also been paid to the creation of easy to make solar light harvesting graphene quantum dots-based photocatalysts for synthesising pharmaceuticals and functional imines compounds. Imines are excellent significant building blocks in pharmaceutical chemistry and excellent examples of these valuable compounds' synthetic intermediates, and the environmentally friendly oxidative synthesis of imines from amines. Therefore, herein, we designed a facile and efficient condensation route to synthesize the Nen-GQDs@PH photocatalyst. This route involves coupling of 2,4-dinitrophenylhydrazine (PH) with nitrogen-enriched graphene quantum dots (Nen-GQDs). The Nen-GQDs@PH as photocatalyst functions in a highly selective and efficient manner, leading to high amines conversion efficiency to imines (95%). Our results highlight a novel and environmentally safe approach for generating highly selective imines from various types of amines, setting a new benchmark in the current research field.

Greener One-step Synthesis of Novel In Situ Selenium-doped Framework Photocatalyst by Melem and Perylene Dianhydride for Enhanced Solar Fuel Production from CO2.

To minimize the ever-increasing global warming and environmental problems, the conversion of atmospheric CO2 into value-added solar chemicals/fuels is one of the most challenging tasks. As a means to accomplish this, herein we have synthesized first time novel in situ selenium-doped polyimide frameworks (Se-PIFs) photocatalyst via thermal co-polymerization approach between melem (M) and perylene 3, 4, 9, 10-tetracarboxylic dianhydride (PTDA) along with selenium (Se) as a dopant. The Se-PIFs photocatalyst shows outstanding photocatalytic stability and activity for high solar fuel production (HCOOH ~ formic acid) from CO2 . The solar light active Se-PIFs photocatalyst was demonstrating the ~ 10-fold higher photo-conversion of CO2 to formic acid with yields of 250. 6 µmol. The current work is providing a facile and scalable avenue as well as sheds light on creating a new route for in situ judicious design highly efficient Se-PIFs photocatalyst. The outcome is a benchmark instance for the use of selenium-doped polyimide frameworks as a highly practical and efficient solar light active photocatalyst for carrying out the selective production of formic acid from environmental CO2 .

Secondary Coordination Effect on Monobipyridyl Ru(II) Catalysts in Photochemical CO2 Reduction: Effective Proton Shuttle of Pendant Brønsted Acid/Base Sites (OH and N(CH3)2) and Its Mechanistic Investigation.

While the incorporation of pendant Brønsted acid/base sites in the secondary coordination sphere is a promising and effective strategy to increase the catalytic performance and product selectivity in organometallic catalysis for CO2 reduction, the control of product selectivity still faces a great challenge. Herein, we report two new trans(Cl)-[Ru(6-X-bpy)(CO)2Cl2] complexes functionalized with a saturated ethylene-linked functional group (bpy = 2,2'-bipyridine; X = -(CH2)2-OH or -(CH2)2-N(CH3)2) at the ortho(6)-position of bpy ligand, which are named Ru-bpyOH and Ru-bpydiMeN, respectively. In the series of photolysis experiments, compared to nontethered case, the asymmetric attachment of tethering ligand to the bpy ligand led to less efficient but more selective formate production with inactivation of CO2-to-CO conversion route during photoreaction. From a series of in situ FTIR analyses, it was found that the Ru-formate intermediates are stabilized by a highly probable hydrogen bonding between pendent proton donors (-diMeN+H or -OH) and the oxygen atom of metal-bound formate (RuI-OCHO···H-E-(CH2)2-, E = O or diMeN+). Under such conformation, the liberation of formate from the stabilized RuI-formate becomes less efficient compared to the nontethered case, consequently lowering the CO2-to-formate conversion activities during photoreaction. At the same time, such stabilization of Ru-formate species prevents the dehydration reaction route (η1-OCHO → η1-COOH on Ru metal) which leads toward the generation of Ru-CO species (key intermediate for CO production), eventually leading to the reduction of CO2-to-CO conversion activity.

Band Gap Engineering in Solvochromic 2D Covalent Organic Framework Photocatalysts for Visible Light-Driven Enhanced Solar Fuel Production from Carbon Dioxide.

Solar light-driven fuel production from carbon dioxide using organic photocatalysts is a promising technique for sustainable energy sources. Band gap engineering in sustainable organic photocatalysts for improving efficiency and fulfilling the requirements is highly anticipated. Here, we present a new strategy to engineer the band gap in covalent organic framework (COF) photocatalysts by varying the push-pull electronic effect. To implement this strategy, we have designed and synthesized four different COFs using a tripodal amine 4,4',4″-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-4-amine)) [Ttba] with 1,3,5-triformylbenzene (COF-1), 2,4,6-triformylphloroglucinol (COF-2), 2,4,6-triformylphenol (COF-3), and 2,4,6-triformylresorcinol (COF-4). On varying the number of hydroxyl units in the aldehyde precursor, the resulting COFs allow the fine-tuning of their band gap and band edge positions and result in different morphologies with varying surface areas. The enhanced optical properties of COF-3 and COF-4 with very suitable band gaps of 2.02 and 1.95 eV, respectively, enable them to demonstrate a high-efficiency photobiocatalytic system for NADH photoregeneration and enhanced visible light-driven formic acid production at a rate of 226.3 µmol g-1 in 90 min. The triazine core enables efficient charge separation, while the hydroxyl groups induce an electronic push-pull effect, regulating their photocatalytic efficiency. The results demonstrated the morphology-guided enhanced surface area and dual keto-enol tautomerism-induced push-pull effect in asymmetrical charge distribution as key features in the fine-tuning of the photocatalysts.

Rapid Exciton Migration and Amplified Funneling Effects of Multi-Porphyrin Arrays in a Re(I)/Porphyrinic MOF Hybrid for Photocatalytic CO2 Reduction.

A porphyrinic metal-organic framework (PMOF) known as PCN-222(Zn) was chemically doped with a molecular Re(I) catalyst-bearing carboxylate anchoring group to form a new type of metal-organic framework (MOF)-Re(I) hybrid photocatalyst. The porphyrinic MOF-sensitized hybrid (PMOF/Re) was prepared with an archetypical CO2 reduction catalyst, (L)ReI(CO)3Cl (Re(I); L = 4,4'-dicarboxylic-2,2'-bipyridine), in the presence of 3 vol % water produced CO with no leveling-off tendency for 59 h to give a turnover number of ≥1893 [1070 ± 80 µmol h-1 (g MOF)-1]. The high catalytic activity arises mainly from efficient exciton migration and funneling from photoexcited porphyrin linkers to the peripheral Re(I) catalytic sites, which is in accordance with the observed fast exciton (energy) migration (≈1 ps) in highly ordered porphyrin photoreceptors and the effective funneling into Re(I) catalytic centers in the Re(I)-doped PMOF sample. Enhanced catalytic performance is convincingly supported by serial photophysical measurements including decisive Stern-Volmer interpretation.

Visible-Light Photocatalytic Conversion of Carbon Dioxide by Ni(II) Complexes with N4S2 Coordination: Highly Efficient and Selective Production of Formate.

The efficient and selective light-driven conversion of carbon dioxide to formate is a scientific challenge for green chemistry and energy science, especially utilizing visible-light energy and earth-abundant catalytic materials. In this report, two mononuclear Ni(II) complexes of pyridylbenzimidazole (pbi) and pyridylbenzothiazole (pbt), such as Ni(pbt)(pyS)2 (1) and Ni(pbi)(pyS)2 (2) (pyS = pyridine-2-thiolate), were prepared and their reactivities studied. The two Ni complexes were examined for CO2 conversion using eosin Y as a photosensitizer upon visible-light irradiation in a H2O/ethanol solvent. The photoreaction of CO2 catalyzed by complexes 1 and 2 selectively affords formate with a high efficiency (14 000 turnover number) and a high catalytic selectivity of ∼99%. Undesirable proton reduction pathways were completely suppressed in the photocatalytic reactions with these sulfur-rich Ni catalysts under CO2. Hydrogen photoproduction was also studied under argon. Their kinetic isotope effects and influence of solution pH for formate and H2 production in the photocatalytic reactions are described in relation to the reaction mechanisms. These bioinspired Ni(II) catalysts with N/S ligation in relation to [NiFe]-hydrogenases are the first examples of early transition metal complexes affording such high selectivity and efficiencies, providing a future path to design solar-to-fuel processes for artificial photosynthesis.

Ultrafast charge transfer coupled with lattice phonons in two-dimensional covalent organic frameworks.

Covalent organic frameworks (COFs) have emerged as a promising light-harvesting module for artificial photosynthesis and photovoltaics. For efficient generation of free charge carriers, the donor-acceptor (D-A) conjugation has been adopted for two-dimensional (2D) COFs recently. In the 2D D-A COFs, photoexcitation would generate a polaron pair, which is a precursor to free charge carriers and has lower binding energy than an exciton. Although the character of the primary excitation species is a key factor in determining optoelectronic properties of a material, excited-state dynamics leading to the creation of a polaron pair have not been investigated yet. Here, we investigate the dynamics of photogenerated charge carriers in 2D D-A COFs by combining femtosecond optical spectroscopy and non-adiabatic molecular dynamics simulation. From this investigation, we elucidate that the polaron pair is formed through ultrafast intra-layer hole transfer coupled with coherent vibrations of the 2D lattice, suggesting a mechanism of phonon-assisted charge transfer.

Highly Improved Solar Energy Harvesting for Fuel Production from CO2 by a Newly Designed Graphene Film Photocatalyst.

Our growing energy demands must be met by a sustainable supply with reduced carbon intensity. One of the most exciting prospects to realize this goal is the photocatalyst-biocatalyst integrated artificial photosynthesis system which affords solar fuel/chemicals in high selectivity from CO2. Graphene based photocatalysts are highly suitable for the system, but their industrial scale use requires immobilization for improved separation and recovery of the photocatalyst. Therefore for practical purposes, design and fabrication of film type graphene photocatalyst with higher solar energy conversion efficiency is an absolute necessity. As a means to achieve this, we report herein the successful development of a new type of flexible graphene film photocatalyst that leads to >225% rise in visible light harvesting efficiency of the resultant photocatalyst-biocatalyst integrated artificial photosynthesis system for highly selective solar fuel production from CO2 compared to conventional spin coated graphene film photocatalyst. It is an important step towards the design of a new pool of graphene film based photocatalysts for artificial photosynthesis of solar fuels from CO2.

Electron delocalization and charge mobility as a function of reduction in a metal-organic framework.

Conductive metal-organic frameworks are an emerging class of three-dimensional architectures with degrees of modularity, synthetic flexibility and structural predictability that are unprecedented in other porous materials. However, engendering long-range charge delocalization and establishing synthetic strategies that are broadly applicable to the diverse range of structures encountered for this class of materials remain challenging. Here, we report the synthesis of K x Fe2(BDP)3 (0 ≤ x ≤ 2; BDP2- = 1,4-benzenedipyrazolate), which exhibits full charge delocalization within the parent framework and charge mobilities comparable to technologically relevant polymers and ceramics. Through a battery of spectroscopic methods, computational techniques and single-microcrystal field-effect transistor measurements, we demonstrate that fractional reduction of Fe2(BDP)3 results in a metal-organic framework that displays a nearly 10,000-fold enhancement in conductivity along a single crystallographic axis. The attainment of such properties in a K x Fe2(BDP)3 field-effect transistor represents the realization of a general synthetic strategy for the creation of new porous conductor-based devices.

Template Free Architecture of Hierarchical Nanostructured ZnIn2S4 Rose-Like Flowers for Solar Hydrogen Production.

We have demonstrated the controlled synthesis of hierarchical nanostructured ZnIn2S4 using a facile template free hydrothermal/solvothermal method. The effect of solvents on the morphology and microstructure of ZnIn2S4 has been studied by using water, methanol and ethylene glycol as a solvents. The hierarchical nanostructure, i.e., rose-like morphology composed of very thin (5­6 nm) nanoplates of length ˜1 µm which was obtained in aqueous mediated ZnIn2S4. The porous structure (distorted flowers) and agglomerated nanoparticles were obtained using methanol-and ethylene glycol-mediated ZnIn2S4. Considering the band gap in the visible region, ZnIn2S4 is used as a solar light driven photocatalyst. An ecofriendly photocatalytic process for the conversion of poisonous H2S into H2 which is a green unconventional energy source has been demonstrated. The nanostructured ZnIn2S4 is employed as a photocatalyst for hydrogen production from H2S via a solar light-driven eco-friendly approach. The stable photocatalytic activity of hydrogen evolution, i.e., 3964 µmol ⁻¹ was obtained using 0.5 gm of such hierarchical nanostructured ZnIn2S4 under visible light irradiation. The unique hierarchical nanostructured ZnIn2S4 ternary semiconductor having hexagonal layer is expected to have potential applications in solar cells, LEDs, charge storage, electrochemical recording, thermoelectricity, other prospective electronic and optical devices.

Highly selective solar-driven methanol from CO2 by a photocatalyst/biocatalyst integrated system.

The successful development of a photocatalyst/biocatalyst integrated system that carries out selective methanol production from CO2 is reported herein. The fine-tuned system was derived from a judicious combination of graphene-based visible light active photocatalyst (CCG-IP) and sequentially coupled enzymes. The covalent attachment of isatin-porphyrin (IP) chromophore to chemically converted graphene (CCG) afforded newly developed CCG-IP photocatalyst for this research endeavor. The current work represents a new benchmark for carrying out highly selective methanol formation from CO2 in an environmentally benign manner.

Quantum confinement controlled solar hydrogen production from hydrogen sulfide using a highly stable CdS(0.5)Se(0.5)/CdSe quantum dot-glass nanosystem.

We have demonstrated unique CdS0.5Se0.5 and CdSe quantum dot-glass nanosystems with quantum confinement effect. The stable, monodispersed CdS0.5Se0.5 and CdSe quantum dots (QDs) of size 2 to 12 nm have been grown in a germanate glass matrix by a simple melt quench technique at moderate temperature. XRD and Raman studies show formation of hexagonal CdS0.5Se0.5 and CdSe in the glass matrix. The quantum confinement of CdS0.5Se0.5 and CdSe was studied using TEM and UV-Vis spectroscopy. The band gap of the glass nanosystem was tuned from 3.6 to 1.8 eV by controlling the CdS0.5Se0.5 quantum dot size in the glass matrix. It can be further tuned to 1.68 eV using growth of CdSe quantum dots in the glass matrix. Considering the tuneable band gap of the CdS0.5Se0.5 and CdSe quantum dot-glass nanosystem for the visible light absorption, a study of size tuneable photocatalytic activity for hydrogen generation from hydrogen sulfide splitting was performed under visible light irradiation for the first time. The utmost hydrogen evolution, i.e. 8164.53 and 7257.36 µmol h(-1) g(-1) was obtained for the CdS0.5Se0.5 and CdSe quantum dot-glass nanosystems, respectively. The apparent quantum yield (AQY) was observed to be 26% and 21% for the CdS0.5Se0.5 and CdSe quantum dot-glass nanosystems, respectively. It is noteworthy that the present glass nanosystem as a photocatalyst was found to be very stable as compared to naked powder photocatalysts.

A photocatalyst-enzyme coupled artificial photosynthesis system for solar energy in production of formic acid from CO2.

The photocatalyst-enzyme coupled system for artificial photosynthesis process is one of the most promising methods of solar energy conversion for the synthesis of organic chemicals or fuel. Here we report the synthesis of a novel graphene-based visible light active photocatalyst which covalently bonded the chromophore, such as multianthraquinone substituted porphyrin with the chemically converted graphene as a photocatalyst of the artificial photosynthesis system for an efficient photosynthetic production of formic acid from CO(2). The results not only show a benchmark example of the graphene-based material used as a photocatalyst in general artificial photosynthesis but also the benchmark example of the selective production system of solar chemicals/solar fuel directly from CO(2).