Molecular surface-dependent light harvesting and photo charge separation in plant-derived carbon quantum dots for visible-light-driven OH radical generation for remediation of aromatic hydrocarbon pollutants and real wastewater.

Despite the growing emphasis on eco-friendly nanomaterials as energy harvesters, scientists are actively searching for metal-free photocatalysts to be used in environmental remediation strategies. Developing renewable resource-based carbon quantum dots (CQDs) as the sole photocatalyst to harvest visible light for efficient pollutant degradation is crucial yet challenging, particularly for addressing the escalating issue of water deterioration. Moreover, the photocatalytic decomposition of H2O2 under visible light irradiation remains an arduous task. Based on this, we designed two types of CQDs, C-CQDs (carboxylic-rich) and A-CQDs (amine-rich) with distinct molecular surfaces. Owing to the higher amount of upward band bending induced by amine-rich molecular surface, A-CQDs efficiently harvest the visible light and prevent recombination kinetics resulting in prolonged lifetimes (25 ps), and augmented charge carrier density (35.7 × 1018) of photoexcited charge carriers. A-CQDs enabled rapid visible-light-driven photolysis of H2O2 (k = 0.058 min-1) and produced higher quantity of •OH radicals (0.158 µmol/sec) for the mineralization of petroleum waste, BETX (i.e. Benzene, Ethylbenzene, Toluene and Xylene) (k = 0.017-0.026 min-1) and real textile wastewater (k = 0.026 min-1). To assess comparative toxicities of both remediated and non-remediated real wastewater samples in a time and dose depended manner, Drosophila melanogaster was used as a model organism. The findings unequivocally demonstrate the potential of remediated wastewater for watering urban forestry.

Unlocking the Molecular Behavior of Natural Amine-Targeted Carbon Quantum Dots for the Synthesis of Diverse Pharmacophore Scaffolds via an Unusual Nanoaminocatalytic Route.

Despite the fact that carbon quantum dots (CQDs) have significant catalytic potential, only emblematic applications that rely on simple acid-base or hydrogen-bonding activation pathways have been reported. In this study, natural amine-targeted CQDs (NAT-CQDs) have been successfully fabricated using a sustainable technique that harnesses a renewable green source. Based on a holistic sustainable assessment, the present approach for the synthesis of NAT-CQDs surpasses previously reported methods in terms of estimated circular and good-manufacturing-practice metrics. A set of spectroscopic and analytical techniques, including FTIR, XPS, conductometric assay, pH titration, 19FNMR, and 13CNMR confirms the presence of the assessable amino-rich groups (0.0083N) at the surface of NAT-CQDs. The occurrence of surface amine groups unlocked the molecular behavior of as-prepared NAT-CQDs and makes them an unprecedented nanoaminocatalytic platform for the synthesis of diverse pharmacophore scaffolds (>40 examples) via a one-pot Knoevenagel/(aza) Michael addition reaction in water at room temperature. The assessable amine group can covalently activate carbonyl groups through nucleophilic iminium activation modes in water and facilitate the ability to build valuable and therapeutic scaffolds on a gram scale. By transferring significant molecular primacy at the frontier of nanoscale materials, NAT-CQDs can thus bridge the gap between the nanoscale and molecular domains. This protocol can also be applied for the preparation of therapeutic anticoagulant drugs, warfarin, and coumachlor. All the reactions exhibited a high atom economy, low E-factor, low process mass intensity (PMI), high reaction mass efficiency (RME), high carbon efficiency (CE), and high catalyst reusability with overall high sustainable values. NAT-CQDs show high recyclability, and the spectral data of reused catalysts indicate that the NAT-CQDs maintained their surface chemistry and electronic properties, suggesting their stability under the tested conditions. This study presents a remarkable instance of NAT-CQDs showcasing covalent catalysis. Expanding on the aforementioned design concept, the utilization of NAT-CQDs' "potential" as distinct colloidal organocatalysts in aqueous environments at the molecular level introduces valuable prospects for aminocatalytic pathways.

Dopant-driven recombination delay and ROS enhancement in nanoporous Cd1-xCuxS heterogeneous photocatalyst for the degradation of DR-23 dye under visible light irradiation.

Developing an efficient heterogeneous photocatalyst for environmental remediation and treatment strategies using visible light harvesting processes is promising but challenging. Herein, Cd1-xCuxS materials have been synthesized and characterized by precise analytical tools. Cd1-xCuxS materials exhibited excellent photocatalytic activity for direct Red 23 (DR-23) dye degradation in visible light irradiation. The operational parameters, like dopant concentration, photocatalyst dose, pH, and initial concentration of dye were investigated during the process. The photocatalytic degradation process follows pseudo-first-order kinetics. As compared to other tested materials, 5% Cu doped CdS material revealed superior photocatalytic performance for the degradation of DR-23 (k = 13.96 × 10-3 min-1). Transient absorption spectroscopy, EIS, PL, and transient photocurrent indicated that adding copper to the CdS matrix improved the separation of photo-generated charge carriers by lowering the recombination rate. Spin-trapping experiments recognized the photodegradation primarily based on secondary redox products, i.e., hydroxyl and superoxide radicals. According to by Mott-Schottky curves, photocatalytic mechanism and photo-generated charge carrier density were elucidated regarding dopant-induced valence and conduction bands shifting. Thermodynamic probability of radical formation in line with the altered redox potentials by Cu doping has been discussed in the mechanism. The identification of intermediates by mass spectrometry study also showed a plausible breakdown mechanism for DR-23. Moreover, samples treated with nanophotocatalyst displayed excellent results when tested for water quality metrics such as DO, TDS, BOD, and COD. Developed nanophotocatalyst shows high recyclability with superior heterogeneous nature. 5% Cu-doped CdS also exhibit strong photocatalytic activity for the degradation of colourless pollutant bisphenol A (BPA) under visible light (k = 8.45 × 10-3 min-1). The results of this study offer exciting opportunities to alter semiconductors' electronic band structures for visible-light-induced photocatalytic activity for wastewater treatment.

Surface functionalized silver-doped ZnO nanocatalyst: a sustainable cooperative catalytic, photocatalytic and antibacterial platform for waste treatment.

The different dyes used and discharged in industrial settings and microbial pathogenic issues have raised serious concerns about the content of bodies of water and the impact that dyes and microbes have on the environment and human health. Efficient treatment of contaminated water is thus a major challenge that is of great interest to researchers around the world. In the present work, we have fabricated functionalized silver-doped ZnO nanoparticles (Ag-doped ZnO NPs) via a hydrothermal method for wastewater treatment. X-ray photoelectron spectroscopy analysis confirmed the doping of Ag with ZnO NPs, and X-ray diffractometry analysis showed a decreasing trend in the crystallite size of the synthesized ZnO NPs with increased Ag concentration. Field emission scanning electron microscopy study of pure ZnO NPs and Ag-doped ZnO NPs revealed nanocrystal aggregates with mixed morphologies, such as hexagonal and rod-shaped structures. Distribution of Ag on the ZnO lattice is confirmed by high-resolution transmission electron microscopy analysis. ZnO NPs with 4 wt% Ag doping showed a maximum degradation of ∼95% in 1.5 h of malachite green dye (80 mg L-1) under visible light and ∼85% in 4 h under dark conditions. Up to five successive treatment cycles using the 4 wt% Ag-doped ZnO NP nanocatalyst confirmed its reusability, as it was still capable of degrading ∼86% and 82% of the dye under visible light and dark conditions, respectively. This limits the risk of nanotoxicity and aids the cost-effectiveness of the overall treatment process. The synthesized NPs showed antibacterial activity in a dose-dependent manner. The zone of inhibition of the Ag-doped ZnO NPs was higher than that of the pure ZnO NPs for all doping content. The studied Ag-doped ZnO NPs thus offer a significant eco-friendly route for the effective treatment of water contaminated with synthetic dyes and fecal bacterial load.

Photosensitized Radical-Anion-Driven Metal-Free Selective Reduction of Aldehydes Using Graphene Oxide as an Electron Relay Mediator under Visible Light.

Despite the modern boost, developing a new photocatalytic system for the reduction of aldehydes is still challenging due to their high negative reduction potential. Herein, we have used a metal-free photoinduced electron-transfer system based on a cheap and readily available organic dye eosin Y (EY), graphene oxide (GO), and ammonium oxalate (AO) for photocatalytic reduction of structurally diverse aldehydes under sustainable conditions. The protocol shows remarkable selectivity for the photocatalytic reduction of aldehydes over ketones. The decisive interaction of GO and AO with the various states of EY (ground, singlet, triplet, and radical anions), which are responsible for the commencement of the reaction, was examined by various theoretical, optical, electrochemical, and photo-electrochemical studies. The synergetic system of GO, EY, and AO is appropriate for enhancing the separation efficiency of visible-light-induced charge carriers. GO nanosheets act as an electron reservoir to accept and transport photogenerated electrons from the photocatalytic system to the reactant. The reduction of the GO during the process ruled out the back transfer of photoexcited charges. Control experiments explained that the reaction involves two stages: electron transfer and protonation. This process eliminates the necessity of precious-metal-based photocatalysts or detrimental sacrificial agents and overcomes the redox potential limitations for the photoreduction of aldehydes.

Sustainable synthesis of biomass-derived carbon quantum dots and their catalytic application for the assessment of α,ß-unsaturated compounds.

Herein, we demonstrate a simple, reproducible, and environment-friendly strategy for the synthesis of carbon quantum dots (CQDs) utilizing the mango (Mangifera indica) kernel as a renewable green carbon source. Various analytical tools characterized the as-prepared CQDs. These fluorescent CQDs showed significant water solubility with a uniform size of about 6 nm. The as-synthesized CQDs show significantly enhanced catalytic activity for the production of α,ß-unsaturated compounds from the derivatives of aromatic alkynes and aldehydes under microwave irradiation in aqueous media. A potential mechanistic pathway and role of carboxylic functionalities were also revealed via various control experiments. The protocol shows outstanding selectivity towards the assessment of α,ß-unsaturated compounds over other possible products. A comparative evaluation suggested the as-synthesized CQDs show higher catalytic activity under microwave radiation as compared to the conventional ways. These recyclable CQDs represent a sustainable alternative to metals in synthetic organic chemistry. A cleaner reaction profile, low catalyst loading, economic viability and recyclability of the catalyst, atom economy, and comprehensive substrate applicability are additional benefits of the current protocol according to green chemistry.

Site-specific role of bifunctional graphitic carbon nitride catalyst for the sustainable synthesis of 3,3-spirocyclic oxindoles in aqueous media.

Functionalized graphitic carbon nitride (Sg-C3N4) has been manufactured and used as a reusable catalyst for the one-pot production of various spiro-pyrano chromenes and spiro indole-3,1'-naphthalene tetracyclic systems in aqueous media. An ultrasound-assisted method has been used for the functionalization of g-C3N4. The catalytic functionalities and the structural integrity of the catalyst were characterized via different analytical tools. The catalytic site-specific role of Sg-C3N4 was confirmed via various control experiments in one-pot reaction sequences. We recognized that Sg-C3N4 acts as a bifunctional acid-base catalyst for the first reaction sequence whereas it is an acidic catalyst for the second reaction sequence during the one-pot production of various spiro-pyrano chromenes. In addition, the bifunctional acid-base catalytic role of Sg-C3N4 has been confirmed for the first reaction sequence whereas it has a basic catalytic role for the second reaction sequence during the one-pot production of spiro indole-3,1'-naphthalene tetracyclic systems. Diverse C-C, C-O, and C-N bonds, six-membered cycles, stereogenic centers, and spiro frameworks were formed in a single reaction, enhancing the biocidal profile and possibly resulting in the discovery of new medicinal properties. The mild reaction environment, simple workup, easy separation, low cost, heterogeneity, and recyclability of Sg-C3N4 are some rewards of this approach.

The graphite-catalyzed ipso-functionalization of arylboronic acids in an aqueous medium: metal-free access to phenols, anilines, nitroarenes, and haloarenes.

An efficient, metal-free, and sustainable strategy has been described for the ipso-functionalization of phenylboronic acids using air as an oxidant in an aqueous medium. A range of carbon materials has been tested as carbocatalysts. To our surprise, graphite was found to be the best catalyst in terms of the turnover frequency. A broad range of valuable substituted aromatic compounds, i.e., phenols, anilines, nitroarenes, and haloarenes, has been prepared via the functionalization of the C-B bond into C-N, C-O, and many other C-X bonds. The vital role of the aromatic π-conjugation system of graphite in this protocol has been established and was observed via numerous analytic techniques. The heterogeneous nature of graphite facilitates the high recyclability of the carbocatalyst. This effective and easy system provides a multipurpose approach for the production of valuable substituted aromatic compounds without using any metals, ligands, bases, or harsh oxidants.

Microwave-assisted nanocatalysis: A CuO NPs/rGO composite as an efficient and recyclable catalyst for the Petasis-borono-Mannich reaction.

A CuO NP decorated reduced graphene oxide (CuO NPs/rGO) composite was synthesized and characterized using various analytical techniques viz. XRD, TEM, SEM, UV-Vis, FT-IR, EDX, XPS and CV. The activity of the catalyst was probed for the Petasis-Borono-Mannich (PBM) reaction of boronic acids, salicylaldehydes, and amines under microwave irradiation (MW). The CuO NPs/rGO composite works as a catalyst as well as a susceptor and augments the overall ability of the reaction mixture to absorb MW. The synergistic effect of MW and CuO NPs/rGO resulted in an excellent outcome of the reaction as indicated by the high TOF value (3.64 × 10-3 mol g-1 min-1). The catalytic activity of the CuO NPs/rGO composite was about 12-fold higher under MW compared to the conventional method. The catalyst was recovered by simple filtration and recycled 8 times without significant loss in activity. This atom-economical protocol includes a much milder procedure, and a catalyst benign in nature, does not involve any tedious work-up for purification, and avoids hazardous reagents/byproducts and the target molecules were obtained in good to excellent yields.