From Bulk Molybdenum Disulfide (MoS2) to Suspensions of Exfoliated MoS2 in an Aqueous Medium and Their Applications.

Two-dimensional (2D) layered materials like graphene, transition-metal dichalcogenides (TMDs), boron nitrides, etc., exhibit unique and fascinating properties, such as high surface-to-volume ratio, inherent mechanical flexibility and robustness, tunable bandgap, and high carrier mobility, which makes them an apt candidate for flexible electronics with low consumption of power. Because of these properties, they are in tremendous demand for advancement in energy, environmental, and biomedical sectors developed through various technologies. The production and scalability of these materials must be sustainable and ecofriendly to utilize these unique properties in the real world. Here, in this current review, we review molybdenum disulfide (MoS2 nanosheets) in detail, focusing on exfoliated MoS2 in water and the applicability of aqueous MoS2 suspensions in various fields. The exfoliation of MoS2 results in the formation of single or few-layered MoS2. Therefore, this Review focuses on the few layers of exfoliated MoS2 that have the additional properties of 2D layered materials and higher excellent compatibility for integration than existing conventional Si tools. Hence, a few layers of exfoliated MoS2 are widely explored in biosensing, gas sensing, catalysis, photodetectors, energy storage devices, a light-emitting diode (LED), adsorption, etc. This review covers the numerous methodologies to exfoliate MoS2, focusing on the various published methodologies to obtain nanosheets of MoS2 from water solutions and their use.

Heteroatom Doping in Pollutant Diesel Soot-Derived Nanocarbon for Enhanced Zn-Ion Storage Performance.

Herein, we have isolated onion-like nanocarbon (ONC) from the exhaust soot of diesel engines and further doped it with nitrogen (N) and sulfur (S) to fabricate N,S-co-doped ONC (N-S-ONC). To explore its application feasibility, we have assembled an aqueous Zn-ion hybrid supercapacitor (ZIHSC) with a N-S-ONC cathode, which attains high specific capacitance with good rate capability. In-depth analyses suggest that the mechanism of charge storage in the ONC is governed by both capacitive-controlled and diffusion-controlled processes, with the capacitive processes leading at all sweep rates. The ZIHSC demonstrated a good energy density of 50 Wh/kg, a maximum power density of 3.6 kW/kg, and an impressive cycle life with 73% capacitance retention after 50,000 charge-discharge cycles. The study suggests the potential possibly for the long-term application of BC derived nanocarbon in electrochemical energy storage systems (EESSs).

Fenton-mediated thermocatalytic conversion of CO2 to acetic acid by industrial waste-derived magnetite nanoparticles.

Iron oxide dust, discarded as industrial waste, has been used here to fabricate magnetic iron oxide nanoparticles (Fe3O4-NPs). We have proposed the thermo-catalytic reduction of carbon dioxide (CO2) using Fe3O4-NPs in the presence of H2O2 to get acetic acid (AcOH) at near ambient conditions (100 °C, 10 bar) with a maximum yield of ∼0.4 M in a batch-reactor. The importance of H2O2 can be described as it facilitates the production of higher concentrations of OH˙ and H+/˙, which consequently supports the synthesis of AcOH.

3D Porous MoS2-Decorated Reduced Graphene Oxide Aerogel as a Heterogeneous Catalyst for Reductive Transformation Reactions.

The MoS2-based reduced graphene oxide aerogel (MoS2-rGOA)-assisted organic transformation reactions are presented. MoS2-rGOA is used as a heterogeneous catalyst for the reduction of benzene derivatives such as benzaldehyde, nitrobenzene, and benzonitrile to benzyl alcohol, aniline, and benzamide and their derivatives, respectively, in green solvents (water/methanol) and green reducing agents (hydrazine hydrate having N2 and H2 as byproducts). The mechanistic features of the reduction pathway, substrate scope, and the best suitable conditions by varying the temperature, solvent, reducing agent, catalyst loading, time, etc. are optimized. All of the synthesized products are obtained in quantitative yield with purity and well characterized based on nuclear magnetic resonance analysis. Further, it is also observed that our catalyst is efficiently recyclable and works well checked up to 5 cycles.

Melamine-Formaldehyde Polymer-Based Nanocomposite for Sunlight-Driven Photodegradation of Multiple Dyes and Their Mixture.

Cadmium sulfide (CdS)-decorated, cross-linked melamine-formaldehyde polymer-based nanocomposite (MFP-CdS) has been synthesized. MFP-CdS is utilized here as a photoactive material for the photodegradation of six model organic dyes and their mixture in an aqueous medium in the presence of sunlight. The half-life values from the kinetic study of multiple dyes strongly support the importance of sunlight on the fast degradation of all six dyes compared to bulb light and control (dark) conditions. A comparative 1H NMR analysis of the dyes and their degraded products has been performed to support the breakdown of the aromatic framework of organic dyes using MFP-CdS in sunlight. The mechanisms involved in the photodegradation of dyes have been investigated based on radical trapping studies that support the significant involvement of superoxide radicals along with holes. Moreover, the dye removal efficiency using MFP-CdS from real industrial wastewater samples is evaluated via the external spiking of organic dyes and their mixture in unknown industrial effluents where they showed similar photodegradation results. Based on the high recyclability of MFP-CdS, these are used for multiple cycles.

Carbon Dots: Classically Defined versus Organic Hybrids on Shared Properties, Divergences, and Myths.

Carbon dots are defined as small carbon nanoparticles with effective surface passivation via organic functionalization. The definition is literally a description of what carbon dots are originally found for the functionalized carbon nanoparticles displaying bright and colorful fluorescence emissions, mirroring those from similarly functionalized defects in carbon nanotubes. In literature more popular than classical carbon dots are the diverse variety of dot samples from "one-pot" carbonization of organic precursors. On the two different kinds of samples from the different synthetic approaches, namely, the classical carbon dots versus those from the carbonization method, highlighted in this article are their shared properties and apparent divergences, including also explorations of the relevant sample structural and mechanistic origins for the shared properties and divergences. Echoing the growing evidence and concerns in the carbon dots research community on the major presence of organic molecular dyes/chromophores in carbonization produced dot samples, demonstrated and discussed in this article are some representative cases of dominating spectroscopic interferences due to the organic dye contamination that have led to unfound claims and erroneous conclusions. Mitigation strategies to address the contamination issues, including especially the use of more vigorous processing conditions in the carbonization synthesis, are proposed and justified.

Non-aqueous onion like nano-carbons from waste diesel-soot used as FRET-based sensor for sensing of nitro-phenols.

Herein, a simple-functionalization method is described to prepare the oleylamine functionalized non-aqueous version of onion-like nanocarbons (ONC-OA), where ONC was isolated from the waste pollutant soot exhausted from the diesel engine. The surface group analysis of ONC-OA has been investigated via Nuclear Magnetic Resonance and X-ray Photoelectron Spectroscopy. ONC-OA shows blue fluorescence with a quantum yield of ∼6% in tetrahydrofuran (THF). The fluorescence-based sensing applications of ONC-OA has been investigated for selective sensing of toxic aromatic nitro-phenols compounds (para-nitro, dinitro, and trinitro phenols) from the tested many nitro organic compounds. Based on the limit of detection values, ONC-OA shows much better results for tri-nitro phenol compared to di and mono nitrophenol. To understand the quenching mechanism, a time-resolved photoluminescence analysis of the sensor with and without the addition of quenchers is performed. The effective lowering in fluorescence lifetime of the sensor after the addition of quenchers concludes that the quenching observed is majorly due to the Förster Resonance Energy Transfer (FRET) mechanism. The real-life application of ONC-OA was analyzed by external spiking of N-PhOHs in soil samples.

Sunlight promoted removal of toxic hexavalent chromium by cellulose derived photoactive carbon dots.

A scalable synthetic procedure for fabricating photoactive carbon dots (CD) from microcrystalline cellulose (MCC) is presented. The MCC was transformed into a photoactive nanosized CD by a one-step acid-assisted thermal-carbonization (~90 °C for 30 min). The efficiency of the obtained CD was determined by photo-removal of toxic hexavalent chromium (Cr(VI)) ions from wastewater. CD obtained from cellulose completely removed 20 ppm of Cr(VI) wastewater within ∼120 min under sunlight illumination. No Cr(VI) removal was observed in dark conditions and with control cellulose material as reference samples. The Cr(VI) removal follows pseudo-first-order kinetics along with a half-life of ∼26 min. Furthermore, the Cr(VI) removal from wastewater was supported via cyclic voltammetry analysis. Using a low-cost, naturally available cellulose material and sulfuric acid, the world's most-used chemical, creates techno-economic prerequisites for a scalable process of photoactive carbon dots.

Sunlight-promoted photodegradation of Congo red by cadmium-sulfide decorated graphene aerogel.

Herein, a simpler-viable methodology for the surface decoration of pear fruit derived graphene aerogel (GA) via cadmium sulfide (CdS) has been presented. GA can be easily synthesized from bio-mass, which provide an economic advantage. Surface decoration via CdS imparts photocatalytic activities in functionalized graphene aerogels (f-GA). CdS-f-GA is being explored here as a photocatalyst for the degradation of a toxic azo dye named Congo red in the presence of sunlight. The rate and mechanism associated with photodegradation were analyzed by performing kinetics and radical trap-based quenching experiments. Nuclear magnetic resonance and fourier transform infrared spectroscopy analyses of the control and photodegraded products were performed to ensure the degradation of the organic framework of Congo red. Additionally, the real-life applicability of CdS-f-GA was also analyzed by degrading the dye in different types of industrial samples (via the method of external spiking), which can advance its practical relevance.

Thiourea-functionalized graphene aerogel for the aqueous phase sensing of toxic Pb(II) metal ions and H2O2.

A simpler approach of functionalization for the fabrication of thiourea-functionalized-Graphene Aerogel (t-GA) is described here. Graphene Aerogel (GA) was synthesized from bio-mass, which on a simpler oxidative treatment get converted to its water-soluble version due to the impregnation of several oxygenous functionalities like carboxylic, hydroxyl, etc. Further, these carboxylated groups have been functionalized with the molecules of thiourea using the long known dicyclohexylcarbodiimide (DCC) as a coupling agent. The as-synthesized t-GA shows bright yellow fluorescence with a quantum yield of ~3% and holds the high-aqueous solubility and photostability. The fluorescence property of t-GA has been used here for the specific and selective sensing of toxic lead (Pb(II)) metal ions from the used many other metal ions via the fluorescence quenching and showed a limit of detection ~7.3 nM. Further, the mechanism for selective sensing was studied in detail and found to be preferable via ligand to metal charge transfer quenching mechanism. The cyclic voltammetry studies supported the selective sensing of Pb(II). Moreover, t-GA has also been studied for the sensing of hydrogen peroxide and as a yellow fluorescent ink.

Fluorescent Carbon Nano-onion as Bioimaging Probe.

Concentrically arranged multilayered fullerenes exhibiting onion-like morphology are popularly known as carbon nano-onion (CNO) and are useful in bioimaging application. On the basis of the origin of the fluorescence, the CNO-based nanoprobes are classified into type I and type II. The type I CNO-based nanoprobe needs a secondary moiety such as organic dyes or an amine functionalization at its surface to induce the fluorescence. On the other hand, the emission in type II does not originate from such an external surface passivating agent. The CNO-based system not only shows structural similarity to the well-known multiwalled carbon nanotube but is also a bit more advantageous because of its low cytotoxicity. These features enable their prolonged use in the biological system for imaging purposes. In particular, we have covered the aspects of synthesis, surface functionalization, the origin of fluorescence, and biocompatibility. In addition, recent developments directed toward in vitro and in vivo imaging studies by utilizing CNO-based nanoprobes are summarized here.

N, S, and P-Co-doped Carbon Quantum Dots: Intrinsic Peroxidase Activity in a Wide pH Range and Its Antibacterial Applications.

Nanozymes have drawn significant scientific interest due to their high practical importance in terms of overcoming the instability, complicated synthesis, and high cost of protein enzymes. However, their activity is generally limited to particular pHs, especially acidic ones. Herein, we report that luminescent N, S, and P-co-doped carbon quantum dots (NSP-CQDs) act as attractive peroxidase mimetics in a wide pH range, even at neutral pH, for the peroxidase substrate 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) in the presence of H2O2. The synergistic effects of multiple heteroatoms doping in CQDs boost the catalytic activity in a wide pH range attributed to the presence of high density of active sites for enzymatic-like catalysis and accelerated electron transfer during the peroxidase-like reactions. A possible reaction mechanism for the peroxidase-like activity of CQDs is investigated based on the radical trapping experiments. Moreover, the multifunctional activity of NSP-CQDs was further utilized for antibacterial assays for both Gram-negative and Gram-positive model species, including Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), respectively. The growths of the employed E. coli and S. aureus were found to be significantly inhibited due to the peroxidase-mediated perturbation of cell walls. The present work signifies the current advance in the rational design of N, S, and P-co-doped CQDs as highly active peroxidase mimics for novel applications in diverse fields, including catalysis, medical diagnostics, environmental chemistry, and biotechnology.

N,P-Doped Carbon Nanodots for Food-Matrix Decontamination, Anticancer Potential, and Cellular Bio-Imaging Applications.

We report a facile one-step thermal treatment method for the synthesis of biocompatible, fluorescent nitrogen-phosphorus-doped carbon nanodots (NPCDs) as multifunctional agents for the food matrix decontamination, cancer targeting, and cellular bio-imaging. NPCDs exhibit high toxicity towards L. monocytogenes, as illustrated by fluorescent live-dead cell counting, disruption of membrane permeability/potential, changes in the levels of cellular ions, genetic materials, and proteins, as well as intracellular production of reactive oxygen species. The tryptophan and protein peaks released in NPCDs treated cells contributed to indole ring breathing and correlated with induced cell death. NPCDs significantly inhibited bacterial biofilm formation on a solid substrate. NPCDs-coated low-density polyethylene (LDPE) film crosslinked with 1% aminopropyltriethoxy silane (APTES) via silane-hydroxyl linking as a food-grade wrap significantly reduced bacterial counts in a raw chicken food model. Furthermore, NPCDs induced apoptosis in HeLa cervical cancer cells, as confirmed by the distorted cell morphology, fluorescence microscopic analysis, presence of fragmented nuclei and the qPCR results of mRNA expression levels of apoptotic markers. Moreover, NPCDs were also applicable in utilized for the cellular bio-imaging of KM12-C colon cancer cells under confocal microscopy owing to their excellent luminescence properties. Overall, NPCDs represent a promising platform to reduce the environmental health risks associated with hazardous pathogens, anticancer targeting, and their application in cellular bio-imaging as multifunctional targets/nanocarriers.

N, S-codoped Carbon Dots for Nontoxic Cell Imaging and As a Sunlight-Active Photocatalytic Material for the Removal of Chromium.

Nitrogen-sulfur codoped carbon dots (NSCD) were synthesized via a single-step microwave-assisted method having a fluorescence quantum yield of ∼12%. The NSCD has been proven to be nontoxic and utilized as a fluorescent imaging nanoprobe for cancer cells (HeLa cells) under UV and blue light excitation (in vitro environment). In addition to the long-known cell imaging application, these NSCD have been used as a sunlight active photomaterial for the removal of toxic hexavalent chromium as Cr(VI). The experimental results reveal that the sunlight active NSCD shows good potential toward the photocatalytic removal of Cr(VI) ions from the wastewater. For the environment and water purification purpose, three different wastewater samples were tested that are synthetic wastewater (up to 100 ppm), laboratory wastewater, and Cr(VI) ion-spiked industrial wastewater for the photocatalytic removal of Cr(VI). The biocompatible NSCD as a fluorescent imaging probe of cancer cells along with its fruitful utilization in photocatalysis under sunlight (compared to the dark condition) demonstrates the overall sustainability of the presented process.

Pollutant-Soot-Based Nontoxic Water-Soluble Onion-like Nanocarbons for Cell Imaging and Selective Sensing of Toxic Cr(VI).

Presently, the technologies associated with using waste materials for the fabrication of newer useful materials have been greatly advanced. For the same purpose, a possible sustainable approach is described for the utilization of globally available dirty dangerous material, known as black carbon (BC), in the form of particulate diesel soot. From the black diesel particulate matter, onion-like nanocarbons (ONC) have been isolated followed by their surface functionalization to yield their amine-functionalized water-soluble version as ONC-NH2, which exhibits a high quantum yield value of ∼20%. Concerning the synthetic protocol, the potential associated with the presented report reveals that these ONC were used without being explicitly synthesized. These were just isolated from the diesel soot, which on amine functionalization have been converted to an efficient, biocompatible fluorescent probe for the imaging of cancer (HeLa) cells and selective sensing of toxic chromium Cr(VI) in water. The detailed surface functionalization by the amine molecules in ONC-NH2, which make them readily soluble in aqueous media, is investigated using several spectroscopic techniques such as XPS, NMR, and FTIR.

Soluble Graphene Nanosheets for the Sunlight-Induced Photodegradation of the Mixture of Dyes and its Environmental Assessment.

Currently, the air and water pollutions are presenting the most serious global concerns. Despite the well known tremendous efforts, it could be a promising sustainability if the black carbon (BC) soot can be utilized for the practical and sustainable applications. For this, the almost complete aqueous phase photodegradation of the three well-known organic pollutant dyes as crystal violet (CV); rhodamine B (RhB); methylene blue (MB) and their mixture (CV + RhB + MB), by using water-soluble graphene nanosheets (wsGNS) isolated from the BC soot under the influence of natural sunlight is described. The plausible mechanism behind the photocatalytic degradation of dyes and their mixture has been critically analyzed via the trapping of active species and structural analysis of photodegraded products. The impact of diverse interfering ions like Ca2+, Fe3+, SO42-, HPO42-, NO3-, and Cl- on the photodegradation efficiency of wsGNS was also investigated. Importantly, the environmental assessment of the whole process has been evaluated towards the growth of wheat plants using the treated wastewater. The initial studies for the fifteen days confirmed that growth of wheat plants was almost the same in the photodegraded wastewater as being noticed in the control sample, while in case of dyes contaminated water it showed the retarded growth. Using the natural sunlight, the overall sustainability of the presented work holds the potential for the utilization of pollutant soot in real-practical applications related to the wastewater remediation and further the practical uses of treated water.

Surface-passivated, soluble and non-toxic graphene nano-sheets for the selective sensing of toxic Cr(vi) and Hg(ii) metal ions and as a blue fluorescent ink.

Non-toxic amine-functionalized soluble graphene nano-sheets (f-GNS) were synthesized by using an old and well-known simple organic procedure. The f-GNS exhibited enhanced optical properties, such as strong blue fluorescence emission with a high value of quantum yield (∼13%). The O,O'-bis-(2-aminopropyl) polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol 800 as block polymeric amine (BPA)-passivized surface of f-GNS exhibited high aqueous solubility and excitation-dependent fluorescence emission behavior with a strong photo-stability performance. These f-GNS were tested for the significant selective sensing of toxic metal ions Cr(vi) and Hg(ii) from various tested toxic metal ions. The sensing experiment was supported by cyclic voltammetry analysis. The dual metal ion sensing method based on fluorescence showed the limit of detection (LOD) of ∼56 nM for Cr(vi) and ∼45 nM for Hg(ii) through a fluorescence quenching process. f-GNS were found to be non-toxic when tested over Escherichia coli (E.coli) cells. Additionally, the strong blue emission properties of f-GNS enabled their use as a suitable blue fluorescent ink under UV light illumination.

Brightly Fluorescent Zinc-Doped Red-Emitting Carbon Dots for the Sunlight-Induced Photoreduction of Cr(VI) to Cr(III).

The present finding deals with a simple and low-cost fabrication of surface-passivated, brightly fluorescent zinc-oxide-decorated, red-emitting excitation-independent ultrafluorescent CDs, denoted as "CZnO-Dots". Surface doping of zinc oxide significantly improved the quantum yield by up to ∼72%, and these brightly fluorescent red-emitting CZnO-Dots have been employed for the aqueous-phase photoreduction of 100 ppm hexavalent chromium(VI) to trivalent chromium(III) under the influence of sunlight irradiation. The overall utility of the prepared CZnO-Dots can be ascertained by their recyclability over seven cycles.

Correction to "Brightly Fluorescent Zinc-Doped Red-Emitting Carbon Dots for the Sunlight-Induced Photoreduction of Cr(VI) to Cr(III)".

[This corrects the article DOI: 10.1021/acsomega.8b00047.].

P2O5 assisted green synthesis of multicolor fluorescent water soluble carbon dots.

A low cost synthesis of multicolor fluorescent carbon dots (C-dots) from edible sugars is described here. Common sugars like dextrose, lactose or maltose in aqueous medium gets dehydrated using phosphorus pentoxide (P2O5). The reaction is facile and completed within few minutes to form insoluble carbon (C-dots) mostly having the graphitic (G-band, Raman) sp2 hybridized carbon atoms (C-atoms). This insoluble carbon on oxidative treatment with nitric acid produced disordered sp3 (D-band retaining G-band, Raman) hybridized C-atoms, originated from the graphitic pool with sp2 hybridized C-atoms. This high density assimilation of self passivated "surfacial defects" become emissive during electronic transitions. Surfacial defects due to high degree of electrophilic carboxylation create the water soluble version of multicolor fluorescent C-dots as "water soluble fluorescent carbon dots" (wsFCDs). wsFCDs being itself self-passivated imposes the tunable multicolor emission throughout the visible spectrum without having any external coating and surface passivation and could be used as multicolor fluorescent probe especially in the emerging field of optical bio-imaging.