Our Biosphere comprises abundant biopolymers such as cellulose, chitin, and chitosan possessing highly desirable traits with biodegradability and renewability being prominent ones. The presence of ...amino groups in chitin/chitosan confer these basic polysaccharides numerous advantages to help generate chemical entities with unique and sought-after functional properties, besides nitrogen-enriched carbonaceous materials. This Perspective article emphasizes some of the appealing prospects these biopolymers provide because of the recent technological developments in nanotechnology field ranging from traditional catalysis to emerging high-value products. A few examples are presented for sustainable chemical transformations and environmental remediation exploiting the abundant biomass, agricultural residues, and seafood waste. Traditional biomass-derived platform chemicals are also introduced as the potential source of renewable feedstocks from these carbon-based materials, which offer many options for production of sustainable products thus circumventing the traditional use of fossil fuel-derived chemicals.
Carbon and graphene quantum dots are prepared using top-down and bottom-up methods. Sustainable synthesis of quantum dots has several advantages such as the use of low-cost and non-toxic raw ...materials, simple operations, expeditious reactions, renewable resources and straightforward post-processing steps. These nanomaterials are promising for clinical and biomedical sciences, especially in bioimaging, diagnosis, bioanalytical assays and biosensors. Here we review green methods for the fabrication of quantum dots, and biomedical and biotechnological applications.
Photocatalysis has been invariably considered as an unselective process (especially in water) for a fairly long period of time, and the investigation on selective photocatalysis has been largely ...neglected. In recent years, the field of selective photocatalysis is developing rapidly and now extended to several newer applications. This review focuses on the overall strategies which can improve the selectivity of photocatalysis encompassing a wide variety of photocatalysts, and modifications thereof, as well as the related vital processes of industrial significance such as reduction and oxidation of organics, inorganics, and CO2 transformation. Comprehensive and successful strategies for enhancing the selectivity in photocatalysis are abridged to reinvigorate and stimulate future investigations. In addition, nonsemiconductor type photocatalysts, such as Ti–Si molecular sieves and carbon quantum dots (CQDs), are also briefly appraised in view of their special role in special selective photocatalysis, namely epoxidation reactions, among others. In the end, a summary and outlook on the challenges and future directions in the research field are included in the comprehensive review.
The supply of safe drinking and clean water is becoming increasingly challenging proposition throughout the world. The deployment of environmentally sustainable nanomaterials with unique advantages ...namely high efficiency and selectivity, earth-abundance, recyclability, low-cost of production processes, and stability, has been a priority although several important challenges and constraints still remained unresolved. Carbon nanomaterials namely activated carbon, multi-walled- and single-walled carbon nanotubes, have been developed and applied as adsorbents for wastewater treatment and purification; graphene and graphene oxide-based nanomaterials as well as carbon and graphene quantum dots-derived nanomaterials have shown significant promise for water and wastewater treatment and purification, especially, for industrial- and pharmaceutical-laden wastes. This review encompasses advanced carbonaceous nanomaterials and methodologies that are deployed for the elimination of contaminants and ionic metals in aqueous media, and as novel nanosorbents for wastewater, drinking and ground water treatment. Additionally, recent trends and challenges pertaining to the sustainable carbon and graphene quantum dots-derived nanomaterials and their appliances for treating and purifying wastewater are highlighted.
Advanced nanomaterials for water treatment comprising carbon nanotubes, carbon- and graphene quantum dots and graphene-based nanomaterials, are highlighted. Display omitted
Microwave-assisted organic synthesis has been widely studied and deliberated, opening up some controversial issues as well. Nowadays, microwave chemistry is a mature technology that has been well ...demonstrated in many cases with numerous advantages in terms of the reaction rate and yield. The strategies toward scaling up find an ally in continuous-flow reactor technology comparing dielectric and conductive heating.
Magnetic attraction not filtration: A magnetic nanoparticle‐supported ruthenium hydroxide catalyst (see figure) was readily prepared from inexpensive starting materials and shown to catalyze the ...hydration of nitriles with excellent yield in a benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity, and the inherent stability of the catalyst system are additional sustainable attributes of this protocol.
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Magnetic attraction not filtration: A magnetic nanoparticle‐supported ruthenium hydroxide catalyst (see figure) was readily prepared from inexpensive starting materials and shown to catalyze the hydration of nitriles with excellent yield in a benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity, and the inherent stability of the catalyst system are additional sustainable attributes of this protocol.
The synthesis, stability, and toxicity of engineered metal nanoparticles (ENPs) have been extensively studied during the past two decades. In contrast, research on the formation, fate, and ecological ...effects of naturally-occurring nanoparticles (NNPs) has become a focus of attention only recently. The natural existence of metal nanoparticles and their oxides/sulfides in waters, wastewaters, ore deposits, mining regions, and hydrothermal vents, as exemplified by the formation of nanoparticles containing silver and gold (AgNPs and AuNPs), Fe, Mn, pyrite (FeS2), Ag2S, CuS, CdS, and ZnS, is dictated largely by environmental conditions (temperature, pH, oxic/anoxic, light, and concentration and characteristics of natural organic matter (NOM)). Examples include the formation of nanoparticles containing pyrite, Cu and Zn-containing pyrite, and iron in hydrothermal vent black smoker emissions. Metal sulfide nanoparticles can be formed directly from their precursor ions or indirectly by sulfide ion-assisted transformation of the corresponding metal oxides under anaerobic conditions. This tutorial focuses on the formation mechanisms, fate, and toxicity of natural metal nanoparticles. Natural waters containing Ag(I) and Au(III) ions in the presence of NOM generate AgNPs and AuNPs under thermal, non-thermal, and photochemical conditions. These processes are significantly accelerated by existing redox species of iron (Fe(II)/Fe(III)). NOM, metal-NOM complexes, and reactive oxygen species (ROS) such as O2˙(-), ˙OH, and H2O2 are largely responsible for the natural occurrence of nanoparticles. AgNPs and AuNPs emanating from Ag(I)/Au(III)-NOM reactions are stable for several months, thus indicating their potential to be transported over long distances from their point of origin. However, endogenous cations present in natural waters can destabilize the nanoparticles, with divalent cations (e.g., Ca(2+), Mg(2+)) being more influential than their monovalent equivalents (e.g., Na(+), K(+)). The toxicity of NNPs may differ from that of ENPs because of differences in the coatings on the nanoparticle surfaces. An example of this phenomenon is presented and is briefly discussed.
A nonclassical heating technique using microwaves, termed “Bunsen burner of the 21st century”, is rapidly becoming popular and is dramatically reducing reaction times. The significant outcomes of ...microwave (MW)-assisted green chemistry endeavors, which have resulted in the development of synthetic protocols for drugs and fine chemicals synthesis that are relatively more sustainable, are summarized. The use of emerging microwave-assisted chemistry techniques in conjunction with greener reaction media is dramatically reducing chemical waste and reaction times in several organic syntheses and chemical transformations. A brief historic account of our own experiences in developing MW-assisted organic transformations, which involve various benign alternatives, such as solid-supported reagents, and greener reaction media, namely, aqueous, ionic liquid, and solvent-free, for the synthesis of various heterocycles, coupling reactions, oxidation–reduction reactions, and some name reactions are described. Synthesis of Heterocycles. The synthetic chemistry community has been under increased pressure to produce, in an environmentally benign fashion, the myriad of heterocyclic systems required by society in a short span of time, and one of the best options to accelerate these synthetic processes is to use MW technology. The efficient use of the MW heating approach for the synthesis of various heterocyclic compounds in aqueous and solvent-free medium is discussed. Organic Named Reactions. The application of MW chemistry for various named reaction such as the Prins reaction, the Suzuki reaction, the Heck reaction, the Aza-Michael reaction, Trost’s γ-addition, and the Cannizzaro reaction are summarized. Synthesis and Application of Ionic Liquids. Ionic liquids (ILs), being polar and ionic, in character couple with MW irradiation very efficiently and are, therefore, ideal MW-absorbing candidates for expediting chemical reactions. MW-assisted solvent-free synthesis and application of ILs are discussed. Oxidation–Reduction Reactions. MW protocols using mineral oxides such as alumina, silica, and clay to immobilize reagents on such solid supports have been extensively explored under “dry” media conditions. Various solvent-free examples of oxidation reactions are discussed that involve mixing of neat substrates with clay-supported iron(III) nitrate (clayfen) or iodobenzene diacetate (IBD) as an oxidant; some interesting MW reduction protocols using borohydrides are also discussed. Protection−Deprotection Reactions. The protection and deprotection of alcohols and amines are common events in multistep organic syntheses. Various protection and deprotection protocols under MW irradiation are discussed, including tetrahydropyranylation and (benzyloxycarbonyl) (Cbz)-protection, which are the most frequently employed methods.
The applications of copper (Cu) and Cu-based nanoparticles, which are based on the earth-abundant and inexpensive copper metal, have generated a great deal of interest in recent years, especially in ...the field of catalysis. The possible modification of the chemical and physical properties of these nanoparticles using different synthetic strategies and conditions and/or via postsynthetic chemical treatments has been largely responsible for the rapid growth of interest in these nanomaterials and their applications in catalysis. In addition, the design and development of novel support and/or multimetallic systems (e.g., alloys, etc.) has also made significant contributions to the field. In this comprehensive review, we report different synthetic approaches to Cu and Cu-based nanoparticles (metallic copper, copper oxides, and hybrid copper nanostructures) and copper nanoparticles immobilized into or supported on various support materials (SiO2, magnetic support materials, etc.), along with their applications in catalysis. The synthesis part discusses numerous preparative protocols for Cu and Cu-based nanoparticles, whereas the application sections describe their utility as catalysts, including electrocatalysis, photocatalysis, and gas-phase catalysis. We believe this critical appraisal will provide necessary background information to further advance the applications of Cu-based nanostructured materials in catalysis.
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