Photocatalytic H2 production and degradation of aqueous 2-chlorophenol over B/N-graphene-coated Cu0/TiO2: A DFT, experimental and mechanistic investigation.

Energy and environmental challenges are global concerns that scientists are interested in alleviating. It is on this premise that we prepared boron/nitrogen graphene-coated Cu0/TiO2 (B/N-graphene-coated Cu/TiO2) photocatalyst of varying B:N ratios with dual functionality of H2 production and 2-Chlorophenol (2-CP) degradation. In-situ coating of Cu0 with B/N-graphene is achieved via solvothermal synthesis and calcination under an inert atmosphere. All B/N-graphene-coated Cu/TiO2 exhibit higher photonic efficiencies (5.68%-7.06% at 300 < λ < 400 nm) towards H2 production than bare TiO2 (0.25% at 300 < λ < 400 nm). Varying the B:N ratio in graphene influences the efficiency of H2 generation. A B:N ratio of 0.08 yields the most active composite exhibiting a photonic efficiency of 7.06% towards H2 evolution and a degradation rate of 4.07 × 10-2 min-1 towards 2-chlorophenol (2-CP). Density functional theory (DFT) investigations determine that B-doping (p-type) enhances graphene stability on Cu0 while N-doping (n-type) increases the reduction potential of Cu0 relative to H+ reduction potential. X-ray photoelectron spectroscopy reveals that increasing the B:N ratio increases p-type BC2O while decreasing n-type pyridinic-N in graphene thus altering the interlayer electron density. Isotopic labelling experiments determine water reduction as the main mechanism by which H2 is produced over B/N-graphene-coated Cu/TiO2. The reactive species involved in the degradation of 2-CP are holes (h+), hydroxyl radical (OH•), and O2•-, of which superoxide (O2•-) plays the major role. This work displays B/N -graphene-coated Cu/TiO2 as a potential photocatalyst for large-scale H2 production and 2-CP degradation.

One-Step Green Synthesis of Water-Soluble Fluorescent Carbon Dots and Its Application in the Detection of Cu2.

Renewable biowaste-derived carbon dots have garnered immense interest owing to their exceptional optical, fluorescence, chemical, and environmentally friendly attributes, which have been exploited for the detection of metals, non-metals, and organics in the environment. In the present study, water-soluble fluorescent carbon dots (CDs) were synthesized via facile green microwave pyrolysis of pine-cone biomass as precursors, without any chemical additives. The synthesized fluorescent pine-cone carbon dots (PC-CDs) were spherical in shape with a bimodal particle-size distribution (average diameters of 15.2 nm and 42.1 nm) and a broad absorption band of between 280 and 350 nm, attributed to a π-π* and n-π* transition. The synthesized PC-CDs exhibited the highest fluorescent (FL) intensity at an excitation wavelength of 360 nm, with maximum emission of 430 nm. The synthesized PC-CDs were an excellent fluorescent probe for the selective detection of Cu2+ in aqueous solution, amidst the presence of other metal ions. The FL intensity of PC-CDs was exceptionally quenched in the presence of Cu2+ ions, with a low detection limit of 0.005 µg/mL; this was largely ascribed to Cu2+ ion binding interactions with the enriched surface functional groups on the PC-CDs. As-synthesized PC-CDs are an excellent, cost effective, and sensitive probe for detecting and monitoring Cu2+ metal ions in wastewater.

Sustainable Hydrothermal and Solvothermal Synthesis of Advanced Carbon Materials in Multidimensional Applications: A Review.

The adoption of green technology is very important to protect the environment and thus there is a need for improving the existing methods for the fabrication of carbon materials. As such, this work proposes to discuss, interrogate, and propose viable hydrothermal, solvothermal, and other advanced carbon materials synthesis methods. The synthesis approaches for advanced carbon materials to be interrogated will include the synthesis of carbon dots, carbon nanotubes, nitrogen/titania-doped carbons, graphene quantum dots, and their nanocomposites with solid/polymeric/metal oxide supports. This will be performed with a particular focus on microwave-assisted solvothermal and hydrothermal synthesis due to their favourable properties such as rapidity, low cost, and being green/environmentally friendly. These methods are regarded as important for the current and future synthesis and modification of advanced carbon materials for application in energy, gas separation, sensing, and water treatment. Simultaneously, the work will take cognisance of methods reducing the fabrication costs and environmental impact while enhancing the properties as a direct result of the synthesis methods. As a direct result, the expectation is to impart a significant contribution to the scientific body of work regarding the improvement of the said fabrication methods.

Graphitic Carbon Nitride: A Highly Electroactive Nanomaterial for Environmental and Clinical Sensing.

Graphitic carbon nitride (g-C3N4) is a two-dimensional conjugated polymer that has attracted the interest of researchers and industrial communities owing to its outstanding analytical merits such as low-cost synthesis, high stability, unique electronic properties, catalytic ability, high quantum yield, nontoxicity, metal-free, low bandgap energy, and electron-rich properties. Notably, graphitic carbon nitride (g-C3N4) is the most stable allotrope of carbon nitrides. It has been explored in various analytical fields due to its excellent biocompatibility properties, including ease of surface functionalization and hydrogen-bonding. Graphitic carbon nitride (g-C3N4) acts as a nanomediator and serves as an immobilization layer to detect various biomolecules. Numerous reports have been presented in the literature on applying graphitic carbon nitride (g-C3N4) for the construction of electrochemical sensors and biosensors. Different electrochemical techniques such as cyclic voltammetry, electrochemiluminescence, electrochemical impedance spectroscopy, square wave anodic stripping voltammetry, and amperometry techniques have been extensively used for the detection of biologic molecules and heavy metals, with high sensitivity and good selectivity. For this reason, the leading drive of this review is to stress the importance of employing graphitic carbon nitride (g-C3N4) for the fabrication of electrochemical sensors and biosensors.

Facile microwave synthesis of pine cone derived C-doped TiO2 for the photodegradation of tetracycline hydrochloride under visible-LED light.

Pine cone derived carbon was doped into TiO2 via a facile microwave procedure at different powers, different from other conventional synthesis methods. The materials were adequately characterized and applied in the photodegradation of 5 mg/L tetracycline hydrochloride (TA) under visible-LED light. The XRD results showed that all materials exist as both anatase and rutile phase. However, both the microwave power and the carbon content of the composite material inhibited the conversion of anatase into rutile. The composite material synthesized at a microwave power of 800 W (CT800), displayed the highest band gap energy (3.14 eV) but showed the least electron-hole recombination rate. Hence, CT800 exhibited the highest apparent rate constant of 9.9 × 10-3 min-1 and a half-life of 70 min. An inverse relationship between OH• radical scavenger (isopropanol) and the percentage degradation by CT800 suggests that OH• is majorly responsible for the degradation of TA. Recyclability studies revealed that after 4 cycles of photocatalytic degradation reactions, CT800 retained approximately 83% performance confirming its stability and reusability.