Waste Polyethylene-Derived Carbon Dots: Administration of Metal-Free Oxidizing Agents for Tunable Properties and Photocatalytic Hyperactivity.

The possibility of converting waste plastics into carbon dots (CDs) with 100% efficiencies using KMnO4 has emerged as a significant discovery in mitigating plastic pollution and upcycling. However, the lack of tunability of their properties, viz. aerial O2 harvesting, light-induced autophagy, and photoactivity using air as a free oxidant, has remained a bottleneck. Besides, the toxicity of KMnO4 makes the process less sustainable. Attempting to bridge these gaps, herein, we demonstrate the preparation of CDs using polyethylene with enormous controllability of their properties by utilizing less-toxic and metal-residue-free oxidizers, e.g., H2O2, HNO3, HClO4, and NaClO. We obtain structurally diverse CDs with controllable luminescent quantum yields (∼0.5-8%), excitonic lifetimes (1.3-2.3 ns), and binding energies (147-290 meV). These CDs exhibit a hugely extended range of molecular O2 harvesting (∼405-650 µM) with different amounts of strongly and weakly surface-bound O2 molecules within an estimated ratio of ∼0.77-2.51. Autophagy varied from 14 days to a nearly "no-autophagy" show. We efficiently utilized their oxygen harvesting and photocatalytic abilities to synthesize imine compounds from the corresponding amines in the open air (rate constant of ∼0.055 min-1), surpassing the literature efficiencies achieved using an O2 flow and noble metals. Notably, due to oxygen harvesting by CDs, no additional rate enhancement was observed after O2 purging, establishing the role of CDs in making free air an excellent oxidizing agent.

Stimuli-Responsive Control over Self-Assembled Nanostructures in Sequence-Specific Functional Block Copolymers.

The precise sequence of a protein's primary structure is essential in determining its folding pathways. To emulate the complexity of these biomolecules, functional block copolymers consisting of segmented triblocks with distinct functionalities positioned in a sequence-specific manner are designed to control the polymer chain compaction. Triblock polymers P- b -C- b -F and P- b -F- b -C and random diblock copolymer P- b -C- r -F consist of a hydrophilic poly(ethylene oxide) (PEO) block and a hydrophobic block with coumarin (C) and ferrocene (F) moieties that are grafted in a sequence-specific or random manner onto the hydrophilic block. External stimuli such as UVB light, redox, and chemical cues influence the functional hydrophobic block to alter the packing parameters that are monitored with spectroscopic and scattering techniques. Interestingly, the positioning of the stimuli-responsive moiety within the hydrophobic block of P- b -C- b -F, P- b -F- b -C, and P- b -C- r -F affects the extent of the hydrophobic-hydrophilic balance in block copolymers that renders orthogonal control in stimuli-responsive transformation of self-assembled vesicles to micelles.

Orthogonal chain collapse in stimuli-responsive di-block polymers leading to self-sorted nanostructures.

We design amphiphilic di-block copolymers (P-b-F and P-b-C) tethered with stimuli-responsive ferrocene and coumarin hydrophobic pendants that exhibit chain collapse behaviour in response to light, redox and chemical cues, with subsequent transformation of the vesicles into micelles. Interestingly, the co-assembled vesicles of the polymer blend under orthogonal stimuli furnish self-sorted micelles and vesicles.

Universal Piezo-Photocatalytic Wastewater Treatment on Realistic Pollutant Feedstocks by Bi4TaO8Cl: Origin of High Efficiency and Adjustable Synergy.

Clean water is a fundamental human right but millions struggle for it daily. Herein, we demonstrate a new piezo-photocatalyst with immense structural diversity for universal wastewater decontamination. Single-crystalline Bi4TaO8Cl nanoplates with exposed piezoelectric facets exhibit visible-light response, piezoelectric behavior with coercive voltages of ±5 V yielding 0.35% crystal deformation, and pressure-induced band-bending of >2.5 eV. Using five common contaminants of textile and pharmaceutical industries, we show that the nanoplates can mineralize them in all piezocatalytic, photocatalytic, and piezo-photocatalytic approaches with efficiencies higher than most catalysts developed for just one contaminant. Their efficiencies for feedstocks differing over 2 orders of magnitude in concentrations, the highest to date, are also demonstrated to simulate real-life situations. These extensive studies established that combining piezocatalytic and photocatalytic approaches can lead to a tremendous synergy exceeding >45%. The origin of synergy has been illustrated for the first time using band-bending models and improved charge transfer from valence and conduction band electronic surfaces. We further quantified synergy across reactants, concentrations, and ultrasonic frequency and power to demonstrate their versatility and unpredictability. Finally, seven parameters that contribute to synergy but create unpredictability have been identified for the rational design of piezo-photocatalysts for wastewater treatment.

Bi4TaO8Cl as a New Class of Layered Perovskite Oxyhalide Materials for Piezopotential Driven Efficient Seawater Splitting.

Piezocatalytic water splitting is an emerging approach to generate "green hydrogen" that can address several drawbacks of photocatalytic and electrocatalytic approaches. However, existing piezocatalysts are few and with minimal structural flexibility for engineering properties. Moreover, the scope of utilizing unprocessed water is yet unknown and may widely differ from competing techniques due to the constantly varying nature of surface potential. Herein, we present Bi4TaO8Cl as a representative of a class of layered perovskite oxyhalide piezocatalysts with high hydrogen production efficiency and exciting tailorable features including the layer number, multiple cation-anion combination options, etc. In the absence of any cocatalyst and scavenger, an ultrahigh production rate is achievable (1.5 mmol g-1 h-1), along with simultaneous generation of value-added H2O2. The production rate using seawater is somewhat less yet appreciably superior to photocatalytic H2 production by most oxides as well as piezocatalysts and has been illustrated using a double-layer model for further development.

Role of interfacial contact between 2D materials and preselected nanostructures in the degradation of toxic dyes: Multifunctional facets of graphene.

Designing intimate interfacial contact between nanostructures and two-dimensional (2D) materials is highly desirable to influence the movement of generated charge carriers. Nanostructured zinc oxide (ZnO) is a fascinating material with unique optical and electrical properties. 2D reduced graphene oxide (rGO) exhibits semiconductor behaviour with tunable catalytic activity and excellent biocompatibility. Hence, we have designed a hybrid material by selecting nanostructures of an oxide semiconductor (ZnO) with reduced graphene oxide (rGO) using a hard integration technique followed by a low-temperature hydrothermal route. The good encapsulation of rGO over the ZnO nanorods was confirmed by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. The photocatalytic activities of ZnO, rGO, and ZnO/rGO were studied under visible-light irradiation using three different toxic dyes, methylene blue (MB), methyl orange (MO), and Congo red (CR). The composite materials exhibited excellent efficiencies of 100, 95, and 90% for the degradation of MB, MO, and CR, respectively. Moreover, the degradation of the dye was found to follow first-order kinetics. The enhanced efficiencies are attributed to the adsorption and efficient charge transfer from rGO to the conduction band of ZnO. The role of the multifunctional facets of graphene was presented to elucidate the visible-light activity of the composite materials for enhanced efficiency. The main reactive species (e-) of the reduction reaction were confirmed through a radical trapping experiment, which showed the generation of highly reactive •OH radicals that decompose the toxic dye. The results provide a perspective for developing graphene-based composite materials with desired preselected nanostructures for solar energy utilisation.

Synthesis of Bi3TaO7-Bi4TaO8Br composites in ambient air and their high photocatalytic activity upon metal loading.

Herein, we show that composites of Bi3TaO7-Bi4TaO8X (X = Cl, Br), two important Bi- and Ta-based light-responsive phases, can be prepared by high temperature, ambient air treatment of the precursors including easily oxidizable BiOX that retain the halide phases in excess of 60% and exhibit high photocatalytic activity. Furthermore, when these phases were loaded with less than 1% noble metals (Pd, Pt, Ag), nearly complete separation of the photogenerated excitons was observed, leading to a significant enhancement in the photocatalytic activity.