Phosphorus-Induced One-Step Synthesis of NiCo2S4 Electrode Material for Efficient Hydrazine-Assisted Hydrogen Production.

Rational control of the reaction parameters is highly important for synthesizing active electrocatalysts. NiCo2S4 is an excellent spinel-based electrocatalyst that is usually prepared through a two-step synthesis. Herein, a one-step hydrothermal route is reported to synthesize P-incorporated NiCo2S4. We discovered that the inclusion of P caused formation of the NiCo2S4 phase in a single step. Computational studies were performed to comprehend the mechanism of phase formation and to examine the energetics of lattice formation. Upon incorporation of the optimum amount of P, the stability of the NiCo2S4 lattice was found to increase steadily. In addition, the Bader charges on both the metal atoms Co and Ni in NiCo2S4 and P-incorporated NiCo2S4 were compared. The results show that replacing S with the optimal amount of P leads to a reduction in charge on both metal atoms, which can contribute to a more stable lattice formation. Further, the electrochemical performance of the as-synthesized materials was evaluated. Among the as-synthesized nickel cobalt sulfides, P-incorporated NiCo2S4 exhibits excellent activity toward hydrazine oxidation with an onset potential of 0.15 V vs RHE without the assistance of electrochemically active substrates like Ni or Co foam. In addition to the facile synthesis method, P-incorporated NiCo2S4 requires a very low cell voltage of 0.24 V to attain a current density of 10 mA cm-2 for hydrazine-assisted hydrogen production in a two-electrode cell. The free energy profile of the stepwise HzOR has been investigated in detail. The computational results suggested that HzOR on P-incorporated NiCo2S4 was more feasible than HzOR on NiCo2S4, and these findings corroborate the experimental evidence.

Trapping and exciton-exciton annihilation assisted ultrafast carrier dynamics in nanosheets of 2H-MoSe2 and Cr doped 1T/2H-MoSe2.

Nanosheets of transition metal dichalcogenides with prospects of photocatalysis and optoelectronics applications have significant potential in device fabrication due to their low-cost production and easily controllable morphology. Here, non-degenerate pump-probe differential transmission studies with varying pump-fluence have been carried out on single-phase 2H-MoSe2 and mixed-phase 1T/2H-MoSe2 nanosheets to characterize their excited carrier dynamics. For both the samples, the differential probe transmission data show photo-induced bleaching at earlier pump-probe delay followed by photo-induced absorption unveiling signatures of exciton-state filling, exciton trapping, defect-mediated photo-induced probe absorption and recombination of defect bound excitons. The exciton trapping and photo-induced absorption by the trapped-carriers are estimated to occur with time constant of ∼430 to 500 fs based on multi-exponential modelling of the differential transmission till pump-probe delay of ∼3.5 ps. Biexponential modeling of the subsequent slow-recovery of the negative differential transmission at pump-probe delay ≳3.5 ps reveals that the exciton recombination happens via two distinct decay channels with ∼25 to 55 ps (τ1) and ≳1 ns (τ2) time constants. Pump-fluence dependent reduction in τ1 and further modelling of exciton population using higher order kinetic rate equation reveals that the two-body exciton-exciton annihilation governs the exciton recombination initially with a decay rate of ∼10-8 cm3s-1. The detailed analysis suggests that the fraction of total excitons that decay via long decay channel decreases with increasing exciton density for 2H-MoSe2, in contrast to 1T/2H-MoSe2 where the fraction of excitons decaying via long decay channel remains constant.

Ligand-Tuned Energetics for the Selective Synthesis of Ni2P and Ni12P5 Possessing Bifunctional Electrocatalytic Activity toward Hydrogen Evolution and Hydrazine Oxidation Reactions.

The occurrence of many phases and stoichiometries of nickel phosphides calls for the development of synthetic levers to selectively produce phases with purity. Herein, thiol (-SH) and carboxylate (-COO-) functional groups in ligands were found to effectively tune the energetics of nickel phosphide phases during hydrothermal synthesis. The initial kinetic product Ni2P transforms into thermodynamically stable Ni12P5 at longer reaction times. The binding of carboxylate onto Ni2P promotes this phase transformation to produce pure-phase Ni12P5 within 5 h compared to previous reports (∼48 h). Thiol-containing ligands inhibit this transformation process by providing higher stability to the Ni2P phase. Cysteine-capped Ni2P showed excellent geometric and intrinsic electrocatalytic activity toward both hydrogen evolution and hydrazine oxidation reactions under alkaline conditions. This bifunctional electrocatalytic nature enables cysteine-capped Ni2P to promote hydrazine-assisted hydrogen generation that requires lower energy (0.46 V to achieve 10 mA/cmgeo2) compared to the conventional overall water splitting (1.81 V to achieve 10 mA/cmgeo2) for hydrogen generation.

Alumina-Based Bifunctional Catalyst for Efficient CO2 Fixation into Epoxides at Atmospheric Pressure.

The quest toward sustainability and decarbonization demands the development of methods for efficient carbon dioxide capture and utilization. The nonreductive CO2 fixation into epoxides to prepare cyclic carbonates has gained attention in recent years. In this work, we report the development of guanidine hydrochloride-functionalized γ alumina (γ-Al2O3), prepared using green solvents, as an efficient bifunctional catalyst for CO2 fixation. The resulting guanidine-grafted γ-Al2O3 (Al-Gh) proved to be an excellent catalyst to prepare cyclic carbonates from epoxides and CO2 with high selectivity. The nitrogen-rich Al-Gh shows increased CO2 adsorption capacity compared to that of γ-Al2O3. The as-prepared catalyst was able to carry out CO2 fixation at 85 °C under atmospheric pressure in the absence of solvents and external additives (e.g., TBAI or KI). The material showed negligible loss of catalytic activity even after five cycles of catalysis. The catalyst successfully converted many epoxides into their respective cyclic carbonates under the optimized conditions. The gram-scale synthesis of commercially important styrene carbonates from styrene oxide and CO2 using Al-Gh was also achieved. Density functional theory (DFT) calculations revealed the role of alumina in activating the epoxide. This activation facilitated the chloride ion to open the ring to react with CO2. The DFT studies also validated the role of alumina in stabilizing the electron-rich intermediates during the course of the reaction.

Design Principle of Monoclinic NiCo2Se4 and Co3Se4 Nanoparticles with Opposing Intrinsic and Geometric Electrocatalytic Activity toward the OER.

Despite predictions of high electrocatalytic OER activity by selenide-rich phases, such as NiCo2Se4 and Co3Se4, their synthesis through a wet-chemical route remains a challenge because of the high sensitivity of the various oxidation states of selenium to the reaction conditions. In this work, we have determined the contribution of individual reactants behind the maintenance of conducive solvothermal reaction conditions to produce phase-pure NiCo2Se4 and Co3Se4 from elemental selenium. The maintenance of reductive conditions throughout the reaction was found to be crucial for their synthesis, as a decrease in the reductive conditions over time was found to produce nickel/cobalt selenites as the primary product. Further, the reluctance of Ni(II) to oxidize into Ni(III) in comparison to the proneness of Co(II) to Co(III) oxidation was found to have a profound effect on the final product composition, as a deficiency of ions in the III oxidation state under nickel-rich reaction conditions hindered the formation of a monoclinic "Co3Se4-type" phase. Despite its lower intrinsic OER activity, Co3Se4 was found to show geometric performance on a par with NiCo2Se4 by virtue of its higher textural and microstructural properties.

Highly Sensitive Upconverting Nanoplatform for Luminescent Thermometry from Ambient to Cryogenic Temperature.

Precise assessment of temperature is crucial in many physical, technological, and biological applications where optical thermometry has attracted considerable attention primarily due to fast response, contactless measurement route, and electromagnetic passivity. Rare-earth-doped thermographic phosphors that rely on ratiometric sensing are very efficient near and above room temperature. However, being dependent on the thermally-assisted migration of carriers to higher excited states, they are largely limited by the quenching of the activation mechanism at low temperatures. In this paper, we demonstrate a strategy to pass through this bottleneck by designing a linear colorimetric thermometer by which we could estimate down to 4 K. The change in perceptual color fidelity metric provides an accurate measure for the sensitivity of the thermometer that attains a maximum value of 0.86 K-1 . Thermally coupled states in Er3+ are also used as a ratiometric sensor from room temperature to ∼140 K. The results obtained in this work clearly show that Yb3+ -Er3+ co-doped NaGdF4 microcrystals are a promising system that enables reliable bimodal thermometry in a very wide temperature range from ultralow (4 K) to ambient (290 K) conditions.

Inception of Co3O4 as Microstructural Support to Promote Alkaline Oxygen Evolution Reaction for Co0.85Se/Co9Se8 Network.

Developing electrocatalysts with abundant active sites is a substantial challenge to reduce the overpotential requirement for the alkaline oxygen evolution reaction (OER). In this work, we have aimed to improve the catalytic activity of cobalt selenides by growing them over the self-supported Co3O4 microrods. Initially, Co3O4 microrods were synthesized through annealing of an as-prepared cobalt oxalate precursor. The subsequent selenization of Co3O4 resulted in the formation of a grainy rodlike Co3O4/Co0.85Se/Co9Se8 network. The structural and morphological analysis reveals the presence of Co3O4 even after the selenization treatment where the cobalt selenide nanograins are randomly covered over the Co3O4 support. The resultant electrode shows superior electrocatalytic activity toward OER in alkaline medium by delivering a benchmark current density of 10 mA/cm2geo at an overpotential of 330 mV. As a comparison, we have developed Co0.85Se/Co9Se8 under similar conditions and evaluated its OER activity. This material consumes an overpotential of 360 mV to deliver the benchmark current density, which signifies the role of the Co3O4 support to improve the electrocatalytic activity of Co0.85Se/Co9Se8. Despite having a low TOF value for Co3O4/Co0.85Se/Co9Se8 (0.0076 s-1) compared to Co0.85Se/Co9Se8 (0.0102 s-1), the improved catalytic activity of Co3O4/Co0.85Se/Co9Se8 is attributed to the presence of a higher number of active sites rather than the improved per site activity. This is further supported from the Cdl (double layer capacitance) measurements where Co3O4/Co0.85Se/Co9Se8 and Co0.85Se/Co9Se8 tender Cdl values of about 8.19 and 1.08 mF/cm2, respectively, after electrochemical precondition. As-prepared Co3O4/Co0.85Se/Co9Se8 also manifests rapid kinetics (low Tafel slope ∼ 91 mV/dec), long-term stability, low charge-transfer resistance, and 82% Faradaic efficiency for alkaline electrocatalysis (pH = 14). Furthermore, the proton reaction order (ρRHE) is found to be 0.65, indicating a proton decoupled electron transfer (PDET) mechanism for alkaline OER. Thus, the Co3O4 support helps in the exposure of more catalytic sites of Co0.85Se/Co9Se8 to deliver the improved catalytic activities in alkaline medium.

Design of Lanthanide-Doped Colloidal Nanocrystals: Applications as Phosphors, Sensors, and Photocatalysts.

The unique optical characteristics of lanthanides (Ln3+) such as high color purity, long excited-state lifetimes, less perturbation of excited states by the crystal field environment, and the easy spectral conversion of wavelengths through upconversion and downconversion processes have caught the attention of many scientists in the recent past. To broaden the scope of using these properties, it is important to make suitable Ln3+-doped materials, particularly in colloidal forms. In this feature article, we discuss the different synthesis strategies for making Ln3+-doped nanoparticles in colloidal forms, particularly ways of functionalizing hydrophobic surfaces to hydrophilic surfaces to enhance their dispersibility and luminescence in aqueous media. We have enumerated the various strategies and sensitizers utilized to increase the luminescence of the nanoparticles. Furthermore, the use of these colloidal nanoparticle systems in sensing application by the appropriate selection of capping ligands has been discussed. In addition, we have shown how the energy transfer efficiency from Ce3+ to Ln3+ ions can be utilized for the detection of toxic metal ions and small molecules. Finally, we discuss examples where the spectral conversion ability of these materials has been used in photocatalysis and solar cell applications.

Classification of Transitions in Upconversion Luminescence of Lanthanides by Two-Dimensional Correlation Analysis.

Upconversion luminescence bands from Yb3+/Er3+ codoped into a matrix such as NaGdF4 can show a very complex structure on account of multiple intra-f shell transitions occurring in the presence of random crystal fields. We demonstrate that two-dimensional correlation analysis, applied to such time-integrated luminescence spectra measured as a function of excitation power, allows us to gain substantial information about the states involved in transitions, without any additional theoretical input. The detailed correlation analysis allows us not only to identify the location of various transitions but further to club them into groups on the basis of their quantum mechanical origin, and finally subclassify the transitions with each group depending on whether they have a common initial or final state.

4-Mercaptobenzoic acid capped terbium(III)-doped CaF2 nanocrystals: a fluorescent probe for nitroaromatic pollutants.

The authors report on an energy transfer based fluorometric approach for the detection of nitroaromatic pollutants. This is achieved using 4-mercaptobenzoic acid (4-MBA)-capped CaF2:Tb3+ nanocrystals that were synthesized by a microwave procedure. 4-MBA acts as both a capping agent and a sensitizer for the Tb3+ ions in CaF2 host matrix. This approach is different from the earlier studies where Ce3+ is generally used as the sensitizer for the Ln3+ ions. The use of capping ligand as sensitizer has the feature that binding of nitroaromatics directly to the sensitizer can alter the energy transfer efficiency between the sensitizer and the Tb3+ ions. The fluorescent nanocrystal probe doped with 2% of Tb3+ displays green emission with a peak at 542 nm if photoexcited at 311 nm. The emission is quenched if the nanocrystals are exposed to nitroaromatic compounds such as 4-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol (picric acid), 4-nitrotoluene, 2,4-dinitrotoluene and 2,4,6-trinitrotoluene. These analytes also cause a (longwave/shortwave) shift in the excitation maxima which helps in identifying the individual nitroaromatic compound using single nanoprobe. The respective detection limits (by applying the 3σ/K criterion) are 0.86 µM, 0.83 µM, 0.78 µM, 0.36 µM, 1.5 µM, and 1.96 µM. Graphical abstract Schematic illustration of the use of 4-mercaptobenzoic acid (MBA)-capped CaF2:Tb3+ nanocrystals as a fluorescent nanoprobe for the detection of nitroaromatic analytes. The Tb3+ ions show strong green fluorescence via 4-MBA-induced ligand sensitization. The specific π interaction between 4-MBA capped CaF2 nanocrystals and nitroaromatics leads to reduction in the fluorescence intensity by inhibiting the energy transfer from 4-MBA to Tb3+ ion in CaF2 nanocrystals.

Ce3+ -Sensitized Tm3+ /Mn2+ -Doped NaYF4 Colloidal Nanocrystals: Intense Cool White Light from a Phosphor-Coated UV LED.

Colloidal NaYF4 :Ce3+ /Tm3+ /Mn2+ nanocrystals found to be an efficient single component phosphor to produce intense white light. The use of Mn2+ ions instead of green- and red-emitting Ln3+ ions is interesting as the later are expensive and less abundant. The single band blue emission of Tm3+ ions was combined with the broadband green-yellow emission of Mn2+ ions to produce strong white light emission using Ce3+ ions as excitation source. Interestingly, there is hardly any re-absorption of the blue emission by Mn2+ ions and the spectrum matches the commercial Ce3+ -doped yttrium aluminium garnet (YAG) phosphor coated over a blue LED. In addition, we have successfully incorporated the colloidal nanocrystals into a polymer matrix to make a nanocomposite as well as transparent films without altering the optical properties of the nanocrystals. The colloidal nanocomposite was coated over a UV LED to fabricate white LEDs. Finally, when the concentration of the dopant (Mn2+ ) ions was tuned the correlated color temperature (CCT) values varied between cool white light and daylight region.

Tuning the Energy Transfer Efficiency between Ce3+ and Ln3+ Ions (Ln=Tm, Sm, Tb, Dy) by Controlling the Crystal Phase of NaYF4 Nanocrystals.

NaYF4 is a superior host matrix to study the luminescence properties of lanthanide (Ln3+ ) ions. Ln3+ ions in hexagonal-phase NaYF4 (ß-phase) nanocrystals (NCs) exhibit strong luminescence via an upconversion process compared to cubic NaYF4 (α-phase) NCs. However, in Ce3+ /Ln3+ -doped NaYF4 NCs (Ln=Tm, Tb, Sm, Dy) the α-phase NaYF4 NCs shows strong luminescence compared to their counterpart ß-phase NCs despite the latter being much larger in size. This is attributed to comparatively large overlap between Ce3+ ions emission band with excited energy levels of those Ln3+ ions in α-phase compared to ß-phase NCs. This difference is attributed to different crystal-field splitting of Ce3+ ions 4f-5d band in different crystal environments of the α-phase (cubic crystal field environment) and ß-phase (trigonal prismatic with equatorials crystal field environment) NaYF4 NCs with respect to their barycenter. The enhanced luminescence from α-phase NaYF4 NCs is advantageous as they are prepared at a relatively lower temperature and shorter reaction times compared to ß-NaYF4 NCs.

A Highly Efficient UV-Vis-NIR Active Ln(3+)-Doped BiPO4/BiVO4 Nanocomposite for Photocatalysis Application.

In this Article, we report the synthesis of Ln(3+) (Yb(3+), Tm(3+))-doped BiPO4/BiVO4 nanocomposite photocatalyst that shows efficient photocatalytic activity under UV-visible-near-infrared (UV-vis-NIR) illumination. Incorporation of upconverting Ln(3+) ion pairs in BiPO4 nanocrystals resulted in strong emission in the visible region upon excitation with a NIR laser (980 nm). A composite of BiPO4 nanocrystals and vanadate was prepared by the addition of vanadate source to BiPO4 nanocrystals. In the nanocomposite, the strong blue emission from Tm(3+) ions via upconversion is nonradiatively transferred to BiVO4, resulting in the production of excitons. This in turn generates reactive oxygen species and efficiently degrades methylene blue dye in aqueous medium. The nanocomposite also shows high photocatalytic activity both under the visible region (0.010 min(-1)) and under the full solar spectrum (0.047 min(-1)). The results suggest that the photocatalytic activity of the nanocomposite under both NIR as well as full solar irradiation is better compared to other reported nanocomposite photocatalysts. The choice of BiPO4 as the matrix for Ln(3+) ions has been discussed in detail, as it plays an important role in the superior NIR photocatalytic activity of the nanocomposite photocatalyst.

Synthesis of Upconverting Hydrogel Nanocomposites Using Thiol-Ene Click Chemistry: Template for the Formation of Dendrimer-Like Gold Nanoparticle Assemblies.

The synthesis of upconverting hydrogel nanocomposites by base-catalyzed thiol-ene click reaction between 10-undecenoic acid capped Yb(3+)/Er(3+)-doped NaYF4 nanoparticles and pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) as tetrathiol monomer is reported. This synthetic strategy for nanocomposite gels is quite different from works where usually the preformed gels are mixed with the nanoparticles. Developing nanocomposites by surface modification of capping ligands would allow tuning and controlling of the separation of the nanoparticles inside the gel network. The hydrogel nanocomposites prepared by thiol-ene click reaction show strong enhancement in luminescence intensity compared to 10-undecenoic acid-capped Yb(3+)/Er(3+)-doped NaYF4 nanoparticles through the upconversion process (under 980 nm laser excitation). The hydrogel nanocomposites display strong swelling characteristics in water resulting in porous structures. Interestingly, the resulting nanocomposite gels act as templates for the synthesis of dendrimer-like Au nanostructures when HAuCl4 is reduced in the presence of the nanocomposite gels.

Strong Single-Band Blue Emission from Colloidal Ce(3+) /Tm(3+) -Doped NaYF4 Nanocrystals for Light-Emitting Applications.

An intense single-band blue emission at λ=450 nm is observed from Tm(3+) ions through Ce(3+) sensitization, for the first time, in colloidal Ce(3+) /Tm(3+) -doped NaYF4 nanocrystals. The intense Tm(3+) emission through broad-band excitation is advantageous for developing luminescent nanocomposites because they can be easily incorporated into polymers. The composites can easily be coated over UV light-emitting diodes (LEDs) to develop phosphor-based blue LEDs.

Methyl oleate-capped upconverting nanocrystals: a simple and general ligand exchange strategy to render nanocrystals dispersible in aqueous and organic medium.

We report a simple and general ligand exchange strategy to functionalize the nanocrystals with both hydrophobic and hydrophilic ligands. This is achieved by first capping the Er/Yb-doped NaYF4 nanocrystals with a weak ligand such as methyl oleate and subsequently ligand exchanged with various organic ligands which can strongly coordinate to the surface of the nanocrystals. The method involves only a simple stirring or sonication of the nanocrystals dispersion with the ligands of interest. Dicarboxylic acids such as sebacic acid, adipic acid, succinic acid, and malonic acid-functionalized nanocrystals which are difficult to achieve via thermal decomposition method were easily prepared by this ligand exchange strategy. In addition, low boiling point ligands like hexanoic acid can easily be coated over the surface of the Er/Yb-doped NaYF4 nanocrystals. Both size and shape of the nanocrystals were preserved after the ligand exchange process. The methyl oleate-capped Er/Yb-doped NaYF4 nanocrystals display strong upconversion emission after ligand exchanged with hydrophobic and hydrophilic molecules. The high stability of the nanocrystals after ligand exchange process is verified by performing time-dependent luminescent measurements at different pH, buffers, etc.

Intense NIR emissions at 0.8 µm, 1.47 µm, and 1.53 µm from colloidal LiYbF4:Ln(3+) (Ln = Tm(3+) and Er(3+)) nanocrystals.

We report on the synthesis of diamond shaped Ln(3+)-doped LiYbF4 (Ln = Tm and Er) nanocrystals with flat edges via the thermal decomposition method. Strong near-infrared emissions at 0.8 µm, 1.47 µm and 1.53 µm are observed from colloidal dispersions of Tm(3+)-doped and Er(3+)-doped LiYbF4 nanocrystals, respectively, under 0.98 µm diode laser excitation. The NIR emission intensities for Tm(3+)-doped and Er(3+)-doped LiYbF4 nanocrystals are comparable with those of the sodium counterpart NaYbF4, suggesting that LiYbF4 is also an excellent host matrix for lanthanide ions to obtain strong NIR emissions in colloidal solutions of LiYbF4 (Tm(3+) or Er(3+)) nanocrystals.

Highly luminescent colloidal Eu(3)+-doped KZnF(3) nanoparticles for the selective and sensitive detection of Cu(II) ions.

This article describes a green synthetic approach to prepare water dispersible perovskite-type Eu3+-doped KZnF3 nanoparticles, carried out using environmentally friendly microwave irradiation at low temperature (85 8C) with water as a solvent. Incorporation of Eu3+ ions into the KZnF3 matrix is confirmed by strong red emission upon ultraviolet (UV) excitation of the nanoparticles. The nanoparticles are coated with poly(acrylic acid) (PAA), which enhances the dispersibility of the nanoparticles in hydrophilic solvents. The strong red emission from Eu3+ ions is selectively quenched upon addition of CuII ions, thus making the nanoparticles a potential CuII sensing material. This sensing ability is highly reversible by the addition of ethylenediaminetetraacetic acid (EDTA), with recovery of almost 90% of the luminescence. If the nanoparticles are strongly attached to a positively charged surface, dipping the surface in a CuII solution leads to the quenching of Eu3+ luminescence, which can be recovered after dipping in an EDTA solution. This process can be repeated for more than five cycles with only a slight decrease in the sensing ability. In addition to sensing, the strong luminescence from Eu3+-doped KZnF3 nanoparticles could be used as a tool for bioimaging.

Microwave synthesis, photoluminescence, and photocatalytic activity of PVA-functionalized Eu3+-doped BiOX (X = Cl, Br, I) nanoflakes.

We report a facile microwave-assisted green synthetic route for colloidal poly(vinyl alcohol) (PVA)-coated europium (Eu(3+))-doped luminescent heavy metal bismuth oxyhalide (BiOX; X = Cl, Br, I) nanoflakes at low temperature and examine their structural, optical, and photocatalytic characteristics. PVA coating onto the surface of the nanoflakes endows them with hydrophilic nature. Both Eu(3+)-doped BiOCl and BiOBr nanoflakes exhibit strong optical properties related to Eu(3+) and Bi(3+) which are quenched in case of Eu(3+)-doped BiOI matrix. These results are supported by Eu(3+) photoluminescence lifetime values of 0.61 ms, 0.59 ms, and 8.9 µs, respectively. The former two matrices have quite similar crystal field environments as deduced from the asymmetric ratios of (5)D0 → (7)F2 (614 nm) and (5)D0 → (7)F1 (591 nm) transitions. In addition to possessing interesting photoluminescence properties, a comparison of the photocatalytic activity of Eu(3+)-doped BiOX (X = Cl, Br, I) nanoflakes, with corresponding estimated band gaps of 3.36, 2.74, and 1.67 eV has been evaluated using Rhodamine B (RhB) dye under visible light irradiation. The nanoflakes exhibited 100% dye degradation under visible light irradiation. Eu(3+)-doped BiOCl nanoflakes manifested higher photocatalytic efficiency compared to the other matrices following apparent first-order kinetics. Such a boost in efficiency is attributed to their high surface area to volume ratios, layered crystalline structures, indirect band gap nature, and ability to utilize broad bands in the solar spectrum.

Functionality Modulation Toward Thianthrene-based Metal-Free Electrocatalysts for Water Splitting.

The development of metal-free bifunctional electrocatalysts for hydrogen and oxygen evolution reactions (HER and OER) is significant but rarely demonstrated. Porous organic polymers (POPs) with well-defined electroactive functionalities show superior performance in hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Precise control of the active sites' local environment requires careful modulation of linkers through the judicious selection of building units. Here, a systematic strategy is introduced for modulating functionality to design and synthesize a series of thianthrene-based bifunctional sp2 C═C bonded POPs with hollow spherical morphologies exhibiting superior electrocatalytic activity. This precise structural tuning allowed to gain insight into the effects of heteroatom incorporation, hydrophilicity, and variations in linker length on electrocatalytic activity. The most efficient bifunctional electrocatalyst THT-PyDAN achieves a current density of 10 mA cm─2 at an overpotential (η10) of ≈65 mV (in 0.5 m H2SO4) and ≈283 mV (in 1 m KOH) for HER and OER, respectively. THT-PyDAN exhibits superior activity to all previously reported metal-free bifunctional electrocatalysts in the literature. Furthermore, these investigations demonstrate that THT-PyDAN maintains its performance even after 36 h of chronoamperometry and 1000 CV cycling. Post-catalytic characterization using FT-IR, XPS, and microscopic imaging techniques underscores the long-term durability of THT-PyDAN.