Time-resolved Photoluminescence Studies Research Articles

Microwave-assisted synthesis of novel pyrazolyl sulfones and their antimicrobial evaluation and time-resolved photoluminescence studies

This article reports an efficient and practical microwave-assisted MMPP-promoted synthesis of novel pyrazolyl sulfones from the corresponding 4-(alkyl/cycloalkylthio)-1H-pyrazoles. The reaction of 4-(alkyl/cycloalkylthio)-1H-pyrazoles with magnesium bis(monoperoxyphthalate)hexahydrate (MMPP) as an oxidizing agent afforded the corresponding 4-(alkyl/cycloalkylsulfonyl)-1,3-disubstituted-1H-pyrazoles in 85–95% yield. This method's benefits include its straightforward operation, simple workup, and use of an inexpensive, halogen-free MMPP oxidant that is easy to use and reasonably stable. All synthesized pyrazolyl sulfones were examined against bacterial and fungal strains, and notable antimicrobial activity was demonstrated by a few of the compounds. In order to investigate the prospect of connecting compounds with the highest yield and antimicrobial activity with their opto-electronic properties, time-resolved photoluminescence investigations for compounds 5a, 5b, and 5d were conducted. The tunable spectrum was observed in the micro-second time domain in all three cases, with fluorescent lifetime found higher in the compound having methyl group, intermediate with phenyl group, and lowest with the p-nitrophenyl group. Our procedures will encourage additional research into the valuable properties of pyrazolyl sulfones now that they are widely available with the structural complexity illustrated here.

Enhancing and broadening the photoresponse of CdS nanowire by constructing core–shell heterostructure

Limited by the severe surface recombination and large bandgap, it is still a challenge to achieve a high-performance broad-spectrum photodetector based on CdS nanowires (NWs). In this work, the CdS/GeS core–shell heterostructure is constructed to enhance and broaden the photoresponse of CdS NWs. The CdS/GeS core–shell heterostructure NWs are prepared by the chemical vapor deposition method, exhibiting smooth surfaces, controlled shell thicknesses, and compositions. From the UV-Vis-near-infrared (NIR) diffuse reflectance spectrum, PL, and time-resolved photoluminescence studies, it is found that the surface recombination is weakened and the light absorption range is widened after the constructing core–shell heterostructure. When configured into photodetectors, the responsivity of the CdS/GeS core–shell heterostructure NWs is up to 76.8 A W−1, which is 10 folds higher than that of pristine CdS NWs. Furthermore, the photoresponse wavelength of the CdS/GeS core–shell heterostructure NWs is extended from 405 to 850 nm. The improved photodetection performance is attributed to the effective separation of photogenerated carriers at the heterostructure interface, weakened surface recombination, and excellent light absorption of the GeS shell. All results imply that constructing core–shell heterostructures is an effective strategy for constructing high-performance photodetectors.

Enhancing and broadening the photoresponse of CdS nanowire by constructing core–shell heterostructure

Limited by the severe surface recombination and large bandgap, it is still a challenge to achieve a high-performance broad-spectrum photodetector based on CdS nanowires (NWs). In this work, the CdS/GeS core–shell heterostructure is constructed to enhance and broaden the photoresponse of CdS NWs. The CdS/GeS core–shell heterostructure NWs are prepared by the chemical vapor deposition method, exhibiting smooth surfaces, controlled shell thicknesses, and compositions. From the UV-Vis-near-infrared (NIR) diffuse reflectance spectrum, PL, and time-resolved photoluminescence studies, it is found that the surface recombination is weakened and the light absorption range is widened after the constructing core–shell heterostructure. When configured into photodetectors, the responsivity of the CdS/GeS core–shell heterostructure NWs is up to 76.8 A W−1, which is 10 folds higher than that of pristine CdS NWs. Furthermore, the photoresponse wavelength of the CdS/GeS core–shell heterostructure NWs is extended from 405 to 850 nm. The improved photodetection performance is attributed to the effective separation of photogenerated carriers at the heterostructure interface, weakened surface recombination, and excellent light absorption of the GeS shell. All results imply that constructing core–shell heterostructures is an effective strategy for constructing high-performance photodetectors.

Effect of Lattice Disorder on Exciton Dynamics in Copper-Doped InP/ZnSexS1-x Core/Shell Quantum Dots.

InP/ZnSexS1-x core/shell quantum dots (QDs) with varying Cu concentrations were synthesized by a one-pot hot-injection method. X-ray diffraction and high-resolution transmission electron microscopy results indicate that Cu doping did not alter the crystal structure or particle size of the QDs. The optical shifts in UV-visible absorption and photoluminescence (PL) suggest changes in the electronic structure and induction of lattice disorder due to Cu doping. Ultrafast transient absorption spectroscopy (TAS) reveled that a higher Cu-doping level leads to faster charge carrier recombination, likely due to increased nonradiative decay from defect states. Time-resolved PL (TRPL) studies show longer average lifetimes of charge carriers with increased Cu doping. These findings informed the development of a kinetic model to better understand how Cu-induced disorder affects charge carrier dynamics in the QDs, which is important for emerging applications of Cu-doped InP/ZnSexS1-x QDs in optoelectronics.

Study of Intrachain Charge Transfer in a Blue Emissive Polyfluorene Random Copolymer.

Photophysics of a blue light-emitting fluorescent random copolymer, consisting of arylated polydioctylfluorene (aryl-F8), polydioctylfluorene (F8), and amine comonomers in a ratio of 80:15:5 is reported. In a solution of 10-6 M, solvatochromism in absorption and photoluminescence (PL) is observed with an increased lifetime of PL as the polarity of the solvent increases. Dual fluorescence is observed in the 10-9 M diluted solution, comprising a structured emission from a localized state in the aryl-F8 comonomer and a broad emission peak from the charge-transfer (CT) state at a lower energy. Emission wavelength-dependent time-resolved photoluminescence studies in different polar media confirm the presence of the emissive intrachain CT state in this copolymer. Analyzing the PL decay kinetics, we calculated the formation rate of the intrachain CT state to be ∼3.0 × 109 s-1. Repopulation of the localized state from the CT state is observed in the lower polarity medium with a rate of 7 × 108 s-1, which is almost absent for the large Stokes-shifted CT emission in the higher polarity medium. Along with the fundamental understanding of the photophysics of the random copolymer, this study suggests that the emission spectrum can be tailored by the concentration of polymer and the polarity of surrounding media.

Synthesis and Photophysical Properties of Bipolar Compound: Triphenylamine/Diazafluorene-Carbazole.

Carbazole and triphenylamine, are two well-known hole transporting units that are attached to electron transporting unit 4,5-diazafluorene in a fascinating way to bring out non-planar configuration of a molecule. The synthesized compound exhibits good thermal stability (Td > 515°C) and high glass transition temperature (Tg, 191°C). Optical bandgap (Egopt) obtained from solid state absorption spectra was calculated to be 2.93eV. Solid state photoluminescence spectra displays the emission maxima at 473nm. The emission characteristics of the compound observed in solvents of different polarity confirms the existence of intramolecular charge transfer in their excited state. Density functional theory studies reveal that HOMO and HOMO-1 localized on triphenylamine is spatially separated from LUMO of 4,5-diazafluorene, which manifest its bipolar character. The realization of long lived charge separated state upon photo-excitation from time resolved photoluminescence studies ascertains the charge transfer from triphenylamine to 4,5-diazafluorene. The experimental and theoretical analysis of the compound proved it to be a promising candidate for the fabrication of OLED devices.

Hydrothermally Synthesized Z-Scheme Nanocomposite of ZIF-9 Modified MXene for Photocatalytic Degradation of 4-Chlorophenol.

4-Chlorophenol (4CP) is a well-known environmental contaminant often detected in wastewater, generally arising from industrial processes such as chemical manufacture, pharmaceutical production, and pesticide formulation. 4CP is a matter of great concern since it is persistent and has the potential to have harmful impacts on both aquatic ecosystems and human health, owing to its hazardous and mutagenic properties. Hence, degradation of 4CP is of utmost significance. This research investigates the photocatalytic degradation of 4CP using a novel Z-scheme heterojunction nanocomposite composed of MXene and ZIF-9. The nanocomposite is synthesized through a two-step hydrothermal method and thoroughly characterized by using XRD, SEM, UV-visible spectroscopy, zeta potential, and electrochemical impedance spectroscopy studies, confirming successful fabrication with improved surface properties. The comparative photocatalytic degradation studies between pristine materials and the nanocomposite were performed, and significant enhancement in performance was observed. The effect of pH on the degradation efficiency is also explored and correlated with the surface charge. The Z-scheme photocatalysis mechanism is proposed, which is supported by time-resolved photoluminescence studies and scavenger experiments. The reusability of the nanocomposite is also evaluated. The study contributes to the development of efficient and sustainable photocatalysts for wastewater treatment.

ZnO/ZIF-8 nanocomposite for orange G dye degradation: synthesis, characterization, photocatalytic activity, and mechanism

Textile dyes are one of the dominant reasons for water pollution. Among these dyes, Orange G is toxic, carcinogenic, and non-biodegradable and can cause a severe threat to humans and marine life. Therefore, in this present work, a novel photocatalyst was synthesized, and systematic degradation of Orange G dye was investigated. The novel ZnO/ZIF-8 nanocomposite has been successfully synthesized via a two-step method, thermal decomposition for ZnO and wet-chemical method for ZnO/ZIF-8 nanocomposite. The band gap of the nanocomposite was calculated using a KM plot and found to be 3.5 eV. The surface charge of the materials was examined using zeta potential measurement, which was found to be suitable for dye degradation. The recombination time of the materials was investigated using Time-Resolved Photoluminescence (TRPL) study, and it was found that nanocomposite has a lower recombination rate than pristine materials. The degradation efficiency of materials towards Orange G dye was calculated to be ∼95% after 120 min illumination. The photocatalysis mechanism was proposed on the basis of Mott–Schottky measurements, which were supported by the scavenger test. Furthermore, to evaluate the reusability of the nanocomposite, a photocatalytic experiment was conducted several times. The ZnO/ZIF-8 nanocomposite could be used for the degradation of textile dye wastewater.

Shedding Light on Host-to-Yb3+ Energy Transfer in Cs2AgBiBr6:Yb3+ (nano)crystals.

The optical properties of Cs2AgBiBr6 double perovskite nanocrystals have attracted considerable attention as lead-free alternatives to lead halide perovskites. A promising strategy to create additional flexibility in the emission color is doping lanthanide ions into Cs2AgBiBr6. Incorporating Yb3+ in the lattice has been shown to give rise to near-infrared (NIR) emission, but the energy transfer mechanism remained unclear. Here, we report on the luminescence and sensitization mechanism of Yb3+ in Cs2AgBiBr6 nano- and microcrystals. We observe that the incorporation of Yb3+ in the host lattice does not strongly affect the broadband red emission of the Cs2AgBiBr6 host but does give rise to an additional and characteristic ∼1000 nm NIR line emission from Yb3+. Temperature-dependent and time-resolved photoluminescence studies of undoped and Yb-doped Cs2AgBiBr6 reveal that the energy transfer does not take place through the red emissive state of the Cs2AgBiBr6 host. Instead, there is a competition between relaxation to the red-emitting state and trapping of the photoexcited charge carriers on Yb3+. Trapping on Yb3+ subsequently results in a charge transfer state that relaxes to the 2F5/2 excited state of Yb3+, followed by NIR narrow line f-f emission to the 2F7/2 ground state.

Exciton localization and dynamics in GaNAsP nanowires

This work investigates exciton localization and dynamics in semiconductor GaNAsP nanowires (NWs) with varying nitrogen concentrations. Through detailed time-resolved photoluminescence studies, we identify a nitrogen composition-dependent difference in exciton transfer between localized states formed due to alloy disorder. With [N] = 0.1%, the localized states exhibit cluster-like, non-interacting behavior, whereas at [N] = 1.1%, a continuous band of localized states is observed. Additionally, the phosphorous incorporation in the NWs appears to enhance the exciton spatial confinement compared to behaviors observed in phosphorous-free GaNAs NWs, emphasizing the role of the alloy composition in the nature of exciton localization. Temperature is highlighted as a significant factor affecting exciton mobility, enabling efficient transfer between the localized states at higher temperatures. This, in turn, influences exciton lifetimes. Our findings, therefore, shed light on the nature of exciton dynamics in GaNAsP NWs, enriching our understanding of these materials and paving the way for their applications in optoelectronics.

Radiative pumping in a strongly coupled microcavity filled with a neat molecular film showing excimer emission.

Strong light-matter interactions have attracted much attention as a means to control the physical/chemical properties of organic semiconducting materials with light-matter hybrids called polaritons. To unveil the processes under strong coupling, studies on the dynamics of polaritons are of particular importance. While highly condensed molecular materials with large dipole density are ideal to achieve strong coupling, the emission properties of such films often become a mixture of monomeric and excimeric components, making the role of excimers unclear. Here, we use amorphous neat films of a new bis(phenylethynyl anthracene) derivative showing only excimer emission and investigate the excited-state dynamics of a series of strongly coupled microcavities, with each cavity being characterised by a different exciton-photon detuning. A time-resolved photoluminescence study shows that the excimer radiatively pumps the lower polariton in the relaxation process and the decay profile reflects the density of states. The delayed emission derived from triplet-triplet annihilation is not sensitive to the cavity environment, possibly due to the rapid excimer formation. Our results highlight the importance of controlling intermolecular interactions towards rational design of organic exciton-polariton devices, whose performance depends on efficient polariton relaxation pathways.

(Invited) Limitation of Molecular Twisting: Upgrading a Donor-Acceptor Dye to Drive H2 Evolution

Dye-sensitized photoelectrochemical cells (DSPECs) have attracted wide attention to convert solar energy into high-energy chemicals. A DSPEC consists of a photoanode performing the oxidation half reaction and aphotocathode performing the reduction half reaction. In this presentation I will demonstrate how the performance of a dye-sensitized photocathode can be manipulated to enhance performance and even produce hydrogen! We have used a state- of-the-art dye (D-A P1 dye) on the surface of optimized NiO, and co-adsorbed myristic acid (Tetradecanoic Acid), which has a carboxyl anchoring group and a long apolar alkyl chain. Time-resolved photoluminescence and Density Functional Theory studies show that twisting lowers the energy levels of the photoexcited D-A dye, while twisting is inhibited in case myristic acid is co-adsorbed on the NiO surface. The presence of myristic acid also favors light-induced charge separation, as apparent from femtosecond transient absorption, and increases the apparent photocurrent. Very interestingly, only in the presence of myristic acid, light-induced H2 evolution is observed in aqueous media, despite the absence of a H2 evolution catalyst. We assign the H2 generation to a synergetic effect of inhibited twisting of the D-A dye radical anion increasing its electrochemical potential, combined with charge transfer and conversion of H+ on the hydroxylated NiO surface. Our work illustrates the importance of understanding effects of photoinduced intramolecular twisting and demonstrates that control thereof offers a simple design approach for efficient solar fuel devices.

(Invited) Interlayer Excitons in Two-Dimensional Perovskite/Monolayer Transition Metal Dichalcogenide Heterostructures

The emergence of two-dimensional (2D) materials has intrigued a great deal of research on novel physical phenomena and various functional applications due to their particular crystal structures and reduced dimensionality. Unlike 3D materials, bulks of 2D materials can be easily thinned to atomic thickness by mechanical exfoliation and atomically thin 2D materials can be arbitrarily stacked to form vertical van der Waals (vdW) heterostructures, which could inherit the unique characteristics of the constituent layers and even exhibit new properties not possessed by them. Particularly, when type-Ⅱ vdW heterostructures are excited, the positive and the negative charges would reside in the different layers after the charge transfer but be limited within a short distance due to the strong quantum confinement effect of 2D materials, leading to strong Coulomb interaction and the formation of interlayer excitons (IXs). IXs are generally equipped with orientated dipole moment and long lifetime, making them ideal media for the future interconnects between optical transmission and electronic computation. Currently, studies on IXs are mainly focused on the vdW heterostructures formed by monolayers of transition-metal dichalcogenides (TMDs). Here, I will first talk about vdW heterostructures formed by 2D perovskites and TMDs for studying IXs. Stacking different kinds of 2D perovskites and TMDs, formation of IXs is confirmed by excitation-power-, temperature-, electric-field-dependent and time-resolved photoluminescence (PL) studies. Notably, robust IX emission can be observed regardless of the stacking sequence and geometric alignment of the constituent layers, showing great advantages over the TMD/TMD vdW heterostructures, which require special twist-angle and thermal annealing. Then, I would like to give a brief introduction on widely tuning the IX emission energy by changing the layer number of the 2D perovskite or the TMD, which shed light on the application of 2D perovskite/TMD vdW heterostructures in broad-spectrum optoelectronics. Furthermore, I would like to next talk about how the selection of organic chains in 2D perovskites influences the properties of the IXs. By using chiral 2D perovskites, the IX emission shows substantial circular polarization and the polarization direction is only related to the chirality of the molecules regardless of the excitation scheme or any other external field, which could open up new passages for controlling valley- or spin-polarization of IXs. By introducing molecules with different dielectric constants, the dielectric screening strength in the vdW heterostructure is changed and hence the binding energy of the IXs is also modified, which offers great opportunities for exploiting tunable excitonic devices and studying exciton condensation. Finally, I will also introduce IX as a non-destructive tool for probing the local phase transition at the surface of the 2D perovskite (BA)2PbI4 flakes. By spatially PL mapping of the (BA)2PbI4/WSe2 heterostructure, two different IX species can be observed to distinguish the low-temperature and the high-temperature phase respectively.

Static anti-solvent treatment on lead iodide in two-step deposition of methylammonium lead iodide perovskite thin films

Static anti-solvent treatment is rarely employed for perovskite thin film fabrication, even though this method is dependent only on fewer thin film growth parameters as compared to the dynamic anti-solvent application. Thus, studies on the influence of static anti-solvent treatment on the properties of perovskite thin films is important to gain insight to the growth processes, which is very scarce as well. In this study, we investigate the static anti-solvent treatment to tailor the morphology of Lead Iodide (PbI2) thin films for the fabrication of precursor-free Methylammonium Lead Iodide (MAPI) perovskite thin films through the two-step deposition method using Chlorobenzene as an anti-solvent. Remarkable influence of the anti-solvent loading time on the film morphology of PbI2 and MAPI thin films is observed. The crystallinity of PbI2 decreases upon increasing the anti-solvent loading time. A complete conversion of the precursors to MAPI along with the largest grain size are attained even at short loading times, ∼5s. Grain size does not increase considerably at higher loading times. Linear absorption studies on MAPI thin films show an increase in the Urbach energy with an increase in the loading time, which indicates an increase in the defect density. The increase in defect density with anti-solvent loading time is attributed to the concurrent decrease in the crystallinity of the PbI2 thin film. Steady-state and time-resolved photoluminescence (PL) studies performed on the MAPI thin films show highest PL intensity and life time at an optimum anti-solvent loading time (∼5s), which arises due to the trade off between largest grain size and lowest defect density. These observations not only highlights the need for an optimum crystallinity in the PbI2 thin films for the fabrication of superior quality MAPI thin films but also infers an optimum static anti-solvent loading time as the increase in grain size and life time enhances the device performance while an increase in defect density degrades the performance.

An AIE active anthracene-based Schiff base probe for “turn-on” detection of Cu2+ ions: Demonstrations with nanostructural investigations, DFT, cellular imaging, and real water analysis

An aggregation induced emission (AIE) active anthracene-based Schiff base probe “(2-((anthracen-9-ylmethylene) amino) phenol); AP” was synthesized via one-pot reaction and utilized in “turn-on” detection of Cu2+ ions. Ultraviolet–visible and photoluminescence (UV–vis/PL) interrogations confirm the AIE between 0 and 99 % water fraction (fw) and high selectivity of AP to Cu2+. PL studies establish the linear regression of Cu2+ between 0 and 24 µM with a detection limit (LOD) of 53.2 nM. The Job plot and high-resolution mass (HR-mass) data affirm 2:1 stoichiometry and the association constant (Ka) value appraised as 1.88 × 10−4 M−2. Time-resolved photoluminescence (TRPL) studies reveal decay kinetics of AIE, Cu2+ sensors and complex's reversibility. Moreover, 1H NMR titration and density functional theory (DFT) investigations identify the binding mode, π-π stacking in AIE, AP − Cu2+ − AP* excimer formation, band gap variations and involvement of photoinduced electron transfer (PET) and chelation enhanced fluorescence (CHEF) mechanism. Crystallinity and nanostructural variations of AIE and Cu2+ sensors are investigated by using powder-X-ray diffraction (PXRD), scanning electron microscope (SEM), transmission electron microscope (TEM), and dynamic light scattering (DLS). AIE and Cu2+ sensory method are validated by MDA-MB-231 cellular imaging studies. Finally, real water-based titrations show nanomolar LODs and recoveries > 97 % with RSDs < 3.5 %.

Local Structure and Speciation-Driven UO22+ → Sm3+ Energy Transfer for Enhanced Luminescence in Li2B4O7.

Herein, we report the uranyl sensitization of Sm3+ emissions in uranium-codoped Li2B4O7:Sm3+ phosphor. The uranyl speciation in codoped [Sm, U] LTB samples was determined by synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy that revealed two coordination shells for U(VI) ions with bond distances of U-Oax (∼1.81 Å) and U-Oeq (∼2.30 Å). EXAFS fitting suggested that the uranyl moiety is present as pentagonal bipyramids (UO7) and hexagonal bipyramids (UO8) with five and six equatorial oxygen ligands, respectively. The alteration of the local structure of Sm3+ from [SmO4] to [SmO7] polyhedra and the changes in the coordination number of equatorial oxygen for uranyl were observed with different codoping concentrations of Sm3+ and uranium. Density functional theory (DFT) calculations suggested the lowering of defect formation energy for Li vacancies on codoping of Sm and U. Hence, we proposed the increase of the equatorial coordination number of UO22+ on the increase in the lithium vacancies in LTB. In addition, DFT supported the feasibility of efficient energy transfer (ET) due to the overlap of uranium and Sm3+ excited state levels. The influence of the same on the spectral features and UO22+ → Sm3+ energy transfer was investigated by time-resolved photoluminescence (PL) studies. The ET efficiency from the UO22+ to Sm3+ was 70.5% in 0.5 mol % codoped [Sm, U] LTB samples. The correlation of EXAFS and luminescence properties indicated a red shift in vibronic features of uranyl emission with increase in the equatorial coordination of the uranyl moiety from five to six. Additionally, a higher probability of ET was observed for uranyl speciation as UO8 hexagonal bipyramids. Temperature-dependent emissions and decay profiles were collected under uranyl excitation to investigate the thermal dependence of ET. A high energy barrier (Ea ∼ 4027 cm-1) was evaluated for the thermal quenching of Sm3+ emissions. This work provides insights into the modulation of luminescence and ET efficiency via structural changes in uranyl and Sm local environment in LTB phosphor.

CuBO2 : A Potential Alternative for NiO as a Hole Acceptor Layer.

P-type metal oxides, and in particular NiO, are typically used as hole accepting layers in dye-sensitized photocathodes. Delafossites (CuMO2 ) with M=B, Al, Cr or Ga have recently been proposed as attractive substitutes for NiO, with theoretically a higher hole mobility than NiO, therefore allowing a higher efficiency when the photocathode is applied in solar to fuel devices. We have experimentally validated the photoelectrochemical performance of photocathodes consisting of nanoporous CuBO2 (CBO) on Fluorine-doped Tin Oxide substrates, photosensitized with a light absorbing P1 dye. Femtosecond transient absorption and time-resolved photoluminescence studies show that light-induced hole injection occurs from the P1 dye into the CBO in a few ps, comparable to the time constant observed for NiO-based photocathodes. Importantly, the CBO-based photocathode shows significantly slower charge recombination than the NiO-based analogue. These results illustrate the promise of CBO as a p-type semiconductor in solar energy conversion devices.

Evidence for an Interface of Hybrid Cocatalysts Favoring Photocatalytic Hydrogen Evolution Kinetics.

Hybrid cocatalysts have great application potential for improving the photocatalytic hydrogen evolution performance of semiconductors. The interfaces between components of hybrid cocatalysts make a great contribution to the improvement, but the associated mechanisms remain unclear. Herein, we prepared and tested three comparative CdS-based photocatalysts with NiS, NiS/Ni9S8, and Ni9S8 as the cocatalysts separately. The emphasis is placed on investigating the effect of the NiS/Ni9S8 interfaces on the photocatalytic hydrogen evolution performance of CdS. NiS/Ni9S8 exhibits a higher ability than NiS and Ni9S8 in making CdS a more active photocatalyst for water splitting. It shows that NiS, NiS/Ni9S8, and Ni9S8 perform similarly in terms of promoting the charge transfer and separation of CdS based on steady-state and time-resolved photoluminescence studies. At the same time, the linear sweep voltammetry and electrochemical impedance spectroscopy tests combined with the density functional theory calculations reveal that the component interfaces of NiS/Ni9S8 enable us to lower the water splitting activation energy, the charge-transfer resistance from the cocatalyst to sacrificial agent, and hydrogen adsorption Gibbs free energy. It is evidenced from this work that component interfaces of hybrid cocatalysts play a vital role in accelerating the dynamics of hydrogen evolution reactions.

Improved charge transport kinetics in PbBi2Nb2O9 photocatalysts: Comparative time-resolved recombination study with N-doped TiO2

(100) layered Aurivillius-phase perovskite single-phase PbBi2Nb2O9 (PBNO) photocatalyst was reported to be an efficient photocatalyst as compared to the conventionally known visible light photocatalyst of N doped TiO2 (NTO). We report here the specific photoluminescence studies of PBNO to understand its improved photocatalytic property. We have synthesized PBNO and NTO photocatalyst films. Further, their structural, optical and photocatalytic degradation properties have been studied. PBNO demonstrated superior methylene blue degradation as compared to NTO, under visible light photons. The steady-state and time-resolved photoluminescence (PL) studies were specially utilized at characterization tool to understand reason of the high photocatalytic activity of PBNO. We analyzed how high crystallinity of PBNO, and the longer recombination lifetime due to charge separation during photocatalytic reaction yields improved activity in PBNO as compared to NTO. Accordingly, mechanistic scheme for methylene blue photodegradation under solar light photons has been proposed. This study also indicates importance of photoluminescence study for photocatalysts.

Photo-Induced Super-Hydrophilicity of Nano-Calcite @ Polyester Fabric: Enhanced Solar Photocatalytic Activity against Imidacloprid.

The present study is pertinent to photo-induced, hydrophilic, nano-calcite grown onto the mercerized surface of polyester fabric (PF), treated with UV (10-50 min) and visible light (1-5 h) in addition to its photocatalytic application. The wicking method has been employed to select the most hydrophilic sample of fabric upon irradiation. The micrographs obtained by scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy indicated the erosions occurring at the surface of nano-calcite after UV light irradiation, maintaining the crystallinity of the photocatalyst. The surface charge has been measured for as-fabricated and irradiated nano-calcite @ PF for the development of high negative zeta potential after UV light irradiation (-24.6 mV). The irradiated nano-calcite @ PF exhibited a significant change in its contact angle, and the wetting property was enhanced to a considerable extent on UV (55.32°) and visible light irradiation (79.00°) in comparison to as-fabricated nano-calcite @ PF (137.54°). The irradiated samples of nano-calcite @ PF delineated the redshift in harvesting of solar spectrum, as revealed by diffuse reflectance spectroscopy comparative spectra. Additionally, the band gap of untreated nano-calcite was found to be 3.5 eV, while UV- and visible light-irradiated PF showed a reduction in band gap up to 2.95 and 3.15 eV upon UV and visible light irradiation. The photocatalytic efficiency of mesoporous nano-calcite was evaluated by photocatalytic degradation of imidacloprid as the probe pollutant. Higher solar photocatalytic degradation of imidacloprid (94.15%) was attained by UV light-irradiated nano-calcite @ PF. The time-resolved photoluminescence study has verified the high photocatalytic activity of UV light-irradiated nano-calcite @ PF for the generation of high concentration of hydroxyl radicals. The highly efficient reusability of a nano-calcite-based solar photocatalytic reactor has been observed for 10 cycles of treatment of imidacloprid bearing wastewater. The enhanced photocatalytic activity of UV light-exposed (20 min), superhydrophilic, nano-calcite @ PF for mineralization of pollutants suggests it to be an efficient solar photocatalyst for environmental applications.