Conformal zinc sulfide coating of vertically aligned ZnO nanorods by two-step hydrothermal synthesis on wide bandgap seed layers for lead-free perovskite solar cells.

Vertically aligned ZnO nanorods (NRs) were grown hydrothermally on the wide bandgap (∼3.86 - 4.04 eV) seed layers (SLs) of grain size ∼162 ± 35 nm, prepared using ball-milled derived ZnO powder. The synthesized ZnO NRs were further decorated with ZnS nanocrystals to achieve a ZnO NR-ZnS core-shell (CS)-like nano-scaffolds by a subsequent hydrothermal synthesis at 70 °C for 1 h. UV-Vis-NIR spectroscopy, x-ray diffractometry (XRD), Raman spectroscopy and Field emission scanning electron microscopy (FESEM) coupled with Energy dispersive x-ray spectroscopy (EDX) analyses confirmed the formation of ZnS atop the vertically aligned ZnO NR arrays of ∼1.79 ± 0.17µm length and ∼165 ± 27 nm diameter. Transmission electron microscopy (TEM)/EDX analyses revealed that vertically aligned ZnO NRs (core dia. ∼181 ± 12 nm) arrays are conformally coated by an ultrathin ZnS (∼25 ± 7 nm) shell layer with a preferential ZnS{111}/ZnO{10-10}-like partial epitaxy. The ZnO NRs exhibited a sharp band edge near ∼384 nm having optical bandgap energy (Eg) of ∼3.23 eV. However, the ZnO NR-ZnS CS exhibited double absorption bands atEg∼ 3.20 eV (ZnO-core) andEg∼ 3.78 eV (ZnS-shell). The ZnS{111}/ZnO{10-10}-nano-scaffolds could be utilized to facilitate the enhanced absorption of UV photons as well as the radial junction formation between the Pb-free perovskite absorber and ZnS/ZnO NRs layers.

Empowering the Water Oxidation Activity of the Bimetallic Metal-Organic Framework by Annexing Gold Nanoparticles over the Catalytic Surface.

Electrocatalytic water splitting to an anodic oxygen evolution reaction (OER) and a cathodic hydrogen evolution reaction (HER) is believed to be the most important application for sustainable hydrogen generation. Being a four-electron, four-proton transfer process, the OER plays the main obstacle for the same. Therefore, designing an effective electrocatalyst to minimize the activation energy barrier for the OER is a research topic of prime importance. The metal-organic framework (MOF) with a highly porous network is considered an appropriate candidate for the OER in alkaline conditions. Apart from several MOFs, the bimetallic one has an advantageous electrocatalytic performance due to the synergistic electronic interaction between two metal ions. However, most bimetallic MOFs have an obstacle to electrocatalytic application due to their low conductive nature, and therefore, they possess a barrier for charge transfer kinetics at the interface. Surface functionalization via various nanoparticles (NPs) is believed to be the most effective strategy for nullifying the conductive issue. In this work, we have designed a CoNi-based bimetallic MOF that was surface-functionalized by Au NPs (Au@CoNi-Bpy-BTC) for the OER under alkaline conditions. Au@CoNi-Bpy-BTC required an overpotential of just 330 mV, which is 56 mV lower as compared to the pristine MOF. Impedance analysis confirms an improved conductivity and charge transfer at the interface, where Au@CoNi-Bpy-BTC possesses a lower Rct value than CoNi-Bpy-BTC materials. Moreover, the Au-decorated MOF shows an 8.5 times increase in the TOF value compared to the pristine MOF. Therefore, this noble strategy toward the surface functionalization of MOFs via noble metal NPs is believed to be the most effective strategy for developing effective electrocatalysts for electrocatalytic application in energy-related fields. Overall, this report displays an exceptional correlation between the decorated NPs over the MOF surface, which can regulate the OER activity, as confirmed by experimental analysis.

DNA-functionalized carbon quantum dots for electrochemical detection of pyocyanin: A quorum sensing molecule in Pseudomonas aeruginosa.

The electrochemical biosensing strategy for pyocyanin (PYO), a virulent quorum-sensing molecule responsible for Pseudomonas aeruginosa infections, was developed by mimicking its extracellular DNA interaction. Calf thymus DNA (ct-DNA) functionalized amine-containing carbon quantum dots (CQDs) were used as a biomimetic receptor for electrochemical sensing of PYO as low as 37 nM in real urine sample. The ct-DNA-based biosensor enabled the selective measurement of PYO in the presence of other interfering species. Calibration and validation of the PYO sensor platform were demonstrated in buffer solution (0-100 µM), microbial culture media (0-100 µM), artificial urine (0-400 µM), and real urine sample (0-250 µM). The sensor capability was successfully implemented for point-of-care (POC) detection of PYO release from Pseudomonas aeruginosa strains during lag and stationary phases. Cross-reactivity of the sensing platform was also tested in other bacterial species such as Bacillus subtilis, Escherichia coli, Klebsiella pneumoniae, Shigella dysenteriae, Staphylococcus aureus, and Streptococcus pneumoniae. Potential clinical implementation of the ct-DNA-based sensor was manifested in detecting the PYO in P. aeruginosa cultured baby diaper and sanitary napkin. Our results highlight that the newly developed ct-DNA-based sensing platform can be used as a potential candidate for real-time POC diagnosis of Pseudomonas aeruginosa infection in clinical samples.

Photo-Electrochemical Water Splitting Behavior of Directionally Aligned CdSe Quantum Dots on Copper(II) Benzene-1,3,5-Tricarboxylate Metal-Organic Frameworks (MOFs).

Herein, a facile synthesis protocol for the development of directional alignment of CdSe quantum dots (QDs) on the surface of Copper benzene-1, 3, 5-tricarboxylate (CuBTC) metal-organic frameworks (MOFs) was proposed. The sensitization of CdSe QDs with MOFs offered enhancement of light-harvesting properties in the visible region of the solar spectrum due to the broad absorption band of CdSe QDs. As a photo-anode, it has generated current density of ˜20 mA/cm² at 1.70 V (vs. Reversible hydrogen electrode (RHE)) during the photo-electrochemical water splitting in 1 M Na2S electrolyte. The present investigation demonstrates the directional attachment of CdSe QDs on CuBTC is beneficial in facilitating light-harvesting and photo-electrochemical properties of CuBTC MOFs.

Enhanced Photoelectrochemical Water Splitting Behaviour of Tuned Band Gap CdSe QDs Sensitized LaB6.

We report the fabrication of tuned band gap quantum dots sensitized LaB6 hybrid nanostructures and their application as a photoanode for photoelectrochemical water splitting. The lanthanum hexaboride (LaB6) obtained by molten salt electrolysis method is sensitized with different sized CdSe quantum dots, which form a multiple-level hierarchical heterostructure and such design enhance the light absorption and charge carrier separation, which in turn showed higher photocurrent density compared to that of pristine LaB6. When LaB6 is sensitized with CdSe quantum dots of different band gaps, which have the absorption in the green and red (530 and 605 nm) regions in visible light, developed a ten times higher photocurrent density (11.0 mA cm(−2)) compared to that of pristine LaB6 (0.5 mA cm(−2) at 0.75 V vs. Ag/AgCl) in 1 M Na2S electrolyte under illumination. These results prove that the tuned band gap quantum dots sensitized LaB6 heterostructures are an ideal candidate for a photoanode in solar water splitting applications.

Large-area (over 50 cm × 50 cm) freestanding films of colloidal InP/ZnS quantum dots.

We propose and demonstrate the fabrication of flexible, freestanding films of InP/ZnS quantum dots (QDs) using fatty acid ligands across very large areas (greater than 50 cm × 50 cm), which have been developed for remote phosphor applications in solid-state lighting. Embedded in a poly(methyl methacrylate) matrix, although the formation of stand-alone films using other QDs commonly capped with trioctylphosphine oxide (TOPO) and oleic acid is not efficient, employing myristic acid as ligand in the synthesis of these QDs, which imparts a strongly hydrophobic character to the thin film, enables film formation and ease of removal even on surprisingly large areas, thereby avoiding the need for ligand exchange. When pumped by a blue LED, these Cd-free QD films allow for high color rendering, warm white light generation with a color rendering index of 89.30 and a correlated color temperature of 2298 K. In the composite film, the temperature-dependent emission kinetics and energy transfer dynamics among different-sized InP/ZnS QDs are investigated and a model is proposed. High levels of energy transfer efficiency (up to 80%) and strong donor lifetime modification (from 18 to 4 ns) are achieved. The suppression of the nonradiative channels is observed when the hybrid film is cooled to cryogenic temperatures. The lifetime changes of the donor and acceptor InP/ZnS QDs in the film as a result of the energy transfer are explained well by our theoretical model based on the exciton-exciton interactions among the dots and are in excellent agreement with the experimental results. The understanding of these excitonic interactions is essential to facilitate improvements in the fabrication of photometrically high quality nanophosphors. The ability to make such large-area, flexible, freestanding Cd-free QD films pave the way for environmentally friendly phosphor applications including flexible, surface-emitting light engines.

Controlled growth of well-aligned GaS nanohornlike structures and their field emission properties.

Here, we report the synthesis of vertically aligned gallium sulfide (GaS) nanohorn arrays using simple vapor-liquid-solid (VLS) method. The morphologies of GaS nano and microstructures are tuned by controlling the temperature and position of the substrate with respect to the source material. A plausible mechanism for the controlled growth has been proposed. It is important to note that the turn-on field value of GaS nanohorns array is found to be the low turn-on field 4.2 V/µm having current density of 0.1 µA/cm(2). The striking feature of the field emission behavior of the GaS nanohorn arrays is that the average emission current remains nearly constant over long time without any degradation.

Ordered fabrication of luminescent multilayered thin films of CdSe quantum dots.

The surface of CdSe nanoparticles was functionalized with 11-hydroxyundecanoic acid (11-HUDA) during in situ preparation to afford stable and highly luminescent quantum dot (QD) solutions. The reactivity of the hydroxyl groups of 11-HUDA was then utilized in carbamate bond forming reactions with diisocyanate-bearing molecules that serve as linkers in the fabrication of the multilayered CdSe quantum dot films. The covalent bond formation readily proceeds at ambient temperature and results in a layer-by-layer formation of thin films comprised of photoluminescent CdSe nanoparticles separated by long chain organic connectors. The successive layer-by-layer approach can be repeated multiple times to get the desired thickness of QD films on glass or silicon substrates. The atomic force microscopy indicated the successful attachment of the QDs on the substrate surface. Importantly, the in situ functionalized CdSe nanoparticles preserve their stable and highly photoluminescent optical properties in the resulting multilayered films. Moreover, there is a gradual increase in the intensities of electronic absorption and photoluminescent bands of the QDs with increasing the number of layers, confirming successful fabrication of the multilayered films. The quantum yield (QY) of the 12-layered film was measured to be 6%. These findings are important for the development of QD-based optical, electronic and sensing devices that can harness the highly photoluminescent properties of these ordered and stable nanocomposite materials.

Chelating ligand-mediated synthesis of hollow ZnS microspheres and its optical properties.

Monodispersed hollow ZnS microspheres have been successfully synthesized by a facile ethylenediamine tetraacetic acid (EDTA) mediated hydrothermal route. The sizes of the hollow spheres vary from 1.5 to 3.5 microm when the reaction temperature varied from 130 to 230 degrees C. The formation of these hollow spheres is attributed to the oriented aggregation of ZnS nanocrystals around the gas-liquid interface between H(2)S and water. EDTA plays important role as chelating ligand and capping reagent, which regulates the release of Zn(2+) ions for the formation of ZnS hollow spheres. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis spectroscopy, photoluminescence, and Raman spectroscopy. The obtained ZnS hollow spheres show a sharp and photostable UV emission approximately 370 nm, which is attributed to the recombination process associated with interstitial sulfur vacancy.

Silica encapsulated Ni nanoparticles: variation of optical and magnetic properties with particle size.

Ni nanoparticles embedded in SiO2 matrix were prepared by sol-gel process. The molar percentages of Ni were varied from 2 to 20% of total SiO2 present in the matrix. Transmission electron microscope (TEM) images revealed that particle sizes varied from 8.0-15.7 nm at an annealing temperature of 773 K with variation of concentration. The optical absorption spectra revealed that the surface plasmon resonance (SPR) peak in the UV region of the spectrum shifted with the particle diameter (D) from that at 247.3 nm for D = 8.0 nm to 250.7 nm for D = 15.7 nm. In hysteresis loop measurements the magnetizations (M) of the nanocomposites also increased with higher Ni content in the matrix and did not saturate in the measuring limit of the magnetic filed (H) of 4 KOe. The anhysteric curves for different samples were analyzed with the law of approach to saturation (LAS). The zero field cooled (ZFC) and field cooled (FC) magnetization measurements at 50 Oe showed increasing broadening of the ZFC curve with the higher Ni content. To calculate the average blocking temperature ((T(B a distribution of the blocking temperatures (T(B)) was assumed to initiate theoretical fittings and it was found to be increasing with the Ni concentration in the matrix.

Surfactant-assisted route to synthesize well-aligned ZnO nanorod arrays on sol-gel-derived ZnO thin films.

Anisotropic growth of ZnO nanorod arrays on ZnO thin films was achieved at a temperature of 90 degrees C by a surfactant-assisted soft chemical approach with control over size and orientation. ZnO thin films with c-axis preferred orientation had been achieved by the sol-gel technique. Lengths, diameters, and the degree of alignment of the ZnO nanorods were controlled by changing the experimental parameters. It was observed that the surfactant was essential to restrict the lateral growth of the nanorods, whereas the pH level of the reaction medium controlled the length of the nanorods. On the other hand, the orientation of the nanorods depended on the crystalline orientation of the film as well as the pH of the reaction medium. Room-temperature photoluminescence studies revealed that the ZnO nanorods with the best alignment exhibited the best emission property. The ZnO nanorods exhibited a strong UV emission peak at approximately 3.22 eV, ascribed to the band-edge emission. The field emission studies of the well-aligned nanorod arrays exhibited a low turn-on field of 1.7 V/microm to get an emission current density of 0.1 microA/cm(2).