Subas Kumar Muduli

Mesoporous cerium oxide nanospheres for the visible-light driven photocatalytic degradation of dyes.

Summary A facile, solvothermal synthesis of mesoporous cerium oxide nanospheres is reported for the purpose of the photocatalytic degradation of organic dyes and future applications in sustainable energy research. The earth-abundant, relatively affordable, mixed valence cerium oxide sample, which consists of predominantly Ce7O12, has been characterized by powder X-ray diffraction, X-ray photoelectron and UV–vis spectroscopy, and transmission electron microscopy. Together with N2 sorption experiments, the data confirms that the new cerium oxide material is mesoporous and absorbs visible light. The photocatalytic degradation of rhodamin B is investigated with a series of radical scavengers, suggesting that the mechanism of photocatalytic activity under visible-light irradiation involves predominantly hydroxyl radicals as the active species.

Understanding the Origins of Nucleophilic Hydride Reactivity of a Sodium Hydride–Iodide Composite

Sodium hydride (NaH) has been commonly used as a Brønsted base in chemical syntheses, while it has rarely been employed to add hydride (H(-) ) to unsaturated electrophiles. We previously developed a procedure to activate NaH through the addition of a soluble iodide source and found that the new NaH-NaI composite can effect even stereoselective nucleophilic hydride reductions of nitriles, imines, and carbonyl compounds. In this work, we report that mixing NaH with NaI or LiI in tetrahydrofuran (THF) as a solvent provides a new inorganic composite, which consists of NaI interspersed with activated NaH, as revealed by powder X-ray diffraction, and both solid-state NMR and X-ray photoelectron spectroscopies. DFT calculations imply that this remarkably simple inorganic composite, which is comprised of NaH and NaI, gains nucleophilic hydridic character similar to covalent hydrides, resulting in unprecedented and unique hydride donor chemical reactivity.

Development of bis(arylimino)acenaphthene (BIAN) copper complexes as visible light harvesters for potential photovoltaic applications

Photovoltaics with dye-sensitized solar cells have been recognized as being promising for the utilization of sunlight to produce electricity and ‘solar chemicals’. One of the remaining unsolved challenges is the development of an affordable, robust dye that has a panchromatic light harvesting range and efficiently provides separated charges for the desired photochemistry. The most commonly employed molecular photosensitizers include the noble metal-based ruthenium and iridium complexes, synthetically challenging porphyrin derivatives, and expensive, functionalized polypyridine compounds. Here, we describe the development of Cu(I) dyes supported by bis(arylimino)acenaphthene (Ar-BIAN) ligands, which can be synthesized in fewer than three steps from affordable, commercially available reagents. The diamagnetic, homoleptic complexes have been characterized by a suite of spectroscopic and analytical methods and exhibit panchromatic light absorption extending to the near infrared (NIR) region. Remarkably, the crystal structure of a complex bearing an ortho-iodoarylimino substituent displays a unique, rhombically distorted square planar geometry around the Cu(I) center, for crystals isolated from two disparate solvent combinations. Density functional theory (DFT) calculations were performed to provide insights into the spectroscopic features and the unusual coordination sphere around the metal center, and allude to non-covalent interactions between the aromatic groups and among the iodide atoms. Preliminary studies were conducted to explore the application of these copper photosensitizers in dye-sensitized solar cells.

Benzyl Alcohol-Treated CH3NH3PbBr3 Nanocrystals Exhibiting High Luminescence, Stability, and Ultralow Amplified Spontaneous Emission Thresholds

We report the high yield synthesis of about 11 nm sized CH3NH3PbBr3 nanocrystals with near-unity photoluminescence quantum yield. The nanocrystals are formed in the presence of surface-binding ligands through their direct precipitation in a benzyl alcohol/toluene phase. The benzyl alcohol plays a pivotal role in steering the surface ligands binding motifs on the NC surface, resulting in enhanced surface-trap passivation and near-unity PLQY values. We further demonstrate that thin films from purified CH3NH3PbBr3 nanocrystals are stable >4 months in air, exhibit high optical gain (about 520 cm-1), and display stable, ultralow amplified spontaneous emission thresholds of 13.9 ± 1.3 and 569.7 ± 6 μJ cm-2 at one-photon (400 nm) and two-photon (800 nm) absorption, respectively. To the best of our knowledge, the latter signifies a 5-fold reduction of the lowest reported threshold value for halide perovskite nanocrystals to date, which makes them ideal candidates for light-emitting and low-threshold lasing applications.

Evolution of hydrogen by few-layered black phosphorus under visible illumination

Recently, a new class of two-dimensional black phosphorus (BP) with a visible direct band gap is predicted as a potential candidate for photo-catalysis applications. Here, we present the first experimental evidence of hydrogen (H2) evolution from aqueous solution by using BP (nanosheets and nanoparticles) under visible light illumination. Our experimental results describe that liquid phase exfoliated BP nanosheets and BP nanoparticles exhibit suitable energy level alignments for electron transfer and further proton reduction reactions in the solution under visible light illumination. Density functional theory (DFT) calculations predict that the H2 evolution activity of bilayer BP is independent of edge or center positions, which is unique in BP as compared to those of other 2D materials.

Modulating Excitonic Recombination Effects through One-Step Synthesis of Perovskite Nanoparticles for Light-Emitting Diodes

The primary advantages of halide perovskites for light-emitting diodes (LEDs) are solution processability, direct band gap, good charge-carrier diffusion lengths, low trap density, and reasonable carrier mobility. The luminescence in 3 D halide perovskite thin films originates from free electron-hole bimolecular recombination. However, the slow bimolecular recombination rate is a fundamental performance limitation. Perovskite nanoparticles could result in improved performance but processability and cumbersome synthetic procedures remain challenges. Herein, these constraints are overcome by tailoring the 3 D perovskite as a near monodisperse nanoparticle film prepared through a one-step in situ deposition method. Replacing methyl ammonium bromide (CH3 NH3 Br, MABr) partially by octyl ammonium bromide [CH3 (CH2 )7 NH3 Br, OABr] in defined mole ratios in the perovskite precursor proved crucial for the nanoparticle formation. Films consisting of the in situ formed nanoparticles displayed signatures associated with excitonic recombination, rather than that of bimolecular recombination associated with 3 D perovskites. This transition was accompanied by enhanced photoluminescence quantum yield (PLQY≈20.5 % vs. 3.40 %). Perovskite LEDs fabricated from the nanoparticle films exhibit a one order of magnitude improvement in current efficiency and doubling in luminance efficiency. The material processing systematics derived from this study provides the means to control perovskite morphologies through the selection and mixing of appropriate additives.

Enhanced Exciton and Photon Confinement in Ruddlesden–Popper Perovskite Microplatelets for Highly Stable Low‐Threshold Polarized Lasing

At the heart of electrically driven semiconductors lasers lies their gain medium that typically comprises epitaxially grown double heterostuctures or multiple quantum wells. The simultaneous spatial confinement of charge carriers and photons afforded by the smaller bandgaps and higher refractive index of the active layers as compared to the cladding layers in these structures is essential for the optical-gain enhancement favorable for device operation. Emulating these inorganic gain media, superb properties of highly stable low-threshold (as low as ≈8 µJ cm-2 ) linearly polarized lasing from solution-processed Ruddlesden-Popper (RP) perovskite microplatelets are realized. Detailed investigations using microarea transient spectroscopies together with finite-difference time-domain simulations validate that the mixed lower-dimensional RP perovskites (functioning as cladding layers) within the microplatelets provide both enhanced exciton and photon confinement for the higher-dimensional RP perovskites (functioning as the active gain media). Furthermore, structure-lasing-threshold relationship (i.e., correlating the content of lower-dimensional RP perovskites in a single microplatelet) vital for design and performance optimization is established. Dual-wavelength lasing from these quasi-2D RP perovskite microplatelets can also be achieved. These unique properties distinguish RP perovskite microplatelets as a new family of self-assembled multilayer planar waveguide gain media favorable for developing efficient lasers.

Investigating the feasibility of symmetric guanidinium based plumbate perovskites in prototype solar cell devices

In this work we have studied the feasibility of highly symmetric guanidinium (GA; CH6N3 +) cation in perovskite based solar cells. It is an alternative to the methyl ammonium (MA; CH3NH3 +) or formamidinium (FA; CH(NH2)2+) ions commonly utilized in the perovskite solar cells, may bring additional advantages due to its triad rotational symmetry and zero dipole moment (μ). We noticed that due to steric factors, GA preferably forms two-dimensional (2D) layer, where GA2PbI4 is favored monoclinic structure (E g = 2.5 eV) and the obtained device efficiency is η = 0.45%. This study provides a guideline for designing guanidinium based perovskite absorbers for solar cell devices. In addition, through further compositional engineering with mixed organic cations using GA may enhance the device performance.