Hollow aluminum microspheres with high mass extinction coefficients in the long wave infrared.

Previous electromagnetic computations of multilayered dielectric/metallic spheres identified the ideal dimensions and composition for achieving optimized mass extinction coefficients (m2/g). A hollow metallic sphere, with a thin metallic shell, is one such example of a spherical structure that can theoretically achieve high mass extinction coefficients in the long wave infrared (LWIR) region (8-12 µm). To this end, we endeavored to demonstrate a cost-effective and scalable manufacturing approach for synthesizing and experimentally validating the mass extinction coefficients of hollow metallic spheres. Specifically, we detail a novel approach for fabricating hollow aluminum spheres using radio frequency (RF) magnetron sputter deposition. Sacrificial high-density polyethylene polymer microspheres were used as substrates for the deposition of thin layers of aluminum. The core shell structures were subsequently thermally processed to form the hollow micron sized aluminum shells. The mass extinction coefficients of the hollow aluminum spheres were subsequently measured and compared to computational results. A strong agreement between experimental and theoretical predictions was observed. Finally, the LWIR mass extinction coefficients of the hollow spheres were compared to high aspect ratio brass flakes, a common pigment used for LWIR attenuation, and other materials and geometries that are used for LWIR filtering applications. This comparison of both performance and availability revealed that the fabricated hollow aluminum spheres exhibited competitive LWIR properties using a more scalable and cost-effective manufacturing approach.

Iterative design of multilayered dielectric microspheres with tunable transparency windows.

Suspensions of microparticles dispersed in air or liquids are useful for designing media with desirable optical extinction properties within the visible or infrared spectrum. We describe here a numerical iterative optimization algorithm used to design multilayered concentric dielectric spheres with prescribed optical scattering properties. Our method integrates a computationally efficient rigorous electromagnetic solver, based on Mie theory, within an optimization loop to determine specific particle configurations that best meet a desired optical response. In particular, we show that this method can be used to design all-dielectric spherical particles that possess narrow tunable transparency windows while removing any angular dependency on the optical response.

Anion-Redox Mechanism of MoO(S2)2(2,2'-bipyridine) for Electrocatalytic Hydrogen Production.

Redox processes of molybdenum-sulfide (Mo-S) compounds are important in the function of materials for various applications from electrocatalysts for the hydrogen evolution reaction (HER) to cathode materials for batteries. Our group has recently described a series of Mo-S molecular HER catalysts based on a MoO(S2)2L2 structural motif. Herein, reductive pathways of MoO(S2)2bpy (Mo-bpy) (bpy = 2,2'-bipyridine) are presented from both experimental and theoretical studies. We tracked chemical reduction of Mo-bpy with UV-vis spectroscopy using sodium napthalenide (NaNpth) as the reducing agent and found that Mo-bpy undergoes anionic persulfide reduction to form the tetragonal Mo(VI) complex [MoOS3]2-. We also identified silver mercury amalgam as an inert working electrode (WE) for spectroectrochemical (SEC) studies. UV-vis spectra in the presence of trifluoroacetic acid with an applied potential confirmed that Mo-bpy maintains its structure during catalytic cycling. Finally, theoretical catalytic reaction pathways were explored, revealing that Mo=O may function as a proton relay. This finding together with the observed anion reduction as the redox center is of broad interest for amorphous Mo-S (a-MoSx) electrocatalytic materials and anion-redox chalcogel battery materials.

[MoO(S2)2L]1- (L = picolinate or pyrimidine-2-carboxylate) Complexes as MoSx-Inspired Electrocatalysts for Hydrogen Production in Aqueous Solution.

Crystalline and amorphous molybdenum sulfide (Mo-S) catalysts are leaders as earth-abundant materials for electrocatalytic hydrogen production. The development of a molecular motif inspired by the Mo-S catalytic materials and their active sites is of interest, as molecular species possess a great degree of tunable electronic properties. Furthermore, these molecular mimics may be important for providing mechanistic insights toward the hydrogen evolution reaction (HER) with Mo-S electrocatalysts. Herein is presented two water-soluble Mo-S complexes based around the [MoO(S2)2L2]1- motif. We present 1H NMR spectra that reveal (NEt4)[MoO(S2)2picolinate] (Mo-pic) is stable in a d6-DMSO solution after heating at 100 °C, in air, revealing unprecedented thermal and aerobic stability of the homogeneous electrocatalyst. Both Mo-pic and (NEt4)[MoO(S2)2pyrimidine-2-carboxylate] (Mo-pym) are shown to be homogeneous electrocatalysts for the HER. The TOF of 27-34 s-1 and 42-48 s-1 for Mo-pic and Mo-pym and onset potentials of 240 mV and 175 mV for Mo-pic and Mo-pym, respectively, reveal these complexes as promising electrocatalysts for the HER.

Tunable Molecular MoS2 Edge-Site Mimics for Catalytic Hydrogen Production.

Molybdenum sulfides represent state-of-the-art, non-platinum electrocatalysts for the hydrogen evolution reaction (HER). According to the Sabatier principle, the hydrogen binding strength to the edge active sites should be neither too strong nor too weak. Therefore, it is of interest to develop a molecular motif that mimics the catalytic sites structurally and possesses tunable electronic properties that influence the hydrogen binding strength. Furthermore, molecular mimics will be important for providing mechanistic insight toward the HER with molybdenum sulfide catalysts. In this work, a modular method to tune the catalytic properties of the S-S bond in MoO(S2)2L2 complexes is described. We studied the homogeneous electrocatalytic hydrogen production performance metrics of three catalysts with different bipyridine substitutions. By varying the electron-donating abilities, we present the first demonstration of using the ligand to tune the catalytic properties of the S-S bond in molecular MoS2 edge-site mimics. This work can shed light on the relationship between the structure and electrocatalytic activity of molecular MoS2 catalysts and thus is of broad importance from catalytic hydrogen production to biological enzyme functions.

Real-space pseudopotential method for computing the vibrational Stark effect.

The vibrational Stark shift is an important effect in determining the electrostatic environment for molecular or condensed matter systems. However, accurate ab initio calculations of the vibrational Stark effect are a technically demanding challenge. We make use of density functional theory constructed on a real-space grid to expedite the computation of this effect. Our format is especially advantageous for the investigation of small molecules in finite fields as cluster boundary conditions eliminate spurious supercell interactions and allow for charged systems, while convergence is controlled by a single parameter, the grid spacing. The Stark tuning rate is highly sensitive to the interaction between anharmonicity in a vibrational mode and the applied field. To ensure this subtle interaction is fully captured, we apply three parallel approaches: a direct finite field, a perturbative method, and a molecular dynamics method. We illustrate this method by applying it to several small molecules containing C-O and C-N bonds and show that a consistent result can be obtained.

Dimeric [Mo2 S12 ](2-) Cluster: A Molecular Analogue of MoS2 Edges for Superior Hydrogen-Evolution Electrocatalysis.

Proton reduction is one of the most fundamental and important reactions in nature. MoS2 edges have been identified as the active sites for hydrogen evolution reaction (HER) electrocatalysis. Designing molecular mimics of MoS2 edge sites is an attractive strategy to understand the underlying catalytic mechanism of different edge sites and improve their activities. Herein we report a dimeric molecular analogue [Mo2 S12 ](2-) , as the smallest unit possessing both the terminal and bridging disulfide ligands. Our electrochemical tests show that [Mo2 S12 ](2-) is a superior heterogeneous HER catalyst under acidic conditions. Computations suggest that the bridging disulfide ligand of [Mo2 S12 ](2-) exhibits a hydrogen adsorption free energy near zero (-0.05 eV). This work helps shed light on the rational design of HER catalysts and biomimetics of hydrogen-evolving enzymes.

A double-acceptor as a superior organic dye design for p-type DSSCs: high photocurrents and the observed light soaking effect.

Herein, we report three novel single donor double acceptor dyes, BH2, 4, and 6, for use in p-type dye sensitized solar cells (DSSCs). BH4 yields one of the highest photocurrents, 7.4 mA cm(-2), to date. The high performance is achieved via a shorter synthetic route and no exotic materials or cell-building techniques. We suggest a structural principle when building dyes whereby one adopts a double acceptor/single anchor when a triphenylamine moiety is incorporated into a dye for p-type DSSCs. This strategy increases the molar extinction coefficient while simultaneously reducing the number of synthetic steps. The molar extinction coefficients (99 980 M(-1) cm(-1)) reported herein are among the highest reported. Finally, we report the first-ever-observed light soaking effect in p-type DSSCs.

Quantitative Structure-Fluorescence Property Relationship Analysis of a Large BODIPY Library.

A quantitative structure-fluorescence property relationship (QSPR) analysis of a large 288-membered library based on a single fluorescent BODIPY scaffold is presented for the first time. BODIPY is a versatile fluorescent scaffold with outstanding photophysical properties. Absorption (λabs ) and fluorescence emission (λem ) wavelength maxima were modeled with help of stepwise multiple linear regression (MLR) and support vector regression (SVR). The models were rigorously validated by 10-times 10-fold cross-validation (CV), y-scrambling CV and with an external validation set. Non-linear SVR models (R(2) =0.92 and Q(2) =0.71 for λabs ; R(2) =0.89 and Q(2) =0.69 for λem ) performed significantly better than linear models. A small root mean squared error (RMSE) of 5.62 nm and 11.07 nm was achieved for λabs and λem , respectively, and confirmed by external validation. A novel intramolecular charge transfer descriptor was developed based on the QSPR analysis and its inclusion in the modeling significantly improved models of λem . We conclude that QSPR is a useful tool for modeling λabs and λem of BODIPY fluorophores and suggest QSPR as an ideal partner for the design of compounds with tailored fluorescence properties in a diversity-oriented fluorescence library approach (DOFLA).