Hemamala I. Karunadasa

A Molecular MoS2 Edge Site Mimic for Catalytic Hydrogen Generation

Edging In on MoS2 Molybdenum disulfide is a widely used catalyst in the petrochemical industry that has recently shown promise for water-splitting applications. Its activity appears to be confined to edge sites with exposed disulfide groups, although the precise geometric details underlying the chemistry remain uncertain. Karunadasa et al. (p. 698) prepared a molecular complex modeling one of these edge sites, in which a triangular Mo-S-S unit is supported by metal coordination to five tethered pyridine rings. The molecule was characterized crystallographically and proved robustly active toward electrochemical generation of hydrogen from water, even when applied to crudely filtered seawater. A small molecule functionally models the active component of an extended solid material with wide catalytic applications. Inorganic solids are an important class of catalysts that often derive their activity from sparse active sites that are structurally distinct from the inactive bulk. Rationally optimizing activity is therefore beholden to the challenges in studying these active sites in molecular detail. Here, we report a molecule that mimics the structure of the proposed triangular active edge site fragments of molybdenum disulfide (MoS2), a widely used industrial catalyst that has shown promise as a low-cost alternative to platinum for electrocatalytic hydrogen production. By leveraging the robust coordination environment of a pentapyridyl ligand, we synthesized and structurally characterized a well-defined MoIV-disulfide complex that, upon electrochemical reduction, can catalytically generate hydrogen from acidic organic media as well as from acidic water.

A Layered Hybrid Perovskite Solar‐Cell Absorber with Enhanced Moisture Stability

Two-dimensional hybrid perovskites are used as absorbers in solar cells. Our first-generation devices containing (PEA)2(MA)2[Pb3I10] (1; PEA=C6H5(CH2)2NH3(+), MA=CH3NH3(+)) show an open-circuit voltage of 1.18 V and a power conversion efficiency of 4.73%. The layered structure allows for high-quality films to be deposited through spin coating and high-temperature annealing is not required for device fabrication. The 3D perovskite (MA)[PbI3] (2) has recently been identified as a promising absorber for solar cells. However, its instability to moisture requires anhydrous processing and operating conditions. Films of 1 are more moisture resistant than films of 2 and devices containing 1 can be fabricated under ambient humidity levels. The larger bandgap of the 2D structure is also suitable as the higher bandgap absorber in a dual-absorber tandem device. Compared to 2, the layered perovskite structure may offer greater tunability at the molecular level for material optimization.

A molecular molybdenum-oxo catalyst for generating hydrogen from water

A growing awareness of issues related to anthropogenic climate change and an increase in global energy demand have made the search for viable carbon-neutral sources of renewable energy one of the most important challenges in science today. The chemical community is therefore seeking efficient and inexpensive catalysts that can produce large quantities of hydrogen gas from water. Here we identify a molybdenum-oxo complex that can catalytically generate gaseous hydrogen either from water at neutral pH or from sea water. This work shows that high-valency metal-oxo species can be used to create reduction catalysts that are robust and functional in water, a concept that has broad implications for the design of ‘green’ and sustainable chemistry cycles.

A Bismuth-Halide Double Perovskite with Long Carrier Recombination Lifetime for Photovoltaic Applications

Despite the remarkable rise in efficiencies of solar cells containing the lead-halide perovskite absorbers RPbX3 (R = organic cation; X = Br(-) or I(-)), the toxicity of lead remains a concern for the large-scale implementation of this technology. This has spurred the search for lead-free materials with similar optoelectronic properties. Here, we use the double-perovskite structure to incorporate nontoxic Bi(3+) into the perovskite lattice in Cs2AgBiBr6 (1). The solid shows a long room-temperature fundamental photoluminescence (PL) lifetime of ca. 660 ns, which is very encouraging for photovoltaic applications. Comparison between single-crystal and powder PL decay curves of 1 suggests inherently high defect tolerance. The material has an indirect bandgap of 1.95 eV, suited for a tandem solar cell. Furthermore, 1 is significantly more heat and moisture stable compared to (MA)PbI3. The extremely promising optical and physical properties of 1 shown here motivate further exploration of both inorganic and hybrid halide double perovskites for photovoltaics and other optoelectronics.

Low-temperature spin freezing in the Dy2Ti2O7 spin ice

We report a study of the low temperature bulk magnetic properties of the spin ice compound

High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties

{\mathrm{Dy}}_{2}{\mathrm{Ti}}_{2}{\mathrm{O}}_{7}

Mechanism for Broadband White-Light Emission from Two-Dimensional (110) Hybrid Perovskites

with particular attention to the

Pressure-Induced Conductivity and Yellow-to-Black Piezochromism in a Layered Cu–Cl Hybrid Perovskite

(Tl4\mathrm{K})

Ba2LnSbO6 and Sr2LnSbO6 (Ln = Dy, Ho, Gd) double perovskites: Lanthanides in the geometrically frustrating fcc lattice

spin freezing transition. While this transition is superficially similar to that in a spin glass, there are important qualitative differences from spin glass behavior: the freezing temperature increases slightly with applied magnetic field, and the distribution of spin relaxation times remains extremely narrow down to the lowest temperatures. Furthermore, the characteristic spin relaxation time increases faster than exponentially down to the lowest temperatures studied. These results indicate that spin-freezing in spin ice materials represents a novel form of magnetic glassiness associated with the unusual nature of geometrical frustration in these materials.

Electrochemical generation of hydrogen from acetic acid using a molecular molybdenum–oxo catalyst

We report the first high-pressure single-crystal structures of hybrid perovskites. The crystalline semiconductors (MA)PbX3 (MA = CH3NH3+, X = Br– or I–) afford us the rare opportunity of understanding how compression modulates their structures and thereby their optoelectronic properties. Using atomic coordinates obtained from high-pressure single-crystal X-ray diffraction we track the perovskites’ precise structural evolution upon compression. These structural changes correlate well with pressure-dependent single-crystal photoluminescence (PL) spectra and high-pressure bandgaps derived from density functional theory. We further observe dramatic piezochromism where the solids become lighter in color and then transition to opaque black with compression. Indeed, electronic conductivity measurements of (MA)PbI3 obtained within a diamond-anvil cell show that the material’s resistivity decreases by 3 orders of magnitude between 0 and 51 GPa. The activation energy for conduction at 51 GPa is only 13.2(3) meV, suggesting that the perovskite is approaching a metallic state. Furthermore, the pressure response of mixed-halide perovskites shows new luminescent states that emerge at elevated pressures. We recently reported that the perovskites (MA)Pb(BrxI1–x)3 (0.2 < x < 1) reversibly form light-induced trap states, which pin their PL to a low energy. This may explain the low voltages obtained from solar cells employing these absorbers. Our high-pressure PL data indicate that compression can mitigate this PL redshift and may afford higher steady-state voltages from these absorbers. These studies show that pressure can significantly alter the transport and thermodynamic properties of these technologically important semiconductors.