Substrate-induced strain in molybdenum disulfide grown by aerosol-assisted chemical vapor deposition.

Transition metal dichalcogenides have been extensively studied in recent years because of their fascinating optical, electrical, and catalytic properties. However, low-cost, scalable production remains a challenge. Aerosol-assisted chemical vapor deposition (AACVD) provides a new method for scalable thin film growth.

Juggling Optoelectronics and Catalysis: The Dual Talents of Bench Stable 1,4-Azaborinines.

Boron- and nitrogen-doped polycyclic aromatic hydrocarbons (B-PAHs) have established a strong foothold in the realm of organic electronics. However, their catalytic potential remains largely untapped. In this study, we synthesise and characterise two bench stable B,N-doped PAH derivatives based on a 1,4-azaborinine motif.

Reeling them in: PhPSiMe in the sequential formation of InP magic-sized clusters.

Indium phosphide magic-sized clusters (MSCs) have been identified as a key step in the growth of InP quantum dots (QDs). However, the need for elevated temperatures to form QDs from MSCs has limited our understanding of this transformation. Herein, we utilize PhPSiMe to identify additional MSC intermediate species, which absorb from 365 nm to 490 nm.

Correction: Synthesis of Ca(PF), formed via nitrosonium oxidation of calcium.

Correction for 'Synthesis of Ca(PF), formed via nitrosonium oxidation of calcium' by Evan N. Keyzer et al., Chem.

Energy transfer and photoluminescence properties of lanthanide-containing polyoxotitanate cages coordinated by salicylate ligands.

Polyoxotitanate (POT) cages have attracted considerable attention recently; much of this from the fact that they can be considered to be structural models for the technologically important semiconductor TiO2. Among the reported POT cages, lanthanide-containing (Ln-POT) cages are of particular interest owing to the fascinating luminescence properties of Ln3+ ions and the versatile coordination environments that they can adopt. In the present study, we report the energy transfer mechanism and photoluminescence properties of a series of isostructural Ln-POT cages coordinated by salicylate ligands, of general formula [LnTi6O3(OiPr)9(salicylate)6] (Ln-1, Ln = La to Er excluding Pm).

On the phase control of CuInS nanoparticles from Cu-/In-xanthates.

In this paper we report the synthesis and single-crystal X-ray characterisation of six novel indium(iii) xanthate complexes. These xanthates have been used as an In-source for the synthesis of highly crystalline CuInS2 nanoparticles in conjunction with a Cu(i)-xanthate. In synthesising the nanoparticles we have also demonstrated an ability to control the phase of the material through choice of solvent.

Black phosphorus with near-superhydrophobic properties and long-term stability in aqueous media.

Black phosphorus is a two-dimensional material that has potential applications in energy storage, high frequency electronics and sensing, yet it suffers from instability in oxygenated and/or aqueous systems. Here we present the use of a polymeric stabilizer which prevents the degradation of nearly 68% of the material in aqueous media over the course of ca. 1 month.

A simple route to complex materials: the synthesis of alkaline earth - transition metal sulfides.

A simple, low-temperature synthesis of a family of alkaline earth metal chalcogenide thin films is reported. These materials have previously only been produced from demanding, high temperature, high pressure reactions. The decomposition of calcium, barium and copper xanthates leads to the clean formation of CaS, BaS, CaCuS, β-BaCuS and β-BaCuS.

Shining a light on transition metal chalcogenides for sustainable photovoltaics.

Transition metal chalcogenides are an important family of materials that have received significant interest in recent years as they have the potential for diverse applications ranging from use in electronics to industrial lubricants. One of their most exciting properties is the ability to generate electricity from incident light. In this perspective we will summarise and highlight the key results and challenges in this area and explain how transition metal chalcogenides are a good choice for future sustainable photovoltaics.

A Modular Approach to Inorganic Phosphazane Macrocycles.

Inorganic macrocycles, based on non-carbon backbones, present exciting synthetic challenges in the systematic assembly of inorganic molecules, as well as new avenues in host-guest and supramolecular chemistry. Here we demonstrate a new high-yielding modular approach to a broad range of trimeric and hexameric S- and Se-bridged inorganic macrocycles based on cyclophosphazane frameworks, using the building blocks [S=(H)P(μ-NR)] . The method involves the in situ generation of the key intermediate [E.

Synthesis of Ca(PF), formed via nitrosonium oxidation of calcium.

The development of rechargeable Ca-ion batteries as an alternative to Li systems has been limited by the availability of suitable electrolyte salts. We present the synthesis of complexes of Ca(PF) (a key potential Ca battery electrolyte salt) via the treatment of Ca metal with NOPF, and explore their conversion to species containing POF under the reaction conditions.

Synthesis, structure and paramagnetic NMR analysis of a series of lanthanide-containing [LnTiO(OPr)(salicylate)] cages.

The influence of paramagnetic Ln ions on the NMR behaviour is investigated via a series of new isostructural lanthanide-containing cages with the general formula [LnTiO(OPr)(salicylate)] (Ln-1, Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er). Compared to conventional coordination compounds containing Ln ions, the peripheral ligands in Ln-1 are separated from the paramagnetic lanthanide centres by oxo-Ti linkages, and therefore experience a weaker paramagnetic influence. As a result, all of the H and C NMR signals of these Ln-1 cages (except for Gd-1) are observed and can be unambiguously assigned, which provides an excellent platform for the in-depth study of the NMR behaviour of paramagnetic Ln ions.

The synthesis and characterization of CuZnSnS thin films from melt reactions using xanthate precursors.

Kesterite, CuZnSnS (CZTS), is a promising absorber layer for use in photovoltaic cells. We report the use of copper, zinc and tin xanthates in melt reactions to produce CuZnSnS (CZTS) thin films. The phase of the as-produced CZTS is dependent on decomposition temperature.

The influence of halides in polyoxotitanate cages; dipole moment, splitting and expansion of d-orbitals and electron-electron repulsion.

Metal-doped polyoxotitanate (M-POT) cages have been shown to be efficient single-source precursors to metal-doped titania [TiO(M)] (state-of-the-art photocatalytic materials) as well as molecular models for the behaviour of dopant metal ions in bulk titania. Here we report the influence halide ions have on the optical and electronic properties of a series of halide-only, and cobalt halide-'doped' POT cages. In this combined experimental and computational study we show that halide ions can have several effects on the band gaps of halide-containing POT cages, influencing the dipole moment (hole-electron separation) and the structure of the valance band edge.

Synthetic routes to iron chalcogenide nanoparticles and thin films.

Iron chalcogenides are earth abundant, cheap and environmentally benign materials that have seen extensive research directed toward a range of applications, most notably for photovoltaics. The most common forms of materials for these applications are either nanoparticles or thin films. This perspective seeks to summarise the key synthetic routes to these materials by highlighting the key aspects that lead to control over phase and morphology.

Novel properties and potential applications of functional ligand-modified polyoxotitanate cages.

Functional ligand-modified polyoxotitanate (L-POT) cages of the general type [TixOy(OR)z(L)m] (OR = alkoxide, L = functional ligand) can be regarded as molecular fragments of surface-sensitized solid-state TiO2, and are of value as models for studying the interfacial charge and energy transfer between the bound functional ligands and a bulk semiconductor surface. These L-POTs have also had a marked impact in many other research fields, such as single-source precursors for TiO2 deposition, inorganic-organic hybrid material construction, photocatalysis, photoluminescence, asymmetric catalysis and gas adsorption. Their atomically well-defined structures provide the basis for the understanding of structure/property relationships and ultimately for the rational design of new cages targeting specific uses.

How Does Substitutional Doping Affect Visible Light Absorption in a Series of Homodisperse Ti11 Polyoxotitanate Nanoparticles--A Comment on the Band Gap Determination of the Fe(II) Cages (Chem. Eur. J. 2015, 21, 11538).

There is no experimental support for the conclusion by Coppens and Chen in a recent paper that the (HOMO-LUMO) band gaps in a series of Fe(II) polyoxotitanate cages are in the range 1.43-1.59 eV.

Synthesis, structure and properties of the manganese-doped polyoxotitanate cage [Ti18MnO30(OEt)20(MnPhen)3] (Phen = 1,10-phenanthroline).

The novel heterometallic polyoxotitanate cage [Ti18MnO30(OEt)20(MnPhen)3] (1), obtained by solvothermal reaction of Ti(OEt)4 with Mn(AcO)3·(H2O)2 and 1,10-phenanthroline (Phen) in EtOH, has a C3 symmetric core structure containing an interstitial tetrahedral Mn(II) ion and is surrounded by three Mn(II)(Phen) fragments. The molecular structure is retained in thin film electrodes of 1 deposited by solution drop-casting onto fluorinated tin oxide (FTO). Both solid state and solution phase electrochemical measurements show dual redox couples, consistent with the two distinct Mn coordination environments in the cage structure.

Theory and practice: bulk synthesis of C3B and its H2- and Li-storage capacity.

Previous theoretical studies of C3B have suggested that boron-doped graphite is a promising H2- and Li-storage material, with large maximum capacities. These characteristics could lead to exciting applications as a lightweight H2-storage material for automotive engines and as an anode in a new generation of batteries. However, for these applications to be realized a synthetic route to bulk C3B must be developed.

Selective lability of ruthenium(II) arene amino acid complexes.

A series of organometallic complexes of the form [(PhH)Ru(amino acid)](+) have been synthesized using amino acids able to act as tridentate ligands. The straightforward syntheses gave enantiomerically pure complexes with two stereogenic centers due to the enantiopurity of the chelating ligands. Complexes were characterized in the solid-state and/or solution-state where the stability of the complex allowed.

A Si photocathode protected and activated with a Ti and Ni composite film for solar hydrogen production.

An efficient, stable and scalable hybrid photoelectrode for visible-light-driven H2 generation in an aqueous pH 9.2 electrolyte solution is reported. The photocathode consists of a p-type Si substrate layered with a Ti and Ni-containing composite film, which acts as both a protection and electrocatalyst layer on the Si substrate.

Ab initio structure search and in situ 7Li NMR studies of discharge products in the Li-S battery system.

The high theoretical gravimetric capacity of the Li-S battery system makes it an attractive candidate for numerous energy storage applications. In practice, cell performance is plagued by low practical capacity and poor cycling. In an effort to explore the mechanism of the discharge with the goal of better understanding performance, we examine the Li-S phase diagram using computational techniques and complement this with an in situ (7)Li NMR study of the cell during discharge.

Structure, photochemistry and applications of metal-doped polyoxotitanium alkoxide cages.

Metal-doped polyoxotitanium cages (M-POTs) of the type [TixOy(OR)zMnXm] (M = a main group, transition metal or lanthanide; X = an anion such as a halide) can be regarded as molecular fragments of metal-doped TiO2. As such M-POTs can be used as structural models for the inclusion of metal ions into the TiO2 lattice and the ways in which well-defined microstructural changes affect photo-induced hole-electron separation. They are also potential organically-soluble redox-catalysts for a range of organic transformations and have been shown to be useful single-source precursors for the deposition of metal-doped TiO2.

A study of the optical properties of metal-doped polyoxotitanium cages and the relationship to metal-doped titania.

To what extent the presence of transition metal ions can affect the optical properties of structurally well-defined, metal-doped polyoxotitanium (POT) cages is a key question in respect to how closely these species model technologically important metal-doped TiO2. This also has direct implications to the potential applications of these organically-soluble inorganic cages as photocatalytic redox systems in chemical transformations. Measurement of the band gaps of the series of closely related polyoxotitanium cages [MnTi14(OEt)28O14(OH)2] (1), [FeTi14(OEt)28O14(OH)2] (2) and [GaTi14(OEt)28O15(OH)] (3), containing interstitial Mn(II), Fe(II) and Ga(III) dopant ions, shows that transition metal doping alone does not lower the band gaps below that of TiO2 or the corresponding metal-doped TiO2.