Injection 3D Printing of Doubly Curved Ceramic Shells in Non-Synthetic Particle Suspensions.

This paper examines the application of non-synthetic particle suspensions as a support medium for the additive manufacturing of complex doubly curved ceramic shells with overhangs between 0° and 90° using clay paste. In this method, the build-up material is injected within a constant volume of air-permeable particle suspension. As the used clay paste does not solidify right after injection, the suspension operates like a support medium and enables various print path strategies.

Influence of Surface and Structural Variations in Donor-Acceptor-Donor Sensitizers on Photoelectrocatalytic Water Splitting.

Conjugated organic chromophores composed of linked donor (D) and acceptor (A) moieties have attracted considerable attention for photoelectrochemical applications. In this work, we compare the optoelectronic properties and photoelectrochemical performance of two D-A-D structural isomers with thiophene--carboxylic acid ( denotes 3 and 2 positions) derivatives and 2,1,3-benzothiadiazole as the D and A moieties, respectively. 5,5'-(Benzo[][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-3-carboxylic acid), , and 5,5'-(benzo[][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carboxylic acid), , were employed in the study to understand how structural isomers affect surface attachments within chromophore-catalyst assemblies and their influence on charge-transfer dynamics.

A Silicon-Based Heterojunction Integrated with a Molecular Excited State in a Water-Splitting Tandem Cell.

Semiconductor-based photocathodes with high light-absorption capability are of interest in the production of solar fuels, but many of them are limited by low efficiencies due to rapid interfacial back electron transfer. We demonstrate here that a nanowire-structured p-type Si (p-Si) electrode, surface-modified with a perylene-diimide derivative (PDI'), can undergo photoreduction of a surface-bound, water reduction catalyst toward efficient H evolution under a low applied bias. At the electrode interface, the PDI' layer converts green light into high-energy holes at its excited state for extraction of photogenerated electrons at the photoexcited p-Si.

Design and reactivity of pentapyridyl metal complexes for ammonia oxidation.

Oxidation of NH3 to N2 by pentapyridyl metal complexes via hydrogen atom abstraction was investigated computationally. Quantum chemical analysis reveals insights on orbital symmetry requirements for efficient NH3 oxidation. The most promising complex, [(PY5)Mo(NH3)]2+, was studied experimentally.

Evaluation of attractive interactions in the second coordination sphere of iron complexes containing pendant amines.

The interactions between pendant amines in the second coordination sphere and ligands in the first coordination sphere are important for understanding the structures and reactivity of complexes containing PR2NR'2 ligands, which have been shown to be highly active H2 oxidation/production catalysts. A series of [Fe(PPh2NBn2)2(X)(Y)]n+ complexes have been prepared and structurally characterized. These complexes have two different ligands with which the pendant amines of the diphosphine ligand can interact.

Anionic guest-dependent slow magnetic relaxation in Co(ii) tripodal iminopyridine complexes.

We report the syntheses and magnetic property characterizations of four mononuclear cobalt(ii) complex salts featuring a tripodal iminopyridine ligand with external anion receptor groups, [CoL5-ONHtBu]X2 (X = Cl (1), Br (2), I (3) and ClO4 (4)). While all four salts exhibit anion binding through pendant amide moieties, only in the case of 1 is field-induced slow relaxation of magnetisation observed, whereas in the other salts this phenomenon is absent at the limits of our instrumentation. The effect of chloride inducing a seventh Co-N interaction and concomitant structural distortion is hypothesized as the origin of the observed dynamic magnetic properties observed in 1.

Modulating Hole Transport in Multilayered Photocathodes with Derivatized p-Type Nickel Oxide and Molecular Assemblies for Solar-Driven Water Splitting.

For solar water splitting, dye-sensitized NiO photocathodes have been a primary target. Despite marginal improvement in performance, limitations remain arising from the intrinsic disadvantages of NiO and insufficient catalysis. We report here a new approach to modifying NiO photocathodes with doped NiO bilayers and an additional layer of macro-mesoporous ITO.

Intramolecular N-H···Cl hydrogen bonds in the outer coordination sphere of a bipyridyl bisurea-based ligand stabilize a tetrahedral FeLCl2 complex.

A bipyridyl-based anion receptor is utilized as a ligand in a tetrahedral FeCl2 complex and demonstrates secondary coordination sphere influence through intramolecular hydrogen bonding to the chloride ligands as evidenced by X-ray crystallography.

A high-throughput on-line microdialysis-capillary assay for D-serine.

A high-throughput method is described for the analysis of D-serine and other neurotransmitters in tissue homogenates. Analysis is performed by microdialysis-capillary electrophoresis (CE) with laser-induced fluorescence (LIF) detection in a sheath flow detection cell. Sample pretreatment is not required as microdialysis sampling excludes proteins and cell fragments.