Mechanistic Aspects of a Highly Active Dinuclear Zinc Catalyst for the Co‐polymerization of Epoxides and CO2

The dinuclear zinc complex reported by us is to date the most active zinc catalyst for the co‐polymerization of cyclohexene oxide (CHO) and carbon dioxide. However, co‐polymerization experiments with propylene oxide (PO) and CO₂ revealed surprisingly low conversions. Within this work, we focused on clarification of this behavior through experimental results and quantum chemical studies. The combination of both results indicated the formation of an energetically highly stable intermediate in the presence of propylene oxide and carbon dioxide. A similar species in the case of cyclohexene oxide/CO₂ co‐polymerization was not stable enough to deactivate the catalyst due to steric repulsion.     

Hybrid Plasmonic–Aerogel Materials as Optical Superheaters with Engineered Resonances

Solar radiation is a versatile source of energy, convertible to different forms of power. A direct path to exploit it is the generation of heat, for applications including passive building heating, but it can also drive secondary energy-conversion steps. We present a novel concept for a hybrid material which is both strongly photo-absorbing and with superior characteristics for the insulation of heat. The combination of that two properties is rather unique, and make this material an optical superheater. To realize such a material, we are combining plasmonic nanoheaters with alumina aerogel. The aerogel has the double function of providing structural support for plasmonic nanocrystals, which serve as nanoheaters, and reducing the diffusion rate of the heat generated by them, resulting in large local temperature increases under a relatively low radiation intensity. This work includes theoretical discussion on the physical mechanisms impacting the system's balanced thermal equilibrium.     

Differential Response of Pentanal and Hexanal Exhalation to Supplemental Oxygen and Mechanical Ventilation in Rats

High inspired oxygen during mechanical ventilation may influence the exhalation of the previously proposed breath biomarkers pentanal and hexanal, and additionally induce systemic inflammation. We therefore investigated the effect of various concentrations of inspired oxygen on pentanal and hexanal exhalation and serum interleukin concentrations in 30 Sprague Dawley rats mechanically ventilated with 30, 60, or 93% inspired oxygen for 12 h. Pentanal exhalation did not differ as a function of inspired oxygen but increased by an average of 0.4 (95%CI: 0.3; 0.5) ppb per hour, with concentrations doubling from 3.8 (IQR: 2.8; 5.1) ppb at baseline to 7.3 (IQR: 5.0; 10.8) ppb after 12 h. Hexanal exhalation was slightly higher at 93% of inspired oxygen with an average difference of 0.09 (95%CI: 0.002; 0.172) ppb compared to 30%. Serum IL-6 did not differ by inspired oxygen, whereas IL-10 at 60% and 93% of inspired oxygen was greater than with 30%. Both interleukins increased over 12 h of mechanical ventilation at all oxygen concentrations. Mechanical ventilation at high inspired oxygen promotes pulmonary lipid peroxidation and systemic inflammation. However, the response of pentanal and hexanal exhalation varies, with pentanal increasing by mechanical ventilation, whereas hexanal increases by high inspired oxygen concentrations.     

Physical mechanisms responsible for the water-induced degradation of PC61BM P3HT photovoltaic thin films

We show that [6,6]-phenyl-C61-butyric acid methyl ester (PC₆₁BM) at the surface of thin film blends of poly(3-hexylthiophene) (P3HT):PC₆₁BM can be patterned by water. Using a series of heating and cooling steps, water droplets condense onto the blend film surface. This is possible due to the liquid-like, water swollen layer of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. Breath pattern water deformation and subsequent drying on the film surface results in isolated PC₆₁BM structures, showing that migration of PC₆₁BM takes place. This was confirmed by selective wavelength illumination to spatially map the photoluminescence from the P3HT and PC₆₁BM. Within a device, redistribution of the surface PC₆₁BM into aggregates would be catastrophic, as it would markedly alter device performance. We also postulate that repeated volume change of the poly(3,4-ethylenedioxythiophene) polystyrene sulfonate layer by water swelling may be, in part, responsible for the delamination failure mechanism in thin film solar cells devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 141–146     

Lithium intercalation into disordered carbon/SiCN composite. Part 2: Raman spectroscopy and <Superscript>7</Superscript>Li MAS NMR investigation of lithium storage sites

Within this work, we analyze the lithium storage sites within carbon/silicon carbonitride (SiCN) composites. Commercial carbons, HD3 (hard carbon) and LD1N and LD2N (soft carbons), of varying porosity are impregnated with polysilazane (HTT 1800) and pyrolysed at 1100 °C. It is found in the first part of this study (Graczyk-Zajac et al. J Solid State Electrochem 19:2763–2769, 2015) that the initial porosity of the carbon phase plays an important role in determining the lithium insertion capacity and rate capability of the composite material. By applying Raman spectroscopy and solid-state ⁷Li MAS NMR on pristine, lithiated, and delithiated samples, we investigate the lithium storage sites within the composite materials. By means of Raman spectroscopy, it has been found that lithium storage in hard carbon-derived composites occurs in a significant extent via adsorption-like process within unorganized carbon, whereas for the soft carbon composites, storage in turbostratic carbon is identified. ⁷Li solid-state NMR confirms these findings revealing that more than 33 % of lithium stored in HD3/SiCN is adsorbed in ionic form at the surface and in pores of the composite, while around 38 % is stored between carbon layers. LD1N and LD2N composites store more than 50 % of lithium in the intercalation-type sites.     

Anion Storage Chemistry of Organic Cathodes for High-Energy and High-Power Density Divalent Metal Batteries

Multivalent batteries show promising prospects for next-generation sustainable energy storage applications. Herein, we report a polytriphenylamine (PTPAn) composite cathode capable of highly reversible storage of tetrakis(hexafluoroisopropyloxy) borate [B(hfip)₄] anions in both Magnesium (Mg) and calcium (Ca) battery systems. Spectroscopic and computational studies reveal the redox reaction mechanism of the PTPAn cathode material. The Mg and Ca cells exhibit a cell voltage >3 V, a high-power density of ∼∼3000 W kg⁻¹ and a high-energy density of ∼∼300 Wh kg⁻¹, respectively. Moreover, the combination of the PTPAn cathode with a calcium-tin (Ca−Sn) alloy anode could enable a long battery-life of 3000 cycles with a capacity retention of 60 %. The anion storage chemistry associated with dual-ion electrochemical concept demonstrates a new feasible pathway towards high-performance divalent ion batteries.     

Catalytic Alkyne Semihydrogenation with Polyhydride Ni/Ga Clusters

The bimetallic, decanuclear Ni₃Ga₇-cluster of the formula [Ni₃(GaTMP)₃(μ²-GaTMP)₃(μ³-GaTMP)] ( 1 , TMP=2,2,6,6-tetramethylpiperidinyl) reacts reversibly with dihydrogen under the formation of a series of (poly-)hydride clusters 2 . Low-temperature 2D NMR experiments at −80 °C show that 2 consist of a mixture of a di- ( 2_Di ), tetra- ( 2_Tetra ) and hexahydride species ( 2_Hexa ). The structures of 2_Di and 2_Tetra are assessed by a combination of 2D NMR spectroscopy and DFT calculations. The cooperation of both metals is essential for the high hydrogen uptake of the cluster. Polyhydrides 2 are catalytically active in the semihydrogenation of 4-octyne to 4-octene with good selectivity. The example is the first of its kind and conceptually relates properties of molecular, atom-precise transition metal/main group metal clusters to the respective solid-state phase in catalysis.