Opening Doors to Future Electrochemical Energy Devices: The Anion‐Conducting Polyketone Polyelectrolytes

The numerous potential benefits of incorporating anion‐exchange membranes (AEMs), in place of proton‐exchange membranes (PEMs), in energy storage and conversion technologies renders their development of fundamental importance for the continued evolution of alternative energy systems. However, the widespread implementation of AEMs is currently plagued by a range of problems including lower conductivity (with respect to PEMs), poor stability, and high cost. This study reports the conversion of polyketone, one of the world's most mass produced and cheap polymers, to a new highly tuneable polymer architecture, functionalized polyketone (FPK), that demonstrates a range of excellent properties rendering it a significant prospect for AEM materials. The thermal, processing, and ion‐conducting properties of FPK are governed by the amount and nature of the newly formed N‐substituted pyrrole pendant side groups. At 80 °C, the quarternized pyridyl FPK derivative (4MPyrFPK) yields ion‐conductivities of 8.6 and 10.5 mS cm^?1 in the iodide and hydroxide forms. In addition, the hydroxide form of 4MPyr‐FPK demonstrates remarkable stability toward the typically problematic alkaline conditions. No chemical decomposition is observed to the membrane after imbibing it in KOH solution for 72 h, and furthermore, the ion‐conductivity is demonstrated to remain constant for at least 30 d at 80 °C.     

Cover Image,Volume 66, Issue 3

The cover image, by Katia Sparnacci et al., is based on the Research Article High temperature surface neutralization process with random copolymers for block copolymer self‐assembly, DOI: 10.1002/pi.5285 .

     

Highly Stable Colloidal “Giant” Quantum Dots Sensitized Solar Cells

Colloidal quantum dots (QDs) are widely studied due to their promising optoelectronic properties. This study explores the application of specially designed and synthesized “giant” core/shell CdSe/(CdS)_x QDs with variable CdS shell thickness, while keeping the core size at 1.65 nm, as a highly efficient and stable light harvester for QD sensitized solar cells (QDSCs). The comparative study demonstrates that the photovoltaic performance of QDSCs can be significantly enhanced by optimizing the CdS shell thickness. The highest photoconversion efficiency (PCE) of 3.01% is obtained at optimum CdS shell thickness ≈1.96 nm. To further improve the PCE and fully highlight the effect of core/shell QDs interface engineering, a CdSe_x S_1?x interfacial alloyed layer is introduced between CdSe core and CdS shell. The resulting alloyed CdSe/(CdSe_x S_1?x )₅/(CdS)₁ core/shell QD‐based QDSCs yield a maximum PCE of 6.86%, thanks to favorable stepwise electronic band alignment and improved electron transfer rate with the incorporation of CdSe_x S_1?x interfacial layer with respect to CdSe/(CdS)₆ core/shell. In addition, QDSCs based on “giant” core/CdS‐shell or alloyed core/shell QDs exhibit excellent long‐term stability with respect to bare CdSe‐based QDSCs. The giant core/shell QDs interface engineering methodology offers a new path to improve PCE and the long‐term stability of liquid junction QDSCs.     

Tuning of a Vertical Spin Valve with a Monolayer of Single Molecule Magnets

The synthesis and the chemisorption from solution of a terbium bis‐phthalocyaninato complex suitable for the functionalization of lanthanum strontium manganite (LSMO) are reported. Two phosphonate groups are introduced in the double decker structure in order to allow the grafting to the ferromagnetic substrate actively used as injection electrode in organic spin valve devices. The covalent bonding of functionalized terbium bis‐phthalocyaninato system on LSMO surface preserves its molecular properties at the nanoscale. X‐ray photoelectron spectroscopy confirms the integrity of the molecules on the LSMO surface and a small magnetic hysteresis reminiscent of the typical single molecule magnet behavior of this system is detected on surface by X‐ray magnetic circular dichroism experiments. The effect of the hybrid magnetic electrode on spin polarized injection is investigated in vertical organic spin valve devices and compared to the behavior of similar spin valves embedding a single diamagnetic layer of alkyl phosphonate molecules analogously chemisorbed on LSMO. Magnetoresistance experiments have evidenced significant alterations of the magneto‐transport by the terbium bis‐phthalocyaninato complex characterized by two distinct temperature regimes, below and above 50 K, respectively.     

Complexation of organic compounds in the presence of Al3+ during micellar flocculation

Complexes of Al and model pollutants phenol, benzoic acid, 2,4-D (2,4-dichlorophenoxyacetic acid) and 2,4-DB (2,4-dichlorophenoxybutiric acid) play a key role in the removal of organic pollutants by co-adsorption on micelles of anionic surfactants flocculated by means of Al(3+). This technique, known as adsorptive micellar flocculation (AMF), is related to removal of organic compounds by coagulation-precipitation with Al and Fe salts. Some of the stoichiometries found (6Al:1L and higher, with "L" the organic compound) indicate that complexes of a cationic nature form in the presence of high excesses of Al, possibly polyaluminium complexes related to the species [Al(13)O(4)(OH)(24)](7+). In the case of phenol it has been established by spectroscopic measures that in the range of [Al(2)(SO(4))(3)](tot) between 5 x 10(-5) and 3 x 10(-4)M and [phenol](tot) between 10(-3) and 6 x 10(-3)M complexes exist at pH as low as 2.4. The results show that AMF may be explained by the chemisorption of molecules of organic compounds able to incorporate into the polyaluminic complexes occurring within the Stern layer of flocculating micelles.     

Materials Science in the Developing World: Challenges and Perspectives for Africa

“Africans believe in something that is difficult to render in English. We call it ubuntu or botho. It means the essence of being human. You know when it is there and when it is absent. It speaks about humanness, gentleness, hospitality, putting yourself out on behalf of others, being vulnerable. It embraces compassion and roughness. It recognizes that my humanity is bound up in yours, for we can only be human together” (Desmond Tutu)     

Optical properties of rotationally twinned InP nanowire heterostructures

We have developed a technique so that both transmission electron microscopy and microphotoluminescence can be performed on the same semiconductor nanowire over a large range of optical power, thus allowing us to directly correlate structural and optical properties of rotationally twinned zinc blende InP nanowires. We have constructed the energy band diagram of the resulting multiquantum well heterostructure and have performed detailed quantum mechanical calculations of the electron and hole wave functions. The excitation power dependent blue-shift of the photoluminescence can be explained in terms of the predicted staggered band alignment of the rotationally twinned zinc blende/wurzite InP heterostructure and of the concomitant diagonal transitions between localized electron and hole states responsible for radiative recombination. The ability of rotational twinning to introduce a heterostructure in a chemically homogeneous nanowire material and alter in a major way its optical properties opens new possibilities for band-structure engineering.     

A New Design Paradigm for Smart Windows: Photocurable Polymers for Quasi‐Solid Photoelectrochromic Devices with Excellent Long‐Term Stability under Real Outdoor Operating Conditions

A new photoelectrochromic device (PECD) is presented in this work proposing the combination of a WO₃‐based electrochromic device (ECD) and a polymer‐based dye‐sensitized solar cell (DSSC). In the newly designed architecture, a photocurable polymeric membrane is employed as quasi‐solid electrolyte for both the ECD and the DSSC. In addition, a photocurable fluoropolymeric system is incorporated as solution‐processable external protective thin coating film with easy‐cleaning and UV‐shielding functionalities. Such new polymer‐based device assembly is characterized by excellent device operation with improved photocoloration efficiency and switching ability compared with analogous PECDs based on standard liquid electrolyte systems. In addition, long‐term (>2100 h) stability tests under continuous exposure to real outdoor conditions reveal the remarkable performance stability of this new quasi‐solid PECD system, attributed to the protective action of the photocurable fluorinated coating that effectively prevents photochemical and physical degradation of the PECD components during operation. This first example of quasi‐solid PECD systems paves the way for a new generation of thermally, electrochemically, and photochemically stable polymer‐based PECDs, and provides for the first time a clear demonstration of their true potential as readily upscalable smart window components for energy‐saving buildings.     

Toward a Magnesium‐Iodine Battery

The quest for new electrolyte and cathode materials is a crucial point for beyond‐lithium‐ion energy storage systems. Following this, an electrolyte for secondary magnesium batteries based on a new iodoaluminate ionic liquid and δ‐MgI₂ is reported. Promising electrochemical performance in terms of Mg plating‐stripping, coulombic efficiency, and conductivity, demonstrates the potential of this iodine‐based system for future Mg secondary batteries.     

Noninvasive ECG as a tool for predicting termination of paroxysmal atrial fibrillation

Atrial fibrillation (AF) is the most common cardiac arrhythmia and entails an increased risk of thromboembolic events. Prediction of the termination of an AF episode, based on noninvasive techniques, can benefit patients, doctors and health systems. The method described in this paper is based on two-lead surface electrocardiograms (ECGs): 1-min ECG recordings of AF episodes including N-type (not terminating within an hour after the end of the record), S-type (terminating 1 min after the end of the record) and T-type (terminating immediately after the end of the record). These records are organised into three learning sets (N, S and T) and two test sets (A and B). Starting from these ECGs, the atrial and ventricular activities were separated using beat classification and class averaged beat subtraction, followed by the evaluation of seven parameters representing atrial or ventricular activity. Stepwise discriminant analysis selected the set including dominant atrial frequency (DAF, index of atrial activity) and average HR (HRmean, index of ventricular activity) as optimal for discrimination between N/T-type episodes. The linear classifier, estimated on the 20 cases of the N and T learning sets, provided a performance of 90% on the 30 cases of a test set for the N/T-type discrimination. The same classifier led to correct classification in 89% of the 46 cases for N/S-type discrimination. The method has shown good results and seems to be suitable for clinical application, although a larger dataset would be very useful for improvement and validation of the algorithms and the development of an earlier predictor of paroxysmal AF spontaneous termination time.