Pre-Activation of CO2 at Cobalt Phthalocyanine-Mg(OH)2 Interface for Enhanced Turnover Rate

Cobalt phthalocyanine (CoPc) anchored on heterogeneous scaffold has drawn great attention as promising electrocatalyst for carbon dioxide reduction reaction (CO₂RR), but the molecule/substrate interaction is still pending for clarification and optimization to maximize the reaction kinetics. Herein, a CO₂RR catalyst is fabricated by affixing CoPc onto the Mg(OH)₂ substrate primed with conductive carbon, demonstrating an ultra-low overpotential of 0.31 ± 0.03 V at 100 mA cm⁻² and high faradaic efficiency of >95% at a wide current density range for CO production, as well as a heavy-duty operation at 100 mA cm⁻² for more than 50 h in a membrane electrode assembly. Mechanistic investigations employing in situ Raman and attenuated total reflection surface-enhanced infrared absorption spectroscopy unravel that Mg(OH)₂ plays a pivotal role to enhance the CO₂RR kinetics by facilitating the first-step electron transfer to form anionic *CO₂⁻ intermediates. DFT calculations further elucidate that introducing Lewis acid sites help to polarize CO₂ molecules absorbed at the metal centers of CoPc and consequently lower the activation barrier. This work signifies the tailoring of catalyst-support interface at molecular level for enhancing the turnover rate of CO₂RR.     

Proximity-Induced Fully Ferromagnetic Order with Eightfold Magnetic Anisotropy in Heavy Transition Metal Oxide CaRuO3

Ferromagnetic materials with a strong spin-orbit coupling (SOC) have attracted much attention in recent years because of their exotic properties and potential applications in energy-efficient spintronics. However, such materials are scarce in nature. Here, a proximity-induced paramagnetic to ferromagnetic transition for the heavy transition metal oxide CaRuO₃ in (001)-(LaMnO₃/CaRuO₃) superlattices is reported. Anomalous Hall effect is observed in the temperature range up to 180 K. Maximal anomalous Hall conductivity and anomalous Hall angle are as large as ∼15 Ω⁻¹ cm⁻¹ and ∼0.93%, respectively, by one to two orders of magnitude larger than those of the typical 3d ferromagnetic oxides such as La_0.67Sr_0.33MnO₃. Density functional theory calculations indicate the existence of avoid band crossings in the electronic band structure of the ferromagnetic CRO layer, which enhances Berry curvature thus strong anomalous Hall effects. Further evidences from polarized neutron reflectometry show that the CaRuO₃ layers are in a fully ferromagnetic state (∼0.8 μ_B/Ru), in sharp contrast to the proximity-induced canted antiferromagnetic state in 5d oxides SrIrO₃ and CaIrO₃ (∼0.1 μ_B/Ir). More than that, the magnetic anisotropy of the (001)-(LaMnO₃/CaRuO₃) superlattices is eightfold symmetric, showing potential applications in the technology of multistate data storage.     

Self-intersections of curves on surfaces

Let M be a compact orientable surface with nonempty boundary (x(M)<0) and fundamental group . Let be a geodesic on M (with a fixed hyperbolic structure), and let W be a (cyclically reduced) word in a fixed set of generators of which represents . In this paper, we give an algorithm to count the number of self-intersections of in terms of W, generalizing a result of Birman and Series, where an algorithm was given to decide if was simple. Some applications of the algorithm to surfaces with one boundary and the Markoff spectrum are also given.     

Study of cross-conjugated iso-polytriacetylenes and related oligoenynes

Two series of monodisperse cross-conjugated oligomers based on enyne repeat units have been realized. The first class of molecules, iso-polytriacetylenes (iso-PTAs, 2), was divergently synthesized using an iterative sequence of palladium-catalyzed cross-coupling reactions of vinyl triflate 5 with terminal alkynes. The second series of oligoenynes (17-20) are based on an octatetrayne backbone, and result from homocoupling of the differentially protected iso-PTA oligomers 8-11. The longest member of this series, 20, spans ca. 5.6 nm from Si atom to Si atom and is composed of a contiguous sequence of 44 sp and sp(2) carbons. The lowest energy electronic absorption band for iso-PTA dimers in the progression 13 --> 9 --> 16 is consistently red-shifted as a result of extending the cross-conjugated structure. A similar comparison within each series (i.e., 16, 6-7, or 17-20), however, suggests little effect on the electronic characteristics of these molecules as oligomer length is increased. The solid-state properties of one derivative, 17, are also described.     

Theoretical approach and the practice to the evaluation of structural parameters characterizing concentration polarization alongside ion-exchange membranes by means of dielectric measurement

As the application of a dielectric theory proposed previously (J Membrane Sci 64:153–161 (1991)), theoretical formulation and the practical procedure of dielectric analysis are developed to calculate the structural parameters such as the conductivity gradient and the thickness of the concentration polarization layer, the capacitances and the conductances of the two adjoining aqueous phases from the observed dielectric parameters. The procedure of calculation consequent upon the theoretical formulation was applied to double relaxation data observed for cation-exchange membrane systems under application of d.c. bias voltage. As a consequence, the structural parameters of concentration polarization were readily obtained with accuracy.     

The uranium-Xylidyl Blue I complex and its application in linear sweep polarography

The linear sweep polarographic wave of the uranium-Xylidyl Blue I complex in ethylenediamine-1,10-phenanthroline-hydrochloric acid medium has been studied. The complex, corresponding to UO(2)(XBI)(2-)(2) with log beta' = 9.09 (by polarography), 8.81 (by spectrophotometry), is strongly adsorbed on the surface of the mercury electrode. The polarographic wave is attributed to the reduction of Xylidyl Blue I in the complex. The method is very sensitive with a detection limit of 3 x 10(-8)M. The wave height is proportional to the concentration of uranium over the range 8 x 10(-8)-7 x 10(-6)M. Solvent extraction is used to separate possible interferences. The recommended procedure has been applied to the determination of trace amounts of uranium in ores.