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    Selective Earth-Abundant System for CO2 Reduction: Comparing Photo- and Electrocatalytic Processes
    (Washington, DC : American Chemical Society, 2019) Steinlechner C.; Roesel A.F.; Oberem E.; Päpcke A.; Rockstroh N.; Gloaguen F.; Lochbrunner S.; Ludwig R.; Spannenberg A.; Junge H.; Francke R.; Beller M.
    The valorization of CO2 via photo- or electrocatalytic reduction constitutes a promising approach toward the sustainable production of fuels or value-added chemicals using intermittent renewable energy sources. For this purpose, molecular catalysts are generally studied independently with respect to the photo- or the electrochemical application, although a unifying approach would be much more effective with respect to the mechanistic understanding and the catalyst optimization. In this context, we present a combined photo- and electrocatalytic study of three Mn diimine catalysts, which demonstrates the synergistic interplay between the two methods. The photochemical part of our study involves the development of a catalytic system containing a heteroleptic Cu photosensitizer and the sacrificial BIH reagent. The system shows exclusive selectivity for CO generation and renders turnover numbers which are among the highest reported thus far within the group of fully earth-abundant photocatalytic systems. The electrochemical part of our investigations complements the mechanistic understanding of the photochemical process and demonstrates that in the present case the sacrificial reagent, the photosensitizer, and the irradiation source can be replaced by the electrode and a weak Brønsted acid. © 2019 American Chemical Society.
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    Comparison of transition metal (Fe, Co, Ni, Cu, and Zn) containing tri-metal layered double hydroxides (LDHs) prepared by urea hydrolysis
    (Cambridge : RSC, 2019) Naseem, Sajid; Gevers, Bianca; Boldt, Regine; Labuschagné, Frederick J. W. J.; Leuteritz, Andreas
    This paper details a successful synthesis and comparison of a range of tri-metal hydrotalcite-like layered double hydroxides (LDHs) using urea hydrolysis. Transition-metal-substituted MgMAl-LDHs were synthesized with M = Fe, Co, Ni, Cu or Zn. 5 mol% and 10 mol% substitutions were performed, where Mg was substituted with Co, Ni, Cu and Zn, and Al with Fe. The successful synthesis of crystalline MgMAl-LDHs was confirmed using X-ray powder diffraction (XRD) analysis. Energy-dispersive X-ray (EDX) spectroscopy was used to identify substituted metals and determine changes in composition. Changes in morphology were studied using scanning electron microscopy (SEM). Thermogravimetric analysis was used to determine the effect of Fe-, Co-, Ni-, Cu- or Zn-substitution on the thermal degradation of the MgMAl-LDH phase. The structure, morphology and thermal behavior of the LDHs were shown to be influenced by the substituted transition metals. The observed thermal stability took the order MgNiAl- > MgFeAl- = MgAl- ≥ MgCoAl- > MgCuAl- > MgZnAl-LDH. The urea hydrolysis method was shown to be a simple preparation method for well-defined crystallite structures with large hexagonal platelets and good distribution of transition metal atoms in the substituted LDHs. © 2019 The Royal Society of Chemistry.
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    Systematic tuning of segmented magnetic nanowires into three-dimensional arrays of 'bits'
    (London : RSC Publishing, 2017) Bochmann, S.; Fernandez-Pacheco, A.; Mačković, M.; Neff, A.; Siefermann, K.R.; Spiecker, E.; Cowburn, R.P.; Bachmann, J.
    A method is presented for the preparation of a three-dimensional magnetic data storage material system. The major ingredients are an inert nanoporous matrix prepared by anodization and galvanic plating of magnetic and non-magnetic metals in wire shape inside the cylindrical pores. The individual nanomagnets consist of a nickel-cobalt alloy, the composition of which is tuned systematically by adjusting the electrolytic bath composition at one optimal applied potential. The lowest magnetocrystalline anisotropy is obtained at the composition Ni60Co40, as quantified by superconducting quantum interference device magnetometry. Wires of this composition experience a pinning-free propagation of magnetic domain walls, as determined by single-wire magneto-optical Kerr effect magnetometry. Adding copper into the electrolyte allows one to generate segments of Ni60Co40 separated by non-magnetic copper. The segment structure is apparent in individual nanowires imaged by scanning electron microscopy, UV-photoelectron emission microscopy, and transmission electron microscopy. The single-domain structure of the wire segments is evidenced by magnetic force microscopy.