Lowering of the oxygen evolution reaction (OER) noble metal catalyst loading on the anode of a polymer electrolyte membrane water electrolysis (PEMWE) is a necessity for enabling the large-scale hydrogen production based on this technology. This study introduces a remarkably active OER catalyst that is based on the dispersion of Ir nanoparticles on a highly conductive oxide support. The catalyst was designed in a way to combine all characteristics that have been reported to enhance the OER activity on an Ir oxide-based catalyst, including high catalyst dispersion and controlling the Ir catalyst particle size, so that this design approach provides both high surface area to Ir mass ratio and at the same time ensures maximum synergetic interaction with the oxide support, termed strong metal−support interaction (SMSI). This was achieved through using a high surface area (50 m 2 /g) and highly conductive antimony-doped tin oxide support (2 S/cm), where combining a high catalyst dispersion and maximum SMSI resulted in a very high OER activity of the Ir/ATO catalyst (≈1100 A/g Ir , at 80 °C and 1.45 V RHE ). This enhanced activity will allow a significant reduction (ca. 75-fold) in the precious metal catalyst loading when this catalyst is implemented in the anode of a PEMWE.
In single-molecule applications, the photostability of fluorescent molecules is a key parameter. We apply fluorescence correlation spectroscopy to compare the photostability of four fluorescein and four borondipyrromethene (BODIPY) dyes of similar structure but different triplet yields. The latter class of dyes are more stable. In the kinetic analysis the, diffusion and photobleaching are treated as competitive processes. Corrections, which account for saturation and for experimental artefacts, are achieved solely by using experimental data. Photobleaching is found to occur mainly through the first excited singlet state S(1), in contrast to previous findings.
The
polymer binders used in most lithium-ion batteries (LIBs) serve
only a structural role, but there are exciting opportunities to increase
performance by using polymers with combined electronic and ionic conductivity.
To this end, here we examine dihexyl-substituted poly(3,4-propylenedioxythiophene)
(PProDOT-Hx2) as an electrochemically stable π-conjugated
polymer that becomes electrically conductive (up to 0.1 S cm–1) upon electrochemical doping in the potential range of 3.2 to 4.5
V (vs Li/Li+). Because this family of polymers is easy
to functionalize, can be effectively fabricated into electrodes, and
shows mixed electronic and ionic conductivity, PProDOT-Hx2 shows promise for replacing the insulating polyvinylidene fluoride
(PVDF) commonly used in commercial LIBs. A combined experimental and
theoretical study is presented here to establish the fundamental mixed
ionic and electronic conductivity of PProDOT-Hx2. Electrochemical
kinetics and electron spin resonance are first used to verify that
the polymer can be readily electrochemically doped and is chemically
stable in a potential range of interest for most cathode materials.
A novel impedance method is then used to directly follow the evolution
of both the electronic and ionic conductivity as a function of potential.
Both values increase with electrochemical doping and stay high across
the potential range of interest. A combination of optical ellipsometry
and grazing incidence wide angle X-ray scattering is used to characterize
both solvent swelling and structural changes that occur during electrochemical
doping. These experimental results are used to calibrate molecular
dynamics simulations, which show improved ionic conductivity upon
solvent swelling. Simulations further attribute the improved ionic
conductivity of PProDOT-Hx2 to its open morphology and
the increased solvation is possible because of the oxygen-containing
propylenedioxythiophene backbone. Finally, the performance of PProDOT-Hx2 as a conductive binder for the well-known cathode LiNi0.8Co0.15Al0.05O2 relative
to PVDF is presented. PProDOT-Hx2-based cells display a
fivefold increase in capacity at high rates of discharge compared
to PVDF-based electrodes at high rates and also show improved long-term
cycling stability. The increased rate capability and cycling stability
demonstrate the benefits of using binders such as PProDOT-Hx2, which show good electronic and ionic conductivity, combined with
electrochemical stability over the potential range for standard cathode
operation.
We report the synthesis and characterization of the missing reference core compound 4,4-Difluoro-4-bora-(3a,4a)-diaza-s-indacene 1 of the BODIPY fluorescent dye class. The compound exhibits a fluorescence lifetime of 7.2 ns and has a high photostability.
We thank the Deutsche Forschungsgemeinschaft (DFG) for their financial support (EXC81, SFB623). We also acknowledge Stephen Hashmi (Heidelberg University) for fruitful discussions. Volker Huch is gratefully acknowledged for X-ray crystallography. Michael Schwering and Dominik Brox have continuously supported the project with their expertise in microscopy.Supporting information for this article, including details of reagents used, instruments, and analytical data, including spectroscopic characterization, is available on the WWW under http://dx.
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