Tetragonal Li10GeP2S12 and Li7GePS8 - exploring the Li ion dynamics in LGPS Li electrolytes

Tetragonal Li10GeP2S12 (LGPS) is the best solid Li electrolyte reported in the literature. In this study we present the first in-depth study on the structure and Li ion dynamics of this structure type. We prepared two different tetragonal LGPS samples, Li10GeP2S12 and the new compound Li7GePS8. The Li ion dynamics and the structure of these materials were characterized using a multitude of complementary techniques, including impedance spectroscopy, Li-7 PFG NMR, Li-7 NMR relaxometry, X-ray diffraction, electron diffraction, and P-31 MAS NMR. The exceptionally high ionic conductivity of tetragonal LGPS of similar to 10(-2) S cm(-1) is traced back to nearly isotropic Li hopping processes in the bulk lattice of LGPS with E-A approximate to 0.22 eV

Rational Strain Engineering in Delafossite Oxides for Highly Efficient Hydrogen Evolution Catalysis in Acidic Media

The rational design of hydrogen evolution reaction (HER) electrocatalysts which are competitive with platinum is an outstanding challenge to make power-to-gas technologies economically viable. Here, we introduce the delafossites PdCrO$_2$, PdCoO$_2$ and PtCoO$_2$ as a new family of electrocatalysts for the HER in acidic media. We show that in PdCoO$_2$ the inherently strained Pd metal sublattice acts as a pseudomorphic template for the growth of a strained (by +2.3%) Pd rich capping layer under reductive conditions. The surface modification continuously improves the electrocatalytic activity by simultaneously increasing the exchange current density j$_0$ from 2 to 5 mA/cm$^2_{geo}$ and by reducing the Tafel slope down to 38 mV/decade, leading to overpotentials $\eta_{10}$ < 15 mV for 10 mA/cm$^2_{geo}$, superior to bulk platinum. The greatly improved activity is attributed to the in-situ stabilization of a $\beta$-palladium hydride phase with drastically enhanced surface catalytic properties with respect to pure or nanostructured palladium. These findings illustrate how operando induced electrodissolution can be used as a top-down design concept for rational surface and property engineering through the strain-stabilized formation of catalytically active phases

Tuning the stacking behaviour of a 2D covalent organic framework through non-covalent interactions

Two-dimensional covalent organic frameworks (COFs) are crystalline porous materials composed of organic building blocks that are connected via covalent bonds within their layers, but through non-covalent interactions between the layers. The exact stacking sequence of the layers is of paramount importance for the optoelectronic, catalytic and sorption properties of these polymeric materials. The weak interlayer interactions lead to a variety of stacking geometries in COFs, which are both hard to characterize and poorly understood due to the low levels of crystallinity. Therefore, detailed insights into the stacking geometry in COFs is still largely elusive. In this work we show that the geometric and electronic features of the COF building blocks can be used to guide the stacking behavior of two related 2D imine COFs (TBI-COF and TTI-COF), which either adopt an averaged "eclipsed'' structure with apparent zero-offset stacking or a unidirectionally slip-stacked structure, respectively. These structural features are confirmed by XRPD and TEM measurements. Based on theoretical calculations, we were able to pinpoint the cause of the uniform slip-stacking geometry and high crystallinity of TTI-COF to the inherent self-complementarity of the building blocks and the resulting donor-acceptor-type stacking of the imine bonds in adjacent layers, which can serve as a more general design principle for the synthesis of highly crystalline COFs

The Stacking Faulted Nature of the Narrow Gap Semiconductor Sc2_{2}Si2_{2}Te6_{6}

Crystals of Sc$_{2}$Si$_{2}$Te$_{6}$ have been grown and its crystal, micro- and electronic structures were investigated. The layered character of the title compound exhibits stacking faults that impede a full structural characterization by single crystal X-ray diffraction due to diffuse scattering. Based on high resolution transmission electron micrographs and diffraction patterns, the stacking faulted nature of the real structure of Sc$_{2}$Si$_{2}$Te$_{6}$ has been revealed. Different stacking models were derived from the idealized, faultless structure and the stacking disorder was quantitatively analyzed by Rietveld refinement of powder X-ray diffraction patterns. An energetic comparison of the stacking models by density functional theory is in line with the experimental observations. Further, the bonding situation was investigated by electronic structure calculations. Sc$_{2}$Si$_{2}$Te$_{6}$ is a narrow gap semiconductor with an indirect band gap of 0.65 eV

Sub-stoichiometric 2D covalent organic frameworks from tri- and tetratopic linkers

Covalent organic frameworks (COFs) are typically designed by breaking down the desired network into feasible building blocks - either simple and highly symmetric, or more convoluted and thus less symmetric. The linkers are chosen complementary to each other such that an extended, fully condensed network structure can form. We show not only an exception, but a design principle that allows breaking free of such design rules. We show that tri- and tetratopic linkers can be combined to form imine-linked [4 + 3] sub-stoichiometric 2D COFs featuring an unexpected bex net topology, and with periodic uncondensed amine functionalities which enhance CO2 adsorption, can be derivatized in a subsequent reaction, and can also act as organocatalysts. We further extend this class of nets by including a ditopic linker to form [4 + 3 + 2] COFs. The results open up possibilities towards a new class of sub-valent COFs with unique structural, topological and compositional complexities for diverse applications

Morphology matters: 0D/2D WO3 nanoparticle-ruthenium oxide nanosheet composites for enhanced photocatalytic oxygen evolution reaction rates

In the field of artificial photosynthesis with semiconductor light harvesters, the default cocatalyst morphologies are isotropic, 0D nanoparticles. Herein, the use of highly anisotropic 2D ruthenium oxide nanosheet (RONS) cocatalysts as an approach to enhance photocatalytic oxygen evolution (OER) rates on commercial WO3 nanoparticles (0D light harvester) is presented. At optimal cocatalyst loadings and identical photocatalysis conditions, WO3 impregnated with RONS (RONS/WO3) shows a fivefold increase in normalized photonic efficiency compared to when it is impregnated with conventional ruthenium oxide (rutile) nanoparticles (RONP/WO3). The superior RONS/WO3 performance is attributed to two special properties of the RONS: i) lower electrochemical water oxidation overpotential for RONS featuring highly active edge sites, and ii) decreased parasitic light absorption on RONS. Evidence is presented that OER photocatalytic performance can be doubled with control of RONS edges and it is shown that compared to WO3 impregnated with RONP, the advantageous optical properties and geometry of RONS decrease the fraction of light absorbed by the cocatalyst, thus reducing the parasitic light absorption on the RONS/WO3 composite. Therefore, the results presented in the current study are expected to promote engineering of cocatalyst morphology as a complementary concept to optimize light harvester-cocatalyst composites for enhanced photocatalytic efficiencyA.G. and S.L. contributed equally to this work. Financial support is gratefully acknowledged from the Max Planck Society, the Cluster of Excellence “e-conversion” (EXC 2089/1–390776260), and the Center for Nanoscience. S.L. is thankful to the Science and Engineering Research Board (SERB), Government of India, for the award of a Ramanujan Fellowship (RJF/2021/000050). A.J.-S. gratefully acknowledges Spanish Ministry of Universities for funding through a Beatriz Galindo Research fellowship BG20/00015. The authors thank Prof. Gisela Schütz (Max Planck Institute for Intelligent Systems, MPI-IS, Stuttgart) for access to XPS analysis at their facilities. The authors are grateful to Dr. Gunther Richter for helpful discussion of XPS data and the MPI-IS for the XPS infrastructure support. The authors thank Andres RodríguezCamargo for FTIR and PXRD measurements and Marie-Luise Schreiber for extensive ICPOES elemental analysis. Open access funding enabled and organized by Projekt DEA

Rational design of carbon nitride photocatalysts by identification of cyanamide defects as catalytically relevant sites

The heptazine-based polymer melon (also known as graphitic carbon nitride, g-C3N4) is a promising photocatalyst for hydrogen evolution. Nonetheless, attempts to improve its inherently low activity are rarely based on rational approaches because of a lack of fundamental understanding of its mechanistic operation. Here we employ molecular heptazine-based model catalysts to identify the cyanamide moiety as a photocatalytically relevant 'defect'. We exploit this knowledge for the rational design of a carbon nitride polymer populated with cyanamide groups, yielding a material with 12 and 16 times the hydrogen evolution rate and apparent quantum efficiency (400 nm), respectively, compared with the unmodified melon. Computational modelling and material characterization suggest that this moiety improves coordination (and, in turn, charge transfer kinetics) to the platinum co-catalyst and enhances the separation of the photogenerated charge carriers. The demonstrated knowledge transfer for rational catalyst design presented here provides the conceptual framework for engineering high-performance heptazine-based photocatalysts

Non symmorphic band degeneracy at the Fermi level in ZrSiTe

Non-symmorphic materials have recently been predicted to exhibit many different exotic features in their electronic structures. These originate from forced band degeneracies caused by the non-symmorphic symmetry, which not only creates the possibility to realize Dirac semimetals, but also recently resulted in the prediction of novel quasiparticles beyond the usual Dirac, Weyl or Majorana fermions, which can only exist in the solid state. Experimental realization of non-symmorphic materials that have the Fermi level located at the degenerate point is difficult, however, due to the requirement of an odd band filling. In order to investigate the effect of forced band degeneracies on the transport behavior, a material that has such a degeneracy at or close to the Fermi level is desired. Here, we show with angular resolved photoemission experiments supported by density functional calculations, that ZrSiTe hosts several fourfold degenerate Dirac crossings at the X point, resulting from non-symmorphic symmetry. These crossings form a Dirac line node along XR, which is located almost directly at the Fermi level and shows almost no dispersion in energy. ZrSiTe is thus the first real material that allows for transport measurements investigating Dirac fermions that originate from non-symmorphic symmetry.Comment: 13 pages, 4 figures, accepted for publication in New Journal of Physic