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- ItemControl of coordinatively unsaturated Zr sites in ZrO2 for efficient C–H bond activation([London] : Nature Publishing Group UK, 2018) Zhang, Yaoyuan; Zhao, Yun; Otroshchenko, Tatiana; Lund, Henrik; Pohl, Marga-Martina; Rodemerck, Uwe; Linke, David; Jiao, Haijun; Jiang, Guiyuan; Kondratenko, Evgenii V.Due to the complexity of heterogeneous catalysts, identification of active sites and the ways for their experimental design are not inherently straightforward but important for tailored catalyst preparation. The present study reveals the active sites for efficient C–H bond activation in C1–C4 alkanes over ZrO2 free of any metals or metal oxides usually catalysing this reaction. Quantum chemical calculations suggest that two Zr cations located at an oxygen vacancy are responsible for the homolytic C–H bond dissociation. This pathway differs from that reported for other metal oxides used for alkane activation, where metal cation and neighbouring lattice oxygen form the active site. The concentration of anion vacancies in ZrO2 can be controlled through adjusting the crystallite size. Accordingly designed ZrO2 shows industrially relevant activity and durability in non-oxidative propane dehydrogenation and performs superior to state-of-the-art catalysts possessing Pt, CrOx, GaOx or VOx species.
- ItemAnharmonic strong-coupling effects at the origin of the charge density wave in CsV3Sb5([London] : Nature Publishing Group UK, 2024) He, Ge; Peis, Leander; Cuddy, Emma Frances; Zhao, Zhen; Li, Dong; Zhang, Yuhang; Stumberger, Romona; Moritz, Brian; Yang, Haitao; Gao, Hongjun; Devereaux, Thomas Peter; Hackl, RudiThe formation of charge density waves is a long-standing open problem, particularly in dimensions higher than one. Various observations in the vanadium antimonides discovered recently further underpin this notion. Here, we study the Kagome metal CsV3Sb5 using polarized inelastic light scattering and density functional theory calculations. We observe a significant gap anisotropy with 2Δmax/kBTCDW≈20, far beyond the prediction of mean-field theory. The analysis of the A1g and E2g phonons, including those emerging below TCDW, indicates strong phonon-phonon coupling, presumably mediated by a strong electron-phonon interaction. Similarly, the asymmetric Fano-type lineshape of the A1g amplitude mode suggests strong electron-phonon coupling below TCDW. The large electronic gap, the enhanced anharmonic phonon-phonon coupling, and the Fano shape of the amplitude mode combined are more supportive of a strong-coupling phonon-driven charge density wave transition than of a Fermi surface instability or an exotic mechanism in CsV3Sb5.
- ItemInterfacial photochemistry at the ocean surface is a global source of organic vapors and aerosols([London] : Nature Publishing Group UK, 2018) Brüggemann, Martin; Hayeck, Nathalie; George, ChristianThe surface of the oceans acts as a global sink and source for trace gases and aerosol particles. Recent studies suggest that photochemical reactions at this air/water interface produce organic vapors, enhancing particle formation in the atmosphere. However, current model calculations neglect this abiotic source of reactive compounds and account only for biological emissions. Here we show that interfacial photochemistry serves as a major abiotic source of volatile organic compounds (VOCs) on a global scale, capable to compete with emissions from marine biology. Our results indicate global emissions of 46.4-184 Tg C yr-1 of organic vapors from the oceans into the marine atmosphere and a potential contribution to organic aerosol mass of more than 60% over the remote ocean. Moreover, we provide global distributions of VOC formation potentials, which can be used as simple tools for field studies to estimate photochemical VOC emissions depending on location and season.
- ItemDirect estimation of the global distribution of vertical velocity within cirrus clouds(London : Nature Publishing Group, 2017) Barahona, Donifan; Molod, Andrea; Kalesse, HeikeCirrus clouds determine the radiative balance of the upper troposphere and the transport of water vapor across the tropopause. The representation of vertical wind velocity, W, in atmospheric models constitutes the largest source of uncertainty in the calculation of the cirrus formation rate. Using global atmospheric simulations with a spatial resolution of 7 km we obtain for the first time a direct estimate of the distribution of W at the scale relevant for cirrus formation, validated against long-term observations at two different ground sites. The standard deviation in W, σ w, varies widely over the globe with the highest values resulting from orographic uplift and convection, and the lowest occurring in the Arctic. Globally about 90% of the simulated σ w values are below 0.1 m s-1 and about one in 104 cloud formation events occur in environments with σ w > 0.8 m s-1. Combining our estimate with reanalysis products and an advanced cloud formation scheme results in lower homogeneous ice nucleation frequency than previously reported, and a decreasing average ice crystal concentration with decreasing temperature. These features are in agreement with observations and suggest that the correct parameterization of σ w is critical to simulate realistic cirrus properties.
- ItemInterface polarization model for a 2-dimensional electron gas at the BaSnO3/LaInO3 interface([London] : Macmillan Publishers Limited, part of Springer Nature, 2019) Kim, Young Mo; Markurt, T.; Kim, Youjung; Zupancic, M.; Shin, Juyeon; Albrecht, M.; Char, KookrinIn order to explain the experimental sheet carrier density n2D at the interface of BaSnO3/LaInO3, we consider a model that is based on the presence of interface polarization in LaInO3 which extends over 2 pseudocubic unit cells from the interface and eventually disappears in the next 2 unit cells. Considering such interface polarization in calculations based on 1D Poisson-Schrödinger equations, we consistently explain the dependence of the sheet carrier density of BaSnO3/LaInO3 heterinterfaces on the thickness of the LaInO3 layer and the La doping of the BaSnO3 layer. Our model is supported by a quantitative analysis of atomic position obtained from high resolution transmission electron microscopy which evidences suppression of the octahedral tilt and a vertical lattice expansion in LaInO3 over 2–3 pseudocubic unit cells at the coherently strained interface.