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991.
Rodriguez-Rivera GJ Kim WB Evans ST Voitl T Dumesic JA 《Journal of the American Chemical Society》2005,127(31):10790-10791
Aqueous polyoxometalate (H3PMo12O40) solution reduced by CO with liquid water using gold nanoparticle catalysts at room temperature, which contains protons in liquid water and electrons associated with the reduced polyoxometalate, can produce gaseous H2 or can hydrogenate benzene over an electrochemical cell consisting of a simple carbon anode, a proton-exchange membrane, and a Pt- or Rh-based cathode. In the present cell, H2 can be produced from the reduced H3PMo12O40 solution at voltages that are lower by about 1.15 V compared to water electrolysis. 相似文献
992.
Vieceli J Roeselova M Potter N Dang LX Garrett BC Tobias DJ 《The journal of physical chemistry. B》2005,109(33):15876-15892
A comparative study of OH, O3, and H2O equilibrium aqueous solvation and gas-phase accommodation on liquid water at 300 K is performed using a combination of ab initio calculations and molecular dynamics simulations. Polarizable force fields are developed for the interaction potential of OH and O3 with water. The free energy profiles for transfer of OH and O3 from the gas phase to the bulk liquid exhibit a pronounced minimum at the surface, but no barrier to solvation in the bulk liquid. The calculated surface excess of each oxidant is comparable to calculated and experimental values for short chain, aliphatic alcohols. Driving forces for the surface activity are discussed in terms of the radial distribution functions and dipole orientation distributions for each molecule in the bulk liquid and at the surface. Simulations of OH, O3, and H2O impinging on liquid water with a thermal impact velocity are used to calculate thermal accommodation (S) and mass accommodation (alpha) coefficients. The values of S for OH, O3, and H2O are 0.95, 0.90, and 0.99, respectively. The approaching molecules are accelerated toward the liquid surface when they are approximately 5 angstroms above it. The molecules that reach thermal equilibrium with the surface do so within 2 ps of striking the surface, while those that do not scatter into the gas phase with excess translational kinetic energy in the direction perpendicular to the surface. The time constants for absorption and desorption range from approximately 35 to 140 ps, and the values of alpha for OH, O3, and H2O are 0.83, 0.047, and 0.99, respectively. The results are consistent with previous formulations of gas-phase accommodation from simulations, in which the process occurs by rapid thermal and structural equilibration followed by diffusion on the free energy profile. The implications of these results with respect to atmospheric chemistry are discussed. 相似文献
993.
Felix Mühlhaus Hendrik Weißbarth Tobias Dahmen Gregor Schnakenburg Andreas Gansuer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(40):14346-14350
A titanocene‐catalyzed regiodivergent radical arylation is described that allows access to either enantiomerically pure tetrahydroquinolines or indolines from a common starting material. The regioselectivity of epoxide opening that results in the high selectivity of heterocycle formation is controlled by two factors, the absolute configuration of the enantiopure ligands of the (C5H4R)2TiX2 catalyst and the inorganic ligand X (X=Cl, OTs). The overall reaction is atom‐economical and constitutes a radical Friedel–Crafts alkylation. 相似文献
994.
Hideyuki Tatsuno Kasper S. Kjær Kristjan Kunnus Tobias C. B. Harlang Cornelia Timm Meiyuan Guo Pavel Chàbera Lisa A. Fredin Robert W. Hartsock Marco E. Reinhard Sergey Koroidov Lin Li Amy A. Cordones Olga Gordivska Om Prakash Yizhu Liu Mads G. Laursen Elisa Biasin Frederik B. Hansen Peter Vester Morten Christensen Kristoffer Haldrup Zoltán Németh Dorottya Sárosiné Szemes Éva Bajnóczi György Vankó Tim B. Van Driel Roberto Alonso-Mori James M. Glownia Silke Nelson Marcin Sikorski Henrik T. Lemke Dimosthenis Sokaras Sophie E. Canton Asmus O. Dohn Klaus B. Møller Martin M. Nielsen Kelly J. Gaffney Kenneth Wärnmark Villy Sundström Petter Persson Jens Uhlig 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(1):372-380
Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub-ps X-ray spectroscopy study of an FeIINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3MLCT state, from the initially excited 1MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3MC state, in competition with vibrational relaxation and cooling to the relaxed 3MLCT state. The relaxed 3MLCT state then decays much more slowly (7.6 ps) to the 3MC state. The 3MC state is rapidly (2.2 ps) deactivated to the ground state. The 5MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition-metal complexes for similar ultrafast decays to optimize photochemical performance. 相似文献
995.
Expedient Iron‐Catalyzed C−H Allylation/Alkylation by Triazole Assistance with Ample Scope 下载免费PDF全文
Dr. Gianpiero Cera Tobias Haven Prof. Dr. Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2016,55(4):1484-1488
Triazole assistance set the stage for a unified strategy for the iron‐catalyzed C?H allylation of arenes, heteroarenes, and alkenes with ample scope. The versatile catalyst also proved competent for site‐selective methylation, benzylation, and alkylation with challenging primary and secondary halides. Triazole‐assisted C?H activation proceeded chemo‐, site‐, and diastereo‐selectively, and the modular TAM directing group was readily removed in a traceless fashion under exceedingly mild reaction conditions. 相似文献
996.
Template‐ and Metal‐Free Synthesis of Nitrogen‐Rich Nanoporous “Noble” Carbon Materials by Direct Pyrolysis of a Preorganized Hexaazatriphenylene Precursor 下载免费PDF全文
Ralf Walczak Dr. Bogdan Kurpil Dr. Aleksandr Savateev Dr. Tobias Heil Dr. Johannes Schmidt Qing Qin Prof. Markus Antonietti Dr. Martin Oschatz 《Angewandte Chemie (International ed. in English)》2018,57(33):10765-10770
The targeted thermal condensation of a hexaazatriphenylene‐based precursor leads to porous and oxidation‐resistant (“noble”) carbons. Simple condensation of the pre‐aligned molecular precursor produces nitrogen‐rich carbons with C2N‐type stoichiometry. Despite the absence of any porogen and metal species involved in the synthesis, the specific surface areas of the molecular carbons reach up to 1000 m2 g?1 due to the significant microporosity of the materials. The content and type of nitrogen species is controllable by the carbonization temperature whilst porosity remains largely unaffected at the same time. The resulting noble carbons are distinguished by a highly polarizable micropore structure and have thus high adsorption affinity towards molecules such as H2O and CO2. This molecular precursor approach opens new possibilities for the synthesis of porous noble carbons under molecular control, providing access to the special physical properties of the C2N structure and extending the known spectrum of classical porous carbons. 相似文献
997.
Zbigniew Galazka Steffen Ganschow Klaus Irmscher Detlef Klimm Martin Albrecht Robert Schewski Mike Pietsch Tobias Schulz Andrea Dittmar Albert Kwasniewski Raimund Grueneberg Saud Bin Anooz Andreas Popp Uta Juda Isabelle M. Hanke Thomas Schroeder Matthias Bickermann 《Progress in Crystal Growth and Characterization of Materials》2021,67(1):100511
In the course of development of transparent semiconducting oxides (TSOs) we compare the growth and basic physical properties bulk single crystals of ultra-wide bandgap (UWBG) TSOs, namely β-Ga2O3 and Ga-based spinels MgGa2O4, ZnGa2O4, and Zn1-xMgxGa2O4. High melting points of the materials of about 1800 -1930 °C and their thermal instability, including incongruent decomposition of Ga-based spinels, require additional tools to obtain large crystal volume of high structural quality that can be used for electronic and optoelectronic devices. Bulk β-Ga2O3 single crystals were grown by the Czochralski method with a diameter up to 2 inch, while the Ga-based spinel single crystals either by the Czochralski, Kyropoulos-like, or vertical gradient freeze / Bridgman methods with a volume of several to over a dozen cm3. The UWBG TSOs discussed here have optical bandgaps of about 4.6 - 5 eV and great transparency in the UV / visible spectrum. The materials can be obtained as electrical insulators, n-type semiconductors, or n-type degenerate semiconductors. The free electron concentration (ne) of bulk β-Ga2O3 crystals can be tuned within three orders of magnitude 1016 - 1019 cm?3 with a maximum Hall electron mobility (μ) of 160 cm2V?1s?1, that gradually decreases with ne. In the case of the bulk Ga-based spinel crystals with no intentional doping, the maximum of ne and μ increase with decreasing the Mg content in the compound and reach values of about 1020 cm?3 and about 100 cm2V?1s?1 (at ne > 1019 cm?3), respectively, for pure ZnGa2O4. 相似文献
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