Effect of surface reconstruction on the photoemission cross-section of the Au(111) surface state

The photoemission cross-section of the Shockley surface state of Au(111) is studied over a wide range of photon energies both experimentally and theoretically. The measurements are fully understood based on the theoretical analysis within a one-step ab?initio theory of photoemission. The constant initial state spectrum is shown to be very sensitive to the structure of the topmost atomic layer. A maximum in the constant initial spectrum at 60?eV is identified as a fingerprint of the Au(111) surface reconstruction.     

Photoinduced Oxygen Atom Transfer to α-Pinene and R-Carvone using a Dioxo-Molybdenum (VI) Complex Incorporated within a Modified UiO-67 (Zr/Ti) MOF

We report a highly selective (100 %) epoxidation of α-pinene and R-carvone using an oxygen atom transfer (OAT) reaction facilitated by a dioxo-Mo complex (Mo^(VI)O₂Cl₂Ln) incorporated into the ligand 5,5’-dicarboxylate-2,2’-bipyridine (bpydc) within a Metal-Organic Framework (MOF) type UiO-67. Photo-stimulated (350 nm) OAT reaction was carried out with oxygen molecular used as the oxidant for 10 h. UiO-67 was synthesized with a mixture of the ligands 2,2′-biphenyl-5,5′-dicarboxylate (bpdc) and 2,2-bipyridine-5,5-dicarboxylate (bpydc) in different molar ratios (67 : 33, 50 : 50, 70 : 30, 0 : 100 bpdc : bpydc) to promote a higher presence of catalytic sites, i. e., the dioxo-Mo complex units. Furthermore, a post-synthetic exchange of Zr for Ti, between 64 : 36 to 78 : 22 Ti : Zr molar ratio, was performed to improve the optical properties of the MOF and promote the photoinduced OAT reaction. The Catalytic system was characterized by FTIR, XRD, ¹H NMR, XPS, TGA, N₂ adsorption/desorption and UV-Vis-DR. The amount of the epoxide monoterpene is proportional to the number of the dioxomolybdenum^(VI) units (MoO₂) incorporated in the UiO-67 (Zr/Ti), and the OAT reaction selectivity is due to the absence of the oxygen radicals in the medium of reaction. Besides, The Mo complex exhibited excellent stability after five cycles of use.     

General Design Concepts for CAPodes as Ionologic Devices

Capacitive analogues of semiconductor diodes (CAPodes) present a new avenue for energy-efficient and nature-inspired next-generation computing devices. Here, we disclose the generalized concept for bias-direction-adjustable n- and p-CAPodes based on selective ion sieving. Controllable-unidirectional ion flux is realized by blocking electrolyte ions from entering sub-nanometer pores. The resulting CAPodes exhibit charge-storage characteristics with a high rectification ratio (96.29 %). The enhancement of capacitance is attributed to the high surface area and porosity of an omnisorbing carbon as counter electrode. Furthermore, we demonstrate the use of an integrated device in a logic gate circuit architecture to implement logic operations (‘OR’, ‘AND’). This work demonstrates CAPodes as a generalized concept to achieve p-n and n-p analogue junctions based on selective ion electrosorption, provides a comprehensive understanding and highlights applications of ion-based diodes in ionologic architectures.