Uncommon and Emissive {[Au2(C3H6NS2)2][Au(C3H6NS2)2]2(PF6)2} Mixed Au+ and Au3+ Pseudotetranuclear Crystalline Compound: Synthesis, Structural Characterization, and Optical Properties.

An uncommon emissive pseudotetranuclear compound, {[Au2(C3H6NS2)2][Au(C3H6NS2)2]2(PF6)2}, was synthesized and characterized in terms of its structure and optical properties. The synthesis produced a crystalline compound composed of four gold atoms with two different oxidation states (Au+ and Au3+) in the same crystalline structure. The title complex belonged to a triclinic crystalline system involving the centrosymmetric P1̅ space group. X-ray diffractometry and vibrational spectroscopy (infrared, Raman, and SERS) were used for structural characterization of the new crystal. The vibrational spectroscopy techniques supported the X-ray diffraction results and confirmed the presence of bonds including Au-Au and Au-S. Optical characterization performed using UV-vis spectroscopy showed that under ultraviolet excitation, the emissive crystalline complex presented characteristic broad luminescent bands centered at 420 and 670 nm.

Total Syntheses of Aporphine Alkaloids via Benzyne Chemistry: An Approach to the Formation of Aporphine Cores.

Total syntheses of lysicamine, (±)-nuciferine, (±)-nornuciferine, (±)-zanthoxyphylline iodide, (±)-O-methylisothebaine, and (±)-trimethoxynoraporphine were accomplished by an approach that involves the formation of aporphine cores through reactions between an isoquinoline derivative and silylaryl triflates promoted by CsF. Unprecedented formations of aporphine cores proceeded in good yields presumably through [4 + 2] cycloaddition reactions followed by hydrogen migrations.

Highly Electroactive Ni Pyrophosphate/Pt Catalyst toward Hydrogen Evolution Reaction.

Robust electrocatalysts toward the resourceful and sustainable generation of hydrogen by splitting of water via electrocatalytic hydrogen evolution reaction (HER) are a prerequisite to realize high-efficiency energy research. Highly electroactive catalysts for hydrogen production with ultralow loading of platinum (Pt) have been under exhaustive exploration to make them cutting-edge and cost-effectively reasonable for water splitting. Herein, we report the synthesis of hierarchically structured nickel pyrophosphate (ß-Ni2P2O7) by a precipitation method and nickel phosphate (Ni3(PO4)2) by two different synthetic routes, namely, simple cost-effective precipitation and solution combustion processes. Thereafter, Pt-decorated nickel pyrophosphate and nickel phosphate (ß-Ni2P2O7/Pt and Ni3(PO4)2/Pt) were prepared by using potassium hexachloroplatinate and ascorbic acid. The fabricated novel nickel pyrophosphate and nickel phosphate/Pt materials were utilized as potential and affordable electrocatalysts for HER by water splitting. The detailed electrochemical studies revealed that the ß-Ni2P2O7/Pt (1 µg·cm-2 Pt) electrocatalyst showed excellent electrocatalytic performances for HER in acidic solution with an overpotential of 28 mV at -10 mA·cm-2, a Tafel slope of 32 mV·dec, and an exchange current density ( j0) of -1.31 mA·cm-2, which were close to the values obtained using the Vulcan/Pt (8.0 µg·cm-2 Pt), commercial benchmarking electrocatalyst with eight times higher Pt amount. Furthermore, the ß-Ni2P2O7/Pt electrocatalyst maintains an excellent stability for over -0.1 V versus RHE for 12 days, keeping j0 equal after the stability test (-1.28 mA cm-2). Very well-distributed Pt NPs inside the "cages" on the ß-Ni2P2O7 structure with a crystalline pattern of 0.67 nm distance to the Ni2P2O7/Pt electrocatalyst, helping the Volmer-Tafel mechanism with the Tafel reaction as a major rate-limiting step, help to liberate very fast the Pt sites after HER. The high electrocatalytic performance and remarkable durability showed the ß-Ni2P2O7/Pt material to be a promising cost-effective electrocatalyst for hydrogen production.

Synthesis and characterization of TiO2 and TiO2/Ag for use in photodegradation of methylviologen, with kinetic study by laser flash photolysis.

This paper reports the synthesis, characterization, and application of TiO2 and TiO2/Ag nanoparticles for use in photocatalysis, employing the herbicide methylviologen (MV) as a substrate for photocatalytic activity testing. At suitable metal to oxide ratios, increases in silver surface coating on TiO2 enhanced the efficiency of heterogeneous photocatalysis by increasing the electron transfer constant. The sol-gel method was used for TiO2 synthesis. P25 TiO2 was the control material. Both oxides were subjected to the same silver incorporation process. The materials were characterized by conventional spectroscopy, SEM micrography, X-ray diffraction, calculation of surface area per mass of catalyst, and thermogravimetry. Also, electron transfers between TiO2 or TiO2/Ag and MV in the absence and presence of sodium formate were investigated using laser flash photolysis. Oxides synthesized with 2.0 % silver exhibited superior photocatalytic activity for MV degradation.