Tandem cyclization/arylation of diaryliodoniums via in situ constructed benzoxazole as a directing group for atom-economical transformation

Linear diaryliodoniums often undergo only single arylation and leave equivalent aryliodide as waste. Herein, we demonstrate that linear unsymmetrical diaryliodoniums could be tuned by dual nickel/palladium metal system to accomplish...

Adsorption and Reaction Mechanisms of Direct Palladium Synthesis by ALD Using Pd(hfac)2 and Ozone on Si (100) Surface

Palladium nanoparticles made by atomic layer deposition (ALD) normally involve formaldehyde or H2 as a reducing agent. Since formaldehyde is toxic and H2 is explosive, it is advantageous to remove this reducing step during the fabrication of palladium metal by ALD. In this work we have successfully used Pd(hfac)2 and ozone directly to prepare palladium nanoparticles, without the use of reducing or annealing agents. Density functional theory (DFT) was employed to explore the reaction mechanisms of palladium metal formation in this process. DFT results show that Pd(hfac)2 dissociatively chemisorbed to form Pd(hfac)* and hfac* on the Si (100) surface. Subsequently, an O atom of the ozone could cleave the C–C bond of Pd(hfac)* to form Pd* with a low activation barrier of 0.46 eV. An O atom of the ozone could also be inserted into the hfac* to form Pd(hfac-O)* with a lower activation barrier of 0.29 eV. With more ozone, the C–C bond of Pd(hfac-O)* could be broken to produce Pd* with an activation barrier of 0.42 eV. The ozone could also chemisorb on the Pd atom of Pd(hfac-O)* to form O3-Pd(hfac-O)*, which could separate into O-Pd(hfac-O)* with a high activation barrier of 0.83 eV. Besides, the activation barrier was 0.64 eV for Pd* that was directly oxidized to PdOx by ozone. Based on activation barriers from DFT calculations, it was possible to prepare palladium without reducing steps when ALD conditions were carefully controlled, especially the ozone parameters, as shown by our experimental results. The mechanisms of this approach could be used to prepare other noble metals by ALD without reducing/annealing agents.

Dissolution of Palladium Metal in Solvent Leaching System with the Presence of Oxidizing Agent

Platinum group metals (PGMs) are important for the manufacture of advanced materials in the field of catalysts and electronic devices. Since the chemical properties of PGMs are very similar to each other, hydrometallurgical processes should be employed to recover PGMs with high purity from either ores or secondary resources. In hydrometallurgical processes for PGMs, the first step is the dissolution of PGMs. For this purpose, inorganic acid solutions with oxidizing agents are generally employed. In this work, nonaqueous solvent leaching systems with a relatively cheap price were employed to investigate the dissolution of pure palladium (Pd) metal. The solvent leaching systems consisted of concentrated hydrochloric acid solution and commercial extractants such as tributyl phosphate (TBP), 7-hydroxydodecan-6-one oxime (LIX 63), and di-n-octyl sulfide (DOS) in the presence of H2O2 as an oxidizing agent. Among the three systems, TBP showed the best efficiency for the dissolution of Pd. The effect of several parameters like TBP concentration, temperature, time, stirring speed and the weight ratio of Pd to TBP/HCl/H2O2 was explored. The dissolution percentage of Pd by the HCl–H2O2–TBP system was higher than by the HCl–H2O–H2O2 system at the same concentration of HCl and H2O2. The role of TBP in enhancing the dissolution of Pd was discussed on the basis of the interaction between HCl and TBP. Compared to aqueous systems, mass transfer is important in the dissolution of Pd metal by the solvent leaching system. Optimum conditions for the complete dissolution of Pd were obtained.

Enhancement of Efficiency of Pd/Al2O3Catalysts in Selective Hydrogenation of Sec-Butylbenzene by Modification with H2SO4 or H2WO4

Hydrogenation of bulky aromatic hydrocarbons is an important problem to be solved in order to improve the quality of fuels. Pd-containing catalysts modified by strong acids have been prepared and studied by diffuse-reflectance IR spectroscopy, and the catalytic activity of the materials has been determined. In studying the selective liquid-phase hydrogenation of sec-butylbenzene as a model substrate, it was shown that modification of Pd/Al2O3 catalysts with acid additives (H2SO4 or H2WO4) results in a significant increase in the hydrogenation activity and selectivity. IR spectroscopy of adsorbed CO and d3-acetonitrile revealed that larger palladium metal particles are formed on the Pd-H2SO4(H2WO4)/Al2O3 catalysts, with ionic states of palladium being present even in the samples reduced in H2.