Sharif Digital Repository

The complexes PdII(qcq)(OAc) and PtII(qcq)Cl have been synthesized using environmentally benign synthesized ligands and characterized by elemental analyses: Fourier transform infrared spectroscopy, UV–visible spectroscopy, 1H NMR spectroscopy, and X-ray diffraction. The catalytic activity of the complex was assessed, in different media, for the Mizoroki–Heck coupling reaction for typical aryl halides and terminal olefins under aerobic conditions. Since the base and the solvent were found to influence the efficiency of the reaction, reaction conditions, temperature, time, and the amount of K3PO4 and a mixture of H2O/PEG, were optimized. We found, for the Mizoroki–Heck reaction coupling less... 

The use of 1,3-bis(N-heterocyclic)carbene ligands with different alkyl wingtip groups (alkyl = methyl, isopropyl and tert-butyl) is an effective method for the palladium-catalysed direct S-arylation of methylphenyl sulfoxide and C-C coupling of various of aryl halides with alkenes. The reactions proceed in moderate to good yields. Interestingly, it is shown experimentally that, by using bulkier bidentate N-heterocyclic carbene ligands, more selective catalytic systems towards cis products in Heck coupling reactions can be achieved  

Liquid phase hydro-purification of crude terephthalic acid (CTA) was performed using supported Pd and Pd-Sn catalysts on functionalized multi-wall carbon nanotubes (FMWCNT). Pd/FMWCNT catalysts were prepared by wet impregnation with Pd loadings of 0.05 to 0.6 wt.%. Pd-Sn/FMWCNT catalysts were prepared by co-impregnation (CI) and successive impregnation (SI) using 0.3 wt.% Pd loading and Sn/Pd molar ratios of 0.1 and 0.35 for the CI method and 0.05 to 0.35 for the SI method. Pd loading of 0.3 wt.% for Pd/FMWCNT was sufficient to decrease the 4-carboxybenzaldehyde (4-CBA) content of CTA from 2100 ppm to 5.5 ppm without excessive hydrogenation of terephthalic acid (TA). The commercial catalyst... 

The solubility of Pd(NO3)2 in water is moderate whereas it is completely soluble in diluted HNO3 solution. Pd/MIL-101(Cr) and Pd/MIL-101-NH2(Cr) were synthesized by aqueous solution of Pd(NO3)2 and Pd(NO3)2 solution in dilute HNO3 and used for CO oxidation reaction. The catalysts synthesized with Pd(NO3)2 solution in dilute HNO3 showed lower activity. The aqueous solution of Pd(NO3)2 was used for synthesis of mono-metal Ni, Pd and bimetallic PdNi nanoparticles with various molar ratios supported on MOF. Pd70Ni30/MIL-101(Cr) catalyst showed higher activity than monometallic counterparts and Pd + Ni physical mixture due to the strong synergistic effect of PdNi nanoparticles, high distribution... 

The solubility of Pd(NO3)2 in water is moderate whereas it is completely soluble in diluted HNO3 solution. Pd/MIL-101(Cr) and Pd/MIL-101-NH2(Cr) were synthesized by aqueous solution of Pd(NO3)2 and Pd(NO3)2 solution in dilute HNO3 and used for CO oxidation reaction. The catalysts synthesized with Pd(NO3)2 solution in dilute HNO3 showed lower activity. The aqueous solution of Pd(NO3)2 was used for synthesis of mono-metal Ni, Pd and bimetallic PdNi nanoparticles with various molar ratios supported on MOF. Pd70Ni30/MIL-101(Cr) catalyst showed higher activity than monometallic counterparts and Pd + Ni physical mixture due to the strong synergistic effect of PdNi nanoparticles, high distribution... 

The solubility of Pd(NO3)2 in water is moderate whereas it is completely soluble in diluted HNO3 solution. Pd/MIL-101(Cr) and Pd/MIL-101-NH2(Cr) were synthesized by aqueous solution of Pd(NO3)2 and Pd(NO3)2 solution in dilute HNO3 and used for CO oxidation reaction. The catalysts synthesized with Pd(NO3)2 solution in dilute HNO3 showed lower activity. The aqueous solution of Pd(NO3)2 was used for synthesis of mono-metal Ni, Pd and bimetallic PdNi nanoparticles with various molar ratios supported on MOF. Pd70Ni30/MIL-101(Cr) catalyst showed higher activity than monometallic counterparts and Pd + Ni physical mixture due to the strong synergistic effect of PdNi nanoparticles, high distribution... 

In the present work, a simple, green, rapid, and catalyst-free procedure for the synthesis of benzamide derivatives by ring opening of azlactones with diamines such as ethylene diamine and 1,3-propylenediamine is described. The present method offers several advantages such as short reaction times, easy work-up, and mild reaction conditions in the absence of catalyst and any toxic solvent and material. In addition, the structure obtained by X-ray crystallography was compared with the theoretical results obtained by density functional theory using the B3LYP functional and cc-pVDZ basis sets  

Palladium nanoparticles (Pd-NPs) were supported on functional and nonfunctional Co-coordination polymers (Pd/CoBDCNH2 and Pd/CoBDC). Advanced analytical techniques revealed that Pd-NPs are supported on the external surface of the polymer framework and the functionalized framework possesses effective influence to prevent Pd-NP aggregation. Supported Pd-NPs were effectively applied as heterogeneous recyclable catalysts in the Mizoroki–Heck C–C cross coupling reactions of iodobenzene and either aromatic or aliphatic terminal alkenes. Catalytic results exhibited that highly dispersed Pd-NPs with low loading (1%) on the functional polymer (Pd/CoBDCNH2) are more effective than aggregated Pd-NPs... 

The present study reports a simple electrochemical approach to the fabrication of a new nanocomposite containing PtPd nanoflowers (NFs) promoted with two-dimensional (2D) nanosheets (NSs) structure cuprous oxide (Cu2O) supported on reduced graphene oxide (rGO) (PtPd-NFs/Cu2O-NSs/rGO). Scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectra, Raman spectroscopy, and energy dispersive X-ray spectroscopy are used for characterization of the PtPd-NPs/Cu2O-NPs/rGO. SEM images showed that vertical-standing arrays of Cu2O with an edge length up to 1 μm and thickness of about 20 nm are electrodeposited on the surface of rGO film. Also, PtPd needle-like NFs with visible and... 

The demonstration of high entropy alloys (HEAs), or more generally multi-principal-element alloys (MPEAs), which display a greater resistance to softening at elevated temperatures and embrittlement at cryogenic temperatures, has offered an accessible alternative alloying process for materials scientists and engineers. Although solidification is a fundamental process in synthesis of alloys which strongly affects their microstructure and properties, a firm understanding of this process in HEAs is scarce. Here, using molecular dynamics (MD) simulations, we study the rapid solidification of the multi-principal-element CoFeNiPd alloy as a prototypical single-phase HEA. Our simulations reveal an... 

Supportless Ni-Pd-0.1CNT foamy nanocatalyst with specific surface area of 611.3 m2/g was produced by electroless deposition of nickel, palladium and multiwall carbon nanotube (MWCNT) on interim polyurethane substrate. Application of temperature programmed reduction (TPR) and temperature programmed oxidation (TPO) data into Kissinger (Redhead) kinetic model showed lessening of their activation energies due to Pd and CNT addition. Presence of foamy Ni/SiC caused 8% higher steam reforming of methane; while Ni-Pd-0.1CNT presence resulted in 22% higher methane conversion. The catalytic behavior of the samples was described by morphological and compositional studies which were carried out by... 

Reaction of 2-pyridinecarboxaldehyde with L-Alaninol (as a chiral amine) or 2-amino-2-methyl-1-propanol (AMP) in the presence of PdCl2 produced the new and attractive palladium(II) complexes which were synthesized by in situ method. The presence of an extra methyl group in AMP other than L-Alaninol induced the different chelating mode and, therefore, several structurally different palladium complexes obtained. Correspondingly, the chiral amine with PdCl2 produced the imine product, (Iminol (1)), and an oxazolidine compound (Imizol (1′)) as minor product. Also, the use of AMP in formation of palladium complexes led to the synthesis of imine (Ampynol (2)) and oxazolidine (Ampyzol (3))... 

Amine-functionalized MIL-101(Cr) has been synthesized by hydrothermal (MNH2) and post-synthetic modification (MNH2-p) approaches. Pd/MNH2 and Pd/MNH2-p have been tested in CO oxidation reaction as a gas phase reaction to clarify the difference between two synthesis approaches. Their performance has also been compared with that of Pd supported on MIL as a common MOF and CuBTC as a commercial one. The results show the significant difference between Pd/MNH2-p and Pd/MNH2, where CO conversion of 100% was not observed for Pd/MNH2-p, whereas Pd/MNH2 outperformed the others and exhibited the high reaction rate thanks to the active sites created by amorphization during the reduction process because... 

For the first time, the effect of calcination process on characteristics and catalytic performances of Pd supported on different MOFs (MIL-101(Cr), NH2-MIL-101(Cr), and HKUST-1) was evaluated. Besides, the various orders of calcination process and reduction one on Pd/MOF and Pd/calcinated-MOF were studied, and their performances in CO oxidation reaction were presented to find the effect of H2 and O2. Results showed that the effect of calcination and reduction processes on the catalytic activities and characteristics strongly depends on the nature of MOF. Among MIL-based catalysts, the catalyst with no calcination treatment showed the best activity. Among MNH2-based catalysts, high activity... 

For the first time, the effect of calcination process on characteristics and catalytic performances of Pd supported on different MOFs (MIL-101(Cr), NH2-MIL-101(Cr), and HKUST-1) was evaluated. Besides, the various orders of calcination process and reduction one on Pd/MOF and Pd/calcinated-MOF were studied, and their performances in CO oxidation reaction were presented to find the effect of H2 and O2. Results showed that the effect of calcination and reduction processes on the catalytic activities and characteristics strongly depends on the nature of MOF. Among MIL-based catalysts, the catalyst with no calcination treatment showed the best activity. Among MNH2-based catalysts, high activity... 

This study forwards a novel and simple approach for encapsulation of Phosphotungstic acid (PTA) into MIL-101(Cr) cavities to develop PTA-MIL-101(Cr) with a high surface area. In this method, the resulting surface area of PTA-MIL-101(Cr) (3563 m2/g) is 1.72 times that of MIL-101(Cr) due to the existence of more accessible pores which are formed by leaching of PTAs incorporated inside MIL-101(Cr) pores during the intense washing. Catalysts are investigated in CO oxidation under atmospheric pressure and feed composition of 1%CO, 20%O2, and 79%He. 3%Pd/PTA-MIL-101(Cr) shows 100%CO conversion at T = 145 °C and outperforms PTA, PTA-MIL-101(Cr), Pd/PTA, 1–3%Pd/MIL-101(Cr), Pd-PTA/MIL-101(Cr), and... 

This study investigated the synthesis of Pd nanoparticles (NPs) using a high-gravity technique mediated by Salvia hispanica leaf extracts. Biological assays confirmed their antibacterial activity against gram positive (S. aureus) and gram negative (E. coli) bacteria with significant antioxidant activity in comparison with the standards as well as low cellular toxicity on PC12 and HEK293 cell lines. To the best of our knowledge, this study can be considered as the first investigation of Pd-NPs synthesized by Salvia hispanica leaf extracts assisted by a high-gravity technique. In addition, the mentioned green synthesis procedure led to the formation of nanoparticles with considerable... 

The present work describes the application of nano CoCuFe2O4 toward the coupling reaction of acyl chlorides with terminal alkynes. By this catalytic system, ynone derivatives were formed in high yields via a palladium-free strategy. This protocol avoids the use of phosphine ligands as well as toxic CO sources. Recovery of catalyst by employing an external magnetic field and its reuse up to 9 consecutive trials confirm the robustness of this catalytic system. © 2017 Elsevier B.V  

The synthesis and catalytic behavior of palladium loaded magnetic nanocomposite based on natural polysaccharide salep modified with poly (amino pyridine) is described. The synthesized support is loaded with relatively large amounts of palladium ions (0.34mmol g−1). This is a simple, ecologically safe and cost-effective route for the preparation of the novel heterogeneous catalyst that shows high activity for Suzuki coupling reactions under remarkably mild conditions. Furthermore, the prepared catalyst is magnetically recovered and effectively reused for seven cycles of reactions without significant loss of its catalytic activity and loaded palladium nanoparticles. © 2017  

For the first time the new 32-membered macrocyclic dinuclear palladium complex of two aza-crown macrocycles, bearing two pyridine arms, Pd2L2Cl4 was synthesized and characterized by elemental analysis, IR, NMR spectroscopy and single crystal X-ray diffraction methods. Pd2L2Cl4 was investigated as a moisture/air-stable catalyst for Sonogashira cross-coupling reaction in the absence of copper and phosphine ligand in DMSO. Thermal stability, possible occurrence of tandem reactions, promoted catalytic performance as well as synergistic effects are of advantageous features of Pd2L2Cl4. By employing Taguchi method, optimum conditions (110 °C, 6 h, KOAc, 2 mol% cat.) were determined. Moreover, the...