Catalytic activity of palladium supported on single wall carbon nanotubes compared to palladium supported on activated carbon Study of the Heck and Suzuki couplings, aerobic alcohol oxidation and selective hydrogenation

Nanoparticles (2–10 nm) of palladium have been deposited on single wall carbon nanotubes (SWNT) by spontaneous reduction from Pd(OAc)₂ or from oxime carbapalladacycle. These catalysts exhibit higher catalytic activity than palladium over activated carbon (Pd/C) for the Heck reaction of styrene and iodobenzene and for the Suzuki coupling of phenylboronic and iodobenzene. This fact has been attributed as reflecting the dramatic influence of the size particle on the activity of the palladium catalyst for CC bond forming reactions as compared to other reaction types less demanding from the point of view of the particle size. Thus, in contrast to the Heck and Suzuki reactions, Pd/C is more active than palladium nanoparticles deposited on SWNT for the catalytic oxidation by molecular oxygen of cinnamyl alcohol to cinnamaldehyde and for the hydrogenation of cinnamaldehyde to 3-phenylpropionaldehyde.     

New emerging trends in synthetic biodegradable polymers - Polylactide: A critique

Polylactide (PLA), the biodegradable synthetic aliphatic polyester, has been studied extensively for a number of applications. With potential applications PLA represents its prospective utility in a number of growing technologies such as orthopedics, drug delivery, sutures, and scaffolds, and have further enhanced the interest of researchers in this novel area. Renewable resource generated monomers possess better mechanical properties and easy processability by conventional methods like thermoforming, injection, and blow molding with non-toxic degradation products, which have made it superior than the other conventional thermoplastics. In order to meet the different performance requirements, PLA can be synthesised by various methods using different catalysts. In this review a collection of more than 100 catalysts for the synthesis of PLA are mentioned, apart from this, efforts have been made to present an updated review on the various aspects of polylactide.     

Activities of octoate salts as novel catalysts for the transesterification of flexible polyurethane foams with diethylene glycol

Polyurethane foams are disposed of not only at the end of their use but also as scrap during slabstock manufacturing, leading to an environmental and economic problem. Flexible polyurethane foams can be advantageously treated by two-phase glycolysis in order to recover their constituent polyols with an improved quality compared to the single phase processes. The glycolysis comprises a transesterification, which has been traditionally catalyzed by alkanolamines, titanium compounds and acetates. In this work, the performance evaluation of new catalysts based on alkaline, alkaline-earth and transition metal octoate salts has been carried out. The carboxylates have showed different catalytic activities according to their basicity and coordination ability. A reaction mechanism for the polyurethane glycolysis in the presence of the carboxylate catalysts studied has also been proposed. The mechanism involves several steps, including the formation of a metal alkoxylate, coordination-insertion of the alkoxide into the urethane group and transfer from recovered polyol to glycol. Among the octoates studied, lithium and stannous octoates showed a remarkable catalytic activity. They yielded the greatest quality for the recovered polyol as well as the highest decomposition rates.     

Fabrication of palladium nanoparticles as effective catalysts by using supramolecular gels

Two-component supramolecular gels were made through self-assembly of tetrazolyl derivatives and Pd(OAc)₂. The robust gels indicated high storage modulus(>10,000 Pa) and loss modulus, which were studied by rheological measurements. The formed Pd nanoparticles(~9 nm) obtained during the formation of the gel showed effective catalytic hydrogenation of nitrobenzene and could be recovered and reused without loss of activity.     

Inside Cover: Ligand Assisted Thermal Atomization of Palladium Clusters: An Inspiring Approach for the Rational Design of Atomically Dispersed Metal Catalysts (Angew. Chem. Int. Ed. 16/2023)

The transformation from metal nanocluster catalysts to metal single-atom catalysts is an important procedure in the rational design of atomically dispersed metal catalysts (ADCs). However, the conversion methods often involve high annealing temperature as well as reducing atmosphere. Herein, we reported a continuous and convenient approach to transfer Pd nanocluster into Pd single-atom in a ligand assisted annealing procedure, by which means we reduced its activating temperature low to 400 °C. Using ex-situ microscopy and spectroscopy, we comprehensively monitored the structural evolution of Pd species though the whole atomization process. Theoretical calculation revealed that the structural instability caused by remaining Cl ligands was the main reason for this low-temperature transformation. The present atomization strategy and mechanistic knowledge for the conversion from cluster to atomic dispersion provides guidelines for the rational design of ADCs.     

Dual-Atomic-Site Catalysts for Molecular Oxygen Activation in Heterogeneous Thermo-/Electro-catalysis

Efficient molecular oxygen activation (MOA) is the key to environmentally friendly catalytic oxidation reactions. In the last decade, single-atomic-site catalysts (SASCs) with nearly 100 % atomic utilization and unique electronic structure have been widely investigated for MOA. However, the single active site makes the activation effect unsatisfactory and difficult to deal with complex catalytic reactions. Recently, dual-atomic-site catalysts (DASCs) have provided a new idea for the effective activation of molecular oxygen (O₂) due to more diverse active sites and synergetic interactions among adjacent atoms. In this review, we systematically summarized the recent research progress of DASCs for MOA in heterogeneous thermo- and electrocatalysis. Finally, we look forward to the challenges and application prospects in the construction of DASCs for MOA.     

An approach utilizing the Response Surface Methodology (RSM) to optimize Adsorption-Desorption of Natural Saudi Arabian Diatomite- with the Box- Behnken Design Technique

Saudi Arabian’s natural diatomite samples were subjected to physical adsorption–desorption characterizations using Brunauer-Emmet-Teller (BET) and the Barrett-Joyner-Halenda (BJH), performed under heating of 140 °C for different periods of hours: 6, 12, 18, and 24 h, to create a central optimization design with surface areas and total pore distributions. Seventeen experimental runs resulted in the primary composite factor design. The surface response describes 100 % variability with a determination coefficient of 1, signifying the quadratic model with an expected correlation coefficient (R²) is satisfied with a standard deviation of 0.2322, demonstrating the high predictability of the model. Moreover, the RSM results have been validated using the t-test with the observed R² value and adjusted R². The model selected with higher F and p values showed<0.0001, which subsequently described the significance of the developed model. The independent components were explained with the help of 3D surface and contour plots that compare the heating time, elapsed time, pressure, and relative pressure against the dependent variable. The plots revealed that the adsorbed quantities well depended on heating time, elapsed time, pressure, relative pressure for isotherm, BET surface area, Langmuir surface area, and t-plot Micropore area.     

Efficient <Emphasis Type="Italic">Baylis-Hillman</Emphasis> Reaction <Emphasis Type="Italic">via</Emphasis> a 1,4-Diazabicyclo[2.2.2]octane-based Ionic Catalyst

Summary. A novel ionic catalyst, 1-butyl-4-aza-1-azoniabicyclo[2.2.2]octane chloride based on 1,4-diazabicyclo[2.2.2]octane was synthesized and applied in the Baylis-Hillman reaction, which occurred readily at room temperature to afford the corresponding adducts in good yield. The ionic catalyst could be recycled for seven runs without diminution in its catalytic activity.     

Molecular iodine: An efficient and environment-friendly catalyst for the synthesis of calix[4]resorcinarenes

Iodine catalyzes the cyclocondensation of various aldehydes with resorcinol to give tetrameric cyclic products, resorcinarenes. Through the reaction of resorcinol with aromatic aldehydes, the product is obtained as a mixture of two isomers, the all-cis isomer (rccc) and the cis-trans-trans isomer (rctt), whereas a single diastereomer, the all-cis, is formed with aliphatic aldehydes. Besides excellent isolated yields, the use of iodine makes this procedure simple, convenient, cost-effective and practical.