Catalytic tandem dehydrochlorination-hydrogenation of PVC towards valorisation of chlorinated plastic waste.

Chemical treatment of end-of-life PVC at high temperature often results in the formation of polyacetylene and eventually aromatic char. These insoluble conjugated polymers lead to industrial reactor blockages, and limit the efficiency in recycling chlorinated plastic waste. To address this challenge, a solvent-based tandem dehydrochlorination-hydrogenation process is proposed for the conversion of PVC to a saturated polymer backbone. When combining tetrabutylphosphonium ionic liquids and homogeneous Rh catalysts under H2 pressure, 81% dehydrochlorination is reached in 2 h, with the hydrogenation proceeding smoothly with minimal catalyst use of 0.5-2.0 mol% Rh. This process for PVC dechlorination yields soluble products that lack aromatics, have high degrees of dechlorination and possess a tunable content of double bonds. The chemical structures of the partially unsaturated polymer products and of the different structural motifs in the product are accurately monitored by a liquid 1H-NMR method. Finally, X-ray absorption spectroscopy (XAS) sheds light on the catalytic Rh species during the tandem process, which are stabilized by the ionic liquid. This tandem process enables rapid PVC conversion to a saturated organic product, with polyethylene segments giving the opportunity for ensuing recycling steps.

Cu-α-diimine Compounds Encapsulated in Porous Materials as Catalysts for Electrophilic Amination of Aromatic C-H Bonds.

Electrophilic amination has emerged as a more environmentally benign approach to construct arene C-N bonds. However, heterogeneous catalysts remain largely unexplored in this area, even though their use could facilitate product purification and catalyst recovery. Here we investigate strategies to heterogenize a Cu(2,2'-bipyridine) catalyst for the amination of arenes lacking a directing group with hydroxylamine-O-sulfonic acid (HOSA). Besides immobilization of Cu on a metal-organic framework (MOF) or covalent organic framework (COF) with embedded 2,2'-bipyridines, a ship-in-a-bottle approach was followed in which the Cu complex is encapsulated in the pores of a zeolite. Recyclability and hot centrifugation tests show that zeolite Beta-entrapped CuII(2,2'-bipyridine) is superior in terms of stability. With N-methylmorpholine as a weakly coordinating, weak base, simple arenes, such as mesitylene, could be aminated with yields up to 59%, corresponding to a catalyst TON of 24. The zeolite could be used in three consecutive runs without a decrease in activity. Characterization of the catalyst by EPR and XAS showed that the active catalytic complex consisted of a site-isolated CuII species with one 2,2'-bipyridine ligand.

Adsorptive separation using self-assembly on graphite: from nanoscale to bulk processes.

Adsorptive separation is a promising lower-energy alternative for traditional industrial separation processes. While carbon-based materials have a long history in adsorptive removal of organic contaminants from solution or gas mixtures, separation using an adsorption/desorption protocol is rarely considered. The main drawbacks are the limited control in bulk adsorption experiments, as often all organic molecules are adsorbed, and lack of desorption methods to retrieve the adsorbed molecules. Using high-resolution on-surface characterization with scanning tunneling microscopy (STM), an increased understanding of the on-surface adsorption behavior under different conditions was obtained. The insight obtained from the nanoscale experiments was used to develop a highly selective separation method using adsorption and desorption on graphite, which was tested for the separation of quinonoid zwitterions. These experiments on adsorptive separation using self-assembly on graphite show its potential and demonstrate the advantage of combining surface characterization techniques with bulk experiments to exploit different possible applications of carbon-based materials.

Ru-Bipyridine Entrapped in the Supercages of EMC-1 Faujasite as Catalyst for the Trifluoromethylation of Arenes.

Trifluoromethyl (CF3) groups are versatile structural motifs especially in the field of agrochemicals and pharmaceuticals. However, current trifluoromethylation reactions are generally associated with stoichiometric amounts of transition metals/metal oxidants, homogeneous catalysts, high temperatures, and expensive trifluoromethylating agents. In this work, the homogeneous photocatalyst Ru(bipy)32+ is entrapped in the pores of a faujasite support (EMC-1) via a "ship-in-a-bottle" strategy. The formation of the coordination compound was confirmed by Fourier transform infrared (FTIR), UV-Vis spectroscopy, and X-ray absorption spectroscopy (XAS). Due to its high stability toward acidified environments, this single-site heterogeneous catalyst is suitable for the trifluoromethylation of synthetically interesting (hetero)arenes under visible-light irradiation at room temperature. Furthermore, the heterogeneous catalyst could efficiently be reused for at least three times with minimal catalyst leaching/deactivation.

Modulator-Mediated Functionalization of MOF-808 as a Platform Tool to Create High-Performance Mixed-Matrix Membranes.

Modulator-mediated functionalization (MoFu) is introduced as a new and versatile platform tool to improve the separation performance of metal-organic framework (MOF)-based membranes, exemplified here by the creation of mixed-matrix membranes (MMMs) with enhanced CO2 separation efficiency. The unique structure of MOF-808 allows incorporation of CO2-philic modulators in the MOF framework during a one-pot synthesis procedure in water, thus creating a straightforward way to functionalize both MOF and corresponding MMM. As a proof of concept, a series of fluorinated carboxylic acids [trifluoroacetic acid (TFA), pentafluoropropionic acid (PFPA), and heptafluorobutyric acid (HFBA)] and nonfluorinated alkyl carboxylic acids (acetic acid (AA), propionic acid (PA), and butyric acid (BA)) were used as a modulator during MOF-808 synthesis. Two of the best MMMs prepared with 30 wt % MOF-TFA (100% increase in CO2/CH4 separation factor, 350% increase in CO2 permeability) and 10 wt % MOF-PFPA (140% increase in CO2/CH4 separation factor, 100% increase in CO2 permeability) scored very close to or even crossed the 2008 and 2018 upper bound limits for CO2/CH4. Because of its facile functionalization (and its subsequent excellent performance), MOF-808 is proposed as an alternative for widely used UiO-66, which is, from a functionalization point-of-view and despite its widespread use, a rather limited MOF.