Recovery of Polyol and Aromatic Amines from Rigid Polyurethane Foams via Ammonolysis.

Polyurethane ranks as one of the most significant plastics globally in terms of production volume and economic value, serving a crucial role in modern society. Due to complexities in the chemical recycling of polyurethane, replacement rates in recycled materials tend to be low, and the recovery of the isocyanate-derived aromatic compounds is often neglected. While many recycling efforts try to address these shortcomings, they primarily focus on TDI-based flexible foams, as recycling rigid PU foams is more challenging.

Chemical upcycling of polybutadiene into size controlled α,ω-dienes and diesters sequential hydrogenation and cross-metathesis.

Plastic waste conversion into valuable chemicals is a promising alternative to landfill or incineration. In particular, the chemical upcycling of polybutadiene rubber (PBR) could provide a renewable route towards highly desirable α,ω-dienes with varying chain lengths, which can find ample industrial application. While previous research has shown that the treatment of polybutadiene with a consecutive hydrogenation and ethenolysis reaction can afford long-chain α,ω-dienes, achieving precise control over the product chain length remains an important bottleneck.

Palladium-catalyzed aerobic homocoupling of aliphatic olefins to dienes: evidence for rate-limiting concerted metalation-deprotonation.

Palladium(ii)-catalyzed dehydrogenative coupling of aliphatic olefins would enable an efficient route to (conjugated) dienes, but remains scarcely investigated. Here, 2-hydroxypyridine (2-OH-pyridine) was found to be an effective ligand for Pd(ii) in the activation of vinylic C(sp)-H bonds. While reoxidation of Pd(0) is challenging in many catalytic oxidations, one can avoid in this reaction that the reoxidation becomes rate-limiting, even under ambient O pressure, by working in coordinating solvents.

Upcycling of Polystyrene to Aromatic Polyacids by Tandem Friedel-Crafts and Oxidation Reactions.

Due to the high demand and the increasing production rate of plastic materials, vast amounts of wastes are generated every year. An important fraction of these wastes contain polystyrene (PS), which is seldom recycled, neither mechanically nor chemically. While several chemical recycling strategies have been developed, they are either very energy-demanding or produce chemicals that can hardly be employed in the synthesis of plastics (e.

Catalytically transforming legacy phthalate esters from plastic waste into benzoic acid and benzoate plasticizers.

This study demonstrates the catalytic conversion of real plastic waste-extracted phthalate plasticizers into benzoic acid (BA), a one-pot hydrolysis-decarboxylation process based on inexpensive CuO and H-beta zeolite, in water as a safe and environmentally benign solvent. As a result of the excellent product selectivity in both reactions, BA was obtained in quantitative yields (>99%). Esterification of the purified carboxylic acid resulted in the production of an alternative benzoate plasticizer, with a total process yield up to 94%.

Shape-Selective Zeolites for Tandem CO Hydrogenation-Carbonylation Reactions.

The valorization of carbon dioxide as a C1 building block in C-C bond forming reactions is a critical link on the road to carbon-circular chemistry. Activation of this inert molecule through reduction with H to carbon monoxide in the reverse water-gas shift (RWGS) reaction can be followed by a wide spectrum of consecutive carbonylation reactions, but the RWGS is severely equilibrium limited at the moderate temperatures of carbonylations. Here we successfully reconcile both reactions in one pot, while avoiding incompatibilities through a zeolite-based compartmentalized approach.

Upcycling polyethylene into closed-loop recyclable polymers through titanosilicate catalyzed C-H oxidation and in-chain heteroatom insertion.

Polyolefins are the most widely produced type of plastics owing to their low production cost and favorable properties. Their polymer backbone consists solely of inert C-C bonds, making them resistant and durable materials. Although this is an extremely useful attribute during their use phase, it complicates chemical recycling.

Overcoming Pd Catalyst Deactivation in the C-H Coupling of Tryptophan Residues in Water Using Air as the Oxidant.

The Pd-catalyzed C-H activation of natural tryptophan residues has emerged as a promising approach for their direct synthetic modification. While using water as the solvent and harnessing air as the oxidant is enticing, these conditions induce catalyst deactivation by promoting the formation of inactive Pd(0) clusters. In this work, we have studied optimized Pd-based catalytic systems via nonsteady state kinetic analysis and X-ray absorption spectroscopy (XAS) to overcome catalyst deactivation, which enables the effective use of lower Pd loadings.

Tandem Electrooxidation - Reductive Amination of Biobased Isohexides Towards Bicyclic Diamines.

Isohexide-derived diamines are considered preferred precursors for the production of biobased polyurethanes and polyamides. However, current synthesis methods from isohexides suffer from serious issues concerning selectivity and the recyclability of the process auxiliaries (e. g.

Effective and sustainable depolymerization of Nylon 66 - a transamidation for the complete recycling of polyamides.

The transamidation of polyamides with short primary amides is reported as an effective recycling technique. This novel depolymerization method is robust and only utilizes cheap and renewable reagents. The process requires a NbO catalyst, assisted by NH, and operates at relatively mild reaction conditions ( 200 °C and 3 bar NH).

Heterogeneous Pt-catalyzed transfer dehydrogenation of long-chain alkanes with ethylene.

The dehydrogenation of long-chain alkanes to olefins and alkylaromatics is a challenging endothermic reaction, typically requiring harsh conditions which can lead to low selectivity and coking. More favorable thermodynamics can be achieved by using a hydrogen acceptor, such as ethylene. In this work, the potential of heterogeneous platinum catalysts for the transfer dehydrogenation of long-chain alkanes is investigated, using ethylene as a convenient hydrogen acceptor.

Adsorption of PFAS by All-Silica Zeolite β: Insights into the Effect of the Water Matrix, Regeneration of the Material, and Continuous PFAS Adsorption.

Per- and polyfluoroalkyl substances (PFAS) are man-made organic compounds ubiquitously present in the environment. Due to their persistency and bioaccumulative nature, and because of increasingly stringent regulations of PFAS, their removal from the environment is necessary. Our initial study identified all-silica zeolite β as an alternative adsorbent with a high selectivity, affinity, and capacity for perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) removal.

Metal-Free Electrocatalytic Diacetoxylation of Alkenes.

1,2-Dioxygenation of alkenes leads to a structural motif ubiquitous in organic synthons, natural products and active pharmaceutical ingredients. Straightforward and green synthesis protocols starting from abundant raw materials are required for facile and sustainable access to these crucial moieties. Especially industrially abundant aliphatic alkenes have proven to be arduous substrates in sustainable 1,2-dioxygenation methods.

Ammonolytic transfer dehydrogenation of amines and amides: a versatile method to valorize nitrogen compounds to nitriles.

The dehydrogenation of amines has been identified as an efficient method for nitrile synthesis. At present, this approach is restricted to (oxidative) dehydrogenations of primary amines, most often with specialized homogeneous catalysts. In this work, amines were transfer dehydrogenated to nitriles using simple and cheap alkenes ( ethylene or propene) as hydrogen scavengers.

Design of an Organic Template for Synthesizing ITR Zeolites under Ge-Free Conditions.

Germanosilicate zeolites with various structures have been extensively synthesized, but the syntheses of corresponding zeolite structures in the absence of germanium species remain a challenge. One such example is an ITR zeolite structure, which is a twin of the ITH zeolite structure. Through the modification of a classic organic template for synthesizing ITH zeolites and thus designing a new organic template with high compatibility to ITR zeolite assisted by theoretical simulation, we, for the first time, show the Ge-free synthesis of an ITR structure including pure silica, aluminosilicate, and borosilicate ITR zeolites.

Copper-cobalt double metal cyanides as green catalysts for phosphoramidate synthesis.

Phosphoramidates are common and widespread backbones of a great variety of fine chemicals, pharmaceuticals, additives and natural products. Conventional approaches to their synthesis make use of toxic chlorinated reagents and intermediates, which are sought to be avoided at an industrial scale. Here we report the coupling of phosphites and amines promoted by a Cu[Co(CN)]-based double metal cyanide heterogeneous catalyst using I as additive for the synthesis of phosphoramidates.

Isopropenyl phosphate as an atom efficient reagent for phosphorylation of alcohols with catalytic base.

The atom efficient transesterification of phosphate esters with catalytic base was investigated using an isopropenyl leaving group, generating acetone as the only by-product. The reaction proceeds in good yields at room temperature, with excellent chemoselectivity towards primary alcohols. Mechanistic insights were obtained by obtaining kinetic data using NMR-spectroscopy.

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.

Catalytic routes towards polystyrene recycling.

Polystyrene (PS) is one of the most popular plastics due to its versatility, which renders it useful for a large variety of applications, including laboratory equipment, insulation and food packaging. However, its recycling is still a challenge, as both mechanical and chemical (thermal) recycling strategies are often cost-prohibitive in comparison to current disposal methods. Therefore, catalytic depolymerization of PS represents the best alternative to overcome these economical drawbacks, since the presence of a catalyst can improve product selectivity for chemical recycling and upcycling of PS.

Dual ligand approach increases functional group tolerance in the Pd-catalysed C-H arylation of -heterocyclic pharmaceuticals.

The excellent functional group tolerance of the Suzuki-Miyaura cross-coupling reactions has been decisive for their success in the pharmaceutical industry. Highly diversified (hetero)aromatic scaffolds can be effectively coupled in the final step(s) of a convergent synthetic route. In contrast, electrophilic Pd catalysts for non-directed C-H activation are particularly sensitive to inhibition by coordinating groups in pharmaceutical precursors.

Oxidative carbonylation of -protected indoles by Rh(III)-zeolites.

The oxidative carbonylation of -protected indoles was investigated to directly synthesize indole-3-carboxylic acids. Using Rh(III)-zeolites as heterogeneous catalysts, the single-site Rh-species reach unprecedented activities (>100 turnovers), while the metal is readily recovered after reaction. X-ray absorption spectroscopy (XAS) provided evidence for site-isolation of Rh(III) species on the zeolite.

Confined Water Cluster Formation in Water Harvesting by Metal-Organic Frameworks: CAU-10-H versus CAU-10-CH.

Several metal-organic frameworks (MOFs) excel in harvesting water from the air or as heat pumps as they show a steep increase in water uptake at 10-30 % relative humidity (RH%). A precise understanding of which structural characteristics govern such behavior is lacking. Herein, CAU-10-H and CAU-10-CH are studied with H, CH corresponding to the functions grafted to the organic linker.

Rational ligand modification maximizes turnover rate in a model Pd-catalyzed C-H arylation.

The direct cross-coupling of (hetero)aromatics without prior functionalization is a promising reaction for the chemical and pharmaceutical industries, enabling the conversion of inexpensive feedstocks in a highly step-efficient manner. However, many C-H arylations rely on high loadings of a Pd catalyst that preclude their use in low-cost applications. In this work, we have maximized the turnover rate of a Pd-catalyzed C-H arylation reaction through rational tuning of the ligands.

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--sulfonic acid (HOSA).