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.

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.

Understanding and Controlling Reactivity Patterns of Pd@CN-Catalyzed Suzuki-Miyaura Couplings.

Using heterogeneous single-atom catalysts (SACs) in the Suzuki-Miyaura coupling (SMC) has promising economic and environmental benefits over traditionally applied palladium complexes. However, limited mechanistic understanding hinders progress in their design and implementation. Our study provides critical insights into the working principles of Pd@CN, a promising SAC for the SMC.

In situ photodeposition of ultra-small palladium particles on TiO.

In situ and operando investigation of photocatalysts plays a fundamental role in understanding the processes of active phase formation and the mechanisms of catalytic reactions, which is crucial for the rational design of more efficient materials. Using a custom-made operando photocatalytic cell, an in situ procedure to follow the formation steps of Pd/TiO photocatalyst by synchrotron-based X-ray absorption spectroscopy (XAS) is proposed. The procedure resulted in the formation of ∼1 nm Pd particles with a much narrower size distribution and homogeneous spreading over TiO support compared with the samples generated in a conventional batch reactor.

Restructuring of Palladium Nanoparticles during Oxidation by Molecular Oxygen.

An interplay between Pd and PdO and their spatial distribution inside the particles are relevant for numerous catalytic reactions. Using in situ time-resolved X-ray absorption spectroscopy (XAS) supported by theoretical simulations, a mechanistic picture of the structural evolution of 2.3 nm palladium nanoparticles upon their exposure to molecular oxygen is provided.

X-ray Spectroscopy at the SuperXAS and Debye Beamlines: from in situ to Operando.

Understanding structure-performance relationships are essential for the rational design of new functional materials or in the further optimization of (catalytic) processes. Due to the high penetration depth of the radiation used, synchrotron-based hard X-ray techniques (with energy > 4.5 keV) allow the study of materials under realistic conditions (in situ and operando) and thus play an important role in uncovering structure-performance relationships.

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.

Droplet-Based Microfluidics Reveals Insights into Cross-Coupling Mechanisms over Single-Atom Heterogeneous Catalysts.

Single-atom heterogeneous catalysts (SACs) hold promise as sustainable alternatives to metal complexes in organic transformations. However, their working structure and dynamics remain poorly understood, hindering advances in their design. Exploiting the unique features of droplet-based microfluidics, we present the first in-situ assessment of a palladium SAC based on exfoliated carbon nitride in Suzuki-Miyaura cross-coupling using X-ray absorption spectroscopy.

Machine Learning for Quantitative Structural Information from Infrared Spectra: The Case of Palladium Hydride.

Infrared spectroscopy (IR) is a widely used technique enabling to identify specific functional groups in the molecule of interest based on their characteristic vibrational modes or the presence of a specific adsorption site based on the characteristic vibrational mode of an adsorbed probe molecule. The interpretation of an IR spectrum is generally carried out within a fingerprint paradigm by comparing the observed spectral features with the features of known references or theoretical calculations. This work demonstrates a method for extracting quantitative structural information beyond this approach by application of machine learning (ML) algorithms.

Probing the Local Structure of Na in NaNO-Promoted, MgO-Based CO Sorbents via X-ray Absorption Spectroscopy.

This work provides insight into the local structure of Na in MgO-based CO sorbents that are promoted with NaNO. To this end, we use X-ray absorption spectroscopy (XAS) at the Na K-edge to interrogate the local structure of Na during the CO capture (MgO + CO ↔ MgCO). The analysis of Na K-edge XAS data shows that the local environment of Na is altered upon MgO carbonation when compared to that of NaNO in the as-prepared sorbent.

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.

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.

Quantitative Structural Description of Zeolites by Machine Learning Analysis of Infrared Spectra.

Application of machine learning (ML) algorithms to spectroscopic data has a great potential for obtaining hidden correlations between structural information and spectral features. Here, we apply ML algorithms to theoretically simulated infrared (IR) spectra to establish the structure-spectrum correlations in zeolites. Two hundred thirty different types of zeolite frameworks were considered in the study whose theoretical IR spectra were used as the training ML set.

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.

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).

Rational Functionalization of UiO-66 with Pd Nanoparticles: Synthesis and In Situ Fourier-Transform Infrared Monitoring.

Functionalization of metal-organic frameworks (MOFs) with noble metal nanoparticles (NPs) is a challenging task. Conventional impregnation by metals often leads to agglomerates on the surface of MOF crystals. Functional groups on linkers interact with metal precursors and promote the homogeneous distribution of NPs in the pores of MOFs, but their uncontrolled localization can block channels and thus hinder mass transport.

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

Trifluoromethyl (CF) 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) is entrapped in the pores of a faujasite support (EMC-1) via a "ship-in-a-bottle" strategy.

Multifunctional Catalyst Combination for the Direct Conversion of CO to Propane.

The production of carbon-rich hydrocarbons via CO valorization is essential for the transition to renewable, non-fossil-fuel-based energy sources. However, most of the recent works in the state of the art are devoted to the formation of olefins and aromatics, ignoring the rest of the hydrocarbon commodities that, like propane, are essential to our economy. Hence, in this work, we have developed a highly active and selective PdZn/ZrO+SAPO-34 multifunctional catalyst for the direct conversion of CO to propane.

Hydrogenation of ethylene over palladium: evolution of the catalyst structure by operando synchrotron-based techniques.

Palladium-based catalysts are exploited on an industrial scale for the selective hydrogenation of hydrocarbons. The formation of palladium carbide and hydride phases under reaction conditions changes the catalytic properties of the material, which points to the importance of operando characterization for determining the relation between the relative fractions of the two phases and the catalyst performance. We present a combined time-resolved characterization by X-ray absorption spectroscopy (in both near-edge and extended regions) and X-ray diffraction of a working palladium-based catalyst during the hydrogenation of ethylene in a wide range of partial pressures of ethylene and hydrogen.

Heterogeneous Single-Site Catalysts for C-H Activation Reactions: Pd(II)-Loaded S,O-Functionalized Metal Oxide-Bisphosphonates.

Heterogeneous single-site catalysts contain spatially isolated, well-defined active sites. This allows not only their easy recovery by solid-liquid separation but also the detailed active site design similar to homogeneous catalysts. Here, heterogeneous Pd(II) single-site catalysts were assembled, based on mesoporous metal oxide-bisphosphonate materials as supports.

In situ formation of surface and bulk oxides in small palladium nanoparticles.

Evolution of surface and bulk palladium oxides in supported palladium nanoparticles was followed in situ using X-ray absorption spectroscopy. The surface oxide was found to be easily reducible in hydrogen at room temperature, while removal of bulk oxide required heating in hydrogen above 100 °C. We also found that the co-presence of hydrogen and oxygen favours a stronger oxidation of palladium particles compared to pure oxygen.